JPH1180570A - Curable composition - Google Patents

Abstract

PROBLEM TO BE SOLVED: To obtain a curable composition containing a vinylic polymer having alkenyl groups at the molecular terminals in a high ratio as a main component. SOLUTION: This curable composition contains (A) a vinylic polymer having alkenyl groups represented by formula I: CH<2> =C(R<1> ) (R<1> is hydrogen or methyl group) at the terminals and (B) a hydrosilyl group-containing compound as essential components. The vinylic polymer having cross linkable alkenyl groups represented by formula I at the terminals is obtained by the following processes. (1) A vinylic monomer is polymerized in the presence of an organic halide or a sulfonyl halide compound as an initiator and a transition metal complex as a catalyst to produce a vinylic polymer having terminal structures of formula II: -C(R<1> )(R<2> )(X) (R<1> , R<2> are each a group bound to the ethylenic unsaturated group of the vinylic monomer; X is chlorine, bromine or iodine). (2) The halogen in the group of formula II is converted into the alkenyl group in the group of formula I.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

TECHNICAL FIELD The present invention relates to a curable composition. More specifically, the present invention relates to a curable composition using a hydrosilylation reaction for a crosslinking reaction.

[0002]

2. Description of the Related Art Polymers having an alkenyl group at a terminal are:
It is known that by using a compound having a hydrosilyl group as a curing agent, a cured product excellent in heat resistance, durability, and deep-section curability is provided. As such a main chain skeleton of a polymer having an alkenyl group at its terminal, various types are known, and polyether polymers such as polyethylene oxide, polypropylene oxide, and polytetramethylene oxide, polybutadiene, and polyisoprene. Hydrocarbon polymers such as polychloroprene, polyisobutylene or hydrogenated products thereof, polyester polymers such as polyethylene terephthalate, polybutylene terephthalate and polycaprolactone, and silicone polymers such as polydimethylsiloxane. .

[0003] Curable compositions using these polymers have various problems. For example, a polyether-based cured product has insufficient heat resistance and weather resistance. It has been pointed out that hydrocarbon-based cured products such as polybutadiene and polyisoprene are also inferior in heat resistance and weather resistance due to internal double bonds remaining in the main chain. A polyisobutylene-based cured product having no internal double bond has a problem that the weather resistance is excellent but the viscosity is very high, and the workability is poor. It has been pointed out that the polyester-based cured product also has poor weather resistance. Although silicone-based cured products are extremely excellent in terms of weather resistance, heat resistance, cold resistance, and workability, they still have problems in paint adhesion and stainability.

[0004] On the other hand, there are a wide variety of types of vinyl monomers capable of undergoing radical polymerization, and polymers having various properties that cannot be obtained with the above-mentioned polyether polymers, hydrocarbon polymers or polyester polymers. Synthesis is possible. For example, a (meth) acrylic polymer has high weather resistance because the main chain is a saturated hydrocarbon type, and also has excellent paint adhesion and stain resistance. Utilizing this property, (meth) acrylic polymers have been synthesized into (meth) acrylic polymers having alkenyl groups in their side chains, and their use as highly weather-resistant paints has been proposed (for example, Kaihei 3-9
5266, JP-A-3-277645, JP-A-7-703
99 etc.).

[0005]

However, since these vinyl polymers have an alkenyl group in the side chain, their cured products have poor elastic properties and are difficult to use as elastomers. Thus, a composition using a vinyl polymer having an alkenyl group at a terminal is desired. JP-A-5-255415 discloses a method for producing a latex by emulsion polymerization of a vinyl monomer and a diene monomer using dialkenyl disulfide as a chain transfer agent.
JP-A-1-247403 discloses a method for producing an acrylic polymer having an alkenyl group at a terminal, characterized in that an allyl group-containing disulfide or thiuram disulfide is used as an initiator. With these methods, a vinyl polymer having alkenyl groups at both terminals can be obtained in principle, but it is not easy to reliably introduce an alkenyl group at the terminals. Japanese Patent Application Laid-Open No. 5-262808 discloses that a vinyl polymer having hydroxyl groups at both ends is obtained by using a polysulfide chain transfer agent having a hydroxyl group in a large excess with respect to an initiator, and to obtain a vinyl polymer having hydroxyl groups at both ends. A method for producing a vinyl polymer having a polymerizable alkenyl group is disclosed. In this method, an alkenyl group is introduced at a relatively high ratio at the terminal, but there is a problem in the production process because an expensive chain transfer agent is used in a large amount.

It is an object of the present invention to provide a curable composition using a vinyl polymer having a high ratio of alkenyl groups at terminals.

[0007]

The curable composition for solving the above-mentioned problems is composed of the following two components: (A) an alkenyl group-terminated (meth) acrylic polymer represented by the general formula 1, CH ₂ = C (R ¹ )-(1) (wherein R ² is hydrogen or a methyl group) A curable composition comprising (B) a compound containing a hydrosilyl group as an essential component. The vinyl polymer of the component (A) can be obtained by the following steps: (1) radical polymerization of a vinyl monomer using an organic halide or a sulfonyl halide compound as an initiator and a transition metal complex as a catalyst to obtain the general formula 2 A vinyl polymer having a halogen atom at the terminal shown is prepared, and -C (R ² ) (R ³ ) (X) (2) (wherein R ² and R ³ are ethylenically unsaturated vinyl monomers. X represents chlorine, bromine or iodine.) (2) It is produced by converting the terminal halogen of the polymer into an alkenyl group of the general formula 1.

[0008]

BEST MODE FOR CARRYING OUT THE INVENTION The curable composition of the present invention comprises the following 2
Ingredients: (A) a vinyl polymer having an alkenyl group at the terminal represented by the general formula 1, CH ₂ ＣC (R ¹ )-(1) (in the above formula, R ¹ is a hydrogen or a methyl group) Group-containing compound as an essential component. Hereinafter, the curable composition of the present invention will be described in detail. [Regarding the vinyl polymer of the component (A)] The alkenyl group of the general formula 1 which is a crosslinkable group of the vinyl polymer of the component (A) is specifically described below. First, the general formula 3 CH ₂ = C ( R ¹ ) —R ⁴ —O— (3) (wherein R ¹ is the same as above, R ⁴ is a direct bond or a divalent organic group having 1 to 20 carbon atoms, and at least one ether (Which may contain a bond). As R ⁴ , for example,
_{(CH 2) n -, (} n an integer of 0~20), - CH ₂ CH
_{(CH 3) -, - CH} 2 CH (CH 3) CH 2 -; - CH 2
OCH ₂ CH ₂ —, —CH ₂ OCH ₂ CH ₂ CH ₂ —, —CH
₂ CH ₂ OCH ₂ CH ₂ —, —CH ₂ CH ₂ OCH ₂ CH ₂ CH
_{2 -; o-, m-, p} -C 6 H 4 -, o-, m-, p-C
_{H 2 -C 6 H 4 -,} o-, m-, p-CH 2 -C 6 H 4 -CH
_2- and the like.

Next, general formula 4 or 5: CH ₂ ＣC (R ¹ ) —R ⁴ —OC (O) — (4) CH ₂ ＣC (R ¹ ) —R ⁴ —C (O) O— ( 5) (wherein, R ¹ and R ⁴ are the same as described above). As R ⁴ , any of those described above can be suitably used.

The group represented by the general formula 6 is also a specific example of the alkenyl group of the formula 1. CH ₂ ＣC (R ¹ ) -R ^5- (6) (wherein R ¹ is the same as above, R ⁵ is a direct bond or a divalent hydrocarbon group having 1 to 20 carbon atoms) And hydrogen-based groups. The ^{_{R 5 - (CH 2) n}} - (n is 0 to an integer _{of), - CH 2 CH (CH} 3) -, - CH 2
CH (CH ₃₎ CH ₂ - and the like.

The alkenyl group of the formula 1 is further represented by the formula 7 CH ₂ ＣC (R ¹ ) -R ⁴ -OC (O) O- (7) (wherein R ¹ and R ⁴ are the same as above). And a group having a carbonate bond. Further, a group having an electron withdrawing group represented by the formula 8 is also exemplified as a specific example of the alkenyl group of the formula (1). CH ₂ ＣC (R ¹ ) -R ⁴ -C (R ⁶ ) (R ⁷ )-(8) (wherein R ¹ and R ⁴ are the same as above, and R ⁶ and R ⁷ are both carbanion C ⁻ ) A stabilizing electron-withdrawing group, or one of which is the aforementioned electron-withdrawing group and the other is hydrogen or a carbon atom having 1 to 1
0 alkyl group or phenyl group) At least one of R ⁶ and R ⁷ is an electron withdrawing group for stabilizing the carbanion, and specific examples thereof include —CO ₂ R
(Ester group), -C (O) R (keto group), -CON
(R ₂₎ (amide group), - COSR (thioester group), - CN (nitrile group), - NO ₂ (nitro group), and the like. The substituent R is an alkyl group having 1 to 20 carbon atoms, an aryl group having 6 to 20 carbon atoms or 7 to 20 carbon atoms.
And preferably an alkyl group having 1 to 10 carbon atoms or a phenyl group. As R ⁶ and R ⁷ , —CO ₂ R, —C (O) R and —CN are particularly preferred.

The monomer forming the main chain of the vinyl polymer (A) is not particularly limited, and various monomers can be used. For example, (meth) acrylic acid, methyl (meth) acrylate, ethyl (meth) acrylate, n-propyl (meth) acrylate, isopropyl (meth) acrylate, n- (meth) acrylate 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)
2-ethylhexyl acrylate, nonyl (meth) acrylate, decyl (meth) acrylate, dodecyl (meth) acrylate, phenyl (meth) acrylate, toluyl (meth) acrylate, benzyl (meth) acrylate, ( 2-methoxyethyl (meth) acrylate, 3-methoxybutyl (meth) acrylate, 2- (meth) acrylate
Hydroxyethyl, 2-hydroxypropyl (meth) acrylate, stearyl (meth) acrylate, (meth)
Glycidyl acrylate, 2-aminoethyl (meth) acrylate, γ- (methacryloyloxypropyl) trimethoxysilane, ethylene oxide adduct of (meth) acrylic acid, trifluoromethylmethyl (meth) acrylate, (meth) acryl 2-trifluoromethylethyl acid, 2-perfluoroethylethyl (meth) acrylate, 2-perfluoroethyl-2- (meth) acrylate
Perfluorobutylethyl, 2-perfluoroethyl (meth) acrylate, perfluoromethyl (meth) acrylate, diperfluoromethylmethyl (meth) acrylate, 2-perfluoromethyl-2- (meth) acrylate
(Meth) acrylic monomers such as perfluoroethylmethyl, 2-perfluorohexylethyl (meth) acrylate, 2-perfluorodecylethyl (meth) acrylate, 2-perfluorohexadecylethyl (meth) acrylate Styrene monomers such as styrene, vinyltoluene, α-methylstyrene, chlorostyrene, styrenesulfonic acid and salts thereof; fluorine-containing vinyl monomers such as perfluoroethylene, perfluoropropylene and vinylidene fluoride; vinyltrimethoxysilane, vinyl Silicon-containing vinyl monomers such as triethoxysilane; maleic anhydride, maleic acid, monoalkyl and dialkyl esters of maleic acid; fumaric acid, monoalkyl and dialkyl esters of fumaric acid; maleimide, methyl ester Maleimide monomers such as imide, ethylmaleimide, propylmaleimide, butylmaleimide, hexylmaleimide, octylmaleimide, dodecylmaleimide, stearylmaleimide, phenylmaleimide, and cyclohexylmaleimide; vinyl monomers containing a nitrile group such as acrylonitrile and methacrylonitrile; acrylamide; Vinyl monomers containing an amide group such as methacrylamide; vinyl esters such as vinyl acetate, vinyl propionate, vinyl pivalate, vinyl benzoate and vinyl cinnamate; alkenes such as ethylene and propylene; conjugated dienes such as butadiene and isoprene Kind;
Examples thereof include vinyl chloride, vinylidene chloride, allyl chloride, allyl alcohol and the like. These may be used alone or a plurality of them may be copolymerized. Among them, styrene-based monomers and (meth) acrylic-acid-based monomers are preferred from the viewpoint of the physical properties of the product. More preferred are acrylate monomers and methacrylate monomers, and even more preferred is butyl acrylate. In the present invention, these preferable monomers may be copolymerized with other monomers. In such a case, it is preferable that these preferable monomers are contained in a weight ratio of 40%.

The molecular weight distribution of the vinyl polymer of component (A), that is, the ratio of the weight average molecular weight to the number average molecular weight measured by gel permeation chromatography is not particularly limited, but is usually less than 1.8. It is preferably at most 1.7, more preferably at most 1.6,
It is more preferably at most 1.5, particularly preferably at most 1.4, most preferably at most 1.3.
In the GPC measurement in the present invention, chloroform is usually used as a mobile phase, the measurement is performed using a polystyrene gel column, and the number average molecular weight and the like can be determined in terms of polystyrene.

The number average molecular weight of the vinyl polymer is not particularly limited, but is preferably in the range of 500 to 1,000,000, more preferably 1000 to 100,000. [Method for producing vinyl polymer as component (A)] The vinyl polymer having an alkenyl group at the terminal represented by the general formula 1 can be obtained by the method described above. In the present invention, the following steps are performed: The vinyl polymer of the component (A) is subjected to the following steps: (1) radical polymerization of a vinyl monomer using an organic halide or a sulfonyl halide compound as an initiator and a transition metal complex as a catalyst to give a general formula 2 A vinyl polymer having a terminal structure shown in the following formula is produced, and -C (R ² ) (R ³ ) (X) (2) (wherein R ² and R ³ are X represents chlorine, bromine or iodine.) (2) The terminal group X of the polymer is converted into a substituent containing an alkenyl group represented by the general formula 1. The manufacturing method is used.

As a method for producing a vinyl polymer having a terminal structure represented by the general formula 2, for example, in polymerization using a halide as a chain transfer agent (telogen), carbon tetrachloride, methylene chloride, carbon tetrabromide, Although a method using methylene bromide or the like is known, it is difficult to surely introduce halogens at both ends with this method. In contrast to this method, the use of atom transfer radical polymerization, which has been energetically studied recently, ensures that a halogen is introduced at the terminal (see, for example, Matyjaszewski et al., J. Am.
Am. Chem. Soc. 1995, 117, 561
4, Macromolecules 1995, 28,
7901, Science 1996, 272, 86
6, or Sawamoto et al., Macromole
cules 1995, 28, 1721). According to these methods, the polymerization speed is generally very high, and the polymerization proceeds in a living manner and the molecular weight distribution is narrow (Mw / Mn = 1.1-1.5)
A polymer is obtained, and the molecular weight can be freely controlled by the charging ratio of the monomer and the initiator.

In this atom transfer radical polymerization, an organic halide, particularly an organic halide having a highly reactive carbon-halogen bond (for example, a carbonyl compound having a halogen at the α-position or a compound having a halogen at the benzyl position) Alternatively, a sulfonyl halide compound is used as an initiator. In order to obtain a crosslinkable vinyl polymer using this polymerization method, an organic halide having two or more starting points or a sulfonyl halide compound is used as an initiator. Specific examples thereof include o
_{-, m-, p-XCH 2} -C 6 H 4 -CH 2 X, o-, m
_{-, p-CH 3 C (} H) (X) -C 6 H 4 -C (H)
_{(X) CH 3, o-,} m-, p- (CH 3) 2 C (X) -
C ₆ H ₄ —C (X) (CH ₃ ) ₂ (where C ₆
H ₄ is a phenylene group, X is chlorine, bromine or _{iodine,) RO 2 C-C (} H) (X) - (CH 2) n -C (H)
_{(X) -CO 2 R, RO} 2 C-C (CH 3) (X) - (C
_{H 2) n -C (CH 3} ) (X) -CO 2 R, RC (O) -C
(H) (X) - ( CH 2) n -C (H) (X) -C (O)
R, RC (O) -C ( CH 3) (X) - (CH 2) n -C
(CH ₃ ) (X) —C (O) R (wherein, R is an alkyl group, aryl group or aralkyl group having 1 to 20 carbon atoms, n is an integer of 0 to 20, X is chlorine, bromine, iodine) _{) XCH 2 -C (O) -CH} 2 X, H 3 C-C (H) (X)
—C (O) —C (H) (X) —CH ₃ , (H ₃ C) ₂ C
(X) -C (O) -C (X) (CH 3) 2, C 6 H 5 C
(H) (X) - ( CH 2) n -C (H) (X) C 6 H 5 ( in the above formula, X is chlorine, bromine or iodine, n represents 0 to 20 integer) XCH ₂ CO ₂ - (CH ₂ ) _n —OCOCH ₂ X, CH ₃ C
_{(H) (X) CO 2} - (CH 2) n -OCOC (H)
_{(X) CH 3, (CH} 3) 2 C (X) CO 2 - (CH 2) n -
OCOC (X) (CH ₃ ) ₂ (where n is an integer of 1 to 20) XCH ₂ C (O) C (O) CH ₂ X, CH ₃ C (H)
(X) C (O) C (O) C (H) (X) CH ₃ , (C
H ₃ ) ₂ C (X) C (O) C (O) C (X) (CH ₃ ) ₂ ,
_{o-, m-, p-XCH 2} CO 2 -C 6 H 4 -OCOCH 2
X, o-, m-, p- CH 3 C (H) (X) CO 2 -C 6
_{H 4 -OCOC (H) (X} ) CH 3, o-, m-, p-
_{(CH 3) 2 C (X} ) CO 2 -C 6 H 4 -OCOC (X)
_{(CH 3) 2, o-,} m-, p-XSO 2 -C 6 H 4 -SO 2
X (wherein X is chlorine, bromine or iodine) The transition metal complex used as the polymerization catalyst is not particularly limited, but is preferably a group 7 or 8 or 9 or 9 of the periodic table.
It is a metal complex complex containing a Group 10, Group or Group 11 element as a central metal. More preferred are zero-valent copper, 1
Complex of divalent copper, divalent ruthenium, divalent iron or divalent nickel. Among them, a copper complex is preferable. Specific examples of monovalent copper compounds include cuprous chloride, cuprous bromide, cuprous iodide, cuprous cyanide, cuprous oxide, cuprous perchlorate, and the like. is there. When a copper compound is used, 2,2'-bipyridyl and its derivatives, 1,10-phenanthroline and its derivatives, tetramethylethylenediamine, pentamethyldiethylenetriamine, hexamethyltris (2-aminoethyl) amine and the like for enhancing the catalytic activity A ligand such as a polyamine is added. Further, a tristriphenylphosphine complex of divalent ruthenium chloride (RuCl ₂ (PPh ₃ ) ₃ ) is also suitable as a catalyst. When a ruthenium compound is used as a catalyst, aluminum alkoxides are added as an activator. Further, bis (triphenylphosphine) complex of divalent iron (FeCl ₂ (PPh ₃ ) ₂ ) and bistriphenylphosphine complex of divalent nickel (NiCl ₂ (PP
h _{3) 2),} and a divalent bis tributylphosphine complex nickel _{(NiBr 2 (PBu 3) 2} ) are also suitable as catalysts.

There are no particular restrictions on the vinyl monomer used in this polymerization, and any of those already exemplified can be suitably used. The polymerization reaction can be performed without a solvent or in various solvents. Examples of the solvent include hydrocarbon solvents such as benzene and toluene;
Ether solvents such as diethyl ether, tetrahydrofuran, diphenyl ether, anisole and dimethoxybenzene; halogenated hydrocarbon solvents such as methylene chloride, chloroform and chlorobenzene; ketone solvents such as acetone, methyl ethyl ketone and methyl isobutyl ketone;
Alcohol solvents such as methanol, ethanol, propanol, isopropanol, n-butyl alcohol and tert-butyl alcohol; nitrile solvents such as acetonitrile, propionitrile and benzonitrile; ester solvents such as ethyl acetate and butyl acetate; ethylene carbonate And carbonate-based solvents such as propylene carbonate. These can be used alone or in combination of two or more. The polymerization can also be carried out in an emulsion system or a system using a supercritical fluid CO ₂ as a medium.

The polymerization can be carried out at a temperature of from 0 to 200 ° C., preferably from room temperature to 150 ° C. The vinyl polymer having a terminal alkenyl group of the formula 1 can be obtained by converting the halogen of the vinyl polymer having a terminal halogen obtained by the above polymerization into an alkenyl group.

Various methods can be used to convert the halogen terminal of Formula 2 into an alkenyl group-containing substituent. For example, by polymerizing a vinyl monomer using an organic halide or a sulfonyl halide compound as an initiator and a transition metal complex as a catalyst, the general formula 2
And a compound having both a polymerizable alkenyl group and at least one other alkenyl group as a second monomer. No particular limitation is imposed on the compound having both a polymerizable alkenyl group other at least one alkenyl group, for example, the general formula _{9 H 2 C = C (R} 1) -R 8 -R 9 -C (R 1 ) = CH ₂ (9) (wherein, R ¹ is hydrogen or a methyl group, which may be the same or different, R ⁸ is —C (O) O— (ester group), or o-, m- , P-phenylene group, and R ⁹ may be a direct bond or a divalent organic group having 1 to 20 carbon atoms, which may contain one or more ether bonds). When R ⁸ is an ester group, it is a (meth) acrylate compound, and when R ⁸ is a phenylene group, it is a styrene compound. The R ⁹ in the general formula 9,
Alkylene groups such as methylene, ethylene and propylene; o
-, m-, p- phenylene, aralkyl groups such as benzyl _{group; -CH 2 CH 2 -O-CH} 2 - or -O-CH ₂ - alkylene group containing an ether bond and the like.

Among the compounds of formula 9, H ₂ C ＣC (H) C (O) O (CH ₂ ) _{n
-CH = CH 2, H 2 C} = C (CH 3) C (O) O (C
H ₂ ) _n —CHＣＨCH ₂ (In each of the above formulas, n is 0 to
20 _{integer) H 2 C = C (H} ) C (O) O (CH 2) n -O- (CH 2)
_m CH = CH ₂ , H ₂ C = C (CH ₃ ) C (O) O (C
In _{H 2) n -O- (CH 2} ) m CH = CH 2 ( above equations, n represents an integer of 1 to 20, m an integer of 0~20) o-, m-, p- divinylbenzene, o-, m-, p-
_{H 2 C = CH-C 6} H 4 -CH 2 CH = CH 2, o-, m
_{-, p-H 2 C =} CH-C 6 H 4 -CH 2 -C (CH 3) =
_{CH 2, o-, m-, p} -H 2 C = CH-C 6 H 4 -CH 2
_{CH 2 CH = CH 2, o-} , m-, p-H 2 C = CH-C 6
_{H 4 -OCH 2 CH = CH 2} , o-, m-, p-H 2 C = C
_{H-C 6 H 4 -OCH 2} -C (CH 3) = CH 2, o-, m
_{-, p-H 2 C =} CH-C 6 H 4 -OCH 2 CH 2 CH = C
_{H 2, o-, m-, p} -H 2 C = C (CH 3) -C 6 H 4 -
_{C (CH 3) = CH 2} , o-, m-, p-H 2 C = C (C
_{H 3) -C 6 H 4 -CH} 2 CH = CH 2, o-, m-, p-
_{H 2 C = C (CH 3} ) -C 6 H 4 -CH 2 C (CH 3) = CH
_{2, o-, m-, p-} H 2 C = C (CH 3) -C 6 H 4 -C
_{H 2 CH 2 CH = CH 2} , o-, m-, p-H 2 C = C (C
_{H 3) -C 6 H 4 -OCH} 2 CH = CH 2, o-, m-, p
_{-H 2 C = C (CH 3} ) -C 6 H 4 -OCH 2 -C (CH 3)
_{= CH 2, o-, m-,} p-H 2 C = C (CH 3) -C 6 H
_{4 -OCH 2 CH 2 CH = CH} 2 ( provided that in the above chemical formula,
C ₆ H ₄ represents a phenylene group. Is preferred.

Further, a compound having at least two alkenyl groups having low polymerizability may be reacted as the second monomer. Such a compound is not particularly limited, and examples thereof include a compound represented by the general formula (10). ^{_{H 2 C = C (R 1}} ) -R-C (R 1) = CH 2 (10) ( wherein, R ¹ is hydrogen or a methyl group, may be the same or different, R represents 1 to 4 carbon atoms The divalent organic group may have at least one ether bond with a divalent organic group of -20 to 20. The compound represented by the general formula 10 is not particularly limited, but is easily available, and therefore, 1,5-hexadiene , 1,7-octadiene and 1,9-decadiene are preferred.

As another method of introducing an alkenyl group at the terminal, a halogen-substituted polymer represented by the formula 2 is substituted with halogen by reacting various organometallic compounds having an alkenyl group with the polymer. A method can also be used. Examples of such organometallic compounds include organic lithium, organic sodium, organic potassium, organic magnesium, organic tin, organic silicon, organic zinc, organic copper, and the like. In particular, organotin and organocopper compounds are preferred because they selectively react with the halogen of the formula 2 and have low reactivity with a carbonyl group.

The organotin compound having an alkenyl group is not particularly limited, but is preferably a compound represented by the following formula (11). H ₂ C ＝ C (R ¹⁰ ) C (R ¹¹ ) (R ¹² ) Sn (R ¹³ ) ₃ (11) (wherein R ¹⁰ , R ¹¹ , and R ¹² are hydrogen or have 1 to 1 carbon atoms)
The alkyl group having 0, the aryl group having 6 to 10 carbon atoms, or the aralkyl group having 7 to 10 carbon atoms may be the same or different. R ¹³ is an alkyl group having 1 to 10 carbon atoms,
(Aryl group or aralkyl group) Specific examples of the organotin compound of the formula 11 include allyltributyltin, allyltrimethyltin, allyltri (n-octyl) tin, and allyltri (cyclohexyl) tin.

Examples of the organic copper compound having an alkenyl group include lithium divinyl copper, lithium diallyl copper, lithium diisopropenyl copper and the like. A vinyl polymer having a terminal alkenyl group can also be obtained by allowing a stabilized carbanion having a terminal alkenyl group represented by the general formula 12 to act on a polymer having a terminal halogen in the formula (2). ^{M + C - (R 6)} (R 7) -R 4 -C (R 1) = CH 2 (12) ( ^{wherein, R 1, R 4, R} 6, R 7 are as defined above, M ⁺ is (Alkali metal ion or quaternary ammonium ion) As described above, at least one of R ⁶ and R ⁷ is an electron withdrawing group for stabilizing a carbanion, and —CO ₂ R,
-C (O) R and -CN are particularly preferred. Also, M ⁺
Is a counter cation of a carbanion, and is exemplified by an alkali metal ion or a quaternary ammonium ion. As the alkali metal ion, lithium ion, sodium ion, potassium ion, and as the quaternary ammonium ion, tetramethylammonium ion, tetraethylammonium ion, trimethylbenzylammonium ion, trimethyldodecylammonium ion,
And tetrabutylammonium ion.

The carbanion of the general formula 12 can be obtained by reacting a basic compound with a precursor thereof and extracting an active proton. Examples of the precursor compound of the carbanion of the general formula 12 include the following compounds: H
_{2 C = CH-CH (CO} 2 CH 3) 2, H 2 C = CH-CH
_{(CO 2 C 2 H 5)} 2, H 2 C = CH- (CH 2) n CH (C
O ₂ CH ₃ ) ₂ , H ₂ C = CH- (CH ₂ ) _n CH (CO ₂ C _{2
H 5) 2, o-, m-} , p-H 2 C = CH-C 6 H 4 -CH
_{(CO 2 CH 3) 2,} o-, m-, p-H 2 C = CH-C 6
_{H 4 -CH (CO 2 C 2} H 5) 2, o-, m-, p-H 2 C =
_{CH-C 6 H 4 -CH 2} CH (CO 2 CH 3) 2, o-, m
_{-, p-H 2 C =} CH-C 6 H 4 -CH 2 CH (CO 2 C 2 H
_{5) 2, H 2 C =} CH-CH (C (O) CH 3) (CO 2 C 2
_{H 5), H 2 C =} CH- (CH 2) n CH (C (O) C
_{H 3) (CO 2 C 2} H 5), o-, m-, p-H 2 C = CH
_{-C 6 H 4 -CH (C (} O) CH 3) (CO 2 C 2 H 5), o
_{-, m-, p-H 2} C = CH-C 6 H 4 -CH 2 CH (C
_{(O) CH 3) (CO} 2 C 2 H 5), H 2 C = CH-CH
_{(C (O) CH 3)} 2, H 2 C = CH- (CH 2) n CH
_{(C (O) CH 3)} 2, o-, m-, p-H 2 C = CH-
_{C 6 H 4 -CH (C (} O) CH 3) 2, o-, m-, p-H
_{2 C = CH-C 6 H} 4 -CH 2 CH (C (O) CH 3) 2, H
_{2 C = CH-CH (CN} ) (CO 2 C 2 H 5), H 2 C = C
_{H- (CH 2) n CH (} CN) (CO 2 C 2 H 5), o-,
_{m-, p-H 2 C =} CH-C 6 H 4 -CH (CN) (CO 2
_{C 2 H 5), o-,} m-, p-H 2 C = CH-C 6 H 4 -C
_{H 2 CH (CN) (CO} 2 C 2 H 5), H 2 C = CH-CH
(CN) ₂ , H ₂ CＣＨCH— (CH ₂ ) _n CH (CN) ₂ ,
_{o-, m-, p-H 2} C = CH-C 6 H 4 -CH (C
_{N) 2, o-, m-,} p-H 2 C = CH-C 6 H 4 -CH 2
_{CH (CN) 2, H 2} C = CH- (CH 2) n NO 2, o
_{-, m-, p-H 2} C = CH-C 6 H 4 -CH 2 NO 2, o
_{-, m-, p-H 2} C = CH-C 6 H 4 -CH 2 CH 2 N
_{O 2, H 2 C = CH} -CH (C 6 H 5) (CO 2 C 2 H 5),
_{H 2 C = CH- (CH 2} ) n CH (C 6 H 5) (CO 2 C
_{2 H 5), o-, m-} , p-H 2 C = CH-C 6 H 4 -CH
(C ₆ H ₅ ) (CO ₂ C ₂ H ₅ ), o-, m-, p-H ₂ C =
_{CH-C 6 H 4 -CH 2} CH (C 6 H 5) (CO 2 C 2 H 5)
(In the above formula, n is an integer of 1 to 10).

The proton is abstracted from the above compound.
Various basic compounds are used to obtain the carbanion of No. 2. These basic compounds include: alkali metals such as sodium, potassium and lithium; sodium methoxide, potassium methoxide, lithium methoxide, sodium ethoxide, potassium ethoxide, lithium ethoxide, sodium-tert-butoxide,
Metal alkoxides such as potassium-tert-butoxide; carbonates such as sodium carbonate, potassium carbonate, lithium carbonate, and sodium hydrogen carbonate; hydroxides such as sodium hydroxide and potassium hydroxide; sodium hydride, potassium hydride, and methyllithium , Hydrides such as ethyl lithium; n-butyl lithium, tert-butyl lithium,
Organic metals such as lithium diisopropylamide and lithium hexamethyldisilazide; ammonia; alkylamines such as trimethylamine, triethylamine and tributylamine; polyamines such as tetramethylethylenediamine and pentamethyldiethylenetriamine; pyridine compounds such as pyridine and picoline; Is done. The amount of the basic compound used may be an equivalent amount or a small excess amount relative to the precursor, and is preferably 1 to 1.2 equivalents.

A quaternary ammonium salt may be used as the above-mentioned carbanion. In this case, it is obtained by preparing an alkali metal salt of a carboxylic acid compound and reacting it with a quaternary ammonium halide. 4
As the secondary ammonium halide, tetramethylammonium halide, tetraethylammonium halide,
Examples include trimethylbenzyl ammonium halide, trimethyl dodecyl ammonium halide, tetrabutyl ammonium halide, and the like.

Examples of the solvent used for reacting the precursor compound and the basic compound include hydrocarbon solvents such as benzene and toluene; ether solvents such as diethyl ether, tetrahydrofuran, diphenyl ether, anisole and dimethoxybenzene; Halogenated hydrocarbon solvents such as methylene chloride and chloroform; acetone,
Ketone solvents such as methyl ethyl ketone and methyl isobutyl ketone; alcohol solvents such as methanol, ethanol, propanol, isopropanol, n-butyl alcohol and tert-butyl alcohol; nitrile solvents such as acetonitrile, propionitrile and benzonitrile; ethyl acetate Solvent solvents such as ethylene carbonate and propylene carbonate; amide solvents such as dimethylformamide and dimethylacetamide; and sulfoxide solvents such as dimethyl sulfoxide. These can be used alone or in combination of two or more.

By reacting the above precursor with a basic compound, a carbanion represented by the general formula 11 is prepared,
By reacting with the halogen-terminated vinyl polymer of the formula (2), the desired vinyl polymer having a terminal alkenyl group represented by the formula (1) can be obtained. As a method for introducing an alkenyl group, an oxyanion having an alkenyl group represented by Formula 13 may be reacted. M ⁺ O ^-- R ⁴ -C (R ¹ ) = CH ₂ (13) (wherein R ¹ , R ⁴ and M ⁺ are the same as above) The precursor of the oxyanion of the general formula (13) is as follows: compounds such _{as: H 2 C = CH-CH} 2 -OH, H 2
_{C = CH-CH (CH 3} ) -OH, H 2 C = C (CH 3)
_{-CH 2 -OH, H 2 C =} CH- (CH 2) n -OH (n
Represents an integer of 2 to 20. _{), H 2 C = CH-} CH 2 -
_{O- (CH 2) 2 -OH,} H 2 C = CH-C (O) O-
_{(CH 2) 2 -OH, H} 2 C = C (CH 3) -C (O) O-
_{(CH 2) 2 -OH, o-} , m-, p-H 2 C = CH-C 6
_{H 4 -CH 2 -OH, o-,} m-, p-H 2 C = CH-C
_{H 2 -C 6 H 4 -CH 2} -OH, o-, m-, p-H 2 C =
_{CH-CH 2 -O-C 6} H 4 alcoholic hydroxyl group-containing compounds such as _{-CH 2 -OH; o-, m-,} p-H 2 C = CH-
_{C 6 H 4 -OH, o-,} m-, p-H 2 C = CH-CH 2 -
_{C 6 H 4 -OH, o-,} m-, p-H 2 C = CH-CH 2 -
A phenolic hydroxyl group-containing compound such as OC ₆ H ₄ —OH;
_{H 2 C = CH-C (} O) -OH, H 2 C = C (CH 3) -
_{C (O) -OH, H 2} C = CH-CH 2 -C (O) -O
_{H, H 2 C = CH- (} CH 2) n -C (O) -OH (n
Represents an integer of 2 to 20. _{), H 2 C = CH- (} C
_{H 2) n -OC (O)} - (CH 2) m -C (O) -OH (m
And n are the same or different and represent an integer of 0 to 19. ), O-, m-, p- H 2 C = CH-C 6 H 4 -C
(O) -OH, o-, m- , p-H 2 C = CH-CH 2 -
_{C 6 H 4 -C (O)} -OH, o-, m-, p-H 2 C = C
_{H-CH 2 -O-C 6} H 4 -C (O) -OH, o-, m
_{-, p-H 2 C =} CH- (CH 2) n -OC (O) -C 6 H
_4- C (O) -OH (n represents an integer of 0 to 13)
And other carboxyl group-containing compounds.

A proton is extracted from the above compound,
Various basic compounds are used to obtain the anion 3, and specific examples thereof include all the basic compounds used when preparing the carbanion of the formula (12). Also, as for the reaction solvent, those used when preparing the carbanion are preferably used.

As another method for introducing an alkenyl group,
It is also possible to use a method of reacting a halogen-terminated vinyl polymer with a metal simple substance or an organometallic compound to form an enolate anion, followed by reaction with an electrophilic compound having an alkenyl group. Zinc is particularly preferable as the metal simple substance in that the generated enolate anion is unlikely to cause a side reaction such as attacking or transferring another ester group. Various kinds of electrophilic compounds having an alkenyl group can be used. Examples thereof include an alkenyl group-containing compound having a leaving group such as a halogen or an acetyl group, a carbonyl compound having an alkenyl group, an isocyanate compound having an alkenyl group, and an acid halide having an alkenyl group. Of these, the use of an alkenyl group-containing compound having a leaving group such as a halogen or an acetyl group is preferable because a hetero atom is not introduced into the main chain and the weather resistance of the vinyl polymer is not lost.

In a process for producing a vinyl polymer, which comprises polymerizing a vinyl monomer using an organic halide or a sulfonyl halide compound as an initiator and a transition metal complex as a catalyst, an organic halide having an alkenyl group is produced. When used as an initiator, a vinyl polymer having an alkenyl group at one terminal and the other terminal having the structure of Formula 2 can be obtained. By converting the halogen at the terminal end of the polymer thus obtained into an alkenyl group-containing substituent, a vinyl polymer having alkenyl groups at both ends can be obtained. As the conversion method, the method already described can be used.

The organic halide having an alkenyl group is not particularly limited, and examples thereof include those having the structure represented by the general formula (14). R ¹⁴ R ¹⁵ C (X) -R ¹⁶ -R ⁹ -C (R ¹ ) = CH ₂ (14) (where R ¹ , R ⁹ and X are the same as above, and R ¹⁴ and R ¹⁵ are hydrogen or An alkyl group having 1 to 20 carbon atoms, an aryl group having 6 to 20 carbon atoms, an aralkyl group having 7 to 20 carbon atoms, or those mutually connected at the other end, wherein R ¹⁵ is —C (O) O—
(Ester group), -C (O)-(keto group), or o
-, M-, p-phenylene group) represented by the general formula 14:
Specific examples of the organic halide having an alkenyl group include XCH ₂ C (O) O (CH ₂ ) _n CH ＝ CH ₂ and H ₃ C
C (H) (X) C (O) O (CH ₂ ) _n CH = CH ₂ ,
_{(H 3 C) 2 C (} X) C (O) O (CH 2) n CH = C
H ₂ , CH ₃ CH ₂ C (H) (X) C (O) O (CH ₂ ) _n
CH = CH ₂ ,

[0034]

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(In each of the above formulas, X represents chlorine, bromine,
Or iodine, n represents an integer of _{0~20) XCH 2 C (O)} O (CH 2) n O (CH 2) m CH = C
H ₂ , H ₃ CC (H) (X) C (O) O (CH ₂ ) _n O (C
H ₂ ) _m CH = CH ₂ , (H ₃ C) ₂ C (X) C (O) O
(CH ₂ ) _n O (CH ₂ ) _m CH = CH ₂ , CH ₃ CH ₂ C
(H) (X) C (O) O (CH ₂ ) _n O (CH ₂ ) _m CH =
CH ₂ ,

[0036]

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(In each of the above formulas, X represents chlorine, bromine,
Or iodine, n represents an integer of 1 to 20, m is an integer of 0~20) o, m, p- XCH 2 -C 6 H 4 - (CH 2) n -CH = C
_{H 2, o, m, p} -CH 3 C (H) (X) -C 6 H 4 - (C
_{H 2) n -CH = CH 2} , o, m, p-CH 3 CH 2 C
_{(H) (X) -C 6} H 4 - in _{(CH 2) n -CH = CH} 2 ( above equations, X is chlorine, bromine or iodine,, n
0-20 integer) o, m, p-XCH 2 -C 6 H 4 - (CH 2) n -O- (C
_{H 2) m -CH = CH 2} , o, m, p-CH 3 C (H)
_{(X) -C 6 H 4 -} (CH 2) n -O- (CH 2) m -CH =
_{CH 2, o, m, p} -CH 3 CH 2 C (H) (X) -C 6 H
₄ - (CH ₂₎ in _{n -O- (CH 2) m CH} = CH 2 ( above equations, X is chlorine, bromine or iodine,, n is 1 to
20 integer, m is 0 to 20 integer) o, m, p-XCH 2 -C 6 H 4 -O- (CH 2) n -CH
_{= CH 2, o, m,} p-CH 3 C (H) (X) -C 6 H 4 -
_{O- (CH 2) n -CH =} CH 2, o, m, p-CH 3 CH
_{2 C (H) (X)} -C 6 H 4 -O- (CH 2) n -CH = C
H ₂ (in each of the above formulas, X is chlorine, bromine, or iodine, and n is an integer of 0 to 20) o, m, p-XCH ₂ —C ₆ H ₄ —O— (CH ₂ ) _n —O—
_{(CH 2) m -CH = CH} 2, o, m, p-CH 3 C (H)
_{(X) -C 6 H 4 -O-} (CH 2) n -O- (CH 2) m -C
_{H = CH 2, o, m} , p-CH 3 CH 2 C (H) (X) -
_{C 6 H 4 -O- (CH 2} ) n -O- (CH 2) m -CH = CH
₂ (In each of the above formulas, X is chlorine, bromine, or iodine, n is an integer of 1 to 20, m is an integer of 0 to 20) Further, as an organic halide having an alkenyl group, a compound represented by the general formula 15 Is mentioned.

H ₂ C ＝ C (R ¹ ) -R ⁹ -C (R ¹⁴ ) (X) -R ¹⁷ -R ¹⁵ (15) (wherein, R ¹ , R ⁹ , R ¹⁴ , R ¹⁵ , X Is the same as above, R ¹⁷
Is a direct bond, -C (O) O- (ester group), -C
(O)-(keto group) or o-, m-, p-phenylene group) R ⁹ is a direct bond or a divalent organic group having 1 to 20 carbon atoms (one or more ether bonds However, in the case of a direct bond, a vinyl group is bonded to the carbon to which the halogen is bonded, and the compound is a halogenated allylic compound. In this case, since the carbon-halogen bond is activated by the adjacent vinyl group, C (O) O is used as R ^17.
It is not always necessary to have a group or a phenylene group, and a direct bond may be used. When R ⁹ is not a direct bond, R ¹⁷ is C 10 to activate a carbon-halogen bond.
(O) O group, C (O) group and phenylene group are preferred.

If the compound of formula 15 is specifically exemplified, CH ₂ ＣＨCHCH ₂ X, CH ₂ ＣC (CH ₃ ) CH
₂ X, CH ₂ ＣＨCHC (H) (X) CH ₃ , CH ₂ ＣC (C
H ₃ ) C (H) (X) CH ₃ , CH ₂ ＣＨCHC (X) (C
H ₃ ) ₂ , CH ₂ （CHC (H) (X) C ₂ H ₅ , CH ₂ ＣC
HC (H) (X) CH (CH 3) 2, CH 2 = CHC
(H) (X) C ₆ H ₅ , CH ₂ ＣＨCHC (H) (X) CH _{2
C 6 H 5, CH 2 =} CHCH 2 C (H) (X) -CO 2 R,
_{CH 2 = CH (CH 2)} 2 C (H) (X) -CO 2 R, CH
_{2 = CH (CH 2) 3} C (H) (X) -CO 2 R, CH 2 =
_{CH (CH 2) 8 C (} H) (X) -CO 2 R, CH 2 = CH
_{CH 2 C (H) (X} ) -C 6 H 5, CH 2 = CH (CH 2) 2
C (H) (X) -C 6 H 5, CH 2 = CH (CH 2) 3 C
(In each formula mentioned above, X is chlorine, bromine or iodine,, R is an alkyl group having 1 to 20 carbon atoms, an aryl group, an aralkyl group) (H) (X) -C 6 H 5 and the like can be given .

Specific examples of the sulfonyl halide compound having an alkenyl group include o-, m-, p-C
_{H 2 = CH- (CH 2)} n -C 6 H 4 -SO 2 X, o-, m
_{-, p-CH 2 = CH-} (CH 2) n -O-C 6 H 4 -SO 2
X (in each of the above formulas, X is chlorine, bromine, or iodine, and n is an integer of 0 to 20).

An organic halide having an alkenyl group,
Alternatively, when a halogenated sulfonyl compound is used as an initiator, a polymer is obtained in which one terminal is an alkenyl group and the other terminal is a halogen terminal represented by the formula 2, which can substitute the halogen of the formula 2 in the polymer. A vinyl polymer having an alkenyl group at the terminal can also be obtained by coupling halogen terminals with a compound having a total of two or more same or different functional groups.

There are no particular restrictions on the group having two or more identical or different functional groups capable of substituting a terminal halogen, but polyols, polyamines, polycarboxylic acids, polythiols, and salts thereof, alkali metal sulfides, etc. Is preferred. Specific examples of these compounds include: ethylene glycol, 1,2-propanediol, 1,3
-Propanediol, 2-methyl-1,3-propanediol, 2,2-dimethyl-1,3-propanediol, 1,4-butanediol, 1,3-butanediol, 1,2-butanediol, , 3-butanediol, pinacol, 1,5-pentanediol, 1,4-
Pentanediol, 2,4-pentanediol, 1,6
-Hexanediol, 1,7-heptanediol, 1,
8-octanediol, 1,9-nonanediol, 1,
10-decanediol, 1,12-dodecanediol,
1,2-cyclopentanediol, 1,3-cyclopentanediol, 1,2-cyclohexanediol, 1,
3-cyclohexanediol, 1,4-cyclohexanediol, glycerol, 1,2,4-butanetriol, catechol, resorcinol, hydroquinone, 1,
2-dihydroxynaphthalene, 1,3-dihydroxynaphthalene, 1,5-dihydroxynaphthalene, 2,6-
Dihydroxynaphthalene, 2,2′-biphenol,
4,4′-biphenol, bis (4-hydroxyphenyl) methane, 4,4′-isopropylidenephenol,
3,3 ′-(ethylenedioxy) diphenol, α,
α′-dihydroxy-p-xylene, 1,1,1-tris (4-hydroxyphenyl) ethane, pyrogallol,
Polyols such as 1,2,4-benzenetriol; and alkali metal salts of the above polyol compounds; ethylenediamine, 1,3-diaminopropane, 1,2-diaminopropane, 1,4-diaminobutane, 1,2-diamino -2-methylpropane, 1,5-diaminopentane,
2,2-dimethyl-1,3-propanediamine, 1,6
-Hexanediamine, 1,7-heptanediamine, 1,
8-octanediamine, 1,9-diaminononane, 1,
10-diaminodecane, 1,12-diaminododecane,
4,4′-methylenebis (cyclohexylamine),
1,2-diaminocyclohexane, 1,3-diaminocyclohexane, 1,4-diaminocyclohexane, 1,
Polyamines such as 2-phenylenediamine, 1,3-phenylenediamine, 1,4-phenylenediamine, α, α′-diamino-p-xylene; and alkali metal salts of the above polyamine compounds; oxalic acid, malonic acid, methylmalon Acid, dimethylmalonic acid, succinic acid, methylsuccinic acid, glutaric acid, adipic acid, 1,7-heptanedicarboxylic acid, 1,8-octanedicarboxylic acid, 1,9-nonanedicarboxylic acid, 1,10-decanedicarboxylic acid, 1,
11-undecanedicarboxylic acid, 1,12-dodecanedicarboxylic acid, 1,2-cyclopentanedicarboxylic acid,
1,2-cyclohexanedicarboxylic acid, 1,3-cyclohexanedicarboxylic acid, 1,4-cyclohexanedicarboxylic acid, 1,3,5-cyclohexanetricarboxylic acid,
Phthalic acid, isophthalic acid, terephthalic acid, 1,2,3-
Polycarboxylic acids such as benzenetricarboxylic acid and 1,2,4,5-benzenetetracarboxylic acid; and alkali metal salts of the above polycarboxylic acids; 1,2-ethanedithiol, 1,3-propanedithiol, 1,4- Butanedithiol, 2,3-butanedithiol, 1,5-pentanedithiol, 1,6-hexanedithiol, 1,7-heptanedithiol, 1,8-octanedithiol, 1,
9-nonanedithiol, 2-mercaptoethyl ether, p-xylene-α, α′-dithiol, 1,2-benzenedithiol, 1,3-benzenedithiol,
A polythiol such as 4-benzenedithiol; and
Alkali metal salts of the above polythiol compounds; lithium sulfide, sodium sulfide, potassium sulfide; and the like.

When the above-mentioned polyols, polyamines, polycarboxylic acids, and polythiols are used, a basic compound is used in combination to promote the substitution reaction, and specific examples thereof include those already exemplified. In addition, as a method for producing a vinyl polymer having an alkenyl group at a terminal, a method of once converting the halogen terminal of Formula 2 into a hydroxyl group-containing substituent and further utilizing the reactivity of the hydroxyl group can be mentioned.

Various methods can be used for converting the terminal into a hydroxyl group-containing substituent. For example, a method in which a vinyl polymer having a terminal represented by the general formula 2 is produced by the above polymerization method, and a compound having both a polymerizable alkenyl group and a hydroxyl group is reacted as a second monomer; A method in which a simple metal or an organometallic compound is allowed to act on a vinyl polymer having a terminal to metallize a halogen and react with a carbonyl compound such as an aldehyde or a ketone. Examples include a method of directly substituting with a metal hydroxide and a method of substituting halogen with a polyalcohol.

As another method of introducing a hydroxyl group into the terminal, a (meth) acrylic monomer is polymerized using a halide having a hydroxyl group as an initiator and a transition metal complex as a catalyst, so that a hydroxyl group is introduced into one terminal. To produce a vinyl polymer having a halogen represented by Formula 2 at the other end,
Thereafter, a method of converting the halogen terminal to a hydroxyl group-containing substituent by the above-described method, or using a compound having a total of two or more identical or different functional groups capable of substituting those halogens, Coupling methods may be mentioned.

Examples of a method for converting a terminal hydroxyl group into an alkenyl group-containing group include a method in which an alkenyl group-containing halide such as allyl chloride is allowed to act on a basic compound such as sodium methoxide, and an alkenyl group such as allyl isocyanate. A method of reacting a group-containing isocyanate compound, a method of reacting an alkenyl group-containing acid halide such as (meth) acrylic acid chloride in the presence of a basic compound such as pyridine, and a method of reacting an alkenyl group-containing carboxylic acid such as acrylic acid with an acid catalyst And the like.

The vinyl polymer having an alkenyl group at the terminal of the component (A) obtained by the above-mentioned various methods may be used alone or as a mixture of two or more. [About the hydrosilyl group-containing compound of the component (B)]
The hydrosilyl group-containing compound as the component (B) is not particularly limited, and various compounds can be used. That is, linear polysiloxanes represented by the general formula 16 or _{^{17 R 18 3 SiO- [Si (}} R 18) 2 O] a - [Si (H) (R 19) O] b - [S i (R 19 _{^{) (R 20) O] c}} -SiR 18 3 (16) HR 18 2 SiO- [Si (R 18) 2 O] a - [Si (H) (R 19) O] b - [Si (R 19) _{^{(R 20) O] c -SiR}} 18 2 H (17) ( wherein R ¹⁸ and R ¹⁹ is an alkyl group having 1 to 6 carbon atoms or a phenyl group, R ²⁰ is an alkyl group having 1 to 10 carbon atoms Aralkyl group, a is 0 ≦ a ≦ 100, b is 2 ≦ b
≦ 100, c is an integer of 0 ≦ c ≦ 100), a cyclic siloxane represented by the general formula 18

[0048]

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(Wherein R ²¹ and R ²² are an alkyl group having 1 to 6 carbon atoms or a phenyl group, and R ²³ is a group having 1 to 10 carbon atoms.
Wherein d is 0 ≦ d ≦ 8, e
Is an integer of 2 ≦ e ≦ 10, f is an integer of 0 ≦ f ≦ 8, and 3
≦ d + e + f ≦ 10). These may be used alone or in combination of two or more. Among these siloxanes, from the viewpoint of compatibility with the (meth) acrylic polymer, having a phenyl group,
Chain siloxanes represented by the general formulas 19 and 20 and cyclic siloxanes represented by the general formulas 21 and 22 are preferable. _{(CH 3) 3 SiO- [Si} (H) (CH 3) O] g - [Si (C 6 H 5) 2 O] h -Si (CH 3) 3 (19) (CH 3) 3 SiO- [ Si (H) (CH ₃ ) O] _g- [Si (CH ₃ ) ｛CH ₂ C (H) (R ²⁴ ) C ₆ H ₅ ｝ O] _h -Si (CH ₃ ) ₃ (20) Wherein R ²⁴ is hydrogen or a methyl group, and g is 2 ≦ g ≦ 10
0 and h are integers of 0 ≦ h ≦ 100, and C ₆ H ₅ represents a phenyl group)

[0050]

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(Wherein R ²⁴ is hydrogen or a methyl group, i
Is 2 ≦ i ≦ 10, j is 0 ≦ j ≦ 8, and 3 ≦ i + j ≦ 1
An integer of 0, and C ₆ H ₅ is a phenyl group) As the compound having at least a hydrosilyl group of the component (B), a low-molecular compound having two or more alkenyl groups in the molecule is represented by the following formulas 16 to 22: A compound obtained by subjecting the indicated hydrosilyl group-containing compound to an addition reaction so that a part of the hydrosilyl group remains even after the reaction can also be used. Various compounds can be used as the compound having two or more alkenyl groups in the molecule. For example, 1,4-pentadiene, 1,5-pentadiene
Hydrocarbon compounds such as hexadiene, 1,6-heptadiene, 1,7-octadiene, 1,8-nonadiene, 1,9-decadiene, O, O'-diallylbisphenol A, 3,3'-diallylbisphenol A, etc. And ester compounds such as diallyl phthalate, diallyl isophthalate, triallyl trimellitate and tetraallyl pyromellitate, and carbonate compounds such as diethylene glycol diallyl carbonate.

In the presence of a hydrosilylation catalyst, an excess amount of the compound containing a hydrosilyl group represented by the formulas 16 to 22 is added.
The compound can be obtained by slowly dropping the above-mentioned alkenyl group-containing compound. Among these compounds, the following compounds are preferred in consideration of the availability of raw materials, the ease of removal of excess siloxane, and the compatibility of the component (A) with the polymer.

[0053]

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[Preparation Method of Cured Product] The polymer (A) and the curing agent (B) can be mixed in an arbitrary ratio. It is preferably in the range of 0.2.
It is particularly preferred that it is 5 to 0.4. When the molar ratio is 5 or more, only a hardened product with insufficient curing and stickiness is obtained, and when it is less than 0.2, a large amount of active hydrosilyl groups remains in the cured product even after curing. ,
Cracks and voids are generated, and a uniform and strong cured product cannot be obtained.

The curing reaction between the polymer (A) and the curing agent (B) proceeds by mixing and heating the two components.
To proceed the reaction more quickly, a hydrosilylation catalyst is added. Such hydrosilylation catalysts include:
Examples include radical initiators such as organic peroxides and azo compounds, and transition metal catalysts. The radical initiator is not particularly limited, and various types can be used. Illustratively, di-t-butyl peroxide, 2,5-dimethyl-2,5-di (t-butylperoxy) hexane,
Such as 2,5-dimethyl-2,5-di (t-butylperoxy) -3-hexyne, dicumyl peroxide, t-butylcumyl peroxide, α, α′-bis (t-butylperoxy) isopropylbenzene Dialkyl peroxides, benzoyl peroxide, p-chlorobenzoyl peroxide, m-chlorobenzoyl peroxide, 2,4-dichlorobenzoyl peroxide, diacyl peroxides such as lauroyl peroxide, peracid esters such as t-butyl perbenzoate, Peroxydicarbonates such as diisopropyl carbonate, di-2-ethylhexyl percarbonate, 1,1-di (t-butylperoxy) cyclohexane, 1,1-di (t-butylperoxy) -3,3,5-trimethyl Peroxyke such as cyclohexane Lumpur, and the like.

As the transition metal catalyst, for example, a platinum solid, a dispersion of platinum solid in a carrier such as alumina, silica, carbon black or the like, chloroplatinic acid, chloroplatinic acid and alcohol, aldehyde, ketone, etc. Complex, platinum-
An olefin complex and a platinum (0) -divinyltetramethyldisiloxane complex are exemplified. Examples of catalysts other than platinum compounds include RhCl (PPh ₃ ) ₃ , RhCl ₃ , and Ru.
Cl ₃ , IrCl ₃ , FeCl ₃ , AlCl ₃ , PdCl _{2
· H 2 O, NiCl 2,} TiCl 4 , and the like. These catalysts may be used alone or in combination of two or more. The amount of the catalyst is not particularly limited,
10 ^-1 to 1 based on 1 mol of the alkenyl group of the component (A).
It is good to use in the range of 0 ^-8 mol, preferably 10 ^-3 mol.
It is preferable to use in the range of from 10 to ⁶ mol. 10 ^-8 mol
If the amount is less, the curing does not proceed sufficiently. Since the hydrosilylation catalyst is expensive, it is preferable not to use 10 ^-1 mol or more.

If the two components (A) and (B) of the present invention and, if necessary, a hydrosilylation catalyst are mixed and cured,
A uniform cured product excellent in deep part curability can be obtained without a phenomenon such as foaming. The curing conditions are not particularly limited, but are generally 0 ° C to 200 ° C, preferably 30 ° C to 15 ° C.
It is preferred to cure at 0 ° C. for 10 seconds to 24 hours. Especially 80 ° C
At a high temperature of up to 150 ° C., one that cures in a short time of about 10 seconds to 1 hour can be obtained. The properties of the cured product depend on the main chain skeleton and molecular weight of the polymer of the component (A) and the curing agent of the component (B).

When preparing a cured product, the component (A)
In addition to the component (B) and the hydrosilylation catalyst, a solvent, an adhesion improver, a storage stability improver, a plasticizer, a filler, an antioxidant, an ultraviolet absorber, and an ozone deterioration inhibitor, depending on the purpose of use. Various additives such as a light stabilizer, a lubricant, a pigment, and a foaming agent can be appropriately added. Specific applications of the cured product obtained from the composition include sealing materials, adhesives, pressure-sensitive adhesives, elastic adhesives, paints, powder coatings, foams, potting materials for electric and electronic devices, films, gaskets, Various molding materials, artificial marble, and the like.

[0059]

EXAMPLES Specific examples of the present invention will be described below, but the present invention is not limited to the following examples. (Production Example 1) Production example of 2-allyloxyethyl methacrylate In a three-necked flask equipped with a stirrer, a thermometer, a reflux condenser, and a Dean-Stark tube, methacrylic acid (137.7) was added.
g, 1.6 mol), ethylene glycol monoallyl ether (80.7 g, 0.8 mol), p-toluenesulfonic acid (0.76 g, 4.0 mmol), and toluene (650 mL). After reacting at 120 ° C. for 5 hours, 0.12 g of p-toluenesulfonic acid was further added, and further reacted at the same temperature for 6 hours, and 0.1 g of p-toluenesulfonic acid was further added. The reaction was continued at the same temperature for another 9 hours to complete the reaction. During this time, methacrylic acid and ethylene glycol monoallyl ether were followed by liquid chromatography, and the conversion reached 98% finally.
An aqueous solution of NaHCO ₃ was added for neutralization, and the two layers were separated.
The aqueous layer was extracted once with toluene, the organic layer was dried over CaCl ₂ , and volatiles were distilled off under reduced pressure. By distilling the crude product under reduced pressure (60 ° C., 2 mmHg), 98.7 g of 2-allyloxyethyl methacrylate represented by the following formula was obtained (yield: 73%). _{H 2 C = C (CH 3} ) CO 2 (CH 2) 2 OCH 2 CH = CH
₂ (Production Example 2) Production Example of Initiator Having Alkenyl Group A 50 mL two-necked flask was purged with nitrogen, 2-allyloxyethanol (2.5 mL, 23.4 mmol), pyridine (3 mL), and THF (10 mL). Was charged. The solution was cooled to 0 ° C. and 2-bromopropionic chloride (2 mL, 19.52 mmol) was slowly added dropwise. After stirring was continued for 1 hour at the same temperature, ethyl acetate (10 mL) was added, and the formed hydrochloride of pyridine was removed by filtration. The filtrate was diluted with diluted hydrochloric acid (10 mL), Na
HCO ₃ aqueous solution (10 mL) and brine (10 m
L). The organic layer was dried over Na ₂ SO ₄ and volatiles were distilled off under reduced pressure. By distilling the obtained crude product under reduced pressure, allyloxyethyl-2-bromopropionate represented by the following formula was obtained. (78.5-81 ° C (1.3m
mHg), 2.986 g).

CH ₃ C (H) (Br) C (O) O—CH ₂
CH ₂ —O—CH ₂ CH ＝ CH ₂ (Production Example 3) Production example of initiator having hydroxyl group Ethylene glycol (10.9 mL, 1
95 mmol) and pyridine (3 g, 39 mmol)
2-bromopropionic acid chloride (2 mL, 3.35 g, 19.5 mmol) was added to an HF solution (10 mL) at 0 ° C.
And slowly dripped. The solution was stirred for 2 hours at the same temperature. Dilute hydrochloric acid (20 mL) and ethyl acetate (30 mL)
Was added and the two layers were separated. The organic layer was washed with diluted hydrochloric acid and brine, dried over Na ₂ SO ₄ , and the volatiles were distilled off under reduced pressure to obtain a crude product (3.07 g). The crude product was distilled under reduced pressure (70-73 ° C., 0.5 m
mHg) to give hydroxyethyl-2-bromopropionate represented by the following formula (2.14 g, 56%). CH ₃ C (H) (Br) C (O) O (CH ₂ ) ₂ —OH (Preparation Example 4) Preparation Example 1 of Carboxylate Having Alkenyl Group 1 / 2N ethanol solution of potassium hydroxide (200 m
L) to undecylenic acid (18.8 g, 0.102 mo)
1) was slowly added dropwise at 0 ° C. while stirring. The volatile product was distilled off under reduced pressure to obtain a crude product. The crude product was washed with acetone and then heated under reduced pressure to obtain a white solid of potassium undecylenic acid represented by the following formula (8.
88 g, 88% yield). _{CH 2 = CH- (CH 2)} 8 -CO 2 - K + ( Production Example 5) Preparation of carboxylates having an alkenyl group 2 methanol - le (245 mL) to 4-pentenoic acid (49 g,
0.489 mol) and potassium tert-butoxide (54.9 g, 0.489 mol) were charged and stirred at 0 ° C. The volatiles were distilled off under reduced pressure to obtain potassium pentenoate shown by the following formula. _{CH 2 = CH- (CH 2)} 2 -CO 2 - K + in (Production Example 6) pressure glass reaction vessel 30 mL,-n-butyl acrylate (2.5 mL, 2.24 g, 17.4
5 mmol), α, α′-dibromo-p-xylene (9
2.5 mg, 0.35 mmol), cuprous bromide (50 m
g, 0.35 mmol), 2,2′-bipyridyl (16
3 mg, 1.05 mmol) and ethyl acetate (2 m
L) and acetonitrile (0.5 mL) were charged, nitrogen gas was blown for 10 minutes to remove dissolved oxygen, and the tube was sealed. The mixture was heated to 130 ° C. and reacted for 1 hour. After cooling to room temperature, 2-allyloxyethyl methacrylate prepared in Preparation Example 1 (600 mg, 3.5 mmol)
Was added under a nitrogen gas atmosphere and the tube was sealed. Mix 80
C. and reacted for 1 hour. After the mixture was diluted with ethyl acetate (20 mL) and the resulting insoluble solid was filtered, the filtrate was washed twice with dilute hydrochloric acid and once with brine. The organic layer was dried over Na ₂ SO ₄ , and volatile components were distilled off under reduced pressure to obtain 1.97 g of poly (n-butyl acrylate) having an alkenyl group at a terminal (polymerization yield: 88%). The number average molecular weight of the polymer was determined to be 670 by GPC measurement (in terms of polystyrene).
0 and the molecular weight distribution was 1.60. The alkenyl group introduced per oligomer molecule is ¹ H NM
From R analysis, it was 5.4. (Production Example 7) Poly (methyl acrylate) having an alkenyl group at a terminal was obtained in the same manner as in Production Example 6, except that methyl acrylate was used instead of n-butyl acrylate (yield: 93). %). The number average molecular weight of the polymer was determined to be 790 by GPC measurement (in terms of polystyrene).
0 and the molecular weight distribution was 2.0. In addition, oligomer 1
The alkenyl groups introduced per molecule are identified by ¹ H NMR
The average was 3.3 from the analysis. (Production Example 8) In a 50 mL pressure-resistant glass reaction vessel, n-butyl acrylate (10 mL, 8.94 g, 69.8 m
mol), α, α′-dibromo-p-xylene (370
mg, 1.4 mmol), cuprous bromide (200 mg,
1.4 mmol), 2,2'-bipyridyl (433 m
g, 2.8 mmol) and methyl isobutyl ketone (10 mL), and nitrogen gas was blown in for 10 minutes to remove dissolved oxygen, followed by sealing. The mixture was heated to 130 ° C. and reacted for 20 minutes. After cooling to room temperature, the mixture was diluted with ethyl acetate (20 mL), and the resulting insoluble solid was filtered. The filtrate was washed twice with diluted hydrochloric acid and once with brine. The organic layer was dried over Na ₂ SO ₄ and volatiles were distilled off under reduced pressure to obtain 5.21 g of poly (n-butyl acrylate) having a bromine terminal (58%). The number average molecular weight of the polymer was determined to be 370 by GPC measurement (in terms of polystyrene).
0 and the molecular weight distribution was 1.41.

Next, the poly (n-butyl acrylate) obtained as described above was placed in a 30 mL pressure-resistant reaction tube.
(2.0 g), p-divinylbenzene (281 mg,
2.16 mmol), cuprous bromide (77 mg, 0.54
mmol), 2,2'-bipyridyl (167 mg, 1.
08 mmol) and methyl isobutyl ketone (4 m
L) was charged, nitrogen gas was blown for 10 minutes to remove dissolved oxygen, and the tube was sealed. Heating the mixture to 130 ° C.,
The reaction was performed for 30 minutes. After cooling to room temperature, the mixture was diluted with ethyl acetate (10 mL), the resulting insoluble solid was filtered, and the filtrate was washed twice with dilute hydrochloric acid and once with brine.
The organic layer was dried over Na ₂ SO ₄ and volatiles were distilled off under reduced pressure.
2.11 g of poly (n-butyl acrylate) having an alkenyl group at the terminal was obtained. The number average molecular weight of the polymer is GP
As a result of C measurement (in terms of polystyrene), the molecular weight distribution was 7,300, and the molecular weight distribution was 2.47. The alkenyl group introduced per oligomer molecule was determined by ¹ H NMR analysis.
2.1. (Production Example 9) In a 500 mL three-necked flask equipped with a reflux tube,
Cuprous bromide (1.50 g, 10.5 mmol
l), using pentamethyldiethylenetriamine (1.65 mL) as a ligand, diethyl-2,5-dibromoadipate (9.42 g, 26.2 mol) as an initiator, and acetonitrile (30 mL) as a solvent to obtain acrylic acid- n-butyl (300 mL) in a nitrogen atmosphere at 70 ° C
When the conversion of n-butyl acrylate is 93%, 1,7-octadiene (38.6 mL, 0.2
61 mol) and heated at the same temperature. The reaction mixture was diluted with ethyl acetate, the catalyst was removed through a column of activated alumina, and volatile matter was distilled off under reduced pressure to obtain a polymer having an alkenyl group at a terminal. The number average molecular weight of the polymer was 1380 by GPC measurement (in terms of polystyrene).
0, molecular weight distribution was 1.28. The number of alkenyl groups introduced per oligomer-1 molecule was 1.84 by ¹ H NMR analysis. (Production Example 10) In a 30 mL pressure-resistant glass reaction vessel, n-butyl acrylate (7.5 mL, 6.72 g, 51.
3 mmol), α, α'-dibromo-p-xylene (2
70 mg, 1.03 mmol), cuprous bromide (150 m
g, 1.03 mmol), 2,2′-bipyridyl (32
2 mg, 2.06 mmol), ethyl acetate (6 mL),
And acetonitrile (1.5 mL) was charged, nitrogen gas was blown for 10 minutes to remove dissolved oxygen, and the tube was sealed. The mixture was heated to 130 ° C. and reacted for 1.5 hours. After the mixture was diluted with ethyl acetate (20 mL) and the resulting insoluble solid was filtered, the filtrate was washed twice with dilute hydrochloric acid and once with brine. The organic layer was dried over Na ₂ SO ₄ , and volatiles were distilled off under reduced pressure to obtain 5.0 g of poly (n-butyl acrylate) having a terminal halogen (polymerization yield: 75).
%). The number average molecular weight of the polymer was 5,600 by GPC measurement (in terms of polystyrene), and the molecular weight distribution was 1.32.

The above polymer (5.00 g), potassium undecylenate synthesized in Production Example 4 (476 mg, 2.
14 mmol) and dimethylacetamide (10 m
L), and reacted at 70 ° C. for 6 hours under a nitrogen atmosphere. After the volatiles of the mixture were distilled off under reduced pressure, ethyl acetate was added and the insolubles were filtered off. The filtrate was evaporated under reduced pressure to obtain 4.77 g of poly (n-butyl acrylate) having an alkenyl group at a terminal. The number of alkenyl groups introduced per oligomer-1 molecule was 1.70 by ¹ H NMR analysis. (Production Example 11) In the same manner as in Production Example 10, cuprous bromide (1.50 g, 10.5 mmol) was used as a catalyst, and pentamethyldiethylenetriamine (0.69 m
L) Using diethyl-2,5-dibromoadipate (9.42 g, 26.2 mol) as an initiator and acetonitrile (30 mL) as a solvent, n-butyl acrylate (300 mL) at 70 ° C. under a nitrogen atmosphere. Poly (n-butyl acrylate) which is polymerized and has a terminal at the terminal
I got The number average molecular weight of the polymer was 11,300 by GPC measurement (in terms of polystyrene), and the molecular weight distribution was 1.16.

Next, poly (n-butyl acrylate) having an alkenyl group at the terminal was obtained in the same manner as in Production Example 10 using potassium pentenoate produced in Production Example 5 as a carboxylate. Was. The alkenyl group introduced per oligomer-1 molecule was determined by ¹ H NMR analysis.
The number was 1.84. (Production Example 12) A 30 mL pressure-resistant glass reaction vessel was charged with n-butyl acrylate (5 mL, 4.47 g, 34.9 m).
mol), α, α′-dibromo-p-xylene (180
mg, 0.69 mmol), cuprous bromide (98 mg,
0.69 mmol), 2,2'-bipyridyl (319
g, 2.06 mmol) and ethyl acetate (4 m
L) and acetonitrile (1 ml) were charged, nitrogen gas was blown for 10 minutes to remove dissolved oxygen, and the tube was sealed.
The mixture was heated to 130 ° C. and reacted for 1 hour. After cooling the mixture, allyltributyltin (0.5
1 mL, 1.64 mmol) and reacted at 100 ° C. for 1 hour. The mixture was diluted with ethyl acetate (20 mL), the resulting insoluble solid was filtered, and the filtrate was diluted with dilute hydrochloric acid.
Twice, once with brine. The organic layer was dried over Na ₂ SO ₄ and volatiles were distilled off under reduced pressure to obtain a mixture of n-butyl polyacrylate having a terminal alkenyl group and bromotributyltin (yield 4.48 g). The number average molecular weight of the polymer was 6 according to GPC measurement (polystyrene conversion).
300, molecular weight distribution was 1.57. The alkenyl group introduced per oligomer molecule is ¹ HN
According to MR analysis, the number was 2.2. (Production Example 13) In a 30 mL pressure-resistant glass reaction vessel, n-butyl acrylate (2.5 mL, 2.24 g, 17.
45 mmol), the initiator having an alkenyl group obtained above (165 mg, 0.698 mmol), cuprous bromide (100 mg, 0.698 mmol), 2,2′-bipyridyl (218 mg, 1.40 mmol), acetonitrile (0.5 mL) and ethyl acetate (2 mL).
After removing dissolved oxygen by blowing nitrogen gas for 10 minutes,
Sealed. The mixture was heated to 130 ° C. and reacted for 50 minutes. After cooling to room temperature, the mixture was treated with ethyl acetate (20 m
After diluting with L) and filtering the resulting insoluble solid, the filtrate was washed twice with dilute hydrochloric acid and once with brine. Organic layer
_After drying over ₂ SO ₄ , the volatiles were distilled off under reduced pressure to obtain 1.90 g of poly (n-butyl acrylate) having an alkenyl group at one end and bromine at the other end (79%). . The number average molecular weight of the polymer was 3,600 by GPC measurement (in terms of polystyrene), and the molecular weight distribution was 1.51.
The number of alkenyl groups introduced per oligomer molecule was 0.75 by ¹ H NMR analysis.

Next, 50 m provided with a stirrer and a reflux condenser.
L in a three-necked flask, the polymer (1.90 g) obtained as described above, Na ₂ S.9H ₂ O (70.2 mg,
0.293 mmol) and ethanol (3 mL), and the mixture was stirred at reflux temperature for 3 hours. After cooling to room temperature, ethyl acetate (10 mL) and dilute hydrochloric acid (10 mL) were added, and the two layers were separated. The organic layer was washed with diluted hydrochloric acid and brine, dried over Na ₂ SO ₄ , and the volatiles were distilled off under reduced pressure to obtain 1.69 g of poly (n-butyl acrylate) having an alkenyl group at the terminal. Was. The number average molecular weight of the polymer was 5,100 by GPC measurement (in terms of polystyrene), and the molecular weight distribution was 1.73. (Production Example 14) In a 30 mL pressure-resistant glass reaction vessel, methyl acrylate (5 mL, 4.78 g, 55.5 mmol) was added.
l), allyl 2-methyl-2-bromopropionate (0.354 mL, 460 mg, 2.22 mmol),
Cuprous bromide (318 mg, 2.22 mmolmmo
l), 2,2'-bipyridyl (1.04 g, 6.66 m
mol), acetonitrile (1 mL), ethyl acetate (4
mL), vacuum degassing was performed three times to remove dissolved oxygen, and the tube was sealed. The mixture was heated to 80 ° C. and reacted for 3 hours. After cooling to room temperature, the mixture was treated with ethyl acetate (2
0 mL), and the resulting insoluble solid was filtered. The filtrate was washed twice with diluted hydrochloric acid and once with brine. The organic layer was dried over Na ₂ SO ₄ and volatiles were distilled off under reduced pressure to obtain 3.93 g of poly (methyl acrylate) having an alkenyl group at one end and bromine at the other end (75%). ). The number average molecular weight of the polymer was 2,700 by GPC measurement (in terms of polystyrene), and the molecular weight distribution was 1.48. The alkenyl group introduced per oligomer molecule is ¹ H
From NMR analysis, it was 0.81.

Next, 50 m provided with a stirrer and a reflux condenser.
L in a three-necked flask, the polymer (1.17 g) obtained as described above, Na ₂ S · 9H ₂ O (57.6 mg,
0.240 mmol) and ethanol (2 mL) and stirred at reflux for 3 hours. After cooling to room temperature, ethyl acetate (10 mL) and dilute hydrochloric acid (10 mL) were added, and the two layers were separated. The organic layer was washed with diluted hydrochloric acid and brine, dried over Na ₂ SO ₄ , and the volatiles were distilled off under reduced pressure to obtain 1.11 g of poly (methyl acrylate) having an alkenyl group at the terminal. The number average molecular weight of the polymer was 420 by GPC measurement (in terms of polystyrene).
0 and the molecular weight distribution was 1.71. (Production Example 15) In a 100 mL pressure-resistant glass reaction vessel, n-butyl acrylate (10 mL, 8.94 g, 69.
8 mmol), an initiator having an alkenyl group produced in Production Example 5 (332 mg, 1.40 mmol), cuprous bromide (200 mg, 1.40 mmol), 2,2′-bipyridyl (433 mg, 2.80 mmol), Acetonitrile (2 mL) and ethyl acetate (8 mL) were charged, nitrogen gas was blown for 10 minutes to remove dissolved oxygen, and the tube was sealed. The mixture was heated to 130 ° C. and reacted for 1.5 hours. After cooling to room temperature, p-divinylbenzene (364 mg, 2.80 mmol) was added under a nitrogen gas atmosphere, and the tube was sealed. The mixture was heated to 100 ° C. and reacted for 2 hours. The mixture was diluted with ethyl acetate (30 mL), the resulting insoluble solid was filtered, and the filtrate was diluted with dilute hydrochloric acid.
Twice, once with brine. The organic layer was dried over Na ₂ SO ₄ , the volatiles were distilled off under reduced pressure, and 6.4 g of poly (n-butyl acrylate) having an alkenyl group at both terminals represented by the following formula was obtained.
3 g were obtained (69%). The number average molecular weight of the polymer was 3,900 by GPC measurement (in terms of polystyrene), and the molecular weight distribution was 5.35. The alkenyl group introduced per oligomer molecule was determined by ¹ H NMR analysis to be 1.
There were 73. (Production Example 16) Acrylic acid-n was placed in a 1 L pressure-resistant reaction vessel.
-Butyl (112 mL, 100 g, 0.78 mol),
The hydroxyl-containing initiator obtained in Production Example 3 (3.07 g, 1
5.6 mmol), cuprous bromide (2.24 g, 15.6)
mmol), 2,2′-bipyridyl (4.87 g, 3
1.2 mmol), ethyl acetate (90 mL), and acetonitrile (22 mL) were charged, the dissolved oxygen was removed by bubbling nitrogen, and the tube was sealed. The mixture was heated to 130 ° C. and reacted for 2 hours. Return the reaction vessel to room temperature,
2-hydroxyethyl methacrylate (3.92 mL,
4.06 g, 31.2 mmol) at 110 ° C.
Allowed to react for hours. The mixture was diluted with ethyl acetate (200 mL), the insoluble matter was filtered off, and the filtrate was diluted with 10% hydrochloric acid.
Twice, once with brine. After the organic layer was dried over Na ₂ SO ₄ , the solvent was distilled off under reduced pressure to obtain 82 g of poly (n-butyl acrylate) having a terminal hydroxyl group. The number average molecular weight of the polymer was 5,100 by GPC measurement (in terms of polystyrene), and the molecular weight distribution was 1.29.

Next, the poly (n-butyl acrylate) having a hydroxyl group at the terminal obtained as described above (50%) was prepared.
g) and pyridine (10 mL) in toluene (10 mL).
0 mL) in a nitrogen atmosphere at 75 ° C. at 7.2 ° C. with undecenoic acid chloride (7.22 mL, 6.81 g, 33.6 mmol).
l) was slowly added dropwise, and the mixture was stirred at 75 ° C for 3 hours. The resulting white solid was filtered and the organic layer was washed with dilute hydrochloric acid and brine. The organic layer was dried over Na ₂ SO ₄ and concentrated under reduced pressure to obtain poly (n-butyl acrylate) having an alkenyl group at a terminal (43 g). (Examples 1 to 14) Preparation of cured product The polymer having an alkenyl group at the terminal obtained in Production Examples 6 to 16 was converted to aluminum silicate (Kyowa Chemical Co., Ltd., Kyoward 700).
PEL) to remove trace impurities in the polymer.

Next, a purified poly (acrylate), a polyvalent hydrogen silicon compound, and
A 1,1,3,3-tetramethyl-1,3-divinyldisiloxane complex of zero-valent platinum (8.3 × 10 ⁻⁸ mol / L xylene solution) was mixed well. As polyvalent hydrogen silicon compounds, the following compounds (S-1, S-
2) or methyl hydrogen siloxane partially modified with α-methylstyrene (S-3: SiH value 7.6)
9 mmol / g). The amount of the polyvalent hydrogen silicon compound used is such that the molar ratio of the alkenyl group of the polymer to the SiH group of the hydrogen silicon compound is 1 / 1.2.
量 1 / 1.5. The platinum catalyst was used in a predetermined amount based on the alkenyl group of the polymer.

A part of the composition thus obtained was replaced with 1
A curing test was performed on a hot plate at 30 ° C., and the gelation time was measured. The remaining composition was degassed under reduced pressure, poured into a mold, heated and cured, and heated to 100 ° C. to obtain a rubber-like cured product. The cured product was immersed in toluene for 24 hours, and the gel fraction was measured from the change in weight before and after. The results are shown in Table 1.

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[Table 1]

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According to the curable composition of the present invention, a vinyl polymer having a terminal alkenyl group introduced at a high ratio is used, so that a cured product having excellent curing properties can be obtained.

 ────────────────────────────────────────────────── ─── Continuing on the front page (72) Inventor Masayuki Fujita 1-80 Yoshida-cho, Hyogo-ku, Kobe Kobe Research Institute

Claims (8)

[Claims] 1. The following two components: (A) a vinyl polymer having a terminal alkenyl group represented by the general formula 1, CH ₂ ＣC (R ¹ )-(1) (wherein R ¹ is hydrogen Or a methyl group) (B) a curable composition comprising a hydrosilyl group-containing compound as an essential component. The component (A) comprises the following steps: (1) radical polymerization of a vinyl monomer using an organic halide or a sulfonyl halide compound as an initiator and a transition metal complex as a catalyst to obtain a compound represented by the following general formula 2: A vinyl polymer having a halogen atom at the terminal shown is prepared, and -C (R ² ) (R ³ ) (X) (2) (wherein R ² and R ³ are ethylenically unsaturated vinyl monomers. X represents chlorine, bromine or iodine.) (2) A vinyl-based polymer obtained by converting a terminal halogen of the polymer into a substituent having an alkenyl group of the general formula 1. The curable composition according to claim 1, which is a united product. 3. The curable composition according to claim 1, wherein the main chain of the vinyl polymer is obtained by polymerizing a (meth) acrylic acid monomer. 4. The curable composition according to claim 3, wherein the (meth) acrylic acid-based monomer is a (meth) acrylic acid ester monomer. 5. The curable composition according to claim 4, wherein the (meth) acrylate monomer is an acrylate monomer. 6. The curable composition according to claim 1, wherein the main chain of the vinyl polymer is obtained by polymerizing a styrene monomer. 7. The vinyl polymer as the component (A) has a ratio (Mw / Mw) between the weight average molecular weight (Mw) and the number average molecular weight (Mn) measured by gel permeation chromatography.
7. The curable composition according to claim 1, wherein the value of n) is less than 1.8. 8. The vinyl polymer as the component (A) has a number average molecular weight in the range of 1,000 to 100,000. 3. The curable composition according to item 1.