JP5731266B2 - Method for producing vinyl polymer - Google Patents

Description

  The present invention relates to a method for producing a vinyl polymer and a purification method for removing a metal complex.

  A living polymerization method is generally known as a precision synthesis method for vinyl polymers. In the living polymerization, not only the molecular weight and molecular weight distribution can be controlled, but also a polymer having a clear terminal structure can be obtained. Therefore, living polymerization can be cited as one effective method for introducing a functional group to the polymer terminal. Recently, also in radical polymerization, a polymerization system capable of living polymerization has been found, and research on living radical polymerization has been actively conducted. In particular, a vinyl polymer having a narrow molecular weight distribution can be obtained by utilizing atom transfer radical polymerization. As an example of atom transfer radical polymerization, an organic halide or a sulfonyl halide compound is used as an initiator, and a metal complex having a group 7 element, 8 group, 9 group, 10 group, or 11 element as a central metal is used as a catalyst. And a polymerization system.

  However, since a transition metal complex as a polymerization catalyst remains in a vinyl polymer produced by atom transfer radical polymerization, problems such as coloring of the polymer, influence on physical properties, and environmental safety arise. For example, in a vinyl polymer having an alkenyl group at the terminal produced using an atom transfer radical polymerization method, the remaining catalyst or the like acts as a catalyst poison for the hydrosilylation reaction. There arises a problem that a large amount of the catalyst is required. Therefore, in practice, it is necessary to remove the polymerization catalyst from the polymer after the polymerization reaction.

  As a method for removing the polymerization catalyst, for example, the vinyl polymer is purified by bringing it into contact with an adsorbent such as activated carbon, activated alumina, aluminum silicate and silicon dioxide disclosed in Patent Document 1 and subsequently removing the adsorbent. Methods. Patent Document 2 describes a method in which a solid organic acid is added to destroy a complex and insolubilize and remove the metal.

  However, in the former method, there are cases where the adsorbent is expensive, takes time for adsorption, or is incompletely adsorbed. In the latter method, the solubility of the solid acid in the solvent is low, it is necessary to add the solid acid to the complex excessively, and the catalyst deactivation reaction may take a long time.

  Further, Patent Document 3, Patent Document 4, and Patent Document 5 also report a method of removing a metal catalyst by bringing a polymer into contact with water. However, in the operations disclosed in Patent Document 3 and Patent Document 4, It is necessary to dissolve the polymer in an organic solvent, contact with water, and then distill off the organic phase under reduced pressure.Then, it is necessary to re-precipitate the polymer and dry it. Although Reference 5 does not dilute with an organic solvent, several hundred ppm of catalyst metal remains in the product after contact with washing water, and the removal rate of the catalyst metal is low, so the practicality is low. ing.

JP-A-11-193307 JP 2003-147015 A JP 2005-105265 A JP 2002-356510 A JP 2006-299070 A

  The present invention provides a method for producing a vinyl polymer capable of economically and efficiently removing a metal complex in a vinyl polymer.

  The inventor of the present invention has disclosed a metal complex in a vinyl polymer by dissolving a vinyl polymer polymerized by atom transfer radical polymerization in an organic solvent and bringing the polymer solution into contact with washing water in which water and an acid component are mixed. Has been found to be efficiently removed and a vinyl polymer for hydrosilylation reactive composition can be obtained, and the present invention has been completed.

  That is, the present invention dissolves, in an organic solvent, a vinyl polymer polymerized by atom transfer radical polymerization using a metal complex centered on a transition metal of Groups 7, 8, 9, 10, and 11 of the periodic table as a catalyst. The present invention relates to a method for producing a vinyl polymer, characterized in that a metal complex remaining in a vinyl polymer is removed by bringing a polymer solution into contact with washing water in which water and an acid component are mixed.

  The acid component contained in the washing water is preferably an inorganic acid.

  The inorganic acid is preferably sulfuric acid.

  The acid component contained in the washing water is preferably an organic acid.

  The organic acid is preferably acetic acid.

  It is preferable to add a salt to the washing water.

  The organic solvent for dissolving the vinyl polymer is preferably an alcohol.

  The organic solvent dissolved in the vinyl polymer is preferably a linear alcohol having 4 or more carbon atoms. The central metal of the transition metal complex is preferably copper.

  In the vinyl polymer solution dissolved in the organic solvent, the vinyl polymer content is preferably 5 wt% or more and 90 wt% or less.

  The present invention relates to a vinyl polymer obtained by the production method described above.

  The present invention relates to a method for producing a vinyl polymer having a crosslinkable silyl group obtained by reacting the above vinyl polymer with a silane compound having a hydrosilyl group.

  The present invention relates to a hydrosilyl reactive composition containing a vinyl polymer obtained by the production method described above.

  The present invention relates to a vinyl polymer having a crosslinkable silyl group obtained by hydrosilylating the vinyl polymer described above and a silane compound having a hydrosilyl group.

  It relates to the purification method described above.

  According to the method for producing a vinyl polymer of the present invention, it is possible to easily obtain a vinyl polymer for a hydrosilylation reactive composition in which the content of the transition metal complex used in the polymerization is significantly reduced. By washing with water as compared with removing the catalyst, it is possible to reduce solid waste and to shorten the time required to remove the adsorbent by solid-liquid separation operation or the like. As a result, it is possible to provide a production process advantageous in terms of equipment cost while improving productivity, and its industrial value is very large.

  The present invention will be described in more detail, but the present invention is not limited to the following production method.

  In the present invention, a vinyl polymer polymerized by atom transfer radical polymerization is dissolved in an organic solvent using a metal complex mainly composed of transition metals of Groups 7, 8, 9, 10, and 11 of the periodic table as a catalyst, In this method, the metal catalyst remaining in the vinyl polymer is removed by bringing the polymer solution into contact with the washing water mixed with the acid component.

Atom transfer radical polymerization First, atom transfer radical polymerization will be described in detail. The atom transfer radical polymerization in the present invention is one of living radical polymerizations, and a vinyl monomer is prepared using a metal complex having an organic halide or a sulfonyl halide as an initiator and a transition metal (M) as a central metal as a catalyst. This is a method of radical polymerization. Specifically, for example, Matyjaszewski et al., Journal of American Chemical Society (J. Am. Chem. Soc.) 1995, 117, 5614, Macromolecules 1995, 28. 7901, Science 1996, 272, 866, WO 96/30421, WO 97/18247, WO 98/01480, WO 98/40415, or Sawamoto et al., Macromolecules ( Macromolecules) 1995, 28, 1721, JP-A-9-208616, JP-A-8-41117, and the like.

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), or a halogenated compound. A sulfonyl compound or the like is used as an initiator. For example,
_{C 6 H 5 -CH 2 X,} C 6 H 5 -C (H) (X) CH 3,
_{C 6 H 5 -C (X)} (CH 3) 2
(However, in the above chemical 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,
(Wherein 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, and 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 an alkyl group having 1 to 20 carbon atoms, an aryl group, or an aralkyl group, and X is chlorine, bromine, or iodine)
Etc.

By performing atom transfer radical polymerization of a vinyl monomer using an organic halide or a sulfonyl halide compound as an initiator, a vinyl polymer having a terminal structure represented by the general formula (1) is obtained.
-C (R ¹ ) (R ² ) (X) (1)
(In the formula, R ¹ and R ² represent a group bonded to an ethylenically unsaturated group of a 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 a specific reactive functional group that does not initiate polymerization together with a functional group that initiates 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 is obtained. Examples of such specific reactive functional groups include alkenyl groups, crosslinkable silyl groups, hydroxyl groups, epoxy groups, amino groups, amide groups, and the like. By utilizing the reactivity of these reactive functional groups, other appropriate functional groups can be introduced into the vinyl polymer through a one-step or several-step reaction.

It does not limit as an organic halide which has an alkenyl group, For example, what has a structure shown in General formula (2) is illustrated.
^{R 6 R 7 C (X)} -R 8 -R 9 -C (R 5) = CH 2 (2)
(Wherein R ⁵ is hydrogen or a methyl group, R ⁶ and R ⁷ are hydrogen, or a monovalent alkyl group having 1 to 20 carbon atoms, an aryl group, or aralkyl, or those interconnected 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 1 carbon atom -20 divalent organic groups which may contain one or more ether linkages, X is chlorine, bromine or iodine)
Specific examples of the substituents R ⁶ and R ⁷ include hydrogen, methyl group, ethyl group, n-propyl group, isopropyl group, butyl group, pentyl group, hexyl group and the like. R ⁶ and R ⁷ may be linked 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,

(In the above formulas, X is chlorine, bromine or iodine, and n is an integer of 0 to 20)
_{XCH 2 C (O) O (} CH 2) n O (CH 2) m CH = CH 2,
_{H 3 CC (H) (X} ) C (O) O (CH 2) n O (CH 2) m CH = CH 2,
_{(H 3 C) 2 C (} X) C (O) O (CH 2) n O (CH 2) m CH = CH 2,
_{CH 3 CH 2 C (H)} (X) C (O) O (CH 2) n O (CH 2) m CH = CH 2,

(In each of the above formulas, X is chlorine, bromine, or iodine, n is an integer of 1 to 20, and m is an integer of 0 to 20)
_{o, m, p-XCH 2} -C 6 H 4 - (CH 2) n -CH = CH 2,
_{o, m, p-CH 3} C (H) (X) -C 6 H 4 - (CH 2) n -CH = CH 2,
_{o, m, p-CH 3} CH 2 C (H) (X) -C 6 H 4 - (CH 2) n -CH = CH 2,
(In the above formulas, X is chlorine, bromine or iodine, and n is an integer of 0 to 20)
_{o, m, p-XCH 2} -C 6 H 4 - (CH 2) n -O- (CH 2) m -CH = CH 2,
_{o, m, p-CH 3} C (H) (X) -C 6 H 4 - (CH 2) n -O- (CH 2) m -CH = CH 2,
_{o, m, p-CH 3} CH 2 C (H) (X) -C 6 H 4 - (CH 2) n -O- (CH 2) m CH = CH 2,
(In each of the above formulas, X is chlorine, bromine, or iodine, n is an integer of 1 to 20, and m is an integer of 0 to 20)
_{o, m, p-XCH 2} -C 6 H 4 -O- (CH 2) n -CH = CH 2,
_{o, m, p-CH 3} C (H) (X) -C 6 H 4 -O- (CH 2) n -CH = CH 2,
_{o, m, p-CH 3} CH 2 C (H) (X) -C 6 H 4 -O- (CH 2) n -CH = CH 2,
(In the above formulas, X is chlorine, bromine or iodine, and n is an integer of 0 to 20)
_{o, m, p-XCH 2} -C 6 H 4 -O- (CH 2) n -O- (CH 2) m -CH = CH 2,
_{o, m, p-CH 3} C (H) (X) -C 6 H 4 -O- (CH 2) n -O- (CH 2) m -CH = CH 2,
_{o, m, p-CH 3} CH 2 C (H) (X) -C 6 H 4 -O- (CH 2) n -O- (CH 2) m -CH = CH 2,
(In each of the above formulas, X is chlorine, bromine, or iodine, n is an integer of 1 to 20, and m is an integer of 0 to 20)

Examples of the organic halide having an alkenyl group further include a compound represented by the general formula (3).
_{^{H 2 C = C (R 5}} ) -R 9 -C (R 6) (X) -R 10 -R 7 (3)
(Wherein R ⁵ , R ⁶ , R ⁷ , R ⁹ , X are the same as above, R ¹⁰ is a direct bond, —C (O) O— (ester group), —C (O) — (keto group) Or an o-, m-, p-phenylene group)

R ⁹ is a direct bond or a divalent organic group having 1 to 20 carbon atoms (which may contain one or more ether bonds), and in the case of a direct bond, carbon to which a halogen is bonded Is a halogenated allylic compound. In this case, since the carbon-halogen bond is activated by the adjacent vinyl group, it is not always necessary to have a C (O) O group, a phenylene group or the like as R ¹⁰ , and a direct bond may be used. In the case where R ⁹ is not a direct bond, R ¹⁰ is preferably a C (O) O group, a C (O) group, or a phenylene group in order to activate the carbon-halogen bond.

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

If the specific example of the sulfonyl halide compound which has an alkenyl group is given,
_{o-, m-, p-CH 2} = CH- (CH 2) n -C 6 H 4 -SO 2 X,
_{o-, m-, p-CH 2} = CH- (CH 2) n -O-C 6 H 4 -SO 2 X,
(In the above formulas, X is chlorine, bromine or iodine, and n is an integer of 0 to 20)
Etc.

It does not specifically limit as said organic halide which has a crosslinkable silyl group, For example, what has a structure shown in General formula (4) is illustrated.
^{R 6 R 7 C (X)} -R 8 -R 9 -C (H) (R 5) CH 2 - [Si (R 11) 2-b (Y) b O] m -Si (R 12) 3- _a (Y) _a (4)
(Wherein R ⁵ , R ⁶ , R ⁷ , R ⁸ , R ⁹ and X are the same as above, R ¹¹ and R ¹² are all alkyl groups, aryl groups, aralkyl groups having 1 to 20 carbon atoms, or (R ′) ₃ SiO— (R ′ is a monovalent hydrocarbon group having 1 to 20 carbon atoms, and three R ′ may be the same or different). Represents an organosiloxy group, and when two or more R ¹¹ or R ¹² are present, they may be the same or different, Y represents a hydroxyl group or a hydrolyzable group, and Y represents two or more When present, they may be the same or different, a represents 0, 1, 2, or 3, and b represents 0, 1, or 2. m is an integer from 0 to 19. (Provided that a + mb ≧ 1)
If the compound of general formula (4) is specifically illustrated,
XCH ₂ C (O) O (CH ₂ ) _n Si (OCH ₃ ) ₃ ,
_{CH 3 C (H) (X} ) C (O) O (CH 2) n Si (OCH 3) 3,
(CH ₃ ) ₂ C (X) C (O) O (CH ₂ ) _n Si (OCH ₃ ) ₃ ,
_{XCH 2 C (O) O (} CH 2) n Si (CH 3) (OCH 3) 2,
_{CH 3 C (H) (X} ) C (O) O (CH 2) n Si (CH 3) (OCH 3) 2,
_{(CH 3) 2 C (X} ) C (O) O (CH 2) n Si (CH 3) (OCH 3) 2,
(In the above formulas, X is chlorine, bromine, iodine, n is an integer of 0-20)
_{XCH 2 C (O) O (} CH 2) n O (CH 2) m Si (OCH 3) 3,
_{H 3 CC (H) (X} ) C (O) O (CH 2) n O (CH 2) m Si (OCH 3) 3,
_{(H 3 C) 2 C (} X) C (O) O (CH 2) n O (CH 2) m Si (OCH 3) 3,
_{CH 3 CH 2 C (H)} (X) C (O) O (CH 2) n O (CH 2) m Si (OCH 3) 3,
_{XCH 2 C (O) O (} CH 2) n O (CH 2) m Si (CH 3) (OCH 3) 2,
_{H 3 CC (H) (X} ) C (O) O (CH 2) n O (CH 2) m -Si (CH 3) (OCH 3) 2,
_{(H 3 C) 2 C (} X) C (O) O (CH 2) n O (CH 2) m -Si (CH 3) (OCH 3) 2,
_{CH 3 CH 2 C (H)} (X) C (O) O (CH 2) n O (CH 2) m -Si (CH 3) (OCH 3) 2,
(In the above formulas, X is chlorine, bromine, iodine, n is an integer of 1 to 20, and m is an integer of 0 to 20)
_{o, m, p-XCH 2} -C 6 H 4 - (CH 2) 2 Si (OCH 3) 3,
_{o, m, p-CH 3} C (H) (X) -C 6 H 4 - (CH 2) 2 Si (OCH 3) 3,
_{o, m, p-CH 3} CH 2 C (H) (X) -C 6 H 4 - (CH 2) 2 Si (OCH 3) 3,
_{o, m, p-XCH 2} -C 6 H 4 - (CH 2) 3 Si (OCH 3) 3,
_{o, m, p-CH 3} C (H) (X) -C 6 H 4 - (CH 2) 3 Si (OCH 3) 3,
_{o, m, p-CH 3} CH 2 C (H) (X) -C 6 H 4 - (CH 2) 3 Si (OCH 3) 3,
_{o, m, p-XCH 2} -C 6 H 4 - (CH 2) 2 -O- (CH 2) 3 Si (OCH 3) 3,
_{o, m, p-CH 3} C (H) (X) -C 6 H 4 - (CH 2) 2 -O- (CH 2) 3 Si (OCH 3) 3,
_{o, m, p-CH 3} CH 2 C (H) (X) -C 6 H 4 - (CH 2) 2 -O- (CH 2) 3 Si (OCH 3) 3,
_{o, m, p-XCH 2} -C 6 H 4 -O- (CH 2) 3 Si (OCH 3) 3,
_{o, m, p-CH 3} C (H) (X) -C 6 H 4 -O- (CH 2) 3 Si (OCH 3) 3,
_{o, m, p-CH 3} CH 2 C (H) (X) -C 6 H 4 -O- (CH 2) 3 -Si (OCH 3) 3,
_{o, m, p-XCH 2} -C 6 H 4 -O- (CH 2) 2 -O- (CH 2) 3 -Si (OCH 3) 3,
_{o, m, p-CH 3} C (H) (X) -C 6 H 4 -O- (CH 2) 2 -O- (CH 2) 3 Si (OCH 3) 3,
_{o, m, p-CH 3} CH 2 C (H) (X) -C 6 H 4 -O- (CH 2) 2 -O- (CH 2) 3 Si (OCH 3) 3,
(In the above formulas, X is chlorine, bromine, or iodine)
Etc.

Examples of the organic halide having a crosslinkable silyl group further 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, Y are the same as above)
If such a compound is specifically illustrated,
_{(CH 3 O) 3 SiCH 2} CH 2 C (H) (X) C 6 H 5,
_{(CH 3 O) 2 (CH} 3) SiCH 2 CH 2 C (H) (X) C 6 H 5,
_{(CH 3 O) 3 Si (} CH 2) 2 C (H) (X) -CO 2 R,
_{(CH 3 O) 2 (CH} 3) Si (CH 2) 2 C (H) (X) -CO 2 R,
_{(CH 3 O) 3 Si (} CH 2) 3 C (H) (X) -CO 2 R,
_{(CH 3 O) 2 (CH} 3) Si (CH 2) 3 C (H) (X) -CO 2 R,
_{(CH 3 O) 3 Si (} 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 (CH} 3) Si (CH 2) 4 C (H) (X) -C 6 H 5,
(In the above formulas, X is chlorine, bromine, or iodine, R is an alkyl group having 1 to 20 carbon atoms, an aryl group, or an aralkyl group)
Etc.

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

(In the above formulas, X is chlorine, bromine, or iodine, R is a hydrogen atom or an alkyl group having 1 to 20 carbon atoms, an aryl group, an aralkyl group, and n is an integer of 1 to 20)

  In order to obtain a polymer having two or more reactive functional groups in one molecule, an organic halide having two or more starting points or a sulfonyl halide compound is preferably used as an initiator. For example,

Etc.

  Although it does not specifically limit as a transition metal complex used as a polymerization catalyst, Preferably it is a metal complex which uses a periodic table group 7, 8, 9, 10, or 11 element as a central metal. More preferable examples include a complex of zero-valent copper, monovalent copper, divalent ruthenium, divalent iron, or divalent nickel. Of these, a copper complex is preferable. Specific examples of monovalent copper compounds include cuprous chloride, cuprous bromide, cuprous iodide, cuprous cyanide, cuprous oxide, cuprous perchlorate, etc. is there.

  In order to enhance the activity of the catalyst, it is preferable to add a nitrogen-containing ligand, and it is more preferable that the nitrogen-containing ligand is a chelate ligand having two or more coordination sites. The catalyst in this case is preferably produced by a reaction between a halogenated M and a nitrogen-containing ligand.

  As the chelate ligand having two or more coordination sites, 2,2′-bipyridyl or a derivative thereof, 1,10-phenanthroline or a derivative thereof, or tetramethylethylenediamine, pentamethyldiethylenetriamine, or hexamethyltris (2-amino And polyamines such as ethyl) amine. When the metal M is copper, the nitrogen-containing ligand is preferable.

A tristriphenylphosphine complex of divalent ruthenium chloride (RuCl ₂ (PPh ₃ ) ₃ ) is also suitable as a catalyst. When a ruthenium compound is used as a catalyst, an aluminum alkoxide is added as an activator. Furthermore, a divalent iron bistriphenylphosphine complex (FeCl ₂ (PPh ₃ ) ₂ ), a divalent nickel bistriphenylphosphine complex (NiCl ₂ (PPh ₃ ) ₂ ), and a divalent nickel bistributylphosphine A complex (NiBr ₂ (PBu ₃ ) ₂ ) is also suitable as a catalyst.

  There is no restriction | limiting in particular as a vinyl-type monomer used in this superposition | polymerization, For example, (meth) acrylic acid, (meth) acrylic acid methyl, (meth) acrylic acid ethyl, (meth) acrylic acid-n-propyl, (meth) acrylic Isopropyl acid, (meth) acrylic acid-n-butyl, (meth) acrylic acid isobutyl, (meth) acrylic acid-tert-butyl, (meth) acrylic acid-n-pentyl, (meth) acrylic acid-n-hexyl, (Meth) acrylic acid cyclohexyl, (meth) acrylic acid-n-heptyl, (meth) acrylic acid-n-octyl, (meth) acrylic acid-2-ethylhexyl, (meth) acrylic acid nonyl, (meth) acrylic acid decyl , Dodecyl (meth) acrylate, phenyl (meth) acrylate, toluyl (meth) acrylate, (meth) a Benzyl yllate, 2-methoxyethyl (meth) acrylate, 3-methoxybutyl (meth) acrylate, 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, (meth ) Stearyl acrylate, glycidyl (meth) acrylate, 2-aminoethyl (meth) acrylate, γ- (methacryloyloxypropyl) trimethoxysilane, ethylene oxide adduct of (meth) acrylic acid, (meth) acrylic acid tri Fluoromethyl methyl, 2-trifluoromethyl ethyl (meth) acrylate, 2-perfluoroethyl ethyl (meth) acrylate, 2-perfluoroethyl-2-perfluorobutyl ethyl (meth) acrylate, (meth) acryl 2-perfluoroethyl acid, perfluoromethyl (meth) acrylate Chill, diperfluoromethylmethyl (meth) acrylate, 2-perfluoromethyl-2-perfluoroethylmethyl (meth) acrylate, 2-perfluorohexylethyl (meth) acrylate, 2- (meth) acrylic acid 2- (Meth) acrylic monomers such as perfluorodecylethyl and 2-perfluorohexadecylethyl (meth) acrylate; styrenes such as styrene, vinyltoluene, α-methylstyrene, chlorostyrene, styrenesulfonic acid and their salts Monomers; Fluorine-containing vinyl monomers such as perfluoroethylene, perfluoropropylene, and vinylidene fluoride; Silicon-containing vinyl monomers such as vinyltrimethoxysilane and vinyltriethoxysilane; Maleic anhydride, maleic acid, and monoalkyl esters of maleic acid And dial Fumaric acid, monoalkyl esters and dialkyl esters of fumaric acid; maleimides such as maleimide, methylmaleimide, ethylmaleimide, propylmaleimide, butylmaleimide, hexylmaleimide, octylmaleimide, dodecylmaleimide, stearylmaleimide, phenylmaleimide, cyclohexylmaleimide, etc. Monomers; Nitrile group-containing vinyl monomers such as acrylonitrile and methacrylonitrile; Amide group-containing vinyl monomers such as acrylamide and methacrylamide; Vinyl acetate, vinyl propionate, vinyl pivalate, vinyl benzoate, vinyl cinnamate, etc. Esters; Alkenes such as ethylene and propylene; Conjugated dienes such as butadiene and isoprene; Vinyl chloride, vinylidene chloride, allyl chloride And allyl alcohol. These may be used alone or a plurality of these may be copolymerized. Of these, a styrene monomer and a (meth) acrylic acid monomer are preferable from the physical properties of the product. Acrylic acid ester monomers and methacrylic acid ester monomers are more preferred, acrylic acid ester monomers are particularly preferred, and butyl acrylate, ethyl acrylate, and 2-methoxyethyl acrylate are more preferred. 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 solvent, but can also be carried out in various solvents. The type of solvent is not particularly limited. For example, hydrocarbon solvents such as benzene and toluene; ether solvents such as diethyl ether, tetrahydrofuran, diphenyl ether, anisole, and dimethoxybenzene; methylene chloride, chloroform, chlorobenzene, and the like. Halogenated hydrocarbon solvents; ketone solvents such as acetone, methyl ethyl ketone, methyl isobutyl ketone; alcohol solvents such as methanol, ethanol, propanol, isopropanol, n-butyl alcohol, tert-butyl alcohol; acetonitrile, propionitrile, benzo Nitrile solvents such as nitrile; ester solvents such as ethyl acetate and butyl acetate; carbonate solvents such as ethylene carbonate and propylene carbonate; N, N-dimethylformamide , N, amide solvents such as N- dimethylacetamide. These may be used alone or in combination of two or more. Polymerization can also be performed in an emulsion system or a system using supercritical fluid CO ₂ as a medium.

  Although not limited, the polymerization can be performed in the range of 0 to 200 ° C, and preferably in the range of room temperature to 150 ° C.

Will be described in detail vinyl polymer in the present invention will now for the vinyl polymer.

  The vinyl polymer is not particularly limited, but is produced by atom transfer radical polymerization of a vinyl monomer. Such vinyl monomers are not particularly limited, and those already exemplified can be used. These vinyl monomers may be used alone or a plurality of them may be copolymerized. Of these, a styrene monomer and a (meth) acrylic acid monomer are preferable from the physical properties of the product. More preferred are acrylate monomers and methacrylate monomers, particularly preferred are acrylate monomers, and even more preferred are butyl acrylate, ethyl acrylate, 2-methoxyethyl acrylate, and stearyl acrylate. is there. In the present invention, these preferred monomers may be copolymerized with other monomers, and further block copolymerized, and in that case, these preferred monomers are preferably contained in a weight ratio of 40% or more. .

  The molecular weight distribution of the vinyl polymer, that is, the ratio of the weight average molecular weight and the number average molecular weight measured by gel permeation chromatography is not particularly limited, but is preferably less than 1.8, preferably 1.7 or less. More preferably 1.6 or less, even more preferably 1.5 or less, particularly preferably 1.4 or less, and most preferably 1.3 or less. In the GPC measurement in the present invention, chloroform is usually used as the mobile phase, the measurement is performed 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. If the molecular weight is too low, the original characteristics of the vinyl polymer are hardly expressed, and conversely if it is too high, handling becomes difficult.

  The purification method of the present invention may be performed immediately after the polymerization of the vinyl polymer, or may be performed after attaching a reactive functional group in the molecule of the vinyl polymer after polymerization. When it has a reactive functional group in the molecule, it may be present at either the side chain or the end of the molecular chain. Although it does not specifically limit as a reactive functional group, For example, an alkenyl group, a hydroxyl group, an amino group, a crosslinkable silyl group, a polymerizable carbon-carbon double bond group etc. are mentioned.

Furthermore, the method for introducing the functional group is not particularly limited, and various methods are used. For example, the following methods are exemplified.
(1) A method of copolymerizing a vinyl monomer having a functional group with a predetermined vinyl monomer under atom transfer radical polymerization conditions,
(2) A method in which an olefin compound having a low radical polymerizability having a functional group is reacted with a terminal halogen group of a vinyl polymer under atom transfer radical polymerization conditions,
(3) A method of substituting a terminal halogen group of a vinyl polymer with a specific compound having a functional group,
(4) Terminal halogen of vinyl polymer and general formula (6)
A ^{+ −} OC (O) C (R) ═CH ₂ (6)
(In the formula, R represents hydrogen or an organic group having 1 to 20 carbon atoms. A ⁺ represents an alkali metal or a quaternary ammonium ion.)
A method of reacting a compound represented by the formula:

  A reactive functional group can also be converted to another suitable functional group in one or several steps. For example, also in the present invention, a vinyl polymer having an alkenyl group is synthesized by converting a reactive functional group such as a hydroxyl group.

  Among them, when hydrosilylation is performed, it is preferable to obtain a vinyl polymer having an alkenyl group at the terminal by the method (2). The method (2) will be described below. A vinyl polymer obtained by atom transfer radical polymerization of a vinyl monomer is reacted with a compound having at least two alkenyl groups having low polymerizability (hereinafter referred to as “diene compound”).

At least two alkenyl groups of the diene compound may be the same or different from each other. The alkenyl group is 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; Two 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. Examples of the organic group having 1 to 20 carbon atoms include an alkyl group having 1 to 20 carbon atoms, an aryl group having 6 to 20 carbon atoms, and 7 to 7 carbon atoms. Twenty aralkyl groups are preferred. Among these, as R, hydrogen or a methyl group is particularly preferable.

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

  Specific examples of the diene compound include isoprene, piperylene, butadiene, myrcene, 1,5-hexadiene, 1,7-octadiene, 1,9-decadiene, 4-vinyl-1-cyclohexene, and the like. 5-hexadiene, 1,7-octadiene and 1,9-decadiene are preferred.

Next, a method for purifying a vinyl polymer in the present invention will be described in detail. The present invention is not limited to the following purification method.

  In the present invention, a vinyl polymer polymerized by atom transfer radical polymerization is dissolved in an organic solvent using a metal complex mainly composed of transition metals of Groups 7, 8, 9, 10, and 11 of the periodic table as a catalyst, And (A) a purification step of mixing and stirring the polymer and water to remove the metal catalyst remaining in the vinyl polymer by bringing the polymer solution into contact with the washing water mixed with the acid component. After performing this purification method, (B) a dehalogenation step in which dehalogenation is performed to reduce the amount of halogen atoms in 1 kg of the polymer to 1000 mg or less, and (C) a purification step in which the polymer and water are mixed and separated by stirring. A production method for obtaining a vinyl polymer through the above is preferred.

<(A) Purification step of mixing and stirring polymer and water>
Since the vinyl polymer solution obtained by polymerization contains a polymer and a transition metal complex that is a catalyst, it is necessary to eliminate the polymerization activity and separate and remove these transition metals. In the present invention, the transition metal complex is removed by purification using an aqueous solution containing a water-insoluble solvent and an acid component.

  The purification operation of the present invention is performed after the vinyl polymer is dissolved in a water-insoluble solvent. Various solvents such as the following can be selected for dissolving the polymer. Examples of water-insoluble solvents include saturated hydrocarbon solvents such as n-hexane, cyclohexane, and methylcyclohexane; aromatic hydrocarbon solvents such as benzene, toluene, xylene, and anisole; methylene chloride, carbon tetrachloride, chloroform, and the like. Halogenated hydrocarbon solvents; ester solvents such as ethyl acetate, butyl acetate, and isoamyl acetate; alcohol solvents such as methanol, ethanol, n-propanol, n-butanol, n-pentanol, and n-hexanol. . These may be used alone or in combination of two or more. Among these, a preferable solvent is an alcohol solvent. Of these, alcohols having 4 or more carbon atoms are preferable, and n-butanol is more preferable.

  The amount of the solvent used is not particularly limited. Usually, it is preferable to add a solvent so that the vinyl polymer is in the range of 5 wt% to 90 wt%, and the vinyl polymer is preferably in the range of 10 to 50 wt% from the viewpoint of economy and operation.

  There is no selection condition for water to be used other than considering prevention of contamination of the polymer. Water through a filter of 50 μm or less is preferable, and pure water treated with an ion exchange resin is more preferable.

  In the present invention, an acid component is mixed with water in order to remove the metal complex in the polymer solution. An example of an acid component that dissolves in water is preferably an inorganic acid or an organic acid. Examples of the inorganic acid include sulfuric acid, hydrochloric acid, nitric acid, phosphoric acid and the like. Among these, sulfuric acid is preferable in terms of equipment protection. As the organic acid, oxalic acid, acetic acid, citric acid, adipic acid and the like can be used alone or in combination. From the economical viewpoint, acetic acid or the like is preferable.

  Although the content of the acid added to water is not particularly limited, it is preferable to adjust the addition amount corresponding to the solubility of the acid. In order to promote the removal of the metal catalyst after mixing the aqueous acid solution and the polymer solution, the amount of addition in the case of an inorganic acid is preferably 0.001 to 5 wt%, which reduces the wastewater treatment load. Therefore, the content is preferably 0.01 to 0.5 wt%. In the case of an organic acid, the addition amount is preferably 0.01 to 10 wt%, and preferably 0.5 to 3 wt% in order to reduce the wastewater treatment load.

  Moreover, in order to improve the separability from the polymer solution, a salt component may be mixed in water. Examples of salt components that dissolve in water are sodium chloride, sodium sulfate, sodium acetate, sodium acrylate, sodium phosphate, sodium citrate, sodium tartrate, sodium benzoate, sodium sorbate, sodium phthalate, sodium acrylate and Sodium methacrylate. These sodium salts may be potassium salts or ammonium salts. Among these, sodium sulfate and sodium chloride are preferable, and sodium sulfate is more preferable because it is easily available and is a neutral salt and has a low load in wastewater treatment.

  Although the content of the salt component added to water is not particularly limited, it is necessary to completely dissolve the salt component. Therefore, it is preferable to adjust the addition amount corresponding to the solubility of the salt component. In order to promote the separability after mixing the mixed aqueous solution of the salt component and water and the polymer solution, it is preferable to add the salt component in an amount of 0.1 to 15 wt%, thereby reducing the wastewater treatment load. Therefore, the content is preferably 0.1 to 10 wt%.

  The amount of water used when bringing the aqueous solution in which the acid is dissolved into contact with the polymer solution is not particularly limited, but water is preferably in the range of 10 to 2000 parts by weight with respect to 100 parts by weight of the vinyl polymer. More preferably, it is 100 to 300 parts by weight from the viewpoint of economy and operation.

  Various embodiments are possible for the liquid-liquid contact between the acid-dissolved aqueous solution and the polymer solution. However, in addition to the batch method in which stirring and mixing and liquid-liquid separation are performed in a batch operation, water and the polymer are counterflowed. An extraction tower system or a spray tower system for passing through the container can also be used. Furthermore, in addition to mixing and dispersing by stirring, various operations for improving the dispersion efficiency such as shaking of the container and use of ultrasonic waves can be incorporated as necessary. Examples of methods that do not require a driving force for mixing the two phases include methods called flow mixers such as spray towers, packed towers, baffle towers, perforated plate extraction towers, orifice towers, and static mixers. Examples of the method that requires a driving force include a pulsating packed tower, a pulsating perforated plate tower, a vibrating plate tower, a centrifugal extraction device such as a Podovirniak extractor and a Lewesta extractor. There are various types of apparatuses using a stirring system as a driving force, such as a mixer-settler extraction apparatus, a Seibel tower, a rotating disk extraction tower, an Old shoe-Rushton tower, and an ARD tower.

  The temperature at which the aqueous solution in which water or an acid or a salt component is dissolved and the polymer solution are brought into contact with each other is not particularly limited, and may generally be 0 to 200 ° C. Preferably it is 20-100 degreeC, More preferably, it is 30-80 degreeC. A higher temperature is preferable because the viscosity of the polymer solution decreases and the number of dispersed oil droplets decreases, so that the contact area with water increases and the extraction of the metal catalyst is promoted. However, if it is too high, the quality of the vinyl polymer may be deteriorated.

  The time for performing the contact is not particularly limited as long as the object of the present invention can be achieved. There are also combinations in which purification is completed by mixing and stirring for about 1 minute by limiting the types of water-insoluble solvents, acids, and inorganic salts that dissolve the polymer. Other combinations can be usually performed in about 5 to 300 minutes.

  For oil-water separation between an aqueous solution in which water, acid, or salt components are dissolved, and a polymer solution, centrifugal separation or static separation utilizing a specific gravity difference, or electrostatic oil purification utilizing a difference in electrical properties is used. I can do it. The time for performing the oil / water separation is not particularly limited as long as the object of the present invention can be achieved. Usually, it can be performed in about 1 to 300 minutes.

  The number of times of contact and oil-water separation between the aqueous solution in which the acid component is dissolved and the polymer solution is not particularly limited, and it may be performed once or several times. Further, after washing with an acid component, it may be washed with an aqueous solution in which a pure or salt component is dissolved.

  By the above purification treatment, the content of the transition metal component in the polymer of the present invention can be reduced to 1 mg or less with respect to 1 kg of the polymer.

  In the above, the method according to the present invention can be widely applied in the production of vinyl polymers by atom transfer radical polymerization.

<(B) Dehalogenation Step>
(A) The halogen-containing vinyl polymer obtained by the purification step of mixing and stirring the polymer and water is preferably dehalogenated by the following two methods.
(A) Heating method: The halogen-containing vinyl polymer is dehalogenated by heating.
(B) Substitution method: Dehalogenation is performed by substituting the terminal halogen of the vinyl polymer with an oxyanion compound.
Hereinafter, (a) will be described in detail.

(A) Heating method The halogen-containing vinyl polymer can be dehalogenated by heating. The processing temperature is not particularly limited. Higher temperatures are preferable for shortening the treatment time, but if the temperature is too high, the vinyl polymer will decompose, so the vinyl polymer will be heated in a temperature range where the vinyl polymer will not significantly decompose. It is preferable to process. Specifically, it is preferably 100 ° C. or higher and 250 ° C. or lower, more preferably 120 ° C. or higher and 250 ° C. or lower, still more preferably 140 ° C. or higher and 250 ° C. or lower, particularly preferably 170 ° C. or higher and 250 ° C. or lower, and 190 ° C. or higher and 250 ° C. or lower. Most preferred.

  Further, the heat treatment is preferably performed under reduced pressure.

A vinyl polymer having a group represented by the general formula (A) at the terminal produced by atom transfer radical polymerization of a vinyl monomer is dehalogenated by the above heat treatment.
-C (R ¹ ) (R ² ) (X) (A)
(In the formula, R ¹ and R ² represent a group bonded to an ethylenically unsaturated group of a vinyl monomer. X represents chlorine, bromine or iodine.)
Here, R ¹ and R ² are groups bonded to the ethylenically unsaturated group of the vinyl monomer, but are preferably groups bonded to the ethylenically unsaturated group of the (meth) acrylic acid monomer.

In the case where acid liberation due to high-temperature heat treatment, polymer degradation such as molecular weight jump, or the influence on the functional group of the vinyl polymer becomes a problem, it is preferable to convert the halogen-containing structure into a specific structure. For example, a group represented by the general formula (A) is converted into a group represented by the following general formula (B), and heat treatment is performed to quickly dehalogenate while suppressing coupling between polymers. proceed.
_{^{-C (R 1) (R 2}} ) -CH 2 -CH (X) - (B)
(In the formula, R ¹ and R ² represent a group bonded to an ethylenically unsaturated group of a vinyl monomer. X represents chlorine, bromine or iodine.)
Here, R ¹ and R ² are groups bonded to the ethylenically unsaturated group of the vinyl monomer, but are preferably groups bonded to the ethylenically unsaturated group of the (meth) acrylic acid monomer.

In addition, when the halogen-containing structure is a γ-halocarboxylic acid structure, γ-halocarboxylate structure or γ-haloester structure (hereinafter referred to as γ-halocarboxylic acid structure, etc.), it can be easily dehalogenated by heat treatment. Therefore, the halogen-containing structure is more preferable as a dehalogenation method. Although it does not specifically limit as (gamma) -halocarboxylic acid structure etc., The group represented by the following general formula (D) is more preferable.
^{_{-C (R 50) (CO 2}} R 51) -CH 2 -CH (X) -CH (R 52) -R 53 (D)
(Wherein X is chlorine, bromine, or iodine, R ⁵⁰ is a hydrogen atom or an organic group having 1 to 10 carbon atoms, R ⁵¹ is a hydrogen atom, an organic group having 1 to 20 carbon atoms or an alkali metal atom, R ⁵² is Hydrogen atom, hydroxyl group or organic group, R ⁵³ is hydrogen atom, hydroxyl group or organic group)
Here, R ⁵⁰ is a hydrogen atom or an organic group having 1 to 10 carbon atoms, preferably a hydrogen atom or a hydrocarbon group having 1 to 5 carbon atoms, more preferably a hydrogen atom or a methyl group, most preferably a hydrogen atom. is there.

R ⁵¹ is a hydrogen atom, an organic group having 1 to 20 carbon atoms, or an alkali metal atom. Examples of the organic group having 1 to 20 carbon atoms include an alkyl group having 1 to 20 carbon atoms, an aryl group having 6 to 20 carbon atoms, an aralkyl group having 7 to 20 carbon atoms, and the like. An alkoxyalkyl group having 2 to 20 carbon atoms and the like may be exemplified. R ⁵¹ is preferably a hydrogen atom, an alkali metal atom, an alkyl group having 1 to 20 carbon atoms, or an alkoxyalkyl group having 2 to 20 carbon atoms, a hydrogen atom, a sodium atom, a potassium atom, an alkyl group having 1 to 20 carbon atoms, An alkoxyalkyl group having 2 to 20 carbon atoms is more preferable, and an alkyl group having 1 to 20 carbon atoms and an alkoxyalkyl group having 2 to 20 carbon atoms are particularly preferable.

R ⁵² and R ⁵³ may be a hydrogen atom, a hydroxyl group, a monovalent or divalent organic group, and R ⁵² and R ⁵³ may be the same or different groups. When R ⁵² and R ⁵³ are organic groups, they may contain one or more ether bonds or one or more ester bonds. R ⁵² and R ⁵³ may be connected at the other end to form a cyclic skeleton. Moreover, the bivalent organic group couple | bonded with polymers, such as a vinyl type polymer, may be sufficient. Moreover, the bivalent organic group couple | bonded with functional groups, such as an ethylenically unsaturated group, a hydroxyl group, an amino group, and a silyl group, may be sufficient. R ⁵² is preferably a hydrogen atom or a hydrocarbon group having 1 to 20 carbon atoms, and particularly preferably a hydrogen atom or a methyl group. When R ⁵³ is a monovalent organic group, it is preferably an organic group having 1 to 20 carbon atoms, and a hydrocarbon group having 1 to 20 carbon atoms is particularly preferable. When R ⁵³ is a divalent organic group bonded to a functional group or a polymer, an organic group having 1 to 20 carbon atoms is preferable, and a hydrocarbon group having 1 to 20 carbon atoms is particularly preferable. The functional group is preferably an ethylenically unsaturated group or a hydroxyl group.

  The vinyl polymer having a group represented by the general formula (D) is dehalogenated through lactone ring formation. At this time, since halogen is eliminated as an organic halide, generation of free acid is suppressed.

  The method for producing a vinyl polymer having a group represented by the general formula (A), a group represented by the general formula (B), or a group represented by the general formula (D) is not particularly limited, but an atom transfer radical It can be produced directly or indirectly using polymerization. Specific production examples are shown below.

The vinyl polymer having a group represented by the general formula (A) is produced, for example, by polymerizing a vinyl monomer by the above-described atom transfer radical polymerization method. In particular, when the vinyl monomer is a (meth) acrylic acid monomer, a vinyl polymer having a group represented by the general formula (C) at the terminal is produced. In this case, R ⁵⁰ and CO ₂ R ⁵¹ which are substituents of the group represented by the general formula (C) are groups derived from a group bonded to the ethylenically unsaturated group of the (meth) acrylic acid monomer. .
_{^{-C (R 50) (CO 2}} R 51) -X (C)
(In the formula, X is chlorine, bromine, or iodine, R ⁵⁰ is a hydrogen atom or an organic group having 1 to 10 carbon atoms, R ⁵¹ is a hydrogen atom, an organic group having 1 to 20 carbon atoms, or an alkali metal atom)
A vinyl polymer having a group represented by the general formula (B) is produced as a vinyl polymer having a group represented by the general formula (A), and the terminal halogen is reacted with an ethylenically unsaturated group-containing compound. It is manufactured by.

  A vinyl polymer having a group represented by the general formula (D) is produced by atom transfer radical polymerization of a vinyl monomer, and pentene is added to the terminal halogen of the vinyl polymer having a group represented by the general formula (A). It is produced by a method of reacting an ethylenically unsaturated group-containing compound such as an acid or a derivative thereof.

  Moreover, the vinyl polymer which has group represented by general formula (D) is manufactured also with the following method.

A vinyl polymer having a group represented by the following general formula (C) at the terminal is produced using atom transfer radical polymerization of a vinyl monomer, and the terminal halogen of the vinyl polymer is represented by the following general formula (E). It can convert into the group represented by the above-mentioned general formula (D) by making the ethylenically unsaturated group containing compound represented.
_{^{-C (R 50) (CO 2}} R 51) -X (C)
(Wherein X is chlorine, bromine, or iodine, R ⁵⁰ is a hydrogen atom or an organic group having 1 to 10 carbon atoms, R ⁵¹ is a hydrogen atom, an organic group having 1 to 20 carbon atoms or an alkali metal atom, R ⁵² is Hydrogen atom, hydroxyl group or organic group, R ⁵³ is hydrogen atom, hydroxyl group or organic group)
Here, R ⁵⁰ is a hydrogen atom or an organic group having 1 to 10 carbon atoms, preferably a hydrogen atom or a hydrocarbon group having 1 to 5 carbon atoms, more preferably a hydrogen atom or a methyl group, most preferably a hydrogen atom. is there.

R ⁵¹ is a hydrogen atom, an organic group having 1 to 20 carbon atoms, or an alkali metal atom. Examples of the organic group having 1 to 20 carbon atoms include an alkyl group having 1 to 20 carbon atoms, an aryl group having 6 to 20 carbon atoms, an aralkyl group having 7 to 20 carbon atoms, and the like. An alkoxyalkyl group having 2 to 20 carbon atoms and the like may be exemplified. R ⁵¹ is preferably a hydrogen atom, an alkali metal atom, an alkyl group having 1 to 20 carbon atoms, or an alkoxyalkyl group having 2 to 20 carbon atoms, a hydrogen atom, a sodium atom, a potassium atom, an alkyl group having 1 to 20 carbon atoms, An alkoxyalkyl group having 2 to 20 carbon atoms is more preferable, and an alkyl group having 1 to 20 carbon atoms and an alkoxyalkyl group having 2 to 20 carbon atoms are particularly preferable.
^{_{CH 2 = CH-CH (R}} 52) -R 53 (E)
(Wherein R ⁵² is a hydrogen atom, hydroxyl group or organic group, and R ⁵³ is a hydrogen atom, hydroxyl group or organic group)
Here, R ⁵² and R ⁵³ may be a hydrogen atom, a hydroxyl group or an organic group, and R ⁵² and R ⁵³ may be the same or different groups. When R ⁵² and R ⁵³ are organic groups, they may contain one or more ether bonds or one or more ester bonds, or may be a polymer. R ⁵² and R ⁵³ may be connected at the other end to form a cyclic skeleton. )
In the ethylenically unsaturated group-containing compound represented by the general formula (E), R ⁵² and R ⁵³ are a hydrogen atom, a hydroxyl group, a monovalent or divalent organic group, and R ⁵² and R ⁵³ are the same or different groups. It may be. When R ⁵² and R ⁵³ are organic groups, they may contain one or more ether bonds or one or more ester bonds. R ⁵² and R ⁵³ may be connected at the other end to form a cyclic skeleton. Moreover, the bivalent organic group couple | bonded with polymers, such as a vinyl type polymer, may be sufficient. Moreover, the bivalent organic group couple | bonded with functional groups, such as an ethylenically unsaturated group, a hydroxyl group, an amino group, and a silyl group, may be sufficient. R ⁵² is preferably a hydrogen atom or a hydrocarbon group having 1 to 20 carbon atoms, and particularly preferably a hydrogen atom or a methyl group. When R ⁵³ is a monovalent organic group, it is preferably an organic group having 1 to 20 carbon atoms, and a hydrocarbon group having 1 to 20 carbon atoms is particularly preferable. When R ⁵³ is a divalent organic group bonded to a functional group or a polymer, an organic group having 1 to 20 carbon atoms is preferable, and a hydrocarbon group having 1 to 20 carbon atoms is particularly preferable. The functional group is preferably an ethylenically unsaturated group or a hydroxyl group.

Although the manufacturing method of the vinyl polymer which has the group represented by general formula (C) at the terminal is not specifically limited, Since the manufacturing method using atom transfer radical polymerization of a (meth) acrylic acid type monomer is simple, it is preferable. . R ⁵⁰ and CO ₂ R ⁵¹ in the group represented by the general formula (C) of the vinyl polymer produced by atom transfer radical polymerization using the (meth) acrylic acid monomer are those of the (meth) acrylic monomer. It is a group bonded to an ethylenically unsaturated group.

Although it does not specifically limit as an ethylenically unsaturated group containing compound represented by general formula (E), A compound with low radical polymerization activity is preferable. Such a compound is preferably a hydrocarbon-based compound, for example, an ethylenically unsaturated group-containing aliphatic hydrocarbon-based compound such as CH ₂ ═CH— (CH ₂ ) _n —CH ₃ (n is an integer of 0 to 20). And an ethylenically unsaturated group-containing aromatic hydrocarbon compound such as CH═CH— (CH ₂ ) _n —C ₆ H ₅ (n is an integer of 1 to 20).

  A compound having a plurality of ethylenically unsaturated groups in the molecule is also preferably used. When using a compound having a plurality of ethylenically unsaturated groups in the molecule, the coupling between polymers or the ethylenicity to the polymer can be controlled by adjusting the molar ratio between the ethylenically unsaturated group and the molecular chain terminal. An unsaturated group can be introduced. Examples of such a compound include non-conjugated diene compounds such as 1,7-octadiene.

  An ethylenically unsaturated group-containing compound having a functional group such as a hydroxyl group or an amino group in the molecule is also preferably used. In this case, functional groups such as hydroxyl groups and amino groups can be introduced into the polymer.

  The reaction method of the terminal halogen of the vinyl polymer having a group represented by the general formula (C) at the terminal and the ethylenically unsaturated group-containing compound represented by the general formula (E) is not particularly limited, A method using a “reaction system of mobile radical polymerization” is preferred. “Atom transfer radical polymerization reaction system” means a reaction system used in atom transfer radical polymerization. That is, a transition metal that is suitably used in atom transfer radical polymerization using a vinyl polymer having a group represented by the general formula (C) as an organic halide corresponding to an initiator in atom transfer radical polymerization This refers to reacting an ethylenically unsaturated group-containing compound with a halogen of a vinyl polymer under conditions suitable for atom transfer radical polymerization using a complex, a ligand, an activator, a solvent, and the like. Accordingly, an ethylenically unsaturated group-containing compound is added to the polymerization system during or at the end of the atom transfer radical polymerization of the vinyl monomer, and the vinyl monomer polymerization step and the vinyl polymer and the ethylenically unsaturated group-containing compound are added. It is not limited to the method of completing the reaction step in one pot, but is a method of reacting an ethylenically unsaturated group-containing compound with a vinyl polymer under the reaction conditions of atom transfer radical polymerization in a step separate from the vinyl monomer polymerization step. There may be. Moreover, the polymerization conditions for the vinyl monomer and the conditions for reacting the ethylenically unsaturated compound with the vinyl polymer may be the same or different.

  The group represented by the general formula (C) causes the molecular weight jump of the vinyl polymer by the dehalogenation treatment, and therefore when the molecular weight jump becomes a problem, it is represented as completely as possible by the general formula (D). It is preferable to convert it to a group. However, the vinyl polymer having the group represented by the general formula (D) and the vinyl polymer having the group represented by the general formula (D) without completely converting the group represented by the general formula (C). In the case of a mixture of polymers, the ratio of the group represented by the general formula (C) to the group represented by the general formula (D) [the number of moles of the group represented by the general formula (C)] / [ The number of moles of the group represented by the general formula (D)] is preferably 0.01 or more and 0.2 or less, more preferably 0.01 or more and 0.1 or less, and still more preferably 0.01 or more and 0.05 or less. The remaining group represented by the general formula (C) is preferably 0.1 mmol or more and 10 mmol or less, more preferably 0.1 mmol or more and 5.0 mmol or less, relative to 1 kg of the vinyl polymer. It is particularly preferably 0.1 mmol or more and 3.0 mmol or less.

  When the halogen compound liberated from the polymer during dehalogenation adversely affects the quality of the product, production equipment, etc., it is preferable to carry out the dehalogenation reaction while removing the halogen compound under reduced pressure. Preferably it is 100 torr or less, More preferably, it is 20 torr or less. Moreover, it is more preferable to heat and depressurize with good surface renewal by stirring or the like.

<(C) Purification step of mixing and stirring polymer and water>
Since the dehalogenated vinyl polymer solution contains hydrosilylation inhibitors, for the purpose of removing these inhibitors, a purification step of further mixing and stirring the polymer and water may be performed. The purification operation is the same as in (A), but it is preferable to use a neutral aqueous solution as the washing water.

Hydrosilylation Reaction The vinyl polymer subjected to the above-described purification treatment can be used for the hydrosilylation reaction, and a rubber-like cured product is obtained by crosslinking.

Examples of a method for obtaining a rubber-like cured product using a hydrosilylation reaction include the following two points.
(I) A method of obtaining a cured product by preparing a composition containing a vinyl polymer having an alkenyl group in the molecule and a hydrosilyl group-containing compound and performing a hydrosilylation reaction.
(II) Hydrosilylation reaction of a vinyl polymer having an alkenyl group in the molecule and a hydrosilane compound having a crosslinkable silyl group to obtain a vinyl polymer having a crosslinkable silyl group, and the resulting crosslinkable silyl A method for producing a cured product by preparing a composition containing a vinyl polymer having a group and crosslinking crosslinkable silyl groups.

<Method (I)>
The hydrosilyl group-containing compound used in the method (I) preferably has at least 1.1 hydrosilyl groups in the molecule in order to give a cured product by a hydrosilylation reaction. Although it does not specifically limit as a compound which has at least 1.1 hydrosilyl group in such a molecule, For example, linear polysiloxane represented by General formula (22) or (23);
^{_{R 23 3 SiO- [Si (R}} 23) 2 O] a - [Si (H) (R 24) O] b - [Si (R 24) (R 25) O] c -SiR 23 3 (22)
HR ²³ ₂ SiO- [Si (R ²³ ) ₂ O] _a- [Si (H) (R ²⁴ ) O] _b- [Si (R ²⁴ ) (R ²⁵ ) O] _c -SiR ²³ ₂ H (23)
(Wherein R ²³ and R ²⁴ represent an alkyl group having 1 to 6 carbon atoms or a phenyl group, and R ²⁵ represents an alkyl group having 1 to 10 carbon atoms or an aralkyl group. A represents 0 ≦ a ≦ 100, b Represents an integer satisfying 2 ≦ b ≦ 100 and c satisfying 0 ≦ c ≦ 100.)
A cyclic siloxane represented by the general formula (24);

(Wherein R ²⁶ and R ²⁷ represent an alkyl group having 1 to 6 carbon atoms or a phenyl group, and R ²⁸ represents an alkyl group having 1 to 10 carbon atoms or an aralkyl group. D represents 0 ≦ d ≦ 8, e Represents an integer of 2 ≦ e ≦ 10, f represents an integer of 0 ≦ f ≦ 8, and satisfies 3 ≦ d + e + f ≦ 10.)
Etc. can be used.

These may be used alone or in combination of two or more. Among these siloxanes, from the viewpoint of compatibility with (meth) acrylic polymers, chain siloxanes represented by the following general formulas (25) and (26) having a phenyl group, and general formulas (27), ( The cyclic siloxane represented by 28) is preferred.
_{(CH 3) 3 SiO- [Si} (H) (CH 3) O] g - [Si (C 6 H 5) 2 O] h -Si (CH 3) 3 (25)
_{(CH 3) 3 SiO- [Si} (H) (CH 3) O] g - [Si (CH 3) {CH 2 C (H) (R 28) C 6 H 5} O] h -Si (CH 3 ₃ (26)
(In the formula, R ²⁸ represents hydrogen or a methyl group. G represents an integer of 2 ≦ g ≦ 100 and h represents an integer of 0 ≦ h ≦ 100. C6H5 represents a phenyl group.)

(In the formula, R ²⁹ represents hydrogen or a methyl group. I represents an integer satisfying 2 ≦ i ≦ 10 and j satisfying 0 ≦ j ≦ 8 and 3 ≦ i + j ≦ 10.

  As a compound having at least 1.1 hydrosilyl groups, a hydrosilyl group-containing compound represented by the general formulas (22) to (28) is further used for a low molecular compound having two or more alkenyl groups in the molecule. A compound obtained by addition reaction such that a part of the hydrosilyl group 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, hydrocarbon compounds such as 1,4-pentadiene, 1,5-hexadiene, 1,6-heptadiene, 1,7-octadiene, 1,8-nonadiene, 1,9-decadiene, O, O Ether compounds such as' -diallyl bisphenol A, 3,3'-diallyl bisphenol A, ester compounds such as diallyl phthalate, diallyl isophthalate, triallyl trimellitate, tetraallyl pyromellitate, carbonates such as diethylene glycol diallyl carbonate System compounds.

  The compound can be obtained by slowly dropping the above-mentioned alkenyl group-containing compound in the presence of a hydrosilylation catalyst with respect to the excessive amount of the hydrosilyl group-containing compound represented by the general formulas (22) to (28). it can. Of these compounds, the following are preferred in view of the availability of raw materials, the ease of removal of excessive siloxane, and the compatibility with vinyl polymers.

  The vinyl polymer having an alkenyl group in the molecule and the hydrosilyl group-containing compound can be mixed at an arbitrary ratio, but from the viewpoint of curability, the molar ratio of the alkenyl group to the hydrosilyl group is in the range of 5 to 0.2. It is preferable to be in the range of 2.5 to 0.4. When the molar ratio is 5 or more, curing is insufficient and only a cured product having low tackiness and a low strength can be obtained. When the molar ratio is less than 0.2, a large amount of active hydrosilyl groups remain in the cured product even after curing. Cracks and voids are generated, and a uniform and strong cured product cannot be obtained.

  The curing reaction between a vinyl polymer having an alkenyl group in the molecule and a hydrosilyl group-containing compound proceeds by mixing and heating the two components, but a hydrosilylation catalyst is added to accelerate the reaction. can do. Such 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, and examples thereof include di-t-butyl peroxide, 2,5-dimethyl-2,5-di (t-butylperoxy) hexane, 2,5-dimethyl-2,5-di ( t-butylperoxy) -3-hexyne, dicumyl peroxide, t-butylcumyl peroxide, dialkyl peroxides such as α, α′-bis (t-butylperoxy) isopropylbenzene, benzoyl peroxide, p-chlorobenzoyl peroxide, m-chlorobenzoyl peroxide, 2,4-dichlorobenzoyl peroxide, diacyl peroxides such as lauroyl peroxide, peracid esters such as t-butyl perbenzoate, diisopropyl percarbonate, di-2-ethylhexyl percarbonate Peroxydicarbonate such as 1,1 Examples thereof include peroxyketals such as -di (t-butylperoxy) cyclohexane and 1,1-di (t-butylperoxy) -3,3,5-trimethylcyclohexane.

Also, it is not particularly limited as a transition metal catalyst, for example, platinum simple substance, alumina, silica, carbon black or the like dispersed in a platinum solid, chloroplatinic acid, chloroplatinic acid and alcohol, aldehyde, ketone, etc. Complex, platinum-olefin complex, and platinum (0) -divinyltetramethyldisiloxane complex. Examples of the catalyst other than platinum _{compounds, RhCl (PPh 3) 3,} RhCl 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. Although there is no restriction | limiting in particular as a catalyst amount, It is good to use in the range of 10 ^{< -1} > ^-10 <^-8> mol with respect to 1 mol of alkenyl groups of (A) component, Preferably it is the range of 10 ^{< -3} > ^-10 <^-6> mol. It is good to use. If it is less than 10 ⁻⁸ mol, curing does not proceed sufficiently. In addition, the hydrosilylation catalyst is generally expensive and corrosive, and a large amount of hydrogen gas may be generated to cause foaming of the cured product. Therefore, it is preferable not to use 10 ⁻¹ mol or more.

  Although there is no restriction | limiting in particular about hardening temperature, Generally it is good to make it harden | cure at 0 to 200 degreeC, Preferably it is 30 to 150 degreeC, More preferably, it is 80 to 150 degreeC. Thereby, a curable composition can be obtained in a short time.

<Method (II)>
Although there is no restriction | limiting in particular as a hydrosilane compound which has a crosslinkable silyl group used for the method of (II), When a typical thing is shown, the compound shown by General formula 29 will be illustrated.
^{_{H- [Si (R 11) 2}} -b (Y) b O] m -Si (R 12) 3-a (Y) a (29)
{In the formula, R ¹¹ and R ¹² are all alkyl groups having 1 to 20 carbon atoms, aryl groups having 6 to 20 carbon atoms, aralkyl groups having 7 to 20 carbon atoms, or (R ′) ₃ SiO— (R 'Is a monovalent hydrocarbon group having 1 to 20 carbon atoms, and three R's may be the same or different, and represents a triorganosiloxy group represented by R ¹¹ or When two or more R ¹² are present, they may be the same or different. Y represents a hydroxyl group or a hydrolyzable group, and when two or more Y exist, they may be the same or different. a represents 0, 1, 2, or 3, and b represents 0, 1, or 2. m is an integer of 0-19. However, it shall be satisfied that a + mb ≧ 1. }
Examples of the hydrolyzable group include commonly used groups such as a hydrogen atom, an alkoxy group, an acyloxy group, a ketoximate group, an amino group, an amide group, an aminooxy group, a mercapto group, and an alkenyloxy group. 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.

  Hydrolyzable groups and hydroxyl groups can be bonded to one silicon atom in the range of 1 to 3, and (a + Σb) is preferably in the range of 1 to 5. When two or more hydrolyzable groups or hydroxyl groups are bonded to the crosslinkable silyl group, they may be the same or different. The number of silicon atoms forming the crosslinkable silyl group is one 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, in particular, the general formula 30
H-Si (R ¹² ) _3-a (Y) _a (30)
(Wherein R ¹² , Y and a are the same as above)
The compound which has a crosslinkable group shown by is preferable from a point with easy acquisition.

  The following method can be considered as a method for obtaining a vinyl polymer having an alkenyl group in the molecule used in the method (II).

(A) When synthesizing a vinyl polymer by atom transfer radical polymerization, for example, a compound having both a polymerizable alkenyl group and a low polymerizable alkenyl group in one molecule as shown in the following general formula (9) To react as a second monomer.
_{^{H 2 C = C (R 14}} ) -R 15 -R 16 -C (R 17) = CH 2 (9)
(In the formula, R ¹⁴ represents hydrogen or a methyl group, R ¹⁵ represents —C (O) O—, or o-, m-, p-phenylene group, R ¹⁶ represents a direct bond, 20 represents a divalent organic group of 20 and may contain one or more ether bonds. R ¹⁷ represents hydrogen or an organic group having 1 to 20 carbon atoms)
In the general formula (9), R ¹⁷ is hydrogen or an organic group having 1 to 20 carbon atoms. 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. 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 -CH 3, -C 6 H 5, - _{C 6 H 5 (CH 3)} , - C 6 H 5 (CH 3) 2, - (CH 2) n -C 6 H 5, - (CH 2) n -C 6 H 5 (CH 3), - ( _{CH 2) n -C 6 H 5} (CH 3) 2
(N is an integer of 0 or more, and the total carbon number of each group is 20 or less)
Of these, R ¹⁷ is more preferably hydrogen or a methyl group.

  There is no limitation on the timing of reacting a compound having both a polymerizable alkenyl group and a low polymerizable alkenyl group in one molecule, but a cured product obtained by curing a vinyl polymer is expected to have rubber-like properties. In some cases, it is preferable to react as the second monomer at the end of the polymerization reaction or after completion of the reaction of the predetermined monomer.

  (B) When a vinyl polymer is synthesized by atom transfer radical polymerization, for example, 1,5-hexadiene, 1,7-octadiene, 1,9-decadiene, etc. at the end of the polymerization reaction or after completion of the reaction of a predetermined monomer A method of reacting a compound having at least two alkenyl groups having low polymerizability as described above.

  (C) An alkenyl group such as organotin such as allyltributyltin and allyltrioctyltin is added to a vinyl polymer having at least one highly reactive carbon-halogen bond at the terminal obtained by atom transfer radical polymerization. A method in which halogen is substituted by reacting various organometallic compounds.

(D) Reacting a stabilized carbanion having an alkenyl group as shown in the general formula (10) to a vinyl polymer having at least one highly reactive carbon-halogen bond at the terminal obtained by atom transfer radical polymerization. To replace the halogen.
^{M + C - (R 18)} (R 19) -R 20 -C (R 17) = CH 2 (10)
^{(Wherein, R 17} is the same ^{.R 18, R 19} together carbanion C ^- or an electron withdrawing group stabilizing, or one of the other is hydrogen or a 1 to 10 carbon atoms in the electron-withdrawing group 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 group for R ¹⁸ and 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. .

  (E) A vinyl polymer having at least one highly reactive carbon-halogen bond at the terminal obtained by atom transfer radical polymerization is allowed to react with an enolate anion by reacting a metal alone or an organometallic compound such as zinc. And then having an alkenyl group such as an alkenyl group-containing compound having a leaving group such as a halogen or an acetyl group, a carbonyl compound having an alkenyl group, an isocyanate compound having an alkenyl group, an acid halide having an alkenyl group, etc. A method of reacting with an electrophilic compound.

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

  Among the methods (a) to (f), the methods (b) and (f) are preferred because they are easier to control.

  A vinyl polymer having a crosslinkable silyl group in the molecule can be obtained by hydrosilylation reaction of the hydrosilane compound and a vinyl polymer having an alkenyl group in the molecule.

  A vinyl polymer having at least 1.1 crosslinkable silyl groups in the molecule is crosslinked to give a cured product.

As the crosslinkable silyl group, 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 all alkyl groups having 1 to 20 carbon atoms, aryl groups having 6 to 20 carbon atoms, aralkyl groups having 7 to 20 carbon atoms, or (R ′) ₃ SiO— (R 'Is a monovalent hydrocarbon group having 1 to 20 carbon atoms, and three R's may be the same or different, and represents a triorganosiloxy group represented by R ¹¹ or When two or more R ¹² are present, they may be the same or different. Y represents a hydroxyl group or a hydrolyzable group, and when two or more Y exist, they may be the same or different. a represents 0, 1, 2, or 3, and b represents 0, 1, or 2. m is an integer of 0-19. However, it shall be satisfied that a + mb ≧ 1. }
And a group represented by

  Examples of the hydrolyzable group include commonly used groups such as a hydrogen atom, an alkoxy group, an acyloxy group, a ketoximate group, an amino group, an amide group, an aminooxy group, a mercapto group, and an alkenyloxy group. 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.

Hydrolyzable groups and hydroxyl groups can be bonded to one silicon atom in the range of 1 to 3, and (a + Σb) is preferably in the range of 1 to 5. When two or more hydrolyzable groups or hydroxyl groups are bonded to the crosslinkable silyl group, they may be the same or different. The number of silicon atoms forming the crosslinkable silyl group is one or more, but in the case of silicon atoms linked by a siloxane bond or the like, it is preferably 20 or less. In particular, the general formula 32
^{_{-Si (R 12) 3-a}} (Y) a (32)
A crosslinkable silyl group represented by the formula (wherein R ¹² , Y and a are the same as described above) is preferable because it is easily available.

  When a rubber-like property is particularly required for a cured product obtained by curing a vinyl polymer having a crosslinkable silyl group, the molecular weight between crosslink points that greatly affects rubber elasticity can be increased. At least one of the groups is preferably at the end of the molecular chain. More preferably, it has all functional groups at the molecular chain ends.

  The ratio of the vinyl polymer having an alkenyl group in the molecule and the hydrosilane compound having both a crosslinkable silyl group is not particularly limited, but the hydrosilyl group is preferably equivalent to or more than the alkenyl group.

  A hydrosilylation catalyst can be added to advance the hydrosilylation reaction more rapidly. As such a hydrosilylation catalyst, those already exemplified may be used.

  Although there is no restriction | limiting in particular about reaction temperature, Generally it is 0 to 200 degreeC, Preferably it is 30 to 150 degreeC, More preferably, it is 80 to 150 degreeC.

  In curing a curable composition containing a vinyl polymer having a crosslinkable silyl group, a condensation catalyst may or may not be used. Condensation catalysts include titanates such as tetrabutyl titanate and tetrapropyl titanate; organic compounds such as dibutyltin dilaurate, dibutyltin diacetylacetonate, dibutyltin maleate, dibutyltin diacetate, dibutyltin dimethoxide, tin octylate and tin naphthenate Tin compound; 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, morpholine , N-methylmorpholine, amine compounds such as 1,3-diazabicyclo (5,4,6) undecene-7 or their carboxylates; amine compounds such as a reaction product or mixture of laurylamine and tin octylate Reaction product and mixture of silane and organotin compound; low molecular weight polyamide resin obtained from excess polyamine and polybasic acid; reaction product of excess polyamine and epoxy compound; silane coupling agent having amino group, for example, γ- One type or two or more types of 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 terminal. When an alkoxy group is used as the hydrolyzable group Y, it is preferable to use a curing catalyst because only this polymer has a slow curing rate.

  EXAMPLES Although this invention is demonstrated further in detail based on an Example, this invention is not limited only to these Examples.

The measuring method of the residual ratio of copper in the following examples was measured using the analyzer shown below.
Analyzer: Rigaku Denki Kogyo Co., Ltd. Energy dispersive X-ray fluorescence spectrometer SPECTRO XEPOS
Measurement method: A measurement sample was taken in a cell and set in a fluorescent X-ray analyzer for measurement. Elements contained in the sample are excited by primary X-rays from an X-ray tube, and a spectrum intensity proportional to the element content is obtained. Comparison was made with a calibration curve stored in advance as a database in the apparatus, and after various correction calculations, it was digitized.

[Production Example 1] (Polymerization of n-butyl acrylate)
Hereinafter, the required amount per 100 kg of the polymer will be described. CuBr (0.84 kg) was charged into a reactor equipped with a stirrer and a jacket, and the inside of the reaction vessel was purged with nitrogen. Acetonitrile (8.79 kg) was added, warm water was passed through the jacket, and the mixture was stirred at 80 ° C. for 30 minutes. To this were added butyl acrylate (100 kg) and diethyl 2,5-dibromoadipate (3.51 kg), and the mixture was further stirred at 80 ° C. for 25 minutes. To this, pentamethyldiethylenetriamine (hereinafter referred to as triamine) was added to initiate the reaction. Triamine was appropriately added during the reaction, and 6 hours after the start of the reaction, 1,7-octadiene (21.5 kg) and triamine were added and stirring was continued for 6 hours to obtain a polymer solution. The solvent was removed from the polymer solution under vacuum conditions at 80 ° C. to obtain a copper catalyst-containing vinyl polymer [polymer 1] having an alkenyl terminal. When the GPC analysis of the obtained vinyl polymer (System: GPC system manufactured by Waters, column: Shodex K-804 (polystyrene gel) manufactured by Showa Denko KK) was performed, the number average molecular weight Mn was 12700. The molecular weight distribution Mw / Mn was 1.18.

[Example 1]
[Polymer solution 1] was obtained by adding 200 g of n-butanol to 100 g of [Polymer 1] obtained in Production Example 1, followed by stirring. A 1 L separable flask (with a stirrer and a jacket) was charged with 200 g of a 0.1 wt% sulfuric acid aqueous solution as washing water, heated to 45 ° C., and [Polymer solution 1] was added dropwise. Stirring was performed. After the stirring was stopped, the oil phase and the aqueous phase were quickly separated, and the oil phase turned pale yellow and the aqueous phase turned blue. After standing for 20 minutes, the oil phase was recovered, and 200 g of water was further added, followed by stirring for 5 minutes. After the stirring was stopped, the oil phase and the aqueous phase were promptly separated, and after standing for 20 minutes, the oil phase was recovered. The solvent and water | moisture content were depressurizingly distilled for the oil phase using the rotary evaporator. Next, as a dehalogenation step, 0.1 g of Sumilizer GS was added, and stirring was performed at 185 ° C. for 12 hours under vacuum conditions. Thereafter, as a purification step, 200 g of n-butanol and 200 g of pure water were added, mixed at 45 ° C. for 10 minutes, allowed to stand for 20 minutes, separated into two phases of an oil phase and an aqueous phase, and the oil phase was recovered. After repeating this purification step twice, the solvent and water were distilled off under reduced pressure at 100 ° C. under vacuum to obtain a vinyl polymer [polymer 2] having an alkenyl terminal. When the [polymer 2] was analyzed for copper, the residual ratio of copper in the polymer was 1 ppm or less.

  A 300 ml four-necked flask was charged with 50 g of [Polymer 2], stirred, and heated to 100 ° C. under reduced pressure. After reversion with nitrogen, 0.861 ml of methyl orthoformate and 0.019 ml of xylene solution of 1,1,3,3-tetramethyl-1,3-divinyldisiloxane complex of zerovalent platinum were added under a nitrogen stream After mixing, 2.914 ml of DMS (dimethoxymethylsilane) was added, heated and stirred at 100 ° C. for 2 to 5 hours, and devolatilized to obtain a vinyl polymer having an alkoxysilyl group. When the alkenyl group in the vinyl polymer was measured by NMR analysis (JMN-LA400 manufactured by JEOL Ltd.), the residual rate was 1% or less.

[Example 2]
[Polymer 3] was prepared in the same manner as in Example 1 except that 198 g of a 0.1 wt% sulfuric acid aqueous solution was used as the wash water, and 2 g of anhydrous sodium sulfate (hereinafter referred to as sodium sulfate) was added. Obtained. When the [polymer 3] was analyzed for copper, the residual ratio of copper in the polymer was 1 ppm or less.

  This [Polymer 3] was used in the same manner as in Example 1 to obtain a vinyl polymer having an alkoxysilyl group. When the alkenyl group in the vinyl polymer was measured by NMR analysis (JMN-LA400 manufactured by JASCO Corporation), the residual rate was 1% or less.

Example 3
[Polymer 4] was obtained in the same manner as in Example 1 except that 198 g of 1 wt% acetic acid aqueous solution was used as the washing water, and 2 g of anhydrous sodium sulfate (hereinafter referred to as mirabilite) was added. . When the [polymer 4] was analyzed for copper, the residual ratio of copper in the polymer was 1 ppm or less.

  This [Polymer 4] was used in the same manner as in Example 1 to obtain a vinyl polymer having an alkoxysilyl group. When the alkenyl group in the vinyl polymer was measured by NMR analysis (JMN-LA400 manufactured by JASCO Corporation), the residual rate was 1% or less.

[Comparative Example 1]
[Polymer 5] was obtained in the same manner as in Example 1 except that 200 g of a 1 wt% aqueous solution of sodium sulfate was used as the washing water. When [copper 5] was analyzed for copper, the residual ratio of copper in the polymer was 6 ppm.

  This [Polymer 5] was used in the same manner as in Example 1 to obtain a vinyl polymer having an alkoxysilyl group. When the alkenyl group in the vinyl polymer was measured by NMR analysis (JMN-LA400 manufactured by JASCO Corporation), the residual rate was 10%.

Claims (11)

Using a metal complex mainly composed of transition metals of Groups 7, 8, 9, 10, and 11 of the periodic table as a catalyst, a vinyl polymer polymerized by atom transfer radical polymerization is dissolved in an organic solvent, and water and an acid component are dissolved. by the mixed washing water is contacted with the polymer solution, the production of adsorbent metal catalyst remaining in the vinyl polymer is extracted into the wash water without using a vinyl polymer which is characterized in that removal Method. The manufacturing method of Claim 1 whose acid component contained in washing water is an inorganic acid. The production method according to claim 2, wherein the inorganic acid is sulfuric acid. The manufacturing method of Claim 1 whose acid component contained in washing water is an organic acid. The manufacturing method of Claim 4 whose organic acid is an acetic acid. The manufacturing method of any one of Claims 1-5 which mixes a salt with washing | cleaning water further. The manufacturing method of any one of Claims 1-6 whose organic solvent which melt | dissolves a vinyl polymer is alcohol. The manufacturing method of any one of Claims 1-7 whose organic solvent which melt | dissolves in a vinyl type polymer is a C4 or more linear alcohol. The manufacturing method of any one of Claims 1-8 whose center metal of a transition metal complex is copper. The manufacturing method of any one of Claims 1-9 whose content rate of a vinyl polymer is 5 to 90 wt% in the solution of the vinyl polymer melt | dissolved in the organic solvent. The method for producing a vinyl polymer according to any one of claims 1 to 10, and
A method for producing a vinyl polymer having a crosslinkable silyl group, comprising a method for reacting a vinyl polymer obtained by the method with a silane compound having a hydrosilyl group.