TW200951148A - Cyclic olefin addition polymerized polymer and preparation method thereof - Google Patents

Abstract

The invention relates to a cyclic olefin addition polymerized polymer obtained by addition polymerizing functional silicone containing cyclic olefins shown in the following formula (1) (in the formula, R.supra.1 is 1-valence organic group that does not have the same or different aliphatic unsaturated bond. s is an integer from 0-2. j represents 0 or 1). The invention takes the forgoing functional silicone containing cyclic olefins as a monomer so as to obtain cyclic olefin addition polymerized polymer having excellent transparency, heat resistance, solubility with respect to organic solvents and polysiloxane solvent, preservation stability and treatment.

Description

200951148 6. INSTRUCTIONS OF THE INVENTION: TECHNICAL FIELD The present invention relates to a cyclic dilute hydrocarbon addition polymer comprising a decane structure and a process for producing the same. [Prior Art] [Background Art] φ Polycycloolefin has excellent transparency, thermal stability, strength, gas permeability, and good film forming properties, and therefore, it is an optical material, a gas separation membrane material, and a coating. Functional plastic for film forming materials. On the other hand, the organopolysiloxane is a functional polymer excellent in heat resistance, water resistance and chemical resistance, and is practically used in a wide range of fields. A resin having such a polycycloolefin structure and a polyoxyalkylene structure has a high functional polymer having both characteristics. Up to now, as a material having excellent transparency and heat resistance, the following is proposed as a ring-opening polymer of a cyclic olefin compound and a hydrogenated product thereof or an addition polymer of a cyclic olefin compound. Japanese Patent Publication No. 60-26024 (Patent Document 1), Japanese Patent No. 3 0 0 0 196 (Patent Document 2), JP-A-1-132625 (Patent Document 3), and Japanese Patent Laid-Open Japanese Laid-Open Patent Publication No. JP-A-61-292601 (Patent Document 5), Japanese Patent Application Laid-Open No. Hei. No. Hei. No. Hei. C hem · M acr 〇m ο 1. S ymp . V 〇 1 4 7 83 (1991) (Non-Patent Document 1) The polymer-based cyclic olefin compound is opened 200951148 Ring polymer and its hydride, or It is an addition polymer of a cyclic olefin compound and a linear hydrocarbon, and has excellent processability or solubility. However, the glass transition temperature is mostly in the state of less than 17 (TC), and it is mostly in the state of heat resistance. Further, regarding the ring-opening polymer, heat resistance is improved, and therefore, it is necessary to carry out hydrogenation of a double bond. Japanese Patent Laid-Open No. Hei 4-63-807 (Patent Document 7), Japanese Patent Application Publication No. Hei. No. Hei. No. Hei. No. Hei. Japanese Patent No. 3476466 (Patent Document 10), Japanese Patent Laid-Open No. Hei 7-196736 (Document 11), International Publication No. 97/2087 No. 1 brochure (Special Offer 12), and International Publication No. 98/203 No. 94 (Patent 1 3), Japanese Patent No. 3 80 0 0 8 (Patent Document 14), and Chem. Soc. Polymer Preprints Vol 40 (2), 782 (1 999) (Library 2) The adduct of the polymer-derived spinane-based compound has transparency and heat resistance. However, these polymers exhibit an organic solvent having a strong polarity, for example, an aromatic solvent such as toluene, benzene or xylene, dichloromethane, or the like. The nature and deficiency of halogenated hydrocarbon solvents such as vinyl chloride and chlorobenzene For the weakly polar hexane, octane, decane, etc., the aliphatic medium 'hexamethyldioxane' methyltris(trimethylformamoxy), decamethylcyclopentasiloxane, etc. The solubility of the decane-based solvent is not limited, and it is used in the Japanese Patent Laid-Open Publication No. SHO 60-26024. Manufactured by the Japanese Patent Laid-Open Publication No. Hei. No. 9-200951148 [Patent Document 3] Japanese Laid-Open Patent Publication No. Hei No. Hei No. Hei 1-132325 [Patent Document 4] [Patent Document 5] Japanese Laid-Open Patent Publication No. Hei. No. Hei. No. Hei. No. Hei. No. Hei. No. Hei. No. Hei. No. Hei. Japanese Patent Publication No. Hei. No. Hei. No. Hei. No. Hei. No. Hei. No. Hei. No. Hei. No. Hei. No. Hei. No. Hei. [Patent Document 12] International Publication No. 97/20871 Introduction Booklet [Patent Document 13] International Publication No. 98 / 203 No. 94 publication [Patent Document 14] Japanese Patent No. 3 80 1 0 1 8 [Patent Document 15] International Publication No. 02/062859 Introduction Booklet [Patent Document 16] Japanese Patent Laid-Open No. 2003_252 8 8 1 [Patent Document 17] German Patent Application Publication No. 4 1 28932, pp. [Patent Document 18] Japanese Laid-Open Patent Publication No. 2007-77252 [Patent Document 19] Japanese Patent Application Laid-Open No. Hei. No. 20 07-703 No. 20] Japanese Laid-Open Patent Publication No. 2007-291 1-50 [Non-Patent Document 1] Makromol. Chem. Macromol. Symp. Vol 47, 83 (1 99 1 ) [Non-Patent Document 2] Am. Chem. Soc. Polymer Preprints Vol 40(2), 782(1999) 200951148 [Disclosure of the Invention] [Disclosure of the Invention] [Problems to be Solved by the Invention] The present invention has been made in view of the foregoing circumstances, and an object thereof is to provide a cyclic olefin functionality. A cyclic olefin addition polymer having a function of both a polycycloolefin and a decane as a monomer, and a method for producing the same. .

[Means for Solving the Problem] @ The present inventors have made a thorough review in order to achieve the above-mentioned object, and as a result, it has been found that the addition polymerization is selected from the chemical formulas (1), (2), (3). The cyclic olefin addition polymer having a specific structure obtained by at least one oxoxane of the cyclic olefin functional siloxane is excellent in transparency, heat resistance, solubility in an organic solvent, and preservation. The stability and handling materials are such that the present invention is completed. Accordingly, the present invention provides a cyclic olefin addition polymer shown below and a process for producing the same. 〇 [Patent No. 1 of the patent application] A cyclic olefin addition polymer is obtained by addition polymerization of a cyclic olefin functional oxime represented by the following chemical formula (Π).

SiR1s(OSiR1j)[5-s] (1) 200951148 (In the formula, R1 is a monovalent organic group having no aliphatic or unsaturated bonds which are the same or different from each other, and an integer of s is 〇~2, and j is a 〇 Or 1). [Scope of Patent Application No. 2] A cyclic olefin addition polymer is obtained by addition polymerization of a cyclic olefin functional oxime represented by the following chemical formula (2). [Chemical 2]

(wherein R 2 is a monovalent organic group having no aliphatic or unsaturated bonds which are the same or different from each other, t is an integer of 2 to 5, and k is 0 or 1). [Patent 3] The φ-type cyclic olefin addition polymer is obtained by addition polymerization of a cyclic olefin functional oxime represented by the following chemical formula (3). [化3]

(3) (SiR^O^riSiR^mz'tRVa- (SiR32〇), »4-(SiR52)m5~ (R^ni-iSiR^OUT-SiRj (wherein, R3 systems do not have the same or phase a monovalent hydrocarbon group of an aliphatic unsaturated bond, R0 is an alkyl group, and R' is a monovalent hydrocarbon group having no aliphatic or unsaturated bond which is the same or different from each other; X represents 0 or 1. ml, m2 M3 -9- 200951148, m5, m6, m7 are 0 or 1, and m4 represents an integer of 1 or more. [Application No. 4] A cyclic olefin addition polymer selected from the group consisting of addition polymerization At least two types of cyclic olefin functional siloxanes represented by the chemical formulas (1), (2), and (3) described in the first, second, and third aspects of the patent application are obtained.

[Scope of Patent Application No. 5] A cyclic olefin addition polymer obtained by addition polymerization of a cyclic olefin compound represented by the following chemical formula (4) and selected from the first and second terms of the patent application range The at least one of the cyclic olefin functional siloxanes represented by the chemical formulas (1), (2), and (3) is derived from the chemical formulas (1), (2), and (3) described above. The ratio of the structural unit of the cyclic olefin functional siloxane is 50 mol% or more in the copolymer.

【化4】

-10- 200951148. The i system indicates 〇 or 1). [Calculation No. 6] The cyclic rare hydrocarbon addition polymer according to any one of claims 1 to 5, which is in the form of a film, a sheet or a film. [Patent Application No. 7] - A method for producing a cyclic thin smoke addition polymer, which is a compound selected from a transition metal of a nickel, a precursor, and a pin of a polymerization catalyst, and/or a transition metal compound and a super acid The denatured compound and at least one compound selected from the group consisting of a Lewis acidic compound, a Lewis acidic boron compound, an ionic compound, and an ionic boron compound, and the addition polymerization is selected from the aforementioned chemical formulas (1), (2), ( 3) One or more of the cyclic olefin functional siloxanes represented by the above or one or more of the cyclic olefin functional siloxanes, or more than 50% by mole and the above chemical formula (4) The cyclic olefin compound represented by hydrazine is 50% by mole or less. [Effect of the Invention] According to the present invention, the above-mentioned cyclic olefin functional siloxane is used as the monomer ', and excellent transparency, heat resistance, dissolution to an organic solvent and a polyoxyalkylene solvent are obtained. Sexual, storage stability and handling of cyclic smoldering addition polymers. [Embodiment] -11 - 200951148 [Best Mode for Carrying Out the Invention] The cyclic olefin addition polymer of the present invention is represented by addition polymerization of the following chemical formulas (1), (2), (3) At least one of a cyclic olefin functional siloxane is obtained. 【化5】

sirVosir^ (1)

(wherein R1 is an integer of 0 to 2 having no monovalent organic group of the aliphatic unsaturated bond which is the same or different from each other, and j is 〇 or 1). (2) '1(OSIR22)t" (wherein R2 is a monovalent organic group having no aliphatic or unsaturated bonds which are the same or different from each other, t is an integer of 2 to 5, and k is represented by 0 or 1). (3) ^SiR3i°)m1-(SiR32)in2'(R%Il3-(SiR32O)in4-(SiR32)IIl5-(R0)m6-(SiR32O)in7-SiR,: (wherein R3 is a monovalent hydrocarbon group which does not have an aliphatic unsaturated bond which is the same or different from each other, and is a monovalent hydrocarbon group which does not have an aliphatic unsaturated bond which is the same or different from each other. 0 or 1. ml, m2, m3 -12- 200951148, m5, m6, m7 are 0 or 1, and m4 means an integer of 1 or more).

In the above chemical formulas (1) to (3), R1, R2, and R3 are a monovalent organic group which does not have an aliphatic unsaturated bond which may be the same or different from each other, and preferably has a carbon number of 1 to 20, more preferably carbon. The monovalent organic group of 1 to 10, for example, an alkyl group such as a methyl 'ethyl group, a η-propyl group, a butyl group or a pentyl group, an aryl group such as a phenyl group, a tolyl group or a xylyl group, or a 2-benzene group. One or more of these hydrogen atoms, such as an arylalkyl group such as an ethyl group or a 3-phenylpropyl group, may be substituted with a halogen atom such as a fluorine, chlorine or bromine atom. In the above chemical formula (3), the alkyl group as R0 has a carbon number of 1 to 4, particularly 1 to 2, and the alkylene group is linear or branched. The series of monovalent hydrocarbon groups having no aliphatic unsaturated bond as R' is the same as the carbon number of 1 to 20' of R1, R2 and R3, particularly a carbon number of 1 to 1 Å. The cyclic suspected hydrocarbon functional sand oxide system represented by the chemical formula (1) may be exemplified by the following compounds, but the present invention is not limited to these specific examples. Here, Me means a methyl group, and Ph means a phenyl group. [化8] πχ ^^^SiMePhOSiMe^ πχ ^^^SIPh2OSiMe3

SiMePhOSiPh3 The cyclic olefin functional siloxane having the chemical formula (2) may be exemplified by the following compounds. However, the present invention is not limited to these specific examples. Here, Me means a methyl group. -13- 200951148 【化9】 Me Me

The cyclic olefin functional oxiranane represented by the chemical formula (3) is particularly preferably a group represented by the following chemical formulas (5) and (6). © 【化1 0】 (5)

(6) (SiR32O)-(SiR32)-(R0)-(SiR32O)in4-(SiR32)-(R0)-SiR,3 In the above chemical formulae (5) and (6), m4 is an integer of 1 or more However, it is preferably an integer of 2 to 80, more preferably an integer of 2 to 60. Further, R3, V, R, and X are as described above. The cyclic olefin functional siloxanes represented by the above chemical formulas (3), (5), and (6) may be exemplified by the following compounds. However, the present invention is not limited to these specific examples. Here, 'Me means a methyl group, and Bu means a butyl group. 200951148 【化1 1】

SiMe2〇SiMe2CH2CH2SiMe2(OSiM«2)1,0OSiMe2CH2CH2SiMej The cyclic olefin functional siloxanes represented by the chemical formulas (1) to (3) may be used alone or in combination of two or more. Here, when two or more types are used in combination, for example, a compound of two or more kinds of the chemical formula (1) may be used in combination, and a compound of the chemical formula (1) and the chemical formula (2) may be used in combination, for example. The status takes place. In the present invention, the cyclic olefin represented by the following chemical formula (4) may be added to at least one of the cyclic olefin functional siloxanes represented by the chemical formulas (1), (2), and (3). The copolymerization is carried out for the purpose of use, and the heat resistance of the obtained cyclic olefin addition polymer of the present invention, solubility to an organic solvent, storage stability, and handleability are adjusted.

In the chemical formula (4), 'A1 to A4 are each independently selected from a halogen atom such as a hydrogen atom, a fluorine atom, a chlorine atom or a bromine atom, a methyl group having a carbon number of 1 to 10, an ethyl group, a propyl group or an isopropyl group. An alkyl group such as a butyl group, an isobutyl group, a tert-butyl group, a pentyl group, a neopentyl group, a hexyl group, an octyl group, a decyl group or a fluorenyl group; a cycloalkyl group having a ring of 200951148 or the like; a phenyl group or a tolyl group; An alkoxy group such as an aryl group such as a xylyl group or a naphthyl group; an alkoxy group such as a methoxy group, an ethoxy group or a propoxy group; an aryloxy group such as a phenoxy group; or a 3,3,3-trifluoropropyl group; a group of a halogenated hydrocarbon group such as -(perfluorobutyl)ethyl, 2-(perfluorooctyl)ethyl or P-chlorophenyl, or an oxetanyl group, a methoxycarbonyl group, a tert- A preferred alkoxy group such as a butoxycarbonyl group has a polar substituent having 1 to 10 carbon atoms, particularly 1 to 6 alkoxycarbonyl groups. Further, A1 and A2 or A1 and A3 may form an alicyclic structure, an isocyanato group or an acid anhydride group at the same time as each bonded carbon atom. The i system indicates 〇 or 1. In this state, the carbon number is 4 to 10 as a series of alicyclic structures. In exemplifying these structures, as described below. Further, in the following examples, Me represents a methyl group, and Ph represents a phenyl group. [化1 3] mmmm

Isocyanate anhydride group

The cyclic olefin compound represented by the chemical formula (4) may be exemplified by the following compounds. However, the present invention is not limited to these specific examples-16 to 200951148, and a bicyclo[2.2·1]heptyl_2_ may be exemplified. Hydrocarbon, 5-methyl-bicyclo[2.2.1]heptyl-2-olefin, 5-ethyl-bicyclo[2.2.1]heptyl-2-olefin '5-propyl-bicyclo[2.2 .1] heptyl-2-olefin '5-butyl-bicyclo[2.2.1]heptyl-2-olefin, 5-pentyl-bicyclo[2.2.1]heptyl-2-olefin, 5- Hexyl-bicyclo[2.2.1] heptyl-2-olefin, 5-octyl-bicyclo[2.2.1]heptyl-2-olefin, 5-fluorenyl-bicyclo[2.2.1]heptyl- 2-olefin, 5-phenyl-bicyclo[2.2.1]heptyl-2-olefin, 5-cyclohexyl-bicyclo[2.2.1]heptyl-2-olefin, 5-fluoro-bicyclo[ 2.2.1] heptyl-2-olefin, 5-chloro-bicyclo[2.2.1]heptyl-2-olefin, bicyclo[2.2.1]heptyl-5-olefin-2-carboxylic acid methyl, Bicyclo[2.2.1]heptyl-5-olefin-2-carboxylic acid ethyl, bicyclo[2.2.1]heptyl-5-olefin-2-carboxylic acid butyl, 2-methyl-bicyclo[ 2.2.1] Heptyl-5-olefin-2-carboxylic acid methyl, 2-methyl-bicyclo[2.2.1] heptyl-5-olefin-2-carboxylic acid ethyl, 2-methyl-di Ring [2.2.1] heptyl-5-olefin-2-carboxylic acid propyl, 2- Base-bicyclo[2.2.1]heptyl-5-olefin-2-carboxylic acid trifluoroethyl, 2-methyl-bicyclo[2.2.1]heptyl-2-butenylacetate ethyl, acrylic acid 2-methyl-bicyclo[2.2.1]heptyl-5-butenyl, methacrylic acid φ 2-methyl-bicyclo[2.2.1]heptyl-5-butenyl, bicyclo[2.2 .1]heptyl-5-olefin-2,3-dicarboxylic acid dimethyl, tricyclo[4.3.0.12'5]deca-3-olefin, tetracyclo[4.4.0.12>5.17'10]12 -3-olefins and the like. These may be used alone or in combination of two or more. The cyclic olefin functional siloxane having the chemical formulas (1) to (3) can be produced by the method shown below (refer to the publication of International Publication No. 02/062859 (Patent Document 15), Japanese Patent Laid-Open Japanese Patent Application Publication No. 4 289 32 (Patent Document 17), JP-A-2007- -17-200951148 No. 77252 (Patent Document 18), Japanese Special Japanese Laid-Open Patent Publication No. 2007-70337 (Patent Document 19) and JP-A No. 200-7-29U50 (Patent Document 20). As the first method, the synthesis can be carried out by a Diels-Alders reaction (Diels-Alder reaction) of a olefin having a terminal olefin and dicyclopentadiene. Here, Me means a methyl group, and Ph means a phenyl group. [Chemical 1 4] + 2CH2=CHSi(OSiMe3)3

Si(OSiMe5)j

2CH2=CHSiMePhOSiMe3

❹ As a second method, the addition reaction can be carried out in the presence of a platinum catalyst, and the addition reaction is carried out in the same manner as the SiH functional polyxite of the original sinister hydrocarbon. Here, 'Me means a methyl group, and BU means a butyl group. -18- 200951148 【化1 5】 0) + HSIMe2(OSiMe2)4〇OSiMe2Bi

Pt

The loading ratio of the cyclic olefin functional oxime represented by the chemical formulas (1), (2), and (3) in the state of using the cyclic olefin represented by the chemical formula (4) in the state of SiMe2(〇SiMe2)40OSiMe2Bu The physical properties (transparency, heat resistance, solubility, storage stability, and handleability, etc.) of the cyclic olefin addition polymer of the present invention are arbitrarily adjusted for the purpose of use, but the copolymerization obtained therefrom The structure of the chemical formulae (1) to (3) in the product is preferably 50 mol% or more in total, and preferably 70 mol% or more. When the structure of the cyclic olefin represented by the chemical formula (4) is 50 mol% or more in the cyclic olefin addition polymer of the present invention, the solubility in the organic solvent is lowered. The cyclic olefin addition polymer of the present invention is a cyclic olefin functional oxirane represented by the chemical formulas (1), (2) and (3) by the purpose of blending in the presence of an addition polymerization catalyst. At least one of the cyclic olefins represented by the chemical formula (4) is produced by addition polymerization. As the addition polymerization catalyst system, the following single component catalyst (A) or multicomponent catalyst (B) may be used, but the present invention is not limited thereto. The (A) single component catalyst system may, for example, be a compound of the following (A-1) to (A-3). (A-1) A compound represented by the following chemical formula (a) [LYMLV [A]· (a) -19- 200951148 (the oxime of the chemical formula (a) means nickel (Ni), cobalt (Co) or ( Pd) L1, L2, and L3 are ligands of ruthenium, one of which has a sigma bond, and has a Γ bond of 1 to 3 in all ligands. A lanthanide group represents an anion pair. L1, L2, and L3 systems It is selected from the group consisting of a cyclic diene having 6 to 12 carbon atoms, a raw spinane diene, a cyclic triene having 10 to 20 carbon atoms, and an aromatic compound having 6 to 20 carbon atoms. The anion pair of A is preferably BFr or PF. / '

SbFs, S03F·, AsF6·, SbF6·, CF3C02·, C2F5C〇2, B[C6F5]4_, B[C6H3(CF3)2]4·). © As a specific example of the compound represented by the chemical formula (a), [( 7? 3 - octadecyl) Ni (cyclohexa-1,5-diolefin) nB (C6H3(CF3)2) 4], [( τ?3-octadecyl)Ni (cyclohexa-1,5-diolefin)][PF6],[(6-methoxy-bicyclo[2.2.1]heptyl-2-olefin-endo-5σ , 2ττ ) Pd (cyclohexa-1,5-diolefin)][SbF6], [( 7? 3-ally)Pd][BF4], [(cyclohexa-1,5-diolefin) Pd(CH3) Cl][B (C6H3(CF3)2) 4] and the like. (A-2) The compound represented by the following chemical formula (b): [Pd(H)(L4)4][A]2 (herein, the A-line anion pair is the same as (A-1). L4 is selected from the group consisting of a nitrile compound, a tertiary amine compound, and a triarylphosphine compound). Specific examples of the compound represented by the chemical formula (b) are [Pd(C6H5CN)4][BF4]2, [Pd(C6H5CN)4][SbF6]2, [Ph3PdCH3][B(C6H3(CF3)2) 4] (here, Ph represents a phenyl group) and the like. (A-3) Aromatic Hydrocarbons of Ni(C6F5)2 or Ni(SiCl3)2-20- 200951148 As a specific example thereof, toluene·Ni(C6F5)2, xylene·Ni(C6F5)2, toluene.Ni (SiCl3) 2 and so on. The (B) multicomponent catalyst system can be exemplified by (B-1) to (B-3) shown below. (B-1) Transition metal compound As the transition metal compound series, one compound selected from the group listed below is used. a) a compound selected from the group consisting of an organic carboxylate of nickel (Ni), cobalt (Co), and palladium (Pd), an organic phosphite, an organic phosphate, an organic sulfonate, a diketone compound, and the like, specifically, nickel acetate, Nickel octoate, nickel 2-ethyl hexanoate, nickel oleate, nickel stearate, nickel dibutyl phosphate, nickel dioctoate, nickel lauryl benzene sulfonate, nickel bis(ethyl decyl acetate), double (Ethyl pyruvate) nickel, cobalt 2-ethylhexanoate (π), cobalt 2-ethylhexanoate (BI), cobalt dodecanoate (ruthenium), tris(acetonitrile) Acid esters: cobalt (melon), palladium acetate, palladium 2-ethyl hexanoate, bis(ethyl phthalate) palladium, and the like. b) The above-mentioned nickel (Ni) 'cobalt (Co) and palladium (Pd) organic carboxylate and super acid denatured compound as a series of super acid examples of hexafluorinated acetone, hexafluoroantimonic acid, tetrafluoro Boric acid, trifluoroacetic acid, and the like. 200951148 C) Nickel diene or nickel toluene miscide specifically enumerates [(π 3-octadecyl)Ni (cyclohexa-1,5-diolefin) nB(C6H3(CF3)2)4], [double (two Ring [2.2.1] heptyl-2,5-diolefin)

Ni], [(cyclod-12-1,5,9-triolefin) Ni], and the like. d) The complex compound of a ligand having an atom of phosphorus (P), nitrogen (N), oxygen (0) or the like in nickel coordination specifically (PPh3)2NiCl2, (PPh3)2NiBr2, (PPh3)2 φ ( :〇(:12, bis[1(3-161^-butyl-salicylidene)phenyl alatto orange]1^, Ni(0C(0)(C6H4)PPh2)(H)(PCy3), Ni (0C(0)(C6H4)PPh2)(H) (PPh3), Ni(COD)2 and Ph3P = CHC(0)Ph reactants (here,

Ph is a phenyl group, Cy is a cyclohexyl group, and COD is a 1,5-cyclooctadiene). Wait. (B-2) The organoaluminum compound specifically exemplifies methyl amidine, butyl alum, partially mixed trialkylaluminum quinone methylmethyl alum, trimethylaluminum, triisobutylaluminum, diisobutylaluminum hydrogenation , diethyl aluminum chloride, and the like. (B-3) The compound to be added for increasing the polymerization activity specifically includes an ether of boron trifluoride or aluminum trifluoride, a complex of an amine, a phenol, or the like, tris(pentafluorophenyl)borane, and three ( 3,5-di-trifluoromethylphenyl) borane, tris(pentafluorophenyl)aluminum, etc., a boron compound exhibiting Lewis acidity and an aluminum compound 'further', exemplified by triphenylcarbon gun tetrakis(pentafluorophenyl)borate -22- 200951148 Ester, Tributyl Aluminum Tetrakis(pentafluorophenyl)borate, N,N-Dimethylaluminum tetrakis(pentafluorophenyl)borate, Triphenylcarbamate Tetrakis(pentafluorobenzene) An ionic boron compound such as an aluminate or a triphenylcarbenyltetrakis(2,4,6-trifluorophenyl)aluminate or an ionic aluminum compound. Even among these, in order to increase the polymerization activity, a compound selected from a transition metal of nickel, cobalt, and palladium, and a denatured compound of the transition metal compound and a super acid are preferably used as one of the polymerization catalysts. φ At least one compound selected from the group consisting of a Lewis acidic aluminum compound, a Lewis acidic boron compound, an ionic aluminum compound, and an ionic boron compound is added. These catalyst components are used in the following ranges. The transition metal compound such as a nickel compound, a cobalt compound or a palladium compound is 0.01 to 100 mmol atoms with respect to the monomer 1 molar, and the organoaluminum compound is 1 to 1 with respect to the transition metal compound 1 molar atom. 00 0 mole, and the Lewis acidic boron compound and the aluminum compound, or the ionic boron compound and the aluminum compound are 0.5 to 100 moles with respect to the nickel or cobalt 1 molar precursor. The cyclic olefin addition polymer of the present invention can be obtained by using the above-mentioned single component catalyst or multicomponent catalyst, and can be used in an alicyclic hydrocarbon solvent selected from cyclohexane, cyclopentane or the like, hexane, and octane. An aliphatic hydrocarbon solvent such as an alkane; an aromatic hydrocarbon solvent such as toluene, benzene or xylene; a halogenated hydrocarbon solvent such as dichloromethane, tetrachloroethylene or chlorobenzene; octamethylcyclotetraoxane or decamethylcyclohexane; One or two or more kinds of solvents, such as a cyclic polyoxane solvent, such as pentaoxane, are polymerized. The amount of the solvent used is preferably a mass ratio of the solvent (S) and a monomer composed of the above-mentioned cyclic olefin-23 to 200951148 (the compound represented by the above chemical formula (〇~(4)) (Μ) (S/ M) is in the range of 1 to 30, particularly in the range of 1 to 20. When the amount of the solvent used is less than the above-mentioned mass ratio, the viscosity of the solution becomes high, and the handleability becomes difficult, which is higher than the above. In the mass ratio, there is a state in which the polymerization activity is deteriorated. As a polymerization method, a solvent composed of the above-mentioned cyclic olefin and the above-mentioned addition polymerization are charged under a nitrogen or argon atmosphere. The catalyst is polymerized into the reaction vessel and polymerized at a temperature ranging from -20 ° C to 1 ° C. ❹ The polymerization reaction is preferably carried out at -2 (TC~10 (TC, especially 0 to 8 〇 °C) When the reaction temperature is excessively low, the state in which the polymerization activity is deteriorated occurs, and when it is excessively high, gelation or a state in which the molecular weight is not easily adjusted may occur. Adding a molecular weight regulator to the polymerization system. As a molecule The regulator series is an aromatic vinyl compound such as an α-olefin such as hydrogen, ethylene, butylene or hexene, styrene, 3-methylstyrene or divinylbenzene, or tris(trimethylmethoxy). a vinyl fluorene compound such as vinyl decane, divinyl quinone, or vinylcyclotetraoxane. Further, the ratio of the solvent to the monomer, the polymerization temperature, the polymerization time, and the molecular weight regulator are It is significantly affected by the catalyst 'monomer structure and the like used, and therefore, it is not easy to be completely limited. It must be used separately for the purpose. By the amount of the polymerization catalyst and the amount of the molecular weight regulator, the monomer is used. The conversion to the polymer, or the polymerization temperature, adjusts the molecular weight of the polymer. -24- 200951148 The termination of the polymerization is carried out by a compound selected from the group consisting of water, alcohol, ketone, organic acid, etc. The solution is added with water and an alcohol compound of acid such as lactic acid, malic acid, or oxalic acid, and the catalyst residue is separated and removed from the polymer solution. Further, the catalyst residue can be removed and used. The adsorption of carbon, diatomaceous earth, alumina, cerium oxide, etc. is removed by filtration or the like by filtration or the like. The polymer can be placed in methanol or ethanol by adding the polymer solution. In the ketones such as alcohols, acetone, methyl ethyl ketone, etc., it is obtained by solidification and drying under reduced pressure. In this step, the catalyst residue or unreacted monomer remaining in the polymer solution is also removed. The cyclic olefin addition polymer of the present invention obtained as described above comprises an addition of a cyclic olefin functional oxirane represented by the chemical formulas (1), (2), and (3) as a monomer. Any one or two or more kinds of repeating units represented by the following chemical formulas (7), (8), and (9) formed by polymerization.

SiRV〇SiRl3)M (wherein, R1, s, and j are the same as in the chemical formula (1) -25- 200951148 [Chem. 1 7]

(wherein R2, t and k are the same as in the formula (2)). [化1 8]

(SiR^O^rCSiR^z-CRVriSiR^OUi-CSiR^-CRVe-iSiR^OW-SiRj (wherein R3, R〇, R', ml~m7 are the same as chemical formula (3)) » In addition, this The cyclic olefin addition polymer of the invention may comprise a repeating unit represented by the following chemical formula (1) which is formed by addition polymerization of a cyclic olefin represented by the chemical formula (4).

(10) (wherein, A1 to A4 and i are the same as in the chemical formula (4)). Here, the repeating unit represented by the chemical formulas (7) to (10) shows that the 2,3 addition structural unit may include a ring represented by the chemical formulas (1) to (3). The 2,7 addition structural unit is formed by addition polymerization of the olefin functional siloxane and the cyclic olefin compound represented by the chemical formula (4) as a monomer. In the addition polymer of the cyclic olefin functional siloxane of the present invention, the total ratio is usually 50% by mole or less, preferably 30, in the state of the structural unit represented by the chemical formula (1 〇). Mole% or less. When the total ratio of the structural units represented by the formula (10) exceeds 50 mol%, there is a decrease in the aliphatic hydrocarbon solvent for hexane, octane, decane, etc., hexamethyldioxane, and ten. The solubility state of the polyoxane solvent such as methylcyclopentaoxane occurs. Further, the structural unit represented by the chemical formula (10) may be randomly present in the addition polymer of the cyclic olefin functional siloxane, or may be block-oriented in the addition of the cyclic olefin functional siloxane. Into the polymer. The molecular weight of the cyclic olefin addition polymer of the present invention is a polystyrene-equivalent number average molecular weight (1^11) measured by gel permeation chromatography using toluene as a solvent, and is preferably 10,000 to 1,000,000. 30,000 to 500,000 > The weight average molecular weight (Mw) is 20,000 to 2,000,000, preferably 40,000 to 1,600,00 (). When the number average molecular weight is less than 10, 〇〇〇 or the weight average molecular weight is less than 20,000, it is liable to become brittle and crack when it becomes a film, a film and a sheet. On the other hand, when the number average molecular weight exceeds 1,000,000 or the weight average molecular weight exceeds 2,000,000, there is a state in which the formability is lowered or the viscosity of the solution is lowered to lower the handleability. In the present invention, it is easy to obtain a cyclic olefin addition polymerization having a narrow molecular weight distribution in which the weight average molecular weight (Mw) and the number average molecular weight (?η) ratio 値 (Mw/Μη) are in the range of 2.0 to 5.0. Things. Therefore, it is excellent in cracking or brittleness when it is applied to a film such as a coating film, a film or a sheet. The glass transition temperature of the cyclic olefin addition polymer of the present invention is measured using a differential scanning calorimeter (DSC). The glass transition temperature of the cyclic olefin addition polymer of the present invention evaluated in this manner is not particularly limited, but is processed in a state in which the cyclic olefin addition polymer of the present invention is contained in a state of being too excessively low. At the time of use or when it is used, problems such as thermal deformation may occur. Further, in the state where the glass transition temperature is excessively high, the processing temperature is excessively high at the time of hot working, and the molded body containing the cyclic olefin addition polymer of the present invention may be thermally deteriorated. Therefore, the glass transition temperature of the cyclic olefin addition polymer of the present invention can be adjusted in the range of 170 to 35 °C for the purpose of blending. The cyclic olefin addition polymer of the present invention can be confirmed by nuclear magnetic resonance spectroscopy (CH-NMR, 29Si-NMR). For example, in 1H-NMR (in heavy chloroform), the absorption by 7.8~6.5ppm of -Si-C6H5, -0-Si(C6H5)-〇-C6H5, from 〇.6~3.0ppm Absorption of cyclic hydrocarbons, 〇.〇~0.6PPm of -Si·C.H2-, _Si-CH3, absorption of -〇_Si-CH3, -〇·1~0.〇PPm-O-SUCHs)- . - absorption> and, in 29Si-NMR (in heavy benzene), is absorbed by the unit (R4: methyl, 1〇·〇~5.〇PPm) from the following chemical formula (11), from D Absorption of units (R4: methyl, -15.0--25.0 ppm, R4: phenyl, -35.0 to -55.Oppm), absorption from T units (R4: alkyl, -65.0 200951148 to - 70.0) The integral ratio is confirmed by the structure. [化2 0]

(11) (M unit) (D unit) (T unit) (wherein R4 is the same as R1 in the chemical formula (1), R2 in the chemical formula (2), and R3 in the chemical formula (3). The addition polymer of the cyclic olefin functional siloxane of the present invention is preferably used in the form of a film, a sheet or a film. The thickness of the film, sheet or film is not particularly limited, but is usually adjusted to a range of 10 Onm to 3 mm for the purpose of blending. The method of forming the film, the sheet or the film shape is not particularly limited, and it can be formed by any method. However, it is preferable to dissolve the polymer of the present invention in terms of suppressing deterioration of the polymer due to the heat history. A solution casting method in which a solvent is applied to a support and then a solvent is dried (melting method) or a water surface unrolling film method in which the polymer solution of the present invention is dropped onto a water surface and then taken up by a support or the like is formed. . The solvent used in the solution casting method or the water surface developing film method must be a solvent for dissolving the addition polymer of the present invention. Many of the addition polymers of the present invention can be dissolved in an aliphatic hydrocarbon solvent such as cyclopentane, hexane, cyclohexane or decane, an aromatic hydrocarbon solvent such as toluene, xylene or ethylbenzene, or dichloride. a halogenated hydrocarbon solvent such as methane or chloroform, a hexamethyldioxane, a methyl tri-29-200951148 (trimethylformamoxy) decane, a decamethylcyclopentaoxane or the like. These solvents are used alone or in combination of one or more solvents. The cyclic olefin addition polymer of the present invention exhibits excellent solubility in any of the above-mentioned solvents, but it may be in a state in which the residual solvent cannot be removed during drying due to the film thickness or the coating conditions. Therefore, it is preferred to use a solvent having a relatively low boiling point of hexane, cyclohexane, toluene or the like as a main component. Further, in consideration of the influence on the human body or the load on the environment, it is preferable to use a highly safe polyoxyalkylene solvent such as methyltris(trimethylformamoxy)decane or decamethyl. A solvent such as cyclopentaoxane is used as a main component. Further, the above-mentioned solution containing the cyclic olefin addition polymer of the present invention can be used to improve the oxidation stability by absorbing a conventional oxidation preventing agent. As a series of oxidation inhibitors, 2,6-di-t-butyl-4-methylphenol, 4,4'-thiobis-(6-bubutyl-3-methylphenol), 1,1'-double -(4-hydroxyphenyl)cyclohexane, 2,5-di-t-butyl hydroquinone, pentaerythritol tetrakis[3-(3,5-di-t-butyl-4-hydroxyphenyl) Phenolic acid esters such as propionate or p-benzoic acid, tris(4-methoxy-3,5-diphenyl)phosphate, tris(nonylphenyl)phosphate, and tris(2,4) Phosphorus such as di-butylphenyl phosphate, bis(2,4-di-t-butylphenyl)pentaerythritol diphosphate, or even a thioether system or a lactone compound. Even in these compounds, the decomposition temperature (5% mass reduction temperature) is preferably 250 ° C or higher. In addition, the amount of the antioxidant is from 5% to 5.0 parts by mass based on 1 part by mass of the cyclic olefin addition polymer of the present invention. -30-200951148 [Examples] The examples and comparative examples of the present invention are shown below, but the present invention is not limited at all by these examples. The molecular weight, total light transmittance, refractive index, glass transition temperature, and solubility in an organic solvent were evaluated by the following methods. (1) Molecular weight (weight average molecular weight, number average molecular weight)·· φ was measured at 40 ° C using a TOSOH (HLC-8220GPC) gel permeation chromatography apparatus using toluene as a solvent. The molecular weight obtained is converted to standard polystyrene. (2) Total light transmittance: The total light transmittance was measured using a spectrophotometer device manufactured by Hitachi High-Tech Co., Ltd. (U-3310) at a predetermined thickness (100 μm) film and sheet. Reference (3) Refractive index: Determination of refractive index n25D 〇(4) glass transfer of D-rays (5 89 nm) at 25 ° C using a multi-wavelength Abbe refractometer manufactured by Atago Co., Ltd. (DR-M2/1 550) Temperature: Using a DSC (DSC820) apparatus manufactured by METTLER Co., Ltd., the temperature was raised and measured at 10 ° C / min from room temperature. -31 - 200951148 (5) Solubility to organic solvent: Toluene, xylene, decane, cyclohexane, hexane, dichloromethane, hexamethyldioxane, methyltris (three) are used as the solvent system. Methyl decyloxy) decane and decamethylcyclopentaoxane were prepared and evaluated by preparing a 10% by mass solution. [Example 1] Into a 1 L reaction vessel, 500 mmol of the compound A shown below was charged as a monomer in a nitrogen atmosphere, and 522 g of toluene was charged as a solvent. There, polymerization was carried out by charging bis(acetamidoacetate) nickel 0.50 mmol and tris(pentafluorophenyl)borane 2.50 mmol. The polymerization was carried out at 50 ° C for 24 hours. The polymerization was stopped with methanol. The obtained polymer solution was placed in 3 L of methanol, and the polymer was solidified to remove unreacted monomers and catalyst residues. The solidified polymer was dried to obtain a polymer P ( 1 ). [Chem. 2 1]

Si (OSIMej),

Compound A shows the 1H-NMR chart of polymer P(1) in Figure 1'. Further, the polystyrene-converted average molecular weight (?n) of the polymer P(l) is 29,100, and the weight average molecular weight (Mw) is 61,1, -32- 200951148.

Mw / Mn is 2.1. The results of the polymerization reaction are shown in Table 丨, and the solubility of the polymer in the organic solvent is shown in Table 2. The polymer P(l) was dissolved in toluene to prepare a polymer solution of 1% by mass. The solution was melt cast to prepare a film of thickness ΙΟΟμηη. The results of various physical property evaluations of the film are shown in Table 3. [Example 2] 聚合物 The same procedure as in Example 1 was carried out except that 250 mmol of the compound B of the following compound B was used as the monomer, and the polymer p ( 2 ) was obtained. [Chemical 2 2]

-Si-〇' Β Compound Β The 1 H-NMR chart of the polymer ρ(2) is shown in Fig. 2'. Further, the number average molecular weight (?η) of the polymer P(2) in terms of polystyrene was 29,000, the weight average molecular weight (Mw) was 78,300, and the Mw/Mn system was 2.7. The results of the polymerization reaction are shown in Table 1, and the solubility of the polymer in the organic solvent is shown in Table 2. The polymer P(2) was dissolved in toluene to prepare a polymer of -33 to 200951148 in an amount of 1% by mass. This solution was melt-cast to prepare a film F ( 2 ) having a thickness of ΙΟΟμηη. The results of various physical property evaluations of the film are shown in Table 3. [Example 3] A polymer p ( 3 ) ° was obtained in the same manner as in Example 1 except that 500 mmol of the compound C shown below was used as a monomer.

[化2 3]

Compound C In Figure 3, a 1 H-NMR chart of polymer P(3) is shown. Further, the number average molecular weight (?η) of the polymer P(3) in terms of polystyrene is 41,800, and the weight average molecular weight (Mw) is 83,600'.

Mw/Mn is 2.0. The results of the polymerization are shown in Table 2. The solubility of the polymer in the organic solvent is shown in Table 2. The polymer P(3) was dissolved in toluene to prepare 10 masses. /. The polymer solution. This solution was melt-cast to prepare a film F (3) having a thickness of ΙΟΟμη. The results of various physical properties of the film were shown in Table 3. [Comparative Example 1] -34- 200951148 Into a 1 L reaction vessel 'under a nitrogen atmosphere' was charged 300 mmol of compound c and 200 mmol of compound D shown below as a monomer 'filled with 522 g of toluene. As a solvent. There, polymerization was carried out by charging bis(ethyl decyl acetate) nickel 0-50 mmol and tris(pentafluorophenyl)borane 2.5 mM. The polymerization was carried out at 25 ° C for 5 hours, and the polymerization was stopped with methanol. The obtained copolymer solution was placed in 3 L of methanol, and the copolymerized product was solidified to remove unreacted monomers and catalyst residues. The solidified copolymer was dried to obtain a copolymer P ( 4 ). [Chem. 2 4]

The content of the compound D derived from the compound D in the copolymer was 61.2 mol%. The measurement was carried out by iH-NMR measurement. Further, the polystyrene-equivalent number average molecular weight (?n) of the copolymer P(4) was 99,000, and the weight average molecular weight (??) was 19.8,000,000, and the Mw/Mn system was 2.0. The results of the polymerization reaction are shown in Table 1, and the solubility of the copolymer to the organic solvent is shown in Table 2. The copolymer P(4) was dissolved in toluene to prepare a copolymer solution of 1% by mass. The solution was melt cast to form a film F (4) having a thickness of ΙΟΟμηι. The results of evaluation of various physical properties of the film are shown in Table 3 ° -35 - 200951148 [Table i] Example Comparative Example Polymer No. Conversion (%) Polymer composition (mol%) Number average molecular weight (Μη) Molecular weight Distribution (Mw/Mn) 里里十 PdyJ J里(Mw) Example 1 P(1) 56 A=100 61,100 29,100 2.1 Example 2 P(2) 40 B=100 78,3〇〇29,000 2.7 Example 3 P(3 ) 62 C=100 83,600 41,800 2.0 Comparative Example 1 P(4) 67 C/D=38.8/61.2 198,000 99,000 2.0 [Table 2]

EXAMPLES Comparative Example Polymer No. Solubility (10% by mass solution) Toluene xylene cyclohexane decane hexane dichloromethane D5 M3T M2 Example 1 P(1) 〇〇〇〇〇Δ 〇〇〇 Example 2 P ( 2) 〇〇〇〇〇〇Δ 〇〇 Example 3 P(3) 〇〇〇〇〇〇X △ 〇Comparative Example 1 P(4) 〇〇〇〇Δ 〇XXX Evaluation)〇:Dissolution, △: slightly Dissolved, X: hardly dissolved. Polyoxyalkylene solvent) D5: decamethylcyclopentaoxane, M3T: methyltris(trimethylformamoxy)decane, M2: hexamethyldioxane. EXAMPLES Comparative Example Film No. Total Light Transmittance (%T: 400 nm) Refractive Index (n25D: 589 nm) Glass Transition Temperature CC) Example 1 F(l) 90 1.44 191 Example 2 F(2) 90 1.47 213 Example 3 F(3) 89 1.54 232 Comparative Example 1 F(4) 89 1.53 301 -36- 200951148 [Industrial Applicability] Addition of a cyclic olefin functional siloxane having the present invention The polymer material has excellent optical transparency and heat resistance, and therefore has optical parts for a light guide plate, a polarizing film, a surface protective film, a retardation film, an antireflection film, a optical disk, an optical fiber, a lens, and an LED element. Electronic parts, sealants, etc. Further, the addition polymer of the cyclic olefin functional siloxane of the present invention also has excellent dissolution properties for an organic solvent and a polyoxyalkylene solvent. Therefore, application to an oxygen-rich film, a contact lens, a coating film forming material for cosmetics, and the like can be expected. [Simple description of the map]

Figure 1 is a 1 Η - N MR chart of the polymer P ( 1 ) obtained in Example 1. 2 is an ijj-NMR chart of the polymer ρ(2) obtained in Example 2.

Fig. 3 is a 1H-NMR chart of the polymer p(3) obtained in Example 3. -37-

Claims (1)

200951148 VII. Patent application scope: 1. A cyclic olefin addition polymer characterized by: addition polymerization of a cyclic olefin functional oxirane represented by the following chemical formula (1); 1】 (1) ❹ (wherein 'R1 is an integer of 0 to 2 which does not have an aliphatic unsaturated bond which is the same or different from each other', and j represents 0 or 1). 2. A cyclic olefin addition polymer characterized by addition polymerization of a cyclic olefin functional oxirane represented by the following chemical formula (2); [Chemical 2] (2) 〇 (wherein R2 is a monovalent organic group having no aliphatic or unsaturated bond which is the same or different from each other, t is an integer of 2 to 5, and k is 0 or 1). 3. A cyclic olefin addition polymer characterized by addition polymerization of a cyclic olefin functional oxirane represented by the following chemical formula (3); -38- 200951148 [Chem. 3] (3) (^«-(SiRtOU-SiR, (wherein R3 is a monovalent hydrocarbon group having no aliphatic or unsaturated bonds which are the same or different from each other, a alkyl group, and an R' system which does not have the same or phase a monovalent hydrocarbon group of an aliphatic unsaturated bond; x is a hydrazine or I; ml, m2, m3, m5, m6, m7 is 0 or 1, and m4 is an integer of 1 or more.) 4. A cyclic olefin An addition polymer characterized by addition polymerization of a cyclic olefin functional group represented by the chemical formulas (1), (2), and (3) described in the first, second, and third aspects of the patent application. a cyclic olefin addition polymer characterized by addition polymerization of a cyclic olefin compound represented by the following chemical formula (4) and selected from the scope of application of the patent. In the first, second, and third terms, at least one of the cyclic olefin functional siloxanes represented by the chemical formulas (1) and (2) '(3) is obtained from the above formula (1), (2) The ratio of the structural unit of the cyclic olefin functional oxime represented by (3) is 50 mol% or more in the copolymer; (4) (wherein, A1 to A4 are each independently selected from the group consisting of a hydrogen atom, a halogen atom, an alkyl group having a carbon number of 1 to fluorene, a cycloalkyl group, an aryl group, an alkoxy group, an aryloxy group, and a halogenated hydrocarbon group-39 a substituent of 200951148 or a polar substituent selected from the group consisting of oxetane and alkoxycarbonyl; in addition, A1 and A2 or A1 and A3 may simultaneously form an alicyclic structure with each bonded carbon atom, An aromatic ring structure, an isocyanato group or an acid anhydride group; i is a hydrazine or 1). 6. The cyclic olefin addition polymer according to any one of claims 1 to 5, which is in the form of a film, a sheet or a film. 7. A method for producing a cyclic olefin addition polymer, characterized by: a compound using a transition metal of nickel, cobalt and palladium selected from a polymerization catalyst and/or a denatured compound of the transition metal compound and a super acid, and an aluminum compound selected from the group consisting of Lewis acid, a boron compound of Lewis acid, an ionic aluminum compound, and The at least one compound of the ionic boron compound is one or more selected from the group consisting of the cyclic olefin functional siloxanes represented by the following chemical formulas (1), (2), and (3) or One or more of the cyclic olefin functional siloxanes, 50% by mole or more, and 50% by mole or less of the cyclic olefin compound represented by the following chemical formula (4); 【化5】 SiRVoSi^j) [(4) -40- 1 2 (wherein R1 does not have the same or different aliphatic unsaturated bonds, and the 3 1 organic group 's is an integer of 0 to 2, and j is a 〇 or 1) (2) 200951148 【化6】 (wherein R2 is a monovalent organic group having no aliphatic or unsaturated bond which is the same or different from each other, t is an integer of 2 to 5, and k is 0 or 1) (3) e (S) «32〇)mi-(SiR32)m2>(R0)IBj-(SiR32O)in4-(SiR32)mr(Re)in6-(SiR32O)in7-SiR,3 (wherein R3 systems do not have the same or phase a monovalent nicotyl group of an aliphatic unsaturated bond: R*5 is an alkylene group, and R is a monovalent hydrocarbon group having no aliphatic or unsaturated bonds which are the same or different from each other; X is a hydrazine or I; , m2, m3, m5, m6, m7 system or 1, m4 means an integer of 1 or more) ❹ [Chemical 8] (4) (wherein A1 to A4 are each independently substituted with a hydrogen atom, a halogen atom, a carbon number of 1 to 1 Å, a cycloalkyl group, an aryl group, an alkoxy group, an aryloxy group, and a halogenated hydrocarbon group. a substituent having a polarity selected from or selected from the group consisting of oxetane and alkoxycarbonyl; in addition, 'A1 and A2 or A1 and A3 may simultaneously form an alicyclic structure, an aromatic ring structure, and each bonded carbon atom. Isocyanate or anhydride group; i is hydrazine or 1). -41 -