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

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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
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WO
WIPO (PCT)
Prior art keywords
ethylene
polymer composition
cross
copolymer
propylene
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.)
Ceased
Application number
PCT/NL1995/000441
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English (en)
Inventor
Johannes Fredericus Repin
Wilhelmus Gerardus Marie Bruls
Ivan CHODÁK
Igor CHORVÁTH
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.)
Koninklijke DSM NV
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DSM NV
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Filing date
Publication date
Application filed by DSM NV filed Critical DSM NV
Publication of WO1996020247A1 publication Critical patent/WO1996020247A1/fr
Anticipated expiration legal-status Critical
Ceased legal-status Critical Current

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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
    • C08K5/14—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 four or more carbon atoms
    • C08L23/0815—Copolymers of ethene with unsaturated hydrocarbons only containing four or more carbon atoms with aliphatic 1-olefins containing one carbon-to-carbon double bond
    • 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—Ethylene-propylene or ethylene-propylene-diene copolymers
    • 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

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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 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 Ceased WO1996020247A1 (fr)

Applications Claiming Priority (2)

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

Publications (1)

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

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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
EP1186618A1 (fr) * 2000-09-08 2002-03-13 ATOFINA Research Polymères hétérophasiques de propylène à rhéologie réglable
WO2000078858A3 (fr) * 1999-06-24 2002-09-26 Dow Chemical Co Compositions polyolefiniques a resistance superieure aux chocs
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 (17)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
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
US6841620B2 (en) 1999-06-24 2005-01-11 Dow Global Technologies Inc. Polyolefin composition with improved impact properties
US6593005B2 (en) 2000-01-24 2003-07-15 Dow Global Technologies Inc. Composition and films thereof
US7141182B2 (en) 2000-05-04 2006-11-28 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
US6776924B2 (en) 2000-05-04 2004-08-17 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
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
US7902300B2 (en) 2000-09-08 2011-03-08 Total Petrochemicals Research Feluy Controlled rheology polypropylene heterophasic copolymers
EP1186618A1 (fr) * 2000-09-08 2002-03-13 ATOFINA Research Polymères hétérophasiques de propylène à rhéologie réglable
US6800669B2 (en) 2000-12-22 2004-10-05 Dow Global Technologies Inc. Propylene copolymer foams
EP1544219A1 (fr) 2001-11-14 2005-06-22 Total Petrochemicals Research Feluy Polypropylène à résistance au choc élevée
WO2003042257A1 (fr) * 2001-11-14 2003-05-22 Atofina Research Polypropylene a haute resistance au choc
US7659349B2 (en) 2001-11-14 2010-02-09 Total Petrochemicals Research Feluy Impact strength polypropylene
EP1312617A1 (fr) * 2001-11-14 2003-05-21 ATOFINA Research Polypropylène à résistance au choc élevée

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Publication number Publication date
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