JP2003171416A - Method for purifying acrylic polymer - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a method for purifying a vinylic polymer for using the vinylic polymer as a component of a hydrosilylating reactive composition. <P>SOLUTION: This method for purifying the vinylic polymer produced by atom transfer radical polymerization of a vinylic monomer using a transition metal complex as a polymerization catalyst comprises passing the vinylic polymer through an adsorption column filled with an adsorbent. In the method, a mixture of the polymer with water is fed to the adsorption column. The mixture liquid of the vinylic polymer produced by the atom transfer radical polymerization with the water is subjected to a purification treatment in the adsorption column filled with the adsorbent to afford the vinylic polymer for the hydrosilylating reactive composition. <P>COPYRIGHT: (C)2003,JPO

Description

Detailed Description of the Invention

[0001]

TECHNICAL FIELD 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 The hydrosilylation reaction is one of the industrially very useful reactions, which is utilized for functional group conversion, crosslinking reaction and the like. For example, a polymer having an alkenyl group as a functional group at the terminal of the molecular chain is crosslinked and cured by using a hydrosilyl group-containing compound as a curing agent to give an excellent cured product such as 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 an alkenyl group at the terminal with a hydrosilyl group-containing compound having a crosslinkable silyl group. These hydrosilylation reactions proceed by heating, but a hydrosilylation catalyst is added in order to accelerate the reaction. Examples of such hydrosilylation catalysts include radical initiators such as organic peroxides and azo compounds, and transition metal catalysts. In particular, it is known that the use of a transition metal catalyst enables the hydrosilylation to proceed rapidly in a catalytic amount.

On the other hand, a living polymerization method is generally known as a precise synthesis method of a polymer. Living polymerization not only allows control of molecular weight and molecular weight distribution, but also gives a polymer having a clear terminal structure. Therefore,
Living polymerization is mentioned as one of the effective methods of introducing a functional group into the polymer terminal. Recently, in radical polymerization as well, a polymerization system capable of living polymerization has been found, and living radical polymerization has been actively studied. Particularly, by utilizing atom transfer radical polymerization, a vinyl polymer having a narrow molecular weight distribution can be obtained. As an example of atom transfer radical polymerization, an organic halide or a sulfonyl halide compound is used as an initiator, and a group 8, 9 or 10 of the periodic table,
Alternatively, a polymerization system in which a metal complex containing a Group 11 element as a central metal is used as a catalyst can be used. (For example, Matyjazeze
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 the transition metal complex which is a polymerization catalyst remains in the vinyl polymer produced by atom transfer radical polymerization, coloring of the polymer,
This will affect the physical properties and cause problems such as environmental safety. For example, in a vinyl polymer having an alkenyl group at the terminal produced by using an atom transfer radical polymerization method, the residual catalyst acts as a catalyst poison for the hydrosilylation reaction, which inhibits the hydrosilylation reaction and results in an expensive transition. The problem arises that a large amount of metal catalyst is required.

The present inventors have found that hydrosilylation activity is improved by bringing a vinyl polymer obtained by atom transfer radical polymerization into contact with an adsorbent such as aluminum silicate for purification (JP-A-11-193307). ). However, since the adsorbent treatment at that time was carried out in a batch system, a subsequent solid-liquid separation operation was required, and if it is carried out industrially on a large scale, a large-scale solid-liquid separation device will be required unless special measures are taken. There was a problem that it became necessary.

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.

[0007]

[Means for Solving the Problems] (1) In the present invention, a vinyl polymer produced by atom transfer radical polymerization of a vinyl monomer using a transition metal complex as a polymerization catalyst is placed in an adsorption tower filled with an adsorbent. A method for purifying a vinyl polymer to be passed through, which is characterized in that a mixture of the polymer and water is supplied to an adsorption tower. (2) Further, the present invention is an adsorption method in which a vinyl polymer having at least one alkenyl group in the molecule or an intermediate product obtained during the step of producing the vinyl polymer is filled with an adsorbent. A method for purifying the vinyl polymer or the intermediate product which is passed through the tower, which is characterized in that the polymer or the intermediate purified product is mixed with water and then supplied to an adsorption tower. . (3) Further, in the present invention, the vinyl polymer having at least one alkenyl group in the molecule is produced by atom transfer radical polymerization of a vinyl monomer using a transition metal complex as a polymerization catalyst. It is also a purification method characterized by the above.

In the present invention, the alkenyl group is preferably present at the molecular chain terminal of the vinyl polymer.

Further, in the present invention, the vinyl polymer is added with a compound having two or more carbon-carbon double bonds having low polymerizability during the polymerization reaction of atom transfer radical polymerization or after the completion of the polymerization reaction. It is preferably manufactured. (4) The present invention also provides a method for purifying a vinyl polymer, which is a component of a hydrosilylation-reactive composition, wherein a vinyl polymer is adsorbed onto a mixture of the polymer and water. It is also a purification method characterized by being supplied to a tower. (5) The present invention also provides a vinyl polymer obtained by the above-mentioned purification methods (1) to (4) and a hydrosilylation-reactive composition containing the polymer.

In the present invention, it is preferable that the vinyl polymer obtained by atom transfer radical polymerization and water are mixed in a mixing tank, and then the mixture of the vinyl polymer and water is supplied to an adsorption tower. .

In the present invention, the adsorbent is preferably an inorganic adsorbent or activated carbon.

In the present invention, the inorganic adsorbent is
It is preferably selected from the group consisting of activated clay or aluminum silicate, aluminum silicate, activated alumina or hydrotalcite-type compounds.

Further, in the present invention, the central metal of the transition metal complex is preferably an element of Group 8, 9, 10 or 11 of the periodic table.

In the present invention, the central metal of the transition metal complex is preferably iron, nickel, ruthenium or copper.

Further, in the present invention, it is preferable to use a polyamine compound as a catalyst ligand for atom transfer radical polymerization.

In the present invention, it is preferable to use a triamine compound as a catalyst ligand for atom transfer radical polymerization. (6) Further, the present invention provides (A) a vinyl-based polymer having an alkenyl group obtained by the above-mentioned purification methods (1) to (4), and (B) at least 1.1 hydrosilyl groups in the molecule. It is also a curable composition containing the compound having.

In the present invention, the component B is preferably a hydrosilane compound having a crosslinkable silyl group, and the curable composition preferably contains a platinum catalyst. (7) Further, the present invention provides a crosslink obtained by hydrosilylating a hydrosilyl group-containing compound having both a vinyl polymer having an alkenyl group and a crosslinkable silyl group, which are obtained by the purification methods of (1) to (4) above. It is also a vinyl polymer having a silyl group.

In the present invention, the crosslinkable silyl group is preferably a hydrolyzable silyl group.

Further, in the present invention, the hydrolyzable silyl group is preferably a hydrosilyl group or an alkoxysilyl group. (8) The present invention also provides a curable composition containing the vinyl polymer having a crosslinkable silyl group.

In the present invention, the vinyl polymer is preferably a (meth) acrylic polymer.

In the present invention, the vinyl polymer is preferably an acrylic ester polymer, more preferably a butyl acrylate polymer.

In the present invention, the vinyl polymer preferably has a number average molecular weight of 500 to 100,000.

Further, in the present invention, the value of the molecular weight distribution of the vinyl polymer is preferably less than 1.8.

[0024]

BEST MODE FOR CARRYING OUT THE INVENTION The present invention provides a method for purifying a vinyl polymer produced by utilizing atom transfer radical polymerization of a vinyl monomer using a transition metal complex as a polymerization catalyst,
The purification method is characterized in that a mixed liquid of the polymer and water is passed through an adsorption tower filled with an adsorbent, and the vinyl polymer to be purified is produced by using atom transfer radical polymerization. Not limited to those, general radical polymerization,
It may be a vinyl polymer obtained by another production method.

The mixture of the vinyl polymer and water in the present invention is usually a slurry in which droplets of the aqueous phase are dispersed in the organic phase. Atom Transfer Radical Polymerization First, the 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 monomer 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
Volume 8, 7901, Science 19
1996, 272, 866 pages, WO96 / 30421, WO97 / 18247, WO98 / 014
No. 80, WO98 / 40415, or S
awamoto et al., Macromolecules (Macro
, 1995, 28, 1721
Page, JP-A-9-208616, JP-A-8-411.
No. 17, for example.

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. As a specific 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 in the above formula, 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 , (in the formula, R ³ and R ⁴ are a hydrogen atom or an alkyl group having 1 to 20 carbon atoms, an aryl group, or an aralkyl group. , X is chlorine, bromine, or iodine) R ³ -C ₆ H ₄ -SO ₂ X (In the above formulas, R ³ is a hydrogen atom or a carbon number 1)
To an alkyl group, an aryl group, or an aralkyl group, and X is chlorine, bromine, or iodine).

By carrying out 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) (In the formula, R ¹ and R ² represent a group bonded to the ethylenically unsaturated group of the vinyl monomer. X represents chlorine, bromine or iodine. As an initiator of atom transfer radical polymerization, 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 also be used. 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 can be obtained. Examples of such a specific reactive functional group include an alkenyl group, a crosslinkable silyl group, a hydroxyl group, an epoxy group, an amino group and an amide group. Other appropriate functional groups can be introduced into the vinyl-based polymer by utilizing the reactivity of these reactive functional groups to undergo a one-step or several-step reaction.

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 methyl, R ^6, R ⁷ is hydrogen or a carbon A monovalent alkyl group, an aryl group, or an aralkyl of the numbers 1 to 20, or those linked to each other at the other end, R ⁸ is —C (O) O— (ester group), —C (O) — ( Keto group), or o-, m-, p
-Phenylene group, R ⁹ is a direct bond or has 1 to 2 carbon atoms.
A divalent organic group of 0, which may contain one or more ether bonds, X is chlorine, bromine, or iodine) Specific examples of the substituents R ⁶ and R ⁷ are hydrogen, methyl group, and ethyl group. , N-propyl group, isopropyl group, butyl group,
Examples thereof include a pentyl group and a hexyl group. R ⁶ and R ⁷ may be connected at the other end to form a cyclic skeleton.

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

[0030]

[Chemical 1] (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 (C
H ₂ ) _m CH = CH ₂ , (H ₃ C) ₂ C (X) C (O) O
(CH ₂ ) _n O (CH ₂ ) _m CH = CH ₂ , CH ₃ CH ₂ C
(H) (X) C (O) O (CH ₂ ) _n O (CH ₂ ) _m CH =
CH ₂ ,

[0031]

[Chemical 2] (In each of the above formulas, X is chlorine, bromine, or iodine.
(Prime, n is an integer of 1 to 20, m is an integer of 0 to 20) o, m, p-XCH₂-C₆H_Four-(CH₂)_n-CH = C
H₂, O, m, p-CH₃C (H) (X) -C₆H_Four-(C
H₂)_n-CH = CH₂, O, m, p-CH₃CH₂C
(H) (X) -C₆H_Four-(CH₂)_n-CH = CH₂, (In each of the above formulas, X is chlorine, bromine, or iodine.
(Prime, n is an integer from 0 to 20) o, m, p-XCH₂-C₆H_Four-(CH₂)_n-O- (C
H₂)_m-CH = CH₂, O, m, p-CH₃C (H)
(X) -C₆H_Four-(CH₂)_n-O- (CH₂)_m-CH =
CH₂, O, m, p-CH₃CH₂C (H) (X) -C₆H
_Four-(CH₂)_n-O- (CH₂)_mCH = CH₂, (In each of the above formulas, X is chlorine, bromine, or iodine.
(Prime, n is an integer of 1 to 20, m is an integer of 0 to 20) o, m, p-XCH₂-C₆H_Four-O- (CH₂)_n-CH
= CH₂, O, m, p-CH₃C (H) (X) -C₆H_Four−
O- (CH₂)_n-CH = CH₂, O, m, p-CH₃CH
₂C (H) (X) -C₆H_Four-O- (CH₂)_n-CH = C
H ₂, (In each of the above formulas, X is chlorine, bromine, or iodine.
(Prime, n is an integer from 0 to 20) o, m, p-XCH₂-C₆H_Four-O- (CH₂)_n-O-
(CH₂)_m-CH = CH₂, O, m, p-CH₃C (H)
(X) -C₆H_Four-O- (CH₂)_n-O- (CH₂)_m-C
H = CH₂, O, m, p-CH₃CH₂C (H) (X)-
C₆H_Four-O- (CH₂)_n-O- (CH ₂)_m-CH = CH
₂, (In each of the above formulas, X is chlorine, bromine, or iodine.
(Prime, n is an integer of 1 to 20, m is an integer of 0 to 20) Further as an organic halide having an alkenyl group
Examples thereof include compounds represented by the general formula (3). H₂C = C (R^Five) -R⁹-C (R⁶) (X) -R^Ten-R⁷  (3) (In the formula, 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
(May contain one or more ether bonds)
Is a direct bond, the halogen-bonded carbon
Vinyl group is bonded to the element,
is there. In this case, carbon-halogenation is caused by adjacent vinyl groups.
R is because the bond is activated.^TenAs C (O) O
It is not always necessary to have a group or phenylene group, etc.
It may be a bond. R⁹Is not a direct bond, charcoal
In order to activate the elementary-halogen bond, R^TenAs C
(O) O group, C (O) group and phenylene group are preferred.

To specifically exemplify the compound of the general formula (3), CH ₂ ═CHCH ₂ X, CH ₂ ═C (CH ₃ ) CH
₂ X, CH ₂ = CHC (H) (X) CH ₃ , CH ₂ = C (C
H ₃ ) C (H) (X) CH ₃ , CH ₂ ═CHC (X) (C
_{H 3) 2, CH 2 =} CHC (H) (X) C 2 H 5, CH 2 = C
HC (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 = CH (CH 2) 3} C (H) (X) -CO 2 R, CH 2 =
_{CH (CH 2) 8 C (} H) (X) -CO 2 R, CH 2 = CH
_{CH 2 C (H) (X} ) -C 6 H 5, CH 2 = CH (CH 2) 2
C (H) (X) -C 6 H 5, CH 2 = CH (CH 2) 3 C
_{(H) (X) -C 6} H 5, ( in each formula above, X is chlorine, bromine or iodine, R represents an alkyl group having 1 to 20 carbon atoms, an aryl group, an aralkyl group,) and the like, etc. it can.

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

Organic halogen having the above-mentioned crosslinkable silyl group
The compound is not particularly limited and is represented by, for example, the general formula (4).
An example is one having a structure. R⁶R⁷C (X) -R⁸-R⁹-C (H) (R^Five) CH₂-[Si (R¹¹)_2-b(Y)_b O]_m-Si (R¹²)_3-a(Y)_a  (4) (In the formula, R^Five, R⁶, R⁷, R⁸, R⁹, X is the same as above,
R¹¹, R¹²Are all alkyl groups having 1 to 20 carbon atoms,
Aryl group, aralkyl group, or (R ')₃SiO-
(R 'is a monovalent hydrocarbon group having 1 to 20 carbon atoms,
The three R's may be the same or different.
And a triorganosiloxy group represented by¹¹Well
Or R¹²When two or more exist, they are the same
May be different. Y is a hydroxyl group or water
A decomposable group is shown, and when two or more Y are present, they are the same.
It 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. However, if a + mb ≧ 1
Be satisfied) To specifically exemplify the compound of the general formula (4), XC
H₂C (O) O (CH₂)_nSi (OCH₃)₃, CH₃C
(H) (X) C (O) O (CH₂)_nSi (OCH₃)₃,
(CH₃)₂C (X) C (O) O (CH₂)_nSi (OCH
₃)₃, XCH₂C (O) O (CH₂)_nSi (CH₃) (O
CH₃)₂, CH₃C (H) (X) C (O) O (CH₂)_n
Si (CH₃) (OCH₃)₂, (CH₃)₂C (X) C
(O) O (CH₂)_nSi (CH₃) (OCH₃)₂, (In each of the above formulas, X is chlorine, bromine, iodine, and n is
An integer from 0 to 20) XCH₂C (O) O (CH₂)_nO (CH₂)_mSi (OC
H₃)₃, H₃CC (H) (X) C (O) O (CH₂)_nO
(CH₂)_mSi (OCH₃)₃, (H₃C)₂C (X) C
(O) O (CH₂)_nO (CH₂)_mSi (OCH₃)₃, C
H₃CH₂C (H) (X) C (O) O (CH₂)_nO (CH
₂)_mSi (OCH₃)₃, XCH₂C (O) O (CH₂)_n
O (CH₂)_mSi (CH₃) (OCH₃)₂, H₃CC
(H) (X) C (O) O (CH₂)_nO (CH₂)_m-Si
(CH₃) (OCH₃)₂, (H₃C)₂C (X) C (O)
O (CH₂)_nO (CH₂)_m-Si (CH₃) (OCH₃)
₂, CH₃CH₂C (H) (X) C (O) O (CH₂)_nO
(CH₂)_m-Si (CH₃) (OCH₃)₂, (In each of the above formulas, X is chlorine, bromine, iodine, and n is
1 to 20 integer, m is 0 to 20 integer) o, m, p-XCH₂-C₆H_Four-(CH₂)₂Si (OC
H₃)₃, O, m, p-CH₃C (H) (X) -C₆H_Four−
(CH₂)₂Si (OCH₃)₃, O, m, p-CH₃CH₂
C (H) (X) -C₆H_Four-(CH₂)₂Si (OC
H₃)₃, O, m, p-XCH₂-C₆H_Four-(CH₂)₃S
i (OCH₃)₃, O, m, p-CH₃C (H) (X)-
C₆H_Four-(CH₂)₃Si (OCH₃)₃, O, m, p-C
H₃CH₂C (H) (X) -C₆H_Four-(CH₂)₃Si (O
CH₃)₃, O, m, p-XCH₂-C₆H_Four-(CH₂)₂
-O- (CH₂)₃Si (OCH₃)₃, O, m, p-CH
₃C (H) (X) -C₆H_Four-(CH₂)₂-O- (CH₂)
₃Si (OCH₃)₃, O, m, p-CH₃CH₂C (H)
(X) -C₆H_Four-(CH₂)₂-O- (CH₂)₃Si (O
CH₃)₃, O, m, p-XCH₂-C₆H_Four-O- (C
H₂)₃Si (OCH₃)₃, O, m, p-CH₃C (H)
(X) -C₆H_Four-O- (CH₂)₃Si (OCH₃)₃,
o, m, p-CH₃CH₂C (H) (X) -C₆H_Four-O-
(CH₂)₃-Si (OCH₃)₃, O, m, p-XCH₂
-C₆H_Four-O- (CH₂)₂-O- (CH₂)₃-Si (O
CH₃)₃, O, m, p-CH₃C (H) (X) -C₆H_Four
-O- (CH₂)₂-O- (CH₂)₃Si (OCH₃)₃,
o, m, p-CH₃CH₂C (H) (X) -C₆H_Four-O-
(CH₂)₂-O- (CH ₂)₃Si (OCH₃)₃, (In each of the above formulas, X is chlorine, bromine, or iodine.
And the like.

Further examples of the organic halide having a crosslinkable silyl group include those having a structure represented by the general formula (5). ^{_{(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. If such a compound is specifically exemplified, (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) -C
O 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 the following compounds are exemplified. 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, Base,
(Aryl group, aralkyl group, n is an integer of 1 to 20) The organic halide having the above 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.

[0037]

[Chemical 3] (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,
Aryl group, aralkyl group, 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,
Alternatively, a sulfonyl halide compound is preferably used as an initiator. To give a concrete example,

[0038]

[Chemical 4]

[0039]

[Chemical 5] Etc.

The transition metal complex used as the polymerization catalyst is not particularly limited, but is preferably No. 7 of the Periodic Table.
It is a metal complex whose central metal is an element of Group 10, Group 8, Group 10, Group 10 or Group 11. More preferred are complexes of 0-valent copper, 1-valent copper, 2-valent ruthenium, 2-valent iron or 2-valent nickel. Of these, a copper complex is preferable. If a monovalent copper compound is specifically exemplified,
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 its derivative, 1,10-phenanthroline or its derivative, or tetramethylethylenediamine, pentamethyldiethylenetriamine or hexamethyltris (2-aminoethyl) amine is used in order to enhance the catalytic activity. Polyamine or the like is added as a ligand. In addition, divalent ruthenium chloride tristriphenylphosphine complex (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, a bivalent iron bistriphenylphosphine complex (FeCl ₂ (PP
h ₃ ) ₂ ), divalent nickel bistriphenylphosphine complex (NiCl ₂ (PPh ₃ ) ₂ ) and divalent nickel bistributylphosphine complex (NiBr ₂ (P
Bu ₃ ) ₂ ) is also suitable as a catalyst.

The vinyl monomer used in this polymerization is not particularly limited, and examples thereof include (meth) acrylic acid, methyl (meth) acrylate, ethyl (meth) acrylate, -n-propyl (meth) acrylate, ( Isopropyl methacrylate, n-butyl (meth) acrylate, isobutyl (meth) acrylate, tert-butyl (meth) acrylate, n-pentyl (meth) acrylate, (meth) acrylic acid-n -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, ( (Meth) acrylic acid-2-methoxyethyl, (meth) acrylic acid-3-methoxybutyl, (meth) acrylic acid-2-
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) acrylic Acid 2-trifluoromethylethyl, (meth) acrylic acid 2-perfluoroethylethyl, (meth) acrylic acid 2-perfluoroethyl-2-
Perfluorobutylethyl, 2-perfluoroethyl (meth) acrylate, perfluoromethyl (meth) acrylate, diperfluoromethylmethyl (meth) acrylate, 2-perfluoromethyl-2-methacrylate
(Meth) acrylic acid-based monomers such as perfluoroethyl methyl, (meth) acrylic acid 2-perfluorohexylethyl, (meth) acrylic acid 2-perfluorodecylethyl, and (meth) acrylic acid 2-perfluorohexadecylethyl Styrene-based 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 Maleimide-based monomers such as imide, ethylmaleimide, propylmaleimide, butylmaleimide, hexylmaleimide, octylmaleimide, dodecylmaleimide, stearylmaleimide, phenylmaleimide, cyclohexylmaleimide; nitrile group-containing vinyl monomers such as acrylonitrile and methacrylonitrile; acrylamide, Amide group-containing vinyl monomers 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 and allyl alcohol. These may be used alone or a plurality of them may be copolymerized. Of these, styrene-based monomers and (meth) acrylic acid-based monomers are preferable in view of the physical properties of the product. Acrylic acid ester monomers and methacrylic acid ester monomers are more preferable, acrylic acid ester monomers are particularly preferable, and butyl acrylate is still more preferable. In the present invention, these preferred monomers may be copolymerized with other monomers, and further may be block copolymerized,
In that case, the weight ratio of these preferable monomers is 40%.
It is preferably included. In the above expression format, for example, (meth) acrylic acid represents acrylic acid and / or methacrylic acid.

The polymerization reaction can be carried out without any solvent, but can also be carried out in various solvents. The type of solvent is not particularly limited, and examples thereof include hydrocarbon solvents such as benzene and toluene; diethyl ether, tetrahydrofuran,
Ether solvents such as diphenyl ether, anisole, dimethoxybenzene; methylene chloride, chloroform,
Halogenated hydrocarbon solvents such as chlorobenzene; ketone solvents such as acetone, methyl ethyl ketone, 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; N, N- Examples thereof include amide solvents such as dimethylformamide and N, N-dimethylacetamide. These may be used alone or in combination of two or more. Polymerization can also be carried out in an emulsion system or a system using CO ₂ as a medium.

Polymerization may be, but is not limited to, 0-200 ° C.
Can be carried out in the range of, preferably room temperature to 150 ℃
Is the range. Vinyl Polymer Next, the vinyl polymer in the present invention will be described in detail.

The vinyl polymer is not particularly limited, but is preferably one produced by atom transfer radical polymerization of a vinyl monomer. Such a vinyl-based monomer is not particularly limited, and those already exemplified can be used. These vinyl-based monomers may be used alone or a plurality of them may be copolymerized. Of these, styrene-based monomers and (meth) acrylic acid-based monomers are preferable in view of the physical properties of the product. Acrylic acid ester monomers and methacrylic acid ester monomers are more preferable, acrylic acid ester monomers are particularly preferable, and butyl acrylate is still more preferable. In the present invention, these preferred monomers may be copolymerized with other monomers, and may be further block copolymerized. In that case, it is preferable that these preferred monomers are contained in an amount of 40% by weight or more. .

Molecular weight distribution of vinyl polymer, that is,
The ratio of the weight average molecular weight to the number average molecular weight measured by gel permeation chromatography is not particularly limited, but is preferably less than 1.8, preferably 1.7 or less, and 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 of the present invention, chloroform is usually used as the mobile phase, the measurement is carried out with 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 original characteristics of the vinyl polymer are difficult to be expressed, and when it is too high, the handling becomes difficult.

The vinyl polymer may have a reactive functional group in the molecule. When it has a reactive functional group in the molecule, it may be present in 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. It is also possible to convert the reactive functional group into another suitable functional group in one step 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. Vinyl Polymer Having Alkenyl Group Next, the vinyl polymer having an alkenyl group will be described in detail. 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 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 is obtained by hydrosilylating a hydrosilane compound having a crosslinkable functional group with a vinyl polymer having at least one alkenyl group in the molecule.

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

Although the alkenyl group in the present invention is not limited, it 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 an alkyl group having 1 to 20 carbon atoms, an aryl group having 6 to 20 carbon atoms, and an aralkyl group having 7 to 20 carbon atoms are preferable, and specifically, 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 is an integer of 0 or more, the total number of carbon atoms in each group is 20 or _{less) n -C 6 H 5 (CH} 3) 2 Of these, hydrogen as R ¹³ Or a methyl group is more preferable.

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

The bond form between the alkenyl group and the main chain of the polymer is not particularly limited, but it may be bonded via 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 required to have rubber-like properties, it has a great influence on rubber elasticity. At least one of the alkenyl groups is preferably at the terminal of the molecular chain because the molecular weight between the crosslinking points can be large. More preferably, it has all alkenyl groups at the molecular chain ends. It is more preferable that it exists at the terminal of the molecule.

The number of alkenyl groups is not particularly limited,
In order to obtain a cured product having a higher cross-linking property, one or more on average, preferably 1.2 or more, more preferably 1.5 or more.
More than one.

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

(Aa) When synthesizing a vinyl polymer by atom transfer radical polymerization, for example, a polymerizable alkenyl group in a molecule and a low polymerizability as shown in the following general formula (9) are used. A method of reacting a compound having an alkenyl group 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 o-, m-, p-phenylene group, R ¹⁶ represents a direct bond or a divalent organic group having 1 to 20 carbon atoms, and contains at least one ether bond. You may stay. R ¹⁷ represents hydrogen or an organic group having 1 to 20 carbon atoms) In the general formula (9), R ¹⁷ is 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 an alkyl group having 1 to 20 carbon atoms, an aryl group having 6 to 20 carbon atoms, and an aralkyl group having 7 to 20 carbon atoms are preferable, and specifically, 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 is an integer of 0 or more, the total number of carbon atoms in each group is 20 or _{less) n -C 6 H 5 (CH} 3) 2 Of these, hydrogen as R ¹⁷ Or a methyl group is more preferable.

The compound having both a polymerizable alkenyl group and a low polymerizable alkenyl group in one molecule may be reacted at any time, but the cured product obtained by curing the vinyl polymer has rubber-like properties. When it is expected, it is preferable to react as the second monomer at the end of the polymerization reaction or after the reaction of the predetermined monomer.

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

(A-c) Vinyl-based polymers having at least one highly reactive carbon-halogen bond at the terminal obtained by atom transfer radical polymerization, such as organotins such as allyltributyltin and allyltrioctyltin. A method of substituting halogen by reacting various organometallic compounds having such an alkenyl group.

(A-d) A 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 represented by the general formula (10). A method of reacting a stabilized carbanion to replace halogen. ^{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 Is an electron-withdrawing group, or one is the electron-withdrawing group and the other is hydrogen or a carbon number of 1 to 10
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. ) As the electron-withdrawing groups _{^{R 18, R 19, -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.

(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 metal element such as zinc or an organometallic compound. To prepare an enolate anion, followed by alkenyl group-containing compound having a leaving group such as halogen or acetyl group, carbonyl compound having an alkenyl group, isocyanate compound having an alkenyl group, acid halide having an alkenyl group, etc. , A method of reacting with an electrophilic compound having an alkenyl group.

(Af) A vinyl-based polymer having at least one highly reactive carbon-halogen bond at the terminal, which is obtained by atom transfer radical polymerization, is represented by, for example, the general formula (1)
A method of substituting halogen by reacting an oxyanion or a carboxylate anion having an alkenyl group as shown in 1) 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 and M ⁺ are the same as above, and R ²² is a direct bond or a divalent organic group having 1 to 20 carbon atoms and may contain one or more ether bonds).

Among the methods (Aa) to (Af), the methods (Ab) and (Af) are preferable because they are easier to control. The method of introducing (Ab) and (Af) will be described in detail below. Diene compound addition method [(Ab) method] (Ab) method is 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, "diene compound") is reacted.

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 = 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, 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, and One R (or two R ′) may be the same or different from each other. Any two of the two substituents of two R and two R ′ may be bonded to each other to have a cyclic structure. ], But a terminal alkenyl group is more preferable. R is hydrogen or an organic group having 1 to 20 carbon atoms, and as the organic group having 1 to 20 carbon atoms, 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 preferable. Of these, R or hydrogen is particularly preferable as R.

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,
5-hexadiene, 1,7-octadiene, 1,9-decadiene, 4-vinyl-1-cyclohexene and the like can be mentioned, but 1,5-hexadiene, 1,7-octadiene and 1,9-decadiene are preferable.

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

The amount of the diene compound added needs to be adjusted depending on 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 compound may be in an equivalent amount or a small excess amount with respect to the polymerization growth end, but when the reactivity of the two alkenyl groups is equal to or little different from each other, the diene compound may have a large difference. Since both alkenyl groups react and the polymerization terminals are coupled to each other, the amount of the diene compound added is preferably an excess amount with respect to the polymer growth terminal, preferably 1.5 times or more, and more preferably It is 3 times or more, particularly preferably 5 times or more. Nucleophilic substitution method [(Af) method] The (Af) method is a method in which an alkenyl group is added to a vinyl-based polymer having at least one highly reactive carbon-halogen bond at the terminal obtained by atom transfer radical polymerization. It is characterized by reacting an oxyanion or a carboxylate anion that it has to replace halogen.

The oxy anion or carboxylate anion having an alkenyl group is not particularly limited, and examples thereof include 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 and M ⁺ are the same as above, R ²² is a direct bond or a divalent organic group having 1 to 20 carbon atoms and may contain one or more ether bonds. Are, for example, ammonia; alkylamines such as trimethylamine, triethylamine and tributylamine;
The amount of the basic compound such as a polyamine such as tetramethylethylenediamine and pentamethyldiethylenetriamine; a pyridine compound such as pyridine and picoline may be used in an equivalent amount or a small excess amount with respect to the precursor, and preferably 1 to 1.2 equivalents. is there.

Examples of the solvent used when 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; allyl phenol, ants. Examples thereof include alkenyl group-containing phenolic hydroxyl group salts such as loxyphenol; alkenyl group-containing carboxylic acid salts such as 10-undecylenic acid, 4-pentenoic acid and vinylacetic acid;

M ⁺ is a counter cation, and examples of M ⁺ include alkali metal ions, specifically lithium ion, sodium ion, potassium ion, and quaternary ammonium ion. Examples of the quaternary ammonium ion include tetramethylammonium ion, tetraethylammonium ion, tetrabenzylammonium ion, trimethyldodecylammonium ion, tetrabutylammonium ion and dimethylpiperidinium ion, and sodium ion and 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, still more preferably 1.0 to 1.2. It is equivalent.

The solvent for carrying out this reaction is not particularly limited, but a solvent having a relatively high polarity is preferable, and for example, ether solvents such as diethyl ether, tetrahydrofuran, diphenyl ether, anisole, dimethoxybenzene; 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-based solvents such as butyl acetate; Carbonate-based solvents such as ethylene carbonate and propylene carbonate;
Examples thereof include amide solvents such as dimethylformamide and dimethylacetamide; sulfoxide solvents such as dimethyl sulfoxide. These may 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 preferable. Although the reaction temperature is not limited, it is generally 0 to 150 ° C., and more preferably room temperature to 100 ° C.

Further, amines, ammonium salts, crown ethers, etc. may be added to the reaction system as reaction accelerators.

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

When there is an ester group in the side chain or main chain of the vinyl polymer, transesterification may occur when an oxyanion having a high nucleophilicity is used, so that a carboxylate anion having a low nucleophilicity is obtained. Is more preferably used. Method for converting a hydroxyl group into an alkenyl group A 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 of reacting a hydroxyl group of a vinyl polymer having at least one hydroxyl group with a base such as sodium methoxide and reacting it with an alkenyl group-containing halide such as allyl chloride.

(Ah) A method of reacting an alkenyl group-containing isocyanate compound such as allyl isocyanate 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 the hydroxyl group of the 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, 1
A method of reacting an alkenyl group-containing carboxylic acid such as 0-undecenoic acid in the presence of an acid catalyst.

(Ak) A method in which a vinyl polymer having a hydroxyl group is reacted with a diisocyanate compound, and a compound having both an alkenyl group and a hydroxyl group is reacted with the residual 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, but any conventionally known diisocyanate compound can be used. For example, toluylene diisocyanate, 4,4'-
Diphenylmethane diisocyanate, hexamethyldiisocyanate, xylylene diisocyanate, metaxylylene diisocyanate, 1,5-naphthalene diisocyanate, hydrogenated diphenylmethane diisocyanate,
Isocyanate compounds such as hydrogenated toluylene diisocyanate, hydrogenated xylylene diisocyanate, and isophorone diisocyanate; These may be used alone or in combination of two or more. Blocked isocyanate may also be used.

In order to take advantage of the better weather resistance, it is preferable to use a diisocyanate compound having no aromatic ring, such as hexamethylene diisocyanate or hydrogenated diphenylmethane diisocyanate. 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 a vinyl polymer having a hydroxyl group are as follows. However, the method is not limited to these methods.

(Ba) When synthesizing a vinyl polymer 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 mentioned in 5). ^{_{H 2 C = C (R 14}} ) -R 15 -R 16 -OH (15) ( ^{wherein, R 14, R 15, R} 16 are as defined above) The polymerization of the alkenyl group and a hydroxyl group per molecule There is no limitation on the timing of reacting the compound having both of the two, but particularly in living radical polymerization, when rubber properties are expected, the reaction is performed 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 synthesizing a vinyl polymer by atom transfer radical polymerization, at the end of the polymerization reaction or after the reaction of a predetermined monomer, for example, 10-undecenol, 5-hexenol, allyl alcohol, etc. A method of reacting alkenyl alcohol.

(Bf) The halogen 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. A method of introducing a hydroxyl group into.

(B-g) A vinyl-based polymer having at least one highly reactive carbon-halogen bond at the terminal obtained by atom transfer radical polymerization has a hydroxyl group as represented by the general formula (16). Method of reacting a halogenated carbanion to replace 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-based polymer having at least one highly reactive carbon-halogen bond at the terminal obtained by atom transfer radical polymerization is reacted with a metal element such as zinc or an organometallic compound. A method of preparing an enolate anion by reacting with an aldehyde or a ketone.

(Bi) A vinyl-based polymer having at least one highly reactive carbon-halogen bond at the terminal obtained by atom transfer radical polymerization, and a hydroxyl group represented by the general formula (17) or 18, for example. A method of substituting halogen by reacting an oxyanion or a carboxylate anion having. ^{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 the above) Regarding M ⁺ , reaction conditions, solvent, etc., all those described in the description of (Af) can be preferably used. (Bj) When synthesizing a vinyl polymer by atom transfer radical polymerization, an alkenyl group having low polymerizability in one molecule and A method of reacting a compound having a hydroxyl group. Although such a compound is not particularly limited, examples thereof include the 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) However, it is easy to obtain, so 10-
Alkenyl alcohols such as undecenol, 5-hexenol, allyl alcohol are preferred.

Among the synthetic methods (B-a) to (B-j), (B-b) and (B-
Method i) is preferred. Regarding the adsorbent treatment by the adsorption tower, the purification method of the present invention is characterized in that the mixture of the polymer or the intermediate product and water is passed through the adsorption tower filled with the adsorbent to carry out the adsorbent treatment. ..

The adsorption tower in the present invention is not limited to a so-called tower shape, and may be, for example, a horizontal type in which the above mixture flows in the horizontal direction, or a relatively low floor surface. It may be installed at a position.

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 is
It can also be applied to a vinyl polymer obtained by a production method other than the atom transfer radical polymerization method.

Examples of the adsorbent include activated carbon, synthetic resin adsorbents such as ion exchange resins, and inorganic adsorbents such as zeolite. Any of these can be preferably used. The adsorbents used in the present purification method are exemplified by (Ca) to (Cc) below, but the present invention is not limited to these adsorbents. (C-a) Activated carbon The activated carbon is mostly carbonaceous carbon and has high adsorptivity.
As a manufacturing method, for example, wood, lignite, peat or the like is treated with zinc chloride, phosphoric acid or the like as an activator and carbonized, 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 manufacturing process, chemically activated carbons are acidic and steam activated carbons are essentially basic. (Cb) Synthetic resin-based adsorbent An example of the synthetic resin-based adsorbent is an ion exchange resin. As the ion exchange resin, a general acidic or basic ion exchange resin may be used. Also, chelate ion exchange resins may be used. Examples of the functional group of the acidic ion exchange resin include a carboxylic acid group and a sulfonic acid group, and examples of the functional group of the basic ion exchange resin include an amino group, and functional groups of the chelate ion exchange resin such as iminodiacetic acid group and polyamine group. Etc. are illustrated. (C-c) Inorganic adsorbent The inorganic adsorbent has a solid acid, a solid base, or a neutral character, and the particles have a porous structure, so that the adsorbability is very high. Another feature is that it can be used from low temperatures to high temperatures. The inorganic adsorbent is not particularly limited, but typical examples thereof include those containing aluminum, magnesium, silicon or the like as a main component or a combination thereof. For example, silicon dioxide; magnesium oxide; silica gel; silica-alumina, aluminum silicate; magnesium silicate; activated alumina; clay-based adsorbents such as acid clay, activated clay; hydrous aluminosilicate minerals such as sodium aluminum silicate Examples thereof include a system adsorbent; a dawsonite compound, and a hydrotalcite compound.

Zeolites include naturally-occurring and synthetic zeolites, and both may be used.

Silicon dioxide is known to be of various types such as 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 acid such as Carplex # 80 (all of which are Shionogi Pharmaceutical Co., Ltd.) are included, but the invention is not limited thereto.

Further, aluminum silicate is a material in which a part of silicon of silicic acid is replaced by aluminum, and pumice, fly ash, kaolin, bentonite, activated clay, diatomaceous earth and the like are known. Among these, synthetic aluminum silicate has a large specific surface area and a high adsorption capacity. Examples of synthetic aluminum silicates include Kyoward 700 series (made by Kyowa Kagaku).
It is not limited to these.

Hydrotalcite compounds are divalent metals (Mg ²⁺ , Mn ²⁺ , Fe ²⁺ , Co ²⁺ , Ni ²⁺ , Cu ²⁺ ,
Zn ^2+, etc. and trivalent metals (Al ³⁺ , Fe ³⁺ , Cr ³⁺ , C
o ³⁺ , In ^3+, etc.) or a part of the hydroxyl groups of the above-mentioned hydroxides are halogen ions, NO ₃ ⁻ , CO ₃ ²⁻ , SO _{4
^{2-, Fe (CN) 6 3-}} , CH 3 CO 2 -, oxalic acid ion,
It is an anion such as salicylate ion.
Of these, the divalent metal is Mg ²⁺ and the trivalent metal is Al ³⁺
However, hydrotalcites in which a part of the hydroxyl groups are exchanged with CO ₃ ^2- are preferable, and examples of the synthetic products include Kyoward 500 series and Kyoward 1000 series (both manufactured by Kyowa Chemical Co., Ltd.). , But is not limited to these. Further, an adsorbent obtained by firing the above hydrotalcites is also suitably used.
Among them, divalent metal is Mg ²⁺ and trivalent metal is Al ^3+.
MgO obtained by firing hydrotalcites that are
-AlO ₃ type solid solution is preferable, for example, Kyoward 2
000 (manufactured by Kyowa Chemical Co., Ltd.), but not limited thereto. In the present invention, fired products of hydrotalcites are also classified as hydrotalcites.

As the adsorbent used, the inorganic adsorbents exemplified in (C-c) are preferable, and aluminum silicate and hydrotalcites are more preferable. It is particularly preferable to use aluminum silicate and hydrotalcites together.

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

As a method of adding water, there are a method of simply supplying to the line immediately before the adsorption tower and a method of supplying to the line in which a static mixer is installed. Further, there is a method of using a mixing tank in order to mix water more sufficiently. In this case, it is possible to mix by a stirring method, a pump circulation method, or the like.

When the polymer and water are mixed, they may be solvent-free or diluted with a solvent. However, it is often preferable to dilute with a solvent in order to facilitate passage through the column and to enhance dispersibility of water. A general solvent may be used as the diluting solvent. When a solvent is used, it is necessary to consider the load of desolventization later, and the amount of the solvent used is preferably 100 parts by weight or less with respect to 100 parts by weight of the vinyl polymer. The temperature of the liquid used for the treatment in the adsorption tower is not particularly limited, but it is generally 0 ° C to 200 ° C, preferably room temperature to 180 ° C.

The amount of water added to the polymer before adsorption is preferably 0.1 to 100 parts by weight, preferably 1 to 10 parts by weight, based on the polymer.
More preferably parts by weight.

After the adsorption tower, in general, a cartridge type filter or the like may be used for removing fine powder that may slightly leak, and in this case, the same measure may be taken as necessary. it can.

The adsorption treatment may be performed on the vinyl polymer (crude product) as the final product, but may be performed on the intermediate product for producing the vinyl polymer.
For example, for a vinyl-based polymer having an alkenyl group obtained by atom transfer radical polymerization, a vinyl-based polymer having a highly reactive carbon-halogen bond which is an intermediate product for producing the polymer or the vinyl-based polymer. Polymer,
The adsorption treatment can also be performed on a vinyl polymer such as a vinyl polymer having a hydroxyl group. Hydrosilylation Reactive Composition The hydrosilylation reactive composition of the present invention contains the vinyl polymer which has been 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 hydrosilyl group-containing compound. .

The vinyl polymer as the component A is a vinyl polymer having an alkenyl group in the molecule obtained by utilizing the above-mentioned atom transfer radical polymerization, and the above-mentioned ones may be used. The hydrosilyl group-containing compound as the B component is not particularly limited and various compounds can be used. For example, a compound having at least 1.1 hydrosilyl groups in the molecule, a hydrosilane compound having a crosslinkable silyl group, and the like can be mentioned. 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)).

Within such a molecule at least 1.1
The compound having a hydrosilyl group is not particularly limited.
Is represented by the general formula (22) or (23),
Chain polysiloxane R^{twenty three} ₃SiO- [Si (R^{twenty three})₂O]_a-[Si (H) (R^{twenty four}) O]_b-[Si (R ^{twenty four} ) (R^{twenty five}) O]_c-SiR^{twenty three} ₃  (22) HR^{twenty three} ₂SiO- [Si (R^{twenty three})₂O]_a-[Si (H) (R^{twenty four}) O]_b-[Si ( R^{twenty four}) (R^{twenty five}) O]_c-SiR^{twenty three} ₂H (23) (In the formula, 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 alkyl having 1 to 10 carbons
Represents a group or an 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 cyclic siloxane represented by the general formula (24);

[0107]

[Chemical 6] (In the formula, R²⁶And R²⁷Is an alkyl group having 1 to 6 carbon atoms,
Or a phenyl group, R ²⁸Is alkyl having 1 to 10 carbons
Represents a group or an 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. ) Etc.
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 general formulas (27) and (27) The cyclic siloxane represented by 28) is preferable. _{(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) ( formula In the formula, R ²⁴ represents hydrogen or a methyl group, and g is 2 ≦ g.
≦ 100 and h are integers of 0 ≦ h ≦ 100. C ₆ H ₅ represents a phenyl group. )

[0109]

[Chemical 7] (In the formula, 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 as the component B, the hydrosilyl groups represented by the general formulas (22) to (28) can be used for low-molecular compounds having two or more alkenyl groups in the molecule. A compound obtained by subjecting a group-containing compound to an addition reaction so that a part of hydrosilyl groups remains 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,
Ether compounds such as O'-diallyl bisphenol A and 3,3'-diallyl bisphenol A, ester compounds such as diallyl phthalate, diallyl isophthalate, triallyl trimellitate and tetraallyl pyromellitate, and diethylene glycol diallyl carbonate Examples thereof include carbonate compounds.

The above-mentioned alkenyl group-containing compound was 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 give the compound. Obtainable. Among these compounds, the following compounds are preferable in consideration of availability of raw materials, easiness of removing excess siloxane, and compatibility with vinyl polymers.

[0111]

[Chemical 8] The vinyl polymer of the component A and the hydrosilyl group-containing compound of the component B can be mixed at any ratio, but from the viewpoint of curability, the molar ratio of the alkenyl group to the hydrosilyl group is 5
Is preferably in the range of 0.2 to 2.5, more preferably 2.5
It is particularly preferable that it is ˜0.4. If the molar ratio is 5 or more, curing will be insufficient and only a cured product with low tackiness and low strength will be obtained, and if it is less than 0.2, a large amount of active hydrosilyl groups will remain in the cured product after curing. However, 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 hydrosilyl group-containing compound of the component B proceeds by mixing and heating the two components. Can be added. Such a hydrosilylation catalyst is not particularly limited, and examples thereof include radical initiators such as organic peroxides and azo compounds, and transition metal catalysts.

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 peroxides, benzoyl peroxides, p-chlorobenzoyl peroxides, m-chlorobenzoyl peroxides, 2,4-dichlorobenzoyl peroxides, lauroyl peroxides, peracid esters such as perbenzoic acid-t-butyl, perdialkyl peroxides. Peroxydicarbonates such as diisopropyl carbonate, di-2-ethylhexyl perdicarbonate, 1,1-di (t-butylperoxy) cyclohexane, 1,1-di (t-butylperoxy) -3,3,5-trimethyl Peroxyke like cyclohexane It can be mentioned Lumpur and the like.

The transition metal catalyst is also not particularly limited, and examples thereof include platinum solid, a dispersion of platinum solid in a carrier such as alumina, silica, carbon black, chloroplatinic acid, chloroplatinic acid and alcohol, aldehyde, Examples thereof include complexes with ketones, platinum-olefin complexes, and platinum (0) -divinyltetramethyldisiloxane complexes. 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 kinds. The amount of the catalyst is not particularly limited, but it is 1 per 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 will not proceed sufficiently. Also, hydrosilylation catalysts are generally expensive and corrosive, and
Since a large amount of hydrogen gas may be generated and the cured product may foam, it is preferable not to use 10 ^-1 mol or more.

The curing temperature is not particularly limited, but it is generally 0 ° C. to 200 ° C., preferably 30 ° C. to 150 ° C., and more preferably 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,
Typical examples include the compounds represented by the general formula 29. _{^{H- [Si (R 11) 2}} -b (Y) b O] m -Si (R 12) 3-a (Y) a (29) { wherein, R ^11, R ¹² are both carbons 1 ~ 20 alkyl groups, C6-20 aryl groups, C7-20
Or an aralkyl group of (R ′) ₃ SiO— (R ′ is a monovalent hydrocarbon group having 1 to 20 carbon atoms and has 3 R ′
May be the same or different), and R ¹¹ or R ¹² is 2
When there are one or more, they may be the same or different. Y represents a hydroxyl group or a hydrolyzable group, and when two or more Y 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. } As the hydrolyzable group, for example, a hydrogen atom, an alkoxy group, an acyloxy group, a ketoximate group, an amino group,
Examples include commonly used groups such as amide group, aminooxy group, mercapto group and alkenyloxy group.
Among these, an alkoxy group, an amide group, and an aminooxy group are preferable, but an alkoxy group is particularly preferable in terms of mild hydrolyzability and easy handling.

The hydrolyzable group and hydroxyl group can be bonded to one silicon atom in the range of 1 to 3;
The range of b) is preferably 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 the crosslinkable silyl group is 1 or more, but in the case of silicon atoms linked by a siloxane bond or the like, it is preferably 20 or less.

Among these hydrosilane compounds, 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 described above) is particularly preferable. A compound having a group is preferable because it is 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.
The vinyl-based polymer having at least 1.1 crosslinkable silyl groups in the molecule and the curable composition containing the vinyl-based polymer (curable composition (2)) obtained by the above method are also included in the present invention. Is one.

[0120] As the crosslinkable silyl group of the present invention have the 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 are each an alkyl group having 1 to 20 carbon atoms, an aryl group having 6 to 20 carbon atoms, and 7 to 20 carbon atoms.
Or an aralkyl group of (R ′) ₃ SiO— (R ′ is a monovalent hydrocarbon group having 1 to 20 carbon atoms and has 3 R ′
May be the same or different), and R ¹¹ or R ¹² is 2
When there are one or more, they may be the same or different. Y represents a hydroxyl group or a hydrolyzable group, and when two or more Y 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. } The group represented by these is mentioned.

Examples of the hydrolyzable group include commonly used groups such as hydrogen atom, alkoxy group, acyloxy group, ketoximate group, amino group, amido group, aminooxy group, mercapto group and alkenyloxy group. To be Among these, an alkoxy group, an amide group, and an aminooxy group are preferable, but an alkoxy group is particularly preferable in terms of mild hydrolyzability and easy handling.

The hydrolyzable group or hydroxyl group can be bonded to one silicon atom in the range of 1 to 3;
The range of b) is preferably 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 the crosslinkable silyl group is 1 or more, but in the case of silicon atoms linked by a siloxane bond or the like, it is preferably 20 or less. Particularly, the crosslinkable silyl group represented by the general formula 32-Si (R ¹² ) _3-a (Y) _a (32) (wherein R ¹⁰ , Y and a are the same as described above) is easily available. Therefore, it is preferable.

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

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 equivalent to or more than the alkenyl group.

A hydrosilylation catalyst can be added to accelerate the hydrosilylation reaction. As such a 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.

When curing the curable composition (2), a condensation catalyst may or may not be used. As the condensation catalyst, titanic acid esters 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 their carboxylic acid salts; amine compounds such as reaction products or mixtures of laurylamine and tin octylate Reactions and mixtures of compounds with organotin compounds; low molecular weight polyamide resins obtained from excess polyamines and polybasic acids; reaction products of excess polyamines with epoxy compounds;
A 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 necessary. The amount used is preferably 0 to 10% by weight based on the vinyl polymer having a crosslinkable silyl group at the end. When an alkoxy group is used as the hydrolyzable group Y, the curing rate is slow with only this polymer.
It is preferable to use a curing catalyst. <Curable composition> In the curable composition (1) and the curable composition (2), various additives such as a flame retardant, an antioxidant, a filler, and a plasticizer are added to adjust the physical properties. , Physical property modifier, reaction diluent, adhesion promoter, storage stability improver, solvent, radical inhibitor, metal deactivator, ozone deterioration inhibitor, phosphorus peroxide decomposer, lubricant, pigment, foaming An agent, a photocurable resin and the like may be appropriately blended as necessary. These various additives may be used alone or in combination of two or more.

Further, since vinyl polymers are inherently excellent in durability, antiaging agents are not always necessary, but conventionally known antioxidants, ultraviolet absorbers, light stabilizers and the like are appropriately used. Can be used. <Filler> The filler to be blended is not particularly limited, but in order to impart physical properties such as strength, for example, fine powder silica, calcium carbonate, talc, titanium oxide, diatomaceous earth, barium sulfate, carbon black, surface-treated fine particles. Examples include 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 kinds. Among these, fine silica powder is preferable, and hydrous silica obtained by a wet production method or the like, dry silica obtained by a dry production method or the like can be used. Among these, anhydrous silica is particularly preferable because if the composition contains a large amount of water, side reactions may occur during the curing reaction. Furthermore, it is particularly preferable that the surface of the anhydrous silica is subjected to a hydrophobic treatment because it easily exhibits fluidity suitable for molding. In addition, a filler which is not very strong in reinforcement can be used for increasing the amount or adjusting the physical properties. <Plasticizer> The plasticizer that can be blended is not particularly limited, but depending on the purpose of adjusting physical properties, adjusting properties, etc., 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, isodecyl succinate; butyl oleate, methyl acetylricinoleate, etc. Aliphatic esters; polyalkylene glycol esters such as diethylene glycol dibenzoate, triethylene glycol dibenzoate, pentaerythritol ester; phosphoric acid esters such as tricresyl phosphate, tributyl phosphate; trimellitic acid esters;
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; process oils Polyethers such as polyethylene glycol, polypropylene glycol and polytetramethylene glycol, and polyethers such as derivatives obtained by converting the hydroxyl groups of these polyether polyols into ester groups, ether groups, etc .; epoxidized soybean oil, benzyl epoxystearate Epoxy plasticizers such as; dibasic acids such as sebacic acid, adipic acid, azelaic acid, phthalic acid and ethylene glycol, diethylene glycol, triethylene glycol, propylene glycol Polyester-based plasticizers obtained from dihydric alcohols such as vinyl alcohol and dipropylene glycol; vinyl-based polymers obtained by polymerizing vinyl-based monomers such as acrylic plasticizers by various methods, alone or Two or more kinds can be mixed and used,
It is not always necessary. It should be noted that these plasticizers can be added 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 thickening during storage and significant change in curing rate after storage, and examples thereof include benzothiazole and dimethylmalate. <Solvent> Examples of the solvent that can be mixed include aromatic hydrocarbon solvents such as toluene and xylene, ester solvents such as ethyl acetate, butyl acetate, amyl acetate and cellosolve, ketones such as methyl ethyl ketone, methyl isobutyl ketone and diisobutyl ketone. Examples include system solvents. 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 alkylalkoxysilanes such as methyltrimethoxysilane, dimethyldimethoxysilane, trimethylmethoxysilane, and n-propyltrimethoxysilane; alkyl such as dimethyldiisopropenoxysilane and methyltriisopropenoxysilane. Isopropenoxysilane; vinyl type unsaturated group-containing silanes such as vinyltrimethoxysilane, vinyldimethylmethoxysilane, vinyltriethoxysilane, γ-methacryloyloxypropylmethyldimethoxysilane, γ-acroyloxypropylmethyltriethoxysilane; Silicone varnishes; polysiloxanes and the like can be mentioned.

Among them, organic groups having an atom other than carbon atom and hydrogen atom such as epoxy group, (meth) acryl group, isocyanate group, isocyanurate group, carbamate group, amino group, mercapto group and carboxyl group in the molecule. And a silane coupling agent having both a crosslinkable silyl group are preferred. When these are specifically exemplified, the 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; and alkoxy silanes having an isocyanurate group, Isocyanurate silanes such as tris (trimethoxysilyl) isocyanurate;
Examples of alkoxysilanes 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 and γ-mercaptopropyl. Mercapto group-containing silanes such as methyldimethoxysilane and γ-mercaptopropylmethyldiethoxysilane; alkoxysilanes having a carboxyl group include β-
Carboxyethyltriethoxysilane, β-carboxyethylphenylbis (2-methoxyethoxy) silane,
Carboxysilanes such as N-β- (carboxymethyl) aminoethyl-γ-aminopropyltrimethoxysilane; as alkoxysilanes having a halogen group,
Examples thereof include halogen-containing silanes such as γ-chloropropyltrimethoxysilane.

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

Of these, alkoxysilanes having an epoxy group or a (meth) acryl group in the molecule are more preferable from the viewpoint of curability and adhesiveness. More specifically exemplifying the alkoxysilanes having an epoxy group, γ-glycidoxypropylmethyldimethoxysilane, γ-glycidoxypropyltrimethoxysilane, γ-glycidoxypropyltriethoxysilane, β -(3,4-epoxycyclohexyl) ethyltrimethoxysilane, β- (3,4-epoxycyclohexyl) ethyltriethoxysilane, γ-glycidoxypropylmethyldiisopropenoxysilane, etc. As the alkoxysilanes that have,
γ-methacryloxypropyltrimethoxysilane, γ-
Methacryloxypropyltriethoxysilane, γ-acryloxypropyltrimethoxysilane, γ-acryloxypropyltriethoxysilane, methacryloxymethyltrimethoxysilane, methacryloxymethyltriethoxysilane, acryloxymethyltrimethoxysilane, acryloxymethyltri Examples include ethoxysilane.
These may be used alone or in combination of two or more.

Further, 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 the crosslinkable silyl group condensation catalyst,
Dibutyltin dilaurate, dibutyltin diacetylacetonate, dibutyltin dimethoxide, organotin compounds such as tin octylate, organoaluminum compounds such as aluminum acetylacetonate, tetraisopropoxy titanium,
Examples thereof include organic titanium compounds such as tetrabutoxytitanium.

Specific examples other than the silane coupling agent are not particularly limited, and examples thereof include epoxy resin, phenol resin, sulfur, alkyl titanates, aromatic polyisocyanate and the like.

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

The above adhesion-imparting agents may be used alone or in combination of two or more. Addition of these adhesiveness-imparting agents can improve the adhesiveness to the adherend. <Molding method> The molding method when the curable composition of the present invention is used as a molded body is not particularly limited, and various commonly used molding methods can be used. Examples include cast molding, compression molding, transfer molding, injection molding, extrusion molding, rotational molding, hollow molding, and thermoforming. In particular, injection molding is preferable because it can be automated and continuous and is excellent in productivity.
In addition, when used as a gasket, it is possible to have both a wet type in which 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 in which it is cured and then sandwiched. Is. <Use> The curable composition of the present invention is not limited,
Sealing materials for elastic sealing materials for construction and sealing materials for double glazing, electrical / electronic component materials such as solar cell backside encapsulation materials, electrical insulating materials such as electric wire / cable insulation coating materials, adhesives, adhesives, Elastic adhesives, paints, powder paints, coating materials, foams, potting materials for electric and electronic use, films, gaskets, casting materials, artificial marble,
It can be used for various molding materials, and various applications such as rustproof and waterproof sealing materials for meshed glass and laminated glass end faces (cut parts).

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 automobile field, it can be used as a body part for a sealing material for maintaining airtightness, a vibration-proof material for glass, a vibration-proof material for vehicle body parts, particularly a wind seal gasket and a gasket for door glass. As a chassis part, it can be used for vibration and soundproof engines and suspension rubbers, especially engine mount rubbers. As an engine part, it can be used for hoses for cooling, fuel supply, exhaust control, etc., and sealing material for engine oil. Also, it can be used for exhaust gas purifying device parts and brake parts. In the field of home appliances, it can be used for packing, O-rings, belts, etc. Specifically, decorations for lighting equipment, waterproof packings, anti-vibration rubbers, insect-proof packings, vibration-proof / sound-absorbing and air-sealing materials for cleaners, drip-proof covers for electric water heaters, waterproof packings, heater parts Packing, electrode packing, safety valve diaphragm, hose for sake bottle, waterproof packing, solenoid valve, waterproof packing for steam oven range and jar rice cooker, water tank packing, water absorption valve, water receiving packing, connecting hose, belt, heat insulation Oil packing for combustion equipment such as heater packing, steam outlet seal, O-ring, drain packing, pressure tube, blower tube, air intake / air intake packing, anti-vibration rubber,
Examples include a filler gasket, an oil meter packing, an oil feed pipe, a diaphragm valve, an air feed pipe, and the like, a speaker gasket for audio equipment, a speaker edge, a turntable sheet, a belt, a pulley, and the like. In the construction field, structural gaskets (zipper gaskets), air film structure roofing materials,
It can be used as a waterproof material, regular sealing material, vibration damping material, soundproofing material, setting block, sliding material, etc. In the sports field, it can be used as an all-weather pavement material as a sports floor, a gym floor, a shoe sole material, a midsole material as sports shoes, and a golf ball as a ball for ball games. 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, etc. In the marine and civil engineering fields, as a structural material, rubber expansion joints, bearings, waterstops,
Rubber sheets, rubber packers, rubber skirts, sponge mats, mortar strainers, etc. as construction auxiliary materials such as waterproof sheets, rubber dams, elastic pavement, anti-vibration pads, protective bodies, etc., rubber sheets, air hoses etc. as construction auxiliary materials It can be used as a rubber buoy, wave-breaking material, etc. as a safety measure product, and as an oil fence, silt fence, antifouling material, marine hose, dredging hose, oil skimmer, etc. as an environmental protection product. In addition, it can also be used for plate rubber, mats, foam plates and the like.

[0137]

EXAMPLES Specific examples will be shown below, but the invention is not limited to the following examples. (Curing test) Polymer, an average of 5 hydrosilyl groups and an average of 5 α-methylstyrene groups in the molecule (Note that the α-methylstyrene group in the present invention is formed by a hydrosilylation reaction of α-methylstyrene. A chain siloxane containing a substituent on silicon (Si—H value:
3.70 mmol / g) and 1,0,3 of 0-valent platinum
Xylene solution of 3-tetramethyl-1,3-divinyldisiloxane complex (platinum concentration: 1.3 × 10 ⁻⁵ mmol / μ)
l) and 1) were mixed by hand at room temperature to obtain a composition. The chain siloxane was used in an amount such that the alkenyl group and the hydrosilyl group were in a molar ratio of 1 / 1.5, and the platinum catalyst amount was in a molar ratio with respect to the alkenyl group. A part of the composition was heated on a hot plate at 130 ° C. with stirring under an air atmosphere, and the gelation time was measured. (Measurement of Copper Content) Ultra-high purity nitric acid and ultra-high purity sulfuric acid were mixed with the polymer and subjected to microwave decomposition. ICP mass spectrometer (Yokogawa Analytical Systems Co., Ltd. HP-45
00) was used to quantify the amount of copper remaining in the decomposed product, and the amount of copper remaining in the polymer was measured. (Production Example 1) Method for producing alkenyl-terminated vinyl polymer CuBr was added to a 250 L reactor equipped with a stirrer and a jacket.
(1740 g) was charged and the inside of the reaction vessel was replaced with nitrogen.
Acetonitrile (13.5 kg) was added, warm water was passed through the jacket, and the mixture was stirred at 80 ° C. for 30 minutes. Butyl acrylate (212 kg) and diethyl 2,5-dibromoadipate (3692 g) were added to this, and the mixture was further stirred at 80 ° C. for 25 hours.
Stir for minutes. To this, pentamethyldiethylenetriamine (hereinafter referred to as triamine) was added to start the reaction. Triamine (961 g) was appropriately added during the reaction, and 8 hours after the start of the reaction, 1,7-octadiene (16.5 k
g), triamine (607 g) was added and stirring was continued for 6 hours.

The polymer solution was treated at 100 ° C. under vacuum to evaporate acetonitrile and 1,7-octadiene, and then dissolved with the same weight of toluene. As an adsorbent, Kyoward 500SH (hydrotalcites, manufactured by Kyowa Chemical) and Kyoward 700SL
(Aluminum silicate, manufactured by Kyowa Chemical Co., Ltd.) for each 2
A part by weight was added, and the polymer solution was heated at 100 ° C. for 2 hours. This solution is a DeLaval centrifuge (12800G,
Solid-liquid separation was performed with a residence time of 2 minutes) to remove the solid and the adsorbent. (Production Example 2) Production method of alkenyl-terminated vinyl polymer Subsequent to Production Example 1, addition of an adsorbent and solid-liquid separation by heating and centrifugation were repeated once again as in Production Example 1. (Production Example 3) Method for producing alkenyl-terminated vinyl polymer CuBr was added to a 250 L reactor equipped with a stirrer and a jacket.
(1740 g) was charged and the inside of the reaction vessel was replaced with nitrogen.
Acetonitrile (13.5 kg) was added, warm water was passed through the jacket, and the mixture was stirred at 80 ° C. for 30 minutes. Butyl acrylate (212 kg) and diethyl 2,5-dibromoadipate (3692 g) were added to this, and the mixture was further stirred at 80 ° C. for 25 hours.
Stir for minutes. To this, pentamethyldiethylenetriamine (hereinafter referred to as triamine) was added to start the reaction. Triamine (961 g) was appropriately added during the reaction, and 8 hours after the start of the reaction, 1,7-octadiene (16.5 k
g), triamine (607 g) was added and stirring was continued for 6 hours.

The polymer solution was treated at 100 ° C. under vacuum to evaporate acetonitrile and 1,7-octadiene, and then dissolved with the same weight of methylcyclohexane. This solution was added to a DeLaval centrifuge (1
Solid-liquid separation was carried out by 2800 G, residence time 2 minutes) to remove solids. (Production Example 4) Production method of alkenyl-terminated vinyl polymer CuBr was added to a 250 L reactor equipped with a stirrer and a jacket.
(1.01 kg) was charged and the inside of the reaction vessel was replaced with nitrogen. Acetonitrile (10.55 kg) was added, warm water was passed through the jacket, and the mixture was stirred at 80 ° C. for 30 minutes. Butyl acrylate (120 kg) and diethyl 2,5-dibromoadipate (2.11 kg) were added to this, and a further 80
Stir at 25 ° C. for 25 minutes. Triamine was added to this to initiate the reaction. Triamine was appropriately added during the reaction, and 6 hours after the start of the reaction, 1,7-octadiene (12.90 k
g), triamine was added and stirring was continued for 6 hours. This polymer solution was treated at 80 ° C. under vacuum conditions to evaporate acetonitrile and 1,7-octadiene, and dissolved with the same weight of methylcyclohexane. This polymer solution was subjected to solid-liquid separation by a DeLaval centrifuge (12800G, residence time 2 minutes). Kyo word 500
SH (manufactured by Kyowa Chemical Co., Ltd.) and Kyoward 700SL (manufactured by Kyowa Chemical Co., Ltd.) were added to the polymer in an amount of 2 parts by weight each, and the temperature was 100 ° C.
The polymer solution was heated for an hour. This solution was subjected to solid-liquid separation by a DeLaval centrifuge (12800G, residence time 2 minutes) to remove solids, to obtain a polymer solution. The polymer obtained by concentrating the polymer solution had a number average molecular weight of 25832 and a molecular weight distribution of 1.26 by GPC measurement (in terms of polystyrene), and the average number of alkenyl groups introduced per molecule of the polymer was determined by ¹ H NMR. According to the analysis, 1.
It was 77. The Cu content in the polymer was measured and found to be 12 ppm by weight. As a result of carrying out a curing test using this polymer, a curing time of 3 was obtained with 0.002 equivalent of a platinum catalyst.
It was 0 seconds. Comparative Example 1 The polymer solution obtained in Production Example 1 was heated to 140 ° C. in a preheating tank, and then the jacket temperature was adjusted to 1
The solution was passed through a double-tube adsorption tower at 65 ° C., and 10 kg was passed therethrough. The amount of copper, which had an initial concentration of 700 weight ppm before the treatment, was 80 weight ppm after the treatment.

The size of the adsorption tower is a cylindrical shape having an inner diameter of 0.028 m and a length of 0.75 m, and the adsorption tower is installed vertically.
The liquid was used by passing it from the bottom to the top at a flow rate of 30 g / min. A granular hydrotalcite-based adsorbent (270 g; Kyoward 500G-7, manufactured by Kyowa Chemical Co., Ltd.) was used as the adsorbent in the adsorption tower. (Example 1) The same operation as in Comparative Example 1 was carried out except that 2 parts by weight of ion-exchanged water was charged to the polymer in addition to the polymer solution in the preheating tank, and the mixture was stirred and mixed and heated.

The mixture of the polymer solution and ion-exchanged water was a slurry in which water droplets were dispersed in the organic phase.

The amount of copper, which had an initial concentration of 700 ppm by weight before the treatment, became 40 ppm by weight after the treatment.
It was halved compared to. (Example 2) The polymer solution obtained in Production Example 2 and 2 parts by weight of ion-exchanged water with respect to the polymer were charged in a preheating tank, stirred and mixed and heated to 140 ° C, and then a double pipe having a jacket temperature of 165 ° C. The solution was passed through the adsorption tower to carry out a 27 kg solution treatment. The amount of copper, which had an initial concentration of 150 ppm by weight before the treatment, continued to be maintained at 10 ppm by weight or less after the treatment.
Since no apparent leakage of the adsorbent was visually observed, it was not necessary to separate a large amount of solids by a new solid-liquid separator as in batch processing.

The size of the adsorption tower is a cylindrical shape having an inner diameter of 0.028 m and a length of 0.75 m. The adsorption tower is installed vertically.
The liquid was used by passing it from the bottom to the top at a flow rate of 30 g / min. A granular hydrotalcite-based adsorbent (270 g; Kyoward 500G-7, manufactured by Kyowa Chemical Co., Ltd.) was used as the adsorbent in the adsorption tower. (Example 3) The polymer solution obtained in Production Example 3 and 2 parts by weight of ion-exchanged water with respect to the polymer were charged in a preheating tank, stirred and mixed and heated to 140 ° C, and then a double pipe having a jacket temperature of 165 ° C. The solution was passed through the adsorption tower and treated at 20 kg. The amount of copper, whose initial concentration was 700 ppm by weight, continued to be maintained at 50 ppm by weight or less after the treatment. As in Example 2,
No visible leakage of the adsorbent was visually observed.

The size of the adsorption tower is a cylindrical shape having an inner diameter of 0.028 m and a length of 0.35 m, and is installed vertically.
The liquid was used by passing it from bottom to top at a flow rate of 60 g / min. A granular hydrotalcite-type adsorbent (127 g; Kyoward 500G-7, manufactured by Kyowa Chemical Co., Ltd.) was used as the adsorbent in the adsorption tower. (Example 4) 2 parts by weight of ion-exchanged water with respect to the polymer solution obtained in Production Example 4 and the polymer were charged into a preheating tank and heated to 140 ° C, and then the jacket temperature was changed to 165.
The solution was passed through a double-tube adsorption tower at ℃. Almost no fine powder was found in the treatment liquid by visual inspection, but filtration was performed with a filter aid (Showa Chemical Industry Co., Ltd., Radiolite # 300) instead of the cartridge filter that is commonly used after the adsorption tower in industrial operations. After that, a curing test was conducted using the polymer obtained by evaporating the solvent, and as a result, the platinum catalyst
The curing time was 30 seconds at 001 equivalent weight. The amount of copper after the treatment was 10 ppm by weight or less.

The size of the adsorption tower is a cylindrical shape having an inner diameter of 0.028 m and a length of 0.75 m, and the adsorption tower is installed vertically.
The liquid was used by passing it from bottom to top at a flow rate of 5 g / min. Granular hydrotalcite adsorbent (110 g; Kyoward 500G-7, manufactured by Kyowa Chemical Co., Ltd.) and granular aluminum silicate (130 g; manufactured by Kyowa Chemical Co., Ltd.) were used in the adsorption tower. Used from the bottom up in order. (Example 5) The polymer solution obtained in Production Example 4 and 2 parts by weight of ion-exchanged water with respect to the polymer were charged in a preheating tank and heated to 140 ° C., and the temperature of the jacket filled with the adsorbent in the following order: The solution was passed through a double-tube adsorption tower at 165 ° C. Almost no fine powder was observed in the treatment liquid, but after filtering with a filter aid (Radiolite # 300, Showa Chemical Industry Co., Ltd.) instead of the cartridge filter, the polymer obtained by evaporating the solvent was obtained. As a result of carrying out a curing test using the catalyst, a curing time was 30 seconds with 0.0005 equivalent of a platinum catalyst. The amount of copper after the treatment was 10 ppm by weight or less.

The size of the adsorption tower is a cylindrical shape having an inner diameter of 0.028 m and a length of 0.75 m, and the adsorption tower is installed vertically.
The liquid was used by passing it from bottom to top at a flow rate of 5 g / min. In the adsorption tower, granular aluminum silicate as adsorbent (130 g; Kyoward 715, manufactured by Kyowa Chemical Co., Ltd.)
And a granular hydrotalcite-type adsorbent (110 g; Kyoward 500G-7, manufactured by Kyowa Chemical Co., Ltd.) were used in this order from the bottom.

Here, the results of the above Examples and Comparative Examples (the amount of Cu contained in the alkenyl group-containing polymer, the catalyst equivalent used in the curing test of the alkenyl group-containing polymer,
And the curing time when a curing test is performed with the catalyst equivalent) are summarized in Table 1. From Table 1, the effect of the present invention can be easily understood.

[0148]

[Table 1]

[0149]

According to the present invention, the adsorbent is separated by purifying a mixed liquid of a vinyl polymer produced by atom transfer radical polymerization and water using an adsorbent packed in an adsorption tower. The polymer can be used as a component of the hydrosilylation-reactive composition without the need for an expensive solid-liquid separation device to do so.

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Claims (32)

[Claims] 1. A method for purifying a vinyl polymer in which a vinyl polymer produced by atom transfer radical polymerization of a vinyl monomer using a transition metal complex as a polymerization catalyst is passed through an adsorption tower filled with an adsorbent. A purification method comprising providing a mixture of the polymer and water in an adsorption tower. 2. A vinyl polymer having at least one alkenyl group in the molecule or an intermediate product obtained during the step of producing the vinyl polymer is passed through an adsorption tower filled with an adsorbent. A method for purifying the vinyl polymer or the intermediate product, which comprises mixing the polymer or the intermediate purified product with water and then supplying the mixture to an adsorption tower. 3. The purification according to claim 2, wherein the vinyl polymer having at least one alkenyl group in the molecule is produced by atom transfer radical polymerization of a vinyl monomer using a transition metal complex as a polymerization catalyst. Method. 4. The purification method according to claim 2, wherein the alkenyl group is present at the terminal of the molecular chain of the vinyl polymer. 5. A vinyl polymer is produced by adding a compound having two or more carbon-carbon double bonds having low polymerizability during or after the polymerization reaction of atom transfer radical polymerization. Item 4. The purification method according to Item 4. 6. A method for purifying a vinyl polymer for obtaining a vinyl polymer which is one component of a hydrosilylation-reactive composition, which comprises supplying a mixture of the polymer and water to an adsorption tower. A purification method characterized by: 7. The vinyl polymer obtained by atom transfer radical polymerization and water are mixed in a mixing tank, and then the mixture of the vinyl polymer and water is supplied to an adsorption tower. Item 7. A purification method according to any one of items 1 to 6. 8. The purification method according to claim 1, wherein the adsorbent is an inorganic adsorbent or activated carbon. 9. The purification method according to claim 1, wherein the inorganic adsorbent is activated clay or aluminum silicate. 10. The purification method according to claim 1, wherein the inorganic adsorbent is aluminum silicate. 11. The purification method according to any one of claims 1 to 10, wherein the inorganic adsorbent is activated alumina or a hydrotalcite compound. 12. The purification method according to claim 1, wherein the inorganic adsorbent is a hydrotalcite compound. 13. The central metal of the transition metal complex is an element of Group 8, Group 9, Group 10 or Group 11 of the periodic table.
The purification method according to any one of 1 to 12. 14. The purification 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 any one of claims 1 to 17. 19. A hydrosilylation-reactive composition containing a vinyl polymer obtained by the purification method according to any one of claims 1 to 18. 20. A hydrosilylation containing (A) a vinyl polymer having an alkenyl group in the molecule obtained by the purification method according to any one of claims 1 to 19 and (B) 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. A method according to claim 19, further comprising a platinum catalyst.
The hydrosilylation-reactive composition according to any one of 1. 24. A vinyl polymer having a crosslinkable silyl group, which is obtained by hydrosilylating 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 any one of claims 24 to 26. 28. The purification method according to any one of claims 1 to 17, wherein the vinyl polymer is a (meth) acrylic polymer. 29. The purification method according to claim 1, wherein the vinyl-based polymer is an acrylic ester-based polymer. 30. The purification method according to any one of claims 1 to 17, 28 and 29, wherein the vinyl polymer is a butyl acrylate polymer. 31. The number average molecular weight of the vinyl polymer is 50.
The purification method according to any one of claims 1 to 17 and 28 to 30, which is 0 to 100,000. 32. The purification method according to any one of claims 1 to 17 and 28 to 31, wherein the vinyl polymer has a molecular weight distribution value of less than 1.8.