JPH0651746B2 - Method for producing silane compound-modified polymer - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION [Field of Industrial Application] The present invention is obtained by reacting a specific silane compound with an active group terminal of a living polymer, and a white filler such as silica, calcium carbonate or magnesium carbonate. The present invention relates to a method for producing a silane compound-modified polymer which has a high affinity with, and exhibits good tensile properties and wear resistance.

[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 filler 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 this 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, JP-B-49-36957 (hereinafter referred to as "Prior Art 1") discloses a lithium-terminated polymer obtained by polymerizing a monomer using an organolithium compound as a catalyst for the purpose of improving processability. A compound having at least three reactive sites, for example, a silicon tetrahalide such as silicon tetrahalide, silicon tetrabromide or silicon tetraiodide, or a trihalosilane such as trichloromethylsilane or trichloroethylsilane. A method of forming a branched polymer centered on a compound has been proposed. However, in the polymer obtained by the prior art 1, all the halogen atom terminals bonded to the silane compound react with the lithium terminal polymer, and a 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 a halogenated alkylsilane compound, an alkoxysilane compound, and a halogenated silane compound are used during the polymerization of a monomer using an organolithium catalyst. A method for producing a silane compound-modified polymer by continuously adding a coupling agent composed of a silane compound such as

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-56-104906 (hereinafter referred to as "Prior Art 3") discloses one molecule per active end of a living polymer obtained by polymerizing a monomer using an alkali metal or an organic alkali metal as a catalyst. At least 2 in
Disclosed is a polymer in which one or more molecules of a silane compound having one hydrolyzable functional group 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 hydrolysis and condensation reactions 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. It is an object of the present invention to provide a method for producing a silane compound-modified polymer which has high tensile strength and abrasion resistance, is not substantially hydrolyzed by ordinary operations, and is easy to produce.

[Means for solving problems]

The inventors of the present invention have made extensive studies in view of the above-mentioned problems of the prior art, and a silane compound-modified polymer obtained by reacting a specific silane compound with a living polymer at a specific ratio,
Since it has a specific amount of a functional group capable of reacting with silica or the like, it has high affinity with a white filler such as silica, and this vulcanized product has been found to exhibit good tensile properties, and has arrived at the present invention. .

That is, according to the present invention, per one active end of a liming polymer obtained by polymerizing a monomer in an inert organic solvent using an organic alkali metal catalyst, a compound represented by the general formula (I) X _n Si (OR) _{4 -n} ... (I) (In the formula, X represents a halogen atom which is a chlorine atom, a bromine atom or an iodine atom, R is a hydrocarbon group having 1 to 20 carbon atoms, and n is 0 to (Representing an integer of 2) by reacting a silane compound represented by the ratio of 0.4 to 0.6 molecule,
It is intended to provide a method for producing a silane compound-modified polymer having a Si—O—R bond which couples two molecules of living polymer and which does not substantially hydrolyze.

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 dimethoxydibenzene, tetrahydrofuran, dimethoxyethane, diethylene glycol dibutyl ether,
Diethylene glycol dimethyl ether, triethylamine, pyridine, N-methylmorpholine, N, N,
N ', N'-tetramethylethylenediamine, 1,2-
Examples thereof include ethers such as dipiperidinoethane and tertiary amines.

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

The monomer used in the present invention includes all monomers that can be living polymerized using an organometallic catalyst, for example, conjugated dienes, vinyl aromatic compounds, vinyl pyridine, acrylonitrile, methacrylonitrile, methyl methacrylate. , Acrylic acid ester, and the like.

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

Here, as the conjugated diene, 1,3-butadiene,
2,3-dimethylbutadiene, isoprene, chloroprene, 1,3-pentadiene, hexadiene and the like can be mentioned, but 1,3-dimethylbutadiene is easily copolymerizable with other monomers.
Butadiene or isoprene are preferred.

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 represents a hydrogen atom, an alkyl group having 1 to 10 carbon atoms, or a halogen atom.) The ratio when the conjugated diene and the aromatic vinyl compound are used in combination is the 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,
It is 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 polymer of the present invention is substantially hydrolyzed by reacting a specific amount of a specific silane compound with the active terminal of the living polymer thus obtained in the polymerization system and coupling two molecules of the living polymer. Si-not decomposed
It is a polymer having an OR bond. The silane compound reacted with the living polymer of the present invention is a silane compound having four functional groups in one molecule and is represented by the following general formula (I).

X _n Si (OR) _4-n ... (I) (In the formula, X represents a halogen atom which is a chlorine atom, a bromine atom or an iodine atom, and R represents a carbon atom having 1 to 20 carbon atoms. That is, the hydrogen group, n represents an integer of 0 to 2) That is, the silane compound of the present invention is an alkoxysilane compound that may have a halogen atom, and among these, R has three carbon atoms bonded to the α-position carbon. And a hydrocarbon group in which a hydrocarbon group having 2 or more carbon atoms is bonded to the β-position carbon, or an aromatic hydrocarbon group represented by a phenyl group or a toluyl group. Also, n is 0
In the case of, tetraalkoxysilane, when n is 1, it is a monohalogenated triacylsilane, and when n is 2,
In the case of, it is a dihalogenated dialkoxysilane, and any functional group is a compound having reactivity with the active end of the living polymer.

Particularly, a dihalogenated dialkoxysilane in which n is 2 is preferable from the viewpoint of improving processability by coupling a living polymer and imparting a functional group having a high affinity with silica or the like to the polymer.

As described above, the number of halogen atoms in the general formula (that is, n) is 2 or less. That is, the silicon-halogen atom bond of the silane compound of the present invention has high reactivity and reacts with the living polymer prior to the alkoxy group which is another functional group, and usually, the silicon-halogen atom bond is present at the polymer terminal. Does not remain.

However, when a living polymer is reacted with a silane compound containing three or more halogen atoms, silicon-terminated at the polymer end.
Halogen atom bonds are likely to remain, and the proportion of other functional alkoxy groups decreases, so that the amount of free functional groups bonded to silicon atoms decreases, resulting in a decrease in affinity with silica. Further, a polymer having a silicon atom-halogen atom bond is easily hydrolyzed by moisture to generate hydrogen halide when it is dissolved from the polymer solution by steam or when it is stored in air,
It is not preferable in terms of handling.

Specific examples of the silane compound used in the present invention include tetraethoxysilane, tetra-t-butoxysilane, tetraphenoxysilane, triethoxymonochlorosilane, tri-t-butoxymonochlorosilane, triphenoxymonochlorosilane, and diethoxy. Dichlorosilane, di-t-butoxydichlorosilane, diphenoxydichlorosilane, ditolyldichlorosilane, triethoxymonobromsilane, tri-t-butoxymonobromsilane, triphenoxymonobromsilane, diethoxydibromosilane, di-t -Butoxydibromosilane, diphenoxydibromosilane, triethoxymonoiodosilane, tri-t-butoxymonoiodosilane, triphenoxymonoiodosilane, diethoxydiiodosilane, di-t-butoxydiio Silane, diphenoxylate Siji iodo silane, tetra - (2-ethyl - hexanoxy) silane, and the like. Among these silane compounds, diphenoxydichlorosilane and tetra- (2-
Ethylhexanoxy) silane and ditolyldichlorosilane are preferred.

These silane compounds may be used alone or in combination of two or more.

The silane compound-modified polymer of the present invention contains the silane compound in an amount of 0.4 to 0.4 per active terminal of the living polymer.
It is obtained by reacting 0.6 molecule, preferably 0.5 molecule.

That is, when less than 0.4 molecule of the tetrafunctional silane compound of the present invention is reacted with one active end of the living polymer, the unreacted functional groups derived from the silane compound are 2 per produced silane compound-modified polymer. Polymer containing 5
The polymer containing 0% or less and one unreacted functional group is 5
It becomes 0% or more, and even if a vulcanized product is produced using this polymer, the amount of free functional groups remaining during vulcanization is too small and the vulcanized physical properties deteriorate. On the other hand, when the tetrafunctional silane compound of the present invention is reacted in an amount of more than 0.6 molecule per one active end of the living polymer, the unreacted functional group derived from the silane compound per silane compound-modified polymer produced is produced. 50% or less of the polymer containing 2 of the above and 50% or more of the polymer containing 3 of the unreacted functional groups, the crosslinking reaction easily occurs in the production process of the polymer, and the functional group is further generated in the production process. Disappears, which causes deterioration of physical properties of vulcanization.

When the tetrafunctional silane compound of the present invention is reacted with 0.4 to 0.6 molecule per active end of a living polymer, the unreacted functional group derived from the silane compound is generated in the produced silane compound-modified polymer. 0 to 1 polymer containing 1
A polymer containing 5%, 50% to 90% of a polymer containing 2 and a polymer substantially free of a polymer containing 3 is obtained, and crosslinking is unlikely to occur even in the subsequent coagulation step of the polymer, and Even when it is blended with a filler such as silica to form a composition, a polymer having an affinity for the filler such as silica and having excellent vulcanized physical properties can be obtained.

In the present invention, the reaction between the active end of the living polymer and the silane compound having four functional groups is carried out by adding the compound to the solution of the living polymer polymerization system or by adding it to an organic solution containing the silane compound. It is carried out by adding a solution of the living polymer. The reaction temperature is
-120 to + 150 ° C, preferably -80 to + 120 ° C
And the reaction time is 1 minute to 5 hours, preferably 5 minutes to
2 hours.

In addition, in a silane compound having a silicon atom-halogen atom, the reactivity of the halogen atom is fast, and the reaction ends almost at the same time as the addition of the silane compound, but the reaction between the alkoxy group and the living polymer is considerably higher than that of the halogen atom. slow.

After the reaction is completed, 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 polymer is dried by heating on a hot roll or under reduced pressure. You can get coalesced.

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

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

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

Furthermore, the silane compound-modified polymer of the present invention shows, for example, by infrared absorption spectrum, absorption near 1,100 cm ⁻¹ due to Si—O—C bond, 1,250 cm ⁻ due to Si—O—φ bond. ¹ near 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 polymer of the present invention can be used alone or in natural rubber, cis-1,4 polyisoprene, emulsion-polymerized styrene-butadiene copolymer, solution-polymerized styrene-butadiene copolymer, low cis-1. , 4 polybutadiene, high cis-1,4 polybutadiene, ethylene propylene diene copolymer, chloroprene, halogenated butyl rubber, NBR, etc. are used by blending, and if necessary, oils such as aromatic, naphthene and paraffin oils Expanded, then white filler such as carbon black, silica, magnesium carbonate, calcium carbonate, glass fiber, ordinary vulcanized rubber compounding agent such as stearic acid, zinc white, antioxidant, vulcanization accelerator and vulcanizing agent Can be added to form a composition.

In the composition, dibutyltin diacetate, dibutyltin cioctoate, 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 sealing materials 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.

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 condition is that the applied load is 0.5k.
g, surface speed of grindstone is 100m / sec, test piece speed is 13
0m / sec, slip rate 30%, sand fall 20g / min,
The measurement temperature was room temperature.

The Lambourn abrasion index was shown with the styrene-butadiene copolymer not modified with a silicon compound being 100. The larger the value, the better the abrasion resistance.

Example 1 An autoclave having an inner volume of 5 with a stirrer and a jacket was dried and replaced with nitrogen. 2,500 g of cyclohexane, 100 g of styrene, 400 g of 1,3-butadiene and 25 g of tetrahydrofuran, which had been purified and dried in advance, were introduced into this autoclave. Next, after the temperature inside the autoclave was set to 10 ° C., cooling water was stopped while stirring at 2 revolutions per minute, 0.350 g of n-butyllithium was added, and polymerization was performed for 30 minutes. A part of this polymer solution was taken out and the Mooney viscosity (ML _{1 + 4} , 100 ° C.) was measured to be 10 or less, and the infrared absorption spectrum of this product is shown in FIG. 1a.

Next, 5.47 ml of a cyclohexane solution of diphenoxydichlorosilane (concentration: 0.50 mol /, the molar ratio of diphenoxydichlorosilane to n-butyllithium corresponds to 0.50) was added to the remaining polymer solution. However, the yellow-red color of the living anion disappeared and the solution viscosity increased. Furthermore, the reaction was carried out at 50 ° C. for 30 minutes.

Then 2,6-di-t-butylphenol (BHT)
Was added to 0.7 g per 100 g of the polymer, a part of the polymer was dried under reduced pressure, and the remaining polymer solution was dissolved by steam and then heated to 100 ° C.
Dried on a hot roll.

The total yield of the obtained silane compound-modified polymer was 495 g, and the Mooney viscosity (ML _{1 + 4} , 100 ° C.) was 32.
Met. This polymer had no insoluble matter when dissolved in tetrahydrofuran.

The infrared absorption spectrum of this modified polymer is shown in FIG. 1b. It can be seen from FIG. 1b that the polymer of the present invention has Si—O—φ bonds even after steam treatment.

Also in the following examples, it was confirmed that Si—O—φ bonds were present.

The silane compound-modified polymer was vulcanized with the following formulation,
The physical properties were evaluated. That is, the polymer, silica, DBTDL, stearic acid, and zinc oxide were premixed with a hot roll of 145 ° C., and then the remaining compounding ingredients were mixed with a roll of 50 ° C. The compound was molded and press vulcanized at 145 ° C.

Also in the following examples, vulcanization was performed by the same method. The results of this example 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 ^{* 30} .6 DM ^{* 4} 1.2 Triethanolamine 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 Example 1 Instead of the diphenoxydichlorosilane of Example 1, the same amount of tetrachlorosilane described in JP-B-49-36957 was used. The styrene-butadiene copolymer was modified in the same manner as in Example 1. Table 1 shows the polymerization results and the vulcanized physical properties of the obtained polymer.

Comparative Example 1 Comparative Example 1 except that the amount of n-butyllithium in Comparative Example 1 was increased to 0.375 g and the amount of tetrachlorosilane added was reduced to a 0.25 molar ratio with respect to n-butyllithium.
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.

From Example 1 and Comparative Examples 1 and 2, the polymer of the present invention has a Si—O—R bond that is not substantially hydrolyzed even when coupled with a silane compound and further steam-dissolved. Tensile strength and wear resistance are remarkable,
The specificity of the silane compound of the present invention is clear.

Comparative Example 3 The amount of n-butyllithium used in Example 1 was 0.210 g.
Except that methyltriethoxysilane described in JP-A-56-104906 was used in an equimolar amount with n-butyllithium instead of diphenoxydichlorosilane.
The styrene-butadiene copolymer was modified in the same manner as in Example 1.

Table 1 shows the polymerization results and the vulcanized physical properties of the obtained polymer.

It is considered that the polymer of the present invention uses, on average, two of the four functional groups of the silane compound for coupling, and the remaining two functional groups for reaction with the compounding agent, The end-reactive polymer described in JP-A-56-104906 shown in Comparative Example 3 clearly shows a unique tensile property.

Examples 2-3 The diphenoxydichlorosilanes of Example 1 were each n-typed.
0.40 molar ratio to butyl lithium and 0.60
The styrene-butadiene copolymer was modified in the same manner as in Example 1 except that the molar ratio was changed. Table 1 shows the results of the polymerization and the vulcanization properties of the obtained polymer.

Comparative Example 4 A styrene-butadiene copolymer was used in the same manner as in Example 1 except that the amount of n-butyllithium used in Example 1 was reduced to 0.210 g and diphenoxydichlorosilane was used in an equimolar amount with respect to n-butyllithium. Was denatured. Table 1 shows the results of the polymerization and the vulcanization properties of the obtained polymer.

From Comparative Example 4, it can be seen that the molar ratio of the living anion and the silane compound is important.

Example 4 A styrene-butadiene copolymer was modified in the same manner as in Example 1 except that the same molar amount of di-t-butoxydichlorosilane was used instead of the diphenoxydichlorosilane of Example 1. The polymerization results and the vulcanized physical properties of the obtained polymer are shown first.

Example 5 After reducing the amount of n-butyllithium of Example 1 to 0.250 g and polymerizing 500 g of 1,3-butadiene, tetra- (2-ethyl-hexanoxy) silane was used instead of diphenoxydichlorosilane; [CH ₃ CH ₂ CH ₂ CH ₂ CH (C ₂ H ₅ ) CH
_A butadiene polymer was modified in the same manner as in Example 1 except that ₂ O] ₄ Si was used in a molar ratio of 0.50 to n-butyllithium. Table 1 shows the results of the polymerization and the vulcanization properties of the obtained polymer.

Comparative Example 5 By the same polymerization method as in Example 1, n-butyllithium was added to 0.2
The weight was reduced to 175 g and 500 g of 1,3-butadiene was polymerized. At this time, modification with a silane compound was not carried out. The results of polymerization and the vulcanized physical properties of the obtained polymer are first described.
Shown in the table.

Comparative Example 6 Diphenoxydichlorosilane was reduced to 0.415 g,
The styrene-butadiene copolymer was modified in the same manner as in Example 1 except that the molar ratio was 0.3 with respect to n-butyllithium. Table 1 shows the results of the polymerization and the vulcanization properties of the obtained polymer.

From Comparative Example 6, it can be seen that the molar ratio of the living anion and the silane compound is important.

[Effects of the Invention] The present invention, by subjecting a living polymer obtained by polymerizing a monomer using an organic alkali metal in an inert organic solvent and a specific silane compound to a coupling reaction at a specific ratio, a substantial Is a method for producing a silane compound-modified polymer having a Si—O—R bond that is not hydrolyzed.
The obtained silane compound-modified polymer exhibits high tensile strength even when blended with a white filler such as silica, which has not been conventionally obtained with high tensile strength. A vulcanizate having properties can be provided.

[Brief description of drawings]

1a and 1b are infrared absorption spectra.

Claims (5)

[Claims] 1. A living polymer obtained by polymerizing a monomer in an inert organic solvent using an organic alkali metal catalyst, has a compound represented by the general formula (I) X _n Si (OR) _4-n per active terminal. (I) (In the formula, X represents a halogen atom which is a chlorine atom, a bromine atom or an iodine atom, R is a hydrocarbon group having 1 to 20 carbon atoms, and n is 0 to 2 A method for producing a silane compound-modified polymer, which comprises reacting a silane compound represented by an integer of 0.4 to 0.6 molecule. 2. The method for producing a silane compound-modified polymer according to claim 1, wherein the monomer is a conjugated diene compound and / or a vinyl aromatic compound. 3. 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
The hydrocarbon group in which two or more carbon atoms are bonded to the carbon at the position, or an aromatic hydrocarbon group represented by a phenyl group or a toluyl group, according to claim 1 or 2. Process for producing silane compound-modified polymer. 4. An n of a silane compound represented by the general formula (I).
The method for producing a silane compound-modified polymer according to claim 1, 2, or 3, wherein is 2. 5. The Mooney viscosity (ML _{1 + 4} , 100 ° C.) even when the silane compound-modified polymer is steamed under atmospheric pressure.
Claims 1 and 2 in which the rise of
The method for producing a silane compound-modified polymer according to item 3, 3 or 4.