CA1119742A - Impact resistant polyphenylene ether resin compositions containing hydrogenated radial teleblock copolymers - Google Patents
Impact resistant polyphenylene ether resin compositions containing hydrogenated radial teleblock copolymersInfo
- Publication number
- CA1119742A CA1119742A CA000292241A CA292241A CA1119742A CA 1119742 A CA1119742 A CA 1119742A CA 000292241 A CA000292241 A CA 000292241A CA 292241 A CA292241 A CA 292241A CA 1119742 A CA1119742 A CA 1119742A
- Authority
- CA
- Canada
- Prior art keywords
- molding composition
- weight
- styrene
- parts
- radial teleblock
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Expired
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Classifications
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L25/00—Compositions of, homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by an aromatic carbocyclic ring; Compositions of derivatives of such polymers
- C08L25/02—Homopolymers or copolymers of hydrocarbons
- C08L25/04—Homopolymers or copolymers of styrene
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G81/00—Macromolecular compounds obtained by interreacting polymers in the absence of monomers, e.g. block polymers
- C08G81/02—Macromolecular compounds obtained by interreacting polymers in the absence of monomers, e.g. block polymers at least one of the polymers being obtained by reactions involving only carbon-to-carbon unsaturated bonds
- C08G81/021—Block or graft polymers containing only sequences of polymers of C08C or C08F
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G81/00—Macromolecular compounds obtained by interreacting polymers in the absence of monomers, e.g. block polymers
- C08G81/02—Macromolecular compounds obtained by interreacting polymers in the absence of monomers, e.g. block polymers at least one of the polymers being obtained by reactions involving only carbon-to-carbon unsaturated bonds
- C08G81/021—Block or graft polymers containing only sequences of polymers of C08C or C08F
- C08G81/022—Block or graft polymers containing only sequences of polymers of C08C or C08F containing sequences of polymers of conjugated dienes and of polymers of alkenyl aromatic compounds
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L51/00—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
- C08L51/04—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 rubbers
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- 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
- C08L71/123—Polyphenylene oxides not modified by chemical after-treatment
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- 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
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- 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
Abstract
ABSTRACT OF THE DISCLOSURE
Thermoplastic compositions moldable to articles of high impact strength are disclosed which comprise an intimate admixture of a polyphenylene ether resin, a styrene resin, and a radial teleblock copolymer comprising a vinyl aromatic compound, a saturated rubber, and a coupling agent.
Also included within the scope of this invention are reinforced and flame-retardant compositions of said thermo-plastic materials.
Thermoplastic compositions moldable to articles of high impact strength are disclosed which comprise an intimate admixture of a polyphenylene ether resin, a styrene resin, and a radial teleblock copolymer comprising a vinyl aromatic compound, a saturated rubber, and a coupling agent.
Also included within the scope of this invention are reinforced and flame-retardant compositions of said thermo-plastic materials.
Description
~ ,~ 8 CH 2419 This invention relates to thermoplastic molding compositions of a polyphenylene ether resin, a styrene resin, - and a radial teleblock copolymer of a vinyl aromatic compound and a saturated rubber. The compositions of this invention provide molded articles having good mechanical properties, including improved impact resistance. Reinforced and flame-retardant compositions are also provided.
The polyphenylene ether resins are a family of engineering thermoplastics that are well known to the polymer art. These polymers may be made by a variety of catalytic and non-catalytic processes from the corresponding phenols or reactive derivatives thereof. By way of illustration, certain of the polyphenylene ethers are disclosed in Hay, U.S. 3,306,874 dated February 28, 1967 and 3,306,875 dated February 28, 1967; and in Stamatoff, U.S. 3,257,357 dated June 21, 1966 and 3,257,358 dated June 21, 1966. In the Hay patents, the polyphenylene ethers are prepared by an oxidative coupling reaction comprisiny passing an oxygen-containing gas through a reac-tion solution of a phenol and a metal-amine complex catalys-t. Other disclosures relating to processes for preparing polyphenylene ether resins, including graft copolymers of polyphenylene ethers with styrene type compounds, are ~ound in Fox, U.S. 3,356,761 dated December 5, 1967; Sumitomo, U.K. 1,291,609; Bussink et al., U.S. 3,337,499 dated August 22, 1967; Blanchard et al., U.S. 3,219,626 November 23, 1965; Laakso et al., U.S.
3, 34~
3,342,892 dated September 19, 1967; Borman, U.S. ~,~4,1~
dated September 26, 1967; ~lori et al, U.S. 3,384,619 dated May 21, 1968; Faurote et al., U.S. 3,440, 217 dated April 22, 1969; and disclosures relating to metal based catalysts which do not include amines, are known from patents such as ~ieden et al., U.S. 3,442,885 dated May 6r 1969 (copper-- 1 ~
~ ~ 8CH-2419 amidines); Nakashio et al, U.S. Patent 3,573,257 dated March 30, 1971 (metal-alcoholate or -phenolate); Xobayashi et al, U.S.
Patent 3,455,880 dated July 15, 1969 (cobalt chelates); and the like. In the Stamatoff patents, the polyphenylene ethers are produced by reacting the corresponding phenolate ion with an initiator, such as peroxy acid salt, an acid peroxide, a hypohalite, and the like, in the presence of a complexing agent. Disclosures relating to non-catalytic processes, such as oxidation with lead dioxide, silver oxide, etc., are described in Price et al, U.S. Patent 3,382,212 dated May 7, 1968.
Cizek, U.S. Patent 3,383,435 dated May 14, 1968 disclosures polyphenylene ether-styrene resin compositions.
The processing of polyphenylene ether resins on injection molding and extrusion equipment is enhanced when the polyphenylene ethers are combined with styrene resins, e.g., crystal homopolystyrene or rubber modified high-impact poly-styrenes. These polymers are combinable in a wide range of ; proportions, e.g., from 1 to 99 parts of polyphenylene ether and from 99 to 1 parts of styrene resin. Compositions com-prising from 10 to 60 parts of polyphenylene ether and 90 to - 40 parts of styrene resin offer an especially wide range of desirable design properties.
Such combinations are disc]osed in Cizek, U~S.
Patent 3,383,435 dated May 14, 1968. The thermoplastic composition disclosed in Cizek can include a rubber-modified high-impact styrene resin, as well as a homopo]ystyrene.
High-impact styrene resins are especially useful in providing polyphenylene ether compositions which possess good resistance to impact.
It is disclosed in copending, commonly assigned Canadian patent application Serial No. 274,750 filed
The polyphenylene ether resins are a family of engineering thermoplastics that are well known to the polymer art. These polymers may be made by a variety of catalytic and non-catalytic processes from the corresponding phenols or reactive derivatives thereof. By way of illustration, certain of the polyphenylene ethers are disclosed in Hay, U.S. 3,306,874 dated February 28, 1967 and 3,306,875 dated February 28, 1967; and in Stamatoff, U.S. 3,257,357 dated June 21, 1966 and 3,257,358 dated June 21, 1966. In the Hay patents, the polyphenylene ethers are prepared by an oxidative coupling reaction comprisiny passing an oxygen-containing gas through a reac-tion solution of a phenol and a metal-amine complex catalys-t. Other disclosures relating to processes for preparing polyphenylene ether resins, including graft copolymers of polyphenylene ethers with styrene type compounds, are ~ound in Fox, U.S. 3,356,761 dated December 5, 1967; Sumitomo, U.K. 1,291,609; Bussink et al., U.S. 3,337,499 dated August 22, 1967; Blanchard et al., U.S. 3,219,626 November 23, 1965; Laakso et al., U.S.
3, 34~
3,342,892 dated September 19, 1967; Borman, U.S. ~,~4,1~
dated September 26, 1967; ~lori et al, U.S. 3,384,619 dated May 21, 1968; Faurote et al., U.S. 3,440, 217 dated April 22, 1969; and disclosures relating to metal based catalysts which do not include amines, are known from patents such as ~ieden et al., U.S. 3,442,885 dated May 6r 1969 (copper-- 1 ~
~ ~ 8CH-2419 amidines); Nakashio et al, U.S. Patent 3,573,257 dated March 30, 1971 (metal-alcoholate or -phenolate); Xobayashi et al, U.S.
Patent 3,455,880 dated July 15, 1969 (cobalt chelates); and the like. In the Stamatoff patents, the polyphenylene ethers are produced by reacting the corresponding phenolate ion with an initiator, such as peroxy acid salt, an acid peroxide, a hypohalite, and the like, in the presence of a complexing agent. Disclosures relating to non-catalytic processes, such as oxidation with lead dioxide, silver oxide, etc., are described in Price et al, U.S. Patent 3,382,212 dated May 7, 1968.
Cizek, U.S. Patent 3,383,435 dated May 14, 1968 disclosures polyphenylene ether-styrene resin compositions.
The processing of polyphenylene ether resins on injection molding and extrusion equipment is enhanced when the polyphenylene ethers are combined with styrene resins, e.g., crystal homopolystyrene or rubber modified high-impact poly-styrenes. These polymers are combinable in a wide range of ; proportions, e.g., from 1 to 99 parts of polyphenylene ether and from 99 to 1 parts of styrene resin. Compositions com-prising from 10 to 60 parts of polyphenylene ether and 90 to - 40 parts of styrene resin offer an especially wide range of desirable design properties.
Such combinations are disc]osed in Cizek, U~S.
Patent 3,383,435 dated May 14, 1968. The thermoplastic composition disclosed in Cizek can include a rubber-modified high-impact styrene resin, as well as a homopo]ystyrene.
High-impact styrene resins are especially useful in providing polyphenylene ether compositions which possess good resistance to impact.
It is disclosed in copending, commonly assigned Canadian patent application Serial No. 274,750 filed
- 2 -~ 8 CH 2419 March 25, 1977 that compositions of a polyphenylene ether resin, a styrene resin, and a radial telebloclc copolymer of a vinyl aromatic compound and a conjugated diene, e.g., a styrene-butadiene radial teleblock copolymer, provide molded articles of good impact strength.
It has now been surprisingly discovered that when compositions are prepared from a polyphenylene ether resin, a styrene resin, and a hydrogenated radial teleblock copolymer of a vinyl aromatic compound and a saturated rubber, the re-sulting compositions provide molded articles of improved surface gloss. The radial hydrogenated teleblock copolymers employed in the present invention have been found to be compatible with, and effective for, compositions of relatively high polyphenylene ether resin content, e.g., 50 parts by weight or more, and low molecular weight crystal polystyrene, as well as compositions of relatively low polyphenylene ether resin content, e.g., 35 parts by weight or less, and high-impact polystyrene.
As used herein, the term "hydrogenated radial tele-block copolymer" refers to branched polymers having segments, or blocks, which are comprised of a saturated rubber, blocks of a vinyl aromatic polymer, and a coupling agent. More particu-larly, in the copolymer structure r several chains of the rubber, usually three or more, e~tend from a coupling agent, with each chain terminating at its other end with a block of the vinyl aromatic polymer. It is generally believed that incompatibility of the block segments in the radial teleblock copolymer promotes the formation of a two-phase system with blocks of the vinyl aromatic polymer coalescing to form discrete regions, or "domains". These domains simulate the effect of cross-links between the chains of elastomer, and a branched elastomeric network is thus formed comprising blocks ~97~ 8CH-2419 of a saturated rubber, blocks of vinyl aroma-tic polymer, and a coupling agent.
Radial teleblock copolymers are known in the art.
For instance, detailed descriptions of these materials are given by Marrs et al in ADHESIVES AGE, December, 1971, pp.
15-20 and by Haws et al. in RUBB~R WORLD, January, 1973, pp.
27-32. Hydrogenation of radial teleblock copolymers is also known in the art.
It is, therefore, a primary object of this invention to provide improved compositions based on poly-phenylene ether resins, styrene resins, and hydrogenated radial teleblock copolymers.
Another object of this invention is to provide molding compositions and molded articles based on polyphenylene ether resins, styrene resins, and hydrogenated radial teleblock copolymers that have improved surface gloss.
Still another object of this invention is to provide molding compositions and molded articles based on polyphenylene ether resins, styrene resins, and hydrogenated radial teleblock copolymers that have improved impact strength.
It is also an object of this invention to provide the above-described, improved molding compositions in reinforced and/or flame-retardant embodiments.
According to the present invention, there are provided thermoplastic molding compositions which comprise an intimate admixture of:
(i) a polyphenylene ether resin;
(ii) a styrene resin; and (iii) a hydrogenated radial teleblock copolymer of a vinyl aromatic compound, a saturated rubber, and a coupling agent.
8 CH 2~19 Within the invention broadly described above, the styrene resin component (ii) can be ei-ther homopolystyrene or a rubber-modified high-impact polystyrene. The radial teleblock copolymer (iii) is preferably a branched copolymer of styrene and hydrogenated rubber containing a relatively small, effective amount of a coupling agent selected from ~M
among epoxidized-polybutadiene (e.g., Oxiron 2000 or Oxiron ~ -~
2001), SiC14, or mixtures thereof.
The polyphenylene ether resin (i) is preferably one of a family having repeating units represented by the formula: -Q
wherein the oxygen ether atom of one unit is connected to the `
benzene nucleus of the next adjoining unit, n is a posi-tive integer and is at least 50, and each Q is a monovalent sub-stituent selected from the group consisting of hydrogen,halogen, hydrocarbon radicals free of a tertiary alpha-carbon atom, halohydrocarbon radicals having at least two carbon atoms between the halogen atom and the phenyl nucleus, hydrocarbonoxy radicals, and halohydrocarbonoxy radicals ~`
having at least two carbon atoms between the halogen atom and the phenol nucleus.
Examples of polyphenylene ethers corresponding to the above formula can be found in the above-re~erenced patents of Hay and Stamatoff.
For purposes of the present invention an especially preferred family of polyphenylene ethers includes those having alkyl substitution in the two positions ortho to the oxygen ether atom, i.e. those of the above formula wherein each Q
is alkyl, most preferably having from 1 to 4 carbon atoms.
Illustrative members of this class are: poly(2,6-dimethyl-- 1,4-phenylene)ether; poly(2,6~diethyl-1,4-phenylene)ether;
poly(2-methyl-6-ethyl-1,4-phenylene)ether; poly(2-methyl-6-propyl-1,4-phenylene)ether; poly(2,6-dipropyl-1,4-phenylene)-` ether; poly(2-ethyl-6-propyl-1,4-phenylene)ether; and the like.
The most preferred polyphenylene ether resin is poly(2.6-dimethyl-1,4-phenylene)ether, preferably having an intrinsic viscosity of about 0.5 deciliters per gram as measured in chloroform at 30~.
The preferred styrene resins (ii) will be those having at least 25% by weight of repeating units derived from a vinyl aromatic monomer of the formula:
CR = CHR
~II) ~ ~ ~ R3 wherein Rl and R2 are se]ec-ted from the group consisting of hydrogen and lower alkyl or alkenyl groups of from 1 to 6 carbon atoms; R3 and R4 are selected from the group consisting of chloro, bromo, hydrogen, and lower alkyl groups of from 1 to 6 carbon atoms; and R5 and R6 are selected from the group consisting of hydrogen and lower slkyl and alkenyl groups of from 1 to 6 carbon atoms or R5 and R6 may be concatenated together with hydrocarbyl groups to form a naphthyl group. These compounds are free of any substituent that has a tertiary carbon atom.
~ ' ~1197~2 8 CH 2419 ~:`. Specific examples of vinyl aromatic monomers include styrene, chlorostyrene, ~ -methylstyrene, vinyl xylene, divinylbenzene, and vinyl naphthalene.
..~
~ The vinyl aromatic monomer may be copolymerized .~
:i i with materials such as those having the general formula:
.~ 8 ;. R
~ R - C(H)n ~ ~ - C ~ ~ (CH2)m ..... .
; ~ , .
wherein the dotted lines each represent a single or a double carbon to carbon bond; R7 and R8 taken together represent a I C) C--O--C linkage; R is selected from the group consis~ting of : hydrogen, vinyl, alkyl of from 1 to 12 carbon atoms, alkenyl of ; from 1 to 12 carbon atoms, alkylcarboxylic of from 1 to 12 ~ :.
carbon atoms, and alkenylcarboxylic of from 1 to 12 carbon ~.
~ ~ .
atoms; n is 1 or 2, depending on the position of the carbon- ;
carbon double bond; and m is an integer of fxom 0 to about 1~. . .
li Examples include maleic anhydride, citraconic anhydride, ita- :
;',,,~! 20 conic anhydride, aconitic anhydride, and the like.
,:
i Merely by way of illustration, the styrene resins (ii) include homopolymers such as polystyrene and monochloro~
; polystyrene, the modified polystyrenes, such ~s rubber~ ~:
" ~
modified, high-impact polystyrene, and the styrene containing i copolymers, such as the styrene-acrylonitrile copolymers, ~! styrene-butadiene copolymers, styrene~acrylonitrile-o~ kyl .. styrene copolymers, styrene-acrylonitrile-butadiene copolymers, : ,, ~- poly-~ -methyl-styrene, copolymers of ethylvinylbenzene, and divinylbenzene, styrene-maleic anhydride copolymers, styrene- ~.
i 30 butadiene-styrene block copolymers and styrene-butadiene block copolymers, and styrene-butadiene-styrene maleic ~ anhydride block copolymers. -~ 8 C~ 2419 The styrene-maleic anhydride copolymers are described in U.S. 3,336,267 dated August 15, 1967 and U.S.
2,769,804 dated November 6, 1956.
Especially preferred styrene resins are homopoly-styrene and rubber-modified high-impact polystyrene resins, i.e., those which have been modified by natura] or synthetic polymeric materials which are elastomers at room temperature, e.g., 20 to 25C~, such as polystyrene resins containing poly-butadiene or ruhbery styrene-butadiene copolymers.
A preferred high-impact polystyrene is FG 834, available from Foster-Grant Co., which is a rubber-modiEied high-impact polystyrene containing about 8% polybutadiene rubber. A preferred low molecular weight homopolystyrene is KPTL-5, commercially available from Arco Polymers, Inc., Pittsburgh, Pa., having a number average molecular weight of about 40,000. A preferred homopolystyrene of relatively high molecular weight is DYL-8G, with a number average molecular weight of about 150,000, also available from Arco.
Radial teleblock copolymers are available commercially or can be prepared by following the teachings of the prior art. As an illustration, they can be made by poly-merizing conjugated dienes, e.g., butadier~e, and vinyl aromatic compounds, e.g., styrene in the presence of an organo-metallic initiator, e.g., n-butyllithium, to produce copolymers which contain an ac-tive metal atom, such as lithium, on one end of each of the polymer chains. These metal atom-terminated polymers are then reacted wi-th a coupling agent which has at least three active sites capable of reacting with the carbon-metal atom bonds on the polymer chains and replacing the metal atoms on the chains. This results in polymers which have relatively long branches which radiate from a nucleus formed by the poly~functional coupling agent. Such a method of ~ 8CH 2419 .'~
preparation is described in detail in Zelinski et al., U.S.
It has now been surprisingly discovered that when compositions are prepared from a polyphenylene ether resin, a styrene resin, and a hydrogenated radial teleblock copolymer of a vinyl aromatic compound and a saturated rubber, the re-sulting compositions provide molded articles of improved surface gloss. The radial hydrogenated teleblock copolymers employed in the present invention have been found to be compatible with, and effective for, compositions of relatively high polyphenylene ether resin content, e.g., 50 parts by weight or more, and low molecular weight crystal polystyrene, as well as compositions of relatively low polyphenylene ether resin content, e.g., 35 parts by weight or less, and high-impact polystyrene.
As used herein, the term "hydrogenated radial tele-block copolymer" refers to branched polymers having segments, or blocks, which are comprised of a saturated rubber, blocks of a vinyl aromatic polymer, and a coupling agent. More particu-larly, in the copolymer structure r several chains of the rubber, usually three or more, e~tend from a coupling agent, with each chain terminating at its other end with a block of the vinyl aromatic polymer. It is generally believed that incompatibility of the block segments in the radial teleblock copolymer promotes the formation of a two-phase system with blocks of the vinyl aromatic polymer coalescing to form discrete regions, or "domains". These domains simulate the effect of cross-links between the chains of elastomer, and a branched elastomeric network is thus formed comprising blocks ~97~ 8CH-2419 of a saturated rubber, blocks of vinyl aroma-tic polymer, and a coupling agent.
Radial teleblock copolymers are known in the art.
For instance, detailed descriptions of these materials are given by Marrs et al in ADHESIVES AGE, December, 1971, pp.
15-20 and by Haws et al. in RUBB~R WORLD, January, 1973, pp.
27-32. Hydrogenation of radial teleblock copolymers is also known in the art.
It is, therefore, a primary object of this invention to provide improved compositions based on poly-phenylene ether resins, styrene resins, and hydrogenated radial teleblock copolymers.
Another object of this invention is to provide molding compositions and molded articles based on polyphenylene ether resins, styrene resins, and hydrogenated radial teleblock copolymers that have improved surface gloss.
Still another object of this invention is to provide molding compositions and molded articles based on polyphenylene ether resins, styrene resins, and hydrogenated radial teleblock copolymers that have improved impact strength.
It is also an object of this invention to provide the above-described, improved molding compositions in reinforced and/or flame-retardant embodiments.
According to the present invention, there are provided thermoplastic molding compositions which comprise an intimate admixture of:
(i) a polyphenylene ether resin;
(ii) a styrene resin; and (iii) a hydrogenated radial teleblock copolymer of a vinyl aromatic compound, a saturated rubber, and a coupling agent.
8 CH 2~19 Within the invention broadly described above, the styrene resin component (ii) can be ei-ther homopolystyrene or a rubber-modified high-impact polystyrene. The radial teleblock copolymer (iii) is preferably a branched copolymer of styrene and hydrogenated rubber containing a relatively small, effective amount of a coupling agent selected from ~M
among epoxidized-polybutadiene (e.g., Oxiron 2000 or Oxiron ~ -~
2001), SiC14, or mixtures thereof.
The polyphenylene ether resin (i) is preferably one of a family having repeating units represented by the formula: -Q
wherein the oxygen ether atom of one unit is connected to the `
benzene nucleus of the next adjoining unit, n is a posi-tive integer and is at least 50, and each Q is a monovalent sub-stituent selected from the group consisting of hydrogen,halogen, hydrocarbon radicals free of a tertiary alpha-carbon atom, halohydrocarbon radicals having at least two carbon atoms between the halogen atom and the phenyl nucleus, hydrocarbonoxy radicals, and halohydrocarbonoxy radicals ~`
having at least two carbon atoms between the halogen atom and the phenol nucleus.
Examples of polyphenylene ethers corresponding to the above formula can be found in the above-re~erenced patents of Hay and Stamatoff.
For purposes of the present invention an especially preferred family of polyphenylene ethers includes those having alkyl substitution in the two positions ortho to the oxygen ether atom, i.e. those of the above formula wherein each Q
is alkyl, most preferably having from 1 to 4 carbon atoms.
Illustrative members of this class are: poly(2,6-dimethyl-- 1,4-phenylene)ether; poly(2,6~diethyl-1,4-phenylene)ether;
poly(2-methyl-6-ethyl-1,4-phenylene)ether; poly(2-methyl-6-propyl-1,4-phenylene)ether; poly(2,6-dipropyl-1,4-phenylene)-` ether; poly(2-ethyl-6-propyl-1,4-phenylene)ether; and the like.
The most preferred polyphenylene ether resin is poly(2.6-dimethyl-1,4-phenylene)ether, preferably having an intrinsic viscosity of about 0.5 deciliters per gram as measured in chloroform at 30~.
The preferred styrene resins (ii) will be those having at least 25% by weight of repeating units derived from a vinyl aromatic monomer of the formula:
CR = CHR
~II) ~ ~ ~ R3 wherein Rl and R2 are se]ec-ted from the group consisting of hydrogen and lower alkyl or alkenyl groups of from 1 to 6 carbon atoms; R3 and R4 are selected from the group consisting of chloro, bromo, hydrogen, and lower alkyl groups of from 1 to 6 carbon atoms; and R5 and R6 are selected from the group consisting of hydrogen and lower slkyl and alkenyl groups of from 1 to 6 carbon atoms or R5 and R6 may be concatenated together with hydrocarbyl groups to form a naphthyl group. These compounds are free of any substituent that has a tertiary carbon atom.
~ ' ~1197~2 8 CH 2419 ~:`. Specific examples of vinyl aromatic monomers include styrene, chlorostyrene, ~ -methylstyrene, vinyl xylene, divinylbenzene, and vinyl naphthalene.
..~
~ The vinyl aromatic monomer may be copolymerized .~
:i i with materials such as those having the general formula:
.~ 8 ;. R
~ R - C(H)n ~ ~ - C ~ ~ (CH2)m ..... .
; ~ , .
wherein the dotted lines each represent a single or a double carbon to carbon bond; R7 and R8 taken together represent a I C) C--O--C linkage; R is selected from the group consis~ting of : hydrogen, vinyl, alkyl of from 1 to 12 carbon atoms, alkenyl of ; from 1 to 12 carbon atoms, alkylcarboxylic of from 1 to 12 ~ :.
carbon atoms, and alkenylcarboxylic of from 1 to 12 carbon ~.
~ ~ .
atoms; n is 1 or 2, depending on the position of the carbon- ;
carbon double bond; and m is an integer of fxom 0 to about 1~. . .
li Examples include maleic anhydride, citraconic anhydride, ita- :
;',,,~! 20 conic anhydride, aconitic anhydride, and the like.
,:
i Merely by way of illustration, the styrene resins (ii) include homopolymers such as polystyrene and monochloro~
; polystyrene, the modified polystyrenes, such ~s rubber~ ~:
" ~
modified, high-impact polystyrene, and the styrene containing i copolymers, such as the styrene-acrylonitrile copolymers, ~! styrene-butadiene copolymers, styrene~acrylonitrile-o~ kyl .. styrene copolymers, styrene-acrylonitrile-butadiene copolymers, : ,, ~- poly-~ -methyl-styrene, copolymers of ethylvinylbenzene, and divinylbenzene, styrene-maleic anhydride copolymers, styrene- ~.
i 30 butadiene-styrene block copolymers and styrene-butadiene block copolymers, and styrene-butadiene-styrene maleic ~ anhydride block copolymers. -~ 8 C~ 2419 The styrene-maleic anhydride copolymers are described in U.S. 3,336,267 dated August 15, 1967 and U.S.
2,769,804 dated November 6, 1956.
Especially preferred styrene resins are homopoly-styrene and rubber-modified high-impact polystyrene resins, i.e., those which have been modified by natura] or synthetic polymeric materials which are elastomers at room temperature, e.g., 20 to 25C~, such as polystyrene resins containing poly-butadiene or ruhbery styrene-butadiene copolymers.
A preferred high-impact polystyrene is FG 834, available from Foster-Grant Co., which is a rubber-modiEied high-impact polystyrene containing about 8% polybutadiene rubber. A preferred low molecular weight homopolystyrene is KPTL-5, commercially available from Arco Polymers, Inc., Pittsburgh, Pa., having a number average molecular weight of about 40,000. A preferred homopolystyrene of relatively high molecular weight is DYL-8G, with a number average molecular weight of about 150,000, also available from Arco.
Radial teleblock copolymers are available commercially or can be prepared by following the teachings of the prior art. As an illustration, they can be made by poly-merizing conjugated dienes, e.g., butadier~e, and vinyl aromatic compounds, e.g., styrene in the presence of an organo-metallic initiator, e.g., n-butyllithium, to produce copolymers which contain an ac-tive metal atom, such as lithium, on one end of each of the polymer chains. These metal atom-terminated polymers are then reacted wi-th a coupling agent which has at least three active sites capable of reacting with the carbon-metal atom bonds on the polymer chains and replacing the metal atoms on the chains. This results in polymers which have relatively long branches which radiate from a nucleus formed by the poly~functional coupling agent. Such a method of ~ 8CH 2419 .'~
preparation is described in detail in Zelinski et al., U.S.
3,281,383 dated October 25, 1966.
The coupling agents for radial teleblock copolymers ~~ can be chosen from among polyepoxides, polyisocyanates, poly-^~ imines, polyaldehydes, polyketones, polyanhydrides, polyesters, polyhalides and the like. These materials can contain two or more types of functional groups, such as the ;:;
combination of epoxy and aldehyde groups or isocyanate and halide groups. The coupling agents are described in detail - 10 in the above-mentioned U.S. 3,281,383 dated October 25, 1966.
The conjugated dienes of radial teleblock copolymers include compounds such as 1,3-butadiene, isoprene, 2,3-dimethyl 1,3-butadiene, 1,3-pentadiene, 3-butyl-1, .
3-octadiene, and the like.
The vinyl aromatic polymers may be prepared from ~i - vinyl aromatic compounds of Formula II. They include styrene, l-vinylnaphthalene, 2-vinylnaphthalene, and the alkyl, cyclo-alkyl, aryl, alkaryl, and aralkyl derivatives thereof.
Examples include 3-methylstyrene, 4-n-propylstyrene,
The coupling agents for radial teleblock copolymers ~~ can be chosen from among polyepoxides, polyisocyanates, poly-^~ imines, polyaldehydes, polyketones, polyanhydrides, polyesters, polyhalides and the like. These materials can contain two or more types of functional groups, such as the ;:;
combination of epoxy and aldehyde groups or isocyanate and halide groups. The coupling agents are described in detail - 10 in the above-mentioned U.S. 3,281,383 dated October 25, 1966.
The conjugated dienes of radial teleblock copolymers include compounds such as 1,3-butadiene, isoprene, 2,3-dimethyl 1,3-butadiene, 1,3-pentadiene, 3-butyl-1, .
3-octadiene, and the like.
The vinyl aromatic polymers may be prepared from ~i - vinyl aromatic compounds of Formula II. They include styrene, l-vinylnaphthalene, 2-vinylnaphthalene, and the alkyl, cyclo-alkyl, aryl, alkaryl, and aralkyl derivatives thereof.
Examples include 3-methylstyrene, 4-n-propylstyrene,
4-cyclohexylstyrene, 4-dodecylstyrene, 2-ethyl-4-benzylstyrene, , !
4-p-tolystyrene, 4-(4-phenyl-n-butyl) styrene, and the like.
I ~ .
Hydrogenation of radial teleblock copolymers to ; form the hydrogenated radial teleblock copolymers (iii) can;
be carried out by any of several known procedures. See by i way of illustration, de Vault, U.S. 3,696,088.
In preferred compositions, the hydrogenated radial teleblock copolymer will be a radial teleblock copolymer of styrene and a saturated rubber, with terminal blocks derived from styrene, and a coupling agent selected from epoxidized polybutadiene, SiC14, or mixtures thereof. Especially preferred epoxidized polybutadiene coupling agents are available commer-., .
.~ _ g _ X
.
' ' ' ` "' ~ CEi 2~19 ,"
cially under the trade names Oxiron 2000 and O~iron 2001.
The molecular weight of the hydrogenated radial teleblock copolymer and the ratios of the co-monomers thereof can vary broadly. In preferred embodiments the molecular weight of the hydrogenated radial teleblock copolymer will be from about 75,000 to about 350,000 and will comprise from 1 to 45 parts by weight of the vinyl aromatic compound and from 99 to 55 parts by weight of the saturated rubber, based on the weight of the radial teleblock copolymer. The amount of coupling agent in the copolymer will depend on the particular agent and the amount of organometal:Lic initiator used. Gen-erally, relatively small amounts of coupling agent, e.g., from 0.1 to l part by weight per 100 parts of resin are em-ployed.
Preferred hydrogenated radial teleblock copolymers . r~
include Solprene 502 and 512 (containing about 70 parts by weight of hydrogenated butadiene units and about 30 parts by weight of styrene units), which are available commercially from Philips Petroleum Co., Stowe, Ohio. These ma-terials also include a relatively ~linor amount of a coupling agent, e.g., less than l part by weight of a coupling agent per 100 parts by weight of copolymer.
Components (i), (ii), and (iii) are combinable in a fairly wide range of proportions. Preferably, the compo-sitions of this invention will comprise from about 10 to about 65 parts by weight of polyphenylene ether resin (i), from about 90 to about 35 parts by weight of styrene resin (ii), and from about 1 to about 25 parts by weight of hydrogenated radial teleblock copolymer (iii), based on the total weight of the composition.
The compositions of the invention can also include other ingredients, such as flame-retardants, extenders, processing aids, pigments, stabilizers, and the like, for ~ 8 CH 2419 their conventionally employed purposes. Reinforcing fillers, in amounts sufficient to impart reinforcement, can be used, such as aluminum, iron or nickel, and the like, and non-metals, such as carbon filaments, silicates, such as acicular calcium silicate, asbestos, titanium dioxide, potassium titanate and titanate whiskers, glass flakes and fibers, and the like.
It is to be understood that, unless the filler adds to the strength and stiffness of the composition, it is only a filler and not a reinforcing filler as contemplated herein. In particular, the reinforcing fillers increase the flexural strength, the flexural modulus, the tensile strength and the heat distortion temperature.
Although it is only necessary to have at least a reinforcing amount of the reinforcement present, in general, the combination of components (i), (ii), and (iii) will comprise from about 10 to about 90 parts by weight and the filler will comprise from about 10 to about 90 parts by weight of the total composition.
In particular, the preferred reinforcing fillers are of glass, and it. is preferred to use fibrous glass fila-ments comprised of lime-aluminum borosilicate glass that is relatively soda free. This is known as "E" glass. However, other glasses are useful where electrical properties are not so important, e.g., the low soda glass known as "C" glass.
The filaments are made by standard processes, e.g., by steam or air blowing, by flame blowing, or by mechanical pulling.
The preferred filaments for plastics reinforcement are made by mechanical pulling. The filament diameters range from ; about 0.000112" to 0.00075", but this is not critical to the present invention.
In general, the best properties will be obtained if the sized filamentous glass reinforcement comprises from 7~
about 1 -to about 80% by weight based on the combined weight of glass and polymers and preferably from about 10 to about 50% by weight. Especially preferably the glass will comprise from about 10 to about 40% by weight based on the combined weight of glass and resin. Generally, for direct molding use, up to about 60% of glass can be present without causing flow ; problems. However, it is useful also to prepare the compositions containing substantially greater quantities, e.g., up to 70-80% by weight of glass. These concentrates can then be custom blended with resin compostions that are not glass reinforced to provide any desired glass content of a lower value.
The length of the glass filaments and whether or not they are bundled into fibers and the fibers bundled in turn to yarns, ropes or rovings/ or woven into mats, and the like, are also not critical to the invention. However, in preparing the p:resent compositions it is convenient to use the filamentous glass in the form of chopped strands of from about 1/8" to about 1" long, preferab]y less than 1/4" long.
In articles molded from the compositions, on the other hand, even shorter lengths will be encountered because, during compounding, considerable fragmentation will occur. This is desirable, however, because the best properties are exhibited by thermoplastic injection molded articles in which the fila-ment lengths lie between about 0.000005" and 0.125'l Because i* has been found that certain commonly used flammable sizings on the glass, e.g., dextrinized starch or synthetic polymers, contribute flammability often in greater proportion than expected from the amount present, it is preferred to use lightly sized or unsized glass rein-forcements in those compositions of the present invention which are flame-.retardant. Sizings, if present, can readily ~ 8 CH 2419 be removed by heat cleaning or other techniques well known to those skilled in the art.
It is a preferred feature of this invention also to provide flame-retardant thermoplastic compositions, as defined above, by modifying the composition to include a flame-retardant additive in a minor proportion but in an amount at least sufficient to render the composition non-burning or self-extinguishing.
A preferred feature of the invention is a flame-retardant composition as above defined, which also includes a halogenated organic compound, a halogenated organic compound in admixture with an antimony compound r elemental phosphorus, or a phosphorus compound or compounds containing phosphorus-nitrogen bonds, or a mixture of two or more of the foregoing.
When used herein, the terms "non-burning", "self extinguishing", and "non-dripping" are used to describe compo-sitions which meet the standards of ASTM test method D-635 and Underwriters' Laboratories Bulletin No.94. Another recognized procedure to determine flame resistance of resinous compositions is the Oxygen Index Test or LOI (Limiting Oxygen Index). This test is a direct measure of a products combus-tibility based on the oxygen content of the combustion atmo-sphere. Appropriate specimens are placed in a combustion chimney, and the oxygen is reduced stepwise until the material no longer supports a flame. The IOI is defined as the percent oxygen times 100 divided by the sum of the percentages of nitrogen and oxygen in the gas used to burn the material under test. Further details of the Oxygen Index Test are found in ASTM test Method D-2863~ The compositions of this invention which contain flame~retardant additives in the speci~ied amounts have a substantially higher oxygen index and thus are much less combustible than the controls.
~ 7,~ 8 CH 2419 The flame-retardant additives useful in this inven-tion comprise a family of chemica] compounds well known to those skilled in the axt. Cenerally speaking, the more important of these compounds contain chemical elements employed for their ability to impart flame resistance, e.g., bromine, chlorine, antimony, phosphorus, and nitrogen. It is preferred tha-t the flame-retardant additive comprise a halogenated organic compound (brominated or chlorinated); a halogen-containing organic compound in admixture with antimony oxide; elemental phosphorus or a phosphorus compound; a halogen-containing compound in admixture with a phosphorus compound or compounds containing phosphorus-nitrogen bonds;
or a mixture of two or more of the foregoing.
The amount of flame-retardant additive used is not critical to the invention, so long as it is present in a minor proportion based on the thermoplastic composition -- major proportions will detract from physical properties -- but at least sufficient to render the composition non-burning or self-extinguishing. Those skilled in the art are well aware that the amount will vary with the nature of the polymers in the composition and with the efficiency of the additive. In gen-eral, however, the amount of additive will be from about 0.5 to 50 parts be weight per hundred parts of components (i), (ii), and (iii). A preferred range will be from about 3 to 25 parts and an especially preferred range will be from about
4-p-tolystyrene, 4-(4-phenyl-n-butyl) styrene, and the like.
I ~ .
Hydrogenation of radial teleblock copolymers to ; form the hydrogenated radial teleblock copolymers (iii) can;
be carried out by any of several known procedures. See by i way of illustration, de Vault, U.S. 3,696,088.
In preferred compositions, the hydrogenated radial teleblock copolymer will be a radial teleblock copolymer of styrene and a saturated rubber, with terminal blocks derived from styrene, and a coupling agent selected from epoxidized polybutadiene, SiC14, or mixtures thereof. Especially preferred epoxidized polybutadiene coupling agents are available commer-., .
.~ _ g _ X
.
' ' ' ` "' ~ CEi 2~19 ,"
cially under the trade names Oxiron 2000 and O~iron 2001.
The molecular weight of the hydrogenated radial teleblock copolymer and the ratios of the co-monomers thereof can vary broadly. In preferred embodiments the molecular weight of the hydrogenated radial teleblock copolymer will be from about 75,000 to about 350,000 and will comprise from 1 to 45 parts by weight of the vinyl aromatic compound and from 99 to 55 parts by weight of the saturated rubber, based on the weight of the radial teleblock copolymer. The amount of coupling agent in the copolymer will depend on the particular agent and the amount of organometal:Lic initiator used. Gen-erally, relatively small amounts of coupling agent, e.g., from 0.1 to l part by weight per 100 parts of resin are em-ployed.
Preferred hydrogenated radial teleblock copolymers . r~
include Solprene 502 and 512 (containing about 70 parts by weight of hydrogenated butadiene units and about 30 parts by weight of styrene units), which are available commercially from Philips Petroleum Co., Stowe, Ohio. These ma-terials also include a relatively ~linor amount of a coupling agent, e.g., less than l part by weight of a coupling agent per 100 parts by weight of copolymer.
Components (i), (ii), and (iii) are combinable in a fairly wide range of proportions. Preferably, the compo-sitions of this invention will comprise from about 10 to about 65 parts by weight of polyphenylene ether resin (i), from about 90 to about 35 parts by weight of styrene resin (ii), and from about 1 to about 25 parts by weight of hydrogenated radial teleblock copolymer (iii), based on the total weight of the composition.
The compositions of the invention can also include other ingredients, such as flame-retardants, extenders, processing aids, pigments, stabilizers, and the like, for ~ 8 CH 2419 their conventionally employed purposes. Reinforcing fillers, in amounts sufficient to impart reinforcement, can be used, such as aluminum, iron or nickel, and the like, and non-metals, such as carbon filaments, silicates, such as acicular calcium silicate, asbestos, titanium dioxide, potassium titanate and titanate whiskers, glass flakes and fibers, and the like.
It is to be understood that, unless the filler adds to the strength and stiffness of the composition, it is only a filler and not a reinforcing filler as contemplated herein. In particular, the reinforcing fillers increase the flexural strength, the flexural modulus, the tensile strength and the heat distortion temperature.
Although it is only necessary to have at least a reinforcing amount of the reinforcement present, in general, the combination of components (i), (ii), and (iii) will comprise from about 10 to about 90 parts by weight and the filler will comprise from about 10 to about 90 parts by weight of the total composition.
In particular, the preferred reinforcing fillers are of glass, and it. is preferred to use fibrous glass fila-ments comprised of lime-aluminum borosilicate glass that is relatively soda free. This is known as "E" glass. However, other glasses are useful where electrical properties are not so important, e.g., the low soda glass known as "C" glass.
The filaments are made by standard processes, e.g., by steam or air blowing, by flame blowing, or by mechanical pulling.
The preferred filaments for plastics reinforcement are made by mechanical pulling. The filament diameters range from ; about 0.000112" to 0.00075", but this is not critical to the present invention.
In general, the best properties will be obtained if the sized filamentous glass reinforcement comprises from 7~
about 1 -to about 80% by weight based on the combined weight of glass and polymers and preferably from about 10 to about 50% by weight. Especially preferably the glass will comprise from about 10 to about 40% by weight based on the combined weight of glass and resin. Generally, for direct molding use, up to about 60% of glass can be present without causing flow ; problems. However, it is useful also to prepare the compositions containing substantially greater quantities, e.g., up to 70-80% by weight of glass. These concentrates can then be custom blended with resin compostions that are not glass reinforced to provide any desired glass content of a lower value.
The length of the glass filaments and whether or not they are bundled into fibers and the fibers bundled in turn to yarns, ropes or rovings/ or woven into mats, and the like, are also not critical to the invention. However, in preparing the p:resent compositions it is convenient to use the filamentous glass in the form of chopped strands of from about 1/8" to about 1" long, preferab]y less than 1/4" long.
In articles molded from the compositions, on the other hand, even shorter lengths will be encountered because, during compounding, considerable fragmentation will occur. This is desirable, however, because the best properties are exhibited by thermoplastic injection molded articles in which the fila-ment lengths lie between about 0.000005" and 0.125'l Because i* has been found that certain commonly used flammable sizings on the glass, e.g., dextrinized starch or synthetic polymers, contribute flammability often in greater proportion than expected from the amount present, it is preferred to use lightly sized or unsized glass rein-forcements in those compositions of the present invention which are flame-.retardant. Sizings, if present, can readily ~ 8 CH 2419 be removed by heat cleaning or other techniques well known to those skilled in the art.
It is a preferred feature of this invention also to provide flame-retardant thermoplastic compositions, as defined above, by modifying the composition to include a flame-retardant additive in a minor proportion but in an amount at least sufficient to render the composition non-burning or self-extinguishing.
A preferred feature of the invention is a flame-retardant composition as above defined, which also includes a halogenated organic compound, a halogenated organic compound in admixture with an antimony compound r elemental phosphorus, or a phosphorus compound or compounds containing phosphorus-nitrogen bonds, or a mixture of two or more of the foregoing.
When used herein, the terms "non-burning", "self extinguishing", and "non-dripping" are used to describe compo-sitions which meet the standards of ASTM test method D-635 and Underwriters' Laboratories Bulletin No.94. Another recognized procedure to determine flame resistance of resinous compositions is the Oxygen Index Test or LOI (Limiting Oxygen Index). This test is a direct measure of a products combus-tibility based on the oxygen content of the combustion atmo-sphere. Appropriate specimens are placed in a combustion chimney, and the oxygen is reduced stepwise until the material no longer supports a flame. The IOI is defined as the percent oxygen times 100 divided by the sum of the percentages of nitrogen and oxygen in the gas used to burn the material under test. Further details of the Oxygen Index Test are found in ASTM test Method D-2863~ The compositions of this invention which contain flame~retardant additives in the speci~ied amounts have a substantially higher oxygen index and thus are much less combustible than the controls.
~ 7,~ 8 CH 2419 The flame-retardant additives useful in this inven-tion comprise a family of chemica] compounds well known to those skilled in the axt. Cenerally speaking, the more important of these compounds contain chemical elements employed for their ability to impart flame resistance, e.g., bromine, chlorine, antimony, phosphorus, and nitrogen. It is preferred tha-t the flame-retardant additive comprise a halogenated organic compound (brominated or chlorinated); a halogen-containing organic compound in admixture with antimony oxide; elemental phosphorus or a phosphorus compound; a halogen-containing compound in admixture with a phosphorus compound or compounds containing phosphorus-nitrogen bonds;
or a mixture of two or more of the foregoing.
The amount of flame-retardant additive used is not critical to the invention, so long as it is present in a minor proportion based on the thermoplastic composition -- major proportions will detract from physical properties -- but at least sufficient to render the composition non-burning or self-extinguishing. Those skilled in the art are well aware that the amount will vary with the nature of the polymers in the composition and with the efficiency of the additive. In gen-eral, however, the amount of additive will be from about 0.5 to 50 parts be weight per hundred parts of components (i), (ii), and (iii). A preferred range will be from about 3 to 25 parts and an especially preferred range will be from about
5 to 15 parts of additive per 100 parts of (i), (ii), and (iii).
Smaller amounts of compounds highly concentrated in the ele-ments responsible for flame-retardance will be sufficient, e.g., elemental red phosphorus will be preferred at about 0.5 to 10 parts by weight per hundred parts of (i), (ii), and (iii), while phosphorus in the form of triphenyl phosphate will be used at about 5 to 25 parts of phosphate per part of ~ 8 C~ 2419 (i~, (ii), and (iii), and so forth. Halogenated aromatics will be used at about 2 to 20 parts and synergists, e.g., antimony oxide, will be used at about 1 to 10 parts by weight per 100 parts of components (i), (ii), and (iii).
Among the useful halogen containing compounds are those of the formula ( ~ ~ ~ b ~ ~ c ) wherein n is 1 to 10 and R is an alkylene, alkylidene, or cycloaliphatic linkage, e.g., methylene, ethylene, propylene, isopropylene, isopropylidene, butylene, isobutylene, amylene, cyclohexylene, cyclopentylidene, and the like; or a linkage selected from the group consisting of ether; carbonyl; amine;
a sulfur-containing linkage, e.g., sulfide, sulfoxide, or sulfone; carbonate; a phosphorus-containing linkage; and the like. R can also consist of two or more alkylene or alkylidene lin]cages connected by such groups as aromatic, amino, ether, ester, carbonyl, sulfide, sulfoxide, sulfone, a phosphorus-containing linkage, and the like. R can be dihydric phenol, e.g., bisphenol-A, carbonate linkage. Other groups which are represented by R will occur to those skilled in the art.
Ar and Ar' are ~mono- or polycarbocyclic aromatic groups such as phenylene, biphenylene, terphenylene, naphthylene, and the like. Ar and Ar' may be the same or different.
X is a monovalent hydrocarbon group exemplified by ' ~ 8 ~H 2419 `
the following: alkyl groups, such as methyl, ethyl, propyl, isopropyl, butyl, decyl, and the like, aryl groups, such as phenyl, naphthyl, biphenyl, xylyl, totyl, and the like; aralkyl groups, such as benzyl, ethylphenyl, and the like; cyclo-aliphatic groups, such as cyclopentyl, cyclohexyl, and the li]~e, as well as monovalent hydrocarbon groups containing inert substituents therein. It will be understood that where more than one X is used, they may be alike or different.
Y is a substituent selected from the group consisting of organic, inorganic, and organometallic radicals. The sub-stituents represented by Y include (1) halogen, eOg., chlorine, bromine, iodine, or fluorine, (2) ether groups of the general formula OE, wherein E is a monovalent hydrocarbon radical ~; similar to X, (3) monovalent hydrocarbon groups of the type represented by R, and (4) other substituents, e.g., nitro, cyano, etc., said substituents being essentially inert provided there be at least one and pxeferably two halogen atoms per aryl, e.g., phenyl, nucleus.
The letter d represents a whole number ranging from 1 to a maximum equivalent to the number of replaceable hydrogens substituted on the aromatic rings comprising Ar or Ar'.
The letter e represents a whole number ranging from 0 to a maximum controlled by the number of replaceable hydrogens on R. The letters a,b, and c represent whole numbers including 0. When b is not 0, neither a nor c may be 0, and when b is 0, either a or c, but not both, may be 0. Where b is 0, the aromatic groups are ~oined by a direct carbon-carbon bond.
The hydroxyl and Y substituents on the aromatic groups, Ar and Ar', can be varied in the ortho, meta, or para positions on the aromatic rings, and -the groups can be in any possible geometric relationship with respect to one another.
~ 8 ~H 2419 :
Included withln the scope of the above formula are di-aromatics of which the following axe representative 2,2-bi.s (3,5-dichlorophenyl~propane bis-(2-chlorophenyl)methane bis-(2,6-dibromophenyl)methane l,l-bis-(4-iodophenyl)ethane 1,2-bis-(2,6-dichlorophenyl)ethane l,l-bis-(2-chloro-4-iodophenyl)ethane l,l-bis-(2-chloro-4-methylphenyl)ethane 1,1-bis-(3,5-dichlorophenyl)ethane 2,2-bis-(3-phenyl~4-bromophenyl)ethane 2,3-bis-(4,6-dichloronaphthyl)propane 2,2-bis-(2,6-dichlorophenyl)pentane 2,2-bis-(3,5-dichromophenyl)hexane bis-(4-chlorophenyl)phenylmethane bis-(3,5-di.chlorophenyl)cyclohexylmethane bis-(3-nitro-4-bromophenyl)methane bis-(4-hydroxy-2,6-dichloro-3-methoxyphenyl)methane 2,2-bis-(3,5-dichloro-4-hydroxyphenyl~propane 2,2-bis-(3-bromo-4-hydroxyphenyl)propane The preparation of these and other applicable bi-phenyls are known in the art~ In the above examples sulfide, sulfoxy, and the like may be substituted in place of the di-valent aliphatic group.
Included within the above structural formula are substituted benzenes exemplified by tetrabromobenzene, hexachlorobenzene, hexabromobenzene, and biphenyls such as 2,2'-dichlorobiphenyl, 2,4'-dibromobiphenyl, 2,4'-dichloro-biphenyl, hexabromobiphenyl, octabromobiphenyl, decabromo-biphenyl, and halogenated diphenyl ethers containing from 2 to lO halogen atoms.
The preferred halogen compounds for this invention ~ 7~ 8 CH 2419 are aromatic halogen compounds such as chlorinated benzene, brominated benzene r chlorinated biphenyl, chloxinated terphenyl, brominated biphenyl, brominated terphenyl, or a compound comprising two phenyl radicals separated by a divalent alkylene group and having at least two chlorine or bromine atoms per phenyl nucleus, or mixtures of at least two of the foregoing.
Especially preferred are hexabromobenzene and chlorinated biphenyls or terphenyls, alone, or mixed with antimony oxideO
Special mention is made of flame-retardant additives consisting of aromatic carbonate homopolymers having repeating units of the formula.
(Xl~m Rl (~2)r ~ \\ 11 ~
~ c ~ o c~oJ
wherein R and R are hydrogerL, (:Lower)alkyl or phenyl, Xl and x2 are bromo or chloro and m and r are from 1 to 4. These materials may be prepared by techniques well known to those skilled in the art. Also preferred are aromatic carbonate copolymers in which from 25 to 75 weight percent of the repeating units comprise chloro- or bromo-substituted dihydric phenol, glycol or dicarboxylic acid units. See, e.g., A. D. Wambach, U.S. 3,915,926 dated October 28, 1975 above mentioned.
An especially preferred flame-retardant agent will comprise an aromatic carbonate copolymer of tetrabromobis-phenol-A and bisphenol-A, preferably in a 50:50 ratio, in ~ CH 2419 combination with an organic or inorganic antimony containing compound, e.g., antimony oxide, prepared as described in U.S. 3,915,926 above mentioned.
In general, the preferred phosphate compounds are selected from the group of elemental phosphorus and organic phosphonic acids, phosphonates, phosphinates, phosphonites, phosphinites, phosphene oxides, phosphines, phosphites, and phosphates. Illustrative is triphenyl phosphene oxide. These can be used alone or mixed with hexabromobenzene or a chlori-nated biphenyl and, optionally, antimony oxide.
Typical of the preferred phosphorus compounds to be employed in this invention would be those having the general formula O .
Il .
QO -~ P - OQ
OQ
and nitrogen analogs thereof where each Q represents the same or different radicals including hydrocarbon radicals such as alkyl, cycloalkyl, aryl, alkyl substituted aryl, and aryl substituted alkyl; halogen; hydrogen; and combinations thereof provided that at least one of said Q's is aryl. Typical examples of suitable phosphates include, phenylbisdodecyl phosphate, phenylbisneopentyl phosphate, phenylethylene hydrogen phosphate, phenylbis~(3,5,5'-trimethylhexyl phosphate), ethyl-diphenyl phosphate, 2-ethylhexyl di(p-tolyl) phosphate, diphenyl hydrogen phosphate, bis(2-ethylhexyl? p-tolylphosphate, tritolyl phosphate, bis-(2-ethylhexyl)-phenyl phosphate, tri - (nonylphenyl) phosphate, phenylmethyl hydrogen phosphate, di(dodecyl) p-tolyl phosphate~ tricresyl phosphate, triphenyl ~' phosphate, halogenated triphenyl phosphate, dibutylphenyl phosphate, 2-chloroethyl-diphenyl phosphate, p-toly:L bis( 2,5,5'-trimethylhexyl) phosphate, 2-ethylhexyldiphenyl phosphate, diphenyl hydrogen phosphate, and the like. The preferred phosphates are those where each Q is aryl. The most preferred phosphate is triphenyl phosphate. It is also pre-ferred to use triphenyl phosphate in combination with hexabromobenzene and, optionally, antimony oxide.
Also suitable as flame-retardant additives for this invention are compounds containing phosphorus-nitrogen bonds, such as phosphonitrilic chloride, phosphorus ester amides, phosphoric acid amides, phosphonic acid amides, phosphinic acid amides, tris(axiridinyl)phosphine oxide, or tetrakis (hydroxymethyl) phosphonium chloride. These flame-retardant additives are commercially available.
The compositions of the invention may be formed by conventional techniques, that is, by first dry mixing the components to form a premix, and then passing the premix through an extruder at an elevated temperature, e.g., 425 to 640 F.
By way of illustration, glass roving (a bundle of strands of filaments) is chopped into small pieces, e.g., l/8" to l" in length, and preferably less than l/4" in length and put into an extrusion compounder with (i) the polyphenylene ether resin, (ii) the styrene resin, (iii) the hydroyenated radial teleblock copolymer, and (iv) the flame-retardant additive (s), to produce molding pellets. The fibers are shortened and predispersed in the process, coming out a~ less than l/16" long. In another procedure, glass filaments are ground or milled to short lengths, are mixed with the polyphenylene ether resin, the styrene resin, the radial teleblock copolymer, and optionally, flame-retardant - 20 ~
~ 8 CH 2419 additive, by dry blending, and then are either fluxed on a mill and ground, or are extruded and chopped.
In addition~ compounding should be carried out to insure that the residence time in the machine is short;
that the temperature is carefully controlled; that -the frictional heat is utilized; and that an intimate mixture between the resins and the additives is obtained.
The following examples are set forth as further illustration of the invention and are not to be construed as limiting the invention thereto.
Comparative Example I. (Sample A) A premix comprised of 55 parts by weight of poly-(2,6-dimethyl-1,4-phenylene)ether resin (PPO), and 45 parts by weight of Foster-Grant's Fostuflex 834 (FG 834), a rubber-modified polystyrene containing about 8% polybutadiene rubber was prepared by dry mixing these components with 4 parts tri-phenyl phosphate, 1.5 parts polyethylene, 1 part tridecyl-phosphite, 0.15 parts zinc sulfide, and 0~15 parts zinc oxide.
The premix was then compounded on a 28mm twin-screw extruder at about 500F. The extrudate was cooled and chopped into pellets~ and the pellets were molded into test bars on a Newbury injection molding machine.
Example I. (Sample B) Comparative Example I was repeated with the ex-ception that the 45 parts of FG 834 were replaced by 30 parts of Sinclair-Kopper Co.'s Dylene-8G (DYL-8G), "crystal'~ poly-styrene, and phillips Petroleum's Solprene 502CX ~SOL-502), which is a radial teleblock copolymer containing hydrogenated rubber blocks.
Example II.
The composition prepared in the Comparative Example and Example I were tested, and the results were as follows:
7~
Composition ToY~ T.E. Izod GIMP HDT GLOSS MV
Sample A 8900 83 3.0 210 245 53 2100 Sample B 7900 20 6.0 225 259 65 2150 T.Y. - Tensile Yield Strength (psi) T.E. - Tensile Elongation ~%) Izod - Notched Izod Impact Strength (ft. lbs./in. notch) GIMP - Gardner Impact (in. lbs.) HDT - Heat Deflection Temperature ( F) &LOSS - 45" Surface Gloss (dimensionless) MV - Melt Viscosity @ 540F, 1500 sec 1 (poise) As can be seen above, a thermoplastic composition in accordance with the invention, Sample B, demonstrated improved impact resistance and unexpected improvements in surface gloss over a typical commercial composition, Sample A.
Comparative Example II. (Sample C) A premix comprised of 50 par-ts by weight of PPO and 50 parts by weight FG 834 was prepared by dry mixing these components with 3 parts triphenyl phosphate, 1.5 parts poly-ethylene, 1 part tridecylphosphite, 0.15 parts zinc sulfide, 0.15 parts zinc oxide, and 3 parts titanium dioxide. The pre-- mix was then compounded on a 28mm twin-screw extruder at about 500F. The extrudate was cooled and chopped into pellets, and the pe]lets were molded into test bars on a Newbury injection molding machine.
Comparative Exam~le III. (Sample D) Comparative Example II was repeated with the exception that the 50 parts of FG 834 were replaced by 42 parts of DYL-8G and 8 parts of Phillips Petroleum's Solprene 411 (SOL-411), a radial teleblock copolymer comprising styrene and butadiene.
~ 8 CH 2419 Example III. (Sample E) ,, The procedure of Comparative Example II was repeated with the exception that the 50 parts of FG 834 were replaced by 38 parts of DYL-8G and 12 parts o~ SOL-502.
Example IV.
The compositions prepared in Comparative Examples II
and III and Example II were tested to determine the effect of aging, and the results were as follows:
Izod T.E.
. _ Days @ 115C _ D _ C D
Smaller amounts of compounds highly concentrated in the ele-ments responsible for flame-retardance will be sufficient, e.g., elemental red phosphorus will be preferred at about 0.5 to 10 parts by weight per hundred parts of (i), (ii), and (iii), while phosphorus in the form of triphenyl phosphate will be used at about 5 to 25 parts of phosphate per part of ~ 8 C~ 2419 (i~, (ii), and (iii), and so forth. Halogenated aromatics will be used at about 2 to 20 parts and synergists, e.g., antimony oxide, will be used at about 1 to 10 parts by weight per 100 parts of components (i), (ii), and (iii).
Among the useful halogen containing compounds are those of the formula ( ~ ~ ~ b ~ ~ c ) wherein n is 1 to 10 and R is an alkylene, alkylidene, or cycloaliphatic linkage, e.g., methylene, ethylene, propylene, isopropylene, isopropylidene, butylene, isobutylene, amylene, cyclohexylene, cyclopentylidene, and the like; or a linkage selected from the group consisting of ether; carbonyl; amine;
a sulfur-containing linkage, e.g., sulfide, sulfoxide, or sulfone; carbonate; a phosphorus-containing linkage; and the like. R can also consist of two or more alkylene or alkylidene lin]cages connected by such groups as aromatic, amino, ether, ester, carbonyl, sulfide, sulfoxide, sulfone, a phosphorus-containing linkage, and the like. R can be dihydric phenol, e.g., bisphenol-A, carbonate linkage. Other groups which are represented by R will occur to those skilled in the art.
Ar and Ar' are ~mono- or polycarbocyclic aromatic groups such as phenylene, biphenylene, terphenylene, naphthylene, and the like. Ar and Ar' may be the same or different.
X is a monovalent hydrocarbon group exemplified by ' ~ 8 ~H 2419 `
the following: alkyl groups, such as methyl, ethyl, propyl, isopropyl, butyl, decyl, and the like, aryl groups, such as phenyl, naphthyl, biphenyl, xylyl, totyl, and the like; aralkyl groups, such as benzyl, ethylphenyl, and the like; cyclo-aliphatic groups, such as cyclopentyl, cyclohexyl, and the li]~e, as well as monovalent hydrocarbon groups containing inert substituents therein. It will be understood that where more than one X is used, they may be alike or different.
Y is a substituent selected from the group consisting of organic, inorganic, and organometallic radicals. The sub-stituents represented by Y include (1) halogen, eOg., chlorine, bromine, iodine, or fluorine, (2) ether groups of the general formula OE, wherein E is a monovalent hydrocarbon radical ~; similar to X, (3) monovalent hydrocarbon groups of the type represented by R, and (4) other substituents, e.g., nitro, cyano, etc., said substituents being essentially inert provided there be at least one and pxeferably two halogen atoms per aryl, e.g., phenyl, nucleus.
The letter d represents a whole number ranging from 1 to a maximum equivalent to the number of replaceable hydrogens substituted on the aromatic rings comprising Ar or Ar'.
The letter e represents a whole number ranging from 0 to a maximum controlled by the number of replaceable hydrogens on R. The letters a,b, and c represent whole numbers including 0. When b is not 0, neither a nor c may be 0, and when b is 0, either a or c, but not both, may be 0. Where b is 0, the aromatic groups are ~oined by a direct carbon-carbon bond.
The hydroxyl and Y substituents on the aromatic groups, Ar and Ar', can be varied in the ortho, meta, or para positions on the aromatic rings, and -the groups can be in any possible geometric relationship with respect to one another.
~ 8 ~H 2419 :
Included withln the scope of the above formula are di-aromatics of which the following axe representative 2,2-bi.s (3,5-dichlorophenyl~propane bis-(2-chlorophenyl)methane bis-(2,6-dibromophenyl)methane l,l-bis-(4-iodophenyl)ethane 1,2-bis-(2,6-dichlorophenyl)ethane l,l-bis-(2-chloro-4-iodophenyl)ethane l,l-bis-(2-chloro-4-methylphenyl)ethane 1,1-bis-(3,5-dichlorophenyl)ethane 2,2-bis-(3-phenyl~4-bromophenyl)ethane 2,3-bis-(4,6-dichloronaphthyl)propane 2,2-bis-(2,6-dichlorophenyl)pentane 2,2-bis-(3,5-dichromophenyl)hexane bis-(4-chlorophenyl)phenylmethane bis-(3,5-di.chlorophenyl)cyclohexylmethane bis-(3-nitro-4-bromophenyl)methane bis-(4-hydroxy-2,6-dichloro-3-methoxyphenyl)methane 2,2-bis-(3,5-dichloro-4-hydroxyphenyl~propane 2,2-bis-(3-bromo-4-hydroxyphenyl)propane The preparation of these and other applicable bi-phenyls are known in the art~ In the above examples sulfide, sulfoxy, and the like may be substituted in place of the di-valent aliphatic group.
Included within the above structural formula are substituted benzenes exemplified by tetrabromobenzene, hexachlorobenzene, hexabromobenzene, and biphenyls such as 2,2'-dichlorobiphenyl, 2,4'-dibromobiphenyl, 2,4'-dichloro-biphenyl, hexabromobiphenyl, octabromobiphenyl, decabromo-biphenyl, and halogenated diphenyl ethers containing from 2 to lO halogen atoms.
The preferred halogen compounds for this invention ~ 7~ 8 CH 2419 are aromatic halogen compounds such as chlorinated benzene, brominated benzene r chlorinated biphenyl, chloxinated terphenyl, brominated biphenyl, brominated terphenyl, or a compound comprising two phenyl radicals separated by a divalent alkylene group and having at least two chlorine or bromine atoms per phenyl nucleus, or mixtures of at least two of the foregoing.
Especially preferred are hexabromobenzene and chlorinated biphenyls or terphenyls, alone, or mixed with antimony oxideO
Special mention is made of flame-retardant additives consisting of aromatic carbonate homopolymers having repeating units of the formula.
(Xl~m Rl (~2)r ~ \\ 11 ~
~ c ~ o c~oJ
wherein R and R are hydrogerL, (:Lower)alkyl or phenyl, Xl and x2 are bromo or chloro and m and r are from 1 to 4. These materials may be prepared by techniques well known to those skilled in the art. Also preferred are aromatic carbonate copolymers in which from 25 to 75 weight percent of the repeating units comprise chloro- or bromo-substituted dihydric phenol, glycol or dicarboxylic acid units. See, e.g., A. D. Wambach, U.S. 3,915,926 dated October 28, 1975 above mentioned.
An especially preferred flame-retardant agent will comprise an aromatic carbonate copolymer of tetrabromobis-phenol-A and bisphenol-A, preferably in a 50:50 ratio, in ~ CH 2419 combination with an organic or inorganic antimony containing compound, e.g., antimony oxide, prepared as described in U.S. 3,915,926 above mentioned.
In general, the preferred phosphate compounds are selected from the group of elemental phosphorus and organic phosphonic acids, phosphonates, phosphinates, phosphonites, phosphinites, phosphene oxides, phosphines, phosphites, and phosphates. Illustrative is triphenyl phosphene oxide. These can be used alone or mixed with hexabromobenzene or a chlori-nated biphenyl and, optionally, antimony oxide.
Typical of the preferred phosphorus compounds to be employed in this invention would be those having the general formula O .
Il .
QO -~ P - OQ
OQ
and nitrogen analogs thereof where each Q represents the same or different radicals including hydrocarbon radicals such as alkyl, cycloalkyl, aryl, alkyl substituted aryl, and aryl substituted alkyl; halogen; hydrogen; and combinations thereof provided that at least one of said Q's is aryl. Typical examples of suitable phosphates include, phenylbisdodecyl phosphate, phenylbisneopentyl phosphate, phenylethylene hydrogen phosphate, phenylbis~(3,5,5'-trimethylhexyl phosphate), ethyl-diphenyl phosphate, 2-ethylhexyl di(p-tolyl) phosphate, diphenyl hydrogen phosphate, bis(2-ethylhexyl? p-tolylphosphate, tritolyl phosphate, bis-(2-ethylhexyl)-phenyl phosphate, tri - (nonylphenyl) phosphate, phenylmethyl hydrogen phosphate, di(dodecyl) p-tolyl phosphate~ tricresyl phosphate, triphenyl ~' phosphate, halogenated triphenyl phosphate, dibutylphenyl phosphate, 2-chloroethyl-diphenyl phosphate, p-toly:L bis( 2,5,5'-trimethylhexyl) phosphate, 2-ethylhexyldiphenyl phosphate, diphenyl hydrogen phosphate, and the like. The preferred phosphates are those where each Q is aryl. The most preferred phosphate is triphenyl phosphate. It is also pre-ferred to use triphenyl phosphate in combination with hexabromobenzene and, optionally, antimony oxide.
Also suitable as flame-retardant additives for this invention are compounds containing phosphorus-nitrogen bonds, such as phosphonitrilic chloride, phosphorus ester amides, phosphoric acid amides, phosphonic acid amides, phosphinic acid amides, tris(axiridinyl)phosphine oxide, or tetrakis (hydroxymethyl) phosphonium chloride. These flame-retardant additives are commercially available.
The compositions of the invention may be formed by conventional techniques, that is, by first dry mixing the components to form a premix, and then passing the premix through an extruder at an elevated temperature, e.g., 425 to 640 F.
By way of illustration, glass roving (a bundle of strands of filaments) is chopped into small pieces, e.g., l/8" to l" in length, and preferably less than l/4" in length and put into an extrusion compounder with (i) the polyphenylene ether resin, (ii) the styrene resin, (iii) the hydroyenated radial teleblock copolymer, and (iv) the flame-retardant additive (s), to produce molding pellets. The fibers are shortened and predispersed in the process, coming out a~ less than l/16" long. In another procedure, glass filaments are ground or milled to short lengths, are mixed with the polyphenylene ether resin, the styrene resin, the radial teleblock copolymer, and optionally, flame-retardant - 20 ~
~ 8 CH 2419 additive, by dry blending, and then are either fluxed on a mill and ground, or are extruded and chopped.
In addition~ compounding should be carried out to insure that the residence time in the machine is short;
that the temperature is carefully controlled; that -the frictional heat is utilized; and that an intimate mixture between the resins and the additives is obtained.
The following examples are set forth as further illustration of the invention and are not to be construed as limiting the invention thereto.
Comparative Example I. (Sample A) A premix comprised of 55 parts by weight of poly-(2,6-dimethyl-1,4-phenylene)ether resin (PPO), and 45 parts by weight of Foster-Grant's Fostuflex 834 (FG 834), a rubber-modified polystyrene containing about 8% polybutadiene rubber was prepared by dry mixing these components with 4 parts tri-phenyl phosphate, 1.5 parts polyethylene, 1 part tridecyl-phosphite, 0.15 parts zinc sulfide, and 0~15 parts zinc oxide.
The premix was then compounded on a 28mm twin-screw extruder at about 500F. The extrudate was cooled and chopped into pellets~ and the pellets were molded into test bars on a Newbury injection molding machine.
Example I. (Sample B) Comparative Example I was repeated with the ex-ception that the 45 parts of FG 834 were replaced by 30 parts of Sinclair-Kopper Co.'s Dylene-8G (DYL-8G), "crystal'~ poly-styrene, and phillips Petroleum's Solprene 502CX ~SOL-502), which is a radial teleblock copolymer containing hydrogenated rubber blocks.
Example II.
The composition prepared in the Comparative Example and Example I were tested, and the results were as follows:
7~
Composition ToY~ T.E. Izod GIMP HDT GLOSS MV
Sample A 8900 83 3.0 210 245 53 2100 Sample B 7900 20 6.0 225 259 65 2150 T.Y. - Tensile Yield Strength (psi) T.E. - Tensile Elongation ~%) Izod - Notched Izod Impact Strength (ft. lbs./in. notch) GIMP - Gardner Impact (in. lbs.) HDT - Heat Deflection Temperature ( F) &LOSS - 45" Surface Gloss (dimensionless) MV - Melt Viscosity @ 540F, 1500 sec 1 (poise) As can be seen above, a thermoplastic composition in accordance with the invention, Sample B, demonstrated improved impact resistance and unexpected improvements in surface gloss over a typical commercial composition, Sample A.
Comparative Example II. (Sample C) A premix comprised of 50 par-ts by weight of PPO and 50 parts by weight FG 834 was prepared by dry mixing these components with 3 parts triphenyl phosphate, 1.5 parts poly-ethylene, 1 part tridecylphosphite, 0.15 parts zinc sulfide, 0.15 parts zinc oxide, and 3 parts titanium dioxide. The pre-- mix was then compounded on a 28mm twin-screw extruder at about 500F. The extrudate was cooled and chopped into pellets, and the pe]lets were molded into test bars on a Newbury injection molding machine.
Comparative Exam~le III. (Sample D) Comparative Example II was repeated with the exception that the 50 parts of FG 834 were replaced by 42 parts of DYL-8G and 8 parts of Phillips Petroleum's Solprene 411 (SOL-411), a radial teleblock copolymer comprising styrene and butadiene.
~ 8 CH 2419 Example III. (Sample E) ,, The procedure of Comparative Example II was repeated with the exception that the 50 parts of FG 834 were replaced by 38 parts of DYL-8G and 12 parts o~ SOL-502.
Example IV.
The compositions prepared in Comparative Examples II
and III and Example II were tested to determine the effect of aging, and the results were as follows:
Izod T.E.
. _ Days @ 115C _ D _ C D
6 4.5 4.0 4.3 94 89 25 11 3.0 3.3 2.5 30 20 16 28 2.2 2.1 2.4 16 7 13 1.0 1.1 1.9 6 6 10 63 1.8 9 91 1.3 8 The results unquestionably show the improved reten-tion of ductility during heat aging of Sample E, a composition in accordance with the invention, over Samples C and D, two known compositions.
Claims (22)
1. A thermoplastic molding composition which comprises an intimate admixture of:
(i) a polyphenylene ether resin;
(ii) a styrene resin; and (iii) a hydrogenated radial teleblock copolymer comprising a vinyl aromatic compound, a saturated rubber, and a coupling agent.
(i) a polyphenylene ether resin;
(ii) a styrene resin; and (iii) a hydrogenated radial teleblock copolymer comprising a vinyl aromatic compound, a saturated rubber, and a coupling agent.
2. A thermoplastic molding composition which comprises an intimate admixture of:
(i) a polyphenylene ether resin;
(ii) a styrene resin; and liii) a hydrogenated radial teleblock copolymer comprising a vinyl aromatic compound, a hydrogenated conjugated diene, and a coupling agent.
(i) a polyphenylene ether resin;
(ii) a styrene resin; and liii) a hydrogenated radial teleblock copolymer comprising a vinyl aromatic compound, a hydrogenated conjugated diene, and a coupling agent.
3. The molding composition of claim 2 wherein the polyphenylene ether resin (i) has repeating units of the structural formula:
wherein the oxygen ether atom of one unit is connected to the benzene nucleus of the next adjoining unit, n is a positive integer and is at least 50, and each Q is a monovalent substituent selected from the group consisting of hydrogen, halogen, hydrocarbon radicals free of a tertiary alpha-carbon atom, halohydrocarbon radicals having at least two carbon atoms between the halogen atom and the phenol nucleus; and wherein, in said styrene resin (ii), at least 25% by weight of repeating units of the styrene resin (ii) are derived from a vinyl aromatic monomer of the formula:
wherein R1 and R2 are selected from the group consisting of hydrogen and lower alkyl or alkenyl groups of from 1 to 6 carbon atoms; R3 and R4 are selected from the group consisting of chloro, bromo, hydrogen, and lower alkyl groups of from 1 to 6 carbon atoms; and R5 and R6 are selected from the group consisting of hydrogen and lower alkyl and alkenyl groups of from 1 to 6 carbon atoms or R5 and R6 may be concatenated together with hydrocarbyl groups to form a naphthyl group, these compounds being free of any substituent having a tertiary carbon atom.
wherein the oxygen ether atom of one unit is connected to the benzene nucleus of the next adjoining unit, n is a positive integer and is at least 50, and each Q is a monovalent substituent selected from the group consisting of hydrogen, halogen, hydrocarbon radicals free of a tertiary alpha-carbon atom, halohydrocarbon radicals having at least two carbon atoms between the halogen atom and the phenol nucleus; and wherein, in said styrene resin (ii), at least 25% by weight of repeating units of the styrene resin (ii) are derived from a vinyl aromatic monomer of the formula:
wherein R1 and R2 are selected from the group consisting of hydrogen and lower alkyl or alkenyl groups of from 1 to 6 carbon atoms; R3 and R4 are selected from the group consisting of chloro, bromo, hydrogen, and lower alkyl groups of from 1 to 6 carbon atoms; and R5 and R6 are selected from the group consisting of hydrogen and lower alkyl and alkenyl groups of from 1 to 6 carbon atoms or R5 and R6 may be concatenated together with hydrocarbyl groups to form a naphthyl group, these compounds being free of any substituent having a tertiary carbon atom.
4. The molding composition of claim 3 wherein, in said polyphenylene ether resin (i), each Q is methyl and in said styrene resin (ii), the units are derived from styrene monomer.
5. The molding composition of claim 2 wherein said styrene resin (ii) is a low molecular weight homopolystyrene.
6. The molding composition of claim 2 wherein said styrene resin (ii) is a rubber-modified high-impact polystyrene.
7. The molding composition of claim 2 wherein said radial teleblock copolymer (iii) comprises from 1 to 45 parts by weight of the vinyl aromatic compound and from 99 to 55 parts by weight of the hydrogenated conjugated diene, and a relatively small amount of a coupling agent, based on the weight of the radial teleblock copolymer.
8. The molding composition of claim 7 wherein, in said radial teleblock copolymer (iii), the coupling agent is a polymer selected from the group consisting of polyepoxides, polyisocyanates, polyimines, polyaldehydes, polyketones, polyanhydrides, polyesters, and polyhalides.
9. The molding composition of claim 2 wherein, in said radial teleblock copolymer (iii), the vinyl aromatic compound is styrene, the saturated rubber is hydrogenated butadiene, and the coupling agent is selected from the group consisting of epoxidized polybutadiene, SiC14, and mixtures thereof.
10. The molding composition of claim 2 wherein said polyphenylene ether resin (i) is present in an amount of from about 10 to about 65 parts by weight, said styrene resin (ii) is present in an amount of from about 90 to about 35 parts by weight, and said radial teleblock copolymer (iii) is present in an amount of from about 1 to about 25 parts by weight, based on the total weight of the composition.
11. The molding composition of claim 2 which further comprises a reinforcing amount of a reinforcing filler.
12. A thermoplastic molding composition which comprises an intimate admixture of:
(i) from about 10 to about 65 percent by weight of poly(2,6-dimethyl-1,4-phenylene)ether;
(ii) from about 90 to about 35 percent by weight of polystyrene; and (iii) from about 1 to 25 percent by weight of a hydro-genated radial teleblock copolymer of styrene, hydrogenated butadiene, and an epoxidized polybutadiene coupling agent, based on the total weight of the composition.
(i) from about 10 to about 65 percent by weight of poly(2,6-dimethyl-1,4-phenylene)ether;
(ii) from about 90 to about 35 percent by weight of polystyrene; and (iii) from about 1 to 25 percent by weight of a hydro-genated radial teleblock copolymer of styrene, hydrogenated butadiene, and an epoxidized polybutadiene coupling agent, based on the total weight of the composition.
13. The molding composition of claim 12 wherein said polystyrene (ii) is homopolystyrene.
14. The molding composition of claim 12 wherein said polystyrene (ii) is a rubber-modified high-impact polystyrene.
15. The molding composition of claim 12 which further comprises a glass reinforcing filler in an amount of from about 10 to about 40%, based on the combined weight of glass and resin.
16. The molding composition of claim 12 which further comprises a flame-retardant amount of a flame-retardant additive.
17. The molding composition of claim 16 wherein said flame-retardant is a halogenated organic compound, a halogenated organic compound in admixture with an antimony compound, elemental phosphorous, or a phosphorous compound or compounds containing phosphorous-nitrogen bonds, or a mixture of two or more of the foregoing.
18. The molding composition of claim 16 wherein the flame-retardant comprises a mixture of an organic bromine containing compound with antimony oxide.
19. The molding composition of claim 16 wherein the flame-retardant is triphenylphosphate.
20. A thermoplastic molding composition which comprises an intimate admixture of (i) from about 10 to about 65 parts by weight of polyphenylene ether resin;
(ii) from about 90 to about 35 parts by weight of styrene resin; and (iii) from about 1 to about 25 parts by weight of hydrogenated radial teleblock copolymer comprising a vinyl aromatic compound, a hydrogenated conjugated diene, and a coupling agent, based on the total weight of the composition.
(ii) from about 90 to about 35 parts by weight of styrene resin; and (iii) from about 1 to about 25 parts by weight of hydrogenated radial teleblock copolymer comprising a vinyl aromatic compound, a hydrogenated conjugated diene, and a coupling agent, based on the total weight of the composition.
21. The molding composition of claim 2 wherein said styrene resin (ii) comprises rubber-modified polystyrene that is modified by polymerizing styrene monomer in the presence of the rubber.
22. The molding composition of claim 12 wherein the polystyrene (ii) comprises rubber-modified polystyrene that is modified by polymerizing styrene monomer in the presence of the rubber.
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| US75202476A | 1976-12-20 | 1976-12-20 | |
| US752,024 | 1976-12-20 |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CA1119742A true CA1119742A (en) | 1982-03-09 |
Family
ID=25024524
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CA000292241A Expired CA1119742A (en) | 1976-12-20 | 1977-12-02 | Impact resistant polyphenylene ether resin compositions containing hydrogenated radial teleblock copolymers |
Country Status (12)
| Country | Link |
|---|---|
| JP (1) | JPS5394540A (en) |
| AU (1) | AU513181B2 (en) |
| BR (1) | BR7708529A (en) |
| CA (1) | CA1119742A (en) |
| DD (1) | DD133962A5 (en) |
| DE (1) | DE2750242A1 (en) |
| FR (1) | FR2374378A1 (en) |
| GB (1) | GB1559052A (en) |
| IT (1) | IT1088289B (en) |
| MX (1) | MX146397A (en) |
| NL (1) | NL7712660A (en) |
| SU (1) | SU865130A3 (en) |
Families Citing this family (12)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS55145752A (en) * | 1979-05-01 | 1980-11-13 | Asahi Chem Ind Co Ltd | Aromatic polyether resin composition |
| NL8005597A (en) * | 1979-10-15 | 1981-04-21 | Gen Electric | MIXTURES OF POLYPHENYLENE OXIDE AND SOFTENER. |
| US4309514A (en) * | 1979-11-30 | 1982-01-05 | General Electric Company | Molding compositions comprising polyphenylene ether and hydrogenated radial block copolymer of vinyl aromatic compound and diene rubber |
| US4313864A (en) | 1980-01-21 | 1982-02-02 | General Electric Company | Polyphenylene oxide/plasticizer/hydrogenated radial teleblock copolymer blends |
| JPS571733A (en) * | 1980-06-06 | 1982-01-06 | Asahi Chem Ind Co Ltd | Injection-molded form of polyphenylene ether resin having good appearance |
| US4423189A (en) * | 1981-10-28 | 1983-12-27 | General Electric Company | Compositions of a polyphenylene ether resin, low molecular weight polystyrene and a block copolymer |
| US4383082A (en) * | 1981-12-01 | 1983-05-10 | General Electric Company | Polyphenylene ether resin compositions containing polyolefin in high amount |
| DE3219048A1 (en) * | 1982-05-21 | 1983-11-24 | Basf Ag, 6700 Ludwigshafen | THERMOPLASTIC MOLDS |
| DE3434978A1 (en) * | 1984-09-24 | 1986-04-03 | Basf Ag, 6700 Ludwigshafen | THERMOPLASTIC MOLDS |
| US4994508A (en) * | 1987-07-16 | 1991-02-19 | Asahi Kasei Kogyo Kabushiki Kaisha | Specific hydrogenated block copolymer composition and process for producing the same |
| DE68922460T2 (en) * | 1988-11-01 | 1996-02-15 | Asahi Chemical Ind | Thermoplastic polymer composition. |
| EP0476366A3 (en) * | 1990-09-18 | 1992-09-30 | General Electric Company | Polyphenylene ether compositions of improved melt strength |
Family Cites Families (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US3281383A (en) * | 1962-08-09 | 1966-10-25 | Phillips Petroleum Co | Branched polymers prepared from monolithium-terminated polymers and compounds having at least three reactive sites |
| US3696088A (en) * | 1970-09-11 | 1972-10-03 | Phillips Petroleum Co | Hydrogenation process |
| JPS4830151A (en) * | 1971-08-21 | 1973-04-20 | ||
| DE2434848C2 (en) * | 1973-08-13 | 1986-09-04 | General Electric Co., Schenectady, N.Y. | Thermoplastic mass |
-
1977
- 1977-11-10 DE DE19772750242 patent/DE2750242A1/en active Granted
- 1977-11-17 NL NL7712660A patent/NL7712660A/en not_active Application Discontinuation
- 1977-11-18 GB GB48047/77A patent/GB1559052A/en not_active Expired
- 1977-11-25 IT IT30048/77A patent/IT1088289B/en active
- 1977-12-02 CA CA000292241A patent/CA1119742A/en not_active Expired
- 1977-12-16 DD DD77202721A patent/DD133962A5/en unknown
- 1977-12-16 JP JP15232177A patent/JPS5394540A/en active Pending
- 1977-12-16 MX MX171781A patent/MX146397A/en unknown
- 1977-12-19 FR FR7738187A patent/FR2374378A1/en active Granted
- 1977-12-19 SU SU772554603A patent/SU865130A3/en active
- 1977-12-19 AU AU31702/77A patent/AU513181B2/en not_active Expired
- 1977-12-20 BR BR7708529A patent/BR7708529A/en unknown
Also Published As
| Publication number | Publication date |
|---|---|
| FR2374378B1 (en) | 1983-10-28 |
| GB1559052A (en) | 1980-01-16 |
| MX146397A (en) | 1982-06-23 |
| AU513181B2 (en) | 1980-11-20 |
| JPS5394540A (en) | 1978-08-18 |
| NL7712660A (en) | 1978-06-22 |
| AU3170277A (en) | 1979-06-28 |
| DE2750242A1 (en) | 1978-06-22 |
| FR2374378A1 (en) | 1978-07-13 |
| BR7708529A (en) | 1978-08-08 |
| DD133962A5 (en) | 1979-01-31 |
| IT1088289B (en) | 1985-06-10 |
| SU865130A3 (en) | 1981-09-15 |
| DE2750242C2 (en) | 1989-02-09 |
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