CA2092142A1 - Synthetic mineral fibre reinforced polymers - Google Patents

Synthetic mineral fibre reinforced polymers

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Publication number
CA2092142A1
CA2092142A1 CA002092142A CA2092142A CA2092142A1 CA 2092142 A1 CA2092142 A1 CA 2092142A1 CA 002092142 A CA002092142 A CA 002092142A CA 2092142 A CA2092142 A CA 2092142A CA 2092142 A1 CA2092142 A1 CA 2092142A1
Authority
CA
Canada
Prior art keywords
blend
fibres
reaction product
ethylene
polymer
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.)
Abandoned
Application number
CA002092142A
Other languages
French (fr)
Inventor
Lambertus Adrianus Van Der Groep
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.)
BENNET BV
Original Assignee
Lambertus Adrianus Van Der Groep
Bennet B. 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 Lambertus Adrianus Van Der Groep, Bennet B. V. filed Critical Lambertus Adrianus Van Der Groep
Publication of CA2092142A1 publication Critical patent/CA2092142A1/en
Abandoned legal-status Critical Current

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Classifications

    • CCHEMISTRY; METALLURGY
    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08LCOMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L23/00Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers
    • C08L23/02Compositions 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
    • C08L23/10Homopolymers or copolymers of propene
    • C08L23/12Polypropene
    • CCHEMISTRY; METALLURGY
    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08KUse of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K7/00Use of ingredients characterised by shape
    • C08K7/02Fibres or whiskers
    • C08K7/04Fibres or whiskers inorganic
    • CCHEMISTRY; METALLURGY
    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08LCOMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L23/00Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers
    • C08L23/02Compositions 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
    • C08L23/04Homopolymers or copolymers of ethene
    • C08L23/06Polyethene
    • CCHEMISTRY; METALLURGY
    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08LCOMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L25/00Compositions of, homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by an aromatic carbocyclic ring; Compositions of derivatives of such polymers
    • C08L25/02Homopolymers or copolymers of hydrocarbons
    • C08L25/04Homopolymers or copolymers of styrene
    • CCHEMISTRY; METALLURGY
    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08LCOMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L25/00Compositions of, homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by an aromatic carbocyclic ring; Compositions of derivatives of such polymers
    • C08L25/02Homopolymers or copolymers of hydrocarbons
    • C08L25/04Homopolymers or copolymers of styrene
    • C08L25/08Copolymers of styrene
    • C08L25/12Copolymers of styrene with unsaturated nitriles
    • CCHEMISTRY; METALLURGY
    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08LCOMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L55/00Compositions of homopolymers or copolymers, obtained by polymerisation reactions only involving carbon-to-carbon unsaturated bonds, not provided for in groups C08L23/00 - C08L53/00
    • C08L55/02ABS [Acrylonitrile-Butadiene-Styrene] polymers
    • CCHEMISTRY; METALLURGY
    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08LCOMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L77/00Compositions of polyamides obtained by reactions forming a carboxylic amide link in the main chain; Compositions of derivatives of such polymers
    • CCHEMISTRY; METALLURGY
    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08LCOMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L2205/00Polymer mixtures characterised by other features
    • C08L2205/02Polymer mixtures characterised by other features containing two or more polymers of the same C08L -group
    • CCHEMISTRY; METALLURGY
    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08LCOMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L2205/00Polymer mixtures characterised by other features
    • C08L2205/03Polymer mixtures characterised by other features containing three or more polymers in a blend
    • CCHEMISTRY; METALLURGY
    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08LCOMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L2205/00Polymer mixtures characterised by other features
    • C08L2205/03Polymer mixtures characterised by other features containing three or more polymers in a blend
    • C08L2205/035Polymer mixtures characterised by other features containing three or more polymers in a blend containing four or more polymers in a blend
    • CCHEMISTRY; METALLURGY
    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08LCOMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L23/00Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers
    • C08L23/02Compositions 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
    • C08L23/04Homopolymers or copolymers of ethene
    • C08L23/08Copolymers of ethene
    • C08L23/0807Copolymers of ethene with unsaturated hydrocarbons only containing more than three carbon atoms
    • C08L23/0815Copolymers of ethene with aliphatic 1-olefins
    • CCHEMISTRY; METALLURGY
    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08LCOMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L23/00Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers
    • C08L23/02Compositions 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
    • C08L23/04Homopolymers or copolymers of ethene
    • C08L23/08Copolymers of ethene
    • C08L23/0846Copolymers of ethene with unsaturated hydrocarbons containing other atoms than carbon or hydrogen atoms
    • C08L23/0853Vinylacetate
    • CCHEMISTRY; METALLURGY
    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08LCOMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L23/00Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers
    • C08L23/02Compositions 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
    • C08L23/16Elastomeric ethene-propene or ethene-propene-diene copolymers, e.g. EPR and EPDM rubbers

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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

ABSTRACT
The invention relates to a blend of rockwool and/or slagwool fibres and a reaction product of at least one EPDM rubber, at least one ethylene-vinyl acetate copolymer and at least one ethylene copolymer.

Description

Title: Synthetic mineral fibre reinforced polymers.

The present invention relates to a blend of rockwool or slagwool, and a compatibilizer, to the use of said blend for preparing synthetic mineral fibre reinforced polymers and to a process for preparing said reinforced polymers.
It is known in the art to reinforce polymers, such as polyolefins, polyamides, styrene polymers and engineering plastics, with various kinds of fibres. The use of chopped glass fibres in polymers is known to result in an increase in modulus with a large decrease in toughness. It has been tried to incorporate rockwool or slagwool fibres in polymers.
However this resulted in such a decrease in the fibre length, that it only resulted in a slight increase of the mechanical properties, such as the modulus of the polymers.
It is an object of the invention to provide a system that makes it possible to incorporate fibres of rockwool or slagwool in polymers without the problems inherent to the ~ conventional use of said fibres in polymers.
The invention provides a blend of stone fibres, uch as rockwool or slagwool, and a reaction product of at least one EPDM rubber, at least one ethylene-vinyl acetate copolymer and at least one ethylene copolymer. Said blend can be a physical mixture obtained by simply dry blending the stone fibres and the reaction products. Such a dry blend can be mixed with the polymer or blend of polymers to be modified, and subsequently extruded at a temperature above the melt temperature of the polymer. In a preferred embodiment of the invention the said blend has been obtained by blending the fibres and the reaction product at a temperature above the melting point of the reaction product. In this way the fibres remain homogeneously distributed throughout the reaction product and can be mixed into the polymer or blend of polymers to be modified in a reproducible manner. Surprisingly it has been 20~21~2 found that the incorporation of the fibres in the reaction product can and preferably should be done at high shear, i.e.
in a standard multipurpose polyethylene extruder at a screw speed of 150 to 500 min~l.
The weight ratio of fibres and the reaction product in the blend varies in dependence of the use, but will generally lie between 10 to 1 and 1 to 10. A preferred ratio is between 7.5 to 1 and 1 to 1. Within this ratio it is possible to obtain the optimal results, i.e. the length of the fibres is maintained as good as possible.
The said reaction product is preferably prepared by reaction of the components at elevated temperature, more in particular at a temperature above the melting point of the polymers, more in particular above 200C. The various components are respectively EPDM rubber, ethylene-vinyl acetate copolymer and ethylene copolymer. The EPDM rubber is a conventional rubber based upon ethylene and propylene, - optionally combined with one or more comonomers, such as at least one non-conjugated diene. Preferred dienes are 1,4-hexadiene or dicyclopentadiene. The ethylene-vinylacetate - polymer can be the conventional polymers, prepared by high pressure radical polymerisation. Suitable vinylacetate contents are between 10 and 35 %. The ethylene copolymer can be any suitable polymer of ethylene, other than those already described herein. Examples of suitable polymers are LLDPE, VLDPE and other copolymers of ethylene with comonomers, such as l-alkenes, like l-butene, l-hexene, l-oc~ene and mixtures of two or more thereof, optionally in combination with comonomers having reactive groups, like carboxyl-groups. ;`
The reaction product that is preferably used is described in European patent applications Nos. 287,140 and 316,037, the contents of which is incorporated herein by reference.
According to one preferred embodiment the reaction product of the latter application is used, which reaction product is defined as based upon 1-10 wt.% of EPDM rubber, 35-65 wt.~ of 2~921~2 ethylene-vinyl acetate copolymer and 30-60 wt.% ethylene/1-(~4-C8)alkylene copolymer.
According to another embodiment the material defined in European patent application No. 287,140 is used, namely the reaction product of 30-70 wt.% of EPDM rubber, 30-70 wt.~ of ethylene-vinyl acetate copolymer and 1-25 wt.% ethylene/1- (C4-) alkylene copolymer. Finally, it is also possible to use acombination of both reaction products. The ethylene/1-(c4-c8)alkylene copolymer can be any suitable copolymer, although the use of 1-hexene and 1-octene copolymers are preferred.
The said reaction product can be prepared in the manner disclosed in the two cited European patent applications. More in particular this can be done by melt-mixing the components in the required ratio in a suitable extruder, providing sufficient shear and heat to obtain the reaction. The required melt temperature for the reaction is usually at least 150C, - more in particular between 175 and 275C.
The fibres should preferably be made of rockwool or slagwool. Said product has a fibre length wich can range from - 50 to 800 ~m. The thickness of the fibres is usually between 1 and 10 ~m.
In a preferred embodiment the fibres have been coated with a silane coating agent or any other coating agent suitable for said fibres, usually based on silicons. The said coating agent may be a conventional silane coating agent or a modified silane coating agent, for example containing one or more substituents, like carboxy-, alkoxy-, hydroxyl-, amine-, and/or amidegroups. Accordin~ to this preferred embodiment the improvement of the properties, that is obtained by using the blend for modifying a polymer or polymeric composition is more pronounced. More in particular a coating is used that may react with the said reaction product.
The blend according to the invention is useful for modifying polymers or polymeric blends. More in particular the blend, when incorporated in a polymer composition improves the 2~92142 stiffness or modulus of the polymers, without causing an unacceptable decrease in the other properties. In fact it has been observed that in a glass fibre reinforced product having a comparable modulus, the decrease of properties like toughness and Izod are much larger. The blend of the pesent invention thus allows a much better compromise between the various properties. In addition the blend of the invention may provide an improvement in other properties of the composition, like barrier properties or ageing resistance.
A further important aspact of the present invention is the improvement in flame ~esistant properties, obtained through the use of the specific blend in thermoplastic and other polymers. It has been found that a-polymer modified in accordance with the invention shows a much better flame resistance than polymers modified with, for example, glass fibres.
Suitable polymers to be modified by the blend of the - present invention are the conventional bulk polymers, like polyolefins, styrene polymers, polyesters, polyamides and the like. More in particular the following examples can be - mentioned: polyethylene, polypropylene, nylon 6, nylon 66, polystyrene, HIPS, MIPS, SAN, SMA, ABS, AES, PBT and PET.
In a preferred embodiment of the invention the blend is used in a composition of two or more polymers that are generally considered as incompatible. Through the use of the reaction product, and more in particular the reaction product of the European patent No. 287,140, not only the synthetic mineral fibres retain their properties in the polymer composition, but also the components of the composition become compatible with each other.
Generally the properties of a polymer composition that can be improved are rigidity, orientation/warpage, temperature resistance, flowability/processability, flame retardent properties, surface finish, homogenity and/or recyclability.
According to a specific embodiment of the invention the blend can be used for modifying recycled polymeric material ~Q~2142 such as polymer scrap to a composition from which products with improved properties can be prepared.
The preparation of the polymeric composition modified with the blend according to the invention can be done in any S manner known in the art, for example by dry blending followed by extrusion at a temperature above the melting point of the components. In the same manner as described in relation to the preparation of the blend also the polymeric composition according to the invention can and should preferably be subjected to a high shear, for example more than 200 rpm of the extruder screw. ~ --The invention is now elucidated in and by tne followingexamples, without being limited thereto.

EXAMP~ES

Various polymer compositions were prepared by moulding a - dry blend of rockwool fibres, a reaction product and a polymer at various moulding conditions.-The weight-ratio of the said three components was in all experiments 30/5/65.
- The rockwool fibres were conventional silane coated fibres. The reaction product was the reaction product of an EPDM rubber, an ethylene-vinyl acetate copolymer (28% VA) and an ethylene copolymer, i.e. ethylene/l-C8-alkylene copolymer, obtained by reaction of the said components in a ratio of 5/45/50 at a temperature of 215C.
A medium impact polystyrene (MIPS 512-31, Vestyron/Huls) was blended as indicated above with rockwool and the reaction product and moulded at 300 rpm~1, mould temperature 60C, barrel temperature 240C, using a 25 LD screw, PE
configuration. The results of were compared with the results of the pure MIPS.

2~921~2 Blend Pure Breakstress (MPa) 29.8 18.5 Breakstrain (~) 2 13.2 Flex modulus (MPa) 4526 2455 IZOD (Notched, kJ/m2) 2.2 4.9 MFI 2.16/230 (dg/min) 7.9 16.9 A general purpose polystyrene (GPPS GA100 Norsolor) was blended as indicated above with rockwool and the reaction product and moulded at g00 -rpm~1, mould temperature 60C, barrel temperature 240C, using a 25 LD screw, PE
configuration. The results of were compared with the results of the pure polystyrene.
Blend Pure - - Breakstress (MPa) 51.6 50.3 Breakstrain (%) 3.4 4.0 Flex modulus (MPa) 5821 3436 - IZOD (Notched, kJ/m2) 1.7 1.8 MFI 2.16/230 (dg/min) 2.3 6.1 An ABS (Monsanto QE 1083) was blended with rockwool and the reaction product in a ratio of 75/20/5 (Example 3) and at a ratio of 65/30/5 (Example 4). These blends were moulded at 200 rpm~l, mould temperature 80C, barrel temperature 240C, using a 25 LD screw, PE configuration.

~32i~

Example 3 Example 4 Yieldstress (MPa) 42.3 4L.3 Yieldstrain (%) 3.8 3.0 Breakstress (MPa) 39.8 39.6 Breakstrain (~) 5.5 3.8 Flex modulus (MPa) 6009 6922 IZOD (Notched, kJ/m2) 3.3 3.4 In the same manner as indicated above three blends were prepared using HDPE, PP and Ny~on 6.

HDPE PP Nylon 6 Yieldstress (MPa) 31.7 25.2 82.0 Yieldstrain (~) 2.9 3.3 3.2 Breakstress (MPa) 30.5 17.0 81.9 - - Breakstrain (%) 5.0 36.7 4.0 Flex modulus (MPa) 2433 2051 4056 IZOD (Notched, kJ/m2) 4.1 5.8 5.2 MFI (ISO 1133, g/lOmin) 3.48 1.16 HDT (ISO 75, 0.45N/mm2) 90.5C 156.5C
VICAT (ISO 306, 50N) 79.2C 184.5C

Claims (8)

1. Blend of rockwool and/or slagwool fibres and at least one reaction product of at least one EPDM rubber, at least one ethylene-vinyl acetate copolymer and at least one ethylene copolymer.
2. Blend according to claim 1, wherein an ethylene/1-(C4-C8)alkylene copolymer is used.
3. Blend according to claim 1 or 2, wherein the ratio of said fibres to reaction product is between 10 to 1 and 1 to 10, preferably between 7.5 to 1 and 1 to 1.
4. Blend according to claim 1-3, wherein the fibres have been coated with a silane coating agent, such as a conventional silane coating agent or a modified silane coating agent, containing one or more substituents, like carboxy-, alkoxy-, hydroxyl-, amine-, and/or amidegroups.
5. Polymer composition comprising at-least one polymer and 1 to 40 wt.% of the blend of any one of the claims 1-4.
6. Polymer composition according to claim 5, wherein the said at least one polymer is chosen from the group of polyethylene, polypropylene, nylon 6, nylon 66, polystyrene, HIPS, MIPS, SAN, SMA, ABS, AES, PBT and PET.
7. Process for preparing a blend according to claim 1, comprising feeding the said fibres and the at least one reaction product to an extruder and mixing the components at a temperature above the melting point of the reaction product until a homogeneous dispersion has been obtained, at a high shear rate.
8. Process for preparing a polymer composition according to claim 5 or 6, comprising feeding the blend and the at least one polymer to an extruder and mixing the components at a temperature above the melting point of the components until a homogeneous dispersion has been obtained, at a high shear rate.
CA002092142A 1992-03-20 1993-03-22 Synthetic mineral fibre reinforced polymers Abandoned CA2092142A1 (en)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
EP92200815 1992-03-20
EP92200815.6 1992-03-20

Publications (1)

Publication Number Publication Date
CA2092142A1 true CA2092142A1 (en) 1993-09-21

Family

ID=8210495

Family Applications (1)

Application Number Title Priority Date Filing Date
CA002092142A Abandoned CA2092142A1 (en) 1992-03-20 1993-03-22 Synthetic mineral fibre reinforced polymers

Country Status (4)

Country Link
EP (1) EP0561477A1 (en)
CA (1) CA2092142A1 (en)
FI (1) FI931213A (en)
NO (1) NO931001L (en)

Families Citing this family (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN107118432A (en) * 2017-05-08 2017-09-01 深圳市科聚新材料有限公司 Modified polypropylene composite material and preparation method thereof

Family Cites Families (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4122061A (en) * 1976-12-23 1978-10-24 General Electric Company Impact modified polyester compositions
US4101502A (en) * 1977-04-01 1978-07-18 Gaf Corporation Interpolymers of poly (butylene terephthalate)
JPS61185546A (en) * 1985-02-13 1986-08-19 Showa Denko Kk Olefin polymer composition
NL8702640A (en) * 1987-11-05 1989-06-01 Lambertus Adrianus Van Der Gro POLYMER COMPOSITION, METHOD FOR PREPARING A POLYMER COMPOSITION AND USE OF SUCH A POLYMER COMPOSITION.
DE3860769D1 (en) * 1987-03-13 1990-11-15 Lambertus Adrianus Van D Groep POLYMER COMPOSITION, METHOD FOR THE PRODUCTION AND USE THEREOF.

Also Published As

Publication number Publication date
FI931213A0 (en) 1993-03-19
NO931001D0 (en) 1993-03-19
FI931213A (en) 1993-09-21
EP0561477A1 (en) 1993-09-22
NO931001L (en) 1993-09-21

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