Note: Descriptions are shown in the official language in which they were submitted.
2~ ,37
-1- 336-2220 (8CV-5048/83)
POLY(AL~Y~ENE CYCLOaEX~N~DICARBOXY~AT~)-
POLYCARBONATE CO~POSITIONS AND ~ODIPICATIO~S
CROSS-R~F~RE~C~ TO RELaTE~ APPL$CATIONS
This application is related to the following
commonly owr.ed, concurrently filed U.S. patent applications.
SERIAL ATTY ' S SUBJECT
NO. DOC~ET MATTER APPLICANT(S)
_ _ _ _ . . _ . _
336-2221 Modifications of Poly- W.F.H. Borman
(8CV-5084/ (alkylene cyclohexane- N-I Liu
_ 10 5118) dicarboxylate) Blends
336-2222 Poly(alkylene cyclohexane- ~Y.F.H. Borman
(8CV 5125) dicarboxylate)-(alkylene
terephthalate) Copolyesters
336-22~3 Poly(alkylene cyclohexane- W.F.H. Borman
(8CV-5117) dicarboxylate) Binary 31ends N-I Liu
FIELD OF ~e IDVE~TION
This invention relates to compositions comprised of
(A) polyester resins comprising the reaction product of at
least one straight chain, branched, or cycloaliphatic C2-C10
alkane diol or a chemical equivalent thereof, and at least
one cycloaliphatic diacid or a chemical equivalent thereof;
and (B) a polycarbonate resin, as well as to such compositions
modified by the addition of an effective modulus modifying
amount of a core-shell mul~i-stage polymer h~ving a rubbery
core derived from an acrylate or (meth)acrylate, a diene or a
mixture of any of the foregoing and a vinyl-based polymer ~r
co-polymer outer shell or of a vinyl cyanide-conjugated
diolefin-alkyl aromatic AB~-type terpolymer. Also included
are modified compositions further comprising an additional
polyester resin which may be the same as or different than
the first polyester resin as well as filled and/or flame
retardant compositions.
These unmodified compositions are homogeneous and
retain transparency. All of the compositions of the present
invention, both modified and unmodified, exhibit significantly
2as~,~?3
-2- 336-2220 (8CV-5048/83)
higher stiffness than that of the individual components,
enhanced melt flow, and retain excellent impact strength.
BAC~GRO~MD OF T~ I~V~TION
.
Novel compositions comprising a polyester resin
which i5 the reaction product of at least one straight chain,
brancAed, or cycloaliphatic C2-C10 alkane diol or a chemical
equivalent thereof and at least one cycloaliphatic diacid or
a chemical equivalent thereof combined with a polycarbonate
resin have been discovered which are homogeneouc and trans-
parent, have significantly higher stiffness measured as fl~xura
modulus than the modulus of either component, and retain
excellent impact strength at a wide range of temperatures.
Modified compositions comprising the compositions
above and an appropriate core-shell multi-stage polymer
lS modifier or A~-type polymer modifier as well as such
modified compositions containing an additional polyester
resin, retain superior stiffness and impact properties as
well.
Weatherable, UV radiation resistant, solvent
resistant, resilient, high impact polymers have great
application in the manufacture of molded or thermoformed
products such as automobile external parts, lawn and garden
equipment, and sporting goods.
Crystallizable polyesters of cycloaliphatic diacids
or derivatives thereof with aliphatic and/or cycloaliphatic
diols have relatively high melting points and are quite UV
resistant as they do not appreciably absorb near-UV light.
Many of these polyesters were explored for use as hot melt
adhesives. See, Jackson et al., J. Applied Polymer Review,
Vol. 14, 685-98, (1970); U.S. Patent No. 3,515,628.
Wilfong, J. Polymer Sci., Vol. 54, 385-410 (1961),
referred to polyesters of hexahydro terephthalic acid, the
cis-/tran~-mixture of cyclohexanedicarboxylic acids obtained
by the hydrogenation of terephthalic acid. See, Caldwell et
al, U.S. Patent No. 2,891,830 including poly(neopentyl
.: .
3 Jl
-3- 336-2220 (8Cv-5048/83)
cyclohexane dicarboxylate); Carpenter, Journal of Soc. Dyers
and Colorists, Vol. 65, 469 (1941).
Kibler et al, U.S. Patent No. 2,901,466, disclose
linear polyesters and polyester-amides prepared by condensing
cis- and/or trans-1,4-cyclohexanedimethanol with one or more
bifunctional reactants, which because of high melting
temperatures, are advantageous for the preparation of fibers
for use in fabrics and films for use as support for
photographic emulsion
Friction activatable solvent-free adhesives
~' comprising a thermoplastic linear polyester derived from one
or more saturated aliphatic dicarboxylic acid and/or aromatic
dicarboxylic acids and one or more saturated aliphatic diols,
a tackifier, and a plasticizer are disclosed by Wayne et al,
U.S. Patent No. 4,066,600.
Scott, U.S. Patent No. 4,125,572, describes a
thermoplastic molding composition and articles molded
therefrom that retain optical clarity comprising a
polycarbonate, a poly(l,4-butylene terephthalate), and a
copolyester of an aliphatic or cycloaliphatic diol and a
mixture of terephthalic and isoterephthalic acids. Scott
discloses that blends of polycarbonate and polyalkylene
terephthalate, as described in U.S. Patent No. 3,218,372,
~end to lose their transparency when the amount of
poly(l,4-butylene terephthalate) is greater than about 10
percent or when they are heat aged.
Cohen et al, U.S. Patent No. 4,257,937, discuss
compositions comprising a poly(l,4-butylene terephthalate)
resin modified by a combination of a polyacrylate resin and
an aromatic polycarbonate resin.
Jackson et al, U.S. Patent No. 4,327,206, disclose
a process for the preparation of poly(l,4-cyclohexane-
dicarboxylate~ polyesters with high trans-isomer content
comprising heating, in the presence of a suitable catalyst,
,
`
.
.
2 ~r V'~ r~ I
-~- 336-2220 (~CV-5048/83)
an ester of trans-1,4-cyclohexanedicarboxylic acid and a
diacyl derivative of an aromatic diol.
Avakian, U.S. Patent No. 4,555,540, discloses flame
retardant blends of aromatic polycarbonates and polyesters
incorporating certain phosphorous containing materials for
stability.
Nelson, U.S. Patent No. 4,760,107, discloses resin
compositions comprising at least one aromatic polycarbonate
resin, at least one polyester resin and a mixture of at least
one polyol and at least one epoxide, the latter being
necessary in the mixture to combat yellowing.
Copending application, DeRudder, U.S. Serial No.
06/947,671 filed on December 30, 1986, discloses low
temperature impact resistant compositions of an aromatic
polycarbonate resin, a polyester resin derived from a
cyclohexane dimethanol and a hexacarbocyclic dicarboxylic
acid, and an impact modifier comprising a core-shell acrylate
(co-) polymer. The polyesters of the DeRudder compositions
differ from alkane diol cyclohexanedicarboxylate-based resins
of the present invention.
Copending application, DeRudder et al, U.S. Serial
No. 07/271~222 filed on November 14, 1988, now allowed,
discloses in Example 19 a comparative composition comprising
poly(l,4-butylene terephthalate), poly(bisphenol-A carbonate)
and ACRYLOID- KM 653, also known as PARALOID' EXL 3691 tRohm
~aas Company) which did not have acceptable gloss properties.
Copending applications, U.S. Serial Nos. 07/271,246
filed on November 14, 1988,- and 07/356,356 filed on May 29,
1989, disclose polyester/polycarbonate blends modified by
combinations of at least two different organosiloxane-based
polyorganosiloxane/polyvinyl-based or diene rubber-based
graft copolymers. However, the polyester resins of the
present invention differ because they comprise alkane
diol/cyclohexanedicarboxylate-based units.
.
-5- 336-2220 ( ~CV-5048/83 )
A shortcoming of the previous compositions ha~ been
their inability to withstand gamma-radiation without the
necessary addition of property enhancers at the sacrifice of
tensile, flexural, and impact properties along with a loss of
transparency.
Many of these shortcomings are overcome by the
various embodiments of the compositions of the present
invention. The unmodified compositions of the present
invention are homogeneous and transparent, and all of the
compositions of the present invention exhibit desirable
stiffness and impact properties.
S~MM~R~ OF T~E I~V~TION
According to the present invention, there are
provided compositions comprising ~A) a first polyester resin
comprising the reaction product of (a) at least one straight
chain, branched, or cycloaliphatic C2-C10 alkane diol or
chemical equivalent thereof; and (b) at least one
cycloaliphatic diacid or chemical equivalent thereof; and (3)
an aromatic polycarbonate resin, an aromatic polyester
carbonate resin, an aromatic dihydric phenol sulfone
carbonate resin, or a mixture of any of the foregoing.
In a preferred embodiment, polyester (A) is the
reaction product of (a) at least one straight chain oc
branched C2-C10 alkane diol and (b) as above.
Also contemplated by the invention are compositions
as described above further comprising (C) an effective
modulus modifying amount o-f (a) a core-shell multi-stage
polymer having a rubbery core derived from an acrylate or
(meth)acrylate, diene or a mixture of any of the foregoing
and a vinyl-based polymer or copoly~er outer shell; (b) a
vinyl cyanide-conjugated diolefin-alkyl aromatic terpolymer;
or (c) a combination of (a) and (b). Additionally compositions
comprising components (A), (~), and (C) above and (D) an
additional polyester resin which may be same as or different
than (A) are provided.
~5r~7
-6- 336-2220 (8CV-5048/83)
In preferred embodiments, the compositions consist
essentially of components (A) and (B), components tA), (B),
and (C), or components (A), (B), (C), and (D).
In another embodiment, component (A)(a) can
comprise at least one straight chain or branched C2-C10
alkane diol or chemical equivalent thereof.
DerAILED D~SCRIPTION OF Tse INV~NTION
The diols useful in the preparation of the first
polyester resins (A) of the present invention are straight
chain, branched, or cycloaliphatic but preferably straight
chain or branched alkane diols and may contain 2 to 10 carbon
atoms. Examples of such glycols include but are not limited
to ethylene glycol; propylene glycol, i.e., 1,2- and
1,3-propylene glycol; butane diol, i.e., 1,3- and 1,4-butane
lS diol; diethylene glycol; 2,2-dimethyl-1,3-propane diol;
2-ethyl, 2-methyl, 1,3-propane diol; 1,3- and 1,5-pentane
diol; dipropylene glycol; 2-methyl-1,5-pentane diol;
1,6-hexane diol; 1,4-cyclohexane dimethanol and particularly
its Ci8- or trans-enantiomers; triethylene glycol; 1,10-decane
diol; and mixtures of any of the foregoing. Particularly
preferred is l,4-butanediol. If a cycloaliphatic diol or
chemical equivalent thereof and particularly 1,4-cyclohexane
dimethanol or chemical equivalent thereof are to be used as
the diol component, it is preferred that a mixture of cis to
trans enantiomer thereof, ranging from 1 to 4 to 4 to 1, and
preferably, a ratio of 1 to 3 is used.
Chemical equivalents of these diols include esters
and ethers such as dialkyl esters, diaryl esters, polytetra-
methylene oxide, and the like.
The diacids (A)(b) useful in the preparation of the
polyester resins (A) of the present invention are
cycloaliphatic diacids. This is meant to include carboxylic
acids having two carboxyl groups each of which is attached to
a saturated carbon in a saturated ring. A preferred diacid
is 1,4-cyclohexanedicarboxylic acid and most preferred is
'
-7- 336-222C (8CV-5048/83)
trans-1,4-cyclohexane dicarboxylic acid as further explained
below.
Cyclohexanedicarboxylic acids and their chemical
equivalents can be prepared, for example, by the hydrogenation
of cycloaromatic diacids and corresponding derivatives such
as isophthalic acid or terephthalic acid in a suitable
solvent, water or acetic acid at room temperature and at
atmospheric pressure using suitable catalysts such as rhodium
supported on a suitable carrier of carbon or alumina. See,
Freifelder et al, Journal of Organic ChemistrY, 31, 3438
(1966); U.S. Patent Nos. 2,675,390 and 4,754,064. They may
also be prepared by the use of an inert liquid medium in
which a phthalic acid is at least partially soluble under
reaction conditions and a catalyst of palladium or ruthenium
in carbon or silica, or by the hydrogenation of an alkali
salt of trimelletic anhydride. See, U.S. Patent Nos.
2,888,484 and 3,444,237.
Typically in the hydrogenation, two enantiomers are
obtained in which the carboxylic acid groups are in cis- or
trans- positions. The cis- and trans-enantiomers can be
separated by crystallization with or without a solvent, for
example, n-heptane, or by distillation. The cis-enantiomer
tends to blend better; however, the trans-enantiomer has
higher melting and crystallization temperatures and is
especially preferred. Mixtures of the cis- and trans-
enantiomers are useful herein as well, and preferably when
such a mixture is used, the trans-enantiomer will comprise at
least about 75 parts by weight and the cis-enantiomer will
comprise the remainder based upon 100 parts by weight of
cis- and trans-enantiomer combined.
When the mixture of enantiomers or more than one
diacid is used, a copolyester or a mixture of two polyesters
for use as component (A) may be used.
Chemical equivalents of the diacids include esters,
e.g., dialkyl esters, diaryl esters, anhydrides, acid
?J~ ,37
-8- 336-2220 (8CV-5048/83)
chlorides, acid bromides, and the like. The preferred
chemical equi~alents comprise the dialkyl esters of the
cycloaliphatic diacids, and the most preferred chemical
equivalent comprises the dimethyl ester of the acid,
particularly dimethyl-trans-1,4-cyclohexanedicarboxylate.
Dimethyl-1,4-cyclohexanedicarboxylate can be
obtained by ring hydrogenation of dimethylterephthalate, and
two enantiomers having the carboxylic acid groups in the cis-
or trans- positions are obtained. The enantiomers can be
separated as above, and the trans-enantiomer is especially
preferred for the reasons above. ~ixtures of the enantiomers
are suitable as explained above and preferably in the amounts
as explained above.
The polyester resins (A) of the present invention
are typically obtained through the condensation or ester
interchange poly~erization of the diol or diol equivalent
co~ponent (A)(a) with the diacid or diacid equivalent
component (A)~b) and have recurring units of the
formula
~ o o
to_R_o_c_Rl_ct
wherein R represents an alkyl or cycloalkyl radical
containing 2 to 10 carbon atoms and which is the residue of a
straight chain, branched, or cycloaliphatic alkane diol
having 2 to 10 carbon atoms or chemical equivalents thereof;
and
Rl is a cycloaliphatic radical which is the decarboxylated
residue derived from a cycloaliphatic diacid or chemical
equivalent thereof. They particularly have recurring units
of the formula
t c~2 c~32_CH2_c~2_0_c~c~
., . ~, . .
~ J ;-' ~ 7 i
-g- 336-2220 (8CV-5048/83)
wherein R from above is derived from 1,4-butane diol and
wherein Rl from above is a cyclohexane ring derived from
cyclohexanedicarboxylate or a chemical equivalent thereof and
is selected fron the cis- or trans-enantiomers thereof.
S All such polyesters can be made following the
teachings of, for example, U.S. Patent Nos. 2,465,319 and
3,047,539.
The reaction is 3enerally run with an excess of the
diol component and in the presence of a suitable catalyst
such as a tetrakis(2-ethyl hexyl)titanate, in a suitable
a~ount, typically about 20 to 200 ppm of titanium based upon
the final product.
The polycarbonate resin component (B) can comprise
non-aromatic as well as aromatic forms. With respect to
aromatic polycarbonate resins, these can be made by those
skilled in this art or can be obtained from a variety of
commercial sources. They may be prepared by reacting a
dihydroxy compound such as a dihydric phenol and/or a
polyhydroxy compound with a carbonate precursor, such as
phosgene, a haloformate or a carbonate ester such as a
diester of carbonic acid. Typically, they will have
recurring structural units of the formula
~ o - A- O -C ~
wherein A is a divalent aromatic radical of the dihydric
phenol employed in the polymer producing reaction. Preferably,
the aromatic polymers have an intrinsic viscosity ranging
from 0.30 to 1.0 dl/g (measured in methylene chloride at
25C). Dihydric phenols are meant to include mononuclear or
polynuclear aromatic compounds containing two hydroxy
radicals, each of which is attached to a carbon atom of an
aromatic nucleus. Typically, dihydric phenols include
2,2-bis-(4-hydroxyphenyl)propane; 2,2-bis-(3,5-dimethyl-4-
hydroxyphenyl)propane; 4,4'-dihydroxydiphenylether;
~'J ~3 C~ 3 7
-10- 336-2220 (8CV-5048/83)
bist2-hydroxyphenyl)methane; mixtures thereof and the like.
The preferred aromatic carbonate polymer as component (8) is
a homopolymer derived from 2,2-bis(4-hydroxyphenyl)propane-
(bisphenol-A), poly(bisphenol-A carbonate).
Poly(ester-carbonate) resins for use in the
invention are known and can be obtained commercially.
Generally, they are copolyesters comprising recurring
carbonate group~:
~0--C -07--
carboxylate groups:
O ~ .
~C-O~
and aromatic carbocyclic groups in the linear polymer chain,
in which at least some of the carboxylate groups and at least
some of the carbonate groups are bonded directly to ring
carbon atoms of the aromatic carbocyclic groups. ~hese
poly(ester carbonates), in general, are prepared by reacting
a difunctional carboxylic acid, such as phthalic acid;
isophthalic acid; terephthalic acid; homophthalic acid; o-,
m-, and p-phenylenediacetic acid; the polynuclear aromatic
acids, such as diphenic acid; 1,4-naphthalic acid; mixtures
of any of the foregoing; and the like, with a dihydric phenol
and a carbonate precursor,-of the types described above. A
particularly useful poly(ester carbonate) is derived from
bisphenol-A, isophthalic acid, terephthalic acid, or ~
mixture of isophthalic acid and terephthalic acid, or the
reactive derivatives of these acids such as terephthaloyl
dichloride, isophthaloyl dichloride, or a mixture thereof,
and phosgene. The molar oroportions of dihydroxy diaryl
units to benezenedicarboxylate units to carbonate units can
range from 1:0.30-0.80:0.70-0.20 and the molar range of
2 ~ 3 7l
~ 336-2220 (8CV-5048/a3)
terephthalate units to isophthalate units can range from 9:1
to 2:8 in this preferred family of resins.
The aromatic dihydric phenol sulfone resins useful
as component (B) are a family of resins which can be made by
those skilled in this art. For example, homopolymers of
dihydric phenol, and a dihydroxydiphenol sulfone and a
carbonate precursor as well as copolymers of a dihydric
phenol and a carbonate precursor can be made according to the
description in Schnell et al, U.S. Patent No. 3,271,367. A
preferred material is made by polymerizing bis-(3,5-dimethyl-
4-hydroxy phenyl) sulfone, alone or especially in combination
with bisphenol-A with phosgene or a phogene precursor, in
accordance with the description in Fox, U.5. Patent No.
3,737,409. Especially preferred is a copolymer made by
reacting 40 to 99 weight percent of the sulfone and 1 to 60
weight percent of the bisphenol with phosgene.
Mixtures of any of the foregoing polycarbonate
resins are suitable for use as component (B) as well.
The modifiers (C)(a) of the present invention
comprise core-shell multi-stage polymers. The modifier core
can comprise an acrylate or a (meth)acrylate, a diene, or a
mixture of the foregoing.
In a preferred embodiment, the core is polymerized
from a Cl to C6 alkyl acrylate resulting in an acrylic rubber
coce having a Tg below about 10C and preferably it contains
cross-linking monomer and/or graft-linking monomer. The
preferred acrylate is n-butyl acrylate.
The cross-linking monomer is a polyethylenically
unsaturated monomer having a plurality of addition
polymerizable reactive groups all of which polymerize at
substantially the same rate of reaction. Suitable
cross-linking monomers include polyacrylic and poly(methacryli_
esters) of polyols such as butylene diacrylate and
dimethacrylate, trimethylol propane trimethacrylate and the
like, di- and tri-vinyl benzene, vinyl acrylate and
.
I
-12- 336-2220 (8CV-5048/83)
methacrylate and the like. The preferred cross-linking
monomer is butylene diacrylate.
The graft-linking monomer is a polyethylenically
unsaturated monomer having a plurality of addition
polymerizable reactive groups, at least one of which
polymerizes at a substantially different rate of polymerization
from at least one other of said reactive groups. The
function of the graft-linking monomer is to provide a
residual level of unsaturation in the elastomeric phase,
particularly in the latter stages of polymerization, and
consequently, at or near the surface of the elastomer
particles. When the rigid thermoplastic shell stage is
subsequently polymerized at the surface of the elastomer, the
residual unsaturated, addition polymerizable reactive group
contributed by the graft-linking monomer participates in the
subsequent reaction so that at least a portion of the rigid
shell stage is chemically attached to the surface of the
elastomer.
Among the effective graft-linking monomers are
allyl group-containing monomers of allyl esters of
ethylenically unsaturated diacids, such as allyl acryllte,
allyl methacrylate, diallyl maleate, diallyl fumarate,
diallyl itaconate, allyl acid maleate, allyl acid fumarate,
and allyl acid itaconate. Somewhat less preferred are the
diallyl esters of polycarboxylic acids which do not contain
polymerizable unsaturation. The preferred graft-linking
monomers are allyl methacrylate and diallyl maleate. The
final or outer shell stage monomer can be comprised of Cl-C16
methacrylate, styrene, acrylonitrile, alkyl acrylates, alkyl
methacrylate, dialkyl methacrylate, and the like. Preferably,
the final outer shell stage monomer includes a major portion
of a Cl-C4 alkyl methacrylate.
One type of preferred core-shell multi-stage
polymer (C)(a) has only two stages, the first stage or core
being polymerized from a monomer system comprising butylene
~ ~ ~ '3 ~ 3 7 !
-13- 336-2220 (aCV-5048/83)
diacrylate as a cross-linking agent, allyl methacrylate or
diallyl maleate as a graft-linking aqent and with a final
stage or outer shell of polymerized methyl methacrylate. A
preferred two stage core-shell multi-stage polymer of this
type is commercially available under the tradename, ACRYL~ID-
KM ~30, also known as PARALOID- EXL 3330, from Rohm & Haas
Company.
These core-shell multi-stage polymers are prepared
sequentially by emulsion polymerization techniques wherein
each successive outer stage or shell coats the previous stage
polymer. By way of illustration, the monomeric Cl-C6
acrylate, the cross-linking monomer and the graft-linking
monomer are copolymerized in water in the presence of a
free-radical generating catalyst and a polymerization
regulator which serves as a chain transfer agent at a
temperature on the order of from 15C to 80C. The first
elastomeric phase is formed in situ to provide a latex of the
core copolymer.
Thereafter, the second rigid thermoplastic phase
monomers are added and are emulsion polymerized with the core
copolymer latex to form the core-shell multi-stage polymers.
More detailed description of the preparation of the
acrylate-based core-shell multi-stage polymers for use herein
as component (C) are found in U.S. Patent Nos. 4,034,013 and
4,096,202.
In another preferred embodiment, the amorphous
copolymer resin for use herein as component (C)(a) comprises
a diene~based and preferably a butadiene-based core-shell
multi-stage polymer resin. These diene-based core shell
multi-stage polymers generally comprise a conjugated
diene-based core, an intermediate graft shell of polymerized
vinyl monomer units and a final or outer shell comprised of a
polymerized monomeric component selected from the group
consisting of an alkyl acrylate, preferably a Cl-C6 alkyl
acrylate; an alkyl methacrylate, preferably a Cl-C5 alkyl
2 ~
14- 336-2220 (8CV-5048/83)
methacrylate: acrylic acid; methacrylic acid: or a mixture of
any of the foregoing with a cross-linking monomer.
More particularly, the core stage of diene or
butadiene-based core-shell multi-stage polymer component
(C)(a) comprises polymerized conjugated diene units of a
copolymer of polymerized diene units with polymerized units
of a vinyl aromatic compound or mixtures of such compounds.
Suitable conjugated dienes for use in said core stage include
butadiene, isoprene, 1,3-pentadiene and the like. Illustrative
vinyl aromatic compounds include styrene, alphamethylstyrene,
vinyl toluene, paramethylstyrene, and the like and esters of
acrylic or methacrylic acid. The core of these copolymers
should comprise a major portion of diene units. The
preferred core-shell multi-stage polymer of this type
includes a core of a styrene-butadiene copolymer having a
molecular weight within the range of about 150,000 to
500,000. The core stage may also include a cross-linking
monomer.
Although it is optional but preferred, the
butadiene-based core-shell polymer may include a second
intermediate stage of a polymerized vinyl monomer graft2d to
the core stage. Suitable vinyl monomers for use in the
second intermediate shell stage include, but are not limited
to, styrene, vinyl toluene, alphamethylstyrene, halogenated
styrene, naphthalene, or divinylbenzene. Styrene and vinyl
cyanide compounds such as acrylonitriles, methacrylonitriles,
and alphahalogenated acrylonitriles, are especially
preferred. These vinyl monomers can be used either alone or
in admixture.
The final or outer shell stage of the diene-based
core-shell multi-stage polymer comprises polymerized units of
a monomeric compound selected from the group consisting of
alkyl acrylates, especially Cl-C6 alkyl acrylate; alkyl
methacrylate, especially Cl-C6 alkyl methacrylates; acrylic
acid; methacrylic acid; or a mixture of any of the foregoing
2 3 7
-15- 336-2220 (8CV-5048/83)
together with a cross-linking monomer. More particularly,
the monomeric compound may be a Cl-C6 alkyl acrylate, e.g.,
methyl acrylate, ethyl acrylate, hexyl acrylate, and the
like: a Cl-C6 alkyl methacrylate, e.g., methyl methacrylate,
ethyl methacrylate, hexyl methacrylate, and the like acrylic
acid or methacrylic acid. Methyl methacrylate is preferred.
In addition to the monomeric compound, the final or
outer shell stage of the diene-based core shell multi-stage
polymer also includes a cross-linking monomer. The
cross-linking monomer, as described above, is a poly-
ethylenically unsaturated monomer having a plurality of
addition polymerizable reactive groups, all of which
polymerize at substantially the same reaction rate. Suitable
cross-linking monomers include poly acrylic and poly meth-
acrylic acid esters of polyols such as butylene diacrylate
and dimethacrylate, trimethylol propane trimethacrylate and
the like, divinyl- and trivinylbenzene, vinyl acrylate and
methacrylate and the like. The preferred cross-linking
monomer is butylene diacrylate.
A particularly preferred core shell multi-stage
polymer for use as component (C)(a) herein is a core-shell
polymer having a core polymerized from butadiene and styrene,
methylmethacrylate and divinylbenzene, a second, intermediate
stage or shell polymerized from styrene, and a third stage or
outer shell polymerized from methyl methacrylate and
1,3-butylene glycol dimethacrylate. Such a commercially
available core-shell multi-stage polymer is ACRYLDID~ RM 653,
also known as PARALOID- E~L 3691, from Rohm and Haas Co.
The diene-based core-shell multi-stage polymers are
also prepared sequentially by emulsion polymerization
techniques wherein each successive stage or shell _oats the
previous stage polymer. The diene~based core-shell multi-
stage polymers and the methods for their preparation are more
fully described in U.S. Patent No. 4,180,494.
. ' '
3 ~
-16- 336-2220 (8CV-5048/83)
The modifiers (C)(b) of the present invention
comprise acrylonitrile-butadiene-styrene ~A8S) graft
copolymers well known to those of ordinary skill in the art.
Particularly suitable ABS impact modifier can be
produced according to the procedures as set forth in U.S.
Patent No. 4,764,563.
These ABS impact modifiers are prepared by grafting
particular ratios of styrene and acrylonitrile on butadiene-
based rubber substrates.
Specifically, these impact modifiers are A~S graft
copolymer resins prepared by graft polymerizing particular
ratios of styrene and acrylonitrile in the presence of
particular styrene-butadiene rubber substrates.
The butadiene-based rubber substrates useful in
preparing such impact modifiers are conventional copolymers
of styrene and butadiene which optionally include up to 15
weight percent of acrylonitrile and/or an alkyl acrylate in
which the alkyl group contains 4 or more carbon atoms, and
comprise from 78 to 95 weight percent butadiene and from 22
to 5 weight percent styrene. The rubber substrate may
further include up to 2 weight percent of additional
copolymerizable cross-linking monomers such as divinylbenzene,
triallylcyanurate or the like, up to 2 weight percent of
chain transfer agents, such as tertiary dodecyl mercaptan,
and up to 2 weight percent of graft enhancers such as alkyl
methacrylate, diallylmaleate and the like. Diene polymer ~nd
copolymer rubbers are well known and widely employed
commercially for a number ~f purposes. The preparation of
such rubbers may be accomplished by any of a variety of
processes well known and conventionally used. Particularly
used are emulsion polymerization processes which provide the
rubber in latex focm suitable for use in subsequent ~raft
polymerization processes~
These preferred A3S-type impact modifiers are
prepared by graft polymerizing from about 40 to about 70,
2 ~5T~ 2 ~ I ~
-17- 336-2220 (8CV-5048/83)
preferably from 47 to 61 parts by weight of a grafting
monomer mixture comprising a monovinyl aromatic compound
(MVA), such as styrene, a methyl styrene, p-methyl styrene or
a combination thereof and an ethylenically unsaturated
nitrile (EUN~ such as acrylonitrile and/or methacrylonitrile
in the presence of 100 parts by weight of butadiene-based
rubber substrate. The impact modifier is thus a high rubber
graft copolymer having a rubber content of from about 50 to
about 80 weight percent, preferably fro~ 62 to 78 weight
percent and, correspondingly, a graft monomer component or
superstrate of from about 50 to 20, preferably from 48 to 22
weight percent.
The weight ratio of the MVA to the EUN in the
grafting monomer mixture will be in the range of from 3:1 to
5:1 and preferably, from 3.8:1 to 4.2:1.
This graft polymerization of the MVA/EUN monomer
mixture in the presen~e of the rubbery substrate may be
carried out by any of the graft polymerization processes well
known and widely used in the polymerization art for preparing
ABS resins, including emulsion, suspension and bulk
processes. Typical of such processes are emulsion graft
polymerization processes wherein the grafting monomers are
added together with surfactants and chain tran~fer agents as
desired, to an emulsion latex of the rubbery substrate and
polymerized using an initiator. The initiator may be any of
the commonly used free-radical generators including pecoxides
such as alcumyl peroxide or azo initiators such as azobisiso-
butyronitrile. Alternatively, any of the variety of redox
polymerization catalysts such as the combination of cumene
hydroperoxide with ferrous sulfate and sodium formaldehyde
sulfoxylate which are well known and widely used in such
proceesses may be employed. The graft polymerization process
used in the preparation of these ABS impact modifiers, as
well as those processes used in coagulating and isolating the
impact modifier for further use, are thus well known and
2~Q2~
-18- 336-2220 (8CV-5048~83)
conventional, and the application of such pcocesses to the
preparation of these impact modifiers for further use, are
thus well known and conventional, and apparent to those
skilled in the art.
The ABS impact polymer suitable for use in the
present invention may also comprise a styrenic polymer which
comprises a rigid portion and a rubber portion. The rigid
portion is formed from at least two ethylenically unsaturated
monomers, one of which comprises styrene and/or substituted
styrene. Preferred substituted styrenes inelude, but are not
'' limited to, halogen-substituted styrene, particularly wherein
the halogen is substituted on the aromatic ring, alpha-methyl
sytrene and para-methyl styrene. The ~ther ethylenically
unqaturated monomer which is used in forming the rigid
portion may be selected from acrylonitrile, substituted
acrylonitriles, acrylates, alkyl, substituted acrylates,
methacrylate~, alkyl substituted methacrylates, and
ethylenically unsaturated carboxylic acids, diacids,
dianhydrides, acid esters, diacid esters, amides, imides and
alkyl and aryl substituted imides. Preferably, the second
monomer which is used to form the rigid portion is selected
from the group consisting of acrylonitrile, methacrylonitriler
alkyl methacrylates, malaic, anhydride, maleimide, alkyl
maleimides and aryl maleimides, and mixtures thereof. It is
further preferred that the rigid portion is formed from about
60 to about 95 weight percent, and more preferably 60 to 80
weight percent of the styrene and/or substituted styrene
monomers, and from about 5 to about 40 weight percent, and
more perferably 20 to 40 weight percent of the second
monomer.
The rubber portion may be formed from polymers or
copolymers of one or more conjugated dienes, copolymers of
conjugated dienes and non-diene vinyl monomers, alkyl
acrylate polymers, and copolymers of ethylenically unsaturat_d
-
: ~ .
.
.~5~371
-19- 336-2220 (8CV-5048/83)
olefins and non-conjugated diene polymers (EPDM) rubbers. A
preferred rubber portion includes polybutadiene.
The styrenic polymer component may be formed such
that the rigid portion is grafted to the rubber portion.
Alternatively, the rigid portion may be blended with the
rubber portion. When the rigid portion is blended with the
rubber portion, it is preferred that the rubber portion has
been previously grafted with one or more grafting monomers.
Accordingly, the styrenic polymer component may be so
produced by any method known in the art, for example,
emulsion, bulk, mass or suspension polymerization processes.
It is preferred that the styrenic polymer component contains
from about 10 to 90 weight percent of the rubber portion and
from about 10 to 90 weight percent of the rigid portion,
based on the rubber portion and the rigid portion. More
preferably, the styrenic polymer component comprises from
about 40 to about 80 weight percent of the rubber portion and
from about 20 to about 60 weight percent of the rigid
portion, based on the rubber portion and the rigid portion.
Combinations of the above core-shell multi-stage
modifiers and ABS modifiers are suitable for use in the
present invention as well.
In another aspect, the compositions of the present
invention may include a second polyester resin (D) which may
be the same as or different than (A) in addition to
components (A), (8) and ~C~.
Polyesters (D) suitable for use herein may include
those of (A) above and may be saturated or unsaturated. They
are preferably, however, derived from an aliphatic or cyclo-
aliphatic diol, or mixtures thereof, containing from 2 to
about 10 carbon atoms, and at least one aromatic dicarboxylic
acid. Preferred saturated polyester resins comprise the
reaction product of a dicarboxylic acid or a chemical
equivalent thereof and a diol. Preferred polyesters are
derived from an aliphatic diol and an aromatic dicarboxylic
~a~a~,37,
-20- 336-2220 (8CV-5048/83)
acid and have repeated units of the following general
formula:
- I CH2 3n - - C
wherein n is an integer of from 2 to 4.
The most preferred polyesters are poly(ethylene
terephthalate) and poly(l,4-butylene terephthalate).
Also contemplated herein are the above polyesters
with minor amoun~s, e.g., from 0.5 to about 2 percent by
weight, of units derived from aliphatic acid and~or aliphatic
polyols to form copolyesters. The aliphatic polyols include
glycols, such as poly~ethylene glycol). All such polyesters
can be made following the teachings of, for example, U.S.
Patent Nos. 2,465,319 and 3,047,539.
The polyesters which are derived from a
cycloaliphatic diol and an aromatic dicarboxylic acid are
prepared, for example, by condensing either the cis- or
trans-isomer (or mixtures thereof) of, for example,
1,4-cyclohexanedimethanol with an aromatic dicarboxylic
acid to produce a polyester having recurring units of t~e
following formula:
~ O
- - O - CH ~ CH2 - O - C - R - ~
wherein the cyclohexane ring is selected from the cis- and
trans-isomers thereof and R represents an aryl r~dical
containing 6 to 20 carbon atoms and which is the decarboxvlated
cesidue derived from an aromatic dicarboxylic acid.
Examples of ~romatic dicarboxylic acids represented
by the decarboxylated residue R are isophthalic or terephthalic
acid, 1,2-di(p-carboxyphenyl) ethane, 4,4'-dicarboxvdi?henvl
2 ~ ~ O ~ 37
-21- 336-2220 (8CV-5048/83)
ether, etc., and mixtures of these. All of these acids
contain at least one aromatic nucleus. Acids containing
fused rings can also be present, such as in 1,4- or
1,5-naphthalenedicarboxylic acids. The preferred dicarboxylic
acids are terephthalic acid or a mixture of terephthalic and
isophthalic acids.
Another preferred polyester may be derived from the
reaction of either the cis- or trans-isomer (or a mixture
thereof~ of 1,4-cyclohexanedimethanol with a mixture of
isophthalic and terephthalic acids. Such a polyest~r would
have repeating units of the formula: -
- O - CH2~CH2 - O - C~ C -- -
Still another preferred polyester is a copolyester
derived from a cyclohexanedimethanol, an alkylene glycol and
an aromatic dicarboxylic acid. These copolyesters are
prepared by condensing either the cis- or trans-isomer (or
mixtures thereof) of, for example, 1,4-cyclohexanedimethanol
and an alkylene glycol with an aromatic dicarboxylic acid so
as to produce a copolyester having units of the following
formula:
O - CH2 ~ CH2 - O - C - R
~ --t CH2 ~ 0 - C - R - C
y
wherein the cyclohexane ring is selected from the cis- and
trans-isomers thereof, ~ is as previously defined, n is an
integer of 2 to 4, the x units comprise from about 10 to
:
2 ~ ? 3 7 1
-22- 336-2220 (8CV-5048/83)
about 90 percent by weight and the y units comprise from
about 90 to about lO percent by weight.
Such a preferred copolyester may be derived from
the reaction of either the cis- or trans-isomer (or mixtures
thereof) of l,4-cyclohexanedimethanol and ethylene glycol
with terephthalic acid in a molar ratio of 1:2:3. These
copolyesters have repeating units of the following formula:
_~\ ~ C ~
~ 0~ CH2~ - ~C
wherein x and y are as previously defined.
The polyesters described herein are either
commercially available or can be produced by methods well
known in the art, such as those set forth in, for example,
U.S. Patent No. 2,901,466.
The polyesters used herein as compon nt (~) have an
intrinsic viscosity of from about 0.4 to about 2.0 dl/g as
measureZ in a 60:40 phenol:tetrachloroethane mixture or
similar solvent at 23-30C.
Special mention is made of blends comprising the
compositions of the present invention. Additionally, the
compositions of the present invention may be molded,
extruded, or thermoformed into articles by conventional
methods known to one of ordinary skill in the art.
In the two component compocitions of the present
invention, component (A), the first polyester resin,
comprises a minor portion and component (B), the polycarbonate
resin, comprises a major portion of the polyoster/polycarbonate
composi~ion. Preferably, the first polyester component (~)
comprises from about l to about g9 parts by weight and the
2~S ~37
- -23- 336-2220 (aCV-5048/83)
polycarbonate resin comprises from about 99 to about 51 parts
by weight based upon 100 parts by weight of (A) and (B)
combined, and most preferably, the first polyester component
(A) comprises from about 1 to about 25 by weight and
especially 25 parts by weight and the polycarbonate component
(B) comprises from about 99 to about 75 parts by weight and
especially 75 parts by weight based upon 100 parts by weight
of (A) and (~) combined.
In the modified compositions of the present inventio
component (A) comprises a minor amount and component (8)
~' comprises a major amount of (A) and (B) combined as above and
components (A) and (B) combined compriqe from about 80 to
about 99 parts by weight and component (C) comprises from
aDout 20 to about 1 part by weight based upon 100 parts by
weight of (A), (B) and (C) combined.
In the modified compositions containing an
additional polyester resin (D), component (A) comprises a
minor amount and component (B) comprises a major amount of
(A) and (B) combined as above and components (A) and (8)
combined comprise from about 50 to about 75 parts by weight,
component (C) comprises from about 1 to about 20 parts by
weight, and component (D) comprises from about ~ to about 35
parts by weight based upon 100 parts by weight of (A), (B),
(C), and (D) combined.
Conventional processes for mixing thermop~astic
polymers can be used for the manufacture of compositions
within the present invention. For example, the compositions
can be manufactured using any suitable mixing equipment,
cokneaders, or extruders under conditions known to one of
ordinary skill in the art.
Additionally, additives such as flow promoters,
antioxidants, nucleating agents, other stabilizers,
reinforcing agents, fillers, pigments, flame retardants, or
combinations of any of the foregoing may be added to
compositions of the present invention.
,
; ,
2g~.237
-24- 336-2220 (8CV-5048/83)
DESCRIPTION OP TLR PReFERR~D e~BODI~NTS
The following examples illustrate the invention with-
out limitation. All parts are given by weight unless otherwise
indicated. Impact strengths are represented as notched and
unnotched Izods according to ASTM-D-256 or Dynatup impact at
room temperature (RT) (23~C) unless otherwise specified.
Tensile properties are measured by ASTM-D-638 and flexural
properties are measured by ASTM-D-790. Appearances are
recorded as either opaque, transparent or clear and colorless.
~ PLe 1
A well mixed dry blend of 25.0 parts of
poly(l,4-butylene-trans-1,4-cyclohexanedicarboxylate) (PBCD)
(melt viscosity 1100 poise at 250C), 74.65 parts of a
polycarbonate resin (P~) (poly(bisphenol-A carbonate) -
Lexan- 141 - General Electric Company - Pittsfield, MA), and
0.35 part of a stabilizer packaqe was extruded on a 2.5" HPM
extruder operating at 100 rpm with barrel zones at 250C.
The extruded blend was observed to be homogeneous
and transparent. Tensile, notched Izod, and Dynatup bars
were molded on a 3.5 oz. Van Dorn injection molding machine
at 250C barrel temperatures and 75C mold temperature in a
30 second cycle.
Properties are summarized in Table 1.
CO~PARATIVE ~XAMPLE lA*
The procedure of Example 1 was followed substituting
100.0 parts by weight of PBCD (melt viscosity 2400 poise at
250C) for the dry blend.
Properties ace summarized in Table 1.
COMPARATIVE eXAHPLE lB~
The procedure of Example 1 was followed substituting
a dry blend of 99.65 parts of poly(l,4-butylene tarephthalate)
(P~T) (Valox~ 315 - Beneral ~lectric Company) and 0.35 part
of a stabilizer package.
2 iJ ~ ~ ~ 3 7
-25- 336-2220 (8CV-5048/83)
Properties are summarized in Table 1.
COMPARATIVE ~XA#PLE lC~
The procedure of Example 1 was followed substituting
a dry blend of 98.97 parts of PBCD (melt viscosity 2500 poise
at 250C) and 1.03 parts of stabilizer package.
Properties are summarized in Table 1.
COMPARAT}V2 ~SA~PL~ ID~
The procedure of Example 1 was followed substituting
a dry blend of 98.97 parts by weight of P8T (Valox- 315 -
General Electric Company) and 1.03 parts of a stabilizer
package.
Properties are summarized in Table 1.
COMPaRATIV2 EXA~PL~
~he procedure of Example 1 was followed substituting
a dry blend of 100.0 parts of PC (poly(bisphenol-A carbonate) -
Lexan~ 141 - General Electric Company) and a trace of a
stabilizer package.
Properties are summarized in ~able 1.
EXAMP~ 2
A copolyester comprising a 23:77 ratio of cis- ~o
trans-1,4-butylene-1,4-cyclohexanedicarboxylate monomer a was
prepared by reacting 515.0 parts of trans-dimethyl-trans-1,4-
cyclohexane dicarboxylate and 265.0 parts of a 60:40 mixture
of cis- and trans-dimethyl-1,4-cyclohexanedicarboxylate
(DMCD-HP - Eastman Chemical - Rochester, NY) with 550.0 Darts
of l,4-butane diol in the present of 1.0 part of tit~nium in
the form of tetra (2-ethylhexyl) titanate under the
interchange condition, recovering the excess butane diol at
260C under vacuum. ~ C13 NMR analysis indicated that the
resultant copolyester contains 23 percent of the cis-cyclo-
hexane dicarboxylate residue. Diffecential scanning
-26- 336-2220 (8CV-5048/83)
calorimetry indicated a peak crystallization temperature of
13~C and a heat of fusion of 18.3 J/g.
A well mixed dry blend of 25.0 parts of the
copolyester from above and 75.0 parts of a polycarbonate
resin (poly(bisphenol-A carbonate) - Lexan~ 141 - General
Electric Company) was extruded and molded as in Example 1.
rhe test pieces were transparent as molded. Some
of the test pieces were annealed in an oven for 4 hours at
100C without turning opaque. Other test pieces were
annealed in an oven for 4 hours at 120C without turning
opaque, but some bubbles developed in these pieces due to the
presence of moisture.
Properties are summarized in Table 1.
EXAMPLE 3
lS The procedure of Example 2 was followed substituting
a dry blend of 25.0 parts of PBCD (poly(1,4-butylene-trans-
1,4-cyclobexanedicarboxylate~) and 75.0 parts of a poly-
carbonate resin (poly(bisphenol-A carbonate~ - Lexan- 141 -
General Electric Company).
The test pieces were transparent as ~olded, but
upon annealing, turned opaque due to crystallization of the
polyester component.
Properties are summarized in Table 1.
Example 1 shows that PBCD/PC compositions cetain
the transparency of polycarbonates. Examples 1-3, when
compared with Comparative-Examples lA*-lE*, illustrate the
improvement in flexural modulus PBCD/PC compositions provide
over that of the individual components and over other
polyester resins such as PBT, as well as the excellent
retention of practical impact streng~h as measured by
unnotched Izod impact strength and Dynatup impact strength
and the retention of transparency of the compositions of the
present invention.
r~ L~
-27- 336-2220 ( 8CV-5048/83 )
T~BLe 1
_.
PBCD/PC OO~POSITIO~8
Exam~le 1 lA* lB~ lC* lD* lE* 2 3
Composition
P8CDA/
viscosity (p) 25.0/1100 100~0/2400 - 98.97/2500 - - - 25.0/-
P~CD - - - - - - 25.0
p~TC _ - 99.65 - 9~-97
pcD 74.65 - - - - 100.075.0 75.0
Stabillzers0.35 - 0.35 1.03 1.03 trace
Propestie~
Appearance
as molded T O O - - T ~ T
AppearanceE
after annealing
4 hrq. @ 100C O - - - - - T O
Appear~nceF
after annealing
4 hrs. @ 120C O ~ TB D
Flexur31
Modulus (Rpsi) 442 107 340 66 340 340
Flexural
Strength tRPsi~ 17 4.3 12 - - 14
Tensile
Strength (Rpsi) 7.1 4.7 7.5 3~9 7.5 9
Tensile
Elongation (~) 76 337 200 450 300 130
Dynatup Impact
~ 23C at Max
LoaB ~fpi) 61 - - - - _ 47
Izod Impact
Notched ~ 23C
~fpi) 1.0 0.5 1.0 - - 15
Notched @ -30C
(~pi) - - - 0.~ 0.5 - -
Unnotched
~ 23C (fpi) NB NB NB - - NB
D/B Transition
C - - - 30 30 - - -
2 ;, j !3 ~ 3 ~
-28- 336-2220 ~8CV-5048/83)
TA8L~ 1 (cont'd)
A - poly(l,4-butylene-trans-1,4-cyclohexanedicarboxylate)
- copolyester of 23 77 cis to trans poly(1,4-butylene-1,4-
cyclohexanedicarboxylate) monomers
C - poly(l,4-butylene tereph~halate) - Valox- 315 - General
Electric Company
D - poly(bisphenol-A carbonate) - Lexan- 141 - General
Electric Company
E - O = opaque; T = transparent; TB = transparent with
bubbles.
_
~r~ r ,~37
-29- 336-2220 (8CV-5048/~3)
EXAMPLE 4
The procedure of Example 1 was followed substituting
a dry blend of 39.0 parts of PBCD (poly(1,4-butylene-trans-
1,4-cyclohexanedicarboxylate) melt viscosity 1100 poise at
250C), 49c25 parts of PC (poly(bisphenol-A carbonate) -
Lexan~ 141 - General Electric Company), 10.5 parts of a
core-shell multi-stage polymer (CJS modifier) (core =
polymerized butadiene and styrene, methylmethacrylate and
divinylbenze~e second stage/shell = polymerized styrene -
outer shell 5 polym~rized methylmethacrylate and 1,3-butylene
glycol dimethacrylate - ACRYLOID- KM 653, also known as
PARALOID- EXL 3691 - Rohm & Haas Company - Philadelphia, PA)
and 1.2S parts of a stabilizer package.
The extruded composition was observed to be opaque
in appearance. Properties are su~marized in Table 2.
COMPARATIVE EXA~PLe 4A~
The procedure of Example 1 was followed substituting
A dry blend of 39.0 parts of PBT (poly(1,4-butylene
terephthalate) - Valox~ 315 - General Electric Company),
49.25 parts of PC (poly(bisphenol-A carbonate) - Lexan~ 141 -
General Electric Company), 10.5 parts of C/S modifier
(ACRYLOID- KM 653, also known as PARALOID EXL 3691 - Rohm &
Haas Company), and 1.25 parts of a stabilizer package.
Properties are summarized in Table 2.
eXA~PL~ S
The procedure of Example 1 was followed substituting
a dry blend of 38.34 parts of PBCD (poly(1,4-butylene-trans-
1,4-cyclohexanedicarboxylate) melt viscosity 2500 pois~ at
250C), 46.0 parts of PC (poly(bisphenol-A carbonate) -
Lexan' 141 - General Electric Company), 14.0 parts of _/S
modifier (ACRYLOID' KM 653, also known as PARALOID~ EXL 3691 -
Rohm & Haas Company), and 1.66 parts of a stabilizer ?ackage.
Properties are summarized in Table 2.
3 ~
-30- 336-2220 (8CV-5048/83)
CO~PARATIV~ ~AMPL~ 5A~
The procedure of Sxample 1 was followed substituting
a dry blend of 38.34 parts of P~T (poly~1,4-butylene
terephthalate) - Valox- 315 - General Electric Company), 46.0
parts of PC (poly(bisphenol-A carbonate) - Lexan~ 141 -
General Electric Company), 14.0 parts of C/S modifier
(ACRYLOID- KM 653, also known as PARALOID^ EXL 3691 - Rohm &
Haas Company) and 1.66 parts of a stabilizer package.
Properties are summarized in Table 2.
~ ~ .,
e~A~PLE 6
The procedure of Example is followed substituting a
dry blend of 39.0 parts of PBCD (poly(1,4-butylene-trans-1,4-
cyclohexanedicarboxylate) melt viscosity 1100 poise at
250C), 49.25 parts of PC (poly(bisphenol-A carbonate) -
15 Lexan- 141 - General Electric Company), 10.5 parts of an
acrylonitrile-butadiene-styrene graft copolymer modifier
(ABS-BLENDEX- 338 General Electric Company), and 1.25 parts
of a stabilizer package.
Typical properties will be substantially the same
as those of Example 4 and are summarized in Table 2.
Examples 4, 5 and 6 demonstrate that modified
PBCD/PC co~positions retain higher than average stiffness and
excellent impact strength as well as excellent low temperature
properties. When compared with Comparative Examples lA* and
lC~, they illustrate that the modified compositions perform
better than the individual- components.
3 7
I
-31- 336-2220 (8CV-5048~83)
TABLe 2
MODIFIeD P~CD~PC CO~POSITIONS
Example 4 4A* 5 SA* 6
Composition
PBCDA 39.0 - _ _ 39.0
PBCDB _ _ 38.34
PBT - 39.0 - 38.34
pcD 49.25 49~25 46.0 46.0 49.25
ModifierE 10.5 10.5 14.0 14.0
ModifierF _ _ _ _ 10.5
Stabilizers 1.25 1.25 1.66 1.66 1.25
Properties
AppearanceG O O - - same as
Example 4
Plexural same as
Modulus (Rpsi) 307 296 295 290 Example 4
Flexural same as
Strength (Kpsi) 10.7 12.3 - - Example 4
Tensile same as
Strength (Kpsi) 4.7 7.7 6.7 6.7 Example 4
Tensile same as
Elongation (~) 117 120 150 150 Example 4
Dynatup Impact
@ 23C at Max same as
Load (fpi~ 43 40 -- Example 4
Izod Impact
Notched ~ 23C same as
(fpi) 15.2 13.3 - - Example 4
Notched @ -30C - same as
(fpi) - - 14.0 12.0Example 4
Unnotched same as
@ 23C (fpi) NB NB -- Example 4
D/B TransitionC - - -65 -55 same as
Example 4
~3~,37
-32- 336-2220 (8CV-5048~83)
TABLE 2 (cont'd)
A - poly(l,4-butylene-trans-1,4-cyclohexanedicarboxylate) - mel~
viscosity 1100 poise at 250C.
- poly(l,4-butylene-trans-1,4-cyclohexanedicarboxylate) - melt
viscosity 2500 poise at 250C.
C - poly(l,4-butylene terephthalate) - Valox- 315 - General
Electric Co.
D - poly(bisphenol-A carbonate) - Lexan- 141 - General Electric
Co .
E - core-shell multi-stage polymer - core = polymerized butadiene
and styrene, methylmethacrylate and divinylbenzene - second
stage/shell - polymerized styrene - outer shell = polymerized
methylmethacrylate and 1,3-~utylene glycol dimethacrylate -.
(AC~YLOID- KM 653, also known as PARALOID- EXL 3691 - Rohm &
Haas Company - Philadelphia, PA)
F - Acrylonitrile-butadiene-styrene graft copolymer (ABS~ -
BLENDEX- 338 - General Electric Co.
G - O = opaque; T = transparent
H - Typical properties obtain will be substantially the same
as those of Example 4.
2 ~ 3 7
.,
-33- 336-2220 (8CV-5048/B3)
EXA~PLe 7
The procedure of Example 1 was followed substituting
a dry blend of 10.0 parts of PBCD (poly(1,4-butylene-trans-
1,4-cyclohexanedicarboxylate) (~elt viscosity -2500 poise at
250C), 28.34 parts of PBT (poly(1,4-butylene terephthalate) -
Valox- 315 - General Electric Company), 46.0 parts of PC
(poly(bisphenol-A carbonate) - Lexan- 141 - General Electric
Company), 14.0 parts of CJS modifier (ACRYLOID- RM 653, also
known as PARALOID- EXL 3691 - Rohm & Haas Company), and 1.66
parts of stabilizer package.
Properties are su~marized in Table 3.
EXAHPLg 8
The procedure of Example 1 was followed substituting
20 parts of P8CD (poly(1,4-butylene-trans-1,4-cyclohexane-
lS dicarboxylate) (melt viscosity -2500 poise at 250C), 18.34
parts of PBT (poly(1,4-butylene terephthalate) - Valox- 315 -
General Electric Company), 46.0 parts of PC (poly(bisphenol-A
carbonate) - Lexan' 141 - General Electric Company), 14.0
parts of C/S modifier (ACRYLOID- KM 653, also known as
PARALOID- EXL 3691 - Rohm & Haas Company), and 1.66 parts of
stabilizer package.
Properties are summarized in Table 3.
EXA~PLE 9
The procedure of Example 1 was followed substituting
28.34 parts of PBCD (poly(1,4-butylene-trans-1,4-cyclohexane-
dicarboxylate) (melt viscosity 2500 poise at 250C), 10.0
parts of PBT ~poly(1,4-butylene terephthalate) - Valox' 315 -
General Electric Company), 46.0 parts of PC (poly(bisphenol-A
carbonate) - Lexan' 141 - General Electric Company), 14.0
parts of C/S modifier (ACRYL~ID~ K~ 653, also known as
PARALOID~ EXL 3691 - Rohm & ~aas Company), and 1.66 parts of
stabilizer packa~e.
Properties are summarized in Table 3.
,
2~ iJ~37
-34- 336-22Z0 (8CV-5048/83)
EXAMP~ 10
The procedure of Example 1 is followed substituting
a dry blend of 10.0 parts of PBCD (poly(1,4-butylene-trans-
1,4-cyclohexanedicarboxyla~e) melt viscosity 2500 poise at
250C), 28.34 parts of PBT (poly(1,4-butylene terephthalate) -
Valox- 315 - General Electric Company), 46.0 parts of
acrylonitrile-butadiene-styrene graft copolymer modifier (ABS
BLENDEX- 338 - General Electric Companyl, and 1.66 parts of a
stabilizer package.
Typical properties will be substantially the same
as those of Example 7 and are summarized in Table 3.
Examples 7, 8, 9 and 10 demonstrate that modified
PBCD/PC/PE compositions retain higher than average stiffness,
excellent impact strength~ and excellent tensile properties
at all temperatures.
2~ 937
I
-35- 336-2220 (8CV-5048/83)
TABLE 3
. . .
MODI~IED P~CD~PC/PE CO~POSITIONS
ExamDle 7 8 9 loF
Composition
PBCDA 10.0 20.0 28.34 10.0
PBTB 28.34 18.34 10.0 28.34
pcC 46.0 46.0 ~6.0 46.0
ModifierD 14.0 14.0 14.0
ModifierE - - - 14.0
Stabilizers 1.66 1.6~ 1.66 1.66
Properties
Flexural same as
Modulus (Kpsi) 290 310 320 Example 7
Ten~ile same as
Strength (Rpsi) 6.7 6.5 6.5 Example 7
Tensile same as
Elongation (%) 110 150 140 Example 7
Izod Impact
Notched @ -30C same as
(fpi) 13.0 13.0 14.0 Example 7
D/B TransitionC -55 -60 -65 same as
Example 7
A - poly(l,4-butylene-trans-1,4-cyclohexanedicarboxylate) -
melt viscosity 2500 poise.
8 - poly(l,4-butylene terephthalate) - Valox8 315 - General
Electric Co.
C - poly(bi~phenol-A carbonate) - Lexan~ 141 - ~eneral
Electric Co.
D - core-shell multi-stage polymer - core - polymerized
butadiene and sytrene, methylmethacrylate and
divinylbenzene - second stage = polymerized styrene -
outer shell = polymerized methylmethacrylate and
1,3-butylene glycol dimethacrylat~ - (AC~YL~IDL K.~ 6~3,
also known as PARALOID- EXL 3691 - Rohm & Haas Company -
Philadelphia, PA).
E - acrylonitrile-butadiene-styrene graft copolymer (A~S) -
BLENDEX- 338 - General Electric Co.
F - typical properties obtained will be substantially the
same a~ those i~ Example 7.
~ '
2 ~ .' 3 7
-36- 336-2220 (8CV-5048/83)
EXA~PLE 11
A well mixed dry blend of 50.0 parts of a
copolyester of a 25:75 ratio of -is- to trans-1,4-cyclo-
hexanedimethanol and dimethyl trans-1,4-cyclohexane-
dicarboxylate (PCCD) having a melt viscosity of 3000 poise at
250C and 50.0 parts of a polycarbonate resin (poly(bisphenol-
carbonate) - Lexan- 141 - General Electric Company) was
extruded and molded as in Example 1.
The molded pieces were transparent. Differential
scanning colorimetry indicated that the blend had essentially
no crystallinity and showed no tendency to crystallize at
annealing temperatures.
Properties are summarized in Table 4.
EXAMPLE 12
A well mixed dry blend of 49.8 parts of PCCD, a
copolyester of a 25:75 ratio of cis- to trans-1,4-cyclo-
hexanedimethanol and dimethyl trans-1,4-cyclohexane-
dicarboxylate having a melt viscosity of 3000 poise at 250C,
49.8 parts of a polycarbonate resin (poly(bisphenol-A
carbonate) - Lexan- 141 - General Electric Company) and 0.4
part of a stabili~er package was extruded, molded, and tested
as in Example 1.
Properties are summarized in rable 4.
E~A~PLE 13
A well mixed dry blend of 49.975 parts of a
copolyester of PCCD, a 25:75 ratio of cis- to trans-1,4-cyclo-
hexanedimethanol and dimethyl trans-1,4-cyclohexane-
dicarboxylate having a melt viscosity of 3000 poise ~t 250 Or
49.975 parts of a polycarbonate resin (polytbisphenol-~
carbonate) - LexanD 141 - General Electric Company) modified
with a small amount of blue dye to mask a slightly yellow
hue, and 0.05 par~ of stabilizet package was extruded, molded
and tested as in Example 1.
2 ~ 3 ~
I
-37- 336-2220 (8CV-5~48/83)
The molded pieces were water clear and colorless.
Properties are summarized in Table 4.
Examples 11-13 demonstrate the combination of
transparency and excellent ductility of the unmodified
compositions of the present invention.
~ ..
2 ~ 3 ~
-3a- 336-2220 (~CV-5048/83)
TABL~ 4
PCCD/PC COMPOSITIONS
Example _ 12 13_
Composition
PCCD 50,0 49.8 49.975
pcB 50.0 49.8 49.97S
Stabilizers - 0.4 0.05
Dye - - Trace
_ Properties
AppearanceD T T C
Melt Viscosity
@ 250C (poise) - 10600
Flexural
Modulus (Kpsi) - 237
Flexural
Strength (Kpsi) - 11.4
Tensile
Strength Yield/
Break (Rpsi) - 7.0/- 7.26/6.33
Tensile
Elongation (~) - 150 108
Dynatup Impact
Q 23C at
Max Load (fpi) - 34.0
Total - 38.1
Izod Impact
Notched @ 23C
(fpi) _ 38.9
Notched @ -30C
(fpi) - 15.~ -
. ,,
. ~ , . .
2 ~S ~f~,3
-39- 336-2220 (~CV-5048/83)
TABLL 4 (cont'd)
A - copolyester of 25:75 cis:trans 1,4-cyclohexanedimethanol
and dimethyl tran~-1,4-cyclohexanedicarboxylate - melt
viscosity 3000 poise at 250C.
B - poly(bisphenol-A carbonate) - Lexan~ 141 - General
Electric Co.
C - Blue dye to mask yellow hue.
D - O ~ opaque; T = transparent C - water clear and
colorless.
~5~',7,37
-~0- 336-2220 (8CV-5084/83)
E~A~PL~ 14
The general procedure of Examples 11-13 is repeated
substituting a dry blend of 39.0 parts of PCCD, a copolyester
of a 25:75 ratio of cis- to trans-1,4-cyclohexanedimethanoi
and dimethyl trans-1,4-cyclohexanedicarboxylate having a melt
viscosity of 3000 poise at 250C, 49.25 parts of PC
(poly(bisphenol-A carbonate) - Lexan- 141 - General Electric
Company), 10.5 parts of a core shell multi-stage polymer (C/S
modifier) (core = polymerized butadiene and styrene,
methylmethacrylate and divinylbenzene second stage/shell =
polymerized styrene - outer shell ~ polymerized
methylmethacrylate and 1,3-butylene glycol dimethacrylate -
ACRYLOID' KM 653, also known as PARALOID- EXL 3691 - Rohm &
Haas Company - Philadelphia, PA) and 1.25 parts of a
stabilizer package as indicated in Table 5.
Substantially the same results as Examples 11-13
will be obtained, except stiffness is reduced and the sample
is opaque.
EXA~PL~ 15
The general procedure of Examples 11-13 is repeated
substituting a dry blend of 39.0 parts of PCCD (a copolyester
of a 25:75 ratio of cis- to trans-1,4-cyclohexane dicarboxylat
having a melt viscosity of 3000 poise at 250C), 49.25 parts
of PC (poly(bisphenol-A carbonate) - Lexan' 141 - General
Electric Company), 10.5 parts of an acrylonitrile-butadiene-
styrene graft copolymer modifier (ABS BLENDEX~ 338 - General
Electric Company), and 1.25 parts of a stabilizer ~ackage as
indicated in ~able 5.
Substantially the same results as Examples 11-13
will be obtained, except stiffness is reduced and the sample
is opaque.
~XAMPL~ 16
The gener~l procedure of Examples 11-13 ia repeated
substituting a dry blend of 10.0 parts of PCCD, a copolyester
2~3 ~37
!
-41- 336-2220 (8CV-5048/83)
of a 25:75 ratio of cis- to trans-1,4-cyclohexanedimethanol
and dimethyl trans-1,4-cyclohexanedicarboxylate having a melt
viscosity of 3000 poise at 250C, 28.34 parts of P8T
(poly(1,4-butylene terephthalate) - Valox~ 315 - General
Electric Company), 46.0 parts of PC (poly(bisphenol-A
carbonate) - Lexan- 141 - General Electric Company), 14.0
parts of C/S modifier (ACRYLOID- KM 653, also known as
PARALOID- EXL 3691 - Rohm & Haas Company), and 1.66 parts of
a stabilizer package as indicated in Table 5.
Substantially the same results as Examples 11-13
~' will be obtained, except stiffness is reduced, and the sample
is opaque.
E~A~PL~ 17
The procedure of Example 1 is followed substituting
a dry blend of 10.0 parts of PCCD, a copolyester of a 25:75
ratio of cis- to trans-1,4-cyclohexanedimethanol and dimethyl
trans-1,4-cyclohexanedicarboxylate having a melt viscosity of
3000 poise at 250C, 28.34 parts of PBT (poly(1,4-butylene
terephthalate - Valox- 315 - General Electric Company), 46.0
par~s of acrylonitrile-butadienestyrene graft copolymer
modifier (ABS - BLENDEX 338 - General Electric Company), and
1.66 parts of a stabilizer package as indicated in Table 5.
Substantially the same results as Examples 11-13
will be obtained, except stiffness is reduced, and the sample
is opaque.
2 ~
-42- 336-2220 (aCV-5048/83)
TABLE 5
~ODIFILD PCCD/PC AND MODIPI~D PCCD/PC/PLT COMPOSITIONS
Exam~le 14 15 16 17
Composition
PCCDA 39.0 39 0 10 0 10.0
P8TB - _ 28 34 28.34
pcC 49.25 49.25 46.0 46.0
ModifierD 10.5 - 14.0
ModifierE - 10 5 - 14.0
Stabilizers 1.25 1.25 1 66 1.66
A - copolyester of 25 75 cis:trans 1,4-cyclohexanedimethanol
and dimethyl trans-1,4-cyclohexanedicarboxylate - ~elt
viscosity 3000 poise at 250C
B - poly(l,4-butylene terephthalate) - Valox- 315 - General
Electric Co.
C - poly(bisphenol-A carbonate) - Lexan- 141 - General
Electric Co.
D - core-shell multi-stage polymer - core = polymerized
butadiene and styrene, methylmethacrylate and
divinylbenzene second stage/shell = polymerized
styrene - outer shell - polymerized methylmethacrylate
and 1,3-butylene glycol dimethacrylate - (ACRYL~ID- K~
653, also know as PARALOID- EXL 3691 - Rohm & ~aas
Company - Philadelphia, P~)
E - Acrylonitrile-butadiene-styrene graft copolymer (ABS) -
BLENDEX- 338 - General Electric Co
- ~ .
- . -
.- -
2 ~ ;?, 3l 7
_43- 336-2220 (8CV-5048/83)
All patents, publications, applications and test
methods mentioned above are hereby incorporated by reference.
Many variations of the present invention will
suggest themselves to those skilled in this art in light of
the above, detailed description. All such obvious variations
are within the full intended scope of the appended claims.
