WO1994005726A1 - Rubber compositions containing epoxidized natural rubber and natural rubber - Google Patents

Rubber compositions containing epoxidized natural rubber and natural rubber Download PDF

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Publication number
WO1994005726A1
WO1994005726A1 PCT/US1993/008494 US9308494W WO9405726A1 WO 1994005726 A1 WO1994005726 A1 WO 1994005726A1 US 9308494 W US9308494 W US 9308494W WO 9405726 A1 WO9405726 A1 WO 9405726A1
Authority
WO
WIPO (PCT)
Prior art keywords
enr
natural rubber
rubber
component
elastomeric composition
Prior art date
Application number
PCT/US1993/008494
Other languages
English (en)
French (fr)
Inventor
Patrick J. Curtin
Timothy M. Lipinski
William E. Russell
Original Assignee
The Moore Company
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 The Moore Company filed Critical The Moore Company
Priority to JP6507532A priority Critical patent/JPH08501338A/ja
Priority to DE69312499T priority patent/DE69312499D1/de
Priority to AU48533/93A priority patent/AU674159B2/en
Priority to EP93921442A priority patent/EP0658176B1/en
Publication of WO1994005726A1 publication Critical patent/WO1994005726A1/en

Links

Classifications

    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L15/00—Compositions of rubber derivatives
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L63/00—Compositions of epoxy resins; Compositions of derivatives of epoxy resins
    • C08L63/08—Epoxidised polymerised polyenes
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L7/00—Compositions of natural rubber
    • 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
    • C08L51/04—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 rubbers

Definitions

  • the present invention relates to elastomeri 5 compositions comprising blends of epoxidized natural rubber an natural rubber.
  • elastomer used for form fitting clothing have a unique set of requirements. These include a low stretch modulus, high dimensional stabilit 5 (to retain the article's shape), low permanent set (to avoi losing the snug fit of a garment) , and tear resistance (to avoi tearing while being punctured by the sewing needle) .
  • Thes demands are compounded, for example, when the garment is swimwear.
  • the garment may be exposed to large amounts of sunlight, chlorine from pool water, salt-water, and oils from body perspiration and sun protection lotions.
  • Neoprene tape A common synthetic substitute for natural rubber in clothing is Neoprene tape, which has excellent resistance to oil, ozone, abrasion and solvents.
  • Neoprene is not as elastic as the natural rubber, and it takes a permanent set when it stretches that can range up to 25%, which greatly distorts a garment. Neoprene is also much more expensive than natural rubber and has a lower yield due to its higher specific gravity.
  • ENR epoxidized natural rubber
  • ENR epoxidized natural rubber
  • a key advantage that is gained by this modification is increased resistance to swelling by hydrocarbon oils and solvents.
  • ENR also has excellent tensile strength and fatigue properties.
  • a high degree of reinforcement may be obtained with silica fillers, even in the absence of a coupling agent.
  • the surface characteristics (i.e., the look and feel) of the epoxidized natural rubber do not match those of natural rubber, making epoxidized natural rubber a less than ideal choice for garments.
  • Epoxidized natural rubber is also more difficult to sew than natural rubber, partly because of a tendency to tear due to the sewing needle.
  • ENR also has an undesirably high permanent set.
  • compositions for use in elastication of garments that has the superior qualities of both natural rubber and epoxidized natural rubber. It is another object that the composition have high chlorine, salt-water, and oil resistance; a low permanent set; snug gather; and resistance to sunlight exposure.
  • an elastic composite having natural rubber and epoxidized natural rubber components that are blended together in proportions described below.
  • the composition When formed in a tape, the composition is extremely useful for legbands, straps and contours of swimwear and other garments.
  • a composition comprising a component of natural rubber and a component of epoxidized natural rubber (ENR) is provided.
  • ENR epoxidized natural rubber
  • epoxidized natural rubber is epoxidized in solution by acids, such as perbenzoic, perphthallic, and peracetic acids.
  • acids such as perbenzoic, perphthallic, and peracetic acids.
  • ENR25 25 mole % epoxidized
  • ENR50 50 mole % epoxidized
  • Other grades of epoxidized natural rubber may be used.
  • the natural rubber component is preferably supplied in a bulk crumb form.
  • the natural rubber and epoxidized natural rubber are mixed in a BANBURY internal heated mixer for a time sufficient to mix the two components into a uniform blend, although it is assumed that the mixing only occurs on the granular level, and not the molecular level.
  • the resulting blends have a high degree of homogeneity.
  • Other conventional mixers such as an open mill mixer, rubber mill, Brabender mixer, or twin-screw continuous mixer may also be used.
  • ingredients are added, which may include, but are not limited to, accelerators, antioxidants, prevulcanization inhibitors, reinforcement fibers, pigments, dyes, and process oils. These and other processing aids are added in normal fashion depending on the specific mixing protocol used. The specific components and their parts per hundred rubber are shown in Table 1. Alternate vulcanizing/accelerator combinations commonly used for rubber compounding may also be used with similar results.
  • the filler listed may be a talc or calcium carbonate or other soft filler and may include titanium dioxide, which can be totally or partially replaced with Silica filler and/or clays, for some applications, it is contemplated that up to 60 parts per hundred rubber of filler might be used.
  • the activator preferably includes zinc oxide and stearic acid.
  • the accelerators preferably include benzothiazyl disulfide and di-morpholino disulfide.
  • the vulcanizing agents preferably include sulfur and alkyl phenol disulfide.
  • methacrylate grafted NR is added as a compatibility improvement agent.
  • MGNR methacrylate grafted NR
  • Both the natural rubber and epoxidized natural rubber exhibit increased compatibility with the MGNR than with each other, so the MGNR acts as a bridge to improve the bond between adjacent grains of natural rubber and epoxidized natural rubber.
  • Compatabilizing agents other than MGNR can also be used, such as other graft or block copolymers that preferably have at least one segment which is compatible with the natural rubber being used and at least one segment that is compatible with epoxidized natural rubber.
  • An example is SIS (styrene-isoprene-styrene) copolymer.
  • the preferred epoxidation level of the ENR is 50. Since ENR with varied epoxidation levels can be produced, it is preferred that the amount of the ENR satisfy the following equation:
  • the preferred and alternate compositions according to the present invention provide as good or better elasticity than natural rubber alone or neoprene.
  • the oil resistance of the two compositions, as measured by the growth in the volume of a sample (oil swell %) and the rise in percentage weight over time (oil absorption %) is from 2 to 10 times better than natural rubber alone.
  • the oil properties can be determined in a known manner, such as by immersion in oil for several hours.
  • the present compositions exhibit a lower modulus of elasticity with respect to either natural rubber alone or neoprene.
  • the oil swell and oil absorption properties are also lower than natural rubber, and in the case of the alternate embodiment, lower than both.
  • the permanent set, i.e., the non-recoverable stretch, of the ENR-NR compositions is half that for neoprene and lower than that for natural rubber alone.
  • the tear strength of the present compositions is higher than for ENR alone.
  • most common elastomers used in swimwear turn yellow after prolonged exposure to light and/or chlorinated pool water, the ENR-NR compositions turn bluer, adding to the aesthetic appeal of the ENR-NR compositions.
  • the composition of the present invention is particularly useful in forming an article of manufacture that achieves several optimum properties simultaneously. Previous compositions provided benefits in terms of one or two properties while lacking in others.
  • the composition can be used in an article that has the advantageous properties of low oil swell and oil absorption, low permanent set, low modulus of elasticity, and high tear strength.
  • the composition of the present invention can be use in the manufacture of garments, such as swimwear, which would take advantage of the enhanced properties of the present composition.

Landscapes

  • 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)
  • Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)
  • Professional, Industrial, Or Sporting Protective Garments (AREA)
  • Epoxy Resins (AREA)
PCT/US1993/008494 1992-09-04 1993-09-03 Rubber compositions containing epoxidized natural rubber and natural rubber WO1994005726A1 (en)

Priority Applications (4)

Application Number Priority Date Filing Date Title
JP6507532A JPH08501338A (ja) 1992-09-04 1993-09-03 天然ゴムおよびエポキシ化天然ゴムを含むゴム組成物
DE69312499T DE69312499D1 (de) 1992-09-04 1993-09-03 Kautschukzusammensetzungen enthaltend epoxidierten naturkautschuk und naturkautschuk
AU48533/93A AU674159B2 (en) 1992-09-04 1993-09-03 Rubber compositions containing epoxidized natural rubber andnatural rubber
EP93921442A EP0658176B1 (en) 1992-09-04 1993-09-03 Rubber compositions containing epoxidized natural rubber and natural rubber

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
US94024792A 1992-09-04 1992-09-04
US940,247 1992-09-04

Publications (1)

Publication Number Publication Date
WO1994005726A1 true WO1994005726A1 (en) 1994-03-17

Family

ID=25474486

Family Applications (1)

Application Number Title Priority Date Filing Date
PCT/US1993/008494 WO1994005726A1 (en) 1992-09-04 1993-09-03 Rubber compositions containing epoxidized natural rubber and natural rubber

Country Status (9)

Country Link
US (1) US5447976A (GUID-C5D7CC26-194C-43D0-91A1-9AE8C70A9BFF.html)
EP (1) EP0658176B1 (GUID-C5D7CC26-194C-43D0-91A1-9AE8C70A9BFF.html)
JP (1) JPH08501338A (GUID-C5D7CC26-194C-43D0-91A1-9AE8C70A9BFF.html)
AU (1) AU674159B2 (GUID-C5D7CC26-194C-43D0-91A1-9AE8C70A9BFF.html)
DE (1) DE69312499D1 (GUID-C5D7CC26-194C-43D0-91A1-9AE8C70A9BFF.html)
ES (1) ES2106366T3 (GUID-C5D7CC26-194C-43D0-91A1-9AE8C70A9BFF.html)
IL (1) IL106891A (GUID-C5D7CC26-194C-43D0-91A1-9AE8C70A9BFF.html)
TW (1) TW252992B (GUID-C5D7CC26-194C-43D0-91A1-9AE8C70A9BFF.html)
WO (1) WO1994005726A1 (GUID-C5D7CC26-194C-43D0-91A1-9AE8C70A9BFF.html)

Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP2036945A1 (de) * 2007-09-12 2009-03-18 Robert Bosch GmbH Gummimaterial
WO2009047153A1 (de) 2007-10-01 2009-04-16 Robert Bosch Gmbh Gummimaterial eines wischblattes für scheibenwischer und verfahren zu dessen herstellung

Families Citing this family (20)

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Publication number Priority date Publication date Assignee Title
US6436529B1 (en) * 1997-01-21 2002-08-20 3M Innovative Properties Company Elatomeric laminates and composites
US6220323B1 (en) * 1998-01-29 2001-04-24 The Goodyear Tire & Rubber Company Composition and tire with tread containing calcium carbonate
WO1999055538A1 (en) * 1998-04-27 1999-11-04 The Moore Company Epoxidized natural rubber printing plate
DE60022260T2 (de) * 1999-05-28 2006-06-08 Société de Technologie Michelin Gefärbte Kautschukzusammensetzung für Reifen
BR0208477A (pt) * 2001-03-30 2004-03-09 Pirelli Pneu para rodas de veìculo, composição elastomérica, e, produto manufaturado elastomérico vulcanizado
US6845797B2 (en) * 2001-10-12 2005-01-25 Bridgestone Corporation Tire compositions comprising epoxidized natural rubber and a functionalized polyolefin
US20040121692A1 (en) * 2002-12-23 2004-06-24 Taylor Jack Draper Oil-resistant elastic laminates
JP4518751B2 (ja) * 2003-06-02 2010-08-04 株式会社ブリヂストン 変性天然ゴムおよびその製造方法
MY146353A (en) 2003-06-02 2012-08-15 Bridgestone Corp Modified natural rubber or modified natural rubber latex, and rubber composition and pneumatic tire
JP4518750B2 (ja) * 2003-06-02 2010-08-04 株式会社ブリヂストン ゴム組成物および空気入りタイヤ
JP4860162B2 (ja) * 2005-02-14 2012-01-25 住友ゴム工業株式会社 ゴム組成物およびそれからなるタイヤ
JP2007169431A (ja) * 2005-12-21 2007-07-05 Sumitomo Rubber Ind Ltd サイドウォール用ゴム組成物
JP5265093B2 (ja) * 2006-05-19 2013-08-14 株式会社ブリヂストン ゴム組成物及びそれを用いたタイヤ
CN101688030B (zh) * 2007-05-15 2012-05-30 住友橡胶工业株式会社 轮胎用橡胶组合物及充气轮胎
EP2415617B1 (en) * 2010-07-30 2014-05-14 Sumitomo Rubber Industries, Ltd. Polymer sheet for inner liner, polymer laminate for inner liner, and pneumatic tire
RU2014100856A (ru) 2011-07-28 2015-09-10 Сумитомо Раббер Индастриз, Лтд. Пневматическая шина
JP5663455B2 (ja) * 2011-10-26 2015-02-04 住友ゴム工業株式会社 紙送りローラおよびゴム組成物
JP5443554B2 (ja) 2012-08-01 2014-03-19 住友ゴム工業株式会社 インナーライナーを備えた空気入りタイヤ
WO2020028903A1 (en) * 2018-08-03 2020-02-06 Birla Carbon U.S.A., Inc. Rubber composition with surface-modified carbon black and functionalized process oil
CN113429646B (zh) * 2021-07-20 2023-05-23 安徽工程大学 一种含有牺牲键的高撕裂高定伸应力的橡胶及其制备方法和应用

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US4341672A (en) * 1977-12-19 1982-07-27 Phillips Petroleum Company Sulfur or peroxy cured epoxidized diene rubbers
US4366289A (en) * 1981-04-20 1982-12-28 The Dow Chemical Company Acrylate-grafted elastomers as polymer modifiers
US4621121A (en) * 1984-10-19 1986-11-04 Degussa Aktiengesellschaft Vulcanizable mixture containing bis-(2-ethylamino-s-triazin-6-yl)-tetrasulfide
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JPH03126737A (ja) * 1989-10-11 1991-05-29 Ohtsu Tire & Rubber Co Ltd :The トレッド用ゴム組成物

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US4341672A (en) * 1977-12-19 1982-07-27 Phillips Petroleum Company Sulfur or peroxy cured epoxidized diene rubbers
US4366289A (en) * 1981-04-20 1982-12-28 The Dow Chemical Company Acrylate-grafted elastomers as polymer modifiers
US4621121A (en) * 1984-10-19 1986-11-04 Degussa Aktiengesellschaft Vulcanizable mixture containing bis-(2-ethylamino-s-triazin-6-yl)-tetrasulfide
US4674622A (en) * 1985-08-14 1987-06-23 Bridgestone Corporation Conveyor belt
US4769416A (en) * 1986-03-19 1988-09-06 The Malaysian Rubber Producers' Research Association Elastoplastic compositions
US4898223A (en) * 1989-01-30 1990-02-06 The Goodyear Tire & Rubber Company Stiff rubber composition and articles having components thereof
JPH03126737A (ja) * 1989-10-11 1991-05-29 Ohtsu Tire & Rubber Co Ltd :The トレッド用ゴム組成物

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See also references of EP0658176A4 *

Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP2036945A1 (de) * 2007-09-12 2009-03-18 Robert Bosch GmbH Gummimaterial
WO2009047153A1 (de) 2007-10-01 2009-04-16 Robert Bosch Gmbh Gummimaterial eines wischblattes für scheibenwischer und verfahren zu dessen herstellung

Also Published As

Publication number Publication date
ES2106366T3 (es) 1997-11-01
DE69312499D1 (de) 1997-09-04
EP0658176B1 (en) 1997-07-23
US5447976A (en) 1995-09-05
AU4853393A (en) 1994-03-29
EP0658176A4 (en) 1995-09-13
IL106891A0 (en) 1993-12-28
IL106891A (en) 1997-07-13
AU674159B2 (en) 1996-12-12
EP0658176A1 (en) 1995-06-21
TW252992B (GUID-C5D7CC26-194C-43D0-91A1-9AE8C70A9BFF.html) 1995-08-01
JPH08501338A (ja) 1996-02-13

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