WO1998054262A1 - Composition de polycetone renforcee - Google Patents

Composition de polycetone renforcee Download PDF

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Publication number
WO1998054262A1
WO1998054262A1 PCT/GB1998/001534 GB9801534W WO9854262A1 WO 1998054262 A1 WO1998054262 A1 WO 1998054262A1 GB 9801534 W GB9801534 W GB 9801534W WO 9854262 A1 WO9854262 A1 WO 9854262A1
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WO
WIPO (PCT)
Prior art keywords
composition
graft copolymer
polyketone
amount
resin
Prior art date
Application number
PCT/GB1998/001534
Other languages
English (en)
Inventor
James Graham Bonner
Original Assignee
Bp Chemicals Limited
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
Priority claimed from GBGB9711129.8A external-priority patent/GB9711129D0/en
Priority claimed from GBGB9717355.3A external-priority patent/GB9717355D0/en
Application filed by Bp Chemicals Limited filed Critical Bp Chemicals Limited
Priority to AU75437/98A priority Critical patent/AU7543798A/en
Publication of WO1998054262A1 publication Critical patent/WO1998054262A1/fr

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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
    • C08L73/00—Compositions of macromolecular compounds obtained by reactions forming a linkage containing oxygen or oxygen and carbon in the main chain, not provided for in groups C08L59/00 - C08L71/00; Compositions of derivatives of such polymers

Definitions

  • the present invention relates to polymer compositions containing a polyketone polymer which have improved toughness.
  • polyketones are defined as linear polymers having an alternating structure of (a) units derived from carbon monoxide and (b) units derived from one or more olefinically unsaturated compounds.
  • Such polyketones have the formula:
  • Polyketones have use as thermoplastics for the production of eg containers or parts for the automotive industry. Such uses require the polymer to have suitable impact properties. Accordingly, it is known to incorporate into polyketones additives which improve the impact resistance properties of the polymer.
  • EP-A-451918 discloses that improved impact resistance, as measured by the Gardner test, can be obtained by blending into the polyketone a minor amount of a high rubber graft copolymer, obtainable by graft-polymerising a rigid (when polymerised) vinyl nitrile monomer in the presence of a preformed rubbery substrate selected from 1,3-diene polymers and rubbery copolymers thereof.
  • An example is a rigid styrene/acrylonitrile graft copolymer on a 1,3 diene substrate.
  • EP 0457374 relates to a polymer blend composition comprising:
  • a graft rubber composition comprising a substrate rubber having a glass transition temperature below 0°C and monomers comprising a vinyl aromatic monomer and one or more polar monomers selected from the group consisting of Ci to C 4 alkyl acrylates, Ci to C 4 alkyl methacrylates, methacrylonitrile and acrylonitrile, said monomers having been polymerised in the presence of and grafted on to the substrate rubber;
  • (C) a carboxylic acid containing ethylene/alkyl acrylate copolymer having a glass transition temperature below 20°C.
  • the present invention provides a polymer composition which comprises essentially:
  • SAN styrene/acrylonitrile
  • (B) can be a copolymer of an olefin e.g. propylene with ethylene, butene or other unsaturated aliphatic hydrocarbons or ethylene with propylene and a diene.
  • an olefin e.g. propylene with ethylene, butene or other unsaturated aliphatic hydrocarbons or ethylene with propylene and a diene.
  • Such copolymers are known and any such polymer can be used.
  • the elastomer used as the backbone of the graft copolymer is an ethylene-propylene rubber or an ethylene/propylene/diene polymer (EPDM), most preferably EPDM.
  • EPDM is an amorphous elastomeric polyolefin having a random distribution of units derived from ethylene, propylene and one or more dienes (e.g.
  • the styrene/acrylonitrile (SAN) resin is a copolymer formed from a vinyl nitrile monomer such as acrylonitrile and a vinyl aromatic monomer such as styrene or substituted styrenes.
  • Illustrative substituted styrenes include ⁇ -methyl styrene, ⁇ -ethylstyrene, p-methylstyrene, m-methylstyrene, p-ethylstyrene, m- isopropylstyrene, divinyl benzene, ⁇ ,4-dimethylstyrene, chlorostyrene and vinyl benzene chloride.
  • the amount of units derived from the vinyl nitrile monomer which are present in the copolymer may typically be from 5 to 50 % by weight, preferably 15 to 30 % by weight of the resin. Such resins are widely known and commercially available.
  • the amount of styrene/acrylonitrile (SAN) resin which is graft copolymerised with the polyolefinic elastomeric backbone may typically be from 5 to 60%, more preferably from 10 to 30% by weight of the graft copolymer.
  • Component (B) of the polymer composition of the present invention may comprise a mixture of two or more graft copolymers.
  • Methods for preparing graft copolymers are well known and any suitable method can be used to prepare the graft copolymer of the polyolefinic elastomer and the styrene/acrylonitrile (SAN) resin.
  • One such suitable method comprises blending together the polyolefinic elastomer and the styrene/acrylonitrile (SAN) resin in the presence of a free radical initiator, such as an organic peroxide or hydroperoxide, at a temperature which is above the melting point of the polyolefinic elastomer and which provides a suitable half-life of the free radical initiator.
  • a free radical initiator such as an organic peroxide or hydroperoxide
  • This grafting process can be carried out using known mixing equipment such as, for example, a Brabender mixer, a B anbury mixer or a roll mill.
  • the grafting process is carried out in a closed vessel.
  • a convenient method of preparing the graft copolymer is therefore to extrude the polyolefinic elastomer which forms the backbone of the graft copolymer, the styrene/acrylonitrile (SAN) resin and an organic peroxide or hydroperoxide through a single or multiple screw extruder.
  • SAN styrene/acrylonitrile
  • polyolefinic elastomer which forms the backbone of the graft copolymer may be dissolved or suspended in a solvent and the resulting solution or suspension is mixed with the styrene/acrylonitrile (SAN) resin and the free radical initiator.
  • SAN styrene/acrylonitrile
  • polyketones are defined as linear polymers having an alternating structure of (a) units derived from carbon monoxide and (b) units derived from one or more olefinically unsaturated compounds.
  • Suitable olefinic units are those derived from C 2 to C 2 - alpha-olefins or substituted derivatives thereof or arylaliphatic olefinically unsaturated compounds such as styrene or alkyl substituted derivatives of styrene. It is preferred that such olefin or olefins are selected from C to C ⁇ normal alpha-olefins (i.e. straight chain alpha-olefins) and it is particularly preferred that the olefin units are either derived from ethylene or most preferred of all from a mixture of ethylene and one or more C 3 to C ⁇ normal alpha-olefin(s) especially propylene or butene. In these most preferable materials it is further preferred that the molar ratio of ethylene units to C 3 to C ⁇ normal alpha-olefin units is greater than or equal to 1 most preferably between 2 and 30.
  • the polyketones employed in the invention preferably have a number average molecular weight of from 1000 to 500,000, preferably from 15,000 to
  • the melting point of the polyketones is preferably between 175 and 300°C, preferably from 180 to 225°C.
  • the graft copolymer (B) is incorporated in the polyketone in an amount of between 0.5 and 50% by weight, preferably from 5 to 40% and more preferably from 10 to 30% by weight, based on the weight of the polyketone plus graft copolymer.
  • composition of the present invention may also contain conventional additives such as antioxidants, stabilisers, processing aids, fillers etc.
  • composition of the present invention may optionally contain further toughening components other than components (B) and (C) of EP 0457374 as hereinbefore described.
  • the present invention provides a polyketone polymer composition having significant impact strength improvement compared with the unmodified polyketone polymer.
  • a further aspect of the invention relates to the use of a graft copolymer (B) to increase the impact strength of a polyketone polymer.
  • B graft copolymer
  • the following Examples illustrate the invention. Determination of Melt Flow Rate The Melt Flow Rate (MFR) of the polyketone was measured using a Davenport Melt Index Tester. Tests were carried out at a temperature of 240°C and an applied load of 5 kg.
  • the MFR was calculated from the mass of extrudate pushed through a die (2.095 mm diameter) over a 30 second period on application of the load 4 minutes after charging the polymer into the barrel of the instrument at a temperature of 240°C. Otherwise standard MFR procedures were followed (e.g. ISO 1133).
  • Polyketone/graft copolymer compositions were prepared using a PRISM TSE16 co-rotating twin screw extruder.
  • the extruder was operated at a screw speed of 200rpm and with the following set of temperatures: zone 1 (feed) 195- 200°C; zone 2, 205-215°C; zone 3 (die) 215-230°C.
  • zone 1 (feed) 195- 200°C; zone 2, 205-215°C; zone 3 (die) 215-230°C zone 1 (feed) 195- 200°C; zone 2, 205-215°C; zone 3 (die) 215-230°C.
  • zone 1 (feed) 195- 200°C
  • zone 2, 205-215°C zone 3 (die) 215-230°C.
  • the appropriate amount of graft copolymer was either preblended with the polyketone prior to being fed into the extruder or fed independently via an additional feeder.
  • Appropriate levels of stabilisers and antioxidants were premixed with the polyketone.
  • the polyketone used was a terpolymer of ethylene, propylene and carbon monoxide, and had a melting point of 194°C and a melt flow rate (MFR) of 9g/10minutes at 240°C and a 5kg load.
  • the graft copolymer was an ethylene/propylene/non-conjugated diene (EPDM) grafted with styrene/acrylonitrile (SAN) resin.
  • EPDM ethylene/propylene/non-conjugated diene
  • SAN-g-EPDM used was Royaltuf 372 P20 or Royaltuf 372 PX (which differ in viscosity) supplied by Uniroyal Chemical.
  • the polyketone/graft copolymer composition was compression moulded into plaques, 150 x 150 x 4mm, using the following conditions: Temp: 20°C above polyketone melting point
  • Samples for Izod impact testing were machined from the plaques and tested according to ASTM D256. Notched samples were tested, with a notch radius of 0.25mm. A pendulum weight and position was employed, such that it had a potential energy of 1545mJ.
  • the samples prepared from compositions according to the present invention had such improved impact strength compared with the unmodified polyketone that they did not break when the Izod impact test was carried out at a temperature of 23 °C.
  • the Izod impact test was performed at a temperature of -40°C, a 2 fold increase in impact strength value was observed.

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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)

Abstract

Composition polymère contenant essentiellement (A) une quantité principale d'une polycétone présentant une structure linéaire alternée comprenant (a) des motifs dérivés de monoxyde de carbone et (b) des motifs dérivés d'un ou plusieurs composés oléfiniquement insaturés; et (B) une quantité secondaire d'un polymère greffé présentant un squelette élastomère polyoléfinique, dont la température de transition vitreuse est inférieure à 0 °C, greffé à une résine styrène/acrylonitrile (SAN). Le squelette élastomère polyoléfinique peut être un caoutchouc éthylène-propylène ou de l'EPDM.
PCT/GB1998/001534 1997-05-29 1998-05-27 Composition de polycetone renforcee WO1998054262A1 (fr)

Priority Applications (1)

Application Number Priority Date Filing Date Title
AU75437/98A AU7543798A (en) 1997-05-29 1998-05-27 Toughened polyketone composition

Applications Claiming Priority (4)

Application Number Priority Date Filing Date Title
GBGB9711129.8A GB9711129D0 (en) 1997-05-29 1997-05-29 Toughened polyketones composition
GB9711129.8 1997-08-16
GBGB9717355.3A GB9717355D0 (en) 1997-08-16 1997-08-16 Toughened polyketones composition
GB9717355.3 1997-08-16

Publications (1)

Publication Number Publication Date
WO1998054262A1 true WO1998054262A1 (fr) 1998-12-03

Family

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Family Applications (2)

Application Number Title Priority Date Filing Date
PCT/GB1998/001532 WO1998054261A2 (fr) 1997-05-29 1998-05-27 Composition de polycetone renforcee
PCT/GB1998/001534 WO1998054262A1 (fr) 1997-05-29 1998-05-27 Composition de polycetone renforcee

Family Applications Before (1)

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PCT/GB1998/001532 WO1998054261A2 (fr) 1997-05-29 1998-05-27 Composition de polycetone renforcee

Country Status (4)

Country Link
EP (1) EP0985002A2 (fr)
JP (1) JP2002500692A (fr)
AU (2) AU7543698A (fr)
WO (2) WO1998054261A2 (fr)

Cited By (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US6093463A (en) * 1997-12-12 2000-07-25 Intella Interventional Systems, Inc. Medical devices made from improved polymer blends
US6099926A (en) * 1997-12-12 2000-08-08 Intella Interventional Systems, Inc. Aliphatic polyketone compositions and medical devices
WO2017057847A1 (fr) * 2015-10-02 2017-04-06 삼성전자주식회사 Composition polymère, procédé de production de composition polymère, appareil électronique, et procédé de fabrication d'appareil électronique

Families Citing this family (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
KR101755708B1 (ko) * 2011-09-09 2017-07-10 현대자동차주식회사 내충격성 및 유연성이 향상된 폴리케톤 조성물
KR101705647B1 (ko) * 2015-05-27 2017-02-10 주식회사 효성 폴리케톤 섬유로 이루어지는 플렉시블 컨테이너 및 이의 제조방법
KR101867940B1 (ko) * 2017-01-19 2018-06-15 주식회사 효성 말레산무수물 그라프트 고무를 적용한 폴리케톤 조성물
KR101849200B1 (ko) * 2017-01-19 2018-04-16 주식회사 효성 충격강도가 개선된 폴리케톤 조성물
CN107513263B (zh) * 2017-10-19 2020-08-04 威海联桥新材料科技股份有限公司 一种热塑性弹性体垫片材料及其生产方法
CN109666256A (zh) * 2018-11-15 2019-04-23 广州敬信高聚物科技有限公司 一种无卤阻燃热塑性弹性体组合物及其制备方法和应用

Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4900789A (en) * 1988-12-22 1990-02-13 Shell Oil Company Polymer blend of carbon monoxide/olefin copolymer and conjugated alkadiene
EP0451918A2 (fr) * 1990-04-12 1991-10-16 Shell Internationale Researchmaatschappij B.V. Compositions de polycétones et de polymères
EP0457374A2 (fr) * 1990-02-12 1991-11-21 Shell Internationale Researchmaatschappij B.V. Composition polycétone/polymère comprenant un polymère linéaire alterné de monoxyde de carbone et d'un composé éthyléniquement insaturé

Family Cites Families (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4520169A (en) * 1982-09-02 1985-05-28 E. I. Du Pont De Nemours And Company Elastomeric sol/gel blends
DE68911597T2 (de) * 1988-06-08 1994-04-07 Shell Int Research Harzzusammensetzung.
US5369170A (en) * 1993-12-13 1994-11-29 Shell Oil Company Composite systems of polyketone and aminated, modified polyolefins

Patent Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4900789A (en) * 1988-12-22 1990-02-13 Shell Oil Company Polymer blend of carbon monoxide/olefin copolymer and conjugated alkadiene
EP0457374A2 (fr) * 1990-02-12 1991-11-21 Shell Internationale Researchmaatschappij B.V. Composition polycétone/polymère comprenant un polymère linéaire alterné de monoxyde de carbone et d'un composé éthyléniquement insaturé
EP0451918A2 (fr) * 1990-04-12 1991-10-16 Shell Internationale Researchmaatschappij B.V. Compositions de polycétones et de polymères

Cited By (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US6093463A (en) * 1997-12-12 2000-07-25 Intella Interventional Systems, Inc. Medical devices made from improved polymer blends
US6099926A (en) * 1997-12-12 2000-08-08 Intella Interventional Systems, Inc. Aliphatic polyketone compositions and medical devices
WO2017057847A1 (fr) * 2015-10-02 2017-04-06 삼성전자주식회사 Composition polymère, procédé de production de composition polymère, appareil électronique, et procédé de fabrication d'appareil électronique
US10851238B2 (en) 2015-10-02 2020-12-01 Samsung Electronics Co., Ltd. Polymeric composition, method for producing polymeric composition, electronic apparatus, and method for manufacturing electronic apparatus

Also Published As

Publication number Publication date
AU7543798A (en) 1998-12-30
EP0985002A2 (fr) 2000-03-15
WO1998054261A3 (fr) 1999-03-04
WO1998054261A2 (fr) 1998-12-03
AU7543698A (en) 1998-12-30
JP2002500692A (ja) 2002-01-08

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