CN100462373C

CN100462373C - Process for producing cycloolefin addition polymer

Info

Publication number: CN100462373C
Application number: CNB2004800237793A
Authority: CN
Inventors: 大嶋升; 海津充孝; 江幡敏; 今村孝
Original assignee: JSR Corp
Current assignee: JSR Corp
Priority date: 2003-08-20
Filing date: 2004-08-04
Publication date: 2009-02-18
Anticipated expiration: 2024-08-04
Also published as: JP4203739B2; JP2005060639A; CN1839161A

Abstract

A process for producing a cycloolefin addition polymer in which one or more cycloolefin monomers can be (co)polymerized by addition polymerization with a small palladium catalyst amount to produce a cycloolefin addition (co)polymer while attaining high catalytic activity. The process for cycloolefin addition polymer production is characterized by addition-polymerizing one or more cycloolefin monomers comprising a cycloolefin compound represented by a specific formula in the presence of a multi-component catalyst comprising (a) a palladium compound and (b) a specific phosphorus compound.

Description

The preparation method of cycloolefin addition polymer

Technical field

The present invention relates to the preparation method of cycloolefin addition polymer.Specifically, the present invention relates to carry out the addition polymerization of cycloalkene compound in the presence of the special catalyst that contains the good palladium compound of polymerization activity, preparation is applicable to the method for the cycloolefin addition polymer of optical applications etc.

Background technology

In recent years, along with lightweight, requirement small-sized, densification are more and more higher, use the optical component such as lens class, sealing material of unorganic glass in the past, and all adopted the optical clear resin to substitute now in the fields such as liquid crystal display device such as mirror backlight, light guiding plate, TFT substrate, touch pad.As this optical clear resin, the norbornylene (two ring [2.2.1] heptan-2-alkene) with feature of high-clarity, high heat resistance, low water absorbable is that addition polymer just attracts tremendous attention.

In addition, as except possessing above-mentioned characteristic, possess also that linear expansivity is little, thermal dimensional stability is good, the chemical-resistant characteristic, with other parts engage the good transparent resin of binding property, also proposed norbornylene (two ring [2.2.1] heptan-2-alkene) and had the addition polymer and the crosslinked body (with reference to patent documentation 1) thereof of the cyclenes of water-disintegrable silyl.

The addition polymer that with the norbornylene is the cyclenes of representative has used the catalyzer of transistion metal compounds such as Ni, Pd, Ti, Zr, Cr by employing, carries out cyclenes and is monomeric addition polymerization and obtain (for example, with reference to non-patent literature 1).

In addition, side chain has the addition polymer of the cyclenes based compound of polar substituent and nonpolar cyclenes based compound as except possessing good thermotolerance and transparency, also crosslinkableization is useful to improve joint binding property, dimensional stability and chemical-resistant multipolymer, as the polymerizing catalyst that obtains these multipolymers, mainly adopt single complex compound of back cycle transition metal Ni, Pd or contained the multicomponent series catalysts (with reference to patent documentation 1,2, non-patent literature 2～11) of Ni, Pd compound.

In these catalyzer, in order to omit numerous and diverse catalyzer synthesis procedure, it is the Pd catalyzer single catalysts of crossing that industrial circle in most cases adopts multicomponent more.

In addition, as the good catalyzer of polymerization activity, known to the cationic part of Pd and neutral to body use phosphine compound or amine compound, use super acids negatively charged ion (with reference to patent documentation 1,3～6, non-patent literature 12) as weak counter anion part (weak counter anion ligand).

These multicomponent series catalysts as prior art obtain by modulating following composition arbitrarily.

(catalyzer is I)

1) Pd compound

2) neutral phosphine or amine compound

3) can become the ionic compound of the cationic weak counter anion of Pd

4) organo-aluminium compound

(catalyzer is II)

1) with neutral phosphine or amine compound is the Pd compound of part

2) can become the ionic compound of the cationic weak counter anion of Pd

3) organo-aluminium compound

(catalyzer is III)

1) to have.The neutrality of Pd-C keys such as-alkyl, σ-aryl, π-allyl group is the Pd compound of part to body

2) can become the ionic compound of the cationic weak counter anion of Pd

(catalyzer is IV)

1) to body the Pd compound of part with neutrality with Pd-C keys such as σ-alkyl, σ-aryl, π-allyl groups

2) lewis acid compound

All comprise phosphine or the amine compound of giving body as neutral in these catalyzer.But, with neutrality with Pd-C keys such as σ-alkyl, σ-aryl, π-allyl groups to body be part the Pd compound since its complex compound synthetic more numerous and diverse we can say not to be suitable for industrial circle.In the past, do not know with ionic microcosmic salt and substitute this neutrality to the catalyzer as the constituent of catalyzer such as body.

In addition, adopt the neutral donor catalyst of prior art, for example, 5-the trialkoxysilyl two that has water-disintegrable silyl in varsol is encircled the polymerization of two ring [2.2.1] heptan-2-alkene (norbornylene) of [2.2.1] heptan-2-alkene and side chain unsubstituted, the then easy polymkeric substance with composition distribution that generates is separated out phenomenon in the polymerization sometimes or gonorrhoea appears in resulting polymers sometimes.Its reason is as described below, promptly because the reactivity of 5-trialkoxysilyl, two ring [2.2.1] heptan-2-alkene is higher than the reactivity of two ring [2.2.1] heptan-2-alkene, enter into polymkeric substance so react, generate the polymkeric substance that has from the higher part of the ratio of the structural unit of 5-trialkoxysilyl, two ring [2.2.1] heptan-2-alkene at most 5-trialkoxysilyl of polymerization initial stage two ring [2.2.1] heptan-2-alkene.That is to say, distribute because the structural unit of polymkeric substance has produced to form, thus the solvability in polymer solvent or with polyreaction the second half in the consistency of the polymkeric substance that generates descend.

In addition, if the structural unit from 5-trialkoxysilyl, two ring [2.2.1] heptan-2-alkene produces the composition distribution, when then utilizing water-disintegrable silyl to carry out the crosslinked body of crosslinked generation, inequality can appear in the cross-linked network in the crosslinked sometimes body, and dimensional stability can deterioration.

Therefore,, have continuously or in polymerization system, add a kind of monomer methods one by one as not producing the polymerization process that this composition distributes in fact, if but the monomeric reactivity of carrying out copolymerization have than big-difference, then be difficult to control.

Even distribute and also can prevent the method for separating out in polymerization process as producing above-mentioned composition, can exemplify the method that makes 5-trialkoxysilyl, two ring [2.2.1] heptan-2-alkene and carbonatoms carry out copolymerization at the cyclenes based compound of the alkyl more than 3 with side chain substituents, but in this case or when forming film, sheet material etc., though show flexibility, but it is big that linear expansivity becomes, and goes wrong aspect dimensional stability sometimes.In addition, form distribution in this case sometimes and can become bigger, the homogeneity of the transparency of resulting polymers or the cross-linked network when forming crosslinked body is prone to problem.

In addition, have the cyclenes based compound of ester group or oxetanyl and the polyreaction of two ring [2.2.1] heptan-2-alkene and be different from aforementioned situation with cyclenes based compound of water-disintegrable silyl, owing to have the reactivity that the reactivity of the cyclenes based compound of ester group or oxetanyl is lower than two ring [2.2.1] heptan-2-alkene, so at the ratio lower polymkeric substance of polymerization initial stage generation from the structural unit of cyclenes based compound with ester group or oxetanyl, but it is identical with the situation of the cyclenes based compound with water-disintegrable silyl that situation about distributing is formed in the generation in this polymerization, produces same problem sometimes.

Therefore, wish to find have water-disintegrable silyl, in the polyreaction of ester group or substituent cyclenes based compound of oxetanyl isopolarity and nonpolar cyclenes based compound, do not generate above-mentioned composition in fact and distribute, thereby can in the polymerization of having used varsol, not separate out or the catalyzer system of gonorrhoea phenomenon can not appear in resulting polymers.

In addition,,, then can occur painted or aspect transparency, go wrong, therefore wish to find just can carry out the higher catalyzer of polymeric polymerization activity with less catalytic amount if the Pd catalyzer is residual more in polymkeric substance because the price of Pd catalyzer is higher.

In addition, the multicomponent series catalysts that contains above-mentioned Pd compound to the patience of water, methyl alcohol etc. be higher than contain before the Ti, the multicomponent series catalysts of Zr compound in cycle, if but have oxygen when storing, then the neutral phosphine of body of giving of conduct that adds for the raising polymerization activity sometimes easily is oxidized to phosphine oxide, causes polymerization activity to descend.Particularly in the polymerization of carrying out with less catalytic amount, even exist the oxygen of trace also can cause the catalyst component difference, its influence is bigger.

Therefore, even wish to obtain to have in industrial production the oxygen of trace to be present in polymerization system, the also less catalyzer system of fluctuation appears in the quality of polymerization velocity, the polymkeric substance that generated.

Have when engaging binding property or solvent resistance, the crosslinked body of chemical-resistant cycloolefin addition polymer in preparation, usually possess to make and have the substituent cyclenes based compound of water-disintegrable silyl, ester group isopolarity and the nonpolar cyclenes based compound that become crosslinked group and carry out polyaddition reaction, preparation is as the operation of the interpolymer of crosslinked body precursor, but the interpolymer that in most cases is difficult to form from this polyaddition reaction is removed the palladium atom.Therefore, exist the residual palladium of this interpolymer more, the problem that causes optical clarity to descend.

Patent documentation 1:USP 6,455,650

Patent documentation 2:USP 3,330,815

Patent documentation 3: 5-No. 262821 communiques of Japanese patent laid-open

No. 00/20472, patent documentation 4:WO

Patent documentation 5: 10-No. 130323 communiques of Japanese patent laid-open

Patent documentation 6: the Japanese Patent spy opens communique 2001-No. 98035

Non-patent literature 1:Christoph Janiak, Paul G.Lassahn, Macromol.RapidCommun.22, p479 (2001)

Non-patent literature 2:R.G.Schultz, Polym.Lett.VOL.4, p541 (1996)

Non-patent literature 3:Stefan Breunig, Wilhelm Risse, Markromol.Chem.193,2915 (1992)

Non-patent literature 4:Adam L.Safir, Bruce M.Novak Macromolecules, 28,5396 (1995)

Macromolecules such as non-patent literature 5:Joice P.Mathew, 29,2755-2763 (1996)

Macromol.Rapid Commun.17 such as non-patent literature 6:Annette Reinmuth, 173-180 (1996)

Non-patent literature 7:B.S.Heinz, Acta Polymer 48,385 (1997)

Macromol.Rapid Commun.19 such as non-patent literature 8:B.S.Heinz, 251 (1998)

J.Polym.Sci.Part B such as non-patent literature 9:Nicole R.Grove, 37,3003 (1999)

Organometallics such as non-patent literature 10:April D.Hennis, 20,2802 (2001)

J.Polym.Sci.Part A Polym.Chem.41 such as non-patent literature 11:Seung UK Son, 76 (2003)

Macromolecules such as non-patent literature 12:John Lipian, 35,8969-8977 (2002)

The present invention is the invention of In view of the foregoing finishing, and its problem provides just can carry out cyclenes with less palladium catalyst amount and be monomeric addition polymerization (copolymerization), can prepare the preparation method that cyclenes is the cycloolefin addition polymer of addition polymerization (copolymerization) thing by high reactivity.

In addition, when problem of the present invention provides the polymerization of the monomer composition that has carried out comprising specific cyclenes based compound and had the substituent cyclenes based compound of water-disintegrable silyl isopolarity, from the structural unit of the cyclenes based compound preparation method of cycloolefin addition polymer of catalyzer of high polymerization activity that do not had use that forming distributes generates in fact with polar substituent.

In addition, the present invention also is provided in cyclenes based compound (being total to) polymerization, even exist the oxygen of trace also little to the influence of polymerization activity, when comprising monomer and carrying out (being total to) polymerization, used the preparation method of cycloolefin addition polymer of the catalyzer of the novelty of can high reactivity carrying out addition polymerization (copolymerization) with the substituent cyclenes based compound of water-disintegrable silyl isopolarity.

The announcement of invention

The preparation method's of cycloolefin addition polymer of the present invention feature is in the presence of the multicomponent series catalysts, to comprise following general formula (1)

The cyclenes of the cyclenes based compound of expression is monomeric addition polymerization, in the formula (1), and A ¹～A ⁴Be the atom or the group of the alkyl, the cycloalkyl that are selected from hydrogen atom, halogen atom, carbonatoms 1～15, aryl, ester group, oxetanyl, alkoxyl group, trialkylsilkl, hydroxyl independently of one another, they can be by carbonatoms 1～20 alkylidene group, binding group and the ring structure that comprises the carbonatoms 0～10 of at least a kind of atom that is selected from Sauerstoffatom, nitrogen-atoms and sulphur atom link, in addition, A ¹And A ²Can form the heterocycle of the alicyclic ring of the replacement of alkylidene group, carbonatoms 5～20 of carbonatoms 1～5 or non-replacement or aromatic ring, carbonatoms 2～20, A ¹And A ³Can form the heterocycle of the alicyclic ring of the replacement of carbonatoms 5～20 or non-replacement or aromatic ring, carbonatoms 2～20, m is 0 or 1;

Described multicomponent series catalysts comprises

(a) palladium compound,

(b) be selected from the phosphorus compound more than a kind of following (b-1), (b-2),

(b-1) microcosmic salt of general formula (b1) expression,

[PR ²R ³R ⁴R ⁵] ⁺[CA ₁] ^-……(b1)

In the general formula (b1), P is a phosphorus atom, R ²Be the substituting group of the alkyl that is selected from hydrogen atom, carbonatoms 1～20, cycloalkyl, aryl, R ³～R ⁵Be alkyl, the cycloalkyl that is selected from carbonatoms 1～20, the substituting group of aryl, [CA independently of one another ₁] ^-For being selected from carboxylate anion, sulfonic acid anion or containing the atom that is selected from B, P or Sb and the anionic counter anion of super acids of F atom,

(b-2) cone angle (θ deg) is 170～200 the phosphine compound and the addition complex of organo-aluminium compound, and this phosphine compound has the substituting group of the alkyl, cycloalkyl and the aryl that are selected from carbonatoms 3～15.

There are following 2 kinds of forms preferably in the preparation method of cycloolefin addition polymer of the present invention.

1. the multicomponent series catalysts is for comprising (a) palladium compound, and (b-1) Biao Shi phosphorus compound (c) is selected from the form of the compound of ionic boron compound, ionic aluminum compound, lewis acidity aluminum compound and lewis acidity boron compound.

2. the multicomponent series catalysts is for comprising (a) palladium compound, (b-2) Biao Shi phosphorus compound and (d) form of organo-aluminium compound.

The content that is preferably the organo-aluminium compound (d) in above-mentioned 2 is 0.1～200 mole corresponding to palladium 1 grammeatom of palladium compound (a).

In the manufacture method of cycloolefin addition polymer of the present invention, be preferably aforementioned palladium compound (a) and be the organic carboxylate of palladium or β-dione compounds.

In the manufacture method of cycloolefin addition polymer of the present invention, be preferably the multicomponent series catalysts at the catalyzer that exists modulated to get that is selected from least a kind of compound with the two ring polycyclic monoolefines of [2.2.1] heptan-2-alkene structures or non-conjugated diene, monocycle shape non-conjugated diene and straight chain shape non-conjugated diene.

In the manufacture method of cycloolefin addition polymer of the present invention, be preferably the multicomponent series catalysts for two the ring [2.2.1] heptan-2-alkene and/or have the carbonatoms 1～15 more than 1 alkyl two the ring [2.2.1] heptan-2-ene derivatives the catalyzer that exists modulated to get.

In the manufacture method of cycloolefin addition polymer of the present invention, being preferably cyclenes is the cyclenes based compound that monomer comprises following general formula (2)-1 or (2)-2 expression,

In formula (2)-1 and the formula (2)-2, R ¹, R ²Be the substituting group of the alkyl, cycloalkyl or the aryl that are selected from carbonatoms 1～10, X is the alkoxyl group or the halogen atom of carbonatoms 1～5, and Y is the residue of hydroxyl of the aliphatic diol of carbonatoms 2～4, and k is 0～2 integer, and n is 0 or 1.

Among the preparation method of the cycloolefin addition polymer of the invention described above, the cyclenes based compound that is preferably the expression of aforementioned formula (2)-1 and/or general formula (2)-2 is at cyclenes to be the ratio use that total accounts for 0.1～30 mole of % in the monomer total amount.

Among the preparation method of cycloolefin addition polymer of the present invention, be preferably the A in the aforementioned formula (1) ¹～A ⁴Be monomer being to account for 50 moles of ratios more than the % in the monomer total amount to use at cyclenes for the cyclenes of the alkyl of hydrogen atom or carbonatoms 1～15 independently of one another.

The application requires No. 2003-296507, the special hope of Japanese Patent and special right of priority of being willing to 2004-No. 23576, quotes above-mentioned application by reference.

The best mode that carries out an invention

Among the preparation method of cycloolefin addition polymer of the present invention, adopting the multicomponent series catalysts that comprises palladium compound (a) and specific phosphorus compound (b) to carry out cyclenes is monomeric addition polymerization.

(multicomponent series catalysts)

The used multicomponent series catalysts of the present invention comprises

(a) palladium compound,

(b-1) microcosmic salt of general formula (b1) expression,

[PR ²R ³R ⁴R ⁵] ⁺[CA ₁] ^-……(b1)

(b-2) cone angle (θ deg) is 170～200 the phosphine compound and the addition complex of organo-aluminium compound, and this phosphine compound has the substituting group of the alkyl, cycloalkyl and the aryl that are selected from carbonatoms 3～15.This multicomponent series catalysts of the present invention also comprises (c) as required and is selected from the compound of ionic boron compound, ionic aluminum compound, lewis acidity aluminum compound and lewis acidity boron compound and/or (d) organo-aluminium compound.

Below, each composition of the used multicomponent series catalysts of the present invention is described.

(a) palladium compound

Palladium compound (a) can exemplify organic carboxylate, organic phosphite, organophosphate, organic sulfonate, β-dione compounds, halogenide of palladium etc., wherein, the organic carboxylate of palladium or β-dione compounds are owing to be soluble in varsol, and polymerization activity is higher, so more satisfactory.

Can exemplify the acetate of palladium as the concrete example of these compounds, propionic salt, maleate, fumarate, butyrates, adipate, 2-thylhexoic acid salt, naphthenate, oleate, lauroleate, neodecanoic acid, 1,2-cyclohexane dicarboxylic acid salt, two rings [2,2.1] heptan-5-alkene-2-carboxylate salt, 5-norbornylene-2-carboxylate salt, benzoate, phthalate, terephthalate, the organic carboxylate of palladiums such as naphthoate, the triphenyl phosphine complex compound of acid chloride, three (tolyl) phosphine complex compound of acid chloride, the complex compound of the organic carboxyl acid of palladiums such as the tricyclohexyl phosphine complex compound of acid chloride, the dibutyl phosphite of palladium, dibutylphosphoric acid salt, dioctylphosphate, phosphites such as dibutyl phosphate salt, phosphoric acid salt, the lauryl benzene sulfonate of palladium, the organic sulfonate of palladiums such as tosilate, two (methyl ethyl diketone) palladium, two (hexafluoroacetylacetone) palladium, two (ethylacetoacetone(EAA,HEAA)) palladium, β-the dione compounds of palladiums such as two (phenyl methyl ethyl diketone) palladium, dichloro two (triphenylphosphine) palladium, dichloro two [three (tolylphosphine)] palladium, dibromo two [three (tolylphosphine)] palladium, dichloro two [three (m-xylene base phosphine)] palladium, dibromo two [three (m-xylene base phosphine)] palladium, [C ₃H ₅N ₂] ₂[PdCl ₄] expression imidazol complex, [Ph ₃PCH ₂C (O) CH ₃] ₂[Pd ₂Cl ₆] the halogenation complex compound etc. of palladiums such as acetonyl triphenyl phosphorus complex compound of expression.In addition, can exemplify also that specific phosphine compound in above-mentioned (b-2) of the present invention expression makes up with halogenide such as aroyl chloride, Benzoyl chloride, bromobenzene, chlorobenzene, bromonaphthalenes down and the palladium compound of 0 valency of formation aryl or halogenation Allylpalladium, for example dibenzylideneacetonepalladium palladium [Pd ₂(dba) ₃], four [triphenyl phosphine] palladium [Pd (P (Ph ₃)) ₄] etc.

Among the present invention,, also can use the compound of following general formula (a1) expression as palladium compound (a),

Pd(R)(X)……(a1)

In the formula (a1), R represents to be selected from the negatively charged ion of organic carboxyl acid, organic sulfonic acid, organic phosphoric acid, list or bisphosphate, organic phosphorous acid and the β-diketone of carbonatoms 1～20, and X represents halogen atom.

Compound concrete example to above-mentioned general formula (a1) expression is not particularly limited, and can exemplify the II valency halogenation palladium compounds such as Palladous chloride, chlorination lauryl Phenylsulfonic acid palladium, chlorination tosic acid palladium, acetyl chloride acetone palladium of chlorination acid chloride, chlorination 2-thylhexoic acid palladium, chlorination naphthenic acid palladium, chlorination oleic acid palladium, chlorination lauric acid palladium, chlorination neodecanoic acid palladium, chlorination dibutyl phosphorous acid palladium, chlorination dibutylphosphoric acid palladium, dibutyl phosphate.

(b) phosphorus compound

As phosphorus compound (b), can exemplify the phosphorus compound more than a kind that is selected from following (b-1), (b-2).

(b-1) microcosmic salt of general formula (b1) expression,

[PR ²R ³R ⁴R ⁵] ⁺[CA ₁] ^-……(b1)

In the general formula (b1), P is a phosphorus atom, R ²Be the substituting group of the alkyl that is selected from hydrogen atom, carbonatoms 1～20, cycloalkyl, aryl, R ³～R ⁵Be alkyl, the cycloalkyl that is selected from carbonatoms 1～20, the substituting group of aryl, [CA independently of one another ₁] ^-For being selected from carboxylate anion, sulfonic acid anion, β-diketone or containing the atom that is selected from B, P or Sb and the anionic counter anion of super acids of F atom,

Below, above-mentioned each phosphorus compound is described.

(b-1) be the microcosmic salt of above-mentioned general formula (b1) expression.Concrete example to this used microcosmic salt of the present invention is not particularly limited, can exemplify tetraphenylphosphonium four (pentafluorophenyl group) borate, thricyclohexyl phosphorus four (pentafluorophenyl group) borate, thricyclohexyl phosphorus a tetrafluoro borate, thricyclohexyl phosphorus octylate, thricyclohexyl phosphorus acetate, thricyclohexyl phosphorus trifluoro-methanyl sulfonate, thricyclohexyl phosphorus tosilate, thricyclohexyl phosphorus hexafluoroacetylacetone thing, thricyclohexyl phosphorus hexafluoro antimonate, thricyclohexyl phosphorus lauryl benzene sulfonate, triphenyl phosphorus four (pentafluorophenyl group) borate, the triphenyl phosphorus hexafluorophosphate, three (3-aminomethyl phenyl) phosphorus four (3,5-trifluoromethyl) borate, trioctylphosphine phosphorus four (3,5-trifluoromethyl) borate, trioctylphosphine phosphorus tosilate, three (o-tolyl) phosphorus four (pentafluorophenyl group) borate, three (pentafluorophenyl group) phosphorus fluoroform sulphonate, three (tertiary butyl) phosphorus fluoroform sulphonate etc.Be preferably thricyclohexyl microcosmic salt, three (pentafluorophenyl group) microcosmic salt, three (o-tolyl) microcosmic salt.

Among the present invention, by using this microcosmic salt (b-1) as phosphorus compound (b), utilize copolyreaction few multipolymer that to form distribute, so can prevent well that the significant polymer of the cycloolefin addition polymer that generates from quantizing, polymers soln is converted into the precipitation of solidifying swelling state or polymkeric substance.Therefore, the cycloolefin addition polymer of gained can be applicable to and utilize solution casting method to carry out shaping processing of film, sheet material, film etc.

(b-2) be that cone angle (θ deg) is 170～200 the phosphine compound and the addition complex of organo-aluminium compound, this phosphine compound has the substituting group of the alkyl, cycloalkyl and the aryl that are selected from carbonatoms 3～15.Among the present invention, using this specific phosphine compound as the raw material of (b-2) composition is the important techniques important document.Adopt the polymer of the cycloolefin addition polymer that other phosphine compound generates to quantize significantly, polymers soln is and solidifies the swelling state or precipitation appears in polymkeric substance sometimes, in this case, is difficult to be undertaken by solution casting method the shaping processing of film, sheet material and film.

As the used phosphine compound of the raw material of (b-2) is to be the substituent tervalent electronics phosphorus compound (tertiary phosphine compounds) of giving with alkyl, cycloalkyl or aryl.Here, the cone angle of tertiary phosphine compounds (θ deg) calculates by C.A.Tolman (Chem.Rev.Vol.77,313 (1977)), and it is with 2.28

Atoms metal and the cone angle θ of the bond distance of phosphorus atom, the model determination that forms by three substituting groups of metal and phosphorus atom.

The used taper angle theta deg of the present invention is that 170～200 phosphine compound can exemplify tricyclohexyl phosphine, di-tert-butyl-phenyl phosphine, three neo-pentyl phosphines, three (tertiary butyl) phosphine, three (pentafluorophenyl group) phosphine, three (o-tolyl) phosphine etc.In addition, can exemplify di-t-butyl-2-xenyl phosphine, di-t-butyl-2 '-dimethylamino-2-xenyl phosphine, dicyclohexyl-2-xenyl phosphine, dicyclohexyl-2 '-sec.-propyl-2-xenyl phosphine etc.

The organo-aluminium compound that uses as (b-2) raw material plays lewis acidic effect, and it is the compound that forms addition complex with above-mentioned phosphine compound, is the compound that has 1 aluminium-alkyl bond at least.This organo-aluminium compound better is a method with record in the document of utilization " three etc.; catalyzer; Vol.7, p43 (1965) " when making xanthone be coordinated in organo-aluminium compound, shift value (the △ v of the absorption spectrum of the stretching vibration of the carbonyl (C=O) of the xanthone by infrared measurement _C=0) at 50cm ^-1The organo-aluminium compound of above acidity.

This organo-aluminium compound better can exemplify methylaluminium dichloride, ethylaluminium dichloride, dichloride butyl aluminium, tri-chlorination diethyl aluminum, diethylaluminum chloride, fluoridize diethyl aluminum, bromination diethyl aluminum, chlorination dibutyl aluminium, triethyl aluminum, trimethyl aluminium, tri-butyl aluminum, three hexyl aluminium, hydrogenation dibutyl aluminium etc.Consider that from the acidity aspect less-than-ideal is alkanol alkylaluminium cpds such as ethanol diethyl aluminum, methyl alcohol diethyl aluminum, di-alcohol aluminium triethyl.

The addition complex (b-2) of above-mentioned specific phosphine compound and the organo-aluminium compound normally ratio of components of phosphine compound and organo-aluminium compound is the complex compound of 1:1 with the molar ratio computing.This addition complex is for example by making 1～10 mole organoaluminum and 1 mole specific phosphine compound reaction form in 0～100 ℃ temperature range.When forming complex compound, for 1 mole specific phosphine compound, 1.0 moles organo-aluminium compound is just enough, and superfluous organo-aluminium compound plays the effect as (d) organoaluminum of catalyst aid composition described later.

Among the present invention, when having used this addition complex (b-2), compare with the phosphine compound that does not form complex compound as phosphorus compound (b), corresponding to the oxidation-resistance increase of oxygen, even also very stable with the solution state preservation for a long time, so more satisfactory.In addition, when having used this addition complex (b-2), even exist oxygen also can reduce the decline degree of polymerization activity in the polymerization system, so more satisfactory.

(c) be selected from ionic boron compound, ionic aluminum compound, lewis acidity aluminum compound and Louis The compound of this acid boron compound

When using the phosphorus compound of (b-1) as above-mentioned (b) composition in the used multicomponent series catalysts of the present invention, particularly preferably comprise the compound that (c) is selected from ionic boron compound, ionic aluminum compound, lewis acidity aluminum compound and lewis acidity boron compound.

Ionic boron compound can exemplify triphenylcarbenium four (pentafluorophenyl group) borate, triphenylcarbenium four [3,5-two (trifluoromethyl) phenyl] borate, triphenylcarbenium four (2,4,6-trifluorophenyl) borate, triphenylcarbenium tetraphenyl borate salts, tributyl four (pentafluorophenyl group) ammonium borate, N, N-xylidine four (pentafluorophenyl group) borate, N, N-Diethyl Aniline four (pentafluorophenyl group) borate, N, N-phenylbenzene aniline four (pentafluorophenyl group) borate, four (pentafluorophenyl group) lithium tetraborate etc.

Ionic aluminum compound can exemplify triphenylcarbenium four (pentafluorophenyl group) aluminate, triphenylcarbenium four [3,5-two (trifluoromethyl) phenyl] aluminate, triphenylcarbenium four (2,4,6-trifluorophenyl) aluminate, triphenylcarbenium tetraphenyl aluminate etc.

Louis's property aluminum compound can exemplify aluminum trifluoride ether complexes, difluoro aluminium triethyl, difluoroethoxy aluminium, three (pentafluorophenyl group) aluminium, three (3,5-difluorophenyl) aluminium, three (3,5-two (trifluoromethyl) phenyl) aluminium etc.

The lewis acidity boron compound can exemplify three (pentafluorophenyl group) boron, three (3,5-difluorophenyl) boron, three (3,5-two (trifluoromethyl) phenyl) boron, boron trifluoride ether complexes etc.

In these (c) compositions of the present invention, consider that from the polymerization activity aspect best is ionic boron compound.

(d) organo-aluminium compound

When the used multicomponent series catalysts of the present invention used phosphine compound conduct (b) composition of above-mentioned (b-2), special good was to contain (d) organo-aluminium compound as catalyst aid.

(d) organo-aluminium compound is the aluminum compound with at least 1 aluminium-alkyl, for example can use alkylaluminoxane compounds such as methylaluminoxane (alumoxane), ethyl aikyiaiurnirsoxan beta, butyl aikyiaiurnirsoxan beta, trialkyl aluminium compounds such as trimethyl aluminium, triethyl aluminum, triisobutyl aluminium, diisobutylaluminium hydride, diethylaluminum chloride, fluoridize alkylaluminium cpd and halogenated alkyl aluminum compounds such as diethyl aluminum, tri-chlorination diethyl aluminum, ethylaluminium dichloride, or the mixture of abovementioned alkyl aluminium alkoxide compound and abovementioned alkyl aluminum compound etc.

The modulation of multicomponent series catalysts

Multicomponent series catalysts of the present invention contains above-mentioned (a) composition, (b) composition and above-mentioned (c) that use as required and/or (d) composition.Among the present invention, though be not particularly limited, above-mentioned each catalyst component preferably is used with the consumption in the following ranges.

(a) palladium compound-as be monomer corresponding to 1 mole cyclenes, in the scope of 0.0005～0.05 mmole Pd atom, use, be preferably the scope of 0.001～0.05 mmole Pd atom, more preferably the scope of 0.005～0.01 mmole Pd atom.If particularly use organic carboxylate or β-dione compounds as palladium compound, can be monomer then corresponding to 1 mole of cyclenes, generally with below 0.01 milligram, be preferably 0.001～0.01 mmole Pd atom and carry out addition polymerization.

(b) specific phosphorus compound is used in 0.05～20 mole scope usually corresponding to Pd 1 grammeatom of palladium compound (a).When having used above-mentioned microcosmic salt (b-1) as (b) composition, (b-1) corresponding to Pd 1 grammeatom of palladium compound (a) usually at 0.5～20 mole, use in 0.5～5 mole the scope more fortunately.In addition, when having used above-mentioned addition complex (b-2),, in 0.1～10 mole scope, better be in 0.5～3.0 mole scope, to use usually (b-2) corresponding to Pd 1 grammeatom of palladium compound (a) as (b) composition.

Special good is to use (c) ionic boron compound etc. when adopting (b-1) as (b) composition, and can use (c) ionic boron compound etc. as required when using (b-2), when so the multicomponent series catalysts contains (c) composition, Pd 1 grammeatom corresponding to palladium compound (a), at 0.2～20 mole, better be at 0.5～10 mole, be more preferably and in 0.5～5 mole scope, use (c).

Special good is to use (d) organo-aluminium compound when adopting (b-2) as (b) composition, also can use (d) organo-aluminium compound when using (b-1) composition as required, by using organo-aluminium compound, can expect the raising of polymerization activity and catalyzer system effects such as increase for the patience of impurity such as oxygen.When the multicomponent series catalysts contained organo-aluminium compound (d), organo-aluminium compound (d) in 0.1～200 mole scope, better was to use in 0.5～200 mole scope corresponding to Pd 1 grammeatom of palladium compound (a).When particularly using above-mentioned microcosmic salt (b-1) as (b) composition, organo-aluminium compound (d) is corresponding to Pd 1 grammeatom of palladium compound (a), in 0.5～10 mole scope, use, when using above-mentioned addition complex (b-2) as (b) composition, organo-aluminium compound (d) uses in 0.5～20 mole scope corresponding to Pd 1 grammeatom of palladium compound (a).

Among the present invention, can there be the multicomponent series catalysts that contains above-mentioned each composition in the polymerization system, the modulator approach and the using method of the interpolation sequential scheduling of each catalyzer is not particularly limited.That is, being added into cyclenes after these compositions that constitute the multicomponent series catalysts can be pre-mixed is monomer, also can simultaneously or one by one these compositions be added directly in the polymerization system that cyclenes is the monomer existence.

In addition, multicomponent series catalysts of the present invention can be as mentioned above be modulated or modulate by being added into polymerization system by mixing simply, but preferably modulates in the presence of the compound that is selected from polycyclic monoolefine compound, its non-conjugated diene, monocycle shape and straight catenate conjugated diolefine and non-conjugated diene with two ring [2.2.1] heptan-2-alkene structures compounds such as (below be also referred to as) diene.Particularly as (b) composition when using above-mentioned addition complex (b-2) composition, be preferably in the modulation of carrying out catalyzer under the existence of compounds such as diene.During modulation multicomponent series catalysts, under the situation of using compounds such as diene, compounds such as these diene can use in 0.5～1000 mole scope usually corresponding to Pd 1 grammeatom of palladium compound (a).Being modulated at when carrying out under straight chain shape and/or the existence of single cyclic monoolefine compound of multicomponent series catalysts, the not enough composition of the polymerization activity of catalyzer sometimes.In addition, during being modulated at the above polyenoid of straight catenate conjugation or unconjugated alkatrienes and carrying out under existing of multicomponent series catalysts, catalyzer is insoluble to solvent or resulting polymers gelation sometimes sometimes.

Among the present invention, use polycyclic monoolefine with two ring [2.2.1] heptan-2-alkene structures as monomer, each catalyst component is imported when carrying out polymerization in the polymerization system that has this monomer to exist, can not adopt polymerization single polymerization monomer compounds such as diene in addition to carry out the modulation of multicomponent series catalysts in addition.

Spendable polycyclic monoolefine compound with two ring [2.2.1] heptan-2-alkene structures during as modulation multicomponent series catalysts can exemplify two ring [2.2.1] heptan-2-alkene, the three ring [5.2.1.0 that for example also can be used as specific monomer described later (1) and use ^2,6] last of the ten Heavenly stems-8-alkene, three the ring [6.2.1.0 ^2,7] ten---9-alkene, Fourth Ring [6.2.1.1 ^3,6.0 ^2,7] carbonatoms of 10 two-4-alkene and these compounds is that 1～15 alkyl, cycloalkyl and aryl replace body etc.

As polycyclic non-conjugated diene compound, can exemplify two ring [2.2.1] heptan-2,5-diene, three ring [5.2.1.0 with two ring [2.2.1] heptan-2-alkene structures ^2,6] last of the ten Heavenly stems-3,8-diene, Fourth Ring [6.2.1.1 ^3,6.0 ^2,7] 10 two-4,9-diene, five rings [9.2.0 ^2,10.0 ^3,8.1 ^1,11.1 ^4,7] ten five-5,12-diene, 1,4-two (2-two ring [2.2.1] heptan-5-thiazolinyls) butane, 1,4-two (2-two ring [2.2.1] heptan-5-thiazolinyls) hexane, 1,4-two (2-two ring [2.2.1] heptan-5-thiazolinyl methyl) benzene, dimethyl two (2-two ring [2.2.1] heptan-5-thiazolinyl methyl) silane, methyl three (2-two ring [2.2.1] heptan-5-thiazolinyl methyl) silane, 5-vinyl, two ring [2.2.1] heptan-2-alkene, 5-vinylidene, two ring [2.2.1] heptan-2-alkene, 5-isopropylidene, two ring [2.2.1] heptan-2-alkene etc.

As straight chain shape conjugated diene compound, can exemplify 1,3-divinyl, 2-methyl-1,3-divinyl, 2,3-dimethyl-1,3-divinyl, 2-phenyl-1,3-divinyl, 1,3-pentadiene, 1,3-hexadiene etc.

As monocycle shape conjugated diene compound, can exemplify 1,3-cyclohexadiene, 1,3-cyclooctadiene etc.

As straight chain shape non-conjugated diene compound, can exemplify 1,4-hexadiene, 1,5-hexadiene etc.

As monocycle shape non-conjugated diene compound, can exemplify 1,4-cyclohexadiene, 1,5-cyclooctadiene etc.

Consider from the polymerization activity aspect, carry out under the compound that the modulation of multicomponent series catalysts of the present invention is preferably in the polycyclic monoolefine with two ring [2.2.1] heptan-2-alkene structures that is selected from wherein, its non-conjugated diene, single cyclic non-conjugated diene compound exists.

By above-mentioned (a) and (b) and (c) that use as required, the solubleness in varsol is lower sometimes for the catalyzer that (d) composition forms, difference because of the kind of polymer solvent, when being added into polymerization and being, temporarily separate out sometimes and cause polymerization activity to descend, if but the modulation of multicomponent series catalysts of the present invention carries out, then can alleviate or eliminate the problem that this polymerization activity reduces in the presence of compounds such as diene.Think the generation of this effect be because compounds such as above-mentioned diene have modulated multicomponent series catalysts the time, between compound such as diene and catalyzer, form the cause of complex compound.In addition, when the complex compound that forms between compounds such as diene and catalyzer became the basic point of polyreaction, polymer chain extended to 2 directions during polymerization, also may obtain the wider polymkeric substance of molecular weight distribution.

As the method that has modulated multicomponent series catalysts at compounds such as diene, can exemplify a) in the presence of compounds such as above-mentioned diene, after being pre-mixed catalyst component (a) and (b) and (c) that use as required, (d) modulation catalyst, in the mixture of monomer and polymer solvent, be added into the method for this catalyzer; B) (c), the methods such as method of (d) each composition modulation catalyst of in the mixture of compounds such as monomer, polymer solvent and above-mentioned diene, adding the catalyst component (a) and (b) directly, one by one and using as required.In these methods, the interpolation of catalyst component is not particularly limited in proper order.

In addition, method as modulation multicomponent series catalysts, also can exemplify c) in the presence of the mixture of monomer and varsol, form specific phosphine compound and complex compound and form, add (c) composition of catalyst component (a) and use as required and/or (d) method of composition with behind the addition complex (b-2) of organo-aluminium compound.In this method, be used to form excessive organo-aluminium compound that the specific phosphine compound corresponding to 1 mole in the organo-aluminium compound of addition complex (b-2) surpassed 1 mole and play the effect of using as required, therefore can reduce or omit the addition of organo-aluminium compound of conduct (d) composition of last interpolation as the organo-aluminium compound of (d) composition of catalyst aid.

(cyclenes is a monomer)

Among the preparation method of cycloolefin addition polymer of the present invention, the cyclenes that contains the cyclenes based compound (hereinafter referred to as specific monomer (1)) of following general formula (1) expression is monomeric addition polymerization.

In the formula (1), A ¹～A ⁴Be the atom or the group of the alkyl, the cycloalkyl that are selected from hydrogen atom, halogen atom, carbonatoms 1～15, aryl, ester group, oxetanyl, alkoxyl group, trialkylsilkl, hydroxyl independently of one another, they can be by carbonatoms 1～20 alkylidene group, binding group and the ring structure that comprises the carbonatoms 0～10 of at least a kind of atom that is selected from Sauerstoffatom, nitrogen-atoms and sulphur atom link, in addition, A ¹And A ²Can form the heterocycle of the alicyclic ring of the replacement of alkylidene group, carbonatoms 5～20 of carbonatoms 1～5 or non-replacement or aromatic ring, carbonatoms 2～20, A ¹And A ³Can form the heterocycle of the alicyclic ring of the replacement of carbonatoms 5～20 or non-replacement or aromatic ring, carbonatoms 2～20, m is 0 or 1.

As specific monomer (1) but the following compound of concrete example illustration, but the present invention is not limited in these concrete examples.

Two ring [2.2.1] heptan-2-alkene, 5-methyl-two ring [2.2.1] heptan-2-alkene, 5-ethyl, two ring [2.2.1] heptan-2-alkene, 5-propyl group, two ring [2.2.1] heptan-2-alkene, 5-butyl, two ring [2.2.1] heptan-2-alkene, 5-(1-butenyl) two ring [2.2.1] heptan-2-alkene, 5-amyl group, two ring [2.2.1] heptan-2-alkene, 5-hexyl, two ring [2.2.1] heptan-2-alkene, 5-heptyl, two ring [2.2.1] heptan-2-alkene, 5-octyl group, two ring [2.2.1] heptan-2-alkene, 5-decyl, two ring [2.2.1] heptan-2-alkene, 5-lauryl, two ring [2.2.1] heptan-2-alkene, 5-cyclohexyl-two ring [2.2.1] heptan-2-alkene, 5-vinyl, two ring [2.2.1] heptan-2-alkene, 5-allyl group, two ring [2.2.1] heptan-2-alkene, 5-ethylene ring [2.2.1] heptan-2-alkene, 5-phenyl, two ring [2.2.1] heptan-2-alkene, 5,6-dimethyl, two ring [2.2.1] heptan-2-alkene, 5-methyl-6-ethyl, two ring [2.2.1] heptan-2-alkene, 5-fluorine-two ring [2.2.1] heptan-2-alkene, 5-chlorine-two ring [2.2.1] heptan-2-alkene, 5-phenmethyl-two ring [2.2.1] heptan-2-alkene, 5-indanyl-two ring [2.2.1] heptan-2-alkene, 5-trimethyl silyl-two ring [2.2.1] heptan-2-alkene, 5-triethylsilyl-two ring [2.2.1] heptan-2-alkene, 5-methoxyl group-two ring [2.2.1] heptan-2-alkene, 5-oxyethyl group-two ring [2.2.1] heptan-2-alkene, three ring [5.2.1.0 ^2,6] last of the ten Heavenly stems-8-alkene, three the ring [5.2.1.0 ^2,6] last of the ten Heavenly stems-3,8-diene, three ring [6.2.1.0 ^2,7] ten---9-alkene, Fourth Ring [6.2.1.1 ^3,6.0 ^2,7] 10 two-4-alkene, 9-methyl Fourth Ring [6.2.1.1 ^3,6.0 ^2,7] 10 two-4-alkene, 9-ethyl Fourth Ring [6.2.1.1 ^3,6.0 ^2,7] 10 two-4-alkene, two ring [2.2.1] heptan-5-alkene-2-carboxylate methyl esters, two ring [2.2.1] heptan-5-alkene-2-carboxylic acid tert-butyl esters, two ring [2.2.1] heptan-5-alkene-2,3-dicarboxylic acid methyl esters, two ring [2.2.1] heptan-5-alkene-2,3-carboxylic acid anhydride, two ring [2.2.1] heptan-5-alkene-N-cyclohexyl-2,3-carbodiimide, two ring [2.2.1] heptan-5-alkene-N-phenyl-2,3-carbodiimide, two ring [2.2.1] heptan-5-alkene-2-spiral shell-3 '-exo-succinyl oxides, two ring [2.2.1] heptan-5-alkene-2-methyl carboxylic acids methyl esters-2-carboxylate methyl esters, two ring [2.2.1] heptan-5-alkene-2-spiral shell-butyrolactone, two ring [2.2.1] heptan-5-alkene-2-spiral shell-N-cyclohexyl-succinimides, two ring [2.2.1] heptan-5-alkene-2-spiral shell-N-phenyl-succinimides, Fourth Ring [6.2.1.1 ^3,6.0 ^2,7] 10 two-9-alkene-4-carboxylate methyl ester, 4-methyl Fourth Ring [6.2.1.1 ^3,6.0 ^2,7] 10 two-9-alkene-4-carboxylate methyl ester, 5-[(3-ethyl-3-oxetanyl) methoxyl group], two ring [2.2.1] heptan-2-alkene, 5-[(3-oxetanyl) methoxyl groups] two encircle [2.2.1] heptan-2-alkene, spiral shell-5-(3-oxetanyl) two ring [2.2.1] heptan-2-alkene, two encircle [2.2.1] heptan-5-alkene-2-carboxylic acid (3-ethyl-3-oxetanyl) methyl esters.

This specific monomer (1) can a kind be used separately, also can be used in combination more than 2 kinds.

Among the present invention, be monomer, be preferably the A in the aforementioned formula (1) as cyclenes ¹～A ⁴Independently of one another for the specific monomer (1) of the alkyl of hydrogen atom or carbonatoms 1～15 being to account for 50 moles of ratios more than the % in the monomer total amount to use at cyclenes.

Among the present invention, cyclenes is that monomer is more preferably except specific monomer (1), also comprises the cyclenes based compound (hereinafter referred to as specific monomer (2)) of following general formula (2)-1 and/or following general formula (2)-2 expression.When having used the cyclenes that contains specific monomer (2) to be monomer, also can give the gained cycloolefin addition polymer with bridging property.That is, the cyclenes that contains specific monomer (2) by use is a monomer, can import water-disintegrable silyl in the molecule of cycloolefin addition polymer, and this water-disintegrable silyl works as the cross-linking part of utilizing siloxane bond.In addition, this water-disintegrable silyl is also as working with other components bonding adherent position, so can expect to help cycloolefin addition polymer and the fusible raising of engaging of other parts.

As the concrete example of the specific monomer (2) of above-mentioned general formula (2)-1 and (2)-2 expression, but the following compound of illustration, but the present invention is not limited to these concrete examples.

Specific monomer (2) as general formula (2)-1 expression for example can exemplify following compound.

5-trimethoxysilyl-two ring [2.2.1] heptan-2-alkene, 5-triethoxysilyl-two ring [2.2.1] heptan-2-alkene, 5-methyl dimethoxy oxygen base silyl-two ring [2.2.1] heptan-2-alkene, 5-methyl diethoxy silyl-two ring [2.2.1] heptan-2-alkene, 5-methyl dichloro silyl-two ring [2.2.1] heptan-2-alkene, 9-trimethoxysilyl-Fourth Ring [6.2.1.1 ^3,6.0 ^2,7] 10 two-4-alkene, 9-triethoxysilyl-Fourth Ring [6.2.1.1 ^3,6.0 ^2,7] 10 two-4-alkene, 9-methyl dimethoxy oxygen base silyl-Fourth Ring [6.2.1.1 ^3,6.0 ^2,7] 10 two-4-alkene, 9-ethyl dimethoxy silyl-Fourth Ring [6.2.1.1 ^3,6.0 ^2,7] 10 two-4-alkene, 9-cyclohexyl dimethoxy silyl-Fourth Ring [6.2.1.1 ^3,6.0 ^2,7] 10 two-4-alkene, 9-phenyl dimethoxy silyl-Fourth Ring [6.2.1.1 ^3,6.0 ^2,7] 10 two-4-alkene, 9-dimethylmethoxysilylgroups groups-Fourth Ring [6.2.1.1 ^3,6.0 ^2,7] 10 two-4-alkene, 9-Trichloromonosilane base-Fourth Ring [6.2.1.1 ^3,6.0 ^2,7] 10 two-4-alkene, 9-dichloromethyl silyl-Fourth Ring [6.2.1.1 ^3,6.0 ^2,7] 10 two-4-alkene, 9-Chlorodimethyl silyl-Fourth Ring [6.2.1.1 ^3,6.0 ^2,7] 10 two-4-alkene, 9-chlorine dimethoxy silyl-Fourth Ring [6.2.1.1 ^3,6.0 ^2,7] 10 two-4-alkene, 9-dichloro methoxyl group silyl-Fourth Ring [6.2.1.1 ^3,6.0 ^2,7] 10 two-4-alkene, 9-chloromethyl methoxy methyl silylation-Fourth Ring [6.2.1.1 ^3,6.0 ^2,7] 10 two-4-alkene.

These compounds can a kind use separately, also can be used in combination more than 2 kinds.

In addition, the specific monomer (2) as aforementioned formula (2)-2 expression for example can exemplify following compound.

5-[1 '-methyl-2 ', 5 '-two oxa-s-1 '-sila cyclopentyl]-two ring [2.2.1] heptan-2-alkene, 5-[1 '-phenyl-2 ', 5 '-two oxa-s-1 '-sila cyclopentyl]-two ring [2.2.1] heptan-2-alkene, 9-[1 '-methyl-2 ', 5 '-two oxa-s-1 '-sila cyclopentyl]-Fourth Ring [6.2.1.1 ^3,6.0 ^2,7] 10 two-4-alkene, 9-[1 '-phenyl-2 ', 5 '-two oxa-s-1 '-sila cyclopentyl]-Fourth Ring [6.2.1.1 ^3,6.0 ^2,7] 10 two-4-alkene.

These compounds can a kind use separately, also can be used in combination more than 2 kinds.In addition, as specific monomer (2), the compound of use aforementioned formula also capable of being combined (2)-1 expression more than a kind and more than a kind of compound represented of aforementioned formula (2)-2.

In these specific monomer (2), be preferably 5-trimethoxysilyl-two ring [2.2.1] heptan-2-alkene, 5-triethoxysilyl-two ring [2.2.1] heptan-2-alkene, 5-methyl dimethoxy oxygen base silyl-two ring [2.2.1] heptan-2-alkene, 9-trimethoxysilyl-Fourth Ring [6.2.1.1 ^3,6.0 ^2,7] 10 two-4-alkene, 9-methyl dimethoxy oxygen base silyl-Fourth Ring [6.2.1.1 ^3,6.0 ^2,7] 10 two-4-alkene, 9-triethoxysilyl-Fourth Ring [6.2.1.1 ^3,6.0 ^2,7] 10 two-4-alkene, 5-[1 '-methyl-2 ', 6 '-two oxa-s-4 ', 4 '-dimethyl-1 '-sila cyclohexyl]-two ring [2.2.1] heptan-2-alkene, 5-[1,-methyl-2 ', 6 '-two oxa-s-4 '-methyl-1 '-sila cyclohexyl]-two ring [2.2.1] heptan-2-alkene.

Among the present invention, consumption to specific monomer (1) and specific monomer (2) is not particularly limited, as long as suitably select according to the desired characteristic of resulting polymers, but the usage ratio of common specific monomer (1) corresponding to the monomer total amount at 50 moles more than the %.In addition, the usage ratio of specific monomer (2) is 0.1～30 mole of % corresponding to the monomer total amount usually.

Among the present invention, be preferably and be used in combination specific monomer (1) and specific monomer (2), in this case, the total of specific monomer (1) and specific monomer (2) generally reaches 80 moles more than the % corresponding to the monomer total amount, their ratio [(1)/(2)] converts with mole and is generally 70～99.8/30～0.2, be preferably 80～97/20～3, more preferably 85～95/15～5.Use with aforementioned proportion, except improving engaging binding property and can suppressing in fact suction (wet) is out of shape of resulting polymers and other material, also can make being cross-linked to form of particular polarity group that is used to from specific monomer (2) become easy, and the linear expansivity that makes the crosslinked body of gained becomes extremely low, so more satisfactory.

Among the present invention, cyclenes is when containing specific monomer (2) in the monomer, is preferably specific monomer (2) to account for the ratio use that cyclenes is 0.1～30 mole of % of monomer total amount, is more preferably 2～30 moles of %, further is more preferably 5～20 moles of %.

When having used the cyclenes that comprises specific monomer (2) with above-mentioned amount to be monomer, because multipolymer forms the cycloolefin addition polymer that contains water-disintegrable silyl, institute is so that during the crosslinked membranization of gained addition polymer, can form anti-solvent chemical resistant properties, heat-shrinkable little possess the fusible film of joint, therefore more satisfactory.In addition, cyclenes be in the monomer specific monomer (2) if ratio surpass 30 moles of %, then the water-absorbent of the polymerization activity addition polymer that can descend or generate can increase and causes suction and be out of shape sometimes.

In addition, have the alkyl of carbonatoms 3～15 or the compound of alkenyl as specific monomer (1) if use, then the linear expansivity of the crosslinked body of the alkene unsaturated link(age) hydrogenation of resulting polymers or resulting polymers and the crosslinked acquisition of hydrogenated products that forms has the tendency of increase, can go wrong on the purposes that thermal distortion is had strict demand sometimes.Specific monomer (2) also is so, if use the compound of the alkyl with carbonatoms 3～15, then the linear expansivity of the crosslinked body of the crosslinked acquisition of resulting polymers has the tendency of increase, can go wrong on the purposes that thermal distortion is had strict demand sometimes.

Among the present invention, can also and with can with the monomer (hereinafter referred to as co-polymerized monomer) of above-mentioned specific monomer (1) or (2) copolymerization.This monomeric concrete example can exemplify cyclenes such as cyclopentenes, tetrahydrobenzene, suberene, cyclooctene, cyclic diene such as cyclopentadiene, cyclohexadiene or their alkyl-substituted derivative etc.The consumption of these co-polymerized monomers can be done suitably to select according to the desired characteristic of resulting polymers, is 0～50 mole of % corresponding to the monomer total amount usually, more preferably 0～20 mole of %.

Used under the situation of cyclic diene, for prevent resulting polymers because of heat or light cause painted, preferably alkene unsaturated link(age) remaining after the polymerization is carried out hydrogen treatment.In addition, hydrogenation ratio is high more good more, usually more than 90%.

As being not particularly limited, cyclenes is that monomer does not preferably comprise specific monomer (1) and specific monomer (2) monomer in addition among the present invention.

(preparation of cycloolefin addition polymer)

Addition polymerization

Among the preparation method of the present invention, in the presence of the multicomponent series catalysts that forms by mentioned component, above-mentioned monomer is carried out addition polymerization.

Among the present invention, except the multicomponent series catalysts that forms by mentioned component, also can with specific olefin(e) compound, then can expect the raising of polymerization activity by also also with specific olefin(e) compound.As the concrete example of this specific olefin(e) compound, can exemplify ethene, vinylchlorid, vinyl-acetic ester and acrylate etc., wherein be preferably ethene.These specific olefin(e) compounds can use in 1～10000 mole scope corresponding to Pd 1 grammeatom of palladium compound (a).

Addition polymerization of the present invention is carried out in polymer solvent usually.Among the present invention, as the solvent that can be used for addition polymerization, can exemplify ester ring type varsols such as hexanaphthene, pentamethylene, methylcyclopentane, aliphatic hydrocarbon kind solvents such as hexane, heptane, octane, aromatic hydrocarbon solvents such as toluene, benzene, dimethylbenzene, ethylbenzene, Lay, methylene dichloride, 1,2-ethylene dichloride, 1, halon solvents such as 1-ethylene dichloride, tetrachloroethane, chlorobenzene, dichlorobenzene etc. if use non-halogen solvent, then help environment.Among the present invention, these solvents can use separately also can mix use more than 2 kinds.

In the addition polymerization among the present invention, polymerization temperature is generally-20～120 ℃, is preferably 20～100 ℃, and temperature can change in time to some extent.

Among the present invention, the mode that can adopt the mode that monomer is once all added also can adopt to add one by one etc.If when using the monomer more than 2 kinds, then can the multipolymer that generate can be controlled to be the random copolymers that does not have the composition distribution and form the multipolymer that distributes according to the difference and the monomeric adding method of copolyreaction to having.In addition, can adopt the intermittence type polymerization mode as polymerization methods or utilize in the successive polymerization mode of tank reactor, tower reactor or tube-type reactor etc. any.

Among the present invention,, form the structural unit of following general formula (3) expression by being that monomer carries out addition polymerization to the cyclenes that contains above-mentioned specific monomer (1).The structural unit of general formula (3) expression also can form by the polymkeric substance that generates is carried out hydrogenation after addition polymerization as described later.

In the formula (3), A ¹～A ⁴And m is identical with the definition in the general formula (1).

In addition, monomer contains above-mentioned specific monomer (2)-1 and/or (2)-2 o'clock, by the addition polymerization of specific monomer (1) and specific monomer (2), except that the structural unit of general formula (3) expression, also forms the structural unit of general formula (4)-1 or (4)-2 expression.

In formula (4)-1 and the formula (4)-2, R ¹, R ², X, Y, k and n be identical with the definition in formula (2)-1 and the formula (2)-2.

Among the present invention, addition polymerization is stopped, can in polymers soln, adding the compound that is selected from organic carboxyl acid compound, alkylol cpd, primary～tertiary amine compound, hydroxylamine compound, ammonia, hydrogen, allyl halide, halogenation methyl aryl compound, tertiary alkyl halogenide, etheride, has a silane compound etc. of Si-H key polymerization is stopped.

Among the present invention, for example adopt alkene such as ethene, propylene, 1-butylene, 1-hexene, trimethyl silyl ethene, trimethoxy ethene, triethoxy ethene, vinylbenzene, silane compounds such as cyclopentenes, cyclohexadiene, triethyl silicane, diethylsilane, phenyl silane, diphenyl silane, Virahol, water, hydrogen etc. carry out the control of the molecular weight of cycloolefin addition polymer, because ethene can control molecular weight on a small quantity, and it is can not exert an influence, so more satisfactory to polymerization activity.

Hydrogenation

Among the present invention, used the situation of specific monomer (1) etc. with alkene unsaturated link(age), exist in the gained addition polymer under the situation of alkene unsaturated link(age), because the painted or gelation meeting that heat or photoconduction cause causes deterioration, so preferably this alkene unsaturated link(age) is carried out hydrogen treatment.Hydrogenation ratio is high more good more, usually more than 90%, is preferably more than 95%, more preferably more than 99%.

Method for hydrogenation is not particularly limited, can adopts and common the alkene unsaturated link(age) is carried out the hydrogenant method carry out.General in the presence of hydrogenation catalyst, in inert solvent, carry out hydrogenation with the hydrogen pressure of 0.5～15MPa and 0～200 ℃ temperature of reaction.When having aromatic ring (aryl) in the polymkeric substance, this aromatic ring is more stable to heat or light ratio, and is helpful to optical characteristics or thermotolerance sometimes, so might not be hydrogenated.Must be according to desirable characteristic, the condition of selecting this aromatic ring not to be hydrogenated in fact.

As the inert solvent that can be used for hydrogenation, can exemplify the aliphatic hydrocarbon of carbonatomss 5～14 such as hexane, heptane, octane, dodecane, the clicyclic hydrocarbon of carbonatomss 5～14 such as hexanaphthene, suberane, cyclodecane, methylcyclohexane, when under the unhydrided condition of aromatic ring, carrying out hydrogenation, also can use the aromatic hydrocarbons of carbonatomss 6～14 such as benzene,toluene,xylene, ethylbenzene.

As hydrogenation catalyst, the solid catalyst that can adopt VIII family metals such as nickel, palladium, platinum, cobalt, ruthenium, rhodium or its compound to be supported at porous carriers such as carbon, aluminum oxide, silicon-dioxide, sial, diatomite and form, perhaps organic carboxylate, β-dione compounds and the organoaluminum of IV family～VIII families such as cobalt, nickel, palladium or the combination of organolithium, or the homogeneous catalysts such as complex compound of ruthenium, rhodium, iridium etc.

Remove catalyzer

Among the preparation method of the present invention, the used catalyzer of hydrogenation that is used for the catalyzer of polyreaction and enforcement as required is preferably in except that being removed in the catalyzer operation.Be not particularly limited being used for this method of removing the catalyzer operation, can do suitably to select according to the proterties or the shape of used catalyzer.

Among the present invention, stop polymerization, the solution of resulting polymers or its hydrogenated products is removed catalyzer by handling with the aqueous solution of hydroxycarboxylic acids such as lactic acid, oxyacetic acid, β-methyl-β-hydroxy-propionic acid, γ-hydroxybutyric acid or trolamine, dialkyl group thanomin, edetate etc. or handling with sorbent materials such as diatomite, silicon-dioxide, aluminum oxide, gacs.

Then, desolventize by directly steaming from the solution of having removed catalyzer, perhaps solidify dryly with alcohols such as methyl alcohol, ethanol, propyl alcohol or ketone such as acetone, ethyl methyl ketone again, acquisition is as the cycloolefin addition polymer of purpose product.

Reclaim

Among the preparation method of the present invention, through polymerization or remove operation such as catalyzer and the cycloolefin addition polymer that makes can pass through known method, for example adopt means such as heating or decompression from the solution that contains this polymkeric substance, directly to remove the method for desolvating, the lean solvent that perhaps will contain the solution of this polymkeric substance and this polymkeric substance such as alcohol or ketone mixes, and solidifies the method for separating this polymkeric substance etc. and is recovered.In addition, directly adopt this solution, utilize solution casting method (casting) that it is configured as film or sheet material also can reclaim as raw material.

(cycloolefin addition polymer)

Utilize the second-order transition temperature (Tg) of the cycloolefin addition polymer of preparation method's acquisition of the present invention to determine with amount by being used for the monomeric kind of polymeric, can do suitably to select according to the purposes that polymkeric substance is used, be generally 150～450 ℃, be preferably 180～400 ℃, more preferably 200～380 ℃.If the second-order transition temperature of this polymkeric substance less than 150 ℃, then can have problems aspect thermotolerance sometimes, on the other hand, if surpass 450 ℃, the polymkeric substance rigidity that becomes then, toughness descends, and easily breaks.

The second-order transition temperature of cycloolefin addition polymer of the present invention by the peak temperature according to the temperature dispersion of the Tan δ of Measurement of Dynamic Viscoelasticity try to achieve (storage elastic modulus: E ', loss elastic modulus: E ", Tan δ=E "/E ').

Among the present invention, the molecular weight of cycloolefin addition polymer is solvent with the orthodichlorobenzene, records by gel permeation chromatography in 120 ℃, the number-average molecular weight of polystyrene conversion (Mn) is 10000～300000, weight-average molecular weight (Mw) is 30000～500000, being preferably number-average molecular weight (Mn) is 30000～200000, and weight-average molecular weight (Mw) is 5000～300000.

Number-average molecular weight (Mn) is if less than 10000, and weight-average molecular weight (Mw) is easily broken when then forming film or sheet material sometimes less than 30000.On the other hand, if number-average molecular weight (Mn) surpasses 300000, weight-average molecular weight (Mw) surpasses 500000, and the soltion viscosity of polymkeric substance becomes too high when then utilizing solution casting method to make film or sheet material, is difficult for sometimes handling.

In the cycloolefin addition polymer of the present invention of 100 weight parts, add 0.001～5 weight part, be preferably the oxidation inhibitor that is selected from phenol system, phosphorus system, thioether system, lactone system of 0.01～5 weight part, can improve resistance to thermal deterioration.

In order to improve mechanical characteristicies such as processibility and toughness etc., ratio that can 0.1～90 weight % is mixed other cycloolefin addition polymer, addition copolymer, the crystallinity alpha-olefin polymer of the cyclenes opening polymerization polymer, α-alkene and the cyclenes that are hydrogenated in cycloolefin addition polymer of the present invention, and α-olefin copolymer more than 3 of elastomeric ethene and carbonatoms, the butadiene-based polymkeric substance that is hydrogenated, the butadiene styrene block copolymerization thing that is hydrogenated, isoprene based polymer of being hydrogenated etc.

Also can carry out crosslinked to cyclenes based polymer of the present invention.For example in the shaping of above-mentioned film, sheet material, as mentioned above the polymers soln that contains acidogenic agent or dispersion are carried out after solution casting handles, before drying process, in the process or be used in the dried operation can carry out crosslinked from external heated or rayed.

When having water-disintegrable silyl or oxetanyl in the structural unit of at least a portion of cycloolefin addition polymer of the present invention, by mixing the compound (acidogenic agent) that acid is produced in the effect that utilizes heat or light, carry out rayed or heat treated again, can form the cycloolefin addition polymer that is crosslinked.

The cycloolefin addition polymer with said structure unit (4)-1 or (4)-2 (hereinafter referred to as the polymkeric substance that contains water-disintegrable silyl) that utilizes preparation method's acquisition of the present invention is owing to have water-disintegrable silyl as side chain substituents, so, can form with the crosslinked crosslinked body of siloxane bond by being hydrolyzed and condensation under the acid existence.This crosslinked body is in film forming or when being configured as sheet material, and linear expansivity is significantly reduced, and anti-solvent chemical or anti-liquid crystal liquid crystal property are good.

Among the present invention, in containing the polymers soln of water-disintegrable silyl, mix the acidic compound of effect (acidogenic agent) that can utilize light or heat, behind solution casting method formation film or sheet material, it is crosslinked to utilize rayed or heat treated that the acid generation is carried out, and can obtain above-mentioned crosslinked body.

The used acidogenic agent of the present invention can exemplify and be selected from following 1), 2), 3) and 4) compound, preferably corresponding to the polymkeric substance that contains water-disintegrable silyl of 100 weight parts, at 0.0001～5 weight part, better be to use at least a kind of compound therefrom selecting in the scope of 0.001～5 weight part.

1) produces Brensted acid or lewis acidic compound by rayed; for example; do not replace or have an alkyl; the diazonium salt of aryl or heterocyclic radical; ammonium salt; salt compounded of iodine; sulfonium salt; microcosmic salt; counter anion is a sulfonic acid; boric acid; phosphoric acid; the salt of metaantimmonic acid or carboxylic acid; halogen-containing diazole; halogen-containing triaizine compounds; halogen-containing aceotphenone compound; halogenated organic compounds such as halogen-containing benzophenone cpd; 1; 2-benzoquinones diazido-4-sulphonate; 1; 2-naphthoquinones diazido-quinone diazido compounds such as 4-sulphonate, α, α '-two (alkylsulfonyl) diazomethane; diazomethane compounds such as α-carbonyl-α '-alkylsulfonyl diazomethane etc.

2) temperature that is heated to more than 50 ℃ can be produced the compound of acid, and for example, counter anion is for being selected from BF ₄, PF ₆, AsF ₆, SbF ₆, B (C ₆F ₅) ₄Deng the molysite etc. of aromatics sulfonium salt, aromatics ammonium salt, aromatics pyridinium salt, aromatics microcosmic salt, aromatics salt compounded of iodine, hydrazine (hydrazinium) salt or metallocenes.

3) in the presence of water or under the non-existent state of water, the temperature that is heated to more than 50 ℃ heats the compound that acid is produced in meeting, for example, ester cpds of the trialkylsilkl ester of the hemiacetal ester of the ester of the secondary alcohol of trialkyl phosphite, triarylphosphite, dialkyl phosphites, an alkyl phosphorous acid ester, phosphinate, organic carboxyl acid or the tertiary alcohol, organic carboxyl acid, organic carboxyl acid or organic sulfonic acid and the secondary alcohol or the tertiary alcohol etc.

4) metal oxides such as tin, aluminium, zinc, titanium, antimony, alkoxide cpd, phenates compound, β-dione compounds, alkylate, halogenide, organic acid salt compound.

Wherein, be preferably and be selected from 1), 2) and 3) compound, particularly 3) compound is good with the intermiscibility of the polymkeric substance that contains water-disintegrable silyl, and the storage stability when mixing the solution that comprises the polymkeric substance with water-disintegrable silyl is good, so more satisfactory.These acidogenic agents can also can be used in combination more than 2 kinds in a kind of independent use.

Cyclenes based polymer of the present invention or the manufacturing process that contains the composition of this polymkeric substance are not particularly limited, for example can behind supporting mass, make the solution casting method of solvent seasoning be configured as film, sheet material and film etc. the solution coat that forms by making the cyclenes based polymer or containing the composition dissolves of this polymkeric substance or be scattered in solvent.Utilize the shaping of solution casting method can suppress the influence of thermal hysteresis, so more satisfactory to polymkeric substance.

As utilizing this solution casting method to be configured as the concrete grammar of film, sheet material or film, can exemplify make the concentration that is modulated into regulation, as required through filtration and the solution that contains polymkeric substance that deaeration is handled after spreading on the stripper plate that rolls on roller, level and smooth the using between the roller that makes it use roller and link to each other with this roller by curtain coating, when adjusting thickness, make surface smoothingization, evaporating solvent then, remove stripper plate, make its method again by drying machine.When residual solvent is had strict demand, carry out also preferably carrying out 2 times drying 1 drying except utilizing drying machine, promptly, impregnated in lower boiling halogen solvents such as methylene dichloride, 1,2-ethylene dichloride or be exposed under its vapor atmosphere or it is contacted with water vapour, reheat to 80～220 ℃.

In addition, the crosslinked of film, sheet material or film can be by after carrying out solution casting to the polymers soln that contains acidogenic agent or dispersion as mentioned above, before drying process, in the process or be used in the dried operation carry out from external heated or rayed.

Utilize residual solvent levels in film, sheet material or the film that aforesaid method obtains below 5000ppm, be preferably below the 2000ppm, more preferably below the 1000ppm.If this residual solvent levels surpasses 5000ppm, when then in decompression system, film, sheet material or film being carried out surface treatment such as evaporation or sputter, produce a large amount of volatile components, under the pollution that causes equipment, decompression degree the degradation, the linear expansivity of film, sheet material or film is increased, cause dimensional stability to descend sometimes.

As mentioned above, cycloolefin addition polymer of the present invention better is to utilize solution casting method to form processing, if but the second-order transition temperature of polymkeric substance below 250 ℃, then can adopt injection forming or melt extrude the processing of melt-shapings such as shaping, blow molding.In addition, even the second-order transition temperature of polymkeric substance surpasses 250 ℃, be shaped or blow molding is configured as sheet material, film or film by mixing softening agent etc. or utilize solvent to make this polymkeric substance swelling, also can adopt to melt extrude.

In order further to improve the resistance to oxidation deterioration or the coloring resistance deterioration of cycloolefin addition polymer of the present invention, can be corresponding to the polymkeric substance of 100 weight parts, the phenol that is selected from that mixes 0.001～5 weight part is that oxidation inhibitor, lactone are that oxidation inhibitor, phosphorus are that oxidation inhibitor, thioether are the compound of oxidation inhibitor.

In addition, for mechanical characteristicies such as the processibility of improving cycloolefin addition polymer of the present invention and toughness, ratio that can 0.1～90 weight % is mixed other cycloolefin addition polymer, addition copolymer, the crystallinity alpha-olefin polymer of the cyclenes opening polymerization polymer, α-alkene and the cyclenes that are hydrogenated, and α-olefin copolymer more than 3 of elastomeric ethene and carbonatoms, the butadiene-based polymkeric substance that is hydrogenated, the butadiene styrene block copolymerization thing that is hydrogenated, isoprene based polymer of being hydrogenated etc.

It is electric component, medicine equipment, electrically insulating material or the wrapping material etc. of representative that the cycloolefin addition polymer that utilizes manufacture method of the present invention to obtain can be used for the optical material component.

For example, the optical recording substrate, TFT that can be used for light guiding plate, protective membrane, moveable diaphragm, phasic difference film, touch pad, transparent electrode substrate, CD, MD, DVD etc. as optical material is with substrate, color filter substrate etc. or optical lens class, sealing material etc.Can be used for container, plate rail, carrier band, barrier film, washing container, body, pipe as electric component etc.Can be used for drug container, ampoule, syringe, transfusion with bag, sample receiver, test tube, heparin tube, sterilising vessel, pipe, pipe etc. as medicine equipment.Can be used for as the insulating material of the office machines such as coating material, computer, printer and duplicating machine of the electric wire of electrically insulating material, the insulating material of printed base plate etc.Can be used for packing film as the food of wrapping material or medicine etc. etc.

Utilize the present invention, available less palladium series catalyst amount is carried out addition (being total to) polymerization with high polymerization activity to the cyclenes based compound, prepares cycloolefin addition polymer with good productivity.

Utilize the present invention, when particularly to adopt the multicomponent series catalysts comprise the specific microcosmic salt of (a) palladium compound, (b-1), (d) organo-aluminium compound to carry out cyclenes be monomeric polymerization, obtain not have in fact and form the cycloolefin addition polymer that distributes.

In addition, utilize the present invention, particularly adopt and comprise (a) palladium compound, (b-2) the specific phosphine compound and the addition complex of organo-aluminium compound, (c) the multicomponent series catalysts of ionic boron compound etc. is when to carry out cyclenes be monomeric polymerization, can carry out addition (being total to) polymerization to the cyclenes based compound with high polymerization activity, prepare cycloolefin addition polymer with good productivity, even there is the oxygen of trace in the polymerization system, influence to polymerization activity is also very little, even have polar group comprising, when the monomer composition that particularly has a cyclenes based compound of water-disintegrable silyl carries out copolymerization, also can carry out addition copolymerization with high polymerization activity.

Embodiment

Below, based on embodiment the present invention is carried out more specific description, but the present invention is not limited in these embodiment.

In addition, the randomness in molecular weight, total light transmittance, second-order transition temperature, tensile strength elongation, the copolyreaction is measured or is estimated according to following method.

(1) molecular weight

By WATERS corporate system 150C type gel permeation chromatography (GPC) device, utilize the system H of TOSOH Co., Ltd. type post, be that solvent is measured in 120 ℃ with the orthodichlorobenzene.The gained molecular weight is the polystyrene standard scaled value.

(2) total light transmittance

With ASTM-D1003 is benchmark, measures the total light transmittance of the film of the about 150 μ m of thickness.

(3) second-order transition temperature

Second-order transition temperature by according to the Tan δ of Measurement of Dynamic Viscoelasticity (storage elastic modulus E ' and loss elastic modulus E " than Tan δ=E "/E ') the peak temperature of temperature dispersion measure.The mensuration of dynamic viscoelastic adopts Rheovibron DDV-01FP (Orientec corporate system), and with the mensuration frequency of 10Hz, 4 ℃/minute heat-up rate, the vibration amplitude of the vibration modes of single waveform and 2.5 μ m is measured the peak temperature of Tan δ.

(4) linear expansivity

Adopt TMA (thermal analysis) SS6100 (Seiko instrument Co., Ltd. system), as the test shape, the diaphragm of the about 150 μ m of thickness, vertical 10mm, horizontal 10mm is upright, fixing, loading the heavy load of 1g by probe, is the thermal hysteresis of removing striping, temperature temporarily is warming up to 200 ℃ from room temperature with 5 ℃/min after, begin to heat up from room temperature with 5 ℃/min once more, try to achieve linear expansivity by the inclination angle that the diaphragm-operated between 50～150 ℃ extends.

(5) tensile strength elongation

According to JIS K7113, with the draw speed determination test sheet of 3mm/min.

(6) remaining quantity of solvent

Sample is put into 200 ℃ hotblast stove 3 hours, by the weight change determination residual solvent amount of front and back.

(7) compositional analysis of the polymkeric substance in the copolyreaction

In the copolyreaction of specific monomer (1) and specific monomer (2), in being scope below 20%, the transformation efficiency of polymkeric substance stops polymerization at monomer, with 270MHz's with Virahol ¹H-NMR (solvent: C ₆D ₆) alkoxysilyl, ester group and the oxetanyl of the polymkeric substance that measure to generate of device, obtain the content of above-mentioned group in the multipolymer of generation.

Methoxyl group uses the absorption (SiOCH of 3.5ppm ₃CH ₃), oxyethyl group adopts the absorption (SiOCH of 3.9ppm ₂CH ₃CH ₂).Methoxycarbonyl adopts absorption (C (O) OCH of 3.5ppm ₃), ethoxycarbonyl adopts absorption (C (O) OCH of 3.9ppm ₂CH ₃CH ₂).Oxetanyl uses absorption (the adjacent CH of 4 yuan of ring O atoms of 4.2-4.6ppm ₂).

¹When the characteristic absorption of H-NMR is overlapping, utilize vapor-phase chromatography that the residual monomer of polymers soln is analyzed, obtain the amount that is directed in multipolymer.

Randomness with in the polymkeric substance from the ratio (Rp) of the structural unit of specific monomer (2) and all the ratio (r) of the ratio (Rm) of the specific monomer (2) in the monomer be index.

r＝Rp/Rm

R is good more near 1 randomness more.R＜1 or r〉1 o'clock, r is poor more from 1 randomness far away more.

Embodiment 1

Toluene 30.7g, the hexanaphthene 30.7g through dehydration, 5-triethoxysilyl, two ring [2.2.1] heptan-2-alkene 79g (7.0 mmole), two ring [2.2.1] heptan-2-alkene 8.75g (93 mmole) that in the glass pressure bottle of 100ml, add moisture 6ppm.Serum cap sealing bottleneck with the band cap.Then, import the gasiform ethene of 30ml by the serum cap of pressure bottle.

Solvent and monomeric pressure bottle will be housed heat, add 2-thylhexoic acid palladium (is 0.00133 milligram-atom as the Pd atom), thricyclohexyl phosphorus pentafluorophenyl group borate 0.00133 mmole and triethyl aluminum 0.00667 mmole successively, the beginning polymerization to 75 ℃.

After polymerization began 15 minutes, system took out the polymers soln of a part from polymerization, and forming branch obtains the transformation efficiency that is formed polymkeric substance by monomer admittedly by it, and utilizes 270MHz's ¹H-NMR obtains the ratio from the structural unit of 5-triethoxysilyl two ring [2.2.1] heptan-2-alkene in the polymkeric substance.Transformation efficiency is 19%, and the ratio of encircling the structural unit of [2.2.1] heptan-2-alkene from 5-triethoxysilyl two in the polymkeric substance is 11 moles of %, and randomness index r is 1.6.

In 75 ℃ carry out 3 hours polyreaction after, polymers soln does not become turbid and is transparence.The Deanol that adds 1ml in this solution stops polymerization.Solid formation by polymers soln divides mensuration, and trying to achieve the transformation efficiency that forms polymkeric substance is 96%.

Carry out Virahol that 2 usefulness contains lactic acid water and extract the operation of residual catalyst, in 2 liters Virahol, add polymers soln, polymkeric substance is solidified from polymers soln.Solidify the drying that carried out 17 hours the back under 80 ℃ of decompressions, obtain polymer A.

Utilize 270MHz's ¹H-NMR obtains the ratio from the structural unit of 5-triethoxysilyl two ring [2.2.1] heptan-2-alkene in the polymer A.The ratio of encircling the structural unit of [2.2.1] heptan-2-alkene from 5-triethoxysilyl two is 6.7 moles of %.About molecular weight, number-average molecular weight (Mn) is 74000, and weight-average molecular weight (Mw) is 185000, and second-order transition temperature (Tg) is 360 ℃.

Embodiment 2

Except substituting thricyclohexyl phosphorus pentafluorophenyl group borate 0.00133 mmole with thricyclohexyl phosphorus-2-thylhexoic acid salt, 0.00133 mmole and triphenylcarbenium four (pentafluorophenyl group) borate 0.00133 mmole, other is operated similarly to Example 1.

The transformation efficiency that polymerization began after 12 minutes is 18%, and the ratio of encircling the structural unit of [2.2.1] heptan-2-alkene from 5-triethoxysilyl two in the polymkeric substance is 12%.Gonorrhoea does not appear in polymerization system when polymerization in 3 hours finishes, and the transformation efficiency that forms polymkeric substance is 97%.

More than the number-average molecular weight of the polymer B of Huo Deing (Mn) is 63000, and weight-average molecular weight (Mw) is 167000, and second-order transition temperature (Tg) is 365 ℃.In addition, the ratio of encircling the structural unit of [2.2.1] heptan-2-alkene from 5-triethoxysilyl two in the polymer B is 6.8 moles of %, and randomness index r is 1.7.

Embodiment 3

Except substituting two ring [2.2.1] heptan-2-alkene 93 mmoles and 5-triethoxysilyl, two ring [2.2.1] heptan-2-alkene 7 mmoles with two ring [2.2.1] heptan-2-alkene 90 mmoles, 5-trimethoxysilyl, two ring [2.2.1] heptan-2-alkene 10 mmoles, other is operated similarly to Example 1.

The transformation efficiency that polymerization began after 15 minutes is 18%, and the ratio of encircling the structural unit of [2.2.1] heptan-2-alkene from 5-trimethoxysilyl two in the polymkeric substance is 15%.Gonorrhoea does not appear in polymerization system when polymerization in 3 hours finishes, and transformation efficiency is 95%.

More than the number-average molecular weight (Mn) of the polymkeric substance C of Huo Deing is 72000, and weight-average molecular weight (Mw) is 177000, and second-order transition temperature (Tg) is 360 ℃.In addition, the ratio of encircling the structural unit of [2.2.1] heptan-2-alkene from 5-trimethoxysilyl two among the polymkeric substance C is 9.7 moles of %, and randomness index r is 1.5.

Embodiment 4

Except with 4-methyl Fourth Ring [6.2.1.1 ^3,6.0 ^2,7] 10 two-9-alkene-4-carboxylate methyl ester, 10 mmoles substitute outside 5-trimethoxysilyl, two ring [2.2.1] heptan-2-alkene 10 mmoles, other is operated similarly to Example 3.

The transformation efficiency that polymerization began after 20 minutes is 19%, in the polymkeric substance from 4-methyl Fourth Ring [6.2.1.1 ^3,6.0 ^2,7] ratio of structural unit of 10 two-9-alkene-4-carboxylate methyl ester is 6%.Gonorrhoea does not appear in polymerization system when polymerization in 3 hours finishes, and transformation efficiency is 91%.

More than the number-average molecular weight (Mn) of the polymkeric substance D of Huo Deing is 62000, and weight-average molecular weight (Mw) is 156000, and second-order transition temperature (Tg) is 360 ℃.In addition, among the polymkeric substance D from 4-methyl Fourth Ring [6.2.1.1 ^3,6.0 ^2,7] ratio of structural unit of 10 two-9-alkene-4-carboxylate methyl ester is 9.2 moles of %, randomness index r is 0.6.

Embodiment 5

Except use two ring [2.2.1] heptan-2-alkene 80 mmoles and endo body to account for 95% three ring [5.2.1.0 as monomer ^2,6] outside the last of the ten Heavenly stems-8-alkene 20 mmoles, other operation is carried out similarly to Example 2.Gc analysis by the residual monomer in the polymers soln knows, in the polymkeric substance from three ring [5.2.1.0 ^2,6] ratio of structural unit of the last of the ten Heavenly stems-8-alkene is 12 moles of %.Gonorrhoea not occurring to 3 hours copolymer solutions, is 92% to the transformation efficiency of polymkeric substance.

More than the number-average molecular weight (Mn) of the polymkeric substance E of Huo Deing is 64000, and weight-average molecular weight (Mw) is 177000, and second-order transition temperature (Tg) is 365 ℃.

Comparative example 1

Except substituting the thricyclohexyl phosphorus pentafluorophenyl group borate with tricyclohexyl phosphine, other carries out polymerization similarly to Example 1, but polymerization does not take place.

Comparative example 2

Except substituting thricyclohexyl phosphorus-2-thylhexoic acid salt with tricyclohexyl phosphine, other carries out polymerization similarly to Example 2.

The transformation efficiency that polymerization began after 12 minutes is 18%, and the ratio of encircling the structural unit of [2.2.1] heptan-2-alkene from 5-triethoxysilyl two in the polymkeric substance is 17%.Polymerization system when polymerization is carried out 1 hour begins to occur gonorrhoea, and polymerization system is the gonorrhoea shape during to 3 hours, and polymkeric substance is separated out with gel.The transformation efficiency that forms polymkeric substance is 90%.

More than the polymkeric substance F of Huo Deing is dissolved in chlorobenzene, orthodichlorobenzene.The number-average molecular weight of polymkeric substance F (Mn) is 53000, and weight-average molecular weight (Mw) is 187000, and second-order transition temperature (Tg) is 365 ℃.In addition, the ratio of encircling the structural unit of [2.2.1] heptan-2-alkene from 5-triethoxysilyl two among the polymkeric substance F is 6.8 moles of %, and randomness index r is 2.4.

Reference example 1

The 10g polymer A is dissolved in the mixed solvent of methylcyclohexane 10ml and dimethylbenzene 40ml, polymkeric substance corresponding to 100 weight parts, add respectively 0.6 weight part as four [3-(3 of oxidation inhibitor, 5-di-t-butyl-4-hydroxy phenyl) propionic acid] pentaerythritol ester and three (2,4-di-tert-butyl-phenyl) phosphorous acid ester adds tributyl phosphate as 1.4 weight parts of linking agent corresponding to the polymkeric substance of 100 weight parts.

Membrane filter with aperture 10 μ m filters this polymers soln, remove foreign matter after, on polyester film, carry out curtain coating in 25 ℃, slowly atmosphere temperature is risen to 50 ℃, the dry mixed solvent carries out membranization.

After residual solvent in film reaches 5～10 weight %, be exposed in 180 ℃ the steam 2 hours, make film form crosslinked body.This film is exposed in the methylene dichloride vapor atmosphere 30 minutes in 25 ℃, removes residual solvent.Then,, remove methylene dichloride, make the crosslinked film A-1 of process of thick 150 μ m in 80 ℃ of vacuum-dryings of carrying out 30 minutes.The residual solvent amount of gained film A-1 is below 0.3 weight %.Evaluation result is shown in table 1.

Reference example 2

Except with the polymer B replace polymeric A, other is same with reference example 1, obtains to pass through the film B-1 of crosslinked thick 150 μ m.The residual solvent amount of gained film B-1 is below 0.3 weight %.Evaluation result is shown in table 1.

Reference example 3

Except with the polymkeric substance C replace polymeric A, other is same with reference example 1, obtains to pass through the film C-1 of crosslinked thick 150 μ m.The residual solvent amount of gained film C-1 is below 0.3 weight %.Evaluation result is shown in table 1.

Reference example 4

Except with the polymkeric substance D replace polymeric A, other and reference example 1 are same, carry out membranization, obtain the film D-1 of partial cross-linked thick 150 μ m.The residual solvent amount of gained film D-1 is below 0.3 weight %.Evaluation result is shown in table 1.

Compare reference example 1

Except with the polymkeric substance E replace polymeric A, other and reference example 1 are same, carry out membranization, obtain the film E-1 of thick 150 μ m.The residual solvent amount of gained film E-1 is below 0.3 weight %.Evaluation result is shown in table 1.Owing to do not exist and crosslinked relevant water-disintegrable silyl among the polymkeric substance E, so think that gained film E-1 does not carry out crosslinked.

Compare reference example 2

Except with polymkeric substance F replace polymeric A, to use chlorobenzene as outside the curtain coating solvent, other obtains the film F-1 through crosslinked thick 150 μ m similarly to Example 1.The residual solvent amount of gained film F-1 is below 0.3 weight %.Evaluation result is shown in table 1.

Table 1

	The film numbering	Total light transmittance (%)	Tensile strength (MPa)	Elongation (%)	Linear expansivity (ppm/ ℃)
	The film numbering	Total light transmittance (%)	Tensile strength (MPa)	Elongation (%)	Linear expansivity (ppm/ ℃)	Reference example 1	A-1	91	61	6.5	41
Reference example 2	B-1	91	60	6.3	41	Reference example 1	A-1	91	61	6.5	41
Reference example 2	B-1	91	60	6.3	41	Reference example 3	C-1	91	62	6.0	40
Reference example 4	D-1	91	61	6.2	40	Reference example 3	C-1	91	62	6.0	40
Reference example 4	D-1	91	61	6.2	40	Compare reference example 1	E-1	91	55	6.8	53
Compare reference example 2	F-1	88	56	5.2	45	Compare reference example 1	E-1	91	55	6.8	53

Reference example 5

In the 50ml flask, under nitrogen atmosphere, tricyclohexyl phosphine 1.0g (3.57 mmole) is dissolved in deuterate benzene 10ml, modulate the solution of 0.357 mmole/ml.

Use trimethyl phosphite (140ppm) as external standard, with Japanese beam split system JEOL-270 type nuclear magnetic resonance device (NMR) mensuration tricyclohexyl phosphine ³¹P-NMR (nucleus magnetic resonance) spectrum.

Consequently, the absorption spectrum of tricyclohexyl phosphine is measured at 9.2ppm.

Reference example 6

The part of the deuterate benzole soln of reference example 5 is packed in another flask, and pack into to convert with Sauerstoffatom and be equivalent to the air of 1 mmole, make their contacts 2 days in 25 ℃ corresponding to tricyclohexyl phosphine 1 mmole.The tricyclohexyl phosphine solution that mensuration contacts with this air ³¹P-NMR.Consequently, do not record the absorption spectrum of the 9.2ppm of tricyclohexyl phosphine, but newly measure the absorption spectrum of thricyclohexyl phosphine oxide at 45.7ppm.

Reference example 7

The part of the deuterate benzole soln of reference example 5 is packed in another flask, and pack into and be equivalent to the triethyl aluminum of 1 mmole corresponding to tricyclohexyl phosphine 1 mmole, reaction was carried out 30 minutes in 25 ℃, synthetic addition complex in deuterate benzene.

Measure the complex solution of the mol ratio 1:1 of this tricyclohexyl phosphine and triethyl aluminum ³¹P-NMR.Consequently, do not record the absorption spectrum of the 9.2ppm of tricyclohexyl phosphine, but newly measure absorption spectrum with the tricyclohexyl phosphine of triethyl aluminum addition complexization at-4.0ppm.

Reference example 8

Except the complex compound with the mol ratio 1:1 of tricyclohexyl phosphine and triethyl aluminum substitutes the tricyclohexyl phosphine, other and reference example 6 are same, and it is contacted with air.

Reference example 9

Except substituting with diethylaluminum chloride the triethyl aluminum, other and reference example 7 are same, the addition complex of the mol ratio 1:1 of synthesizing tricyclic hexyl phosphine and diethylaluminum chloride.

Embodiment 6

In the glass pressure bottle of 100ml, hexanaphthene 37.6g, the 9-trimethoxysilyl Fourth Ring [6.2.1.1 of toluene 9.4g, the moisture 5ppm of the process dehydration of adding moisture 6ppm under nitrogen atmosphere ^3,60 ^2,7] 10 two-4-alkene, 10 mmoles, two the ring [2.2.1] heptan-2-alkene 9 mmoles.Serum cap sealing bottleneck with the band cap.Then, the serum cap by pressure bottle imports the gas shape ethene 30ml as the 0.1MPa of molecular weight regulator.

Solvent and monomeric pressure bottle will be housed heat to 75 ℃, adding as the Pd atom successively is 2 * 10 ^-4The addition complex 2 * 10 of the tricyclohexyl phosphine of the acid chloride of milligram-atom, reference example 7 acquisitions and the mol ratio 1:1 of triethyl aluminum ^-4Mmole, triphenylcarbenium four (pentafluorophenyl group) borate [Ph ₃CB (C ₆F ₅) ₄] 2.4 * 10 ^-4Mmole, the beginning polymerization.

Polyreaction has been carried out 3 hours in 75 ℃, but polymers soln do not become turbid, and is transparence.In this solution, add triethyl silicane 0.1 mmole, polymerization is stopped.The solid branch mensuration that forms by polymers soln knows that the transformation efficiency that forms polymkeric substance reaches 95%.

Carry out 2 times and in polymers soln, add the operation that the water 30ml that contains trolamine 1.0 mmoles extracts residual catalyst, in 2 liters Virahol, add polymers soln, polymkeric substance is solidified.Solidify the drying that carried out 17 hours the back under 90 ℃ of decompressions, obtain polymkeric substance G.Recording kish Pd atom by the atomic absorption analysis among the polymkeric substance G is 0.5ppm, and the Al atom is 1.5ppm.

Utilize 270MHz's ¹H-NMR obtain among the polymkeric substance G from 9-trimethoxysilyl Fourth Ring [6.2.1.1 ^3,60 ^2,7] ratio of structural unit of 10 two-4-alkene.Consequently, from 9-trimethoxysilyl Fourth Ring [6.2.1.1 ^3,60 ^2,7] ratio of structural unit of 10 two-4-alkene is 9.7 moles of %.About molecular weight, number-average molecular weight (Mn) is 74000, and weight-average molecular weight (Mw) is 185000, and second-order transition temperature (Tg) is 360 ℃.

Embodiment 7

Except the addition complex with reference example 8 contacted the addition complex of the tricyclohexyl phosphine of complex compound alternative reference example 7 of gained and triethyl aluminum with air, other similarly to Example 6.

The transformation efficiency that forms polymkeric substance is 97%.

The number-average molecular weight of resulting polymers H (Mn) is 73000, and weight-average molecular weight (Mw) is 187000, and second-order transition temperature (Tg) is 365 ℃.In addition, the ratio of encircling the structural unit of [2.2.1] heptan-2-alkene from 5-triethoxy two among the polymkeric substance H is 9.8 moles of %.

Embodiment 8

Except at triphenylcarbenium four (pentafluorophenyl group) borate [Ph as catalyst component ₃CB (C ₆F ₅) ₄] interpolation after add triethyl aluminum 10 * 10 ^-4Mmole, and substitute 9-trimethoxysilyl Fourth Ring [6.2.1.1 with 5-trimethoxysilyl two ring [2.2.1] heptan-2-alkene 10 mmoles ^3,60 ^2,7] 10 two-4-alkene, 10 mmoles, before beginning, polymerization adds 5.0 mmoles, and added 1.0 mmoles every 20 minutes afterwards and add altogether outside 5 times, other carries out similarly to Example 6.

Finish post polymerization system to polymerization in 3 hours and gonorrhoea do not occur, the transformation efficiency that forms polymkeric substance is 98%.

More than the number-average molecular weight (Mn) of the polymkeric substance I of Huo Deing is 72000, and weight-average molecular weight (Mw) is 177000, and second-order transition temperature (Tg) is 360 ℃.In addition, the ratio of encircling the structural unit of [2.2.1] heptan-2-alkene from 5-trimethoxysilyl two among the polymkeric substance I is 9.7 moles of %.

Polymkeric substance I is modulated into the solution of 20 weight % of p-Xylol, utilizes solution casting method to form, obtain the optical clear film.Then, make the film that has added the tosic acid cyclohexyl crosslinked, obtain the good crosslinked film of process of transparent chemical resistant properties and solvent resistance with steam.

Embodiment 9

Except with 4-methyl Fourth Ring [6.2.1.1 ^3,60 ^2,7] the alternative 9-trimethoxysilyl Fourth Ring [6.2.1.1 of 10 two-9-alkene-4-carboxylate methyl ester, 10 mmoles ^3,60 ^2,7] outside 10 two-4-alkene, 10 mmoles, other carries out similarly to Example 6.

Finish post polymerization system to polymerization in 3 hours and gonorrhoea do not occur, the transformation efficiency that forms polymkeric substance is 91%.

More than the number-average molecular weight (Mn) of the polymkeric substance J of Huo Deing is 62000, and weight-average molecular weight (Mw) is 156000, and second-order transition temperature (Tg) is 360 ℃.In addition, among the polymkeric substance J from 4-methyl Fourth Ring [6.2.1.1 ^3,60 ^2,7] ratio of structural unit of 10 two-9-alkene-4-carboxylate methyl ester is 9.2 moles of %.

Embodiment 10

Adding is as hexanaphthene 37.6g, the toluene 9.4g of solvent, as two ring [2.2.1] heptan-2-alkene 97 mmoles of monomer cyclenes, as monomeric 9-trimethoxysilyl Fourth Ring [6.2.1.1 in the glass pressure bottle of 100ml ^3,60 ^2,7] 10 two-4-alkene, 3 mmoles, as ring suffering-1, the 4-diene 10 * 10 of ring-type non-conjugated diene ^-4Mmole adds triethyl aluminum 10 * 10 again ^-4Mmole and tricyclohexyl phosphine 1.4 * 10 ^-4Mmole.With the serum cap sealing bottleneck of band cap, in 30 ℃ with the addition complex that formed triethyl aluminum and tricyclohexyl phosphine in 10 minutes after, import ethene 30ml as the gasiform 0.1MPa of molecular weight regulator, add acid chloride (as the Pd atom) 2 * 10 again ^-4Mmole, triphenylcarbenium four (pentafluorophenyl group) borate [Ph ₃CB (C ₆F ₅) ₄] 2.4 * 10 ^-4Mmole is in 75 ℃ of beginning polymerizations.

Polymers soln after 3 hours is transparence, and the transformation efficiency that forms polymkeric substance reaches 99%, with Virahol polymkeric substance is solidified, and is dry then, obtains polymkeric substance K.

More than the number-average molecular weight (Mn) of the polymkeric substance K of Huo Deing is 64000, and weight-average molecular weight (Mw) is 177000, among the polymkeric substance K from 9-trimethoxysilyl Fourth Ring [6.2.1.1 ^3,60 ^2,7] ratio of structural unit of 10 two-4-alkene is 3.0 moles of %, second-order transition temperature (Tg) is 375 ℃.

Embodiment 11

Except the ratio that uses endo body/exo body as monomer is 5-n-hexyl, two ring [2.2.1] heptan-2-alkene 100 mmoles of 20/80, as the addition complex 1.5 * 10 of catalyst component with the mol ratio 1:1 of the tricyclohexyl phosphine of reference example 9 and diethylaluminum chloride ^-4Outside the addition complex of the mol ratio 1:1 of alternative tricyclohexyl phosphine of mmole and triethyl aluminum, other carries out similarly to Example 6.

1.5 the transformation efficiency of the formation polymkeric substance after hour is 82%, stops polymerization, obtains polymkeric substance L.

Polymers soln is transparence, is that the film of cyclohexane solution by the solution casting method gained of 20 weight % also is transparent with polymkeric substance L.

Embodiment 12

In the glass pressure bottle of 100ml, hexanaphthene 37.6g, the 9-trimethoxysilyl Fourth Ring [6.2.1.1 of toluene 9.4g, the moisture 5ppm of the process dehydration of adding moisture 6ppm under nitrogen atmosphere ^3,60 ^2,7] 10 two-4-alkene, 10 mmoles, two ring [2.2.1] heptan-2-alkene 90 mmoles, with the serum cap sealing bottleneck of band cap.Then, the serum cap by pressure bottle imports gasiform ethene 35ml.

To be 3 * 10 as the Pd atom ^-4The addition complex 3 * 10 of the tricyclohexyl phosphine of two (methyl ethyl diketone) palladium of milligram-atom, reference example 7 acquisitions and the mol ratio 1:1 of triethyl aluminum ^-4Mmole, triphenylcarbenium four (pentafluorophenyl group) borate [Ph ₃CB (C ₆F ₅) ₄] 3.4 * 10 ^-4Mmole and two ring [2.2.1] heptan-2,5-diene 15 * 10 ^-4Mmole in advance in the solution of toluene 2ml in 60 ℃ of catalyzer of carrying out 30 minutes slaking and obtaining import by heat to 75 ℃ contain in solvent and the monomeric pressure bottle beginning polymerization.

Polyreaction has been carried out 3 hours in 75 ℃, and polymers soln does not become turbid, and is transparence.In this solution, add dimethylaminoethanol 1ml, polymerization is stopped.The solid branch mensuration that forms by polymers soln knows that the transformation efficiency that forms polymkeric substance is 92%.

Among the resulting polymers M from 9-trimethoxysilyl Fourth Ring [6.2.1.1 ^3.60 ^2,7] ratio of structural unit of 10 two-4-alkene is 9.6 moles of %.

The molecular weight of polymkeric substance M counts 48000 with number-average molecular weight (Mn), and (Mw) counts 235000 with weight-average molecular weight, and it is the slightly wide polymkeric substance of molecular weight distribution.

Embodiment 13

Add in pressure bottle the air of 30ml after adding gasiform ethene 30ml, other carries out similarly to Example 6 again.The transformation efficiency of the formation polymkeric substance after 3 hours is 96%.

Among the resulting polymers N from 9-trimethoxysilyl Fourth Ring [6.2.1.1 ^3,60 ^2,7] ratio of structural unit of 10 two-4-alkene is 9.8 moles of %.Molecular weight counts 76000 with number-average molecular weight (Mn), and weight-average molecular weight (Mw) counts 187000.

Compare with embodiment 6,, also can not exert an influence polymerization activity and molecular weight even in polymerization system, add air.

Comparative example 3

Except using tricyclohexyl phosphine 2.0 * 10 ^-4Mmole substitutes the addition complex 2.0 * 10 of the mol ratio 1:1 of tricyclohexyl phosphine and triethyl aluminum ^-4Outside the mmole, other carries out polymerization similarly to Example 6.The transformation efficiency of the formation polymkeric substance after 3 hours is 95%.

Comparative example 4

Except having carried out the tricyclohexyl phosphine 2.0 * 10 that contacts with air with reference example 2 is synthetic ^-4Mmole substitutes the addition complex 2.0 * 10 of the mol ratio 1:1 of tricyclohexyl phosphine and triethyl aluminum ^-4Outside the mmole, other carries out polymerization similarly to Example 6.

The transformation efficiency of the formation polymkeric substance after 3 hours is 0%.

Comparative example 5

Except using tricyclohexyl phosphine 2.0 * 10 ^-4Mmole substitutes the addition complex 2.0 * 10 of the mol ratio 1:1 of tricyclohexyl phosphine and triethyl aluminum ^-4Outside the mmole, other carries out polymerization similarly to Example 13.The transformation efficiency of the formation polymkeric substance after 3 hours is that the transformation efficiency after 65%, 7 hour is 78%.

In the polymkeric substance from 9-trimethoxysilyl Fourth Ring [6.2.1.1 ^3,60 ^2,7] ratio of structural unit of 10 two-4-alkene is 9.8 moles of %.Molecular weight counts 56000 with number-average molecular weight (Mn), and weight-average molecular weight (Mw) counts 137000.Compare with embodiment 6 and embodiment 13,, occur the decline of polymerization activity decline and molecular weight sometimes by in polymerization system, adding air.

The possibility of utilizing on the industry

The cycloolefin addition polymer that utilizes the present invention to obtain can be used for electric parts, medicine equipment, electrically insulating material or the packaging material take optical material as representative.

Can be used for as optical material such as optical recording substrate of LGP, diaphragm, moveable diaphragm, phasic difference film, touch pad, transparent electrode substrate, CD, MD, DVD etc. etc. or optical lens class, encapsulant etc.

Can be used for such as liquid crystal display cells, crystal liquid substrate, container, plate rail, carrier band, barrier film, washing container, body, tube etc. as electric parts.

Can be used for such as drug container, ampoule, syringe, infusion bag, sample container, test tube, heparin tube, sterilization container, pipe, tube etc. as medicine equipment.

Can be used for the insulating materials of the office machines such as the clad material such as electric wire, computer, printer and duplicator as electrically insulating material, the insulating materials of printed base plate etc.

Claims

1. the preparation method of cycloolefin addition polymer is characterized in that, in the presence of the multicomponent series catalysts, comprises following general formula (1)

The cyclenes of the cyclenes based compound of expression is monomeric addition polymerization, in the formula (1), and A ¹～A ⁴Be the atom or the group of the alkyl, the cycloalkyl that are selected from hydrogen atom, halogen atom, carbonatoms 1～15, aryl, ester group, oxetanyl, alkoxyl group, trialkylsilkl, hydroxyl independently of one another, they can be by carbonatoms 1～20 alkylidene group or binding group and the ring structure that comprises the carbonatoms 0～10 of at least a kind of atom that is selected from Sauerstoffatom, nitrogen-atoms and sulphur atom link A ¹And A ²Can form the alkylidene group of carbonatoms 1～5, replacement or the alicyclic ring of non-replacement or the heterocycle of aromatic ring or carbonatoms 2～20 of carbonatoms 5～20, A ¹And A ³Can form replacement or the alicyclic ring of non-replacement or the heterocycle of aromatic ring or carbonatoms 2～20 of carbonatoms 5～20, m is 0 or 1;

Described multicomponent series catalysts comprises:

(a) palladium compound,

(b) be selected from the phosphorus compound more than a kind of following (b-1),

(b-1) microcosmic salt of general formula (b1) expression,

[PR ²R ³R ⁴R ⁵] ⁺[CA ₁] ^-……(b1)

In the general formula (b1), P is a phosphorus atom, R ²Be the substituting group of the alkyl that is selected from hydrogen atom, carbonatoms 1～20, cycloalkyl, aryl, R ³～R ⁵Be alkyl, the cycloalkyl that is selected from carbonatoms 1～20, the substituting group of aryl, [CA independently of one another ₁] ^-For being selected from carboxylate anion, sulfonic acid anion or containing the atom that is selected from B, P or Sb and the anionic counter anion of super acids of F atom, and

(c) be selected from the compound of ionic boron compound, ionic aluminum compound, lewis acidity aluminum compound and lewis acidity boron compound.

2. the preparation method of cycloolefin addition polymer is characterized in that, in the presence of the multicomponent series catalysts, comprises following general formula (1)

The cyclenes of the cyclenes based compound of expression is monomeric addition polymerization, in the formula (1), and A ¹～A ⁴Be the atom or the group of the alkyl, the cycloalkyl that are selected from hydrogen atom, halogen atom, carbonatoms 1～15, aryl, ester group, oxetanyl, alkoxyl group, trialkylsilkl, hydroxyl independently of one another, they can be by carbonatoms 1～20 alkylidene group or binding group and the ring structure that comprises the carbonatoms 0～10 of at least a kind of atom that is selected from Sauerstoffatom, nitrogen-atoms and sulphur atom link A ¹Can form the alkylidene group of carbonatoms 1～5, replacement or the alicyclic ring of non-replacement or the heterocycle of aromatic ring or carbonatoms 2～20 of carbonatoms 5～20, A with A ¹And A ³Can form replacement or the alicyclic ring of non-replacement or the heterocycle of aromatic ring or carbonatoms 2～20 of carbonatoms 5～20, m is 0 or 1;

Described multicomponent series catalysts comprises:

(a) palladium compound,

(b) be selected from the phosphorus compound more than a kind of following (b-2),

3. the preparation method of cycloolefin addition polymer as claimed in claim 2, its feature is that also the multicomponent series catalysts also comprises (d) organo-aluminium compound.

4. the preparation method of cycloolefin addition polymer as claimed in claim 3, its feature is that also the content of organo-aluminium compound (d) is 0.1～200 mole corresponding to palladium 1 grammeatom of palladium compound (a).

5. as the preparation method of each described cycloolefin addition polymer in the claim 1～4, its feature is that also aforementioned palladium compound (a) is the organic carboxylate or the β-dione compounds of palladium.

6. as the preparation method of each described cycloolefin addition polymer in the claim 1～4, its feature also is, the multicomponent series catalysts is the catalyzer that exists modulated to get at least a kind of compound of the polycyclic non-conjugated diene, monocycle shape non-conjugated diene and the straight chain shape non-conjugated diene that are selected from polycyclic monoolefine with two ring [2.2.1] heptan-2-alkene structures, have two ring [2.2.1] heptan-2-alkene structures.

7. as appointing in the claim 1～4-preparation method of a described cycloolefin addition polymer, its feature also is, the multicomponent series catalysts is at two ring [2.2.1] heptan-2-alkene and/or have the catalyzer that exists modulated to get of two ring [2.2.1] heptan-2-alkene of the alkyl of the carbonatoms 1～15 more than 1.

8. as the preparation method of each described cycloolefin addition polymer in the claim 1～4, its feature is that also cyclenes is the cyclenes based compound that monomer comprises following general formula (2)-1 or (2)-2 expression,

9. the preparation method of cycloolefin addition polymer as claimed in claim 8, its feature also be, the cyclenes based compound of aforementioned formula (2)-1 or general formula (2)-2 expression is being to add up to the ratio that accounts for 0.1～30 mole of % to use in the monomer total amount at cyclenes.

10. as the preparation method of each described cycloolefin addition polymer in the claim 1～4, its feature also is, the A in the aforementioned formula (1) ¹～A ⁴Be monomer being to account for 50 moles of ratios more than the % in the monomer total amount to use at cyclenes for the cyclenes of the alkyl of hydrogen atom or carbonatoms 1～15 independently of one another.