WO2005040279A1 - Composition comprising functionalized poly(arylene ether) and ethylene-alkyl (meth)acrylate copolymer, method for the preparation thereof, and articles prepared therefrom - Google Patents
Composition comprising functionalized poly(arylene ether) and ethylene-alkyl (meth)acrylate copolymer, method for the preparation thereof, and articles prepared therefrom Download PDFInfo
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- WO2005040279A1 WO2005040279A1 PCT/US2004/028275 US2004028275W WO2005040279A1 WO 2005040279 A1 WO2005040279 A1 WO 2005040279A1 US 2004028275 W US2004028275 W US 2004028275W WO 2005040279 A1 WO2005040279 A1 WO 2005040279A1
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- C08G65/00—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule
- C08G65/34—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule from hydroxy compounds or their metallic derivatives
- C08G65/48—Polymers modified by chemical after-treatment
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- C08F283/00—Macromolecular compounds obtained by polymerising monomers on to polymers provided for in subclass C08G
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- C08F290/00—Macromolecular compounds obtained by polymerising monomers on to polymers modified by introduction of aliphatic unsaturated end or side groups
- C08F290/02—Macromolecular compounds obtained by polymerising monomers on to polymers modified by introduction of aliphatic unsaturated end or side groups on to polymers modified by introduction of unsaturated end groups
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- C08F290/00—Macromolecular compounds obtained by polymerising monomers on to polymers modified by introduction of aliphatic unsaturated end or side groups
- C08F290/02—Macromolecular compounds obtained by polymerising monomers on to polymers modified by introduction of aliphatic unsaturated end or side groups on to polymers modified by introduction of unsaturated end groups
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- C08G65/00—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule
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- C08L23/04—Homopolymers or copolymers of ethene
- C08L23/08—Copolymers of ethene
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- C08L33/00—Compositions of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides or nitriles thereof; Compositions of derivatives of such polymers
- C08L33/04—Homopolymers or copolymers of esters
- C08L33/06—Homopolymers or copolymers of esters of esters containing only carbon, hydrogen and oxygen, which oxygen atoms are present only as part of the carboxyl radical
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- C08L53/00—Compositions of block copolymers containing at least one sequence of a polymer obtained by reactions only involving carbon-to-carbon unsaturated bonds; Compositions of derivatives of such polymers
- C08L53/02—Compositions of block copolymers containing at least one sequence of a polymer obtained by reactions only involving carbon-to-carbon unsaturated bonds; Compositions of derivatives of such polymers of vinyl-aromatic monomers and conjugated dienes
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- C08L71/00—Compositions of polyethers obtained by reactions forming an ether link in the main chain; Compositions of derivatives of such polymers
- C08L71/08—Polyethers derived from hydroxy compounds or from their metallic derivatives
- C08L71/10—Polyethers derived from hydroxy compounds or from their metallic derivatives from phenols
- C08L71/12—Polyphenylene oxides
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- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K5/00—Use of organic ingredients
- C08K5/49—Phosphorus-containing compounds
- C08K5/51—Phosphorus bound to oxygen
- C08K5/53—Phosphorus bound to oxygen bound to oxygen and to carbon only
- C08K5/5313—Phosphinic compounds, e.g. R2=P(:O)OR'
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- C08L51/08—Compositions of graft polymers in which the grafted component is obtained by reactions only involving carbon-to-carbon unsaturated bonds; Compositions of derivatives of such polymers grafted on to macromolecular compounds obtained otherwise than by reactions only involving unsaturated carbon-to-carbon bonds
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- C08L71/00—Compositions of polyethers obtained by reactions forming an ether link in the main chain; Compositions of derivatives of such polymers
- C08L71/08—Polyethers derived from hydroxy compounds or from their metallic derivatives
- C08L71/10—Polyethers derived from hydroxy compounds or from their metallic derivatives from phenols
- C08L71/12—Polyphenylene oxides
Definitions
- Thermoplastic compositions comprising poly(arylene ether) resins and ethylene-alkyl acrylate copolymers are known in the art.
- U.S. Patent No. 4,442,251 to Haaf et al. generally describes compositions of polyphenylene ether resin, optionally containing an impact modifier, and small amounts of a copolymer of ethylene and methyl acrylate.
- U.S. Patent No. 5,008,333 to Yates et al. generally describes thermoplastic blends prepared from a polyphenylene ether, a linear polyester such as poly(alkylene dicarboxylate), a polymer containing a substantial proportion or aromatic polycarbonate units, and property improving amounts of an alkylene acrylate copolymer.
- U.S. Patent No. 5,162,435 to Shibuya et al. generally describes a resin composition comprising 20-77 weight percent of a polyolefm, 20-77 weight percent of a polyphenylene ether resin, 2-50 weight percent of a polymer including an alkenyl aromatic polymerization chain and an aliphatic hydrocarbon chain, and 1-25 weight of an ester-group-containing ethylene copolymer.
- a resin composition comprising 20-77 weight percent of a polyolefm, 20-77 weight percent of a polyphenylene ether resin, 2-50 weight percent of a polymer including an alkenyl aromatic polymerization chain and an aliphatic hydrocarbon chain, and 1-25 weight of an ester-group-containing ethylene copolymer.
- One embodiment of the invention is a composition, comprising: a functionalized poly(arylene ether); and an olefin-alkyl acrylate copolymer.
- Other embodiments, including a method of preparing the composition and articles comprising the composition, are described below.
- a composition comprising: a functionalized poly(arylene ether); and an olefm-alkyl acrylate copolymer.
- the functionalized poly(arylene ether may be a capped poly(arylene ether), a ring-functionalized poly(arylene ether), or a maleic anhydride-functionalized poly(arylene ether).
- the functionalized poly(arylene ether) may be a capped poly(arylene ether).
- a capped poly(arylene ether) is defined herein as a poly(arylene ether) in which at least 50%, preferably at least 75%, more preferably at least 90%, yet more preferably at least 95%o, even more preferably at least 99%, of the free hydroxyl groups present in the corresponding uncapped poly(arylene ether) have been functionalized by reaction with a capping agent.
- the capped poly(arylene ether) may be represented by the structure
- Q is the residuum of a monohydric, dihydric, or polyhydric phenol, preferably the residuum of a monohydric or dihydric phenol, more preferably the residuum of a monohydric phenol; y is 1 to 100; J comprises repeating structural units having the formula
- R 1 and R 3 are each independently hydrogen, halogen, primary or secondary C ⁇ -C ⁇ 2 alkyl, C -C ⁇ 2 alkenyl, C 2 -C ⁇ 2 alkynyl, C ⁇ -C] 2 aminoalkyl, C ⁇ -C ⁇ 2 hydroxyalkyl, phenyl, C]-C ⁇ 2 haloalkyl, C 1 -C 12 hydrocarbonoxy, C 2 -C ⁇ 2 halohydrocarbonoxy wherein at least two carbon atoms separate the halogen and oxygen atoms, or the like; R 2 and R 4 are each independently halogen, primary or secondary C ⁇ -C .
- K is a capping group produced by reaction of a phenolic hydroxyl group on the poly(arylene ether) with a capping reagent. The resulting capping group may be
- R 5 is -C 12 alkyl, or the like
- R 6 -R 8 are each independently hydrogen, C]-C ⁇ hydrocarbyl, alkyl, C 2 -C ⁇ 8 hydrocarbyloxycarbonyl, nitrile, formyl, carboxylate, imidate, thiocarboxylate, or the like
- R -R " are each independently hydrogen, halogen, C 1 -C 12 alkyl, hydroxy, amino, or the like
- Y is a divalent group such as
- hydrocarbyl refers to a residue that contains only carbon and hydrogen.
- the residue may be aliphatic or aromatic, straight-chain, cyclic, branched, saturated or unsaturated.
- the hydrocarbyl residue when so stated however, may contain heteroatoms over and above the carbon and hydrogen members of the substituent residue.
- the hydrocarbyl residue when specifically noted as containing such heteroatoms, may also contain carbonyl groups, amino groups, hydroxyl groups, or the like, or it may contain heteroatoms within the backbone of the hydrocarbyl residue.
- haloalkyl includes alkyl groups substituted with one or more halogen atoms, including partially and fully halogenated alkyl groups.
- Q is the residuum of a phenol, including polyfunctional phenols, and includes radicals of the structure
- R and R" are each independently hydrogen, halogen, primary or secondary C 1 -C 1 alkyl, C 2 -C 12 alkenyl, C -C ⁇ 2 alkynyl, C ⁇ -C] 2 aminoalkyl, C1- 2 hydroxyalkyl, phenyl, C1-C 12 haloalkyl, C]-C] 2 hydrocarbonoxy, C 2 -C
- R and R are each independently halogen, primary or secondary C 1 - 2 alkyl, C 2 - 2 alkenyl, C 2 -C] 2 alkynyl, C ⁇ -C] 2 aminoalkyl, -C 12 hydroxyalkyl, phenyl, C ⁇ -C ⁇ 2 haloalkyl, C1-C 12 hydrocarbonoxy, C2-C12 halohydrocarbonoxy wherein at least two carbon atoms separate the halogen and oxygen atoms, or the like;
- X may be hydrogen, C 1 -C 12 alkyl, C 6 -C ⁇ 8 aryl, C -C ⁇ 8 alkyl-substituted aryl, C 7 -C ⁇ 8 aryl-substituted alkyl, or any of the foregoing hydrocarbon groups containing at least one substituent such as carboxylic acid, aldehyde, alcohol, amino radicals, or the like;
- X also may be sulfur, sulfonyl, sulfur
- the capped poly(arylene ether) is produced by capping a poly(arylene ether) consisting essentially of the polymerization product of at least one monohydric phenol having the structure
- R 1 and R 3 are each independently hydrogen, halogen, primary or secondary Ci-Ci 2 alkyl, C 2 -C ⁇ alkenyl, C 2 -C ⁇ alkynyl, C1- 2 aminoalkyl, C1-C12 hydroxyalkyl, phenyl, C 1 -C 12 haloalkyl, C1-C12 hydrocarbonoxy, C 2 -C] 2 halohydrocarbonoxy wherein at least two carbon atoms separate the halogen and oxygen atoms, or the like;
- R 2 and R 4 are each independently halogen, primary or secondary C]-C ⁇ 2 alkyl, C -C ] alkenyl, C 2 -C] 2 alkynyl, C ⁇ -C ]2 aminoalkyl, C ⁇ -C ⁇ 2 hydroxyalkyl, phenyl, C ⁇ -C ]2 haloalkyl, C]-C] 2 hydrocarbonoxy, C 2 -C12 halohydrocarbonoxy wherein at
- Suitable monohydric phenols include those described in U.S. Patent No. 3,306,875 to Hay, and highly preferred monohydric phenols include 2,6-dimethylphenol and 2,3,6-trimethylphenol.
- the poly(arylene ether) may be a copolymer of at least two monohydric phenols, such as 2,6-dimethylphenol and 2,3,6-trimethylphenol.
- the capped poly(arylene ether) comprises at least one capping group having the structure
- R 6 -R 8 are each independently hydrogen, C ⁇ C ⁇ 8 hydrocarbyl, alkyl, C 2 -C ⁇ 8 hydrocarbyloxycarbonyl, nitrile, for yl, carboxylate, imidate, thiocarboxylate, or the A 7 R like.
- the capped poly(arylene ether) comprises at least one capping group having the structure
- R is C 1 -C 12 alkyl, preferably C . -C 0 alkyl, more preferably methyl, ethyl, or isopropyl.
- the capped poly(arylene ether) comprises at least one capping group having the structure
- R 9 -R 13 are each independently hydrogen, halogen, C1-C 12 alkyl, hydroxy, amino, or the like.
- the capped poly(arylene ether) comprises at least one capping group having the structure
- A is a saturated or unsaturated C 2 -C12 divalent hydrocarbon group such as, for example, ethylene, 1 ,2-propylene, 1,3-propylene, 2-methyl-l,3-propylene, 2,2-dimethyl-l,3-propylene, 1,2-butylene, 1 ,3-butylene, 1 ,4-butylene,
- capped poly(arylene ether) resins may conveniently be prepared, for example, by reaction of an uncapped poly(arylene ether) with a cyclic anhydride capping agent.
- cyclic anhydride capping agents include, for example, maleic anhydride, succinic anhydride, glutaric anhydride, adipic anhydride, phthalic anhydride, and the like.
- the capped poly(arylene ether) may be formed by the reaction of an uncapped poly(arylene ether) with a capping agent.
- Capping agents include compounds known in the literature to react with phenolic groups. Such compounds include both monomers and polymers containing, for example, anhydride, acid chloride, epoxy, carbonate, ester, isocyanate, cyanate ester, or alkyl halide radicals. Capping agents are not limited to organic compounds as, for example, phosphorus and sulfur based capping agents also are included.
- capping agents include, for example, acetic anhydride, succinic anhydride, maleic anhydride, salicylic anhydride, polyesters comprising salicylate units, homopolyesters of salicylic acid, acrylic anhydride, methacrylic anhydride, glycidyl acrylate, glycidyl methacrylate, acetyl chloride, benzoyl chloride, diphenyl carbonates such as di(4-nitrophenyl)carbonate, acryloyl esters, methacryloyl esters, acetyl esters, phenylisocyanate, 3-isopropenyl-alpha,alpha-dimethylphenylisocyanate, cyanatobenzene, 2,2-bis(4-cyanatophenyl)propane), 3-(alpha-chloromethyl)styrene, 4-(alpha-chloromethyl)styrene, allyl bromide, and the like, carbonate and
- the capped poly(arylene ether) may be prepared by reaction of an uncapped poly(arylene ether) with an anhydride in an alkenyl aromatic monomer as solvent.
- This approach has the advantage of generating the capped poly(arylene ether) in a form that can be immediately blended with other components to form a curable composition; using this method, no isolation of the capped poly(arylene ether) or removal of unwanted solvents or reagents is required.
- a capping catalyst may be employed in the reaction of an uncapped poly(arylene ether) with an anhydride.
- Such compounds include those known to the art that are capable of catalyzing condensation of phenols with the capping agents described above.
- Useful materials are basic compounds including, for example, basic compound hydroxide salts such as sodium hydroxide, potassium hydroxide, tetraalkylammonium hydroxides, and the like; tertiary alkylamines such as tributyl amine, triethylamine, dimethylbenzylamine, dimethylbutylamine and the like; tertiary mixed alkyl-arylamines and substituted derivatives thereof such as N,N-dimethylaniline; heterocyclic amines such as imidazoles, pyridines, and substituted derivatives thereof such as 2-methylimidazole, 2-vinylimidazole, 4-(dimethylamino)pyridine, 4-(l-pyrrolino)pyridine, 4-(l-
- organometallic salts such as, for example, tin and zinc salts known to catalyze the condensation of, for example, isocyanates or cyanate esters with phenols.
- organometallic salts useful in this regard are known to the art in numerous publications and patents well known to those skilled in this art.
- the functionalized poly(arylene ether) may be a ring-functionalized poly(arylene ether).
- the ring-functionalized poly(arylene ether) is a poly(arylene ether) comprising repeating structural units of the formula
- each L i -L ⁇ 4 is independently hydrogen, an alkenyl group, or an alkynyl group; wherein the alkenyl group is represented by
- L 5 - TL 7 are independently hydrogen or methyl, and a is an integer from 0 to 4; wherein the alkynyl group is represented by
- L is hydrogen, methyl, or ethyl
- b is an integer from 0 to 4
- about 0.02 mole percent to about 25 mole percent of the total L'-L 4 substituents in the ring-functionalized poly(arylene ether) are alkenyl and/or alkynyl groups.
- the ring-functionalized poly(arylene ether) may be prepared according to known methods.
- an unfunctionalized poly(arylene ether) such as poly(2,6- dimethyl-l,4-phenylene ether) may be metalized with a reagent such as n-butyl lithium and subsequently reacted with an alkenyl halide such as allyl bromide and/or an alkynyl halide such as propargyl bromide.
- a reagent such as n-butyl lithium
- an alkenyl halide such as allyl bromide and/or an alkynyl halide such as propargyl bromide.
- the ring-functionalized poly(arylene ether) is the product of the melt reaction of a poly(arylene ether) and an ⁇ , ⁇ -unsaturated carbonyl compound or a ⁇ -hydroxy carbonyl compound.
- ⁇ , ⁇ -unsaturated carbonyl compounds include, for example, maleic anhydride, citriconic anhydride, and the like.
- ⁇ -hydroxy carbonyl compounds include, for example, citric acid, and the like.
- Such functionalization is typically carried out by melt mixing the poly(arylene ether) with the desired carbonyl compound at a temperature of about 190 to about 290°C.
- poly(arylene ether)s described herein as “uncapped” or “unfunctionalized” comprise repeating structural units having the formula
- each Z is independently hydrogen, halogen, primary or secondary C1-C 12 alkyl, C 1 -C 12 aminoalkyl, C]-C] 2 hydroxyalkyl, phenyl, C ⁇ -C ⁇ 2 haloalkyl, C1-C 12 hydrocarbonoxy, C]-C] 2 halohydrocarbonoxy wherein at least two * 9 carbon atoms separate the halogen and oxygen atoms, or the like; and each Z is independently halogen, primary or secondary C1-C 1 2 alkyl, C 1 -C 12 aminoalkyl, C1-C 12 hydroxyalkyl, phenyl, C 1 -C 12 haloalkyl, C 1 -C1 .2 hydrocarbonoxy, C ⁇ -C ⁇ 2 halohydrocarbonoxy wherein at least two carbon atoms separate the halogen and 1 • 9 oxygen atoms, or the like.
- each Z is C ⁇ _ 4 alkyl, and each Z is hydrogen or methyl.
- the composition may comprise a functionalized poly(arylene ether) having a number average molecular weight of about 3,000 to about 25,000 atomic mass units (AMU). Within this range, it may be preferable to use a functionalized poly(arylene ether) having a number average molecular weight of at least about 10,000 AMU, more preferably at least about 15,000 AMU.
- the composition may comprise a functionalized poly(arylene ether) having an intrinsic viscosity of about 0.1 to about 0.6 deciliters per gram (dL/g) as measured in chloroform at 25°C.
- the functionalized poly(arylene ether) intrinsic viscosity may preferably be at least about 0.2 dL/g, more preferably at least 0.25 dL/g.
- the functionalized poly(arylene ether) intrinsic viscosity may preferably be up to about 0.5 dL/g, still more preferably up to about 0.4 dL/g.
- the intrinsic viscosity of a functionalized poly(arylene ether) will vary insignificantly from the intrinsic viscosity of the corresponding unfunctionalized poly(arylene ether). Specifically, the intrinsic viscosity of a functionalized poly(arylene ether) will generally be within 10% of that of the unfunctionalized poly(arylene ether). It is expressly contemplated to employ blends of at least two functionalized poly(arylene ether)s having different molecular weights and intrinsic viscosities.
- the composition may comprise a blend of at least two functionalized poly(arylene ethers).
- Such blends may be prepared from individually prepared and isolated functionalized poly(arylene ethers).
- such blends may be prepared by reacting a single poly(arylene ether) with at least two functionalizing agents.
- a poly(arylene ether) may be reacted with two capping agents, or a poly(arylene ether) may be metalized and reacted with two unsaturated alkylating agents.
- a mixture of at least two poly(arylene ether) resins having different monomer compositions and/or molecular weights may be reacted with a single functionalizing agent.
- the composition may comprise the functionalized poly(arylene ether) in an amount of about 25 to about 95 parts by weight per 100 parts by weight total of the functionalized poly(arylene ether) and the olefm-alkyl (meth)acrylate copolymer.
- a functionalized poly(arylene ether) amount of at least about 30 parts by weight, more preferably at least about 35 parts by weight.
- the composition comprises an olefm-alkyl (meth)acrylate copolymer.
- the olefm- alkyl (meth)acrylate copolymer is preferably the polymerization product of (a) ethylene or a C -C 8 ⁇ -olefm, and (b) an alkyl (meth)acrylate, wherein the alkyl is C ⁇ - C 8 alkyl and (meth)acrylate signifies either acrylate or methacrylate.
- the copolymer is preferably formed by polymerizing the two monomer types in a ratio of about 60 to about 95 weight percent of the olefm and about 5 to about 40 weight percent of the alkyl (meth)acrylate per 100 parts by weight total monomer.
- the monomer ratio range it may be preferably to use at least about 15 weight percent alkyl (meth)acrylate, more preferably at least about 20 weight percent alkyl (meth)acrylate, still more preferably at least about 25 weight percent alkyl (meth)acrylate.
- the olefm used to prepare the olefm-alkyl (meth)acrylate copolymer is preferably ethylene, propylene, 1-butene, 1-pentene, 1-hexene, 1-heptene, 1-octene, 4-methyl-l- pentene, or the like.
- the alkyl (meth)acrylate monomer used to prepare the olefm- alkyl (meth)acrylate copolymer the alkyl group is preferably methyl, ethyl, propyl, n- butyl, n-pentyl, n-hexyl, n-heptyl, n-octyl, or the like. Highly preferred alkyl groups include methyl.
- the olefm-alkyl (meth)acrylate copolymer is preferably ethylene- methyl acrylate copolymer, ethyl ene-ethyl acrylate copolymer, ethyl ene-methyl methacrylate copolymer, ethylene-ethyl methacrylate copolymer, or the like.
- Highly preferred olefm-alkyl (meth)acrylate copolymers include ethyl ene-methyl acrylate copolymer.
- the olefm-alkyl (meth)acrylate copolymer is the polymerization product of monomers consisting of the olefm and alkyl (meth)acrylate described above.
- the monomers may further comprise a polar comonomer such as maleic anhydride, maleic acid, acrylic acid, methacrylic acid, carbon monoxide, phenyl vinyl ketone, maleimide, glycidyl (meth)acrylate, hydroxyethyl (meth)acrylate, or the like.
- the product copolymer is a terpolymer.
- Suitable terpolymers include ethylene-methyl acrylate-glycidyl methacrylate terpolymer, ethylene methyl acrylate maleic anhydride terpolymer, ethylene-methyl acrylate-carbon monoxide terpolymer, ethylene-methyl acrylate- methacrylic acid terpolymer, ethylene-methyl acrylate-triethoxysilylethylene terpolymer, and the like.
- Use of one or more of these polar comonomers may modify the miscibility of the olefm-alkyl (meth)acrylate copolymer and the functionalized poly(arylene ether).
- the polar monomer may comprise about 1 to about 25 weight percent of the total monomer used to prepare the olefin- alkyl (meth)acrylate copolymer.
- the olefm-alkyl (meth)acrylate copolymer is the polymerization product of the olefm and alkyl (meth)acrylate described above and further comprises grafted ⁇ , ⁇ -unsaturated carbonyl compounds or ⁇ -hydroxycarbonyl compounds.
- Representative examples of ⁇ , ⁇ -unsaturated carbonyl compounds include maleic anhydride, malonic acid, and the like.
- Representative examples of ⁇ -hydroxycarbonyl compounds include citric acid, isocitric acid, malic acid, and the like.
- the graft copolymers of this embodiment include, for example, polyethylene- methylacrylate-graft-maleic anhydride.
- the olefm-alkyl (meth)acrylate copolymer preferably has a solubility parameter greater than 17.5 J 1/2 /cm 2 , preferably greater than 18 J 1/2 /cm /2 , still more preferably 1 /9 ⁇ /9 greater than 18.2 J /cm " .
- Solubility parameter values may be calculated according to the group contribution methods described in D. W. Van Krevelen, "Properties of Polymers," Elsevier Scientific Publishing, New York, 1976, pages 129-143. Methods of preparing olefm-alkyl (meth)acrylate copolymers are known in the art. Suitable methods are described, for example, in U.S. Patent Nos.
- useful olefm-alkyl (meth)acrylate copolymers include ethylene-methyl acrylate copolymer available from Chevron Chemical Company as PE 2205 (methyl acrylate content of 20%> by weight and a melt index of 2.4 grams/minute (g/min); and from Atofma as LOTRYL® 7BA01 having an acrylic ester content of 6 to 8% by weight and a melt flow rate of from 1 to 1.5 g/min, as well as LOTRYL® 15MA05, 18MA05, 24MA005, 24MA07, 28MA07, 29MA03, 35MA05.
- PE 2205 methyl acrylate content of 20%> by weight and a melt index of 2.4 grams/minute (g/min)
- LOTRYL® 7BA01 having an acrylic ester content of 6 to 8% by weight and a melt flow rate of from 1 to 1.5 g/min, as well as LOTRYL® 15MA05, 18MA05, 24MA005, 24MA07, 28MA07, 29MA03, 35
- LOTRYL® ethylene-n-butyl acrylates available from Atochem under the designation LOTRYL® such as LOTRYL® 17BA04 (containing 16 to 19%> by weight of acrylic ester and having a melt flow rate of 3.5 to 4.5 g/min at 190°C. and 9.8 g/min at 230°C); and LOTRYL® 17BA07 having an acrylic ester content of 16 to 19% by weight and a melt flow rate of 6.5 to about 8 g/min.
- LOTRYL® 17BA04 containing 16 to 19%> by weight of acrylic ester and having a melt flow rate of 3.5 to 4.5 g/min at 190°C. and 9.8 g/min at 230°C
- LOTRYL® 17BA07 having an acrylic ester content of 16 to 19% by weight and a melt flow rate of 6.5 to about 8 g/min.
- the composition may comprise about 5 to about 75 parts by weight of the olefm-alkyl (meth)acrylate copolymer per 100 parts by weight total of the functionalized poly(arylene ether) and the olefm-alkyl (meth)acrylate copolymer.
- the olefm-alkyl (meth)acrylate copolymer amount may preferably be at least about 15 parts by weight, more preferably at least about 30 parts by weight, still more preferably at least about 45 parts by weight.
- the olefm-alkyl (meth)acrylate copolymer amount may preferably be up to about 65 parts by weight, more preferably up to about 55 parts by weight.
- the composition may, optionally, comprise an impact modifier.
- Suitable impact modifiers include natural and synthetic elastomeric polymers such as natural rubbers, synthetic rubbers and thermoplastic elastomers. They are typically derived from monomers such as olefms (e.g., ethylene, propylene, 1-butene, 4-methyl-l-pentene), alkenyl aromatic monomers (e.g., styrene and ⁇ -methyl styrene), conjugated dienes (e.g., butadiene, isoprene, and chloroprene), and vinylcarboxylic acids and their derivatives (e.g., vinyl acetate, acrylic acid, and acrylonitrile).
- olefms e.g., ethylene, propylene, 1-butene, 4-methyl-l-pentene
- alkenyl aromatic monomers e.g., styrene and ⁇ -methyl styrene
- conjugated dienes
- Polyolefms suitable for use as impact modifiers include polyethylene, polypropylene and polyisobutylene with preferred homopolymers being polyethylene, LLDPE (linear low density polyethylene), HDPE (high density polyethylene) and MDPE (medium density polyethylene) and isotactic polypropylene.
- LLDPE linear low density polyethylene
- HDPE high density polyethylene
- MDPE medium density polyethylene
- Copolymers of polyolefms may also be used such as copolymers of ethylene and alpha olef ⁇ ns like propylene and 4-methylpentene-l .
- Copolymers of ethylene and C 3 -C ⁇ o monoolefms and non-conjugated dienes, herein referred to as EPDM copolymers are also suitable.
- suitable C 3 -C ⁇ 0 monoolef ⁇ ns for EPDM copolymers include propylene, propene, 1-butene, 2-butene, 1-pentene, 2-pentene, 1-hexene, 2-hexene and 3-hexene.
- Suitable dienes include 1 ,4-hexadiene and monocylic and polycyclic dienes. Ratios of ethylene to other C 3 -C 10 monoolefm monomers can range from 95:5 to 5:95 with diene units being present in the amount of from 0.1 to 10 mole percent. EPDM copolymers may be functionalized with an acyl group or electrophilic group for grafting onto the polyphenylene ether as disclosed in U.S. Patent No. 5,258,455 to Laughner et al.
- Suitable impact modifiers include conjugated diene homopolymers and random copolymers. Examples include polybutadiene, butadiene-styrene copolymers, butadiene-acrylate copolymers, isoprene-isobutene copolymers, chlorobutadiene polymers, butadiene acrylonitrile polymers, and polyisoprene.
- the impact modifier is a block copolymer of an alkenyl aromatic compound and a conjugated diene.
- the block copolymer is a copolymer comprising (A) at least one block derived from an alkenyl aromatic compound and (B) at least one block derived from a conjugated diene, in which the aliphatic unsaturated group content in the block (B) is reduced by hydrogenation.
- the arrangement of blocks (A) and (B) includes a linear structure, a grafted structure, and a radial teleblock structure with or without a branched chain.
- linear structures embracing diblock (A-B block), triblock (A-B-A block or B-A-B block), tetrablock (A-B-A-B block), and pentablock (A-B-A-B-A block or B-A-B-A-B block) structures as well as linear structures containing 6 or more blocks in total of A and B. More preferred are diblock, triblock, and tetrablock structures, with the A-B-A triblock structure being particularly preferred.
- the alkenyl aromatic compound providing the block (A) is represented by formula
- R 16 and R 17 each independently represent a hydrogen atom, a C ⁇ -C 8 alkyl group, a C 2 -C 8 alkenyl group, or the like;
- R and R each independently represent a hydrogen atom, a C ⁇ -C 8 alkyl group, a chlorine atom, a bromine atom, a carboxylic acid group (-CO 2 H), a hydroxy group or the like;
- R 19 -R 21 each independently represent a hydrogen atom, a C C 8 alkyl group, a C 2 -C 8 alkenyl group, or the like, or R 18 and R 19 are taken together with the central aromatic ring to form a naphthyl group, or R 19 and R 20 are taken together with the central aromatic ring to form a naphthyl group.
- alkenyl aromatic compounds include styrene, p-methylstyrene, alpha-methylstyrene, vmylxylenes, vmyltoluenes, vinylnaphthalenes, divinylbenzenes, bromostyrenes, chlorostyrenes, and the like, and combinations comprising at least one of the foregoing alkenyl aromatic compounds.
- styrene, alpha-methylstyrene, p-methylstyrene, vmyltoluenes, and vmylxylenes are preferred, with styrene being more preferred.
- the conjugated diene examples include 1,3-butadiene, 2-methyl-l,3- butadiene, 2,3-dimethyl-l,3-butadiene, 1,3-pentadiene, and the like. Preferred among them are 1,3-butadiene and 2-methyl-l,3-butadiene, with 1,3-butadiene being more preferred.
- the hydrogenated block copolymer may contain a small proportion of a lower olefmic hydrocarbon such as, for example, ethylene, propylene, 1-butene, dicyclopentadiene, a non-conjugated diene, or the like.
- the block copolymer may optionally be hydrogenated. When it is hydrogenated, it is preferably hydrogenated to such a degree that fewer than 50%>, more preferably fewer than 20%), yet more preferably fewer than 10%>, of the unsaturated bonds in the aliphatic chain moiety derived from the conjugated diene remain unreduced.
- the aromatic unsaturated bonds derived from the alkenyl aromatic compound may be hydrogenated to a degree of up to about 25%.
- the block copolymer may, optionally, comprise either grafted maleic anhydride functions or terminal hydroxyl groups.
- Particularly preferred block copolymers are triblock copolymers and radial block copolymers.
- triblock copolymers are polystyrene-polybutadiene- polystyrene (SBS), hydrogenated polystyrene-polybutadiene-polystyrene (SEBS), polystyrene-polyisoprene-polystyrene (SIS), hydrogenated polystyrene-polyisoprene- polystyrene (SEPS), and poly(alpha methylstyrene)-polyisoprene-poly(alpha methylstyrene).
- SBS polystyrene-polybutadiene- polystyrene
- SEBS hydrogenated polystyrene-polybutadiene-polystyrene
- SEBS hydrogenated polystyrene-polybutadiene-polystyrene
- SIS
- Radial block copolymers generally comprise about 60 to 95 weight percent polymerized alkenyl aromatic monomer and about 40 to 5 weight percent polymerized conjugated diene monomer.
- the radial block copolymer has at least three polymer chains that form a radial configuration. Each chain terminates in a substantially nonelastic segment, to which the elastic polymer segment is joined.
- block copolymers are such materials further containing grafted functionality capable of crosslinking or forming covalent bonds with other components of the blend.
- Such groups include maleic anhydride, trialkoxysiloxane and the like.
- the impact modifier when present, may be used in an amount of about 0.1 to about 30 parts by weight per 100 parts by weight for the total of the functionalized poly(arylene ether) and the olefm-alkyl (meth)acrylate copolymer.
- the impact modifier amount may preferably be at lease about 1 part by weight, more preferably at least about 2 parts by weight, still more preferably at least 5 parts by weight.
- the impact modifier amount may preferably be up to about 25 parts by weight, more preferably up to about 20 parts by weight, still more preferably up to about 15 parts by weight, even more preferably up to about 10 parts by weight.
- the composition may optionally comprise a flame retardant.
- Suitable flame retardants include halosubstituted diaromatic compounds, such as 2,2-bis-(3,5- dichlorophenyl)propane, and phosphorous compounds as described in U.S. Pat. No. 5,461,096 to Bopp et al.
- Other examples of halosubstituted diaromatic flame retardant additives include brominated benzene, chlorinated biphenyl, brominated polystyrene, chlorine-containing aromatic polycarbonates or compounds comprising two phenyl radicals separated by a divalent alkylene group and having at least two chlorine or two bromine atoms per nucleus, and mixtures thereof.
- the preferred flame retardant compounds employed in the compositions of the present invention are free of halogen. These preferred compounds include phosphorous compounds such as elemental phosphorous, organic phosphonic acids, phosphonates, phosphinates, phosphinites, phosphine oxides such as triphenylphosphine oxide, phosphines, phosphites and phosphates.
- phosphorous compounds such as elemental phosphorous, organic phosphonic acids, phosphonates, phosphinates, phosphinites, phosphine oxides such as triphenylphosphine oxide, phosphines, phosphites and phosphates.
- Suitable phosphates include phenylbisdodecyl phosphate, phenylbisneopentyl phosphate, phenyl ethylene hydrogen phosphate, phenyl-bis-3,5,5'-trimethylhexyl phosphate, ethyldiphenyl phosphate, 2- ethylhexyl di(p-tolyl), phosphate, diphenyl hydrogen phosphate, bis(2-ethyl-hexyl)p- tolylphosphate, tritolyl phosphate, bis(2-ethylhexyl)-phenyl phosphate, tri(nonylphenyl)phosphate, phenyl-methyl hydrogen phosphate, di(dodecyl)p-tolyl phosphate, tricresyl phosphate, triphenyl phosphate, isopropylated triphenyl phosphate, halogenated triphenyl phosphate, dibutylphen
- Preferred phosphates include triphenyl phosphate, alkylated triphenyl phosphates, including isopropylated and butylated triphenyl phosphates, bis-neopentyl piperidinyl diphosphate, tetraphenyl bisphenol-A diphosphate, tetraphenyl resorcinol diphosphate, tetraphenyl hydroquinone diphosphate, bisphenol-A poly(phenylphosphate), mixtures of these compounds and derivatives of these compounds. Also included are aluminum salts of phosphates, phosphinate, and phosphonates.
- Representative examples include aluminum tris(O-methylmethylphosphonate), aluminum tris(O- ethylmethylphosphonate) aluminum tris(O-ethylethylphosphonate).
- Other suitable flame retardants include magnesium hydroxide, zinc borate, and the like.
- the flame retardant comprises a metallophosphorous flame retardant having the formula
- each occurrence of R * and R is independently CpCis hydrocarbyl; and each occurrence of m and n is 0 or 1.
- each occurrence of R 23 and R 24 is independently C ⁇ -C 6 alkyl.
- each occurrence of R 23 and R 24 is methyl or ethyl.
- each occurrence of m and n is zero.
- Suitable metallophosphorous flame retardants include, for example, zinc and aluminum salts of dimethylphosphinate, diethylphosphinate, di-n-propylphosphinate, di-n-butylphosphinate, di-n- hexylphosphinate, dicyclohexylphosphinate, di-2-ethylhexylphosphinate, diphenylphosphinate, di-o-tolylphosphinate, dimethylphosphate, diethylphosphate, di- n-propylphosphate, di-n-butylphosphate, di-n-hexylphosphate, dicyclohexylphosphate, di-2-ethylhexylphoshate, diphenylphosphate, di-o-tolylphosphate, and the like, and mixtures thereof.
- a preferred metallophosphorous flame retardant is aluminum tris(diethylphosphinate). Preparation of metallophosphorous flame retardants is described, for example, in U.S. Patent Nos. 6,255,371 and 6,547,992 to Schlosser et al., and 6,355,832 and 6,534,673 to Weferling et al.
- the composition comprises the metallophosphorous flame retardant
- it may be present at about 0.1 to about 50 parts by weight per 100 parts by weight total of the functionalized poly(arylene ether) and the acryloyl monomer.
- the metallophosphorous flame retardant amount may preferably be at least about 1 part by weight, more preferably at least about 4 parts by weight, still more preferably at least about 8 parts by weight.
- the metallophosphorous flame retardant amount may preferably be up to about 40 parts by weight, more preferably up to about 30 parts by weight, still more preferably up to about 20 parts by weight.
- Suitable flame retardants include compounds containing a phosphorus- nitrogen bond include phosphonitrilic chloride, phosphorus ester amides, phosphoric acid amides, phosphonic acid amides, and phosphinic acid amides.
- Bis- phosphoramide materials derived from piperazine and hydroxyaromatic compounds are especially useful.
- Suitable phosphorous flame retardant additives are commercially available and methods for preparing the phosphate flame retardants are generally known in the art.
- the compounds may be prepared by reacting a halogenated phosphate compound with various dihydric or trihydric phenolic compounds until the desired number of phosphate functional groups are obtained.
- the phenolic compounds are dihydroxy aromatic compounds such as resorci ol and hydroqninone.
- the flame retardant may be used in an amount of about 0.5 to about 30 weight percent, based on the total weight of the composition.
- a preferred level for the phoshorous flame retardants is about 9 to about 17 weight percent.
- compositions may, optionally, further comprise other additives to modify the properties of the composition.
- additives for example, dye, pigments, colorants, and mineral fillers may be included in the composition such as titanium dioxide, calcium carbonate, talc, silica, mica, etc.
- Mineral fillers may be included in amounts of about 1 to about 40 weight percent, preferably about 5 to about 35 weight percent, based on the total weight of the composition.
- additives that may be included in the compositions include metal particles, reinforcing agents (e.g., glass fibers), conductive fillers (e.g., conductive carbon black, carbon fibers, stainless steel fibers, metal flakes and metal powders), antioxidants, heat stabilizers, light stabilizers, antiblocking agents, antistatic agents, plasticizers, processing aids, lubricants, drip retardants, flow modifiers, and the like.
- metal particles e.g., glass fibers
- conductive fillers e.g., conductive carbon black, carbon fibers, stainless steel fibers, metal flakes and metal powders
- antioxidants e.g., heat stabilizers, light stabilizers, antiblocking agents, antistatic agents, plasticizers, processing aids, lubricants, drip retardants, flow modifiers, and the like.
- heat stabilizers e.g., light stabilizers, antiblocking agents, antistatic agents, plasticizers, processing aids, lubricants, drip retardants, flow modifiers
- the composition may comprise about 1 to about 50 parts by weight of unfunctionalized poly(arylene ether) per 100 parts by weight for the total of the functionalized poly(arylene ether) and the olefm-alkyl (meth)acrylate copolymer.
- the composition after molding may have a flammability rating of V-l, more preferably V-0, measured according to UL-94.
- the composition after molding may have a tensile strength at maximum load of at least 1 megapascal, preferably at least 3 megapascals, still more preferably at least 7 megapascals, measured at 25°C according to ASTM D638.
- the composition may have a tensile elongation at break of at least -100 percent, preferably at least 150 percent, still more preferably at least 200 percent, even more preferably at least 100 percent, yet more preferably at least 150 percent, and still more preferably at least 200 percent, measured at 25°C according to ASTM D638.
- the composition comprises a capped poly(arylene ether); an olefm-alkyl (meth)acrylate copolymer; a copolymer of an alkenyl aromatic compound and a conjugated diene; and a halogen-free flame retardant.
- the composition comprises about 25 to about 95 parts by weight of a methacrylate-capped poly(arylene ether); about 5 to about 75 parts by weight of an ethylene-methyl acrylate copolymer; about 5 to about 20 parts by weight of a copolymer of an alkenyl aromatic compound and a conjugated diene; and about 0.5 to about 30 parts by weight of a halogen-free flame retardant; wherein all parts by weight are based on 100 parts by weight total of the methacrylate-capped poly(arylene ether) and the ethylene-methyl acrylate copolymer.
- compositions comprising: a poly(arylene ether); an olefin- alkyl (meth)acrylate copolymer; and a metallophosphorous flame retardant having the formula
- the poly(arylene ether) may be a functionalized poly(arylene ether), as described above.
- the poly(arylene ether) may be an unfunctionalized poly(arylene ether), also described above.
- the unfunctionalized poly(arylene ether) resin may have an intrinsic viscosity of about 0.1 to about 0.6 dL/g.
- Another embodiment is a method of preparing a composition, comprising: blending a functionalized poly(arylene ether) and an olefm-alkyl acrylate copolymer to form an intimate blend.
- Any known apparatus may be used to carry out the method. Utilization of the method on a laboratory scale may employ a lab-scale mixer such as, for example, a Labo Plastomill available from Toyo Seiki Company, Hyogo, Japan.
- Preferred apparatuses for conducting the method on a larger scale include single-screw and twin-screw extruders, with twin-screw extruders being more preferred. Extruders for melt blending of thermoplastics are commercially available from, for example, Coperion in Ramsey, New Jersey.
- compositions wherein the specified components have reacted to form reaction products are compositions wherein the specified components have reacted to form reaction products.
- another embodiment is a composition comprising the reaction product of a functionalized poly(arylene ether); and an olefm-alkyl (meth)acrylate copolymer.
- the invention includes articles comprising any of the above compositions and their reactions products.
- one embodiment is an article comprising a composition comprising a functionalized poly(arylene ether) and an olefm-alkyl (meth)acrylate copolymer.
- Another embodiment is a composition comprising the reaction product of a functionalized poly(arylene ether) and an olefm-alkyl (meth)acrylate copolymer.
- the composition is particularly useful for fabricating insulation for cable and wire, because, in addition to exhibiting the improved properties described herein, the composition avoids the environmental concerns associated with the polyvinyl chloride resins currently used in such applications.
- Articles may be fabricated by known techniques for forming thermoplastic articles, including injection molding, blow molding, wire extrusion, and the like.
- insulated wire and cable comprising the cured composition as insulation
- examples of insulated wire and cable comprising the cured composition as insulation include an electric cable in which at least the conductor is covered with an insulating layer comprising the cured composition. It is possible to change the conductor parts into aggregated wires, install a semiconducting layer between the conductor and insulating layer, or alternatively, form a flame retardant resin layer on the outer side of the insulating layer, if desired.
- Examples of the electric wire and cable may include a cable comprising a wire which is formed from an aggregate of copper wires, a semiconducting layer which is covering the wire and formed by a resin composition to which a conductive carbon or metal powder has been added, an insulating layer which is covering the semiconducting layer and formed by the cured composition, a covering or semiconducting layer which is covering the insulating layer and formed by a metal sheet, and a flame-retardant cured composition that is provided on the outermost side; and a cable comprising an aggregate of covered- copper wires and a flame-retardant cured composition that is provided on the outermost side of the aggregate, wherein the covered-copper wire comprise a single copper wire, a semiconductor layer covering the wire, an insulating layer covering the semiconducting layer and formed by the cured composition, and a metal film layer further provided onto the insulating layer; and the like.
- Another embodiment is a composition comprising a poly(arylene ether) and a polyolefm.
- the poly(arylene ether) and the polyolefm may be compatibilized by the presence of a graft copolymer comprising a polyolefm backbone and one or more poly(arylene ether) grafts.
- This copolymer may be formed by irradiating porous polyolefm, thereby forming radical sites on the polyolefm, and then melt blending the irradiated porous polyolefm with a reactive-capped poly(arylene ether).
- the copolymer may also be formed by initiating polymerization of a phenol, such as 2,6- dimethylphenol, on the radical sites of the poly olefm.
- the composition may further comprise polystyrene, rubber modified polystyrene, glass beads, glass fibers, poly(methyl methacrylate), modified polypropylene, styrene-butadiene block copolymer (SB), styrene-isoprene block copolymer (SI), hydrogenated styrene- butadiene block copolymer (SEB), hydrogenated styrene-isoprene block copolymer (SEP), styrene-butadiene-styrene triblock copolymer (SBS) and its hydrogenated counterpart (SEBS), styrene-isoprene-styrene triblock copolymer (SBS) and its hydrogenated counterpart (SEBS), styrene-is
- methacrylate- capped poly(arylene ether), polypropylene, and free radical initiator are fed into an extruder at the same or different position along the stream.
- methacrylate-capped poly(arylene ether), and porous polypropylene could be irradiated prior to melting reaction in extruder to generate "trapped free radical sites" on polymer chains.
- the methacrylate-capped poly(arylene ether) is fed at the feed throat to melt.
- the irradiated polypropylene is introduced downstream to achieve the grafting to the methacrylate-capped poly(arylene ether).
- the methacrylate-capped poly(arylene ether) may experience delayed melting.
- methacrylate-capped poly(arylene ether) having low intrinsic viscosity e.g. 0.12 dL/g
- both methacrylate-capped poly(arylene ether) and polypropylene may be fed to the extruder at the same time.
- free radical initiator may, optionally, be fed into extruder to adjust reaction process and control final product quality.
- Example 1 a blend was prepared comprising 500 grams of methacrylate-capped poly(phenylene ether) (500g) as prepared in Preparative Example A and 500g of poly(ethylene-c ⁇ -methyl acrylate) (6.5%> methyl acrylate) obtained from Atofina and having a with methyl acrylate content of 6.5%>.
- the resulting test specimens were used to measure tensile strength at maximum load (expressed in megapascals, MPa) and tensile elongation at break (expressed in percent) according to ASTM D638. The results are shown in Table 1.
- the unfunctionalized poly(arylene ether) was the poly(2,6- dimethylphenyl ether) resin having an intrinsic viscosity of 0.30 dL/g that was used in Preparative Example A. All poly(ethylene-co-methyl acrylate) resins were obtained from Atofma and had the methyl acrylate contents specified in Table 1.
- the impact modifier used in Example 7, KRATON® G 1701 is a hydrogenated styrene-isoprene copolymer having a styrene content of about 37 weight percent.
- Compositions and properties are summarized in Table 1. The results show that Examples 1 and 2, with functionalized poly(arylene ether) exhibit improved compatibility compared to Comparative Examples 1 and 2 with unfunctionalized poly(arylene ether), which delaminated. The results also show that the composition of Example 2, containing a poly(ethylene-co-methyl acrylate) with 6.5% methyl acrylate, exhibits improved tensile strength and elongation compared to the pure PPE composition of Comparative Example 7. Furthermore, the results show that Example 7, which includes an impact modifier, exhibits outstanding tensile elongation while maintaining high impact strength.
- Example 1 The procedure of Example 1 was used to prepare compositions further comprising a flame retardant.
- the poly(ethylene-c ⁇ -mefhyl acrylate) had a methyl acrylate content of 27 weight percent and was obtained from Atofma.
- the poly(arylene ether) was unfunctionalized poly(2,6-dimethylphenyl ether) resin having an intrinsic viscosity of 0.40 dL/g prepared as in Preparative Example A.
- the impact modifier was a hydrogenated styrene-isoprene-styrene triblock copolymer obtained as KRATON® G1701 from Kraton Polymers.
- the halogen-free flame retardant was aluminum tris(diethylphosphinate) obtained as OP930 from Clariant.
- the desirable UL-94 V-0 rating requires, inter alia, that specimens may not burn with flaming combustion for more than 10 seconds after either application of the test flame, and that specimens may not drip flaming particles that ignite the dry absorbent surgical cotton located 300 mm below the test specimen. Standard deviations reflect measurements on three samples per test. Compositions and properties are summarized in Table 2. The results show that the composition of Example 10, containing 17.5 weight percent flame retardant, achieves a desirable V-0 rating in the UL-94 flammability test.
Abstract
Description
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JP2006533864A JP2007507586A (en) | 2003-10-03 | 2004-08-31 | Composition comprising functionalized poly (arylene ether) and ethylene-alkyl (meth) acrylate copolymer, process for its preparation and product thereof |
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WO2019116309A1 (en) * | 2017-12-13 | 2019-06-20 | Sabic Global Technologies B.V. | Process for the manufacture of thermosetting poly(arylene ether) copolymer and compositions |
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JP6909342B1 (en) * | 2020-07-31 | 2021-07-28 | アイカ工業株式会社 | Resin composition and adhesive sheet using it |
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- 2004-08-31 EP EP04782702A patent/EP1678255B1/en not_active Not-in-force
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EP1838780A1 (en) * | 2004-12-30 | 2007-10-03 | Cheil Industries Inc. | Flameproof styrenic resin composition |
EP1838780A4 (en) * | 2004-12-30 | 2009-05-06 | Cheil Ind Inc | Flameproof styrenic resin composition |
CN102321332A (en) * | 2006-08-03 | 2012-01-18 | 旭化成化学株式会社 | The modification method of the extrusion moulding property of electric wire |
US8901214B2 (en) | 2006-08-03 | 2014-12-02 | Asahi Kasei Chemicals Corporation | Flame-retardant resin composition |
Also Published As
Publication number | Publication date |
---|---|
US7211639B2 (en) | 2007-05-01 |
CN1886458A (en) | 2006-12-27 |
EP1678255B1 (en) | 2012-11-14 |
KR20060083987A (en) | 2006-07-21 |
KR100796108B1 (en) | 2008-01-21 |
JP2007507586A (en) | 2007-03-29 |
CN100506915C (en) | 2009-07-01 |
US20050075472A1 (en) | 2005-04-07 |
EP1678255A1 (en) | 2006-07-12 |
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