JPH0768307B2 - Method for producing rubber polymer modified with silane compound - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION [Field of Industrial Application] The present invention is obtained by reacting a living polymer with a silane compound having a non-hydrolyzable alkoxy group at the active group terminal in a specific ratio. calcium,
High affinity with white fillers such as magnesium carbonate,
The present invention relates to a method for producing a silane compound-modified rubbery polymer showing good tensile properties, wear resistance and exothermic properties.

[Conventional technology]

Conventionally, a (co) polymer obtained by polymerizing a conjugated diene compound and / or a vinyl aromatic compound using an organic alkali metal catalyst in an inert organic solvent (hereinafter simply referred to as “polymer”) is Widely used as synthetic rubber or synthetic resin.

However, a vulcanized product obtained by mixing a white filler such as silica or magnesium carbonate with this polymer has a low tensile strength, and therefore a large amount of a silane coupling agent or titanium is added as a reinforcing aid for the purpose of improving the tensile strength. A coupling agent is used.

To develop a polymer that has sufficiently high tensile properties even with a vulcanizate using a white filler without using a reinforcing aid such as a silane coupling agent and has a simple manufacturing process, Introducing a functional group with good affinity for fillers such as silica into the coalescence, and this functional group is stable during polymer production and storage, and interacts with silica and filler during vulcanizate production. It is necessary.

From such a point of view, as a polymer modified with a silane compound having a high affinity for silica, for example, the following prior arts have been proposed.

That is, Japanese Patent Publication No. 49-36957 (hereinafter referred to as "Prior Art 1").
In order to improve processability, a lithium-terminated polymer obtained by polymerizing a monomer using an organolithium compound as a catalyst is added to a compound having at least three reactive sites, such as silicon tetrahalide, Silicon tetrahalides such as silicon tetrabromide and silicon tetraiodide, or trichloromethylsilane,
A method has been proposed in which a branched polymer centered on the silane compound is produced by reacting trihalosilane such as trichloroethylsilane. However, in the polymer obtained according to the prior art 1, all the halogen atom terminals bonded to the silane compound react with the lithium terminal polymer, and the functional group having reactivity with silica does not remain in the silicon atom. Therefore, the affinity for silica is low, and the tensile strength of the vulcanized product using silica as a filler is insufficient.

Further, Japanese Patent Publication No. 52-5071 (hereinafter referred to as "Prior Art 2") discloses that halogenated alkylsilane compounds, alkoxysilane compounds, halogenated compounds are used during the polymerization of monomers using an organolithium compound as a catalyst. A method for producing a silane compound-modified polymer by continuously adding a coupling agent composed of a silane compound such as a silane compound is disclosed. However, in the polymer obtained by this prior art 2, most of the halogen atoms and alkoxy groups in the silane compound react with the active end of the polymer and disappear at the end of the polymerization reaction. Even if a composition is produced by using as a filler, the affinity with silica is low, and the tensile strength of the vulcanized product using this is insufficient.

Further, JP-A-54-94597 (hereinafter referred to as "Prior Art 3") discloses a living anion obtained by polymerizing a monomer in the presence of a monoalkali metal compound, an alkoxysilane group and other reactions. A silane compound having a group (for example,
(γ-glycidyloxypropyltrimethoxysilane) is disclosed to produce a linear and / or radial polymer. However, in the prior art 3, the specific silane compound having an epoxy group and an alkoxy group has a characteristic that the coupling efficiency is good, but when considering an industrial production method, the unreacted epoxy group is not reacted. However, there is a problem that it is difficult to control the molecular weight.

Furthermore, Japanese Patent Laid-Open No. 56-104906 (hereinafter referred to as "Prior Art 4") discloses that 1 per active end of a living polymer obtained by polymerizing a monomer using an alkali metal or an organic alkali metal as a catalyst. A polymer is disclosed in which one or more molecules of a silane compound having at least two hydrolyzable functional groups in a molecule are reacted to modify only the polymer terminal with the silane compound. However, since this polymer has a hydrolyzable functional group at the terminal and has a large amount of the functional group, it easily causes a hydrolysis and a condensation reaction and becomes insoluble in an organic solvent.

For this reason, there is a fatal problem that steam solidification cannot be carried out when demolition in the manufacturing process.

Further, since this polymer is liable to undergo hydrolysis or condensation reaction, many functional groups having an affinity for silica are already lost during production, storage or compounding for obtaining a vulcanized product. However, even a vulcanized product using silica does not show sufficiently high tensile strength characteristics.

[Problems to be solved by the invention]

The present invention has been made against the background of the above-mentioned conventional technical problems, and even in a vulcanized product using a white filler such as silica, without using a reinforcing aid such as a conventional silane coupling agent, it is sufficient. An object of the present invention is to provide a method for producing a silane compound-modified rubber-like polymer which has high tensile strength, wear resistance, and good exothermic properties, is not substantially hydrolyzed by ordinary operations, and is easy to produce. To do.

[Means for solving problems]

The inventors of the present invention have made extensive studies in view of the problems of the conventional techniques, and as a result, a silane compound-modified rubber-like polymer obtained by reacting a specific silane compound with a living polymer has a functional group capable of reacting with silica or the like. To have
It has been found that the vulcanizate has a high affinity with a white filler such as silica and exhibits good tensile properties, abrasion resistance, and good exothermic properties, and has reached the present invention.

That is, the present invention relates to the active terminal 1 of a living polymer obtained by polymerizing a monomer using an organic alkali metal catalyst.
Per unit of the general formula (I) X _n Si (OR) _m R ′ _4-mn ... (I) (wherein, X is a halogen atom which is a chlorine atom, a bromine atom or an iodine atom, and R is the number of carbon atoms. A hydrocarbon group of 4 to 20, R'represents an alkyl group having 1 to 20 carbon atoms, an aryl group, a vinyl group or a halogenated alkyl group, m is an integer of 1 to 4, and n is
Is an integer of 0 to 2, and the sum of m and n is 2 to 4. )
The present invention provides a method for producing a silane compound-modified rubber-like polymer, which comprises reacting a silane compound represented by the formula at a ratio of 0.7 molecule or more.

Examples of the inert organic solvent used in the present invention include pentane, hexane, cyclohexane, heptane, benzene, xylene, toluene, tetrahydrofuran and diethyl ether.

Further, at this time, in the case of copolymerization, it is a randomizing agent, and when a conjugated diene is used as a monomer at the same time, a Lewis base is optionally used as a regulator of the microstructure of the conjugated diene. And examples thereof include dimethoxybenzene, tetrahydrofuran, dimethoxyethane, diethylene glycol dibutyl ether, diethylene glycol dimethyl ether, triethylamine, pyridine, N-methylmorpholine, N, N, N ', N'-.
Examples thereof include ethers such as tetramethylethylenediamine and 1,2-dipiperidinoethane, and tertiary amines.

The organic alkali metal catalyst used in the present invention includes n-butyllithium, sec-butyllithium and t-butyllithium.
Butyllithium, 1,4-dilithiobutane, alkyllithium such as a reaction product of butyllithium and divinylbenzene, alkylenedilithium, phenyllithium, stilbendilithium, diisopropenylbenzenedilithium, sodium naphthalene, lithium naphthalene, etc. You can

The monomer used in the present invention includes all monomers that can be subjected to living polymerization using an organic alkali metal catalyst, and examples thereof include conjugated dienes, vinyl aromatic compounds, vinyl pyridine, acrylonitrile, methacrylonitrile, and methyl metha. An acrylate, an acrylic ester, etc. can be mentioned.

Of these, conjugated dienes and / or vinyl aromatic compounds are preferred.

Here, as the conjugated diene, 1,3-butadiene, 2,3-
Dimethyl butadiene, isoprene, chloroprene, 1,3
-Pentadiene, hexadiene and the like can be mentioned, but 1,3-butadiene or isoprene is preferable from the viewpoint of easy copolymerizability with other monomers.

Such conjugated dienes can be used alone or in combination of two or more.

The repeating units of the conjugated diene are mainly as follows.

(However, R ¹ represents a hydrogen atom, a methyl group or a chlorine atom.) Examples of the aromatic vinyl compound include styrene and
Examples thereof include α-methylstyrene, p-methylstyrene, o-methylstyrene, p-butylstyrene, vinylnaphthalene, and the like, with styrene being preferred. Such aromatic vinyl compounds may be used alone or in combination of two or more.

The repeating units of the aromatic vinyl compound are mainly as follows.

(However, R ² is a hydrogen atom, an alkyl group having 1 to 10 carbon atoms,
Alternatively, it represents a halogen atom. ) In addition, the ratio when the conjugated diene and the aromatic vinyl compound are used in combination is a conjugated diene / aromatic vinyl compound (molar ratio) = 100/0 to 40/60, preferably 95/5 to 55/45. .

The method for polymerizing the living polymer used in the present invention includes a reaction system in which the polymerization system is replaced with nitrogen, an inert organic solvent used in the present invention, a monomer and an organic alkali metal catalyst, and a Lewis acid if necessary. Polymerization is carried out by adding a base all at once or intermittently or continuously.

The polymerization temperature is usually −120 to + 150 ° C., preferably −80 to
+ 120 ° C., polymerization time is usually 5 minutes to 24 hours, preferably 10 minutes to 10 hours.

Regarding the polymerization temperature, the reaction may be carried out at a constant temperature within the above temperature range, or the temperature may be elevated or the polymerization may be carried out under adiabatic conditions. Also,
The polymerization reaction may be batch type or continuous type.

The monomer concentration in the solvent is usually 5 to 50% by weight, preferably 10 to 35% by weight.

Further, in order to produce a living polymer, in order not to deactivate the organic alkali metal catalyst and the living polymer, it is necessary to mix a compound having a deactivating action such as a halogenated compound, oxygen, water or carbon dioxide gas into the polymerization system as much as possible. Care must be taken to eliminate it.

The modified rubber-like polymer obtained according to the present invention is obtained by reacting a specific silane compound with the active terminal of the living polymer thus obtained in the polymerization system, thereby substantially not hydrolyzing the Si—O—R bond ( Here, R is the same as the above, and is a modified rubbery polymer.

Here, the term "substantially does not hydrolyze" means that 60 g of a rubber sheet molded with a roll interval of 0.5 mm of a 120 ° C heat roll is charged with 3 l of warm water in a 10 l stainless steel container, and steam is blown to boil the warm water. While being left for 30 minutes, the increase in Mooney viscosity (ML _{1 + 4} , 100 ° C.) of the polymer after drying is 10 points or less, preferably 5 points or less as compared with the untreated polymer.

The silane compound to be reacted with the living polymer of the present invention is a silane compound having a non-hydrolyzable alkoxy group in one molecule and is represented by the following general formula (I).

X _n Si (OR) _m R ′ _4-mn ··· (I) (In the formula, X is a halogen atom which is a chlorine atom, a bromine atom or an iodine atom, R is a hydrocarbon group having 4 to 20 carbon atoms, That is, OR is a non-hydrolyzable alkoxy group having 4 to 20 carbon atoms, R'is an alkyl group, aryl group, vinyl group or halogenated alkyl group having 1 to 20 carbon atoms, and m is 1 to 4 , N is an integer of 0 to 2, and the sum of m and n is 2 to 4. That is, the silane compound of the present invention is an alkoxysilane compound having a non-hydrolyzable alkoxy group. Of these, R is a hydrocarbon group in which three carbon atoms are bonded to the α-position carbon or a hydrocarbon group in which one or more carbon atoms is bonded to the β-position carbon, or a phenyl group or a toluyl group. The aromatic hydrocarbon groups shown are preferred.

In R ', an alkyl group is a methyl group, an ethyl group, an n-propyl group, a t-butyl group, etc., an aryl group is a phenyl group, a toluyl group, a naphthyl group, etc., and a halogenated alkyl group is Examples thereof include a chloromethyl group, a bromomethyl group, an iodomethyl group and a chloroethyl group.

In the general formula (I), when n is 0 and m is 2, a dialkyl dialkoxy silane is used, when n is 0 and m is 3, a monoalkyl trialkoxy silane is used, and when n is 0 and m is 4, tetra is used. Alkoxysilane, when n is 1 and m is 1, monohalogenated dialkylmonoalkoxysilane, n
Is 1 and m is 2, a monohalogenated monoalkyl dialkoxysilane, a monohalogenated trialkoxysilane when n is 1 and m is 3, and a dihalogenated monoalkyl mono is n is 2 and m is 1. Alkoxysilane, when n is 2 and m is 2, it is a dihalogenated dialkoxysilane, both of which are reactive with the active end of the living polymer.

In particular, a monoalkyltrialkoxysilane in which n is 0 and m is 3, a tetraalkoxysilane in which n is 0 and m is 4, and a monohalogenated monoalkyldialkoxysilane in which n is 1 and m is 2 is living. It is preferable from the viewpoint of improving processability by coupling a polymer and imparting a functional group having a high affinity with silica or the like to the polymer.

Specific examples of the silane compound represented by the general formula (I) used in the present invention include, for example, tetrakis (2-ethylhexyloxy) silane, tetraphenoxysilane,
Methyltris (2-ethylhexyloxy) silane, ethyltris (2-ethylhexyloxy) silane, ethyltriphenoxysilane, vinyltris (2-ethylhexyloxy) silane, vinyltriphenoxysilane,
Methylvinylbis (2-ethylhexyloxy) silane, ethylvinyldiphenoxysilane, tri-t-butoxymonochlorosilane, triphenoxymonochlorosilane, monochloromethyldiphenoxysilane, monochloromethylbis (2-ethylhexyloxy) silane, monobromo Ethyldiphenoxysilane, monobromovinyldiphenoxysilane, monobromoisopropenylbis (2-
Ethylhexyloxy) silane, dichloro-di-t-butoxysilane, ditolyldichlorosilane, di-t-butoxydiiodosilane, diphenoxydiiodosilane, methyltris (2-methylbutoxy) silane, vinyltris (2-methylbutoxy) silane , Monochloromethylbis (2-methylbutoxy) silane, vinyltris (3-
Methyl butoxy) silane etc. can be mentioned.

Among these silane compounds, n is a silane compound having 0 or 1, and among these, monochloromethyldiphenoxysilane and vinyltris (2-ethylhexyloxy)
Silane and monochlorovinylbis (2-ethylhexyloxy) silane are preferred. These silane compounds are 1
They can be used alone or in combination of two or more.

In the present invention, the silane compound represented by the general formula (I) is reacted with the active end of the living polymer, and the amount of the silane compound used at this time is preferably 0.7 molecule per active end of the living polymer. Or more, preferably 0.7
~ 5.0, more preferably obtained by reacting 0.7 to 2.0 molecules, less than 0.7 mol of the branched polymer is often generated, the fluctuation of the molecular weight distribution is large, it becomes difficult to control the molecular weight and the molecular weight distribution, 5.0 mol If it exceeds, the effect of improving the physical properties is saturated, which is not economically preferable.

At this time, a small amount of a silane compound is first added to the active end of the living polymer to form a polymer having a branched structure, and then the remaining active end is further modified with another silane compound. Stage addition is also possible.

In the present invention, the reaction between the active end of the living polymer and the silane compound having a functional group is carried out by adding the compound to a solution of the living polymer in the polymerization system or by adding the living polymer to an organic solution containing the silane compound. It is carried out by adding a solution.

The reaction temperature is −120 to + 150 ° C., preferably −80 to +120.
The reaction time is 1 minute to 5 hours, preferably 5 minutes to 2 hours.

After completion of the reaction, steam is blown into the polymer solution to remove the solvent, or a poor solvent such as methanol is added to solidify the silane compound-modified polymer, and the silane compound-modified rubber is dried by heating on a hot roll or under reduced pressure. Polymers can be obtained.

Further, the solvent may be directly removed from the polymer solution under reduced pressure to obtain a silane compound-modified rubbery polymer.

The molecular weight of the silane compound-modified rubber-like polymer of the present invention can be varied over a wide range, but its Mooney viscosity (ML _{1 + 4} , 100 ° C.) is usually 10 to 150,
It is preferably in the range of 10 to 100.

When the silane compound-modified rubbery polymer obtained by the present invention is a copolymer, it may be a block copolymer or a random copolymer according to the structure of the living polymer.

The silane compound-modified rubber-like polymer obtained by the present invention has, for example, an infrared absorption spectrum, an absorption near 1,100 cm ⁻¹ due to a Si—O—C bond and a 1,250 cm due to a Si—O—φ bond. cm ^-1 vicinity absorption, or the like absorption around 1,160Cm ^-1 attributable to Si-C bonds, it is possible to confirm the structure.

Thus, the silane compound-modified rubber-like polymer obtained by the present invention can be used alone or in a blend with another diene rubber, but in this case, it is necessary to contain the polymer of the present invention in an amount of 20% by weight or more. Is. If it is less than 20% by weight, the effect of improving the reinforcing effect of the filler is not recognized.

Other diene rubbers include natural rubber, cis-1,4 polyisoprene, emulsion polymerization styrene-butadiene copolymer, solution polymerization styrene-butadiene copolymer, low cis-1,4 polybutadiene, high cis- 1,4 polybutadiene,
Ethylene propylene diene copolymer, chloroprene, halogenated butyl rubber, NBR, etc. can be blended and used.

The amount of the inorganic filler to be added to the rubber component containing the silane compound-modified rubbery polymer of the present invention is 10 to 100 parts by weight with respect to 100 parts by weight of the rubber component, and the filler reinforcing effect is less than 10 parts by weight. On the other hand, if the amount is less than 100 parts by weight, the workability and fracture properties are poor, which is not preferable. Examples of the inorganic filler include white fillers such as silica, magnesium carbonate, calcium carbonate, and glass fiber, in addition to carbon black.

If necessary, oil-extend with an aromatic, naphthenic, paraffinic, etc. oil, and then add ordinary vulcanized rubber compounding agents such as stearic acid, zinc white, antioxidants, vulcanization accelerators and vulcanizing agents. It can be a composition.

In the composition, dibutyltin diacetate, dibutyltin dioctoate, dibutyltin laurate, stannous acetate, ferrous octoate, lead naphthenate, zinc caprylate, which are known as silanol condensing agents, 2 -Ethylhexane iron, cobalt naphthenate, titanate ester,
A chelate compound may be added.

The composition obtained is vulcanized after molding, and is used for tires such as treads, undertreads, sidewalls and beet parts, hoses, belts, shoe soles, window frames,
It can be used for applications such as sealants and other industrial products.

〔Example〕

Hereinafter, the present invention will be described in more detail with reference to Examples, but the present invention is not limited to the following Examples without departing from the gist thereof.

In the examples, parts and% mean parts by weight and% by weight unless otherwise specified.

Further, various measurements in the examples were based on the following methods.

That is, the reaction between the active end of the living polymer and the silane compound was confirmed by the change in Mooney viscosity and the change in infrared absorption spectrum of the copolymer before and after the reaction.

The Mooney viscosity was measured by preheating for 1 minute, measurement for 4 minutes, and temperature at 100 ° C.

The microstructure of the butadiene portion was determined by the infrared absorption spectrum method (Morero method).

The styrene content was measured by an infrared absorption spectrum method based on the absorption of a phenyl group at 699 cm ^-1 according to a calibration curve previously obtained.

Glass transition temperature (Tg) is low temperature DSC manufactured by Rigaku Denki Co., Ltd.
Main body; CN8208A2 type, low temperature DSC, DTA, UNIT; CN8059L2 type, and program temperature controller PTC-10A type were used, and measurement was carried out according to a previously determined calibration curve.

The vulcanized physical properties were measured according to JIS K6301.

The Lambourn abrasion index, which is an abrasion resistance test, was measured by the Lambourn abrasion method. The measurement conditions are a load of 4.5 kg,
The surface velocity of the grindstone was 100 m / sec, the test piece velocity was 130 m / sec, the slip ratio was 30%, the amount of sand fall was 20 g / min, and the measurement temperature was room temperature.

In Table 1, the Lambourn abrasion index is shown by setting the styrene-butadiene copolymer (vinyl content = 60%, styrene content = 20%) unmodified to a silicon compound as 100. The larger the value, the better the abrasion resistance. In Table 2, the Lambourn wear amount is shown by the volume of the vulcanized rubber worn per unit time in the wear resistance test. The larger the value, the better the abrasion resistance. In addition, in Table 2, the slip ratio is shown as data of 20% and 30%.

The impact resilience (%) by the Dunlop impact resilience test was used as an index of heat generation characteristics. The larger the value is, the less the heat is generated, and the better.

Example 1 An autoclave with an internal volume of 5 l equipped with a stirrer and a jacket was dried and replaced with nitrogen. Pre-purified and dried cyclohexane 2,500g, styrene 100g, 1,
400 g of 3-butadiene and 25 g of tetrahydrofuran were introduced. Then, the temperature inside the autoclave was adjusted to 10 ° C., the cooling water was stopped while stirring at 2 revolutions per minute, 0.300 g of n-butyllithium was added, and polymerization was carried out for 30 minutes. A part of this polymer solution was taken out and the Mooney viscosity (ML _{1 + 4} , 100
It was 12 when measured.

Next, to the remaining polymer solution, 9.38 ml of monochloromethyldiphenoxysilane in cyclohexane (concentration 0.50 mol
The molar ratio of monochloromethyldiphenoxysilane to / l, n-butyllithium corresponds to 1.00. ) Was added, the yellow color of the living anion disappeared and the solution viscosity increased. Furthermore, the reaction was carried out at 50 ° C for 30 minutes. After a predetermined time, 0.7 g of 2,6-di-t-butylphenol (BHT) was added to 100 g of the polymer, the solution was removed with steam, and the solution was dried with a hot roll at 100 ° C. The polymer yield was obtained almost quantitatively. The polymer yield was also quantitative in the following examples.

This polymer had no insoluble matter when dissolved in tetrahydrofuran. In addition, in the infrared absorption spectrum of this modified polymer, absorption based on the Si—O—φ bond was present at 1250 cm ⁻¹ .

On the other hand, as described above, when molded with a hot roll and subjected to steam heat treatment under the same conditions as described above, the Mooney viscosity is
43 was almost the same as before the treatment.

This silane compound-modified rubbery polymer was vulcanized with the following formulation to evaluate the physical properties.

That is, polymer, silica, DBTD on a hot roll at 145 ° C
L, stearic acid, zinc oxide are pre-kneaded and then 50
The remaining compounding ingredients were kneaded with a roll at ℃.

The compound was molded and press vulcanized at 145 ° C. Vulcanization was performed by the same method in all of the following examples. The results are shown in Table 1. Formulation (part) Polymer 100 Silica 40 (Nipsil VN3, manufactured by Nippon Silica Co., Ltd.) Stearic acid 2 Zinc oxide 3 Anti-aging agent: 810NA ^{* 1} 1 〃 TP ^{* 2} 0.8 Vulcanization accelerator; D ^{* 3} 0.6 〃 DM ^{* 4} 1.2 Triethanolamine 1.5 Sulfur 1.5 DBTDL ^{* 5} 1.0 Total 151.1 * 1) N-phenyl-N'-isopropyl-p-phenylenediamine * 2) Sodium dibutyldithiocarbamate * 3) Diphenylguanidine * 4) Dibenzothiazyl Disulfide * 5) Dibutyltin dilaurate Comparative Examples 1 and 2 Same as Example 1 except that tetrachlorosilane (Comparative Example 1) and methyltriethoxysilane (Comparative Example 2) were used instead of monochloromethyldiphenoxysilane. A polymer was produced. Table 1 shows the polymerization results and the vulcanized physical properties of the obtained polymer.

From Example 1 and Comparative Examples 1 and 2, it can be seen that monochloromethyldiphenoxysilane specifically acts to improve the tensile strength and the Lambourn abrasion index.

Example 2 Styrene was prepared in the same manner as in Example 1 except that the amount of monochloromethyldiphenoxysila used in Example 1 was doubled.
The butadiene copolymer was modified. Table 1 shows the results of the polymerization and the vulcanization properties of the obtained rubber-like polymer.

Examples 3 to 5 Instead of the monochloromethyldiphenoxysilane of Example 1, vinyltris (2-ethylhexyloxy) silane (Example 3), monochlorovinyl (2-ethylhexyloxy) silane (Example 4), tetraphenoxysilane. Example 1 except that was used in a double molar amount (Example 5).
The styrene-butadiene copolymer was modified in the same manner as in. Table 1 shows the polymerization results and the vulcanized physical properties of the obtained polymer.

Examples 6 to 7 The styrene-butadiene copolymer was modified in the same manner as in Example 1 except that the charged amount of styrene was halved (Example 6). Further, the modification of the styrene-butadiene polymer was performed in the same manner as in Example 1 except that the amount of tetrahydrofuran in Example 1 was reduced and styrene was not used (Example 7).
Table 1 shows the results of the polymerization and the vulcanization properties of the obtained polymer.

Comparative Example 3 A styrene-butadiene copolymer was modified in the same manner as in Example 1 except that the amount of monochloromethyldiphenoxysilane used in Example 1 was 0.30 times the molar amount of the n-butyllithium used. It was Table 1 shows the results of the polymerization and the vulcanization properties of the obtained rubber-like polymer.

Comparative Example 4 A polymer similar to that of Example 1 was produced except that methyltri-n-propoxysilane was used instead of the monochloromethyldiphenoxysilane of Example 1. The polymerization results are shown in Table 1.

It can be seen that the obtained polymer is hydrolyzed by steam treatment to increase the Mooney viscosity, and the produced rubber is highly hydrolyzable.

Example 8 After producing a living polymer in the same manner as in Example 1, tetraphenoxysilane (0.188 g; the molar ratio of tetraphenoxysilane to n-butyllithium corresponds to 0.10) was gradually added, and after 30 minutes. A silane compound-modified rubbery polymer was prepared by adding 9.38 ml of a cyclohexane solution of monochloromethyldiphenoxysilane (concentration: 0.50 mol / l, the molar ratio of monochlorodiphenoxysilane to n-butyllithium is 1.00). did. Table 1 shows the polymerization results and the vulcanized physical properties of the obtained polymer.

Example 9 The silane compound-modified rubber-like polymer (A
-1) 80%, except that (A-
20% of rubber-like polymer (B-1) obtained in the same manner as 1)
Compounding and vulcanization were carried out in the same manner as in Example 1 using the rubber component consisting of, and the physical properties were evaluated. The results are shown in Table 2.

The rubbery polymer (B-1) had a Mooney viscosity (ML
_{1 + 4} , 100 ° C) 32, vinyl bond content 61%, styrene content 21
%Met.

When the silane compound-modified rubbery polymer was blended with another polymer for evaluation, only the silane compound-modified rubbery polymer and silica were kneaded and then used for preliminary kneading. The same applies to the following examples.

Example 10 The silane compound-modified rubbery polymer (A
-1) The same compounding and vulcanization as in Example 1 was carried out using a rubber component consisting of 20% and 80% of a commercially available emulsion-polymerized styrene-butadiene copolymer (JSR 1,500 manufactured by Japan Synthetic Rubber Co., Ltd.). The physical properties were evaluated. The results are shown in Table 2.

Example 11 50% of a rubber-like polymer (A-2) obtained according to the rubber-like polymer (A-1) except that the vinyl bond content was 30% and the styrene content was 0%. Using a rubber component consisting of 50% of cis-1,4 polybutadiene (JSR BR01 manufactured by Japan Synthetic Rubber Co., Ltd.), the same compounding and vulcanization as in Example 1 was carried out,
Physical properties were evaluated. The results are shown in Table 2.

Example 12 Except that the compounding amount of silica was changed from 40 parts to 70 parts, compounding and vulcanization were carried out in accordance with Example 1 and physical properties were evaluated. The results are shown in Table 2.

[Effect of the invention] The present invention is a coupling reaction by adding a specific amount of a specific silane compound to a living polymer obtained by polymerizing a monomer using an organic alkali metal catalyst, and substantially not hydrolyzing Si A method for producing a silane compound-modified rubbery polymer having an —O—R bond, wherein the obtained silane compound-modified rubbery polymer is a compound of a white filler such as silica, which has hitherto been unable to obtain high tensile strength. Also exhibits high tensile strength, and as a result, it is possible to provide a vulcanized product having high tensile strength capable of coloring, good abrasion resistance, and exothermic properties.

Claims (4)

[Claims] 1. A living polymer obtained by polymerizing a monomer using an organic alkali metal catalyst, has a compound represented by the general formula (I) X _n Si (OR) _m R ′ _4-mn ... (I) (wherein X is a halogen atom which is a chlorine atom, a bromine atom or an iodine atom, R is a hydrocarbon group having 4 to 20 carbon atoms, R'is an alkyl group or aryl group having 1 to 20 carbon atoms, Represents a vinyl group or a halogenated alkyl group, m is an integer of 1 to 4, and n
Is an integer of 0 to 2 and the sum of m and n is 2 to 4), and a silane compound-modified rubbery polymer is produced by reacting the silane compound at a ratio of 0.7 molecule or more. Law. 2. The method for producing a silane compound-modified rubbery polymer according to claim 1, wherein the monomer is a conjugated diene compound and / or a vinyl aromatic compound. 3. An n of a silane compound represented by the general formula (I).
The method for producing a silane compound-modified rubber polymer according to claim 1 or 2, wherein is 0 or 1. 4. R of the silane compound represented by the general formula (I).
Is a hydrocarbon group in which three carbon atoms are bonded to the α-position carbon, β
A hydrocarbon group in which one or more hydrocarbon groups have one or more carbon atoms bonded to the carbon at the position, or an aromatic hydrocarbon group represented by a phenyl group or a toluyl group.
A method for producing the silane compound-modified rubber-like polymer according to item 2 or 3.