Polar polyolefins and methods for producing the same

Abstract

The present invention provides polar polyolefins in which the content and distribution of polar groups are highly controlled, and a method for producing the same. [Solution] The polar polyolefin according to the present invention is a unit represented by the following formula (1) (for example, X 1 =CH2, R 1 Each unit (e.g., R = H, l=1, m=3, n=1) or represented by the following formula (2) has the following characteristics. 2 It has (=H, p=7). The polar polyolefin according to the present invention can be produced by coordination polymerization of a predetermined monomer in the presence of a palladium catalyst. TIFF2026082653000058.tif51169

Description

[Technical Field]

[0001] The present invention relates to polar polyolefins obtained by introducing polar groups into polyolefins and to a method for producing the same. [Background technology]

[0002] Polyolefins are widely used as structural materials in various fields due to their low cost and excellent mechanical properties. Furthermore, numerous attempts have been made to introduce polar groups into polyolefins in order to impart various functionalities.

[0003] Polyolefins having hydroxyl groups as polar groups have already been put into practical use. For example, ethylene-vinyl alcohol copolymers (EVOH), which have ethylene units and vinyl alcohol units, exhibit excellent gas barrier properties and are widely used in food packaging materials and other applications. In recent years, copolymers having hydroxyl group-containing units other than vinyl alcohol have also been investigated. Patent Document 1 describes a method for producing hydroxyl group-containing allyl monomer copolymers obtained by copolymerizing α-olefins having 1 to 7 carbon atoms with allyl alcohol using a specific metal complex as a catalyst.

[0004] Polyolefins with pyrrolidone groups introduced as polar groups have already been put into practical use. For example, copolymers of α-olefin and N-vinylpyrrolidone are known to improve water resistance and skin protection when incorporated into topical skin preparations, and are widely used, especially in the field of cosmetics. Patent document 2 describes an emulsified composition comprising a copolymer of polyvinylpyrrolidone and α-olefin, a nonionic surfactant with an HLB of 8 or higher, a higher fatty acid soap, and an oil, wherein the amount of oil is 5 to 50 times that of the copolymer of polyvinylpyrrolidone and α-olefin. [Prior art documents] [Patent Documents]

[0005] [Patent Document 1] Japanese Patent Publication No. 2011-68881 [Patent Document 2] Japanese Patent Application Publication No. 7-89826 [Overview of the project] [Problems that the invention aims to solve]

[0006] However, since polar polyolefins, which are obtained by introducing polar groups into polyolefins, are basically random copolymers of α-olefins and monomers containing polar groups, it has been difficult to control the content and distribution of polar groups in polar polyolefins, and it has also often been difficult to increase the content of polar groups.

[0007] Therefore, the present invention aims to provide a polar polyolefin in which the content and distribution of polar groups are highly controlled, and a method for producing the same. [Means for solving the problem]

[0008] The present invention relates to the following formula (1): [ka] (In formula (1), X 1 is a methylene group or a divalent cyclohexane residue, R 1 (where l is a hydrogen atom, an alkyl group, or a silyl group, l is 0 or 1, m is an integer from 0 to 30, and n is an integer from 0 to 4.) This is a polar polyolefin having unit A represented by [the formula shown].

[0009] The present invention relates to a method for producing a polar polyolefin having unit A represented by the above formula (1), In the presence of a palladium catalyst, the following equation (11): [ka] (In formula (11), X 11 is a methyl group or a cyclohexyl group, R 11is an alkyl group or a silyl group, and l, m, and n are the same as l, m, and n in formula (1).) comprising a step of coordinatively polymerizing monomer a represented by a method.

[0010] The present invention relates to the following formula (2a):

Chemical formula

Chemical formula

[0011] The present invention relates to unit B represented by the above formula (2a) 1 and unit B represented by the above formula (2b) 2 a method for producing a polar polyolefin having, comprising in the presence of a palladium catalyst, the following formula (21a):

Chemical formula

Chemical formula

[0012] The present invention relates to the following formula (2ax): [ka] (In formula (2ax), R 2 R is a hydrogen atom, an alkylsulfonyl group, an arylsulfonyl group, an alkyloxycarbonyl group, or an aryloxycarbonyl group. 2x (This is a hydrogen atom or an alkyl group.) Unit B represented by 1x and, The following equation (2b): [ka] (In equation (2b), p is an integer between 3 and 27.) Unit B represented by 2 and It has, Furthermore, the following equation (2a): [ka] Unit B represented by 2 It is a polar polyolefin which may have polar properties.

[0013] The present invention relates to unit B represented by the above formula (2ax) 1x And, unit B represented by the above formula (2b) 2 Unit B, which has the above formula (2a), 1 A method for producing polar polyolefins which may have, Using an alkyl alcohol solution of an alkali metal hydroxide, Unit B represented by the above formula (2a) 1 And, unit B represented by the above formula (2b) 2 The process includes opening at least a portion of the pyrrolidone ring in a polar polyolefin having the following characteristics: It is a method.

[0014] The present invention relates to the following formula (2a): [ka] (In formula (2a), R 2 (This is a hydrogen atom, an alkylsulfonyl group, an arylsulfonyl group, an alkyloxycarbonyl group, or an aryloxycarbonyl group.) Unit B represented by 1 , and / or The following equation (2ax): [ka] (In formula (2ax), R 2 R is a hydrogen atom, an alkylsulfonyl group, an arylsulfonyl group, an alkyloxycarbonyl group, or an aryloxycarbonyl group. 2x (This is a hydrogen atom or an alkyl group.) Unit B represented by 1x and, The following equation (2ay): [ka] (In formula (2ay), R 2 R is a hydrogen atom, an alkylsulfonyl group, an arylsulfonyl group, an alkyloxycarbonyl group, or an aryloxycarbonyl group. 2y (This is a hydrogen atom or an alkyl group.) Unit B represented by 1y and, The following equation (2b): [ka] (In equation (2b), p is an integer between 3 and 27.) Unit B represented by 2 and It is a polar polyolefin having [a certain characteristic].

[0015] The present invention relates to Unit B represented by the above formula (2a) 1and / or Unit B represented by the above formula (2ax) 1x And, unit B represented by the above formula (2ay) 1y And, unit B represented by the above formula (2b) 2 A method for producing polar polyolefins having the following characteristics: In the presence of diarylketones, unit B represented by the above formula (2ax) 1x And, unit B represented by the above formula (2b) 2 Unit B, which has the above formula (2a), 1 By irradiating a polar polyolefin, which may have, with light, the unit B 1x The process includes a step of splitting at least a portion of it. It is a method. [Effects of the Invention]

[0016] According to the present invention, it is possible to provide polar polyolefins in which the content and distribution of polar groups are highly controlled, and a method for producing the same. [Brief explanation of the drawing]

[0017] [Figure 1] This is the 1H-NMR chart (solvent: CDCl3, room temperature) of the polar polyolefin (X1=CH2, R1=SiiPr3, l=1, m=3, n=1) obtained in Example 1-1. [Figure 2] This is the 1H-NMR chart (solvent: CDCl3, room temperature) of the polar polyolefin (X1=CH2, R1=SiMe2 tBu, l=1, m=3, n=1) obtained in Examples 1-8. [Figure 3] This is the 1H-NMR chart (solvent: CDCl3, room temperature) of the polar polyolefin (X1=CH2, R1=H, l=1, m=3, n=1) obtained in Examples 1-8. [Figure 4] This is the 1H-NMR chart (solvent: CDCl3, room temperature) of the polar polyolefin (X1=C6H10, R1=SiMe2 tBu, l=0, m=2, n=2) obtained in Examples 1-17. [Figure 5]This is the 1H-NMR chart (solvent: C2D2Cl4, 130°C) of the polar polyolefin (X1=C6H10, R1=H, l=0, m=2, n=2) obtained in Examples 1-17. [Figure 6] This is the 1H-NMR chart (solvent: CDCl3, room temperature) of the polar polyolefin (R2=Ts, p=7) obtained in Example 2-1. [Figure 7] This is the 1H-NMR chart (solvent: CDCl3, room temperature) of the polar polyolefin (R2=H, p=7) obtained in Example 2-1. [Figure 8] This is the 1H-NMR chart of the polar polyolefin obtained in Example 3-1 (solvent: DMSO-d6, room temperature). [Modes for carrying out the invention]

[0018] <First Embodiment> The polar polyolefin according to the first embodiment of the present invention has a unit A represented by the following formula (1). That is, it is a polar polyolefin having a structure represented by the following formula (1).

[0019] [ka] (In formula (1), X 1 is a methylene group or a divalent cyclohexane residue, R 1 (where l is a hydrogen atom, an alkyl group, or a silyl group, l is 0 or 1, m is an integer from 0 to 30, and n is an integer from 0 to 4.)

[0020] In formula (1), X 1 This is a methylene group or a divalent cyclohexane residue. Specific examples of divalent cyclohexane residues include cyclohexane-1,1-diyl, cyclohexane-1,2-diyl, cyclohexane-1,3-diyl, and cyclohexane-1,4-diyl. Among these, the cyclohexane-1,4-diyl group is preferred. 1 These units may be the same or different in each unit of the polar polyolefin.

[0021] In formula (1), R 1 is a hydrogen atom, an alkyl group, or a silyl group. Specific examples of alkyl groups include C1-C6 alkyl groups such as methyl, ethyl, propyl, isopropyl, butyl, sec-butyl, isobutyl, tert-butyl, pentyl, and hexyl groups. Among these, C1-C3 alkyl groups are preferred, and methyl or ethyl groups are more preferred. Specific examples of silyl groups include trialkylsilyl groups such as trimethylsilyl (TMS), triethylsilyl (TES), triisopropylsilyl (TIPS), and tert-butyldimethylsilyl (TBDMS), and tert-butyldiphenylsilyl (TBDPS). Among these, trialkylsilyl groups are preferred, and trimethylsilyl, triethylsilyl, triisopropylsilyl, or tert-butyldimethylsilyl groups are more preferred. 1 These units may be the same or different in each unit of the polar polyolefin.

[0022] In formula (1), l is 0 or 1, m is an integer from 0 to 30, and n is an integer from 0 to 4. l is preferably 1. m is preferably an integer from 1 to 24, and more preferably an integer from 3 to 18. n is preferably 1 or 2, and more preferably 1. l, m, and n may be the same or different in each unit of the polar polyolefin.

[0023] The number-average molecular weight (Mn) of the polar polyolefin is preferably 500 to 50,000, more preferably 1,000 to 40,000, and even more preferably 5,000 to 30,000. The molecular weight distribution (Mw / Mn) of the polar polyolefin is preferably 1.1 to 3.5, and more preferably 1.2 to 2.5. The number-average molecular weight (Mn) and molecular weight distribution (Mw / Mn) of the polar polyolefin can be measured by GPC (eluent: tetrahydrofuran).

[0024] With polar polyolefins as described above, it becomes possible to highly control the content and distribution of polar groups. That is, while the number of carbon atoms in the main chain of unit A is (m+n+4), one unit A contains one polar group (-OR 1 Because of the bonding, the content of polar groups in polar polyolefins can be controlled, for example, by the values ​​of m and n in unit A. Furthermore, the distribution of polar groups in polar polyolefins can be controlled, for example, by including multiple types of unit A with different m and n values.

[0025] The above polar polyolefins can be produced, for example, by coordination polymerization of monomer a represented by the following formula (11) in the presence of a palladium catalyst.

[0026] [ka] (In formula (11), X 11 is a methyl group or a cyclohexyl group, R 11 (where l, m, and n are the same as l, m, and n in formula (1).)

[0027] In other words, the coordination polymerization of monomer a proceeds as shown in the following reaction equation.

[0028] [ka]

[0029] In formula (11), X 11 The group is either a methyl group or a cyclohexyl group. Furthermore, the target polar polyolefin X 1 If it is a methylene group, then the X of monomer a 11 This is a methyl group, and the X of the target polar polyolefin 1 If it is a divalent cyclohexane residue, then the X of monomer a 11 It is a cyclohexyl group.

[0030] In formula (11), R11 R is an alkyl group or a silyl group. A specific example of an alkyl group is R in formula (1) mentioned above. 1 Examples of alkyl groups are similar to those mentioned above. An example of a silyl group is the R in formula (1) above. 1 Examples of silyl groups that result in this can be found. Furthermore, the R of the target polar polyolefin is... 1 If it is an alkyl group or a silyl group, then the R of monomer a 11 R 1 It is preferable that it is the same alkyl group or silyl group as R 1 The R of the target polar polyolefin may be a different alkyl or silyl group. 1 If R is a hydrogen atom, 11 R can be appropriately selected from alkyl groups or silyl groups. In that case, the R in the resulting polymer 11 By deprotecting and substituting with a hydrogen atom, R 1 This allows for the production of polar polyolefins in which hydrogen atoms are present.

[0031] In equation (11), l, m, and n are selected to be the same as l, m, and n in equation (1).

[0032] Note that the monomer a(R) for which l in equation (11) is 1 11 =H) can be produced, for example, by reacting fatty acid methyl and alkenyl bromide in the presence of lithium diisopropylamide (LDA), as shown in the reaction equation below, and further reducing the ester group with lithium aluminum hydride (LiAlH4). Furthermore, if necessary, the hydrogen atom of the -OH group of this monomer a can be reduced by R 11 It can also be substituted with an alkyl group or silyl group.

[0033] [ka]

[0034] Also, the monomer a(R) for which l in equation (11) is 0 11=H) can be produced, for example, by reducing the ester group of fatty acid methyl with diisobutylaluminum hydride (DIBAL) as shown in the reaction equation below, and reacting the resulting aldehyde with alkenyl magnesium bromide (also alkenyl magnesium chloride). Furthermore, if necessary, the hydrogen atom of the -OH group of this monomer a can be R 11 It is also possible to substitute it with an alkyl group or silyl group.

[0035] [ka]

[0036] The coordination polymerization of monomer a is carried out in the presence of a palladium catalyst. As the palladium catalyst, for example, a palladium compound cationized with an organoaluminum compound or a boron compound can be used. Among these, from the viewpoint of reactivity, it is preferable to use an imine-type palladium complex cationized with a boron compound.

[0037] As an imine-type palladium complex, for example, a palladium mononuclear complex represented by the following formula (3) can be used. A specific example of the palladium mononuclear complex represented by the following formula (3) is also described in Japanese Patent Application Publication No. 2008-239980.

[0038] [ka] (In formula (3), L 31 and L 32 Each of these is independently a hydrogen atom, a halogen atom, an alkyl group, an aralkyl group, an aryl group, a silyl group, a siloxy group, an alkoxy group, an aralkyloxy group, or an aryloxy group, and R 31 and R 32 Each of these is independently a hydrocarbon group having 1 to 30 carbon atoms, and R 33 and R 34 Each of these is independently a hydrogen atom or a hydrocarbon group having 1 to 20 carbon atoms, and R 33 and R 34They may be joined to each other to form a ring.

[0039] In formula (3), L 31 and L 32 Each of these is independently a hydrogen atom, a halogen atom, an alkyl group, an aralkyl group, an aryl group, a silyl group, a siloxy group, an alkoxy group, an aralkyloxy group, or an aryloxy group, but a halogen atom or an alkyl group is preferred. Specific examples of halogen atoms include fluorine, chlorine, bromine, and iodine atoms. Among these, chlorine or bromine atoms are preferred, and chlorine atoms are more preferred. Specific examples of alkyl groups include linear alkyl groups such as methyl, ethyl, and n-butyl groups; branched alkyl groups such as isopropyl, isobutyl, tert-butyl, and neopentyl groups; and cyclic alkyl groups such as cyclohexyl and cyclooctyl. Among these, linear alkyl groups are preferred, linear alkyl groups having 1 to 12 carbon atoms are more preferred, and methyl groups are even more preferred. 31 and L 32 A combination of a halogen atom and an alkyl group is preferred, and a combination of a chlorine atom and a methyl group is more preferred.

[0040] In formula (3), R 31 and R 32Each of these is independently a hydrocarbon group having 1 to 30 carbon atoms, and the hydrocarbon group is preferably an alkyl group, an aralkyl group, or an aryl group, and more preferably an aryl group.Specific examples of aryl groups include phenyl groups; monoalkylphenyl groups such as 2-methylphenyl, 2-ethylphenyl, 2-n-propylphenyl, 2-isopropylphenyl, 2-n-butylphenyl, 2-isobutylphenyl, 2-n-hexylphenyl, and 4-methylphenyl; 2,6-dimethylphenyl, 2,6-diethylphenyl, 2,6-di-n-propylphenyl, 2,6-diisopropylphenyl, 2,6-di-n-butylphenyl, 2,6-diisobutylphenyl, and 2,6-di-n - Dialkylphenyl groups such as hexylphenyl group, 2-methyl-6-ethylphenyl group, 2-methyl-6-n-propylphenyl group, 2-methyl-6-isopropylphenyl group, 2-methyl-6-butylphenyl group, 2-ethyl-6-n-propylphenyl group, 2-ethyl-6-n-butylphenyl group, 2-n-propyl-6-isopropylphenyl group, 2-n-propyl-6-n-butylphenyl group, and 2-isopropyl-6-n-butylphenyl group; 2,4,6-trimethylphenyl 2,4-dimethyl-6-(2-methylphenyl)phenyl group, 2,4-dimethyl-6-(2-ethylphenyl)phenyl group, 2,4-dimethyl-6-(2-n-propylphenyl)phenyl group, 2,4-dimethyl-6-(2-isopropylphenyl)phenyl group, 2,4-dimethyl-6-(2,6-dimethylphenyl)phenyl group, 2,4-dimethyl-6-(2,6-diethylphenyl)phenyl group, 2,4-dimethyl-6-(2,6-di-n-propylphenyl)phenyl group, 2,4-dimethyl-6-(2,6-diisopropylphenyl)phenyl group Examples of trialkylphenyl groups include 2,4-dimethyl-6-(2-methyl-6-ethylphenyl)phenyl group, 2,4-dimethyl-6-(2-methyl-6-n-propylphenyl)phenyl group, 2,4-dimethyl-6-(2-methyl-6-isopropylphenyl)phenyl group, 2,4-dimethyl-6-(2-ethyl-6-n-propylphenyl)phenyl group, 2,4-dimethyl-6-(2-ethyl-6-isopropylphenyl)phenyl group, and 2,4-dimethyl-6-(1-naphthyl)phenyl group.Among these, the trialkylphenyl group is preferred, and the 2,4,6-trimethylphenyl group is more preferred. R. 31 and R 32 It is preferable that they be the same.

[0041] In formula (3), R 33 and R 34 Each of these is independently a hydrogen atom or a hydrocarbon group having 1 to 20 carbon atoms, but the hydrocarbon group is preferably an alkyl group or an aryl group, and more preferably an aryl group. 33 and R 34 These groups may be bonded to each other to form a ring, in which case they are preferably divalent groups forming an aliphatic or aromatic ring, and more preferably divalent groups forming an aromatic ring. Specific examples of divalent groups forming an aromatic ring include the 1,2-phenylene group and the naphthalene-1,8-diyl group. Among these, the naphthalene-1,8-diyl group is preferred.

[0042] Examples of imine-type palladium complexes include the palladium mononuclear complex represented by the following formula (3a).

[0043] [ka] (In formula (3a), A is independently an alkyl group having 1 to 4 carbon atoms, and B is a hydrogen atom, a halogen atom, an alkyl group having 1 to 4 carbon atoms, an alkoxy group having 1 to 4 carbon atoms, or an alkyl ester group having 1 to 4 carbon atoms.)

[0044] In formula (3a), A is independently an alkyl group having 1 to 4 carbon atoms. Specific examples of alkyl groups having 1 to 4 carbon atoms include methyl, ethyl, propyl, isopropyl, butyl, sec-butyl, isobutyl, and tert-butyl groups. Among these, methyl or isopropyl groups are more preferred.

[0045] In formula (3a), B is, independently of one another, a hydrogen atom, a halogen atom, an alkyl group having 1 to 4 carbon atoms, an alkoxy group having 1 to 4 carbon atoms, or an alkyl ester group having 1 to 4 carbon atoms. Specific examples of the halogen atom include a fluorine atom, a chlorine atom, a bromine atom, an iodine atom, and a francium atom. Specific examples of the alkyl group having 1 to 4 carbon atoms include a methyl group, an ethyl group, a propyl group, an isopropyl group, a butyl group, a sec-butyl group, an isobutyl group, and a tert-butyl group. Specific examples of the alkoxy group having 1 to 4 carbon atoms include a methoxy group, an ethoxy group, a propoxy group, an isopropoxy group, a butoxy group, a sec-butoxy group, an isobutoxy group, and a tert-butoxy group. Specific examples of the alkyl ester group having 1 to 4 carbon atoms include a methoxycarbonyl group, an ethoxycarbonyl group, a propoxycarbonyl group, an isopropoxycarbonyl group, a butoxycarbonyl group, a sec-butoxycarbonyl group, an isobutoxycarbonyl group, and a tert-butoxycarbonyl group. Among these, a methyl group is preferred.

[0046] As the imine-type palladium complex, for example, a palladium cyclic dinuclear complex represented by the following formula (4) can be used. Specific examples of the palladium cyclic dinuclear complex represented by the following formula (4) are also described in JP-A-2015-117237.

[0047] [Chemical formula] (In formula (4), L 41 , L 42 , L 43 , and L 44 are, independently of one another, a hydrogen atom, a hydrocarbon group having 1 to 20 carbon atoms, an alkoxy group having 1 to 10 carbon atoms, an aryloxy group having 6 to 20 carbon atoms, an ester group having 2 to 10 carbon atoms, a substituted amino group having 1 to 12 carbon atoms, a thiocyanate group, or a halogen atom, and R 41 and R 42is, independently of each other, a divalent hydrocarbon group having 1 to 20 carbon atoms, a divalent hydrocarbon group having 1 to 20 carbon atoms substituted with a hydroxyl group, a divalent hydrocarbon group having 2 to 20 carbon atoms substituted with an alkoxy group having 1 to 10 carbon atoms, a divalent hydrocarbon group having 3 to 20 carbon atoms substituted with an ester group having 2 to 10 carbon atoms, a divalent hydrocarbon group having 4 to 20 carbon atoms substituted with a silyl group having 3 to 18 carbon atoms, or a divalent hydrocarbon group having 1 to 20 carbon atoms substituted with a halogen atom, R 43 R 44 R 45 and R 46 are, independently of each other, a hydrogen atom, a halogen atom, a hydrocarbon group having 1 to 20 carbon atoms, a hydrocarbon group having 1 to 20 carbon atoms substituted with a halogen atom, a hydrocarbon group having 2 to 20 carbon atoms substituted with an alkoxy group having 1 to 10 carbon atoms, an alkoxy group having 1 to 10 carbon atoms, or a substituted amino group having 1 to 20 carbon atoms, R 43 and R 44 and R 45 and R 46 may be independently bonded to each other to form a ring.)

[0048] In formula (4), L 41 L 42 L 43 and L 44 are, independently of each other, a hydrogen atom, a hydrocarbon group having 1 to 20 carbon atoms, an alkoxy group having 1 to 10 carbon atoms, an aryloxy group having 6 to 20 carbon atoms, an ester group having 2 to 10 carbon atoms, a substituted amino group having 1 to 12 carbon atoms, a thiocyanate group, or a halogen atom, and the hydrocarbon group is preferably an alkyl group, a cycloalkyl group, an alkenyl group, or an aryl group. L 41 L 42 L 43 and L 44Each of these is preferably an independent hydrocarbon group having 1 to 20 carbon atoms or a halogen atom. Specific examples of hydrocarbon groups having 1 to 20 carbon atoms include linear alkyl groups such as methyl, ethyl, and n-butyl groups; branched alkyl groups such as isopropyl, isobutyl, tert-butyl, and neopentyl groups; and cyclic alkyl groups such as cyclohexyl and cyclooctyl. Among these, linear alkyl groups having 1 to 10 carbon atoms are preferred, and methyl groups are more preferred. Specific examples of halogen atoms include fluorine, chlorine, bromine, and iodine atoms. Among these, chlorine or bromine atoms are preferred, and chlorine atoms are more preferred. 41 and L 42 , and L 43 and L 44 In all cases, a combination of a halogen atom and an alkyl group is preferred, and a combination of a chlorine atom and a methyl group is more preferred.

[0049] In formula (4), R 41 and R 42 Each of these is independently a divalent hydrocarbon group having 1 to 20 carbon atoms, a divalent hydrocarbon group having 1 to 20 carbon atoms substituted with a hydroxyl group, a divalent hydrocarbon group having 2 to 20 carbon atoms substituted with an alkoxy group having 1 to 10 carbon atoms, a divalent hydrocarbon group having 3 to 20 carbon atoms substituted with an ester group having 2 to 10 carbon atoms, a divalent hydrocarbon group having 4 to 20 carbon atoms substituted with a silyl group having 3 to 18 carbon atoms, or a divalent hydrocarbon group having 1 to 20 carbon atoms substituted with a halogen atom. The hydrocarbon group is preferably an alkylene group having 1 to 12 carbon atoms, a phenylene group, an alkylene-phenylene-alkylene group, a biphenylene group, or a diarylalkyl group, and more preferably a diarylalkyl group. Specific examples of diarylalkyl groups include divalent diarylalkyl groups having 14 to 20 carbon atoms, such as 2,3,6,7,9,9-hexamethylxanthene-4,5-diyl group and 2,7-t-butyl-9,9-dimethylxanthene-4,5-diyl group. Among these, the 2,3,6,7,9,9-hexamethylxanthene-4,5-diyl group is preferred.

[0050] In formula (4), R 43 , R44 , R 45 , and R 46 are each independently a hydrogen atom, a halogen atom, a hydrocarbon group having 1 to 20 carbon atoms, a hydrocarbon group having 1 to 20 carbon atoms substituted with a halogen atom, a hydrocarbon group having 2 to 20 carbon atoms substituted with an alkoxy group having 1 to 10 carbon atoms, an alkoxy group having 1 to 10 carbon atoms, or a substituted amino group having 1 to 20 carbon atoms, and the hydrocarbon group is preferably an alkyl group or an aryl group, and more preferably an aryl group. R 43 and R 44 , and R 45 and R 46 may each independently be bonded to each other to form a ring, and in that case, they are each independently preferably a divalent group that forms an aliphatic ring or an aromatic ring, and more preferably a divalent group that forms an aromatic ring. Specific examples of the divalent group that forms an aromatic ring include a 1,2-phenylene group and a naphthalene-1,8-diyl group. Among them, a naphthalene-1,8-diyl group is preferable.

[0051] Examples of the imine-type palladium complex as described above include a palladium cyclic dinuclear complex represented by the following formula (4a).

[0052] [Chemical formula]

[0053] As the component for cationizing the palladium compound, for example, an organoaluminum compound or a boron compound can be used, and a boron compound is preferable. As the boron compound, for example, a boron compound represented by the following formula (5) or the following formula (6) can be used. Among them, it is preferable to use a boron compound represented by the following formula (6). Specific examples of the boron compound represented by the following formula (5) or the following formula (6) are also described in JP-A-2008-239980.

[0054] BR 51 R 52 R 53 (5) (In formula (5), R 51 , R 52 , and R 53 are each independently a halogen atom, a hydrocarbon group having 1 to 20 carbon atoms, a halogenated hydrocarbon group having 1 to 20 carbon atoms, a silyl group having 1 to 20 carbon atoms, a siloxy group having 1 to 20 carbon atoms, an amino group substituted with a hydrocarbon group having 2 to 20 carbon atoms, an amide group substituted with a hydrocarbon group having 2 to 20 carbon atoms, or an imide group substituted with a hydrocarbon group having 2 to 20 carbon atoms.)

[0055] Q + (BR 61 R 62 R 63 R 64 ) - (6) (In formula (6), Q + is an inorganic or organic cation, and R 61 , R 62 , R 63 , and R 64 are each independently a halogen atom, a hydrocarbon group having 1 to 20 carbon atoms, a halogenated hydrocarbon group having 1 to 20 carbon atoms, a silyl group having 1 to 20 carbon atoms, a siloxy group having 1 to 20 carbon atoms, an amino group substituted with a hydrocarbon group having 2 to 20 carbon atoms, an amide group substituted with a hydrocarbon group having 2 to 20 carbon atoms, or an imide group substituted with a hydrocarbon group having 2 to 20 carbon atoms.)

[0056] In formula (5), R 51 , R 52 , and R 53 are each independently a halogen atom, a hydrocarbon group having 1 to 20 carbon atoms, a halogenated hydrocarbon group having 1 to 20 carbon atoms, a silyl group having 1 to 20 carbon atoms, a siloxy group having 1 to 20 carbon atoms, an amino group substituted with a hydrocarbon group having 2 to 20 carbon atoms, an amide group substituted with a hydrocarbon group having 2 to 20 carbon atoms, or an imide group substituted with a hydrocarbon group having 2 to 20 carbon atoms, provided that the hydrocarbon group is preferably an alkyl group, a cycloalkyl group, an alkenyl group, or an aryl group. In formula (5), R 51 , R 52 , and R 53Each of these is preferably independently a halogen atom, a hydrocarbon group having 1 to 20 carbon atoms, or a halogenated hydrocarbon group having 1 to 20 carbon atoms, more preferably a fluorinated hydrocarbon group having 1 to 20 carbon atoms containing at least one fluorine atom, and even more preferably a fluorinated aryl group having 6 to 20 carbon atoms containing at least one fluorine atom.

[0057] In formula (6), Q + These are inorganic or organic cations. Among these, alkali metal cations such as lithium cations, sodium cations, and potassium cations, or organic cations such as organic phosphonium cations, organic ammonium cations, organic sulfonium cations, organic iodonium cations, and carbenium cations are preferred.

[0058] In formula (6), R 61 , R 62 , R 63 , and R 64c Each of these is independently a halogen atom, a hydrocarbon group having 1 to 20 carbon atoms, a halogenated hydrocarbon group having 1 to 20 carbon atoms, a silyl group having 1 to 20 carbon atoms, a siloxy group having 1 to 20 carbon atoms, an amino group substituted with a hydrocarbon group having 2 to 20 carbon atoms, an amide group substituted with a hydrocarbon group having 2 to 20 carbon atoms, or an imide group substituted with a hydrocarbon group having 2 to 20 carbon atoms, but the hydrocarbon group is preferably an alkyl group, a cycloalkyl group, an alkenyl group, or an aryl group. In formula (6), R 61 , R 62 , R 63 , and R 64 Each of these is preferably independently a halogen atom, a hydrocarbon group having 1 to 20 carbon atoms, or a halogenated hydrocarbon group having 1 to 20 carbon atoms, more preferably a fluorinated hydrocarbon group having 1 to 20 carbon atoms containing at least one fluorine atom, and even more preferably a fluorinated aryl group having 6 to 20 carbon atoms containing at least one fluorine atom.

[0059] Specific examples of boron compounds represented by formula (6) include lithium tetrakis(3,5-bistrifluoromethylphenyl) borate, sodium tetrakis(3,5-bistrifluoromethylphenyl) borate, potassium tetrakis(3,5-bistrifluoromethylphenyl) borate, tetrabutylphosphonium tetrakis(pentafluorophenyl) borate, tetraphenylphosphonium tetrakis(pentafluorophenyl) borate, tetramethylammonium tetrakis(pentafluorophenyl) borate, trimethylsulfonium tetrakis(pentafluorophenyl) borate, diphenyliodonium tetrakis(pentafluorophenyl) borate, triphenylcarbenium tetrakis(pentafluorophenyl) borate, and triphenylcarbenium tetrakis(3,5-bistrifluoromethylphenyl) borate. Among these, lithium tetrakis(3,5-bistrifluoromethylphenyl) borate, sodium tetrakis(3,5-bistrifluoromethylphenyl) borate, or potassium tetrakis(3,5-bistrifluoromethylphenyl) borate are preferred, with sodium tetrakis(3,5-bistrifluoromethylphenyl) borate being more preferred.

[0060] The amount of organoaluminum compound or boron compound used to cationize the palladium compound is preferably 1.0 to 1.4 moles, and more preferably 1.1 to 1.3 moles, per mole of palladium in the palladium compound.

[0061] The coordination polymerization of monomer a is preferably carried out in an inert gas such as nitrogen or argon. As solvents, halogenated hydrocarbons such as methylene chloride, 1,2-dichloroethane, 1,1,2,2-tetrachloroethane, chlorobenzene, and chloroform; aromatic hydrocarbons such as toluene; and aliphatic hydrocarbons such as pentane and hexane can be used. Among these, methylene chloride, 1,2-dichloroethane, 1,1,2,2-tetrachloroethane, chlorobenzene, chloroform, or toluene are preferred. The reaction temperature can be, for example, -40°C to 80°C, and is preferably -20°C to 60°C.

[0062] According to the first embodiment described above, it is possible to provide a polar polyolefin in which the content and distribution of polar groups are highly controlled, and a method for producing the same.

[0063] <Second Embodiment> The polar polyolefin according to the second embodiment of the present invention is unit B represented by the following formula (2a) 1 And, unit B, which is represented by the following formula (2b) 2 It has the following characteristics. That is, it is a polar polyolefin having a structure represented by the following formula (2).

[0064] [ka] (In formula (2a), R 2 (This is a hydrogen atom, an alkylsulfonyl group, an arylsulfonyl group, an alkyloxycarbonyl group, or an aryloxycarbonyl group.)

[0065] [ka] (In equation (2b), p is an integer between 3 and 27.)

[0066] [ka] (In formula (2), R 2 R in equation (2a) 2This is identical, and p is identical to p in equation (2b).

[0067] In formula (2a), R 2 This group consists of a hydrogen atom, an alkylsulfonyl group, an arylsulfonyl group, an alkyloxycarbonyl group, or an aryloxycarbonyl group. Specific examples of alkylsulfonyl groups include C1-C6 alkylsulfonyl groups such as methylsulfonyl group, ethylsulfonyl group, propylsulfonyl group, isopropylsulfonyl group, butylsulfonyl group, sec-butylsulfonyl group, isobutylsulfonyl group, tert-butylsulfonyl group, pentylsulfonyl group, and hexylsulfonyl group. Among these, C1-C3 alkylsulfonyl groups are preferred, and methylsulfonyl groups or ethylsulfonyl groups are more preferred. Specific examples of arylsulfonyl groups include benzenesulfonyl group; toluenesulfonyl group (o-toluenesulfonyl group, m-toluenesulfonyl group, p-toluenesulfonyl group); and xylenesulfonyl group (o-xylenesulfonyl group, m-xylenesulfonyl group, p-xylenesulfonyl group). Among these, toluenesulfonyl groups are preferred, and p-toluenesulfonyl groups are more preferred. Specific examples of alkyloxycarbonyl groups include alkyloxycarbonyl groups having 1 to 6 carbon atoms, such as methoxycarbonyl group, ethoxycarbonyl group, propoxycarbonyl group, isopropoxycarbonyl group, butytoxycarbonyl group, sec-butoxycarbonyl group, isobutoxycarbonyl group, tert-butoxycarbonyl group, pentyloxycarbonyl group, and hexyloxycarbonyl group. Among these, alkyloxycarbonyl groups having 4 carbon atoms are preferred, and tert-butoxycarbonyl groups are more preferred. Specific examples of aryloxycarbonyl groups include phenoxycarbonyl group; tolyloxycarbonyl groups (o-tolyloxycarbonyl group, m-tolyloxycarbonyl group, p-tolyloxycarbonyl group); and xylyloxycarbonyl groups (o-xylyloxycarbonyl group, m-xylyloxycarbonyl group, p-xylyloxycarbonyl group). Among these, a phenoxycarbonyl group or a tolyloxycarbonyl group is preferred, and a phenoxycarbonyl group is more preferred.2 These units may be the same or different in each unit of the polar polyolefin.

[0068] In formula (2b), p is an integer between 3 and 27. Preferably, p is an integer between 4 and 21, and more preferably between 5 and 15. p may be the same or different in each unit of the polar polyolefin.

[0069] Unit B contained in polar polyolefins 1 and Unit B 2 Unit B for the total 1 The proportion (B 1 / ( B 1 +B 2 The value of )) is preferably 0.10 to 0.70, more preferably 0.15 to 0.60, and even more preferably 0.20 to 0.50. Note that Unit B contained in polar polyolefins 1 and Unit B 2 Unit B for the total 1 The proportion (B 1 / ( B 1 +B 2 )) is a polar polyolefin 1 It can be calculated from the proton integral ratio derived from each unit by 1H-NMR analysis (solvent: CDCl3, room temperature).

[0070] The number-average molecular weight (Mn) of the polar polyolefin is preferably 500 to 50,000, more preferably 1,000 to 30,000, and even more preferably 3,000 to 10,000. The molecular weight distribution (Mw / Mn) of the polar polyolefin is preferably 1.1 to 3.5, and more preferably 1.2 to 2.5. The number-average molecular weight (Mn) and molecular weight distribution (Mw / Mn) of the polar polyolefin can be measured by GPC (eluent: tetrahydrofuran).

[0071] With polar polyolefins like the ones described above, it becomes possible to highly control the content and distribution of polar groups. That is, Unit B1 The main chain of [unit] has 4 carbon atoms, and for unit B 2 the main chain has (3 + p) carbon atoms, and for one unit B 1 one polar group (-NR 2 ) is bonded, so the content of the polar groups in the polar polyolefin can be controlled, for example, by the ratio of unit B 1 to unit B 2 with respect to the total of unit B 1 (B 1 / (B 1 + B 2 )) and the value of p in unit B 2 . Also, the distribution of the polar groups in the polar polyolefin can be controlled, for example, by including multiple types of unit B 2 with different p values.

[0072] The above-mentioned polar polyolefin can be produced, for example, by coordinative copolymerization of monomer b 1 represented by the following formula (21a) and monomer b 2 represented by the following formula (21b) in the presence of a palladium catalyst.

[0073] [Chemical formula] (In formula (21a), R 21 is an alkylsulfonyl group, an arylsulfonyl group, an alkyloxycarbonyl group, or an aryloxycarbonyl group.)

[0074] [Chemical formula] (In formula (21b), p is the same as p in formula (2b).)

[0075] That is, the coordinative copolymerization of monomer b 1 and monomer b 2 proceeds by alternating copolymerization while forming a pyrrolidone ring as shown in the following reaction formula.

[0076] [ka]

[0077] In formula (21a), R 21 R is an alkylsulfonyl group, an arylsulfonyl group, an alkyloxycarbonyl group, or an aryloxycarbonyl group. A specific example of an alkylsulfonyl group is R in formula (2a) mentioned above. 2 Examples of alkylsulfonyl groups are similar to those mentioned above. An example of an arylsulfonyl group is the R in formula (2a) above. 2 Examples of aryl sulfonyl groups are similar to those mentioned above. Examples of alkyloxycarbonyl groups include the R in formula (2a) above. 2 Examples of alkyloxycarbonyl groups are similar to those mentioned above. An example of an aryloxycarbonyl group is the R in formula (2a) above. 2 Examples of aryloxycarbonyl groups that result in this can be found. 2 If monomer b is an alkylsulfonyl group, arylsulfonyl group, alkyloxycarbonyl group, or aryloxycarbonyl group, 1 R 21 R 2 It is preferable that the group is the same alkylsulfonyl group, arylsulfonyl group, alkyloxycarbonyl group, or aryloxycarbonyl group as R 2 It may be a different alkylsulfonyl group, arylsulfonyl group, alkyloxycarbonyl group, or aryloxycarbonyl group. The target polar polyolefin R 2 If R is a hydrogen atom, 21 The group can be appropriately selected from alkylsulfonyl groups, arylsulfonyl groups, alkyloxycarbonyl groups, or aryloxycarbonyl groups. In that case, the R in the resulting polymer 21 By deprotecting and substituting with a hydrogen atom, R 2 This allows for the production of polar polyolefins in which hydrogen atoms are present.

[0078] Note that monomer b represented by formula (21a) 1 For example, it can be produced by reacting an allylamine compound with acryloyl chloride, as shown in the reaction equation below.

[0079] [ka]

[0080] In equation (21b), p is selected to be the same as p in equation (2b).

[0081] The coordination polymerization of monomer a is carried out in the presence of a palladium catalyst. As the palladium catalyst, for example, the same one as in the first embodiment can be used. However, from the viewpoint of reactivity, it is preferable to use a palladium cyclic dinuclear complex represented by formula (4) as the imine-type palladium complex, and more preferably to use a palladium cyclic dinuclear complex represented by formula (4a). The polymerization conditions and the like can also be the same as in the first embodiment.

[0082] According to the second embodiment described above, it is possible to provide a polar polyolefin in which the content and distribution of polar groups are highly controlled, and a method for producing the same.

[0083] <Third Embodiment> The polar polyolefin according to the third embodiment of the present invention is unit B represented by the following formula (2ax) 1x And, unit B, which is represented by the following formula (2b) 2 Unit B, which has the following formula (2a), 1 It may also have this.

[0084] [ka] (In formula (2ax), R 2 R is a hydrogen atom, an alkylsulfonyl group, an arylsulfonyl group, an alkyloxycarbonyl group, or an aryloxycarbonyl group. 2x(This is a hydrogen atom or an alkyl group.)

[0085] [ka] (In equation (2b), p is an integer between 3 and 27.)

[0086] [ka] (In formula (2a), R 2 (This is a hydrogen atom, an alkylsulfonyl group, an arylsulfonyl group, an alkyloxycarbonyl group, or an aryloxycarbonyl group.)

[0087] In formula (2ax), R 2 This is R in formula (2a) shown in the second embodiment. 2 It is similar to that.

[0088] In formula (2ax), R 2x C1-C4 alkyl groups are hydrogen atoms or alkyl groups. Specific examples of alkyl groups include C1-C6 alkyl groups such as methyl, ethyl, propyl, isopropyl, butyl, sec-butyl, isobutyl, tert-butyl, pentyl, and hexyl groups. Among these, C1-C4 alkyl groups are preferred, C1-C4 linear alkyl groups are more preferred, and methyl or n-butyl groups are even more preferred.

[0089] Unit B represented by equation (2b) 2 This is Unit B shown in the second embodiment. 2 It is similar to that.

[0090] Unit B represented by equation (2a) 1 This is Unit B shown in the second embodiment. 1 It is similar to that.

[0091] In other words, the polar polyolefin according to the third embodiment is unit B represented by formula (2a) in the polar polyolefin according to the second embodiment. 1It has a structure in which at least a portion (or all or part) of the pyrrolidone ring contained within is open.

[0092] Unit B contained in polar polyolefins 1 and Unit B 1x and Unit B 2 Unit B for the total 1 and Unit B 1x The total percentage ((B 1 +B 1x ) / (B 1 +B 1x +B 2 The value of )) is preferably 0.10 to 0.70, more preferably 0.15 to 0.60, and even more preferably 0.20 to 0.50. Note that Unit B contained in polar polyolefins 1 and Unit B 1x and Unit B 2 Unit B for the total 1 and Unit B 1x The total percentage ((B 1 +B 1x ) / (B 1 +B 1x +B 2 )) is a polar polyolefin 1 It can be calculated from the proton integral ratio derived from each unit by 1H-NMR analysis (solvent: CDCl3, room temperature).

[0093] Unit B contained in polar polyolefins 1 and Unit B 1x Unit B for the total 1x The proportion (B 1x / ( B 1 +B 1x The ring-opening rate of the pyrrolidone ring is preferably 0.30 to 1.00 (all rings open), more preferably 0.50 to 0.99, and even more preferably 0.70 to 0.98. Note that Unit B contained in polar polyolefins 1 and Unit B 1x Unit B for the total 1x The proportion (B 1x / ( B 1 +B1x ) is a polar polyolefin 1 It can be calculated from the proton integral ratio derived from each unit by 1H-NMR analysis (solvent: CDCl3, room temperature).

[0094] The number-average molecular weight (Mn) of the polar polyolefin is preferably 500 to 50,000, more preferably 1,000 to 30,000, and even more preferably 3,000 to 10,000. The molecular weight distribution (Mw / Mn) of the polar polyolefin is preferably 1.1 to 3.5, and more preferably 1.2 to 2.5. The number-average molecular weight (Mn) and molecular weight distribution (Mw / Mn) of the polar polyolefin can be measured by GPC (eluent: tetrahydrofuran).

[0095] With polar polyolefins like those described above, it becomes possible to highly control the content and distribution of polar groups.

[0096] The above polar polyolefin is, for example, obtained by using an alkyl alcohol solution of an alkali metal hydroxide to obtain unit B represented by formula (2a) in the polar polyolefin according to the second embodiment. 1 It can be manufactured by opening at least a portion (or all or part) of the pyrrolidone ring contained in it.

[0097] A specific example of an alkyl group in an alkyl alcohol is the R in the aforementioned formula (2ax). 2x Examples of alkyl groups that are similar to those shown are given. Note that the alkyl group in the alkyl alcohol is unit B represented by formula (2a) in the polar polyolefin according to the second embodiment. 1 By opening the pyrrolidone ring contained in, unit B represented by formula (2ax) is formed. 1x In R 2x Therefore, the R of the target polar polyolefin 2x If is an alkyl group, then the alkyl group in the alkyl alcohol is R 2x It is preferable that it is the same alkyl group as R 2xIt may be a different alkyl group. The R of the target polar polyolefin 2x If the atom is a hydrogen atom, the alkyl group in the alkyl alcohol can be appropriately selected from the alkyl groups mentioned above. In that case, the ester group (-COOR) in the resulting polymer 2x By hydrolyzing ) and substituting it with a hydrogen atom, R 2x This allows for the production of polar polyolefins in which hydrogen atoms are present.

[0098] Specific examples of alkali metal hydroxides include lithium hydroxide (LiOH), sodium hydroxide (NaOH), potassium hydroxide (KOH), rubidium hydroxide (RbOH), cesium hydroxide (CsOH), and francium hydroxide (FrOH). Among these, lithium hydroxide (LiOH), sodium hydroxide (NaOH), or potassium hydroxide (KOH) are preferred, and lithium hydroxide (LiOH) or sodium hydroxide (NaOH) are more preferred.

[0099] The amount of alkyl alcohol used is preferably 0.1 to 10 mL, and more preferably 1 to 5 mL, per 10 mg of polymer. The amount of alkali metal hydroxide is preferably 1 to 50 times, and more preferably 1 to 20 times, the amount of pyrrolidone ring contained in the polar polyolefin.

[0100] According to the third embodiment described above, it is possible to provide a polar polyolefin in which the content and distribution of polar groups are highly controlled, and a method for producing the same.

[0101] <Fourth Embodiment> The polar polyolefin according to the fourth embodiment of the present invention is a unit B represented by the following formula (2a) 1 and / or Unit B represented by the following formula (2ax) 1x And, unit B, which is represented by the following formula (2ay) 1y And, unit B, which is represented by the following formula (2b) 2 It has the following characteristics.

[0102] [ka] (In formula (2a), R 2 (This is a hydrogen atom, an alkylsulfonyl group, an arylsulfonyl group, an alkyloxycarbonyl group, or an aryloxycarbonyl group.)

[0103] [ka] (In formula (2ax), R 2 R is a hydrogen atom, an alkylsulfonyl group, an arylsulfonyl group, an alkyloxycarbonyl group, or an aryloxycarbonyl group. 2x (This is a hydrogen atom or an alkyl group.)

[0104] [ka] (In formula (2ay), R 2 R is a hydrogen atom, an alkylsulfonyl group, an arylsulfonyl group, an alkyloxycarbonyl group, or an aryloxycarbonyl group. 2y (This is a hydrogen atom or an alkyl group.)

[0105] [ka] (In equation (2b), p is an integer between 3 and 27.)

[0106] Unit B represented by equation (2a) 1 This is Unit B shown in the second embodiment. 1 It is similar to that.

[0107] Unit B represented by equation (2ax) 1x This is Unit B shown in the third embodiment. 1x It is similar to that.

[0108] In formula (2ay), R 2 This is R in formula (2a) shown in the second embodiment. 2 It is the same as above. In equation (2ay), R2y This is R of formula (2ax) shown in the third embodiment. 2x It is similar to that.

[0109] Unit B represented by equation (2b) 2 This is Unit B shown in the second embodiment. 2 It is similar to that.

[0110] In other words, the polar polyolefin according to the fourth embodiment is unit B represented by formula (2ax) in the polar polyolefin according to the third embodiment. 1x It has a structure in which at least a part (all or part) of the ring-opened pyrrolidone structure contained within is cleaved.

[0111] Unit B contained in polar polyolefins 1 and Unit B 1x and Unit B 1y and Unit B 2 Unit B for the total 1 and Unit B 1x and Unit B 1y The total percentage ((B 1 +B 1x +B 1y ) / (B 1 +B 1x +B 1y +B 2 The value of )) is preferably 0.10 to 0.70, more preferably 0.15 to 0.60, and even more preferably 0.20 to 0.50. Note that Unit B contained in polar polyolefins 1 and Unit B 1x and Unit B 1y and Unit B 2 Unit B for the total 1 and Unit B 1x and Unit B 1y The total percentage ((B 1 +B 1x +B 1y ) / (B 1 +B 1x +B 1y +B 2 )) is a polar polyolefin 1It can be calculated from the proton integral ratio derived from each unit by 1H-NMR analysis (solvent: CDCl3, room temperature).

[0112] Unit B contained in polar polyolefins 1 and Unit B 1x and Unit B 1y Unit B for the total 1x and Unit B 1y The total percentage ((B 1x +B 1y ) / (B 1 +B 1x +B 1y The ring-opening rate of the pyrrolidone ring is preferably 0.30 to 1.00 (all rings open), more preferably 0.50 to 0.99, and even more preferably 0.70 to 0.98. Note that Unit B contained in polar polyolefins 1 and Unit B 1x and Unit B 1y Unit B for the total 1x and Unit B 1y The total percentage ((B 1x +B 1y ) / (B 1 +B 1x +B 1y )) is a polar polyolefin 1 It can be calculated from the proton integral ratio derived from each unit by 1H-NMR analysis (solvent: CDCl3, room temperature).

[0113] Unit B contained in polar polyolefins 1x and Unit B 1y Unit B for the total 1y The proportion (B 1y / ( B 1x +B 1y The cleavage rate of the ring-opened pyrrolidone structure is preferably 0.10 to 0.90, more preferably 0.20 to 0.80, and even more preferably 0.30 to 0.70. Note that Unit B contained in polar polyolefins 1x and Unit B 1y Unit B for the total 1y The proportion (B1y / ( B 1x +B 1y )) is a polar polyolefin 1 It can be calculated from the proton integral ratio derived from each unit by 1H-NMR analysis (solvent: CDCl3, room temperature).

[0114] The number-average molecular weight (Mn) of the polar polyolefin is preferably 500 to 50,000, more preferably 1,000 to 30,000, and even more preferably 3,000 to 10,000. The molecular weight distribution (Mw / Mn) of the polar polyolefin is preferably 1.1 to 3.5, and more preferably 1.2 to 2.5. The number-average molecular weight (Mn) and molecular weight distribution (Mw / Mn) of the polar polyolefin can be measured by GPC (eluent: tetrahydrofuran).

[0115] With polar polyolefins like those described above, it becomes possible to highly control the content and distribution of polar groups.

[0116] The polar polyolefin described above is obtained, for example, by irradiating the polar polyolefin according to the third embodiment with light in the presence of a diaryl ketone, thereby producing unit B of the polar polyolefin. 1x It can be produced by cleaving at least a portion of the ring-opened pyrrolidone structure contained in it.

[0117] Specific examples of solvents include dimethyl sulfoxide, N,N-dimethylformamide, N,N-dimethylacetamide, 1,3-dimethyl-2-imidazolidinone, tetrahydrofuran, acetone, acetonitrile, and benzonitrile. Among these, dimethyl sulfoxide, N,N-dimethylformamide, N,N-dimethylacetamide, and 1,3-dimethyl-2-imidazolidinone are preferred. The amount of solvent used is preferably 0.1 to 10 mL, and more preferably 0.1 to 5 mL, per 10 mg of polar polyolefin.

[0118] Specific examples of diaryl ketones include benzophenone, 4,4'-dimethylbenzophenone, 4,4'-dimethoxybenzophenone, 4,4'-bis(dimethylamino)benzophenone, 4,4'-bis(diethylamino)benzophenone, 4,4'-difluorobenzophenone, 4,4'-dichlorobenzophenone, 4,4'-dibromobenzophenone, 4,4'-di-tert-butylbenzophenone, decafluorobenzophenone, 1,4-dibenzoylbenzene, 4-methylbenzophenone, 4-methoxybenzophenone, phenyl[4-(trifluoromethyl)phenyl]methanone, 4-methoxy-4'trifluoromethylbenzophenone, 9-fluorenone, xanthone, thioxanthone, and anthraquinone. Among these, benzophenone, 4,4'-dimethoxybenzophenone, 4,4'-dichlorobenzophenone, 4-methoxybenzophenone, phenyl[4-(trifluoromethyl)phenyl]methanone, 4-methoxy-4'trifluoromethylbenzophenone, 9-fluorenone, xanthone, thioxanthone, and anthraquinone are preferred. The amount of additive used is preferably 0.5 to 10 times, and more preferably 1 to 5 times, the amount of ring-opened pyrrolidone structure contained in the polar polyolefin.

[0119] The wavelength of the irradiated light is preferably 280 to 780 nm, and more preferably 300 to 400 nm. The irradiation time is preferably 1 to 120 hours, and more preferably 4 to 72 hours.

[0120] According to the fourth embodiment described above, it is possible to provide a polar polyolefin in which the content and distribution of polar groups are highly controlled, and a method for producing the same. [Examples]

[0121] <Example 1-1> To a 25 mL Schlenk tube containing palladium cyclic dinuclear complex C1 (0.0034 mmol, 4.0 mg) represented by formula (4a) and sodium tetrakis(3,5-bistrifluoromethylphenyl) borate (0.0080 mmol, 7.1 mg), 0.34 mL of anhydrous methylene chloride (manufactured by Kanto Chemical Co., Ltd.) was added and the mixture was stirred for 3 minutes under an argon atmosphere. Subsequently, monomer a, 4-(triisopropylsiloxymethyl)octa-1-ene(X) represented by formula (11), was added. 11 =CH3, R 11 =Si i Add Pr3 (l=1, m=3, n=1) (0.67 mmol, 0.20 g), and polymerize at room temperature with stirring for 24 hours to obtain unit A(X) represented by formula (1). 1 =CH2, R 1 =Si i 0.10 g of polar polyolefin having Pr3, l=1, m=3, n=1 was obtained. The number-average molecular weight (Mn) of the obtained polar polyolefin was 12400, and the molecular weight distribution (Mw / Mn) was 3.1. The results are shown in Table 1.

[0122] Furthermore, this polar polyolefin 1 ¹H-NMR (CDCl3, room temperature) analysis revealed, as shown in Figure 1, signals originating from the triisopropylsilyl group (δ1.05), the methylene group adjacent to the oxygen atom (δ3.55), and a signal originating from the oligomethylene chain of the polymer backbone (δ1.26). On the other hand, the signal originating from the methyl group at the branched end (δ0.89) was small, and the selectivity for the ω,1-structure was calculated to be 77%.

[0123] <Example 1-2> To a 25 mL Schlenk tube containing palladium cyclic dinuclear complex C1 represented by formula (4a) (0.0022 mmol, 2.6 mg) and sodium tetrakis(3,5-bistrifluoromethylphenyl) borate (0.0052 mmol, 4.6 mg), 0.22 mL of anhydrous methylene chloride (manufactured by Kanto Chemical Co., Ltd.) was added and the mixture was stirred for 3 minutes under an argon atmosphere. Subsequently, monomer a, 4-(triisopropylsiloxymethyl)tetradeca-1-ene (X), represented by formula (11), was added.11 =CH3, R 11 =Si i Add Pr3 (l=1, m=9, n=1) (0.44 mmol, 0.17 g), and polymerize at room temperature with stirring for 24 hours to obtain unit A(X) represented by formula (1). 1 =CH2, R 1 =Si i 0.14 g of polar polyolefin having Pr3, l=1, m=9, n=1 was obtained. The number-average molecular weight (Mn) of the obtained polar polyolefin was 53100, and the molecular weight distribution (Mw / Mn) was 1.5. The results are shown in Table 1.

[0124] <Examples 1-3> To a 25 mL Schlenk tube containing palladium mononuclear complex C2 (A=CH3, B=CH3, 0.01 mmol, 5.7 mg) represented by formula (3a) and sodium tetrakis(3,5-bistrifluoromethylphenyl) borate (0.012 mmol, 10.6 mg), 0.50 mL of anhydrous methylene chloride (manufactured by Kanto Chemical Co., Ltd.) was added and the mixture was stirred for 3 minutes under an argon atmosphere. Subsequently, monomer a, 4-(triisopropylsiloxymethyl)octa-1-ene(X) represented by formula (11), was added. 11 =CH3, R 11 =Si i Add Pr3 (l=1, m=3, n=1) (1.0 mmol, 0.30 g) and polymerize at room temperature with stirring for 24 hours to obtain unit A(X) represented by formula (1). 1 =CH2, R 1 =Si i 0.10 g of polar polyolefin having Pr3, l=1, m=3, n=1 was obtained. The number-average molecular weight (Mn) of the obtained polar polyolefin was 11000, and the molecular weight distribution (Mw / Mn) was 1.5. The results are shown in Table 1.

[0125] <Examples 1-4> To a 25 mL Schlenk tube containing palladium mononuclear complex C2 (A=CH3, B=CH3, 0.0052 mmol, 3.0 mg) represented by formula (3a) and sodium tetrakis(3,5-bistrifluoromethylphenyl) borate (0.0063 mmol, 5.5 mg), 0.26 mL of anhydrous methylene chloride (manufactured by Kanto Chemical Co., Ltd.) was added and the mixture was stirred for 3 minutes under an argon atmosphere. Subsequently, monomer a, 4-(triisopropylsiloxymethyl)tetradeca-1-ene (X), represented by formula (11), was added. 11 =CH3, R 11 =Si i Add Pr3 (l=1, m=9, n=1) (1.0 mmol, 0.30 g) and polymerize at room temperature with stirring for 24 hours to obtain unit A(X) represented by formula (1). 1 =CH2, R 1 =Si i 0.10 g of polar polyolefin having Pr3, l=1, m=9, n=1 was obtained. The number-average molecular weight (Mn) of the obtained polar polyolefin was 25300, and the molecular weight distribution (Mw / Mn) was 1.3. The results are shown in Table 1.

[0126] <Examples 1-5> To a 25 mL Schlenk tube containing palladium mononuclear complex C2 (A=CH3, B=CH3, 0.01 mmol, 5.7 mg) represented by formula (3a) and sodium tetrakis(3,5-bistrifluoromethylphenyl) borate (0.012 mmol, 10.6 mg), 0.50 mL of anhydrous methylene chloride (manufactured by Kanto Chemical Co., Ltd.) was added and the mixture was stirred for 3 minutes under an argon atmosphere. Subsequently, monomer a, 4-methyl-5-(triisopropylsiloxy)penta-1-ene (X), represented by formula (11), was added. 11 =CH3, R 11 =Si i Add Pr3 (l=1, m=0, n=1) (1.0 mmol, 0.26 g), and polymerize at room temperature with stirring for 48 hours to obtain unit A(X) represented by formula (1). 1 =CH2, R 1 =Si i0.074 g of polar polyolefin having Pr3, l=1, m=0, n=1 was obtained. The number-average molecular weight (Mn) of the obtained polar polyolefin was 900, and the molecular weight distribution (Mw / Mn) was 1.3. The results are shown in Table 1.

[0127] <Examples 1-6> To a 25 mL Schlenk tube containing palladium mononuclear complex C2 (A=CH3, B=CH3, 0.005 mmol, 2.9 mg) represented by formula (3a) and sodium tetrakis(3,5-bistrifluoromethylphenyl) borate (0.006 mmol, 5.3 mg), 0.25 mL of anhydrous methylene chloride (manufactured by Kanto Chemical Co., Ltd.) was added and the mixture was stirred for 3 minutes under an argon atmosphere. Subsequently, monomer a, 3-(triisopropylsiloxymethyl)nona-1-ene (X), represented by formula (11), was added. 11 =CH3, R 11 =Si i Add Pr3 (l=1, m=0, n=1) (0.5 mmol, 0.16 g), and polymerize at room temperature with stirring for 90 hours to obtain unit A(X) represented by formula (1). 1 =CH2, R 1 =Si i 0.036 g of polar polyolefin having Pr3, l=1, m=0, n=1 was obtained. The number-average molecular weight (Mn) of the obtained polar polyolefin was 9500, and the molecular weight distribution (Mw / Mn) was 1.3. The results are shown in Table 1.

[0128] <Examples 1-7> To a 25 mL Schlenk tube containing palladium mononuclear complex C2 (A=CH3, B=CH3, 0.01 mmol, 5.7 mg) represented by formula (3a) and sodium tetrakis(3,5-bistrifluoromethylphenyl) borate (0.012 mmol, 10.6 mg), 0.50 mL of anhydrous methylene chloride (manufactured by Kanto Chemical Co., Ltd.) was added and the mixture was stirred for 3 minutes under an argon atmosphere. Subsequently, monomer a, 3-(triisopropylsiloxy)penta-1-ene(X) represented by formula (11), was added. 11 =CH3, R 11 =Si iAdd Pr3 (l=0, m=1, n=0) (1.0 mmol, 0.24 g) and polymerize at room temperature with stirring for 72 hours to obtain unit A(X) represented by formula (1). 1 =CH2, R 1 =Si i 0.048 g of polar polyolefin having Pr3 (l=0, m=1, n=0) was obtained. The number-average molecular weight (Mn) of the obtained polar polyolefin was 5800, and the molecular weight distribution (Mw / Mn) was 1.3. The results are shown in Table 1.

[0129] <Examples 1-8> To a 25 mL Schlenk tube containing palladium mononuclear complex C2 (A=CH3, B=CH3, 0.0078 mmol, 4.5 mg) represented by formula (3a) and sodium tetrakis(3,5-bistrifluoromethylphenyl) borate (0.0094 mmol, 8.3 mg), 0.39 mL of anhydrous methylene chloride (manufactured by Kanto Chemical Co., Ltd.) was added and the mixture was stirred for 3 minutes under an argon atmosphere. Subsequently, monomer a, 4-(tert-butyldimethylsiloxymethyl)octa-1-ene(X) represented by formula (11), was added. 11 =CH3, R 11 =SiMe2 t Add Bu (l=1, m=3, n=1) (0.78 mmol, 0.20 g), and polymerize at room temperature with stirring for 24 hours to obtain unit A(X) represented by formula (1). 1 =CH2, R 1 =SiMe2 t 0.15 g of polar polyolefin having Bu (l=1, m=3, n=1) was obtained. The number-average molecular weight (Mn) of the obtained polar polyolefin was 14600, and the molecular weight distribution (Mw / Mn) was 1.2. The results are shown in Table 1.

[0130] Furthermore, this polar polyolefin 1 ¹H-NMR (CDCl3, room temperature) analysis revealed, as shown in Figure 2, signals originating from the tert-butyldimethylsilyl group (δ0.03, 0.89), a signal originating from the methylene group adjacent to oxygen (δ3.45), and a signal originating from the oligomethylene chain of the polymer backbone at δ1.25.

[0131] Furthermore, methanol (0.47 mL) is added to a 25 mL Schlenk tube containing the polar polyolefin (40 mg) obtained above, and acetyl chloride (0.0020 mL) is added under an argon atmosphere. The mixture is reacted at room temperature with stirring for 24 hours to obtain unit A(R) represented by formula (1). 1 A polar polyolefin with (=H, l=1, m=3, n=1) was obtained. The results are shown in Table 1.

[0132] Furthermore, this polar polyolefin 1 ¹H-NMR (CDCl3, room temperature) analysis revealed, as shown in Figure 3, that the signal (δ0.03) originating from the tert-butyldimethylsilyl group had disappeared, indicating that the tert-butyldimethylsilyl group on the oxygen atom had been converted to hydrogen.

[0133] <Examples 1-9> To a 25 mL Schlenk tube containing palladium cyclic dinuclear complex C1 represented by formula (4a) (0.0029 mmol, 3.4 mg) and sodium tetrakis(3,5-bistrifluoromethylphenyl) borate (0.0069 mmol, 6.1 mg), 0.29 mL of anhydrous methylene chloride (manufactured by Kanto Chemical Co., Ltd.) was added and the mixture was stirred for 3 minutes under an argon atmosphere. Subsequently, monomer a, 4-tert-butyldimethylsiloxymethylocta-1-ene (X), represented by formula (11), was added. 11 =CH3, R 11 =SiMe2 t Add Bu (l=1, m=3, n=1) (0.57 mmol, 0.15 g), and polymerize at room temperature with stirring for 72 hours to obtain unit A(X) represented by formula (1). 1 =CH2, R 1 =SiMe2 t A homopolymer of 4-tert-butyldimethylsiloxymethylocta-1-ene (Bu, l=1, m=3, n=1) was obtained at 0.13 g. The number-average molecular weight (Mn) of the obtained polymer was 19600, and the molecular weight distribution (Mw / Mn) was 1.5. The results are shown in Table 1.

[0134] <Examples 1-10> To a 25 mL Schlenk tube containing palladium cyclic dinuclear complex C1 (0.0022 mmol, 2.6 mg) represented by formula (4a) and sodium tetrakis(3,5-bistrifluoromethylphenyl) borate (0.0052 mmol, 4.7 mg), 0.22 mL of anhydrous methylene chloride (manufactured by Kanto Chemical Co., Ltd.) was added and the mixture was stirred for 3 minutes under an argon atmosphere. Subsequently, monomer a, represented by formula (11), 5-tert-butyldimethylsiloxide dodeca-1-ene (X 11 =CH3, R 11 =SiMe2 t Add Bu (l=0, m=6, n=2) (0.44 mmol, 0.13 g), and polymerize at room temperature with stirring for 72 hours to obtain unit A(X) represented by formula (1). 1 =CH2, R 1 =SiMe2 t A homopolymer of 5-tert-butyldimethylsiloxide dodeca-1-ene (Bu, l=0, m=6, n=2) was obtained at 0.13 g. The number-average molecular weight (Mn) of the obtained polymer was 6600, and the molecular weight distribution (Mw / Mn) was 1.8. The results are shown in Table 1.

[0135] <Example 1-11> The palladium mononuclear complex C3(A=) is represented by formula (3a). i 0.25 mL of dichloromethane (manufactured by Kanto Chemical Co., Ltd.) was added to a 25 mL Schlenk tube containing Pr, B=CH3, 0.005 mmol, 3.3 mg and sodium tetrakis(3,5-bistrifluoromethylphenyl) borate (0.006 mmol, 5.3 mg), and the mixture was stirred for 3 minutes under an argon atmosphere. Subsequently, 5-trimethylsiloxy-6-cyclohexyl-hexa-1-ene (X), monomer a represented by formula (11), was added. 11 =C6H 11 , R 11 Add SiMe3 (l=0, m=1, n=2) (0.5 mmol, 0.127 g), and polymerize at room temperature with stirring for 24 hours to obtain unit A(X) represented by formula (1). 1 =C6H 10 , R 10.0045 g of polar polyolefin having (=H, l=0, m=1, n=2) was obtained. The number-average molecular weight (Mn) of the obtained polar polyolefin was 2300, and the molecular weight distribution (Mw / Mn) was 1.2. The results are shown in Table 1.

[0136] <Examples 1-12> The palladium mononuclear complex C3(A=) is represented by formula (3a). i 0.25 mL of dichloromethane (manufactured by Kanto Chemical Co., Ltd.) was added to a 25 mL Schlenk tube containing Pr, B=CH3, 0.005 mmol, 3.3 mg and sodium tetrakis(3,5-bistrifluoromethylphenyl) borate (0.006 mmol, 5.3 mg), and the mixture was stirred for 3 minutes under an argon atmosphere. Subsequently, 5-triethylsiloxy-6-cyclohexyl-hexa-1-ene (X), which is monomer a represented by formula (11), was added. 11 =C6H 11 , R 11 Add SiEt3 (l=0, m=1, n=2) (0.5 mmol, 0.148 g), carry out polymerization at room temperature with stirring for 24 hours, and obtain unit A(X) represented by formula (1). 1 =C6H 10 , R 1 0.0034 g of polar polyolefin having (=SiEt3, l=0, m=1, n=2) was obtained. The number-average molecular weight (Mn) of the obtained polar polyolefin was 1900, and the molecular weight distribution (Mw / Mn) was 1.4. The results are shown in Table 1.

[0137] <Examples 1-13> The palladium mononuclear complex C3(A=) is represented by formula (3a). i 0.50 mL of dichloromethane (manufactured by Kanto Chemical Co., Ltd.) was added to a 25 mL Schlenk tube containing Pr, B=CH3, 0.005 mmol, 3.3 mg and sodium tetrakis(3,5-bistrifluoromethylphenyl) borate (0.006 mmol, 5.3 mg), and the mixture was stirred for 3 minutes under an argon atmosphere. Then, the monomer a represented by formula (11), 5-tert-butyldimethylsiloxy-6-cyclohexyl-hexa-1-ene (X) was added. 11 =C6H 11 , R11 =SiMe2 t Add Bu (l=0, m=1, n=2) (0.5 mmol, 0.148 g), and polymerize at room temperature with stirring for 24 hours to obtain unit A(X) represented by formula (1). 1 =C6H 10 , R 1 =SiMe2 t 0.0316 g of polar polyolefin having Bu (l=0, m=1, n=2) was obtained. The number-average molecular weight (Mn) of the obtained polar polyolefin was 6400, and the molecular weight distribution (Mw / Mn) was 1.4. The results are shown in Table 1.

[0138] <Examples 1-14> The palladium mononuclear complex C3(A=) is represented by formula (3a). i 0.50 mL of dichloromethane (manufactured by Kanto Chemical Co., Ltd.) was added to a 25 mL Schlenk tube containing Pr, B=CH3, 0.005 mmol, 3.3 mg and sodium tetrakis(3,5-bistrifluoromethylphenyl) borate (0.006 mmol, 5.3 mg), and the mixture was stirred for 3 minutes under an argon atmosphere. Then, 5-(triisopropylsiloxy)-6-cyclohexyl-hexa-1-ene (X), which is monomer a represented by formula (11), was added. 11 =C6H 11 , R 11 =Si i Add Pr3 (l=0, m=1, n=2) (0.5 mmol, 0.169 g), and polymerize at room temperature with stirring for 24 hours to obtain unit A(X) represented by formula (1). 1 =C6H 10 , R 1 =Si i 0.0715 g of polar polyolefin having Pr3 (l=0, m=1, n=2) was obtained. The number-average molecular weight (Mn) of the obtained polar polyolefin was 6500, and the molecular weight distribution (Mw / Mn) was 1.5. The results are shown in Table 1.

[0139] <Examples 1-15> The palladium mononuclear complex C3(A=) is represented by formula (3a). i0.50 mL of dichloromethane (manufactured by Kanto Chemical Co., Ltd.) was added to a 25 mL Schlenk tube containing Pr, B=CH3, 0.005 mmol, 3.3 mg and sodium tetrakis(3,5-bistrifluoromethylphenyl) borate (0.006 mmol, 5.3 mg), and the mixture was stirred for 3 minutes under an argon atmosphere. Then, monomer a, represented by formula (11), 5-tert-butyldimethylsiloxy-6-cyclohexyl-deca-1-ene (X 11 =C6H 11 , R 11 =SiMe2 t Add Bu (l=0, m=1, n=6) (0.5 mmol, 0.176 g), and polymerize at room temperature with stirring for 24 hours to obtain unit A(X) represented by formula (1). 1 =C6H 10 , R 1 =SiMe2 t 0.0567 g of polar polyolefin having Bu (l=0, m=1, n=6) was obtained. The number-average molecular weight (Mn) of the obtained polar polyolefin was 7700, and the molecular weight distribution (Mw / Mn) was 1.3. The results are shown in Table 1.

[0140] <Example 1-16> The palladium mononuclear complex C3(A=) is represented by formula (3a). i 0.50 mL of dichloromethane (manufactured by Kanto Chemical Co., Ltd.) was added to a 25 mL Schlenk tube containing Pr (0.01 mmol, B=CH3, 6.6 mg) and sodium tetrakis(3,5-bistrifluoromethylphenyl) borate (0.012 mmol, 10.6 mg), and the mixture was stirred for 3 minutes under an argon atmosphere. Subsequently, 5-trimethylsiloxy-7-cyclohexyl-hepta-1-ene (X), which is monomer a represented by formula (11), was added. 11 =C6H 11 , R 11 Add (=SiMe3, l=0, m=2, n=2) (1.0 mmol, 0.269 g), carry out polymerization at room temperature with stirring for 24 hours, and obtain unit A(X) represented by formula (1). 1 =C6H 10 , R 10.133 g of polar polyolefin having (=H, l=0, m=2, n=2) was obtained. The number-average molecular weight (Mn) of the obtained polar polyolefin was 9000, and the molecular weight distribution (Mw / Mn) was 1.7. The results are shown in Table 1.

[0141] <Example 1-17> The palladium mononuclear complex C3(A=) is represented by formula (3a). i 0.50 mL of dichloromethane (manufactured by Kanto Chemical Co., Ltd.) was added to a 25 mL Schlenk tube containing Pr (0.01 mmol, B=CH3, 6.6 mg) and sodium tetrakis(3,5-bistrifluoromethylphenyl) borate (0.012 mmol, 10.6 mg), and the mixture was stirred for 3 minutes under an argon atmosphere. Then, the monomer a represented by formula (11), 5-tert-butyldimethylsiloxy-7-cyclohexyl-hepta-1-ene (X 11 =C6H 11 , R 11 =SiMe2 t Add Bu (l=0, m=2, n=2) (1.0 mmol, 0.311 g), and polymerize at room temperature for 30 minutes while stirring to obtain unit A(X) represented by formula (1). 1 =C6H 10 , R 1 =SiMe2 t 0.263 g of polar polyolefin having Bu (l=0, m=2, n=2) was obtained. The number-average molecular weight (Mn) of the obtained polar polyolefin was 31700, and the molecular weight distribution (Mw / Mn) was 1.2. The results are shown in Table 1.

[0142] Furthermore, this polar polyolefin 1 ¹H-NMR (CDCl3, room temperature) analysis revealed, as shown in Figure 4, signals originating from the tert-butyldimethylsilyl group (δ 0.03, 0.88), the methylene group adjacent to oxygen (δ 3.58), and signals originating from the oligomethylene chain / cyclohexane ring of the polymer backbone appeared at δ 1.14, 1.26, 1.39, 1.56, 1.70, and 1.72.

[0143] Furthermore, methanol (4 mL) is added to a 25 mL Schlenk tube containing the polar polyolefin (92 mg) obtained above, and acetyl chloride (0.20 mL) is added under an argon atmosphere. The mixture is then reacted at room temperature with stirring for 24 hours to obtain unit A(X) represented by formula (1). 1 =C6H 10 , R 1 A polar polyolefin having (=H, l=0, m=2, n=2) was obtained. The number-average molecular weight (Mn) of the obtained polar polyolefin was 35,000, and the molecular weight distribution (Mw / Mn) was 1.2. The results are shown in Table 1.

[0144] Furthermore, this polar polyolefin 1 ¹H-NMR (CDCl3, room temperature) analysis revealed, as shown in Figure 5, that the signal (δ0.03) originating from the tert-butyldimethylsilyl group had disappeared, indicating that the tert-butyldimethylsilyl group on the oxygen atom had been converted to hydrogen.

[0145] <Examples 1-18> The palladium mononuclear complex C3(A=) is represented by formula (3a). i 0.50 mL of dichloromethane (manufactured by Kanto Chemical Co., Ltd.) was added to a 25 mL Schlenk tube containing Pr, B=CH3, 0.01 mmol, 6.6 mg and sodium tetrakis(3,5-bistrifluoromethylphenyl) borate (0.012 mmol, 10.6 mg), and the mixture was stirred for 3 minutes under an argon atmosphere. Then, monomer a, represented by formula (11), 9-tert-butyldimethylsiloxy-11-cyclohexylundeca-1-ene (X 11 =C6H 11 , R 11 =SiMe2 t Add Bu (l=0, m=2, n=6) (1.0 mmol, 0.367 g), and polymerize at room temperature for 30 minutes while stirring to obtain unit A(X) represented by formula (1). 1 =C6H 10 , R 1 =SiMe2 t0.322 g of polar polyolefin having Bu (l=0, m=2, n=6) was obtained. The number-average molecular weight (Mn) of the obtained polar polyolefin was 19600, and the molecular weight distribution (Mw / Mn) was 1.5. The results are shown in Table 1.

[0146] Furthermore, methanol (0.47 mL) is added to a 25 mL Schlenk tube containing the polar polyolefin (40 mg) obtained above, and acetyl chloride (0.0020 mL) is added under an argon atmosphere. The mixture is reacted at room temperature with stirring for 24 hours to obtain unit A(X) represented by formula (1). 1 =C6H 10 , R 1 A polar polyolefin having (=H, l=0, m=2, n=6) was obtained. The number-average molecular weight (Mn) of the obtained polar polyolefin was 20,000, and the molecular weight distribution (Mw / Mn) was 1.7. The results are shown in Table 1.

[0147] [Table 1]

[0148] <Example 2-1> A 25 mL Schlenk tube containing palladium cyclic dinuclear complex C1 (0.0050 mmol, 6.0 mg) represented by formula (4a) and sodium tetrakis(3,5-bistrifluoromethylphenyl) borate (0.012 mmol, 10.6 mg) was mixed with 0.50 mL of anhydrous methylene chloride (manufactured by Kanto Chemical Co., Ltd.) and stirred for 3 minutes under an argon atmosphere. Subsequently, monomer b represented by formula (21a) was added. 1 N-allyl-N-(p-toluenesulfonyl)acrylamide (R 21 =Ts)(2.0 mmol, 0.53 g) and monomer b represented by formula (21b) 2 Add 1-decene (p=7) (0.5 mmol, 0.095 mL), and polymerize at room temperature with stirring for 72 hours to obtain unit B represented by formula (2a). 1 (R 2 Unit B represented by equation (2b) =Ts) and equation (2b) 20.092 g of polar polyolefin having (p=7) was obtained. The proportion of repeating structures derived from N-allyl-N-(p-toluenesulfonyl)acrylamide in the obtained polar polyolefin was 45% (B 1 / ( B 1 +B 2 The ratio was 0.45. Furthermore, the number-average molecular weight (Mn) of the polar polyolefin was 9400, and the molecular weight distribution (Mw / Mn) was 2.7. The results are shown in Table 2.

[0149] Furthermore, this polar polyolefin 1 ¹H-NMR (CDCl3, room temperature) analysis revealed, as shown in Figure 6, signals originating from the p-toluenesulfonyl group (δ2.43, 7.33, 7.90), signals originating from the methylene group adjacent to nitrogen (δ3.29, 3.62, 3.78, 4.01), and a signal originating from the oligomethylene chain of the polymer backbone at δ1.55. 1 / ( B 1 +B 2 The integral ratios were calculated from these integral ratios. On the other hand, the signals originating from the methyl groups at the branched ends (δ 0.83, 0.88) were small, and the linear selectivity was 91%.

[0150] Furthermore, to a 25 mL Schlenk tube containing the polar polyolefin (50 mg) and 2-phenyl-N,N'-dimethylbenzimidazoline (27.8 mg) obtained above, acetonitrile (0.7 mL) and water (1 drop) are added, and the mixture is stirred at 40°C under an argon atmosphere while being irradiated with light (470 nm) for 20 hours to produce unit B represented by formula (2a). 1 (R 2 Unit B represented by =H) and equation (2b) 2 A polar polyolefin with p=7 was obtained. The results are shown in Table 2.

[0151] Furthermore, this polar polyolefin 1¹H-NMR (CDCl3, room temperature) analysis revealed, as shown in Figure 7, that the signal originating from the p-toluenesulfonyl group (δ2.43, 7.33, 7.90) was reduced, while the signal originating from the methylene group adjacent to nitrogen was shifted (δ2.93, 3.04, 3.36, 3.45), indicating that the p-toluenesulfonyl group on nitrogen was converted to hydrogen. Based on the integral ratios, the reaction rate was 89%.

[0152] <Example 2-2> The polar polyolefin (R) was prepared in the same manner as in Example 2-1, except that the amount of N-allyl-N-(p-toluenesulfonyl)acrylamide (7.3 mmol, 1.95 g) and the amount of 1-decene (1.8 mmol, 0.35 mL) were changed and the reaction time was set to 72 hours. 2 We obtained a result of (=Ts, p=3). The yield was 0.26 g. The results are shown in Table 2.

[0153] <Example 2-3> Except for setting the reaction temperature to 50°C, the polar polyolefin (R) was reacted in the same manner as in Example 2-1. 2 We obtained a result of (=Ts, p=3). The yield was 0.054 g. The results are shown in Table 2.

[0154] <Example 2-4> Except for changing the amount of N-allyl-N-(p-toluenesulfonyl)acrylamide (1.0 mmol, 0.27 g) and 1-decene (0.5 mmol, 0.095 mL), a polar polyolefin (R) was prepared in the same manner as in Example 2-1. 2 We obtained a result of (=Ts, p=3). The yield was 0.11g. The results are shown in Table 2.

[0155] <Example 2-5> Monomer b 2 Except for changing to 1-hexene (p=3) (0.5 mmol, 0.062 mL) and setting the reaction time to 72 hours, the polar polyolefin (R) was prepared in the same manner as in Example 2-1. 2 We obtained a result of (=Ts, p=3). The yield was 0.044g. The results are shown in Table 2.

[0156] <Example 2-6> The amount of N-allyl-N-(p-toluenesulfonyl)acrylamide (1.0 mmol, 0.27 g) was changed, and monomer b 2 Except for changing to 1-hexene (p=3) (0.5 mmol, 0.062 mL), the polar polyolefin (R) was prepared in the same manner as in Example 2-1. 2 We obtained a result of (=Ts, p=3). The yield was 0.061 g. The results are shown in Table 2.

[0157] <Example 2-7> Monomer b 2 Except for changing to 1-octadecene (p=15) (0.5 mmol, 0.16 mL) and setting the reaction time to 72 hours, the polar polyolefin (R) was prepared in the same manner as in Example 2-1. 2 We obtained a result of (=Ts, p=15). The yield was 0.048 g. The results are shown in Table 2.

[0158] <Example 2-8> The amount of N-allyl-N-(p-toluenesulfonyl)acrylamide (1.0 mmol, 0.27 g) was changed, and monomer b 2 Except for changing to 1-octadecene (p=15) (0.5 mmol, 0.16 mL), the polar polyolefin (R) was prepared in the same manner as in Example 2-1. 2 We obtained a result of (=Ts, p=3). The yield was 0.051 g. The results are shown in Table 2.

[0159] <Example 2-9> Monomer b 1 R 21 Except for changing to tert-butoxycarbonyl group (BOC) (2.0 mmol, 0.22 g) and setting the reaction time to 96 hours, the polar polyolefin (R) was prepared in the same manner as in Example 2-1. 2 We obtained BOC (=BOC, p=3). The results are shown in Table 2.

[0160] <Example 2-10> Monomer b 1 R 21Except for changing to a tert-butoxycarbonyl group (BOC) (1.0 mmol, 0.11 g), the polar polyolefin (R) was prepared in the same manner as in Example 2-1. 2 We obtained BOC (=BOC, p=3). The results are shown in Table 2.

[0161] <Example 2-11> The solvent was changed to 0.50 mL of anhydrous chlorobenzene (Aldrich), and the amount of N-allyl-N-(p-toluenesulfonyl)acrylamide (1.0 mmol, 0.27 g) was changed to monomer b. 2 Except for changing to 1-hexene (p=3) (0.5 mmol, 0.062 mL), the polar polyolefin (R) was prepared in the same manner as in Example 2-1. 2 We obtained (=Ts, p=3). The results are shown in Table 2.

[0162] <Example 2-12> The method was the same as in Example 2-1, except that the solvent was changed to 0.50 mL of anhydrous chlorobenzene (Aldrich) and the amount of N-allyl-N-(p-toluenesulfonyl)acrylamide (1.0 mmol, 0.27 g), to produce polar polyolefin (R 2 We obtained (=Ts, p=7). The results are shown in Table 2.

[0163] <Example 2-13> The solvent was changed to 0.50 mL of anhydrous chlorobenzene (Aldrich), and the amount of N-allyl-N-(p-toluenesulfonyl)acrylamide (1.0 mmol, 0.27 g) was changed, and monomer b 2 Except for changing to 1-octadecene (p=15) (0.5 mmol, 0.16 mL), the polar polyolefin (R) was prepared in the same manner as in Example 2-1. 2 We obtained (=Ts, p=15). The results are shown in Table 2.

[0164] <Example 2-14> The solvent was changed to 0.50 mL of anhydrous chlorobenzene (Aldrich), and monomer b 1 R 21Except for changing to a 4-methoxyphenylsulfonyl group (As) (1.0 mmol, 0.28 g), the polar polyolefin (R) was prepared in the same manner as in Example 2-1. 2 We obtained (=As, p=7). The results are shown in Table 2.

[0165] [Table 2]

[0166] <Example 3-1> Polymer (B) obtained under the same conditions as in Example 2-12 1 / ( B 1 +B 2 45 mg of (0.49, number average molecular weight (Mn) 16900, molecular weight distribution (Mw / Mn) 2.2) was dissolved in methylene chloride (3 mL), and the resulting polymer solution was cast onto a petri dish. A polymer film was prepared by evaporating the methylene chloride. 2.5 mL of 9.2 M-NaOH methyl alcohol solution was added dropwise to the obtained polymer film and allowed to stand at room temperature for 48 hours to open the pyrrolidone ring. Subsequently, the polymer was recovered and vacuum-dried overnight at room temperature to obtain unit B represented by formula (2a). 1 (R 2 Unit B, represented by equation (2ax) = Ts). 1x (R 2 =Ts, R 2x Unit B, represented by equation (2b) =Me) and equation (2b) 2 43.7 mg of polar polyolefin with p=7 was obtained.

[0167] Furthermore, this polar polyolefin 1 ¹H-NMR (DMSO-d6, room temperature) analysis revealed, as shown in Figure 8, a signal originating from the p-toluenesulfonyl group before ring opening (δ7.85) was observed, as well as a signal originating from the p-toluenesulfonyl group before ring opening at δ7.65. From the integral ratio of these signals, the ring-opening rate of the pyrrolidone ring in the obtained polymer (B 1x / ( B 1 +B 1x The percentage was 97%.

[0168] <Example 3-2> Polymer (B) obtained under the same conditions as in Example 2-12 1 / ( B 1 +B 2 98 mg of (m³=0.50, number average molecular weight (Mn) 12700, molecular weight distribution (Mw / Mn) 1.9) was dissolved in methylene chloride (3 mL), and the resulting polymer solution was cast onto a petri dish. A polymer film was prepared by evaporating the methylene chloride. On the obtained polymer film, 5.0 mL of 1.2 M-NaOH n-butyl alcohol solution was added and allowed to stand at room temperature for 60 hours to perform the ring-opening reaction of the pyrrolidone ring. Subsequently, the polymer was recovered and vacuum-dried overnight at room temperature to obtain unit B represented by formula (2a). 1 (R 2 Unit B, represented by equation (2ax) = Ts). 1x (R 2 =Ts, R 2x Unit B, represented by equation (2b) = n-Bu, and equation (2b) 2 58.3 mg of polar polyolefin with (p=7) was obtained. The ring-opening rate of the pyrrolidone ring in the obtained polymer (B 1x / ( B 1 +B 1x The percentage was 97%.

[0169] <Example 3-3> 98 mg of the polymer obtained in Example 2-14 was dissolved in methylene chloride (3 mL), the resulting polymer solution was cast onto a petri dish, and a polymer film was prepared by evaporating the methylene chloride. 5.0 mL of 1.2 M NaOH methyl alcohol solution was added to the polymer film, and the mixture was left to stand at room temperature for 60 hours to allow the pyrrolidone ring to open. The polymer was then collected and vacuum-dried overnight at room temperature to obtain unit B represented by formula (2a). 1 (R 2 Unit B represented by equation (2ax) = As) 1x (R 2 =As, R 2x Unit B, represented by equation (2b) =Me) and equation (2b) 270.3 mg of polar polyolefin with p=7 was obtained. The ring-opening rate of the pyrrolidone ring in the obtained polymer (B 1x / ( B 1 +B 1x ) was 89%.

[0170] <Example 4-1> 10 mg of the polymer obtained in Example 3-1, 9.4 mg of benzophenone, and 1 mL of dimethyl sulfoxide were added to a 5 mL sample bottle and irradiated with 365 nm light at room temperature. After a reaction time of 5 hours, the number-average molecular weight (Mn) of the polymer was 3600 and the molecular weight distribution (Mw / Mn) was 4.4. After a reaction time of 48 hours, the number-average molecular weight (Mn) of the polymer was 2500 and the molecular weight distribution (Mw / Mn) was 4.5.

[0171] <Example 4-2> 10 mg of the polymer obtained in Example 3-3, 8.1 mg of benzophenone, and 1 mL of dimethyl sulfoxide were added to a 5 mL sample bottle and irradiated with 365 nm light at room temperature. After a reaction time of 5 hours, the number-average molecular weight (Mn) of the polymer was 3600 and the molecular weight distribution (Mw / Mn) was 4.8. After a reaction time of 48 hours, the number-average molecular weight (Mn) of the polymer was 1900 and the molecular weight distribution (Mw / Mn) was 4.2.

Claims

1. The following formula (1): 【Chemistry 1】 (In formula (1), X １ R is a methylene group or a divalent cyclohexane residue, １ (where l is a hydrogen atom, an alkyl group, or a silyl group, l is 0 or 1, m is an integer from 0 to 30, and n is an integer from 0 to 4.) A polar polyolefin having unit A represented by [the symbol].

2. The number-average molecular weight (Mn) is between 500 and 50,000. The polar polyolefin according to claim 1.

3. A method for producing a polar polyolefin according to claim 1 or 2, In the presence of a palladium catalyst, the following formula (11): 【Chemistry 2】 (In formula (11), X １１ is a methyl group or a cyclohexyl group, R １１ (where l, m, and n are the same as l, m, and n in formula (1).) The process involves coordinating polymerization of monomer a, represented by the following steps: method.

4. The aforementioned palladium catalyst is obtained by cationizing an imine-type palladium complex with a boron compound. The method according to claim 3.

5. The imine-type palladium catalyst is defined by the following formula (3): 【Transformation 3】 (In formula (3), L ３１ and L ３２ are each independently a hydrogen atom, a halogen atom, an alkyl group, an aralkyl group, an aryl group, a silyl group, a siloxy group, an alkoxy group, an aralkyloxy group, or an aryloxy group, R ３１ and R ３２ are each independently a hydrocarbon group having 1 to 30 carbon atoms, R ３３ and R ３４ are each independently a hydrogen atom or a hydrocarbon group having 1 to 20 carbon atoms, and R ３３ and R ３４ may be bonded to each other to form a ring.) This is a palladium mononuclear complex represented by The method according to claim 4.

6. The imine-type palladium catalyst is defined by the following formula (3a): 【Chemistry 4】 (In formula (3a), A is independently an alkyl group having 1 to 4 carbon atoms, and B is a hydrogen atom, a halogen atom, an alkyl group having 1 to 4 carbon atoms, an alkoxy group having 1 to 4 carbon atoms, or an alkyl ester group having 1 to 4 carbon atoms.) This is a palladium mononuclear complex represented by The method according to claim 5.

7. The imine-type palladium catalyst is defined by the following formula (4): 【Transformation 5】 (In formula (4), L ４１ , L ４２ , L ４３ , and L ４４ Each of these is independently a hydrogen atom, a hydrocarbon group having 1 to 20 carbon atoms, an alkoxy group having 1 to 10 carbon atoms, an aryloxy group having 6 to 20 carbon atoms, an ester group having 2 to 10 carbon atoms, a substituted amino group having 1 to 12 carbon atoms, a thiocyanate group, or a halogen atom, R ４１ and R ４２ Each of these is independently a divalent hydrocarbon group having 1 to 20 carbon atoms, a divalent hydrocarbon group having 1 to 20 carbon atoms substituted with a hydroxyl group, a divalent hydrocarbon group having 2 to 20 carbon atoms substituted with an alkoxy group having 1 to 10 carbon atoms, a divalent hydrocarbon group having 3 to 20 carbon atoms substituted with an ester group having 2 to 10 carbon atoms, a divalent hydrocarbon group having 4 to 20 carbon atoms substituted with a silyl group having 3 to 18 carbon atoms, or a divalent hydrocarbon group having 1 to 20 carbon atoms substituted with a halogen atom, and R ４３ , R ４４ , R ４５ , and R ４６ Each of these is independently a hydrogen atom, a halogen atom, a hydrocarbon group having 1 to 20 carbon atoms, a hydrocarbon group having 1 to 20 carbon atoms substituted with a halogen atom, a hydrocarbon group having 2 to 20 carbon atoms substituted with an alkoxy group having 1 to 10 carbon atoms, an alkoxy group having 1 to 10 carbon atoms, or a substituted amino group having 1 to 20 carbon atoms, R ４３ and R ４４ , and R ４５ and R ４６ These elements may be independent of each other, or they may be joined together to form a ring. This is a palladium cyclic dinuclear complex represented by The method according to claim 4.

8. The imine-type palladium catalyst is defined by the following formula (4a): 【Transformation 6】 This is a palladium cyclic dinuclear complex represented by The method according to claim 7.

9. The aforementioned R １ If it is a hydrogen atom, R in the obtained polymer １１ The process involves deprotecting and substituting with hydrogen atoms. The method according to claim 3.

10. The following formula (2a): 【Transformation 7】 (In formula (2a), R ２ (This is a hydrogen atom, an alkylsulfonyl group, an arylsulfonyl group, an alkyloxycarbonyl group, or an aryloxycarbonyl group.) Unit B represented by １ and, The following equation (2b): 【Transformation 8】 (In equation (2b), p is an integer between 3 and 27.) Unit B represented by ２ and A polar polyolefin having [a certain characteristic].

11. Unit B １ and Unit B ２ The sum of the units B １ The proportion (B １ / (B １ +B ２ )) is between 0.10 and 0.70 The polar polyolefin according to claim 10.

12. The number-average molecular weight (Mn) is between 500 and 50,000. The polar polyolefin according to claim 10.

13. A method for producing a polar polyolefin according to any one of claims 10 to 12, In the presence of a palladium catalyst, the following formula (21a): 【Chemistry 9】 (In formula (21a), R ２１ (This group is an alkylsulfonyl group, an arylsulfonyl group, an alkyloxycarbonyl group, or an aryloxycarbonyl group.) Monomer b represented by １ and, The following equation (21b): 【Chemistry 10】 (In equation (21b), p is the same as p in equation (2b).) Monomer b represented by ２ and The process involves a step of coordination copolymerization. method.

14. The aforementioned palladium catalyst is obtained by cationizing an imine-type palladium complex with a boron compound. The method according to claim 13.

15. The imine-type palladium catalyst is defined by the following formula (4): 【Chemistry 11】 (In formula (4), L ４１ , L ４２ , L ４３ , and L ４４ Each of these is independently a hydrogen atom, a hydrocarbon group having 1 to 20 carbon atoms, an alkoxy group having 1 to 10 carbon atoms, an aryloxy group having 6 to 20 carbon atoms, an ester group having 2 to 10 carbon atoms, a substituted amino group having 1 to 12 carbon atoms, a thiocyanate group, or a halogen atom, R ４１ and R ４２ Each of these is independently a divalent hydrocarbon group having 1 to 20 carbon atoms, a divalent hydrocarbon group having 1 to 20 carbon atoms substituted with a hydroxyl group, a divalent hydrocarbon group having 2 to 20 carbon atoms substituted with an alkoxy group having 1 to 10 carbon atoms, a divalent hydrocarbon group having 3 to 20 carbon atoms substituted with an ester group having 2 to 10 carbon atoms, a divalent hydrocarbon group having 4 to 20 carbon atoms substituted with a silyl group having 3 to 18 carbon atoms, or a divalent hydrocarbon group having 1 to 20 carbon atoms substituted with a halogen atom, and R ４３ , R ４４ , R ４５ , and R ４６ Each of these is independently a hydrogen atom, a halogen atom, a hydrocarbon group having 1 to 20 carbon atoms, a hydrocarbon group having 1 to 20 carbon atoms substituted with a halogen atom, a hydrocarbon group having 2 to 20 carbon atoms substituted with an alkoxy group having 1 to 10 carbon atoms, an alkoxy group having 1 to 10 carbon atoms, or a substituted amino group having 1 to 20 carbon atoms, R ４３ and R ４４ , and R ４５ and R ４６ These elements may be independent of each other, or they may be joined together to form a ring. This is a palladium cyclic dinuclear complex represented by The method according to claim 14.

16. The imine-type palladium catalyst is defined by the following formula (4a): 【Chemistry 12】 This is a palladium cyclic dinuclear complex represented by The method according to claim 15.

17. The aforementioned R ２ If it is a hydrogen atom, R in the obtained polymer ２１ The process involves deprotecting and substituting with hydrogen atoms. The method according to claim 13.

18. The following equation (2ax): 【Chemistry 13】 (In formula (2ax), R ２ R is a hydrogen atom, an alkylsulfonyl group, an arylsulfonyl group, an alkyloxycarbonyl group, or an aryloxycarbonyl group. ２ｘ (This is a hydrogen atom or an alkyl group.) Unit B represented by １ｘ and, The following equation (2b): 【Chemistry 14】 (In equation (2b), p is an integer between 3 and 27.) Unit B represented by ２ and It has, The following formula (2a): 【Chemistry 15】 (In formula (2a), R ２ (This is a hydrogen atom, an alkylsulfonyl group, an arylsulfonyl group, an alkyloxycarbonyl group, or an aryloxycarbonyl group.) Unit B represented by １ A polar polyolefin which may have a polarity.

19. Unit B １ and Unit B １ｘ and Unit B ２ The sum of the units B １ and Unit B １ｘ The total percentage ((B １ +B １ｘ ) / (B １ +B １ｘ +B ２ )) is between 0.10 and 0.70 The polar polyolefin according to claim 18.

20. Unit B １ and Unit B １ｘ The sum of the units B １ｘ The proportion (B １ｘ / (B １ +B １ｘ The value is between 0.30 and 1.

00. The polar polyolefin according to claim 18.

21. The number-average molecular weight (Mn) is between 500 and 50,000. The polar polyolefin according to claim 18.

22. A method for producing a polar polyolefin according to any one of claims 18 to 21, The step involves using an alkyl alcohol solution of an alkali metal hydroxide to open at least a portion of the pyrrolidone ring in the polar polyolefin described in any one of claims 10 to 12. method.

23. The alkali metal hydroxide is lithium hydroxide or sodium hydroxide. The method according to claim 22.

24. The alkyl alcohol is methyl alcohol or n-butyl alcohol. The method according to claim 22.

25. The aforementioned R ２ｘ If it is a hydrogen atom, The process involves hydrolyzing the ester groups in the resulting polymer and substituting them with hydrogen atoms. The method according to claim 24.

26. The following formula (2a): 【Chemistry 16】 (In formula (2a), R ２ (This is a hydrogen atom, an alkylsulfonyl group, an arylsulfonyl group, an alkyloxycarbonyl group, or an aryloxycarbonyl group.) Unit B represented by １ , and / or The following equation (2ax): 【Chemistry 17】 (In formula (2ax), R ２ R is a hydrogen atom, an alkylsulfonyl group, an arylsulfonyl group, an alkyloxycarbonyl group, or an aryloxycarbonyl group. ２ｘ (This is a hydrogen atom or an alkyl group.) Unit B represented by １ｘ and, The following formula (2ay): [Chemistry 18] (In formula (2ay), R ２ R is a hydrogen atom, an alkylsulfonyl group, an arylsulfonyl group, an alkyloxycarbonyl group, or an aryloxycarbonyl group. ２ｙ (This is a hydrogen atom or an alkyl group.) Unit B represented by １ｙ and, The following equation (2b): 【Chemistry 19】 (In equation (2b), p is an integer between 3 and 27.) Unit B represented by ２ and A polar polyolefin having [a certain characteristic].

27. the unit B １ and the unit B １ｘ and the unit B １ｙ and the unit B ２ the unit B relative to the total of １ and the unit B １ｘ and the unit B １ｙ Xthe ratio of the total ((B １ + B １ｘ + B １ｙ ) / (B １ + B １ｘ + B １ｙ + B ２ )) is .10 to.70 It should be noted that there seems to be some unclear or potentially incorrect notations in the original text (such as the repeated "B" with different tags without clear indication of their differences in meaning). The translation is done as accurately as possible based on the provided text. The polar polyolefin according to claim 26.

28. Unit B １ and Unit B １ｘ and Unit B １ｙ The sum of the units B １ｘ and Unit B １ｙ The total percentage ((B １ｘ +B １ｙ ) / (B １ +B １ｘ +B １ｙ The value is between 0.30 and 1.

00. The polar polyolefin according to claim 26.

29. The number-average molecular weight (Mn) is between 500 and 50,000. The polar polyolefin according to claim 26.

30. A method for producing a polar polyolefin according to any one of claims 26 to 29, By irradiating the polar polyolefin according to any one of claims 18 to 20 with light in the presence of a diaryl ketone, the unit B １ｘ The process involves cleaving at least a portion of the ring-opened pyrrolidone structure contained within. method.

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