Note: Descriptions are shown in the official language in which they were submitted.
CA 02666585 2009-04-16
WO 2008/051321 PCT/US2007/015704
-1-
POLYESTER COMPOSITIONS
FIELD OF THE INVENTION
[0001] The present invention generally relates to polyester compositions made
from terephthalic acid, or an ester thereof, and mixtures thereof, 2,2,4,4-
tetramethyl-1,3-cyclobutanediol, ethylene glycol, and optionally, 1,4-
cyclohexanedimethanol, or chemical equivalents have certain combinations of
two or more of high notched Izod impact strength, certain glass transition
temperature (Tg), certain inherent viscosities, flexural modulus, good
clarity, and
good color, which allow them to be easily formed into articles, for example,
thermoformed sheet and film applications.
BACKGROUND OF THE INVENTION
[0002] Certain commercial polymers, such as bisphenol A polycarbonates,
have glass transition temperatures and notched Izod impact strength desirable
for thermoformed film and sheet but are believed to require drying prior to
thermoforming. Other commercial polymers, such as acrylics and certain impact
modified acrylics, are believed to have the glass transition temperatures
desired
for thermoformed fiim and sheet and are not believed to require drying p~ior
to
thermoforming; however, they are believed to have room temperature notched
lzod impact strengths of typically less than 2 ft-lb/in which is often not
desirable
for certain end use applications. Thus, there is a commercial need for a
polymeric material with a combination of properties making it desirable for
certain
applications, for example, thermoformed film and sheet applications, including
a
combination of two or more of high notched Izod impact strength, certain glass
transition temperature (T9), certain inherent viscosities, certain flexural
modulus,
good clarity, and good color.
[0003] Also, there is a commercial need for a polymeric material with a
combination of properties making it desirable for certain applications, for
CA 02666585 2009-04-16
WO 2008/051321 PCT/US2007/015704
-2-
example, thermoformed film and sheet applications, including a combination of
three or more of high notched Izod impact strength, certain glass transition
temperature (T9), certain inherent viscosities, certain flexural modulus, good
clarity, and good color.
[0004] Tin based catalysts are believed to be efficient for incorporation of
2,2,4,4-tetramethyl-1,3-cyclobutanediol into a polyester. However, tin based
catalysts are believed to produce a yellow to amber colored polyester in the
presence of ethylene glycol. Titanium based catalysts are reported to be
ineffective at incorporating 2,2,4,4-tetramethyl-1,3-cyclobutanediol into a
polyester. See Kelsey et al, Macromolecules 2000, 33, 5810.
100051 In addition, in one embodiment, there is a need in the art for
polyesters
comprising 2,2,4,4-tetramethyl-1,3-cyclobutanediol, ethylene glycol, and,
optionally, cyclohexanedimethanol, which have good color and/or good clarity
and for process(es) to prepare these polyesters.
[0006] Further, in one embodiment, there is a need in the art for a process
which makes it easier to produce the polyesters of the inventions without at
least
one of the following occurring: bubbling, splay formation, color formation,
foaming, off-gassing, and erratic melt levels, i.e., pulsating of the
polyester or the
polyester's production and processing systems. There is also a need in the art
for a process which makes it easier to produce the polyesters of the invention
in
large quantities (for example, pilot run scale and/or commercial production)
without at least one of the aforesaid difficulties occurring.
SUMMARY OF THE INVENTION
[0007] It is believed that certain polyester compositions formed from
terephthalic acid, an ester thereof, and/or mixtures thereof, ethylene glycol,
2,2,4,4-tetramethyl-1,3-cyclobutanediol, and optionally,
cyclohexanedimethanol,
comprising certain thermal stabilizers, reaction products thereof, and
mixtures
thereof, are superior to certain commercial polymers with respect to one or
more
of high notched Izod impact strength, certain glass transition temperature
(Tg),
certain inherent viscosities, good clarity, good color, and certain flexural
modulus.
CA 02666585 2009-04-16
WO 2008/051321 PCT/US2007/015704
-3-
[0008] In certain embodiments of the invention, certain polyesters and/or
polyester compositions of the invention are superior to certain commercial
polymers with respect to a combination of two or more of high notched Izod
impact strength, certain inherent viscosities, certain glass transition
temperature
(T9), certain flexural modulus, good clarity, and good color.
[0009] In some embodiments of the invention, certain polyesters and/or
polyester compositions of the invention are superior to certain commercial
polymers with respect to three or more of high notched Izod impact strength,
certain inherent viscosities, certain glass transition temperature (T9),
certain
flexural modulus, good clarity, and good color.
[0010] In certain embodiments of the invention, certain polyesters and/or
polyester compositions of the invention are superior to certain commercial
polymers with respect to a combination of four or more of high notched Izod '
impact strength, certain inherent viscosities, certain glass transition
temperature
(Tg), certain flexural modulus, good clarity, and good color.
[0011] In other embodiments of the invention, certain polyesters and/or
polyester compositions of the invention are superior to certain commercial
polymers with respect to a combination of all of the following properties:
high
notched Izod impact strength, certain inherent viscosities, certain glass
transition
temperature (T9), certain flexural modulus, good clarity, and good color.
[0012] In one embodiment, copolyesters containing 2,2,4,4-tetramethyl-1,3-
cyclobutanediol and ethylene glycol can be prepared with titanium based
catalysts. In another embodiment, the incorporation of 2,2,4,4-tetramethyl-1,3-
cyclobutanediol can be further improved by use of tin based catalysts in
addition
to the titanium based catalysts_ It is believed that the color of these
copolyesters
can be improved with the addition during poiymerization of certain levels of
phosphorus containing compounds.
[0013] In one embodiment, it is believed that when at least one phosphorus
compound described herein is used during the processes of making the
polyesters according to the present invention, the polyesters can be more
easily
produced without at least one of the following occurring: bubbling, splay
formation, color formation, foaming, off-gassing, and erratic melt levels,
i.e.,
CA 02666585 2009-04-16
WO 2008/051321 PCT/US2007/015704
-4-
pulsating of the polyester or the polyester's production and processing
systems.
In another embodiment, it is believed that at least one process of the
invention
provides a means to more easily produce the polyesters useful in the invention
in
large quantities (for example, pilot run scale and/or commercial production)
without at least one of the aforesaid difficulties occurring. The term "large
quantities" as used herein includes quantities of polyester(s) useful in the
invention which are produced in quantities larger than 100 pounds. In one
embodiment, the term "large quantities", as used herein, includes quantities
of
polyester(s) useful in the invention which are produced in quantities larger
than
1000 pounds.
100141 In one aspect, the processes of making the polyesters useful in the
invention can comprise a batch or continuous process.
[0015] In one aspect, the processes of making the polyesters useful in the
invention comprise a continuous process.
[0016] In one aspect, the invention relates to a polyester composition
comprising at least one polyester which comprises:
(a) a dicarboxylic acid component comprising:
(i) about 90 to about 100 mole % of terephthalic acid residues;
(ii) about 0 to about 10 mole % of aromatic and/or aliphatic
dicarboxylic acid residues having up to 20 carbon atoms; and
(b) a glycol component comprising:
(i) about 1 to less than 90 mole % 2,2,4,4-tetramethyl-1,3-
cyclobutanediol residues; and
(ii) about 0 to about 89 mole % cyclohexanedimethanol
residues;
(iii) greater than 10 mole % ethylene glycol residues, and
(iv) less than about 2 mole % of a modifying glycol having from 3
to 16 carbon atoms;
(c) titanium atoms and phosphorus atoms;
wherein the total mole % of the dicarboxylic acid component is 100 mole %, and
wherein the total mole % of the glycol component is 100 mole %; and
CA 02666585 2009-04-16
WO 2008/051321 PCT/US2007/015704
-5-
wherein the inherent viscosity of the polyester is from 0.50 to 1.2 dUg as
determined in 60/40 (wt/wt) phenol/ tetrachloroethane at a concentration of
0.25
g/50 ml at 25 C.
[00171 In one aspect, the invention relates to a polyester composition
comprising at least one polyester which comprises:
(a) a dicarboxylic acid component comprising:
(i) about 90 to about 100 mole % of terephthalic acid residues;
(ii) about 0 to about 10 mole % of aromatic and/or aliphatic
dicarboxylic acid residues having up to 20 carbon atoms; and
(b) a glycol component comprising:
(i) , about 20 to about 40 mole % 2,2,4,4-tetramethyl-1,3-
cyclobutanediol residues; and
(ii) about 20 to about 40 mole % cyclohexanedimethanol
residues;
(iii) ethylene glycol residues, and
(iv) less than about 2 mole % of a modifying glycol having from 3
to 16 carbon atoms;
(c) titanium atoms and phosphorus atoms;
wherein the total mole % of the dicarboxylic acid component is 100 mole %, and
wherein the total mole % of the glycol component is 100 mole %; and
wherein the inherent viscosity of the polyester is from 0.50 to 1.2 dUg as
determined in 60/40 (wt/wt) phenol/ tetrachloroethane at a concentration of
0.25
g/50 ml at 25 C.
[0018] In one aspect, this invention relates to a polyester composition
comprising at least one polyester which comprises:
(a) a dicarboxylic acid component comprising:
(i) about 90 to about 100 mole % of terephthalic acid residues;
(ii) about 0 to about 10 mole % of aromatic and/or aliphatic
dicarboxylic acid residues having up to 20 carbon atoms; and
(b) a glycol component comprising:
(i) about 20 to about 40 mole % 2,2,4,4-tetramethyl-1,3-
cyclobutanediol residues; and
CA 02666585 2009-04-16
WO 2008/051321 PCT/US2007/015704
-6-
(ii) about 20 to about 40 mole % cyclohexanedimethanol
residues;
(iii) ethylene glycol residues, and
(iv) less than about 2 mole % of a modifying glycol having from 3
to 16 carbon atoms;
(c) titanium atoms and phosphorus atoms;
wherein the total mole % of the dicarboxylic acid component is 100 mole %; and
wherein the total mole % of the glycol component is 100 mole %;
wherein the inherent viscosity of the polyester is from 0.50 to 1.2 dUg as
determined in 60/40 (wt/wt) phenol/ tetrachloroethane at a concentration of
0.25
g/50 mi at 25 C; and
optionally, wherein at least one branching agent is added before and/or during
polymerization of the polyester.
[0019] In one aspect, the invention relates to a polyester composition
comprising at least one polyester which comprises:
(a) a dicarboxylic acid component comprising:
(i) about 90 to about 100 mole % of terephthalic acid residues;
(ii) about 0 to about 10 mole % of aromatic and/or aliphatic
dicarboxylic acid residues having up to 20 carbon atoms; and
(b) a glycol component comprising:
(i) about 20 to about 40 mole % 2,2,4,4-tetramethyl-1,3-
cyclobutanediol residues; and
(ii) about 20 to about 40 mole % cyclohexanedimethanol
residues;
(iii) ethylene glycol residues, and
(iv) less than about 2 mole % of a modifying glycol having from 3
to 16 carbon atoms;
(c) titanium atoms and phosphorus atoms;
wherein the total mole % of the dicarboxylic acid component is 100 mole %, and
wherein the total mole % of the glycol component is 100 mole %;
CA 02666585 2009-04-16
WO 2008/051321 PCT/US2007/015704
-7-
wherein the inherent viscosity of the polyester is from 0.50 to 1.2 dUg as
determined in 60/40 (wt/wt) phenol/ tetrachloroethane at a concentration of
0.25
g/50 ml at 25 C; and
wherein the polyester has at least one of the following properties chosen
from: a
Tg of from about 100 to about 110 C as measured by a TA 2100 Thermal Analyst
Instrument at a scan rate of 20 C/min, a flexural modulus at 23 C equal to or
greater than 290,000 psi as defined by ASTM D790, and a notched Izod impact
strength equal to or greater than 10 ft-lb/in according to ASTM D256 with a 10-
mil
notch using a 1/8-inch thick bar at 23 C.
[0020] In one aspect, this invention relates to a polyester composition
comprising:
(I) at least one polyester which comprises which comprises:
(a) a dicarboxylic acid component comprising:
(i) about 90 to about 100 mole % of terephthalic acid
residues;
(ii) about 0 to about 10 mole % of aromatic and/or
aliphatic dicarboxylic acid residues having up to 20 carbon atoms;
and
(b) a glycol component comprising:
(i) about 20 to about 40 mole % 2,2,4,4-tetramethyl-1,3-
cyclobutanediol residues; and
(ii) about 20 to about 40 mole % cyclohexanedimethanol
residues;
(iii) ethylene glycol residues, and
(iv) less than about 2 mole % of a modifying glycol having
from 3 to 16 carbon atoms;
(c) titanium atoms and phosphorus atoms; and
(II) at least one phosphorus compound chosen from at least one of
alkyl phosphate esters, aryl phosphate esters, mixed alkyl aryl
phosphate esters, reaction products thereof, and mixtures thereof;
wherein the total mole % of the dicarboxylic acid component is 100 mole %, and
CA 02666585 2009-04-16
WO 2008/051321 PCT/US2007/015704
-8-
wherein the total mole % of the glycol component is 100 mole %;
wherein the sum of the mole percentages of 2,2,4,4-tetramethyl-1,3-
cyclobutanediol and cyclohexanedimethanol is from 40 to less than 70 mole % of
the total mole % of the glycol component, and
wherein the inherent viscosity of the polyester is from 0.50 to 1.2 dUg as
determined in 60/40 (wt/wt) phenol/ tetrachloroethane at a concentration of
0.25
g/50 ml at 25 C;
wherein the polyester has at least one of the following properties chosen
from: a
T. of from about 100 to about 110 C as measured by a TA 2100 Thermal Analyst
Instrument at a scan rate of 20 C/min, a flexural modulus at 23 C equal to or
greater than 290,000 psi as defined by ASTM D790, and a notched Izod impact
strength equal to or greater than 10 ft-lb/in according to ASTM D256 with a 10-
mil
notch using a 1/8-inch thick bar at 23 C.
[0021] In one aspect, In one aspect, this invention relates to a polyester
composition comprising:
(I) at least one polyester which comprises which comprises:
(a) a dicarboxylic acid component comprising:
(i) about 90 to about 100 mole % of terephthalic acid
residues;
(ii) about 0 to about 10 mole % of aromatic and/or
aliphatic dicarboxylic acid residues having up to 20 carbon atoms;
and
(b) a glycol component comprising:
(i) . about 20 to about 40 mole % 2,2,4,4-tetramethyl-1,3-
cyclobutanediol residues; and
(ii) about 20 to about 40 mole % cyclohexanedimethanol
residues;
(iii) ethylene glycol residues, and
(iv) less than about 2 mole % of a modifying glycol having
from 3 to 16 carbon atoms;
(c) optionally, at least one branching agent;
CA 02666585 2009-04-16
WO 2008/051321 PCT/US2007/015704
-9-
(II) at least one phosphorus compound chosen from at least one of
alkyl phosphate esters, aryl phosphate esters, mixed alkyl aryl
phosphate esters, reaction products thereof, and mixtures thereof;
and
(III) titanium atoms and phosphorus atoms;
wherein the total mole % of the dicarboxylic acid component is 100 mole %, and
wherein the total mole % of the glycol component is 100 mole %;
wherein the sum of the mole percentages of 2,2,4,4-tetramethyl-1,3-
cyclobutanediol and cyclohexanedimethanol is from 40 to less than 70 mole % of
the total mole % of the glycol component, and
wherein the inherent viscosity of the polyester is from 0.50 to 1.2 dUg as
determined in 60/40 (wt/wt) phenol/ tetrachloroethane at a concentration of
0.25
g/50 ml at 25 C.
[0022] In one aspect, this invention relates to a process comprising the
following steps:
(I) heating a mixture at at least one temperature chosen from 150 C to
250 C, under at least one pressure chosen from the range of 0 psig to 75
psig wherein said mixture comprises:
(a) a dicarboxylic acid component comprising:
(i) about 90 to about 100 mole % of terephthalic acid
residues;
(ii) about 0 to about 10 mole % of aromatic and/or
aliphatic dicarboxylic acid residues having up to 20 carbon
atoms; and
(b) a glycol component comprising:
(i) about 1 to less than 90 mole % 2,2,4,4-tetramethyl-
1,3-cyclobutanediol residues; and
(ii) about 0 to about 89 mole % cyclohexanedimethanol
residues;
(iii) greater than 10 mole % ethylene glycol residues, and
less than about 2 mole % of a modifying glycol having from 3 to 16
carbon atoms;
CA 02666585 2009-04-16
WO 2008/051321 PCT/US2007/015704
-10-
wherein the molar ratio of glycol component/dicarboxylic acid
component added in Step (I) is 1.01-3.0/1.0;
wherein the mixture in Step (I) is heated in the presence of:
(i) at least one catalyst comprising at least one titanium compound,
and, optionally, at least one catalyst chosen from tin, gallium, zinc,
antimony, cobalt, manganese, magnesium; germanium, lithium,
aluminum compounds and an aluminum compound with lithium
hydroxide or sodium hydroxide; and (ii) at least one phosphorus
compound, reaction products thereof, and mixtures thereof;
(II) heating the product of Step (I) at a temperature of 230 C to 320 C
for 1 to 6 hours, under at least one pressure chosen from the range of the
final pressure of Step (I) to 0.02 torr absolute, to form a final polyester;
wherein the total mole % of the dicarboxylic acid component of the final
polyester
is 100 mole %; and wherein the total mole % of the glycol component of the
final
polyester is 100 mole %;
wherein the inherent viscosity of the polyester is from 0.50 to 1.2 dUg as
determined in 60/40 (wt/wt) phenol/ tetrachloroethane at a concentration of
0.25
g/50 ml at 25 C.
[0023] In one aspect, this invention relates to a process comprising the
following steps:
(I) heating a mixture at at least one temperature chosen from 150 C to
250 C, under at least one pressure chosen from the range of 0 psig to 75
psig wherein said mixture'comprises:
(a) a dicarboxylic acid component comprising:
(i) about 90 to about 100 mole % of terephthalic acid
residues;
(ii) about 0 to about 10 mole % of aromatic and/or
aliphatic dicarboxylic acid residues having up to 20 carbon
atoms; and
(b) a glycol component comprising:
(i) about 1 to less than 90 mole % 2,2,4,4-tetramethyl-
1,3-cyclobutanediol residues; and
CA 02666585 2009-04-16
WO 2008/051321 PCT/US2007/015704
-11-
(ii) about 1 to about 89 mole % cyclohexanedimethanol
residues;
(iii) greater than 10 mole % ethylene glycol residues, and
(iv) less than about 2 mole % of a modifying glycol having from 3
to 16 carbon atoms;
wherein the molar ratio of glycol component/dicarboxylic acid
component added in Step (I). is 1.01-3.0/1.0;
wherein the mixture in Step (I) is heated in the presence of:
(i) at least one catalyst comprising at least one titanium compound,
and, optionally, at least one catalyst chosen from tin, gallium, zinc,
antimony, cobalt, manganese, magnesium, germanium, lithium,
aluminum compounds and an aluminum compound with lithium
hydroxide or sodium hydroxide; and (ii) at least one phosphorus
compound;
(II) heating the product of Step (I) at a temperature of 230 C to 320 C
for I to 6 hours, under at least one pressure chosen from the range of the
final pressure of Step (I) to 0.02 torr absolute, to form a final polyester;
wherein the total mole % of the dicarboxylic acid component of the final
polyester
is 100 mole %; wherein the total mole % of the glycol component of the final
polyester is 100 mole %; and
wherein the inherent viscosity of the polyester is from 0.50 to 1.2 dUg as
determined in 60/40 (wt/wt) phenol/ tetrachloroethane at a concentration of
0.25
g/50 ml at 25 C.
[0024] In one aspect, the invention relates to a process for making a
polyester
comprising the following steps:
(I) heating a mixture at at least one temperature chosen from 150 C to
250 C, under at least one pressure chosen from the range of 0 psig to 75
psig wherein said mixture comprises:
(a) a dicarboxylic acid component comprising:
(i) about 90 to about 100 mole % of terephthalic acid
residues;
CA 02666585 2009-04-16
WO 2008/051321 PCT/US2007/015704
-12-
(ii) about 0 to about 10 mole % of aromatic and/or
aliphatic dicarboxylic acid residues having up to 20 carbon
atoms; and
(b) a glycol component comprising:
(i) about 20 to about 40 mole % 2,2,4,4-tetramethyl-1,3-
cyclobutanediol residues; and
(ii) about 20 to about 40 mole % cyclohexanedimethanol
residues;
(iii) ethylene glycol residues, and
(iv) less than about 2 mole % of a modifying glycol having
from 3 to 16 carbon atoms;
wherein the molar ratio of glycol component/dicarboxylic acid
component added in Step (I) is 1.01-3.0/1.0;
wherein the mixture in Step (I) is heated in the presence of:
(i) at least one catalyst comprising at least one titanium compound,
and, optionally, at least one catalyst chosen from tin, gallium, zinc,
antimony, cobalt, manganese, magnesium, germanium, lithium,
aluminum compounds and an aluminum compound with lithium
hydroxide or sodium hydroxide; and (ii) at least one phosphorus
compound;
(II) heating the product of Step (I) at a temperature of 230 C to 320 C
for 1 to 6 hours, under at least one pressure chosen from the range of the
final pressure of Step (I) to 0.02 torr absolute, to form a final polyester;
wherein the total mole % of the dicarboxylic acid component of the final
polyester
is 100 mole %; wherein the total mole % of the glycol component of the final
polyester is 100 mole %; and
wherein the inherent viscosity of the polyester is from 0.50 to 1.2 dUg as
determined in 60/40 (wt/wt) phenol/ tetrachloroethane at a concentration of
0.25
g/50 ml at 25 C.
[0025] In one aspect, the invention relates to a process for making a
polyester
comprising the following steps:
CA 02666585 2009-04-16
WO 2008/051321 PCT/US2007/015704
-13-
(I) heating a mixture at at Ieast one temperature chosen from 150 C to
250 C, under at least one pressure chosen from the range of 0 psig to 75
psig wherein said mixture comprises:
(a) a dicarboxylic acid component comprising:
(i) about 90 to about 100 mole % of terephthalic acid
residues;
(ii) about 0 to about 10 mole % of aromatic and/or
aliphatic dicarboxylic acid residues having up to 20 carbon
atoms; and
(b) a glycol component comprising:
(i) about 1 to less than 90 mole % 2,2,4,4-tetramethyl-
1,3-cyclobutanediol residues; and
(ii) about 0 to about 89 mole % cyclohexanedimethanol
residues;
(iii) greater than 10 mole % ethylene glycol residues, and
(iv) less than about 2 mole % of a modifying glycol having
from 3 to 16 carbon atoms;
wherein the molar ratio of glycol component/dicarboxylic acid
component added in Step (I) is 1.01-3.0/1.0;
wherein the mixture in Step (I) is heated in the presence of:
(i) at least one catalyst comprising at least one titanium compound,
at least one tin compound, and optionally, at least one catalyst
chosen from gallium, zinc, antimony, cobalt, manganese,
magnesium, germanium, lithium, aluminum compounds and an
aluminum compound with lithium hydroxide or sodium hydroxide;
and (ii) at least one phosphorus compound;
(II) heating the product of Step (I) at a temperature of 230 C to 320 C
for 1 to 6 hours, under at least one pressure chosen from the range of the
final pressure of Step (I) to 0.02 torr absolute, to form a final polyester;
wherein the total mole % of the dicarboxylic acid component of the final
polyester
is 100 mole %; and wherein the total mole % of the glycol component of the
final
polyester is 100 mole %; and
CA 02666585 2009-04-16
WO 2008/051321 PCT/US2007/015704
-14-
wherein the inherent viscosity of the polyester is from 0.50 to 1.2 dUg as
determined in 60/40 (wt/wt) phenol/ tetrachloroethane at a concentration of
0.25
g/50 ml at 25 C.
[0026] In one aspect, the invention relates to a process for making a
polyester
comprising the following steps:
(I) heating a mixture at at least one temperature chosen from 150 C to
250 C, under at least one pressure chosen from the range of 0 psig to 75
psig wherein said mixture comprises:
(a) a dicarboxylic acid component comprising:
(i) about 90 to about 100 mole % of terephthalic acid
residues;
(ii) about 0 to about 10 mole % of aromatic and/or
aliphatic dicarboxylic acid residues having up to 20 carbon
atoms; and
(b) a glycol component comprising:
(i) about 20 to about 40 mole % 2,2,4,4-tetramethyl-1,3-
cyclobutanediol residues; and
(ii) about 20 to about 40 mole % cyclohexanedimethanol
residues;
(iii) about 30 to about 60 mole % ethylene glycol residues,
and
(iv). less than about 2 mole % of a modifying glycol having
from 3 to 16 carbon atoms;
wherein the molar ratio of glycol component/dicarboxylic acid
component added in Step (I) is 1.01-3.0/1.0;
wherein the mixture in Step (I) is heated in the presence of:
(i) at least one catalyst comprising at least one titanium compound,
at least one tin compound, and optionally, at 1east one catalyst
chosen from gallium, zinc, antimony, cobalt, manganese,
magnesium, germanium, lithium, aluminum compounds and an
aluminum compound with lithium hydroxide or sodium hydroxide;
and (ii) at least one phosphorus compound;
CA 02666585 2009-04-16
WO 2008/051321 PCT/US2007/015704
-15-
(II) heating the product of Step (I) at a temperature of 230 C to 320 C
for 1 to 6 hours, under at least one pressure chosen from the range of the
final pressure of Step (I) to 0.02 torr absolute, to form a final polyester;
wherein the total mole % of the dicarboxylic acid component of the final
polyester
is 100 mole %; and wherein the total mole % of the glycol component of the
final
polyester is 100 mole %; and
wherein the inherent viscosity of the polyester is from 0.50 to 1.2 dUg as
determined in 60/40 (wt/wt) phenol/ tetrachloroethane at a concentration of
0.25
g/50 ml at 25 C.
[0027] In one aspect, the invention relates to a process for making a
polyester
comprising the following steps:
(I) heating a mixture at at least one temperature chosen from 150 C to
250 C, under at least one pressure chosen from the range of 0 psig to 75
psig wherein said mixture comprises:
(a) a dicarboxylic acid component comprising:
(i) about 90 to about 100 mole % of terephthalic acid
residues;
(ii) about 0 to about 10 mole % of aromatic and/or
aliphatic dicarboxylic acid residues having up to 20 carbon
atoms; and
(b) a glycol component comprising:
(i) about 20 to about 40 mole % 2,2,4,4-tetramethyl-1,3-
cyclobutanediol residues; and
(ii) about 20 to about 40 mole % cyclohexanedimethanol
residues;
(iii) ethylene glycol residues, and
(iv) less than about 2 mole % of a modifying glycol having
from 3 to 16 carbon atoms;
wherein the molar ratio of glycol component/dicarboxylic acid
component added in Step (I) is 1.01-3.0/1.0;
wherein the mixture in Step (I) is heated in the presence of:
CA 02666585 2009-04-16
WO 2008/051321 PCT/US2007/015704
-16-
(i) at least one catalyst comprising at least one titanium compound,
at least one tin compound, and optionally, at least one catalyst
chosen from gallium, zinc, antimony, cobalt,~ manganese,
magnesium, germanium, lithium, aluminum compounds and an
aluminum compound with lithium hydroxide or sodium hydroxide;
and (ii) at least one phosphorus compound;.
(11) heating the product of Step (I) at a temperature of 230 C to 320 C
for 1 to 6 hours, under at least one pressure chosen from the range of the
final pressure of Step (I) to 0.02 torr absolute, to for,,m a final polyester;
wherein the total mole % of the dicarboxylic acid component of the final
polyester
is 100 mole %; and wherein the total mole % of the glycol component of the
final
polyester is 100 mole %;
wherein the sum of the mole percentages of 2,2,4,4-tetramethyl-1,3-
cyclobutanediol and cyclohexanedimethanol of the final polyester is from 40 to
less than 70 mole % of the total mole % of the glycol component, and
wherein the inherent viscosity of the polyester is from 0.50 to 1.2 dUg as
determined in 60/40 (wt/wt) phenol/ tetrachloroethane at a concentration of
0.25
g/50 ml at 25 C.
[0028] In one aspect, for the polyester(s) useful in the invention and for the
processes useful in the invention, the b* values for the polyesters useful in
the
invention can be from -12 to less than 12, [in one embodiment, in the presence
of
and/or in the absence of toner(s)], as determined by the L*a*b* color system
of
the CIE (international Commission on Illumination) (translated), wherein L*
represents the lightness coordinate, a* represents the red/green coordinate,
and
b* represents the yellow/blue coordinate. In one embodment, the b* values for
the polyesters useful in the invention [in one embodiment, in the presence of
and/or in the absence of toner(s)] can be from 0 to 10. In one embodment, the
b*
values for the polyesters useful in the invention [in one embodiment, in the
presence of and/or in the absence of toner(s)] can be from -0 to 5.
[0029] In one aspect, the invention includes thermoformed sheet(s) which can
comprise any of the polyester compositions of the invention.
CA 02666585 2009-04-16
WO 2008/051321 PCT/US2007/015704
-17-
[0030] In one aspect, the polyesters useful in the invention can comprise at
least one phosphate ester whether or not present as a thermal stabilizer.
[0031] In one aspect, the polyesters useful in the invention can comprise at
least one phosphate ester described herein which is present as a thermal
stabilizer.
[0032] In one aspect, the polyesters useful in the invention contain no
branching agent, or alternatively, at least one branching agent is added
either
prior to or during polymerization of the polyester.
[0033] In one aspect, the polyesters useful in the invention contain at least
one branching agent without regard to the method or sequence in which it is
added.
[0034] In one aspect, certain polyesters useful in the invention may be
amorphous or semicrystalline. In one aspect, certain polyesters useful in the
invention can have a relatively low crystallinity. Certain polyesters useful
in the
invention can thus have a substantially amorphous morphology, meaning that the
polyesters comprise substantially unordered regions of polymer.
[0035] In one aspect, the polyesters, polyester compositions and/or processes
of the invention useful in the invention can comprise at least one phosphorus
compound.
[0036] In one aspect, the polyesters, polyester compositions and/or processes
of the invention useful in the invention can comprise phosphorus atoms.
[0037] In one aspect, the polyesters and/or polyester compositions of the
invention can comprise titanium atoms and tin atoms.
[0038] In one aspect, the polyesters, polyester compositions and/or processes
of the invention can comprise phosphorus atoms, tin atoms, and titanium atoms.
100391 In one aspect, the polyesters, polyester compositions and/or processes
of the invention useful in the invention can comprise phosphorus atoms and
titanium atoms.
[0040] In one aspect, the invention can comprise phosphorus atoms, tin
atoms, and titanium atoms.
[0041] In one aspect, any of the polyester(s), polyester compositions and/or
processes of the invention may comprise at least one phosphorus compound.
CA 02666585 2009-04-16
WO 2008/051321 PCT/US2007/015704
-18-
[0042] In one aspect, any of the polyester(s), polyester compositions and/or
processes of the invention may comprise at least one titanium compound.
[0043] In one aspect, any of the polyester(s), polyester compositions and/or
processes of the invention may comprise at least one titanium compound and at
least one phosphorus compound.
[0044] In one aspect, any of the polyester(s), polyester compositions and/or
processes of the invention may comprise (i) at least one titanium compound, at
and optionally, at least one compound chosen from tin, gallium, zinc,
antimony,
cobalt, manganese, magnesium, germanium, lithium, aluminum compounds and
an aluminum compound with lithium hydroxide or sodium hydroxide; and (ii) at
least one phosphorus compound. The term "phosphorus compound" is intended
to include reaction products thereof.
[0045] In one aspect, any of the polyester(s), polyester compositions and/or
processes of the invention may comprise (i) at least one titanium compound, at
least one tin compound, and optionally, at least one compound chosen from
gallium, zinc, antimony, cobalt, manganese, magnesium, germanium, lithium,
aluminum compounds and an aluminum compound with lithium hydroxide or
sodium hydroxide; and (ii) at least one phosphorus compound.
[0046] In one aspect, any of the polyester(s), polyester compositions and/or
processes of making the polyesters useful in the invention may comprise at
least
one tin compound and at least one titanium compound.
[0047] In one aspect, any of the polyester(s), polyester compositions and/or
processes of making the polyesters useful in the invention may comprise at
least
one tin compound, at least one titanium compound, and at least one phosphorus
compound.
[0048] In one aspect, at least one phosphorus compound useful in the
invention comprise phosphoric acid, phosphorous acid, phosphonic acid,
phosphinic acid, phosphonous acid, and various esters and salts thereof. The
esters can be alkyl, branched alkyl, substituted alkyl, difunctional alkyl,
alkyl
ethers, aryl, and substituted aryl.
[0049] In one aspect, at least one phosphorus compound useful in the
invention comprise at least one phosphorus compound chosen from at least one
CA 02666585 2009-04-16
WO 2008/051321 PCT/US2007/015704
-19-
of substituted or unsubstituted alkyl phosphate esters, substituted or
unsubstituted aryl phosphate esters, substituted or unsubstituted mixed alkyl
aryl
phosphate esters, diphosphites, salts of phosphoric acid, phosphine oxides,
and
mixed alkyl aryl phosphites, reaction products thereof, and mixtures thereof.
The
phosphate esters include esters in which the phosphoric acid is fully
esterified or
only partially esterified.
[0050] In one aspect, at least one phosphorus compound useful in the
invention comprise at least one phosphorus compound chosen from at least one
of substituted or unsubstituted alkyl phosphate esters, substituted or -
unsubstituted aryl phosphate esters, mixed substituted or unsubstituted alkyl
aryl
phosphate esters, reaction products thereof, and mixtures thereof. The
phosphate esters include esters in which the phosphoric acid is fully
esterified or
only partially esterified.
[0051] In one aspect, at least one phosphorus compound useful in the
invention are chosen from at least one of alkyl phosphate esters, aryl
phosphate
esters, mixed alkyl aryl phosphate esters, reaction products, thereof, and
mixtures thereof.
[0052] In one aspect, at least one phosphorus compound useful in the
invention may comprise at least one aryl phosphate ester.
[0053] In one aspect, at least one phosphorus compound useful in the
invention may comprise at least one unsubstituted aryl phosphate ester.
[0054] In one aspect, at least one phosphorus compound useful in the
invention may comprise at least one aryl phosphate ester which is not
substituted
with benzyl groups.
[0055] In one aspect, at least one phosphorus compound useful in the
invention may comprise at least one triaryl phosphate ester.
[0056] In one aspect, at least one phosphorus compound useful in the
invention may comprise at least one triaryl phosphate ester which is not
substituted with benzyl groups.
[0057] In one aspect, at least one phosphorus compound useful in the
invention may comprise at least one alkyl phosphate ester.
CA 02666585 2009-04-16
WO 2008/051321 PCT/US2007/015704
-20-
[0058] In one aspect, at least one phosphorus compound useful in the
invention may comprise triphenyl phosphate and/or Merpol A. In one
embodiment, any of the polyester compositions of the invention may comprise
triphenyl phosphate.
[0059] In one aspect, any of the processes described herein for making any of
the polyester compositions and/or polyesters can comprise at least one mixed
alkyl aryl phosphite, such as, for example, bis(2,4-
dicumylphenyl)pentaerythritol
diphosphite also known as Doverphos S-9228 (Dover Chemicals, CAS# 154862-
43-8).
[0060] In one aspect, any of the processes described herein for making any of
the polyester compositions and/or polyesters can comprise at least one one
phosphine oxide.
[0061] In one aspect, any of the processes described herein for making any of
the polyester compositions and/or polyesters can comprise at least one salt of
phosphoric acid such as, for example, KH2PO4 and Zn3(PO4)2.
[0062] In one aspect, any of processes described herein for making the
polyester compositions and/or polyesters comprise at least one of the
phosphorus compounds described herein.
[0063] It is believed that any of the processes of making the polyesters
useful
in the invention may be used to make any of the polyesters useful in the
invention.
[0064] In one aspect, the pressure used in Step (I) of any of the processes of
the invention consists of at least one pressure chosen from 0 psig to 75 psig.
In
one embodiment, the pressure used in Step (I) of any of the processes of the
invention consists of at least one pressure chosen from 0 psig to 50 psig.
[0065] In one aspect, the pressure used in Step (II) of any of the processes
of
the invention consists of at least one pressure chosen from 20 torr absolute
to
0.02 torr absolute; in one embodiment, the pressure used in Step (II) of any
of the
processes of the invention consists of at least one pressure chosen from 10
torr
absolute to 0.02 torr absolute; in one embodiment, the pressure used in Step
(II)
of any of the processes of the invention consists of at least one pressure
chosen
from 5 torr absolute to 0.02 torr absolute; in one embodiment, the pressure
used
CA 02666585 2009-04-16
WO 2008/051321 PCT/US2007/015704
-21-
in Step (lI) of any of the processes of the invention consists of at least one
pressure chosen from 3 torr absolute to 0.02 torr absolute; in one embodiment,
the pressure used in Step (11) of any of the processes of the invention
consists of
at least one pressure chosen from 20 torr absolute to 0.1 torr absolute; in
one
embodiment, the pressure used in Step (II) of any of the processes of the
invention consists of at least one pressure chosen from 10 torr absolute to
0.1
torr absolute; in one embodiment, the pressure used in Step (II) of any of the
processes of the invention consists of at least one pressure chosen from 5
torr
absolute to 0.1 torr absolute; in one embodiment, the pressure used in Step
(II) of
any of the processes of the invention consists of at least one pressure chosen
from 3 torr absolute to 0.1 torr absolute.
[0066] In one aspect, the molar ratio of glycol component/dicarboxylic acid
component added in Step (I) of any of the processes of the invention is 1.0-
3.0/1.0; in one aspect, the molar ratio of glycol component/dicarboxylic acid
component added in Step (I) of any of the processes of the invention is 1.0-
2.5/1.0; in one aspect, the molar ratio of glycol component/dicarboxylic acid
component added in Step (I) of any of the processes of the invention is 1.0-
2.0/1.0; in one aspect, the molar ratio of glycol component/dicarboxylic acid
component added in Step (I) of any of the processes of the invention is 1.0-
1.75/1.0; in one aspect, the molar ratio of glycol component/dicarboxylic acid
component added in Step (I) of any of the processes of the invention is 1.0-
1.5/1Ø
[0067] In one aspect, the molar ratio of glycol component/dicarboxylic acid
component added in Step (I) of any of the processes of the invention is 1.01-
3.0/1.0; in one aspect, the molar ratio of glycol component/dicarboxylic acid
component added in Step (I) of any of the processes of the invention is 1.01-
2.5/1.0; in one aspect, the molar ratio of glycol component/dicarboxylic acid
component added in Step (I) of any of the processes of the invention is 1.01-
2.0/1.0; in one aspect, the molar ratio of glycol component/dicarboxylic acid
component added in Step (I) of any of the processes of the invention is 1.01-
1.75/1.0; in one aspect, the molar ratio of glycol component/dicarboxylic acid
CA 02666585 2009-04-16
WO 2008/051321 PCT/US2007/015704
-22-
component added in Step (I) of any of the processes of the invention is 1.01-
1.5/1Ø
[0068] In any of the process embodiments for making the polyesters useful in
the invention, the heating time of Step (II) may be from 1 to 5 hours. In any
of the
process embodiments for making the polyesters useful in the invention, the
heating time of Step (II) may be from 1 to 4 hours. In any of the process
embodiments for making the polyesters useful in the invention, the heating
time
of Step (II) may be from 1 to 3 hours. In any of the process embodiments for
making the polyesters useful in the invention, the heating time of Step (II)
may be
from 1.5 to 3 hours. In any of the process embodiments for making the
polyesters useful in the invention, the heating time of Step (II) may be from
1 to 2
hours.
[0069] In one aspect, the addition of the phosphorus compound(s) in the
process(es) of the invention can result in a weight ratio of total phosphorus
atoms
to total tin atoms in the final polyester of 0-20:1. In one embodiment, the
addition
of the phosphorus compound(s) in the process(es) of the invention can result
in a
weight ratio of total phosphorus atoms to total tin atoms in the final
polyester of 1-
20:1.
[0070] In one aspect, the addition of the phosphorus compound(s) in the
process(es) of the invention can result in a weight ratio of total phosphorus
atoms
to total tin atoms in the final polyester of 0-15:1. In one embodiment, the
addition
of the phosphorus compound(s) in the process(es) of the invention can result
in a
weight ratio of total phosphorus atoms to total tin atoms in the final
polyester of 1-
15:1.
[0071] In one aspect, the addition of the phosphorus compound(s) in the
process(es) can result in a weight ratio of total phosphorus atoms to total
tin
atoms in the final polyester of 0-10:1. In one embodiment, the addition of the
phosphorus compound(s) in the process(es) of the invention can result in a
weight ratio of total phosphorus atoms to total tin atoms in the final
polyester of 1-
10:1.
[0072] In one aspect, the addition of the phosphorus compound(s) in the
process(es) can result in a weight ratio of total phosphorus atoms to total
tin
CA 02666585 2009-04-16
WO 2008/051321 PCT/US2007/015704
-23-
atoms in the final polyester of 0-5:1. In one embodiment, the addition of the
phosphorus compound(s) in the process(es) of the invention can result in a
weight ratio of total phosphorus atoms to total tin atoms in the final
polyester of 1-
5:1.
[0073] In one aspect, the addition of the phosphorus compound(s) in the
process(es) can result in a weight ratio of total phosphorus atoms to total
tin
atoms in the final polyester of 0-3:1. In one embodiment, the addition of the
phosphorus compound(s) in the process(es) can result in a weight ratio of
total
phosphorus atoms to total tin atoms in the final polyester of 1-3:1.
[0074] For example, the weight of tin atoms and phosphorus atoms present in
the final polyester can be measured in ppm and can result in a weight ratio of
total phosphorus atoms to total tin atoms in the final polyester of any of the
aforesaid weight ratios.
[0075] In one aspect, the addition of the phosphorus compound(s) in the
process(es) of the invention can result in a weight ratio of total phosphorus
atoms
to total titanium atoms in the final polyester of 0-20:1. In one embodiment,
the
addition of the phosphorus compound(s) in the process(es) of the invention can
result in a weight ratio of total phosphorus atoms to total titanium atoms in
the
final polyester of 1-20:1.
[0076] In one aspect, the addition of the phosphorus compound(s) in the
process(es) of the invention can result in a weight ratio of total phosphorus
atoms
to total titanium atoms in the final polyester of 0-15:1. In one embodiment,
the
addition of the phosphorus compound(s) in the process(es) of the invention can
result in a weight ratio of total phosphorus atoms to total titanium atoms in
the
final polyester of 1-15:1.
[0077] In one aspect, the addition of the phosphorus compound(s) in the
process(es) can result in a weight ratio of total phosphorus atoms to total
titanium
atoms in the final polyester of 0-10:1. In one embodiment, the addition of the
phosphorus compound(s) in the process(es) of the invention can result in a
weight ratio of total phosphorus atoms to total titanium atoms in the final
polyester of 1-10:1.
CA 02666585 2009-04-16
WO 2008/051321 PCT/US2007/015704
-24-
[0078] In one aspect, the addition of the phosphorus compound(s) in the
process(es) can result in a weight ratio of total phosphorus atoms to total
titanium
atoms in the final polyester of 0-5:1. In one embodiment, the addition of the
phosphorus compound(s) in the process(es) of the invention can result in a
weight ratio of total phosphorus atoms to total titanium atoms in the final
polyester of 1-5:1.
[0079] In one aspect, the addition of the phosphorus compound(s) in the
process(es) can result in a weight ratio of total phosphorus atoms to total
titanium
atoms in the final polyester of 0-3:1. In one embodiment, the addition of the
phosphorus compound(s) in the process(es) can result in a weight ratio of
total
phosphorus atoms to total titanium atoms in the final polyester of 1-3:1.
[0080] For example, the weight of titanium atoms and phosphorus atoms
present in the final polyester can be measured in ppm and can result in a
weight
ratio of total phosphorus atoms to total titanium atoms in the final polyester
of any
of the aforesaid weight ratios.
100811 In one aspect, the amount of tin atoms in the polyesters useful in the
invention can be from 0 to 400 ppm tin atoms based on the weight of the final
polyester.
[0082] In one aspect, the amount of tin atoms in the polyesters useful in the
invention can be from 15 to 400 ppm tin atoms based on the weight of the final
polyester.
[0083] In one aspect, the amount of titanium atoms in the polyesters useful in
the invention can be from 0 to 400 ppm titanium atoms based on the weight of
the final polyester.
[0084] In one aspect, the amount of titanium atoms in the polyesters useful in
the invention can be from 15 to 400 ppm titanium atoms based on the weight of
the final polyester.
[0085] In one aspect, the amount of phosphorus atoms in the polyesters
useful in the invention can be from 1 to 500 ppm phosphorus atoms based on the
weight of the final polyester.
[0086] In one aspect, the amount of phosphorus atoms in the polyesters
useful in the invention can be from 1 to 500 ppm phosphorus atoms based on the
CA 02666585 2009-04-16
WO 2008/051321 PCT/US2007/015704
-25-
weight of the final polyester and the amount of titanium atoms in the
polyester
can be from 1 to 100 ppm titanium atoms based on the weight of the final
polyester.
[0087] In one aspect, the amount of phosphorus atoms in the polyesters
useful in the invention can be from 1 to 500 ppm phosphorus atoms based on the
weight of the final polyester and the amount of titanium atoms in the
polyester
can be from I to 400 ppm titanium atoms based on the weight of the final
polyester.
[0088] In one aspect, the amount of phosphorus atoms in the polyesters
useful in the invention can be from 1 to 500 ppm phosphorus atoms based on the
weight of the final polyester and the amount of titanium atoms in the
polyester
can be from 1 to 100 ppm titanium atoms based on the weight of the final
polyester.
[0089] In one aspect, the amount of phosphorus atoms in the polyester(s)
useful in the invention can be from 1 to 500 ppm phosphorus atoms based on the
weight of the final polyester, the amount of tin atoms in the polyester(s)
useful in
the invention can be from 1 to 400 ppm tin atoms based on the weight of the
final
polyester, and the amount of titanium atoms in the polyester can be from 1 to
100
ppm titanium atoms based on the weight of the final polyester.
[0090] In one aspect, the polyester compositions are useful in articles of
manufacture including, but not limited to, extruded, calendered, and/or molded
articles including, but not limited to, injection molded articles, extruded
articles,
cast extrusion articles, profile extrusion articles, melt spun articles,
thermoformed
articles, extrusion molded articles, injection blow molded articles, injection
stretch
blow molded articles, extrusion blow molded articles and extrusion stretch
blow
molded articles. These articles can include, but are not limited to, films,
bottles,
containers, sheet and/or fibers.
[0091] In one aspect, the polyester compositions useful, in the invention may
be used in various types of film and/or sheet, including but not limited to
extruded
film(s) and/or sheet(s), calendered film(s) and/or sheet(s), compression
molded
film(s) and/or sheet(s), solution casted film(s) and/or sheet(s). Methods of
CA 02666585 2009-04-16
WO 2008/051321 PCT/US2007/015704
-26-
making film and/or sheet include but are not limited to extrusion,
calendering,
compression molding, and solution casting.
[0092] In one aspect, the invention is related to thermoformed film(s) and/or
sheet(s) comprising the polyester(s) and/or polyester compositions of the
invention.
[0093] In one aspect, the invention is related to articles of manufacture
which
incorporate the thermoformed film and/or sheet of the invention.
[0094] In one aspect, the invention provides a process for preparing
polyesters containing ethylene glycol, 2,2,4,4-tetramethyl-1,3-
cyclobutanediol,
and optionally, cyclohexanedimethanol with improved color and/or clarity.
[0095] Also, in one aspect, a process of making thermoformed film and/or
sheet is provided wherein the step of drying the films and/or sheets prior to
thermoforming is eliminated.
100961 In one aspect, the polyesters useful in the invention can be amorphous
or semicrystalline. In one aspect, certain polyesters useful in the invention
can
have a relatively low crystallinity. Certain polyesters useful in the
invention can
thus have a substantially amorphous morphology, meaning that the polyesters
comprise substantially unordered regions of polymer.
DETAILED DESCRIPTION OF THE INVENTION
[0097] The present invention may be understood more readily by reference to
the following detailed description of certain embodiments of the invention and
the
working examples. In accordance with the purpose(s) of this invention, certain
embodiments of the invention are described in the Summary of the Invention and
are further described herein below. Also, other embodiments of the invention
are
described herein.
[0098] It is believed that certain polyesters and/or polyester composition(s)
of
the invention formed from terephthalic acid, an ester thereof, and/or mixtures
thereof, ethylene glycol, 2,2,4,4-tetramethyl-1,3-cyclobutanediol, and
optionally,
cyclohexanedimethanol, comprising certain thermal stabilizers, reaction
products
thereof, and mixtures thereof, can have a unique combination of two or more of
CA 02666585 2009-04-16
WO 2008/051321 PCT/US2007/015704
-27-
high notched lzod impact strength, certain inherent viscosities, certain glass
transition temperature (Tg), certain flexural modulus, good clarity, and good
color.
[0099] In some embodiments of the invention, certain polyesters and/or
polyester compositions of the invention can have a unique combination of three
or more of high notched Izod impact strength, certain inherent viscosities,
certain
glass transition temperature (T9), certain flexural modulus, good clarity, and
good
color.
[00100] In certain embodiments of the invention, certain polyesters and/or
polyester compositions of the invention can have a unique combination of four
or
more of high notched kzod impact strength, certain inherent viscosities,
certain
glass transition temperature (T9), certain flexural modulus, good clarity, and
good
color.
[00101] In other embodiments of the invention, certain polyesters and/or
polyester compositions of the invention can have a unique combination of all
of
the following properties: high notched Izod impact strength, certain inherent
viscosities, certain glass transition temperature (T9), certain flexural
modulus,
good clarity, and good color.
[00102] While polyesters and/or polyester compositions containing some or all
of the aforementioned properties are useful in many applications, these
properties are particularly useful for thermoformed sheet applications.
[00103] In one embodiment, it is believed that when at least one thermal
stabilizer comprising at least one phosphorus compound described herein are
used during the processes of making the polyesters according to the present
invention, the polyesters can be more easily produced without at least one of
the
following occurring: bubbling, splay formation, color formation, foaming, off-
gassing, and erratic melt levels, i.e., pulsating of the polyester or the
polyester's
production and processing systems. In another embodiment, it is believed that
at
least one process of the invention provides a means to more easily produce the
polyesters useful in the invention in large quantities (for example, pilot run
scale
and/or commercial production) without at least one of the aforesaid
difficulties
occurring.
CA 02666585 2009-04-16
WO 2008/051321 PCT/US2007/015704
-28-
[00104] The term "large quantities" as used herein includes quantities of
polyester(s) useful in the invention which are produced in quantities larger
than
100 pounds. In one embodiment, the term "large quantities", as used herein,
includes quantities of polyester(s) useful in the invention which are produced
in
quantities larger than 1000 pounds.
[00105] In one embodiment, the processes of making the polyesters useful in
the invention can comprise a batch or continuous process.
[00106] In one embodiment, the processes of making the polyesters useful in
the invention comprise a continuous process.
[00107] In one embodiment, copolyesters containing 2,2,4,4-tetramethyl-1,3-
cycfobutanediol and ethylene glycol can be prepared with titanium based
catalysts. In another embodiment, the incorporation of 2,2,4,4-tetramethyl-1,3-
cyclobutanediol can be further improved by use of tin based catalysts in
addition
to the titanium based catalysts. It is believed that the color of these
copolyesters
can be improved with the addition during polymerization of certain levels of
phosphorus containing compounds.
[00108] When tin is added to to the polyesters and/or polyester compositions
and/or process of making the polyesters of the invention, it is added to the
process of making the polyester in the form of a tin compound. The amount of
the tin compound added to the polyesters of the invention and/or polyester
compositions of the invention and/or processes of the invention can be
measured
in the form of tin atoms present in the final polyester, for example, by
weight
measured in ppm.
[00109] When titanium is added to to the polyesters and/or polyester
compositions and/or process of making the polyesters of the invention, it is
added
to the process of making the polyester in the form of a titanium compound. The
amount of the titanium compound added to the polyesters of the invention
and/or
polyester compositions of the invention and/or processes of the invention can
be
measured in the form of titanium atoms present in the final polyester, for
example, by weight measured in ppm.
[00110] When phosphorus is added to to the polyesters and/or polyester
compositions and/or process of making the polyesters of the invention, it is
added
CA 02666585 2009-04-16
WO 2008/051321 PCT/US2007/015704
-29-
to the process of making the polyester in the form of a phosphorus compound.
In
one embodiment, this phosphorus compound can comprise at least one
phosphate ester(s). The amount of phosphorus compound, [for example,
phosphate ester(s)] added to the polyesters of the invention and/or polyester
compositions of the invention and/or processes of the invention can be
measured
in the form of phosphorus atoms present in the final polyester, for example,
by
weight measured in ppm.
[001111 The term "polyester", as used herein, is intended to include
"copolyesters" and is understood to mean a synthetic polymer prepared by the
reaction of one or more difunctional carboxylic acids and/or multifunctional
carboxylic acids with one or more difunctional hydroxyl compounds and/or
multifunctional hydroxyl compounds, for example, branching agents. Typically
the difunctional carboxylic acid can be a dicarboxylic acid and the
difunctional
hydroxyl compound can be a dihydric alcohol such as, for example, glycols and
diols. The term "glycol" as used herein includes, but is not limited to,
diols,
glycols, and/or multifunctional hydroxyl compounds, for example, branching
agents. Alternatively, the difunctional carboxylic acid may be a hydroxy
carboxylic acid such as, for example, p-hydroxybenzoic acid, and the
difunctional
hydroxyl compound may be an aromatic nucleus bearing 2 hydroxyl substituents
such as, for example, hydroquinone. The term "residue", as used herein, means
any organic structure incorporated into a polymer through a polycondensation
and/or an esterification reaction from the corresponding monomer. The term
"repeating unit", as used herein, means an organic structure having a
dicarboxylic
acid residue and a diol residue bonded through a carbonyloxy group. Thus, for
example, the dicarboxylic acid residues may be derived from a dicarboxylic
acid
monomer or its associated acid halides, esters, salts, anhydrides, and/or
mixtures
thereof. Furthermore, as used herein, the term "diacid" includes
multifunctional
acids, for example, branching agents. As used herein, therefore, the term
"dicarboxylic acid" is intended to include dicarboxylic acids and any
derivative of
a dicarboxylic acid, including its associated acid halides, esters, half-
esters, salts,
half-salts, anhydrides, mixed anhydrides, and/or mixtures thereof, useful in a
reaction process with a diol to make polyester. As used herein, the term
CA 02666585 2009-04-16
WO 2008/051321 PCT/US2007/015704
-30-
"terephthalic acid" is intended to include terephthalic acid ;itseif and
residues
thereof as well as any derivative of terephthalic acid, including its
associated acid
halides, esters, half-esters, salts, half-salts, anhydrides, mixed anhydrides,
and/or
mixtures thereof or residues thereof useful in a reaction process with a diol
to
make polyester.
[00112] The polyesters used in the present invention typically can be prepared
from dicarboxylic acids and diols which react in substantially equal
proportions
and are incorporated into the polyester polymer as their corresponding
residues.
The polyesters of the present invention, therefore, can contain substantially
equal
molar proportions of acid residues (100 mole%) and diol (and/or
multifunctional
hydroxyl compound) residues (100 mole%) such that the total moles of repeating
units is equal to 100 mole%. The mole percentages provided in the present
disclosure, therefore, may be based on the total moles of acid residues, the
total
moles of diol residues, or the total moles of repeating units. For example, a
polyester containing 10 mole% isophthalic acid, based on the total acid
residues,
means the polyester contains 10 mole% isophthalic acid residues out of a total
of
100 mole% acid residues. Thus, there are 10 moles of isophthalic acid residues
among every 100 moles of acid residues. In another exarnple, a polyester
containing 30 mole% 2,2,4,4-tetramethyl-1,3-cyclobutanediol, based on the
total
diol residues, means the polyester contains 30 mole% 2,2,4,4-tetramethyl-1,3-
cyclobutanediol residues out of a total of 100 mole% diol residues. Thus,
there
are 30 moles of 2,2,4,4-tetramethyl-1,3-cyclobutanediol residues among every
100 moles of diol residues.
[00113] In other aspects of the invention, the Tg of the polyesters useful in
the
polyester compositions of the invention can be at least one of the following
ranges: 80 to 200 C; 80 to 190 C; 80 to 180 C; 80 to 170 C; 80 to 160 C; 80 to
155 C; 80 to 150 C; 80 to 145 C; 80 to 140 C; 80 to 138 C; 80 to 135 C; 80 to
130 C; 80 to 125 C; 80 to 120 C; 80 to 115 C; 80 to 110 C; 80 to 105 C; 80 to
100 C; 80 to 95 C; 80 to 90 C; 80 to 85 C; 85 to 200 C; 85 to 190 C; 85 to
180 C; 85 to 170 C; 85 to 160 C; 85 to 155 C; 85 to 150 C; 85 to 145 C; 85 to
140 C; 85 to 138 C; 85 to 135 C; 85 to 130 C; 85 to 125 C; 85 to 120 C; 85 to
115 C; 85 to 110 C; 85 to 105 C; 85 to 100 C; 85 to 95 C; 85 to 90 C; 90 to
CA 02666585 2009-04-16
WO 2008/051321 PCT/US2007/015704
-31 -
200 C; 90 to 190 C; 90 to 180 C; 90 to 170 C; 90 to 160 C; 90 to 155 C; 90 to
150 C; 90 to 145 C; 90 to 140 C; 90 to 138 C; 90 to 135 C; 90 to 130 C; 90 to
125 C; 90 to 120 C; 90 to 115 C; 90 to 110 C; 90 to 105 C; 90 to 100 C; 90 to
95 C; 95 to 200 C; 95 to 190 C; 95 to 180 C; 95 to 170 C; 95 to 160 C; 95 to
155 C; 95 to 150 C; 95 to 145 C; 95 to 140 C; 95 to 138 C; 95 to 135 C; 95 to
130 C; 95 to 125 C; 95 to 120 C; 95 to 115 C; 95 to 110 C; 95 to 105 C; 95 to
100 C; 100 to 200 C; 100 to 190 C; 100 to 180 C; 100 to 170 C; 100 to 160 C;
100 to 155 C; 100 to 150 C; 100 to 145 C; 100 to 140 C; 100 to 138 C; 100 to
135 C; 100 to 130 C; 100 to 125 C; 100 to 120 C; 100 to 115 C; 100 to 110 C;
105 to 200 C; 105 to 190 C; 105 to 180 C; 105 to 170 C; 105 to 160 C; 105 to
155 C; 105 to 150 C; 105 to 145 C; 105 to 140 C; 105 to 138 C; 105 to 135 C;
105 to 130 C; 105 to 125 C; 105 to 120 C; 105 to 115 C; 105 to 110 C; 110 to
200 C; 110 to 190 C; 110 to 180 C; 110 to 170 C; 110 to 160 C; 110 to 155 C;
110 to 150 C; 110 to 145 C; 110 to 140 C; 110 to 138 C; 110 to 135 C; 110 to
130 C; 110 to 125 C; 110 to 120 C; 110 to 115 C; 115 to 200 C; 115 to 190 C;
115 to 180 C; 115 to 170 C; 115 to 160 C; 115 to 155 C; 115 to 150 C; 115 to
145 C; 115 to 140 C; 115 to 138 C; 115 to 135 C; 110 to 130 C; 115 to 125 C;
115 to 120 C; 120 to 200 C; 120 to 190 C; 120 to 180 C; 120 to 170 C; 120 to
160 C; 120 to 155 C; 120 to 150 C; 120 to 145 C; 120 to 140 C; 120 to 138 C;
120 to 135 C; 120 to 130 C; 125 to 200 C; 125 to 190 C; 125 to 180 C; 125 to
170 C; 125 to 165 C; 125 to 160 C; 125 to 155 C; 125 to 150 C; 125 to 145 C;
125 to 140 C; 125 to 138 C; 125 to 135 C; 127 to 200 C; 127 to 190 C;' 127 to
180 C; 127 to 170 C; 127 to 160 C; 127 to 150 C; 127 to 145 C; 127 to 140 C;
127 to 138 C; 127 to 135 C; 130 to 200 C; 130 to 190 C; 130 to 180 C; 130 to
170 C; 130 to 160 C; 130 to 155 C; 130 to 150 C; 130 to 145 C; 130 to 140 C;
130 to 138 C; 130 to 135 C; 135 to 200 C; 135 to 190 C; 135 to 180 C; 135 to
170 C; 135 to 160 C; 135 to 155 C; 135 to 150 C; 135 to 145 C; 135 to 140 C;
140 to 200 C; 140 to 190 C; 140 to 180 C; 140 to 170 C; 140 to 160 C; 140 to
155 C; 140 to 150 C; 140 to 145 C; 148 to 200 C; 148 to 190 C; 148 to 180 C;
148 to 170 C; 148 to 160 C; 148 to 155 C; 148 to 150 C; greater than 148 to
200 C; greater than 148 to 190 C; greater than 148 to 180 C; greater than 148
to
170 C; greater than 148 to 160 C; greater than 148 to 155 C; 150 to 200 C; 150
CA 02666585 2009-04-16
WO 2008/051321 PCT/US2007/015704
-32-
to 190 C; 150 to.180 C; 150 to 170 C; 150 to 160; 155 to 190 C; 155 to 180 C;
155 to 170 C; and 155 to 165 C.
[00114] In other aspects of the invention, the glycol component for the
polyesters useful in the invention include but are not limited to at least one
of the
following combinations of ranges: about 1 to less than 90 mole % 2,2,4,4-
tetramethyl-1,3-cyclobutanediol, greater than 10 mole % ethylene glycol
residues,
and about 0 to about 89 mole % cyclohexanedimethanol; 1 to 85 mole % 2,2,4,4-
tetramethyl-1,3-cyclobutanediol and 15 to 99 mole % ethylene glycol; 1 to 80
mole % 2,2,4,4-tetramethyl-1,3-cyclobutanediol and 20 to 99 mole % ethylene
glycol, 1 to 75 mole % 2,2,4,4-tetramethyl-1,3-cyclobutanediol and 25 to 99
mole
% ethylene glycol; 1 to 70 mole % 2,2,4,4-tetramethyl-1,3-cyclobutanediol and
30
to 99 mole % ethylene glycol; 1 to 65 mole % 2,2,4,4-tetramethyl-1,3-
cyclobutanediol and 35 to 99 mole % ethylene glycol; 1 to 60 mole % 2,2,4,4-
tetramethyl-1,3-cyclobutanediol and 40 to 99 mole % ethylene glycol; 1 to 55
mole % 2,2,4,4-tetramethyl-1,3-cyclobutanediol and 45 to 99 mole % ethylene
glycol; 1 to 50 mole % 2,2,4,4-tetramethyl-1,3-cyclobutanediol and 50 to 99
mole
% ethylene glycol; 1 to 45 mole % 2,2,4,4-tetramethyl-1,3-cyclobutanediol and
55 to 99 mole % ethylene glycol; 1 to 40 mole % 2,2,4,4-tetramethyl-1,3-
cyclobutanediol and 60 to 99 mole % ethylene glycol; 1 to, 35 mole % 2,2,4,4-
tetramethyl-1,3-cyclobutanediol and 65 to 99 mole % ethylene glycol; 1 to 30
mole % 2,2,4,4-tetramethyl-1,3-cyclobutanediol and 70 to 99 mole % ethylene
glycol; 1 to 25 mole % 2,2,4,4-tetramethyl-1,3-cyclobutanediol and 75 to 99
mole
% ethylene glycol; 1 to 20 mole % 2,2,4,4-tetramethyl-1,3-cyclobutanediol and
80 to 99 mole % ethylene glycol; I to 15 mole % 2,2,4,4-tetramethyl-1,3-
cyclobutanediol and 85 to 99 mole % ethylene glycol; 1 to'10 mole % 2,2,4,4-
tetramethyl-1,3-cyclobutanediol and 90 to 99 mole % ethylene glycol; and 1 to
5
mole % 2,2,4,4-tetramethyl-1,3-cyclobutanediol and 95 to 99 mole % ethylene
glycol.
[00115) In other aspects of the invention, the glycol component for the
polyesters useful in the invention include but are not limited to at least one
of the
following combinations of ranges: 3 to 10 mole % 2,2,4,4-tetramethyl-1,3-
cyclobutanediol and 90 to 97 mole % ethylene glycol; 3 to 9 mole % 2,2,4,4-
CA 02666585 2009-04-16
WO 2008/051321 PCT/US2007/015704
-33-
tetramethyl-1,3-cyclobutanediol and 91 to 97 mole % ethylene glycol; and 3 to
8
mole % 2,2,4,4-tetramethyl-1,3-cyclobutanediol and 92 to 97 mole % ethylene
glycoll.
[00116] In other aspects of the invention, the glycol component for the
polyesters useful in the invention include but are not limited to at least one
of the
following combinations of ranges: about 5 to less than 90"mole % 2,2,4,4-
tetramethyl-1,3-cyclobutanediol and greater than 10 to 95 mole % ethylene
glycol; 5 to 85 mole % 2,2,4,4-tetramethyl-1,3-cyclobutanediol and 15 to 95
mole
% ethylene glycol; 5 to 80 mole % 2,2,4,4-tetramethyl-1,3-cyclobutanediol and
20
to 95 mole % ethylene glycol, 5 to 75 mole % 2,2,4,4-tetramethyl-1,3-
cyclobutanediol and 25 to 95 "mole % ethylene glycol; 5 to 70 mole % 2,2,4,4-
tetramethyl-1,3-cyclobutanediol and 30 to 95 mole % ethylene glycol; 5 to 65
mole % 2,2,4,4-tetramethyl-1,3-cyclobutanediol and 35 to 95 mole % ethylene
glycol; 5 to 60 mole % 2,2,4,4-tetramethyl-1,3-cyclobutanediol and 40 to 95
mole
% ethylene glycol; 5 to 55 mole % 2,2,4,4-tetramethyl-1,3-cyclobutanediol and
45
to 95 mole % ethylene glycol; and 5 to 50 mole % 2,2,4,4-tetramethyl-1,3-
cyclobutanediol and 50 to 95 mole % ethylene glycol.
[00117] In other aspects of the invention, the glycol component for the
polyesters useful in the invention include but are not limited to at least one
of the
following combinations of ranges: 5 to less than 50 mole % 2,2,4,4-tetramethyl-
1,3-cyclobutanediol and greater than 50 to 95 mole % ethylene glycol; 5 to 45
mole % 2,2,4,4-tetramethyl-1,3-cyclobutanediol and 55 to 95 mole % ethylene
glycol; 5 to 40 mole % 2,2,4,4-tetramethyl-1,3-cyclobutanediol and 60 to 95
mole
% ethylene glycol; 5 to 35 mole % 2,2,4,4-tetramethyl-1,3-cyclobutanediol and
65 to 95 mole % ethylene glycol; 5 to less than 35 mole % 2,2,4,4-tetramethyl-
1,3-cyclobutanediol and greater than 65 to 95 mole % ethylene glycol; 5 to 30
mole % 2,2,4,4-tetramethyl-1,3-cyclobutanediol and 70 to 95 mole % ethylene
glycol; 5 to 25 mole % 2,2,4,4-tetramethyl-1,3-cyclobutanediol and 75 to 95
mole
% ethylene glycol; 5 to 20 mole % 2,2,4,4-tetramethyl-1,3-cyclobutanediol and
80
to 95 mole % ethylene glycol; 5 to 15 mole % 2,2,4,4-tetramethyl-1,3-
cyclobutanediol and 85 to 95 mole % ethylene glycol; 5 to 10 mole % 2,2,4,4-
tetramethyl-1,3-cyclobutanediol and 90 to 95 mole % ethylene glycol; greater
CA 02666585 2009-04-16
WO 2008/051321 PCT/US2007/015704
-34-
than 5 to less than 10 mole % 2,2,4,4-tetramethyl-1,3-cyclobutanediol and less
than 90 to greater than 95 mole % ethylene glycol; 5.5 mole % to 9.5 mole %
2,2,4,4-tetramethyl-1,3-cyclobutanediol and 94.5 mole % to 90.5 mole %
ethylene
glycol; and 6 to 9 mole % 2,2,4,4-tetramethyl-1,3-cyclobutanedioI and 94 to 91
mole % ethylene glycol.
[00118] In other aspects of the invention, the glycol component for the
polyesters useful in the invention include but are not limited to at least one
of the
following combinations of ranges: about 10 to less than 90 mole % 2,2,4,4-
tetramethyl-1,3-cyclobutanediol and greater than 10 to about 90 mole %
ethylene
glycol; 10 to 85 mole % 2,2,4,4-tetramethyl-1,3-cyclobutanedioI and 15 to 90
mole % ethylene glycol; 10 to 80 mole % 2,2,4,4-tetramethyl-1,3-
cyclobutanedioI
and 20 to 90 mole % ethylene glycol; 10 to 75 mole % 2,2;4,4-tetramethyl-1,3-
cyclobutanediol and 25 to 90 mole % ethylene glycol; 10 to 70 mole % 2,2,4,4-
tetramethyl-1,3-cyclobutanediol and 30 to 90 mole % ethylene glycol; 10 to 65
mole % 2,2,4,4-tetramethyl-1,3-cyclobutanedioI and 35 to 90 mole % ethylene
glycol; 10 to 60 mole % 2,2,4,4-tetramethyl-1,3-cyclobutanedioI and 40 to 90
mole % ethylene glycol; 10 to 55 mole % 2,2,4,4-tetramethyl-1,3-
cyclobutanedioI
and 45 to 90 mole % ethylene glycol; 10 to 50 mole % 2,2,4,4-tetramethyl-1,3-
cyclobutanediol and 50 to 90 mole % ethylene glycol; 10 to less than 50 mole %
2,2,4,4-tetramethyl-1,3-cyclobutanedioI and greater than 50 to 90 mole %
ethylene glycol; 10 to 45 mole % 2,2,4,4-tetramethyl-1,3-cyclobutanedioI and
55
to 90 mole % ethylene glycol; 10 to 40 mole % 2,2,4,4-tetramethyl-1,3-
cyclobutanediol and 60 to 90 mole % ethylene glycol; 10 to 35 mole % 2,2,4,4-
tetramethyl-1,3-cyclobutanediol and 65 to 90 mole % ethylene glycol; 10 to
less
than 35 mole % 2,2,4,4-tetramethyl-1,3-cyclobutanedioI and greater than 65 to
90
% ethylene glycol; 10 to 30 mole % 2,2,4,4-tetramethyl-1,3-cyclobutanedioI and
70 to 90 mole % ethylene glycol; 10 to 25 mole % 2,2,4,4-tetramethyl-1,3-
cyclobutanediol and 75 to 90 mole % ethylene glycol; 10 to 20 mole % 2,2,4,4-
tetramethyl-1,3-cyclobutanediol and 80 to 90 mole % ethylene glycol; and 10 to
15 mole % 2,2,4,4-tetramethyl-1,3-cyclobutanedioI and 85 to 90 mole % ethylene
glycol.
CA 02666585 2009-04-16
WO 2008/051321 PCT/US2007/015704
-35-
[00119] In other aspects of the invention, the glycol component for the
polyesters useful in the invention include but are not limited to at least one
of the
following combinations of ranges: greater than 10 to less than 90 mole %
2,2,4,4-tetramethyl-1,3-cyclobutanediol and greater than 10 to less than 90
mole
% ethylene glycol; greater than 10 to 85 mole % 2,2,4,4-tetramethyl-1,3-
cyclobutanediol and 15 to less than 90 mole % ethylene glycol; greater than 10
to
80 mole % 2,2,4,4-tetramethyl-1,3-cyclobutanediol and 20 to less than 90 mole
%
ethylene glycol; greater than 10 to 75 mole % 2,2,4,4-tetramethyl-1,3-
cyclobutanediol and 25 to less than 90 mole % ethylene glycol; greater than 10
to
70 mole % 2,2,4,4-tetramethyl-1,3-cyclobutanedioi and 30'to less than 90 mole
%
ethylene glycol; greater than 10 to 65 mole % 2,2,4,4-tetramethyl-1,3-
cyclobutanediol and 35 to less than 90 mole % ethylene glycol; greater than 10
to
60 mole % 2,2,4,4-tetramethyl-1,3-cyclobutanediol and 40 to less than 90 mole
%
ethylene glycol; greater than 10 to 55 mole % 2,2,4,4-tetramethyl-1,3-
cyclobutanediol and 45 to less than 90 mole % ethylene glycol; greater than 10
to
50 mole % 2,2,4,4-tetramethyl-1,3-cyclobutanediol and 50'to less than 90 mole
%
ethylene glycol; greater than 10 to less than 50 mole % 2,2,4,4-tetramethyl-
1,3-
cyclobutanediol and greater than 50 to less than 90 mole % ethylene glycol;
greater than 10 to 45 mole % 2,2,4,4-tetramethyl-1,3-cyclobutanediol and 55 to
less than 90 mole % ethylene glycol; greater than 10 to 40 mole % 2,2,4,4-
tetramethyl-1,3-cyclobutanediol and 60 to less than 90 mole % ethylene glycol;
greater than 10 to 35 mole % 2,2,4,4-tetramethyl-1,3-cyclobutanedioi and 65 to
less than 90 mole % ethylene glycol; 10 to less than 34 mole % 2,2,4,4-
tetramethyl-1,3-cyclobutanediol and greater than 66 to 90 % ethylene glycol;
greater than 10 to 30 mole % 2,2,4,4-tetramethyl-1,3-cyclobutanedio! and 70 to
less than 90 mole % ethylene glycol; greater than 10 to 25 mole % 2,2,4,4-
tetramethyl-1,3-cyclobutanediol and 75 to less than 90 mole % ethylene glycol;
greater than 10 to 20 mole % 2,2,4,4-tetramethyl-1,3-cyclobutanediol and 80 to
less than 90 mole % ethylene glycol; and greater than 10 to 15 mole % 2,2,4,4-
tetramethyl-1,3-cyclobutanediol and 85 to less than 90 mole % ethylene glycol.
1001201 In other aspects of the invention, the glycol component for the
polyesters useful in the invention include but are not limited to at least one
of the
CA 02666585 2009-04-16
WO 2008/051321 PCT/US2007/015704
-36-
following combinations of ranges: about 11 to less than 90 mole % 2,2,4,4-
tetramethyl-1,3-cyclobutanediol and greater than 10 to about 89 mole %
ethylene
glycol; 11 to 85 mole % 2,2,4,4-tetramethyl-1,3-cyclobutanediol and 15 to 89
mole % ethylene glycol; 11 to 80 mole % 2,2,4,4-tetramethyl-1,3-
cyclobutanediol
and 20 to 89 mole % ethylene glycol; 11 to 75 mole % 2,2,4,4-tetramethyl-1,3-
cyclobutanediol and 25 to 89 mole % ethylene glycol; 11 to 70 mole % 2,2,4,4-
tetramethyl-1,3-cyclobutanediol and 30 to 89 mole % ethylene glycol; 11 to 65
mole % 2,2,4,4-tetramethyl-1,3-cyclobutanediol and 35 to 89 mole % ethylene
glycol; 11 to 60 mole % 2,2,4,4-tetramethyl-1,3-cyclobutanediol and 40 to 89
mole % ethylene glycol; 11 to 55 mole % 2,2,4,4-tetramethyl-1,3-
cyclobutanediol
and 45 to 89 mole % ethylene glycol; 11 to 50 mole % 2,2,4,4-tetramethyl-1,3-
cyclobutanediol and 50 to 89 mole % ethylene glycol; 11 to less than 50 mole %
2,2,4,4-tetramethyl-1,3-cyclobutanediol and greater than 50 to 89 mole %
ethylene glycol; 11 to 45 mole % 2,2,4,4-tetramethyl-1,3-cyclobutanediol and
55
to 89 mole % ethylene glycol; 11 to 40 mole % 2,2,4,4-tetramethyl-1,3-
cyclobutanediol and 60 to 89 mole % ethylene glycol; 11 to 35 mole % 2,2,4,4-
tetramethyl-1,3-cyclobutanediol and 65 to 89 mole % ethylene glycol; 11 to 30
mole % 2,2,4,4-tetramethyl-1,3-cyclobutanediol and 70 to 89 mole % ethylene
glycol; 11 to 24 mole % 2,2,4,4-tetramethyl-1,3-cyclobutanediol and 76 to 89
mole % ethylene glycol; and 11 to 25 mole % 2,2,4,4-tetramethyl-1,3-
cyclobutanediol and 75 to 89 mole % ethylene glycol.
[00121] In other aspects of the invention, the glycol component for the
polyesters useful in the invention include but are not limited to at least one
of the
following combinations of ranges: 12 to less than 90 mole % 2,2,4,4-
tetramethyl-
1,3-cyclobutanediol and greater than 10 to 88 mole % ethylene glycol; 12 to 85
mole % 2,2,4,4-tetramethyl-1,3-cyclobutanediol and 15 to 88 mole % ethylene
glycol; 12 to 80 mole % 2,2,4,4-tetramethyl-1,3-cyclobutanediol and 20 to 88
mole % ethylene glycol; 12 to 75 mole % 2,2,4,4-tetramethyl-1,3-
cyclobutanediol
and 25 to 88 mole % ethylene glycol; 12 to 70 mole % 2,2,4,4-tetramethyl-1,3-
cyclobutanediol and 30 to 88 mole % ethylene glycol; 12 to 65 mole % 2,2,4,4-
tetramethyl-1,3-cyclobutanediol and 35 to 88 mole % ethylene glycol; 12 to 60
mole % 2,2,4,4-tetramethyl-1,3-cyclobutanediol and 40 to 88 mole % ethylene
CA 02666585 2009-04-16
WO 2008/051321 PCT/US2007/015704
-37-
glycol; 12 to 55 mole % 2,2,4,4-tetramethyl-1,3-cyclobutanedioI and 45 to 88
mole % ethylene glycol; 12 to 50 mole % 2,2,4,4-tetramethyl-1,3-
cyclobutanediol
and 50 to 88 mole % ethylene glycol; 12 to less than 50 mole % 2,2,4,4-
tetramethyl-1,3-cyclobutanediol and greater than 50 to 88 mole % ethylene
glycol; 12 to 45 mole % 2,2,4,4-tetramethyl-1,3-cyclobutanedioI and 55 to 88
mole % ethylene glycol; 12 to 40 mole % 2,2,4,4-tetramethyl-1,3-
cyclobutanedioI
and 60 to 88 mole % ethylene glycol; 12 to 35 mole % 2,2,4,4-tetramethyl-1,3-
cyclobutanediol and 65 to 88 mole % ethylene glycol; 12 to 30 mole % 2,2,4,4-
tetram ethyl- 1, 3-cyclobuta ned iol and 70 to 88 mole % ethylene glycol; 12
to 24
mole % 2,2,4,4-tetramethyl-1,3-cyclobutanedioI and 76 to 88 mole % ethylene
glycol; and 12 to 25 mole % 2,2,4,4-tetramethyl-1,3-cyclobutanediol and 75 to
88
mole % ethylene glycol.
[00122] In other aspects of the invention, the glycol component for the
polyesters useful in the invention include but are not limited to at least one
of the
following combinations of ranges: about 15 to less than 90 mole % 2,2,4,4-
tetramethyl-1,3-cyclobutanediol and greater than 10 to about 85 mole %
ethylene
glycol; 15 to 85 mole % 2,2,4,4-tetramethyl-1,3-cyclobutanedioI and 15 to 85
mole % ethylene glycol; 15 to 80 mole % 2,2,4,4-tetramethyl-1,3-
cyclobutanedioI
and 20 to 85 mole % ethylene glycol; 15 to 75 mole % 2,2,4,4-tetramethyl-1,3-
cyclobutanediol and 25 to 85 mole % ethylene glycol; 15 to 70 mole % 2,2,4,4-
tetramethyl-1,3-cyclobutanediol and 30 to 85 mole % ethylene glycol; 15 to 65
mole % 2,2,4,4-tetramethyl-1,3-cyclobutanedioI and 35 to 85 mole % ethylene
glycol; 15 to 60 mole % 2,2,4,4-tetramethyl-1,3-cyclobutanedioI and 40 to 85
mole % ethylene glycol; 15 to 55 mole % 2,2,4,4-tetramethyl-1,3-
cyclobutanedioI
and 45 to 85 mole % ethylene glycol; 15 to 50 mole % 2,2,4,4-tetramethyl-1,3-
cyclobutanediol and 50 to 85 mole % ethylene glycol; 15 to less than 50 mole %
2,2,4,4-tetramethyl-1,3-cyclobutanedioI and greater than 50 to 85 mole %
ethylene glycol; 15 to 45 mole % 2,2,4,4-tetramethyl-1,3-cyclobutanedioI and
55
to 85 mole % ethylene glycol; 15 to 40 mole % 2,2,4,4-tetramethyl-1,3-
cyclobutanediol and 60 to 85 mole % ethylene glycol; 15 to 35 mole % 2,2,4,4-
tetrarnethyl-1,3-cyclobutanediol and 65 to 85 mole % ethylene glycol; 15 to 30
mole % 2,2,4,4-tetramethyl-1,3-cyclobutanedioI and 70 to 85 mole % ethylene
CA 02666585 2009-04-16
WO 2008/051321 PCT/US2007/015704
-38-
glycol; 15 to 25 mole % 2,2,4,4-tetramethyl-1,3-cyclobutanediol and 75 to 85
mole % ethylene glycol; and 15 to 24 mole % 2,2,4,4-tetramethyl-1,3-
cyclobutanediol and 76 to 85 mole % ethylene glycol.
[00123] In other aspects of the invention, the glycol component for the
polyesters useful in the invention include but are not limited to at least one
of the
following combinations of ranges: about 20 to less than 90 mole % 2,2,4,4-
tetramethyl-1,3-cyclobutanediol and greater than 10 to about 80 mole %
ethylene
glycol; 20 to 85 mole % 2,2,4,4-tetramethyl-1,3-cyclobutanediol and 15 to 80
mole % ethylene glycol; 20 to 80 mole % 2,2,4,4-tetramethyl-1,3-
cyclobutanediol
and 20 to 80 mole % ethylene glycol; 20 to 75 mole % 2,2,4,4-tetramethyl-1,3-
cyclobutanediol and 25 to 80 mole % ethylene glycol; 20 to 70 mole % 2,2,4,4-
tetrarnethyl-1,3-cyclobutanediol and 30 to 80 mole % ethylene glycol; 20 to 65
mole % 2,2,4,4-tetramethyl-1,3-cyclobutanediol and 35 to 80 mole % ethylene
glycol; 20 to 60 mole % 2,2,4,4-tetramethyl-1,3-cyclobutanediol and 40 to 80
mole % ethylene glycol; 20 to 55 mole % 2,2,4,4-tetramethyl-1,3-
cyclobutanediol
and 45 to 80 mole % ethylene glycol; 20 to 50 mole % 2,2,4,4-tetramethyl-1,3-
cyclobutanediol and 50 to 80 mole % ethylene glycol; 20 to less than 50 mole %
2,2,4,4-tetramethyl-1,3-cyclobutanedioi and greater than 50 to 80 mole %
ethylene glycol; 20 to 45 mole % 2,2,4,4-tetramethyl-1,3-cyclobutanediol and
55
to 80 mole % ethylene glycol; 20 to 40 mole % 2,2,4,4-tetramethyl-1,3-
cyclobutanediol and 60 to 80 mole % ethylene glycol; 20 to 35 mole % 2,2,4,4-
tetrarnethyl-1,3-cyclobutanediol and 65 to 80 mole % ethylene glycol; 20 to 30
mole % 2,2,4,4-tetramethyl-1,3-cyclobutanediol and 70 to 80 mole % ethylene
glycol; and 20 to 25 mole % 2,2,4,4-tetramethyl-1,3-cyclobutanediol and 75 to
80
mole % ethylene glycol.
[00124] In other aspects of the invention, the glycol component for the
polyesters useful in the invention include but are not limited to at least one
of the
following combinations of ranges: about 25 to less than 90 mole % 2,2,4,4-
tetramethyl-1,3-cyclobutanediol and greater than 10 to 75 mole % ethylene
glycol; 25 to 85 mole % 2,2,4,4-tetramethyl-1,3-cyclobutanediol and 15 to 75
mole % ethylene glycol; 25 to 80 mole % 2,2,4,4-tetramethyl-1,3-
cyclobutanediol
and 20 to 75 mole % ethylene glycol; 25 to 75 mole % 2,2,4,4-tetramethyl-1,3-
CA 02666585 2009-04-16
WO 2008/051321 PCT/US2007/015704
-39-
cyclobutanediol and 25 to 75 mole % ethylene glycol; 25 to 70 mole % 2,2,4,4-
tetramethyl-1,3-cyclobutanediol and 30 to 75 mole % ethylene glycol; 25 to 65
mole % 2,2,4,4-tetramethyl-1,3-cyclobutanediol and 35 to 75 mole % ethylene
glycol; 25 to 60 mole % 2,2,4,4-tetramethyl-1,3-cyclobutanediol and 40 to 75
mole % ethylene glycol; 25 to 55 mole % 2,2,4,4-tetramethyl-1,3-
cyclobutanediol
and 45 to 75 mole % ethylene glycol; 25 to 50 mole % 2,2,4,4-tetramethyl-1,3-
cyclobutanediol and 50 to 75 mole % ethylene glycol; 25 to less than 50 mole %
2,2,4,4-tetramethyl-1,3-cyclobutanediol and greater than 50 to 75 mole %
ethylene glycol; 25 to 45 mole % 2,2,4,4-tetramethyl-1,3-cyclobutanediol and
55
to 75 mole % ethylene glycol; 25 to 40 mole % 2,2,4,4-tetramethyl-1,3-
cyclobutanediol and 60 to 75 mole % ethylene glycol; 25 to 35 mole % 2,2,4,4-
tetramethyl-1,3-cyclobutanediol and 65 to 75 mole % ethylene glycol; and 25 to
30 mole % 2,2,4,4-tetramethyl-1,3-cyclobutanediol and 70 to 75 mole % ethylene
glycol.
[00125] In other aspects of the invention, the glycol component for the
polyesters useful in the invention include but are not limited to at least one
of the
following combinations of ranges: about 30 to less than 90 mole % 2,2,4,4-
tetramethyl-1,3-cyclobutanediol and greater than 10 to about 70 mole %
ethylene
glycol; 30 to 85 mole % 2,2,4,4-tetramethyl-1,3-cyclobutanediol and 15 to 70
mole % ethylene glycol; 30 to 80 mole % 2,2,4,4-tetramethyl-1,3-
cyclobutanediol
and 20 to 70 mole % ethylene glycol; 30 to 75 mole % 2,2,4,4-tetramethyl-1,3-
cyclobutanediol and 25 to 70 mole % ethylene glycol; 30 to 70 mole % 2,2,4,4-
tetramethyl-1,3-cyclobutanediol and 30 to 70 mole % ethylene glycol; 30 to 65
mole % 2,2,4,4-tetramethyl-1,3-cyclobutanediol and 35 to 70 mole % ethylene
glycol; 30 to 60 mole % 2,2,4,4-tetramethyl-1,3-cyclobutanediol and 40 to 70
mole % ethylene glycol; 30 to 55 mole % 2,2,4,4-tetramethyi-1,3-
cyclobutanediol
and 45 to 70 mole % ethylene glycol; 30 to 50 mole % 2,2,4,4-tetramethyl-1,3-
cyclobutanediol and 50 to 70 mole % ethylene glycol; 30 to less than 50 mole %
2,2,4,4-tetramethyl-1,3-cyclobutanediol and greater than 50 to 70 mole %
ethylene glycol; 30 to 45 mole % 2,2,4,4-tetramethyl-1,3-cyclobutanediol and
55
to 70 mole % ethylene glycol; 30 to 40 mole % 2,2,4,4-tetramethyl-1,3-
CA 02666585 2009-04-16
WO 2008/051321 PCT/US2007/015704
- 40 -
cycfobutanediol and 60 to 70 mole % ethylene glycol; 30 to 35 mole % 2,2,4,4-
tetramethyl-1,3-cyclobutanediol and 65 to 70 mole % ethylene glycol.
[00126] In other aspects of the invention, the glycol component for the
polyesters useful in the invention include but are not limited to at least one
of the
following combinations of ranges: about 35 to less than 90 mole % 2,2,4,4-
tetramethyl-1,3-cyclobutanediol and greater than 10 to about 65 mole %
ethylene
glycol; 35 to 85 mole % 2,2,4,4-tetramethyl-1,3-cyclobutanediol and 15 to 65
mole % ethylene glycol; 35 to 80 mole % 2,2,4,4-tetramethyl-1,3-
cyclobutanediol
and 20 to 65 mole % ethylene glycol; 35 to 75 mole % 2,2,4,4-tetramethyl-1,3-
cyclobutanediol and 25 to 65 mole % ethylene glycol; 35 to 70 mole % 2,2,4,4-
tetramethyl-1,3-cyclobutanediol and 30 to 65 mole % ethylene glycol; 35 to 65
mole % 2,2,4,4-tetramethyl-1,3-cyclobutanediol and 35 to 65 mole % ethylene
glycol; 35 to 60 mole % 2,2,4,4-tetramethyl-1,3-cyclobutanediol and 40 to 65
mole % ethylene glycol; 35 to 55 mole % 2,2,4,4-tetramethyl-1,3-
cyclobutanediol
and 45 to 65 mole % ethylene glycol; 35 to 50 mole % 2,2,4,4-tetramethyl-1,3-
cyclobutanediol and 50 to 65 mole % ethylene glycol; 35 to less than 50 mole %
2,2,4,4-tetramethyl-1,3-cyclobutanediol and greater than 50 to 65 mole %
ethylene glycol; 35 to 45 mole % 2,2,4,4-tetramethyl-1,3-cyclobutanediol and
55
to 65 mole % ethylene glycol; 35 to 40 mole % 2,2,4,4-tetramethyl-1,3-
cyclobutanediol and 60 to 65 mole % ethylene glycol.
[00127] In other aspects of the invention, the glycol component for the
polyesters useful in the invention include but are not limited to at least one
of the
following combinations of ranges: about 40 to less than 90 mole % 2,2,4,4-
tetramethyl-1,3-cyclobutanediol and greater than 10 to about 60 mole %
ethylene glycol; 40 to 85 mole % 2,2,4,4-tetramethyl-1,3-cyclobutanediol and
15
to 60 mole % ethylene glycol; 40 to 80 mole % 2,2,4,4-tetramethyl-1,3-
cyclobutanediol and 20 to 60 mole % ethylene glycol; 40 to 75 mole % 2,2,4,4-
tetramethyl-1,3-cyclobutanediol and 25 to 60 mole % ethylene glycol; 40 to 70
mole % 2,2,4,4-tetramethyl-1,3-cyclobutanediol and 30 to 60 mole % ethylene
glycol; 40 to 65 mole % 2,2,4,4-tetramethyl-1,3-cyclobutanediol and 35 to 60
mole % ethylene glycol; 40 to 60 mole % 2,2,4,4-tetramethyl-1,3-
cyclobutanediol
and 40 to 60 mole % ethylene glycol; 40 to 55 mole % 2,2,4,4-tetramethyl-1,3-
CA 02666585 2009-04-16
WO 2008/051321 PCT/US2007/015704
-41 -
cyclobutanediol and 45 to 60 mole % ethylene glycol; 40 to less than 50 mole %
2,2,4,4-tetramethyl-1,3-cyclobutanediol and greater than 50 to 60 mole %
ethylene glycol; 40 to 50 mole % 2,2,4,4-tetramethyl-1,3-cyclobutanediol and
50
to 60 mole % ethylene glycol; and 40 to 45 mole % 2,2,4,4-tetramethyl-1,3-
cyclobutanediol and 55 to 60 mole % ethylene glycol.
[00128] In other aspects of the invention, the glycol component for the
polyesters useful in the invention include but are not limited to at least one
of the
following combinations of ranges: about 45 to less than 90 mole % 2,2,4,4-
tetramethyl-1,3-cyclobutanediol and greater than 10 to about 55 mole %
ethylene
glycol; 45 to 85 mole % 2,2,4,4-tetramethyl-1,3-cyclobutanediol and 15 to 55
mole % ethylene glycol; 45 to 80 mole % 2,2,4,4-tetramethyl-1,3-
cyclobutanediol
and 20 to 55 mole % ethylene glycol; 45 to 75 mole % 2,2,4,4-tetramethyl-1,3-
cyclobutanediol and 25 to 55 mole % ethylene glycol; 45 to 70 mole % 2,2,4,4-
tetramethyl-1,3-cyclobutanediol and 30 to 55 mole % ethylene glycol; 45 to 65
mole % 2,2,4,4-tetramethyl-1,3-cyclobutanediol and 35 to 55 mole % ethylene
glycol; 45 to 60 mole % 2,2,4,4-tetramethyl-1,3-cyclobutanediol and 40 to 55
mole % ethylene glycol; greater than 45 to 55 mole % 2,2,4,4-tetramethyl-1,3-
cyclobutanediol and 45 to less than 55 mole % ethylene glycol; 45 to 55 mole %
2,2,4,4-tetramethyl-1,3-cyclobutanediol and 45 to 55 mole % ethylene glycol;
and
45 to 50 mole % 2,2,4,4-tetramethyl-1,3-cyclobutanediol and 50 to 60 mole %
ethylene glycol. -
[00129] In other aspects of the invention, the glycol component for the
polyesters useful in the invention include but are not limited to at least one
of the
following combinations of ranges: greater than 50 to less than 90 mole %
2,2,4,4-tetramethyl-1,3-cyclobutanediol and greater than 10 to less than 50
mole
% ethylene glycol; greater than 50 to 85 mole % 2,2,4,4-tetramethyl-1,3-
cyclobutanediol and 15 to less than 50 mole % ethylene glycol; greater than 50
to
80 mole % 2,2,4,4-tetramethyl-1,3-cyclobutanediol and 20 to less than 50 mole
%
ethylene glycol; greater than 50 to 75 mole % 2,2,4,4-tetramethyl-1,3-
cyclobutanediol and 25 to less than 50 mole % ethylene glycol; greater than 50
to
70 mole % 2,2,4,4-tetramethyl-1,3-cyclobutanediol and 30 to less than 50 mole
%
ethylene glycol; greater than 50 to 65 mole % 2,2,4,4-tetramethyl-1,3-
CA 02666585 2009-04-16
WO 2008/051321 PCT/US2007/015704
-42-
cyclobutanediol and 35 to less than 50 mole % ethylene glycol; greater than 50
to
60 mole % 2,2,4,4-tetramethyl-1,3-cyclobutanediol and 40 to less than 50 mole
%
ethylene glycol.
[00130] In other aspects of the invention, the glycol component for the
polyesters usefui in the invention include but are not limited to at least one
of the
following combinations of ranges: about 55 to less than 90 mole % 2,2,4,4-
tetramethyl-1,3-cyclobutanediol and greater than 10 to about 45 mole %
ethylene
glycol; 55 to 85 mole % 2,2,4,4-tetramethyl-1,3-cyclobutanediol and 15 to 45
mole % ethylene glycol; 55 to 80 mole % 2,2,4,4-tetramethyl-1,3-
cyclobutanediol
and 20 to 45 mole % ethylene glycol; 55 to 75 mole % 2,2,4,4-tetramethyl-1,3-
cyclobutanediol and 25 to 45 mole % ethylene glycol; 55 to 70 mole % 2,2,4,4-
tetramethyl-1,3-cyclobutanediol and 30 to 45 mole % ethylene glycol; 55 to 65
mole % 2,2,4,4-tetramethyl-1,3-cyclobutanediol and 35 to 45 mole % ethylene
.glycol; and 55 to 60 mole % 2,2,4,4-tetramethyl-1,3-cyclobutanediol and 40 to
45
mole % ethylene glycol.
[00131] In other aspects of the invention, the glycol component for the
polyesters useful in the invention include but are not limited to at least one
of the
following combinations of ranges: about 60 to less than 90 mole % 2,2,4,4-
tetramethyl-1,3-cyclobutanediol and greater than 10 to about 40 mole %
ethylene
glycol; about 60 to about 85 mole % 2,2,4,4-tetramethyl-1,3-cyclobutanediol
and
about 15 to about 40 mole % ethylene glycol; about 60 to about 80 mole %
2,2,4,4-tetramethyl-1,3-cyclobutanediol and about 20 to about 40 mole %
ethylene glycol; 60 to 75 mole % 2,2,4,4-tetramethyl-1,3-cyclobutanediol and
25
to 40 mole % ethylene glycol; and 60 to 70 mole % 2,2,4,4-tetramethyl-1,3-
cyclobutanediol and 30 to 40 mole % ethylene glycol.
[00132] In other aspects of the invention, the glycol component for the
polyesters useful in the invention include but are not limited to at least one
of the
following combinations of ranges: about 65 to less than 90 mole % 2,2,4,4-
tetramethyl-1,3-cyclobutanediol and greater than 10 to about 35 mole %
ethylene
glycol; 65 to 85 mole % 2,2,4,4-tetramethyl-1,3-cyclobutanediol and 15 to 35
mole % ethylene glycol; 65 to 80 mole % 2,2,4,4-tetramethyl-1,3-
cyclobutanediol
and 20 to 35 mole % ethylene glycol; 65 to 75 mole % 2,2,4,4-tetramethyl-1,3-
CA 02666585 2009-04-16
WO 2008/051321 PCT/US2007/015704
-43-
cyclobutanediol and 25 to 35 mole % ethylene glycol; and 65 to 70 mole %
2,2,4,4-tetramethyl-1,3-cyclobutanediol and 30 to 35 mole % ethylene glycol.
(00133] In other aspects of the invention, the glycol component for the
polyesters useful in the invention include but are not limited to at least one
of the
following combinations of ranges: about 70 to less than 90 mole % 2,2,4,4-
tetramethyl-1,3-cyclobutanediol and greater than 10 to about 30 mole %
ethylene
glycol; about 70 to about 85 mole % 2,2,4,4-tetramethyl-1,3-cyclobutanediol
and
about 15 to about 30 mole % ethylene glycol; about 70 to about 80 mole %
2,2,4,4-tetramethyl-1,3-cyclobutanediol and about 20 to about 30 mole %
ethylene glycol; about 70 to about 75 mole % 2,2,4,4-tetramethyl-1,3-
cyclobutanediol and about 25 to about 30 mole % ethylene glycol.
[00134] In other aspects of the invention, the glycol component for the
polyesters useful in the invention include but are not limited to at least one
of the
following combinations of ranges: about 75 to less than 90 mole % 2,2,4,4-
tetramethyl-1,3-cyclobutanediol and greater than 10 to about 25 mole %
ethylene
glycol; and 75 to 85 mole % 2,2,4,4-tetramethyl-1,3-cyclobutanediol and 15 to
25
mole % ethylene glycol.
[00135] In other aspects of the invention, the glycol component for the
polyesters useful in the invention include but are not limited to at least one
of the
following combinations of ranges: about 80 to less than 90 mole % 2,2,4,4-
tetramethyl-1,3-cyclobutanediol and greater than 10 to about 20 mole %
ethylene
glycol.
[00136] In other aspects of the invention, the glycol component for the
polyesters useful in the invention include but are not limited to at least one
of the
following combinations of ranges 37 to 80 mole % 2,2,4,4-tetramethyl-1,3-
cyclobutanediol and 20 to 63 mole % ethylene glycol; 40 to less than 45 mole %
2,2,4,4-tetramethyl-1,3-cyclobutanediol and greater than 55 to 60 mole %
ethylene glycol; greater than 45 to 55 mole % 2,2,4,4-tetramethyl-1,3-
cyclobutanediol and 45 to less than 55 mole % ethylene glycol; and 46 to 55
mole % 2,2,4,4-tetramethyl-1,3-cyclobutanediol and 45 to 54 mole % ethylene
glycol; and 46 to 65 mole % 2,2,4,4-tetramethyl-1,3-cyclobutanediol and 35 to
54
mole % ethylene glycol.
CA 02666585 2009-04-16
WO 2008/051321 PCT/US2007/015704
-44-
[001371 In other aspects of the invention, the glycol component for the
polyesters useful in the invention include but are not limited to at least one
of the
following combinations of ranges: 0.01 to 15 mole % 2,2,4,4-tetramethyl-1,3-
cyclobutanediol and 85 to 99.99 mole % ethylene glycol; 0.01 to less than 15
mole % 2,2,4,4-tetramethyl-1,3-cyclobutanediol and greater than 85 to 99.99
mole % ethylene glycol; 0.01 to 14 mole % 2,2,4,4-tetramethyl-1,3-
cyclobutanediol and 86 to 99.99 mole % 1,4-ethylene glycol; 0.01 to 13 mole %
2,2,4,4-tetramethyl-1,3-cyclobutanediol and 87 to 99.99 mole % ethylene
glycol;
0.01 to 12 mole % 2,2,4,4-tetramethyl-1,3-cyclobutanediol and 88 to 99.99 mole
% 1,4-cyclohexanedimethano; 0.01 to 11 mole % 2,2,4,4-tetramethyl-1,3-
cyclobutanediol and 89 to 99.99 mole % ethylene glycol; 0.01 to 10 mole %
2,2,4,4-tetramethyl-1,3-cyclobutanediol and 90 to 99.99 mole % ethylene
glycol;
0.01 to less than 10 mole % 2,2,4,4-tetramethyl-1,3-cyclobutanediol and
greater
than 90 to 99.99 mole % ethylene glycol; 0.01 to 9 mole % 2,2,4,4-tetramethyl-
1,3-cyclobutanediol and 91 to 99.99 mole % ethylene glycol; 0.01 to 8 mole %
2,2,4,4-tetramethyl-1,3-cyclobutanediol and 92 to 99.99 mole % ethylene
glycol;
0.01 to 7 mole % 2,2,4,4-tetramethyl-1,3-cyclobutanediol and 93 to 99.99 mole
%
ethylene glycol; 0.01 to 5 mole % 2,2,4,4-tetramethyl-1,3-cyclobutanediol and
95
to 99.99 mole % ethylene glycol; 0.01 to less than 5 mole % 2,2,4,4-
tetramethyl-
1,3-cyclobutanediol and greater than 95 to 99.99 mole % ethylene glycol; 0.01
to
4.5 mole % 2,2,4,4-tetramethyl-1,3-cyclobutanediol and 95.5 to 99.99 mole %
ethylene glycol; 0.01 to 4 mole % 2,2,4,4-tetramethyl-1,3-cyclobutanediol and
96
to 99.99 mole % ethylene glycol; 0.01 to 3.5 mole % 2,2,4,4-tetramethyl-1,3-
cyclobutanediol and 96.5 to 99.99 mole % ethylene glycol; 0.01 to 3 mole %
2,2,4,4-tetramethyl-1,3-cyclobutanediol and 97 to 99.99 mole % ethylene
glycol;
0.01 to 2.5 mole % 2,2,4,4-tetramethyl-1,3-cyclobutanediol and 97.5 to 99.99
mole % ethylene glycol; 0.01 to 2 mole % 2,2,4,4-tetramethyl-1,3-
cyclobutanediol
and 98 to 99.99 mole % ethylene glycol; 0.01 to 1.5 mole % 2,2,4,4-tetramethyl-
1,3-cyclobutanediol and 98.5 to 99.99 mole % ethylene glycol; 0.01 to 1 mole %
2,2,4,4-tetramethyl-1,3-cyclobutanediol and 99 to 99.99 mole % ethylene
glycol;
and 0.01 to 0.5 mole % 2,2,4,4-tetramethyl-1,3-cyclobutanediol and 99.5 to
99.99
mole % ethylene glycol.
CA 02666585 2009-04-16
WO 2008/051321 PCT/US2007/015704
- 45 -
[00138] In embodiments where the mole % of 2,2,4,4-tetramethyl-1,3-
cyclobutanediol residues, is 0.01 to 5 mole % based on the mole percentages
for
the diol component equaling 100 mole % and where the presence of
cyclohexanedimethanol is required, the glycol component for the polyesters
useful the invention include but are not limited to at least of the following
combinations of ranges: 0.01 to 5 mole % of 2,2,4,4-tetramethyl-1,3-
cyclobutanediol residues, 89 to 94.99 mole % of ethylene glycol residues, and
5
to 10 mole % of cyclohexanedimethanot; 0.01 to 5 mole % of 2,2,4,4-tetramethyl-
1,3-cyclobutanediol residues, 89 to 94.99 mole % of ethylene glycol residues,
and 5 to 10 mole % of cyclohexanedimethanol; 0.01 to 5 mole % of 2,2,4,4-
tetramethyl-1,3-cyclobutanediol residues, 84 to 89.99 mole % of ethylene
glycol
residues, and 10 to 15 mole % of cyclohexanedimethanol; 0.01 to 5 mole % of
2,2,4,4-tetramethyl-1,3-cyclobutanedioI residues, 79 to 84.99 mole % of
ethylene
glycol residues, and 15 to 20 mole % of cyclohexanedimethanol; 0.01 to 5 mole
% of 2,2,4,4-tetramethyl-1,3-cyclobutanedioI residues, 74 to 79.99 mole % of
ethylene glycol residues, and 20 to 25 mole % of cyclohexanedimethanol; 0.01
to
mole % of 2,2,4,4-tetramethyl-1,3-cyclobutanedioI residues, 69 to 74.99 mole
% of ethylene glycol residues, and 25 to 30 mole % of cyclohexanedimethanol;
0.01 to 5 mole % of 2,2,4,4-tetramethyl-1,3-cyclobutanedioI residues, 64 to
69.99
mole % of ethylene glycol residues, and 30 to 35 mole % of
cyclohexanedimethanol; 0.01 to 5 mole % of 2,2,4,4-tetramethyl-1,3-
cyclobutanediol residues, 59 to 64.99 mole % of ethylene Iglycol residues, and
35
to 40 mole % of cyclohexanedimethanol; 0.01 to 5 mole % of 2,2,4,4-tetramethyl-
1,3-cyclobutanediol residues, 54 to 59.99 mole % of ethylene glycol residues,
and 40 to 45 mole % of cyclohexanedimethanol; 0.01 to 5 mole % of 2,2,4,4-
tetramethyl-1,3-cyclobutanediol residues, 49 to 54.99 mole % of ethylene
glycol
residues, and 45 to 50 mole % of cyclohexanedimethanol; 0.01 to 5 mole % of
2,2,4,4-tetramethyl-1,3-cyclobutanedioI residues, 44 to 49:99 mole % of
ethylene
glycol residues, and 50 to 55 mole % of cyclohexanedimethanol; 0.01 to 5 mole
% of 2,2,4,4-tetramethyl-1,3-cyclobutanedioI residues, 39 to 44.99 mole % of
ethylene glycol residues, and 55 to 60 mole % of cyclohexanedimethanol; 0.01
to
5 mole % of 2,2,4,4-tetramethyl-1,3-cyclobutanedioI residues, 34 to 39.99 mole
%
CA 02666585 2009-04-16
WO 2008/051321 PCT/US2007/015704
-46-
of ethylene glycol residues, and 60 to 65 mole % of cyclohexanedimethanol;
0.01
to 5 mole % of 2,2,4,4-tetramethyl-1,3-cyclobutanediol residues, 29 to 34.99
mole
% of ethylene glycol residues, and 65 to 70 mole % of cyclohexanedimethanol;
0.01 to 5 mole % of 2,2,4,4-tetramethyl-1,3-cyclobutanediol residues, 24 to
29.99
mole % of ethylene glycol residues, and 70 to 75 mole % of
cyclohexanedimethanol; 0.01 to 5 mole % of 2,2,4,4-tetrainethyl-1,3-
cyclobutanediol residues, 19 to 24.99 mole % of ethylene glycol residues, and
75
to 80 mole % of cyclohexanedimethanol; 0.01 to 5 mole % of 2,2,4,4-tetramethyl-
1,3-cyclobutanediol residues, 14 to 19.99 mole % of ethylene glycol residues,
and 80 to 85 mole % of cyclohexanedimethanol; 0.01 to 5 mole % of 2,2,4,4-
tetramethyl-1,3-cyclobutanediol residues, 9 to 14.99 mole % of ethylene glycol
residues, and 85 to 90 mole % of cyclohexanedimethanol; 0.01 to 5 mole % of
2,2,4,4-tetramethyl-1,3-cyclobutanediol residues, 4 to 9.99 mole % of ethylene
glycol residues, and 90 to 95 mole % of cyclohexanedimethanol; 0.01 to 5 mole
% of 2,2,4,4-tetramethyl-1,3-cyclobutanediol residues, 95 to 99.99 mole % of
ethylene glycol residues, and 0 to 5 mole % of cyclohexanedimethanol.
[00139] In other aspects of the invention, the glycol component for the
polyesters useful in the invention include but are not limited to at least one
of the
following combinations of ranges: 20 to 40 mole % 2,2,4,4-tetramethyl-1,3-
cyclobutanediol, 20 to 40 mole % cyclohexanedimethanol and 30 to 60 mole %
ethylene glycol; 20 to 35 mole % 2,2,4,4-tetramethyl-1,3-cyclobutanediol, 20
to
40 mole % cyclohexanedimethanol and 30 to 60 mole % ethylene glycol; 20 to 30
mole % 2,2,4,4-tetramethyl-1,3-cyclobutanediol, 20 to 40 mole %
cyclohexanedimethanol and 30 to 60 mole % ethylene glycol; and 20 to 25 mole
% 2,2,4,4-tetramethyl-1,3-cyclobutanediol, 20 to 40 mole %
cyclohexanedimethanol and 30 to 60 mole % ethylene glycol.
[00140] In other aspects of the invention, the glycol component for the
polyesters useful in the invention include but are not limited to at least one
of the
following combinations of ranges: 25 to 40 mole % 2,2,4,4-tetramethyl-1,3-
cyclobutanediol, 20 to 40 mole % cyclohexanedimethanol and 30 to 55 mole %
ethylene glycol; 25 to 35 mole % 2,2,4,4-tetramethyl-1,3-cyclobutanediol, 20
to
40 mole % cyclohexanedimethanol and 30 to 55 mole % ethylene glycol; and 25
CA 02666585 2009-04-16
WO 2008/051321 PCT/US2007/015704
- 47 -
to 30 mole % 2,2,4,4-tetramethyl-1,3-cyclobutanediol, 20 to 40 mole %
cyclohexanedimethanol and 30 to 55 mole % ethylene glycol.
[00141] In other aspects of the invention, the glycol component for the
polyesters useful in the invention include but are not limited to at least one
of the
following combinations of ranges: 30 to 40 mole % 2,2,4,4-tetramethyl-1,3-
cyclobutanediol, 20 to 40 mole % cyclohexanedimethanol and 30 to 50 mole %
ethylene glycol; 30 to 35 mole % 2,2,4,4-tetramethyl-1,3-cyclobutanediol, 20
to
40 mole % cyclohexanedimethanol and 30 to 50 mole % ethylene glycol.
[00142] In other aspects of the invention, the glycol component for the
polyesters useful in the invention include but are not limited to at least one
of the
following combinations of ranges: 20 to 40 mole % 2,2,4,4-tetramethyl-1,3-
cyclobutanediol, 20 to 35 mole % cyclohexanedimethanol and 30 to 60 mole %
ethylene glycol; 20 to 40 mole % 2,2,4,4-tetramethyl-1,3-cyclobutanediol, 20
to
30 mole % cyclohexanedimethanol and 30 to 60 mole % ethylene glycol; and 20
to 40 mole % 2,2,4,4-tetramethyl-1,3-cyclobutanediol, 20 to 25 mole %
cyclohexanedimethanol and 30 to 60 mole % ethylene glycol.
[00143] In other aspects of the invention, the glycol component for the
polyesters useful in the invention include but are not limited to at least one
of the
following combinations of ranges: 20 to 40 mole % 2,2,4,4-tetramethyl-1,3-
cyclobutanediol, 25 to 40 mole % cyclohexanedimethanol and 30 to 55 mole %
ethylene glycol; 20 to 40 mole % 2,2,4,4-tetramethyl-1,3-cyclobutanediol, 25
to
35 mole % cyclohexanedimethanol and 30 to 55 mole % ethylene glycol; and 20
to 40 mole % 2,2,4,4-tetramethyl-1,3-cyclobutanediol, 25 to 30 mole %
cyclohexanedimethanol and 30 to 55 mole % ethylene glycol.
[00144] In other- aspects of the invention, the glycol component for the
polyesters useful in the invention include but are not limited to at least one
of the
following combinations of ranges: 20 to 40 mole % 2,2,4,4-tetramethyl-1,3-
cyclobutanediol, 30 to 40 mole % cyclohexanedimethanol and 30 to 50 mole %
ethylene glycol; 20 to 40 mole % 2,2,4,4-tetramethyl-1,3-cyclobutanediol, 30
to
35 mole % cyclohexanedimethanol and 30 to 50 mole % ethylene glycol.
[00145] In one embodiment, the glycol component of the polyester(s) useful in
the invention comprises 2,2,4,4-tetramethyl-1,3-cyclobutanediol and
CA 02666585 2009-04-16
WO 2008/051321 PCT/US2007/015704
-48-
cyclohexanedimethanol wherein the sum of the mole percentages of 2,2,4,4-
tetramethyl-1,3-cyclobutanediol and cyclohexanedimethanol is from 40 to less
than 70 mole % of the total mole % of the total glycol component.
[00146] In any embodiment where the mole % of 2,2,4,4-tetramethyl-1,3-
cyclobutanediol residues, is 0.01 to 5 mole % based on the mole percentages
for
the diol component equaling 100 mole % and where the presence of
cyclohexanedimethanol is required, the glycol component for the polyesters
useful the invention can also include embodiments where 0.01 to less than 5
mole % 2,2,4,4-tetramethyl-1,3-cyclobutanediol residues is present and a
corresponding reduction in either cyclohexanedimethanol residues and/or
ethylene glycol residues would be contemplated within the scope of this
invention.
[00147] The glycol component may also contain one of the following ranges of
2,2,4,4-te#ramethyl-1,3-cyclobutanediol residues: 0.01 to 10 mole%; 0.01 to
9.5
mole % 0.01 to 9 mole %; 0.01 to 8.5 mole %; 0.01 to 8 mole %; 0.01 to 7.5
mole
%; 0.01 to 7.0; 0.01 to 6.5 mole %; 0.01 to 6 mole %; 0.01 to 5.5 mole %; 0.01
to
mole %; 0.01 to less than 5 mole %; 0.01 to 4.5 mole %; 0.01 to 4 mole %; 0.01
to 3.5 mole %; 0.01 to 3 mole %; 0.01 to 2.5 mole %; 0.01 to 2.0 mole %; 0.01
to
2.5 mole %; 0.01 to 2 mole %; 0.01 to 1.5 mole %; 0.01 to 1.0 mole %; and 0.01
to 0.5 mole %.
[00148] In certain embodiments, the remainder of the glycol component can
include, but is not limited, to any amount of cyclohexanedimethanol and/or
ethylene glycol residues so long as the total amount of the glycol component
equals 100 mole % and so long as the total amount of ethylene glycol in the
final
polyester is greater than 10 mole %.
[00149] For embodiments of the invention, the polyesters useful in the
invention
may exhibit at least one of the following inherent viscosities as determined
in
60/40 (wt/wt) phenol/ tetrachloroethane at a concentration of 0.25 g/50 ml at
25 C: 0.50 to 1.2 dUg; 0.50 to 1.1 dUg; 0.50 to 1 dUg; 0.50 to less than 1
dUg;
0.50 to 0.98 dUg; 0.50 to 0.95 dUg; 0.50 to 0.90 dUg; 0.50 to 0.85 dUg; 0.50
to
0.80 dUg; 0.50 to 0.75 dUg; 0.50 to less than 0.75 dUg; 0.50 to 0.72 dUg; 0.50
to 0.70 dUg; 0.50 to less than 0.70 dUg; 0.50 to 0.68 dUg; 0.50 to less than
0.68
CA 02666585 2009-04-16
WO 2008/051321 PCT/US2007/015704
-49-
dUg; 0.50 to 0.65 dUg; 0.55 to 1.2 dUg; 0.55 to 1.1 dUg; 0.55 to 1 dUg; 0.55
to
less than 1 dUg; 0.55 to 0.98 dUg; 0.55 to 0.95 dUg; 0.55 to 0.90 dUg; 0.55 to
0.85 dUg; 0.55 to 0.80 dUg; 0.55 to 0.75 dUg; 0.55 to less than 0.75 dUg; 0.55
to 0.72 dUg; 0.55 to 0.70 dUg; 0.55 to less than 0.70 dUg; 0.55 to 0.68 dUg;
0.55 to less than 0.68 dUg; 0.55 to 0.65 dUg; 0.58 to 1.2 dUg; 0.58 to 1.1
dUg;
0.58 to 1 dUg; 0.58 to less than 1 dUg; 0.58 to 0.98 dUg; 0_58 to 0.95 dUg;
0.58
to 0.90 dUg; 0.58 to 0.85 dUg; 0.58 to 0.80 dUg; 0.58 to 0.75 dUg; 0.58 to
less
than 0.75 dUg; 0.58 to 0.72 dUg; 0.58 to 0.70 dUg; 0.58 to less than 0.70 dUg;
0.58 to 0.68 dUg; 0.58 to less than 0.68 dUg; 0.58 to 0.65 dUg; 0.60 to 1.2
dUg;
0.60 to 1.1 dUg; 0.60 to 1 dUg; 0.60 to less than 1 dUg; 0.60 to 0.98 dUg;
0.60
to 0.95 dUg; 0.60 to 0.90 dUg; 0.60 to 0.85 dUg; 0.60 to 0.80 dUg; 0.60 to
0.75
dUg; 0.60 to less than 0.75 dUg; 0.60 to 0.72 dUg; 0.60 to 0.70 dUg; 0.60 to
less
than 0.70 dUg; 0.60 to 0.68 dUg; 0.60 to less than 0.68 dUg; 0.60 to 0.65 dUg;
0.65 to 1.2 dUg; 0.65 to 1.1 dUg; 0.65 to 1 dUg; 0.65 to less than 1 dUg; 0.65
to
0.98 dUg; 0.65 to 0.95 dUg; 0.65 to 0.90 dUg; 0_65 to 0.85 dUg; 0.65 to 0.80
dUg; 0.65 to 0.75 dUg; 0_65 to less than 0.75 dUg; 0.65 to 0.72 dUg; 0.65 to
0.70 dUg; 0.65 to less than 0.70 dUg; 0.68 to 1.2 dUg; 0.68 to 1.1 dUg; 0.68
to 1
dUg; 0.68 to less than 1 dUg; 0.68 to 0.98 dUg; 0.68 to 0.95 dUg; 0.68 to 0.90
dUg; 0.68 to 0.85 dUg; 0.68 to 0.80 dUg; 0.68 to 0.75 dUg; 0.68 to less than
0.75 dUg; 0.68 to 0.72 dUg.
[00150] It is contemplated that compositions useful in the invention can
possess at least one of the inherent viscosity ranges described herein and at
least one of the monomer ranges for the compositions described herein unless
otherwise stated. It is also contemplated that compositions useful in the
invention
can possess at least one of the T. ranges described herein and at least one of
the monomer ranges for the compositions described herein unless otherwise
stated. It is also contemplated that compositions useful in the invention can
possess at least one of the inherent viscosity ranges described herein, at
least
one of the Tg ranges described herein, and at least one of the monomer ranges
for the compositions described herein unless otherwise stated.
[00151] In one embodiment, terephthalic acid may be used as the starting
material. In another embodiment, dimethyl terephthalate may be used as the
CA 02666585 2009-04-16
WO 2008/051321 PCT/US2007/015704
-50-
starting material. In yet another embodiment, mixtures of terephthalic acid
and
dimethyl terephthalate may be used as the starting material and/or as an
intermediate material.
[00152] In certain embodiments, terephthalic acid or an ester thereof, such
as,
for example, dimethyl terephthalate or a mixture of terephthalic acid residues
and
an ester thereof can make up a portion or all of the dicarboxylic acid
component
used to form the polyesters useful in the invention. In certain embodiments,
terephthalic acid residues can make up a portion or all of the dicarboxylic
acid
component used to form the polyesters useful in the invention. In certain
embodiments, higher amounts of terephthalic acid can be used in order to
produce a higher impact strength polyester. For purposes of this disclosure,
the
terms "terephthalic acid" and "dimethyl terephthalate" are used
interchangeably
herein. In one embodiment, dimethyl terephthalate is part or all of the
dicarboxylic acid component used to make the polyesters useful in the present
invention. In all embodiments, ranges of from 70 to 100 mole %; or 80 to 100
mole %; or 90 to 100 mole %; or 99 to 100 mole %; or 100 mole % terephthalic
acid and/or dimethyl terephthalate and/or mixtures thereof may be used.
[00153] In addition to terephthalic acid, the dicarboxylic acid component of
the
polyesters useful in the invention can comprise up to 10 mole %, up to 5
mole%,
or up to 1 mole % of one or more modifying aromatic dicarboxylic acids. Yet
another embodiment contains 0 mole % modifying aromatic dicarboxylic acids.
Thus, if present, it is contemplated that the amount of one or more modifying
aromatic dicarboxylic acids can range from any of these preceding endpoint
values including, for example, 0.01 to 10 mole %, from 0.01 to 5 mole % and
from
0.01 to 1 mole %. In one embodiment, modifying aromatic dicarboxylic acids
that may be used in the present invention include but are not limited to those
having up to 20 carbon atoms, and which can be linear, para-oriented, or
symmetrical. Examples of modifying aromatic dicarboxylic acids which may be
used in this invention include, but are not limited to, isophthalic acid, 4,4'-
biphenyldicarboxylic acid, 1,4-, 1,5-, 2,6-, 2,7-naphthalenedicarboxylic acid,
and
trans-4,4'-stilbenedicarboxylic acid, and esters thereof. In one embodiment,
the
modifying aromatic dicarboxylic acid is isophthalic acid.
CA 02666585 2009-04-16
WO 2008/051321 PCT/US2007/015704
-51 -
[00154] The carboxylic acid component of the polyesters useful in the
invention
can be further modified with up to 10 mole %, such as up to 5 mole % or up to
1
mole % of one or more aliphatic dicarboxylic acids containing 2-16 carbon
atoms,
such as, for example, cyclohexanedicarboxylic, malonic, succinic, glutaric,
adipic,
pimelic, suberic, azelaic and dodecanedioic dicarboxylic acids. Certain
embodiments can also comprise 0.01 to 10 mole %, such as 0.1 to 10 mole %, 1
or 10 mole %, 5 to 10 mole % of one or more modifying aliphatic dicarboxylic
acids. Yet another embodiment contains 0 mole % modifying aliphatic
dicarboxylic acids. The total mole % of the dicarboxylic acid component is 100
mole %. In one embodiment, adipic acid and/or glutaric acid are provided in
the
modifying aliphatic dicarboxylic acid component of the invention.
[00155] The modifying dicarboxylic acids of the invention can include indan
dicarboxylic acids, for example, indan-1,3-dicarboxylic acids and/or
phenylindan
dicarboxylic acids. In one embodiment, the dicarboxylic acid may be chosen
from at least one of 1,2,3-trimethyl-3-phenylindan-4',5-dicarboxylic acid and
1,1,3-trimethyl-5-carboxy-3-(4-carboxyphenyl)indan dicarboxylic acid. For the
purposes of this invention, any of the indan dicarboxylic acids described in
United
States Patent Application Publication No. 2006/0004151A1 entitled "Copolymers
Containing Indan Moieties and Blends Thereof' by Shaikh et al., assigned to
General Electric Company may be used as at least one modifying dicarboxylic
acid within the scope of this invention; United States Patent Application
Publication No. 2006/0004151A1 is incorporated herein by reference with
respect
to any of the indan dicarboxylic acids described therein.
[00156] Esters of terephthalic acid and the other modifying dicarboxylic acids
or
their corresponding esters and/or salts may be used instead of the
dicarboxylic
acids. Suitable examples of dicarboxylic acid esters include, but are not
limited
to, the dimethyl, diethyl, dipropyl, diisopropyl, dibutyl, and diphenyl
esters. In one
embodiment, the esters are chosen from at least one of the following: methyl,
ethyl, propyl, isopropyl, and phenyl esters.
[00157] For the desired polyester, the molar ratio of cis/trans 2,2,4,4-
tetramethyl-1,3-cyclobutanediol can vary from the pure form of each and
mixtures
thereof. In certain embodiments, the molar percentages for cis and/or trans
CA 02666585 2009-04-16
WO 2008/051321 PCT/US2007/015704
-52-
2,2,4,4,-tetramethyl-1,3-cyclobutanediol are greater than 50 mole % cis and
less
than 50 mole % trans; or greater than 55 mole % cis and less than 45 mole %
trans; or 30 to 70 mole % cis and 70 to 30 mole % trans; or 40 to 60 mole %
cis
and 60 to 40 mole % trans; or 50 to 70 mole % trans and 50 to 30 mole % cis;
or
50 to 70 mole % cis and 50 to 30 mole % trans; or 60 to 70 mole % cis and 30
to
40 mole % trans; or greater than 70 mole % cis and less than 30 mole % trans;
wherein the total mole percentages for cis- and trans- 2,2,4,4-tetramethyl-1,3-
cyclobutanediol is equal to 100 mole %. In an additional embodiment, the molar
ratio of cis/trans 2,2,4,4-tetramethyl-1,3-cyclobutanediol can vary within the
range
of 50/50 to 0/100, for example, between 40/60 to 20/80.
[00158] The cyclohexanedimethanol may be cis, trans, or a mixture thereof, for
example, a cis/trans ratio of 60:40 to 40:60 or a cis/trans ratio of 70:30 to
30:70.
In another embodiment, the trans-cyclohexanedimethanol can be present in an
amount of 60 to 80 mole % and the cis-cyclohexanedimethanol can be present in
an amount of 20 to 40 mole % wherein the total percentages of cis-
cyclohexanedimethanol and trans-cyclohexanedimethanol is equal to 100 mole
%. In particular embodiments, the trans-cyclohexanedimethanol can be present
in an amount of 60 mole % and the cis-cyclohexanedimethanol can be present in
an amount of 40 mole %. In particular embodiments, the trans-
cyclohexanedimethanol can be present in an amount of 70 mole % and the cis-
cyclohexanedimethanol can be present in an amount of 30 mole %. Any of 1,1-,
1,2-, 1,3-, 1,4- isomers of cyclohexanedimethanol or mixtures thereof may be
present in the glycol component of this invention. Cis and trans isomers do
not
exist for 1,1-cyclohexanedimethanol.
[00159] In one embodiment, the polyesters useful in the invention comprise
1,4-cyclohexanedimethanol. In another embodiment, the polyesters useful in the
invention comprise 1,4-cyclohexanedimethanol and 1,3-cyclohexanedimethanol.
The molar ratio of cis/trans 1,4-cyclohexandimethanol can vary within the
range
of 50/50 to 0/100, for example, between 40/60 to 20/80.
[00160] In one embodiment, the glycol component of the polyester portion of
the polyester compositions useful in the invention can contain 30 mole % or
less
of one or more modifying glycols which are not 2,2,4,4-tetramethyl-1,3-
CA 02666585 2009-04-16
WO 2008/051321 PCT/US2007/015704
-53-
cyclobutanediol or cyclohexanedimethanol or ethylene glycol; in one
embodiment, the glycol component of the polyester portion of the polyester
compositions useful in the invention can contain 25 mole % or less of one or
more modifying glycols-which are not 2,2,4,4-tetramethyl-1,3-cyclobutanediol
or
cyclohexanedimethanol or ethylene glycol; in one embodiment, the glycol
component of the polyester portion of the polyester compositions useful in the
invention can contain 20 mole % or less of one or more modifying glycols which
are not 2,2,4,4-tetramethyl-1,3-cyclobutanediol or cyclohexanedimethanol or
ethylene glycol; in one embodiment, the polyesters useful in the invention may
contain less than 15 mole % or of one or more modifying glycols. In another
embodiment, the polyesters useful in the invention can contain 10 mole % or
less
of one or more modifying glycols. In another embodiment, the polyesters useful
in the invention can contain 5 mole % or less of one or more modifying
glycols.
In another embodiment, the polyesters useful in the invention can contain 3
mole
% or less of one or more modifying glycols. In another embodiment, the
polyesters useful in the invention can contain 2 mole % or less of one or more
modifying glycols. In another embodiment, the polyesters useful in the
invention
can contain 0 mole % modifying glycols.
[00161] Modifying glycols useful in the polyesters useful in the invention
refer to
diols other than 2,2,4,4-tetramethyl-1,3-cyclobutanediol,
cyclohexanedimethanol
and ethylene glycol and can contain 2 to 16 carbon atoms. Examples of suitable
modifying glycols include, but are not limited to, diethylene glycol, 1,2-
propanediol, 1,3-propanediol, neopentyl glycol, 1,4-butanediol, 1,5-
pentanediol,
1,6-hexanediol, p-xylene glycol, polytetramethylene glycol, and mixtures
thereof.
In another embodiment, the modifying glycols include, but are not limited to,
at
least one of 1,3-propanediol and 1,4-butanediol. In one embodiment, at least
one
modifying glycol is diethylene glycol. In one embodiment, the diethylene
glycol is
not added as a separate monomer but is formed during polymerization.
[00162] The polyesters useful in the polyester compositions of the invention
can comprise from 0 to 10 mole percent, for example, from 0.01 to 5 mole
percent, from 0.01 to 1 mole percent, from 0.05 to 5 mole percent, from 0.05
to 1
mole percent, or from 0.1 to 0.7 mole percent, based the total mole
percentages
CA 02666585 2009-04-16
WO 2008/051321 PCT/US2007/015704
-54-
of either the diol or diacid residues; respectively, of one or more residues
of a
branching monomer, also referred to herein as a branching agent, having 3 or
more carboxyl substituents, hydroxyl substituents, or a combination thereof.
In
certain embodiments, the branching monomer or agent may be added prior to
and/or during and/or after the polymerization of the polyester. The
polyester(s)
useful in the invention can thus be linear or branched.
[00163] Examples of branching monomers include, but are not limited to,
multifunctional acids or multifunctional alcohols such as trimellitic acid,
trimellitic
anhydride, pyromellitic dianhydride, trimethylolpropane, glycerol,
pentaerythritol,
citric acid, tartaric acid, 3-hydroxyglutaric acid and the like. In one
embodiment,
the branching monomer residues can comprise 0.1 to 0.7 mole percent of one or
more residues chosen from at least one of the following: trimellitic
anhydride,
pyromellitic dianhydride, glycerol, sorbitol, 1,2,6-hexanetriol,
pentaerythritol,
trimethylolethane, and/or trimesic acid. The branching monomer may be added to
the polyester reaction mixture or blended with the polyester in the form of a
concentrate as described, for example, in U.S. Patent Nos. 5,654,347 and
5,696,176, whose disclosure regarding branching monomers is incorporated
herein by reference.
[00164] The polyesters of the invention can comprise at ileast one chain
extender. Suitable chain extenders include, but are not limited to,
multifunctional
(including, but not limited to, bifunctional) isocyanates, multifunctional
epoxides,
including for example epoxylated novolacs, and phenoxy resins. In certain
embodiments, chain extenders may be added at the end of the polymerization
process or after the polymerization process. If added after the polymerization
process, chain extenders can be incorporated by compounding or by addition
during conversion processes such as injection molding or extrusion. The amount
of chain extender used can vary depending on the specific monomer composition
used and the physical properties desired but is generally about 0.1 percent by
weight to about 10 percent by weight, such as about 0.1 to about 5 percent by
weight, based on the total weight of the polyester.
CA 02666585 2009-04-16
WO 2008/051321 PCT/US2007/015704
-55-
[00165] The glass transition temperature (Ty) of the polyesters useful in the
invention was determined using a TA DSC 2920 from Thermal Analyst Instrument
at a scan rate of 20 C/min.
[00166] Because of the long crystallization half-times (e.g., greater than 5
minutes) at 170 C exhibited by certain polyesters useful in the present
invention,
it can be possible to produce articles, including but not limited to,
injection molded
parts, injection blow molded articles, injection stretch blow molded articles,
extruded film, extruded sheet, extrusion blow molded articles, extrusion
stretch
blow molded articles, and fibers. A thermoformable sheet is an example of an
article of manufacture provided by this invention. The polyesters of the
invention
can be amorphous or semicrystalline. In one aspect, certain polyesters useful
in
the invention can have relatively low crystallinity. Certain polyesters useful
in the
invention can thus have a substantially amorphous morphology, meaning that the
polyesters comprise substantially unordered regions of polymer.
[00167] In one embodiment, an "amorphous" polyester can have a
crystallization half-time of greater than 5 minutes at 170 C or greater than
10
minutes at 170 C or greater than 50 minutes at 170 C or greater than 100
minutes at 170 C. In one embodiment, of the invention, the crystallization
half-
times can be greater than 1,000 minutes at 170 C. In another embodiment of the
invention, the crystallization half-times of the polyesters useful in the
invention
can be greater than 10,000 minutes at 170 C. The crystallization halftime of
the
polyester, as used herein, may be measured using methods well-known to
persons of skill in the art. For example, the crystallization half time of the
polyester, t 1/2, can be determined by measuring the light transmission of a
sample via a laser and photo detector as a function of time on a temperature
controlled hot stage. This measurement can be done.by exposing the polymers
to a temperature, Tm., and then cooling it to the desired temperature. The
sample can then be held at the desired temperature by a hot stage while
transmission measurements are made as a function of time. Initially, the
sample
can be visually clear with high light transmission and becomes opaque as the
sample crystallizes. The crystallization half-time is the time at which the
light
CA 02666585 2009-04-16
WO 2008/051321 PCT/US2007/015704
-56-
transmission is halfway between the initial transmission and the final
transmission. Tma, is defined as the temperature required to melt the
crystalline
domains of the sample (if crystalline domains are present). The sample can be
heated to Tmax to condition the sample prior to crystallization half time
measurement. The absolute Tm. temperature is different for each composition.
For example PCT can be heated to some temperature greater than 290 C to melt
the crystalline domains.
[00168] In one embodiment, certain polyesters useful in this invention can be
visually clear. The term "visually clear" is defined herein as an appreciable
absence of cloudiness, haziness, and/or muddiness, when inspected visually. In
another embodiment, when the polyesters are blended with polycarbonate,
including but not limited to, bisphenol A polycarbonates, the blends can be
visually clear.
[00169] In one embodiment, the polyesters useful in the invention and/or the
polyester compositions of the invention, [in one embodiment, in the presence
of
and/or in the absence of toner(s)], can have color values L*, a* and b* which
can
be determined using a Hunter Lab Ultrascan Spectra Colorimeter manufactured
by Hunter Associates Lab Inc., Reston, Va. The color determinations are
averages of values measured on either pellets of the polyesters or plaques or
other items injection molded or extruded from them. They are determined by the
L*a*b* color system of the CIE (International Commission on Illumination)
(translated), wherein L* represents the lightness coordinate, a* represents
the
red/green coordinate, and b* represents the yellow/blue coordinate. In certain
embodiments, the b* values for the polyesters useful in the invention [in one
embodiment, in the presence of and/or in the absence of toner(s)] can be from -
12 to less than 12 and the L* values can be from 50 to 90. In other
embodiments, the b* values for the polyesters useful in the invention [in one
embodiment, in the presence of and/or in the absence of toner(s)] can be
present in one of the following ranges: from -10 to 10; -10 to less than 10; -
10 to
9; -10 to 8; -10 to 7; -10 to 6; -10 to 5; -10 to 4; -10 to 3; -10 to 2; from -
5 to 9; -5
to 8; -5 to 7; -5 to 6; -5 to 5; -5 to 4; -5 to 3; -5 to 2; 0 to 9; 0 to 8; 0
to 7; 0 to 6; 0
to 5; 0 to 4; 0 to 3; 0 to 2; 1 to 10; 1 to 9; 1 to 8; 1 to 7; 1 to 6; 1 to 5;
1 to 4; 1 to
CA 02666585 2009-04-16
WO 2008/051321 PCT/US2007/015704
-57-
3; and 1 to 2. In other embodiments, the L* value for the polyesters useful in
the
invention can be present in one of the following ranges: 50 to 60; 50 to 70;
50 to
80; 50 to 90; 60 to 70; 60 to 80; 60 to 90; 70 to 80; 79 to 90.
[00170] Deleterious color interactions are believed to occur with tin
catalysts or
with titanium catalysts used to prepare polyesters containing ethylene glycol.
In
one embodiment of this invention, the b* color values for the polyesters
useful in
the invention made using at least one titanium compound and at least one tin
compound in combination with at least one phosphorus compound as described
herein are believed to be a significant improvement over using tin catalysts
alone
in the production of these polyesters. The use of at least one titanium
catalyst in
combination with at least one phosphorus compound to make the polyesters
useful in the invention is also believed to be a significant improvement over
the
use of titanium catalysts alone in the production of these polyesters.
1001711 Notched Izod impact strength, as described in ASTM D256, is a
common method of measuring toughness. Notched Izod impact strength is
measured herein at 23 C with a 10-mil notch in a 3.2mm (1/8-inch) thick bar
determined according to ASTM D256. In one embodiment, certain polyesters
useful in the invention can exhibit a notched Izod impact strength of at least
500
J/m (10 ft-lb/in) at 23 C with a 10-mil notch in a 3.2mm (1/8-inch) thick bar
determined according to ASTM D256. In one embodiment, certain polyesters
useful in the invention can exhibit a notched lzod impact strength of from
about
ft-lb/in to about 35 ft-lb/in at 23 C with a 10-mil notch in a 3.2mm (1/8-
inch)
thick bar determined according to ASTM D256. In another embodiment, certain
polyesters useful in the invention can exhibit a notched lzod impact strength
of-
from about 10 ft-lb/in to no break at 23 C with a 10-mil notch in a 3.2mm (1/8-
inch) thick bar determined according to ASTM D256.
[00172] In one embodiment, certain polyesters useful in the invention can
exhibit a density of greater than 1.2 g/mI at 23 C.
[00173] In one embodiment, certain polyesters useful in the invention can
exhibit a flexural modulus at 23 C equal to or greater than 290,000 psi as
defined
by ASTM D790. In another embodiment, certain polyesters useful in the
invention can exhibit a flexural modulus at 23 C from about 290,000 psi to
about
CA 02666585 2009-04-16
WO 2008/051321 PCT/US2007/015704
-58-
370,000 psi as defined by ASTM D790. In another embodiment, certain
polyesters useful in the invention can exhibit a flexural modulus at 23 C from
about 290,000 psi to about 350,000 psi as defined by ASTM D790.
[00174] Certain polyesters useful in the invention can possess at least one of
the following properties: a T9 of from about 100 to about -110 C as measured
by
a TA 2100 Thermal Analyst Instrument at a scan rate of 20 C/min; a flexural
modulus at 23 C equal to or greater than 290,000 psi as defined by ASTM D790;
and a notched Izod impact strength equal to or greater than 10 ft-IbCn
according
to ASTM D256 with a 10-mil notch using a 1/8-inch thick bar at 23 C.
[00175] Other polyesters useful in the invention can possess at least one of
the
following properties: a T. of from about 100 to about 110 C as measured by a
TA 2100 Thermal Analyst Instrument at a scan rate of 20 C/min; a flexural
modulus at 23 C from about 290,000 psi to about 370,000 psi as defined by
ASTM D790; and a notched Izod impact strength of greater than 10 ft-Ibrin to
no
break according to ASTM D256 with a 10-mil notch using a 1/8-inch thick bar at
23 C.
[00176] Other polyesters useful in the invention can possess at least one of
the
following properties: a T9 of from about 100 to about 110 C as measured by a
TA 2100 Thermal Analyst Instrument at a scan rate of 20 C/min; a flexural
modulus at 23 C from about 290,000 psi to about 370,000 psi as defined by
ASTM D790; and a notched Izod impact strength of greater than 10 ft-lb/in to
35
ft-lb/in according to ASTM D256 with a 10-mil notch using a 1/8-inch thick bar
at
23 C.
[00177] In some embodiments, use of the polyester compositions useful in the
invention minimizes and/or eliminates the drying step priorto melt processing
and/or thermoforming.
[00178] In one embodiment, the phosphorus compound(s) useful in the
invention can be an organic compound such as, for example, a phosphorus acid
ester containing halogenated or non-halogenated organic substituents. The
phosphorus compound(s) useful in the invention can comprise a wide range of
phosphorus compounds well-known in the art such as, for example, phosphines,
CA 02666585 2009-04-16
WO 2008/051321 PCT/US2007/015704
-59-
phosphites, phosphinites, phosphonites, phosphinates, phosphonates, phosphine
oxides, and phosphates.
[00179] Examples of phosphorus compounds useful in the invention can
include tributyl phosphate, triethyl phosphate, tri-butoxyethyl phosphate, t-
butylphenyl diphenyl phosphate, 2-ethylhexyl diphenyl phosphate, ethyl
dimethyl
phosphate, isodecyl diphenyl phosphate, trilauryl phosphate, triphenyl
phosphate,
tricresyl phosphate, trixylenyl phosphate, t-butylphenyl diphenylphosphate,
resorcinol bis(diphenyl phosphate), tribenzyl phosphate, phenyl ethyl
phosphate,
trimethyl thionophosphate, phenyl ethyl thionophosphate, dimethyl
methylphosphonate, diethyl methylphosphonate, diethyl pentylphosphonate,
dilauryl methylphosphonate, diphenyl methylphosphonate, dibenzyl
methylphosphonate, diphenyl cresylphosphonate, dimethyl cresylphosphonate,
dimethyl methylth ionophos phonate, phenyl diphenylphosphinate, benzyl
diphenylphosphinate, methyl diphenylphosphinate, trimethyl phosphine oxide,
triphenyl phosphine oxide, tribenzyl phosphine oxide, 4-methyl diphenyl
phosphine oxide, triethyl phosphite, tributyl phosphite, trilauryl phosphite,
triphenyl phosphite, tribenzyl phosphite, phenyl diethyl phosphite, phenyl
dimethyl
phosphite, benzyl dimethyl phosphite, dimethyl methylphosphonite, diethyl
pentylphosphonite, diphenyl methylphosphonite, dibenzyl methylphosphonite,
dimethyl cresylphosphonite, methyl dimethylphosphinite, methyl
diethylphosphinite, phenyl diphenylphosphinite, methyl diphenylphosphinite,
benzyl diphenylphosphinite, triphenyl phosphine, tribenzyl phosphine, and
methyl
diphenyl phosphine. In one embodiment, triphenyl phosphine oxide is excluded
as a thermal stabilizer in the process(es) of making the polyesters useful in
the
invention and/or in the polyester composition(s) of the invention.
[00180] In one embodiment, phosphorus compounds useful in the invention
can be any of the previously described phosphorus-based acids wherein one or
more of the hydrogen atoms of the acid compound (bonded to either oxygen or
phosphorus atoms) are replaced with alkyl, branched alkyl, substituted alkyl,
alkyl
ethers, substituted alkyl ethers, alkyl-aryl, alkyl-substituted aryl, aryl,
substituted
aryl, and mixtures thereof. In another embodiment, phosphorus compounds
useful in the invention, include but are not limited to, the above described
CA 02666585 2009-04-16
WO 2008/051321 PCT/US2007/015704
-60-
compounds wherein at least one of the hydrogen atoms bonded to an oxygen
atom of the compound is replaced with a metallic ion or an ammonium ion.
[00181] The esters can contain alkyl, branched alkyl, substituted alkyl, alkyl
ethers, aryl, and/or substituted aryl groups. The esters can also have at
least
one alkyl group and at least one aryl group. The number of ester groups
present
in the particular phosphorus compound can vary from zero up to the maximum
allowable based on the number of hydroxyl groups present on the phosphorus
compound used. For example, an alkyl phosphate ester can include one or more
of the mono-, di-, and tri alkyl phosphate esters; an aryl phosphate ester
includes
one or more of the mono-, di-, and tri aryl phosphate esters; and an alkyl
phosphate ester and/or an aryl phosphate ester also include, but are not
limited
to, mixed alkyl aryl phosphate esters having at least one alkyl and one aryl
group.
[00182] In one embodiment, the phosphorus compounds useful in the invention
include but are not limited to alkyl, aryl or mixed alkyl aryl esters or
partial esters
of phosphoric acid, phosphorus acid, phosphinic acid, phosphonic acid, or
phosphonous acid. The alkyl or aryl groups can contain one or more
substituents.
[00183] In one aspect, the phosphorus compounds useful in the invention
comprise at least one phosphorus compound chosen from at least one of
substituted or unsubstituted alkyl phosphate esters, substituted or
unsubstituted
aryl phosphate esters, substituted or unsubstituted mixed alkyl aryl phosphate
esters, diphosphites, salts of phosphoric acid, phosphine oxides, and mixed
aryl
alkyl phosphites, reaction products thereof, and mixtures thereof. The
phosphate
esters include esters in which the phosphoric acid is fully esterified or only
partially esterified.
[00184] In one embodiment, for example, the phosphorus compounds useful in
the invention can include at least one phosphate ester.
[00185] In one aspect, the phosphorus compounds useful in the invention
comprise at least one phosphorus compound chosen from at least one of
substituted or unsubstituted alkyl phosphate esters, substituted or
unsubstituted
aryl phosphate esters, substituted or unsubstituted mixed alkyl aryl phosphate
esters, reaction products thereof, and mixtures thereof. The phosphate esters
CA 02666585 2009-04-16
WO 2008/051321 PCT/US2007/015704
-61 -
include esters in which the phosphoric acid is fully esterified or only
partially
esterified.
[00186] In one embodiment, for example, the phosphorus compounds useful in
the invention can include at least one phosphate ester.
[00187] In another embodiment, the phosphate esters useful in the invention
can include but are not limited to alkyl phosphate esters, aryl phosphate
esters,
mixed alkyl aryl phosphate esters, and/or mixtures thereof.
(00188] In certain embodiments, the phosphate esters useful in the invention
are those where the groups on the phosphate ester include are alkyl, alkoxy-
alkyl, phenyl, or substituted phenyl groups. These phosphate esters are
generally
referred to herein as alkyl and/or aryl phosphate esters. Certain preferred
embodiments include trialkyl phosphates, triaryl phosphates, alkyl diaryl
phosphates, dialkyl aryl phosphates, and mixtures of such. phosphates, wherein
the alkyl groups are preferably those containing from 2 to 12 carbon atoms,
and
the aryl groups are preferably phenyl.
[00189] Representative alkyl and branched alkyl groups are preferably those
containing from 1-12 carbon atoms, including, but not limited to, ethyl,
propyl,
isopropyl, butyl, hexyl, cyclohexyl, 2-ethylhexyl, octyl, decyl and dodecyl.
Substituted alkyl groups include, but are not limited to, those containing at
least
one of carboxylic acid groups and esters thereof, hydroxyl groups, amino
groups,
keto groups, and the like.
[00190]. Representative of alkyl-aryl and substituted alkyl-aryl groups are
those
wherein the alkyl portion contains from 1-12 carbon atoms, and the aryl group
is
phenyl or substituted phenyl wherein groups such as alkyl, branched alkyl,
aryl,
hydroxyl, and the like are substituted for hydrogen at any carbon position on
the
phenyl ring. Preferred aryl groups include phenyl or substituted phenyl
wherein
groups such as alkyl, branched alkyl, aryl, hydroxyl and the like are
substituted
for hydrogen at any position on the phenyl ring.
[00191] In one embodiment, the phosphate esters useful in the invention
include but are not limited to dibutylphenyl phosphate, triphenyl phosphate,
tricresyl phosphate, tributyl phosphate, tri-2-ethylhexyl phosphate, trioctyl
CA 02666585 2009-04-16
WO 2008/051321 PCT/US2007/015704
-62-
phosphate, and/or mixtures thereof, including particularly mixtures of
tributyl
phosphate and tricresyl phosphate, and mixtures of isocetyl diphenyl phosphate
and 2-ethylhexyl diphenyl phosphate.
[00192] In one embodiment, at least one phosphorus compound useful in the
invention comprises at least one aryl phosphate ester.
[00193] In one embodiment, at least one phosphorus compound useful in the
invention comprises at least one unsubstituted aryl phosphate ester.
[00194] In one aspect, at least one phosphorus compound useful in the
invention comprises at least one aryl phosphate ester which is not substituted
with benzyl groups.
[00195] In one aspect, any of the phosphorus compounds useful in the
invention may comprise at least one alkyl phosphate ester.
[00196] In one embodiment, the phosphate esters useful in the invention as
thermal stabilizers and/or color stabilizers include but are not limited to,
at least
one of the following: trialkyl phosphates, triaryl phosphates, alkyl diaryl
phosphates, and mixed alkyl aryl phosphates.
[00197] In one embodiment, the phosphate esters useful in the invention as
thermal stabilizers and/or color stabilizers include but are not limited to,
at least
one of the following: triaryl phosphates, alkyl diaryl phosphates, and mixed
alkyl
aryl phosphates.
1001981 In one embodiment, the phosphate esters useful as thermal stabilizers
and/or color stabilizers in the invention can include but are not limited to,
at least
one of the following: triaryl phosphates and mixed alkyl aryl phosphates.
[00199] In one embodiment, at least one phosphorus compound useful in the
invention can comprise, but is not limited to, triaryl phosphates, such as,
for
example, triphenyl phosphate. In one embodiment, at least one one thermal
stabilizer comprises, but is not limited to Merpol A. In one embodiment, at
least
one thermal stabilizer useful in the invention comprises, but is not limited
to, at
least one of triphenyt phosphate and Merpol A. Merpol A is a phosphate ester
commercially available from Stepan Chemical Co and/or E.I. duPont de Nemours
& Co. The CAS Registry number for Merpol A is believed to be CAS Registry #
37208-27-8.
CA 02666585 2009-04-16
WO 2008/051321 PCT/US2007/015704
-63-
[00200] In one aspect, any of the phosphorus compounds useful in the
invention may comprise at least one triaryl phosphate ester which is not
substituted with benzyl groups.
[00201] In one embodiment, the polyester compositions and/or processes of
the invention may comprise 2-ethylhexyl diphenyl phosphate.
[00202] In one embodiment, any of the processes described herein for making
any of the polyester compositions and/or polyesters can comprise at least one
mixed alkyl aryl phosphite, such as, for example, bis(2,4-
dicumylphenyl)pentaerythritol diphosphite also known as Doverphos S-9228
(Dover Chemicals, CAS# 154862-43-8).
[00203] In one embodiment, any of the processes described herein for making
any of the polyester compositions and/or polyesters can comprise at least one
one phosphine oxide.
[00204] In one embodiment, any of the processes described herein for making
any of the polyester compositions and/or polyesters can comprise at least one
salt of phosphoric acid such as, for example, KH2PO4 and Zn3(PO4)2.
[00205] The term "thermal stabilizer" is intended to include the reaction
product(s) thereof. The term "reaction product" as used in connection with the
thermal stabilizers of the invention refers to any product of a
polycondensation or
esterification reaction between the thermal stabilizer and any of the monomers
used in making the polyester as well as the product of a polycondensation or
esterification reaction between the catalyst and any other type of additive.
[00206] In one embodiment of the invention, the phosphorus compounds useful
in the invention may act as thermal stabilizers. In one embodiment of the
invention, the phosphorus compounds useful in the invention may not act as a
thermal stabilizer but may act as a color stabilizer. In one embodiment of the
invention, the phosphorus compounds useful in the invention may act as both a
thermal stabilizer and a color stabilizer.
[00207] When phosphorus is added to the polyesters and/or polyester
compositions and/or process of making the polyesters of the invention, it is
added
in the form of a phosphorus compound, for example, at least one phosphate
ester(s). The amount of phosphorus compound(s), (for example, at least one
CA 02666585 2009-04-16
WO 2008/051321 PCT/US2007/015704
-64-
phosphate ester), is added to the polyesters of the invention and/or polyester
compositions of the invention and/or processes of the invention .can be
measured
in the form of phosphorus atoms present in the final polyester, for example,
by
weight measured in ppm.
[00208] Amounts of phosphorus compound(s) added during polymerization
and/or post manufacturing can include but are not limited to: 1 to 5000 ppm; 1
to
1000 ppm, 1 to 900 ppm, 1 to 800 ppm, 1 to 700 ppm. 1 to 600 ppm, 1 to 500
ppm, 1 to 400 ppm, 1 to 350 ppm, 1 to 300 ppm, 1 to 250 ppm, 1 to 200 ppm, 1
to 150 ppm, 1 to 100 ppm;10 to 5000 ppm; 10 to 1000 ppm, 10 to 900 ppm, 10 to
800 ppm, 10 to 700 ppm. 10 to 600 ppm, 10 to 500 ppm, 10 to 400 ppm, 10 to
350 ppm, 10 to 300 ppm, 10 to 250 ppm, 10 to 200 ppm, 10 to 150 ppm, 10 to
100 ppm; based on the total weight of the polyester composition.
[00209] In one embodiment, amounts of the phosphate ester of the invention
added during polymerization are chosen from the following: 1 to 5000 ppm; 1 to
1000 ppm, 1 to 900 ppm, 1 to 800 ppm, 1 to 700 ppm. 1 to 600 ppm, 1 to 500
ppm, 1 to 400 ppm, 1 to 350 ppm, 1 to 300 ppm, 1 to 250 ppm, 1 to 200 ppm, 1
to 150 ppm, 1 to 100 ppm; 1 to 60 ppm; 2 to 5000 ppm; 2 to 1000 ppm, 2 to 900
ppm, 2 to 800 ppm, 2 to 700 ppm. 2 to 600 ppm, 2 to 500 ppm, 2 to 400 ppm, 2
to 350 ppm, 2 to 300 ppm, 2 to 250 ppm, 2 to 200 ppm, 2 to 150 ppm, 2 to 100
ppm; 2 to 60 ppm; 2 to 20 ppm, 3 to 5000 ppm; 3 to 1000 ppm, 3 to 900 ppm, 3
to 800 ppm, 3 to 700 ppm. 3 to 600 ppm, 3 to 500 ppm, 3 to 400 ppm, 3 to 350
ppm, 3 to 300 ppm, 3 to 250 ppm, 3 to 200 ppm, 3 to 150 ppm, 3 to 100 ppm; 3
to 60 ppm; 3 to 20 ppm, 4 to 5000 ppm; 4 to 1000 ppm, 4 to 900 ppm, 4 to 800
ppm, 4 to 700 ppm, 4 to 600 ppm, 4 to 500 ppm, 4 to 400 ppm, 4 to 350 ppm, 4
to 300 ppm, 4 to 250 ppm, 4 to 200 ppm, 4 to 150 ppm, 4 to 100 ppm; 4 to 60
ppm; 4 to 20 ppm, 5 to 5000 ppm; 5 to 1000 ppm, 5 to 900 ppm, 5 to 800 ppm, 5
to 700 ppm, 5 to 600 ppm, 5 to 500 ppm, 5 to 400 ppm, 5 to 350 ppm, 5 to 300
ppm, 5 to 250 ppm, 5 to 200 ppm, 5 to 150 ppm, 5 to 100 ppm; 5 to 60 ppm; 5 to
20 ppm, 6 to 5000 ppm; 6 to 1000 ppm, 6 to 900 ppm, 6 to 800 ppm, 6 to 700
ppm, 6 to 600 ppm, 6 to 500 ppm, 6 to 400 ppm, 6 to 350 ppm, 6 to 300 ppm, 6
to 250 ppm, 6 to 200 ppm, 6 to 150 ppm, 6 to 100 ppm; 6 to 60 ppm; 6 to 20
ppm, 7 to 5000 ppm; 7 to 1000 ppm, 7 to 900 ppm, 7 to 800 ppm, 7 to 700 ppm,
CA 02666585 2009-04-16
WO 2008/051321 PCT/US2007/015704
-65-
7 to 600 ppm, 7 to 500 ppm, 7 to 400 ppm, 7 to 350 ppm, 7 to 300 ppm, 7 to 250
ppm, 7 to 200 ppm, 7 to 150 ppm, 7 to 100 ppm; 7 to 60 ppm; 7 to 20 ppm, 8 to
5000 ppm; 8 to 1000 ppm, 8 to 900 ppm, 8 to 800 ppm, 8-to 700 ppm, 8 to 600
ppm, 8 to 500 ppm, 8 to 400 ppm, 8 to 350 ppm, 8 to 300 -ppm, 8 to 250 ppm, 8
to 200 ppm, 8 to 150 ppm, 8 to 100 ppm; 8 to 60 ppm; 8 to 20 ppm, 9 to 5000
ppm; 9 to 1000 ppm, 9 to 900 ppm, 9 to 800 ppm, 9 to 700 ppm, 9 to 600 ppm, 9
to 500 ppm, 9 to 400 ppm, 9 to 350 ppm, 9 to 300 ppm, 9 to 250 ppm, 9 to 200
ppm, 9 to 150 ppm, 9 to 100 ppm; 9 to 60 ppm; 9 to 20 ppm, 10 to 5000 ppm; 10
to 1000 ppm, 10 to 900 ppm, 10 to 800 ppm, 10 to 700 ppm. 10 to 600 ppm, 10
to 500 ppm, 10 to 400 ppm, 10 to 350 ppm, 10 to 300 ppm, 10 to 250 ppm, 10 to
200 ppm, 10 to 150 ppm, 10 to 100 ppm, 10 to 60 ppm, 10 to 20 ppm, 50 to 5000
ppm, 50 to 1000 ppm, 50 to 900 ppm, 50 to 800 ppm, 50 to 700 ppm, 50 to 600
ppm, 50 to 500 ppm, 50 to 400 ppm, 50 to 350 ppm, 50 to 300 ppm, 50 to 250
ppm, 50 to 200 ppm, 50 to 150 ppm, 50 to 100 ppm; 50 to 80 ppm, 100 to 5000
ppm, 100 to 1000 ppm, 100 to 900 ppm, 100 to 800 ppm, 100 to 700 ppm, 100
to 600 ppm, 100 to 500 ppm, 100 to 400 ppm, 100 to 350 ppm, 100 to 300 ppm,
100 to 250 ppm, 100 to 200 ppm, 100 to 150 ppm; 150 to 5000 ppm, 150 to
1000 ppm, 150 to 900 ppm, 150 to 800 ppm, 150 to 700 ppm, 150 to 600 ppm,
150 to 500 ppm, 150 to 400 ppm, 150 to 350 ppm, 150 to 300 ppm, 150 to 250
ppm, 150 to 200 ppm, 200 to 5000 ppm, 200 to 1000 ppm, 200 to 900 ppm, 200
to 800 ppm, 200 to 700 ppm, 200 to 600 ppm, 200 to 500 ppm, 200 to 400 ppm,
200 to 350 ppm, 200 to 300 ppm, 200 to 250 ppm, 250 to 5000 ppm, 250 to
1000 ppm, 250 to 900 ppm, 250 to 800 ppm, 250 to 700 ppm, 250 to 600 ppm,
250 to 500 ppm, 250 to 400 ppm, 250 to 350 ppm, 250 to 300 ppm, 500 to 5000
ppm, 300 to 1000 ppm, 300 to 900 ppm, 300 to 800 ppm, 300 to 700 ppm, 300
to 600 ppm, 300 to 500 ppm, 300 to 400 ppm, 300 to 350 ppm, 350 to 5000 ppm,
350 to 1000 ppm, 350 to 900 ppm, 350 to 800 ppm, 350 to 700 ppm, 350 to 600
ppm, 350 to 500 ppm, 350 to 400 ppm; based on the total weight of the
polyester
composition and as measured in the form of phosphorus atoms in the final
polyester.
[00210] In one embodiment, suitable catalysts for use in the processes of the
invention to make the polyesters useful in the invention include at least one
CA 02666585 2009-04-16
WO 2008/051321 PCT/US2007/015704
-66-
titanium compound. The polyester compositions of the invention may also
comprise at least one of the titanium compounds useful in the processes of the
invention. Other catalysts could possibly be used in the invention in
combination
with the at least one titanium compound Other catalysts may include, but are
not
limited to, those based on tin, gallium, zinc, antimony, cobalt, manganese,
magnesium, germanium, lithium, aluminum compounds, and an aluminum
compound with lithium hydroxide or sodium hydroxide. In one embodiment, the
catalyst can be a combination of at least one tin compound and at least one
titanium compound.
[00211] Catalyst amounts can range from 10 ppm to 20,000 ppm or 10
to10,000 ppm, or 10 to 5000 ppm or 10 to 1000 ppm or 10 to 500 ppm, or 10 to
300 ppm or 10 to 250 ppm based on the catalyst metal and based on the weight
of the final polymer. The process can be carried out in either a batch or
continuous process. In one embodiment, the process is carried out in a
continuous process.
1002121 In one embodiment, the catalyst comprises a titanium compound. In
one embodiment, the titanium compound can be used in either the esterification
reaction or the polycondensation reaction or both reactions. In one
embodiment,
the catalyst comprises a titanium compound used in the esterification
reaction. In
one embodiment, the catalyst comprises a titanium compound used in the
polycondensation reaction. In another embodiment, the catalyst consists
essentially of a titanium compound useful in the polyesters useful in the
invention
and/or the processes of making the polyesters of the invention. Generally, in
one
embodiment, the titanium compound is used in amounts of from about 0.005% to
about 0.2% based on the weight of the dicarboxylic acid or dicarboxylic acid
ester. Generally, in one embodiment, less than about 700 ppm elemental
titanium
can be present as residue in the polyester based on the total weight of the
polyester.
[00213] When titanium is added to to the polyesters and/or polyester
compositions and/or process of making the polyesters of the invention, it is
added
to the process of making the polyester in the form of a titanium compound. The
amount of the titanium compound added to the polyesters of the invention
and/or
CA 02666585 2009-04-16
WO 2008/051321 PCT/US2007/015704
- 67 -
polyester compositions of the invention and/or processes of the invention can
be
measured in the form of titanium atoms present in the final polyester, for
example, by weight measured in ppm.
[00214] In another embodiment, the catalyst consists essentially of a titanium
compound used in the esterification reaction in the amount of 10 ppm to 20,000
ppm or 10 to10,000 ppm, or 10 to 5000 ppm or 10 to 4500 ppm or 10 to 4000
ppm or 10 to 3500 ppm or 10 to 3000 ppm or 10 to 2500 ppm or 10 to 2000 ppm
or or 10 to 1500 ppm or 10 to 1000 ppm or 10 to 500 ppm, or 10 to 300 ppm or
to 250 ppm or 15 ppm to 20,000 ppm or 15 to10,000 ppm, or 15 to 5000 ppm
or or 15 to 4500 ppm or 15 to 4000 ppm or 15 to 3500 ppm or 15 to 3000 ppm or
to 2500 ppm or 15 to 2000 ppm or or 15 to 1500 ppm or 15 to 1000 ppm or 15
to 500 ppm, or 15 to 400 ppm or 15 to 300 ppm or 15 to 250 ppm or 20 ppm to
20,000 ppm or 20 to10,000 ppm, or 20 to 5000 ppm or or 20 to 4500 ppm or 20
to 4000 ppm or 20 to 3500 ppm or 20 to 3000 ppm or 20 to 2500 ppm or 20 to
2000 ppm or or 20 to 1500 ppm or 20 to 1000 ppm or 20 to 500 ppm, or 20 to
300 ppm or 20 to 250 ppm 25 ppm to 20,000 ppm or 25 to-10,000 ppm, or 25 to
5000 ppm or or 25 to 4500'ppm or 25 to 4000 ppm or 25 to 3500 ppm or 25 to
3000 ppm or 25 to 2500 ppm or 25 to 2000 ppm or or 25 to 1500 ppm or 25 to
1000 ppm or 25 to 500 ppm, or 25 to 400 ppm, or 25 to 300 ppm or 25 to 250
ppm or 30 ppm to 20,000 ppm or 30 to10,000 ppm, or 30 to 5000 ppm or 30 to
4500 ppm or 30 to 4000 ppm or 30 to 3500 ppm or 30 to 3000 ppm or 30 to 2500
ppm or 30 to 2000 ppm or or 30 to 1500 ppm pr 30 to 1000 ppm or 30 to 500
ppm, or 30 to 300 ppm or 30 to 250 ppm or 35 ppm to 20,000 ppm or 35 to10,000
ppm, or 35 to 5000 ppm or 35 to 4500 ppm or 35 to 4000 ppm or 35 to 3500 ppm
or 35 to 3000 ppm or 35 to 2500 ppm or 35 to 2000 ppm or or 35 to 1500 ppm or
35 to 1000 ppm or 35 to 500 ppm, or 35 to 300 ppm or 35 to 250 ppm or 40 ppm
to 20,000 ppm or 40 to10,000 ppm, or 40 to 5000 ppm or or 40 to 4500 ppm or
40 to 4000 ppm or 40 to 3500 ppm or 40 to 3000 ppm or 40 to 2500 ppm or 40 to
2000 ppm or or 40 to 1500 ppm or 40 to 1000 ppm or 40 to 500 ppm, or 40 to
300 ppm or 40 to 250 ppm or 40 to 200 ppm or 45 ppm to 20,000 ppm or 45
to10,000 ppm, or 45 to 5000 ppm or 45 to 4500 ppm or 45 to 4000 ppm or 45 to
3500 ppm or 45 to 3000 ppm or 45 to 2500 ppm or 45 to 2000 ppm or 45 to 1500
CA 02666585 2009-04-16
WO 2008/051321 PCT/US2007/015704
-68-
ppm or 45 to 1000 ppm or 45 to 500 ppm, or 45 to 300 ppm or 45 to 250 ppm or
50 ppm to 20,000 ppm or 50 to10,000 ppm, or 50 to 5000 ppm or 50 to 4500 ppm
or 50 to 4000 ppm or 50 to 3500 ppm or 50 to 3000 ppm or 50 to 2500 ppm or 50
to 2000 ppm or or 50 to 1500 ppm or 50 to 1000 ppm or 50 to 500 ppm, or 50 to
300 ppm or 50 to 250 ppm or 50 to 200 ppm or 50 to 150 ppm 50 to 125 ppm,
based on the weight of the final polyester, as measured in the form of
titanium
atoms in the final polyester.
[00215] In another embodiment, the polyesters of the invention can be
prepared using at least one tin compound in addition to the titanium compound
as
catalyst(s). For example, see U.S. Pat. No. 2,720,507, where the portion
concerning tin catalysts is incorporated herein by reference. These catalysts
are
tin compounds containing at least one organic radical. These catalysts include
compounds of both divalent or tetravalent tin which have the general formulas
set
forth below:
A. M2(Sn(OR)4)
B. MH(Sn(OR)4)
C. M'(Sn(OR)4)
D. M'(HSn(OR)4)2
E. M2(Sn(OR)6)
F. MH(Sn(OR)6)
G. M'(Sn(OR)6)
H. M'(HSn(OR)6)2
1. Sn(OR)2
CA 02666585 2009-04-16
WO 2008/051321 PCT/US2007/015704
-69-
J. Sn(OR)4
K. SnR'2
L. SnR'4
M. R'2SnO
N.
R OR
Sn
/ \
R OM
0.
R OR
Sn
R OR
P.
R'~ /CI
Sn
/ ~ .
Rp CI
Q
CA 02666585 2009-04-16
WO 2008/051321 PCT/US2007/015704
-70-
R OAc
Sn
/ \
R OAc
wherein M is an alkali metal, e.g. lithium, sodium, or potassium, M' is an
alkaline
earth metal such as Mg, Ca or Sr, each R represents an alkyl radical
containing
from 1 to 8 carbon atoms, each R' radical represents a substituent selected
from
those consisting of alkyl radicals containing from 1 to 8 carbon atoms (i. e.
R
radicals) and aryl radicals of the benzene series containing from 6 to 9
carbon
atoms (e.g. phenyl, tolyi, benzyl, phenylethyl, etc., radicals), and Ac
represents
an acyl radical derived from an organic acid containing from 2 to 18 carbon
atoms
(e.g. acetyl, butyryl, lauroyl, benzoyl, stearoyl, etc. ).
[00216] The novel bimetallic alkoxide catalysts can be made as described by
Meerwein, Ann. 476, 113 (1929). As shown by Meerwein, these catalysts are not.
merely mixtures of the two metallic alkoxides. They are definite compounds
having a salt-like structure. These are the compounds depicted above by the
Formulas A through H. Those not specifically described by Meerwein can be
prepared by procedures analogous to the working examples and methods set
forth by Meerwein.
[00217] The other tin compounds can also be made by various methods such
as those described in the following literature: For the preparation of diaryl
tin
dihalides (Formula P) see Ber. 62, 996 (1929); J. Am. Chem. Soc. 49, 1369
(1927). For the preparation of dialkyl tin dihalides (Formula P) see J. Am.
Chem.
Soc. 47, 2568 (1925) ; C.A. 41, 90 (1947). For the preparation of diaryl tin
oxides
(Formula M) see J. Am. Chem. Soc. 48, 1054 (1926). For the preparation of
tetraaryl tin compounds (Formula K) see C.A. 32, 5387 (1938). For the
preparation of tin alkoxides (Formula J) see C.A. 24, 586 (1930). For the
preparation of alkyl tin salts (Formula Q) see C.A. 31, 4290. For the
preparation
of alkyl tin compounds (Formula K and L) see C.A. 35, 2470 (1941): C.A. 33,
5357 (1939). For the preparation of mixed alkyl aryl tin (Formulas K and L)
see
CA 02666585 2009-04-16
WO 2008/051321 PCT/US2007/015704
-71 -
C.A. 31, 4290 (1937): C.A. 38, 331 (1944). For the preparation of other tin
compounds not covered by these citations see "Die Chemie der Metal-
Organischen Verbindungen." by Krause and V. Grosse, published in Berlin, 1937,
by Gebroder-Borntrager.
[00218] The tin alkoxides (Formulas I and J) and the bimetallic alkoxides
(Formulas A through H) contain R substituents which can represent both
straight
chain and branched chain alkyl radicals, e.g. diethoxide, tetramethoxide,
tetrabutoxide, tetra-tert-butoxide, tetrahexoxide, etc.
[00219] The alkyl derivatives (Formulas K and L) contain one or more alkyl
radicals attached to a tin atom through a direct C-Sn linkage, e.g. dibutyl
tin,
dihexyl tin, tetra-butyl tin, tetraethyl tin, tetramethyl tin, dioctyl tin,
etc. Two of the
tetraalkyl radicals can be replaced with an oxygen atom to form compounds
having Formula M, e.g. dimethyl tin oxide, diethyl tin oxide, dibutyl tin
oxide,
diheptyl tin oxide, etc. In one embodiment, the tin catalyst comprises
dimethyl tin
oxide.
[00220] Complexes can be formed by reacting dialkyl tin oxides with alkali
metal alkoxides in an alcohol solution to form compounds having Formula N,
which compounds are especially useful catalysts, e.g. react dibutyl tin oxide
with
sodium ethoxide, etc. This formula is intended to represent the reaction
products
described. Tin compounds containing alkyl and alkoxy radicals are also useful
catalysts (see Formula 0), e.g. diethyl tin diethoxide, dibutyl tin
dibutoxide,
dihexyl tin dimethoxide, etc.
[00221] Salts derived from dialkyl tin oxides reacted with carboxylic acids or
hydrochloric acid are also of particular value as catalysts; see Formulas P
and Q.
Examples of these catalytic condensing agents include dibutyl tin diacetate,
diethyl tin dibutyrate, dibutyl tin dilauroate, dimethyl tin dibenzoate,
dibutyl tin
dichloride, diethyl tin dichloride, dioctyl tin dichloride, dihexyl tin
distearate, etc.
[00222] The tin compounds having Formulas K, L and M~can be prepared
wherein one or more of the R' radicals represents an aryl radical of the
benzene
series, e.g. phenyl, tolyi, benzyl, etc. Examples include diphenyl tin,
tetraphenyl
tin, diphenyl dibutyl tin, ditolyl diethyl tin, diphenyl tin oxide, dibenzyl
tin,
tetrabenzyl tin, di([B-phenylethyl) tin oxide, dibenzyl tin oxide, etc.
CA 02666585 2009-04-16
WO 2008/051321 PCT/US2007/015704
-72-
[00223] Examples of catalysts useful in the present invention include, but are
not limited to, one of more of the following: butyltin tris-2-ethylhexanoate,
dibutyltin diacetate, dibutyltin oxide, and dimethyl tin oxide.
[00224] In one embodiment, catalysts useful in the present invention include,
but are not limited to, one or more of the following: butyltin tris-2-
ethylhexanoate,
dibutyltin diacetate, dibutyltin oxide, and dimethyl tin oxide.
[00225] Processes for preparing polyesters using tin-based catalysts are well
known and described in the aforementioned U.S. Pat. No. 2,720, 507.
[00226] The titanium-containing compounds useful in this invention include any
compound containing titanium including but not limited to: tetraethyl
titanate,
acetyltripropyl titanate, tetrapropyl titanate, tetrabutyl titanate, polybutyl
titanate,
2-ethylhexyltitanate, octyleneglycol titanate, lactate titanate,
triethanolamine
titanate, acetylacetonate titanate, ethylacetoacetic ester titanate,
isostearyl
titanate, acetyl triisopropyl titanate, titanium tetraisopropoxide titanium
glycolates,
titanium butoxide, hexylene glycol titanate, and tetraisooctyl titanate,
titanium
dioxide, titanium dioxide/silicon dioxide coprecipitates, and titanium
dioxide/zirconium dioxide coprecipitates. This invention includes but is not
limited
to the titanium dioxide/silicon dioxide coprecipitate catalyst described in
United
States Patent 6,559,272.
[00227] The polyester portion of the polyester compositions useful in the
invention can be made by processes known from the literature such as, for
example, by processes in homogenous solution, by transesterification processes
in the melt, and by two phase interfacial processes. Suitable methods include,
but are not limited to, the steps of reacting one or more dicarboxylic acids
with
one or more glycols at a temperature of 100 C to 315 C at a pressure of 0.1 to
760 mm Hg for a time sufficient to form a polyester. See U.S. Patent No.
3,772,405 for methods of producing polyesters, the disclosure regarding such
methods is hereby incorporated herein by reference.
[00228] The polyester in general may be prepared by condensing the
dicarboxylic acid or dicarboxylic acid ester with the glycol in the presence
of the
titanium catalyst and/or titanium and tin catalysts described herein at
elevated
CA 02666585 2009-04-16
WO 2008/051321 PCT/US2007/015704
-73-
temperatures increased gradually during the course of the condensation up to a
temperature of about 225 -310 C., in an inert atmosphere, and conducting the
condensation at low pressure during the latter part of the condensation, as
described in further detail in U.S. Pat. No. 2, 720, 507 incorporated herein
by
reference.
[00229] In another aspect, this invention relates to a process for preparing
copolyesters of the invention. In one embodiment, the process relates to
preparing copolyesters comprising terephthafic acid, 2,2,4,4-tetramethyl-1,3-
cyclobutanediol, and 1,4-cyclohexanedimethanol. This process comprises the
steps of:
(A) heating a mixture comprising the monomers useful in the polyesters
of the invention in the presence of at least one tin catalyst and at
least one phosphate ester at a temperature of 150 to 250 C for a
time sufficient to produce an initial polyester;
(B) polycondensing the product of Step (A) by heating it at a
temperature of 230 to 320 C for 1 to 6 hours; and
(C) removing any unreacted glycols.
[00230] Reaction times for the esterification Step (A) are dependent upon the
selected temperatures, pressures, and feed mole ratios of.glycol to
dicarboxylic
acid.
[00231] In one embodiment, step (A) can be carried out until 50% by weight or
more of the 2,2,4,4-tetramethyl-l,3-cyclobutanedioi has been reacted. Step (A)
may be carried out under pressure, ranging from 0 psig to 100 psig. The term
"reaction product" as used in connection with any of the catalysts useful in
the
invention refers to any product of a polycondensation or esterification
reaction
with the catalyst and any of the monomers used in making the polyester as well
as the product of a polycondensation or esterification reaction between the
catalyst and any other type of additive.
[00232] Typically, Step (B) and Step (C) can be conducted at the same time.
These steps can be carried out by methods known in the art such as by placing
the reaction mixture under a pressure ranging, from 0.002 psig to below
atmospheric pressure, or by blowing hot nitrogen gas over the mixture.
CA 02666585 2009-04-16
WO 2008/051321 PCT/US2007/015704
-74-
[00233] In one embodiment, the invention relates to a process hereinafter
referred to as "PROCESS COMPRISING TITANIUM", for making a polyester
comprising the following steps:
(I) heating a mixture at at least one temperature chosen from 150 C to
250 C, under at least one pressure chosen from the range of 0 psig to 75
psig wherein said mixture comprises:
(a) a dicarboxylic acid component comprising:
(a) a dicarboxylic acid component comprising:
(i) about 90 to about 100 mole % of terephthalic acid
residues;
(ii) about 0 to about 10 mole % of aromatic and/or
aliphatic dicarboxylic acid residues having up to 20 carbon
atoms; and
(b) a glycol component comprising:
(i) about 1 to less than 90 mole % 2,2,4,4-tetramethyl-
1,3-cyclobutanediol residues; and
(ii) about 0 to about 89 mole % cyclohexanedimethanol
residues;
(iii) greater than 10 mole % ethylene glycol residues, and
(iv) less than about 2 mole % of a modifying glycol having
from 3 to 16 carbon atoms;
wherein the molar ratio of glycol component/dicarboxylic acid
component added in Step (I) is 1.01-3.0/1.0;
wherein the mixture in Step (I) is heated in the presence of:
(i) at least one catalyst comprising at least one titanium compound,
and, optionally, at least one catalyst chosen from tin, gallium, zinc,
antimony, cobalt, manganese, magnesium, germanium, lithium,
aluminum compounds and an aluminum compound with lithium
hydroxide or sodium hydroxide; and (ii) at least one phosphorus
compound, reaction products thereof, and mixtures thereof;
CA 02666585 2009-04-16
WO 2008/051321 PCT/US2007/015704
-75-
(II) heating the product of Step (1) at a temperature of 230 C to 320 C
for 1 to 6 hours, under at least one pressure chosen from the range of the
final pressure of Step (I) to 0.02 torr absolute, to form a final polyester;
wherein the total mole % of the dicarboxylic acid component of the final
polyester
is 100 mole %; and wherein the total mole % of the glycol component of the
final
polyester is 100 mole %;
and
wherein the inherent viscosity of the polyester is from 0.50 to 1.2 dUg as
determined in 60/40 (wt/wt) phenol/ tetrachloroethane at a concentration of
0.25
g/50 ml at 25 C.
[002341 In one embodiment, the invention relates to a process, hereinafter
referred to as "PROCESS COMPRISING TIN AND TITANIUM", for making a
polyester comprising the following steps:
(I) heating a mixture at at least one temperature chosen from 150 C to
250 C, under at least one pressure chosen from the range of 0 psig to 75
psig wherein said mixture comprises:
(a) a dicarboxylic acid component comprising:
(i) about 90 to about 100 mole % of terephthalic acid
residues;
(ii) about 0 to about 10 mole % of aromatic and/or
aliphatic dicarboxylic acid residues having up to 20 carbon
atoms; and
(b) a glycol
(i) about 1 to less than 90 mole % 2,2,4,4-tetramethyl-
1,3-cyclobutanediol residues; and
(ii) about 0 to about 89 mole % cyclohexanedimethanol
residues;
(iii) greater than 10 mole % ethylene glycol residues, and
(iv) less than about 2 mole % of a modifying glycol having
from 3 to 16 carbon atoms;
wherein the molar ratio of glycol component/dicarboxylic acid
component added in Step (I) is 1.01-3.0/1.0;
CA 02666585 2009-04-16
WO 2008/051321 PCT/US2007/015704
-76-
wherein the mixture in Step (I) is heated in the presence of:
(i) at least one catalyst comprising at least one titanium compound,
at least one tin compound, and optionally, at least one catalyst
chosen from gallium, zinc, antimony, cobalt, manganese,
magnesium, germanium, lithium, aluminum compounds and an
aluminum compound with lithium hydroxide or sodium hydroxide;
and (ii) at least one phosphorus compound, reaction products
thereof, and mixtures thereof;
(II) heating the product of Step (I) at a temperature of 230 C to 320 C
for 1 to 6 hours, under at least one pressure chosen from the range of the
final pressure of Step (I) to 0.02 torr absolute, to form a final polyester;
wherein the total mole % of the dicarboxylic acid component of the final
polyester
is 100 mole %; and wherein the total mole % of the glycol component of the
final
polyester is 100 mole %;
and
wherein the inherent viscosity of the polyester is from 0.50 to 1.2 dUg as
determined in 60/40 (wt/wt) phenol/ tetrachloroethane at a concentration of
0.25
g/50 ml at 25 C.
[00235] In the processes of the invention referred to as "PROCESS
COMPRISING TITANIUM", and "PROCESS COMPRISING TITANIUM AND
TIN", at least one phosphorus compound, for example, at least one phosphate
ester, can be added to Step (I), Step (II) and/or Steps (I) and (II) and/or
after
Steps (I) and (II).
[00236] In any of the processes of the invention useful in making the
polyesters
useful in the invention, at least one phosphorus compound, reaction products
thereof, and mixtures thereof can be added either during esterification,
polycondensation, or both and/or it can be added post-polymerization. In one
embodiment, the phosphorus compound useful in any of the processes of the
invention can be added during esterificaton. In one embodiment, if the
phosphorus compound added after both esterification and polycondensation, it
is
added in the amount of 0 to 2 weight % based on the total weight of the final
polyester. In one embodiment, if the phosphorus compound added after both
CA 02666585 2009-04-16
WO 2008/051321 PCT/US2007/015704
-77-
esterification and polycondensation, it is added in the amount of 0.01 to 2
weight
% based on the total weight of the final polyesterln one embodiment, the
phosphorus compound can comprise at least one phosphate ester. In one
embodiment, the phosphorus compound can comprise at least one phosphorus
compound which is added during the esterificaton step. In one embodiment, the
phosphorus compound can comprise at least one phosphate ester, for example,
which is added during the esterificaton step.
[00237] It is believed that any of the processes of making the polyesters
useful
in the invention may be used to make any of the polyesters useful in the
invention.
[00238] Reaction times for the esterification Step (I) of any of the processes
of
the invention are dependent upon the selected temperatures, pressures, and
feed mole ratios of glycol to dicarboxylic acid.
[00239] In one embodiment, the pressure used in Step (II) of any of the
processes of the invention consists of at least one pressure chosen from 20
torr
absolute to 0.02 torr absolute; in one embodiment, the pressure used in Step
(II)
of any of the processes of the invention consists of at least one pressure
chosen
from 10 torr absolute to 0.02 torr absolute; in one embodiment, the pressure
used
in Step (II) of any of the processes of the invention consists of at least one
pressure chosen from 5 torr absolute to 0.02 torr absolute;. in one
embodiment,
the pressure used in Step (I1) of any of the processes of the invention
consists of
at least one pressure chosen from 3 torr absolute to 0.02 torr absolute; in
one
embodiment, the pressure used in Step (II) of any of the pr.ocesses of the
invention consists of at least one pressure chosen from 20,torr absolute to
0.1
torr absolute; in one embodiment, the pressure used in Step (II) of any of the
processes of the invention consists of at least one pressure chosen from 10
torr
absolute to 0.1 torr absolute; in one embodiment, the pressure used in Step
(II) of
any of the processes of the invention consists of at least one pressure chosen
from 5 torr absolute to 0.1 torr absolute; in one embodiment, the pressure
used in
Step (II) of any of the processes of the invention consists of at least one
pressure
chosen from 3 torr absolute to 0.1 torr absolute.
CA 02666585 2009-04-16
WO 2008/051321 PCT/US2007/015704
-78-
[00240] In one embodiment, the molar ratio of glycol component/dicarboxylic
acid component added in Step (I) of any of the processes of the invention is
1.0-
2.0/1.0; in one embodiment, the molar ratio of glycol component/dicarboxylic
acid
component added in Step (I) of any of the processes of the invention is 1.01-
2.0/1.0; in one embodiment, the molar ratio of glycol component/dicarboxylic
acid
component added in Step (1) of any of the processes of the invention is 1.01-
1.7/1.0; in one embodiment, the molar ratio of glycol component/dicarboxylic
acid
component added in Step (I) of any of the processes of the invention is 1.01-
1.5/1.0; in one embodiment, the molar ratio of glycol component/dicarboxylic
acid
component added in Step (I) of any of the processes of the invention is 1.01-
1.2/1Ø
[00241] In any of the process embodiments for making the polyesters useful in
the invention, the heating time of Step (II) may be from 1 to 5 hours or 1 to
4
hours or 1 to 3 hours or 1.5 to 3 hours or 1 to 2 hours. In one embodiment,
the
heating time of Step (11) can be from 1.5 to 3 hours.
[00242] In one aspect, the polyesters, polyester compositions and/or processes
of the invention useful in the invention can comprise phosphorus atoms.
[00243] In one aspect, the polyesters and/or polyester compositions and/or
processes useful in the invention can comprise titanium atoms and tin atoms.
[002441 In one aspect, the polyesters, polyester compositions and/or processes
of the invention useful in the inventioncan comprise phosphorus atoms and
titanium atoms.
(00245] In one aspect, the polyesters, polyester compositions and/or processes
of the invention useful in the invention can comprise phosphorus atoms, tin
atoms, and titanium atoms.
[00246] In one embodiment, any of the polyester(s), polyester compositions
and/or processes of the invention may comprise at least one phosphorus
compound.
[00247] In one embodiment, any of the polyester(s), polyester compositions
and/or processes of the invention may comprise at least one titanium compound.
CA 02666585 2009-04-16
WO 2008/051321 PCT/US2007/015704
-79-
[00248] In one embodiment, any of the polyester(s), polyester compositions
and/or processes of the invention may comprise at least one titanium compound
and at least one phosphorus compound.
[00249] In one embodiment, any of the polyester(s), polyester compositions
and/or processes of making the polyesters useful in the invention may comprise
at least one tin compound and at least one titanium compound.
[00250] In one embodiment, any of the polyester(s), polyester compositions
and/or processes of making the polyesters useful in the invention may comprise
at least one tin compound, at least one titanium compound, and at least one
phosphorus compound.
[00251] In one embodiment, the addition of the phosphorus compound(s) in the
process(es) of the invention can result in a weight ratio of total phosphorus
atoms
to total tin atoms in the final polyester of 0-20:1. In one embodiment, the
addition
of the phosphorus compound(s) in the process(es) of the invention can result
in a
weight ratio of total phosphorus atoms to total tin atoms in the final
polyester of 1-
20:1. In one embodiment, the addition of the phosphorus compound(s) in the
process(es) of the invention can result in a weight ratio of total phosphorus
atoms
to total tin atoms in the final polyester of 0-15:1. In one embodiment, the
addition
of the phosphorus compound(s) in the process(es) of the invention can result
in a
weight ratio of total phosphorus atoms to total tin atoms in the final
polyester of 1-
15:1. In one embodiment, the addition of the phosphorus compound(s) in the
process(es) can result in a weight ratio of total phosphorus atoms to total
tin
atoms in the final polyester of 0-10:1. In one embodiment, the addition of the
phosphorus compound(s) in the process(es) of the invention can result in a
weight ratio of total phosphorus atoms to total tin atoms in the final
polyester of 1-
10:1. In one embodiment, the addition of the phosphorus compound(s) in the
process(es) can result in a weight ratio of total phosphorus atoms to total
tin
atoms in the final polyester of 0-5:1. In one embodiment, the addition of the
phosphorus compound(s) in the process(es) of the invention can result in a
weight ratio of total phosphorus atoms to total tin atoms in the final
polyester of 1-
5:1. In one embodiment, the addition of the phosphorus compound(s) in the
process(es) can result in a weight ratio of total phosphorus atoms to total
tin
CA 02666585 2009-04-16
WO 2008/051321 PCT/US2007/015704
-80-
atoms in the final polyester of 0-3:1. In one embodiment, the addition of the
phosphorus compound(s) in the process(es) can result in'a weight ratio of
total
phosphorus atoms to total tin atoms in the final polyester of 1-3:1. For
example,
the weight of tin atoms and phosphorus atoms present in the final polyester
can
be measured in ppm and can result in a weight ratio of total phosphorus atoms
to
total tin atoms in the final polyester of any of the aforesaid weight ratios.
[00252] In one embodiment, the amount of tin atoms in the polyesters useful in
the invention can be from 0 to 400 ppm tin atoms based on the weight of the
final
polyester.
[00253] In one embodiment, the amount of tin atoms in the polyesters useful in
the invention can be from 15 to 400 ppm tin atoms based on the weight of the
final polyester.
[00254] In one embodiment, the amount of titanium atoms in the polyesters
useful in the invention can be from 0 to 400 ppm titanium atoms based on the
weight of the final polyester.
[00255] In one embodiment, the amount of titanium atoms in the polyesters
useful in the invention can be from 15 to 400 ppm titanium atoms based on the
weight of the final polyester.
[00256] In one embodiment, the amount of phosphorus atoms in the polyesters
useful in the invention can be from 1 to 500 ppm phosphorus atoms based on the
weight of the final polyester.
[00257] In one embodiment, the amount of tin atoms in the polyesters useful in
the invention.can be from 1 to 400 ppm tin atoms based on the weight of the
final
polyester and the amount of phosphorus atoms in the final polyesters useful in
the invention can be from 1 to 500 ppm phosphorus atoms based on the weight
of the final polyester.
[00258] In one embodiment, the amount of phosphorus atoms in the polyesters
useful in the invention can be from 1 to 500 ppm phosphorus atoms based on the
weight of the final polyester and the amount of titanium atoms in the
polyester
can be from 1 to 100 ppm titanium atoms based on the weight of the final
polyester.
CA 02666585 2009-04-16
WO 2008/051321 PCT/US2007/015704
-81 -
[00259] In one embodiment, the amount of phosphorus atoms in the polyesters
useful in the invention can be from 1 to 500 ppm phosphorus atoms based on the
weight of the final polyester and the amount of tin atoms in the polyester can
be
from 1 to 400 ppm titanium atoms based on the weight of the final polyester.
[00260] In one embodiment, the amount of phosphorus.atoms in the polyesters
useful in the invention can be from 1 to 500 ppm phosphorus atoms based on the
weight of the final polyester and the amount of titanium atoms in the
polyester
can be from 1 to 100 ppm titanium atoms based on the weight of the final
polyester.
[00261] In one embodiment, the amount of phosphorus atoms in the
polyester(s) useful in the invention can be from 1 to 500 ppm phosphorus atoms
based on the weight of the final polyester, the amount of tin atoms in the
polyester(s) useful in the invention can be from I to 400 ppm ppm titanium
atoms
based on the weight of the final polyester, and the amount of titanium atoms
in
the polyester can be from 1 to 100 ppm titanium atoms based on the weight of
the final polyester.
[00262] The invention further relates to the polyester compositions made by
the process(es) described above.
[00263] The invention further relates to a polymer blend.. The blend
comprises:
(a) from 5 to 95 weight % of at least one of the polyesters described
above; and
(b) from 5 to 95 weight % of at least one of the polymeric components.
[00264] Suitable examples of the polymeric components include, but are not
limited to, nylon; polyesters different than those described herein;
polyamides
such as ZYTEL from DuPont; polystyrene; polystyrene copolymers; styrene
acrylonitrile copolymers; acrylonitrife butadiene styrene copolymers;
poly(methylmethacrylate); acrylic copolymers; poly(ether-imides) such as
ULTEM (a poly(ether-imide) from General Electric); polyphenylene oxides such
as poly(2,6-dimethylphenylene oxide) or poly(phenylene oxide)/polystyrene
blends such as NORYL 10000 (a blend of poly(2,6-dimethylphenylene oxide) and
polystyrene resins from General Electric); polyphenylene sulfides;
polyphenylene
CA 02666585 2009-04-16
WO 2008/051321 PCT/US2007/015704
-82-
sulfide/sulfones; poly(ester-carbonates); polycarbonates such as LEXAN (a
polycarbonate from General Electric); polysulfones; polysulfone ethers; and
poly(ether-ketones) of aromatic dihydroxy compounds; or mixtures of any of the
foregoing polymers. The blends can be prepared by conventional processing
techniques known in the art, such as melt blending or solution blending. In
one
embodiment, polycarbonate is not present in the polyester composition. If
polycarbonate is used in a blend in the polyester compositions of the
invention,
the blends can be visually clear. However, polyester compositions useful in
the
invention also contemplate the exclusion of polycarbonate as well as the
inclusion of polycarbonate.
[00265] Polycarbonates useful in the invention may be prepared according to
known procedures, for example, by reacting the dihydroxyaromatic compound
with a carbonate precursor such as phosgene, a haloformate or a carbonate
ester, a molecular weight regulator, an acid acceptor and a catalyst. Methods
for
preparing polycarbonates are known in the art and are described, for example,
in
U.S. Patent 4,452,933, where the disclosure regarding the preparation of
polycarbonates is hereby incorporated by reference herein.
[00266] Examples of suitable carbonate precursors include, but are not limited
to, carbonyl bromide, carbonyl chloride, and mixtures thereof; diphenyl
carbonate; a di(halophenyl)carbonate, e.g., di(trichlorophenyl) carbonate,
di(tribromophenyl) carbonate, and the like; di(alkylphenyl)carbonate, e.g.,
di(tolyl)carbonate; di(naphthyl)carbonate; di(chloronaphthyl)carbonate, and
mixtures thereof; and bis-haloformates of dihydric phenols.
[00267] Examples of suitable molecular weight regulators include, but are not
limited to, phenol, cyclohexanol, methanol, alkylated phenols, such as
octylphenol, para-tertiary-butyl-phenol, and the like. In one embodiment, the
molecular weight regulator is phenol or an alkylated phenol.
[00268] The acid acceptor may be either an organic or an inorganic acid
acceptor. A suitable organic acid acceptor can be a tertiary amine and
includes,
but is not limited to, such materials as pyridine, triethylamine,
dimethylaniline,
tributylamine, and the like. The inorganic acid acceptor can be either a
hydroxide,
a carbonate, a bicarbonate, or a phosphate of an alkali or alkaline earth
metal.
CA 02666585 2009-04-16
WO 2008/051321 PCT/US2007/015704
-83-
[002691 The catalysts used in making the polycarbonates useful in the
invention
that can be used include, but are not limited to, those that typically aid the
polymerization of the monomer with phosgene. Suitable catalysts include, but
are
not limited to, tertiary amines such as triethylamine, tripropylamine, N,N-
dimethylaniline, quatemary ammonium compounds such as, for example,
tetraethylammonium bromide, cetyl triethyl ammonium bromide, tetra-n-
heptylammonium iodide, tetra-n-propyl ammonium bromide, tetramethyl
ammonium chloride, tetra-methyl ammonium hydroxide, tetra-n-butyl ammonium
iodide, benzyltrimethyl ammonium chloride and quaternary phosphonium
compounds such as, for example, n-butyltriphenyl phosphonium bromide and
rriethyltriphenyl phosphonium bromide.
[00270] The polycarbonates useful in the polyester blends of the invention
also
may be copolyestercarbonates such as those described in U.S. Patents
3,169,121; 3,207,814; 4,194,038; 4,156,069; 4,430,484, 4,465, 820, and
4,981,898, where the disclosure regarding copolyestercarbonates from each of
the U.S. Patents is incorporated by reference herein.
[00271] Copolyestercarbonates useful in this invention can be available
commercially and/or may be prepared by known methods in the art. For example,
they can be typically obtained by the reaction of at least one
dihydroxyaromatic
compound with a mixture of phosgene and at least one dicarboxylic acid
chloride,
especially isophthaloyl chloride, terephthaloyl chloride, or both.
[00272] In addition, the polyester compositions and the polymer blend
compositions useful in the invention may also contain from 0.01 to 25% by
weight
of the overall composition common additives such as colorants, toner(s), dyes,
mold release agents, flame retardants, plasticizers, nucleating agents,
stabilizers,
including but not limited to, UV stabilizers, thermal stabilizers other than
the
phosphorus compounds describe herein, and/or reaction products thereof,
fillers,
and impact modifiers. Examples of typical commercially available impact
modifiers well known in the art and useful in this invention include, but are
not
limited to, ethylene/propylene terpolymers, functionalized polyolefins such as
those containing methyl acrylate and/or glycidyl methacrylate, styrene-based
block copolymeric impact modifiers, and various acrylic core/shell type impact
CA 02666585 2009-04-16
WO 2008/051321 PCT/US2007/015704
-84-
modifiers. Residues of such additives are also contemplated as part of the
polyester composition.
[00273] In addition, certain agents which colorize the polymer can be added to
the melt. In one embodiment, a bluing toner is added to the melt in order to
reduce the b* of the resulting polyester polymer melt phase product. Such
bluing
agents include blue inorganic and organic toner(s). In addition, red toner(s)
can
also be used to adjust the a* color. Organic toner(s), e.g., blue and red
organic
toner(s), such as those toner(s) described in U.S. Pat. Nos. 5,372,864 and
5,384,377, which are incorporated by reference in their entirety, can be used.
The organic toner(s) can be fed as a premix composition. The premix
composition may be a neat blend of the red and blue compounds or the
composition may be pre-dissolved or slurried in one of the polyester's raw
materials, e.g., ethylene glycol.
[00274] The total amount of toner components added depends, of course, on
the amount of inherent yellow color in the base polyester and the efficacy of
the
toner. Generally, a concentration of up to about 15 ppm of combined organic
toner components and a minimum concentration of about 0.5 ppm are used. The
total amount of bluing additive typically ranges from 0.5 to' 10 ppm.
[00275] The toner(s) can be added to the esterification zone or to the
polycondensation zone. Preferably, the toner(s) are added to the
esterification
zone or to the early stages of the polycondensation zone, such as to a
prepolymerization reactor.
[00276] Reinforcing materials may be useful in the compositions of this
invention. The reinforcing materials may include, but are not limited to,
carbon
filaments, silicates, mica, clay, talc, titanium dioxide, Wollastonite, glass
flakes,
glass beads and fibers, and polymeric fibers and combinations thereof. In one
embodiment, the reinforcing materials include glass, such as, fibrous glass
filaments, mixtures of glass and talc, glass and mica, and glass and polymeric
fibers.
[00277] The invention further relates to the film(s) and/or sheet(s)
comprising
the polyester compositions and/or polymer blends of the invention. The methods
of forming the polyesters and/or blends into film(s) and/or sheet(s) are well
known
CA 02666585 2009-04-16
WO 2008/051321 PCT/US2007/015704
-85-
in the art. Examples of film(s) and/or sheet(s) of the invention including but
not
limited to extruded film(s) and/or sheet(s), calendered film(s) and/or
sheet(s),
compression molded fiim(s) and/or sheet(s), solution casted film(s) and/or
sheet(s). Methods of making film and/or sheet include but are not limited to
extrusion, calendering, compression molding, and solution casting.
[00278] Examples of potential articles made from film and/or sheet useful in
the
invention include, but are not limited, to uniaxially stretched film,
biaxially
stretched film, shrink film (whether or not uniaxially or biaxially
stretched), liquid
crystal display film (including, but not limited to, diffuser sheets,
compensation
films and protective films), thermoformed sheet, graphic arts film, outdoor
signs,
skylights, coating(s), coated articles, painted articles, laminates, laminated
articles, and/or multiwall films or sheets.
[00279] "Graphic art film," as used herein, is a film having a thermally-
curable
ink (e.g., heat-curable ink or air-curable ink) or radiation-curable ink
(e.g., ultra-
violet-curable ink) printed thereon or therein. "Curable" refers to capable of
undergoing polymerization and/or crosslinking. In addition to the ink, the
graphic
art film may optionally also include varnishes, coatings, laminates, and
adhesives.
1002801 Exemplary thermally or air-cured inks involve pigment(s) dispersed in
one or more standard carrier resins. The pigment can be 4B Toner (PR57), 2B
Toner (PR48), Lake Red C (PR53), lithol red (PR49), iron oxide (PR101),
Permanent Red R (PR4), Permanent Red 2G (P05), pyrazolone orange (P013),
diaryl yellows (PY12, 13, 14), monoazo yellows (PY3,5,98), phthalocyanine
green
(PG7), phthalocyanine Blue, 0 form (PB15), ultramarine (PB62), permanent
violet
(PV23), titanium dioxide (PW6), carbon black (furnace/channel) (PB7), PMTA
pink, green, blue, violet (PR81, PG1, PB1, PV3,), copper ferrocyanide dye
complexes (PR169, PG45, PB62, PV27), or the like. (Parenthetical
identifications
in the foregoing refer to the generic color index prepared by the Society of
Dyers
and Colourists.) Such pigments and combinations thereof can be used to obtain
various colors including, but not limited to, white, black, blue, violet, red,
green,
yellow, cyan, magenta, or orange.
CA 02666585 2009-04-16
WO 2008/051321 PCT/US2007/015704
-86-
[00281] Other exemplary inks, including radiation-cured inks are disclosed in
U.S. Patent No. 5,382,292, where the disclosure of such inks are incorporated
herein by reference.
[00282] Examples of typical carrier resins used in standard inks include those
which have nitrocellulose, amide, urethane, epoxide, acrylate, and/or ester
functionalities. Standard carrier resins include one or more of
nitrocellulose,
polyamide, polyurethane, ethyl cellulose, cellulose acetate propionate,
(meth)acrylates, poly(vinyl butyral), poly(vinyl acetate), poly(vinyl
chloride), and
the like. Such resins can be blended, with widely used blends including
nitrocellulose/polyamide and nitrocellulose/polyurethane.
[00283] Ink resin(s) normally can be solvated or dispersed in one or more
solvents. Typical solvents employed include, but are not limited to, water,
alcohols (e.g., ethanol, 1-propanol, isopropanol, etc.), acetates (e.g., n-
propyl
acetate), aliphatic hydrocarbons, aromatic hydrocarbons (e.g., toluene), and
ketones. Such solvents typically can be incorporated in amounts sufficient to
provide inks having viscosities, as measured on a #2 Zahn cup as known in the
art, of at least 15 seconds, such as at least 20 seconds, at least 25 seconds,
or
from 25 to 35 seconds.
[00284] In one embodiment, the polyester have sufficient Tg values to allow
thermoformability, and to allow ease of printing.
[00285] In one embodiment, the graphic art film has at least one property
chosen from thermoformability, toughness, clarity, chemical resistance, T9,
and
flexibility.
[00286] Graphic art films can be used in a variety of applications, such as,
for
example, in-mold decorated articles, embossed articles, hard-coated articles.
The graphic art film can be smooth or textured.
[00287] Exemplary graphic art films include, but are not limited to,
nameplates;
membrane switch overlays (e.g., for an appliance); point of purchase displays;
flat or in-mold decorative panels on washing machines; flat touch panels on
refrigerators (e.g., capacitive touch pad arrays); flat panel on ovens;
decorative
interior trim for automobiles (e.g., a polyester laminate) ; instrument
clusters for
automobiles; cell phone covers; heating and ventilation control displays;
CA 02666585 2009-04-16
WO 2008/051321 PCT/US2007/015704
-87-
automotive console panels; automotive gear shift panels; control displays or
warning signals for automotive instrument panels; facings, dials or displays
on
household appliances; facings, dials or displays on washing machines; facings,
dials or displays on dishwashers; keypads for electronic devices; keypads for
mobile phones, personal digital assistants (PDAs, or hand-held computers) or
remote controls; displays for electronic devices; displays for hand-held
electronic
devices such as phones and PDAs; panels and housings for mobile or standard
phones; logos on electronic devices; and logos for hand-held phones_
[00288] Multiwall film or sheet refers to sheet extruded as a profile
consisting of
multiple layers that are connected to each other by means of vertical ribs.
Examples of multiwall film or sheet include but are not limited to outdoor
shelters
(for example, greenhouses and commercial canopies).
[00289] Examples of extruded articles comprising the polyester compositions
useful in this invention include, but are not limited to, thermoformed sheet,
film for
graphic arts applications, outdoor signs, skylights, multiwall film, plastic
film for
plastic glass laminates, and liquid crystal display (LCD) films, including but
not
limited to, diffuser sheets, compensation films, and protective films for
LCDs.
[00290] In one embodiment, the present invention comprises a thermoplastic
article, typically in the form of sheet material, having a decorative material
embedded therein which comprise any of the compositions described herein.
[00291] "Outdoor sign," as used herein, refers to a surface formed from the
polyester described herein, or containing symbols (e.g., numbers, letters,
words,
pictures, etc.), patterns, or designs coated with the polyester or polyester
film
described herein. In one embodiment, the outdoor sign comprises a polyester
containing printed symbols, patterns, or designs. In one embodiment, the sign
is
capable of withstanding typical weather conditions, such as rain, snow, ice,
sleet,
high humidity, heat, wind, sunlight, or combinations thereof, for a sufficient
period
of time, e.g., ranging from one day to several years or more.
[00292] Exemplary outdoor signs include, but are not limited to, billboards,
neon signs, electroluminescent signs, electric signs, fluorescent signs, and
light
emitting diode (LED) displays. Other exemplary signs include, but are not
limited
CA 02666585 2009-04-16
WO 2008/051321 PCT/US2007/015704
-88-
to, painted signs, vinyl decorated signs, thermoformed signs, and hardcoated
signs. -
[00293] In one embodiment, the outdoor sign has at least one property chosen
from thermoformability, toughness, clarity, chemical resistance, and T9.
[00294] A "vending machine display panel," as used herein, refers to a front
or
side panel on a vending machine that allows a customer to view the items for
sale, or advertisement regarding such items. In one embodiment, the vending
machine display panel can be a visually clear panel of a vending machine
through which a consumer can view the items on sale. In other embodiments,
the vending machine display panel can have sufficient rigidity to contain the
contents within the machine and/or to discourage vandalism and/or theft.
[00295] In one embodiment, the vending machine display panel can have
dimensions well known in the art, such as planar display panels in snack,
beverage, popcorn, or sticker/ticket vending machines, and capsule display
panels as in, e.g., gumball machines or bulk candy machines.
[00296] In one embodiment, the vending machine display panel can optionally
contain advertising media or product identification indicia. Such information
can
be applied by methods well known in the art, e.g., silk screening.
[00297] In one embodiment, the vending machine display panel can be
resistant to temperatures ranging from -100 to 120 C. In another embodiment,
the vending machine display panel can be UV resistant by the addition of,
e.g., at
least one UV additive, as disclosed herein.
[00298] In one embodiment, the vending machine display panel has at least
one property chosen from thermoformability, toughness, clarity, chemical
resistance, and T9.
[00299] "Point of purchase display," as used herein, refers to a wholly or
partially enclosed casing having at least one visually clear panel for
displaying an
item. Point of purchase displays are often used in retail stores to for the
purpose
of catching the eye of the customer. Exemplary point of purchase displays
include enclosed wall mounts, countertops, enclosed poster stands, display
cases (e.g., trophy display cases), sign frames, and cases for computer disks
such as CDs and DVDs. The point of purchase display can include shelves, and
CA 02666585 2009-04-16
WO 2008/051321 PCT/US2007/015704
-89-
additional containers, such as holders for magazines or pamphlets. One of
ordinary skill in the art can readily envision the shape and dimensions for
the
point of purchase display depending on the item to be displayed. For example,
the display can be as small as a case for jewelry, or a larger enclosed
cabinet for
displaying multiple trophies.
[00300] In one embodiment, the point of purchase display has at least one
property chosen from toughness, clarity, chemical resistance, T9, and
hydrolytic
stability.
[00301] "Appliance parts," as used herein, refers to a rigid piece used in
conjunction with an appliance. In one embodiment, the appliance part is partly
or
wholly separable from the appliance. In another embodiment, the appliance part
is one that is typically made from a polymer. In one embodiment, the appliance
part is visually clear.
[00302] Exemplary appliance parts include those requiring toughness and
durabilty, such as cups and bowls used with food processers, mixers, blenders,
and choppers; parts that can withstand refrigerator and freezer temperatures
(e.g., refrigerator temperatures ranging from greater than 0 C (e.g., 2 C) to
5 C,
or freezer temperatures, e.g., at temperatures less than 0 C, such as
temperatures ranging from -20 to 0 C, e.g., -18 C), such as refrigerator and
freezer trays, bins, and shelves; parts having sufficient hydrolytic stability
at
temperatures up to 90 C, such as washing machine doors, steam cleaner
canisters, tea kettles, and coffee pots; and vacuum cleaner canisters and dirt
cups.
1003031 In one embodiment, these appliance parts have at least one property
chosen from toughness, clarity, chemical resistance, T9, hydrolytic stability,
and
dishwasher stability. The appliance part can also be chosen from steam cleaner
canisters, which, in one embodiment, can have at least one property chosen
from
toughness, clarity, chemical resistance, T9, and hydrolytic stability.
1003041 In one embodiment, the polyesters useful in the appliance part has a
Ty
of 105 to 140 C and the appliance part is chosen from vacuum cleaner canisters
and dirt cups. In another embodiment, the polyesters useful in the appliance
part
CA 02666585 2009-04-16
WO 2008/051321 PCT/US2007/015704
-90-
has a T. of 120 to 150 C and the appliance part is chosen from steam cleaner
canisters, tea kettles and coffee pots.
[00305] "Skylight," as used herein, refers to a light permeable panel secured
to
a roof surface such that the panel forms a portion of the ceiling. In one
embodiment, the panel is rigid, e.g., has dimensions sufficient to achieve
stability
and durability, and such dimensions can readiliy be determined by one skilled
in
the art. In one embodiment, the skylight panel has a thickness greater than
3/16
inches, such as a thickness of at least 1/2 inches.
[00306] In one embodiment, the skylight panel is visually clear. In one
embodiment, the skylight panel can transmit at least 35% visible light, at
least
50%, at least 75%, at least 80%, at least 90%, or even at least 95% visible
light.
In another embodiment, the skylight panel comprises at least one UV additive
that allows the skylight panel to block up to 80%, 90%, or up to 95% UV light.
[00307] In one.embodiment, the skylight has at least one property chosen from
thermoformability, toughness, clarity, chemical resistance, and Tg.
[00308] "Outdoor shelters," as used herein, refer to a roofed and/or walled
structure- capable of affording at least some protection from the elements,
e.g.,
sunlight, rain, snow, wind, cold, etc., having at least one rigid panel. In
one
embodiment, the outdoor shelter has at least a roof and/or one or more walls.
In
one embodiment, the outdoor shelter has dimensions sufficient to achieve
stability and durability, and such dimensions can readiliy be determined by
one
skilled in the art. In one embodiment, the outdoor shelter panel has a
thickness
greater than 3/16 inches.
[00309] In one embodiment, the outdoor shelter panel is visually clear. In one
embodiment, the outdoor shelter panel can transmit at least 35% visible light,
at
least 50%, at least 75%, at least 80%, at least 90%, or even at least 95%
visible
light. In another embodiment, the outdoor shelter panel comprises at least one
UV additive that allows the outdoor shelter to block up to 80%, 90%, or up to
95%
UV light.
[00310] Exemplary outdoor shelters include security glazings, transportation
shelters (e.g., bus shelters), telephone kiosks, and smoking shelters. In one
embodiment, where the shelter is a transportation shelter, telephone kiosk, or
CA 02666585 2009-04-16
WO 2008/051321 PCT/US2007/015704
-91 -
smoking shelter, the shelter has at least one property chosen from
thermoformability, toughness, clarity, chemical resistance, and Tg. In one
embodiment, where the shelter is a security glazing, the shelter has at least
one
property chosen from toughness, clarity, chemical resistance, and Tg.
[00311] A"canopy, as used herein, refers to a roofed structure capable of
affording at least some protection from the elements, e.g., sunlight, rain,
snow,
wind, cold, etc. In one embodiment, the roofed structure comprises, either in
whole or in part, at least one rigid panel, e.g., has dimensions sufficient to
achieve stability and durability, and such dimensions can readiliy be
determined
by one skilled in.the art. In one embodiment, the canopy panel has a thickness
greater than 3/16 inches, such as a thickness of at least 1/2 inches.
[003121 In one embodiment, the canopy panel is visually clear. In one
embodiment, the canopy panel can transmit at least 35% visible light, at least
50%, at least 75%, at least 80%, at least 90%, or even at least 95% visible
light.
In another embodiment, the canopy panel comprises at least one UV additive
that
allows the canopy to block up to 80%, 90%, or up to 95% UV light.
[00313] Exemplary canopies include covered walkways, roof lights, sun rooms,
airplane canopies, and awnings. In one embodiment, the canopy has at least
one property chosen from toughness, clarity, chemical resistance, T9, and
flexibility.
[00314] A "sound barrier," as used herein, refers to a rigid structure capable
of
reducing the amount of sound transmission from one point on a side of the
structure to another point on the other side when compared to sound
transmission between two points of the same distance without the sound
barrier.
The effectiveness in reducing sound transmission can be assessed by methods
known in the art. In one embodiment, the amount of sound transmission that is
reduced ranges from 25 % to 90 %.
[00315] In another embodiment, the sound barrier can be rated as a sound
transmission class value, as described in, for example, ASTM E90, "Standard
Test Method for Laboratory Measurement of Airborne Sound Transmission Loss
of Building Partitions and Elements," and ASTM E413, "Classification of Rating
Sound Insulation." An STC 55 barrier can reduce the sound of a jet engine,
CA 02666585 2009-04-16
WO 2008/051321 PCT/US2007/015704
-92-
-130 dBA, to 60 dBA, which is the sound level within a typical office. A sound
proof room can have a sound level ranging from 0-20 dBA. One of ordinary skill
in the art can construct and arrange the sound barrier to achieve a desired
STC
rating. In one embodiment, the sound barrier has an STC rating of at least 20,
such as a rating ranging from 20 to 60.
[00316] In one embodiment, the sound barrier comprises a plurality of panels
connected and arranged to achieve the desired barrier outline. The sound
barriers can be used along streets and highways to dampen automotive noises.
Alternatively, the sound barriers can be used in the home or office, either as
a
discrete panel or panels, or inserted within the architecture of the walls,
floors,
ceilings, doors, and/or windows.
1003171 In one embodiment, the sound barrier is visually clear. In one
embodiment, the sound barrier can transmit at least 35% visible light, at
least
50%, at least 75%, at least 80%, at least 90%, or even at least 95% visible
light.
In another embodiment, the sound barrier comprises at least one UV additive
that
allows the sound barrier to block up to 80%, 90%, or up to 95% UV light.
1003181 In one embodiment, the sound barrier has at least one property chosen
from toughness, clarity, chemical resistance, and T.
[00319] A "greenhouse," as used herein, refers to an enclosed structure used
for the cultivation and/or protection of plants. In one embodiment, the
greenhouse is capable of maintaining a humidity and/or gas (oxygen, carbon
dioxide, nitrogen, etc.) content desirable for cultivating plants while being
capable
of affording at least some protection from the elements, e.g., sunlight, rain,
snow,
wind, cold, etc. In one embodiment, the roof of the greenhouse comprises,
either
in whole or in part, at least one rigid panel, e.g., has dimensions sufficient
to
achieve stability and durability, and such dimensions can readiliy be
determined
by one skilled in the art. In one embodiment, the greenhouse panel has a
thickness greater than 3/16 inches, such as a thickness of at least 1/2
inches.
[00320] In one embodiment, the greenhouse panel is visually clear. In another
embodiment, substantially all of the roof and walls of the greenhouse are
visually
clear. In one embodiment, the greenhouse panel can transmit at least 35%
visible
light, at least 50%, at least 75%, at least 80%, at least 90%, or even at
least 95%
CA 02666585 2009-04-16
WO 2008/051321 PCT/US2007/015704
-93-
visible light. In another embodiment, the greenhouse panel comprises at least
one UV additive that allows the greenhouse panel to block up to 80%, 90%, or
up
to 95% UV light.
[00321] In one embodiment, the greenhouse panel has at least one property
chosen from toughness, clarity, chemical resistance, and Tg.
[00322] An "optical medium," as used herein, refers to an information storage
medium in which information is recorded by irradiation with a laser beam,
e.g.,
light in the visible wavelength region, such as light having a wavelength
ranging
from 600 to 700 nm. By the irradiation of the laser beam, the irradiated area
of
the recording layer is locally heated to change its physical or chemical
characteristics, and pits are formed in the irradiated area of the recording
layer.
Since the optical characteristics of the formed pits are different from those
of the
area having been not irradiated, the digital information is optically
recorded. The
recorded information can be read by reproducing procedure generally comprising
the steps of irradiating the recording layer with the laser beam having the
same
wavelength as that employed in the recording procedure, and detecting the
light-
reflection difference between the pits and their periphery.
(00323] In one embodiment, the optical medium comprises a transparent disc
having a spiral pregroove, a recording dye layer placed in the pregroove on
which
information is recorded by irradiation with a laser beam, and a light-
reflecting
layer. The optical medium is optionally recordable by the consumer. In one
embodiment, the optical medium is chosen from compact discs (CDs) and digital
video discs (DVDs). The optical medium can be sold with prerecorded
information, or as a recordable disc.
[00324] In one embodiment, at least one of the following comprises the
polyester of the invention: the substrate, at least one protective layer of
the
optical medium, and the recording layer of the optical medium.
[00325] In one embodiment, the optical medium has at least one property
chosen from toughness, clarity, chemical resistance, Tg, and hydrolytic
stability.
[00326] A "glass laminate," as used herein, refers to at least one coating on
a
glass, where at least one of the coatings comprises the polyester. The coating
can be a film or a sheet. The glass can be clear, tinted, or reflective. In
one
CA 02666585 2009-04-16
WO 2008/051321 PCT/US2007/015704
-94-
embodiment, the laminate is permanently bonded to the glass, e.g., applying
the
laminate under heating and pressure to form a single, solid laminated glass
product. One or both faces of the glass can be laminated. In certain
embodiments, the glass laminate contains more than one coating comprising the
polyester compositions of the present invention. In other embodiments, the
glass
laminate comprises multiple glass substrates, and more than one coating
comprising the polyester compositions of the present invention.
[00327] Exemplary glass laminates include windows (e.g., windows for high
rise buildings, building entrances), safety glass, windshields for
transportation
applications (e.g., automotive, buses, jets, armored vehicles), bullet proof
or
resistant glass, security glass (e.g., for banks), hurricane proof or
resistant glass,
airplane canopies, min-ors, solar glass panels, flat panel displays, and blast
resistant windows. The glass laminate can be visually clear, be frosted,
etched,
or patterned.
[00328] In one embodiment the glass laminate can be resistant to temperatures
ranging from -100 to 120 C. In another embodiment, the glass laminate can be
UV resistant by the addition of, e.g., at least one UV additive, as disclosed
herein.
[00329] Methods for laminating the films and/or sheets of the present
invention
to the glass are well known to one of ordinary skill in the art. Lamination
without
the use of an adhesive layer may be performed by vacuum lamination. To obtain
an effective bond between the glass layer and the laminate, in one embodiment,
the glass has a low surface roughness.
[00330] Alternatively, a double-sided adhesive tape, an adhesive layer, or a
gelatin layer, obtained by applying, for example, a hotmelt, a pressure- or
thermo-
sensitive adhesive, or a UV or electron-beam curable adhesive, can be used to
bond the laminate of the present invention to the glass. The adhesive layer
may
be applied to the glass sheet, to the laminate, or to both, and may be
protected
by a stripping layer, which can be removed just before lamination.
1003311 In one embodiment, the glass laminate has at least one property
chosen from toughness, clarity, chemical resistance, hydrolytic stability, and
T9.
[00332] For the purposes of this invention, the term "wt" means "weight".
CA 02666585 2009-04-16
WO 2008/051321 PCT/US2007/015704
-95-
[00333] The following examples further illustrate how the polyesters of the
invention can be made and evaluated, and are intended to be purely exemplary
of the invention and are not intended to limit the scope thereof. Unless
indicated
otherwise, parts are parts by weight, temperature is in degrees C or is at
room
temperature, and pressure is at or near atmospheric.
CA 02666585 2009-04-16
WO 2008/051321 PCT/US2007/015704
-96-
EXAMPLES
[00334] The following examples illustrate in general how copolyesters of this
invention are prepared and the effect of using 2,2,4,4-tetramethyl-
1,3-cyclobutanediol, 1,4-cyclohexanedimethanol, and ethylene glycol on various
copolyester properties such as glass transition temperature, notched Izod
impact
strength, and flexural modulus, in comparison to other copolyesters based on
2,2,4,4-tetramethyl-1,3-cyclobutanediol. Additionally, based on the following
examples, the skilled artisan will understand how certain catalyst systems and
thermal stabilizers can be used in the preparation of polyesters of the
invention.
Measurement Methods
[00335] The inherent viscosity of the polyesters was determined in 60/40
(wbwt) phenol/tetrachloroethane at a concentration of 0.5 g/100 ml at 25 C,
and
is reported in dUg.
[00336] Unless stated otherwise, the glass transition temperature (Tg) was
determined using a TA DSC 2920 instrument from Thermal Analyst Instruments
at a scan rate of 20 C/min according to ASTM D3418.
[00337] The glycol content and the cis/trans ratio of the compositions were
determined by proton nuclear magnetic resonance (NMR) spectroscopy. All
NMR spectra were recorded on a JEOL Eclipse Plus 600MHz nuclear magnetic
resonance spectrometer using either chloroform-trifluoroacetic acid (70-30
volume/volume) for polymers or, for oligomeric samples, 60/40(wt/wt) phenol/
tetrachloroethane with deuterated chloroform added for lock. Peak assignments
for 2,2,4,4-tetramethyl-1,3-cyclobutanediol resonances were made by
comparison to model mono- and dibenzoate esters of 2,2,4,4-tetramethyl-
1,3-cyclobutanediol. These model compounds closely approximate the
resonance positions found in the polymers and oligomers.
[00338] Unless stated otherwise, the polymers were dried in a dessicant dryer
at 80 C overnight prior to injection molding in a Boy 22S molding machine into
1/8x1/2x5-inch flexure bars. These bars were cut to a length of 2.5 inch and
notched down the '/2 inch width with a 10-mil notch. The Izod impact strength
was determined as an average from measurements on 5 specimens and in
CA 02666585 2009-04-16
WO 2008/051321 PCT/US2007/015704
-97-
accordance with ASTM D256. The flexural modulus was determined according
to the procedures of ASTM D790.
[00339] Color values reported herein are CIELAB L*, a*, and b* values
measured following ASTM D 6290-98 and ASTM E308-99, using measurements
from a Hunter Lab Ultrascan XE Spectrophotometer (Hunter Associates
Laboratory Inc., Reston, VA) with the following parameters: (1) D65
illuminant,
(2) 10 degree observer, (3) reflectance mode with specular angle included, (4)
large area view, (5) 1" port size. Unless stated otherwise, the measurements
were performed on polymer granules ground to pass a 6 mm sieve. Haze was
measured on 4x4x1/8" plaques according to ASTM D-1003.
[00340] The amount of tin (Sn) and titanium (Ti) in the examples below is
reported in parts per million (ppm) of metal and was measured by x-ray
fluorescence (xrf) using a PANanalytical Axios Advanced wavelength dispersive
x-ray fluorescence spectrometer. The amount of phosphorous is similarly
reported as ppm of elemental phosphorus and was also measured by xrf using
the same instrument. The values reported in the column "P measured" in the
following examples were obtained by measuring phosphorous as described
above.
[00341] Unless otherwise specified, the cis/trans ratio of the
1,4 cyclohexanedimethanol used in the following examples was approximately
30/70, and could range from 35/65 to 25l75. Unless otherwise specified, the
cis/trans ratio of the 2,2,4,4-tetramethyl-1,3-cyclobutanediol used in the
following
examples was approximately 50/50 and could range from 45/55 to 55/45.
CA 02666585 2009-04-16
WO 2008/051321 PCT/US2007/015704
-98-
[00342] The following abbreviations apply throughout the working examples
and figures: -
CHDM 1,4-cyclohexanedimethanol
DBTO Dibutyltin oxide
DMT Dimethyl therephthalate
DEG Diethylene glycol
DMTO Dimethyl tin oxide
EG Ethylene glycol
IV Inherent viscosity
T9 Glass transition temperature
TIIP Titanium Isopropoxide
TMCD 2,2,4,4-tetramethyl-1,3-cyclobutanediol
TPA Terephthalic acid
TPP Triphenyl phosphate
Example 1
[00343] This example illustrates the preparation of polyesters comprising
dimethyl terephthalate (DMT), 1,4-cyclohexanedimethanol (CHDM),
2,2,4,4-tetramethyl-1,3-cyclobutanediol (TMCD), and ethylene glycol (EG).
[00344] The DMT was purchased from Cape Industries, the CHDM (min. 98
%), the EG, and the TMCD (min. 98 %) were from Eastman Chemical Company.
The tin compound was dibutyltin (IV) oxide (Fascat 4201; from Aldrich). The
titanium compound was titanium (IV) isopropoxide (Aldrich). The phosphorus
compound was triphenyl phosphate (TPP, from Aldrich (98 %) or FERRO, Corp.).
Unless otherwise indicated below, the source of phosphorous was added upfront,
with the rest of the polyester reagents. The cis/trans ratio of the CHDM and
TMCD was as described above.
CA 02666585 2009-04-16
WO 2008/051321 PCT/US2007/015704
-99-
Example 1A
[003451 This example illustrates the preparation of a copolyester with a
target
composition of 100 mole % dimethyl terephthalate residues, 30 mol %
2,2,4,4-tetramethyl-1,3-cyclobutanediol residues, and 30 mol%
1,4-cyclohexanedimethanol residues, and the rest ethylene glycol residues.
[003461 A mixture of 99.71 g of dimethyl terephthalate, 21.63 g of
1,4-cyclohexanedimethanol, 37.86 g of 2,2,4,4-tetramethyl-1,3-cyclobutanediol,
and 20.95 g of ethylene glycol was placed in a 500-milliliter flask equipped
with
an inlet for nitrogen, a metal stirrer, and a short distillation column. In
addition,
0.0077 g of dibutyltin (IV) oxide, 0.0218 g of titanium (IV) isopropoxide, and
0.50
g of triphenyl phosphate was added to the 500-milliliter flask. The flask was
placed in a Wood's metal bath already heated to 200 C. The stirring speed was
set to 200 RPM at the beginning of the experiment. The contents of the flask
were heated at 200 C for 60 minutes and then the temperature was gradually
increased to 210 C over 5 minutes. The reaction mixture was held at 210 C for
60 minutes and then heated up to 275 C in 90 minutes. Once at 275 C, vacuum
was gradually applied over the next 10 minutes with a set point of 100 mm of
Hg
and the stirring.speed was also reduced to 100 RPM. The pressure inside the
flask was further reduced to a set point of 0.3 mm of Hg over the next 5
minutes
and the stirring speed was reduced to 50 RPM. This pressure was maintained
for a total time of 220 minutes to remove excess unreacted diols. This process
resulted in a high melt viscosity, visually clear, and colorless to very
slightly
yellow polymer with a glass transition temperature of 107 C and an inherent
viscosity of 0.67 dl/g. NMR analysis showed that the copolyester was composed
of 30 mole % 1,4-cyclohexanedimethanol residues, 30 mole %
2,2,4,4-tetramethyl-1,3-cyclobutanediol residues, and 40 mole % ethylene
glycol
resid ues.
Example 1 B to Example 1 K
1003471 A variety of polyesters were prepared as described above from 100
mole% dimethyl terephthalate. However, different amounts of triphenyl
CA 02666585 2009-04-16
WO 2008/051321 PCT/US2007/015704
- 100 -
phosphate were added to the initial reaction mixture as indicated in Table 1.
The
mole% of TMCD and CHDM for the experiments of this example is also reported
in Table 1, with the glycol balance being EG. The glycol/acid ratio was 1.5/1
with
the glycol feed having 20 mole% CHDM, 35 mole% TMCD and 45 mole% EG.
The set points and data collection were facilitated by a Camile process
control
system. Once the reactants were melted, stirring was initiated and slowly
increased. The Camile sequence shown below was used in the preparation of
these copolyesters.
[00348] Camile Sequence for Example 1 B to Example 1 K
T- :.~..:~
;S_ ta aTime m~nutes ~Tem'" ,ratgre; acuum~ tor,r, x ~~St1rnn
1 0.5 200 730 0
2 4.5 200 730 200
3 60 200 730 200
4 5 210 730 200
60 210 730 100
6 90 275 730 100
7 5 275 400 50
8 5 275 100 50
9 5 275 0.3 50
220 275 0.3 50
[00349] In stage 10, the stir rate was dropped to 25 rpm and even to 10 rpm if
the viscosity was too high. The holding time in stage 10 for Examples G and H
was 130 minutes.
CA 02666585 2009-04-16
WO 2008/051321 PCT/US2007/015704
-101-
O~ MLf) M O
DO tD U~ f-
O) (C 00 U') Z Z
LC) 1~ 1+ N st
t~') M t [r) IT I~
~- N
' , , ' ' z z
O) 1~ N O) Q)
~ CD LA O N ap
Oi 1~ CO aD 1- N 2
~ ~ ~ ti ` Z z
_
d t[) 1- N N Cq O) CC V
E ~.
~ V t0 1- 00 O O N N
RS
x
l1J
~ 00 CO O (O ~ oD
0 ~ '
~ E ~ c*-j
~ Q 10
~
~, E z z
o
CL a~ 07 f N(~D O N(O ~~
(D
O V N.-
~ a '
o a
r a O CV I- NU') O O C)
O tl) Lo O M O O
V) a p~ W O O - cM N N
~ t0) C) C) O O O O 0 O
!0 N
> E O M tO N cM N
O. M M M M M CM mr,
ay z z
to c`r)
C E M M M C")
Z Z
<O N 1, f7
O O O O O C C C
o G E r
0 0
0 ~~ ~ I" tn O) OcO CU ~ p
O Oo Q) Q) ~- QO CO N N
CM N N) N N M
2 = O N N ~
_ v E E
N >`
a OD M C7 CM -: O N 00 Q
E V O N c0~) cr*-~) M t~~) c~~) c) cM~)
V E
O Cr) 1- CO ~~
Of 1- tI) C) f~ W) Q) V CO y 4)
CP 0) I- I- 1~ CO (O (P E E
~ O C O O O O O O O O
Z (I)
d iI W
a ~ m
~ QmOOWU.C~z~
tt~
CA 02666585 2009-04-16
WO 2008/051321 PCT/US2007/015704
-102-
Example 2
[00350] This example illustrates the effect of thermal stabilizer levels on
polymer color and inherent viscosity of copolyesters with a target composition
of
100 mole% dimethyl terephthalate residues, 30 mole% 2,2,4,4-tetramethyl-
1,3-cyclobutanedioi residues, 30 mole % 1,4-cyclohexanedimethanol residues,
and 40 mole% ethylene glycol residues using a combination of tin and titanium
catalysts. Unless otherwise specified, the source of monomers, catalysts, and
thermal stabilizers is the same as in Example 1.
Example 2A
[00351] A mixture of 99.71 g of dimethyl terephthalate, 21.63 g of
1,4-cyclohexanedimethanol, 37.86 g of 2,2,4,4-tetramethyl-1,3-cyclobutanediol,
and 20.95 g of ethylene glycol was placed in a 500-milliliter flask equipped
with
an inlet for nitrogen, a metal stirrer, and a short distillation column. In
addition,
0.0077 g of dibutyltin (IV) oxide and 0.0218 g of titanium (IV) isopropoxide
were
added to the 500-milliliter flask. The flask was placed in a Wood's metal bath
already heated to 200 C. The stirring.speed was set to 200 RPM at the
beginning of the experiment. The contents of the flask were heated at 200 C
for
60 minutes and then the temperature was gradually increased to 210 C over 5
minutes. The reaction mixture was held at 210 C for 60 minutes and then heated
up to 275 C in 90 minutes. Once at 275 C, vacuum was gradually applied over
the next 10 minutes with a set point of 100 mm of Hg and the stirring speed
was
also reduced to 100 RPM. The pressure inside the flask was further reduced to
a
set point of 0.3 mm of Hg over the next 5 minutes and the stirring speed was
reduced to 50 RPM. This pressure was maintained for a total time of 220
minutes to remove excess unreacted diols. This process resulted in a polymer
with a glass transition temperature of 117.7 C and an inherent viscosity of
1.011 dUg. NMR analysis showed that the copolyester wa's composed of 29
mole % 1,4-cyclohexanedimethanol residues, 37 mole % 2,2,4,4-tetramethyl-
1,3-cyclobutanediol residues, and 34 mole % ethylene glycol residues. While
CA 02666585 2009-04-16
WO 2008/051321 PCT/US2007/015704
-103-
outside the scope of the originally-filed claims, this example is included
here to
show the effect of the level of thermal stabilizer on color and inherent
viscosity.
Example 2B to Example 2E
[00352] A variety of polyesters were prepared as described above from 100
mole% dimethyl terephthalate. However, different amounts of triphenyl
phosphate were added to the initial reaction mixture as indicated in Table 2.
The
mole% of TMCD and CHDM for the experiments of this example is also reported
in Table 2, with the glycol balance being EG. The glycol/acid ratio was 1.5/1
with
the glycol feed having 20 mole% CHDM, 35 mole% TMCD and 45 mole% EG.
The set points and data collection were facilitated by a Camile process
control
system. Once the reactants were melted, stirring was initiated and slowly
increased. The Camile sequence shown below was used in the preparation of
these copolyesters. -
[00353] Camile Sequence for Example 2B to Example 2E
~ Sta= e`~I `~Tim~e minu~es ~~ i~Tem e .r`ature~C~ ~Vac uu m" rr .~~S tim n ~,
= ;RPM a
~. _ _ _._
1 0.5 200 730 0
2 4.5 200 730 200
3 60 200 730 200
4 5 210 730 200
60 210 730 100
6 90 275 730 100
7 5 275 400 50
8 5 275 100 50
9 5 275 0.3 50
220 275 0.3 50
[00354] In stage 10, the stir rate was dropped to 25 rpm and even to 10 rpm if
the viscosity was too high.
CA 02666585 2009-04-16
WO 2008/051321 PCT/US2007/015704
-104-
00
d
N M N O
r (fl ~
1n La Irt
cc 0
CO CO M lcn
t 1- 1f)
J OCD M fl- co
r- n N. ~ 1*-
N
O) Lf) ~ M
f- tf'> 1~ C7 di
` e- ~.- r- O
a.+
N OO O> t~
L a'S Nv~~
a
ad
c E
co
2 O U-> c0 co o
o a o v co r-
` Qt
a~.
~
~ O CV O ui co
cv >. n. oui O o rn
- N M
Q H O O o 0 0 0 0
~ U
0 Q`C c MM c~~ c'O~) C~) CM~)
~
a M MVv
M M M
U O.
N 47 r- ~ 0R
\
0 O O o 0 0
W O
`o o E
t O
~ N ~ N M N
Qi Oi Qi o0 Oi
0
= p N N N N N
a V E
93 17 Lo N tn N
~o c' ch M M Mm
al V O
W E
M t- lw N fl
Na)
n O Q) 1~
O O O O
~ O
0
W
a o
E QmUOUJ~
m
x
W
CA 02666585 2009-04-16
WO 2008/051321 PCT/US2007/015704
-105-
Example 3
[00355] This example illustrates the effect of catalyst choice and amount of
thermal stabilizer on the final color and inherent viscosity of a copolyester
with a
target composition of 100 mole % dimethyl terephthalate residues, 30 mole%
2,2,4,4-tetramethyl-1,3-cyclobutanediol residues, 30 mole%
1,4-cyclohexanedirnethanol residues, and 40 mole% ethylene glycol residues.
[00356] A mixture of 99.71 g of dimethyl terephthalate, 21.63 g of
1,4-cyclohexanedimethanol, 37.86 g of 2,2,4,4-tetramethyl-1,3-cyclobutanediol,
and 20.95 g of ethylene glycol was placed in a 500-milliliter flask equipped
with
an inlet for nitrogen, a metal stirrer, and a short distillation column.
Various
amounts of dibutyltin (IV) oxide, titanium (IV) isopropoxide, and triphenyl
phosphate were added to the 500-milliliter flask. The flask was placed in a
Wood's metal bath already heated to 200 C. The stirring speed was set to 200
RPM at the beginning of the experiment. The contents of the flask were heated
at 200 C for 60 minutes and then the temperature was gradually increased to
210 C over 5 minutes. The reaction mixture was held at 210 C for 60 minutes
and then heated up to 275 C in 90 minutes. Once at 275 C, vacuum was
gradually applied over the next 10 minutes with a set point of 100 mm of
Hg.and
the stirring speed was also reduced to 100 RPM. The pressure inside the flask
was further reduced to a set point of 0.3 mm of Hg over the next 5 minutes and
the stirring speed was reduced to 50 RPM. This pressure was maintained for a
total time of 220 minutes to remove excess unreacted diols. All samples were
prepared by the same method using the catalyst and triphenyl phosphate levels
reported in Table 3. The final TMCD and CHDM mole % for these copolyesters
is reported also in Table 3, with the diol balance being EG. The effect of the
catalyst system and thermal stabilizer on 2,2,4,4-tetramethyl-1,3-
cyclobutanediol
incorporation, copolyester color, and inherent viscosity are shown in Table 3.
Examples G, H, and I in Table 3 below correspond to Example 2A, Example 2D,
and Example 1A respectively and are included in Table 3 to facilitate
comparison
among polyesters prepared using different catalyst systems and different
levels
of phosphorous.
CA 02666585 2009-04-16
WO 2008/051321 PCT/US2007/015704
-106-
Table 3
Effect of catalyst and triphenyl phosphate levels on
TMCD incorporation, color, and inherent viscosity
TIIP (g)/ DBTO (g)/ppm TPP TMCD In CHDM In IV
Example ppm Ti Sn (g) polyesoter polyester b* (dUg)
mole /o (mole /
A 0 0.0154/ 60 ppm 0.00 40.0 29.1 15.1 0.78
B 0 0.0154/ 60 ppm 0.20 28.5 31.2 2.6 0.18
C 0 0.0154/ 60 ppm 0.50 24.1 30.7 3.7 0.17
D 0.042/ 60 ppm 0 0.00 28.7 29.4 21.1 0.91
E 0.042/ 60 ppm 0 0.20 27.7 31.0 11.1 0_78
F 0.042/ 60 ppm 0 0.50 25.5 31.0 10.6 0.56
G 0.021/ 30 ppm 0.077/ 30 ppm 0.00 37.1 29.2 18.0 1.01
H 0.021/ 30 ppm 0.077/ 30 ppm 0.21 38.5 28.3 6.2 0.74
I 0.021/ 30 ppm 0.077/ 30 ppm 0.50 29.8 30.1 4.9 0_67
[00357] While outside the scope of the originally-filed claims, Examples A, D,
and G are included here to show the effect of the catalyst system and thermal
stabilizer on TMCD incorporation, color, and inherent viscosity.
Example 4
[00358] This example illustrates the preparation of polyesters comprising
dimethyl terephthalate (DMT), 2,2,4,4-tetramethyl-1,3-cyclobutanediol (TMCD),
and ethylene glycol (EG).
1003591 Unless otherwise specified, the source of monomers, catalysts, and
thermal stabilizers is the same as in Example 1. A variety of polyesters were
prepared from 100 mole% dimethyl terephthalate with the following procedure. A
mixture of 99.71 g of dimethyl terephthalate, 34.07 g of 2,2,4,4-tetramethyl-
1,3-cyclobutanediol, and 31.89 g of ethylene glycol was placed in a 500-
milliliter
flask equipped with an inlet for nitrogen, a metal stirrer, and a short
distillation
column. In addition, 0.0069 g of dibutyltin (IV) oxide and 0.019 g of titanium
(IV)
isopropoxide were added to the 500-milliliter flask. The flask was placed in a
Wood's metal bath already heated to 200 C. The stirring speed was set to 200
RPM at the beginning of the experiment. The contents of the flask were heated
at 200 C for 60 minutes and then the temperature was gradually increased to
210 C over 5 minutes. The reaction mixture was held at 210 C for 60 minutes
and then heated up to 275 C in 90 minutes. Once at 275 C, vacuum was
gradually applied over the next 10 minutes with a set point of 100 mm of Hg
and
CA 02666585 2009-04-16
WO 2008/051321 PCT/US2007/015704
-107-
the stirring speed was also reduced to 100 RPM. The pressure inside the flask
was further reduced to a set point of 0.3 mm of Hg over the next 5 minutes and
the stirring speed was reduced to 50 RPM. This pressure was maintained for a
total time of 220 minutes to remove excess unreacted diols.
[00360] Copolyesters were prepared using this method employing the amounts
of triphenyl phosphate reported in Table 4. The phosphorous source was added
to the reaction mixture at the same time the catalysts were added. The mole%
of
TMCD for the experiments of this example is also reported in Table 4, with the
glycol balance being EG. The glycol/acid ratio was 1.5/1 with 32 mol% TMCD in
the glycol feed and the rest being EG. The set points and data collection were
facilitated by a Camile process control system. Once the reactants were
melted,
stirring was initiated and slowly increased.
[00361] Camile Sequence used in the preparation of the copolyesters of this
example:
~, ta e~~ ~Time m~outes ~ Tiem e atu`~C~ ~/a.cuum~ to~r,r, ~~Stir'in''"~,RPM ~
_
1 0.5 200 730 0
2 4.5 200 730 200
3 60 200 730 200
4 5 210 730 200
60 210 730 100
6 90 275 730 100
7 5 275 400 50
8 5 275 100 50
9 5 275 0.3 50
220 275 0.3 50
[00362] In stage 10, the stir rate was dropped to 25 rpm and even to 10 rpm if
the viscosity was too high.
CA 02666585 2009-04-16
WO 2008/051321 PCT/US2007/015704
-108-
00 00 -tt 00 QO N tM (V ~ OD
N C,j O~ t- N c7 f~ O~ O tn
I-T cn (N aD (D co Lo 1~ v
.--
sr co N m (V OD Crl e- co 4
st d OLa NU~ CO
H ~ ~ ~ N N ~ CV ~ ~
M M OtO N I~ M
* O O 1~ ~j OD ~ aj c7 CO CD
~ J a~o aNO ~~~~ a~o ~~ o~o aC)o
~
CM ~ C7 O(O 00 W 7 (q c~ v7
E
Q3 1T 0 ~ N - LO I~ M c7 I- tn Itt CM
X v O O O) O O CD O C) O O
w
`~- ~ N~ 00 N f- C~) O~~ O
O
a <D O a0 C7 t0 c'n tA <O O
~ y
a> E
i n a1 i
E
0
Q a 1~ M N O O CO O C'1 (O r- C)
N ~ t0 cM N(O Nr a0 ~ aD
4) O ~ fV fV %r
~ at
O CL
.-
CO co O M O co O O O O
Q, Q~ O O N I- NL=) O fV N
~ a p~ r- N M~ O O r- O - - N
O O O O O O O O O C
~ N
> a~ M c~+) c~ CO~) rNi c~ ) cN+> i c~ ) i
a
(D
C. ~ N cN~ c'O') c~ ~ c M c'N~ ~ M
a
~ a I~ n cp 1- c L[) u) co c0 tm t~
~- o 0 0 0 0 0 0 0 0 0 0
o c E a
p o
V Q y M O) M<D N Ch N Mv CO E-u
C C ~ ~ N O ---. LA t/7
t[~ tn LO
(D
E
=
N ~ o >.
O 0
Q ~ 0) u) I~ t~ -n t~ 00 c+) tD I-
E N N , 1~ --it M Nv v M(V ~
0 ~. O M c7 M N C7 C7 C7 C7 C7 f'') C7 C
V H E
N 1- O 00 I~ v ~(O c'n - O N
~? ~O N(O Q) M CD O O~ C") C'7 N
~A 1n V O 1- 1- I~ 1~ (D <O
O O O O O O O O O O O
.... ~
~ W
C. ~
Ea QmUOwU- (D
x
W
CA 02666585 2009-04-16
WO 2008/051321 PCT/US2007/015704
-109-
Example 5
[00363] This example illustrates the effect of thermal stabilizer levels on
polymer color and inherent viscosity copolyesters with a target composition of
100 mole % dimethyl terephthalate residues, 33 mole % 2,2,4,4-tetramethyl-
1,3-cyclobutanediol residues, and 67 mole % ethylene glycol residues using a
combination of tin and titanium catalysts.
[00364] Unless otherwise specified, the source of monomers, catalysts, and
thermal stabilizers is the same as in Example 1. A variety of polyesters were
prepared from 100 mole% dimethyl terephthalate with the following procedure. A
mixture of 99.71 g of dimethyl terephthalate, 34.07 g of 2,2,4,4-tetramethyl-
1,3-cyclobutanediol, and 31.89 g of ethylene glycol was placed in a 500-
milliliter
flask equipped with an inlet for nitrogen, a metal stirrer, and a short
distillation
column. In addition, 0.0069 g of dibutyltin (IV) oxide and 0.019 g of titanium
(IV)
isopropoxide were added to the 500-milliliter flask. The flask was placed in a
Wood's metal bath already heated to 200 C. The stirring speed was set to 200
RPM at the beginning of the experiment. The contents of the flask were heated
at 200 C for 60 minutes and then the temperature was gradually increased to
210 C over 5 minutes. The reaction mixture was held at 210 C for 60 minutes
and then heated up to 275 C in 90 minutes. Once at 275 C, vacuum was
gradually applied over the next 10 minutes with a set point of 100 mm of Hg
and
the stirring speed was also reduced to 100 RPM. The pressure inside the flask
was further reduced to a set point of 0.3 mm of Hg over the next 5 minutes and
the stirring speed was reduced to 50 RPM. This pressure was maintained for a
total time of 220 minutes to remove excess unreacted diols.
[00365] Copolyesters were prepared using this method employing the amounts
of triphenyl phosphate reported in Table 5. The phosphorous source was added
to the reaction mixture at the same time the catalysts were added. The mole%
of
TMCD for the experiments of this example is also reported in Table 5, with the
glycol balance being EG. The glycol/acid ratio was 1.5/1 with 32 mol% TMCD in
the glycol feed and the rest being EG. The set points and data collection were
CA 02666585 2009-04-16
WO 2008/051321 PCT/US2007/015704
-110-
facilitated by a Camile process control system. Once the reactants were
melted,
stirring was initiated and slowly increased.
[00366] Camile Sequence used in the preparation of the copolyesters of this
example:
Sta" e~'~ ~Time~ m~nut s~T~em er~ture, C" Vacuuin~i to,.. ~Stirr.in ~;RPM ~
1 0.5 200 730 0
2 4.5 200 730 200
3 60 200 730 200
4 5 210 730 200
60 210 730 100
6 90 275 730 100
7 5 275 400 50
8 5 275 100 50
9 5 275 0.3 50
220 275 0.3 50
[00367] In stage 10, the stir rate was dropped to 25 rpm and even to 10 rpm if
the viscosity was too high. While outside the scope of the originally-filed
claims,
Example A is included here to show the effect of the level of thermal
stabilizer on
color and inherent viscosity.
CA 02666585 2009-04-16
WO 2008/051321 PCT/US2007/015704
-111-
0O N O) (D ~
+ CC) N .--
N
~ O 0) CO tD M
ln M r- f~ (O
CO (V rl,~
lV r- ~ ~ ~ ~
~ i
~ w co
CO ~ M CO CD
J ul 0) C CV
.N
ti n 8 (p r N -: O)
m 00 I~ "s- .~r O
O O O O O
T f~ r r r
rt~
C) oD (O
N d ~~..
E
CL ~
-0 a a1
C E
m
C a C> C4 ONi ti v
~ M
C) C- L
Q
N
8
~A O~ O O O
cm O O - N
~ Q H O O O O O
O n~ M M M M M
y + Q
C
r E cr! N M N
O a c+) M Cr) M M
V
~ 4~ CD p 0 o c o
W o
o E
L 0
a C M
N CM N~V m
` N N N O O
0
Lt) Ll') w 11') 11')
d
E
O
+
Z 0'
M ( Q) Ge
fl ) N
~ U o M C~) M.
w L1 A
~E
Co 11- CD cM OD N
~' (O I- 0) ~ 00 E
a0 1_ (fl (O
O O O O O0
~
~ W
a
E Q m w
K
W
CA 02666585 2009-04-16
WO 2008/051321 PCT/US2007/015704
-112-
[00368] The invention has been described in detail with reference to the
embodiments disclosed herein, but it will be understood that variations and
modifications can be effected within the spirit and scope of the invention.
