[go: up one dir, main page]

WO1998014517A1 - Composition d'alliage a base de fluoroelastomeres et presentant d'excellentes proprietes a basse temperature - Google Patents

Composition d'alliage a base de fluoroelastomeres et presentant d'excellentes proprietes a basse temperature Download PDF

Info

Publication number
WO1998014517A1
WO1998014517A1 PCT/US1997/017607 US9717607W WO9814517A1 WO 1998014517 A1 WO1998014517 A1 WO 1998014517A1 US 9717607 W US9717607 W US 9717607W WO 9814517 A1 WO9814517 A1 WO 9814517A1
Authority
WO
WIPO (PCT)
Prior art keywords
fluoroelastomer
fluoroelastomers
units
total weight
composition
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.)
Ceased
Application number
PCT/US1997/017607
Other languages
English (en)
Inventor
Ronald D. Stevens
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.)
DuPont Performance Elastomers LLC
Original Assignee
DuPont Dow Elastomers LLC
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 DuPont Dow Elastomers LLC filed Critical DuPont Dow Elastomers LLC
Publication of WO1998014517A1 publication Critical patent/WO1998014517A1/fr
Anticipated expiration legal-status Critical
Ceased legal-status Critical Current

Links

Classifications

    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
    • C09K3/00—Materials not provided for elsewhere
    • C09K3/10—Materials in mouldable or extrudable form for sealing or packing joints or covers
    • C09K3/1006—Materials in mouldable or extrudable form for sealing or packing joints or covers characterised by the chemical nature of one of its constituents
    • C09K3/1009—Fluorinated polymers, e.g. PTFE
    • 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
    • C08K5/0025—Crosslinking or vulcanising agents; including accelerators
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L27/00—Compositions of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a halogen; Compositions of derivatives of such polymers
    • C08L27/02—Compositions of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a halogen; Compositions of derivatives of such polymers not modified by chemical after-treatment
    • C08L27/12—Compositions of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a halogen; Compositions of derivatives of such polymers not modified by chemical after-treatment containing fluorine atoms
    • C08L27/16—Homopolymers or copolymers or vinylidene fluoride

Definitions

  • This invention relates to alloy compositions of two or more fluoroelastomer copolymers which are co-curable with peroxides and, in particular, to seals made from these compositions.
  • Elastomeric copolymers having interpolymerized units of vinylidene fluoride (VF 2 ) and comonomers such as hexafluoropropylene (HFP), tetrafluoroethylene (TFE), and perfluoro(alkyl vinyl) ethers (PAVE) are well- known, commercially available materials which exhibit outstanding chemical, thermal and oxidative stability.
  • Fluoroelastomer copolymers which additionally contain iodine or bromine end-groups or copolymerized iodine-containing or bromine-containing cure site monomers are also known.
  • the iodinated or brominated fluoroelastomers may be cured with organic peroxides to produce vulcanizates having excellent tensile strength and compression set properties (see e.g. U.S. Patent No. 4,035,565 and U.S. Patent No. 4,973,633).
  • fluoroelastomers The major end use for fluoroelastomers is seals. Because of their chemical stability, fluoroelastomer seals are useful in demanding environments under conditions which cause degradation of seals made from less stable elastomers. For example, shaft seals or o-rings for internal combustion engines must be capable of withstanding exposure to harsh solvents, such as Fuel C and Fuel C/ethanol mixtures, with minimal swelling. Further, leakage must be prevented over temperature ranges which reach at least as low as -40°C. It is difficult to produce a single fluoroelastomer composition economically which has both the required resistance to fuel swell and low temperature leak properties necessary for such end uses.
  • the present invention provides fluoroelastomer alloy compositions which may be cured with organic peroxides in the presence of coagents to produce seals which have a leak temperature of less than or equal to -40°C (as described in the Test Method hereinafter) and a fuel swell (168 hours at 23°C in Fuel C) of less than 7 volume percent (as described in the Test Method hereinafter).
  • the fluoroelastomer composition of this invention comprises a curable alloy formed by blending: a) at least two fluoroelastomers, each fluoroelastomer having copolymerized units of vinylidene fluoride and tetrafluoroethylene, and at least one of the fluoroelastomers having copolymerized units of perfluoro(methyl vinyl) ether, wherein the total weight percentage of vinylidene fluoride units, based on the total weight of fluoroelastomers, is 50 to 55; the total weight percentage of tetrafluoroethylene units, based on the total weight of fluoroelastomers, is 10 to 16; and the total weight percentage of perfluoro(methyl vinyl) ether units, based on the total weight of fluoroelastomers, is 20 to 30; each fluoroelastomer having 0.1 to 1.0 weight percent of a halogen selected from the group consisting of bromine and iodine; b) 0.5
  • the present invention is further directed to seals such as, but not limited to, shaft seals and o-rings made from the cured fluoroelastomer alloy compositions.
  • seals such as, but not limited to, shaft seals and o-rings made from the cured fluoroelastomer alloy compositions.
  • Such seals may find use in internal combustion engines.
  • the fluoroelastomer component of the alloys of the present invention comprises at least two fluoroelastomer copolymers.
  • Each of the copolymers includes copolymerized units of vinylidene fluoride and tetrafluoroethylene.
  • at least one of the copolymers has copolymerized units of perfluoro(methyl vinyl) ether (PMVE).
  • Fluoroelastomers containing higher perfluoro(alkyl vinyl) ethers are therefore not suitable for use in the present invention.
  • the copolymers suitable for use in the present invention may also include copolymerized units of other fluorinated comonomers, including hexafluoropropylene (HFP), 1 -hydropentafluoro- propylene, 2-hydropentafluoropropylene, and chlorotrifluoroethylene.
  • HFP hexafluoropropylene
  • 1 -hydropentafluoro- propylene 1, 2-hydropentafluoropropylene
  • chlorotrifluoroethylene chlorotrifluoroethylene
  • each of the fluoroelastomer copolymer components must be peroxide curable. That is, each fluoroelastomer copolymer must contain about 0.1 to about 1 weight percent bromine or iodine, either as a polymer endgroup or incorporated into the polymer in a cure site monomer, or both.
  • suitable brominated and iodinated cure site monomers and modifiers include 4-bromo- 3,3,4,4-tetrafluoro-butene-l (BTFB); bromotrifluoroethylene; 2-bromoperfluoro- (ethyl vinyl) ether; methylene iodide; 1,4-diiodoperfluorobutane and the like (e.g.
  • each fluoroelastomer copolymer and the relative amount of each copolymer used in the alloy is chosen so that the fluoroelastomer component of the resulting alloy will have a total of 50 to 55 weight percent units of vinylidene fluoride (all percentages are based on the total weight of the fluoroelastomers unless otherwise indicated), 10 to 16 weight percent units of tetrafluoroethylene, and 20 to 30 weight percent units of perfluoro(methyl vinyl) ether.
  • the present invention it is the total amount of vinylidene fluoride units, tetrafluoroethylene units, and perfluoro(methyl vinyl) ether units present in the fluoroelastomer component of the alloy which is important to attainment of low temperature properties and low fuel swell, not the particular comonomer content of each fluoroelastomer present in the alloy.
  • the alloy will contain a fluoroelastomer having copolymerized units of hexafluoropropylene, which will be present in amounts of from 5 to 14 weight percent, based on the total weight of the fluoroelastomers.
  • each fluoroelastomer copolymer While it is necessary that each fluoroelastomer copolymer contain units of vinylidene fluoride and tetrafluoroethylene, it is not necessary that each copolymer contain hexafluoropropylene or perfluoro(methyl vinyl) ether.
  • fluoroelastomer copolymers, and their method of preparation are well known in the art, (see for example, U.S. Patent Nos. 4,035,565; 4,214,060; 4,973,633; 5,032,655; 4,948,852; and 5,077,359, the disclosures of which are hereby incorporated by reference).
  • the organic peroxide used as a curative in the alloys of the present invention is selected from those peroxides which generate free radicals at curing temperatures.
  • a dialkyl peroxide which decomposes above 50°C is especially preferred.
  • a di-t-butylperoxide having a tertiary carbon atom attached to a peroxy oxygen is particularly preferred.
  • peroxides can be selected from such compounds as dicumyl peroxide, dibenzoyl peroxide, t-butyl perbenzoate, and di[l,3-dimethyl-3- (t-butylperoxy)butyl]carbonate.
  • organic peroxide is used in the compositions of this invention. Preferably, 1 to 3 wt.% is utilized.
  • a peroxide curing coagent which is capable of cooperating with the peroxide to effect a useful cure, such as triallylisocyanurate (TAIC), trimethylallylisocyanurate (TMAIC), tris(diallylamine)-s-triazine, triallyl phosphite, and the like (U.S. Patent No. 5,032,655) is additionally present in the compositions of this invention.
  • TAIC triallylisocyanurate
  • TMAIC trimethylallylisocyanurate
  • TMAIC tris(diallylamine)-s-triazine
  • triallyl phosphite triallyl phosphite
  • TAIC and TMAIC are preferred coagents.
  • a preferred fluoroelastomer blend component of the alloy is a mixture of a) 60-80 weight percent of a fluoroelastomer copolymer having copolymerized VF 2 units, TFE units, PMVE units, and BTFB units with b) 40-20 weight percent of a fluoroelastomer copolymer having copolymerized VF 2 units, TFE units, HFP units, BTFB units and iodine endgroups derived from the chain transfer agent CH 2 I 2 which is present during polymerization.
  • a particularly preferred blend is one wherein the first copolymer is a fluoroelastomer having about 54 wt.% VF 2 units, about 10 wt.% TFE units, about 35 wt.% PMVE units, and about 1.2 wt.% units of BTFB, and the second copolymer is a fluoroelastomer having about 50 wt.% VF 2 units, about 20 wt.% TFE units, about 29 wt.% HFP units, about 0.6 wt.% BTFB units and an iodine content of about 0.2 wt.%.
  • the fluoroelastomer alloys of the present invention are prepared by blending together two or more fluoroelastomer copolymers, an organic peroxide curing agent, and a coagent for the peroxide. Blending will be carried out most generally in a Banbury mixer, internal mixer, or on a rubber mill.
  • the fluoroelastomer alloy composition may also include other well known additives useful in rubber compounding, for example fillers, such as carbon black, non-fibrillating fluoropolymers, clay, silica, talc, metal oxides, divalent metal hydroxides, calcium carbonate, pigments, antioxidants, stabilizers and the like; plasticizers such as dibutylsebacate, dioctylphthalate and the like.
  • fillers such as carbon black, non-fibrillating fluoropolymers, clay, silica, talc, metal oxides, divalent metal hydroxides, calcium carbonate, pigments, antioxidants, stabilizers and the like
  • plasticizers such as dibutylsebacate, dioctylphthalate and the like.
  • shaped fluoroelastomers are generally cured. Typically, curing is carried out by heating the composition for about 1-60 minutes at about 150°-200°C. Conventional rubber curing presses, molds, extruders, and the like provided with suitable heating and curing means can be used. Also, for maximum heat resistance and dimensional stability, it is preferred to carry out a post curing operation wherein the molded or extruded article is heated in an oven or the like for an additional period of about 1-48 hours, usually from about 180°-300°C.
  • the fluoroelastomer alloy compositions of the invention are useful for producing o-ring seals, for use in fuel, lubricant and hydraulic systems, and in automotive shaft seals.
  • Cured seals produced from the fluoroelastomer alloy compositions of the present invention have a leak temperature of less than or equal to -40°C and a fuel swell, in Fuel C for 168 hours at 23 °C, of less than 7 volume percent, preferably less than 6.5 vol.%.
  • Fluoroelastomer Copolymer A (“A") was a tetrapolymer containing copolymerized units of VF 2 , TFE, PMVE, and BTFB units in a weight ratio of about 54:10:35:1.2
  • the copolymer was prepared according to the emulsion polymerization process disclosed in U.S. Patent 4,035,565 and had a Mooney viscosity, ML-10 (121°C) of approximately 85.
  • Fluoroelastomer Copolymer B (“B") was a tetrapolymer containing copolymerized units of VF 2 , TFE, HFP, and BTFB units in a weight ratio of about 50:20:29:0.6
  • the copolymer contained about 0.2 wt.% iodine, had a Mooney viscosity, ML-10 (121°C) of 25, and was prepared according to the emulsion polymerization process disclosed in U.S. Patent 4,973,633.
  • Peroxide co-curable fluoroelastomer alloy compositions of this invention and controls of peroxide curable compositions of Fluoroelastomer Copolymer A (Control A) and of Fluoroelastomer Copolymer B (Control B) were prepared by mixing the ingredients shown in Table I in a B anbury mixer.
  • the compositions of Table I were molded into 75 mil (1.9 mm) thick 3-inch x 6-inch (7.6 cm x 15 cm) slabs and press cured at 177° C for 10 minutes under greater than 20 tons (276 MPa) pressure, followed by a post cure at 232 °C for 24 hours in an air oven.
  • the physical properties were measured by the above test methods and are reported in Table I.
  • O-rings were prepared, in the same manner as the slabs, for TR-10 and leak temperature testing. As can be seen from the test results, the cured slabs prepared from samples 1-3 of the invention have excellent physical properties, particularly Fuel Volume swells of less than 7 vol.%. O-rings had leak temperatures of -40°C or less.

Landscapes

  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Health & Medical Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • Compositions Of Macromolecular Compounds (AREA)

Abstract

L'invention concerne des compositions d'alliage à base de fluoroélastomères et pouvant être durcies par des peroxydes. Ces compositions, une fois durcies, produisent des scellements présentant d'excellentes caractéristiques de scellement à basse température et de résistance au gonflement en volume en présence de carburants.
PCT/US1997/017607 1996-10-01 1997-10-01 Composition d'alliage a base de fluoroelastomeres et presentant d'excellentes proprietes a basse temperature Ceased WO1998014517A1 (fr)

Applications Claiming Priority (4)

Application Number Priority Date Filing Date Title
US2821596P 1996-10-01 1996-10-01
US60/028,215 1996-10-01
US93114197A 1997-09-16 1997-09-16
US08/931,141 1997-09-16

Publications (1)

Publication Number Publication Date
WO1998014517A1 true WO1998014517A1 (fr) 1998-04-09

Family

ID=26703436

Family Applications (1)

Application Number Title Priority Date Filing Date
PCT/US1997/017607 Ceased WO1998014517A1 (fr) 1996-10-01 1997-10-01 Composition d'alliage a base de fluoroelastomeres et presentant d'excellentes proprietes a basse temperature

Country Status (1)

Country Link
WO (1) WO1998014517A1 (fr)

Cited By (8)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US6864336B2 (en) 2002-09-12 2005-03-08 3M Innovative Properties Company Fluoroelastomers having low temperature characteristics and solvent resistance
US7148300B2 (en) 2002-09-12 2006-12-12 3M Innovative Properties Company Fluoroelastomers with improved permeation resistance and method for making the same
EP1591508A4 (fr) * 2003-02-06 2008-05-28 Nok Corp Composition de produit d'etancheite a base de fluorocaoutchouc et produit d'etancheite a base de fluorocaoutchouc
US7390842B2 (en) 2003-10-01 2008-06-24 Merck Patent Gesellschaft Mit Beschrankter Haftung Pigment composition for plastics
WO2010120745A1 (fr) * 2009-04-14 2010-10-21 Dupont Performance Elastomers L.L.C. Systèmes de gestion de combustible comportant un article en caoutchouc fluoré en contact avec du combustible biodiesel
EP1950245A4 (fr) * 2005-11-17 2010-12-01 Unimatec Co Ltd Fluorocopolymère allié
EP2557109A1 (fr) * 2011-08-11 2013-02-13 3M Innovative Properties Company Procédé de liaison d'un composé fluoroélastomère sur un substrat métallique utilisant des hydrocarbures fonctionnels à faible poids moléculaire en tant que promoteur de liaison
WO2018221518A1 (fr) * 2017-06-02 2018-12-06 Ａｇｃ株式会社 Polytétrafluoroéthylène modifié et procédé pour sa production

Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP0600090A1 (fr) * 1992-05-11 1994-06-08 Asahi Kasei Kogyo Kabushiki Kaisha Composition fluoroelastomere et moulage obtenu a partir de cette composition
JPH06329860A (ja) * 1993-05-19 1994-11-29 Asahi Glass Co Ltd 弗素ゴム組成物

Patent Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP0600090A1 (fr) * 1992-05-11 1994-06-08 Asahi Kasei Kogyo Kabushiki Kaisha Composition fluoroelastomere et moulage obtenu a partir de cette composition
JPH06329860A (ja) * 1993-05-19 1994-11-29 Asahi Glass Co Ltd 弗素ゴム組成物

Cited By (13)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US6864336B2 (en) 2002-09-12 2005-03-08 3M Innovative Properties Company Fluoroelastomers having low temperature characteristics and solvent resistance
US7148300B2 (en) 2002-09-12 2006-12-12 3M Innovative Properties Company Fluoroelastomers with improved permeation resistance and method for making the same
EP1591508A4 (fr) * 2003-02-06 2008-05-28 Nok Corp Composition de produit d'etancheite a base de fluorocaoutchouc et produit d'etancheite a base de fluorocaoutchouc
US7390842B2 (en) 2003-10-01 2008-06-24 Merck Patent Gesellschaft Mit Beschrankter Haftung Pigment composition for plastics
EP1950245A4 (fr) * 2005-11-17 2010-12-01 Unimatec Co Ltd Fluorocopolymère allié
WO2010120745A1 (fr) * 2009-04-14 2010-10-21 Dupont Performance Elastomers L.L.C. Systèmes de gestion de combustible comportant un article en caoutchouc fluoré en contact avec du combustible biodiesel
EP2557109A1 (fr) * 2011-08-11 2013-02-13 3M Innovative Properties Company Procédé de liaison d'un composé fluoroélastomère sur un substrat métallique utilisant des hydrocarbures fonctionnels à faible poids moléculaire en tant que promoteur de liaison
WO2013022729A1 (fr) * 2011-08-11 2013-02-14 3M Innovative Properties Company Procédé de collage d'un composé élastomère fluoré à un substrat métallique à l'aide d'hydrocarbures fonctionnels de faible masse moléculaire utilisés comme promoteurs de collage
CN103732712A (zh) * 2011-08-11 2014-04-16 3M创新有限公司 利用低分子量官能团烃作为粘合促进剂将含氟弹性体配混物粘合至金属基材的方法
US9567450B2 (en) 2011-08-11 2017-02-14 3M Innovative Properties Company Method of bonding a fluoroelastomer compound to a metal substrate using low molecular weight functional hydrocardons as bonding promoter
WO2018221518A1 (fr) * 2017-06-02 2018-12-06 Ａｇｃ株式会社 Polytétrafluoroéthylène modifié et procédé pour sa production
CN110662778A (zh) * 2017-06-02 2020-01-07 Ａｇｃ株式会社 改性聚四氟乙烯及其制造方法
CN110662778B (zh) * 2017-06-02 2021-08-17 Ａｇｃ株式会社 改性聚四氟乙烯及其制造方法

Similar Documents

Publication Publication Date Title
US5554680A (en) Heat-resistant perfluoroelastomer composition
US5268405A (en) Low temperature perfluoroelastomers
EP1400563A1 (fr) Composition d'élastomère fluoré
US6921796B2 (en) Fluoroelastomer compositions, their preparation, and their use
EP1353998B1 (fr) Compositions de fluoroelastomeres durcissables contenant des hydrosiloxanes ou des hydrosilazanes
PL189665B1 (pl) Układ wulkanizujący dla elastomerów fluorowych, sposób wulkanizacji elastomerów fluorowych i zastosowanie wulkanizowanych elastomerów fluorowych
JP2509345B2 (ja) 高い引張強度を有するフッ素ゴム加硫組成物
CA2028428A1 (fr) Fluoroelastomeres et chlorofluoroelastomeres durcissables au peroxyde, a sites de durcissement brome et iode, et leur preparation
WO1996026243A1 (fr) Melange elastomere vulcanisable avec fluoroelastomere vulcanise
KR20070004625A (ko) 개선된 저온 특성을 지닌 불소탄성중합체 및 이것의 제조방법
KR101022727B1 (ko) 내투과성이 향상된 플루오로엘라스토머 및 이의 제조 방법
EP1109844A1 (fr) Composition d'elastomere fluore possedant une excellente transformabilite et d'excellentes proprietes a basses temperatures
US4550132A (en) Peroxide-curable bromine-containing fluoroelastomers containing a sulfone
JP3758323B2 (ja) 含フッ素エラストマーの製造法
WO1998014517A1 (fr) Composition d'alliage a base de fluoroelastomeres et presentant d'excellentes proprietes a basse temperature
JP2877975B2 (ja) シリコーンゴムパウダー含有含フッ素エラストマー加硫組成物
US10513593B2 (en) Fluoroelastomer composition
JPH09143327A (ja) ブレンドゴム組成物
EP0824121A1 (fr) Elastomere fluore
WO2022149595A1 (fr) Composition de caoutchouc fluoré et élément d'étanchéité

Legal Events

Date Code Title Description
AK Designated states

Kind code of ref document: A1

Designated state(s): JP

AL Designated countries for regional patents

Kind code of ref document: A1

Designated state(s): AT BE CH DE DK ES FI FR GB GR IE IT LU MC NL PT SE

DFPE Request for preliminary examination filed prior to expiration of 19th month from priority date (pct application filed before 20040101)
121 Ep: the epo has been informed by wipo that ep was designated in this application
NENP Non-entry into the national phase

Ref country code: JP

Ref document number: 1998516797

Format of ref document f/p: F

122 Ep: pct application non-entry in european phase