WO2008084885A1 - Method for manufacturing a bis(silatranylalkyl) polysulfide, method for manufacturing a mixture of bis(silatranylalkyl) polysulfide etc., a mixture of bis(silatranylalkyl) polysulfide etc., and rubber composition - Google Patents

Method for manufacturing a bis(silatranylalkyl) polysulfide, method for manufacturing a mixture of bis(silatranylalkyl) polysulfide etc., a mixture of bis(silatranylalkyl) polysulfide etc., and rubber composition Download PDF

Info

Publication number
WO2008084885A1
WO2008084885A1 PCT/JP2008/050659 JP2008050659W WO2008084885A1 WO 2008084885 A1 WO2008084885 A1 WO 2008084885A1 JP 2008050659 W JP2008050659 W JP 2008050659W WO 2008084885 A1 WO2008084885 A1 WO 2008084885A1
Authority
WO
WIPO (PCT)
Prior art keywords
bis
polysulfide
silatranylalkyl
trialkoxysilylalkyl
general formula
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/JP2008/050659
Other languages
French (fr)
Inventor
Takeaki Saiki
Makoto Iwai
Anil Kumar Tomar
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 Toray Specialty Materials KK
Dow Silicones Corp
Original Assignee
Dow Corning Toray Co Ltd
Dow Corning Corp
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 Dow Corning Toray Co Ltd, Dow Corning Corp filed Critical Dow Corning Toray Co Ltd
Priority to US12/522,835 priority Critical patent/US8093323B2/en
Priority to EP08703509A priority patent/EP2104678A1/en
Priority to CN2008800016407A priority patent/CN101578291B/en
Publication of WO2008084885A1 publication Critical patent/WO2008084885A1/en
Anticipated expiration legal-status Critical
Ceased legal-status Critical Current

Links

Classifications

    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
    • C07F7/00—Compounds containing elements of Groups 4 or 14 of the Periodic Table
    • C07F7/02—Silicon compounds
    • C07F7/08—Compounds having one or more C—Si linkages
    • C07F7/18—Compounds having one or more C—Si linkages as well as one or more C—O—Si linkages
    • C07F7/1804—Compounds having Si-O-C linkages
    • C07F7/1872—Preparation; Treatments not provided for in C07F7/20
    • C07F7/188—Preparation; Treatments not provided for in C07F7/20 by reactions involving the formation of Si-O linkages
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
    • C07F7/00—Compounds containing elements of Groups 4 or 14 of the Periodic Table
    • C07F7/02—Silicon compounds
    • C07F7/08—Compounds having one or more C—Si linkages
    • C07F7/18—Compounds having one or more C—Si linkages as well as one or more C—O—Si linkages
    • C07F7/1804—Compounds having Si-O-C linkages

Definitions

  • the present invention relates to a novel method for manufacturing a bis(silatranylalkyl) polysulfide; to a method for manufacturing a mixture of a bis(silatranylalkyl) polysulfide and a (silatranylalkyl) (trialkoxysilylalkyl) polysulfide; to a method for manufacturing a mixture of a bis(silatranylalkyl) polysulfide, a
  • Patent Literature 1 Japanese Unexamined Patent Application Publication ⁇ hereinafter referred to as "Kokai" ⁇ S50- 108225, i.e., JP50- 108225 A
  • Patent Reference 2 Korean Unexamined Patent Application Publication ⁇ hereinafter referred to as "Kokai" ⁇ S50- 108225, i.e., JP50- 108225 A
  • Patent Reference 2 Korean Unexamined Patent Application Publication ⁇ hereinafter referred to as "Kokai" ⁇ S50- 108225, i.e., JP50- 108225 A
  • Patent Reference 2 Korean Unexamined Patent Application Publication ⁇ hereinafter referred to as "Kokai” ⁇ S50- 108225, i.e., JP50- 108225 A
  • Patent Reference 2 Korean Unexamined Patent Application Publication ⁇ hereinafter referred to as "Kokai" ⁇ S50- 108225, i.e., JP50- 108225 A
  • Example 13 added to the specification of Patent Reference 2 after the publication of the application describes synthesis of a bis(silatranylpropyl) tetrasulfide by mixing 2 moles of a silatranylpropylmercaptane with 3 moles of a sulfur powder under heating conditions.
  • Example 13 of Patent Reference 2 describes a synthesized bis(silatranylpropyl) tetrasulfide, which is a white crystalline substance having no melting point.
  • the bis(silatranylpropyl) tetrasulfide is a crystalline substance having no melting point, dispersion thereof in such substances as a natural rubber or synthetic rubber and a silica filler presents a problem, even when the mixture is kneaded with application of a shear force, e.g., in a two-roll mill.
  • the present invention relates to a method for manufacturing a bis(silatranylalkyl) polysulfide represented by the general formula (3):
  • R is an alkylene group having 1 to 10 carbon atoms and "x" is a number from 2 to 8) and a (silatranylalkyl) (trialkoxysilylalkyl) polysulfide represented by the general formula (4):
  • Fig. 1 illustrates a 29 Si-NMR chart for the bis(silatranylpropyl) disulfide synthesized in
  • FIG. 2 illustrates a 13 C-NMR chart for the bis(silatranylpropyl) disulfide synthesized in
  • Fig. 3 illustrates a 29 Si-NMR chart for the mixture of the bis(silatranylpropyl) disulfide
  • Fig. 4 illustrates a 13 C-NMR chart for the mixture of the bis(silatranylpropyl) disulfide
  • Fig. 5 illustrates a 29 Si-NMR chart for the bis(silatranylpropyl) tetrasulfide synthesized in
  • FIG. 6 illustrates a 13 C-NMR chart for the bis(silatranylpropyl) tetrasulfide synthesized in
  • the present invention relate to the following; [1] A method for manufacturing a bis(silatranylalkyl) polysulfide represented by the general formula (3):
  • R is an alkylene group having 1 to 10 carbon atoms and "x" is a number from 2 to 8) and a (silatranylalkyl) (trialkoxysilylalkyl) polysulfide represented by the general formula (4):
  • R is an alkylene group having 1 to 10 carbon atoms, and "x" is a number from 2 to 8) and a (silatranylalkyl) (trialkoxysilylalkyl) polysulfide represented by the general formula (4):
  • R is an alkylene group having 1 to 10 carbon atoms
  • x is a number from
  • a rubber composition comprising:
  • a rubber composition comprising: 100 parts by weight of an uncured organic rubber (A),
  • the method of the present invention for synthesis of the bis(silatranylalkyl) polysulfide is highly safe since it does not use sulfur as a starting material and does not generate toxic hydrogen sulfide in the synthesis process.
  • the method of the present invention for manufacturing a mixture of a bis(silatranylalkyl) polysulfide and a (silatranylalkyl) (trialkoxysilylalkyl) polysulfide is highly safe, since it does not use sulfur as a starting material and does not generate toxic hydrogen sulfide in the manufacturing process.
  • the mixtures of the present invention are intermediate reaction products between the aforementioned bis(silatranylalkyl) polysulfide and bis(trialkoxysilylalkyl) polysulfide, which can be easily mixed with a rubber, a silica filler, and the like, since the mixtures are liquid at ambient temperature.
  • a vulcanizate of the rubber composition of the present invention has improved properties.
  • R is an alkylene group having 1 to 10 carbon atoms, and "x" is a number from 2 to 8), which is the target product of the manufacturing procedure, alkylene groups having 1 to 10 carbon atoms bond to sulfur atoms on both ends of the polysulfide that has 2 to 8 sulfur atoms, and silicon atoms of the silatranyl groups bond to carbon atoms on the terminals of the aforementioned alkylene groups.
  • R represents alkylene groups having 1 to 10 carbon atoms.
  • alkylene groups can be exemplified by ethylene, propylene, butylene, pentylene, hexylene, heptylene, and octylene groups.
  • propylene to decylene groups have a linear molecular structure, but may also have a branched or cyclic structure. From the viewpoint of ease of production, it is advantageous to use propylene or butylene with a linear or branched molecular structure. From the viewpoint of ease of production, it is recommended to have 2 to 4 sulfur atoms.
  • bis(silatranylalkyl) polysulfide bis(silatranylethyl) disulfide, bis(silatranylethyl) tetrasulfide, bis(silatranylpropyl) disulfide, bis(silatranylpropyl) tetrasulfide, bis(silatranylbutyl) tetrasulfide, bis(silatranylpropyl) hexylsulfide, and bis(silatranylbutyl) hexylsulfide.
  • the bis(trialkoxysilylalkyl) polysulfide represented by the general formula (1):
  • R designates an alkylene group having 1 to 10 alkylene atoms
  • R 1 is an alkyl group having 1 to 4 carbon atoms
  • "x" is a number from 2 to 8
  • R 1 is an alkyl group having 1 to 4 carbon atoms.
  • Such an alkyl group can be exemplified by methyl, ethyl, propyl, and butyl groups. Normally, the propyl and butyl groups have a linear molecular structure but a branched structure is also possible. From the viewpoint of ease of substituted with silatranyl group the use of methyl groups and, especially, ethyl groups, is preferable.
  • the alkylene groups designated by R can be exemplified by ethylene, propylene, butylene, pentylene, hexylene, heptylene, and octylene groups.
  • the groups from propylene to decylene have a liner molecular structure, but may also have a branched or cyclic structure as well.
  • the propylene group and butylene group with the linear or branched molecular structure are preferable for ease of production.
  • bis(trialkoxysilylalkyl) polysulfide represented by the general formula (1): bis(trimethoxysilylpropyl) disulfide, bis(trimethoxysilylbutyl) disulfide, bis(triethoxysilylpropyl) disulfide, bis(triethoxysilylbutyl) disulfide, bis(trimethoxysilylpropyl) tetrasulfide, bis(triethoxysilylpropyl) tetrasulfide, bis(tripropoxysilylpropyl) tetrasulfide, bis(trimethoxysilylbutyl) tetrasulfide, bis(trimethoxysilylbutyl) tetrasulfide, bis(tripropoxysilylbutyl) tetrasulfide, bis(trimethoxysilylpropyl) hexy
  • the reaction should be carried out in the presence of an alkali metal alcoholate used in a catalytic quantity.
  • the alkali metal alcoholate can be represented by sodium methoxide, sodium ethoxide, potassium methoxide, potassium ethoxide, or lithium ethoxide. It is recommended to use alkali metal alcoholate in the amount of 0.1 to 5.0 mole % per 1 mole of the bis(trialkoxysilylalkyl) polysulfide represented by the general formula (1). Since the alkali metal alcoholate is a solid, it is added to the bis(trialkoxysilylalkyl) polysulfide represented by the general formula (1) preferably in a form of an alcohol solution.
  • the reaction between the bis(trialkoxysilylalkyl) polysulfide represented by the general formula (1) and the triethanolamine can be carried out for about 30 min. to 4 hours under a reduced pressure and at a temperature in the range of 120 to 180 0 C.
  • the alcohol developed in the reaction is removed by distillation under heating and reduced-pressure conditions. If the product of the reaction contains residual triethanolamine that has been supplied to the reaction, it also can be removed together with the alcohol by distillation under heating and reduced-pressure conditions.
  • a mixture of the present invention is composed of a bis(silatranylalkyl) polysulfide represented by the general formula (3):
  • R is an alkylene group having 1 to 10 carbon atoms, and "x" is a number from 2 to 8) and a (silatranylalkyl) (trialkoxysilylalkyl) polysulfide represented by the general formula (4):
  • Another mixture of the present invention is composed of a mixture of a bis(silatranylalkyl) polysulfide represented by the general formula (3):
  • R 1 is an alkyl group having 1 to 4 carbon atoms.
  • Appropriate rubber compositions to which the bis(silatranylalkyl) polysulfide or the aforementioned mixtures that have been produced by the method of the present invention are added may consist mainly of an uncured organic rubber (A) and a silica filler (B), or an uncured organic rubber (A), a silica filler (B), and a carbon black (D).
  • An uncured organic rubber is usually referred to merely as "rubber”. This component is an organic polymer that exhibits resiliency when vulcanized.
  • the appropriate uncured organic rubber comprises a highly unsaturated organic polymer compound, in particular, a diene-type polymer compound with an iodine number in the range of 20 to 450.
  • the uncured organic rubber is exemplified by an uncured styrene/butadiene copolymer rubber, uncured polybutadiene rubber, uncured isoprene/butadiene copolymer rubber, uncured styrene/isoprene copolymer rubber, uncured styrene/isoprene/butadiene copolymer rubber, uncured acrylonitrile/butadiene copolymer rubber, uncured polyisoprene rubber, uncured natural rubber, or a similar uncured conjugated diene-type rubber, uncured chloroprene rubber, and uncured partially-hydrogenated diene-type rubber.
  • silica filler (B) and carbon black (D) are fillers that are used for reinforcing the rubber obtained after vulcanization.
  • a silica filler may comprise reinforcing silica such as fumed silica (dry-process silica) or precipitated silica (wet-process silica). These fillers may be hydrophobized by treating their surfaces with an organic silicon compound such as hexamethyldisilazane, dimethyldichlorosilane, trimethylchlorosilane, or octamethyltetracyclosiloxane.
  • Carbon black may comprise the one normally used for rubber reinforcement and may be represented, e.g., by furnace black, channel black, lamp black, thermal black, or acetylene black. Carbon black can be used in a pellet-type form or in the form of non-pelletized aggregated lumps.
  • Component (B) is contained in an amount of 5 to 150 parts by weight, preferably 10 to 100 parts by weight, and most preferably, 30 to 90 parts by weight per 100 parts by weight of component (A).
  • carbon black (D) When carbon black (D) is contained, it should be contained in an amount of 0.1 to 80 parts by weight and, preferably, 5 to 50 parts by weight per 100 parts by weight of component (A). However, the total weight of components (B) and (D) should not exceed 120 parts by weight per 100 weight of component (A). If the aforementioned filler is contained in amounts less than the recommended lower limit, the obtained rubber will not be sufficiently strong. If, on the other hand, the added amount exceeds the recommended range, this will create difficulties for mixing and kneading the fillers with component (A).
  • component (C) The bis(silatranylalkyl) polysulfide or the aforementioned mixtures containing this compound and obtained by the method of the present invention (hereinafter referred to as component (C)) is added to the rubber composition in an amount of 0.1 to 50 wt.%, preferably, 0.1 to 30 wt.% per weight of component (B), or in an amount of 0.1 to 50 wt.%, preferably, 0.1 to 30 wt.% per total weight of components (B) and (D).
  • Component (C) can be mixed with components (B) and (A) in the form of an alkyleneglycol or a polyalkyleneglycol solution. This improves dispersibility in components (A) and (B). Concentration of component (C) in the solution should be in the range of 30 to 95 wt.%.
  • component (C) can be pre-mixed with component (B) and then the mixture is added and mixed with component (A).
  • component (C) can be added to a mixture of components (A) and (B).
  • the rubber composition of the present invention may be combined with other conventional additives such as weight-increasing fillers, organic fibers, naphthene-type process oil or similar softeners, pigments, foaming agents, ultraviolet-ray absorbers, aging inhibitors, antioxidants, scorch inhibitors, waxes, etc.
  • additives such as weight-increasing fillers, organic fibers, naphthene-type process oil or similar softeners, pigments, foaming agents, ultraviolet-ray absorbers, aging inhibitors, antioxidants, scorch inhibitors, waxes, etc.
  • the rubber composition containing component (C) of the present invention can be produced by methods known in the art.
  • the components for the rubber composition can be uniformly mixed and kneaded in a Banbury mixer, two-axis roller, kneader-mixer, two-axis extruder, etc. During mixing, the rubber composition should have a temperature in the range of 120 to 18O 0 C.
  • Vulcanization agents such as sulfur, insoluble sulfur, sulfur compound, etc.
  • vulcanization-assisting agents and vulcanization accelerators can also be added.
  • the vulcanization assistants may comprise zinc oxide, stearic acid, etc.
  • the vulcanization accelerators may comprise mercaptobenzothiazol (MBT) 5 benzothiazyldisulfide (MBTS), N-tert-butyl-2- benzothiazolylsulfenamide (TBBS), N-cyclohexyl-2-benzothiazyl-sulfmamide (CBS), or similar thiazol-type accelerators. Because mixing may cause heating and premature vulcanization, mixing can be carried out with cooling.
  • MBT mercaptobenzothiazol
  • TBBS N-tert-butyl-2- benzothiazolylsulfenamide
  • CBS N-cyclohexyl-2-benzothiazyl-sulfmamide
  • the rubber composition that contains the vulcanization agent and if necessary other additives, is subjected to heating and molding in a mold. If necessary, after primary vulcanization, the vulcanizate can be subjected to a secondary vulcanization.
  • molded rubber products that can be obtained by vulcanizing the rubber composition that contains component (C) are tires such as automobile tires, aircraft tires, bicycle tires, etc., but the most preferable are passenger-car tires, truck tires, race-car tires, and aircraft tires.
  • Other molded rubber products may comprise rubber- coated rollers, packings, rubber tubes, rubber sheets, rubber-coated wires, etc.
  • a flask equipped with a stirrer, thermometer, and condenser was filled with 47.5 g (0.1 mole) of bis(triethoxysilylpropyl) disulfide, 29.8 g (0.2 mole) of triethanolamine, and . 0.34 g (0.001 mole) of a 20% ethanol solution of sodium ethylate.
  • the mixture was then stirred for 2 hours at 150°C while the pressure was reduced to 200 mmHg. After 2-hour stirring, the pressure was further reduced, the ethanol generated in the process was removed by distillation, and 50.1 g of the bis(silatranylpropyl) disulfide shown below were obtained with the yield of 99%.
  • a flask equipped with a stirrer, thermometer, and condenser was filled with 47.5 g (0.1 mole) of bis(triethoxysilylpropyl) disulfide, 14.9 g (0.1 mole) of triethanolamine, and 0.34 g (0.001 mole) of a 20% ethanol solution of sodium ethylate. The mixture was then stirred for 2 hours at 150°C while the pressure was reduced to 200 mmHg.
  • silatranyl groups constitute 50 mole % of the sum of silatranyl groups and triethoxysilyl groups.
  • EXAMPLE 3 A flask equipped with a stirrer, thermometer, and condenser was filled with 47.5 g (0.1 mole) of bis(triethoxysilylpropyl) disulfide, 7.5 g (0.05 mole) of triethanolamine, and 0.34 g (0.001 mole) of a 20% ethanol solution of sodium ethylate. The mixture was then stirred for 2 hours at 15O 0 C while the pressure was reduced to 200 mmHg.
  • silatranyl groups constitute 25 mole % of the sum of silatranyl groups and triethoxysilyl groups.
  • a flask equipped with a stirrer, thermometer, and condenser was filled with 53.9 g (0.1 mole) of bis(triethoxysilylpropyl) tetrasulfide, 29.8 g (0.2 mole) of triethanolamine, and 0.34 g (0.001 mole) of a 20% ethanol solution of sodium ethylate.
  • the mixture was then stirred for 2 hours at 150 0 C while the pressure was reduced to 200 mniHg. After 2-hour stirring, the pressure was further reduced, the ethanol generated in the process was removed by distillation, and 55.8 g of the bis(silatranylpropyl) tetrasulfide shown below were obtained with the yield of 98%.
  • Test Piece A 16O 0 C x 11 min.
  • Test Piece C 16O 0 C x 18 min.
  • Block Test Piece A 16O 0 C x 16 min.
  • Test Piece C 16O 0 C x 23 min.
  • Specimen angle-shaped without slitting (perpendicular to grain direction).
  • Measurement temperature O 0 C, 6O 0 C Dynamic strain: 0.1%
  • Tester Viscosity measuring instrument RSA-II, the product of Rheometrics Co.
  • the ratio of aforementioned tan ⁇ (O 0 C) to tan ⁇ (6O 0 C) is indicated as (0°C/60°C). The greater is the ratio, the better is the tire balance (wet skidding and low fuel consumption properties).
  • the method of the present invention for manufacturing a bis(silatranylalkyl) polysulfide is useful for manufacturing the bis(silatranylalkyl) polysulfide in a simple manner and with a high yield without generating hydrogen sulfide.
  • the method of the present invention for manufacturing a mixture of the bis(silatranylalkyl) polysulfide and a (silatranylalkyl)(trialkoxysilylalkyl) polysilfide is useful for manufacturing the mixture in a simple manner and with a high yield without generating hydrogen sulfide.
  • the method of the present invention for manufacturing a mixture of the bis(silatranylalkyl) polysulfide, a (silatranylalkyl)(trialkoxysilylalkyl) polysilfide, and bis(trialkoxysilylalkyl) polysulfide is useful for manufacturing the mixture in a simple manner and with a high yield without generating hydrogen sulfide.
  • the aforementioned mixture of the present invention is useful for adding to rubbers for improving properties.
  • the rubber composition containing the aforementioned mixture of the present invention is useful for manufacturing tires, specifically tire trades.

Landscapes

  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Compositions Of Macromolecular Compounds (AREA)

Abstract

A method for manufacturing a bis(silatranylalkyl) polysulfide by heating a bis(trialkoxysilylalkyl) polysulfide and triethanolamine in the presence of a catalytic quantity of an alkali-metal alcoholate, thus substituting all Si-bonded alkoxy groups of the bis(trialkoxysilylalkyl) polysulfide with a (OCH2CH2)3N group; a method for the preparation of a mixture of a bis(silatranylalkyl) polysulfide and a (silatranyalkyl) (trialkoxysilyl) disulfide or a mixture of a bis(silatranylalkyl) polysulfide, a (silatranylalkyl) (trialkoxysilyl) disulfide, and a bis(trialkoxysilylalkyl) polysulfide by heating a bis(trialkoxysilylalkyl) polysulfide and triethanolamine in the presence of a catalytic quantity of an alkali-metal alcoholate, thus substituting a part of Si-bonded alkoxy groups of the bis(trialkoxysilylalkyl) polysulfide with a (OCH2CH2)3N group; a mixture of a bis(silatranylalkyl) polysulfide and a (silatranylalkyl) (trialkoxysilyl) disulfide; a mixture of a bis(silatranylalkyl) polysulfide, a (silatranylalkyl) (trialkoxysilyl) disulfide, and a bis(trialkoxysilylalkyl) polysulfide; and a rubber composition containing the aforementioned mixture.

Description

DESCRIPTION
METHOD FOR MANUFACTURING A BIS(SILATRANYLALKYL) POLYSULFIDE, METHOD FOR MANUFACTURING A MIXTURE OF BIS(SILATRANYLALKYL) POLYSULFIDE ETC., A MIXTURE OF BIS(SILATRANYLALKYL) POLYSULFIDE ETC., AND RUBBER COMPOSITION
TECHNICAL FIELD
[0001] The present invention relates to a novel method for manufacturing a bis(silatranylalkyl) polysulfide; to a method for manufacturing a mixture of a bis(silatranylalkyl) polysulfide and a (silatranylalkyl) (trialkoxysilylalkyl) polysulfide; to a method for manufacturing a mixture of a bis(silatranylalkyl) polysulfide, a
(silatranylalkyl) (trialkoxysilylalkyl) polysulfide, and a bis(trialkoxysilylalkyl) polysulfide; to a mixture of a bis(silatranylalkyl) polysulfide and a (silatranylalkyl) (trialkoxysilylalkyl) polysulfide; to a mixture of a bis(silatranylalkyl) polysulfide, a
(silatranylalkyl) (trialkoxysilylalkyl) polysulfide, and a bis(trialkoxysilylalkyl) polysulfide; and to a rubber composition containing the aforementioned mixture.
BACKGROUND ART [0002] A bis(silatranylalkyl) polysulfide and a method for manufacturing thereof are known from the published literature (see Patent Literature 1 (Japanese Unexamined Patent Application Publication {hereinafter referred to as "Kokai"} S50- 108225, i.e., JP50- 108225 A), Patent Reference 2 (Kokai S60-33838, i.e., JP60-33838A), and Patent Reference 3 (Kokai 2001-31798, i.e., JP 2001-31798A)). Example 13 added to the specification of Patent Reference 2 after the publication of the application describes synthesis of a bis(silatranylpropyl) tetrasulfide by mixing 2 moles of a silatranylpropylmercaptane with 3 moles of a sulfur powder under heating conditions.
[0003] This synthesis develops hydrogen sulfide, which normally is in a gaseous state and is characterized by very high toxicity. Therefore, the aforementioned method is associated with such problems as the use of synthesis equipment that prevents leakage of the generated hydrogen sulfide into the environment and the necessity of constantly wearing an antitoxic mask.
[0004] Example 13 of Patent Reference 2 describes a synthesized bis(silatranylpropyl) tetrasulfide, which is a white crystalline substance having no melting point. SILATRAN (OS34=Si79), which is the same as the aforementioned bis(silatranylpropyl) tetrasulfide, were mixed with a natural rubber, active silicic acid, or the like, the mixture was vulcanized, and physical properties of the product were measured. However, since the bis(silatranylpropyl) tetrasulfide is a crystalline substance having no melting point, dispersion thereof in such substances as a natural rubber or synthetic rubber and a silica filler presents a problem, even when the mixture is kneaded with application of a shear force, e.g., in a two-roll mill.
SUMMARY OF THE INVENTION [0005] Based on a thorough study aimed at the solution of the above-described problems of the prior art, the inventors herein have found that if a bis(trialkoxysilylalkyl) polysulfide and a triethanolamine are heated in the presence of a specific catalyst with the resulting substitution of alkoxy groups with silatranyl group, then the by-product which is evolved in this process is merely an alcohol. The process is especially safe for the environment when alkoxy groups are represented by ethoxy groups, since in this case the developed by-product is ethanol which is an alcohol of high environmental safety.
The inventors also noticed that partial substitution of alkoxy groups of the bis(trialkoxysilylalkyl) polysulfide with silatranyl groups facilitates mixing with rubbers, silica fillers, and the like.
In view of the above, it is an object of the present invention to provide a new manufacturing method which does not use sulfur as a starting material, and does not generate toxic hydrogen sulfide during synthesis of the bis(silatranylalkyl) polysulfide. It is another object to provide an intermediate reaction mixture of a bis(trialkoxysilylalkyl) polysulfide and a bis(silatranylalkyl) polysulfide, as well as a method of the preparation of the aforementioned mixture. [0006] The present invention relates to a method for manufacturing a bis(silatranylalkyl) polysulfide represented by the general formula (3):
N(CH2CH2O)3 SiRSxRSi (OCH2CH2)3N (3)
(wherein R is an alkylene group having 1 to 10 carbon atoms, and "x" is a number from 2 to 8), to a mixture of a bis(silatranylalkyl) polysulfide represented by the general formula (3):
N(CH2CH2O)3 SiRSxRSi (OCH2CH2)3N (3)
(wherein R is an alkylene group having 1 to 10 carbon atoms and "x" is a number from 2 to 8) and a (silatranylalkyl) (trialkoxysilylalkyl) polysulfide represented by the general formula (4):
N(CH2CH2O)3 SiRSxRSi (ORJ)3 (4)
(wherein R and "x" are the same as defined above, and R1 is an alkyl group having 1 to 4 carbon atoms); to a mixture of a bis(silatranylalkyl) polysulfide represented by the general formula (3): N(CH2CH2O)3 SiRSxRSi (OCH2CH2)3N (3)
(wherein R is an alkylene group having 1 to 10 carbon atoms, and "x" is a number from 2 to 8), a (silatranylalkyl) (trialkoxysilylalkyl) polysulfide represented by the general formula (4):
N(CH2CH2O)3 SiRSxRSi (ORJ)3 (4) (wherein R and "x" are the same as defined above and R1 is an alkyl group having 1 to 4 carbon atoms), and a bis(trialkoxysilylalkyl) polysulfide represented by the general formula (1):
(R1O)3 SiRSxRSi (OR!)3 (1)
(wherein R, R1, and "x" are the same as defined above), by heating a bis(trialkoxysilylalkyl) polysulfide represented by the general formula (1):
(R1O)3 SiRSxRSi (OR^3 (1)
(wherein R and "x" are the same as defined above, and R1 is an alkyl group having 1 to 4 carbon atoms) and a triethanolamine represented by the formula (2):
(HOCH2CH2)3N (2) in the presence of an alkali metal alcoholate used in a catalytic quantity; and to a rubber composition containing the aforementioned mixture. BRIEF DESCRIPTION OF THE DRAWINGS
[0041]
Fig. 1 illustrates a 29Si-NMR chart for the bis(silatranylpropyl) disulfide synthesized in
EXAMPLE 1. Fig. 2 illustrates a 13C-NMR chart for the bis(silatranylpropyl) disulfide synthesized in
EXAMPLE l.
Fig. 3 illustrates a 29Si-NMR chart for the mixture of the bis(silatranylpropyl) disulfide,
(silatranylpropyl)(triethoxysilylpropyl) disulfide, and bis(triethoxysilylpropyl) disulfide synthesized in EXAMPLE 2. Fig. 4 illustrates a 13C-NMR chart for the mixture of the bis(silatranylpropyl) disulfide,
(silatranylpropyl)(triethoxysilylpropyl) disulfide, and bis(triethoxysilylpropyl) disulfide synthesized in EXAMPLE 2.
Fig. 5 illustrates a 29Si-NMR chart for the bis(silatranylpropyl) tetrasulfide synthesized in
EXAMPLE 4. Fig. 6 illustrates a 13C-NMR chart for the bis(silatranylpropyl) tetrasulfide synthesized in
EXAMPLE 4.
DISCLOSURE OF THE INVENTION
[0007] The present invention relate to the following; [1] A method for manufacturing a bis(silatranylalkyl) polysulfide represented by the general formula (3):
N(CH2CH2O)3 SiRSxRSi (OCH2CH2)3N (3)
(wherein R is an alkylene group having 1 to 10 carbon atoms, and "x" is a number from 2 to 8), the method being characterized by heating a bis(trialkoxysilylalkyl) polysulfide represented by the general formula (1):
(R1O)3 SiRSxRSi (OR^3 (1)
(wherein R and "x" are the same as defined above, and R1 is an alkyl group having 1 to 4 carbon atoms) and a triethanolamine represented by the formula (2):
(HOCH2CH2)3N (2) in the presence of an alkali metal alcoliolate used in a catalytic quantity, thus substituting all Si-bonded (OR!)3 groups of the bis(trialkoxysilylalkyl) polysulfide represented by the general formula (1) with a group represented by the formula: (OCH2CH2)3N. [2] A method for manufacturing a mixture of a bis(silatranylalkyl) polysulfide represented by the general formula (3):
N(CH2CH2O)3 SiRSxRSi (OCH2CH2)3N (3)
(wherein R is an alkylene group having 1 to 10 carbon atoms and "x" is a number from 2 to 8) and a (silatranylalkyl) (trialkoxysilylalkyl) polysulfide represented by the general formula (4):
N(CH2CH2O)3 SiRSxRSi (OR!)3 (4)
(wherein R and "x" are the same as defined above, and R1 is an alkyl group having 1 to 4 carbon atoms), the method being characterized by heating a bis(trialkoxysilylalkyl) polysulfide represented by the general formula (1):
(R1O)3 SiRSxRSi (OR^3 (1)
(wherein R, R1, and "x" are the same as defined above) and a triethanolamine represented by the formula (2):
(HOCH2CH2)3N (2) in the presence of an alkali metal alcoholate used in a catalytic quantity, thus substituting a part of Si-bonded (OR^3 groups of the bis(trialkoxysilylalkyl) polysulfide represented by the general formula (1) with a group represented by the formula: (OCH2CH2)3N.
[3] A method for manufacturing a mixture of a bis(silatranylalkyl) polysulfide represented by the general formula (3):
N(CH2CH2O)3 SiRSxRSi (OCH2CH2)3N (3)
(wherein R is an alkylene group having 1 to 10 carbon atoms, and "x" is a number from 2 to 8), a (silatranylalkyl) (trialkoxysilylalkyl) polysulfide represented by the general formula (4): N(CH2CH2O)3 SiRSxRSi (OR^3 (4)
(wherein R and "x" are the same as defined above and R1 is an alkyl group having 1 to 4 carbon atoms), and a bis(trialkoxysilylalkyl) polysulfide represented by the general formula (1):
(R1O)3 SiRSxRSi (OR^3 (1) (wherein R, R1, and "x" are the same as defined above), the method being characterized by heating a bis(trialkoxysilylalkyl) polysulfide represented by the general formula (1): (R1O)3 SiRSxRSi (OR^3 (1) (wherein R, R1, and "x" are the same as defined above) and a triethanolamine represented by the formula (2):
(HOCH2CH2)3N (2) in the presence of an alkali metal alcoholate used in a catalytic quantity, thus substituting a part of Si-bonded (OR!)3 groups of the bis(trialkoxysilylalkyl) polysulfide represented by the general formula (1) with a group represented by the formula: (OCH2CH2)3N.
[4] A mixture of a bis(silatranylalkyl) polysulfide represented by the general formula
(3): N(CH2CH2O)3 SiRSxRSi (OCH2CH2)3N (3)
(wherein R is an alkylene group having 1 to 10 carbon atoms, and "x" is a number from 2 to 8) and a (silatranylalkyl) (trialkoxysilylalkyl) polysulfide represented by the general formula (4):
N(CH2CH2O)3 SiRSxRSi (OR^3 (4) (wherein R and "x" are the same as defined above, and R1 is an alkyl group having 1 to 4 carbon atoms).
[5] A mixture of a bis(silatranylalkyl) polysulfide represented by the general formula
(3): N(CH2CH2O)3 SiRSxRSi (OCH2CH2)3N (3)
(wherein R is an alkylene group having 1 to 10 carbon atoms, and "x" is a number from
2 to 8), a (silatranylalkyl) (trialkoxysilylalkyl) polysulfide represented by the general formula (4):
N(CH2CH2O)3 SiRSxRSi (OR^3 (4) (wherein R and "x" are the same as defined above, and R1 is an alkyl group having 1 to 4 carbon atoms), and a bis(trialkoxysilylalkyl) polysulfide represented by the general formula (1):
(R1O)3 SiRSxRSi (OR1):, (1)
(wherein R, R1, and "x" are the same as defined above).
[6] A rubber composition comprising:
100 parts by weight of an uncured organic rubber (A), 5.0 to 150 parts by weight of a silica filler (B), and the mixture (C) claimed in [4] or [5] which is contained in an amount of 0.1 to 50 wt.% of the weight of component (B).
[7] A rubber composition comprising: 100 parts by weight of an uncured organic rubber (A),
5.0 to 150 parts by weight of silica filler (B),
0.1 to 80 parts by weight of carbon black (D), and the mixture (C) claimed in [4] or [5] which is contained in an amount of 0.1 to 50 wt.% of the total weight of components (B) and (D).
[0008] The method of the present invention for synthesis of the bis(silatranylalkyl) polysulfide is highly safe since it does not use sulfur as a starting material and does not generate toxic hydrogen sulfide in the synthesis process.
The method of the present invention for manufacturing a mixture of a bis(silatranylalkyl) polysulfide and a (silatranylalkyl) (trialkoxysilylalkyl) polysulfide is highly safe, since it does not use sulfur as a starting material and does not generate toxic hydrogen sulfide in the manufacturing process.
The method of the present invention for manufacturing of a mixture of a bis(silatranylalkyl) polysulfide, a (silatranylalkyl) (trialkoxysilylalkyl) polysulfide, and bis(trialkoxysilylalkyl) polysulfide, since it does not use sulfur as a starting material and does not generate toxic hydrogen sulfide in the manufacturing process.
The mixtures of the present invention are intermediate reaction products between the aforementioned bis(silatranylalkyl) polysulfide and bis(trialkoxysilylalkyl) polysulfide, which can be easily mixed with a rubber, a silica filler, and the like, since the mixtures are liquid at ambient temperature.
A vulcanizate of the rubber composition of the present invention has improved properties.
BEST MODE FOR CARRYING OUT THE INVENTION
[0009] The method of the present invention for manufacturing a bis(silatranylalkyl) polysulfide represented by the general formula (3):
N(CH2CH2O)3 SiRSxRSi (OCH2CH2)3N (3) (wherein R is an alkylene group having 1 to 10 carbon atoms, and "x" is a number from 2 to 8), the method being characterized is characterized by heating a bis(trialkoxysilylalkyl) polysulfide represented by the general formula (1):
(R1O)3 SiRSxRSi (OR^3 (1) (wherein R and "x" are the same as defined above, and R1 is an alkyl group having 1 to 4 carbon atoms) and a triethanolamine represented by the formula (2):
(HOCH2CH2)3N (2) in the presence of an alkali metal alcoholate used in a catalytic quantity, thus substituting a part of Si-bonded (OR^3 groups of the bis(trialkoxysilylalkyl) polysulfide represented by the general formula (1) with a groups represented by the formula: (OCH2CH2)3N.
[0010] In the bis(silatranylalkyl) polysulfide represented by the general formula (3):
N(CH2CH2O)3 SiRSxRSi (OCH2CH2)3N (3)
(wherein R is an alkylene group having 1 to 10 carbon atoms, and "x" is a number from 2 to 8), which is the target product of the manufacturing procedure, alkylene groups having 1 to 10 carbon atoms bond to sulfur atoms on both ends of the polysulfide that has 2 to 8 sulfur atoms, and silicon atoms of the silatranyl groups bond to carbon atoms on the terminals of the aforementioned alkylene groups.
In the above formula, R represents alkylene groups having 1 to 10 carbon atoms. These alkylene groups can be exemplified by ethylene, propylene, butylene, pentylene, hexylene, heptylene, and octylene groups. Normally, propylene to decylene groups have a linear molecular structure, but may also have a branched or cyclic structure. From the viewpoint of ease of production, it is advantageous to use propylene or butylene with a linear or branched molecular structure. From the viewpoint of ease of production, it is recommended to have 2 to 4 sulfur atoms.
[0011] The following are specific examples of the bis(silatranylalkyl) polysulfide: bis(silatranylethyl) disulfide, bis(silatranylethyl) tetrasulfide, bis(silatranylpropyl) disulfide, bis(silatranylpropyl) tetrasulfide, bis(silatranylbutyl) tetrasulfide, bis(silatranylpropyl) hexylsulfide, and bis(silatranylbutyl) hexylsulfide. [0012] The bis(trialkoxysilylalkyl) polysulfide represented by the general formula (1):
(R1O)3 SiRSxRSi (OR^3 (1)
(wherein R designates an alkylene group having 1 to 10 alkylene atoms, R1 is an alkyl group having 1 to 4 carbon atoms, and "x" is a number from 2 to 8) is a starting material used for the production. In the above formula, R1 is an alkyl group having 1 to 4 carbon atoms. Such an alkyl group can be exemplified by methyl, ethyl, propyl, and butyl groups. Normally, the propyl and butyl groups have a linear molecular structure but a branched structure is also possible. From the viewpoint of ease of substituted with silatranyl group the use of methyl groups and, especially, ethyl groups, is preferable.
The alkylene groups designated by R can be exemplified by ethylene, propylene, butylene, pentylene, hexylene, heptylene, and octylene groups. Normally, the groups from propylene to decylene have a liner molecular structure, but may also have a branched or cyclic structure as well. The propylene group and butylene group with the linear or branched molecular structure are preferable for ease of production.
[0013] The following are specific examples of the bis(trialkoxysilylalkyl) polysulfide represented by the general formula (1): bis(trimethoxysilylpropyl) disulfide, bis(trimethoxysilylbutyl) disulfide, bis(triethoxysilylpropyl) disulfide, bis(triethoxysilylbutyl) disulfide, bis(trimethoxysilylpropyl) tetrasulfide, bis(triethoxysilylpropyl) tetrasulfide, bis(tripropoxysilylpropyl) tetrasulfide, bis(trimethoxysilylbutyl) tetrasulfide, bis(trimethoxysilylbutyl) tetrasulfide, bis(tripropoxysilylbutyl) tetrasulfide, bis(trimethoxysilylpropyl) hexylsulfide, bis(triethoxysilylpropyl) hexylsulfide, and bis(trimethoxysilylbutyl) hexylsulfide.
[0014] The triethanolamine, which is a starting material for the product of the present invention and is represented by the formula (2):
(HOCH2CH2)3N (2)
, is reacted with the (R1O)3Si groups of the bis(trialkoxysilylalkyl) polysulfide represented by the general formula (I)5 whereby three moles OfR1OH groups are generated and silatranyl groups are formed. Since the bis(trialkoxysilylalkyl) polysulfide represented by the general formula (1) contains in one molecule two (R1O)3Si groups, at least two moles of the triethanolamine are required. In order to complete the substitution reaction, it is recommended to provide 2.0 to 2.4 moles of triethanolamine per 1 mole of the bis(trialkoxysilylalkyl) polysulfide represented by the general formula (1).
[[0015] Since mere heating of the bis(trialkoxysilylalkyl) polysulfide represented by the general formula (1) and triethanolamine is not sufficient for rapid substitution, the reaction should be carried out in the presence of an alkali metal alcoholate used in a catalytic quantity. The alkali metal alcoholate can be represented by sodium methoxide, sodium ethoxide, potassium methoxide, potassium ethoxide, or lithium ethoxide. It is recommended to use alkali metal alcoholate in the amount of 0.1 to 5.0 mole % per 1 mole of the bis(trialkoxysilylalkyl) polysulfide represented by the general formula (1). Since the alkali metal alcoholate is a solid, it is added to the bis(trialkoxysilylalkyl) polysulfide represented by the general formula (1) preferably in a form of an alcohol solution.
[0016] The reaction between the bis(trialkoxysilylalkyl) polysulfide represented by the general formula (1) and the triethanolamine can be carried out for about 30 min. to 4 hours under a reduced pressure and at a temperature in the range of 120 to 1800C. Upon completion of the reaction, the alcohol developed in the reaction is removed by distillation under heating and reduced-pressure conditions. If the product of the reaction contains residual triethanolamine that has been supplied to the reaction, it also can be removed together with the alcohol by distillation under heating and reduced-pressure conditions.
[0017] A mixture of the present invention is composed of a bis(silatranylalkyl) polysulfide represented by the general formula (3):
N(CH2CH2O)3 SiRSxRSi (OCH2CH2)3N (3)
(wherein R is an alkylene group having 1 to 10 carbon atoms, and "x" is a number from 2 to 8) and a (silatranylalkyl) (trialkoxysilylalkyl) polysulfide represented by the general formula (4):
N(CH2CH2O)3 SiRSx RSi (OR^3 (4)s (wherein R and "x" are the same as defined above, and R1 is an alkyl group having 1 to 4 carbon atoms).
[0018] Another mixture of the present invention is composed of a mixture of a bis(silatranylalkyl) polysulfide represented by the general formula (3):
N(CH2CH2O)3 SiRSxRSi (OCH2CH2)3N (3)
(wherein R is an alkylene group having 1 to 10 carbon atoms, and "x" is a number from 2 to 8), a (silatranylalkyl) (trialkoxysilylalkyl) polysulfide represented by the general formula (4): N(CH2CH2O)3 SiRSxRSi (OR^3 (4)
(wherein R and "x" are the same as defined above, and R1 is an alkyl group having 1 to 4 carbon atoms), and a bis(trialkoxysilylalkyl) polysulfide represented by the general formula (1):
(R1O)3 SiRSxRSi (OR^3 (1) (wherein R, R1, and "x" are the same as defined above).
[0019] The mixture composed of a bis(silatranylalkyl) polysulfide represented by the general formula (3):
N(CH2CH2O)3 SiRSxRSi (OCH2CH2)3N (3) (wherein R is an alkylene group having 1 to 10 carbon atoms, and "x" is a number from 2 to 8) and a (silatranylalkyl) (trialkoxysilylalkyl) polysulfide represented by the general formula (4):
N(CH2CH2O)3 SiRSxRSi (OR^3 (4)
(wherein R and "x" are the same as defined above, and R1 is an alkyl group having 1 to 4 carbon atoms) or the mixture composed of a bis(silatranylalkyl) polysulfide represented by the general formula (3):
N(CH2CH2O)3 SiRSxRSi (OCH2CH2)3N (3)
(wherein R is an alkylene group having 1 to 10 carbon atoms, and "x" is a number from 2 to 8), a (silatranylalkyl) (trialkoxysilylalkyl) polysulfide represented by the general formula (4):
N(CH2CH2O)3 SiRSxRSi (OR*)3 (4) (wherein R, R1, and "x" are the same as defined above), and a bis(trialkoxysilylalkyl) poly sulfide represented by the general formula (1):
(R1O)3 SiRSxRSi (OR^3 (1)
(wherein R, R1, and "x" are the same as defined above) can be produced when the bis(trialkoxysilylalkyl) polysulfide represented by the general formula (1) :
(R1O)3 SiRSxRSi (OR^3 (1)
(wherein the R, R1, and "x" are the same as defined above) and the triethanolamine represented by the formula (2):
(HOCH2CH2)3N are heated in the presence of an alkali metal alcoholate used in a catalytic quantity, whereby a part of the silicon-bonded (OR^3 groups of the bis(trialkoxysilylalkyl) polysulfide represented by the general formula (1) is substituted with a (OCH2CH2)3N group.
[0020] By providing less than 2.0 moles of the triethanolamine per 1 mole of the bis(trialkoxysilylalkyl) polysulfide represented by the general formula (1) in the aforementioned heating reaction, it becomes possible to substitute a part of silicon- bonded (ORJ)3 groups with a (OCH2CH2)3N group.
For example, when 1.75 moles of the triethanolamine per 1 mole of the bis(trialkoxysilylalkyl) polysulfide represented by the general formula (1) are provided to the reaction, it becomes possible to produce a mixture of almost equivalent quantities of the bis(silatranylalkyl) polysulfide represented by the general formula (3): N(CH2CH2O)3 SiRSxRSi (OCH2CH2)3N (3) (wherein R is an alkylene group having 1 to 10 carbon atoms, and "x" is a number from 2 to 8) and the (silatranylalkyl) (trialkoxysilylalkyl) polysulfide represented by the general formula (4):
N(CH2CH2O)3 SiRSxRSi (OR^3 (4)
(wherein and "x" are the same as defined above and R1 is an alkyl group having 1 to 4 carbon atoms).
In order to prevent the bis(trialkoxysilylalkyl) polysulfide represented by the general formula (1) from remaining in the reaction product, it is recommended to supply triethanolamine to the reaction in an amount of 1.75 moles or more but 2.0 moles or less per 1 mole of the bis(trialkoxysilylalkyl) polysulfide represented by the general formula
(I)-
[0021] For example, when the reaction is carried out by supplying to the reaction 1.0 mole of the triethanolamine per 1.0 mole of the bis(trialkoxysilylalkyl) polysulfide represented by the general formula (1), then the mixture of the bis(silatranylalkyl) polysulfide represented by the general formula (3):
N(CH2CH2O)3 SiRSxRSi (OCH2CH2)3N (3) (wherein R is an alkylene group having 1 to 10 carbon atoms, and "x" is a number from 2 to 8), the (silatranylalkyl) (trialkoxysilylalkyl) polysulfide represented by the general formula (4):
N(CH2CH2O)3 SiRSxRSi (OR*)3 (4)
(wherein R and "x" are the same as defined above, and R1 is an alkyl group having 1 to 4 carbon atoms), and the bis(trialkoxysilylalkyl) polysulfide represented by the general formula (1):
(R1O)3 SiRSxRSi (OR^3 (1)
(wherein R, R1, and "x" are the same as defined above) is obtained almost in a ratio of 1:2:1.
[0022] Appropriate rubber compositions to which the bis(silatranylalkyl) polysulfide or the aforementioned mixtures that have been produced by the method of the present invention are added may consist mainly of an uncured organic rubber (A) and a silica filler (B), or an uncured organic rubber (A), a silica filler (B), and a carbon black (D).
(A) An uncured organic rubber is usually referred to merely as "rubber". This component is an organic polymer that exhibits resiliency when vulcanized.
There are no special restrictions with regard to this uncured organic rubber, provided that it is suitable for manufacturing tires and especially tire treads. The appropriate uncured organic rubber comprises a highly unsaturated organic polymer compound, in particular, a diene-type polymer compound with an iodine number in the range of 20 to 450. The uncured organic rubber is exemplified by an uncured styrene/butadiene copolymer rubber, uncured polybutadiene rubber, uncured isoprene/butadiene copolymer rubber, uncured styrene/isoprene copolymer rubber, uncured styrene/isoprene/butadiene copolymer rubber, uncured acrylonitrile/butadiene copolymer rubber, uncured polyisoprene rubber, uncured natural rubber, or a similar uncured conjugated diene-type rubber, uncured chloroprene rubber, and uncured partially-hydrogenated diene-type rubber.
[0023] In the composition of the present invention, silica filler (B) and carbon black (D) are fillers that are used for reinforcing the rubber obtained after vulcanization. A silica filler may comprise reinforcing silica such as fumed silica (dry-process silica) or precipitated silica (wet-process silica). These fillers may be hydrophobized by treating their surfaces with an organic silicon compound such as hexamethyldisilazane, dimethyldichlorosilane, trimethylchlorosilane, or octamethyltetracyclosiloxane. Carbon black may comprise the one normally used for rubber reinforcement and may be represented, e.g., by furnace black, channel black, lamp black, thermal black, or acetylene black. Carbon black can be used in a pellet-type form or in the form of non-pelletized aggregated lumps.
Component (B) is contained in an amount of 5 to 150 parts by weight, preferably 10 to 100 parts by weight, and most preferably, 30 to 90 parts by weight per 100 parts by weight of component (A). When carbon black (D) is contained, it should be contained in an amount of 0.1 to 80 parts by weight and, preferably, 5 to 50 parts by weight per 100 parts by weight of component (A). However, the total weight of components (B) and (D) should not exceed 120 parts by weight per 100 weight of component (A). If the aforementioned filler is contained in amounts less than the recommended lower limit, the obtained rubber will not be sufficiently strong. If, on the other hand, the added amount exceeds the recommended range, this will create difficulties for mixing and kneading the fillers with component (A).
[0024] The bis(silatranylalkyl) polysulfide or the aforementioned mixtures containing this compound and obtained by the method of the present invention (hereinafter referred to as component (C)) is added to the rubber composition in an amount of 0.1 to 50 wt.%, preferably, 0.1 to 30 wt.% per weight of component (B), or in an amount of 0.1 to 50 wt.%, preferably, 0.1 to 30 wt.% per total weight of components (B) and (D).
Component (C) can be mixed with components (B) and (A) in the form of an alkyleneglycol or a polyalkyleneglycol solution. This improves dispersibility in components (A) and (B). Concentration of component (C) in the solution should be in the range of 30 to 95 wt.%.
Various methods can be used for mixing component (C) with other components. For example, component (C) can be pre-mixed with component (B) and then the mixture is added and mixed with component (A). Alternatively, component (C) can be added to a mixture of components (A) and (B).
[0025] If necessary, the rubber composition of the present invention may be combined with other conventional additives such as weight-increasing fillers, organic fibers, naphthene-type process oil or similar softeners, pigments, foaming agents, ultraviolet-ray absorbers, aging inhibitors, antioxidants, scorch inhibitors, waxes, etc. There are no special restrictions with regard to the amounts in which these additives can be added to the rubber composition, and the aforementioned amounts can be appropriately selected, provided that the additives in the selected amounts do not adversely affect tire performance.
[0026] The rubber composition containing component (C) of the present invention can be produced by methods known in the art. The components for the rubber composition can be uniformly mixed and kneaded in a Banbury mixer, two-axis roller, kneader-mixer, two-axis extruder, etc. During mixing, the rubber composition should have a temperature in the range of 120 to 18O0C.
[0027] Vulcanization agents such as sulfur, insoluble sulfur, sulfur compound, etc., can be added to the composition in a two-roll mill, two-axis extruder, etc., for vulcanization and formation of tires, and especially tire treads. If necessary, vulcanization-assisting agents and vulcanization accelerators can also be added. The vulcanization assistants may comprise zinc oxide, stearic acid, etc. The vulcanization accelerators may comprise mercaptobenzothiazol (MBT)5 benzothiazyldisulfide (MBTS), N-tert-butyl-2- benzothiazolylsulfenamide (TBBS), N-cyclohexyl-2-benzothiazyl-sulfmamide (CBS), or similar thiazol-type accelerators. Because mixing may cause heating and premature vulcanization, mixing can be carried out with cooling.
The rubber composition that contains the vulcanization agent and if necessary other additives, is subjected to heating and molding in a mold. If necessary, after primary vulcanization, the vulcanizate can be subjected to a secondary vulcanization.
[0028] An example of the molded rubber products that can be obtained by vulcanizing the rubber composition that contains component (C) are tires such as automobile tires, aircraft tires, bicycle tires, etc., but the most preferable are passenger-car tires, truck tires, race-car tires, and aircraft tires. Other molded rubber products may comprise rubber- coated rollers, packings, rubber tubes, rubber sheets, rubber-coated wires, etc.
EXAMPLES
[0029] The present invention is further described with reference to practical examples and comparative examples. In the EXAMPLES, 29Si-NMR measurements of the bis(silatranylpropyl) disulfide; a mixture of the bis(silatranylpropyl) disulfide, the (silatranylpropyl)(triethoxysilylpropyl) disulfide, and the bis(triethoxysilylpropyl) disulfide; and the bis(silatranylpropyl) tetrasulfide were carried out in heavy deuteriumchloroform by using a JEOL JNM-EX400 (product of JEOL.CO.JP) spectrometer and employing tetramethylsilane as an internal reference.
The presence of silatranyl groups in the bis(silatranylpropyl) disulfide, the aforementioned mixture, and bis(silatranylpropyl) tetrasulfide was detected in the same manner as above by observing peaks in 29Si-NMR and 13C-NMR charts. The amounts of the bis(silatranylpropyl) disulfide, the (silatranylpropyl)(triethoxysilylpropyl) disulfide, and bis(triethoxysilylpropyl) disulfide were determined by calculating ratios of the starting materials. Weights are given in terms of wt.%. "Et" designates ethyl groups. [0030] EXAMPLE 1
A flask equipped with a stirrer, thermometer, and condenser was filled with 47.5 g (0.1 mole) of bis(triethoxysilylpropyl) disulfide, 29.8 g (0.2 mole) of triethanolamine, and . 0.34 g (0.001 mole) of a 20% ethanol solution of sodium ethylate. The mixture was then stirred for 2 hours at 150°C while the pressure was reduced to 200 mmHg. After 2-hour stirring, the pressure was further reduced, the ethanol generated in the process was removed by distillation, and 50.1 g of the bis(silatranylpropyl) disulfide shown below were obtained with the yield of 99%.
Figure imgf000018_0001
[0031] EXAMPLE 2
A flask equipped with a stirrer, thermometer, and condenser was filled with 47.5 g (0.1 mole) of bis(triethoxysilylpropyl) disulfide, 14.9 g (0.1 mole) of triethanolamine, and 0.34 g (0.001 mole) of a 20% ethanol solution of sodium ethylate. The mixture was then stirred for 2 hours at 150°C while the pressure was reduced to 200 mmHg. After 2-hour stirring, the pressure was further reduced, the ethanol generated in the process was removed by distillation, and 48.0 g of a mixture of the bis(silatranylpropyl) disulfide, the (silatranylpropyl)(triethoxysilylpropyl) disulfide, and the bis(triethoxysilylpropyl) disulfide shown below were obtained with the yield of 99%.
Figure imgf000018_0002
(In the above formula, silatranyl groups constitute 50 mole % of the sum of silatranyl groups and triethoxysilyl groups.)
[0032] EXAMPLE 3 A flask equipped with a stirrer, thermometer, and condenser was filled with 47.5 g (0.1 mole) of bis(triethoxysilylpropyl) disulfide, 7.5 g (0.05 mole) of triethanolamine, and 0.34 g (0.001 mole) of a 20% ethanol solution of sodium ethylate. The mixture was then stirred for 2 hours at 15O0C while the pressure was reduced to 200 mmHg. After 2-hour stirring, the pressure was further reduced, the ethanol generated in the process was removed by distillation, and 47.8 g of a mixture of the bis(silatranylpropyl) disulfide, the (silatranylpropyl)(triethoxysilylpropyl) disulfide, and the bis(triethoxysilylpropyl) disulfide shown below were obtained with the yield of 99%.
Figure imgf000019_0001
(In the above formula, silatranyl groups constitute 25 mole % of the sum of silatranyl groups and triethoxysilyl groups.)
[0033] EXAMPLE 4
A flask equipped with a stirrer, thermometer, and condenser was filled with 53.9 g (0.1 mole) of bis(triethoxysilylpropyl) tetrasulfide, 29.8 g (0.2 mole) of triethanolamine, and 0.34 g (0.001 mole) of a 20% ethanol solution of sodium ethylate. The mixture was then stirred for 2 hours at 1500C while the pressure was reduced to 200 mniHg. After 2-hour stirring, the pressure was further reduced, the ethanol generated in the process was removed by distillation, and 55.8 g of the bis(silatranylpropyl) tetrasulfide shown below were obtained with the yield of 98%.
Figure imgf000019_0002
[0034] APPLICATION EXAMPLE 1 and REFERENTIAL APPLICATION EXAMPLE 1
A rubber composition for specimen B and a rubber composition for specimen C composed of components shown in Table 1 were prepared. Table 1
Figure imgf000020_0001
[0035]
A more detailed description of the aforementioned components is given below in Table 2.
Table 2
Figure imgf000021_0001
[0036] In the preparation of the rubber composition, mixing and kneading of the components were carried out in accordance with JIS K6299 "Preparation of Test Pieces for Testing Rubber"
Mixing and Kneading Conditions (One-step kneading in a tightly sealed kneader)
Test machine - Laboplast Mill - IOOC 100 type
Rotor: B600 (Banbury type, 600 cm3)
Rotor speed: 50 rpm Filling rate: 70% Set temperature: 12O0C Maximal temperature at the exit: 15O0C Duration of kneading: 4 min. (Two-stage kneading: roller-type kneading machine)
Roller dimensions: diameter. 8" x 18" Front roller speed: 20 rpm Front/rear roller speed ratio: 1:1.5
[0037] Each aforementioned composition was vulcanized under the following condition. Sheet
Test Piece A: 16O0C x 11 min. Test Piece C: 16O0C x 18 min. Block Test Piece A: 16O0C x 16 min.
Test Piece C: 16O0C x 23 min.
[0038] Characteristics of the rubber compositions for aforementioned test pieces and characteristics of the rubbers obtained by vulcanizing the rubber compositions were measured under conditions given below. The results of measurements are shown in Table 3. <Methods of Measuring Characteristics of Rubber Compositions and Rubbers>
1. Mooney Viscosity
This characteristic was measured in accordance with the provisions of JIS K6300 "Physical testing methods for unvulcanized rubber" Measurement temperature: 1000C Die vulcanization test-A method Oscillation amplitude:+l°5 oscillation frequency: 1.67 Hz
2. Elongation (%)
This characteristic was measured in according with the provisions of JIS K6251 "Method of testing tensile strength of vulcanized rubber". Specimen: JIS No. 3 for tensile test
3. Tear Strength (N/mm)
This characteristic was measured in according with the provisions of JIS K6252 "Method of testing tear strength of vulcanized rubber".
Specimen: angle-shaped without slitting (perpendicular to grain direction).
4. Hardness (Durometer hardness)
This characteristic was measured in according with the provisions of JIS K6253 "Method of testing hardness of vulcanized rubber and thermoplastic rubber".
5. Worn Volume (cm3)
This characteristic was measured by the Acron wear method test (A-2) in according with the provisions of JIS K6264 "Method of testing wear of vulcanized resin". Load: 44.1N (4.50 kgf)
Angle: 10°
Preliminary test: 500 revolutions
Basic test: 1000 revolutions
6. Tan δ
This characteristic was measured in according with the provisions of JIS K7244-4 "Method of testing dynamic characteristics of plastics - Part 4: Tensile vibrations —Non- resonant vibration method".
Measured items: dynamic storage modulus of elasticity E' dynamic loss modulus of elasticity E" tangent of loss tan δ
Sample dimensions: 1 mm x 5 mm x 30 mm Measurement mode: tensile mode Measurement frequency: 10 Hz Heating rate: 2°C/min
Measurement temperature: O0C, 6O0C Dynamic strain: 0.1% Tester: Viscosity measuring instrument RSA-II, the product of Rheometrics Co.
7. Characteristic Balance
The ratio of aforementioned tan δ (O0C) to tanδ (6O0C) is indicated as (0°C/60°C). The greater is the ratio, the better is the tire balance (wet skidding and low fuel consumption properties).
[0039] Measurement results of Test Piece "B" and Test Piece "C" are shown in Table 3.
Table 3
Figure imgf000024_0001
INDUSTRIAL APPLICABILITY
[0040] The method of the present invention for manufacturing a bis(silatranylalkyl) polysulfide is useful for manufacturing the bis(silatranylalkyl) polysulfide in a simple manner and with a high yield without generating hydrogen sulfide. The method of the present invention for manufacturing a mixture of the bis(silatranylalkyl) polysulfide and a (silatranylalkyl)(trialkoxysilylalkyl) polysilfide is useful for manufacturing the mixture in a simple manner and with a high yield without generating hydrogen sulfide.
The method of the present invention for manufacturing a mixture of the bis(silatranylalkyl) polysulfide, a (silatranylalkyl)(trialkoxysilylalkyl) polysilfide, and bis(trialkoxysilylalkyl) polysulfide is useful for manufacturing the mixture in a simple manner and with a high yield without generating hydrogen sulfide. The aforementioned mixture of the present invention is useful for adding to rubbers for improving properties.
The rubber composition containing the aforementioned mixture of the present invention is useful for manufacturing tires, specifically tire trades.

Claims

1. A method for manufacturing a bis(silatranylalkyl) polysulfide represented by the general formula (3): N(CH2CH2O)3 SiRSxRSi (OCH2CH2)3N (3)
(wherein R is an alkylene group having 1 to 10 carbon atoms, and "x" is a number from 2 to 8), the method being characterized by heating a bis(trialkoxysilylalkyl) polysulfide represented by the general formula (1):
(R1O)3 SiRSxRSi (OR^3 (1) (wherein R and "x" are the same as defined above, and R1 is an alkyl group having 1 to 4 carbon atoms and a triethanolamine represented by the formula (2):
(HOCH2CH2)3N (2) in the presence of an alkali metal alcoholate used in a catalytic quantity, thus substituting all Si-bonded (OR*)3 groups of the bis(trialkoxysilylalkyl) polysulfide represented by the general formula (1) with a group represented by the formula:
(OCH2CH2)3N.
2. A method for manufacturing a mixture of a bis(silatranylalkyl) polysulfide represented by the general formula (3): N(CH2CH2O)3 SiRSxRSi (OCH2CH2)3N (3)
(wherein R is an alkylene group having 1 to 10 carbon atoms and "x" is a number from 2 to 8) and a (silatranylalkyl) (trialkoxysilylalkyl) polysulfide represented by the general formula (4):
N(CH2CH2O)3 SiRSxRSi (OR^3 (4) (wherein R and "x" are the same as defined above, and R1 is an alkyl group having 1 to 4 carbon atoms, the method being characterized by heating a bis(trialkoxysilylalkyl) polysulfide represented by the general formula (1):
(R1O)3 SiRSxRSi (OR!)3 (1)
(wherein R, R1, and "x" are the same as defined above) and a triethanolamine represented by the formula (2) :
(HOCH2CH2)3N (2) in the presence of an alkali metal alcoholate used in a catalytic quantity, thus substituting a part of Si-bonded (OR*)3 groups of the bis(trialkoxysilylalkyl) polysulfide represented by the general formula (1) with a group represented by the formula: (OCH2CH2)3N.
3. A method for manufacturing a mixture of a bis(silatranylalkyl) polysulfide represented by the general formula (3):
N(CH2CH2O)3 SiRSxRSi (OCH2CH2)3N (3)
(wherein R is an alkylene group having 1 to 10 carbon atoms, and "x" is a number from 2 to 8), a (silatranylalkyl) (trialkoxysilylalkyl) polysulfide represented by the general formula (4): N(CH2CH2O)3 SiRSxRSi (OR^3 (4)
(wherein R and "x" are the same as defined above, and R1 is an alkyl group having 1 to 4 carbon atoms), and a bis(trialkoxysilylalkyl) polysulfide represented by the general formula (1):
(R1O)3 SiRSxRSi (OR^3 (1)
(wherein R, R1, and "x" are the same as defined above), the method being characterized by heating a bis(trialkoxysilylalkyl) polysulfide represented by the general formula (1): (R1O)3 SiRSxRSi (OR^3 (1)
(wherein R, R1, and "x" are the same as defined above) and a triethanolamine represented by the formula (2):
(HOCH2CH2)3N (2) in the presence of an alkali metal alcoholate used in a catalytic quantity, thus substituting a part of Si-bonded (0R!)3 groups of the bis(trialkoxysilylalkyl) polysulfide represented by the general formula (1) with a group represented by the formula: (OCH2CH2)3N.
4. A mixture of a bis(silatranylalkyl) polysulfide represented by the general formula (3):
N(CH2CH2O)3 SiRSxRSi (OCH2CH2)3N (3) (wherein R is an alkylene group having 1 to 10 carbon atoms, and "x" is a number from 2 to 8) and a (silatranylalkyl) (trialkoxysilylalkyl) polysulfide represented by the general formula (4):
N(CH2CH2O)3 SiRSxRSi (OR^3 (4) (wherein R and "x" are the same as defined above, and R1 is an alkyl group having
1 to 4 carbon atoms).
5. A mixture of a bis(silatranylalkyl) polysulfide represented by the general formula
(3): N(CH2CH2O)3 SiRSxRSi (OCH2CH2)3N (3)
(wherein R is an alkylene group having 1 to 10 carbon atoms, and "x" is a number from 2 to 8), a (silatranylalkyl) (trialkoxysilylalkyl) polysulfide represented by the general formula (4):
N(CH2CH2O)3 SiRSxRSi (ORJ)3 (4) (wherein R and "x" are the same as defined above, and R1 is an alkyl group having 1 to 4 carbon atoms), and a bis(trialkoxysilylalkyl) polysulfide represented by the general formula (1):
(R1O)3 SiRSxRSi (OR^3 (1)
(wherein R, R1, and "x" are the same as defined above).
6. A rubber composition comprising:
100 parts by weight of an uncured organic rubber (A),
5.0 to 150 parts by weight of a silica filler (B), and the mixture (C) claimed in claims 4 or 5 which is contained in an amount of 0.1 to 50 wt.% of the weight of component (B).
7. A rubber composition comprising:
100 parts by weight of an uncured organic rubber (A), 5.0 to 150 parts by weight of silica filler (B), 0.1 to 80 parts by weight of carbon black (D), and the mixture (C) claimed in claims 4 or 5 which is contained in an amount of 0.1 to 50 wt.% of the total weight of components (B) and (D).
PCT/JP2008/050659 2007-01-12 2008-01-11 Method for manufacturing a bis(silatranylalkyl) polysulfide, method for manufacturing a mixture of bis(silatranylalkyl) polysulfide etc., a mixture of bis(silatranylalkyl) polysulfide etc., and rubber composition Ceased WO2008084885A1 (en)

Priority Applications (3)

Application Number Priority Date Filing Date Title
US12/522,835 US8093323B2 (en) 2007-01-12 2008-01-11 Method for manufacturing a bis(silatranylalkyl) polysulfide, method for manufacturing a mixture of bis(silatranylalkyl) polysulfide etc., a mixture of bis(silatranylalkyl) polysulfide etc., and rubber composition
EP08703509A EP2104678A1 (en) 2007-01-12 2008-01-11 Method for manufacturing a bis(silatranylalkyl) polysulfide, method for manufacturing a mixture of bis(silatranylalkyl) polysulfide etc., a mixture of bis(silatranylalkyl) polysulfide etc., and rubber composition
CN2008800016407A CN101578291B (en) 2007-01-12 2008-01-11 Process for the preparation of bis(aziasilyltricyclylalkyl) polysulfides, process for the preparation of mixtures of bis(aziasilyltricyclylalkyl) polysulfides, bis(aziasilyltricyclylalkyl) polysulfides etc. mixtures, and rubber compositions

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
JP2007-004762 2007-01-12
JP2007004762A JP5193470B2 (en) 2007-01-12 2007-01-12 Method for producing bis (silatranylalkyl) polysulfide and the like, and mixture of bis (silatranylalkyl) polysulfide and the like

Publications (1)

Publication Number Publication Date
WO2008084885A1 true WO2008084885A1 (en) 2008-07-17

Family

ID=39267947

Family Applications (1)

Application Number Title Priority Date Filing Date
PCT/JP2008/050659 Ceased WO2008084885A1 (en) 2007-01-12 2008-01-11 Method for manufacturing a bis(silatranylalkyl) polysulfide, method for manufacturing a mixture of bis(silatranylalkyl) polysulfide etc., a mixture of bis(silatranylalkyl) polysulfide etc., and rubber composition

Country Status (6)

Country Link
US (1) US8093323B2 (en)
EP (1) EP2104678A1 (en)
JP (1) JP5193470B2 (en)
CN (1) CN101578291B (en)
TW (1) TW200835675A (en)
WO (1) WO2008084885A1 (en)

Cited By (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE102008054967A1 (en) 2008-12-19 2010-06-24 Evonik Degussa Gmbh Silatran-containing particles
EP2246355A4 (en) * 2008-02-22 2012-02-22 Bridgestone Corp Organic silicon compound, and rubber compositions, tires, primer compositions, paint compositions, and adhesives using same
CN102459288A (en) * 2009-05-20 2012-05-16 株式会社普利司通 Organosilicon compound, and rubber composition, tire, primer composition, coating composition, and adhesive using same
CN102574875A (en) * 2009-08-26 2012-07-11 株式会社普利司通 Process for production of silane coupling agents

Families Citing this family (16)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
ZA200711159B (en) * 2006-12-28 2009-03-25 Bridgestone Corp Amine-containing alkoxysilyl-functionalized polymers
JP5513013B2 (en) * 2009-05-20 2014-06-04 株式会社ブリヂストン Organosilicon compound, and rubber composition, tire, primer composition, coating composition and adhesive using the same
WO2010116712A1 (en) * 2009-04-06 2010-10-14 株式会社ブリヂストン Organosilicon compound, and rubber composition, tire, primer composition, coating composition and adhesive each using the organosilicon compound
WO2010116713A1 (en) * 2009-04-06 2010-10-14 株式会社ブリヂストン Organosilicon compound, and rubber composition, tire, primer composition, coating composition and adhesive each using the organosilicon compound
JP5513010B2 (en) * 2009-05-20 2014-06-04 株式会社ブリヂストン Organosilicon compound, and rubber composition, tire, primer composition, coating composition and adhesive using the same
WO2010134339A1 (en) * 2009-05-20 2010-11-25 株式会社ブリヂストン Process for production of silane coupling agent
WO2010134341A1 (en) * 2009-05-20 2010-11-25 株式会社ブリヂストン Organosilicon compound, and rubber composition, tire, primer composition, coating composition and adhesive agent each comprising same
JPWO2010134340A1 (en) * 2009-05-20 2012-11-08 株式会社ブリヂストン Method for producing silane coupling agent
TWI597286B (en) 2013-03-28 2017-09-01 國立中正大學 Mercaptoalkylsilatrane derivative having protecting group and method of manufacturing the same
JP6248597B2 (en) 2013-12-13 2017-12-20 信越化学工業株式会社 Sulfur-containing organosilicon compound and production method thereof, compounding agent for rubber, and rubber composition
JP6866348B2 (en) 2015-07-29 2021-04-28 株式会社ブリヂストン Methods for preparing functionalized polymers, related functionalized compounds, and their preparation
DE102015224436A1 (en) * 2015-12-07 2017-06-08 Evonik Degussa Gmbh rubber compounds
JP2017141351A (en) * 2016-02-10 2017-08-17 日立化成株式会社 Friction material composition, friction material and friction member using the friction material composition
WO2019199866A1 (en) * 2018-04-10 2019-10-17 Kraton Polymers Llc Tire compositions and methods for making thereof
US11680157B2 (en) 2018-04-10 2023-06-20 Kraton Corporation Tire compositions and methods for making thereof
KR102576576B1 (en) * 2018-12-27 2023-09-08 에스케이이노베이션 주식회사 Etching composition, method for etching insulating layer of semiconductor devices using the same and method for preparing semiconductor devices

Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4129585A (en) * 1977-03-24 1978-12-12 Deutsche Gold- Und Silber-Scheideanstalt Vormals Roessler Process for the production of sulfur containing organosilicon compounds
JP2001031798A (en) * 1999-06-26 2001-02-06 Bayer Ag Microgel-containing rubber compound containing sulfur- containing organosilicon compound
WO2007085521A1 (en) * 2006-01-28 2007-08-02 Evonik Degussa Gmbh Rubber mixtures

Family Cites Families (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
SU580840A3 (en) * 1974-02-07 1977-11-15 Дегусса (Фирма) Method of preparing sulfur-containing silicones
EP0819694B1 (en) * 1996-07-18 2002-10-02 Degussa AG Mixtures of organo-polysulfanes and process for the preparation of rubber mixtures containing them

Patent Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4129585A (en) * 1977-03-24 1978-12-12 Deutsche Gold- Und Silber-Scheideanstalt Vormals Roessler Process for the production of sulfur containing organosilicon compounds
JP2001031798A (en) * 1999-06-26 2001-02-06 Bayer Ag Microgel-containing rubber compound containing sulfur- containing organosilicon compound
US6399706B1 (en) * 1999-06-26 2002-06-04 Bayer Aktiengesellschaft Microgel-containing rubber compounds which comprise sulfur-containing organosilicon compounds
WO2007085521A1 (en) * 2006-01-28 2007-08-02 Evonik Degussa Gmbh Rubber mixtures

Cited By (13)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP2246355A4 (en) * 2008-02-22 2012-02-22 Bridgestone Corp Organic silicon compound, and rubber compositions, tires, primer compositions, paint compositions, and adhesives using same
US8183403B2 (en) 2008-02-22 2012-05-22 Bridgestone Corporation Organosilicon compound as well as rubber composition, tire, primer composition, paint composition and adhesive using the same
CN103756021A (en) * 2008-12-19 2014-04-30 赢创德固赛有限公司 Particle containing silatrane
CN101759891A (en) * 2008-12-19 2010-06-30 赢创德固赛有限责任公司 Particle containing silatrane
EP2206742A1 (en) * 2008-12-19 2010-07-14 Evonik Degussa GmbH Particle containing silatrane
DE102008054967A1 (en) 2008-12-19 2010-06-24 Evonik Degussa Gmbh Silatran-containing particles
US8716375B2 (en) 2009-05-20 2014-05-06 Bridgestone Corporation Organosilicon compound as well as rubber composition, tire primer composition, paint composition and adhesive using the same
CN102459288A (en) * 2009-05-20 2012-05-16 株式会社普利司通 Organosilicon compound, and rubber composition, tire, primer composition, coating composition, and adhesive using same
CN102459288B (en) * 2009-05-20 2014-09-03 株式会社普利司通 Silicone compound and rubber composition, tire, primer composition, coating composition and adhesive using same
EP2433945A4 (en) * 2009-05-20 2014-12-24 Bridgestone Corp Organosilicon compound, and rubber composition, tire, primer composition, coating composition and adhesive agent each utilizing same
EP2471798A4 (en) * 2009-08-26 2013-07-31 Bridgestone Corp PROCESS FOR PRODUCING SILANE COUPLING AGENTS
CN102574875A (en) * 2009-08-26 2012-07-11 株式会社普利司通 Process for production of silane coupling agents
US9150595B2 (en) 2009-08-26 2015-10-06 Bridgestone Corporation Process for producing silane coupling agent

Also Published As

Publication number Publication date
CN101578291A (en) 2009-11-11
US20100120950A1 (en) 2010-05-13
US8093323B2 (en) 2012-01-10
JP5193470B2 (en) 2013-05-08
CN101578291B (en) 2012-07-04
JP2008169157A (en) 2008-07-24
TW200835675A (en) 2008-09-01
EP2104678A1 (en) 2009-09-30

Similar Documents

Publication Publication Date Title
US8093323B2 (en) Method for manufacturing a bis(silatranylalkyl) polysulfide, method for manufacturing a mixture of bis(silatranylalkyl) polysulfide etc., a mixture of bis(silatranylalkyl) polysulfide etc., and rubber composition
EP2426169B1 (en) Pneumatic tire
US7531588B2 (en) Silane compositions, processes for their preparation and rubber compositions containing same
EP2681272B1 (en) Rubber composition containing blocked mercaptosilanes and articles made therefrom
EP2602262B1 (en) Organosilicon compound and method for preparing same, compounding agent for rubber, and rubber composition.
JP2012149189A (en) Rubber composition for tire and pneumatic tire
JP3445620B2 (en) Rubber composition and pneumatic tire using the same
JP6018001B2 (en) Rubber composition and pneumatic tire
JPWO1997048264A1 (en) Rubber composition and pneumatic tire using same
EP2125836B1 (en) Bisýtri(hydroxypolyalkyleneoxy)silylalkyl¨polysulfide, method of manufacturing bisýtri(hydroxypolyalkyleneoxy)silylalkyl¨polysulfide, tire rubber additive, and tire rubber composition
JP2008163125A (en) Rubber composition and pneumatic tire using the same
EP2883878B1 (en) Sulfur-containing organosilicon compound, making method, rubber compounding ingredient, and rubber composition
CA2223390A1 (en) Low-reversion cross-linking agents
JP6206152B2 (en) Sulfur-containing organosilicon compound and production method thereof, compounding agent for rubber, and rubber composition
JP6125323B2 (en) Rubber composition and pneumatic tire
JP6113583B2 (en) Method for producing rubber composition and pneumatic tire
JP2015205844A (en) Sulfur-containing organosilicon compound and production method thereof, rubber compounding agent, rubber composition, and tire
JP2012240927A (en) Organosilicon compound and method for producing the same, compounding agent for rubber, rubber composition, and tire

Legal Events

Date Code Title Description
WWE Wipo information: entry into national phase

Ref document number: 200880001640.7

Country of ref document: CN

121 Ep: the epo has been informed by wipo that ep was designated in this application

Ref document number: 08703509

Country of ref document: EP

Kind code of ref document: A1

WWE Wipo information: entry into national phase

Ref document number: 2366/KOLNP/2009

Country of ref document: IN

NENP Non-entry into the national phase

Ref country code: DE

REEP Request for entry into the european phase

Ref document number: 2008703509

Country of ref document: EP

WWE Wipo information: entry into national phase

Ref document number: 2008703509

Country of ref document: EP

WWE Wipo information: entry into national phase

Ref document number: 12522835

Country of ref document: US