JPWO2016125692A1 - Vinyl polymer having hydrolyzable silyl group at terminal, method for producing the same, and curable composition - Google Patents

Abstract

Produced in obtaining a vinyl polymer having a hydrolyzable silyl group at the terminal, characterized by having a structure in which a hydrolyzable silyl group is introduced at the polymer terminal and the halogen derived from the initiator is eliminated from the polymer. It is an object to obtain a vinyl polymer by a method that is superior to conventional processes in terms of performance and waste reduction. The present invention relates to a vinyl monomer having a hydrolyzable silyl group at the end of a vinyl polymer (P) which is a living polymer of a vinyl monomer (A) using an initiator (B) having a carbon-halogen bond. The present invention relates to a vinyl polymer having a hydrolyzable silyl group at the terminal, which has a structure derived from (C) and a structure in which a halogen atom derived from an initiator (B) is eliminated from the polymer.

Description

The present invention relates to a vinyl polymer having a hydrolyzable silyl group at the terminal obtained by living polymerization of a vinyl monomer using an initiator having a carbon-halogen bond, a method for producing the same, and curability Relates to the composition.

Several techniques for living polymerization of vinyl monomers using dissociation of carbon-halogen bonds are known. Atom transfer radical polymerization (Atom Transfer Radical Polymerization: ATRP, Non-Patent Document 1, Non-Patent Document 2), One-Electron Transfer Polymerization (SET-LRP, Non-Patent Document 3, Non-Patent Document 4), and recently Examples include reversible chain transfer catalyzed polymerization (RTCP, Non-patent Document 5, Patent Document 1) and the like.

In particular, paying attention to atom transfer radical polymerization, this method can control the structure, molecular weight and molecular weight distribution of the polymer as required. By using a transition metal catalyst as a polymerization catalyst and reversibly activating (bonding / dissociating) the carbon-halogen bond in the initiator, the polymerization of the vinyl monomer proceeds. As the transition metal catalyst, a transition metal and / or a transition metal compound is usually used, and an amine compound or the like is used as a metal ligand.

As an example of industrially utilizing an atom transfer radical polymer, there is a polymer having a hydrolyzable silyl group introduced. This polymer can be produced by the technique shown in Patent Document 2, but in Patent Document 2, (1) an adsorption process using a solvent, a multi-stage filtration process, and (2) a high temperature (120 ° C.-250 C.) Dehalogenation method by treatment Further, (3) Hydrosilylation reaction using an expensive platinum catalyst for polymers subjected to these processes is disclosed, which is a low-productivity and uneconomical process.

In contrast to Patent Document 2, Patent Document 3 and Patent Document 4 disclose a method of introducing a hydrolyzable silyl group into an atom transfer radical polymer in one pot and one step. Specifically, monomer polymerization is carried out in two stages, and the hydrolyzable silyl group-containing monomer is polymerized in the second stage. However, there is no clear method for the halogen removal operation. In order to industrially use the polymer obtained by atom transfer radical polymerization, it is necessary to remove the halogen atom derived from the initiator from the end of the polymer. For example, if a halogen atom remains in the polymer, for example, (1) the quality of the product due to the free acid derived from the halogen, an adverse effect on the production facility, and (2) the radical due to the thermal dissociation of the carbon-halogen bond. This is because molecular weight and molecular weight distribution increase due to the occurrence.

On the other hand, in Patent Document 5 relating to NMP polymerization (polymerization with nitroxide-mediated polymerization, nitroxide), monomer polymerization is carried out in two stages, vinyltrimethoxysilane monomer is polymerized in the second stage, and hydrolysis is carried out at the end of the polymer. Sex silyl group is introduced. However, the NMP polymerization method is originally a living polymerization method that does not involve a halogen atom. A vinyl polymer having high productivity (for example, one-pot, one-step production method) and having a hydrolyzable silyl group introduced by an economical process is produced by utilizing the dissociation of a carbon-halogen bond. Living polymerization technology has not been developed yet.

JP 2014-111798 A JP 2003-292531 A JP-A-9-272714 JP 2010-539265 A Special table 2013-523929 gazette

J. et al. Am. Chem. Soc. 1995, 117, 5614 Macromolecules 1995, 28, 1721 J. et al. Am. Chem. Soc. 2006, 128, 14156 J. et al. Polym. Sci. : Part A: Polym. Chem. 2007, 45, 1607 Living Radical Polymerization Controlled by Organic Catalysts Polymer Papers 68, 223-231 (2011)

The present invention provides a vinyl polymer having a hydrolyzable silyl group at a terminal, wherein a hydrolyzable silyl group is introduced at a polymer terminal and a halogen derived from an initiator is eliminated from the polymer. It is an object to obtain a vinyl polymer that is superior to conventional processes in terms of productivity and reduction of waste reduction.

In view of the above circumstances, as a result of intensive studies by the present inventor, it has been found that the above problems can be solved, and the present invention has been obtained.

That is, the present invention has a hydrolyzable silyl group at the terminal of the vinyl polymer (P) which is a living polymer of the vinyl monomer (A) using the initiator (B) having a carbon-halogen bond. A vinyl polymer having a hydrolyzable silyl group at the terminal, having a structure derived from a vinyl monomer (C) and a structure in which a halogen atom derived from an initiator (B) is eliminated from the polymer About.

The living polymer is preferably an atom transfer radical polymer.

The vinyl polymer (P) is preferably a (meth) acrylic acid ester polymer.

The initiator (B) having a carbon-halogen bond is preferably diethyl 2,5-dibromoadipate or ethyl 2-bromoisobutyrate.

The hydrolyzable silyl group is preferably a hydrolyzable silyl group represented by the following general formula (1).
—Si (R ¹ ) _n (OR ² ) _3-n (1)
Wherein R ¹ is an alkyl group having 1 to 8 carbon atoms, an aryl group or an aralkyl group, R ² is hydrogen or an alkyl group having 1 to 8 carbon atoms, an aryl group or an aralkyl group, and n is an integer of 0 to 2. Show.)

（式中、Ｒ^１は炭素数１〜８のアルキル基、アリール基またはアラルキル基、Ｒ^２は水素原子または炭素数１〜８のアルキル基、アリール基もしくはアラルキル基、Ｒ^４は水素原子または炭素数１〜８のアルキル基、アリール基もしくはアラルキル基、Ｒ^５は直接結合、（Ｃ_６Ｈ_４）で示されるフェニル基または（ＣＨ_２）_ｍ（ｍは１〜８の整数）で示される２価の炭化水素基、ｎは０〜２の整数を示す。）The vinyl monomer (C) having a hydrolyzable silyl group preferably has a structure represented by the following general formula (3).

Wherein R ¹ is an alkyl group having 1 to 8 carbon atoms, an aryl group or an aralkyl group, R ² is a hydrogen atom or an alkyl group having 1 to 8 carbon atoms, an aryl group or an aralkyl group, and R ⁴ is a hydrogen atom or carbon. A number 1 to 8 alkyl group, aryl group or aralkyl group, R ⁵ is a direct bond, a phenyl group represented by (C ₆ H ₄ ), or (CH ₂ ) _m (m is an integer of 1 to 8) 2 Valent hydrocarbon group, n represents an integer of 0 to 2.)

The vinyl monomer (C) having a hydrolyzable silyl group is preferably vinyltrimethoxysilane or vinyldimethoxymethylsilane.

（式中、Ｒ^１は炭素数１〜８のアルキル基、アリール基またはアラルキル基、Ｒ^２は水素または炭素数１〜８のアルキル基、アリール基もしくはアラルキル基、ｎは０〜２の整数、Ｒ^３はメチル基、エチル基、ブチル基、２−メトキシエチル基またはステアリル基をそれぞれ示す。（Ａ）はビニル系モノマー（Ａ）由来の繰り返し単位、（Ｂ）は開始剤残基、ｘは正の整数をそれぞれ示す。）It is preferable that the vinyl polymer having a hydrolyzable silyl group at the terminal has a structure selected from the structure represented by the following general formula (2).

(Wherein R ¹ is an alkyl group having 1 to 8 carbon atoms, an aryl group or an aralkyl group, R ² is hydrogen or an alkyl group having 1 to 8 carbon atoms, an aryl group or an aralkyl group, n is an integer of 0 to 2, R ³ represents a methyl group, an ethyl group, a butyl group, a 2-methoxyethyl group or a stearyl group, (A) is a repeating unit derived from the vinyl monomer (A), (B) is an initiator residue, x is Each positive integer is indicated.)

The present invention also relates to a curable composition containing a vinyl polymer having a hydrolyzable silyl group at the terminal described above.

The present invention also includes a step of living polymerizing a vinyl monomer (A) using an initiator (B) having a carbon-halogen bond to obtain a vinyl polymer (P), and a vinyl polymer (P ) And a vinyl monomer (C) having a hydrolyzable silyl group, and the step of introducing a hydrolyzable silyl group into the terminal of the vinyl polymer (P) includes a hydrolyzable silyl group at the terminal described above. The present invention relates to a method for producing a vinyl-based polymer having

According to the present invention, a vinyl-based polymer having a hydrolyzable silyl group at the terminal is characterized in that a hydrolyzable silyl group is introduced at the polymer terminal and the halogen derived from the initiator is eliminated from the polymer. Coalescence can be gained in terms of productivity and waste reduction compared to conventional processes.

The form for implementing this invention is demonstrated below.

The present invention relates to a vinyl type having a hydrolyzable silyl group at the terminal of a vinyl polymer (P) which is a living polymer of a vinyl type monomer (A) using an initiator (B) having a carbon-halogen bond. The present invention relates to a vinyl polymer having a hydrolyzable silyl group at the terminal, which has a structure derived from a monomer (C) and a structure in which a halogen atom derived from an initiator (B) is eliminated from the polymer.
The vinyl monomer (B) is living polymerized with respect to the initiator (B) having a carbon-halogen bond, and the vinyl monomer (B) having a hydrolyzable silyl group is obtained with respect to the obtained vinyl polymer (P). By reacting C), a structure derived from the vinyl monomer (C) is introduced into the terminal of the vinyl polymer (P) and a terminal having a structure in which the halogen atom derived from the initiator is eliminated from the polymer. A vinyl polymer having a hydrolyzable silyl group is obtained.

Hereinafter, the vinyl monomer (A), the initiator (B) having a carbon-halogen bond, living radical polymerization conditions, the vinyl monomer (C), and the vinyl polymer will be described in detail with examples.

(Vinyl monomer (A))
There is no restriction | limiting in particular as a vinyl-type monomer (A) used by this invention, The various thing used by living polymerization can be used. For example, (meth) acrylic acid; (meth) acrylic acid methyl, (meth) acrylic acid ethyl, (meth) acrylic acid-n-propyl, (meth) acrylic acid isopropyl, (meth) acrylic acid-n- Butyl, isobutyl (meth) acrylate, (tert-butyl) (meth) acrylate, n-pentyl (meth) acrylate, n-hexyl (meth) acrylate, cyclohexyl (meth) acrylate, (meth) acryl Acid-n-heptyl, (meth) acrylic acid-n-octyl, (meth) acrylic acid-2-ethylhexyl, (meth) acrylic acid nonyl, (meth) acrylic acid decyl, (meth) acrylic acid dodecyl, (meth) Stearyl acrylate, isobornyl (meth) acrylate, phenyl (meth) acrylate, toluyl (meth) acrylate, (meth ) Benzyl acrylate, 2-methoxyethyl (meth) acrylate, 2-ethoxyethyl (meth) acrylate, 3-methoxybutyl (meth) acrylate, 2-hydroxyethyl (meth) acrylate, ( (Meth) acrylic acid-2-hydroxypropyl, (meth) acrylic acid glycidyl, (meth) acrylic acid 2-aminoethyl, γ- (methacryloyloxypropyl) trimethoxysilane, (meth) acrylic acid ethylene oxide adduct, ( Trifluoromethylmethyl (meth) acrylate, 2-trifluoromethylethyl (meth) acrylate, 2-perfluoroethylethyl (meth) acrylate, 2-perfluoroethyl-2-perfluorobutylethyl (meth) acrylate , 2-Perfluoroethyl (meth) acrylate, (meth) acrylic Perfluoromethyl acid, diperfluoromethyl methyl (meth) acrylate, 2-perfluoromethyl-2-perfluoroethyl methyl (meth) acrylate, 2-perfluorohexyl ethyl (meth) acrylate, (meth) acrylic (Meth) acrylic acid ester monomers such as 2-perfluorodecylethyl acid, 2-perfluorohexadecylethyl (meth) acrylate; styrene, vinyltoluene, α-methylstyrene, chlorostyrene, styrenesulfonic acid and salts, etc. Styrenic monomers of: fluorine-containing vinyl monomers such as perfluoroethylene, perfluoropropylene, vinylidene fluoride; silicon-containing vinyl monomers such as vinyltrimethoxysilane and vinyltriethoxysilane; maleic anhydride, maleic acid, maleic acid Monoal Fumaric acid, monoalkyl and dialkyl esters of fumaric acid; maleimide, methylmaleimide, ethylmaleimide, propylmaleimide, butylmaleimide, hexylmaleimide, octylmaleimide, dodecylmaleimide, stearylmaleimide, phenylmaleimide, cyclohexylmaleimide, etc. Maleimide monomers: nitrile group-containing vinyl monomers such as acrylonitrile and methacrylonitrile; amide group-containing vinyl monomers such as acrylamide and methacrylamide; vinyl acetate, vinyl propionate, vinyl pivalate, vinyl benzoate, vinyl cinnamate Vinyl esters such as ethylene; alkenes such as ethylene and propylene; conjugated dienes such as butadiene and isoprene; vinyl chloride Nyl, vinylidene chloride, allyl chloride, allyl alcohol and the like.
These may be used singly or plural may be copolymerized. Among these, styrenic monomers, (meth) acrylic acid and (meth) acrylic acid ester monomers are preferable in view of the physical properties of the product, and the reactivity of the functional group introduction reaction is low and the glass transition point is low. For this reason, (meth) acrylic acid ester monomers are more preferable. Examples of (meth) acrylic acid ester monomers include butyl (meth) acrylate ((meth) acrylic acid-n-butyl, (meth) acrylic acid isobutyl, (meth) acrylic acid-tert-butyl), and (meth) acrylic. Ethyl acid, stearyl (meth) acrylate, and 2-methoxyethyl (meth) acrylate are preferred.

(Initiator having carbon-halogen bond (B))
The initiator (B) having a carbon-halogen bond is an organic halide having a highly reactive carbon-halogen bond, and is used as a polymerization initiator. In the present invention, living polymerization, more specifically living radical polymerization, is carried out utilizing dissociation of the carbon-halogen bond of the initiator (B).

Examples of the initiator (B) include a carbonyl compound having a halogen at the α-position, a compound having a halogen at the benzyl-position, a halogenated sulfonyl compound, and the like.
C ₆ H ₅ -CH ₂ X,
_{C 6 H 5 -C (H)} (X) CH 3,
_{C 6 H 5 -C (X)} (CH 3) 2
(In the above chemical formulas, C ₆ H ₅ is a phenyl group, X is a halogen group),
_{^{R 6 -C (H) (X}} ) -CO 2 R 7,
_{^{R 6 -C (CH 3) (}} X) -CO 2 R 7,
^{R 6 -C (H) (X} ) -C (O) R 7,
_{^{R 6 -C (CH 3) (}} X) -C (O) R 7
(In the above formulas, R ⁶ and R ⁷ are a hydrogen atom or an alkyl group having 1 to 20 carbon atoms, an aryl group, or an aralkyl group, and X is chlorine, bromine, or iodine),
^{_{R 8 -C 6 H 4 -SO 2}} X
(Wherein R ⁸ is a hydrogen atom or an alkyl group having 1 to 20 carbon atoms, an aryl group, or an aralkyl group, and X is a halogen group).

An organic halide having two or more starting points or a sulfonyl halide compound may be used as an initiator.

Specific examples of the initiator (B) having a carbon-halogen bond include diethyl 2,5-dibromoadipate (2,5- Diethyl dibromoadipate) is preferred, and for initiators with one starting point, ethyl 2-bromoisobutyrate is preferred.

It is a feature of living radical polymerization that the desired polymer molecular weight can be set by adjusting the ratio of the monomer and the initiator amount.
The initiator (B) is preferably used in an amount of 0.1 to 30 parts by weight, more preferably 0.2 to 20 parts by weight, based on 100 parts by weight of the vinyl monomer (A).

(Vinyl polymer (P))
The vinyl polymer (P) used in the present invention is a living polymer obtained by living polymerizing a vinyl monomer (A) using an initiator (B) having a carbon-halogen bond.
The vinyl polymer (P) is preferably a (meth) acrylic acid ester polymer.

(Living radical polymerization conditions)
The present invention utilizes living polymerization utilizing dissociation of carbon-halogen bonds. Among them, it is preferable to use living radical polymerization. For example, the following polymerization techniques are applicable.

Living radical polymerization method of vinyl monomer using transition metal complex consisting of transition metal or transition metal compound and ligand, represented by ATRP and SET-LRP, and RTCP not using these transition metals as catalyst Etc.

Living radical polymerization using a transition metal complex as a catalyst is currently considered in two ways: ATRP and SET-LRP.
In ATRP, for example, when a copper complex is used as a catalyst, the monovalent copper complex pulls out the halogen at the end of the polymer to generate radicals to become a divalent copper complex. The divalent copper complex returns a halogen to the radical at the polymerization end to become a monovalent copper complex. Living radical polymerization consisting of these equilibrium is ATRP.
On the other hand, in SET-LRP, when a copper complex is used as a catalyst, a zero-valent metal copper or copper complex extracts a halogen at a polymer terminal to generate a radical to form a divalent copper complex. The divalent copper complex returns a halogen to the radical at the polymerization terminal to become a zero-valent copper complex. The monovalent copper complex is disproportionated to become zero-valent and divalent copper complexes. Living radical polymerization consisting of these equilibrium is SET-LRP.
In the present application, both are not particularly distinguished, and a living radical polymerization system using a transition metal or a transition metal compound and a ligand as a catalyst is treated as a polymerization system that can be used in the present invention.

In addition, by reducing the number of highly oxidized transition metal complexes that cause polymerization delay and termination using a reducing agent, the polymerization reaction can be rapidly advanced to a high reaction rate even under low catalyst conditions with few transition metal complexes. Activators Regenerated by Electron Transfer: (hereinafter referred to as ARGET or ARGET ATRP) (Macromolecules. 2006, 39, 39) has been reported as an improved formulation of ATRP. As described above, in the present application, a living radical polymerization system using a transition metal or a transition metal compound and a ligand as a catalyst is treated as a polymerization system that can be used in the present invention, and ARGET is also included in this.

In the present invention, it is preferable to use atom transfer radical polymerization (ATRP, SET-LRP, ARGET). Therefore, the vinyl polymer (P) is preferably an atom transfer radical polymer.

<Polymerization catalyst>
Regardless of whether a reducing agent is used or not, an atom transfer radical polymerization system uses a metal complex having a group 7 element, 8 group, 9 group, 10 group, or 11 element as a central metal in the periodic table. Monovalent copper, divalent copper, divalent ruthenium, and divalent iron are preferred. Examples of the copper catalyst include cuprous chloride, cupric chloride, cuprous bromide, cupric bromide, cuprous iodide, cupric iodide, cuprous cyanide, cuprous oxide, Examples include cuprous acetate and cuprous perchlorate. When using a copper compound, an amine ligand is added in order to increase the catalytic activity. As the ruthenium catalyst, divalent tris triphenylphosphine complex of ruthenium chloride _{(RuCl 2 (PPh 3) 3} ) is preferable. When this catalyst is used, an aluminum compound such as trialkoxyaluminum is added to increase its activity. As the iron catalyst, a tristriphenylphosphine complex of divalent iron chloride (FeCl ₂ (PPh ₃ ) ₃ ) is preferable.

Among these, a copper catalyst which is an inexpensive metal catalyst is preferable because it is economically superior.
Among these, cupric bromide, cupric chloride, and cupric iodide are preferable from the viewpoint of industrial availability.

The polymerization catalyst is preferably used in an amount of 0.2 to 10 parts by weight, more preferably 0.5 to 7 parts by weight, based on 100 parts by weight of the vinyl monomer (A).

<Multidental amine>
The higher the catalyst activity, the faster the polymerization rate and the better from the viewpoint of productivity. Therefore, in the present invention, it is preferable to use a polydentate amine that particularly increases the catalyst activity as an amine ligand in combination with a copper catalyst. The polydentate amine is exemplified below, but is not limited thereto.
Bidentate polydentate amines: 2,2-bipyridine, 4,4′-di- (5-nonyl) -2,2′-bipyridine, N- (n-propyl) pyridylmethanimine, N- (n -Octyl) pyridylmethanimine.
Tridentate polydentate amines: N, N, N ′, N ″, N ″ -pentamethyldiethylenetriamine, N-propyl-N, N-di (2-pyridylmethyl) amine.
Tetradentate polydentate amine: hexamethyltris (2-aminoethyl) amine (often abbreviated as Me ₆ TREN), N, N-bis (2-dimethylaminoethyl) -N, N′-dimethyl Ethylenediamine, 2,5,9,12-tetramethyl-2,5,9,12-tetraazatetradecane, 2,6,9,13-tetramethyl-2,6,9,13-tetraazatetradecane, 4, 11-dimethyl-1,4,8,11-tetraazabicyclohexadecane, N ′, N ″ -dimethyl-N ′, N ″ -bis ((pyridin-2-yl) methyl) ethane-1,2- Diamine, tris [(2-pyridyl) methyl] amine, 2,5,8,12-tetramethyl-2,5,8,12-tetraazatetradecane.
A pentadentate polydentate amine: N, N, N ′, N ″, N ′ ″, N ″ ″, N ″ ″-heptamethyltetraethylenetetramine.
Hexadentate polydentate amine: N, N, N ′, N′-tetrakis (2-pyridylmethyl) ethylenediamine.
Polyamine: Polyethyleneimine.
Among these, N, N, N ′, N ″, N ″ -pentamethyldiethylenetriamine, hexamethyltris (2-aminoethyl) amine (Me6TREN), and tris [ (2-Pyridyl) methyl] amine is preferred.

The polydentate amine is preferably used in an amount of 0.15 to 1 part by weight, more preferably 0.13 to 0.5 part by weight, based on 100 parts by weight of the polymerization catalyst.

<Base>
A base may be added to neutralize the acid present in the polymerization system or the acid generated and prevent acid accumulation. Examples of the base include, but are not limited to, the following.
Monoamine: Monoamine means an amine compound having only one site acting as a base as defined above in one molecule, and is exemplified below, but is not limited thereto. Primary amines such as methylamine, aniline and lysine, secondary amines such as dimethylamine and piperidine, tertiary amines such as trimethylamine and triethylamine, aromatics such as pyridine and pyrrole, ammonia and the like.
Polyamine type: diamines such as ethylenediamine and tetramethylethylenediamine, triamines such as diethylenetriamine and pentamethyldiethylenetriamine, tetramines such as triethylenetetramine, hexamethyltriethylenetetramine and hexamethylenetetramine, polyethyleneimine and the like.
Inorganic base: Inorganic base means a simple substance of Group 1 or Group 2 element of the periodic table or a compound composed thereof, and is exemplified below, but is not limited thereto. A simple substance of a group 1 or group 2 element of the periodic table such as lithium, sodium, calcium and the like. Sodium methoxide, potassium ethoxide, methyl lithium, sodium hydroxide, potassium hydroxide, potassium carbonate, sodium bicarbonate, ammonium bicarbonate, trisodium phosphate, disodium hydrogen phosphate, tripotassium phosphate, dihydrogen phosphate Compounds composed of Group 1 or Group 2 elements of the periodic table such as potassium, sodium acetate, potassium acetate, sodium oxalate, potassium oxalate, phenoxy sodium, phenoxy potassium, sodium ascorbate, potassium ascorbate and the like.
Salts of weak acids and strong bases: ammonium hydroxide and the like.
Among these, triethylamine and potassium carbonate are preferable from the viewpoint of industrial availability.

These may be used alone or in combination.
The base may be added directly to the reaction system or may be generated in the reaction system.

The base is preferably used in an amount of 0.01 to 0.3 parts by weight, more preferably 0.02 to 0.1 parts by weight, based on 100 parts by weight of the vinyl monomer (A).

<Reducing agent>
In atom transfer radical polymerization using a transition metal catalyst (for example, copper complex) as a catalyst, it has been found that the activity is improved by using a reducing agent in combination (ARGET ATRP). This ARGET ATRP is thought to improve its activity by reducing and reducing highly oxidized transition metal complexes that are caused by coupling of radicals during polymerization and causing reaction delay and termination. It is possible to reduce the necessary transition metal catalyst to several tens of ppm to several tens to several hundred ppm.
Also in the present invention, a reducing agent can be used for the same purpose as ARGET ATRP.

Reducing agents are classified into those that generate an acid during the reduction of the complex and those that do not. Although the reducing agent which can be used by the system which uses a copper catalyst is illustrated below, it is not limited to these reducing agents.

<Reducing agent that does not generate acid when reducing copper complex>
Metals: Alkali metals such as lithium, sodium and potassium; alkaline earth metals such as beryllium, magnesium, calcium and barium; typical metals such as aluminum and zinc; transition metals such as copper, nickel, ruthenium and iron It is done. These metals may be in the state of an alloy (amalgam) with mercury.
Metal compounds: Examples include salts of typical metals or transition metals and salts with typical elements, and complexes in which carbon monoxide, olefins, nitrogen-containing compounds, oxygen-containing compounds, phosphorus-containing compounds, sulfur-containing compounds and the like are coordinated. Specifically, compounds of metal and ammonia / amine, titanium trichloride, titanium alkoxide, chromium chloride, chromium sulfate, chromium acetate, iron chloride, copper chloride, copper bromide, tin chloride, zinc acetate, zinc hydroxide, Carbonyl complexes such as Ni (CO) ₄ and Co ₂ CO ₈ , and olefin complexes such as [Ni (cod) ₂ ], [RuCl ₂ (cod)] and [PtCl ₂ (cod)] (where cod is cyclooctadiene) ), [RhCl (P (C ₆ H ₅ ) ₃ ) ₃ ], [RuCl ₂ (P (C ₆ H ₅ ) ₃ ) ₂ ], [PtCl ₂ (P (C ₆ H ₅ ) ₃ ) ₂ ], etc. And phosphine complexes.
Tin compounds: organic tin compounds such as dibutyltin diacetate, dibutyltin dilaurate, dibutyltin mercaptide, dibutyltin thiocarboxylate, dibutyltin dimaleate, dioctyltin thiocarboxylate; tin carboxylates such as tin octylate and tin 2-ethylhexanoate Examples include salts.
Phosphorus or phosphorus compound: phosphorus, trimethylphosphine, triethylphosphine, triphenylphosphine, trimethylphosphite, triethylphosphite, triphenylphosphite, hexamethylphosphorustriamide, hexaethylphosphorustriamide and the like.
Sulfur or sulfur compounds: Sulfur, Rongalite, hydrosulfite, thiourea dioxide, etc. Rongalite is a formaldehyde derivative of sulfoxylate, represented by MSO ₂ · CH ₂ O (M represents Na or Zn), and specifically, sodium formaldehyde sulfoxylate, zinc formaldehyde sulfoxylate, etc. Is mentioned. Hydrosulfite is a general term for sodium hyposulfite and formaldehyde derivatives of sodium hyposulfite.

<Reducing agent that generates acid when reducing copper complex (hydride reducing agent)>
Metal hydride: sodium hydride; germanium hydride; tungsten hydride; diisobutylaluminum hydride, lithium aluminum hydride, sodium aluminum hydride, sodium triethoxyaluminum hydride, sodium bis (2-methoxyethoxy) aluminum hydride, etc. Aluminum hydrides; organic tin hydrides such as triphenyltin hydride, tri-n-butyltin hydride, diphenyltin hydride, di-n-butyltin hydride, triethyltin hydride, trimethyltin hydride, and the like.
Silicon hydride: trichlorosilane, trimethylsilane, triethylsilane, diphenylsilane, phenylsilane, polymethylhydrosiloxane and the like.
Boron hydride: borane, diborane, sodium borohydride, sodium trimethoxyborate, sodium borohydride, sodium borohydride, sodium borohydride, lithium borohydride, lithium borohydride, lithium triethylborohydride, hydrogenated Examples include tri-s-butyl boron lithium, hydrogenated tri-t-butyl boron lithium, calcium borohydride, potassium borohydride, zinc borohydride, tetra-n-butylammonium borohydride, and the like.
Nitrogen and hydrogen compounds: hydrazine, diimide and the like.
Phosphorus or phosphorus compound: Specific examples include phosphine and diazaphospholene.
Sulfur or sulfur compounds: hydrogen sulfide and the like.
hydrogen.
Organic compounds exhibiting a reducing action: alcohols, aldehydes, phenols, organic acid compounds and the like. Examples of the alcohol include methanol, ethanol, propanol, and isopropanol. Examples of the aldehyde include formaldehyde, acetaldehyde, benzaldehyde, formic acid and the like. Examples of phenols include phenol, hydroquinone, dibutylhydroxytoluene, tocopherol and the like. Examples of the organic acid compound include citric acid, oxalic acid, ascorbic acid, ascorbate, ascorbate ester and the like.

Among these reducing agents, ascorbic acid and tin 2-ethylhexanoate are preferable in terms of industrial availability and ease of dissolution in organic solvents.
These reducing agents may be used alone or in combination of two or more.
Further, the reducing agent may be added directly to the reaction system or may be generated in the reaction system. The latter includes electrolytic reduction. In electrolytic reduction, it is known that electrons generated at the cathode exhibit a reducing action immediately or once solvated. That is, a reducing agent produced by electrolysis can also be used.

The reducing agent is preferably used in an amount of 0.001 to 0.2 parts by weight, more preferably 0.005 to 0.1 parts by weight, based on 100 parts by weight of the vinyl monomer (A).

<Solvent>
The atom transfer radical polymerization that can be used in the present invention can be performed without a solvent, but a solvent can also be used. Examples of the solvent include, but are not limited to, the following.
High polar aprotic solvents: dimethyl sulfoxide (DMSO), dimethylformamide (DMF), N, N-dimethylacetamide (DMAc), N-methylpyrrolidone and the like.
Carbonate solvents: ethylene carbonate, propylene carbonate, etc.
Alcohol solvents: methanol, ethanol, propanol, isopropanol, n-butyl alcohol, tert-butyl alcohol and the like.
Nitrile solvents: acetonitrile, propionitrile, benzonitrile and the like.
Ketone solvents: acetone, methyl ethyl ketone, methyl isobutyl ketone and the like.
Ether solvents: diethyl ether, tetrahydrofuran and the like.
Halogenated carbon solvents: methylene chloride, chloroform and the like.
Ester solvent: ethyl acetate, butyl acetate and the like.
Hydrocarbon solvents: pentane, hexane, cyclohexane, octane, decane, benzene, toluene and the like.
Ionic liquid.
water.
Supercritical fluid.
The said solvent can be used individually or in mixture of 2 or more types.

In the atom transfer radical polymerization (ARGET) system using a reducing agent, the transition metal or transition metal compound, polydentate amine, base, reducing agent, monomer and initiator are mixed uniformly in the reaction system. , More preferable in terms of polymerization reaction rate, ease of preparation, and scale-up risk. Therefore, it is preferable to select a solvent that can uniformly mix them. For example, ethanol, methanol, propanol, and ethyl acetate are preferable.

The solvent is preferably used in an amount of 0 to 50 parts by weight, more preferably 5 to 20 parts by weight, based on 100 parts by weight of the vinyl monomer (A).

(Vinyl monomer having hydrolyzable silyl group (C))
As a hydrolysable silyl group of the vinyl-type monomer (C) used by this invention, what is shown by General formula (1) is preferable.
—Si (R ¹ ) _n (OR ² ) _3-n (1)
Wherein R ¹ is an alkyl group having 1 to 8 carbon atoms, an aryl group or an aralkyl group, R ² is a hydrogen atom or an alkyl group having 1 to 8 carbon atoms, an aryl group or an aralkyl group, and n is an integer of 0 to 2 Is shown.)
R ¹ is preferably a methyl group or an ethyl group, and R ² is preferably a hydrogen atom, a methyl group or an ethyl group. n is preferably 0 or 1.

（Ｒ^１、Ｒ^２、ｎの定義は上記式（１）と同じ。Ｒ^４は水素原子または炭素数１〜８のアルキル基、アリール基もしくはアラルキル基、Ｒ^５は直接結合、（Ｃ_６Ｈ_４）で示されるフェニル基または（ＣＨ_２）_ｍ（ｍは１〜８の整数）で示される２価の炭化水素基を示す。）
原料の入手性や、得られるビニル系重合体の末端の反応性の高さの観点から、Ｒ^１としてはメチル基またはエチル基が好ましい。Ｒ^２としては水素原子、メチル基またはエチル基が好ましい。ｎとしては０または１が好ましい。Ｒ^４としては水素原子が好ましい。Ｒ^５としては直接結合が好ましい。More specifically, the vinyl monomer (C) preferably has a structure represented by the following general formula (3) including a hydrolyzable silyl group represented by the general formula (1).

(The definitions of R ¹ , R ² and n are the same as in the above formula (1). R ⁴ is a hydrogen atom or an alkyl group having 1 to 8 carbon atoms, an aryl group or an aralkyl group, R ⁵ is a direct bond, (C ₆ H ₄ ) or a divalent hydrocarbon group represented by (CH ₂ ) _m (m is an integer of 1 to 8).
From the viewpoint of availability of raw materials and high reactivity of the terminal of the vinyl polymer to be obtained, R ¹ is preferably a methyl group or an ethyl group. R ² is preferably a hydrogen atom, a methyl group or an ethyl group. n is preferably 0 or 1. R ⁴ is preferably a hydrogen atom. R ⁵ is preferably a direct bond.

Specific compound names include vinyltrimethoxysilane, vinyltriethoxysilane, vinyldimethoxymethylsilane, vinyldiethoxyethylsilane, vinylmonomethoxydimethylsilane, vinylmonoethoxydiethylsilane, styryltrimethoxysilane, styryltriethoxy. Examples thereof include silane, styryl dimethoxymethyl silane, styryl diethoxyethyl silane, styryl monomethoxydimethyl silane, and styryl monoethoxydiethyl silane.

Among these, vinyltrimethoxysilane, vinyldimethoxymethylsilane, vinyltriethoxysilane, and styryltrimethoxysilane are preferable from the viewpoint of availability of raw materials. Of these, vinyltrimethoxysilane, vinyldimethoxymethylsilane, and vinyltriethoxysilane are more preferable because of their relatively low cost and high reactivity. In particular, vinyltrimethoxysilane and vinyldimethoxymethylsilane are preferable from the viewpoint of removing the raw material after the reaction under reduced pressure.

The vinyl monomer (C) is preferably used in an amount of 1 to 30 parts by weight, more preferably 2 to 20 parts by weight, based on 100 parts by weight of the vinyl monomer (A).

(Vinyl polymer having hydrolyzable silyl group at the end)
The vinyl polymer having a hydrolyzable silyl group at the end of the present invention has a structure in which a structure derived from a vinyl monomer (C) having a hydrolyzable silyl group at the end of the vinyl polymer (P) exists. . Moreover, it has a structure in which the halogen atom derived from the initiator (B) is eliminated from the polymer.
The vinyl polymer having a hydrolyzable silyl group at the terminal is preferably a (meth) acrylic acid ester polymer.

The hydrolyzable silyl group at the end of the polymer is derived from the vinyl monomer (C). Therefore, the hydrolyzable silyl group is preferably the one represented by the general formula (1).

The method for producing a vinyl polymer having a hydrolyzable silyl group at the terminal of the present invention comprises living polymerizing a vinyl monomer (A) using an initiator (B) having a carbon-halogen bond, A step of obtaining a polymer (P), and a reaction between the vinyl polymer (P) and a vinyl monomer (C) having a hydrolyzable silyl group, and a hydrolyzable silyl group at the terminal of the vinyl polymer (P). The process of introducing.

In the step of reacting the vinyl polymer (P) with the vinyl monomer (C) having a hydrolyzable silyl group, the vinyl polymer (P) obtained by polymerizing the vinyl monomer (A) is isolated. In addition, the polymerization may be carried out as it is under the polymerization conditions of the vinyl monomer (A), or it may be isolated without purification or isolated from the vinyl polymer (P) after purification, and the living polymerization conditions again. It may be carried out with the following.

Considering the reduction of productivity and waste reduction, it is better to react the vinyl monomer (C) as it is without isolating the vinyl polymer (P) obtained after the completion of the polymerization of the vinyl monomer (A). Good.

When the vinyl monomer (C) is reacted as it is without isolating the vinyl polymer (P) obtained after the polymerization of the vinyl monomer (A), the polymerization conditions of the vinyl monomer (A) are used as they are. Alternatively, the reaction conditions may be changed within a range that does not hinder the reaction of the vinyl monomer (C).

For example, a polymerization catalyst and a polymerization solvent used in the polymerization of the vinyl monomer (A) may be additionally added, or an additive may be newly added. When the vinyl monomer (A) remains in the reaction system, it may be distilled off under reduced pressure, or the vinyl monomer (C) may be polymerized without distillation under reduced pressure.

When the reaction of the vinyl monomer (C) is carried out without distilling off the vinyl monomer (A), there is no particular limitation, but 80% or more of the total weight of the vinyl monomer (A) is consumed. This is desirable in terms of productivity. Preferably it is 90% or more, more preferably 95% or more.

In addition, the vinyl polymer (P) obtained after the completion of the polymerization of the vinyl monomer (A) is further polymerized with other vinyl monomers (A) under living polymerization conditions to obtain hydrolyzable silyl groups. The vinyl monomer (C) having

Even when the vinyl monomer (C) is reacted after the vinyl polymer (P) obtained after the polymerization of the vinyl monomer (A) is isolated, the living polymerization conditions are the same as those for the polymerization of the vinyl monomer (A). The conditions may be used as they are, or the reaction conditions may be changed within a range that does not hinder the reaction of the vinyl monomer (C).

When the vinyl polymer (P) is isolated after purification, the purification operation is not particularly limited. For example, reprecipitation operation using a solvent, adsorption treatment using an adsorbent, filtration using a filter aid or a filter. Mention may be made of processing and centrifugal filtration using a centrifuge.

After completion of the reaction of the vinyl monomer (C), the reaction system is devolatilized at a temperature of 50 ° C. to 150 ° C., and volatile raw materials and auxiliary raw materials such as a solvent and unreacted vinyl monomers are distilled off.

（式中、Ｘはハロゲン基を示し、Ｉｎｉｔはハロゲン基を除く開始剤構造を示す。Ｒ^１、Ｒ^２、Ｒ^４、Ｒ^５、ｎの定義は上記式（３）と同じ。）When the initiator (B) having a carbon-halogen bond is shown as Init-X (X represents a halogen group and Init represents an initiator structure excluding the halogen group), the vinyl monomer (A) is an initiator (B ) And the vinyl monomer (C) having a hydrolyzable silyl group having the structure represented by the general formula (3) and the reaction proceeds as shown in the following reaction formula: Conceivable.

(In the formula, X represents a halogen group, and Init represents an initiator structure excluding the halogen group. The definitions of R ¹ , R ² , R ⁴ , R ⁵ , and n are the same as in the above formula (3).)

The “structure in which the halogen atom derived from the initiator (B) is eliminated from the polymer” means a structure obtained by elimination of at least one halogen atom derived from the initiator (B) from the polymer. To do. Therefore, the structure includes a structure in which a part of the halogen atom derived from the initiator (B) remains and a structure that does not contain any halogen atom derived from the initiator (B).
Specifically, as shown in the above reaction formula, a structure in which a halogen atom does not exist and a carbon-carbon double bond (C═C) exists in at least one polymer terminal can be mentioned. The presence of the carbon-carbon double bond can be confirmed with a nuclear magnetic resonance analyzer ( ¹ H-NMR).
Moreover, 4000 ppm or less is preferable and, as for the halogen content which the vinyl polymer of this invention contains, 3000 ppm or less is more preferable. The halogen content can be stimulated by ICPMS (inductively coupled plasma mass spectrometry) or a fluorescent X-ray analyzer.

In the process of producing the vinyl polymer of the present invention, a purification operation may be carried out to remove auxiliary materials such as a catalyst and various impurities generated in the polymerization step, but this is not restrictive. Examples of the purification operation include a reprecipitation operation using a solvent, an adsorption treatment using an adsorbent, a filtration treatment using a filter aid and a filter, and centrifugal filtration using a centrifuge.

The production process used in the present invention has a feature that a vinyl polymer having a hydrolyzable silyl group that has been dehalogenated can be produced in one pot, and is disclosed in Patent Document 2 in several steps. There is no need to go through a refining process, and the amount of secondary raw materials used is small, and it is not necessary to carry out a hydrosilylation reaction using an expensive platinum catalyst. That is, the manufacturing process used in the present invention is economically advantageous, is effective in reducing waste, and has a high productivity.

The number average molecular weight of the vinyl polymer having a hydrolyzable silyl group at the end of the present invention is not particularly limited.
The molecular weight distribution, that is, the ratio (Mw / Mn) of the weight average molecular weight (Mn) and the number average molecular weight (Mw) measured by gel permeation chromatography (GPC) is preferably 1.1 to 1.8. More preferably, it is 1.1-1.7, More preferably, it is 1.1-1.5, Most preferably, it is 1.1-1.3. In GPC measurement, chloroform is usually used as a mobile phase, the measurement is performed with a polystyrene gel column, and the number average molecular weight and the like can be determined in terms of polystyrene.

The main chain of the vinyl polymer of the present invention may be linear or branched.

（式中、Ｒ^１、Ｒ^２、ｎの定義は上記式（１）と同じ。Ｒ^３はメチル基、エチル基、ブチル基、２−メトキシエチル基またはステアリル基を示す。（Ａ）はビニル系モノマー（Ａ）由来の繰り返し単位、（Ｂ）は開始剤残基、ｘは正の整数をそれぞれ示す。）As the structure of the vinyl polymer having a hydrolyzable silyl group, the structure represented by the following general formula (2) is preferable in that it is easy to adjust the physical properties regardless of the application in industrial use.

(Wherein R ¹ , R ² and n are defined as in the above formula (1). R ³ represents a methyl group, ethyl group, butyl group, 2-methoxyethyl group or stearyl group. (A) is vinyl. (A repeating unit derived from the monomer (A), (B) is an initiator residue, and x is a positive integer.)

R ¹ is preferably a methyl group or an ethyl group, R ² is preferably a hydrogen atom, a methyl group, or an ethyl group, and n is preferably 0 or 1 in view of the availability of raw materials and the high reactivity of the polymer terminal. . R ³ is preferably ethyl, butyl (n-butyl, isobutyl, tert-butyl), or 2-methoxyethyl.
CO ₂ R ³ is a group derived from the vinyl monomer (A).

(Curable composition)
The present invention also relates to a curable composition containing the vinyl polymer having a hydrolyzable silyl group of the present invention.
According to the intended use properties, other resins / polymers, fillers, plasticizers, stabilizers, curing catalysts / curing agents, compounding agents are added to the vinyl polymer having a hydrolyzable silyl group at the end of the present invention. Etc. can be mixed to obtain the curable composition of the present invention.

Examples of other resins and polymers include, but are not limited to, the following. Polyether polymers, vinyl polymers other than the present invention, and the like.

Examples of the filler include, but are not limited to, the following. Calcium carbonate, silica, carbon black, titanium oxide, talc, etc.

Examples of plasticizers include, but are not limited to, the following. Phthalate ester compounds, non-aromatic dibasic acid esters, phosphate esters, polyether polyols, epoxy group-containing plasticizers, polyester plasticizers, vinyl polymers, and the like.

Stabilizers include, but are not limited to: Anti-light stabilizers such as thioether-based antioxidants, phosphorus-based antioxidants, hindered phenol-based antioxidants, ultraviolet absorbers, hindered amine-based light stabilizers, and benzoate-based light stabilizers.

Various curing catalysts / curing agents include, but are not limited to, the following. Intramolecular coordination derivatives of dialkyl tin, tetravalent tin compounds such as oxy derivatives of dialkyl tin compounds, and divalent tin such as tin octylate.

Examples of the compounding agent include, but are not limited to, dehydrating agents, adhesion imparting agents such as silane coupling agents, and thixotropic properties.
Specific applications of the curable composition of the present invention include sealing materials, adhesives, adhesives, elastic adhesives, paints, powder paints, foams, potting materials for electric and electronic materials, films, molding materials, artificial marble, etc. Can be mentioned.

Specific examples of the present invention are shown below, but the present invention is not limited to the following examples.
In the following Examples and Comparative Examples, “parts” and “ppm” represent “parts by weight” and “parts by weight”, respectively.
“Number average molecular weight” and “molecular weight distribution (ratio of weight average molecular weight to number average molecular weight)” were calculated by a standard polystyrene conversion method using gel permeation chromatography (GPC). However, a GPC column filled with polystyrene cross-linked gel (shodex GPC K-804; manufactured by Showa Denko KK) was used as the GPC solvent with chloroform.

For analysis of bromine content in the polymer, ICPMS (Inductively Coupled Plasma Mass Spectrometry) or X-ray fluorescence analyzer was used.

In consideration of industrialization, reagents were used in the reaction without any purification or other treatment after obtaining mass-produced reagents.

(Production Example 1)
200 g of n-butyl acrylate, 81.6 g of modified ethanol (AS-1 manufactured by Nippon Alcohol Sales Co., Ltd. (mixed solvent consisting of 85.5 wt% ethanol, 13.4 wt% ethyl acetate, 1.1 wt% 2-propanol) )), 17.6 g of diethyl 2,5-dibromoadipate were placed in a jacketed stirring reactor (1) and stirred for 30 minutes while bubbling nitrogen to obtain a homogeneous solution.

Another stirring vessel (2) was prepared, and in that vessel, cupric bromide (CuBr ₂ ) 28 mg, hexamethyltris (2-aminoethyl) amine (Me ₆ TREN) 29 mg, triethylamine 13 mg, denatured ethanol (AS -1) 0.97 g was charged and stirred under a nitrogen stream until a uniform solution was obtained.

Further, another stirring vessel (3) was prepared, and in that vessel, 100 g of denatured ethanol (AS-1), 15 g of ascorbic acid, and 17.2 g of triethylamine were stirred for 30 minutes under a nitrogen stream to obtain a uniform solution.

The solution in the stirring vessel (2) is put into the jacketed stirring reactor (1) and stirred for 10 minutes, the jacket temperature of the jacketed stirring reactor (1) is set to 70 ° C, and the internal temperature becomes 65 ° C or higher. The polymerization reaction was started by starting dropping the solution in the stirring vessel (3).
The ascorbic acid solution prepared in the stirring vessel (3) was dropped intermittently so that 28 mg of ascorbic acid was added to the stirring reactor with jacket (1) in 1 hour. When the polymerization reaction started and the internal temperature of the jacketed stirred reactor (1) reached 75 ° C. due to the heat of polymerization, dropwise addition of 800 g of butyl acrylate that had been subjected to nitrogen bubbling for 30 minutes was started. The dropping speed was adjusted so that the whole amount of n-butyl acrylate (800 g) was dropped into the jacketed stirred reactor (1) in 90 minutes. The total monomer molar amount (M) added at this time corresponds to 160 equivalents of the molar amount (I) of the initiator (diethyl 2,5-dibromoadipate in this case) (hereinafter referred to as M / I = 160).

While the ascorbic acid solution was dropped intermittently, the inner temperature was adjusted to 80 ° C. or less by appropriate jacket operation, and when the reaction rate of n-butyl acrylate reached 98 mol%, The pressure was reduced and volatile components were removed to obtain a polymer [1].

300 g of this polymer [1] and 300 g of butyl acetate were mixed to obtain a uniform dope solution. To this solution, 3 g of Kyoward 500SH (manufactured by Kyowa Chemical Industry Co., Ltd.) and 3 g of Kyoward 700SEN-S (manufactured by Kyowa Chemical Industry Co., Ltd.) were added, put into a stirrer with a jacket, and under a nitrogen atmosphere at 100 ° C. Agitation was performed. After the solution temperature was lowered to room temperature, filter filtration was performed, the solvent was removed under reduced pressure, and purification of the polymer [1] was completed.

At this time, the polymer [1] had a number average molecular weight of 23,000 and a molecular weight distribution of 1.25. The number of bromine ends per polymer [1] molecule determined by ¹ H-NMR analysis was 1.7.

Example 1
50 g of the purified polymer [1] obtained in (Production Example 1), 50 g of modified ethanol (AS-1), and 8 g of vinyltrimethoxysilane (A171; manufactured by Momentive Performance Materials) are mixed to obtain a uniform solution. The mixture was placed in a jacketed stirring device (4) and stirred for 30 minutes while bubbling nitrogen.

1.95 g of a copper solution having the same composition ratio as the copper solution prepared by the stirring device (2) of (Production Example 1) was placed in the stirring device (4) and stirred for 10 minutes. The same composition as the ascorbic acid solution prepared by the stirring device (3) of (Production Example 1) while adjusting the jacket temperature so that the internal temperature of the stirring device (4) is 65 ° C. to 70 ° C. in a nitrogen atmosphere. The ascorbic acid solution was intermittently added dropwise so that 245 mg of ascorbic acid entered the stirring device (4) in one hour. The dropping of the ascorbic acid solution was completed in 2 hours, and 30 minutes later, the stirring apparatus was depressurized and the solvent and unreacted vinyltrimethoxysilane were distilled off to obtain a polymer [2].
The number of steps required to obtain the polymer [2] having a hydrolyzable silyl group was 2 steps including 1 step in (Production Example 1).

50 g of this polymer [2] and 50 g of butyl acetate were mixed to obtain a uniform dope solution. To this solution, 0.5 g of KYOWARD 500SH (KW500SH; manufactured by Kyowa Chemical Industry Co., Ltd.) and 0.5 g of KYOWARD 700SEN-S (KW700SEN-S; manufactured by Kyowa Chemical Industry Co., Ltd.) are added and placed in a jacketed stirring apparatus. Then, stirring was performed under a nitrogen atmosphere at 100 ° C. After the solution temperature was lowered to room temperature, filter filtration was performed, the solvent was removed under reduced pressure, and purification of the first-stage polymer [2] was completed.

Furthermore, this polymer [2] was dissolved in 30 g of methanol, and reprecipitation purification was performed. Reprecipitation purification was performed three times in total by adding methanol of the same weight as the methanol solution fractionated by the reprecipitation operation to the polymer solution. Finally, methanol was removed under reduced pressure, and the second-stage polymer [2] Purification was completed and purification of the polymer [2] was completed.

At this time, the polymer [2] had a number average molecular weight of 33,000 and a molecular weight distribution of 1.38. The number of trimethoxysilyl ends per molecule of the polymer [2] determined by ¹ H-NMR analysis was 1.9. When the amount of bromine was analyzed with a fluorescent X-ray analyzer, it was found that 1800 ppm was contained in the polymer [2].

(Example 2)
100 g of the purified polymer [1] obtained in (Production Example 1), 100 g of denatured ethanol (AS-1), and 24.3 g of vinyltrimethoxysilane (A171; manufactured by Momentive Performance Materials) were mixed and homogeneously mixed. The resulting solution was placed in a jacketed stirring device (5) and stirred for 30 minutes while nitrogen was bubbled.
1.2 g of a copper solution having the same composition as the copper solution prepared by the stirring device (2) of (Production Example 1) was placed in the stirring device (5) and stirred for 10 minutes. The same solution as the ascorbic acid solution prepared with the stirring device (3) of (Production Example 1) while adjusting the jacket temperature so that the internal temperature of the stirring device (5) is from 65 ° C to 70 ° C under a nitrogen atmosphere Was prepared again, and the ascorbic acid solution was dropped intermittently so that 100 mg of ascorbic acid entered the stirrer (5) in 1 hour. The dropping of the ascorbic acid solution was completed in 6 hours. After 3 hours, the stirring apparatus was depressurized, and the solvent and unreacted vinyltrimethoxysilane were distilled off to obtain a polymer [3].
The number of steps required to obtain the polymer [3] having a hydrolyzable silyl group was 2 steps including 1 step in (Production Example 1).

100 g of this polymer [3] was dissolved in 60 g of methanol, and reprecipitation purification was performed. Reprecipitation purification was performed a total of 3 times by adding methanol of the same weight as the methanol solution separated by reprecipitation operation to the polymer solution. Finally, methanol was removed under reduced pressure, and the second-stage polymer [3] Purification was completed and purification of the polymer [3] was completed.
At this time, the polymer [3] had a number average molecular weight of 30,000 and a molecular weight distribution of 1.40. The number of terminals of trimethoxysilyl per molecule of the polymer [3] determined by ¹ H-NMR analysis was 3.0. The amount of bromine in the polymer analyzed by ICPMS was 2749 ppm.

(Example 3)
200 g of n-butyl acrylate, 89.9 g of denatured ethanol (AS-1 manufactured by Nippon Alcohol Sales Co., Ltd.), 0.19 g of triethylamine, and 19.0 g of ethyl 2-bromoisobutyrate are placed in a jacketed stirring reactor (6), and nitrogen is added. Stirring was performed for 30 minutes while bubbling to obtain a uniform solution.

1.95 g of a copper solution having the same composition ratio as the copper solution prepared by the stirring device (2) of (Production Example 1) was placed in the stirring device (6) and stirred for 10 minutes. Under a nitrogen atmosphere, the jacket temperature of the stirring device (6) is set to 70 ° C., and a solution having the same composition ratio as the ascorbic acid solution prepared by the stirring device (3) of (Production Example 1) is prepared again. Was added dropwise to initiate the polymerization reaction. Polymerization proceeds by intermittently dropping the ascorbic acid solution so that 32 mg of ascorbic acid enters the stirrer (6) in one hour, and the internal temperature of the stirrer (6) reaches 75 ° C. by the heat of polymerization. At that time, 800 g of n-butyl acrylate, which had been subjected to nitrogen bubbling for 30 minutes, was started to be dropped. The dropping speed was adjusted so that the total amount of n-butyl acrylate (800 g) was dropped into the stirring device (6) in 90 minutes.

While the ascorbic acid solution was dropped intermittently, the inner temperature was adjusted to 80 ° C. or less by appropriate jacket operation, and when the reaction rate of n-butyl acrylate reached 98 mol%, The pressure was reduced and volatile components were removed to obtain a polymer [4]. The amount of ascorbic acid added before obtaining the polymer [4] was 154 ppm based on the total monomer charge weight (M / I = 160).

At this time, the polymer [4] had a number average molecular weight of 11909 and a molecular weight distribution of 1.21. The number of bromine terminals per molecule of the polymer [4] determined by ¹ H-NMR analysis was 0.8.

Next, 250 g of denatured ethanol that had been bubbled with nitrogen for 30 minutes, 217 g of vinyltrimethoxysilane, 0.15 g of triethylamine, and a copper solution prepared with the stirring apparatus (2) of (Production Example 1) 10.4 g of a copper solution having the same composition ratio was added, and mixed sufficiently under a nitrogen stream until a uniform solution was obtained. The temperature of the jacket is adjusted so that the temperature of the polymer solution in the stirring device is 65 ° C. to 70 ° C., and stirring is performed so that 1000 mg of ascorbic acid enters the stirring reaction device (6) in one hour (Production Example 1). The ascorbic acid solution prepared by the apparatus (3) was dropped intermittently. After 5.5 hours, dropping of the ascorbic acid solution was completed, the inside of the reaction vessel was depressurized, and volatile components were removed to obtain a polymer [5]. The total amount of ascorbic acid added during 5.5 hours was 5637 ppm relative to the total monomer charge.

Polymer [5] (100 parts) was dissolved in 100 parts of butyl acetate and placed in a jacketed agitator together with Kyoward 500SH (1 part) and Kyoward 500SEN-S (1 part). The temperature was adjusted to 100 ° C. and the mixture was stirred for 30 minutes under a nitrogen atmosphere. Then, filter filtration was performed with filter aid R100S (1 part; manufactured by Showa Chemical Industry Co., Ltd.) to separate the solid and liquid. Volatile components of the obtained polymer solution were removed under reduced pressure with an evaporator to obtain a purified polymer [5].

At this time, the number average molecular weight of the polymer [5] was 11870, and the molecular weight distribution was 1.17. The number of trimethoxysilyl ends per molecule of polymer [5] determined by ¹ H-NMR analysis was 2.0. The number of steps required to obtain the polymer [5] having a hydrolyzable silyl group was one step.

Example 4
The same procedure as in Example 3 except that 100 parts of methanol was used instead of butyl acetate for the unpurified polymer [5], and the temperature of the polymer solution was adjusted to 55 ° C. Purification was performed at

The number average molecular weight of the polymer [5] at this time was 11465, and the molecular weight distribution was 1.13. The number of trimethoxysilyl ends per molecule of polymer [5] determined by ¹ H-NMR analysis was 2.0. The number of steps required to obtain the polymer [5] having a hydrolyzable silyl group was one step.

(Comparative Example 1)
CuBr (8.4 g, 58.5 mmol) was charged into a 2 L separable flask equipped with a reflux tube and a stirrer, and the inside of the reaction vessel was purged with nitrogen. Acetonitrile (88 g) was added, and the mixture was stirred in an oil bath at 70 ° C. for 30 minutes. To this, n-butyl acrylate (200 g), diethyl 2,5-dibromoadipate (17.6 g, 48.8 mmol), pentamethyldiethylenetriamine (0.407 mL, 0.338 g, 2.0 mmol) (hereinafter referred to as triamine) The reaction was started. While heating and stirring at 70 ° C., n-butyl acrylate (800 g) was continuously added dropwise. Triamine was added during the dropwise addition of n-butyl acrylate.

When the monomer reaction rate reached 96%, the remaining monomer and acetonitrile were devolatilized at 70 ° C. to obtain a polymer [6] (M / I = 160). The number average molecular weight of the polymer [6] was 23800, and the molecular weight distribution was 1.23. The number of bromine ends per molecule of the polymer [6] determined from ¹ H-NMR analysis was 1.7. As a result of elemental analysis, the amount of bromine contained in the polymer [6] was 4900 mg with respect to 1 kg of the polymer. The total amount of triamine dropped during the polymerization was 1.52 g.

To the polymer [6], 1,7-octadiene (144 mL, 107 g, 975 mmol), which is an ethylenically unsaturated group-containing compound, is added, further acetonitrile (264.1 g) is added, and 3.38 g of triamine is added. Subsequently, the mixture was heated and stirred at 70 ° C. In this reaction, an ethylenically unsaturated group is introduced at the end of the polymer [6].

The reaction mixture was devolatilized by heating, diluted to 100 parts of toluene, and the polymerization catalyst was removed by passing the mixture through a column of activated alumina. The polymer solution is concentrated, dissolved in 100 parts of methylcyclohexane with respect to the polymer, 4 parts of adsorbent (2 parts of Kyoward 500SH / 2 parts of Kyoward 700SL: both manufactured by Kyowa Chemical Co., Ltd.) are added, and oxygen is added. -The mixture was heated and stirred under a nitrogen mixed gas atmosphere. The insoluble matter was removed, and the polymer solution [7] was obtained by concentrating the polymer solution. The number average molecular weight of the polymer [7] was 23800, and the molecular weight distribution was 1.23. As a result of ICPMS analysis, the amount of bromine contained in the polymer [7] was 4900 ppm. ^{From 1} H-NMR analysis, the number of ethylenically unsaturated groups introduced per molecule of the polymer [6] was 2.0.

Polymer [7] was heated and devolatilized at 180 ° C. for 6 hours (decompression degree: 10 torr or less) to obtain an ethylenically unsaturated group-containing poly (n-butyl acrylate) having a reduced bromine content. As a result of ICPMS analysis, the amount of bromine contained in the polymer was 370 ppm. The number average molecular weight was 24100, and the molecular weight distribution was 1.25.

To this ethylenically unsaturated group-containing poly (n-butyl acrylate), 2.6 g of dimethoxymethylsilane (3 molar equivalents relative to the ethylenically unsaturated group) and 0.85 g of methyl orthoformate (relative to the ethylenically unsaturated group) 3 molar equivalents), platinum catalyst [bis (1,3-divinyl-1,1,3,3-tetramethyldisiloxane) platinum complex catalyst xylene solution 0.04 g: hereinafter referred to as platinum catalyst] (1 kg of polymer as platinum) 10 mg), and stirred under heating at 80 ° C. for 1 hour under a nitrogen atmosphere. The disappearance of the ethylenically unsaturated group was confirmed by ¹ H-NMR analysis, and the reaction mixture was concentrated to obtain a polymer [8] containing a dimethoxysilyl group which is a hydrolyzable silyl group. The number average molecular weight was 26600, and the molecular weight distribution was 1.41.

The number of steps required to obtain the polymer [8] having a hydrolyzable silyl group is one step of polymerization and ethylenically unsaturated group introduction reaction, one step of purification using an adsorbent and filtration performed before hydrosilylation. When the process and the debromination process by heating are counted as one process and the hydrosilylation process is counted as one process, the total number of processes is four. In order to complete the hydrosilylation reaction, the purification step by adsorbent and filtration and the debromination step are indispensable and counted as the number of steps necessary to obtain the polymer [8] having a hydrolyzable silyl group. doing.

(Example 5)
200 g of n-butyl acrylate, 81.6 g of denatured ethanol (AS-1 manufactured by Japan Alcohol Sales Co., Ltd.), 35.1 g of diethyl 2,5-dibromoadipate are placed in a jacketed stirring reactor (1), and nitrogen bubbling is performed. However, stirring was carried out for 30 minutes to obtain a uniform solution.

A stirring vessel (2) was prepared, and in that vessel, cupric bromide (CuBr ₂ ) 53 mg, hexamethyltris (2-aminoethyl) amine (Me ₆ TREN) 54 mg, triethylamine 24 mg, denatured ethanol (AS-1) ) 1.82 g was charged and stirred under a nitrogen stream until a uniform solution was obtained.

Further, a stirring vessel (3) was prepared, and 100 g of denatured ethanol (AS-1), 15 g of ascorbic acid, and 17.2 g of triethylamine were stirred for 30 minutes in a nitrogen stream to obtain a uniform solution.

Put the contents of the stirring vessel (2) into the jacketed stirring reactor (1), stir for 10 minutes, set the jacket temperature of the jacketed stirring reactor (1) to 70 ° C, and the internal temperature is 65 ° C or higher Then, the polymerization reaction was started by starting the dropping of the solution in the stirring vessel (3).
The ascorbic acid solution prepared in the stirring vessel (3) was dropped intermittently so that 29 mg of ascorbic acid entered the jacketed stirring reactor (1) in 1 hour. When the polymerization reaction started and the internal temperature of the jacketed stirred reactor (1) reached 75 ° C. due to the heat of polymerization, dropwise addition of 800 g of butyl acrylate that had been subjected to nitrogen bubbling for 30 minutes was started. The dropping speed was adjusted so that the entire amount of n-butyl acrylate (800 g) was dropped into the jacketed stirred reactor (1) in 90 minutes (M / I = 80).

While the ascorbic acid solution was dropped intermittently, the internal temperature was adjusted to 80 ° C. or less by appropriate jacket operation, and when the reaction rate of n-butyl acrylate reached 97 mol%, ascorbic acid was dropped. Was temporarily terminated. The amount of ascorbic acid added so far was 182 ppm with respect to the total monomer charge weight.

Next, 193.4 g of vinyl dimethoxymethyl silane that was nitrogen bubbled for 30 minutes, 13.65 g of copper catalyst solution (same composition as the copper catalyst solution prepared in the stirring vessel (2)), and 0.24 g of triethylamine were mixed for 10 minutes. Stir to make a homogeneous solution. Ascorbic acid solution prepared by the stirring device (3) of (Production Example 1) while adjusting the jacket temperature so that the inner temperature of the stirring reactor with jacket (1) is 60 ° C to 80 ° C under a nitrogen atmosphere A solution having the same composition ratio was prepared again, and the ascorbic acid solution was dropped intermittently so that 1000 mg of ascorbic acid entered the jacketed stirred reactor (1) in 1 hour. The dropping of the ascorbic acid solution was completed in 7 hours, and 30 minutes later, nitrogen gas containing 6 vol% oxygen was sealed in the reaction solution, and heated and stirred at 60 ° C. to 80 ° C. for 20 minutes to completely deactivate the copper catalyst. I let you. Polymer [9] was obtained as an ethanol solution.
The number of steps required to obtain the polymer [9] having a hydrolyzable silyl group was one step.

To this ethanol solution, 918.4 g of denatured ethanol (AS-1) was additionally mixed to obtain a uniform ethanol solution. 20 g of Kyoward 500SH (KW500SH; manufactured by Kyowa Chemical Industry Co., Ltd.) and 20 g of Kyoward 700SEN-S (KW700SEN-S; manufactured by Kyowa Chemical Industry Co., Ltd.) were added to this solution, and the mixture was placed in a jacketed agitator and a nitrogen atmosphere. The mixture was stirred under heating at 80 ° C. for 1 hour. Thereafter, the solution temperature was lowered to room temperature, filter filtration was performed, the solvent was removed under reduced pressure, and purification of the polymer [9] was completed.

At this time, the polymer [9] had a number average molecular weight of 15,130 and a molecular weight distribution of 1.45. The number of terminals of methyldimethoxysilyl per molecule of the polymer [9] determined by ¹ H-NMR analysis was 0.7.

(Comparative Example 2)
CuBr (8.4 g, 58.5 mmol) was charged into a 2 L separable flask equipped with a reflux tube and a stirrer, and the inside of the reaction vessel was purged with nitrogen. Acetonitrile (88 g) was added, and the mixture was stirred in an oil bath at 70 ° C. for 30 minutes. To this, n-butyl acrylate (200 g), diethyl 2,5-dibromoadipate (35.1 g, 97.5 mmol), pentamethyldiethylenetriamine (1.63 mL, 1.35 g, 8.0 mmol) (hereinafter referred to as triamine) The reaction was started. While heating and stirring at 70 ° C., n-butyl acrylate (800 g) was continuously added dropwise. Triamine was added during the dropwise addition of n-butyl acrylate.

When the monomer reaction rate reached 95%, the remaining monomer and acetonitrile were devolatilized at 70 ° C. to obtain a polymer [10] (M / I = 80). The number average molecular weight of the polymer [10] was 11790, and the molecular weight distribution was 1.08. The number of bromine ends per molecule of the polymer [10] determined by ¹ H-NMR analysis was 2.0.

To the polymer [10], 1,7-octadiene (288 mL, 215 g, 1950 mmol), which is an ethylenically unsaturated group-containing compound, is added, further acetonitrile (351.7 g) is added, and 6.76 g of triamine is added. Subsequently, the mixture was heated and stirred at 70 ° C. In this reaction, an ethylenically unsaturated group is introduced at the terminal of the polymer [10].

The reaction mixture was heated and stirred at 80 ° C. for 4 hours under a 6 vol% oxygen / nitrogen mixed gas atmosphere. Then, it volatilizes at 80 degreeC, It dilutes to 100 parts of butyl acetate, The polymerization catalyst was removed by letting a solvent mixture pass to the column of 1 part of filter aids (radiolite).

Next, add 2 parts of adsorbent (20 g) (1 part of KYOWARD 500SH; 1 part of KYOWARD 700SL; 10 g: both manufactured by Kyowa Chemical Co., Ltd.), stir at 80 ° C. for 1 hour, and filter filter. Insoluble solids were removed. After repeating this adsorption treatment operation once more, the obtained polymer solution was concentrated under reduced pressure to obtain a polymer [11]. At this time, the polymer [11] had a number average molecular weight of 12,620 and a molecular weight distribution of 1.15.

Polymer [11] was heated and desorbed at 190 ° C. for 2 hours with 1.1 parts (11 g) of an adsorbent (Kyoward 500SH 1 part; 10 g / Kyoward 700SL 0.1 part; both manufactured by Kyowa Chemical Co., Ltd.). Volatile (the degree of vacuum is 10 torr or less), followed by 100 parts of butyl acetate (1000 g), 1.1 parts of adsorbent (11 g) (1 part of Kyoward 500SH; 0.1 part of Kyoward 700SL; 1 g: Kyowa both together (Chemical Co., Ltd.) was mixed and stirred, heated and stirred at 185 ° C. for 6 hours, cooled to room temperature, and filtered to obtain ethylenically unsaturated group-containing poly (butyl acrylate) having a reduced bromine content. It was.

To this ethylenically unsaturated group-containing poly (n-butyl acrylate), 3.5 g of dimethoxymethylsilane (2 molar equivalents relative to the ethylenically unsaturated group), 0.88 g of methyl orthoformate (relative to the ethylenically unsaturated group) 0.5 molar equivalent), platinum catalyst [bis (1,3-divinyl-1,1,3,3-tetramethyldisiloxane) platinum complex catalyst xylene solution 0.04 g: hereinafter referred to as platinum catalyst] 10 mg / kg of the combined product) was mixed, and the mixture was heated and stirred at 115 ° C. for 1 hour in a nitrogen atmosphere. The disappearance of the ethylenically unsaturated group was confirmed by ¹ H-NMR analysis, and the reaction mixture was concentrated to obtain a polymer [12] containing a dimethoxysilyl group which is a hydrolyzable silyl group. The number average molecular weight was 12700, and the molecular weight distribution was 1.17.

The number of steps necessary to obtain a polymer [12] having a hydrolyzable silyl group is one step of polymerization, ethylenically unsaturated group introduction reaction, and heating and stirring in a 6 vol% oxygen / nitrogen mixed gas atmosphere. Heating and stirring with an auxiliary agent, filtering, followed by heating and stirring with an adsorbent and filtering, 1 step, debromination step by heating at 185 ° C and 190 ° C, 1 step, hydrosilylation step as 1 step, total 4 steps. In order to complete the hydrosilylation reaction, a filtration step with a filter aid and an adsorbent, and a debromination step at high temperatures (185 ° C. and 190 ° C.) are essential, and a polymer having a hydrolyzable silyl group It is counted as the number of steps necessary to obtain [12].

（Ｍ／Ｉ＝１６０の場合）
表１に示すように、加水分解性シリル基を有する重合体（Ｍ／Ｉ＝１６０）を得るまでに必要な工程数は、実施例１、２、３、４は比較例１よりも少なく、本発明のビニル系重合体を製造するプロセスは生産性に優れる製造工程であるといえる。

(When M / I = 160)
As shown in Table 1, the number of steps required to obtain a polymer having a hydrolyzable silyl group (M / I = 160) was less in Examples 1, 2, 3, and 4 than in Comparative Example 1. It can be said that the process for producing the vinyl polymer of the present invention is a production process with excellent productivity.

Moreover, when the bromine content in the polymer which did not pass through a refinement | purification and a debromination process is compared, Example 1, 2 is 1800 ppm and 2749 ppm, and the comparative example 1 is 4900 ppm. In particular, comparison between Example 2 and Comparative Example 1 measured by ICPMS revealed that initiator-derived bromine can be eliminated from the vinyl polymer without special debromination and purification.
Further, when the devolatilized vinyl polymer (polymers [2], [3], [5], [9]) was analyzed by ¹ H-NMR, an unsaturated double bond (C = C) was present.
From these results, it is presumed that after the monomer (C) reacts with the terminal of the vinyl polymer (P), the terminal bromine derived from the initiator is detached from the vinyl polymer as HX or R ⁴ X. .

As shown in Tables 1 and 2, when the amount of the auxiliary raw material used is compared with the amount of monomer charged per kg, Examples 3 and 4 require significantly less than Comparative Example 1, and The process for producing a vinyl polymer is an effective production process in terms of reducing waste reduction.

(When M / I = 80)
As shown in Table 1, the number of steps required to obtain a polymer having a hydrolyzable silyl group (M / I = 80) was less in Example 5 than in Comparative Example 2, and the vinyl polymer of the present invention. It can be said that the process of manufacturing is a manufacturing process with excellent productivity.

As shown in Tables 1 and 2, when the amount of the auxiliary raw material used is compared with the amount of monomer charged per kg, Example 5 requires significantly less than Comparative Example 2, and the vinyl type of the present invention The process for producing a polymer is an effective production process in terms of reducing waste reduction.

Claims (10)

Vinyl monomer (C) having a hydrolyzable silyl group at the terminal of vinyl polymer (P) which is a living polymer of vinyl monomer (A) using initiator (B) having a carbon-halogen bond Having a structure derived from,
A vinyl polymer having a hydrolyzable silyl group at the terminal, wherein the halogen atom derived from the initiator (B) has a structure desorbed from the polymer. The vinyl polymer having a hydrolyzable silyl group at the terminal according to claim 1, wherein the living polymer is an atom transfer radical polymer. The vinyl polymer having a hydrolyzable silyl group at the terminal according to claim 1 or 2, wherein the vinyl polymer (P) is a (meth) acrylic acid ester polymer. 4. The hydrolyzable silyl at the terminal according to claim 1, wherein the initiator (B) having a carbon-halogen bond is diethyl 2,5-dibromoadipate or ethyl 2-bromoisobutyrate. Vinyl polymer having a group. The hydrolyzable silyl group is a hydrolyzable silyl group represented by the following general formula (1). The vinyl polymer having a hydrolyzable silyl group at a terminal according to any one of claims 1 to 4.
—Si (R ¹ ) _n (OR ² ) _3-n (1)
Wherein R ¹ is an alkyl group having 1 to 8 carbon atoms, an aryl group or an aralkyl group, R ² is hydrogen or an alkyl group having 1 to 8 carbon atoms, an aryl group or an aralkyl group, and n is an integer of 0 to 2. Show.) The hydrolyzable silyl group at the terminal according to any one of claims 1 to 5, wherein the vinyl monomer (C) having a hydrolyzable silyl group has a structure represented by the following general formula (3). A vinyl polymer having

Wherein R ¹ is an alkyl group having 1 to 8 carbon atoms, an aryl group or an aralkyl group, R ² is a hydrogen atom or an alkyl group having 1 to 8 carbon atoms, an aryl group or an aralkyl group, and R ⁴ is a hydrogen atom or carbon. A number 1 to 8 alkyl group, aryl group or aralkyl group, R ⁵ is a direct bond, a phenyl group represented by (C ₆ H ₄ ), or (CH ₂ ) _m (m is an integer of 1 to 8) 2 Valent hydrocarbon group, n represents an integer of 0 to 2.) The hydrolyzable silyl at the terminal according to any one of claims 1 to 6, wherein the vinyl monomer (C) having a hydrolyzable silyl group is vinyltrimethoxysilane or vinyldimethoxymethylsilane. Vinyl polymer having a group. The vinyl polymer having a hydrolyzable silyl group at the terminal according to any one of claims 1 to 7, wherein the vinyl polymer has a structure selected from structures represented by the following general formula (2).

(Wherein R ¹ is an alkyl group having 1 to 8 carbon atoms, an aryl group or an aralkyl group, R ² is hydrogen or an alkyl group having 1 to 8 carbon atoms, an aryl group or an aralkyl group, n is an integer of 0 to 2, R ³ represents a methyl group, an ethyl group, a butyl group, a 2-methoxyethyl group or a stearyl group, (A) is a repeating unit derived from the vinyl monomer (A), (B) is an initiator residue, x is Each positive integer is indicated.) A curable composition comprising a vinyl polymer having a hydrolyzable silyl group at a terminal according to claim 1. A step of living polymerizing the vinyl monomer (A) using the initiator (B) having a carbon-halogen bond to obtain a vinyl polymer (P); and
The method includes the step of reacting a vinyl polymer (P) with a vinyl monomer (C) having a hydrolyzable silyl group and introducing a hydrolyzable silyl group into the terminal of the vinyl polymer (P). 8. A method for producing a vinyl polymer having a hydrolyzable silyl group at a terminal thereof according to any one of 8 above.