EP1165681A1 - Feste silika kupplungsmittelzusammensetzungen in silika kautschuk - Google Patents

Feste silika kupplungsmittelzusammensetzungen in silika kautschuk

Info

Publication number
EP1165681A1
EP1165681A1 EP00916135A EP00916135A EP1165681A1 EP 1165681 A1 EP1165681 A1 EP 1165681A1 EP 00916135 A EP00916135 A EP 00916135A EP 00916135 A EP00916135 A EP 00916135A EP 1165681 A1 EP1165681 A1 EP 1165681A1
Authority
EP
European Patent Office
Prior art keywords
silica
coupling agent
rubber
tire component
bis
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.)
Withdrawn
Application number
EP00916135A
Other languages
English (en)
French (fr)
Inventor
Joy A. Foust
William J. O'briskie
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.)
Bridgestone Americas Tire Operations LLC
Original Assignee
Bridgestone Americas Tire Operations LLC
Bridgestone Research 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 Bridgestone Americas Tire Operations LLC, Bridgestone Research LLC filed Critical Bridgestone Americas Tire Operations LLC
Publication of EP1165681A1 publication Critical patent/EP1165681A1/de
Withdrawn legal-status Critical Current

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.

Landscapes

  • Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Mechanical Engineering (AREA)
  • Health & Medical Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Organic Chemistry (AREA)
  • Compositions Of Macromolecular Compounds (AREA)
EP00916135A 1999-03-10 2000-03-08 Feste silika kupplungsmittelzusammensetzungen in silika kautschuk Withdrawn EP1165681A1 (de)

Applications Claiming Priority (3)

Application Number Priority Date Filing Date Title
US26521299A 1999-03-10 1999-03-10
US265212 1999-03-10
PCT/US2000/005919 WO2000053671A1 (en) 1999-03-10 2000-03-08 Solid silica coupling agent composites in silica rubber

Publications (1)

Publication Number Publication Date
EP1165681A1 true EP1165681A1 (de) 2002-01-02

Family

ID=23009504

Family Applications (1)

Application Number Title Priority Date Filing Date
EP00916135A Withdrawn EP1165681A1 (de) 1999-03-10 2000-03-08 Feste silika kupplungsmittelzusammensetzungen in silika kautschuk

Country Status (4)

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

Cited By (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

Families Citing this family (10)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CA2425330A1 (fr) * 2000-10-13 2002-04-18 Jean-Claude Tardivat Composition de caoutchouc comportant a titre d'agent de couplage un organosilane polyfonctionnel
EP2141199B1 (de) * 2006-07-06 2011-11-02 Sumitomo Rubber Industries, Ltd. Gummimischung und Reifen damit
WO2008149588A1 (ja) * 2007-06-05 2008-12-11 Sumitomo Rubber Industries, Ltd. タイヤ用ゴム組成物、タイヤ部材、ベーストレッド用ゴム組成物、ベーストレッドおよびタイヤ
FR2940290B1 (fr) 2008-12-22 2010-12-31 Michelin Soc Tech Agent de couplage mercaptosilane bloque
FR2945815B1 (fr) 2009-05-20 2011-07-01 Michelin Soc Tech Composition de caoutchouc comportant un agent de couplage organosilane
FR2947552B1 (fr) 2009-05-20 2011-08-26 Michelin Soc Tech Agent de couplage organosilane
JP5256262B2 (ja) 2009-12-07 2013-08-07 住友ゴム工業株式会社 タイヤ用ゴム組成物及び空気入りタイヤ
FR3053337B1 (fr) 2016-06-30 2018-07-06 Compagnie Generale Des Etablissements Michelin Polysulfure de monohydroxysilane
FR3053345B1 (fr) 2016-06-30 2018-07-06 Compagnie Generale Des Etablissements Michelin Composition de caoutchouc comprenant un agent de couplage polysulfure de monohydroxysilane
FR3060565A1 (fr) 2016-12-16 2018-06-22 Michelin & Cie Polysulfure d'alcoxysilane

Family Cites Families (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
FR2512037B1 (fr) * 1981-09-03 1986-02-14 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

Non-Patent Citations (1)

* Cited by examiner, † Cited by third party
Title
See references of WO0053671A1 *

Cited By (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

Also Published As

Publication number Publication date
JP2003522065A (ja) 2003-07-22
WO2000053671A1 (en) 2000-09-14
CA2367339A1 (en) 2000-09-14

Similar Documents

Publication Publication Date Title
US5780538A (en) Silica reinforced rubber composition and tire with tread
US5914364A (en) Silica reinforced rubber composition and tire with tread
US5719207A (en) Silica reinforced rubber composition and tire with tread
EP0995775B1 (de) Herstellung stärkehaltiger Kautschuke, Reife aus vulcanisiertem Gummi und hergestellter Gegenstand
US5605951A (en) Silica reinforced rubber compostition and tire with tread thereof
CA2157845C (en) Silica reinforced rubber preparation and tire with tread thereof
US6458871B2 (en) Preparation of starch reinforced rubber and use thereof in tires
US10087306B2 (en) Additive for silica reinforced rubber formulations
JP2000001572A (ja) シリカで強化されたゴム組成物及びそのトレッドを備えたタイヤ
US6355719B1 (en) Heterogeneous silica carbon black-filled rubber compound
EP0994150B1 (de) Herstellung gefüllter Kautschuke
EP0732362A1 (de) Mit Kieselsäure verstärkte Kautschukzusammensetzung und ihre Verwendung in Reifen
US9163126B2 (en) Silica-rich rubber compositions and methods of making same
CA2209575A1 (en) Silica reinforced rubber composition and use in tires
US7247669B2 (en) Rubber prepared with precipitated silica and carbon black pellet composites of controlled hardness and tire with component derived therefrom
US7640957B2 (en) Tire with rubber tread highly loaded with a combination of filler reinforcement and oil
EP0896978A2 (de) Kautschukzusammensetzung und Reifen mit daraus hergestellter Lauffläche
EP1165681A1 (de) Feste silika kupplungsmittelzusammensetzungen in silika kautschuk
US6306949B1 (en) Preparation of reinforced rubber and use in tires
EP0794221A1 (de) Verfahren zur Herstellung von mit Teilchen verstärkte Kautschukzusammensetzung
US6111008A (en) Tire with silica reinforced tread which contains specified carbon black
CA2154634A1 (en) Silica reinforced rubber composition and tire with tread
MXPA97001752A (en) Hollow composition reinforced with silice, and rim with rodamie band
MXPA99002037A (en) Composition of reinforced rubber with silica and pneumatic with a contact surface with the p

Legal Events

Date Code Title Description
PUAI Public reference made under article 153(3) epc to a published international application that has entered the european phase

Free format text: ORIGINAL CODE: 0009012

17P Request for examination filed

Effective date: 20010920

AK Designated contracting states

Kind code of ref document: A1

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

RAP1 Party data changed (applicant data changed or rights of an application transferred)

Owner name: BRIDGESTONE/FIRESTONE NORTH AMERICA TIRE LLC

STAA Information on the status of an ep patent application or granted ep patent

Free format text: STATUS: THE APPLICATION HAS BEEN WITHDRAWN

18W Application withdrawn

Withdrawal date: 20020619

RBV Designated contracting states (corrected)

Designated state(s): DE ES FR GB IT NL