CA2033899A1 - Polycarbonate and polyester blends modified with polyorganosiloxane graft polymers combined with diene rubber-based graft polymers - Google Patents

Abstract

337-2167 (8CT-4861) ABSTRACT OF THE DISCLOSURE
Polycarbonate and polyester blends are prepared with a combination of modifiers comprising a multi-stage polyorganosiloxane-based graft polymer composition and a diene rubber-based graft polymer composition imparting a wide range of excellent physical properties on the PC
and PE blends.

Description

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-1- 337-2167 ( aCT-4861 ) lPOLYCARBOe~AT~ AlaD POLYI~STi~ Llel~DS
tlODIFIE~D WITEI PO~YORGAa~O~IL02~ANE~ GRAI~T
POLY~I~RS COMBI~E:D ~ITEI DII~ RUBiBER--BASED GRAF~P POL~qEElS
. .
C~O~S-~F~R~ OE TO R~LATED APP~ICATIO~S
5This application is ~elated to the following commonly owned, concurrently-filed U.S. patent applications:
ATTY'S SUa~CT
S~RIAL ~0. DOC~T ~T~R APP~ICAMT(51 337-2159 Polyorganosilo- I-C. W. Wang (8CT-4838/ xane/polyvinyl 60) based Graft Polymers~ Process and Thermoplastic Composition~ Containing the Same 337-2160 Thermoplastic J.L DeRudder (8CT-4839) Molding Composi F~Jo Traver tion~ Containing I-Co W~ Wang Polyorganosilo-xane/Polyvinyl-based Graft Polymer Modifiers 337-2161 Low Gloss Molded J.L. DeRudder (8CT-4840) Articles Using H. Savenije polyorganosiloxane/ I-C. W. Wang polyvinyl-based Graft Polymers 337-21S2 Polyphenylene ether M~A. Alsamarraie (8CT-4856) or Polyphenylene W.R. Haaf ether/Polystyrene W.J. Peascoe with Polyorgano- I-C~ W. Wang siloxane/polyvinyl-based Graft Po.ymer Modifier~ -., .

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-2- 337-2167 (aCT-~861) A~TY'S SUBJBCT
SERIAL ~O. DOe~T ~A~T~R APPLICA~T~S) 337-2163 Polyorgano- M.A. Alsamarraie (8C'r-4857) siloxane/poly- S.Y. Hobbs vinyl-based I-C. ~. Wang Graft (meth)- V.H. Watkins acryla~e Polymer~
337-2164 Polyester, Poly- M~A. Alsamarraie (8CT-4858) carbonate and/ S.Y. ~obbs or Polyphenylene I--C. W. Wang ether wi~h Poly- V.~. Watkins organosiloxane/
polyvinyl-based Graft (meth)-acrylate Polymer 337-2165 Flame Retardant I-C. W. Wang (8CT-4859) Polyorganosiloxane~
based Graft Polymer~
337-2168 Polyesters JoL~ DeRudder ~0 (8CT-4862) Modified with I C. W. Wang Polyorganosiloxane~
polyvinyl-based Graft Polymers ) O~ 0-This inven~ion relates to hermoplastic polycarbonate resins and blends with a thermoplastic polyester resin modified by a combination of a multi-stage polyorganosiloxane-based gra~t polymer composition and a diene rubber-based graft polymer composition.

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-3- 337-2167 (~CT-4861) ACRGR~D OF T~E I~V~TION
There have been many at~e~pts in the art to provide polyorganosiloxane-based graft polymers which may be useful as impact streng~h modifiers for thermoplastic re~ins. See, for example, U.S~ Patent No.
2,891,920 (J.F. Hyde, et al.); and O. Graiver, et al., Rubber Chem. Tech., 56 ~5) t 918 tl383).
U.S. Pat. 3,898,300 states that a polyorgano siloxane-based graft copolymer for improving the impact strength of S/AN resin is formed by grafting S/AN
comonomers in an emulsion system onto the vinylsiloxane or allylsiloxane containing silicone substrate. U.S.
Pat. 4,071,577 describes a similar approach by using a mercaptosiloxane in place of vinyl-group containing siloxanes. European Pat~nt 0,166,900 reports further improvement of polysiloxane-based graft poly~ers and increased S/AN impact streng~h by using acryloxy-functionalized siloxane as the graft-linkin~ agent.
These graft polymers are utilized in connection with the impact modification of S/AN~ British Patent No. 1,59Q,549 describes the use of a polyorganosiloxane graft copolymer in various plastic molding compositions.
Similarly, European Patent Application 0,249,964 describes the use of a polyorganosiloxane graft copolymer in the polycarbonate containing blends.
None of the refe~ences disclose the in-situ co-homopolymerization of vinyl monomerq in the presence of siloxanes in an emulsion system, as de~cribed hereinbelow.` The present invention is also directed to the use of graft polymer~ provided by subsequ~nt gra~t polymerization of vinyl monomers (e.g. polyme~hyl (meth)acrylate, polystyrene or styrene/acrylonitrile copolymer) in the presence o~ such a co-homopolymerized polyorganosiloxane/vinyl-based substrate.
The use of a diene or acrylic rubber-based :

,~

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-4- 337-2167 (8CT-4861) impact modifiers in thermoplas~ic resins has become a common practice in the art~ The selection of either material depends largely on the end use purposes, such as weatherability or low temperature impact resistance.
Uniform color appearance of molded parts is a benefit which is gained by using a diene-based impact modifier over acrylics. However, the unsaturated moieties of the diene rubber restrict its ou~door use to some extent due to its tendency to oxidize and yellow.
Surprisingly, it has been found that partial replacement of the oxidation or ozone sensitive rubber by a silicone-based rubber effects more improvements, such as low temperature ductility, low gloss, and impact and discoloring resistance against thermal aging on the blends described hereinafter. Unexpectedly, it is now possible to prepare low gloss polycarbonate and polyester blends having both excellent low temperature impact resistance and discoloration re istance by the addition of an effective amount of a silicone based impact modifier to a diene-based impact modifier.
Mention is also made to EPO 0,260,558 which discloses a combina~ion of a silicone-based impact modifier wi~h an alkylacrylate-based modifierO The patentee, however, makes no mention of the use of a diene-based impact modifier.
S~ARY OF T~ I~V2~TION
According to the present invention there are provided compositions comprising a polyc~rbonate resin (A); a mixtu~e (A-l) comprising (i) a p~lycarbonate resin and (ii) a saturated polyes~er resin; a mixture (A-2) comprising (i) a polycarbonate re in and (iii) a poly(etherester) elatomer, a poly(etherimide ester) elastomer or a mixture thereof; a mixture (A-3) comprising (i) a polycarbonate re~in, (ii) a satura~ed polyester recin and (iii) a poly(etherester) elastomer, . ~ , ~ . . . .

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-5- 337-2167 (8CT-4861) a poly(etherimide ester) elastomer or a mixture thereo~;
or a mixture (A-4) of any of ~he foregoing; and an effective amount of a modifier composition (B) comprising in combination a multi-stage polyorganosiloxane-based grat polymer composition (B-l) comprising (a) as a first stage, (i) an organosiloxane polymer, units derived from a cross-linking agent or agents and optionally units which serve as a graft-linking agent or agents; or ~ii) a polymeric co-homopolym~rized substrate comprised of~ in combination, an organo-siloxane polymer, a vinyl polymer F and optionall~ units derived from a cross-linking agent or agen~s; units which serve as a graf~-linking agent or agents;
units deriv d from a cross-linking agent or agents and graft-linking agent or agents, or a mixture of any of the foregoing units or a mixture of (i) and (ii); and (b) at least one subsequent stage or stages graft polymerized in the presence of any previous stage and which is comprised of a vinyl-based polymer or a cross-linked vinyl-based polymeri and a diene rubber-based graft polymer composition (B-2) comprising (a) as a first stage a po~ymeric . "
. substrate comprised o~units of a diene rubber an~ units which serve as graft-linking agent or agents; and (b) at l~as~ one subsequent stage graft polymerized in the presence of any previous stages and which i5 comprised of a vinyl-based polymer or a cross- ~

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-6- 337 2167 (8CT-4861) linked vinyl-based polymer, the weight ratio of B-l to B-2 being from 1 to 9:g to 1.
A preferred cvmposition comprises a mixture i (A-l) comprising (i) a polycarbonate re~in and (ii) a saturated polyester resin.
Preerably component A, A-l, A-2, A-3 or A-4 comprises from 1 to 99 parts by weight and components B-l and B-2 comprises from 99 to 1 pa~t by weight per 100 parts by weight of A, A-l, A-2, A-3 or A-4 and B-l and B-2 combined. Preferably the first stages ~a) in B-l and B-2 comprise approximately 30 to 90 weight percent of the total weight of each graft polymer composition. In modifier B-l it is p~eferred tha~ the first stage substrate (a)(ii) is comprised of . approximately 5 to 45 weight percent vinyl-based polymer.
Preferred organosiloxane polymers are comprised primarily of units of the ormula RnSiOt4 n)/2 wherein R is hydrogen or a monovalent hydrocaebon radical of about 1 to 16 carbon atoms and n i5 0, 1 or 2. Preferred vinyl-based polymer componsnts of the first stage substrate a-l (a)~ii) comprise ptimarily alkenyl aromatic uni~s, tmeth)acryla~e units or mixture~
thereof. Especially preferred is polystyrene.
Preferred vinyl-based polymers of subsequent stages B-l(b) and B-2(b) comprise at leas~ one selected from ?
the group consisting o~ alkenyl aromatic compounds, tmeth)acrylate compounds~ vinyl cyanide c`ompounds, maleimide compounds and acrylamide compounds. Especially p~eferred are polystyrene, styrene/acrylonitrile copolymer and s~yrene/methyl methacrylate copolymer.
Preferred embodiments of the diene rubber- ~:
based graft polymer are a first~stage (~-2)(a) comprising uni~s of a polybutadiene rubber and a subsequent stage or stages comprising poly(methyl meth~

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-7- 337-2167 (8CT-4861) acrylate) or me~hyl methacrylate/styrene copolymer.
Among the preferred features of the present invention are subsequent stages in components B-l and B-2 comprising S ~b)(i) a second stage comprising at least one vinyl polymer and optionally units ~erived from a cross-linkiny agent or agents, or and units which serve as a graft-linking agent or ayents, units derived from a cross-linking agent or agents and units from the same agent or agents which serve as a graft-linking agent or agen~s, or a mixture of any of the oreyoing; and (b~ii) a third stage comprising at least one vinyl-based polymer or a cross-linked vinyl-based polymer which is the same different than ~b)(i).
Preferably the ratio of first stage substrate B-l(a) and B-2~a) to second s~age polymer (bl(i) i5 10:90 to 90:10 and the amount of third stage polymer (b)(ii) comprises fro~ about 10 to about 90 parts by weight per 100 parts by weight of (a)~ ~b)(i~ and (b)(ii) combined. Especially preferred in (B-l) subsequent stage (b)(i~ is a composition which comprises a cros5-linked butyl acrylate polymer and a subsequent stage (b)(ii) which comprises a styrene/acr-ylopitrile copolymer.
Preferr~d saturated polyester ~esins comprise the reaction product of a dicarboxylic acid or a chemical equivalent th~reof and a.diol. Especia}ly preferred is poly(l,4-bu~ylene terephthalate).
Polyester elastomers preerably comprise a block copolymer consisting of (1) polyester segments and (2) polyeth~r or poly(etherimid~) segments. Pre~erred are polyester segments comprising poly(1,4 butylene terephthalate) and polyether or poly(etherimide) - : :
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-8~ 337~2167 (8CT-4861) segments comprising a polyalkylene ether glycol, or an imide acid capped polyalkylene ether diamine, or a mixture of such segments.
Also contemplated are compositions including an effective amount of flame retardant agents and reinforcing fillers or a combination ~hereof; and molded, ex~ruded or thermoformed articles made from the above-defined compositions~
DBTAIL5D D~SCRIPTIO~ OF T~l~ I~NTIO~
Polycarbonate resins, suitable for use in this invention, can comprise non-aromatic as well aR 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 lS be prepared by reacting a dihydric phenol with a carbonate precursor, such as phosgene, a haloformate or a carbonate ester. Typically, they will have recurring structural units of the formula~
O \

t ~ A - 0 - C ~
wherein A is a divalent aromatic radical of the dihydric phenol employed in the polymer producing reaction.
Preferably, the aromatic carbonate polymers have an intrinsic viscosity ranging from 0.30 to 1.0 dl/g (measured in methylene chloride at 25C), By dihydrio phenols is meant 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 includ~ 2,2-bis-(4-hydroxy- :
phenyl)propane; 2,2-bis-(3,5-dimethyl-4-hydroxyphenyl) propane; ~,4'-di-hydroxydiphenyl ether; bis(2-hydroxy-phenyl)methane, mixtures thereof and the like. The pre erred aromatic carbonate polymer for component (A) ... . . .... : ~ ,. : : . :
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-9~ 337-2167 ~8CT-4861) is a homopolymer derived from 2,2-bis(4-hydroxyphenyl) propane(bisphenol-A)~
Poly(ester carbonates~ for use in the invention are known and can be obtained co~mercially~
Generally~ ~hey are copolyesters comprising recurring carbonate groups:
O
t - c - t carboxylate groups O~ \
t - t 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. These poly(ester carbona~es) in general, are lS prepared by reacting a difunc~ional 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 presursor, of the ~ypes described above~ A
particularly useful poly(ester carbonate~ is derived from bisphenol-A, isophthalic acid, terephthalic acid, or a mixture of isophthalic acid and t~reph~halic acid, or the reactive derivatives of these acids such as terephthaloyl dichloride, or a mixture thereof, and phosgene. The molar proportions o~ dihydroxy diaryl units to benzenedicarboxyla~e units to carbonate units can range from 1:0~30-0.80:0.70-0.20 and the molar range -, ' ~33~

-10~ 337 2167 (8CT-4861) of terephthalate units to isophthalate units can range from 9:1 to 2:8 in this preferred family of resins.
The aromatic dihydric phenol sulfone polymer resins useful in component (A) are a family of resins which can be made by those skilled in this art. For example homopolymers of dihydric phenol, and a dihydroxydiphenyl sulfone and a carbonate precursor can be prepared as well as copolymers of a dihydric phenol and a carbonate precursor can be made accordiny to the description in Schnell, et al., U~S. 3,271,367. A
preferred material is made by polymerizing bis-(3,5-dimethyl-4-hydroxyphenyl~sulfone, alone, or especially in combina~ion with bisphenol-A with phosgene or a phosgene precursor, in accordance with the description in Fox, U.S. Pat. No. 3,737,4~9. Especially preferred is a copolymer made by reacting 40 to 99 weight percent of the sulfone, 1 to 60 weight percent of the bisphenol wi~h phosgene.
Polyeste~s suitable ~or use herein may be saturated or unsatura~ed Qr polyester elastomers and are generally derived from an aliphatic or cycloaliphatic diol, or mixtures the~eof, containing from 2 to about 10 carbon atoms and at least one aromatic dicarboxylic acid. Preferred polyesters are derived from an aliphatic diol and an aromatic dicarboxylic acid have repeated units of the following gener~l formula:

~ O

~ CB 2 ~ --C--~C--wherein n is an int~ger of ~om 2 to 4. The most preferred polyester is poly(ethylene terephthalate).
Also contemplated herein are the above polyesters with minor amounts, e.g., from 0.5 to about 2 .. ..
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-11- 337-2167 (8CT-4861) percent by w~ight, 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 polyes~ers can be made following the teachings of, for example, U.S. Pat. Nos. 2,465,319 and 3,047,539.
ThP 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 as to produce a polyester having recurring units of the following formula: -O O
~\ 11 11 - O - CH - ~ CH2 - O - C - R - C -wherein the cyclohexane ring is selec~ed from the cis-and trans-isomers thereof and R represents an aryl radical containing 6 to 20 carbon atoms and which is the decarboxylated residue derived from an aromatic dicarboxylic acid.
Examples of aromatic dicarboxylic acids represented by the decarboxylated residue R are isophthalic or terephthalic acid, 1,2-di(p carboxyphenyl) ethane, ~,4'-dicarboxydiphenyl ether, etc., and mixtures of the.e. All o~ these acids contain~a~ least one aromatic nucleus. Acids containing fused rings can also be pre~ent, such as in 1~4- or 1,5-naphthàlenedicarboxylic acids. The preferred dicarboxylic acids ase terephthalic acid or a mixture of terephthalic a~d isophthalic acids.
Another preferred polye~ter may be derived from the reaction o~ ei~her the cis- or tran~-isomer (or a mixture thereof) of 1,4-cyclohexanedimethanol with a mixture of isophthalic and terephthalic acids. Such a . ' : . . ~. ' :
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-12- 337-2167 (8CT-4861) polyester would have repeating units of the for~ula:

- O - CH2 0_ CE32 - O - C ~ Oyc Still another preferred polyester is a copoly-ester 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 ~o produce a copolyester having units of the followin~ formula:

O
` ~O-C~2-~C~2-o-C-~-CT

~ 0--~C~2 ~ 0 C - R - C ~

~ . ' wherein the cyclohexane ring~is ~elected from the cis-and trans-isomers thereof, R is as previously definedt n is an integer of 2 to 4, the x units compris~ from about lO to about 90 parcent by weight and the.y units comprise from abou~ 90 to abou~ lO perce~ by weight.
Such a preferred copolyester may be derived ~;
from the reaction of either the cis- or trans~isomer (or mixtures thereof) of 1,4-cyclohexanedime~hanol:and ethylene glycol with terephthalic acid in a molar ra~io of 1:2:3, Thes2 copolyesters have repeating unit~ of the following formula:

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-13- 337-2167 (8CT-4861) o - ca2 3 CH2 - O - C _~1 ~x ~ O ~ CH2~ 0 - C~)--C

wherein x and y are as previously defined.
The polyesters described herein are either commercially available or can be produced by methods S well known in the art, such as those set forth in, for example, U.SA Pat. No. 2,901,466.
The polyesters used herein have an intrinsic viscosity of from about 0.4 ~o about 2.0 dl/g as measured in a 60:40 phenol:tetrachloroethane mixture or similar solvent a~ 23 - 30C.
The poly(etherimide ester) elastomers (ii~
used herein may be prepared from one or more diols, one or more dicarboxylic acids and one or more high molecular weight polyoxyalkylene diimide diacids.
Preparation of such materlals is described in detail in U.S. Patent No. 4,556,705 o~ R.J~ McCready, issued December 3, 1985 and hereby incorporated by reference.
The poly(etherimide ester) elastomers used herein may be prepa~ed by conventional processes, such as esterification and condensation reactlons~for the production of polyes ers~ to provid~ random o~ block .
copolymers~ Thus, poly(etherimide esters) may be generally characterized as the reaction product of the aforementioned diols and acids. -:
The a~ounts of co~ponents (A) and ~B) ca~ vary broadly, but will usually be in the range of from about 1 to about 9g parts by weigh~ of (~) to from about 99 to about 1 part by weight of (~), per 100 parts by weight .
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-14- 337-2167 (8CT-48613 of (A) and (B) toge~her. Preferably (A) comprises from about 99 to about 30 parts by weiyht and (~ comprises from about 1 to abou~ 70 parts by weight.
The multi-stage polyorganosiloxane-oased gra~t polymers may be prepared with or ~ithout the incorporation of a vinyl-based polymer. Where incorpora~ion of the vinyl-based polymer is desired, the process is generally described hereinbelow by a co-homopolymerization process.
Co-homopolymerization refers to a polymerization step where two distinct polymerization mechanisms are effected concurrently, including ~imultaneously. In particular, the first stage co-hompolymerization may encompass a siloxane polymerization (e.g., ring opening and condensation mechanism) in conjunction with a concurren~ vinyl polymerization. The discrete mechanisms are not seen as competing with each other, but rather, two homopolymers are concurren~ly produced each retaining its own structure.
The co-homopolymerization process may provide two discrete networks rather than a random copolymer.
While not intending to be bound by any theory~ 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 g}ass transition temperatures which can be detected by differential scanning calorimetry. Pre~erably, the p~oduct of the co-homopolymerization pEocess is rubber~ instead of a resin-like powde~.
Subsequent to the co-homopolymerization of the siloxanes and vinyl-based monomers of the ~irst step, at least one additional graft polymerization process is utilized to achieve~th~multi-stage polyorganosiloxane/poly-vinyl-based graft polymers of the present invention.

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-15- 337-2167 ~8CT-4861) The subsequent graft polymeri~ation is preferably of at least one vinyl-based type ~onomer. It has been found that a styrene/acrylonitrile copolymer or an alkyl(meth)acrylate polymer is particularly effective as the second stage graft polymer or copolymer r or as the ou~ermos~ stage when intermediary stages are optionally utilized.
The foregoing polyorganosiloxane/polvinyl-based graft polymer can be isolated and u~ilized, for example, a~ an impact improving agent for theromplastic resins as will be discussed in detail belowl Additional cross-linking and/or graft-linking agent can be utilized in this initial stage to provide co-homopolymerized networks from both polymeric lS constituents which provide gr~ater rubber integrity.
The first s~age rubbery sub~trate i~ 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 premixed ingredients are homogenized by conventional means~ The reactions may begin at ~his early stage of the proces bu~ these reactions are generally slow at room temperature. The homogeni~ed reactants may be direc~ed to a reactor vessel, typically stainless steel or glass flasks, under a ni~rogen blanket. Heat is applied to facilitate the reaction. For~typical S to 50 gallon stainless steel reactor~, a 3 to ~ hour residence time at 75 to 90 degrees centigrade is adequate ~o complete the co-homopolymerization. Cooling for 2 to 6 hours will ~ypically reduce the ~emperature to at lea~
room temperature where the reaction mass can be held for 3 to 72 hours. Cooling to lower temperatures (e.g. 5 degrees centigrade) may sometimes be preferred since :

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-16- 337~2167 (8CT-4861) this may enhance the properties of the newly formed 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 phy~ical properties of the product for certain applica~ions. Generally7 lower temperatures are preferred when it is desired to optimize the elasticity of the formed polyorganosiloxane/
polyvinyl-based substrateO
The initiator for the siloxane component can be any ionic ring opening type initiator when cyclic ~iloxanes are utilized, such as alkylarylsulfonic acids, alkyldiaryldisulfonic acids, alkylsulfonic acids~ and the like. The best suited example is dodecylbenzenesulfonic acid which can act as an initia~or and at the same time as an emulsifier. In some cases, the joint use of a metal salt of an aforementioned sulfonic acid is also preferred~
The initiator for the optional styrenic or other vinyl-based monomers in the co-homopolymerization process can be any organic soluble radical initiator, such as azobisisobutyronitrile (AIBN) and the organic peroxides, e.g. benzoyl peroxide, dichlorobenzoyl peroxide, and ter~-butyl perbenzoate. Also suitable are water-soluble radical initiators such as the persulfates.
Although it i5 possible to charge this type of initiator at the beginning of the process, it is pre~erred tha~ it be charged continuously or incrementally.during the co-homopolymerization periodO Since persulfate is less stable in the acid conditions o~ 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 proce~s.

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-17- 337-2167 (8CT-4861) A latex rubber emulsion prepared as described above will generally con~ain particles having an average diameter of 100 to 800 nanometers and preferably 150 to 400 nanometer The particle size is particularly i influenced by the homogenization pressure land 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 pre~erred. ~ultiple pasces through the homogenizer may be preferred but on a large scale a single pass may be most practical.
The foregoing reaction steps must be followed by a suitable neutralization process to provide the products of the inven~ion. The main object of the neutralization is to quench ehe siloxane polymerization~
This is accomplished by adding a caustic solution such as sodium hydroxide, potassium hydroxide, potassium or sodium carbonate, sodium hydrogen carbonate, triethanol-amine or triethylamine. The pH of the reaction ~olution may be raised from a level of 1 to 3 to a pH of at least 6.5, and preferably 7 ts 9.
It is often desirable to add additional soap or surfactant to the emulsion formed at the end of the first stage, prior to t~e neutralization step.
Additional surfactant tends to facilitate avoidance of premature agglomeration or flocculation of the co-homopolymerized rubber in the quench step.
The foregoing co-homopolymeriz~tion process provides a rub~ery network composed of a polyorgano-siloxane/polyvinyl based substrate. This substrate isthe first stage of the graft polymer of the presen~
invention. Optionally, a first stage comprising an organosiloxane polymer with unitR derived from a cross-linking agent or agents and optionally uni~s which serve as a graft-linking agent or agents may be employed.

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-18- 337-2167 (~CT-4861) The organosiloxane polymer can be pcepared in a manner .
according to the prior art, e.g. EPO 0,16~,900. Also contemplated are mixtures of the co-homopolymerized substrate with silicone substrates.
In general, the first stage comprising the co-homopolymerized polyorganosiloxane/polyYinyl-based substrate will comprise approximately 5 to 95 weight percent of the total graft polymer based upon the weight of the first stage and the subsequent stage or stages taken together. Preferably the first stage will comprise approximately 30 to ~0 weight percent on the same basis.
Correspondingly, the subsesquent stages, comprising the additional grafted vinyl polymers will cumprise approximately 95 to S weight percent and preferably approximately 70 to lS 10 weight percent on the same basis. In the multi-stage systems, preferably, the ratio of fir3t stage substrate tB-l)(a) and (B-2)(a) to second stage polymer (b)(i) is 10:90 to 90:10 and the amount of third stage polymer (b~(ii) comprises from about 10 to abou~ 90 parts by weight of (B-l)(a~, (8-2~(a), (b)(i) and (b)(ii) combined.
Th~ organosiloxanPs useful in the first stage of the composition are any of those known to produce silicone elastomers and may include those which are hydroxy-, vinyl-, hydride- or mercapto- end capped linear organosiloxane oligomers.
Th~ polyorganosiloxanes will be comprised primarily of units of the formula RnSiO(4_n)/2 wherein R is hydrogen or a monovalent hydrocarbon radical of abou~ 1 to 16 carbon atoms and n is 0, 1 or 2c Preferred among the organosiloxanes are those in cyclic form having three or more siloxane units and most preferred are those having three to six units.

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.. ..

2~33~

19- 337 2167 (8CT-4861) Such organosiloxanes include, without limitation, for example, hexamethylcyclotrisiloxane, oc~amethylcyclo-tetrasiloxane, decamethylcyclopentasiloxane, dodeca-methylcyclohexasiloxane, ~rimethyltriphenylcyclotri-siloxane, tetramethyltetraphenylcyclotetrasiloxane,tetramethyltetravinylcyclotetrasiloxane and octaphenylcyclotetrasiloxane. These or similar organosiloxanes may be used alone or in combination.
The v`inyl-based monomers useful in conjunction with the co-homopolymerization of organosiloxanes in the first stage are preferred to be alkenyl aromatic compounds such as styrene, divinylbenzene, alpha-me~hyl-styrene, vinyltoluene, vinylnaphthalene, vinylanthracene, and halogenated styrene or its derivatives. Other suitable vinyl-based monomers include acrylic acids and acrylates such as methyl-, ethyl-, alkyl-, or butyl-acrylate; methacrylates such as methyl me~hacrylate, or 2-ethylhexyl methacrylate; vinyl cyanides uch as acrylo-nitrile, and methacrylonitrile; olefins such as ethylene, propylene, butadiene, isoprene, and chloroprene; and other vinyl compounds such as vinyl imidazole, 5 vinyl-2-norborn~ne, vinyl pyrilidine, vinyl pyrrolidinone, vinyl acetate, vinyl alkyl ethers, vinyl chloride, vinyl furan, N-vinylcarbazole, allyl (meth)acrylate, triallyl isocyannurate, ethylene di(meth)acrylate, bu~ylene di(meth) acrylate, diallyl maleate, .~aleic anhydride;
maleimide compounds such as maleimide, N.phenyl (or alkyl) maleimides acrylamides; N-(mono ,or disubstituted) acrylamides; and mix~ures of any of:thesë monomers. In general, any rubbery or glassy vi~yl type monomer may be used which can be mixable with the organosiloxane. ~`
Typically the vinyl-based component of the first stage co-homopolymer will be presçnt in an amount of approximately 3 to g7 weight percent and correspondingly 35 the organosiloxane component will be precent in an ~.

., . . ,, , .~ ,..

:, .
,, ,, ,. : ' .

~3~$

-20~ 337-2167 (8CT-4861) 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.
The cross-linker composition used in conjunction with the organosiloxane component o~ the present compositions can have the general formula:

R n ~ Sl(R )4-n wherein n is 0, 1 or 2, preferably 0 or 1, and each independently represents hydrogen or a monovalent hydrocarbon radical sPlec~ed from among alkyl or aryl radicals having 1 to 16 carbon atoms, preferably methyl, ethyl and phenyl. R can be the same as Rl or can be a vinyl, alkenyl, thio, or (meth)acryloxy alkyl func~ional radical. When R2 is a vinyl, alkenyl, thio or acryloxy alkyl radical and the n is 1 the cross-linker compound can also act as a graft-linker.
A preferred cross-linker compound is tetra-ethoxysilane. A combination cross-linking and graft-linking compound is vinyltrie~hoxysilane. ~nother suitablechoice is gamma-methacryloxypropyltrime~hoxysilane.
The multi-stage polyorganosiloxane/polyvinyl-based yraft product of the present invention can be isQlated by conventional means such as hot solution coagulation. For example, an electrolytic solutio~ of about 0.5 to 5 p~rcent aluminum sulfate or magnesium sulfa~e in water can b~ prepared ~nd he~ted to about 75 to 95C. When the latex is added, with agita~ion, the graft product-will precipitate and can be held at an elevated temperature for about 10 minu~es whereupon it may be filter washed. Commerical latex isolation techniques such as spray dryers may also be utilized.
The grafted polymers will preferably be the .:

~3~8~

-21- 337-2167 (8CT-4861) product of a vinyl polymerization process. Suitable vinyl monomers for graft polymerization include, without limitation, alkenyl aromatlc compounds such as styrene, divinylbenzene, alpha-methylstyrene, vinyl toluene, halogenated styrene and the like; methacryla~es such as metnyl methacrylate and 2-ethylhexyl methacrylate;
acrylates such as acrylic acid, methyl acrylate, ethyl acrylate and butyl acrylate; vinyl cyanide compounds such as acrylonitrile and methacrylonitrile; olefins such as ethylene, propylene, butadiene, isoprene, and chloroprene; other vinyl compounds such as acrylamides, N-(mono or di-substituted)alkyl acrylamides, vinyl acetate, vinyl chloride, vinyl alkyl ethers, allyl (meth)acrylate, triallyl isocyannurate, ethylene dimethacrylate, diallyl malea~e, maleic anhydride; and maleimide compounds such as maleimide, and N-phenyl (or alkyl) maleimide; and mixtures of these monomersO
The vinyl polymeriæation is accomplished in an emulsion; therefore, water-soluble initiators are suitable, e.g. po~assium persulfate, sodium persulfate and ammonium persulfate. It i5 practical to add the initiator at the beginning of this s~ep, prior to charging the vinyl monomer for the second stage polymerization. Other Redox initia~or systems, such as cumene hydrope~oxide/ferrous sulfate/glucose/sodium pyrophosphate, can also be utilized at thi~ stage as well as other organic peroxides.
The diene rubber-based graft polymer compositions comprise a first stage substrate of units derived from a diene rubber and op~ionally units derived from a cross-linking agent or agents. Dienes are generally classified as hydrocarbon-based molecules having a~ lea~t two conjugated double bonds. Other examples of diene rubbers are styrene/butadiene rubber, acrylonitrile/butadiene, isoprene rubber, chloroprene :

~ -22- 337 2167 (8CT-4861) rubber o~ l,3-dimethylbutadiene rubber.
Vinyl-based polymers useful in the subsequent stages are selected from alkenyl a~omatic co~pounds~
(meth~acrylate compounds, vinyl cyanide compounds and 5 acrylamide compounds.
Alkenyl aroma~ic polymer ~esins useful as component B-l(b) and B-2~b) are in general those having at least 25 percent of their units derived from a monomer having the formula CRl=CHR2 ~ =R.3 wherein Rl and R2 are selected from the group consisting of lower alkyl or alkenyl groups of from 1 to 6 carbon atoms and hydrogen; R3 and R4 are selected from the group consisting of chloro~ bromo, hydrogen and lower lS alkyl of from l to 6 carbon atoms; R5 and R~ are selacted from the group consisting of hydrogen and lower alkyl and alkenyl groups of ~rom 1 to 6 carbons or R5 and R6 may be concatenated together with hydrocarbyl groups to form a naphthyl group.
Materials that may be copolymerized with the units of the alkenyl aromatic monomer include those having the general formula:
R7 - C~ = C t C~2trnR

wherein R7 and R8 represent a sub tituent selected from the group consisting of hydrogen, halogen, an alkyl group of l - 4 carbon atoms, carboalkoxy or R7 and R8 .
,~ ,, 2~ 8~
23- 337-2167 (8CT~4361) taken toge~her represent an anhydride linkage (-COOOC-) and R9 is hydrogen, vinyl, an alkyl or alkenyl group having 1 to 12 carbon a~oms, cycloalkyl, carboalkoxy, alkoxy-alkyl, alkyl carboxyl, ketoxy, halog~n, carboxy, S cyano or pyridyl and n is 0 or a whole number between 1 and 9.
(Meth)acrylates are generally produced in a two-step process wherein an acetone is reacted with a hydrogen cyanide to form an acetone cyanohydrin which is then heated in the presence of an alcohol ~o produce the (meth)acrylate. Preferred (meth)acrylates are methyl acrylate, ethyl acrylate, butyl acrylate and methyl methacrylate.
Vinyl cyanides useful in the practice of the present invention are comprised of the following general formula CN
CH2 = CRl wherein Rl is an alkyl group of from 1 to 6 carbon atoms.
Acrylamide ar~ well known in the art and generally compris2 hydrocarbons having a group comprising the following general formula C~2 = CH - C - NH2 The thermoplastic resin compos *ion may also contain an efective amoun~ of any suitable additives such as addition rub ers, polymersj ~iIlers, pigments, dyes, antioxidants, stabilizers, ultraviolet light absorbers and mold release agents.
The reinforcing filler can be comprised of any organic or inorganic fille~ including but not limited to 30 glass fiber, carbon fiber, aramid fiber, metallic fiber, ~.

. ..

, " . ~ ,' .
.~ , -24- 337~2167 (8CT-4861) asbestos, whisker, glass beads, glass flakes, calcium carbonate, talc, mica, aluminum oxide, magnesium hydroxide, boron extrude, beryllium oxide, calcium silicate, clay or metal powde~.
Platinum compounds are often utilized in conjunction with polyorganosiloxane compositions in order to enhance the flame retardance of the latter.
Platinum complexes are also used as catalysts in cer~ain hydrosilation processes although such ca~alysts are not necessary for the practice of the present invention. As flame retarding additives; however, there may be utilized the reaction product of ehloroplatinic acid and organosilicon compounds as described in U.S. Patent No.
3,220,972. Another platinum compound is seen in U.S.
Patent No. 3,775,452 describing platinum-containing polyorganosiloxanesO Other fire eetardants are compounds based on elemen~ary red phosphorous compounds, other phosphorous compounds, halogens, antimony oxides, iron oxid~s, zinc oxides and the like.
~ ~ ~
The following examples illustrate the present invention. ~hey are not to be construed to limit the claims in any manner whatsoever.
A single slash is used between momoners of a single stage and a double slash or a hyphen is used as a shorthand method of indicating separa~ion between stages. The first stage to be polymerized is written first before the double slash or hyphen, and subsequent stages are written subsequently~
30~KPL

Copolymer (GSiM) Synthe~is To deionized water, 400 pa~ts, containing 1.33 parts of dodecylbenzenesulfonic acid dissolved therein is added a mixture comprisiny 90 parts of -. ~ ~
.
:~ .

2~33~
-25 337-2157 (8CT-4861) octamethylcyclotetrasiloxane, 5 parts of tetravinyl tetramethylcyclotetrasiloxane, 5.5 parts of vinyltri-ethoxysilane, 1.7 parts of tetraethoxysilane, 1.43 parts of gamma-me~hacryloxypropyltrimethoxysilane, 0.67 parts of divinylben~ene an~ 0~093 parts of a platinum catalyst (Silicone Product No. 88034). The emulsion is homogenized by passing twice through a homogenizer at a pressure of 7600 to 8600 psi. The emulsion is then stored for S hours at 75C and cooled for 13 hours overnight. The silicone emulsion i~ ~hen neutralized to pH 7.5 by adding 5 parts of 15 percent aqueous potassium carbonate solution. The silicone rubber has a yield of about 83.5 percent, gel content of about 71.3 percent and a 14.6 degree of swelling. The sol fraction possesses a Mw/Mn of 4~,600/19,700 measured by gel permeation chromatography against polystyrene standards.
To the core latex is then graft polymerized at 75/25 mixture of s~yrene/acrylonitrile for 6 hours at 75~C
which is persulfate initiated. The polymers are then isolated by coagulation and vacuum dried at 65C
resulting with a silicone-styrene/acrylonitrile weight ratio of 72:28 based on final conversion. The S/AN
graft efficiency is 25 percent.
General Procedure for Blend Preparatlon A dry blend of polybutylene terephthalate, Lexan- 141, stabilizers and silicone-S/AN (GSiM) graft polymer are tumble mixed to give a homogeneous powder dispersion within the pelletsO The blend is then fed into a Werner Pfleiderer 30 mm twin scr~w extruder under the followin~ conditions:
Screw Speed 200 RPM
Throu~hput Rate 20 lb/hr zone 1 195C
Zone 2 210~C
Zone 3-5, die 230-250C

, ., , , . ; . ~ :
` ' 2~33~9~
-26- 337-2167 (8CT-4861) The extrudate is pelletized, dried at 140F
and then injection molded on a 75 ton Newbury molding machine. Tests are according to AST~ methodsO
For comparison purposes, tes specimens of LexanD 141 are formed with polybutylene terephthalate and the silicone-styrene/acrylonitrile ~GSiM) respeotively. The results and compositional data are set forth in Table l.

., :

~ ' -. :. :- - . -., . - . .-. ; .
. .' ' .~ ' :' . .
;: - , . . .
;: ~ ' ' ' ~ ~ ' , 2~338~
-27- 337-2167 (8CT 4861) T~L13 1 POLYl~STER/POL~C~BO~AT~ GSi~ ODIFIE~R E~L~NDS
`~
~a~ple lA* I8~ I
Co~osi~ion Valox~ 315, wt% 39 39 39 Lexan3 141, wt ~ 45.75 45.75 45.75 KM653, wt % 14 - 7 GSiM, wt ~ - 14 7 Sta~ilizers, wt ~ 1O25 1.25 1~25 Propertie~
60 Gloss, ~ 96.0 68~3 62.3 NI, ft-lbs/in 1/8~ 12.1 11.4 12.6 thermal aging*~ 10.8 3,0 11.~
Retention, % 89.3 26.3 87.3 Delta Yellow Index*** 18.9 4.9 5.5 Charpy NI, f~-lbs/in R.T. - 8.1 10C - 6.1 0C 8.8 ~.8 8.1 -10C 8.0 2.9 7.6 -20C 3.1 - 5.1 -30C 2.9 ~.0 2.7 Tensile Strength Yield, Kpsi 801 6.9 6~7 Break h.6 6.1 5.6 Tensile Modulus Kpsi 15.5 14.4 14.9 Elongation, ~
Yield 8.6 7.9 7.3 Break 169 29 42 , .,,",,, _ . _ * = Con~rol Sample Valox~ 315 = a poly(l,4-butylene terephthalate) Lexan~ 141 = a poly (bisphenol-~ carbonate) KM653 = Rohm & Haas Acryloid; butadi~ne rubber substrate S/MMA outer stage GSiM = Silicone-styren~/acrylon~trile prepared as described above NI = Notched impact ** = thermal aging at 96 hours at 125C
RT = room temperature *** = yellowness increase after aging for 96 hours at 125C.

- . . .-, : - ,, :. . ~ , .. : ..... .. .. , :~

~33~

-28- 337-2167 (8CT-4861) As is clearly demonstrated from the table above, only the example containing both the diene-based modifier and the GSiM modifier in combination exhibits uniformly good physical properties, possessing good impact resistance, low temperature ductility, tensile strength, desirably low gloss and resistance to yellowing and property loss b~cause of thermal aging~
The blend containing only the diene-based modifier while exhibiting good strength related characteristics exhibits poor resistance to yellowing and has a high gloss. The blend containing only th~ GSiM modifier (lB*) does not exhibit good low temperature ductility in the blends, has poor thermal stability, and is inferior to the blend combination in most other respects as well.
BXA~PL~S 2 - 4 To 400 parts of deionized water containing 1.33 parts o~ dodecylbenzenesulfonic acid dis~olved therein is admixed an organic mixture comprising 90 parts of octamethylcyclotetrasiloxane, 10 parts of tetravinyltetramethylcyclotetrasiloxane, 1.7 parts of tetraethoxy~ilane, 1.43 parts of gamma-methacryloxypropyl-trimethoxysilane, 0.097 parts of a platinum catalyst solution, 33.3 parts of styrene and 0O67 parts o divinylbenzene. The mixture is stirred and the ~5 homogeni~ed twice under an impinging pressure of about 8000 psi. The crude emulsion is the~ polymerized at 75C for 6 hours followed by overnight cooling down to room temperature. A potassium persulfa~e solution (0.17 parts in 8.17 parts deionized water) i5 added over the first four hours at 75C as a sty~ene polymerization initiator. The silicone/pslystyrene substrate emulsion is then quenched by neutralization from pH 1.7 to 8.1 following an optional addition of 0.67 parts of GAFAC
RE610 which is predissolved in 6 parts of deionized water. The silicone~polys~yrene rubber ha~ a .

- ~

.
: ' ~3~
-29- 337-2167 (8C~-4861) polymerization yield of 8703 peccent, a mean diameter of 230 nmr a gel content of 78 percent and a 13.6 degree of swelling. To the substrate latex is grafted polymerized a 75/25 S/AN mixture for a total of 6 hours at 75C
using potassium pèrsulfate as the initiator. The substrate to S/AN weight ratio is 70:30 and the second stage graft efficiency i5 measured a~ 60 percent using MEX Soxhlet extraction.
Comparison examples are also tested varying the amounts and types of modifiers employed. The results and compositional da~a are set forth below in Table 2.

- . ', . '` ' ., . ~ ~ ' , , , " ` , .. . . . , ,, ~ : , " . ~, . . , :
~ ' , : , ~33~

-30- 337 2167 (8CT-4861) TABL~ 2 R~D PIG~TXD BL~DS
=
E~a~ples 2A~ 2B~ 2 3 4 Valox~ 315 (39%), gms 780 780 780 780 780 Lexan~ 141 (44,75~), gms 895 895 ag~ ~95 895 Lexan ML4545 (1~), gms 20 20 20 20 20 KM-653 4~ 230 - 70 140 210 CSiM (1 ), gms 280 210 140 70 Red 624 (1%), gms 20 20 20 20 20 Stabilizers, gms 25 25 25 25 25 Pro~erties DG, ft-lbs/in 32.2 13.7 20.024.3 28.6 N.I., ft-lbs/in RT 14.1 12.2 13.913.3 14.4 96 hrs, 125C 12dO 2.9 9.8ll.l 12.3 ~ Retention 85.1 23.8 70.583O5 85.4 Color Appearance Good Dull Dull Good Good 60 Gloss 94.2 27.2 35.3 50.7 70.7 , * = Control Sample Valox~ 315 = a poly(l,4-butylene terephthalate) Lexan~ 141 = a poly(bisphenol A carbonate) Lexan ~L4545 =polycarbonate powdez (Lexan 141~
KM-653 = Rohm ~ ~aas Acryloid~ , Impact Modifier CSiM = silicone/polys~yrene-based impact . modifier prepared as described above (Examples 2 - 4) Red 624 = red coloran~
DG ~ 1/8 n = double gate impact strength N.I. = notched izod RT - room temperature . . . . .

.

~3~

-31- 337-2167 (8CT-4861) As can be seen from the above table, the samples containing the combined modifiers exhibit good impact resistance, appearance and low gloss characteristics. Sample 2A* containing no CSiM, while 5 exhibi~ing good strength characteristics is glossy and thus not useful in desired low gloss applications.
~L?Le S
The procedure of Example l is follow2d, except dry blending i5 performed with no polyester resin. A
composition will be formed in accoedance with the appended claims.
e~ll?LI: 6 The procedure of Example 2 is followed substituting butyl acrylate for styrene as the vinyl-based polymer component of the substrate latex~ A composition will be formed in accordance with the appended claims.
eX~PL~S 7 - 8 The procedure of ~xample 2 is followed substitu~ing polystyrene, and poly(methyl methacrylate~, for styrene/acrylonitrile copolymer as the graft stageO
Compo~itions will be formPd in accordance with the appended claims.
~P e g The proceduee of Example 2 is rep~ated to produce the silicone/polystyrene first stage substrate.
However, at the second stage to the silicone~polystyrene latex is added one stream containing butyl acrylate, butylene glycol diacrylate, diallyl maleate, deionized water and sodium dodecylbenzene sulfona~e concurr~ntly with another aqueous stream:consisting of a water-soluble initiator over a period of l to 3 hours at 75C. ~he butyl acrylate to the dry silicone/polystyrene substrate weight ratio is aimed at 35:35. The S/AN g~afting procedure of Example 2 is then repeated as are ~he isolation steps. A composition will be formed in .

2~3~
-32- 337-2167 ~8CT-4861) accordance with the appended claims.
~A~PL~S lO 12 Example 2 i5 repeated three times adding respectively an effective amount of red phosphorous flame retardant, an effective amount of glass fiber and an effective amount of bo~h red phosphorous and glas~
fiber. Compositions will be formed in accordance with the appended claims.
The above~mentioned patents, patent applications and publications are incorported herein by reference as are the Standard Test Me~hods.
Many variations of the present invention will suggest themselves to ~hose skilled in ~he a~t in light of the above detailed description. For example, the aromatic polycarbonate can be replaced in whole or in part wi~h a polyes~er car~onate containing units derived from bisphenol-A, phosgene and terephthaloyl chloride and/or isophthaloyl chloride. The aromatic polycarbonate can be replaced in whole or in part by a polycarbonate containing units of bis(3,5-dimethyl-4-hydroxy phenyl)sulfone, alone, or combined with bisphenol-A.
The poly(ethylene terephthalate) can be replaced in whole or in part by poly(l,4-butylene ~ereph~halate) or by a polyester derived from l,4-cyclohexanedimethanol alone or combined with ethylene glycol and terephthalic acid and/or isophthalic ac:id. Platinum complexes may be employed as catalysts in the hydrosila~ion process~ All such modifications are within the full intended scope of the appended claims.

,. . . .

Claims (38)

-33- 337-2167 (8CT-4861) CLAIMS:

1. A composition comprising a polycarbonate resin (A); a mixture (A-1) comprising (i) a polycarbonate resin and (ii) a saturated polyester resin; a mixture (A-2) comprising (i) a polycarbonate resin and (iii) a poly(etherester) elastomer, a poly(etherimide ester) elastomer or a mixture thereof; a mixture (A-3) comprising (i) a polycarbonate resin, (ii) a sa~urated polyester resin and (iii) a poly(etherester) elastomer, a poly(etherimide ester) elastomer or a mixture thereof;
or a mixture of (A-4) of any of the foregoing; and an effective amount of a modifier composition (B) comprising in combination a multi-stage polyorganosiloxane-based graft polymer composition (B-1) comprising (a) as a first stage, (i) an organosiloxane polymer, units derived from a cross-linking agent or agents and optionally units which serve as a graft-linking agent or agents; or (ii) a polymeric co-homopolymerized substrate comprised of, in combination, an organosiloxane polymer and at least one vinyl-based polymer; or a mixture of (i) and (ii); and (b) at least one subsequent stage or stages graft polymerized in the presence of any previous stage and which is.comprised of a vinyl-based polymer or a cross-linked vinyl-based polymer; and a diene rubber-based graft copolymer composition (B-2) comprising (a) as a first stage a polymeric substrate comprised of units of a diene rubber and optionally units derived from a cross-linking agent or agents; and -34- 337-2167 (8CT-4861) (b) at least one subsequent stage graft polymerized in the presence of any previous stages and which is comprised of a vinyl-based polymer or a cross-linked vinyl-based polymer, the weight ratio of B-1 to B-2 being from 1 to 9:9 to 1.

2. A composition as defined in Claim 1 comprising a mixture (A-1) comprising (i) a polycarbonate resin and (ii) a saturated polyester resin.

3. A composition as defined in Claim 1 wherein said polymeric co-homopolymerized first stage substrate (B-1)(a)(ii) contains units which are derived from a cross-linking agent or agents.

4. A composition as defined in Claim 1 wherein said polymeric co-homopolymerized first stage substrate (B-1)(a)(ii) contains units which serve as a graft-linking agent or agents.

5. A composition a defined in Claim 1 wherein said polymeric co homopolymerized first stage substrate (B-l)(a)(ii) contains units which are derived from a cross-linking agent or agents and the same or different units which serve as a graft-linking agent or agents.

6. A composition as defined in any of Claims 1, 3, 4 or 5 wherein component A, A-l, A-2, A-3 or A-4 comprises from 1 to 99 parts by weight and components B-1 and B-2 comprise from 99 to 1 part by weight per 100 parts by weight of A, A-l, A-2, A-3 or A-4 and B 1 and B-2 combined.

-35- 337-2167 (8CT-4861)

7. A composition as defined in any of Claims 1, 3, 4 or 5 wherein said first stages (a) in B-1 and B-2 comprise approximately 5 to 95 weight percent of the total graft polymer composition based upon the weight of said first stage and any subsequent graft stages taken together.

8. A composition as defined in Claim 7 wherein said first stages (a) comprise approximately 30 to 90 weight percent of the total weight of each graft polymer composition.

9. A composition as defined in any of Claims 1, 3, 4 or 5 wherein in said modifier B-1 said first stage substrate (a)(ii) is comprised of approximately 3 to 97 weight percent organosiloxane-based polymer and correspondingly about 97 to 3 weight percent vinyl-based polymer.

10. A composition as defined in Claim 9 wherein said first stage substrate (B-1)(a)(ii) is comprised of approximately 5 to 45 weight percent vinyl based polymer.

11. A composition as defined in any of Claims 1, 3, 4 or 5 wherein said organosiloxane polymer is comprised primarily of units of the formula RnSiO(4-n)/2 wherein R is hydrogen or a monovalent hydrocarbon radical of about 1 to 16 carbon atoms and n is 0, 1 or 2.

12. A composition as defined in any of Claims 1, 3, 4 or 5 wherein in said modifier B-1 the vinyl-based polymer component of said first stage substrate (a)(ii) is comprised primarily of alkenyl aromatic units, (meth)acrylate units or a mixture thereof.

-36- 337-2167 (8CT-4861)

13. A composition as defined in Claim 12 wherein said vinyl-based polymer component comprises polystyrene.

14. A composition as defined in any of Claims 1, 3, 4 or 5 wherein said vinyl-based polymer in the subsequent stage or stages B-1(b) and B-2(b) comprise at least one selected from the group consisting of alkenyl aromatic compounds, (meth)acrylate compounds, vinyl cyanide compounds, maleimide compounds, and acrylamide compounds.

l5. A composition as defined in Claim 14 wherein said vinyl-based polymer is selected from the group consisting of polystyrene, styrene/acrylonitrile copolymer, poly(methyl methacrylate~ and styrene/methyl methacrylate copolymer.

16. A composition as defined in any of Claims 1, 3, 4 or 5 wherein said first stage substrate (B-2)(a) comprises units of a polybutadiene rubber.

17. A composition as defined in Claim 16 wherein said subsequent stage or stages B-2(b) comprise poly(methyl methacrylate), a methyl methacrylate/styrene copolymer or a (styrene/acrylonitrile) copolymer.

-37- 337-2167 (8CT-4861)

18. A composition as defined in any of Claims 1, 3, 4 or 5 wherein said subsequent stages in components B-1 and B-2 comprise (b)(i) a second stage comprising at least one vinyl polymer and optionally units derived from a cross-linking agent or agents, units which serve as a graft linking agent or agents, units derived from a cross-linking agent or agents and units from the same agent or agents which serve as a graft-linking agent agents, or a mixture of any of the foregoing; and (b)(ii) a third stage comprising at least one vinyl-based polymer or cross-linked vinyl-based polymer which is the same or different than (b)(i).

19. A composition as defined in Claim 18 wherein the ratio of first substrate B-1(a) and B-2(a) to second stage polymer (b)(i) is 10:90 to 90:10 and the amount of third stage polymee (b)(ii) comprises from about 10 to about 90 parts by weight per 100 parts by weight of B-1(a), B-2(a), (b)(i), and (b)(ii) combined.

20. A composition as defined in Claim 18 wherein in B-1 subsequent stage (b)(i) comprises a cross-linked butyl acrylate polymer and subsequent stage (b)(ii) comprises a styrene/acrylonitrile copolymer.

21. A composition as defined in any of Claims 1, 3, 4 or 5 wherein said polycarbonate resin (A) comprises poly(bisphenol-A) carbonate.

22. A composition as defined in any of Claims 1, 3, 4 or 5 wherein said saturated polyester resin (A) (ii) comprises the reaction product of a dicarboxylic acid or chemical equivalent:thereof and a diol.

-38- 337-2167 (8CT-4861)

23. A composition as defined in Claim 22 wherein said saturated polyester resin ( A) (ii) comprises poly(l,4-butylene terephthalate).

24. A composition as defined in any of Claims 1, 3, 4 or 5 wherein said poly(etherester) elastomer, poly(etherimide ester) elastomer or mixture thereof, (A) (iii), comprises a block copolymer consisting of (1) polyester segments and (2) polyether or poly(etherimide) segments.

25. A composition as defined in Claim 24 wherein said polyester segments comprise poly(l,4-butylene terephthalate) and said polyether or poly(etherimide) segments comprise a polyalkylene ether glycol or an imide acid capped polyalkylene ether diamine, or a mixture of such segments.

26. A composition as defined in any of Claims 1, 3, 4 or 5 which also includes (C) an effective amount of a flame retardant agent.

27. A composition as defined in any of Claims 1, 3, 4 or 5 which also includes D) an effective amount of a reinforcing filler .

. 28. A composition as defined in any of Claims 1, 3, 4 or 5 which also includes (C) an effective amount of flame retardant agent; and (D) an effective amount of reinforcing filler.

29. An article molded from a composition as defined in any of Claims 1, 3, 4 or 5.

30. An article extruded from a composition as defined in any of Claims 1, 3, 4 or 5.

31. An article thermoformed from a composition as defined in any of Claims 1, 3, 4 or 5 .

-39- 337-2167 (8CT-4861)

32. A composition as defined in Claim 18 which also includes (C) an effective amount of a flame retardant agent.

33. A composition as defined in Claim 18 which also includes (D) an effective amount of a reinforcing filler.

34. A composition as defined in Claim 18 which also includes (C) an effective amount of a flame retardant agent; and (D) an effective amount of a reinforcing filler.

35. An article molded from a composition as defined in Claim 18.

36. An article extruded from a composition as defined in Claim 18.

37. An article thermformed from a composition as defined in Claim 18.

38. The invention as defined in any of the preceding claims including any further features of novelty disclosed.