This invention relates to compositions containing polycarbonate and chlorinated polyethylene, and to methods of preDaration of such compositions

A polymeric blend containing polycarbonate and chlorinated polyethylene forms a useful composition for molding purp- ses Such a composition is particularly desirable when an ethyienically unsaturated monomer is graft polymerized to the chlorinated polyethylene, when the composition also contains another molding polymer sucn as an epoxy resin or a polyester, when the composition also contains additives wnich imDart flame or ignition resistance, when the composition also contains a vinyl aromatic/vmyi nitπle copolymer containing a high level of vinyl nitrile comDound, or when the composition also contains additives which impart stability against thermal degradation

In one aspect, this invention involves a composition of matter containing, in admixture, polycarbonate, and chlorinated polyethylene to which an ethyienically unsaturated monomer has been graft polymer zed In another aspect, this invention involves a composition of matter containing, in admixture, polycarbonate, chlorinated polyethylene and a molding polymer In yet another aspect, this invention involves a composition of matter containing n admixture, polycarbonate, chlorinated polyethylene and an additive which imparts flame or ignition resistance to the composition In a further aspect, this invention involves a composition of matter containing, in admixture, polycarbonate, chlorinated polyethylene and a vinyl aromatic/vinyl nitπle copolymer which contains a high level of vinyl nitπle compound This invention also involves a method of improving properties such as the impact resistance, ignition resistance, thermal stability and/or pamtability of a polycarbonate/chlorinated polyethylene blend by graft polymerizing one or more ethyienically unsaturated monomers to the chlorinated polyethylene, and/or by admixing with such blend the other components of the compositions of this invention recited below

It has been found that articles molded from the compositions of this invention exhibit desirably high levels of ignition and impact resistance, and stability against thermal degradation

The compositions of this invention are useful, for example, in the production of films, fibers, extruded sheets, multi-layer laminates and molded DΓ shaped articles of virtually all varieties, especially data storage apparatus, appliance and irstrument housings, motor vehicle body panels and other parts and components for use in the automotive, electrical and electronics industries The methods of this invention are useful for preparing compositions and molded articles having applications which are the same as or similar to the foregoing

Detailed Description of the Invention

The comoositiors of this invention are those in which (a) polycarbonate has been admixed in a polymeric blend with (b) chlorinated polyethylene The compositions of this invention may, optionally, also contain (c) a styrenic copolymer, (d) an elastomeπc impact modifier, and (e) one or more additional molding polymers Suitable ranges of content for components (a) and (b) in the compositions of this invention, and suitable ranges of content for components (c), (d) and (e) when they are present, expressed in Darts by weight of the total composition, are as follows ^*

(a) polycarbonate at least 5 parts, advantageously at least 20 parts, preferably at least 30 parts, and more preferably at least 40 parts, and yet not more than 95 parts, advantageously not more than 90 parts, preferably not more than 85 p-jrts, ard more preferably not more than 75 Darts;

(b) chlorinated polyethylene at least 2 parts, advantageously at least 15 parts, preferably at least 20 parts, and more preferably at least 30 parts, and yet not more than 95 parts, advantageously rot more than 80 parts, preferably not more than 60 parts, and more preferably not more than 50 parts,

(c) styrenic copolymer at least 5 parts, advantageously at least 10 parts, preferably at least 15 parts, and more preferably at least 20 parts, and yet not more than 75 parts, advantageously not more than 55 parts, preferably not more than 50 parts, and more preferably not more than 45 parts,

(d) elastomeπc impact modifier at least 0 1 part, advantageously at least 1 parts, preferably at least 3 parts, and more preferably at least 5 parts, and yet not more than 50 parts, advantageously not more than 45 parts, preferably not more than 40 parts, and more preferably not more than 35 parts, and (e) molding polymer at least 0 1 part, advantageously at least 1 parts, preferably at least 3 parts, and more preferably at least 5 parts, and yet not more than 65 parts, advantageously not more than 45 parts, preferably not more than 40 parts, and more preferably not more than 35 parts

The number of weight parts of the various components from which the compositions of this invention may be prepared may, but need not necessarily, total to 100 weight parts

Also included within this invention are the reaction products, if any, of the above named components when idmixed in the compositions of this invention

Preparation of the compositions of this invention can be accomplished by any suitable mixing means known in the art Typically the polycarbonate and chlorinated polyethylene, and other components or additives which are optionally present in the compositions of this invention, are dry blended in a tum bler or shaker in powder or particulate

form with sufficient agitation to obtain thorough distribution thereof. If desired, the dry- blended formulation can further be subjected to maiaxation, or to shearing stresses at a temperature sufficient to cause heat plastification thereof, for example in an extruder with or without a vacuum. Other apparatus which can be used in the mixing process include, for example, a roller mill, a Henschel mixer, a ribbon blender, a Banbury mixer, or a reciprocating screw injection molding machine. The components may be mixed simultaneously or in any sequence.

When softened or melted by the application of heat, the compositions of this invention can undergo fabrication and can therein be formed or molded using conventional techniques such as compression, injection mole ng, gas assisted injection molding, calendering, vacuum forming, thermoforming, extrusion and/or blow molding techniques, alone or in combination. The compositions can also be formed, spun or drawn into films, fibers, multi¬ layer laminates or extruded sheets, or can be compounded with one or more organic or inorganic substances, on any machine suitable for such purpose.

Component (a) in the compositions of this invention is a polycarbonate, which can be prepared from a dihydroxy compo. id such as a bisphenol, and a carbonate precursor such as a disubstituted carbonic acid derivative, a haloformate (such as a bishaloformate of a glycol or dihydroxy benzene), or a carbonate ester such as diphenyl carbonate or a substituted derivative thereof. These components are often reacted by means of the phase boundary process in which the dihydroxy compound is dissolved and deprotonated in an aqueous alkaline solution to form bisphenolate and the carbonate precursor is dissolved in an organic solvent.

These components are often reacted by means of a mixture prepared initially from the aromatic dihydroxy compour.d, water and a non-reactive organic solvent immiscible with water selected from among those in which the carbonate precursor and polycarbonate product are soluble.

A carbonate precursor is contacted with an agitated mixture of the aqueous alkaline soiution of the dihydroxy compound. Tr e mixture is agitated in a manner which is sufficient to disperse or suspend droplets of the solvent containing the carbonate precursor in the aqueous alkaline solution. Reaction between the organic and aqueous phases created by such agitation yields the b s(carbonate precursor) ester of the dihydroxy compound. For example, if the carbonate precursor is a carbonyl halide such as phosgene, the products of this initial phase of the process are monomers or oligomers which are either mono- or dichloroformates, or contain a phenolate ion at each terminus

These intermediate mono- and oligocarbonates dissolve in the organic solvent as they form, and they can then be condensed to a higher molecular weight polycarbonate by contact with a coupling catalyst of which the following are representative: a tertiary amine such as triethyl amine, dimethyl amino pyridine or Λ/,Λ/-dimethyl aniline. Such a catalyst may be added to the reaction mixture before or after a dihydroxy compound is contacted with a carbonate precursor, and is typically used in an amount of 0.01 to 0.1 moles per mole of dihydroxy compound.

Upon completion of polymerization, the organic and aqueous phases are separated to allow purification of the organic phase and recovery of the polycarbonate product therefrom. The organic phase is washed as needed in a centrifuge with dilute base, water and/or dilute acid until free of unreacted monomer, residual process chemicals and/or other electrolytes. Recovery of the polycarbonate product can be effected by spray drying, steam devolatilization, direct devolatilization in a vented extruder, or precipitation by use of an anti-solvent such as toluene, cyclohexane, neptane, methanol, hexanol, or methyl ethyl ketone.

Polycarbonate can also be prepared by transesterifica; on or in a homogeneous solution.

Examples of some dihydroxy compounds suitable for the preparation of polycarbonate include variously bridged, substituted or unsubstituted aromatic dihydroxy compounds (or mixtures thereof) represented by the formula

wherein: (I) Z is (A) a divalent radical , of which all or different portions can be (i) linear, branched, cyclic or bicyclic, (ii) aliphatic or aromatic, and/or (iii) saturated or unsaturated, said divalent radical being composed of 1 -35 carbon atoms together with up to five oxygen, nitrogen, sulfur, phosphorous and/or halogen (such as fluorine, chlorine and/or bromine) atoms; or (B) S, S ₂ , SO, S0 ₂ , O or CO; or (C) a single bond;

(ID each X is independently hydrogen, a halogen (such as flourine, chlorine and/or bromine), a C_-C_ ₂ , preferably C.-C , linear or cyclic alkyl, aryl, alkaryl, aralkyl, alkoxy or aryloxy radical, such as methyl, ethyl, isopropyl, cyclope ^** tyl, cyclohexyl, methoxy, ethoxy, benzyl, tolyl, xylyl, phenoxy and/or xylynoxy; or a nitro or nitrile radical ; and

(III) m is O or 1

For example, the bridging radical represented by Z in the above formula can be a C ₂ -C ₃₀ alkyl, cycloalkyi, alkylidene or cycloalkyidene radical, or two or more thereof connected by an aromatic or etner linkage, or can be a carbon atom to which is bonded one or more groups such as CH ₃ , C ₂ H , C ₃ H., n-C_H _? , i-C H ₇ , cyclohexyl, bicyclo[2.2.1 ]heptyl, benzyl, CF ₂ , CF ₃ CCI,, CF ₂ CI, CN, (CH ₂ ) ₂ COOCH ₃ , or PO(0CH ₃ ) ₂ .

Representative examples of dihydroxy compounds of particular interest are the bis(hydroxyphenyl)alkanes, the bis(hydroxyphenyl)cycloalkanes, the dihydroxydiphenyls and the bis(hydroxyphenyl)sulfones, and in particular are 2,2-bis(4-hydroxyphenyl)propane ("Bisphenol-A" or "Bis-A"); 2,2-bis(3,5-dihalo-4-hydroxyphenyl)propane ("Tetrahalo

Bisphenol-A") where the halogen can be fluorine, chlorine, bromine or iodine, for example 2,2- bis(3,5-dibromo-4-hydroxyphenyl)propane ("Tetrabromo Bisphenol-A" or "TBBA"); 2,2- bis(3,5-dialkyl-4-hydroxyphenyl)propane ("Tetraalkyl Bisphenol-A") where the alkyl can be methyl or ethyl, for example 2,2-bis(3,5-dimethyl-4-hydroxyphenyl)propane ("Tetramethyl Bisphenol-A"); 1 , 1-bis(4-hydroxyphenyl)- 1 -phenyl ethane ("Bisphenol-AP" or "Bis-AP"); Bishydroxy phenyl fluorene; and 1 ,1-bis(4-hydroxyphenyl)cyclohexane.

Using a process such as is generally described above, a polycarbonate product can be obtained having a weight average molecular weight, as determined by light scattering or o gel permeation chromatography, of 8,000 to 200,000 and preferably 15,000 to 40,000, and/or a melt flow value of 3 to 150, preferably 10 to 80 (as determined by ASTM Designation D 1238-89, Condition 300/1.2), although values outside these ranges are permitted as well. Molecular weight can be controlled by addition to the reaction mixture of a chain terminator which may be selected from monofunctional substances such as phenols, alcohols, amines, imides, 5 carbonic acid chlorides, sulfonic acid chlorides, benzyltriethyl ammonium chloride, or phenylchiorocarbonates. A chain terminator may be added to the reaction mixture before or after a dihydroxy compound is contacted with a carbonate precursor, and is typically used in an amount of 0.01 to 0.1 moles per mole of dihydroxy compound.

0 branched rather than linear polycarbonate molecule can be obtained by adding to the reaction mixture a tri- or polyfunctional monomer.

The preferred process of this invention is that in which an aromatic polycarbonate is prepared. An aromatic polycarbonate is defined herein with reference to the oxygen atoms, 5 of the one or more dihydroxy compounds present in the polycarbonate chain, which are bonded to a carbonyl carbon. In an aromatic polycarbonate, all such oxygen atoms are bridged by a dihydroxy compound residue some portion of which is an aromatic ring.

Also included within the term "polycarbonate", as used herein, are various 0 copolycarbonates, certain of which can be prepared by incorporating one or more different dihydroxy compounds into the reaction mixture. When a dicarboxylic acid such terephthalic acid or isophthalic acid (or an ester-for ning derivative thereof) or a hydroxycarboxylic acid is used in the reaction mixture, or to form an oligomeric prepolymer, instead of one of the "different" dihydroxy compounds mentioned above, a poly(ester/carbonate) is obtained In a 5 preferred embodiment, the compositions of this invention exclude a poly(ester/carbonate).

Copolycarbonates can also be prepared, for example, by reaction of one or more dihydroxy compounds with a carbonate precursor in the presence of a chlorine- or amino-

terminated polysiloxane, with a hydroxy-terminated poly(phenylene oxide) or poly(methyl methacrylate), or with phosphonyl dichloride or an aromatic ester of a phosphonic acid. Siloxane/carbonate block copolymers are discussed in greater detail in Paul, USP 4,596,970.

The methods generally described above for preparing carbonate polymers suitable for use in the practice of this invention are well known; for example, several methods are discussed in detail in Schnell, USP 3,028,365; Glass, USP 4,529,791 ; and Grigo, USP 4,677,162.

Component (b) in the compositions of this invention is chlorinated polyethylene ("CPE"). CPE can be prepared in a process in which a chlorine radical, generated from Cl ₂ in a free-radical mechanism catalyzed by ultraviolet light or initiators, abstracts a hydrogen atom from a polyethylene chain, leaving a carbon radical. The carbon radical reacts with a molecule of chlorine to bond a chlorine atom to the polyethylene chain and liberates the other to continue the chain reaction. An alternative to Cl as the chlorinating agent is C! λ Polyethylene which retains regions of crystallinity during the reaction exhibit biock chlorination whereas amorphous polyethylene, in which most or all portions of the polymer chain are accessible, exhibit random chlorination.

The polyethylene which i? subjected to chlorination can be a homopolymer of ethylene or a copolymer of ethylene an,., one or more higher 1 -alkenes such as propyiene, butylene or octene. These polyethylenes typically have a density of 0.90-0.97 g/cm ³ , preferably 0.935-0.967 g/cm ³ , and a melt index of 0.01-40 dg/min, preferably 0.1-12 dg/min, and more preferably 0.15-3 dg/min. Chlorination can occur in solution wherein a solvent such as a carbon tetrachloride is used at a temperature of 60-1 10°C. However, the process is more commonly run in an aqueous suspension whe ein, in a first step, 2 to 23 weight percent chlorination occL -s at a temperature below the agglomeration temperature of the ethylene polymer, followed by chlorination to an extent of up to 75 percent, preferably up to 48 percent, by weight in a second step at a temperature above the first temperature but at least 2°C below the crystalline melting point of the ethylene pol /mer. Wetting agents such as sulfonates or polyphosphates may be advantageously employed in the aqueous process. Such an aqueous process and others are more particularly described in U.S. Patents 3,454,544 and 3,563,974, each of which is incorporated herein. Chlorination can aiso occur in an anhydrous process wherein powdered polyethylene is agitated while contacted with a stream or atmosphere of heated chlorine gas, as more particularly described in U .S. Patent 4,425,206, which is incorporated herein, or by reacting the polymers in molten form, as more particularly described in U.S. Patent 3,909,486, which is also incorporated herein.

The chlorine content of the CPE thus produced can be 25 to 50 percent by weight, is preferably 30 to 45 percent by weight, and is more preferably 34 to 42 percent by weight.

The weight average molecular weight of CPE may be 50,000 to 350,000, preferably 80,000 to 240,000, and more preferably 175,000 to 225,000 CPE is typicauy low in crystallmity, as measured by differential scanning caloπmetry, for example below 3 cal/gram In a preferred embodiment, the residual crystallmity of CPE is at or below 1 cal/gram In an alternative embodiment, the CPE used in the compositions of this invention can be a chlorosulfonated polyethylene ("CSM") In the preparation of CSM, a carbon radical is generated on the polyethylene chain in a manner analogous to the preparation of CPE Addition of a chlorine atom or a molecule of S0 ₂ then follows a: tne site of tne carbon radical If S0 ₂ is aααed at the carbon ra :al, a sulfur radical is generated, and addition of a chlorine atom then occurs at the sulfur radical In a typical CSM, --CH - groups, --CHCI-- groups and - CHS0 ₂ C- groups are present ^* n a ratio of 108/32/1 Preparation c ^* CSM car occur in a homogenous solution using, for example, carbon tetracnloπce or methylene chloπαe as the solvent When chloroberzene is the solvent, a temp- ^** ature of 105- 1 10°C at atmospheric pressure is typical An initiator such as 2-methyl-2,2'-azobιsDropanenιtrιie is used A process such as the foregoing is more pan cularly descπoed in U S Pa ^τ --nt 3,299,014, which is incorporated herein

Component (b) in the compositions of this invention also includes a CPE in which one or more ethyienically unsaturated monomers has been graft polymerized onto the polyethylene backbone Such graft polymerization may be accomplished via a free radical mechanism and is commenced after the CPE has been in contact with the ethyienically unsaturated grafting monomer(s) allowing the ethyienically unsaturated monomer(s) to disperse into the CPE The purpose of this contact time is to enable the grafting monomer(s) to penetrate the CPE thereby permitting enhanced graft polymerization during the polymerization step to orm a network structure of CPE and grafted polymers or copolymers A CPE whicn is not grafted with ethyienically unsaturated monomers may be employed in combination witn a CPE which is graft polymerized

Ethyienically unsaturated grafting monomers, such as ethyienically unsaturated carboxy c acid esters, useful in preparation of a grafteα CPE can be aliphatic or aromatic and include one cr more of the following acrylates, alkvl acr/lates, lower alkyl acylates, alkyl metnacrylates, lower alkyl methacrylates, and c her carπoxylic acid esters including vinyl esters for example vinyl acetate, vinyl propionate, vinyl butyrate, vinyl stearate, vinyl benzoate and vinyl p-chlorobenzoate, and monovmyl aromatic compounds, including styrene, alpha methyl styrene, t-butyl styrene, acrylonitπle, and other ethyienically unsaturated monomers suitable for copolymeπzation with a styrenic monomer as described below with reference to a styrenic copolymer

Preferred grafting monomers are the alkyl me nacrylates, the lower alkyl methacrylates, vinyl acetate, and stvrene, with the most preferred being methyl methacylate Another highly preferred monomer is vinyl acetate Preferred mixtures of monomers include

mixtures of acrylates and styrenics, of alkyl acrylates and styrenics, of lower alkyl acrylates and styrenics, of alkyl methacrylates and styrenics, of lower alkyl methacrylates and styrenics, of acrylates and vinyl esters, of alkyl acrylates and vinyl esters, of lower alkyl acrylates and vinyl esters, of alkyl methacrylates and vinyl esters, and of lower alkyl methacrylates and vinyl esters A highly preferred mixture is of methyl methacrylate and styrene Another highly preferred mixture is of methyl methacrylate and vinyl acetate As used in the description of the grafting monomers, the term alkyl refers to alkyl groups having from 1 to 8 carbon atoms Tne term lower alkyl refers to alkyl groups having from 1 to 4 carbon atoms

The polymeπzable mixture comprises in a preferred embodiment from 60 to 95 parts, more preferably from 80 to 90 parts, by weight CPE and from 5 to Λ0, more preferably from 10 to 20, parts by weight of an ethyienically unsaturated grafting monomer or comonomer mixture of monomers

The preferre process for making a grafted CPE involves the mixing of CPE resin, an ethyienically unsaturated grafting monomer or mixture of monomers, water, initiators, and o ^τ ner additives such as a suspending agent in a suspension process reactor The reactants are mixed through conventional stιr ^** eα agitation and form a slurry suspension Prior to the copoiymeπzation in the aqueous suspension slurry it is important to disperse the monomers or comonomers into suspended CPE by diffusion This intimately mixed CPE and monomer network will then copolymeπze by free-radical initiation to form a network structure of CPE and grafted copolymers

The reactor is then heated to a temperature of from 70°C to 1 10°C for a time of from 4 hours to 14 hours Preferably the reactor is heated to a temperature of from 75°C to 95°C for a time of from 6 hours to 12 hours, and more preferably is heated to a temperature of from 80°C to 90°C for a ti me of from 8 hou rs to 10 hou rs After polymerization is complete, the grafted CPE product is dewatered and dried, for example, in a fluidized bed dryer, from 4 to 10 hours at a temperatur ^■ of 50°C o 75°C, preferably from 5 to 10 hours at a temperature of 55°C to 70°C, and more preferably from 6 to 9 hours at a temperature of 60°C to 65°C

Initiators useful in this preferred free radical polymerization process are the known organic perester and peroxide type initiators Especially useful are the organic perester and peroxide initiators having a one hour half-life temperature of 90°C - 120°C Typical and useful perester and organic peroxide mitiators are benzoyl peroxide, lauroyl pe ^r oxιde, 1 , 1-dι-(t- amylperoxy)-cyclohexdne, 1 -1 -dι-(t-butylperoxy)-cyclohexane, and tertiary butyl peroctoate Tertiary butyl peroctoate having a one hour half-life temperature of 1 15°C ιs the most preferred initiator

- ^• or obtaining a good suspension, vigorous stirring is performed and a suspension stabilizer or suspending agent is used The conventional suspension stabilizers are preferred in this invention and include such organic materials as the polyvinyl alcohols, polyalkylene oxides

and cellulose derivatives, with the cellulose derivatives oeing most preferred Typical of the most preferred cellulose derivatives are methyl cellulose, hydroxyme+hvl cellulose, and methyl hydroxypropyl cellulose with hydroxymethyl cellulose c eing most preferred

Methods for making a grafted CPE resin are discussed in greater detail in commonly assigned U S application s N 07/868,908, filed Apt I 16, 1992, which is incorponted herein

Component (c) in the comoositions ot tnis invention is a styrenic copolymer prepared from one or more styrenic monomers and one or more ethyienically unsaturated monomers cooolymeπza ¹ - e with a styrenic monomer Tne styrenic copoivmer mav be a random, alternate, bloc or grafted copolymer, and a mixture ot more than one styrenic copolymer may be used as well

Styrenic monomers of particular interest for use in prepara ^t ion of a styrenic copolymer, in addition to styrene itself, include one or more of the substituted styrenes or vinyl aromatic compounds described by the following formula (it being understood tnat a reference to "styrene" herein is to be read as a reference to any of the styrenic or vinyl aromatic monomers described herein or any others of like k.nd)

Component (e) in the compositions of this invention is a molding polymer selected from (i) polyacetal, (n) polyacrylate, (in) polyamide, (iv) an epoxy resin, (v) ethylene/carbon monoxide copolymer, (vi) polyester, (vn) poly(phenylene ether), (vin) polystyrene, (ix) polyurethane, and (x) poly(vιnyl chloride), and mixtures thereof

Component (e)(ιι) is an acrylate polymer, which is defined as a polymer prepared by homooolymeπzation of an alkyl acrylate or an alkyl methacrylate or by copolymenzation of a mixture ot the two, and includes a mixture of any such homopoiymers or copolymers

Component (e)(ιv) is an eooxy resin An eooxy resin as utilized in the compositions of this ιnvep ^** ιon is typically prepared from an epihalonydπn such as epichloronydπn, whicn .s reacted in the presence of a oase witn a compound containing at least two active hydrogen atoms Representative materials used as a base for such purpose include caustics such as the alkali metal and alkaline earth oxides and hydroxides An active hydrogen atom is one which can be a >tracted by such a base to form an anion When the active-hydrogen-containing compound is reacted with epichlorohydrin, each anion formed thereon by the deprotonating or catalytic action of ^* he base opens the epoxide ring at the alpha carbon on an epichlorohydrin molecule to create a hydroxyl group on the beta carbon Dehydrohalogenation then occurs at each such location to regenerate an eooxide ring at the

beta and gamma carbons If, in the active-hydrogen-containing compound, hydrogen was abstracted from oxygen, the product at tnis point may for practical purposes be represented as the diglycidyl ether of the active-hydrogen-containing compound When other molecules of the deprotonated active-hydrogen-containing compound attack unreacted epichlorohydrin or attack the epoxide ring having been formed as each terminus of tne diglycidyl ether of the active-hydrogen-containing compound, a polymer is formed which is a poly(hyoroxy ether) containing epoxide rings at its termini It is c ssible that one terminus of such polymer could be occupied by an unabstracted hydrogen atom rather than an eooxide ring An epoxy resin suitable for ue herein can generally be represented by the following structure

10

wherein Q is the residue of the active-hydrogen-containing compound, R is hydrogen or C1- 15 alkyl or alkoxy, and p, which can ranqe from zero to 100, is the degree of polymerization 2Q (number of repeating units) P ca ^* \ foi example, be less thεn sixty, is advantageously less than forty, is preferably less than twenty, and is more preferably less than ten P can, for example, be 0 to 20, 0 to 10, 1 to 10, or 1 to 5

Use of an excess of epichlorohydrin SL. .presses the molecular weight of the epoxy 2 ₅ resin, a ratio of as little as 2/1 , epichlorohydrin to active-hydrogen-containing compound, is typically sufficient to yield a degree of polymerization of 0 35 or less however, higher molecular weight epoxy resins can be prepared using the process described above oy reacting the active-hydrogen-containing compound with only a slignt excess of epichlorohydrin In this direct (or taffy) process, the resins usually produced are those whicn have a degree of -,n polymerization of 4 or less

In the fusion process, the diglycidyl ether of the acti ve-hydrogen-containing compound is reacted with an additional charge of the active-hydrogen-containi ng compound Caustic (or other proton acceptor such as triethanolamine, a substiti uted imidazole or Na2C03) , _r IS used in the reaction in only a catalytic amount as the oxyanion regenerates itself each time an epoxide ring is opened and secondary hydroxyl group is formed Reaching high molecular weight is dependent on employment of agitation, and of higher temperature (up to 150°C) and pressure than used in the direct method, because of the viscosity of the reaction mass Epoxy

resins with a degree of polymerization of 30 or more can be prepared by the fusion process Epoxy resins can also be prepared by direct epoxidation of the C = C ond in an olefin by a peracid such as peroxybenzoic acid, C6H5C020H

Epoxy resins, prepared as described above, can be esteπfied with saturated or unsaturated fatty acids at either the te ^r mιnal epoxide ring or at a pendant hyoroxyl site along the polymer backbone Such an esteπfication reaction is typically conducted in an inert atmosphe ^r e at 225-260°C, with the removal of water as a by-product

Oxyanions for use in the preparation of an epoxy resin can be derived from the various bisphenols such as are described aoove witn respect to the preparation of polycarbonate Use of oxyanions prepared from bisphenols yields an epoxy resin of the type which is frequently referred to as a onenoxy resin However, oxvanions can also be prepared from bis o-hydroxy phenyl fiuorene, from a bisphenol where the aromatic rings are hydrogenated, with tne use of tnshydroxy phenols or any of the oranching agents mentioned above with respect to the preparation of polycarbonate, or from a C2-C18 alkyl or alkylidene or a C4-C20 cycloalkyi or cycloalkylidene diol or tπol

Bisphenol-A is an example of an especially preferred aromatic diol to be used in the preparation of the epoxy resin of this invention When a halogenated bisphenol

(containing, for example, bromine) is used to prepare the epoxy resin, an epoxy resin having good flame retardant properties, such as D E R ® 542 epoxy resin (available from The Dow Chemical Company), is obtained An exemplary halogenated epoxy resin can be represented by the following general formula

H, H„

where each T can independently be hydrogen or an aliphatic hydrocarbyl group having from 1 to 3 carbon atoms and is preferably hydrogen, each M is independently chlorine or bromine and is preferably bromine in each occurrence, each i is independently 1 or 2 and is preferably 2 in each occurrence, each L is independently a divalent hydrocarbyl group havi g f rom 1 to 12 carbon atoms, preferably 3 carbon atoms, and q can be any value from 0 to 20 (not necessarily

an integer) and is preferably from 0 to 6, more preferably from 0 to 1. The term hydrocarbyl as employed herein means any aliphatic, cycloaliphatic or aromatic groups. Compounds of this type are commercially available as DER 542, DER 51 1 and QUATREX 6410 brands of epoxy resin from The Dow Chemical Company and DP 452 orand epoxy resin from Ciba Geigy. The epoxy resins useful in this invention can also be prepared from the reaction of a novolac and epihalohydrin. Representative novolacs are phenol/formaidehyde condensates in which multiple phenol functionalities are joined by methylene bridges. In novolac epoxies, multiepoxy functionality can increase with increasing molecular weight because the polymer is formed from the methylene bridges, leaving each phenolic hydroxyl group free to react with epichlorohydrin to form a pendant epoxide ring. The novolac may additionally be prepared from a substituted phenol. Novolac epoxies may be generally represented by a formula such as

where d is O to 10 and each R2 is independently hydrogen or C1 -15 alkyl or alkoxy. An example of a novola epoxy suitable for use herein is D.E.N. ^® 431 epoxy resin (available from The Dow Chemical Company).

Epoxy resins such as are described above, and methods for preparing same, are discussed in greater detail in Perry, USP 3, 148,855 and Doorakian, USP 4,302,574, each of which is incorporated herein.

Component (e)(v) is a polyester. Suitable reactants for making the polyester used in this invention, in addition to hydroxycarboxyiic acids, are diols and dicarboxylic acids either or both of which can be aliphatic or ar atic. A polyester which is _u poly(alkylene alkanedicarboxylate), a poly(alkylene arylenedicarboxylate), a poly(arylene aiKanedicarboxylate), or a poly(arylene arylenedicarboxylate) is therefore appropriate for use herein. Alkyl portions of the polymer chain can be substituted with, for example, halogens, C1 - C8 alkoxy groups or C I -C8 alkyl side chains and can contain divalent heteroatomic groups (such

as -0-, -Si-, -S- or -S02-) in the oaraffinic segment of the chain The cnain can also contain unsatu ration and C6-C10 non-aromatic rings Aromatic rings can contain substituents such as halogens, C1 -C8 alkoxy or C1-C8 alkyl groups, and can be joined to tne polymer backbone in any ring position and directly to the alcohol or acid functionality or to mtervenmg atoms Typical aliphatic diols used in ester formation are the C2-C10 primary and secondary glycols, such as ethylene-, propylene-, and butylene glycol Alkanedicarboxy c acids frequently used are oxalic ac d, adipic acid and sebaci acid Diols which contain rings can be, for example, a 1 ,4-cycloo xylenyl glycol or a 1 cvclohexane-dimethyiene glycol, resorcinol, hydroquinone, 4,4'-thιodiDhenol, bιs-(4-hydroxypnenyl)sulfone, a oihydroxynaphthalene, a xylylene diol, or can be one o ne many bisphenols such as 2,2-bιs-(4-hyoroxypnenyl)propane Aromat'C diacids include, for example, terephthahc acid, isophthalic acid, naphthalenedicarboxy c acid, diphenyletherdicarboxyhc acid, diphenyldicarboxyhc acid, diphenylsulfonεoicarboxylic acid, diphenoxyethanedicarboxy c acid

In addition to polyesters formed from one diol and one diacid only, the term "polyester" as used herein includes random, patterned or olock copolyesters, for example those formed from two or more different diols and/or two or more different diacids, and/or rom other αivaient heteroatomic groups Mixtures of such copolyesters, mixtures of polyesters derived from one diol and diacid only, and mixtures of members from both of such groups, are also all suitable for use in this invention, and are all included in the term "polyester" For example, use of cyclohexanedimethylol together with ethylene glycol in esterification with terephthahc acid forms a clear, amorphous copolyester ("PETG") of particular interest Also contemplated are PCTG, liquid crystalline polyesters derived from mixtures of 4- hydroxybenzoic acid and 2-hydroxy-6-naphthoιc acιd, or mixtures of terephthahc acid, 4- hydroxybenzoic acid and ethylene glycol, or mixtures of terephthahc acid, 4-hydroxybenzoιc acid and 4,4'-dιhydroxybιphenyl

Aromatic polyesters, those prepared from an aromatic diacid, such as the poly(alkylene arylenedicarboxylates) polyethylene terephthalate and polybutylene terephthalate, or mixtures thereof, are oarti larly useful in nis invention A polyester suitable for use herein may have an intrinsic viscosity of 0 4 to 1 04, although values outside this range are permitted as well

Methods and materials useful for the production of polyesters, as described above, are discussed in greater detail in Whmfield, USP 2,465,319, Pengilly, USP 3,047,539, Schwarz, USP 3,374,402, Russell, USP 3,756,986 and East, USP 4,393, 191 , each of which is incorporated herein by reference

Component (e)(vι) is an ethylene/carbon monoxide copolymer, or an ethylene/carbon monoxide copolymer to which one or more ethyienically unsaturated

monomers have been graft polymerized, suitable varities of which are described in Laughner, USP 4,929,673, which is incorporated herein by reference.

CA, CHA

wherein each A is independently hydrogen, a C1 -C6 alkyl radical or a halogen atom such as chlorine or bromine; and each E :S independently hydrogen, a C1 -C10 alkyl, cyclou kyl, alkenyl, cycloalkenyl, aryl, aikaryl, aralkyi or alkoxv radical, a halogen atom such as chlorine or oromine, or two E's may be joined to form a naphthalene structure. Representative examples of suitable styrer ; monomers, in addition to styrene itself, include one or more of the following: ring- substituted alkyl styrenes, for example vinyl toluene, o-ethylstyrene, p-ethylst> -ene, ar-(t- butyl)styrene, 2,4-dimethylstyrene; ring-substituted halostyrenes, for example, o- chlorostyrene, p-chlorostyrene, o-bromostyrene, 2,4-dichlorostyrene; ring-alkyl, ring-halo- substituted styrenes, for example 2-chloro-Δ- ithylstyrene and 2,6-dichloro-^-methylstyrene; ar-methoxy styrene, vinyl naphthalene or anthracene, p-diisopropenylbenzene, divinyl benzene, vinylxylene, alpha-methylstyrene, and alpha-methylvinyltoluene.

Ethyienically unsaturated monomers of particular interest ^; or copolymerization with a styrenic monomer include one or more of those described by the formula: D~ CH = = C(D)-(CH2)n-G, wherein each D independently represents a substituent selected from the group consisting of hydrogen, halogen (such as fluorine, chlorine or bromine), C1 -C6 alkyl or alkoxy, or tak n together represent an anhydride linkage; G is hydrogen, vinyl, C1-C12 alkyl, cycloalkyi, alkenyl, cycloalkenyl, alkaryl, arylalkyl, alkoxy, aryloxy, ketoxy, halogen (such as fluorine, chlorine or bromine), cyano or pyridyl; and n is 0-9.

Representative examples of ethyienically unsaturated monomers copolymerizable with a styrenic monomer are those which bear a polar or electronegative group and include one or more of the following: a vinyl nitrile compound such as acrylonitrile,

methacrylonitπle, ethacrylonitrile, alphachloroacrylonitrile and fumaronitriie, a diene such as butadiene, isoprene, isobutylene, pioerylene, cyclooentadiene, natural rubber, chlorinated rubber, 1 ,2-hexaoιene, methyl-1 ,3-pentadιene, 2,3-dιmethyl- 1 ,3-1 ,3-oentadιene, 2-methyl-3- ethyl- 1 ,3-butadιene, 2-ethyl-1 ,3-pentadιene, 1 ,3- and 2,4-hexaoιenes, chloro- and bromo- substituted butadienes such as dichlorobutadiene, bromobutadiene, chlcroprene and dibromobutadiene, and butadiene/isoprene and isoprene/isobutylene copolymers; 1 ,3- divinylbenzene, 2-phenyl propene; a C2-C10 aκylene compound including halo-substituted derivatives thereof such as vinyl or vinyl ^* !ιne chloride, the alpha, beta-ethylenically unsaturated carboxy c acids, such as acrylic acid, methacry c acid, maleic acid, succmic acid, acotmic acid and itaconic acid, and their anhydrides and C 1 - C10 alkyl, ami noal kyl and hydroxyaikyl esters and amides, such as alkyl acrylates and methacrylates such as methyl acrylate, prooyl acrylate, butyl acrylate, octyl acrylate, methyl aloha-chloro acrylate, methyl, etnyl or isobutyl methacrylate, hydroxyethyl and hydroxypropyl acrylates, amiroethyl acrylate and glycidyl me -acrylate; maleic annydπde, an alkyl or aryl maleate or fumarate such as diethylcNoromaleate or diethyl fumarate; an aliphatic or aromatic maleimide, such as N- phenyl maleimide, including the reaction product of a C1 - C10 alkyl or C6 - C14 aryl primary amine and maleic anhydride, methacrylamide, acrylamide or N N-dietnyl acrylamide, vinyl ketones such as methyl vinyl ketone or metnyl isoproper/l ketone, vinyl or allvl acetate and higher alkyl or aryl vinyl or allyl este-s, vinyl alcohols; vinyl et-iers sucn as C1 -C6 alkyl vinyl ether and their alkyl-substituted halo derivatives, vinyl pyndines; vinyl furans, vinyl aldehydes such as acrolem or crotonaldehyde, vinyl carbazole, vinyl pyrro done, N-vinylphthahmide, and an oxazo ne compound includes those of the general formula

C ( J„ ) = = C ( J ) — C = =N-- C ( J ₀ ) -- C ( J, ) ~ 0

where each J is independently hydrogen, halogen, a C1 -C10 alkyl radical or a Cδ-C14 aryl radical;

Examples of preferred styrenic copolymers are vinyl aromatic/vinyl nitπle copolymers such as styrene/acrylonitπle copolymer ("SAN "), styrene/maieic anhydride copolymer, styrene/glycidyl methacrylate cooolymer, aryl maleimimde/vinyl nitπle/diene/styrenic copolymer, strene/alkyl methacrylate fooolymer, styrene/alkyl methacrylate/glydicyl methacrylate copolymer, styrene/butyl acrylate copolymer, methyl

methacryalte/acrylonitrile/butadiene/styrene copolymer, or a rubber-modified vinyl aromatic/vinyl nitrile copolymer such as an ASS, AES or ASA copolymer.

AES (acrylonitrile/butadieπe/s -ene copolymer) is an elastomeric-thermoplastic composite in which vinyl aromatic/vinyl n< ϋ ^** ι ^' =. copolymer is grafted onto a polybutadiene substrate latex. The polybutadiene forms r rticles of rubber - the rubber modifier or elastomeric component - which are dispersed as a discrete phase in a thermoplastic matrix formed by random vinyl aromatic vinyl nitrile cooolymer. Typically, vinyl aromatic/vinyl nitrile copolymer is both occluded in and grafted to the particles of rubber. AES (acrylonitrile/EPDM/styrene) copolymer is a styrenic copolymer which s obtained when vinyl aromatic/vinyl ni trile copolymer is rubber-modified by grafting viny' o'natio'vinyl nitrile cope mer tc itrate made up of an EPDM (ethyiene/ρropylene/π n-conjugated diene) rubber. AES c 'ers are discussed in greater de— . in Henton, USP 4,765, 175, which is incorporated a: hereof. A vinyl aromatic/vinyl nitrile copolymer can also be crosslinked to an aikyl acrylai*. , stomer to form a rubber-modified styrenic copolymer, as in the case of an ASA (acrylonitrile styrene/acrylate) copolymer, which is discussed in greater detail in Yu, US? 3,944,631 , which is also incorporated as a part hereof.

The monomers copolymerized to form a styrenic copolymer may each be used in virtually any amount from 1 to 99 weight percent, but a styrenic copolymer will typically contain at least 15 percent by weight, preferably at least 35 percent by weight, and more preferably at least 60 percent by weight of a styrenic monomer, with the balance being made up of one or more copolymerizable ethyienically unsaturated monomers. When rubber modified, a styrenic copolymer will typically contain at least 15 percent by weight, preferably at least 25 percent by weight, and more preferably at least 35 percent by weight of a styrenic monomer, with the balance being made up of one or more copoiymerizable ethyienically unsaturated monomers. In certain embodiments, a vinyl nitrile monomer is used in a styrenic copolymer in an amount of greater than 35 percent, typically greater than 40 percent, advantareously greater than 45 percent, desirably greater than 50 percent, preferably greater than 55 percent, and more preferably greater than 60 percent, by weight of the styrenic copolymer.

The elastomeric phase of a rubber-modified styrenic copolymer as employed in the compositions of this invention is up to 45 percent, preferably 5 to 40 percent, more preferably 10 to 35 percent, by weight of the copolymer. The preferr d elastomeric phase exhibits a glass transition temperature (Tg) generally less than 0°C, more preferably less than - 30°C, and most preferably from -1 10°C to -50°C as determined by ASTM D-746-52T or -56T. The elastomeric phase advantageously has an average particle size of 10 microns or less, preferably

in the range from 0 05 to 5 microns, and more preferably in the range from 0 1 to 0 3 microns, and typically exnibits an intrinsic viscosity, as determined at 25°C in toluene, of 0 1 to 5 In addition to the aforementioned monomeπc components, it should be understood that the elastomeric phase may also contain relatively small amounts, usually less than 2 weight percent based on the rubber, of a crosslinking agent such a divinyl benzene, diallylmaleate, ethylene glycol dimethacrylate provided that such crosslinking does not eliminate the desired elastomeric character of rubber

A stvrenic copolymer may be made by an emulsion, suspension or mass (pjlk) 0 method

Methods for making AB5 or other styrenic :ooolymers, as described aoove, are discussed in greater detail in Chiiders, USP 2,820,773, Calvert, USP 3,238,275, Carrock, USP 3,515,692, Acker an, USP 4, 151 , 128, <ruse, USP 4 187,250, Simon, USP 4,252,91 1 Weoer, USP ₅ 4,526,926, Rudd, USP 4, 163,762 ano Weber, USP 4,524,986, each being herepy incorporated as a part nereot

Component (d) in the compositions of this invention is an elastomeric impact modifier, several different varieties of which, or a mixture thereof, are suitable for use herein o The elastomeric impact modifier as used herein typically has an elastomer or rubber content of greater than 45 percent by weight One form which such elastomeric impact modifier may take is a thermoplastic elastomer, that is that which is frequently characterized, for example, in that it can be melted and recooled, or dissolved and reformed upon recovery from solvent, without undergoing any significant change in properties A thermoplastic elastomer is usually also 5 characterized by the randomness of the shape and size it assumes when mixed by shearing forces with the otner components contained in the compositions of this invention, especially when heat is applied during such mixing Because a thermoplastic elastomer is typ.cally a long chain molecule, segments of a thermoolast'c elastomer in the polymer composition matrix are generally elongated, linear ribbons or bands Tne molecules teno to fuse and flow together in 0 a continuous structure However, chain coiling can yield globule-shaped segments of tnermoplastic elastomer in the matrix

One example of a thermoplastic elastomer is a block copolymer whicn can be either linear, branched, radial or teleblock, and can be either a dι-bloc< ("A-B") copolymer, tπ- 5 block ("A-B-A") copolymer, or radial teleblock copolymer with or without tapered sections, that is portions of the polymer where the monomers alternate Dr are in random order close to the point of transition between the A and B blocks The A portion is frequently prepared by polymerizing one or more vinyl aromatic hydrocarbon monomers, ano has a weight average

molecular weight of 4,000 to 1 15,000, preferably 8,000 to 60,000. The B portion of the block copolymer typically results from polymerizing a diene and has a weight average molecular weight of 20,000 to 450,000, preferably 50,000 to 300,000. In an A-B di-block copolymer, each block, A or B, can vary from 10-90% of the total weicnt of the copolymer. In an A-B-A tri-block copolymer, the A end groups typically constitute 2 wt% to 55 wt% of the whole block copolymer, and preferably are between 5 wt% and 45 wt% of the whoie block copolymer.

The A bloc ^' of the block copolymer has properties characteristic of thermoplastic substances in that it has the stability necessary for processing at elevated temperatures and yet possesses good strength below the temperature at which it softens. The A block of a vinyl aromatic block copolymer is polymerized predominantly from the various styrenic monomers described above with respect to a styrenic copolymer, but minor proportions of other copolymerizable ethyienically unsaturated monomers (also described above in the same context) may be _sed as well. The polymerization can be initiated by lithium metal, or alkyl- or aryl lithium compounds such as butyl lithium or isoamyl lithium. Polymerization is normally conducted at temperatures ranging from -20°C to 100°C.

The 3 block of the copolymer can be formed, for example, simply by injecting suitable monomer into the reaction vessel and displacing the lithium radical from the just- polymerized A block, which then acts as an initiator because it is still charged. The B block is formed predominantly from substituted or unsubstituted C2-C10 dienes, particularly conjugated dienes such as butadiene or isoprene. Other diene or copolymerizable ethyienically unsaturated monomers (described above in connection with a styrenic copolymer) may be used in the formation of the B b'ock provided that they are present at a level low enough to not alter the fundamental olefinic character of the B block. The B block will be characterized by elastomeric properties which allow it to to absorb and dissipate an applied stress and then regain its shace. In the A-B-A tri-block copolymer, the second end block A can be formed in a manner similar to the first, by injecting appropriate vinyl aromatic monomer into the reaction vessel.

To reduce oxidative and thermal instability, the block copolymers used herein can also desirably be hydrogenated to reduce the degree of unsaturation on the polymer chain and on the pendant aromatic rings. The block copolymer may be selectively hydrogenated by hydrogenating only the elastomeric block B. Typical hydrogenation catalysts utilized are Raney nickel, molybdenum sulfide, finely divided palladium and platinum oxide. The hy .irogenation reaction is typically run at 75-450°F and at 100-1 ,000 psig for 10-25 hours.

The most preferred vinyl aromatic block copolymers are vinyl aromatic/conjugated diene block copolymers formed from styrene and butadiene or styrene and isoprene. When the styrene/butadiene copolymers are hydrogenated, they are frequently represented as styrene/(ethylene/butylene) copolymer in the di-block form, or as styrene/(ethylene/butylene)/styrene copolymer in the tri-block form. When the styrene/isoprene copolymers are hydrogenated, they are frequently represented as styrene/(ethylene/propylene) copolymer in the di-block form, or as styrene/(ethylene/prooylene)/styrene copolymer in the tri-block form. Vinyl aromatic/diene block cc-olymers such as are describe ^** : above are discussed in greater detail in Holden, USP 3,265,755, Haefele, USP 3,333,024, Waid, USP 3,595,942, and Witsiepe, USP 3,651 ,014, each of which is incorporated herein, and many are available commercially as the varios Kraton™ elastomers from Shell Chemical Company.

Linear, branched, radial or teleblock A-B-A or A-B block copolymer thermoplastic elastomers can also be prepared from materials other than vinyl aromatic systems. These other copolymers also have a rigid block " V having a Tg above room temperature (approximately 23-25°C) and a rubbery block "B" having a Tg below room temperature. Examples of typical pairings of the various materials used to form the respective A and B blocks of sucn other block copolymer thermoplastic eiastorr ^* s are shown below in Table I.

Table I Block Copolymer Pairings

A block B block polyethylene ethylene/butylene copolymer polyurethane polyester polyether polyester polyether polypropylene EPDM rubber

These non-vinyl aromatic block copolymer thermoplastic elastomers can also be prepared, for example, by anionic polymerization using an alkyl-lithium initiator. Thermoplastic elastomers based on urethane are discussed in greater detail in Schollenberger, USP 3,015,650 and Saunders, USP 3,214,41 1 ; and those based on copolyester-ether are discussed in Witsiepe, USP 3,651 ,014, each of which is incorporated herein.

Other thermoplastic elastomers useful in the compositions of this invention are those based generally on a long-chain, hydrocarbon backbone ("olefinic elastomers"), which may be prepared predominantly from various mono- or dialkenyl monomers and may be grafted with one or more styrenic monomers. Representative examples of a few olefinic elastomers which illustrate the variation in the known substances which would suffice for such purpose are as follows: butyl rubber; chlorinated polyethylene rubber; chlorosulfonated polyethylene rubber; an olefin polymer or copolymer such as ethylene/propylene copolymer or ethylene/propylene/diεne copolymer, which may be grafted with one or more styrenic monomers; neoprene rubber; nitrile rubber; polybutadiene and polyisoprene.

An example of a preferred olefinic elastomer is a copolymer which has a a glass transition tem perature (To less than 0°C prepared from (i) at least one olefin monomer such as ethylene, propylene, isopropylene, butylene or isobutylene, or at least one conjugated diene such as butadiene, , cr mixtures thereof; and (ii) an ethyienically unsaturated monomer carrying an epoxide group (for example, glycidyl methacrylate), and, optionally, (iii) an ethyienically unsaturated monomer which does not carry an epoxide group (for example, vinyl acetate). Tg is the temperature or temperature range at which a polymeric material shows an abrupt change in its physical properties, including, for example, mechanical strength. Tg can be determined by differential scanning calorimetry.

Tne random shape and size assumed in the polymer composition matrix by a thermoplastic elastomer is to be distinguisned from the shaoe and size assumed by a core-shell graft copolymer A core-shell graft copolymer is typically present in t~s polymer matrix in a bead shape both before and after mixing by application of shearing forces, whether heat is used or not, and is usually present in a rather narrow size range, for example 0 05-0 8 microns The retention of this core-shell, or spherical, shape by the graft copolymer, even after heating and mixing, results from the fact that the outer layers, which jrround the core, are formed by grafting appropriate monomers onto the core A core-shell graft copolymer typicaliv cannot be melted and recooled without a significant change in properties because the grart copolymer will tend to decompose or crosslink, and the bead-shaped segments of graft cooolymer will tend to agglomerate uoon melting, making dispersion of them oy mixing difficult

Representative examples of the core-shell graft cooolymer elastomers suitable for use herein are those which are based on either a diene rubPer, an alkyl acrylate rubber, or on mixtures tnereof For example, its core may comprise a conjugated diene or a C1-C15 acrylate, said core having a gi ss transition temperature beiow about 0°C, and its grafted phase may comprise a carboxyhc acid ester of a saturated aliphatic alcohol, acrylic or methacry c acid, a vinyl nitrile compound, a vinyl aromatic compound, or a mixture thereof

Component (e) in the compositions of this invention is a molding polymer selected from (i) polyacetal, (n) polyacrylate, (in) polyamide, (iv) an epoxy resin, (v) ethylene/carbon monoxide copolymer, (vi) polyester, (vn) poly(phenylene ether), (vin) polystyrene, (ix) polyurethane, and (x) poly(vιnyl chloride), and mixtures thereof

Component (e)(ιι) is an acrylatϊ polymer, which is defined as a polymer prepared by homcoolymeπzation of an alkyl acrylate or an alkyl methacrylate or by copolymeπzation of a mixture of the two; and includes a mixture of any such homooolymers or copolymers

Component (e)(ι v) is an epoxy resin An eooxy resin as utilized in the compositions of this inventio n is typically prepared from an epinalonydπn such as epichlorohydrin, which is reacted in the presence of a base with a compound containing at least two active hydrogen atoms Representative materials used as a oase for such purpose include caustics such as the alkali metal and alkaline earth oxides and hydroxides An active hydrogen atom is one which can be abstracted by such a base to form an anion When the active-hydrogen-containing compound is reacted with epichlorohydrin, each anion formed tnereon by the deprotonating or catalytic action of the base opens the epoxide ring at the alpha carbon on an epichlorohydrin molecule to create a nydroxyl group on the beta carbon Dehydrohalogenation then occurs at each such location to regenerate an epoxide ring at the

beta and gamma carbons. If, in the active-hydrogen-containing compound, hydrogen was abstracted from oxygen, the product at this point may for practical purposes be represented as the diglycidyl ether of the active-hydrogen-containing compound. When other molecules of the deprotonated active-hydrogen-containing compound attack unreacted epichlorohydrin or attack the epoxide ring having been formed as each terminus of the diglycidyl ether of the active-hydrogen-containing compound, a polymer is formed which is a poly(hydroxy ether) containing epoxide rings at its termini. It is possible that one terminus of such polymer could be occupied by an unabstracted hydrogen atom rather than an eooxide ring. An epoxy resin suitable for use herein can generally be represented by the following structure:

10

wherein Q is the residue of the active-hydrogen-containing compound; R is hydrogen or C1 -15 alkyl or alkoxy; and p, which can range from zero to 100, is the degree of polymerization 2 (number of repeating units). P can, for example, be .ess than sixty, is advantageously less than forty, is preferably less than twenty, and is more preferably less than ten. P can, for example, be 0 to 20, 0 to 10, 1 to 10, or 1 to 5.

Use of an excess of epichlorohydrin suppresses the molecular weight of the epoxy -,r resin; a ratio of as little as 2/1 , epichlorohydrin to active-hydrogen-containing compound, is typically sufficient to yield a degree of polymerization of 0.35 or less. However, higher molecular weight epoxy resins can be prepared using the process described above by reacting the active-hydrogen-containing compound with only a slight excess of epichlorohydrin. In this direct (or taffy) process, the resins usually produced are those which have a degree of -,Q polymerization of 4 or less.

In the fusion process, the diglycidyl ether of the active-hydrogen-containing compound is reacted with an additional charge of the active-hydrogen-containing compound. Ca ^: .stic (or other proton acceptor such as triethanolamine, a substitiuted imidazole or Na2C03) ₃₅ is .ised in the reaction in only a catalytic amount as the oxyanion regenerates itself each time an epoxide ring is opened and secondary hydroxyl group is formed. Reaching high molecular weight is dependent on employment of agitation, and of higher temperature (up to 150°C) and pressure than used in the direct method, because of the viscosity of the reaction mass. Epoxy

resins with a degree of polymerization of 30 or more can be prepared by the fusion process Epoxy resins can also be prepared by direct epoxidat on of the C = C bond in an olefin by a peracid such as peroxybenzoic acid, C6H5C020H

Epoxy resins, prepared as described above, can be esteπfied with saturated or unsaturated fatty acids at either the terminal epoxide ring or at a pendant hydroxyl site along the polymer backbone Such an esteπ ication reaction is typically conducted in an inert atmospnere at 225-250°C, with the removal of water as a by-product

Oxyanions for use in the preparation of an epoxy resin can oe deri ved from the various bisphenols such as are described aoove with respect to the preparation of polycarbonate Use of oxyanions prepared from bisphenols yie'ds an epoxy resin of the type which is trequently referred to as a phenoxy resin However, oxyan.ons can also be prepared from bis p-hydroxy phenyl fluorene, from a bispnenol where the aromatic rings are hyd-ogenated, witn the use of trisnydroxy phenols or any of the branchi ng agents mentioned above with respect to the preparation of polvcarbonate, or from a C2-C 3 alkyl or alkylidene or a C4-C20 cycloalkyi or cycloalky dene diol or tπol

Bisphenol-A is an example of an especially preferred aromatic diol to be used in the preparation of the epoxy resin of this invention When a halogenated bisphenol

(containing, for example, bromine) is used to prepare the epoxy resin, an epoxy resin having good flame retardant properties, such as D E R ^φ 542 epoxy resin (available from The Dow Chemical Company), is obtained An exemplary halogenated epoxy resin can be represented by the following general formula

H H ₂

where each T can independently be hydrogen or an aliphatic hydrocarbyl group having from 1 0 to 3 carbon atoms and is preferably hydrogen; each is independently chiorine or b omine and is preferably bromine in eacn occurrence; each i is independently 1 or 2 anci is preferably 2 in each occurr ice; each L is independently a divalent hydrocarbyl group havir zj from 1 to 12 carbon atoms, preferably 3 carbon atoms; and q can be any value from 0 to 20 (not necessarily an integer) and is preferably from 0 to 6, more preferably from 0 to 1. The term hydrocarbyl as 5 employed herein means any aliphatic, cycloaiiphatic or aromatic groups. Compounds of this type are commercially available as DER 5-12, DER 51 1 and QUATREX 6410 brands of epoxy resin from The Dow Chemical Company and DP 452 brand epoxy resin from Ciba Geigy.

The epoxy resins useful in this invention can also be prepared from the reaction of Q a novolac and epihalohydrin. Representative novolacs are phenol/formaldehyde condensates in which multiple phenol functionalities are joined by methylene bridges. In novolac epoxies, multiepoxy functionality can increase with increasing molecular weight because the polymer is formed from the methylene bridges, leaving each phenolic hydroxyl group free to react with epichlorohydrin to form a pendant epo <ide ring. The novolac may additionally be prepared c from a substituted phenol . Novolac epoxies may be generally represented by a formula such as

where d is 0 to 10 and each R2 is independently hydrogen or C1 -15 alkyl or alkoxy An example of a novolac epoxy suitable for use herein is D E N ^® 431 epoxy resin (available from The Dow Chemical Company)

Eooxv resins such as are described above, and methods for preparing same, are discussed in greater detail in Perry, USP 3,948,855 and Doorakian, USP 4,302,574, each of which is incorporated nerein

Component (e)(v) is a polyester Suitable reactants for making the polyester used n this invention, in addition to hydroxycarboxyhc acids, are diols and dicarboxvhc acids either or ooth of whicn can be a ohatic or aromatic A polyester which is a poly(alkyiene alkanedicarboxylate), a polyiaikyiene arylenedicarboxylate), a poly(arylene alkanedicarooxylate), or a poly(ary ene arylenedicarboxylate) is therefore appropriate for use herein Alkyl portions of the polymer cnain can oe substituted with, for e<amole, halogens, C1 - C8 alkoxy groups or C1-C8 alkyl sioe chains and can contain divalent heteroatomic groups (such as -0-, -Si-, -S- or -S02-) in the paraffmic segment of the chain The chain can also contain unsaturaticn and C6-C10 non-aromatic rings Aromatic ri ngs can contain substituεnts sue ^* ι as halogens, C1 -C8 alkoxy or C1 -C8 alkyl groups, and can be joined to the polymer backbone in any ring position and directly to the alcohol or acid functionality or to intervening atoms Typical aliphatic diols used in es^er formation are the C2-C10 primary and secondary glycols, such as ethylene-, propylene-, and butylene glycol Alkanedicarboxylic acids frequently used are oxalic acid, adipic acid and sebacic acid Diols which contain rings can be, for example, a 1 ,4-cyclohexylenyl glycol or a 1 ,4-cyclohexane-dιmethylene glycol, resorcinol, hydroqumone, 4,4'-thιodιphenol, bιs-(4-hydroxypheny!)sulfone, a dihydroxynaphthalene, a xylylene diol, or can be one of the many bisphenols such as 2,2-bιs-(4-hydroxyphenyl)propane Aromatic diacids include, ^* or example, terephthahc acid, isophthahc acid, naphthalenedicarboxyhc acid, diohenyletherdicarooxyhc acid, diphenyldicarboxylic acid, diOhenylsulfoneoicarboxyhc acid, diphenoxyethaneoicarboxy c acid

In addition to polyesters formed from one oiol and one diacid only, the term "polyester" as used herein includes random, patterned or olpck copolyesters, for example those formed from two or more different diols and/or two or more different diacids, and/or from other divalent heteroatomic groups Mixtures of such copolyesters, mixtures of polyesters derived from one 0 ol and diacid only, and mixtures of members from both of such groups, are also all suitable for use in this invention, and are all included in the term "polyester" For example, use of cyclohexanedimetnylol together with ethylene glycol in esterification with terephthahc acα forms a clear, amorphous c oolyester ("PETG") of particular interest Also contemplated are PCTG, liquid crystalline polyesters derived from mixtures of 4- hydroxybenzoic acid and 2-hydroxy-6-naphthoιc acid, or mixtures of terephthahc acid, 4-

hydroxvbenzoic acid and etnylene glycol , or mixtures of terephthahc acid, 4-hyαroxvbenzoιc acid and 4,4'-dιhydroxybιphenyl

Ar omatic polyesters, those prepared from an aromatic diacid, such as the poly(alkylene arylenedicarboxylates) polyethylene terephthalate and polybutylene terephthalate, or mixtures thereof, are particularly useful in this invention A polyester suitable for use herein may have an intrinsic viscosity of 0 4 to 1.04, although values outside this range are permitted as well

Methods ano materials use ^** fpr the production of polyesters, as described above, are discussed in greater detail in Wnmfield, USP 2,465,319, Pengilly, USP 3,047,539, o Schwarz, USP 3,374,402, Russell, USP 3,756,936 and East, USP 4,393, 191 , each of which is incorporated herein by reference

Component (e)(vι) is an ethylene/carbon monoxide copolymer, or an ethvlene/carbon monoxide copolymer to whicn one or more etnylenically unsaturated 5 monomers have been graft polymerized, suitable varities of which are described in Laughner, USP 4,929,673, which is incorporated herein by reference

Component (e)(vιι) is a poly(phenylene ether) [also known as a poiy(pnenylene oxide)], which is often blended with component (e)(vιιι), polystyrene, a styrenic copolymer [as 0 described above with relation to component (c)], and/or with a polystyrene or styrenic copolymer which has been rubber modified by being blended or grafted with a polymer formed from diene and/or olefin monomers Such a blend is typically made up of 20 to 99 parts, preferably 30 to 90 parts, poly(phenylene ether) by weight, with the balance being made up of the polyst rene or styrenic copolymer, as mentioned The rubber-modified polystyrene 5 or styrenic copolymer is typically 70 to 98 weight percent styrene or styrenic cooolymer and 2 to 30 weigh" percent blended or grafted pc , ner prepared from diene and/or olefin monomer, and is often referred to as high impact polystyrene ("HIPS")

Component (e)(ix) in the compositions of this invention is a polyurethane, 0 suitable varities of which are described in the commonly assigned, concurrently filed U S application bearing attorney's docket number C-40,431 , which is incorporated herein

A variety of a_ Jitives may be adv ntageously employed to promote flame retardance or ignition resistance in the compositions of this invention Representative 5 examples thereof include the oxides and ha des of the metals of Groups IVA and VA of the periodic table such as the oxides and ha des of antimony, bismuth, arsenic, tin and lead such as antimony oxide, antimony chloride, antimony oxychloπde, stannic oxide, stannic chloride and arsenous oxide, the organic and inorganic compounds of phosphorous, nitrogen, boron and

sulfur such as aromatic pnosphates and phosphonates (including halogenated derivatives thereof), alkyl acid phospnates -ibutoxyetnyl phosphate, 1 ,3-dιchloro-2-oropanol phosphate, 3,9-trιbrρmoneopentoxy-2,4,8, 10-tetraoxa-3,9-dιphosohaspιro(5 5)undecane-3,9-dιoxιde, phosphme oxides, ammonium phosphate, zinc borate, thiourea, urea, ammonium sulfamate, ammonium polyphosphoric acid and stannic sulfide, the oxides, halides and hydrates of other metais such as titanium, vanadium, chromium and magnesium such as titanium dioxide, chronic oromide, z'rconium oxide, ammonium molybdate and stannous oxide hydrate, antimony compounds such as antimony phosphate, sodium antimonate, KSb(OH)5, NH4SbF6 and SbS3, antimonic esters of inorganic acids, cyclic alkyl antimonite esters and aryl antimonic acid compounds such as potass.um antimony tartrate, the antimony salt of caoroic acid, Sb(OCH2CH3), Sb[OCH(CH3)C-2Ch3]3, antimony polyethylene glycorate, pentaerythπtol antimonite and tπohenyl antimony, boric acid, aiumina tphydrate, ammonium fluoroborate, molybdenum oxide, nalogenateo nydrocaroons sucn as hexabromocyclodecane, decaoromomdiphenyl oxide, 1 ,2-bιs(2,4,6-trιbromopnenoxy) ethane, nalogena ed carbonate o gomers such as those prepared f ^r om Tetrabromobispnenol-A, haiogenateo eooxy resins such as brominated glycidyl ethers, tetrabromo pnthahc annydπde, fluoπnated olefin polymers or copolymers such as poiy(tetrafluoroethylene), ocτabromodiphenyl oxide, ammonium bromide, isopropyl dι(4-amιno benzovl) isostearoyl titanate, and metal salts of aromatic sulfur compounds such as sulfates, bisulfates, sulfonates, sulfonamides and sulfimides, other alkali metal and alkaline earth metal salts of sulfur, phosphorus and nitrogen compounds, and others as set forth in Laughner, USP 4,786,686, which is incorporated herein, and the like, and mixtures th ^* .reof A preferred flame retardant additive is antimony tnoxide (Sb203) When a flame retardant is used in the compositions of this invention, it is typically used in an amount of up to 15 percent, advantageously from 0 01 "o 15 percent, preferably from 0 1 to 10 percent and more preferably from 0 5 to 5 percent, by weight of the total composition

A variety of additives may be advantageously used in the compositions o this invention for other purposes such as the following antimicrobial agents such as organometal cs, isothtazolones, organosulfurs and me-captans, antioxidants such as phenolics, secondary amines, phophites and thioestsrs, ant, sta ic agents such as quaternary ammonium compounds, amines, and ethoxylated, propoxylated or glycerol compounds, fillers and reinforcing agents such as talc, clay, mica, silica, quartz, kaolin, aluminum nitride, Tι02, calcium sulfate, B203, alumina, giass flakes, beads, whiskers or filaments, nickel powder and metal or graphite fibers, hydrolytic stabilizers, lubricants such as fatty acids, fatty alcohols, esters, fatty amides, metallic stearates, paraffinic and microcrystal ne waxes, sihcones and orthoohosphoπc acid esters, mold release agents such as fine-particle or powdereα solids, soaps, waxes, sihcones, polyglycols and complex esters such as trimethylolpropane tristearate or

pentaeryτnπtol tetrastearate, pigments, dyes and colorants, plasticizers such as esters of dibas.c acids (or their anhydrides) with monohydπc alconols such as o-phthalates, adipates and benzoates, heat stabilizers such as organotin mercaptides an octyl ester of thioglyco c acid and a barium or cadmium carboxyalte, ultraviolet light stabilizers such as a hindered amine, an o-hvdroxy-phenylbenzotπazole, a 2-hydroxy,4-alkoxybenzophenone, a sa cylate, a cyanoacrylate, a nickel chelate and a benzyhdene malonate and oxalani de A preferred hindered phenolic antioxidant is Irganox'" 1076 antioxidant, avaiiaole rom Ciba-Geigy Corp Such additives, if used, typically do not exceed 45 percent by weight of the total composition, ano are advantageously from 0 001 to 15 percent, preferaoly from 0 01 to 10 percent and more o preferably from 0 1 to , 0 percent, oy weight of the total composition

An acd acceptor or scavenger may be advantageously used in the compositions of this invention to enhance tnermai stability in « ^* ιew of the tendency of CPE to liberate HCI when heated Suitable acid acceptors are barium phospnate, epoxidized soybean oil and calcium 5 stearate When an acid acceptor is used in the compositions of this invention, it is typically used in an amount of uo to 10 percent, advantageously from 0 001 to 10 percent, preferably from 0 01 to 5 percent and more preferably from 0 01 to 1 percent, by weight of the total composition

0 To illustrate the practice f this invention, examples of several preferred embodiments are set forth below It is not intended, however, that these examples should in any manner restrict the scope of this invention

Examples 1-2 The compositions of Examples 1 and 2 were prepared by mixing 5 polycarbonate with epoxidized soybean oil in a Lightnin blender for 30 seconds To this was added C*Ε, barium phosphate and Irganox ^T " 1076 antioxidant The resulting mixture was blended for another 30 seconds without the internal blade and again for 30 seconds with the blade This final dry-blenαed formulation was passed througn a 30 mm emer-Pfleiderer twin-screw extruder, with all barrel zones at 190°C, and pelletized The extruded pellets were 0 dπeo in an air draft oven for at least 3 hours at 90°C The dried pel'ets were nen molded into bars (1/8" x 1/2" x 5") and plaques (1/8" x 2i" x ό÷") on a 55 ton Negπ Bossi molding machine, with a 220°C barrel temperature on all zones, for testing

The formulations of Examples 1 and 2 both contain 52 6 weignt percent 80 melt 5 flow rate Bisphenol-A polycarbonate, 0 5 weight percent epoxidized soybean oil, 1 8 weight percent barium phosphate and 0 1 weight percent Irganox ^™ 1076 antioxidant Example 1 contains 45 weight percent chlorinated polyethylene containing 42 weight percent chlorine Ex mple 2 contains 45 weight percent graf' copolymer prepared from 85 weight percent

chlorinated polyethylene (containing 42 weight percent chlorine) to which methyl methacrylate was graft polymerized such that the methy methacrylate constitutes 15 weight percent of the graft copolymer

5 The following tests were performed on Examples 1 and 2 Impact resistance was measured by the Izod test according to ASTM Designation D 256-84 (Method A) at 73°F The notch was 10 mιls (0 254 mm) in radius Izod results were reported in ft-lb/in

"H D T U L " is heat defection temperature under load as measured in 1 o accordance with ASTM Designation D 648-82 at 264 psi

Flexural modulus was measured in accordance witn ASTM Designation D 790-84a Results were reported in kpsi

15 Tensile strength at break was both measured in accordance with ASTM

Designation D 638-84 Results were reported in kosi

Molecular weight change was the decrease in the weight average molecular weight (as determined by gel permeation chromatography) of the polycarbonate caused by 20 the molding operation, and was determined by subtracting the molecular weight of the polycarbonate in the molded bars from nat in the pellets before molding

Specular gloss was measured according to ASTM Designation D 523-85 using a Dr Bruno Lange Reflectometer RB The beam axis angle was 20°

25

Paintabihty was determined by the distinctness of image ("D O I ") test (ASTM

E430-78, which measures the snarpness of an image reflected from a painted c coated glossly surface by goniophotometry; the Crosshatch adnesion test (A JTM D3359-87B), which measures the adhesion to surface of paint which had been scored, and the dime rub test ( eneral Motors

30 9506-P), an abrasion test which measures the durability of a coat of pa nt

The testing reults for Examples 1 and 2 were shown in Table II

35

Table II

Example 1 Example 2

Izod 12 15

H.D.T.U.L., °F 214 217

Flexural modulus 148 152

Tensile strength 5,723 6,307

Molecular weight 2,000 1,200 change n i 1 20° Gloss 90 91

D.O.I. 95 95

Crosshatc adhesion #5 #5

Dime rub Pass Pass

15

T ^** ese results show that a polycarbonate/CPE blend was a useful molding composition. Stabilizers such as an acid scavenger, such as barium phosphate, and a phenolic antioxidant were preferred so that CPE can be melt processed at a temperature at which it ^***' - ^' might otherwise degrade. This was indicated by the good mechanical properties, the paintability and the quality of paint adhesion displayed by the bars and plaques molded from the compositions of Examples 1 and 2. Particularly desirable properties were displayed by Example 2, in which methyl methacrylate was graft polymerized to CPE.

- ^*•** ' Examples 3-5. The compositions of Examples 3-5 were prepared by mixing polycarbonate, CPE and SAN or ABS in a Lightnin blenoer for 30 seconds with agitation. Epoxidized soybean oil vas added and the blender was run for an additional 30 seconds with agitation. Barium phosphate, Irganox™ 1076 antioxidant, Sb203 and, in some formulations, PTFE were then added, and the resulting mixture was blended for another 30 seconds without

3 ^< - ^* agitation and again for 30 seconds with agitation. This final dry-blended formulation was passed through a 30 mm Werner-Pfleiderer twin-screw extruder, with all barrel zones at 190°C, and peiletized. The extruded pellets were dried in an air draft oven for at least 3 hours at 90°C. The dried pellets were then molded into bars for testing (0.318 cm x 1.27 cm x 1.27 cm) and (0.157 cm x 1.27 cm x 1.27 cm) on a 55 ton Negri Bossi molding machine with a 225°C barrel

^* " temperature on all zones.

The formulations in weight percent for Examples 3-5 were shown in Table III. In Table III,

"PC" was 80 melt flow rate Bisphenol-A polycarbonate,

"CPE I" was chlorinated polyethylene prepared with water washing and no deblocking agent,

"CPE II" was chlorinated polyethylene containing 40.8 weight percent chlorine,

"CPE III" was chlorinated polyethylene to which methyl methacrylate was graft polymerized,

"ABS I" was acrylonitrile/butadiene/styrene copolymer containing 1 1 weight percent butadiene and 1 5 weight percent acrylonitrile,

"ABS II" was acrylonitrile/butadiene/styrene copolymer containing 16 weight percent butadiene and 23 weight percent acrylonitrile,

"PTFE" was poly(tetrafluoroethylene),

"E.S.O." was epoxidized soybean oil, and "1-1076" was rganox '" 1076 antioxidant.

In addition to testing for Izod and fiexural modulus, as described above in relation to Examples 1 and 2, the U.L. (Underwriters Laboratory) 94 burn test was performed on Examples 3-5. T ^{' *} e Izod test was conducted at room temperature (23-25°C). Izod was reported in ft-lbs, and fiexural modulus was reported in kpsi. Results were reported in Table III.

Table 3

These results show, as do those for Examples 1 -2, that a polycarbonate/CPE blend was a useful molding composition which had mechanical properties in a desirable range. A composition such as that in Example 4 was particularly desirable because, when an ABS with a higher acryionitrile content was used, a higher fiexural modulus was obtained. Good mechanical properties were alsp obtained even in the absence of ABS where the CPE was grafted with methyl methacrylate, such as in Example 5. The use of Sb203 together with PTFE imparts a V-0 rating to the composition, as shown by Examples 4-5.

Example 5. Example 6 was prepared by premi ,ing 6 weight percent of a chlorinated polyethylene which contains 36 weight percent chlorine, 7 weight percent of a brominted epoxy resin (QUATREX ^® 6410 epoxy resin from The Dow Chemical Company), 3 weight percent Sb203, and 0.3 weight percent barium phosphate. The premixed material was added to 45 weight percent 14 MFR Bisphenol-A polycarbonate and 38.7 weight percent ABS. All these components were dry blended in a Lightnin blender for 30 seconds without the internal agitator and for 30 seconds with the internal agitator This final dry-blended

formulation was passed through a 30 mm Werner-Pfleiderer twin-screw extruder, with all barrel zones at 250°C, and peiletized. The extruded pellets were dried in an air draft oven for at least 3 hours at 90°C. The ^* ιed pellets were then molded on a 70-ton Arburg molding machine, using a 230°C barrel temperature, into bars (1/8" x 1/2" x 5") and (1/16" x 1/2" x 5") for testing. When subjected to the U.L.-94 burn test, the composition of Example 6 rates both V-0 at 1/16" and 5V at 1/8", which demonstrates that a polycarbonate/CPE composition having desirable flame properties can be prepared without the use of PTFE.