WO2003054054A1 - Preventing discoloration in an elastomer rubber - Google Patents
Preventing discoloration in an elastomer rubber Download PDFInfo
- Publication number
- WO2003054054A1 WO2003054054A1 PCT/US2002/039438 US0239438W WO03054054A1 WO 2003054054 A1 WO2003054054 A1 WO 2003054054A1 US 0239438 W US0239438 W US 0239438W WO 03054054 A1 WO03054054 A1 WO 03054054A1
- Authority
- WO
- WIPO (PCT)
- Prior art keywords
- phr
- elastomer rubber
- rubber composition
- discoloration
- ethylene
- Prior art date
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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
- C08L23/16—Elastomeric ethene-propene or ethene-propene-diene copolymers, e.g. EPR and EPDM rubbers
-
- 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
- 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
- C08L23/08—Copolymers of ethene
-
- 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
- C08L23/12—Polypropene
-
- 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
- C08L51/06—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 homopolymers or copolymers of aliphatic hydrocarbons containing only one carbon-to-carbon double bond
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K5/00—Use of organic ingredients
- C08K5/0008—Organic ingredients according to more than one of the "one dot" groups of C08K5/01 - C08K5/59
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2312/00—Crosslinking
Definitions
- the present invention relates to methods for preventing or minimizing discoloration of elastomer rubbers and the products formed thereby. More particularly, the present invention relates to the addition of polar functional groups to ethylene propylene elastomer rubbers to prevent discoloration, even after weathering and exposure to ozone.
- elastomeric rubbers such as ethylene- ⁇ -olefin elastomers, including ethylene-propylene-diene terpolymer (EPDM) rubbers and ethylene-propylene (EP) rubber, and styrene-butadiene copolymer rubber (SBR), have been used to form these rubber parts.
- EPDM ethylene-propylene-diene terpolymer
- EP ethylene-propylene
- SBR styrene-butadiene copolymer rubber
- Ethylene- ⁇ -olefin elastomers are excellent all-purpose rubbers, especially suitable for a wide variety of automotive applications.
- rubber is defined to mean a polymeric material that is capable of recovering from large deformations quickly and forcibly and is essentially insoluble in solvents.
- EPDM rubber is a rubber comprising ethylene and propylene repeating units with a smaller amount of diene units to effect crosslinking of the polymer chains.
- various additives are incorporated into the base rubber. These additives can include carbon black and various processing oils.
- Carbon black is used as a filler and reinforcing agent and to improve ozone and UV-light resistance.
- Processing oils are used to reduce the viscosity of the rubber, which provides advantages in processing.
- the EPDM rubbers are typically cured using a sulfur or peroxide cure system. Sulfur cure systems are generally preferred since they are effective, inexpensive and require no special processing techniques. While EPDM parts provide good performance in many automotive applications, they often suffer from surface discolorations. These surface discolorations include sulfur blooming, in which the sulfur or other curatives migrate to the surface of the molded or extruded part imparting a crystalline whitish film on the part surface, and iridescence (or "bronzing"), which is the phenomenon of "oil on water” color formation in carbon black filled rubber.
- Iridescence often manifests itself as a yellowish, greenish or bluish sheen on the part surface.
- iridescence and bronzing are used interchangeably and both refer to this non-crystalline color formation on a rubber surface resulting from curatives or other additives migrating to the rubber surface. These surface discolorations grow more pronounced when the part is subjected to weathering, oxygen and ozone exposure.
- _ethylene- ⁇ -o_!efin rubber compositions that do not exhibit iridescence, blooming or other discoloration phenomenon often associated with such rubbers, and the compositions formed thereby.
- the principle of the present invention is based on formulating the rubber, including a specific curing system, in a manner that has been found to reduce or eliminate the appearance of iridescence and other sheen phenomenon that has been observed in EPDM and other ethylene- ⁇ -olefin elastomers.
- the effect of varying the base rubber, accelerators, and cure conditions was investigated. It was determined that the use of a lower ethylene content EPDM will decrease the amount of iridescence in the final product. Preferably, an EPDM base compound containing less than 58% ethylene by weight is used. Likewise, a lower accelerator content will help to minimize iridescence. Preferably, less than 4 parts per hundred resin (phr) of total accelerator is incorporated into the rubbers of the present invention. In addition, a high degree of cure will also decrease iridescence. Prefererably, cure time is greater than 5 minutes at 204°C.
- the addition of polar functional groups to the rubber prevented discoloration in a state of the art optimized EPDM rubber. It is believed that the groups increased the polarity of the compound, which increased the solubility of compounds responsible for iridescence and thus decreased their migration to the rubber surface ⁇ .
- the polar functional groups are grafted onto a non-polar compound, such as EPDM or ethylene-propylene rubber, which is then introduced into the base rubber composition.
- the non-polar compound is miscible with the base rubber, and allows the grafted polar functional groups to disperse within the base rubber.
- the polar functional groups may simply be monomer units in a polymer, such as a styrene-butadiene copolymer. It was found that the addition of maleic anhydride grafted polyethylene to the rubber composition nearly completely eliminated any discoloration on the surface of the cured rubber, even after ozone aging for 24 hours.
- Figure 1 is a graph depicting the dependence of discoloration in an EPDM sample on the concentration of CaC0 3 and clay filler.
- Figure 2 is a graph depicting the dependence of discoloration in an EPDM sample on the concentration of CaC0 3 and clay filler.
- The- present -invention - relates- to a method for preventing discoloration of elastomer rubber compounds and the resulting products. Specifically, the method is specifically tailored for reducing iridescence and blooming on the surface of carbon black filled rubber.
- the present invention finds utility in any sulfur-cured, relatively non- polar elastomer rubber that is susceptible to blooming or iridescence.
- a preferred group of rubber compounds for use as the base compound in the present invention are ethylene- ⁇ -olefin-diene rubbers (EODM's).
- EODM rubbers suitable for use in the present invention may comprise various monomers.
- Suitable ⁇ -olefins include, but are not limited to, propylene, 1-butene, 1-pentene, 1-hexene, 1-octene and 1-decene.
- a preferred ⁇ -_olefin is__polypropylene.
- a preferred group of EODM compounds suitable for the present invention are ethylene-propylene- diene terpolymer (EPDM) rubbers.
- Suitable dienes include, but are not limited to, nonconjugated dienes such as 1 ,4-pentadiene, 5-ethylidene-2- norbornene, cyclopentadiene, cyclohexadiene, and 5-butylidene-2- norbornene as well as other straight chain, cyclic and bridged cyclic dienes.
- a preferred EPDM for use as the base compound of the present invention is ethylene-propylene-ethylidene-norbornene terpolymer.
- EPDM will be used herein as the base compound as an example and for convenience in describing the invention. As stated previously, however, it _is contemplated that other .sulfur-cured elastomer rubbers may also be used.
- EPDM rubbers of the present invention are preferably cured using sulfur, a sulfur donor, and/or one or more cure accelerators.
- other cure systems are also contemplated by the invention.
- Suitable sulfur donors and accelerators include, but are not limited-to, tetramethylthiuram disulfide (TMTD), dipentamethylenethiuram tetrasulfide (DPTT), 2-mercaptobenzothiazole (MBT), 2-
- MBTS zinc-2- mercaptobenozothiazolate
- ZMBT zinc diethyldithiocarbamatezinc
- ZDBC zinc dibutyldithiocarbamate
- DPTT dipentamethylenethiuram tetrasulfide
- TDEC tellurium diethyldithiocarbamate
- ZDMC zinc dimethyldithiocarbamate
- DTDM dithiodimorpholine
- TBBS N-t- butylbenzothiazole-2-sulfanamide
- the preferred EPDM rubbers may also include carbon black and processing oil in any concentration that does not adversely affect the properties of the final rubber composition in a significant manner.
- a typical concentration of carbon black is from about 130 to about 200 phr with a preferred range of about 140 to about 180 phr.
- the processing oil to carbon black concentration ratio is about 0.4 to 0.6.
- the EPDM rubbers _j5Eoduced_accordLDg_io he invention may contain various other ingredients in amounts that do not detract from the properties of the resultant composition.
- these ingredients can include, but are not limited to, activators such as zinc oxide and other metal oxides; fatty acids such as stearic acid and salts thereof; fillers and reinforcers such as calcium or magnesium carbonate, silica, aluminum silicates, and the like; plasticizers and extenders such as dialkyl organic acids, naphthalenic and paraffinic oils and the like; antidegradants; softeners; waxes; and pigments.
- the high molecular weight EPDM along with the various curatives, accelerators and other components, are mixed using standard equipment and techniques known in the industry for a temperature and time necessary to obtain a uniform mixing.
- the blends may be accelerated on a mill and cured under typical vulcanization temperatures and time conditions.
- the selection of EPDM rubber that is used in a molded product can affect the degree of discoloration in the resulting final rubber composition. It was discovered that the use of higher ethylene content EPDM base rubber will increase iridescence irrthe-final-eompositiort.
- an EPDM with less than 58% ethylene by weight is used as the base compound for the rubber compositions of the present invention.
- the effect of particular fillers such as whitening agents on rubber discoloration was investigated. It was discovered that lowering the amount of CaC0 3 while increasing the amount of clay filler will decrease discoloration in the final rubber composition.
- the amount of CaCO ⁇ in the final compound is about 0 to about 40 phr and the concentration of clay is from about 20 to about 80 phr.
- the amount of CaC0 3 in the final composition is about 0 to about 20 phr and the amount of clay is about 50 to about 70 phr.
- the effect of sulfur and total accelerator content on discoloration in the final compound was investigated.
- a cure system comprising sulfur in an amount of about 1.0 to about 1.5 phr and total accelerators in an amount of about 2.0 to about 4.5 phr is used in the present invention.
- the effect of stearic acid concentration and accelerator identity on discoloration in the final composition was investigated. It was discovered that increasing the amount of stearic acid and the amount of DTDM in the composition decreased iridescence while the addition of TMTD, ZDBC and ZDMC tended to increase iridescence.
- a cure system comprising sulfur in a concentration of about 1.0 to abouU J phr, DTDM (80%) at about 0.4 to about 1.0 phr, DPTT (67%) at about 0.5 to about 1.0 phr, MBTS (67%) at about 0.2 to about 0.6 phr and TDEC (67%) at about 1.2 to about 2.0 phr is used.
- stearic acid is added to the rubber composition in a concentration of about 1.2 to about 2.0 phr.
- the effect of cure time on the amount of discoloration exhibited _by_the final rubber composition was investigated. It was discovered that samples with shorter cure times exhibited a higher degree ofxliscoloration that those with- longer cure-times.
- the final rubber compositions of the present invention are cured for longer than about 5 minutes at 204°C.
- the effect of the addition of polar polymers to the base composition on the discoloration of the final rubber composition was investigated. It was discovered that the addition of certain polar functional groups reduced discoloration in the final product.
- the polar functional groups are preferably grafted onto a polymer backbone and the resulting grafted polymer is subsequently introduced into the base rubber composition.
- any polymer that is miscible with the base rubber compound may be used as the backbone on which the polar functional groups may be grafted.
- suitable grafting polymers include, but are not limited to, polyethylene, - )olyp ⁇ opyle ⁇ e,_ethylene propylene. rubber (EP) and ethylene- ⁇ -olefin- diene rubber. All monomers mentioned previously as suitable for the ethylene- ⁇ -olefin-diene rubber of the base compound are suitable for use in the grafting polymers as well.
- Any polar functional group that is easily grafted to a polymer and that will increase the solubility of the compounds responsible for iridescence and blooming are suitable for use in the present invention.
- Suitable functional groups include, but are not limited to, acrylic acid, acrylic acid ethyl ester, acrylic acid butyl ester, N-methylol-acrylimide, N- ethylol-acrylimide (and higher homologues of this class), allyl glycidylether, and maleic anhydride.
- the polar group will be from about 3% to about 20% by weight of the entire grafted polymer.
- a preferred polar functional group additive is maleic anhydride grafted polyethylene wherein the maleic anhydride comprises about 3.5% by weight of the compound.
- the maleic anhydride grafted polyethylene is added to the base composition in a concentration of from
- the amount of discoloration is not easily quantifiable and although the reported numbers are not the products of any numeric formulation, they are a qualitative indication of the amount of discoloration exhibited by particular samples. Thus, the lower the number assigned to a sample, the less discoloration exhibited by that sample, and vice versa. Some of the results in the trials of the present disclosure report discoloration of samples using this number scale. Other trials simply state the results in purely descriptive terms (i.e. more or less discoloration). When present, it should be remembered that a sample with a lower number represents a sample with less surface discoloration than a sample with a higher number.
- the state of cure of the rubber was investigated and its effect upon the degree of iridescence in a final product. It was found that when the cure time is approximately 3 to 5 minutes, there is severe bronzing on the surface of the molded rubber. When the cure time is greater than 8 minutes, there is .no bronzing on the.surface.
- polar functional groups added to the rubber formulations.
- the goal was to eliminate iridescence by adding a polymer which was still highly miscible with EPDM but possessed sufficient polarity (in the form of grafted polar groups) to .increaseJhe_solubJlity_of_polar_chemic.als.that contributed to iridescence.
- Four different polar additives were investigated. These were styrene- butadiene rubber (SBR 1551), chlorosulfonated polyethylene (Hypalon PC5850), chloroprene rubber (Bayprene 111) and maleic anhydride grafted polyethylene (Adland 8).
- SBR 1551 styrene- butadiene rubber
- Hypalon PC5850 chlorosulfonated polyethylene
- Bayprene 111 chloroprene rubber
- Adland 8 maleic anhydride grafted polyethylene
- chlorosulfonated polyethylene compounds had a deleterious effect upon bronzing. Such compounds caused severe bronzing on the surface of the molded rubber. Chloroprene rubber compounds were unacceptable as they caused a film on the surface of the molded rubber. Compounds with SBR were generally acceptable since the higher the SBR, the less the blue tint or color. Compounds comprising maleic anhydride grafted polyethylene were identified to be the best. Samples containing Adland 8 exhibited no discoloration on their surface, even after exposure in an ozone chamber for 24 hours.
- the cured elastomer rubber compositions of the present invention may be used, in addition to other applications, to fashion molded and extruded rubber parts for the motor vehicle industry.
- the rubber compositions of the present invention may be used to make a variety of parts, including glass run channels, gaskets, hoses, weatherstrips and various seals.
- Such a glass run channel will typically have a longitudinally extending main body member with a generally "U" shaped cross-sectional configuration having a bottom wall and two substantially vertical side walls.
- the glass run channel will preferably have at least one sealing lip to engage and seal against a vehicle window and at least one retention spur to hold the glass run channel securely in a vehicle door frame.
Abstract
Description
Claims
Priority Applications (6)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
AU2002357131A AU2002357131A1 (en) | 2001-12-07 | 2002-12-06 | Preventing discoloration in an elastomer rubber |
MXPA04005333A MXPA04005333A (en) | 2001-12-07 | 2002-12-06 | Preventing discoloration in an elastomer rubber. |
CA002469285A CA2469285A1 (en) | 2001-12-07 | 2002-12-06 | Preventing discoloration in an elastomer rubber |
JP2003554767A JP2005513221A (en) | 2001-12-07 | 2002-12-06 | Method for preventing discoloration in elastic rubber |
KR10-2004-7008773A KR20040074995A (en) | 2001-12-07 | 2002-12-06 | Preventing discoloration in an elastomer rubber |
EP02805561A EP1451240A1 (en) | 2001-12-07 | 2002-12-06 | Preventing discoloration in an elastomer rubber |
Applications Claiming Priority (2)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
US10/011,152 US6653386B2 (en) | 2001-12-07 | 2001-12-07 | Preventing discoloration in an elastomer rubber |
US10/011,152 | 2001-12-07 |
Publications (1)
Publication Number | Publication Date |
---|---|
WO2003054054A1 true WO2003054054A1 (en) | 2003-07-03 |
Family
ID=21749096
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
PCT/US2002/039438 WO2003054054A1 (en) | 2001-12-07 | 2002-12-06 | Preventing discoloration in an elastomer rubber |
Country Status (8)
Country | Link |
---|---|
US (1) | US6653386B2 (en) |
EP (1) | EP1451240A1 (en) |
JP (1) | JP2005513221A (en) |
KR (1) | KR20040074995A (en) |
AU (1) | AU2002357131A1 (en) |
CA (1) | CA2469285A1 (en) |
MX (1) | MXPA04005333A (en) |
WO (1) | WO2003054054A1 (en) |
Cited By (2)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN104513433A (en) * | 2014-12-17 | 2015-04-15 | 建新赵氏集团有限公司 | Preparation method of high-temperature-resistant and anti-fatigue modified ethylene propylene diene monomer rubber |
US10723176B2 (en) | 2015-03-06 | 2020-07-28 | The Yokohama Rubber Co., Ltd. | Rubber composition for sidewalls, and pneumatic tire using same |
Families Citing this family (9)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US7278528B2 (en) * | 1999-02-19 | 2007-10-09 | Ronald H. Ball | Method of and apparatus for applying a film optionally including advertising or other visible material, to the surface of a handrail for an escalator or moving walkway |
US20040006179A1 (en) * | 2002-07-01 | 2004-01-08 | Cooper Technology Services Llc | Reducing friction of EPDM and related rubbers |
ITVI20060185A1 (en) * | 2006-06-16 | 2007-12-17 | Fitt Spa | FLEXIBLE TUBE IN THERMOPLASTIC MATERIALS WITHOUT LIQUID PLASTICIZING AGENTS |
EP2052022A1 (en) * | 2006-08-04 | 2009-04-29 | ExxonMobil Chemical Patents Inc. | Polymer compositions comprising cyclic olefin copolymers and polyolefin modifiers |
JP4752674B2 (en) * | 2006-08-21 | 2011-08-17 | 豊田合成株式会社 | Weather strip manufacturing method |
US8206528B2 (en) * | 2007-11-09 | 2012-06-26 | Ehc Canada, Inc. | Method of applying a film to an endless moving handrail having a layer with a barrier coating |
CN108017842A (en) * | 2016-11-04 | 2018-05-11 | 德尔福派克电气系统有限公司 | A kind of automotive wire bundle low smell EPDM rubber and preparation method thereof |
JP6817041B2 (en) * | 2016-11-24 | 2021-01-20 | Eneos株式会社 | Conductive thermoplastic elastomer composition |
KR102313487B1 (en) * | 2021-05-31 | 2021-10-14 | 남재현 | Color rubber for wireless charger pads with anti-discoloration effects in natural conditions |
Citations (1)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US5798413A (en) * | 1994-03-04 | 1998-08-25 | E. I. Du Pont De Nemours And Company | Flexible polar thermoplastic polyolefin compositions |
Family Cites Families (8)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
IT1195773B (en) | 1980-04-16 | 1988-10-27 | Dow Corning Ltd | ORGANOPOLYSILOSSANIC COMPOSITIONS FORMING ELASTOMERS |
JP2553537B2 (en) | 1987-01-23 | 1996-11-13 | 東燃化学 株式会社 | Polypropylene fiber yarn-proofing composition |
US5157081A (en) | 1989-05-26 | 1992-10-20 | Advanced Elastomer Systems, L.P. | Dynamically vulcanized alloys having two copolymers in the crosslinked phase and a crystalline matrix |
US5183613A (en) | 1990-08-22 | 1993-02-02 | Gencorp Inc. | Process for the preparation of solventless, low friction, abrasion-resistant coatings for elastomeric substrates |
US5502112A (en) | 1992-07-30 | 1996-03-26 | Exxon Chemical Patents Inc. | Thermoplastic olefins |
CA2089978C (en) | 1993-02-19 | 2005-04-12 | Tadeusz Borys | Automotive trim piece |
EP0719637B1 (en) | 1994-12-27 | 2001-05-30 | Toyoda Gosei Co., Ltd. | Method of decorating rubber extruded product |
JP3261562B2 (en) | 1996-01-19 | 2002-03-04 | 豊田合成株式会社 | Automotive weather strip |
-
2001
- 2001-12-07 US US10/011,152 patent/US6653386B2/en not_active Expired - Fee Related
-
2002
- 2002-12-06 MX MXPA04005333A patent/MXPA04005333A/en not_active Application Discontinuation
- 2002-12-06 WO PCT/US2002/039438 patent/WO2003054054A1/en not_active Application Discontinuation
- 2002-12-06 JP JP2003554767A patent/JP2005513221A/en active Pending
- 2002-12-06 EP EP02805561A patent/EP1451240A1/en not_active Withdrawn
- 2002-12-06 AU AU2002357131A patent/AU2002357131A1/en not_active Abandoned
- 2002-12-06 CA CA002469285A patent/CA2469285A1/en not_active Abandoned
- 2002-12-06 KR KR10-2004-7008773A patent/KR20040074995A/en not_active Application Discontinuation
Patent Citations (1)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US5798413A (en) * | 1994-03-04 | 1998-08-25 | E. I. Du Pont De Nemours And Company | Flexible polar thermoplastic polyolefin compositions |
Cited By (2)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN104513433A (en) * | 2014-12-17 | 2015-04-15 | 建新赵氏集团有限公司 | Preparation method of high-temperature-resistant and anti-fatigue modified ethylene propylene diene monomer rubber |
US10723176B2 (en) | 2015-03-06 | 2020-07-28 | The Yokohama Rubber Co., Ltd. | Rubber composition for sidewalls, and pneumatic tire using same |
Also Published As
Publication number | Publication date |
---|---|
MXPA04005333A (en) | 2004-09-13 |
JP2005513221A (en) | 2005-05-12 |
CA2469285A1 (en) | 2003-07-03 |
EP1451240A1 (en) | 2004-09-01 |
US20030125438A1 (en) | 2003-07-03 |
AU2002357131A1 (en) | 2003-07-09 |
US6653386B2 (en) | 2003-11-25 |
KR20040074995A (en) | 2004-08-26 |
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