JP4842887B2 - Method for producing branched polymer and polymer - Google Patents

Description

The present invention relates to a method for producing a branched polymer in which a macromonomer of a vinyl polymer having a polymerizable carbon-carbon double bond at a terminal is polymerized.

Graft copolymers having a comb-like structure have attracted attention in the field of polymer materials together with block copolymers. The reason is that these polymers have characteristics as constituent segments as seen in thermoplastic elastomers and impact-resistant plastics and can exhibit unique functions based on a microphase-separated structure.

Although graft polymers have long been used to modify polymers, it has only recently been possible to synthesize polymers with well-controlled structures. The concept of a high molecular weight monomer was shown by Milkovich et al., And by copolymerizing this, it became possible to synthesize a polymer having a clear comb-like structure.

On the other hand, a star polymer is a polymer in which a linear arm is radially extended from a central portion, and is known to have various properties different from those of a linear polymer.

There are roughly two types of methods for synthesizing star polymers. One is a method of growing a polymer as an arm from a central compound or polymer, and the other is a method in which a polymer as an arm is first formed and connected to form a star. As a method of connecting the arms, there is a method of reacting a compound having a plurality of functional groups that react with the terminal functional group of the polymer serving as the arm, a method of adding a compound having a plurality of polymerizable groups after the polymerization of the arm, or polymerization at the terminal. And a method of polymerizing a polymer having a functional group (hereinafter referred to as “macromonomer” in the present specification).

As the polymer constituting such a star polymer, there are both homopolymers and copolymers, and there are various types such as polystyrene, poly (meth) acrylate, polydiene, polyether, polyester, polysiloxane and the like. . In order to obtain a controlled star structure, anionic polymerization, living cationic polymerization, or degeneracy is often used because the polymerization needs to be controlled in any method.

In contrast to the polymer obtained by ionic polymerization or condensation polymerization exemplified above, a vinyl polymer obtained by radical polymerization and having a star-shaped structure has not been practically used yet. Among them, the method of building chain extension or star structure by combining macromonomers has not been successful yet. Vinyl polymers generally have characteristics that cannot be obtained with the above-mentioned polyether polymers, hydrocarbon polymers, or polyester polymers, such as high weather resistance and transparency. Those having a silyl group in the side chain are used for paints having high weather resistance.

If a macromonomer is used in this way, a graft polymer or a star polymer can be obtained, but it is still not easy to synthesize the macromonomer. In particular, a macromonomer of a vinyl polymer that is generally polymerized by radical polymerization is hardly synthesized because the polymerization may be difficult to control. Especially, since the polymerization control of an acrylic polymer is not easy due to the side reaction, it is difficult to produce a macromonomer having a polymerizable group at the terminal.

In view of the above, an object of the present invention is to provide a method for producing a branched polymer using a macromonomer of a vinyl polymer produced by radical polymerization.

The present invention is a vinyl polymer produced by radical polymerization, and polymerizes a macromonomer (I) having one group having a polymerizable carbon-carbon double bond per molecule at the molecular end. This invention relates to a method for producing a branched polymer.

The group having a polymerizable carbon-carbon double bond is preferably represented by the general formula (1):
—OC (O) C (R) ═CH ₂ (1)
(In the formula, R represents hydrogen or a monovalent organic group having 1 to 20 carbon atoms.)
R is more preferably hydrogen or a methyl group.

The main chain of the macromonomer (I) is not limited, but is preferably produced by living radical polymerization, more preferably atom transfer radical polymerization. The atom transfer radical polymerization is preferably carried out using a transition metal complex having a group 7 element, group 8, group 9, group 10, or group 11 element as a central metal in the periodic table, more preferably, The metal complex used as a catalyst is a metal complex selected from the group consisting of copper, nickel, ruthenium and iron, and it is particularly preferable to use a copper complex as a catalyst.

The main chain of the macromonomer (I) is not limited, but is preferably a (meth) acrylic polymer or a styrene polymer, and more preferably an acrylate polymer.

Although it does not limit as macromonomer (I), Preferably, it is manufactured by substituting the terminal halogen group of a vinyl polymer with the compound which has a radically polymerizable carbon-carbon double bond. More preferably, the general formula (2):
-CR ¹ R ² X (2)
(In the formula, R ¹ and R ² are groups bonded to an ethylenically unsaturated group of a vinyl monomer. X represents chlorine, bromine, or iodine.)
A vinyl polymer having a terminal halogen group represented by general formula (3):
M ^{+ −} OC (O) C (R) ═CH ₂ (3)
(In the formula, R represents hydrogen or a monovalent organic group having 1 to 20 carbon atoms. M ⁺ represents an alkali metal or a quaternary ammonium ion.)
It is manufactured by substituting with the compound shown by.

Further, the macromonomer (I) includes a vinyl polymer having a hydroxyl group at the terminal, and the general formula (4):
XC (O) C (R) = CH ₂ (4)
(In the formula, R represents hydrogen or a monovalent organic group having 1 to 20 carbon atoms. X represents chlorine, bromine, or a hydroxyl group.)
A method of reacting with a compound represented by
A vinyl polymer having a hydroxyl group at the terminal is reacted with a diisocyanate compound to form a residual isocyanate group and a general formula (5):
HO—R′—OC (O) C (R) ═CH ₂ (5)
(In the formula, R represents hydrogen or a monovalent organic group having 1 to 20 carbon atoms. R ′ represents a divalent organic group having 2 to 20 carbon atoms.)
It may be produced by a method of reacting with the compound represented by

In these, what is manufactured by the method of substituting said terminal halogen group is more preferable.

The number average molecular weight of the polymer of the macromonomer (I) is not limited, but is preferably 3000 or more, and the weight average molecular weight (Mw) and number average of the macromonomer (I) measured by gel permeation chromatography. The value of the molecular weight (Mn) ratio (Mw / Mn) is preferably less than 1.8.

The method for polymerizing the macromonomer (I) of the present invention is not limited, but is preferably radical polymerization, more preferably living radical polymerization, and still more preferably atom transfer radical polymerization. The atom transfer radical polymerization is preferably carried out using a transition metal complex having a group 7 element, group 8, group 9, group 10, or group 11 element as a central metal in the periodic table, more preferably, The metal complex used as a catalyst is a metal complex selected from the group consisting of copper, nickel, ruthenium, and iron, and it is particularly preferable to use a copper complex as a catalyst.

In addition, as a method for polymerizing the macromonomer (I), polymerization that initiates polymerization by active energy rays and polymerization that initiates polymerization by heating are also preferable.

The method for polymerizing the macromonomer (I) may be anionic polymerization.

A star-shaped polymer is obtained by polymerizing the macromonomer (I) of the present invention alone, and graft copolymer is obtained by copolymerizing the macromonomer (I) with a copolymerizable monomer (II) other than the macromonomer. A polymer is obtained, and a polyfunctional compound having at least two groups having macromonomer (I) and a polymerizable carbon-carbon double bond per molecule, preferably a polymer having the double bond at the molecular end A crosslinked polymer (gel) is obtained by copolymerizing (III).

The present invention is also a branched polymer obtainable by the process of the present invention.

Although the use of the polymer of this invention is not limited, it is utilized as a thermoplastic elastomer, an impact resistance improving material, and an adhesive.

In the present invention, a vinyl polymer macromonomer in which a group having a polymerizable carbon-carbon double bond such as a (meth) acryloyl group is introduced at a high ratio at the terminal is used, so that synthesis has been performed so far. Graft copolymers, star polymers, gels, and the like that have a vinyl polymer branch as a branch are easily synthesized. Further, by producing a macromonomer using living radical polymerization, particularly atom transfer radical polymerization, a polymer having a well-controlled side chain molecular weight can be obtained.

The present invention polymerizes macromonomer (I), which is a vinyl polymer produced by radical polymerization, having one group per molecule having a polymerizable carbon-carbon double bond at the molecular end. Is a method for producing a branched polymer.

The group having a polymerizable carbon-carbon double bond is preferably a group represented by the general formula (1).

In the general formula (1), the specific example of R is not particularly limited as long as it is a monovalent organic group having 1 to 20 carbon atoms. For example, a substituted or unsubstituted hydrocarbon group having 1 to 20 carbon atoms, ether Group, acyl group, carbon, nitrogen-containing group, carbon, sulfur-containing group, carbon, oxygen-containing group, etc., specifically, for example, —H, —CH ₃ , —CH ₂ CH ₃ , — (CH ₂ ) _n CH ₃ (n represents an integer of 2 to 19), —C ₆ H ₅ , —CH ₂ OH, —CN and the like, preferably —H and —CH ₃ . .

<Main chain of macromonomer (I)>
There is no restriction | limiting in particular as a monomer which comprises the principal chain of macromonomer (I) of this invention, A various thing 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, (tert-butyl) (meth) acrylate, n-pentyl (meth) acrylate, n-hexyl (meth) acrylate, cyclohexyl (meth) acrylate, (meth) acryl Acid-n-heptyl, (meth) acrylic acid-n-octyl, (meth) 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) acrylic acid-3-methoxybutyl, (meth) acrylic acid-2-hydroxyethyl, (meth) acrylic acid-2-hydroxypropyl, (meth) acrylic acid stearyl, (meth) acrylic acid glycidyl, (meth) 2-aminoethyl acrylate, γ- (methacryloyloxypropyl) trimethoxysilane, ethylene oxide adduct of (meth) acrylic acid, trifluoromethylmethyl (meth) acrylate, 2-trifluoromethylethyl (meth) acrylate , 2-perfluoroethylethyl (meth) acrylate, 2-perfluoroethyl-2-perfluorobutylethyl (meth) acrylate, 2-perfluoroethyl (meth) acrylate, perfluoromethyl (meth) acrylate , (Perfluoromethylmethyl) (meth) acrylate, (me T) 2-perfluoromethyl-2-perfluoroethylmethyl acrylate, 2-perfluorohexylethyl (meth) acrylate, 2-perfluorodecylethyl (meth) acrylate, 2-perfluoro (meth) acrylate (Meth) acrylic acid monomers such as hexadecylethyl; styrene monomers such as styrene, vinyltoluene, α-methylstyrene, chlorostyrene, styrenesulfonic acid and their salts; perfluoroethylene, perfluoropropylene, vinylidene fluoride, etc. Fluorine-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 Dialkyl esters; maleimide monomers such as maleimide, methylmaleimide, ethylmaleimide, propylmaleimide, butylmaleimide, hexylmaleimide, octylmaleimide, dodecylmaleimide, stearylmaleimide, phenylmaleimide, cyclohexylmaleimide; 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 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. More preferred are acrylic ester monomers and methacrylic ester monomers, and even more preferred is butyl acrylate. In the present invention, these preferable monomers may be copolymerized with other monomers, and in this case, it is preferable that these preferable monomers are contained in a weight ratio of 40%.

The macromonomer (I) of the present invention has a molecular weight distribution, that is, the ratio of the weight average molecular weight to the number average molecular weight measured by gel permeation chromatography is preferably less than 1.8, more preferably 1.7 or less. More preferably 1.6 or less, particularly 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, usually, a polystyrene gel column or the like is used with chloroform or tetrahydrofuran as a mobile phase, and the molecular weight value is obtained in terms of polystyrene. The narrower the molecular weight distribution, the lower the viscosity of the macromonomer and the better the structure of the branched polymer produced by the process of the present invention.

The number average molecular weight of the macromonomer (I) of the present invention is preferably in the range of 500 to 100,000, more preferably 3000 to 40,000. When the molecular weight is 500 or less, the original characteristics of the vinyl polymer are hardly expressed, and when it is 100,000 or more, handling becomes difficult.

<Polymerization of macromonomer (I) main chain>
The vinyl polymer that is the main chain of the macromonomer (I) of the present invention is produced by radical polymerization. The radical polymerization method uses an azo compound, a peroxide, or the like as a polymerization initiator, and a “general radical polymerization method” in which a monomer having a specific functional group is simply copolymerized with a vinyl monomer, a terminal, etc. This can be classified as a “controlled radical polymerization method” in which a specific functional group can be introduced at a controlled position.

The “general radical polymerization method” is a simple method. However, in this method, a monomer having a specific functional group is introduced into the polymer only in a probabilistic manner, so an attempt is made to obtain a polymer having a high functionalization rate. In such a case, it is necessary to use the monomer having the specific functional group in a considerably large amount. On the other hand, there is a problem in that the proportion of the polymer in which the specific functional group is not introduced increases when the small amount is used. Moreover, since it is free radical polymerization, there is also a problem that only a polymer having a wide molecular weight distribution and a high viscosity can be obtained.

“Controlled radical polymerization method” further includes a “chain transfer agent method” in which a vinyl polymer having a specific functional group at a terminal is obtained by performing polymerization using a chain transfer agent having a specific functional group, It can be classified as a “living radical polymerization method” in which a polymer having a molecular weight almost as designed can be obtained by growing the polymerization growth terminal without causing a termination reaction or the like.

In the “chain transfer agent method”, a polymer having a high functionalization rate can be obtained, but a chain transfer agent having a considerably large amount of a specific functional group with respect to the initiator is required. There is an economic problem. Further, like the above-mentioned “general radical polymerization method”, there is also a problem that only a polymer having a wide molecular weight distribution and a high viscosity can be obtained because of free radical polymerization.

Unlike these polymerization methods, the “living radical polymerization method” is a radical polymerization that is difficult to control because it has a high polymerization rate and is likely to cause a termination reaction due to coupling between radicals. The reaction hardly occurs and a polymer having a narrow molecular weight distribution (Mw / Mn is about 1.1 to 1.5) is obtained, and the molecular weight can be freely controlled by the charging ratio of the monomer and the initiator.

Accordingly, 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. The method for producing the vinyl polymer having the specific functional group is more preferable.

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.

The “living radical polymerization method” has been actively researched by various groups in recent years. Examples thereof include those using a cobalt porphyrin complex as shown in, for example, Journal of American Chemical Society (J. Am. Chem. Soc.), 1994, 116, 7943, Macromolecules. (Macromolecules), 1994, Vol. 27, p. 7228, using a radical scavenger such as a nitroxide compound, and “atom transfer radical polymerization” using an organic halide as an initiator and a transition metal complex as a catalyst ( Atom Transfer Radical Polymerization (ATRP).

Among the “living radical polymerization methods”, the “atom transfer radical polymerization method” in which a vinyl monomer is polymerized using an organic halide or a sulfonyl halide compound as an initiator and a transition metal complex as a catalyst is the above “living radical polymerization method”. In addition to the characteristics of `` legal method '', it has a halogen which is relatively advantageous for functional group conversion reaction at the end, and has a large degree of freedom in designing initiators and catalysts. It is further preferable as a manufacturing method. As this atom transfer radical polymerization method, for example, Matyjazewski et al., Journal of American Chemical Society (J. Am. Chem. Soc.) 1995, 117, 5614, Macromolecules 1995, 28, 7901, Science 1996, 272, 866, WO96 / 30421, WO97 / 18247, WO98 / 01480, WO98 / 40415, or Sawamoto et al., Macromolecules. Macromolecules 1995, 28, 1721, JP-A-9-208616, JP-A-8-41117, and the like.

In the present invention, there is no particular restriction as to which of these methods is used, but basically, controlled radical polymerization is utilized, and living radical polymerization is preferred from the viewpoint of ease of control, and particularly, atom transfer radical polymerization method. Is preferred.

First, one of controlled radical polymerizations, polymerization using a chain transfer agent will be described. Although it does not specifically limit as radical polymerization using a chain transfer agent (telomer), The following two methods are illustrated as a method of obtaining the vinyl polymer which has a terminal structure suitable for this invention.

That is, a method for obtaining a halogen-terminated polymer using a halogenated hydrocarbon as a chain transfer agent as disclosed in JP-A-4-132706, and JP-A-61-271306 and JP-A-2594402. JP-A-54-47782 discloses a method for obtaining a hydroxyl-terminated polymer using a hydroxyl group-containing mercaptan or a hydroxyl group-containing polysulfide as a chain transfer agent.

Next, living radical polymerization will be described.

First, a method using a radical scavenger such as a nitroxide compound will be described. In this polymerization, a stable nitroxy free radical (= N-O.) Is generally used as a radical capping agent. Examples of such compounds include, but are not limited to, 2,2,6,6-substituted-1-piperidinyloxy radical, 2,2,5,5-substituted-1-pyrrolidinyloxy radical, and the like. Nitroxy free radicals from cyclic hydroxyamines are preferred. As the substituent, an alkyl group having 4 or less carbon atoms such as a methyl group or an ethyl group is suitable. Specific nitroxy free radical compounds include, but are not limited to, 2,2,6,6-tetramethyl-1-piperidinyloxy radical (TEMPO), 2,2,6,6-tetraethyl-1- Piperidinyloxy radical, 2,2,6,6-tetramethyl-4-oxo-1-piperidinyloxy radical, 2,2,5,5-tetramethyl-1-pyrrolidinyloxy radical, 1, Examples include 1,3,3-tetramethyl-2-isoindolinyloxy radical, N, N-di-t-butylamineoxy radical, and the like. Instead of the nitroxy free radical, a stable free radical such as a galvinoxyl free radical may be used.

The radical capping agent is used in combination with a radical generator. It is considered that the reaction product of the radical capping agent and the radical generator serves as a polymerization initiator and the polymerization of the addition polymerizable monomer proceeds. The combination ratio of both is not particularly limited, but 0.1 to 10 mol of radical initiator is appropriate for 1 mol of radical capping agent.

As the radical generator, various compounds can be used, but a peroxide capable of generating a radical under the polymerization temperature condition is preferable. Examples of the peroxide include, but are not limited to, diacyl peroxides such as benzoyl peroxide and lauroyl peroxide, dialkyl peroxides such as dicumyl peroxide and di-t-butyl peroxide, diisopropyl peroxydicarbonate, bis There are peroxycarbonates such as (4-t-butylcyclohexyl) peroxydicarbonate, alkyl peresters such as t-butylperoxyoctate and t-butylperoxybenzoate. Benzoyl peroxide is particularly preferable. Furthermore, radical generators such as radical-generating azo compounds such as azobisisobutyronitrile may be used instead of peroxide.

As reported in Macromolecules 1995, 28, 2993, instead of using a radical capping agent and a radical generator in combination, the following alkoxyamine compound may be used as an initiator.

When an alkoxyamine compound is used as an initiator, a polymer having a functional group such as a hydroxyl group at the terminal can be obtained by using a compound having a functional group such as a hydroxyl group as shown above. When this is used in the method of the present invention, a polymer having a functional group at the terminal can be obtained.

In the above-described polymerization using a radical scavenger such as a nitroxide compound, polymerization conditions such as a monomer used, a solvent, and a polymerization temperature are not limited, but may be the same as those used for atom transfer radical polymerization described below.

Next, a more preferred atom transfer radical polymerization method as the living radical polymerization of the present invention will be described.

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, 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
(In the above chemical formulas, C ₆ H ₅ is a phenyl group, X is chlorine, bromine, or iodine)
^{_{R 3 -C (H) (X}} ) -CO 2 R 4, R 3 -C (CH 3) (X) -CO 2 R 4, R 3 -C (H) (X) -C (O) R 4 _{^{, R 3 -C (CH 3)}} (X) -C (O) R 4,
(In each formula, R ³ and R ⁴ are a hydrogen atom or 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, X is chlorine, bromine, or iodine. )
R ³ —C ₆ H ₄ —SO ₂ X
(R ³ is a hydrogen atom or 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, and X is chlorine, bromine, or iodine).

As an initiator of atom transfer radical polymerization, an organic halide or a sulfonyl halide compound having a functional group other than the functional group for initiating polymerization can also be used. In such a case, a vinyl polymer having a structure represented by the general formula (2) at one end of the main chain and the other end is produced. Examples of such functional groups include alkenyl groups, crosslinkable silyl groups, hydroxyl groups, epoxy groups, amino groups, amide groups, and the like.

It does not limit as an organic halide which has an alkenyl group, For example, what has a structure shown in General formula (6) is illustrated.
^{R 6 R 7 C (X)} -R 8 -R 9 -C (R 5) = CH 2 (6)
(In the formula, R ⁵ is hydrogen or a methyl group, R ⁶ and R ⁷ are hydrogen, a monovalent alkyl group having 1 to 20 carbon atoms, an aryl group having 6 to 20 carbon atoms, or 7 to 20 carbon atoms. Aralkyl groups of the above, or those linked to each other at the other end, R ⁸ is —C (O) O— (ester group), —C (O) — (keto group), or o—, m—, p—. A phenylene group, R ⁹ is a direct bond, or a divalent organic group having 1 to 20 carbon atoms and may contain one or more ether bonds, X is chlorine, bromine, or iodine)

Specific examples of the substituents R ⁶ and R ⁷ are not particularly limited, and examples thereof include hydrogen, methyl group, ethyl group, n-propyl group, isopropyl group, butyl group, pentyl group, and hexyl group. R ⁶ and R ⁷ may be linked at the other end to form a cyclic skeleton.

（上記の各式において、Ｘは塩素、臭素、またはヨウ素、ｎは０〜２０の整数）
ＸＣＨ_２Ｃ（Ｏ）Ｏ（ＣＨ_２）_ｎＯ（ＣＨ_２）_ｍＣＨ＝ＣＨ_２、
Ｈ_３ＣＣ（Ｈ）（Ｘ）Ｃ（Ｏ）Ｏ（ＣＨ_２）_ｎＯ（ＣＨ_２）_ｍＣＨ＝ＣＨ_２、
（Ｈ_３Ｃ）_２Ｃ（Ｘ）Ｃ（Ｏ）Ｏ（ＣＨ_２）_ｎＯ（ＣＨ_２）_ｍＣＨ＝ＣＨ_２、
ＣＨ_３ＣＨ_２Ｃ（Ｈ）（Ｘ）Ｃ（Ｏ）Ｏ（ＣＨ_２）_ｎＯ（ＣＨ_２）_ｍＣＨ＝ＣＨ_２、

（上記の各式において、Ｘは塩素、臭素、またはヨウ素、ｎは１〜２０の整数、ｍは０〜２０の整数）
ｏ，ｍ，ｐ−ＸＣＨ_２−Ｃ_６Ｈ_４−（ＣＨ_２）_ｎ−ＣＨ＝ＣＨ_２、
ｏ，ｍ，ｐ−ＣＨ_３Ｃ（Ｈ）（Ｘ）−Ｃ_６Ｈ_４−（ＣＨ_２）_ｎ−ＣＨ＝ＣＨ_２、
ｏ，ｍ，ｐ−ＣＨ_３ＣＨ_２Ｃ（Ｈ）（Ｘ）−Ｃ_６Ｈ_４−（ＣＨ_２）_ｎ−ＣＨ＝ＣＨ_２、
（上記の各式において、Ｘは塩素、臭素、またはヨウ素、ｎは０〜２０の整数）
ｏ，ｍ，ｐ−ＸＣＨ_２−Ｃ_６Ｈ_４−（ＣＨ_２）_ｎ−Ｏ−（ＣＨ_２）_ｍ−ＣＨ＝ＣＨ_２、
ｏ，ｍ，ｐ−ＣＨ_３Ｃ（Ｈ）（Ｘ）−Ｃ_６Ｈ_４−（ＣＨ_２）_ｎ−
Ｏ−（ＣＨ_２）_ｍ−ＣＨ＝ＣＨ_２、
ｏ，ｍ，ｐ−ＣＨ_３ＣＨ_２Ｃ（Ｈ）（Ｘ）−Ｃ_６Ｈ_４−（ＣＨ_２）_ｎ−
Ｏ−（ＣＨ_２）_ｍＣＨ＝ＣＨ_２、
（上記の各式において、Ｘは塩素、臭素、またはヨウ素、ｎは１〜２０の整数、ｍは０〜２０の整数）
ｏ，ｍ，ｐ−ＸＣＨ_２−Ｃ_６Ｈ_４−Ｏ−（ＣＨ_２）_ｎ−ＣＨ＝ＣＨ_２、
ｏ，ｍ，ｐ−ＣＨ_３Ｃ（Ｈ）（Ｘ）−Ｃ_６Ｈ_４−Ｏ−（ＣＨ_２）_ｎ−ＣＨ＝ＣＨ_２、
ｏ，ｍ，ｐ−ＣＨ_３ＣＨ_２Ｃ（Ｈ）（Ｘ）−Ｃ_６Ｈ_４−Ｏ−（ＣＨ_２）_ｎ−ＣＨ＝ＣＨ_２、
（上記の各式において、Ｘは塩素、臭素、またはヨウ素、ｎは０〜２０の整数）
ｏ，ｍ，ｐ−ＸＣＨ_２−Ｃ_６Ｈ_４−Ｏ−（ＣＨ_２）_ｎ−Ｏ−（ＣＨ_２）_ｍ−ＣＨ＝ＣＨ_２、
ｏ，ｍ，ｐ−ＣＨ_３Ｃ（Ｈ）（Ｘ）−Ｃ_６Ｈ_４−Ｏ−（ＣＨ_２）_ｎ−
Ｏ−（ＣＨ_２）_ｍ−ＣＨ＝ＣＨ_２、
ｏ，ｍ，ｐ−ＣＨ_３ＣＨ_２Ｃ（Ｈ）（Ｘ）−Ｃ_６Ｈ_４−Ｏ−（ＣＨ_２）_ｎ−
Ｏ−（ＣＨ_２）_ｍ−ＣＨ＝ＣＨ_２、
（上記の各式において、Ｘは塩素、臭素、またはヨウ素、ｎは１〜２０の整数、ｍは０〜２０の整数） Specific examples of the organic halide having an alkenyl group represented by the general formula (6) include, for example,
_{XCH 2 C (O) O (} CH 2) nCH = 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 (7).
_{^{H 2 C = C (R 5}} ) -R 9 -C (R 6) (X) -R 10 -R 7 (7)
(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 ⁸ 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 the general formula (7) is specifically exemplified,
_{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 to General formula (8) 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 (8)
(In the formula, 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 having 1 to 20 carbon atoms, aryl having 6 to 20 carbon atoms. Group, or an aralkyl group 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 ′ are the same. And may be different, when two or more R ¹¹ or R ¹² are present, they may be the same or different, and Y is a hydroxyl group. Or a hydrolyzable group, when two or more Y are present, they may be the same or different, a is 0, 1, 2, or 3, and b is 0,1. , Or 2. m is an integer from 0 to 19, provided that a + mb ≧ 1. It shall be)

If the compound of the general formula (8) is specifically exemplified,
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 (9).
^{_{(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 (9)
(Wherein R ⁵ , R ⁶ , R ⁷ , 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 having 6 to 20 carbon atoms, or an aralkyl group having 7 to 20 carbon atoms)
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)
(Wherein X is chlorine, bromine, or iodine, R is a hydrogen atom or 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, n is 1 to 1) An integer of 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)
(Wherein X is chlorine, bromine, or iodine, R is a hydrogen atom or 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, n is 1 to 1) An integer of 20)

（式中、Ｘは塩素、臭素、またはヨウ素、Ｒは水素原子または炭素数１〜２０のアルキル基、炭素数６〜２０のアリール基、または炭素数７〜２０のアラルキル基、ｎは１〜２０の整数） The organic halide having the epoxy group or the sulfonyl halide compound is not particularly limited, and examples thereof include the following.

(Wherein X is chlorine, bromine, or iodine, R is a hydrogen atom or 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, n is 1 to 1) An integer of 20)

等があげられる。上記各式中、Ｘはハロゲン原子を表す。 Since the macromonomer of the present invention has a polymerizable carbon-carbon bond at one end, it is usually preferable to use a single-end initiator as described above. In some cases, an organic halide having two or more starting points or a sulfonyl halide compound may be used. Such an initiator can be polymerized with the macromonomer of the present invention to obtain a crosslinked polymer (gel), and a polymer having a polymerizable carbon-carbon double bond at two or more terminals. Suitable for manufacturing. For example,

Etc. In the above formulas, X represents a halogen atom.

There is no restriction | limiting in particular as a vinyl-type monomer used in this superposition | polymerization, All already illustrated can be used suitably.

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. When a copper compound is used, 2,2′-bipyridyl and its derivatives, 1,10-phenanthroline and its derivatives, tetramethylethylenediamine, pentamethyldiethylenetriamine, hexamethyltris (2-aminoethyl) amine, etc. in order to increase the catalytic activity A ligand such as a polyamine is added. 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.

The polymerization can be carried out without solvent or in various solvents. Solvent types include hydrocarbon solvents such as benzene and toluene, ether solvents such as diethyl ether and tetrahydrofuran, halogenated hydrocarbon solvents such as methylene chloride and chloroform, and ketones such as acetone, methyl ethyl ketone, and methyl isobutyl ketone. Solvents, alcohol solvents such as methanol, ethanol, propanol, isopropanol, n-butyl alcohol, tert-butyl alcohol, nitrile solvents such as acetonitrile, propionitrile, benzonitrile, ester solvents such as ethyl acetate, butyl acetate, Examples thereof include carbonate solvents such as ethylene carbonate and propylene carbonate, and these can be used alone or in admixture of two or more. Moreover, superposition | polymerization can be performed in the range of room temperature-200 degreeC, Preferably it is 50-150 degreeC.

<Functional group introduction method>
Below, introduction | transduction of the terminal functional group of a polymer to macromonomer (I) in this invention is demonstrated.

The method for introducing the group represented by the general formula (1) to the terminal of the polymer of the present invention is not limited, but examples thereof include the following methods.
(1) A method for producing a vinyl polymer by replacing the terminal halogen group with a compound having a radical polymerizable carbon-carbon double bond. As a specific example, a method of reacting a vinyl polymer having a terminal structure represented by the general formula (2) with a compound represented by the general formula (3).
(2) A method of reacting a vinyl polymer having a hydroxyl group at the terminal with the compound represented by the general formula (4).
(3) A method in which a diisocyanate compound is reacted with a vinyl polymer having a hydroxyl group at the terminal, and a reaction between the residual isocyanate group and the compound represented by the general formula (5) is performed.

Each of these methods will be described in detail below.

<Functional group introduction method (1)>
The method (1) will be described.
The vinyl polymer having a terminal structure represented by the general formula (2) is a method of polymerizing a vinyl monomer using the above-described organic halide or sulfonyl halide compound as an initiator and a transition metal complex as a catalyst, or The former is preferably produced by a method of polymerizing a vinyl monomer using a halogen compound as a chain transfer agent.

Although it does not specifically limit as a compound represented by General formula (3), It will not specifically limit if it is a C1-C20 monovalent organic group, for example, C1-C20, for example. It may be a substituted or unsubstituted hydrocarbon group, ether group, acyl group, carbon, nitrogen-containing group, carbon, sulfur-containing group, carbon, oxygen-containing group, and specifically, for example, -H _{, -CH 3, -CH 2 CH 3} , - (CH 2) n CH 3 (n represents an integer of _{2~19), - C 6 H 5} , -CH 2 OH, -CN, and the like are exemplified, preferably -H, a -CH _3. M ⁺ is a counter cation of an oxyanion, and examples of M ⁺ include alkali metal ions, specifically, lithium ions, sodium ions, potassium ions, and quaternary ammonium ions. Examples of the quaternary ammonium ion include tetramethylammonium ion, tetraethylammonium ion, tetrabenzylammonium ion, trimethyldodecylammonium ion, tetrabutylammonium ion, and dimethylpiperidinium ion, preferably sodium ion and potassium ion. The usage-amount of the oxyanion of General formula (3) becomes like this. Preferably it is 1-5 equivalent with respect to the halogen terminal of General formula (2), More preferably, it is 1.0-1.2 equivalent.

The solvent for carrying out this reaction is not particularly limited but is preferably a polar solvent because it is a nucleophilic substitution reaction. For example, tetrahydrofuran, dioxane, diethyl ether, acetone, dimethyl sulfoxide, dimethylformamide, dimethylacetamide, hexamethylphosphoric Triamide, acetonitrile, etc. are used. Although the temperature which performs reaction is not limited, Generally it is 0-150 degreeC, In order to hold | maintain a polymeric terminal group, Preferably it carries out at room temperature-100 degreeC.

<Introduction of terminal functional groups (2)>
The method (2) will be described.
Although it does not specifically limit as a compound represented by the said General formula (4), It will not specifically limit if it is a C1-C20 monovalent organic group, for example, C1-C20, for example. Substituted or unsubstituted hydrocarbon group, ether group, acyl group, carbon, nitrogen-containing group, carbon, sulfur-containing group, carbon, oxygen-containing group, etc., specifically, for example, _{, -H, -CH 3, -CH 2} CH 3, - (CH 2) n CH 3 (n represents an integer of _{2~19), - C 6 H 5} , -CH 2 OH, -CN, and the like Among them, preferred is -H, -CH _3.

A vinyl polymer having a hydroxyl group at the terminal is a method of polymerizing a vinyl monomer using the above-described organic halide or sulfonyl halide compound as an initiator and a transition metal complex as a catalyst, or chain transfer of a compound having a hydroxyl group. Although it is manufactured by a method of polymerizing a vinyl monomer as an agent, the former is preferred. Although the method for producing a vinyl polymer having a hydroxyl group at the terminal by these methods is not limited, the following methods are exemplified.

(A) When synthesizing a vinyl polymer by living radical polymerization, a compound represented by the following general formula (10) or the like and having a polymerizable alkenyl group and hydroxyl group in one molecule is used as a second monomer. How to make.
_{^{H 2 C = C (R 13}} ) -R 14 -R 15 -OH (10)
(In the formula, R ¹³ is a monovalent organic group having 1 to 20 carbon atoms, preferably hydrogen or methyl group, and R ¹⁴ is —C (O) O— (ester group), or o-, m- or p—. Represents a phenylene group, R ¹⁵ represents a direct bond or a divalent organic group having 1 to 20 carbon atoms which may have one or more ether bonds, wherein R ¹⁴ is an ester group (meth) Acrylate compounds and those in which R ¹⁴ is a phenylene group are styrene compounds.)
Although there is no limitation on the timing of reacting the compound having both a polymerizable alkenyl group and a hydroxyl group in one molecule, particularly when a rubber-like property is expected, at the end of the polymerization reaction or after completion of the reaction of a predetermined monomer, It is preferable to react as the second monomer.

(B) When synthesizing a vinyl polymer by living radical polymerization, the second monomer has a low polymerizable alkenyl group and hydroxyl group as the second monomer after the end of the polymerization reaction or after completion of the reaction of the predetermined monomer. A method of reacting a compound.
Although it does not specifically limit as such a compound, The compound etc. which are shown by General formula (11) are mentioned.
_{^{H 2 C = C (R 13}} ) -R 16 -OH (11)
(In the formula, R ¹³ is the same as described above. R ¹⁶ represents a C 1-20 divalent organic group which may contain one or more ether bonds.)
Although it does not specifically limit as a compound shown by the said General formula (11), From an easy acquisition, alkenyl alcohol like 10-undecenol, 5-hexenol, and allyl alcohol is preferable.

(C) A vinyl polymer having at least one carbon-halogen bond represented by the general formula (2) obtained by atom transfer radical polymerization by a method disclosed in JP-A-4-132706. A method of introducing a hydroxyl group at a terminal by hydrolysis or reaction with a hydroxyl group-containing compound.

(D) A stabilized carbanion having a hydroxyl group represented by the general formula (12) is added to a vinyl polymer having at least one carbon-halogen bond represented by the general formula (2) obtained by atom transfer radical polymerization. A method of replacing halogen by reaction.
^{M + C - (R 17)} (R 18) -R 16 -OH (12)
(Wherein, R ¹⁶ are the same as those described above .R ¹⁷ and R ¹⁸ together carbanion C ^- an electron withdrawing group or one of the other from 1 to 10 hydrogen carbon atoms or by the electron-withdrawing group, stabilized As the electron withdrawing group for R ¹⁷ and R ¹⁸ , for example, —CO ₂ R (ester group), —C (O) R (keto group), —CON (R ² ) ( amide group), - COSR (thioester group), - CN (nitrile group), -. NO ₂ (nitro group), etc. the substituent R is an alkyl group having 1 to 20 carbon atoms, aryl having 6 to 20 carbon atoms Or an aralkyl group having 7 to 20 carbon atoms, preferably an alkyl group or phenyl group having 1 to 10 carbon atoms, and R ¹⁷ and R ¹⁸ include —CO ₂ R, —C (O) R and — CN is special Preferred.)

(E) A single metal such as zinc or an organometallic compound is allowed to act on a vinyl polymer having at least one carbon-halogen bond represented by the general formula (2) obtained by atom transfer radical polymerization. To prepare an enolate anion and then react with an aldehyde or a ketone.

(F) A hydroxyl group-containing oxyanion represented by the following general formula (13) or the following general formula is added to a vinyl polymer having at least one halogen represented by the general formula (2) above, A method of reacting the hydroxyl group-containing carboxylate anion represented by the formula (14) to replace the halogen with a hydroxyl group-containing substituent.
HO-R ^{< 16 >} -OM ^<+> (13)
(In the formula, R ¹⁶ and M ⁺ are the same as those described above.)
HO-R ^{< 16 >} -C (O) OM ^<+> (14)
(Wherein R16 and M ⁺ are the same as those described above.)

In the present invention, when halogen is not directly involved in the method of introducing a hydroxyl group as in (a) to (b), the method of (b) is more preferable because control is easier.

In addition, when a hydroxyl group is introduced by converting the halogen of a vinyl polymer having at least one carbon-halogen bond such as (c) to (f), control is easier (f). The method is more preferable.

<Introduction of terminal functional group (3)>
The method (3) will be described.
Although it does not specifically limit as a compound represented by the said General formula (5), It will not specifically limit if it is a C1-C20 monovalent organic group, for example, C1-C20, for example. Substituted or unsubstituted hydrocarbon group, ether group, acyl group, carbon, nitrogen-containing group, carbon, sulfur-containing group, carbon, oxygen-containing group, etc., specifically, for example,- H, —CH ₃ , —CH ₂ CH ₃ , — (CH ₂ ) _n CH ₃ (n represents an integer of 2 to 19), —C ₆ H ₅ , —CH ₂ OH, —CN, and the like. , Preferably —H, —CH ₃ . A specific compound includes 2-hydroxypropyl methacrylate.

The above-mentioned thing can be used for the vinyl polymer which has a hydroxyl group at the terminal.

The diisocyanate compound is not particularly limited, and any conventionally known one can be used. For example, toluylene diisocyanate, 4,4′-diphenylmethane diisocyanate, hexamethyl diisocyanate, xylylene diisocyanate, metaxylylene diisocyanate, And isocyanate compounds such as 1,5-naphthalene diisocyanate, hydrogenated diphenylmethane diisocyanate, hydrogenated toluylene diisocyanate, hydrogenated xylylene diisocyanate, and isophorone diisocyanate. These can be used alone or in combination of two or more. Moreover, you may use block isocyanate.

In order to make better weather resistance, for example, it is preferable to use a diisocyanate compound having no aromatic ring such as hexamethylene diisocyanate, hydrogenated diphenylmethane diisocyanate.

<Polymerization method of the polymer of the present invention>
The method for polymerizing the macromonomer (I) of the present invention is not limited, but is preferably radical polymerization, more preferably living radical polymerization, and still more preferably atom transfer radical polymerization. The atom transfer radical polymerization is preferably carried out using a transition metal complex having a group 7 element, group 8, group 9, group 10, group 11 or group 11 element of the periodic table as a central metal, more preferably a catalyst. Is a metal complex selected from the group consisting of copper, nickel, ruthenium, and iron, and it is particularly preferable to use a copper complex as a catalyst.

In addition, as a method for polymerizing the macromonomer (I), polymerization in which polymerization is initiated by active energy rays and polymerization in which polymerization is initiated by heating are also preferable.

The method for polymerizing the macromonomer (I) may be anionic polymerization.

A star-shaped polymer is obtained by polymerizing the macromonomer (I) of the present invention alone, and graft copolymerization is achieved by copolymerizing the macromonomer (I) and a copolymerizable monomer (II) other than the macromonomer. A polyfunctional compound having at least two groups having a polymerizable carbon-carbon double bond and a macromonomer (I), preferably a polymer having the double bond at the molecular end (III ) Is copolymerized to obtain a gel.

Details of the method for polymerizing the macromonomer (I) will be described below.

(Anionic polymerization)
The initiator used for anionic polymerization is not particularly limited, and examples thereof include monofunctional initiators such as sec-butyl lithium and t-butyl lithium, 1,4-dilithiobutane, dilithiobutadiene, and dilithionaphthalene. These may be used as an initiator system in combination with diphenylethylene, α-methylstyrene and the like.

Examples of the copolymerizable monomer (II) other than the macromonomer include anionic polymerizable monomers such as styrene, α-methylstyrene, p-methylstyrene, o-methylstyrene, p-butylstyrene, methoxystyrene, 1- Aromatic monomers such as vinylnaphthalene, 3-ethyl-1-biphenylnaphthalene, pN, N-dimethylaminostyrene; (meth) acrylic acid, methyl (meth) acrylate, ethyl (meth) acrylate, (meth) Acrylic acid-n-propyl, (meth) acrylic acid isopropyl, (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- -Heptyl, (meth) acrylic acid-n-octyl, (meth) acrylic acid-2-ethylhexyl, (meth) acrylic acid nonyl, (meth) acrylic acid decyl, (meth) acrylic acid dodecyl, (meth) acrylic acid phenyl , Toluyl (meth) acrylate, benzyl (meth) acrylate, 2-methoxyethyl (meth) acrylate, 3-methoxybutyl (meth) acrylate, 2-hydroxyethyl (meth) acrylate, (meth ) -2-hydroxypropyl acrylate, stearyl (meth) acrylate, glycidyl (meth) acrylate, 2-aminoethyl (meth) acrylate, γ- (methacryloyloxypropyl) trimethoxysilane, (meth) acrylate tri Fluoromethylmethyl, 2-trifluoromethylethyl (meth) acrylate, (meta 2-perfluoroethylethyl acrylate, 2-perfluoroethyl-2-perfluorobutylethyl (meth) acrylate, 2-perfluoroethyl (meth) acrylate, perfluoromethyl (meth) acrylate, (meth) Diperfluoromethylmethyl acrylate, 2-perfluoromethyl-2-perfluoroethylmethyl (meth) acrylate, 2-perfluorohexylethyl (meth) acrylate, 2-perfluorodecylethyl (meth) acrylate, (Meth) acrylic acid monomers such as (meth) acrylic acid 2-perfluorohexadecylethyl; 1,3-butadiene, 1,3-pentadiene, 2,3-dimethyl-1,3-butadiene, 2,4- Conjugated dienes such as hexadiene, 2-phenyl-1,3-butadiene and isoprene; Nitriles such as Rironitoriru and the like. 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. More preferred are acrylic ester monomers and methacrylic ester monomers, and even more preferred is butyl acrylate. In the present invention, these preferable monomers may be copolymerized with other monomers, and in this case, it is preferable that these preferable monomers are contained in a weight ratio of 40%.

Anionic polymerization can be carried out in the absence of a solvent, but can also be carried out in the presence of a suitable organic solvent. Examples of the organic solvent include aromatic hydrocarbon solvents such as benzene, toluene and xylene; aliphatic hydrocarbon solvents such as n-hexane, n-octane and isooctane; fats such as methylcyclopentane, cyclohexane and cyclooctane. Cyclic hydrocarbon solvents; ether solvents such as tetrahydrofuran, dioxane, diethyl ether and the like.

As the polymerization conditions, the polymerization conditions employed in normal anionic polymerization can be used. However, in order not to deactivate the polymerization initiator and the living site at the end of the polymer, oxygen, carbon dioxide or water in the polymerization system is used. It is preferable to carry out under conditions that do not mix. For example, a polymerization initiator is added to a degassed / dehydrated solvent under a high vacuum or a nitrogen atmosphere containing almost no water, and then the anionic polymerizable monomer is added to perform anionic polymerization. You may superpose | polymerize, adding gradually, without adding a polymerization initiator and the whole quantity of a monomer at once.

A polymer having an arbitrary monomer composition can be obtained by polymerizing two or more of the above anionic polymerizable monomers. In addition, after the polymerization of one type of monomer is completed, a block copolymer or diblock copolymer having an arbitrary monomer composition and structure is obtained by successively polymerizing with another type of monomer. Polymers, triblock copolymers, multiblock copolymers and the like can be obtained. If the macromonomer (I) is added during the polymerization, a graft copolymer in which the macromonomer (I) is incorporated at an appropriate position can be obtained.

The polymerization temperature varies depending on the type of polymerization initiator, monomer, solvent and the like used, but is usually preferably in the range of −100 ° C. to 150 ° C., more preferably in the range of −78 ° C. to 80 ° C. The polymerization time varies depending on the polymerization initiator, monomer, solvent, reaction temperature, etc. used, but is usually in the range of 10 minutes to 10 hours. The polymerization reaction can be carried out by any of batch, semi-batch and continuous methods.

(Radical polymerization)
It does not specifically limit as radical polymerization, You may implement by any methods, such as normal free radical polymerization, chain transfer radical polymerization, and living radical polymerization.

In radical polymerization, as the monomer (II) copolymerized with the macromonomer (I), all radical polymerizable monomers described in the method for producing the main chain of the macromonomer (I) can be used. .

The radical polymerization may be carried out without a solvent, and all solvents described in the method for producing the main chain of the macromonomer (I) can be used.

The initiator used for the free radical polymerization is not particularly limited, but organic peroxides such as benzoyl peroxide and tert-butyl peroxide, 2,2′-azobisisobutyronitrile, Such as 2'-azobis (4-methoxy-2,4-dimethylvaleronitrile), 2,2'-azobis (2-cyclopropylpropionitrile), 2,2'-azobis (2-methylbutyronitrile), etc. And radical initiators such as azo compounds.

Chain transfer radical polymerization is carried out by adding a chain transfer agent to the free radical polymerization, and the above-mentioned initiators can be used. Although it does not specifically limit as a chain transfer agent, n-dodecyl mercaptan, t-dodecyl mercaptan, n-octyl mercaptan, n-octadecyl mercaptan, 3-mercaptopropyltrimethoxysilane, 3-mercaptopropyltriethoxysilane, 3-mercaptopropyl methyldimethoxysilane, 3-mercaptopropyl methyl diethoxy _{silane, (H 3 CO) 3 Si} -S-S-Si (OCH 3) 3, CH 3 (H 3 CO) 2 Si-S-S-SiCH 3 (OCH _{3) 2, (C 2 H} 5 O) 3 Si-S-S-Si (OC 2 H 5) 3, CH 3 (C 2 H 5 O) 2 Si-S-S-SiCH 3 (OC 2 H 5 ) ₂ , (H ₃ CO) ₃ Si—S ₃ —Si (OCH ₃ ) ₃ , (H ₃ CO) ₃ Si—S ₄ —Si ( OCH _{3) 3,} can be used _{(H 3 CO) 3 Si-} S 6 -Si (OCH 3) 3 and the like. In particular, when a chain transfer agent having an alkoxysilyl group in the molecule, for example, 3-mercaptopropyltrimethoxysilane, an alkoxysilyl group can be introduced at the terminal.

Although it does not limit as living radical polymerization, SFRP (Stable Free Radical Polymerization) which captures a polymerization growth terminal radical by TEMPO (tetramethyl piperidine oxide), a cobalt porphyrin complex, etc., the macromonomer of the present invention Atom transfer radical polymerization described for the polymerization of the main chain of (I) can be mentioned, the latter being preferred. These polymerizations are carried out under the conditions already described. When the macromonomer (I) is polymerized by living radical polymerization, it is expected that the molecular weight and molecular weight distribution of the polymer chain obtained by this polymerization are controlled. As a result, in the case of copolymerizing with another monomer (II), a graft copolymer in which the number of side chains in the polymer is also more controlled than in general free radical polymerization can be obtained. When I) is polymerized alone, the number of arms in the star polymer is more controlled than in general free radical polymerization.

(Polymerization by active energy rays)
The macromonomer (I) of the present invention can be polymerized by an active energy ray such as UV or electron beam.

This method is not limited, but is more suitable when the macromonomer (I) and the polymer (III) having a polymerizable carbon-carbon double bond at two or more terminals are polymerized to form a gel. .

When polymerizing with active energy rays, it is preferable to contain a photopolymerization initiator.

Although there is no restriction | limiting in particular as a photoinitiator used for this invention, A photoradical initiator and a photoanion initiator are preferable, and a photoradical initiator is especially preferable. For example, acetophenone, propiophenone, benzophenone, xanthol, fluorin, benzaldehyde, anthraquinone, triphenylamine, carbazole, 3-methylacetophenone, 4-methylacetophenone, 3-pentylacetophenone, 4-methoxyacetophene, 3-bromo Acetophenone, 4-allylacetophenone, p-diacetylbenzene, 3-methoxybenzophenone, 4-methylbenzophenone, 4-chlorobenzophenone, 4,4'-dimethoxybenzophenone, 4-chloro-4'-benzylbenzophenone, 3-chloroxanthone 3,9-dichloroxanthone, 3-chloro-8-nonylxanthone, benzoyl, benzoin methyl ether, benzoin butyl ether, bis (4-dimethyl) Minofeniru) ketone, benzyl methoxy ketal, 2-chlorothioxanthone tone, and the like. These initiators may be used alone or in combination with other compounds. Specifically, combinations with amines such as diethanolmethylamine, dimethylethanolamine, and triethanolamine, further combinations with iodonium salts such as diphenyliodonium chloride, and combinations with dyes and amines such as methylene blue are included. It is done.

Moreover, you may use a near-infrared light absorptive cationic dye as a near-infrared photoinitiator. As the near-infrared light-absorbing cationic dye, it is excited by light energy in the region of 650 to 1500 nm, for example, near-infrared light absorption disclosed in JP-A-3-111402, JP-A-5-194619, etc. It is preferable to use a cationic cationic dye-borate anion complex or the like, and it is more preferable to use a boron sensitizer together.

The addition amount of the photopolymerization initiator is not particularly limited since it only needs to slightly functionalize the system, but is preferably 0.001 to 10 parts by weight with respect to 100 parts of the polymer of this composition.

The method of polymerizing with active energy rays is not particularly limited, but depending on the nature of the photopolymerization initiator initiator, light and electrons from a high pressure mercury lamp, low pressure mercury lamp, electron beam irradiation device, halogen lamp, light emitting diode, semiconductor laser, etc. Irradiation of a line is mentioned.

(Polymerization by heat)
The macromonomer (I) of the present invention can be polymerized by heat.

This method is not limited, but is more suitable when the macromonomer (I) and the polymer (III) having a polymerizable carbon-carbon double bond at two or more terminals are polymerized to form a gel. .

When polymerizing by heat, it is preferable to contain a thermal polymerization initiator.

Although there is no restriction | limiting in particular as a thermal-polymerization initiator used for this invention, An azo initiator, a peroxide, a persulfuric acid, and a redox initiator are contained.

Suitable azo initiators include, but are not limited to, 2,2'-azobis (4-methoxy-2,4-dimethylvaleronitrile) (VAZO 33), 2,2'-azobis (2- Amidinopropane) dihydrochloride (VAZO 50), 2,2'-azobis (2,4-dimethylvaleronitrile) (VAZO 52), 2,2'-azobis (isobutyronitrile) (VAZO 64), 2, 2'-azobis-2-methylbutyronitrile (VAZO 67), 1,1-azobis (1-cyclohexanecarbonitrile) (VAZO 88) (all available from DuPont Chemical), 2,2'-azobis (2- Cyclopropylpropionitrile), and 2,2′-azobis (methylisobutylate) (V-601) (available from Wako Pure Chemical Industries, Ltd.) And the like.

Suitable peroxide initiators include, but are not limited to, benzoyl peroxide, acetyl peroxide, lauroyl peroxide, decanoyl peroxide, dicetyl peroxydicarbonate, di (4-t-butylcyclohexyl). Peroxydicarbonate (Perkadox 16S) (available from Akzo Nobel), di (2-ethylhexyl) peroxydicarbonate, t-butyl peroxypivalate (Lupersol 11) (available from Elf Atochem), t-butyl per Oxy-2-ethylhexanoate (Trigonox 21-C50) (available from Akzo Nobel), dicumyl peroxide, and the like.

Suitable persulfate initiators include, but are not limited to, potassium persulfate, sodium persulfate, and ammonium persulfate.

Suitable redox initiators include, but are not limited to, combinations of the above persulfate initiators with reducing agents such as sodium metabisulfite and sodium bisulfite; Examples include systems based on tertiary amines, such as systems based on benzoyl peroxide and dimethylaniline; and systems based on organic hydroperoxides and transition metals, such as systems based on cumene hydroperoxide and cobalt naphthate.

Other initiators include, but are not limited to, pinacol such as tetraphenyl 1,1,2,2-ethanediol.

A preferred thermal radical initiator is selected from the group consisting of azo initiators and peroxide initiators. More preferred are 2,2'-azobis (methylisobutylate), t-butyl peroxypivalate, and di (4-t-butylcyclohexyl) peroxydicarbonate, and mixtures thereof.

The thermal initiator used in the present invention is present in a catalytically effective amount, and such amount is typically but not limited to the macromonomer (I) and other monomers and oligomers added to it. When the total amount of the mixture is 100 parts by weight, it is about 0.01 to 5 parts by weight, more preferably about 0.025 to 2 parts by weight. If a mixture of initiators is used, the total amount of initiator mixture is an amount equal to the amount used when only one initiator is used.

In the present invention, the method for thermal polymerization is not particularly limited, but the temperature varies depending on the type of thermal initiator, macromonomer (I), compound to be added, etc., but is usually in the range of 50 ° C to 250 ° C. Is preferable, and the inside of the range of 70 degreeC-200 degreeC is more preferable. The polymerization time varies depending on the polymerization initiator, monomer, solvent, reaction temperature, etc. used, but is usually in the range of 1 minute to 10 hours.

(gel)
When the macromonomer (I) of the present invention is polymerized with a polyfunctional compound (monomer / oligomer), preferably a polymer (III) having a polymerizable carbon-carbon double bond at two or more ends, a gel (crosslinking) Polymer).

The polymer (III) can be produced by the same production method as that for the macromonomer (I). In particular, when atom transfer radical polymerization is used, a method of polymerizing using a polyfunctional initiator to convert the functional group at the terminal can be mentioned.

Examples of polyfunctional monomers include neopentyl glycol polypropoxydiacrylate, trimethylolpropane polyethoxytriacrylate, bisphenol F polyethoxydiacrylate, bisphenol A polyethoxydiacrylate, dipentaerythritol polyhexanolide hexaacrylate, tris (hydroxy) Ethyl) isocyanurate polyhexanolide triacrylate, tricyclodecane dimethylol diacrylate 2- (2-acryloyloxy-1,1-dimethyl) -5-ethyl-5-acryloyloxymethyl-1,3-dioxane, tetra Bromobisphenol A diethoxydiacrylate, 4,4-dimercaptodiphenyl sulfide dimethacrylate, polytetraethylene glycol diacrylate, 1,9 Nonanediol diacrylate, and ditrimethylolpropane tetraacrylate.

Polyfunctional oligomers include bisphenol A type epoxy acrylate resins, phenol novolac type epoxy acrylate resins, cresol novolac type epoxy acrylate resins, and other epoxy acrylate resins, COOH group-modified epoxy acrylate resins, polyols (polytetramethylene glycol, ethylene glycol) And adipic acid polyester diol, ε-caprolactone modified polyester diol, polypropylene glycol, polyethylene glycol, polycarbonate diol, hydroxyl-terminated hydrogenated polyisoprene, hydroxyl-terminated polybutadiene, hydroxyl-terminated polyisobutylene, etc.) and organic isocyanate (tolylene diisocyanate, isophorone diisocyanate) , Diphenylmethane diisocyanate, hexamethylene di Urethane resin obtained from socyanate, xylylene diisocyanate, etc.) reacts with hydroxyl-containing (meth) acrylate {hydroxyethyl (meth) acrylate, hydroxypropyl (meth) acrylate, hydroxybutyl (meth) acrylate, pentaerythritol triacrylate, etc.} Examples thereof include urethane acrylate resins obtained by the above, resins obtained by introducing (meth) acrylic groups into the above polyols through ester bonds, polyester acrylate resins, and the like.

<Application>
The branched polymer of the present invention can be used for the same applications as existing elastomers. Specifically, resin and asphalt modification applications, resin and block compound applications (plasticizers, fillers, stabilizers, etc. may be added if necessary), thermosetting resin shrinkage inhibitors It can be used as a base polymer for adhesives and damping materials. Specific application fields include automotive interior / exterior parts, electrical / electronic fields, food packaging films and tubes, pharmaceutical / medical containers, sealing articles, and the like.

Further, the branched polymer of the present invention itself can be a molding material as a resin having impact resistance. However, when it is used in a mixture with various thermoplastic resins and thermosetting resins, the branched polymer is highly sophisticated. It can be an impact resistance improver capable of imparting impact resistance. In addition, they can be used as processability improvers, compatibilizers, matting agents, heat resistance improvers, and the like.

Examples of the thermoplastic resin which can improve the impact resistance by adding the branched polymer of the present invention include polymethyl methacrylate resin, polyvinyl chloride resin, polyethylene resin, polypropylene resin, cyclic olefin copolymer resin, polycarbonate resin, 70-100% by weight of at least one vinyl monomer selected from the group consisting of polyester resins, mixtures of polycarbonate resins and polyester resins, aromatic alkenyl compounds, vinyl cyanide compounds and (meth) acrylic acid esters, and Polymerizes 0 to 30% by weight of other vinyl monomers such as ethylene, propylene, vinyl acetate and / or conjugated diene monomers such as butadiene and isoprene that can be copolymerized with vinyl monomers. Homopolymer or copolymer, polystyrene Fat, polyphenylene ether resin, and the like mixture of polystyrene resin and polyphenylene ether resin, these without limitation, a thermoplastic resin resin widely available. In particular, a polymethyl methacrylate resin, a polyvinyl chloride resin, a polypropylene resin, a cyclic polyolefin resin, a polycarbonate resin, a polyester resin, and the like are preferable because they easily provide characteristics such as weather resistance and impact resistance.

Examples of a method for adding the branched polymer of the present invention to various resins include a method of mechanically mixing and shaping into pellets using a known apparatus such as a Banbury mixer, a roll mill, or a twin screw extruder. Can do. Extruded shaped pellets can be molded over a wide temperature range, and ordinary injection molding machines, blow molding machines, extrusion molding machines, etc. are used for molding.

Furthermore, an impact resistance improver, a stabilizer, a plasticizer, a lubricant, a flame retardant, a pigment, a filler, and the like can be added to the resin composition as necessary. Specifically, impact modifiers such as methyl methacrylate-butadiene-styrene copolymer (MBS resin), acrylic graft copolymer, acrylic-silicone composite rubber graft copolymer; triphenyl phosphite, etc. Stabilizers; lubricants such as polyethylene wax and polypropylene wax; phosphate flame retardants such as triphenyl phosphate and tricresyl phosphate; brominated flame retardants such as decabromobiphenyl and decabromobiphenyl ether; flame retardants such as antimony trioxide; Examples thereof include pigments such as titanium oxide, zinc sulfide and zinc oxide; fillers such as glass fiber, asbestos, wollastonite, mica, talc and calcium carbonate.

The branched polymer, particularly the star polymer of the present invention is not particularly limited, but is useful as an additive, preferably a viscosity modifier (viscosity index improving additive) such as a lubricating oil. The amount of the polymer of the present invention added to the lubricating oil is not particularly limited, but is preferably about 0.1 wt% to about 30 wt%, more preferably about 1 wt% to about 10 wt%. The target lubricating oil is not particularly limited, but oils used for automobiles, aircraft, ships, railways, etc., for example, oils used for spark ignition, compression ignition, synthetic oils such as summer oil or winter oil, and mineral oils It may be. A typical lubricating oil preferably has a boiling point of about 300 ° C to about 350 ° C. To facilitate the addition of the polymer of the present invention to a lubricating oil, a concentrate comprising about 1-50 wt%, preferably about 5-20 wt%, of the polymer of the present invention in a synthetic or mineral oil. Is preferably used.

The branched polymer of the present invention can be made into an adhesive composition.

The pressure-sensitive adhesive composition of the present invention is preferably composed mainly of a (meth) acrylic polymer, so that it is not always necessary to add a tackifying resin, but various types are used as necessary. can do. Specific examples include phenol resin, modified phenol resin, cyclopentadiene-phenol resin, xylene resin, coumarone resin, petroleum resin, terpene resin, terpene phenol resin, rosin ester resin and the like.

In the pressure-sensitive adhesive composition of the present invention, various additives such as an anti-aging material, a plasticizer, a physical property modifier, and a solvent may be blended in order to adjust physical properties.

Since acrylic polymers are inherently excellent in durability, anti-aging agents are not always necessary, but conventionally known antioxidants and ultraviolet absorbers can be used as appropriate.

As plasticizers, phthalates such as dibutyl phthalate, diheptyl phthalate, di (2-ethylhexyl) phthalate, butyl benzyl phthalate, etc .; non-dioctyl adipate, dioctyl sebacate, etc. Aromatic dibasic acid esters; esters of polyalkylene glycols such as diethylene glycol dibenzoate and triethylene glycol dibenzoate; phosphate esters such as tricresyl phosphate and tributyl phosphate; chlorinated paraffins; alkyl diphenyl, partially hydrogenated Hydrocarbon oils such as terphenyl can be used alone or in admixture of two or more, but this is not always necessary. These plasticizers can also be blended at the time of polymer production.

Examples of the solvent include aromatic hydrocarbon solvents such as toluene and xylene, ester solvents such as ethyl acetate, butyl acetate, amyl acetate, and cellosolve, ketone solvents such as methyl ethyl ketone, methyl isobutyl ketone, and diisobutyl ketone. It is done. Those solvents may be used in the production of the polymer.

Moreover, you may add various adhesive improvement agents to the adhesive composition of this invention in order to improve the adhesiveness with respect to various support bodies (plastic film, paper, etc.). Illustrative examples include alkylalkoxysilanes such as methyltrimethoxysilane, dimethyldimethoxysilane, trimethylmethoxysilane, and n-propyltrimethoxysilane; dimethyldiisopropenoxysilane, methyltriisopropenoxysilane, and γ-glycidoxy Alkylisopropenoxysilane such as propylmethyldiisopropenoxysilane, γ-glycidoxypropylmethyldimethoxysilane, γ-glycidoxypropyltrimethoxysilane, vinyltrimethoxysilane, vinyldimethylmethoxysilane, γ-aminopropyltri Methoxysilane, N- (β-aminoethyl) -γ-aminopropyltrimethoxysilane, N- (β-aminoethyl) -γ-aminopropylmethyldimethoxysilane γ-mercaptopropyltrimethoxysilane, - alkoxysilanes having a functional group such as mercaptopropyl methyldimethoxysilane; silicone varnishes; polysiloxane, and the like.

The pressure-sensitive adhesive composition of the present invention can be widely applied to tapes, sheets, labels, foils and the like. For example, solvent-type, emulsion-type, hot-melt type, etc. for substrate materials such as films made of synthetic resin or modified natural products, paper, all kinds of cloth, metal foil, metalized plastic foil, asbestos or glass fiber cloth The pressure-sensitive adhesive composition may be applied and cured by active energy rays or heat.

In addition to these, the polymer of the present invention can be used for sealing materials, paints, coating materials, sealing materials, adhesives, potting materials, casting materials, molding materials, and the like.

Specific examples of the present invention will be described below together with comparative examples, but the present invention is not limited to the following examples.
In the following examples, “part” and “%” represent “part by weight” and “% by weight”, respectively.
In the following Examples, “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 was used, and chloroform was used as a GPC solvent.
In the following examples, “average number of terminal (meth) acryloyl groups” is “number of (meth) acryloyl groups introduced per molecule of polymer”, calculated by ¹ H NMR analysis and number average molecular weight determined by GPC. did.

Production Example 1 Synthesis example of Br group-terminated poly (butyl acrylate) (1)
CuBr (5.54 g, 38.6 mmol) was charged into a 2 L separable flask equipped with a reflux tube and a stirrer, and the inside of the reaction vessel was purged with nitrogen. Acetonitrile (73.8 mL) was added, and the mixture was stirred in an oil bath at 70 ° C. for 30 minutes. To this was added butyl acrylate (132 g), methyl 2-bromopropionate (14.4 mL, 0.129 mol) and pentamethyldiethylenetriamine (4.69 mL, 0.022 mol) to initiate the reaction. While heating and stirring at 70 ° C., butyl acrylate (528 g) was continuously added dropwise over 90 minutes, and further heated and stirred for 80 minutes.

The reaction mixture is diluted with toluene, passed through an activated alumina column, and the volatile matter is distilled off under reduced pressure to obtain poly (butyl acrylate) having a Br group at one end (hereinafter referred to as polymer [1]). It was. The number average molecular weight of the polymer [1] was 5800, and the molecular weight distribution was 1.14.

Production Example 2 A synthetic flask of potassium acrylate was charged with methanol (500 mL) and cooled to 0 ° C. Thereto, t-butoxypotassium (78 g) was added in several portions. The reaction solution was kept at 0 ° C., and a methanol solution of acrylic acid (50 g) was added dropwise. After completion of the dropping, the temperature of the reaction solution is returned from 0 ° C. to room temperature, and then the volatile component of the reaction solution is distilled off under reduced pressure to obtain potassium acrylate (hereinafter referred to as carboxylate [1]) represented by the following formula. It was.
CH ₂ = CHCO ₂ K

Production Example 3 Methanol (800 mL) was charged into a potassium methacrylate synthetic flask and cooled to 0 ° C. Thereto, t-butoxypotassium (130 g) was added in several portions. The reaction solution was kept at 0 ° C., and a methanol solution of methacrylic acid (100 g) was added dropwise. After completion of the dropping, the temperature of the reaction solution is returned from 0 ° C. to room temperature, and then the volatile content of the reaction solution is distilled off under reduced pressure to obtain potassium methacrylate (hereinafter referred to as carboxylate [2]) represented by the following formula. It was.
_{CH 2 = C (CH 3)} CO 2 K

Example 1 Synthesis of acryloyl group-type macromonomer In a 500 mL flask with a reflux tube, the polymer [1] (150 g) obtained in Production Example 1 and the carboxylate [1] (6.61 g obtained in Production Example 2) were obtained. ) And dimethylacetamide (150 mL) were charged and stirred at 70 ° C. for 3 hours to obtain poly (butyl acrylate) having an acryloyl group at one end (hereinafter referred to as macromonomer [1]). Dimethylacetamide was distilled off from the reaction mixture, dissolved in toluene, passed through an activated alumina column, and then toluene was distilled off to purify macromonomer [1]. Macromonomer [1] had an average terminal acryloyl group number of 1.1, a number average molecular weight of 6000, and a molecular weight distribution of 1.14.

Example 2 Synthesis of methacryloyl group-type macromonomer In a 500 mL flask with a reflux tube, the polymer [1] (150 g) obtained in Production Example 1 and the carboxylate [2] obtained in Production Example 3 (7.45 g) ) And dimethylacetamide (150 mL) were charged and stirred at 70 ° C. for 3 hours to obtain poly (butyl acrylate) having a methacryloyl group at one end (hereinafter referred to as macromonomer [2]). Dimethylacetamide was distilled off from the reaction mixture, dissolved in toluene, passed through an activated alumina column, and then toluene was distilled off to purify macromonomer [2]. Macromonomer [2] had an average terminal methacryloyl group number of 1.0, a number average molecular weight of 6000, and a molecular weight distribution of 1.13.

Example 3 Synthesis of Star Polymer (1)
To the macromonomer [1] (100 parts), diethoxyacetophenone (0.2 parts) as a photoradical generator was mixed well to obtain a composition. After degassing the composition under reduced pressure, the composition was poured into a glass mold and covered with a glass plate so that the surface did not come into contact with air. Using a high-pressure mercury lamp (SHL-100UVQ-2; manufactured by Toshiba Lighting & Technology Co., Ltd.), the polymer was radical polymerized by irradiating light at an irradiation distance of 20 cm for 5 minutes. As a result, a high molecular weight compound (number average molecular weight 112000, Formation of molecular weight distribution 1.28) was confirmed.

Example 4 Synthesis of Star Polymer (2)
To the macromonomer [1] (100 parts), diethoxyacetophenone (0.2 part) as a photoradical generator and lauryl mercaptan (1.0 part) as a chain transfer agent were mixed well to obtain a composition. After degassing the composition under reduced pressure, the composition was poured into a glass mold and covered with a glass plate so that the surface did not come into contact with air. Using a high pressure mercury lamp (SHL-100UVQ-2; manufactured by Toshiba Lighting & Technology Co., Ltd.), the polymer was radically polymerized by irradiating light at an irradiation distance of 20 cm for 5 minutes. As a result, a high molecular weight body (number average molecular weight 17500, Formation of molecular weight distribution 1.38) was confirmed.

Example 5 Synthesis of Star Polymer (3)
In Example 4, the same operation was performed except that the macromonomer [2] (100 parts) was used instead of the macromonomer [1] (100 parts). As a result, a high molecular weight substance (number average molecular weight 30000, molecular weight distribution 1) was obtained. .17) was confirmed.

Example 6 Synthesis of Graft Copolymer In a 100 mL three-necked flask with a reflux tube, macromonomer [2] (5.0 g), methyl methacrylate (7.5 mL, 70 mmol), 2,2-azobisisobutyronitrile ( 0.460 g, 2.8 mmol) and toluene (10 mL) were charged, and nitrogen gas was blown for 15 minutes to remove dissolved oxygen. The graft copolymer was obtained by heating and stirring at 60 ° C. for 4 hours. The graft copolymer was purified by repeated reprecipitation into methanol. The number average molecular weight of the graft copolymer was 36000, and the molecular weight distribution was 1.71.

By this experiment, a graft copolymer having poly (methyl methacrylate) as the trunk polymer and poly (butyl acrylate) as the branch polymer was obtained.

Production Example 4 Synthesis of acryloyl group poly (butyl acrylate) at both ends Polymerization of n-butyl acrylate using cuprous bromide as a catalyst, pentamethyldiethylenetriamine as a ligand, and diethyl-2,5-dibromoadipate as an initiator Thus, a terminal bromine group poly (n-butyl acrylate) having a number average molecular weight of 10800 and a molecular weight distribution of 1.15 was obtained.

300 g of this polymer was dissolved in N, N-dimethylacetamide (300 mL), 7.4 g of carboxylate [1] was added, and the mixture was heated and stirred at 70 ° C. for 3 hours in a nitrogen atmosphere. Acid n-butyl) (hereinafter referred to as telechelic oligomer [1]). After N, N-dimethylacetamide in this mixture was distilled off under reduced pressure, toluene was added to the residue, and the insoluble matter was removed by filtration. The toluene in the filtrate was distilled off under reduced pressure to purify the telechelic oligomer [1].
The average terminal acryloyl group number of the telechelic oligomer [1] was 2.0.

Examples 7 to 9 Preparation of adhesive cured product Macromonomer [1], telechelic oligomer [1], and diethoxyacetophenone were mixed well in the ratios shown in Table 1. These compositions were degassed under reduced pressure, filled into a mold, and the surface was covered with a glass plate to prepare a sample. These samples were irradiated with light by a high-pressure mercury lamp (SHL-100UVQ-2; manufactured by Toshiba Lighting & Technology Co., Ltd.) (irradiation conditions: irradiation time: 5 minutes, irradiation distance: 20 cm). A cured product was obtained.

About the obtained hardened | cured material, the gel fraction was measured. However, the gel fraction was calculated | required by the weight ratio of the hardened | cured material before extraction of the unhardened part of hardened | cured material and after extraction. Extraction of the uncured portion was performed by immersing the cured product in toluene. The results are also shown in Table 1.

Example 10 Preparation of Adhesive Sheet and Adhesive Sheet Test 70 parts of macromonomer [1], 30 parts of telechelic oligomer [1] and 2 parts of diethoxyacetophenone were mixed well to obtain an adhesive composition. The obtained adhesive composition was applied to a corona-treated polyethylene terephthalate film (manufactured by Toray Industries, Inc.) having a thickness of 50 μm, and a high-pressure mercury lamp (SHL-100UVQ-2; Toshiba Lighting & Technology Corp.) under a nitrogen atmosphere. )) For 10 minutes to be cured by light irradiation.

When the obtained adhesive sheet was subjected to an inclined ball tack test in accordance with JIS Z-0237, the maximum ball number was 3. However, the runway was 100 mm, the measurement part was 100 mm, and the inclination angle was 20 degrees.

Claims (18)

A vinyl polymer prepared by radical polymerization, polymerizable carbon - 1 per molecule a group having a carbon double bond, possess at its molecular end, the macromonomer number average molecular weight of 3,000 or more (I)
A branched polymer produced by polymerizing styrene alone. A vinyl polymer prepared by radical polymerization, polymerizable carbon - 1 per molecule a group having a carbon double bond, possess at its molecular end, the macromonomer number average molecular weight of 3,000 or more A branched polymer produced by copolymerizing (I) with a polyfunctional compound having two or more groups having a polymerizable carbon-carbon double bond per molecule. A group having a polymerizable carbon-carbon double bond is represented by the general formula (1):
—OC (O) C (R) ═CH ₂ (1)
(In the formula, R represents hydrogen or a monovalent organic group having 1 to 20 carbon atoms.)
The branched polymer according to claim 1, wherein the branched polymer is a group represented by the formula: The branched polymer according to claim 3, wherein R is hydrogen or a methyl group. The branched polymer according to any one of claims 1 to 4, wherein the main chain of the macromonomer (I) is composed of a vinyl polymer produced by living radical polymerization. 5. The branched heavy chain according to claim 1, wherein the main chain of the macromonomer (I) is composed of a vinyl polymer produced by polymerization of a vinyl monomer using a chain transfer agent. Coalescence. The branched polymer according to any one of claims 1 to 6, wherein the main chain of the macromonomer (I) is a (meth) acrylic polymer. The branched polymer according to claim 7, wherein the polymer main chain of the macromonomer (I) is an acrylate polymer. The branched polymer according to any one of claims 1 to 6, wherein the main chain of the macromonomer (I) is a styrenic polymer. Any of claims 1-9 value of the ratio (Mw / Mn) of weight average molecular weight of gel permeation macromonomer as measured by chromatography (I) (Mw) to the number average molecular weight (Mn) of less than 1.8 A branched polymer according to claim 1. The branched polymer according to any one of claims 1 to 10 , wherein the method of polymerizing the macromonomer (I) is radical polymerization. The branched polymer according to any one of claims 1 to 10 , wherein the method of polymerizing the macromonomer (I) is polymerization in which polymerization is initiated by active energy rays. The branched polymer according to any one of claims 1 to 10 , wherein the method of polymerizing the macromonomer (I) is polymerization in which polymerization is initiated by heating. The branched polymer according to any one of claims 1 to 10 , wherein the method of polymerizing the macromonomer (I) is anionic polymerization. Polymer in which a polyfunctional compound having two or more groups having a polymerizable carbon-carbon double bond per molecule has two or more groups having a polymerizable carbon-carbon double bond at one molecule end The branched polymer according to claim 2, which is (III). The thermoplastic elastomer which has as a main component the branched polymer of any one of Claims 1-15 . The impact resistance improving material which has as a main component the branched polymer of any one of Claims 1-15 . An adhesive mainly comprising the branched polymer according to any one of claims 1 to 15 .