Note: Descriptions are shown in the official language in which they were submitted.
2 0 ~
--1--
COPOLYESTERCARBONATE POLYMERS
DERIVED FROM DIARYL DICARBOXYLIC ACIDS
AND THEIR DERIVATIVES AND BLENDS THEREOF
This invention relates to copolyestercarbon-
ate polymers, resins, and blends thereof and more
~ 5 particularly to such polymers prepared from a diaryl
dicarboxylic acid compound.
A wide variety of polycarbonate and copolyes-
tercarbonate resins are known and usefully employed asthermoplastics for a variety o~ molded articles and com-
ponents. In spite of the wide diversity of physical
properties associated with the known resins, there re-
mains a need for even more diverse physical properties.
For some of today's current applications it
is desirable to provide copolyestercarbonate resins with
improved physical properties including increased tensile
and impact properties, improved hydrolytic and solvent
resistance and reduced sensitivity to ~V radiation.
Typically, copolyestercarbonate resins are
prepared by reacting a dihydroxy compound with a dicar-
boxylic acid compound and a carbonate precursor. The
367665~F -1-
2 0 ~
dicarboxylic acid compounds most commonly employed are
those of terephthalic acid and isophthalic acid.
It has now been discovered that the desirable
improvements in such physical properties of copolyester-
carbonate polymer resins can be obtained by using alter-
native dicarboxylic acid compounds.
In one aspect, this invention is a copolyester-
carbonate polymer prepared by contacting a dihydroxycompound with a dicarboxylic acid compound and a car-
bonate precursor characterized in that (a) at least 50
mols percent of the dicarboxylic acid compound employed
comprises a diaryl dicarboxylic acid compound containing
two or more aromatic rings which are connected together
~ by a positionally and angularly well defined rigid in
ternal linking group, and (b) the mole ratio of dicar-
boxylic acid compound to carbonate precursor is such
that the pol~mer has a molar ratio of diester:carbonate
groups from 0~02:1 to 20:1.
In another aspect, this invention is a ther-
moplastic polymer blend comprising a thermoplastic poly-
mer and a copolyestercarbonate polymer characterized inthat the copolyestercarbonate polymer is prepared by
contacting a dihydroxy compound with a dicarboxylic acid
compound and a carbonate precursor wherein (a) at least
50 mole percent of the dicarboxylic acid compound
employed comprises a diaryl dicarboxylic acid compound
containing two or more aromatic rings which are con-
nected together by a positionally and angularly well
defined rigid internal linking group, (b) the mole ratio
of dicarboxylic acid compound to carbonate precursor is
such that the polymer has a molar ratio of diester:car-
36,665-F -2
- ;,
20~l16
--3--
bonate groups from 0.02:1 to 20:1 and ~c) in that the
polymer blend contains at least 0.5 weight percent of
th~ said cupolye3Lercarbona~e by to~al weight of
thermoplastic polymer and copolyestercarbonate polymer
present.
Surprisingly, it has been found that the poly-
mers of the present invention exhibit improved proper-
ties including impact strengths, glass transition tem-
peratures, and reduced ultraviolet radiation sensitiv-
ity. Even more surprisingly, it has been found that the
polymers of the present invention may be used~ for exam-
ple, in preparing films where the thickness of the film
prepared can be greater than that for other polymers in
the prior art without the problem of a crystallinity
- buildup.
As described hereinabove, this invention is a
copolyestercarbonate polymer prepared by contacting a
2~ dihydroxy compound with a dicarboxylic acid compound and
a carbonate precursor. The polymer is characterized in
that the mole ratio of dicarboxylic acid compound and
carbonate precursor with respect to the dihydroxy com-
pound is such that the resulting polymer has a molarratio of diester:carbonate groups from 0.02:1 to 20:1,
preferably from 0.05:1 to 15:1 and more preferably from
0.06:1 to 10:1. The optimum ratio of diester groups to
carbonate groups in the copolyestercarbonate polymer
depends on the intended application of the polymer and
should be determined by trial and error. Diester groups
originate from the reaction of the dihydroxy compounds
with the dicarboxylic acid compound, and carbonate
- groups from the reaction of the dihydroxy compound and
carbonate precursor.
36,665-F _3_
-
.
.
2 0 ~
--4--
The polymer is further characterized in that
of the tutal dicar~oxylic acid culllylJuild employed to pre-
pare the polymer, at least about 50 mole percent, pre~-
erably at least about 70 mole percent and more prefer-
ably at least about 85 mole percent is a diaryl dicar-
boxylic acid compound containing two aromatic rings
which are connected together by a positionally and
angularly well defined rigid internal linking group.
1~
The rigid internal linking group confers a
rod-like geometry to the diaryl dicarboxylic acid com-
pound. Exemplary of such rigid internal linking groups
are a covalent bond, a cycloaliphatic or heterocyclic
ring (wherein preferably the aryl groups o~ the dicar-
~ boxylic acid are associated with the same atom center of
the. ring), -C=C-, -C 3 C- , -COO- ~ ~NHCO-, -NHCOO-, -C_N-,
--C=C-C--,
ll Fl il
-ISI- , -S- , -C-
o
36,665-F _4_
.
:
: ' " ' ~ ,
.. ~ ... . .
20~4~16
--5--
and -N=C-N-. The preferred rigid internal linking group
for the copolyestercarbonate polymers of the present
ln~-erl~io~ is a co-~alent bond.
The diaryl dicarboxylic acid compound is a
dicarboxylic acid, a dicarboxylic chloride or mixtures
thereof. Each aryl ring is substituted by at least one
carboxylic acid or carboxylic acid chloride group. In
addition, the aryl aromatic rings are optionally and
independently substituted with from 1 to 4 substituents
exemplary of which when not hydrogen are halogen, C1_
alkyl groups~ oxy-C1-6 alkyl groups, oxyaryl, phenyl,
benzyl, or mi~tures thereof. Preferred substituents for
the present invention when not hydrogen are chlorine,
bromine, C1_6 alkyl groups, especially methyl, though it
- is most preferred when none of these substituents are
present on the aryl ring.
Exemplary of suitable diaryl dicarboxylic acid
compounds for use in the present invention include
4,4'-biphenyldicarboxylic acid, 3,4'-biphenyldicarbox-
ylic acid, 4,4'-biphenyldicarboxylic acid chloride,
3,4'-biphenyldicarboxylic acid chloride and mixtures
thereof. Especially preferred are the 4,4'-dicarboxylic
acid and acid chloride isomers. The remaining mole
fraction of dicarboxylic acid compound required, if any,
for preparing the polymer can be composed of one or more
suitable dicarboxylic acids or dicarboxylic acid
chlorides, different than the diaryl dicarboxylic acid
compound described hereinabove, and familiar to one
skilled in the art of preparing polyester polymers.
Suitable dicarboxylic acid compounds can be
aliphatic, alicyclic, heterocyclic, aromatic, cr
36,665-F _5_
` 20~4~1~
--6--
mixtures thereof. Hydroxy acids may also be used in
small quantities in the preparation of the polymers of
thi3 il-lv~r~ti~r-l.
Suitable aliphatic dibasic acids are those
derived from straight-chain paraffin hydrocarbons such
as oxalic, malonic, dimethyl malonic, succinic, glu-
taric, adipic, pimelic, subaric, azelaic, and sebacic
acid. Also included are the halogen-substituted ali-
phatic dibasic acids. Aliphatic carboxylic acids con-
taining heteroatoms and their aliphatic chain, such as
thiodiglycollic or dlglycollic acid may also be ~sed.
Also useful are such unsaturated acids as maleic or
fumaric.
~ Suitable alicyclic dicarboxylic acids include
trans-1,4-cyclohexanedicarboxylic acid, cis-1,4-cyclo-
hexanedicarboxylic acid, and 1,3 cyclohexanedicarboxylic
acids; and alkyl-, alkoxy-, or halogen-substituted
derivatives o~ the above said alicyclic dicarboxylic
acids.
,:
Aromatic dicarboxylic acids suitable ~or use in
the making o~ polymers of the present inventlon include
terephthalic acid, 4,4'-triphenyldicarboxylic acid,
2,6-naphthalenedicarboxylic acid, biphenylether-4,4'-
` -dicarboxylic acid, diphenoxyethane-4,4'-dicarboxylic
acid, diphenoxybutane-4j4'-dicarboxylic acid, biphenyl-
ethane-4,4'-dicarboxylic acid, isophthalic acid, biphe-
nylether-3,3'-dicarboxylic acid, diphenoxyethane-3.3'-
-dicarboxylic acid, biphenylethane-3,3'-dicarboxylic
acid, naphthalene-1,6-dicarboxylic acid and 1,5-
-anthraquinonedicarboxylic acid; and alkyl-, alkoxy-, or
halogen-substituted derivatives of the above said aro-
36,665-F -6-
:
. ~
.: , : ~.
: , ' :
2~444~
--7--
matic dicarboxylic acids such as chloro terephthalic
acid, dichloro terephthalic acid, bromo terephthalic
acid~ mathyl terepfltnalic acid, dimethyl t~-rapllt~-lalie
acid, ethyl terephthalic acid, methoxy terephthalic acid
and ethoxy terephthalic acid.
Examples of hydroxy acids are hydroxy glutaric
acid, mandelic acid, the various isomers of hydroxy ben-
zoic acid and hydroxy biphenyl carboxylic acid.
The mono- and diacid chloride derivatives of
the above-mentioned dicarboxylic acids are also suitable
for preparing the polymers of the present invention.
Further examples of suitable dicarboxylic acid compo~lnd~
or hydroxy carboxylic acid compounds are given in U.S.
~ Patents 3,637,595; 3,975,487; and 4?118,372. When the
diaryl dicarboxylic acids are used in combination with
other suitable dicarboxylic acids, preferred are the
above-mentioned aromatic carboxylic acids.
The dihydroxy compound used in preparing the
copolyestercarbonate polymer of the invention can be an
aliphatic, alicyclic, heterocyclic or aromatic dihydroxy
compound which has two hydroxyl groups capable of react~
ing with the carboxylic acid or acid chloride and car-
bonate precursor to give the polymer of the present
invention. Combinations of one or more of these dihy-
droxyl compounds can be used to make the copolyester-
carbonate polymers.
It is preferred for this present inventionthat the dihydroxy compound employed comprises at least
about 50 mole percent, preferably at least about 70 mole
percent and most preferably from 90 to 10Q mole percent
36,665-F -7-
,
` ` 2 ~ 1 6
--8--
of a dihydroxy diaryl compound. The dihydroxy diaryl
compound is represented by the formula
H~ (A~m ~ - B-H
(X)y (X)y
wherein A is selected from the group consisting of a
divalent hydroc~rbon containing from one to about 15
car~on a~oms, a halogen-substituted divalent hydrocarbon
. radical containing from one to about 15 carbon atoms and
; 15 divalent groups such as -S-, -S-s-? --? -C=C-~ -C=N-,
O O
8 11 11
~ c , s , s
.. o
:` 20
.
a covalent bond or any other rigid linking group as
defined hereinabove; B independently is oxygen, sulfur
or a divalent radical such as -ORO-, wherein R is a C1_6
hydrocarbon; X, when not hydrogen, is independently
. selected from the group consisting of halogen, a mono-
valent hydrocarbon radical such as an alkyl group or
from 1 to 6 carbon atoms, an aryl group of from 6 to 18
carbon atoms, an aralkyl group of from 7 to 14 carbon
3 atoms, an oxyalkyl group of from 1 to 6 carbon atoms,
and an oxyaryl group of from 6 to 18 carbon atoms; m is
O or l and y is a whole number integer of from O to 4.
Typical of some of the dihydroxy diaryl com-
:~ pounds that are advantageously employed are bisphenols
36,665-F -8-
~`
, , ; .~, ,
.
~., ,, . ;
- ~ . ' : ' . .
,
2 0 ~
g
such as bis(4-hydroxyphenyl)methane, 1,1-bis(4-hydroxy-
phenyl)-l-phenylethane, 2,2 bis(4-hydroxyphenyl)propane
(dlso ~o~ onl~ k~low~l as bisphenol A), 2,2-uis(4-llydruxy-
-3-methylphenyl)propane, 4,4-bis(4-hydroxyphenyl)hep-
tane, 2,2-bis(4-hydroxy-3,5-dichlorophenyl)propane, 2,2-
-bis(4-hydroxy-3,5-dibromophenyl)propane;
dihydroxyphenyl ethers such as bis(4-hydroxy-
phenyl)ether, bis(3,5-dichloro-4-hydroxyphenyl)ether;
dihydroxy biphenyls such as 4,4'-dihydroxybiphenyl,
3,3'-dichloro-4,4'-dihydroxy biphenyl, 2,2',6,6'-
-tetrabromo-3,3',5,5'-tetramethyl-4,4'-dihydroxybiphe-
nyl; dihydroxy aryl sulfones such as bis(4-
-hydroxyphenyl)sulfone, bis(3,5-dimethyl-4-
-hydroxyphenyl)sulfone; and dihydroxy biphenyl sulfides
and sulfoxides such as bis(4-hydroxyphenyl)sulfide and
~ bis~4-hydroxyphenyl)sulfoxide; or mixtures thereof.
The preferred dihydroxy diaryl compounds are
the bisphenol compounds, especially the 4,4'-bisphenols
optionally substituted by a halogen or a C1_6 hydrocar-
bon radical and biphenyl compounds. Exemplary of such
diaryl dihydroxy compounds are 2,2-bis(4-hydroxyphe-
- nyl)propane, l,l-bis(4-hydroxyphenyl)-1-phenylethane,
2,2',6,6'-tetrabromo-3,3',5,5'-tetramethyl-4,4'-dlhy-
droxybiphenyl, 2,2-bis~4-hydroxy-3,5-dichlorophenyl)-
propane, 2,2-bis(4-hydroxy-3,5-dibromophenyl)propane,
4,4'-dihydroxybiphenyl and bis(4-hydroxyphenyl)sulfide
also referred to as 4,4'-thiodiphenol.
The remaining portion of dihydroxy compound
required in the reaction of preparing the copolyester-
carbonate polymer of the present invention may be com-
posed of a dihydroxy diaryl compound different from the
preferred compounds described hereinabove or it may
36,665-F -9-
,
20~4416
-10-
consi~t of one or more aliphatic, alicyclic or aromatic
diols commonly used in the preparation of polyester or
polycarbonate poLyoi3.
Suitable diols are aliphatic diols including
straight-chain and branched aliphatic diols sueh as eth-
ylene glycol, propylene glycol, butylene glycol, and
neopentyl glycol; alicyclic diols such as trans-1,4-cy
clohexanediol, cis-1,4-cyclohexanediol, trans~1,4-cyclo-
hexanedimethanol, cis-1,4-cyclohexanedimethanol, trans-
-1~3-cyclohexanedimethanol; and alkyl-, alkoxy-, or
halogen-substituted derivatives of the above said ali-
cyclic diols such as trans-1,4-(1-methyl)cyclohexanediol
and trans-1,4-(1-chloro)cyclohexanediûl.
- Suitable aromatic diols include hydroquinone,
resorcinol, 2,6-naphthalenediol, 1,6-naphthalenediol~ A
variety of additional aromatic diols are also available
and are disclosed in U.S. Patents 2,999,835; 3,028,365
and 3,153,008.
It is also possible to use, in addition to
the aromatio diols, aromatic mercaptophenols, aromatic
hydroxy amines and aromatic diamines. Exemplary of ~uch
compounds are benzene-1,4-dithiol, benzene-1,3-dithiol,
2,6-naphthalenedithiol 9 2,7-naphthalenedithiol, 4-mer-
captophenol, 3-mercaptophenol, 6-mercaptonaphthol,
7-mercaptonaphthol, 4-aminophenol, n-methyl-4-
-aminophenol, 1,4-phenyldiamine, 3-aminophenol,
3-methyl-4-aminophenol, 2-chloro-4-aminophenol, 4-amino-
-1-naphthol, 4-amino-4'-hydroxybiphenyl and mixtures
thereof. Additional aromatic hydroxy amines and
aromatic diamines are disclosed in U.S. Patent
4,726,998.
36,665-F -10-
- , ,
.
' ~ ' ~ ' ' '. , , ;'` ' ' '
204~
1 1 .
The carbonate precursor may be either a car-
vonyi naiide, a diaryl car-bonate or a bishaloforma1e.
The carbonyl halides include carbonyl bromide, carbonyl
chloride and mixtures thereof. The bishaloformates
suitable for use include the bishaloformates of dihydric
phenols such as bischloroformates of 2,2-bis(4-hydroxy-
; phenyl)propane, 2,2-bis(4-hydroxy-3,5-dichlorophenyl)-
propane, hydroquinone or bishaloformates of glycols such
as ethylene glycol. While all of the above described
carbonate precursors are useful, carbonyl chloride, also
known as phosgene, is preferred.
The copolyestercarbonate polymers of the pres-
ent invention may be obtained by various known processes
~ using solution or interfacial polymerization techniques
such as described, for example, in the EncyclopediaofPoly-
merScienceandTechnology, 1969, Vol. lO, p. 726 and the
publication "Polyester", Pergamon Press (1965) p. 448
etseq.. Exemplary of methods by which copolyestercarbon-
ates may be produced are those methods described in U.S.
Patents 3,169,121; 4,105,633; 4,156,069; 4,194,038;
4,238,596; 4,238,597; 4,252,93g; 4,255,556; 4,260,731;
4,287,787; 4,330,662; 4,355,150: ~,360,656; 4,369,303;
4,374,973; and 4,388~455.
~'
The polymers of the invention may9 in addition
to being used for molding purposes, be employed as the
base for preparing thermoplastic molding compositions by
being compounded with conventional molding aids such as,
for example, antioxidants, antistatic agents, inert
fillers such as glass, talc, mica, clay, hydrolytic
stabilizers such as the epoxides as disclosed in U.S.
Patents 3,489,716; 3,839,247; and 4,138,379; color
36,665-F
' `
2~4~41~
-12-
stabilizers such as organophosphites, thermal
stabilizers such as phosphites; flame retardants and
mold release ageht3~ The polyulers Ol the invention show
reduced sensitivity to UV radiation over those of the
prior art but if required UV radiation absorbers such as
benzophenone~ and benzotriazoles can be incorporated
into the thermoplastic molding composition.
The copolyestercarbonate polymers of the
present invention can also be employed with other ther-
moplastic polymers to prepare thermoplastic polymer
blends. Suitable thermoplastic polymers for this pur-
pose include thermoplastic polyurethanes, polyesters,
polycarbonates, polyalkylenes such as polypropylene and
polyethylene, copolymers thereof and mixtures thereof.
-
When the copolyestercarbonate polymers of thepresent invention are used to prepare thermoplastic
polymer blends, advantageously the blend comprises at
least 0.5 weight percent, preferably at least 5 weight
percent, and more preferably frum 10 to 99 weight
percent of said copolyestercarbonate polymer by total
weight thermoplastic polymer and copolyestercarbonate
polymer present.
The following examples are given to further
illustrate the invention as construed by the inventors.
However, these examples are not to be interpreted as
limiting the scope of the invention in any way. Unless
stated otherwise, all parts and percentages are given by
weight.
36,665 F -12-
. .~
.
20~441~
-13-
Where reported, the following tests are carried
out to characterize the polymers of the invention using
the ~est pruee~ures ~s in~ic~ted. -Inherent visc03ity
(IV) is determined in methylene chloride at 25C and
using a concentration of 0.5 gtdL. The glass transition
temperature (Tg) is determined by differential scanning
calorimetry at a heating rate of 20C/minute. The
extrapolated onset value is reported.
The following tests are performed using
compression molded specimens (0.125 inch (3.2 mm)
thickness) prepared at 80C to 120C above Tg. Notched
Izod impact resistance is determined according to ASTM
D-256, wherein a 0.01-inch (0.254 mm) notch radius is
employed. Tensile properties including tensile modulus
- (TM), tensile strength at yield ~TY), elongation at
yield (EY), and post-yield stress drop (PYSD) are
measured according to ASTM D-638. The determination of
PYSD is described by Bubeck et al. in PolymerEngineering
andScience, 24, 1142 (1984). Specific gravity (SG) is
measured by ASTM D-792. Resistance to hydrolysis is
determined by measuring the weight loss resulting from
immersion in 10N NaOH solution. The critical strain for
crazing is determined after a 30-minute exposure period
according to the procedure of Wyzgoski, GeneralMotors
Research Publication (~MR-3779 ( 1981 ) .
The sensitivity of the polymer to ultraviolet
(UV) radiation is determined by measuring the change in
yellowness index (YI) of compression moldings after
exposure to a Hanovia 450W medium pressure mercury arc
lamp or a Q~V testing chamber. YI is determined
according to ASTM D-1925.
36,665-F -13-
: .
. .
: -
;
204~41~
-14-
~xampie 1
This example describes the synthesis of a bis-
phenol A/4,4'-biphenyldicarboxylate copolyestercarbonate
having a diester~carbonate molar ratio of 1.0:1.
A two-liter (L) flask equipped with a thermom-
eter, nitrogen and phosgene inlets,-and a paddle stirrer
0 connected to a Cole Parmer Servodyne is charged with
99.44 g (0.436 mole) of bisphenol A, 89.7 g (1.134 mole)
of pyridine, and 1.18 L of methylene chloride. The
resulting clear solution is stirred at 300 rpm, cooled
to about 16C, and then 60.79 g (0.218 mole) of 4,4'--bi-
_ phenyldicarboxylic acid chloride is added to the flask
over a period of about 4 minutes, resulting in an exo-
therm to about 20C. The clear solution is ~tirred for
10 minutes, 1.64 g (0.011 mole) of p-tertiary-butylphe~
nol is added, and then 22.5 g (0.23 mole) of phosgene is
added to the flask over 15 minutes, while maintaining
the contents of the flask at 14C to 29C. ~ethanol (3
mL) and HCl (3N, 160 mL) are added, the contents of the
flask are stirred an additional 30 minutes, and then
poured into a 2-L separatory-funnel. The methylene
chloride phase containing the copolyestercarbonate is
separated, washed again using 215 mL of 0.5N HC1, and
then passed through a column (300~mL bed volume) of
macroporous cation-exchange resin. The polymer is then
isolated by adding one volume of the methylene chloride
solution to a mixture of 2.4 volumes of hexane and 1.2
volumes of acetone in an explosion-resistant blender,
and then collecting the resulting precipitated product
by filtration.
36,665-F _14_
~' '
2~416
-15-
The precipitated product is then dried in a
vacuum oven at about 120C for 48 hours. The resulting
product weighs 136.5 g, has an IV of 0.72 dL/g, and
exhibits a diester:carbonate ratio of t.0:1 as deter-
mined by nuclear magnetic resonance and infrared spec-
troscopy. This material is designated Sample No. 1.
For purposes of comparison, the general proce-
dure of` this example is employed to prepare a bisphenolA/terephthalate copolyestercarbonate polymer having a
diester~carbonate ratio of 1.0:1. For this comparison
material, designated Sample No. G1, terephthaloyl chlo-
ride is employed instead of 4,4'-biphenyldicarboxylic
acid chloride.
-
The properties determined for Samples No. 1and C1 are set forth in Table I. As can be seen ~rom
these results, the compositions according to the present
invention exhibit improvements in Tg, Notched Izod, ten-
sile properties, hydrolytic stability and solvent
resistance when compared to comparative compositions.
;:
,
'
36,665-F -15-
- . ': ~ . .
.' ' '
- 2 ~ 1 6
-16-
TABLE I
Sample No. 1 C1*
IV, dL/g 0.72 0.68
Tg, C ~ 204 186
N. I~od, ft-lb/in (J/m) 6~7 5.0
(357.8) (267.0)
TY, psi (MPa~ 9,219 9,042
(63.56) (62.34)
EY, % 10.0 8.6
PYSD, (%) 4.8 8.1
TM, 105 psl MPa 3.3 3.3
(2,275.27) (2,275.27)
Weight Loss in 10N NaOH, %, 500 hr 3.4 13.7
Critical Strain, Isopropanol, % 3.0 Z.O
SG 1.20 1.20
*Not an example of the invention
Example 2
To further describe the scope of this inven-
tion, additional bisphenol A/4,4'-biphenyldicarboxylate
copolyestercarbonate polymers having diester:carbonate
molar ratios from 0.06:1 to 10:1 are prepared according
to the general procedure of Example 1. These results
are.recorded in Table II.
The molecular weight of the resulting polymer
is observed through the inherent viscosities (IV).
Higher inherent viscosity values indicate polymer with
greater molecular weight. Examples 2 to 11 are prepared
so as to have the inherent viscosities as reported in
Table II.
36,665-F -16-
,
: ,
.: . . .
204~416
-17
In Samples 4 and 5, and Examples 6 and 7, the
difl~r~ t inherar,t vL3co~i~ies are obtained by using
different quantities of p-tertiary-butylphenol. Smaller
quantities provide for higher molecular weights as
evidenced by greater inherent viscosities.
,
36,665-F -17-
2~D~4416
--18--
V~ ~ N N N N N N N N
al 3 3 ~ ~ S 3.~, 5 3 ~ a a
~, 3 ~ .,,3 ~ Z
N N N N N N N 01
â N Lf~ ~) O
O ~ t`~) N -O co (~) O a a
N ~ r-
L~ O U~ D O O Lr~
a
~7~D 5 ~D O ~ N N C)~ U~ ~ ~ 3 =s- ~o
N O ~ ~ O U~ ~ a a
D~ CL. a~ .o .o ~o~ ~ ~ ~~ ~ ;z z
~ 0- ~ ^ ~ ` N --- ^ J
E~ ~ EItl r--N Ln:a- l~, ~ N CJ~
^ a a
~ a:~'D U~ 3 3 ~ N ~--
Z
` ~ ~ Ln cr~ u~ N t-- o ~ ~-~
o N
E~ ~ ~ ~ ~ N N N Z
~d
b~ Ln L~ N ~ L~ /:~ ~o
::~ ` L~ Ln Ln ~D ~O 00 Ln ~O ~ Ln E
~:; o o o o o o o a~ ~
E
9 ~ ~ ~ ~ o o o o o o o
~ ~ ~ u~ Ln Ln o o o n
~1 ' ~ ~ Ln o ~ ~
a~ q) o
E3 ol ~ ~ ~r Ln ~o ~ co ~ o ~ v~ I
a Q
~ Z
36, 665-F -18-
'
2044~1~
_1 9
Example 3
To furtner describe ths utility of this inven-
tion, bisphenol A/4,4'-biphenyldicarboxylate (BP) co-
polyestercarbonate polymers are exposed to UV radiation,
as shown in Table III (Sample Nos. 1, 4, 12). For
comparison, bisphenol A/terephthalate (T) copoly-
estercarbonate polymers are also exposed (Sample Nos.
C1-C3). Sample Nos. 12, C2 and C3 are prepared accord-
ing to the general procedure of Example 1. As evidenced
by the resulting change in YI ~YI), the compositions
of the present invention exhibit a significant reduction
in yellowing following UV exposure.
36,665-F -1g-
.
', ' ' ':
~ .
.
: ' . , - .
l g
--20--
~I ~ t-- ~ ~D ~ ~
-
a)'~ o o
a~ o.~ o
X,E N ~1
a)
~ o ~ *
~ U~
H
:Q
a~
C~ O O ~ ~ O O
O
O O O
o43
O
U~
~5
a~
a~ ~
E ol ~ ~ 5 ~ N ~ ~d o
~ Z
u~ o
~ . 2 ~
*
36, 665-F -20-
2 0 ~
-21-
Example 4
To fur~her describe the scope of this invan-
tion, additional copolyestercarbonate polymers are pre~
pared according to the general procedure of Example 1.
Diols utilized for the compositions of this example
include bisphenol A (BA); 2,2-bis(4-hydroxy-3,5-dichlo-
rophenyl)propane (TCBA); 2,2-bis~4-hydroxy-3,5-dibromo-
phenyl)propane (TBBA); 4~4'-dihydroxybiphenyl (DHB);
4,4'-thiodiphenol (TDP); 1,1-bis(4-hydroxyphenyl)-1-
tO -phenylethane (also known as bisphenol AP, BAP); and
2,2',6,6'-tetrabromo-3,3',5,5'-tetramethyl-4,4'-dihy-
droxybiphenyl (TTDHB). Esters utilized include 4,4'-
-biphenyldicarboxylate (BP), terephthalate (T), and
isophthalate (I). The results for these compositions
are set forth in Table IV (Sample Nos. 13 22).
.
36,665-F -21-
,
~.
.
-` 2~4~
--22--
E~ t~ C ~ O 1~ N
_ ~ ~ ~ ~ ~ ~ ~ ~
,_
=r ~ ~ ~r ~ In ~~ o s
~:3 O O O O O O O O O O
~) ~ ~ ~ ~ ~ ~ O ~ O O
~. ~) t~) ~ ~) ~7 ~ LS~ \ O
:a O O O O O O O O ~ U~
H U~
:~ ¢
~ ~ ma~ P~ In m m m m m m m m
::
3 ~3 ô d o m o ~ ô ~ ô U~
ol ¢ ¢ m ~ tn m N Q r~
a ¢~ m-- m~ m ~ ~o~ O
:'
~ ~ u~ o .- ~ o
E~ Z¦ ~ ~ ~ ~ ~ ~~ ~I N N E~
U~ :
36, 665-F -22-
:
:: ~ - . . . . .
204~6
-23-
Example 5
To further describe the scope o~ this inven-
tion, this example describe~ the preparation of a ther-
moplastic polymer blend of bisphenol A polycarbonate
resin and a copolyestercarbonate polymer resin of the
present invention.
Bisphenol A/4~4'-biphenyldicarboxylate copoly-
estercarbonate polymer (87.6 g~ prepared according to
the general procedure of Example 1 and having I~ - 0.56
dL/g and a diester:carbonate ratio of 1.0:1) is mixed
with a bisphenol A polycarbonate polymer (32.4 g, IV =
0.53 dL/g) in one liter of methylene chloride. The
blend is then isolated by precipitation using hex-
_ ane/acetone and an explosion-resistant blender. The
precipitated product is dried in a vacuum oven and then
compression molded. The following results are obtained
for the molded blend composition: notched izod = 7.7
ft-lb/in (411.2 J/m); TY - 9,261 psi (63.85 MPa); EY -
8.8 psrcent; PYSD - 9.0 percent; and TM = 300,000 psi
(2,068.43 MPa).
Example 6
An additional advantage of the composition of
this invention is resistance to crystallization during
the solvent-casting of films. The preparation of films
of bisphenol A polycarbonates in a thickness of at least
3 0.005 ~0.127 mm) inch by solvent-casting from a
methylene chloride solution results in crystalline
films, as evidenced by opacity and a melting transition
(differential scanning calorimetry analysis). Non-
-crystalline films of comparative bisphenol
A/terephthalate copolyestercarbonate polymers can be
3h,665-F -23-
2 ~ 1 6
-~4-
prepared when the diester:carbonate ratio is in the
range of 0.05 to 1.5. In contrast, the corre~ponding
die3tee~:c~rbonate r~nge for non-cey~taiiirle fil[n prepa-
ration is from 0.05 to 10.0 for the bisphenol
A/biphenyldicarboxylate copolyestercarbonate polymers of
this invention.
;~
36,665-F -24-
:
"
; .
~ .
