CN101291961A

CN101291961A - Polymerization methods using the catalysts

Info

Publication number: CN101291961A
Application number: CNA2006800387465A
Authority: CN
Inventors: 郑永根; 郑溢九; 全成浩; 朴迎焕; 崔大胜; 尹性澈; 林兑宣; 李贞旼
Original assignee: LG Chemical Co Ltd
Current assignee: LG Corp
Priority date: 2005-10-17
Filing date: 2006-10-17
Publication date: 2008-10-22
Anticipated expiration: 2026-10-17
Also published as: TWI333961B; KR100804822B1; TW200718718A; KR20070042091A; JP2009511731A; CN101291961B

Abstract

Provided is a method of preparing a cyclic olefin polymer by addition polymerization of a cyclic olefin monomer, the method including contacting a metal catalyst complex represented by Formula 1 below with a cyclic olefin monomer. <Formula 1 > [M(L1)x(Ll2)y(L3)z]a[Ani]b wherein M is a Group X metal; [M(Li)x(L'2)y(L3)z] is a cationic complex; Li is an anionic hydrocarbyl-containing ligand; U2 is a neutral ligand; L3 is an N-heterocyclic carbene ligand; [Ani] is an anion capable of weakly coordinating with the metal M; x is 1 or 2; y is 0 to 4; z is 1 or 2;2<=x+y+z<=6; a and b are respectively the number of cations and the number of anions capable of weakly coordinating with the metal M and are each a number of 1-10 which is used to satisfy the net charge balance of the metal catalyst complex, and wherein for each of L1, L2, and L3, when a plurality of ligands are present in a molecule of the metal catalyst complex, the ligands may be the same or different. According to the method of the present invention, a high molecular weight cyclic olefin addition polymer can be produced in a high yield even when using a polar functional group-containing cyclic olefin monomer. A polymer produced using the method shows good thermal stability.

Description

Use the polymerization process of catalyzer

Technical field

The present invention relates to a kind of method of using metal catalyst complexes to prepare cyclic olefin polymer, and the polymkeric substance that uses this method preparation.More specifically, the present invention relates to the metal catalyst complexes that a kind of use comprises N-heterocycle carbine (NHC) part and prepare the method for cyclic olefin polymer, and the polymkeric substance that uses this method preparation.

Background technology

The polymkeric substance that cyclic olefin polymer is made up of cycloolefin monomers (for example norbornylene), itself and the polymer phase ratio of routine based on alkene, have transparency, thermotolerance and chemical-resistant preferably, and have much lower birefringence and water absorbability, therefore but widespread use acts on the optical material of CD, DVD or POF (plastic optical fiber), the information and the electronic material that are used for capacitor film or low-dielectric are used for the low medical material that absorbs syringe or Blister Package etc.Especially, polynorbornene is the amorphism polymkeric substance with high glass-transition temperature, high refractive index and low-k, therefore has been widely used as electronic material.People such as Heitz carry out many researchs [(a) T.F.A.Haselwander, W.Heitz, the S.A.Krugel about polynorbornene energetically, J.H.Wendorff, Macromolecules, 1997,30,534. (b) T.F.A.Haselwander, W.Heitz, S.A.Krugel, J.H.Wendorff, Macromol.Chem, Phys.1996,197,3435.].

Because of it can be easy to change into polymkeric substance in the presence of various palladiums or nickel complex and promotor, norbornene monomer can easily carry out polymerization [Ni:(a) WO95 14048A1 (1995), B.F.Goodrich Co., invs.:B.L.Goodall, G.M.Benedikt, L.H.Mclntosh III, D.A.Barnes; Chem.Abstr.1995,123,341322p. (b) EP 445755 A2 (1991), Idemitsu Kosan Co.Ltd., invs.:H.Maezawa, J.Aiura, S.Asahi.Chem.Abstr 1991,115,256943g. Pd:(a) US 3330815 (1967), Union Carbide Corp., invs.:J.E.McKeon, P.S.Starcher; Chem.Abstr.1967,67,648 84g. (b) F.Hojabri, M.M.Mohaddes, A.Talab, Polymer 1976,17, and 710].

Yet the norbornene monomer with stable hydrocarbon ring structure is insoluble in the organic solvent and to needs and uses its metal as electronic material to have relatively poor adsorptivity etc., thereby has limited the application of norbornene monomer.Because these problems are carried out extensive studies energetically.In order to be easy to change the physical properties of polymkeric substance, for example improve the solubility of conventional polynorbornene and offer the new physical properties of polynorbornene, the method that has proposed to change the method for norbornene monomer chemical structure and new functional group has been introduced norbornene monomer.Particularly, can be easy to overcome the low-solubility of norbornene monomer in organic solvent by polar functional group being introduced norbornene monomer.Perhaps, carried out research [(a) H.Cherdron, M.J.Brekner energetically about norbornylene/ethane copolymerization, F.Osan, Angew.Makromol.Chem.1994,223,121. (b) M.Arndt, I.Beulich, Macromol.Chem.Phys.1998,199,1221] or research [T.F.A.Haselwander, the W.Heitz of norbornylene/functionalized norbornylene copolymerization, M.Maskos, Macromol, Rapid.Commun.1997,198,3963].These copolymerizations also can help multipolymer and other object better to adsorb.

The main catalyzer that uses is the catalyst complexes of giving the organic phosphine compound of body part as σDian Zi that comprises as promotor in the cyclic olefin polymer preparation.For example, U.S. Patent No. 6,455,650 disclose by [(R ') _zM (L ') _x(L ") _y] _b[WCA] _dThere is the functionalized monomer based on norbornylene of polymerization down in the catalyst complexes of expression, and wherein phosphine is used as part with the hydrocarbon that comprises alkyl (for example, allyl group).People such as Sen [Organometallics 2001, Vol.20,2802-2812] have reported by [(1, the 5-cyclooctadiene) (CH ₃) Pd (Cl)] catalysis and by phosphine (PPh ₃) and [Na] ⁺[B (3,5-(CF ₃) ₂C ₆H ₃) ₄] ^-Help catalytic ester norbornylene (esternorbornene) polymerization.

Yet the independent adding of phosphine promotor need be used for catalyst Precursors is converted into the independent step of deactivated catalyst and is comprising the remarkable activity of such catalysts that reduces in the presence of the cycloolefin monomers of polar functional group.

Recently, in open No.2004-0052612 of Korean Patent and 2004-0074307 the preparation that comprises the norbornene polymer of polar functional group in the presence of the phosphorus compound as promotor is disclosed.

(for example: stilbene (stilbene)), EP 0721953B1 discloses the metal catalyst complexes that comprises N-heterocycle carbine (NHC) part rather than phosphine part for the synthesis of aromatic olefinic monomer.Yet the enforcement embodiment of this patent documentation discloses the NHC part and has mainly simply been replaced by alkyl or sulfonated alkyl.

As being used to one of several different methods of improving the metal catalyst performance, proposed to replace the method for part with multiple functional moieties.This method has been considered the electronic effect of part.In several pieces of documents, reported by the electronic effect of regulating part and improved catalyst performance.For example, the substituting group of having reported by changing this (Grubbs) ruthenium carbone catalyst part of croup improves catalyst activity [(a) Trnka, T.M. with the electronic effect of regulating ligand; Grubbs, R.H.Acc.Chem.Res.2001,34,18-29. (b) Love, J.A.; Sanford, M.S.; Day, M.W.; Grubbs, R.H.J.Am.Chem.Soc.2003,125,10103-10109].

About the catalyzer that uses in polymkeric substance is synthetic, Waymouth has found that in the presence of zirconocene catalyst the part electronic effect is to play an important role in the stereoselectivity of regulating propylene polymerization [Lin, S.; Hauptman, E.; Lal, T.K.; Waymouth, R.M.; Quan, R.W.; Ernst, A.B.J.Mol.Catal.A:Chem.1998,136,23-33].Coates has reported copolymerization carbonic acid gas (CO in the presence of β-diimino acid zinc alkoxide catalysis (β-diiminate zincalkoxide catalyst) ₂) when the epoxide, the part with part of cyano group replaces can enlarge markedly rate of polymerization [Moore, D.R.; Cheng, M.; Lobkovsky, E.B-Coates, G.W.Angew.Chem., Int.Ed.2002,41,2599-2602].

Yet, so far, not about further improve the report of metal catalyst performance by the part electronic effect that obtains with the multiple functional moieties replacement NHC part that influences the ligand electron density.Therefore, a kind of use of exploitation is necessary by the new polymerization process that the metal catalyst complexes that shows better performance with the multiple replacement NHC of functional group part prepares cyclic olefin polymer.

Summary of the invention

Technical problem

The invention provides a kind of method of using metal catalyst complexes to prepare cyclic olefin polymer.

The present invention also provides a kind of cyclic olefin polymer that uses this method preparation.

Technical scheme

According to an aspect of the present invention, provide a kind of addition polymerization by cycloolefin monomers to prepare the method for cyclic olefin polymer, this method comprises that the metal catalyst complexes that makes by following general formula 1 expression contacts with the cycloolefin monomers of being represented by following general formula 2:

＜general formula 1 〉

[M(L ₁) _x(L′ ₂) _y(L ₃) _z] _a[Ani] _b

Wherein, M is an X family metal,

[M (L ₁) _x(L ' ₂) _y(L ₃) _z] be cationic complexes,

L ₁For comprising the anion ligand of alkyl,

L ' ₂Be neutral ligand,

L ₃Be the N-heterocyclic carbene ligand,

[Ani] be can with coordinate negatively charged ion a little less than the metal M,

X is 1 or 2; Y is 0～4; Z is 1 or 2; 2≤x+y+z≤6,

A and b be respectively cationic number and can with the anionic number of coordinate a little less than the metal M, and 1～10 the number of respectively doing for oneself, in order to satisfying the net charge balance of described metal catalyst complexes,

Wherein, for each L ₁, L ' ₂And L ₃, when having a plurality of part in the metal catalyst complexes molecule, described part can be identical or different, and

＜general formula 2 〉

Wherein, m is 0～4 integer,

R ₇, R ' ₇, R " ₇And R " ' ₇Be independently of one another polar functional group or nonpolar functional group and

R ₇, R ' ₇, R " ₇And R " ' ₇Can be connected to form the saturated or unsaturated cyclic group of C4～C12 or C6～C24 aromatic ring,

Wherein, nonpolar functional group is: be selected from by hydrogen; Halogen; C1～C20 straight or branched alkyl, haloalkyl, alkenyl or halogenated alkenyl; C3～C20 straight or branched alkynyl or halo alkynyl; Do not replace or by the C3～C12 cycloalkyl of alkyl, alkenyl, alkynyl, halogen, haloalkyl, halogenated alkenyl or halo alkynyl substituted; Do not replace or by the C6～C40 aryl of alkyl, alkenyl, alkynyl, halogen, haloalkyl, halogenated alkenyl or halo alkynyl substituted; In replacement or the group that C7～the C15 aralkyl is formed, still be not limited to illustrational example by alkyl, alkenyl, alkynyl, halogen, haloalkyl, halogenated alkenyl or halo alkynyl substituted, and

Wherein, described polar functional group is at least a nonhydrocarbon polar group that comprises in oxygen, nitrogen, phosphorus, sulphur, silicon and the boron, and is selected from by-R ⁸OR ⁹,-OR ⁹,-OC (O) OR ⁹,-R ⁸OC (O) OR ⁹,-C (O) R ⁹,-R ⁸C (O) R ⁹,-OC (O) R ⁹,-R ⁸C (O) OR ⁹,-C (O) OR ⁹,-R ⁸OC (O) R ⁹,-(R ⁸O) _k-OR ⁹,-(OR ⁸) _k-OR ⁹,-C (O)-O-C (O) R ⁹,-R ⁸C (O)-O-C (O) R ⁹,-SR ⁹,-R ⁸SR ⁹,-SSR ⁸,-R ⁸SSR ⁹,-S (=O) R ⁹,-R ⁸S (=O) R ⁹,-R ⁸C (=S) R ⁹,-R ⁸C (=S) SR ⁹,-R ⁸SO ₃R ⁹,-SO ₃R ⁹,-R ⁸N=C=S ,-N=C=S ,-NCO, R ⁸-NCO ,-CN ,-R ⁸CN ,-NNC (=S) R ⁹,-R ⁸NNC (=S) R ⁹,-NO ₂,-R ⁸NO ₂,-P (R ⁹) ₂,-R ⁸P (R ⁹) ₂,-P (=O) (R ⁹) ₂,-R ⁸P (=O) (R ⁹) ₂,

In the group of forming, but be not limited to illustrational example.

In polar functional group, R ⁸And R ¹¹Respectively be C1～C20 straight or branched alkylidene group, halo alkylidene group, alkylene group or halo alkylene group; C3～C20 straight or branched alkynylene (alkynylene) or halo alkynylene (haloalkynylene); Do not replace or encircle alkylidene group by the C3～C12 of alkyl, alkenyl, alkynyl, halogen, haloalkyl, halogenated alkenyl or halo alkynyl substituted; Do not replace or by the C6～C40 arylidene of alkyl, alkenyl, alkynyl, halogen, haloalkyl, halogenated alkenyl or halo alkynyl substituted; Perhaps do not replace or by the inferior aralkyl of C7～C15 of alkyl, alkenyl, alkynyl, halogen, haloalkyl, halogenated alkenyl or halo alkynyl substituted,

R ⁹, R ¹², R ¹³And R ¹⁴Respectively be: hydrogen; Halogen; C1～C20 straight or branched alkyl, haloalkyl, alkenyl or halogenated alkenyl; C3～C20 straight or branched alkynyl or halo alkynyl; Do not replace or by the C3～C12 cycloalkyl of alkyl, alkenyl, alkynyl, halogen, haloalkyl, halogenated alkenyl or halo alkynyl substituted; Do not replace or by the C6～C40 aryl of alkyl, alkenyl, alkynyl, halogen, haloalkyl, halogenated alkenyl or halo alkynyl substituted; Do not replace or by the C7～C15 aralkyl of alkyl, alkenyl, alkynyl, halogen, haloalkyl, halogenated alkenyl or halo alkynyl substituted; Perhaps alkoxyl group, halogenated alkoxy, silyl, siloxy-, aryloxy, halo aryloxy, ketonic oxygen base or halo carbonyl oxygen base; With

Each k is 1～10 integer.

The embodiment of the method according to this invention, at least a in the group that compound that the following general formula 3A～3D of the optional freedom of described N-heterocyclic carbene ligand represents is formed:

＜general formula 3A〉＜general formula 3B〉＜general formula 3C〉＜general formula 3D 〉

Wherein, R ₂₅, R ₂₆, R ₂₇, R ₂₈, R ₂₉With R30 be independently of one another: hydrogen, C1～C20 straight or branched alkyl, C3～C12 cycloalkyl, C2～C20 straight or branched alkenyl, C6～C15 cycloalkenyl group, C3～C20 straight or branched allyl group, C6～C30 aryl, C6～C30 comprise heteroatomic aryl or C7～C30 aralkyl, and it respectively can be replaced by at least a alkyl and/or the hetero atom substituents that are selected from C1～C5 straight or branched alkyl or haloalkyl, C2～C5 straight or branched alkenyl or halogenated alkenyl, halogen, sulphur, oxygen, nitrogen, phosphorus and the phenyl.Herein, described phenyl can not necessarily be replaced by C1～C5 straight or branched alkyl or haloalkyl, halogen or heteroatoms, but is not limited to illustrational example, and described alkenyl can comprise allyl group or vinyl.

Another embodiment of the method according to this invention, described [Ani] be can with coordinate negatively charged ion a little less than the X family metal M, and for being selected from by borate, aluminate, [SbF ₆]-, [PF ₆]-, [AsF ₆]-, perfluor acetate moiety [CF ₃CO ₂]-, perfluorinated acid root [C ₂F ₅CO ₂]-, perfluorobutyric acid root [CF ₃CF ₂CF ₂CO ₂]-, perchlorate [ClO ₄]-, tosic acid root [p-CH ₃C ₆H ₄SO ₃]-, [SO ₃CF ₃A kind of in boric acid benzene]-, (boratabenzene) and the group that do not replace or form by the carborane that halogen replaces.

Another embodiment of the method according to this invention, described borate or aluminate negatively charged ion that following general formula 4A or 4B represent of can serving as reasons:

＜general formula 4A 〉

[M′(R ₃₀) ₄]

＜general formula 4B 〉

[M′(OR ₃₀) ₄]

Wherein, M ' be boron or aluminium and

R ₃₀Be independently respectively: halogen; C1～C20 straight or branched alkyl or the alkenyl that does not replace or replace by halogen; C3～C12 the cycloalkyl that does not replace or replace by halogen; C6～C40 the aryl that does not replace or replace by halogen or hydrocarbon; C6～C40 aryl by C3～C20 straight or branched trialkylsiloxy or C18～C48 straight or branched triaryl siloxy-replacement; C7～C15 the aralkyl that does not perhaps replace or replace by halogen or hydrocarbon.

Another embodiment of the method according to this invention, described metal catalyst complexes can be represented by following general formula 5:

＜general formula 5 〉

Wherein, M, L ₁, L ₂', L ₃, [Ani], a and b be as above-mentioned definition.

Another embodiment of the method according to this invention, described metal catalyst complexes can be and be selected from a kind of in the group that the compound represented by following general formula 6A～6D forms:

＜general formula 6A〉＜general formula 6B 〉

＜general formula 6C〉＜general formula 6D 〉

Wherein, M, L ₁, L ₂', [Ani], a and b such as above-mentioned definition and

R ₁～R ₆Be independently of one another: hydrogen; Halogen; C1～C20 straight or branched alkyl, alkoxyl group, allyl group, alkenyl or vinyl; Do not replace or by the C3～C12 cycloalkyl of alkyl, alkenyl, alkynyl, halogen, haloalkyl, halogenated alkenyl or halo alkynyl substituted; Do not replace or by the C6～C40 aryl of alkyl, alkenyl, alkynyl, halogen, haloalkyl, halogenated alkenyl or halo alkynyl substituted; Do not replace or by the C7～C15 aralkyl of alkyl, alkenyl, alkynyl, halogen, haloalkyl, halogenated alkenyl or halo alkynyl substituted; Perhaps C3～C20 alkynyl.Herein, described alkenyl can comprise allyl group or vinyl.

R ₁～R ₆In at least a for halogen or comprise alkyl, aryl, aralkyl or the alkaryl of halogen.

Another embodiment of the method according to this invention, described metal catalyst complexes can be represented by following general formula 7:

＜general formula 7 〉

Wherein, M, L ₁, L ₂', [Ani], R ₁, R ₂, R ₅, a and b be as above-mentioned definition.

Another embodiment of the method according to this invention, described metal catalyst complexes can be represented by following general formula 8:

＜general formula 8 〉

Wherein, M, L ₂', [Ani], R ₁, R ₂, R ₅, a and b such as above-mentioned definition and

For the C3 allyl group and

R ₁, R ₂And R ₅In at least a for halogen or comprise alkyl, aryl, aralkyl or the alkaryl of halogen.

The embodiment of the method according to this invention, in the method for the invention in the metal catalyst complexes of Shi Yonging, R ₁, R ₂And R ₅In at least a for halogen or comprise alkyl, aryl, aralkyl or the alkaryl of halogen.

The embodiment of the method according to this invention can install to this metal catalyst complexes on the microparticle support.

Another embodiment of the method according to this invention, described microparticle support can be silicon-dioxide, titanium dioxide, silicon-dioxide/chromic oxide, silicon-dioxide/chromic oxide/titanium dioxide, silica/alumina, phosphaljel, silanized silica, silica hydrogel, montmorillonitic clay or zeolite.

Another embodiment of the method according to this invention, described metal catalyst complexes can be used as its solution that is dissolved in the organic solvent acquisition that is selected from the group of being made up of methylene dichloride, ethylene dichloride, toluene, chlorobenzene and composition thereof is used.

Another embodiment of the method according to this invention, described metal catalyst complexes can be used as solid phase and is introduced in the monomer solution.

Another embodiment of the method according to this invention, described cycloolefin addition polymer can be for having the cycloolefin homopolymers of polar functional group; Multipolymer with cycloolefin monomers of opposed polarity functional group; Or cycloolefin monomers with polar functional group and multipolymer with cycloolefin monomers of nonpolar functional group.

Another embodiment of the method according to this invention, the weight-average molecular weight of described cycloolefin addition polymer (Mw) can be 20,000～500,000.

The method according to this invention provides a kind of cyclic olefin polymer that uses this method preparation, its cycloolefin addition polymer for having 20,000～500,000 weight-average molecular weight and comprising polar functional group on the other hand.

According to the embodiment of polymkeric substance of the present invention, described cyclic olefin polymer can be represented by following general formula 9:

＜general formula 9 〉

Wherein m, R7, R7 ', R7 " and R7 " ' such as above-mentioned about above-mentioned general formula 2 definition,

R ₇, R ₇', R ₇" and R ₇" ' at least a be polar functional group and

N is the polymerization degree and is 100～5,000 real number.

According to another embodiment of polymkeric substance of the present invention, described cyclic olefin polymer can be represented by following general formula 10:

＜general formula 10 〉

R ₇, R ₇', R ₇" and R ₇" ' at least a be polar functional group,

R ₁₇, R ₁₇', R ₁₇" and R ₁₇The nonpolar functional group of " ' be, and be selected from independently of one another by hydrogen; Halogen; C1～C20 straight or branched alkyl, haloalkyl, alkenyl or halogenated alkenyl; C3～C20 straight or branched alkynyl or halo alkynyl; Do not replace or by the C3～C12 cycloalkyl of alkyl, alkenyl, alkynyl, halogen, haloalkyl, halogenated alkenyl or halo alkynyl substituted; Do not replace or by the C6～C40 aryl of alkyl, alkenyl, alkynyl, halogen, haloalkyl, halogenated alkenyl or halo alkynyl substituted; Not in replacement or the group that C7～the C15 aralkyl is formed by alkyl, alkenyl, alkynyl, halogen, haloalkyl, halogenated alkenyl or halo alkynyl substituted.

M can be different,

N ' for the polymerization degree and be 100～2,500 real number and

C and d are molar ratio, c+d=1,0.1≤c≤0.95 and 0.05≤d≤0.9.

According to another embodiment of polymkeric substance of the present invention, described cyclic olefin polymer can be represented by following general formula 11:

＜formula 11 〉

R ₇, R ₇', R ₇" and R ₇" ' at least a be polar functional group,

M can be different,

N " for the polymerization degree and be 100～2,500 real number and

E and f are molar ratio, e+f=1,0.1＜e＜0.9 and 0.1＜f＜0.9 and

The repeating unit that satisfies molar ratio e is different from the repeating unit that satisfies molar ratio f.

Hereinafter the present invention will be described in further detail.

According to the method for preparing cyclic olefin polymer of the present invention, even when use has the cycloolefin monomers of polar functional group, also can prepare the cycloolefin addition polymer by high yield.Use the good thermotolerance of polymkeric substance performance of this method preparation.

Beneficial effect

According to the method for preparing cyclic olefin polymer of the present invention, even when use contains the cycloolefin monomers of polar functional group, also can prepare high-molecular weight cycloolefin addition polymer by high yield.Use the good thermostability of polymkeric substance performance of this method preparation.

Description of drawings

Fig. 1 is the X-ray crystalline texture of the metal catalyst complexes of preparation in embodiment 10.

Fig. 2 is TGA (thermogravimetric analysis) graphic representation of the norbornylene homopolymer of preparation in embodiment 16～18 and the comparing embodiment 4.

Embodiment

The invention provides the method that a kind of addition polymerization by cycloolefin monomers prepares cyclic olefin polymer, this method comprises that the metal catalyst complexes that makes by following general formula 1 expression contacts with the cycloolefin monomers of being represented by following general formula 2:

＜general formula 1 〉

[M(L ₁) _x(L′ ₂) _y(L ₃) _z] _a[Ani] _b

Wherein, M is an X family metal; [M (L ₁) _x(L ' ₂) _y(L ₃) _z] be cationic complexes; L ₁For comprising the anion ligand of alkyl; L ' ₂Be neutral ligand, L ₃Be the N-heterocyclic carbene ligand; [Ani] be can with coordinate negatively charged ion a little less than the metal M; X is 1 or 2; Y is 0～4; Z is 1 or 2; 2≤x+y+z≤6; A and b be respectively cationic number and can with the anionic number of coordinate a little less than the metal M, and 1～10 the number of respectively doing for oneself is in order to satisfy the net charge balance of described metal catalyst complexes; And for each L ₁, L ' ₂And L ₃, when having a plurality of part in the metal catalyst complexes molecule, described part can be identical or different.

In above-mentioned general formula 1, M can be arbitrary X family metal.Yet, be preferably nickel or palladium.

In above-mentioned general formula 1, L ₁For comprising the anion ligand of alkyl.The described anion ligand that comprises hydrocarbon is arbitrary hydrocarbyl ligand, when described part when the center metal M is removed, in its closed shell electronic configuration, have negative charge, and can be selected from hydrogen part, C1～C20 straight or branched alkyl part, C5～C10 cycloalkyl part, C2～C20 straight or branched alkenyl part, C6～C15 cycloalkenyl group part, allyl group part or its conventionally form; C6～30 aromatic ligands; C6～C30 comprises heteroatomic aromatic ligand; With can be not necessarily by being selected from C7～C30 aralkyl part that alkyl in C1～C5 straight or branched alkyl or haloalkyl, C2～C5 straight or branched alkenyl or halogenated alkenyl, halogen, sulphur, oxygen, nitrogen, phosphorus and the phenyl and/or hetero atom substituents replace.Herein, phenyl can not necessarily be replaced by C1～C5 straight or branched alkyl or haloalkyl, halogen or heteroatoms, but is not limited to illustrational example, and described alkenyl can comprise vinyl.

The described also optional free R ' C of anion ligand (O) O, R ' C (O) CHC (O) R ' that comprises hydrocarbon, R ' C (O) S, R ' C (S) O, R ' C (S) S, R ' O and (R ') ₂In the part that N represents, the L of R ' and above-mentioned definition wherein ₁Identical.

Described cycloalkyl part and cycloalkenyl group part can be monocycle or encircle part more, and described aromatic ligand can be monocycle part (for example, phenyl) or condensed ring (for example, naphthyl).Any cycloalkyl, any cycloalkenyl group and any aryl also can be connected to form condensed ring.

In above-mentioned general formula 1, L ₂Being neutral ligand, and can comprising reactive thinner, reactive monomer, DMF, DMSO, C4～C10 aliphatics diene, C4～C10 cycloaliphatic diene, more specifically is divinyl, 1,6-hexadiene, cyclooctadiene etc.Also preferably water, enpara, alcohol, ether, ketone, nitrous acid ester, aromatic hydrocarbons, phosphine oxide, organic carbon hydrochlorate or ester etc.

＜general formula 2 〉

Wherein, m is 0～4 integer,

Nonpolar functional group can for: be selected from by hydrogen; Halogen; C1～C20 straight or branched alkyl, haloalkyl, alkenyl or halogenated alkenyl; C3～C20 straight or branched alkynyl or halo alkynyl; Do not replace or by the C3～C12 cycloalkyl of alkyl, alkenyl, alkynyl, halogen, haloalkyl, halogenated alkenyl or halo alkynyl substituted; Do not replace or by the C6～C40 aryl of alkyl, alkenyl, alkynyl, halogen, haloalkyl, halogenated alkenyl or halo alkynyl substituted; In replacement or the group that C7～the C15 aralkyl is formed, still be not limited to illustrational example by alkyl, alkenyl, alkynyl, halogen, haloalkyl, halogenated alkenyl or halo alkynyl substituted.

Described polar functional group is at least a nonhydrocarbon polar group that comprises in oxygen, nitrogen, phosphorus, sulphur, silicon and the boron, and is selected from by-R ⁸OR ⁹,-OR ⁹,-OC (O) OR ⁹,-R ⁸OC (O) OR ⁹,-C (O) R ⁹,-R ⁸C (O) R ⁹,-OC (O) R ⁹,-R ⁸C (O) OR ⁹,-C (O) OR ⁹,-R ⁸OC (O) R ⁹,-(R ⁸O) _k-OR ⁹,-(OR ⁸) _k-OR ⁹,-C (O)-O-C (O) R ⁹,-R ⁸C (O)-O-C (O) R ⁹,-SR ⁹,-R ⁸SR ⁹,-SSR ⁸,-R ⁸SSR ⁹,-S (=O) R ⁹,-R ⁸S (=O) R ⁹,-R ⁸C (=S) R ⁹,-R ⁸C (=S) SR ⁹,-R ⁸SO ₃R ⁹,-SO ₃R ⁹,-R ⁸N=C=S ,-N=C=S ,-NCO, R ⁸-NCO ,-CN ,-R ⁸CN ,-NNC (=S) R ⁹,-R ⁸NNC (=S) R ⁹,-NO ₂,-R ⁸NO ₂,-P (R ⁹) ₂,-R ⁸P (R ⁹) ₂,-P (=O) (R ⁹) ₂,-R ⁸P (=O) (R ⁹) ₂,

In the group of forming, but be not limited to illustrational example.

In polar functional group, R ⁸And R ¹¹Respectively be C1～C20 straight or branched alkylidene group, halo alkylidene group, alkylene group or halo alkylene group; C3～C20 straight or branched alkynylene or halo alkynylene; Do not replace or encircle alkylidene group by the C3～C12 of alkyl, alkenyl, alkynyl, halogen, haloalkyl, halogenated alkenyl or halo alkynyl substituted; Do not replace or by the C6～C40 arylidene of alkyl, alkenyl, alkynyl, halogen, haloalkyl, halogenated alkenyl or halo alkynyl substituted; Perhaps do not replace or by the inferior aralkyl of C7～C15 of alkyl, alkenyl, alkynyl, halogen, haloalkyl, halogenated alkenyl or halo alkynyl substituted,

Each k is 1～10 integer.

In the method for the invention in the metal catalyst complexes of Shi Yonging, L3 is at least a in the compound represented of N-heterocycle carbine (NHC) part and the following general formula 3A～3D of optional freedom, but be not limited to illustrational example, and can use known all NHC compounds in the association area:

In the method for the invention in the metal catalyst complexes of Shi Yonging, [Ani] be can with coordinate negatively charged ion a little less than the X family metal M, and for being selected from by borate, aluminate, [SbF ₆]-, [PF ₆]-, [AsF ₆]-, perfluor acetate moiety [CF ₃CO ₂]-, perfluorinated acid root [C ₂F ₅CO ₂]-, perfluorobutyric acid root [CF ₃CF ₂CF ₂CO ₂]-, perchlorate [ClO ₄]-, tosic acid root [p-CH ₃C ₆H ₄SO ₃]-, [SO ₃CF ₃A kind of in]-, boric acid benzene and the group that do not replace or form by the carborane that halogen replaces.

More specifically, in the method for the invention in the metal catalyst complexes of Shi Yonging, described borate or the aluminate negatively charged ion that following general formula 4A or 4B represent of can serving as reasons:

＜general formula 4A 〉

[M′(R ₃₀) ₄]

＜general formula 4B 〉

[M′(OR ₃₀) ₄]

Wherein, M ' be boron or aluminium and

The metal catalyst complexes that uses in the method for the present invention can be represented by following general formula 5:

＜general formula 5 〉

More preferably, described metal catalyst complexes can be and is selected from the compound of being represented by following general formula 6A～6D:

＜general formula 6A〉＜general formula 6B 〉

＜general formula 6C〉＜general formula 6D 〉

R ₁～R ₆Be independently of one another: hydrogen; Halogen; C1～C20 straight or branched alkyl, alkoxyl group or alkenyl; Do not replace or by the C3～C12 cycloalkyl of alkyl, alkenyl, alkynyl, halogen, haloalkyl, halogenated alkenyl or halo alkynyl substituted; Do not replace or by the C6～C40 aryl of alkyl, alkenyl, alkynyl, halogen, haloalkyl, halogenated alkenyl or halo alkynyl substituted; Do not replace or by the C7～C15 aralkyl of alkyl, alkenyl, alkynyl, halogen, haloalkyl, halogenated alkenyl or halo alkynyl substituted; Perhaps C3～C20 alkynyl.But be not limited to illustrational example.Described alkenyl can comprise allyl group or vinyl.R ₁～R ₆In at least a for halogen or comprise alkyl, aryl, aralkyl or the alkaryl of halogen.

In the compound of above-mentioned 6A～6D, R ₁～R ₆Also can comprise the polar functional group that comprises at least a rather than halogen in oxygen, nitrogen, phosphorus, sulphur, silicon and the boron.Described polar functional group is not restricted especially, as long as it can provide electronic effect by inducing electrophilic or power supply.Preferred polar functional group can be silylation, alkylsulfonyl, nitro, amino, cyano group, ethanoyl, ester group, carbonyl, ether etc.

Again more preferably, described metal catalyst complexes can be represented by following general formula 7:

＜general formula 7 〉

More preferably, described metal catalyst complexes can be represented by following general formula 8:

＜general formula 8 〉

Wherein, M, L ₂', R ₁, R ₂, R ₅[Ani] is as above-mentioned definition.

And, R ₁, R ₂And R ₅In at least a for halogen or contain alkyl, aryl, aralkyl or the alkaryl of halogen.

More specifically, described metal catalyst complexes can be represented by following general formula 8A:

＜general formula 8A 〉

Wherein, a and b be as above-mentioned definition,

R ₂₁And R ₂₂Be C1～C20 straight or branched alkyl independently of one another,

For the C3 allyl group and

X is a halogen.

In the method for preparing cyclic olefin polymer according to the present invention, this metal catalyst complexes can be installed on the microparticle support.Described microparticle support can be silicon-dioxide, titanium dioxide, silicon-dioxide/chromic oxide, silicon-dioxide/chromic oxide/titanium dioxide, silica/alumina, phosphaljel, silanized silica, silica hydrogel, montmorillonitic clay or zeolite.The metal catalyst complexes that use installs on the microparticle support can be according to the molecular weight distribution of the application-specific telomerized polymer of polymkeric substance, and strengthens the apparent density of polymkeric substance.

In the method for preparing cyclic olefin polymer according to the present invention, described metal catalyst complexes can be used as and it is dissolved in the solution that the organic solvent that is selected from the group of being made up of methylene dichloride, ethylene dichloride, toluene, chlorobenzene and composition thereof obtains uses.Based on monomeric gross weight in the monomer solution (100 weight part), organic solvent content can be 10～800 weight parts, more preferably 50～400 weight parts.If organic solvent content is less than 10 weight parts, then because viscosity is too high, so but can be difficult to stir and the monomer of remained unreacted, thus the polymerization yield reduced.In addition, must use excessive solvent diluting reaction solution to compensate too high viscosity.On the other hand,, then can reduce speed of reaction, thereby cause the yield of product and molecular weight to reduce if organic solvent content surpasses 800 weight parts.Perhaps, also metal catalyst complexes can be introduced in the monomer solution as solid phase.

In the method for preparing cyclic olefin polymer according to the present invention, all monomeric molar ratios can be 1/50～1/100 in described metal catalyst complexes and the monomer solution, and 000, more preferably 1/100～1/20,000.If the molar ratio of metal catalyst complexes surpasses 1/100, then may be difficult to remove the catalyst residue on the polymkeric substance.On the other hand, if it less than 1/20,000, then can reduce the polymerization yield.

In the method for preparing cyclic olefin polymer according to the present invention, described cyclic olefin polymer can be the cycloolefin homopolymers with polar functional group, the multipolymer with cycloolefin monomers of opposed polarity functional group; Or cycloolefin monomers with polar functional group and multipolymer with cycloolefin monomers of nonpolar functional group.

Use the norbornylene addition polymer that contains polar functional group of method preparation of the present invention can comprise the norbornene monomer that contains polar functional group of 0.1-99.9 mole % at least.At this moment, the norbornene monomer that contains polar functional group can be the mixture of endo isomer and exo isomer, and the not restriction of the mixture ratio of endo isomer and exo isomer.In following enforcement embodiment, will provide its detailed description.

Can carry out polyaddition of the present invention based on the identical mode of the ordinary method of the polymkeric substance of norbornylene with preparation, it comprises: in solvent, mix monomer and catalyzer based on norbornylene, and the polymerization of the mixture that makes.The method according to this invention can obtain 40% or the cycloolefin addition polymer that contains polar functional group of higher high yield, and it can have 20,000 or bigger high weight-average molecular weight (M _w).Therefore, the method according to this invention can high yield preparation have the cycloolefin addition polymer that high-molecular weight contains polar functional group.If the molecular weight of cyclic olefin polymer less than 20,000, can reduce mechanical properties.On the other hand, if it surpasses 500,000, can reduce the workability of polymkeric substance.

The present invention also provides a kind of cyclic olefin polymer of this method preparation, its cycloolefin addition polymer for having 20,000～500,000 weight-average molecular weight and comprising polar functional group.

More specifically, described cyclic olefin polymer can be represented by following general formula 9:

＜general formula 9 〉

R ₇, R ₇', R ₇" and R ₇" ' at least a be polar functional group and

N is the polymerization degree and is 100～5,000 real number.

Described cyclic olefin polymer also can be represented by following general formula 10:

＜general formula 10 〉

R ₇, R ₇', R ₇" and R ₇" ' at least a be polar functional group,

M can be different,

N ' for the polymerization degree and be 100～2,500 real number and

C and d are molar ratio, c+d=1,0.1≤c≤0.95 and 0.05≤d≤0.9.

Described cyclic olefin polymer can be represented by following general formula 11:

＜formula 11 〉

R ₇, R ₇', R ₇" and R ₇" ' at least a be polar functional group,

M can be different,

N " for the polymerization degree and be 100～2,500 real number and

E and f are molar ratio, e+f=1,0.1＜e＜0.9 and 0.1＜f＜0.9 and

The polymkeric substance based on norbornylene that contains polar functional group prepared in accordance with the present invention is transparent and has good adhesion with metal or polymkeric substance with opposed polarity functional group, has the low-k that is applicable to the insulation electron device and the cyclic olefin polymer of good thermal stability and intensity.In addition, the norbornylene based polyalcohol that contains polar functional group has adhesivity with electric substrate not existing under the coupling agent, and has good adhesion with copper for example, silver or golden metal substrate.Again in addition, the polymkeric substance based on norbornylene that contains polar functional group has good optical properties, and therefore can be used as the protective membrane material of polaroid.And the polymkeric substance based on norbornylene that contains polar functional group can be used as for example material of the electronic installation of unicircuit, printed circuit board (PCB) or multi-chip module (multichip module).

Hereinafter, with reference to following enforcement embodiment the present invention is described more specifically.Following enforcement embodiment only is not used for limiting the scope of the invention for the purpose of illustration.

In following enforcement embodiment, use standard Schlenk technology or glove box technology are used to handle whole operations of the compound that is subject to air or water influence.Use Bruker 300 spectrometers to obtain the NMR wave spectrum.Under 300MHz and 75MHz, measure respectively ¹H NMR wave spectrum with ¹³C NMR wave spectrum.Use the molecular weight and the molecular weight distribution of polystyrene standard sample measurement polymkeric substance by GPC (gel permeation chromatography).(TGA 2050 to use the TA instrument; Heating rate: 10K/min) carry out thermogravimetric analysis (TGA).By distillation purifying toluene from potassium/benzophenone, and pass through from CaH ₂Middle distillation purifying methylene dichloride and chlorobenzene.

Monomeric synthetic

Synthetic embodiment 1

5-norbornylene-2-carboxylate methyl ester (monomer b) (endo isomer: exo isomer=100: 0) synthetic

Dissolving 5-norbornylene-2-carboxylic acid (mixture of endo isomer and exo isomer) in distilled water (3.8g, 27.5mmol).In reaction mixture, add the I that is dissolved in the 112ml distilled water ₂(9.4g is 37.1mmol) with KI (19g, solution 114mmol), and the mixture of generation was hatched 3 hours.Behind the reaction terminating, be somebody's turn to do the solution that generates with extracted with diethyl ether.Remove from organic layer and to desolvate to obtain oily iodine lactone.This compound of dissolving in the trace ethyl acetate, and with the solution of this generation of hexane recrystallize to obtain pure crystalline iodine lactone (yield: 50%).

This iodine lactone of dissolving in the 70ml Glacial acetic acid (4.4g, 16.6mmol).With the solution that generates be cooled to 0 ℃ and to wherein add gradually zinc powder (21.5g, 328mmol).Make this reaction mixture reaction 3 hours at 15 ℃, at room temperature reacted then 2 hours.Leach undissolved inorganic substance, and this filtrate of dilute with water and use extracted with diethyl ether.Collected organic layer is by anhydrous MgSO ₄Drying, and by the fractionation purifying to make 5-norbornylene-2-carboxylic acid (endo isomer).This endo isomer of dissolving and Na in acetone ₂CO ₃, and to wherein adding CH gradually ₃I.From the solution that generates, remove and desolvate, then carry out silica gel column chromatography to make pure endo isomer (monomer b).

Synthetic embodiment 2

5-norbornylene-2-carboxylate methyl ester (monomer b) (endo isomer: exo isomer=5: 95) synthetic

Dissolving 5-norbornylene-2-carboxylic acid (mixture of endo isomer and exo isomer) in distilled water (3.8g, 27.5mmol).In reaction mixture, add the I that is dissolved in the 112ml distilled water ₂(9.4g is 37.1mmol) with KI (19g, solution 114mmol), and at room temperature make the mixture reaction 3 hours of generation.Behind the reaction terminating, with the solution of extracted with diethyl ether generation.Use 5%H ₂SO ₄The oxidation water layer, and use extracted with diethyl ether.Remove from organic layer and to desolvate, and by fractionation purifying residue to make 5-norbornylene-2-carboxylic acid (mixture of endo isomer and exo isomer, endo isomer: exo isomer=5: 95).This compound of dissolving and Na in acetone ₂CO ₃, and to wherein adding CH gradually ₃I.From the solution that generates, remove and desolvate, then carry out silica gel column chromatography to make exo isomer (monomer b).

The preparation of pre-catalyst

Embodiment 1

Compound 1 (ArN=CH-CH=NAr, Ar ≡ 2,6-Me ₂ -4-BrC ₆ H ₂ ) preparation

Dissolving 4-bromo-2 in methyl alcohol (30ml), the 6-xylidine (5.6g, 28mmol) and oxalic dialdehyde (40% solution, 1.58ml (14mmol)), and to wherein adding formic acid (1ml).Stirred this reaction mixture 48 hours.It is also dry in a vacuum to obtain compound 1 yellow crystals (4.1g, yield: 70%) to filter the solution that generates.

¹H NMR(CDCl ₃)：8.06(s，2H)，7.24(s，4H)，2.15(s，12H)，

¹³C NMR(CDCl ₃)：δ163.98，149.08，131.37，129.07，118.16，18.52

HRMS m/z calcd：419.9386，obsd：419.9387

Embodiment 2

Compound 2 (ArN=CH-CH=NAr, Ar ≡ 2,6-iPr ₂ -4-IC ₆ H ₂ ) preparation

Dissolving 4-iodo-2 in methyl alcohol (30ml), the 6-diisopropyl aniline (8.5g, 28mmol) and oxalic dialdehyde (40% solution, 1.58ml (14mmol)), and to wherein adding formic acid (1ml).Stirred this reaction mixture 48 hours.It is also dry in a vacuum to obtain compound 2 yellow crystals (6.4g, yield: 73%) to filter the solution that generates.

¹H NMR(CDCl ₃)：8.04(s，2H)，7.28(s，4H)，2.85(m，4H)，1.16(d，12H，6.9Hz)，

¹³C NMR(CDCl ₃)：δ163.53，149.06，139.66，132.91，90.57，28.44，23.58

HRMSm/z calcd：628.0811，obsd：628.0812

Embodiment 3

Compound 3 (ArN=CH-CH=NAr, Ar ≡ 2,6-iPr ₂ -4-BrC ₆ H ₂ ) preparation

Dissolving 4-bromo-2 in methyl alcohol (30ml), the 6-diisopropyl aniline (7.2g, 28mmol) and oxalic dialdehyde (40% solution, 1.58ml (14mmol)), and to wherein adding formic acid (1ml).Stirred this reaction mixture 48 hours.It is also dry in a vacuum to obtain compound 3 yellow crystals (5.2g, yield: 70%) to filter the solution that generates.

¹H NMR(CDCl ₃)：8.07(s，2H)，7.32(s，4H)，2.87(m，4H)，1.18(d，12H，6.9Hz)，

¹³C NMR(CDCl ₃)：δ163.68，147.26，139.50，126.90，119.24，90.57，28.59，23.63

HRMS m/z calcd：532.1088，obsd：532.1089

Embodiment 4

Compound 4[N, N '-two (4-bromo-2,6-3,5-dimethylphenyl) imidazole salts muriate] preparation

Dissolved compound 1 in toluene (30ml) (3g, 7.1mmol) and paraformaldehyde (0.22g, 7.1mmol) and be back to paraformaldehyde at 100 ℃ and dissolve fully.The solution that generates is cooled to 40 ℃, and is dissolved in diox (1.7ml, 7.1mmol) the 4M HCl in to wherein adding gradually.Then, reaction mixture is cooled to 70 ℃, refluxed about 1 hour, at room temperature stirred 3 hours, filter, and dry in a vacuum to obtain compound 4 grey powder (1.8g, yield: 54%).

¹H NMR(CDCl ₃)：11.65(s，1H)，7.56(s，2H)，7.40(s，4H)，2.22(s，12H)

¹³C NMR(CDCl ₃)：δ137.70，137.34，132.57，131.96，125.23，124.71

HRMSm/z calcd：432.9914，obsd：432.9911

Embodiment 5

Compound 5[N, N '-two (4-iodo-2,6-diisopropyl phenyl) imidazole salts muriate] preparation

Dissolved compound 2 in toluene (30ml) (4.5g, 7.1mmol) and paraformaldehyde (0.22g, 7.1mmol) and be back to paraformaldehyde at 100 ℃ and dissolve fully.The solution that generates is cooled to 40 ℃, and is dissolved in diox (1.7ml, 7.1mmol) the 4M HCl in to wherein adding gradually.Then, reaction mixture is cooled to 70 ℃, refluxed about 1 hour, at room temperature stirred 3 hours, filter, and dry in a vacuum to obtain compound 5 grey powder (2.7g, yield: 60%).

¹H NMR(C2D6SO)：10.24(s，1H)，8.55(s，2H)，7.81(s，4H)，4.25(m，4H)，1.24(d，12H，6.9Hz)，1.14(d，12H，6.9Hz)

HRMS m/z calcd：628.0811，obsd：628.0812

Embodiment 6

Compound 6[N, N '-two (4-bromo-2,6-diisopropyl phenyl) imidazole salts muriate] preparation

Dissolved compound 3 in toluene (30ml) (3.8g, 7.1mmol) and paraformaldehyde (0.22g, 7.1mmol) and be back to paraformaldehyde at 100 ℃ and dissolve fully.The solution that generates is cooled to 40 ℃, and is dissolved in diox (1.7ml, 7.1mmol) the 4M HCl in to wherein adding gradually.Then, reaction mixture is cooled to 70 ℃, refluxed about 1 hour, at room temperature stirred 3 hours, filter, and dry in a vacuum to obtain compound 6 grey powder (2.32g, yield: 60%).

¹H NMR(CDCl ₃)：11.24(s，1H)，7.76(s，2H)，7.45(s，4H)，2.36(m，4H)，1.24(dd，12H，5.7Hz)

HRMS m/z calcd：545.1166，obsd：545.1167

Embodiment 7

Compound 7[chlorine (η ³-allyl group)-(N, N '-two (4-bromo-2,6-3,5-dimethylphenyl imidazoles-2-subunit)-palladium] preparation

Dissolved compound 4 in tetrahydrofuran (THF) (1.5g, 3.2mmol) and potassium tert.-butoxide (0.39g, 3.2mmol).Stir this reaction mixture 4 hours and remove in a vacuum and desolvate.In glove box, residue is dissolved in the toluene, and filters resulting solution by the pillar that is filled with Sai Lite (cellite).Under reduced pressure remove toluene, make carbene compound gray solid (0.9g, 65%).(0.9g is 2.1mmol) with Allylpalladium muriate dimer [(allyl group) PdCl] for this carbene compound of dissolving in tetrahydrofuran (THF) ₂(0.38g 1.05mmol), and stirred this reaction mixture 1 hour.Then, under reduced pressure remove and desolvate, with pentane wash residual thing, and the solid product that filtration generates is to make compound 7 grey powder (1.2g, 92%).

¹H NMR(300Mz，CDCl ₃)：7.33(s，4H)，7.11(s，2H)，4.91(m，1H)，3.95(d，1H)，3.21(d，1H)，2.87(d，1H)，2.23(s，6H)，2.21(s，6H)，1.82(d，1H)，

¹H NMR(CDCl ₃)：7.33(s，4H)，7.11(s，2H)，4.91(sep，1H，9Hz)，3.95(dd，1H，1.5Hz)，3.21(d，1H，6Hz)，2.87(d，1H，13.5Hz)，2.22(d，12H，10.2Hz)，1.82(d，1H，11.7Hz)

¹³C NMR(CDCl ₃)：δ138.32，137.60，132.42，131.70，123.45，123.37，115.07，77.62，73.52，49.97，18.67

HRMSm/zcalcd：578.9262，obsd：578.9263

Embodiment 8

Compound 8[chlorine (η ³ -allyl group)-(N, N '-two (4-iodo-2.6-diisopropyl phenyl) imidazoles-2-subunit)-palladium] Preparation

Dissolved compound 5 in tetrahydrofuran (THF) (2.0g, 3.2mmol) and potassium tert.-butoxide (0.39g, 3.2mmol).Stirred reaction mixture 4 hours also removes in a vacuum and desolvates.In glove box, residue is dissolved in the toluene and and filters the solution that generates by the pillar that is filled with Sai Lite.Under reduced pressure remove toluene to make carbene compound gray solid (1.24g, 65%).(1.24g is 2.1mmol) with Allylpalladium muriate dimer [(allyl group) PdCl] for this carbene compound of dissolving in tetrahydrofuran (THF) ₂(0.38g 1.05mmol), and stirred this reaction mixture 1 hour.Then, under reduced pressure remove and desolvate, with pentane wash residual thing, and the solid product that filtration generates is to obtain compound 8 grey powder (1.49g, 90%).

¹H NMR(CDCl ₃)：7.50(s，4H)，7.01(s，2H)，4.78(m，1H，7.2Hz)，3.89(dd，1H，1.5Hz)，2.97(dd，1H，6Hz)，2.95(dd，2H，6.9Hz)，2.68(dd，2H，6.6Hz)，1.57(d，1H，12.3Hz)，1.28(d，6H，6.6Hz)，1.22(d，6H，6.6Hz)，1.08(d，6H，6.6Hz)，0.98(d，6H，6.6Hz)

¹³C NMR(CDCl ₃)：δ145.53，132.54，130.30，127.61，127.43，126.29，125.13，68.29，29.48，25.96，24.99，24.27，13.54，12.74

HRMSm/zcalcd：787.0237，obsd：787.0238

Embodiment 9

Compound 9[chlorine (η ³ -allyl group)-(N, N '-two (4-bromo-2,6-diisopropyl phenyl) imidazoles-2-subunit)-palladium] Preparation

Dissolved compound 6 in tetrahydrofuran (THF) (1.74g, 3.2mmol) and potassium tert.-butoxide (0.39g, 3.2mmol).Stirred reaction mixture 4 hours also removes in a vacuum and desolvates.In glove box, residue is dissolved in the toluene and and filters the solution that generates by the pillar that is filled with Sai Lite.Under reduced pressure remove toluene to make carbene compound gray solid (1.02g, 63%).(1.02g is 2.0mmol) with Allylpalladium muriate dimer [(allyl group) PdCl] for this carbene compound of dissolving in tetrahydrofuran (THF) ₂(0.36g 1.0mmol), and stirred this reaction mixture 1 hour.Then, under reduced pressure remove and desolvate, with pentane wash residual thing, and the solid product that filtration generates is to obtain compound 9 grey powder (1.24g, 90%).

¹H NMR(CDCl ₃)：7.37(s，4H)，7.13(s，2H)，4.84(m，1H，5.7Hz)，3.95(dd，1H，1.5Hz)，3.08(m，3H)，2.84(d，1H，13.5Hz)，2.78(dd，2H，6.9Hz)，1.62(s，1H)，1.36(d，6H，6.6Hz)，1.30(d，6H，6.6Hz)，1.16(d，6H，6.6Hz)，1.06(d，6H，6.6Hz)

¹³C NMR(CDCl ₃)：δ145.5，132.5，130.3，127.6，127.4，126.2，125.1，68.2，29.4，25.9，24.9，24.2，13.5，12.7

HRMSm/z calcd：691.0514，obsd：691.0516

The compound 1～9 of preparation is by shown in the following reaction process 1 in embodiment 1～9.

＜reaction process 1 〉

The preparation of metal catalyst complexes (catalyzer)

Embodiment 10

The preparation of compound 10

At 5ml CH ₂Cl ₂In dissolved compound 9 (0.2g, 0.351mmol) and AgBF ₄(68mg, 0.351mmol) and stirred reaction mixture 1 hour.By the Sai Lite filtering reacting solution and except that desolvating to obtain compound 10 grey powder (0.2g, 92%).

¹H NMR(CDCl ₃)：7.43(s，4H)，7.24(s，2H)，4.84(m，1H)，4.45(br，1H)，3.34(br，1H)，2.64(br，4H)，2.32(m，1H)，2.21(m，1H)，1.30(m，12H)，1.19(m，12H)

The X-ray crystalline texture of compound 10 is shown among Fig. 1.

The preparation of homopolymer and multipolymer

The monomer and the pre-catalyst that use in following polyreaction are as follows.

Monomer

Pre-catalyst

Embodiment 11: norbornylene (monomer equal polymerization a)

In the 100ml Schlenk flask that toluene (15ml) is housed, add norbornylene (5g, 53.1mmol).In glove box with pre-catalyst B and silver tetrafluoroborate (AgBF ₄) be dissolved in the mixing solutions of 5ml methylene dichloride and toluene (1: 1), and stirred this reaction mixture 1 hour.Then, in flask, add, and this flask was stirred 20 hours at 25 ℃ by the filtering palladium catalyst of the pillar that is filled with Sai Lite (0.53mmol).Then, adding the solution that generates in excessive methyl alcohol precipitates to make white polymer.Filter this throw out by glass funnel, and in vacuum drying oven 80 ℃ of following dried recovered products 24 hours to obtain norbornene polymer (yield: 99%).

Embodiment 12

With with mode identical in embodiment 11, use catalytic amount, polymer solvent and polymerization time and the pre-catalyst C identical be summarized in the following table 1 to prepare norbornene polymer with embodiment 11.

Embodiment 13

With with mode identical in embodiment 11, use catalytic amount, polymer solvent and polymerization time and the pre-catalyst E identical be summarized in the following table 1 to prepare norbornene polymer with embodiment 11.

Comparing embodiment 1

With with mode identical in embodiment 11, use amount, polymer solvent and polymerization time and the pre-catalyst A be summarized in the catalyzer identical in the following table 1 to prepare norbornene polymer with embodiment 11.

Comparing embodiment 2

With with mode identical in embodiment 11, use catalytic amount, polymer solvent and polymerization time and the pre-catalyst D identical be summarized in the following table 1 to prepare norbornene polymer with embodiment 11.

Table 1

1): in tetrahydrofuran (THF), do not dissolve

2): use polystyrene standard to measure by GPC

3): the yield after separating fully

Embodiment 14

The polymerization of 5-norbornylene-2-carboxylate methyl ester (exo isomer: endo isomer=95: 5, monomer b)

In the 100ml Schlenk flask that 15ml toluene is housed, add 5-norbornylene-2-carboxylate methyl ester (exo isomer: endo isomer=95: 5,5ml (33.0mmol)).In glove box with pre-catalyst B and silver tetrafluoroborate (AgBF ₄) be dissolved in the mixing solutions of 5ml methylene dichloride and toluene (1: 1), and stirred this reaction mixture 1 hour.Then, in flask, add, and this flask was stirred 20 hours at 25 ℃ by the filtering palladium catalyst of the pillar that is filled with Sai Lite (0.33mmol).Then, adding the solution that generates in excessive methyl alcohol precipitates to make white polymer.Filter this throw out by glass funnel, and in vacuum drying oven 80 ℃ of following dried recovered products 24 hours to obtain polymkeric substance (yield: 71%).

Embodiment 15

With with mode identical in embodiment 14, use catalytic amount, polymer solvent and polymerization time and the pre-catalyst C identical be summarized in the following table 2 to prepare 5-norbornylene-2-carboxylate methyl ester polymkeric substance with embodiment 14.

Comparing embodiment 3

With with mode identical in embodiment 14, use catalytic amount, polymer solvent and polymerization time and the pre-catalyst A identical be summarized in the following table 2 to prepare 5-norbornylene-2-carboxylate methyl ester polymkeric substance with embodiment 14.

Table 2

	Monomer ¹⁾	Pre-catalyst	[M]/pre-catalyst	[Ani]	Time (h)	Solvent	Mn	Mw	Mw/ Mn ²⁾	Yield (%) ³⁾
	Monomer ¹⁾	Pre-catalyst	[M]/pre-catalyst	[Ani]	Time (h)	Solvent	Mn	Mw	Mw/ Mn ²⁾	Yield (%) ³⁾	Embodiment 14	b(95∶5)	B	100/1	BF ₄ ^-	20	Toluene	9,253	20,211	2.18	71
Embodiment 15	b(95∶5)	C	100/1	BF ₄ ^-	20	Toluene	6,928	22,021	2.89	75	Embodiment 14	b(95∶5)	B	100/1	BF ₄ ^-	20	Toluene	9,253	20,211	2.18	71
Embodiment 15	b(95∶5)	C	100/1	BF ₄ ^-	20	Toluene	6,928	22,021	2.89	75	Comparing embodiment 3	b(95∶5)	A	100/1	BF ₄ ^-	20	Toluene	10,922	20,424	1.87	70

1): the numeral endo isomer in the bracket and the ratio of exo isomer

2): use polystyrene standard to measure by GPC

3): the yield after separating fully

Embodiment 16

The polymerization of 5-norbornylene-2-carboxylate methyl ester (exo isomer: endo isomer=50: 50, monomer b)

In the 100ml Schlenk flask that 15ml toluene is housed, add 5-norbornylene-2-carboxylate methyl ester (exo isomer: endo isomer=50: 50,5ml (33.0mmol)).In glove box with pre-catalyst C and silver tetrafluoroborate (AgBF ₄) be dissolved in the mixing solutions of 5ml methylene dichloride and toluene (1: 1), and stirred this reaction mixture 1 hour.Then, in flask, add, and this flask was stirred 20 hours at 25 ℃ by the filtering palladium catalyst of the pillar that is filled with Sai Lite (0.33mmol).Then, adding the solution that generates in excessive methyl alcohol precipitates to make white polymer.Filter this throw out by glass funnel, and in vacuum drying oven 80 ℃ of following dried recovered products 24 hours to obtain polymkeric substance (yield: 55%).

Embodiment 17

In the 100ml Schlenk flask that the 15ml chlorobenzene is housed, add 5-norbornylene-2-carboxylate methyl ester (exo isomer: endo isomer=50: 50,5ml (33.0mmol)).In glove box with pre-catalyst B and hexafluoro-antimonic acid silver (AgSbF ₆) be dissolved in the 5ml chlorobenzene, and stirred this reaction mixture 1 hour.Then, in flask, add, and this flask was stirred 6 hours at 25 ℃ by the filtering palladium catalyst of the pillar that is filled with Sai Lite (0.33mmol).Then, adding the solution that generates in excessive methyl alcohol precipitates to make white polymer.Filter this throw out by glass funnel, and in vacuum drying oven 80 ℃ of following dried recovered products 24 hours to obtain polymkeric substance (yield: 92%).

Embodiment 18

With with mode identical in embodiment 17, use catalytic amount, polymer solvent and polymerization time and the pre-catalyst C identical be summarized in the following table 3 to prepare 5-norbornylene-2-carboxylate methyl ester polymkeric substance with embodiment 17.

Comparing embodiment 4

With with mode identical in embodiment 17, use catalytic amount, polymer solvent and polymerization time and the pre-catalyst A identical be summarized in the following table 3 to prepare 5-norbornylene-2-carboxylate methyl ester polymkeric substance with embodiment 17.

Table 3

	Monomer ¹⁾	Pre-catalyst	[M]/pre-catalyst	[Ani]	Time (h)	Solvent	Mn	Mw	Mw/ Mn ²⁾	Yield (%) ³⁾
	Monomer ¹⁾	Pre-catalyst	[M]/pre-catalyst	[Ani]	Time (h)	Solvent	Mn	Mw	Mw/ Mn ²⁾	Yield (%) ³⁾	Embodiment 16	b(50∶50)	C	100/1	BF ₄ ^-	20	Toluene	2,500	5,600	2.22	55
Embodiment 17	b(50∶50)	B	100/1	SbF ₆ ^-	6	Chlorobenzene	40,929	57,311	1.40	92	Embodiment 16	b(50∶50)	C	100/1	BF ₄ ^-	20	Toluene	2,500	5,600	2.22	55
Embodiment 17	b(50∶50)	B	100/1	SbF ₆ ^-	6	Chlorobenzene	40,929	57,311	1.40	92	Embodiment 18	b(50∶50)	C	100/1	SbF ₆ ^-	6	Chlorobenzene	77,702	104,482	1.34	95
Comparing embodiment 4	b(50∶50)	A	100/1	SbF ₆ ^-	6	Chlorobenzene	25,901	34,438	1.32	93	Embodiment 18	b(50∶50)	C	100/1	SbF ₆ ^-	6	Chlorobenzene	77,702	104,482	1.34	95

1): the numeral endo isomer in the bracket and the ratio of exo isomer

2): use polystyrene standard to measure by GPC

3): the yield after separating fully

Embodiment 19

The polymerization of 5-norbornylene-2-carboxylate methyl ester (exo isomer: endo isomer=20: 80, monomer b)

In the 100ml Schlenk flask that the 15ml chlorobenzene is housed, add 5-norbornylene-2-carboxylate methyl ester (exo isomer: endo isomer=20: 80,5ml (33.0mmol)).In glove box with pre-catalyst B and hexafluoro-antimonic acid silver (AgSbF ₆) be dissolved in the 5ml chlorobenzene, and stirred this reaction mixture 1 hour.Then, in flask, add, and this flask was stirred 12 hours at 25 ℃ by the filtering palladium catalyst of the pillar that is filled with Sai Lite (0.33mmol).Then, adding the solution that generates in excessive methyl alcohol precipitates to make white polymer.Filter this throw out by glass funnel, and in vacuum drying oven 80 ℃ of following dried recovered products 24 hours to obtain polymkeric substance (yield: 48%).

Embodiment 20

With with mode identical in embodiment 19, use catalytic amount, polymer solvent and polymerization time and the pre-catalyst C identical be summarized in the following table 4 to prepare 5-norbornylene-2-carboxylate methyl ester polymkeric substance with embodiment 19.

Comparing embodiment 5

With with mode identical in embodiment 19, use catalytic amount, polymer solvent and polymerization time and the pre-catalyst A identical be summarized in the following table 4 to prepare 5-norbornylene-2-carboxylate methyl ester polymkeric substance with embodiment 19.

Table 4

	Monomer ¹⁾	Pre-catalyst	[M]/pre-catalyst	[Ani]	Time (h)	Solvent	Mn	Mw	Mw/ Mn ²⁾	Yield (%) ³⁾
	Monomer ¹⁾	Pre-catalyst	[M]/pre-catalyst	[Ani]	Time (h)	Solvent	Mn	Mw	Mw/ Mn ²⁾	Yield (%) ³⁾	Embodiment 19	b(20∶80)	B	100/1	SbF ₆ ^-	12	Chlorobenzene	7,524	11,049	1.46	48
Embodiment 20	b(20∶80)	C	100/1	SbF ₆ ^-	12	Chlorobenzene	11,257	15,857	1.40	52	Embodiment 19	b(20∶80)	B	100/1	SbF ₆ ^-	12	Chlorobenzene	7,524	11,049	1.46	48
Embodiment 20	b(20∶80)	C	100/1	SbF ₆ ^-	12	Chlorobenzene	11,257	15,857	1.40	52	Comparing embodiment 5	b(20∶80)	A	100/1	SbF ₆ ^-	12	Chlorobenzene	6,242	8,543	1.36	75

1): the numeral endo isomer in the bracket and the ratio of exo isomer

2): use polystyrene standard to measure by GPC

3): the yield after separating fully

Embodiment 21

The polymerization of 5-norbornylene-2-butyl carboxylate (exo isomer: endo isomer=95: 5, monomer c)

To 15ml toluene and methylene dichloride (CH are housed ₂Cl ₂) add 5-norbornylene-2-butyl carboxylate (exo isomer: endo isomer=95: 5,5ml (34.4mmol)) in the 100ml Schlenk flask of mixing solutions of (1: 1).In glove box with pre-catalyst B and silver tetrafluoroborate (AgBF ₄) be dissolved in the mixing solutions of 5ml methylene dichloride and toluene (1: 1), and stirred this reaction mixture 1 hour.Then, in flask, add, and this flask was stirred 12 hours at 25 ℃ by the filtering palladium catalyst of the pillar that is filled with Sai Lite (0.17mmol).Then, adding the solution that generates in excessive methyl alcohol precipitates to make white polymer.Filter this throw out by glass funnel, and in vacuum drying oven 80 ℃ of following dried recovered products 24 hours to obtain polymkeric substance (yield: 74%).

Embodiment 22

With with mode identical in embodiment 21, use catalytic amount, polymer solvent and polymerization time and the pre-catalyst C identical be summarized in the following table 5 to prepare 5-norbornylene-2-butyl carboxylate polymkeric substance with embodiment 21.

Comparing embodiment 6

With with mode identical in embodiment 21, use catalytic amount, polymer solvent and polymerization time and the pre-catalyst A identical be summarized in the following table 5 to prepare 5-norbornylene-2-butyl carboxylate polymkeric substance with embodiment 21.

Comparing embodiment 7

In the 100ml Schlenk flask that the 15ml chlorobenzene is housed, add 5-norbornylene-2-butyl carboxylate (exo isomer: endo isomer=95: 5,5ml (34.4mmol)).In glove box with pre-catalyst A and silver tetrafluoroborate (AgBF ₄) be dissolved in the 5ml chlorobenzene, and stirred this reaction mixture 1 hour.Then, in flask, add, and this flask was stirred 20 hours at 25 ℃ by the filtering palladium catalyst of the pillar that is filled with Sai Lite (0.34mmol).Then, adding the solution that generates in excessive methyl alcohol precipitates to make white polymer.Filter this throw out by glass funnel, and in vacuum drying oven 80 ℃ of following dried recovered products 24 hours to obtain polymkeric substance (yield: 76%).

Table 5

	Monomer ¹⁾	Pre-catalyst	[M]/pre-catalyst	[Ani]	Time (h)	Solvent	Mn	Mw	Mw/ Mn ²⁾	Yield (%) ³⁾
	Monomer ¹⁾	Pre-catalyst	[M]/pre-catalyst	[Ani]	Time (h)	Solvent	Mn	Mw	Mw/ Mn ²⁾	Yield (%) ³⁾	Embodiment 21	c(95∶5)	B	200/1	BF ₄ ^-	12	Toluene/CH ₂Cl ₂	40,322	49,345	1.22	74
Embodiment 22	c(95∶5)	C	200/1	BF ₄ ^-	12	Toluene/CH ₂Cl ₂	70,417	94,148	1.33	82	Embodiment 21	c(95∶5)	B	200/1	BF ₄ ^-	12	Toluene/CH ₂Cl ₂	40,322	49,345	1.22	74
Embodiment 22	c(95∶5)	C	200/1	BF ₄ ^-	12	Toluene/CH ₂Cl ₂	70,417	94,148	1.33	82	Comparing embodiment 6	c(95∶5)	A	200/1	BF ₄ ^-	12	Toluene/CH ₂Cl ₂	65,026	83,835	1.20	73
Comparing embodiment 7	c(95∶5)	A	100/1	BF ₄ ^-	20	Chlorobenzene	9,313	15,544	1.66	76	Comparing embodiment 6	c(95∶5)	A	200/1	BF ₄ ^-	12	Toluene/CH ₂Cl ₂	65,026	83,835	1.20	73

1): the numeral endo isomer in the bracket and the ratio of exo isomer

2): use polystyrene standard to measure by GPC

3): the yield after separating fully

Embodiment 23

In the 100ml Schlenk of the mixing solutions that 15ml toluene and methylene dichloride (1: 1) are housed flask, add 5-norbornylene-2-butyl carboxylate (exo isomer: endo isomer=95: 5,5ml (34.4mmol)).In glove box with pre-catalyst C and hexafluoro-antimonic acid silver (AgSbF ₆) be dissolved in the mixing solutions of 5ml methylene dichloride and toluene (1: 1), and stirred this reaction mixture 1 hour.Then, in flask, add, and this flask was stirred 12 hours at 25 ℃ by the filtering palladium catalyst of the pillar that is filled with Sai Lite (0.17mmol).Then, adding the solution that generates in excessive methyl alcohol precipitates to make white polymer.Filter this throw out by glass funnel, and in vacuum drying oven 80 ℃ of following dried recovered products 24 hours to obtain polymkeric substance (yield: 95%).

Embodiment 24

As in following table 6, summing up ground, except the ratio of monomer and pre-catalyst is 1000/1, with mode identical in embodiment 23, use and embodiment 23 identical negatively charged ion, polymer solvent and polymerization times prepare 5-norbornylene-2-butyl carboxylate polymkeric substance.

Embodiment 25

As in following table 6, summing up ground, except the ratio of monomer and pre-catalyst is 5000/1, with mode identical in embodiment 23, use and embodiment 23 identical negatively charged ion, polymer solvent and polymerization times prepare 5-norbornylene-2-butyl carboxylate polymkeric substance.

Comparing embodiment 8

As in following table 6, summing up ground, except the ratio that uses pre-catalyst A and monomer and pre-catalyst is 1000/1, with with mode identical in embodiment 23, use negatively charged ion, polymer solvent and the polymerization time identical to prepare 5-norbornylene-2-butyl carboxylate polymkeric substance with embodiment 23.

Comparing embodiment 9

As in following table 6, summing up ground, except the ratio that uses pre-catalyst A and monomer and pre-catalyst is 5000/1, with with mode identical in embodiment 23, use negatively charged ion, polymer solvent and the polymerization time identical to prepare 5-norbornylene-2-butyl carboxylate polymkeric substance with embodiment 23.

Table 6

	Monomer ¹⁾	Pre-catalyst	[M]/pre-catalyst	[Ani]	Time (h)	Solvent	Mn	Mw	Mw/ Mn ²⁾	Yield (%) ³⁾
	Monomer ¹⁾	Pre-catalyst	[M]/pre-catalyst	[Ani]	Time (h)	Solvent	Mn	Mw	Mw/ Mn ²⁾	Yield (%) ³⁾	Embodiment 23	c(95∶5)	C	200/1	SbF ₆ ^-	12	Toluene/CH ₂Cl ₂	51,980	69,306	1.33	95
Embodiment 24	c(95∶5)	C	1000/1	SbF ₆ ^-	12	Toluene/CH ₂Cl ₂	93,570	118,215	1.26	45	Embodiment 23	c(95∶5)	C	200/1	SbF ₆ ^-	12	Toluene/CH ₂Cl ₂	51,980	69,306	1.33	95
Embodiment 24	c(95∶5)	C	1000/1	SbF ₆ ^-	12	Toluene/CH ₂Cl ₂	93,570	118,215	1.26	45	Embodiment 25	c(95∶5)	C	5000/1	SbF ₆ ^-		Toluene/CH ₂Cl ₂	103,579	143,974	1.39	42
Comparing embodiment 6	c(95∶5)	A	1000/1	SbF ₆ ^-	12	Toluene/CH ₂Cl ₂	53,429	74,804	1.40	40	Embodiment 25	c(95∶5)	C	5000/1	SbF ₆ ^-		Toluene/CH ₂Cl ₂	103,579	143,974	1.39	42
Comparing embodiment 6	c(95∶5)	A	1000/1	SbF ₆ ^-	12	Toluene/CH ₂Cl ₂	53,429	74,804	1.40	40	Comparing embodiment 7	c(95∶5)	A	5000/1	SbF ₆ ^-	12	Toluene/CH ₂Cl ₂	61,382	89,004	1.45	39

1): the numeral endo isomer in the bracket and the ratio of exo isomer

2): use polystyrene standard to measure by GPC

3): the yield after separating fully

Embodiment 26

The polymerization of 5-norbornylene-2-methyl acetic acid ester (exo isomer: endo isomer=40: 60, monomer d)

In the 100ml Schlenk flask that contains 15ml toluene, add 5-norbornylene-2-methyl acetic acid ester (exo isomer: endo isomer=40: 60,5ml (30.9mmol)).In glove box with pre-catalyst B and silver tetrafluoroborate (AgBF ₄) be dissolved in the mixing solutions of 5ml methylene dichloride and toluene, and stirred reaction mixture 1 hour.Then, in flask, add by the filtering palladium catalyst of the pillar that is filled with Sai Lite (0.031mmol), and 25 ℃ of stirred flask 20 hours.Then, adding the solution that generates in excessive methyl alcohol precipitates to make white polymer.Filter this throw out by glass funnel, and in vacuum drying oven 80 ℃ of dried recovered products 24 hours to obtain polymkeric substance (yield: 62%).

Embodiment 27

With with mode identical in embodiment 26, use catalytic amount, negatively charged ion, polymer solvent and polymerization time and the pre-catalyst C identical be summarized in the following table 7 to prepare 5-norbornylene-2-methyl acetic acid ester polymer with embodiment 26.

Comparing embodiment 10

With with mode identical in embodiment 26, use catalytic amount, negatively charged ion, polymer solvent and polymerization time and the pre-catalyst A identical be summarized in the following table 7 to prepare 5-norbornylene-2-methyl acetic acid ester polymer with embodiment 26.

Table 7

	Monomer ¹⁾	Pre-catalyst	[M]/pre-catalyst	[Ani]	Time (h)	Solvent	Mn	Mw	Mw/ Mn ²⁾	Yield (%) ³⁾
	Monomer ¹⁾	Pre-catalyst	[M]/pre-catalyst	[Ani]	Time (h)	Solvent	Mn	Mw	Mw/ Mn ²⁾	Yield (%) ³⁾	Embodiment 26	d(40∶60)	B	1000/1	20	Toluene	52,370	103,692	1.98	62
Embodiment 27	d(40∶60)	C	1000/1		20	Toluene	47,940	89,648	1.87	57	Embodiment 26	d(40∶60)	B	1000/1	20	Toluene	52,370	103,692	1.98	62
Embodiment 27	d(40∶60)	C	1000/1		20	Toluene	47,940	89,648	1.87	57	Comparing embodiment 10	d(40∶60)	A	1000/1	20	Toluene	40,554	77,864	1.92	55

1): the numeral endo isomer in the bracket and the ratio of exo isomer

2): use polystyrene standard to measure by GPC

3): the yield after separating fully

Embodiment 28

Norbornylene (monomer a) with the copolymerization of 5-norbornylene-2-carboxylate methyl ester (monomer b) (3: 1)

In 100ml Schlenk flask, add norbornylene (3g, 31.9mmol), 5-norbornylene-2-carboxylate methyl ester (1.6ml, 10.6mmol) and toluene (14mL).In glove box with pre-catalyst B and silver tetrafluoroborate (AgBF ₄) be dissolved in the mixing solutions of 5ml methylene dichloride and toluene (1: 1), and stirred reaction mixture 1 hour.Then, in flask, add by the filtering palladium catalyst of the pillar that is filled with Sai Lite (0.42mmol), and 25 ℃ of stirred flask 20 hours.Then, adding the solution that generates in excessive methyl alcohol precipitates to make white copolymer.Filter this throw out by glass funnel, and in vacuum drying oven 80 ℃ of dried recovered products 24 hours to obtain polymkeric substance (yield: 70%).

Embodiment 29

With with mode identical in embodiment 28, the multipolymer that uses catalytic amount, polymerization time, negatively charged ion and the polymer solvent identical be summarized in the following table 8 and pre-catalyst C to prepare norbornylene and 5-norbornylene-2-carboxylate methyl ester with embodiment 28.

Comparing embodiment 11

With with mode identical in embodiment 28, the multipolymer that uses catalytic amount, polymerization time, negatively charged ion and the polymer solvent identical be summarized in the following table 8 and pre-catalyst A to prepare norbornylene and 5-norbornylene-2-carboxylate methyl ester with embodiment 28.

Embodiment 30

In 100ml Schlenk flask, add norbornylene (3g, 31.9mmol), 5-norbornylene-2-carboxylate methyl ester (1.6ml, 10.6mmol) and toluene (14ml).In glove box with pre-catalyst C and hexafluoro-antimonic acid silver (AgSbF ₆) be dissolved in the chlorobenzene, and stirred reaction mixture 1 hour.Then, in flask, add by the filtering palladium catalyst of the pillar that is filled with Sai Lite (0.42mmol), and 25 ℃ of stirred flask 12 hours.Then, adding the solution that generates in excessive methyl alcohol precipitates to make white copolymer.Filter this throw out by glass funnel, and in vacuum drying oven 80 ℃ of dried recovered products 24 hours to obtain polymkeric substance (yield: 98%).

Table 8

1): numeral monomer a in the bracket and the molar ratio of monomer b (endo isomer among the monomer b: the ratio of exo isomer is 5: 95)

2): in tetrahydrofuran (THF), do not dissolve

3): use polystyrene standard to measure by GPC

4): use NMR to measure

5): the yield after separating fully

Embodiment 31

Norbornylene (monomer a) with 5-norbornylene-2-butyl carboxylate's (monomer c) (3: 1) copolymerization

In 100ml Schlenk flask, add norbornylene (3g, 31.9mmol), 5-norbornylene-2-butyl carboxylate (1.54ml, 10.6mmol) and toluene (14ml).In glove box with pre-catalyst B and silver tetrafluoroborate (AgBF ₄) be dissolved in the mixing solutions of 5ml methylene dichloride and toluene (1: 1), and stirred reaction mixture 1 hour.Then, in flask, add by the filtering palladium catalyst of the pillar that is filled with Sai Lite (0.42mmol), and 25 ℃ of stirred flask 20 hours.Then, adding the solution that generates in excessive methyl alcohol precipitates to make white copolymer.Filter this throw out by glass funnel, and in vacuum drying oven 80 ℃ of dried recovered products 24 hours to obtain polymkeric substance (yield: 72%).

Embodiment 32

With with mode identical in embodiment 31, use catalytic amount, polymerization time, negatively charged ion and polymer solvent and the pre-catalyst C identical be summarized in the following table 9 to prepare norbornylene and 5-norbornylene-2-butyl carboxylate multipolymer with embodiment 31.

Comparing embodiment 12

With with mode identical in embodiment 31, use catalytic amount, polymerization time, negatively charged ion and polymer solvent and the pre-catalyst A identical be summarized in the following table 9 to prepare norbornylene and 5-norbornylene-2-butyl carboxylate multipolymer with embodiment 31.

Embodiment 33

In 100ml Schlenk flask, add norbornylene (3g, 31.9mmol), 5-norbornylene-2-butyl carboxylate (1.54ml, 10.6mmol) and toluene (14ml).In glove box with pre-catalyst C and hexafluoro-antimonic acid silver (AgSbF ₆) be dissolved in the chlorobenzene, and stirred reaction mixture 1 hour.Then, in flask, add by the filtering palladium catalyst of the pillar that is filled with Sai Lite (0.42mmol), and 25 ℃ of stirred flask 12 hours.Then, adding the solution that generates in excessive methyl alcohol precipitates to make white copolymer.Filter this throw out by glass funnel, and in vacuum drying oven 80 ℃ of dried recovered products 24 hours to obtain polymkeric substance (yield: 87%).

Table 9

1): numeral monomer a in the bracket and the molar ratio of monomer c (endo isomer among the monomer c: the ratio of exo isomer is 5: 95)

2): in tetrahydrofuran (THF), do not dissolve

3): use polystyrene standard to measure by GPC

4): use NMR to measure

5): the yield after separating fully

Embodiment 34

Norbornylene (monomer a) with the copolymerization of 5-norbornylene-2-carboxylate methyl ester (monomer b) (5: 1)

In 100ml Schlenk flask, add norbornylene (4g, 42.5mmol), 5-norbornylene-2-carboxylate methyl ester (1.3ml, 8.5mmol) and toluene (14ml).In glove box with pre-catalyst B and silver tetrafluoroborate (AgBF ₄) be dissolved in the mixing solutions of methylene dichloride and toluene (1: 1), and stirred reaction mixture 1 hour.Then, in flask, add by the filtering palladium catalyst of the pillar that is filled with Sai Lite (0.42mmol), and 25 ℃ of stirred flask 20 hours.Then, adding the solution that generates in excessive methyl alcohol precipitates to make white copolymer.Filter this throw out by glass funnel, and in vacuum drying oven 80 ℃ of dried recovered products 24 hours to obtain polymkeric substance (yield: 82%).

Embodiment 35

With with mode identical in embodiment 34, use catalytic amount, polymerization time, negatively charged ion and polymer solvent and the pre-catalyst C identical be summarized in the following table 10 to prepare norbornylene and 5-norbornylene-2-carboxylate methyl ester (5: 1) multipolymer with embodiment 34.

Comparing embodiment 13

Embodiment 36

In 100ml Schlenk flask, add norbornylene (4g, 42.5mmol), 5-norbornylene-2-carboxylate methyl ester (1.3ml, 8.5mmol) and toluene (14ml).In glove box with pre-catalyst C and hexafluoro-antimonic acid silver (AgSbF ₆) be dissolved in the chlorobenzene, and stirred reaction mixture 1 hour.Then, in flask, add by the filtering palladium catalyst of the pillar that is filled with Sai Lite (0.42mmol), and 25 ℃ of stirred flask 12 hours.Then, adding the solution that generates in excessive methyl alcohol precipitates to make white copolymer.Filter this throw out by glass funnel, and in vacuum drying oven 80 ℃ of dried recovered products 24 hours to obtain polymkeric substance (yield: 98%).

Table 10

2): in tetrahydrofuran (THF), do not dissolve

3): use polystyrene standard to measure by GPC

4): use NMR to measure

5): the yield after separating fully

Embodiment 37

Norbornylene (monomer a) with 5-norbornylene-2-butyl carboxylate's (monomer c) (5: 1) copolymerization

In 100ml Schlenk flask, add norbornylene (4g, 42.5mmol), 5-norbornylene-2-butyl carboxylate (1.2ml, 8.5mmol) and toluene (14ml).In glove box with pre-catalyst B and silver tetrafluoroborate (AgBF ₄) be dissolved in the mixing solutions of methylene dichloride and toluene (1: 1), and stirred reaction mixture 1 hour.Then, in flask, add by the filtering palladium catalyst of the pillar that is filled with Sai Lite (0.42mmol), and 25 ℃ of stirred flask 20 hours.Then, adding the solution that generates in excessive methyl alcohol precipitates to make white copolymer.Filter this throw out by glass funnel, and in vacuum drying oven 80 ℃ of dried recovered products 24 hours to obtain polymkeric substance (yield: 74%).

Embodiment 38

In 100ml Schlenk flask, add norbornylene (4g, 42.5mmol), 5-norbornylene-2-butyl carboxylate (1.2ml, 8.5mmol) and toluene (14ml).In glove box with pre-catalyst C and hexafluoro-antimonic acid silver (AgSbF ₆) be dissolved in the chlorobenzene, and stirred reaction mixture 1 hour.Then, in flask, add by the filtering palladium catalyst of the pillar that is filled with Sai Lite (0.42mmol), and 25 ℃ of stirred flask 12 hours.Then, adding the solution that generates in excessive methyl alcohol precipitates to make white copolymer.Filter this throw out by glass funnel, and in vacuum drying oven 80 ℃ of dried recovered products 24 hours to obtain polymkeric substance (yield: 89%).

Embodiment 39

With with mode identical in embodiment 37, use catalytic amount, polymerization time, negatively charged ion and polymer solvent and the pre-catalyst C identical be summarized in the following table 11 to prepare norbornylene and 5-norbornylene-2-butyl carboxylate (5: 1) multipolymer with embodiment 37.

Comparing embodiment 14

With with mode identical in embodiment 37, use catalytic amount, polymerization time, negatively charged ion and polymer solvent and the pre-catalyst A identical be summarized in the following table 11 to prepare norbornylene and 5-norbornylene-2-butyl carboxylate (5: 1) multipolymer with embodiment 37.

Table 11

1): numeral monomer a in the bracket and the molar ratio of monomer c (endo isomer among the monomer b: the ratio of exo isomer is 5: 95)

2): in tetrahydrofuran (THF), do not dissolve

3): use polystyrene standard to measure by GPC

4): use NMR to measure

5): the yield after separating fully

Comparing embodiment 15

Use [(allyl group) PdCl] ₂Replace pre-catalyst A, carry out the experiment identical with embodiment 11.But, do not react.Summed up experimental result in the following table 12.

Comparing embodiment 16

Do not use salt compound AgBF ₄, carry out the experiment identical with embodiment 11.But, do not react.Summed up experimental result in the following table 12.

Table 12

1): in tetrahydrofuran (THF), do not dissolve

2): use polystyrene standard to measure by GPC

3): the yield after separating fully

As mentioned among the embodiment 1～39 as seen, under the situation that metal catalyst complexes according to the present invention exists, when unsubstituted norbornene monomer or contain the norbornene monomer of polar functional group and when equal polymerization of another monomer or copolymerization, in most of polyreaction,, polar functional group do not reduce activity of such catalysts owing to obtaining the addition polymer of high yield.In addition, different with the polymerization under the situation about existing at the pre-catalyst (pre-catalyst A) that replaces without halogen, pre-catalyst that halogen replaces (pre-catalyst B (I) and the polymerization under pre-catalyst C (the Br)) situation about existing produce and have at least 5,000 (is 20 in embodiment 17～18 and comparing embodiment 4,000 or bigger, in embodiment 19～20 and comparing embodiment 5, be 5,000 or bigger, in embodiment 22 and comparing embodiment 6, be 10,000 or bigger, in embodiment 25 and comparing embodiment 8, be 40,000 or bigger, in embodiment 26～27 and comparing embodiment 10, be 10,000 or bigger) weight average molecular weight (M _w) polymkeric substance.This shows that the performance of the pre-catalyst that halogen replaces is much better than the performance of the catalyzer that replaces without halogen.The enhancing of this catalyst performance is owing to the electronic effect of part.

Particularly, use in the method for the present invention and carbenes coordinate catalyzer, thereby compare, increase the weight-average molecular weight (M of polymkeric substance with the catalyzer that uses the electronic effect that does not have part with functional group of the electronic effect that part can be provided _w) or yield.

Particularly, consider that the norbornylene that comprises polar substituent has low reactivity usually, therefore think under existing preparation according to the situation of metal catalyst complexes of the present invention have higher yields and 5,000 or the norbornene polymer of bigger Mw have important commercial significance.

For example, people such as Sen [Organometallics 2001, Vol.20,2802-2812] pass through by [(1, the 5-cyclooctadiene) (CH ₃) Pd (Cl)] catalysis and by phosphine (PPh ₃) and [Na] ⁺[B (3,5-(CF ₃) ₂C ₆H ₃) ₄] ^-Syncatalytic polymerization prepares the ester norbornene polymer.Yet catalyzer and monomeric ratio are that the polymerization yield is 40% or littler, and the molecular weight of polymkeric substance only is 6500 under about 1/400 the experiment condition therein.

U.S. Patent No. 6,455,650 disclose a kind of by [(R ') _zM (L ') _x(L ") _y] _b[WCA] _dThe catalyst complexes of expression exists polymerization down based on the method for functionalized norbornene monomer, and phosphine is used as part with the hydrocarbon that comprises alkyl (for example allyl group) in described catalyst complexes.Yet in this case, the polymerization that contains the norbornene monomer of polar functional group (for example, carbonyl) only is 5% extremely low yield.

Heat stability testing (TGA)

Use Perkin-Elmer TGA-7,, blow nitrogen (N with the flow rate of 5ml/min by under the heating rate of 10 ℃/min ₂) carry out about 4.4～4.6mg polynorbornene 2-carboxylate methyl ester (exo isomer: TGA endo isomer=50: 50).The TGA result of the homopolymer of preparation in embodiment 16～18 and the comparing embodiment 4 has been described among Fig. 2.With reference to figure 2, all polymkeric substance show good thermal stability under 300 ℃ or higher temperature, and imponderability changes.

Claims

1, a kind of addition polymerization by cycloolefin monomers prepares the method for cyclic olefin polymer, and this method comprises: the metal catalyst complexes by following general formula 1 expression is contacted with the cycloolefin monomers of being represented by following general formula 2:

＜general formula 1 〉

[M(L ₁) _x(L′ ₂) _y(L ₃) _z] _a[Ani] _b

Wherein, M is an X family metal,

[M (L ₁) _x(L ' ₂) _y(L ₃) _z] be cationic complexes,

L ₁For comprising the anion ligand of alkyl,

L ' ₂Be neutral ligand,

L ₃Be the N-heterocyclic carbene ligand,

X is 1 or 2; Y is 0～4; Z is 1 or 2; 2≤x+y+z≤6,

＜general formula 2 〉

Wherein, m is 0～4 integer,

Wherein, nonpolar functional group is: be selected from by hydrogen; Halogen; C1～C20 straight or branched alkyl, haloalkyl, alkenyl or halogenated alkenyl; C3～C20 straight or branched alkynyl or halo alkynyl; Do not replace or by the C3～C12 cycloalkyl of alkyl, alkenyl, alkynyl, halogen, haloalkyl, halogenated alkenyl or halo alkynyl substituted; Do not replace or by the C6～C40 aryl of alkyl, alkenyl, alkynyl, halogen, haloalkyl, halogenated alkenyl or halo alkynyl substituted; Do not replace or the group that C7～the C15 aralkyl is formed by alkyl, alkenyl, alkynyl, halogen, haloalkyl, halogenated alkenyl or halo alkynyl substituted in, and

Wherein, described polar functional group is: comprise at least a nonhydrocarbon polar group in oxygen, nitrogen, phosphorus, sulphur, silicon and the boron, and be selected from by-R ⁸OR ⁹,-OR ⁹,-OC (O) OR ⁹,-R ⁸OC (O) OR ⁹,-C (O) R ⁹,-R ⁸C (O) R ⁹,-OC (O) R ⁹,-R ⁸C (O) OR ⁹,-C (O) OR ⁹,-R ⁸OC (O) R ⁹,-(R ⁸O) _k-OR ⁹,-(OR ⁸) _k-OR ⁹,-C (O)-O-C (O) R ⁹,-R ⁸C (O)-O-C (O) R ⁹,-SR ⁹,-R ⁸SR ⁹,-SSR ⁸,-R ⁸SSR ⁹,-S (=O) R ⁹,-R ⁸S (=O) R ⁹,-R ⁸C (=S) R ⁹,-R ⁸C (=S) SR ⁹,-R ⁸SO ₃R ⁹,-SO ₃R ⁹,-R ⁸N=C=S ,-N=C=S ,-NCO, R ⁸-NCO ,-CN ,-R ⁸CN ,-NNC (=S) R ⁹,-R ⁸NNC (=S) R ⁹,-NO ₂,-R ⁸NO ₂,-P (R ⁹) ₂,-R ⁸P (R ⁹) ₂,-P (=O) (R ⁹) ₂,-R ⁸P (=O) (R ⁹) ₂,

In the group of forming, R wherein ⁸And R ¹¹Respectively be C1～C20 straight or branched alkylidene group, halo alkylidene group, alkylene group or halo alkylene group; C3～C20 straight or branched alkynylene or halo alkynylene; Do not replace or encircle alkylidene group by the C3～C12 of alkyl, alkenyl, alkynyl, halogen, haloalkyl, halogenated alkenyl or halo alkynyl substituted; Do not replace or by the C6～C40 arylidene of alkyl, alkenyl, alkynyl, halogen, haloalkyl, halogenated alkenyl or halo alkynyl substituted; Perhaps do not replace or by the inferior aralkyl of C7～C15 of alkyl, alkenyl, alkynyl, halogen, haloalkyl, halogenated alkenyl or halo alkynyl substituted,

Each k is 1～10 integer.

2, method according to claim 1, wherein, described N-heterocyclic carbene ligand is to be selected from least a in the group that the compound represented by following general formula 3A～3D forms:

Wherein, R ₂₅, R ₂₆, R ₂₇, R ₂₈, R ₂₉And R ₃₀Be independently of one another: hydrogen, C1～C20 straight or branched alkyl, C3～C12 cycloalkyl, C2～C20 straight or branched alkenyl, C6～C15 cycloalkenyl group, C3～C20 straight or branched allyl group, C6～C30 aryl, C6～C30 comprises heteroatomic aryl or C7～C30 aralkyl, its each freely be selected from C1～C5 straight or branched alkyl or haloalkyl, C2～C5 straight or branched alkenyl or halogenated alkenyl, halogen, sulphur, oxygen, nitrogen, phosphorus and by C1～C5 straight or branched alkyl or haloalkyl, at least a alkyl in the phenyl that halogen or heteroatoms replace and/or hetero atom substituents replace.

3, method according to claim 1, wherein, described [Ani] be can with coordinate negatively charged ion a little less than the X family metal M, and for being selected from by borate, aluminate, [SbF ₆]-, [PF ₆]-, [AsF ₆]-, perfluor acetate moiety [CF ₃CO ₂]-, perfluorinated acid root [C ₂F ₅CO ₂]-, perfluorobutyric acid root [CF ₃CF ₂CF ₂CO ₂]-, perchlorate [ClO ₄]-, tosic acid root [p-CH ₃C ₆H ₄SO ₃]-, [SO ₃CF ₃A kind of in]-, boric acid benzene and the group that do not replace or form by the carborane that halogen replaces.

4, method according to claim 3, wherein, described borate or the aluminate negatively charged ion that following general formula 4A or 4B represent of serving as reasons:

＜general formula 4A 〉

[M′(R ₃₀) ₄]

＜general formula 4B 〉

[M′(OR ₃₀) ₄]

Wherein, M ' be boron or aluminium and

5. method according to claim 1, wherein, described metal catalyst complexes is represented by following general formula 5:

＜general formula 5 〉

Wherein, M, L ₁, L ₂', L ₃, [Ani], a and b as defined in claim 1.

6, method according to claim 1, wherein, described metal catalyst complexes is to be selected from the compound of being represented by following general formula 6A～6D:

＜general formula 6A〉＜general formula 6B 〉

＜general formula 6C〉＜general formula 6D 〉

Wherein, M, L ₁, L ₂', [Ani], a and b as defined in claim 1 and

R ₁～R ₆Be independently of one another: hydrogen; Halogen; C1～C20 straight or branched alkyl, alkoxyl group, allyl group, alkenyl or vinyl; Do not replace or by the C3～C12 cycloalkyl of alkyl, alkenyl, alkynyl, halogen, haloalkyl, halogenated alkenyl or halo alkynyl substituted; Do not replace or by the C6～C40 aryl of alkyl, alkenyl, alkynyl, halogen, haloalkyl, halogenated alkenyl or halo alkynyl substituted; Do not replace or by the C7～C15 aralkyl of alkyl, alkenyl, alkynyl, halogen, haloalkyl, halogenated alkenyl or halo alkynyl substituted; Perhaps C3～C20 alkynyl.

7, method according to claim 1, wherein, described metal catalyst complexes is represented by following general formula 7:

＜general formula 7 〉

Wherein, M, L ₁, L ₂', [Ani], a and b as defined in claim 1 and

R ₁, R ₂And R ₅Be independently of one another: hydrogen; Halogen; C1～C20 straight or branched alkyl, alkoxyl group, allyl group, alkenyl or vinyl; Do not replace or by the C3～C12 cycloalkyl of alkyl, alkenyl, alkynyl, halogen, haloalkyl, halogenated alkenyl or halo alkynyl substituted; Do not replace or by the C6～C40 aryl of alkyl, alkenyl, alkynyl, halogen, haloalkyl, halogenated alkenyl or halo alkynyl substituted; Do not replace or by the C7～C15 aralkyl of alkyl, alkenyl, alkynyl, halogen, haloalkyl, halogenated alkenyl or halo alkynyl substituted; Perhaps C3～C20 alkynyl.

8, method according to claim 1, wherein, described metal catalyst complexes is represented by following general formula 8:

＜general formula 8 〉

Wherein, M, L ₂', [Ani], a and b as defined in claim 1,

R ₁, R ₂And R ₅Be independently of one another: hydrogen; Halogen; C1～C20 straight or branched alkyl, alkoxyl group, allyl group, alkenyl or vinyl; Do not replace or by the C3～C12 cycloalkyl of alkyl, alkenyl, alkynyl, halogen, haloalkyl, halogenated alkenyl or halo alkynyl substituted; Do not replace or by the C6～C40 aryl of alkyl, alkenyl, alkynyl, halogen, haloalkyl, halogenated alkenyl or halo alkynyl substituted; Do not replace or by the C7～C15 aralkyl of alkyl, alkenyl, alkynyl, halogen, haloalkyl, halogenated alkenyl or halo alkynyl substituted; Perhaps C3～C20 alkynyl and

Be the C3 allyl group.

9, method according to claim 1, wherein, described metal catalyst complexes is installed on the microparticle support.

10, method according to claim 9, wherein, described microparticle support is silicon-dioxide, titanium dioxide, silicon-dioxide/chromic oxide, silicon-dioxide/chromic oxide/titanium dioxide, silica/alumina, phosphaljel, silanized silica, silica hydrogel, montmorillonitic clay or zeolite.

11, method according to claim 1, wherein, described metal catalyst complexes is dissolved in the organic solvent that is selected from methylene dichloride, ethylene dichloride, toluene, chlorobenzene and composition thereof.

12, method according to claim 1, wherein, described metal catalyst part is introduced in the monomer solution as solid phase.

13, method according to claim 1, wherein, described cyclic olefin polymer is the cycloolefin homopolymers with polar functional group, the multipolymer with cycloolefin monomers of opposed polarity functional group; Or cycloolefin monomers with polar functional group and multipolymer with cycloolefin monomers of nonpolar functional group.

14, method according to claim 1, wherein, described cyclic olefin polymer has 20,000～500,000 weight-average molecular weight (Mw).

15, use the cyclic olefin polymer of each described method preparation in the claim 1～14, its cycloolefin addition polymer for having 20,000～500,000 weight-average molecular weight and comprising polar functional group.

16, cyclic olefin polymer according to claim 15, this cyclic olefin polymer is represented by following general formula 9:

＜general formula 9 〉

Wherein, m, R7, R7 ', R7 " and R7 " ' as defined in claim 1,

R ₇, R ₇', R ₇" and R ₇" ' at least a be polar functional group and

N is the polymerization degree and is 100～5,000 real number.

17, cyclic olefin polymer according to claim 15, this cyclic olefin polymer is represented by following general formula 10:

＜general formula 10 〉

Wherein, m, R7, R7 ', R7 " and R7 " ' as defined in claim 1,

R ₇, R ₇', R ₇" and R ₇" ' at least a be polar functional group,

R ₁₇, R ₁₇', R ₁₇" and R ₁₇The nonpolar functional group of " ' be, and be independently of one another: be selected from by hydrogen; Halogen; C1～C20 straight or branched alkyl, haloalkyl, alkenyl or halogenated alkenyl; C3～C20 straight or branched alkynyl or halo alkynyl; Do not replace or by the C3～C12 cycloalkyl of alkyl, alkenyl, alkynyl, halogen, haloalkyl, halogenated alkenyl or halo alkynyl substituted; Do not replace or by the C6～C40 aryl of alkyl, alkenyl, alkynyl, halogen, haloalkyl, halogenated alkenyl or halo alkynyl substituted; Not in replacement or the group that C7～the C15 aralkyl is formed by alkyl, alkenyl, alkynyl, halogen, haloalkyl, halogenated alkenyl or halo alkynyl substituted.

M can be different,

N ' for the polymerization degree and be 100～2,500 real number and

C and d are molar ratio, c+d=1,0.1≤c≤0.95 and 0.05≤d≤0.9.

18, cyclic olefin polymer according to claim 15, this cyclic olefin polymer is represented by following general formula 11:

＜formula 11 〉

Wherein, m, R7, R7 ', R7 " and R7 " ' as defined in claim 1,

R ₇, R ₇', R ₇" and R ₇" ' at least a be polar functional group,

M can be different,

N " for the polymerization degree and be 1 00～2,500 real number and

E and f are molar ratio, e+f=1,0.1＜e＜0.9 and 0.1＜f＜0.9 and