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Radiation-crosslinked polyolefin compositions

Info

Publication number
CA2527057A1
CA2527057A1 CA 2527057 CA2527057A CA2527057A1 CA 2527057 A1 CA2527057 A1 CA 2527057A1 CA 2527057 CA2527057 CA 2527057 CA 2527057 A CA2527057 A CA 2527057A CA 2527057 A1 CA2527057 A1 CA 2527057A1
Authority
CA
Grant status
Application
Patent type
Prior art keywords
article
radiation
crosslinked
thermoset
polyethylene
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.)
Granted
Application number
CA 2527057
Other languages
French (fr)
Other versions
CA2527057C (en )
Inventor
Peter Jackson
Marcus P. Heydrich
Karen Schnuelle
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.)
Shawcor Ltd
Original Assignee
Shawcor 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

Links

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
    • 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
    • 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
    • C08L23/10Homopolymers or copolymers of propene
    • 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
    • CCHEMISTRY; METALLURGY
    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08LCOMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L2312/00Crosslinking
    • C08L2312/06Crosslinking by radiation
    • YGENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10TECHNICAL SUBJECTS COVERED BY FORMER USPC
    • Y10STECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10S522/00Synthetic resins or natural rubbers -- part of the class 520 series
    • Y10S522/906Preparing shrinkable material

Abstract

An article suitable for use as an insulating or coating material comprises a radiation-crosslinked composition comprising a polyethylene, a polypropylene and optionally an ethylene-propylene elastomer. The polyethylene component is selected from high density polyethylene (HDPE), medium density polyethylene (MDPE) and linear medium density polyethylene (LMDPE) and the polypropylene component is either a homopolymer or copolymer. The composition is predominantly based on the polyethylene component and contains the polyethylene component in an amount of at least 50 percent by weight. The article is radiation-crosslinked to a sufficient degree that it possesses thermoset properties, such that when the article is heated to a temperature above the crystalline melting point of the polypropylene homopolymer or copolymer, it is softened but does not become liquid. The article is formed by first blending the polyethylene, polypropylene and optionally the ethylene-propylene elastomer, melt processing the blend to produce an article, crosslinking the article by exposing it to radiation, and optionally heating, stretching and cooling the article to impart heat shrinkability to the article.

Claims (25)

1. A radiation-crosslinked article comprised of a polymer composition, the polymer composition comprising:
(a) at least 50 percent by weight of a polyethylene selected from the group consisting of high density polyethylene (HDPE), medium density polyethylene (MDPE) and linear medium density polyethylene (LMDPE); and (b) from about 5 percent by weight to less than 50 percent by weight of a polypropylene selected from the group consisting of polypropylene homopolymer and polypropylene copolymers;
wherein the article is crosslinked by exposure to radiation and possesses a sufficient degree of crosslinking such that when the article is heated to a temperature above the crystalline melting point of the polypropylene, it is softened but does not become liquid.
2. The radiation-crosslinked, thermoset article according to claim 1, further comprising:
(c) up to about 40 percent by weight of an ethylene-propylene elastomer.
3. The radiation-crosslinked, thermoset article according to claim 2, wherein the ethylene-propylene elastomer comprises about 40 to 95 percent by weight ethylene monomer.
4. The radiation-crosslinked, thermoset article according to claim 2, wherein the ethylene-propylene elastomer comprises an ethylene-propylene-diene terpolymer.
5. The radiation-crosslinked, thermoset article according to claim 1, wherein the amount of the polyethylene in the composition is from about 60 to 80 percent.
6. The radiation-crosslinked, thermoset article according to claim 1, wherein the amount of the polypropylene in the composition is from about 15 to 30 percent.
7. The radiation-crosslinked, thermoset article according to claim 2, wherein the amount of the ethylene-propylene elastomer in the composition is from about to 10 percent.
8. The radiation-crosslinked, thermoset article according to claim 1, said article being heat-shrinkable.
9. The radiation-crosslinked, thermoset article according to claim 1, wherein the polypropylene comprises a copolymer of propylene and ethylene.
10. The radiation-crosslinked, thermoset article according to claim 1, wherein the polypropylene is functionalized with one or more reactive functional groups selected from the group consisting of silanes, acrylic acids, methacrylic acids, acrylates, methacrylates, glycidyl methacrylates and anhydrides.
11. The radiation-crosslinked, thermoset article according to claim 4, wherein the ethylene-propylene-diene terpolymer is polymerized using a metallocene catalyst.
12. The radiation-crosslinked, thermoset article according to claim 11, wherein the metallocene catalyst comprises a highly stereospecific, single-site, constrained geometry metallocene catalyst.
13. The radiation-crosslinked, thermoset article according to claim 4, wherein the ethylene-propylene-diene terpolymer is prepared by copolymerizing propylene with ethylene and a diene monomer selected from the group consisting of 5-ethylidene-2-norbornene, dicyclopentadiene and 1,4-hexadiene.
14. The radiation-crosslinked, thermoset article according to claim 4, wherein the ethylene-propylene-diene terpolymer comprises from about 40 to about 95 percent by weight ethylene and from about 0.5 to about 10 percent by weight diene monomer.
15. The radiation-crosslinked, thermoset article according to claim 1, further comprising one or more additional ingredients selected from the group comprising radiation sensitizers, compatibilizers, pigments, antioxidant stabilizers, heat stabilizers, ultra-violet stabilizers, mineral fillers, halogenated flame retardants and process aids.
16. The radiation-crosslinked, thermoset, article according to claim 15, wherein the compatibilizer comprises one or more members of the group consisting of:
high density polyethylene (HDPE); medium density polyethylene (MDPE); linear medium density polyethylene (LMDPE); polypropylene homopolymer and polypropylene copolymers optionally modified with reactive functional groups selected from the group consisting of silanes, acrylic acids, methacrylic acids, acrylates, methacrylates, glycidyl methacrylates and anhydrides; ethylene-propylene copolymers; ethylene-propylene diene elastomers; crystalline propylene-ethylene elastomers; thermoplastic polyolefin elastomers;
metallocene polyolefins; cyclic olefin copolymers; polyoctenamers; copolymers of ethylene with vinyl acetate, vinyl alcohol, and/or alkyl acrylates; polybutenes;
hydrogenated and non-hydrogenated polybutadienes; butyl rubber; polyolefins modified with reactive functional groups selected from the group consisting of silanes, alcohols, amines, acrylic acids, methacrylic acids, acrylates, methacrylates, glycidyl methacrylates, and anhydrides; polyolefin ionomers;
polyolefin nanocomposites; and block copolymers selected from the group consisting of styrene-butadiene, styrene-butadiene-styrene, styrene-ethylene/propylene and styrene-ethylene/butylene-styrene.
17. The radiation-crosslinked, thermoset article according to claim 1, wherein the article has a gel fraction of from about 20 to 90 percent.
18. The radiation-crosslinked, thermoset article according to claim 16, wherein the compatibilizer comprises from about 5 to about 10 percent of the composition.
19. A process for producing a radiation-crosslinked, thermoset article, comprising:
(a) forming a blend comprising at least 50 percent by weight of a polyethylene selected from the group consisting of high density polyethylene (HDPE), medium density polyethylene (MDPE) and linear medium density polyethylene (LMDPE), and from about 5 percent by weight to less than 50 percent by weight of a polypropylene selected from the group consisting of polypropylene homopolymer and polypropylene copolymers;
(b) melt processing the blend to produce a melt-processed article having a first set of dimensions; and (c) crosslinking the melt-processed article by exposure to radiation to thereby produce said radiation-crosslinked, thermoset article, wherein a dosage of said radiation is sufficient to impart thermoset characteristics to the article, such that, when the article is heated to a temperature above the crystalline melting point of the polypropylene, it is softened but does not become liquid.
20. The process of claim 19, further comprising:
(d) heating the radiation-crosslinked, thermoset article to a first temperature at which it is softened but not melted;
(e) stretching the softened article such that the article is expanded beyond the first set of dimensions; and (f) cooling the stretched article to a second temperature below the temperature at which the article is softened while holding the article in its stretched form.
21. The process of claim 19, wherein steps (a) and (b) are performed simultaneously.
22. The process of claim 19, wherein melt-mixing step (a) is performed prior to step (b) using a machine selected from the group comprising a continuous twin-screw compounder, a kneader and an internal batcher.
23. The process of claim 19, wherein melt processing step (b) comprises extruding or molding.
24. The process of claim 19, wherein crosslinking step (c) is performed in an electron beam accelerator, and wherein the radiation comprises electron beam radiation, the dosage being about 1 to 20 megarads.
25. The process of claim 24, wherein the dosage is about 5 to 10 megarads.
CA 2527057 2005-02-02 2005-11-15 Radiation-crosslinked polyolefin compositions Expired - Fee Related CA2527057C (en)

Priority Applications (2)

Application Number Priority Date Filing Date Title
US11048833 US7456231B2 (en) 2005-02-02 2005-02-02 Radiation-crosslinked polyolefin compositions
US11/048,833 2005-02-02

Publications (2)

Publication Number Publication Date
CA2527057A1 true true CA2527057A1 (en) 2006-08-02
CA2527057C CA2527057C (en) 2012-01-17

Family

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Family Applications (1)

Application Number Title Priority Date Filing Date
CA 2527057 Expired - Fee Related CA2527057C (en) 2005-02-02 2005-11-15 Radiation-crosslinked polyolefin compositions

Country Status (5)

Country Link
US (2) US7456231B2 (en)
CA (1) CA2527057C (en)
DE (1) DE602005024506D1 (en)
EP (1) EP1688458B1 (en)
ES (1) ES2355830T3 (en)

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Also Published As

Publication number Publication date Type
US7579387B2 (en) 2009-08-25 grant
US20080242758A1 (en) 2008-10-02 application
US20060173089A1 (en) 2006-08-03 application
ES2355830T3 (en) 2011-03-31 grant
EP1688458A1 (en) 2006-08-09 application
DE602005024506D1 (en) 2010-12-16 grant
EP1688458B1 (en) 2010-11-03 grant
US7456231B2 (en) 2008-11-25 grant
CA2527057C (en) 2012-01-17 grant

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