WO2002014401A1

WO2002014401A1 - Process for the production of block copolymers, block copolymers produced by the process, and use of the copolymers

Info

Publication number: WO2002014401A1
Application number: PCT/JP2001/006845
Authority: WO
Inventors: Hiroshi Matsutani; Hiromasa Kawai; Haruaki Sue; Hideyasu Tsuiki; Toshihiko Takasaki; Takashi Kumaki; Tetsushi Maruyama; Shigeki Katogi
Original assignee: Hitachi Chemical Co., Ltd.
Priority date: 2000-08-11
Filing date: 2001-08-09
Publication date: 2002-02-21
Also published as: JP4239589B2; KR20030022166A; KR100544525B1; AU2001278703A1; CN1446240A; JP2009074093A; WO2002014401A8; CN1237090C

Abstract

A process for the production of block copolymers which comprises metathesis-polymerizing a metathesis-polymerizable unsaturated monocyclic compound (A) with a metathesis -polymerizable unsaturated polycyclic compound (B) by the use of a metal-carbene complex catalyst (C), wherein the metathesis polymerization is conducted by mixing the whole of the component (A) with the whole of the component (C), making the obtained mixture react, and then adding the component (B) to the resulting mixture to conduct a reaction; block copolymers produced by this process; and use of the block copolymers.

Description

Description Process for producing block copolymers, resulting block copolymers and their applications

The present invention relates to a method for producing a homogeneous block copolymer using a metathesis polymerization reaction, a block copolymer obtained by the production method, and uses of the block copolymer. The block copolymer obtained by the present invention is usefully used for adhesives for circuit connection used for electric and electronic parts such as semiconductor packages, and other uses. Background art

Using a two-component metathesis polymerization catalyst (chloride of tungsten or molybdenum and its activator), two types of metathesis polymerizable monomers having a carbon-carbon double bond are alternately added, and the block is formed. It is known to synthesize polymers (for example, Japanese Patent Application Laid-Open No. 52-501500).

There is also known an example in which a metal carbene complex of a metathesis polymerization catalyst is used to synthesize a block copolymer of metathesis polymerizable monomers having similar structures (Macrololecules Vol. 28, p. 4709, 1995, Macro lolecules, Vol. 30, p. 3137, 1997, Journal of the American Chemical Society, Vol. 118, p. 784, 1996).

In the field of electronics, the characteristics of materials used for such parts (semiconductor package materials, optical materials, etc.) are becoming ever higher with the recent technological advances in information and communications, multimedia, and personal computers. The required characteristic items that are required are, for example, adhesives for electronic materials, low-temperature adhesion, short-time adhesion, moisture resistance, embedding, film forming ability, etc. High levels must be met.

Also, each block of the block copolymer (monomer of the block source) is mixed. It is known that block copolymers with two molecular chains that do not mix (have different properties) form a microphase-separated structure and exhibit unique properties. As an example, styrene-butadiene-styrene block copolymer (SBS resin) has microphase separation consisting of rigid molecular chains (hard segments) derived from polystyrene and flexible molecular chains (soft segments) derived from polybutadiene. It is a block copolymer that forms a structure. This SBS resin is one of the thermoplastic resins in which the hard segment acts as a cross-linking point at room temperature and the soft segment acts as a rubber component. (Polymer Society of Japan, Polymer Data Handbook Application, Baifukan, 1980) 6, p. 299-307). ,

An example of a polyethylene-polyethylene glycol block copolymer is a nonionic high molecular surfactant having a nonpolar molecular chain and a polar molecular chain, which is used as an anti-foaming agent or an antifoaming agent. (Refer to Sigma-Aldrich's home page and CAS Registry Number: 979953—22—5).

The method disclosed in the above-mentioned Japanese Patent Application Laid-Open No. 52-150500 has problems in handling such as instability of the catalyst after mixing the two components against air and moisture and necessity of a dry nitrogen atmosphere. There are also restrictions on the functional groups of the raw material monomers that can be used and the choice of solvents. In addition, starting monomers (or solvents) having a functional group with high proton releasing ability, formyl group, ketone group or ester group induce a termination reaction and become a catalyst poison and cannot be used in this reaction system. Ed., “Synthesis and Reaction of Polymer (1)”, p. 393 (Kyoritsu Shuppan, published in 1990)).

In the synthesis of block copolymers using metal carbene derivatives, examples of synthesis using two types of monomers having similar structures are known, but block copolymers using two types of monomers having greatly different structures are known. The production method of the union is not yet known.

If a block copolymer can be obtained from two types of metathesis-polymerizable monomers that have significantly different structures and / or polarities from each other, the block copolymer will have the ability to form a microphase-separated structure. It is expected that the polymer region consisting of a molecular chain having a molecular weight will promote adhesion to metal. In addition, a polymer region composed of a non-polar molecular chain such as a polyalkylene chain acts as an elastomer, and the polymer itself Can be expected to lower elasticity and contribute to strengthening of adhesive strength.

Furthermore, by changing the types of the two raw materials in various ways, it is expected that various physical properties such as low water absorption, low dielectric constant, low elasticity, and transparency of the block copolymer can be further improved. Furthermore, it is expected that the physical properties of the monomer can be finely controlled by changing the amount of the raw material monomer. Disclosure of the invention

An object of the present invention is to provide a production method capable of easily synthesizing a homogeneous block copolymer even when two types of metathesis polymerizable monomers having greatly different structures and / or polarities are used as raw materials. Still another object of the present invention is to use the obtained block copolymer as an adhesive for circuit connection of electric and electronic components such as semiconductor packages.

The present inventors have proposed that when a stable and highly active ruthenium carbene complex catalyst is used to carry out a copolymerization reaction between a norbornene derivative as a raw material for synthesis and a cycloalkene, a cycloalkene and a necessary ruthenium carbene are first used. It was found that a desired homogeneous block copolymer could be stably obtained by reacting the entire amount of the catalyst complex catalyst and then adding a norpolenene derivative, and the following invention was completed using this as a starting point. Reached.

The present invention provides a metathesis polymerization reaction between a metathesis-polymerizable unsaturated monocyclic compound (A) and a metathesis-polymerizable unsaturated polycyclic compound (B) using a metal carbene complex catalyst (C). At this time, first, the unsaturated monocyclic compound (A) and the required amount of the metal carbene complex catalyst (C) are mixed and reacted, and then the unsaturated polycyclic compound (B) is added and reacted. This is a method for producing a copolymer.

At this time, after the above reaction, a polymerization terminator is further added to stop the polymerization reaction, and the catalytically active site derived from the catalyst (C) bonded to one end of the polymer is removed, and the center of the catalyst (C) is removed. It is preferable to remove halogen atoms and the like coordinated to the metal.

The present invention also relates to a block copolymer produced by the above production method. One type of block copolymer produced is the block of the copolymer. —The other block consists of a molecular chain (mA; —AAA—AAA—; block A) in which m molecular species (A) having an unsubstituted or substituted methylene group in the main chain are linked in a chain. The molecular species (B) having a cyclocyclic structure in the main chain is composed of n molecular chains (nB; —BBB—BBB—; block B), and at one end of the copolymer molecule, It is a block copolymer in which residues other than the catalytically active site derived from the metal carbene complex catalyst (C) are bonded.

Another type of block copolymer to be produced is a copolymer in which the other end of the copolymer molecule further has a catalytically active site derived from the metal carbene complex catalyst (C) bonded thereto.

In the production method of the present invention, when a polymerization reaction terminator capable of terminating the polymerization reaction and removing the catalytically active site of the catalyst (C) is used, a block of the former type is used. Give a copolymer.

In the above production method, before adding a reaction terminator or without adding a reaction terminator, or a reaction terminator that terminates the polymerization reaction but cannot remove the catalytically active site derived from the catalyst (C) bonded to one end of the polymer In the case of using, the latter type of copolymer is used.

The degree of dispersion of the molecular weight distribution of the above block copolymer is usually from 1.0 to 2.5, preferably from 1.0 to 2.0. Here, the degree of dispersion of the molecular weight distribution is a value calculated by the ratio (Mw / Mn) between the weight average molecular weight (Mw) and the number average molecular weight (Mn).

Further, with respect to any of the above block copolymers, it is preferable that one block of the block copolymer has a molecular species (A) having a methylene group substituted or unsubstituted with a nonpolar group in its main chain. The other block consists of a m-chain nonpolar and flexible molecular chain (mA), and the other block contains a cyclocyclic structure in the main chain and a molecular species (B) having a polar substituent on the cyclocyclic ring. It is a block copolymer composed of polar and rigid molecular chains (nB) linked in n chains.

In addition, the present invention provides a nonpolar and flexible molecular chain (mA) in which a molecular species (A) having a methylene group substituted or unsubstituted with a nonpolar group in the main chain is connected in m chains. The main chain contains any of cycloalkane derivatives, cycloalkene derivatives, oxacycloalkane derivatives, oxacycloalkene derivatives, thiacycloalkane derivatives, and thiacycloalkene derivatives, and a polar substituent on the cyclo ring. And a polar and rigid molecular chain (n B) in which n molecular species (B) having the following structure are linked in a chain.

Furthermore, the present invention relates to an adhesive for circuit connection containing the block copolymer. BRIEF DESCRIPTION OF THE FIGURES

FIG. 1 is a GPC chromatogram of the polymer obtained in Example 1 and the polymer obtained in Comparative Example.

FIG. 2 is a ¹ H-NMR spectrum of the polymer obtained in Example 1. BEST MODE FOR CARRYING OUT THE INVENTION

First, a method for producing a block copolymer will be described. The manufacturing method usually comprises the following step (i) and step (ii).

Step (i): Metathesis-polymerizable unsaturated monocyclic compound (A; monomer A; also referred to as molecular species A) and the total amount of the required amount of metal carbene complex catalyst (C; also referred to as catalyst) are added and mixed. Then, ring-opening metathesis polymerization is performed. A molecular chain having a catalytically active site (Cata) derived from a metal carbene complex catalyst at the end (ie, Cata-AAA—A

AA-lyst). Here, Cata means a metal-containing site derived from the metal carbene complex catalyst and lyst means its residue.

Step (ii): Subsequently, a metathesis-polymerizable unsaturated polycyclic compound (B; monomer B; also referred to as ^ "species B) is added to the reaction system and mixed.

From the catalytically active site (Cata) end of (Cata-AAA to AAA), the diblock having a catalytically active site (Cata) at the end, with the BBB to BBB chain extending to incorporate monomer B sequentially. Polymer (Cata-BBB…: BBB-AAA-AAA-lyst) is produced. Even if monomer B and the entire amount of catalyst (C) are added, mixed and reacted, and then monomer A is added and reacted, a homogeneous diblock copolymer is not formed. Also, even if the jib mouth copolymer represented by Cata-AAA to AAA-BBB ...: BBB-lyst is partially formed, the yield or yield is low.

The reason that such a diblock copolymer (Cata-BBB ... BBB—AAA to AAA-lyst) can be synthesized with high yield by the production method of the present invention is that polymerization of monomer A promoted by catalyst (C) is started. The reaction rate is higher than the polymerization elongation reaction rate, so that the majority of the product in step (i) is 0 & 88-88-8-3 and remains as a single catalyst (C). It is estimated that there is not.

On the other hand, since the polymerization elongation reaction rate of monomer B promoted by catalyst (C) is higher than the polymerization initiation reaction rate, the reverse order, ie, when monomer B and the total amount of catalyst (C) are added first, the process In (i), Cata-BBB ••• BBB-lyst is formed while leaving unreacted catalyst (C). The remaining catalyst (C) is used in the next step

Cata-AAA ~ AAA-lyst is formed as a reaction catalyst in (ii), reducing the yield of diblock copolymer (Cata-AAA-AAA-BBB-BBB-lyst), and the product is heterogeneous It is considered that the polymer becomes

After step (ii), if monomer A is further added to the reaction system, the monomer is sequentially added from the catalytically active site of the diblock copolymer (Cata-BBB to BBB-AAA-AAA-lyst). A can be incorporated to form a triblock copolymer (Cata-AA8… AA—BBB…: BBB—AAA to AAA-lyst). Following the above step (ii), preferably, a step (step (iii)) of adding a reaction terminator to terminate the metathesis polymerization reaction is added.

Examples of the reaction terminator include those that stop the metathesis polymerization reaction and also remove the catalytically active site derived from the catalyst (C) bonded to one end of the polymer. For example, a double bond at the molecular end and electron withdrawing at the adjacent position Vinyl acetate, ethyl vinyl ether, phenyl vinyl sulfide, N-vinyl pyrrolidone, and other vinyl sulfide compounds having a functional group; coordinating compounds having a large electron donating ability, such as 4-vinyl pyridine; and exo methylene compounds. is there. Among these, vinyl acetate and ethyl Vinyl ethers are preferably used. In addition, imidazole, 2,2, -bipyridine, 4-methylpyridine and the like that stop the metathesis polymerization reaction but do not remove the catalytically active site derived from the catalyst (C) bonded to one end of the polymer are included. Hereinafter, the monomer A, the monomer B, and the catalyst (C) used in the present invention will be described in order. Examples of the unsaturated monocyclic compound (monomer A) used in the present invention include compounds that can undergo ring-opening metathesis polymerization and give a polymer having no ring structure after ring-opening polymerization. Preferably, a substituted or unsubstituted cycloalkene derivative having a carbon-carbon double bond in the molecule is used.

The elements constituting the cyclo ring of the cycloalkene derivative are usually 3 to 14 carbon atoms, preferably 4 to 9 carbon atoms, and some of the carbon atoms are a silicon atom or a boron atom. May be replaced by An oxygen atom, a sulfur atom, a nitrogen atom or a phosphorus atom may be used instead of some of the carbon atoms constituting the cyclo ring. In this case, the molecular chain mA (block A) shows polarity.

The substituent Y ² in the case where there is a substituent on the cycloalkyl ring, but like an alkyl group or a halogen atom carbon atoms 1-2 0, is preferably an alkyl group of from 1 to 2 0 carbon atoms .

In addition to the above substituents, carboxy, cyano, isocyano, nitro, siloxy, alkoxycarbonyl having 2 to 20 carbon atoms, alkylcarbonyl having 2 to 20 carbon atoms Hydroxy, amino, amide, formyl, hydroxyl, hydroxyalkyl having 1 to 20 carbon atoms, alkoxyalkyl having 2 to 20 carbons, acyloxy having 3 to 20 carbons Alkyl group, cyanoalkyl group having 2 to 20 carbon atoms, alkoxy group having 1 to 20 carbon atoms, alkylthio group having 1 to 20 carbon atoms, alkylsulfinyl group having 1 to 20 carbon atoms, carbon Alkyl sulfonyl groups having 1 to 20 atoms, alkyl sereno groups having 1 to 20 carbon atoms, alkyl seleninyl groups having 6 to 20 carbon atoms, and alkyl selenonyl groups having 1 to 20 carbon atoms, etc. is there. In this case, the molecular chain mA (block A) shows polarity.

Specific examples of the cycloalkene derivative used in the present invention include, for example, Cyclobutene, cyclopentene, cyclooctene, cyclododecene, 5-methoxy-1-cyclooctene, 5-promo-1-cyclooctene, 5-isopropoxy_1-cyclooctene, 5-formyl1-1-cyclooctene, ethyl crooctone-1-5 —Carboxylate, trimethylsilyl = cyclooctene-5-carboxylate and the like; and cyclopentenes and / or cyclopentene is preferably used. In addition, unsaturated monocyclic compounds having two or more double bonds can also be used. _C Such unsaturated monocyclic compounds include, for example, 1,5-cyclooctadiene, 1,3,5,7 —Cyclooctatetraene, 1,5,7—cyclododecatriene and the like.

Examples of the unsaturated polycyclic compound (B) used in the present invention include a compound which is capable of metathesis polymerization and gives a polymer having a ring structure in the main chain after ring-opening polymerization. One of the preferable examples is a substituted or unsubstituted norbornene derivative, for example, a compound represented by the following formula (III).

In the formula (III), m represents an integer of 0 to 3, preferably 0 to 2, more preferably 0 or 1.

R ^{5 to} R ⁸ are each independently a hydrogen atom, the number of carbon atoms; To 20 alkyl groups, cycloalkyl groups having 3 to 20 carbon atoms, aryl groups having 6 to 20 carbon atoms, halogen atoms, carbonyl groups, cyano groups, isocyano groups, nitro groups, siloxy groups, carbon atoms Alkoxycarbonyl group having 2 to 20 carbon atoms, alkylcarbonyloxy group having 2 to 20 carbon atoms, amino group, amide group, formyl group, hydroxyl group, hydroxyalkyl group having 1 to 20 carbon atoms, carbon Alkoxyalkyl group having 2 to 20 atoms, acyloxyalkyl group having 3 to 20 carbon atoms, cyanoalkyl group having 2 to 20 carbon atoms, alkoxy group having 1 to 20 carbon atoms, 1 carbon atom ~ 2 0 alkylthio group, 1 to 20 carbon atom alkylsulfinyl group, 1 to 20 carbon atom alkylsulfonyl group, 1 to 20 carbon atom alkylseleno group, 1 to 20 carbon atom alkylseleninyl group And an alkyl selenonyl group having 1 to 20 carbon atoms, at least one of which is a hydrogen atom. Among them, a hydrogen atom, an alkyl group having 1 to 10 carbon atoms, a carbon atom, an alkyl group having 3 to 12 carbon atoms, an aryl group having 6 to 12 carbon atoms, a halogen atom, a carbonyl group, It is preferably selected from a cyano group, a nitro group, a siloxy group, an alkoxycarbonyl group having 2 to 10 carbon atoms, an amide group, a formyl group, and a hydroxyl group. It is more preferable that the alkoxy group is selected from the group consisting of an alkoxy group and an amide group.

In addition, one or two of R ⁵ to R ⁸ are bonded to one or two groups to form one CO—0—CO— group (acid anhydride), one CO—0_ group (lactone), _CO—NR ⁹ —CO —Group (imide) and —CO—NR ⁹ —group (lactam). Here, R ⁹ is selected from a hydrogen atom, an alkyl group having 1 to 4 carbon atoms, a cycloalkyl group having 3 to 6 carbon atoms, and an aryl group having 6 to 20 carbon atoms. Among them, one CO—0—CO— group (acid anhydride) or one CO—NR ⁹ —CO— group (imide) is preferable. In the case of imid, R ⁹ is a hydrogen atom, and has 1 to 4 carbon atoms. An alkyl group or an aryl group having 6 to 12 carbon atoms is preferable, and an alkyl group having 1 to 4 carbon atoms is more preferable.

X ⁵ and X ⁶ are each independently selected from an oxygen atom, a sulfur atom and C (R ¹⁰ ) ₂ . The two R ^{1Q s} may be the same or different, and each represents a hydrogen atom, a halogen atom, an alkyl group having 1 to 4 carbon atoms, a cycloalkyl group having 3 to 6 carbon atoms, and 6 to 20 carbon atoms. From the group of Ariel. Two R ^1Qs may combine to form a 3- to 8-membered ring structure, or may form a spiro ring. When R ^1D is other than a hydrogen atom or a halogen atom, it may be substituted with any of an alkyl group having 1 to 3 carbon atoms, a halogen atom, a cyano group, a carboxyl group, an amino group and an amide group. Among them, an oxygen atom or C (R ¹⁰ ) ₂ is preferable, and R ^1G is a hydrogen atom, an alkyl group having 1 to 4 carbon atoms or a carbon atom. A cycloalkyl group having 3 to 6 atoms is preferred, and a hydrogen atom or a methyl group is more preferred. X ⁵ and X ⁶ are preferably the same.

Specific compounds represented by the formula (III) include, for example, norbornene, methylnorbornene, dimethylnorbornene, ethylnorportene, ethylidenenorbornene, butylnorbornene, 5-acetyl_2-norporene, N-hydroxyl 5-Norbornene-2,3-dicarboximid, 5-Norpolene-12-forced nitrile, 5-Norbornene-12-forced aldehyde, 5-norbornene-1,2,3-dicarboxylic acid monomethyl ester, 5-Norpolonene 1,2-dicarboxylic acid dimethyl ester, 5-norbornene-1,2,3-dicarboxylic acid getyl ester, 5-norbornene-1,2,3-dicarbonic acid di-n-butyl ester, 5-norbornene-2,3-dicarboxylic acid Acid dicyclohexyl ester, 5-norbornene-1,2,3-dicarboxylic acid dibe Benzyl ester, 5-norporene-2,3-dicarboxylic anhydride, 5-norbornene-1,2,3-dicarboxylic acid, 5-norbornene-2-methanol, 5-norbornene-2,3-dimethanol, 2,3-bis (methoxymethyl 1) 5-norbornene, N-methyl-5-norpolene-2,3-carboxyimid, 6-triethoxysilyl-12-norbornene, 5-norporen-12-ol, etc., bicyclic norpolene, dicyclopentadiene (cyclopentadiene) Tricyclic norbornene such as dihydrodisocyane, tetracyclic norbornene such as tetracyclododecene, methyltetracyclododecene and dimethylcyclotetradodecene; tricyclopentagene (trimer of cyclopentadiene); Tetracyclopentadiene (tetramer of cyclopentadiene Pentacyclic or more norbornene etc., tetracyclododecanyl Zhen, such compounds that have a two or more norbornene groups, such as symmetric tri cyclopentadiene.

Among them, 5-methyl-norbornene-1,2,3-dicarboxylic acid monomethyl ester, which has a polar group and is not highly reactive, 5-norbornene-2,3-dicarboxylic acid methyl ester, 5-norbornene-1,2,3-dicarboxylic acid Acid acetyl ester, 5-Norbornene-2,3-dicarboxylic acid dicyclohexyl ester and 5-nornorpene-1,2,3-dicarponic acid dibenzyl ester are preferable, 5-norbornene_2,3-dicarponic acid dimethyl ester, 5-norbornene-2,3 —Getyl dicarboxylate and dicyclohexyl 5-norbornene-1,2,3-dicarboxylate are more preferred.

In addition, 7-oxabicyclo [2.2.1] hepter-5-one-1,2,3-dicarboxylic anhydride, 7-oxabicyclo [2.2.1.2.1] hepta-5-one-1,2,3 —Dicarboxylic acid, 2-carboxy-13-methoxycarbonyl-17-oxabicyclo [2.2.1] hept-1-5-ene, 2,3-dimethoxycarbonyl—7-oxabicyclo [2.2.1] ] Hepta-5-ene, 2,3-diethoxypropanol-1 7-oxabicyclo [2.2.1] Hepter 5-ene, 2,3-dihexyloxycarbonyl-17-oxabicyclo [2.2] 1] Hepta-5-ene, 2,3-dibenzyloxycarpinoru 7-oxabicyclo [2.2.1] Hepta_5_ene, 2,3-bis (hydroxymethyl) -17 Oxabicyclo [2.2.1] hepta-1-ene, 2,3_bis (methoxymethyl) -7-oxabicyclo [2.2.1] hepta-1-ene, N-methyl-1-oxabicyclo [2.2.1] hepta-5-ene-2,3-carboxyimide, 7-thiabicyclo [2.2.1] hepta-5-ene-2,3-dicarboxylic anhydride , 2-Felpoxy_3 -Methoxycarbonyl-1 7-thiabicyclo [2.2.1] hepter 5-ene, 2,3-Dimethoxycarbonyl-1 7-thiasabicyclo [2.2.1] Hepta-5 , 2,3-bis (hydroxymethyl) -17-thiabicyclo [2.2.1] hepta-15-ene, and the like can also be exemplified as specific compounds of the formula (III).

In addition, 2,3-bis (methoxycarbonyl) bicyclo [2.2.1] hepta2,5-gen, 2,3-bis (methoxycarbonyl) 17-oxapisik [2.2.1] Compounds containing two (or more) double bonds, such as hepter 2,5-gen, 2,3-bis (methoxycarbol) _7-thiabicyclo [2.2.1] hepta-1,2,5-gen Is also used. When the compound represented by the formula (III) is used as a monomer, a carbon-carbon double bond represented by the following formula (Ilia) is present in the molecular chain opened by the metathesis polymerization reaction.

In the formula, m, R ^{5 to} R ⁸ , X ⁵ and X ⁶ have the same meanings as in formula (III). The amount of each of the unsaturated monocyclic compound (A) and the unsaturated polycyclic conjugate (B) may be determined according to the intended block copolymer. At this time, it is considered that a block copolymer having a composition ratio (A / B) substantially equal to the molar ratio of the unsaturated monocyclic compound (A) and the unsaturated polycyclic compound (B) used is obtained.

The metal carbene complex catalyst (C) used in the present invention is a catalyst that catalyzes a metathesis polymerization reaction using an unsaturated monocyclic compound (A) and an unsaturated polycyclic compound (B) as raw materials. I just need. Preferred are compounds represented by the following formula (I) or (II). These compounds, along with a stable to oxygen and moisture, therefore _c is excellent in copolymerization of two monomers with each other with different properties, the polymerization reaction is carried out in an inert gas atmosphere, as well as possible in the air is there. The metal carbene complex catalyst (C) may be used alone or in combination of two or more.

In the formulas (I) and (II), M is ruthenium, osmium or iron, preferably The other is ruthenium.

X ^{1 to} X ⁴ are anionic ligands (atoms or atomic groups) capable of coordinating to the central metal M and having a negative charge on the coordinating atom, for example, a hydrogen atom, a fluorine atom, a chlorine atom , a bromine atom, a halogen atom such as iodine _{_{atom, CF 3 C0 2 _, CH}} 3 C0 2 -, CF 2 HC0 2 _, CFH 2 C0 2 -, (CH 3) 3 CO -, (CF 3) 2 (CH ₃ ) CO—, (CF ₃ ) (CH ₃ ) ₂ CO_, a linear or branched alkoxy group having 1 to 5 carbon atoms, a substituted or unsubstituted phenoxy group, a trifluoromethanesulfonate group, and the like. Of these, a halogen atom is preferred, and a chlorine atom is more preferred. More preferably, X ¹ and X ² and X ³ and X ⁴ are all halogen atoms (such as chlorine atoms).

L ¹ ~ L ⁴ represents an electron donating group capable of coordinating neutral to the central metal M, for example, in p _{_{_R}} ll _R 12 _R 13 (wherein, R "to R" are each independently a substituted or An unsubstituted aryl group having 6 to 20 carbon atoms, a linear or branched alkyl group having 1 to 10 carbon atoms and a cycloalkyl group having 3 to 10 carbon atoms). Imidazole compounds such as substituted pyridine and 1,3-disubstituted imidazole; In particular, phosphines such as tricyclohexylphosphine, tricyclopentylphosphine, and triisopropylphosphine;

Preferred are imidazole compounds such as 1,3-dimesitylimidazole-2-ylidene and 4,5-dihydro-1,3dimesitylimidazole-2-iriten, and more preferred is tricyclohexylphosphine.

Is independently a hydrogen atom, an alkyl group having 1 to 20 carbon atoms, an alkenyl group having 2 to 20 carbon atoms, an alkynyl group having 2 to 20 carbon atoms, an aryl group having 6 to 20 carbon atoms. A carboxylate group having 1 to 20 carbon atoms, an alkoxy group having 1 to 20 carbon atoms, an alkenyloxy group having 2 to 20 carbon atoms, an aryloxy group having 6 to 20 carbon atoms, and 2 to 20 carbon atoms Alkoxycarbonyl group, alkylthio group having 1 to 20 carbon atoms, alkylsulfonyl group having 1 to 20 carbon atoms, alkylsulfinyl group having 1 to 20 carbon atoms, alkylseleno group having 1 to 20 carbon atoms Alkyl selenis having 1 to 20 carbon atoms Selected from an alkyl group having 1 to 20 carbon atoms, an alkyl group having 1 to 5 carbon atoms, a halogen atom, an alkoxy group having 1 to 5 carbon atoms or a carbon atom. The aryl group may be substituted with an aryl group having a number of 6 to 20, and the aryl group may be substituted with a halogen atom, an alkyl group having 1 to 5 carbon atoms, or an alkoxy group having 1 to 5 carbon atoms. Is also good.

Specific conjugates represented by the above formula (I) or (II) include, for example, compounds represented by the following formulas (V) to (XIV), among which the formulas (V) and (VI) ), (VII) or (VIII) are preferably used.

The amount of the metal carbene complex catalyst (C) used is determined in consideration of the desired molecular weight of the block copolymer. The higher the amount used, the lower the molecular weight of the block copolymer. Usually, 0.001 to 20 parts by weight, preferably 0.001 to: 10 parts by weight, more preferably 100 parts by weight based on 100 parts by weight of the total of the unsaturated monocyclic compound (A) and the unsaturated polycyclic compound (B). Is 0.05-; L 0 parts by weight.

In the polymerization reaction of the present invention, first, the entire amount of the unsaturated monocyclic compound (A) and the required metal carbene complex catalyst (C) are mixed and reacted, and thereafter, the unsaturated polycyclic compound ( General polymerization reaction conditions can be used, except for adding and reacting B).

The reaction time of the polymerization reaction is not particularly limited as long as a block copolymer can be obtained. In step (i), the reaction time is 10 minutes to 6 hours, preferably 0.5 to 2 hours. In step (ii), the reaction time is preferably 1 to 6 hours after the reaction of (i). Let react for 2-6 hours.

The reaction temperature of the polymerization reaction is not particularly limited as long as a block copolymer is obtained, and is preferably from _20 to 200 ° C, more preferably from 0 to 100 ° C, from the viewpoint of reactivity. In the polymerization reaction, it is preferable to use a solvent. The solvent used in the present invention includes an unsaturated monocyclic compound (A), an unsaturated polycyclic compound (B), and a catalyst.

There is no particular limitation as long as (C) can be dissolved. Examples of such a solvent include ketone solvents such as acetone, 2-butanone, 2-pentanone, 3-pentanone, 4-methyl-3-pentanone, cyclopentanone, cyclohexanone, cycloheptanone, and cyclooctanone. And ether solvents such as dimethyl ether, methyl tert-butyl ether, tetrahydrofuran, 1,4-dioxane and ethylene glycol dimethyl ether.

When a solvent is used, the amount of the solvent is preferably 60 to 95% by weight based on the entire reaction system (the total amount of the monomers A and B, the catalyst and the solvent), from the viewpoint of easiness of the polymerization reaction. It is more preferably 70 to 90% by weight, particularly preferably 80 to 90% by weight. If the catalyst (C) is dissolved in a solvent and left for a long time, the decomposition reaction proceeds little by little. After dissolving the unsaturated monocyclic compound (A) in the solvent, the (powder-like) catalyst (C) Or a catalyst solution dissolved in the same solvent (small amount) as the solvent used for dissolving the monocyclic compound (A).

In the copolymer synthesized through step (i), step (ii), and further step (iii), a carbon-carbon double bond still exists. In order to avoid aging due to this double bond (degradation due to oxidation, cross-linking reaction with other molecules, etc.), the obtained copolymer is further hydrogenated and remains in the polymer molecule. Preferably, the unsaturated bond is saturated.

The hydrogenation reaction can be performed using a known method such as a catalytic reduction method using a known metal catalyst 触媒 a hydrazine reduction method.

The block copolymer obtained by the above-mentioned production method can be obtained by selecting the starting monomer, and then selecting a non-polar, non-polar or m-type molecular species (A) having a methylene group substituted in the main chain. And flexible molecular chains (mA, ie —AA A-AA A-) and any of cycloalkane derivatives, cycloalkene derivatives, oxacycloalkyne derivatives, oxacycloalkene derivatives, thiacycloalkane derivatives or thiacycloalkene derivatives In the main chain, the cyclic ring structure of A block copolymer comprising a polar and rigid molecular chain (nB, ie, one BBB-BBB-) in which n molecular species (B) having a polar substituent on the top are connected in a chain form is obtained. A block copolymer having homogeneity with a molecular weight distribution of the polymer of 1.0 to 2.5 can be obtained. These also include modified block copolymers, that is, block copolymers (triblock copolymers) such as molecular chain mA—molecular chain nB—molecular chain mA.

The number of repetitions m of the molecular species (A) of such a block copolymer (diblock copolymer) and the number of repetitions n of the molecular species (B) are basically based on the raw materials (monomer A, Determined by the amount of NOMA B and catalyst C) used. The number of repetitions m and n is usually between 5 and 5000, preferably between 10 and 1000, respectively. If it is less than 5, it is difficult to exhibit the properties of the molecular chain mA and the molecular chain nB, that is, the flexibility (soft segment) of the molecular chain mA and the rigidity (hard segment) of the molecular chain nB, respectively. It is also difficult to exert the polarity of the molecular chain mA and the non-polarity of the molecular chain nB. On the other hand, if it exceeds 5000, the synthesis reaction takes time. The ratio of the number of repetitions m and n (m / n) is a number balanced with each other, and is usually 95 to 5/95, preferably 90 to 10/90.

For the polarity of each of the molecular chain mA and molecular chain nB, the raw material monomer can be selected based on the organic conceptual diagram. Organic conceptual maps are an effective method for predicting various physical properties from the chemical structure of organic compounds (see Yoshio Koda, Organic Conceptual Diagrams: Basics and Applications, Sankyo Publishing (1984)). In other words, an organic conceptual diagram divides the properties of a compound into “organic value indicating covalent bonding” and “inorganic value indicating ionic bonding”, and all the organic compounds are regarded as an organic axis. It is shown as one point on the Cartesian coordinate system called the axis. The organic value based on this is based on the assumption that the numerical value of the organic value can be measured by the number of carbon atoms representing the methylene group in the molecule as a unit, and the basic carbon number is 1 The numerical value is based on the average value of 20 ° C of the increase in boiling point due to the addition of one carbon atom near the carbon number of 5 to 10 in the linear compound, and is set to 20 based on this. On the other hand, inorganic values The magnitude of the influence of the substituents on the boiling point is determined based on the hydroxyl group, and the difference between the boiling point curve of the linear alcohol and the boiling point curve of the normal paraffin near the carbon number of 5 is about 100 ° C. Therefore, the influence of one hydroxyl group is set to 100 numerically. Based on this, the influence of other functional groups is determined as a value proportional to this. These inorganic values and organic values are set to correspond one-to-one on the graph. The inorganic value and the organic value of the organic compound are calculated from these values. Organic compounds with high inorganic values have high polarity, and organic compounds with high organic values have low polarity.

When the organic conceptual diagram is used as a guide, the ratio of inorganic to organic of the molecular species (A) in the present invention (inorganic Z organic) is usually 0 to 0.3, preferably 0 to 0.3. 25. When the molecular species (A) is methylene, the ratio of inorganicity to organicity is 0, which means that the polymethylene chain of the molecular chain mA has nonpolar and flexible properties.

In the molecular chain (nB), the polar substituent on the cyclo ring can be selected using the “substituent constant based on the polar group effect” and I, which are separated from the Hammett's substituent constant and the substituent constant. (See M. Chart 0 n, Prog. Phys. Org. Chem., 13, 119-251 (1981)). The values of I and I are larger as the polarity of the substituent is higher, with the hydrogen atom being 0. The polar substituent I on the cyclo ring in the molecular chain (nB) is usually from +0.05 to +0.80, preferably from +0.10 to +0.80.

The ratio of the inorganicity to the organicity of the molecular species (B) in the organic conceptual diagram is usually 0.4 to 10.0, and preferably 0.45 to 7.5.

The obtained block copolymer may be used in the following manner: a curable binder and a curing agent are added thereto, and if necessary, a base resin and other additives are added in an appropriate amount. can do. The adhesive can be in various forms depending on the application, for example, a film, a sheet, a tape, a liquid, a paste, and the like. When the adhesive for circuit connection is prepared, the compounding ratio of each is 100 parts by weight of the curable compound and about 1 to about 100 parts by weight of the curing agent. When the copolymer is used, the amount may be more than 100 parts by weight), and the amount of the block copolymer is about 5 to about 500 parts by weight.

i) Curable compound

The curable compound is a substance having a functional group that can be polymerized by a curing agent (described below), and may be a monomer or an oligomer. Specific examples include an ionically polymerizable epoxy compound and a radically polymerizable acrylate compound / methacrylate compound.

i i) Curing agent

A curing agent is a compound that initiates the polymerization of the curable compound described above. Usually, a curing agent is used which generates polymerization active species by heating or irradiation with energy yarn. Examples of such a curing agent include radicals generated by heating an imidazole derivative having a latent potential (a microcapsule), an ionic polymerizable monomer such as a sulfonium salt, an organic peroxide, or an azoid compound. Radical polymerizable monomers.

i i i) Base resin

As the base resin, a resin having high film forming ability, excellent stress relaxation at the time of hardening, and high adhesion can be used. Examples of such a resin include a phenoxy resin having a hydroxyl group in the molecule and having a molecular weight of 100,000 or more.

iv) Other additives

Conductive particles can be added and dispersed in order to absorb the height and variations of the circuit electrodes and to positively impart anisotropic conductivity. Further, for the purpose of improving connection reliability and the like, a coupling agent, a filler, an antioxidant, and the like can be added. Example

Example 1 (A / B of charged monomer = 50 Z50 (molar ratio), solvent used: cyclohexanone)

In a 100 ml glass flask, 0.791 g (7.13 mmo 1) of cyclooctene as monomer A is dissolved in 8 ml of cyclohexanone and heated to 60, and then the ruthenium carbabe of the formula (V) is dissolved. 39.2 mg (0.048 mmo 1) was added to the mixture, and the mixture was reacted at 60 ° C. for 1 hour while stirring with a mechanical stirrer (step (i)). During the reaction, a small amount of the reaction solution was withdrawn from the reaction system, vinyl acetate was added thereto, and the reaction was stopped to obtain a sample for GPC measurement.

Thereafter, 1.50 g (7.13 mmo 1) of endo-5-norpolenene-2,3-dimethylester (endo-DME, manufactured by Lancaster) as monomer B was added, and the mixture was further reacted for 2 hours. (Step (ii)). During the reaction, a small amount of the reaction solution was withdrawn from the reaction system, and the reaction was stopped by adding vinyl acetate.

Thereafter, 0.55 ml (6. Ommo 1) of butyl acetate and 6 ml of cyclohexanone were added and reacted for 5 minutes (step (iii)), and the cooled reaction solution was added to 200 ml of methanol. And a white precipitate (polymer) was obtained at a yield of 63%.

The obtained polymer is dissolved in tetrahydrofuran (manufactured by Wako Pure Chemical Industries, HPLC), When the molecular weight was measured by GPC using tetrahydrofuran as an eluent, the number average molecular weight Mn was 74,000, the weight average molecular weight Mw was 143,000, and the polydispersity of the molecular weight distribution was 1.93 in terms of standard polystyrene. Was. GPC was measured using a GL-A150 column (Hitachi Kasei gel pack, exclusion limit 5 × 10 ⁵ ) at a flow rate of lcm ³ Z and a column temperature of 40 ° C. The GPC chromatogram is shown in FIG.

The obtained polymer was used as a double-mouthed form solution, and the iH-NMR spectrum was measured. The results are shown in FIG.

From the ratio of the integrated value and endo- integral value of methyl hydrogens main butoxy group portion DME was opened methylene hydrogen H ^a where Shikurookuten occurs by ring-opening, the respective raw materials Ingredient molar ratio in the polymer As a result of calculation, the molar ratio of cyclooctene / endo-DME was 52/48.

In addition, the inorganic Z organic value in the organic conceptual diagram of the cyclooctene ring-opening polymer chain in the poly (cyclooctene) monoblock-poly (endo-5-norpolenene_2,3-dicarboxylate) of the obtained polymer is It is calculated to be 0.01, and the substituent constant and I based on the polar group effect of the methoxycarbonyl group on the cyclohexane ring are +0.32.

Example 2 (A / B of charged monomer = 20 to 80 (molar ratio))

Conducted except that the amount of cyclooctene used was 0.319 g (2.85 mmo 1) and the amount of endo-5-norpolonene 1,2,3-dimethyl ester was 2.41 g (11.4 mmo 1) A polymer was obtained in the same manner as in Example 1. The yield was 82%, Mr i 52,000, Mw was 105,560, and the polydispersity of the molecular weight distribution was 2.03. The molar ratio of each raw material component was calculated in the same manner as in Example 1. As a result, the molar ratio of cyclooctene / endo-DME in the polymer was 18 Z 82.

Example 3 (A / B of charged monomer = 80Z20 (molar ratio))

Example except that the amount of cyclooctene used was 1.257 g (11.4 mmol) and the amount of endo-5-norportene 1,2,3-dimethyl ester was 0.60 g (2.85 mmol). In the same manner as in 1, a polymer was obtained. 86% yield, Mn in standard polystyrene conversion was 60,700, Mw was 105,618, and the degree of molecular weight distribution was 1.74. The molar ratio of each raw material component was calculated in the same manner as in Example 1. As a result, the molar ratio of cyclooctene Zendo-DME was 81/19. Comparative Example 1

Endo-5-norporene-1,2,3-dimethylester as monomer B (endo-DME, manufactured by Lancaster) in a 100-ml glass flask with 1.50 g (7.13 mmo 1) of cyclohexanone 8 Dissolve in m1 60. After heating to C, 39.2 mg (0.048 mmo 1) of a ruthenium carbene complex of the formula (V) (manufactured by STREM CHEMICAL) was added, and the mixture was reacted at 60 ° C. for 1 hour while stirring with a mechanical stirrer. . Thereafter, 0.791 g (7.13 mmo 1) of cyclooctene as monomer A was added, and the mixture was further reacted for 2 hours.After that, 0.55 ml of vinyl acetate (6.Ommo 1) and 6 m of cyclohexanone were used as a reaction terminator. 1 was added and reacted for 5 minutes, and then the cooled reaction solution was poured into 200 ml of methanol to obtain a white precipitate (polymer).

FIG. 1 shows a GPC chromatogram of the polymer of Comparative Example 1 measured in the same manner as in the example. The molar ratio of cyclooctene / endo-DE in the polymer measured in the same manner as in Example 1 was 46/54.

Comparative Example 2

In a 100 ml glass flask, 0.791 g (7.13 mmo 1) of cyclooctane as monomer A was dissolved in 8 ml of cyclohexanone and heated to 60 ° C. Ruthenium carbene complex (STREM CHEMICAL) 39.2 mg (0.048 mmo 1) was added, and the mixture was reacted at 60 ° C for 1 hour while stirring with a mechanical stirrer. 55 ml (6. Ommo 1) and 6 ml of cyclohexanone were added and reacted for 5 minutes. Then, the cooled reaction solution was poured into 200 ml of methanol and a white precipitate (polymer from monomer A) was added. I got

FIG. 1 shows a GPC chromatogram of the polymer of Comparative Example 2 measured in the same manner as in the example. In Comparative Example 1, two peaks are observed, indicating that these are a mixture of two types of polymers (homopolymers or copolymers), and that at least a homogeneous block copolymer has not been obtained. On the other hand, in Example 1, one peak shifted to the higher molecular weight side than Comparative Example 2 (polymerization of monomer A alone) was obtained, so that the copolymer was not a mixture of monomer A and monomer B but a copolymer. This was confirmed. Further, the polymer of Example 1 was formed into a film, and the glass transition temperature (Tg) was measured using a dynamic viscoelasticity measuring device (manufactured by Rheometrics). From these two points, it was confirmed that the polymer of Example 1 was not a random copolymer but a block copolymer.

As in Example 1, the polymers of Examples 2 and 3 were confirmed to be block copolymers from the measurement results of GPC and Tg.

Examples:! In Nos. 1 to 3, block copolymers having a raw material component molar ratio (copolymerization ratio) almost equal to the charged molar ratio of the raw material monomers were obtained.

Example 4 (A / B of charged monomer = 50/50 (molar ratio), solvent used: tetrahydrofuran)

Using tetrahydrofuran as a solvent, the amount of cyclooctene used is 11 g (lOOmmol), the amount of endo-5-norbornene-2,3-dimethylester used is 21 g (10 Omo1), and the formula ( A polymer was obtained in the same manner as in Example 1 except that the amount of the ruthenium carbene complex used in V) was 0.27 g (0.33 mmo 1). The yield was 90%, the Mn in terms of standard polystyrene was 103, 000, and the ^: degree in the molecular weight distribution was 1.91. The molar ratio of each raw material component was calculated in the same manner as in Example 1. As a result, the molar ratio of cyclooctene / endo-DME in the polymer was 50:50. This was consistent with the charge ratio of the rain monomer.

Example 5 (A / B of charged monomer = 80 to 20 (molar ratio))

In the same manner as in Example 4 except that the amount of cyclooctene used was 70 g (640 mm 01) and the amount of endo-5-norbornene-1,2-dimethyl ester was 34 g (16 Ommo 1) ( The amount of the ruthenium carbene complex represented by the formula (V) was 0.33 mmo1), and a polymer was obtained. 85% yield, standard polystyrene equivalent 1 ^ 11 was 75,000, and the degree of dispersion of the molecular weight distribution was 1.6. The molar ratio of each raw material component was calculated in the same manner as in Example 1. As a result, the molar ratio of cyclooctene "endo-DME" in the polymer was 78:22.

Example 6 (AZB of charged monomer = 50/50 (molar ratio), use of a large amount of catalyst) The amount of the ruthenium carbene complex of the formula (V) was changed to 3.3 mmo 1 which was 10 times the amount of Example 4 A polymer was obtained in the same manner as in Example 4, except that The yield was 90%, Mn in terms of standard polystyrene was 33,000, and the polydispersity of the molecular weight distribution was 1.9. The molar ratio of each raw material component was calculated in the same manner as in Example 1. As a result, the molar ratio of cyclooctene Zendo-DME in the polymer was 53:47.

Example 7 (ΑΖΒ ^ δ 0/20 of the charged monomer (molar ratio), use of a large amount of catalyst) In the same manner as in Example 5 except that the amount of the ruthenium carbene complex used was changed to 10 g (13 mmo 1). A polymer was obtained. The yield was 8896, the Mn in terms of standard polystyrene was 24,000, and the polydispersity of the molecular weight distribution was 1.9. The molar ratio of each raw material component was calculated in the same manner as in Example 4, and as a result, the molar ratio of cyclooctene / endo-DME in the polymer was 79:21.

Example 8 Preparation of film-like adhesive for circuit connection

20 g of PKHC (phenoxy resin, manufactured by Union Carbide), 30 g of Epoxy YL-983 U (bisphenol F type liquid epoxy resin, manufactured by Yuka Shellepoxy) and the block weight prepared in Example 4 Combine (number-average molecular weight: 103,000, molecular weight distribution: 1.91) weigh 20 g and dissolve in a mixed solvent of toluene / ethyl acetate = 50/50 (weight ratio) to obtain a solution with a solid content of 40%. did. To this, 30 g of Novakiure HX-3394 HP (latent curing agent, manufactured by Asahi Ciba) was added and mixed, and 1.5 g of epoxysilane compound (A_187, manufactured by Nihon Nikka Co., Ltd.) as a silane coupling agent was added Mixed. Then, a conductive layer having an average particle diameter of 10 / m and a specific gravity of 2.0 (a nickel layer having a thickness of 0.2 m is provided on the surface of particles having polystyrene cores). 2 01%) was mixed and dispersed at 3% by volume (based on the solid content), and this mixture was applied to a 80 / m thick fluororesin film using a coating device. 70 ° C, 10 minutes By hot air drying, a film-like adhesive for circuit connection having a thickness of 25 was obtained on the fluororesin film.

Example 9 Preparation of circuit connector

Using the film-like adhesive (25 m thick) for circuit connection with one side covered with a fluororesin film obtained above, 500 copper circuits with a line width of 50 m, a pitch of 100 m, and a thickness of 18 in are used. Flexible circuit board (FPC) and glass (thickness: 1 lmm, surface resistance: 20 Ω) on which a thin layer of 0.2 m indium oxide (ITO) is formed at 180 ° C and 4 MPa. The connection was made by heating and pressing for 20 seconds over a width of 2 mm.

At this time, the adhesive surface of the film adhesive was heated and pressed at 70 ° C and 0.5 MPa for 5 seconds on IT 仮 glass for temporary connection, and then the fluororesin film was peeled off. It was connected to the FPC, which was the adherend, to form a connected body.

When the resistance value between the adjacent circuits of the obtained connection body was measured, the average of the 150 points of the resistance between the adjacent circuits was 2.7Ω, indicating good connection characteristics.

The adhesive strength of this connector was measured by a 90-degree peeling method in accordance with JIS Z0237. The adhesive strength was 80 ON / m, indicating a sufficient adhesive strength. The adhesive strength was measured using Toyo Baldwin's Tensilon UTM-4 (peeling speed 5 Omm / min, 25 ° C). Industrial applicability

According to the method for producing a block copolymer of the present invention, a block copolymer in which molecular species A and molecular species B are respectively chained and connected using two different raw materials monomers (A, B) is obtained. Obtained easily. Also, the structures of the two different raw material monomers (A, B) may be extremely different. Also, the two molecular species A and ^^ species B incorporated into the copolymer reflect the amount (mol) of monomer charged, so that the product (block copolymer) can be easily controlled. Further, the structural design of the polymer (block copolymer) is easy, and a desired block copolymer can be effectively produced. The block copolymer obtained in the present invention is a novel block copolymer. Ma Also, it has low elasticity, high strength, low stress, high adhesiveness, moisture resistance, heat resistance, film forming ability, and excellent compatibility with other components. Therefore, it can be widely used in the fields of adhesive materials for electronic materials such as semiconductor packages, compatibilizers, solubilizers, and nonionic polymer surfactants, and has great industrial value.

The adhesive for circuit connection of the present invention is used for circuit connection of electric and electronic components such as semiconductor packages, and exhibits good connection characteristics and adhesive strength.

Claims

The scope of the claims

1. When performing a metathesis polymerization reaction between a metathesis-polymerizable unsaturated monocyclic compound (A) and a metathesis-polymerizable unsaturated polycyclic compound (B) using a metal carbene complex catalyst (C), First, a method of producing a block copolymer in which the entire amount of the monocyclic compound (A) and the required metal carbene complex catalyst (C) are mixed and reacted, and then the polycyclic compound (B) is added and reacted.

2. The block copolymer according to claim 1, further comprising a step of adding a reaction terminator to terminate the polymerization reaction and removing a catalyst active site derived from the catalyst (C) bonded to one end of the polymer. Manufacturing method.

3. The method for producing a block copolymer according to claim 2, further comprising a step of saturating the remaining unsaturated double bond by a hydrogenation reaction.

4. The process for producing a block copolymer according to claim 1, wherein the unsaturated monocyclic compound (A) is a substituted or unsubstituted cycloalkene compound.

5. The process for producing a block copolymer according to claim 1, wherein the unsaturated polycyclic compound (B) is a substituted or unsubstituted norbornene compound.

6. A block copolymer produced by the production method according to any one of claims 1 to 5.

7. One block of the block copolymer is composed of a molecular chain (mA) in which m kinds of molecular species (A) having an unsubstituted or substituted methylene group in the main chain are connected in a chain, and the other block is A block copolymer comprising a molecular chain (n B) in which molecular species (B) having a cyclocyclic structure in the main chain are linked in n chains,

A block copolymer characterized in that a residue other than the catalytically active site derived from the metal carbene complex catalyst (C) is bonded to one end of the copolymer molecule.

8. The block copolymer according to claim 7, wherein a catalyst active site derived from the metal carbene complex catalyst (C) is further bonded to the other end of the copolymer molecule.

9. The degree of dispersion of the molecular weight distribution of the copolymer (weight average molecular weight, number average molecular weight) is 1.

9. The block copolymer according to claim 7, which is 0 or more and 2.5 or less.

10. A non-polar and flexible molecular chain in which one block of the block copolymer is composed of m molecular species (A) having a methylene group substituted or unsubstituted in the main chain in the main chain. mA)

The other block comprises a polar and rigid molecular chain (nB) in which the molecular species (B) having a cyclocyclic structure in the main chain and having a polar substituent on the cyclo ring is connected in n chains. A block copolymer according to item 7 above.

11. The molecular species (A) has a ratio of inorganic to organic on the organic conceptual diagram of 0 to 0.3, and the polar substituent on the cyclo ring of the molecular species (B) has a substituent constant ( And the block copolymer according to claim 10, wherein I) is a group of not less than 0.05 and not more than 0.80.

1 2. A nonpolar and flexible molecular chain (mA) in which m kinds of molecular species (A) having a methylene group substituted or unsubstituted by a nonpolar group in the main chain are connected in a m-chain form;

The main chain contains a cyclo ring structure of a cycloalkane compound, a cycloalkene compound, an oxacycloalkane compound, an oxacycloalkene compound, a thiacycloalkane compound, or a thiacycloalkene compound, and has a polar substitution on the cyclo ring. Polar and rigid molecular chains (n

B) A block copolymer comprising:

13. The molecular species (A) has a ratio of inorganic to organic on the organic conceptual diagram of 0 to 0.3, and the polar substituent on the cyclo ring of the molecular species (B) has a substituent constant ( And I) is 0.

13. The block copolymer according to claim 12, wherein the group is a group of not less than 0.5 and not more than 0.8.

14. An adhesive for circuit connection, comprising the block copolymer according to any one of claims 6 to 13.