JP2003113212A - Vinyl sulfide group-containing polymer and curable composition - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide both a polymer having vinyl sulfide groups and capable of simplifying a purification step and performing an aqueous polymerization and a curable composition consisting essentially of the polymer and affording a cured product having excellent heat, weather and oil resistances. SOLUTION: This polymer is derived from a polymer obtained by polymerizing at least one monomer selected from acrylic esters, methacrylic esters, acrylic acid, methacrylic acid, styrene, α-methylstyrene, butadiene, isoprene, vinyl chloride, vinyl acetate, acrylonitrile and methacrylonitrile, and has at least the one vinyl sulfide group in the molecule. The curable composition consists essentially of the polymer.

Description

Detailed Description of the Invention

[0001]

TECHNICAL FIELD The present invention relates to a vinyl sulfide group-containing polymer, a curable composition containing the polymer, and a cured product. More specifically, it relates to a polymer having a vinyl sulfide group at its terminal, a curable composition containing the polymer as an essential component, and a cured product.

[0002]

2. Description of the Related Art It is known that a polymer having an alkenyl group as a functional group is crosslinked when combined with an appropriate curing agent to give a cured product excellent in heat resistance and durability. For example, the polymer having an alkenyl group is crosslinked and cured by using a compound having a hydrogen-silicon bond as a curing agent or by utilizing a photoreaction. It can also be cured by utilizing a radical crosslinking reaction using a peroxide or sulfur.

As a main chain skeleton of a polymer having an alkenyl group at a terminal, a polyether polymer such as polyethylene oxide or polypropylene oxide; polyisobutylene, polybutadiene, polyisoprene, polychloroprene, hydrogenated polybutadiene, hydrogenated polyisoprene, etc. Of the above-mentioned hydrocarbon polymers; polyester-based polymers such as polyethylene terephthalate, polybutylene terephthalate, and polycaprolactone; silicone-based polymers such as polydimethylsiloxane. These polymers are used in various applications depending on the type of main chain skeleton and the difference in cross-linking form. In addition to these, in order to obtain a cured product with excellent weather resistance and heat resistance, an alkenyl group is introduced into the vinyl polymer obtained by polymerizing vinyl monomers such as acrylic acid ester and methacrylic acid ester. How to do it is being researched. However, with respect to such a vinyl polymer having an alkenyl group introduced therein, no convenient method for industrial production has been found.

Japanese Unexamined Patent Publication (Kokai) No. 5-255415 discloses a method of synthesizing a vinyl polymer having alkenyl groups at both ends by using an alkenyl group-containing disulfide compound as a chain transfer agent. JP-A-5-26280
No. 8 discloses a vinyl polymer having hydroxyl groups at both ends using a disulfide compound having a hydroxyl group as a chain transfer agent, and the reactivity of the hydroxyl group is utilized to further produce an alkenyl group at both ends. A method for synthesizing a vinyl-based polymer having a is disclosed. However, it is difficult for these methods to reliably introduce alkenyl groups at both ends, and when such a polymer is used, a cured product having satisfactory properties cannot be obtained. Furthermore, in order to surely introduce an alkenyl group at both ends, it is necessary to use a large amount of chain transfer agent, which causes problems in manufacturing process and cost. Further, when a large amount of such a chain transfer agent is used, the molecular weight of the obtained polymer becomes too low, and thus a cured product having satisfactory properties cannot be obtained.

For the purpose of solving such a problem, a method of introducing an alkenyl group at the terminal of a polymer using an organometallic compound (Japanese Patent Laid-Open No. 9-272714),
A method such as a method of performing an atom transfer radical polymerization using an organic halide or the like as an initiator with a transition metal complex as a catalyst, and introducing an alkenyl group by a reaction utilizing a terminal halogen atom (Japanese Patent Laid-Open No. 2000-128924). Is proposed. However, in these methods, since a large amount of metal compound is used, there are problems that the obtained polymer is colored and that a purification step is required and the manufacturing step is complicated. In addition, these metal complexes sometimes inhibit the hydrosilylation reaction, and there is a problem that a large amount of hydrosilylation catalyst is required. Further, there is a manufacturing problem that water-based polymerization cannot be applied.

Further, in comparison with a commonly used alkenyl group such as a vinyl group or an allyl group, a vinyl sulfide group has a contribution of a sulfur atom when radically crosslinked, so that the crosslinking reaction proceeds more effectively. There is an advantage. However, it has been difficult to introduce such a vinyl sulfide group into the polymer.

On the other hand, regarding the production of vinyl copolymers,
Reversible Addition-Desorption Chain Transfer (Revers) in that the molecular weight and molecular weight distribution can be controlled, and a wide range of monomers and a wide range of polymerization methods including water-based polymerization can be used.
Ible Addition-Fragmentati
on Chain Transfer (RAFT) polymerization method is excellent, and for example, WO98 / 01478, WO99 / 05099, WO99 / 3114.
4, gazette, Macromolecules, 1998.
31: 5559, Macromolecule
les, 1999, 32, 2071, Mac
romolecules, 1999, 32, 697
Page 7, and Macromolecules, 20
The details, including the reaction mechanism, are described in 2000, Vol. 33, page 243, etc. However, it does not describe a method of introducing a vinyl sulfide group as a functional group, nor does it mention a curable composition. The present invention relates to a vinyl sulfide group-containing polymer and a curable composition containing the polymer, and preferably a vinyl sulfide group is introduced into the polymer obtained by using the RAFT polymerization method.

[0008]

SUMMARY OF THE INVENTION The present invention has been made to solve the above-mentioned conventional problems, and its object is to provide a curable composition which can be produced by aqueous polymerization, is easy to purify, and is a curable composition. The purpose of the present invention is to provide a polymer in which a cured product can be easily obtained, in particular, a polymer having a vinyl sulfide group at the terminal, and the cured product containing such a polymer as an essential component has heat resistance and weather resistance. It is to provide a curable composition having excellent properties and oil resistance.

[0009]

Means for Solving the Problems The inventors of the present invention have made extensive studies to solve the above problems, and have reached the following inventions.
Polymerize at least one monomer selected from acrylic acid ester, methacrylic acid ester, acrylic acid, methacrylic acid, styrene, α-methylstyrene, butadiene, isoprene, vinyl chloride, vinyl acetate, acrylonitrile, and methacrylonitrile. Derived from the polymer obtained by the method of formula (1)

[0010]

[Chemical 7] A vinyl sulfide group-containing polymer having at least one vinyl sulfide group in each molecule.

In a preferred embodiment, the vinyl sulfide group-containing polymer has a vinyl sulfide group at the end of the molecular chain.

In a preferred embodiment, the vinyl sulfide group-containing polymer has a linear molecular structure and has vinyl sulfide groups at both ends of the molecular chain.

In a preferred embodiment, the monomer is at least one selected from acrylic acid ester, methacrylic acid ester, and acrylonitrile.

In a preferred embodiment, the vinyl sulfide group-containing polymer is a polymer block obtained by polymerizing a monomer containing 50% by weight or more of a methacrylic acid ester, and a polymer block containing 50% by weight or more of an acrylic acid ester. And a polymer block obtained by polymerizing the monomer.

In a preferred embodiment, the vinyl sulfide group-containing polymer is obtained by the step of reacting a polymer having at least one mercapto group in one molecule with acetylene.

[0016] In a preferred embodiment, the step of reacting with the above-mentioned acetylene is carried out in the presence of a base.

In a preferred embodiment, the above-mentioned polymer having at least one mercapto group in one molecule is a polymer having at least one thiocarbonylthio group in one molecule, a base, an acid, and hydrogen- It is obtained by a step of treating with at least one treating agent selected from nitrogen bond-containing compounds.

In a preferred embodiment, the treating agent is a base.

In a preferred embodiment, the polymer having at least one thiocarbonylthio group in one molecule is obtained by the step of polymerizing the above monomer in the presence of a compound having a thiocarbonylthio group. The compound having the thiocarbonylthio group is at least one compound selected from the general formula (2) and the general formula (3):

[0020]

[Chemical 8] (In the formula, R ¹ is a p-valent organic group having 1 or more carbon atoms, and contains at least one of a nitrogen atom, an oxygen atom, a sulfur atom, a halogen atom, a silicon atom, a phosphorus atom, and a metal atom. May be a high molecular weight compound; Z ¹
Is a hydrogen atom, a halogen atom, or a monovalent organic group having 1 or more carbon atoms, and the monovalent organic group is a nitrogen atom, an oxygen atom, a sulfur atom, a halogen atom, a silicon atom, or a phosphorus atom. It may contain at least one and may be a high molecular weight compound; p is an integer of 1 or more, and when p is 2 or more, Z ¹ may be the same or different), and

[0021]

[Chemical 9] (In the formula, R ² is a monovalent organic group having 1 or more carbon atoms, and contains at least one of a nitrogen atom, an oxygen atom, a sulfur atom, a halogen atom, a silicon atom, a phosphorus atom, and a metal atom. Or a high molecular weight compound; Z ²
Is a sulfur atom (when q = 2), an oxygen atom (when q = 2), a nitrogen atom (when q = 3), or a q-valent organic group having 1 or more carbon atoms. The group is a nitrogen atom,
It may contain at least one of an oxygen atom, a sulfur atom, a halogen atom, a silicon atom, and a phosphorus atom, and may be a high molecular weight compound; q is an integer of 2 or more and R ² is the same. But it may be different).

In a preferred embodiment, the compound having a thiocarbonylthio group is a compound represented by the general formula (4):

[0023]

[Chemical 10] (In the formula, R ³ is a divalent organic group, and is a nitrogen atom, an oxygen atom, a sulfur atom, a halogen atom, a silicon atom, a phosphorus atom,
And at least one of a metal atom and may be a high molecular weight compound; Z ¹ is a hydrogen atom, a halogen atom, or a monovalent organic group having 1 or more carbon atoms; The valent organic group may contain at least one of a nitrogen atom, an oxygen atom, a sulfur atom, a halogen atom, a silicon atom and a phosphorus atom, and may be a high molecular weight substance; Z ¹ is the same. But it may be different). In a preferred embodiment, the vinyl sulfide group-containing polymer has a number average molecular weight of 1,000 to 100,000 as determined by gel permeation chromatography analysis.

In a preferred embodiment, the vinyl sulfide group-containing polymer has a molecular weight distribution of 1.8 or less as determined by gel permeation chromatography analysis.

The curable composition of the present invention comprises the following three components (a), (b), and (c) as essential components: (a) a vinyl sulfide group-containing polymer as described above, (B) A compound having a hydrogen-silicon bond, and (c) a hydrosilylation catalyst.

In a preferred embodiment, the above component (b)
The compound having a hydrogen-silicon bond is a compound having two or more hydrogen-silicon bonds in one molecule.

In a preferred embodiment, the above component (b)
The compound having a hydrogen-silicon bond is a compound having a crosslinkable silyl group.

In a preferred embodiment, the above component (c)
The hydrosilylation catalyst is a platinum-containing compound.

In another form of the curable composition of the present invention, the following two components (a) and (d) are essential components: (a) The vinyl sulfide group-containing polymer described in any one of the above. , (D) a crosslinking agent.

In a preferred embodiment, an unsaturated bond-containing compound is contained as a component other than the above (a) and (d).

The cured product of the present invention is obtained by curing any of the curable compositions described above.

[0032]

BEST MODE FOR CARRYING OUT THE INVENTION The vinyl sulfide group-containing polymer of the present invention comprises acrylic acid ester, methacrylic acid ester, acrylic acid, methacrylic acid, styrene, α-methylstyrene, butadiene, isoprene, vinyl chloride, vinyl acetate, acrylonitrile. And a polymer obtained by polymerizing at least one monomer selected from methacrylonitrile, and having the formula (1)

[0033]

[Chemical 11] At least one vinyl sulfide group represented by is included in one molecule. The curable composition of the present invention contains the vinyl sulfide group-containing polymer as an essential component. Hereinafter, a method for preparing the vinyl sulfide group-containing polymer of the present invention, components for preparation, and the composition of the present invention will be sequentially described.

The method for producing the vinyl sulfide group-containing polymer of the present invention is not particularly limited. As described above, the vinyl sulfide group-containing polymer is an acrylic acid ester, a methacrylic acid ester, acrylic acid, methacrylic acid, styrene, α-methylstyrene, butadiene,
It is derived from a polymer obtained by polymerizing at least one monomer selected from isoprene, vinyl chloride, vinyl acetate, acrylonitrile, and methacrylonitrile.
This polymer is preferably a polymer having at least one thiocarbonylthio group in one molecule from the viewpoint that a vinyl sulfide group can be reliably introduced. For example, a thiocarbonylthio group of a polymer having at least one thiocarbonylthio group in one molecule is converted to a mercapto group to obtain a polymer having at least one mercapto group in one molecule, and this is reacted with acetylene. By letting
The vinyl sulfide group-containing polymer of the present invention is obtained.

The method for polymerizing the above monomers to prepare a polymer having a thiocarbonylthio group is not particularly limited, but a compound having a thiocarbonylthio group is used as a reversible addition-elimination chain transfer agent, Method of radically polymerizing the monomer in the presence of the compound (RAFT polymerization)
It is preferable to apply the above because the thiocarbonylthio group can be surely introduced into the polymer and the molecular weight and the molecular weight distribution can be controlled.

The polymer is then treated with at least one selected from bases, acids, and hydrogen-nitrogen bond containing compounds.
The thiocarbonylthio group of the polymer is converted into a mercapto group by reacting with a treating agent composed of a seed compound.

Then, the obtained mercapto group-containing polymer is reacted with acetylene to obtain a vinyl sulfide group-containing polymer.

Monomers constituting the vinyl sulfide group-containing polymer of the present invention include acrylic acid ester, methacrylic acid ester, acrylic acid, methacrylic acid, styrene, α-
It is at least one monomer selected from methylstyrene, butadiene, isoprene, vinyl chloride, vinyl acetate, acrylonitrile, and methacrylonitrile. The above monomers may be polymerized alone, or a plurality of them may be copolymerized. When the copolymer is used, its form is arbitrary and is not limited, such as random copolymer, alternating copolymer, block copolymer, and graft copolymer.

Of the above monomers, specific examples of the acrylate ester include, but are not limited to, the following compounds: methyl acrylate, ethyl acrylate, n-propyl acrylate, isopropyl acrylate, N-Butyl acrylate, hexyl acrylate, 2-ethylhexyl acrylate, cyclohexyl acrylate, octyl acrylate, decyl acrylate, phenyl acrylate, toluyl acrylate, benzyl acrylate, isobornyl acrylate, 2-methoxyethyl acrylate , 3-methoxybutyl acrylate, acrylic acid 2
-Hydroxyethyl, 2-hydroxypropyl acrylate, stearyl acrylate, glycidyl acrylate, 2
-Acryloyloxypropyldimethoxymethylsilane, 2-acryloyloxypropyltrimethoxysilane, trifluoromethyl acrylate, pentafluoroethyl acrylate, 2,2,2-trifluoroethyl acrylate, 3-dimethylaminoethyl acrylate, acrylic Acid isobutyl, 4-hydroxybutyl acrylate, t-butyl acrylate, dodecyl acrylate, alkyl-modified dipentaerythritol acrylate, ethylene oxide-modified bisphenol A diacrylate, carbitol acrylate, ε-caprolactone-modified dipentaerythritol acrylate , Caprolactone modified tetrahydrofurfuryl acrylate, caprolactone modified hydroxypivalic acid neopentyl glycol ester diacrylate, dicapro Limethylolpropane tetraacrylate, dipentaerythritol hexaacrylate, dipentaerythritol pentaacrylate, tetraethylene glycol acrylate, tetrahydrofurfuryl acrylate, tripropylene glycol acrylate, trimethylolpropane ethoxytriacrylate, trimethylolpropane triacrylate, neo Pentyl glycol diacrylate, neopentyl glycol hydroxypivalate diacrylate, acrylic acid 1,9-nonanediol, acrylic acid 1,4-
Butanediol, 2-propenoic acid [2-
[1,1-Dimethyl-2-[(1-oxo-2-propenyl) oxy] ethyl] -5-ethyl-1,3-dioxan-5-yl] methyl ester, acrylic acid 1,6-
Hexanediol, pentaerythritol triacrylate, 2-acryloyloxypropyl hydrogen phthalate, methyl 3-methoxyacrylate, 2-aminoethyl acrylate, 2- (N, N-dimethylamino) ethyl acrylate, 3-aminoacrylate Propyl, 3- (N, N-diethylamino) propyl acrylate, allyl acrylate and the like. These may be used alone or in combination of two or more.

Of the above monomers, specific examples of the methacrylic acid ester include, but are not limited to, the following compounds: methyl methacrylate, ethyl methacrylate, n-butyl methacrylate, isobutyl methacrylate, T-Butyl methacrylate, 2-ethylhexyl methacrylate, dodecyl methacrylate, tridecyl methacrylate, stearyl methacrylate, cyclohexyl methacrylate, benzyl methacrylate, 2-hydroxyethyl methacrylate, 2-hydroxypropyl methacrylate, diethylaminoethyl methacrylate. , Glycidyl methacrylate, tetrahydrofurfuryl methacrylate, ethylene glycol dimethacrylate, triethylene glycol dimethacrylate, tetraethylene glycol dimethacrylate, dimethac 1,3-butylene glycol triacrylate, trimethylolpropane trimethacrylate, isopropyl methacrylate, pentyl methacrylate, hexyl methacrylate, heptyl methacrylate, octyl methacrylate, nonyl methacrylate, decyl methacrylate, phenyl methacrylate, methacrylic acid Toluyl, isobornyl methacrylate, 2-methoxyethyl methacrylate,
3-Methoxybutyl methacrylate, 2-aminoethyl methacrylate, 2-methacryloyloxypropyltrimethoxysilane, 2-methacryloyloxypropyldimethoxymethylsilane, trifluoromethyl methacrylate, pentafluoroethyl methacrylate, 2- (N , N-dimethylamino) ethyl, 3-aminopropyl methacrylate, 3- (N, N-diethylamino) propyl methacrylate, 2,2,2-trifluoroethyl methacrylate and the like. These may be used alone or in combination of two or more.

Among the above monomers, acrylic acid ester, methacrylic acid ester, and acrylonitrile are preferable because the resulting polymer has excellent heat resistance, weather resistance, and oil resistance. In terms of availability and price, esters of acrylic acid with alcohols having 1 to 4 carbon atoms such as methyl acrylate, ethyl acrylate, n-butyl acrylate, t-butyl acrylate, and 2-methoxyethyl acrylate; More preferred are esters of methacrylic acid with an alcohol having 1 to 4 carbon atoms such as methyl methacrylate, ethyl methacrylate, n-butyl methacrylate, t-butyl methacrylate, and 2-methoxyethyl methacrylate; and acrylonitrile.

When the vinyl sulfide group-containing polymer of the present invention is used as a thermoplastic elastomer, it is a block copolymer having a hard segment and a soft segment in one molecule. From the viewpoint of heat resistance and weather resistance, the hard segment preferably contains a monomer containing 50% by weight or more of a methacrylic acid ester as a constituent component, and the soft segment includes an acrylic acid ester 5
It is preferable to use a monomer containing 0% by weight or more as a constituent component. As the monomer constituting the hard segment, in terms of heat resistance, weather resistance, and strength of the resulting copolymer,
It is preferable to use a monomer containing 80% by weight or more of a methacrylic acid ester, and more preferable to use a monomer containing 90% by weight or more of a methacrylic acid ester. The methacrylic acid ester constituting the hard segment is not particularly limited, and the above-mentioned methacrylic acid ester can be used, but methyl methacrylate is preferable in terms of availability, cost, and strength and weather resistance of the resulting polymer. Of the monomers constituting the hard segment, the monomers other than the methacrylic acid ester are not particularly limited as long as they are copolymerizable with the methacrylic acid ester. Examples of such monomers include acrylic acid esters, methacrylic acid esters other than the above, acrylic acid, methacrylic acid, styrene, α-methylstyrene, butadiene, isoprene, vinyl chloride, vinyl acetate, acrylonitrile,
And at least one selected from methacrylonitrile
Seed monomers can be used. As the monomer constituting the soft segment, in terms of heat resistance, weather resistance, and flexibility of the resulting copolymer, it is preferable to use a monomer containing 80% by weight or more of an acrylic ester,
It is more preferable to use a monomer containing 90% by weight or more of an acrylic ester. The acrylic ester that constitutes the soft segment is not particularly limited, and the above acrylic ester can be used. However, in terms of availability, cost, and flexibility and cold resistance of the resulting polymer, n-butyl acrylate is used. preferable. Of the monomers constituting the soft segment, the monomers other than the acrylic acid ester are not particularly limited as long as they are monomers copolymerizable with the acrylic acid ester. Examples of such a monomer include acrylic acid esters, methacrylic acid esters other than the above,
At least one monomer selected from acrylic acid, methacrylic acid, styrene, α-methylstyrene, butadiene, isoprene, vinyl chloride, vinyl acetate, acrylonitrile, and methacrylonitrile can be used.

As described above, the method for producing the vinyl sulfide group-containing polymer is not particularly limited. A method of using a polymer as a constituent and having at least one thiocarbonylthio group in one molecule is preferable.

The method for synthesizing such a polymer having at least one thiocarbonylthio group in one molecule is not particularly limited, but as described above, the control of the molecular weight is easy and the molecular weight distribution Since a narrow polymer can be obtained and a thiocarbonylthio group can be surely introduced into the terminal, a method of RAFT-polymerizing the above monomer in the presence of a compound having a thiocarbonylthio group Is preferred. Examples of the compound having a thiocarbonylthio group include compounds selected from the group consisting of compounds represented by the following general formulas (2) and (3):

[0045]

[Chemical 12] (In the formula, R ¹ is a p-valent organic group having 1 or more carbon atoms, and the p-valent organic group includes a nitrogen atom, an oxygen atom, a sulfur atom, a halogen atom, a silicon atom, a phosphorus atom, and a metal atom. It may contain at least one of them, and may be a high molecular weight compound; Z ¹ is a hydrogen atom, a halogen atom, or a monovalent organic group having 1 or more carbon atoms, and the monovalent organic group is , A nitrogen atom, an oxygen atom, a sulfur atom, a halogen atom, a silicon atom, and a phosphorus atom, and may be a high molecular weight compound; p is 1
Is an integer of 2 or more, and when p is 2 or more, Z ¹ may be the same or different), and

[0046]

[Chemical 13] (In the formula, R ² is a monovalent organic group having 1 or more carbon atoms, and the monovalent organic group includes a nitrogen atom, an oxygen atom, a sulfur atom, a halogen atom, a silicon atom, a phosphorus atom, and a metal atom. It may contain at least one of them, and may be a high molecular weight compound; Z ² is a sulfur atom (when q = 2), an oxygen atom (when q = 2), a nitrogen atom (when q = 3). Case),
Or, it is a q-valent organic group having 1 or more carbon atoms, and the q-valent organic group may contain at least one of a nitrogen atom, an oxygen atom, a sulfur atom, a halogen atom, a silicon atom, and a phosphorus atom. Well, it may be a high molecular weight substance;
q is an integer of 2 or more; R ² may be the same or different).

R ¹ of the compound (2) having the thiocarbonylthio group is not particularly limited. In view of availability of the compound, preferably, R ¹ has 1 to 20 carbon atoms, and p is 6 or less. Examples of R ¹ are an alkyl group, a substituted alkyl group, an aralkyl group, a substituted aralkyl group, a divalent or higher valent aliphatic hydrocarbon group, a divalent or higher valent aromatic hydrocarbon group, and a divalent or higher valent fatty acid having an aromatic ring. Group hydrocarbon group, divalent or more aromatic hydrocarbon group having an aliphatic group, divalent or more aliphatic hydrocarbon group containing a hetero atom, divalent or more aromatic substituted hydrocarbon group containing a hetero atom, etc. is there.
The following groups are preferable in terms of availability of the compound and polymerization activity: benzyl group, 1-phenylethyl group, 2- (2-phenylpropyl) group, 1-acetoxyethyl group, 1-
(4-Methoxyphenyl) ethyl group, ethoxycarbonylmethyl group, 2- (2-ethoxycarbonylpropyl)
Group, 2- (2-cyanopropyl) group, t-butyl group,
1,1,3,3-tetramethylbutyl group, 2- (2-
(P-chlorophenyl) propyl) group, vinylbenzyl group, t-butylsulfide group, 2-carboxyethyl group, carboxymethyl group, cyanomethyl group, 1-cyanoethyl group, 2- (2-cyanobutyl) group, and Organic groups shown:

[0048]

[Chemical 14]

[0049]

[Chemical 15]

[0050]

[Chemical 16]

[0051]

[Chemical 17] (In the formula, R^FourRepresents a divalent organic group having 1 or more carbon atoms, and n
Is an integer of 1 or more, r is an integer of 0 or more, and r is
May be the same or different). N in the above formula and
And r are preferably 500 or less in terms of availability of the compound.
Is. R^FourThe carbon number of is preferably 1 to 20.
R^FourThe structure of, for example,-(CH₂) _n-(N is 1
Above integer), -C₆H_Four-, -CH₂-C₆H_Four-CH₂−
However, the present invention is not limited to these.

Further, R ¹ may be a high molecular weight compound as described above, and examples thereof include the following groups: a hydrocarbon group having a polyethylene oxide structure and a hydrocarbon having a polypropylene oxide structure. Group, a hydrocarbon group having a polytetramethylene oxide structure, a hydrocarbon group having a polyethylene terephthalate structure, a hydrocarbon group having a polybutylene terephthalate structure, a hydrocarbon group having a polydimethylsiloxane structure, a hydrocarbon group having a polycarbonate structure, A hydrocarbon group having a polyethylene structure, a hydrocarbon group having a polypropylene structure, a hydrocarbon group having a polyacrylonitrile structure, and the like. These hydrocarbon groups may contain at least one of oxygen atom, nitrogen atom, and sulfur atom, and may contain cyano group, alkoxy group and the like. Their molecular weight is usually 500 or more. Hereinafter, in the present invention, the high molecular weight group refers to the above group. Z ¹ of the compound (2) having a thiocarbonylthio group is not particularly limited. From the viewpoint of availability of the compound, when Z ¹ is an organic group, the carbon number thereof is preferably 1 to 20. Examples of Z ¹ are alkyl group, substituted alkyl group, alkoxy group, aryloxy group, aryl group, substituted aryl group, aralkyl group, substituted aralkyl group, heterocyclic group, N-aryl-N-alkylamino group, N , N-diarylamino group, N, N-dialkylamino group, thioalkyl group and dialkylphosphinyl group. The following groups are preferred from the viewpoint of availability of compounds and polymerization activity: phenyl group, methyl group, ethyl group, benzyl group, 4-chlorophenyl group, 1-naphthyl group, 2-naphthyl group, diethoxyphosphinyl group. , N-
Butyl group, t-butyl group, methoxy group, ethoxy group, thiomethyl group (methyl sulfide), phenoxy group, thiophenyl group (phenyl sulfide), N, N-dimethylamino group, N, N-diethylamino group, N-phenyl-
N-methylamino group, N-phenyl-N-ethylamino group, thiobenzyl group (benzyl sulfide), pentafluorophenoxy group, and the following formula

[0053]

[Chemical 18] An organic group represented by.

R ² of the compound (3) having a thiocarbonylthio group is not particularly limited. From the viewpoint of availability of the compound, R ² preferably has 1 to 20 carbon atoms. R ²
Examples of include an alkyl group, a substituted alkyl group, an aralkyl group, a substituted aralkyl group, and the like. The following groups are preferable in terms of availability of the compound and polymerization activity: a benzyl group,
1-phenylethyl group, 2- (2-phenylpropyl)
Group, 1-acetoxyethyl group, 1- (4-methoxyphenyl) ethyl group, ethoxycarbonylmethyl group, 2-
(2-Ethoxycarbonylpropyl) group, 2- (2-cyanopropyl) group, t-butyl group, 1,1,3,3-tetramethylbutyl group, 2- (2- (p-chlorophenyl) propyl) group , Vinylbenzyl group, t-butyl sulfide group, 2-carboxyethyl group, carboxymethyl group, cyanomethyl group, 1-cyanoethyl group, 2-
A (2-cyanobutyl) group and an organic group represented by the following formula:

[0055]

[Chemical 19] (In the formula, n is an integer of 1 or more, and r is an integer of 0 or more). In the above formula, n and r are preferably 500 or less in terms of availability of the compound.

Z ² of the compound (3) having a thiocarbonylthio group is not particularly limited. In view of availability of the compound, when Z ² is an organic group, its carbon number is preferably 1 to 20, and q is 6 or less. Examples of Z ² include a divalent or higher aliphatic hydrocarbon group, a divalent or higher aromatic hydrocarbon group, a divalent or higher aliphatic hydrocarbon group having an aromatic ring, or a divalent or higher aromatic having an aliphatic group. Examples thereof include a group hydrocarbon group, a divalent or higher valent aliphatic hydrocarbon group containing a hetero atom, and a divalent or higher valent aromatic substituted hydrocarbon group containing a hetero atom.
In terms of compound availability and polymerization activity, the following formula:

[0057]

[Chemical 20] (In the formula, n is an integer of 1 or more, and r is an integer of 0 or more). In the above formula, n and r are preferably 500 or less in terms of availability of the compound.

Among the above-mentioned compounds having a thiocarbonylthio group, it is preferable to use the compound represented by the following general formula (4) from the viewpoint that a telechelic polymer having thiocarbonylthio groups at both ends can be obtained. :

[0059]

[Chemical 21] (In the formula, R ³ is a divalent organic group having 1 or more carbon atoms, and the divalent organic group includes a nitrogen atom, an oxygen atom, a sulfur atom, a halogen atom, a silicon atom, a phosphorus atom, and a metal atom. It may contain at least one of them, and may be a high molecular weight compound; Z ¹ is a hydrogen atom, a halogen atom, or a monovalent organic group having 1 or more carbon atoms, and the monovalent organic group is , A nitrogen atom, an oxygen atom, a sulfur atom, a halogen atom, a silicon atom, and a phosphorus atom, and may be a high molecular weight compound; Z ¹ may be the same or different).

R ³ of the compound (4) having a thiocarbonylthio group is not particularly limited. From the viewpoint of availability of the compound, when R ³ is an organic group, the carbon number thereof is preferably 1 to 20. From the viewpoint of availability of the compound and polymerization activity, a group represented by the following formula is preferable:

[0061]

[Chemical formula 22]

[0062]

[Chemical formula 23] (In the formula, R ⁴ represents a divalent organic group having 1 or more carbon atoms, and n
Is an integer of 1 or more, and r is an integer of 0 or more. r may be the same or different). In the above formula, n and r are preferably 500 or less in terms of availability of the compound.

R ⁴ of the compound (4) having a thiocarbonylthio group is not particularly limited. The carbon number of R ⁴ is preferably 1 to 20. In terms of availability of the compound, the structure represented by the following formula is preferable:

[0064]

[Chemical formula 24] (In the formula, n is an integer of 1 or more, r is an integer of 0 or more, and r may be the same or different). In the above formula, n and r are preferably 500 or less in terms of availability of the compound.

Specific examples of the compound having a thiocarbonylthio group include, but are not limited to, the compounds represented by the following formulas:

[0066]

[Chemical 25]

[0067]

[Chemical formula 26]

[0068]

[Chemical 27]

[0069]

[Chemical 28]

[0070]

[Chemical 29]

[0071]

[Chemical 30]

[0072]

[Chemical 31] (In the formula, Me is a methyl group, Et is an ethyl group, Ph is a phenyl group, Ac is an acetyl group; R ⁴ is a divalent organic group having 1 or more carbon atoms; and n is an integer of 1 or more. , R are integers of 0 or more, and r may be the same or different. In the above formula, n and r are preferably 500 or less in terms of availability of the compound. The carbon number of R ⁴ is preferably 1 to 20. The structure of R ^4, for _{example, - (CH 2) n -} (n is an integer of 1 or more), - C ₆ H
₄ -, and _{-CH 2 -C 6 H 4 -CH 2} - and the like can be mentioned, but not limited to.

The amount of the above-mentioned compound having a thiocarbonylthio group is not particularly limited and can be calculated from the stoichiometry of the monomer and the polymerization initiator used. In general, the number of moles of the obtained polymer is almost equal to the number of moles of the compound having a thiocarbonylthio group. It is possible to control the molecular weight of the coalescence. When the molecular weight of the monomer used is Mm, the amount of the monomer used is x mole, the molecular weight of the compound having a thiocarbonylthio group is Mr, and the amount of the compound having a thiocarbonylthio group is y mole, a single amount 100 body reaction rate
%, The theoretical molecular weight of the resulting polymer is (x / y)
It is shown by × Mm + Mr. Therefore, the amount of the compound having a thiocarbonylthio group used may be calculated from the number average molecular weight of the target polymer and used. When the reaction rate of the monomer is less than 100%, the value may be calculated by multiplying the number of moles of the monomer used by the desired reaction rate.

In the present invention, the form of radical polymerization of the above monomers in the presence of a compound having a thiocarbonylthio group is not particularly limited. It is possible to apply commonly used methods such as bulk polymerization, solution polymerization, emulsion polymerization, suspension polymerization and fine suspension polymerization. A compound having a thiocarbonyl group may be present in these polymerization reaction systems. Of these, in terms of cost and safety,
Aqueous polymerization such as emulsion polymerization, suspension polymerization and fine suspension polymerization is preferable. Further, when the conversion reaction to the mercapto group is continuously performed after the polymerization, the solution polymerization is preferable in terms of high productivity. The monomers to be polymerized may be charged all at once in the reactor for reaction, or may be added sequentially.

Solvents used in solution polymerizing the above monomers include, but are not limited to, the following solvents: heptane, hexane, octane, cyclohexane, methylcyclohexane, hydrocarbons such as mineral spirits. System solvent; ethyl acetate, n-butyl acetate,
Ester-based solvents such as isobutyl acetate, ethylene glycol monomethyl ether acetate, diethylene glycol monobutyl ether acetate; ketone-based solvents such as acetone, methyl ethyl ketone, methyl isobutyl ketone, diisobutyl ketone, cyclohexanone; methanol, ethanol, isopropanol, n-butanol, sec-butanol , Alcohol solvents such as isobutanol, ethylene glycol, propylene glycol; ether solvents such as tetrahydrofuran, diethyl ether, dibutyl ether, dioxane, ethylene glycol dimethyl ether, ethylene glycol diethyl ether; dimethylformamide, diethylformamide, dimethylacetamide, diethylacetamide Amide solvents such as Toluene, xylene, benzene,
Swazol 310 (manufactured by Cosmo Oil Co., Ltd.), Swazol 1000 (manufactured by Cosmo Oil Co., Ltd.), Swazol 1500
Aromatic petroleum solvents such as (manufactured by Cosmo Oil Co., Ltd.).
These may be used alone or in combination of two or more. Regarding the type and amount of the solvent used, the solubility of the monomer, the solubility of the obtained polymer, the concentration of the polymerization initiator and the concentration of the monomer suitable for achieving a sufficient reaction rate, and a thiocarbonylthio group are included. It may be determined in consideration of solubility of the compound, influence on human body and environment, availability, price, etc., and is not particularly limited. In terms of solubility, availability, and price, industrially, ethyl acetate, toluene, dimethylformamide, tetrahydrofuran, and acetone are preferable, and dimethylformamide and toluene are more preferable.

When emulsifying or finely suspension polymerizing the above monomers, the emulsifiers used include, but are not limited to, the following emulsifiers: fatty acid soaps,
Rosin acid soap, sodium naphthalenesulfonate formalin condensate, sodium alkylsulfonate (for example, sodium dodecylsulfonate), sodium alkylbenzenesulfonate, sodium alkylsulfate (for example, sodium dodecylsulfate), ammonium alkylsulfate, triethanolamine alkylsulfate, Anionic surfactants such as sodium dialkyl sulfosuccinate, sodium alkyl diphenyl ether disulphonate, sodium polyoxyethylene alkyl ether sulfate, sodium polyoxyethylene alkylphenyl ether sulfate; polyoxyethylene alkyl ether,
Nonionic interface such as polyoxyethylene higher alcohol ether, sorbitan fatty acid ester, polyoxyethylene sorbitan fatty acid ester, polyoxyethylene sorbitol fatty acid ester, glycerin fatty acid ester, polyoxyethylene fatty acid ester, polyoxyethylene alkylamine, alkylalkanolamide Activators; cationic surfactants such as alkyl trimethyl ammonium chloride. These emulsifiers may be used alone or in combination of two or more. If necessary, a cationic surfactant such as alkylamine hydrochloride may be used, and a dispersant for suspension polymerization described below may be added. The amount of emulsifier used is not particularly limited,
From the viewpoint that the emulsified state is good and the polymerization proceeds smoothly, 0.1 to 20 parts by weight is preferable with respect to 100 parts by weight of the monomer.

When the above monomers are subjected to suspension polymerization, as the dispersant to be used, it is possible to use any of the commonly used dispersants. Examples include, but are not limited to, the following dispersants: partially saponified polyvinyl acetate, polyvinyl alcohol, methyl cellulose,
Carboxymethyl cellulose, gelatin, polyalkylene oxide, a combination of anionic surfactant and dispersion aid, etc. These may be used alone or in combination of two or more. You may use together the said emulsifier of emulsion polymerization as needed. Although the amount of the dispersant used is not particularly limited, it is preferably 0.1 to 20 parts by weight with respect to 100 parts by weight of the monomer, because polymerization proceeds smoothly.

The polymerization initiator used in the radical polymerization or the polymerization initiation method is not particularly limited, and a commonly used polymerization initiator or a polymerization initiation method can be used. For example, polymerization initiators include, but are not limited to, the following compounds: methyl ethyl ketone peroxide, methyl isobutyl ketone peroxide, cyclohexanone peroxide, methyl cyclohexanone peroxide, isobutyryl peroxide, 3,5,5-trimethyl. Hexanoyl peroxide, lauroyl peroxide, benzoyl peroxide, t-butyl hydroperoxide, cumene hydroperoxide, diisopropylbenzene hydroperoxide, p-menthane hydroperoxide, 1,1,3,3-tetramethylbutylhydro Peroxide, di-t-butyl peroxide, t-butyl-α-cumyl peroxide, di-α-cumyl peroxide, 1,4-bis [(t-butylperoxide) Xy) isopropyl] benzene, 1,3-bis [(t-butylperoxy) isopropyl] benzene, 2,5-dimethyl-
2,5-bis (t-butylperoxy) hexane, 2,
5-dimethyl-2,5-bis (t-butylperoxy)
-3-hexyne, 1,1-bis (t-butylperoxy) -3,3,5-trimethylcyclohexane, n-butyl-4,4-bis (t-butylperoxy) valerate, 2,2-bis (T-butylperoxy) butane, t
-Butyl peroxyacetate, t-butyl peroxyisobutyrate, t-butyl peroxy octoate,
t-butyl peroxypivalate, t-butyl peroxy neodecanoate, t-butyl peroxy-3,5
5-trimethylhexanoate, t-butylperoxybenzoate, t-butylperoxylaurate, 2,
5-dimethyl-2,5-bis (benzoylperoxy)
Hexane, bis (2-ethylhexyl) peroxydicarbonate, diisopropyl peroxydicarbonate, di-sec-butyl peroxydicarbonate, di-n-propyl peroxydicarbonate, bis (3-
Methoxybutyl) peroxydicarbonate, bis (2
-Ethoxyethyl) peroxydicarbonate, bis (4-t-butylcyclohexyl) peroxydicarbonate, Ot-butyl-O-isopropylperoxycarbonate, peroxide polymerization initiators such as succinic acid peroxide; 2,2'-azobis- (2-amidinopropane) dihydrochloride, dimethyl 2,2'-azobisisobutyrate, 2,2'-azobis- (4-methoxy-2,4-dimethylvaleronitrile), 2,2 '-Azobis (isobutyronitrile), 1,1'-azobis (cyclohexane-1-carbonitrile), azocumene, 2,2'-azobis (2-methylbutyronitrile), 2,2'-azobis- ( 2,4-dimethylvaleronitrile), 4,4'-
Azobis (4-cyanovaleric acid), 2- (t-butylazo) -2-cyanopropane, 2,2'-azobis (2,2
Azo polymerization initiators such as 4,4-trimethylpentane) and 2,2′-azobis (2-methylpropane); inorganic peroxides such as potassium persulfate and sodium persulfate; Vinyl-based monomers that generate radical species; compounds that generate radical species by light, such as benzoin derivatives, benzophenone, acylphosphine oxide, and photoredox systems; sodium sulfite, sodium thiosulfate, sodium formaldehyde sulfoxylate. , Redox type polymerization initiators using ascorbic acid, ferrous sulfate, etc. as reducing agents and potassium peroxodisulfate, hydrogen peroxide, t-butyl hydroperoxide, etc. as oxidizing agents. These polymerization initiators may be used alone or in combination of two or more. Besides, it is also possible to utilize a polymerization initiation system by electron beam irradiation, X-ray irradiation, radiation irradiation, or the like. Regarding such a polymerization initiation method, Moad and So
lomon "The Chemistry of Fr
eeRadical Polymerizatio
n ", Pergamon, London, 1995, 5
The method described on page 3-95 can be used.

The amount of the polymerization initiator used in the practice of the present invention is not particularly limited, but in that a polymer having a narrow molecular weight distribution can be obtained, the amount of radical species generated during the polymerization is thiocarbonylthio group. 1 mol or less is preferable and 0.5 mol or less is more preferable with respect to 1 mol of the thiocarbonylthio group of the compound having. In addition, in order to control the amount of radical species generated during the polymerization, in combination with the amount of the polymerization initiator used, in the case of a thermal initiator that dissociates thermally, adjust the temperature, by using light or electron beams. In the case of a polymerization initiation system that generates radicals, it is preferable to adjust the amount of irradiation energy. From the viewpoint of easy control of polymerization, a polymerization initiator that thermally dissociates is used, and its half-life is 0.5 to 5
Polymerization is preferably carried out at a temperature of 0 hour, more preferably at a half-life of 1 to 20 hours, more preferably at a half-life of 5 to 15 hours. Is particularly preferable.

The method of introducing a vinyl sulfide group into the polymer is not particularly limited, but a method of utilizing a polymer molecule having a mercapto group is preferable because it can be introduced simply and surely. As a method of synthesizing a polymer having at least one mercapto group in one molecule, a monomer is polymerized in the presence of a compound having a thiocarbonylthio group to obtain a polymer having a thiocarbonylthio group, Method of converting thiocarbonylthio group of the polymer into mercapto group; Method of polymerizing monomer containing mercapto group as monomer component; Polymerization of monomer using polymerization initiator having mercapto group Method: a method of polymerizing a monomer using a polymerization initiator having a disulfide bond and reducing the polymer, and the like. Of these, as mentioned above,
A method via a polymer having a thiocarbonylthio group is simple, reliable and preferable. In other methods, surely introducing a mercapto group at the end of the polymer molecular chain, controlling the number average molecular weight of the polymer, to obtain a polymer with a narrow molecular weight distribution, and a mercapto group at both ends. It is difficult to obtain the telechelic polymer having.

Among the above methods, the method of passing through a polymer having a thiocarbonylthio group will be described below.

By treating the polymer having at least one thiocarbonylthio group in one molecule with a treating agent, the thiocarbonylthio group of the polymer is converted into a mercapto group. The treating agent used here is not particularly limited, but it is preferable to employ a compound selected from a base, an acid, and a hydrogen-nitrogen bond-containing compound in terms of high reaction efficiency.

Of the above treating agents, the base is not particularly limited, but the following compounds may be mentioned: Alkali metal hydroxides such as sodium hydroxide, potassium hydroxide, lithium hydroxide; calcium hydroxide, hydroxide. Alkaline earth metal hydroxides such as magnesium, barium hydroxide and cesium hydroxide; transition metal hydroxides such as aluminum hydroxide and zinc hydroxide; sodium methylate, sodium ethylate, sodium phenylate, lithium ethylate, Alkali metal alcoholates such as lithium butyrate; Alkaline earth metal alcoholates such as magnesium methylate and magnesium ethylate; Metal hydrides such as sodium hydride, lithium hydride, calcium hydride, lithium aluminum hydride, sodium borohydride Carbonic acid Salts of strong bases and weak acids such as lithium, potassium carbonate, sodium acetate, potassium acetate; organometallic reagents such as hydrosulfite, n-butyllithium, t-butyllithium, ethylmagnesium bromide, phenylmagnesium bromide; triethylamine, tri-n -A tertiary amine compound such as butylamine. Further, alkali metals such as metallic lithium, metallic sodium and metallic potassium; alkaline earth metals such as metallic magnesium and metallic calcium can also be used. These may be used alone or in combination of two or more.

Of the above treating agents, the acid is not particularly limited, but the following compounds may be mentioned: hydrochloric acid, nitric acid, sulfuric acid, phosphoric acid, hydrofluoric acid, hydrobromic acid, borofluoric acid, chloro. Inorganic acids such as sulfonic acid, hydroiodic acid, arsenic acid, hydrosilicofluoric acid; p-toluenesulfonic acid, trifluoromethylsulfonic acid, acetic acid, trifluoroacetic acid, methylphosphoric acid, ethylphosphoric acid, n-propylphosphoric acid, Organic acids such as isopropyl phosphoric acid, n-butyl phosphoric acid, lauryl phosphoric acid, stearyl phosphoric acid, 2-ethylhexyl phosphoric acid, isodecyl phosphoric acid, dimethyldithiophosphoric acid, diethyldithiophosphoric acid, diisopropyldithiophosphoric acid, phenylphosphonic acid; strong acid ion exchange Resin, weakly acidic ion exchange resin, etc. Furthermore, a compound which reacts with a small amount of water and exhibits acidity can also be used. Examples of such a compound include acid anhydrides such as acetic anhydride, propionic anhydride, trifluoroacetic anhydride, phthalic anhydride, and succinic anhydride; acyl halides such as acetic acid chloride and benzoic acid chloride; titanium tetrachloride, aluminum chloride. , Metal halides such as silicon chloride and thionyl chloride. These may be used alone or in combination of two or more.

Of the above treating agents, the hydrogen-nitrogen bond-containing compound is not particularly limited, but for example, ammonia,
Examples thereof include hydrazine, primary amine compounds, secondary amine compounds, amide compounds, amine hydrochloride compounds, hydrogen-nitrogen bond-containing polymers, and hindered amine light stabilizers (HALS).

Of the above-mentioned hydrogen-nitrogen bond-containing compounds, 1
Specific examples of the primary amine compound include N- (2-aminoethyl) ethanolamine, 12-aminododecanoic acid,
3-amino-1-propanol, allylamine, isopropylamine, 3,3′-iminobis (propylamine), monoethylamine, 2-ethylhexylamine,
3- (2-ethylhexyloxy) propylamine, 3
-Ethoxypropylamine, 3- (diethylamino) propylamine, 3- (dibutylamino) propylamine, n-butylamine, t-butylamine, sec-butylamine, n-propylamine, 3- (methylamino) propylamine, 3- (Dimethylamino) propylamine, N-methyl-3,3'-iminobis (propylamine), 3-methoxypropylamine, 2-aminoethanol, ethylenediamine, diethylenetriamine,
Triethylenetetramine, tetraethylenepentamine,
Pentaethylenehexamine, N-carboxy-4,4 '
-Methylenebiscyclohexylamine, 1,4-diaminobutane, 1,2-diaminopropane, 1,3-diaminopropane, diaminomaleonitrile, cyclohexylamine, ATU (manufactured by Ajinomoto Co., Inc.), CTU guanamine (Ajinomoto Co., Inc.) Manufactured), thiourea dioxide, 2-hydroxyethylaminopropylamine, hexamethylenediamine, n-hexylamine, monomethylamine, monomethylhydrazine, 3- (lauryloxy) propylamine, anisidine, aniline, p-aminoacetanilide, p- Aminobenzoic acid, p-aminobenzoic acid ethyl ester, 2-amino-4-chlorophenol, 2-aminothiazole, 2-aminothiophenol, 2-amino-5-nitrobenzonitrile, aminophenol, p-
Aminobenzaldehyde, 4-aminobenzonitrile,
Anthranilic acid, 3-isopropoxyaniline, 4-amino-5-hydroxy-2,7-naphthalenesulfonic acid monosodium salt, 6-amino-4-hydroxy-2-
Naphthalenesulfonic acid, xylidine, m-xylylenediamine, p-cresidine, dianisidine, 4,4'-diaminostilbene-2,2'-disulfonic acid, 2-amino-5-naphthol-7-sulfonic acid, 1,4 -Diaminoanthraquinone, 4,4'-diamino-3,3'-diethyldiphenylmethane, 4,4'-diaminobenzanilide, diaminodiphenyl ether, 3,3'-dimethyl-4,4'-diaminodiphenylmethane, stefanilic acid, Tobiasic acid, 2,4,5-trichloroaniline, o-tolidine, toluidine, toluylenediamine,
Sodium naphthionate, nitroaniline, m-nitro-p-toluidine, o-chloro-p-toluidine-m-
Sulfonic acid, phenylhydrazine, phenylenediamine, phenetidine, phenethylamine, benzylamine, benzophenonehydrazone, mesidine, methanilic acid, 2-methyl-4-nitroaniline, leuco-1,4
-Diaminoanthraquinone, paramine, aminopyridine, 1- (2-aminoethyl) piperazine, N- (3-
Aminopropyl) morpholine, 1-amino-4-methylpiperazine, bis (aminopropyl) piperazine, benzoguanamine, melamine, o-chloroaniline, 2,5
-Dichloroaniline, 3,4-dichloroaniline, 3,
5-dichloroaniline, 2-amino-4-chlorobenzoic acid, o-chloro-p-nitroaniline, 5-chloro-2
-Nitroaniline, 2,6-dichloro-4-nitroaniline, 2- (2-chlorophenyl) ethylamine, 3,
3'-dichloro-4,4'diaminodiphenylmethane,
3,3'-dichloro-4,4'-diaminobiphenyl,
2,4-difluoroaniline, o-fluoroaniline,
Examples thereof include N-β- (aminoethyl) -γ-aminopropyltrimethoxysilane, N-β- (aminoethyl) -γ-aminopropylmethyldimethoxysilane, and γ-aminopropyltriethoxysilane. It is not limited to these.

Of the above-mentioned hydrogen-nitrogen bond-containing compounds, 2
Specific examples of the primary amine compound include N-methylethanolamine, diallylamine, diisopropylamine,
Diethylamine, diisobutylamine, di-2-ethylhexylamine, iminodiacetic acid, 3,3'-iminodipropionitrile, bis (hydroxyethyl) amine, N
-Ethylethylenediamine, ethyleneimine, dicyclohexylamine, 1,1-dimethylhydrazine, di-n
-Butylamine, di-t-butylamine, dimethylamine, sodium N-methylacetate, N-ethylaniline,
Diphenylamine, dibenzylamine, 7-anilino-
4-hydroxy-2-naphthalenesulfonic acid, N-methylaniline, 2-methyl-4-methoxydiphenylamine, imidazole, 2-methylimidazole, 2-ethyl-4-methylimidazole, 2-phenylimidazole, 2-undecylimidazole , 1,3-di (4-piperidyl) propane, 2,5-dimethylpiperazine,
2,6-dimethylpiperazine, 3,5-dimethylpyrazole, 5,5'-bi-1H-tetrazole, 5-phenyl-1H-tetrazole, 5-methyl-1H-tetrazole, 1,2,3,4-tetrahydro Examples include, but are not limited to, quinoline, (hydroxyethyl) piperazine, pipecoline, 2- (1-piperazinyl) pyrimidine, piperazine, piperidine, pyrrolidine, N-methylpiperazine, 2-methylpiperazine, morpholine, and the like.

Of the above hydrogen-nitrogen bond-containing compounds, specific examples of the amide compounds include 2-acrylamido-
2-methylpropanesulfonic acid, adipic acid dihydrazide, N-isopropylacrylamide, Nt-octylacrylamide, carbohydrazide, guanylthiourea, glycylglycine, N- [3- (dimethylamino)
Propyl] acrylamide, N- [3- (dimethylamino) propyl] methacrylamide, N, N'-ethylenebis (stearoamide), oleic acid amide, stearic acid amide, N, N'-methylenebis (stearoamide), N- ( (Hydroxymethyl) stearamide, diacetone acrylamide, thioacetamide, thiocarbohydrazide, thiosemicarbazide, thiourea, dodecanedioic acid dihydrazide, adipic acid dihydrazide, sebacic acid dihydrazide, isophthalic acid dihydrazide, 1,6
-Hexamethylenebis (N, N-dimethylsemicarbazide), formamide, methacrylamide, N, N'-methylenebis (acrylamide), N-methylolacrylamide, acetanilide, acetoacetic acid o-anisidide, acetoacetic acid anilide, acetoacetic acid m-xylidide , Acetoacetic acid o-chloroanilide, acetoacetic acid 2,5
-Dimethoxy-4-chloroanilide, acetoacetic acid toluidide, 1,1,1 ', 1'-tetramethyl-4,4'
-(Methylenedi-p-phenylene) disemicarbazide,
Toluenesulfonamide, p-hydroxyphenylacetamide, phthalimide, isocyanuric acid, 3-carbamoyl-2-pyrazinecarboxylic acid, succinimide,
5,5-dimethylhydantoin, 1,3-bis (hydrazinocarboethyl) -5-isopropylhydantoin,
Hydantoin, phenylpyrazolidone, 3-methyl-5
-Pyrazolone, 1-methylol-5,5-dimethylhydantoin, 3- (4-chlorophenyl) -1,1-dimethylurea, bromvalerylurea, 2,6-difluorobenzamide, and 2,2,2-trifluoroacetamide However, the present invention is not limited to these.

Of the above hydrogen-nitrogen bond-containing compounds, specific examples of amine hydrochloride compounds include acetamidine hydrochloride, 2,2'-azobis- (2-amidinopropane) dihydrochloride and monomethylamine hydrochloride. , Dimethylamine hydrochloride, monoethylamine hydrochloride, diethylamine hydrochloride, monopropylamine hydrochloride, dipropylamine hydrochloride, monobutylamine hydrochloride, dibutylamine hydrochloride, semicarbazide hydrochloride, guanidine hydrochloride, aminoguanidine hydrochloride, 2-chloro Examples thereof include, but are not limited to, ethylamine hydrochloride, disteamine hydrochloride, and t-butylhydrazine monohydrochloride.

Of the above hydrogen-nitrogen bond-containing compounds, specific examples of the hydrogen-nitrogen bond-containing polymer include polyment (manufactured by Nippon Shokubai Co., Ltd.), polyethyleneimine, aminopolyacrylamide, nylon 6, nylon 66, nylon. 610, nylon 612, nylon 11, nylon 1
2, nylon MXD6, nylon 46, polyamideimide, polyallylamine, polyurethane, and the like, but are not limited thereto.

Of the above hydrogen-nitrogen bond-containing compounds, H
As ALS, ADEKA STAB LA-77 (manufactured by Asahi Denka Co., Ltd.), Chimassorb 944LD (manufactured by Ciba Specialty Chemicals), Tinuvin
144 (manufactured by Ciba Specialty Chemicals),
ADEKA STAB LA-57 (manufactured by Asahi Denka Kogyo KK), ADEKA STAB LA-67 (manufactured by Asahi Denka Kogyo KK), ADEKA STAB LA-68 (manufactured by Asahi Denka Kogyo KK), ADEKA STAB LA-87 (Asahi Denka Kogyo) Co., Ltd.) and Goodr
ite UV-3034 (manufactured by Goodrich) and the like, but not limited thereto.

Of these compounds, a compound selected from a base and a compound containing a hydrogen-nitrogen bond is preferable in terms of high reaction efficiency. In the case of reacting a polymer having at least one mercapto group in one molecule obtained by the above reaction with acetylene, it is not necessary to add a new catalyst, and the reaction can be carried out continuously. The method of doing is more preferable.

In the above conversion reaction from the thiocarbonylthio group to the mercapto group, the amount of the treating agent used is not particularly limited. When using a base or acid as the treatment agent,
The amount used is not particularly limited, but from the viewpoint of ease of handling and reactivity, the polymer 10 having a thiocarbonylthio group is used.
0.01 to 100 parts by weight is preferable with respect to 0 parts by weight,
0.05 to 50 parts by weight is more preferable, and 0.1 to 30 parts by weight is particularly preferable. When a hydrogen-nitrogen bond-containing compound is used in the above conversion reaction, the hydrogen-nitrogen bond-containing compound is added in an amount of 0.5 to 1 mol with respect to 1 mol of the thiocarbonylthio group of the above-mentioned polymer in that the introduction rate of the mercapto group is high. It is preferably used in a proportion of 1000 mol, more preferably 1 to 500 mol.

The method for obtaining the vinyl sulfide group-containing polymer of the present invention is not particularly limited, but as described above, the method of reacting the mercapto group-containing polymer with acetylene is preferable. The reaction between a mercapto group and acetylene is generally called a Reppe reaction, and the reaction conditions are not particularly limited, and the conditions and reagents usually used in the art can be applied.

When reacting a polymer having at least one mercapto group in one molecule with acetylene, it is preferable to use a base as a catalyst because the reaction proceeds efficiently. The base is not particularly limited, and the above-mentioned base can be used as the treating agent. These may be used alone or in combination of two or more. Of these, from the viewpoints of price, availability, handleability, and reactivity, alkali metal hydroxides such as sodium hydroxide, potassium hydroxide and lithium hydroxide; alkali metal such as sodium metal and lithium; hydrogen; Alkali metal hydrides such as sodium hydride and lithium hydride are preferred.

When carrying out the reaction with the above treating agent, an organic solvent can be used. As such an organic solvent, a hydroxyl group, a mercapto group, a carboxyl group,
Those which do not have a functional group such as a carbonyl group which reacts with acetylene under Reppe reaction conditions are preferable. Organic solvents include, but are not limited to, the following organic solvents: n-pentane, n-hexane, 2-
Aliphatic hydrocarbon solvents such as ethylhexane, n-octane, cyclohexane, methylcyclohexane; aromatic hydrocarbon solvents such as benzene, toluene, xylene, mesitylene; 1,2-dimethoxyethane, propylene glycol dimethyl ether, diethyl ether, diphenyl ether, Ether solvents such as anisole, 1,4-dioxane and tetrahydrofuran. Of these, toluene, xylene, and n in terms of price and availability
-Hexane is preferred.

The amount of acetylene used is not particularly limited, but from the viewpoint that a vinyl sulfide group can be reliably formed, it is preferably 0.5 mol or more, more preferably 1 mol or more, relative to 1 mol of the mercapto group in the polymer. . Further, in terms of production cost, 1 is used for 1 mol of the mercapto group in the polymer.
The amount is preferably 0000 mol or less, more preferably 5000 mol or less. Excess acetylene can be recovered and reused.

The vinyl sulfide group-containing polymer of the present invention thus obtained has a polymer block derived from the above-mentioned specific monomer, and further has the formula (1)

[0099]

[Chemical 32] At least one vinyl sulfide group represented by is included in one molecule.

The vinyl sulfide group-containing polymer of the present invention can be cured by a crosslinking reaction utilizing a vinyl sulfide group. From the viewpoint of the strength of the obtained cured product, the polymer is preferably a polymer having vinyl sulfide groups at the ends of the molecule, and a linear polymer having the vinyl sulfide groups at both ends of the molecule. Is more preferable. Generally, a linear polymer having such functional groups at both ends is called a telechelic polymer.

The polymer of the present invention has an excellent balance between strength after curing by cross-linking and processability, and has a number average molecular weight (Mn) of 1,000 to 100,000 as determined by gel permeation chromatography (GPC) analysis. It is preferably in the range, more preferably in the range of 2000 to 80,000, and particularly preferably in the range of 3000 to 50,000.

The polymer of the present invention is excellent in strength, durability and processability after curing due to the above-mentioned crosslinking, and therefore, the weight average molecular weight (Mw) and number average molecular weight determined by gel permeation chromatography (GPC) analysis. The molecular weight distribution (Mw / Mn) represented by the ratio with (Mn) is preferably 1.8 or less, and more preferably 1.5 or less.

In the present invention, gel permeation chromatography (GPC) analysis is carried out using chloroform, tetrahydrofuran, or dimethylformamide as an eluent, a polystyrene gel column, and a polystyrene standard sample as a reference.

The vinyl sulfide group-containing polymer of the present invention can be widely used as a raw material for various molded products, a raw material for adhesives and adhesives, a polymerizable macromonomer, a thermoplastic elastomer, a resin modifier and the like. When used as a thermoplastic elastomer, the polymer is a block copolymer having a hard segment and a soft segment in one molecule, as described above. The block copolymer having a hard segment and a soft segment in one molecule is, for example, a polymer block containing a monomer containing 50% by weight or more of a methacrylic acid ester as a constituent as a vinyl sulfide group-containing polymer ( A block copolymer having a hard segment) and a polymer block (soft segment) containing a monomer containing acrylic acid ester in an amount of 50% by weight or more as a constituent component.

The vinyl sulfide group-containing polymer (a) of the present invention can be used as a curable composition by combining the compound (b) having a hydrogen-silicon bond and the hydrosilylation catalyst (c). .

The compound (b) having a hydrogen-silicon bond (hereinafter referred to as H-Si compound) is not particularly limited, and examples thereof include compounds represented by the general formulas (5), (6), and (7). Can be:

[0107]

[Chemical 33] (In the formula, R ⁵ represents a halogen atom, a hydroxyl group, a mercapto group, a monovalent organic group having 1 or more carbon atoms, or a siloxy group, which may be the same or different; r is 0 or more. And may be the same or different from each other; m is an integer of 0 or more, and a and b
Are each independently 0, 1, 2, or 3, and 1 ≦
(Satisfying a + b + m)),

[0108]

[Chemical 34] (In the formula, R ⁵ represents a halogen atom, a hydroxyl group, a mercapto group, a monovalent organic group having 1 or more carbon atoms, or a siloxy group, which may be the same or different; n is 1 or more. Is an integer of 0, c is an integer of 0 or more, and 3 ≦ (c + n) is satisfied, and

[0109]

[Chemical 35] (In the formula, R ⁵ represents a halogen atom, a hydroxyl group, a mercapto group, a monovalent organic group having 1 or more carbon atoms, or a siloxy group, which may be the same or different; R ⁶ is A divalent organic group having 1 or more carbon atoms, a divalent siloxy group, or an oxygen atom; d, e, f, and g
Is an integer of 0 or more, and 1 ≦ (d + g), 2 ≦ (d +
e) 2 ≦ (f + g) is satisfied). In the above formula, r and m are preferably 100 or less in view of availability of the compound, and n, c, d, e, f, and g are preferably 20 or less in view of availability of the compound. is there. From the viewpoint of availability of the compound, the carbon number of R ⁵ and R ⁶ is preferably 1 to 20.
Is.

Examples of R ^{5 in the} above H—Si compound include, but are not limited to, the following groups:
Alkyl groups such as methyl group, ethyl group, n-propyl group, isopropyl group, n-butyl group, t-butyl group; 2
-Methoxyethyl group, 2-methoxypropyl group, 2-ethoxymethyl group, 2,2,2-trifluoroethyl group,
Substituted alkyl groups such as benzyl group, 2-phenylethyl group, 2- (4-methoxyphenyl) ethyl group; aryl groups such as phenyl group, 1-naphthyl group, 2-naphthyl group; 4-methylphenyl group, 4- Methoxyphenyl group,
Substituted aryl groups such as 3,5-dimethylphenyl group and pentafluorophenyl group; methoxy group, ethoxy group, 2
-Methoxyethoxy group, phenyloxy group, 4-methylphenyloxy group, and other alkoxy groups; chlorine atom, fluorine atom, and other halogen atoms; hydroxyl group; mercapto group; acetoxy group, benzoyloxy group, and other acyloxy groups; dimethyl ketoxy Ketoximate groups such as mate group, diethyl ketoximate group, diphenyl ketoximate group, methyl isobutyl ketoximate group; trimethylsilyl group, triethylsilyl group, dimethylphenylsilyl group, dimethoxymethylsilyl group, diethoxymethylsilyl group, triethoxymethylsilyl group Silyl groups such as methoxysilyl group, triethoxysilyl group, dichloromethylsilyl group, chlorodimethylsilyl group; trimethylsiloxy group, triethylsiloxy group, dimethylphenylsiloxy group, trimethoxysiloxy group, Methoxymethyl siloxy group, triethoxysiloxy group, diethoxymethyl siloxy group, a siloxy group such as trimethylsiloxy dimethylsiloxy group. Of these, the following groups are preferable in terms of availability and stability: methyl group, ethyl group, phenyl group, 2,
2,2-trifluoroethyl group, methoxy group, ethoxy group, dimethoxymethylsiloxy group, trimethoxymethylsiloxy group, diethoxymethylsiloxy group, triethoxysiloxy group, acetoxy group, and benzoyloxy group. More preferred are a methyl group, an ethyl group, a phenyl group, a methoxy group, an acetoxy group, and a benzoyloxy group, and a methyl group, an ethyl group, a phenyl group, and a methoxy group are particularly preferred.

Examples of R ^{6 in the} above H—Si compound include, but are not limited to, the structures represented by the following formulas:

[0112]

[Chemical 36] (In the formula, R ⁵ represents a halogen atom, a hydroxyl group, a mercapto group, a monovalent organic group having 1 or more carbon atoms, or a siloxy group, which may be the same or different; n is 1 or more. , And r is an integer of 0 or more, and r may be the same or different).

Specific examples of the H-Si compound (b) include, but are not limited to, the following compounds: dimethoxymethylsilane, dimethoxyphenylsilane, diethoxymethylsilane, diethoxyphenylsilane, trimethoxy. Silane, triethoxysilane, methyldichlorosilane, phenyldichlorosilane, trimethylsilane, triethylsilane, dimethylphenylsilane,
Dimethylsilane, diethylsilane, diphenylsilane,
Methylphenylsilane, pentamethyldisiloxane, 1
-Phenyl-1,1,3,3-tetramethyldisiloxane, 1,3-dihydrotetramethyldisiloxane, heptamethyltrisiloxane, 1,5-dihydrohexamethyltrisiloxane, 1,3-dihydro-1,3 -Dimethyl-1,3-diphenyldisiloxane, 1,3,5-trihydro-1,1,5,5-tetramethyl-3-phenyltrisiloxane, 1,3,5-trihydropentamethyltrisiloxane, 1 , 3,5-Trihydrotrimethylcyclotrisiloxane, 1,3,5,7-tetrahydrotetramethylcyclotetrasiloxane, 1,3,5-trihydrotriphenylcyclotrisiloxane, 1,3
5,7-tetrahydrotetraphenylcyclotetrasiloxane, α, ω-dihydropolydimethylsiloxane,
α, ω-dihydropolydiethylsiloxane, α, ω-dihydropolydiphenylsiloxane, 1,5-dihydro-
3-vinylpentamethyltrisiloxane, methyl hydrogen silicone oil, 1,3-dihydrotetramethoxydisiloxane, 1,5-dihydrohexamethoxytrisiloxane, 1,5-dihydro-3-ethoxytetramethyltrisiloxane, 1,3 , 5,7-Tetrahydrotetramethoxycyclotetrasiloxane, 1,3,5-trihydrotriethoxycyclotrisiloxane, α, ω-dihydropolydimethoxysiloxane, dimethoxysilane, diethoxysilane, 1,3-dihydro-1, 3-dimethoxydimethyldisiloxane, 1,5-dihydro-3-methoxypentaphenyltrisiloxane, 1,4-bis (dimethylsilyl) benzene, 1,3,5-tris (dimethylsilyl) benzene, 1,4-bis (Dimethylsilyl) butane, and with the formula Compounds shown:

[0114]

[Chemical 37] (In the formula, Me represents a methyl group, h is an integer of 2 or more, i is an integer of 4 or more, and h may be the same as or different from each other). In the above formula, h is preferably 20 or less from the viewpoint of availability of the compound, and i in the above formula is preferably 500 or less from the viewpoint of availability of the compound. These may be used alone or in combination of two or more.

Of these, compounds having two or more hydrogen-silicon bonds in one molecule and compounds having a crosslinkable silyl group are preferable from the viewpoint of the strength of the cured product. In terms of availability, dimethoxymethylsilane, dimethoxyphenylsilane, diethoxymethylsilane, diethoxyphenylsilane, triethoxysilane, methyldichlorosilane, phenyldichlorosilane, α, ω-dihydropolydimethylsiloxane, methyl hydrogen silicone oil, 1, 3, 5
-Trihydrotrimethylcyclotrisiloxane and 1,3,5,7-tetrahydrotetramethylcyclotetrasiloxane are more preferred.

The curable composition of the present invention may contain a chain extender for controlling the physical properties of the resulting cured product. This chain extender is intended to crosslink the molecules of the H-Si compound (b) with each other to form a relatively large molecule. Therefore, the chain extender is preferably a compound having two or more alkenyl groups in one molecule. Such compounds having two or more alkenyl groups in one molecule include, but are not limited to, the following compounds: butadiene, isoprene, chloroprene, 1,4-pentadiene, 1,5-hexadiene, 1,6-heptadiene, 1,7-octadiene, 1,8-nonadiene, 1,9-decadiene, 1,
2-divinylbenzene, 1,4-divinylbenzene,
1,2-diallylbenzene, 1,4-diallylbenzene, 1,2-divinylcyclohexane, 1,4-divinylcyclohexane, 1,2-diallylcyclohexane,
1,4-diallylcyclohexane, 1,3,5-trivinylbenzene, 1,3,5-triallylbenzene, 1,
2,4,5-tetravinylbenzene, 1,2,4,5-
Tetraallylbenzene, hexavinylbenzene, hexaallylbenzene, 1,4-divinylnaphthalene, 1,5
-Divinylnaphthalene, 1,4-diallylnaphthalene,
1,5-diallylnaphthalene, 1,8-divinylnaphthalene, 1,8-diallylnaphthalene, 9,10-divinylanthracene, 9,10-diallylanthracene,
3,3'-diallyl bisphenol A, 4-vinyl-α
Hydrocarbon compounds such as methylstyrene; diallyl ether, divinyl ether, bisphenol A diallyl ether, 1,2-diallyloxybenzene, 1,4-
Diallyloxybenzene, trimethylolpropane diallyl ether, trimethylolpropane triallyl ether, pentaerythritol diallyl ether, pentaerythritol triallyl ether, pentaerythritol tetraallyl ether, ethylene glycol diallyl ether, propylene glycol diallyl ether,
Ether-based compounds such as diethylene glycol diallyl ether, dipropylene glycol diallyl ether, polyethylene glycol diallyl ether, polypropylene glycol diallyl ether, 1,6-hexanediol diallyl ether; diallyl terephthalate, diallyl phthalate, diallyl isophthalate, diallyl trimellitate. , Triallyl trimellitate, diallyl pyromellitic acid, triallyl pyromellitic acid, tetraallyl pyromellitic acid, diallyl succinate, diallyl oxalate,
Ester-based compounds such as allyl vinyl acetate, allyl vinyl propionate, allyl acrylate, allyl methacrylate, diallyl carbonate, diethylene glycol diallyl carbonate, diallyl dodecanedioate; triallyl isocyanurate, triallyl cyanurate, trimetallyl isocyanurate, etc. Cyanurate compounds, etc.

When a compound having a crosslinkable silyl group in one molecule is used as the H-Si compound (b), the condensation reaction utilizing the crosslinkable silyl group may be used in addition to the hydrosilylation reaction. It is also possible to cure the curable composition.

Here, the crosslinkable silyl group means, as a substituent on a silicon atom, a hydroxyl group, 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, Examples thereof include a mercapto group and an alkenyloxy group. Of these substituents, an alkoxy group, an acyloxy group, and a ketoximate group are preferable, and an alkoxy group is most preferable, because they have high stability and do not interfere with the hydrosilyl reactability.

When curing by a condensation reaction utilizing a crosslinkable silyl group, a condensation catalyst can be used if necessary. As such a condensation catalyst, a condensation catalyst usually used in this field is used. Such condensation catalysts include, but are not limited to, the following compounds: titanic acid esters such as tetrabutyl titanate, tetrapropyl titanate; dibutyltin dilaurate, dibutyltin maleate, dibutyltin diacetate, tin octylate, naphthenes. Tin acid, tin stearate, dibutyltin dioctoate, dibutyltin dioleyl maleate, dibutyltin dibutyl maleate, 1,
1,3,3-Tetrabutyl-1,3-dilauryloxycarbonyl-distannoxane, dibutyltin diacetylacetonate, dibutyltin bis (o-phenylphenoxide), dibutyltin oxide, dibutyltin bistriethoxysilicate, dibutyltin distearate, dibutyltin bisisoate Organic tin compounds such as nonyl 3-mercaptopropionate, dibutyltin bisisooctylthioglycolate, dioctyltin distearate, dioctyltin oxide, dioctyltin dilaurate, dioctyltin diacetate, dioctyltin diversate; lead octylate, etc. Of organic lead compounds;
Butylamine, octylamine, dibutylamine, monoethanolamine, diethanolamine, triethanolamine, diethylenetriamine, triethylenetetramine, oleylamine, octylamine, cyclohexylamine, benzylamine, diethylaminopropylamine, xylylenediamine, triethylenediamine, guanidine, diphenylguanidine. , 2,4,6-tris (dimethylaminomethyl) phenol, morpholine, N
-Methylmorpholine, 1,3-diazabicyclo [5.
4.6] Amine compounds such as undecene-7 or carboxylates thereof; low molecular weight polyamide resins obtained from excess polyamine and polybasic acid; reaction product of excess polyamine and epoxy compound; γ-amino A silane coupling agent having an amino group such as propyltrimethoxysilane and N- (β-aminoethyl) aminopropylmethyldimethoxysilane. These may be used alone or in combination of two or more.

The hydrosilylation catalyst (c) contained in the curable composition of the present invention is not particularly limited, and a commonly used catalyst can be used. Such hydrosilylation catalysts include the following compounds: cyclohexanone peroxide, 3,3,5-trimethylcyclohexanone peroxide, methylcyclohexanone peroxide, 1,1-bis (t-butylperoxy) -3. , 3,5-Trimethylcyclohexane, 1,1-bis (t-butylperoxy) cyclohexane, n-butyl-4,4-bis (t-butylperoxy) valerate, cumene hydroperoxide, 2,
5-Dimethylhexane-2,5-dihydroperoxide, 1,3-bis (t-butylperoxy) -m-isopropyl) benzene, 2,5-dimethyl-2,5-di (t-butylperoxy) ) Hexane, diisopropylbenzene peroxide, t-butylcumyl peroxide, decanoyl peroxide, lauroyl peroxide, benzoyl peroxide, 2,4-dichlorobenzoyl peroxide, bis (t-butylcyclohexyl) peroxydicarbonate, t -Peroxide polymerization initiators such as butyl peroxybenzoate and 2,5-dimethyl-2,5-di (benzoylperoxy) hexane; 2,2'-azobis (isobutyronitrile), 1,
1-azobis (cyclohexane-1-carbonitrile), azocumene, 2,2'-azobis (2-methylbutyronitrile), 2,2'-azobisdimethylvaleronitrile, 4,4'-azobis (4-cyano Valeric acid), 2
-(T-butylazo) -2-cyanopropane, 2,2 '
-Azobis (2,4,4-trimethylpentane), 2,
2'-azobis (2-methylpropane), dimethyl 2,
Azo-based polymerization initiators such as 2′-azobis (2-methylpropionate); metals selected from Group VIII transition metal elements such as platinum, rhodium, cobalt, palladium and nickel, compounds containing the metals, the metals Such as complex containing. From the viewpoint of hydrosilylation reactivity, the following compounds are preferable: chloroplatinic acid (H ₂ PtCl ₆ .6H ₂ O), platinum-vinylsiloxane complex, platinum-olefin complex, platinum bisacetylacetonate, Pt metal, RhCl.
(PPh ₃ ) ₃ , RhCl ₃ , Rh / Al ₂ O ₃ , RuC
l ₃ , IrCl ₃ , FeCl ₃ , AlCl ₃ , PdCl ₂ ·
2H ₂ O, NiCl ₂ , TiCl _4, etc. Chloroplatinic acid (H ₂
PtCl ₆ .6H ₂ O), platinum-vinylsiloxane complex,
Platinum-olefin complexes, platinum-containing compounds such as platinum bisacetylacetonate and platinum-containing complexes are more preferable, and platinum-vinylsiloxane complexes and platinum-olefin complexes are particularly preferable. Here, with the platinum-vinylsiloxane complex, a siloxane having a vinyl group in the molecule as a ligand, a polysiloxane having a vinyl group, a cyclic siloxane having a vinyl group, and the like are coordinated with a platinum atom. Is a general term for compounds. Specific examples of the ligand of the platinum-vinylsiloxane complex include 1,1,3,3
-Tetramethyl-1,3-divinyldisiloxane and the like. Specific examples of the olefin ligand of the platinum-olefin complex include 1,5-hexadiene, 1,7-octadiene, 1,9-decadiene, 1,11-dodecadiene, and 1,5-cyclooctadiene. .
Among the above ligands, 1, in terms of high catalytic activity,
1,3,3-Tetramethyl-1,3-divinyldisiloxane and 1,9-decadiene are particularly preferred. The hydrosilylation catalyst used in the present invention may be used alone or in combination of two or more. The platinum-vinylsiloxane complex and the platinum-olefin complex are disclosed in Japanese Patent Publication No. 8-9006.

The curable composition of the present invention comprises the above-mentioned vinyl sulfide group-containing polymer (a), H-Si compound (b),
And a hydrosilylation catalyst (c) and, if necessary, a chain extender, a condensation catalyst, an additive and the like.

In the above-mentioned curable composition, the composition ratio of the vinyl sulfide group-containing polymer (a) and the H-Si compound (b) is arbitrary, but the vinyl sulfide group is based on 1 mol of hydrogen-silicon bond. Is preferably 0.2 to 5 mol, more preferably 0.4 to 2.5 mol, and particularly preferably 0.8 to 1.5 mol. When the amount of the vinyl sulfide group is less than 0.2 mol per mol of hydrogen-silicon bond, a large amount of active hydrogen-silicon bond remains in the cured product, so that cracks and voids are easily generated and the strength is increased. It may decrease. If it exceeds 5 moles, curing may be insufficient and a cured product having sufficient strength may not be obtained.

The content of the hydrosilylation catalyst (c) is not particularly limited. 1 mol of vinyl sulfide group,
A ratio of 10 ^-1 to 10 ^-8 mol is preferable, and 10 ^-3 to 10
^-6 mol is more preferred. If it is less than 10 ^-8 mol, curing may not proceed sufficiently, and if it is more than 10 ^-1 mol, it is economically disadvantageous, and problems such as coloring may occur.

The curable composition of the present invention is cured to give a cured product having the desired physical properties. For example,
The composition of the present invention can be a thermoplastic elastomer. For example, when α, ω-dihydropolydimethylsiloxane is used as the H-Si compound (b), a hydrosilylation reaction produces a block copolymer having polydimethylsiloxane as a polymer block. Since polydimethylsiloxane has a low glass transition temperature, it can be a soft segment. Therefore, by selecting, as the vinyl sulfide group-containing polymer contained in the curable composition, a polymer having a glass transition temperature of 50 ° C. or higher that can be a hard segment, the cured product has elastomeric properties. Examples of such a vinyl sulfide group-containing polymer include, but are not limited to, polyacrylonitrile, polymethyl methacrylate, polyvinyl chloride, polymethacrylonitrile, and the like. Among these, polymethyl methacrylate having a vinyl sulfide group is preferable in terms of cost. An elastomer can be similarly obtained by using α, ω-dihydropolydiethylsiloxane, α, ω-dihydropolydiphenylsiloxane or the like instead of α, ω-dihydropolydimethylsiloxane.

Since the vinyl sulfide group-containing polymer contained in the curable composition of the present invention contains a sulfur atom, it has good compatibility with polar resins and the like, and when each component of the composition is mixed, A uniform composition is obtained. It also has excellent adhesion to metal surfaces.

The vinyl sulfide group-containing polymer of the present invention can also be cured by radical crosslinking,
As the curable composition, a blend of the vinyl sulfide group-containing polymer (a) and the crosslinking agent (d) can also be used. A general rubber cross-linking agent can be used as the cross-linking agent (d) and is not particularly limited. Specific examples of the crosslinking agent (d) include precipitated sulfur, highly dispersible sulfur, surface-treated sulfur,
Examples thereof include sulfur-based crosslinking agents such as insoluble sulfur, dimorpholine sulfide, and alkylphenol disulfide; organic peroxides such as benzoyl peroxide described above as a polymerization initiator. The amount of the crosslinking agent (d) used is not particularly limited, but in terms of reaction efficiency and cost,
The amount is preferably 0.01 to 20 parts by weight, more preferably 0.1 to 10 parts by weight, based on 100 parts by weight of the vinyl sulfide group-containing polymer (a).

In the curable composition which is cured by radical crosslinking, the following unsaturated bond-containing compound may be added as a crosslinking aid, if necessary. Polyfunctional vinyl monomers such as divinylbenzene and triallyl cyanurate; Polyfunctional methacrylate monomers such as ethylene glycol dimethacrylate, diethylene glycol dimethacrylate, trimethylolpropane trimethacrylate and allyl methacrylate; polyethylene glycol dimethacrylate, ethylene-propylene-diene Monomer copolymer, polybutadiene, polyisoprene, α, ω-divinylpolydimethylsiloxane, α, ω
-Unsaturated bond-containing polymers such as diallyl polyisobutylene.

In addition to the above components, the curable composition of the present invention may contain one or more additives, if necessary, for the purpose of adjusting the physical properties of the cured product. Additives are not particularly limited, but include phthalates, trialkyl phosphates, adipates, polyester plasticizers, epoxy plasticizers, stearic acid plasticizers, plasticizers such as chlorinated paraffins; sodium isethionate,
Thixotropy improver such as sodium salt of 2-sulfoethyl stearate; phosphoric acid, sodium hydrogen sulfate, benzoic acid, citric acid, succinic acid, aspartic acid, glutamic acid, fumaric acid, maleic acid, lactic acid, oleic acid, hydrotalcite , Zeolite, aluminosilicate, metal salt of perchlorate, etc. heat resistance improver; stabilizer for vinyl chloride, organotin stabilizer, lead stabilizer, metal soap stabilizer, etc .; phenolic antioxidant Agents, antioxidants such as sulfur-based antioxidants and phosphorus-based antioxidants; salicylic acid-based UV absorbers, benzophenone-based UV absorbers, benzotriazole-based UV absorbers, cyanoacrylate-based UV absorbers, nickel-based UV absorbers UV absorbers such as bis (2,2,6,6-tetramethyl-4-piperidyl) sebacate , Adeka Stab LA series (manufactured by Asahi Denka Co., Ltd.) and other hindered amine light stabilizers (HALS); poly (oxyethylene) alkylamines, poly (oxyethylene) alkyl ethers, glycerin fatty acid esters, alkylsulfonates, alkylsulfates, Antistatic agents such as alkyl phosphates, quaternary ammonium chloride, alkyl betaines, alkyl imidazolines, conductive resins; halogen-based flame retardants, phosphorus-based flame retardants, antimony trioxide, tin oxide, aluminum hydroxide, magnesium hydroxide, poly Flame retardants such as siloxane flame retardants; colorants; azodicarbonamide, N, N'-nitrosopentamethylenetetramine, p
-Foaming agent such as toluenesulfonylhydrazine; paraffin, polyolefin wax, animal oil, coconut oil, rice bran wax, montan wax, fatty acid amide, calcium stearate, zinc stearate, higher fatty acid ester, and other lubricants; Crystal nucleating agents such as 2,2′-methylenebis (4,6-di-t-butylphenyl) sodium phosphate and alkyl-substituted dibenzylidene sorbitol; hexamethylenetriamine,
1,3-diphenylguanidine, N, N'-diphenylthiourea, dilaurylthiourea, 2-mercaptobenzothiazole, dibenzothiazyl disulfide, tetramethylthiuram disulfide, tetramethylthiuram monosulfide, sodium diethyldithiocarbamate,
Vulcanization accelerator such as zinc dibutyldithiocarbamate; 6
-Ethoxy-1,2-dihydro-2,2,4-trimethylquinoline, dialkyldiphenylamine, di (α-methylbenzyl) phenol, 2,5-di-t-butylhydroquinone, 2-mercaptobenzimidazole, dibutyldithiocarbamic acid Antiaging agents such as nickel, tris (nonylphenyl) phosphite, distearyl thiodipropionate, and Sannock (manufactured by Ouchi Shinko Chemical Industry Co., Ltd.); p-quinonedioxime, poly p-dinitrosobenzene, 2, Vulcanizing agents such as 4,6-trimercapto-s-triazine and brominated alkylphenol formaldehyde resins; anti-scorch agents such as phthalic anhydride O;
A mastication accelerator such as O'-dibenzamide diphenyl disulfide; Takkyrol 101 (Taoka Chemical Industry Co., Ltd.)
), Modified alkylphenol formaldehyde resin and other tackifiers; acetic acid cyclohexylamine salt and other latex coagulants; Exton K1 (Kawaguchi Chemical Co., Ltd.), PA-20 (Kanebuchi Chemical Co., Ltd.), etc. Processing aids; calcium silicate, acetylene black,
Inorganic fillers such as calcium carbonate, clay, talc, titanium oxide and diatomaceous earth; at least one material selected from natural rubber can be used. These additives may be appropriately selected depending on the polymer used, the H-Si compound, the type and composition of the hydrosilylation catalyst, the application in which the curable composition is used, and the like.

Among the above additives, from the viewpoint of excellent heat resistance, weather resistance, light resistance, and storage stability, antioxidants, ultraviolet absorbers, light stabilizers, antiaging agents, and storage stability improvers are selected. It is preferable to contain at least one additive selected from the group consisting of:

The method for mixing the components of the curable composition of the present invention is not particularly limited, and any commonly used method can be applied. When mixing each component, an organic solvent may be used, and may be melt-kneaded using a roll kneader, a kneader, an extruder, a plastomill, a Banbury mixer, or when any of the components is liquid. May be mixed as they are.

The method for curing the curable composition of the present invention is not particularly limited, and any commonly used method can be applied. It may be heated and stirred in an organic solvent, or may be melt-kneaded using a roll kneader, a kneader, an extruder, a plastomill, a Banbury mixer, or the like. Further, a composition kept in an arbitrary shape such as a sheet, a film, a hose, a tube, and a column may be heated and cured, or may be cured by using an injection molding machine.

The curable composition of the present invention comprises various molded products such as films and sheets, refractory materials, flame retardant materials, pressure sensitive adhesives, adhesives, hot melt adhesives, reactive hot melt adhesives, thermoplastics. It is widely applicable to elastomers, reactive thermoplastic elastomers, compatibilizers, resin modifiers, primers, sealing materials, potting materials, paints, coating materials, caulking materials and the like.

[0133]

EXAMPLES The present invention will be described below based on examples.
The present invention is not limited to these examples.

In this example, the weight average molecular weight (M
w), number average molecular weight (Mn), and molecular weight distribution (Mw)
/ Mn) was determined by gel permeation chromatography (GPC) analysis. Chloroform, tetrahydrofuran,
Alternatively, dimethylformamide was used as an eluent, a polystyrene gel column was used, and analysis was performed using a polystyrene standard sample as a reference. The GPC analyzer is GP manufactured by Waters
Shodex K manufactured by Showa Denko KK using the C system
A -804 column was used.

In this embodiment, the compression set is JIS
According to K6301, the cylindrical molded body was held at 70 ° C. for 22 hours under the condition of a compression rate of 25%, left at room temperature for 30 minutes, and then the thickness of the molded body was measured to calculate the residual strain.

In this example, oil resistance is ASTM D
In accordance with ASTM No. 638, the molded article of the composition was kept at 150 ° C. according to ASTM oil No. It was soaked in 3 for 72 hours and the weight change rate was obtained.

In this example, the heat resistance was evaluated by measuring the flow starting temperature. Shimadzu Corporation Koka type flow tester CFT-500C type is used to heat the resin at a heating rate of 5 ° C./min, and extrude from a nozzle having an inner diameter of 1 mm and a length of 10 mm under a load of 60 kgf / cm ^2. The temperature at the start of extrusion (Tfb) at that time was taken as the flow start temperature.

Example 1 A 1 L reactor equipped with a stirrer, a thermometer, a nitrogen gas introducing tube, a reflux cooling tube, and a dropping funnel was placed in an emulsifier sodium dodecylsulfonate 41.
0 mg and 400 g of distilled water were added, and nitrogen substitution was performed while heating and stirring at 80 ° C. As a compound having a thiocarbonylthio group, the following formula

[0139]

[Chemical 38] 23.34 g of the compound represented by is dissolved in 50 g of n-butyl acrylate as a monomer and added,
After stirring for 0 minutes under a nitrogen stream, 7.0 g of 4,4′-azobis (4-cyanovaleric acid) as a polymerization initiator was added together with 25 g of distilled water. When the mixture was stirred at 80 ° C. for 30 minutes, a mixed solution of 100 g of monomer n-butyl acrylate and 50 g of 2-methoxyethyl acrylate was added dropwise from the dropping funnel over 1 hour and 30 minutes. 80 more
After stirring at 0 ° C for 4 hours, the emulsion was cooled to room temperature, and salted out, filtered, washed, and dried to obtain n-butyl acrylate having 2-thiocarbonylthio groups at both ends / 2-methoxyethyl acrylate random co-polymer. A polymer was obtained. GP
According to C analysis (chloroform eluate) and ¹ H NMR analysis, this polymer had Mw = 4320, Mn = 3970,
It was Mw / Mn = 1.09, and it was confirmed that the introduction rate of the thiocarbonylthio group was 97% based on both ends.

180 g of this polymer having thiocarbonylthio groups at both ends was dissolved in 400 mL of toluene, 20 g of monoethylamine was added as a treating agent, and the mixture was added at 10 ° C. at 10 ° C.
After stirring for an hour and distilling off excess monoethylamine, the mixture was poured into 1 L of methanol to precipitate a polymer, and n-butyl acrylate / acrylic acid 2-having a mercapto group at both ends was used.
A methoxyethyl random copolymer was obtained. This polymer was dissolved in 400 mL of toluene, placed in a pressure vessel, charged with 0.2 g of potassium hydroxide as a base and 25 g of acetylene, and reacted at 80 ° C. for 12 hours to give an acrylic resin having vinyl sulfide groups at both ends. An n-butyl acid / 2-methoxyethyl acrylate random copolymer was obtained. As a result of GPC analysis (chloroform eluate), Mw
= 4450, Mn = 4000, and Mw / Mn = 1.11.

100 parts by weight of the thus obtained random copolymer having vinyl sulfide groups at both ends was added with H
-Containing 4.2 parts by weight of 1,3,5-tris (dimethylsilyl) benzene as the Si compound, and 0.5 part by weight of chloroplatinic acid (hexahydrate) as the hydrosilylation catalyst,
It was a curable composition. A 40 μm thick PET film (manufactured by Kuraray Co., Ltd.) obtained by subjecting this curable composition to a corona discharge treatment.
Apply with an applicator on top, and at 50 ℃ for 2 hours, 80 ℃
Heated for 2 hours. Since the cured product on the obtained film has tackiness, the film having the cured product on its surface could be used as an adhesive film or an adhesive sheet.

(Example 2) In a 1 L reactor equipped with a stirrer, a thermometer, a nitrogen gas introducing tube, and a reflux cooling tube, 181 g of n-butyl acrylate as a monomer and 1,1 'as a polymerization initiator. -Azobis (1-cyclohexanecarbonitrile) 40 mg, as a compound having a thiocarbonylthio group, represented by the following formula:

[0143]

[Chemical Formula 39] 1,4-bis (thiobenzoylthiomethyl) represented by
635 mg of benzene and 300 mL of toluene were added, and the system was replaced with nitrogen. 90 ° C while stirring the reaction solution
Heated for 5 hours. Sampling and GPC analysis (chloroform eluate) were carried out, Mw = 77,000, Mn = 5
6900, formation of a polymer with Mw / Mn = 1.35 was confirmed. ¹ H NMR measurement was performed, and it was confirmed that a thiocarbonylthio group was introduced at both terminals of poly (n-butyl acrylate), and the introduction rate was 93% based on both terminals. The reaction rate of n-butyl acrylate was 55%.

30 g of monoethylamine as a treating agent was added to the thus obtained toluene solution of poly (n-butyl acrylate) having thiocarbonylthio groups at both ends, and the mixture was stirred at 10 ° C. for 5 hours. Sampling ¹ H NM
R measurement was carried out, and it was confirmed that the introduction rate of the mercapto group was 90% on the basis of both ends, which was poly (n-butyl acrylate) having mercapto groups at both ends.

Excess monoethylamine was distilled off from the reaction solution, and the obtained toluene solution was put into a pressure resistant reactor. To 100 parts by weight of the polymer, 0.1 parts by weight of potassium hydroxide as a base was added, and acetylene gas was supplied while adjusting the pressure in the reactor to 5 kg / cm ² at 80 ° C. It was stirred for 10 hours. Vacuum devolatilized washed with water and the toluene solution, ¹ of the resultant polymer H N
From the MR spectrum, it was confirmed to be poly (n-butyl acrylate) having vinyl sulfide groups at both ends.
The introduction rate of the vinyl sulfide group was 85% based on both ends. From GPC analysis (chloroform eluate), Mw
= 86400, Mn = 61200, Mw / Mn = 1.4
It was confirmed to be 1.

The hydrosilylation of 1,9-decadiene and 1,3,5,7-tetramethylcyclotetrasiloxane was carried out on 100 parts by weight of n-butyl polyacrylate having vinyl sulfide groups at both ends thus obtained. The following formula, which is a reactant

[0147]

[Chemical 40] (In the formula, Me represents a methyl group) (H
-Si compound) 0.45 parts by weight and 0.3 parts by weight of a xylene solution (3% by weight) of a platinum-1,3-divinyltetramethyldisiloxane complex, which is a hydrosilylation catalyst, were mixed to prepare a curable composition. .

It was confirmed that a cured product was obtained by putting the obtained curable composition in a sheet-shaped mold and heating it at 100 ° C. for 30 minutes. The physical properties of the obtained cured product are shown in Table 1.
Shown in.

(Example 3) A 300 mL reactor equipped with a stirrer, a thermometer, a nitrogen gas introducing tube, and a reflux cooling tube was added,
90.5 g of n-butyl acrylate as a monomer, 20 mg of 1,1′-azobis (1-cyclohexanecarbonitrile) as a polymerization initiator, and the following formula as a compound having a thiocarbonylthio group

[0150]

[Chemical 41] 1,4-bis (thiobenzoylthiomethyl) represented by
701 mg of benzene and 140 mL of toluene were added, and the system was replaced with nitrogen. 90 ° C while stirring the reaction solution
Heated at 40 hours. Sampling the reaction solution, GPC
From analysis, Mw = 56500, Mn = 41100, Mw /
Polymer formation with Mn = 1.37 was confirmed. Then ¹ H
From the NMR measurement, it was confirmed that the thiocarbonylthio group was introduced at both ends of the poly (n-butyl acrylate), and the introduction rate was 95% based on both ends.

Subsequently, sodium hydroxide, which is a base, was added.
A solution prepared by dissolving 3 g in 3 g of isopropanol was added and stirred at 80 ° C. for 5 hours. ¹ H N for sampling
As a result of MR measurement, it was confirmed that the polyacrylate was n-butyl polyacrylate having mercapto groups at both ends, and the introduction rate of the mercapto groups was 90% based on both ends.

This toluene solution was placed in a pressure vessel, acetylene gas was supplied while adjusting the pressure in the reactor to 5 kg / cm ^2, and the mixture was stirred at 80 ° C. for 10 hours. The toluene solution was washed with water and then devolatilized under reduced pressure. From the ¹ H NMR spectrum of the obtained polymer, it was confirmed that the polymer was n-butyl polyacrylate having vinyl sulfide groups at both ends. The introduction rate of vinyl sulfide groups was 88% on the basis of both ends. As a result of GPC analysis (chloroform eluate) of the vinyl sulfide group-containing poly (n-butyl acrylate) thus obtained, Mw = 60400, Mn =
42100 and Mw / Mn = 1.43.

To 40 g of the thus obtained poly (n-butyl acrylate) having vinyl sulfide groups at both ends, H-
103 mg of 1,3,5,7-tetrahydrotetramethylcyclotetrasiloxane as a Si compound, and a xylene solution (3% by weight) of platinum-1,3-divinyltetramethyldisiloxane complex as a hydrosilylation catalyst 0.25
Add mL and add 100 between the two glass plates.
The mixture was heated at 0 ° C for 20 minutes to be cured. The obtained cured product was a transparent and uniform sheet.

Example 4 300 mL equipped with a stirrer, a thermometer, a nitrogen gas introduction tube, a dropping funnel, and a reflux condenser.
110 mg of sodium dodecyl sulfonate as an emulsifier and 100 g of distilled water were placed in a reactor, and the system was replaced with nitrogen while heating and stirring at 80 ° C. The following formula, which is a compound having a thiocarbonylthio group

[0155]

[Chemical 42] 217 mg of 2- (2-phenylpropyl) dithiobenzoate represented by are dissolved in 3.0 g of methyl methacrylate, which is a monomer, and added, and 20 minutes later, 4,4′-azobis (4 -Cyanovaleric acid) 185m
g was added with 4 g of distilled water. After stirring at 80 ° C. for 20 minutes, 17.5 g of methyl methacrylate was added dropwise from the dropping funnel over 90 minutes. After 30 minutes, 20.0 g of monomer n-butyl acrylate was added dropwise from the dropping funnel over 1 hour. After stirring for 5 hours at 80 ° C., the emulsion was salted out with calcium carbonate and washed with distilled water to obtain 31.2 g of methyl methacrylate-n-butyl acrylate diblock copolymer. As a result of GPC analysis (chloroform eluate), Mw = 59900, Mn = 44300,
Mw / Mn = 1.35, and as a result of ¹ H NMR measurement, a thiocarbonylthio group was introduced at the n-butyl side end of the polyacrylate of the methyl methacrylate-n-butyl acrylate diblock copolymer. It was confirmed that the introduction rate was 82% on the basis of one end.

20 g of the obtained polymer was added to 100 m of toluene.
A solution prepared by dissolving 0.2 g of sodium hydroxide, which is a base, in 10 mL of ethanol was added, and the mixture was stirred at 80 ° C. for 5 hours. From ¹ H NMR measurement of the polymer obtained by sampling, it was confirmed that the polymer was a methyl methacrylate-n-butyl acrylate diblock copolymer having a mercapto group at the n-butyl polyacrylate side terminal. The introduction rate of the mercapto group was 77% on the basis of one end.

The poly (n-butyl acrylate) thus obtained was methyl methacrylate having a mercapto group at the terminal.
Acetylene gas was supplied to a toluene solution of an n-butyl acrylate diblock copolymer while adjusting the pressure in the reactor to always be 5 kg / cm ^2, and the temperature was adjusted to 1 at 80 ° C.
Stir for 0 hours. The toluene solution was washed with water and then devolatilized under reduced pressure. From the ¹ H NMR spectrum of the obtained polymer, methyl methacrylate-n-butyl acrylate diblock copolymer having a vinyl sulfide group at the terminal of n-butyl polyacrylate was obtained. It was confirmed that they were united. The introduction rate of the vinyl sulfide group was 73% on the basis of one end. GPC of the vinyl sulfide group-containing copolymer thus obtained
As a result of analysis (chloroform eluate), Mw = 6220
0, Mn = 45500, and Mw / Mn = 1.37.

The diblock copolymer 10 thus obtained
0,3 parts by weight of H-Si compound as 1,3,5,7
0.11 parts by weight of tetrahydrotetramethylcyclotetrasiloxane and platinum as hydrosilylation catalyst
A curable composition was prepared by adding 0.1 part by weight of a xylene solution (3% by weight) of a 1,3-divinyltetramethyldisiloxane complex.

This curable composition was placed in a sheet form frame and heated at 100 ° C. for 20 minutes to obtain a sheet form body. The physical properties of the obtained molded product are shown in Table 1.

Example 5 To 100 parts by weight of the vinyl sulfide group-containing methyl methacrylate-n-butyl acrylate diblock copolymer obtained in Example 4,
0.11 part by weight of 1,3-dihydrotetramethyldisiloxane as an H-Si compound, and 0.05 part by weight of a platinum-1,3-divinyltetramethyldisiloxane complex xylene solution (3% by weight) as a hydrosilylation catalyst. Was blended to obtain a curable composition.

This curable composition was placed in a sheet form frame and heated at 100 ° C. for 60 minutes to obtain a sheet form body. The physical properties of the obtained molded product are shown in Table 1.

(Example 6) In a 1 L pressure resistant reactor equipped with a stirrer, a thermometer, a nitrogen gas introducing pipe, and a reflux cooling pipe, 181 g of n-butyl acrylate as a monomer and 1,1 as a polymerization initiator. '-Azobis (1-cyclohexanecarbonitrile) 40 mg, as a compound having a thiocarbonylthio group, represented by the following formula:

[0163]

[Chemical 43] 635 mg of the compound shown by and 300 m of toluene
L was added and the system was replaced with nitrogen. The reaction was heated at 90 ° C. for 5 hours with stirring. By sampling and GPC analysis (chloroform eluent), Mw = 77,000, M
It was confirmed that a polymer having n = 56900 and Mw / Mn = 1.35 was produced. As a result of ¹ H NMR measurement, it was confirmed that a thiocarbonylthio group was introduced at both ends of poly (n-butyl acrylate), and the introduction rate was 95% based on both ends.

In a toluene solution of n-butyl polyacrylate having thiocarbonylthio groups at both ends, 0.5 g of sodium hydroxide as a base and 5 g of isopropanol were added.
The solution dissolved in was added and stirred at 100 ° C. for 5 hours. Isopropanol was removed by distillation, sampling was carried out and ¹ H NMR measurement was carried out to confirm the production of poly (n-butyl acrylate) having mercapto groups at both ends, and the introduction rate of mercapto groups was 90% based on both ends. I confirmed that there is.

Acetylene gas was supplied to the thus obtained toluene solution of poly (n-butyl acrylate) having mercapto groups at both ends, while adjusting the pressure in the reactor to 5 kg / cm ^{2 at} all times. The mixture was stirred at 0 ° C for 10 hours. The toluene solution was washed with water and then devolatilized under reduced pressure. From the ¹ H NMR spectrum of the obtained polymer, n-butyl polyacrylate having vinyl sulfide groups at both ends was obtained. GPC analysis of the vinyl sulfide group-containing poly (n-butyl acrylate) thus obtained (chloroform eluent)
As a result, Mw = 78300, Mn = 57700, Mw /
It was Mn = 1.36.

With respect to 100 parts by weight of this n-butyl polyacrylate, 0.24 of 1,3,5,7-tetrahydrotetramethylcyclotetrasiloxane as an H-Si compound was used.
Parts by weight and platinum-1,3 as hydrosilylation catalyst
-0.35 parts by weight of a xylene solution of divinyltetramethyldisiloxane complex (3% by weight) was mixed to obtain a curable composition. The cured product obtained by heating this curable composition at 100 ° C. for 2 hours was a cured product usable as an adhesive.

Example 7 In a 100 mL pressure-resistant reactor equipped with a stirrer, a thermometer, a nitrogen gas introducing tube, and a reflux cooling tube, 28.0 g of methyl methacrylate as a monomer and 2,2 as a polymerization initiator. 38 mg of'-azobis (isobutyronitrile), the following formula as a compound having a thiocarbonylthio group

[0168]

[Chemical 44] 2- (2-phenyl) propyldithiobenzoate (1.19 g) and toluene (50 mL) were added, and the system was replaced with nitrogen. Stir the reaction mixture at 60 ° C for 10
Heated for hours. Sampling and GPC analysis (chloroform eluate) were performed, Mw = 3750, Mn = 310
0, formation of polymethylmethacrylate with Mw / Mn = 1.21 was confirmed. As a result of ¹ H NMR measurement, it was confirmed that a thiocarbonylthio group was introduced at one end of polymethylmethacrylate, and the introduction rate was 98% based on the one end.

Next, 0.15 of sodium hydroxide as a base
g and 1.0 g of ethanol were added, and the mixture was mixed at 80 ° C for 5
Stir for hours. ¹ H of polymer obtained by sampling
From the NMR measurement, it was confirmed to be polymethylmethacrylate having a mercapto group at one end. The introduction rate of the mercapto group was 94% on the basis of one end.

To the toluene solution of polymethylmethacrylate having a mercapto group at one end thus obtained, acetylene gas was supplied while controlling the pressure in the reactor to be 5 kg / cm ² at 80 ° C. Stir for 10 hours. After the reaction, the toluene solution was poured into 100 mL of methanol, and a precipitate was deposited to obtain a polymer ¹ H NM
From the R spectrum, it was confirmed to be polymethyl methacrylate having a vinyl sulfide group at one end. The introduction rate of the vinyl sulfide group was 91% on the basis of one end. As a result of GPC analysis (chloroform eluate), Mw =
It was 3700, Mn = 2950, and Mw / Mn = 1.25.

With respect to 100 parts by weight of polymethylmethacrylate having a vinyl sulfide group at one end, H--Si was added.
77.1 parts by weight of α, ω-dihydropolydimethylsiloxane having a number average molecular weight of 5000 as a compound, and 0.85 parts by weight of a platinum-1,3-divinyltetramethyldisiloxane complex xylene solution (3% by weight) as a hydrosilylation catalyst. Was blended to obtain a curable composition. A cured product obtained by heating this curable composition at 100 ° C. for 2 hours is methyl methacrylate-dimethylsiloxane-methyl methacrylate.
It was a triblock copolymer. The physical properties of the cured product are shown in Table 1.

Example 8 In a 100 mL pressure-resistant reactor equipped with a stirrer, a thermometer, a nitrogen gas introducing tube, and a reflux cooling tube, 28.3 g of methyl methacrylate as a monomer and 2,2 as a polymerization initiator were added. '-Azobis (isobutyronitrile) 40 mg, as a compound having a thiocarbonylthio group, represented by the following formula:

[0173]

[Chemical formula 45] 121 mg of 2- (2-phenyl) propyldithiobenzoate represented by and toluene 20 mL were put, and the system was replaced with nitrogen. The reaction solution was heated at 60 ° C. for 8 hours while stirring. Sampling and GPC analysis (chloroform eluate) were performed, Mw = 35800, Mn = 2980
0, formation of polymethylmethacrylate with Mw / Mn = 1.20 was confirmed. As a result of ¹ H NMR measurement, it was confirmed that a thiocarbonylthio group was introduced at one end of polymethylmethacrylate, and the introduction rate was 94% based on the one end.

Next, 0.1 g of sodium hydroxide as a base
Add a mixed solution of 0.5g of isooctanol and 80 ℃
It was stirred for 5 hours. Of the polymer obtained by sampling
^{From 1} HNMR measurement, it was confirmed to be polymethylmethacrylate having a mercapto group at one end. The introduction rate of the mercapto group was 90% on the basis of one end.

To the toluene solution of polymethylmethacrylate having a mercapto group at one end thus obtained, acetylene gas was supplied while adjusting the pressure in the reactor to 5 kg / cm ^2, and at 80 ° C. Stir for 10 hours. After the reaction, the toluene solution was poured into 100 mL of methanol, and a precipitate was deposited to obtain a polymer ¹ H NM
From the R spectrum, it was confirmed to be polymethyl methacrylate having a vinyl sulfide group at one end. The introduction rate of the vinyl sulfide group was 86% on the basis of one end. As a result of GPC analysis (chloroform eluate), Mw =
35500, Mn = 30000, Mw / Mn = 1.18
Met.

H-Si was added to 100 parts by weight of polymethylmethacrylate having a vinyl sulfide group at one end.
14.3 parts by weight of α, ω-dihydropolydimethylsiloxane having a number average molecular weight of 10,000 as a compound, 1 part by weight of a xylene solution (3% by weight) of a platinum-1,3-divinyltetramethyldisiloxane complex as a hydrosilylation catalyst,
And 1 part by weight of dimethylmalate was blended as a storage stability improver to obtain a curable composition. A cured product obtained by heating this curable composition at 120 ° C. for 2 hours is methyl methacrylate-dimethylsiloxane-methyl methacrylate.
It was a triblock copolymer and exhibited properties as a thermoplastic elastomer. The physical properties of the cured product are shown in Table 1.

(Example 9) 300 mL equipped with a stirrer, a thermometer, a nitrogen gas introducing tube, a dropping funnel, and a reflux cooling tube
110 mg of sodium dodecyl sulfonate as an emulsifier and 100 g of distilled water were placed in a reactor, and the system was replaced with nitrogen while heating and stirring at 80 ° C. As a compound having a thiocarbonylthio group, the following formula

[0178]

[Chemical formula 46] 217 mg of 2- (2-phenyl) propyldithiobenzoate represented by is dissolved in 3.0 g of methyl methacrylate, which is a monomer, and added, and 20 minutes later, 4,4′-azobis (4-) which is a polymerization initiator is added. Cyanovaleric acid) 185m
g was added with 4 g of distilled water. After stirring at 80 ° C. for 20 minutes, 17.5 g of methyl methacrylate was added dropwise from the dropping funnel over 90 minutes. After 30 minutes, 20.0 g of monomer n-butyl acrylate was added dropwise from the dropping funnel over 1 hour. After stirring at 80 ° C. for 5 hours, the emulsion was salted out with sodium chloride and washed with distilled water to obtain 31.2 g of methyl methacrylate-n-butyl acrylate diblock copolymer. As a result of GPC analysis (chloroform eluate), Mw = 66000, Mn = 44300,
Mw / Mn = 1.49, and as a result of ¹ H NMR measurement, a thiocarbonylthio group was introduced at the poly (n-butyl acrylate) side terminal of the methyl methacrylate-n-butyl acrylate diblock copolymer. It was confirmed that the introduction rate was 82% on the basis of one end.

20 g of the obtained polymer was added to 100 m of toluene.
It was dissolved in L, 8 g of diethylamine as a treating agent was added, and the mixture was stirred at room temperature for 2 hours and at 50 ° C. for 3 hours, and then degassed under reduced pressure. From ¹ H NMR measurement of the obtained polymer, it was confirmed to be a methyl methacrylate-n-butyl acrylate diblock copolymer having a mercapto group at the n-butyl polyacrylate side terminal. The introduction rate of the mercapto group was 77% on the basis of one end.

The poly (n-butyl acrylate) thus obtained was methyl methacrylate having a mercapto group at the terminal.
12 g of n-butyl diblock copolymer acrylate was dissolved in 20 mL of toluene, and the solution was placed in a pressure resistant reactor together with 0.1 g of a 10% methanol solution of sodium methylate as a base having a catalytic action. The pressure inside the reactor is always 5 kg
The acetylene gas was supplied while adjusting so that the pressure was / cm ^2, and the mixture was stirred at 80 ° C. for 10 hours. After the reaction, the toluene solution was poured into 80 mL of methanol to deposit a precipitate. From the ¹ H NMR spectrum of the obtained polymer, it was confirmed that the polymer was a methyl methacrylate-n-butyl acrylate diblock copolymer having a vinyl sulfide group at the n-butyl polyacrylate end. The introduction rate of the vinyl sulfide group was 73% on the basis of one end. GPC of the vinyl sulfide group-containing copolymer thus obtained
As a result of analysis (chloroform eluate), Mw = 7140
0, Mn = 45200, and Mw / Mn = 1.58.

With respect to 100 parts by weight of the methyl methacrylate-n-butyl acrylate diblock copolymer having a vinyl sulfide group, 4.23 of α, ω-dihydropolydimethylsiloxane having a number average molecular weight of 5000 as an H-Si compound was used. By weight, 0.5 part by weight of chloroplatinic acid hexahydrate as a hydrosilylation catalyst was blended to obtain a curable composition.

A cured product obtained by heating this curable composition at 100 ° C. for 2 hours exhibited properties as a thermoplastic elastomer. The physical properties of the cured product are shown in Table 1.

(Example 10) Stirrer, thermometer, pressure gauge,
In a 20 L pressure resistant reactor equipped with a nitrogen gas introducing tube, a monomer introducing tube, and a reflux cooling tube, 155.3 g of a 3% aqueous solution of polyvinyl alcohol was used as a dispersant, and di-2-ethylhexyl peroxydicarbonate was used as a polymerization initiator. 3.33 g of the alcohol solution of

[0184]

[Chemical 47] O-ethyl-S-cyanomethylxanthate (9.32 g) and distilled water (18640 g) were added, and the atmosphere in the system was replaced with nitrogen. From the monomer introduction pipe, vinyl chloride monomer 46
60 g was introduced. The reaction solution was heated to a temperature of 57 ° C. and stirred for 10 hours. Unreacted monomer was distilled off, and the suspension was filtered and washed with methanol to give polyvinyl chloride 21
40 g was obtained. As a result of GPC measurement using tetrahydrofuran (THF) as an eluent, Mw = 53500, Mn = 3
7600 and Mw / Mn = 1.42 were confirmed. As a result of ¹ H NMR measurement, it was confirmed that the obtained polyvinyl chloride had a thiocarbonylthio group at one end and the introduction rate was 82% based on the one end.

100 g of this polyvinyl chloride was added to THF10
1 g of sodium methylate, a base, dissolved in 00 g
Was added and the mixture was stirred at room temperature for 10 hours. The obtained polymer is polyvinyl chloride having a mercapto group at one end,
As a result of ¹ H NMR measurement, the introduction rate of the mercapto group was 78% on the basis of one end.

The thus obtained THF solution of polyvinyl chloride having a mercapto group at one end was placed in a pressure resistant reactor, 50 g of acetylene was added, and the mixture was stirred at 50 ° C. for 15 hours. From ¹ H NMR spectrum of the polymer obtained after devolatilization under reduced pressure, it was confirmed to be polyvinyl chloride having a vinyl sulfide group at one end. The introduction rate of the vinyl sulfide group was 73% on the basis of one end. As a result of GPC analysis (tetrahydrofuran eluate) of the vinyl sulfide group-containing polymer thus obtained, Mw = 5520
0, Mn = 38700, and Mw / Mn = 1.43.

With respect to 100 parts by weight of vinyl chloride having a vinyl sulfide group thus obtained, 0.13 parts by weight of 1,3,5,7-tetrahydrotetramethylcyclotetrasiloxane as an H-Si compound, and a hydrosilylation catalyst. As a curable composition, 0.3 part by weight of a solution of platinum-1,3-divinyltetramethyldisiloxane complex in xylene (3% by weight) was blended.

It was confirmed that the curable composition was cured at 80 ° C. for 4 hours to be cured to obtain a molded product.

Example 11 Polyvinyl chloride 100 having a vinyl sulfide group at one end obtained in Example 10
Number-average molecular weight of 10 as H-Si compound with respect to parts by weight
000 α, ω-dihydropolydimethylsiloxane 5
5.1 parts by weight, 0.5 part by weight of 1,7-octadiene as a chain extender, platinum-1,3 as a hydrosilylation catalyst
-0.5 parts by weight of a xylene solution of divinyltetramethyldisiloxane complex (3% by weight) was mixed and roll-kneaded. The obtained curable composition is heated at 80 ° C. for 5 hours,
A cured product was obtained. This vinyl chloride-based cured product was a vinyl chloride-based resin that could be easily molded at 100 to 120 ° C. without the need to add a plasticizer. The physical properties of the cured product are shown in Table 1.

(Example 12) A 2 L reactor equipped with a stirrer, a thermometer, a nitrogen gas introducing tube, a dropping funnel, and a reflux condenser was charged with 490 g of distilled water and 0.56 g of sodium dodecyl sulfate as an emulsifier. The system was replaced with nitrogen while heating and stirring at 80 ° C. 8.8 g of acrylonitrile as a monomer and the following formula as a compound having a thiocarbonylthio group

[0191]

[Chemical 48] The mixed solution with 2- (2-phenyl) propyldithiobenzoate represented by
Stir at 20 ° C. for 20 minutes. As a polymerization initiator, 0.93 g of 4,4'-azobis (4-cyanovaleric acid) was added to 25 g of distilled water.
And put it in the reactor. At the time of stirring at 80 ° C. for 30 minutes, 45.0 g of acrylonitrile was added dropwise over 1 hour from the attempted addition. After the completion of the dropping, sampling was carried out at the time of stirring at 80 ° C. for 5 hours, and polyacrylonitrile (Mw = 13) was obtained from GPC analysis (dimethylformamide eluate).
700, Mn = 10300, Mw / Mn = 1.33) was confirmed.

Subsequently, 20.0 g of n-butyl acrylate as a monomer was added, and 0.40 g of 4,4'-azobis (4-cyanovaleric acid) as a polymerization initiator was added together with 10 g of distilled water. After stirring at 80 ° C. for 1 hour, 80.0 g of n-butyl acrylate was added dropwise over 2 hours from the attempted addition. After completion of dropping, the mixture was stirred at 80 ° C. for 5 hours, sampled and subjected to GPC analysis (chloroform eluate), and acrylonitrile-n-butyl acrylate diblock copolymer (Mw = 48600, Mn = 34500, Mw /
Generation of Mn = 1.41) was confirmed. ¹ H NMR analysis confirmed the presence of a thiocarbonylthio group at one end of the polymer.

Subsequently, 15 g of a methanol solution of sodium methylate as a base (30% by weight) was added, and the mixture was heated at 80 ° C.
The thiocarbonylthio group was converted to a mercapto group by stirring for 3 hours. The emulsion was salted out, filtered and washed to obtain an acrylonitrile-n-butyl acrylate diblock copolymer having a mercapto group at one end.

50 g of this copolymer was dissolved in 300 g of toluene and placed in a pressure resistant reactor, and the pressure inside the reactor was always 5
The acetylene gas was supplied while adjusting the pressure to be kg / cm ^2, and the mixture was stirred at 80 ° C. for 10 hours. The obtained toluene solution was washed with water and then poured into 500 mL of methanol,
By depositing a precipitate, an acrylonitrile-n-butyl acrylate diblock copolymer having a vinyl sulfide group at one end was obtained. GPC analysis (chloroform eluent) of the vinyl sulfide group-containing copolymer thus obtained showed Mw = 51200 and Mn = 3580.
0 and Mw / Mn = 1.43.

The diblock copolymer 10 thus obtained
0, 1 part by weight of H-Si compound for 1,3,3
0.19 parts by weight of tetramethyldisiloxane and a xylene solution of platinum-1,3-divinyltetramethyldisiloxane complex as a hydrosilylation catalyst (3% by weight)
0.8 part by weight was blended to obtain a curable composition.

A cured product obtained by heating this curable composition at 100 ° C. for 1 hour exhibited properties as a thermoplastic elastomer. The physical properties of the cured product are shown in Table 1.

(Example 13) 300 equipped with a stirrer, a thermometer, a nitrogen gas introducing pipe, a dropping funnel, and a reflux cooling pipe.
A mL reactor was charged with 110 mg of sodium dodecylsulfonate as an emulsifier and 100 g of distilled water, and the inside of the system was replaced with nitrogen while stirring at 80 ° C. As a compound having a thiocarbonylthio group, the following formula

[0198]

[Chemical 49] 217 mg of 2- (2-phenyl) propyldithiobenzoate represented by is dissolved in 1.6 g of acrylonitrile, which is a monomer, and added, and 20 minutes later, 4,4′-azobis (4-cyanokyl) is used as a polymerization initiator. 185m
g was added along with 5 g of distilled water. After stirring at 80 ° C for 20 minutes, 5 g of acrylonitrile (9.3 g) was added from the dropping funnel.
It was added dropwise over 0 minutes. After completion of the dropping, the mixture was stirred at 80 ° C. for 3 hours, sampled and subjected to GPC analysis (dimethylformamide eluate) to give polyacrylonitrile (Mw = 18100, Mn = 12700, Mw / Mn =).
1.42) was confirmed.

Then, 10.0 g of n-butyl acrylate as a monomer and 7.8 ethyl acrylate were added from the dropping funnel.
The mixed liquid with g was added dropwise over 1 hour. After stirring at 80 ° C. for 5 hours, sampling was performed, and an acrylonitrile- (n-butyl acrylate / ethyl acrylate) diblock copolymer having a thiocarbonylthio group at a terminal (Mw =
48500, Mn = 31600, Mw / Mn = 1.5
3; generation of GPC (chloroform eluate) was confirmed.

To this emulsion was added 0.2 g of sodium hydroxide as a base, and the mixture was stirred at 80 ° C. for 5 hours, salted out, filtered, washed and dried to give a diblock having a vinyl sulfide group at the end. A copolymer was obtained. 12 g of this diblock copolymer was dissolved in 50 mL of toluene and placed in a pressure resistant reactor, and acetylene gas was supplied while adjusting the pressure in the reactor to always be 5 kg / cm ^2, and stirred at 80 ° C. for 10 hours. did. The obtained toluene solution was washed with water, poured into 200 mL of methanol, a precipitate was deposited and dried, and an acrylonitrile- (n-butyl acrylate / ethyl acrylate) diblock copolymer having a vinyl sulfide group at one end was obtained. Got GPC analysis (chloroform eluent) of the vinyl sulfide group-containing copolymer thus obtained showed Mw = 48900, Mn = 3210.
0 and Mw / Mn = 1.52.

The diblock copolymer 10 thus obtained
0, 1 part by weight of H-Si compound, 1, 3, 3,
0.21 parts by weight of tetramethyldisiloxane, and a xylene solution of platinum-1,3-divinyltetramethyldisiloxane complex which is a hydrosilylation catalyst (3% by weight).
0.7 part by weight was blended to obtain a curable composition.

When this curable composition was heated and cured at 100 ° C. for 3 hours, an acrylonitrile- (n-butyl acrylate / ethyl acrylate) -acrylonitrile triblock copolymer was obtained, which was used as a thermoplastic elastomer. Showed the property of. The physical properties of the cured product are shown in Table 1.

(Example 14) n-butyl acrylate having vinyl sulfide groups at both ends obtained in Example 1 /
2-methoxyethyl acrylate random copolymer 10
5 parts by weight of Perhexa 25B (manufactured by NOF CORPORATION) as a cross-linking agent, 5 parts by weight of ethylene glycol dimethacrylate as a cross-linking aid, and Irganox 1010 (manufactured by Ciba Specialty Chemicals Inc.) as an antioxidant, relative to 0 parts by weight. ) 0.2 parts by weight were blended and kneaded for 15 minutes at 180 ° C. using a Labo Plastomill (manufactured by Toyo Seiki Co., Ltd.) (screw rotation speed 100 rpm). The obtained cured product was hot press molded at 150 ° C. The physical properties of the cured product are shown in Table 1.

Example 15 To 100 parts by weight of polymethylmethacrylate having a vinyl sulfide group at one end obtained in Example 7, 7 parts by weight of benzoyl peroxide as a crosslinking agent and trimethylolpropane as a crosslinking auxiliary agent 5 parts by weight of trimethacrylate and 0.2 parts by weight of Irganox 1010 (manufactured by Ciba Specialty Chemicals Co., Ltd.) as an antioxidant were blended and used at 15 ° C. at 200 ° C. using Labo Plastomill (manufactured by Toyo Seiki Co., Ltd.) Kneading was performed for one minute (screw rotation speed 100 rpm). The obtained cured product was hot press molded at 150 ° C. The physical properties of the cured product are shown in Table 1.

(Example 16) 100 parts by weight of a methyl methacrylate-n-butyl acrylate diblock copolymer having a vinyl sulfide group at the n-butyl side of the polyacrylate obtained in Example 9 was crosslinked. 8 parts by weight of Perhexa 25B (manufactured by NOF CORPORATION) as an agent, 2 parts by weight of triallyl isocyanurate as a crosslinking aid, and 0.2 parts by weight of Irganox 1010 (manufactured by Ciba Specialty Chemicals) as an antioxidant. Blend and use Labo Plastomill (manufactured by Toyo Seiki Co., Ltd.) at 220 ° C for 15
Kneading was performed for one minute (screw rotation speed 100 rpm). The obtained cured product was hot press molded at 180 ° C. The physical properties of the cured product are shown in Table 1.

Example 17 100 parts by weight of an acrylonitrile-n-butyl acrylate diblock copolymer having a vinyl sulfide group at one end, obtained in Example 12, was used as a crosslinking agent, Perhexa 25B (NOF 5 parts by weight), 1 part by weight of triallyl isocyanurate as a crosslinking aid, Irganox 1010 as an antioxidant (manufactured by Ciba Specialty Chemicals)
0.2 parts by weight were blended and kneaded for 15 minutes at 180 ° C. using a Labo Plastomill (manufactured by Toyo Seiki Co., Ltd.) (screw rotation speed 100 rpm). The resulting cured product is 18
Hot press molding was performed at 0 ° C. The physical properties of the cured product are shown in Table 1.

(Example 18) Acrylonitrile having a vinyl sulfide group at one end obtained in Example 13
To 100 parts by weight of (n-butyl acrylate / ethyl acrylate) diblock copolymer, 6 parts by weight of Perhexa 25B (manufactured by NOF Corporation) as a crosslinking agent and 2 parts by weight of triallyl isocyanurate as a crosslinking aid. , Irganox 1010 (Ciba Specialty
Chemicals Co., Ltd.) 0.2 part by weight was blended and kneaded for 15 minutes at 180 ° C. using a Labo Plastomill (Toyo Seiki Co., Ltd.) (screw rotation speed 100 rpm). The obtained cured product was hot press molded at 180 ° C. The physical properties of the cured product are shown in Table 1.

[0208]

[Table 1]

[0209]

INDUSTRIAL APPLICABILITY The vinyl sulfide group-containing polymer of the present invention can be manufactured inexpensively and safely because the purification process can be simplified and the aqueous polymerization is possible. Further, the vinyl sulfide group-containing polymer of the present invention and the cured product obtained by curing the curable composition have excellent heat resistance, weather resistance and oil resistance. Furthermore, the vinyl sulfide group-containing polymer of the present invention and the cured product obtained by curing the curable composition can also be used as a thermoplastic elastomer.

   ─────────────────────────────────────────────────── ─── Continued front page    F term (reference) 4J002 BC021 BD031 BF021 BG031                       BG091 BL001 EX026 FD146                 4J100 AB01P AC03P AG04P AL04P                       AL05P AL08P AL09P AS02P                       AS03P BA04P BC04P BC07P                       BC43P HA35 HA62 HC01                       HC44 HE14

Claims (20)

[Claims] 1. At least one unit selected from acrylic acid ester, methacrylic acid ester, acrylic acid, methacrylic acid, styrene, α-methylstyrene, butadiene, isoprene, vinyl chloride, vinyl acetate, acrylonitrile, and methacrylonitrile. It is derived from a polymer obtained by polymerizing a monomer and has the formula (1) A vinyl sulfide group-containing polymer having at least one vinyl sulfide group in each molecule. 2. The above formula (1): The polymer according to claim 1, which has a vinyl sulfide group represented by the following at the terminal of the molecular chain. 3. A compound having a linear molecular structure and having the formula (1): The polymer according to any one of claims 1 and 2, which has a vinyl sulfide group represented by the following at both ends of the molecular chain. 4. The polymer according to claim 1, wherein the monomer is at least one selected from acrylic acid ester, methacrylic acid ester, and acrylonitrile. 5. A polymer block obtained by polymerizing a monomer containing 50% by weight or more of a methacrylic acid ester, and a polymer block obtained by polymerizing a monomer containing 50% by weight or more of an acrylic acid ester. The polymer according to any one of claims 1 to 4. 6. The polymer according to claim 1, which is obtained by a step of reacting a polymer having at least one mercapto group in one molecule with acetylene. 7. The polymer according to claim 6, wherein the step of reacting with acetylene is performed in the presence of a base. 8. The polymer having at least one mercapto group in one molecule is a polymer having at least one thiocarbonylthio group in one molecule, which is selected from a base, an acid, and a hydrogen-nitrogen bond-containing compound. The polymer according to claim 6, obtained by a step of treating with at least one treating agent selected. 9. The polymer according to claim 8, wherein the treating agent is a base. 10. A polymer having at least one thiocarbonylthio group in one molecule is obtained by the step of polymerizing the monomer in the presence of a compound having a thiocarbonylthio group, and the thiocarbonylthio group is obtained. The polymer according to claim 8 or 9, wherein the compound having: is at least one compound selected from the general formula (2) and the general formula (3): (In the formula, R ¹ is a p-valent organic group having 1 or more carbon atoms, and contains at least one of a nitrogen atom, an oxygen atom, a sulfur atom, a halogen atom, a silicon atom, a phosphorus atom, and a metal atom. May be a high molecular weight compound; Z ¹
Is a hydrogen atom, a halogen atom, or a monovalent organic group having 1 or more carbon atoms, and the monovalent organic group is a nitrogen atom, an oxygen atom, a sulfur atom, a halogen atom, a silicon atom, or a phosphorus atom. It may contain at least one and may be a high molecular weight compound; p is an integer of 1 or more, and when p is 2 or more, Z ¹ may be the same or different, and Chemical 5] (In the formula, R ² is a monovalent organic group having 1 or more carbon atoms, and contains at least one of a nitrogen atom, an oxygen atom, a sulfur atom, a halogen atom, a silicon atom, a phosphorus atom, and a metal atom. Or a high molecular weight compound; Z ²
Is a sulfur atom (when q = 2), an oxygen atom (when q = 2), a nitrogen atom (when q = 3), or a q-valent organic group having 1 or more carbon atoms. The group is a nitrogen atom,
It may contain at least one of an oxygen atom, a sulfur atom, a halogen atom, a silicon atom, and a phosphorus atom, and may be a high molecular weight compound; q is an integer of 2 or more and R ² is the same. But it may be different). 11. The polymer according to claim 10, wherein the compound having a thiocarbonylthio group is represented by the general formula (4): (In the formula, R ³ is a divalent organic group, and is a nitrogen atom, an oxygen atom, a sulfur atom, a halogen atom, a silicon atom, a phosphorus atom,
And at least one of a metal atom, and may be a high molecular weight compound; Z ¹ is a hydrogen atom, a halogen atom, or a monovalent organic group having 1 or more carbon atoms; The valent organic group may contain at least one of a nitrogen atom, an oxygen atom, a sulfur atom, a halogen atom, a silicon atom and a phosphorus atom, and may be a high molecular weight substance; Z ¹ may be the same. May be different). 12. The number average molecular weight (Mn) determined by gel permeation chromatography analysis is from 1000 to 1000.
The polymer according to any one of claims 1 to 11, which is in the range of 00. 13. The polymer according to claim 1, which has a molecular weight distribution (Mw / Mn) determined by gel permeation chromatography analysis of 1.8 or less. 14. A curable composition comprising the following three components (a), (b) and (c) as essential components: (a) The polymer according to any one of claims 1 to 13,
(B) a compound having a hydrogen-silicon bond, and
(C) Hydrosilylation catalyst. 15. The curable composition according to claim 14, wherein the compound (b) having a hydrogen-silicon bond has two or more hydrogen-silicon bonds in one molecule. 16. The curable composition according to claim 14 or 15, wherein the compound (b) having a hydrogen-silicon bond is a compound having a crosslinkable silyl group. 17. The curable composition according to claim 14, wherein the hydrosilylation catalyst (c) is a platinum-containing compound. 18. A curable composition comprising the following two components (a) and (d) as essential components: (a) The polymer according to any one of claims 1 to 13, and (d) a cross-linking agent. . 19. The curable composition according to claim 18, which contains an unsaturated bond-containing compound as a component other than the components (a) and (d). 20. A cured product obtained by curing the curable composition according to claim 14.