Claims
- 1. A process for producing a modified conjugated diene polymer which comprises the steps of (I) polymerizing a conjugated diene in an inert organic solvent in the presence of a catalyst comprising (a) a lanthanum series rare earth metal compound, (b) an organoaluminum compound represented by the general formula, AlR.sup.1 R.sup.2 R.sup.3 (wherein R.sup.1, R.sup.2 and R.sup.3, which may be same or different, are hydrogen atoms or hydrocarbon groups of 1 to 8 carbon atoms and at least one of R.sup.1, R.sup.2 and R.sup.3 is said hydrogencarbon group) and, if necessary, (c) a Lewis acid and/or (d) a Lewis base and (II) modifying the resulting reactive polymer with a modifying compound of an organometal halide compound represented by the general formula, R.sup.4.sub.n MX.sub.4-n (wherein R.sup.4 is an alkyl group of 1 to 20 carbon atoms or an aryl group, M is a tin atom, X is a halogen atom, and n is an integer of 1 to 3),
- 2. A process according to claim 1, wherein the conjugated diene is 1,3-butadiene, isoprene or a mixture thereof.
- 3. A process according to claim 1, wherein the lanthanum series rare earth element compound (a) is a compound represented by the general formula, LnY.sup.2.sub.3 (wherein Ln is at least one lanthanum series rare earth element having an atomic number of 57 to 71 and Y.sup.2 is a hydrocarbon residue, an alkoxide residue, a thioalkoxide residue, an amide residue, a phosphoric acid salt residue, a phosphorous acid salt residue or a carboxylic acid salt residue.
- 4. A process according to claim 3, wherein the Ln is at least one member selected from the group consisting of cerium, preseodymium, neodymium and gadolinium.
- 5. A process according to claim 3, wherein the Ln is neodymium.
- 6. A process according to claim 3, wherein the LnY.sup.2.sub.3 compound is a compound represented by the general formula, LnR.sub.3, Ln(OR).sub.3, Ln(SR).sub.3, Ln(NR.sub.2).sub.3, ##STR12## LnX.sub.3 or (RCOO).sub.3 Ln (wherein Ln has the same definition as given above, R and R', which may be same or different, are hydrocarbon groups of 1 to 20 carbon atoms, and X is a halogen atom).
- 7. A process according to claim 3, wherein the lanthanum series rare earth element compound (a) is selected from the group consisting of neodymium trichloride, didymium trichloride (the didymium is a rare earth metal mixture consisting of 72% by weight of neodymium, 20% by weight of lanthanum and 8% by weight of praseodymium), neodymium 2-ethylhexanoate, didymium 2-ethylhexanoate, neodymium naphthenate, neodymium 2,2-diethylhexanoate, neodymium trimethacrylate and polymers of neodymium trimethacrylate.
- 8. A process according to claim 1, wherein the organoaluminum compound (b) is trimethylaluminum, triethylaluminum, triisopropylaluminum, tributylaluminum, triisobutylaluminum, trihexylaluminum, tricyclohexylaluminum, diisobutylaluminum hydride, diethylaluminum hydride, dipropylaluminum hydride, ethylaluminum dihydride, propylaluminum dihydride or isobutylaluminum dihydride.
- 9. A process according to claim 1, wherein the Lewis acid (c) is selected from the group consisting of aluminum halide compounds represented by the general formula, AlR.sup.5.sub.m X.sub.3-m (wherein R.sup.5 is a hydrocarbon group having 1 to 8 carbon atoms, m is 0 or a positive number of 1 to 3, and X is a halogen atom), halogen elements, tin halides and titanium halides.
- 10. A process according to claim 1, wherein the Lewis acid (c) is selected from the group consisting of dimethylaluminum chloride, diethylaluminum chloride, dibutylaluminum chloride, ethylaluminum sesquichloride, ethylaluminum dichloride, and bromides and iodides corresponding to them.
- 11. A process according to claim 1, wherein the Lewis base (d) is selected from the group consisting of acetylacetone, tetrahydrofuran, pyridine, N,N-dimethylformamide, thiophene, diphenyl ether, triethylamine, organic phosphorus compounds and mono- or dihydric alcohols.
- 12. A process according to claim 1, wherein the mole ratio of the component (b)/the component (a) is 10 to 150.
- 13. A process according to claim 1, wherein the mole ratio of the component (b)/the component (a) is 15 to 100.
- 14. A process according to claim 12, wherein the catalyst consists of the component (a) and the component (b).
- 15. A process according to claim 12, wherein the mole ratio of the component (c)/the component (a) is from 0 to 6.
- 16. A process according to claim 13, wherein the mole ratio of the component (c)/the component (a) is from 0.5 to 5.0.
- 17. A process according to claim 12, wherein the mole ratio of the component (d)/the component (a) is from 0 to 20.
- 18. A process according to claim 13, wherein the mole ratio of the component (d)/the component (a) is from 1 to 15.
- 19. A process according to claim 1, wherein the catalyst is prepared previously by mixing the components (a) to (d) in the presence or absence of a conjugated diene in a polymerization solvent, subjecting the mixture to reaction and then aging the reaction mixture.
- 20. A process according to claim 19, wherein the polymerization solvent is at least one member selected from the group consisting of aromatic hydrocarbons, aliphatic hydrocarbons, alicyclic hydrocarbons and halogenated hydrocarbons.
- 21. A process according to claim 1, wherein the polymerization in the step (I) is conducted at -20.degree. C. to 150.degree. C.
- 22. A process according to claim 20, wherein the monomer concentration in the solvent is 5 to 50% by weight.
- 23. A process according to claim 1, wherein the modification in the step (II) is conducted at 160.degree. C. or less for 0.1 to 10 hours with stirring.
- 24. A process according to claim 1, wherein the organotin halide compound is triphenyltin chloride, tributyltin chloride, triisopropyltin chloride, diphenyltin dichloride, dioctyltin dichloride, dibutyltin dichloride, phenyltin trichloride or butyltin trichloride.
- 25. A process according to claim 1, wherein the mole ratio of the organometal halide/the compound (a) is from 0.1 to 100.
Parent Case Info
This is a division of application Ser. No. 07/090,347, filed on Aug. 28, 1987 now U.S. Pat. No. 4,906,706.
US Referenced Citations (1)
Number |
Name |
Date |
Kind |
4026865 |
Uraneck |
May 1977 |
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Foreign Referenced Citations (1)
Number |
Date |
Country |
87407 |
May 1982 |
JPX |
Divisions (1)
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Number |
Date |
Country |
Parent |
90347 |
Aug 1987 |
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