WO1996020247A1 - COMPOSITION POLYMERE RETICULEE CONTENANT UN COPOLYMERE POLYPROPYLENE-ETHYLENE ET UN COPOLYMERE ETHYLENE-α-OLEFINE - Google Patents

COMPOSITION POLYMERE RETICULEE CONTENANT UN COPOLYMERE POLYPROPYLENE-ETHYLENE ET UN COPOLYMERE ETHYLENE-α-OLEFINE Download PDF

Info

Publication number
WO1996020247A1
WO1996020247A1 PCT/NL1995/000441 NL9500441W WO9620247A1 WO 1996020247 A1 WO1996020247 A1 WO 1996020247A1 NL 9500441 W NL9500441 W NL 9500441W WO 9620247 A1 WO9620247 A1 WO 9620247A1
Authority
WO
WIPO (PCT)
Prior art keywords
ethylene
polymer composition
cross
copolymer
propylene
Prior art date
Application number
PCT/NL1995/000441
Other languages
English (en)
Inventor
Johannes Fredericus Repin
Wilhelmus Gerardus Marie Bruls
Ivan CHODÁK
Igor CHORVÁTH
Original Assignee
Dsm N.V.
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 Dsm N.V. filed Critical Dsm N.V.
Publication of WO1996020247A1 publication Critical patent/WO1996020247A1/fr

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
    • C08K5/04—Oxygen-containing compounds
    • C08K5/14—Peroxides
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L23/00—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers
    • C08L23/02—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers not modified by chemical after-treatment
    • C08L23/10—Homopolymers or copolymers of propene
    • C08L23/12—Polypropene
    • 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
    • C08L23/00—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers
    • C08L23/02—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers not modified by chemical after-treatment
    • C08L23/04—Homopolymers or copolymers of ethene
    • C08L23/08—Copolymers of ethene
    • C08L23/0807—Copolymers of ethene with unsaturated hydrocarbons only containing more than three carbon atoms
    • C08L23/0815—Copolymers of ethene with aliphatic 1-olefins
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L23/00—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers
    • C08L23/02—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers not modified by chemical after-treatment
    • C08L23/16—Elastomeric ethene-propene or ethene-propene-diene copolymers, e.g. EPR and EPDM rubbers
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L2312/00—Crosslinking

Definitions

  • the invention relates to a cross-linked polymer composition containing 40-90 wt.% propylene-ethylene copolymer and 10-60 wt.% ethylene- ⁇ -olefin copolymer.
  • a polymer composition of this type is known from
  • cross-linked polymer composition containing propylene-ethylene copolymer and ethylene- ⁇ - olefin copolymer having a high impact resistance at low temperature and also has good flow properties.
  • a drawback of the polymer composition described above is that the stiffness of these products with a high impact resistance is too low.
  • the aim of the invention is to obtain a polymer composition that does not present the above drawback.
  • the invention is characteriezd in that the propylene-ethylene copolymer contains 8-20 wt.% ethylene, the ethylene- ⁇ -olefin copolymer contains 75-90 wt.% ethylene and has a density of 920-890 kg/m 3 and in that the polymer composition has a notched Izod impact strength
  • JP-A-61/85462 describes a cross-linked polymer composition containing 60-85 wt.% of a propylene-ethylene block copolymer and 15-40 wt.% of an ethylene- ⁇ -olefin random copolymer.
  • This polymer composition has, as the polymer composition according to DE-A-32,30,516, a high impact strength at low temperatures.
  • the cross-linked polymer composition according to JP-A-61/85462 has as a drawback that the stiffness of this product is too low. The stiffness of a polymer composition is reflected by the flexural modulus, determined according to ASTM D790.
  • the impact strength of a polymer composition is reflected by the notched Izod impact strength, determined according to ASTM D256.
  • the polymer composition has a notched Izod impact strength ⁇ 10 kJ/m 2 at -30°, determined according to ASTM D256.
  • propylene-ethylene copolymers are: random copolymers of propylene, ethylene and an ⁇ -olefin containing 4-10 carbon atoms, block copolymers of propylene, ethylene and an ⁇ -olefin containing 4-10 carbon atoms, and reactor mixtures a propylene homopolymer and ethylene homopolymer or ethylene copolymer containing ethylene and one or more ⁇ -olefins with 3-10 carbon atoms.
  • the propylene-ethylene copolymer is a propylene-ethylene block copolymer. Polymer compositions with the highest impact strength are obtained when a propylene-ethylene block copolymer is used in the polymer composition according to the invention.
  • the cross-linked polymer composition according to the invention also contains 10-60 wt.% ethylene- ⁇ - olefin copolymer relative to the total amount of propylene-ethylene copolymer and ethylene- ⁇ -olefin copolymer present.
  • 'Ethylene- ⁇ -olefin copolymer' is in the context of this invention understood to mean random copolymers of ethylene with one or more olefinic comonomers containing 3-10 carbon atoms, containing 75-90 wt.% ethylene with a density of 920-890 kg/m 3 .
  • the density of the ethylene- ⁇ -olefin copolymer is too low when the ethylene content in the ethylene- ⁇ - olefin copolymer is under 75 wt.%. Than also the stiffness of the crosslinked polymer composition decreases.
  • the impact resistance of the polymer composition at low temperatures decreases.
  • 1-butene, 1-hexene and/or 1-octene are used as ⁇ -olefin in the ethylene- ⁇ -olefin copolymer.
  • ethylene- ⁇ -olefin copolymers are low-density polyethylene (LDPE), very-low-density polyethylene (VLDPE) and ultra-low-density polyethylene (ULDPE) and linear-low-density polyethylene (LLDPE).
  • the cross-linked polymer composition according to the invention can be prepared by kneading and melting a mixture of the propylene-ethylene copolymer and the ethylene- ⁇ -olefin copolymer in the required ratio in the presence of a radical-forming agent and a cross-linking agent.
  • the radical-forming agent can be chosen from among peroxides or azo compounds.
  • peroxides are used.
  • peroxides are benzyl peroxide, t-butyl perbenzoate, t-butyl peracetate, t-butyl peroxyisopropylcarbonate, 2,5-dimethyl-2,5- di(benzoylperoxy)hexane, 2,5-dimethy1-2,5- di(benzoylperoxy)hexyn-3, t-butyl diperadipate, t-butyl peroxy-3,5,5-trimethylhexanoate, methylethylketone peroxide, cyclohexanone peroxide, di-t-butyl peroxide, dicumyl peroxide, 2,5-dimethyl-2,5-di (t-butylperoxy)- hexane, 2,5-dimethyl-2 ,5-di(t-butylperoxy)
  • the amount of radical-forming agent present during the melting and kneading of the propylene-ethylene copolymer and the ethylene- ⁇ -olefin copolymer is usually between 0.01 and 3 wt.%, relative to the amount of propylene-ethylene copolymer plus ethylene- ⁇ -olefin copolymer.
  • the amount of radical-forming agent is 0.05-2 wt.%, relative to the amount of propylene- ethylene copolymer plus ethylene- ⁇ -olefin copolymer.
  • the cross-linking agent can be chosen from the group comprising compounds containing dihydroxy, divinyl, diallyl or triallyl containing compounds, such as 1,2-, 1,3- and 1,4-dihydroxybenzene, divinyl benzene or diallylphthalate.
  • 1,4-dihydroxybenzene is used as the cross-linking agent.
  • An amount of between 0.001 and 3 wt.% cross- linking agent, relative to the amount of propylene- ethylene copolymer plus ethylene- ⁇ -olefin copolymer, is usually present during the melting and kneading of the propylene-ethylene copolymer and the ethylene- ⁇ -olefin copolymer.
  • an amount of between 0.005 and 0.5 wt.% cross-linking agent is present.
  • a peroxide inhibitor is also present during the melting, kneading and mixing of the propylene- ethylene copolymer and the ethylene- ⁇ -olefin in the presence of a peroxide and a cross-linking agent.
  • the peroxide inhibitor ensures that the cross-linking reaction does not take place immediately when the melting and kneading are started. That way a good degree of mixing of the propylene-ethylene copolymer and the ethylene- ⁇ -olefin copolymer can be achieved before the cross-linking of the polymer composition takes place.
  • Various compounds may be used as the peroxide inhibitor, such as 1, -dihydroxybenzene, 2,6-di-t-butyl-p- cresol, t-butylcatechol, 4,4 '-butylidene-bis-(3-methyl-6- t-butylphenol) , 2,2 '-methylene-bis-(4-methyl-6-t- butylphenol) , 4,4 '-thio-bis(6-t-butyl-3-methylphenol) , mercaptobenzothiazole, dibenzothiazoledisulphide, 2,2,4- trimethyl-l,2-dihydroquinone polymers, phenyl- ⁇ - naphthylamine, N,N'-di- ⁇ -naphthyl-p-phenylenediamine and N-nitrosodiophenylamine.
  • the amount of peroxide inhibitor present during the melting and kneading of the polypropylene and the polyethylene is 0-0.5 wt.%, relative to the amount of propylene-ethylene copolymer plus ethylene- ⁇ -olefin copolymer.
  • both the cross-linking agent and the peroxide inhibitor are 1,4-dihydroxybenzene and between 0.005 and 0.5 wt.% 1, -dihydroxybenzene, relative to the amount of propylene-ethylene copolymer plus ethylene- ⁇ - olefin copolymer, is added.
  • the propylene-ethylene copolymer and ethylene- ⁇ - olefin copolymer are kneaded and melted together with the radical-forming agent, the cross-linking agent and optionally the peroxide inhibitor in the usual equipment, such as mixers, kneaders and single- or twin-screw extruders.
  • the temperature during the melting and kneading is 165 to 270°C.
  • the cross-linked polymer composition according to the invention may furthermore contain the usual additives such as fibres, fillers, nucleating agents, plasticizers, flame retardants, flow-promoting agents, lubricants, stabilisers and impact improving agents.
  • additives such as fibres, fillers, nucleating agents, plasticizers, flame retardants, flow-promoting agents, lubricants, stabilisers and impact improving agents.
  • the cross-linked polymer composition according to the invention is suitable for use large injection moulded parts for the automotive industry that are exposed to low temperatures, such as bumpers.
  • the impact strength (Izod) was determined according to ASTM D256.
  • the viscosity (SSV) was determined according to ASTM D3835 using a G ⁇ ttfert 1500 Viscotester at a shear rate of 115 s" 1 and a temperature of 240°C.
  • the diameter of the capillary tube was 1 mm, its length 30 mm and the entry angle was 180°C. The measurement was started after the material had been melted for 6 min.
  • the melt index (MI) was determined according to
  • the flexural modulus was determined according to
  • PE Ethylene- ⁇ -olefin copolymer
  • the polymer compositions were prepared by melting and kneading the various components in a Haake twin-screw extruder at a temperature of 175°C and a throughput of 20 g/min. TABLE 1

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

Composition polymère réticulée contenant 40 à 90 % en poids d'un copolymère propylène-éthylène dont 8 à 20 % en poids d'éthylène et 10 à 60 % en poids d'un copolymère éthylène-α-oléfine dont 75 à 90 % en poids d'éthylène. Ladite composition possède une densité de 920 à 890 kg/m3, une résistance aux essais de flexion dynamique Izod » de 10kJ/m2 à -20 °C et un module d'élasticité en flexion supérieur à 500 MPa. Ladite composition polymère réticulée est préparée par fonte et malaxage du copolymère propylène-éthylène et du copolymère éthylène-α-oléfine en présence d'un agent de formation de radicaux, d'un agent de réticulation et éventuellement d'un inhibiteur de peroxyde.
PCT/NL1995/000441 1994-12-27 1995-12-21 COMPOSITION POLYMERE RETICULEE CONTENANT UN COPOLYMERE POLYPROPYLENE-ETHYLENE ET UN COPOLYMERE ETHYLENE-α-OLEFINE WO1996020247A1 (fr)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
BE9401165A BE1009007A3 (nl) 1994-12-27 1994-12-27 Vernette polymeersamenstelling bevattende polypropeen en polyetheen.
BE9401165 1994-12-27

Publications (1)

Publication Number Publication Date
WO1996020247A1 true WO1996020247A1 (fr) 1996-07-04

Family

ID=3888553

Family Applications (1)

Application Number Title Priority Date Filing Date
PCT/NL1995/000441 WO1996020247A1 (fr) 1994-12-27 1995-12-21 COMPOSITION POLYMERE RETICULEE CONTENANT UN COPOLYMERE POLYPROPYLENE-ETHYLENE ET UN COPOLYMERE ETHYLENE-α-OLEFINE

Country Status (2)

Country Link
BE (1) BE1009007A3 (fr)
WO (1) WO1996020247A1 (fr)

Cited By (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2000078858A2 (fr) * 1999-06-24 2000-12-28 The Dow Chemical Company Compositions polyolefiniques a resistance superieure aux chocs
EP1186618A1 (fr) * 2000-09-08 2002-03-13 ATOFINA Research Polymères hétérophasiques de propylène à rhéologie réglable
EP1312617A1 (fr) * 2001-11-14 2003-05-21 ATOFINA Research Polypropylène à résistance au choc élevée
US6593005B2 (en) 2000-01-24 2003-07-15 Dow Global Technologies Inc. Composition and films thereof
US6776924B2 (en) 2000-05-04 2004-08-17 Dow Global Technologies Inc. Molecular melt and methods for making and using the molecular melt
US6800669B2 (en) 2000-12-22 2004-10-05 Dow Global Technologies Inc. Propylene copolymer foams
US6939919B2 (en) 2000-05-26 2005-09-06 Dow Global Technologies Inc. Polyethylene rich/polypropylene blends and their uses

Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE3230516A1 (de) * 1981-08-20 1983-03-24 Mitsubishi Petrochemical Co., Ltd., Tokyo Olefinblockmischpolymerisat und vernetzungsprodukt
JPS59223740A (ja) * 1983-06-02 1984-12-15 Mitsui Petrochem Ind Ltd ポリプロピレン組成物の製造方法
JPS6185462A (ja) * 1984-10-02 1986-05-01 Idemitsu Petrochem Co Ltd ポリプロピレン樹脂組成物の製造方法
WO1988008865A1 (fr) * 1987-05-07 1988-11-17 Norsolor Compositions thermoplastiques, leur procede de preparation et leur application a l'obtention d'articles industriels

Patent Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE3230516A1 (de) * 1981-08-20 1983-03-24 Mitsubishi Petrochemical Co., Ltd., Tokyo Olefinblockmischpolymerisat und vernetzungsprodukt
JPS59223740A (ja) * 1983-06-02 1984-12-15 Mitsui Petrochem Ind Ltd ポリプロピレン組成物の製造方法
JPS6185462A (ja) * 1984-10-02 1986-05-01 Idemitsu Petrochem Co Ltd ポリプロピレン樹脂組成物の製造方法
WO1988008865A1 (fr) * 1987-05-07 1988-11-17 Norsolor Compositions thermoplastiques, leur procede de preparation et leur application a l'obtention d'articles industriels

Non-Patent Citations (2)

* Cited by examiner, † Cited by third party
Title
DATABASE WPI Section Ch Week 8505, Derwent World Patents Index; Class A17, AN 85-028507, XP002001086 *
DATABASE WPI Section Ch Week 8624, Derwent World Patents Index; Class A17, AN 86-152561, XP002001087 *

Cited By (18)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US6841620B2 (en) 1999-06-24 2005-01-11 Dow Global Technologies Inc. Polyolefin composition with improved impact properties
WO2000078858A2 (fr) * 1999-06-24 2000-12-28 The Dow Chemical Company Compositions polyolefiniques a resistance superieure aux chocs
WO2000078858A3 (fr) * 1999-06-24 2002-09-26 Dow Chemical Co Compositions polyolefiniques a resistance superieure aux chocs
US6472473B1 (en) 1999-06-24 2002-10-29 Dow Global Technology Inc. Polyolefin composition with improved impact properties
US6593005B2 (en) 2000-01-24 2003-07-15 Dow Global Technologies Inc. Composition and films thereof
US6776924B2 (en) 2000-05-04 2004-08-17 Dow Global Technologies Inc. Molecular melt and methods for making and using the molecular melt
US7141182B2 (en) 2000-05-04 2006-11-28 Dow Global Technologies Inc. Molecular melt and methods for making and using the molecular melt
US7326361B2 (en) 2000-05-04 2008-02-05 Dow Global Technologies, Inc. Molecular melt and methods for making and using the molecular melt
US7399808B2 (en) 2000-05-04 2008-07-15 Dow Global Technologies Inc. Molecular melt and methods for making and using the molecular melt
US6939919B2 (en) 2000-05-26 2005-09-06 Dow Global Technologies Inc. Polyethylene rich/polypropylene blends and their uses
WO2002020628A1 (fr) * 2000-09-08 2002-03-14 Atofina Research Copolymeres heterophasique de polypropylene a rheologie regulee
EP1186618A1 (fr) * 2000-09-08 2002-03-13 ATOFINA Research Polymères hétérophasiques de propylène à rhéologie réglable
US7902300B2 (en) 2000-09-08 2011-03-08 Total Petrochemicals Research Feluy Controlled rheology polypropylene heterophasic copolymers
US6800669B2 (en) 2000-12-22 2004-10-05 Dow Global Technologies Inc. Propylene copolymer foams
WO2003042257A1 (fr) * 2001-11-14 2003-05-22 Atofina Research Polypropylene a haute resistance au choc
EP1312617A1 (fr) * 2001-11-14 2003-05-21 ATOFINA Research Polypropylène à résistance au choc élevée
EP1544219A1 (fr) 2001-11-14 2005-06-22 Total Petrochemicals Research Feluy Polypropylène à résistance au choc élevée
US7659349B2 (en) 2001-11-14 2010-02-09 Total Petrochemicals Research Feluy Impact strength polypropylene

Also Published As

Publication number Publication date
BE1009007A3 (nl) 1996-10-01

Similar Documents

Publication Publication Date Title
EP1619218B1 (fr) Vulcanisats thermoplastiques a refroidissement renforcé et produits obtenus
US7872075B2 (en) Peroxide-cured thermoplastic vulcanizates and process for making the same
WO1996032442A1 (fr) Compositions de caoutchouc thermoresistantes
US5523356A (en) Vulcanized polyolefinic plastoelastomer composition and a process for its preparation
EP0229156A1 (fr) Composition d'elastomere thermoplastique.
KR20010032217A (ko) 에틸렌의 열가소성 랜덤 공중합체를 사용한 열가소성가황물의 개질
US4716197A (en) Polyethylene/EPDM-graft polystyrene blends
US11780991B2 (en) Compositions comprising carbon fibers and at least one thermoplastic polyolefin elastomer
JPH0424376B2 (fr)
AU659722B2 (en) Thermoplastic blends containing graft copolymers of polyacrylates as impact modifiers
JPH06299017A (ja) 熱可塑性オレフィンエラストマーおよびその製造法
WO1996020247A1 (fr) COMPOSITION POLYMERE RETICULEE CONTENANT UN COPOLYMERE POLYPROPYLENE-ETHYLENE ET UN COPOLYMERE ETHYLENE-α-OLEFINE
US6710129B2 (en) Injection molding soft resin composition and users thereof
EP1751230B1 (fr) Modificateurs pour alliages thermoplastiques et alliages fabriques au moyen de ces modificateurs
US20040176540A1 (en) Olefinic rubber composition
JP2001031801A (ja) 重合体組成物
JPS6365100B2 (fr)
KR19990075714A (ko) 내충격성이 우수한 폴리프로필렌 수지 조성물
JP2022517896A (ja) 押出発泡ポリマー組成物および押出発泡ポリマー組成物を作製するための方法
US20040242781A1 (en) Elastomeric composition for the insulation of electric cables
JPS60231747A (ja) 熱可塑性エラストマ−
JPH0598087A (ja) ポリオレフイン組成物
JPH0557297B2 (fr)
JPH0665486A (ja) ポリエステル樹脂組成物
JPH04275363A (ja) 熱可塑性樹脂組成物

Legal Events

Date Code Title Description
AK Designated states

Kind code of ref document: A1

Designated state(s): CN JP US

AL Designated countries for regional patents

Kind code of ref document: A1

Designated state(s): AT BE CH DE DK ES FR GB GR IE IT LU MC NL PT SE

DFPE Request for preliminary examination filed prior to expiration of 19th month from priority date (pct application filed before 20040101)
121 Ep: the epo has been informed by wipo that ep was designated in this application
122 Ep: pct application non-entry in european phase