JPS591513A - Production of branched conjugated diene polymer - Google Patents

Abstract

PURPOSE:To produce the titled high-hardness, high-modulus polymer, by polymerizing a conjugated diene with the aid of an organolithium compound initiator in a hydrocarbon solvent in the presence of an ether or a tert. amine and then coupling the resulting polymer with a specified organotin compound. CONSTITUTION:100pts.wt. conjugated diene (e.g., butadiene) or monomer mixture of this monomer and a vinylaromatic compound (e.g., styrene) is dissolved in 200-2,000pts.wt. hydrocarbon solvent (e.g., pentane), and (co)polymerized at -20-150 deg.C with the aid of an organolithium compound initiator (e.g., ethyllithium) in the presence of an ether (e.g., diethyl ether) and/or a tert. amine (e.g., pyridine). The produced (co)polymer is coupled at 0-150 deg.C with an organotin compund of the formula, wherein R<1-4> are each aryl, phenyl, phenyl- substituted methyl or cyclopentadienyl.

Description

DETAILED DESCRIPTION OF THE INVENTION The present invention relates to a method for producing a rubber-like branched conjugated diene polymer, which is characterized by using a novel organotin compound as a coupling agent.

Furthermore, the polymerization of a conjugated diene or the copolymerization of a conjugated diene and a vinyl aromatic compound is carried out in a hydrocarbon solvent using an IJ tium compound as an initiator in the presence of an ether or a tertiary aban. After Shimata.

The coupling reaction is carried out with an organotin compound represented by the general formula S n R'R"R"R' (where RIR2RIR4 is a group selected from an aryl group, a phenyl-substituted methyl group, and a cyclopentadienyl group). The present invention relates to a method for producing a branched conjugated diene polymer called I\fIlk.

As a method for producing a branched polymer bonded by tin-charcoal purple bonds, a conventional method was disclosed in Japanese Patent Publication No. 41-9433. % Kosho 44-4996
The use of tin compounds such as vinyl tin compounds, allyl tin compounds, halogenated tin compounds, sialtyl tin oxide compounds, and alkyl alkoxy tin compounds is known, as shown in the following, but the tetraaryl tin compounds shown in the present invention, Tetraalkylaryltin compounds.

By using known tin compounds such as tetraphenyl-substituted methyltin compounds, properties such as breaking strength, 9 impact resilience, etc., which are useful as rubber phase materials for tires, are impaired, and properties such as high hardness, high modicolus, and branched steel are formed. 82 diene polymer can be obtained.

Carbohydrate army? Polymerization of a conjugated diene in the presence of an ether or tertiary amine using an organolithium compound as an initiator in i4 medium or a conjugated diene and a vinyl aromatic compound (50% by weight based on the content of the vinyl aromatic compound in the shell) After carrying out both of the following).

General formula S n R'R"R"R' (R1, Rm
Rq loss is an aryl group, a phenyl-substituted methyl group.

f'
It is obtained by performing a coupling reaction with a ditin tin compound. Examples of the conjugated diene include 1,3-butadiene and imprene, but 1,3-butadiene is preferred. Vinyl aromatic compounds and R7 include styrene and vinyltoluene.

Compounds such as P-methylstyrene, 0-methylstyrene, m-methylstyrene, r-ethylstyrene, and m-ethylstyrene vinylnaphthalene are used.

Pentane, hexane, heptane, octane, methylpentane, cyclohexane as hydrocarbon carriers.

Compounds such as benzene, xylene, toluene, etc. are used, and 1 part by weight of 200 to 2,000 parts per 100 m+##a of monomers is used.

Fact 4: Ih starting M organic lithium compounds include ethyllithium, propyllithium, butyllithium, amyllithium, 1.4-dilithiobutane, 1.5-dilithiopentane, phenyllithium, 1.3-bis(1-IJthio-3 -methylpentyl)benzene.

1.3-bis(1-lithio-1,3-dimethylpentyl)benzene, 1.1.4.4-tetraphenyl-1,4
- Compounds such as dirithiobutane are used,
It is used in a range of 0.02 to 5*iit parts per 00 parts by weight.

Ethers or tertiary amines are necessary not only as randomizing agents for styrene-butadiene, but also because they can increase the coupling efficiency in the coupling reaction.

As ethers, diethyl ether, dibutyl ether,
Dioctyl ether, tetrahydrofuran.

Compounds such as dioxane, aninyl dimethoxybenzene, 2-methoxymethyltetrahydrofuran, ethylene glycol dimethyl ether, ethylene glycol dibutyl ether, and diethylene glycol dimethyl ether are used, and as tertiary amines, triethylamine, pyridine, N-methylmorpholine, and triethylene diamine are used. , NNN'N'-tetramethylethylenediamine,
Compounds such as 1,2 dibiberazinoethane are used.

The river of 1 tertiary amine in ether is 1 tL it t
4: Used in a range of 0.01 to 50' per 100 parts by weight.

M1 polymerization degree is -20~150C, preferably 0~120
It may be carried out at a static temperature or at an elevated temperature within the range of C.

The present tin compound 11 used in the coupling reaction of the present invention has the general formula Sn R'lt"R3R' (R7R5R
B, R'&: 1 aryl group, phenyl? A compound represented by a group selected from a substituted methyl group and a cyclopentagenyl group.

RI R2R3R4 carbon'&! ! , is preferably 5 to 12. Specifically, tetraphenyltin and tetraxyltin.

Tetratolyltin, tetraethylphenyltin.

Examples include compounds such as tetranaphthyltin, tetrabenzyltin, tetrabiphenylmethyltin, and detracyclobentadienyltin.

An analogy for organotin compounds is organolithium initiator lithium 11
01 to 5 mol per 9 children, preferably ij 0
．． It is used in a range of 5 to 1.5 moles. If it deviates from this range by 6, the impact elasticity and tensile strength will be poor, so it is not preferable [7 is not acceptable].

In the case of styrene and butadiene copolymerization, the coupling reaction can be effectively carried out by adding 1 to 20 moles of 1,3-butadiene per 1 atom of lithium organolithium initiator to the side where the organotin compound is added. It is done.

Coupling reaction: 0-150°C, preferably 30-1
It is carried out in the range of 20C.

The d-coupling reaction substantially occurs under ocgr.
50C or higher is not preferable because the active cylindrical end is deactivated.

The branched butadiene polymer obtained by the method of the present invention has a bonded vinyl aromatic compound content of 50% by weight or less, or at least 20% more than the proportion l of the branched polymer in the dipolymer,
The vinyl content of the butadiene moiety is 30-95%, Mooney viscosity [10-1501 preferably t'Lt 20-]0
The V combination of 0 has particularly high destructive strength.

Anti-J^elastic VC superior t1. Due to its high strength, hardness, and high modulus, it can be suitably used as a rubber material for tire treads.

The present invention will be comprehensively illustrated and illustrated by the following examples, but the present invention is not intended to be limited by these examples as long as they do not go beyond the gist thereof.

In each implementation mode, the method of infrared absorption of Molecuchi et al. (cbim e ind 417
58 (1959)).

The content of bonded vinyl aromatic 4r compound '11 is 100 M
It was determined from H2H-NMR. The proportion of the branched polymer in the polymer was determined from the proportion of the part on the madder molecule side in a Gelbermiesian solar chromatograph.

After vulcanization, for every 100 parts of rVi polymer, 50 parts of HAF carbon, 2 parts of stearin, 3 parts of zinc, anti-aging agent N-phenyl-R-isopropyl-P-
Phenyldiamine 111fm.

(iN general rule N-cyclohexyl-2-benzothiacylsulfenamide 06 parts by weight, 2-mercaptobenzothiazole 0.6 parts by weight, 1,3-diphenylguanidine 04 parts by weight, sulfur 1.5 parts by weight) using the part.

Mixed and blended with Brabender and roll, 145C2
It was obtained by vulcanization for 5 minutes.

The tensile test was measured according to JIS K6301.

Repulsion was measured using a Dunlop trypsometer.

Measured at 70C.

Example 1 7! A reactor was charged with 2250P of cyclohexane, 37Off of 1,3-butadiene, 125I of styrene, and 11.25Y of tetrahydrofuran, adjusted to 20C, drained, and 0.32I of n-butyllithium was added to initiate polymerization. After 35 minutes, the combined temperature HX F'i reached 900 due to heat storage, and the single polymerization conversion rate was 100%.

1.3-Butadiene 5Pt was added, and after 10 minutes, tetravinyltin in tetrahydrofuran was added at 85C for 30 minutes.

After adding 26-ditardiarypteru-P-cresol 25z to the 111 combined solution, the solvent was removed and dried to obtain a polymer. The properties of the 1″ coalescence and the properties of the vulcanizate are shown in Table 1.

Ratio 1k12 fpil 1 Example 1 except that 0.18 p'i of tetrachlorotin was used instead of detraphenyltin o and 4aP flJ
A polymer having the same proportion of the branched polymer as in Example 1 was obtained by carrying out the same procedure as in Example 1.

The properties of the polymer and of the vulcanizate are shown in Table 1.

2500 f of n-hexane, 50 (1 f) of n-hexane, 50 (1 f) of n-hexane, and 7.5 mm of tetrahydrofuran were charged into a reactor of 27.0 C, and after adjusting the temperature to 30 C, n-butyl lithium was added to 0.0 C of n-hexane.
30 Lt was added to start polymerization. After 35 minutes, the polymerization temperature reached 100 C due to heat accumulation.

The polymerization conversion rate was determined to be 100% by solid content measurement.

Tetrabenzyltin dissolved in tetrahydrofuran2.
26fi' was added and the coupling reaction was carried out for 30 minutes. Add 26-ditark-yarypteru-P- to the polymer bath solution.
After adding 2.5 Pk of cresol, the solvent was removed and dried to obtain a polymer.

The properties of the polymer and the properties of the vulcanizate fjM are shown in Table 1.

Ratio V, Example 2 Example 2 Example 2 except that 1.067'i of tetravinyltin was used instead of tetrabenzyltin 2.26) in Example 2 and the branched polymer in the polymer in &+12. Polymers with the same percentage of coalescence were obtained.

The properties of the polymer and of the vulcanizate are shown in Table 1.

Claims (1)

[Claims] (1) After polymerizing a conjugated diene or a conjugated diene and a vinyl aromatic compound in a hydrocarbon solvent using an organolithium compound as an initiator in the presence of an ether or a tertiary amine, the general formula S nR'RlR''R' (in the formula R1, R''
, R3, I-4 are groups selected from an aryl group, a phenyl-substituted methyl group, and a cyclopentadienyl group). Method for producing a polymer.