WO2017046963A1 - シリカ配合用変性溶液重合ジエン系ゴムの製造法およびそのゴム組成物 - Google Patents
シリカ配合用変性溶液重合ジエン系ゴムの製造法およびそのゴム組成物 Download PDFInfo
- Publication number
- WO2017046963A1 WO2017046963A1 PCT/JP2015/076805 JP2015076805W WO2017046963A1 WO 2017046963 A1 WO2017046963 A1 WO 2017046963A1 JP 2015076805 W JP2015076805 W JP 2015076805W WO 2017046963 A1 WO2017046963 A1 WO 2017046963A1
- Authority
- WO
- WIPO (PCT)
- Prior art keywords
- compound
- diene rubber
- rubber
- modified solution
- polymerized
- Prior art date
Links
Classifications
-
- 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
- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/02—Elements
- C08K3/04—Carbon
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08C—TREATMENT OR CHEMICAL MODIFICATION OF RUBBERS
- C08C19/00—Chemical modification of rubber
- C08C19/25—Incorporating silicon atoms into the molecule
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08C—TREATMENT OR CHEMICAL MODIFICATION OF RUBBERS
- C08C2/00—Treatment of rubber solutions
- C08C2/06—Wining of rubber from solutions
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F2/00—Processes of polymerisation
- C08F2/04—Polymerisation in solution
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F236/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, at least one having two or more carbon-to-carbon double bonds
- C08F236/02—Copolymers of compounds having one or more unsaturated aliphatic radicals, at least one having two or more carbon-to-carbon double bonds the radical having only two carbon-to-carbon double bonds
- C08F236/04—Copolymers of compounds having one or more unsaturated aliphatic radicals, at least one having two or more carbon-to-carbon double bonds the radical having only two carbon-to-carbon double bonds conjugated
- C08F236/10—Copolymers of compounds having one or more unsaturated aliphatic radicals, at least one having two or more carbon-to-carbon double bonds the radical having only two carbon-to-carbon double bonds conjugated with vinyl-aromatic monomers
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F4/00—Polymerisation catalysts
- C08F4/42—Metals; Metal hydrides; Metallo-organic compounds; Use thereof as catalyst precursors
- C08F4/44—Metals; Metal hydrides; Metallo-organic compounds; Use thereof as catalyst precursors selected from light metals, zinc, cadmium, mercury, copper, silver, gold, boron, gallium, indium, thallium, rare earths or actinides
- C08F4/46—Metals; Metal hydrides; Metallo-organic compounds; Use thereof as catalyst precursors selected from light metals, zinc, cadmium, mercury, copper, silver, gold, boron, gallium, indium, thallium, rare earths or actinides selected from alkali metals
- C08F4/48—Metals; Metal hydrides; Metallo-organic compounds; Use thereof as catalyst precursors selected from light metals, zinc, cadmium, mercury, copper, silver, gold, boron, gallium, indium, thallium, rare earths or actinides selected from alkali metals selected from lithium, rubidium, caesium or francium
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F8/00—Chemical modification by after-treatment
- C08F8/12—Hydrolysis
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F8/00—Chemical modification by after-treatment
- C08F8/42—Introducing metal atoms or metal-containing groups
-
- 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
- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/34—Silicon-containing compounds
- C08K3/36—Silica
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L15/00—Compositions of rubber derivatives
Definitions
- the present invention relates to a method for producing a terminal-modified solution-polymerized diene rubber for blending with silica having physical properties such as storage stability and excellent impact resilience, and a rubber composition.
- the terminal-modified solution-polymerized diene rubber obtained by this production method has high strength and impact resilience, and when used for a tire rubber, it is optimal for an automobile tire having good processability and excellent fuel efficiency.
- Silica-containing rubber compositions are effective for low fuel consumption tires.
- a solution-polymerized diene rubber modified with an alkoxysilane compound that efficiently disperses silica is effective in improving the resilience or viscoelasticity test tan ⁇ , which is a laboratory indicator of low fuel consumption.
- the Si-OR group contained in this modified solution polymerized diene rubber is hydrolyzed with moisture such as in the air and further causes a condensation reaction, increasing the molecular weight during storage, and silica essential for improving physical properties. There has been a problem in that the reactivity of the is lowered.
- the functional group at one end that does not contain an alkoxysilyl group has a relatively low interaction between silica and rubber when kneaded, and is considered to have an excellent structure that is easily crosslinked with silica or other molecules during the vulcanization reaction.
- many problems still remain in the process of producing a silica-modified modified solution-polymerized diene rubber with stable quality and good industrial productivity.
- Patent Document 1 and Patent Document 2 the inventors made a reaction by reacting an alkoxysilane compound having a large steric hindrance that hardly causes hydrolysis after polymerization of styrene and butadiene using alkyllithium as a polymerization initiator.
- a method for producing a modified solution polymerized diene rubber for blending silica having an alkoxysilyl group was disclosed, and industrial production was started.
- alkoxysilane compounds do not have polar groups containing N atoms and the like, and diene rubbers modified with this compound have a slightly low reactivity with silica.
- Patent Document 3 discloses a modified SBR produced by reacting an aminoalkoxysilane compound after polymerizing styrene and butadiene using alkyllithium as a polymerization initiator, and discloses the evaluation result of blending with carbon black alone.
- Patent Document 4 discloses SBR for silica blending with good storage stability by reacting an aminoalkoxysilane compound similar to Patent Document 3 at a specific ratio after polymerization of styrene and butadiene using alkyllithium as a polymerization initiator. Is disclosed.
- Patent Document 5 discloses a property evaluation result only by blending carbon black by synthesizing coupling SBR by adding tin tetrachloride after polymerizing styrene and butadiene using lithium morpholinide as a polymerization initiator. ing.
- Patent Document 6 the inventors do not mix with silica, but alkyllithium containing an amino group or the like is used as a polymerization initiator, and after block copolymerization of styrene and butadiene, an aminoalkoxysilane compound is reacted, and a butadiene moiety A process for producing a hydrogenated polymer is disclosed.
- Patent Document 7 and Patent Document 8 physical property evaluation results of a silica compound of a polymer obtained by reacting an aminoalkoxysilane compound after polymerization of styrene and butadiene as a post-reaction initiator by adding a small amount of monomer to aminoalkyl lithium Is disclosed.
- the polymerization initiator has a special structure, and the synthesis is industrially complicated and difficult to produce stably.
- Patent Document 9 after polymerization of styrene and butadiene using alkyllithium as a polymerization initiator and before reaction with an aminoalkoxysilane compound, coupling was performed with an equivalent tin halide compound equivalent to half of the alkyllithium used. SBR for blending carbon black is disclosed.
- SBR for blending carbon black
- Silica-blended tires have improved fuel efficiency compared to carbon black-blown tires, but alkoxysilane-modified solution polymerized diene rubbers suitable for silica blends have a problem of changing Mooney viscosity (MV) during storage, In addition, there is an increasing demand for further improvement in fuel efficiency.
- MV Mooney viscosity
- Japanese Patent Publication No. 6-51746 Japanese Examined Patent Publication No. 7-68307 Japanese Patent Publication No. 6-53768 JP 2013-53293 A Japanese Examined Patent Publication No.59-38209 Japanese Patent No. 3988495 Japanese Patent No. 4289111 Japanese Patent No. 4655706 Japanese Patent No. 2625876
- the problem to be solved by the present invention is an end-modified solution polymerized diene rubber having excellent rebound resilience, good steam removal, excellent storage stability and processability during compounding, and It is to provide the rubber composition.
- the inventors of the present invention have a fast initial vulcanization rate in the presence of an organic lithium compound or a secondary amine compound as appropriate. After polymerizing the monomer in a small amount, the other conjugated diene compound and aromatic vinyl compound are subsequently polymerized in hydrocarbon, and after completion of the polymerization, a specific tin compound and a specific silane compound are added in order to determine the coupling efficiency. After controlling at a ratio, by adding a metal halide compound under specific conditions in the absence of active diene rubber, and then increasing the coupling efficiency by steam coagulation, the productivity is stable and the storage stability is improved. In addition, the present inventors have developed a method for producing a modified solution polymerization diene rubber excellent in the present invention and completed the present invention.
- the present invention relates to the following. [1] i) Initiating polymerization of a conjugated diene compound and an aromatic vinyl compound in a hydrocarbon in the presence of an organolithium compound or a secondary amine compound, ii) After completion of the polymerization, a tin compound represented by the formula (1) is added, and the diene rubber is treated so that the content of three or more branches is 5 to 30%.
- a silane compound represented by the formula (2) is added and treated so that the bi-branched component of the diene rubber is 30% or less, iv)
- the obtained polymer composition is steam-coagulated and dried, and the components having two or more branches are increased by 10 to 50% with respect to the state before steam coagulation, and the Mooney viscosity (a ) Is further heat-stabilized to such an extent that the Mooney viscosity (b) fluctuates by not more than 10 when heat-treated for 20 minutes in a subsequent roll mill at 130 ° C., a method for producing a modified solution-polymerized diene rubber.
- R 1 is an alkyl group having 1 to 12 carbon atoms, an aromatic group or an allyl group
- X is a halogen compound of iodine, bromine or chlorine
- n is an integer, 0 or 1 It is.
- R 2 is an alkyl group or aromatic group having 1 to 12 carbon atoms, an allyl group, or an alkyl group, aromatic group or allyl group containing a nitrogen atom in these functional groups
- R 3 is a carbon atom.
- L is the number of moles of the organolithium compound added at the start of polymerization
- A is the number of moles of the tin compound of the formula (1) added
- B is the metal halide compound shown by the added formula (3)
- N and p are integers represented by formula (1) and formula (3), respectively.
- the first invention of the present invention is: i) polymerization of a conjugated diene compound and an aromatic vinyl compound in a hydrocarbon in the presence of an organic lithium compound or a secondary amine compound, ii) After completion of the polymerization, a tin compound represented by the formula (1) is added, and the diene rubber is treated so that the content of three or more branches is 5 to 30%.
- a silane compound represented by the formula (2) is added and treated so that the bi-branched component of the diene rubber is 30% or less, iv)
- the obtained polymer composition is steam-coagulated and dried, and the components having two or more branches are increased by 10 to 50% with respect to the state before steam coagulation, and the Mooney viscosity (a ) Is further heat-stabilized to such an extent that the Mooney viscosity (b) fluctuates by not more than 10 when heat-treated for 20 minutes in a subsequent roll mill at 130 ° C., a method for producing a modified solution-polymerized diene rubber.
- R 1 is an alkyl group having 1 to 12 carbon atoms, an aromatic group or an allyl group
- X is a halogen compound of iodine, bromine or chlorine
- n is an integer, 0 or 1 It is.
- R 2 is an alkyl group or aromatic group having 1 to 12 carbon atoms, an allyl group, or an alkyl group, aromatic group or allyl group containing a nitrogen atom in these functional groups
- R 3 is a carbon atom.
- the second invention of the present invention relates to several more optimal methods for producing the modified solution polymerized diene rubber.
- the metal halide compound represented by the formula (3) in an amount satisfying the formula (4) is added, and then the iv) the steam coagulation / drying in the step A method for producing a solution-polymerized diene rubber.
- M is a tin atom or a silicon atom
- R 4 is an alkyl group having 1 to 12 carbon atoms, an aromatic group, an allyl group, or a carboxyl group
- X is any one of iodine, bromine, and chlorine Halogen compound
- p is an integer and is 0 or 1.
- the third invention of the present invention relates to a rubber composition for silica compounding containing the above modified solution polymerized diene rubber in a total rubber component of 20 phr or more.
- the present invention relates to a process for producing a modified solution polymerized diene rubber for compounding silica having excellent solvent removal, excellent storage stability, good workability, and excellent physical properties such as strength and impact resilience, and its rubber composition. It is about.
- Examples of the conjugated diene compound used in the present invention include 1,3-butadiene, isoprene, 1,3-pentadiene (piperine), 2,3-dimethyl-1,3-butadiene, 1,3-hexadiene, and the like. Can do. Among these, 1,3-butadiene and isoprene are preferable from the viewpoint of easy availability and physical properties of the resulting modified solution polymerization diene rubber. In particular, 1,3-butadiene is preferred.
- the amount of the conjugated diene compound used is usually 40 to 100% by weight, preferably 50 to 95% by weight, based on all monomers. If it is less than 40% by weight, the hysteresis loss increases.
- aromatic vinyl compound used in the present invention examples include styrene, ⁇ -methylstyrene, vinyltoluene, vinylnaphthalene, divinylbenzene, trivinylbenzene, and divinylnaphthalene.
- styrene is preferable from the viewpoint of availability and physical properties of the resulting modified solution polymerization diene rubber.
- the amount of the aromatic vinyl compound used is usually 60% by weight or less, preferably 50 to 5% by weight based on all monomers.
- the organic lithium compound used in the present invention is a lithium compound having 2 to 20 carbon atoms.
- N-butyllithium, sec-butyllithium, and tert-butyllithium are preferable from the viewpoint of industrial availability and stability, and n-butyllithium and sec-butyllithium are particularly preferable.
- the secondary amine compound used in the present invention is a compound represented by formula (5) or formula (6).
- R 5 and R 6 are an alkyl group, cycloalkyl group or aralkyl group having 1 to 20 carbon atoms, R 5 and R 6 may be the same or different, and R 7 is 3 to A divalent alkylene, bicycloalkane, oxy- or amino-alkylene group having 12 methylene groups.
- R 5 and R 6 in the formula (5) include methyl, ethyl, butyl, hexyl, octyl, cyclohexyl, 3-phenyl-1-propyl, isobutyl and the like. Specific examples include methylethylamine, diethylamine, dibutylamine, ethylbutylamine, dihexylamine, dioctylamine, butyloctylamine, octylcyclohexylamine, diisobutylamine, butyl (3-phenyl-1-propyl) amine and the like. Preferred are dioctylamine and dihexylamine, which have good industrial availability and solubility in hydrocarbon solvents.
- R 7 groups of formula (6) include, for example, trimethylene, tetramethylene, hexamethylene, oxydiethylene, N-alkylazadiethylene and the like. Specific examples include pyrrolidine, piperidine, hexamethyleneimine or heptamethyleneimine. Moreover, bicyclic bodies such as decahydroisoquinoline and perhydroindole may be used. Particularly preferred are pyrrolidine, piperidine, hexamethyleneimine or heptamethyleneimine.
- Examples of the compound that is prepolymerized in the coexistence of the organolithium compound and the secondary amine compound include compounds having a vulcanization rate higher than that of butadiene. Specifically, isoprene, 1,3-pentadiene (piperine), 2,3- Dimethyl-1,3-butadiene. Isoprene is preferred from the standpoint of industrial availability and vulcanization speed.
- Specific examples of the tin compound represented by the formula (1) include the following compounds.
- silane compound represented by the formula (2) include the following compounds.
- ketoxime silanes and trimethoxylanes preferred are ketoxime silanes and trimethoxylanes, triethoxysilanes, tripropoxysilanes, or modified solution polymerized diene rubbers which are relatively easily hydrolyzed while increasing the storage stability.
- ketoxime silanes and trimethoxylanes preferred are ketoxime silanes and trimethoxylanes, triethoxysilanes, tripropoxysilanes, or modified solution polymerized diene rubbers which are relatively easily hydrolyzed while increasing the storage stability.
- aminoethoxysilanes that are presumed to promote reactivity with silica.
- aminoalkoxysilane compounds are shown below. Dimethylaminomethyltrimethoxysilane, 2-dimethylaminoethyltrimethoxysilane, 3-dimethylaminopropyltrimethoxysilane, 4-dimethylaminobutyltrimethoxysilane, dimethylaminomethyldimethoxymethylsilane, 2-dimethylaminoethyldimethoxymethylsilane, 3-dimethylaminopropyldimethoxymethylsilane, 4-dimethylaminobutyldimethoxymethylsilane, dimethylaminomethyltriethoxysilane, 2-dimethylaminoethyltriethoxysilane, 3-dimethylaminopropyltriethoxysilane, 3-diethylaminopropyltrimethoxysilane 4-dimethylaminobutyltriethoxysilane, dimethylaminomethyldiethoxymethylsi
- alkoxysilane compounds having protecting groups that become primary amino groups after hydrolysis include N, N-bis (trimethylsilyl) -3-aminopropyltrimethoxysilane, N, N-bis (trimethylsilyl) -3-aminopropyltrimethyl.
- the metal halide compound represented by the formula (3) include the following compounds.
- tin tetrachloride, ethyl tin trichloride, propyl tin trichloride, butyl tin chloride, octyl tin chloride, cyclohexyl tin chloride, tin tetrabromide, ethyl triodor which are tin compounds represented by the formula (1) Tin iodide, propyl tin tribromide, butyl tin bromide, octyl tin tribromide, cyclohexyl tin tribromide, tin tetraiodide, tin triiodide iodide, tin propyl triiodide, tin butyl triiodide, Mention may be made of octyl tin triiodide and cyclohexyl
- Silicon compounds such as silicon tetrachloride, methyl silicon trichloride, ethyl silicon trichloride, propyl silicon trichloride, butyl silicon trichloride, octyl silicon trichloride, cyclohexyl silicon trichloride, silicon tetrabromide, methyl silicon tribromide, ethyl Silicon tribromide, propyl silicon tribromide, butyl silicon tribromide, octyl silicon tribromide, cyclohexyl silicon tribromide, silicon tetraiodide, silicon triiodide, propyl silicon triiodide, butyl triiodide Examples include silicon, octyl silicon triiodide, and cyclohexyl silicon triiodide.
- silicon tetrachloride preferred are silicon tetrachloride, methyl silicon trichloride, ethyl silicon trichloride, tin tetrachloride, and octyl tin trichloride. Particularly preferred are silicon tetrachloride and methyl silicon trichloride.
- the usage conditions such as the amount of raw material used to produce the solution-polymerized diene rubber, the reaction temperature, and the reaction time are as follows.
- a solution polymerization reaction of a diene rubber is performed by a commonly used method.
- a conjugated diene compound or an aromatic vinyl compound is heated at 10 to 120 ° C. in the presence of an organic lithium compound and a polar compound such as an ether compound or an amine compound.
- Polymerization is carried out at a temperature of several tens of minutes to several hours.
- the amount of the organic lithium compound used is usually in the range of 0.1 to 10 mmol per 100 g of diene rubber. If the molecular weight is less than 0.1 mmol, the molecular weight becomes too high and the solution viscosity increases and the MV viscosity becomes high, which causes problems in rubber production processes and tire manufacturing processes. On the other hand, if it exceeds 10 mmol, the molecular weight of the diene rubber becomes too low, and the vulcanized physical properties are greatly lowered.
- ether compounds for adjusting the microstructure of the diene monomer portion of the diene rubber particularly vinyl content
- amine compounds include triethylamine, pyridine, N, N, N ′, N′-tetramethylethylenediamine, dipiperidinoethane, methyl ether of N, N-diethylethanolamine, ethyl ether of N, N-diethylethanolamine, Tertiary amine compounds such as N, N-diethylethanolamine butyl ether are used.
- Preferred compounds include tetrahydrofuran (THF) and 2,2-di (2-tetrahydrofuryl) propane (DTHP) in view of polymerization rate and modification efficiency.
- the amount of these compounds to be added is usually 0.01 to 10 mol, preferably 0.2 to 5 mol, relative to 1 mol of the organic lithium compound when a plurality of N atoms, O atoms, etc. are contained.
- a compound having one O atom in the molecule such as tetrahydrofuran is preferably added in an amount of 0.05 to 10% based on the solvent.
- hydrocarbon solvent Suitable hydrocarbon solvents are selected from aliphatic hydrocarbons, aromatic hydrocarbons and alicyclic hydrocarbons, especially propane, n-butane, iso-butane, n-pentane having 3 to 12 carbon atoms, iso-pentane, n-hexane, cyclohexane, n-heptane, propene, 1-butene, iso-butene, trans-2-butene, cis-2-butene, 1-pentene, 2-pentene, 1-hexene, 2- Hexene, benzene, toluene, xylene, ethylbenzene and the like.
- Preferred are n-pentane, iso-pentane, n-hexane, cyclohexane and n-heptane. These solvents can be used as a mixture of two or more.
- a conjugated diene compound or a conjugated diene compound and an aromatic vinyl compound are anionically polymerized, and the active diene rubber is coupled with a tin compound and then reacted with a silane compound.
- These modification reactions are usually 0 to 120 ° C., preferably 50 to 100 ° C., and the reaction time is 1 to 30 minutes, preferably 5 to 20 minutes.
- the polymerization mode used in the present invention can be either a batch polymerization method or a continuous polymerization method.
- the batch polymerization method is suitable for the modified solution polymerized diene rubber characterized by rebound resilience
- the continuous polymerization method is suitable for the modified solution polymerized diene rubber characterized by wear resistance and processability.
- the tin compound represented by the formula (1) is added to the active diene rubber before modification to first produce a diene rubber coupled with a tri- or higher functional tin compound.
- the proportion of three or more branches of the diene rubber is preferably 5 to 30%. If it is less than 5%, the reactivity with carbon black usually used in combination with silica is lowered, and crumbs (a mass of undried rubber of several mm to several centimeters) are fused to each other in the steam demelting and drying process. It becomes difficult to dry. If it exceeds 30%, the component that reacts with silica decreases, and the rubber vulcanized physical properties of silica compound are lowered.
- a more preferable ratio of the three-branched component of the diene rubber is 10 to 25%.
- tin tetrachloride it is 0.0125 to 0.075 mol equivalent based on the active diene rubber. More preferably, it is 0.0125 to 0.05 mol equivalent.
- the ratio of these branched structures can be measured by GPC.
- a silane compound represented by the formula (2) is added to produce a diene rubber so that the bifurcated structure is 30% or less.
- the amount of the silane compound added is preferably an amount corresponding to 0.8 to 2 times the number of molecules per active diene rubber remaining in step ii), more preferably 1.0 to 1. 5 times.
- it is less than 0.8, the number of alkoxysilyl groups introduced into the active diene rubber is reduced and the reactivity with silica is lowered. If it is twice or more, the storage stability is deteriorated.
- the modified solution polymerized diene rubber having a structure in which one molecule of silane compound is bonded to the diene rubber is very unstable and causes a problem that the Mooney viscosity increases during storage. Therefore, in order to convert into a structure that is stable during storage and reacts with silica when blended with rubber, drying is performed so that the components of two or more branches after steam coagulation increase by 10 to 50%.
- the branched structure after steam coagulation / drying is the following two-branched structure-A, which is stable when storing rubber and is highly reactive with silica when compounded with silica. ing.
- the bifurcated structure-A is formed by condensation of (Rubber) -Si-OH in which (Rubber) -Si-OR modified with the silane compound of formula (2) is hydrolyzed.
- the reactivity with silica is low. Therefore, it is preferable to increase the proportion of the bifurcated structure-A, and this proportion is preferably 10 to 50%.
- Bifurcated structure A structure of the present invention: (Rubber) -Si-O-Si- (Rubber)
- Bifurcated structure B conventional structure: (Rubber) -Si- (Rubber)
- the proportion of these branched structures is determined by GPC in the manufacturing process.
- the formula (2) is followed by the step iii).
- the silane compound shown is reacted with the active diene rubber under the conditions where the number of components of the bifurcated structure is as small as possible.
- the metal halide compound shown by the formula (3) is added before the steam coagulation / drying in the step iv. You may do it.
- This metal halide compound is added under conditions satisfying the formula (4), and is deactivated by impurities contained in the solvent or monomer, or neutralizes the lithium compound by-produced by the reaction between the active diene rubber and the silane compound. Because.
- the addition amount of the metal halide compound is preferably L- (4-n) A ⁇ (4-p) B ⁇ 2L. More preferably, L ⁇ (4-n) A ⁇ (4-p) B ⁇ 1.5L.
- L- (4-n) A> (4-p) B the neutralization is insufficient and the workability at the time of steam coagulation of the modified solution polymerized diene rubber and the storage stability are deteriorated.
- (4-p) B> 2L the acidity of the rubber becomes too strong and the storage stability deteriorates, causing problems such as metal corrosion.
- the weight average molecular weight of the modified solution polymerization diene rubber obtained in the present invention is 100,000 to 1,000,000, preferably 150,000 to 700,000 in terms of polystyrene. If it is less than 100,000, the strength, abrasion resistance, impact resilience, etc. of the resulting rubber composition are not sufficient, while if it exceeds 1,000,000, the processability is inferior, and the filler dispersibility during kneading deteriorates, Strength, abrasion resistance, impact resilience, etc. deteriorate.
- the Mooney viscosity of the modified solution polymerized diene rubber obtained in the present invention (abbreviated as MV, and ML 1 + 4/100 ° C. when expressing measurement conditions) is preferably in the range of 20 to 150. If it is less than 150, the strength, wear resistance, and impact resilience are deteriorated.
- the vinyl content of the diene portion of the modified solution polymerization diene rubber in the present invention can be changed within a range of 20 to 80%. Considering the vulcanization physical properties of the diene rubber, it is preferable to change it by 30 to 70%. If the wear resistance is important, the vinyl content should be low, and if the brake performance on wet roads is important, the vinyl content should be high.
- Extending oil can be added to the polymerization reaction solution containing the modified solution polymerization diene rubber of the present invention.
- extending oil those usually used in the rubber industry can be used, and examples thereof include paraffinic extending oil, aromatic extending oil, and naphthenic extending oil.
- the pour point of the extending oil is preferably ⁇ 20 to 50 ° C., more preferably ⁇ 10 to 30 ° C. If it is this range, it will be easy to extend and the rubber composition excellent in the balance of a tensile characteristic and low exothermic property will be obtained.
- the suitable aroma carbon content (CA%, Kurz analysis method) of the extender oil is preferably 20% or more, more preferably 25% or more, and the suitable paraffin carbon content (CP%) of the extender oil is , Preferably 55% or less, more preferably 45%. If CA% is too small or CP% is too large, tensile properties will be insufficient.
- the content of the polycyclic aromatic compound in the extending oil is preferably less than 3%. This content is measured by the IP346 method (the testing method of The Institute Petroleum, UK).
- the content of the extending oil is preferably 1 to 50 parts by weight, more preferably 5 to 30 parts by weight with respect to 100 parts by weight of the rubber composition. When the content of the extending oil is within this range, the viscosity of the rubber composition containing silica becomes appropriate, and the balance between tensile properties and low exothermic properties is excellent.
- the modified solution polymerized diene rubber of the present invention is used as a rubber composition for tires, natural rubber, isoprene rubber, butadiene rubber, emulsion-polymerized styrene butadiene rubber, etc., as long as the effects of the present invention are not essentially impaired.
- a reinforcing agent such as silica and / or carbon black and various compounding agents with a roll mill or Banbury mixer, sulfur, vulcanization accelerator, etc. are added, and tires such as treads, sidewalls, carcass, etc. Rubber can be used.
- These compositions can also be used in belts, anti-vibration rubber and other industrial products.
- a filler having a hydroxyl group on the surface is most suitable as a reinforcing material to be filled when the modified solution polymerization diene rubber of the present invention is used for a tire, particularly a tire tread. Further, carbon black can be used in combination.
- the filling amount of the filler is preferably 20 to 150 phr, more preferably 30 to 100 phr with respect to 100 phr of all rubber components.
- silica examples include dry silica, wet silica, colloidal silica, and precipitated silica. Among these, wet silica containing hydrous silicic acid as a main component is particularly preferable. These silicas can be used alone or in combination of two or more.
- the particle size of primary particles of silica is not particularly limited, but is 1 to 200 nm, more preferably 3 to 100 nm, and particularly preferably 5 to 60 nm. When the particle size of the primary particles of silica is within this range, the balance between tensile properties and low heat build-up is excellent. The particle size of the primary particles can be measured with an electron microscope, a specific surface area, or the like.
- a silane coupling agent is preferably compounded at the time of rubber compounding for the purpose of further improving the tensile properties and low heat build-up.
- the silane coupling agent include ⁇ - (3,4-epoxycyclohexyl) ethyltrimethoxysilane, N- ( ⁇ -aminoethyl) - ⁇ -aminopropyltrimethoxysilane, and bis (3-triethoxysilylpropyl).
- Tetrasulfide bis (3-tri-iso-propoxysilylpropyl) tetrasulfide, bis (3-tributoxysilylpropyl) tetrasulfide, ⁇ -trimethoxysilylpropyldimethylthiocarbamyl tetrasulfide, ⁇ -trimethoxysilylpropylbenzo Tetrasulfides such as thiazyl tetrasulfide, bis (3-triethoxysilylpropyl) disulfide, bis (3-tri-iso-propoxysilylpropyl) disulfide, bis (3-tributoxysilylpropyl) disulfide, Examples thereof include ⁇ -trimethoxysilylpropyldimethylthiocarbamyl disulfide and ⁇ -trimethoxysilylpropylbenzothiazyl disulfide.
- the silane coupling agent preferably has 4 or less sulfur contained in one molecule. More preferably, those having 2 or less sulfur are preferred. These silane coupling agents can be used alone or in combination of two or more.
- the amount of the silane coupling agent is preferably 0.1 to 30 parts by weight, more preferably 1 to 20 parts by weight, and particularly preferably 2 to 10 parts by weight with respect to 100 parts by weight of silica.
- carbon black examples include grades such as N110, N220, N330, N440, and N550. These carbon blacks can be used alone or in combination of two or more.
- the specific surface area of carbon black is not particularly limited, but is preferably a nitrogen adsorption specific surface area (N 2 SA), preferably 5 to 200 m 2 / g, more preferably 50 to 150 m 2 / g, particularly preferably 80 to 130 m 2. / G. When the nitrogen adsorption specific surface area is within this range, the tensile properties are more excellent.
- the DBP adsorption amount of carbon black is not particularly limited, but is preferably 5 to 300 ml / 100 g, more preferably 50 to 200 ml / 100 g, and particularly preferably 80 to 160 ml / 100 g. When the DBP adsorption amount is within this range, a rubber composition having more excellent tensile properties can be obtained. Further, as carbon black, the adsorption (CTAB) specific surface area of cetyltrimethylammonium bromide disclosed in JP-A-5-230290 is 110 to 170 m 2 / g, and compression is repeated four times at a pressure of 24,000 psi.
- CTAB adsorption
- Abrasion resistance can be improved by using high structure carbon black having a DBP (24M4DBP) oil absorption of 110 to 130 ml / 100 g after addition.
- the compounding amount of the carbon black is 1 to 50 parts by weight, preferably 2 to 30 parts by weight, particularly preferably 3 to 20 parts by weight with respect to 100 parts by weight of the rubber component.
- the vulcanizing agent can be used in the range of preferably 0.5 to 10 phr, more preferably 1 to 6 phr with respect to 100 phr of all rubber components.
- Typical examples of the vulcanizing agent include sulfur, and other examples include sulfur-containing compounds and peroxides.
- a vulcanization accelerator such as sulfenamide, guanidine, or thiuram may be used in combination with a vulcanizing agent as required.
- zinc white, vulcanization aid, anti-aging agent, processing aid, and the like may be used as required.
- various compounding agents for the rubber composition obtained using the modified solution-polymerized diene rubber of the present invention are not particularly limited, but include improved workability during kneading, wet skid characteristics, impact resilience, and abrasion resistance.
- compatibilizers such as epoxy group-containing compounds, carboxylic acid compounds, carboxylic acid ester compounds, ketone compounds, ether compounds, aldehyde compounds, hydroxyl group-containing compounds and amino group-containing compounds are selected.
- a silicone compound selected from alkoxysilane compounds, siloxane compounds and aminosilane compounds It can be added when kneading.
- the weight average molecular weight (Mw) of the polymer was measured by gel permeation chromatography “GPC: HLC-8020 manufactured by Tosoh Corporation, column: GMHXL manufactured by Tosoh Corporation (two in series)”, and the refractive index (R1) was used. The measurement was performed in terms of polystyrene using dispersed polystyrene as a standard.
- the coupling efficiencies (Cp) shown in Tables 1 and 2 were calculated as follows.
- the “four-branched structure by Sn compound (Cp 1 )” is a diene rubber coupled with a molecular weight peak area of an uncoupled diene rubber on the GPC chart and a nearly four times molecular weight when tin tetrachloride is used. It was calculated
- the “steam coagulation test” shown in Tables 1 and 2 was performed as follows, and the determination was made according to the following criteria.
- a normal dispersant is placed in a 50 L vessel with a stirrer, heated to 90 ° C. with steam, and 1 L of the polymerization solution is poured from 35 vessels with 3 mm diameter holes while maintaining at 90 ° C. or higher. It was dropped over 5 minutes and stirred for 60 minutes.
- the crumb shape to be generated was quantified by 1-5. The larger the value, the better the steam coagulation test. 5: The crumbs have the same size, and the crumbs do not stick together even if stirring is continued.
- the styrene unit content in the polymer was calculated from the integral ratio of 1 H-NMR spectrum.
- the glass transition point (Tg) of the polymer was measured using a differential scanning calorimeter (DSC) type 7 apparatus manufactured by PerkinElmer, Inc., under the condition of cooling to ⁇ 100 ° C. and then increasing the temperature at 10 ° C./min.
- the kneading characteristics and physical properties of the vulcanized rubber were measured by the following methods, and the Mooney viscosity of the rubber composition was measured as follows.
- the kneading for preparing the vulcanizate of the rubber composition was in accordance with JIS K6299: 2001 “Rubber—Method of Preparing Test Sample”.
- the kneading conditions (A kneading) of the rubber composition not containing the vulcanizing agent were using a Laboplast Mill Banbury mixer manufactured by Toyo Seiki Seisakusho Co., Ltd., with a filling rate of about 65% (volume ratio), and a rotor rotational speed of 50 rpm.
- the kneading start temperature was 90 ° C.
- a kneading condition (B kneading) for blending the vulcanizing agent in the rubber composition after kneading was blended with a vulcanizing agent at room temperature using an 8-inch roll manufactured by Daihan Co., Ltd.
- the temperature dispersion of the viscoelasticity test is in accordance with JIS K7244-7: 2007 "Plastics-Test method for dynamic mechanical properties-Part 7: Torsional vibration-Non-resonant method” using "TA INSTRUMENTS viscoelasticity measuring device RSA3"
- the measurement frequency is 10 Hz
- the measurement temperature is ⁇ 50 to 80 ° C.
- the dynamic strain is 0.1%
- the heating rate is 4 ° C./min
- the specimen shape is “width 5 mm ⁇ length 40 mm ⁇ thickness 1 mm”. Measured with samples. The smaller tan ⁇ (60 ° C.), the lower the heat generation.
- Abrasion resistance is determined according to JIS K 6264-2: 2005 "vulcanized rubber and thermoplastic rubber-Determination of wear resistance-Part 2: Test method", Akron abrasion test, B method, abrasion of vulcanized rubber composition The amount was measured. The abrasion resistance of the control sample was taken as 100, and the index was displayed as an abrasion resistance index. A larger index is better.
- the Mooney viscosity was measured in accordance with JIS K6300-2001 at a temperature of 100 ° C. [ML 1 + 4/100 ° C. ].
- the Mooney viscosities shown in Tables 1 and 2 were calculated as follows. “MV (a) after steam coagulation / drying” measured the Mooney viscosity after drying the steam-coagulated crumb at a roll temperature of 110 ° C. for 30 minutes. In “MV (b) after 130 ° C. roll mill”, the drying temperature of the rubber was further raised to 130 ° C. and passed through the roll mill for 20 minutes, and then the Mooney viscosity was measured. “ ⁇ MV” is the difference in MV measured above, and the amount of increase in MV indicated by (b ⁇ a). The smaller this value, the better the storage stability.
- Example [Example 1] and [Comparative Example 1] An autoclave having an internal volume of 10 L was sufficiently substituted with dry nitrogen, charged with 5500 g of cyclohexane, 556 mg (3.02 mmol) of 2,2-di (2-tetrahydrofuryl) propane (DTHFP), 200 g (1.92 mol) ) Styrene, 760 g (14.05 mol) of 1,3-butadiene was placed in an autoclave.
- DTHFP 2,2-di (2-tetrahydrofuryl) propane
- Example 1 2,6-di-tert-butyl-p-cresol was added to the polymerization solution. 3000 g of the polymerization solution was dried by a direct removal method. This rubber was designated as (Comparative Example 1). The remaining solution was dissolved by a steam coagulation method and dried with a roll at 110 ° C. This rubber was referred to as (Example 1). Table 1 summarizes the results of analysis such as GPC analysis, styrene content and vinyl content in diene rubber. Although the difference between Example 1 and Comparative Example 1 is the drying method, the direct dehydration method of Comparative Example 1 has a large difference in storage stability, which is a big problem for industrial production.
- Example 2 A modified solution polymerized diene rubber was produced in the same manner as in Example 1 except that 163 mg of tin tetrachloride corresponding to half the equivalent of n-butyllithium used as the polymerization initiator in Example 1 was added. The analysis results are summarized in Table 1. Compared with Example 1, the 4-branch structure by Sn compound is increasing about 3 times.
- Example 2 A modified solution polymerized diene rubber was produced in the same manner as in Example 1 except that the isoprene used in the prepolymerization was eliminated in Example 1. The analysis results are summarized in Table 1. There is no significant difference in manufacturing.
- Example 3 a modified solution polymerized diene rubber was produced in the same manner as in Example 1 except that the coupling with tin tetrachloride was eliminated.
- the analysis results are summarized in Table 1. In the steam coagulation test, crumbs adhere to each other, which is a big problem for industrial production.
- Example 3 A modified solution-polymerized diene rubber was produced in the same manner as in Example 1 except that the isoprene used for the prepolymerization in Example 1 and the addition of silicon tetrachloride were eliminated. The analysis results are summarized in Table 1. Regarding production, the steam coagulation test was slightly worse, but no other significant difference was seen.
- Example 4 The autoclave with an internal volume of 10 L was sufficiently substituted with dry nitrogen, charged with 5500 g of cyclohexane, 154 g of tetrahydrofuran (THF), 200 g (1.92 mol) of styrene, 760 g (14.05 mol) of 1,3-butadiene. Placed in autoclave. After adjusting the temperature in the autoclave to 25 ° C., 428 mg (5.03 mmol) piperidine and 322 mg (5.03) mmol) n-butyllithium were sequentially added directly to the autoclave to initiate polymerization. The polymerization increased adiabatically and the maximum temperature reached 91 ° C.
- THF tetrahydrofuran
- Example 5 a modified solution polymerized diene rubber was produced in the same manner as in Example 4 except that the amount of styrene was increased to 250 g, the initial 1,3-butadiene was reduced by 710 g, and piperidine was not used.
- the analysis results are summarized in Table 2. There is no significant difference in manufacturing.
- Example 6 A modified solution polymerized diene rubber was produced in the same manner as in Example 4 except that equimolar (N, N-dimethyl-3-aminopropyl) triethoxysilane was used in place of methyltriethoxysilane.
- Table 2 The analysis results are summarized in Table 2. There is no significant difference in manufacturing.
- Example 7 a modified solution-polymerized diene rubber was produced in the same manner as in Example 6 except that silicon tetrachloride was not used after addition of the silane compound.
- the analysis results are summarized in Table 2. The steam coagulation test is a bit worse, but there is no significant difference for other productions.
- Example 6 a modified solution-polymerized diene rubber was produced in the same manner as in Example 6 except that piperidine as a polymerization initiator component, tin tetrachloride after polymerization, and silicon tetrachloride after addition of the silane compound were not used.
- the analysis results are summarized in Table 2. The steam coagulation test deteriorated, and the storage stability deteriorated greatly.
- Examples 8 to 14 and Comparative Examples 5 to 7 The modified solution polymerized diene rubbers experimentally produced in Examples 1 to 7 and Comparative Examples 2 to 4 were blended according to the vulcanized physical composition recipes shown in Table 3, and the vulcanized physical properties were evaluated. The evaluation results are shown in Table 4. In Comparative Example 1, the storage stability was very poor and the evaluation of physical properties was omitted because the industrial possibility was low. Table 4 shows the formulation MV, tensile strength, elongation at break, modulus ratio of M 300 / M 100 , acron wear resistance, and dynamic viscoelasticity test results. The physical property values shown in the index are represented by Comparative Example 5 as 100, and the larger the numerical value of any item, the better the physical properties.
- Comparative Example 5 is a low blending MV, but the modulus ratio is small and the reinforcing property with silica is considered low, and the vulcanized physical properties are not good.
- the tan ⁇ (0 ° C.) was mainly governed by the styrene content and vinyl structure of the diene rubber, and there was no significant difference in any of the diene rubbers prototyped in the present invention.
- Tan ⁇ (60 ° C.) is influenced by the reinforcing property with silica and the dispersibility of silica, and the higher the reinforcing property and the better the dispersibility, the larger the value. From these physical property evaluation results and the like, the modified solution polymerized diene rubber of the present invention has good productivity, high storage stability, and good vulcanized physical properties.
Abstract
Description
一方、反発弾性等を改良するにはゴムの分子設計上、片末端をアルコキシシリル基のようなシリカと反応する官能基を導入する必要がある。これまでのところさらに他の片末端、つまり開始末端もシリカと反応しやすい構造にした両末端変性ジエン系ゴムは、シリカと結合し分子運動が抑えられ、低燃費性が向上すると考えられていた。しかし、実際のところ、両末端をアルコキシシリル基のようなシリカと反応性の高い官能基を導入すると、シリカと混練りするときに凝集したシリカを効率良く分散できないことも分かってきた。
そのため、アルコキシシリル基を含まない片末端の官能基は混練り時にはシリカとゴムとの相互作用が比較的低く、加硫反応時にシリカもしくは他分子と架橋がかかりやすい構造が優れていると考えられてきたが、品質の安定した工業生産性の良いシリカ配合用変性溶液重合ジエン系ゴムの製法にはまだ多くの課題が残ったままである。
しかしながら、近年ますます地球温暖化防止やエネルギー問題等から自動車の低燃費性改良の要求も強くなっている。シリカ配合タイヤはカーボンブラック配合タイヤに比較して低燃費性は改善されているものの、シリカ配合に好適なアルコキシシラン変性溶液重合ジエン系ゴムは保存時にムーニー粘度(MV)が変化する問題があり、またさらなる低燃費性の改善要求が強くなっている。
[1]i)共役ジエン化合物と芳香族ビニル化合物を炭化水素中で、有機リチウム化合物もしくは二級アミン化合物の共存下で重合を開始し、
ii)重合終了後に式(1)で示されるスズ化合物を添加して、ジエン系ゴムの3分岐以上の成分が5~30%になるように処理し、
iii)引続いて式(2)で示されるシラン化合物を添加して、ジエン系ゴムの2分岐の成分が30%以下になるように処理し、
iv)得られた重合体組成物をスチーム凝固、乾燥して、2分岐以上の成分がスチーム凝固前の状態に対して10~50%増加し、かつ、スチーム凝固・乾燥後のムーニー粘度(a)が、更にその後の130℃のロールミルで20分間熱処理した場合のムーニー粘度(b)に対して10以下しか変動しない程度に熱安定化させてなる変性溶液重合ジエン系ゴムの製造方法。
[2]有機リチウム化合物と二級アミン化合物の共存下で重合を開始する[1]に記載の変性溶液重合ジエン系ゴムの製造方法。
[3]有機リチウム化合物でイソプレンを予備重合後、他の共役ジエン化合物と芳香族ビニル化合物を重合する[1]または[2]に記載の変性溶液重合ジエン系ゴムの製造方法。
[4]有機リチウム化合物と二級アミン化合物、イソプレンの共存下で予備重合後、他の共役ジエン化合物と芳香族ビニル化合物を重合する[1]~[3]のいずれかに記載の変性溶液重合ジエン系ゴムの製造方法。
[5]前掲iv)工程のスチーム凝固・乾燥が、2分岐以上の成分がスチーム凝固・乾燥前の状態に対して20~40%増加するようになされた[1]~[4]のいずれかに記載の変性溶液重合ジエン系ゴムの製造方法。
[6]有機リチウム化合物で全モノマーの10重量%以下のイソプレンを予備重合後、他の共役ジエン化合物と芳香族ビニル化合物を重合する[1]、[3]および[5]のいずれかに記載の変性溶液重合ジエン系ゴムの製造方法。
[8][1]~[7]のいずれかに記載の変性溶液重合ジエン系ゴムを少なくとも20phr以上含む全ゴム成分100phrに対して、少なくともシリカ20~150phrを含むゴム組成物。
[9][1]~[8]のいずれかに記載の変性溶液重合ジエン系ゴムを少なくとも20phr以上含む全ゴム成分100phrに対して、少なくともシリカ20~150phrとカーボンブラックを5~30phrを含むゴム組成物。
ii)重合終了後に式(1)で示されるスズ化合物を添加して、ジエン系ゴムの3分岐以上の成分が5~30%になるように処理し、
iii)引続いて式(2)で示されるシラン化合物を添加して、ジエン系ゴムの2分岐の成分が30%以下になるように処理し、
iv)得られた重合体組成物をスチーム凝固、乾燥して、2分岐以上の成分がスチーム凝固前の状態に対して10~50%増加し、かつ、スチーム凝固・乾燥後のムーニー粘度(a)が、更にその後の130℃のロールミルで20分間熱処理した場合のムーニー粘度(b)に対して10以下しか変動しない程度に熱安定化させてなる変性溶液重合ジエン系ゴムの製造方法。
前掲iii)工程後、iv)工程の前に式(4)の条件を満たす量の式(3)で示されるハロゲン化金属化合物を添加してから、iv)工程のスチーム凝固・乾燥を行う変性溶液重合ジエン系ゴムの製造方法。
本発明のうち第三の発明は、上記の変性溶液重合ジエン系ゴムを全ゴム成分中20phr以上含むシリカ配合用ゴム組成物に関するものである。
共役ジエン化合物の使用量は、通常、全モノマー中に40~100重量%、好ましくは50~95重量%である。40重量%未満では、ヒステリシスロスが大きくなる。
本発明で用いられる芳香族ビニル化合物としては、スチレン、α-メチルスチレン、ビニルトルエン、ビニルナフタレン、ジビニルベンゼン、トリビニルベンゼン、およびジビニルナフタレン等を例示することができる。中でも、入手容易性や、得られる変性溶液重合ジエン系ゴムの物性の観点から、スチレンが好ましい。
芳香族ビニル化合物の使用量は、通常、全単量体中に60重量%以下、好ましくは50~5重量%である。
式(1)で示されるスズ化合物として、具体的には次のような化合物が挙げられる。
例えば、四塩化スズ、エチル三塩化スズ、プロピル三塩化スズ、ブチル三塩化スズ、オクチル三塩化スズ、シクロヘキシル三塩化スズ、四臭化スズ、エチル三臭化スズ、プロピル三臭化スズ、ブチル三臭化スズ、オクチル三臭化スズ、シクロヘキシル三臭化スズ、四ヨウ化スズ、エチル三ヨウ化スズ、プロピル三ヨウ化スズ、ブチル三ヨウ化スズ、オクチル三ヨウ化スズ、シクロヘキシル三ヨウ化スズを挙げることができる。これらの中で、好ましいものは四塩化スズ、オクチル三塩化スズ、四臭化スズである。特に好ましいのは四塩化スズである。
例えばテトラメトキシシラン、テトラエトキシシラン、テトラプロポキシシラン、テトラブトキシシラン、テトラフェノキシシラン、テトラトルイロキシシラン、メチルトリメトキシシラン、メチルトリエトキシシラン、メチルトリプロポキシシラン、メチルトリブトキシシラン、メチルトリフェノキシシラン、エチルトリメトキシシラン、エチルトリエトキシシラン、エチルトリプロポキシシラン、エチルトリブトキシシラン、エチルトリフェノキシシラン、ジメチルジメトキシシラン、ジメチルジエトキシシラン、ジメチルジプロポキシシラン、ジメチルジブトキシシラン、ジメチルジフェノキシシラン、ジエチルジメトキシシラン、ジエチルジエトキシシラン、ジエチルジプロポキシシラン、ジエチルジブトキシシラン、ジエチルジフェノキシシラン、ビニルトリメトキシシラン、ビニルトリエトキシシラン、ビニルトリプロポキシシラン、ビニルトリブトキシシラン、ビニルトリフェノキシシラン、ビニルトリ(2-メトキシエトキシ)シラン、ビニルトリ(メチルエチルケトオキシム)シラン、メチルトリ(メチルエチルケトオキシム)シラン、
例えば、式(1)で示されるスズ化合物である四塩化スズ、エチル三塩化スズ、プロピル三塩化スズ、ブチル三塩化スズ、オクチル三塩化スズ、シクロヘキシル三塩化スズ、四臭化スズ、エチル三臭化スズ、プロピル三臭化スズ、ブチル三臭化スズ、オクチル三臭化スズ、シクロヘキシル三臭化スズ、四ヨウ化スズ、エチル三ヨウ化スズ、プロピル三ヨウ化スズ、ブチル三ヨウ化スズ、オクチル三ヨウ化スズ、シクロヘキシル三ヨウ化スズを挙げることができる。
またケイ素化合物として四塩化ケイ素、メチル三塩化ケイ素、エチル三塩化ケイ素、プロピル三塩化ケイ素、ブチル三塩化ケイ素、オクチル三塩化ケイ素、シクロヘキシル三塩化ケイ素、四臭化ケイ素、メチル三臭化ケイ素、エチル三臭化ケイ素、プロピル三臭化ケイ素、ブチル三臭化ケイ素、オクチル三臭化ケイ素、シクロヘキシル三臭化ケイ素、四ヨウ化ケイ素、エチル三ヨウ化ケイ素、プロピル三ヨウ化ケイ素、ブチル三ヨウ化ケイ素、オクチル三ヨウ化ケイ素、シクロヘキシル三ヨウ化ケイ素を挙げることができる。
これらの中で、好ましいものは四塩化ケイ素、メチル三塩化ケイ素、エチル三塩化ケイ素、四塩化スズ、オクチル三塩化スズである。特に好ましいのは四塩化ケイ素、メチル三塩化ケイ素である。
有機リチウム化合物の使用量はジエン系ゴム100g当たり通常、0.1~10ミリモルの範囲が良い。0.1ミリモル未満では分子量が高くなりすぎ溶液粘度の上昇やMV粘度が高くなり、ゴムの生産工程やタイヤ製造等の工程で問題が生じる。また、10ミリモルを超えるとジエン系ゴムの分子量が低くなりすぎ、加硫物性が大きく低下する。
アミン化合物として、トリエチルアミン、ピリジン、N,N,N’,N’-テトラメチルエチレンジアミン、ジピペリジノエタン、N,N-ジエチルエタノールアミンのメチルエーテル、N,N-ジエチルエタノールアミンのエチルエーテル、N,N-ジエチルエタノールアミンのブチルエーテルなどの3級アミン化合物が使用される。
好ましい化合物としては、重合速度や変性効率を考慮するとテトラヒドロフラン(THF)、2,2-ジ(2-テトラヒドロフリル)プロパン(DTHFP)が挙げられる。
これらの化合物の添加量は、複数のN原子やO原子等含む場合有機リチウム化合物1モルに対して通常0.01~10モル、好ましくは0.2~5モルである。テトラヒドロフランのような分子内に一つのO原子をもつ化合物は溶剤に対して、0.05~10%添加するのが好ましい。
具体的に四塩化スズの場合、活性ジエン系ゴムに対して0.0125~0.075mol当量である。さらに好ましくは0.0125~0.05mol当量である。
これらの分岐構造の割合はGPCで測定できる。
しかしながら、このジエン系ゴムに1分子のシラン化合物が結合した構造の変性溶液重合ジエン系ゴムは非常に不安定で保管時にムーニー粘度が上昇する問題が発生する。そのために、保管時には安定でゴム配合時にはシリカと反応する構造に変換するために、スチーム凝固後の2分岐以上の成分が10~50%増加するように乾燥を行う。
2分岐構造A(本発明の構造):(Rubber)-Si-O-Si-(Rubber)
2分岐構造B(従来の構造):(Rubber)-Si-(Rubber)
これらの分岐構造の割合等は製造工程のGPCで求められる。
ハロゲン化金属化合物の添加量はL-(4-n)A≦(4-p)B≦2Lが好ましい。さらに好ましくはL-(4-n)A≦(4-p)B≦1.5Lである。
L-(4-n)A>(4-p)Bの場合、中和が不十分で変性溶液重合ジエン系ゴムのスチーム凝固時の作業性や、保存安定性が悪くなる。(4-p)B>2Lの場合、ゴムの酸性が強くなりすぎ保存安定性が悪くなり、金属腐食等の問題が発生する。
本発明で得られる変性溶液重合ジエン系ゴムのムーニー粘度(MVと略し、測定条件を表記する場合はML1+4 /100℃とする。)は20~150の範囲であることが好ましく、20未満では強力、耐摩耗性、反発弾性が悪化し、一方、150を超えると加工性等が低下する。
伸展油の流動点は、好ましくは-20~50℃、より好ましくは-10~30℃である。この範囲であれば、伸展しやすく、引張特性と低発熱性のバランスに優れたゴム組成物が得られる。伸展油の好適なアロマ炭素含有量(CA%、クルツ分析法)は、好ましくは20%以上、より好ましくは25%以上であり、また、伸展油の好適なパラフィン炭素含有量(CP%)は、好ましくは55%以下、より好ましくは45%である。CA%が小さすぎたり、CP%が大きすぎたりすると、引張特性が不十分となる。伸展油の中の多環芳香族系化合物の含有量は、好ましくは3%未満である。この含有量は、IP346法(英国のThe Institute Petroleumの検査方法)により測定される。
伸展油の含有量は、ゴム組成物100重量部に対して、好ましくは1~50重量部、より好ましくは5~30重量部である。伸展油の含有量がこの範囲にあると、シリカを配合したゴム組成物の粘度が適度となり、かつ引張特性および低発熱性のバランスに優れる。
シリカの一次粒子の粒径は、特に制限されないが、1~200nmであり、より好ましくは3~100nmで、特に好ましくは5~60nmである。シリカの一次粒子の粒径がこの範囲であると、引張特性および低発熱性のバランスに優れる。なお、一次粒子の粒径は、電子顕微鏡や比表面積等で測定できる。
混練時のスコーチを避けられるので、シランカップリング剤は、一分子中に含有される硫黄が4個以下のものが好ましい。さらに好ましくは硫黄が2個以下のものが好ましい。これらのシランカップリング剤は、それぞれ単独で、あるいは2種以上を組み合わせて使用することができる。
シランカップリング剤の配合量は、シリカ100重量部に対して、好ましくは0.1~30重量部、より好ましくは1~20重量部、特に好ましくは2~10重量部である。
カーボンブラックの比表面積は、特に制限はないが、窒素吸着比表面積(N2SA)で、好ましくは5~200m2/g、より好ましくは50~150m2/g、特に好ましくは80~130m2/gである。窒素吸着比表面積がこの範囲であると、より引張特性に優れる。また、カーボンブラックのDBP吸着量も、特に制限はないが、好ましくは5~300ml/100g、より好ましくは50~200ml/100g、特に好ましくは80~160ml/100gである。DBP吸着量がこの範囲であると、より引張特性に優れたゴム組成物が得られる。さらに、カーボンブラックとして、特開平5-230290号公報に開示されているセチルトリメチルアンモニウムブロマイドの吸着(CTAB)比表面積が110~170m2/gであり、24,000psiの圧力で4回繰り返し圧縮を加えた後のDBP(24M4DBP)吸油量が110~130ml/100gであるハイストラクチャーカーボンブラックを用いることにより、耐摩耗性を改善できる。
カーボンブラックの配合量は、ゴム成分100重量部に対して、1~50重量部、好ましくは2~30重量部、特に好ましくは3~20重量部である。
加硫剤としては、代表的には硫黄を、また、その他に硫黄含有化合物、過酸化物などを挙げることができる。
第1表と第2表に示すカップリング効率(Cp)は次のように計算した。
「Sn化合物による4分岐構造(Cp1)」は四塩化スズを用いた場合、GPCチャートの未カップリングのジエン系ゴムの分子量のピーク面積と、ほぼ4倍の分子量のカップリングしたジエン系ゴムに対応するピーク面積の割合より求めた。この構造はスチーム凝固しても実質的にカップリング効率に変化はなかった。
「Si化合物による2分岐構造以上(Cp2)」のサンプルは十分に窒素置換した容器にシラン化合物変性直後の重合溶液を取出し、希釈後分析した。GPCチャートのカップリング前のほぼ2倍の分子量のピーク面積の全ピーク面積に対する割合から求めた。本発明の条件ではシラン化合物変性後のGPCチャートでは3分岐構造に対応するピーク面積は実質的に無視することができた。
「スチーム凝固後の2分岐構造以上(Cp3)」はシラン化合物で変性されたジエン系ゴムもスチーム凝固すると、3分岐構造以上の割合が増加し、スズ化合物でカップリングされたピークと重なった。そのため、カップリング前分子量の2倍以上のピーク面積の割合より求めた。
「スチーム凝固後の増加カップリング効率増加量(ΔCp=Cp3-Cp1-Cp2)」はスチーム凝固前と後のカップリング効率の差である。この値が大きいほど一般的に保存安定性が増加する。
5:クラムの大きさが揃い、撹拌を続けてもクラム同士が凝着しない。
(工業生産で大きな問題は発生しないと推定される。)
3:クラムの大きさは少し不揃いであり、撹拌を続けるとクラム同士の凝着量が増加する。(工業生産で問題が発生し、何らかの対策が必要と推定される。)
1:クラムは不揃いで、落下後すぐにクラム同士の凝着が始まる。
(工業生産で大きな問題が発生し、生産できないか、何らの大きな技術的対策が必須である。)
4、2:はそれぞれの中間である。
加硫剤を含まないゴム組成物の混練条件(A練り)は東洋精機製作所(株)製のラボプラストミルバンバリー形ミキサーを用い、充てん率が約65%(体積比)、ローター回転数が50rpm、混練り開始温度を90℃で実施した。
A練り後のゴム組成物に加硫剤を配合する混練条件(B練り)は(株)ダイハンDaihan Co., Ltd.製8インチロールを用いて、室温で加硫剤を配合した。
tan δ(60℃)が小さい程、低発熱性である。
第1表と第2表に示すムーニー粘度は次のように計算した。
「スチーム凝固・乾燥後のMV(a)」はスチーム凝固したクラムをロールの温度110℃で、30分間乾燥後、ムーニー粘度を測定した。
「130℃ロールミル後のMV(b)」は、このゴムを乾燥温度をさらに130℃に上げてロールミルで、20分間通した後で、ムーニー粘度を測定した。
「ΔMV」は上記で測定したMVの差、(b-a)で示されるMVの増加量であり、この値が小さいほど、保存安定性は良好である。
[実施例1]および[比較例1]
内容積が10Lのオートクレーブを乾燥窒素で十分に置換し、5500gのシクロヘキサン、を入れ、556mg(3.02mmol)の2,2-ジ(2-テトラヒドロフリル)プロパン(DTHFP),200g(1.92mol)のスチレン、760g(14.05mol)の1,3-ブタジエンをオートクレーブに入れた。オートクレーブ内の温度を25℃に調整後、別容器のシクロヘキサン中で10gのイソプレンと428mg(5.03mmol)のピペリジン、322mg(5.03mmol)のn-ブチルリチウムの反応物を全量オートクレーブに添加して重合を開始した。重合は断熱的に昇温し、最高温度が88℃に達した。この時点で、30gの1,3-ブタジエンを追加し、さらに5分間重合を行った。その後、52.4mg(0.201mmol)の四塩化スズを添加し、5分間反応した。ここで、オートクレーブから20mLの重合溶液を十分に窒素置換した容器に分析用として抜き出し、後ほど希釈してGPC分析を行い、残りはスチーム凝固した。引続いて1.29g(4.20mmol)のメチルトリス[2-(ジメチルアミノ)エトキシ]シランをオートクレーブに加え、15分間反応した。GPC分析によると、活性ジエン系ゴムとシラン化合物のモル比は1.3であった。さらに213mg(1.26mmol)の四塩化ケイ素を添加して5分間反応した。最後に2,6-ジ-tert-ブチル-p-クレゾールを重合溶液に加えた。3000gの重合溶液は直脱法で乾燥した。このゴムを(比較例1)とした。 残りの溶液はスチーム凝固法で脱溶し、110℃のロールで乾燥した。このゴムを(実施例1)とした。GPC分析、ジエン系ゴム中のスチレン含量、ビニル含量等の分析結果を第1表にまとめた。実施例1と比較例1の違いは乾燥方法であるが、比較例1の直脱乾燥方法では保存安定性に大きな差が出ており、工業生産には大きな課題である。
実施例1で、重合開始剤として用いたn-ブチルリチウムの半分の当量に相当する163mgの四塩化スズを添加した以外は実施例1と同様に変性溶液重合ジエン系ゴムを製造した。分析結果を第1表にまとめた。Sn化合物による4分岐構造が実施例1に比較して、およそ3倍に増加している。
実施例1で、予備重合に用いたイソプレンを無くした以外は実施例1と同様に変性溶液重合ジエン系ゴムを製造した。分析結果を第1表にまとめた。製造に関しては特に大きな差は見られない。
実施例1で、四塩化スズでカップリングすることを無くした以外は実施例1と同様に変性溶液重合ジエン系ゴムを製造した。分析結果を第1表にまとめた。スチーム凝固試験でクラム同士が凝着する現象がみられ、工業生産には大きな問題である。
実施例1で、予備重合に用いたイソプレンを無くし、さらに四塩化ケイ素の添加を無くした以外は実施例1と同様に変性溶液重合ジエン系ゴムを製造した。分析結果を第1表にまとめた。製造に関してはスチーム凝固試験がわずかに悪くなったが、これ以外は大きな差は見られない。
内容積が10Lのオートクレーブを乾燥窒素で十分に置換し、5500gのシクロヘキサンを入れ、154gのテトラヒドロフラン(THF),200g(1.92mol)のスチレン、760g(14.05mol)の1,3-ブタジエンをオートクレーブに入れた。オートクレーブ内の温度を25℃に調整後、428mg(5.03mmol)のピペリジン、322mg(5.03)mmol)のn-ブチルリチウムを順次オートクレーブに直接添加して重合を開始した。重合は断熱的に昇温し、最高温度が91℃に達した。この時点で、40gの1,3-ブタジエンを追加し、さらに5分間重合を行った。その後、52.4mg(0.201mmol)の四塩化スズを添加し、5分間反応した。ここで、オートクレーブから20mLの重合溶液を十分に窒素置換した容器に分析用として抜き出し、後ほど希釈してGPC分析を行い、残りはスチーム凝固した。引続いて0.861g(4.83mmol)のメチルトリエトキシシランをオートクレーブに加え、15分間反応した。GPC分析によると、活性ジエン系ゴムとシラン化合物のモル比は1.5であった。さらに213mg(1.26mmol)の四塩化ケイ素を添加して5分間反応した。最後に2,6-ジ-tert-ブチル-p-クレゾールを重合溶液に加えた。この溶液はスチーム凝固法で脱溶し、110℃のロールで乾燥した。このゴムを(実施例4)とした。分析結果は第2表にまとめた。
実施例4で、スチレンの量を250gに増加し、最初の1,3-ブタジエンを710g減量し、ピペリジンを使用しなかった以外は実施例4と同様に変性溶液重合ジエン系ゴムを製造した。分析結果を第2表にまとめた。製造に関しては大きな差は見られない。
実施例4で、メチルトリエトキシシランの代わりに等モルの(N,N-ジメチル-3-アミノプロピル)トリエトキシシラン使用した以外は実施例4と同様に変性溶液重合ジエン系ゴムを製造した。分析結果を第2表にまとめた。製造に関しては大きな差は見られない。
実施例6で、シラン化合物添加後に四塩化ケイ素を使用しなかった以外は実施例6と同様に変性溶液重合ジエン系ゴムを製造した。分析結果を第2表にまとめた。スチーム凝固試験が少し悪くなったが、他の製造に関しては大きな差は見られない。
実施例6で、重合開始剤成分のピペリジンと重合後に四塩化スズ、シラン化合物添加後に四塩化ケイ素を使用しなかった以外は実施例6と同様に変性溶液重合ジエン系ゴムを製造した。分析結果を第2表にまとめた。スチーム凝固試験が悪くなり、保存安定性も大きく悪化した。
実施例1~実施例7と比較例2~比較例4で試作した変性溶液重合ジエン系ゴムを第3表の加硫物性配合処方に従って配合し、加硫物性を評価した。評価結果は第4表に示した。比較例1は保存安定性が非常に悪く、工業性の可能性が低いので物性評価を省略した。
第4表には配合MVと引張強さ、切断時延び、M300/M100のモジュラス比、アクロン耐摩耗性、動的粘弾性試験結果を示した。指数表示の物性値は比較例5を100として表し、いずれの項目も数値が大きいほど良好な物性を示す。
補強性の目安となるモジュラス比が大きい値、配合MVは低い値の方が良好である。比較例5は低い配合MVであるが、モジュラス比が小さく、シリカとの補強性が低いと考えられ、加硫物性は良くない。
引張強さはシリカとの補強性が高いほど、大きな値となり、アクロン耐摩耗性と相関関係が高い。
tan δ(0℃)は主にジエン系ゴムのスチレン含量とビニル構造に支配され、本発明で試作のジエン系ゴムはいずれも顕著な差は無かった。
tan δ(60℃)はシリカとの補強性やシリカの分散性に影響され、補強性が高く、分散性の良いほど、大きな数値を示す。
これらの物性評価結果等から、本発明の変性溶液重合ジエン系ゴムは生産性が良好で、保存安定性が高く、しかも加硫物性が良好である。
Claims (9)
- i)共役ジエン化合物と芳香族ビニル化合物を炭化水素中で、有機リチウム化合物もしくは二級アミン化合物の共存下で重合を開始し、
ii)重合終了後に式(1)で示されるスズ化合物を添加して、ジエン系ゴムの3分岐以上の成分が5~30%になるように処理し、
iii)引続いて式(2)で示されるシラン化合物を添加して、ジエン系ゴムの2分岐の成分が30%以下になるように処理し、
iv)得られた重合体組成物をスチーム凝固、乾燥して、2分岐以上の成分がスチーム凝固前の状態に対して10~50%増加し、かつ、スチーム凝固・乾燥後のムーニー粘度(a)が、更にその後の130℃のロールミルで20分間熱処理した場合のムーニー粘度(b)に対して10以下しか変動しない程度に熱安定化させてなる変性溶液重合ジエン系ゴムの製造方法。
- 有機リチウム化合物と二級アミン化合物の共存下で重合を開始する請求項1に記載の変性溶液重合ジエン系ゴムの製造方法。
- 有機リチウム化合物でイソプレンを予備重合後、他の共役ジエン化合物と芳香族ビニル化合物を重合する請求項1または2に記載の変性溶液重合ジエン系ゴムの製造方法。
- 有機リチウム化合物と二級アミン化合物、イソプレンの共存下で予備重合後、他の共役ジエン化合物と芳香族ビニル化合物を重合する請求項1~3のいずれか一項に記載の変性溶液重合ジエン系ゴムの製造方法。
- 前掲iv)工程のスチーム凝固・乾燥が、2分岐以上の成分がスチーム凝固・乾燥前の状態に対して20~40%増加するようになされた請求項1~4のいずれか一項に記載の変性溶液重合ジエン系ゴムの製造方法。
- 有機リチウム化合物で全モノマーの10重量%以下のイソプレンを予備重合後、他の共役ジエン化合物と芳香族ビニル化合物を重合する請求項1、3および5のいずれか一項に記載の変性溶液重合ジエン系ゴムの製造方法。
- 前掲iii)工程後、iv)工程の前に式(4)の条件を満たす量の式(3)で示されるハロゲン化金属化合物を添加してから、iv)工程のスチーム凝固・乾燥を行う請求項1~6のいずれか一項に記載の変性溶液重合ジエン系ゴムの製造方法。
- 請求項1~7のいずれか一項に記載の変性溶液重合ジエン系ゴムを少なくとも20phr以上含む全ゴム成分100phrに対して、少なくともシリカ20~150phrを含むゴム組成物。
- 請求項1~8のいずれか一項に記載の変性溶液重合ジエン系ゴムを少なくとも20phr以上含む全ゴム成分100phrに対して、少なくともシリカ20~150phrとカーボンブラックを5~30phrを含むゴム組成物。
Priority Applications (6)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
RU2018114111A RU2709516C2 (ru) | 2015-09-18 | 2015-09-18 | Способ получения модифицированного диенового каучука, получаемого полимеризацией в растворе, подлежащего смешиванию с диоксидом кремния, и каучуковой композиции, содержащей его |
US15/760,703 US10428161B2 (en) | 2015-09-18 | 2015-09-18 | Method for producing modified solution-polymerized diene rubber to be blended with silica, and rubber composition containing same |
KR1020187010070A KR20180054673A (ko) | 2015-09-18 | 2015-09-18 | 실리카 배합용 변성 용액 중합 디엔계 고무의 제조 방법 및 이의 고무 조성물 |
CN201580083214.2A CN108026205B (zh) | 2015-09-18 | 2015-09-18 | 二氧化硅混合用改性溶液聚合二烯类橡胶的制造方法及其橡胶组合物 |
PCT/JP2015/076805 WO2017046963A1 (ja) | 2015-09-18 | 2015-09-18 | シリカ配合用変性溶液重合ジエン系ゴムの製造法およびそのゴム組成物 |
EP15904148.2A EP3351569B1 (en) | 2015-09-18 | 2015-09-18 | Method for producing modified solution-polymerized diene rubber to be blended with silica, and rubber composition containing same |
Applications Claiming Priority (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
PCT/JP2015/076805 WO2017046963A1 (ja) | 2015-09-18 | 2015-09-18 | シリカ配合用変性溶液重合ジエン系ゴムの製造法およびそのゴム組成物 |
Publications (1)
Publication Number | Publication Date |
---|---|
WO2017046963A1 true WO2017046963A1 (ja) | 2017-03-23 |
Family
ID=58288471
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
PCT/JP2015/076805 WO2017046963A1 (ja) | 2015-09-18 | 2015-09-18 | シリカ配合用変性溶液重合ジエン系ゴムの製造法およびそのゴム組成物 |
Country Status (6)
Country | Link |
---|---|
US (1) | US10428161B2 (ja) |
EP (1) | EP3351569B1 (ja) |
KR (1) | KR20180054673A (ja) |
CN (1) | CN108026205B (ja) |
RU (1) | RU2709516C2 (ja) |
WO (1) | WO2017046963A1 (ja) |
Cited By (1)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
WO2023190934A1 (ja) * | 2022-03-31 | 2023-10-05 | 有限会社Etic | ジエン系ゴム組成物およびその製造方法 |
Families Citing this family (1)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
FR3039556A1 (fr) * | 2015-07-29 | 2017-02-03 | Michelin & Cie | Pneumatique d'avion |
Citations (4)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JP2000281835A (ja) * | 1999-03-31 | 2000-10-10 | Nippon Zeon Co Ltd | 油展ゴム、ゴム組成物および架橋物 |
JP2004018795A (ja) * | 2002-06-20 | 2004-01-22 | Jsr Corp | 共役ジオレフィン(共)重合ゴム、該(共)重合ゴムの製造方法、ゴム組成物およびタイヤ |
WO2008029814A1 (fr) * | 2006-09-04 | 2008-03-13 | Bridgestone Corporation | Composition de caoutchouc et bandage pneumatique utilisant celle-ci |
JP2009287018A (ja) * | 2008-04-28 | 2009-12-10 | Bridgestone Corp | 変性低分子量共役ジエン系重合体 |
Family Cites Families (21)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JPS5938209A (ja) | 1982-08-28 | 1984-03-02 | Japan Synthetic Rubber Co Ltd | 分岐状共役ジエン系重合体 |
JPH0651746B2 (ja) | 1986-03-31 | 1994-07-06 | 日本合成ゴム株式会社 | シラン化合物変性重合体の製造方法 |
JPH0653768B2 (ja) | 1986-12-27 | 1994-07-20 | 住友化学工業株式会社 | 変性ジエン系重合体ゴムの製造方法 |
JPH0768307B2 (ja) | 1987-01-14 | 1995-07-26 | 日本合成ゴム株式会社 | シラン化合物変性ゴム状重合体の製造法 |
EP0341496B1 (en) * | 1988-05-02 | 1993-10-20 | Sumitomo Chemical Company, Limited | Modified diene polymer rubbers |
JP2625876B2 (ja) | 1988-05-10 | 1997-07-02 | 住友化学工業株式会社 | 変性ジエン系重合体ゴムの製造方法 |
US6344518B1 (en) * | 1998-11-10 | 2002-02-05 | Jsr Corporation | Conjugated diolefin copolymer rubber and rubber composition |
US6313210B1 (en) * | 2000-07-31 | 2001-11-06 | Bridgestone Coporation | Silica-reinforced rubber compounds containing moisture stabilized polymers |
ES2307678T3 (es) | 2001-03-26 | 2008-12-01 | Jsr Corporation | Polimero modificado hidrogenado, procedimiento para producir el mismo y composicion que contiene el mismo. |
JP3988495B2 (ja) | 2001-03-26 | 2007-10-10 | Jsr株式会社 | 水添変性重合体及びその製造方法並びにそれを含む組成物 |
US7342070B2 (en) | 2001-09-27 | 2008-03-11 | Jsr Corporation | Conjugated diolefin (co)polymer rubber, process for producing (co)polymer rubber, rubber composition, composite, and tire |
US7339005B2 (en) | 2003-01-31 | 2008-03-04 | Sumitomo Chemical Company, Limited | Process for producing modified diene polymer rubber |
JP4289111B2 (ja) | 2003-04-15 | 2009-07-01 | 住友化学株式会社 | 変性ジエン系重合体ゴム及びその製造方法 |
TWI385182B (zh) | 2004-03-15 | 2013-02-11 | Jsr Corp | Conjugated diene (co) poly rubber and method for producing the same |
JP5276249B2 (ja) * | 2004-08-06 | 2013-08-28 | Jsr株式会社 | 共役ジエン系共重合ゴムの製造方法 |
KR101157295B1 (ko) | 2004-08-06 | 2012-06-15 | 제이에스알 가부시끼가이샤 | 공액 디엔계 공중합 고무의 제조 방법 |
JP4655706B2 (ja) | 2005-03-17 | 2011-03-23 | 住友化学株式会社 | 変性ジエン系重合体ゴム及びその製造方法 |
CN100500709C (zh) | 2006-01-26 | 2009-06-17 | 中国石油化工股份有限公司 | 一种共轭二烯烃均聚和共聚合工艺的凝胶抑制方法 |
US20080103261A1 (en) | 2006-10-25 | 2008-05-01 | Bridgestone Corporation | Process for producing modified conjugated diene based polymer, modified conjugated diene based polymer produced by the process, rubber composition, and tire |
RU2451693C2 (ru) | 2007-03-23 | 2012-05-27 | Джей эс а КОРПОРЕЙШН | Способ получения модифицированного полимера сопряженного диена, модифицированный полимер и каучуковая композиция |
TWI466898B (zh) | 2011-08-31 | 2015-01-01 | Tsrc Corp | 共軛二烯橡膠的製造方法及其組成物 |
-
2015
- 2015-09-18 CN CN201580083214.2A patent/CN108026205B/zh active Active
- 2015-09-18 EP EP15904148.2A patent/EP3351569B1/en active Active
- 2015-09-18 RU RU2018114111A patent/RU2709516C2/ru active
- 2015-09-18 US US15/760,703 patent/US10428161B2/en active Active
- 2015-09-18 KR KR1020187010070A patent/KR20180054673A/ko unknown
- 2015-09-18 WO PCT/JP2015/076805 patent/WO2017046963A1/ja active Application Filing
Patent Citations (4)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JP2000281835A (ja) * | 1999-03-31 | 2000-10-10 | Nippon Zeon Co Ltd | 油展ゴム、ゴム組成物および架橋物 |
JP2004018795A (ja) * | 2002-06-20 | 2004-01-22 | Jsr Corp | 共役ジオレフィン(共)重合ゴム、該(共)重合ゴムの製造方法、ゴム組成物およびタイヤ |
WO2008029814A1 (fr) * | 2006-09-04 | 2008-03-13 | Bridgestone Corporation | Composition de caoutchouc et bandage pneumatique utilisant celle-ci |
JP2009287018A (ja) * | 2008-04-28 | 2009-12-10 | Bridgestone Corp | 変性低分子量共役ジエン系重合体 |
Cited By (1)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
WO2023190934A1 (ja) * | 2022-03-31 | 2023-10-05 | 有限会社Etic | ジエン系ゴム組成物およびその製造方法 |
Also Published As
Publication number | Publication date |
---|---|
CN108026205A (zh) | 2018-05-11 |
EP3351569A4 (en) | 2019-06-12 |
KR20180054673A (ko) | 2018-05-24 |
RU2709516C2 (ru) | 2019-12-18 |
EP3351569A1 (en) | 2018-07-25 |
EP3351569B1 (en) | 2020-11-04 |
RU2018114111A3 (ja) | 2019-10-21 |
US10428161B2 (en) | 2019-10-01 |
RU2018114111A (ru) | 2019-10-21 |
CN108026205B (zh) | 2021-01-29 |
US20180273650A1 (en) | 2018-09-27 |
Similar Documents
Publication | Publication Date | Title |
---|---|---|
JP4775582B2 (ja) | ゴム組成物 | |
EP2123687B1 (en) | Conjugated diolefin copolymer rubber, method for producing the same, rubber composition and tire | |
KR101938580B1 (ko) | 변성 공액 디엔계 중합체 및 그의 제조 방법, 중합체 조성물, 가교 중합체, 및 타이어 | |
JP5994784B2 (ja) | 変性共役ジエン系重合体の製造方法 | |
JP5994783B2 (ja) | 変性共役ジエン系重合体の製造方法 | |
KR20110003557A (ko) | 변성 중합체를 함유하는 고무 조성물을 사용한 타이어 | |
US10428161B2 (en) | Method for producing modified solution-polymerized diene rubber to be blended with silica, and rubber composition containing same | |
JP2001131229A (ja) | 重合体、その製造方法、及びそれを用いたゴム組成物 | |
JP6342752B2 (ja) | シリカ配合用変性溶液重合ジエン系ゴムの製造法およびそのゴム組成物 | |
JP2009161778A (ja) | 変性ブタジエンゴム組成物 | |
JP6651787B2 (ja) | タイヤ用ゴム組成物 | |
JP2009126360A (ja) | 重荷重用タイヤ | |
JP2018520256A (ja) | シラン官能化ポリマー並びにそれらを作製及び使用するためのプロセス | |
JP2009197237A (ja) | 変性ジエン系ゴム組成物 | |
JP5171017B2 (ja) | ゴム組成物及びそれを用いた空気入りタイヤ | |
JP6496191B2 (ja) | ゴム組成物及び重荷重用タイヤ | |
JP6651788B2 (ja) | タイヤ用ゴム組成物 | |
WO2023190934A1 (ja) | ジエン系ゴム組成物およびその製造方法 | |
TWI663177B (zh) | 二氧化矽調配用改質溶液聚合二烯系橡膠的製造方法及其橡膠組成物 | |
US20240132706A1 (en) | Rubber composition for tires and tire | |
US20230312889A1 (en) | Polymer composition, method for producing same, formulation, crosslinked product, and tire |
Legal Events
Date | Code | Title | Description |
---|---|---|---|
121 | Ep: the epo has been informed by wipo that ep was designated in this application |
Ref document number: 15904148 Country of ref document: EP Kind code of ref document: A1 |
|
WWE | Wipo information: entry into national phase |
Ref document number: 15760703 Country of ref document: US |
|
NENP | Non-entry into the national phase |
Ref country code: DE |
|
ENP | Entry into the national phase |
Ref document number: 20187010070 Country of ref document: KR Kind code of ref document: A |
|
WWE | Wipo information: entry into national phase |
Ref document number: 2015904148 Country of ref document: EP Ref document number: 2018114111 Country of ref document: RU |
|
NENP | Non-entry into the national phase |
Ref country code: JP |