EP0016040A1 - Binary and ternary thermoplastic polycarbonate alloys - Google Patents

Binary and ternary thermoplastic polycarbonate alloys

Info

Publication number
EP0016040A1
EP0016040A1 EP79900647A EP79900647A EP0016040A1 EP 0016040 A1 EP0016040 A1 EP 0016040A1 EP 79900647 A EP79900647 A EP 79900647A EP 79900647 A EP79900647 A EP 79900647A EP 0016040 A1 EP0016040 A1 EP 0016040A1
Authority
EP
European Patent Office
Prior art keywords
styrene
polycarbonate
carbonate
polystyrene
alloy
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.)
Withdrawn
Application number
EP79900647A
Other languages
German (de)
English (en)
French (fr)
Other versions
EP0016040A4 (en
Inventor
Gim Fun Lee Jr.
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
General Electric Co
Original Assignee
General Electric Co
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 General Electric Co filed Critical General Electric Co
Publication of EP0016040A4 publication Critical patent/EP0016040A4/en
Publication of EP0016040A1 publication Critical patent/EP0016040A1/en
Withdrawn legal-status Critical Current

Links

Classifications

    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L25/00—Compositions of, homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by an aromatic carbocyclic ring; Compositions of derivatives of such polymers
    • 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
    • C08L33/12—Homopolymers or copolymers of methyl methacrylate
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L69/00—Compositions of polycarbonates; Compositions of derivatives of polycarbonates
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L25/00—Compositions of, homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by an aromatic carbocyclic ring; Compositions of derivatives of such polymers
    • C08L25/02—Homopolymers or copolymers of hydrocarbons
    • C08L25/04—Homopolymers or copolymers of styrene
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • 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

Definitions

  • Polycarbonate polymers are known as being excellent molding materials since products made therefrom exhibit such properties as high impact strength, toughness, high trans ⁇ parency, wide temperature limits (high impact resistance o o
  • aromatic polycarbonate resins are relatively costly to produce and attempts have been made to reduce this cost by combining the polycarbonate with other
  • U. S. Patent 3, 162, 695 discloses blends of polycarbonate and methyl methacrylate butadiene-styrene (MBS) which have improved properties such as tensile, elongation, impact, hardness and the like.
  • MBS methyl methacrylate butadiene-styrene
  • OMPI an alkyl cellulose ether, and a polyurethane elastomer. These blends are considered to be more resistant to environmental stress crazing and cracking.
  • U. S. Patent 3, 862, 998 discloses a polycarbonate- styrene/ maleic acid anhydride copolymer blend having improved hot water stability.
  • U. S. Patent 3, 873, 641 discloses blends of polycarbonate with a mixture of a butadiene polymer and a copolymer of styrene, OQ -methyl styrene, methyl methacrylate and mixtures thereof, and a copolymer of acrylonitrile, metha- crylonitrile, methyl methacrylate and mixtures thereof. These blends are considered to have improved thermal stability and moduli of elasticity.
  • U. S. Patent 3, 891, 719 discloses an improved thermo- plastic molding composition consisting of a blend of poly ⁇ carbonate and a graft copolymer of styrene and acrylonitrile and an acrylic acid ester homo- and/or co-polymer.
  • U. S. Patent 3, 954, 905 discloses an improved thermo ⁇ plastic molding composition consisting of a blend of a poly- carbonate and (1) a graft copolyxper of styrene, methyl metha ⁇ crylate or mixtures thereof and acrylonitrile or acrylic acid esters onto a butadiene homo- or co-polymer; and (2) a co ⁇ polymer of styrene and/or or a copolymer of acrylonitrile and/or acrylic acid ester.
  • U. S. Patent 3, 966, 842 discloses a blend of polycarbonate with a rubber reinforced styrene /maleic anhydride composition having copolymerized therein styrene, maleic anhydride and rubber.
  • Polycarbonate-polystyrene blends are disclosed and dis- cussed in a paper entitled Structure and Properties of Hetero- phase and Blended Polymers given at the PI Research Meet ⁇ ing No. 4 on April 8, 1975 at the University of- Bristol.
  • a ' W1 A blend of tetramethyl bisphenol -A (2, 2-bis (4-hydroxy- phenyl) propane) with polystyrol grafted on natural rubber base to obtain a composition having high impact and long term creep strength is dis closed in a paper entitled Structure and Proper- ties of Multi-Phas e Synthetics - II/Natural Rubber- Modified Polycarbonates by G. Humme, H. Roehr and V. Serini which appeared in DieAngewandte Makromalekulare Chemie, 158 / 59 (1977), 85- 94 (No. 860).
  • compositions or alloys of this invention consist of binary blends of polycarbonate and polystyrene and ternary blends of polycarbonate polystyrene and methyl methacrylate butadiene- styrene (MBS) . While the properties of the polycar ⁇ bonate are modified, thos e of the polystyrene are improved.
  • the binary and ternary blends of the invention result in compositions or alloys that are not only more economical to produce, but which also exhibit good flow, proces sing, tensile and heat distortion properties enabling them to be used over a wide range of applications .
  • alloy as used herein is intended to mean and should be understood as meaning a composite material made by blending polymers or copolymers with other polymers or elastomers .
  • any of the aromatic poly ⁇ carbonates can be employed that are prepared by reacting a diphenol with a carbonate precursor.
  • diphenols that can be employed are bisphenol-A (2, 2-bis(4- 5 hydroxyphenyl) propane), bis (4 -hydroxyphenyl) methane, 2, 2-bis (4-hydroxy-3-methylphenyl)propane, 4, 4-bis(4-hydroxyphenyl) heptane, 2, 2-(3, 5, 3", 5'-tetrachloro-4, 4'-dihydroxydiphenyl) propane, 2, 2-(3, 5, 3', 5'-tetrabromo-4, 4'-dihydroxydiphenyl) propane, (3, 3'-dichloro-4, 4'-dihydroxyphenyl)methane.
  • Other 0 halogenated and nonhalogenated diphenols of the bisphenoltype can also be used such as are disclosed in U. S. Patents 2, 999, 835, 3, 028,
  • the carbonate precursor used can be either a carbonyl halide, a carbonate ester or a halof ormate.
  • the carbonyl halides can be carbonyl bromide, carbonyl chloride and mixtures thereof.
  • the carbonate esters can be diphenyl carbonate, di- ⁇ (halophenyl) carbonates such as di- (chlorophenyl) carbonate, di- (bromophenyl) carbonate, di-(trichlorophenyl) carbonate, di-(tri- bromophenyl) carbonate, etc. , di- (alkylphenyl) carbonate such as
  • OM di(tolyl) carbonate, etc. di(naphthyl) carbonate, di-(chloronaphthayl) carbonate, phenyl tolyl carbonate, chlorophenyl chloronaphthyl carbonate, etc., or mixtures thereof.
  • the haloformates that can be used include bis-haloformates of dihydric phenols (bischloro-formates of hydroquinone, etc.) or glycols (bishaloformates of ethylene glycol, neopentyl glycol, polyethylene glycol, etc.) While other carbonate precursors will occur to those skilled in the art, carbonyl chloride, also known as phosgene, is preferred.
  • polymeric derivatives of dihydric phenol, a dicarboxylic acid and carbonic acid such as disclosed in U.S. Patent 3,169,121 which is incorporated herein by reference, and which are particularly preferred.
  • This class of compounds is generally referred to as copolyester- carbonates.
  • Molecular weight regulators, acid acceptors and catalysts can also be used in obtaining the aromatic polycarbonates of this invention.
  • the useful molecular weight regulators include monohydric phenols such as phenol, chroman-I, paratertiary- butylphenol, parabromophenol, primary and secondary amines, etc.
  • phenol is employed as ' the molecular weight regulator.
  • a suitable acid acceptor can be either an organic or an inorganic acid acceptor.
  • a suitable organic acid acceptor is a tertiary amine such as pyridine, trieth lamine, dimethylaniline. tributylamine, etc.
  • the inorganic acid acceptor can be either a hydroxide, a carbonate, a bicarbonate, or a phosphate of an alkali or alkaline earth metal.
  • the catalysts which can be employed are those that typically aid the polymerization of the diphenol with phosgene.
  • Suitable catalysts include tertiary amines such as trieth lamine, tripropyl- a ine, N,N-dimethylaniline, quaternary ammonium compounds such as, for example, tetraethylammonium bromide, cetyl triethyl ammonium bromide, tetra-n- heptylammonium iodide, tetra-n-propyl ammonium bromide, tetramethylammonium chloride, tetramethyl ammonium hydroxide, tetra-n-butyl ammonium iodide, benzyltrimethyl ammonium chloride and quaternary phosphoniu compounds such as, for example, n-butyltriphenyl phosphonium bromide and methyltri- phenyl phosphonium bromide.
  • quaternary ammonium compounds such as, for example, n-butyltriphenyl
  • branched polycarbonates wherein a pol functional aromatic compound is reacted with the diphenol and carbonate precursor to provide a thermoplastic randomly branched poly ⁇ carbonate.
  • These polyfunctional aromatic compounds contain at least three functional groups which are carboxyl, carboxylic anhydride, haloformyl, or mixtures thereof.
  • polyfunctional aromatic compounds which can be employed include trimellitic anhydride, trimellitic acid, trimellityl trichloride, 4-chloroformyl phthalic anhydride, pyromellitic acid, pyromellitic dianhydride, mellitic acid, mellitic anhydride, trimesic acid, benzophenonetetracarboxylic acid, benzophenone- tetracarboxylic anhydride, and the like.
  • the preferred polyfunctional aromatic compounds are trimellitic anhydride and trimellitic acid or their acid halide derivatives.
  • Blends of linear and branched aromatic poly ⁇ carbonates are also included within the scope of this invention.
  • polystyrene resins that can be employed in the practice of this invention are those such as are disclosed in U.S. Patent 4,073,765 and which are commercially available such as from the Foster Grant Company under their product identification 834. ' Illustrative of these styrene resins are those having at least 25 percent by weight polymer units derived from the compound having the formula:
  • styrene resin as used throughout this disclosure and in the claims and as defined by the above formula includes, by way of example, homopolymers, such as polystyrene and polychlorostyrene, the modified polystyrenes, such as rubber-modified polystyrenes and the styrene containing copolymers such as the styrene-acrylonitrile copolymers (SAN) , styrene-butadiene copolymers, styrene-maleic anhydride, styrene-acrylonitrile-butadiene copolymers (ABS) , poly -methylstyrene, copolymers of ethylvinyl benzene and divinylbenzene
  • SAN styrene-acrylonitrile copolymers
  • ABS styrene-maleic anhydride
  • ABS styrene-acrylonitrile-butadiene copo
  • the styrene resin is a rubber- modified, high impact styrene resin, such as poly- styrene which has been modified with natural and sunthetic rubber, such as polybutadiene, polyisoprene rubbery, copolymers of dienes with other co-monomers, such as styrene, acrylonitrile, acrylic esters and the like, including block copolymers of the A-B-A and A-B type wherein A is a vinyl aromatic, such as styrene, and B is a diene such as butadiene, as well as EPDM rubber and the like.
  • the polystyrene is one modified with a butadiene rubber.
  • MMS methyl methacrylate- butadiene-styrenes
  • EXAMPLE 1 One hundred (100) parts of an aromatic poly ⁇ carbonate, prepared by reacting a copolymer of tetra- bromo-bisphenol-A (2,2-bis(4-hydroxyphenyl)propane) and bisphenol-A with phosgene in the presence of an acid acceptor and a molecular weight regulator and having an intrinsic viscosity of 0.57 was mixed with polystyrene and MBS at the weight ratios shown in the Table by tumbling the ingredients together in a laboratory tumbler. The resulting mixture was then fed through an extruder which was operated at about
  • test bars were then injection molded at about 490°F into test bars of about 6.35 cm x 0.32 cm (2-1/2 in. by 1/8 in.) and into test bars of about 6.35 cm x 1.27 cm (2-1/2 in. by 1/2 in.) by about 0.32 cm (1/8 in.) thick.
  • the test bars (5 for each test listed in the Table) were subject to the test procedures set forth below.
  • PC identifies the polycarbonate
  • PS identifies the polystyrene
  • MFS methyl methacrylate butadiene-styrene components of the alloy.

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)
EP79900647A 1978-06-09 1980-01-10 Binary and ternary thermoplastic polycarbonate alloys Withdrawn EP0016040A1 (en)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
US91417578A 1978-06-09 1978-06-09
US914175 1978-06-09

Publications (2)

Publication Number Publication Date
EP0016040A4 EP0016040A4 (en) 1980-09-29
EP0016040A1 true EP0016040A1 (en) 1980-10-01

Family

ID=25434008

Family Applications (1)

Application Number Title Priority Date Filing Date
EP79900647A Withdrawn EP0016040A1 (en) 1978-06-09 1980-01-10 Binary and ternary thermoplastic polycarbonate alloys

Country Status (3)

Country Link
EP (1) EP0016040A1 (enrdf_load_stackoverflow)
JP (1) JPS56500140A (enrdf_load_stackoverflow)
WO (1) WO1980000027A1 (enrdf_load_stackoverflow)

Families Citing this family (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4624986A (en) * 1983-04-22 1986-11-25 The Dow Chemical Company Low temperature impact resistant carbonate polymer blends
US4526926A (en) * 1983-04-22 1985-07-02 The Dow Chemical Company Low gloss carbonate polymer blends
EP0175161B1 (de) * 1984-09-15 1990-04-04 Hüls Aktiengesellschaft Formmassen auf Basis von Thermoplasten
US5100974A (en) * 1990-12-04 1992-03-31 General Electric Company Blends of polycarbonate, alkylnaphthalene formalite and impact modifier

Family Cites Families (12)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3162695A (en) * 1961-06-26 1964-12-22 Borg Warner Blends of polycarbonates with butadiene-styrene, methyl methacrylate, styrene graft copolymer
US3792122A (en) * 1971-04-21 1974-02-12 Rohm & Haas Polyphenylene ether resins containing a butadiene-acrylic-styrene polymer modifier
JPS52503B2 (enrdf_load_stackoverflow) * 1971-12-29 1977-01-08
JPS5433259B2 (enrdf_load_stackoverflow) * 1972-02-09 1979-10-19
JPS557864B2 (enrdf_load_stackoverflow) * 1972-06-03 1980-02-28
US3988389A (en) * 1972-12-06 1976-10-26 Bayer Aktiengesellschaft Moulding compositions contain polycarbonate and graft copolymer of a resin forming monomer on a rubber
JPS52504B2 (enrdf_load_stackoverflow) * 1973-01-24 1977-01-08
JPS5137936B2 (enrdf_load_stackoverflow) * 1973-04-18 1976-10-19
US3954905A (en) * 1973-06-09 1976-05-04 Bayer Aktiengesellschaft Moulding composition of a polycarbonate, a graft copolymer and a copolymer and moulded articles therefrom
DE2329585C2 (de) * 1973-06-09 1984-01-05 Bayer Ag, 5090 Leverkusen Polycarbonat-Formmassen
DE2329546A1 (de) * 1973-06-09 1975-01-02 Bayer Ag Polycarbonat-formmassen zusatz in: 2353383
US4105711A (en) * 1974-01-17 1978-08-08 Bayer Aktiengesellschaft PVC moulding compounds with high dimensional stability to heat

Also Published As

Publication number Publication date
WO1980000027A1 (en) 1980-01-10
EP0016040A4 (en) 1980-09-29
JPS56500140A (enrdf_load_stackoverflow) 1981-02-12

Similar Documents

Publication Publication Date Title
US4123436A (en) Polycarbonate composition plasticized with esters
US4130530A (en) Cyclic siloxane plasticized polycarbonate composition
JPH0733472B2 (ja) 低光沢の熱可塑性ブレンド
US4224215A (en) Filled polycarbonate compositions
EP0016791A1 (en) Ductile and solvent resistant polycarbonate compositions having improved flame resistance
US4129546A (en) Plasticized with a minor amount of an oligomeric polymeric polycarbonate
US4105711A (en) PVC moulding compounds with high dimensional stability to heat
US4148773A (en) Polycarbonate composition containing siloxane plasticizer
US4211679A (en) Organoboron plasticized polycarbonate composition
JPS6142942B2 (enrdf_load_stackoverflow)
US4218357A (en) Plasticized polycarbonate composition
US4184994A (en) Plasticized polycarbonate composition employing solid ketones
US4831082A (en) Impact modified aromatic carbonate compositions
US4145329A (en) Plasticized polycarbonate composition
EP0016040A1 (en) Binary and ternary thermoplastic polycarbonate alloys
US4143023A (en) Plasticized polycarbonate composition
US4290934A (en) Plasticized polycarbonate composition
JPH04226563A (ja) 改良された加工性と性能を有するエンジニアリング熱可塑性樹脂組成物
US4839426A (en) Misciblizing blends of polycarbonate and styrene copolymers
US4111883A (en) Plasticized polycarbonate composition
CA1101581A (en) Plasticized polycarbonate composition
US4119603A (en) Plasticized polycarbonate composition
KR100258647B1 (ko) 하이드록시 작용화 그라프트 공중합체에 의해 수득된 저 광택 폴리카보네이트/에이비에스 블렌드
US4243570A (en) Plasticized polycarbonate composition
EP0269861B1 (en) Impact modified aromatic carbonate compositions

Legal Events

Date Code Title Description
PUAI Public reference made under article 153(3) epc to a published international application that has entered the european phase

Free format text: ORIGINAL CODE: 0009012

17P Request for examination filed
AK Designated contracting states

Designated state(s): DE FR GB

STAA Information on the status of an ep patent application or granted ep patent

Free format text: STATUS: THE APPLICATION HAS BEEN WITHDRAWN

18W Application withdrawn

Withdrawal date: 19810807

RIN1 Information on inventor provided before grant (corrected)

Inventor name: LEE JR., GIM FUN