Note: Descriptions are shown in the official language in which they were submitted.
8CV 04284
-- 1 --
ELPSTO~ERIC C~POSITIO~S
~ he present invention relates to novel thermn-
plastic elastomeric molding compositions. Depending
upon their compositional ma~eup, these compncitions
have a number of excellent and highly desirable
physical properties including excellent tensile
elongatinn and ln~ temperature impact strength as well
as other highly desira~le stress-strength
characteristics including the ability to absorb high
energy and "spring ba~k" with little or no permanent
deformation'upnn impact. Specifically, the
compositions of the instart invention comprise poly-
etherimide esters or p~lyetherester imides having
admixed there~ith a combination of:
a) a high molecular weight polyester, and
b) a homopo]y~er or copolymer modifier resin
having as a major substituent units derived
from one or more monvmers selected from the
group consi'sting of vinyl aromatic monomer,
esters of acrylic and alk~-l acrylic acids and
conjugated dienes, and, optionally
C) cl 2y filler.
Polyether ester imides are well known havina b~en
described in numerous publications and patents includ-
ing for example, ~onore et al, ~Synthecis and Study of
~7ario-~s Reactive ~ligmer~ ~nd of Poly~ester-imide-
ether)s," European Polymer Journa Vol. 16, pp.
905-916, ~cto~er 12, 1979; and in Kluiber et al, ~
Patent ~n. 3,274,159 and ~olfe Jr., U.S. Patent Nos.
4,37],692 and 4,37~,693, respectively. ~ore recertly,
30 ~cCready in United States Patent Number 4,556,705
which issued December 3, 1985-, disc]nsed a novel
class of polyetherimide esters having superior elastn-
meric and other desired characteristics.
~ 3 ~ CV 042~4
While the foregoing polymers having ether, imide
and ester units have many desired properties includirg
good flexibility, impact strength snd mol2ability,
these compositions are limited to certain applications
where physical integrity or stiffness of the part is
not desired or necessary due to their very low fleY.-
ural modulus. Additionally, these composi.tions have
verv poor heat sag resistance. Thus, molded parts
from these compositions severely sag upon exposure to
high temperatures, eg. greater than 250P.
It is an object of the present invention to pro-
vide novel thermoplastic molding compositionC having
excellent elastomeric properties including the ability
to absorb and withstand high energy impact and n spring
back" to its previouC state or shape upon removal of
the impinging energv with little or no pe~manent
deformation.
It is also an object of the present invention to
provide novel thermoplastic molding compositions ha~-
ing e~cellent impact strength, particularly low te~p-
erature impact strength, while, where desired, retain-
~ ing good flexibility.
Furthermore, it is an object of the present inven-
tion to provide novel thermoplastic molding co~.posi-
tions which ha~le surprisingly high ter.sile elongaticnas well as e~cellent melt and crystallization temper-
atures and related characteristics.
It has no~ been discovered that novel thermo-
plastic molding compositions ma~ he prepared which
overcome the foregoing deficiencies and have good
overall phy=ical characteristics including high
strength and stress-strain properties, good impact
re~iFtance and good moldability.
S~MMARY
In accordance with the present invention there
are provided novel thermoplastic compositions havin~
3~
- 3 - 8CV 4284
excellent impact strength, particularly low temperature
impact strength, and excellent tensile elongation and/or
Dynatup properties comprising an admixture cf
A) one or more thermoplastic elastomeric polymers
characterized as having ether, ester and imide linkages
and wherein the ether linkages are present as high
molecular weight, i.e. average number MW of from about
400 to about 12000, polyoxyalkylene or copolyoxyalkylene
units derived from long chain ether glycols and/or long
chain ether diamines,
B) one or more high molecular weight thermoplastic
polyesters,
C) one or more homopolymer or copolymer modifier
resins having as a major constituent units derived from
one or more monomers selected from the group consisting
of vinyl aromatics, esters of acrylic and alkylacrylic
acids and conjugated dienes, and, optically,
~) clay filler.
Depending upon the desired physical properties of
and the end use application for the resultant
composition, these compositions are generically
comprised of from about 90 to about 5 parts by weight A,
from about 5 to about 90 parts by weight B, from about 5
to about 35 parts by weight C and from 0 to about 30
parts by weight D. Preferred compositions are those
having good flexibility combined with impact strength,
consequently these preferred compositions will comprise
from about 90 to about ~0 parts by weicJht A, I:rom aho-lt
S to about S0 parts by we:ight B, from about 50 to abo-lt
30 35 parts by weight C and from 0 to about 30 parts by
weight D.
Detailed Description _f tho Invention
Thermoplastic elastomeric polymers (A) suitable ~`or
use in the practice of the present invention are
characterized as containing imide, ester and ether
$~
3~
- 4 - 8CV 42?34
linkages wherein the ether linkages are present as high
molecular weight, i.e. from about 400 to about 12000
number average MW, preferably from about 900 to about
4000, polyoxyalkylene or copolyoxyalkylene units derived
from lone chain either glycols and/or long chain ether
diamines. Typically these thermoplastic elastomeric
polymers are referred to as poly(etherester imide)s,
poly(ester imide ethers) and poly(etherimide ester)s.
Suitable poly(etherester imide)s and pol~ester-
imide ether)s and their manufacture are described in,for example, Honore et al "Synthesis and Study of
Various Reactive Oligomers and of Poly(esterimide
ethers)", European Polymer Journal, Vol. 16 pp. 909-916,
October 12, 1979 and in Wolfe Jr., United States Patent
Numbers 4,371,692 and 4,371,693. These are
characterized as comprising units of the formulas:
O O O O
Il 11 11 11
~ ~ N-Q-N ~ C-O-G-O-
11 11
O O
and
O O o o
Il 11 11 11
- C ~ ~ N-Q-N ~ C-O-D-O- II
Il 11
O O
20 or
O O
Il 11
- C ~ C \ O III
~ N-Q'-C-O-G-O-
C
o
J., _,1,
! !~ ~, `.
3~''3'~
- 5 - 8cv 4284
and
O O
Il 11
-C~ C \ O
N - Q ' -C-0- D- O- IV
C
o
or mixtures thereof wherein G is a divalent radical
remaining after the removal of terminal (or as nearly
terminal as possible) hydroxyl groups from a long chain
poly(oxyalkylene)glycol having a number average molecular
weight of from about 400 to about 12000; D is a divalent
radical remaining after the removal of hydroxyl groups from
a diol having a molecular weight less than about 300; Q is a
divalent radical remaining after removal of amino groups
from an aliphatic primary diamine having a molecular weight
of less than 350 and Q' is a divalent radical remaining
after removal of an amino group and a carboxyl group from an
aliphatic primary amino acid having a molecular weight of
less than 250, with the proviso that from about 0.5 to about
10 D units are present for each G unit.
Each of the above esterimide units exemplified by
formulas I and II and formulas III and IV contain a diimide-
diacid radical or an imide-diacid radical, respectively. As
described in Wolfe, these are preferably prepared by
reacting the respective aliphatic diamine or amino acid with
trimellitic anhydride either in a separate step pr:i.or to
polymeri.zatiorl or dur:ing the po:l.ymeri.7,(lt:i.0rl :i.tc;e.l.f.
Lonq cha:in ether g.Lycols which can be used to pro-
vide the -G- radicals in the thermoplastic elastomers
are preferably poly(oxyalkylene)gl.ycols and copoly(oxy-
alkylene)glycols of number average molecular weight of
from about 400 -to 12000. Preferred poly(oxyal.kylene)
units are derived from long chain ether glycols of from
~ ;~ L~ ~ ~ C6~ 3 ~L
- 6 - 8CV 428~
about 900 to about 4000 number average molecular weight
and having a carbon~to-oxygen ratlo of from about 1.8 to
about 4.3, exclusive of any side chains.
Representative of suitable poly~oxyalkylene)glycols
there may be given poly(ethylene ether)glycol; poly-
(prcpylene ether)glycol; poly(tetramethylene ether)-
glycol; random or block copolymers of ethylene oxide and
propylene oxide, including ethylene oxide capped poly-
(propylene ether)glycol and predominately poly(ethylene
ether) backbone, copoly(propylene etherethylene ether)-
glycol and random or block copolymers of tetrahydrofuran
with minor amounts of a second monomer such as ethylene
oxide, propylene oxide, or methyltetrahydrofuran (used
in proportions such that the carbon-to-oxygen ratio does
not exceed about 4.3). Polyformal glycols prepared by
reacting formaldehyde with diols such as 1,4-butanediol
and 1,5-pentanediol are also useful. Especially
preferred poly(oxyalkylene)glycols are poly(propylene
ether)glycol, polytetramethylene ether)glycol and
predominately poly(ethylene ether) backbone
copoly(propylene etherethylene ether)glycol.
Low molecular weight diols which can be used to
provide the -D- radicals re saturated and unsaturated
aliphatic and cycloaliphatic dihydroxy compounds as well
as aromatic dihydroxy compounds. These diols are
preferably of a low molecular weight, i.e. having a
molecular weight of about 300 or less. When used
herein, the term "diols" and "low molecular weight
cliols" should be construed to inclucle e-f~livalerlt e-;ter
forming derivatives the~eol, providecl, tlC)WC!VC`r, thLlt the
molecular weight requirement pertaills to the cliol only
and not to its derivatives. Exemplary of ester forming
derivatives there may be given the acetates of the diols
as well as, for example, ethylene oxide or ethylene
carbonate ~For ethylene glycol.
......
3~3'~
Preferred saturated and unsaturated aliphatic an~
cycloaliphatic diols are those having from about 2 to
19 carbon atoms. Exemplary of these diols there may
be given ethylene glycol; propanediol; butanediol;
pentanedio], 2-methyl prc,panediol; 2,2-dimethyl propane-
diol; hexanediol; decanediol; 2-octyl undecanediol;
l,?-, 1,3- and 1,4- dihydroxy cyclohexane; 1,2-, 1,3-
and 1,4-cy_lohexane dimethanol; butene~iol; hexene
diol, etc. Especially preferred are 1,4-~utanediol
and mixtures thereof with he~arediol or butenediol,
moct preferably 1,4-but2n~Adiol.
Aroma~ic diols suitable for use in the prepara-
tion of the thermoplas~ic elastomers are generally
those h2ving from 6 to about 13 carbon atoms. In-
clucAed a~ong the aromatic dihydroxy compounds arer~sorcinol; hydroquinone; I,5-dihydroxy naphthalene,
4,4'-dihydroxv diphenyl; bis(p-hydroxv phenyl)methan~
an~A ?,2-bis(p-hydroxy pheny]) propane.
Especially preferred diols are the saturated ali-
phatic diols, mixtures thereof and mixtures of a satur-
ated diol(s) with an unsaturated d,iol(s~, wherein each
~ diol contains from 2 to about 8 carbon atoms. ~here
~ore than one ~iol is employe~, it is preferred that
at least about 60 mole ~, based on the total diol con-
tent, be the same dio], most prefer2~1y at leRst 80
mG]~ ~. As m~ntioned above, the preferred thermo-
pla~tic elastomers are those in which 1,4- butanediol
is precent in a pr~dominant amount, moct pre~erably
~hen 1,4-butanedic,l is the only dicl.
3n Diamines which can br used to prcvide the -~-
ra~Aicals in the polymerfi of this invention are ali-
phatic (including cvc~oaliphatic) primary ~iamines
having a mnlerular weight of less thar about 350, pre-
~erablA~ be]ow ab~ut ?50. Diaminec containing aro~atic
rinqs ir which both amino groups are attached to ali-
phatic carbons, such as p-~vlylene diamin~, are also
3~
~CV 428~
meant to be included. Representative aliphatic (and
cycloaliphatic) primary diamines are ethylene diamine,
1,2-propylene diamine, methylene diamine, 1,3- and
1,4-diaminocyclohexane, 2,4- and 2,6-diaminomethyl-
~cyclohexane, m- and p-xylylene diamine and bis-
(4-aminocyclohexyl)methane. Of these diamines,
ethylene diamine and bis(4-aminocyclohexyl~methane are
preferred because they are readily available and yield
polymers having excellent physical properties.
Amino acids which can be used to pro~ide the -Q'-
radicals in the polymers of this invention are all-
phatic (including cycloaliphatic) primary amino acids
having a molecular weight of less than about 250.
A~ino acids containing aromatic rings in which the
amino sroup is attached to aliphatic carbon, such as
phenylalanine or 4-(B-aminoethyl)benzoic acid, are
also meant to be included. Representative aliphatic
and cycloaliphatic primary amino acids are glycine,
alanine, B-alanine, phenylalanine, 6-aminohexanoic
acid, ll-aminoundecanoic acid and 4-aminocyclohexanoic
acid. Of these amino acids, glycine and B~alanine are
preferred because they are readily available and yield
polymers having excellent physical properties.
A second and preferred class of thermoplastic
elastomers (a) suitable for use in the practice of the
present invention are the poly(etherimide esters) as
described in McCready, in ~nited States PAtent Number
4,556,705 issued December 3, 1985 ancl ~nil-ed States
Pat~nt Number 4,556,683 which p~tent i~sued
December 3, 1985 entitled "Thermoplas-tic Polyetherimide
Ester Elastomers". In gener~l, the
poly(etherimide esters) of McCready are random and
block copolymers prepared by conventional processes
from (i) one or more diols, (ii) one or more dicar-
boxylic acids and (iii) one or more polyoxyalkylene
diimide diacids or the reactants therefore. The pre-
3~
- 9 - 8CV 4284
ferred poly(etherimide esters) are prepared from (i) a
C2 to clg aliphatic and/or cycloaliphatic diol,
(ii) a C4 to C19 aliphatic, cycloaliphatic and/or
aromatic dicarboxylic acid or ester derivative thereof
and (iii) a polyoxyalkylene diimide diacid wherein the
weight ratio of the diimide diacid (iii) to
dicarboxylic acid (li) is from about 0.25 to 2.0,
preferably from about 0.4 to 1.4.
The diols (i) suitable for use herein are
essentially the same as those used to provide the -D-
radical in formulas II and IV as described above.
Dicarboxylic acids (ii) which are suitable for
use in the preparation of the poly(etherimide esters)
are aliphatic, cycloaliphatic, and/or aromatic
dicarboxylic acids. These acids are preferably of a
low molecular weight, i.e., having a molecular weight
of less than about 350; however, higher molecular
weight dicarboxylic acids, especially dimer acids, may
also be used. The term "dicarboxylic acids" as used
herein, includes equivalents of dicarboxylic acids
having two functional carboxyl groups which perform
substantially like dicarboxylic acids in reaction with
glycols and diols in forming polyester polymers.
These equivalents include esters and ester-forming
derivatives, such as acid halides and anhydrides. The
molecular weight preference, mentioned above, pertains
to the acid and not to its e~uivalent ester or ester-
forming der:ivative. rl'hu~., an ef;ter of a d:icarboxylic
acid having a molecular weiyht greater than 350 or an
acid equivalent of a dicarboxylic acid having a
molecular weight greater than 350 are included
provided the acid has a molecular weight below about
350. Additionally, the dicarboxylic acids may contain
any substituent group(s) or combinations which do not
substantially interfere with the polymer formation and
use of the polymer of this invention.
3~
- 10 - 8CV 4284
Ali.phatic dicarboxylic acids, as the term is used
herein, refers to carboxylic acids having two carboxyl
groups each of which is attached to a saturated carbon
atom. If the carbon atom to which the carboxyl group
is attached is saturated and is in a riny, the acid is
cycloaliphatic.
Aromatic dicarboxylic acids, as the term is used
herein, are dicarboxylic acids having two carboxyl
groups each of which is attached to a earbon atom in
an isolated or fused benzene ring system. It is not
necessary that both functional carboxyl groups be
attached to the same aromatic ring and where more than
one ring is present, they can be joined by aliphatic
or aromatic divalent radicals or divalent radicals
such as -O- or -S02--
Representative aliphatie and cycloaliphatic acidswhich can be used are sebacic acid, 1,2-cyclohexane
dicarboxylic acid, 1,3-cyclohexane dicarboxylic acid,
1,4-cyclohexane dicarboxylic acid, adipic acid, glutaric
acid, succinic acid, oxalic acid, azelaic acid,
diethylmalonic acid, allylmalonic acid, dimer acid,
4-cyclohexene-1,2-dicarboxylic acid, 2-ethylsuberic
aeid, tetramethylsuccinic acid, cyclopentane
diearboxylic aeid, deeahyclro-1,5-naphthalene
dicarboxylic acid, 4,4'-bicyclohexyl dicarboxylic acid,
deeahydro-2,6 naphthalene dicarboxylic acid, 4,4
methylenebis-(cyclohexane carboxylic acid), 3,4-furan
dicarboxylic acid, and l,l-cyclobutane dicarboxylic
acid. Preferred aliphatic acids are cyelohexane
dicarboxyli.c acids, sebclcic acicl, d:ime:r aci.d, cJ:Lutclr:ic
acid, aze:l.a:i.c ac:id and adl.p:ic aci.d.
Representative aromatic dicarboxylic acids which
can be used include terephthalic, phthal.ic and iso-
phthalic acids, bi-benzoic acid, substituted dicarboxy
compounds with two benzene nuclei such as bis(p-carb-
oxyphenyl) methane, oxybis(benzoic acid), ethylene-
~ 8CV 4284
1,2-bis-~p-oxybenzoic acid), 1,5-naphthalene dicarb-
oxylic acid, 2,6-naphthalene dicarboxylic acid, 2,7-
naphthalene dicarboxylic acid, phenanthrene dicarb-
oxylic acid, anthracene dicarboxylic acid, 4,4'-
sulfonyl dibenzoic acid, and halo and C1-Cl2 alkyl,
alkoxy, and aryl ring substitution derivatives thereof.
Hydroxy acids such as p(~-hydroxyethoxy)benzoic acid can
also be used provided an aromatic dicarboxylic acid is
also present.
Preferred dicarboxylic acids for the preparation of
the polyetherimide esters are the aromatic dicarboxylic
acids, mixtures thereof and mixtures of one or more
dicarboxylic acid with an aliphatic and/or cyclo-
aliphatic dicarboxylic acid, most preferably the
aromatic dicarboxylic acids. 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 preparation of the poly(etherimide
ester), it is preferred that at least about 60 mole %,
preferably at least about 80 mole %, based on 100 mole %
of dicarboxylic acid (ii) be of the same dicarboxylic
acid or ester derivative thereof. As mentioned above,
the preferred poly(etherimide esters) are those in which
dimethylterephthalate is the predominant dicarboxylic
acid, most preferably when dimethylterephthal~te is the
only dicarboxylic acid.
Polyoxyalkylene diimide d:iacids (iii) are high
molecular weight diimide diacids wherein the number
average molecular weight is greater than about 700, most
preferably greater than about 900. They may be prepared
by the imidization reac-tion of one or more tricarb-
oxylic acid compounds containing two vicinal carboxyl
.3 ~ ~
- 12 - 8CV 4284
groups or an anhydride group and an additional carboxyl
group, which must be esterifiable and preferably is
nonimidizable, with a high molecular weight
polyoxylalkylene diamine.
In general, the polyoxyalkylene diimide diacids are
characterized by the following formula:
O o
Il 11
/C\ C\
R'OOC- R N- G-N R- COOR' V
\ C / \ C/
Il 11
O O
wherein each R is independently a trivalent organic
radical, preferably a C2 to C20 aliphatic, aromatic
or cycloaliphatic trivalent organic radical; each R' is
independently hydrogen or a monovalent organic radical
preferably selected from the group consisting of Cl to
C12 aromatic radicals, e.g. benzyl, most preferably
hydrogen; and G is the radical remaining after removal
of the terminal amine groups of a long chain poly(oxy-
alkylene)diamine equivalent to the long chain poly(oxy-
alkylene)glycol as described above in formulas I and II.
The tricarboxylic component may be almost any
carboxylic acid anhydride containing an additional
carboxylic group or the corresponding acid thereof
containing two imide-formlng vicinal carboxyl groups in
lieu of the anhydricle group. M:ixtures thereol are a:l.so
suitable. The add:itionaL carboxylic group must be
esterifiable and preferably is substantially
non-imidizable.
Further, while trimellitic anhydride :is preferred
as the tricarboxylic component, any of a number of
suitable tricarboxylic acid constituents will occur to
those skilled in the art including 2,6,7 naphthalene
~ -;
,,f~.,
trlcarboxylic anhydride; 3,3',4 diphenyl tricarboxylic
anhydride; 3,3',4 benzophenone tricarboxylic anhydr-
ide; 1,3,4 cyclopentane tricarboxylic anhydride;
2,2',3 diphenyl ~ricarboxylic anhy~ride; diphenyl
sulfone - 3,3',4 tricarboxylic anhydride, ethylene
tricarboxylic anhydride; 1,2,5 naphthalene tricarb-
oxylic anhydride; 1,2,4 butane tricarboxylic anhyd-
ride; diphenyl isopropylidene 3,3',4 tricarboxyli~
anhydride; 3,4 dicarboxyphenyl 3'-carboxylphenyl ether
anhydride; 1,3,4 cyclohexane tricarboxylic anhydride;
etc. These tricarboxylic acid materials can be
characterized by the following formula:
o
R'OOC-R ~ / O IV
where R is a trivalent organic radical, preferably a
C2 to C20 aliphatic, aromatic, or cycloaliphatic tri-
valent organic radical and R' is preferably hydrogen
or a monovalent organic radical preferably selected
from the group consisting of Cl to C6 aliphatic and/or
cycloaliphatic radicals and C6 to C12 aromatic radi-
cals/ e.g. benzy; most preferably hydrogen.
In the preparation of the poly(etherimideester)s, the diimide diacid may be preformed in a sep-
arate step prior to polymerization or they may be
formed during polymerization ltself. In the latter
instance, the polyoxyalkylene diamine and tricar-
boxylic acid component may be directly added to the
reactor together with the diol and dicarboxylic acid,
whereupon imidization occurs concurrently with ester-
ification. Alternat:ively, the polyoxyalkylene diimide
diacids may be preformed prior to polymerization by
known imidization reactions including melt synthesis
or by synthesizing in a solvent system. Such reac-
3~
- 14 - 8CV 4284
tions will generally occur at temperatures of from
lOODC. to 300DC., preferably at from about 150DC. to
about 250C. while drawing off water or in a solvent
system at the reflux temperature of the solvent or
azeotropic (solvent) mixture. Preferred polyetherimide
esters are those in which the weight ratio of the poly-
oxyalkylene diimide diacid (iii) to dicarboxylic acid
(ii) is from about 0.25 to about 2, preferably from
about 0.4 to about 1.4.
Especially preferred polyetherimide esters comprise
the reaction product of dimethylterephthalate,
optionally 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 polyoxyalkylene diimide
diacid prepared from a polyoxyalkylene diamine of number
average molecular weight of from about 400 to about
12000, 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.
As mentioned, the polyetherimide esters may be
prepared by conventional esterification/condensation
reactions for the production of polyesters. Exemplary
of the processes that may be practiced are as set forth
in, for example, United States Patent Numbers 3,023,192;
3,763,109; 3,651,014; 3,663,653 and 3,801,547.
The second component (B) of the compositions o~` the
instant invention are hi~Jh moLec~llar weL(Jht thermo-
plastic polyesters derived from one or lllore diols and
one or more dicarboxylic acids. Suitable diols and
dicarboxylic acids useful in the preparation of the
polyester component include those diols and dicarb-
oxylic acids (ii) mentioned above for use in thepreparation of the polyetherimide esters of McCready.
, ,,~;
3'3~
15 - 8CV 4284
Preferred polyesters are the aromatic polyesters derived
from one or more aliphatic and/or cycloaliphatic diols
and an aromatic dicarboxylic acid. Aromatic
dicarboxylic acids from which the aromatic polyesters
may be derived include for example the phthalic,
isophthalic and terephthalic acids; naphthalene
2,6-dicarboxylic acid and the ester derivatives there of
as well as other aromatic dicarboxylic acids mentioned
above. Additionally, these polyesters may also contain
minor amounts of other units such as aliphatic dicarb-
oxylic acids and aliphatic polyols and/or polyacids.
Preferred aromatic polyesters will generally have
repeating units of the following formula:
o
Il
O --~ C -- O --
D - OC ~ VII
where D is as defined above in formulas II and IV for
aliphatic and cycloaliphatic diols. Most preferably D
is derived from a C2 to C6 aliphatic diol.
Exemplary of the preferred aromatic polyesters there may
be given poly(butylene terephthalate), poly(butylene
terephthalate-co-isophthalate), poly(ethylene
terephthalate) and blends thereof, most preferably
poly(butylene terephthalate).
The polyesters described above are either
commercially available or can be produced by methods
well known in the art, such as tho~e set forth in United
States Patent Numbers 2,465,319; 3,047,539 and
2,910,466. Illustratively, the high molecular weight
thermoplastic polyesters (b) will have an intrinsic
viscosity of at least about 0.4 decilliters/gram and,
preferably, at least about 0.7 decilliters/gram as
measured in a 60:40 phenol/tetrachloroethane mixture at
30 D C
- 16 - 8CV 428
The third required component (C) of the
compositions of the instant invention is a modifier
resin or resin combination wherein the modifier resin
is derived from one or more monomers selected from the
S group consisting of vinyl aromatic monomer, esters of
acrylic or alkylacrylic acid and conjugated dienes.
Typically, the preferred modifier resins will comprise
a predominate amount of monomer or monomers selected
from the foregoing group. Additionally, preferred
modifier resins will be of a rubbery nature. Further,
as will be obvious from the more detailed description
below, many of the preferred modifier resins are
derived from two or more of the required monomeric
units.
The first class of modifier resins are those
derived from the vinyl aromatic monomers. These
include both homopolymers and copolymers, including
random, block, radial block, and core-shell copoly-
mers. Specifically, suitable vinyl aromatic modifier
resins include for example modified and unmodified
polystyrenes, ABS type graft copolymers; AB and ABA
type block and radial block copolymers and vinyl
aromatic conjugated diene core-shell yraft copolymers.
Modified and unmodified polystyrenes include
homopolystyrene and rubber modified polystyrenes such
as butadiene rubber modified polystyrene otherwise
referred to as high impact polystyrene or HIPS.
Additional useful polystyrenes include copolymers of
styrene and various monomers, inc:Ludin~ for exlmp:Le
poly(styrene-acry:LonitriLe (SAN) as well as the
modified alpha and para substituted styrenes and any
of the styrene resins disclosed in U.S. Patent Number
3,383,435.
ABS type graft copolymers and processes for their
production are well known and widely available com-
mercially. Typically, these copolymers are prepared
Y~
- 17
by polymerizing a conjugated diene alone or in com-
bination with a monomer copolymerizable therewith to
form a rubbery polymeric backbone. After formation of
the backbone, at least one qrafting monomer and prefer-
ably two, are polymerized in the presence of the prepolymexized backbone to obtain the graft copolymeE.
Suitable conjugated dienes may be substituted or
non-substituted and include, but are not limited to,
butadiene, isoprene, 1,3-heptadiene, methyl-1,3-
-pentadiene, 2,3-dimethyl-1,3-butadiene, 2-ethyl-1,3-
-pentadiene; 1,3- and 2,4-hexadienes, dichlorobuta-
diene, bromobutadiene, dibromobutadiene, and mixtures
thereof. Monomers copolymerizable therewith to form
the rubber backbone include the monoalkenyl arene
monomers, the acrylonitriles and the acrylic acid
esters, as hereinafter defined. Preferred rubbery
backbone polymers are derived from butadiene, alone ox
in combination with styrene or acrylonitrile, most
preferably polybutadiene.
One class of graft monomer or comonomers that may
be polymerized in the presence of the prepolymerized
backbone are the monoalkenyl arene monomers and substi-
tuted derivatives thereof. Exemplary of such suitable
substituted and non-substituted monoalkenyl arene
monomers include styrene, 3-methylstyrene; 3,5-di-
ethylstyrene, 4-n-propylstyrene, alpha-methylstyrene,
alpha-methyl vinyltoluene, alpha-chlorostyrene, alpha-
-bromostyrene, dichlorostyrene, dibromostyrene, tetra-
-chlorostyrene, mixtures thereof, and the like. The
preferred monovinylaromatic hydrocarbons used are
styrene and/or alpha-methylstyrene.
A second class of suitable graft comonomers are
the acrylic monomers such as the acrylonitriles and
the acrylic and alkyl acrylic acid esters. Exemplary
of such suitable graft monomers include, but are not
limited to acrylonitrile, ethacrylonitrile, methacrylo-
9~
- l~ - 8CV 4284
nitrile, alpha-chloroacrylonltrile, beta-chloroacrylo-
nitrile, alpha-bromoacrylonitrile, and beta-bromo-
acrylonitrile, methyl acrylate, methyl methacrylate,
ethyl acrylate, butyl acrylate, propyl acrylate,
isopropyl acrylate, and mixtures thereof. The
preferred acrylic monomer is acrylonitrile and the
preferred acrylic acid esters are ethyl acrylate and
methyl methacrylate.
Typically, the conjugated diene polymer or
~0 copolymer backbone comprises from about 5 to about 50,
preferably, from about 20 to about 50, percent by
weight of the total graft copolymer; the reminder
comprising the graft component. Additionally, the mono
alkenyl arene monomer will comprise from about 30 to
about 70 percent by weight of the total graph copolymer
and is preferably styrene. Finally, where the second
group of graft monomers is present, exemplified by
acrylonitrile, ethyl acrylate or methyl methacrylate,
they will comprise from about 10 to about 40 percent by
weight of the total graft copo]ymer.
An additional class of vinyl aromatic resin
modifiers within the scope of the present invention are
the block copolymers comprising mono alkenyl arene
blocks and hydrogenated, partially hydrogenated and
non-hydrogenated conjugated diene blocks and
represented clS AB and ABA block copolymers. Suitable
mono alkenyl arene and conjugated diene monomers for
use in the preparation of the block copolymers include
those mentioned above for the preparation of the AI~S
type graft copolymers. Of course it w:i1l be understood
that both blocks A and B may be either homopolymer or
random copolymer blocks as long as each block
predominates in at least one class o~ the monomers
characteriæing the blocks and as long as the A blocks
individually predominate in monoalkenyl arenes and the
B blocks individually predominate in dienes. The term
. j~ ,,
.,s.;,-:
3~9'~
- 19 ~ 8CV 4284
"monoalkeny arene" will be taken to include especially
styrene and its analogs and homologs including alpha-
methylstyrene and ring-substituted styrenes, particu-
larly ring-methylated styrenes. The preferred mono-
alkenyl arenes are styrene and alpha-methylstyrene,
most preferably styrene. The B blocks may comprise
homopolymers of butadiene or isoprene and copolymers of
one of these two dienes with a monoalkenyl arene as
long as the B blocks predominate in conjugated diene
units. When the monomer employed is butadiene, it is
preferred that between about 35 and about 55 mole
percent of the condensed butadiene units in the
butadiene polymer block have 1,2 configuraticn. Thus,
when a hydrogenated or partially hydrogenated block
copolymer is desired, it is or has segments which are
or resemble a regular copolymer block of ethylene and
butene-l (EB). If the conjugated diene employed is
isoprene, the resulting hydrogenated product is or
resembles a regular copolymer block of ethylene and
propylene (EP).
When hydrogenation of the block copolymer is
desired, it may be and is preferably effected by use of
a catalyst comprising the reaction products of an
aluminum alkyl compound with nickel or cobalt
carboxylates or alkoxides under such conditions as to
preferably substantially completely hydrogenate at
least 80% of the aliphatic double bonds while
hydrogenating no more than about 25% of the alkenyl
arene aromatic double bonds. PreEerred hydroycnated
block copolymers are thosc where at leclst 99~ of the
aliphatic double bonds are hydrogenated while less than
5% of the aromatic double bonds are hydrogenated.
The average molecular weights of the individual
blocks may vary within certain limits. In most
instances, the monoalkenyl arene blocks will have
number average molecular weights in the order of
~'
- 20 - 8CV 4284
5,000-125,000 preferably 7,000-60,000 while the
conjugated diene blocks either before or after hydro-
genation will have number average molecular weights in
the order of 10,000-300,000, preferably 30,000-150,000.
The total number average molecular weight of the block
copolymer is typically in the order of 25,000 to about
350,000, preferably from about 35,000 to about 300,000.
These molecular weights are most accurately determined
by tritium counting methods or osmotic pressure
measurements.
The proportion of the monoalkenyl arene blocks
should be between about 8 and 55% by weight of the block
copolymer, preferably between about 10 and 30 percent by
weight.
These block copolymers may have a variety of
geometrical structures, since the invention does not
depend on any specific geometrical structure, but rather
upon the chemical constitution of each of the polymer
blocks. Thus, the structures may be linear, radial or
branched. The specific structure of the polymers is
determined by their methods of polymerization. For
example, linear polymers result by sequential introduction
of the desired monomers into the reaction vessel when
using such initiators as lithium-alkyls or
dilithiosti:Lbene and the like, or by coupling a two
segment block copolymer with a difunctional coupling
agent. Branched structures, on the other hand, may be
obtained by the use of suitable coupling agents having a
functionality with respect to the polymers or precul-sor
polymers, where hydrogenation of: the l:in,.l.L b:L.ock pol.ymer
is desired, of three or more. ~oup.Ling may be effected
with multifunctional coupling agents such as dihaloal~anes
or dihaloalkenes and divinyl benzene as well as certain
polar compounds such as silicon halides, siloxanes or
esters of monohydric a.l.cohols with carboxylic aci~s.
1~4.~
- 21 - 8CV 4284
The presence of any coupling residues in the polymer
may be ignored ~or an adequate description of the
polymers forming a part of the compositions of this
invention. Likewise, in the generic sense, the
specific structures also may be ignored.
Various methods, including those as mentioned
above, for the preparation of the block copolymers are
known in the art. For example, AB type block
copolymers and processes for the production thereof are
disclosed in for example United States Patent Numbers
3,078,254; 3,402,159; 3,297,793; 3,265,765; and
3,594,452 and U.K. Patent Number 1,264,741. Exemplary
of typical species of AB block copolymers there may be
given:
polystyrene-polybutadiene (SBR)
polystyrene-polyisoprene and
poly(alpha-methylstyrene)-polybutadiene.
Such AB block copolymers are available commercially
from a number of sources including Phillips under the
trademark Solprene.
Additionally, ABA triblock copolymers and
processes for their production as well as
hydrogenation, lf desired, are disclosed in United
States Patent Numbers 3,149,182; 3,231,635; 3,462,162;
3,287,333, 3,595,942; 3,694,523 and 3,842,029. In such
processes, particular preference is made to the use of
lithium based catalysts and especially lithium alkyls
for the preparation of the block polymers.
Exemplary of typical species of triblock
copolymers there may be ~iven:
polystyrene-polybutadlene-polystyrene (SBS)
polystyrene-polyisoprene-polystyrene (SIS)
poly(alpha-methylstyrene)-polybutadiene-poly-
(alpha-methylstyrene) and
poly(alpha-methylstyrene)-polyisoprene-poly-
(alpha-rnethylstyrene).
1 ~ 47$3~
- 22 - 8CV 4284
A particularly preferred class of such copolymers are
available commercially as KRATONR and KRATON GR from
Shell. The Kraton block copolymers comprising at least
two monoalkenyl arene polymer end blocks A and at least
one hydrogenated, partially hydrogenated or
non-hydrogenated conjugated diene polymer mid block B,
said block copolymer having an 8 to 55 percent by weight
monoalkenyl arene polymer block content, each polymer
block A having a number average molecular weight of
between about 5,000 and about 125,000, and each polymer
block B having a number average molecular weight of
between about 10,000 and about 300,000.
The second class of modifier resins are those derived
Erom the esters of acrylic or alkyl acrylic acid.
Exemplary of such modifier resins there may be given the
homopolymers and copolymers of alkyl acrylates and alkyl
methacrylates in which the alkyl group contains from 1 to
8 carbon atoms: including for example methyl acrylate,
ethyl acrylate, butyl acrylate, methyl methacrylate, ethyl
methacrylate and butyl methacrylate. Suitable copolymers
include the copolymers of the foregoing with vinyl or
allyl monomers (e.g. acrylonitrile, N-allymaleimide or
N-vinyl maleimide) or with alpha-olefins (e.g. ethylene).
Especially preferred alkyl acrylate resins are the
homopolymers and copolymers of methyl methacrylate (e.g.
polymethyl methacrylate).
The third class of modifier resins are those
described from con~ugated dienes. While marly copo]ymers
contain:ing conjugated dienes have beell d~ .;cu~;sed above,
additional conjuqated cliene modiEier resins include for
example homopolymers and copolymers oE one or more
con~ugated dlene including for example polybutadiene
rubber or polyisoprene rubber. Finally, ethylene-
propylene-diene monomer rubbers are also intended to be
with the scope of the present invention. These
.,, ~
~1'` i`'~:
3~J`~3'~
- 23 - 8CV 4284
EPDMs are typified as comprising predominately ethylene
units, a moderate amount of propylene units and only a
minor amount, up to about 20 mole percent of diene
monomer units. Many such EPDM's and processes for the
production thereof are discLosed in U.S. Patent numbers
2,933,480; 3,000,866; 3,407,158; 3,093,621 and
3,379,701.
Finally, one group of modifier resins which
transcends all of the above classes are the core-shell
type graft copolymers. In general these are
characterized as having a predominately conjugated
diene rubbery core or a predominately crosslinked
acrylate rubbery core and one or more shells
polymerized thereon and derived from monoalkenyl arene
and/or acrylic monomers alone or, preferably, in
combination with other vlnyl monomers.
More particularly, the first or core phase of the
core-shell copolymer preferably comprises polymerized
conjugated diene units of one or more conjugated dienes
alone or copolymerized with units of a vinyl monomer or
mixture of vinyl monomers. Suitable conjugated dienes
for use in said core phase include butadiene, isoprene,
l,3-pentadiene and the like. Illustrative of the vinyl
monomers copolymerizable therewith include the vinyl
aromatic compounds such as styrene, alpha-methylstyrene,
vinyl toluene, para-methylstyrene and the like; esters of
acrylic and methacrylic acid, including for example
methyl acrylate, ethy'l acrylate, blltyl acry:Late, methyl
methacrylate and ethyl methacrylate; and ullsaturatecl
aliphatic nitr:iles such as acry:Lonitri:Le, methacrylo-
nitrile and the like. The core of said copolymer should
comprise at least about 50 percent by weight of the
conjugated diene. Preferred grafted core-shell
copolymers for use here:in comprise a core of p~lybuta-
diene homopolymer or a styrene-butadiene copolymer
~ 24 - 8CV 42~4
comprising about 10 to 50% by weight styrene and about
90 to 50% by weight of butadiene, having a molecular
weight of from about 150,000 to about 500,000. The
core phase may also include a cross-linking monomer,
more particularly described below.
On the other hand, as the cross-linked
elastomeric trunk polymer for use in preparing graft-
copolymer of the present invention, a homopolymer of a
C4 to Clo-alkyl acrylate or a copolymer containing
not less than 50% by weight of the alkyl acrylate is
utilized, particularly, butyl acrylate, octyl acrylate
and the like. The rubber-like properties of the thus
prepared graft-copolymer is exhibited only in the case
of using not less than 50% by weight of the alkyl
acrylate, the graft copolymer containing less than 50%
by weight of the alkyl acrylate being undesirable
because of the poor pliability of the composition of
polyester-block copolymer prepared by using the
graft-copolymer. As the monomer which is
copolymerized with the alkyl acrylate in an amount of
less than 50% by weight, aromatic vinyl monomers such
as styrene, alpha-methylstyrene and the like, alkyl
methacrylates such as methyl methacrylate, ethyl
methacrylate and the like, unsaturated aliphatic
nitriles such as acrylonitrile, methacrylonitrile, and
the like, and diene compounds such as butadiene,
chloroprene and the like are mentioned.
The final or shell phase of the copolymer
comprises polymerized units of a monoalkenyl arene
and/or esters of acrylic or methacrylic aC.i.tl, a:lolle~ or
copolyme~rize(l with olle or more other viny:L monomers
wherein at least 10 mole percent preferably at least
40 mole percent, of the graft component is derived
from the monoalkenyl arene monomer and/or esters of
acrylic or methacrylic acid. Preferred monoalkenyl
arene monomers are styrene, alpha-methylstyrene,
~.
i~ ~,3~3 ~
- 25 - 8CV 4284
para-methylstyrene and the like, most preferably
styrene. Preferred esters of acrylic and methacrylic
acid include ethyl acrylate, methyl acrylate, butyl
acrylate, methyl methacrylate, ethyl methacrylate,
butyl methacrylate and the like most preferably methyl
methacrylate. Addltional monomers that may be
copolymerized therewith include unsaturated aliphatic
nitrile such as acrylonitrile and methacrylonitrile
and vinyl halides such as vinyl chloride and vinyl
bromide. Especially preferred shells particularly for
the conjugated diene rubbery core polymers are those
derived from polymerized units of styrene and/or
methyl methacrylate wherein each is present in an
amount of from 10 to 90 mole %. Additionally, these
shells may also have copolymerized therewith a minor
amount, preferably less than 10 mole % of one or more
of the other aforementioned monomer units. These
shells may also be used with the acrylate rubbery core
however, where such a core is employed it is preferred
to have a polymethyl methacrylate shell or a
polymethyl methacrylate shell copolymerized with a
minor amount, preferably less than 10 mole percent, of
an additional monomer. As with the core, the shell
phase may also include a cross-linking monomer as
discussed more fully below.
Optionally, the core-shell copolymers may further
comprise one or more cross-linked or non-cross-linked
intermediate layers which is grafted to the core and
upon which the final shell layer is ~raftecl, derived
from one or more polymer.ized viny:L monomer. Suitable
vinyl monomers Eor use in these intermediate layers
include but are not limited to those mentioned above,
especially polystyrene. Where such intermediate
layers are present in the core-shell copolymer and are
derived from at least 10 mole % of a monoalkenyl arene
monomer, the final or shell phase may comprise up to
- 26 - 8CV 4284
and including 100 mole % monomer units which are not
monoalkenyl arene units. Especially preferred in such
instances are multi-phase copolymers wherein the
intermediate phase comprises polystyrene and the final
stage comprises polymethylmethacrylate.
As mentioned each of the individual stages of the
core-shell copolymers may contain a cross-linking
monomer which may serve not only to cross-link the
units of the individual layers but also graft-link the
shell to the core. As the cross-linking agent for use
in preparation of the core-shell copolymers, those
which copolymerize smoothly with the monomer in the
respective stages of the reaction should be selec~ed.
Representative cross-linking agents include, but are
not limited to aromatic polyfunctional vinyl compounds
such as divinyl benzene, trivinyl benzene, divinyl
toluene and the like; di and tri- methacrylates and di
and triacrylates of polyols represented by
monoethylene-, diethylene- and triethylene glycols,
1,3-butanediol and glycerin allyl esters of
unsaturated aliphatic carboxylic acid such as allyl
acrylate, allyl methacrylate and the like and di- and
triallyl compounds such as diallyl phthalate, diallyl
sebacate, triallytriazine and the li]ce are mentioned.
While the amount of cross-linking agent employed
is from about 0.01 to 3.0% by weight based on the
monomer charge for each stage of the reaction,
generally, the total amount of cross-linking agent in
the final graft copolymer will preEerably be less tha
3.0 weight percent.
The core-shel:L copolymers su:itable~ for use herein
generally comprise from about 50 to about 90 weight
percent of the core and from about 10 up to 50 weight
percent of the graft or shell phase. Where an inter-
mediate phase or layer is present in the graft copoly-
mer the shell and intermediate phase will each com-
3~
- 27 - 8C~ ~2~4
prise from about 5 to about 25 weight percent of the
copolymer.
In a most preferred embodiment, where a core-shell
copolymer is employed as the modifier resin it is
desirable to precompound the core-shell copolymer with
the poly(butylene terephthalate) or a portion thereof.
As identified by Yusa et al. (U.S. 4,442,262~, the use
of core-shell copolymers in general with copolyether-
esters results in the occurrence of surface roughness
and fisheyes. Applicant has now surprisingly found that
otherwise unsuitable core-shell copolymers may be
employed without the occurrence of fisheye if the core-
shell copolymer is precompounded with the poly(butylene
terephthalate). Equally surprising is the finding that
the use of the pre-compounded core-shell copolymer
results in composition having unexpectedly improved
physical properties as compared to those compositions
wherein the poly(butylene terephthalate) and core-shell
copolymers were not precompounded. In practice most any
ratio of core-shell copolymer to poly(butylene
terephthalate) may be used; however, it is preferred
that the ratio of 4:1 to 1:4, most preferably 3:2 to
2:3, be employed to provide greater dispersibility of
the core-shell copolymer in the final composition.
Finally, while the foregoing is concerned with
precompounding of the core-shell copolymer, the concept
of precompounding is equally applicable to any of
modifier resins (C).
The core-shell graft copolymer.s for ~se in th(~
present invent:ion are prep(lrecl by tlle convent:iorlal
method of em~lls:ion polymerization, however, in an
alternative method, graft copolymerization may be
carried out after suitably coagulating the latex of
cross-linked trunk polymer for ad~usting the size of
the latex particles of the trunk polymer.
~24~3~.9~
- 28 - 8CV 428~
Also, during polymerization the monomeric
components used in the graft copolymerization may be
brought into reaction in one step, or in multiple steps
while supplying them in portions of suitable ratio of
the present invention between the components.
Specific examples of suitable core-shell craft
copolymers and the production thereof are disclosed in
for example U.S. Patent Numbers 4,180,494; 4,034,0~3;
4,096,202; 3,808,180 and 4,292,233. Commercially
available grafted core-shell copolymers for use herein
include the KM653TM and KM611TM butadiene based
core-shell copolymers and the KM330TM acrylate based
core-shell copolymers from Rohm and Haas Chemical
Company.
Optionally, the modifier combination (B) may
further comprise clay filler. Clays are well known and
widely available commercially. Preferred clays are the
crystalline and paracrystalline clays. Especially
preferred are the crystalline clays, most preferably the
Kaolin clays. The clays, partlcularly the Kaolin clays,
may be in the hydrous form or in the calcined, anhydrous
form. Exemplary of commercially available, suitable
clays there may be given the clays available under
WhitexTM and TranslinkTM from Freeport Kaolin.
Additionally, it is preferred, although not
required, to utllize clay fillers which have been
treated with a titanate or silane coupling agent.
Exemplary of such coupling agents there may be given
vinyl tris 2-methoxy ethoxy silane and gamma-amino-
propyl triethyoxy si:Lane (A-lL00TM, Un:io~l Carbide).
The formulation oL the composition of the present
invention may vary widely depending upon the desired
physical properties of and the anticipated end use
application for the final composition. Generally any
combination of components A through C may be employed:
- 29 - 8CV 4284
where component D, clay filler, is employed it should
comprise no more than 50% by weight of the total
composition.
Typically, the compositions of the present
invention will comprise, in parts by weight, from about
90 to about 5 parts A, from about 5 to about 90 parts B,
from about 5 to about 35 parts C and from 0 up to about
30 parts D. While compositions of greater than about 50
parts by weight of component B are especially suited for
applications re~uiring very stiff or rigid materials, an
especially preferred class of composition within the
scope of the present invention are those which have the
excellent stress-strength characteristics of the more
rigid compositions yet retain excellent flexibility.
Such compositions will generally comprise, in parts by
weight, from about 90 to about 40 preferably from about
70 to about 45 parts component A; from about 5 to about
55, preferably from about 20 to about 45 parts,
component B; from about 5 to about 30, preferably from
about lO to about 20 parts component C; and, optionally
up to about 25, preferably up to about 15, parts
component D.
While the compositions of this inventlon possess
many desirable properties, it is sometimes advisable and
preferred to further stabilize certain of the
compositions against thermal or oxidative degradation as
well as degradation due to ultraviolet light. This can
be done by incorporating stabilizers into the blend
compositions. Satisfactory stabilizers compr:ise phenols
and their derivatives, amines and the:ir deri.vat:ives,
compounds containing both hydroxyl and amine groups,
hydroxyazines, oximes, polymeric phenolic esters and
salts of multivalent metals in which the metal is in its
lower state.
Representative phenol derivatives useful as
stabilizers include 3,5-di-tert-butyl-4-hydroxy hydro-
j,~
3~3~:~
- 30 - ~CV ~284
cinnamic triester with 1,3,5-tris-(2-hydroxyethyl-s-
triazine-2,4,6-(lH, 3H, 5H) trione; 4,4'-bis(2,6-
ditertiary-butylphenyl); 1,3,5-trimethyl-2,4,6-tris-
(3,5-ditertiary-butyl-4-hydroxylbenzyl)benzene and 4,~'-
butylidene-bis(6-tertiary-butyl m-cresol). Various
inorganic metal salts or hydroxides can be used as well as
organic complexes such as nickel dibutyl dithiocarbamate,
manganous salicylate and copper 3-phenyl-salicy:late.
Typically amine stabilizers include N,N'-bis(beta-
naphthyl)-p-phenylenediamine; N,N'-bis(1-methylheptyl)-p-
phenylenediamine and either phenyl-beta-napththyl amine or
its reaction products with aldehydes. Mixtures of
hindered phenols with esters of thiodipropior.ic acid,
mercaptides and phosphite esters are particularly useful.
~dditional stabilization to ultraviolet light can be
obtained by compounding with various UV absorbers such as
substituted benzophenones and/or benzotriazoles.
The compositions of the present invention may be
prepared by any of the well known techniques for
preparing polymer blends or admixtures, with extrusion
blending belng preferred. Suitable devices for the
blending include single screw extruders, twin screw
extruders, internal mixers such as the Bambury Mixer,
heated rubber mills (electric or oil heat) or Farrell
continuous mixers. In~ection molding equipment can also
be used to accomplish blending just prior to molding, but
care must be taken to provide sufficient time and
agitation to insure uniform blending prior to moLding.
Alternatively, the compos:itiolls Or t~lC? prC`';ellt
invention may be prepared by dry blellcli~ the components
prior to ex-trusion or inject:ion mo:Lding. Finally, as
mentioned, any two or more of the components, preferably
at least B and C where C is a core-shell copolymer, may be
pre-compounded prior to compounding with the copolyether-
imide ester.
.~,$'~, .,
- 31 - 8CV ~2~4
The polymer compositions prepared in accordance with
the present invention are suitable for a broad range of
applicatlons~ These compositions manifest excellent
physical attributes making them especially suited for
applications requiring excellent stress-strength
characteristics and low temperature impact strength yet
maintaining good flexibility.
The following examples are given as exemplary of the
present invention and are not to be construed as limiting
thereto.
Detailed Description of the Preferred Embodiments
The following ASTM methods were used in determining
the physical characteristics of the compositions:
Flexural Modulus ASTM D790
Tensile elongation ASTM D638
Notched Izod ASTM D256
Unnotched Izod ASTM D256
Other physical properties were determined in
accordance with procedures known and accepted in the art.
Dynatup is a measure of stress-strength properties of the
composition and is expressed as Exam/Etotal whereln Exam
is the maximum energy the standard part can withstand
under deflection before permanent deformation (i.e.
non-recoverable deflection) and Etotal is the total energy
the part can withstand before mixture.
All compositions were prepared by melt blending the
thermoplastic elastomer with the thermoplastic polyester
in a Prodex single screw extruder. Further, all
compositions contained 0.5 - 0.7 parts hy weiclht
stahilizer.
PEIE A-C
PEIE A-C are polyetherimide ethers prepared ~rom
butanediol, dimethylterephthalate, poly(propylene ether)
diamine (number average MW 2000) and trimellitic anhy-
~. ~
- 32 - 8CV 4284
dride, wherein the weight ratio of dimethyltere-
phthalate to diimide diacid was such as to produce
polymers of flexural modulus as follows:
PEIE A 10,000 psi
PEIE B 15,00~ psi
PEIE C 25,000 psi
Examples 1 and 2 Comparative Examples A-C
Two series of compositions employing two
different modulus copolyetherimide ester were
prepared. Each series demonstrates polyester modified
copolyetherimide esters and such compositions further
containing a copolymer as taught by the present
invention. The specific formulations and the physical
properties thereof are presented in Table l.
As is apparent from the results shown in Table 1,
the compositions of the present invention have
markedly superior low temperature impact strength as
compared to polyester modified copolyetherimide
esters. Additionally, by practicing the present
invention, compositions are attainable which have
excellent flexibility, as evident by the lower
flexural modulus, combined with the excellent impact
properties.
Examples 3 - 19
A second series of compositions within the scope
of the present invention were prepared demonstrating
the broad scope of the teachings hereof. The specific
formulations and the physical properties thereof were
as presented in Table 2. As is apparent composit:ions
of excellent physical propertles are atta:inclble within
a wide variation of formulations.
~'
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- 33 ~ 8CV 4284
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~34 ~ 8CV 4284
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8CV 04284
- 35 -
Examples 2n-23
An additional series of compositions were pre-
pared further demonctrating the ~readth of the present
inventicn. These compositions e~emplify compositions
within the scop~ of the present invention in which
various copolymer modifier resins w~re employed. The
specific formulations and the properties of these
compositions were as shown in Table 3.
Examples 24-37
A final series of examples were prepared demon-
strating clay filled comp~sitions having reduced hea~
sag. These compositions and the physical properties
thereof were aE presented in Table 4.
Obviouslv, other modifications will suggest the~-
seives to those Ekilled in the art in light of theabove, detailed description. ~.11 such modifications
are within the full intended scope of the present
lnvention as defined by the appended claims.
989'~L
- 36 - ~ CV 4284
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- 37 - ~3CV 4284
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