EP0641367A1 - Composition polymere - Google Patents

Composition polymere

Info

Publication number
EP0641367A1
EP0641367A1 EP93911395A EP93911395A EP0641367A1 EP 0641367 A1 EP0641367 A1 EP 0641367A1 EP 93911395 A EP93911395 A EP 93911395A EP 93911395 A EP93911395 A EP 93911395A EP 0641367 A1 EP0641367 A1 EP 0641367A1
Authority
EP
European Patent Office
Prior art keywords
polymer composition
composition according
opaque polymer
ethylene
opaque
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.)
Withdrawn
Application number
EP93911395A
Other languages
German (de)
English (en)
Other versions
EP0641367A4 (fr
Inventor
John O'leary
Stuart Musgrave
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.)
Orica Australia Pty Ltd
Original Assignee
ICI Australia Operations Pty Ltd
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 ICI Australia Operations Pty Ltd filed Critical ICI Australia Operations Pty Ltd
Publication of EP0641367A1 publication Critical patent/EP0641367A1/fr
Publication of EP0641367A4 publication Critical patent/EP0641367A4/fr
Withdrawn legal-status Critical Current

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
    • 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
    • C08L23/06—Polyethene
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L51/00—Compositions of graft polymers in which the grafted component is obtained by reactions only involving carbon-to-carbon unsaturated bonds; Compositions of derivatives of such polymers
    • C08L51/006—Compositions of graft polymers in which the grafted component is obtained by reactions only involving carbon-to-carbon unsaturated bonds; Compositions of derivatives of such polymers grafted on to block copolymers containing at least one sequence of polymer obtained by reactions only involving carbon-to-carbon unsaturated bonds
    • 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

Definitions

  • the present invention relates to scratch-resistant polymer compositions and moulded articles.
  • Plastics materials are utilised in a wide variety of applications, many of which require the material to maintain its aesthetic appeal notwithstanding various scratches and scuffs to which it is subjected during its useful life. Plastics materials are particularly susceptible to degradation of surface finish and the subsequent loss of aesthetic appeal. In particular, opaque plastics materials show a far greater loss of aesthetic appeal than either transparent or translucent plastics materials. It is believed that micro-tearing and stress whitening of the plastics material occurs around any scratches in the surface of the plastics material. This damage is far more visible, and hence much more of a problem, in opaque plastics materials.
  • Opaque plastics materials find considerable use in applications which require a resistance to scratches and scuffs.
  • car manufacturers utilise coloured plastics materials (typically polypropylene) for the interior trim of their vehicles.
  • the interior trim of a car is subjected to considerable scratching and scuffing.
  • a plastics material which may be pigmented as desired but is able to resist the scratches and scuffs of everyday use.
  • scratch resistance is required in opaque materials.
  • an opaque polymer composition comprising a blend of: a matrix polymer selected from the group consisting of polypropylene, high density polyethylene and poly- 4-methylpentene -1; at least one impact modifier wherein said impact modifier is a copolymer or terpolymer of ethylene and at least one other ⁇ -olefin or diolefin; at least one opacifier selected from the group consisting of colourants and fillers and combinations thereof; and at least one block copolymer of at least one styrenic monomer and at least one olefinic or diolefinic monomer.
  • polymer compositions of the present invention comprising polypropylene as matrix polymer exhibits particularly marked resistance to damage associated with scratching.
  • polypropylene is utilised as matrix polymer we have found that it is preferable that the polypropylene be selected from is isotactic polypropylene homopolymers and random copolymers of ethylene and propylene.
  • isotactic polypropylene typically comprises approximately 3% atactic polypropylene. It is preferred that the amount of atactic polypropylene is less than 8%.
  • the random copolymer of ethylene and propylene may be manufactured by introducing the ethylene monomer into the copolymer in a mixed feed with propylene. This generates random statistical ethylene-propylene copolymer (EP copolymer) chains.
  • the overall proportion of ethylene units in the random copolymer used in the invention is typically from 3 to 15, more usually 5 to 12 and especially about 6 (for example 5 to 7), mole % based on total monomer. The remainder of the units are derived from propylene although a small proportion of other olefin monomers can be included, for example up to 10% by weight of the propylene units of C 4 to C 10 alpha olefin monomers.
  • the polypropylene has a melt flow index, ASTM D1238 CONDITION L of 0.5-60 g/10 min and a xylene- soluble content of from 2-6% w/w. More preferably the melt flow index ASTM D1238 CONDITION L of the polypropylene is in the range of 4 to 20 g/10 min and more preferably in the range of 15 to 20 g/10 min.
  • high density polyethylene (HDPE) is selected as matrix polymer it is preferred that the HDPE has a melt flow index ASTM D1238 CONDITION E in the range of from 0.5 to 80 g/10 min, more preferably in the range of from 4 to 40 g/10 min. It is preferred that the density of the HDPE is in the range of from 940 to 965 kg/m , more preferably in the range of from 950 to 960 kg/m 3 .
  • the matrix polymer may also contain effective amounts of additional polymers such as nylon 6, nylon 66 and polyphenylene oxide.
  • the impact modifier, the polymer of ethylene and ⁇ - olefin typically has a density in the range from 860 to 930 kg/m 3 , preferably 890 to 920 kg/m 3 .
  • the melt flow index ASTM D1238 CONDITION E of the polymer of ethylene and ⁇ -olefin is typically in the range of from 0.1 to 40 g/10 min, preferably in the range of from 0.3 to 4 g/10 min.
  • the polymer of ethylene and ⁇ -olefin typically comprises up to 70 mole percent of ⁇ -olefin.
  • the crystalinity of the polymer of ethylene and ⁇ -olefin is related to the ⁇ -olefin content.
  • the ⁇ -olefin content is in the range of from 2 to 30 mole percent.
  • the ⁇ -olefin is preferably selected from propene, butene, hexene, octene and 1-methyl ⁇ entene.
  • the impact modifier be selected from the group consisting of linear low density polyethylene (LLDPE), low density polyethylene (LDPE), ethylene-propylene terpolymer (EPT or EPDM) and ethylene- propylene rubber (EPR) .
  • LLDPE linear low density polyethylene
  • LDPE low density polyethylene
  • EPT or EPDM ethylene-propylene terpolymer
  • EPR ethylene- propylene rubber
  • the impact modifier is LLDPE and has a melt flow index ASTM D1238 CONDITION E in the range of from 0.5 to 80 g/10 min, more preferably in the range of from 4 to 40 g/10 min.
  • the LLDPE typically has a density in the range of from 860 to 930 kg/m 3 , more preferably 890 to 920 kg/m 3 .
  • the impact modifier may be blended with the matrix polymer or manufactured in situ with the matrix polymer. Wherein the impact modifier is manufactured in situ with the matrix polymer it is conveniently manufactured utilising a 2 step cascade reactor.
  • polypropylene/EPR block copolymers and polypropylene/LLDPE block copolymers may be manufactured in this manner.
  • the block copolymer of at least one styrenic monomer and at least one olefinic or diolefinic monomer be grafted with from 0.1 to 20, more preferably 1 to 6, mole percent of a carboxylic acid, acid anhydride or sulphonate functionality.
  • the block copolymers are preferably selected from the group consisting of:
  • A is a styrenic block preferably polymerised from styrene or methylstyrene monomers or combinations thereof, wherein B is an olefinic or diolefinic block preferably polymerised from isoprene, butadiene or combinations thereof, and optionally halogenated to form blocks of ethylene/butylene or ethylene/propylene sequences.
  • X is a multivalent cation or a multifunctional moiety and n is the valency or functionality of X.
  • X is silicon or organosilane.
  • the styrenic monomers for use in this invention are elected from styrene itself and homologues such as ⁇ -methyl styrene and the mixed isomers sold commercially as "vinyl toluene". It is preferred that the copolymers contain from 25-35 mole percent of styrenic monomer.
  • B is a random copolymer block of ethylene and either butylene or propylene made by halogenating butadiene or isoprene blocks.
  • block copolymers of the type A-B-A are selected from the group consisting of styrene/ethylene/ -butylene/styrene and styrene/ethylene/ propylene/styrene block copolymers (hereinafter SEBS and SEPS respectively) and may be selected from any such polymers known to the art which comply with the parameters mentioned herein.
  • the SEBS and SEPS copolymers may be prepared by the sequential anionic polymerisation of the monomers using known initiators such as alkyl lithium initiators.
  • block copolymers of the type (A-B) n X are selected from the group consisting of radial SEB and radial SEP block copolymers.
  • the SEB and SEP copolymers for the radial block copolymers may be prepared by sequential anionic polymerisation using known initiators. The polymers are then coupled together by using multifunctional coupling agents known to the art, for example polychlorosilanes.
  • the block copolymers for use in this invention are preferably grafted with from 0.1 to 20 mole percent of a carboxylic acid, acid anhydride or sulphonate functionality.
  • the preferred acid is acrylic acid and the preferred acid anhydride is maleic anhydride.
  • block copolymers for use in the present invention are hydrogenated.
  • Hydrogenated block copolymers provide improved weatherability characteristics in the polypropylene composition.
  • the olefins may be hydrogenated by known means.
  • opacifier it is meant that the polymer composition is substantially opaque to visible light.
  • the opacifier is present in amounts sufficient to render the polymer composition substantially opaque.
  • the opacifier is either a colourants or a filler or a combination thereof. Typically colourants are present in amounts in the range of 0.1 to 5% by weight of the polymer composition.
  • Colourants for us in the present invention may be any of those known to the art and which comply with the parameters mentioned hereinabove. Examples of colourants useful in polymer compositions of the present invention include titanium dioxide, carbon black, iron oxide pigments, phthalocyanines, lead chromates and the like.
  • fillers are present in amounts in the range of from 5 to 50 percent by weight of the polymer composition.
  • Fillers for use in the present invention may be any of those known to the art and which comply with the parameters mentioned hereinabove.
  • Examples of fillers useful in polymer compositions of the present invention include chalk, dolomite, fibrous and plate-like inorganic fillers.
  • Plate-like fillers are those fillers whose particles have a length and width substantially greater than their depth. The presence of a plate like inorganic filler in the composition of the invention gives the composition increased stiffness.
  • Suitable plate like inorganic fillers include mineral fillers such as clays, mica and especially talc.
  • a particularly useful talc is LUZENAC 15 MOO (Talc de Luzenac) .
  • Fibrous fillers include aramid glass and carbon fibres.
  • the multivalent metal cations may preferably be selected from the group consisting of calcium, zinc, titanium, chronium and vanadium. More preferably the multivalent metal cation is zinc.
  • the multivalent metal cations may be residues from catalysts used in the manufacture of the matrix polymer or impact modifier.
  • the multivalent metal cations may also be in the form of acid acceptors used in the compounding of the matrix polymer or impact modifier.
  • acid acceptors useful in providing multivalent metal cations are zinc oxide, zinc stearate and calcium stearate. It is preferred that the multivalent metal cation is provided in the form of zinc stearate in amounts in the range of from 100 to 3000 ppm based on the total weight of polymer. While not wishing to be bound by theory it is believed that the block copolymer forms an interface between the matrix polymer and the impact modifier.
  • the compatibility of the olefinic or diolefinic block with both the matrix polymer and the impact modifier is important in allowing the block copolymer to form the interface between the matrix polymer and the impact modifier. It is believed the styrenic blocks form glassy vinyl/aromatic domains on both sides of the interface forming melt reversible crosslinks which generally add to the interfacial strength.
  • the block copolymer is grafted as hereinabove defined, it is believed that inside these glassy domains the grafted acidic groups form ionic domains with multivalent metal ions, such as those residual from the catalyst or acid acceptors used in the manufacture of the matrix polymer. These ionic bonds within the ionic domains are also melt reversible and further increase the strength of the interface between the matrix polymer and the impact modifier.
  • Suitable fatty acid amides are of fatty acids with CIO to C25, especially C16 to C22, carbon chains.
  • a particularly suitable fatty acid amide is erucamide, available as CRODAMIDE E (Croda Chemicals).
  • the amount of fatty acid amide will usually be up to 1 weight % of the composition, particularly 0.1 to 0.8%, and especially about 0.5% by weight of the composition.
  • compositions of the invention may also contain ingredients well known to the art to be useful in such compositions, these being included in art-recognised quantities.
  • ingredients include antioxidants, UV stabilisers and nucleating agents.
  • compositions 1 to 4 were prepared according to conventional automotive interior formulations and compared with the example constructed according to the invention, composition 5.
  • the composition of Examples 1 to 5 are shown in Table
  • Propathene LZM186, GWMlOl and GYM45 are polypropylene grades ex ICI Australia. Chimmasorb 944 and Tinuvin 770 are ex Ciba-Geigy. LLDPE; NUC MG 265 is ex Nippon ⁇ nicar and Kraton FG190IX is ex Shell.
  • Propathene LZM186 and GWMlOl are ethylene propylene block copolymers and GYM45 is a propylene hom polymer having a melt flow indices (MED) of 24, 4.5 and 15 respectively (ASTM D1238 CONDITION L) . Each has been adequately heat stabilised and contains between 500 and 1000 ppm Zinc Stearate.
  • NUC MG2 5 is a hexene-based LLDPE of MFI 5.0 (ASTM D1238 CONDITION E) .
  • compositions 1 to 4 were prepared by tumble blending all ingredients for 15 minutes prior to compounding in a 50mm Farrel Continuous Mixer.
  • Composition 5 was prepared by first compounding the homopoly er, LLDPE and Kraton in a cavity transfer mixer (CTM, Rapra Technologies) of 50mm diameter. The resultant granulated compound was tumble blended with the remaining ingredients prior to extrusion compounding on a 38mm single screw extruder.
  • CTM cavity transfer mixer
  • Each compounded composition was injection moulded into textured plaques of size 160 x 130mm with four automotive grained surfaces ranging from fine stipple to cowhide look.
  • the plaques were set aside for seven days to allow annealing and scratched using a hand operated scratch tester using weights of 100 to 900g in lOOg increments applied to a 1mm hemispherical tungsten stylus which was drawn across the grained surface.
  • the scratches were visually assessed by a panel of four independent observers.
  • the plaques ranked according to the visibility of the visible scratch) .
  • the rankings of the panel were aggregated to give an overall ranking. Table 1 shows the results. On the polished surface of the plaque, the results were identical, but no damage was found for Composition 5 whilst the other plaques showed considerable scratching.
  • composition 5 which is the subject of this patent, composition 5, gave moulded plaques which were far superior to the conventional compositions of Examples 1 to 4.

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

Compositions polymères opaques et articles moulés possédant une meilleure résistance à l'abrasion, cette composition polymère comprenant: un mélange d'un polymère matriciel sélectionné dans le groupe formé par le polypropylène, le polyéthylène haute densité et le poly-4-méthylpentène-1; au moins un agent modifiant le choc qui est un copolymère ou un terpolymère d'éthylène et d'au moins une autre oléfine-α ou dioléfine; au moins un opacifiant sélectionné dans le groupe constitué de colorants et de matières de remplissage, et de mélanges de ces derniers; et au moins un copolymère en masse formé d'au moins un monomère styrénique et d'au moins un monomère oléfinique ou dioléfinique.
EP93911395A 1992-04-09 1993-04-13 Composition polymere. Withdrawn EP0641367A4 (fr)

Applications Claiming Priority (3)

Application Number Priority Date Filing Date Title
AUPL180692 1992-04-09
AU1806/92 1992-04-09
PCT/AU1993/000166 WO1993021269A1 (fr) 1992-04-09 1993-04-13 Composition polymere

Publications (2)

Publication Number Publication Date
EP0641367A1 true EP0641367A1 (fr) 1995-03-08
EP0641367A4 EP0641367A4 (fr) 1996-02-07

Family

ID=3776083

Family Applications (1)

Application Number Title Priority Date Filing Date
EP93911395A Withdrawn EP0641367A4 (fr) 1992-04-09 1993-04-13 Composition polymere.

Country Status (4)

Country Link
EP (1) EP0641367A4 (fr)
CN (1) CN1077466A (fr)
MY (1) MY113372A (fr)
WO (1) WO1993021269A1 (fr)

Families Citing this family (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
NO309384B1 (no) * 1995-01-16 2001-01-22 Borealis Holding As Polyolefinlegering med forbedret overflatehårdhet og ripefasthet
US6541568B1 (en) 2000-06-01 2003-04-01 Solvay Engineered Polymers Polyolefin materials having enhanced surface durability
CN101747555B (zh) * 2008-12-16 2013-03-20 金发科技股份有限公司 一种具有耐划伤性能的聚丙烯组合物
CN102498165B (zh) * 2009-09-18 2015-02-11 巴斯夫欧洲公司 具有改善抗刮性、改善机械稳定性和改善雾度的聚合物组合物
CN103225232B (zh) * 2013-01-24 2015-10-07 浙江凯伦特种材料有限公司 聚氨酯合成革用离型纸离型层热熔树脂组合物及其采用该离型层的离型纸和制备方法
CN104004271B (zh) * 2014-06-02 2016-09-07 江苏凯力新型材料科技有限公司 一种耐低温聚丙烯专用料
KR101987575B1 (ko) * 2018-01-12 2019-06-10 한화토탈 주식회사 내백화 특성을 갖는 무도장용 메탈릭 폴리프로필렌 수지 조성물

Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP0168203A2 (fr) * 1984-06-30 1986-01-15 Mitsubishi Petrochemical Co., Ltd. Partie extérieure de voiture, moulée à partir d'une composition de copolymères thermoplastiques
EP0212831A1 (fr) * 1985-07-12 1987-03-04 Sumitomo Chemical Company, Limited Compositions copolymères élastomères moulables
EP0463963A1 (fr) * 1990-06-27 1992-01-02 Nissan Motor Co., Ltd. Composition de résine à base de copolymère éthylène-propylène pour pare-chocs d'automobiles

Family Cites Families (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPS61291247A (ja) * 1985-06-19 1986-12-22 Nissan Motor Co Ltd 自動車用バンパ
JP2902496B2 (ja) * 1991-03-28 1999-06-07 宇部興産株式会社 自動車バンパー用樹脂組成物

Patent Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP0168203A2 (fr) * 1984-06-30 1986-01-15 Mitsubishi Petrochemical Co., Ltd. Partie extérieure de voiture, moulée à partir d'une composition de copolymères thermoplastiques
EP0212831A1 (fr) * 1985-07-12 1987-03-04 Sumitomo Chemical Company, Limited Compositions copolymères élastomères moulables
EP0463963A1 (fr) * 1990-06-27 1992-01-02 Nissan Motor Co., Ltd. Composition de résine à base de copolymère éthylène-propylène pour pare-chocs d'automobiles

Non-Patent Citations (1)

* Cited by examiner, † Cited by third party
Title
See also references of WO9321269A1 *

Also Published As

Publication number Publication date
MY113372A (en) 2002-02-28
CN1077466A (zh) 1993-10-20
WO1993021269A1 (fr) 1993-10-28
EP0641367A4 (fr) 1996-02-07

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