WO1997031062A1 - Composition claire contenant un ether de polyphenylene et un copolymere sequence - Google Patents

Composition claire contenant un ether de polyphenylene et un copolymere sequence Download PDF

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Publication number
WO1997031062A1
WO1997031062A1 PCT/US1997/002641 US9702641W WO9731062A1 WO 1997031062 A1 WO1997031062 A1 WO 1997031062A1 US 9702641 W US9702641 W US 9702641W WO 9731062 A1 WO9731062 A1 WO 9731062A1
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WIPO (PCT)
Prior art keywords
block copolymer
range
block
composition according
molecular weight
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Application number
PCT/US1997/002641
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English (en)
Inventor
Michael John Modic
Ronald Wroczynski
James Scobbo
Gim Lee
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Shell Oil Company
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Publication of WO1997031062A1 publication Critical patent/WO1997031062A1/fr

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    • 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
    • C08K5/13—Phenols; Phenolates
    • C08K5/134—Phenols containing ester groups
    • C08K5/1345—Carboxylic esters of phenolcarboxylic acids
    • 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
    • C08L53/025—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 modified
    • 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 polyphenylene ether blend compositions.
  • Polyphenylene ethers also known as polyphenylene oxide (PPO®) are naturally clear high melting thermoplastic engineering resins. Because of their high melting points the polymers by themselves are of limited utility. However, PPE is highly miscible in polystyrene and highly miscible in many high impact polystyrenes produced by rubber modification (HIPS) . Such blends are lower melting and thus constitute the type of PPE compositions typically employed in commerce. While PPE is a high strength material, it has low impact strength as measured by notch sensitive tests such as notched Izod. The incorporation of high impact polystyrene improves impact strength but results in a loss of clarity.
  • A-B-A triblock linear polymers which are generally designated A-B-A can be produced either by the sequential polymerization of the monovinylarene monomer followed by the conjugated diene monomer, followed by a second aliquot of monovinyl aromatic monomer or by the coupling of the A-B species with a difunctional coupling agent.
  • polyfunctional coupling agents can be utilized to give a radial or star configuration.
  • polymers are defined in terms of their total monovinyl aromatic content since resinous products are produced from predominantly polymerized monovinyl aromatic component whereas rubbery materials result from predominantly conjugated diene compositions.
  • a clear PPE composition containing 2 to 30 weight percent of a hydrogenated conjugated diene/monovinyl aromatic linear block copolymer, said copolymer having:
  • polymerized monovinyl aromatic blocks having a molecular weight within the range of 23,000-100,000; polymerized conjugated diene blocks of less than 150,000 molecular weight; and a total molecular weight in the case of A-B polymers within the range of 40,000-225,000, and in the case Of A-B-A polymers, 80,000-350,000.
  • PPE resins suitable for use in this invention are commercially available and are produced by techniques well known in the art such as by oxidizing a phenol with an oxygen-containing gas in the presence of a catalyst system comprising a cuprous salt and a tertiary amine.
  • Suitable PPE resins are homo- and copolymers with repeating units of the formula
  • Q, Q', Q" and Q 1 '' are independently selected from the group consisting of hydrogen, hydrocarbon radicals, halohydrocarbon radicals having at least two carbon atoms between the halogen atom and the phenol nucleus, hydrocarbonoxy radicals and halohydrocarbonoxy radicals having at least two carbon atoms between the halogen atom and the phenol nucleus, and Q', Q" and Q' ' ' in addition may be halogen with the proviso that Q and Q' are preferably free of any tertiary carbon atoms; and n represents the total number of monomer residues and is an integer of at least 50.
  • poly(2,6-dimethyl-l,4- phenylene)ether is Especially preferred.
  • the monovinyl aromatic/conjugated diene copolymers can be made by anionic polymerization with an alkali metal catalyst such as sec-butyllithium as disclosed for instance in Bean, Jr., U.S. 4,764,572 (August 16, 1988), Holden et al, U.S. 3,231,635 (January 25, 1966), Wald et al, U.S. 3,700,633 (October 24, 1972, and Stevens et al, U.S. 5,194,530 (March 16, 1993), the disclosures of which are hereby incorporated by reference.
  • the monovinyl aromatic monomer suitable for producing the resinous block of the block copolymers of this invention is styrene or ⁇ -methylstyrene, most preferably styrene.
  • the conjugated diene monomers suitable for producing the rubbery block of the block copolymers utilized in this invention are preferably conjugated alkadienes having 4 to 8 carbon atoms.
  • Illustrative of such conjugated alkadienes are 1,3-butadiene (butadiene), 2-methyl-l,3- butadiene (isoprene), 1-3-pentadiene (piperylene) , 1,3- octadiene, and 2-methyl-l,3-pentadiene.
  • Preferred conjugated alkadienes are butadiene and isoprene, most preferably isoprene.
  • the block copolymers utilized in this invention are those which have been selectively hydrogenated to remove most of the ethylenic or vinyl unsaturation and to leave unaffected most of the aromatic unsaturation.
  • Suitable known catalysts for accomplishing this include nickel compounds in combination with a reducing agent such as an aluminum alkyl. Hydrogenation is taught in U.S. Patents 3,494,942, 3,634,594, 3,670,054, 3,700,633, and Reissue 27,145, the disclosures of which are hereby incorporated by reference.
  • the hydrogenation is effective to remove a majority generally at least 90%, more generally at least 95% of the original unsaturation in the polymerized diene component and to remove no more than 50%, preferably no more than 25%, more preferably no more than 10% of the aromatic unsaturation in the polymerized monovinylarene component.
  • the block copolymers utilized in this invention have a weight percent polymerized monovinyl arene content within the range of 45 to 58.
  • the individual polymerized monovinyl arene blocks have a molecular weight within the range of 23,000-100,000, preferably a molecular weight within the range of 40,000- 80,000.
  • the polymerized conjugated diene blocks have a molecular weight of less than 150,000.
  • the total molecular weight of the block copolymers is within the range of 40,000-225,000 for the A-B diblock polymers, preferably 60,000-160,000 and for the A-B-A polymers, the molecular weight is within the range of 80,000-350,000, preferably 100,000-275,000.
  • Molecular weights of linear polydienes are conveniently measured by Gel Permeation Chromatography (GPC) , where the GPC system has been appropriately calibrated. Polymers of known molecular weight are used to calibrate and these must be of the same molecular structure and chemical composition as the unknown linear polymers or segments that are to be measured. For anionically polymerized linear polymers, the polymer is essentially monodispersed and it is both convenient and adequately descriptive to report the "peak" molecular weight of the narrow molecular weight distribution observed. As used herein, references to molecular weight mean "peak" molecular weight. These techniques are known in the art as disclosed for instance by Erickson et al, U.S.
  • the block copolymer is present in the compositions of this invention in an amount within the range of 2-30, preferably 5-25, more preferably 10-25 weight percent based on the weight of the copolymer and PPE component.
  • the PPE resin and the block copolymer can be combined by either melt blending or solution blending, but preferably are combined by melt blending.
  • the composition cannot contain any additional ingredients which would significantly impart haze.
  • a small amount of polystyrene may be added to improve the processability of the blends.
  • the polystyrene should not be added in an amount high enough to affect the haze properties (i.e. less than 10% weight) .
  • the compositions will, however, in almost all instances contain a small amount of stabilizer such as an antioxidant, so as to prevent degradation of the polymer.
  • Such ingredients are generally present in an amount within the range of 0.01 to 2 weight percent, more generally 0.05 to 0.5 weight percent. Suitable stabilizers disclosed for instance in St.
  • composition of the invention may have some slight haze imparted by the copolymer. However, the compositions are such that they have a visual appearance of clarity and preferably a luminous transmittance of at least 20% of that of the unmodified PPE.
  • the compositions consist essentially of the PPE resin, the block copolymer, and the stabilizer with the stabilizer preferably being present in an amount within the range of 0.05 to 0.5 weight percent based on the weight of the PPE and block copolymer. Alternatively it consists essentially of these ingredients plus the polystyrene. Most preferably the compositions consist essentially of PPE, A-B block copolymer and antioxidant, again with the antioxidant being present in an amount within the range of 0.05 to 0.5 weight percent based on the weight of the polymeric ingredients.
  • compositions of this invention are useful for consumer items such as lighting fixtures.
  • EXAMPLES In the following examples, a styrene-isoprene A-B block copolymer was prepared utilizing an organolithium initiator in cyclohexane solvent and subsequent to the recovery of the polymers, they were each hydrogenated utilizing a nickel/aluminum catalyst to give a product wherein 2% of the original unsaturation in the polymerized isoprene remains and no more than 5% of the original unsaturation of the styrene is removed.
  • the PPE utilized was a product sold under the trade designation PPO 806 by GE Plastics.
  • the PPE and each of the block copolymers was melt blended on a 25 mm co- rotating twin screw extruder at 300°C and a screw speed of 300 RPM. All of the ingredients, including antioxidant, were dry tumble blended together prior to addition to the twin screw extruder. The blend extrudates were collected as pellets. The resulting blends were molded into test specimens on a 25 ton injection molding machine. The results of the analysis of these test specimens is shown herein below in Table 1.
  • Run 1 the neat PPE has excellent clarity but low impact strength.
  • Run 2 a block copolymer having only 22 weight percent styrene improves the impact strength but destroys clarity.
  • Runs 3-5 clarity is improved compared with Run 2 if the percentage polymerized styrene content is greater.
  • Run 4 with the same block copolymer as Run 3 at a higher level shows that 200,000 total molecular weight is close to the upper acceptable limit for total molecular weight with an AB polymer. As can be seen by comparing Run 4 with Run 6, the poor clarity in Run 4 is the result of the total molecular weight being almost too high, not the 50-50 weight ratio of resinous to rubbery component.
  • Run 7 shows that 12,000 total molecular weight is too low because at this molecular weight clarity is destroyed. Finally, Run 7 shows that the absolute size of the styrene block as well as the percent styrene is important since Run 7 had 50% styrene but gave unacceptable results.

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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)
  • Graft Or Block Polymers (AREA)

Abstract

Cette invention se rapporte à une composition claire d'un éther de polyphénylène présentant une résilience améliorée et contenant ledit éther de polyphénylène et un copolymère séquencé ayant un bloc résineux et un bloc caoutchouteux, ledit bloc résineux ayant un poids moléculaire relativement élevé et provenant soit du styrène soit du butadiène, la teneur en fraction résineuse dudit copolymère séquencé étant comprise entre 45 et 58 % en poids.
PCT/US1997/002641 1996-02-23 1997-02-20 Composition claire contenant un ether de polyphenylene et un copolymere sequence WO1997031062A1 (fr)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
US08/606,181 1996-02-23
US08/606,181 USH1725H (en) 1996-02-23 1996-02-23 Clear polyphenylene ether/block copolymer composition

Publications (1)

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WO1997031062A1 true WO1997031062A1 (fr) 1997-08-28

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Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP0799857A2 (fr) * 1996-04-03 1997-10-08 Shell Internationale Researchmaatschappij B.V. Composition résistant au choc à base de poly(éther de phénylène), polymère de styrène, et élastomère

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FR2354368A1 (fr) * 1976-06-07 1978-01-06 Shell Int Research Compositions contenant des copolymeres sequences hydrogenes et des resines thermoplastiques pour constructions mecaniques
US4196116A (en) * 1977-11-28 1980-04-01 General Electric Company Impact resistant polyphenylene ether compositions containing EPDM rubber-modified alkenyl aromatic resins and hydrogenated diblock copolymers
US4341879A (en) * 1980-03-17 1982-07-27 Mitsubishi Gas Chemical Company, Inc. Polyphenylene ether resin composition having improved heat stability and impact strength
WO1983001254A1 (fr) * 1981-10-02 1983-04-14 Gen Electric Compositions thermoplastiques ameliorees a resistance elevee aux chocs contenant un modificateur dibloc de choc
EP0367188A2 (fr) * 1988-11-01 1990-05-09 Asahi Kasei Kogyo Kabushiki Kaisha Composition de polymère thermoplastique
EP0409657A2 (fr) * 1989-07-21 1991-01-23 Novacor Chemicals (Canada) Ltd. Mélanges thermoplastiques à résistance au choc modifiée
JPH0386756A (ja) * 1989-08-30 1991-04-11 Asahi Chem Ind Co Ltd 耐衝撃、透明、耐熱樹脂組成物
EP0611802A2 (fr) * 1988-08-31 1994-08-24 Idemitsu Kosan Company Limited Compositions polymérique à base de styrène

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WO1983001254A1 (fr) * 1981-10-02 1983-04-14 Gen Electric Compositions thermoplastiques ameliorees a resistance elevee aux chocs contenant un modificateur dibloc de choc
EP0611802A2 (fr) * 1988-08-31 1994-08-24 Idemitsu Kosan Company Limited Compositions polymérique à base de styrène
EP0367188A2 (fr) * 1988-11-01 1990-05-09 Asahi Kasei Kogyo Kabushiki Kaisha Composition de polymère thermoplastique
EP0409657A2 (fr) * 1989-07-21 1991-01-23 Novacor Chemicals (Canada) Ltd. Mélanges thermoplastiques à résistance au choc modifiée
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Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP0799857A2 (fr) * 1996-04-03 1997-10-08 Shell Internationale Researchmaatschappij B.V. Composition résistant au choc à base de poly(éther de phénylène), polymère de styrène, et élastomère
EP0799857A3 (fr) * 1996-04-03 1997-12-29 Shell Internationale Researchmaatschappij B.V. Composition résistant au choc à base de poly(éther de phénylène), polymère de styrène, et élastomère

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Publication number Publication date
USH1725H (en) 1998-05-05

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