JP7638642B2 - Macromonomer and polymer using said macromonomer - Google Patents

Description

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

Polystyrene, polyolefins, and (meth)acrylic polymers, which are widely used as molding materials or food packaging materials for home appliances, office equipment, miscellaneous goods, and housing equipment, are generally produced industrially using addition polymerization (chain polymerization) by copolymerizing vinyl monomers as raw materials with various monomers as necessary. Such addition polymerization is classified as cationic polymerization, anionic polymerization, radical polymerization, etc., and by the attributes of the growing end, and polymerization proceeds by repeated growth reactions of growing ends with monomers that have a specific chemical structure and properties.

Patent Documents 1 and 2 are examples of techniques related to addition polymerization. Patent Document 1 discloses a highly branched styrene-based resin composition that has an excellent balance between melt tension and melt extensibility by containing a highly branched ultra-high molecular weight copolymer obtained by copolymerizing a multifunctional vinyl copolymer with styrene. Patent Document 2 discloses a styrene-based copolymer that contains a specified conjugated divinyl compound and a specified monovinyl compound in an appropriate content ratio, and discloses that this makes it possible to provide a styrene-based copolymer that has excellent moldability and little gel-like material.

JP2013-100432A JP 2017-218575 A

However, the vinyl groups present in the multifunctional vinyl copolymer described in Patent Document 1 are aromatic vinyl groups, and there is a drawback in that the rate of branched polystyrene formation during copolymerization with styrene in the production of branched polystyrene is slow, resulting in low productivity. In addition, since the conjugated vinyl groups in the conjugated divinyl compound described in Patent Document 2 are (meth)acrylate groups, it has been found that there is room for further improvement in copolymerizability.

Therefore, the present invention aims to solve the above problems by providing a novel macromonomer that has a fast reaction rate, can efficiently impart a branched structure through copolymerization, and improves the productivity of branched polymers.

As a result of intensive research conducted by the inventors to achieve the above object, they discovered that the above problems could be solved by a macromonomer having at least one type of unsaturated bond group at the end to which two or more electron-withdrawing groups are bonded and containing addition-polymerizable monomer units as the main chain, and thus completed the present invention. That is, the present invention is as follows.

[1] This embodiment is a macromonomer that has at least one type of unsaturated bond group at the end to which two or more electron-withdrawing groups are bonded, and contains addition-polymerizable monomer units as the 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 this embodiment, an organic group having a valence of 2 to 6,
The following general formula (I) is directly bonded to the bond of the organic group:

(In the above general formula (I), L represents a single bond or an alkylene group having 1 to 10 carbon atoms (wherein, -CH ₂ - in the alkylene group may be replaced with -O-, -S-, or -NH- so as not to be adjacent to each other, and further, -CH ₂ -CH ₂ - in the alkylene group may be replaced with -CH═CH-),
M represents an addition polymerizable monomer unit;
Z represents a single bond or an alkylene group having 1 to 10 carbon atoms (wherein —CH ₂ — in the alkylene group may be replaced by —O—, —S— or —NH—);
n represents the degree of polymerization;
X represents a hydrogen atom or an unsaturated bond group to which two or more electron-withdrawing groups are bonded. * in the general formula (I) represents a bond to an atom contained in the organic group.
It is preferable that the aryl group has up to six kinds of groups represented by the following formula:

[3] In this embodiment, the organic group preferably represents a mesogenic group having a divalent to hexavalent aromatic ring or an alkylene group having 3 to 15 carbon atoms (wherein _-CH2 - _CH2- in the alkylene group may be replaced by -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 this embodiment is preferably represented by the following general formula (1).

(In the above general formula (1),
B ¹ represents an organic group having a valence of 2 to 6;
L represents a single bond or an alkylene group having 1 to 10 carbon atoms (provided that -CH ₂ - in the alkylene group may be replaced with -O-, -S- or -NH- so as not to be adjacent to each other, and further -CH ₂ -CH ₂ - in the alkylene group may be replaced with -CH═CH-);
M represents an addition polymerizable monomer unit;
Z represents a single bond or an alkylene group having 1 to 10 carbon atoms (wherein —CH ₂ — in the alkylene group may be replaced by —O—, —S— or —NH—);
n represents an integer from 0 to 10,000;
X represents a hydrogen atom or an unsaturated bond group having two or more electron-withdrawing groups bonded thereto, and at least one of the k X's is an unsaturated bond group having two or more electron-withdrawing groups bonded thereto;
k represents an integer of 2 or more and 6 or less. In addition, L, M, Z and X present in general formula (1) may be independently 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 this embodiment is preferably represented by the following general formula (2).

(In the above general formula (2), ^B2 represents an alkylene group having 3 to 15 carbon atoms (wherein _--CH2 -- _CH2-- in the alkylene group may be replaced with --CH=CH--),
^L1 and ^L2 each independently represent an alkylene group having 1 to 10 carbon atoms (wherein _-CH2- in the alkylene group may be replaced by -O-, -S- or -NH-);
M ¹ and M ² each independently represent an addition polymerizable monomer unit, Z ¹ and Z ² each independently represent an alkylene group having 1 to 10 carbon atoms (wherein -CH ₂ - in the alkylene group may be substituted with -O-, -S- or -NH-),
ⁿ¹ and ⁿ² each independently represent an integer from 1 to 10,000;
^X1 and ^X2 each independently represent a hydrogen atom or an unsaturated bond group having two or more electron-withdrawing groups bonded thereto, and at least one of ^X1 to ^X2 represents an unsaturated bond group having two or more electron-withdrawing groups bonded thereto.

According to the present invention, it is possible to efficiently impart a branched structure through copolymerization, thereby improving the productivity of branched polymers.

FIG. 1 is a graph showing the relationship between reaction time and Mz in the examples and comparative examples.

The following describes in detail an embodiment of the present invention (hereinafter referred to as the "present embodiment"); however, the present invention is not limited to the following description and can be modified in various ways within the scope of the gist of the present invention.

The present invention relates to a macromonomer having at least one type of unsaturated bond group at the terminal end to which two or more electron-withdrawing groups are bonded, and containing addition-polymerizable monomer units as the main chain.
By having an unsaturated bond group to which two or more electron-withdrawing groups are bonded at the end, copolymerization with vinyl monomers, particularly styrene monomer units, is easily promoted. 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 to carry out copolymerization, but in order to be able to carry out copolymerization even with a small amount of macromonomer, it is advantageous, particularly in the case of styrene, to have a functional group with high alternating copolymerizability. In this specification, "easily promoted copolymerization" means that copolymerization proceeds even when a small amount of macromonomer is added.

In this specification, the term "addition polymerizable monomer unit" refers to a monomer unit that polymerizes by cleaving an unsaturated bond, and includes, for example, radical and anion polymerizable monomer units. In addition, in this specification, the term "monomer unit" refers to a repeating unit in a polymer obtained by polymerizing a monomer, and for example, a "styrene-based monomer unit" refers to a structural unit in which an unsaturated double bond in a styrene-based monomer becomes a single bond through a polymerization reaction or a crosslinking reaction. Specific examples of addition polymerizable monomers include conjugated diene-based monomers such as butadiene, isoprene, myrcene, and farnesene; styrene-based monomers such as styrene, α-methylstyrene, and para-methylstyrene; and (meth)acrylate-based monomers such as methyl (meth)acrylate, ethyl (meth)acrylate, propyl (meth)acrylate, and butyl (meth)acrylate. In addition, the addition polymerizable monomer may be composed of two or more of these monomers.

In this specification, the term "unsaturated bond group having two or more electron-withdrawing groups bonded thereto" refers to a group in which a substituent that is easily negatively charged due to the induction effect or resonance effect is covalently bonded to a carbon atom that constitutes a carbon-carbon unsaturated bond group. Examples of such substituents 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 the unsaturated bond group 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, maleic acid monoamide, and maleimide. From the viewpoint of high reactivity with styrene-based monomers, maleic acid diester or maleic acid monoester is preferred. Moreover, the unsaturated bond group may be either E-form or Z-form.
In the present invention, the unsaturated bond group having two or more electron-withdrawing groups bonded thereto 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, a -NHR ^a group, or a -R ^a O group (R ^a represents a hydrogen atom or an alkyl group having 1 to 10 carbon atoms), and W ² represents -NH-, -NR ^b- , -N=, or -O-(R ^b ) _q (R ^b represents an alkylene group having 1 to 10 carbon atoms, and q represents an integer of 0 to 1). However, when W ¹ is a single bond, W ² may be -N=, and W ¹ and W ² may be bonded to form a maleimide. * in general formula (i) represents a bond to the molecular chain that is the main chain.)
In the above general formula (i), R ^a is preferably a hydrogen atom, a methyl group, an ethyl group, or a linear or branched propyl group.

In the present invention, suitable examples of the unsaturated bond group having two or more electron-withdrawing groups bonded thereto include the following formulas (i-1) to (i-17), and among them, (i-1) to (i-9) are preferred from the viewpoint of high reactivity with vinyl monomers.

In this specification, the term "terminal" can be the position at the very end of the molecular chain, but if an unsaturated bond group to which two or more electron-withdrawing groups are bonded is present near the terminal (or near the terminal), the frequency of collision between the unsaturated bond group and the polymer radical required for reaction increases, and the unsaturated bond group has effective reactivity with the vinyl monomer. Therefore, in this embodiment, the term "terminal" can also be a portion (end portion) that is in the molecular chain and includes the position (atom) at the very end of the molecular chain (in other words, the unsaturated bond group to which two or more electron-withdrawing groups are bonded can be located near the terminal). The portion that is in a certain range is not limited, but is preferably 10% or less of the extended chain length of the molecular chain extending from the center of this macromonomer, more preferably 5% or less, even more preferably 3% or less, and even more preferably 1% or less.

The number average molecular weight (Mn) of the macromonomer according to the present invention is preferably from 1,000 to 200,000, more preferably from 5,000 to 150,000, and even more preferably from 10,000 to 100,000. The number average molecular weight (Mn) of the macromonomer was measured under the conditions described in the Examples section below.
The macromonomer according to the present invention comprises an organic group having a valence of 2 to 6, and a compound represented by the following general formula (I) which is directly bonded to the bond of the organic group:

(In the above general formula (I), L represents a single bond or an alkylene group having 1 to 10 carbon atoms (wherein, -CH ₂ - in the alkylene group may be replaced with -O-, -S- or -NH- so as not to be adjacent to each other, and further, -CH ₂ -CH ₂ - in the alkylene group may be replaced with -CH═CH-),
M represents an addition polymerizable monomer unit;
Z represents a single bond or an alkylene group having 1 to 10 carbon atoms (wherein —CH ₂ — in the alkylene group may be replaced by —O—, —S— or —NH—);
n represents the degree of polymerization;
X represents a hydrogen atom or an unsaturated bond group to which two or more electron-withdrawing groups are bonded. * in the general formula (I) represents a bond to an atom contained in an organic group.
and preferably has, in one molecule, at least one type of unsaturated bond group to which two or more electron-withdrawing groups are bonded.
In the macromonomer according to the present invention, the number of groups represented by general formula (I) is the same as the valence of the organic group having a valence of 2 to 6. The macromonomer according to the present invention preferably has at least one type of unsaturated bond group having two or more electron-withdrawing groups bonded thereto in one molecule of the macromonomer (in other words, has at least one type of group represented by the above general formula (I) that satisfies the condition that X is an unsaturated bond group having two or more electron-withdrawing groups bonded thereto), and contains M, which is an addition polymerizable monomer unit, as the main chain.

The organic group in general formula (I) refers to a hydrocarbon group in which carbon atoms are covalently bonded to each other, and the organic group having divalent to hexavalent bonds preferably represents a mesogenic group having an aromatic ring having divalent to hexavalent bonds, an alkylene group having 3 to 15 carbon atoms (wherein _-CH2 - _CH2- in the alkylene group may be replaced by -CH=CH-), or a group in which 0 to 4 hydrogen atoms have been removed from the alkylene group.

In this embodiment, the term "organic group having a divalent to hexavalent bond" refers to an atomic group obtained by removing 0 to 4 hydrogen atoms from a divalent organic group, and is preferably a group obtained by removing 0 to 4 hydrogen atoms from the divalent mesogen group having an aromatic ring as described above, or a group obtained by removing 0 to 4 hydrogen atoms from the alkylene group having 3 to 15 carbon atoms as described above.

A mesogenic group having an aromatic ring is a group in which one aromatic ring or two or more aromatic rings are condensed. Examples of mesogenic groups having a divalent aromatic ring include a substituted or unsubstituted phenylene group, a substituted or unsubstituted naphthalenediyl group, a substituted or unsubstituted binaphthalenediyl group, a substituted or unsubstituted anthracenediyl group, a substituted or unsubstituted fluorenediyl group, a substituted or unsubstituted triphenylenediyl group, a substituted or unsubstituted phenanthrenediyl group, a substituted or unsubstituted benzophenanthrenediyl group, a substituted or unsubstituted dibenzophenanthrenediyl group, a substituted or unsubstituted chrysenediyl group, a substituted or unsubstituted benzochrysenediyl group, a substituted or unsubstituted picenediyl group, and a substituted or unsubstituted pyrenediyl group. In addition, a mesogenic group having a trivalent to hexavalent aromatic ring is preferably a group obtained by removing 1 to 4 hydrogen atoms from the divalent mesogenic group described above.

The alkylene group having 3 to 15 carbon atoms (wherein -CH2 _{- CH2-} may be replaced by -CH=CH-) includes a divalent saturated hydrocarbon represented by _the general formula _CmH2m (m is an integer of 3 or more and 15 or less) and a divalent unsaturated hydrocarbon represented by the general formula _{CmH2m -2} (m is an integer of 3 or more and 15 or less). The alkylene group is preferably a saturated hydrocarbon group selected from the group consisting of 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, and a linear or branched decylene group, as well as an unsaturated hydrocarbon group in which _{-CH2- CH2-} in the saturated hydrocarbon is replaced by -CH=CH-. Furthermore, --CH ₂ --CH ₂ -- in a saturated hydrocarbon may be replaced by one or more --CH═CH-- groups, so long as they are not adjacent to each other.

In this embodiment, the term "organic group having a divalent to hexavalent bond" refers to an atomic group obtained by removing 0 to 4 hydrogen atoms from a divalent organic group, and is preferably a group obtained by removing 0 to 4 hydrogen atoms from the divalent mesogen group having an aromatic ring as described above, or a group obtained by removing 0 to 4 hydrogen atoms from the alkylene group having 3 to 15 carbon atoms as described above.

In this specification, the alkylene group having 1 to 10 carbon atoms is preferably a linear or branched alkylene group, and 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 preferably 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, and more preferably 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, or a linear or branched octylene group.

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 pentylene group, a cyclopentylene group, a linear or branched hexylene group, a cyclohexylene group, a linear or branched heptylene group, a cycloheptylene group, a linear or branched octylene group, a cyclooctylene group, a linear or branched nonylene group, or a linear or branched decylene group, and is more preferably 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, or a cyclohexylene group.

In the above general formula (I), M represents an addition polymerizable monomer unit, and specifically, it is preferable that M is a conjugated diene monomer unit, a styrene monomer unit, or a (meth)acrylate monomer unit. More specifically, it is preferable that M in the above general formula (I) 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, Y ¹ and Y ² each independently represent -C(═O)-O-R ⁱ or a substituted or unsubstituted phenyl group, s, t and r each independently represent 0 or 1, 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 each independently represent preferably a hydrogen atom or a linear or branched alkyl group having 1 to 7 carbon atoms, more preferably a hydrogen atom or a linear alkyl group having 1 to 5 carbon atoms.
In the above general formula (ii), ^Y1 and ^Y2 each preferably independently represent -C(=O)-O- ^Ri or an unsubstituted phenyl group, where ^Ri 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, a -NHR ^a group, or a -R ^a O group (R ^a represents a hydrogen atom or an alkyl group having 1 to 10 carbon atoms), and W ² represents -NH-, -NR ^b- , -N=, or -O-(R ^b ) _q (R ^b represents an alkylene group having 1 to 10 carbon atoms, and q represents an integer of 0 to 1). However, when W ¹ is a single bond, W ² may be -N=, and W ¹ and W ² may be bonded to form a maleimide. * in general formula (i) represents a bond to the molecular chain that is the main chain.)
In the above general formula (i), R ^a is preferably a hydrogen atom, a methyl group, an ethyl group, or a linear or branched propyl group. Among these, X in the above general formula (ii) is preferably any of the above formulas (i-1) to (i-9) from the viewpoint of high reactivity with vinyl monomers.

（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 above general formula (I), n represents the degree of polymerization, and is preferably 0.1 to 10,000, and more preferably 1 to 5,000.
The macromonomer according to the present invention is represented by the following general formula (1):

(In the above general formula (1),
B ₁ represents an organic group having a valence of 2 to 6;
L represents a single bond or an alkylene group having 1 to 10 carbon atoms (provided that -CH ₂ - in the alkylene group may be replaced with -O-, -S- or -NH- so as not to be adjacent to each other, and further -CH ₂ -CH ₂ - in the alkylene group may be replaced with -CH═CH-);
M represents a single bond or an addition polymerizable monomer unit (preferably a conjugated diene monomer unit), provided that at least one of the n M's is an addition polymerizable monomer unit; Z represents a single bond or an alkylene group having 1 to 10 carbon atoms (provided that _-CH2- in the alkylene group may be substituted with -O-, -S- or -NH-);
n represents the degree of polymerization;
X represents a hydrogen atom or an unsaturated bond group having two or more electron-withdrawing groups bonded thereto, provided that at least one of the k X's is an unsaturated bond group having two or more electron-withdrawing groups bonded thereto.
k represents an integer of 2 or more and 6 or less. In addition, L, M, Z and X present in general formula (I) may each be independently the same or different from each other.
Due to the structure of the macromonomer represented by the above general formula (I), a branched structure can be efficiently imparted by copolymerization with a vinyl monomer, particularly a styrene monomer unit, and the productivity of the branched polymer, particularly the productivity of polystyrene, can be improved.

In the above general formula (1), L, M, Z and X each exist in an amount of 2 to 6, corresponding to the number of bonds in ^B1 . In this case, for example, L exists in an amount of 2 to 6, and 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. Furthermore, in the macromonomer of this embodiment, the number of unsaturated bond groups having two or more electron-withdrawing groups bonded thereto, present in one macromonomer molecule, is preferably equal to or less than the value of k, and the number of unsaturated bond groups having two or more electron-withdrawing groups bonded thereto, present in one macromonomer molecule, is preferably equal to the value of k.

In addition, in the above general formula (1), the preferred aspects of L, M, Z, and X, as well as n and ^B1 , are the same as the preferred aspects of L, M, Z, and X, as well as n and ^B1 , in the above general formula (I), and therefore will not be repeated here.

Preferred embodiments of the macromonomer according to the present invention will be described below. All of the compounds represented by the following general formulas (2) to (6) are preferred embodiments 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 has an unsaturated bond group having two or more electron-withdrawing groups bonded thereto at (maximum) two positions, which is preferable from the viewpoint of forming a branched structure when copolymerized with a vinyl monomer. In addition, when an organic group having a trivalent to hexavalent bond is used, the macromonomer has an unsaturated bond group having two or more electron-withdrawing groups bonded thereto at (maximum) three to six positions, which is more preferable because the copolymerization of the macromonomer with the vinyl monomer can proceed efficiently. On the other hand, when an organic group having a heptavalent or higher bond is used, the macromonomer has an unsaturated bond group having two or more electron-withdrawing groups bonded thereto at (maximum) seven or more positions, which is more likely to lead to local gelation when copolymerized with a vinyl monomer.
The macromonomer according to the present invention is preferably represented by the following general formula (2).

(In the above general formula (2), ^B2 represents a mesogenic group having a divalent aromatic ring or an alkylene group having 3 to 15 carbon atoms (wherein _-CH2 - _CH2- in the alkylene group may be replaced by -CH=CH-),
^L1 and ^L2 each independently represent an alkylene group having 1 to 10 carbon atoms (wherein _-CH2- in the alkylene group may be replaced by -O-, -S- or -NH-);
M ¹ and M ² each independently represent an addition polymerizable monomer unit, Z ¹ and Z ² each independently represent an alkylene group having 1 to 10 carbon atoms (wherein -CH ₂ - in the alkylene group may be substituted with -O-, -S- or -NH-),
ⁿ¹ and ⁿ² each independently represent an integer from 1 to 10,000;
^X1 and ^X2 each independently represent a hydrogen atom or an unsaturated bond group having two or more electron-withdrawing groups bonded thereto, and at least one of ^X1 and ^X2 represents an unsaturated bond group having two or more electron-withdrawing groups bonded thereto.

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, a linear or branched hexylene group, 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), examples of the mesogenic group having a divalent aromatic ring include a 1,2-phenylene group, a 1,3-phenylene group, a 1,4-phenylene group, a 1,8-naphthylene group, a 1,2-naphthylene group, a 1,3-naphthylene group, a 1,2-naphthylene group, a 1,4-naphthylene group, a 1,5-naphthylene group, a 1,6-naphthylene group, a 1,7-naphthylene group, a 2,7-naphthylene group, and a 2,3-naphthylene group. Preferred are anthracene, 2,5-naphthylene, 2,6-naphthylene, 1,8-phenanthrenediyl, 2,7-phenanthrenediyl, 3,6-phenanthrenediyl, 4,5-phenanthrenediyl, 1,8-anthracenediyl, 1,5-anthracenediyl, 1,4-anthracenediyl, 2,3-anthracenediyl, and 2,6-anthracenediyl groups.

In the above general formula (2), L ¹ and L ² are each independently preferably 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, more preferably 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, or a linear or branched octylene group, and even more preferably a linear or branched butylene group, a linear or branched pentylene group, a linear or branched hexylene group, or a linear or branched heptylene group.

In the above general formula (2), ^M1 and ^M2 are each preferably independently a conjugated diene monomer unit, a styrene monomer unit, or a (meth)acrylate 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, Y ¹ and Y ² each independently represent -C(═O)-O-R ⁱ or a substituted or unsubstituted phenyl group, s, t and r each independently represent 0 or 1, 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 each independently represent preferably a hydrogen atom or a linear or branched alkyl group having 1 to 7 carbon atoms, more preferably a hydrogen atom or a linear alkyl group having 1 to 5 carbon atoms.
In the above general formula (2), ⁿ¹ and ⁿ² each independently represent preferably 5 to 10,000, more preferably 25 to 750, and even more preferably 50 to 500.
In the above general formula (2), X ¹ and X ² are preferably each independently 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, a -NHR ^a group, or 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- , or -O-(R ^b ) _q (R ^b represents an alkylene group having 1 to 10 carbon atoms, and q represents an integer of 0 or more and 1 or less); when W ¹ is a single bond, it may be bonded to W ² to form a maleimide.)
A 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 general formula (2) include the following formulae (2-1) to (2-37). The following structural formulae are examples of the present invention. The macromonomer in this embodiment may be interpreted as including those having vinyl addition and 1,4-addition as addition modes in the examples where M in the above general formula (2) is a conjugated diene monomer unit.

(In the above formulas (2-1) to (2-37), ^m1 and ^m2 are each preferably independently 5 to 10,000.)
Among the compounds represented by the above formulae (2-1) to (2-37), those represented by formulae (2-1) to (2-14) are particularly preferred. In the present embodiment, when an organic group having a trivalent bond is used, this leads to the macromonomer having unsaturated bond groups to which two or more electron-withdrawing groups are bonded at (maximum) three positions, and copolymerization of the macromonomer with the vinyl monomer can be efficiently promoted, which is preferable.
The macromonomer according to the present invention is preferably represented by the following general formula (3).

(In the above general formula (3), ^B3 represents an organic group (1) formed by removing one arbitrary hydrogen atom from a mesogen group having a trivalent aromatic ring, an alkylidyne group having 3 to 15 carbon atoms, or an alkylene group having 3 to 15 carbon atoms (wherein _{-CH2- CH2-} in the alkylene group may be replaced by -CH=CH-),
M ¹ , M ² , and M ³ each independently represent a single bond or an addition polymerizable monomer unit (conjugated diene monomer unit), Z ₁ to Z ₃ each independently represent an alkylene group having 1 to 10 carbon atoms (wherein -CH ₂ - in the alkylene group may be substituted with -O-, -S-, or -NH-),
n ₁ , n ₂ and n ₃ each independently represent an integer from 1 to 10,000;
X ₁ , X ₂ and X ₃ each independently represent a hydrogen atom or an unsaturated bond group having two or more electron-withdrawing groups bonded thereto, and at least one of X ₁ to X ₃ represents an unsaturated bond group having two or more electron-withdrawing groups bonded thereto.

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 mesogenic group having a trivalent aromatic ring include those represented by formulae (b-1) to (b-3).

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

(In the above formulas (3-1) to (3-8), m ¹ , m ² and m ³ each independently preferably represent an integer of 5 to 10,000.)
In the present embodiment, when an organic group having a tetravalent bond is used, this leads to the macromonomer having unsaturated bond groups to which two or more electron-withdrawing groups are bonded at (a maximum) four positions, and copolymerization of the macromonomer with the vinyl monomer can be efficiently carried out, which is preferable.
The macromonomer according to the present invention is preferably represented by the following general formula (4).

(In the above general formula (4), ^B4 represents an organic group ( ₂ ) in which two arbitrary hydrogen atoms have been removed from a mesogen group having a tetravalent aromatic ring, a carbon atom, or an alkylene group having 3 to 15 carbon atoms (wherein _-CH2 -CH2- in the alkylene group may be replaced with -CH=CH-),
M ¹ , M ² , M ³ and M ⁴ each independently represent a single bond or an addition polymerizable monomer unit (conjugated diene monomer unit), Z ₁ to Z ⁴ each independently represent an alkylene group having 1 to 10 carbon atoms (wherein -CH ₂ - in the alkylene group may be substituted with -O-, -S- or -NH-),
n ¹ , n ² , n ³ and n ⁴ each independently represent an integer from 1 to 10,000;
X ¹ , X ² , X ³ and X ⁴ each independently represent a hydrogen atom or an unsaturated bond group having two or more electron-withdrawing groups bonded thereto, and at least one of X ¹ to X ⁴ represents an unsaturated bond group having two or more electron-withdrawing groups bonded thereto.

（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 mesogenic group having a tetravalent aromatic ring include (c-1) to (c-3).

(In the above formula, * represents a bond bonded 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 this embodiment, examples of the macromonomer represented by general formula (4) include the following formulae (4-1) to (4-8).

(In the above formulas (4-1) to (4-8), m ¹ , m ² , m ³ and m ⁴ each independently preferably have an integer of 5 to 10,000.)
In the present embodiment, when an organic group having a pentavalent bond is used, the macromonomer has unsaturated bond groups to which two or more electron-withdrawing groups are bonded at (a maximum) five positions, and copolymerization of the macromonomer with the vinyl monomer can be efficiently carried out, which is preferable.
The macromonomer according to the present invention is preferably represented by the following general formula (5).

(In the above general formula (4), ^B5 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 monomer unit), Z ₁ to Z ⁵ each independently represent an alkylene group having 1 to 10 carbon atoms (wherein -CH ₂ - in the alkylene group may be substituted with -O-, -S- or -NH-),
n ¹ , n ² , n ³ , n ⁴ and n ⁵ each independently represent an integer of 1 to 10,000;
^X1 , ^X2 , ^X3 , ^X3 and ^X5 each independently represent a hydrogen atom or an unsaturated bond group having two or more electron-withdrawing groups bonded thereto, and at least one of ^X1 to ^X5 represents an unsaturated bond group having two or more electron-withdrawing groups bonded thereto.

（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。） In the above general formula (5), examples of the pentavalent organic group (2) include (d-1) to (d-3).

(In the above formula, * represents a bond bonded 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), ^B6 represents a mesogenic group having a hexavalent aromatic ring,
L ¹ to L ⁶ each independently represent a single bond or an alkylene group having 1 to 10 carbon atoms (wherein -CH ₂ - in the alkylene group may be replaced by -O-, -S- or -NH-, and further, -CH ₂ -CH ₂ - in the alkylene group may be replaced by -CH═CH-);
M ¹ to M ⁶ each independently represent a single bond or an addition polymerizable monomer unit;
Z ¹ to Z ⁶ each independently represent a single bond or an alkylene group having 1 to 10 carbon atoms (wherein —CH ₂ — in the alkylene group may be replaced by —O—, —S— or —NH—);
n ¹ to n ⁶ each independently represent an integer from 0 to 10,000;
X ¹ to X ⁶ each independently represent a hydrogen atom or an unsaturated bond group having two or more electron-withdrawing groups bonded thereto, and at least two of X ₁ to X ₆ represent an unsaturated bond group having two or more electron-withdrawing groups bonded thereto.

（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 mesogenic group having a hexavalent aromatic ring include (e-1) to (e-3).

(In the above formula, * represents a bond bonded to L ¹ to L ⁶ )

(Method for producing macromonomer)
An example of the method for producing the macromonomer according to the present invention will now be described.
When the macromonomer according to the present invention has a mesogenic group having a divalent to hexavalent aromatic ring, it is preferable to have the reaction step (1).

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

In this embodiment, the aromatic compound having at least two vinyl groups refers to a compound in which 2 to 6 hydrogen atoms in an aromatic compound are substituted with vinyl groups (CH ₂ ═CR ^h — (R ^h is a hydrogen atom or an alkyl group having 1 to 5 carbon atoms).

The aromatic compound that can be used in the present embodiment is not particularly limited, and examples thereof include benzene, naphthalene, azulene, anthracene, phenanthrene, pyrene, chrysene, naphthacene, triphenylene, acenaphthene, coronene, fluorene, fluoranthene, pentacene, perylene, pentaphene, picene, pyranthrene, anthranthrene, and the like. Furthermore, the aromatic compound may have a substituent such as a halogen or an alkyl group, if necessary. Therefore, the aromatic compound having at least two vinyl groups is preferably a compound in which 2 to 6 hydrogen atoms in the above-exemplified aromatic compounds are substituted with a vinyl group (CH ₂ ═CR ^h - (R ^h is a hydrogen atom or an alkyl group having 1 to 5 carbon atoms).

In this embodiment, the organolithium is not particularly limited as long as it can be used as a polymerization initiator, and examples thereof include organolithium of a low molecular weight compound or a solubilized oligomer. Examples include organolithium having a carbon-lithium bond, organolithium having a nitrogen-lithium bond, and organolithium having a tin-lithium bond.

Examples of the organic lithium having a carbon-lithium bond include n-butyllithium, sec-butyllithium, tert-butyllithium, n-hexyllithium, benzyllithium, phenyllithium, and stilbenelithium. Examples of the organic lithium having a nitrogen-lithium bond include lithium dimethylamide, lithium diethylamide, lithium dipropylamide, lithium di-n-hexylamide, lithium diisopropylamide, lithium hexamethyleneimide, lithium pyrrolidide, lithium piperidide, lithium heptamethyleneimide, and lithium morpholide.

In addition, in this embodiment, the organolithium may be not only the monoorganolithium described above, but also a polyfunctional organolithium, or a monoorganolithium and a polyfunctional organolithium may be used in combination and polymerized.

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

In this embodiment, the addition polymerizable monomer is preferably a conjugated diene monomer such as butadiene, isoprene, myrcene, or farnesene; a styrene monomer unit such as styrene, α-methylstyrene, or paramethylstyrene; or a (meth)acrylate monomer such as methyl (meth)acrylate, ethyl (meth)acrylate, propyl (meth)acrylate, or butyl (meth)acrylate. The addition polymerizable monomer may be composed of two or more of these monomers.

In this embodiment, the hetero three-membered ring compound is preferably a compound having an oxirane ring or a compound having an aziridine ring, and examples thereof include ethylene oxide, propylene oxide, cyclohexene oxide, styrene oxide, epoxidized soybean oil, epoxidized natural rubber, bisphenol A diglycidyl ether, glycerin triglycidyl ether, N,N,N',N'-tetraglycidyldiaminodiphenylmethane, thiirane, methylthiirane, phenylthiirane, ethyleneimine, propyleneimine, N-phenylethyleneimine, N-(β-cyanoethyl)ethyleneimine, and 2,5-bis(1-aziridinyl)-p-benzoquinone.

In this embodiment, examples of compounds containing an unsaturated bond group having two or more electron-withdrawing groups bonded thereto are preferably maleic anhydride, maleic diester, maleic monoester, fumaric diester, fumaric monoester, maleic diamide, maleic monoamide, and maleimide. The compounds containing an unsaturated bond group having two or more electron-withdrawing groups bonded thereto correspond to the unsaturated bond group having two or more electron-withdrawing groups bonded thereto in the macromonomer according to the present invention.

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

(In the compound of step 4 above, ^R1 each independently represents a hydrogen atom or an alkyl group having 1 to 10 carbon atoms, and m1 and m2 each independently represent an integer from 0 to 10,000.)

When the macromonomer according to the present invention has an alkylene group having 3 to 15 carbon atoms (wherein --CH ₂ --CH ₂ -- in the alkylene group may be replaced by --CH═CH--), it is preferable to have the reaction step (2).

The reaction step (2) preferably comprises a step (f) of mixing an addition polymerizable monomer with a polymerization initiator to prepare a reaction mixture (4), and a step (g) of mixing a compound containing an unsaturated bond group having two or more electron-withdrawing groups bonded thereto with the reaction mixture (4) to prepare a macromonomer.
In the above reaction step (b), the carbon anion is reacted with a hetero three-membered ring compound to convert it into a heteroatom anion, and then it is converted into a functional group having active hydrogen (e.g., a hydroxyl group, an amino group, etc.), so that it can be reacted in a desired manner with a compound containing an unsaturated bond group to which two or more electron-withdrawing groups are bonded. If it is attempted 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), the carbonyl group reacts with the carbon anion to generate a ketone group, and the generated ketone reacts with the unreacted carbon anion to generate 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, polymerization can be carried out in a solvent using an addition polymerizable monomer and a radical polymerization initiator.

In this embodiment, examples of the radical polymerization initiator include peroxide initiators and azo initiators. Peroxide compounds and azo compounds having active hydrogen such as hydroxyl groups or amino groups are preferable. For example, by using hydrogen peroxide, a polymer having a hydroxyl group at the end can be produced. This allows the hydroxyl group to react with a compound containing an unsaturated bond group to which two or more electron-withdrawing groups are bonded, and the unsaturated bond group to which two or more electron-withdrawing groups are bonded can be introduced to the end.

Examples of the radical polymerization initiator include azo compounds such as 2,2'-azobisisobutyronitrile, 2,2'-azobis-(2,4-dimethylvaleronitrile), and 2,2'-azobis-(4-methoxy-2,4-dimethylvaleronitrile); organic peroxides such as benzoyl peroxide, lauroyl peroxide, t-butyl peroxypivalate, t-butylperoxyethylhexanoate, 1,1'-bis-(t-butylperoxy)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.

In the above step (f), examples of solvents that can be used for radical polymerization include ketone-based solvents such as acetone, methyl ethyl ketone, methyl n-propyl ketone, methyl isopropyl ketone, methyl n-butyl ketone, methyl isobutyl ketone, methyl n-amyl ketone, methyl n-hexyl ketone, diethyl ketone, ethyl n-butyl ketone, di-n-propyl ketone, diisobutyl ketone, cyclohexanone, and phorone; ether-based solvents such as ethyl ether, isopropyl ether, n-butyl ether, diisoamyl ether, 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, and isopropyl acetate. Examples of the solvent include ester solvents such as isopropyl, n-butyl acetate, n-amyl acetate, 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, and ethyl-3-ethoxypropionate; alcohol solvents such as methanol, ethanol, isopropyl alcohol, n-butyl alcohol, isobutyl alcohol, diacetone alcohol, 3-methoxy-1-propanol, 3-methoxy-1-butanol, and 3-methyl-3-methoxybutanol; and 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 this embodiment, examples of the compound containing an unsaturated bond group having two or more electron-withdrawing groups bonded thereto are preferably maleic anhydride, maleic diester, maleic monoester, fumaric diester, fumaric monoester, maleic diamide, maleic monoamide, and maleimide. The compound containing an unsaturated bond group having two or more electron-withdrawing groups bonded thereto corresponds to the unsaturated bond group having two or more electron-withdrawing groups bonded thereto in the macromonomer according to the present invention.
In this embodiment, the reaction may be carried out under either an air atmosphere or an inert gas atmosphere.
In the above step (g), the method for introducing an unsaturated bond group having two or more electron-withdrawing groups bonded to the terminal end is not particularly limited, and examples thereof include an esterification reaction using an acid anhydride group, an ester exchange reaction using an ester group, an esterification reaction using a carboxyl group, an amidation reaction using an acid anhydride group, and a maleimidization reaction using an acid anhydride group.
In the above step (g), in order to efficiently proceed with the reaction, it is preferable that the water content in the reaction mixture is 0.1 parts by mass or less.
In the above step (g), the reaction temperature is preferably 0° C. to 150° C. If the reaction temperature is lower than 0° C., the viscosity of the reaction system increases, the diffusion of the compound containing an unsaturated bond group to which two or more electron-withdrawing groups are bonded slows down, and the reaction does not proceed easily, whereas if the reaction temperature is higher than 150° C., the unsaturated bond groups to which two or more electron-withdrawing groups are bonded in the macromonomer react with each other, making it impossible to obtain a macromonomer having a desired structure, which is not preferable.
In the above step (g), examples of the solvent that can be used in the reaction include ketone solvents such as acetone, methyl ethyl ketone, methyl n-propyl ketone, methyl isopropyl ketone, methyl n-butyl ketone, methyl isobutyl ketone, methyl n-amyl ketone, methyl n-hexyl ketone, diethyl ketone, ethyl n-butyl ketone, di-n-propyl ketone, diisobutyl ketone, cyclohexanone, and phorone; ethyl ether, isopropyl ether, n-butyl ether, diisoamyl ether, ethylene glycol dimethyl ether, ethylene glycol diethyl ether, diethylene glycol dimethyl ether, diethylene glycol, dioxane, tetrahydrofuran, and the like. Examples of the solvent include ether solvents such as hydrofuran, ethyl formate, propyl formate, n-butyl formate, ethyl acetate, n-propyl acetate, isopropyl acetate, n-butyl acetate, n-amyl acetate, 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, and ethyl-3-ethoxypropionate, as well as 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 above reaction step (g), a polymerization inhibitor can be used from the viewpoint of preventing polymerization of the macromonomer during the reaction. Specific examples of the polymerization inhibitor include N-oxy radical compounds such as 4-hydroxy-2,2,6,6-tetramethylpiperidine-N-oxyl, 4-acetamino-2,2,6,6-tetramethylpiperidine-N-oxyl, 4-benzooxy-2,2,6,6-tetramethylpiperidine-N-oxyl, 4-oxo-2,2,6,6-tetramethylpiperidine-N-oxyl, and 2,2,6,6-tetramethylpiperidine-N-oxyl; hydroquinone, hydroquinone monomethyl ether, 2,6-di- Examples of the compounds include phenolic compounds such as 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(3-methyl-6-t-butylphenol), and 4,4'-butylidene-bis(3-methyl-6-t-butylphenol); quinone compounds such as benzoquinone and 2,5-di-t-butylhydroquinone; and copper compounds such as cuprous chloride and copper dimethyldithiocarbamate. These compounds may be used alone or in combination of two or more.
In this embodiment, examples of radical polymerization initiators that can be used in copolymerizing a vinyl monomer and a macromonomer include peroxide initiators and azo initiators. Examples of the radical polymerization initiator include azo compounds such as 2,2'-azobisisobutyronitrile, 2,2'-azobis-(2,4-dimethylvaleronitrile), and 2,2'-azobis-(4-methoxy-2,4-dimethylvaleronitrile); organic peroxides such as benzoyl peroxide, lauroyl peroxide, t-butyl peroxy pivalate, t-butyl peroxy ethylhexanoate, 1,1'-bis-(t-butylperoxy)cyclohexane, t-amyl peroxy-2-ethylhexanoate, and t-hexyl peroxy-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。 As an example of a method for synthesizing a macromonomer according to the present invention, a second reaction scheme (an example of reaction process (2)) is shown below. In reaction process (2) of this embodiment, process (f) corresponds to steps 1 to 3 in the second reaction scheme, and process (g) corresponds to step 4.

(In the above formula (2-5), m0, m1, and m2 each independently represent an integer of 0 to 10,000.)
Although the embodiment of the present invention has been described above, the present invention is not limited to the above example and can be modified as appropriate.

The present invention will be specifically described below with reference to examples and comparative examples, but it should not be construed that the present invention is limited to these examples.
First, the evaluation methods used to evaluate the Examples and Comparative Examples will be described below.
"Evaluation Method"
(1) Measurement of Number Average Molecular Weight Mn, Weight Average Molecular Weight Mw, and Z Average Molecular Weight Mz The number average molecular weight (Mn), weight average molecular weight (Mw), and z average molecular weight (Mz) of the obtained macromonomer and the copolymer of a vinyl monomer and a macromonomer were measured by gel permeation chromatography (GPC) under the following conditions.
Sample preparation: Dissolve styrene copolymer resin in tetrahydrofuran to a concentration of approximately 0.05% by mass. Measurement conditions: Instrument: TOSOH HLC-8220GPC
(Gel Permeation Chromatography)
Column: super HZM-H
Temperature: 40°C
Carrier: THF 0.35 mL/min
Detector: RI, UV: 254 nm
Calibration curve: Using standard PS manufactured by TOSOH

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

"Raw materials"
"Example 1"
Synthesis of polyisoprene main chain macromonomer (macromonomer A) 200 g of polyisoprene diol polyip was placed in a flask, 20 g of maleic anhydride and 0.1 g of antioxidant tertiary butyl catechol were added thereto, and the flask was immersed in an oil bath heated to 70°C and stirred. After 6 hours of reaction, the flask was removed from the oil bath and the reaction was stopped. The reduction rate of hydroxyl groups in polybutadiene diol was measured by ^1H -NMR and found to be 98%, confirming that the reaction proceeded almost quantitatively.

"Example 2"
Synthesis of hydrogenated polyisoprene main chain macromonomer (macromonomer B) 200 g of hydrogenated polyisoprene diol Epole was placed in a flask, 20 g of maleic anhydride and 0.1 g of antioxidant tertiary butyl catechol were added thereto, and the flask was immersed in an oil bath heated to 70°C and stirred. After 6 hours of reaction, the flask was removed from the oil bath and the reaction was stopped. The reduction rate of hydroxyl groups in the hydrogenated polyisoprene diol was measured by ^1H -NMR and found to be 97%, confirming that the reaction had proceeded almost quantitatively.

"Example 3"
Synthesis of polyisoprene main chain macromonomer (by anionic polymerization) (macromonomer C) <Preparation of reagents>
Isoprene (Tokyo Chemical Industry Co., Ltd.), cyclohexane (Fuji Film Wako Pure Chemical Industries Co., Ltd.), 1,3-diisopropylbenzene (Tokyo Chemical Industry Co., Ltd.), tetramethylethylenediamine (Fuji Film Wako Pure Chemical Industries Co., Ltd., hereinafter TMEDA), triethylamine (Tokyo Chemical Industry Co., Ltd., hereinafter TEA), and butylene oxide (Tokyo Chemical Industry Co., Ltd.) were prepared by heating and drying alumina granules (Fuji Film Wako Pure Chemical Industries Co., Ltd.) at 200°C, allowing them to cool to room temperature in a desiccator, and then polymerizing 10% or more of the liquid volume of each compound to dehydrate them. s-Butyllithium (1.3 mol/L hexane-cyclohexane solution, Fuji Film Wako Pure Chemical Industries Co., Ltd.) was used as purchased.
<Solution preparation>
For the polymerization, the following solutions A to E were prepared.
(Solution A) 5.0 mL of cyclohexane and 1.5 mL of TEA were added to a flask, and the mixture was stirred with a stirrer to obtain a homogeneous solution.
(Solution B) 6.0 mL of cyclohexane and 1.0 mL of diisopropylbenzene were added to a flask, and the mixture was stirred with a stirrer to obtain a homogeneous solution.
(Solution C) 9.0 mL of cyclohexane and 0.30 mL of TMEDA were added to a flask, and the mixture was stirred with a stirrer to obtain a homogeneous solution.
(Solution D) 45.0 mL of cyclohexane and 7.5 mL of isoprene were added to a flask, and the mixture was stirred to obtain a homogeneous solution.
(Solution E) 5.0 mL of cyclohexane and 5.0 mL of ethylene oxide (0.8 mol/L hexane solution) were added to a flask, and the mixture was stirred to obtain a homogeneous 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 to obtain a homogeneous solution. Then, 2.0 mL of solution A was added, and 1.8 mL of solution B was further added. The flask was heated to 50° C. in a heated oil bath and reacted 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 solution C was added, and the mixture was reacted for 10 minutes while stirring to prepare a mixed solution (1) (reaction mixture (1)). 10.0 mL of solution D was added to the mixed solution (1), and the mixture was reacted for 2 hours at 25°C. Then, 1.2 mL of the initiator solution was added, and the mixture was reacted for another 10 minutes at 25°C 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 reacted for another 10 minutes. Then, 1.0 mL of a degassed mixed solvent of methanol/tetrahydrofuran = 1/1 (wt/wt) was added to stop the reaction. Hereinafter, this liquid is referred to as a post-polymerization-stopped solution (reaction mixture (3)).
"Recovery process"

300 mL of methanol, a poor solvent, was placed in a beaker, and the polymerization-stopping solution was added dropwise to it using a dropper. The solution became cloudy as it was added. After the addition was completed, the solution was left to stand for 12 hours, and a precipitate was deposited at the bottom of the beaker. The supernatant was removed and the solution was dried in a desiccator to obtain a polyisoprene diol terminated at both ends. The molecular weight was measured by GPC, and it was found to be Mn=20,000 (PS equivalent). Furthermore, ¹ H-NMR analysis showed that the hydroxyl group introduction rate was 98%.

"Maleic acid esterification reaction step (step (g))"
0.10 g of the polyisoprene diol at both ends, 0.5 mg of maleic anhydride, 0.05 mg of paramethoxyphenol, and 0.90 g of ethylbenzene were weighed out and added to a flask equipped with a stirrer. The flask was immersed in an oil bath heated to 80° C. and reacted for 6 hours.
The molecular weight was measured by GPC and found to be Mn=20200 (PS equivalent). Furthermore, ¹ H-NMR analysis showed that 99% of the hydroxyl groups had been consumed and the introduction rate of maleic ester was 99%.

"Example 4"
In a flask equipped with a three-way cock, 0.040 g of 2,2-bis(4,4-di-t-butylperoxycyclohexyl)propane (hereinafter referred to as Pertetra A) was added as an initiator, 83.86 g of styrene, 16.00 g of ethylbenzene, and 0.10 g of Macromonomer A were added, and the solution was homogenized using a stirrer. The solution was immersed in an oil bath set at 100°C and reacted for 6 hours. The solution was subjected to high vacuum removal of volatile components in a vacuum dryer set at 230°C for 10 minutes, yielding a colorless and transparent resin. The evaluation results obtained by the above-mentioned production method are shown in Table 1.

"Example 5"
0.040g of Pertetra A, 83.86g of styrene, 16.00g of ethylbenzene, and 0.10g of Macromonomer B were added to a flask equipped with a three-way cock, and the solution was homogenized using a stirrer. The solution was immersed in an oil bath set at 100°C and reacted for 6 hours. The solution was then placed in a vacuum dryer set at 230°C for 10 minutes to remove volatile components under high vacuum, yielding a colorless and transparent resin. The evaluation results obtained by the above-mentioned manufacturing method are shown in Table 1.

"Example 6"
0.040g of Pertetra A, 83.86g of styrene, 16.00g of ethylbenzene, and 0.10g of Macromonomer C were placed in a flask equipped with a three-way cock, and the solution was homogenized using a stirrer. The solution was immersed in an oil bath set at 100°C and reacted for 6 hours. The solution was then placed in a vacuum dryer set at 230°C for 10 minutes to remove volatile components under high vacuum, yielding a colorless, transparent resin. The evaluation results obtained by the above-mentioned manufacturing method are shown in Table 1.

"Example 7"
In a flask equipped with a three-way cock, 0.040 g of 1,1-di-t-butylperoxycyclohexane (hereinafter referred to as Perhexa C) as an initiator, 99.96 g of styrene, and 0.10 g of Macromonomer C were added and the solution was homogenized using a stirrer. The solution was immersed in an oil bath set at 100°C and reacted for 3 hours. The solution was then placed in a vacuum dryer set at 230°C for 10 minutes to remove volatile components under high vacuum, yielding a colorless and transparent resin. The evaluation results obtained by the above-mentioned manufacturing method are shown in Table 1.

"Example 8"
0.040g of Perhexa C, 99.96g of styrene, and 0.10g of Macromonomer C were placed in a flask equipped with a three-way cock, and the solution was homogenized using a stirrer. The solution was immersed in an oil bath set at 100°C and reacted for 6 hours. The solution was then placed in a vacuum dryer set at 230°C for 10 minutes to remove volatile components under high vacuum, yielding a colorless, transparent resin. The evaluation results obtained by the above-mentioned manufacturing method are shown in Table 1.

"Comparative Example 1"
0.040 g of Partetra 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 homogenized using a stirrer. The solution was immersed in an oil bath set at 100°C and reacted for 6 hours. The solution was placed in a vacuum dryer set at 230°C for 10 minutes to remove volatile components under high vacuum, resulting in a colorless and transparent resin. The evaluation results obtained by the above-mentioned manufacturing method are shown in Table 1. Comparative Example 1 is used as the experimental result of the standard in which no macromonomer is present.

"Comparative Example 2"
0.040g of Partetra A, 83.86g of styrene, 16.00g of ethylbenzene, and 0.10g of polyisoprene diol were placed in a flask equipped with a three-way cock, and the solution was homogenized with a stirrer. The solution was immersed in an oil bath set at 100°C and reacted for 6 hours. The solution was subjected to high vacuum for 10 minutes in a vacuum dryer set at 230°C to remove volatile components, resulting in a colorless and transparent resin. The evaluation results obtained by the above-mentioned manufacturing method are shown in Table 1. Since there was no maleic acid ester at the end, the additive did not copolymerize with styrene, and the molecular weight was equivalent to that of Comparative Example 1. Furthermore, under these conditions, no copolymerization was observed in the double bonds in the polyisoprene.

"Comparative Example 3"
0.040g of Partetra A, 83.86g of styrene, 16.60g of ethylbenzene, and 0.10g of polyisoprene diacrylate were placed in a flask equipped with a three-way cock, and the solution was homogenized using a stirrer. The solution was immersed in an oil bath set at 100°C and reacted for 6 hours. The solution was placed in a vacuum dryer set at 230°C for 10 minutes to remove volatile components under high vacuum, resulting in a colorless and transparent resin. The evaluation results obtained by the above-mentioned manufacturing method are shown in Table 1.
As shown in the evaluation results, the Mw and Mz of the resin in Comparative Example 3 were larger than those in Comparative Examples 1 and 2, but smaller than those in Example 4. This result indicates that the macromonomer having a double bond to which two electron-withdrawing substituents are bonded is more likely to undergo copolymerization with styrene, and that the PS molecular weight can be efficiently extended with the same amount of addition.

"Comparative Example 4"
0.040g of Perhexa C, 99.96g of styrene, and 0.10g of polyisoprene diacrylate were placed in a flask equipped with a three-way cock, and the solution was homogenized using a stirrer. The solution was immersed in an oil bath set at 100°C and reacted for 3 hours. The solution was then placed in a vacuum dryer set at 230°C for 10 minutes to remove volatile components under high vacuum, yielding a colorless, transparent resin. The evaluation results obtained by the above-mentioned manufacturing method are shown in Table 1.
As shown in the evaluation results, compared with Example 7, the copolymer using the macromonomer in Comparative Example 4 had smaller Mw and Mz.

"Comparative Example 5"
0.040g of Perhexa C, 99.96g of styrene, and 0.10g of polyisoprene diacrylate were placed in a flask equipped with a three-way cock, and the solution was homogenized using a stirrer. The solution was immersed in an oil bath set at 100°C and reacted for 6 hours. The solution was then placed in a vacuum dryer set at 230°C for 10 minutes to remove volatile components under high vacuum, yielding a colorless, transparent resin. The evaluation results obtained by the above-mentioned manufacturing method are shown in Table 1.
As shown in the evaluation results, compared with Example 8, the copolymer using the macromonomer in Comparative Example 5 had smaller Mw and Mz.

(Relationship between reaction time and Mz)
Furthermore, regarding the experimental results of Example 7, Example 8, Comparative Example 4, and Comparative Example 5, a graph in which 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 in Figure 1, when the polyisoprene acrylates of Comparative Examples 4 and 5 were used, the molecular weight (interpolated value) reached in a polymerization reaction time of 4.2 hours was 80 x ^104. On the other hand, when the macromonomer C of Examples 7 and 8 was used, it was found that the reaction time to reach the molecular weight was shortened to 3 hours (approximately 1.2 hours shorter). In other words, it was found that the macromonomer C has high copolymerizability with styrene and can increase the production rate by 140%.

The macromonomer according to the present invention can be widely used as a crosslinking agent in copolymerization with addition-polymerizable monomers, as an adhesive, or as a sealant for electronic materials.

Claims (3)

A macromonomer having at least one type of unsaturated bond group at an end thereof to which two or more electron-withdrawing groups are bonded, and including an addition polymerizable monomer unit as a main chain,
A macromonomer represented by the following general formula (1):

(In the above general formula (1),
^B1 represents a mesogenic group having an aromatic ring having a divalent to tetravalent bond, and examples of the mesogenic group having a divalent aromatic ring include a 1,2-phenylene group, a 1,3-phenylene group, a 1,4-phenylene group, a 1,8-naphthylene group, a 1,2-naphthylene group, a 1,3-naphthylene group, a 1,2-naphthylene group, a 1,4-naphthylene group, a 1,5-naphthylene group, a 1,6-naphthylene group, a 1,7-naphthylene group, a 2,7-naphthylene group, a 2,3-naphthylene group, a 2,5-naphthylene group, and a 2,6-naphthylene group. the mesogenic group having a trivalent to tetravalent aromatic ring is a group obtained by removing one or two hydrogen atoms from the mesogenic group having a divalent aromatic ring,
L represents a single bond or an alkylene group having 1 to 10 carbon atoms (wherein -CH ₂ - in the alkylene group may be replaced with -O-, -S- or -NH- so as not to be adjacent to each other, and further, -CH ₂ -CH ₂ - in the alkylene group may be replaced with -CH═CH-);
M represents the addition polymerizable monomer unit, which is an isoprene monomer unit or a hydrogenated isoprene monomer unit;
Z represents a single bond or an alkylene group having 1 to 10 carbon atoms (wherein —CH ₂ — in the alkylene group may be replaced by —O—, —S— or —NH—);
n represents an integer from 1 to 10,000;
X represents a hydrogen atom or an unsaturated bond group having two or more electron-withdrawing groups bonded thereto, the unsaturated bond group being represented by any one of the following formulae (i-1) to (i-9), and at least one X among the k X's is an unsaturated bond group having two or more electron-withdrawing groups bonded thereto, the unsaturated bond group being represented by any one of the following formulae (i-1) to (i-9),

k represents an integer of 2 or more and 4 or less. In addition, L, M _, Z and X, each of which is present in the general formula (1), may be independently the same or different from each other. The macromonomer according to claim 1 , represented by the following general formula (2):

(In the above general formula (2), ^B2 represents a mesogenic group having the above divalent aromatic ring,
^L1 and ^L2 each independently represent a linear or branched butylene group, a linear or branched pentylene group, a linear or branched hexylene group, or a linear or branched heptylene group;
M ¹ and M ² each independently represent the addition polymerizable monomer unit and are an isoprene monomer unit; Z ¹ to Z ² each independently represent an alkylene group having 1 to 10 carbon atoms (wherein -CH ₂ - in the alkylene group may be substituted with -O-, -S- or -NH-);
ⁿ¹ and ⁿ² each independently represent an integer from 1 to 10,000;
X ¹ and X ² each independently represent a hydrogen atom or an unsaturated bond group having two or more electron-withdrawing groups bonded thereto, the unsaturated bond group being represented by any one of the following formulae (i-1) to (i-9), and at least one of X ¹ to X ² represents an unsaturated bond group having two or more electron-withdrawing groups bonded thereto, the unsaturated bond group being represented by any one of the following formulae (i-1) to (i-9). 3. The macromonomer according to claim 1 , which has a number average molecular weight (Mn) of 1,000 or more and 200,000 or less.

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