WO2000053671A1 - Composites d'un agent de couplage de silice solide dans des compositions caoutchoutees a base de silice - Google Patents

Composites d'un agent de couplage de silice solide dans des compositions caoutchoutees a base de silice Download PDF

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Publication number
WO2000053671A1
WO2000053671A1 PCT/US2000/005919 US0005919W WO0053671A1 WO 2000053671 A1 WO2000053671 A1 WO 2000053671A1 US 0005919 W US0005919 W US 0005919W WO 0053671 A1 WO0053671 A1 WO 0053671A1
Authority
WO
WIPO (PCT)
Prior art keywords
silica
coupling agent
rubber
tire component
bis
Prior art date
Application number
PCT/US2000/005919
Other languages
English (en)
Inventor
Joy A. Foust
William J. O'briskie
Original Assignee
Bridgestone/Firestone Research, Inc.
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 Bridgestone/Firestone Research, Inc. filed Critical Bridgestone/Firestone Research, Inc.
Priority to CA002367339A priority Critical patent/CA2367339A1/fr
Priority to EP00916135A priority patent/EP1165681A1/fr
Priority to JP2000603305A priority patent/JP2003522065A/ja
Publication of WO2000053671A1 publication Critical patent/WO2000053671A1/fr

Links

Classifications

    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B60—VEHICLES IN GENERAL
    • B60C—VEHICLE TYRES; TYRE INFLATION; TYRE CHANGING; CONNECTING VALVES TO INFLATABLE ELASTIC BODIES IN GENERAL; DEVICES OR ARRANGEMENTS RELATED TO TYRES
    • B60C1/00—Tyres characterised by the chemical composition or the physical arrangement or mixture of the composition
    • B60C1/0016—Compositions of the tread
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B60—VEHICLES IN GENERAL
    • B60C—VEHICLE TYRES; TYRE INFLATION; TYRE CHANGING; CONNECTING VALVES TO INFLATABLE ELASTIC BODIES IN GENERAL; DEVICES OR ARRANGEMENTS RELATED TO TYRES
    • B60C1/00—Tyres characterised by the chemical composition or the physical arrangement or mixture of the composition
    • 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
    • C08K5/54—Silicon-containing compounds
    • C08K5/548—Silicon-containing compounds containing sulfur

Definitions

  • the present invention relates to a silica coupling agent composite containing a solid binder which is utilized in rubber compositions containing silica.
  • a solid silica coupling agent composite has ease of handling benefits such as minimization of agglomeration, enhanced dispersion, the promotion of adhesion between silica and rubber, and ease of identification of the composite.
  • Coupling agents are often utilized to connect silica, a reinforcing agent, to a polymer chain such as a sulfur vulcanizable rubber chain.
  • organosilanes have become popular coupling agents used in rubber compositions.
  • One component of the coupling agent reacts with the surface of a silica and another component reacts with the rubber thereby linking or bridging them as through covalent bonding.
  • the organosilanes which are currently employed commercially present numerous problems in the practicality of their use. Commonly, organosilanes, such as bis(3-triethoxysilypropyl)tetrasulf ⁇ de are in liquid form.
  • silanes examples include SI-69 sold by the Degussa Corporation and A1289 sold by Witco.
  • Organosilanes are also available as a "supported grade", in which organosilanes are mixed with carbon black in various ratios, such as X50-S available from Degussa Corp.
  • the present invention relates to rubber compositions containing silica and a composite comprising a silica coupling agent and a binder.
  • a solid binder is preferred such as a wax, as well as optionally, a polyolefin.
  • the use of the solid silica coupling agent composite is desirable in various tire components such as a tread when it contains silica therein.
  • the composites of the present invention fully melt into a composition, such as a rubber composition, and results in improved dispersion. Such a composite is clean, environmentally friendly, and easily identifiable.
  • An important aspect of the present invention is the addition of a generally solid composite to a silica reinforced rubber composition.
  • the composite comprises a substantially homogenous mixture of a silica coupling agent and a binder.
  • any solid shape can be utilized, such as pellets, cubes, spheres, and the like, with pellets being preferred.
  • any conventional silica coupling agent can be utilized including those which have a functional or reactive group which can react with silica and also another functional or reactive group which can react with the rubber, particularly, a sulfur vulcanizable rubber which contains unsaturated carbon to carbon bonds.
  • the silica coupling agent thus acts as a connecting bridge between the silica and the rubber.
  • Suitable functional groups include amino. vinyl, epoxy. mercapto. chloro. bromo. and iodo. methacryl and methacryoyl. glycidoxyl, nitroso. imido. octyl. oligomeric. ureido. polysulfide groups, and the like.
  • Preferred coupling agents of the present invention include organosilanes of the formula:
  • n is an integer of from 2 to about 7; wherein k and m. independently, is from 0, i.e. non-existent, to about 3. and wherein R 1 through R , independently, is H or an alkyl group having from 1 to 12 carbons.
  • organosilane coupling agents include:
  • organosilane silica coupling agents include bis(3-triethoxysilylpropyl)tetrasulf ⁇ de, bis (3-triethoxysilylpropyl)disulfide. and combinations thereof.
  • organosilane coupling agents include methyltriethoxysilane; methyltrimethoxysilane: vinyltriethoxysilane: vinyltrimethoxysilane:vinyl-tris (2methoxyethoxysilane): vinvltriacetoxvsilane; gammamethacryloxypropyltrimethoxysilane; gamma-methacryloxypropyl-tris-
  • (2-methoxyethoxy)silane beta-(3.4-epoxycyclohexyl)ethyltrimethoxysilane: gammaglycidoxypropyltrimethoxysilane; gamma- mercaptopropyltrimethoxysilane; gamma mercaptopropyltriethoxysilane: gamma-aminopropyltriethoxysilane; gamma-aminopropyltriethoxysilane; gamma-aminopropyltriethoxysilane: aminoalkyl silicone solution: modified aminoorganosilane; gammaaminopropyltrimethoxysilane: N-beta-(aminoethy 1 )- gammaaminopropyltrimethoxysilane: modified aminoorganosilane: triaminofunctional silane.
  • silane modified elastomers that is elastomers having silane functional groups as part of the polymer, proportionately smaller amounts of the above coupling agents are utilized because of the existence of the silica coupling agents contained within the elastomer.
  • the amount of the silica coupling agent based upon 100 parts by wt. of silica is generally from about 0.1 to about 20, desirably from about 0.5 to about 15, and preferably from about 1.0 to about 10 parts by wt.
  • a function of the binder is to act as a carrier for the silica-coupling agent.
  • the term "binder" comprises all components in the composite except the silica- coupling agent.
  • the binder has a higher melting point than the silica coupling agent, and imparts the solid form to the composite at ambient temperatures, for example, about 70°F (21 °C).
  • the binder can be a wax (preferred), a thermoplastic polymer, a compatibilizing agent, a wetting agent, a fatty acid, ethylene vinyl acetate, a stabilizer, and the like as well as combinations thereof.
  • Any natural, synthetic or petroleum based wax can be utilized in the binder. Examples include, but are not limited to, paraffin, microcrystalline. carnauba and beeswax. Microcrystalline wax is preferred.
  • Any thermoplastic polymer can be utilized in the binder of the present invention, such as a polyolefm made from monomers having from 2 to 6 carbon atoms. Thermoplastic polymers are generally optional and are utilized as a blend with the wax or other component.
  • the thermoplastic polymer is oxidized polyethylene, which helps promote compatibility between the silica coupling agent and the binder components.
  • the amount of the binder is generally from about 25 to about 90. desirably from about 28 to about 75. and preferably from about 32 to about 55% by weight based upon a total weight of the silica coupling agent and the binder. While oxidized polyethylene can be utilized alone, it is generally utilized as a minor portion in combination with a wax.
  • the binder composite is formed by combining the silica coupling agent and the binder in a liquid phase where the components can be blended to form a homogeneous mixture. The mixture is processed through conventional methods into a desired usable form such as pellets, spheres or the like.
  • a preferred composite utilized in the present invention is available from Elastochem known as "EF(TESPT)-60".
  • This composite contains bis(3-triethoxysilylpropyl) tetrasulfide in a binder of wax and oxidized polyethylene.
  • This composite is generally free of mineral tillers and carbon black.
  • the amount of the silica coupling agent composite can vary, but generally is from about 0.2 to about 30. desirably from about 3 to about 25. and preferably from about 6 to about 18 parts by weight based upon 100 parts by weight of all silica utilized within the rubber composition.
  • the silica in the rubber composition generally can be any type of silica such as fumed, hydrated and preferably is precipitated silica. Advantages of using silica include reduced rolling resistance in tires and hence improved gasoline mileage of the vehicle.
  • Suitable silicas generally have a BET surface area, as measured utilizing nitrogen gas, of from about 40 to about 600 and preferably from about 50 to about 300 square meters per gram.
  • the ultimate particle size of the silica is generally from about 0.1 to about 100. and desirably from about 5 to about 50 nanometers as measured by an electron microscope although smaller or larger particles can exist.
  • the amount of the silica generalh ranges from about 5 to about 100 . desirably from about 15 to about 80. and preferably from about 25 to about 60 parts by weight per 100 parts by weight of total tire component rubber.
  • Commercially available silicas which can be utilized in the present invention include silicas commercially available from PPG Industries under the Hi-Sil trademark such as designations 190. 210. 233, 243. etc.; silicas from Rhone-Poulenc such as Zl 165MP and Z165GR; silicas available from Degussa AG such as VN2 and VN3; and silicas from Akzo Chemical.
  • the rubber composition of the present invention is made from natural rubber, at least one conjugated diene monomer, or from a conjugated diene and one or more vinyl-substituted aromatic monomers, and optionally from ethylene and propylene monomers, or ethylene-propylene and a non- conjugated diene (i.e., EPDM rubber.)
  • the conjugated diene monomers have a total of from 4 to 10 carbon atoms with examples including 1,3-butiene, isoprene, 1,3-pentadiene, 2,3-dimethyl-l,3-butadiene, 2 -methyl- 1,3-pentadiene, 2.3-dimethyl- 1,3-pentadiene.
  • the one or more vinyl-substituted aromatic monomers have a total of from 8 to 12 carbon atoms such as 1 - vinylnaphthalene, 3-methylstyrene (p- methyl styrene), 3,5-diethylstyrene, and the like with styrene being preferred.
  • Preferred tread rubber compositions generally include natural rubber (cis- 1 ,4- polyisoprene). synthetic polyisoprene. styrene butadiene rubber, modified styrene-butadiene rubber, butadiene rubber, modified butadiene rubber, and the like. Often the rubber is oil extended.
  • the rubber composition of the present invention such as the tread can be compounded by methods and procedures well known to the rubber compounding art and contain various conventional additives in suitable amounts.
  • carbon black, extra conductive carbon black, as well as other types of carbon black, curing aids such as sulfur, sulfur containing compounds and the like are utilized.
  • Vulcanizing accelerators which can be used in the present invention include amines, disulfides. guanidines. thioureas. thiazoles, thiurams. sulfenamides. dithiocarbamates. and the like.
  • Other additives include various oils such as aromatic, naphthenic.
  • various antioxidants such as various phenylenediamines: various antiozonants
  • various aliphatic acids such as steric acid: zinc oxide: various waxes such as micro crystalline waxes; various peptizers. starch, and the like.
  • Various fillers can also be utilized such as clay, for example kaolin, clay, and the like.
  • the rubber composition containing the silica coupling agent composite of the present invention can be utilized in any application wherein it is desirable to use silica coupling agents in a form that is easier to handle, compound and weigh. Specific applications thus include various components in a tire such as a tire tread, tire sidewall, tire casing, carcass plies sub-treads, and the like, and preferably is utilized in a tread.
  • the silica coupling agent composite can also be utilized in many other applications such as in hoses, belts, wire cables, shoe soles, and wherever silica reinforced rubber is utilized.
  • the solid composites of the present invention are a good alternative when compared to a liquid or supported grades of silica coupling agents.
  • the composite is environmentally friendly as it leaves no appreciable residue in containers or handling equipment and therefore less of the product is wasted. Since it is a solid, no stratification or loss to dust collectors will occur.
  • the composite also offers improved batch to batch consistency and is readily visually distinguished from blends containing carbon black with other materials.
  • the Control and Example 1 were prepared as follows: The first mixing stage involved adding the polymer, half of the carbon black, silica coupling agent and all other ingredients except the accelerators and sulfur. It was mixed in a Banbury at a temperature of 300°F for approximately 3 minutes. During the second mixing stage, the rest of the carbon black was added and mixed in a Banbury at approximately 300°F for about 2 minutes.
  • the subsequent remill stage was mixed at temperatures of approximately 260°F for about 1 minute.
  • the final mixing stage involved adding all of the accelerators and sulfur to the batch, and mixing at a temperature of approximately 200°F for 1 minute.
  • Example 2 had the same recipe as Example 1 except a disulfide organosilane coupling agent was utilized. This allowed the recipe to be formulated at a slightly higher temperature during the first stage i.e. 330°F instead of 300°F.
  • the second stage mixing temperature was 300°F whereas the third stage mixing temperature was only 200°F.
  • a fourth stage mixing step was not required since use of the disulfide coupling agent allowed a higher first stage mixing temperature. The elimination of a single stage in a mixing or a compounding operation is a notable advantage.

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  • Engineering & Computer Science (AREA)
  • Mechanical Engineering (AREA)
  • 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)

Abstract

L'invention concerne des compositions caoutchoutées contenant de la silice, du type de celles utilisées dans divers composants de pneumatiques, ces compositions renfermant un composite à base d'un liant et d'un agent de couplage de silice solide.
PCT/US2000/005919 1999-03-10 2000-03-08 Composites d'un agent de couplage de silice solide dans des compositions caoutchoutees a base de silice WO2000053671A1 (fr)

Priority Applications (3)

Application Number Priority Date Filing Date Title
CA002367339A CA2367339A1 (fr) 1999-03-10 2000-03-08 Composites d'un agent de couplage de silice solide dans des compositions caoutchoutees a base de silice
EP00916135A EP1165681A1 (fr) 1999-03-10 2000-03-08 Composites d'un agent de couplage de silice solide dans des compositions caoutchoutees a base de silice
JP2000603305A JP2003522065A (ja) 1999-03-10 2000-03-08 シリカゴム中の固体シリカカップリング剤複合体

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
US26521299A 1999-03-10 1999-03-10
US09/265,212 1999-03-10

Publications (1)

Publication Number Publication Date
WO2000053671A1 true WO2000053671A1 (fr) 2000-09-14

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PCT/US2000/005919 WO2000053671A1 (fr) 1999-03-10 2000-03-08 Composites d'un agent de couplage de silice solide dans des compositions caoutchoutees a base de silice

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Country Link
EP (1) EP1165681A1 (fr)
JP (1) JP2003522065A (fr)
CA (1) CA2367339A1 (fr)
WO (1) WO2000053671A1 (fr)

Cited By (10)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2002031041A1 (fr) * 2000-10-13 2002-04-18 Societe De Technologie Michelin Composition de caoutchouc comportant a titre d'agent de couplage un organosilane polyfonctionnel
US7737209B2 (en) * 2006-07-06 2010-06-15 Sumitomo Rubber Industries, Ltd. Rubber composition and tire using same
WO2010133373A1 (fr) 2009-05-20 2010-11-25 Societe De Technologie Michelin Agent de couplage organosilane
WO2010133371A1 (fr) 2009-05-20 2010-11-25 Societe De Technologie Michelin Composition de caoutchouc comportant un agent de couplage organosilane
US8669321B2 (en) 2009-12-07 2014-03-11 Sumitomo Rubber Industries, Ltd. Tire rubber composition and pneumatic tire
US8921468B2 (en) 2007-06-05 2014-12-30 Sumitomo Rubber Industries, Ltd. Rubber composition for tire, tire member, base tread rubber composition, base tread and tire
US8957155B2 (en) 2008-12-22 2015-02-17 Compagnie Generale Des Etablissements Blocked mercaptosilane coupling agent
WO2018002536A1 (fr) 2016-06-30 2018-01-04 Compagnie Generale Des Etablissements Michelin Composition de caoutchouc comprenant un agent de couplage polysulfure de monohydroxysilane
WO2018002534A1 (fr) 2016-06-30 2018-01-04 Compagnie Generale Des Etablissements Michelin Polysulfure de monohydroxysilane
WO2018109335A1 (fr) 2016-12-16 2018-06-21 Compagnie Generale Des Etablissements Michelin Polysulfure d'alcoxysilane

Families Citing this family (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US10179479B2 (en) 2015-05-19 2019-01-15 Bridgestone Americas Tire Operations, Llc Plant oil-containing rubber compositions, tread thereof and race tires containing the tread

Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
FR2512037A1 (fr) * 1981-09-03 1983-03-04 Rhone Poulenc Chim Base Composition elastomerique renforcee par des silices a grande surface specifique
US5739198A (en) * 1996-03-18 1998-04-14 The Goodyear Tire & Rubber Company Rubber composition and tire with tread thereof

Patent Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
FR2512037A1 (fr) * 1981-09-03 1983-03-04 Rhone Poulenc Chim Base Composition elastomerique renforcee par des silices a grande surface specifique
US5739198A (en) * 1996-03-18 1998-04-14 The Goodyear Tire & Rubber Company Rubber composition and tire with tread thereof

Cited By (14)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
KR100849607B1 (ko) 2000-10-13 2008-07-31 소시에떼 드 테크놀로지 미쉐린 다관능성 오가노실란을 커플링제로서 포함하는 고무 조성물
US7488768B2 (en) 2000-10-13 2009-02-10 Michelin Recherche Et Technique S.A. Rubber composition comprising a polyfunctional organosilane as coupling agent
WO2002031041A1 (fr) * 2000-10-13 2002-04-18 Societe De Technologie Michelin Composition de caoutchouc comportant a titre d'agent de couplage un organosilane polyfonctionnel
US7737209B2 (en) * 2006-07-06 2010-06-15 Sumitomo Rubber Industries, Ltd. Rubber composition and tire using same
US8921468B2 (en) 2007-06-05 2014-12-30 Sumitomo Rubber Industries, Ltd. Rubber composition for tire, tire member, base tread rubber composition, base tread and tire
US8957155B2 (en) 2008-12-22 2015-02-17 Compagnie Generale Des Etablissements Blocked mercaptosilane coupling agent
WO2010133373A1 (fr) 2009-05-20 2010-11-25 Societe De Technologie Michelin Agent de couplage organosilane
WO2010133371A1 (fr) 2009-05-20 2010-11-25 Societe De Technologie Michelin Composition de caoutchouc comportant un agent de couplage organosilane
US8669321B2 (en) 2009-12-07 2014-03-11 Sumitomo Rubber Industries, Ltd. Tire rubber composition and pneumatic tire
WO2018002536A1 (fr) 2016-06-30 2018-01-04 Compagnie Generale Des Etablissements Michelin Composition de caoutchouc comprenant un agent de couplage polysulfure de monohydroxysilane
WO2018002534A1 (fr) 2016-06-30 2018-01-04 Compagnie Generale Des Etablissements Michelin Polysulfure de monohydroxysilane
US10961371B2 (en) 2016-06-30 2021-03-30 Compagnie Generale Des Etablissements Michelin Rubber composition comprising a monohydroxysilane polysulfide coupling agent
WO2018109335A1 (fr) 2016-12-16 2018-06-21 Compagnie Generale Des Etablissements Michelin Polysulfure d'alcoxysilane
US10968333B2 (en) 2016-12-16 2021-04-06 Compagnie Generale Des Etablissements Michelin Alkoxysilane polysulphide

Also Published As

Publication number Publication date
EP1165681A1 (fr) 2002-01-02
CA2367339A1 (fr) 2000-09-14
JP2003522065A (ja) 2003-07-22

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