JP2000143854A - Foamable resin composition and foam prepared therefrom - Google Patents

Abstract

PROBLEM TO BE SOLVED: To obtain a composition which has a high gel fraction and gives a foam excellent in heat resistance, weatherability, coatability, and adhesiveness by using an alkenylated vinyl polymer, a hydrosilylated compound, and a blowing agent as essential ingredients. SOLUTION: This composition contains a vinyl polymer having at least one alkenyl group of the formula: CH2=C(R1)- (wherein R1 is H or CH3) and preferably having a mol.wt. distribution lower than 1.8, a hydrosilylated compound, and a blowing agent preferably being a hydroxyl compound as essential ingredients. Preferably, the vinyl polymer is a (meth)acrylic polymer and/or a polymer obtained by subjecting a vinyl monomer to atom transfer radical polymerization to give a polymer having a terminal structure of the formula: -C(R2)(R3)(X) (wherein R2 and R3 are each a group bonded to an ethylenically unsaturated group of a vinyl monomer; and X is Cl, Br, or I) and converting the terminal halogen of this polymer into an alkenylated substituent.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

The present invention relates to a foamable resin composition and a foam using the same. For more information,
(A) a vinyl polymer having at least one alkenyl group, (B) a compound containing a hydrosilyl group, and (C)
The present invention relates to a foamable resin composition containing a foaming agent as an essential component, and a foam obtained by foaming and curing the composition at room temperature or under heating.

[0002]

2. Description of the Related Art A method for obtaining a foam by injection, spraying, etc. (so-called "in-situ foaming" type) does not require a large facility for foam molding, and can be filled without gaps due to its irregular shape. In addition, when used as a heat insulating material, there are advantages that the heat insulating property can be improved, and when used in the field of civil engineering and construction, the construction period can be shortened and the transportation cost is low. Representative examples of such foams include urethane foam and silicone foam.

[0003] However, in the case of urethane foam, there is a concern that the toxicity of isocyanate, which is one of the main raw materials, is concerned, and that the obtained foam has poor weather resistance and cannot be used particularly in outdoor exposed parts. . In the case of silicone foam, although there is no problem with weather resistance, it cannot be painted because it repels water-based paint, which has recently become widely used, and it is adhered to wallpaper and siding boards using an adhesive. There is a problem such as not being able to adhere even if trying.

[0004]

As a solution to the above problems, a method using an organic polymer containing an alkenyl group containing no siloxane unit in the molecular skeleton as one component of a foamable resin composition has been proposed. WO 96/15194
No. 6,086,045. As a method for synthesizing an organic polymer containing an alkenyl group, in particular, a polyacrylate polymer, a vinyl monomer having an alkenyl group having a low radical polymerizability or a radical polymerizable when the acrylate monomer is radically polymerized. Using a radical chain transfer agent having an alkenyl group having a low alkenyl group is disclosed. It is also suggested that the compound can be obtained by performing polymerization of methyl (meth) acrylate or the like by living polymerization and then terminating the living terminal with a compound having an alkenyl group.

However, the polyacrylate polymer synthesized by the former general radical polymerization (free radical polymerization) has a high viscosity due to a large molecular weight distribution (Mw / Mn value) of about 2. In addition, there is a problem in handleability of the foamable resin composition. Further, even if a vinyl monomer having an alkenyl group having low radical polymerizability or a radical chain transfer agent is used, it is difficult to introduce an alkenyl group into almost all molecular chains, and these compounds must be used more than necessary. This has problems that the cost increases and the degree of freedom in controlling the physical properties decreases.

Although the latter suggests the possibility of introducing an alkenyl group into a terminal by living polymerization, the type of living polymerization, the type of the terminal group, the method of conversion to an alkenyl group, and the conversion to an alkenyl group are also considered. Not disclosed at all.

[0007]

The present invention relates to the following three components: (A) a vinyl polymer having at least one alkenyl group represented by the following general formula (1): CH ₂ ＣC (R ¹ )-(1) In the formula, R ¹ represents hydrogen or a methyl group. By using (B) a hydrosilyl group-containing compound and (C) a foaming agent as essential components, a foamable resin composition having low viscosity and good handleability can be obtained and foamed and cured at room temperature or under heating. A foam having a high gel fraction and excellent in weather resistance, heat resistance, paintability and adhesiveness can be obtained.

[0008]

BEST MODE FOR CARRYING OUT THE INVENTION The foamable resin composition of the present invention comprises the following three components: (A) a vinyl polymer having at least one alkenyl group represented by the following general formula (1), and CH ₂ ＣC (R ¹ )-(1) In the formula, R ¹ represents hydrogen or a methyl group. (B) A compound containing a hydrosilyl group and (C) a foaming agent are essential components. This is a foam obtained by foaming, curing and curing.

First, the foamable resin composition of the present invention will be described in detail. [About the vinyl polymer having at least one alkenyl group as the component (A)] The crosslinkable group of the vinyl polymer as the component (A), and the alkenyl group represented by the general formula (1) is represented by ( Since it is necessary to form a crosslinked product by reacting and curing with the hydrosilyl group-containing compound as the component (B), at least one component may be present in one molecule, and more than one component may be appropriately selected depending on the desired physical properties of the foam. You can choose. If there is at least one alkenyl group, crosslinking and curing cannot be performed.

The alkenyl group represented by the general formula (1) is not particularly limited, but includes, for example, a hydrocarbon alkenyl group represented by the following general formula (3); An alkenyl group having an ether bond,
An alkenyl group bonded to the main chain via an oxygen atom, such as an alkenyl group having an ester bond represented by general formulas (5) and (6) and an alkenyl group having a carbonate bond represented by general formula (7); And the like. ^{_{CH 2 = C (R 1)}} -R 4 - (3) wherein, ^{R 1} is the same as that described above. R ⁴ represents a direct bond or a divalent hydrocarbon group having 1 to 20 carbon atoms.

In the general formula (3), R ⁴ is not particularly limited, but may be, for example,-(CH ₂ ) _n- (n is an integer of 0 to 10), -CH ₂ CH (CH ₃ )-,- CH
_{2 CH (CH 3) CH 2} - and the like. _{^{CH 2 = C (R 1)}} -R 5 -O- (4) CH 2 = C (R 1) -R 5 -OC (O) - (5) CH 2 = C (R 1) -R 5 -C (O) O— (6) CH ₂ ＣC (R ¹ ) —R ⁵ —OC (O) O— (7) In the formula, R ¹ is the same as described above. R ⁵ represents a divalent organic group having 1 to 20 carbon atoms which may have a direct bond or one or more ether bonds.

[0012] the general formula (4), (5), (6) and (7), it is not particularly limited as ^{R 5,} for _{example, - (CH 2) n -} , (n is 0 to 20 integer ),-
_{CH 2 CH (CH 3) -} , - CH 2 CH (CH 3) CH
_{2 -; - CH 2 OCH 2} CH 2 -, - CH 2 OCH 2 C
_{H 2 CH 2 -, - CH} 2 CH 2 OCH 2 CH 2 -, - C
_{H 2 CH 2 OCH 2 CH 2} CH 2 -; o-, m-, p-
_{C 6 H 4 -, o-,} m-, p-CH 2 -C 6 H 4 -, o
_{-, m-, p-CH 2} -C 6 H 4 -CH 2 - , and the like.

A group having an electron-withdrawing group represented by the general formula (8) is also exemplified as the alkenyl group of the general formula (1). CH ₂ ＣC (R ¹ ) -R ⁵ -C (R ⁶ ) (R ⁷ )-(8) In the formula, R ¹ and R ⁵ are the same as those described above. R ⁶ and R ⁷ both represent an electron withdrawing group for stabilizing carbanion C ⁻ , or one represents an electron withdrawing group and the other represents hydrogen or an alkyl group having 1 to 10 carbon atoms or a phenyl group.

R ⁶ and R ⁷ in the above formula (8)
The electron withdrawing group of is not particularly limited, for example,-
CO ₂ R (ester group), - C (O) R (keto group), -
CON _(R 2) (amide group), - COSR (thioester group), - CN (nitrile group), - NO ₂ (nitro group)
And the like. The substituent R is an alkyl group having 1 to 20 carbon atoms, an aryl group having 6 to 20 carbon atoms, or 7 to 20 carbon atoms.
And an alkyl group having 1 to 10 carbon atoms or a phenyl group is preferable. As R ⁶ and R ⁷ , —CO ₂ R, —C (O) R, and —CN are particularly preferable.

The monomer forming the main chain of the vinyl polymer (A) is not particularly limited, and various monomers can be used. For example, (meth) acrylic acid, methyl (meth) acrylate, ethyl (meth) acrylate, n-propyl (meth) acrylate, isopropyl (meth) acrylate, n- (meth) acrylate Butyl, isobutyl (meth) acrylate, -tert-butyl (meth) acrylate, n-pentyl (meth) acrylate, n-hexyl (meth) acrylate, cyclohexyl (meth) acrylate, (meth) acryl Acid-n-heptyl, (meth) acrylic acid-n-octyl, (meth)
2-ethylhexyl acrylate, nonyl (meth) acrylate, decyl (meth) acrylate, dodecyl (meth) acrylate, phenyl (meth) acrylate, toluyl (meth) acrylate, benzyl (meth) acrylate, ( 2-methoxyethyl (meth) acrylate, 3-methoxybutyl (meth) acrylate, 2- (meth) acrylate
Hydroxyethyl, 2-hydroxypropyl (meth) acrylate, stearyl (meth) acrylate, (meth)
Glycidyl acrylate, 2-aminoethyl (meth) acrylate, γ- (methacryloyloxypropyl) trimethoxysilane, ethylene oxide adduct of (meth) acrylic acid, trifluoromethylmethyl (meth) acrylate, (meth) 2-trifluoromethylethyl acrylate, 2-perfluoroethylethyl (meth) acrylate, 2-perfluoroethyl- (meth) acrylate
2-perfluorobutylethyl, (meth) acrylic acid-
2-perfluoroethyl, perfluoromethyl (meth) acrylate, diperfluoromethylmethyl (meth) acrylate, 2-perfluoromethyl (meth) acrylate-
2-perfluoroethylmethyl, (meth) acrylic acid-
(Meth) acrylic acid-based monomers such as 2-perfluorohexylethyl, 2-perfluorodecylethyl (meth) acrylate, and 2-perfluorohexadecylethyl (meth) acrylate; styrene, vinyltoluene, α-
Styrene monomers such as methylstyrene, chlorostyrene, styrenesulfonic acid and salts thereof; fluorine-containing vinyl monomers such as perfluoroethylene, perfluoropropylene, and vinylidene fluoride; silicon-containing vinyl such as vinyltrimethoxysilane and vinyltriethoxysilane Maleic anhydride, maleic anhydride, monoalkyl and dialkyl esters of maleic acid; fumaric acid, monoalkyl and dialkyl esters of fumaric acid; maleimide, methylmaleimide, ethylmaleimide, propylmaleimide, butylmaleimide, hexylmaleimide; Maleimide monomers such as octylmaleimide, dodecylmaleimide, stearylmaleimide, phenylmaleimide, and cyclohexylmaleimide; acrylonitrile, meta Nitrile group-containing vinyl monomers such as Rironitoriru; acrylamide, amide group-containing vinyl monomers such as methacrylamide, vinyl acetate, vinyl propionate, vinyl pivalate, vinyl benzoate,
Vinyl esters such as vinyl cinnamate; alkenes such as ethylene and propylene; conjugated dienes such as butadiene and isoprene; vinyl chloride, vinylidene chloride, allyl chloride;
Allyl alcohol and the like can be mentioned. These may be used alone or in combination of two or more. In the above expression format, for example, (meth) acrylic acid indicates acrylic acid and / or methacrylic acid.

A vinyl polymer having at least one alkenyl group represented by the general formula (1) and obtained by synthesizing at least 40% by weight of a (meth) acrylic acid monomer among the above monomers. (Meth) acrylic polymers are more preferable in terms of physical properties.

The molecular weight distribution of the vinyl polymer having at least one alkenyl group, that is, the weight average molecular weight (M
The ratio (Mw / Mn) of w) to the number average molecular weight (Mn) is not particularly limited. However, it is preferable that the molecular weight distribution is narrow in order to suppress the viscosity of the curable composition to a low level, to facilitate handling, and to obtain sufficient cured physical properties. The value of the molecular weight distribution is preferably less than 1.8, more preferably 1.7 or less, still more preferably 1.
It is 6 or less, more preferably 1.5 or less, further preferably 1.4 or less, and further preferably 1.3 or less. Most commonly, the molecular weight distribution is measured by gel permeation chromatography (GPC). Chloroform or THF is used as the mobile phase, and a polystyrene gel column is used as the column, and the number average molecular weight and the like can be determined in terms of polystyrene.

The molecular weight of the vinyl polymer having at least one alkenyl group is not particularly limited.
It is preferably in the range of 100 to 100,000. When the molecular weight is 500 or less, the intrinsic properties of the vinyl polymer are hardly exhibited, and when it is 100,000 or more, handling becomes difficult.

The vinyl polymer having at least one alkenyl group can be obtained by various polymerization methods, and the method is not particularly limited. However, from the viewpoint of versatility and easy control of monomers, vinyl polymers having a specific functional group that can be directly introduced into an alkenyl group by a radical polymerization method or converted into an alkenyl group in one or several steps of reaction. And converting the specific functional group into an alkenyl group to obtain a vinyl polymer having at least one alkenyl group.

In the radical polymerization method used in the method for synthesizing a vinyl polymer having a specific functional group containing an alkenyl group, a specific functional group is prepared by using an azo compound, a peroxide or the like as a polymerization initiator. It can be classified into a “general radical polymerization method” in which a monomer having the vinyl monomer is simply copolymerized and a “controlled radical polymerization method” in which a specific functional group can be introduced into a controlled position such as a terminal.

The "general radical polymerization method" is a simple method. However, in this method, a monomer having a specific functional group is introduced into the polymer only stochastically. If it is intended to obtain such a monomer, it is necessary to use this monomer in a considerably large amount. Conversely, if the monomer is used in a small amount, there is a problem that the proportion of the polymer into which this specific functional group is not introduced becomes large. In addition, since it is a free radical polymerization, there is a problem that only a polymer having a wide molecular weight distribution and a relatively high viscosity can be obtained.

The "controlled radical polymerization method" further includes a "chain transfer agent method" in which polymerization is carried out using a chain transfer agent having a specific functional group to obtain a vinyl polymer having a functional group at a terminal. The term "living radical polymerization method" can be classified into a "living radical polymerization method" in which a polymer having a molecular weight almost as designed can be obtained by growing a polymer growth terminal without causing a termination reaction or the like.

The "chain transfer agent method" is capable of obtaining a polymer having a high degree of functionalization, but requires a considerably large amount of a chain transfer agent having a specific functional group with respect to the initiator, and requires a treatment. There is a problem in the economy, including that. Further, similarly to the above-mentioned "general radical polymerization method", there is also a problem that since it is a free radical polymerization, only a polymer having a wide molecular weight distribution and a high viscosity can be obtained.

Unlike these polymerization methods, the “living radical polymerization method” is a radical polymerization which is difficult to control because the polymerization rate is high and a termination reaction is likely to occur due to coupling between radicals. The reaction hardly occurs and the molecular weight distribution is narrow (Mw / Mn is 1.
(About 1 to 1.5) A polymer can be obtained, and the molecular weight can be freely controlled by the charging ratio of the monomer and the initiator.

Therefore, the "living radical polymerization method" can obtain a polymer having a narrow molecular weight distribution and a low viscosity, and can introduce a monomer having a specific functional group into almost any position of the polymer. Therefore, the method for producing a vinyl polymer having the above specific functional group is more preferable.

In the narrow sense of living polymerization,
This refers to polymerization in which the molecular chain grows while the terminal always keeps activity.In general, the pseudo-polymer in which the terminal is inactivated and the terminal that is activated grows in an equilibrium state. Living polymerization is also included. The definition in the present invention is also the latter.

The "living radical polymerization method" has been actively studied by various groups in recent years. Examples thereof include, for example, Journal of American Chemical Society (J. Am. Chem. Soc.), 19
1994, Vol. 116, p. 7943, using a cobalt porphyrin complex, Macromolecules, 1994, 2
7, “Atom Transfer Radical Polymerization” using a radical scavenger such as a nitroxide compound as shown in page 7228, an organic halide or the like as an initiator and a transition metal complex as a catalyst
cal Polymerization: ATRP).

Among the "living radical polymerization methods", the "atom transfer radical polymerization method" in which a vinyl monomer is polymerized with an organic halide or a sulfonyl halide compound as an initiator and a transition metal complex as a catalyst is the above-mentioned "living radical polymerization method". In addition to the features of the `` radical polymerization method, '' vinyl-based polymers having specific functional groups have halogens at the terminals that are relatively advantageous for the functional group conversion reaction, and have a high degree of freedom in designing initiators and catalysts. It is more preferable as a method for producing a united product. As this atom transfer radical polymerization method, for example, Mat
yjaszewski et al., Journal of American Chemical Society (J. Am. Chem. So
c. 1995, 117, 5614, Macromolecules 1995
Year, Volume 28, p. 7901, Science
e) 1996, vol. 272, p. 866, WO 96/30
No. 421, WO97 / 18247 or S
awamoto et al., Macromolecules (Macro)
1995, Vol. 28, p. 1721.

In this atom transfer radical polymerization, an organic halide, particularly an organic halide having a highly reactive carbon-halogen bond (for example, a carbonyl compound having a halogen at the α-position or a compound having a halogen at the benzyl position), Alternatively, a sulfonyl halide compound or the like is used as an initiator.

Using this polymerization method, crosslinkable vinyl polymerization
Organic halogens having two or more starting points to obtain the body
Or a sulfonyl halide compound as an initiator
Used. Specific examples thereof include o-, m-, p-XCH₂-C₆H₄-CH₂X, o
-, M-, p-CH₃C (H) (X) -C₆H₄-C
(H) (X) CH₃, O-, m-, p- (CH₃)₂C
(X) -C₆H₄-C (X) (CH₃)₂  In the above formula, C₆H₄Represents a phenylene group. X is chlorine,
Shows bromine or iodine. RO₂CC (H) (X)-(CH₂)_n-C (H)
(X) -CO₂R, RO₂CC (CH₃) (X)-
(CH₂)_n-C (CH₃) (X) -CO₂R, RC
(O) -C (H) (X)-(CH₂)_n-C (H)
(X) -C (O) R, RC (O) -C (CH₃) (X)
− (CH₂)_n-C (CH₃) (X) —C (O) R In the above formula, R is an alkyl group having 1 to 20 carbon atoms, aryl
Group or aralkyl group. n represents an integer of 0 to 20
And X represents chlorine, bromine or iodine. XCH₂-C (O) -CH₂X, H₃CC (H)
(X) -C (O) -C (H) (X) -CH₃, (H
₃C)₂C (X) -C (O) -C (X) (CH₃)₂,
C ₆H₅C (H) (X)-(CH₂)_n-C (H)
(X) C₆H₅  In the above formula, X represents chlorine, bromine or iodine, and n is 0
Represents an integer of up to 20. XCH₂CO₂− (CH₂)_n-OCOCH₂X, CH
₃C (H) (X) CO₂− (CH₂)_n-OCOC
(H) (X) CH₃, (CH₃)₂C (X) CO₂−
(CH₂)_n-OCOC (X) (CH₃)₂  In the above formula, n represents an integer of 1 to 20. XCH₂C (O) C (O) CH₂X, CH₃C (H)
(X) C (O) C (O) C (H) (X) CH₃, (CH
₃)₂C (X) C (O) C (O) C (X) (C
H₃)₂, O-, m-, p-XCH₂CO₂-C₆H₄
-OCOCH₂X, o-, m-, p-CH₃C (H)
(X) CO₂-C₆H₄-OCOC (H) (X) C
H₃, O-, m-, p- (CH₃)₂C (X) CO₂−
C₆H₄-OCOC (X) (CH₃)₂, O-, m-,
p-XSO₂-C₆H₄-SO₂X In the above formula, X represents chlorine, bromine, or iodine.

The transition metal complex used as the polymerization catalyst is not particularly limited, but is preferably 7 in the periodic table.
It is a metal complex complex having a Group 8, 8, 9, 9, or 11 element as a central metal. More preferably,
Examples thereof include complexes of zero-valent copper, monovalent copper, divalent ruthenium, divalent iron, and divalent nickel. Among them, a copper complex is preferable. Specific examples of monovalent copper compounds include cuprous chloride, cuprous bromide, cuprous iodide, cuprous cyanide, cuprous oxide, cuprous perchlorate, and the like. is there. When a copper compound is used, 2,2'-bipyridyl and its derivatives, 1,10-phenanthroline and its derivatives, tetramethylethylenediamine, pentamethyldiethylenetriamine, hexamethyltris (2-aminoethyl) amine and the like for enhancing the catalytic activity A ligand such as a polyamine is added. In addition, a tristriphenylphosphine complex of divalent ruthenium chloride (RuCl ₂ (PP
h ₃ ) ₃ ) are also suitable as catalysts. When a ruthenium compound is used as a catalyst, aluminum alkoxides are added as an activator. Further, bis (triphenylphosphine) complex of divalent iron (FeCl ₂ (PPh ₃ )
₂ ) Bivalent nickel bistriphenylphosphine complex (NiCl ₂ (PPh ₃ ) ₂ ) and divalent nickel bistributylphosphine complex (NiBr ₂ (PB
u ₃ ) ₂ ) are also suitable as catalysts.

The vinyl-based monomer used in the polymerization is not particularly limited, and any of those already exemplified can be suitably used.

The above polymerization reaction can be carried out without a solvent, but can also be carried out in the following various solvents. The solvent is not particularly limited and includes, for example, hydrocarbon solvents such as benzene and toluene; ether solvents such as diethyl ether, tetrahydrofuran, diphenyl ether, anisole and dimethoxybenzene; halogenated hydrocarbon solvents such as methylene chloride, chloroform and chlorobenzene. Solvents: ketone solvents such as acetone, methyl ethyl ketone and methyl isobutyl ketone; methanol, ethanol, propanol, isopropanol, n-butyl alcohol, te
alcohol solvents such as rt-butyl alcohol; nitrile solvents such as acetonitrile, propionitrile and benzonitrile; ester solvents such as ethyl acetate and butyl acetate; carbonate solvents such as ethylene carbonate and propylene carbonate. These may be used alone or in combination of two or more. The polymerization can also be carried out in an emulsion system or a system using a supercritical fluid CO ₂ as a medium.

The polymerization can be carried out in the range of 0 to 200 ° C., preferably in the range of room temperature to 150 ° C.

The method for producing a vinyl polymer having at least one alkenyl group represented by the general formula (1) will be specifically described in the following [A] to [C], but is not limited thereto. Not something. [A] A method in which an alkenyl group is directly introduced into a polymer main chain when a vinyl polymer is synthesized by radical polymerization. [B] at least one halogen represented by the general formula (2)
A method in which the halogen is substituted with an alkenyl group-containing functional group using a vinyl polymer having two or more vinyl polymers. [C] A method of using a vinyl polymer having at least one hydroxyl group and substituting the hydroxyl group with an alkenyl group-containing functional group.

The method for introducing an alkenyl group directly into the polymer main chain in the above synthesis method [A] is not particularly limited,
Specifically, the following methods [Aa] to [Ab] can be exemplified.

[A-a] When a vinyl polymer is synthesized by living radical polymerization, a polymerizable alkenyl group and a polymerizable alkenyl group represented by the following general formula (9) and the like are added together with a predetermined vinyl monomer. A method in which a compound having an alkenyl group having low polymerizability is also reacted. _{^{H 2 C = C (R 1}} ) -R 8 -R 9 -C (R 1) = CH 2 (9) wherein, ^{R 1} represents a hydrogen or a methyl group, optionally being the same or different Good. R ⁸ is —C (O) O—
(Ester group) or an o-, m- or p-phenylene group. R ⁹ represents a direct bond or a divalent organic group having 1 to 20 carbon atoms which may have one or more ether bonds. When R ⁸ is an ester group, it is a (meth) acrylate compound, and when R ⁸ is a phenylene group, it is a styrene compound.

As R ⁹ in the above general formula (9),
Is not particularly limited, for example, methylene, ethylene, alkylene groups such as propylene; o-, m-, p-phenylene group; aralkyl groups such as benzyl group; _-CH 2 CH ₂ -
O-CH ₂ - or -O-CH ₂ - alkylene group containing an ether bond such as and the like.

Among the compounds of the above general formula (9),
The following are preferred in that they are easy to perform. H₂C = C (H) C (O) O (CH₂)_n-CH = CH
₂, H₂C = C (CH₃) C (O) O (CH₂)_n-C
H = CH₂  In each of the above formulas, n represents an integer of 0 to 20. H₂C = C (H) C (O) O (CH₂)_n-O- (CH
₂)_mCH = CH₂, H ₂C = C (CH₃) C (O) O
(CH₂)_n-O- (CH₂)_mCH = CH₂  In each of the above formulas, n is an integer of 1 to 20, and m is 0 to 2
Indicates an integer of 0. o-, m-, p-divinylbenzene, o-, m-, p-
H₂C = CH-C₆H₄-CH₂CH = CH₂, O-,
m-, pH₂C = CH-C₆H₄-CH₂-C (CH
₃) = CH₂, O-, m-, pH₂C = CH-C₆H
₄-CH₂CH₂CH = CH₂, O-, m-, pH₂
C = CH-C₆H₄-OCH₂CH = CH ₂, O-, m
−, PH₂C = CH-C₆H₄-OCH₂-C (CH
₃) = CH ₂, O-, m-, pH₂C = CH-C₆H
₄-OCH₂CH₂CH = CH₂, O-, m-, pH
₂C = C (CH₃) -C₆H₄-C (CH₃) = C
H₂, O-, m-, pH₂C = C (CH₃) -C₆H
₄-CH₂CH = CH₂, O-, m-, pH₂C = C
(CH₃) -C₆H₄-CH₂C (CH₃) = CH₂,
o-, m-, pH₂C = C (CH₃) -C₆H₄-C
H₂CH₂CH = CH₂, O-, m-, pH₂C = C
(CH₃) -C₆H₄-OCH₂CH = CH₂, O-,
m-, pH₂C = C (CH₃) -C₆H₄-OCH₂
-C (CH₃) = CH₂, O-, m-, pH₂C = C
(CH₃) -C₆H₄-OCH₂CH₂CH = CH₂  In each of the above equations, C₆H₄Represents a phenylene group.

The timing of reacting the compound having both the polymerizable alkenyl group and the compound having a low polymerizability alkenyl group is not particularly limited. , As the second monomer.

[Ab] When a vinyl polymer is synthesized by living radical polymerization, at the end of the polymerization reaction or after completion of the reaction of a predetermined monomer, at least two alkenyl groups having low polymerizability are used as the second monomer. A method of reacting a compound having two or more compounds.

Such a compound is not particularly limited, and examples thereof include a compound represented by the general formula (10). _{^{H 2 C = C (R 1}} ) -R 10 -C (R 1) = CH 2 (10), ^{R 1} represents a hydrogen or a methyl group, may be the same or different from each other. R ¹⁰ represents a divalent organic group having 1 to 20 carbon atoms which may contain one or more ether bonds.

The compound represented by the above general formula (10) is not particularly limited, but it is easily available, and therefore, 1,5-hexadiene, 1,7-octadiene,
1,9-decadiene is preferred.

In the method for synthesizing a vinyl polymer having at least one alkenyl group by directly introducing an alkenyl group into the polymer main chain in the above-mentioned synthesis method [A],
The method [A-b] is preferred because it is easier to control the alkenyl group introduced per molecule.

The method for synthesizing the vinyl polymer having at least one halogen represented by the general formula (2) in the above synthesis method [B] is preferably an atom transfer radical polymerization method. The method of substituting the alkenyl group-containing functional group for the halogen in the polymer is not particularly limited, but specific examples include the following methods [Ba] to [Bd].

[Ba] A method in which various organic metal compounds having an alkenyl group are allowed to act on a vinyl polymer having at least one halogen represented by the general formula (2) to replace the halogen.

Examples of such organometallic compounds include organic lithium, organic sodium, organic potassium, organic magnesium, organic tin, organic silicon, organic zinc, organic copper and the like. In particular, organotin and organocopper compounds are preferred because they selectively react with the halogen of the general formula (2) and have low reactivity with a carbonyl group.

The organotin compound having an alkenyl group is not particularly limited, but is preferably a compound represented by the following formula (11). H ₂ C = C (R ¹ ) C (R ¹¹ ) (R ¹² ) Sn (R ¹³ ) ₃ (11) In the formula, R ¹ is the same as described above. R ¹¹ and R ^{12 each} represent hydrogen, an alkyl group having 1 to 10 carbon atoms, an aryl group having 6 to 10 carbon atoms, or an aralkyl group having 7 to 10 carbon atoms. Is also good. R ¹³ represents an alkyl group having 1 to 10 carbon atoms, an aryl group, or an aralkyl group.

Specific examples of the organotin compound represented by the general formula (11) include allyltributyltin, allyltrimethyltin, allyltri (n-octyl) tin, allyltri (cyclohexyl) tin and the like. Examples of the organic copper compound having an alkenyl group include lithium divinyl copper, lithium diallyl copper, lithium diisopropenyl copper, and the like.

[Bb] A vinyl-based polymer having at least one halogen represented by the general formula (2) is reacted with a stabilized carbanion having an alkenyl group represented by the following general formula (12) or the like. Substituting halogen. ^{M + C - (R 6)} (R 7) -R 5 -C (R 1) = CH 2 ^{(12), R 1, R 5, R} 6 and ^{R 7} are the same as those described above. M ⁺ represents an alkali metal ion or a quaternary ammonium ion.

The alkali metal ions include lithium ion, sodium ion and potassium ion, and the quaternary ammonium ions include tetramethylammonium ion, tetraethylammonium ion, trimethylbenzylammonium ion, trimethyldodecylammonium ion and tetrabutylammonium ion. And the like are specific examples.

The carbanion of the general formula (12) is
A basic compound is allowed to act on the precursor of
Can be obtained by pulling it out. General formula
The precursor compound of the carbanion (12) is as follows.
Such compounds can be exemplified. H₂C = CH-CH (CO₂CH₃)₂, H₂C = CH
-CH (CO₂C₂H₅)₂, H₂C = CH- (C
H₂)_nCH (CO₂CH₃)₂, H₂C = CH- (C
H₂)_nCH (CO₂C₂H₅)₂, O-, m-, p-
H₂C = CH-C₆H ₄-CH (CO₂CH₃)₂, O
-, M-, pH₂C = CH-C₆H₄-CH (CO₂
C₂H₅)₂, O-, m-, pH₂C = CH-C₆H
₄-CH₂CH (CO₂CH₃)₂, O-, m-, p-
H₂C = CH-C₆H₄-CH₂CH (CO₂C
₂H₅)₂, H₂C = CH-CH (C (O) CH₃)
(CO₂C₂H₅), H₂C = CH- (CH₂)_nCH
(C (O) CH₃) (CO₂C₂H₅), O-, m-,
pH₂C = CH-C₆H₄-CH (C (O) CH₃)
(CO₂C ₂H₅), O-, m-, pH₂C = CH-
C₆H₄-CH₂CH (C (O) CH₃) (CO₂C₂
H₅), H₂C = CH-CH (C (O) CH₃)₂, H
₂C = CH- (CH₂)_nCH (C (O) CH₃)₂,
o-, m-, pH₂C = CH-C₆H₄-CH (C
(O) CH₃)₂, O-, m-, pH₂C = CH-C
₆H₄-CH₂CH (C (O) CH₃)₂, H₂C = C
H-CH (CN) (CO ₂C₂H₅), H₂C = CH-
(CH₂)_nCH (CN) (CO₂C₂H₅), O-,
m-, pH₂C = CH-C₆H₄-CH (CN) (C
O₂C₂H₅), O-, m-, pH₂C = CH-C₆
H₄-CH₂CH (CN) (CO₂C₂H ₅), H₂C
= CH-CH (CN)₂, H₂C = CH- (CH₂)_n
CH (CN)₂, O-, m-, pH₂C = CH-C₆
H₄-CH (CN)₂, O-, m-, pH₂C = CH
-C₆H₄-CH₂CH (CN)₂, H₂C = CH-
(CH ₂)_nNO₂, O-, m-, pH₂C = CH-
C₆H₄-CH₂NO₂, O-, m-, pH₂C = C
HC₆H₄-CH₂CH₂NO₂, H₂C = CH-C
H (C₆H₅) (CO₂C₂H₅), H₂C = CH-
(CH₂)_nCH (C₆H ₅) (CO₂C₂H₅), O
-, M-, pH₂C = CH-C₆H₄-CH (C ₆H
₅) (CO₂C₂H₅), O-, m-, pH₂C = C
HC₆H₄-CH ₂CH (C₆H₅) (CO₂C₂H
₅In the above formula, n represents an integer of 1 to 10.

Various basic compounds are used to extract a proton from the above compound to form a carbanion of the general formula (12). These basic compounds are not particularly restricted but include, for example, alkali metals such as sodium, potassium and lithium; sodium methoxide, potassium methoxide, lithium methoxide, sodium ethoxide, potassium ethoxide, lithium ethoxide, sodium- tert-butoxide, potassium-tert-
Metal alkoxides such as butoxide; carbonates such as sodium carbonate, potassium carbonate, lithium carbonate and sodium hydrogen carbonate; hydroxides such as sodium hydroxide and potassium hydroxide; sodium hydride, potassium hydride, methyllithium, ethyllithium and the like Organic metal such as n-butyllithium, tert-butyllithium, lithium diisopropylamide and lithium hexamethyldisilazide; ammonia; alkylamine such as trimethylamine, triethylamine and tributylamine; tetramethylethylenediamine, pentamethyldiethylenetriamine and the like And pyridine compounds such as pyridine and picoline.

The amount of the basic compound used may be an equivalent amount or a small excess amount relative to the precursor, preferably from 1 to 1.
Two equivalents.

A quaternary ammonium salt can also be used as the above-mentioned carbanion. In this case, it is obtained by preparing an alkali metal salt of a carboxylic acid compound and reacting it with a quaternary ammonium halide. Examples of the quaternary ammonium halide include tetramethylammonium halide, tetraethylammonium halide, trimethylbenzylammonium halide, trimethyldodecylammonium halide, and tetrabutylammonium halide.

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

By reacting the above precursor with a basic compound, a carbanion represented by the general formula (12) is prepared. The desired vinyl polymer having a terminal alkenyl group represented by the general formula (1) can be obtained.

[Bc] A vinyl polymer having at least one halogen represented by the general formula (2) is reacted with a simple metal or an organometallic compound to form an enolate anion. To react with an electrophilic compound.

As the metal simple substance, zinc is particularly preferred in that the generated enolate anion is unlikely to cause a side reaction such as attacking or transferring another ester group. Various kinds of electrophilic compounds having an alkenyl group can be used. Examples thereof include an alkenyl group-containing compound having a leaving group such as a halogen or an acetyl group, a carbonyl compound having an alkenyl group, an isocyanate compound having an alkenyl group, and an acid halide having an alkenyl group. Of these, the use of an alkenyl group-containing compound having a leaving group such as a halogen or an acetyl group is preferable because atoms other than carbon are not introduced into the main chain and the weather resistance of the vinyl polymer is not lost.

[Bd] An alkenyl group-containing oxyanion represented by the following general formula (13) or the like or a vinyl polymer having at least one halogen represented by the general formula (2) 14) A method of reacting the alkenyl group-containing carboxylate anion represented by the above formula to replace the halogen with an alkenyl group-containing substituent. _{^{CH 2 = C (R 1)}} -R 5 -O - M + (13) ^{wherein, R 1,} R ⁵ and ^{M +} are the same as those described above. _{^{CH 2 = C (R 1)}} -R 5 -C (O) O - in M + (14) ^{formula, R 1,} R ⁵ and ^{M +} are the same as those described above.

The precursors of the oxyanions represented by the general formulas (13) and (14) are as follows: H ₂ C ＣCH—CH ₂ —OH, H ₂ C ＝ CH—CH (C
_{H 3) -OH, H 2 C} = C (CH 3) -CH 2 -OH,
_{H 2 C = CH- (CH 2} ) n -OH (n represents an integer of _{2~20.), H 2 C =} CH-CH 2 -O- (C
_{H 2) 2 -OH, H 2} C = CH-C (O) O- (C
_{H 2) 2 -OH, H 2} C = C (CH 3) -C (O) O-
_{(CH 2) 2 -OH, o-} , m-, p-H 2 C = CH-
_{C 6 H 4 -CH 2 -OH,} o-, m-, p-H 2 C = C
_{H-CH 2 -C 6 H 4} -CH 2 -OH, o-, m-, p
_{-H 2 C = CH-CH 2} -O-C 6 H 4 -CH 2 -OH
Alcoholic hydroxyl group-containing compounds such as o-, m-, p-
_{H 2 C = CH-C 6} H 4 -OH, o-, m-, p-H 2
_{C = CH-CH 2 -C 6} H 4 -OH, o-, m-, p-
H ₂ C ₌ CH-CH phenolic hydroxyl group-containing compounds such as _{2 -O-C 6 H 4 -OH} ; H 2 C = CH-C (O) -O
_{H, H 2 C = C (} CH 3) -C (O) -OH, H 2 C =
_{CH-CH 2 -C (O)} -OH, H 2 C = CH- (CH
_{. 2) n -C (O)} -OH (n is indicating an integer of _{2~20), H 2 C = CH-} (CH 2) n -OC (O) -
_{(CH 2) m -C (O} ) -OH (m and n are the same or different and are each an integer of 0~19.), O-, m-, p
_{-H 2 C = CH-C 6} H 4 -C (O) -OH, o-, m
_{-, p-H 2 C =} CH-CH 2 -C 6 H 4 -C (O) -
_{OH, o-, m-, p-} H 2 C = CH-CH 2 -O-C
_{6 H 4 -C (O) -OH} , o-, m-, p-H 2 C = C
_{H- (CH 2) n -OC (} O) -C 6 H 4 -C (O) -
A carboxyl group-containing compound such as OH (n represents an integer of 0 to 13);

Various basic compounds are used to extract a proton from the above compound to form an anion of the above formula (13) or (14), and specific examples thereof include a compound of the above formula (12) All basic compounds used in preparing carbanions are preferably used.
As the reaction solvent, any of those used for preparing carbanions is preferably used.

In the above synthesis method (B), since an alkenyl group can be introduced at a high ratio, an atom transfer radical using an organic halide or a sulfonyl halide compound as an initiator and a transition metal complex as a catalyst is used. A method of introducing an alkenyl group by converting a halogen of a vinyl polymer having at least one halogen represented by the general formula (2) obtained by a polymerization method by the method of [Bd] is preferable. Among the methods of [Bd], a method of reacting an alkenyl group-containing carboxylate anion represented by the general formula (14) or the like is more preferable.

A method for producing a vinyl polymer, characterized by using an atom transfer radical polymerization method in which a vinyl monomer is polymerized using an organic halide or a sulfonyl halide compound as an initiator and a transition metal complex as a catalyst, When an organic halide having an alkenyl group is used as an initiator, a vinyl polymer having an alkenyl group at one terminal and the other terminal having the structure represented by the general formula (2) can be obtained. By converting the halogen at the terminal end of the polymer thus obtained into an alkenyl group-containing substituent, a vinyl polymer having alkenyl groups at both ends can be obtained. As the conversion method, the method already described can be used.

The organic halide having an alkenyl group is not particularly limited. For example, the organic halide having the following general formula (15)
Those having the structure shown in FIG. During ^{R 14 R 15 C (X)} -R 16 -R 9 -C (R 1) = CH 2 (15) ^{Equation, R 1,} R ⁹ and X are the same as those described above. R ¹⁴ and R ¹⁵ are hydrogen or an alkyl group having 1 to 20 carbon atoms, an aryl group having 6 to 20 carbon atoms, and 7 to 20 carbon atoms.
Or an aralkyl group of the formula (1) or those linked to each other at the other end. R ¹⁶ is -C (O) O- (ester group),-
C (O)-(keto group) or o-, m-, p-phenylene group.

Specific examples of the organic halide having an alkenyl group represented by the general formula (15) include XCH ₂ C
(O) O (CH ₂ ) _n CH = CH ₂ , H ₃ CC (H)
(X) C (O) O (CH ₂ ) _n CH = CH ₂ , (H
_{3 C) 2 C (X)} C (O) O (CH 2) n CH = C
H ₂ , CH ₃ CH ₂ C (H) (X) C (O) O (C
H ₂ ) _n CH = CH ₂ ,

[0067]

Embedded image

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

[0069]

Embedded image

In the above formulas, X represents chlorine, bromine,
Represents iodine. n is an integer of 1 to 20, m is 0 to 20
Indicates an integer. o, m, p-XCH₂-C₆H₄− (CH₂)_n-CH
= CH₂, O, m, p-CH₃C (H) (X) -C₆H
₄− (CH₂)_n-CH = CH₂, O, m, p-CH₃
CH₂C (H) (X) -C₆H₄− (CH₂)_n-CH
= CH₂  In each of the above formulas, X represents chlorine, bromine, or iodine.
You. n shows the integer of 0-20. o, m, p-XCH₂-C₆H₄− (CH₂)_n-O-
(CH₂)_m-CH = CH₂, O, m, p-CH₃C
(H) (X) -C₆H₄− (CH₂)_n-O- (C
H₂)_m-CH = CH₂, O, m, p-CH₃CH₂C
(H) (X) -C₆H₄− (CH₂)_n-O- (C
H₂)_mCH = CH₂  In each of the above formulas, X represents chlorine, bromine, or iodine.
You. n represents an integer of 1 to 20, m represents an integer of 0 to 20
Show. o, m, p-XCH₂-C₆H₄-O- (CH₂)_n−
CH = CH₂, O, m, p-CH₃C (H) (X) -C
₆H₄-O- (CH₂)_n-CH = CH₂, O, m, p
-CH₃CH₂C (H) (X) -C₆H₄-O- (CH
₂)_n-CH = CH₂  In the above formulas, X represents chlorine, bromine, or iodine.
And n represents an integer of 0 to 20. o, m, p-XCH₂-C₆H₄-O- (CH₂)_n−
O- (CH₂)_m-CH = CH₂, O, m, p-CH₃
C (H) (X) -C₆H₄-O- (CH₂)_n-O-
(CH₂)_m-CH = CH₂, O, m, p-CH₃CH
₂C (H) (X) -C₆H₄-O- (CH₂)_n-O-
(CH₂)_m-CH = CH₂  In each of the above formulas, X represents chlorine, bromine, or iodine.
Show. n represents an integer of 1 to 20, m is an integer of 0 to 20
Is shown.

The organic halide having an alkenyl group further includes a compound represented by the general formula (16). _{^{H 2 C = C (R 1}} ) -R 9 -C (R 14) (X) in ^{-R 17 -R} 15 (16) ^{formula, R 1, R 9, R} 14, R 15, X is as described above Is the same as R ¹⁷ is a direct bond, —C (O) O—
(Ester group), -C (O)-(keto group), or o
-, M-, p-phenylene group.

R ⁹ is a direct bond or a divalent organic group having 1 to 20 carbon atoms (which may contain one or more ether bonds). Is a halogenated allylic compound, in which a vinyl group is bonded to the carbon. In this case, since the carbon-halogen bond is activated by the adjacent vinyl group, R ¹⁷ does not necessarily need to have a C (O) O group or a phenylene group, and may be a direct bond. When R ⁹ is not a direct bond, to activate a carbon-halogen bond,
R ¹⁷ is preferably a C (O) O group, a C (O) group, or a phenylene group.

The compound of the general formula (16) is specifically
Can be exemplified by the following compounds. CH₂= CHCH₂X, CH₂= C (CH₃) CH
₂X, CH₂= CHC (H) (X) CH₃, CH₂= C
(CH₃) C (H) (X) CH₃, CH₂= CHC
(X) (CH₃)₂, CH₂= CHC (H) (X) C₂
H₅, CH₂= CHC (H) (X) CH (CH₃)₂,
CH₂= CHC (H) (X) C₆H₅, CH₂= CHC
(H) (X) CH₂C₆H₅, CH₂= CHCH₂C
(H) (X) -CO₂R, CH₂= CH (CH₂)₂C
(H) (X) -CO₂R, CH₂= CH (CH ₂)₃C
(H) (X) -CO₂R, CH₂= CH (CH₂)₈C
(H) (X) -CO₂R, CH₂= CHCH₂C (H)
(X) -C₆H₅, CH₂= CH (CH ₂)₂C (H)
(X) -C₆H₅, CH₂= CH (CH₂)₃C (H)
(X) -C₆H₅  In each of the above formulas, X represents chlorine, bromine, or iodine.
You. R represents an alkyl group having 1 to 20 carbon atoms, an aryl group,
Represents an aralkyl group.

Specific examples of the halogenated sulfonyl compound having an alkenyl group include the following compounds. _{o-, m-, p-CH 2} = CH- (CH 2) n -C 6 H
_{4 -SO 2 X, o-, m-} , p-CH 2 = CH- (CH
In _{2) n -O-C 6 H} 4 -SO 2 X above wherein, X represents chlorine, bromine, or iodine. n shows the integer of 0-20.

An organic halide having an alkenyl group,
Alternatively, when a halogenated sulfonyl compound or the like is used as an initiator, a polymer having an alkenyl group at one terminal and a halogen terminal at the other terminal represented by the general formula (2) can be obtained. An alkenyl group at the terminal can also be obtained by coupling the halogen terminals with a compound having a total of two or more identical or different functional groups capable of substituting the halogen represented by the general formula (2) of the polymer. Can be obtained.

There are no particular restrictions on the group having two or more identical or different functional groups capable of substituting a terminal halogen, but polyols, polyamines, polycarboxylic acids, polythiols, and salts thereof, alkali metal sulfides, etc. Is preferred. The following compounds can be exemplified as specific examples of these compounds. Ethylene glycol, 1,2-
Propanediol, 1,3-propanediol, 2-methyl-1,3-propanediol, 2,2-dimethyl-
1,3-propanediol, 1,4-butanediol,
1,3-butanediol, 1,2-butanediol,
2,3-butanediol, pinacol, 1,5-pentanediol, 1,4-pentanediol, 2,4-pentanediol, 1,6-hexanediol, 1,7-heptanediol, 1,8-octanediol , 1,9-
Nonanediol, 1,10-decanediol, 1,12
-Dodecanediol, 1,2-cyclopentanediol, 1,3-cyclopentanediol, 1,2-cyclohexanediol, 1,3-cyclohexanediol,
1,4-cyclohexanediol, glycerol, 1,
2,4-butanetriol, catechol, resorcinol, hydroquinone, 1,2-dihydroxynaphthalene,
1,3-dihydroxynaphthalene, 1,5-dihydroxynaphthalene, 2,6-dihydroxynaphthalene, 2,
2′-biphenol, 4,4′-biphenol, bis (4-hydroxyphenyl) methane, 4,4′-isopropylidenephenol, 3,3 ′-(ethylenedioxy) diphenol, α, α′-dihydroxy- p-xylene, 1,1,1-tris (4-hydroxyphenyl)
Polyols such as ethane, pyrogallol, 1,2,4-benzenetriol; and alkali metal salts of the above polyol compounds; ethylenediamine, 1,3-diaminopropane, 1,2-diaminopropane, 1,4-diaminobutane, , 2-diamino-2-methylpropane, 1,
5-diaminopentane, 2,2-dimethyl-1,3-propanediamine, 1,6-hexanediamine, 1,7-
Heptanediamine, 1,8-octanediamine, 1,9
-Diaminononane, 1,10-diaminodecane, 1,1
2-diaminododecane, 4,4'-methylenebis (cyclohexylamine), 1,2-diaminocyclohexane, 1,3-diaminocyclohexane, 1,4-diaminocyclohexane, 1,2-phenylenediamine, 1,
Polyamines such as 3-phenylenediamine, 1,4-phenylenediamine, α, α′-diamino-p-xylene; and alkali metal salts of the above polyamine compounds; oxalic acid, malonic acid, methylmalonic acid, dimethylmalonic acid, succinic acid Acid, methyl succinic acid, glutaric acid, adipic acid, 1,7-heptanedicarboxylic acid, 1,8-octanedicarboxylic acid, 1,9-nonanedicarboxylic acid, 1,10
-Decanedicarboxylic acid, 1,11-undecanedicarboxylic acid, 1,12-dodecanedicarboxylic acid, 1,2-cyclopentanedicarboxylic acid, 1,2-cyclohexanedicarboxylic acid, 1,3-cyclohexanedicarboxylic acid, 1,
4-cyclohexanedicarboxylic acid, 1,3,5-cyclohexanetricarboxylic acid, phthalic acid, isophthalic acid, terephthalic acid, 1,2,3-benzenetricarboxylic acid,
Polycarboxylic acids such as 1,2,4,5-benzenetetracarboxylic acid; and alkali metal salts of the above polycarboxylic acids; 1,2-ethanedithiol, 1,3-propanedithiol, 1,4-butanedithiol, 1,3-butanedithiol, 1,5-pentanedithiol, 1,6-hexanedithiol, 1,7-heptanedithiol, 1,8
-Octanedithiol, 1,9-nonanedithiol, 2
-Mercaptoethyl ether, p-xylene-α, α '
-Dithiol, 1,2-benzenedithiol, 1,3-
Polythiols such as benzenedithiol and 1,4-benzenedithiol; and alkali metal salts of the above polythiol compounds; lithium sulfide, sodium sulfide, and potassium sulfide.

When the above-mentioned polyols, polyamines, polycarboxylic acids, and polythiols are used, a basic compound can be used in combination to promote the substitution reaction, and specific examples thereof include those already exemplified.

In the above synthesis method [C], at least one hydroxyl group
The method for substituting this hydroxyl group with an alkenyl group-containing functional group using a vinyl polymer having two or more vinyl polymers is not particularly limited, and specific examples thereof include the following [Ca] to [Cd].
And the like. The vinyl polymer having at least one hydroxyl group can be obtained by the following methods [Da] to [Df].

[Ca] After a base such as sodium hydroxide or sodium methoxide is allowed to act on a hydroxyl group of a vinyl polymer having at least one hydroxyl group, the hydroxyl group is reacted with an alkenyl group-containing halide such as allyl chloride. How to let. [Cb] A method of reacting a vinyl polymer having at least one hydroxyl group with an alkenyl group-containing isocyanate compound such as allyl isocyanate. [Cc] A method of reacting a vinyl polymer having at least one hydroxyl group with an alkenyl group-containing acid halide such as (meth) acrylic acid chloride in the presence of a base such as pyridine. [Cd] A method of reacting a vinyl polymer having at least one hydroxyl group with an alkenyl group-containing carboxylic acid such as acrylic acid in the presence of an acid catalyst.

The method for producing the vinyl polymer having at least one hydroxyl group used in the method [C] is as follows [D]
-A] to [D-f], but are not limited to these methods. [Da] When a vinyl polymer is synthesized by living radical polymerization, a compound represented by the following general formula (17) or the like having both a polymerizable alkenyl group and a hydroxyl group in one molecule is used as a second monomer. How to react. _{^{H 2 C = C (R 1}} ) -R in 8 -R 9 -OH (17) ^{formula, R 1,} R ⁸ and ^{R 9} are the same as those described above.

It is to be noted that there is no limitation on the timing of reacting a compound having both a polymerizable alkenyl group and a hydroxyl group in one molecule. In particular, when rubber-like properties are expected, the end of the polymerization reaction or the reaction of a predetermined monomer is considered. After completion, it is preferred to react as a second monomer.

[Db] When a vinyl polymer is synthesized by living radical polymerization, at the end of the polymerization reaction or after completion of the reaction of a predetermined monomer, alkenyl having a low polymerizability in one molecule is used as a second monomer. A method of reacting a compound having a group and a hydroxyl group.

Such a compound is not particularly limited, and examples thereof include a compound represented by the general formula (18). _{^{H 2 C = C (R 1}} ) -R 10 -OH (18) In the formula, R ¹ and R ¹⁰ are the same as those described above.

The compound represented by the above general formula (18) is not particularly limited, but alkenyl alcohols such as 10-undecenol, 5-hexenol and allyl alcohol are preferable because they are easily available.

[Dc] By a method as disclosed in JP-A-4-132706 or the like, the carbon-halogen bond represented by the general formula (2) obtained by atom transfer radical polymerization is reduced to at least one. A method of introducing a hydroxyl group into a terminal by hydrolyzing or reacting a halogen of a vinyl polymer having the same with a hydroxyl group-containing compound.

[Dd] The vinyl polymer having at least one carbon-halogen bond represented by the general formula (2) obtained by atom transfer radical polymerization is added to the vinyl polymer represented by the general formula (19)
A method of reacting a stabilized carbanion having a hydroxyl group as described in (1) to replace halogen. ^{M + C - (R 6)} (R 7) -R in 5 -OH (19) ^formula, R 5, ^{R 6} and ^{R 7} are the same as those described above.

[De] A vinyl-based polymer having at least one carbon-halogen bond represented by the general formula (2) obtained by atom transfer radical polymerization may be added to a single metal such as zinc or an organometallic compound. To prepare an enolate anion, followed by reaction with aldehydes or ketones.

[Df] A hydroxyl group-containing oxyanion represented by the following general formula (20) or a hydroxyl group-containing oxyanion represented by the following general formula (21) is added to a vinyl polymer having at least one halogen represented by the general formula (2). A) reacting a hydroxyl group-containing carboxylate anion represented by formula (1) or the like to replace the halogen with a hydroxyl group-containing substituent. ^{HO-R 5 -O - M +} (20) ^{wherein, R 1,} R ⁵ and ^{M +} are the same as those described above. ^{HO-R 5 -C (O)} O - M + (21) ^{wherein, R 1,} R ⁵ and ^{M +} are the same as those described above.

In the present invention, when a halogen is not directly involved in a method for introducing a hydroxyl group such as [Da] to [Db], the method of [Db] is further used because control is easier. preferable. When a hydroxyl group is introduced by converting halogen of a vinyl polymer having at least one carbon-halogen bond represented by the general formula (2) such as [Dc] to [Df], In view of easier control, the method of [D-f] is more preferable.

[Regarding Hydrosilyl Group-Containing Compound as Component (B)] The hydrosilyl group-containing compound as the component (B) is not particularly limited, and various compounds can be used. In other words, the general formula (22) or chain polysiloxane represented by _{^{(23); R 18 3 SiO-}} [Si (R 18) 2 O] a - [Si (H) (R 19) O] b - [ _{^{Si (R 19) (R 20}} ) O] c -SiR 18 3 (22) HR 18 2 SiO- [Si (R 18) 2 O] a - [Si (H) (R 19) O] b - [Si _{^{(R 19) (R 20)}} O] c -SiR 18 in 2 H (23) ^{formula, R 18} and ^{R 19} are an alkyl group having 1 to 6 carbon atoms or a phenyl ^{group, R 20} is 1 to 10 carbon atoms Represents an alkyl group or an aralkyl group. a is 0 ≦ a ≦ 10
0 and b are integers satisfying 2 ≦ b ≦ 100, and c is an integer satisfying 0 ≦ c ≦ 100. A cyclic siloxane represented by the general formula (24);

[0091]

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In the formula, R ²¹ and R ²² have 1 to 6 carbon atoms.
Is an alkyl group or a phenyl group, and R ²³ has 1 carbon atom.
And 10 to 10 alkyl groups or aralkyl groups. d is 0
≦ d ≦ 8, e represents an integer of 2 ≦ e ≦ 10, f represents an integer of 0 ≦ f ≦ 8, and satisfies 3 ≦ d + e + f ≦ 10. And the like.

These may be used alone or as a mixture of two or more.
May be used. Among these siloxanes
From the viewpoint of compatibility with the (meth) acrylic polymer,
Represented by the following general formulas (25) and (26) having a phenyl group
Represented by the general formulas (27) and (28).
Cyclic siloxanes are preferred. (CH₃)₃SiO- [Si (H) (CH₃) O]_g− [Si (C₆H₅)₂O]_h-Si (CH₃)₃ (25) (CH₃)₃SiO- [Si (H) (CH₃) O]_g− [Si (CH₃) ｛CH ₂ C (H) (R²⁴) C₆H₅｝ O]_h-Si (CH₃)₃ (26) where R²⁴Represents hydrogen or a methyl group. g is 2 ≦ g
≦ 100, h represents an integer of 0 ≦ h ≦ 100. C₆H₅
Represents a phenyl group.

[0094]

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In the formula, R ²⁴ represents hydrogen or a methyl group. i is 2 ≦ i ≦ 10, j is 0 ≦ j ≦ 8, and 3 ≦ i +
Indicates an integer satisfying j ≦ 10. C ₆ H ₅ represents a phenyl group.

The hydrosilyl group-containing compound as the component (B) further includes a hydrosilyl group-containing compound represented by any of general formulas (22) to (28) in comparison with a low molecular weight compound having two or more alkenyl groups in the molecule. Can also be used as a compound obtained by performing an addition reaction so that some hydrosilyl groups remain even after the reaction. Various compounds can be used as the compound having two or more alkenyl groups in the molecule. For example, 1,4-pentadiene, 1,5-hexadiene, 1,6-heptadiene,
1,7-octadiene, 1,8-nonadiene, 1,9-
Hydrocarbon compounds such as decadiene, ether compounds such as O, O'-diallylbisphenol A and 3,3'-diallylbisphenol A, diallyl phthalate, diallyl isophthalate, triallyl trimellitate, tetraallyl pyromellitate, etc. And carbonate compounds such as diethylene glycol diallyl carbonate.

The above-mentioned alkenyl group-containing compound is slowly added dropwise to the excess amount of the hydrosilyl group-containing compound represented by the above general formulas (22) to (28) in the presence of a hydrosilylation catalyst to convert the compound. Obtainable. Among these compounds, the following compounds are preferred in consideration of the availability of raw materials, the ease of removal of excess siloxane, and the compatibility of the component (A) with the polymer.

[0098]

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[About the foaming agent of the component (C)] The foaming agent of the component (C) is one which can be foamed during the curing of the vinyl polymer having at least one alkenyl group of the component (A). It is not particularly limited. Examples thereof include volatile hydrocarbon compounds such as propane, butane, pentane and cyclopentane;
Halogenated hydrocarbon compounds such as chlorofluorocarbons and methylene chloride; gases such as air, hydrogen, nitrogen, oxygen, and carbon dioxide. These may be used alone or in combination of two or more.

Further, a hydroxyl group-containing compound which can generate hydrogen by reacting with the hydrosilyl group-containing compound as the component (B) may be used. Such a hydroxyl group-containing compound is not particularly limited. , Alcoholic hydroxyl group-containing compounds, phenolic hydroxyl group-containing compounds, carboxylic acids, water and the like. These may be used alone or in combination of two or more. Moreover, you may use together with said hydrocarbon compound, gas, etc. The hydroxyl group-containing compound may contain an organopolysiloxane or an organopolysiloxane component, but if there is a particular concern about the repellency of the paint or a decrease in the adhesiveness, it is preferable that the compound not containing these components be used. Water; methanol, ethanol, n-propyl alcohol, isopropyl alcohol, n-butanol, isobutanol, t
ert-butanol, ethylene glycol, ethylene glycol monomethyl ether, diethylene glycol,
Alcoholic hydroxyl group-containing compounds such as diethylene glycol and diethylene glycol monomethyl ether; and carboxylic acids such as acetic acid and propionic acid are more preferable.

[Production Method of Foam] The above (A) to (C)
The mixing ratio of the three components is appropriately selected depending on the structure of each component, the desired expansion ratio, and the desired physical properties, and is not particularly limited. However, when the component (C) is a hydroxyl group-containing compound, Is the ratio of the number of moles x of SiH groups in component (B) to the number of moles y of alkenyl groups in component (A) and the number of moles z of OH groups in component (C), where x: y + z is 3
It is preferably 0: 1 to 1:30. More preferably, it is 10: 1 to 1:10. When the molar ratio of SiH is 3
If it exceeds 0, the crosslink density becomes low, and sufficient mechanical strength cannot be obtained. If it is lower than 1/30, sufficient foaming,
No curing occurs.

When the component (C) is a hydroxyl group-containing compound, the ratio of the number of moles y of the alkenyl group of the component (A) to the number of moles z of the OH group of the component (C) is not particularly limited. Expansion ratio, desired physical properties, structure of component (A),
Although it can be appropriately selected depending on the type of the component (C), generally, y: z is preferably from 100: 1 to 1: 100, and preferably 1: 1.
0: 1 to 1:20 is more preferable.

The molding method for foaming and curing the foamable resin composition of the present invention is not particularly limited, and examples thereof include an extrusion foaming method; a continuous foaming method such as a slab foaming method and a double conveyor method; and a method for producing a sandwich panel. In-situ foaming method such as spraying method, injection method, coating method and the like mainly used for architectural heat insulation applications.

The temperature at which the foamable resin composition of the present invention is foamed and cured is not particularly limited. In the case of a so-called in-situ foaming construction method without a sufficient heating device or the like, the temperature is preferably 100 ° C. or less, and more preferably around room temperature. preferable. When a device capable of controlling the temperature is provided, 0 ° C to 200 ° C, preferably 30 ° C to 150 ° C, more preferably 80 ° C to 150 ° C
It is good to cure with.

In the present invention, the addition reaction of the above components (A) and (B) and the dehydrocondensation reaction of the components (B) and (C) when the component (C) is a hydroxyl group-containing compound. , A hydrosilylation catalyst can be added. Such a hydrosilylation catalyst is not particularly limited,
For example, a radical initiator such as an organic peroxide or an azo compound, and a transition metal catalyst can be used.

The radical initiator is not particularly limited.
For example, di-t-butyl peroxide, 2,5-dimethyl-2,5-di (t-butylperoxy) hexane,
Such as 2,5-dimethyl-2,5-di (t-butylperoxy) -3-hexyne, dicumyl peroxide, t-butylcumyl peroxide, α, α′-bis (t-butylperoxy) isopropylbenzene Dialkyl peroxides, benzoyl peroxide, p-chlorobenzoyl peroxide, m-chlorobenzoyl peroxide, 2,4-dichlorobenzoyl peroxide, diacyl peroxides such as lauroyl peroxide, peracid esters such as t-butyl perbenzoate, Peroxydicarbonates such as diisopropyl carbonate, di-2-ethylhexyl percarbonate, 1,1-di (t-butylperoxy) cyclohexane, 1,1-di (t-butylperoxy) -3,3,5-trimethyl Peroxyke such as cyclohexane It can be mentioned Lumpur and the like.

The transition metal catalyst is not particularly limited, and may be, for example, platinum alone, a dispersion of platinum solids in a carrier such as alumina, silica or carbon black, chloroplatinic acid, chloroplatinic acid and an alcohol, an aldehyde, or the like. Examples include a complex with a ketone, a platinum-olefin complex, and a platinum (0) -divinyltetramethyldisiloxane complex. Examples of catalysts other than platinum compounds include RhCl (PPh ₃ ) ₃ ,
RhCl ₃ , RuCl ₃ , IrCl ₃ , FeCl ₃ , A
lCl ₃ , PdCl ₂ .H ₂ O, NiCl ₂ , TiCl
_{4 and the} like. These catalysts may be used alone or in combination of two or more. The amount of the catalyst is not particularly limited, but 1 mol of the alkenyl group of component (A)
It is good to use in the range of 10 ^-1 to 10 ^-8 mol, preferably in the range of 10 ^-3 to 10 ^-6 mol with ^respect to 1. If the amount is less than 10 ⁻⁸ mol, the curing does not proceed sufficiently. Since the hydrosilylation catalyst is expensive, it is preferable not to use 10 ^-1 mol or more. A phosphine compound can be added as a co-catalyst together with the above-mentioned transition metal catalyst.

Further, in the present invention, the volatile hydrocarbon compounds (propane, butane, pentane, cyclopentane, etc.) or the halogenated hydrocarbon compounds (fluorocarbon,
A foaming method utilizing physical properties such as a method of mixing a CFC alternative, methylene chloride, etc.) and evaporating a hydrocarbon compound or a halogenated hydrocarbon compound under reduced pressure or heating to form a foam, an isocyanate compound and A foaming method using chemical and physical properties, such as a method of generating carbon dioxide gas bubbles by adding water and a reaction between the two, a method of using nitrogen gas generated by decomposition of an azo compound, and a method of producing air entrained by mechanical stirring. A mechanical foaming method, such as a method of utilizing as a foam, can also be used in combination.

The foamable resin composition of the present invention contains various additives for adjusting and improving the physical properties, for example, a filler, an antioxidant, an ultraviolet absorber, a light stabilizer, a plasticizer,
An adhesion improver, a flame retardant, a foam stabilizer, a physical property modifier, and the like may be blended.

The above-mentioned adhesion improving agent is not particularly restricted but includes, for example, alkylalkoxysilanes such as methyltrimethoxysilane, dimethyldimethoxysilane, trimethylmethoxysilane, n-propyltrimethoxysilane; dimethyldiisopropenoxysilane; Alkylisopropenoxysilanes such as methyltriisopropenoxysilane and γ-glycidoxypropylmethyldiisopropenoxysilane, γ-glycidoxypropylmethyldimethoxysilane, γ-glycidoxypropyltrimethoxysilane, vinyltrimethoxy Silane, vinyldimethylmethoxysilane, γ-aminopropyltrimethoxysilane, N
Functionalities such as-(β-aminoethyl) -γ-aminopropyltrimethoxysilane, N- (β-aminoethyl) -γ-aminopropylmethyldimethoxysilane γ-mercaptopropyltrimethoxysilane, γ-mercaptopropylmethyldimethoxysilane Alkoxysilanes having a group; silicone varnishes; polysiloxanes and the like.

The foam obtained by foaming and curing the foamable resin composition of the present invention can be used as a cushioning material, a heat insulating material, a soundproofing material, a vibration damping material, a waterproof material, a waterproof material, an airtight material, a protective material, and the like. Can be.

[0112]

EXAMPLES (Production Example 1) In a 500 mL three-necked flask equipped with a reflux tube, cuprous bromide (1.50 g, 10.3 g) was used as a catalyst.
5 mmol), pentamethyldiethylenetriamine (1.65 mL) as a ligand, and diethyl- as an initiator.
2,5-dibromoadipate (9.42 g, 26.2 m
ol), acetonitrile (30 mL) was used as a solvent, and n-butyl acrylate (300 mL) was polymerized at 70 ° C. under a nitrogen atmosphere. When the polymerization rate of n-butyl acrylate was 93%, 1, 7-octadiene (38.6m
L, 0.261 mol) and heated at the same temperature.
The reaction mixture was diluted with ethyl acetate, the catalyst was removed through a column of activated alumina, and volatiles were distilled off under reduced pressure to obtain a polymer [1] having a terminal alkenyl group.

The polymer [1] having at least one alkenyl group was treated with aluminum silicate (Kyowa Chemical Co., Ltd., Kyoward 700PEL) to remove trace impurities in the polymer to obtain a polymer [2]. .

The number average molecular weight of the obtained polymer [2] is G
PC measurement (in terms of polystyrene) showed 13,800, and molecular weight distribution was 1.28. The alkenyl group introduced per oligomer-1 molecule was determined by ¹ H NMR analysis.
The number was 1.84. The viscosity of this polymer is 35 Pa · s
Met.

Example 1 100 g of the polymer [2] obtained in Production Example 1 and a chain siloxane containing an average of 5 hydrosilyl groups and an average of 5 α-methylstyrene groups in the molecule. 1,1,3,3-tetramethyl-1,3-divinyldisiloxane complex of 4 g and 0-valent platinum 0.13
The mixture was manually mixed with the mixture at room temperature and further dissolved while mixing about 2 g of n-propyl alcohol. This mixture was poured into a mold and left at room temperature. After a while, the mixture was foamed and cured to obtain a sponge-like cured product (foam). The amount of the chain siloxane used was 1.5 equivalents in terms of the molar ratio of the hydrosilyl group, and the amount of the platinum catalyst used was about 1 × 10 ⁻³ equivalents in terms of the molar ratio, based on the vinyl groups of the polymer. This sponge-like cured product was immersed in toluene for 24 hours, and the gel fraction was measured from the change in weight before and after, and the gel fraction was about 90%. The state (paintability) when a commercially available water-based paint for construction was applied to the obtained foam,
Table 1 shows the surface condition (heat resistance) after curing at 3 ° C. for 3 days.

Comparative Example 1 Instead of the polymer [2] used in Example 1, the alkenyl-terminated molecular weight was about 1
When a cured product was prepared in the same manner as in Example 1 except that 10,000 polyoxypropylene glycols were used, a sponge-like cured product (foam) was obtained. The amount of chain siloxane used was 1.5 equivalents in terms of molar ratio of hydrosilyl groups and the amount of platinum catalyst used was about 1 × in terms of molar ratio with respect to the vinyl groups of the polymer.
10 ^-3 equivalents. This sponge-like cured product was immersed in toluene for 24 hours, and the gel fraction was measured from the change in weight before and after, and the gel fraction was about 90%. Table 1 shows the state (paintability) when a commercially available water-based paint for construction was applied to the obtained foam, and the surface state (heat resistance) after curing the foam at 150 ° C. for 3 days.

(Comparative Example 2) Instead of the polymer [2] used in Example 1, the alkenyl-terminated molecular weight 1
A cured product was prepared in the same manner as in Example 1 except that 7,200 terminal vinyl polydimethylsiloxane was used to obtain a sponge-shaped cured product (foam). The amount of the chain siloxane used was 1.5 equivalents in terms of the molar ratio of the hydrosilyl group, and the amount of the platinum catalyst used was about 1 × 10 ⁻³ equivalents in terms of the molar ratio, based on the vinyl groups of the polymer. This sponge-like cured product was immersed in toluene for 24 hours, and the gel fraction was measured from the change in weight before and after, and the gel fraction was about 90%.
Table 1 shows the state (paintability) when a commercially available water-based paint for construction was applied to the obtained foam, and the surface state (heat resistance) after curing the foam at 150 ° C. for 3 days.

[0118]

[Table 1]

As is clear from the results shown in Table 1, the foam of Example 1 was excellent in both coating properties and heat resistance. On the other hand, Comparative Example 1 had good coatability, but poor heat resistance. Comparative Example 2 had poor coatability but good heat resistance.

[0120]

The foamable resin composition of the present invention has a low viscosity because the molecular weight distribution of the vinyl polymer having an alkenyl group is narrow, and a foamable resin composition having good handleability can be obtained. The foamed and cured foam has a high gel fraction due to a high alkenyl group introduction rate, and is excellent in heat resistance, weather resistance, paintability, adhesiveness, and the like.

 ──────────────────────────────────────────────────続 き Continuing on the front page (72) Inventor Kazuaki Ono 1-2-80 Yoshida-cho, Hyogo-ku, Kobe-shi, Hyogo Prefecture Kobe Research Institute Functional Materials RD Center Kobe Research Institute 1-2-80 Yoshida-cho, Hyogo-ku, Kobe

Claims (9)

[Claims] (A) a vinyl polymer having at least one alkenyl group represented by the following general formula (1): CH ₂ ＣC (R ¹ )-(1) R ¹ represents hydrogen or a methyl group. A foamable resin composition comprising (B) a hydrosilyl group-containing compound and (C) a foaming agent as essential components. 2. The foamable resin composition according to claim 1, wherein the foaming agent (C) is a hydroxyl group-containing compound. 3. The foamable resin composition according to claim 1, wherein the molecular weight distribution of the vinyl polymer (A) is less than 1.8. 4. The method according to claim 1, wherein the vinyl polymer (A) is (meth)
The foamable resin composition according to any one of claims 1 to 3, which is an acrylic polymer. 5. The foamable resin composition according to claim 1, wherein the vinyl polymer as the component (A) is produced by a living radical polymerization method. 6. The foamable resin composition according to claim 1, wherein the vinyl polymer as the component (A) is produced by an atom transfer radical polymerization method. . 7. Component (A) comprising the following steps: (1) A vinyl polymer having a terminal structure represented by the general formula (2) is produced by polymerizing a vinyl monomer by an atom transfer radical polymerization method. , -C (R ² ) (R ³ ) (X) (2) In the formula, R ² and R ³ represent a group bonded to the ethylenically unsaturated group of the vinyl monomer. X represents chlorine, bromine or iodine. (2) The foamable polymer according to any one of claims 1 to 6, which is a vinyl polymer obtained by converting a terminal halogen of the polymer into a substituent having an alkenyl group represented by the general formula (1). Resin composition. 8. A method for producing a vinyl polymer, wherein the component (A) comprises the following steps: (1) a vinyl monomer is polymerized by a living radical polymerization method;
(2) Subsequently, at least two alkenyl groups having low polymerizability
The foamable resin composition according to any one of claims 1 to 6, wherein the foamable resin composition is a vinyl polymer obtained by reacting a compound having two or more compounds. 9. A foam obtained by foaming and curing the foamable resin composition according to any one of claims 1 to 8.