JP2001323016A - Method for purifying vinyl-based polymer - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a method for purifying a vinyl-based polymer to use the vinyl-based polymer as a component for a hydrosilylation reactive composition. SOLUTION: The vinyl-based polymer produced by an atom transfer radical polymerization is purified by adsorption treatment using both an acidic adsorbent and a basic adsorbent to give the vinyl-based polymer for the hydrosilylation reactive composition.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

The present invention relates to a method for purifying a vinyl polymer, a vinyl polymer, a hydrosilylation-reactive composition and a curable composition.

[0002]

2. Description of the Related Art A hydrosilylation reaction is utilized for functional group conversion, cross-linking reaction and the like, and is one of industrially very useful reactions. For example, a polymer having an alkenyl group as a functional group at the terminal of a molecular chain is cross-linked and cured by using a hydrosilyl group-containing compound as a curing agent, and gives a cured product having excellent heat resistance and durability, It is known that a polymer having a crosslinkable silyl group at the terminal is produced by reacting a polymer having a crosslinkable silyl group with a polymer having a alkenyl group at the terminal. These hydrosilylation reactions proceed by heating, but a hydrosilylation catalyst is added to accelerate the reaction more quickly. Such hydrosilylation catalysts include radical initiators such as organic peroxides and azo compounds, and transition metal catalysts. In particular, it is known that when a transition metal catalyst is used, hydrosilylation can be rapidly performed with a catalytic amount.

On the other hand, a living polymerization method is generally known as a precise synthesis method of a polymer. In the living polymerization, not only can the molecular weight and the molecular weight distribution be controlled, but also a polymer having a clear terminal structure can be obtained. Therefore,
Living polymerization is one of the effective methods for introducing a functional group into a polymer terminal. Recently, a polymerization system capable of living polymerization has been found in radical polymerization, and research on living radical polymerization has been actively conducted. In particular, a vinyl polymer having a narrow molecular weight distribution can be obtained by utilizing atom transfer radical polymerization. As examples of atom transfer radical polymerization, an organic halide or a sulfonyl halide compound is used as an initiator, groups 8, 9 and 10 of the periodic table,
Alternatively, a polymerization system using a metal complex having a Group 11 element as a central metal as a catalyst may be used. (For example, Matyjasze
wski et al. Am. Chem. Soc. 1995,
117, 5614, Macromolecules 1
995, 28, 7901, Science 1996,
272,866, or Sawamoto et al., Mac.
romolecules 1995, 28, 1721).

[0004]

However, since a transition metal complex which is a polymerization catalyst remains in a vinyl polymer produced by atom transfer radical polymerization, coloring of the polymer is difficult.
Problems such as effects on physical properties and environmental safety occur. For example, in a vinyl polymer having an alkenyl group at a terminal produced by the atom transfer radical polymerization method, the remaining catalyst or the like acts as a catalyst poison for the hydrosilylation reaction, so that the hydrosilylation reaction is inhibited and an expensive transition is caused. The problem that many metal catalysts were needed arises.

The present inventors have found that the hydrosilylation activity can be improved by contacting and purifying a vinyl polymer obtained by atom transfer radical polymerization with an adsorbent such as aluminum silicate (JP-A-11-193307). ). However, the amount of the adsorbent used at that time is large, and the load on the environment due to disposal, the increase in the purification cost due to the adsorbent, and the like arise as problems. The present invention solves this problem, and provides an economical and efficient method for purifying a vinyl polymer, a hydrosilylation-reactive polymer, and a composition.

[0006]

Means for Solving the Problems (1) In the present invention, a vinyl polymer produced by utilizing atom transfer radical polymerization of a vinyl monomer using a transition metal complex as a polymerization catalyst is brought into contact with an adsorbent. Is a method for purifying a vinyl polymer by using an acidic adsorbent and a basic adsorbent together as an adsorbent. (2) Further, the present invention relates to a method for producing a vinyl polymer having at least one alkenyl group in a molecule or an intermediate product obtained during the step of producing the vinyl polymer by contacting the vinyl polymer with an adsorbent. In a method for purifying a vinyl polymer or an intermediate product, an acid adsorbent and a basic adsorbent are used in combination as an adsorbent. (3) In the present invention, the vinyl polymer having at least one alkenyl group in the molecule is produced by using atom transfer radical polymerization of a vinyl monomer using a transition metal complex as a polymerization catalyst. It is also a purification method characterized in that it is a product. (4) The present invention also relates to a method for purifying a vinyl polymer for using the vinyl polymer as one component of a hydrosilylation-reactive composition, the method comprising the steps of: using an acidic adsorbent and a basic adsorbent together; It is also a purification method characterized by treatment purification. (5) The present invention is also a vinyl polymer obtained by the purification method of (1) to (4), and a hydrosilylation-reactive composition containing the polymer. (6) The present invention also relates to (A) a vinyl polymer having an alkenyl group obtained by the purification method of (1) to (4), and (B) at least 1.1 hydrosilyl groups in a molecule. It is also a curable composition containing a compound having the same. (7) Further, the present invention relates to a crosslinked polymer obtained by hydrosilylation of a hydrosilyl group-containing compound having both an alkenyl group-containing vinyl polymer obtained by the purification method of (1) to (4) and a crosslinkable silyl group. It is also a vinyl polymer having a hydrophilic silyl group. (9) The present invention is also a curable composition containing the above-mentioned vinyl polymer having a crosslinkable silyl group.

[0007]

DETAILED DESCRIPTION OF THE INVENTION The present invention relates to a vinyl polymer obtained by contacting a vinyl polymer produced by atom transfer radical polymerization of a vinyl monomer with a transition metal complex as a polymerization catalyst with an adsorbent. Is a purification method characterized by using an acidic adsorbent and a basic adsorbent in combination as an adsorbent, and the vinyl polymer to be purified is produced using atom transfer radical polymerization. The polymer is not limited thereto, and may be a vinyl polymer obtained by another production method. Atom transfer radical polymerization First, atom transfer radical polymerization will be described in detail. The atom transfer radical polymerization in the present invention is one of living radical polymerization, in which an organic halide or a sulfonyl halide compound is used as an initiator, and a vinyl complex is radically polymerized using a metal complex having a transition metal as a central metal as a catalyst. Is the way. Specifically, for example, Matyja
szewski et al., Journal of American Chemical Society (J. Am. Chem. Soc.)
1995, 117, 5614, Macromolecules, 1995, 2
8, 7901, Science 19
1996, vol. 272, p. 866, WO96 / 30421, WO97 / 18247, WO98 / 014.
No. 80, WO98 / 40415, or S
awamoto et al., Macromolecules (Macro)
molecules) 1995, 28, 1721
Page, JP-A-9-208616, JP-A-8-411
No. 17 publication.

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. For example, C ₆ H ₅ —CH ₂ X, C ₆ H ₅ —C (H) (X) CH ₃ , C ₆
H ₅ —C (X) (CH ₃ ) ₂ (where C ₆ H ₅ is a phenyl group, X is chlorine, bromine, or iodine) R ³ —C (H) (X) —CO ₂ R ⁴ , R ³ -C (CH ₃ )
^{_{(X) -CO 2 R 4,}} R 3 -C (H) (X) -C (O)
R ⁴ , R ³ —C (CH ₃ ) (X) —C (O) R ⁴ , wherein R ³ and R ⁴ are a hydrogen atom or an alkyl, aryl, or aralkyl group having 1 to 20 carbon atoms , X is chlorine, bromine, or iodine. R ³ —C ₆ H ₄ —SO ₂ X (In each of the above formulas, R ³ is a hydrogen atom or a carbon atom.
To 20 alkyl groups, aryl groups, or aralkyl groups, and X is chlorine, bromine, or iodine).

By performing atom transfer radical polymerization of a vinyl monomer using an organic halide or a sulfonyl halide compound as an initiator, a vinyl polymer having a terminal structure represented by the general formula (1) can be obtained. —C (R ¹ ) (R ² ) (X) (1) (wherein R ¹ and R ² each represent a group bonded to an ethylenically unsaturated group of a vinyl monomer. X represents chlorine, bromine or iodine. An organic halide or a sulfonyl halide compound having both a functional group that initiates polymerization and a specific reactive functional group that does not initiate polymerization can be used as an initiator of atom transfer radical polymerization. In such a case, a vinyl polymer having a specific reactive functional group at one main chain terminal and a terminal structure represented by the general formula (1) at the other main chain terminal is obtained. Such specific reactive functional groups include alkenyl groups, crosslinkable silyl groups, hydroxyl groups, epoxy groups, amino groups, amide groups, and the like. Utilizing the reactivity of these reactive functional groups, one or more steps can be used to introduce other appropriate functional groups into the vinyl polymer.

The organic halide having an alkenyl group is not limited, and examples thereof include those having a structure represented by the general formula (2). R ⁶ R ⁷ C (X) —R ⁸ —R ⁹ —C (R ⁵ ) ＝ CH ₂ (2) (wherein, R ⁵ is hydrogen or a methyl group, and R ⁶ and R ⁷ are hydrogen or carbon A monovalent alkyl group, an aryl group, or an aralkyl group of the formulas 1 to 20, or ones linked to each other at the other end, R ⁸ represents —C (O) O— (ester group), —C (O) — ( Keto group), or o-, m-, p
A phenylene group, R ⁹ is a direct bond, or has 1 to 2 carbon atoms;
X is a divalent organic group which may contain one or more ether bonds. X is chlorine, bromine, or iodine. Specific examples of the substituents R ⁶ and R ⁷ include hydrogen, methyl, and ethyl. , N-propyl group, isopropyl group, butyl group,
Examples include a pentyl group and a hexyl group. R ⁶ and R ⁷ may be linked at the other end to form a cyclic skeleton.

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

[0012]

Embedded image (In each formula mentioned above, X is chlorine, bromine or iodine, n represents an integer of _{0~20,) XCH 2 C (O} ) O (CH 2) n O (CH 2) m CH = C
H ₂ , H ₃ CC (H) (X) C (O) O (CH ₂ ) _n O (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 , CH ₃ CH ₂ C (H) (X) C (O) O (CH ₂ ) _n O (C
H ₂ ) _m CH = CH ₂ ,

[0013]

Embedded image(In each of the above formulas, X represents chlorine, bromine, or iodine.
Prime, n is an integer of 1 to 20, m is an integer of 0 to 20) o, m, p-XCH_Two-C₆H_Four− (CH_Two)_n-CH = C
H_Two, O, m, p-CH_ThreeC (H) (X) -C₆H_Four− (CH_Two)
_n-CH = CH_Two, O, m, p-CH_ThreeCH_TwoC (H) (X) -C₆H_Four− (C
H_Two)_n-CH = CH_Two(In the above formulas, X represents chlorine, bromine, or iodine.
Prime, n is an integer of 0 to 20) o, m, p-XCH_Two-C₆H_Four− (CH_Two)_n-O- (C
H_Two)_m-CH = CH_Two, O, m, p-CH_ThreeC (H) (X) -C₆H_Four− (CH_Two)
_n-O- (CH_Two)_m-CH = CH_Two, O, m, p-CH_ThreeCH_TwoC (H) (X) -C₆H_Four− (C
H_Two)_n-O- (CH_Two)_mCH = CH_Two(In the above formulas, X represents chlorine, bromine, or iodine.
Prime, n is an integer of 1 to 20, m is an integer of 0 to 20) o, m, p-XCH_Two-C₆H_Four-O- (CH_Two)_n-CH
= CH_Two, O, m, p-CH_ThreeC (H) (X) -C₆H_Four-O- (C
H_Two)_n-CH = CH_Two, O, m, p-CH_ThreeCH_TwoC (H) (X) -C₆H_Four-O-
(CH_Two)_n-CH = CH _Two(In the above formulas, X represents chlorine, bromine, or iodine.
Prime, n is an integer of 0 to 20) o, m, p-XCH_Two-C₆H_Four-O- (CH_Two)_n-O-
(CH_Two)_m-CH = CH_Two, O, m, p-CH_ThreeC (H) (X) -C₆H_Four-O- (C
H_Two)_n-O- (CH_Two)_m-CH = CH_Two, O, m, p-CH_ThreeCH_TwoC (H) (X) -C₆H_Four-O-
(CH_Two)_n-O- (CH _Two)_m-CH = CH_Two(In the above formulas, X represents chlorine, bromine, or iodine.
, N is an integer of 1 to 20, m is an integer of 0 to 20) As an organic halide having an alkenyl group,
The compound represented by the general formula (3) is exemplified. H_TwoC = C (R^Five) -R⁹-C (R⁶) (X) -R^Ten-R⁷ (3) (where R^Five, R⁶, R⁷, R⁹, X is the same as above, R
^TenIs a direct bond, -C (O) O- (ester group), -C
(O)-(keto group) or o-, m-, p-phenyl
Represents a len group) R⁸Is a direct bond or a divalent organic group having 1 to 20 carbon atoms
(Which may contain one or more ether bonds)
Is a direct bond, the carbon to which the halogen is bonded
With a vinyl group bonded to the halogenated allylic compound
is there. In this case, the carbon-halogen is linked by an adjacent vinyl group.
Is activated, so that R^TenAs C (O) O
Group or phenylene group is not necessary
It may be a combination. R⁹Is not a direct bond,
In order to activate the halogen-halogen bond, R^TenAs C
(O) O group, C (O) group and phenylene group are preferred.

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

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

Organic halogen having a crosslinkable silyl group
The compound is not particularly limited. For example, the compound represented by the general formula (4)
One having a structure shown in FIG. R⁶R⁷C (X) -R⁸-R⁹-C (H) (R^Five) CH_Two− [Si (R¹¹)_2-b(Y)_b O]_m-Si (R¹²)_3-a(Y)_a (4) (where R^Five, R⁶, R⁷, R⁸, R⁹, X is the same as above,
R¹¹, R¹²Is an alkyl group having 1 to 20 carbon atoms,
Aryl group, aralkyl group, or (R ′)_ThreeSiO-
(R ′ is a monovalent hydrocarbon group having 1 to 20 carbon atoms,
The three R's may be the same or different
I) represents a triorganosiloxy group represented by¹¹Ma
Or R¹²When two or more exist, they are the same.
Or may be different. Y is a hydroxyl group or water
A decomposable group, and when two or more Y
They may be one or different. a is 0, 1,
2, or 3, and b represents 0, 1, or 2.
m is an integer of 0-19. Where a + mb ≧ 1
To specifically exemplify the compound of the general formula (4), XCH_TwoC (O) O (CH_Two)_nSi (OCH_Three)_Three, CH_Three
C (H) (X) C (O) O (CH_Two)_nSi (OC
H_Three)_Three, (CH_Three)_TwoC (X) C (O) O (CH_Two)_nSi
(OCH_Three)_Three, XCH_TwoC (O) O (CH_Two)_nSi (C
H_Three) (OCH_Three)_Two, CH_ThreeC (H) (X) C (O) O
(CH_Two)_nSi (CH_Three) (OCH_Three)_Two, (CH_Three)_TwoC
(X) C (O) O (CH_Two)_nSi (CH_Three) (OCH_Three)
_Two(In each of the above formulas, X is chlorine, bromine, iodine, and n is
An integer from 0 to 20, XCH_TwoC (O) O (CH_Two)_nO (CH_Two)_mSi (OC
H_Three)_Three, H_ThreeCC (H) (X) C (O) O (CH_Two)_nO
(CH_Two)_mSi (OCH_Three)_Three, (H_ThreeC)_TwoC (X) C
(O) O (CH_Two)_nO (CH_Two)_mSi (OCH_Three)_Three, C
H_ThreeCH_TwoC (H) (X) C (O) O (CH_Two)_nO (CH
_Two)_mSi (OCH_Three)_Three, XCH_TwoC (O) O (CH_Two)_n
O (CH_Two)_mSi (CH_Three) (OCH_Three)_Two, H_ThreeCC
(H) (X) C (O) O (CH_Two)_nO (CH_Two)_m-Si
(CH_Three) (OCH_Three)_Two, (H_ThreeC)_TwoC (X) C (O)
O (CH_Two)_nO (CH_Two)_m-Si (CH_Three) (OCH_Three)
_Two, CH_ThreeCH_TwoC (H) (X) C (O) O (CH_Two)_nO
(CH_Two)_m-Si (CH_Three) (OCH_Three)_Two(In each of the above formulas, X is chlorine, bromine, iodine, and n is
An integer of 1 to 20, m is an integer of 0 to 20) o, m, p-XCH_Two-C₆H_Four− (CH_Two)_TwoSi (OC
H_Three)_Three, O, m, p-CH_ThreeC (H) (X) -C₆H_Four−
(CH_Two)_TwoSi (OCH_Three)_Three, O, m, p-CH_ThreeCH_Two
C (H) (X) -C₆H_Four− (CH_Two)_TwoSi (OC
H_Three)_Three, O, m, p-XCH_Two-C₆H_Four− (CH_Two)_ThreeS
i (OCH_Three)_Three, O, m, p-CH_ThreeC (H) (X)-
C₆H_Four− (CH_Two)_ThreeSi (OCH_Three)_Three, O, m, p-C
H_ThreeCH_TwoC (H) (X) -C₆H_Four− (CH_Two)_ThreeSi (O
CH_Three)_Three, O, m, p-XCH_Two-C₆H_Four− (CH_Two)_Two
-O- (CH_Two)_ThreeSi (OCH_Three)_Three, O, m, p-CH
_ThreeC (H) (X) -C₆H_Four− (CH_Two)_Two-O- (CH_Two)
_ThreeSi (OCH_Three)_Three, O, m, p-CH_ThreeCH_TwoC (H)
(X) -C₆H_Four− (CH_Two)_Two-O- (CH_Two)_ThreeSi (O
CH_Three)_Three, O, m, p-XCH_Two-C₆H_Four-O- (C
H_Two)_ThreeSi (OCH_Three)_Three, O, m, p-CH_ThreeC (H)
(X) -C₆H_Four-O- (CH_Two)_ThreeSi (OCH_Three)_Three,
o, m, p-CH_ThreeCH_TwoC (H) (X) -C₆H_Four-O-
(CH_Two)_Three-Si (OCH_Three)_Three, O, m, p-XCH_Two
-C₆H_Four-O- (CH_Two)_Two-O- (CH_Two)_Three-Si (O
CH_Three)_Three, O, m, p-CH_ThreeC (H) (X) -C₆H_Four
-O- (CH_Two)_Two-O- (CH_Two)_ThreeSi (OCH_Three)_Three,
o, m, p-CH_ThreeCH_TwoC (H) (X) -C₆H_Four-O-
(CH_Two)_Two-O- (CH _Two)_ThreeSi (OCH_Three)_Three(In the above formulas, X represents chlorine, bromine, or iodine.
Element) and the like.

As the organic halide having a crosslinkable silyl group, those having a structure represented by the general formula (5) are further exemplified. ^{_{(R 12) 3-a (}} Y) a Si- [OSi (R 11) 2-b (Y) b] m -CH 2 -C (H) (R 5) -R 9 -C (R 6) ( ^{X) -R 10 -R 7 (5} ) ( ^{wherein, R 5, R 7, R} 8, R 9, R 10, R 11, R 12, a,
b, m, X, and Y are the same as above. Specific examples of such a compound include (CH ₃ O) ₃ SiCH ₂ CH ₂ C (H) (X) C ₆ H ₅ ,
(CH ₃ O) ₂ (CH ₃ ) SiCH ₂ CH ₂ C (H) (X)
_{C 6 H 5, (CH 3} O) 3 Si (CH 2) 2 C (H) (X) -
CO ₂ R, (CH ₃ O) ₂ (CH ₃ ) Si (CH ₂ ) ₂ C
_{(H) (X) -CO 2} R, (CH 3 O) 3 Si (CH 2) 3
C (H) (X) -CO 2 R, (CH 3 O) 2 (CH 3) Si
_{(CH 2) 3 C (H} ) (X) -CO 2 R, (CH 3 O) 3 S
_{i (CH 2) 4 C (} H) (X) -CO 2 R, (CH 3 O) 2
_{(CH 3) Si (CH 2} ) 4 C (H) (X) -CO 2 R,
_{(CH 3 O) 3 Si (} CH 2) 9 C (H) (X) -CO
_{2 R, (CH 3 O)} 2 (CH 3) Si (CH 2) 9 C (H)
(X) —CO ₂ R, (CH ₃ O) ₃ Si (CH ₂ ) ₃ C
_{(H) (X) -C 6} H 5, (CH 3 O) 2 (CH 3) Si
_{(CH 2) 3 C (H} ) (X) -C 6 H 5, (CH 3 O) 3 Si
_{(CH 2) 4 C (H} ) (X) -C 6 H 5, (CH 3 O) 2 (C
_{H 3) Si (CH 2)} 4 C (H) (X) -C 6 H 5, ( in each formula above, X is chlorine, bromine or iodine, R represents an alkyl group having 1 to 20 carbon atoms, aryl Group, aralkyl group) and the like.

The organic halide having a hydroxyl group or the sulfonyl halide compound is not particularly limited, and examples thereof include the following. HO- (CH ₂₎ in _{n -OC (O) C (H} ) (R) (X) ( the formulas above, X is chlorine, bromine or iodine, R represents a hydrogen atom or an alkyl having 1 to 20 carbon atoms, Group,
(Aryl group, aralkyl group, n is an integer of 1 to 20) The organic halide having the amino group or the sulfonyl halide compound is not particularly limited, and examples thereof include the following. H ₂ N- (CH ₂₎ in _{n -OC (O) C (H} ) (R) (X) ( the formulas above, X is chlorine, bromine or iodine, R represents a hydrogen atom or 1 to 20 carbon atoms, An alkyl group of
(Aryl group, aralkyl group, n is an integer of 1 to 20) The organic halide having the epoxy group or the sulfonyl halide compound is not particularly limited, and examples thereof include the following.

[0019]

Embedded image (In each of the above formulas, X is chlorine, bromine, or iodine, R is a hydrogen atom or an alkyl group having 1 to 20 carbon atoms,
An aryl group, an aralkyl group, and n is an integer of 1 to 20) In order to obtain a polymer having two or more reactive functional groups in one molecule, an organic halide having two or more starting points or a halogenated compound Preferably, a sulfonyl compound is used as the initiator. To give a concrete example,

[0020]

Embedded image

[0021]

Embedded image And the like.

The transition metal complex used as the polymerization catalyst is not particularly limited, but is preferably 7
It is a metal complex having a Group 8, 8, 9, 10, or 11 element as a central metal. More preferred are complexes of zero-valent copper, monovalent copper, divalent ruthenium, divalent iron or divalent nickel. Among them, a copper complex is preferable. Specific examples of the monovalent copper compound include:
Examples include cuprous chloride, cuprous bromide, cuprous iodide, cuprous cyanide, cuprous oxide, cuprous perchlorate and the like. When a copper compound is used, 2,2'-bipyridyl or a derivative thereof, 1,10-phenanthroline or a derivative thereof, or tetramethylethylenediamine, pentamethyldiethylenetriamine or hexamethyltris (2-aminoethyl) amine is used to increase the catalytic activity. And the like are added as ligands. In addition, a tristriphenylphosphine complex of divalent ruthenium chloride (RuCl
₂ (PPh ₃ ) ₃ ) is also suitable as a catalyst. When a ruthenium compound is used as a catalyst, aluminum alkoxides are added as an activator. Further, bistriphenylphosphine complex of divalent iron (FeCl ₂ (PP
h ₃ ) ₂ ) a divalent nickel bistriphenylphosphine complex (NiCl ₂ (PPh ₃ ) ₂ ) and a divalent nickel bistributylphosphine complex (NiBr ₂ (P
Bu ₃ ) ₂ ) is also suitable as a catalyst.

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

The polymerization reaction can be carried out without a solvent, but can be carried out in various solvents. The type of the solvent is not particularly limited, and examples thereof include hydrocarbon solvents such as bendiene and toluene; diethyl ether, tetrahydrofuran,
Ether solvents such as diphenyl ether, anisole and dimethoxybendiene; methylene chloride, chloroform,
Halogenated hydrocarbon solvents such as chlorobendiene; ketone solvents such as acetone, methyl ethyl ketone and methyl isobutyl ketone; methanol, ethanol, propanol, isopropanol, n-butyl alcohol, ter
alcohol solvents such as t-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; Amide solvents such as dimethylformamide and N, N-dimethylacetamide are exemplified. 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.

Although not limited, the polymerization is carried out at 0-200 ° C.
And preferably at room temperature to 150 ° C.
Range. Will be described in detail vinyl polymer in the present invention will now for the vinyl polymer.

The vinyl polymer is not particularly limited, but is preferably produced by atom transfer radical polymerization of a vinyl monomer. Such vinyl monomers are not particularly limited, and those already exemplified can be used. These vinyl monomers may be used alone or a plurality of them may be copolymerized. Among them, styrene-based monomers and (meth) acrylic-acid-based monomers are preferred from the viewpoint of the physical properties of the product. More preferred are acrylate monomers and methacrylate monomers, particularly preferred are acrylate monomers, and still more preferred is butyl acrylate. In the present invention, these preferred monomers may be copolymerized with other monomers, or further, may be subjected to block copolymerization. In this case, it is preferable that these preferred monomers are contained in a weight ratio of 40%.

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

The number average molecular weight of the vinyl polymer is not particularly limited, but is preferably in the range of 500 to 1,000,000, more preferably 1000 to 100,000. When the molecular weight is too low, the intrinsic properties of the vinyl polymer are hardly exhibited, and when it is too high, handling becomes difficult.

The vinyl polymer may have a reactive functional group in the molecule. When the compound has a reactive functional group in the molecule, it may be present at either the side chain or the terminal of the molecular chain. The reactive functional group is not particularly limited, and examples thereof include an alkenyl group, a hydroxyl group, an amino group, a crosslinkable silyl group, and a polymerizable carbon-carbon double bond group. The reactive functional group can be converted to another suitable functional group in one or several steps. For example, also in the present invention, a vinyl polymer having an alkenyl group is synthesized by converting a reactive functional group such as a hydroxyl group. It will be described in detail vinyl polymer having a next alkenyl group for vinyl polymer having an alkenyl group. The vinyl polymer having an alkenyl group can be used as a component of the hydrosilylation reactive composition.
For example, a vinyl polymer having at least one alkenyl group in the molecule is crosslinked by performing a hydrosilylation reaction using a hydrosilyl group-containing compound as a curing agent to give a cured product. Further, a vinyl polymer having a crosslinkable functional group can be obtained by subjecting a vinyl polymer having at least one alkenyl group in the molecule to a hydrosilylation reaction with a hydrosilane compound having a crosslinkable functional group.

The vinyl polymer having an alkenyl group is produced by utilizing atom transfer radical polymerization.

The alkenyl group in the present invention is not limited, but is preferably one represented by the general formula (6). ^{_{H 2 C = C (R 13}} ) - (6) (. Wherein, R ¹³ represents an organic group having hydrogen or a C 1-20) In the general formula (6), R ¹³ is hydrogen or 1 carbon atoms 20
Is an organic group. The organic group having 1 to 20 carbon atoms is not particularly limited, but is preferably an alkyl group having 1 to 20 carbon atoms, an aryl group having 6 to 20 carbon atoms, or an aralkyl group having 7 to 20 carbon atoms. The following groups are exemplified. _{- (CH 2) n -CH 3} , -CH (CH 3) - (CH 2) n -
_{CH 3, -CH (CH 2 CH} 3) - (CH 2) n -CH 3, -
_{CH (CH 2 CH 3) 2} , -C (CH 3) 2 - (CH 2) n -
_{CH 3, -C (CH 3)} (CH 2 CH 3) - (CH 2) n -C
_{H 3, -C 6 H 5,} -C 6 H 5 (CH 3), - C 6 H 5 (C
_{H 3) 2, - (CH} 2) n -C 6 H 5, - (CH 2) n -C 6 H 5
(CH ₃ ),-(CH ₂ ) _n -C ₆ H ₅ (CH ₃ ) ₂ (n is an integer of 0 or more, and the total number of carbon atoms of each group is 20 or less) Of these, R ¹³ is hydrogen Or a methyl group is more preferable.

Further, although not limited, it is preferable that the alkenyl group of the vinyl polymer is not activated by a carbonyl group, alkenyl group, or aromatic ring conjugated to the carbon-carbon double bond.

The form of bonding between the alkenyl group and the main chain of the polymer is not particularly limited, but may be a carbon-carbon bond, an ester bond, an ester bond, a carbonate bond, an amide bond, a urethane bond, or the like. preferable.

The alkenyl group may be present in the molecule of the vinyl polymer, but when the cured product of the curable composition of the present invention is particularly required to have rubber-like properties, it has a large effect on rubber elasticity. At least one of the alkenyl groups is preferably located at the terminal of the molecular chain, since the molecular weight between the crosslinking points can be increased. More preferably, all the alkenyl groups have at the molecular chain terminal. More preferably, it is present at the molecular end.

Although the number of alkenyl groups is not particularly limited,
In order to obtain a cured product having higher crosslinkability, on average one or more, preferably 1.2 or more, more preferably 1.5 or more
Number or more.

Next, the method for producing a vinyl polymer having an alkenyl group will be described in detail, but the present invention is not limited to these methods.

(Aa) When a vinyl polymer is synthesized by atom transfer radical polymerization, for example, a polymerizable alkenyl group and a polymerizable compound in one molecule as shown in the following general formula (9) are used. A method in which a compound having an alkenyl group is reacted as a second monomer. ^{_{H 2 C = C (R 14}} ) -R 15 -R 16 -C (R 17) = CH 2 (9) ( wherein, R ¹⁴ represents a hydrogen or a methyl group, R ¹⁵ is -C
(O) O- or an o-, m-, p-phenylene group; R ¹⁶ represents a direct bond or a divalent organic group having 1 to 20 carbon atoms, including one or more ether bonds. May be. R ¹⁷ represents hydrogen or an organic group having 1 to 20 carbon atoms) In the general formula (9), R ¹⁷ represents hydrogen or 1 to 20 carbon atoms.
Is an organic group. The organic group having 1 to 20 carbon atoms is not particularly limited, but is preferably an alkyl group having 1 to 20 carbon atoms, an aryl group having 6 to 20 carbon atoms, or an aralkyl group having 7 to 20 carbon atoms. The following groups are exemplified. _{- (CH 2) n -CH 3} , -CH (CH 3) - (CH 2) n -
_{CH 3, -CH (CH 2 CH} 3) - (CH 2) n -CH 3, -
_{CH (CH 2 CH 3) 2} , -C (CH 3) 2 - (CH 2) n -
_{CH 3, -C (CH 3)} (CH 2 CH 3) - (CH 2) n -C
_{H 3, -C 6 H 5,} -C 6 H 5 (CH 3), - C 6 H 5 (C
_{H 3) 2, - (CH} 2) n -C 6 H 5, - (CH 2) n -C 6 H 5
(CH ₃ ),-(CH ₂ ) _n -C ₆ H ₅ (CH ₃ ) ₂ (n is an integer of 0 or more, and the total number of carbon atoms of each group is 20 or less) Of these, R ¹⁷ is hydrogen Or a methyl group is more preferable.

The timing of reacting a compound having both a polymerizable alkenyl group and a low polymerizable alkenyl group in one molecule is not limited. When it is expected that the second monomer is reacted at the end of the polymerization reaction or after completion of the reaction of a predetermined monomer.

(Ab) When synthesizing a vinyl polymer by atom transfer radical polymerization, for example, 1,5-hexadiene, 1,7-octadiene, A method comprising reacting a compound having at least two alkenyl groups having low polymerizability, such as 9,9-decadiene.

(Ac) A vinyl polymer having at least one highly reactive carbon-halogen bond at the terminal obtained by atom transfer radical polymerization may be added to an organic tin such as allyltributyltin or allyltrioctyltin. A method of reacting various organometallic compounds having such an alkenyl group to replace halogen.

(Ad) The vinyl polymer having at least one highly reactive carbon-halogen bond at the terminal obtained by atom transfer radical polymerization has an alkenyl group as shown in the general formula (10). A method in which halogen is substituted by reacting a stabilized carbanion. ^{M + C - (R 18)} (R 19) -R 20 -C (R 17) = CH 2 (10) ( wherein, R ¹⁷ same .R ¹⁸ in the above, R ¹⁹ together carbanion C ^- stable Or one of them is the above-mentioned electron-withdrawing group and the other is hydrogen or a carbon atom having 1 to 10 carbon atoms.
Represents an alkyl group or a phenyl group. R ²⁰ represents a direct bond or a divalent organic group having 1 to 10 carbon atoms, and may contain one or more ether bonds. M ⁺ represents an alkali metal ion or a quaternary ammonium ion. Examples of the electron withdrawing groups for R ¹⁸ and R ¹⁹ include —CO ₂ R (ester group), —C (O) R (keto group), and —CON (R ₂ ).
(Amide group), -COSR (thioester group), -CN
(Nitrile group), - NO ₂ is (nitro group), and the _{like, -CO 2 R, -C (O} ) R and -CN are particularly preferable. The substituent R is an alkyl group having 1 to 20 carbon atoms,
An aryl group having 6 to 20 carbon atoms or an aralkyl group having 7 to 20 carbon atoms, preferably an alkyl group having 1 to 10 carbon atoms or a phenyl group.

(Ae) A vinyl-based polymer having at least one highly reactive carbon-halogen bond at the terminal obtained by atom transfer radical polymerization is reacted with a simple metal such as zinc or an organometallic compound. To prepare an enolate anion, followed by 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. , An electrophilic compound having an alkenyl group.

(Af) A vinyl polymer having at least one highly reactive carbon-halogen bond at the terminal obtained by atom transfer radical polymerization may, for example, be a compound represented by the general formula (1)
1) A method of reacting an oxyanion or a carboxylate anion having an alkenyl group as shown in (12) to replace halogen. ^{_{H 2 C = C (R 17}} ) -R 21 -O - M + (11) ( wherein, R ^17, M ⁺ is the same .R ²¹ above are 1 to 2 carbon atoms
H ₂ C 有機 C (R ¹⁷ ) -R ²² -C (O) O ⁻ M ⁺ (12) ¹⁷ , M ⁺ is the same as described above, and R ²² is a direct bond or a divalent organic group having 1 to 20 carbon atoms which may contain one or more ether bonds.

Among the methods (Aa) to (Af), the methods (Ab) and (Af) are preferable because the control is easier. Hereinafter, the method of introducing (Ab) and (Af) will be described in detail. Diene Compound Addition Method [(Ab) Method] In the (Ab) method, a compound having at least two alkenyl groups having low polymerizability in a vinyl polymer obtained by atom transfer radical polymerization of a vinyl monomer ( (Hereinafter referred to as “diene-based compound”).

At least two alkenyl groups of the diene compound may be the same or different from each other. As the alkenyl group, a terminal alkenyl group [CH ₂ ＣC (R)-
R ′; R is hydrogen or an organic group having 1 to 20 carbon atoms, R ′ is an organic group having 1 to 20 carbon atoms, and R and R ′ may be bonded to each other to have a cyclic structure. Or an internal alkenyl group [R'-C (R) = C (R) -R '; R is hydrogen or an organic group having 1 to 20 carbon atoms, R' is an organic group having 1 to 20 carbon atoms, Two Rs (or two R's) may be the same or different. Any two of the two substituents R and R ′ may be bonded to each other to form a cyclic structure. And a terminal alkenyl group is more preferred. R is hydrogen or an organic group having 1 to 20 carbon atoms. Examples of the organic group having 1 to 20 carbon atoms include an alkyl group having 1 to 20 carbon atoms and 6 to 2 carbon atoms.
An aryl group having 0 and an aralkyl group having 7 to 20 carbon atoms are preferred. Among them, R is particularly preferably hydrogen or a methyl group.

Further, among the alkenyl groups of the diene compound, at least two alkenyl groups may be conjugated.

Specific examples of the diene compound include, for example,
Isoprene, piperylene, butadiene, myrcene, 1,
Examples thereof include 5-hexadiene, 1,7-octadiene, 1,9-decadiene, and 4-vinyl-1-cyclohexene, and 1,5-hexadiene, 1,7-octadiene and 1,9-decadiene are preferred.

Living radical polymerization of a vinyl monomer is carried out, the obtained polymer is isolated from the polymerization system, and the isolated polymer is subjected to a radical reaction with a diene compound to give an alkenyl group at the desired terminal. Although it is possible to obtain a vinyl polymer having the following formula, a method of adding a diene compound to the polymerization reaction system at the end of the polymerization reaction or after the completion of the reaction of a predetermined vinyl monomer is more preferable because it is simple.

It is necessary to adjust the amount of the diene compound to be added according to the radical reactivity of the alkenyl group of the diene compound. When there is a large difference in the reactivity of the two alkenyl groups, the diene-based compound may be in an equivalent amount or a small excess amount with respect to the polymerized growth terminal. Since both of the alkenyl groups react and the polymerization ends are coupled with each other, the amount of the diene compound added is preferably an excess amount with respect to the polymer growing terminal, preferably 1.5 times or more, and more preferably It is at least 3 times, particularly preferably at least 5 times. Nucleophilic Substitution Method ((Af) Method) The (Af) method comprises adding an alkenyl group to a vinyl polymer having at least one highly reactive carbon-halogen bond at a terminal obtained by atom transfer radical polymerization. Characterized by reacting an oxyanion or a carboxylate anion with the halogen to replace the halogen.

The oxyanion or carboxylate anion having an alkenyl group is not particularly restricted but includes, for example, those represented by the general formula (11) or (12). ^{_{H 2 C = C (R 17}} ) -R 21 -O - M + (11) ( wherein, R ^17, M ⁺ is the same .R ²¹ above are 1 to 2 carbon atoms
0 bivalent may contain one or more ether bonds with organic _{groups) H 2 C = C (R} 17) -R 22 -C (O) O - M + (12) ( wherein, R ¹⁷ , M ⁺ is the same as described above, and R ²² may be a direct bond or a divalent organic group having 1 to 20 carbon atoms and may contain one or more ether bonds.) Specific examples of oxy anion or carboxylate anion For example, ammonia; alkylamines such as trimethylamine, triethylamine and tributylamine;
Basic compounds such as polyamines such as tetramethylethylenediamine and pentamethyldiethylenetriamine; and pyridine compounds such as pyridine and picoline may be used in an equivalent amount or a small excess amount with respect to the precursor.
~ 1.2 equivalents.

Examples of the solvent used for reacting the precursor compound with the basic compound include salts of alkenyl alcohols such as allyl alcohol; salts of allyloxy alcohols such as ethylene glycol monoallyl ether; Alkenyl group-containing phenolic hydroxyl groups such as roxyphenol; alkenyl group-containing carboxylate salts such as 10-undecylenic acid, 4-pentenoic acid and vinyl acetic acid;

M ⁺ is a counter cation, and examples of M ⁺ include alkali metal ions, specifically, lithium ions, sodium ions, potassium ions, and quaternary ammonium ions. Examples of the quaternary ammonium ion include a tetramethylammonium ion, a tetraethylammonium ion, a tetrabenzylammonium ion, a trimethyldodecylammonium ion, a tetrabutylammonium ion, and a dimethylpiperidinium ion, and a sodium ion and a potassium ion are preferable.

The oxyanion or carboxylate anion may be used in an excess amount with respect to the halogen, preferably 1 to 5 equivalents, more preferably 1 to 2 equivalents, and still more preferably 1.0 to 1.2 equivalents. Is equivalent.

The solvent for carrying out this reaction is not particularly limited, but a solvent having a relatively high polarity is preferable, for example, ether solvents such as diethyl ether, tetrahydrofuran, diphenyl ether, anisole and dimethoxybendiene; methylene chloride, chloroform Halogenated hydrocarbon solvents such as acetone; methyl ethyl ketone;
Ketone solvents such as methyl isobutyl ketone; methanol, ethanol, propanol, isopropanol, n
Alcohol solvents such as -butyl alcohol and tert-butyl alcohol; nitrile solvents such as acetonitrile, propionitrile and benzonitrile; ethyl acetate;
Ester solvents such as butyl acetate; carbonate solvents such as ethylene carbonate and propylene carbonate;
Amide solvents such as dimethylformamide and dimethylacetamide; sulfoxide solvents such as dimethylsulfoxide; and the like. These can be used alone or in combination of two or more. Among these, acetone,
Polar solvents such as dimethylsulfoxide, dimethylformamide, dimethylacetamide, hexamethylphosphoric triamide, and acetonitrile are more preferred. Although the reaction temperature is not limited, it is generally 0 to 150 ° C, more preferably room temperature to 100 ° C.

Further, amines, ammonium salts, crown ethers and the like may be added to the reaction system as a reaction accelerator.

The oxyanion or carboxylate anion may be prepared by reacting a base with an alcohol or carboxylic acid as a precursor in the reaction system instead of the oxyanion or carboxylate anion.

When an ester group is present in the side chain of the vinyl polymer or in the main chain, use of an oxyanion having a high nucleophilicity may cause transesterification. It is more preferable to use Method for converting hydroxyl group to alkenyl group The vinyl polymer having at least one alkenyl group can be obtained from a vinyl polymer having at least one hydroxyl group, and the methods exemplified below can be used. It is not limited.

(Ag) A method in which a base such as sodium methoxide is allowed to act on a hydroxyl group of a vinyl polymer having at least one hydroxyl group and reacted with an alkenyl group-containing halide such as allyl chloride.

(Ah) A method in which an isocyanate compound containing an alkenyl group such as allyl isocyanate is reacted with a hydroxyl group of a vinyl polymer having at least one hydroxyl group.

(Ai) An alkenyl group-containing acid halide such as (meth) acrylic acid chloride or 10-undecenoic acid chloride is added to a hydroxyl group of a vinyl polymer having at least one hydroxyl group in the presence of a base such as pyridine. How to react.

(Aj) Acrylic acid, pentenoic acid,
A method in which an alkenyl group-containing carboxylic acid such as 0-undecenoic acid is reacted in the presence of an acid catalyst.

(Ak) A method of reacting a vinyl polymer having a hydroxyl group with a diisocyanate compound and reacting a compound having both an alkenyl group and a hydroxyl group with the remaining isocyanate group. The compound having both an alkenyl group and a hydroxyl group is not particularly limited, and examples thereof include alkenyl alcohols such as 10-undecenol, 5-hexenol, and allyl alcohol.

The diisocyanate compound is not particularly limited, and any conventionally known diisocyanate compound can be used. For example, tolylene diisocyanate, 4,4'-
Diphenylmethane diisocyanate, hexamethyl diisocyanate, xylylene diisocyanate, meta-xylylene diisocyanate, 1,5-naphthalene diisocyanate, hydrogenated diphenylmethane diisocyanate,
Isocyanate compounds such as hydrogenated toluylene diisocyanate, hydrogenated xylylene diisocyanate, and isophorone diisocyanate; These can be used alone or in combination of two or more. Further, a blocked isocyanate may be used.

In order to make better use of the weather resistance, it is preferable to use a diisocyanate compound having no aromatic ring, such as hexamethylene diisocyanate and hydrogenated diphenylmethane diisocyanate. The following methods are examples of the method for producing a vinyl polymer having at least one hydroxyl group used in the methods (B) and (Ag) to (Aj) for synthesizing the vinyl polymer having a hydroxyl group. However, the present invention is not limited to these methods.

(Ba) When a vinyl polymer is synthesized by atom transfer radical polymerization, for example, the following general formula (1)
A method of reacting a compound having both a polymerizable alkenyl group and a hydroxyl group in one molecule as the second monomer as described in 5). H ₂ C ＝ C (R ¹⁴ ) —R ¹⁵ —R ¹⁶ —OH (15) (wherein R ¹⁴ , R ¹⁵ and R ¹⁶ are the same as above) A polymerizable alkenyl group and a hydroxyl group in one molecule There is no limitation on the timing of reacting the compound having both of the above. Particularly, in the case of living radical polymerization, when a rubber-like property is expected, the reaction is carried out as the second monomer at the end of the polymerization reaction or after completion of the reaction of a predetermined monomer. Is preferred.

(Bb) When a vinyl polymer is synthesized by atom transfer radical polymerization, at the end of the polymerization reaction or after the reaction of a predetermined monomer is completed, for example, 10-undecenol, 5-hexenol, allyl alcohol or the like is used. A method of reacting alkenyl alcohol.

(Bf) The terminal of the vinyl polymer having at least one highly reactive carbon-halogen bond at the terminal obtained by atom transfer radical polymerization is hydrolyzed or reacted with a hydroxyl group-containing compound to give a terminal. Method of introducing a hydroxyl group into a compound.

(Bg) The vinyl polymer having at least one highly reactive carbon-halogen bond at the terminal obtained by atom transfer radical polymerization has a hydroxyl group-containing stable group represented by the general formula (16). A method of reacting a halogenated carbanion to replace a halogen. ^{M + C - (R 18)} (R 19) -R 20 -OH (16) as an electron withdrawing group ^{(wherein, R 18, R 19, R} 20, are the same) R ^18, R ¹⁹ are, -CO ₂ R (ester group), - C (O) R ( keto group), - CON (R ₂₎
(Amide group), -COSR (thioester group), -CN
(Nitrile group), - NO ₂ is (nitro group), and the _{like, -CO 2 R, -C (O} ) R and -CN are particularly preferable. The substituent R is an alkyl group having 1 to 20 carbon atoms,
An aryl group having 6 to 20 carbon atoms or an aralkyl group having 7 to 20 carbon atoms, preferably an alkyl group having 1 to 10 carbon atoms or a phenyl group.

(Bh) A vinyl polymer having at least one highly reactive carbon-halogen bond at a terminal obtained by atom transfer radical polymerization is reacted with a simple metal such as zinc or an organometallic compound. To prepare an enolate anion and then react with aldehydes or ketones.

(Bi) The vinyl polymer having at least one highly reactive carbon-halogen bond at the terminal obtained by atom transfer radical polymerization may be added to a hydroxyl group represented by the general formula (17) or (18). A oxyanion or a carboxylate anion having the following to replace halogen. ^{HO-R 21 -O - M +} (17) ( wherein, R ²¹ and M ⁺ are the ^{same) HO-R 22 -C (O} ) O - M + (18) ( wherein, R ²² and M ⁺ Is the same as above.) As for M ⁺ , reaction conditions, solvent and the like, all those described in the description of (A-f) can be suitably used. (Bj) When synthesizing a vinyl polymer by atom transfer radical polymerization, at the end of the polymerization reaction or after completion of the reaction of a predetermined monomer, as a second monomer, an alkenyl group having low polymerizability in one molecule and A method of reacting a compound having a hydroxyl group. Such a compound is not particularly limited, and examples thereof include a compound represented by the general formula (19). ^{_{H 2 C = C (R 14}} ) -R 21 -OH (19) ( wherein, R ¹⁴ and R ²¹ are the same as those described above.) In particular limitation is imposed on the compound represented by the above general formula (19) Not available, but 10-
Alkenyl alcohols such as undecenol, 5-hexenol, allyl alcohol are preferred.

Among the synthesizing methods of (Ba) to (Bj), (Bb) and (B-b) are easier to control.
Method i) is preferred. Next will be described in detail adsorption treatment method for the adsorption process.

The adsorption treatment method of the present invention is a method for purifying a vinyl polymer by bringing the vinyl polymer into contact with an adsorbent, wherein an acidic adsorbent and a basic adsorbent are used in combination as the adsorbent. Purification method. The adsorption treatment method of the present invention is also a method for purifying a vinyl polymer for using the vinyl polymer as one component of the hydrosilylation reactive composition. This purification method can also be performed on a vinyl polymer obtained by a production method other than the atom transfer radical polymerization method.

The adsorbent used in the present invention is an acidic adsorbent and a basic adsorbent. The definition of “acidic (or basic) adsorbent” in the present invention is “adsorbent in which the liquid property of the adsorbent is acidic (basic in the case of a basic adsorbent)” or “basic compound (basic adsorption). Adsorbent having a high adsorptivity for acidic compounds in the case of an adsorbent).

Examples of the adsorbent include a synthetic resin adsorbent such as activated carbon and ion exchange resin, and an inorganic adsorbent such as zeolite, and any of them can be suitably used.

Activated carbon is mostly carbonaceous charcoal and has high adsorptivity. In the production method, for example, wood, lignite, peat, etc. are treated with zinc chloride, phosphoric acid, or the like as an activator and dry-distilled, or charcoal or the like is activated with steam. Usually, it is powdery or granular, and any of them can be used. As a result of the activated carbon production process, chemically activated carbon is acidic and steam activated carbon is basic in nature.

An ion exchange resin can be used as the synthetic resin adsorbent. As the ion exchange resin, general ones of acidic and basic ion exchange resins may be used.
Also, chelating type ion exchange resins may be used.

The inorganic adsorbent has a solid acid, a solid base, or a neutral character, and the particles have a porous structure.
The adsorption capacity is very high. Another feature is that it can be used from low to high temperatures. The inorganic adsorbent is not particularly limited, but typical examples include those containing aluminum, magnesium, silicon, or the like as a main component, alone or in combination. For example, silicon dioxide; magnesium oxide; silica gel; silica-alumina; aluminum silicate; activated alumina; clay-based adsorbents such as acid clay and activated clay; Dawsonite compounds; and hydrotalcite compounds.

There are natural and synthetic zeolites, and any of them may be used.

As the silicon dioxide, there are known crystalline, amorphous, amorphous, glassy, synthetic and natural products. Here, powdery silicon dioxide can be used.
As silicon dioxide, silicic acid made from clay mineral obtained by acid treatment of activated clay, Carplex BS30
4, Carplex BS304F, Carplex # 6
7. Synthetic silicic acids such as Carplex # 80 (both Shionogi Pharmaceutical Co.), but are not limited thereto.

The aluminum silicate is obtained by substituting a part of silicon of silicic acid with aluminum, and pumice, fly ash, kaolin, bentonite, activated clay, diatomaceous earth and the like are known. Among them, synthetic aluminum silicate has a large specific surface area and a high adsorption capacity. Examples of the synthetic aluminum silicate include KYOWARD 700 series (manufactured by Kyowa Chemical),
However, it is not limited to these.

The hydrotalcite compounds are made of hydrated hydroxides and carbonates of aluminum and magnesium. Synthetic products include, but are not limited to, Kyoward 500 series and Kyoward 1000 (both manufactured by Kyowa Chemical).

The acidic inorganic adsorbent is generally referred to as acid clay, activated clay, aluminum silicate and the like, and the basic inorganic adsorbent is generally referred to as a hydrous aluminosilicate mineral group such as activated alumina and sodium aluminum silicate. Examples include zeolite-based adsorbents and hydrotalcite compounds.

For the adsorption treatment of the vinyl polymer, an inorganic adsorbent is preferable among the adsorbents. Among them, acidic clay, activated clay, and aluminum silicate are more preferred as the acidic adsorbent, and aluminum silicate is particularly preferred. As the basic adsorbent, zeolite-based adsorbents and hydrotalcite compounds, which are collectively referred to as hydrous aluminosilicate minerals such as activated alumina and sodium aluminum silicate, are more preferable, and hydrotalcite compounds are particularly preferable.

The adsorbents may be used alone or in admixture of two or more.

The vinyl polymer produced by atom transfer radical polymerization can be purified by contacting with an acidic adsorbent and a basic adsorbent. The acidic adsorbent and the basic adsorbent can be mixed and contacted, but they may be contacted in separate steps. When it is brought into contact with the adsorbent, it may be used without a solvent or diluted with a solvent. A general solvent may be used as the diluting solvent. The temperature of the adsorbent treatment is not particularly limited, but is generally 0 ° C to 200 ° C.
C, preferably at room temperature to 180C. Also,
The amount of the adsorbent used is in the range of 0.1 to 500 parts by weight with respect to 100 parts by weight of the vinyl polymer. is there.

Various embodiments are possible for the solid-liquid contact between the adsorbent and the polymer or polymer solution. In addition to the batch type in which the mixing and solid-liquid separation are carried out by a batch operation, the adsorbent is filled in a container. A fixed bed system in which a polymer solution is passed, a moving bed system in which a liquid is passed through a moving bed of an adsorbent, and a fluidized bed system in which an adsorbent is fluidized and adsorbed can be used. Furthermore, in addition to the mixing and dispersion by stirring, various operations for improving the dispersion efficiency, such as shaking of the container and the use of ultrasonic waves, can be incorporated as necessary.

After the polymer or the polymer solution is brought into contact with the adsorbent, the adsorbent is removed by a method such as filtration, centrifugation, sedimentation, etc., and if necessary, dilution and washing are carried out. Obtain a polymer solution.

The adsorption treatment may be performed on a vinyl polymer as a final product, but may be performed on an intermediate product for producing the vinyl polymer. For example, for a vinyl polymer having an alkenyl group obtained by atom transfer radical polymerization, the polymer or a vinyl polymer having a highly reactive carbon-halogen bond, which is an intermediate product for producing the vinyl polymer, is used. Adsorption treatment can also be performed on vinyl polymers such as coalesced and hydroxyl-containing vinyl polymers. Hydrosilylation-Reactive Composition The hydrosilylation-reactive composition of the present invention contains the vinyl polymer subjected to the above-mentioned adsorption treatment.

Examples of the hydrosilylation-reactive composition of the present invention include (A) a vinyl polymer having an alkenyl group in the molecule, and (B) a hydrosilylation-reactive composition containing a compound containing a hydrosilyl group. .

The vinyl polymer of the component A is a vinyl polymer having an alkenyl group in a molecule obtained by the above-mentioned atom transfer radical polymerization, and the above-mentioned one may be used. The hydrosilyl group-containing compound of the component B is not particularly limited, and various compounds can be used. For example, a compound having at least 1.1 hydrosilyl groups in a molecule, a hydrosilane compound having a crosslinkable silyl group in combination, and the like can be given. The specific hydrosilylation reactive composition is shown below. <Hydrosilylation-reactive composition (1)> When the component B is a compound having at least 1.1 hydrosilyl groups in the molecule, the composition gives a cured product by a hydrosilylation reaction. That is, the hydrosilylation-reactive composition is a curable composition (curable composition (I)).

In such a molecule, at least 1.1
The compound having a hydrosilyl group is not particularly limited.
However, for example, represented by the general formula (22) or (23)
Chain polysiloxane; R^{twenty three} _ThreeSiO- [Si (R^{twenty three})_TwoO]_a− [Si (H) (R^{twenty four}) O]_b− [Si (R ^{twenty four} ) (R^{twenty five}) O]_c-SiR^{twenty three} _Three (22) HR^{twenty three} _TwoSiO- [Si (R^{twenty three})_TwoO]_a− [Si (H) (R^{twenty four}) O]_b− [Si (R^{twenty four}) (R^{twenty five}) O]_c-SiR^{twenty three} _TwoH (23) (wherein, R^{twenty three}And R^{twenty four}Is an alkyl group having 1 to 6 carbon atoms,
Or a phenyl group, R ^{twenty five}Is an alkyl having 1 to 10 carbons
Group or aralkyl group. a is 0 ≦ a ≦ 100, b
Is an integer satisfying 2 ≦ b ≦ 100 and c is an integer satisfying 0 ≦ c ≦ 100
Show. A) a cyclic siloxane represented by the general formula (24);

[0092]

Embedded image(Where R²⁶And R²⁷Is an alkyl group having 1 to 6 carbon atoms,
Or a phenyl group, R ²⁸Is an alkyl having 1 to 10 carbons
Group or aralkyl group. d is 0 ≦ d ≦ 8, e is 2
≦ e ≦ 10, f represents an integer of 0 ≦ f ≦ 8, and 3 ≦ d
+ E + f ≦ 10 is satisfied. ))
it can.

These may be used alone or in combination of two or more. Among these siloxanes, from the viewpoint of compatibility with the (meth) acrylic polymer, chain siloxanes represented by the following general formulas (25) and (26) having a phenyl group, and the general formulas (27) and (26) The cyclic siloxane represented by 28) is preferred. _{(CH 3) 3 SiO- [Si} (H) (CH 3) O] g - [Si (C 6 H 5) 2 O] h -S i (CH 3) 3 (25) (CH 3) 3 SiO- [Si (H) (CH ₃ ) O] _g- [Si (CH ₃ ) ｛CH ₂ C (H) (R ²⁴ ) C ₆ H ₅ ｝ O] _h -Si (CH ₃ ) ₃ (26) Wherein R ²⁴ represents hydrogen or a methyl group, and g is 2 ≦ g.
≦ 100, h represents an integer of 0 ≦ h ≦ 100. C ₆ H ₅ represents a phenyl group. )

[0094]

Embedded image (Wherein, R ²⁹ represents hydrogen or a methyl group; i is 2 ≦
i ≦ 10 and j are integers satisfying 0 ≦ j ≦ 8 and 3 ≦ i + j ≦ 10. C ₆ H ₅ represents a phenyl group. As the compound having at least 1.1 hydrosilyl groups of the component B, a low molecular weight compound having two or more alkenyl groups in the molecule may further be selected from hydrosilyl groups represented by the general formulas (22) to (28). A compound obtained by subjecting a group-containing compound to an addition reaction so that a part of the hydrosilyl group remains even after the reaction can also be used. Various compounds can be used as the compound having two or more alkenyl groups in the molecule. For example, 1,4
Hydrocarbon compounds such as -pentadiene, 1,5-hexadiene, 1,6-heptadiene, 1,7-octadiene, 1,8-nonadiene and 1,9-decadiene;
O'-diallylbisphenol A, ether compounds such as 3,3'-diallylbisphenol A, ester compounds such as diallyl phthalate, diallyl isophthalate, triallyl trimellitate and tetraallyl pyromellitate, diethylene glycol diallyl carbonate and the like And carbonate-based compounds.

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 preferable in consideration of the availability of raw materials, the ease of removing excess siloxane, and the compatibility with the vinyl polymer.

[0096]

Embedded image The vinyl polymer of the component A and the hydrosilyl group-containing compound of the component B can be mixed in an arbitrary ratio. However, from the viewpoint of curability, the molar ratio of the alkenyl group to the hydrosilyl group is 5%.
~ 0.2, more preferably 2.5
It is particularly preferred that the value be 0.4. When the molar ratio is 5 or more, only a cured product with insufficient curing and insufficient tackiness is obtained, and when it is less than 0.2, a large amount of active hydrosilyl groups remains in the cured product even after curing. , Cracks and voids are generated, and a uniform and strong cured product cannot be obtained.

The curing reaction between the vinyl polymer of the component A and the compound containing a hydrosilyl group of the component B proceeds by mixing and heating the two components. To accelerate the reaction, a hydrosilylation catalyst is used. Can be added. Such a hydrosilylation catalyst is not particularly limited, and examples thereof include a radical initiator such as an organic peroxide and an azo compound, and a transition metal catalyst.

The radical initiator is not particularly limited.
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 such as dialkyl peroxide, 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 solid in a carrier such as alumina, silica or carbon black, chloroplatinic acid, chloroplatinic acid and alcohol, aldehyde, Examples include a complex with a ketone or the like, a platinum-olefin complex, and a platinum (0) -divinyltetramethyldisiloxane complex. Examples of catalysts other than platinum compounds include RhCl (PPh ₃ ) ₃ , R
hCl ₃ , RuCl ₃ , IrCl ₃ , FeCl ₃ , AlCl
_{3, PdCl 2 · H 2 O} , NiCl 2, TiCl 4 , and the like. These catalysts may be used alone or in combination of two or more. The amount of the catalyst is not particularly limited, but may be 1 to 1 mol of the alkenyl group of the component (A).
It is preferably used in the range of 0 ^-1 to 10 ^-8 mol, and more preferably in the range of 10 ^-3 to 10 ^-6 mol. 10
^If it is less than ^-8 mol, curing does not proceed sufficiently. Also, hydrosilylation catalysts are generally expensive and corrosive, and
Since a large amount of hydrogen gas is generated and a cured product may foam, it is preferable not to use 10 ^-1 mol or more.

The curing temperature is not particularly limited, but is generally from 0 ° C. to 200 ° C., preferably from 30 ° C. to 150 ° C., and more preferably from 80 ° C. to 150 ° C. Thereby, a curable composition can be obtained in a short time. <Hydrosilylation-reactive composition (2)> As the hydrosilyl group-containing compound of the component B, a hydrosilane compound having a crosslinkable silyl group may be used. The hydrosilane compound having a crosslinkable silyl group is not particularly limited,
As a typical example, a compound represented by the general formula 29 is exemplified. H- [Si (R ¹¹ ) _2-b (Y) _b O] _m -Si (R ¹² ) _3-a (Y) _a (29) wherein R ¹¹ and R ¹² each have 1 carbon atom Alkyl group having 20 to 20 carbon atoms, aryl group having 6 to 20 carbon atoms, 7 to 20 carbon atoms
An aralkyl group, or (R ′) ₃ SiO— (R ′ is a monovalent hydrocarbon group having 1 to 20 carbon atoms, and three R ′
May be the same or different), and R ¹¹ or R ¹² is 2
When there are more than one, they may be the same or different. Y represents a hydroxyl group or a hydrolyzable group, and when two or more Ys are present, they may be the same or different. a is 0, 1, 2, or 3
And b represents 0, 1, or 2. m is 0 to 19
Is an integer. However, it is assumed that a + mb ≧ 1 is satisfied.と し て As the hydrolyzable group, for example, a hydrogen atom, an alkoxy group, an acyloxy group, a ketoximate group, an amino group,
Commonly used groups such as an amide group, an aminooxy group, a mercapto group and an alkenyloxy group can be mentioned.
Among these, an alkoxy group, an amide group, and an aminooxy group are preferred, but an alkoxy group is particularly preferred because of its mild hydrolyzability and easy handling.

A hydrolyzable group or a hydroxyl group can be bonded to one silicon atom in the range of from 1 to 3, and (a + Σ
b) is preferably in the range of 1 to 5. When two or more hydrolyzable groups or hydroxyl groups are bonded to the crosslinkable silyl group, they may be the same or different. The number of silicon atoms forming a crosslinkable silyl group is one or more. In the case of silicon atoms linked by a siloxane bond or the like, the number is preferably 20 or less.

Among these hydrosilane compounds, in particular, the crosslinkability represented by the general formula 30 H-Si (R ¹² ) _3-a (Y) _a (30) (wherein R ¹² , Y and a are the same as above) Compounds having a group are preferred because they are easily available.

By hydrosilylating the hydrosilylation-reactive composition using the above-mentioned hydrosilane compound as the component B, a vinyl polymer having a crosslinkable silyl group in the molecule can be obtained.

The vinyl polymer having at least 1.1 crosslinkable silyl groups in the molecule is crosslinked to give a cured product.
A vinyl polymer having at least 1.1 crosslinkable silyl groups in the molecule obtained by the above method and a curable composition containing the vinyl polymer (curable composition (2)) are also one of the present invention. One.

The crosslinkable silyl group of the present invention is represented by the following general formula 31:-[Si (R ¹¹ ) _2-b (Y) _b O] _m -Si (R ¹² ) _3-a (Y) _a (31) In the formula, R ¹¹ and R ¹² each represent an alkyl group having 1 to 20 carbon atoms, an aryl group having 6 to 20 carbon atoms, and 7 to 20 carbon atoms.
An aralkyl group, or (R ′) ₃ SiO— (R ′ is a monovalent hydrocarbon group having 1 to 20 carbon atoms, and three R ′
May be the same or different), and R ¹¹ or R ¹² is 2
When there are more than one, they may be the same or different. Y represents a hydroxyl group or a hydrolyzable group, and when two or more Ys are present, they may be the same or different. a is 0, 1, 2, or 3
And b represents 0, 1, or 2. m is 0 to 19
Is an integer. However, it is assumed that a + mb ≧ 1 is satisfied. And a group represented by｝.

Examples of the hydrolyzable group include groups generally used such as a hydrogen atom, an alkoxy group, an acyloxy group, a ketoximate group, an amino group, an amide group, an aminooxy group, a mercapto group and an alkenyloxy group. Can be Among these, an alkoxy group, an amide group, and an aminooxy group are preferred, but an alkoxy group is particularly preferred because of its mild hydrolyzability and easy handling.

A hydrolyzable group or a hydroxyl group can be bonded to one silicon atom in a range of 1 to 3 and (a + Σ
b) is preferably in the range of 1 to 5. When two or more hydrolyzable groups or hydroxyl groups are bonded to the crosslinkable silyl group, they may be the same or different. The number of silicon atoms forming a crosslinkable silyl group is one or more. In the case of silicon atoms linked by a siloxane bond or the like, the number is preferably 20 or less. In particular, a crosslinkable silyl group represented by the general formula 32-Si (R ¹² ) _3-a (Y) _a (32) (wherein R ¹⁰ , Y and a are as defined above) is easily available. Is preferred.

When a cured product obtained by curing the vinyl polymer having a crosslinkable silyl group of the present invention is particularly required to have rubber-like properties, the molecular weight between crosslinking points which greatly affects rubber elasticity is large. Therefore, it is preferable that at least one of the crosslinkable silyl groups is at the terminal of the molecular chain. More preferably, it has all functional groups at the molecular chain terminals.

The proportion of the hydrosilane compound having both the vinyl polymer of the component A and the crosslinkable silyl group of the component B is not particularly limited, but it is preferable that the hydrosilyl group is at least equivalent to the alkenyl group.

In order to proceed the hydrosilylation reaction more rapidly, a hydrosilylation catalyst can be added. As the hydrosilylation catalyst, those already exemplified may be used.

The reaction temperature is not particularly limited, but is generally 0 ° C. to 200 ° C., preferably 30 ° C. to 150 ° C., more preferably 80 ° C. to 150 ° C.

In curing the curable composition (2), a condensation catalyst may or may not be used. Titanate such as tetrabutyl titanate and tetrapropyl titanate; dibutyltin dilaurate;
Organic tin compounds such as dibutyltin diacetylacetonate, dibutyltin maleate, dibutyltin diacetate, dibutyltin dimethoxide, tin octylate, tin naphthenate; lead octylate, butylamine, octylamine, dibutylamine, monoethanolamine, diethanolamine,
Triethanolamine, diethylenetriamine, triethylenetetramine, oleylamine, octylamine,
Cyclohexylamine, benzylamine, diethylaminopropylamine, xylylenediamine, triethylenediamine, guanidine, diphenylguanidine, 2,
4,6-tris (dimethylaminomethyl) phenol,
Amine compounds such as morpholine, N-methylmorpholine, 1,3-diazabicyclo (5,4,6) undecene-7 or carboxylate thereof; amine compounds such as a reaction product or a mixture of laurylamine and tin octylate Reactants and mixtures of compounds with organotin compounds; low molecular weight polyamide resins obtained from excess polyamines and polybasic acids; reaction products of excess polyamines and epoxy compounds;
Silane coupling agent having an amino group, for example, γ-
One or more known silanol catalysts such as aminopropyltrimethoxysilane and N- (β-aminoethyl) aminopropylmethyldimethoxysilane may be used as needed. The amount used is preferably from 0 to 10% by weight based on the vinyl polymer having a crosslinkable silyl group at the terminal. When an alkoxy group is used as the hydrolyzable group Y, the curing speed is slow only with this polymer,
It is preferred to use a curing catalyst. <Curable composition> The curable composition (1) and the curable composition (2) may contain various additives for adjusting physical properties, for example, a flame retardant, an antioxidant, a filler, and a plasticizer. , Physical property modifier, reaction diluent, adhesion promoter, storage stability improver, solvent, radical inhibitor, metal deactivator, ozone deterioration inhibitor, phosphorus peroxide decomposer, lubricant, pigment, foam An agent, a photocurable resin and the like may be appropriately compounded as necessary. These various additives may be used alone or in combination of two or more.

Further, since the vinyl polymer is originally a polymer having excellent durability, an antioxidant is not necessarily required. Can be used. <Filler> The filler that can be blended is not particularly limited, but for imparting physical properties such as strength, for example, fine powdered silica, calcium carbonate, talc, titanium oxide, diatomaceous earth, barium sulfate, carbon black, surface-treated fine powder Reinforcing fillers such as calcium carbonate, calcined clay, clay and activated zinc white. The reinforcing filler may be used alone or in combination of two or more. Among these, silica fine powder is preferable, and hydrated silica obtained by a wet production method or the like, dry silica obtained by a dry production method or the like can be used. Of these, anhydrous silica is particularly preferred because if the composition contains a large amount of water, a side reaction or the like may occur during the curing reaction. Further, those obtained by subjecting the surface of anhydrous silica to a hydrophobic treatment are particularly preferred because they easily exhibit fluidity suitable for molding. In addition, a filler having not so strong reinforcing property can be used for increasing the amount or adjusting physical properties. <Plasticizer> The plasticizer that can be blended is not particularly limited, but for the purpose of adjusting physical properties, adjusting properties, and the like, for example,
Dibutyl phthalate, diheptyl phthalate, di (2-
Phthalates such as ethylhexyl) phthalate and butylbenzyl phthalate; non-aromatic dibasic esters such as dioctyl adipate, dioctyl sebacate, dibutyl sebacate and isodecyl succinate; butyl oleate and methyl acetyl risilinolate Aliphatic esters; esters of polyalkylene glycols such as diethylene glycol dibenzoate, triethylene glycol dibenzoate, and pentaerythritol ester; phosphates such as tricresyl phosphate and tributyl phosphate; trimellitate;
Polystyrenes such as polystyrene and poly-α-methylstyrene; polybutadiene, polybutene, polyisobutylene, butadiene-acrylonitrile, polychloroprene; chlorinated paraffins; hydrocarbon oils such as alkyldiphenyl and partially hydrogenated terphenyl; Polyether polyols such as polyethylene glycol, polypropylene glycol, and polytetramethylene glycol; and polyethers such as derivatives in which hydroxyl groups of these polyether polyols are converted into ester groups, ether groups, and the like; epoxidized soybean oil, benzyl epoxy stearate And other dibasic acids such as sebacic acid, adipic acid, azelaic acid, and phthalic acid, and ethylene glycol, diethylene glycol, triethylene glycol, and propylene glycol. Polyester plasticizers obtained from dihydric alcohols such as propylene glycol and dipropylene glycol; vinyl polymers obtained by polymerizing vinyl monomers such as acrylic plasticizers by various methods, alone or Although two or more types can be used in combination,
It is not necessary. In addition, these plasticizers can be blended at the time of polymer production. <Storage stability improver> The storage stability improver that can be blended is
The composition is not particularly limited as long as it can suppress the viscosity increase during storage and the remarkable change in the curing rate after storage, and examples thereof include benzothiazole and dimethylmalate. <Solvent> Examples of solvents that can be blended include aromatic hydrocarbon solvents such as toluene and xylene, ester solvents such as ethyl acetate, butyl acetate, amyl acetate, and cellosolve acetate, and ketones such as methyl ethyl ketone, methyl isobutyl ketone, and diisobutyl ketone. And the like. These solvents may be used during the production of the polymer. <Adhesiveness-imparting agent> The adhesiveness-imparting agent that can be blended is not particularly limited as long as it imparts adhesiveness to the cured product, but a crosslinkable silyl group-containing compound is preferable, and a silane coupling agent is more preferable. Specific examples thereof include alkyl alkoxysilanes such as methyltrimethoxysilane, dimethyldimethoxysilane, trimethylmethoxysilane, and n-propyltrimethoxysilane; alkyls such as dimethyldiisopropenoxysilane and methyltriisopropenoxysilane. Isopropenoxysilanes; vinyl-type unsaturated group-containing silanes such as vinyltrimethoxysilane, vinyldimethylmethoxysilane, vinyltriethoxysilane, γ-methacryloyloxypropylmethyldimethoxysilane, and γ-acroyloxypropylmethyltriethoxysilane; Silicone varnishes; polysiloxanes and the like.

Among them, organic groups having atoms other than carbon atoms and hydrogen atoms such as epoxy group, (meth) acrylic group, isocyanate group, isocyanurate group, carbamate group, amino group, mercapto group and carboxyl group in the molecule. And a silane coupling agent having a crosslinkable silyl group. When these are specifically exemplified, alkoxysilanes having an isocyanate group include γ-
Isocyanate group-containing silanes such as isocyanate propyl trimethoxy silane, γ-isocyanate propyl triethoxy silane, γ-isocyanate propyl methyl diethoxy silane, γ-isocyanate propyl methyl dimethoxy silane; alkoxysilanes having an isocyanurate group include: Isocyanurate silanes such as tris (trimethoxysilyl) isocyanurate;
Examples of the alkoxysilane having an amino group include γ-aminopropyltrimethoxysilane, γ-aminopropyltriethoxysilane, γ-aminopropylmethyldimethoxysilane, γ-aminopropylmethyldiethoxysilane, and N- (β-aminoethyl ) -Γ-aminopropyltrimethoxysilane, N- (β-aminoethyl) -γ-aminopropylmethyldimethoxysilane, N- (β-aminoethyl) -γ-aminopropyltriethoxysilane,
N- (β-aminoethyl) -γ-aminopropylmethyldiethoxysilane, γ-ureidopropyltrimethoxysilane, N-phenyl-γ-aminopropyltrimethoxysilane, N-benzyl-γ-aminopropyltrimethoxysilane, Amino group-containing silanes such as N-vinylbenzyl-γ-aminopropyltriethoxysilane; alkoxysilanes having a mercapto group include γ-mercaptopropyltrimethoxysilane, γ-mercaptopropyltriethoxysilane, γ-mercaptopropyl Mercapto group-containing silanes such as methyldimethoxysilane and γ-mercaptopropylmethyldiethoxysilane; and alkoxysilanes having a carboxyl group include β-
Carboxyethyltriethoxysilane, β-carboxyethylphenylbis (2-methoxyethoxy) silane,
Carboxysilanes such as N-β- (carboxymethyl) aminoethyl-γ-aminopropyltrimethoxysilane; alkoxysilanes having a halogen group include
halogen-containing silanes such as γ-chloropropyltrimethoxysilane;

Further, amino-modified silyl polymers, silylated amino polymers, unsaturated aminosilane complexes, phenylamino long-chain alkylsilanes, aminosilylated silicones, silylated polyesters, and the like, which are derivatives of these derivatives, are also used as silane coupling agents. be able to.

Among these, alkoxysilanes having an epoxy group or a (meth) acryl group in the molecule are more preferable from the viewpoint of curability and adhesiveness. When these are exemplified more specifically, alkoxysilanes having an epoxy group include γ-glycidoxypropylmethyldimethoxysilane, γ-glycidoxypropyltrimethoxysilane, γ-glycidoxypropyltriethoxysilane, β -(3,4-epoxycyclohexyl) ethyltrimethoxysilane, β- (3,4-epoxycyclohexyl) ethyltriethoxysilane, γ-glycidoxypropylmethyldiisopropenoxysilane, and the like have a (meth) acryl group. The alkoxysilanes having
γ-methacryloxypropyltrimethoxysilane, γ-
Methacryloxypropyltriethoxysilane, γ-acryloxypropyltrimethoxysilane, γ-acryloxypropyltriethoxysilane, methacryloxymethyltrimethoxysilane, methacryloxymethyltriethoxysilane, acryloxymethyltrimethoxysilane, acryloxymethyltri Ethoxysilane and the like can be mentioned.
These may be used alone or in combination of two or more.

In order to further improve the adhesiveness, a crosslinkable silyl group condensation catalyst can be used together with the above-mentioned adhesiveness-imparting agent. As a crosslinkable silyl group condensation catalyst,
Dibutyltin dilaurate, dibutyltin diacetylacetonate, dibutyltin dimethoxide, organotin compounds such as tin octylate, organoaluminum compounds such as aluminum acetylacetonate, tetraisopropoxytitanium,
Organic titanium compounds such as tetrabutoxytitanium and the like can be mentioned.

Specific examples other than the silane coupling agent are not particularly restricted but include, for example, epoxy resins, phenol resins, sulfur, alkyl titanates, aromatic polyisocyanates and the like.

The adhesion-imparting agent may be a vinyl polymer 10
It is preferable to add 0.01 to 20 parts by weight to 0 part by weight. If the amount is less than 0.01 part by weight, the effect of improving the adhesion is small, and if it exceeds 20 parts by weight, the physical properties of the cured product are adversely affected. Preferably it is 0.1 to 10 parts by weight, more preferably 0.5 to 5 parts by weight.

The above-mentioned adhesiveness-imparting agents may be used alone or in combination of two or more. The addition of these adhesion-imparting agents can improve the adhesion to the adherend. <Molding Method> The molding method when the curable composition of the present invention is used as a molded article is not particularly limited, and various commonly used molding methods can be used. For example, cast molding, compression molding, transfer molding, injection molding, extrusion molding, rotational molding, hollow molding, thermoforming and the like can be mentioned. In particular, injection molding is preferred from the viewpoint that automation and continuity are possible and productivity is excellent.
In addition, when used as a gasket, etc., both a wet type where the curable composition applied to the flange surface etc. is sandwiched from both sides in an uncured state and then cured, and a dry type where the cured composition is sandwiched after being cured are possible It is. <Use> The curable composition of the present invention is not limited,
Sealing materials such as elastic sealing materials for buildings and sealing materials for double glazing, electric and electronic parts materials such as sealing materials for backside of solar cells, electric insulating materials such as insulating coating materials for electric wires and cables, adhesives, adhesives, Elastic adhesives, paints, powder paints, coating materials, foams, potting materials for electric and electronic devices, films, gaskets, casting materials, artificial marble,
It can be used for various applications, such as various molding materials, and a sealing material for rust-proofing and waterproofing on the end face (cut portion) of a netted glass or a laminated glass.

Further, the molded article having rubber elasticity obtained from the curable composition of the present invention can be widely used mainly for gaskets and packings. For example, in the field of automobiles, it can be used as a body part as a sealing material for maintaining airtightness, a vibration preventing material for glass, a vibration damping material for a body part, particularly a window seal gasket, a gasket for door glass. As a chassis component, it can be used for vibration-proof and sound-proof engines and suspension rubbers, especially engine mount rubber. As engine parts, it can be used for hoses for cooling, fuel supply, exhaust control, etc., seals for engine oil, and the like. It can also be used for exhaust gas purifier parts and brake parts. In the field of home appliances, it can be used for packing, O-rings, belts and the like. Specifically, decorations for lighting equipment, waterproof packings, vibration-proof rubbers, insect-proof packings, vibration-proof and sound-absorbing and air-sealing materials for cleaners, drip-proof covers for electric water heaters, waterproof packing, heater parts Packing, electrode part packing, safety valve diaphragm, hoses for sake kettle, waterproof packing, solenoid valve, waterproof packing for steam oven range and jar rice cooker, water supply tank packing, water absorption valve, water receiving packing, connection hose, belt, heat insulation Heater packing, oil packing for combustion equipment such as steam outlet seal, O-ring, drain packing, pressurizing tube, blower tube, sending / suction packing, anti-vibration rubber,
Examples include a filler gasket, a speaker edge, a turntable sheet, a belt, a pulley, and the like for audio equipment, such as a filler port packing, an oil meter packing, an oil supply pipe, a diaphragm valve, and an air supply pipe. In the construction field, structural gaskets (zipper gaskets), air film structural roofing materials,
It can be used for waterproof material, fixed sealing material, vibration-proof material, sound-proof material, setting block, sliding material, etc. In the field of sports, it can be used for sports floors such as all-weather pavement materials, gymnasium floors, etc., for sports shoes for shoe sole materials and midsole materials, and for ball balls for golf balls and the like. In the field of anti-vibration rubber, it can be used as anti-vibration rubber for automobiles, anti-vibration rubber for railway vehicles, anti-vibration rubber for aircraft, fenders and the like. In the marine and civil engineering fields, structural materials include rubber expansion joints, bearings,
Rubber molds, rubber packers, rubber skirts, sponge mats, mortar hoses, mortar strainers, etc. as construction auxiliary materials such as waterproof sheets, rubber dams, elastic pavements, vibration proof pads, protective bodies, etc., rubber sheets, air hoses, etc. as construction auxiliary materials It can be used for rubber buoys and wave absorbers as safety measures products, and for oil fences, silt fences, antifouling materials, marine hoses, dressing hoses, oil skimmers and the like as environmental protection products. In addition, it can be used for rubber plate, mat, foam plate and the like.

[0122]

EXAMPLES Specific examples will be shown below, but the present invention is not limited to the following examples. (Production Example 1) Method for producing alkenyl-terminated vinyl polymer CuBr (42.0 g, 0.29 mol) was charged into a 10-L separable flask equipped with a reflux tube and a stirrer, and the inside of the reaction vessel was purged with nitrogen. Acetonitrile (55
9 mL) and stirred in an oil bath at 70 ° C. for 45 minutes. To this, butyl acrylate (1.00 kg), 2.5
-Diethyldibromoadipate (175 g, 0.488
mol), pentamethyldiethylenetriamine (4.0
(0 mL, 19.2 mmol) (hereinafter triamine) was added to initiate the reaction. While heating and stirring at 70 ° C, butyl acrylate (4.0
0 kg) was continuously added dropwise over 190 minutes. During the dropping of butyl acrylate, triamine (4.00 mL, 1
9.2 mmol) was added. Subsequently, after heating and stirring at 70 ° C. for 60 minutes, 1,7-octadiene (1.44 L, 9.
75 mol), triamine (20.5 mL, 0.097
4 mol), and the mixture was further heated and stirred at 70 ° C. for 210 minutes.

The volatile components of the reaction mixture were distilled off under reduced pressure, dissolved in hexane, and the solid content was separated by filtration to obtain an alkenyl group-terminated polymer (Polymer [1]). The polymer [1] had a number average molecular weight of 14,000 and a molecular weight distribution of 1.34 as measured by GPC (in terms of polystyrene), and the average number of alkenyl groups introduced per molecule of polymer was ¹ HN.
It was 2.5 as determined by MR analysis. (Production Example 2) Br treatment of alkenyl-terminated vinyl polymer
Method The polymer [1] (10 g) obtained in Production Example 1 and potassium benzoate (0.57 g) were charged into a reaction vessel, and N, N-dimethylacetamide (10 mL, referred to as "DMAC").
Was added and the mixture was heated and stirred at 100 ° C. for 4 hours under a nitrogen atmosphere. DMAC was evaporated under reduced pressure while heating, and toluene was added to the resulting mixture. The solid content was separated by filtration, and the filtrate was concentrated to obtain a polymer containing no bromine group (polymer [2]). (Production Example 3) Br treatment of alkenyl-terminated vinyl polymer
Method The polymer [1] (300 g) obtained in Production Example 1 and potassium acetate (6.68 g) were charged into a reaction vessel, and DMAC (30
0 mL), and the mixture was heated and stirred at 100 ° C. for 8 hours under a nitrogen atmosphere. DMAC was evaporated under reduced pressure while heating, and toluene was added to the resulting mixture. The solid content was separated by filtration, and the filtrate was concentrated to obtain a polymer containing no bromine group (polymer [3]).

Polymers [1] to [1] produced in Production Examples 1 to 3
[3] was purified using the adsorbents shown in Table 1. (Example 1) Polymer [1] (5.0 g) was added to toluene (1
5 mL), and as a basic adsorbent, a hydrotalcite-type adsorbent (0.25 g; Kyoward 500P)
L, manufactured by Kyowa Chemical Co., Ltd.), silicon dioxide / aluminum silicate (0.25 g; Mizuka Life P-) as an acidic adsorbent
After addition of 1G (manufactured by Mizusawa Chemical Co., Ltd.), the mixture was heated and stirred at 100 ° C. for 1 hour. After diluting with toluene and filtering off the adsorbent, the toluene was distilled off to obtain a vinyl polymer. A polymer and a chain siloxane containing an average of 5 hydrosilyl groups and an average of 5 α-methylstyrene groups in the molecule (S
i-H value: 3.70 mmol / g) and a xylene solution of 1,1,3,3-tetramethyl-1,3-divinyldisiloxane complex of zero-valent platinum (a platinum concentration of 1.3 × 10 ⁻⁵⁾
(mmol / μl) was manually mixed at room temperature to obtain a composition. The amount of the chain siloxane used was such that the molar ratio of the alkenyl group to the hydrosilyl group was 1 / 1.5, and the amount of the platinum catalyst was the molar ratio to the alkenyl group.

A portion of the composition was heated on a hot plate at 130 ° C. with stirring in an air atmosphere, and the gelation time was measured. Table 1 shows the results. (Examples 2 and 3) After performing an adsorption treatment using an acidic adsorbent and a basic adsorbent in the same manner as in Example 1, a curing test was performed and the gelation time was measured. Table 1 shows the adsorbents used.
Table 2 shows the results. (Comparative Example 1) Polymer [1] (5.0 g) was added to toluene (1
5 mL) and activated clay (0.
After addition of 50 g; Galleon Earth V2, manufactured by Mizusawa Chemical Co., Ltd., the mixture was heated and stirred at 100 ° C. for 1 hour. After diluting with toluene and filtering off the adsorbent, the toluene was distilled off to obtain a vinyl polymer. A polymer and a chain siloxane containing an average of 5 hydrosilyl groups and an average of 5 α-methylstyrene groups in the molecule (Si-H value: 3.70 mmol /
g) and 1,1,3,3-tetramethyl-
A xylene solution of 1,3-divinyldisiloxane complex (platinum concentration: 1.3 × 10 ⁻⁵ mmol / μl) was manually mixed at room temperature to obtain a composition. The amount of the chain siloxane used is such that the molar ratio of the alkenyl group and the hydrosilyl group is 1/1.
, And the amount of platinum catalyst was a molar ratio to the alkenyl group.

A part of the composition was heated while stirring on a hot plate at 130 ° C. in an air atmosphere, and the gelation time was measured. Table 1 shows the results. (Comparative Examples 2 to 13) After performing the adsorption treatment in the same manner as the comparative example, a curing test was performed, and the gelation time was measured. The adsorbent used is shown in Table 1, and the results are shown in Table 2.

As is evident from Table 2, it is necessary to perform the adsorption treatment using the acidic adsorbent and the basic adsorbent in combination, rather than performing the adsorption treatment using only the acidic adsorbent or the basic adsorbent. The amount of platinum catalyst is small. In particular, the combination of a hydrotalcite-type adsorbent and aluminum silicate was highly effective.

[0128]

[Table 1]

[0129]

[Table 2] (Production Example 4) In a 10 L separable flask equipped with a reflux tube and a stirrer, CuBr (36.02 g, 0.251 g) was added.
1 mol), and the inside of the reaction vessel was purged with nitrogen. Add acetonitrile (618 mL) and put in an oil bath at 70 ° C.
For 15 minutes. Add butyl acrylate (360
mL, 2.51 mol), ethyl acrylate (500 m
L, 4.62 mol), 2-methoxyethyl acrylate (375 mL, 2.91 mol), diethyl 2,5-dibromoadipate (150.68 g, 0.419 mol)
l), pentamethyldiethylenetriamine (2.18 m
L, 1.81 g, 10.46 mmol) (hereinafter triamine) was added to initiate the reaction. A mixture of butyl acrylate (1440 mL), ethyl acrylate (2002 mL), and 2-methoxyethyl acrylate (1498 mL) was continuously dropped over 210 minutes while heating and stirring at 70 ° C. Triamine (7.63 mL, 6.33 g, 36.5 mmol) was added during the dropwise addition of the monomer. 330 minutes after the start of the reaction, 1,7-octadiene (1236 mL, 922 g, 8.37 mol),
Triamine (26.16 mL, 21.71 g, 0.12
5 mol), followed by heating and stirring at 70 ° C. for 250 minutes.

After diluting the reaction mixture with toluene and passing through an activated alumina column, volatile components are distilled off under reduced pressure to obtain an alkenyl-terminated copolymer (alkenyl-terminated poly (butyl acrylate, ethyl acrylate, methoxy acrylate). Ethyl) copolymer: Copolymer [1]｝ was obtained.

In a 10 L separable flask equipped with a reflux tube, copolymer [1] (2.87 kg) and potassium acetate (79.
57 g) and N, N-dimethylacetamide (2.9 L) were charged and heated and stirred at 100 ° C. for 12 hours under a nitrogen stream.
After removing N, N-dimethylacetic acid amide under reduced pressure by heating, the mixture was diluted with toluene. Solids insoluble in toluene (K
Br and excess potassium acetate) were filtered over an activated alumina column. The volatile content of the filtrate was distilled off under reduced pressure to obtain a copolymer [2]. (Example 4) In a 10 L separable flask equipped with a reflux tube, copolymer [2] (2.87 kg) and aluminum silicate (143) were placed.
g, Kyowa Chemical Co., Ltd., Kyoward 700SL), a hydrotalcite adsorbent (143 g, Kyowa Chemical Co., Ltd., Kyoward 500SH), and toluene (5.2 L) were charged and heated and stirred at 100 ° C. for 7 hours under a nitrogen stream. After removing the adsorbent by filtration, toluene in the filtrate was distilled off under reduced pressure to obtain a vinyl group-terminated copolymer (copolymer [3]). The number average molecular weight of the obtained copolymer was 18,000 by GPC measurement (in terms of polystyrene), and the molecular weight distribution was 1.
24. The average number of vinyl groups introduced per molecule of the copolymer was 2.2 as determined by ¹ H NMR analysis.

Copolymer [3] (Alkenyl group content 0.15)
8 mmol / g) and linear siloxane (average 5
Of hydrosilyl groups and an average of 5 α-methylstyrene groups: 3.70 mmol / g of Si—H groups). To this mixture, 1,3-divinyl-1,
A 1,3,3-tetramethyldisiloxane platinum complex catalyst (1.3 × 10 ⁻⁵ mmol / μl, xylene solution) was uniformly mixed. The amount of the chain siloxane is determined as follows: the SiH group of the chain siloxane is the alkenyl group of the copolymer [3].
The amount of the platinum catalyst was set so as to be 6.5 × 10 ⁻⁴ equivalent in molar ratio to the alkenyl group by 32 equivalents. A part of the curable composition thus obtained was heated to 150 ° C. and the gelation time was measured to be 14 seconds.

The curable composition was poured into a mold and heated at 150 ° C.
To obtain a cured product having rubber elasticity. (Production Example 5) A 10 L separable flask equipped with a reflux tube and a stirrer was charged with CuBr (50.4 g, 0.35 mol).
l) was charged, and the inside of the reaction vessel was replaced with nitrogen. Acetonitrile (670 mL) was added, and the mixture was placed in an oil bath at 70 ° C. for 30 minutes.
Stirred for minutes. Add butyl acrylate (1.20k
g), diethyl 2,5-dibromoadipate (105
g, 0.29 mol) and pentamethyldiethylenetriamine (2.44 mL, 11.7 mmol) (hereinafter triamine) were added to initiate the reaction. With heating and stirring at 70 ° C., butyl acrylate (4.80 kg) was continuously added dropwise. Triamine (9.8 mL, 47 mmol) was added during the dropwise addition of butyl acrylate. Subsequently, after heating and stirring at 70 ° C., 1,7-octadiene (1.
73L), triamine (18.3mL, 88mmol)
Was added, and the mixture was further heated and stirred at 70 ° C. for 4 hours.

The reaction mixture was diluted with toluene and the solid was filtered off. The filtrate was concentrated to obtain an alkenyl group-terminated polymer (polymer [4]). Polymer [4] is GPC
The number average molecular weight was 257 as measured (in terms of polystyrene).
The molecular weight distribution was 1.30, and the average number of alkenyl groups introduced per molecule of polymer was determined by ¹ H NMR.
It was 2.6 as determined by analysis. (Production Example 6) The polymer [4] (392) obtained in Production Example 5
g) and potassium acetate (7.7 g) were charged into a reaction vessel, and DM
AC (400 mL) was added, and the temperature was increased to 100 ° C. in a nitrogen atmosphere.
For 10 hours. DMAC was evaporated under reduced pressure while heating, and toluene was added to the resulting mixture. The solid content was separated by filtration, and the filtrate was concentrated to obtain a polymer containing no bromine group (polymer [5]). Example 5 The polymer [5] (300) obtained in Production Example 6
g) and xylene (30 mL), hydrotalcite-type adsorbent (3.0 g; Kyoward 500SH, manufactured by Kyowa Chemical Co., Ltd.) as a basic adsorbent, and aluminum silicate (3.0 g; Kyoword 700S
L, manufactured by Kyowa Chemical Industry Co., Ltd.) and then heated and stirred at 150 ° C. for 3 hours. After diluting with toluene and filtering off the adsorbent, the filtrate was concentrated to obtain a polymer (polymer [6]).

A polymer, a chain siloxane having an average of 5 hydrosilyl groups and an average of 5 α-methylstyrene groups in the molecule (Si-H value: 3.70 mmol / g) and 1 of 0-valent platinum , 1,3,3-tetramethyl-1,3-
A xylene solution of a divinyldisiloxane complex (platinum concentration: 1.3 × 10 ⁻⁵ mmol / μl) was manually mixed at room temperature to obtain a composition. The amount of the chain siloxane used is such that the molar ratio of the alkenyl group to the hydrosilyl group is 1 / 1.5, and the amount of the platinum catalyst is 10% in the molar ratio to the alkenyl group.
^-3 equivalents were set. A part of the curable composition thus obtained was heated to 130 ° C., and the gelation time was measured. The result was 40 seconds. (Example 6) The polymer [6] (30) obtained in Example 5
g) was heated under reduced pressure at 100 ° C. After decompression with nitrogen, methyl orthoformate (0.33 mL,
3.0 mmol), a xylene solution of 1,1,3,3-tetramethyl-1,3-divinyldisiloxane complex of zero-valent platinum (1.13 mL; platinum concentration 1.3 × 10 ⁻⁵ mmol)
/ Μl) was added and mixed. After pressurizing to 1.5 MPa with nitrogen, the mixture was heated and stirred at 100 ° C. for 2 hours. By heating and devolatilization, a polymer having an alkoxysilyl group (polymer [7]) was obtained. The polymer [7] had a number average molecular weight of 33,300 and a molecular weight distribution of 1.62 by GPC measurement (in terms of polystyrene), and the average number of silyl groups introduced per polymer molecule was determined by ¹ H NMR analysis. As a result, it was 1.7 pieces. (Example 7) The polymer [7] obtained in Example 6 was added with tetravalent S
n Catalyst (dibutyltin diacetylacetonate) was mixed well to obtain a curable composition. By leaving it at room temperature for 6 hours, a cured product having rubber elasticity was obtained.

[0136]

According to the present invention, the hydrosilylation activity is improved by purifying a vinyl polymer produced by atom transfer radical polymerization by an adsorption treatment using both an acidic adsorbent and a basic adsorbent. The polymer can be used as a component of a hydrosilylation reactive composition.

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Claims (32)

[Claims] 1. A method for purifying a vinyl polymer by bringing a vinyl polymer produced by utilizing atom transfer radical polymerization of a vinyl monomer with a transition metal complex as a polymerization catalyst into contact with an adsorbent. A refining method characterized by using an acidic adsorbent and a basic adsorbent together as an agent. 2. A vinyl polymer obtained by contacting a vinyl polymer having at least one alkenyl group in a molecule or an intermediate product obtained during the step of producing the vinyl polymer with an adsorbent. Alternatively, in a method for purifying an intermediate product, an acidic adsorbent and a basic adsorbent are used in combination as an adsorbent. 3. A vinyl polymer having at least one alkenyl group in the molecule is produced by utilizing atom transfer radical polymerization of a vinyl monomer using a transition metal complex as a polymerization catalyst. The purification method according to claim 2, wherein 4. The method according to claim 2, wherein the alkenyl group is present at a molecular chain terminal of the vinyl polymer. 5. The vinyl polymer according to claim 4, which is produced by adding a compound having two or more carbon-carbon double bonds having low polymerizability during or after polymerization in atom transfer radical polymerization. Purification method. 6. A method for purifying a vinyl polymer for using the vinyl polymer as a component of a hydrosilylation-reactive composition, characterized by purification by adsorption treatment using an acidic adsorbent and a basic adsorbent together. Purification method. 7. The purification method according to any one of claims 1 to 6, wherein the vinyl polymer or the intermediate product is simultaneously brought into contact with both an acidic adsorbent and a basic adsorbent. Characteristic purification method. 8. The purification method according to claim 1, wherein the acidic adsorbent and / or the basic adsorbent is an inorganic adsorbent. 9. The purification method according to claim 1, wherein the acidic adsorbent is activated clay or aluminum silicate. 10. The purification method according to claim 1, wherein the acidic adsorbent is aluminum silicate. 11. The basic inorganic adsorbent is activated alumina or a hydrotalcite compound.
The purification method according to any one of the above. 12. The purification method according to claim 1, wherein the basic inorganic adsorbent is a hydrotalcite compound. 13. The transition metal complex according to claim 1, wherein the central metal is a Group 8, 9, 10, or 11 element of the periodic table.
The purification method according to any one of claims 1 to 12. 14. The method according to claim 1, wherein the central metal of the transition metal complex is iron, nickel, ruthenium or copper. 15. The purification method according to claim 1, wherein the central metal of the transition metal complex is copper. 16. The purification method according to claim 1, wherein a polyamine compound is used as a catalyst ligand for atom transfer radical polymerization. 17. The purification method according to claim 1, wherein a triamine compound is used as a catalyst ligand for atom transfer radical polymerization. 18. A vinyl polymer obtained by the purification method according to claim 1. Description: 19. A hydrosilylation-reactive composition containing a vinyl polymer obtained by the purification method according to claim 1. Description: 20. (A) a vinyl polymer having an alkenyl group in a molecule obtained by the purification method according to any one of claims 1 to 17, and (B) a hydrosilylation containing a compound containing a hydrosilyl group. Reactive composition. 21. The hydrosilylation-reactive composition according to claim 20, wherein the component B is a compound having at least 1.1 hydrosilyl groups in the molecule. 22. The hydrosilylation-reactive composition according to claim 20, wherein the component B is a hydrosilane compound having a crosslinkable silyl group. 23. The method according to claim 19, further comprising a platinum catalyst.
The hydrosilylation-reactive composition according to any one of claims 22 to 22. 24. A vinyl polymer having a crosslinkable silyl group obtained by hydrosilylation of the hydrosilylation-reactive composition according to claim 22 or 23. 25. The vinyl polymer according to claim 24, wherein the crosslinkable silyl group is a hydrolyzable silyl group. 26. The vinyl polymer according to claim 25, wherein the hydrolyzable silyl group is a hydrosilyl group or an alkoxysilyl group. 27. A curable composition containing the vinyl polymer according to claim 24. 28. The purification method according to claim 1, wherein the vinyl polymer is a (meth) acrylic polymer. 29. The purification method according to claim 1, wherein the vinyl polymer is an acrylate ester polymer. 30. The refining method according to claim 1, wherein the vinyl polymer is a butyl acrylate polymer. 31. The vinyl polymer having a number average molecular weight of 50
The purification method according to any one of claims 1 to 17 and 28 to 30, wherein the purification method is 0 to 100,000. 32. The purification method according to any one of claims 1 to 17, and 28 to 31, wherein the value of the molecular weight distribution of the vinyl polymer is less than 1.8.