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US5064910A
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Preparation of conjugated diene polymers modified with an organo-tin or germanium halide
Assignee: JSR Corp
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Filing: 1989-12-11
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Granted: 1991-11-12
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Expires: 2009-12-11
Abstract
Abstract 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 element compound, (b) an organoaluminum compound represented by the general formula, AlR1R2R3 (wherein R1, R2 and R3 which may be same or different, are hydrogen atoms or hydrocarbon groups of 1 to 8 carbon atoms and at least one of R1, R2 and R3 is said hydrocarbon group) and, if necessary, at least one member selected from the group consisting of (c) a Lewis acid and/or (d) a Lewis base, and then (II) modifying the resulting reactive polymer with a modifying compound of the general formula, R4nMX4-n (wherein R4 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).
Inventors
- 👤 Iwakazu Hattori
- 👤 Mitsuhiko Sakakibara
- 👤 Fumio Tsutsumi
- 👤 Masao Yoshizawa
Bibliographic Details
Application Number
—
Jurisdiction
US
Data Source
google_patents
Last Synchronized
2026-11-08 03:27
CPC Classifications
C; C08; C08C; C08C19/00; C08F; C08F36/00; C08F36/02; C08F36/04
Claims Analysis
Total Claims: 26
Claim 1
Independent Claim
173 words
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 1 R 2 R 3 (wherein R 1 , R 2 and R 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 1 , R 2 and R 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 4 n MX 4-n (wherein R 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),
Claim 2
Dependent Claim
173 words
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 1 R 2 R 3 (wherein R 1 , R 2 and R 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 1 , R 2 and R 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 4 n MX 4-n (wherein R 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),
Claim 3
Dependent Claim
17 words
A process according to claim 1, wherein the conjugated diene is 1,3-butadiene, isoprene or a mixture thereof.
Claim 4
Dependent Claim
77 words
A process according to claim 1, wherein the lanthanum series rare earth element compound (a) is a compound represented by the general formula, LnY 2 3 (wherein Ln is at least one lanthanum series rare earth element having an atomic number of 57 to 71 and Y 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.
Claim 5
Dependent Claim
25 words
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.
Claim 6
Dependent Claim
11 words
A process according to claim 3, wherein the Ln is neodymium.
Claim 7
Dependent Claim
74 words
A process according to claim 3, wherein the LnY 2 3 compound is a compound represented by the general formula, LnR 3 , Ln(OR) 3 , Ln(SR) 3 , Ln(NR 2 ) 3 , ##STR12## LnX 3 or (RCOO) 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).
Claim 8
Dependent Claim
67 words
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.
Claim 9
Dependent Claim
32 words
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.
Claim 10
Dependent Claim
68 words
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 5 m X 3-m (wherein R 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.
Claim 11
Dependent Claim
35 words
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.
Claim 12
Dependent Claim
34 words
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.
Claim 13
Dependent Claim
20 words
A process according to claim 1, wherein the mole ratio of the component (b)/the component (a) is 10 to 150.
Claim 14
Dependent Claim
20 words
A process according to claim 1, wherein the mole ratio of the component (b)/the component (a) is 15 to 100.
Claim 15
Dependent Claim
18 words
A process according to claim 12, wherein the catalyst consists of the component (a) and the component (b).
Claim 16
Dependent Claim
21 words
A process according to claim 12, wherein the mole ratio of the component (c)/the component (a) is from 0 to 6.
Claim 17
Dependent Claim
21 words
A process according to claim 13, wherein the mole ratio of the component (c)/the component (a) is from 0.5 to 5.0.
Claim 18
Dependent Claim
21 words
A process according to claim 12, wherein the mole ratio of the component (d)/the component (a) is from 0 to 20.
Claim 19
Dependent Claim
21 words
A process according to claim 13, wherein the mole ratio of the component (d)/the component (a) is from 1 to 15.
Claim 20
Dependent Claim
43 words
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.
Claim 21
Dependent Claim
30 words
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.
Claim 22
Dependent Claim
21 words
A process according to claim 1, wherein the polymerization in the step (I) is conducted at -20° C. to 150° C.
Claim 23
Dependent Claim
19 words
A process according to claim 20, wherein the monomer concentration in the solvent is 5 to 50% by weight.
Claim 24
Dependent Claim
27 words
A process according to claim 1, wherein the modification in the step (II) is conducted at 160° C. or less for 0.1 to 10 hours with stirring.
Claim 25
Dependent Claim
29 words
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.
Claim 26
Dependent Claim
21 words
A process according to claim 1, wherein the mole ratio of the organometal halide/the compound (a) is from 0.1 to 100.
References Cited (Backward Citations)
US4026865A
Cited
JPS5787407A
Cited
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