Note: Descriptions are shown in the official language in which they were submitted.
7.. `~
-1- 336-2221 (8CV-5084/~118)
MODIFICATIONS OF POLY(AL~YLENE
CYCLO~EXANEDICARBOXYLATE) BLENDS
-
CROSS-R~FeRENCE TO RELATED APPLICATIONS
This application is related to the followin~
commonly owned, concurrently filed U.S. patent applications.
SERIAL ATTY'S S~BJECT
NO. DOCKET MATTER APPLICANT(S)
336-2~20 Poly(alkylene cyclohexane- W.F.H. Borman
(8CV-5048/ dicarboxylate)-polycarbonate N-I Liu
83) Compositions and Modifications
336-2222 Poly(alkylene cyclohexane- W.F.H. Borman
(8CV-5125) dicarboxylate)-(alkylene
terephthalate) Copolyesters
336-2223 Poly(alkylene cyclohexane- W.F.H. Borman
(BCV-5117) dicarboxylate) Binary Blends N-I Liu
FI~LD OP T~E I~VE~TION
This invention relates to compositions comprised of
(A) a polyester resin comprising the reaction product of at
least one straight chain, branched, or cycloaliphatic C2_cl0
alkane diol or chemical equivalent thereof, and at least one
cycloaliphatic diacid or chemical equivalent thereof; and (B)
an effective impact strength or tensile property modifying
amount of a substantially amorphous copolymer resin. Filled
and flame retardant compositions are contemplated as well.
These compositions are homogeneous and have excellent light
stability; good chemical resistance, in particular to
gasoline and similar automotive chemicals; excellent impact
strength even at low tempeEatureS; excellent tensile
properties; and enhanced melt flow properties while retaining
excellent impact strength.
BACKGROUND OF T~E I~V~NTION
Novel compositions comprising a polymer resin which
is 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
~" ". ' ,1 ' ~, 1,
-2- 336-2221 (8CV-5084/5118)
achemical equivalent thereof combined with an effective
impact strength or tensile property modifying amount of a
substantially amorphous copolymer resin have been discovered
which are homogeneous and have excellent light stability,
5 good chemical resistance, excellent impact strength even at
low temperature, and excellent tensile properties.
Weatherable, chemical resistant, UY radiation
resistant, resilient, high impact polymer compositions 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 poinits 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 Science,
Vol. 14, 685-98, ~1970): U.S. Patent No. 3,515,628.
~ilfong, J. Polymer Sci., Vol. 54, 385-410 (1961),
referred to polyesters of hexahydro terephthalic acid, the
cis-/trans-mixtures of cyclohexane dicarboxylic acids
obtained by the hydrogenation of terephthalic acid. See,
Caldwell et al, U.S. Patent No. 2,891,930 including
poly(neopentyl 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 emulsions.
Low viscosity thermoplastic adhesives comprising
thermoplastic resin, a linear polyester, a polymer of a
mono-olefinically unsaturated monomer, a viscosity decreasin~
2`~
-3- 336-2221 (8CV-5084/5118)
additive and an optional granular metallic material are
disclosed by Jackson et al, U.S. Patent No, 3,644,627.
Caldwell et al, U.S. Patent No. 3,657,389 blended
polyesters of 1,4-butane diol and terephthalic or trans-1,4-
cyclohexane dicarboxylic acid with polystyrene to improve hot
melt-adhesives.
Friction activatable solvent-free adhesives
comprising a thermoplastic 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.
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,
an ester of trans-1,4-cyclohexanedicarboyxlic acid and a
diacyl derivative of an aromatic diol.
Copending applications, U.S. Serial Nos. 07/271,250,
07/271,248, 07/271,247, 07/271,230, and 07/271,896 all filed
on November 14, 1988, describe polyorganosiloxane/polyvinyl-
based graft polymer modifiers combined with various polyester
resins but ~o not specify the poly(alkylene cyclohex.~ne
dicarboxylate) resins of the present invention.
Copending applications, U.S. Serial Nos. 07/271,246
filed on November 14, 1988 and 07/3S6,356 filed on May 24,
1989, describe combinations of any of organosiloxane-based,
diene rubber-based and polyorganosiloxane/polyvinyl-based
modifiers with polyester resins but do not describe the
polyester resins of the present invention.
Major shorteomings of many of the previous
compositions are their inability to withstand UV radiation
and chemicals such as gasoline, while exhibiting acceptable
impact strength and tensile properties.
~l r, f~
-4- 336-2221 (8CV-5084/5118)
Many of these shortcomings are overcome by
compositions of the present invention. The compositions of
the present invention are homogeneous, exhibit good impact
strength and tensile properties, are chemically resistant in
part due to the fact that the crystalline nature of the
polyester is retained in the compositions, and are ~V light
resistant.
SUMMARY OF TH~ INVE~TION
According to the present invention, there are
provided compositions comprising (A) a polyester resin
comprising the reaction product of la) 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 equiYalent thereof; and (B)
an effective impact strength or tensile property modifying
amount of a substantially amorphous copolymer resin.
In a preferred embodiment, polyester (A) is the
reaction product of (a) at least one straight chain or
branched C2-C10 alkane diol and (b) as above.
Further contemplated by the invention are
compositions as described above wherein the modifier (a) is
selected from the group consisting of (a) an interpolymer
comprising (i) a cross-linked acrylate elastomer, (ii) a
cross-linked alkenyl aromatic-vinyl cyanide copolymer, and
optionally (iii) an additional vinyl-based polymer or
copolymer which may the same as or different than (i) or
(ii) (b) a multi-stage coEe-shell polymer having a rubbery
core derived from an acrylate or a (meth)acrylate, a diene or
a mixture of an~ of the foregoing, and a vinyl-based polymer
or copolymer shell; (c) a multi-stage organosiloxane graft
polymer composition comprising (i) as a first stage (1) an
organosiloxane polymer substrate or (2) a polymeric
co-homopolymerized substrate comprised of, in combination, an
organosiloxane polymer, at least one vinyl-based polymer, and
optional units derived from a cross-linking agent or agents,
h~ rn ~
-5- 336-2221 (8CV-5084/5118)
units which serve as a graft-linking agent or agents, units
derived from a cross-linking agent or agents and units from
the same or different agent or agents which serve as a
graft-linking agent or agents, or a mixture of any of the
foregoing units; and (ii) at least one subsequent stage or
stages graft polymerized in the presence of any previous
stages which i5 comprised of a vinyl-based polymer or a
cross-linked vinyl-based polymer; (d) an ethylene-propylene-
diene terpolymer or grafted derivative thereof; (e) a
styrene-ethylene-butene-styrene polymer; (f) a vinyl cyanide-
conjugated diolefin-alkenyl aromatic terpolymer; or (g) a
combination of any of the foregoing.
DETAILED DESCRIPTION OF T~E I~VENTION
The diols useful in the preparation of the
polyesters resins (A) of the present invention are straight
chain, branched, or cycloaliphatic but preferably straight
chain or branched alkane diols and may contain from 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
diol; diethylene glycol; 2,2-dimethyl-1,3-propane diol;
2-ethyl, 2-methyl, 1,3-propane diol; 1,3and 1,5-pentane diol;
dipropylene glycol; 2-methyl-1,5-pentane diol; 1,6-hexane
diol; l,4-cyclohexane dimethanol and particularly its cis-
and trans-enantiomers; triethylene glycol; 1,10-decane diol;
and mixtures of any of the foregoing. Particularly preferred
is l,~-butane diol. If a cycloaliphatic diol or chemical
equivalent thereof and particularly 1,4-cyclohexane
dimethanol or its chemical equivalents 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 to the diols include esters
and ethers, such as dialkylesters, diaryl esters, polytetra-
methylene oxide and the like.
~" ~ b ! ~? t '~
-6- 336-2221 (8CV-5084/5118)
The diacids (A)(b) useful in the preparation of the
polyester resins (A) of the present invention are cyclo-
aliphatic 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 trans-
1,4-cyclohexanedicarboxylic acid as further explained above.
Cyclohexanedicarboxylic acids and their chemical
equivalents can be prepared, for example, by the hydrogenation
10 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,
15 Friefelder et al, Journal of Or~anic Chemistry, 31, 34-38
(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
20 in carbon or silica. 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
25 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 o~ the cis- and trans-
30 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-enantiomers combined.
-7- 336-2221 (8CV-5084/5118)
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 these diacids include
esters, alkyl esters, e.g., dialkyl esters, diaryl esters,
anhydrides, acid chlorides, acid bromides, and the like. The
preferred chemical equivalents 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-
and trans- positions are obtained. The enantiomers can be
separated as above, and the trans-enantiomer is especially
preferred for the reasons above. Mixtures of the enantiomers
are suitable as explained above and preferably in the amount
as explained above.
The polyester resins (A) of the present invention
are typically obtained through the condensation or ester
interchange polymerization of the diol or diol equivalent
component (A)(a) with the diacid or diacid chemical
equivalent component (A)(b) and have recurring units of the
formula
/ O O
~O-R-O-C-Rl-C--t
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 al~ane diol
having 2 to 10 carbon atoms or chemical equivalents thereof;
and
Rl is a cycloaliphatic cadical which ia the decarboxylated
residue derived from a cycloaliphatic diacid or chemical
equivalent thereof. They particularly have recurring units
-8- 336-2221 (8CV-5084/5118)
of the formula
~O-CH2 -CH2-CH2-CH -0-~~
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 from the cis- or trans-isomers or a mixture of
cis- and trans-isomers thereof.
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 generally 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
amount, typically about 20 to 200 ppm of titanium based upon
the final product.
The substantially amorphous copolymer resin (B) may
comprise one of several different modifiers or combinations
of two or more of these modifiers. Suitable are the groups
of modifiers known as ASA modifiers, acrylate or diene
rubber-based modifiers, organosiloxane modifiers, EPDM
modifiers, SEPS modifiers, and A3S modifiers.
The term ASA modifier is used to refer to
multi-stage interpolymer modifiers having a cross-linked
(meth)acrylate rubbery phase, preferably butyl acrylate.
Associated with this cross-linked rubbery phase is a phase
comprised of cross-linked styrenic resin, preferably styrene,
which interpenetrates the cross-linked rubbery phase.
Incorporation of small amounts of other monomers such as
acrylonitrile or (meth)acrylonitrile within the resin also
provides products within this class of modifiers. The
interpenetrating network is provided when the monomers
forming the resin phase are polymerized and cross-linked in
-9- 336-2221 (8CV-5084/5118)
the presence of the previously polymerized and cross-linked
(meth)acrylate rubbery phase.
The interpolymer compositions may be formed by the
following two-step, sequential polymerization process:
1. emulsion polymerizing an acrylate monomer
charge of at least one C2-C10 alkyl or alkoxyalkyl acrylate,
C8-C12 alkyl or alkoxyalkyl methacrylate, or compatible
mixtures thereof (all of which may be referred to as (meth)-
acrylate), in an aqueous polymerization medium in the
presence of an effective amount of a suitable di- or
polyethylenically unsaturated cross-linking agent for such
type of monomer, with the C4-C8 alkyl or alkoxyalkyl
acrylates being the preferred acrylate monomers for use in
this step;
2. emulsion polymerizing a monomer charge of
styrene or styrene/~meth)acrylonitrile in an aqueous
polymerization medium~ also in the presence of an effective
amount of a suitable di- or polyethylenically unsaturated
cross-linking agent for such monomers, said polymerization
being carried out in the presence of the product from Step 1
so that the cross-linked (meth)acrylate and cross-linked
vinyl aromatic, e.g., styrene or styrene/(meth)acrylonitrile,
components form an interpolymer wherein the respective phases
interpenetrate one another.
The final multi-stage rubbery product that is
formed thereby can be isolated and dried.
O~e manner of proceeding in conducting the aqueous
emulsion polymerization step leading to the preparation of
the cross-linked (meth~acrylate rubbery phase comprises
preferably first preparing a monomer charge comprising an
aqueous mixture containing about 10 to 50 percent by weight,
of one or more monomers, the identity of which will be
described in detail hereinbelow and from about 0.2 to 2.0
percent weight of the monomer mixture, of a water-soluble
catalyst, such as ammonium, sodium or potassium persulfate,
' ~ 3
,,,
-10- 3~6-2221 (8CV-5084/5118)
hydrogen peroxide or a redox system, such as a mixture of a
persulfate with an alkali metal bisulfite, thiosulfate or
hydrosulfite. The mixture is then heated at a temperature of
from about 40C to 95C for a period of about 0.5 to about 8
hours.
The (meth)acrylate elastomer phase comprises
cross-linked (meth)acrylate polymers or copolymers having a
Tg, i.e., glass transition temperature, of less than about
25C. These can be polymerized by means of free radical
10 initiated emulsion techniques. These (meth)acrylate
elastomer polymers should be cross-linked so that they can
retain their integrity during subsequent polymer processing
steps. This cross-linking can be achieved during the
polymerization of the elastomer if a polyfunctional
15 ethylenically unsaturated monomer is included in the
polymerization recipe. The term "cross-linked" with respect
to the ASA modifiers denotes a polymer which at ambient
temperatures is substantially insoluble in organic solvents
such as tetrahydrofuran or cyclohexanone.
Examples of (meth)acrylate elastomers that can be
used include the cross-linked polymers of the C2-C~0 alkyl
acrylate and the C8-C12 alkyl methacrylate monomers,
preferably the C2-C8 alkyl acrylates, s~lcn as poly(n-butyl
acrylate), poly(ethyl acrylate) and poly(2-ethylhexylacrylate).
25 At least one acrylate monomer is utilized in this step. If
desired, ~he monomer charge may contain small amounts, i.e.,
1 to 20 percent by weight of the amount of acrylate monomer,
of optional monomers including styrene, acrylonitrile,
methacrylonitrile, methyl methacrylate, methacrylic acid,
30 acrylic acid, vinylidene chloride, vinyl toluene and any
other ethylenically unsaturated monomer copolymerizable with
the acrylate monomer selected for use. Special mention is
made of alkoxyalkyl (meth)acrylates, specifically ethoxyethyl
and methoxymethyl (meth)acrylates, and acrylonitrile which
35 will improve oil resistance while maintaining a low Tg.
~; m
~ 336-2221 (8CV-50B4/5118)
In order to cross-link the (meth)acrylate monomer,
from about 0.05 to about 10, preferably 0.1 to 5 percent by
weight based on the weight of acrylate monomer, of at least
one cross-linking agent is used. This cross-linking agent
is, for the purposes of this class of modifiers, a di- or
polyfunctional ethylenically unsaturated monomer having at
least one vinyl group of the formula:
H R
H ~ C C_~___
wherein R is hydrogen or lower alkyl. As is well known in
the art, the vinyl groups on the cross-linking monomer can be
the same, e.g., divinylbenzene, trimethylolpropane triacrylate,
etc., or different, e.g., allyl methacrylate, diallyl
fumarate, diallyl maleate, etc. Examples of other suitable
cross-linking monomers which are known to persons in the art
and which can be used are triethylene glycol dimethacrylate,
ethylene glycol dimethacrylate, tetraethylene glycol
dimethacrylate, polyethylene glycol dimethacrylate,
1,3-butylene glycol diacrylate, 1,4-butanediol diacrylate,
diethylene glycol diacrylate, diethylene glycol dimethacrylate,
1,6-hexanediol diacrylate, 2,2-dimethylpropane 1,3-diacrylate,
triallyl isocyanurate, divinylbenzene, pentaerythritol
tetramethacrylate, dipentaerythritol monohydroxy-penta-
acrylate, pentaerythritol triacrylate, ethoxylated
trimethylolpropane triacryl~te, polyethylene glycol
diacrylate, tetraethylene glycol diacrylate, pentaerythritol
tetraacrylate, 1,3-butylene glycol dimethacrylate, tripropylene
glycol diacrylate, ethoxylated bisphenol-A dimethacrylate,
ethoxylated bisphenol-A diacrylate, trimethylolpropane
triacrylate, trimethylolpropane trimethacrylate, mixtures of
any of the foregoing/ and the like.
c~ ; r ~
? : i
-12- 336-2221 (8CV-5084/5118)
Optimum results are obtained by the use of a
cross-linked copolymer containing from about 95 to about 99.9
percent by weight of n-butyl acrylate and from about 0.1 to
about 5 percent by weight, of butylene glycol diacrylate.
The emulsifier which is used is at least one of the
following conventional types: an anionic emulsifier, e.g.,
the C2-C22 carboxylic acids, the sulfates or sulfonates of
C6-C22 alcohols or allyl phenols; a non-ionic emulsifier,
e.g., the addition products of alkylene oxides to fatty
acids, amines or amides; a combination of the foregoing
anionic and non-~onic emulsifiers; or the cationic emulsifiers,
e.g., quarternary ammonium containing compounds. The amount
of emulsifier should be present from about 0.5 to about 5
percent by weight in the emulsion.
In the disclosure of Yu et al, U.S. Patent No.
3,944,631, it has been found that regardless of the
particular emulsifier being utilized in preparing the rubber
polymer latex, its polymerization in large scale commercial
equipment is greatly faciliated by introducing the monomer
charge to the system in several portions over a period of
from 1 to 3 hours. Thus, where this is not done and the
total monomer charge is introduced in one portion, the
resulting exothermic polymerization reaction often becomes
virtually uncontrollable leading to overheating which in
turn, may set up or coagulate the resulting polymer latex.
However, by dividing the monomer charge and introducing it in
about several portions, the resulting polymerization reaction
remains controllable and overheating and coagulation can be
prevented. An initiator is also present in the emulsion in
an amount ranging from about 0.0005 to 2 percent by weight of
the (meth)acrylate monomer. Suitable for use are water
soluble peroxidic compounds, e.g., hydrogen peroxide and
alkali metal and ammonium persulfates, oil soluble organic
peroxides and azo compounds, e.g., benzoylperoxide,
azobisisobutyronitrile and the like, used singly or in
-13- 336-2221 (8CV-5084/5118)
combination. Redox catalysts, e.g., mixtures of peroxidic
catalysts with reducing agents, such as hydrazine, alkali
metal bisulfites, thiosulfates, and hydrosulfites, and
soluble oxidizable sulfoxyl compounds can also be ~sed. A
; preferred initiator is ammonium persulfate.
A chain transfer agent such a5 an alkyl mercaptan,
e.g., t-dodecyl mercaptan, toluene, xylene, chloroform,
halogenated hydrocarbons and the like may also be used. A
buffer to adjust the pH may be used.
The next step in the preparation of the interpolymer
ASA modifiers is the emulsion polymerization of a mixture of
vinyl aromatic monomers, e.g., styrene or styrene and
acrylonitrile, in the presence of a mi~or portion of at least
one difunctional or polyfunctional cross-linking monomer to
form, for example, a cross-linked styrene homopolymer or
styrene-acrylonitrile copolymer. This emulsion polymerization
is carried out in the presence of the cross-linked
(meth)acrylate rubbery phase by addinq the styrene or
styrene-acrylonitrile charge to the previously prepared
aqueous emulsion of cross-linked (meth)acrylate rubbery
phase. The amount of styrene or styrene-acrylonitrile which
is added ranges from about 60 to about 10, preferably
from about 50 to about 20 parts by weight based upon the
weight of the final product which will be formed. When
present, (meth)acrylonitrile preferably comprises from about
15 to about 45 parts by weight to, correspondingly, about 85
to about 55 parts by weight of vinyl aromatic monomer.
The ~nonomer charge of styrene-acrylonitrile, when
such a combination is used, can comprise from about 5;:45 to
about 85:15 weight parts of styrene to acrylonitrile with the
most preferred ratio being about 76:24. If desired, small
amounts, e.g., below about 20 parts by weight, of optional
monomers can be included. Examples are t-butyl styrene,
p-chlorostyrene, alpha-methylstyrene, methyl methacrylate,
alkyl acrylate vinylidene chloride, ethylene, propylene,
'; ,1 r)~
-14- 336-2221 (8CV-5084/5118)
isobutylene and other ethylenic compounds copolymerizable
with styrene and styrene-acrylonitrile.
The cross-linking agent, emulsifiers, initiators
and chain transfer agents discussed in the previous step can
also be used in this step in the same amounts to form the
interpenetrating cross-linked styrene-acrylonitrile resin
phase associated with the rubbery phase.
The term acrylate or diene-rubber based modifier is
used to refer to core-shell multi-sta~e polymers having a
core comprising an acrylate or methacrylate, a diene or a
mixture of any of the foregoing.
In a preferred modifier of this type, the core is
polymerized from a Cl to C6 alkyl acrylate resulting in an
acrylic rubber core having a Tg below about 10C and
containing 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(methacrylic
esters) of polyols such as butylene diacrylate and
dimethacrylate, trimethylol propane trimethacrylate and the
like, di- and tri-vinyl benzene, vinyl acrylate and
methacrylate, and the like. The preferred cross-linking
monomer is butylene diacrylate.
The graft-linking monomer is a polyethylenically
unsaturated monomer havin~ 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
J
-15- 336-2221 (8CV-5084/5118)
particles. When the rigid thermoplastic shell s~age is
subsequently polymerized at the surface of the elastomer, the
eesidual unsaturated, addition polymerizable reactive groups
contributed by the graft-linking monomer participate 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
alkyl group-containing monomers of allyl esters of
ethylenically unsaturated diacids, such as allyl ~crylate,
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 unsaturations. The preferred graft-linking
monomers are allyl methacrylate and diallyl maleate.
The final or shell stage monomer can be comprised
of Cl-C16 methacrylate, styrene, acrylonitrile, alkyl
acrylates, alkyl methacrylate, dialkylaminoalky~ methacrylate,
and the likeO Preferably, the final stage monomer includes a
major portion of a Cl-C4 alkyl methacrylate.
One type of preferred core-shell multi-stage
polymer has only two stages, the first stage or core being
polymerized from a monomer system comprising butyl acrylate
with butylene diacrylate as a cross-linking agent, allyl
methacrylate or diallyl maleate as a graft-linking agent and
a fi~al stage or ou~er shell of polymerized methyl
methacrylate. A preferred two stage core-shell multi-stage
polymer of this type is commercially available under the
tradename ACRYLOID KM 330, 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
-16- ~36-22~1 (8CV-5084/5118)
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 1;C 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 (B) are found in U.S. Patent Nos. 4,034,013 and
4,096,202.
Another amorphous copolymer resin for use herein
comprises a diene-based and preferably a butadiene-based
core-shell multi-stage copolymer resin. These diene-based
core-shell multi-stage copolymers generally comprise a
conjugated diene-based core, an intermediate shell of
polymerized vinyl monomer units and a final 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
methacrylate; acrylic acid; methacrylic acid; or a mixture of
any of the foregoing with a cross-linking monomer.
More particularly, the core stage of the diene or
butadiene-based core-shell copolymer component 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 the core stage include
butadiene, isoprene, 1,3-pentadiene and the like. Illustrative
vinyl aromatic compounds include s~yrene, alphamethylstyrene,
vinyl toluene, paramethylstyrene, and the like and esters of
acrylic or methacrylic acid. The core of these polymers
J~ C~
-17- 336-2221 t8CV-SOa4/5118)
should comprise a major portion of diene units. The
preferred core-shell multi-stage polymer 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
S 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 grafted 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
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 includes a cross-linkins monomer. The cross-linking
monomer, as described above, is a polyethylenically
unsaturated monomer having a plurality of addition
polymerizable reactive groups, all of which polymerize at
substantially the same reaction rate. Suitable cross-linking
2~ ~,t~
-la- 336-2221 (8Cv-5084/511O
monomers include poly acrylic and poly methacrylic 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 herein is a core-shell polymer having a core
polymerized from butadiene and styrene, methylmethacrylate
and divinylbenzene, a second stage or shell polymerized from
styrene, and a third stage or outer shell polymerized from
methyl methacrylate and l,3-butylene glycol dimethacrylate.
Such a commercially available multi-stage core-shell polymer
is ACRYLOID- RM 653, also known as PARALOID- EXL 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 coats the
previous stage polymer. The diene-based core-shell multi-
stage polymers and the methods for their preparation are morefully described in U.S. Patent No. 4,180,494.
The term organosiloxane modifier refers to
multi-stage polyorganosiloxane-based graft polymers prepared
with or without the incorporation of a vinyl-based polymer in
the first stage substrate. Where incorporation of the
vinyl-based polymer is desired, the process is generally
described hereinbelow as a co-homopolymerization process.
Co-homopolymerization refers to a polymerization
step where two distinct polymerization mechanisms are
effected concurrently, including simultaneously. In
particular, the first stage co-homopolymerization may
encompass a siloxane polymerization (e.g., ring opening and
condensation mechanism) in conjunction with a concurrent
vinyl polymerization. The discrete mechanisms are not seen
-19- 336-2221 (8CV-5084/5118)
as competing with each other, but rather, two homopolymers
are concurrently produced each retaining its own structure.
The co-homopolymerization process may provide two
discrete networks rather than a random copolymer. It is
possible that the network(s) comprises two or more distinct
interpenetrating polymer phases, which provide the additional
strength needed in the polyorganosiloxane. This is evidenced
by the two distinct glass transition temperatures which can
be detected by differential scanning calorimetry. Preferably,
the product of the co-homopolymerization process is rubbery
instead of a resin-like powder.
Subsequent to the co-homopolymerization of ~he
siloxanes and vinyl-based monomers of the first step or the
polymerization of the siloxane alone, at least one additional
graft polymerization process is utilized to achieve these
multi-stage polyorganosiloxane/polyvinyl-based graft polymers
or the multi-stage polyorganosiloxane-based graft polymer.
The subsequent graft polymerization is preferably
of at least one vinyl-based type monomer. A styrene/
acrylonitrile copolymer, an alkyl(meth)acrylate polymer or
alkyl(meth)acrylate/acrylonitrile copolymer i5 particularly
effective as the second stage graft polymer or copolymer, or
as the outermost stage when intermediary stages are
optionally utilized, and when two modifier compositions are
utilized in combination.
Additional cross-linking and/or graft-linking agent
ca~n be utilized in this initial stage to provide the co-homo-
polymerized networks from both polymeric constituents which
provide greater rubber integrity.
The first stage rubbery substrate is provided by a
series of sequential processing steps. In a premixing step
the ingredients required for the reaction of the
organosiloxane(s) and optional vinyl-based monomer(s) are
premixed with water and suitable cross-linker(s),
graft-linker(s), initiator(s) and surfactant(s). The
~'r~ 7
-20- 336-2221 (8CV-5084/5118)
premixed ingredients are homogenized by conventional means.
The reactions may begin at this early stage of the process,
but these reactions are generally slow at room temperature.
~he homogenized reactants may be directed to a reactor
vessel, typically stainless steel or glass flasks, under a
nitrogen blanket. Heat is applied to facilitate the
reaction. For typical 5 to 50 gallon stainless steel
reactors, a 3 to 6 hour residence time at 75 to 90 degrees
centigrade is adequate to complete the co-homopolymerization.
Cooling for 2 to 6 hours will typically reduce the temperature
~ to at least room temperature where the reaction mass can be
held for 3 to 72 hours. Cooling to lower temperatures (e.g.
S degrees centigrade) may sometimes be preferred to enhance
the properties of the polyorganosiloxane/polyvinyl-based
substrate.
Cooling to room temperature or lower allows the
polyorganosiloxane portion to build molecular weight, thereby
minimizing the extractable silicone rubber fragments and
optimizing physical properties of the product for certain
applications. Generally, lower temperatures are preferred
when it is desired to optimize the elasticity of the
substrate.
The initiator for the siloxane component can be any
ionic ring opening type initiator when cyclic siloxanes are
utilized, such as alkylarylsulfonic acids, alkyldiaryl-
disulfonic acids, alkylsulfonic acids, and the like. The
best suited example is dodecylbenzenesulfonic acid which can
act as an initiator and at the same time as an emulsifier.
In some cases, the joint use of a metal salt of an afore-
mentioned sulfonic acid is also preferred.
The initiator for the optional styrenic or othervinyl-based monomers in the co-homopolymerization process can
be any organic soluble radical initiator, such as azobisiso-
butyronitrile (AIBN) and the organic peroxides, e.g. benzoyl
peroxide, dichlorobenzoyl peroxide, and tert-butyl perbenzoate.
-21- 336-2221 (8CV-5084/5118)
Also suitable are water-soluble radical initiators such as
the persulfates. Although it is possible to charge this type
of initiator at the beginning of the process, it is preferred
that it be charged continuously or incrementally during the
co-homopolymerization period. Since persulfate is less
stable in the acid conditions of the siloxane polymerization,
it is preferred that the persulfate be added over time to
keep the vinyl polymerization running. Particle size, pH and
total solids measurements can be readily monitored at this
stage of the process. A latex rubber emulsion prepared as
described above will generally contain particles having an
average diameter of 100 to ~00 nanometers and preferably 150
to ~00 nanometers. The particle size is particularly
influenced by the homogenization pressure (and the number of
passes through the homogenizer) and the composition of the
reaction ingredients. A pressure range of 2000 to 12000 psi
is typical, and 3000 to 9000 psi is preferred. Multiple
passes through the homogenizer may be preferred, but on a
large scale, a single pass may be most practical.
The fore~oing reaction steps must be followed by a
suitable neutralization process to provide the polyorgano-
siloxane-based or polyorganosiloxane/polyvinyl-based
modifiers. The main object of the neutralization is to
quench the siloxane polymerization. This is accomplished by
adding a caustic solution such as sodium hydroxide, potassium
hydroxide, potassium or sodium carbonate, sodium hydrogen
carbQnate, triethanolamine or triethylamine. The pH of the
reaction solution may be r~ised from a level of 1 to 3 to a
pH of at least 6.5, and preerably 7 to 9.
It is often desirable to add additional soap or
surfactant to the emulsion formed at the end of the first
stage, prior to the neutralization step. Additional
surfactant tends to facilitate avoidance of premature
agglomeration or flocculation of the co-homopolymerized
rubber in the quench step.
!, ,' : , ' :;
-22- 336-2221 (8CV-5084/5118)
The foregoing co-homopolymerization process
provides a rubbery network composed of a polyorganosiloxane/
polyvinyl-based substrate which may serve as first stage of
the graft polymer of the organosiloxane modifiers. Optionally,
a first stage comprising an organosiloxane polymer with or
without units derived from a cross-linking agent or agents
and optionally units which serve as a graft-linking agent or
agents may be employed. The organosiloxane polymer can be
prepared in a manner according to the prior art, e.g.
European Patent Application No. 0,166,900. Also suitable
are mixtures of the co-homopolymerized substrate with
silicone substrates.
The next stage involves the graft polymerization
of additional vinyl-functional moieties onto graft sites
provided by the rubbery substrate particles on the latex
formed in the first stage.
The grafted polymers may be the product of a vinyl
polymerization process. Sultable vinyl monomers for graft
polymerization include, without limitation, alkenyl aromatic
compounds such as styrene, divinylbenzene, alphamethylstyrene,
vinyl toluene, halogenated styrene and the like; methacrylates
such as methyl methacrylate and 2-ethylhexyl methacrylate;
acrylates such as acrylic acid, methyl acrylate, ethyl
acrylate and butyl acrylate, vinyl cyanicle compounds such as
acrylonitrile and methacrylonitrile; olefins such as
ethylene, propylene, butadiene, isoprene, and chloroprene;
other vinyl compounds such a~ acrylamides, .~-(mono or
di-substituted)alkyl acrylamides, vinyl acetate, vinyl
chloride, vinyl alkyl ethers, allyl (meth)acrylate, triallyl
isocyanurate, ethylene dimethacrylate, diallyl maleate,
maleic anhydride; maleimide compounds such as ~aleimide, and
N-phenyl (or alkyl) maleimide; and mixtures of these
monomers.
The ~inyl-based polymers of subsequent stages
(c)(ii) in the organosiloxane-based or the organosilo~ane/
.s ~ 1~; r' ~3
-23- 336-2221 (8CV-5084/5118)
vinyl-based polymers preferably comprise at least one
selected from the group consisting of alkenyl aromatic
compounds, (meth)acrylate compounds, vinyl cyanide compounds,
maleimide compounds and acrylamide compounds. Especially
preferred are polystyrene, poly(methyl methacrylate)~
styrene/acrylonitrile copolymer, styrene/methyl methacrylate
copolymer and methyl methacrylate/acrylonitrile copolymer.
The vinyl polymerization is accomplished in an
emulsion; therefore, water-soluble initiators are suitable,
e.g. potassium persulfate, sodium persulfate and ammonium
persulfate. It is practical to add the initiator at the
beginning of this step, prior to charging the vinyl monomer
for the second stage polymerization. Other Redox initiator
systems, such as cumene hydroperoxide/ferrous sulfate/glucose/
sodium pyrophosphate, can also be utilized at this stage as
well as other organic peroxides.
Sequential multi-stage polymerization processes of
the type used to produce the organosiloxane-based modifiers
are described as multi-stage graft polymerization processes
wherein the initial stage provides a polymerized organosiloxane
substrate or a co-homopolymerized organosiloxane/vinyl-based
substrate. This substrate may have sufficient grafting sites
for a second or subsequent stage to be grafted thereto.
Grafted polystyrene, poly(meth)acrylate, styrene/acrylonitrile
copolymer, methyl methacrylate/acrylonitrile copolymer or
styrene/divinylbenzene copolymer as the outermost stage is
preferred, yet many other intermediary stages such as a butyl
acrylate stage are useful ~urthermore, the grafting of
additional stages of the same or different kinds is also
possible.
The organosiloxanes useful in the first st~ge o~
these modifiers are any of those known to produce silicone
elastomers and may include those which are hydroxy-, vinyl-,
hydri~e- or mercapto- end capped linear organosiloxane
oligomersO
r r~ r
-24- 336-2221 ( aCV-5084/5118 )
The polyorganosiloxanes will be comprised primarily
of a mixture of units of the ~ormula
wherein R is hydrogen or a monovalent hydrocarbon radical of
about 1 to 16 carbon atoms and n is 0, 1 or 2. ~n~ may be
another integer in a smaller number of organosiloxane units
of the polyorganosiloxane.
The organosiloxanes generally are in cyclic form
and have three or more siloxane units, and preferably are
those having three to six units, although others may be used.
Such organosiloxanes include, without limitation, for
example, hexamethylcyclotrisiloxane, octamethylcyclotetra-
siloxane, decamethylcyclopentasiloxane, dodecamethylcyclo-
hexasiloxane, trimethyltriphenylcyclotrisiloxane, tetramethyl-
tetraphenylcyclotetrasiloxane, tetramethyltetravinylcyclotetra-
siloxane and octaphenylcyclotetrasiloxane. These or similar
organosiloxanes may be used alone or in combination.
The vinyl-based monomers useful in conjunction with
the co-homopolymerization of or~anosiloxanes in the first
stage are preferred to be alkenyl aromatic compounds such as
styrene, divinylbenzene, alpha-methyl-styrene, vinyl toluene,
vinyl naphthalene, vinyl anthracene, and halogenated styrene
or its derivatives. Other suitable vinyl-based monomers
include acrylic acids and acrylates such as methyl-, ethyl-,
alkyl-, or butylacrylate; methacrylates such as methyl
methacrylate, or 2-ethylhexyl methacrylate; vinyl cyanides
such as acrylonitrile, and methacrylonitrile; ole~ins such as
ethylene, propylene, butadiene, isoprene, and chloroprene;
and other vinyl compounds such as vinyl imidazole, 5 vinyl-
2-norbornene, vinyl pyridine, vinyl pyrrolidinone, vinyl
acetate, vinyl alkyl ethers, vinyl chloride, vinyl furan,
N-vinylcarbazole, allyl (meth)acrylate, triallyl isocyanurate,
ethylene di(meth)acrylate, butylene di(meth)acrylate, diallyl
maleate, and maleic anhydride; maleimide compounds such as
j~,f~r~
-25- 336-2221 (8CV-5084/5118)
maleimide, and N-phenyl (or alkyl) maleimides; acrylamides;
N-(mono or disubstituted) acrylamides; and mixtures of any of
these monomers. In general, any rubbery or glassy vinyl type
monomer may be used which can be mixable with the
organosiloxane.
Preferred vinyl-based polymer ^omponents of the
first stage substrate of the polyorganosiloxane/polyvinyl-
based graft copolymer comprise primarily alkenyl aromatic
units, (meth)acrylate units or mixtures thereof. Especially
preferred is polystyrene.
~ ypically, the vinyl-based component of the first
stage co-homopolymer will be present in an amount of
approximately 3 to 97 weight percent and correspondingly the
organosiloxane component will be present in an amount of
approximately 97 to 3 weight percent. Preferably, the
vinyl-based component will comprise approximately 5 to 45
weight percent of the first stage of the co-homopolymerized
substrate.
Most preferably, the vinyl polymer of the first
stage comprises styrene and the ratio of organosiloxane to
styrene is about 88 to 12. Most preferably, the second stage
comprises a styrene/acrylonitrile copolymer with a styrene to
acrylonitrile ratio ranging from about 3 to 1 to about 1 to 1
and preferably 3 to 1 or 1 to 1. Most preferably, in a two
stage composition, the ratio of first stage substrate to
subsequent stage ranges from about 1 to 1 to about 7 to 3 and
preferably 1 to 1 or 7 to 3.
If more than one~ subsequent stage is to be used,
preferably the vinyl polymer of the first stage substrate
will comprise styrene, the intermedi~te stage will comprise a
copolymer of styrene/acrylonitrile, and the outermost stage
will comprise polymerized methylmethacrylate. Most
preferably, the ratio of the components of the first to the
intermediate stages will be as immediately above and the
-26- 336-2221 (8CV-5084~5118)
ratio of first stage substrate to intermediate stage to
third, outermost stage will be 70 to 15 to 15.
The cross-linker composition used in conjunction
with the organosiloxane component of this modifier type can
have the general formula:
R2n ~ Si(OR )4-n
wherein n is 0, 1 or 2, preferably 0 or 1, and each Rl
independently represents hydrogen or a monovalent hydrocarbon
radical selected from among alkyl or aryl radicals having 1
to 16 carbon atoms, preferably methyl, ethyl and phenyl. R2
can be the same as R or can be a vinyl, alkenyl, thio, or
(meth)acryloxy alkyl functional radical. ~hen R2 is a vinyl,
alkenyl, thio or acryloxy alkyl radical and n is 1, ~he
cross-linker compound can also act as a graft-linker.
A preferred cross-linker compound is tetraethoxy-
silane. A combination cross-linking and graft-linking
compound is vinyltriethoxysilane. Another suitable choice is
gamma-methacryloxypropyltrimethoxysilane.
The organosiloxane modifier products can be
isolated by conventional means such as hot solution
coagulation. For example, an electrolytic solution of about
0.5 to 5 percent aluminum sulfate or magnesium sulfate in
water can be prepared and heated to about 75 to 95~C. When
the latex is added, with agitation, the graft product ~ill
~5 precipitate and can be held at an elevated temperature for
about 10 minutes whereupon it may be filter washed.
Commerical latex isolation techniques such as spray dryers
may also be utilized.
The term EPDM modifier encompasses copolymers of
ethylenically unsaturated olefins and non-conjugated diene
polymers. Preferably EPDM modifiers encompass rubbery
terpolymers comprising copolymerized units of ethylene and
propylene and a non-conjugated diolefin and grafted
derivatives thereof and preferably comprising an ethylene-
-27- 336-2221 (8CV-5084/5118)
propylene-diene terpolymer and grafted on derivatives
thereof.
Ethylene-propylene-diene terpolymers are well known
in the art and are rubbery terpolymers comprising copolymerized
units of ethylene, propylene, and a non-conjugated diolefin.
The non-conjugated dienes useful in the preparation
of these terpolymer elastomers may include chain non-conjugated
dienes such as 1,4-hexadiene and also cyclic (especially
bridged ring) non-conjugated dienes such as dicyclopentadiene,
5-methylene-2-norbornene, 5-ethylidene-2-norbornene, and
1,4-cyclooctadiene. Preferred is 5-ethylidene-2-norbornene.
Methods for the preparation of ethylene-propylene-
diene terpolymers are described in U.S. Patent ~os. 2,933,480,
3,000,866 and 3,~00,867.
The grafted derivatives of these terpolymers are
well known in the art as well. These resins may be
characterized as resinous compositions of (A~ polymerized
alkenyl aromatic units and/or (B) polymerized acrylic units
in combination with (C) a rubbery terpolymer comprisin~
copolymerized units of ethylene and propylene and a
non-conjugated diolefin, or as an ethylene-propylene-
non-conjugated diene interpolymer grafted with the homopolymer
or copolymer of monoethylenically unsaturated monomers as
disclosed in UOS. Patent No. 4,202,948, for example, styrene,
styrene-acrylonitrile, methyl methacrylate, styrene-methyl-
methacrylate, halostyrene, alpha-methylstyrene, p-methyl-
styrene, acrylonitrile, methacrylonitrile, acrylic acid,
methacrylic acid, the lower- alkyl esters of acrylic acid and
methacrylic acid, styrene maleic anhydride, and other alkyl
ring substituted styrenes and acrylates including acrylates
and alkacrylates and the like.
Preferably, these graft polymers are produced by
polymerizing the resin forming alkenyl aromatic monomer and
the acrylic monomer in the presence of a rubbery terpoly~er
of ethylene, propylene and a non-conjugated diolefin.
~?,~
-28- 336-2221 (8CV-5084/5118)
~he non-conjugated dienes used in the preparation
of the grafted terpolymer elastomers are as explained above.
Such EPDM modifiers are more fully described in U.S. Patent
No. 4,626,572.
The term SEBS modifier is meant to include
styrene-ethylene/butene-styrene block copolymers. These
copolymers are three segment linear block copolymers with
weight average molecular weights (as estimated in solution by
gel permeation chromatography standardized with reference to
and expressed as polystyrene) of between about 89,000 + 1,000
and about 238,000 + 4,000. The center segment is generally a
hydrogenated polybutadiene and preferably a random copolymer
of ethylene and butylene and the end segments are generally
styrene. Such modifiers are more fully described in U.S.
Patent No. 4,709,982.
The term ABS modifier refers to impact modifiers
which are well known to those skilled in the art and aee
represented principally by graft copolymers of vinyl
cyanide-conjugated diolefin-alkenyl aromatic. ~hey
particularly comprise acrylonitrile-butadiene-styrene graft
copolymers, but also encompass mixtures of analogous
materials.
Particul~rly suitable ABS impact modifier can be
produced according to the procedures as set forth in U.S.
Patent No. 4,764,563.
Such impact modifiers are prepared by gr3fting
particular ratios of sytrene and acrylonitrile on
butadiene-based rubber substrates~
Specifically, these impact modifiers are ABS 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 UD tO 1~
-29- 336-2221 (8CV-5084/5118)
weight percent of acrylonitrile and/or an alkyl acrylate in
which the alkyl group contains 4 or more carbon ato~s, 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 and
copolymer rubbers are well known and widely employed
commercially for a number of 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 form suitable for use in subsequent graft
polymerization processes.
These preferred ABS-type impact modifiers are
prepared by graft polymerizing from about 40 to about 70,
preferably from 47 to 61 parts by weight of a grafting
monomer mixture comprising a monovinyl aromatic compound
(MVA), such as styrene, alpha 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 ha~ing a rubber content of
from about 50 to about 85 weight percent, preferably from 62
to 78 weight percent and, correspondingly, a graft monomer
component or superstrate of from 50 to 15, preferably from 48
to 22 weight percent.
The weight ratio of the MYA 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.
~13~ t~
-30- 336-2221 (8C~-5084/5118)
This graft polymerization of the MVA/EUN monomer
mixture in the presence of the rubbery 5ubstrate may be
carried out by any of the gra~t 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 transfer 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 peroxides
such as dicumyl peroxide or azo initiators such as
azobisisobutyronitrile~ 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 processes may be employed. The graft polymerization
process used in the preparation of the ABS impact modifiers,
as well as those processes used in coa~ulating and isolating
the ABS impact modifier for further use, are thus well known
and conventional, and the application of such processes to
the preparation of the ABS impact modifiers for further use,
are thus well known, conventional, and apparent to those
skilled in the art.
The ABS impact modifier 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 ethylenicaily
unsaturated monomers, one of which comprises styrene and/or
substituted styrene. Preferred substituted styrenes include,
but are not limited to, halogen-substituted styrene,
particularly wherein the halogen is substituted on the
aromatic ring; alpha-methyl styrene and para-methyl styrene.
The other ethylenically unsaturated monomer which is used in
forming the rigid portion may be selected from acrylonitrile,
~ A f) ~3
-31- 336-2221 (8CV-5084/5118)
substituted acrylonitriles, acrylates, alkyl-substituted
acrylates, methacrylates, alkyl-substituted methacrylates,
and ethylenically unsc urated carboxylic acids, diacids,
dianhydrides, acid esters, diacid esters, amides, imides and
S 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, methacrylonitrile,
alkyl methacrylates, maleic anhydride, maleimide, alkyl
maleimides, 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
preferably 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 unsaturated
olefins and non-conjugated diene polymers (EPDM) rubbers as
previously described above~ 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 por~ion and the rigid portion. More
preferably, the styrenic polymer component comprises from
A ( ~ '
Ç.. . :~
-32- 336-2221 (~CV-5084/5118)
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.
Most preferably, the ABS modifier will comprise a
terpolymer of acrylonitrile (AN), butadiene (BD) and styrene
~S) having a S to AN ratio of from about 3.5:1 to 2.5:1 and
most preferably 3.5:1, 3.0:1 or 2.5:1, and a BD to S/AN ratio
of 7:3.
Suitable commercially available ABS modifiers are
available under the tradename BLENDEX- from General Electric
Company. It is preferred at present to use BLENDEX- 338, S
to AN ratio of 3.0:1Ø
The modifiers (B) of the present invention
typically comprise from about 5 to 25 parts by weight based
upon 100 parts by weight of the polyester and the modifier
combined and most preferably from about 15 to about 20 parts
by weight, and the polyester resin correspondingly
comprises from about 95 to about 75 parts by weight, and
preferably from about 85 to about 80 parts by weight of
polyester and modifier combined. Most preferably, the
modifier comprises 15 parts by weight and the polyester resin
comprises 85 parts by weight based upon 100 parts by weight
of polyester and modifier combined.
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.
Conventional processing for mixing thermoplastic
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,
co-kneaders, or extruders under conditions known to one of
ordinary skill in the art.
-33- 336-2221 (8CV-5084/5118)
Additionally, additives such as antioxidants,
nucleating agents such as talc and the like, other stabilizers
including but not limited to UV stabilizers, reinforcing
fillers such as talc, glass fibers and the like, ~lame
retardants, pigments or combinations thereof may be added to
the compositions of the present invention.
D~SCRIPTION O~ TUE PR~P~RR~D ~BODI~E~TS
The following examples illustrate the invention
without 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
ductile/brittle transition temperatures. Tensile properties
are measured by ASTM-D-638 as tensile elongation and tensile
strength, and flexural properties are measured by ASTM-D-790
as flexural strength and flexural modulus. Heat sag is
represented according to ASTM-D-3769-810
eXAMPLE 1
A well mixed dry blend of 79.0 parts of poly(l,4-
butylene-trans-1,4-cyclohexanedicarboxylate) (PBCD) (melt
viscosity 3300 poise at 250C), 20.0 parts of an ASA modifier
(polybutyl acrylate elastomer-styrene/acrylonitrile
interpolymer - Geloy' XSAN - General Electric Company -
Pittsfield, MA) and 1.0 part of a stabilizer package was
ex~ruded on a 2.5" ~PM extruder operating at 100 rpm with
barrel zones at 250C.
The extruded blend was observed to be homogeneous.
Test parts were molded on a 3.5 oz. Van Dorn molder with
barrel temperatures at 250C and mold temperature at 75C and
with a 30 second cycle. Properties are summarized in Table
1.
~XAMPL~ 2
The procedure of Example 1 was followed substituting
a dry blend of 79.0 parts of PBCD (melt viscosity 3300 poise
~ "' ~
-34- 336-2221 (8CV-5084/5118)
at 250C), 20.0 parts of an ASA modifier (polybutyl acrylate
elastomer-styrene/acrylonitrile-additional styrene/
acrylonitrile interpolymer - Geloy- 1120 - General Electric
Company), and 1.0 part of a stabilizer package.
The extruded blend was observed to be homogeneous.
Properties are summarized in Table 1.
XA~PL~ 3
The procedure of Example 1 was followed substituting
a dry blend of 78.5 parts of PBCD (melt viscosity 3300 poise
at 250C), 20.0 parts of an ASA modifier (polybutyl acrylate
elastomer-styrene/acrylonitrile interpolymer - Geloy~ XSAN -
General Electric Company), 1.0 part of a stabilizer package,
and 0.5 part of a nucleating agent.
The extruded blend was homogeneous. Properties are
summarized in Table 1.
~XAMPLE 4
The procedure of Example 1 was followed substituting
a dry blend of 78.5 parts of PBCD (melt viscosity 3300 poise
at 250C), 20.0 parts of an ASA modifer (polybutyl acrylate-
styrene/acrylonitrile-additional styrene/acrylonitrile
interpolymer - Seloy- 1120 - General Electric Company), 1.0
part of a stabilizer package, and 0.5 part of a nucleating
agent.
The extruded blend was homogeneous. Properties are
summarized in Table 1.
~XA~PL~ 5
The procedure of Example 1 was followed substituting
a dry blend of 84.0 parts of PBC~ (melt viscosity 5000 poise
at 250UC), 15.0 parts of diene-based core-shell multi-stage
polymer modifier (core = polymerized butadiene, styrene,
methylmethacrylate and divinylbenzene - second stage shell =
polymerized styrene - outer shell = polymerized
methylmethacrylate and 1,3-butylene glycol dimethacrylate -
~ ~, ! . ' "
-35- 336-2221 (8CV-5084/5118)
ACRYLOID- KM 653, also known as PARALOID~ EXL 3691 - Rohm &
Haas Company - Philadelphia, PA) and 1.0 part of a stabilizer
package.
The extruded blend was observed to be homogeneous.
Properties are summarized in Table 1.
COMPARATIVE EXAMPLE SA~
The procedure of Example 1 was followed substituting
100.0 parts of P8CD (melt viscosity 5000 poise at 250C) for
the dry blend.
Properties are summarized in Table 1.
EXAMPLE 6
The procedure of Example 5 was followed substituting
an acrylate-based core-shell multi-stage polymer modifier
(core = polybutylacrylate - shell = methylmethacrylate -
ACRYLOID- KM 330, also known as PARALOID~ EXL 3330 - Rohm &
Haas Company) for the modifier.
Properties are summarized in Table 1.
EXAMPLE 7
The procedure of Example 5 was followed substituting
an EPDM modifier (EPDM - S/AN - Royaltuf 372-P - ~niroyal
Middlebury, CT) for the modifier.
Properties are summarized in Table 1.
EXA~PL~ 8
The procedure of Example 5 was followed substituting
an organosiloxane-based modifier with a styrene/acrylonitrile
outer most stage (SIM-S/AN, SIM=Si/St, Si:St=88:12, S:AN=3:1,
Si/St:S/AN=70:30) for the modifier.
Properties are summarized in Table 1.
/ , ~, J
-36- 336-2221 (8CV-5084/5118)
EXAMPLE 3
The procedure of Example 5 was followed substituting
an organosiloxane-based modifier with a methylmethacrylate
outer most stage (SIM-MMA) for the modifier.
Properties are summarized in Table 1.
eX~PLE 1 0
The procedure of Example 5 was followed substituting
an ASA modifier (polybutyl acrylate elastomer-styrene
interpolymer - Geloy- XS - General Electric Company) for the
modifier.
Properties are summarized in Table 1.
EXAHPLE 11
The procedure of Example 5 was followed substituting
an ASA modifier (polybutyl acrylate elastomer-styrene/
acrylonitrile interpolymer - Geloy- XSAN - General Electric
Company) for the modifier.
Properties are summarized in Table 1.
~XAMPL~ 12
The procedure of Example 5 was followed substituting
an SEBS modifier (styrene-hydrogenated polybutadiene-styrene
block copolymer-weight average molecular weight = 238,000 +
4,000 - Kraton- G1651 - Shell Chemical Company - Houston, TX)
for the modifier.
Properties are summarized in Table 1.
~XA~PL~ 13
The procedure of Example 5 was followed substituting
an ABS modifier (BLENDEX- 33B - General Electric Company) for
the modifier.
Properties are summarized in Table 1.
~ : ~3~
-37- 336-2221 (8CV-5084/5118)
EXAMPLE 14
The procedure of Example 1 was followed substituting
a dry blend of 83.55 parts of PBCD (melt viscosity 5000 poise
at 250C), 15.0 parts of an AaS modifier (BLENDEX- 338 -
General Electric Company), and 1.45 parts of a stabilizerpackage.
Properties are summarized in Table 1.
EXAMPLE 15
The procedure of Example 1 was followed substituting
a dry blend of 81.98 parts of PBCD (melt viscosity 5000 poise
at 250C), 14.72 parts of an ABS modifier (BLENDEX~ 338 -
General Electric Company), 1.42 parts of a stabilizer package
and 1.88 parts of green pigment.
Properties are summarized in Table 1.
Examples 1-15 illustrate the excellent impact
strength even at low temperatures and the excellent tensile
properties that various compositions according to the present
invention possess.
-~8- ~36-2221 ( 8CV-~084/5118 )
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-40- 336-2221 ( 8CV-5084/;118 )
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-~1- 336-2221 (8CV-5084/5118)
TABL~ 1 (continued)
A - poly(l,4-butylene-trans-1,4-cyclohexanedicarboxylate) -
melt viscosity 3300 poise at 250C
B - poly(l,4-butylene-trans-1,4-cyclohexanedicarboxylate) -
melt viscosity 5000 poise at 250C
C - green pigment
D - polybutyl acrylate elastomer-styrene/acrylonitrile
interpolymer - (Geloy~ XSAN - General Electric Co
Pittsfield, MA)
E - polybutyl acrylate elastomer-styrene/acrylonitrile -
styrene acrylonitrile interpolymer - (Geloy~ 1120
General Electric Co. - Pittsfield, MA)
F - 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 - (ACRYLOID~ ~M 653,
also known as PA~ALOID- E%L 3691 - Rohm & Haas Co
Philadelphia, PA).
G - core-shell multi-stage polymer - core = polymerized
butylacrylate - shell = polymerized methylmethacrylate -
(ACRYLOID~ KM 330, also known as PARALOID~ EXL 3330 -
Rohm & Haas Co. - Philadelphia, PA)
H - EPDM with SAN graft - Royaltuf- 372-P - Uniroyal -
Middlebury, CT)
I - SIM-S/AN multi-stage polymer - SIM=Si/St - Si St=88 12-
S:AN=~:1 5i/S t S/AN=70 30
J - SIM-MMA multi-stage polymer
K - poly(butylacrylate elastomer - styrene/acrylonitrile -
styrene interpolymer - (Geloy- XS - General Electric Co
Pittsfield, MA)
L - SEBS modifier-styrene-hydrogenated polybutadiene-styrene
block copolymer-weight average molecular weight =
238,000 + 4000 (Rraton- G1651 - Shell Chemical Co
Houston, TX)
M - ABS modifier (BLENDEX- 338 - General Electric Co
Pittsfield, MA)
"-" - Value not determined
~ ~ r~
-42- 336-2221 (8CV-50B4/5118)
EXAlfPLE 1 6
A well mixed dry blend of 85.0 parts of poly(l,4-
butylene-trans-1,4-cyclohexanedicarboxylate) (PBCD) and 15.0
parts of an ABS modifier having a S:AN ratio of 4.0:1.0 and a
BD:SAN ratio of 50:50 was extruded, molded and tested as in
Example 1.
Ductile/brittle transition temperature (D/B) was
determined by Notched Izod to be 0C. Properties are
summarized in Table 2.
~XAMPL~ 17
The procedure of Example 16 was followed substituting
an ABS modifier having a S:AN ratio of 3.5:1.0 and a BD:SAN
ratio of 50:50.
D/B was determined to be 0C. Properties are
summarized in Table 2.
EXA~PLE 18
The procedure of Example 16 was followed substituting
an ABS modifier having a S:AN ratio of 3.0:1.0 and a BD:SAN
ratio of 50:50.
D/B was determined to be 0C. Properties are
summarized in Table 2.
EX~MPL~ 19
The procedure of Example 16 was followed substituting
an ABS modifier having a S~AN ratio of 2.5:1.0 and a BD:SAN
ratio of 50:50.
D/B was determined to be 0C. Properties are
summarized in Table 2.
EXAMPL~ 20
The procedure of Example 16 was followed substituting
an ABS modifier having a S:~N ratio of 2.3:1.0 and BD:SAN
ratio of 50:50.
-43- 336-2221 (8CV-5084/5118)
D/B was determined to be 0C. Properties are
summarized in Table 2.
LXAMPL~ 21
The procedure of Example 16 was followed substituting
an ABS modifier having a S:AN ratio of 1.9:1.0 and a BD:SAN
ratio of 50:50.
D/B was determined to be 0C. Properties are
summarized in Table 2.
~XA~PL~ 22
The procedure of Example 16 was followed substituting
an ABS modifier having a S:AN ratio of 3.5:1.0 and a B~:SAN
ratio of 70:30.
D/B was determined to be -45C. Properties are
summarized in Table 2.
eXAMP~E ~3
The procedure of Example 16 was followed substituting
an ABS modifier having a S:AN ratio of 3.0:1.0 and a BD:SAN
ratio of 70:30.
D/B was determined to be -45C. Properties are
summarized in Table 2.
EXA~PL~ 24
The procedure of Example 16 W2s followed substit~ting
an ABS modifier having a S:AN ratio of 2.5:1.0 and a BD:SAN
ratio of 70:30-
D/B was determined to be -35C. Properties are
summarized in Table 2.
Examples 16-24 indicate that an ABS modifier having
a S:AN ratio of 3.0:1.0 and a BD:SAN ratio of 70:30 is close
to the optimum for the modification of PBCD. Low S:AN ratio
may be good for weatherability, but it is detrimental to low
temperature impact strength.
-44- 336-2221 (8CV-5084/5118)
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-45- 336-2221 (8CV-5084/5118)
EXAMPLE 25
A well mixed dry blend of 80.0 parts of poly(l,4-
butylene-trans-1,4-cyclohexane dicarboxylate) (PBCD) and 20.0
parts of an organosiloxane modifier (Si/St-S/AN (Si:St=88:12-
S:AN=3:1-Si/St:S/AN=50:50)) was extruded, molded and tested
as in Example 1.
D/B was determined to be -30C. Properties are
summarized in Table 3.
EXA~PL~ 26
The procedure of Example 25 was followed substituting
a dry blend of 85.0 parts of poly(l,4-butylene-trans-1,4-
cyclohexane dicarboxylate) (PBCD) and 20.0 parts of an
organosiloxane modifier (Si/St-S/AN (Si:St=88:12-S:AN=3:1-
Si/St:S/AN=70:30)).
D/B was determined to be -30C. Properties are
summarized in Table 3.
EXA~PL~ 27
The procedure of Example 26 was followed substituting
an organosiloxane modifier Si/St-S/AN-MMA (Si:St=B8:12-S:AN=
20 1:1-Si/St:S/AN:MMA=70:15:15)).
D/B was determined to be above -30C. Properties
are summarized in Table 3.
~XAMPLE 28
The procedure of Example 26 was followed substituting
25 an organosiloxane modifieE (Si/St-S/AN (Si:St=88:12-S:AN-3:1-
Si/St:S/AN=70:30)) (second sample).
D/B was determined to be 0C. Properties are
summarized in Table 3.
Organosiloxane modifiers having a low S:AN ratio
30 gave better color retention but worse impact properties
similar to the S:AN ratio effect in ABS modifiers.
r~' n ~
-46- 336-2221 (8CV-5084/5118)
TABL~ 3
Optimization of Organosiloxane Modifiers for PBCD Performance
Example 25 26 27 28
PBCDA 80.0 as.o 85.0 85.0
Organosiloxane
Modifier 20.0 15.0 15.0 15.0
Si:St ratio 88:12 88:12 88:12 88:12
S:AN ratio 3:1 3:1 1:1 3:1
Si/St:S/AN:MMA
ratio 50:50:0 70:30:070:15:15 70:30:0
Ductile/Brittle
Transition
Temperature
determined by
Notched Izod (C) -30 -30 >-30 0
A - poly(l,4-bu~ylene-trans-1,4-cyclohexane dicarboxylate).
c; ~ ~, r
-47- 336-2221 ( 8CV-50~4/5118 )
E:XAMPLE 2 9
95.0 parts of a blend prepared by the procedure of
Example 14 were mixed with 5.0 parts of glass reinforcing
fibers. The resultant blend was extruded, molded, and tested
as in Example 1.
Properties are summarized in Table 4.
COMPARATIV~ E&A~PL~ 2gA~
95.0 parts of poly(l,4-butylene-trans-1,4-cyclohexane
dicarboxylate) (PBCD) (melt viscosity 5000 poise at 250C)
were mixed with 5.0 parts of glass reinforcing fibers. The
resultant blend was extruded, molded and tested as in Example
1.
Properties are summarized in Table 4.
~AMPLE 30
lS 90.0 parts of a blend prepared by the procedure of
Example 14 were mixed with 10.0 parts of glass reinforcing
fibers. The resultant blend was extruded, molded and tested
as in Example 1.
Properties are summarized in Table 4.
COMPARATIVE eX~MPLE 30A~
90.0 parts of poly(l,4-butylene-trans-1,4-cyclohexane
dicarboxylate) (PBCD) (melt viscosity 5000 poise at 250C)
were mixed with 10.0 parts of glass reinforcing fibers. The
resultant blend was extruded, molded, and tested as in
Example 1.
Properties are summarized in Table 4.
EXAMPLE 31
90.0 parts o~ a blend prepared by the procedure of
Example 15 were mixed with 10.0 parts of glass reinforcin~
fibers. The result~nt blend was extruded, molded, and tested
as in Example 1.
Properties are summarized in Table 4.
-4a- ~36-2221 (8CV-5084/5118)
EXAMPLE 32
85.0 parts of a blend ~repared by the procedure of
Example 14 were mixed with 15.0 parts of glass reinforcin3
fibers. The re~ultant blend was extruded, molded, and tested
as in Example 1.
Properties are summarized in Table 4.
COMPARATIVE EXA~PLE 32A~
85.0 parts of poly(l,4-butylene-trans-1,4-cyclo-
hexane dicarboxylate) (PBCD) (melt viscosity 5000 poise at
250C) were mixed with 15.0 parts of glass reinforcing
fibers. The resultant blend was extruded, molded, and tested
as in Example 1.
Properties are summarized in Table 4.
EXAMPLE 33
70.0 parts of a blend prepared by the procedure of
Example 14 were mixed with 30.0 parts of glass reinforcing
fibers. The resultant blend was extruded, molded and tested
as in Example 1.
Properties are summarized in Table 4.
~XAMPL~ 34
93.0 parts of a blend prepared by the procedure of
Example 14 were mixed with 5.0 parts of glass reinforcing
fibers and 2.0 parts of talc. The resultant blend was
extruded, molded and tested as in Example 1.
Properties are summarized in Table 4.
Examples 29-34 demonstrate the excellent impact ~nd
tensile properties of various reinforced compositions
according to the present invention.
-49- 336-2221 (8C~;'-5084/5118)
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-50- 336-2221 (8CV-5084/5118)
A - 83.55 parts P8CD ~poly(1,4-butylene-trans-1,4-cyclohexane
dicarboxylate~ (melt viscosity 5000 poise @ 250C), 15.0
parts ABS modifier (BLENDEX- 338 - General Electric
Company), and 1.45 parts of a stabilizer package (Example
14).
8 - 81.98 parts P8CD (poly(1,4-butylene-trans-1,4-cyclohexane
dicarboxylate) (melt viscosity 5000 poise @ 250C), 14.72
parts ABS modifier (BLENDEX- 338 - General Electric
Company), 1.42 parts o~ a stabilizer package, and 1.88
parts of green pigment (Example 15).
C - poly(l,4-butylene-trans-1,4-cyclohexane dicarboxylate) -
melt ViSCQSity 5000 poise at 250C.
D - glass reinforcin~ fibers.
E - talc.
s ~
-51- 336-2221 (8CV-5084/5118)
EXAMPLE 35
A well mixed dry blend of 82.05 parts of a
copolymer of poly(cis- and`~trans-1,4-cyclohexanedimethylene-
trans-1,4-cyclohexanedicarboxylate) (cis:trans=25:75) (PCCD),
15.0 parts of an ABS modifier (~LENDEX- 338 - General
Electric Company), 0.5 part of a nucleating agent, 1.45 parts
of a stabilizer package, and 1.0 part of a light blue pigment
blend was extruded on a single screw ~.5" HPM extruder having
a barrel temperature of 500F. The resultant pellets were
molded into test pieces on a 3.5 oz. Van Dorn injection
molding machine set at 500F barrel temperature and 150F
mold temperature.
The product showed poor distribution of the rubber.
Properties are summarized in Table 5.
COhPARATIVE EXAnPL~ 35A~
The procedure of Exa.~ple 35 was followed substituting
a dry blend of 97.5 parts of PCCD (25:75 copolymer of cis-
and trans-1,4-cyclohexanedimethylene-trans-1,4-cyclohexane-
dicarboxylate), and 2.0 parts of an ionomer (Surlyn^ 8940 -
E. I. DuPont de Nemours 6 Co. Wilmington, DE), and 0.5 part
of a nucleating agent.
Properties are summarized in Table 5.
EXAMPLE 36
Extruded pellets were prepared by the procedure of
Example 35, were reextruded on a Werner Pfleiderer twin screw
extruder, were molded and were tested as in Example 35.
Properties are summarized in Table 5.
EXAMPLE 37
A well mixed dry blend of 80.6 parts of PCCD (25:75
copolymer of cis- and trans 1,4-cyclohexanedimethylene-trans-
1,4-cyclohexanedicarboxylate - melt viscosity 3000 poise at
250C), 15.0 parts of an ABS modifier (~LENDEX~ 338 - General
Electric Company), 4.0 parts of talc and 0.4 part of a
~ J ,r~ n ~
-52- 336-2221 (8CV-5084/5118)
stabilizer package was extruder on a Werner Pfleiderer twin
screw extruder, molded on a 3.5 oz. Van Dorn injection
molding machine, set at 500F barrel temperature at 150F
mold temperature and tested as in Example 1.
Properties are summarized in Table 5.
COMPARATIV~ ~XAMPLE 37A~
The procedure of Example 37 was followed substituting
a dry blend of 96.0 parts of PCCD ~25:75 copolymer of cis- and
trans-1,4-cyclohexanedimethylene-trans-1,4-cyclohexane-
dicarboxylate) and 4.0 part~s of talc.
Properties are summarized in Table 5.
EXAMPL~ 38
The procedure of Example 37 was followed substituting
a diene-based core-shell multi-stage polymer modifier (core =
polymerized butadiene, styrene, methylmethacrylate and
divinylbenzene - second stage shell = polymerized styrene -
outer shell = polymerized methylmethacrylate and 1,3--butylene
glycol dimethacrylate - ACRYLOID- KM653, also known as
PARALOID' EXL 3691 - Rohm 6 Haas Company - Philadelphia, PA)
for the ABS modifier.
Properties are summarized in Table 5.
EXAMPL~ 39
The procedure of Example 37 was followed substituting
an SEBS modifier (styrene-hydrogenated polybutadiene-styrene
block copolymer - weight average molecular weight = 238,000 +
4,000 - Kraton- G1651 - Shell Chemical Company - ~ouston, TX)
for the A8S modifier.
Properties are summarized in Table 5.
~3 r` ~ ~ n ~, ç-)
-53- 336-2221 (8CV-5084/5118)
Examples 35-39 illustrate the excellent impact
strength and the excellent tensile properties that various
compositions according to the present invention possess.
Examples 37-39 illustrate the effect of the
addition of optional fillers.
G'? ,'~ ` /1 t- ~ ?
-54- 336-2221 (8CV-;084/5118)
TABL~ 5
Impact Modified PCCD Compositions
Example 35 35A* 36 37 37A~ 38 39
Composition
PCCD 82.05 97.5 82.05 - 96.0
PCCD3 - D - - 80.6D ~ 80.6 80.6
Modifier 15.0 - 15.0D 15.0 - l~.oE l;.oF
Stabilizer 1.45 - 1.45 0.4 - 0.4 0.4
Nucleating
Agent 0.5 0.5 0.5
Lt. Blue
e~ Pigmen~ Blend 1.0 - 1.0 - - - -
Ionomer - 2.0
Talc - - - 4.0 4.0 4.0 4.0
Properties
Tensile
Slongation
as molde~ (%) 90 135 25 197 25 280 300
annealed (~) - - - 23 - 28 25
Tensile Strength
as molded
(p~i) 5350 5470 4800 4100 5900 3900 3500
anneal~d
(psi)~ - - - 5300 - 5200 4700
Flexural
Strength
as molded
(psi)~ 6900 8000 8100 6aoo 8500 6300 ~700
anneal~d
(psi) 8400 10100 - 8200 11200 8000 7400
Flexural
,~odulus
as molded
(Rpsi) 129 161 146 142 198 129 98
annealed
(Kpsi)~ 161 171 - 165 218 154 135
Unnotched Izod
@ RT as molded
(fpi) 23.7 19.7 13.3 25.7 20.5 25.7 23.2
Notched Izod
@ RT as molded
(~pi) 3.9 1.1 1.6 15.8 0.6 15.7 15.8
anneal~d
(fpi)~ - - - 2.2 - 3.6 2.a
-55- 336-2221 (8CV-5084/5118)
TABL~ 5 (cont'd)
_xample 35 35A* 36 37 37~* 3a 39
Falling Dart
Impact
as molded at
max. load
(ft-lbs)16.6 19.7 9.416.5 20.5 17.4 16.5
total
(ft-lbs)22.5 30.1 20.825.1 28.2 24.4 25.7
annealed~
max. load
(ft-lbs) - - - 14.0 - 17.0 16.0
total
(ft-lbs) - - - 18.0 - 24.0 24.0
Melt Viscosity
(p) at 250C 4500 3500 - 6300 2700 630Q 4200
DSC Results
Tch (C)H - - - 119 ~ 123 123
Hch (J/g) - - - 16 - 15 16
Tm (C)J - - - 224 - 226 228
Hm (J/g) - - - 21 - 20 20
Tcc (C)L - - - 172 - 168 172
Hcc (J/g) - - - 16 - 15 lo
C~ r ~
f~ , ~, . ;.i
-56- 336-2221 (8CV-5084/5118)
A - 25:75 copolymer of poly(cis-/trans-1,4-cyclohexane-
dimethylene-trans-1,4-cyclohexane dicarboxylate).
B - poly(l,4-cyclohexanedimethylene-trans-1,4-cyclohexane
dicarboxylate-melt viscosity 3000 poise at 250C.
C - Surlyn- 8940 - E. I. DuPont de Nemours & Co. - Wilmington,
DE.
D - ABS modifier - BLENDEX- 338 - General Electric Co. -
Pittsfield, MA.
E - core-shell multi-stage polymer - core = polymerized
butadiene and styrene, methylmethacrylate and divinyl-
benzene - 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 Co. -
Philadelphia, PA.
F - SEBS modifier - styrene-hydrogenated polybutadiene-styrene
block copolymer - weight average molecular weight =
238,000 + 4,000 (Kraton- G1651 - Shell Chemical Co. -
Houston, ~X).
G - after storing the parts at 250C for 3 hours.
H - peak crystallization temperature when heated at 20C/min.
from the amorphous state.
I - enthalpy of crystallization when heated at 20C/min. from
the amorphous state.
J - peak melting temperature when heated at 20C/min. from
the amorphous state.
K - enthalpy of melting when heated at 20C/min. from the
amorphous state.
L - peak crystallization temperature when cooled at 60C/min.
from the molten state.
M - enthalpy of crystallization when cooled at 60C/min.
from the molten state.
-57- 336-2221 (8CV-5084/5118)
All patents, applications, publications, and test
methods mentioned above are hereby incorporated by reference.
Many variations of the present i.nvention 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.
