Note: Descriptions are shown in the official language in which they were submitted.
~CV 04220
-- 1 --
T~lERMOPLASTIC POl~YETHERIMIDE :E:SI'ER ELASTOMERS
The present invention relates to n~uel thermD-
plastic elastomers having excellent stress-strain
properties, low tensile ~et, high melting temperatures
and/or excellent rtrength/toughness characteristics as
well as superior flexibility whi~h are especially
~uitable for molding and extrusiDn applications. Spe~
~ifically, novel polyetherimide esters having the
above-mentioned properties have been prepared fr~m one
or more diols, one or more dicarboxyli~ acids and,
mDst importantly, one or more high ~olecular weight
polyoxyalkylene diimide diacids.
Polyether ester imides are well known having been
described in numerous publications and patents includ-
ing for ex~mple, ~onnre et al, "Synthesis and Study of
Various Reactive Oligmers and of Poly(ester-imide-
-ether) 6, ~uropean Pol ~ Vol. 16, pp.
909-916, October 12, 1979; and in Xlui~er et al, U.S.
Patent No. 3,274,1S9 and Wolfe ~r~, U.S. Patent Nos.
4,371,692 and 4,371,693, respecti~ely. However, none
of ~he prior art references tea~h or suggest the novel
poly(etherimide ester~ compositions ~f the present
invention. Fur~hermore, none of these references pro-
vide polyetherimide ester resins havin~ the excellent
physical properties, including hi~h melting point and
~xcellent flexibili~y, as mentioned above, c~mbined
with the rapid crystallizatiDn rate and excellent
moldability characteristics of the novel polyether-
imide esters of the present inventiDn.
Specifically t applicants ha~e now found a novel
3D class of poly(e~herimide e~ter~ elas~omers which are
particularly ~uited for molding and/or extrusion
applications and which are ~haracterized a~ ~aving one
or more of the following enhanced properti~s: ~ress-
~train resistance, toughness/~trength, and tPnsile set
~S~6~
8CV O~Z20
-- 2 --
at low flexural modulus combined with rapid
crystallization rates and excellent moldability
as demonstrated by short cycle times and good mold
releasability, respectively~
I~ is an object of the present
invention to pro~ide copolyetherimide esters
which have improved thermal and oxidative
stability without a loss in other physical
properties.
It is also an object of the present
invention to prcvide copolyetherimide e~ters
having improved solvent resistance without
sacrificing the superior flexibility of the
polyetherimide ester.
Finally, it is an object of the
present invention to provide copolyetherimide
esters having a high melting point and improved
crystallization rates combined with excellent
flexibility.
The novel poly(etherimide esters) of the
present invention may be either random or block and
are prepared by conventional processes from a) one
or more diols, b) one or more dicarboxylic acids
and c) one or more polyoxyalkylene diimide diacids.
Preferred poly(etherimide esters) compositions
encompassed by the present invention may be
prepared from a) one or more C2 - C15
aliphatic and/or cycloaliphatic diols, b) one or
more C~ - C16 aliphatic, cycloaliphatic and/or
aromatic dicarboxylic acids or ester derivatives
thereof and c) one or more polyoxyalkylene diimide
diacids. The amount of polyoxyalkylene diimide
diacid employed is generally dependent upon the
~25~6~
8CV 04220
- 3
desire~ properties of the resultant polyetherimide
ester. In general, the wei~ht ratio of
polyoxyalkylene diimide diacid (c) to dicaxboxylic
acid (b) is from about 0.25 to 2.0, preferably ~rom
about 0.4 to about 1.4. Finally, the compositions may
contain and preferably do contain additional
stabilizers for even greater stabilization and low
temperature impact strength.
It has now also been discovered
that modified copolyetherimide esters having
improved thermal and oxidative stability, solvent
resistance and crystallization and flexibility
characteristics can be prepared by conventional
processes ~rom a) one or more diols, b) one or more
dicarboxylic acids and c) a combination of i) one or
more polyoxylakylene diimide diacids and ii) one
or more dimer acids, wherein the dimer acid is
present in an amount of from about 5 to about 40
weight percent based on the combined weight of ( i )
and ~ii). Pre~erred modified copolyetherimides ester
compositions encompassed by the present invention
may be prepared ~rom a) one or more C2 - Cl5
aliphatic and/or cycloaliphatic diols, b) one or
more C4 - Cl6 aliphatic, cycloaliphatic and/or
aromatic dicarboxylic acids or ester derivatives
thereof and c) a combination of i) a polyoxyalkenylene
diimide diacid and ii) a dimer acid wherein the
dimer acid is present in an amvunt of from about 15
to abvut 30 weight percent based on the combined
weight of (i) and (ii). The speci~ic amounts o~ i)
polyoxyalkylene diimide diacid and ii) dimer acid
employed in the practice of the present invention is
generally dependent upon the desired properties of
8CV 0~220
-- 4 --
the resultant modified polyetherimide ester. In
general, the weight ratio of (c) the combination
of i) polyoxyalkylene diimide diacid and ii) dimer
acid to dicarboxylic acid (b) is from about 0.25
to 2.0, preferably from about 0.4 to about 114.
Finally, the compositions may contain and
preferably do contain additional stabilizers for
even greater stabilization and low temperature
impact strength.
Suitable diols (a) for use in preparing the
compositions of the present invention include
saturated and unsaturated aliphatic and cycloaliphatic
dihydroxy compounds as well as aromatic dihydroxy
compounds as well as aromatic dihydroxy compounds.
These diols are preferably of a low molecular weight,
ie. having a molecular weight of about 250 or less~
When used herein, the term "diols" and "low molecular
weight diols" should be construed to include
equivalent ester forming derivatives thereof,
provided, however, that the molecular weight
requirement pertains to the diol only and not to its
derivatives. Exemplary of ester forming derivatives
there may ~e given the acetates of the diols as well
as for example ethylene oxide or ethylene carbonate
for ethylene glycol.
Preferred saturated and unsatruated
alphatic and cycloaliphatic diols are those
having from about 2 to 15 carbon atoms.
Exemplary of these diols there may be given
ethyleneglycol, propanediol, butanediol,
pentanediol, 2-methyl propanediol, 2,2~dimethyl
propanediol, hexanediol, decanediol, 1,2-, 1,3-
and 1,4- dihydroxy cyclohexane; 1,2-, 1,3-
~5~
8CV ~4220-- 5 --
and l,~cyclohexane di~ethanol; butene diol;
hexene diol, etc. Especially preferred
are 1,4-butanediol and mixtures thereof
with hexanediol or butenediol, most
preferably 1,4-butanediol.
Aromatic diols suitable for use in the
practice of the present invention are generally those
having from 6 to about 15 carbon atoms. Included
among the aromatic dihydroxy compounds are
resorcinol; hydroquinone: 1,5-dihydroxy
napthalene; 4,4'-dihydroxy diphenyl;
bis~p-hydroxy phenyl)methane and bis~p-hydroxy
phenyl) 2,2-propane.
Especially preferred diols are the
saturated aliphatic diols, mixtures thereof and
mixtures of a saturated diol(s) with an unsaturated
diol( 5 ), wherein each diol contains from 2 to
about 8 carbon atoms. W~lere more than one diol is
employed, it is preferred that at least about 60
mole ~, based on the total diol content, be the
same diol, most preferably at least 80 mole ~. ~s
mentioned above, the preferred compositions are those
in which 1,4- butanediol is present in a predominant
amount, most preferably when 1,4-butanediol is the
only diol.
Dicarboxylic acids (b) which are
suitable for use in the practice of the
present invention are aliphatic, clycoaliphatic,
and/or aromatic dicarboxylic acids. These
acids are preferably of a low molecular
8CV 0~220
-- 6 --
weight, i.e., having a molecular weight vf less than
~b~ut 3~0; however, higher molecular weight dicarb~xyl-
ic acids, especially dimer acids, may al~o be used.
~he erm ~aicarboxylic acids~ as used herein, includes
equivalents ~f dicarboxylic a~ids having two func-
tio~al çarboxyl groups which perform substantially
like dicar~oxylic acids in rea~tion with glycols and
diols in forming polyester p~lymers. These equivalents
include esters and ester-forming derivatives, such as
lQ acid halides and anhydrides. The molecular weight
preference, mentioned a~ove, pertains to the acid and
nDt to its equivalent ester or ester-forming deriva-
tive. Thu~, an ester ~f a dicarboxylic acid having a
molecular weight greater than 300 or an acid equiva-
lent of a dicarboxylic acid having a molecular weightgreater than 300 are included provided the acid has a
molecular weight below abDut 300. Additionally, the
dicarboxylic acids may c~ntain any su~stitue~
group(s) or combinations which do not substantially
interfere wikh the p~lymer formation and use of the
polymer of this invention.
Aliphatic dicarb~xylic acids, as the term is used
herein, refers to carboxylic acids having two carboxyl
groups each of which is attached to a satura~ed carbon
atom. If the carbon atom t~ which the carboxyl group
is attached is ~aturated and is in a ring, the acid is
cycloaliphatic.
Aromatic dicarboxylic a~ids, as the term is used
herein, are dicarboxylic acids having two carboxyl
groups each ~f which i~ attached to a carbo~ atom in
an isolated or fused benzene ring system. It is no~
necessary that both functional carboxyl groups be
attached to the same aromatic riny and where ~ore than
one ring ic pre~ent, they oan be joined by aliphatic
or aromatic dival~nt radical6 or divalent radical~
such as ~O- or -SO2-.
6~
8CV 04220
7 _
Representative aliphatic an~ ~ycloaliphatlc acids
which can be used for this invention are ~ebacic acid,
1,2-cyclohexane dicarboxylic acid, 1,3-cyclohexane
dicarboxylic aci~, 1,4-cyclohexane clicarb~xyli~ acid,
5 adipic acid, glutaric acid, ~uccinit acid, Dxalic
acid, azelaic acid, diethylmalDnic acid, allylmalonic
acid, dimer acid, 4-~yclohexene-1,2-- dicarb~xylic
acid, 2-ethyl~uberic acid, tetramethylsuccinic acid,
cyclopentanedicarboxylic acid, decahydro-1,5-naph-
thalene dicarboxylic a~idt 4,4' bicyclohexyl dicar-
boxylic acid, decahydro-2,6-naphthalene dicarb~xylic
~cid, 4,4 methylenebis(~yclohexane carboxylic acid),
3,4-furan dicarboxylic acid, and l,l-cyclobutane dicar-
boxylic acid. Preferred aliphatic acids are cyclo-
hexane dicarboxylic acids,~ebacic acid, dimer acid,glutaric acid, azelaic acid and adipic acid.
Representative ~romatic ~icarboxylic acids which
can be used include terephthalic, phthalic and iso-
phthalic acids, bi-benzoic acid, su~stituted dicarboxy
compounds with two benzene nuclei such as bi~(p-car~-
oxyphenyl) methane, oxybis(benzoic acid), ethylene-
1,2- bis-(p-oxybenzoic acid~, l,5 naphthalene
dicarboxylic acid, 2,6-naphthalene dicarboxylic acid,
~,7-naphthalene dicarboxylic acid, phenanthrene
dicarboxylic acid, anthracene dicarboxylic acid,
4,4'-~ulfonyl dibenzoic acid, and halo ~nd Cl-Cl2
alkyl, alkoxy, and aryl ring substitution deri~atives
thereof. Hydroxy acids ~uch as p~ B-hydroxyethoxy~-
benzoic acid can also be used provided an aromatic
dicarboxylic acid is al~o present.
Pre~erred dicarboxylic acids for ~he preparation
~f the polyetherimide esters of the pre~ent invention
are the ~romati~ di~arboxylic ac-d~, mixtures thereof
and mixtures of ~ne sr more dicarb~xylic acid with an
aliphatic and/or cycloaliphatic di~arboxylic acid,
most prefera~ly the aromatic dicarboxylic acids.
8CV 0~220
Among the aromatic acids, those with 8--16 carbon atoms
are preferred, particularly the benzene dicarboxylic
acids, i.e., phthalic, terephthalic and isophthalic
acids and their dimethyl derivatives. Especially
preferred is dimethyl terephthalate.
Finally, where mixtures of dicarboxylic
acids are employed in the practice of the present
invention, it is preferred that at least about 60
mole %, preferably at least about 80 mole %, based
on 100 mole % of dicarboxylic acid (b) be of the same
dicarboxylic acid or ester derivative thereof. As
mentioned above, the preferred compositions are those
in which dimethylterephthalate is the predominant
dicarboxylic acid, most preferably when
dimethylterephthalate is the only dicarboxylic acid.
The third component to be used in the
practice of the present invention to produce the
modified copoyletherimide esters is a combination (c)
of i ) polyoxyalkylene diimide diacid and ii) dimer
acid wherein the amount of dimer acid present is from
about 5 to about 40 weight percent, preferably from
about 15 to about 30 weight percent, based on the
combined weight of (i) and ~ii).
Polyoxyalkylene diimide diacids (c) or (c)
(i) suitable for use herein are high molecular weight
diimide diacids wherein the average molecular weight
is greater than about 700, most preferably greater
than about 900. They may be prepared by the
imidization reaction of one or more tricarboxylic acid
compounds containing two vicinal carboxyl groups or an
anhydride group and an additional carboxyl group which
must be esterificable and preferably is nonimidizable
~2~
- 9 - 8CV042~0
with a high molecular weight polyoxylalkylene
diamine.
In general, the polyoxylalkylene
dlimide diacids useful herein may be characterized
by the following formula:
O O
R'OOC-R \ N-G-N ~ R-COOR'
\ / \/
C / C
O O
where each R is independently a trivalent
organic radical, preferably a C2 to C20
aliphatic, aromatic, or cycloali.phatic
trivalent organic radical; each R' is independently
hydrogen or a monovalent organic radical
preferably selected from the group consisting
of Cl to C6 aliphatic and cycloaliphatic
radicals and C6 to C12 aromatic radicals,
e.g. benzyl, mos-t preferably hydrogen; and
G is the radical remaining after the removal of
the terminal (or as nearly terminal as possible)
hydroxy groups of a long chain either glycol having
an average molecular weight of from about 6QQ to
Y~
~Lo2d 5iq;~ 690
~CV 04220
-- 10
about 12000, preferably from about 900 to about 4000,
and a carbon~to-oxygen ratio of from about 1.8 to
about 4.3.
Representative long chain ether glycols from
which the polyoxyalkylene diamine is prepared include
poly(ethylene ether)glycol: poly~propylene ether)~
glycol; poly(tetramethylene ether)glycol; random or
block copolymers of ethylene oxide and propylene
oxide, including propylene oxide terminated
poly(ethylene ether)glycol; and random or block
copolymers o~ tetrahydrofuran with minor a~ounts of a
second mono~er such as methyl tetrahydrofuran (used :in
proportion such that the carbon-to-oxygen mole ratio
in the glycol does not exceed about 4.3). Especially
preferred poly(alkylene ether)glycols are
poly(propylene ether) glycol and poly(ethylene
ether)glycols end capped with poly(propylene
ether)glycol and/or propylene oxide.
In general, the polyoxyalkylene dia~ines use.ful
within the scope of the ~resent invention will have an
~,
8CV 04220
~verage molecular of from abDut 600 to 12000, prefer-
ably from ab~ut 900 ts about 4000.
The tricarb~xylic romponent may be alm~st any
carb~xylic acid anhydride c~ntaining an additi~nal
carboxylic gr~up or the corresp~ndiny acid thereof
containing two imide-forming ~icinal carboxyl groups
in lieu of the anhydride gr~up. Mixtures thereof are
als~ suitable. The addi~ional carboxylic group must
be esterifiable and preferably is substantiQlly n~n-
imidizable.
Further, while trimellitic anhydride is preferredas the tricarb~xylic comp~nent, any of a number of
~ui~able tricarboxylic acid constituents will o~cur to
th~se skilled in the art in~luding 2,6,7 naphthalene
tricarb~xylic anhydride; 3,3',4 diphenyl tricarb~xylic
anhydride; 3,3',4 benzophenone tricarboxylic ~nhydr-
ide; 1,3,4 cyclopentane tricarboxylic anhydride;
2,2',3 diphenyl tricarb~xylic ~nhydride; diphenyl
~ulfone - 3,3',4 tricarboxylic anhydride, ethylene
tricarboxylic anhydride; 1,2,5 napthalene tricarb-
oxylic anhydride; 1,2,4 butane tricarb~xylic anhyd-
ride; diphenyl isopr~pylidene 3,3',4 tricarboxylic
anhydride; 3,4 dicarbvxyphenyl 3'-carboxylphenyl eth~r
anhydride; 1,3,4 cyclohexane tricarboxylic anhydride,
et~. These tricarboxylic acid materials can be
chara~terized by the following formula:
/\
III ~'OOC-R ~ / O
where R i~ a trivalent crganic radical, preferably a
C2 to C20 aliphatic, aromatic, or ~yclo~liphatic tri-
3D valent organic radical and R' is preferably hydr~gen
or a m~n~v21ent organic radical pre~era~ly ~ele~ted
from the qroup ~nsisting of Cl to C~ aliphatic and/~r
, .
8CV 0~220
- 12
cycloaliphatic r~dicals and C6 to Cl~
aromatic radicals, e.g. benzy; most preferably
hydrogen.
Briefly, these polyoxyalkylene diimide
diacids may be prepared by known imidi~ation
reactions including melt synthesis or by synthesizing
in a solvent system. Such reactions will generally
occu~ at temperatures of from 100C. to 300C.,
preferably at from about 150C. to about 250C.
while drawing off water or in a solvent system at the
reflux temperature of the solvent or azeotropic
(solvent) mixture.
Although the weight ratio of the above
ingredients is not critical, it is preferred in the
unmodified composition that the diol be present in at
least a molar equivalent amount, preferably a molar
excess, most preferably at least 150 mole ~, basecl on
the moles of dicarboxylic acid ~b) and polyoxylakylene
diimide diacid (c) combined. Such molar excess of
diol will allow for optimal yields, based on the
amount of acids, while accounting for the loss of diol
during esterification/condensation.
Furt~er, while the weight ratio of
dicarboxylic acid (b) to polyoxyalkylene diimide
diacid (c) is not critical to form the novel
polyetherimide esters of the present invention,
preferred compositions are those in which the weight
ratio of the polyoxyalkylene diimide diacid (c~ to
dicarboxylic acid (b) is from about 0.25 to about 2,
preferably from about 0.4 to about 1.4. The actual
weight ratio employed will be dependent upon the
specific polyoxyalkylene diimide diacid used and more
importantly, the desired physical and chemical
8CV 04220
- 13 -
properties of the resultant polyetherimide ester.
In general, the lower the ratio of polyoxyalkylene
diimide diester to dicarboxylic acid the
hetter the strength, crystallization aIId distortion
heat properties of the polymer. Alternatively,
the higher the ratio, the better the
flexibility, tensile set and low temperature impact
characteristics.
In its preferred embodiments, the unmodified
compositions of the present invention will comprise
the reaction product of dimethylterephthalate,
optimally with up to 40 percent mole ~ of another
dicarboxylic acid; 1,4-butanediol, optionally with up
to 40 mole % of another saturated or unsaturated
aliphatic and/or cycloaliphatic diol; and a
polyoxyalkylene diimide diacid prepared from a
polyoxyalkylene dimine of molecular weight of from
about 600 to about 120~0, preferably from about 900 to
about 4000, and trimellitic anhydride. In its
most preferred embodiments, the diol will be 100
mole ~ 1,4- butanediol and the dicarboxylic acid 100
mole % dimethylterephthalate.
Dimer acids (ii) useful in the preparation
of the modified copolyetherimide esters of the
present invention are themselves prepared by the
dimerization of unsaturated fatty acids of 18
carbons. Exemplary of fa~ty acids from which they are
prepared there may be given oleic acid, linoleic acid
and linolenic acid. The preparation and structure of
dimer acid is described in Journal of the American
Oil Chemists Society, 39, 535-545 (1962), Journal of
the American Chemcial Society 66, 84 (1944) and
United States Patent Number 2,347,562. Suitable dimer
8CV ~4220
acid may be employed in its unhydrogenat~d or
hydrogenated form and include the acid functioning
derivatives thereof.
Several grades of dimer acid are available
commercially which vary in mono~er and trimer
content. Inclusive of suitable commercial dimer acids
there may be given those available fxom Emery
Industries under the tradenames EMPOL~ 010 (a
~ "".....
hydrogenated dimer acid) and EMPOL 1014. EMPOL 1010
is reported as typically containing 97% dimer acid, 3
trimer acid and essentially no monobasic acid and
extremely low unsaturation, whereas EMPOL 1014 is
typified as containing 95~, 4~ and 1% of dimer, trimer
and monobasic acids respectively. Also available are
the dimer acids sold under the tradename HYSTRENE from
the Humko Products Division of Witco Chemical
Corporation, especially HYSTRENE 3695 which typically
contain 95% dimer acid and a weight ratio of dimer to
trimer of 36:1. Preferred grades are substantially
free of such monomer and trimer fractions, most
preferably less than 5~ by weight, and are fully
saturated, or substantially so.
~ here desirable, the dimer acid member may
be substantially freed of monomer and trimer fractions
by molecular distillation or other suitable means. In
general, the dimer acid exists in the copolyetherimide
ester as a soft or rubbery segment and accordingly
dimer acids of relatively high molecular weight
(preferably greater than about 500) are preferred 50
that the modified copolyetherimide esters are
resilient, but do not deform until relatively high
temperatures are reached.
The modified copolyetherimide esters may be
prepared having high melting temperatures, faster
8C~ 04220
- 15 -
crystalli~ation rates and greater flexlbility than
unmodified copolyetherimide esters by incorporating
therein dimer acid. Specifically, copolyetherimlde
esters having comparable levels of polyoxyalkylene
diimide diacid incorporated therein have less
flexibility/ resilience and impact propertiesl
including, for example, low temperature impact.
Alternatively, unmodified composition having
essentially the same flexibility properties,
resilience and so forth suffer from greater
susceptabili~y to oxidative and thermal degradation as
well as manifest poorer solvent resistance, as a
c~nsequence of the higher levels of polyether
component in the polymer. Thus by the practice of
applicant's inventions one is able to achieve
compositions of greater flexibility, crystalization
rate solvent resistance and thermal and oxidative
stability.
In general, the benefits of the modified
copolyetherimide esters can be achieved by
incorporating into the copolyetherimide ester from
about 5 to about 40 weight percent, preferably from
about 15 to about 30 weight percent, based on the
combined weight of dimer acid and polyoxyalkylene
diimide diacid of dimer acid.
Although the weight ratio of the above
ingredients is not critical, it is preferred that
the diol be present in at least a molar equivalent
amount, preferably a molar excess, most preferably at
least 150 mole %, based on the moles of dicarboxylic
acid (b) and the combination (c) of i) polyoxyalkylene
diimide diacid and ii) dimer acid, combined. Such
molar excess of diol will allow for optimal yields~
based on the amount of acids, while accounting for the
~ $~ 8CV 0~220
- 16 -
los~ of diol during esterification/condensation.
Further, whi 1P the amount by which the
combination(s) of (i) polyoxyalkylene diimide diacid
and ii) dimer acid incorporated into the polymer is
not critical to make the modified copolyetherimide
esters of the present invention, it is preferred that
the combination (c) be present in weight ratio to
dicarboxylic acid (b) of from about 0.25 to about 2,
preferably from about 0.4 to 1.4. The actual weight
ratio employed will be dependent upon the amount of
dimer acid used, the specific polyo~yalkylene diimide
diacid used and more importantly, the desired
physical and chemical properties of the resultant
polyetherimide ester. In general, the lo~er the
ratio of the combination (c) of (i) polyoxyalkene
diimide diaced (ii) and dimer acid to dicarboxylic
acid the better the strength, crystallization
and heat distortion properties of the polymer.
Alternatively, the higher the ratio, the better
the flexibility, tensile set and low temperature
impact characteristics.
In its preferred embodiments, the modified
copolyetherimide ester compositions of the present
invention will comprise the reaction product of
dimethylterephthalate, optimally with up to 40 mole
of another dicarboxylic acid; 1,4-butanediol,
optionally with up to 40 mole % of another saturated
or unsaturated aliphatic and/or cycloaliphatic diol;
and a combination of i) a polyoxyalkylene diimide
diacid prepared from a polyoxyalkylene diamine of
molecular weight of from about 600 to 12000,
preferably from about 900 to about 4000 and ii) dimer
acid in an amount of from about 10 to about 40~ by
weight, most preferably from about 15 to about 30~
~25~
.~
8CV 04220
- 17 -
by weight based on the combined weight of ~i)
and (ii), and optionally trimellitic anhydride. In
its most preferred embodiments, the diol will be 100
mole ~ 1,4- butanediol and the dicarboxylic acid 100
mole ~ dimethylterephthalate.
The novel polyetherimide esters described
herein may be prepared by conventional
esterification/condensation reactions for the
production of polyesters. Exemplary of the
processes that may be practiced are set
forth in, for example, United States Patent
Numbers 3,023,192; 3,761,109; 3,651,014; 3,563,653
and 3,801,547. Additionally, these compositions may
be prepared by such processes and other known
processes to effect random copolymers, block
copolymers or hybrids thereof wherein both random and
block units are present.
It is customary and preferred to utilize a
catalyst in the process for the production of the
polyetherimide esters of the present invention. In
general, any of the known ester-interchange and
polycondensation catalysts may be used. Although
two separate catalysts or catalyst systems may
be used, one for ester interchange and one for
polycondensation, it is preferred, where appropriate,
to use one catalyst or catalyst system for both. In
those instances where two separate catalysts are used,
it is preferred and advantageous to render the ester-
interchange catalyst ineffective following the com-
, . . .
.
. .
"
~'~5~ 8CV 0~220
- lB - .
pletion of the precondensation reaction ~y means of
known catalys~ inhibi~ors or quenchers, in particular,
phosphorus compounds ~uch as phosphoric acid, phos-
phenic acid, phosph~nic acid and the alkyl or aryl
esters or salts thereof, in order to increase the
thermal ~tability of the resultant polymer.
~ x~mplary of the suitable kno~l ~a alysts there
may be given the acetates, casboxylates, hydroxides,
~xides, alcoholates ~r ~rganic comp:Lex compounds of
1~ zinc, manganese, antimony, ~obalt, lead, ~alcium and
the alkali metals insofar as these compounds are
soluble in the reaction mixture. 5pecific examples
include, zinc acetate, calcium acetate and combina-
tions thereof with antimony tri-~xide and the li~e.
These catalysts as well as additional useful catalysts
are described in United States Patent
Nu~ers 2,465,319; 2,534,028; 2,850,483;. -
2,892,815; :3,937,1~0; 2,998,412; 3,047,539;
3,110,693 and 3i385,830, among others.
Where the reactants and reactions allow, it is
preferred to use the tit~nium catalysts including the
inorganic and ~rganic titanium containing catalysts
~uch as those described in, for ex~mple, - .
2,720,502; 2,727,881; 2,729,619; 2,822,348;
2,906,737; 3,047,515; 3,056,817; 3,056,818;
and 3,075,952, a~ong others. Espe2ially preferred
are the organic titanates such as tetra-butyl titan-
ate, tetra-isopropyl titanate and tetra-D~tyl titanate
and the complex titanates derived fr~m alkali or alka-
line earth metal alkoxides and titanate esters, most
preferably the organic titanat~s. These too may be
u~ed al~ne or in com} ination with o~her c2t31y5ts such
as for example, zin~ acetate, ~anganese ~ce~ate cr
antimony trioxide, and/or with a ~a~aly~ quencher as
described above.
~ 8CV 0~220
-- 19 --
Although the n~vel p~lyetherimide ester ~f the
present inventi~n p~ssess many desirable properties,
it i~ preferred ~ s~a~ ze certain of the c~mp~si-
ti~ns t~ heat, ~xidatiDn, radiativ~ by W light and
the like. This can be accomplished by incorp~rating
6tabilizer material~ int~ the c~mpositions either dur-
i~g pr~ducti~n ~r while in a hot melt ~tage following
p~lymerizati~n~ The particular stabilizers useful
herein are any ~f th~se ~nown in the art which are
~uitable for polyetherimide esters.
Satisfact~ry stabilizers comprise phenols and
their derivatives, amines and their derivatives, com-
p~unds c~ntaining ~oth hydroxyl and amine gr~ups,
hydroxyazines, oximes, p~lymerie phen~lic esters and
~alts of multivalent metals in which the mPtal is in
its lower valence state.
Representative phenol derivatives useful as sta-
bilizers include 3,5-di-tert-butyl-4-hydroxy hydr~-
cinnamic triester with 1,3,5-tris-(2-hydroxyethyl)-s-
triazine-2,4,6-l1~,3~,5H)trione; 4,4'-bis(2,6-diter-
tiary~butylphen~l); 1,3,5-trimethyl-2,4,6-tris(3,5-di-
tertiary-butyl-4-hydroxybenzyl)benzene and 4,4'-butyl-
idene-bis(6-tertiary-butyl-m-cresol). Vari~us in3rgan-
ic metal salts or hydr~xides can be used as well as
~5 ~rgani~ c~mplexes ~uch as nickel dibutyl dithi~carbon-
ate, manganous ~alicylate and copper 3-phenyl-salicy-
late. ~ypical amine ~tabilizers include N,N'-bis(~eta-
naphthyl)-p-phenylene diamine; N,N' bi~ methyl-
heptyl) -p-phenylene diamine and ~ither phe~yl-beta-
naphthyl amine or its reacti~n pr~ducts with~ldehydes. Mixtures ~f hindered phen~l~ wi~h es~ess
of thi~dipr~pionic acid, mercaptides and phosphite
esters ~re particularly useful. Additional ~tabiliza-
ti~n t~ ultravi~let light can be obtained by comp~und-
ing with varivus W ~bs~rber~ 6uch ~s substitutedbenz~phen~nes and/~r ben~tsia2sles.
8Cv 04220
- 20 -
Opti~nally, it m~y be desirable to ~dd a minor
am~unt, up to ab~ut 20 mole ~, preferably up to about
10 mole ~, ~ased on the moles 4f the polyoxyalkylene
diimide diacid, Df a tricar~oxylic c:omponent to the
reaction mixture. While higher amounts of the tri-
carboxylic component may be used, this has the dis-
~dvantage Df reduciny ~ome of th~ beneficial proper-
ties of the present p~lymers. Suita~le tricarb~xylic
components are the ~ame as identified above for the
preparation of the pDly~xyalkylene diimide diacid.
While it is preferred that the additional tricarboxyl-
ic component be th~ same as used in the preparation ~f
the polyoxyalkylene diimide diacid, it is not neces-
~ary. The addition of the tricarboxylic acid com-
ponent will have the added benefit of picking up andreacting with any residual, unreacted amine groups
and, consequen~ly, aiding in the viscosity build of
the polymer itself.
~urther, the properties of these polyesters can
be modified by incorporation of various conventional
inorganic fillers such as carbon black, silica gel,
alumina, clays and chGpped fiberglass. These may be
incorporated in amounts up to ~0~ by wei~ht, prefer-
ably up to about 30~ by weight. In general, these
additives have the effect of increasing the modulus of
~he material at various elo~gations.
DETAI~ED DESCRIPTION _~ THE PREFERRED EMBODIMENTS
The following examples are presented as illustra-
tive of the present invention and are not to be con-
~trued ~s limiting thereof.
Physical properties were determined ~ccording theproper ASTM methods as follows:
~ 8Cv 04220
- 21 -
Flexural Modulus AS~M D 790
Tensile Strength ASTM D 638
Tensile Elongation ASTM D 63~
Shore D Hardness ASTM :D 224D
5 Tensile Set ASTM D 412
In general, all compositi~ns wlere prepared by
placing all reactant~ in ~he rea~tion vessel and heat-
ing to 180~C. After the theoretica.l amount of
methanol was removed, the pot temperature was in-
creased t~ about 250~C. and a vacuum applied ( l~m ~g~
until the desired vi~cosity polymer was ~btained. All
reacticns, unless otherwise specified were catalyzed
with te~raoctyl ti~anate catalyst.
Diimide Diacid A
1~ A polyoxyalkylene diimide diacid was prepared by
the imidization of trimellitic anhydride with Texaco
Chemical Company 16 Jeffamine~ D2000, a polypropylene
ether diamine, average molecular weight 2000,
Diimide Viacid B
A second polyoxyalkylene diimide diacid was pre-
pared by the imidiza~ion of trimellitic anhydride with
Texaco Chemical Company'~ 3effamine ED-900, a predom-
inately polyethyl~ne oxi~e backbone, copoly~ethylene
~xide-propylene oxide) diamine, average molecular
weight 900.
Diimide Diacid C
A third polyoxyalkylene diimide diacid was pre-
pared by the imidization of trimellitic anhyaride with
Texaco Chemical Company'~ Jeffami~e ED-2~1, a predom-
inately polyethylene oxide backbone, ~opoly(ethyleneoxide-propylene oxide)diamine~ average molecular
weiyht 2000~
EXAMPL~S 1-9
: Two ~eries of c~mpo~itions were pr*pared, ~ne
with Diimide Diacid A and the other with Diimide Di-
~cid B at variou~ weight rati~s to di~arboxylio a~id.
;.;. -
8CV 04220
- 22 -
The comp~sitions were as presented :in Table 1. All
reactants are i~ parts by weigh~n AdditiDnally, each
composition contained about 3 % by weight based on the
diimide diacid ~f a ~hermal ~tabili:zer.
S The elast~meric p~lymers ~f these examples had
excellent physical properties and had surpri~ingly
superior processability and moldabi.lity
characteristics.
5~9~
8CV 04220
-- 23 7
~n
~ ~1
N C~ ~ t~
11~ ~1
In u~
U)l ~ ~ ~I O
U~
c: m ~ m ~r ~ ~ o~
'~F I ~ ~ ~ I O _I
I~ ~
_1 ~ ~ 1` ~ o ~ u~,
~ 1 ~ ~ . I N 1~
~` ~
U~~D ~ ~r ~ OD
I~ ~
-
~a ~
_~ C
X
a) rl
~ ~ tq --I ~ ~ ~ O
o ~
~I h V
C~ C J~
~ c: e~ a o ~ ~ cn
E~ ~ 0 E~ ~ _I
~ ~ ~ ~ 0 ~ ~ ~ ~ ~ G)
U2 ~ ~ o ~ c~
a
c Æ 6 E~
~E ~ I
C~ ~ 1 ~ h t:;
~ ~ c:~ ~a a æ E~ ~
8Cv 04220
~ 24 -
EXAMPLES 1~-22
Several ~dditional compositi~ns within he ~cope
Df the present in~ention were prepared d~monstrating
verious different embodiments hereof~ ~or example,
Example 10 demons~rates a cvmposi~iDn derived fro~ a
mixture of dimethylterephthalate and i ophthalic acid
and Examples 11, 15, 17 and 21 demonstrates the u~e of
dimer acid (Hystre2le~ 3695 - Witco Chemical
Corporation).
Finally, Example 16 demonstrate the use
of ethylene glycol as the diol component Ithis
reaction used antimony oxide and zinc acetates as
~atalysts with a phosphite cata}yst quencher)~ Only
those examples as indicated contained a thermal
stabilizer. The composition and physical properties
of these examples were as set forth in Table 2. All
amounts are in parts by weight unless otherwise
specified~ A comparison vf Example 6, above, with
Example 12 demonstrates the improved properties
obtained by use of stabilizer and excess tximellitic
2~ anhydride.
, ~ _
i0`~ 8CV 04220
-- 25 --
C:7 0 ~ 1~') ~ r~l N
t~
~ l J I N
f`J I t~
r
_~ ~
u~ cr. ~r
_11 N _l 1
r ~ u~
_I _I ~ _I
~r) t~l
cr o u~ r~
,:1 t` Cr~
tn O O c ) ~ r c
2 ~rl ~. I ~ I I I I ~ I ~ ~D t,
r- ~D 0 ~U
N Ul 'C1
'O
_/ ~ D O
_
--I ~
a ~ ~ oP o
X t~
0 ~ _~ o ~ ~ ~
O ~-
,) N _I h 'O O ~n .. t ~ 0 Lq
~ ~ ~ u ~ x u ~ V
z q ~ O '
~3 ~ ~ ~ ~ ~ --( ~ ~ ~ ~o ~ u~ O
X ~ X ~ ~
E-~ ill al ~ ~1 t) ~ al H _~ 3
P~ I :~ O t~ E~ ~J ~ ~X u~ sn h ;q
:~ ~ ~ E o ~ ~ e o
c~ -~ ~ a ~ a E~ ~
8Cv 04220
- 26 -
E~AMP~S 23-2?
Additional compositions were p.repared ~gain
further demonstrating the broad ~cope ~f-the present
invention wherein both ~tabilizer and additional
trimellitic anhydride were added to the rea~tion mix.
The compositions and the physical properties thereof
were as ~hown in Example 3.
\
\~
.
~3CV 04220
2 7
. . a
_ ~ Z
.~,
~9 ~ ~ Z
U~
u~
~ _, ~
.
C~
U~
~, . , ~ ~ D
~r
~1
o
~1 D~ O~ O` ~ O
N ¦ O
c) R 1::
a ~rl O
~a ~ h
.C
~ _I ~ t~ "5 _I C
:i: ~ ~ U ~ .a ~)
C) SU ~ O t~ r~
E-l 10 0 ~ H
~ ~ X ~ .C
t~
C) ~, ::: ~ s ~ ~
s~ ~ E
~ ` ~ ~ S h ~ ~) .
t43 ~ D~ p E' ) ~ 9E ~ ~
~CV 0~220
- 28 -
EX~MPLES El-E4, COMPARATIVE EXAMPLES CEl CE6
A series of examples were prepared typifying
the modified copolyetherimide esters of the present
invention and unmodified copolyetherimide esters. In
addition to demonstrating the benefits attributed to
these compositions, these examples demc,nstrate the
broad application of the present teaching giving
examples with different amounts of dimer, varying
weight ratio of i) polyoxyalkylene diimide diacids and
ii) dimer to dicarboxylic acid (b) and various
polyoxyalkylene diimide diacids. The specific
compositions of each example and comparative example
as well as the physical properties therPof are set
forth in Table 4. All component~ are expressed in
parts by weight unless otherwise stated.
~ _ ___
8CV 04220
-- 29 --
~ o ~ ~ ~ rl ~ O
UI ~ r ~
Il') O 0~ N t~ ~ ~ ~D
~ I o O ~
~7 ~ O CD ~ ~ ~ ~r q 5
~ I ~ ~ I ~ I r~ ~ O
.
~ ~ O U~ ~ I O
IL1 Il) E~
0
al
~ ~ o
~ a
N C)
O ,l
X _O
G ~5 al
a e ~ O ~ tn
O ~ ~ ~ ~ 10
~ a s ~ R
~rl a Ç~ t~ V t~ ~ ~ ~ ç G ~P
., `D ~ ~a ~.) . t o o h
N Q) rl _I ~
:~ c a~ l ~ ~ ~
Ei E~ .CI IE~ Cl ~ X ~ h
~r ~ o ~ 0
5~
8CV 04~20
- 30 -
From the examples in Table 4 it is clear
that the modified compositions of the present
invention have improved flexibility at the same or
about ~he same levels of incorporation of
polyoxyalkylene diimide diacid. For example
comparison of Example El, E3 and E4 with comparative
Examples CEl, CE3 and CE4 respectively demonstrates
the improved flexibility of the composition of the
present invention.
Altern~tively, unmodified compositions
having about the same flexibility as the modified
polyetherimide ester compositions of the present
invention require about a 20% increase in the amount
of polyoxyalkylene diimide diacid component. Because
of tne susceptability of the polyether component to
thermal and oxidative degredation as well as attack by
solv~nts, applicant's composition by virtue of lesser
amounts of polyether will have enhanced thermal and
oxidative stability as well as improved solvent
resistance as compared to the unmodified compositions~
Obviously, other modifications and
variations of the present invention are possible in
light of the above teachings. It is therefore to be
understood that changes may be made in the particular
embodiments of the invention described which are
within the full intended scope as defined by the
appended claims.
