CA1102032A - Flame-retardant, impact-resistant polyphenylene ether compositions - Google Patents
Flame-retardant, impact-resistant polyphenylene ether compositionsInfo
- Publication number
- CA1102032A CA1102032A CA291,790A CA291790A CA1102032A CA 1102032 A CA1102032 A CA 1102032A CA 291790 A CA291790 A CA 291790A CA 1102032 A CA1102032 A CA 1102032A
- Authority
- CA
- Canada
- Prior art keywords
- composition
- block
- self
- butadiene
- extinguishing
- 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
Links
Classifications
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K5/00—Use of organic ingredients
- C08K5/49—Phosphorus-containing compounds
- C08K5/51—Phosphorus bound to oxygen
- C08K5/52—Phosphorus bound to oxygen only
- C08K5/521—Esters of phosphoric acids, e.g. of H3PO4
- C08K5/523—Esters of phosphoric acids, e.g. of H3PO4 with hydroxyaryl compounds
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K5/00—Use of organic ingredients
- C08K5/49—Phosphorus-containing compounds
- C08K5/51—Phosphorus bound to oxygen
- C08K5/52—Phosphorus bound to oxygen only
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K5/00—Use of organic ingredients
- C08K5/49—Phosphorus-containing compounds
- C08K5/51—Phosphorus bound to oxygen
- C08K5/52—Phosphorus bound to oxygen only
- C08K5/524—Esters of phosphorous acids, e.g. of H3PO3
- C08K5/526—Esters of phosphorous acids, e.g. of H3PO3 with hydroxyaryl compounds
-
- 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
- C08L25/06—Polystyrene
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L33/00—Compositions of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides or nitriles thereof; Compositions of derivatives of such polymers
- C08L33/04—Homopolymers or copolymers of esters
- C08L33/06—Homopolymers or copolymers of esters of esters containing only carbon, hydrogen and oxygen, which oxygen atoms are present only as part of the carboxyl radical
- C08L33/10—Homopolymers or copolymers of methacrylic acid esters
-
- 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
- C08L53/02—Compositions of block copolymers containing at least one sequence of a polymer obtained by reactions only involving carbon-to-carbon unsaturated bonds; Compositions of derivatives of such polymers of vinyl-aromatic monomers and conjugated dienes
-
- 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
- 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
- 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
Landscapes
- Chemical & Material Sciences (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- Compositions Of Macromolecular Compounds (AREA)
Abstract
ABSTRACT OF THE DISCLOSURE
Self-extinguishing thermoplastic molding compositions having high impact resistance and good surface appearance are disclosed which comprise, in admixture, (a) a normally flammable composition comprising a polyphenylene ether resin and a polymer selected from the group consisting of a hydrogenated A-B-A1 block copolymer and an acrylic resin modified diene rubber containing resin, and (b) an aromatic phosphate compound in an amount at least sufficient to render the normally flammable composition self-extinguishing and, after molding, impact resistant and having a high surface glass as required for use in many commercial applications.
Self-extinguishing thermoplastic molding compositions having high impact resistance and good surface appearance are disclosed which comprise, in admixture, (a) a normally flammable composition comprising a polyphenylene ether resin and a polymer selected from the group consisting of a hydrogenated A-B-A1 block copolymer and an acrylic resin modified diene rubber containing resin, and (b) an aromatic phosphate compound in an amount at least sufficient to render the normally flammable composition self-extinguishing and, after molding, impact resistant and having a high surface glass as required for use in many commercial applications.
Description
~ 32 8CH-2146 This invention relates to novel thermoplastic molding compositions which are self-extinguishing and are moldable to finished articles of good impact resistance and high surface gloss. More particularly, the invention i5 concerned with thermoplastic compositions of a polypheny-lene ether resin, a polymer selected from hydrogenated A-B-A block copolymers and acrylic resin modified diene rubber containing resins, and an aromatic phosphate which is present in amounts sufficient to provide, in addition to flame resistance to the thermoplastic impurities, impact resistance and good surface gloss to the resulting molded articles.
The polyphenylene ether resins are well known in the art as a class of thermoplastics which possess a number of outstanding physical properties. They can be prepared by oxidative and non-oxidative methods, such as are disclosed, for example, in Hay, U.S. Patent 3,306,874 dated February 28, 1967 and 3,306,875 dated February 28, 1967 and Stamatoff, U.S. Patent 3,257,357 dated June 21, 1966 and 3,257,358 dated June 21, 1966.
It has been found that many of the properties of polyphenylene ether resins, e.g., ease of processing, impact strength and solvent resistance, can be improved by combining these resins with other resins, such as, for example, polystyrene. Examples of polyphenylene ether resin-polystyrene compositions are disclosed in Cizek, U.S.
Patent 3,383,435 dated May 14, 1968.
More recently, it has been found that polypheny-lene ether resins can also be combined with block copolymers of the A-B-A type, e.g., polystyrene-polybutadiene-poly-styrene, and with acrylic resin modified diene rubber containing resins, to provide compatible compositions ~k ~2~32 8CH-2146 characterized by a number o~ excellent physical properties in the resulting molded articles. These discoveries are described in Abolins et al, U.S. 3,833,688 dated September 3, 1974 and 3,792,123 dated February 12, 1974 and in Canadian application Serial No. 205,298, filed July 22, 1974, and assigned to the same assignee as in the present application.
It is known in the art that the polyphenylene ethers have excellent flame retardant properties and are classified self-extinguishing and non-dripping according to ASTM Test Method D635 and Underwriters Laboratories Bulletin No. 94. On the other hand, when polyphenylene ethers are combined with other polymers such as the above-mentioned A-B-A block copolymers and acrylic resin modified diene rubber containing resins, many of the resulting com-positions have poor flame retardancy and are not self-extinguishing, but rather burn slowly upon ignition. Con-sequently, many compositions of polyphenylene ether resin and A-B-Al block copolymers or acrylic resin modified diene rubber containing resins are unable to meet the minimum requirements established by various testing laboratories such as the Underwriters Laboratories. This restricts the use of such compositions for many commercial applications.
Flame retardant additives for thermoplastics are known. In general, these are either blended physically with the thermoplastic or are used to unite chemically with the plastic and to modify it. For instance, self-extinguishing blends of a polyphenylene ether resin and a styrene resin using a combination of an aromatic phosphate and an aromatic halogen for flame retardancy are disclosed by Haaf in U.S.
3,639,506 dated February 1, 1972. Other self-extinguishing polyphenylene ether-polystyrene compositions are disclosed 11~2~3z 8CH-2146 by Reinhard in U.S. 3,809,72g, dated May 7, 1974 wherein aromatic halogens combined with antimony compounds are used as flame retardant additives. Still other flame retardant compositions of a polyphenylene ether resin and a styrene resin which include various phosphorus-containing and halogen-containing flame retardant agents, are described by Haaf et al in Canadian Serial No. 242,338 filed December 18, 1975 and assigned to the same assignee as herein.
However, as is also well known, the inclusion of flame retarding compounds in thermoplastic materials not only affects burning characteristics, it frequently changes other physical properties as well, such as color, flexibility, tensile strength, electrical properties, softening point, and moldability characteristics. Thus, for example, aromatic phosphates such as triphenyl phosphate have been added to blends of polyphenylene ethers and styrene resins, with flame retardant properties being improved to the point where the compositions can be classified as self-extinguishing and non-dripping according to the above-noted ASTM Test Method D635 and U.L. Bulletin No. 94.
It has now been surprisingly discovered that molded compositions consisting of polyphenylene ether or various combinations of polyphenylene ether and polystyrene, certain polymeric modifiers, and aromatic phosphate com-pounds exhibit excellent self-extinguishing behavior, impact strength and surface gloss.
The commercial benefits of flame retardancy, good impact resistance and high surface gloss in the composition of this invention are most unexpected, generally in view of the physical properties frequently exhibited by flame retardant compositions of the prior art.
Description of the Invention - According to ' 8c~-2146
The polyphenylene ether resins are well known in the art as a class of thermoplastics which possess a number of outstanding physical properties. They can be prepared by oxidative and non-oxidative methods, such as are disclosed, for example, in Hay, U.S. Patent 3,306,874 dated February 28, 1967 and 3,306,875 dated February 28, 1967 and Stamatoff, U.S. Patent 3,257,357 dated June 21, 1966 and 3,257,358 dated June 21, 1966.
It has been found that many of the properties of polyphenylene ether resins, e.g., ease of processing, impact strength and solvent resistance, can be improved by combining these resins with other resins, such as, for example, polystyrene. Examples of polyphenylene ether resin-polystyrene compositions are disclosed in Cizek, U.S.
Patent 3,383,435 dated May 14, 1968.
More recently, it has been found that polypheny-lene ether resins can also be combined with block copolymers of the A-B-A type, e.g., polystyrene-polybutadiene-poly-styrene, and with acrylic resin modified diene rubber containing resins, to provide compatible compositions ~k ~2~32 8CH-2146 characterized by a number o~ excellent physical properties in the resulting molded articles. These discoveries are described in Abolins et al, U.S. 3,833,688 dated September 3, 1974 and 3,792,123 dated February 12, 1974 and in Canadian application Serial No. 205,298, filed July 22, 1974, and assigned to the same assignee as in the present application.
It is known in the art that the polyphenylene ethers have excellent flame retardant properties and are classified self-extinguishing and non-dripping according to ASTM Test Method D635 and Underwriters Laboratories Bulletin No. 94. On the other hand, when polyphenylene ethers are combined with other polymers such as the above-mentioned A-B-A block copolymers and acrylic resin modified diene rubber containing resins, many of the resulting com-positions have poor flame retardancy and are not self-extinguishing, but rather burn slowly upon ignition. Con-sequently, many compositions of polyphenylene ether resin and A-B-Al block copolymers or acrylic resin modified diene rubber containing resins are unable to meet the minimum requirements established by various testing laboratories such as the Underwriters Laboratories. This restricts the use of such compositions for many commercial applications.
Flame retardant additives for thermoplastics are known. In general, these are either blended physically with the thermoplastic or are used to unite chemically with the plastic and to modify it. For instance, self-extinguishing blends of a polyphenylene ether resin and a styrene resin using a combination of an aromatic phosphate and an aromatic halogen for flame retardancy are disclosed by Haaf in U.S.
3,639,506 dated February 1, 1972. Other self-extinguishing polyphenylene ether-polystyrene compositions are disclosed 11~2~3z 8CH-2146 by Reinhard in U.S. 3,809,72g, dated May 7, 1974 wherein aromatic halogens combined with antimony compounds are used as flame retardant additives. Still other flame retardant compositions of a polyphenylene ether resin and a styrene resin which include various phosphorus-containing and halogen-containing flame retardant agents, are described by Haaf et al in Canadian Serial No. 242,338 filed December 18, 1975 and assigned to the same assignee as herein.
However, as is also well known, the inclusion of flame retarding compounds in thermoplastic materials not only affects burning characteristics, it frequently changes other physical properties as well, such as color, flexibility, tensile strength, electrical properties, softening point, and moldability characteristics. Thus, for example, aromatic phosphates such as triphenyl phosphate have been added to blends of polyphenylene ethers and styrene resins, with flame retardant properties being improved to the point where the compositions can be classified as self-extinguishing and non-dripping according to the above-noted ASTM Test Method D635 and U.L. Bulletin No. 94.
It has now been surprisingly discovered that molded compositions consisting of polyphenylene ether or various combinations of polyphenylene ether and polystyrene, certain polymeric modifiers, and aromatic phosphate com-pounds exhibit excellent self-extinguishing behavior, impact strength and surface gloss.
The commercial benefits of flame retardancy, good impact resistance and high surface gloss in the composition of this invention are most unexpected, generally in view of the physical properties frequently exhibited by flame retardant compositions of the prior art.
Description of the Invention - According to ' 8c~-2146
2~32 I
1 ¦ the present invention there are provided flame retardant 2 ¦ self-extinguishing thermoplastic molding compositions which,
1 ¦ the present invention there are provided flame retardant 2 ¦ self-extinguishing thermoplastic molding compositions which,
3 ¦ after molding, are impact resistant and have high surface gloss,
4 ¦ the compositions comprising an intimate admixture of:
¦ (a) a normally flammable compositi~n 6 ¦ comprising (i) a polyphenylene ether resin and (ii) a polymer 7 selected from the group consisting of a hydrogenated A-B-A
block copolymer and an acrylic resin modified diene rubber-9 containing resin, and "
(b) an aromatic phosphate compound in an 11 amount at least sufficient to render the normally flammable 12 composition self-extinguishing and, after molding, impact 13 resistant and having a high surface gloss.
14 .
The polyphenylene ether resins of (a) are 16 preferably of the type having the structural formula:
~1 - 3~
24 wherein the oxygen ether atom of one unit is connected to the benzene nucleus of the next adjoining unit, n is a positive 26 integer and is at least 50, and each Q is a monovalent 27 substituent selected from the group consisting of hydrogen, 28 halogen, hydrocarbon radicals free of a tertiary alpha-carbon 29 atom, halohydrocarbon radicals having at least two carbon atoms between the halogen atom and the phenyl nucleus, 1~2~3Z
, .' 1 hydrocarbonoxy radicals and halohydrocarbonoxy radicals having 2 a~ least two carbon atoms between the halogen atom and the 3 phenyl nucleus.
An especially preferred class of polyphenylene 6 ether resins for the compositions of this invention includes 7 those of the above formula wherein each Q is alkyl, most preferab~ Y
8 having from 1 to 4 carbon atoms. -Illustratively, members of this 9 class include poly(2,6-dimethyl-1,4-phenylene)ether; poly (2,6-diethyl-1,4-phenylene)ether; poly(2-methyl-6-ethyl-1,4-11 phenylene)ether; poly(2-methyl-6-propyl-1,4-phenylene)ether;
12 poly(2,6-dipropyl-1,4-phenylene)ether; poly(2-ethyl-6-propyl-1, 13 4-phenylene)ether; and the like. Most preferred is poly(2,6-14 dimethyl-1,4-phenylene)ether, preferably having an intrinsic viscosity of about 0.45 decililiters per gram (dl./g.) as measured 16 in chloroform at 30C.
18 The hydrogenated A-B-Al block copolymers of 19 component (a)(ii) are well known. In general, these are block copolymers of the A-B-Al type in which terminal blocks A and A
21 are the same or different and, prior to hydrogenation, comprise 22 homopolymers or copolymers derived from vinyl aromatic hydro-23 carbons and, especially, vinyl aromatics wherein the aromatic 24 moiety can be either monocyclic or polycyclic. Examples of the monomers are styrene, alpha methyl styrene, vinyl xylene, 26 ethyl vinyl xylene, vinyl naphthalene, and the like. Center block B will always be derived from a conjugated diene, e.g., 29 butadiene, isoprene, 1,3-pentadiene, and the like. Preferably, center block B will be comprised of polybutadiene or polyiso-prene.
j~ 8CH- 2146 ~2(;~32 1 . .
2 It is preferred to form t:erminal blocks A and A
having average molecular weights of 4,000 to 115,000 and center 4 block B having average molecular weights of 20,000 to 450,000.
Still more preferably, the terminal blocks will have average molecular weights of 8,000 to 60,000 while the center block 76 has an average molecular weight between about 50,000 and ., 8 300,000. The terminal blocks will preferably comprise from 2 to Il.
9 33% by weight, and more preferably, 5 to 30% by weight of the total block copolymer. Especially preferred are A-B-Al type 11 block copolymers having apolybutadiene center block wherein 12 35 to 55%, or more preferably, 40 to 50% of the carbon atoms 13 present in the butadiene polymer block are in the form of 154 dependent vinyl side chains.
16 The A-B-Al block copolymers will have an 17 unsaturation in the center block B reduced to less than 10%
18 and more preferably, less than 5% of its original value.
The hydrogenated block copolymers are formed 21 by techniques which are well known to those skilled in the art.
22 For instance, the preparation of these materials is described 23 in detail in Jones, U.S. 3,431,323, dated March 4, 24 1969.
26 Hydrogenation can be carried out with a variety 27 of ~ydrogenation catalysts, such as nickel on Kieselguhr, Raney 28 nickel, copper chromate, molybdenum sulfide and finely divided 29 platinum or other noble metals on a low surface area catalyst.
Hydrogenation can be conducted at any desired il 8CH- 2146 1 te~ ~erat~re or press~rè, e g , from anmospheric t~ 3,0~0 p.9.i.g., 2 the usual ange being between 100 and 1,000 p.s.i.g., and at tem-3 ~ peratures from about 75 to 600F., for times between 0.1 and 24 4 hours, preferably 0.2 to 8 hours.
The acrylic resin modified diene rubber resin of com-6 ponent (a)(ii) i9 preferably selected from the group consisting 7 o a resinous composition consisting essentially of a poly(alkyl-8 methacrylate) grafted onto a butadiene-styrene backbone or an 9 acrylonitrile-butadiene-styrene backbone or a resinous composition consisting essentially of a mixture of a poly(alkylmethacrylate) 11 and a butadiene styrene copolymer or an acrylonitrile-butadiene-12 styrene terpolymer.
13 The graft polymerization product of an acrylic monomer 14 and a diene rubber of component (a)(ii) preferably comprises (1) from about 20 to 80% by weight of a backbone copolymer of butadien~
16 and styrene or a backbone terpolymer of acrylonitrile, butadiene 17 and styrene, wherein the butadiene units are present in quantities 18 of at least 40% by weight of the backbone polymer; (2) 80 to 20%
19 by weight of an acrylic monomer graft polymerized to (1), said acrylic monomer units being selected from the group consisting of 21 lower alkyl methacrylates, alicyclic methacrylates and alkyl 22 acrylates, and (3) 0 to 60% by weight of a styrene monomer graft 23 polymerized to (1).
24 The graft polymerization product of an acrylic monomer alone or with styrene monomer and the rubbery diene 26 polymer or copolymer may be prepared by known techniques, 27 typically by emulsion polymerization. They may be formed from 28 a styrene-butadiene copolymer latex and a monomeric material ~ 32 such as methyl methacrylate alone or with another compound having a single vinylidene group copolymerizable therewith, e.g., styrene. For example, in the preparation of a repre-sentative material, 85 to 65 parts by weight of monomeric methyl methacrylate or monomeric methyl methacrylate to the extent of at least 55%, and preferably as much as 75~ by weight, in admixture with another monomer which copolymerizes therewith, such as ethyl acrylate, acrylonitrile, vinylidene chloride, styrene, and similar unsaturated compounds containing a single vinylidene group, is added to 15 to 35 parts by weight of solids in a styrene-butadiene copolymer latex. The copolymer solids in the latex comprise about 10 to 50% by weight of styrene and about 90 to 50~ by weight of butadine and the molecular weight thereof is within the range of about 25,000 to 1,500,000.
The copolymer latex of solids in water contains a dispersing agent, such as sodium oleate or the like, to maintain the copolymer in emulsion. Interpolymerization of the monomer or monomeric mixture with the copolymer solids emulsified in water is brought about in the presence of a free-radical generating catalyst and a polymerization regulator which serves as a chain transfer agent, at a temperature in the range between 15C. and 80C. Coagulation of the interpolymerized product is then effected with a calcium chloride solution, for instance, whereupon it is filtered, washed and dried.
Other graft copolymers which differ from the above only in the ratio of monomeric material comprised solely or preponderantly of methyl methacrylate to the butadiene styrene copolymer latex extend from 85 to 25 parts by weight of the former to 15 to 75 parts by weight of the latter. These 8C~-2146 1~32~3Z
materials can vary in physical properties from relatively rigid compositions to rubbery compositions. A preferred commercially available material is Acryloid KM 611TM, which is sold by Rohm & Haas Company. Additional information on the preparation of these materials is contained in U.S. 2,943,074 dated June 28, 1960 and in U.S. 2,857,360 dated october 21, 1958. A preferred material is described in U.S. 2,943,074, Column 4, preparation "D" with conversion to emulsified polymer "B" described therein.
The aromatic phosphate compound of the compositions of the invention is a compound of the formula:
R30 - P ORl l R2 where Rl, R2 and R3 can be the same or different and are alkyl, cycloalkyl, aryl, alkyl substituted aryl, halogen substituted aryl, aryl substituted alkyl, halogen, hydrogen and combinations of any of the foregoing, provided that at least one of Rl, R2 and R3 is aryl.
Typical examples include phenylbisdodecyl phosphate, phenylbisneopentyl phosphate, phenylethylene hydrogen phosphate, phenyl-bis(3,5,5'-trimethylhextyl phosphate), ethyl-diphenyl phosphate, 2-ethyl-hexyldi(p-tolyl) phosphate, di-phenyl hydrogen phosphate, bis (2-ethylhexyl) p-tolylphosphate, tri-tolyl phosphate, bis (2-ethylhexyl)phenyl phosphate, tri-(nonyl-phenyl) phosphate, phenylmethyl hydrogen phosphate, di(dodecyl) p-tolyl phosphate, tricresyl phosphate, triphenyl phosphate, dibutylphenyl phosphate, 2-chloroethyldiphenyl phosphate, ~2~32 p-tolyl bis (2,5,5'-trimethylhexyl) phosphate, 2-ethylhexyl-diphenyl phosphate, diphenyl hydrogen phosphate, and the like.
The preferred phosphates are those where each R is aryl.
Especially preferred is triphenyl phosphate.
The respective amounts of the components in the present compositions can vary broadly, e.g., from 60 to 99 parts by weight of polyphenylene ether resin to 40 to 1 parts by weight of A-s-Al block copolymer or acrylic resin modified diene rubber containing resin. With respect to the compositions containing A-B-Al block copolymers, the most preferred such compositions contain no less than about 65% by weight of poly-phenylene ether alone or combined with polystyrene resin, based on the total weight of the resinous components in the composi-tion. With respect to the aromatic phosphate flame retarding agent, amounts of from 1 to 40 parts by weight of the total composition can be employed to impart flame retardancy. Par-ticular amounts will, of course, vary depending on the needs of the specific composition.
The compositions of the invention can also further include glass fibers as a reinforcing filler, especially pre-ferably, fibrous glass filaments comprised of line-aluminum borosilicate glass which is relatively soda free, known as "E"
glass. However, other glasses are useful where electrical prop-erties 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, flame blowing and mechanical pulling. The preferred filaments for plastics reinforcement are made by mechanical pulling. The filament diameters range from about 0.000112 to 0.00075 inch, but this is not critical to the present invention.
In general, best properties will be obtained if the sized filamentous glass reinforcement comprise from 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 50% of glass can be present without causing flow problems.
However, it is useful also to prepare the compositions con-taining substantially greater quantities, e.g., up to 70 to 80%
by weight of glass. These concentrates can then be custom blended with blends of resins that are not glass reinforced to provide any desired glass content of a lower value.
Other ingredients, such as stabilizers, pigments, plasticizers, antioxidants, and the like, can be added for their conventionally employed purposes.
The compositions of this invention can be prepared conventionally by tumbling the components to form a preblend, extruding blend into a continuous strand, cutting the strand into pellets or granules, and molding the pellets or granules into the desired shape. These techniques are well known to those skilled in the art and further elaboration herein is not necessary.
Description of the Preferred Embodiments. - The - ¦¦ 8CH-2146 ~02(~3;~
1 following examples illustrate compositions according to the 2 invention. They are set forth for illustrative purposes only, 3 and are not to be construed as limit:ing.
6 The compositions shown in Table I, below, were 7 prepared by preblending the components, extruding the blend 8 and molding the extrudate into test pieces. All amounts are in parts by weight. The values for Izod impact strength are in units of ft.lbs./in.n., and the values for Gardner 11 impact strength are in units of in.-lbs. Tensile yield, 12 tensile break, flexural yield and flexural modulus values 13 are each in units of p.s.i. x 10-3. The gloss values are 45 surfac loss expressed as relative dimensionless units.
29 '~
_ _ - 12 -::: ..... .
~ 2~32 ~
' ., ~ o c~ ..
, . ' a~ u~ ' c,t:~ .
~_ ^~ O
~D
~ O cr~
,_1 ~ ^oo ~ C~
~ r~ o -- ~
~C~ ~, o U~ o U) o o o o o o .
S~ ~ ~
¦ (a) a normally flammable compositi~n 6 ¦ comprising (i) a polyphenylene ether resin and (ii) a polymer 7 selected from the group consisting of a hydrogenated A-B-A
block copolymer and an acrylic resin modified diene rubber-9 containing resin, and "
(b) an aromatic phosphate compound in an 11 amount at least sufficient to render the normally flammable 12 composition self-extinguishing and, after molding, impact 13 resistant and having a high surface gloss.
14 .
The polyphenylene ether resins of (a) are 16 preferably of the type having the structural formula:
~1 - 3~
24 wherein the oxygen ether atom of one unit is connected to the benzene nucleus of the next adjoining unit, n is a positive 26 integer and is at least 50, and each Q is a monovalent 27 substituent selected from the group consisting of hydrogen, 28 halogen, hydrocarbon radicals free of a tertiary alpha-carbon 29 atom, halohydrocarbon radicals having at least two carbon atoms between the halogen atom and the phenyl nucleus, 1~2~3Z
, .' 1 hydrocarbonoxy radicals and halohydrocarbonoxy radicals having 2 a~ least two carbon atoms between the halogen atom and the 3 phenyl nucleus.
An especially preferred class of polyphenylene 6 ether resins for the compositions of this invention includes 7 those of the above formula wherein each Q is alkyl, most preferab~ Y
8 having from 1 to 4 carbon atoms. -Illustratively, members of this 9 class include poly(2,6-dimethyl-1,4-phenylene)ether; poly (2,6-diethyl-1,4-phenylene)ether; poly(2-methyl-6-ethyl-1,4-11 phenylene)ether; poly(2-methyl-6-propyl-1,4-phenylene)ether;
12 poly(2,6-dipropyl-1,4-phenylene)ether; poly(2-ethyl-6-propyl-1, 13 4-phenylene)ether; and the like. Most preferred is poly(2,6-14 dimethyl-1,4-phenylene)ether, preferably having an intrinsic viscosity of about 0.45 decililiters per gram (dl./g.) as measured 16 in chloroform at 30C.
18 The hydrogenated A-B-Al block copolymers of 19 component (a)(ii) are well known. In general, these are block copolymers of the A-B-Al type in which terminal blocks A and A
21 are the same or different and, prior to hydrogenation, comprise 22 homopolymers or copolymers derived from vinyl aromatic hydro-23 carbons and, especially, vinyl aromatics wherein the aromatic 24 moiety can be either monocyclic or polycyclic. Examples of the monomers are styrene, alpha methyl styrene, vinyl xylene, 26 ethyl vinyl xylene, vinyl naphthalene, and the like. Center block B will always be derived from a conjugated diene, e.g., 29 butadiene, isoprene, 1,3-pentadiene, and the like. Preferably, center block B will be comprised of polybutadiene or polyiso-prene.
j~ 8CH- 2146 ~2(;~32 1 . .
2 It is preferred to form t:erminal blocks A and A
having average molecular weights of 4,000 to 115,000 and center 4 block B having average molecular weights of 20,000 to 450,000.
Still more preferably, the terminal blocks will have average molecular weights of 8,000 to 60,000 while the center block 76 has an average molecular weight between about 50,000 and ., 8 300,000. The terminal blocks will preferably comprise from 2 to Il.
9 33% by weight, and more preferably, 5 to 30% by weight of the total block copolymer. Especially preferred are A-B-Al type 11 block copolymers having apolybutadiene center block wherein 12 35 to 55%, or more preferably, 40 to 50% of the carbon atoms 13 present in the butadiene polymer block are in the form of 154 dependent vinyl side chains.
16 The A-B-Al block copolymers will have an 17 unsaturation in the center block B reduced to less than 10%
18 and more preferably, less than 5% of its original value.
The hydrogenated block copolymers are formed 21 by techniques which are well known to those skilled in the art.
22 For instance, the preparation of these materials is described 23 in detail in Jones, U.S. 3,431,323, dated March 4, 24 1969.
26 Hydrogenation can be carried out with a variety 27 of ~ydrogenation catalysts, such as nickel on Kieselguhr, Raney 28 nickel, copper chromate, molybdenum sulfide and finely divided 29 platinum or other noble metals on a low surface area catalyst.
Hydrogenation can be conducted at any desired il 8CH- 2146 1 te~ ~erat~re or press~rè, e g , from anmospheric t~ 3,0~0 p.9.i.g., 2 the usual ange being between 100 and 1,000 p.s.i.g., and at tem-3 ~ peratures from about 75 to 600F., for times between 0.1 and 24 4 hours, preferably 0.2 to 8 hours.
The acrylic resin modified diene rubber resin of com-6 ponent (a)(ii) i9 preferably selected from the group consisting 7 o a resinous composition consisting essentially of a poly(alkyl-8 methacrylate) grafted onto a butadiene-styrene backbone or an 9 acrylonitrile-butadiene-styrene backbone or a resinous composition consisting essentially of a mixture of a poly(alkylmethacrylate) 11 and a butadiene styrene copolymer or an acrylonitrile-butadiene-12 styrene terpolymer.
13 The graft polymerization product of an acrylic monomer 14 and a diene rubber of component (a)(ii) preferably comprises (1) from about 20 to 80% by weight of a backbone copolymer of butadien~
16 and styrene or a backbone terpolymer of acrylonitrile, butadiene 17 and styrene, wherein the butadiene units are present in quantities 18 of at least 40% by weight of the backbone polymer; (2) 80 to 20%
19 by weight of an acrylic monomer graft polymerized to (1), said acrylic monomer units being selected from the group consisting of 21 lower alkyl methacrylates, alicyclic methacrylates and alkyl 22 acrylates, and (3) 0 to 60% by weight of a styrene monomer graft 23 polymerized to (1).
24 The graft polymerization product of an acrylic monomer alone or with styrene monomer and the rubbery diene 26 polymer or copolymer may be prepared by known techniques, 27 typically by emulsion polymerization. They may be formed from 28 a styrene-butadiene copolymer latex and a monomeric material ~ 32 such as methyl methacrylate alone or with another compound having a single vinylidene group copolymerizable therewith, e.g., styrene. For example, in the preparation of a repre-sentative material, 85 to 65 parts by weight of monomeric methyl methacrylate or monomeric methyl methacrylate to the extent of at least 55%, and preferably as much as 75~ by weight, in admixture with another monomer which copolymerizes therewith, such as ethyl acrylate, acrylonitrile, vinylidene chloride, styrene, and similar unsaturated compounds containing a single vinylidene group, is added to 15 to 35 parts by weight of solids in a styrene-butadiene copolymer latex. The copolymer solids in the latex comprise about 10 to 50% by weight of styrene and about 90 to 50~ by weight of butadine and the molecular weight thereof is within the range of about 25,000 to 1,500,000.
The copolymer latex of solids in water contains a dispersing agent, such as sodium oleate or the like, to maintain the copolymer in emulsion. Interpolymerization of the monomer or monomeric mixture with the copolymer solids emulsified in water is brought about in the presence of a free-radical generating catalyst and a polymerization regulator which serves as a chain transfer agent, at a temperature in the range between 15C. and 80C. Coagulation of the interpolymerized product is then effected with a calcium chloride solution, for instance, whereupon it is filtered, washed and dried.
Other graft copolymers which differ from the above only in the ratio of monomeric material comprised solely or preponderantly of methyl methacrylate to the butadiene styrene copolymer latex extend from 85 to 25 parts by weight of the former to 15 to 75 parts by weight of the latter. These 8C~-2146 1~32~3Z
materials can vary in physical properties from relatively rigid compositions to rubbery compositions. A preferred commercially available material is Acryloid KM 611TM, which is sold by Rohm & Haas Company. Additional information on the preparation of these materials is contained in U.S. 2,943,074 dated June 28, 1960 and in U.S. 2,857,360 dated october 21, 1958. A preferred material is described in U.S. 2,943,074, Column 4, preparation "D" with conversion to emulsified polymer "B" described therein.
The aromatic phosphate compound of the compositions of the invention is a compound of the formula:
R30 - P ORl l R2 where Rl, R2 and R3 can be the same or different and are alkyl, cycloalkyl, aryl, alkyl substituted aryl, halogen substituted aryl, aryl substituted alkyl, halogen, hydrogen and combinations of any of the foregoing, provided that at least one of Rl, R2 and R3 is aryl.
Typical examples include phenylbisdodecyl phosphate, phenylbisneopentyl phosphate, phenylethylene hydrogen phosphate, phenyl-bis(3,5,5'-trimethylhextyl phosphate), ethyl-diphenyl phosphate, 2-ethyl-hexyldi(p-tolyl) phosphate, di-phenyl hydrogen phosphate, bis (2-ethylhexyl) p-tolylphosphate, tri-tolyl phosphate, bis (2-ethylhexyl)phenyl phosphate, tri-(nonyl-phenyl) phosphate, phenylmethyl hydrogen phosphate, di(dodecyl) p-tolyl phosphate, tricresyl phosphate, triphenyl phosphate, dibutylphenyl phosphate, 2-chloroethyldiphenyl phosphate, ~2~32 p-tolyl bis (2,5,5'-trimethylhexyl) phosphate, 2-ethylhexyl-diphenyl phosphate, diphenyl hydrogen phosphate, and the like.
The preferred phosphates are those where each R is aryl.
Especially preferred is triphenyl phosphate.
The respective amounts of the components in the present compositions can vary broadly, e.g., from 60 to 99 parts by weight of polyphenylene ether resin to 40 to 1 parts by weight of A-s-Al block copolymer or acrylic resin modified diene rubber containing resin. With respect to the compositions containing A-B-Al block copolymers, the most preferred such compositions contain no less than about 65% by weight of poly-phenylene ether alone or combined with polystyrene resin, based on the total weight of the resinous components in the composi-tion. With respect to the aromatic phosphate flame retarding agent, amounts of from 1 to 40 parts by weight of the total composition can be employed to impart flame retardancy. Par-ticular amounts will, of course, vary depending on the needs of the specific composition.
The compositions of the invention can also further include glass fibers as a reinforcing filler, especially pre-ferably, fibrous glass filaments comprised of line-aluminum borosilicate glass which is relatively soda free, known as "E"
glass. However, other glasses are useful where electrical prop-erties 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, flame blowing and mechanical pulling. The preferred filaments for plastics reinforcement are made by mechanical pulling. The filament diameters range from about 0.000112 to 0.00075 inch, but this is not critical to the present invention.
In general, best properties will be obtained if the sized filamentous glass reinforcement comprise from 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 50% of glass can be present without causing flow problems.
However, it is useful also to prepare the compositions con-taining substantially greater quantities, e.g., up to 70 to 80%
by weight of glass. These concentrates can then be custom blended with blends of resins that are not glass reinforced to provide any desired glass content of a lower value.
Other ingredients, such as stabilizers, pigments, plasticizers, antioxidants, and the like, can be added for their conventionally employed purposes.
The compositions of this invention can be prepared conventionally by tumbling the components to form a preblend, extruding blend into a continuous strand, cutting the strand into pellets or granules, and molding the pellets or granules into the desired shape. These techniques are well known to those skilled in the art and further elaboration herein is not necessary.
Description of the Preferred Embodiments. - The - ¦¦ 8CH-2146 ~02(~3;~
1 following examples illustrate compositions according to the 2 invention. They are set forth for illustrative purposes only, 3 and are not to be construed as limit:ing.
6 The compositions shown in Table I, below, were 7 prepared by preblending the components, extruding the blend 8 and molding the extrudate into test pieces. All amounts are in parts by weight. The values for Izod impact strength are in units of ft.lbs./in.n., and the values for Gardner 11 impact strength are in units of in.-lbs. Tensile yield, 12 tensile break, flexural yield and flexural modulus values 13 are each in units of p.s.i. x 10-3. The gloss values are 45 surfac loss expressed as relative dimensionless units.
29 '~
_ _ - 12 -::: ..... .
~ 2~32 ~
' ., ~ o c~ ..
, . ' a~ u~ ' c,t:~ .
~_ ^~ O
~D
~ O cr~
,_1 ~ ^oo ~ C~
~ r~ o -- ~
~C~ ~, o U~ o U) o o o o o o .
S~ ~ ~
5~ i 0 . ~^~ ' ~:~ . C~t~ ,~
U~ o o o o o o ~
~o ~ ~ CO
~`J
~0~ ~^ . '.
'~ ::
~ 0 P~ ~
-13 _ ~
I~ 2C~3Z 8CH-2146 ~ o o o o .1~ o ., '1~ ~~ `D ~D ~ (~ 1 lc~ l C`J C~
, ..
~1 .~
C C~ O' ~ C~ C~l ~ ~ ~ C~ l_ U~
~J . . . . . .. , , , , ~0Cr~ ~ .~ ~
~ ' ,~
~ .
O . . . . . . . . .
~1 ~ O C`l ~1 00 'D ~ `;t I O
C~u~ D ~ ~ ~
oo a~ o o c~l O ~ ~ ~D~D ~ C~ O O 1, t~
X .
:' ~ ~ o ~ o ~ O u~ 00 , u~ ~ ~ o oO oO 1~ ~D
~ ~ ~ 1 :
C~
_~ .:~
.
~: O CS~ D
a) . . . . . . . . ..
~ a~ ~ a~ D U~ ~O U~ ~ ~ ~
~ .
E~ ~ : ' ~D ~ ~ ~ CO ~ C~ ~ ~
C~ . . . . . . . . ..
~ O~0 0 001~ ,. ~
o .
rl~ ..
~ X ...
I ~ ~ ~7 ~ O 1~ 00 0 0 ~D ~ ~ O
I ~ 1-- ~ O ~D ~ O ~ U~ C`l 1~ ~
I ~ ~ ~ ": , , I ~E~ ~
:~ ..
_ 14_ .
2~32 ll 8CH-2146 I EXAI~LES 11 - 18 2 Additional compositions according to the 3 invention were prepared and tested as in Examples l to lO.
4 The formulations and test results for the additional composition.s are listed in Table II. Unless shown otherwise, 1~ units a as in T~b1e I.
~4 _ .. . ,. ~ ... _ ~
~Z~32 8CH--2146 gl ~ r~ ~ o ~
3 ~
. .
a) ~0 .
~ ~ U~ , ~ P,, ~ a~ a~ a~ co o ~i ~ ,i o $
E~
, ~ ou~ o ou~ ~ :
p , ¢ .
0 ;~ ~
~ h ~' ~
~ ~: U~ O O 1~ ~, .
E~ E~ ~:4 . ~
~. , C~ :.
~s~ . ~a~ ' h ~' ~
a) ~ ~ ~: ~
3 ~ ~ h I ~ U~ o o ~ ~ U~ .. 0 U~ ~ I~ 00 00 CO 00 00 ~
Ch~P- o~3 '.', o ~ .n ~ C
~ 0 ~
U~ o o o o o o ~
~o ~ ~ CO
~`J
~0~ ~^ . '.
'~ ::
~ 0 P~ ~
-13 _ ~
I~ 2C~3Z 8CH-2146 ~ o o o o .1~ o ., '1~ ~~ `D ~D ~ (~ 1 lc~ l C`J C~
, ..
~1 .~
C C~ O' ~ C~ C~l ~ ~ ~ C~ l_ U~
~J . . . . . .. , , , , ~0Cr~ ~ .~ ~
~ ' ,~
~ .
O . . . . . . . . .
~1 ~ O C`l ~1 00 'D ~ `;t I O
C~u~ D ~ ~ ~
oo a~ o o c~l O ~ ~ ~D~D ~ C~ O O 1, t~
X .
:' ~ ~ o ~ o ~ O u~ 00 , u~ ~ ~ o oO oO 1~ ~D
~ ~ ~ 1 :
C~
_~ .:~
.
~: O CS~ D
a) . . . . . . . . ..
~ a~ ~ a~ D U~ ~O U~ ~ ~ ~
~ .
E~ ~ : ' ~D ~ ~ ~ CO ~ C~ ~ ~
C~ . . . . . . . . ..
~ O~0 0 001~ ,. ~
o .
rl~ ..
~ X ...
I ~ ~ ~7 ~ O 1~ 00 0 0 ~D ~ ~ O
I ~ 1-- ~ O ~D ~ O ~ U~ C`l 1~ ~
I ~ ~ ~ ": , , I ~E~ ~
:~ ..
_ 14_ .
2~32 ll 8CH-2146 I EXAI~LES 11 - 18 2 Additional compositions according to the 3 invention were prepared and tested as in Examples l to lO.
4 The formulations and test results for the additional composition.s are listed in Table II. Unless shown otherwise, 1~ units a as in T~b1e I.
~4 _ .. . ,. ~ ... _ ~
~Z~32 8CH--2146 gl ~ r~ ~ o ~
3 ~
. .
a) ~0 .
~ ~ U~ , ~ P,, ~ a~ a~ a~ co o ~i ~ ,i o $
E~
, ~ ou~ o ou~ ~ :
p , ¢ .
0 ;~ ~
~ h ~' ~
~ ~: U~ O O 1~ ~, .
E~ E~ ~:4 . ~
~. , C~ :.
~s~ . ~a~ ' h ~' ~
a) ~ ~ ~: ~
3 ~ ~ h I ~ U~ o o ~ ~ U~ .. 0 U~ ~ I~ 00 00 CO 00 00 ~
Ch~P- o~3 '.', o ~ .n ~ C
~ 0 ~
6" r~ ~ 00 ¢ ¢ O
~ ~ 1 ~
t~ e~
_ _ -'6-~.Q~ 32 8CM-2146 ~ , ..
~ C~ U~ ~ U~ ~ ~1_ U~
- o~
~ I ~ o ~
c~ D ~ ~ ~ 00 :~
~, oo C~ ~ o ~` o ~
o ~ ~ ~ ~ oo oo I
~d ~ c~
. ~E~ .:
.
~: U
tJ ~ :
~_~ h u ~ O ~ ) 0 0 1` : 1 ~ CC ~ ~
~ : :
. ;
. ' ~bl O CO O C~ O 00 r-d Q) O S-l ~ O O ~ '1 .
a~ .
b~ co ~ .~ _ ~Z~32 8CH-2146 Although the above examples illustrate various modifications of the present invention, other variations will suggest themselves to those skilled in the art in the light of the above disclosure. It is to be understood, therefore, that changes may be made in the particular embodiments described above which are within the full intended scope of theinvention as defined in the appended claims.
The instant appllcation discloses and claims subject matter disclosed but not claimed in the related, commonly assigned Canadian Application Serial No. 292,795, filed December 9, 1977.
~ ~ 1 ~
t~ e~
_ _ -'6-~.Q~ 32 8CM-2146 ~ , ..
~ C~ U~ ~ U~ ~ ~1_ U~
- o~
~ I ~ o ~
c~ D ~ ~ ~ 00 :~
~, oo C~ ~ o ~` o ~
o ~ ~ ~ ~ oo oo I
~d ~ c~
. ~E~ .:
.
~: U
tJ ~ :
~_~ h u ~ O ~ ) 0 0 1` : 1 ~ CC ~ ~
~ : :
. ;
. ' ~bl O CO O C~ O 00 r-d Q) O S-l ~ O O ~ '1 .
a~ .
b~ co ~ .~ _ ~Z~32 8CH-2146 Although the above examples illustrate various modifications of the present invention, other variations will suggest themselves to those skilled in the art in the light of the above disclosure. It is to be understood, therefore, that changes may be made in the particular embodiments described above which are within the full intended scope of theinvention as defined in the appended claims.
The instant appllcation discloses and claims subject matter disclosed but not claimed in the related, commonly assigned Canadian Application Serial No. 292,795, filed December 9, 1977.
Claims (27)
1. A self-extinguishing thermoplastic molding composition which, after molding, is impact resistant and has high surface gloss, said composition comprising an intimate admixture of:
(a) a normally flammable composition comprising (i) a polyphenylene ether resin, alone, or in combination with a styrene resin, and (ii) a polymer selected from the group consisting of a hydrogenated A-B-A1 block copolymer wherein, prior to hydrogenation, B is a conjugated diene and A and A1 are independently selected from the group comprising homopolymers and copolymers derived from vinyl aromatic hydrocarbons and an acrylic resin modified diene rubber-containing resin, and (b) an aromatic phosphate compound in an amount at least sufficient to render said normally flammable composition (a) self-extinguishing and, after molding, impact resistant and having a high surface gloss.
(a) a normally flammable composition comprising (i) a polyphenylene ether resin, alone, or in combination with a styrene resin, and (ii) a polymer selected from the group consisting of a hydrogenated A-B-A1 block copolymer wherein, prior to hydrogenation, B is a conjugated diene and A and A1 are independently selected from the group comprising homopolymers and copolymers derived from vinyl aromatic hydrocarbons and an acrylic resin modified diene rubber-containing resin, and (b) an aromatic phosphate compound in an amount at least sufficient to render said normally flammable composition (a) self-extinguishing and, after molding, impact resistant and having a high surface gloss.
2. A self-extinguishing composition as defined in Claim 1 wherein the polyphenylene ether resin (a) (i) is of the 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 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 thephenyl nucleus.
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 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 thephenyl nucleus.
3. A self-extinguishing composition as defined in Claim 2 wherein in said polyphenylene ether resin (a)(i), each Q is alkyl having from 1 to 4 carbon atoms.
4. A self-extinguishing composition as defined in Claim 3 wherein in said polyphenylene ether resin (a)(i), each Q is methyl.
5. A self-extinguishing composition as defined in Claim 1 wherein the A-B-A1 block copolymer of component (a)(ii), prior to hydrogenation, is characterized as follows:
(1) each A is a polymerized mono alkenyl aromatic hydrocarbon block having an average molecular weight of about 4,000 to 115,000;
(2) B is a polymerized butadiene hydrocarbon block having an average molecular weight of about 20,000 to 450,000;
(3) the blocks A constituting 2 to 33 weight percent of the copolymer;
(4) 35 to 55% of the butadiene carbon atoms in block B being vinyl side chains;
(5) and the unsaturation of block B having been reduced to less than 10% of the original unsaturation.
(1) each A is a polymerized mono alkenyl aromatic hydrocarbon block having an average molecular weight of about 4,000 to 115,000;
(2) B is a polymerized butadiene hydrocarbon block having an average molecular weight of about 20,000 to 450,000;
(3) the blocks A constituting 2 to 33 weight percent of the copolymer;
(4) 35 to 55% of the butadiene carbon atoms in block B being vinyl side chains;
(5) and the unsaturation of block B having been reduced to less than 10% of the original unsaturation.
6. A self-extinguishing composition as defined in Claim 5 wherein the A-B-A1 block copolymer of component (a)(ii), prior to hydrogenation, is characterized as follows:
(1) each A is a polymerized styrene block having an average molecular weight of about 8,000 to 60,000;
(2) B is a polymerized butadiene block having an average molecular weight of about 50,000 to 300,000, 40 to 50% of the butadiene carbon atoms in the block being vinyl side-chains;
(3) the blocks A comprising 5 to 30% by weight of the copolymer; the unsaturation of block B having been reduced by hydrogenation to less than 10% of its original value.
(1) each A is a polymerized styrene block having an average molecular weight of about 8,000 to 60,000;
(2) B is a polymerized butadiene block having an average molecular weight of about 50,000 to 300,000, 40 to 50% of the butadiene carbon atoms in the block being vinyl side-chains;
(3) the blocks A comprising 5 to 30% by weight of the copolymer; the unsaturation of block B having been reduced by hydrogenation to less than 10% of its original value.
7. A self-extinguishing composition as defined in Claim 1 wherein the acrylic resin modified diene rubber resin component (a)(ii) is selected from the group consisting of a resinous composition consisting essentially of a poly(alkyl-methacrylate) grafted onto a butadiene-styrene backbone or an acrylonitrile-butadiene-styrene backbone or a resinous composition consisting essentially of a mixture of a poly-(alkylmethacrylate) and a butadiene styrene copolymer or an acrylonitrile-butadiene-styrene terpolymer, component (a)(ii) being present in an amount of from about 10 to about 80% by weight of the total resinous components of the composition.
8. A self-extinguishing composition as defined in Claim 1 wherein the aromatic phosphate flame retarding agent (b) is of the formula:
wherein R1, R2 and R3 are the same or different, and are alkyl, cycloalkyl, aryl, alkyl substituted aryl, halogen substituted aryl, aryl substituted alkyl, halogen, hydrogen and combinations of any of the foregoing, provided that at least one of R1, R2 and R3 is aryl.
wherein R1, R2 and R3 are the same or different, and are alkyl, cycloalkyl, aryl, alkyl substituted aryl, halogen substituted aryl, aryl substituted alkyl, halogen, hydrogen and combinations of any of the foregoing, provided that at least one of R1, R2 and R3 is aryl.
9. A self-extinguishing composition as defined in Claim 8 wherein said aromatic phosphate is triphenyl phosphate.
10. A self-extinguishing composition as defined in Claim 1 which includes a reinforcing amount of a fibrous glass reinforcing filler.
11. A self-extinguishing thermoplastic molding composition which, after molding, is impact resistant and has high surface gloss, said composition comprising an admixture of:
(a) a normally flammable composition comprising (i) a polyphenylene ether resin, alone, or in combination with a styrene resin, and (ii) a hydrogenated A-B-A1 block copolymer wherein, prior to hydrogenation, B is a conjugated diene and A and A1 are independently selected from the group comprising homopolymers and copolymers derived from vinyl aromatic hydro-carbons, and (b) an aromatic phosphate flame retarding agent in an amount at least sufficient to render said normally flammable composition (a) self-extinguishing and, after molding, impact resistant and having a high surface gloss.
(a) a normally flammable composition comprising (i) a polyphenylene ether resin, alone, or in combination with a styrene resin, and (ii) a hydrogenated A-B-A1 block copolymer wherein, prior to hydrogenation, B is a conjugated diene and A and A1 are independently selected from the group comprising homopolymers and copolymers derived from vinyl aromatic hydro-carbons, and (b) an aromatic phosphate flame retarding agent in an amount at least sufficient to render said normally flammable composition (a) self-extinguishing and, after molding, impact resistant and having a high surface gloss.
12. A composition as defined in claim 11 wherein the polyphenylene ether resin (a)(i) is of the 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, hydro-carbon radicals free of a tertiary alpha-carbon atom, halo-hydrocarbon 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 phenyl nucleus.
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, hydro-carbon radicals free of a tertiary alpha-carbon atom, halo-hydrocarbon 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 phenyl nucleus.
13. A composition as defined in claim 12 wherein in said polyphenylene ether resin (a)(i), each Q is alkyl having from 1 to 4 carbon atoms.
14. A composition as defined in claim 13 wherein said polyphenylene ether resin (a)(i), each Q is methyl.
15. A composition as defined in claim 11 wherein the A-B-A1 block copolymer (a)(ii), prior to hydrogenation, is characterized as follows:
(1) each A is a polymerized mono alkenyl aromatic hydrocarbon block having an average molecular weight of about 4,000 to 115,000;
(2) B is a polymerized butadiene hydrocarbon block having an average molecular weight of about 20,000 to 450,000;
(3) the blocks A constituting 2 to 33 weight percent of the copolymer;
(4) 35 to 55% of the butadiene carbon atoms in block B being vinyl side chains;
(5) and the unsaturation of block B having been reduced to less than 10% of the original unsaturation.
(1) each A is a polymerized mono alkenyl aromatic hydrocarbon block having an average molecular weight of about 4,000 to 115,000;
(2) B is a polymerized butadiene hydrocarbon block having an average molecular weight of about 20,000 to 450,000;
(3) the blocks A constituting 2 to 33 weight percent of the copolymer;
(4) 35 to 55% of the butadiene carbon atoms in block B being vinyl side chains;
(5) and the unsaturation of block B having been reduced to less than 10% of the original unsaturation.
16. A composition as defined in claim 11 wherein the A-B-A1 block copolymer (a)(ii), prior to hydrogenation, is characterized as follows:
(1) each A is a polymerized styrene block having an average molecular weight of about 8,000 to 60,000;
(2) B is a polymerized butadiene block having an average molecular weight of about 50,000 to 300,000, 40 to 50%
of the butadiene carbon atoms in the block being vinyl side chains;
(3) the blocks A comprising 5 to 30% by weight of the copolymer; the unsaturation of block B having been reduced by hydrogenation to less than 10% of its original value.
(1) each A is a polymerized styrene block having an average molecular weight of about 8,000 to 60,000;
(2) B is a polymerized butadiene block having an average molecular weight of about 50,000 to 300,000, 40 to 50%
of the butadiene carbon atoms in the block being vinyl side chains;
(3) the blocks A comprising 5 to 30% by weight of the copolymer; the unsaturation of block B having been reduced by hydrogenation to less than 10% of its original value.
17. A composition as defined in claim 11 wherein the aromatic phosphate flame retarding agent (b) is of the formula:
wherein R1, R2 and R3 are the same or different, and are alkyl, cycloalkyl, aryl, alkyl substituted aryl, halogen substituted aryl, aryl substituted alky , halogen, hydrogen and combinations of any of the foregoing, provided that at least one of R1, R2 and R3 is aryl.
wherein R1, R2 and R3 are the same or different, and are alkyl, cycloalkyl, aryl, alkyl substituted aryl, halogen substituted aryl, aryl substituted alky , halogen, hydrogen and combinations of any of the foregoing, provided that at least one of R1, R2 and R3 is aryl.
18. A composition as defined in claim 17 wherein said aromatic phosphate is triphenyl phosphate.
19. A composition as defined in claim 11 which includes a reinforcing amount of a fibrous glass reinforcing filler.
20. A self-extinguishing thermoplastic molding composition which, after molding, is impact resistant and has high surface gloss, said composition comprising an admixture of:
(a) a normally flammable composition comprising (i) a polyphenylene ether resin, alone, or in combination with a styrene resin, and (ii) an acrylic resin modified diene rubber-containing resin, and (b) an aromatic phosphate flame retarding agent in an amount at least sufficient to render the normally flammable composition (a) self-extinguishing and, after molding, impact resistant and having a high surface gloss.
(a) a normally flammable composition comprising (i) a polyphenylene ether resin, alone, or in combination with a styrene resin, and (ii) an acrylic resin modified diene rubber-containing resin, and (b) an aromatic phosphate flame retarding agent in an amount at least sufficient to render the normally flammable composition (a) self-extinguishing and, after molding, impact resistant and having a high surface gloss.
21. A composition as defined in claim 20 wherein the polyphenylene ether resin (a)(i) is of the 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, hydro-carbon radicals free of a tertiary alpha-carbon atom, halo-hydrocarbon 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 phenyl nucleus.
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, hydro-carbon radicals free of a tertiary alpha-carbon atom, halo-hydrocarbon 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 phenyl nucleus.
22. A composition as defined in claim 21 wherein in said polyphenylene ether resin (a)(i), each Q is alkyl having from 1 to 4 carbon atoms.
23. A composition as defined in claim 22 wherein in said polyphenylene ether resin (a)(i), each Q is methyl.
24. A self-extinguishing composition as defined in claim 20 wherein the acrylic resin modified diene rubber resin component (a)(ii) is selected from the group consisting of a resinous composition consisting essentially of a poly(alkyl-methacrylate) grafted onto a butadiene-styrene backbone or an acrylonitrile-butadiene-styrene backbone or a resinous composition consisting essentially of a mixture of a poly(alkylmethacrylate) and a butadiene styrene copolymer or an acrylonitrile-butadiene-styrene terpolymer, component (a)(ii) being present in an amount of from about 10 to about 80% by weight of the total resinous components of the composition.
25. A composition as defined in claim 20 wherein the aromatic phosphate flame retarding agent (b) is of the formula:
wherein R1, R2 and R3 are the same or different, and are alkyl, cycloalkyl, aryl, alkyl substituted aryl, aryl substituted alkyl, halogen, hydrogen and combinations of any of the foregoing, pro-vided that at least one of R1, R2 and R3 is aryl.
wherein R1, R2 and R3 are the same or different, and are alkyl, cycloalkyl, aryl, alkyl substituted aryl, aryl substituted alkyl, halogen, hydrogen and combinations of any of the foregoing, pro-vided that at least one of R1, R2 and R3 is aryl.
26. A composition as defined in claim 25 wherein said aromatic phosphate is triphenyl phosphate.
27. A composition as defined in claim 20 which includes a reinforcing amount of a fibrous glass reinforcing filler.
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| US74976376A | 1976-12-13 | 1976-12-13 | |
| US749,763 | 1976-12-13 |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CA1102032A true CA1102032A (en) | 1981-05-26 |
Family
ID=25015089
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CA291,790A Expired CA1102032A (en) | 1976-12-13 | 1977-11-25 | Flame-retardant, impact-resistant polyphenylene ether compositions |
Country Status (11)
| Country | Link |
|---|---|
| JP (1) | JPS5373248A (en) |
| AU (1) | AU517437B2 (en) |
| BR (1) | BR7708284A (en) |
| CA (1) | CA1102032A (en) |
| DD (1) | DD134113A5 (en) |
| DE (1) | DE2750467A1 (en) |
| FR (1) | FR2373583A1 (en) |
| GB (1) | GB1591137A (en) |
| IT (1) | IT1088288B (en) |
| MX (1) | MX146090A (en) |
| NL (1) | NL7712658A (en) |
Families Citing this family (18)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| DE2752383A1 (en) * | 1976-12-28 | 1978-06-29 | Gen Electric | PLASTIC REINFORCED COMPOSITIONS OF A POLYPHENYLENE ETHER RESIN |
| US4141876A (en) * | 1977-09-23 | 1979-02-27 | Shell Oil Company | Adhesive composition containing a polyphenylene ether resin |
| DE2963672D1 (en) * | 1978-07-04 | 1982-11-04 | Ciba Geigy Ag | Flame-retardant polymer compositions |
| GB2060656A (en) * | 1979-10-15 | 1981-05-07 | Gen Electric | Self-extinguishing polyphenylene oxide/plasticizer blends |
| JPS571733A (en) * | 1980-06-06 | 1982-01-06 | Asahi Chem Ind Co Ltd | Injection-molded form of polyphenylene ether resin having good appearance |
| US4544703A (en) * | 1981-10-02 | 1985-10-01 | General Electric Company | High impact thermoplastic compositions containing diblock impact modifier |
| FR2526437B1 (en) * | 1982-05-07 | 1987-01-23 | Oberle Patrick | LATEX COMPOSITION AND ITS APPLICATION TO THE PRODUCTION OF CARBONIZING RESISTANT FOAM |
| EP0119416A1 (en) * | 1983-02-18 | 1984-09-26 | General Electric Company | Thermoplastic molding compostions having improved dust suppression |
| NL8301569A (en) * | 1983-05-04 | 1984-12-03 | Gen Electric | POLYMER MIXTURE WITH FLAME-RESISTANT PROPERTIES, SUITABLE FOR WIRE COAT EXTRUSION, BASED ON POLYPHENYLENE OXIDE AND ELECTRICALLY CONDUCTIVE WIRE. |
| JPS6084356A (en) * | 1983-10-13 | 1985-05-13 | Mitsubishi Gas Chem Co Inc | Highly impact-resistant polyphenylene ether resin composition |
| JPS6225149A (en) * | 1985-07-25 | 1987-02-03 | Asahi Chem Ind Co Ltd | Highly elastic hydrogenated block copolymer composition |
| US5710206A (en) * | 1986-07-18 | 1998-01-20 | Raychem Limited | Gels comprising block copolymers |
| CA1320775C (en) * | 1987-08-05 | 1993-07-27 | Peter H. Thompson | Thermoplastic blend of polyphenylene ether, polystyrene, hydrogenated block copolymer and polyacrylate |
| JPH08134346A (en) * | 1994-11-14 | 1996-05-28 | Sumitomo Chem Co Ltd | Polypheylene ether resin composition |
| EP0712902A1 (en) * | 1994-11-19 | 1996-05-22 | General Electric Company | Polymer mixture comprising a polyphenylene ether and a hydrogenated diene-vinylaromatic block copolymer; objects formed thereof |
| US8653167B2 (en) | 2011-05-26 | 2014-02-18 | Sabic Innovative Plastics Ip | Molding composition for photovoltaic junction boxes and connectors |
| KR20170106493A (en) | 2015-04-27 | 2017-09-20 | 사빅 글로벌 테크놀러지스 비.브이. | Poly (phenylene ether) compositions and articles |
| CN114479438B (en) * | 2021-12-13 | 2023-05-23 | 贝克兰(厦门)新材料有限公司 | Aluminum hydroxide synergistic red phosphorus flame-retardant PA6 reinforced material and preparation method thereof |
Family Cites Families (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US3833688A (en) * | 1971-10-14 | 1974-09-03 | Gen Electric | Composition of a polyphenylene ether and an acrylic resin in combination with a diene rubber-containing resin |
| DE2434848C2 (en) * | 1973-08-13 | 1986-09-04 | General Electric Co., Schenectady, N.Y. | Thermoplastic mass |
-
1977
- 1977-11-11 DE DE19772750467 patent/DE2750467A1/en not_active Withdrawn
- 1977-11-17 NL NL7712658A patent/NL7712658A/en not_active Application Discontinuation
- 1977-11-17 GB GB47860/77A patent/GB1591137A/en not_active Expired
- 1977-11-25 IT IT30047/77A patent/IT1088288B/en active
- 1977-11-25 CA CA291,790A patent/CA1102032A/en not_active Expired
- 1977-12-09 DD DD77202518A patent/DD134113A5/en unknown
- 1977-12-09 JP JP14867877A patent/JPS5373248A/en active Pending
- 1977-12-12 FR FR7737317A patent/FR2373583A1/en active Granted
- 1977-12-12 AU AU31445/77A patent/AU517437B2/en not_active Expired
- 1977-12-13 MX MX171697A patent/MX146090A/en unknown
- 1977-12-13 BR BR7708284A patent/BR7708284A/en unknown
Also Published As
| Publication number | Publication date |
|---|---|
| DE2750467A1 (en) | 1978-06-15 |
| AU3144577A (en) | 1979-06-21 |
| MX146090A (en) | 1982-05-12 |
| DD134113A5 (en) | 1979-02-07 |
| NL7712658A (en) | 1978-06-15 |
| FR2373583A1 (en) | 1978-07-07 |
| JPS5373248A (en) | 1978-06-29 |
| AU517437B2 (en) | 1981-07-30 |
| GB1591137A (en) | 1981-06-17 |
| FR2373583B1 (en) | 1984-07-13 |
| IT1088288B (en) | 1985-06-10 |
| BR7708284A (en) | 1978-08-15 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CA1102032A (en) | Flame-retardant, impact-resistant polyphenylene ether compositions | |
| US4145377A (en) | Composition of a polyphenylene ether, a styrene resin, a precompounded polymer system and a block copolymer of a vinyl aromatic compound and an olefinic elastomer | |
| US3994856A (en) | Composition of a polyphenylene ether and a block copolymer of a vinyl aromatic compound and a conjugated diene | |
| CA1070884A (en) | Blends of a polyphenylene ether resin, alkenyl aromatic resins modified with epdm rubber and graft polymerized high rubber content polymers | |
| US3835200A (en) | Composition of a polyphenylene ether, a rubber styrene graft copolymer and normally rigid block copolymer of a vinyl aromatic compound and a conjugated diene | |
| US5206276A (en) | Flame retardant flexibilized polyphenylene ether compositions | |
| US3833688A (en) | Composition of a polyphenylene ether and an acrylic resin in combination with a diene rubber-containing resin | |
| US5081185A (en) | Polyphenylene ether composition characterized by improved melt flow | |
| EP0362660B1 (en) | Improved polyphenylene ether resin compositions which are highly resistant to delamination | |
| JPS6034583B2 (en) | Molding composition | |
| US4684682A (en) | Flame retardant flexibilized polyphenylene ether compositions | |
| US4196116A (en) | Impact resistant polyphenylene ether compositions containing EPDM rubber-modified alkenyl aromatic resins and hydrogenated diblock copolymers | |
| US4020124A (en) | Blends of a polyphenylene ether resin, alkenyl aromatic resins modified with EPDM rubber and graft polymerized high rubber content polymers | |
| US3983090A (en) | Composition of a polyphenylene ether and styrene resin and an acrylic resin in combination with a diene rubber-container resin | |
| GB2060656A (en) | Self-extinguishing polyphenylene oxide/plasticizer blends | |
| US4313864A (en) | Polyphenylene oxide/plasticizer/hydrogenated radial teleblock copolymer blends | |
| US5376724A (en) | Polyphenylene ether compositions having improved flow | |
| CA1101579A (en) | Flame-retardant flexibilized polyphenylene ether compositions | |
| US5594054A (en) | Flame retardant flexibilized polyphenylene ether compositions | |
| US4528327A (en) | Composition of polyphenylene ethers with core-shell rubber-modified polystyrene | |
| JPH0341501B2 (en) | ||
| JPS6324622B2 (en) | ||
| AU6777981A (en) | Polyphenylene plasticizer blends | |
| US4423176A (en) | Molding compositions comprising polyphenylene ether, polysulfone and vinyl aromatic-diene block copolymer | |
| CA1141064A (en) | Composition of polyphenylene ethers with core-shell rubber-modified polystyrene |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| MKEX | Expiry |