JP2015187219A - Method for producing ring-opened polymer hydride - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a method for producing a ring-opened polymer hydride having excellent adhesiveness with other material.SOLUTION: There is provided a ring-opened polymer hydride obtained by hydrogenating 70% or more of a carbon-carbon double bond of a ring-opened polymer obtained by ring-opening metathesis polymerization of a monomer containing a compound represented by the following formula (I). (Rrepresents a substituent selected from the group consisting of a hydrocarbon group having 1 to 10 carbon atoms. a halogen atom and a hydrocarbon group having 1 to 10 carbon atoms substituted with a halogen atom; m represents an integer of 0 or more and (6n+6) or less; when m is 1 or more, a bonding position of Ris not limited; when m is 2 or more, Rmay be same or different each other; and n represents an integer of 1 to 3.)

Description

  The present invention relates to a ring-opening polymer hydride that is excellent in adhesion to other materials.

  For example, a ring-opening polymer hydride of dicyclopentadiene as described in Patent Document 1 is a kind of so-called cycloolefin polymer and has excellent water vapor barrier properties, transparency, low birefringence, molding processability, and the like. Therefore, it is used as a material applicable to various uses such as optical use and electronic material use.

  However, after ring-opening polymerization of dicyclopentadiene alone, a hydride obtained by hydrogenating the resulting ring-opened polymer is difficult to adhere to general synthetic resins or metals, and other materials There was a problem that it was difficult to obtain the composite of. Thus, for example, as disclosed in Patent Document 2 and Patent Document 3, a study has been made to improve the adhesion to other materials by introducing a polar group into a cycloolefin polymer.

  However, for example, even the cycloolefin polymers specifically disclosed in Patent Document 2 and Patent Document 3 may not be suitable for use depending on applications, and thus have a structure different from conventional cycloolefin polymers, And the cycloolefin polymer which is excellent in adhesiveness with another material is desired.

Japanese Patent Laid-Open No. 11-124429 JP 2002-317034 A JP 2012-246466 A

  The present invention has been made under such circumstances, and an object thereof is to provide a ring-opened polymer hydride that is excellent in adhesion to other materials.

  As a result of intensive studies to achieve the above object, the present inventors have found that the carbon-carbon of a ring-opening polymer obtained by ring-opening metathesis polymerization of a monomer containing a compound represented by the following formula (I): It has been found that a ring-opened polymer hydride obtained by hydrogenating 70% or more of double bonds is extremely excellent in adhesion to other materials, and the present invention has been completed based on this finding. It was.

Thus, according to the present invention, the following ring-opening polymer hydrides (1) to (3) are provided.
(1) Opening obtained by hydrogenating 70% or more of carbon-carbon double bonds in a ring-opening polymer obtained by ring-opening metathesis polymerization of a monomer containing a compound represented by the following formula (I) Cyclic polymer hydride.

(R ¹ represents a substituent selected from the group consisting of a hydrocarbon group having 1 to 10 carbon atoms, a halogen atom, and a hydrocarbon group having 1 to 10 carbon atoms substituted with a halogen atom. M is 0 or more. , (6n + 6) or less, when m is 1 or more, the bonding position of R ¹ is not limited, and when m is 2 or more, R ¹ may be the same or different from each other. N represents an integer of 1 to 3.)

(2) The ring-opening according to (1), wherein the compound represented by the formula (I) is 4,5-epoxytricyclo [5.2.1.0 ^2,6 ] dec-8-ene. Polymer hydride.
(3) The ring opening according to (1) or (2), wherein the monomer further contains another compound copolymerizable with the compound represented by the formula (I) by ring opening metathesis polymerization. Polymer hydride.

  The ring-opening polymer hydride of the present invention is excellent in adhesion to other materials. Therefore, it can be suitably used for various applications by being used to form a composite with various materials according to the purpose.

  The hydrogenated ring-opening polymer of the present invention is obtained by ring-opening metathesis polymerization of a monomer containing a compound represented by the following formula (I) (hereinafter sometimes referred to as “compound (I)”). This is obtained by hydrogenating 70% or more of the carbon-carbon double bond of the ring-opening polymer.

The ring-opening polymer used in the present invention has a repeating unit derived from compound (I).
In the formula (I), R ¹ is a hydrocarbon group having 1 to 10 carbon atoms (preferably a hydrocarbon group having 1 to 5 carbon atoms), a halogen atom, and a C 1-10 carbon atom substituted with a halogen atom. It represents a substituent selected from the group consisting of a hydrocarbon group (preferably a hydrocarbon group having 1 to 5 carbon atoms substituted with a halogen atom).

Examples of the hydrocarbon group having 1 to 10 carbon atoms of R ¹ include alkyl groups having 1 to 10 carbon atoms such as a methyl group, an ethyl group, and a propyl group; and 2 to 10 carbon atoms such as a vinyl group, a propenyl group, and a crotyl group. Alkenyl group; alkynyl group having 2 to 10 carbon atoms such as ethynyl group, propargyl group and 3-butynyl group; aryl group having 6 to 10 carbon atoms such as phenyl group, 1-naphthyl group and 2-naphthyl group; cyclopropyl group , A cycloalkyl group having 3 to 10 carbon atoms such as a cyclopentyl group and a cyclohexyl group;
Examples of the halogen atom of R ^1, a fluorine atom, a chlorine atom, and bromine atom.
Examples of the hydrocarbon group having 1 to 10 carbon atoms substituted with a halogen atom of R ^1, chloromethyl group, 2-chloroethyl group, a trifluoromethyl group, pentafluoroethyl group and the like.

m is an integer of 0 or more and (6n + 6) or less, preferably an integer of 0 to 4. When m is 1 or more, the bonding position of R ¹ is not limited. When m is 2 or more, the plurality of R ¹ may be the same as or different from each other. n is an integer of 1 to 3, preferably 1 or 2, and more preferably 1.

Specific examples of the compound (I) include 4,5-epoxytricyclo [5.2.1.0 ^2,6 ] dec-8-ene, 4,5-epoxy-8-chlorotricyclo [5.2. .1.0 ^2,6 ] dec-8-ene, 4,5-epoxy-8-methyltricyclo [5.2.1.0 ^2,6 ] dec-8-ene, 4,5-epoxy-8 A compound in which n is 1 in formula (I), such as trifluoromethyltricyclo [5.2.1.0 ^2,6 ] dec-8-ene;
10,11-epoxypentacyclo [6.5.1.1 ^3,6 . 0 ^2,7 . 0 ^9,13] pentadeca-4-ene, 10,11-epoxy-4-chloro-penta cyclo [6.5.1.1 ^{3, 6.} 0 ^2,7 . 0 ^9,13] pentadeca-4, such as ene, compound n is 2 in formula (I);
14,15-epoxy hepta cyclo [10.5.1.1 ^3,10. 1 ^5,8 . 01 ^{3, 17]} eicosa-6-ene, 14,15-epoxy-6-chloro-hept-cyclo [10.5.1.1 ^{3, 10.} 1 ^5,8 . 01 ^3,17 ] compounds in which n in the formula (I) is 3, such as eicosa-6-ene.
Among these, from the viewpoint of availability and the desired ring-opening polymer hydride can be obtained efficiently, a compound in which n is 1 is preferable, and 4,5-epoxytricyclo [5.2.1.0]. ^2,6 ] dec-8-ene is more preferred.

  Compound (I) can be obtained, for example, by epoxidizing a dimer, trimer, or tetramer of cyclopentadiene. In this epoxidation reaction, a known reaction using a heteropolyacid and hydrogen peroxide or the like (for example, JP-A-2006-104110) can be used. Moreover, when reacting using heteropolyacid and hydrogen peroxide, it can selectively epoxidize by adjusting the quantity of hydrogen peroxide.

  The ring-opening polymer used in the present invention is obtained by homopolymerizing (i) one type of compound (I) as a monomer, and (ii) using two or more types of compound (I) as monomers. (Iii) at least one compound (I) and at least one other compound copolymerizable therewith (hereinafter sometimes referred to as “other compounds”) obtained by polymerization. Any of those obtained by copolymerizing a monomer containing it may be used. Among these, since it is easy to obtain the intended effect of the present invention, it is obtained by copolymerizing (iii) a monomer containing at least one compound (I) and at least one other compound. It is preferred that

  When another compound is used as a monomer, the content of the other compound in the monomer is usually 80 parts by weight or less, preferably 100 parts by weight or less, preferably 100 parts by weight in total of the compound (I) and the other compound. 0.001 to 50 parts by weight, more preferably 0.01 to 40 parts by weight, particularly preferably 0.1 to 30 parts by weight.

  The other compound is not particularly limited as long as it is capable of ring-opening copolymerization with compound (I) and does not inhibit the object of the present invention, and examples thereof include cyclic olefin compounds other than the compound (I). Examples of the cyclic olefin compound include monocyclic cyclic olefin compounds and norbornene compounds. The cyclic olefin compound may have a substituent. Examples of the substituent include a hydrocarbon group having 1 to 10 carbon atoms, a halogen atom, and a hydrocarbon group having 1 to 10 carbon atoms substituted with a halogen atom. Specific examples of these substituents include those similar to those exemplified as the substituent of compound (I).

  Specific examples of the monocyclic olefin compounds include cyclobutene, cyclopentene, 3-methylcyclopentene, 4-methylcyclopentene, 3,4-dimethylcyclopentene, 3,5-dimethylcyclopentene, 3-chlorocyclopentene, cyclohexene, 3 -Methylcyclohexene, 4-methylcyclohexene, 3,4-dimethylcyclohexene, 3-chlorocyclohexene, 3-vinylcyclohexene, 4-vinylcyclohexene, cycloheptene, cyclooctene, cyclododecene, 1,3-cyclopentadiene, 1, Examples include 3-cyclohexadiene, 1,4-cyclohexadiene, 5-ethyl-1,3-cyclohexadiene, 1,3-cycloheptadiene, and 1,3-cyclooctadiene.

Specific examples of norbornene compounds include norbornene, 1-methyl-2-norbornene, 5-methyl-2-norbornene, 7-methyl-2-norbornene, 5-ethyl-2-norbornene, and 5-propyl-2-norbornene. 5-phenyl-2-norbornene, 5,6-dimethyl-2-norbornene, 5,5,6-trimethyl-2-norbornene, 5-chloro-2-norbornene, 5,5-dichloro-2-norbornene, 5 -Fluoro-2-norbornene, 5,5,6-trifluoro-6-trifluoromethyl-2-norbornene, 5-chloromethyl-2-norbornene, 5-methylidene-2-norbornene, 5-ethylidene-2-norbornene 5-n-propylidene-2-norbornene, 5-isopropylidene-2-norbornene, 5 Bicycles such as vinyl-2-norbornene, 5-allyl-2-norbornene, 5,6-diethylidene-2-norbornene, 5-cyclohexenyl-2-norbornene, 2,5-norbornadiene; dicyclopentadiene (cyclopentadiene Dimers), 1,2-dihydrodicyclopentadiene, 5,6-dihydrodicyclopentadiene and the like; 1,4,5,8-dimethano-1,2,3,4,4a, 5 8,8a-octahydronaphthalene (TCD), 2-methyl-1,4,5,8-dimethano-1,2,3,4,4a, 5,8,8a-octahydronaphthalene, 2-ethyl-1 , 4,5,8-dimethano-1,2,3,4,4a, 5,8,8a-octahydronaphthalene, 2,3-dimethyl-1,4,5,8-dimethano-1,2,3 , 4,4a 5,8,8a-octahydronaphthalene, 2-hexyl-1,4,5,8-dimethano-1,2,3,4,4a, 5,8,8a-octahydronaphthalene, 2-ethylidene-1, 4,5,8-dimethano-1,2,3,4,4a, 5,8,8a-octahydronaphthalene, 2-fluoro-1,4,5,8-dimethano-1,2,3,4 4a, 5,8,8a-octahydronaphthalene, 1,5-dimethyl-1,4,5,8-dimethano-1,2,3,4,4a, 5,8,8a-octahydronaphthalene, 2- Cyclohexyl-1,4,5,8-dimethano-1,2,3,4,4a, 5,8,8a-octahydronaphthalene, 2,3-dichloro-1,4,5,8-dimethano- 1,2,3,4,4a, 5,8,8a-octahydronaphthalene, 2-isobuty 1,4,5,8-dimethano-1,2,3,4,4a, 5,8,8a-octahydronaphthalene, etc .; pentacycles such as cyclopentadiene trimer; cyclopentadiene A heptacycle such as a tetramer; and the like.
These cyclic olefin compounds can be used alone or in combination of two or more.

  The ring-opening polymer hydride of the present invention is a ring-opening metathesis polymerization of a monomer containing at least one of the compounds (I) and other compounds used as necessary in the presence of a metathesis polymerization catalyst, It can be obtained by hydrogenating the resulting ring-opening polymer.

  The metathesis polymerization catalyst is not particularly limited as long as the monomer used can be ring-opening polymerized, and a known catalyst can be used. For example, a transition metal complex in which a plurality of ions, atoms, polyatomic ions, compounds, and the like are bonded with a transition metal atom as a central atom can be mentioned. In this transition metal complex, atoms of Group 5, Group 6, and Group 8 (according to the long period periodic table; the same applies hereinafter) are usually used as the transition metal atom. Although the atoms of each group are not particularly limited, examples of the Group 5 atom include tantalum, examples of the Group 6 atom include molybdenum and tungsten, and examples of the Group 8 atom include: Examples include ruthenium and osmium. Among these, as the transition metal atom, Group 8 ruthenium or osmium is preferable.

Among these, as the metathesis polymerization catalyst, a complex having ruthenium or osmium as a central atom is preferable, and a complex having ruthenium as a central atom is more preferable.
As the complex having ruthenium as a central atom, a ruthenium carbene complex in which a carbene compound is coordinated to ruthenium is preferable. Here, the “carbene compound” is a general term for compounds having a methylene free group, and refers to a compound having an uncharged divalent carbon atom (carbene carbon) as represented by (> C :).

  Examples of the ruthenium carbene complex include complexes represented by the following formula (II) or formula (III).

R ² and R ³ each independently represent a hydrogen atom; a halogen atom; or a cyclic or chain-like carbon which may contain a halogen atom, an oxygen atom, a nitrogen atom, a sulfur atom, a phosphorus atom or a silicon atom. The hydrocarbon group of number 1-20 is represented. R ² and R ³ may be bonded to each other to form an aliphatic ring or an aromatic ring.

X ¹ and X ² each independently represents an arbitrary anionic ligand. Anionic ligands X ¹ and X ² are ligands having a negative charge when separated from the central atom. For example, halogen atoms such as fluorine atom (F), chlorine atom (Cl), bromine atom (Br), and iodine atom (I); diketonate group; substituted cyclopentadienyl group; alkoxy group; aryloxy group; carboxyl group And the like. Among these, a halogen atom is preferable and a chlorine atom is more preferable.

L ¹ and L ² each independently represents a neutral electron donating compound. The neutral electron donating compounds L ¹ and L ² are ligands that are electrically neutral when pulled away from the central atom.
At least one of L ¹ and L ² is a heteroatom-containing carbene compound. A heteroatom means an atom of groups 15 and 16 of the periodic table, and specifically, a nitrogen atom (N), an oxygen atom (O), a phosphorus atom (P), a sulfur atom (S), an arsenic atom (As), a selenium atom (Se), etc. are mentioned. Among these, N, O, P, and S are preferable, and N is particularly preferable from the viewpoint of obtaining a stable carbene compound.

  Examples of the heteroatom-containing carbene compound include compounds represented by the following formula (IV) or formula (V).

R ^{4 to} R ⁷ are each independently a hydrogen atom; a halogen atom; or a cyclic or chain-like carbon which may contain a halogen atom, an oxygen atom, a nitrogen atom, a sulfur atom, a phosphorus atom or a silicon atom. This represents a hydrocarbon group having a number of 1 to 20. R ^{4 to} R ⁷ may be bonded together in any combination to form an aliphatic ring or an aromatic ring.

  Examples of the compound represented by the formula (IV) or formula (V) include 1,3-dimesitylimidazolidin-2-ylidene, 1,3-di (1-adamantyl) imidazolidin-2-ylidene, 1, 3-dicyclohexylimidazolidine-2-ylidene, 1,3-dimesityloctahydrobenzimidazol-2-ylidene, 1,3-diisopropyl-4-imidazoline-2-ylidene, 1,3-di (1-phenylethyl) ) -4-imidazoline-2-ylidene, 1,3-dimesityl-2,3-dihydrobenzimidazol-2-ylidene, and the like.

  Neutral electron donating compounds other than hetero atom-containing carbene compounds include carbonyls, amines, pyridines, ethers, nitriles, esters, phosphines, thioethers, aromatic compounds, olefins, isocyanides, And thiocyanates. Of these, phosphines, ethers and pyridines are preferable, and trialkylphosphine is more preferable.

In the formulas (II) and (III), R ² , R ³ , X ¹ , X ² , L ¹ and L ² are bonded together in any combination to form a multidentate chelate ligand. Also good.

  Specific examples of the ruthenium carbene complex include benzylidene (1,3-dimesitylimidazolidine-2-ylidene) (tricyclohexylphosphine) ruthenium dichloride, (1,3-dimesitylimidazolidine-2-ylidene) ( 3-methyl-2-buten-1-ylidene) (tricyclopentylphosphine) ruthenium dichloride, benzylidene (1,3-dimesityl-octahydrobenzimidazol-2-ylidene) (tricyclohexylphosphine) ruthenium dichloride, benzylidene [1,3 -Di (1-phenylethyl) -4-imidazoline-2-ylidene] (tricyclohexylphosphine) ruthenium dichloride, benzylidene (1,3-dimesityl-2,3-dihydrobenzimidazol-2-ylidene) (tricyclide) Hexylphosphine) ruthenium dichloride, benzylidene (tricyclohexylphosphine) (1,3,4-triphenyl-2,3,4,5-tetrahydro-1H-1,2,4-triazol-5-ylidene) ruthenium dichloride, ( 1,3-diisopropylhexahydropyrimidin-2-ylidene) (ethoxymethylene) (tricyclohexylphosphine) ruthenium dichloride, benzylidene (1,3-dimesitylimidazolidine-2-ylidene) pyridine ruthenium dichloride, and the like.

  These ruthenium carbene complexes are described in Org. Lett. 1999, Vol. 1, page 953, and Tetrahedron. Lett. 1999, Vol. 40, page 2247, and the like.

The metathesis polymerization catalyst can be used alone or in combination of two or more.
The content of the metathesis polymerization catalyst is usually 1: 2,000 to 1: 2,000,000, preferably 1: 5,000 to the molar ratio (metal atoms in the metathesis polymerization catalyst: whole monomer). The range is from 1: 1,000,000, more preferably from 1: 10,000 to 1: 500,000.

  Ring-opening polymerization using a metathesis polymerization catalyst can be performed in a solvent or without a solvent. When the hydrogenation reaction is carried out as it is without isolating the produced ring-opening polymer after completion of the polymerization reaction, the polymerization is preferably carried out in a solvent.

The solvent used is not particularly limited as long as it dissolves the ring-opening polymer to be produced and does not inhibit the ring-opening polymerization reaction. For example, aliphatic hydrocarbons such as n-pentane, n-hexane, n-heptane, liquid paraffin; cyclopentane, cyclohexane, methylcyclohexane, dimethylcyclohexane, trimethylcyclohexane, ethylcyclohexane, diethylcyclohexane, decahydronaphthalene, bicycloheptane, Alicyclic hydrocarbons such as tricyclodecane, hexahydroindene and cyclooctane; aromatic hydrocarbons such as benzene, toluene, xylene and mesitylene; nitrogen-containing carbonization such as nitromethane, nitrobenzene, acetonitrile, propionitrile and benzonitrile Hydrogen; ethers such as diethyl ether, tetrahydrofuran and dioxane; ketones such as acetone, ethyl methyl ketone, methyl isobutyl ketone, cyclopentanone and cyclohexanone Down like; methyl acetate, ethyl acetate, ethyl propionate, methyl benzoate, chloroform, dichloromethane, 1,2-dichloroethane, chlorobenzene, dichlorobenzene, halogenated hydrocarbons such as chlorobenzene; and the like. Among these, the use of aromatic hydrocarbons or alicyclic hydrocarbons is preferable.
These solvents can be used alone or in combination of two or more.

  When the polymerization is performed in a solvent, the concentration of all monomers in the solvent is preferably 1 to 50% by weight, more preferably 2 to 45% by weight, and still more preferably 5 to 40% by weight. When the concentration of all monomers is less than 1% by weight, the productivity of the ring-opening polymer may be deteriorated. When the concentration exceeds 50% by weight, the viscosity after polymerization is too high, and subsequent hydrogenation becomes difficult. Sometimes.

  The metathesis polymerization catalyst may be dissolved in a solvent and added to the reaction system, or may be added as it is without being dissolved. Examples of the solvent for preparing the catalyst solution include the same solvents as those used in the ring-opening polymerization reaction.

  In the ring-opening polymerization reaction, a molecular weight modifier can be added to the reaction system in order to adjust the molecular weight of the ring-opened polymer. Examples of molecular weight modifiers include α-olefins such as 1-butene, 1-pentene, 1-hexene and 1-octene; styrenes such as styrene and vinyltoluene; ethers such as ethyl vinyl ether, isobutyl vinyl ether and allyl glycidyl ether; Halogen-containing vinyl compounds such as allyl chloride; oxygen-containing vinyl compounds such as allyl acetate, allyl alcohol, and glycidyl methacrylate; nitrogen-containing vinyl compounds such as acrylonitrile and acrylamide can be used. A ring-opening polymer having a desired molecular weight can be obtained by using 0.05 to 50 mol% of a molecular weight modifier with respect to all monomers.

  The ring-opening polymerization temperature is not particularly limited, but is usually −100 ° C. to + 200 ° C., preferably −50 ° C. to + 180 ° C., more preferably −30 ° C. to + 160 ° C., and further preferably 0 ° C. to + 140 ° C. The polymerization time is usually from 1 minute to 100 hours, and can be appropriately adjusted according to the progress of the reaction.

The hydrogenated ring-opening polymer of the present invention is obtained by hydrogenating a carbon-carbon double bond contained in the ring-opening polymer.
In the ring-opening polymer hydride of the present invention, the hydrogenation rate (hydrogenation rate) of the carbon-carbon double bond is 70% or more.

Hydrogenation rate, for example, carbon in the ^{1 H-NMR} spectrum of the ring-opening polymer - a peak intensity derived from the carbon-carbon double bond, carbon in the ^{1 H-NMR} spectrum of the ring-opening polymer hydride - carbon double bond It can obtain | require by comparing with the peak intensity derived from.

The hydrogenation reaction can be performed, for example, using hydrogen gas in the presence of a hydrogenation catalyst.
The hydrogenation catalyst to be used is not particularly limited, such as a homogeneous catalyst and a heterogeneous catalyst, and those generally used for hydrogenation of olefin compounds can be used as appropriate.

  Examples of homogeneous catalysts include transitions such as cobalt acetate and triethylaluminum, nickel acetylacetonate and triisobutylaluminum, a combination of titanocene dichloride and n-butyllithium, zirconocene dichloride and sec-butyllithium, tetrabutoxytitanate and dimethylmagnesium, etc. Ziegler catalyst comprising a combination of a metal compound and an alkali metal compound; ruthenium carbene complex catalyst, dichlorotris (triphenylphosphine) rhodium described in the above section of ring-opening metathesis polymerization catalyst, JP-A-7-2929, JP-A-7-149823 Noble metal complexes comprising ruthenium compounds described in JP-A-11-109460, JP-A-11-158256, JP-A-11-193323, JP-A-11-109460, etc. ; And the like.

  Examples of the heterogeneous catalyst include a hydrogenation catalyst in which a metal such as nickel, palladium, platinum, rhodium, and ruthenium is supported on a carrier such as carbon, silica, diatomaceous earth, alumina, and titanium oxide. More specifically, for example, nickel / silica, nickel / diatomaceous earth, nickel / alumina, palladium / carbon, palladium / silica, palladium / diatomaceous earth, palladium / alumina and the like can be used. These hydrogenation catalysts can be used alone or in combination of two or more.

  Among these, from the viewpoint of efficient hydrogenation, use of a noble metal complex catalyst such as rhodium or ruthenium and a palladium-supported catalyst such as palladium / carbon is preferable, and use of a ruthenium carbene complex catalyst or a palladium-supported catalyst is more preferable.

  The ruthenium carbene complex catalyst described above can be used as a ring-opening metathesis polymerization catalyst and a hydrogenation catalyst. In this case, the ring-opening metathesis reaction and the hydrogenation reaction can be performed continuously.

  In addition, when a ring-opening metathesis reaction and a hydrogenation reaction are continuously performed using a ruthenium carbene complex catalyst, a vinyl compound such as ethyl vinyl ether or a catalyst modifier such as an α-olefin is added to activate the catalyst. Then, the method of starting the hydrogenation reaction is preferably employed. Furthermore, it is also preferable to employ a method of improving the activity by adding a base such as triethylamine or N, N-dimethylacetamide.

  The hydrogenation reaction is usually performed in an organic solvent. As an organic solvent, it can select suitably by the solubility of the hydride to produce | generate, The thing similar to the solvent illustrated as being usable at the time of the said ring-opening polymerization can be used. Therefore, after the ring-opening polymerization reaction, the hydrogenation catalyst can be added to the reaction solution or the filtrate obtained by filtering the metathesis polymerization catalyst from the reaction solution without changing the solvent.

  The conditions for the hydrogenation reaction may be appropriately selected according to the type of hydrogenation catalyst used. The amount of the hydrogenation catalyst used is usually 0.01 to 50 parts by weight, preferably 0.05 to 20 parts by weight, more preferably 0.1 to 10 parts by weight with respect to 100 parts by weight of the ring-opening polymer. . The reaction temperature is usually −10 ° C. to + 250 ° C., preferably −10 ° C. to + 210 ° C., more preferably 0 ° C. to + 200 ° C. At a temperature lower than this range, the reaction rate becomes slow. Conversely, at a high temperature, a side reaction tends to occur. The pressure of hydrogen is usually 0.01 to 10.0 MPa, preferably 0.05 to 8.0 MPa, more preferably 0.1 to 6.0 MPa.

  The time for the hydrogenation reaction is appropriately selected in order to control the hydrogenation rate. The reaction time is usually in the range of 0.1 to 50 hours, and hydrogenates 70% or more, preferably 75% or more, more preferably 80% or more of the carbon-carbon double bonds in the ring-opening polymer. be able to.

  For example, the weight average molecular weight (Mw) of the ring-opened polymer hydride of the present invention obtained as described above is not particularly limited, but is usually 5000 to 500,000, preferably 10,000 to 100,000. In addition, this value is a polystyrene conversion value measured by gel permeation chromatography using toluene as a solvent. The glass transition temperature of the ring-opened polymer hydride of the present invention is not particularly limited, but is usually 50 to 250 ° C, preferably 100 to 180 ° C.

  The ring-opening polymer hydride of the present invention may be used after adding various compounding agents, if necessary. The compounding agents include antioxidants, solvents, crosslinking agents, radiation sensitive compounds, sensitizers, surfactants, latent acid generators, acidic compounds, coupling agents or derivatives thereof, light stabilizers, antifoaming agents. , Pigments, dyes, fillers and the like.

  The ring-opened polymer hydride of the present invention is excellent in cycloolefin polymer, for example, in various properties such as water vapor barrier property, and in excellent adhesion to other materials. Accordingly, for example, adhesion to other materials such as a semiconductor protective film material, a liquid crystal sealing material, a circuit protective material, a planarizing film material, and an electronic component material such as an electrical insulating film material is required. It can be used suitably for a use.

  Hereinafter, the present invention will be described more specifically with reference to examples and comparative examples. However, the present invention is not limited to the examples. Parts and% in each example are based on weight unless otherwise specified.

(1) The number average molecular weight (Mn) and the weight average molecular weight (Mw) of the ring-opened polymer hydride were measured as polystyrene converted values by gel permeation chromatography (GPC) using toluene as a solvent.
(2) The glass transition temperature of the ring-opening polymer hydride was measured using a differential scanning calorimeter (“EXSTAR DSC6220” manufactured by SII Nano Technology) under the temperature increase rate of 10 ° C./min.
(3) hydrogenation rate of the ring-opening polymer hydride, carbon in the ^{1 H-NMR} spectrum of the ring-opening polymer - a peak intensity derived from the carbon-carbon double bond, ^{1 H-NMR} of the ring-opened hydrogenated polymer It calculated from the integral ratio of the peak intensity derived from the carbon-carbon double bond in a spectrum.

[Production Example 1] Synthesis of 4,5-epoxytricyclo [5.2.1.0 ^2,6 ] dec-8-ene Nitrogen gas in a three-necked reactor equipped with a thermometer, a dropping funnel and a stirrer In this reactor, 50.0 g (378.2 mmol) of dicyclopentadiene and 3.39 g (9.46 mmol) of hexadecylpyridinium chloride monohydrate were dissolved in 250 ml of chloroform. Next, while stirring the reactor contents, 5.45 g of 12-tungsto (VI) phosphate n-hydrate was dissolved in 42.88 g (378.2 mmol) of 30% aqueous hydrogen peroxide. The solution was added dropwise over 30 minutes, and then stirring was continued for 3 hours at room temperature (25 ° C., the same below). Next, 150 ml of distilled water and 100 ml of saturated saline were added to the reactor contents, and the organic layer was separated by performing a liquid separation operation. The obtained organic layer was dried by adding anhydrous sodium sulfate, and then sodium sulfate was filtered off. The concentrate obtained by concentrating the filtrate was purified by silica gel column chromatography (ethyl acetate: n-hexane = 1.5: 18.5 (volume ratio, the same shall apply hereinafter)) to give 4,5. -26.3 g of epoxytricyclo [5.2.1.0 ^2,6 ] dec-8-ene was obtained as a white solid (yield 47%).
The structure of the obtained product was identified by ¹ H-NMR.

[Example 1]
Into a nitrogen-substituted glass reactor, 1.18 parts of 4,5-epoxytricyclo [5.2.1.0 ^2,6 ] dec-8-ene obtained in Preparation Example 1, 70% of dicyclopentadiene 28.6 parts of cyclohexane solution, 0.134 part of 1-hexene and 86.8 parts of toluene were added and heated to 60 ° C. Next, as a metathesis polymerization catalyst, 0.0136 parts of benzylidene (1,3-dimesitylmimidazolidine-2-ylidene) (tricyclohexylphosphine) ruthenium dichloride are dissolved in 5.9 parts of toluene to obtain a catalyst solution. Prepared. The obtained catalyst solution was added to the reactor to initiate the polymerization reaction. After stirring at 60 ° C. for 1 hour, the polymerization reaction solution was diluted with toluene and dropped into a large amount of methanol to precipitate a polymer. The precipitated polymer was separated by filtration, washed with acetone, and then dried under reduced pressure at 40 ° C. for 24 hours to obtain a ring-opening polymer 1.

18 parts of the obtained ring-opening polymer 1 and 86.8 parts of toluene were added to an autoclave equipped with a stirrer. Next, 0.064 parts of chlorohydridocarbonyltris (triphenylphosphine) ruthenium (II) was added as a hydrogenation catalyst, and a hydrogenation reaction was performed at a hydrogen pressure of 0.9 MPa and 160 ° C. for 8 hours. The hydrogenation reaction solution was diluted with toluene and dropped into a large amount of methanol to precipitate a polymer. The precipitated polymer was separated by filtration, washed with acetone, and then dried under reduced pressure at 40 ° C. for 24 hours to obtain a ring-opened polymer hydride 1. The obtained ring-opened polymer hydride 1 has a number average molecular weight (Mn) of 1.5 × 10 ⁴ , a weight average molecular weight (Mw) of 5.9 × 10 ⁴ , a glass transition temperature of 107 ° C., and a hydrogenation rate of It was 85%. These results are shown in Table 1.

  5 parts of the obtained ring-opened polymer hydride 1 and pentaerythritol tetrakis [3- (3,5-di-tert-butyl-4-hydroxyphenyl) propionate] (“Irganox 1010”) as an antioxidant , Manufactured by BASF) was dissolved in 10 parts of toluene to prepare a resin solution. The obtained resin solution was applied onto a single-sided easy-adhesion-treated polyethylene terephthalate film (“Cosmo Shine A4100” manufactured by Toyobo Co., Ltd.) having a thickness of 75 μm using a doctor blade having a gap of 50 μm. Next, the single-sided easy-adhesion-treated polyethylene terephthalate film coated with the resin solution is left in an oven at 130 ° C. for 5 minutes, and then allowed to cool to open a 15-μm thick film on the single-sided easy-adhesion-treated polyethylene terephthalate film. A coating film of the ring polymer hydride 1 was obtained.

[Example 2]
In Example 1, the amount of 4,5-epoxytricyclo [5.2.1.0 ^2,6 ] dec-8-ene used was 2.5 parts, and the amount of 1-hexene used was 0.142 parts. In addition, the amount of toluene used was changed to 92.2 parts, and 0.0144 part of benzylidene (1,3-dimesitymimidazolidine-2-ylidene) (tricyclohexylphosphine) ruthenium dichloride was used as a metathesis polymerization catalyst. .Round-opening polymer hydride 2 and ring-opening polymer hydride on single-sided easy-adhesion-treated polyethylene terephthalate film, except that a catalyst solution dissolved in 25 parts of toluene was used Two coatings were obtained. The obtained ring-opening polymer hydride 2 has a number average molecular weight (Mn) of 1.2 × 10 ⁴ , a weight average molecular weight (Mw) of 4.5 × 10 ⁴ , a glass transition temperature of 111 ° C., and a hydrogenation rate of 83%. These results are shown in Table 1.

Example 3
In Example 1, the amount of 4,5-epoxytricyclo [5.2.1.0 ^2,6 ] dec-8-ene used was 5.6 parts, and the amount of 1-hexene used was 0.159 parts. In addition, the amount of toluene used was changed to 105.1 parts, and 0.016 part of benzylidene (1,3-dimesitymimidazolidine-2-ylidene) (tricyclohexylphosphine) ruthenium dichloride was used as a metathesis polymerization catalyst. Except that a catalyst solution dissolved in 94 parts of toluene was used, the ring-opened polymer hydride 3 and the ring-opened polymer hydride 3 on the single-sided easily-adhesive treated polyethylene terephthalate film were the same as in Example 1. Coating film was obtained. The number average molecular weight (Mn) of the obtained ring-opening polymer hydride 3 is 1.1 × 10 ⁴ , the weight average molecular weight (Mw) is 5.0 × 10 ⁴ , the glass transition temperature is 113 ° C., and the hydrogenation rate is 80%. These results are shown in Table 1.

[Comparative Example 1]
In Example 1, 1.18 parts of 4,5-epoxytricyclo [5.2.1.0 ^2,6 ] dec-8-ene, 28.6 parts of a 70% cyclohexane solution of dicyclopentadiene, -Instead of 0.134 parts of hexene and 86.8 parts of toluene, the 70% cyclohexane solution of dicyclopentadiene was changed to 28.6 parts, 0.127 parts of 1-hexene and 77.9 parts of toluene, and a metathesis polymerization catalyst Except that a catalyst solution in which 0.0124 part of benzylidene (1,3-dimesitylimidazolidine-2-ylidene) (tricyclohexylphosphine) ruthenium dichloride was dissolved in 5.56 parts of toluene was used. In the same manner as in Example 1, the ring-opening polymer hydride 1r and the ring-opening polymer hydride 1r on the single-sided easy-adhesion-treated polyethylene terephthalate film To obtain a coating film. The number average molecular weight (Mn) of the obtained ring-opening polymer hydride 1r is 1.0 × 10 ⁴ , the weight average molecular weight (Mw) is 3.2 × 10 ⁴ , the glass transition temperature is 99 ° C., and the hydrogenation rate is It was 98%. These results are shown in Table 1.

  The cross-cut test based on JIS K5600 shown below was performed about the coating film of the ring-opening polymer hydride obtained on Examples 1-3 and Comparative Example 1 on the single-sided easy-adhesion-treated polyethylene terephthalate film. The results are shown in Table 1 below.

[Cross cut test]
From the top of the coating film of the ring-opening polymer hydride on the single-sided easy-adhesion-treated polyethylene terephthalate film, six slits were made vertically and horizontally in a grid pattern at intervals of 1 mm so as to reach the lower film. A cellophane tape was affixed thereon, then the cellophane tape was peeled off, and it was evaluated whether or not there was a part to be peeled out of 25 squares. Evaluation was performed according to the following criteria.
○: No peeling at all.
X: There is a completely peeled mass.

  From Table 1, it can be seen that the ring-opened polymer hydrides of Examples 1 to 3 are superior in adhesion to other materials as compared with the ring-opened polymer hydride of Comparative Example 1.

Claims (3)

A ring-opening polymer obtained by hydrogenating 70% or more of carbon-carbon double bonds of a ring-opening polymer obtained by ring-opening metathesis polymerization of a monomer containing a compound represented by the following formula (I) Hydride.

(R ¹ represents a substituent selected from the group consisting of a hydrocarbon group having 1 to 10 carbon atoms, a halogen atom, and a hydrocarbon group having 1 to 10 carbon atoms substituted with a halogen atom. M is 0 or more. , (6n + 6) or less, when m is 1 or more, the bonding position of R ¹ is not limited, and when m is 2 or more, R ¹ may be the same or different from each other. N represents an integer of 1 to 3.) The ring-opening polymer hydrogen according to claim 1, wherein the compound represented by the formula (I) is 4,5-epoxytricyclo [5.2.1.0 ^2,6 ] dec-8-ene. monster.   The ring-opening polymer hydride according to claim 1 or 2, wherein the monomer further contains another compound copolymerizable with the compound represented by the formula (I) by ring-opening metathesis polymerization.