JP2022035369A - Macro monomer, and polymer including the macro monomer - Google Patents

Abstract

To provide a novel macro monomer that has a vinyl group being highly copolymerizable with an aromatic vinyl compound.SOLUTION: A macro monomer has at least one unsaturated bond group having two or more electron attractive groups combined therewith at an end, and includes an addition polymerizable monomer unit as a main chain.SELECTED DRAWING: None

Description

The present invention relates to a macromonomer and a polymer using the macromonomer.

Polystyrene, polyolefin, (meth) acrylic polymers, etc., which are widely used in molding materials for home appliances, office equipment products, miscellaneous goods, housing equipment, etc., or food packaging materials, are various as necessary using vinyl-based monomers as raw materials. It is generally industrially produced by using addition polymerization (chain polymerization) by copolymerizing with the monomer of. Such addition polymerization is classified by cationic polymerization, anionic polymerization, radical polymerization, etc., and the attributes of the growth terminal thereof, and the growth terminal having a specific chemical structure and its properties repeats the growth reaction with the monomer. Polymerization proceeds.

Examples of the technique related to addition polymerization include Patent Documents 1 and 2. The patent document 1 contains a highly branched ultra-high molecular weight copolymer obtained by copolymerizing a polyfunctional vinyl copolymer and styrene, so that the highly branched styrene has an excellent balance between melt tension and melt stretchability. The based resin composition is disclosed. Further, Patent Document 2 discloses a styrene-based copolymer in which a predetermined conjugated divinyl compound and a predetermined monovinyl compound are contained in an appropriate content ratio, whereby the styrene-based copolymer is excellent in molding processability and is in the form of a gel. It is disclosed that a styrene-based copolymer containing less substance can be provided.

Japanese Unexamined Patent Publication No. 2013-100432 JP-A-2017-218575

However, the vinyl group present in the polyfunctional vinyl copolymer described in Patent Document 1 is an aromatic vinyl group, and the rate of formation of branched polystyrene during copolymerization with styrene in the production of branched polystyrene is high. It had the drawback of being slow and low in productivity. Further, it was found that there is room for further improvement in copolymerizability because the conjugated vinyl group in the conjugated divinyl compound described in Patent Document 2 is a (meth) acrylate group.

Therefore, the present invention solves the above-mentioned problems, and provides a novel macromonomer having a high reaction rate, capable of efficiently imparting a branched structure by copolymerization, and improving the productivity of the branched polymer. The purpose is to do.

As a result of diligent research to achieve the above object, the present inventors have at least one unsaturated bond group having two or more electron-withdrawing groups bonded to the terminal portion, and the addition-polymerizable monomer unit. It has been found that the above-mentioned problems can be solved by a macromonomer containing the above as a main chain, and the present invention has been completed. That is, the present invention is as shown below.

[1] The present embodiment is a macromonomer having at least one unsaturated bond group to which two or more electron-withdrawing groups are bonded at the terminal portion and containing an addition-polymerizable monomer unit as a main chain.

（上記一般式（Ｉ）中、Ｌは、単結合又は炭素原子数１～１０のアルキレン基（但し、当該アルキレン基中の－ＣＨ₂－は隣り合わないよう、－Ｏ－、－Ｓ－、又は－ＮＨ－に置換されてもよく、さらに当該アルキレン基中の－ＣＨ₂－ＣＨ₂－は、－ＣＨ＝ＣＨ－に置換されてもよい）を表し、
Ｍは、付加重合性単量体単位を表し、
Ｚは、単結合又は炭素原子数１～１０のアルキレン基（但し、当該アルキレン基中の－ＣＨ₂－は、－Ｏ－、－Ｓ－、－ＮＨ－に置換されてもよい）を表し、
ｎは、重合度を表し、
Ｘは、水素原子又は２以上の電子吸引基が結合された不飽和結合基を表す。一般式（Ｉ）中の＊は、前記有機基に含まれる原子との結合を表す。）
で表される基を最大６種有することが好ましい。 [2] In the present embodiment, an organic group having a 2- to hexavalent bond and a
The following general formula (I) that directly bonds to the bond of the organic group

(In the above general formula (I), L is a single bond or an alkylene group having 1 to 10 carbon atoms (however, -CH _2- in the alkylene group is not adjacent to each other, -O-, -S-, Alternatively, it may be substituted with -NH-, and -CH ₂ -CH _2- in the alkylene group may be substituted with -CH = CH-).
M represents an addition-polymerizable monomer unit and represents
Z represents a single bond or an alkylene group having 1 to 10 carbon atoms (however, -CH _2- in the alkylene group may be substituted with -O-, -S-, -NH-).
n represents the degree of polymerization
X represents an unsaturated bond group to which a hydrogen atom or two or more electron-withdrawing groups are bonded. * In the general formula (I) represents a bond with an atom contained in the organic group. )
It is preferable to have a maximum of 6 types of groups represented by.

[3] In the present embodiment, the organic group is a mesogen group having a 2 to 6-valent aromatic ring or an alkylene group having 3 to 15 or less carbon atoms (provided that -CH ₂ -CH ₂ in the alkylene group is used. -May be replaced with -CH = CH-).

（上記一般式（１）中、
Ｂ¹は、２～６価の結合手を有する有機基を表し、
Ｌは、単結合又は炭素原子数１～１０のアルキレン基（但し、当該アルキレン基中の－ＣＨ₂－は、隣り合わないよう、－Ｏ－、－Ｓ－、又は－ＮＨ－に置換されてもよく、さらに当該アルキレン基中の－ＣＨ₂－ＣＨ₂－は、－ＣＨ＝ＣＨ－に置換されてもよい）を表し、
Ｍは、付加重合性単量体単位を表し、
Ｚは、単結合又は炭素原子数１～１０のアルキレン基（但し、当該アルキレン基中の－ＣＨ₂－は、－Ｏ－、－Ｓ－、－ＮＨ－に置換されてもよい）を表し、
ｎは、０～１００００の整数を表し、
Ｘは、水素原子又は２以上の電子吸引基が結合された不飽和結合基を表わし、かつｋ個存在するＸのうち少なくとも１種のＸが前記２以上の電子吸引基が結合された不飽和結合基であり、
ｋは、２以上６以下の整数を表す。なお、一般式（１）中に複数存在する、Ｌ、Ｍ、Ｚ及びＸはそれぞれ独立して、互いに同一又は異なっていてもよい。） [4] The macromonomer in the present embodiment is preferably represented by the following general formula (1).

(In the above general formula (1),
B ¹ represents an organic group having a 2- to hexavalent bond.
L is a single bond or an alkylene group having 1 to 10 carbon atoms (however, -CH _2- in the alkylene group is substituted with -O-, -S-, or -NH- so as not to be adjacent to each other. In addition, -CH ₂ -CH _2- in the alkylene group may be substituted with -CH = CH-).
M represents an addition-polymerizable monomer unit and represents
Z represents a single bond or an alkylene group having 1 to 10 carbon atoms (however, -CH _2- in the alkylene group may be substituted with -O-, -S-, -NH-).
n represents an integer from 0 to 10000 and represents
X represents an unsaturated bond group to which a hydrogen atom or two or more electron-withdrawing groups are bonded, and at least one X among k existing Xs is unsaturated to which the two or more electron-withdrawing groups are bonded. It is a binding group
k represents an integer of 2 or more and 6 or less. It should be noted that L, M, Z and X, which are present in a plurality in the general formula (1), may be independent of each other and may be the same or different from each other. )

（上記一般式（２）中、Ｂ²は、炭素原子数３～１５以下のアルキレン基（但し、当該アルキレン基中の－ＣＨ₂－ＣＨ₂－は、－ＣＨ＝ＣＨ－に置換されてもよい）を表し、
Ｌ¹及びＬ²はそれぞれ独立して、炭素原子数１～１０のアルキレン基（但し、当該アルキレン基中の－ＣＨ₂－は、－Ｏ－、－Ｓ－、－ＮＨ－に置換されてもよい）を表し、
Ｍ¹、Ｍ²はそれぞれ独立して、付加重合性単量体単位を表し、Ｚ¹～Ｚ²はそれぞれ独立して、炭素原子数１～１０のアルキレン基（但し、当該アルキレン基中の－ＣＨ₂－は、－Ｏ－、－Ｓ－、－ＮＨ－に置換されてもよい）を表し、
ｎ¹及びｎ²はそれぞれ独立して、１～１００００の整数を表し、
Ｘ¹及びＸ²はそれぞれ独立して、水素原子又は２以上の電子吸引基が結合された不飽和結合基を表わし、かつＸ¹～Ｘ²のうち少なくとも１つが前記２以上の電子吸引基が結合された不飽和結合基を表す。） [5] The macromonomer in the present embodiment is preferably represented by the following general formula (2).

(In the above general formula (2), B ² is an alkylene group having 3 to 15 carbon atoms or less (provided that -CH ₂ -CH _2- in the alkylene group is replaced with -CH = CH-. Good),
L ¹ and L ² are independently alkylene groups having 1 to 10 carbon atoms (however, even if -CH _2- in the alkylene group is replaced with -O-, -S-, -NH-. Good),
M ¹ and M ² each independently represent an addition-polymerizable monomer unit, and Z ¹ to Z ² independently represent an alkylene group having 1 to 10 carbon atoms (however,-in the alkylene group). CH ₂ -represents (may be replaced with -O-, -S-, -NH-).
n ¹ and n ² each independently represent an integer from 1 to 10000.
X ¹ and X ² each independently represent an unsaturated bond group to which a hydrogen atom or two or more electron-withdrawing groups are bonded, and at least one of X ¹ to X ² has the two or more electron-withdrawing groups. Represents a bound unsaturated binding group. )

According to the present invention, the branched structure can be efficiently imparted by copolymerization, and the productivity of the branched polymer can be improved.

FIG. 1 is a graph showing the relationship between reaction time and Mz in Examples and Comparative Examples.

Hereinafter, embodiments of the present invention (hereinafter referred to as “the present embodiment”) will be described in detail, but the present invention is not limited to the following description and is variously modified within the scope of the gist thereof. Can be carried out.

The present invention is a macromonomer having at least one unsaturated bond group to which two or more electron-withdrawing groups are bonded at the terminal portion and containing an addition-polymerizable monomer unit as a main chain.
By having an unsaturated bond group to which two or more electron-withdrawing groups are bonded at the terminal portion, copolymerization with a vinyl-based monomer, particularly a styrene-based monomer unit, can easily proceed. In particular, when a branched polymer such as branched polystyrene is generally produced, a small amount of macromonomer is added to an aromatic vinyl monomer such as styrene for copolymerization, but the copolymerization can be performed even with a small amount of macromonomer. In particular, in the case of styrene, it is advantageous to have a functional group having high alternating copolymerizability. The fact that the copolymerization is easy to proceed in the present specification means that the copolymerization proceeds even when a small amount of macromonomer is added.

As used herein, the term "additionally polymerizable monomer unit" refers to a monomer unit that cleaves an unsaturated bond to polymerize, and includes, for example, a radical or anionic polymerizable monomer unit. Further, the "monomer unit" in the present specification means a repeating unit in a polymer obtained by polymerizing a monomer, and for example, the "styrene-based monomer unit" is a styrene-based simple substance. A structural unit in which an unsaturated double bond in the monomer becomes a single bond by a polymerization reaction or a cross-linking reaction of the polymer. Specific examples of the addition-polymerizable monomer include conjugated diene-based monomers such as butadiene, isoprene, milsen, and farnesene; styrene-based monomers such as styrene, α-methylstyrene, and paramethylstyrene; methyl (meth) acrylates. , Ethyl (meth) acrylate, propyl (meth) acrylate, butyl (meth) acrylate and other (meth) acrylate-based monomers; are preferred. Further, the addition-polymerizable monomer may be composed of two or more kinds of these monomers.

As used herein, the term "unsaturated bond group to which two or more electron-withdrawing groups are bonded" is a substitution in which a carbon atom constituting a carbon-carbon unsaturated bond group is easily negatively charged due to an inductive effect or a resonance effect. A group in which a group is covalently bonded. Examples of the substituent include an ester group, an amide group, a carboxyl group, a ketone group, a cyano group or a halogen atom.

In the present invention, specific examples of unsaturated bond groups to which two or more electron-withdrawing groups are bonded include, for example, maleic acid diester, maleic acid monoester, fumaric acid diester, fumaric acid monoester, maleic acid diamide, and maleic acid monoamide. , Maleimide is preferred. From the viewpoint of high reactivity with the styrene-based monomer, maleic acid diester or maleic acid monoester is preferable. Further, the unsaturated bond group may be either an E-form or a Z-form.
In the present invention, the unsaturated bond group to which two or more electron-withdrawing groups are bonded is preferably an unsaturated bond group represented by the following general formula (i).

(In the above general formula (i), W ¹ represents a single bond, an amino group, an —NHR ^a group, and a —R ^a O group (R ^a represents a hydrogen atom or an alkyl group having 1 to 10 carbon atoms). ), W ² represents -NH-, -NR ^b- , -N =, -O- (R ^b ) _q (R ^b represents an alkylene group having 1 to 10 carbon atoms, and q is 0 or more. It represents an integer of 1 or less.) However, when W ¹ is a single bond, W ² is −N = and W ¹ and W ² may be bonded to form a maleimide. * In (i) represents a bond with a molecular chain that is the main chain.)
In the above general formula (i), Ra is preferably ^a hydrogen atom, a methyl group, an ethyl group or a linear or branched propyl group.

In the present invention, preferable examples of the unsaturated bond group to which two or more electron-withdrawing groups are bonded include the following formulas (i-1) to (i-17), and among them, a vinyl-based single amount. (I-1) to (i-9) are preferable from the viewpoint of high reactivity with the body.

The "terminal" in the present specification can be the position at the most end of the molecular chain, but an unsaturated bond group to which two or more electron-withdrawing groups are bonded should be present near the end (or near the end). For example, it has effective reactivity with vinyl-based monomers because the frequency of collisions between unsaturated bond groups and polymer radicals required for the reaction increases. Therefore, the "end" in the present embodiment may be a portion (end portion) in the molecular chain that includes the position (atom) at the most end of the molecular chain and has a certain range. (In other words, an unsaturated binding group to which two or more electron-withdrawing groups are bound can be located near the terminal). The portion within the certain range is not limited, but is preferably 10% or less, and more preferably 5% or less of the stretched chain length of the molecular chain extending from the center of the macromonomer. % Or less is even more preferable, and 1% or less is even more preferable.

The number average molecular weight (Mn) of the macromonomer according to the present invention is preferably 1000 or more and 200,000 or less, more preferably 5000 or more and 150,000 or less, and more preferably 10,000 or more and 100,000 or less. As a method for measuring the number average molecular weight (Mn) of the macromonomer, the conditions in the column of Examples described later were used.
The macromonomer according to the present invention has the following general formula (I): which directly bonds an organic group having a 2- to 6-valent bond and the bond of the organic group.

(In the above general formula (I), L is a single bond or an alkylene group having 1 to 10 carbon atoms (however, -CH _2- in the alkylene group is not adjacent to each other, -O-, -S- Alternatively, it may be substituted with -NH-, and -CH ₂ -CH _2- in the alkylene group may be substituted with -CH = CH-).
M represents an addition-polymerizable monomer unit and represents
Z represents a single bond or an alkylene group having 1 to 10 carbon atoms (however, -CH _2- in the alkylene group may be substituted with -O-, -S-, -NH-).
n represents the degree of polymerization
X represents an unsaturated bond group to which a hydrogen atom or two or more electron-withdrawing groups are bonded. * In the general formula (I) represents a bond with an atom contained in an organic group. )
It is preferable to have a maximum of 6 types of groups represented by, and at least 1 type of unsaturated bond group to which the 2 or more electron-withdrawing groups are bonded in one molecule.
In the macromonomer according to the present invention, the number of groups represented by the general formula (I) and the valence of the organic group having a 2- to 6-valent bond are the same. Further, the macromonomer according to the present invention has at least one unsaturated bond group in which two or more electron-withdrawing groups are bonded in one molecule of the macromonomer (in other words, an electron-withdrawing group having two or more Xs). It is preferable to have at least one group represented by the above general formula (I) satisfying the condition of a bound unsaturated bonding group) and M, which is an addition-polymerizable monomer unit, as a main chain.

The organic group in the general formula (I) refers to a hydrocarbon group in which carbon atoms are covalently bonded to each other, and the organic group having a 2- to 6-valent bond is a 2- to 6-valent bond. A mesogen group having an aromatic ring, an alkylene group having 3 to 15 carbon atoms (however, -CH ₂ -CH _2- in the alkylene group may be substituted with -CH = CH-) or the alkylene. It is preferable to represent a group obtained by removing 0 to 4 hydrogen atoms in the group.

In the present embodiment, the "organic group having a divalent to 6-valent bond" means an atomic group excluding 0 to 4 hydrogen atoms in the divalent organic group, and has the above-mentioned aromatic ring 2 It is preferable that the group has 0 to 4 hydrogen atoms removed from the valence mesogen group, or 0 to 4 hydrogen atoms have been removed from the above-mentioned alkylene group having 3 to 15 carbon atoms or less.

A mesogen group having an aromatic ring is a group in which one aromatic ring or two or more aromatic rings are fused. Examples of the mesogen group having a divalent aromatic ring include a substituted or unsubstituted phenylene group, a substituted or unsubstituted naphthalenediyl group, a substituted or unsubstituted vinaphthalenediyl group, and a substituted or unsubstituted anthracendyl group. , Substituent or unsubstituted full-orangeyl group, substituted or unsubstituted triphenylenediyl group, substituted or unsubstituted phenantrenyl group, substituted or unsubstituted benzophenantrenyl group, substituted or unsubstituted dibenzophenantrenyl group, substituted. Alternatively, an unsubstituted or unsubstituted chrysendiyl group, a substituted or unsubstituted benzoclysendiyl group, a substituted or unsubstituted pysendiyl group, and a substituted or unsubstituted pyrenziyl group are preferable. The mesogen group having a trivalent to hexavalent aromatic ring is preferably a group obtained by removing 1 to 4 hydrogen atoms from the above-mentioned divalent mesogen group.

The above-mentioned alkylene group having 3 to 15 carbon atoms (however, -CH ₂ -CH _2- in the alkylene group may be substituted with -CH = CH-) is a general formula C _m H _{2 m} (m). Is a divalent saturated hydrocarbon represented by an integer of 3 or more and 15 or less) and a divalent unsaturated hydrocarbon represented by the general formula C _m H _2m-2 (m is an integer of 3 or more and 15 or less). include. The alkylene group may be, for example, a linear or branched propylene group, a linear or branched butylene group, a linear or branched pentylene group, a linear or branched hexylene group, a linear or branched heptylene group, a linear or branched octylene group, or a direct chain. A saturated hydrocarbon group selected from the group consisting of a chain or a branched nonylene group and a linear or branched desilene group, and -CH ₂ -CH _2- in the saturated hydrocarbon are replaced with -CH = CH-. Saturated hydrocarbon groups are preferred. Further, -CH ₂ -CH _2- in the saturated hydrocarbon may be replaced with one or more -CH = CH- as long as they are not adjacent to each other.

In the present embodiment, the "organic group having a divalent to 6-valent bond" means an atomic group excluding 0 to 4 hydrogen atoms in the divalent organic group, and has the above-mentioned aromatic ring 2 It is preferable that the group has 0 to 4 hydrogen atoms removed from the valence mesogen group, or 0 to 4 hydrogen atoms have been removed from the above-mentioned alkylene group having 3 to 15 carbon atoms or less.

The alkylene group having 1 to 10 carbon atoms in the present specification is preferably a linear or branched alkylene group, for example, a methylene group, an ethylene group, a linear or branched propylene group, a linear or branched butylene group. , A linear or branched pentylene group, a linear or branched hexylene group, a linear or branched heptylene group, a linear or branched octylene group, a linear or branched nonylene group, or a linear or branched decylene group is preferable.

In the above general formula (I), L is a methylene group, an ethylene group, a linear or branched propylene group, a linear or branched butylene group, a linear or branched pentylene group, a linear or branched hexylene group, a linear or branched group. A heptylene group, a linear or branched octylene group, a linear or branched nonylene group, a linear or branched decylene group is preferable, a linear or branched propylene group, a linear or branched butylene group, a linear or branched pentylene group, a linear or branched group. A branched hexylene group, a linear or branched heptylene group, a linear or branched octylene group is more preferable.

In the above general formula (I), Z is preferably a linear or branched alkylene group, and is preferably an ethylene group, a linear or branched propylene group, a linear or branched butylene group, a cyclobutylene group, a linear or branched group. Pentylene group, cyclopentylene group, linear or branched hexylene group, cyclohexylene group, linear or branched heptylene group, cycloheptylene group, linear or branched octylene group, cyclooctylene group, linear or branched nonylene group, direct A chain or branched decylene group is preferred, an ethylene group, a linear or branched propylene group, a linear or branched butylene group, a cyclobutylene group, a linear or branched pentylene group, a cyclopentylene group, a linear or branched hexylene group, a cyclohexyl. A silene group is more preferred.

In the above general formula (I), M represents an addition-polymerizable monomer unit, specifically, a conjugated diene-based monomer unit, a styrene-based monomer unit, or a (meth) acrylate-based monomer unit. Is preferable. More specifically, in the above general formula (I), M preferably contains a monomer unit represented by the following general formula (ii).

(In the above general formula (ii), R ^c , R ^d , R ^e , R ^f , R ^g and R ^h each independently represent a hydrogen atom or an alkyl group having 1 to 10 carbon atoms, and Y ¹ And Y ² independently represent -C (= O) -OR ⁱ or a substituted or unsubstituted phenyl group, and s, t and r independently represent 0 or 1, respectively, and s + t + r. Is an integer of 1 or more, and R ⁱ represents a hydrogen atom or an alkyl group having 1 to 10 carbon atoms.)

In the above general formula (ii), R ^c , R ^d , R ^e , R ^f , R ^g and R ^h are each independently composed of a hydrogen atom or a linear or branched alkyl group having 1 to 7 carbon atoms. A hydrogen atom or a linear alkyl group having 1 to 5 carbon atoms is more preferable.
In the above general formula (ii), it is preferable that Y ¹ and Y ² independently represent −C (= O) —OR ⁱ or an unsubstituted phenyl group, respectively. R ⁱ represents a hydrogen atom or an alkyl group having 1 to 5 carbon atoms.

In the above general formula (I), X is preferably a hydrogen atom or an unsaturated bond group represented by the following general formula (i).

(In the above general formula (i), W ¹ represents a single bond, an amino group, an —NHR ^a group, and a —R ^a O group (R ^a represents a hydrogen atom or an alkyl group having 1 to 10 carbon atoms). ), W ² represents -NH-, -NR ^b- , -N =, -O- (R ^b ) _q (R ^b represents an alkylene group having 1 to 10 carbon atoms, and q is 0 or more. It represents an integer of 1 or less.) However, when W ¹ is a single bond, W ² is −N = and W ¹ and W ² may be bonded to form a maleimide. * In (i) represents a bond with a molecular chain that is the main chain.)
In the above general formula (i), Ra is preferably ^a hydrogen atom, a methyl group, an ethyl group or a linear or branched propyl group. Among them, X in the general formula (ii) is preferably the above formulas (i-1) to (i-9) from the viewpoint of high reactivity with the vinyl-based monomer.

（上記一般式（１）中、
Ｂ₁は、２～６価の結合手を有する有機基を表し、
Ｌは、単結合又は炭素原子数１～１０のアルキレン基（但し、当該アルキレン基中の－ＣＨ₂－は、隣り合わないよう、－Ｏ－、－Ｓ－、又は－ＮＨ－に置換されてもよく、さらに当該アルキレン基中の－ＣＨ₂－ＣＨ₂－は、－ＣＨ＝ＣＨ－に置換されてもよい）を表し、
Ｍは、単結合又は付加重合性単量体単位（好ましくは、共役ジエン系単量体単位）を表し、ただし、ｎ個存在するＭのうち少なくとも１つが付加重合性単量体単位であり
Ｚは、単結合又は炭素原子数１～１０のアルキレン基（但し、当該アルキレン基中の－ＣＨ₂－は、－Ｏ－、－Ｓ－、－ＮＨ－に置換されてもよい）を表し、
ｎは、重合度を表し、
Ｘは、水素原子又は２以上の電子吸引基が結合された不飽和結合基を表し、ただし、ｋ個存在するＸのうち少なくとも１つが２以上の電子吸引基が結合された不飽和結合基である。
ｋは、２以上６以下の整数を表す。なお、一般式（Ｉ）中に複数存在する、Ｌ、Ｍ、Ｚ及びＸはそれぞれ独立して、互いに同一又は異なっていてもよい。）
上記一般式（Ｉ）で表されるマクロモノマーの構造により、ビニル系単量体、特にスチレン系単量体単位との共重合にて分岐構造を効率的に付与することができ、分岐ポリマーの生産性、特にポリスチレンの生産性を向上させることができる。 In the general formula (I), n represents the degree of polymerization, preferably 01 to 10000, and more preferably 1 to 5000.
The macromonomer according to the present invention has the following general formula (1):

(In the above general formula (1),
B ₁ represents an organic group having a 2- to hexavalent bond.
L is a single bond or an alkylene group having 1 to 10 carbon atoms (however, -CH _2- in the alkylene group is substituted with -O-, -S-, or -NH- so as not to be adjacent to each other. In addition, -CH ₂ -CH _2- in the alkylene group may be substituted with -CH = CH-).
M represents a single-bonded or addition-polymerizable monomer unit (preferably a conjugated diene-based monomer unit), where at least one of n existing Ms is an addition-polymerizable monomer unit. Represents a single bond or an alkylene group having 1 to 10 carbon atoms (wherein -CH _2- in the alkylene group may be substituted with -O-, -S-, -NH-).
n represents the degree of polymerization
X represents an unsaturated bond group to which a hydrogen atom or two or more electron-withdrawing groups are bonded, except that at least one of the k existing Xs is an unsaturated bond group to which two or more electron-withdrawing groups are bonded. be.
k represents an integer of 2 or more and 6 or less. It should be noted that L, M, Z and X, which are present in a plurality in the general formula (I), may be independently the same or different from each other. )
Due to the structure of the macromonomer represented by the general formula (I), a branched structure can be efficiently imparted by copolymerization with a vinyl-based monomer, particularly a styrene-based monomer unit, and the branched polymer can be provided with a branched structure. Productivity, especially polystyrene productivity, can be improved.

In the above general formula (1), L, M, Z and X each exist in 2 to 6 corresponding to the number of bonds of B ¹ . In this case, for example, there are 2 to 6 L's, but each L may be the same or different. The same applies to the other M, Z and X.
In the above general formula (1), k is preferably an integer of 2 or more and 4 or less. Further, in the macromonomer of the present embodiment, the number of unsaturated bonding groups to which two or more electron-withdrawing groups present in one macromonomer molecule is bonded is not less than the value of k, and is present in one macromonomer molecule. It is preferable that the number of unsaturated bonding groups to which two or more electron-withdrawing groups are bonded and the value of k match.

Further, in the general formula (1), L, M, Z and X, and n and B ¹ are preferred embodiments of L, M, Z and X, and n and B ¹ in the general formula (I). Since it is the same as the preferred embodiment, it is omitted here.

Hereinafter, preferred forms of the macromonomer according to the present invention will be described. The compounds represented by the following general formulas (2) to (6) are all preferable forms of the macromonomer represented by the general formula (1).
In the present embodiment, when an organic group having a divalent bond is used, the macromonomer leads to having two or more unsaturated bond groups to which electron-withdrawing groups are bonded at (maximum) two places, and vinyl. It is preferable from the viewpoint that a branched structure can be formed when copolymerized with a system monomer. Further, when an organic group having a 3- to 6-valent bond is used, the macromonomer has an unsaturated bond group to which two or more electron-withdrawing groups are bonded (maximum) at 3 to 6 positions, respectively. , It is more preferable because the copolymerization of the macromonomer and the vinyl-based monomer can be efficiently promoted. On the other hand, when an organic group having a 7-valent or higher-valent bond is used, the macromonomer has (maximum) 7 or more unsaturated bonding groups to which 2 or more electron-withdrawing groups are bonded, which leads to vinyl. When copolymerized with a system monomer, it tends to lead to local gelation.
The macromonomer according to the present invention is preferably represented by the following general formula (2).

(In the above general formula (2), B ² is a mesogen group having a divalent aromatic ring or an alkylene group having 3 to 15 carbon atoms (however, -CH ₂ -CH _2-- in the alkylene group is -CH = CH- may be replaced),
L ¹ and L ² are independently alkylene groups having 1 to 10 carbon atoms (however, even if -CH _2- in the alkylene group is replaced with -O-, -S-, -NH-. Good),
M ¹ and M ² each independently represent an addition-polymerizable monomer unit, and Z ¹ to Z ² independently represent an alkylene group having 1 to 10 carbon atoms (however,-in the alkylene group). CH ₂ -represents (may be replaced with -O-, -S-, -NH-).
n ¹ and n ² each independently represent an integer from 1 to 10000.
X ¹ and X ² each independently represent an unsaturated bond group to which a hydrogen atom or two or more electron-withdrawing groups are bonded, and at least one of X ¹ and X ² has the two or more electron-withdrawing groups. Represents a bound unsaturated bond group)

In the above general formula (2), examples of the alkylene group having 3 to 15 carbon atoms include a linear or branched propylene group, a linear or branched butylene group, a linear or branched pentylene group, and a linear or branched hexylene group. Examples thereof include a linear or branched heptylene group, a linear or branched octylene group, a linear or branched nonylene group, and a linear or branched decylene group.

In the above general formula (2), the mesogen group having a divalent aromatic ring includes a 1,2-phenylene group, a 1,3-phenylene group, a 1,4-phenylene group, a 1,8-naphthylene group and 1 , 2-naphthylene group, 1,3-naphthylene group, 1,2-naphthylene group, 1,4-naphthylene group, 1,5-naphthylene group, 1,6-naphthylene group, 1,7-naphthylene group, 2, 7-naphthylene group, 2,3-naphthylene group, 2,5-naphthylene group, 2,6-naphthylene group, 1,8-phenant rangeyl group, 2,7-phenant rangeyl group, 3,6-phenant rangeil group, Preferably, a 4,5-phenanthrangeyl group, a 1,8-anthracendyl group, a 1,5-anthracendyl group, a 1,4-anthracendyl group, a 2,3-anthracendyl group, or a 2,6-anthracendyl group. ..

In the above general formula (2), L ¹ and L ² are independently each of a methylene group, an ethylene group, a linear or branched propylene group, a linear or branched butylene group, a linear or branched pentylene group, a linear or branched group. A hexylene group, a linear or branched heptylene group, a linear or branched octylene group, a linear or branched nonylene group, a linear or branched decylene group is preferable, a linear or branched propylene group, a linear or branched butylene group, a straight chain. Alternatively, a branched pentylene group, a linear or branched hexylene group, a linear or branched heptylene group, a linear or branched octylene group is more preferable, a linear or branched butylene group, a linear or branched pentylene group, a linear or branched hexylene group. Groups, linear or branched heptylene groups are more preferred.

In the above general formula (2), M ¹ and M ² are each independently preferably a conjugated diene-based monomer unit, a styrene-based monomer unit, or a (meth) acrylate-based monomer unit. More specifically, in the above general formula (I), M preferably contains a monomer unit represented by the following general formula (ii).

(In the above general formula (ii), R ^c , R ^d , R ^e , R ^f , R ^g and R ^h each independently represent a hydrogen atom or an alkyl group having 1 to 10 carbon atoms, and Y ¹ And Y ² independently represent -C (= O) -OR ⁱ or a substituted or unsubstituted phenyl group, and s, t and r independently represent 0 or 1, respectively, and s + t + r. Is an integer of 1 or more, and R ⁱ represents a hydrogen atom or an alkyl group having 1 to 10 carbon atoms.)

（上記一般式（ｉ）中、Ｗ¹は、単結合、アミノ基、－ＮＨＲ^a基、－Ｒ^aＯ基を表し（Ｒ^aは、水素原子又は炭素原子数１～１０のアルキル基を表す。）、Ｗ²は、－ＮＨ－、－ＮＲ^b-、－Ｏ－（Ｒ^b）_qを表わし（Ｒ^bは炭素原子数１～１０のアルキレン基を表し、ｑは０以上１以下の整数を表す。）、Ｗ¹が単結合の場合は、Ｗ²と結合してマレイミドを形成してもよい。）
当該不飽和結合基の好ましい形態としては、上記式（ｉ－１）～（ｉ－１７）からなる群から選択される１種である。 In the above general formula (ii), R ^c , R ^d , R ^e , R ^f , R ^g and R ^h are each independently composed of a hydrogen atom or a linear or branched alkyl group having 1 to 7 carbon atoms. A hydrogen atom or a linear alkyl group having 1 to 5 carbon atoms is more preferable.
In the above general formula (2), n ¹ and n ² are independent of each other, preferably 5 to 10000, preferably 25 to 750, and preferably 50 to 500.
In the above general formula (2), X ¹ and X ² are independent of each other, and unsaturated bond groups represented by the following general formula (i) are preferable.

(In the above general formula (i), W ¹ represents a single bond, an amino group, an —NHR ^a group, and a —R ^a O group (R ^a represents a hydrogen atom or an alkyl group having 1 to 10 carbon atoms). ), W ² represents -NH-, -NR ^b- , -O- (R ^b ) _q (R ^b represents an alkylene group having 1 to 10 carbon atoms, and q is an integer of 0 or more and 1 or less. ), When W ¹ is a single bond, it may be combined with W ² to form a maleimide.)
The preferred form of the unsaturated bond group is one selected from the group consisting of the above formulas (i-1) to (i-17).

（上記式（２－１）～（２－３７）中、ｍ¹及びｍ²はそれぞれ独立して、５～１００００が好ましい。）
上記式（２－１）～（２－３７）で表わされる化合物のうち、特に式（２－１）～（２－１４）が好ましい。 本実施形態において、３価の結合手を有する有機基を用いた場合は、マクロモノマーが２以上の電子吸引基が結合された不飽和結合基をそれぞれ（最大）３箇所に有することにつながり、マクロモノマーとビニル系単量体との共重合を効率的に進行させることができるため好ましい。
本発明に係るマクロモノマーは以下の一般式（３）で表されることが好ましい。

In this embodiment, examples of the macromonomer represented by the general formula (2) include the following formulas (2-1) to (2-37). Further, the following structural formula shows an example of the present invention. Further, the macromonomer in the present embodiment also includes vinyl addition and 1,4-addition as an addition mode in the case where M in the above general formula (2) is a conjugated diene-based monomer unit. May be interpreted.

(In the above formulas (2-1) to (2-37), m ¹ and m ² are each independently, preferably 5 to 10000.)
Of the compounds represented by the above formulas (2-1) to (2-37), the compounds represented by the formulas (2-1) to (2-14) are particularly preferable. In the present embodiment, when an organic group having a trivalent bond is used, the macromonomer has an unsaturated bond group to which two or more electron-withdrawing groups are bonded at each (maximum) three positions. It is preferable because the copolymerization of the macromonomer and the vinyl-based monomer can be efficiently promoted.
The macromonomer according to the present invention is preferably represented by the following general formula (3).

(In the above general formula (3), B ³ is a mesogen group having a trivalent aromatic ring, an alkyridine group having 3 to 15 carbon atoms, or an alkylene group having 3 to 15 carbon atoms or less (however, the alkylene group). -CH ₂ -CH _2- in-represents an organic group (1) from which any one hydrogen atom has been removed from (which may be substituted with -CH = CH-).
M ¹ , M ² and M ³ independently represent a single bond or an addition-polymerizable monomer unit (conjugated diene-based monomer unit), and Z ₁ to Z ₃ are independent carbon atoms. Represents an alkylene group of numbers 1 to 10 (wherein -CH _2- in the alkylene group may be substituted with -O-, -S-, -NH-).
n ₁ , n ₂ and n ₃ each independently represent an integer from 1 to 10000.
X ₁ , X ₂ and X ₃ each independently represent an unsaturated bond group to which a hydrogen atom or two or more electron-withdrawing groups are bonded, and at least one of X ₁ to X ₃ is the two or more electrons. Represents an unsaturated binding group to which an attracting group is attached)

本実施形態において、一般式（３）で表されるマクロモノマーとしては、例えば、以下の式（３－１）～式（３－８）が挙げられる。

（上記式（３－１）～（３－８）中、ｍ¹、ｍ²及びｍ³はそれぞれ独立して、５～１００００が好ましい。）
本実施形態において、４価の結合手を有する有機基を用いた場合は、マクロモノマーが２以上の電子吸引基が結合された不飽和結合基を（最大）それぞれ４箇所に有することにつながり、マクロモノマーとビニル系単量体との共重合を効率的に進行させることができるため好ましい。
本発明に係るマクロモノマーは以下の一般式（４）で表されることが好ましい。

In the above general formula (3), examples of the mesogen group having a trivalent aromatic ring include formulas (b-1) to (b-3).

In this embodiment, examples of the macromonomer represented by the general formula (3) include the following formulas (3-1) to (3-8).

(In the above formulas (3-1) to (3-8), m ¹ , m ² and m ³ are each independently preferably 5 to 10000).
In the present embodiment, when an organic group having a tetravalent bond is used, the macromonomer leads to having unsaturated bond groups to which two or more electron-withdrawing groups are bonded at (maximum) four positions, respectively. It is preferable because the copolymerization of the macromonomer and the vinyl-based monomer can be efficiently promoted.
The macromonomer according to the present invention is preferably represented by the following general formula (4).

(In the above general formula (4), B ⁴ is a mesogen group having a tetravalent aromatic ring, a carbon atom or an alkylene group having 3 to 15 carbon atoms (provided that -CH ₂ -CH ₂ in the alkylene group is used. -Represents an organic group (2) from which two arbitrary hydrogen atoms have been removed from (which may be substituted with -CH = CH-).
M ¹ , M ² , M ³ and M ⁴ independently represent a single bond or an addition-polymerizable monomer unit (conjugated diene-based monomer unit), and Z ₁ to Z ⁴ are independent of each other. Represents an alkylene group having 1 to 10 carbon atoms (wherein -CH _2- in the alkylene group may be substituted with -O-, -S-, -NH-).
n ¹ , n ² , n ³ and n ⁴ each independently represent an integer from 1 to 10000.
X ¹ , X ² , X ³ and X ⁴ each independently represent an unsaturated bond group to which a hydrogen atom or two or more electron-withdrawing groups are bonded, and at least one of X ¹ to X ⁴ is the above 2. Represents an unsaturated bond group to which the above electron-withdrawing groups are bonded)

（上記一般式中、＊はＬ¹～Ｌ⁴に結合する結合手を表す） In the above general formula (4), examples of the mesogen group having a tetravalent aromatic ring include (c-1) to (c-3).

(In the above general formula, * represents a bond that binds to L ¹ to L ⁴ )

（上記式（４－１）～（４－８）中、ｍ¹、ｍ²、ｍ³及びｍ⁴はそれぞれ独立して、５～１００００が好ましい。）
本実施形態において、５価の結合手を有する有機基を用いた場合は、マクロモノマーが２以上の電子吸引基が結合された不飽和結合基を（最大）それぞれ５箇所に有することにつながり、マクロモノマーとビニル系単量体との共重合を効率的に進行させることができるためこのましい。
本発明に係るマクロモノマーは以下の一般式（５）で表されることが好ましい。

（上記一般式（４）中、Ｂ⁵は、５価の有機基（３）を表し、
Ｍ¹、Ｍ²、Ｍ³、Ｍ⁴及びＭ⁵はそれぞれ独立して、単結合又は付加重合性単量体単位（共役ジエン系単量体単位）を表し、Ｚ₁～Ｚ⁵はそれぞれ独立して、炭素原子数１～１０のアルキレン基（但し、当該アルキレン基中の－ＣＨ₂－は、－Ｏ－、－Ｓ－、－ＮＨ－に置換されてもよい）を表し、
ｎ¹、ｎ²、ｎ³、ｎ⁴及びｎ⁵はそれぞれ独立して、１～１００００の整数を表し、
Ｘ¹、Ｘ²、Ｘ³、Ｘ³及びＸ⁵はそれぞれ独立して、水素原子又は２以上の電子吸引基が結合された不飽和結合基を表わし、かつＸ¹～Ｘ⁵のうち少なくとも１つが前記２以上の電子吸引基が結合された不飽和結合基を表す。） In the present embodiment, examples of the macromonomer represented by the general formula (4) include the following formulas (4-1) to (4-8).

(In the above formulas (4-1) to (4-8), m ¹ , m ² , m ³ and m ⁴ are each independently preferably 5 to 10000).
In the present embodiment, when an organic group having a pentavalent bond is used, the macromonomer leads to having (maximum) five unsaturated bond groups to which two or more electron-withdrawing groups are bonded. This is preferable because the copolymerization of the macromonomer and the vinyl-based monomer can be efficiently promoted.
The macromonomer according to the present invention is preferably represented by the following general formula (5).

(In the above general formula (4), B ⁵ represents a pentavalent organic group (3).
M ¹ , M ² , M ³ , M ⁴ and M ⁵ each independently represent a single bond or an addition-polymerizable monomer unit (conjugated diene-based monomer unit), and Z ₁ to Z ⁵ are independent of each other. Then, it represents an alkylene group having 1 to 10 carbon atoms (however, -CH _2- in the alkylene group may be substituted with -O-, -S-, -NH-).
n ¹ , n ² , n ³ , n ⁴ and n ⁵ each independently represent an integer from 1 to 10000.
X ¹ , X ² , X ³ , X ³ and X ⁵ each independently represent an unsaturated bond group to which a hydrogen atom or two or more electron-withdrawing groups are bonded, and at least one of X ¹ to X ⁵ is attached. One represents an unsaturated bond group to which the two or more electron-withdrawing groups are bonded. )

（上記一般式中、＊はＬ¹～Ｌ⁵に結合する結合手を表す）
本発明に係るマクロモノマーとしては、下記一般式（６）で表されることが好ましい。

（上記一般式（６）中、Ｂ⁶は、６価の芳香族環を有するメソゲン基を表し、
Ｌ¹～Ｌ⁶はそれぞれ独立して、単結合又は炭素原子数１～１０のアルキレン基（但し、当該アルキレン基中の－ＣＨ₂－は、－Ｏ－、－Ｓ－、－ＮＨ－に置換されてもよく、さらに当該アルキレン基中の－ＣＨ₂－ＣＨ₂－は、－ＣＨ＝ＣＨ－に置換されてもよい）を表し、
Ｍ¹～Ｍ⁶はそれぞれ独立して、単結合又は付加重合性単量体単位を表し、
Ｚ¹～Ｚ⁶はそれぞれ独立して、単結合又は炭素原子数１～１０のアルキレン基（但し、当該アルキレン基中の－ＣＨ₂－は、－Ｏ－、－Ｓ－、－ＮＨ－に置換されてもよい）を表し、
ｎ¹～ｎ⁶はそれぞれ独立して、０～１００００の整数を表し、
Ｘ¹～Ｘ⁶はそれぞれ独立して、水素原子又は２以上の電子吸引基が結合された不飽和結合基を表わし、かつＸ₁～Ｘ₆のうち少なくとも２つが前記２以上の電子吸引基が結合された不飽和結合基を表す。） Examples of the pentavalent organic group (2) in the above general formula (5) include (d-1) to (d-3).

(In the above general formula, * represents a bond that binds to L ¹ to L ⁵ )
The macromonomer according to the present invention is preferably represented by the following general formula (6).

(In the above general formula (6), B ⁶ represents a mesogen group having a hexavalent aromatic ring.
L ¹ to L ⁶ are independently single-bonded or alkylene groups having 1 to 10 carbon atoms (however, -CH _2- in the alkylene group is replaced with -O-, -S-, and -NH-. In addition, -CH ₂ -CH _2- in the alkylene group may be substituted with -CH = CH-).
M ¹ to M ⁶ independently represent a single bond or an addition-polymerizable monomer unit.
Z ¹ to Z ⁶ are independently single-bonded or alkylene groups having 1 to 10 carbon atoms (however, -CH _2- in the alkylene group is replaced with -O-, -S-, and -NH-. May be),
Each of n ¹ to n ⁶ independently represents an integer of 0 to 10000.
X ¹ to X ⁶ each independently represent an unsaturated bond group to which a hydrogen atom or two or more electron-withdrawing groups are bonded, and at least two of X ₁ to X ₆ have the two or more electron-withdrawing groups. Represents a bound unsaturated bond group. )

（上記一般式中、＊はＬ¹～Ｌ⁶に結合する結合手を表す） In the above general formula (6), examples of the mesogen group having a hexavalent aromatic ring include (e-1) to (e-3).

(In the above general formula, * represents a bond that binds to L ¹ to L ⁶ )

(Manufacturing method of macromonomer)
Hereinafter, an example of a method for producing a macromonomer according to the present invention will be described.
When the macromonomer according to the present invention has a mesogen group having a 2- to hexavalent aromatic ring, it is preferable to have the reaction step (1).

The reaction step (1) includes a step (a) of mixing an aromatic compound having at least two vinyl groups and organic lithium to prepare a reaction mixture (1), and addition to the reaction mixture (1). A step (b) of mixing a polymerizable monomer to prepare a reaction mixture (2) and a step of mixing a hetero three-membered ring compound and the reaction mixture (2) to prepare a reaction mixture (3). It is preferable to have (c) and a step (d) of mixing a compound containing an unsaturated bond group to which two or more electron-withdrawing groups are bonded and the reaction mixture (3) to prepare a macromonomer. ..

In the present embodiment, the aromatic compound having at least two vinyl groups has 2 to 6 hydrogen atoms in the aromatic compound, and the vinyl group (CH ₂ = CR ^h − (R ^h is a hydrogen atom or the number of carbon atoms). A compound substituted with 1 to 5 alkyl groups).

The aromatic compound that can be used in this embodiment is not particularly limited, and benzene, naphthalene, azulene, anthracene, phenanthrene, pyrene, chrysene, naphthalene, triphenylene, acenaphthene, coronene, fluoranthene, fluoranthene, pentacene, perylene, etc. Examples thereof include pentaphene, picene, pyranthrene and anthrananthrene. Further, the aromatic compound may have a substituent such as a halogen or an alkyl group, if necessary. Therefore, an aromatic compound having at least two vinyl groups means that 2 to 6 hydrogen atoms in the above-exemplified aromatic compound are represented by a vinyl group (CH ₂ = CR ^h − (R ^h is a hydrogen atom or a carbon atom). A compound substituted with an alkyl group (number 1 to 5) is preferable.

In the present embodiment, the organolithium is not particularly limited as long as it can be used as a polymerization initiator, and examples thereof include organolithium as a small molecule compound or a solubilized oligomer. For example, organolithium composed of a carbon-lithium bond, organolithium composed of a nitrogen-lithium bond, organolithium composed of a tin-lithium bond, and the like can be mentioned.

Examples of the organic lithium having a carbon-lithium bond include n-butyllithium, sec-butyllithium, tert-butyllithium, n-hexyllithium, benzyllithium, phenyllithium, and stillbenlithium. Examples of the organic lithium composed of the nitrogen-lithium bond include lithium dimethylamide, lithium diethylamide, lithium dipropylamide, lithiumdi-n-hexylamide, lithium diisopropylamide, lithium hexamethyleneimide, lithium pyrrolidide, and lithium piperidide. , Lithium heptamethyleneimide, lithium morpholid and the like.

Further, in the present embodiment, as the organic lithium, not only the above-mentioned monoorganolithium but also polyfunctional organolithium may be used, or monoorganolithium and polyfunctional organolithium may be polymerized in combination. good.

Examples of the polyfunctional organolithium include 1,4-dilithiobutane, a reaction product of sec-butyllithium and diisopropenylbenzene, 1,3,5-trilithiobenzene, n-butyllithium and 1,3-butadiene and divinyl. Examples thereof include a reaction product of benzene, a reaction product of m-xylene and n-butyllithium, and a reaction product of n-butyllithium and a polyacetylene compound.

In the present embodiment, the addition polymerizable monomer is a conjugated diene-based monomer such as butadiene, isoprene, milsen, and farnesene; a styrene-based monomer unit such as styrene, α-methylstyrene, and paramethylstyrene; methyl ( (Meta) acrylate-based monomers such as meta) acrylate, ethyl (meth) acrylate, propyl (meth) acrylate, and butyl (meth) acrylate are preferable. Further, the addition-polymerizable monomer may be composed of two or more kinds of these monomers.

In the present embodiment, the hetero three-membered ring compound is preferably a compound having an oxylane ring or a compound having an aziridine ring, for example, ethylene oxide, propylene oxide, cyclohexene oxide, styrene oxide, epoxidized soybean oil, epoxidized natural rubber, and the like. Bisphenol A Diglycidyl Ether, Glycerin Triglycidyl Ether, N, N, N', N'-Tetraglycidyldiaminodiphenylmethane, Thiylan, Methyltyylan, Phenyltyylan, Ethylene Imine, Propylene Imine, N-Phenylethyleneimine, N- (β) -Cyanoethyl) ethyleneimine, 2,5-bis (1-aziridinyl) -p-benzoquinone can be mentioned.

In the present embodiment, examples of the compound containing an unsaturated bond group to which two or more electron-withdrawing groups are bonded include maleic anhydride, maleic acid diester, maleic acid monoester, fumaric acid diester, and fumaric acid monoester. Maleic acid diamide, maleic acid monoamide and maleimide are preferable. Further, the compound containing an unsaturated bond group to which two or more electron-withdrawing groups are bonded corresponds to an unsaturated bond group to which two or more electron-withdrawing groups are bonded in the macromonomer according to the present invention.

The first reaction scheme (an example of the reaction step (1)) is shown below as an example of the method for synthesizing the macromonomer according to the present invention. In the reaction step (1) of the present embodiment, the steps (a) and (b) are in step 1 in the first reaction scheme, and the steps (b) and (c) are in steps 2 and 3. d) corresponds to step 4, respectively.

(In the compound of step 4, R ¹ independently represents a hydrogen atom or an alkyl group having 1 to 10 carbon atoms, and m1 and m2 independently represent an integer of 0 to 10000.)

When the macromonomer according to the present invention has an alkylene group having 3 to 15 carbon atoms or less (however, -CH ₂ -CH _2- in the alkylene group may be substituted with -CH = CH-). Preferably has a reaction step (2).

The reaction step (2) is a step (f) of mixing an addition-polymerizable monomer and a polymerization initiator to prepare a reaction mixture (4), and an unsaturated bond to which two or more electron-withdrawing groups are bonded. It is preferable to have a step (g) of preparing a macromonomer by mixing the compound containing a group and the reaction mixture (4).
By reacting with a hetero three-membered ring compound in the above reaction step (b), a carbon anion is converted into a heteroatom anion, and then a functional group having an active hydrogen (for example, a hydroxyl group or an amino group) is obtained. The above electron-withdrawing group can be reacted with a compound containing an unsaturated bonding group in a desired form. When an attempt is made to react with a compound containing an unsaturated bond group to which two or more electron-withdrawing groups are bonded without going through the reaction step (b), a ketone group is generated by the reaction between the carbonyl group and the carbon anion. The reaction between the produced ketone and the unreacted carbon anion can produce a three-dimensional crosslinked structure, making it impossible to obtain the desired macromonomer structure.

In the above step (f), the reaction conditions are not particularly limited, but for example, an addition-polymerizable monomer and a radical polymerization initiator can be used for polymerization in a solvent.

In the present embodiment, examples of the radical polymerization initiator include peroxide-based initiators and azo-based initiators. Peroxide-based compounds and azo-based compounds having active hydrogen such as hydroxyl groups or amino groups are desirable. For example, by using hydrogen peroxide, a polymer having a hydroxyl group at the end can be produced. As a result, the compound containing the unsaturated bond group to which the hydroxyl group and two or more electron-withdrawing groups are bonded can be reacted, and the unsaturated bond group to which two or more electron-withdrawing groups are bonded can be introduced into the terminal portion. can.

Examples of the radical polymerization initiator include 2,2'-azobisisobutyronitrile, 2,2'-azobis- (2,4-dimethylvaleronitrile), and 2,2'-azobis- (4-methoxy). Azo compounds such as -2,4-dimethylvaleronitrile); benzoyl peroxide, lauroyl peroxide, t-butylperoxypivalate, t-butylperoxyethylhexanoate, 1,1'-bis- (t-butylperoxy). Examples thereof include organic peroxides such as cyclohexane, t-amylperoxy-2-ethylhexanoate and t-hexylperoxy-2-ethylhexanoate, and hydrogen peroxide. These may be used alone or in combination of two or more.

Examples of the solvent that can be used for radical polymerization in the above step (f) include acetone, methyl ethyl ketone, methyl-n-propyl ketone, methyl isopropyl ketone, methyl-n-butyl ketone, methyl isobutyl ketone, and methyl-n-amyl ketone. , Methyl-n-hexyl ketone, diethyl ketone, ethyl-n-butyl ketone, di-n-propyl ketone, diisobutyl ketone, cyclohexanone, holon and other ketone solvents; ethyl ether, isopropyl ether, n-butyl ether, diisoamyl ether, Ethereal solvents such as ethylene glycol dimethyl ether, ethylene glycol diethyl ether, diethylene glycol dimethyl ether, diethylene glycol, dioxane, and tetrahydrofuran; ethyl formate, propyl formate, -n-butyl formate, ethyl acetate, -n-propyl acetate, isopropyl acetate, -n acetate. -Esters such as butyl, acetate-n-amyl, ethylene glycol monomethyl ether acetate, ethylene glycol monoethyl ether acetate, diethylene glycol monomethyl ether acetate, diethylene glycol monoethyl ether acetate, propylene glycol monomethyl ether acetate, ethyl-3-ethoxypropionate, etc. Solvents: Alcohol-based solvents such as methanol, ethanol, isopropyl alcohol, n-butyl alcohol, isobutyl alcohol, diacetone alcohol, 3-methoxy-1-propanol, 3-methoxy-1-butanol, 3-methyl-3-methoxybutanol, etc. , Toluene, o-xylene, m-xylene, p-xylene, ethylbenzene, propylbenzene, vinylbenzene, p-methylvinylbenzene and other aromatic solvents and the like. These solvents may be used alone or in combination of two or more.

In the present embodiment, examples of the compound containing an unsaturated bond group to which two or more electron-withdrawing groups are bonded include maleic anhydride, maleic acid diester, maleic acid monoester, fumaric acid diester, and fumaric acid monoester. Maleic acid diamide, maleic acid monoamide and maleimide are preferable. Further, the compound containing an unsaturated bond group to which two or more electron-withdrawing groups are bonded corresponds to an unsaturated bond group to which two or more electron-withdrawing groups are bonded in the macromonomer according to the present invention.
In the present embodiment, the reaction conditions may be either under an air atmosphere or under an inert gas atmosphere.
In the above step (g), the method for introducing an unsaturated bond group to which two or more electron-withdrawing groups are bonded is not particularly limited, and an esterification reaction using an acid anhydride group and an ester group are used. Examples thereof include an ester exchange reaction, an esterification reaction using a carboxyl group, an amidation reaction using an acid anhydride group, and a maleimization reaction using an acid anhydride group.
In the step (g), the water content in the reaction mixture is preferably 0.1 part by mass or less from the viewpoint of efficiently advancing the reaction.
In the step (g), the reaction temperature is preferably 0 ° C to 150 ° C. When the reaction temperature is lower than 0 ° C, the viscosity of the reaction system becomes high, the diffusion of the compound containing the unsaturated bond group to which two or more electron-withdrawing groups are bonded becomes slow, the reaction does not proceed easily, and the reaction is higher than 150 ° C. At a temperature, unsaturated bonding groups to which two or more electron-withdrawing groups are bonded in the macromonomer may react with each other, making it impossible to obtain a macromonomer having a desired structure, which is not preferable.
Examples of the solvent that can be used for the reaction in the above step (g) include acetone, methyl ethyl ketone, methyl-n-propyl ketone, methyl isopropyl ketone, methyl-n-butyl ketone, methyl isobutyl ketone, and methyl-n-amyl ketone. , Methyl-n-hexyl ketone, diethyl ketone, ethyl-n-butyl ketone, di-n-propyl ketone, diisobutyl ketone, cyclohexanone, holon and other ketone solvents; ethyl ether, isopropyl ether, n-butyl ether, diisoamyl ether, Ethereal solvents such as ethylene glycol dimethyl ether, ethylene glycol diethyl ether, diethylene glycol dimethyl ether, diethylene glycol, dioxane, and tetrahydrofuran; ethyl formate, propyl formate, -n-butyl formate, ethyl acetate, -n-propyl acetate, isopropyl acetate, -n acetate. -Esters such as butyl, acetate-n-amyl, ethylene glycol monomethyl ether acetate, ethylene glycol monoethyl ether acetate, diethylene glycol monomethyl ether acetate, diethylene glycol monoethyl ether acetate, propylene glycol monomethyl ether acetate, ethyl-3-ethoxypropionate, etc. Examples thereof include solvents, aromatic solvents such as toluene, o-xylene, m-xylene, p-xylene, ethylbenzene, propylbenzene, vinylbenzene and p-methylvinylbenzene. These solvents may be used alone or in combination of two or more.
In the reaction step (g), a polymerization inhibitor can be used from the viewpoint of preventing the polymerization of the macromonomer during the reaction. Specific examples of the polymerization inhibitor include 4-hydroxy-2,2,6,6-tetramethylpiperidine-N-oxyl and 4-acetamino-2,2,6,6-tetramethylpiperidine-N-oxyl, 4 -Benzoxy-2,2,6,6-tetramethylpiperidine-N-oxyl, 4-oxo-2,2,6,6-tetramethylpiperidine-N-oxyl, 2,2,6,6-tetramethylpiperidine N-oxy radical compounds such as -N-oxyl; hydroquinone, hydroquinone monomethyl ether, 2,6-di-t-butyl-4-methylphenol, 2,2'-methylenebis (4-ethyl-6-t-butylphenol) ), 2,6-di-t-butyl-N, N-dimethylamino-p-cresol, 2,4-methyl-6-t-butylphenol, 4-t-butylcatechol, 4,4'-thio-bis Phenolic compounds such as (3-methyl-6-t-butylphenol), 4,4'-butylidene-bis (3-methyl-6-t-butylphenol); benzoquinone, 2,5-di-t-butylhydroquinone, etc. Kinone-based compounds; Copper compounds such as cuprous chloride and copper dimethyldithiocarbamate can be mentioned. These may be used alone or in combination of two or more.
In the present embodiment, examples of the radical polymerization initiator that can be used in the copolymerization of the vinyl-based monomer and the macromonomer include a peroxide-based initiator and an azo-based initiator. Examples of the radical polymerization initiator include 2,2'-azobisisobutyronitrile, 2,2'-azobis- (2,4-dimethylvaleronitrile), and 2,2'-azobis- (4-methoxy). Azo compounds such as -2,4-dimethylvaleronitrile); benzoyl peroxide, lauroyl peroxide, t-butylperoxypivalate, t-butylperoxyethylhexanoate, 1,1'-bis- (t-butylperoxy). Examples thereof include organic peroxides such as cyclohexane, t-amylperoxy-2-ethylhexanoate and t-hexylperoxy-2-ethylhexanoate, and hydrogen peroxide. These may be used alone or in combination of two or more.

（上記式（２－５）中、ｍ０、ｍ１及びｍ２はそれぞれ独立して、０～１００００の整数を表す。）
以上、本発明の実施形態を説明したが、本発明は、上記例に限定されることは無く、適宜変更を加えることができる。 A second reaction scheme (an example of the reaction step (2)) is shown below as an example of the method for synthesizing the macromonomer according to the present invention. In the reaction step (2) of the present embodiment, the step (f) corresponds to steps 1 to 3 in the second reaction scheme, and the step (g) corresponds to step 4.

(In the above equation (2-5), m0, m1 and m2 each independently represent an integer of 0 to 10000.)
Although the embodiments of the present invention have been described above, the present invention is not limited to the above examples and can be appropriately modified.

Hereinafter, the present invention will be specifically described with reference to Examples and Comparative Examples, but the present invention should not be understood to be limited to these Examples.
First, the evaluation method used to evaluate the examples and comparative examples will be described below.
"Evaluation methods"
(1) Measurement of number average molecular weight Mn, weight average molecular weight Mw, z average molecular weight Mz The number average molecular weight (Mn) and weight average molecular weight of the obtained macromonomer and the copolymer of the vinyl-based monomer and the macromonomer (Mn). Mw) and z average molecular weight (Mz) were measured under the following conditions using gel permeation chromatography (GPC).
Sample preparation: Dissolve styrene-based copolymer resin in tetrahydrofuran so as to be about 0.05% by mass Measurement conditions Equipment: TOSOH HLC-8220GPC
(Gel Permeation Chromatography)
Column: super HZM-H
Temperature: 40 ° C
Carrier: THF 0.35 mL / min
Detector: RI, UV: 254nm
Calibration curve: Uses standard PS made by TOSOH

(2) Quantification of the terminal functional group ratio of the macromonomer The terminal functional group ratio of the polymer having the macromonomer and its raw material, both terminal diols, is determined from the integral ratio of the spectrum measured by the nuclear magnetic resonance ( ¹ H-NMR) device. Quantified. Sample preparation: 75 mg of macromonomer was dissolved in 0.75 mL of d3-chloroform at room temperature.
Measuring equipment: JNM ECA-500 manufactured by JEOL Ltd.
Measurement conditions: Measurement temperature 60 ° C, observation nucleus 1H, integration frequency 256 times, repetition time 45 seconds

"material"
"Example 1"
Synthesis of polyisoprene main chain macromonomer (macromonomer A) Polyisoprene diol polyip was placed in a 200 g flask, 20 g of maleic anhydride and 0.1 g of the antioxidant tertiary butylcatechol were added thereto, and the oil was heated to 70 ° C. The flask was immersed in a bath and stirred. After the reaction time had elapsed 6 hours, the oil bath was taken out and the reaction was stopped. When the reduction rate of the hydroxyl group of the polybutadiene diol was measured by ¹ H-NMR, it was 98%, and it was confirmed that the reaction proceeded almost quantitatively.

"Example 2"
Synthesis of hydrogenated polyisoprene main chain macromonomer (macromonomer B) Hydrogenated polyisoprene diol Epol was placed in a 200 g flask, 20 g of maleic anhydride and 0.1 g of antioxidant tertiary butyl catechol were added to the flask, and the temperature was adjusted to 70 ° C. The flask was immersed in a heated oil bath and stirred. After the reaction time had elapsed 6 hours, the oil bath was taken out and the reaction was stopped. The rate of decrease in the hydroxyl group of the hydrogenated polyisoprene diol was measured by ¹ H-NMR and found to be 97%, confirming that the reaction was proceeding almost quantitatively.

"Example 3"
Synthesis of polyisoprene backbone macromonomer (by anionic polymerization) (macromonomer C) <Preparation of reagents>
Isoprene (manufactured by Tokyo Chemical Industry Co., Ltd.), Cyclohexane (manufactured by Fuji Film Wako Pure Chemical Industry Co., Ltd.), 1,3-diisopropylbenzene (manufactured by Tokyo Chemical Industry Co., Ltd.), Tetramethylethylenediamine (manufactured by Fuji Film Wako Pure Chemical Industry Co., Ltd.), TMEDA), triethylamine (manufactured by Tokyo Chemical Industry Co., Ltd., hereinafter TEA), butylene oxide (manufactured by Tokyo Chemical Industry Co., Ltd.) are alumina granules (manufactured by Fuji Film Wako Pure Chemical Industry Co., Ltd.) dried by heating at 200 ° C. After allowing to cool to room temperature in a desiccator, polymerization of 10% or more of the liquid amount of each compound was added and dehydration was performed. As s-butyllithium (1.3 mol / L hexane-cyclohexane solution, manufactured by Fuji Film Wako Pure Chemical Industries, Ltd.), the purchased one was used as it was.
<Solution adjustment>
The following solutions A to E were prepared for polymerization.
(Solution A) 5.0 mL of cyclohexane and 1.5 mL of TEA were added to the flask and stirred with a stirrer to prepare a uniform solution.
(Solution B) 6.0 mL of cyclohexane and 1.0 mL of diisopropylbenzene were added to the flask and stirred with a stirrer to prepare a uniform solution.
(Solution C) 9.0 mL of cyclohexane and 0.30 mL of TMEDA were added to the flask and stirred with a stirrer to prepare a uniform solution.
(Solution D) 45.0 mL of cyclohexane and 7.5 mL of isoprene were added to the flask and stirred by stirring to prepare a uniform solution.
(Solution E) 5.0 mL of cyclohexane and 5.0 mL of ethylene oxide (0.8 mol / L hexane solution) were added to the flask, and the mixture was stirred to obtain a uniform solution.

"Preparation of initiator solution"
13.0 mL of cyclohexane and 3.0 mL of s-butyllithium solution were added to the flask and stirred by stirring to prepare a uniform solution. Then, 2.0 mL of the solution A was added, 1.8 mL of the solution B was further added, the temperature of the flask was raised to 50 ° C. in a heated oil bath, and the reaction was carried out for 2 hours to prepare an initiator solution.

"Anionic polymerization"
0.41 mL of the initiator solution was added to the flask, 0.157 mL of the solution C was added, and the mixture was reacted for 10 minutes with stirring to prepare a mixed solution (1) (reaction mixture (1)). 10.0 mL of solution D was added to the mixture (1), and the mixture was reacted at 25 ° C. for 2 hours. Then, 1.2 mL of the initiator solution was added, and the mixture was further reacted at 25 ° C. for 10 minutes to prepare a mixed solution (2) (reaction mixture (2)). Then, 0.7 mL of solution E was added to the mixed solution (2), and the mixture was further reacted for 10 minutes. Then, 1.0 mL of the degassed mixed solvent of methanol / tetrahydrofuran = 1/1 (wt / wt) was added to stop the reaction. Hereinafter, this solution is referred to as a solution after polymerization is stopped (reaction mixture (3)).
"Recovery process"

300 mL of methanol, which is a poor solvent, was placed in a beaker, and a polymerization termination solution was added dropwise thereto using a dropper. The solution became cloudy with the dropping. After the dropping was completed, the mixture was allowed to stand for 12 hours, and a precipitate was deposited on the bottom of the beaker. The supernatant was removed and dried in a desiccator to obtain polyisoprene bilateral terminal diols. When the molecular weight was measured by GPC, it was found that Mn = 20000 (PS conversion). Moreover, according to the analysis by ¹ H-NMR, the hydroxyl group introduction rate was 98%.

"Maleic acid esterification reaction step (step (g))"
0.10 g of the polyisoprene both-terminal diol, 0.5 mg of maleic anhydride, 0.05 mg of paramethoxyphenol, and 0.90 g of ethylbenzene were weighed and added to a flask equipped with a stirrer. It was immersed in an oil bath heated to 80 ° C. and reacted for 6 hours.
When the molecular weight was measured by GPC, it was found that Mn = 20200 (PS conversion). Moreover, according to the analysis by ¹ H-NMR, the hydroxyl group was consumed by 99%, and the introduction rate of the maleic acid ester was 99%.

"Example 4"
0.040 g of 2,2-bis (4,4-di-t-butylperoxycyclohexyl) propane (hereinafter referred to as Pertetra A), 83.86 g of styrene, and ethylbenzene as an initiator in a flask equipped with a three-way cock. 16.00 g and 0.10 g of macromonomer A were taken and the solution was made uniform with a stirrer. This was immersed in an oil bath set at 100 ° C. and reacted for 6 hours. When this solution was dried in a vacuum dryer set at 230 ° C. for 10 minutes under high vacuum to remove volatile components, a colorless and transparent resin was obtained. Table 1 shows the evaluation results obtained by the above-mentioned production method.

"Example 5"
0.040 g of Pertetra A, 83.86 g of styrene, 16.00 g of ethylbenzene and 0.10 g of macromonomer B were placed in a flask equipped with a three-way cock, and the solution was made uniform with a stirrer. This was immersed in an oil bath set at 100 ° C. and reacted for 6 hours. When this solution was dried in a vacuum dryer set at 230 ° C. for 10 minutes under high vacuum to remove volatile components, a colorless and transparent resin was obtained. Table 1 shows the evaluation results obtained by the above-mentioned production method.

"Example 6"
0.040 g of Pertetra A, 83.86 g of styrene, 16.00 g of ethylbenzene and 0.10 g of macromonomer C were placed in a flask equipped with a three-way cock, and the solution was made uniform with a stirrer. This was immersed in an oil bath set at 100 ° C. and reacted for 6 hours. When this solution was dried in a vacuum dryer set at 230 ° C. for 10 minutes under high vacuum to remove volatile components, a colorless and transparent resin was obtained. Table 1 shows the evaluation results obtained by the above-mentioned production method.

"Example 7"
In a flask equipped with a three-way cock, take 0.040 g of 1,1-di-t-butylperoxycyclohexane (hereinafter referred to as perhexa C), 99.96 g of styrene, and 0.10 g of macromonomer C as an initiator and stir. The solution was homogenized by the child. This was immersed in an oil bath set at 100 ° C. and reacted for 3 hours. When this solution was dried in a vacuum dryer set at 230 ° C. for 10 minutes under high vacuum to remove volatile components, a colorless and transparent resin was obtained. Table 1 shows the evaluation results obtained by the above-mentioned production method.

"Example 8"
0.040 g of perhexa C, 99.96 g of styrene and 0.10 g of macromonomer C were placed in a flask equipped with a three-way cock, and the solution was made uniform with a stirrer. This was immersed in an oil bath set at 100 ° C. and reacted for 6 hours. When this solution was dried in a vacuum dryer set at 230 ° C. for 10 minutes under high vacuum to remove volatile components, a colorless and transparent resin was obtained. Table 1 shows the evaluation results obtained by the above-mentioned production method.

"Comparative Example 1"
0.040 g of Pertetra A, 83.86 g of styrene and 16.00 g of ethylbenzene were placed in a flask equipped with a three-way cock, and the solution was made uniform with a stir bar. This was immersed in an oil bath set at 100 ° C. and reacted for 6 hours. When this solution was vacuum-dried for 10 minutes in a vacuum dryer set at 230 ° C. to remove volatile components, a colorless and transparent resin was obtained. Table 1 shows the evaluation results obtained by the above-mentioned production method. This Comparative Example 1 is used as a reference experimental result in which no macromonomer is present.

"Comparative Example 2"
0.040 g of Pertetra A, 83.86 g of styrene, 16.00 g of ethylbenzene and 0.10 g of polyisoprene diol were placed in a flask equipped with a three-way cock, and the solution was made uniform with a stirrer. This was immersed in an oil bath set at 100 ° C. and reacted for 6 hours. When this solution was vacuum-dried for 10 minutes in a vacuum dryer set at 230 ° C. to remove volatile components, a colorless and transparent resin was obtained. Table 1 shows the evaluation results obtained by the above-mentioned production method. Since the maleic acid ester was not present at the terminal, the additive did not copolymerize with styrene, and the molecular weight was the same as that of Comparative Example 1. Furthermore, under these conditions, the progress of copolymerization could not be confirmed in the double bond in polyisoprene.

"Comparative Example 3"
0.040 g of Pertetra A, 83.86 g of styrene, 16.60 g of ethylbenzene and 0.10 g of polyisoprene acrylate were placed in a flask equipped with a three-way cock, and the solution was made uniform with a stirrer. This was immersed in an oil bath set at 100 ° C. and reacted for 6 hours. When this solution was vacuum-dried for 10 minutes in a vacuum dryer set at 230 ° C. to remove volatile components, a colorless and transparent resin was obtained. Table 1 shows the evaluation results obtained by the above-mentioned production method.
As shown in the evaluation results, the Mw and Mz of the resin of Comparative Example 3 were larger than those of Comparative Examples 1 and 2, but smaller than those of Example 4. From this result, it is possible to promote the copolymerization with styrene more easily in the macromonomer having a double bond in which two electron-withdrawing substituents are bonded, and to efficiently increase the PS molecular weight with the same addition amount. It has been shown.

"Comparative Example 4"
0.040 g of Perhexa C, 99.96 g of styrene and 0.10 g of polyisoprene acrylate were placed in a flask equipped with a three-way cock, and the solution was made uniform with a stirrer. This was immersed in an oil bath set at 100 ° C. and reacted for 3 hours. When this solution was dried in a vacuum dryer set at 230 ° C. for 10 minutes under high vacuum to remove volatile components, a colorless and transparent resin was obtained. Table 1 shows the evaluation results obtained by the above-mentioned production method.
As shown in the evaluation results, both Mw and Mz of the copolymer using the macromonomer of Comparative Example 4 were smaller than those of Example 7.

"Comparative Example 5"
0.040 g of Perhexa C, 99.96 g of styrene and 0.10 g of polyisoprene acrylate were placed in a flask equipped with a three-way cock, and the solution was made uniform with a stirrer. This was immersed in an oil bath set at 100 ° C. and reacted for 6 hours. When this solution was dried in a vacuum dryer set at 230 ° C. for 10 minutes under high vacuum to remove volatile components, a colorless and transparent resin was obtained. Table 1 shows the evaluation results obtained by the above-mentioned production method.
As shown in the evaluation results, both Mw and Mz of the copolymer using the macromonomer of Comparative Example 5 were smaller than those of Example 8.

(Relationship between reaction time and Mz)
Further, with respect to the experimental results of Example 7, Example 8, Comparative Example 4, and Comparative Example 5, a graph in which the reaction time is plotted on the horizontal axis and Mz is plotted on the vertical axis is shown in FIG.
As shown in the experimental results of FIG. 1, when the polyisoprene acrylates of Comparative Examples 4 and 5 were used, the molecular weight (interpolated value) reached in the polymerization reaction time of 4.2 hours was 80 × 10 ⁴ . On the other hand, it was found that when the macromonomers C of Examples 7 and 8 were used, the reaction time to reach the molecular weight was shortened to 3 hours (reduced by about 1.2 hours). That is, it was found that the macromonomer C has high copolymerizability with styrene and the production rate can be increased to 140%.

The macromonomer according to the present invention can be widely used as a cross-linking agent, an adhesive, a sealing material for electronic materials, etc. in copolymerization with an addition-polymerizable monomer.

Claims (5)

A macromonomer having at least one unsaturated bond group to which two or more electron-withdrawing groups are bonded at the terminal portion and containing an addition-polymerizable monomer unit as a main chain. Organic groups with 2- to hexavalent bonds and
The following general formula (I) that directly bonds to the bond of the organic group

(In the above general formula (I), L is a single bond or an alkylene group having 1 to 10 carbon atoms (however, -CH _2- in the alkylene group is not adjacent to each other, -O-, -S- , Or may be substituted with -NH-, and -CH ₂ -CH _2- in the alkylene group may be substituted with -CH = CH-).
M represents an addition-polymerizable monomer unit and represents
Z represents a single bond or an alkylene group having 1 to 10 carbon atoms (however, -CH _2- in the alkylene group may be substituted with -O-, -S-, -NH-).
n represents the degree of polymerization
X represents an unsaturated bond group to which two or more electron-withdrawing groups are bonded. * In the general formula (I) represents a bond with an atom contained in the organic group. )
The macromonomer according to claim 1, which has up to 6 types of groups represented by and has 1 or more unsaturated bonding groups to which the 2 or more electron-withdrawing groups are bonded. The organic group is a mesogen group having an aromatic ring or an alkylene group having 3 to 15 carbon atoms or less (provided that -CH ₂ -CH _2- in the alkylene group is replaced with -CH = CH-. The macromonomer according to claim 1 or 2, which represents good). The macromonomer according to any one of claims 1 to 3, which is represented by the following general formula (1).

(In the above general formula (1),
B ¹ represents an organic group having a 2- to hexavalent bond.
L is a single bond or an alkylene group having 1 to 10 carbon atoms (however, -CH _2- in the alkylene group is substituted with -O-, -S-, or -NH- so as not to be adjacent to each other. In addition, -CH ₂ -CH _2- in the alkylene group may be substituted with -CH = CH-).
M represents an addition-polymerizable monomer unit and represents
Z represents a single bond or an alkylene group having 1 to 10 carbon atoms (however, -CH _2- in the alkylene group may be substituted with -O-, -S-, -NH-).
n represents an integer from 0 to 10000 and represents
X represents an unsaturated bond group to which a hydrogen atom or two or more electron-withdrawing groups are bonded, and at least one of the k existing Xs is an unsaturated bond to which the two or more electron-withdrawing groups are bonded. Is the basis and
k represents an integer of 2 or more and 6 or less. It should be noted that L, M, Z and X, which are present in a plurality in the general formula (1), may be independent of each other and may be the same or different from each other. ) The macromonomer according to any one of claims 1 to 4, which is represented by the following general formula (2).

(In the above general formula (2), B ² is a mesogen group having a divalent aromatic ring or an alkylene group having 3 to 15 carbon atoms or less (however, -CH ₂ -CH _2-- in the alkylene group is , -CH = CH- may be replaced),
L ¹ and L ² are independently alkylene groups having 1 to 10 carbon atoms (however, even if -CH _2- in the alkylene group is replaced with -O-, -S-, -NH-. Good),
M ¹ and M ² each independently represent an addition-polymerizable monomer unit, and Z ¹ to Z ² independently represent an alkylene group having 1 to 10 carbon atoms (however,-in the alkylene group). CH ₂ -represents (may be replaced with -O-, -S-, -NH-).
n ¹ and n ² each independently represent an integer from 1 to 10000.
X ¹ and X ² each independently represent an unsaturated bond group to which a hydrogen atom or two or more electron-withdrawing groups are bonded, and at least one of X ¹ to X ² has the two or more electron-withdrawing groups. Represents a bound unsaturated binding group. )

Images