Macromonomer and polymer using said macromonomer

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

[Technical field]

[0001] The present invention relates to a macromonomer and a polymer using the macromonomer. [Background technology]

[0002] 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.

[0003] Examples of techniques related to addition polymerization include Patent Documents 1 and 2. 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 is composed of a predetermined conjugated divinyl compound and a predetermined 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 substance. [Prior art documents] [Patent documents]

[0004] [Patent Document 1] JP2013-100432A [Patent Document 2] JP2017-218575A Summary of the Invention [Problem to be solved by the invention]

[0005] However, the vinyl group present in the multifunctional vinyl copolymer described in Patent Document 1 is an aromatic vinyl group, and there is a drawback in that the rate of branched polystyrene production is slow during copolymerization with styrene in the production of branched polystyrene, resulting in low productivity. In addition, since the conjugated vinyl group in the conjugated divinyl compound described in Patent Document 2 is a (meth)acrylate group, it has been found that there is room for further improvement in copolymerizability.

[0006] Therefore, the present invention has been made to solve the above problems, and an object of the present invention is to provide a novel macromonomer which has a fast reaction rate, can efficiently impart a branched structure by copolymerization, and improves the productivity of branched polymers. [Means for solving the problem]

[0007] As a result of intensive research into achieving the above object, the present inventors have found that the above problems can be solved by a macromonomer having at least one type of unsaturated bond group at the end thereof, to which two or more electron-withdrawing groups are bonded, and containing an addition-polymerizable monomer unit as the main chain, and have thus completed the present invention. That is, the present invention is as follows.

[0008] [1] The present embodiment is 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 including addition-polymerizable monomer units as the main chain.

[0009] [2] In this embodiment, an organic group having a divalent to hexavalent bond, The following general formula (I) is directly bonded to the bond of the organic group: [ka] (In the above general formula (I), L represents a single bond or an alkylene group having 1 to 10 carbon atoms (wherein, -CH- in the alkylene group may be substituted with -O-, -S-, or -NH- so as not to be adjacent to each other, and further, -CH-CH- in the alkylene group may be substituted 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- 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 alkyl group has up to six kinds of groups represented by the following formula:

[0010] [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-).

[0011] [4] The macromonomer in this embodiment is preferably represented by the following general formula (1). [ka] (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 (wherein -CH- in the alkylene group may be replaced with -O-, -S-, or -NH- so as not to be adjacent to each other, and further, -CH-CH- 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- 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, each of which is present in general formula (1), may be independently the same or different from each other.

[0012] [5] The macromonomer in this embodiment is preferably represented by the following general formula (2). [ka] (In the above general formula (2), B 2 represents an alkylene group having 3 to 15 carbon atoms (wherein -CH-CH- in the alkylene group may be replaced with -CH=CH-), L 1 and L 2 each independently represents an alkylene group having 1 to 10 carbon atoms (wherein -CH- in the alkylene group may be replaced by -O-, -S-, or -NH-), M 1 , M 2 each independently represents an addition polymerizable monomer unit; Z 1 ~Z 2 each independently represents an alkylene group having 1 to 10 carbon atoms (wherein -CH- in the alkylene group may be replaced by -O-, -S-, or -NH-), n 1 and n 2 each independently represents an integer from 1 to 10,000; X 1 and X 2 each independently represents a hydrogen atom or an unsaturated bond group having two or more electron-withdrawing groups bonded thereto, and X 1 ~X 2 At least one of the groups represents an unsaturated bond group to which two or more electron-withdrawing groups are bonded. Effect of the Invention

[0013] According to the present invention, a branched structure can be efficiently imparted by copolymerization, and the productivity of the branched polymer can be improved. [Brief description of the drawings]

[0014] [Figure 1] FIG. 1 is a graph showing the relationship between reaction time and Mz in the examples and comparative examples. DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS

[0015] 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 implemented in various modified forms within the scope of its gist.

[0016] 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 a 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.

[0017] In this specification, the term "addition polymerizable monomer unit" refers to a monomer unit that is polymerized 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 the addition polymerizable monomer 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.

[0018] In the present 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 an inductive effect or a resonance effect is covalently bonded to a carbon atom constituting a carbon-carbon unsaturated bond group. Examples of the substituent include an ester group, an amide group, a carboxyl group, a ketone group, a cyano group, or a halogen atom.

[0019] 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). [ka]

[0020] (In the above general formula (i), W 1 is a single bond, an amino group, -NHR a group, -R a Represents an O group (R a represents a hydrogen atom or an alkyl group having 1 to 10 carbon atoms; W 2 -NH-, -NR b- , -N=, -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. 1 If is a single bond, W 2 is -N= and W 1 and W 2 may be bonded to form maleimide. In the 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.

[0021] 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. [ka] [ka]

[0022] In this specification, the term "terminal" can be the position at the end of the molecular chain, but if the unsaturated bond group having two or more electron-withdrawing groups bonded thereto is present near the end (or near the end), 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, the term "terminal" in this embodiment can also be a portion (end portion) that is in the molecular chain and that is within a certain range including the position (atom) at the end of the molecular chain (in other words, the unsaturated bond group having two or more electron-withdrawing groups bonded thereto can be positioned near the end). The portion that is within 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 the macromonomer, more preferably 5% or less, even more preferably 3% or less, and even more preferably 1% or less.

[0023] 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 divalent to hexavalent bond, and a compound represented by the following general formula (I) which is directly bonded to the bond of the organic group: [ka]

[0024] (In the above general formula (I), L represents a single bond or an alkylene group having 1 to 10 carbon atoms (wherein, -CH- in the alkylene group may be replaced with -O-, -S- or -NH- so as not to be adjacent to each other, and further, -CH-CH- 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- 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 general formula (I), * represents a bond to an atom contained in an organic group. and preferably has one or more types of unsaturated bond groups to which two or more electron-withdrawing groups are bonded in one molecule. 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 bonds. 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.

[0025] The organic group in general formula (I) refers to a hydrocarbon group in which carbon atoms are bonded to each other by a covalent bond, and the organic group having a divalent to hexavalent bond preferably represents a mesogenic group having an aromatic ring having a divalent to hexavalent bond, 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.

[0026] In this embodiment, the "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 above-mentioned divalent mesogenic group having an aromatic ring, or a group obtained by removing 0 to 4 hydrogen atoms from the above-mentioned alkylene group having 3 to 15 carbon atoms.

[0027] The mesogenic group having an aromatic ring is a group in which one aromatic ring or two or more aromatic rings are condensed. As the mesogenic group having a divalent aromatic ring, for example, 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 are preferable. In addition, as the mesogenic group having a trivalent to hexavalent aromatic ring, a group in which 1 to 4 hydrogen atoms are removed from the above-mentioned divalent mesogenic group is preferable.

[0028] The alkylene group having 3 to 15 carbon atoms (wherein, -CH-CH- may be replaced by -CH=CH-) is represented by the general formula C m H 2m (m is an integer of 3 to 15) and divalent saturated hydrocarbons represented by the general formula C m H 2m-2 (m is an integer of 3 to 15). 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 with -CH=CH-. In addition, -CH2-CH2- in the saturated hydrocarbon may be replaced with one or more -CH=CH- as long as they are not adjacent to each other.

[0029] In this embodiment, the "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 above-mentioned divalent mesogenic group having an aromatic ring, or a group obtained by removing 0 to 4 hydrogen atoms from the above-mentioned alkylene group having 3 to 15 carbon atoms.

[0030] 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.

[0031] 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.

[0032] 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.

[0033] 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): [ka]

[0034] (In the above general formula (ii), R c , R d , R e , R f , R g and R h each independently represents a hydrogen atom or an alkyl group having 1 to 10 carbon atoms; Y 1 and Y 2 are each independently -C(=O)-OR i or a substituted or unsubstituted phenyl group, s, t, and r each independently represent 0 or 1, and s+t+r is an integer of 1 or more, R i represents a hydrogen atom or an alkyl group having 1 to 10 carbon atoms.

[0035] In the above general formula (ii), R c , R d , R e , Rf , R g and R h are each independently preferably a hydrogen atom or a linear or branched alkyl group having 1 to 7 carbon atoms, and more preferably a hydrogen atom or a linear alkyl group having 1 to 5 carbon atoms. In the above general formula (ii), Y 1 and Y 2 are each independently -C(=O)-OR i or preferably represents an unsubstituted phenyl group. i represents a hydrogen atom or an alkyl group having 1 to 5 carbon atoms.

[0036] In the above general formula (I), X is preferably a hydrogen atom or an unsaturated bond group represented by the following general formula (i). [ka]

[0037] (In the above general formula (i), W 1 is a single bond, an amino group, -NHR a group, -R a Represents an O group (R a represents a hydrogen atom or an alkyl group having 1 to 10 carbon atoms; W 2 -NH-, -NR b- , -N=, -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. 1 If is a single bond, W 2 is -N= and W 1 and W 2 may be bonded to form maleimide. In the 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 one of the above formulas (i-1) to (i-9) from the viewpoint of high reactivity with vinyl monomers.

[0038] 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 has the following general formula (1): [ka] (In the above general formula (1), B1 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 (wherein -CH- in the alkylene group may be replaced with -O-, -S-, or -NH- so as not to be adjacent to each other, and further, -CH-CH- 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 (wherein -CH- 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 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.

[0039] In the above general formula (1), L, M, Z and X are each independently selected from the group consisting of B 1In this case, for example, L is present 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.

[0040] In addition, in the above general formula (1), L, M, Z, and X, as well as n and B 1 A preferred embodiment of the formula (I) is represented by the formula (I) above, in which L, M, Z and X, and n and B 1 Since this is similar to the preferred embodiment of the above, it will be omitted here.

[0041] 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 this 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 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 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 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). [ka]

[0042] (In the above general formula (2), B 2 represents a mesogenic group having a divalent aromatic ring or an alkylene group having 3 to 15 carbon atoms (wherein -CH-CH- in the alkylene group may be replaced by -CH=CH-), L 1 and L 2 each independently represents an alkylene group having 1 to 10 carbon atoms (wherein -CH- in the alkylene group may be replaced by -O-, -S-, or -NH-), M 1 , M 2 each independently represents an addition polymerizable monomer unit; Z 1 ~Z 2 each independently represents an alkylene group having 1 to 10 carbon atoms (wherein -CH- in the alkylene group may be replaced by -O-, -S-, or -NH-), n 1 and n 2 each independently represents an integer from 1 to 10,000; X 1 and X 2 each independently represents a hydrogen atom or an unsaturated bond group having two or more electron-withdrawing groups bonded thereto, and X 1 and X 2 At least one of the groups represents an unsaturated bond group to which two or more electron-withdrawing groups are bonded.

[0043] 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.

[0044] 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, a 2,3-naphthylene group, Preferred are anthracene diyl group, 2,5-naphthylene group, 2,6-naphthylene group, 1,8-phenanthrene diyl group, 2,7-phenanthrene diyl group, 3,6-phenanthrene diyl group, 4,5-phenanthrene diyl group, 1,8-anthracene diyl group, 1,5-anthracene diyl group, 1,4-anthracene diyl group, 2,3-anthracene diyl group, and 2,6-anthracene diyl group.

[0045] 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.

[0046] In the above general formula (2), M 1 , M 2 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): [ka]

[0047] (In the above general formula (ii), R c , R d , R e , R f , R g and R h each independently represents a hydrogen atom or an alkyl group having 1 to 10 carbon atoms; Y 1 and Y 2 are each independently -C(=O)-OR i or a substituted or unsubstituted phenyl group, s, t, and r each independently represent 0 or 1, and s+t+r is an integer of 1 or more, R i represents a hydrogen atom or an alkyl group having 1 to 10 carbon atoms.

[0048] In the above general formula (ii), R c , R d , R e , R f , R g and R h are each independently preferably a hydrogen atom or a linear or branched alkyl group having 1 to 7 carbon atoms, and more preferably a hydrogen atom or a linear alkyl group having 1 to 5 carbon atoms. In the above general formula (2), n 1 and n 2 are each independently 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 each independently preferably an unsaturated bond group represented by the following general formula (i). [ka] (In the above general formula (i), W 1 is a single bond, an amino group, -NHR a group, -R a Represents an O group (R a represents a hydrogen atom or an alkyl group having 1 to 10 carbon atoms; W 2 -NH-, -NR b- , -O-(R b ) q (Rb represents an alkylene group having 1 to 10 carbon atoms, and q represents an integer of 0 or more and 1 or less; W 1 If is a single bond, W 2 may be bonded 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).

[0049] 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. [ka] [ka] [ka] [ka] [ka] [ka] [ka] [ka] [ka] (In the above formulas (2-1) to (2-37), m 1 and m 2 are each independently preferably 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 therefore 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). [ka]

[0050] (In the above general formula (3), B 3 represents an organic group (1) obtained by removing any one 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 or less (wherein -CH-CH- in the alkylene group may be replaced by -CH=CH-), M 1 , M 2 , and M 3 each independently represents a single bond or an addition polymerizable monomer unit (conjugated diene monomer unit), Z1 to Z3 each independently represent an alkylene group having 1 to 10 carbon atoms (provided that -CH2- in the alkylene group may be substituted with -O-, -S- or -NH-), n1, n2, and n3 each independently represent an integer of 1 to 10,000. X1, X2, and X3 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 X3 represents an unsaturated bond group having two or more electron-withdrawing groups bonded thereto.

[0051] 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). [ka] In this embodiment, examples of the macromonomer represented by general formula (3) include the following formulae (3-1) to (3-8). [ka] [ka] [ka] [ka] [ka] (In the above formulas (3-1) to (3-8), m 1 , m 2 and m 3 are each independently preferably 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 (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). [ka]

[0052] (In the above general formula (4), B 4 represents an organic group (2) formed by removing two arbitrary hydrogen atoms from a mesogenic group having a tetravalent aromatic ring, a carbon atom, or an alkylene group having 3 to 15 carbon atoms (wherein -CH-CH- in the alkylene group may be replaced by -CH=CH-), M 1 , M 2 , M 3 and M 4 each independently represents a single bond or an addition polymerizable monomer unit (conjugated diene monomer unit), and Z1 to Z 4each independently represents an alkylene group having 1 to 10 carbon atoms (wherein -CH- in the alkylene group may be replaced by -O-, -S-, or -NH-), n 1 , n 2 , n 3 and n 4 each independently represents an integer from 1 to 10,000; X 1 , X 2 , X 3 and X 4 each independently represents a hydrogen atom or an unsaturated bond group having two or more electron-withdrawing groups bonded thereto, and X 1 ~X 4 At least one of the groups represents an unsaturated bond group to which two or more electron-withdrawing groups are bonded.

[0053] In the above general formula (4), examples of the mesogenic group having a tetravalent aromatic ring include (c-1) to (c-3). [ka] (In the above general formula, * represents L 1 ~L 4 (represents a bond that bonds to

[0054] In this embodiment, examples of the macromonomer represented by general formula (4) include the following formulae (4-1) to (4-8). [ka] [ka] [ka] [ka] [ka] [ka] [ka] [ka] (In the above formulas (4-1) to (4-8), m 1 , m 2 , m 3 and m 4 are each independently preferably 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 of 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). [ka] (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 represents a single bond or an addition polymerizable monomer unit (conjugated diene monomer unit), and Z1 to Z 5 each independently represents an alkylene group having 1 to 10 carbon atoms (wherein -CH- in the alkylene group may be replaced by -O-, -S-, or -NH-), n 1 , n 2 , n 3 , n 4 and n 5 each independently represents an integer from 1 to 10,000; X 1 , X 2 , X 3 , X 3 and X 5 each independently represents a hydrogen atom or an unsaturated bond group having two or more electron-withdrawing groups bonded thereto, and X 1 ~X 5At least one of the groups represents an unsaturated bond group to which two or more electron-withdrawing groups are bonded.

[0055] In the above general formula (5), examples of the pentavalent organic group (2) include (d-1) to (d-3). [ka] (In the above general formula, * represents L 1 ~L 5 (represents a bond that bonds to The macromonomer according to the present invention is preferably represented by the following general formula (6). [ka] (In the above general formula (6), B 6 represents a mesogenic group having a hexavalent aromatic ring, L 1 ~L 6 each independently represents a single bond or an alkylene group having 1 to 10 carbon atoms (wherein -CH- in the alkylene group may be replaced by -O-, -S- or -NH-, and further, -CH-CH- in the alkylene group may be replaced by -CH=CH-), M 1 ~M 6 each independently represents a single bond or an addition polymerizable monomer unit, Z 1 ~Z 6 each independently represents a single bond or an alkylene group having 1 to 10 carbon atoms (wherein -CH- in the alkylene group may be replaced by -O-, -S-, or -NH-), n 1 ~n 6 each independently represents an integer from 0 to 10,000; X 1 ~X 6 each independently represents a hydrogen atom or an unsaturated bond group having two or more electron-withdrawing groups bonded thereto, and at least two of X1 to X6 represent an unsaturated bond group having two or more electron-withdrawing groups bonded thereto.)

[0056] In the above general formula (6), examples of the mesogenic group having a hexavalent aromatic ring include (e-1) to (e-3). [ka] (In the above general formula, * represents L 1 ~L 6 (represents a bond that bonds to

[0057] (Method of 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 preferably has the reaction step (1).

[0058] The reaction process (1) preferably comprises the steps of: (a) mixing an aromatic compound having at least two vinyl groups with an organolithium to prepare a reaction mixture (1); (b) mixing the reaction mixture (1) with an addition polymerizable monomer to prepare a reaction mixture (2); (c) mixing a hetero three-membered ring compound with the reaction mixture (2) to prepare a reaction mixture (3); and (d) mixing a compound containing an unsaturated bond group having two or more electron-withdrawing groups bonded thereto with the reaction mixture (3) to prepare a macromonomer.

[0059] In this embodiment, the aromatic compound having at least two vinyl groups is a compound in which 2 to 6 hydrogen atoms in the aromatic compound are substituted with a vinyl group (CH2=CR h -(R h refers to a compound in which a hydrogen atom or an alkyl group having 1 to 5 carbon atoms is substituted.

[0060] 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, an aromatic compound having at least two vinyl groups refers to an aromatic compound in which 2 to 6 hydrogen atoms in the above-exemplified aromatic compound are replaced with a vinyl group (CH2=CR h -(R h is preferably a compound substituted with a hydrogen atom or an alkyl group having 1 to 5 carbon atoms.

[0061] 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 of a low molecular weight compound or a solubilized oligomer. For example, organolithium having a carbon-lithium bond, organolithium having a nitrogen-lithium bond, organolithium having a tin-lithium bond, etc. are included.

[0062] Examples of the organolithium having a carbon-lithium bond include n-butyllithium, sec-butyllithium, tert-butyllithium, n-hexyllithium, benzyllithium, phenyllithium, stilbenelithium, etc. Examples of the organolithium 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, lithium morpholide, etc.

[0063] In the present embodiment, the organolithium may be not only the above-mentioned monoorganolithium but also a polyfunctional organolithium, or a monoorganolithium and a polyfunctional organolithium may be used in combination and polymerized.

[0064] Examples of the polyfunctional organolithium include 1,4-dilithiobutane, a reaction product of sec-butyllithium with diisopropenylbenzene, 1,3,5-trilithiobenzene, a reaction product of n-butyllithium with 1,3-butadiene and divinylbenzene, a reaction product of m-xylene with n-butyllithium, and a reaction product of n-butyllithium with a polyacetylene compound.

[0065] In this embodiment, the addition polymerizable monomer is preferably a conjugated diene monomer such as butadiene, isoprene, myrcene, farnesene, etc., a styrene monomer unit such as styrene, α-methylstyrene, paramethylstyrene, etc., or a (meth)acrylate monomer such as methyl (meth)acrylate, ethyl (meth)acrylate, propyl (meth)acrylate, butyl (meth)acrylate, etc. The addition polymerizable monomer may be composed of two or more of these monomers.

[0066] 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.

[0067] 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.

[0068] 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. [ka]

[0069] (In the compound in step 4 above, R 1 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 of 0 to 10,000.

[0070] When the macromonomer according to the present invention has an alkylene group having 3 to 15 carbon atoms (wherein -CH2-CH2- in the alkylene group may be replaced by -CH=CH-), it is preferable to have the reaction step (2).

[0071] 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.), which allows it to react in a desired manner with a compound containing an unsaturated bond group to which two or more electron-withdrawing groups are bonded. If 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 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.

[0072] 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.

[0073] 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 having two or more electron-withdrawing groups bonded thereto, and the unsaturated bond group having two or more electron-withdrawing groups bonded thereto can be introduced into the end.

[0074] 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.

[0075] In the above step (f), examples of the solvent that can be used for the 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 isoacetate. 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.

[0076] 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 thereto 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 allow the reaction to proceed efficiently, 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 with the 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 to prevent the 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- Phenol 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; copper compounds such as cuprous chloride and copper dimethyldithiocarbamate. These may be used alone or in combination of two or more. In this embodiment, examples of radical polymerization initiators that can be used in copolymerization of 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.

[0077] 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, step (f) corresponds to steps 1 to 3 in the second reaction scheme, and step (g) corresponds to step 4. [ka] (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. EXAMPLES

[0078] 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 the vinyl monomer and the 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 Equipment :TOSOH HLC-8220GPC (Gel Permeation Chromatography) Column: super HZM-H Temperature: 40℃ Carrier: THF 0.35mL / min Detector: RI, UV: 254 nm Calibration curve: Using standard PS manufactured by TOSOH

[0079] (2) Quantitative determination of terminal functional group ratio of macromonomer The terminal functional group ratio of the macromonomer and its raw material, the polymer having diols at both ends, was measured by nuclear magnetic resonance ( 1 Quantification was performed from the integral ratio of the spectrum measured by a H-NMR device. Sample preparation: 75 mg of the macromonomer was dissolved in 0.75 mL of d3-chloroform at room temperature. Measuring equipment: Manufactured by JEOL Ltd., JNM ECA-500 Measurement conditions: Measurement temperature 60℃, observation nucleus 1H, accumulation number 256 times, repeat time 45 seconds

[0080] "Raw materials" "Example 1" Synthesis of polyisoprene main chain macromonomer (macromonomer A) 200 g of polyisoprene diol (poly ip) was placed in a flask, 20 g of maleic anhydride and 0.1 g of antioxidant tertiary butyl catechol were added, 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 to stop the reaction. The reduction rate of hydroxyl groups in polybutadiene diol was calculated. 1 Measurement by 1 H-NMR revealed that the reaction was 98%, confirming that the reaction had proceeded almost quantitatively.

[0081] "Example 2" Synthesis of hydrogenated polyisoprene main chain macromonomer (macromonomer B) 200 g of hydrogenated polyisoprene diol was placed in a flask, 20 g of maleic anhydride and 0.1 g of antioxidant tertiary butyl catechol were added, 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 hydrogenated polyisoprene diol was calculated. 1 Measurement by 1 H-NMR revealed that the reaction was 97%, confirming that the reaction had proceeded almost quantitatively.

[0082] "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., hereafter referred to as TMEDA), triethylamine (Tokyo Chemical Industry Co., Ltd., hereafter referred to as 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 more than 10% 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 form 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 form a homogeneous solution. (Solution C) 9.0 mL of cyclohexane and 0.30 mL of TMEDA were added to a flask and stirred with a stirrer to form a homogeneous solution. (Solution D) 45.0 mL of cyclohexane and 7.5 mL of isoprene were added to a flask and stirred to obtain a homogenous 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.

[0083] "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, followed by 1.8 mL of solution B. The flask was heated to 50°C in a heated oil bath and reacted for 2 hours to prepare an initiator solution.

[0084] "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 the post-polymerization-stopped solution (reaction mixture (3)). "Recovery process"

[0085] 300 mL of methanol, a poor solvent, was placed in a beaker, and the polymerization terminating solution was added dropwise to it using a dropper. As the solution was added, it became cloudy. After the addition was completed, the solution was left to stand for 12 hours, and a precipitate accumulated at the bottom of the beaker. The supernatant was removed and the solution was dried in a desiccator, yielding a polyisoprene diol at both ends. The molecular weight was measured by GPC, and it was found to be Mn=20,000 (PS equivalent). In addition, 1 H-NMR analysis revealed that the rate of hydroxyl group introduction was 98%.

[0086] "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 then 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). 1 According to H-NMR analysis, 99% of the hydroxyl groups were consumed, and the introduction rate of maleic ester was 99%.

[0087] "Example 4" In a flask equipped with a three-way cock, 0.040g of 2,2-bis(4,4-di-t-butylperoxycyclohexyl)propane (hereinafter referred to as Pertetra A) was added as an initiator, 83.86g of styrene, 16.00g of ethylbenzene, and 0.10g of Macromonomer A were added, and the solution was homogenized using a stirrer. This 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 using the above manufacturing method are shown in Table 1.

[0088] "Example 5" 0.040g of Partetra A, 83.86g of styrene, 16.00g of ethylbenzene, and 0.10g of Macromonomer B 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, yielding a colorless, transparent resin. The evaluation results obtained using the above manufacturing method are shown in Table 1.

[0089] "Example 6" 0.040g of Partetra 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. This 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 using the above manufacturing method are shown in Table 1.

[0090] "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 placed and homogenized with a stirrer. This 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 using the above manufacturing method are shown in Table 1.

[0091] "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 stopcock, 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, yielding a colorless, transparent resin. The evaluation results obtained using the above manufacturing method are shown in Table 1.

[0092] "Comparative Example 1" 0.040g of Partetra A, 83.86g of styrene, and 16.00g 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, yielding 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.

[0093] "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 placed in a vacuum dryer set at 230°C for 10 minutes to remove volatile components under high vacuum, and a colorless and transparent resin was obtained. 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 the same as in Comparative Example 1. Furthermore, under these conditions, no copolymerization was observed in the double bonds in the polyisoprene.

[0094] "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, yielding a colorless, transparent resin. The evaluation results obtained using the above 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 copolymerize with styrene, and that the PS molecular weight can be efficiently extended with the same amount of addition.

[0095] "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 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 using the above manufacturing method are shown in Table 1. As shown in the evaluation results, compared with Example 7, the copolymer using the macromonomer of Comparative Example 4 had smaller Mw and Mz.

[0096] "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 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 using the above 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.

[0097] (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 FIG. 1, when the polyisoprene acrylates of Comparative Examples 4 and 5 were used, the molecular weight (interpolated value) reached after 4.2 hours of polymerization reaction was 80×10 4 On the other hand, when the macromonomer C of Examples 7 and 8 was used, it was found that the reaction time required to reach the molecular weight was shortened to 3 hours (shortened by about 1.2 hours). In other words, it was found that the macromonomer C had high copolymerizability with styrene, and the production rate could be increased to 140%.

[0098] [Table 1] [Industrial Applicability]

[0099] The macromonomer according to the present invention can be widely used as a crosslinking agent in copolymerization with addition-polymerizable monomers, an adhesive, a sealing material for electronic materials, and the like.

Claims

1. 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): 【Chemistry 1】 (In the above general formula (1), B １ represents a mesogenic group having an aromatic ring having divalent to tetravalent bonds, 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 is a single bond or an alkylene group having 1 to 10 carbon atoms (provided that the alkylene group does not have —CH ２ - may be replaced by -O-, -S-, or -NH- so as not to be adjacent to each other, and -CH ２ -CH ２ - may be replaced by -CH=CH-; M represents the addition polymerizable monomer unit, which is an isoprene monomer unit or a hydrogenated isoprene monomer unit; Z is a single bond or an alkylene group having 1 to 10 carbon atoms (provided that the alkylene group does not have —CH ２ - may be substituted 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), 【Chemistry 2】 k represents an integer of 2 to 4. In addition, L and M each exist in a plurality of groups in the general formula (1) 、 Z and X may be independently the same or different.

2. The macromonomer according to claim 1 , represented by the following general formula (2): 【Chemistry 3】 (In the above general formula (2), B ２ represents the mesogenic group having a divalent aromatic ring, L １ and L ２ each independently represents 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 , M. ２ each independently represents the addition polymerizable monomer unit, is an isoprene monomer unit, Z １ ~Z ２ each independently represents an alkylene group having 1 to 10 carbon atoms (provided that the —CH ２ - may be substituted by -O-, -S-, or -NH-; n １ and n ２ each independently represents an integer from 1 to 10,000, X １ and X ２ each independently 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 X １ ~X ２ At least one of the formulas (i-1) to (i-9) represents an unsaturated bond group having two or more electron-withdrawing groups bonded thereto.

3. 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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