WO2004072174A1 - シンジオタクティックプロピレン系重合体組成物 - Google Patents
シンジオタクティックプロピレン系重合体組成物 Download PDFInfo
- Publication number
- WO2004072174A1 WO2004072174A1 PCT/JP2004/001060 JP2004001060W WO2004072174A1 WO 2004072174 A1 WO2004072174 A1 WO 2004072174A1 JP 2004001060 W JP2004001060 W JP 2004001060W WO 2004072174 A1 WO2004072174 A1 WO 2004072174A1
- Authority
- WO
- WIPO (PCT)
- Prior art keywords
- propylene
- syndiotactic
- weight
- parts
- olefin
- Prior art date
Links
Classifications
-
- 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
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J5/00—Manufacture of articles or shaped materials containing macromolecular substances
- C08J5/18—Manufacture of films or sheets
-
- 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
- C08L23/14—Copolymers of propene
- C08L23/142—Copolymers of propene at least partially crystalline copolymers of propene with other 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
- C08L2203/00—Applications
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2203/00—Applications
- C08L2203/16—Applications used for films
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2203/00—Applications
- C08L2203/18—Applications used for pipes
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2205/00—Polymer mixtures characterised by other features
- C08L2205/02—Polymer mixtures characterised by other features containing two or more polymers of the same C08L -group
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2207/00—Properties characterising the ingredient of the composition
- C08L2207/10—Peculiar tacticity
- C08L2207/12—Syndiotactic polypropylene
Definitions
- Syndiotactic propylene polymer with excellent abrasion resistance, flexibility and rubber elasticity Syndiotactic propylene polymer with excellent abrasion resistance, flexibility and rubber elasticity
- Composition BACKGROUND ART
- Crosslinked olefin-based thermoplastic elastomers are widely used as energy-saving and resource-saving elastomers, especially as substitutes for natural rubber in automotive parts, industrial machinery parts, electronic and electrical equipment parts, and building materials. .
- non-crosslinked or partially crosslinked olefin thermoplastic elastomers are described in, for example, JP-B-53-21021, JP-B-55-18448, JP-B-56-15741, and JP-B-56 No. -15742, JP-B-58-46138, JP-B-58-56575, JP-B-59-30376, JP-B-62-938, JP-B-62-59139, etc. I have.
- the non-crosslinked or partially crosslinked olefin thermoplastic elastomer used in the present invention desirably contains polypropylene and a non-conjugated gen-containing ethylene ⁇ -olefin homopolymer, but is not limited thereto.
- it may be a non-crosslinked or partially crosslinked olefin thermoplastic elastomer containing polypropylene and an ethylene / olefin random copolymer, and ⁇ -olefins are propylene and butene. It is desirable.
- the crystalline polyolefin resin (II-1) used in the present invention comprises a crystalline high molecular weight solid product obtained by polymerizing one or more monoolefins by either a high pressure method or a low pressure method.
- Such resins include, for example, isotactic and syndiotactic monoolefin polymer resins, with representative resins being commercially available.
- suitable raw materials for the crystalline polyolefin resin, olebuin include ethylene, propylene, 1-butene, 1-pentene, 1-hexene, 2-methylino 1 1-propene, 3_methyl_1-pentene, 4-Methinole 1-pentene, 5-methyl-11-hexene, 1-otaten, 1-decene, etc.
- a mixed olefin obtained by mixing two or more of these olefins.
- ethylene, propylene and 1-butene are particularly preferably used.
- non-conjugated polyene examples include dicyclopentadiene, 1,4-hexadiene, cyclooctadiene, methylenenonolevonolenene, ethylidene nonolepo / renene 4-methinole-1,4 Hexadiene, 5-Methyl-1,4-Hexadiene, 4-Ethynole _ 1,4,1-Hexadiene, 5-Methylenol 1,4,1-butadiene, 5-Ethyl-1,4-Hetadiene, 5-Methylenol 1 1,5-butadiene, 6-methyl-1,5-heptadiene, 5-ethyl-1,5-heptadiene, 4-methyl-1,4-octadiene, 5-methylino 1,4-octadiene, 4-ethyl-1,4-octadiene, 5- 1,4-Octadien, 5-Methinole _
- the content of the non-conjugated gen constituting the a-olefin copolymer rubber used in the present invention is 0.01 to 30 mol 0 /. , Preferably from 0.1 to 20 mole 0/0, the particular rather preferably in the range of 0.1 to 10 mole 0/0.
- the ⁇ -olefin copolymer rubber used in the present invention is, for example, an ethylene / hyolephine having 3 or more carbon atoms non-conjugated polyene copolymer, wherein ethylene and an ex-olefin having 3 or more carbon atoms are used.
- Ethylene / ⁇ -olefin with 3 or more carbon atoms (molar ratio) is 40 ⁇ 60-95 / 5.
- the ⁇ -olefin copolymer rubber ( ⁇ -2) is a total of 100 parts by weight of the crystalline polyolefm resin (A-1) and the ⁇ -olefin copolymer rubber ( ⁇ -2). 90 to 40 parts by weight, preferably 80 to 45 parts by weight.
- ⁇ -olefin copolymer rubber ( ⁇ -2) as described above can be produced by the following method.
- ⁇ -olefin copolymer rubber used in the present invention ( ⁇ -2) can be obtained by copolymerizing ⁇ -olefin having 2 to 20 carbon atoms with a non-conjugated diene in the presence of an olefin polymerization catalyst.
- a softener (A) -3) and / or inorganic fillers (A-4) can be included. , '
- the softener (A-3) is usually used in an amount of 200 parts by weight based on the total amount of 100 parts by weight of the crystalline polyolefin resin (A-1) and the -olefin copolymer rubber (A-2). 0 parts by weight or less, preferably 2 to 100 parts by weight. In the present invention, if the amount of the softener (A-3) exceeds 200 parts by weight, the heat resistance and heat aging resistance of the obtained thermoplastic elastomer composition tend to decrease.
- the inorganic filler (A-4) used in the present invention include calcium carbonate, calcium silicate, clay, carion, talc, silica, diatomaceous earth, mica powder, asbestos, alumina, Examples include barium sulfate, aluminum sulfate, calcium sulfate, basic magnesium carbonate, molybdenum disulfide, graphite, glass fiber, glass spheres, and shirasu balloon.
- the inorganic filler (A-4) is added to 100 parts by weight of the total amount of the crystalline polyolefin resin (A-11) and the ⁇ -olefin copolymer rubber (A-2). On the other hand, it is used in an amount of usually 100 parts by weight or less, preferably 2 to 5.0 parts by weight. In the present invention, when the amount of the inorganic filler (A-4) exceeds 100 parts by weight, the rubber elasticity and the moldability of the obtained thermoplastic elastomer composition tend to decrease.
- the partially crosslinked olefin-based thermoplastic elastomer composition according to the present invention comprises the above-mentioned crystalline polyolefin resin (A-1) and an ⁇ -olefin polymer rubber ( ⁇ -2). And a softener (III-3) and / or an inorganic filler (A-4), which are blended as required, and the above-mentioned ethylene-polyolefin copolymer rubber, ethylene-a-olefin. It can be obtained by dynamically heat-treating a mixture with a conjugated gen copolymer rubber or the like in the presence of an organic peroxide as described below to partially crosslink.
- organic peroxide examples include dicumyl peroxide, di-tert-butyl peroxide, 2,5-dimethyl-2,5-di- (tert-butylinoxy) hexane, 2,5-dimethyl-2,5-di (tert-butylperoxy) hexine-1,3,3-bis (tert-butylperoxyisopropyl) benzene, 1,1-bis (tert-butylpyroxy) 1) 3,3,5-trimethylcyclohexane, 11-butyl-4,4-bis (tert-butylpropyl)
- Such an organic peroxide compound is used in an amount of 100 parts by weight of the total to-be-processed material, that is, the total amount of the crystalline polyolefin resin (A-1) and the ⁇ -olefin copolymer rubber ( ⁇ -2).
- the amount is 0.02 to 3 parts by weight, preferably 0.05 to 1 part by weight. If the amount is less than the above range, the resulting thermoplastic elastomer composition has a low degree of crosslinking, and thus has insufficient heat resistance, tensile properties, elastic recovery, and rebound resilience. If the amount is more than the above range, the obtained thermoplastic 04 001060
- the 9-type elastomer composition has too high a degree of cross-linking to cause a reduction in moldability.
- the vol 8 925 flight 9 75) is as described above value, e.g., 0.5 or more degrees of Relatively Any catalyst system can be used as long as it provides a polymer with a high degree of tacticity.
- a catalyst system consisting of a bridged transition metal compound having asymmetrical ligands and a co-catalyst such as organic aluminum.
- the bridged transition metal compound having an asymmetric ligand include a transition metal compound in which C p 1 and C p 2 are different groups in the compound represented by the general formula (I). More preferably, a transition metal in which one of C p1 and C p2 is a cyclopentyl group or a derivative thereof, and the other group is a fluorenyl group or a derivative thereof.
- bridged transition metal compound that constitutes such a catalyst system examples include diphenylmethylene (cyclopent pentageninole) fluorenehaf dimethyl dichloride and dipheninolemethylene (cyclopent pentageninole) fluorenyl described in the above-mentioned literature.
- Zinoreconidum Mouth Lid, Isopropynole (Cyclopentageninole 1-L / Lenenyl) Painpumedichloride, or Isopropyl (Cyclopentagenil)
- Examples of the organic aluminum include aluminoxane '(also referred to as an alumoxane or an aluminum methoxy compound) or an alkylaluminum.
- Examples of the aluminoxane include those in which an alkylaluminum is condensed with water. Methylaluminoxane is particularly preferred, and those having a degree of polymerization of 5 or more, preferably 10 or more are used.
- the polymerization conditions are not particularly limited, and a solvent polymerization method using an inert medium, a bulk polymerization method substantially free of an inert medium, and a gas phase polymerization method can be used.
- the polymerization temperature is from 100 to + 200 ° C.
- the polymerization pressure is from normal pressure to 100 kg / cm 2 , preferably from _100 to 1100 °. C, normal pressure ⁇ 5 0 kg / cm 2 is employed. Also less than 5 mole 0/0 in the polymerization, preferably 3 moles 0 /.
- ethylene or olefins with 4 or more carbon atoms such as butene-1, pentene-1, hexene-1, heptene-1, 4-methynolepentene-11, vinylcyclohexane, hexadecene 1-1, norbornene and the like; and dienes such as hexadiene, octadiene, decadiene, dicyclopentadiene, 5-ethylidene_2-norporene and the like may be copolymerized.
- ethylene, ⁇ -olefin and the like are copolymerized in the above amounts, a composition having excellent physical properties tends to be obtained.
- the above-mentioned meta-aqueous catalyst is preferably used as the catalyst for producing the above-mentioned syndiotactic propylene- ⁇ -olefin copolymer (C).
- the above-mentioned meta-aqueous catalyst is preferably used.
- a conventionally known titanium catalyst composed of a solid titanium catalyst component and an organic aluminum compound, and a vanadium catalyst composed of a soluble vanadium compound and an organic aluminum compound can also be used.
- syndiotactic structure propylene-a-olefin copolymer (C) is usually obtained as a polymerization solution containing this.
- This polymerization solution is treated by a conventional method to obtain a syndiotactic structure propylene- ⁇ -olefin copolymer (C).
- Syndiotactic structure propylene- ⁇ -olefin copolymer (C) is 5 to 60 parts by weight, preferably 1 to 100 parts by weight of non-crosslinked or partially crosslinked olefinic thermoplastic elastomer (A). It is contained in an amount of 0 to 50 parts by weight, more preferably 10 to 40 parts by weight. When the syndiotactic propylene- ⁇ -olefin copolymer (C) is within this range, the syndiotactic propylene copolymer composition has an excellent balance between heat resistance and abrasion resistance.
- the molded article include known thermoforming methods such as extrusion molding, injection molding, inflation molding, blow molding, extrusion blow molding, injection blow molding, press molding, vacuum molding, calendar molding, and foam molding.
- the obtained molded article is exemplified.
- the molded product will be described below with reference to several examples.
- the molded article according to the present invention is, for example, an extrusion molded article or an injection molded article, its shape and product type are not particularly limited, and examples thereof include sheets, films (unstretched), pipes, hoses, wire coatings, filaments, and the like. Particularly preferred are sheets, skin materials, inner and outer layers of automobiles, and building materials.
- the syndiotactic propylene copolymer composition according to the present invention is obtained by blending the syndiotactic propylene copolymer with a non-crosslinked or partially crosslinked olefinic thermoplastic resin.
- a syndiotactic propylene-based copolymer composition having excellent balance between abrasion resistance and heat resistance while maintaining rubber elasticity can be obtained.
- TMA (° C)
- the JIS hardness (HS) was measured according to JIS K 6301.
- the composition has a tensile modulus of 7 MPa and a TMA of 130.
- C Darros change rate before and after wear ⁇ gloss was 20, permanent elongation was 7, and JIS A hardness was 75.
Abstract
Description
Claims
Priority Applications (4)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
US10/542,240 US7253234B2 (en) | 2003-02-14 | 2004-02-03 | Syndiotactic propylene polymer composition |
DE602004026410T DE602004026410D1 (de) | 2003-02-14 | 2004-02-03 | Syndiotaktisches propylenpolymer enthaltende zusammensetzung |
EP04707638A EP1593708B1 (en) | 2003-02-14 | 2004-02-03 | Syndiotactic propylene polymer composition |
JP2005504947A JP4574550B2 (ja) | 2003-02-14 | 2004-02-03 | シンジオタクティックプロピレン系重合体組成物 |
Applications Claiming Priority (2)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
JP2003035839 | 2003-02-14 | ||
JP2003-035839 | 2003-02-14 |
Publications (1)
Publication Number | Publication Date |
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WO2004072174A1 true WO2004072174A1 (ja) | 2004-08-26 |
Family
ID=32866308
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
PCT/JP2004/001060 WO2004072174A1 (ja) | 2003-02-14 | 2004-02-03 | シンジオタクティックプロピレン系重合体組成物 |
Country Status (7)
Country | Link |
---|---|
US (1) | US7253234B2 (ja) |
EP (1) | EP1593708B1 (ja) |
JP (1) | JP4574550B2 (ja) |
KR (1) | KR100712631B1 (ja) |
CN (1) | CN100369967C (ja) |
DE (1) | DE602004026410D1 (ja) |
WO (1) | WO2004072174A1 (ja) |
Cited By (4)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JP2005336359A (ja) * | 2004-05-27 | 2005-12-08 | Mitsui Chemicals Inc | 自動車内装表皮部材 |
EP1717270A1 (en) * | 2005-04-29 | 2006-11-02 | Japan Polypropylene Corporation | Polypropylene based heat shrinkable film |
JP2007321098A (ja) * | 2006-06-02 | 2007-12-13 | Mitsui Chemicals Inc | プロピレン系重合体組成物、および該組成物を用いてなる成形体 |
JP2008239686A (ja) * | 2007-03-26 | 2008-10-09 | Mitsui Chemicals Inc | 制振性組成物及びその成形体 |
Families Citing this family (11)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
AU2003302033A1 (en) | 2002-10-15 | 2004-06-15 | Exxonmobil Chemical Patents Inc. | Multiple catalyst system for olefin polymerization and polymers produced therefrom |
US7700707B2 (en) | 2002-10-15 | 2010-04-20 | Exxonmobil Chemical Patents Inc. | Polyolefin adhesive compositions and articles made therefrom |
KR100751993B1 (ko) | 2003-01-27 | 2007-08-28 | 미쯔이가가꾸가부시끼가이샤 | 프로필렌계 중합체 조성물 및 그의 용도 |
EP1997851A4 (en) * | 2006-03-17 | 2009-07-22 | Mitsui Chemicals Inc | POLYPROPYLENE RESIN COMPOSITION, FORM BODY, FOIL AND CONTAINER |
US20120240802A1 (en) | 2011-03-22 | 2012-09-27 | Landry-Coltrain Christine J | Laser-engraveable flexographic printing precursors |
US8920692B2 (en) | 2011-03-22 | 2014-12-30 | Eastman Kodak Company | Method for recycling relief image elements |
US8613999B2 (en) | 2011-07-28 | 2013-12-24 | Eastman Kodak Company | Laser-engraveable compositions and flexographic printing precursors comprising organic porous particles |
US8603725B2 (en) | 2011-07-28 | 2013-12-10 | Eastman Kodak Company | Laser-engraveable compositions and flexographic printing precursors |
KR101858787B1 (ko) * | 2011-10-24 | 2018-05-16 | 미쯔비시 케미컬 주식회사 | 열가소성 엘라스토머 조성물 및 그 제조 방법 |
CN104755548A (zh) * | 2012-10-25 | 2015-07-01 | 出光兴产株式会社 | 聚烯烃系成形体 |
US10567084B2 (en) | 2017-12-18 | 2020-02-18 | Honeywell International Inc. | Thermal interface structure for optical transceiver modules |
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2004
- 2004-02-03 KR KR1020057013988A patent/KR100712631B1/ko not_active IP Right Cessation
- 2004-02-03 EP EP04707638A patent/EP1593708B1/en not_active Expired - Fee Related
- 2004-02-03 CN CNB2004800042066A patent/CN100369967C/zh not_active Expired - Fee Related
- 2004-02-03 DE DE602004026410T patent/DE602004026410D1/de not_active Expired - Lifetime
- 2004-02-03 JP JP2005504947A patent/JP4574550B2/ja not_active Expired - Lifetime
- 2004-02-03 WO PCT/JP2004/001060 patent/WO2004072174A1/ja active Application Filing
- 2004-02-03 US US10/542,240 patent/US7253234B2/en not_active Expired - Lifetime
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Cited By (5)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JP2005336359A (ja) * | 2004-05-27 | 2005-12-08 | Mitsui Chemicals Inc | 自動車内装表皮部材 |
EP1717270A1 (en) * | 2005-04-29 | 2006-11-02 | Japan Polypropylene Corporation | Polypropylene based heat shrinkable film |
US7662888B2 (en) | 2005-04-29 | 2010-02-16 | Japan Polypropylene Corporation | Polypropylene based heat shrinkable film |
JP2007321098A (ja) * | 2006-06-02 | 2007-12-13 | Mitsui Chemicals Inc | プロピレン系重合体組成物、および該組成物を用いてなる成形体 |
JP2008239686A (ja) * | 2007-03-26 | 2008-10-09 | Mitsui Chemicals Inc | 制振性組成物及びその成形体 |
Also Published As
Publication number | Publication date |
---|---|
JPWO2004072174A1 (ja) | 2006-06-01 |
EP1593708B1 (en) | 2010-04-07 |
EP1593708A1 (en) | 2005-11-09 |
CN100369967C (zh) | 2008-02-20 |
DE602004026410D1 (de) | 2010-05-20 |
EP1593708A4 (en) | 2006-05-03 |
US7253234B2 (en) | 2007-08-07 |
US20060052543A1 (en) | 2006-03-09 |
CN1751090A (zh) | 2006-03-22 |
KR100712631B1 (ko) | 2007-05-02 |
JP4574550B2 (ja) | 2010-11-04 |
KR20050102629A (ko) | 2005-10-26 |
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