CA2546075A1 - Propylene-based elastomers and uses thereof - Google Patents

Propylene-based elastomers and uses thereof Download PDF

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Publication number
CA2546075A1
CA2546075A1 CA 2546075 CA2546075A CA2546075A1 CA 2546075 A1 CA2546075 A1 CA 2546075A1 CA 2546075 CA2546075 CA 2546075 CA 2546075 A CA2546075 A CA 2546075A CA 2546075 A1 CA2546075 A1 CA 2546075A1
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CA
Canada
Prior art keywords
elastomer
composition
cured
less
propylene
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Granted
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CA 2546075
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French (fr)
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CA2546075C (en
Inventor
Sudhin Datta
Rui Zhao
Srivatsan Srinivas Iyer
Majia Amin
Chia Y. Cheng
Abdelhadi Sahnoune
Periagaram S. Ravishankar
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ExxonMobil Chemical Patents Inc
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Individual
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Classifications

    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F210/00—Copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond
    • C08F210/16—Copolymers of ethene with alpha-alkenes, e.g. EP rubbers
    • C08F210/18—Copolymers of ethene with alpha-alkenes, e.g. EP rubbers with non-conjugated dienes, e.g. EPT rubbers
    • A—HUMAN NECESSITIES
    • A43—FOOTWEAR
    • A43B—CHARACTERISTIC FEATURES OF FOOTWEAR; PARTS OF FOOTWEAR
    • A43B13/00—Soles; Sole-and-heel integral units
    • A43B13/02—Soles; Sole-and-heel integral units characterised by the material
    • A43B13/04—Plastics, rubber or vulcanised fibre
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F210/00—Copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond
    • C08F210/04—Monomers containing three or four carbon atoms
    • C08F210/06—Propene
    • D—TEXTILES; PAPER
    • D01—NATURAL OR MAN-MADE THREADS OR FIBRES; SPINNING
    • D01D—MECHANICAL METHODS OR APPARATUS IN THE MANUFACTURE OF ARTIFICIAL FILAMENTS, THREADS, FIBRES, BRISTLES OR RIBBONS
    • D01D5/00—Formation of filaments, threads, or the like
    • D01D5/08—Melt spinning methods
    • D01D5/098—Melt spinning methods with simultaneous stretching
    • D01D5/0985—Melt spinning methods with simultaneous stretching by means of a flowing gas (e.g. melt-blowing)
    • D—TEXTILES; PAPER
    • D01—NATURAL OR MAN-MADE THREADS OR FIBRES; SPINNING
    • D01F—CHEMICAL FEATURES IN THE MANUFACTURE OF ARTIFICIAL FILAMENTS, THREADS, FIBRES, BRISTLES OR RIBBONS; APPARATUS SPECIALLY ADAPTED FOR THE MANUFACTURE OF CARBON FILAMENTS
    • D01F6/00—Monocomponent artificial filaments or the like of synthetic polymers; Manufacture thereof
    • D01F6/44—Monocomponent artificial filaments or the like of synthetic polymers; Manufacture thereof from mixtures of polymers obtained by reactions only involving carbon-to-carbon unsaturated bonds as major constituent with other polymers or low-molecular-weight compounds
    • D01F6/46—Monocomponent artificial filaments or the like of synthetic polymers; Manufacture thereof from mixtures of polymers obtained by reactions only involving carbon-to-carbon unsaturated bonds as major constituent with other polymers or low-molecular-weight compounds of polyolefins
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F4/00—Polymerisation catalysts
    • C08F4/42—Metals; Metal hydrides; Metallo-organic compounds; Use thereof as catalyst precursors
    • C08F4/44—Metals; Metal hydrides; Metallo-organic compounds; Use thereof as catalyst precursors selected from light metals, zinc, cadmium, mercury, copper, silver, gold, boron, gallium, indium, thallium, rare earths or actinides
    • C08F4/60—Metals; Metal hydrides; Metallo-organic compounds; Use thereof as catalyst precursors selected from light metals, zinc, cadmium, mercury, copper, silver, gold, boron, gallium, indium, thallium, rare earths or actinides together with refractory metals, iron group metals, platinum group metals, manganese, rhenium technetium or compounds thereof
    • C08F4/62—Refractory metals or compounds thereof
    • C08F4/64—Titanium, zirconium, hafnium or compounds thereof
    • C08F4/659—Component covered by group C08F4/64 containing a transition metal-carbon bond
    • C08F4/65908—Component covered by group C08F4/64 containing a transition metal-carbon bond in combination with an ionising compound other than alumoxane, e.g. (C6F5)4B-X+
    • Y—GENERAL 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
    • Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
    • Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
    • Y10T442/00—Fabric [woven, knitted, or nonwoven textile or cloth, etc.]
    • Y10T442/60—Nonwoven fabric [i.e., nonwoven strand or fiber material]
    • Y10T442/674—Nonwoven fabric with a preformed polymeric film or sheet
    • Y10T442/678—Olefin polymer or copolymer sheet or film [e.g., polypropylene, polyethylene, ethylene-butylene copolymer, etc.]

Abstract

The present invention provides curable and cured propylene-based elastomers, optionally including a diene, and having isotactic polypropylene crystallinity, a melting point by DSC equal to or less than 110~C, and a heat of fusion of from 5 J/g to 50 J/g. The present invention also provides blend compositions comprising any of the propylene-based elastomers described herein. The present invention also provides compositions comprising any of the propylene-based elastomers described herein and 1 to 100 parts by weight of inorganic filler per 100 parts of polymer. The present invention also provides films, fibers, non-wovens, molded objects, and extruded forms which include any of the inventive compositions described herein.

Claims (43)

1. An elastomer comprising:
(a) propylene-derived units in an amount of at least 60 wt%, preferably within the range of from 80 to 90 wt%, based on the combined weight of components (a), (b), and (c);
(b) dime-derived units in an amount within the range of from 0.3 to 10 wt%, preferably from 0.3 to 3 wt%, based on the combined weight of components (a), (b), and (c); and (c) ethylene-derived units in an amount of at least 6 wt%, preferably within the range of from 8 to 20 wt%, more preferably within the range of from to 20 wt%, based on the combined weight of components (a), (b), and (c);
wherein the elastomer has isotactic polypropylene crystallinity, a melting point by DSC equal to or less than 110°C, and a heat of fusion of from 5 J/g to 50 J/g.
2. The elastomer according to claim 1, wherein the dime is 5-ethylidene-2-norbornene and is preferably present in an amount within the range of from 1 to 3 wt%, based on the combined weight of components (a), (b), and (c).
3. The elastomer according to claim 1, wherein the dime is 5-vinyl-2-norbornene and is preferably present in an amount within the range of from 0.5 to 1.5 wt%, based on the combined weight of components (a), (b), and (c).
4. The elastomer according to any of the preceding claims, wherein the elastomer has a Mooney viscosity ML(1+4) at 125°C of from 0.5 to 100, preferably from 5 to 40.
5. The elastomer according to any of the preceding claims, wherein the elastomer is partially insoluble and the fractions soluble at 23°C and 31°C, as measured by the extraction method described herein, have ethylene contents differing by 5 wt% or less.
6. The elastomer according to any of the preceding claims, wherein the elastomer has an isotactic propylene triad tacticity of from 65 to 95% and/or the elastomer has an m/r ratio of from 6 to 8 and/or the elastomer has an isotacticity index of from 40 to 55.
7. A curable composition comprising an elastomer according to any of the preceding claims 1 to 6 and a chemical crosslinking formulation as a curing package, not considered part of the polymer or filler content as used herein.
8. The curable composition according to claim 7 which further comprises a dispersed phase comprising a crystalline polymer component having a melting point by DSC of 115°C or higher, preferably isotactic polypropylene having a heat of fusion of at least 50 J/g, preferably at least 75 J/g, dispersed in a matrix formed by the elastomer, and selected from the group consisting of propylene homopolymers, propylene graft copolymers, propylene block copolymers propylene random copolymers, and mixtures thereof.
9. The curable composition according to claim 7 or 8 which further comprises a polymer with no or ethylene type crystallinity, preferably comprising at least 50 mol% ethylene-derived units.
10. The curable composition according to any of claims 7 to 9 which further comprises an EP rubber, optionally containing a dime.
11. The curable composition according to any of claims 7 to 10 which further comprises from 1 to 100 parts by weight of inorganic filler per 100 parts of polymer, wherein the inorganic filler is selected from the group consisting of carbon black, clay, titanium and magnesium oxides, silica, glass fibers, mica, and mixtures thereof.
12. The curable composition according to any of claims 7 to 11 which further comprises less than 30 wt%, optionally less than 10 wt%, based on the total weight of the composition, of an extender oil.
13. The curable composition according to any of claims 7 to 11 which further comprises no extender oil or less than 1 wt% of an extender oil, based on the total weight of the composition.
14. A cured composition in which the composition according to any of claims 7 to 13 is cured to a degree such that the viscosity ratio of the elastomer is from 1 to 10, preferably from 1.2 to 10.
15. A cured composition in which the composition according to any of claims 7 to 14 is cured to a degree such that at least 2 wt%, preferably at least 10 wt%, and especially at least 20 wt%, of the elastomer is cured and optionally less than 95 wt% of the elastomer is cured as determined by the extraction method described herein.
16. The cured composition according to claim 14 or 15 wherein the composition has a tension set after 200% elongation of less than 50% and/or an ultimate tensile strength of at least 1000 psi (6.89 MPa).
17. The cured composition according to any of claims 14 to 16 having a tensile strength (TS), measured in MPa, which conforms to the relationship:
TS = 30*(Shore A hardness/MI@a 190°C)-300+B1, where B1 is at least 2.
18. The cured composition according to any of claims 14 to 17 having a tensile strength (TS), measured in MPa, which conforms to the relationship:
TS = 30*(Shore A hardness/MI@190°C)-300+B1, where B1 is at least 4, preferably at least 6, and especially at least 12.
19. The cured composition according to any of claims 14 to 18 having a Die C
tear strength (Die C), measured in Kn/m, which conforms to the relationship:
Die C = 40*(Shore A hardness/MI@190°C)-400+B2, where B2 is at least 5, preferably at least 10, especially at least 15, and most preferably at least 20.
20. A process for making an extruded article, the process comprising:
(a) extruding a composition according to any of claims 7 to 13 to produce an extruded article, and (b) exposing the extruded article to a cure treatment so as to provide the extruded article having a composition according to any of claims 14 to 19.
21. A fiber or film produced according to the process of claim 20.
22. A non-woven web produced according to the process of claim 20.
23. A molded object produced from a composition according to any of claims 14 to 19.
24. A process for making an extruded article, the process comprising:
(a) extruding a composition comprising an elastomer to produce an extruded article, the elastomer having isotactic polypropylene crystallinity, a melting point by DSC of 110°C or less, a heat of fusion of from 5 to 50 J/g, and comprising:

(i) propylene-derived units in an amount of at least 60 wt%, preferably within the range of from 80 to 97 wt%, more preferably within the range of from 80 to 90 wt%, based on the combined weight of components (i), (ii), and (iii), (ii) ethylene-derived units in an amount of at least 6 wt%, preferably within the range of from 10 to 20 wt%, based on the combined weight of components (i), (ii), and (iii), and (iii) optionally dime-derived units in an amount within the range of from 0.1 to 10 wt%, preferably from 0.3 to 10 wt%, more preferably from 0.3 to 3 wt%, based on the combined weight of components (i), (ii), and (iii); and (b) exposing the extruded article to irradiation to at least partially cure the extruded article.
25. The process according to claim 24 in which the elastomer has a Mooney viscosity ML(1+4) at 125°C of from 0.5 to 100, preferably from 5 to 40.
26. The process according to claim 24 or 25 in which the elastomer is partially insoluble and the fractions soluble at 23°C and 31°C, as measured by the extraction methods described herein, have ethylene contents differing by less than wt%, preferably less than 2 wt%.
27. The process according to any of the preceding claims 24 to 26 in which the elastomer has an isotactic propylene triad tacticity of from 65 to 95%, and/or the elastomer has an m/r ratio of from 6 to 8, and/or the elastomer has an isotacticity index of from 40 to 55.
28. The process according to any of the preceding claims 24 to 27 in which the composition further comprises a dispersed phase comprising a crystalline polymer component having a melting point by DSC of 115°C or higher, preferably isotactic polypropylene having a heat of fusion of at least 50 J/g, preferably at least 75 J/g, dispersed in a matrix formed by the elastomer, and selected from the group consisting of propylene homopolymers, propylene graft copolymers, propylene block copolymers, propylene random copolymers, and mixtures thereof.
29. The process according to any of the preceding claims 24 to 28 in which the composition further comprises a polymer with no or ethylene type crystallinity, preferably comprising at least 50 mol% ethylene-derived units.
30. The process according to any of the preceding claims 24 to 29 in which the composition further comprises an EP rubber, optionally containing a diene.
31. The process according to any of the preceding claims 24 to 30 in which the composition further comprises from 1 to 104 parts by weight of inorganic filler per 100 parts of polymer, wherein the inorganic filler may be carbon black, clay, titanium and magnesium oxides, silica, glass fibers, mica, or mixtures thereof.
32. The process according to any of claims 24 to 31 in which the composition further comprises less than 30 wt%, optionally less than 10 wt%, based on the total weight of the composition, of an extender oil.
33. The process according to any of claims 24 to 31 in which the composition comprises no extender oil or less than 1 wt% of an extender oil, based on the total weight of the composition.
34. The process according to any of claim 24 to 33 in which the composition further comprises a chemical crosslinking formulation as a curing package, not considered part of the polymer of filler content as used herein.
35. The process according to any of claims 24 to 34 in which the composition is cured to a degree such that the viscosity ratio of the elastomer is from 1 to 10, preferably from 1.2 to 10.
36. The process according to any of claims 24 to 35 in which the composition is cured to a degree such that at least 2 wt% preferably at least 10 wt%, and especially at least 20 wt%, of the elastomer is cured and optionally less than wt% of the elastomer is cured as determined by the extraction method described herein.
37. The process according to any of claims 24 to 36 in which the extruded article has a tension set after 200% elongation of less than 50% and/or an ultimate tensile strength of at least 1000 psi (6.89 MPa).
38. The process according to any of claims 24 to 37 in which the extruded article has a tensile strength (TS), measured in MPa, which conforms to the relationship:
TS = 30*(Shore A hardness/MI@190°C)-300+B1, where B 1 is at least 2.
39. The process according to any of claims 24 to 37 in which the extruded article has a tensile strength (TS), measured in MPa, which conforms to the relationship:
TS = 30*(Shore A hardness/MI@190°C)-300+B1, where B1 is at least 4, preferably at least 6, and especially at least 12.
40. The process according to any of claims 24 to 39 in which the extruded article has a Die C tear strength (Die C), measured in Kn/m, which conforms to the relationship:
Die C = 40*(Shore A hardness/MI@190°C)-400+B2, where Ba is at least 5, preferably at least 10, especially at least 15, and most preferably at least 20.
41. A fiber produced according to the process of any of the preceding claims 24 to 40.
42. A non-woven web produced according to the process of any of the preceding claims 24 to 40.
43. A film produced according to the process of any of the preceding claims 24 to 40.
CA 2546075 2003-11-14 2004-11-12 Propylene-based elastomers and uses thereof Expired - Fee Related CA2546075C (en)

Applications Claiming Priority (3)

Application Number Priority Date Filing Date Title
US51997503P 2003-11-14 2003-11-14
US60/519,975 2003-11-14
PCT/US2004/037833 WO2005049670A1 (en) 2003-11-14 2004-11-12 Propylene-based elastomers and uses thereof

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CA2546075A1 true CA2546075A1 (en) 2005-06-02
CA2546075C CA2546075C (en) 2010-12-14

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CA 2545203 Expired - Fee Related CA2545203C (en) 2003-11-14 2004-11-12 Transparent and translucent crosslinked propylene-based elastomers, and their production and use
CA 2546075 Expired - Fee Related CA2546075C (en) 2003-11-14 2004-11-12 Propylene-based elastomers and uses thereof

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US (4) US7605217B2 (en)
EP (2) EP1687346B1 (en)
JP (2) JP5525680B2 (en)
CN (2) CN1878799B (en)
CA (2) CA2545203C (en)
WO (3) WO2005049672A1 (en)

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