Method for producing modified conjugated diene polymer and rubber composition
Disclosed are a method for producing a modified conjugated diene polymer improved in quality stability, more enhanced in low heat buildup and reinforcing ability when used in a rubber composition, excellent in wear resistance, mechanical characteristics and processability, and improved in cold flow; and a rubber composition using the same. The method includes a step of modifying an active end of an active end-containing conjugated diene polymer having a cis-1,4-bond content of 75% or more with an alkoxysilane compound containing at least one functional group selected from the group consisting of (a) an epoxy group, (b) an isocyanate group and (c) a carboxyl group, and a step of adding a condensation accelerator to conduct condensation reaction of the alkoxysilane compound (residue) in an aqueous solution having a pH of 9 to 14 and a temperature of 85 to 180° C.
1. A method for producing a modified conjugated diene polymer, the method comprising two steps of:
a step of modifying an active end of an active end-containing conjugated diene polymer having a cis-1,4-bond content of 75% or more with an alkoxysilane compound containing at least one functional group selected from the group consisting of (a) an epoxy group, (b) an isocyanate group and (c) a carboxyl group, and
a step of adding a condensation accelerator to conduct condensation reaction of the alkoxysilane compound (residue) in an aqueous solution having a pH of 9 to 14 and a temperature of 85 to 180° C.
2. The method according to claim 1 , wherein the alkoxysilane compound is at least one compound selected from the group consisting of 2-glycidoxyethyltrimethoxysilane, 2-glycidoxyethyltriethoxysilane, (2-glycidoxyethyl)methyldimethoxysilane, 3-glycidoxypropyltrimethoxysilane, 3-glycidoxypropyltriethoxysilane, (3-glycidoxypropyl)methyldimethoxysilane, 2-(3,4-epoxycyclohexyl)ethyltrimethoxysilane, 2-(3,4-epoxycyclohexyl)ethyltriethoxysilane, 2-(3,4-epoxycyclohexyl)ethyl(methyl)dimethoxysilane, 3-isocyanatopropyltrimethoxysilane, 3-isocyanatopropyltriethoxysilane, 3-isocyanatopropylmethyldiethoxysilane, 3-isocyanatopropyltriisopropoxysilane, 3-methacryloyloxypropyltriethoxysilane, 3-methacryloyloxypropyltrimethoxysilane, 3-methacryloyloxypropylmethyldiethoxysilane and 3-methacryloyloxypropyltriisopropoxysilane.
3. The method according to claim 1 , wherein a compound containing at least one functional group selected from the group consisting of (d) an amino group, (e) an imino group and (f) a mercapto group is further added.
4. The method according to claim 1 , wherein the conjugated diene compound constituting the modified conjugated diene polymer is at least one conjugated diene compound selected from the group consisting of 1,3-butadiene, isoprene and 2,3-dimethyl-1,3-butadiene.
5. The method according to claim 1 , wherein the active end-containing conjugated diene polymer has a Mooney viscosity at 100° C. (ML 1+4 , 100° C.) of 5 to 50.
6. The method according to claim 1 , wherein the active end-containing conjugated diene polymer is a polymer obtained by polymerization using a catalyst containing the following components (g) to (i) as main components:
Component (g); a compound containing a rare earth element having an atomic number of 57 to 71 in the periodic table or a reaction product of the compound with a Lewis base;
Component (h); an alumoxane and/or an organic aluminum compound corresponding to AlR 1 R 2 R 3 (wherein R 1 and R 2 , which may be the same or different, are hydrogen atoms or hydrocarbon groups having 1 to 10 carbon atoms, and R 3 is a hydrocarbon group having 1 to 10 carbon atoms, and may be the same as said R 1 and R 2 , or different therefrom);
Component (i); a halogen-containing compound.
7. The method according to claim 1 , wherein the condensation accelerator is at least one selected from the group consisting of the following components (j) and (k):
Component (j); a carboxylate of divalent tin;
Component (k); a hydroxyl group-containing or carboxyl group-containing tetravalent tin compound.
8. The method according to claim 3 , wherein the condensation accelerator is at least one selected from the group consisting of the following components (j) and (k):
Component (j); a carboxylate of divalent tin;
Component (k); a hydroxyl group-containing or carboxyl group-containing tetravalent tin compound.
9. The method according to claim 3 , wherein the functional group-containing compound is 3-diethylaminopropyl(triethoxy)silane, 3-dimethylaminopropyl(triethoxy)silane, 3-aminopropyltriethoxysilane, 3-(1-hexamethyleneimino)propyl(triethoxy)silane, N-(1-methylpropylidene)-3-(triethoxysilyl)-1-propaneamine, N-(1,3-dimethylbutylidene)-3-(triethoxysilyl)--1-propaneamine, 3-(1-hexamethyleneimino)propyl(triethoxy)silane, (1-hexamethyleneimino)methyl(trimethoxy)silane, 1-[3-(triethoxysilyl)propyl]-4,5-dihydroimidazole, 1-[3-(trimethoxysilyl)propyl]-4,5-dihydroimidazole, N-(3-triethoxysilylpropyl)-4,5-dihydroimidazole or 3-mercaptopropyltriethoxysilane.
10. The method according to claim 7 , wherein the condensation accelerator is tin bis(n-octanoate), tin bis(2-ethylhexanoate), tin bis(laurate), tin bis(naphthoate), tin bis(stearate), tin bis(oleate), dibutyltin diacetate, dibutyltin di-n-octanoate, dibutyltin 2-ethylhexanoate, dibutyltin dilaurate, dibutyltin maleate, dibutyltin bis(benzylmaleate), dibutyltin bis(2-ethylhexylmaleate), di-n-octyltin diacetate, di-n-octyltin di-n-octanoate, di-n-octyltin di-2-ethylhexanoate, di-n-octyltin dilaurate, di-n-octyltin maleate, di-n-octyltin bis(benzylmaleate) or di-n-octyltin bis(2-ethylhexylmaleate).