CA1276386C

CA1276386C - Compositions of rubber and polyethylene

Info

Publication number: CA1276386C
Application number: CA 513539
Authority: CA
Inventors: Peter Y. Kelly
Original assignee: DuPont Canada Inc
Current assignee: DuPont Canada Inc
Priority date: 1985-07-16
Filing date: 1986-07-10
Publication date: 1990-11-13
Anticipated expiration: 2007-11-13
Also published as: GB2177706A; GB8517935D0; GB2177706B

Abstract

ABSTRACT OF THE DISCLOSURE

A melt processable composition comprising 30 to 90%
by weight of linear low density polyethylene and 10 to 70% by weight of ground vulcanized rubber having a particle size of less than about 1.5 mm is disclosed. The polyethylene has a density of less than 0.915 g/cm3. In an embodiment, the rubber particles are coated with an organic peroxide cross-linking agent. The composition may be formed into articles using melt processing techniques e.g. injection moulding. The articles may, for example, be mud-flaps for vehicles.

Description

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COMPOSITIONS OF RUBBER AND POLYETHYLENE
The present invention relates to melt~processable compositions of ru~ber and polyethylene and especially to such compositions in which the rubber is ground scrap rubber obtained from, for instance, used automobile tires.
Some motor vehicles, especially trucks and other large vehicles, have rubber mudflaps near the rear of the wheels of the vehicle. These mudflaps are intended to deflect downwards water, mud, sand, stones and the like that are thrown up by the wheels of the vehicle as the vehicle travels along a road, thereby reducing the safety hazards of flying objects and the annoyance to motorists of spray of water, mud and the like.
Mudflaps are normally made from rubber compositions using compression vulcanization processesO Whil~ such processes have produced commercially-acceptable products, it is believed that other fabrication processes ofer the potential of greater versatility, faster cycle times, better economics and/or improved properties.
Mudflaps and similar products may be manufactured from thermoplastic polymers such as polyethylene, poly- -propylene and polyvinyl chloride by melt-forming processes e.g. injection moulding and sheet extrusion. However, such products tend to lack the appearance and flexibility of rubber that is often expected by consumers.
Mudflaps and similar products may al~o be manufac-tured from blends of powdered rubber and polyethylene. The resultant products have the appearance and feel of rubber but have a lower resistance to flexural cracking than products made from polyethylene or rubber only~
It has now been found that rubber-like articles of improved physical properties may be manufactured from compositions of rubber and polyethylene.
Accordingly, the present invention provides a melt . . I

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processable composition comprising:
(a) 30 to 90% by weight of a linear low density polyethylene, said polyethylene having a density of less than 0.915 g/cm3, and;
(b) 10 to 70% by weight of ground vulcanized rubber of a particle size of less than about 1.5 mm.
The present invention also provides a process for forming an article having the appearance of rubber, said process comprising (i) feeding to melt processing apparatus a composition comprising:
(a) 30 to 90~ by weight of a linear low density polyethylene, said polyethylene having a density of less than 0.915 g/cm3, and;
(b) 10 to 70% by weight of ground vu~lcanized rubber of a particle size of less than about 1~.5 mm, (ii) admixing said composition wi~hin said apparatus under melt conditions; and (iii) forming the resultant admixed molten composition into an article.
In preferred embodiments of the composition and process of the present invention, the rubber is ground scrap rubber, especially ground scrap rubber obtained from automobile tires.
In a further embodiment, the rubber particles have been coated with 2000 ~o 10 000 ppm, based on the weight of rubber, of an organic cross linking agent, especi~lly an organic peroxide cross-linking agentO
The composition of the present invention is comprised of polyethylene and rubber. The polyethylene is a linear low density polyethylene having a density of less than 0.915 g/cm3 and especially in the range of about 0.880 g~cm3 to 0.915 g/cm3~ Such polyethylenes may be copolymers of ethylene with an alpha-olefin homologue of ethylene e.g. a C4 - Clo alpha-olefin, examples of which are butene 1, .

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hexene-l and octene-l. Alternatively, the polyethylene may be a copolymer of ethylene with more than one alpha-olefin homologue of ethylene e.g. polymers of ethylene with more than one C3 - Clo alpha-olefin e.g. more than one of propylene, butene-l, hexene-l and octene~l. The molecular weight of the polyethylene may be varied over a wide range, depending in particular on the intended end-use of articles fabricated from the composition of polyethylene and rubber, and the proportion of polyethylene in the compositionO An example of a polyethylene of the type described above is DFDA _-1137 polyethylene which has density of 0.906 g/cm and a meltindex of 0.8 dg/min. and i5 available from Vnion Carbide Corporation of Danbury, Conn., U.S.A. ~-The rubber of the composition is a groùnd vulcanized rubber. The rubber should be ground -to a particle size that will facilitate adequate mixing of the polyethylene and rubber during processing of the composition. Thus the particle sizes that may be used will depend for-instance on the mixing capabilities of the melt processing apparatus, e.g. injection moulding apparatus or extrusion apparatus.
The intended end-use of art}cles formed from the composition may also be a factor because the homogeneity of the composition as formed into an article may affect the properties of that article. The particle size of the rubber should be less than 1.5 mm, especially less than 1.0 mm and in particular less than 0.5 mm. The rubber should be classified so that all, or at least essentially all, of the rubber has a particle size of less than 1.5 mm; larger particles tend to have detrimental effects on properties of the resultant products.
In a preferred embodiment, the ground vulcanized rubber is obtained from automobile tires or the like, especially scrap automobile tires. Such tires may be ground to a suitable particle size for the compositions of the .

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present inventioll. Techniques for grinding rubber are known in the art.
In embodiments of the present invention, the compositions may also contain an organic cross-linking agent, especially an organic peroxide cross-linking agent coated onto the surface of the rubber particles. Any such cross-linking agent must be coated onto the particles of the ground rubber prior to the admixing of rubber and polyethylene;
addition of peroxide into the compositions in the form of a concentrate or directly compounding peroxide into the polyethylene does not result in significant improvements in flex life of the product and/or results in processing difficulties e.g. due to cross-linking of the polymer. It is preferred that the coating of the particles be carried out in a uniform manner, to improve the uniformity of ~ke resultant product. For instance~ the coating may be applied using a solution of cross~linking agent and inert solvent by admixing the solution and rubber particles and subsequently removing the solvent. In a preferred method~ the coating may be applied using a Henschel* mixer.
The amount of the cross-linking agent may be about 2000 to 10 000 ppm, especially 2500 to 6000 ppm, based on the amount of rubber. The preferred cross-linking agents are organic peroxide cross-linking agents, especially a bis(tertO
alkyl peroxyalkyl~benzene, dicumyl peroxide and/or an acetylenic diperoxy compound. For instance, the cross-link-ing agent may be 2,5-dimethyl-2,5~di(t-butylperoxy) hexyne-3 which is available commercially under the trade mark Lupersol 6 130 from Pennwalt Corp, of Buffalo, New York, U.S.A. Alter-natively, the cross-linking agent may be 2,5-dimethyl-2,5 bis (tertbutyl peroxyisopropyl) benzene which is available commercially under the trade mark Vulcup from Hercules Incorporated. A co-curing agent may also be incorporated into the composition in association with the cross-linking agent. Examples of co-curing agents include triallyl * denotes trade mark .~.a,~ 33~3~

cyanurate/ triallyl isocyanurate and 1,2-po:Lybutadiene.
The compositions of the present invention may also contain stabili~ers e.g. antioxidants and/or ultra violet stabili~ers, pigments, fillers and the like, as is known for rubber compositions.
The compositions contain 30 to 90% by weight of the linear low density polyethylene and 10 to 70% by weight of the rubber. In preferred embodiments the compositions contain 40 to 60% by weight of polyethylene and 40 to 60% by weight of rubber. However, it is to be understood that the relative amounts of polyethylene and rubber, and the type of polyethylene, will depend in particular on the properties required in the articles fabricated from the compositions.
The compositions of the present invention are particularly intended for use in an injection mo~lding or a sheet extrusion process, especially for the manufacture of articles that have the appearance of being fabricated from rubber. Such articles include mudflaps and other protective devices for use on motor vehicles, especially trucks and other large vehicles.
In an injection moulding process, the compositions are admixed under melt conditions. Although the compositions could be so admixed prior to being fed to the injection moulding apparatus, it is preferred that the admixing occur in the injection moulding apparatus immediately prior to injection of the admixed composition into the mould of the apparatus. The amount of admixing should be sufficient to provide a degree of homogenei~y in tha moulded article subsequently obtained that is commensurate with the intended end-use of the article; homogeneity is one factor that is pertinent to the properties of the moulded article, Thus, apart from the mixing characteristics of the injection moulding apparatus, matters such as the particle si~e of the components of the co~position, the relative particle sizes between different components and the uniformity of the ' .

3~6 particle si~es e.g. particle size distribution, of the components may be important with respect to the propertles oP
the articles that are obtained. Such factors will be understood by those skilled in the art.
The compositions of the present invention are also intended for use in melt processes other than injection moulding. For instance, the compositions may be fed to extrusion apparatus, especially extrusion apparatus for the manufacture of sheet products. Mixing characteristics of the extrusion apparatus, particle sizes of the components of the compositions, relative particle sizes between different components and the uniformity of the particle sizes, e.g.
particle size distribution, may be important with respect to the properties of the articles that are obtained~
Articles fabricated from the compositi~ons of the present invention may be used in a variety of end uses. In particular, the articles may be in the form of mudflaps for vehicles~
The present invention is illustrated by the following examples.
Example I
A number of compositions of the present invention and comparative compositions were prepared. The polyethylene was in the form of pellets. The ru~ber was obtained from scrap automobile tires and had been ground to a particle size of 1~0 mm. Organic peroxide, if present, had heen coated onto the rubber particles, prior to admixing of rubber and polyethylene, in a Henschel mixer.
To test the properties of such compositions;
so-called "tensile bars" were prepared. These tensile bars had a length of 130 mm, a width of 13 mm and a thickness of 3 mm, and were moulded on an Engel* injection moulding machine from a dry blend of polyethylene pellets and rubber powder.
In preparing the sample tensile bars, the melt temperature used was 220C, which was selected so as to acti~ate any * denotes trade mark , . ' ', ' ' ' .
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organic peroxide present in the composition being moulded while maintaining decomposition of the rubber at an acceptable level. The screw speed and back pre~sure on the injection moulding apparatus were both set at the maximum ~or the apparatus to maximize the decyree of polymer/rubber homogeneity. Mould closure time was kept to a minimum to reduce any tendency for the rubber to decompose~
The injection moulded tensile bars were subjected to the following tests:
(a) Flex test ..... The bars were flexed to 90 degrees on each side of the axis of the bars, at ambient temperature and at a rate of 42 cycles/minute. The bars were considered to have failed when a crack of more than 3 mm in length had appeared at the point of flexure of t~he bars.
(b) Notched Flex test .... The proced~.re described above for the flex test was repeated except that a slit having a depth of 3 mm was cut into one side of the bars at the point of fle~ureO The bars were considered.to have failed when this cut had grown by 3 mm in length.
(c) Tensile Impact test .~. Type L tensile impact bars were cut from the injection moulded bars, according to the procedure of ASTM D-1822-68. The tensile impact test was carried out at -40C.

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~ N:l.* 1 2 3 ~ 5 6 7 8 9 P~y~e* 100 50 50 100 SO 50 0 50 50 fp~rts ~ WE~iÇht) Rut~er 0 50 50 0 50 50 100 50 50 (E~rtS ~ wei~ht) C~nic Pe~a~ O 0 3000 0 0 3~00 0 0 3000 ~m) Elex~;t>21 ~00>21 OCO>21 000 3001000 3175>21 ~0050~0 I~DO

N~td~d Flex ~st>31 00018 000>31 000900 300 900; >21 ~

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d~i3~6 _ 9 _ * Note: (i) Runs 1, 4 to 7 and 9 are comparative runs ~ii) In Runs 1 to 3, 8 and 9, the polyethylene was an ethylene/butene-l/oetena-l terpolymer having a density of 0.9102 g/cm3 and a melt index of 1.6 dg/min.
In Runs 4 ~o 6, the polyethylene was an ethylene/butene-l copolymer having a density of 0.924 g/cm3 and a melt index of 5.1 dg/min.
tiii) The organic peroxide was Lupersol 130.
(iv) The samples of Run 7 were prepared by compression moulding, not by injection moulding.
(v) In Run 8, the polyethylene and ru~ber were poorly mixed.
~vi) In Run 9~ the particle size of the rubber was 2.0 mm.
Runs 2 and 5 show the improvement in properties that is obtained when a lower density polyethylene is used.
Runs 2 and 3 and Runs 5 and 6 show the effects of the addition of organic peroxide on the flex life of articles moulded from the compositions. Runs 1, 3 and 7 show that the flex life of articles moulded from polyethylene and peroxide-treated rubber may be as good as articles injection moulded from polyethylene or compression moulded from rubber.

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Claims

1. A composition comprising:

(a) 30 to 90% by weight of a linear low density polyethylene, said polyethylene having a density of less than 0.915 g/cm3, and (b) 10 to 70% by weight of ground vulcanized rubber of a particle size of less than about 1.5 mm.

2. The composition of Claim 1 in which the particle size of the ground rubber is less than 1.0 mm.

3. The composition of Claim 1 in which the polyethylene has a density in the range of 0.880 to 0.915 g/cm3.

4. The composition of Claim 3 in which there is 40 to 60% by weight of polyethylene and 40 to 60% by weight of ground rubber.

5. The composition of any one of Claim 1, Claim 3 and Claim 4 in which the particles of ground rubber have been coated with 2000 to 10 000 ppm of an organic peroxide cross-linking agent.

6. The composition of any one of Claim 1, Claim 3 and Claim 4 in which the particles of rubber have been coated with an organic peroxide cross-linking agent selected from the group consisting of a bis(tert. alkyl peroxyalkyl) benzene, dicumyl peroxide and an acetylenic diperoxy compound, and mixtures thereof.

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7. The composition of any one of Claim 1, Claim 3 and Claim 4 in which the particles of rubber have been coated with an organic peroxide cross-linking agent selected from the group consisting of 2,5-dimethyl-2,5-di(tert-butyl peroxy) hexyne-3 and 2,5-dimethyl-2,5-bis(tert-butyl peroxy isopropyl) benzene.

8. The composition of any one of Claim 1, Claim 3 and Claim 4 in which the linear low density polyethylene is a copolymer of ethylene and one C4-C10 alpha-olefin.

9. The composition of any one of Claim 1, Claim 3 and Claim 4 in which the linear low density polyethylene is a copolymer of ethylene and more than one C3-C10 alpha-olefin.

10. A process for forming an article having the appearance of rubber, said process comprising:

(i) feeding to melt processing apparatus a composition comprising (a) 30 to 90% by weight of a linear low density polyethylene, said polyethylene having a density of less than 0.915 g/cm3, and (b) 10 to 70% by weight of ground vulcanized rubber of a particle size of less than about 1.5 mm;

(ii) admixing said composition within said apparatus under melt conditions: and (iii) forming the resultant molten composition into an article.

11. The process of Claim 10 in which the particle size of the ground rubber is less than 1.0 mm.

12. The process of Claim 10 in which the polyethylene has a density in the range of 0.880 to 0.915 g/cm3.

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13. The process of Claim 12 in which there is 40 to 60% by weight of polyethylene and 40 to 60% by weight of ground rubber.

14. The process of any one of Claim 10, Claim 12 and Claim 13 in which the particles of ground rubber have been coated with 2000 to 10 000 ppm of an organic peroxide cross-linking agent.

15. The process of any one of Claim 10, Claim 12 and Claim 13 in which the particles of ground rubber have been coated with an organic peroxide cross-linking agent selected from the group consisting of a bis(tert. alkyl peroxyalkyl) benzene, dicumyl peroxide and an acetylenic diperoxy compound, and mixtures thereof.

16. The process of of any one of Claim 10, Claim 12 and Claim 13 in which the particles of rubber have been coated with an organic peroxide cross-linking agent selected from the group consisting of 2,5-dimethyl-2,5 di(tert-butyl peroxy) hexyne-3 and 2,5-dimethyl-2,5-bis(tert-butyl peroxy isopropyl) benzene.

17. The process of any one of Claim 10, Claim 12 and Claim 13 in which the linear low density polyethylene is a copolymer of ethylene and one C4-C10 alpha-olefin.

18. The process of any one of Claim 10, Claim 12 and Claim 13 in which the linear low density polyethylene is a copolymer of ethylene and more than one C3-C10 alpha-olefin.

19. The process of Claim 10 in the form of an injection moulding process.

20. The process of Claim 10 in the form of a sheet extrusion process.