WO1981002020A1 - Improve polyphenylene plasticizer blends - Google Patents

Improve polyphenylene plasticizer blends Download PDF

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Publication number
WO1981002020A1
WO1981002020A1 PCT/US1981/000044 US8100044W WO8102020A1 WO 1981002020 A1 WO1981002020 A1 WO 1981002020A1 US 8100044 W US8100044 W US 8100044W WO 8102020 A1 WO8102020 A1 WO 8102020A1
Authority
WO
WIPO (PCT)
Prior art keywords
composition
block
plasticizer
thermoplastic molding
composition according
Prior art date
Application number
PCT/US1981/000044
Other languages
English (en)
French (fr)
Inventor
W Haaf
G Lee
Original Assignee
Gen Electric
Priority date (The priority date 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 date listed.)
Filing date
Publication date
Application filed by Gen Electric filed Critical Gen Electric
Priority to BR8105866A priority Critical patent/BR8105866A/pt
Priority to JP50353581A priority patent/JPS58500833A/ja
Publication of WO1981002020A1 publication Critical patent/WO1981002020A1/en

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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
    • 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
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K5/00—Use of organic ingredients
    • C08K5/04—Oxygen-containing compounds
    • C08K5/10—Esters; Ether-esters
    • C08K5/11—Esters; Ether-esters of acyclic polycarboxylic acids
    • 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
    • C08K5/04—Oxygen-containing compounds
    • C08K5/10—Esters; Ether-esters
    • C08K5/12—Esters; Ether-esters of cyclic polycarboxylic acids
    • 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

Definitions

  • This invention relates to novel thermpoplastic molding compositions which have good processing characteristics and are moldable into finished articles having good impact resistance. More particularly, the invention is concerned with thermoplastic compositions of a polyphenylene ether resin, a polymer selected from hydrogenated A-B-A 1 block copolymer and unsaturated A-B-A 1 block copolymers, and a plasticizer composition which is present in an amount sufficient to provide improved processing characteristics to the resultant molded article while, at the same time, rendering the total composition food compatible.
  • 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. Patents Nos. 3,306,874 and 3,306,875 and Stamatoff U.S. Patents Nos. 3,257,357 and 3,257,358.
  • polystyrene resin-polystyrene compositions are disclosed in Cizek, U.S. Patent No. 3,383,435.
  • polyphenylene ether resins can also be combined with block copolymers of the A-B-A 1 - type, e.g., polystyrene-polybutadiene-polystyrene, and with acrylic resin modified diene rubber containing resins, to provide compatible compositions characterized by a number of excellent physical properties in the resulting molded articles.
  • thermoplastics are also known. In general, these are either blended physically with the thermoplastic or are used to unite chemically with the plastics and to modify it.
  • 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. Patent No. 3,693,506.
  • Other self-extinguishing polyphenylene etherpolystyrene compositions are disclosed by Reinhard in U.S. Patent No. 3,809,729, wherein aromatic halogens combined with antimony compounds are used as flame retardant additives.
  • 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.
  • compositions consisting of polyphenylene ether or various combinations of polyphenylene ether and certain polymeric modifiers, and aromatic phosphare compounds exhibit excellent self-extinguishing behavior, Impact strength and acceptable surface gloss.
  • Such compositions are disclosed by Haaf et al. in copending application Serial No. 870,984, filed January 20, 1978, and assigned to the same assignee as the present invention.
  • compositions achieve a combination of high heat distortion, good impact strength and good self-extinguishing properties, they encounter some difficulty in processing and yield a product which has surface gloss characteristics which, while good, has deficiencies which can be improved upon via the utilization of minor amounts of low molecular weight polystyrene, as has been disclosed by Lee et al. in copending application Serial No. 84,746, filed October 15, 1979, which application is also assigned to the same assignee as the present invention.
  • compositions vhich exhibit a combination of high heat distortion, good impact strength, good self-extinguishing properties and in some instance ease of processability and high surface gloss characteristics in the resultant molded articles, such results are achieved via the utilization of compositions as flame retardant plasticizers and the like vhich are not compatible with FDA requirements controlling the use of such compositions in contact with edible food products, thereby rendering these compositions unsuitable for use as packaging materials and the like.
  • such compositions as have been disclosed in the art, suffer from additional limitations in the physical characteristics of the- resultant molded articles, such as to render them inappropriate for use in a number of specialized applications as will be apparent to those skilled in the art.
  • thermoplastic molding compositions which have improved processing characteristics and, after molding, have improved impact resistance, comprising an intimate admixture of:
  • composition comprising (i) a polyphenylene ether resin and (ii) a polymer selected from the group consisting of hydrogenated A-B-A- 1 block copolymers, and unsaturated A-B-A 1 block copolymers, and
  • polyphenylene ether resins of (a) are preferably of the type having the structural formula:
  • n is a positive integer and is at least 50
  • 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 phenyl nucleus , hydrocarbonoxy radicals and halohydrocarbonoxy radicals having at least two carbon atoms between the halogen atom and the phenyl nucleus.
  • polyphenylene ether resins for the compositions of this invention includes those of the above formula wherein each Q is alkyl, most preferably having from 1 to 4 carbon atoms .
  • members of this class include poly(2, 6-dimethyl-l, 4- ⁇ he ⁇ iylene) ether; poly (2, 6-diethyl-l,4-phenylene) ether ; poly(2-methyl-6-ethyl-l,4- pheny lene) ether; poly (2-methyl-6-propyl-l, 4-phenylene) ether; poly (2 , 6- dipropyl- 1 , 4-pheny lene) ether; poly (2- ethyl- 6 -propyl-1 ,
  • 4-phenylene) ether and the like.
  • poly(2 , 6- dimfithyl-l ,4-phenylene) ether preferably having an intrinsic viscosity of about 0. 45 deciliters per gram (dl. /g. ) as measured in chloroform at 30 oC.
  • the A-B-A 1 block copolymers of component (a) (ii) are well known. In general , these are block copolymers of the A-B-A 1 type in which terminal blocks A and A 1 are the same or different and, prior to hydrogenation , comprise homo polymers of copolymers derived. from vinyl aromatic hydrocarbons and, especially, vinyl aromatics vhaxein the aromatic moiety can be either monocyclic or polycyclic. Examples of the monomers are styrene, alpha methyl styrene, vinyl xylene, ethyl vinyl xylene, vinyl naphthalene, and the like.
  • Center block B will always be derived from a conjugated diene, e.g., butadiene, isoprene, 1,3-pentadiene, and the like.
  • center block B will be comprised of polybutadiene or polyisoprene.
  • terminal blocks A and A 1 having average molecular weights of 4,000 to 115,000 and center 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 has an average molecular weight between about 50,000 and 300,000.
  • the terminal blocks will preferably comprise from 2 to 331 by weight, and more preferably, 5 to 30% by weight of the total block copolymer.
  • Especially preferred axe A-B-A 1 type block copolymers having a polybutadiene center block wherein 35 to 55%, or more preferably, 40 to 50% of the carbon atoms present in the butadiene polymer block are in the form of dependent vinyl side chains.
  • the A-B-A 1 block copolymers will have an unsaturation in the center block B reduced to less than 10% and more preferably, less than 5%, of its original value.
  • the hydrogenated block copolymers are formed by techniques which are well known to those skilled in the art. For instance, the preparation of these materials is described in detail in Jones, U.S. Patent No. 3,431,323, the disclosure of which is incorporated herein by reference.
  • Hydrogenation can be carried out with a variety of hydrogenation catalysts, such as nickel on Kieselguhr, Raney nickel, copper chromate, molybdenum sulfide and finely divided platinum or other noble metals on a low surface area catalyst.
  • hydrogenation catalysts such as nickel on Kieselguhr, Raney nickel, copper chromate, molybdenum sulfide and finely divided platinum or other noble metals on a low surface area catalyst.
  • Hydrogenation can be conducted at any desired temperature or pressure, e.g., from atmospheric to 3,000 p.s.i.g., the usual range being between 100 and 1,000 p.s.i.g., and at temperatures from about 75o to 600oF., for times between 0.1 and 24 hours, preferably 0.2 to 8 hours.
  • Particular preferred block copolymers are Kraton 1101, an unsaturated polystyrene-polybutadiene-polystyrene block copolymer commercially available from Shell Chemical Company and Kraton G 1652, a hydrogenated polystyrene-polybutadiene-polystyrene block copolymer commercially available from Shell Chemical Company.
  • the plasticizers of the present invention are compositions selected from the group consisting essentially of the alkyl adipates, alkyl phthalates and paraffinic oils amongst which the most preferred compositions are dioctyl adipate, trimellitate ester, butyl phthaly butyl glycolcate, dioctyl phthalate, mineral oil and extra heavy mineral oil.
  • Dioctyl adipate, trimellitate ester (as Santicizer 79TM), butyl phthaly butyl glycolate (as Santicizer B-16) and dioctyl phthalate are all commercially available from Monsanto Chemical Company.
  • Mineral oil (as Shellflex 371) is commercially available from Shell Chemical Company and extra heavy mineral oil (as KAYDOL ® ) is commercially available from Witco Chemical Company.
  • the respective amounts of the major 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-B-A 1 block copolymer.
  • the most preferred such compositions contain no less than about 65% by weight of polyphenylene ether, based on the total weight of the resinous components in the composition.
  • amounts of from 1 to 40 parts by weight of the total composition can be employed to yield a good combination of properties in the resultant product with from 10 to 25 parts by weight being preferred. Particular amounts will, of course, vary depending on the needs of the specific composition.
  • compositions of the invention can also further include glass fibers as a reinforcing filler, especially preferably, fibrous glass filaments comprised of lime-altaainum borosilicate glass which is relatively soda free, known as "E" glass.
  • glass fibers as a reinforcing filler
  • fibrous glass filaments comprised of lime-altaainum borosilicate glass which is relatively soda free, known as "E" glass.
  • 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, flame blowing and mechanical pulling.
  • the preferred filaments for plastics reinforcement are made by mechanical pulling.
  • the filament diameters range from about
  • 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.
  • up to about 50% of glass can be present without causing flow problems.
  • 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.
  • compositions accordingto the invention are set forth for illustrative purposes only, and are not to be construed as limiting.
  • compositions shown in Table 1, were prepared by preblending the components, extruding the blend 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.1bs./in.n., and the values for Gardner impact strength are in units of in.-1bs.
  • Tensile yield, tensile break, flexural yield and flexural modulus values are each in units of p.s.i. x 10- 3 .
  • Tensile elongation values are in percent (Z) ; Heat Distortion Temperature (HDT) in oF., and melt viscosity in poise.

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  • 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)
PCT/US1981/000044 1980-01-14 1981-01-13 Improve polyphenylene plasticizer blends WO1981002020A1 (en)

Priority Applications (2)

Application Number Priority Date Filing Date Title
BR8105866A BR8105866A (pt) 1980-01-14 1981-01-13 Misturas plastificantes de polifenileno aperfeicoadas
JP50353581A JPS58500833A (ja) 1981-01-13 1981-05-26 電気機械の固定子端部巻線を支持する装置

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
US11198680A 1980-01-14 1980-01-14
US111986 1980-01-14

Publications (1)

Publication Number Publication Date
WO1981002020A1 true WO1981002020A1 (en) 1981-07-23

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ID=22341519

Family Applications (1)

Application Number Title Priority Date Filing Date
PCT/US1981/000044 WO1981002020A1 (en) 1980-01-14 1981-01-13 Improve polyphenylene plasticizer blends

Country Status (5)

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EP (1) EP0043836A4 (enrdf_load_stackoverflow)
JP (1) JPS57500152A (enrdf_load_stackoverflow)
AU (1) AU6777981A (enrdf_load_stackoverflow)
BR (1) BR8105866A (enrdf_load_stackoverflow)
WO (1) WO1981002020A1 (enrdf_load_stackoverflow)

Cited By (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP0119416A1 (en) * 1983-02-18 1984-09-26 General Electric Company Thermoplastic molding compostions having improved dust suppression
WO1984004314A1 (en) * 1983-05-04 1984-11-08 Gen Electric Polymer mixture having flame-retarding properties, suitable for wire insulation extrusion, on the basis of polyphenylene oxide and electrically conductive wire
US4732928A (en) * 1985-10-02 1988-03-22 Asahi Kasei Kogyo Kabushiki Highly elastic thermoplastic elastomer composition
US6509412B1 (en) 2000-09-29 2003-01-21 Bridgestone Corporation Soft gel compatibilized polymer compound for high temperature use
WO2014085313A1 (en) * 2012-11-30 2014-06-05 Sabic Innovative Plastics Ip B.V. Poly(phenylene ether) article and composition
US8957143B2 (en) 2011-06-03 2015-02-17 Sabic Global Technologies B.V. Impact-resistant poly(arylene ether) resins with improved clarity

Citations (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3960808A (en) * 1974-02-08 1976-06-01 General Electric Company Polyphenylene ether composition
US4102850A (en) * 1977-04-13 1978-07-25 General Electric Company High impact polyphenylene ether resin compositions containing mineral oil
US4104323A (en) * 1977-04-18 1978-08-01 Shell Oil Company Adhesive composition containing a pre-blended polyphenylene ether resin
US4123410A (en) * 1977-09-30 1978-10-31 General Electric Company Polyphenylene ether resin compositions of reduced melt viscosity
US4141876A (en) * 1977-09-23 1979-02-27 Shell Oil Company Adhesive composition containing a polyphenylene ether resin
US4154712A (en) * 1977-09-30 1979-05-15 General Electric Company Low molecular weight polyphenylene ether compositions

Family Cites Families (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
AU4779472A (en) * 1971-11-22 1974-04-26 Gen Electric Polyphenylene ether and a block copolymer of a vinyl aroma- tic compound and a conjugated diene
AU506630B2 (en) * 1975-12-31 1980-01-17 General Electric Company Flexibilized compostions of polyhenlene
AU1988776A (en) * 1975-12-31 1978-06-01 Gen Electric ether resins
DE2751496C2 (de) * 1976-12-21 1994-09-22 Gen Electric Flammhemmende, biegsam gemachte Polyphenylenäther-Zusammensetzungen
DE2752383A1 (de) * 1976-12-28 1978-06-29 Gen Electric Plastizierte verstaerkte zusammensetzungen aus einem polyphenylenaetherharz

Patent Citations (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3960808A (en) * 1974-02-08 1976-06-01 General Electric Company Polyphenylene ether composition
US4102850A (en) * 1977-04-13 1978-07-25 General Electric Company High impact polyphenylene ether resin compositions containing mineral oil
US4104323A (en) * 1977-04-18 1978-08-01 Shell Oil Company Adhesive composition containing a pre-blended polyphenylene ether resin
US4141876A (en) * 1977-09-23 1979-02-27 Shell Oil Company Adhesive composition containing a polyphenylene ether resin
US4123410A (en) * 1977-09-30 1978-10-31 General Electric Company Polyphenylene ether resin compositions of reduced melt viscosity
US4154712A (en) * 1977-09-30 1979-05-15 General Electric Company Low molecular weight polyphenylene ether compositions

Cited By (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP0119416A1 (en) * 1983-02-18 1984-09-26 General Electric Company Thermoplastic molding compostions having improved dust suppression
WO1984004314A1 (en) * 1983-05-04 1984-11-08 Gen Electric Polymer mixture having flame-retarding properties, suitable for wire insulation extrusion, on the basis of polyphenylene oxide and electrically conductive wire
EP0124916A1 (en) * 1983-05-04 1984-11-14 General Electric Company Flame retardant polyphenylene ether composition
US4732928A (en) * 1985-10-02 1988-03-22 Asahi Kasei Kogyo Kabushiki Highly elastic thermoplastic elastomer composition
US6509412B1 (en) 2000-09-29 2003-01-21 Bridgestone Corporation Soft gel compatibilized polymer compound for high temperature use
US8957143B2 (en) 2011-06-03 2015-02-17 Sabic Global Technologies B.V. Impact-resistant poly(arylene ether) resins with improved clarity
WO2014085313A1 (en) * 2012-11-30 2014-06-05 Sabic Innovative Plastics Ip B.V. Poly(phenylene ether) article and composition

Also Published As

Publication number Publication date
EP0043836A1 (en) 1982-01-20
BR8105866A (pt) 1981-11-24
JPS57500152A (enrdf_load_stackoverflow) 1982-01-28
AU6777981A (en) 1981-08-07
EP0043836A4 (en) 1982-04-29

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