JPH115815A - Polymer, method for producing the polymer, and curable composition using the polymer - Google Patents

Abstract

PROBLEM TO BE SOLVED: To obtain a vinyl-based polymer utilizable as a composition component of cured product useful for sealing materials and excellent in weather resistance and curing characteristics by introducing an alkenyl group into main chain end at a high ratio without passing through hetero atom. SOLUTION: This method for producing a vinyl-based polymer having an alkenyl group of formula III in at least one main end comprises producing a vinyl-based polymer having a group of formula I (R<1> and R<2> are each monofunctional organic group; X is chlorine, bromine or iodine) at at least one end and substituting the terminal halogen with an alkenyl group-containing a carbanion of formula II (at least one of R<3> and R<4> is an electron-absorbing substituted group and the other is H, a 1-10C alkyl, etc.; R<5> is a bifunctional 1-10C organic group, etc.; R<6> is H, a 1-10C alkyl, etc.; M<+> is an alkali metal ion, etc.).

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

TECHNICAL FIELD The present invention relates to a vinyl polymer having an alkenyl group or a crosslinkable silyl group at a main chain terminal, a method for producing the polymer, and a curable composition using the polymer.

[0002]

2. Description of the Related Art A polymer having a crosslinkable functional group at a main chain terminal is crosslinked by itself or in combination with an appropriate curing agent to give a cured product having excellent heat resistance and durability. It has been known. Among them, a polymer having an alkenyl group or a crosslinkable silyl group at a main chain terminal is a typical example. The polymer having an alkenyl group at the terminal of the main chain is cross-linked and cured by using a hydrosilyl group-containing compound as a curing agent or by utilizing a photoreaction. The polymer having a crosslinkable silyl group at the terminal of the main chain gives a cured product by absorbing moisture in the presence of a suitable condensation catalyst.

The main chain skeleton of such a polymer having an alkenyl group or a crosslinkable silyl group at the terminal of the main chain includes polyether polymers such as polyethylene oxide, polypropylene oxide and polytetramethylene oxide; polybutadiene and polyisoprene. And hydrocarbon polymers such as polychloroprene, polyisobutylene and hydrogenated products thereof; and polyester polymers such as polyethylene terephthalate, polybutylene terephthalate and polycaprolactone. These polymers are used for various purposes based on their main chain skeleton and cross-linking type.

[0004] These polymers can be obtained by ionic polymerization or polycondensation, but vinyl polymers obtained by radical polymerization and having a crosslinkable functional group at the terminal of the main chain have hardly been put to practical use. Among vinyl polymers, (meth)
Acrylic polymers have properties, such as high weather resistance and transparency, which cannot be obtained with the above-mentioned polyether polymers, hydrocarbon polymers and polyester polymers. For example,
(Meth) acrylic polymers having an alkenyl group or a crosslinkable silyl group at the side chain, not at the terminal of the main chain, are used for highly weather-resistant paints and the like.

[0005] In contrast to such a vinyl polymer having a crosslinkable functional group in the side chain, a vinyl polymer having a crosslinkable functional group at the terminal of the main chain can obtain a cured product having excellent curability. it can. Therefore, many researchers have studied simple methods for producing them, but it is not easy to produce them industrially.

[0006] JP-A-1-247403 discloses that an alkenyl group-containing disulfide is used as a chain transfer agent.
A method for synthesizing a vinyl polymer having alkenyl groups at both terminals is disclosed. Also, JP-A-6-21192
No. 2 discloses a method of synthesizing a vinyl polymer having a hydroxyl group at both terminals using disulfide having a hydroxyl group as a chain transfer agent, and further having an alkenyl group at both terminals using the reactivity of the hydroxyl group. A method for synthesizing a vinyl polymer is disclosed. However, in these methods, a large amount of a chain transfer agent must be used in order to surely introduce an alkenyl group at both ends, and there is a problem in the production process. Further, in the vinyl polymer obtained by these methods, since the alkenyl group is bonded to the polymer main chain via a sulfur atom, it adversely affects the weather resistance, which is the intrinsic property of the vinyl polymer, Further, there is an odor problem peculiar to sulfur.

On the other hand, JP-A-59-168014 discloses a method in which a disulfide compound having a crosslinkable silyl group is used as a chain transfer agent and crosslinkable silyl groups are introduced into both terminals of a vinyl polymer. Have been. JP-A-61-133201 discloses a method of introducing a crosslinkable silyl group into both terminals of a vinyl polymer by using a hydrosilane or a halogenated silane having a crosslinkable silyl group. . However, even with these methods, it is difficult to reliably introduce a crosslinkable silyl group at both ends, and a cured product having satisfactory properties cannot be obtained. In addition, since ordinary radical polymerization is used in these methods, the molecular weight and molecular weight distribution (ratio of weight average molecular weight to number average molecular weight) of the resulting polymer are obtained.
Is difficult to control.

[0008]

DISCLOSURE OF THE INVENTION In view of the above situation, the present invention relates to a vinyl-based compound in which an alkenyl group or a crosslinkable silyl group is introduced into a main chain terminal at a high ratio without a hetero atom such as sulfur. It is an object of the present invention to provide a polymer, a method for producing the polymer, and a curable composition containing the polymer as a main component.

[0009]

The present invention is a vinyl polymer having an alkenyl group represented by the following general formula (1) at at least one main chain terminal. ^{_{-CH 2 -C (R 1) (}} R 2) -C (R 3) (R 4) -R in ^{5 -C (R 6) = CH} 2 (1) formula, R ¹ and R ² are the same or Differently, it represents a monovalent organic group. R ³ and R ⁴ are the same or different and each represents an electron-withdrawing substituent, or one represents an electron-withdrawing substituent, and the other represents hydrogen, an alkyl group having 1 to 10 carbon atoms or a phenyl group. Represents R ⁵ represents a direct bond or a divalent organic group having 1 to 10 carbon atoms which may contain one or more ether bonds. R ⁶ represents hydrogen, an alkyl group having 1 to 10 carbon atoms, an aryl group having 6 to 10 carbon atoms, or an aralkyl group having 7 to 10 carbon atoms.

The present invention is also a vinyl polymer having a crosslinkable silyl group represented by the following general formula (2) at at least one main chain terminal. ^{_{-CH 2 -C (R 1) (}} R 2) -C (R 3) (R 4) -R 5 -CH (R 6) -CH 2 - [Si (R 7) 2-b (Y) b O _{^{] m -Si (R 8) 3}} -a (Y) a (2) wherein, R ¹ to R ⁶ are as defined above. R ⁷ and R ⁸ are the same or different and are 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 (R ′) ₃ SiO— (formula In the formula, R ′ represents a monovalent hydrocarbon group having 1 to 20 carbon atoms, and three R ′s may be the same or different.) Represent. When two or more R ⁷ or R ⁸ are present, they may be the same or different. Y represents a hydroxyl group or a hydrolyzable group,
When two or more are present, they may be the same,
It may be different. a represents 0, 1, 2, or 3.
b represents 0, 1 or 2. m is an integer of 0 to 19. However, it is assumed that a + mb ≧ 1 is satisfied.

The present invention further provides a vinyl polymer having at least one terminal having a group represented by the following general formula (3) by polymerizing a vinyl monomer. This is also a method for producing a vinyl polymer having at least one alkenyl group represented by the general formula (1) at the terminal of the main chain, which is substituted with an alkenyl group-containing carbanion represented by the general formula (4). —CH ₂ —C (R ¹ ) (R ² ) (X) (3) In the formula, R ¹ and R ² are as defined above. X represents chlorine, bromine or iodine. ^{M + C - (R 3)} (R 4) -R 5 -C (R 6) = CH 2 (4) wherein, R ³ to R ⁶ are as defined above. M ⁺ represents an alkali metal ion or a quaternary ammonium ion.

The present invention further provides a vinyl polymer having at least one terminal represented by the above general formula (3) by polymerizing a vinyl monomer, and producing a halogen at the terminal of the polymer. Is substituted with a crosslinkable silyl group-containing carbanion represented by the following general formula (5), wherein the vinyl polymer having a crosslinkable silyl group represented by the above general formula (2) at at least one main chain terminal is used. It is a manufacturing method. ^{M + C - (R 3)} (R 4) -R 5 -CH (R 6) -CH 2 - [Si (R 7) 2-b (Y) b O] m -Si (R 8) 3-a (Y) _a (5) In the formula, R ^{3 to} R ⁸ , Y, M, a, b, and m are the same as described above.

The present invention further comprises reacting the vinyl polymer having an alkenyl group at a main chain terminal with a hydrosilane compound having a crosslinkable silyl group represented by the following general formula (6). This is also a method for producing a vinyl polymer having the crosslinkable silyl group represented by 2) at at least one main chain terminal. _{^{H- [Si (R 7) 2}} -b (Y) b O] m -Si (R 8) in _{3-a (Y) a (} 6) ^{formula, R 7, R 8, Y} , a, b and m Is the same as above.

The present invention also provides (A) a vinyl polymer having the alkenyl group at the terminal of the main chain, (B) a curable composition containing a hydrosilyl group-containing compound, and (C) a crosslinkable silyl group. Is a curable composition containing, as a main component, a vinyl-based polymer having a main chain terminal. Hereinafter, the present invention will be described in detail.

[0015]

BEST MODE FOR CARRYING OUT THE INVENTION The vinyl polymer having an alkenyl group at the terminal of at least one main chain of the present invention has the alkenyl group represented by the above formula (1) at the terminal of at least one main chain. As is clear from the general formula (1),
Since the alkenyl group is bonded to the main chain of the vinyl polymer through a carbon-carbon bond that is difficult to be cleaved, the cured product obtained from this polymer has the weather resistance, which is an intrinsic property of the vinyl polymer. And other properties are not impaired.

In the above general formula (1), R ¹ and R ²
Represents the same or different and represents a monovalent organic group. The monovalent organic group is not particularly limited, and may be derived from a group bonded to a vinyl group of a vinyl monomer used for producing a main chain of the polymer of the present invention specifically exemplified later. .

In the above general formula (1), R ³ and R ⁴
May both represent an electron-withdrawing substituent, only one of them may represent an electron-withdrawing substituent, and the other may be hydrogen, having 1 to 1 carbon atoms.
It may represent 10 alkyl groups or phenyl groups. That is, at least one of R ³ and R ⁴ is an electron-withdrawing substituent, which is necessary for producing the vinyl polymer of the present invention, as described later. When R ³ and R ⁴ both represent an electron-withdrawing substituent, they may be the same or different.

The electron-withdrawing substituent is not particularly limited, and may be a conventionally known electron-withdrawing substituent. Specific examples of this 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. In each of the above formulas, R is an alkyl group having 1 to 20 carbon atoms,
Represents an aryl group having 20 or an aralkyl group having 7 to 20 carbon atoms, preferably an alkyl group having 1 to 10 carbon atoms or a phenyl group. Of these, -CO ₂ R, -C
(O) R and -CN are particularly preferred.

In the above general formula (1), R ⁵ represents a direct bond or a divalent organic group having 1 to 10 carbon atoms. The it is not particularly restricted but includes divalent organic groups, for _{example, - (CH 2) n -} (n represents an integer of 1 to 10), o-, m-, p- C 6 H 4 - ( phenylene Group) and the like. Among them, - (CH _{2) n} - is preferred. The divalent organic group may have one or more ether bonds, and specific examples thereof include -CH
_{2 -O-CH 2 -, -} (CH 2) 2 -O-CH 2 -, -
_{(CH 2) 3 -O-CH} 2 -, - (CH 2) 2 -O-
(CH ₂ ) _2- and the like.

In the general formula (1), R ⁶ represents hydrogen, an alkyl group having 1 to 10 carbon atoms, an aryl group having 6 to 10 carbon atoms or an aralkyl group having 7 to 10 carbon atoms. Among them, hydrogen is preferred from the viewpoint of reactivity when the polymer of the present invention is used as a curable resin.

The vinyl polymer having an alkenyl group at the terminal of at least one main chain of the present invention has a molecular weight distribution, that is, gel permeation chromatography (GP).
The ratio (Mw / Mn) between the weight average molecular weight (Mw) and the number average molecular weight (Mn) measured in C) is preferably a value of 1.8 or less. More preferably, it is 1.6 or less,
More preferably, it is 1.3 or less. GPC in the present invention
In the measurement, chloroform is usually used as a mobile phase, and the measurement is performed using a polystyrene gel column. The number average molecular weight and the like can be determined in terms of polystyrene.

The number average molecular weight of the vinyl polymer having an alkenyl group at the terminal of at least one main chain of the present invention is not particularly limited, but is preferably in the range of 500 to 100,000, more preferably in the range of 3,000 to 50,000. When the molecular weight is 500 or less, the intrinsic characteristics of the vinyl polymer are hardly exhibited, and when the molecular weight is 100,000 or more,
It is not preferable because handling becomes difficult.

The vinyl polymer having a crosslinkable silyl group at at least one main chain terminal of the present invention is a vinyl polymer having at least one crosslinkable silyl group represented by the above general formula (2) at the main chain terminal. It is a system polymer. General formula (2)
As is clear from the above, since the crosslinkable silyl group is bonded to the main chain of the vinyl polymer via a hardly-cleavable carbon-carbon bond, the cured product obtained from this polymer is a vinyl polymer. The properties such as weather resistance, which are the original properties, are not impaired.

In the general formula (2), R ¹ , R ² ,
R ³ , R ⁴ , R ⁵ and R ⁶ are the same as described above, and those exemplified above are used.

In the above general formula (2), R ⁷ and R ⁸
Are the same or different and each have an alkyl group having 1 to 20 carbon atoms;
It represents an aryl group having 6 to 20 carbon atoms, an aralkyl group having 7 to 20 carbon atoms, or a triorganosiloxy group represented by (R ′) ₃ SiO—. In the above formula, R ′ has 1 to 1 carbon atoms.
It represents 20 monovalent hydrocarbon groups, and three R's may be the same or different. In addition, R ⁷ or R ⁸
When two or more are present, they may be the same or different. Specific examples of R ⁷ and R ⁸ include, for example, an alkyl group such as a methyl group and an ethyl group; a cycloalkyl group such as a cyclohexyl group; an aryl group such as a phenyl group; an aralkyl group such as a benzyl group; And triorganosiloxy groups such as phenylsiloxy groups.

In the above formula (2), Y represents a hydroxyl group or a hydrolyzable group, and when two or more are present, they may be the same or different. The hydrolyzable group is not particularly limited, and may be a conventionally known group. Specific examples include a hydrogen atom, a halogen atom, an alkoxy group, an acyloxy group, a ketoximate group, an amino group, an amide group, an acid amide group, an aminooxy group, a mercapto group, and an alkenyloxy group. Above all,
In terms of mild hydrolysis and easy handling,
Alkoxy groups are preferred.

In the general formula (2), a is 0,
Represents 1, 2 or 3. B represents 0, 1 or 2. m represents an integer of 0 to 19. However, a, b, and m satisfy a + mb ≧ 1.
The hydrolyzable group and / or hydroxyl group can be bonded to one silicon atom in the range of 1 to 3. Also, a
+ Mb, that is, the sum of the hydrolyzable groups and / or hydroxyl groups is preferably in the range of 1 to 5. When two or more hydrolyzable groups are bonded to a silicon atom, they may be the same or different. The number of silicon atoms contained in the general formula (2) may be one, or two or more. In the case of silicon atoms linked by a siloxane bond, the number may be up to about 20.

The vinyl monomer used for producing the main chain of the vinyl polymer of the present invention is not particularly limited, and various types can be used. For example, (meth) acrylic acid, methyl (meth) acrylate, (meth)
Ethyl acrylate, n-propyl (meth) acrylate, isopropyl (meth) acrylate, n-butyl (meth) acrylate, isobutyl (meth) acrylate,
-Tert-butyl (meth) acrylate, n-pentyl (meth) acrylate, n-hexyl (meth) acrylate, cyclohexyl (meth) acrylate, n-heptyl (meth) acrylate, (meth) -N-octyl acrylate, 2-ethylhexyl (meth) acrylate,
Nonyl (meth) acrylate, decyl (meth) acrylate, dodecyl (meth) acrylate, phenyl (meth) acrylate, toluyl (meth) acrylate, benzyl (meth) acrylate, (meth) acrylic acid-2- Methoxyethyl, 3-methoxybutyl (meth) acrylate, 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, stearyl (meth) acrylate, glycidyl (meth) acrylate, (Meta)
2-aminoethyl acrylate, γ- (methacryloyloxypropyl) trimethoxysilane, ethylene oxide adduct of (meth) acrylic acid, trifluoromethylmethyl (meth) acrylate, (meth) acrylic acid-2-
Trifluoromethylethyl, (meth) acrylic acid-2-
Perfluoroethylethyl, (meth) acrylic acid-2-
Perfluoroethyl-2-perfluorobutylethyl,
2-perfluoroethyl (meth) acrylate, perfluoromethyl (meth) acrylate, diperfluoromethylmethyl (meth) acrylate, (meth) acrylic acid-
2-perfluoromethyl-2-perfluoroethylmethyl, 2-perfluorohexylethyl (meth) acrylate, 2-perfluorodecylethyl (meth) acrylate, 2-perfluorohexyl (meth) acrylate (Meth) acrylic acid monomers such as decylethyl; styrene monomers such as styrene, vinyltoluene, α-methylstyrene, chlorostyrene, styrenesulfonic acid and salts thereof; perfluoroethylene, perfluoropropylene, vinylidene fluoride, etc. Fluorine-containing vinyl monomers;
Silicon-containing vinyl monomers such as vinyltrimethoxysilane and vinyltriethoxysilane; maleic anhydride, maleic acid, monoalkyl and dialkyl esters of maleic acid; fumaric acid, monoalkyl and dialkyl esters of fumaric acid; maleimide, methyl Maleimide monomers such as maleimide, 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 acetate, vinyl propionate, vinyl pivalate, vinyl benzoate Le, vinyl esters such as vinyl cinnamate, ethylene, alkenes such as propylene, butadiene, conjugated dienes such as isoprene, 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.

The vinyl polymer having an alkenyl group at the terminal of at least one main chain of the present invention can be produced, for example, by the following method. That is, a vinyl-based monomer is polymerized to produce a vinyl-based polymer having at least one group represented by the above general formula (3) at the terminal of the main chain. By substituting with an alkenyl group-containing carbanion represented by the formula (4), the above polymer is obtained.

The vinyl-based monomer used in the above-mentioned production method is not particularly limited, and those exemplified above can be used.

In the above general formula (3), R ¹ and R ²
Is the same group as described above. X represents chlorine, bromine or iodine.

The vinyl polymer having the group represented by the general formula (3) at at least one terminal of the main chain can be obtained by polymerization using a halogen-based chain transfer agent or a living radical which has been energetically studied recently. Polymerization (eg, Matyjasz
ewski et al., Journal of Chemical Society (J. Am. Chem. Soc.), 1995.
Year 117, 5614; Macromolecules (M
acromolecules), 1995, volume 28,
7901; Science, 1996.
Year 272, 866 pages, or Sawamoto et al.
Macromolecules, 1995, 28, 1721
Page, etc.). Among them, living radical polymerization is preferred because the reaction and the structure of the product are easily controlled. Hereinafter, a method for producing a vinyl polymer having a terminal structure represented by the above general formula (3) using living radical polymerization will be described in detail.

In the living radical polymerization, an organic halide (eg, an ester compound having a halogen at the α-position or a compound having a halogen at the benzyl position) or a sulfonyl halide compound is used as an initiator, and a transition metal is used as a catalyst. The polymerization of a vinyl monomer using a complex. When this polymerization method is used, it is possible to control the molecular weight and the molecular weight distribution of the vinyl polymer, which have been difficult in the conventional radical polymerization (molecular weight distribution: 1.1 to 1.1).
1.8).

In the above organic halide or sulfonyl compound, since the carbon to which the halogen is bonded is bonded to a carbonyl group, a phenyl group or a sulfonyl group, the carbon-halogen bond is easily activated and the initiator is activated. Can function as Specific examples of these compounds include C ₆ H ₅ —CH ₂ X and C ₆ H ₅ —C (H) (X) C
H ₃ , C ₆ H ₅ —C (X) (CH ₃ ) ₂ (where C ₆ H
₅ represents a phenyl group. X represents chlorine, bromine or iodine. ); R '' - C ( H) (X) -CO 2
R ''',R'' - C (CH 3) (X) -CO 2
R "", R "-C (H) (X) -C (O)
R ''',R'' - C (CH 3) (X) -C (O)
R "" (wherein, R "and R""are the same or different and each represent a hydrogen atom, an alkyl group having 1 to 20 carbon atoms, an aryl group having 6 to 20 carbon atoms, or a group having 7 to 20 carbon atoms. .X representing the aralkyl group represents chlorine, bromine or _{iodine);. R'-C 6 H} 4 -SO 2 X ( wherein, R 'represents a hydrogen atom, an alkyl group having 1 to 20 carbon atoms, carbon Number 6-20
Or an aralkyl group having 7 to 20 carbon atoms. X represents chlorine, bromine or iodine. ) And the like.

As the initiator of the living radical polymerization, an organic halide or a sulfonyl halide compound having a functional group other than the functional group that initiates the polymerization can also be used. In such a case, a vinyl polymer having a structure represented by the general formula (3) at one main chain terminal and a functional group at the other main chain terminal is produced. Examples of such a functional group include an alkenyl group, a crosslinkable silyl group, a hydroxyl group, an epoxy group, an amino group, and an amide group.

The organic halide having an alkenyl group is not particularly limited, and examples thereof include a compound represented by the following general formula (8). ^{R 9 R 10 C (X)} -R 11 -R 12 -C (R 13) = CH 2 (8) ( wherein, R ¹³ represents hydrogen or a methyl group .R ⁹ and R ¹⁰
Is the same or different and represents hydrogen, a monovalent alkyl group having 1 to 20 carbon atoms, an aryl group having 6 to 20 carbon atoms, or an aralkyl group having 7 to 20 carbon atoms, and R ⁹ and R ¹⁰ are The other ends may be connected to each other. R ¹¹ is -C
(O) O- (ester group), -C (O)-(keto group),
Or, it represents an o-, m-, p-phenylene group. R ¹² is
It represents a divalent organic group having 1 to 20 carbon atoms which may contain a direct bond or one or more ether bonds. X represents chlorine, bromine or iodine. )

Specific examples of the substituents R ⁹ and R ¹⁰ include hydrogen, methyl, ethyl, n-propyl, isopropyl, n-butyl, pentyl and hexyl. R ⁹ and R ¹⁰ may be linked at the other end to form a cyclic skeleton, and in such a case, —R ⁹ —R ¹⁰ —
For _{example, -CH 2 CH 2 -, -} CH 2 CH 2 CH 2
_{-, - CH 2 CH 2 CH} 2 CH 2 -, - CH 2 CH 2 C
H ₂ CH ₂ CH ₂ -, etc. are exemplified.

Specific examples of the organic halide having an alkenyl group represented by the general formula (8) include XCH ₂ C (O) O (CH ₂ ) _n CHＣＨCH ₂ , 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 ,

[0039]

Embedded image

(In the above formulas, X represents chlorine, bromine,
Or iodine, and n is an integer of 0 to 20) XCH_Two C (O) O (CH_Two )_n O (CH_Two )_m CH =
CH_Two , H_Three CC (H) (X) C (O) O (CH_Two )_n 
O (CH_Two )_m CH = CH_Two , (H_Three C)_Two C (X) C
(O) O (CH_Two )_n O (CH_Two )_m CH = CH_Two , C
H_Three CH_Two C (H) (X) C (O) O (CH_Two )_n O
(CH_Two )_m CH = CH _Two ,

[0041]

Embedded image

(In each of the above formulas, X is the same as above,
n is an integer of 1 to 20, m is an integer of 0 to 20) o, m, p-XCH_Two -C₆ H_Four − (CH_Two )_n -CH
= CH_Two , O, m, p-CH_Three C (H) (X) -C₆ H_Four 
− (CH_Two )_n -CH = CH_Two , O, m, p-CH_Three C
H_Two C (H) (X) -C₆ H_Four − (CH_Two )_n -CH =
CH_Two , (In the above formulas, X is the same as above, and n is
O, m, p-XCH_Two -C₆ H_Four − (CH_Two )_n -O-
(CH_Two )_m -CH = CH_Two , O, m, p-CH_Three C
(H) (X) -C₆ H_Four − (CH_Two )_n -O- (CH
_Two ) _m -CH = CH_Two , O, m, p-CH_Three CH_Two C
(H) (X) -C₆ H_Four − (CH_Two )_n -O- (CH
_Two )_m CH = CH_Two , (In each of the above formulas, X is
N is an integer of 1 to 20, m is an integer of 0 to 20
O), m, p-XCH_Two -C₆ H_Four -O- (CH_Two )_n −
CH = CH_Two , O, m, p-CH_Three C (H) (X) -C
₆ H_Four -O- (CH_Two )_n -CH = CH _Two , O, m, p
-CH_Three CH_Two C (H) (X) -C₆ H_Four -O- (CH
_Two )_n -CH = CH_Two , (In each of the above formulas, X is
N is an integer of 0 to 20) o, m, p-XCH_Two -C₆ H_Four -O- (CH_Two )_n −
O- (CH_Two )_m -CH = CH_Two , O, m, p-CH_Three 
C (H) (X) -C₆ H_Four -O- (CH_Two )_n -O-
(CH _Two )_m -CH = CH_Two , O, m, p-CH_Three CH
_Two C (H) (X) -C₆ H_Four -O- (CH_Two )_n -O-
(CH_Two )_m -CH = CH_Two , (In each of the above equations,
X is the same as above, n is an integer of 1 to 20, m is 0 to 20
Which is an integer).

The organic halide having an alkenyl group further includes a compound represented by the following general formula (9). ^{_{H 2 C = C (R 13}} ) -R 12 -C (R 9) (X) -R 14 -R 10 (9) ( ^{wherein, R 9, R 10, R} 12, R 13, X in the above Same as R
¹⁴ is a direct bond, -C (O) O- (ester group), -C
(Representing (O)-(keto group) or o-, m-, p-phenylene group) In the general formula (9), R ¹² is a direct bond or a group having 1 to 1 carbon atoms.
20 divalent organic groups (which may contain one or more ether bonds), but in the case of a direct bond, the vinyl group is bonded to the carbon to which the halogen is bonded, Allylated. In this case, since the carbon-halogen bond is activated by the adjacent vinyl group, R
^It is not necessary to have a C (O) O group, a phenylene group, or the like as ¹⁴ , but a direct bond may be used. When R ¹² is not a direct bond, R ¹⁴ is preferably a C (O) O group, a C (O) group, or a phenylene group in order to activate a carbon-halogen bond.

If the compound of the general formula (9) is specifically exemplified, CH ₂ ＝ CHCH 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 ＣＨCHC (H) (X) CH (CH ₃ ) ₂ , CH ₂ ＣC
HC (H) (X) C ₆ H ₅ , CH ₂ ＣＨCHC (H) (X) C
_{H 2 C 6 H 5, CH} 2 = CHCH 2 C (H) (X) -C
_{O 2 R, CH 2 = CH} (CH 2) 2 C (H) (X) -C
_{O 2 R, CH 2 = CH} (CH 2) 3 C (H) (X) -C
_{O 2 R, CH 2 = CH} (CH 2) 8 C (H) (X) -C
_{O 2 R, CH 2 = CHCH} 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 (H) (X) -C 6 H
₅ , (In each of the above formulas, X is chlorine, bromine, or iodine, and R is an alkyl group, an aryl group, or an aralkyl group having 1 to 20 carbon atoms).

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 the above formulas, X is chlorine, bromine, or iodine, and n is an integer of 0 to 20) and the like.

When polymerization is carried out using the above-mentioned initiator having an alkenyl group, there is a possibility that the alkenyl group of the initiator may react with the polymerization growth terminal during the polymerization reaction. Attention should be paid to the conditions.

The organic halide having a crosslinkable silyl group is not particularly limited, and examples thereof include those having a structure represented by the following general formula (10). ^{R 9 R 10 C (X)} -R 11 -R 12 -C (H) (R 13) CH 2 - [Si (R 15) 2-b (Y) b O] m -Si (R 16) 3- _a (Y) _a (10) [wherein, R ⁹ , R ¹⁰ , R ¹¹ , R ¹² , R ¹³ and X are the same as above. R ¹⁵ and R ¹⁶ are the same or different and each have 1 to 2 carbon atoms.
An alkyl group having 0, an aryl group having 6 to 20 carbon atoms, an aralkyl group having 7 to 20 carbon atoms, or (R ′) ₃ SiO—
(R ′ is a monovalent hydrocarbon group having 1 to 20 carbon atoms,
Three R ′s may be the same or different), and when two or more R ¹⁵ or R ¹⁶ are present, they may be the same. , May be different. Y represents a hydroxyl group or a hydrolyzable group, and when two or more Ys are present, they may be the same or different. a is 0, 1, 2
Or 3 is represented. b represents 0, 1 or 2. m is 0 to 19
Represents an integer. However, it is assumed that a + mb ≧ 1 is satisfied. ]

Specific examples of the compound of the general formula (10)
XCH_Two C (O) O (CH_Two )_n Si (OCH_Three )_Three ,
CH_Three C (H) (X) C (O) O (CH_Two )_n Si (O
CH_Three )_Three , (CH_Three )_Two C (X) C (O) O (CH
_Two )_n Si (OCH_Three )_Three , XCH_Two C (O) O (CH
_Two )_n Si (CH_Three ) (OCH_Three )_Two , CH_Three C (H)
(X) C (O) O (CH_Two )_n Si (CH_Three ) (OCH
_Three )_Two , (CH_Three )_Two C (X) C (O) O (CH_Two )_n 
Si (CH_Three ) (OCH_Three )_Two , (In each of the above equations,
X is chlorine, bromine, iodine, n is an integer of 0 to 20, XCH_Two C (O) O (CH_Two )_n O (CH_Two )_m Si
(OCH_Three )_Three , H_Three CC (H) (X) C (O) O (CH
_Two )_n O (CH_Two )_m Si (OCH_Three )_Three, (H_Three C)_Two
 C (X) C (O) O (CH_Two )_n O (CH_Two )_m Si
(OCH_Three ) _Three , CH_Three CH_Two C (H) (X) C (O)
O (CH_Two )_n O (CH_Two )_m Si (OCH_Three )_Three , X
CH_Two C (O) O (CH_Two )_n O (CH_Two )_m Si (C
H_Three ) (OCH_Three )_Two , H_Three CC (H) (X) C (O) O
(CH_Two )_n O (CH_Two )_m -Si (CH_Three ) (OCH
_Three )_Two , (H_Three C)_Two C (X) C (O) O (CH_Two )_n 
O (CH_Two )_m -Si (CH_Three ) (OCH_Three )_Two , CH
_Three CH_Two C (H) (X) C (O) O (CH_Two )_n O (C
H_Two )_m -Si (CH_Three ) (OCH_Three )_Two , (Each of the above
In the formula, X is chlorine, bromine, iodine, and n is 1-20.
An integer, m is an integer of 0 to 20) o, m, p-XCH_Two -C₆ H_Four − (CH_Two )_Two Si
(OCH_Three )_Three , O, m, p-CH_Three C (H) (X) -C
₆ H_Four − (CH_Two )_Two Si (OCH_Three )_Three, O, m, p
-CH_Three CH_Two C (H) (X) -C₆ H_Four − (CH_Two )_Two 
Si (OCH _Three )_Three , O, m, p-XCH_Two -C₆ H_Four 
− (CH_Two )_Three Si (OCH_Three )_Three , O, m, p-CH
_Three C (H) (X) -C₆ H_Four − (CH_Two )_Three Si (OCH
_Three )_Three, O, m, p-CH_Three CH_Two C (H) (X) -C₆
 H_Four − (CH_Two )_Three Si (OCH_Three )_Three , O, m, p
-XCH_Two -C₆ H_Four − (CH_Two )_Two -O- (CH_Two )
_Three Si (OCH_Three )_Three , O, m, p-CH_Three C (H)
(X) -C₆ H_Four − (CH_Two )_Two -O- (CH_Two ) _Three S
i (OCH_Three )_Three , O, m, p-CH_Three CH_Two C (H)
(X) -C₆ H_Four − (CH_Two )_Two -O- (CH_Two )_Three S
i (OCH_Three )_Three , O, m, p-XCH_Two -C₆ H_Four −
O- (CH_Two )_Three Si (OCH_Three )_Three , O, m, p-C
H_Three C (H) (X) -C₆ H_Four -O- (CH_Two )_Three Si
(OCH _Three )_Three , O, m, p-CH_Three CH_Two C (H)
(X) -C₆ H_Four -O- (CH_Two )_Three -Si (OCH
_Three )_Three , O, m, p-XCH_Two -C₆ H_Four -O- (CH
_Two )_Two -O- (CH_Two )_Three -Si (OCH_Three )_Three , O,
m, p-CH_Three C (H) (X) -C₆ H_Four -O- (CH
_Two )_Two -O- (CH _Two )_Three Si (OCH_Three )_Three , O,
m, p-CH_Three CH_Two C (H) (X) -C₆ H_Four -O-
(CH_Two )_Two -O- (CH_Two )_Three Si (OCH_Three )_Three ,
(In each of the above formulas, X is chlorine, bromine, or iodine.)
And the like.

As the organic halide having a crosslinkable silyl group, those having the structure represented by the general formula (11) are further exemplified. ^{_{(R 16) 3-a (}} Y) a Si- [OSi (R 15) 2-b (Y) b] m -CH 2 -C (H) (R 13) -R 12 -C (R 9) ( ^{X) -R 14 -R 10 (11} ) ( ^{wherein, R 9, R 10, R} 12, R 13, R 14, R 15, R 16,
a, b, m, X and Y are the same as above)

Specific examples of such compounds include (CH ₃ O) ₃ SiCH ₂ CH ₂ C (H) (X) C ₆ H
₅ , (CH ₃ O) ₂ (CH ₃ ) SiCH ₂ CH ₂ C
(H) (X) C ₆ H ₅ , (CH ₃ O) ₃ Si (CH ₂ )
₂ C (H) (X) -CO ₂ R, (CH ₃ O) ₂ (CH
_{3) Si (CH 2) 2} C (H) (X) -CO 2 R, (C
_{H 3 O) 3 Si (CH} 2) 3 C (H) (X) -CO 2
R, (CH ₃ O) ₂ (CH ₃ ) Si (CH ₂ ) ₃ C
_{(H) (X) -CO 2} R, (CH 3 O) 3 Si (CH
_{2) 4 C (H) (} X) -CO 2 R, (CH 3 O) 2 (C
_{H 3) Si (CH 2)} 4 C (H) (X) -CO 2 R,
_{(CH 3 O) 3 Si (} CH 2) 9 C (H) (X) -CO
_{2 R, (CH 3 O)} 2 (CH 3) Si (CH 2) 9 C
_{(H) (X) -CO 2} R, (CH 3 O) 3 Si (CH
₂ ) ₃ C (H) (X) -C ₆ H ₅ , (CH ₃ O) ₂ (C
_{H 3) Si (CH 2)} 3 C (H) (X) -C 6 H 5,
_{(CH 3 O) 3 Si (} CH 2) 4 C (H) (X) -C 6
H ₅ , (CH ₃ O) ₂ (CH ₃ ) Si (CH ₂ ) ₄ C
_{(H) (X) -C 6} H 5, ( in each formula above, X is chlorine, bromine, or iodine, R represents an alkyl group having 1 to 20 carbon atoms, an aryl group, an aralkyl group) and the like.

The organic halide or the sulfonyl halide compound having a hydroxyl group is not particularly limited, and examples thereof include the following compounds. _{HO- (CH 2) n -OC (} O) C (H) (R) (X) ( wherein, X is chlorine, .R representing bromine or iodine, hydrogen, alkyl group having 1 to 20 carbon atoms , An aryl group having 6 to 20 carbon atoms, or an aralkyl group having 7 to 20 carbon atoms. N represents an integer of 1 to 20.)

The organic halide or sulfonyl halide compound having an amino group is not particularly restricted but includes the following compounds. H ₂ N- (CH ₂₎ in _{n -OC (O) C (H} ) (R) (X) ( wherein, X is chlorine, .R representing bromine or iodine, hydrogen, 1 to 20 carbon atoms Represents an alkyl group, an aryl group having 6 to 20 carbon atoms, or an aralkyl group having 7 to 20 carbon atoms, and n represents an integer of 1 to 20.

The organic halide or sulfonyl halide compound having an epoxy group is not particularly limited, and the following compounds are exemplified.

[0054]

Embedded image

Wherein X represents chlorine, bromine or iodine. R is hydrogen, an alkyl group having 1 to 20 carbon atoms, an aryl group having 6 to 20 carbon atoms, or an aralkyl having 7 to 20 carbon atoms. Represents a group, and n represents an integer of 1 to 20.)

In the above living radical polymerization, when polymerization is carried out using an organic halide or a sulfonyl halide compound having two or more starting points as an initiator,
A vinyl polymer having the alkenyl group represented by the general formula (1) at two or more main chain terminals can be produced. That is, when polymerization is performed using an initiator having two initiation points, a vinyl polymer having alkenyl groups at both ends of the main chain is obtained. To illustrate this initiator specifically,

[0057]

Embedded image

(Wherein C ₆ H ₄ represents a phenylene group; X represents chlorine, bromine or iodine; R is an alkyl group having 1 to 20 carbon atoms, an aryl group having 6 to 20 carbon atoms or Represents an aralkyl group having 7 to 20 carbon atoms, and n is 0 to 2
Represents an integer of 0. )

[0059]

Embedded image

(Wherein X represents chlorine, bromine or iodine)
You. n represents an integer of 0 to 20. C ₆ H_Four Is a pheny
Represents a len group. ) And the like.

The living radical polymerization can be carried out without a solvent or in various solvents. As the solvent,
For example, hydrocarbon solvents such as benzene and toluene; ether solvents such as diethyl ether and tetrahydrofuran; halogenated hydrocarbon solvents such as methylene chloride and chloroform; ketone solvents such as acetone, methyl ethyl ketone and methyl isobutyl ketone; Alcohol solvents such as 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, propylene And carbonate-based solvents such as carbonate. These can be used alone or in combination of two or more. The polymerization can be carried out at a temperature in the range of room temperature to 200 ° C., preferably in the range of 50 to 150 ° C.

As a catalyst for the above living radical polymerization
The transition metal complex to be used is not particularly limited and is preferably
Monovalent copper, divalent ruthenium, divalent iron
Alternatively, a complex of divalent nickel is given. Above all, copper
Are preferred. Specific examples of monovalent copper compounds
Then cuprous chloride, cuprous bromide, cuprous iodide, shea
Cuprous oxide, cuprous oxide, cuprous perchlorate and the like. copper
When a compound is used, 2,2 ′
-Bipyridyl and its derivatives, 1,10-phenanthro
Phosphorus and its derivatives, pentamethyldiethylenetriamido
And a ligand such as a polyamine. Also divalent
Tristriphenylphosphine complex of ruthenium chloride in water
(RuCl_Two (PPh_Three )_Three ) Are also suitable as catalysts
You. When a ruthenium compound is used as a catalyst,
Aluminum alkoxides are added as an agent.
Further, bistriphenylphosphine complex of divalent iron (F
eCl _Two (PPh_Three )_Two ) Bivalent nickel bistri
Phenylphosphine complex (NiCl_Two (PPh_Three )
_Two ) And divalent nickel bistributylphosphite
Complex (NiBr_Two (PBu_Three )_Two ) Is also a good catalyst
Suitable.

The polymerization in the production method of the present invention may be a polymerization using a halide as a chain transfer agent (telogen) in addition to the above living radical polymerization. As the halide, carbon tetrachloride, carbon tetrabromide, methylene chloride, methylene bromide and the like are used.

The terminal halogen of the vinyl polymer having a terminal structure represented by the above general formula (3) produced by the above production method is replaced with an alkenyl group-containing carbanion represented by the above general formula (4). By the substitution, a vinyl polymer having the alkenyl group of the present invention at the terminal of the main chain is obtained. Hereinafter, the substitution method using an alkenyl group-containing carbanion will be described in detail.

In the general formula (4) representing the alkenyl group-containing carbanion, R ³ , R ⁴ , R ⁵ and R ⁶
Is the same substituent as described above, and specific examples thereof include all those exemplified above.

In the above formula (4), M ⁺ is a counter cation of a carbanion and represents an alkali metal ion or a quaternary ammonium ion. Examples of the alkali metal ion include a lithium ion, a sodium ion, and a potassium ion. Examples of the quaternary ammonium ion include a tetramethylammonium ion, a tetraethylammonium ion, a trimethylbenzylammonium ion, a trimethyldodecylammonium ion, a tetrabutylammonium ion, and a dimethylpiperidinium ion. Preferred M ⁺ is a sodium ion or a potassium ion.

[0067] Formula (4) carbanion C in the compounds of ^- the negative charge is Hikyoku localization to the electron-withdrawing substituent is bonded one or two. A carbanion with a non-polarized negative charge is more stable than a carbanion that is not. Further, since the reactivity is mild, it selectively reacts with the terminal halogen in the general formula (3) and does not react with other substituents such as an ester group, so that an alkenyl group is efficiently introduced into the main chain terminal. It is possible.

The alkenyl group-containing carbanion represented by the general formula (4) can be obtained by allowing a basic compound to act on the precursor and extracting active protons of the precursor.

As the above precursor, the following compound
Object: H_Two C = CH-CH (CO_Two CH_Three)_Two , H_Two C =
CH-CH (CO_Two C_Two H_Five )_Two , H_Two C = CH- (C
H_Two )_nCH (CO_Two CH_Three )_Two , H_Two C = CH- (C
H_Two )_n CH (CO_Two C_Two H_Five ) _Two , O-, m-, p-
H_Two C = CH-C₆ H_Four -CH (CO_Two CH_Three )_Two , O
-, M-, pH_Two C = CH-C₆ H_Four -CH (CO_Two 
C_Two H_Five )_Two , O-, m-, pH_Two C = CH-C₆ H
_Four -CH_Two CH (CO_Two CH_Three )_Two , O-, m-, p-
H_Two C = CH-C₆ H_Four -CH_Two CH (CO_Two C_Two H
_Five )_Two , H_Two C = CH-CH (C (O) CH_Three ) (CO
_Two C_Two H_Five ), H_Two C = CH- (CH_Two )_n CH (C
(O) CH_Three ) (CO_Two C_Two H_Five ), O-, m-, p-
H_Two C = CH-C ₆ H_Four -CH (C (O) CH_Three ) (C
O_Two C_Two H_Five ), O-, m-, pH_Two C = CH-C₆ 
H_Four -CH_Two CH (C (O) CH_Three ) (CO_Two C_Two H
_Five ), H_Two C = CH-CH (C (O) CH_Three )_Two , H_Two 
C = CH- (CH_Two )_n CH (C (O) CH_Three )_Two , O
-, M-, pH_Two C = CH-C₆ H_Four -CH (C
(O) CH _Three )_Two , O-, m-, pH_Two C = CH-C
₆ H_Four -CH_Two CH (C (O) CH _Three )_Two , H_Two C = C
H-CH (CN) (CO_Two C_Two H_Five ), H_Two C = CH-
(CH_Two )_n CH (CN) (CO_Two C_Two H_Five ), O-,
m-, pH_Two C = CH-C ₆ H_Four -CH (CN) (C
O_Two C_Two H_Five ), O-, m-, pH_Two C = CH-C ₆ 
H_Four -CH_Two CH (CN) (CO_Two C_Two H_Five ), H_Two C
= CH-CH (CN) _Two , H_Two C = CH- (CH_Two )_n 
CH (CN)_Two , O-, m-, pH_Two C = CH-C₆ 
H_Four -CH (CN)_Two , O-, m-, pH_Two C = CH
-C₆ H_Four -CH_Two CH (CN)_Two , H_Two C = CH-
(CH_Two )_n NO_Two , O-, m-, pH _Two C = CH-
C₆ H_Four -CH_Two NO_Two , O-, m-, pH_Two C = C
HC₆ H _Four -CH_Two CH_Two NO_Two , H_Two C = CH-C
H (C₆ H_Five ) (CO_Two C_Two H_Five ), H_Two C = CH-
(CH_Two )_n CH (C₆ H_Five ) (CO_Two C_Two H_Five ), O
-, M-, pH_Two C = CH-C₆ H_Four -CH (C₆ H
_Five ) (CO_Two C_Two H_Five ), O-, m-, pH_Two C = C
HC₆ H_Four -CH_Two CH (C₆ H_Five ) (CO_Two C_Two H
_Five ) Is exemplified. In the above formula, n represents an integer of 1 to 10.
Represent. C₆ H_Four Represents a phenylene group;₆ H_Five Is
Represents a phenyl group.

An active proton is extracted from the precursor,
Various bases are used to obtain the alkenyl group-containing carbanion of the general formula (4). These bases include sodium methoxide, potassium methoxide, lithium methoxide, sodium ethoxide, potassium ethoxide, lithium ethoxide, sodium tert-
Butoxide, potassium-tert-butoxide, sodium carbonate, potassium carbonate, lithium carbonate, sodium bicarbonate, sodium hydride, potassium hydride, methyllithium, ethyllithium, n-butyllithium, ter
t-butyllithium, lithium diisopropylamide,
Lithium hexamethyldisilazide and the like are exemplified. The base may be used in an equivalent amount or a small excess amount relative to the precursor, and is preferably 1 to 1.2 equivalents.

Solvents used for reacting the above precursor with the above base include, for example, hydrocarbon solvents such as benzene and toluene; ether solvents such as diethyl ether and tetrahydrofuran; halogenated solvents such as methylene chloride and chloroform. Hydrocarbon solvents; 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 propylene solvents; carbonate solvents such as propylene carbonate; amide solvents such as dimethylformamide and dimethylacetamide. These can be used alone or in combination of two or more.

An alkenyl group-containing carbon of the general formula (4)
The specific method of producing the onion will be further described. For example,
As the above precursor, H_Two C = CH-CH_Two CH (CO_Two 
C_Two H _Five )_Two When using (diethyl allylmalonate)
If it is, a base,
For example, potassium-tert-butoxide was charged, and tet
Suspended and dispersed in an ether solvent such as lahydrofuran
You. The above-mentioned diethyl allylmalonate is equimolarly added to this dispersion.
And react at room temperature to reflux temperature for 10 minutes to 1 hour.
And the acidic proton was replaced by potassium ion
A carbanion is obtained.

In order to obtain an alkenyl group-containing carbanion in which M ⁺ is a quaternary ammonium ion, one in which M ⁺ is an alkali metal ion is prepared by the above-mentioned method, and then a quaternary ammonium halide is allowed to act. 4 above
As the secondary ammonium halide, tetramethylammonium halide, tetraethylammonium halide,
Examples include trimethylbenzyl ammonium halide, trimethyl dodecyl ammonium halide, tetrabutyl ammonium halide, and the like.

The alkenyl group-containing carbanion of the general formula (4) prepared by the above method is reacted with a vinyl polymer having a terminal structure of the general formula (3) to give a compound of the general formula (1) A vinyl polymer having an alkenyl group represented by at the end of the main chain is obtained. This reaction can be carried out at 0 to 150 ° C. in the above-mentioned solvent. The amount of the carbanion of the general formula (4) to be used may be an equivalent amount or a small excess with respect to the halogen terminal of the general formula (3), and is preferably 1 to 1.2 equivalents.

The vinyl polymer having at least one crosslinkable silyl group represented by the above general formula (2) at the terminal of the main chain has, for example, a halogen terminal represented by the above general formula (3) by the above-mentioned method. It can be produced by producing a vinyl polymer and reacting a terminal halogen of the polymer with a crosslinkable silyl group-containing carbanion represented by the following general formula (5). ^{M + C - (R 3)} (R 4) -R 5 -CH (R 6) -CH 2 - [Si (R 7) 2-b (Y) b O] m -Si (R 8) 3-a (Y) _a (5) wherein R ^{3 to} R ⁸ , Y, a, b, m, and M ⁺ are the same as above.

This method is based on the same methodology as the above-mentioned method for producing a vinyl polymer having an alkenyl group at the terminal represented by the general formula (1). R ³ , R ⁴ ,
As M ⁺ , all of those described above can be used.

The carbanion of the general formula (5) is
Of a basic compound on the precursor of
Can be obtained by pulling it out. General above
The precursor of the carbanion represented by the formula (5) is as follows.
Compounds such as: (CH_Three O)_Three Si (CH_Two )_n −
CH (CO_Two C_Two H_Five )_Two , (CH_Three O)_Three Si (CH
_Two )_n CH (CO_Two CH_Three )_Two , O-, m-, p- (C
H_Three O)_Three SiCH_Two CH_Two -C₆ H_Four -CH (CO_Two 
CH_Three )_Two , O-, m-, p- (CH_Three O)_Three SiCH
_Two CH_Two -C₆ H_Four -CH (CO_Two C_Two H_Five )_Two , O
-, M-, p- (CH_Three O)_Three SiCH_Two CH_Two -C₆ 
H_Four -CH_Two CH (CO_Two CH_Three )_Two , O-, m-, p
− (CH_Three O)_Three SiCH_Two CH_Two -C₆ H_Four -CH_Two 
CH (CO_TwoC_Two H_Five )_Two , (CH_Three O)_Three Si (CH_Two
 )_n -CH (C (O) CH_Three ) (CO_Two CH_Three ),
(CH_Three O)_Three Si (CH_Two )_n -CH (C (O) CH
_Three ) (CO_Two C_Two H_Five ), O-, m-, p- (CH_Three 
O)_Three SiCH_Two CH_Two -C₆ H_Four-CH (C (O) C
H_Three ) (CO_Two C_Two H_Five ), O-, m-, p- (CH_Three 
O) _Three SiCH_Two CH_Two -C₆ H_Four -CH_Two CH (C
(O) CH_Three ) (CO_Two C_Two H _Five ), (CH_Three O)_Three S
i (CH_Two )_n CH (C (O) CH_Three )_Two , O-, m
−, P- (CH_Three O)_Three SiCH_Two CH_Two -C₆ H_Four −
CH (C (O) CH_Three )_Two, O-, m-, p- (CH_Three 
O)_Three SiCH_Two CH_Two -C₆ H_Four -CH_Two CH (C
(O) CH_Three )_Two , (CH_Three O)_Three Si (CH_Two )_n C
H (CN) (CO_Two C _Two H_Five ), O-, m-, p- (C
H_Three O)_Three SiCH_Two CH_Two -C₆ H_Four -CH (CN)
(CO_Two C_Two H_Five ), O-, m-, p- (CH_Three O)_Three 
SiCH_Two CH _Two -C₆ H_Four -CH_Two CH (CN) (C
O_Two C_Two H_Five ), (CH_Three O)_Three Si (CH_Two )_n CH
(CN)_Two , O-, m-, p- (CH_Three O)_Three SiCH
_Two CH_Two-C₆ H_Four -CH (CN)_Two , O-, m-, p
− (CH_Three O)_Three SiCH_Two CH _Two -C₆ H_Four -CH_Two 
CH (CN)_Two , (CH_Three O)_Three Si (CH_Two )_n CH
_TwoNO_Two , O-, m-, p- (CH_Three O)_Three SiCH_Two 
CH_Two -C₆ H_Four -CH_TwoNO_Two , O-, m-, p-
(CH_Three O)_Three SiCH_Two CH_Two -C₆ H_Four -CH_TwoC
H_Two NO_Two , (CH_Three O)_Three Si (CH_Two )_n -CH
(C₆ H_Five ) (CO_Two C _Two H_Five ), O-, m-, p-
(CH_Three O)_Three SiCH_Two CH_Two -C₆ H_Four -CH (C
₆ H_Five ) (CO_Two C_Two H_Five ), O-, m-, p- (CH
_Three O)_Three SiCH_TwoCH_Two -C₆ H_Four -CH_Two CH (C₆
 H_Five ) (CO_Two C_Two H_Five ), (CH_Three O) _Two (CH
_Three ) Si (CH_Two )_n -CH (CO_Two C_Two H_Five )_Two ,
(CH_Three O)_Two (CH_Three ) Si (CH_Two )_n CH (CO
_Two CH_Three )_Two , O-, m-, p- (CH_ThreeO)_Two (CH_Three
 ) SiCH_Two CH_Two -C₆ H_Four -CH (CO_Two CH
_Three )_Two , O-, m-, p- (CH_Three O)_Two (CH_Three ) S
iCH_Two CH_Two -C₆ H_Four -CH (CO_Two C_Two H_Five )
_Two , O-, m-, p- (CH_Three O)_Two (CH_Three ) SiC
H_Two CH _Two -C₆ H_Four -CH_Two CH (CO_Two CH_Three )
_Two , O-, m-, p- (CH_Three O) _Two (CH_Three ) SiC
H_Two CH_Two -C₆ H_Four -CH_Two CH (CO_Two C_Two H_Five )
_Two , (CH_Three O)_Two (CH_Three ) Si (CH_Two )_n -CH
(C (O) CH_Three ) (CO_TwoCH_Three ), (CH_Three O)_Two 
(CH_Three ) Si (CH_Two )_n -CH (C (O) CH_Three)
(CO_Two C_Two H_Five ), O-, m-, p- (CH_Three O)_Two 
(CH_Three ) SiCH_TwoCH_Two -C₆ H_Four -CH (C
(O) CH_Three ) (CO_Two C_Two H_Five ), O-, m-, p-
(CH_Three O)_Two (CH_Three ) SiCH_Two CH_Two -C₆ H_Four 
-CH_Two CH (C (O) CH_Three ) (CO_Two C_Two H_Five ),
(CH_Three O)_Two (CH_Three ) Si (CH_Two )_nCH (C
(O) CH_Three )_Two , O-, m-, p- (CH_Three O)_Two 
(CH_Three ) SiCH_Two CH_Two -C₆ H_Four -CH (C
(O) CH_Three )_Two , O-, m-, p- (CH_ThreeO)_Two 
(CH_Three ) SiCH_Two CH_Two -C₆ H_Four -CH_Two CH
(C (O) CH_Three ) _Two , (CH_Three O)_Two (CH_Three ) Si
(CH_Two )_n CH (CN) (CO_Two C_Two H_Five), O-,
m-, p- (CH_Three O)_Two (CH_Three ) SiCH_Two CH_Two 
-C₆ H_Four -CH (CN) (CO_Two C_Two H_Five ), O-,
m-, p- (CH_Three O)_Two (CH_Three ) SiCH_Two CH_Two 
-C₆ H_Four -CH_Two CH (CN) (CO_Two C_Two H_Five ),
(CH _Three O)_Two (CH_Three ) Si (CH_Two )_n CH (C
N)_Two , O-, m-, p- (CH _Three O)_Two (CH_Three ) S
iCH_Two CH_Two -C₆ H_Four -CH (CN)_Two , O-, m
−, P- (CH_Three O)_Two (CH_Three ) SiCH_Two CH_Two −
C₆ H_Four -CH_Two CH (CN)_Two , (CH_Three O)_Two (C
H_Three ) Si (CH_Two )_n CH_Two NO_Two , O-, m-, p
− (CH_Three O)_Two (CH_Three ) SiCH_Two CH_Two -C₆ H
_Four -CH_Two NO_Two , O-, m-, p- (CH_Three O)_Two 
(CH_Three ) SiCH_Two CH_Two -C₆ H_Four -CH _Two CH_Two 
NO_Two , (CH_Three O)_Two (CH_Three ) Si (CH_Two )_n −
CH (C₆ H_Five) (CO_Two C_Two H_Five ), O-, m-, p
− (CH_Three O)_Two (CH_Three ) SiCH_TwoCH_Two -C₆ H_Four
 -CH (C₆ H_Five ) (CO_Two C_Two H_Five ), O-, m
−, P- (CH_Three O)_Two (CH_Three ) SiCH_Two CH_Two −
C₆ H_Four -CH_Two CH (C₆ H_Five ) (CO_Two C_Two H_Five )
(In the above formula, n represents an integer of 1 to 10.
You. ).

By reacting the above-mentioned basic compound on these precursors, a carbanion represented by the above general formula (5) is prepared, and a vinyl polymer having a halogen terminal represented by the above general formula (3) and By reacting
The desired vinyl polymer having a crosslinkable silyl group represented by the general formula (2) at the terminal can be obtained.

The vinyl polymer having at least one crosslinkable silyl group at the terminal of the main chain represented by the general formula (2) has at least one alkenyl group of the general formula (1).
It can also be produced by subjecting a vinyl polymer having two main chain terminals to an addition reaction with a hydrosilane compound having a crosslinkable silyl group represented by the following general formula (6). In this case, the vinyl polymer having the alkenyl group of the above general formula (1) at at least one terminal of the main chain may be used alone or in combination of two or more. _{^{H- [Si (R 7) 2}} -b (Y) b O] m - Si (R 8) 3-a (Y) a (6) ^{wherein, R 7, R 8, Y} , a, b, m Is the same as above.

Among the hydrosilane compounds represented by the above general formula (6), in particular, the following general formula (7): H-Si (R ⁸ ) _3-a (Y) _a (7) (wherein R ⁸ , Y and a are the same as those described above.) A hydrosilyl group-containing compound having a crosslinkable silyl group is preferred from the viewpoint of easy availability.

The crosslinkable silyl represented by the general formula (6)
Specific examples of the hydrosilane compound having a group include, for example,
For example, HSiCl_Three , HSi (CH_Three ) Cl_Two , HSi
(CH_Three)_Two Cl, HSi (OCH_Three )_Three , HSi (C
H_Three ) (OCH_Three )_Two , HSi (CH_Three )_Two OCH_Three ,
HSi (OC_Two H_Five )_Three , HSi (CH_Three ) (OC_Two H
_Five)_Two , HSi (CH_Three )_Two OC_Two H_Five , HSi (OC_Three
 H₇ )_Three , HSi (C_TwoH_Five ) (OCH_Three )_Two , HSi
(C_Two H_Five )_Two OCH_Three , HSi (C₆ H_Five ) (OCH
_Three )_Two , HSi (C₆ H_Five )_Two (OCH_Three ), HSi
(CH_Three ) (OC (O) CH_Three )_Two , HSi (CH_Three )
_Two O- [Si (CH_Three )_Two O]_Two-Si (CH _Three ) (OC
H_Three )_Two , HSi (CH_Three ) [ON = C (CH_Three )_Two]
_Two (However, in the above chemical formula, C₆ H_Five Represents a phenyl group
And the like).

When adding such a hydrosilyl group-containing compound having a crosslinkable silyl group to a vinyl polymer having an alkenyl group at the terminal, a hydrosilylation catalyst can be used. As such a hydrosilylation catalyst, any of those described in detail below can be used.

The vinyl polymer having an alkenyl terminal at the terminal obtained by the above method can be used as a curable composition containing the vinyl polymer as a main component. The curable composition,
(A) a vinyl polymer having an alkenyl group at a terminal,
(B) a compound containing a hydrosilyl group. The vinyl polymer having an alkenyl group at the terminal of the component (A) may be used alone or in combination of two or more. The molecular weight of the component (A) is not particularly limited, but is preferably in the range of 500 to 100,000, more preferably 3000 to 50,000. When the molecular weight is 500 or less, the intrinsic properties of the vinyl polymer are hardly exhibited. .

The hydrosilyl group-containing compound as the component (B) is not particularly limited, and various compounds can be used. That is, the following general formula (12) or general formula (13)
(R ¹⁷ ) ₃ SiO— [Si (R ¹⁷ ) ₂ O] _a — [Si (H) (R ¹⁸ ) O] _b — [Si (R ¹⁸ ) (R ¹⁹ ) O] _C -Si (R ¹⁷ ) ₃ (12) H (R ¹⁷ ) ₂ SiO- [Si (R ¹⁷ ) ₂ O] _a- [Si (H) (R ¹⁸ ) O] _b- [Si (R ^{18 _{) (R 19) O] C}} -Si (R 17) 2 H (13) ( wherein R ¹⁷ and R ¹⁸ are the same or different, an alkyl group having 1 to 6 carbon atoms, or a phenyl group. R
¹⁹ is an alkyl group having 1 to 10 carbon atoms or 7 to 10 carbon atoms
Represents an aralkyl group. a is 0 ≦ a ≦ 100, b is 2 ≦
b ≦ 100, C is an integer of 0 ≦ C ≦ 100, respectively), a cyclic siloxane represented by the following general formula (14);

[0085]

Embedded image

(Wherein R ¹⁷ , R ¹⁸ and R ¹⁹ are the same as above. D is 0 ≦ d ≦ 8, e is 2 ≦ e ≦ 10, and f is 0 ≦ f ≦
8, each representing an integer, and 3 ≦ d + e + f ≦ 1
0) can be used.

These may be used alone or as a mixture of two or more.
May be used. Making these hydrosilyl group-containing
Among the compounds, from the viewpoint of compatibility with the vinyl polymer,
Having a phenyl group, represented by the following general formula (15) or (16)
And the following general formulas (17) and (1)
The cyclic siloxane represented by 8) is preferred. (CH_Three )_Three SiO- [Si (H) (CH_Three ) O]_g − [Si (C₆ H_Five )_Two O]_h -Si (CH_Three )_Three (15) (CH_Three )_Three SiO- [Si (H) (CH_Three ) O]_g − [Si (CH_Three ) ｛CH _Two C (H) (R²⁰) C₆ H_Five ｝ O]_h -Si (CH_Three )_Three (16) (where R²⁰Represents a hydrogen or a methyl group. g is 2 ≦ g
≦ 100, h is an integer of 0 ≦ h ≦ 100, respectively.
You. C₆ H_Five Represents a phenyl group)

[0088]

Embedded image

(Wherein, R ²¹ represents hydrogen or a methyl group; i is 2 ≦ i ≦ 10; j is 0 ≦ j ≦ 8;
It is an integer and 3 ≦ i + j ≦ 10. C ₆ H ₅
Is a phenyl group)

Among the components (B), the compound having at least two or more hydrosilyl groups includes the low molecular weight compounds having two or more alkenyl groups in the molecule.
Compounds obtained by subjecting the hydrosilyl group-containing compounds represented by the above general formulas (12) to (18) to an addition reaction so that some hydrosilyl groups remain even after the reaction can be used. The low molecular compound having two or more alkenyl groups in the molecule is not particularly limited, and various compounds can be used. For example, 1,4-pentadiene, 1,5-hexadiene, 1,6-heptadiene, 1,7-octadiene, 1,8-nonadiene, 1,
Hydrocarbon compounds such as 9-decadiene; ether compounds such as O, O'-diallylbisphenol A and 3,3'-diallylbisphenol A; diallyl phthalate, diallyl isophthalate Ester compounds such as triaryltrimellitate and tetraallylpyromellitate; and carbonaceous compounds such as diethylene glycol diallyl carbonate.
And the like compounds.

The above addition reaction is carried out, for example, by the general formula (1)
It can be carried out by slowly dropping the alkenyl group-containing compound mentioned above in the presence of a hydrosilylation catalyst with respect to the excess amount of the hydrosilyl group-containing compound shown in 2) to (18). Thus, the target compound can be obtained. Among such compounds, the availability of raw materials,
The following are preferred in consideration of the ease of removal of the siloxane used in excess and the compatibility of the component (A) with the polymer.

[0092]

Embedded image

The polymer (A) and the hydrosilyl group-containing compound (B) can be mixed at an arbitrary ratio, but from the viewpoint of curability, the alkenyl group in the polymer (A) and the component ( The molar ratio of the hydrosilyl group in B) is 5 to 5.
It is preferably in the range of 0.2, more preferably 2.5 to 0.4. If the molar ratio is more than 5, curing may be insufficient and only a cured product with a low tackiness may be obtained, and if it is less than 0.2, a large amount of active hydrosilyl groups will remain in the cured product even after curing. , Cracks and voids are generated, and a uniform and strong cured product may not be obtained.

The curing reaction between the polymer (A) and the hydrosilyl group-containing compound (B) proceeds by mixing and heating the two components. can do. Examples of such a hydrosilylation catalyst include a radical initiator such as an organic peroxide and an azo compound, and a transition metal catalyst.

The radical initiator is not particularly limited, and various types can be used. To illustrate,
Di-t-butyl peroxide, 2,5-dimethyl-2,
5-di (t-butylperoxy) hexane, 2,5-dimethyl-2,5-di (t-butylperoxy) -3-hexyne, dicumyl peroxide, t-butylcumyl peroxide, α, α′-bis Dialkyl peroxides such as (t-butylperoxy) isopropylbenzene;
Benzoyl peroxide, p-chlorobenzoyl peroxide, m-chlorobenzoyl peroxide, 2,4-
Diacyl peroxides such as dichlorobenzoyl peroxide and lauroyl peroxide; perbenzoic acid-t-
Peroxyesters such as diisopropyl percarbonate and di-2-ethylhexyl percarbonate; 1,1-di (t-butylperoxy) cyclohexane, 1,1-di ( Peroxyketals such as (t-butylperoxy) -3,3,5-trimethylcyclohexane and the like.

Examples of the above transition metal catalyst include those in which platinum solid is dispersed in a carrier such as platinum alone, alumina, silica, carbon black, etc .; chloroplatinic acid; chloroplatinic acid and alcohol, aldehyde, ketone Complexes with etc .;
Platinum-olefin complexes, platinum (0) -divinyltetramethyldisiloxane complexes, and the like can be mentioned. Examples of catalysts other than platinum compounds include RhCl (PPh ₃ ) ₃ and RhC
l ₃ , RuCl 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,
Two or more types may be used in combination.

The amount of the catalyst is not particularly limited.
10 ^-1 to 10 ^-8 m per 1 mol of the alkenyl group of the component
ol, and more preferably 10
The range is from ^-3 to 10 ^-6 mol. If it is less than 10 ^-8 mol, curing may not proceed sufficiently. Since the hydrosilylation catalyst is expensive, it is preferable not to use 10 ^-1 mol or more.

If the above 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 to 200 ° C, preferably 30 to 150 ° C.
For 10 seconds to 24 hours. Especially 80 to 15
At a high temperature of 0 ° C., a material which cures in a short time of about 10 seconds to 1 hour can be obtained.

The properties of the cured product depend on the polymer of the component (A) used and the main chain skeleton and molecular weight of the curing agent (B). can do.

Specific applications of the cured product obtained from the composition of the present invention include sealing materials, adhesives, pressure-sensitive adhesives, elastic adhesives, paints, powder coatings, foams, and potting materials for electric and electronic equipment. , Films, gaskets, various molding materials, artificial marble and the like.

The vinyl polymer having a crosslinkable silyl group at the terminal obtained as described above can be used as a curable composition containing the vinyl polymer as a main component. The vinyl polymer as the main component may be used alone or in combination of two or more. The molecular weight is not particularly limited, but is preferably in the range of 500 to 100,000, more preferably 3000 to 50,000. When the molecular weight is 500 or less, the intrinsic properties of the vinyl polymer are hardly exhibited, and when it is 100,000 or more, handling may be difficult, which is not preferable.

A vinyl polymer having a hydrolyzable silyl group at the terminal is three-dimensionally cured by a crosslinking reaction when it comes into contact with moisture. Since the hydrolysis rate varies depending on the temperature, humidity, and type of the hydrolyzable group, an appropriate hydrolyzable group must be selected according to the use conditions. In addition, it is preferable that the vinyl polymer having a hydrolyzable silyl group at the end thereof be kept from contact with moisture as much as possible during storage.

A condensation catalyst may be added to accelerate the above curing reaction. Examples of the condensation catalyst include alkyl titanates, organosilicon titanates, metal salts of carboxylic acids such as tin octylate and dibutyltin dilaurate; amine salts such as dibutylamine-2-ethylhexoate; Acidic and basic catalysts can be used.
The amount of use is not particularly limited, but it is preferable to use 0.01 to 5% by weight based on the vinyl polymer having a crosslinkable silyl group at the terminal.

If a condensation catalyst is mixed with the vinyl polymer having a crosslinkable silyl group at the terminal, which is the main component, as required, and cured, a uniform cured product can be obtained. The curing conditions are not particularly limited, but are generally 0 to 100 ° C, preferably 10 to 50 ° C, for about 1 hour to 1 week. The properties of the cured product depend on the main chain skeleton and molecular weight of the polymer used, but it can be widely prepared from rubbery to resinous.

Specific applications of the cured product obtained from the above composition include sealing materials, adhesives, pressure-sensitive adhesives, elastic adhesives, paints, powder paints, foams, potting materials for electric and electronic devices, Films, molding materials, artificial marble and the like.

[0106]

The present invention will be described in more detail with reference to the following examples, but the present invention is not limited to these examples.

Production Example 1Poly with terminal halogen
(Acrylic acid ester)  In a 1 L pressure-resistant glass reaction vessel, add methyl acrylate (10
0 mL, 1.11 mol), α, α'-dibromo-p-
Xylene (5.89 g, 22.2 mmol), first bromide
Copper (3.18 g, 22.2 mmol), 2,2'-bipi
Lysyl (10.4 g, 66.7 mmol), acetonitrile
Lil (20 mL) and ethyl acetate (80 mL)
And blow in nitrogen gas for 10 minutes to remove dissolved oxygen
And then sealed. The mixture was heated to 130 ° C and
For 30 minutes. After cooling to room temperature, the reaction mixture is
After diluting with ethyl acetate and filtering the resulting insoluble solid,
The solution was washed twice with dilute hydrochloric acid and once with brine. Organic layer
Dry over anhydrous sodium sulfate and evaporate the volatiles under reduced pressure.
9 poly (methyl acrylate) having bromine at both ends
0.1 g was obtained. Result of GPC measurement (polystyrene conversion)
As a result, the number average molecular weight (Mn) of the polymer was 5000,
The distribution (Mw / Mn) was 1.31. In addition, oligo
Bromine introduced per molecule of mer is¹1 H NMR
From the analysis, it was 1.78.

Production Example 2Poly with terminal halogen
(Acrylic acid ester)  In a 30 mL pressure-resistant reactor, methyl acrylate (7.5 m
L, 7.17 g, 83.4 mmol), α, α'-dib
Lomo-p-xylene (438 mg, 1.67 mmol
l), cuprous bromide (239 mg, 1.67 mmol),
2,2'-bipyridyl (518 mg, 3.34 mmol
l), acetonitrile (1.5 mL) and ethyl acetate
(6.0 mL) and blow nitrogen gas for 10 minutes
After removing dissolved oxygen, the tube was sealed. This mixture is
The mixture was heated to 30 ° C. and reacted for 45 minutes. Vinegar reaction mixture
Diluted with ethyl acetate (20 mL), and diluted with diluted hydrochloric acid three times.
Washes once. Dry the organic layer over anhydrous sodium sulfate
And the volatiles are distilled off under reduced pressure.
(Methyl acrylate) was obtained (yield 4.72 g). GP
As a result of C measurement (in terms of polystyrene), the number average of the polymer
The molecular weight (Mn) is 3630, and the molecular weight distribution (Mw / Mn) is
1.21. In addition, the number of molecules per oligomer
The bromine entered,¹According to 1 H NMR analysis, 1.62
there were.

Embodiment 1Has an alkenyl group at the end of the main chain
Preparation of vinyl polymer  Ethyl allyl malonate in a 50 mL 3-neck round bottom flask
(0.1 mL, 0.51 mmol), potassium-ter
t-butoxide (80 mg, 0.72 mmol), and
And tetrahydrofuran (1.0 mL)
The reaction was performed for 1 hour at the reflux temperature under an atmosphere. Production Example 1
Tet of poly (methyl acrylate) (1.0 g) formed
Add a solution of lahydrofuran (2 mL) at reflux temperature
Stirred for hours. The reaction mixture is made up to about 50 mL with ethyl acetate
Dilute and wash twice with 2% hydrochloric acid and once with brine. Yes
After the organic layer was dried over anhydrous sodium sulfate, the solvent was removed under reduced pressure.
The product was isolated by evaporation. Product in a small amount of ethyl acetate
The polymer was purified by dissolving and reprecipitating from hexane.
Made. Alkenyl introduced per oligomer molecule
The radical is¹According to 1 H NMR analysis, the number was 0.62.

Embodiment 2Has an alkenyl group at the end of the main chain
Preparation of vinyl polymer  Oily sodium hydride in a 50 mL 3-neck round bottom flask
(106 mg, 2.64 mmol) in a nitrogen atmosphere
Washed sodium hydride several times with dry hexane
Thereafter, dimethylacetamide (3.0 mL) was added. Sa
Allylmalononitrile (292 mg, 2.76 mm
ol) in dimethylacetamide (1.0 mL).
C. and the mixture was stirred at the same temperature for 1 hour. According to Production Example 2
D of synthesized poly (methyl acrylate) (1.0 g)
Add MAc (2.0 mL) solution and stir at room temperature for 1 hour
did. After neutralizing the reaction mixture with ice water-dilute hydrochloric acid, acetic acid
Extract with ethyl (30 mL) and wash the organic layer with 2% hydrochloric acid.
Twice, once with brine. The organic layer was dried over anhydrous sodium sulfate.
The solvent was distilled off under reduced pressure to isolate the product.
Was. Dissolve the product in a small amount of ethyl acetate and add
The polymer was purified by reprecipitation (Fn (alkane).
Nyl) = 1.68).

Embodiment 3Having a crosslinkable silyl group at the end
Preparation of vinyl polymer  The alkenyl-terminated polymer obtained in Example 2
React with dimethoxymethylsilane using a platinum complex.
As a result, a polymer having a crosslinkable silyl terminal was obtained.

Embodiment 4Preparation of curable composition  The alkenyl-terminated polymer obtained in Example 2
-Mix polyvalent hydrosilyl compound and platinum complex and heat
As a result, a rubbery cured product was obtained.

Example 5 When the tin-based condensation curing catalyst and water were mixed with the polymer having a crosslinkable silyl terminal at the end obtained in Example 3, a rubber-like cured product was obtained.

[0114]

According to the present invention, the alkenyl group or the crosslinkable silyl group has a high ratio of terminal groups in the main chain due to a carbon-carbon bond which does not pass through a hetero atom such as sulfur and is hardly cleaved. A vinyl polymer introduced into, and
These simple manufacturing methods are provided. Since these polymers do not contain a hetero atom in the main chain, the resulting cured product has good weather resistance. Further, since the crosslinkable functional group is reliably introduced at the terminal of the main chain, a cured product having excellent curing properties can be obtained.

──────────────────────────────────────────────────の Continued on the front page (51) Int.Cl. ⁶ Identification code FI C08F 20/04 C08F 20/04 30/08 30/08 C08L 25/00 C08L 25/00 33/00 33/00 43/04 43 / 04 (72) Inventor Masato Kusakabe 1-2-80 Yoshida-cho, Hyogo-ku, Kobe-shi, Hyogo Pref.

Claims (22)

[Claims] An alkenyl group represented by the general formula (1)
At at least one end of the main chain.
Vinyl polymer. -CH_Two -C (R¹ ) (R^Two ) -C (R^Three ) (R^Four ) -R^Five -C (R⁶ ) = CH_Two (1) (where R¹ And R^Two Are the same or different and are monovalent
Indicates a machine group. R^Three And R ^Four Are the same or different
Represents an electron-withdrawing substituent, or one of them represents an electron-withdrawing substituent.
Represents an attractive substituent, the other being hydrogen, an alkyl having 1 to 10 carbon atoms.
Represents a kill group or a phenyl group. R^Five Is a direct bond,
Or a carbon optionally containing one or more ether linkages
Represents a divalent organic group represented by Formulas 1 to 10. R⁶ Is hydrogen, carbon
An alkyl group having 1 to 10 carbon atoms and an aryl group having 6 to 10 carbon atoms
Or an aralkyl group having 7 to 10 carbon atoms. ) 2. A crosslinkable silyl group represented by the general formula (2)
At at least one end of the main chain.
Vinyl polymer. -CH_Two -C (R¹ ) (R^Two ) -C (R^Three ) (R^Four ) -R^Five -CH (R⁶ ) -CH_Two − [Si (R⁷ )_2-b (Y)_b O]_m -Si (R⁸ )_3-a (Y)_a (2) [wherein, R¹ And R^Two Are the same or different and are monovalent
Indicates a machine group. R^Three And R ^Four Are the same or different
Represents an electron-withdrawing substituent, or one of them represents an electron-withdrawing substituent.
Represents an attractive substituent, the other being hydrogen, an alkyl having 1 to 10 carbon atoms.
Represents a kill group or a phenyl group. R^Five Is a direct bond,
Or a carbon optionally containing one or more ether linkages
Represents a divalent organic group represented by Formulas 1 to 10. R⁶ Is hydrogen, carbon
An alkyl group having 1 to 10 carbon atoms and an aryl group having 6 to 10 carbon atoms
Or an aralkyl group having 7 to 10 carbon atoms. R⁷ And R
⁸ Are the same or different and have 1 to 20 carbon atoms
Group, an aryl group having 6 to 20 carbon atoms, and an aryl group having 7 to 20 carbon atoms.
An aralkyl group or (R ′)_Three SiO- (wherein R '
Represents a monovalent hydrocarbon group having 1 to 20 carbon atoms.
R ′ may be the same or different. )so
Represents the triorganosiloxy group represented. R⁷ Or R⁸ 
When two or more are present, they may be the same
And may be different. Y is a hydroxyl group or a hydrolyzable
Represents a group, and when two or more are present, they are the same
Or may be different. a is 0, 1, 2, or
3 is represented. b represents 0, 1 or 2. m is 0 to 19
Is an integer. However, it is satisfied that a + mb ≧ 1.
It shall be. ] 3. The method according to claim 1, wherein the electron-withdrawing substituent is -CO ₂ R (where R is an alkyl group having 1 to 20 carbon atoms, 6 to ₂ carbon atoms).
Represents an aryl group having 0 or an aralkyl group having 7 to 20 carbon atoms. ), -C (O) R (R is as defined above), and-
3. A group selected from the group consisting of CN.
The polymer as described. 4. The polymer according to claim 1, wherein the main chain is a polymer of a (meth) acrylic acid monomer. 5. The polymer according to claim 4, wherein the (meth) acrylic monomer is an acrylic ester monomer. 6. The polymer according to claim 4, wherein the (meth) acrylic acid-based monomer is a methacrylic acid ester-based monomer. 7. The polymer according to claim 5, wherein the acrylate monomer is butyl acrylate. 8. The polymer according to claim 1, wherein the main chain is obtained by polymerizing a styrene monomer. 9. The ratio (Mw / Mn) of the weight average molecular weight (Mw) to the number average molecular weight (Mn) measured by gel permeation chromatography is a value of 1.8 or less. Or the polymer according to item 1. 10. The number average molecular weight is from 500 to 10,000.
The polymer according to any one of claims 1 to 9, which is in a range of 0. 11. A vinyl-based monomer is polymerized to produce a vinyl-based polymer having a group represented by the following general formula (3) at at least one terminal, and the terminal halogen of the polymer is converted to a compound represented by the following general formula (3) 4. Substitution with an alkenyl group-containing carbanion represented by 4).
11. A method for producing a vinyl polymer having the alkenyl group according to any one of 9 or 10 at at least one main chain terminal. —CH ₂ —C (R ¹ ) (R ² ) (X) (3) (wherein R ¹ and R ² are the same or different and represent a monovalent organic group. X is chlorine, bromine or represents ^{iodine) M + C -. (R} 3) (R 4) -R 5 -C (R 6) = CH 2 (4) ( wherein, R ³ and R ⁴ are both the same or different, or represents an electron-withdrawing group, or, one represents an electron-withdrawing substituent, is .R ⁵ other represents hydrogen, an alkyl group or phenyl group having 1 to 10 carbon atoms, a direct bond, or one (The above represents a divalent organic group having 1 to 10 carbon atoms which may contain an ether bond. M ⁺ represents an alkali metal ion or a quaternary ammonium ion.) 12. A vinyl-based monomer is polymerized to produce a vinyl-based polymer having a group represented by the following general formula (3) at at least one terminal, and the terminal halogen of the polymer is converted into a compound represented by the following general formula ( 5. Substitution with a crosslinkable silyl group-containing carbanion represented by 5).
0. A method for producing a vinyl polymer having the crosslinkable silyl group according to any one of 0 above at at least one main chain terminal. —CH ₂ —C (R ¹ ) (R ² ) (X) (3) (wherein R ¹ and R ² are the same or different and represent a monovalent organic group. X is chlorine, bromine or represents ^{iodine) M + C -. (R} 3) (R 4) -R 5 -CH (R 6) -CH 2 - [Si (R 7) 2-b (Y) b O] m -Si (R ⁸ ) _3-a (Y) _a (5) wherein R ³ and R ⁴ are the same or different and each represents an electron-withdrawing substituent, or one represents an electron-withdrawing substituent And the other represents hydrogen, an alkyl group having 1 to 10 carbon atoms or a phenyl group. R ⁵ represents a direct bond or a divalent organic group having 1 to 10 carbon atoms which may contain one or more ether bonds. R ⁶ represents hydrogen, an alkyl group having 1 to 10 carbon atoms, an aryl group having 6 to 10 carbon atoms, or an aralkyl group having 7 to 10 carbon atoms. R ⁷ and R ⁸
Are the same or different and are 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 (R ′) ₃ SiO— (wherein R ′
Represents a monovalent hydrocarbon group having 1 to 20 carbon atoms, and three R's may be the same or different. ) Represents a triorganosiloxy group. R ⁷ or R ⁸
When two or more are present, they may be the same or different. Y represents a hydroxyl group or a hydrolyzable group, and when two or more are present, they may be the same or different. a represents 0, 1, 2, or 3. b represents 0, 1 or 2. m is 0 to 19
Is an integer. However, it is assumed that a + mb ≧ 1 is satisfied. M ⁺ represents an alkali metal ion or a quaternary ammonium ion. ] 13. The method according to claim 11, wherein M ⁺ is a sodium ion or a potassium ion. 14. A crosslinkable silyl group represented by the following general formula (6), wherein a vinyl polymer having an alkenyl group at the terminal of a main chain according to any one of claims 1, 3 to 9 or 10 is added. The method for producing a vinyl polymer having a crosslinkable silyl group at at least one main chain terminal according to any one of claims 2 to 10, characterized by reacting a hydrosilane compound having the following formula: _{^{H- [Si (R 7) 2}} -b (Y) b O] m -Si (R 8) 3-a (Y) a (6) wherein, R ⁷ and R ⁸ are the same or different, 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 (R ′) ₃
Tri- represented by SiO- (wherein R 'represents a monovalent hydrocarbon group having 1 to 20 carbon atoms, and three R's may be the same or different). Represents an organosiloxy group. When two or more R ⁷ or R ⁸ are present, they may be the same or different. Y represents a hydroxyl group or a hydrolyzable group, and when two or more are present,
They may be the same or different. a
Represents 0, 1, 2 or 3. b represents 0, 1 or 2. m is an integer of 0 to 19. Where a + mb ≧
1 is satisfied. ] 15. A vinyl monomer is polymerized by using an organic halide or a sulfonyl halide compound as an initiator, and using a transition metal complex as a catalyst.
15. The production method according to 1 to 14. 16. The method according to claim 15, wherein the transition metal complex is a metal complex selected from the group consisting of copper, nickel, ruthenium, and iron. 17. The method according to claim 16, wherein the transition metal complex is a copper complex. 18. The method according to claim 11, wherein the vinyl monomer is polymerized in the presence of a chain transfer agent. (A) a vinyl polymer having an alkenyl group according to any one of (1), (3) to (9) or (10) at the terminal of the main chain thereof, and (B) a compound containing a hydrosilyl group Curable composition characterized by the above-mentioned. 20. The curable composition according to claim 19, wherein the molar ratio of the alkenyl group contained in the component (A) to the hydrosilyl group contained in the component (B) is in the range of 0.2 to 5. . 21. A curable composition comprising, as a main component, a vinyl-based polymer having the crosslinkable silyl group according to claim 2 at a main chain terminal. 22. The curable composition according to claim 21, comprising a curing catalyst in an amount of 0.01 to 5% by weight based on the polymer according to any one of claims 2 to 10.