JP4988267B2 - Method for producing vinyl polymer having functional group at terminal - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a method for effectively producing a vinylic polymer having a functional group at the terminal with a small amount of a catalyst. <P>SOLUTION: The method for producing the vinylic polymer (I) involves using (B) a reducing agent in combination when producing the vinylic polymer (I) having (A) an olefin compound added to the terminal by adding the olefin compound (A) having an alkenyl group with low polymerizability to an atom-transfer radical polymerization system. Preferably, the olefin compound (A) has a functional group, and the vinylic polymer (I) having the olefin compound (A) added to the terminal has the functional group at the terminal. <P>COPYRIGHT: (C)2008,JPO&amp;INPIT

Description

The present invention relates to a method for producing a vinyl polymer having a functional group at a terminal.

It is known that a polymer having a functional group at the terminal is crosslinked by itself or in combination with an appropriate curing agent to give a cured product having excellent heat resistance and durability. Among them, polymers having an alkenyl group, a hydroxyl group or a crosslinkable silyl group at the terminal are representative examples thereof. A polymer having an alkenyl group at the terminal is crosslinked and cured by using a hydrosilyl group-containing compound as a curing agent or by utilizing a photoreaction. A polymer having a hydroxyl group at the end forms a urethane crosslink by reacting with a polyisocyanate and cures. Moreover, the polymer which has a crosslinkable silyl group at the terminal gives a hardened | cured material by absorbing moisture in presence of a suitable condensation catalyst.

On the other hand, a vinyl polymer obtained by radical polymerization and having a functional group at the terminal has not been practically used yet. In general, (meth) acrylic polymers among vinyl polymers have characteristics such as high weather resistance and transparency that cannot be obtained with the above polyether polymers, hydrocarbon polymers, or polyester polymers. Those having an alkenyl group or a crosslinkable silyl group in the side chain are used for paints having high weather resistance. On the other hand, the polymerization control of the acrylic polymer is not easy due to the side reaction, and it is very difficult to introduce a functional group to the terminal.

If a vinyl polymer having an alkenyl group at the molecular chain end can be obtained by a simple method, a cured product having excellent cured product properties can be obtained as compared with those having a crosslinkable group in the side chain. Therefore, many researchers have studied the production method so far, but it is not easy to produce them industrially.
We have found that when an olefin that is not activated (low polymerizability) is added to a vinyl monomer polymerization system by atom transfer radical polymerization, only about one is added to the growth terminal, By utilizing this, a method for producing a polymer having various functional groups at its terminals has been invented (see Patent Documents 1 and 2).
However, in the above-described method, there are cases where it is necessary to use a large amount of an atom transfer radical polymerization catalyst in order to reliably introduce a functional group or improve the reaction rate. In this case, it is necessary to use a large amount of adsorbent or the like in order to remove the polymerization catalyst, or the polymerization catalyst remaining in the polymer may cause the polymer to be colored.
JP 2000-044626 A JP 2003-292505 A

An object of the present invention is to provide a method for effectively producing a vinyl polymer having a functional group at a terminal with a small amount of catalyst.

As a result of intensive studies to solve the above problems, the inventors of the present invention added an olefin compound (A) having a low polymerizable alkenyl group to an atom transfer radical polymerization system, and an olefin compound ( When the vinyl polymer (I) added with A) is produced, it has been found that the above problem can be effectively solved by a method using the reducing agent (B) in combination, and the present invention has been achieved.

That is, the present invention produces a vinyl polymer (I) having an olefin compound (A) added to the terminal by adding an olefin compound (A) having a low alkenyl group to the atom transfer radical polymerization system. In this case, the present invention relates to a method for producing a vinyl polymer (I), characterized by using a reducing agent (B) in combination.
In the present invention, the olefin compound (A) has a functional group, and the vinyl polymer (I) to which the olefin compound (A) is added at the terminal has the functional group at the terminal. It relates to a manufacturing method.

Furthermore, in the present invention, the olefin compound (A) has the general formula (1):

{In the formula, R ³ represents a hydroxyl group, an amino group, an epoxy group, a carboxylic acid group, an ester group, an ether group, an amide group, a silyl group, a general formula (2):

(R ⁴ represents a hydrogen atom or a hydrocarbon group having 1 to 20 carbon atoms)
Or a hydrocarbon group having 1 to 20 carbon atoms not containing a polymerizable olefin,
R ¹ is an alkylene group having 1 to 20 carbon atoms, or general formula (3):

(Wherein, R ⁵ is a divalent organic group oxygen atom or a nitrogen atom to carbon atoms, which may have 1 to 20, or, an oxygen atom, R ⁶ is a hydrogen atom or 1 to carbon atoms 20 hydrocarbon groups, and a plurality of R ⁶ may be the same or different)
Represents a group represented by
R ² represents a hydrogen atom or a methyl group}
It is related with the said manufacturing method which is a compound represented by these.

In the present invention, the olefin compound (A) is represented by the general formula (4):

{In the formula, R ¹ represents an alkylene group having 1 to 20 carbon atoms, or General Formula (3):

(Wherein, R ⁵ is a divalent organic group oxygen atom or a nitrogen atom to carbon atoms, which may have 1 to 20, or, an oxygen atom, R ⁶ is a hydrogen atom or 1 to carbon atoms 20 hydrocarbon groups, and a plurality of R ⁶ may be the same or different)
Represents a group represented by
R ² represents a hydrogen atom or a methyl group,
R ⁴ represents a hydrogen atom or a hydrocarbon group having 1 to 20 carbon atoms}
It is related with the said manufacturing method which is a compound represented by these.

Furthermore, in the present invention, the olefin compound (A) has the general formula (5):

(Wherein r represents an integer of 1 to 20)
The above production method, which is a compound represented by:
The above production method wherein the olefin compound (A) is 1,5-hexadiene, 1,7-octadiene or 1,9-decadiene;
An olefin compound (A) is added in an excessive amount with respect to the growth terminal of the polymer;
Olefin compound (A), in the general formula (1), R ³ is a hydroxyl group, an amino group, an epoxy group, a carboxylic acid group, an ester group, the compound is an ether group, a group selected from the group consisting of amide groups and silyl groups The above production method;
Olefin compound (A), in the general formula (1) or (4) a compound wherein R ² is a hydrogen atom, the production method;
It is related with the said manufacturing method whose olefin compound (A) is alkenyl alcohol or alkenylamine.

Moreover, this invention is the said manufacturing method whose vinyl polymer (I) which the olefin compound (A) added to the terminal is a (meth) acrylic acid ester type polymer;
The above production method wherein the number average molecular weight of the vinyl polymer (I) having the olefin compound (A) added to the terminal is 3000 or more;
Of the ratio (Mw / Mn) of the weight average molecular weight (Mw) and the number average molecular weight (Mn) measured by gel permeation chromatography (GPC) of the vinyl polymer (I) having the olefin compound (A) added to the terminal. The above production method having a value of less than 1.8;
The present invention relates to the above production method, wherein the metal used for the catalyst for atom transfer radical polymerization is a metal selected from copper, nickel, ruthenium and iron.

Furthermore, the present invention provides the above production method, wherein the reducing agent (B) is a metal and / or a metal compound;
The above production method, wherein the metal and / or metal of the metal compound is a metal selected from copper, nickel, ruthenium and iron;
The above production method, wherein the metal and / or metal of the metal compound is the same metal as a metal used for a catalyst for atom transfer radical polymerization;
The above production method, wherein the reducing agent (B) is a metal hydride;
The above production method wherein the reducing agent (B) is an organotin compound;
The above production method, wherein the reducing agent (B) is at least one selected from the group consisting of silicon hydride, boron hydride, nitrogen compound, phosphorus, phosphorus compound, sulfur and sulfur compound;
The above production method wherein the reducing agent (B) is hydrogen;
The above production method, wherein the reducing agent (B) is an organic compound exhibiting a reducing action;
The above production method, wherein the organic compound exhibiting a reducing action is alcohol or aldehyde;
The present invention relates to the above production method, wherein the reducing agent (B) is produced by electrolysis.

The present invention is described in detail below.
In the production method of the vinyl polymer (I) in which the olefin compound (A) is added to the terminal of the present invention, the olefin compound (A) having a low alkenyl group is added to the atom transfer radical polymerization system, When the vinyl polymer (I) added with the olefin compound (A) is produced, a reducing agent (B) is used in combination.

<< Vinyl polymer (I) >>
<Polymer main chain>
It does not specifically limit as a vinyl-type monomer which comprises the principal chain of vinyl polymer (I) which the olefin compound (A) added to the terminal of this invention, Various things can be used. For example, (meth) acrylic acid, methyl (meth) acrylate, ethyl (meth) acrylate, (meth) acrylic acid-n-propyl, (meth) acrylic acid isopropyl, (meth) acrylic acid-n- Butyl, isobutyl (meth) acrylate, (meth) acrylic acid-t-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, (meth) acrylic acid dodecyl, (meth) Phenyl acrylate, toluyl (meth) acrylate, benzyl (meth) acrylate, 2-methoxyethyl (meth) acrylate, (meth ) -3-methoxybutyl acrylate, 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, stearyl (meth) acrylate, glycidyl (meth) acrylate, (meth) acrylic acid 2-aminoethyl, γ- (methacryloyloxypropyl) trimethoxysilane, ethylene oxide adduct of (meth) acrylic acid, trifluoromethylmethyl (meth) acrylate, 2-trifluoromethylethyl (meth) acrylate, ( (Meth) acrylic acid 2-perfluoroethyl ethyl, (meth) acrylic acid 2-perfluoroethyl-2-perfluorobutyl ethyl, (meth) acrylic acid 2-perfluoroethyl, (meth) acrylic acid perfluoromethyl, ( (Meth) acrylic acid diperfluoromethylmethyl, (meth) a 2-perfluoromethyl-2-perfluoroethylmethyl crylate, 2-perfluorohexylethyl (meth) acrylate, 2-perfluorodecylethyl (meth) acrylate, 2-perfluorohexadecyl (meth) acrylate (Meth) acrylic acid monomers such as ethyl; styrene monomers such as styrene, vinyltoluene, α-methylstyrene, chlorostyrene, styrenesulfonic acid and salts thereof; fluorine such as perfluoroethylene, perfluoropropylene and vinylidene fluoride -Containing vinyl monomers; silicon-containing vinyl monomers such as vinyltrimethoxysilane and vinyltriethoxysilane; maleic anhydride, maleic acid, monoalkyl esters and dialkyl esters of maleic acid; fumaric acid, monoalkyl esters of fumaric acid and dia Kill esters; maleimide monomers such as maleimide, methylmaleimide, ethylmaleimide, propylmaleimide, butylmaleimide, hexylmaleimide, octylmaleimide, dodecylmaleimide, stearylmaleimide, phenylmaleimide, cyclohexylmaleimide; containing nitrile groups such as acrylonitrile and methacrylonitrile Vinyl monomers; amide group-containing vinyl monomers such as acrylamide and methacrylamide; vinyl esters such as vinyl acetate, vinyl propionate, vinyl pivalate, vinyl benzoate and vinyl cinnamate; alkenes such as ethylene and propylene; butadiene And conjugated dienes such as isoprene; vinyl chloride, vinylidene chloride, allyl chloride, allyl alcohol and the like.

These monomers may be used alone or a plurality of monomers 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 acrylic ester monomers and methacrylic ester monomers, and particularly preferred are acrylic ester monomers.
In the present invention, these preferable monomers (styrene monomer and (meth) acrylic acid monomer) may be copolymerized with other monomers (other than the preferable monomers among the above examples), and further block copolymerized. In that case, it is preferable that 60% or more of these preferable monomers are contained by weight ratio. Further, preferable monomers may be copolymerized or further block copolymerized.
In the above expression format, for example, (meth) acrylic acid represents acrylic acid and / or methacrylic acid.

The number average molecular weight of the vinyl polymer (I) having the olefin compound (A) added to the terminal of the present invention is not particularly limited, but the lower limit is preferably 3000 or more, more preferably 5000 or more, and the upper limit is preferably 1000000 or less, more preferably 500000 or less. That is, 3000 to 1000000 is preferable, and 5000 to 500000 is more preferable.

Molecular weight distribution of vinyl polymer (I) having olefin compound (A) added to the terminal of the present invention, that is, weight average molecular weight (Mw) and number average molecular weight (Mn) measured by gel permeation chromatography (GPC) The ratio (Mw / Mn) is not particularly limited, but is preferably less than 1.8, more preferably less than 1.7, still more preferably less than 1.5, and particularly preferably less than 1.3. It is. 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 main chain of the vinyl polymer (I) of the present invention may be linear or branched.

<Synthesis method of main chain>
Radical polymerization is generally considered to be difficult to control because it has a high polymerization rate and tends to cause a termination reaction due to coupling between radicals. However, although living radical polymerization and atom transfer radical polymerization are radical polymerizations, a termination reaction hardly occurs and a polymer having a narrow molecular weight distribution (Mw / Mn is about 1.1 to 1.5) is obtained. The molecular weight can be freely controlled by the charge ratio of the initiator. Therefore, the living radical polymerization method can obtain a polymer having a narrow molecular weight distribution and a low viscosity, and a monomer having a specific functional group can be introduced at almost any position of the polymer. It is more preferable as a method for producing a vinyl polymer having a specific functional group.

In the narrow sense, living polymerization refers to polymerization in which the terminal always has activity and the molecular chain grows, but in general, the terminal is inactivated and the terminal is activated. It also includes pseudo-living polymerization that grows in an equilibrium state. The definition in the present invention is also the latter.
As this living polymerization method, particularly atom transfer radical polymerization method, for example, Matyjazewski et al., Journal of American Chemical Society (J. Am. Chem. Soc.) 1995, 117, 5614; Macromolecules (Macromolecules) 1995, 28, 7901; Science 1996, 272, 866; WO 96/30421; WO 97/18247 or Sawamoto et al., Macromolecules 1995, 28, page 1721 etc. are mentioned.

The atom transfer radical polymerization method for constructing the main chain of the vinyl polymer (I) of the present invention is not particularly limited. For example, a conventionally known method described in JP-A-2000-072809 is used. Can do.

When this atom transfer radical polymerization method is used, the transition metal used for the catalyst is preferably copper, nickel, ruthenium, or iron, and copper is particularly preferred.
The compound used as the catalyst ligand is not particularly limited, and examples thereof include 2,2′-bipyridyl and derivatives thereof, 1,10-phenanthroline and derivatives thereof, alkylamines such as tributylamine, tetramethylethylenediamine, Examples thereof include ligands such as polyamines such as pentamethyldiethylenetriamine and hexamethyltriethylenetetraamine. A ligand such as triphenylphosphine can also be used.

As a method for adding the catalyst, the catalyst itself may be added, or a method of adding only a compound that becomes a ligand of the catalyst may be used. The latter method is a method invented by the inventors of the present invention, but is a coordination that can produce catalytic activity by adding a transition metal compound and / or a transition metal complex as a catalyst raw material in the reaction system in advance. This is a method in which a child is added later as needed to generate catalytically active species in the system.
The amount of the catalyst added is not particularly limited, but is preferably 0.0001 to 50 parts by weight, more preferably 0.001 to 10 parts by weight, with respect to 100 parts by weight of the total amount of vinyl monomers. 5 parts by weight is more preferable. When the amount is less than 0.0001 part by weight, the catalytic activity tends to be hardly exhibited, and when the amount exceeds 50 parts by weight, removal from the polymer tends to be difficult after the reaction.

<< Olefin compound (A) >>
Examples of the olefin compound (A) having a low polymerizable alkenyl group include those selected from compounds represented by the following general formula (1).

{In the formula, R ³ represents a hydroxyl group, an amino group, an epoxy group, a carboxylic acid group, an ester group, an ether group, an amide group, a silyl group, a general formula (2):

(R ⁴ represents a hydrogen atom or a hydrocarbon group having 1 to 20 carbon atoms)
Or a hydrocarbon group having 1 to 20 carbon atoms not containing a polymerizable olefin,
R ¹ is an alkylene group having 1 to 20 carbon atoms, or general formula (3):

(Wherein, R ⁵ is a divalent organic group oxygen atom or a nitrogen atom to carbon atoms, which may have 1 to 20, or, an oxygen atom, R ⁶ is a hydrogen atom or 1 to carbon atoms 20 hydrocarbon groups, and a plurality of R ⁶ may be the same or different)
Represents a group represented by
R ² represents a hydrogen atom or a methyl group}

Among them, examples of the olefin compound having two low-polymerizability alkenyl groups used for introducing an alkenyl group include those selected from compounds represented by the following general formula (4).

{In the formula, R ¹ represents an alkylene group having 1 to 20 carbon atoms, or General Formula (3):

(Wherein, R ⁵ is a divalent organic group oxygen atom or a nitrogen atom to carbon atoms, which may have 1 to 20, or, an oxygen atom, R ⁶ is a hydrogen atom or 1 to carbon atoms 20 hydrocarbon groups, and a plurality of R ⁶ may be the same or different)
Represents a group represented by
R ² represents a hydrogen atom or a methyl group,
R ⁴ represents a hydrogen atom or a hydrocarbon group having 1 to 20 carbon atoms}

R ² is a hydrogen atom or a methyl group, and is preferably a hydrogen atom.
R ⁴ is a hydrogen atom or a hydrocarbon group having 1 to 20 carbon atoms, preferably a hydrogen atom.
When R ¹ is an alkylene group having 1 to 20 carbon atoms, the structure is not particularly limited, but preferred examples of the olefin compound (A) include compounds represented by the following general formula (5).

(Wherein r represents an integer of 1 to 20)
In view of easy availability of raw materials, r is preferably 2, 4, or 6. That is, 1,5-hexadiene, 1,7-octadiene, and 1,9-decadiene are preferable.

In the general formula (1), specific examples of R ¹ include
_{- (CH 2) n - (} n is an integer of 1 to 20),
_{-CH (CH 3) -, -} CH (CH 2 CH 3) -, - C (CH 3) 2 -, - C (CH 3) (CH 2 CH 3) -, - C (CH 2 CH 3) 2 _{-, - CH 2 CH (CH} 3) -,
_{- (CH 2) n -O-} CH 2 - (n is 1 to 19 integer),
_{-CH (CH 3) -O-CH} 2 -, - CH (CH 2 CH 3) -O-CH 2 -, - C (CH 3) 2 -O-CH 2 -, - C (CH 3) (CH _{2 CH 3) -O-CH 2} -, - C (CH 2 CH 3) 2 -O-CH 2 -,
_{- (CH 2) n -O- (} CH 2) m -
(M and n are integers of 1 to 19, where 2 ≦ m + n ≦ 20),
_{- (CH 2) n -C (} O) O- (CH 2) m -
(M and n are integers of 1 to 19, where 2 ≦ m + n ≦ 20),
_{- (CH 2) n -OC (} O) - (CH 2) m -C (O) O- (CH 2) l -,
(L is an integer from 0 to 18, m and n are integers from 1 to 17, where 2 ≦ l + m + n ≦ 20),
_{- (CH 2) n -o-,} m-, p-C 6 H 4 -,
_{- (CH 2) n -o-,} m-, p-C 6 H 4 - (CH 2) m -,
(M is an integer of 0 to 13, n is an integer of 1 to 14, where 1 ≦ m + n ≦ 14),
_{- (CH 2) n -o-,} m-, p-C 6 H 4 -O- (CH 2) m -,
(M is an integer of 0 to 13, n is an integer of 1 to 14, where 1 ≦ m + n ≦ 14),
_{- (CH 2) n -o-,} m-, p-C 6 H 4 -O-CH (CH 3) -,
(N is an integer from 1 to 12),
_{- (CH 2) n -o-,} m-, p-C 6 H 4 -O-C (CH 3) 2 -,
(N is an integer from 1 to 11),
_{- (CH 2) n -o-,} m-, p-C 6 H 4 -C (O) O- (CH 2) m -,
(M and n are integers of 1 to 12, where 2 ≦ m + n ≦ 13),
_{- (CH 2) n -OC (} O) -o-, m-, p-C 6 H 4 -C (O) O- (CH 2) m -,
(M and n are integers of 1 to 11, where 2 ≦ m + n ≦ 12),
_{- (CH 2) n -o-,} m-, p-C 6 H 4 -OC (O) - (CH 2) m -,
(M and n are integers of 1 to 12, where 2 ≦ m + n ≦ 13),
_{- (CH 2) n -C (} O) O-o-, m-, p-C 6 H 4 - (CH 2) m -,
(M and n are integers of 1 to 11, where 2 ≦ m + n ≦ 12),
Etc. Incidentally, an alkylene group having 1 to 20 carbon atoms of R ¹ may include an arylene group (e.g. phenylene group) therein.

Preferred examples of R ³ include the following groups.

(Wherein R ⁷ and R ⁸ 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 ⁷ or When two or more R ⁸ are present, 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 are the same. A may be 0, 1, 2 or 3, and b may be 0, 1 or 2. m represents an integer of 0 to 19, provided that a + mb ≧ 1. R ⁹ represents a hydrogen atom or a hydrocarbon group having 1 to 20 carbon atoms.)

The hydrolyzable group represented by Y is not particularly limited, and conventionally known hydrolyzable groups can be used. Specifically, hydrogen atoms, halogen atoms, alkoxy groups, acyloxy groups, ketoximate groups, amino groups, amides can be used. Groups, acid amide groups, aminooxy groups, mercapto groups, alkenyloxy groups and the like, and alkoxy groups are particularly preferred from the viewpoint that they are mild and easy to handle.

Specific examples of R ⁹ include the following groups.
_{- (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 4 (CH 3)} ,
_{-C 6 H 3 (CH 3)} 2,
_{- (CH 2) n -C 6} H 5,
_{- (CH 2) n -C 6} H 4 (CH 3),
_{- (CH 2) n -C 6} H 3 (CH 3) 2
(N is an integer of 0 or more, and the total carbon number of each group is 20 or less)
The polymerization of the hydrocarbon group having 1 to 20 carbon atoms that does not contain olefins of R ³ may include those similar to the aforementioned exemplary R ^9.
The silyl group is not particularly limited, but preferably m = 0 in the above formula.

When a compound having an amino group, a hydroxyl group or a carboxylic acid group is reacted at the polymerization end, it may be reacted as it is, but those groups may affect the polymerization end or catalyst. A compound with a protecting group may be used. Examples of the protecting group include an acetyl group, a silyl group, and an alkoxy group having 1 to 20 carbon atoms.

The olefin compound (A) is a compound in which R ³ is a group selected from a hydroxyl group, an amino group, an epoxy group, a carboxylic acid group, an ester group, an ether group, an amide group, and a silyl group in the general formula (1). Preferably there is.
Furthermore, the olefin compound (A) is preferably a compound in which R ² is a hydrogen atom in the general formula (1) or (4).
The olefin compound (A) is preferably alkenyl alcohol or alkenylamine.

<Introduction method of olefin compound (A)>
As a method for introducing the olefin compound (A) to the terminal of the vinyl polymer (I), a conventionally known method described in, for example, JP-A No. 2000-044626 can be used. This means that by adding an unactivated (low polymerizing) olefin to the atom transfer radical polymerization system, only one olefin is added to the polymer growth terminal, and various functional groups are added to the terminal. It is the method of manufacturing the polymer which has.

The addition amount of the olefin compound (A) used for introducing these functional groups is not particularly limited. It is preferable to use a small excess amount from the same amount to 1.2 times the polymer growth terminal. On the other hand, since the reactivity of the alkenyl group of the olefin compound (A) is not so high, it is possible to increase the addition amount in order to increase the reaction rate. In this case, the addition amount is preferably 1.2 times or more. More preferably 5 times or more, more preferably 3 times or more, and particularly preferably 5 times or more. On the other hand, when it is not desired to leave unreacted olefin compound (A) in the polymer, it is possible to make the amount from 0.7 times to an equivalent amount with respect to the polymer growth terminal. Therefore, the addition amount of the olefin compound (A) is not particularly limited, and can be optimized depending on the situation in consideration of the reactivity and cost of the olefin compound (A) and the cost and productivity required for recovering the unreacted product. Good.
Moreover, it is preferable that the addition amount of the compound having two or more low-polymerizability alkenyl groups used for introducing an alkenyl group at the terminal is an excessive amount with respect to the polymer growth terminal. When the amount is equal or less than the terminal, both of the two olefins may react and couple the polymerization terminal. For compounds where the reactivity of the two olefins is equal, the probability of coupling occurring is statistically determined by the amount added in excess. Therefore, the addition amount of the compound having two or more alkenyl groups having low polymerizability is more preferably 1.5 times or more, further preferably 3 times or more, particularly preferably 5 times or more, relative to the polymer growth terminal. is there.

When the olefin compound (A) having an alkenyl group having low polymerizability is added during or at the end of the atom transfer radical polymerization, the olefin compound (A) is added almost one by one to the terminal. When the olefin compound (A) has a functional group, as a result, the functional group of the olefin compound (A) is introduced into the end of the polymer. In the olefin compound (A) represented by the general formula (1), R ³ corresponds to the functional group.
The olefin compound (A) is preferably added after 80% by weight of the radical polymerizable monomer is consumed by atom transfer radical polymerization, and more preferably added when 85% by weight is consumed, It is more preferable to add when 90% by weight is consumed, and it is particularly preferable to add when 95% by weight is consumed. If the olefin compound (A) is added before the radical polymerizable monomer is sufficiently consumed, the molecular weight of the vinyl polymer tends to be smaller than the set value. The amount of the radical polymerizable monomer is the amount finally charged in the polymerization solution. The radical polymerizable monomer means the vinyl monomer.

When the olefin compound (A) is added to the atom transfer radical polymerization system, depending on the type of the olefin compound (A), the catalytic activity may be insufficient due to a decrease in the polarity of the reaction system. In this case, a compound having a dielectric constant higher than that of the olefin compound (A) (for example, a hydrocarbon compound such as benzene and toluene; an ether compound such as diethyl ether and tetrahydrofuran; a halogenated hydrocarbon compound such as methylene chloride and chloroform; Ketone compounds such as acetone, methyl ethyl ketone, methyl isobutyl ketone; alcohol compounds such as methanol, ethanol, propanol, isopropanol, n-butyl alcohol, tert-butyl alcohol; nitrile compounds such as acetonitrile, propionitrile, benzonitrile; Ester compounds such as ethyl acetate and butyl acetate; carbonate compounds such as ethylene carbonate and propylene carbonate) can be added.

<< Reducing agent (B) >>
Generally, in atom transfer radical polymerization, when radicals at the growth terminals are coupled to each other, the transition metal complex used as a catalyst becomes a complex having a high oxidation number by the amount of the coupling, and the polymerization reaction is slowed down. In a normal atom transfer radical polymerization system, the radical-radical coupling reaction does not occur so much, so this is not a problem, but the olefin compound (A) is added to the terminal by adding the olefin compound (A) of the present invention. When the vinyl polymer (I) is produced, the reaction may slow down.
In this case, it is possible to improve the speed by adding a catalyst used for atom transfer radical polymerization. However, in the present invention, it has been found that the speed can be improved by adding a reducing agent (B).

Although the reducing agent used by this manufacturing method is illustrated below, this invention is not limited to these reducing agents.
(B-1) Metal. Specific examples include alkali metals such as lithium, sodium and potassium; alkaline earth metals such as beryllium, magnesium, calcium and barium; aluminum; typical metals such as zinc; transition metals such as copper, nickel, ruthenium and iron Etc. These metals may be in the state of an alloy (amalgam) with mercury.

(B-2) Metal compound. Examples include salts of typical metals or transition metals, salts with typical elements, and complexes in which carbon monoxide, olefins, nitrogen-containing compounds, oxygen-containing compounds, phosphorus-containing compounds, sulfur-containing compounds and the like are coordinated. Specifically, compounds of metal and ammonia / amine, titanium trichloride, titanium alkoxide, chromium chloride, chromium sulfate, chromium acetate, iron chloride, copper chloride, copper bromide, tin chloride, zinc acetate, zinc hydroxide, Carbonyl complexes such as Ni (CO) ₄ and Co ₂ CO ₈ , and olefin complexes such as [Ni (cod) ₂ ], [RuCl ₂ (cod)] and [PtCl ₂ (cod)] (where cod is cyclooctadiene) ), [RhCl (P (C ₆ H ₅ ) ₃ ) ₃ ], [RuCl ₂ (P (C ₆ H ₅ ) ₃ ) ₂ ], [PtCl ₂ (P (C ₆ H ₅ ) ₃ ) ₂ ], etc. And phosphine complexes.

(B-3) Metal hydride. Specific examples include sodium hydride; germanium hydride; tungsten hydride; diisobutylaluminum hydride, lithium aluminum hydride, sodium aluminum hydride, sodium triethoxyaluminum hydride, sodium bis (2-methoxyethoxy) aluminum hydride, etc. And aluminum hydrides such as triphenyltin hydride, tri-n-butyltin hydride, diphenyltin hydride, di-n-butyltin hydride, triethyltin hydride, and trimethyltin hydride. .
(B-4) Organotin compound. Specific examples include tin octylate, tin 2-ethylhexylate, dibutyltin diacetate, dibutyltin dilaurate, dibutyltin mercaptide, dibutyltin thiocarboxylate, dibutyltin dimaleate, dioctyltin thiocarboxylate and the like.

(B-5) Silicon hydride. Specific examples include trichlorosilane, trimethylsilane, triethylsilane, diphenylsilane, phenylsilane, polymethylhydrosiloxane, and the like.
(B-6) Boron hydride. Specifically, borane, diborane, sodium borohydride, sodium trimethoxyborate, sodium borohydride, sodium cyanoborohydride, lithium borohydride, lithium borohydride, lithium triethylborohydride, hydrogen Tri-s-butyl boron hydride, lithium tri-t-butyl boron hydride, calcium borohydride, potassium borohydride, zinc borohydride, tetra-n-butylammonium borohydride and the like.
(B-7) Nitrogen compounds. Specific examples include hydrazine and diimide.

(B-8) Phosphorus or phosphorus compound. Specific examples include phosphorus, phosphine, trimethylphosphine, triethylphosphine, triphenylphosphine, trimethylphosphite, triethylphosphite, triphenylphosphite, hexamethylphosphorustriamide, hexaethylphosphorustriamide, and the like.
(B-9) Sulfur or a sulfur compound. Specifically, sulfur, Rongalite, hydrosulfite, thiourea dioxide and the like can be mentioned. Rongalite is a formaldehyde derivative of sulfoxylate and is represented by MSO ₂ · CH ₂ O (M represents Na or Zn). Specific examples include sodium formaldehyde sulfoxylate and zinc formaldehyde sulfoxylate. Hydrosulfite is a general term for sodium hyposulfite and formaldehyde derivatives of sodium hyposulfite.
(B-10) Hydrogen.

(B-11) An organic compound exhibiting a reducing action. Specific examples include alcohols, aldehydes, phenols, and organic acid compounds. Examples of the alcohol include methanol, ethanol, propanol, and isopropanol. Examples of the aldehyde include formaldehyde, acetaldehyde, benzaldehyde, formic acid and the like. Examples of phenols include phenol, hydroquinone, dibutylhydroxytoluene, tocopherol and the like. Examples of the organic acid compound include citric acid, ascorbic acid, and salts and esters thereof.

These reducing agents (B) may be used alone or in combination of two or more.
The reducing agent (B) may be added directly to the reaction system or may be generated in the reaction system. The latter includes electrolytic reduction. In electrolytic reduction, it is known that electrons generated at the cathode exhibit a reducing action immediately or once solvated. That is, the reducing agent (B) produced by electrolysis can also be used.

Among these, as the reducing agent (B), metals such as aluminum, zinc, copper, nickel, ruthenium and iron; organotin compounds such as tin octylate, tin 2-ethylhexylate and dibutyltin diacetate; alcohols, aldehydes, Organic compounds exhibiting a reducing action such as citric acid and ascorbic acid are preferred.
When a metal or a metal compound is used as the reducing agent (B), the metal in the reducing agent (B) may be different from the metal used for the catalyst for atom transfer radical polymerization or may be the same metal, From the viewpoint of the purification load of the polymer, the same metal is preferable.

When the reducing agent (B) of the present invention is solid, its shape is not particularly limited, and a lump, plate, sheet, film, rod, wire, granular / powder, etc. may be used. Or they may be porous. It does not specifically limit regarding the shape of powder, All kinds of things can be used. For example, a spherical shape, a flake shape, a dentrite shape (dendritic shape), a spindle shape, an agglomerated shape, and an indefinite shape are used. In order to promote the reaction, a larger surface area is preferable, but an appropriate shape can be selected in view of ease of handling and stability against air oxidation.
The particle size and particle size distribution of the reducing agent (B) of the present invention are not particularly limited. In order to promote the reaction, a smaller particle size is preferable because the surface area becomes larger, but in view of ease of handling, stability against air oxidation, and the like, an appropriate particle size / particle size distribution can be selected.

The reducing agent (B) of the present invention may be coated to improve convenience during handling and to prevent oxidation. The coating substance is not particularly limited, and may be an inorganic compound or an organic compound.
As an inorganic compound used for coating, for example, a silicon compound salt, an aluminum compound salt, a tin compound salt, a zinc compound salt, a zirconium compound salt, a titanium compound salt, or the like can be used.
As an organic compound used for coating, for example, a saturated fatty acid, an unsaturated fatty acid, a nitrogen-containing organic compound, a sulfur-containing organic compound, a silane coupling agent, and the like can be used.

Examples of saturated fatty acids used for coating include enanthic acid (C ₆ H ₁₃ COOH), caprylic acid (C ₇ H ₁₅ COOH), pelargonic acid (C ₈ H ₁₇ COOH), and capric acid (C ₉ H ₁₉ COOH). , Undecyl acid (C ₁₀ H ₂₁ COOH), lauric acid (C ₁₁ H ₂₃ COOH), tridecyl acid (C ₁₂ H ₂₅ COOH), myristylic acid (C ₁₃ H ₂₇ COOH), pentadecylic acid (C ₁₄ H ₂₉ COOH) , Palmitic acid (C ₁₅ H ₃₁ COOH), heptadecylic acid (C ₁₆ H ₃₃ COOH), stearic acid (C ₁₇ H ₃₅ COOH), nonadecanoic acid (C ₁₈ H ₃₇ COOH), arachidic acid (C ₁₉ H ₃₉ COOH) And behenic acid (C ₂₁ H ₄₃ COOH) and the like.
Examples of unsaturated fatty acids used for coating include acrylic acid (CH ₂ ═CHCOOH), crotonic acid (CH ₃ CH═CHCOOH), isocrotonic acid (CH ₃ CH═CHCOOH), and undecylenic acid (CH ₂ ═CH (CH) ₂ ) ₉ COOH), oleic acid (C ₁₇ H ₃₃ COOH), elaidic acid (CH ₃ (CH ₂ ) ₇ CH═CH (CH ₂ ) ₇ COOH), setoleic acid (CH ₃ (CH ₂ ) ₉ CH═CH (CH ₂ ) ₉ COOH), brassic acid (C ₂₁ H ₄₁ COOH), erucic acid (C ₂₁ H ₄₁ COOH), sorbic acid (C ₅ H ₇ COOH), linoleic acid (C ₁₇ H ₃₁ COOH), linolenic acid (C ₁₇ H ₂₉ COOH) and arachidonic acid (C ₁₃ H ₃₁ COOH).

Examples of the nitrogen-containing organic compound used for coating include 1,2,3-benzotriazole, carboxybenzotriazole, N ′, N′-bis (benzotriazolylmethyl) urea, 1H-1,2,4- And triazole compounds having a substituent such as triazole and 3-amino-1H-1,2,4-triazole.
Examples of the sulfur-containing organic compound used for coating include mercaptobenzothiazole, thiocyanuric acid, and 2-benzimidazolethiol.
Examples of the silane coupling agent used for coating include a vinyltrimethoxysilane coupling agent, an aminosilane coupling agent, a tetramethoxysilane coupling agent, a methyltrimethoxysilane coupling agent, and a diphenyldimethoxysilane coupling agent. It is done.
One of these coating agents may be used alone, or two or more thereof may be used in combination.

<How to use reducing agent (B)>
The addition method of a reducing agent (B) is not specifically limited, You may add before an olefin compound (A) with respect to a reaction system, you may add simultaneously, and you may add later. Further, the whole amount may be added all at once or in divided portions. Furthermore, when reacting the olefin compound (A), a catalyst used for atom transfer radical polymerization may be added together with the reducing agent (B), but from the viewpoint of reducing the amount of catalyst, atom transfer radical polymerization is also possible. It is preferable not to add any additional catalyst.

Although the addition amount of a reducing agent (B) is not specifically limited, 0.0001-10 weight part is preferable with respect to 100 weight part of vinyl-type total addition amount, 0.001-5 weight part is more preferable, and 0.001. More preferred is 01 to 1 part by weight. When the amount of the reducing agent (B) added is less than 0.0001 part by weight, the effect of improving the reaction rate is hardly exhibited, and when it is more than 10 parts by weight, the excess reducing agent (B) can be removed from the polymer. Tend to be difficult.

<< Usage >>
The vinyl polymer (I) with the olefin compound (A) added to the terminal obtained in the present invention is not particularly limited, but it can be made curable composition alone or by blending various additives. it can. Although it does not specifically limit as an additive for preparing a physical property, For example, a filler, a plasticizer, anti-aging agent, a pigment, a physical property modifier, a solvent etc. can be mix | blended.

The use of the curable composition thus obtained is not particularly limited, but includes electrical / electronic components (heavy electrical components, weak electrical components, electrical / electronic equipment circuits and circuit board sealing materials (refrigerators, freezers, washing machines). , Gas meter, microwave oven, steam iron or earth leakage breaker sealant), potting material (transformer high voltage circuit, printed circuit board, high voltage transformer with variable resistance, electrical insulation component, semiconductive component, conductive component, solar cell or TV flyback transformer potting), coating materials (thick film resistors for high voltage or hybrid IC circuit elements; HIC; electrical insulation components; semiconductive components; conductive components; modules; printed circuits; ceramic substrates; diodes, transistors Or bonding wire buffer material; semi-conductor element; or optical communication Optical fiber coatings), photoresist materials or adhesives (CRT wedges, necks, electrical insulation parts, semiconductive parts or conductive parts); wire coating repair materials; wire joint parts insulation seal materials; rolls for OA equipment Vibration absorbing agent; or gel or capacitor encapsulating), automotive parts (gaskets for automotive engines, electrical components or oil filter sealing materials; igniter HIC or automotive hybrid IC botting materials; automotive bodies, automotive windows Coating material for glass or engine control board; or gasket for oil pan, timing belt cover gasket, molding, headlamp lens, sunroof seal or mirror adhesive; fuel injection device, fuel heating device Air damper, pressure detection device, oil cooler for heat exchanger resin tank, variable compression ratio engine, cylinder device, regulator for compressed natural gas, pressure vessel, fuel supply system for in-cylinder direct injection internal combustion engine or O-ring for high pressure pump) , Ships (wiring connection branch boxes, electrical system parts or electrical wire sealing materials; or electrical wires or glass adhesive), aircraft or railway vehicles, civil engineering / architecture (commercial building glass screen construction joints, sashes) Building material sealant used for joints around glass, interior joints in toilets, washrooms or showcases, joints around bathtubs, outer wall expansion joints for prefabricated houses, joints for sizing boards; sealing materials for multilayer glass; Civil engineering sealants used for road repair; metal, glass, stone, slate, Paints / adhesives for concrete or roof tiles; or adhesive sheets, waterproof sheets or anti-vibration sheets), medical care (medical rubber stoppers, syringe gaskets or rubber seals for decompression blood vessels) or leisure (swimming caps, diving masks) Or a swimming member for ear plugs; or a gel cushioning member for sports shoes or baseball gloves).

By the production method of the present invention, a vinyl polymer having a functional group at the terminal can be obtained with a small amount of catalyst. For this reason, it becomes easy to remove the catalyst from the polymer, and the amount of adsorbent and the like used for removing the catalyst can be reduced.

Hereinafter, the present invention will be described in more detail with reference to examples. However, the present invention is not limited to the following examples.
In the following examples and comparative examples, “parts” and “%” represent “parts by weight” and “% by weight”, respectively.
“Number average molecular weight” and “molecular weight distribution (ratio of weight average molecular weight to number average molecular weight)” were calculated by a standard polystyrene conversion method using gel permeation chromatography (GPC). However, a GPC column filled with polystyrene cross-linked gel (shodex GPC K-802; manufactured by Showa Denko KK) was used as the GPC solvent with chloroform.
The number of functional groups introduced per molecule of the polymer was calculated based on the concentration analysis by ¹ H-NMR and the number average molecular weight determined by GPC.

Example 1
40 parts of n-butyl acrylate, 0.84 part of copper (I) bromide, and 8.8 parts of acetonitrile were charged and stirred at 80 ° C. under a nitrogen stream. To this was added 3.5 parts of diethyl 2,5-dibromoadipate, and the mixture was further stirred at 80 ° C. To this, 0.034 parts of pentamethyldiethylenetriamine (hereinafter referred to as triamine) was added to initiate the reaction. On the way, 60 parts of n-butyl acrylate was intermittently added, and further, heating and stirring were continued while appropriately adding triamine so that the temperature of the reaction solution became 80 ° C to 90 ° C. After the reaction rate of butyl acrylate reached 94%, the inside of the reaction vessel was depressurized to remove volatile components. The amount of triamine used so far was 0.15 part.
To this, 22 parts of 1,7-octadiene, 35 parts of acetonitrile, and 0.37 part of copper powder were added and stirred at 80 ° C. for 6 hours to obtain a polymer [1]. The number average molecular weight of the polymer [1] is 13500, the molecular weight distribution is 1.2, the number of alkenyl groups introduced per polymer molecule is 2.4, and the number of unreacted bromine ends is 0.0. there were.

(Comparative Example 1)
40 parts of n-butyl acrylate, 0.84 part of copper (I) bromide, and 8.8 parts of acetonitrile were charged and stirred at 80 ° C. under a nitrogen stream. To this was added 3.5 parts of diethyl 2,5-dibromoadipate, and the mixture was further stirred at 80 ° C. To this, 0.017 part of pentamethyldiethylenetriamine (hereinafter referred to as triamine) was added to initiate the reaction. On the way, 60 parts of n-butyl acrylate was intermittently added, and further, heating and stirring were continued while appropriately adding triamine so that the temperature of the reaction solution became 80 ° C to 90 ° C. After the reaction rate of butyl acrylate reached 95%, the inside of the reaction vessel was depressurized to remove volatile components. The amount of triamine used so far was 0.15 part.
To this, 22 parts of 1,7-octadiene, 35 parts of acetonitrile and 0.17 part of triamine were added and heated and stirred at 80 ° C. One hour after the addition of 1,7-octadiene, 0.17 part of triamine was added. Six hours after the addition of 1,7-octadiene, there were 0.32 unreacted bromine ends per polymer molecule, so 0.17 part of triamine was added. 13 hours after the addition of 1,7-octadiene, the number of unreacted bromine ends per polymer molecule was 0.13, so 0.17 part of triamine was further added. After 19 hours from the addition of 1,7-octadiene, comparative polymer [1] was obtained. The number average molecular weight of the comparative polymer [1] is 11700, the molecular weight distribution is 1.1, 1.8 alkenyl groups are introduced per polymer molecule, and 0.05 unreacted bromine ends are present. Met.

The results of Example 1 and Comparative Example 1 are shown in Table 1. In Example 1, 1,7-octadiene could be introduced into the polymer terminal in a short time and with a small amount of catalyst (amount of triamine) by adding copper powder as a reducing agent.

(Example 2)
40 parts of n-butyl acrylate, 0.84 part of copper (I) bromide, and 8.8 parts of acetonitrile were charged and stirred at 80 ° C. under a nitrogen stream. To this, 1.8 parts of diethyl 2,5-dibromoadipate was added, and the mixture was further stirred at 80 ° C. To this, 0.034 parts of pentamethyldiethylenetriamine (hereinafter referred to as triamine) was added to initiate the reaction. On the way, 60 parts of n-butyl acrylate was intermittently added, and further, heating and stirring were continued while appropriately adding triamine so that the temperature of the reaction solution became 80 ° C to 90 ° C. After the reaction rate of butyl acrylate reached 95%, the inside of the reaction vessel was depressurized to remove volatile components. The amount of triamine used so far was 0.17 parts.
To this, 22 parts of 1,7-octadiene, 35 parts of acetonitrile and 0.52 part of ascorbic acid were added, and the mixture was heated and stirred at 80 ° C. for 6 hours to obtain a polymer [2]. The number average molecular weight of the polymer [2] is 23200, the molecular weight distribution is 1.2, the number of alkenyl groups introduced per polymer molecule is 1.3, and the number of unreacted bromine ends is 0.6. there were.

(Comparative Example 2)
A comparative polymer [2] was obtained in the same manner as in Example 2 except that no ascorbic acid was added in Example 2. The number average molecular weight of the comparative polymer [2] is 22600, the molecular weight distribution is 1.2, 0.3 alkenyl groups are introduced per polymer molecule, and 1.2 unreacted bromine ends are present. Met.

The results of Example 2 and Comparative Example 2 are shown in Table 2. In Example 2 and Comparative Example 2, the catalyst amount (triamine amount) is the same, but in Example 2, by adding ascorbic acid as a reducing agent, olefin compound (1,7-octadiene) and As a result, it was possible to reduce the number of unreacted polymer ends.

By the production method of the present invention, a vinyl polymer having a functional group at the terminal can be obtained with a small amount of catalyst. For this reason, it becomes easy to remove the catalyst from the polymer, and the amount of adsorbent and the like used for removing the catalyst can be reduced.

Claims (22)

When an olefin compound (A) having an alkenyl group having a low polymerization property is added to an atom transfer radical polymerization system to produce a vinyl polymer (I) having an olefin compound (A) added to the terminal, a reducing agent (B ) In combination with a vinyl polymer (I),
The olefin compound (A) is represented by the general formula (1):

{In the formula, R ³ represents a hydroxyl group, an amino group, an epoxy group, a carboxylic acid group, an ester group, an ether group, an amide group, a silyl group, a general formula (2):

(R ⁴ represents a hydrogen atom or a hydrocarbon group having 1 to 20 carbon atoms)
Or a hydrocarbon group having 1 to 20 carbon atoms not containing a polymerizable olefin,
R ¹ is an alkylene group having 1 to 20 carbon atoms, or general formula (3):

(Wherein, R ⁵ is a divalent organic group oxygen atom or a nitrogen atom to carbon atoms, which may have 1 to 20, or, an oxygen atom, R ⁶ is a hydrogen atom or 1 to carbon atoms 20 hydrocarbon groups, and a plurality of R ⁶ may be the same or different)
Represents a group represented by
R ² represents a hydrogen atom or a methyl group}
A method for producing a vinyl polymer (I), which is a compound represented by the formula: The olefin compound (A) is represented by the general formula (4):

{In the formula, R ¹ represents an alkylene group having 1 to 20 carbon atoms, or General Formula (3):

(Wherein, R ⁵ is a divalent organic group oxygen atom or a nitrogen atom to carbon atoms, which may have 1 to 20, or, an oxygen atom, R ⁶ is a hydrogen atom or 1 to carbon atoms 20 hydrocarbon groups, and a plurality of R ⁶ may be the same or different)
Represents a group represented by
R ² represents a hydrogen atom or a methyl group,
R ⁴ represents a hydrogen atom or a hydrocarbon group having 1 to 20 carbon atoms}
In a compound represented by the production method of the vinyl polymer according to claim 1 (I). The olefin compound (A) is represented by the general formula (5):

(Wherein r represents an integer of 1 to 20)
The manufacturing method of the vinyl polymer (I) of Claim 1 or 2 which is a compound represented by these. The method for producing a vinyl polymer (I) according to claim 3, wherein the olefin compound (A) is 1,5-hexadiene, 1,7-octadiene or 1,9-decadiene. The method for producing a vinyl polymer (I) according to any one of claims 2 to 4 , wherein the olefin compound (A) is added 1.2 times or more with respect to the growth terminal of the polymer. . Olefin compound (A), in the general formula (1), R ³ is a hydroxyl group, an amino group, an epoxy group, a carboxylic acid group, an ester group, the compound is an ether group, a group selected from the group consisting of amide groups and silyl groups The method for producing a vinyl polymer (I) according to claim 1, wherein Olefin compound (A), Oite the general formula (1) are compounds wherein R ² is a hydrogen atom, a vinyl polymer according to any one of claims 1, 2, 5 and 6 (I ) Manufacturing method. The olefin compound (A) is represented by R in the general formula (4). ² The method for producing a vinyl polymer (I) according to claim 2 or 5, wherein is a compound in which is a hydrogen atom. The method for producing a vinyl polymer (I) according to any one of claims 1 and 6 to 8 , wherein the olefin compound (A) is alkenyl alcohol or alkenylamine. The vinyl polymer according to any one of claims 1 to 9 , wherein the main chain of the vinyl polymer (I) to which the olefin compound (A) is added is a (meth) acrylic acid ester polymer. The manufacturing method of (I). The method for producing a vinyl polymer (I) according to any one of claims 1 to 10 , wherein the number average molecular weight of the vinyl polymer (I) having the olefin compound (A) added to the terminal is 3000 or more. . Of the ratio (Mw / Mn) of the weight average molecular weight (Mw) and the number average molecular weight (Mn) measured by gel permeation chromatography (GPC) of the vinyl polymer (I) having the olefin compound (A) added to the terminal. The method for producing a vinyl polymer (I) according to any one of claims 1 to 11 , wherein the value is less than 1.8. The method for producing a vinyl polymer (I) according to any one of claims 1 to 12 , wherein the metal used for the catalyst for atom transfer radical polymerization is a metal selected from copper, nickel, ruthenium and iron. The method for producing a vinyl polymer (I) according to any one of claims 1 to 13 , wherein the reducing agent (B) is a metal and / or a metal compound. The method for producing a vinyl polymer (I) according to claim 14 , wherein the metal and / or metal of the metal compound is a metal selected from copper, nickel, ruthenium and iron. The method for producing a vinyl polymer (I) according to claim 14 or 15 , wherein the metal and / or metal of the metal compound is the same metal as that used for a catalyst for atom transfer radical polymerization. The method for producing a vinyl polymer (I) according to any one of claims 1 to 13 , wherein the reducing agent (B) is a metal hydride. The method for producing a vinyl polymer (I) according to any one of claims 1 to 13 , wherein the reducing agent (B) is an organotin compound. Reducing agent (B), silicon hydride, boron hydride, nitrogen compounds, phosphorus, phosphorus compounds, at least one selected from the group consisting of sulfur and sulfur compounds, in any one of claims 1 to 13 The manufacturing method of vinyl polymer (I) of description. The method for producing a vinyl polymer (I) according to any one of claims 1 to 13 , wherein the reducing agent (B) is hydrogen. The method for producing a vinyl polymer (I) according to any one of claims 1 to 13 , wherein the reducing agent (B) is an alcohol, an aldehyde, a phenol, or an organic acid compound . The method for producing a vinyl polymer (I) according to claim 21 , wherein the reducing agent (B) is an alcohol or an aldehyde.