CN101012314B - Optical anisotropy thin film and display device containing same - Google Patents
Optical anisotropy thin film and display device containing same Download PDFInfo
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- CN101012314B CN101012314B CN2007100004500A CN200710000450A CN101012314B CN 101012314 B CN101012314 B CN 101012314B CN 2007100004500 A CN2007100004500 A CN 2007100004500A CN 200710000450 A CN200710000450 A CN 200710000450A CN 101012314 B CN101012314 B CN 101012314B
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- alkynyl
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- norbornylene
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- 150000002899 organoaluminium compounds Chemical class 0.000 description 1
- 150000001282 organosilanes Chemical class 0.000 description 1
- TWNQGVIAIRXVLR-UHFFFAOYSA-N oxo(oxoalumanyloxy)alumane Chemical compound O=[Al]O[Al]=O TWNQGVIAIRXVLR-UHFFFAOYSA-N 0.000 description 1
- 238000004806 packaging method and process Methods 0.000 description 1
- 238000012856 packing Methods 0.000 description 1
- XKHXKJLNOCSETN-UHFFFAOYSA-N pentane-2,3-dione;sodium Chemical compound [Na].CCC(=O)C(C)=O XKHXKJLNOCSETN-UHFFFAOYSA-N 0.000 description 1
- VLTRZXGMWDSKGL-UHFFFAOYSA-M perchlorate Inorganic materials [O-]Cl(=O)(=O)=O VLTRZXGMWDSKGL-UHFFFAOYSA-M 0.000 description 1
- VLTRZXGMWDSKGL-UHFFFAOYSA-N perchloric acid Chemical compound OCl(=O)(=O)=O VLTRZXGMWDSKGL-UHFFFAOYSA-N 0.000 description 1
- 229910000073 phosphorus hydride Inorganic materials 0.000 description 1
- 239000004033 plastic Substances 0.000 description 1
- 229920003023 plastic Polymers 0.000 description 1
- 229910052697 platinum Inorganic materials 0.000 description 1
- 229920000636 poly(norbornene) polymer Polymers 0.000 description 1
- 229920006254 polymer film Polymers 0.000 description 1
- 230000037048 polymerization activity Effects 0.000 description 1
- 229920002223 polystyrene Polymers 0.000 description 1
- 238000012805 post-processing Methods 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- 239000012429 reaction media Substances 0.000 description 1
- 230000035484 reaction time Effects 0.000 description 1
- 238000002310 reflectometry Methods 0.000 description 1
- 238000007790 scraping Methods 0.000 description 1
- DCKVNWZUADLDEH-UHFFFAOYSA-N sec-butyl acetate Chemical compound CCC(C)OC(C)=O DCKVNWZUADLDEH-UHFFFAOYSA-N 0.000 description 1
- 239000004065 semiconductor Substances 0.000 description 1
- 125000004469 siloxy group Chemical group [SiH3]O* 0.000 description 1
- 229910052708 sodium Inorganic materials 0.000 description 1
- 238000004611 spectroscopical analysis Methods 0.000 description 1
- 238000001228 spectrum Methods 0.000 description 1
- 230000003335 steric effect Effects 0.000 description 1
- 150000005846 sugar alcohols Polymers 0.000 description 1
- 238000001149 thermolysis Methods 0.000 description 1
- 230000009466 transformation Effects 0.000 description 1
- 229920006304 triacetate fiber Polymers 0.000 description 1
- 125000005389 trialkylsiloxy group Chemical group 0.000 description 1
- 150000003682 vanadium compounds Chemical class 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F32/00—Homopolymers and copolymers of cyclic compounds having no unsaturated aliphatic radicals in a side chain, and having one or more carbon-to-carbon double bonds in a carbocyclic ring system
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F232/00—Copolymers of cyclic compounds containing no unsaturated aliphatic radicals in a side chain, and having one or more carbon-to-carbon double bonds in a carbocyclic ring system
- C08F232/08—Copolymers of cyclic compounds containing no unsaturated aliphatic radicals in a side chain, and having one or more carbon-to-carbon double bonds in a carbocyclic ring system having condensed rings
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F4/00—Polymerisation catalysts
- C08F4/42—Metals; Metal hydrides; Metallo-organic compounds; Use thereof as catalyst precursors
- C08F4/44—Metals; Metal hydrides; Metallo-organic compounds; Use thereof as catalyst precursors selected from light metals, zinc, cadmium, mercury, copper, silver, gold, boron, gallium, indium, thallium, rare earths or actinides
- C08F4/60—Metals; Metal hydrides; Metallo-organic compounds; Use thereof as catalyst precursors selected from light metals, zinc, cadmium, mercury, copper, silver, gold, boron, gallium, indium, thallium, rare earths or actinides together with refractory metals, iron group metals, platinum group metals, manganese, rhenium technetium or compounds thereof
- C08F4/70—Iron group metals, platinum group metals or compounds thereof
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G61/00—Macromolecular compounds obtained by reactions forming a carbon-to-carbon link in the main chain of the macromolecule
- C08G61/02—Macromolecular compounds containing only carbon atoms in the main chain of the macromolecule, e.g. polyxylylenes
- C08G61/04—Macromolecular compounds containing only carbon atoms in the main chain of the macromolecule, e.g. polyxylylenes only aliphatic carbon atoms
-
- G—PHYSICS
- G02—OPTICS
- G02B—OPTICAL ELEMENTS, SYSTEMS OR APPARATUS
- G02B1/00—Optical elements characterised by the material of which they are made; Optical coatings for optical elements
- G02B1/04—Optical elements characterised by the material of which they are made; Optical coatings for optical elements made of organic materials, e.g. plastics
Abstract
Disclosed is a method for preparing a cycloolefin polymer containing polar functional groups, comprising: preparing a catalyst mixture including i) a precatalyst, containing a Group 10 transition metal having a ligand containing oxygen ions bonded to the metal; ii) a first cocatalyst which is an organic compound containing a Group 15 element; and iii) a second cocatalyst which is capable of providing an anion and weakly coordinating to the metal of the precatalyst; and subjecting a monomer solution comprising a norbornene-based compound containing a polar functional group to an addition polymerization reaction in the presence of an organic solvent and the catalyst mixture, at a temperature of 80-200 DEG C, the total amount of the organic solvent being 50-800 % by weight based on the total weight of the monomer contained in the monomer solution, and the product yield of the polymer being 50% by weight or more based on the total weight of the monomer.
Description
Related application
The application is one and divides an application, the application number of original application is 200380100180.0 (international application no is PCT/KR2003/002634), the applying date is on December 3rd, 2003, and invention and created name is " polymerization contains the method for polar functional group cyclic olefin polymer and uses the electronics of this polymerized cycloolefins ".
Technical field
The present invention relates to cyclic olefin polymer, more particularly, relate to and a kind ofly contain the method for the high molecular cyclic olefin polymer of polar functional group, and use the electronics of this cyclic olefin polymer with the high yield polymerization.
Background technology
Inorganic materials such as silicon-dioxide or nitride mainly utilize in information and electronic industry.Technical development and the demand new for small-sized efficient equipment need new high performance material.In this respect, have the ideal physics-chem characteristic and attracted many attentions as the polymkeric substance of low specific inductivity and rate of moisture absorption, good metal adhesion, intensity, thermostability and transparency and high glass transformation temperature (Tg＞250 ℃).
This polymkeric substance can be as insulation film, polarizing plate protecting film, multichip module, unicircuit (IC), printed circuit board (PCB), the moulding compound of electronic component, the optical material of semi-conductor and TFT-LCD, for example flat-panel monitor etc.As a kind of new high performance material, compare cyclic olefin polymer with traditional olefin polymer and show many improvement characteristics, be that they demonstrate high-clarity, thermotolerance and chemical resistant properties and have low degree of birefringence and rate of moisture absorption.Therefore, this cyclic olefin polymer can be used for various application, and for example optical element such as CD, DVD and POF (plastic optical fibre), information and electronic component such as capacitor film, low insulation body and medical treatment product are as low absorption syringe, blister packaging etc.
Well-known cyclic olefin polymer prepares by one of three kinds of following methods: ROMP (ring-opening metathesis polymerization), ethylene copolymerization and use contain the addition polymerization of the catalyzer of transition metal such as Ni and Pd.Describe in these methods reaction scheme 1 below.Depend on central metal, the ligand and the promotor of the catalyzer that uses in polyreaction, the structure of polymerization characteristic and polymkeric substance and characteristic can change.
Reaction formula 1
Each monomeric repeating unit of polymkeric substance by the preparation of ROMP method has a two key, and therefore, this polymkeric substance has low thermal stability and oxidative stability, and mainly as thermosetting resin.Tenny etc. are in U.S. Pat 5,011, disclose this thermosetting resin in 730 to be made into printed circuit board (PCB) by reactive injection molding.
In order to improve physics-chem characteristic, ROMP-polymkeric substance hydrogenant method under the situation that palladium or Raney nickel catalyst are arranged has been proposed by the polymkeric substance of ROMP method preparation.The hydrogenant polymkeric substance demonstrates the oxidative stability of improvement, but still needs to improve its thermostability.And the cost that increases owing to additional program has hindered its commercial applications.
Well-known ethene-norborneol multipolymer uses titanium base Ziegler-Natta catalyst by for the first time synthetic (by Koinzer, P. equals to deliver in the German Patent 109,244) by Leuna company.But remaining impurities makes the transparency variation in multipolymer, and its second-order transition temperature (Tg) is very low promptly 140 ℃ or lower.Though, it is reported and use zirconium base metallocene catalyst can generate high molecular weight polymers (the Plastic News of narrow molecular weight distribution, Feb.27,1995, p.24), thereby but since in reaction medium the concentration of cycloolefin monomers increase catalytic activity and reduce, and resulting multipolymer has low second-order transition temperature (Tg＜200 ℃).In addition, this multipolymer has relatively poor physical strength and chemical resistant properties, particularly anti-halogenated hydrocarbon solvent.
United States Patent (USP) the 3rd, 330 discloses a kind of method for preparing cyclic olefin polymer in the presence of palladium-based catalyst No. 815.But the molecular weight of this cyclic olefin polymer it is reported to be 10,000 or lower.A kind of use of report such as Gaylord [Pd (C
6H
5CN) Cl
2]
2Polymerization (Gaylord, N.G. as the norbornylene of catalyzer; Deshpande, A.B.; Mandal, B.M.; Martan, M.J.Macromol.Sci.-Chem.1977, All (5), 1053-1070).In addition, a kind of polymerization of norbornylene homogeneous (Kaminsky, W. that uses zirconium base metallocene catalyst of reports such as Kaminsky; Bark, A.; Drake, I.Stud.Surf.Catal.1990,56,425).These polymkeric substance have high-crystallinity, and thermolysis at high temperature reaches and can not dissolve substantially in common organic solvents before their fusings.
Polymkeric substance adhere to inorganics surface as the binding property of silicon, silicon-dioxide, silicon nitride, aluminum oxide, copper, aluminium, gold and silver, platinum, nickel, titanium and chromium for as the reliability aspect of the polymkeric substance of electronic material key factor normally.U.S. Pat 4,831,172 disclose benzocyclobutene (BCB)-functional organosilane tackiness agent auxiliary agent to increase the binding property between inorganics surface and the polymkeric substance.
Introduce chemistry and the physical properties that functional group can control the gained norbornene polymer to norbornene monomer.U.S. Pat 3,330,815 disclose a kind of method of producing polynorbornene with the norbornene monomer that contains polar functional group.But catalyzer is because the polar functional group of norbornene monomer and inactivation, and this causes the early stopping of crossing of polyreaction, thereby produces and have molecular weight 10,000 or lower norbornene polymer.
In order to make great efforts to overcome these problems, Fink, suggestions such as G are a kind of in the method (Macromol.Chem.Phys.1999,200,881) that contains the norbornene derivative of polar functional group with silane, aluminum alkyls or borane compound pre-treatment norbornene derivative post polymerization.But this method has limited introduces polymer chain with the pre-treatment norbornylene, and has limited the increase of polymerization activity.In addition, this method further needs a post-processing step to be used to remove silane, aluminium or borane compound.
U.S. Pat 5,179,171 disclose a kind of vinyl polymerization unit and unitary multipolymer of at least one cyclic olefin polymerization of comprising, wherein cycloolefin need not open loop in the presence of the catalyzer that is formed by soluble vanadium compound and organo-aluminium compound and be added in the polymer chain.But Zhi Bei polymer thermostable is poor like this, and common physics and the chemical property of this polymkeric substance, and the metlbond characteristic does not have big improvement.
(Risse et al., Macromolecules, 1996, Vol.29,2755-2763 have been carried out studying in the polymerization aspect of the norbornylene that contain ester, ethanoyl or silyl relevant with the introducing of polar functional group; Risse et al., Makromol.Chem.1992, Vol.193,2915-2927; Sen et al., Organometallics 2001, Vol.20,2802-2812; Goodall et al., United States Patent (USP) U.S.5,705,50; Lipian et al., United States Patent (USP) U.S.No.6,455,650).
Sen etc. have reported a kind of at [Pd (CH
3CN)
4] [BF
4]
2There is the method for the various ester norbornene monomers of polymerization down in catalyzer, wherein selectively polymerization of exo isomer quilt, and also polymerization yield rate is low.(Sen?et?al.，J.Am.Chem.Soc.1981，Vol.103，4627-4629).
Disclose the polymkeric substance by the norbornylene preparation that contains polar functional group in the U.S. Pat 5,705,503 that Risse and Goodall etc. delivers, wherein most of monomer is made of endo isomer.But, only containing therein in the polyreaction that the polarity norbornene derivative of ester group is aggregated, catalyzer and this monomeric mol ratio are about 1/100, this is unfavorable economically.
In the polyreaction of the polar functionalities norbornylene that contains ester group or ethanoyl, having reported needs excessive catalyzer (with respect to monomer 1/100 to 1/400), and it is very difficult to remove catalyst residue after the polymerization.In the U.S. Pat 6,455,650 that Lipian etc. delivers, disclose a kind of in the presence of little amount of catalyst the method for polymerization norbornene derivative.But the polymeric productive rate of polar monomer such as ester-norbornylene only is 5%.
Sen etc. have reported and have a kind ofly comprised 1,5-cyclooctadiene methyl chloride close palladium ([(1,5-Cyclooctadiene) (CH
3) Pd (Cl)]), PPh
3And Na
+[3,5-(CF
3)
2C
6H
3]
4B
-Catalyst system have the method for polyester-norbornylene down, wherein the polymerization yield rate of this ester-norbornylene is 40% or lower, the molecular weight of this polymkeric substance is 6,500 or lower, and the molar weight of employed catalyzer is about monomeric 1/400 (Sen et al., Organometallics 2001, Vol.20,2802-2812).
Risse etc. have reported a kind of at the [(η as catalyzer
3-allyl group) PdCl]
2And AgBF
4Or AgSbF
6The method of polymerization methyl esters-norbornylene under existing (Risse et al., Macromolecules, 1996, Vol.29,2755-2763).This polymerization yield rate is about 60%, and the molecular weight of the polymkeric substance of generation is about 12,000.In addition, 1/50 the excess catalyst that is about this monomer molar amount is used.Use the reason of excess catalyst to be interpreted as activity of such catalysts position and monomeric polar functional group such as ester group or ethanoyl coordination, thereby cause steric effect and stop norbornene derivative to be close on this reactive site, or cationic reactive site reaches electrical neutralization by polar functional group, cause weak interaction (the Risse et al. of the two keys of norbornylene, Macromolecules, 1996, Vol.29,2755-2763; Risse et al., Makromol.Chem.1992, Vol.193,2915-2927).
Therefore, the polymerization ordinary method that contains the cycloolefin of polar functional group can not satisfy the molecular weight of polymkeric substance of polymerization yield rate, generation and certain desired level of catalyzer and monomeric mol ratio aspect.
Summary of the invention
On the one hand, the invention provides a kind of method that is used for containing the high molecular cyclic olefin polymer of polar functional group with produced in high yields.
On the other hand, the invention provides the multipolymer that is used to the monomeric unit for preparing the polar loop olefin homo or comprise identical or different polar functionalities cycloolefin or comprise polarity and the method for the polar functionalities multipolymer of nonpolar cycloolefin monomers.
Advance on the one hand, the invention provides a kind of method that is used to prepare the cyclic olefin polymer that contains polar functional group, this cyclic olefin polymer has chemical resistant properties, toughness and the metal adhesion of low specific inductivity, low rate of moisture absorption, high glass transition temperature, desired thermal stability and oxidation-resistance, expectation.
Again on the other hand, the invention provides a kind of method that is used to prepare the cyclic olefin polymer that contains polar functional group, this cyclic olefin polymer is to having sufficient adhesive power as metal base such as copper, silver, gold.
Again on the other hand, the invention provides a kind of method that is used to prepare the cyclic olefin polymer that contains polar functional group, this cyclic olefin polymer has the desired optical characteristics such as protective membrane as optical thin film, polaroid.
Again on the other hand, the invention provides a kind of method that is used to prepare the cyclic olefin polymer that contains polar functional group, this cyclic olefin polymer can be used the material of conduct as the electronic component of unicircuit (IC), printed circuit board (PCB) and multichip module.
Again on the other hand, the invention provides a kind of method that is used to prepare the cyclic olefin polymer that contains polar functional group, this cyclic olefin polymer has not having that the substrate to electronic component has competent adhesive power under the situation of coupling agent.
Again on the other hand, the invention provides a kind of optical thin film for preparing by the cyclic olefin polymer that contains polar functional group of method manufacturing of the present invention.
On the one hand, provide a kind of method that is used to prepare the cyclic olefin polymer that contains polar functional group, comprising:
The preparation catalyst mixture:
I) pre-catalyst represented of Chemical formula 1, this pre-catalyst contain the 10th group 4 transition metal that has with the ligand of the oxygen-carrying ion of the 10th group 4 transition metal bonding;
It ii) is first promotor that contains the organic compound of the 15th family's element; With
Second promotor that is coordinated to the metal of pre-catalyst a little less than negatively charged ion and the energy iii) can be provided; With
Under 80～200 ℃ of temperature, in the presence of organic solvent and catalyst mixture, make the monomer solution that comprises the norbornylene based compound that contains polar functional group carry out polyaddition reaction, the total amount of this organic solvent be in the monomer solution contained total monomer weight 50～800%, and the productive rate of polymkeric substance be total monomer weight 50% or more.
Chemical formula 1
[-O-(A)-O-]
nM(R
1)
2-n
Wherein
M is the 10th group 4 transition metal;
N is 1 or 2;
A represents linear or dendritic C
1-20Alkyl, aryl, aralkyl, thiazolinyl or contain the heteroatomic linearity that comprises Si, Ge, S, O or N or dendritic C
1-20Alkyl, aryl, aralkyl or thiazolinyl;
R
1Be hydrogen; Linear or dendritic C
1-20Alkyl, thiazolinyl or vinyl; Alkyl replaces or unsubstituted C
3-12Cycloalkyl; Alkyl replaces or unsubstituted C
6-40Aryl; Contain at least one heteroatomic C
6-40Aryl; Alkyl replaces or unsubstituted C
7-15Aralkyl; Or C
3-20Alkynyl.
On the other hand, the invention provides a kind of optical anisotropic film, it comprises that having molecular weight is 100,000 or the higher cyclic olefin polymer that contains polar functional group.
Again on the one hand, provide a kind of display apparatus, it comprises that having molecular weight is 100,000 or the optical anisotropic film of the higher cyclic olefin polymer that contains polar functional group.
Hereinafter, will carry out more detailed description to the present invention.
According to the present invention, the high molecular cyclic olefin polymer uses the special catalyst system to be prepared from by the monomer mixture that comprises the norbornylene based compound that contains polar functional group under given conditions.
According to the present invention, have molecular weight and be at least 100,000 cyclic olefin polymers and be produced with 50% or the higher high yield that contains monomeric gross weight in the monomer mixture, simultaneously even under high reaction temperature, keep activity of such catalysts with a spot of catalyzer.
It is heat-staple that the catalyst system that the present invention uses is determined under 80 ℃ or higher temperature according to spectroscopic analysis.Although be not subjected to the constraint of particular theory, but think that the catalytic site of catalyst system is activated by the interaction between the polar functional group that suppresses cycloolefin monomers, and cationic catalyst at high temperature is prevented from, and two keys of cycloolefin monomers are inserted into the catalytic site that is activated of catalyzer.Therefore, polyreaction just finishes up to forming high molecular weight polymers.
Catalyst system of the present invention comprises i) pre-catalyst represented of Chemical formula 1, this pre-catalyst contains the 10th group 4 transition metal that has with the ligand of the oxygen-carrying ion of the 10th group 4 transition metal bonding; It ii) is first promotor that contains the organic compound of the 15th family's element; Second promotor that is coordinated to the metal of pre-catalyst a little less than negatively charged ion and the energy iii) can be provided.
Chemical formula 1
[-O-(A)-O-]
nM(R
1)
2-n
In Chemical formula 1,
M is the 10th group 4 transition metal;
N is 1 or 2;
A represents linear or dendritic C
1-20Alkyl, aryl, aralkyl, thiazolinyl or contain the heteroatomic linearity that comprises Si, Ge, S, O or N or dendritic C
1-20Alkyl, aryl, aralkyl or thiazolinyl;
R
1Be hydrogen; Linear or dendritic C
1-20Alkyl, thiazolinyl or vinyl; Alkyl replaces or unsubstituted C
3-12Cycloalkyl; Alkyl replaces or unsubstituted C
6-40Aryl; Contain at least one heteroatomic C
6-40Aryl; Alkyl replaces or unsubstituted C
7-15Aralkyl; Or C
3-20Alkynyl.
The organic compound of first promotor has unshared electron pair and as electron donor, is represented by Chemical formula 2 or 3.
Chemical formula 2
D-(R
2)
3-c[X(R
2)
d]
c
In Chemical formula 2,
D is the 15th family's element,
C is 0～3 integer,
X is oxygen, sulphur, nitrogen or silicon,
When X was oxygen or sulphur, d was 1; When X was nitrogen-atoms, d was 2; Or when X was silicon, d was 3,
R
2Be hydrogen; Linear or dendritic C
1-20Alkyl, alkoxyl group, allyl group, thiazolinyl or vinyl; Alkyl replaces or unsubstituted C
3-12Cycloalkyl; Alkyl replaces or unsubstituted C
6-40Aryl; Alkyl replaces or unsubstituted C
7-15Aralkyl; C
3-20Alkynyl; Three (linear or dendritic C
1-10Alkyl) silyl or three (linear or dendritic C
1-10Alkoxyl group) silyl; Three (alkyl replacement or unsubstituted C
3-12Cycloalkyl) silyl; Three (alkyl replacement or unsubstituted C
6-40Aryl) silyl; Three (alkyl replacement or unsubstituted C
6-40Aryloxy) silyl; Three (linear or dendritic C
1-10Alkyl) siloxy-; Three (alkyl replacement or unsubstituted C
3-12Cycloalkyl) siloxy-; Three (alkyl replacement or unsubstituted C
6-40Aryl) siloxy-, wherein all these substituting groups can be replaced by linear or dendritic alkylhalide group or halogen.
Chemical formula 3
(R
3)
2D-(R
4)-D(R
3)
2
In chemical formula 3,
D is the 15th family's element,
R
3As R in the Chemical formula 2
2Definition;
R
4Be linear or dendritic C
1-5Alkyl, thiazolinyl or vinyl; Alkyl replaces or unsubstituted C
3-12Cycloalkyl; Alkyl replaces or unsubstituted C
6-20Aryl; Alkyl replaces or unsubstituted C
7-15Aralkyl.
Second promotor is the salt of chemical formula 4 expressions.
Chemical formula 4
[positively charged ion]
a[negatively charged ion]
b
Wherein
Positively charged ion is selected from by proton; The positively charged ion of the 1st family and group II metal; With contain the group that these can be formed in conjunction with the cationic organic group of the unshared electron pair of the organic compound of first promotor.
Negatively charged ion be a kind of can a little less than be coordinated to the negatively charged ion of pre-catalyst metal M, and be selected from by borate, aluminate, [SbF
6], [PF
6], [AsF
6], perfluoro acetate ([CF
3CO
2]), perfluoro propionic salt ([C
2F
5CO
2]), perfluoro butyrates ([CF
3CF
2CF
2] CO
2)), perchlorate ([ClO
4]), p-tosylate ([p-CH
3C
6H
4SO
3]), [SO
3CF
3], boric acid benzene, halogen atom replace or unsubstituted carborane is formed group; With
A and b are respectively positively charged ion and negatively charged ion number, are that elementary charge neutral number is determined by satisfying positively charged ion and negatively charged ion.
The cationic organic group that contains chemical formula 4 is selected from by ammonium, [NH (R
5)
3]
+, [NH
2(R
5)
2]
+, [NH
3(R
5)
1]
+[N (R
5)
4]
+Phosphine, [PH (R
5)
3]
+, [PH
2(R
5)
2]
+, [PH
3(R
5)
1]
+[P (R
5)
4]
+Carbonium ion, [C (R
5)
3]
+[H (OEt
2)
2]
+[Ag]
+[Cp
2Fe]
+The group of forming, wherein R
5Be linear or dendritic C
1-20Alkyl; Alkyl or silyl that halogen replaces; Alkyl replaces or unsubstituted C
3-12Cycloalkyl; Halogen replaces or unsubstituted cycloalkyl or silyl cycloalkyl; Alkyl replaces or unsubstituted C
6-40Aryl; Halogen replaces or unsubstituted aryl or silyl aryl; Alkyl replaces or unsubstituted C
7-15Aralkyl; Or the aralkyl or the silyl aralkyl of halogen replacement.
The borate of chemical formula 4 or aluminate are represented by chemical formula 4a or 4b negatively charged ion.
Chemical formula 4a
[M′(R
6)
4]
Chemical formula 4b
[M′(OR
6)
4]
In chemical formula 4a and chemical formula 4b,
M ' is boron or aluminium;
R
6It is halogen; Halogen atom replaces or unsubstituted linearity or dendritic C
1-20Alkyl, thiazolinyl; Halogen replaces or unsubstituted C
3-12Cycloalkyl; Alkyl replaces or unsubstituted C
6-40Aryl; Linear or dendritic C
3-20The C that trialkylsiloxy is linear or dendritic
18-48The C that the triaryl siloxy-replaces
6-40Aryl; Or halogen replaces or unsubstituted C
7-15Aralkyl.
Catalyst mixture comprises containing by pre-catalyst and first and helps cationic complex that catalyst aid makes and the metal catalyst complex of the anion complex made by second promotor.
In one embodiment of the invention, catalyst mixture contains the pre-catalyst of the 10th group 4 transition metal based on 1mol, comprise 1～3mol contain first promotor of organic compound of the 15th family's element and 1～2mol can provide negatively charged ion and can a little less than be coordinated to second promotor of the metal of pre-catalyst.
According to the present invention, catalyst mixture comprises: pre-catalyst, this pre-catalyst contain have with Chemical formula 1 in the 10th group 4 transition metal of ligand of oxygen-carrying ion of the 10th group 4 transition metal bonding; First promotor that contains the organic compound of the 15th family's element; Second promotor of the metal of pre-catalyst is provided a little less than can providing negatively charged ion also.Then, under the situation of organic solvent and catalyst mixture existence, under 80～200 ℃ of temperature, make the monomer solution that comprises the norbornylene based compound that contains polar functional group carry out polyaddition reaction.Preferred 80～170 ℃ of the temperature of polyreaction, more preferably 80～150 ℃.
Preferably, organic solvent is selected from the group of being made up of methylene dichloride, ethylene dichloride, toluene, chlorobenzene and composition thereof.In reaction system the total amount of organic solvent be in the monomer solution contained total monomer weight 50～800%.The total amount of organic solvent can change in restricted portion in reaction system, for example in the monomer solution 50～400% of contained total monomer weight, or 50～200%.
In polymerization reaction system, be 1: 2 based on the catalyst mixture of the 10th group transition metal compound with the scope of contained monomeric mol ratio in monomer solution, 500～1: 100,000.This catalyzer is far smaller than the employed ratio of conventional polymerization reaction system that is used to prepare the polar loop olefin polymer with this monomeric ratio, but, be enough to show activity of such catalysts in the method that is used for preparing the high molecular cyclic olefin polymer of the present invention.Preferably, catalyst system and monomeric mol ratio are 1: 5,000～1: 20,000, and based on the 10th group transition metal compound of pre-catalyst.
Catalyzer in the method contains the organic compound of the 15th family's element and provides the mixture of anionic salt or complex form to be added in the polymerization reaction system in the catalyst system for preparing with i.e. the 10th group transition metal compound of catalyst component separately.Further, each catalyst component need not preparation and can directly join in the polymerization reaction system.
In the method, the norbornylene based compound is used to prepare the polar functionalities cyclic olefin polymer.This norbornene monomer or derivatives thereof refers to and contains the unitary monomer of at least one norbornylene by following chemical formula 5 expressions (two ring [2.2.1] seven-2-alkene).
The polar functional group of the norbornylene based compound that contains in monomer solution is preferably ester group or ethanoyl.
The norbornene monomer that contains polar functional group can be the mixture of endo isomer and exo isomer, and the ratio of the component between the isomer does not limit particularly.
In one embodiment of the invention, contain the norbornylene based compound of polar functional group by 5 expressions of following chemical formula.
Chemical formula 5
In chemical formula 5,
M is 0～4 integer,
R
7, R
8, R
9And R
10In at least one is a polar functional group, other be non-polar functional group, R
7, R
8, R
9And R
10Can be combined together to form saturated or undersaturated C
1-20Cyclic group or C
6-24Aromatic nucleus;
Nonpolar functional group comprises hydrogen; Halogen; Linear or dendritic C
1-20Alkyl; Linear or dendritic C
1-20Alkylhalide group; Linear or dendritic C
1-20Thiazolinyl; Linear or dendritic C
1-20Haloalkenyl; Linear or dendritic C
3-20Alkynyl; Linear or dendritic C
3-20Alkynyl halide; Alkyl, thiazolinyl, alkynyl, halogen, alkylhalide group, haloalkenyl or alkynyl halide replace or unsubstituted C
3-12Cycloalkyl; Alkyl, thiazolinyl, alkynyl, halogen, alkylhalide group, haloalkenyl or alkynyl halide replace or unsubstituted C
6-40Aryl; Alkyl, thiazolinyl, alkynyl, halogen, alkylhalide group, haloalkenyl or alkynyl halide replace or unsubstituted C
7-15Aralkyl;
Polar functional group is to contain at least one O, N, and P, S, the nonhydrocarbon polar group of Si and B, and be selected from by the group that comprises following material: OR
12, OC (O) OR
12, R
11OC (O) OR
12, C (O) R
12, R
11C (O) R
12, OC (O) R
12, R
11OC (O) R
12, (R
11O) pOR
12, (OR
11) pOR
12, C (O) OC (O) R
12, R
11C (O) OC (O) R
12, SR
12, R
11SR
12, SSR
12, R
11SSR
12, S (=O) R
12, R
11S (=O) R
12, R
11C (=S) R
12, R
11C (=S) SR
12, R
11SO
3R
12, SO
3R
12, R
11N=C=S, NCO, R
11NCO, CN, R
11CN, NNC (=S) R
12, R
11NNC (=S) R
12, NO
2, R
11NO
2,
R
12, R
13And R
14Be hydrogen independently of one another; Halogen; Linear or dendritic C
1-20Alkyl; Linear or dendritic C
1-20Alkylhalide group; Linear or dendritic C
1-20Thiazolinyl; Linear or dendritic C
1-20Haloalkenyl; Linear or dendritic C
3-20Alkynyl; Linear or dendritic C
3-20Alkynyl halide; Replace or unsubstituted C with alkyl, thiazolinyl, alkynyl, halogen, alkylhalide group, haloalkenyl or alkynyl halide
3-12Cycloalkyl; Replace or unsubstituted C with alkyl, thiazolinyl, alkynyl, halogen, alkylhalide group, haloalkenyl or alkynyl halide
6-40Aryl; Replace or unsubstituted C with alkyl, thiazolinyl, alkynyl, halogen, alkylhalide group, haloalkenyl or alkynyl halide
7-15Aralkyl; Or alkoxyl group, halogen alkoxyl group, carbonyl oxygen base, halogen carbonyl oxygen base; With
P is 1～10 integer.
This monomer solution further comprises the cyclic olefins that contains nonpolar functional group.The cyclic olefins mol ratio that contains nonpolar functional group be in the monomer solution monomer integral molar quantity 30%.
The method according to this invention, homopolymer is prepared from by the identical norbornene monomer that polymerization contains polar functional group, or the multipolymer that comprises dicopolymer, three multipolymers and many multipolymers is prepared from by polymerization opposed polarity function norbornene monomer, or the multipolymer that comprises dicopolymer, three multipolymers and many multipolymers forms fully by polymerization polar functionalities norbornene monomer and cycloolefin monomers system with nonpolar functional group.
The method according to this invention, have molecular weight 100,000 or the higher cycloolefin monomers that contains polar functional group can with 50% or higher productive rate be produced.In order to use cyclic olefin polymer to make optical thin film, the molecular weight of this cyclic olefin polymer preferably is controlled at 100,000～1,000,000.
In the polymerization system of routine, the output of the cyclic olefin polymer that contains polar functional group that is produced is very low and molecular weight is low, yet present method produces the cyclic olefin polymer that high-molecular weight contains polar functional group with high yield.
In addition, the method according to this invention can be avoided the reduction of the catalyst activity that caused by the endo isomer that contains polar functional group.In addition, can obtain the cyclic olefin polymer of high yield with a spot of catalyzer.And, the norbornylene based polyalcohol that prepared according to the methods of the invention contains polar functional group is transparent, have metal or contain the sufficient binding property of polymkeric substance, thermostability and the intensity of opposed polarity functional group, and show the low-k that is enough to as the insulation electronic material.The cyclic olefin polymer of being produced by the present invention need not coupling agent and to the adhesive power with expectation of electronic component substrate, and simultaneously, to having sufficient adhesive power as copper, silver and golden metal base.And cyclic olefin polymer of the present invention shows desired optical, so that can be used as polaroid and as the material of the protective membrane of electronic components such as unicircuit (IC), printed circuit board (PCB) and multichip module.
The cyclic olefin polymer that contains polar functional group by present method preparation is made into optical anisotropic film by using general method well known in the art.Zhi Bei optical anisotropic film has the length of delay (R of 70～1000nm like this
Th), such as following equation 1 definition.
(equation 1)
R
th＝Δ(n
y-n
z)×d
In equation 1, n
yBe specific refractory power, under wavelength 550nm, measure along quick shaft direction in the plane;
n
zBe specific refractory power, under wavelength 550nm, measure along thickness direction; With
D is a film thickness.
Equation 2 below the specific refractory power of this optical anisotropic film satisfies.
(equation 2)
In equation 2, n
xBe specific refractory power along slow-axis direction in the plane, n
yBe specific refractory power along quick shaft direction in the plane, n
zIt is the specific refractory power in thickness direction.
Optical anisotropic film can be used as the negative C template optical compensating film of liquid-crystal display.
Embodiment
Hereinafter, will be explained in more detail the present invention with reference to the following examples.But, provide these embodiment and be in order to explain this purpose, rather than the scope that is construed as limiting the invention.
In the following embodiments, carry out according to the Schlenk technology or the loft drier technology of standard for all operations of processing the compound of air or water sensitive.NMR (Nuclear Magnetic Resonance) spectrum uses Bruker400 and 600 spectrographs to obtain.The molecular weight of polymkeric substance and molecular distribution use the polystyrene sample of standard to determine by GPC (gel permeation chromatography).Heat is analyzed, and for example TGA and DSC use TA instrument (TGA2050; Heating rate 10K/min) carries out.
Toluene distills and purifying in sodium/benzophenone, and methylene dichloride and chlorobenzene are at CaH
2Middle distillation and purifying.
The preparation of preparation embodiment 1:5-norbornylene-2-carboxylate methyl ester
DCPD (dicyclopentadiene, Aldrich, 256.5mL, 1.9mol), methyl acrylate (Aldrich, 405mL, 4.5mol) and Resorcinol (3.2g 0.03mol) pack in the 2L autoclave, and temperature rises to 220 ℃.The mixture that generates was with 300rpm stirring reaction 5 hours.After this reaction was finished, the reaction mixture cooling was transferred in the distiller then.This reaction mixture use vacuum pump under reduced pressure 1torr produce title compound (output: 57.6%, external form/interior type=58/42) in 50 ℃ of distillations.
1H-NMR (600MHz, CDCl
3), interior type: δ 6.17 (dd, 1H), 5.91 (dd, 1H), 3.60 (s, 3H), 3.17 (b, 1H), 2.91 (m, 1H), 2.88 (b, 1H), 1.90 (m, 1H), 1.42 (m, 2H), 1.28 (m, 1H); External form: δ 6.09 (m, 2H), 3.67 (s, 3H), 3.01 (b, 1H), 2.88 (b, 1H), 2.20 (m, 1H), 1.88 (m, 1H), 1.51 (d, 1H), 1.34 (m, 2H).
Preparation embodiment 2: the preparation of type 5-norbornylene in rich-2-carboxylate methyl ester
DCPD (dicyclopentadiene, Aldrich, 256.5mL, 1.9mol), methyl acrylate (Aldrich, 405mL, 4.5mol) and Resorcinol (3.2g 0.03mol) pack in the 2L autoclave, and temperature rises to 180 ℃.The mixture that generates was with 300rpm stirring reaction 5 hours.After this reaction was finished, the reaction mixture cooling was transferred in the distiller then.This reaction mixture use vacuum pump under reduced pressure 1torr produce title compound (output: 85%, external form/interior type=41/59) in 50 ℃ of distillations.
1H-NMR (600MHz, CDCl
3), interior type: δ 6.17 (dd, 1H), 5.91 (dd, 1H), 3.60 (s, 3H), 3.17 (b, 1H), 2.91 (m, 1H), 2.88 (b, 1H), 1.90 (m, 1H), 1.42 (m, 2H), 1.28 (m, 1H); External form: δ 6.09 (m, 2H), 3.67 (s, 3H), 3.01 (b, 1H), 2.88 (b, 1H), 2.20 (m, 1H), 1.88 (m, 1H), 1.51 (d, 1H), 1.34 (m, 2H).
Preparation embodiment 3:5-norbornylene-2-butyl carboxylate's preparation
DCPD (dicyclopentadiene, Aldrich, 180mL, 1.34mol), butyl acrylate (Junsei, 500mL, 3.49mol) and Resorcinol (2.7g 0.025mol) pack in the 2L autoclave, and temperature rises to 190 ℃.The mixture that generates was with 300rpm stirring reaction 5 hours.After this reaction was finished, the reaction mixture cooling was transferred in the distiller then.This reaction mixture uses vacuum pump to produce title compound (output: 78%, external form/interior type=55/45) in 80 ℃ of distillations under decompression 1torr.
1H-NMR(600MHz?in?CDCl
3)：6.12(m，2H)，4.09(t，2H)，3.17(s，1H)，3.04(s，1H)，2.92(m，1H)，2.20(m，1H)，1.90(m，1H)，1.60(m，2H)，1.40(m，4H)，0.94(t，3H)
The preparation of preparation embodiment 4:5-norbornylene-2-carboxylic acid benzyl ester
DCPD (dicyclopentadiene, Aldrich, 67.32mL, 0.5mol), benzyl acrylate (Lancaster, 163g, 1.0mol) and Resorcinol (0.23g 2.1mmol) pack in the 2L autoclave, and temperature rises to 200 ℃.The mixture that generates was with 300rpm stirring reaction 5 hours.After this reaction was finished, the reaction mixture cooling was transferred in the distiller then.This reaction mixture uses vacuum pump to produce title compound (output: 65%, external form/interior type=56/44) for twice in 190 ℃ of distillations under decompression 1torr.
1H-NMR(600MHz，CDCl
3)：δ7.32(m，5H)，6.15～6.07(m，2H)，5.11～5.04(m，2H)，3.02～2.88(m，2H)，2.96?&?2.20(m，1H)，1.92(m，2H)，1.52～1.22(m，1H)，1.38(m，1H)
The preparation of preparation embodiment 5:5-norbornylene-2-acetic acid allyl ester
DCPD (dicyclopentadiene, Aldrich, 248mL, 1.852mol), the acetic acid allyl ester (Aldrich, 500mL, 4.63mol) and Resorcinol (0.7g 0.006mol) pack in the 2L autoclave, and temperature rises to 190 ℃.The mixture that generates was with 300rpm stirring reaction 5 hours.After this reaction was finished, the reaction mixture cooling was transferred in the distiller then.This reaction mixture uses vacuum pump to produce title compound (output: 30%, external form/interior type=57/43) for twice in 56 ℃ of distillations under decompression 1torr.
1H-NMR(600MHz，CDCl
3)：δ6.17～5.91(m，2H)，4.15～3.63(m，2H)，2.91～2.88(m，2H)，2.38(m，1H)，2.05(s，3H)，1.83(m，1H)，1.60～1.25(m，2H)，0.57(m，1H).
Preparation embodiment 6:(allyl group) Pd's (acac) is synthetic
(allyl group) Pd (acac) is according to (Aust.J.Chem., 1978, Vol.31,1073) such as (Bull.Chem.Soc.Jpn., 1969, Vol.42,805) such as Imamura and Jackson.
[(allyl group) PdCl]
2(1.83g, 5.0mmol) and methyl ethyl diketone sodium (1.22g, 10mmol) the 250mL Schlenk flask of packing into is then to wherein adding benzene (50ml).The gained mixture at room temperature reacted 1 hour.After this reaction is finished, remove desolvate and obtain pure (allyl group) Pd (acac) (output 85%, 1.04g).
Embodiment 1: the polymerization of 5-norbornylene-2-carboxylate methyl ester (catalyzer: Pd (acac) in methylene dichloride
2, the boratory mol ratio of catalyzer and promotor is 1: 2)
Pd (acac)
2(Acetyl Acetone=acac; 3.5mg; 11 μ mol) and xylidine four (pentafluorophenyl group) borate (1 7.6mg; 22 μ mol) and tricyclohexyl phosphine (3.0mg; 11 μ mol) be enclosed in 250mL Schlenk flask in the loft drier as catalyzer, then to wherein adding the 5ml methylene dichloride.(MENB, 10mL 55.6mmol) at room temperature join in the flask 5-norbornylene-2-carboxylate methyl ester of preparation in preparation embodiment 1.When temperature of reaction was raised to 90 ℃, methylene dichloride was removed under partial vacuum.After this, this reaction mixture reacted 18 hours down at 90 ℃.Along with the disappearance of time, this reaction mixture becomes viscosity, after 10 hours, and final hardening.After this reaction is finished, add 50ml toluene in the viscous soln to dilute it.This solution is injected into and is settled out white polymer in the excess ethanol, this white polymer is filtered by glass funnel, use washing with alcohol, under 80 ℃ dry in a vacuum 24 hours with the polymkeric substance of producing 7.06g 5-norbornylene-2-carboxylate methyl ester (monomeric gross weight 67.5%).
Embodiment 2～4: under various polymerization temperatures in methylene dichloride the polymerization of 5-norbornylene-2-carboxylate methyl ester (catalyzer: Pd (acac)
2, the boratory mol ratio of catalyzer and promotor is 1: 2)
The polymkeric substance of 5-norbornylene-2-carboxylate methyl ester is by the preparation of the same procedure described in the embodiment 1, except the Pd (acac) as catalyzer
2Become 5,000 with the mol ratio of monomeric amount: 1 and 10,000: 1, as shown in table 1, and polymerization temperature becomes 100 ℃ and 110 ℃.The result is shown in following table 1.
Table 1
| The embodiment numbering | Monomer (mL) | Monomer/Pd (mol) | Temperature (℃) | Time (h) | Productive rate | Mw | ?Mw/Mn | |
| ?[g] | ?[％] | |||||||
| Embodiment 1 | ?MENB(10) | 5000/1 | 90 | 18 | ?7.06 | ?67.5 | ?185,100 | 2.16 |
| Embodiment 2 | ?MENB(10) | 5000/1 | 100 | 10 | ?7.98 | ?76.3 | ?166,300 | 2.15 |
| Embodiment 3 | ?MENB(10) | 5000/1 | 110 | 10 | ?8.30 | ?79.4 | ?149,400 | 2.45 |
| Embodiment 4 | ?MENB(17) | 10000/1 | 110 | 10 | ?13.57 | ?76.3 | ?155,800 | 2.13 |
Embodiment 5: the polymerization of 5-norbornylene-2-carboxylate methyl ester (catalyzer: Pd (acac) in methylene dichloride
2, the boratory mol ratio of catalyzer and promotor is 1: 2)
Pd (acac)
2) (4mg), xylidine four (pentafluorophenyl group) borate (21.1mg) and tricyclohexyl phosphine (3.7mg) are enclosed in 250mLSchlenk flask in the loft drier as catalyzer, then to wherein adding the 5ml methylene dichloride.5-norbornylene-2-the carboxylate methyl ester (10mL) of preparation at room temperature joins in the flask in preparation embodiment 1.When temperature of reaction was raised to 80 ℃, this reaction mixture reacted 18 hours down at 80 ℃.After this reaction was finished, 50ml toluene was added in the hardened polymkeric substance to dissolve this polymkeric substance.This solution is injected into and is settled out white polymer in the excess ethanol, this white polymer is filtered by glass funnel, use washing with alcohol, under 80 ℃ dry in a vacuum 24 hours with the polymkeric substance of producing 6.75g 5-norbornylene-2-carboxylate methyl ester (monomeric gross weight 66.8%).The molecular weight of this polymkeric substance (Mw) is 100,400, and Mw/Mn is 1.93.
Embodiment 6: the polymerization of 5-norbornylene-2-carboxylate methyl ester (catalyzer: Pd (acac) in methylene dichloride
2, the boratory mol ratio of catalyzer and promotor is 1: 1)
7.43g (monomeric gross weight 71.0%) 5-norbornylene-2-carboxylate methyl ester polymkeric substance is by the preparation of the same procedure described in the embodiment 1, except using 8.8mg (11 μ mol) xylidine four (pentafluorophenyl group) borate.The molecular weight of this polymkeric substance (Mw) is 184,500, and Mw/Mn is 2.08.
Embodiment 7: the polymerization of 5-norbornylene-2-carboxylate methyl ester (catalyzer: Pd (acac) in methylene dichloride
2, the boratory mol ratio of catalyzer and promotor is 1: 1)
7.95g (monomeric gross weight 76.0%) 5-norbornylene-2-carboxylate methyl ester polymkeric substance is by the preparation of the same procedure described in the embodiment 6, except polymerization temperature becomes 100 ℃.The molecular weight of this polymkeric substance (Mw) is 181,800, and Mw/Mn is 2.13.
Embodiment 8: the polymerization of 5-norbornylene-2-carboxylate methyl ester in methylene dichloride (catalyzer:
Palladium, the boratory mol ratio of catalyzer and promotor is 1: 2)
8.95g (monomeric gross weight 85.6%) 5-norbornylene-2-carboxylate methyl ester polymkeric substance by the preparation of the same procedure described in the embodiment 1, replaces Pd (acac) except using catalyst acetic acid palladium (2.5mg, 11 μ mol)
2The molecular weight of this polymkeric substance (Mw) is 195,300, and Mw/Mn is 2.3.
Embodiment 9: the polymerization of 5-norbornylene-2-carboxylate methyl ester in methylene dichloride (catalyzer:
(allyl group) Pd (acac), the boratory mol ratio of catalyzer and promotor is 1: 2)
8.5g (monomeric gross weight 81.3%) 5-norbornylene-2-carboxylate methyl ester polymkeric substance by the preparation of the same procedure described in the embodiment 1, replaces Pd (acac) except using catalyzer (allyl group) Pd (acac) (2.7mg, 11 μ mol)
2The molecular weight of this polymkeric substance (Mw) is 185,000, and Mw/Mn is 2.2.
Embodiment 10: under 90 ℃ of temperature in methylene dichloride the polymerization of 5-norbornylene-2-carboxylate methyl ester (catalyzer: Pd (acac)
2, the boratory mol ratio of catalyzer and promotor is 1: 2)
Pd (acac)
2(3.4mg, 11 μ mol), xylidine four (pentafluorophenyl group) borate (17.6mg, 22 μ mol) and tricyclohexyl phosphine (3.0mg, 11 μ mol) be enclosed in the 250mLSchlenk flask in the loft drier, as catalyzer then to wherein adding the 3ml methylene dichloride.Type 5-norbornylene-2-carboxylate methyl ester (10mL, 55.6 μ mol) at room temperature joins in the flask in the richness of preparation in preparation embodiment 2.After temperature of reaction was raised to 90 ℃, this reaction mixture reacted 18 hours down at 90 ℃.After this reaction was finished, 50ml toluene was added in the viscous soln to dilute it.This solution is injected into and is settled out white polymer in the excess ethanol, this white polymer is filtered by glass funnel, use washing with alcohol, dry in a vacuum 24 hours polymkeric substance (67.2 weight % of monomeric gross weight) under 80 ℃ to produce 7.03g 5-norbornylene-2-carboxylate methyl ester.The molecular weight of this polymkeric substance (Mw) is 167,898, and Mw/Mn is 2.3.
Embodiment 11: under 100 ℃ of temperature in methylene dichloride rich in polymerization (catalyzer: the Pd (acac) of type 5-norbornylene-2-carboxylate methyl ester
2, the boratory mol ratio of catalyzer and promotor is 1: 2)
6.9g (monomeric gross weight 66.0%) 5-norbornylene-2-carboxylate methyl ester polymkeric substance is by the preparation of the same procedure described in the embodiment 10, except polymerization temperature becomes 100 ℃.The molecular weight of this polymkeric substance (Mw) is 157,033, and Mw/Mn is 2.4.
Embodiment 12～14: under various polymerization temperatures in methylene dichloride 5-norbornylene-2-butyl carboxylate's polymerization (catalyzer: Pd (acac)
2, the boratory mol ratio of catalyzer and promotor is 1: 2)
5-norbornylene-2-butyl carboxylate polymkeric substance is by the preparation of the same procedure described in the embodiment 1, and norbornylene-the 2-butyl carboxylate is as monomer except using 5-, and polymerization temperature is as shown in table 2 to become 90,100 and 120 ℃.The result is shown in following table 2.
Table 2
| The embodiment numbering | Monomer (mL) | Temperature (℃) | Time (h) | Productive rate | Mw | ?Mw/Mn | |
| Embodiment 12 | BENB(20) | 90 | 18 | 14.02 | 72.1 | 186,200 | 2.07 |
| Embodiment 13 | BENB(20) | 100 | 10 | 18.43 | 95.0 | 157,100 | 1.88 |
| Embodiment 14 | BENB(20) | 120 | 4 | 16.30 | 84.0 | 130,000 | 1.85 |
Embodiment 15～17: under various polymerization temperatures in chlorobenzene 5-norbornylene-2-butyl carboxylate's polymerization (catalyzer: Pd (acac)
2, the boratory mol ratio of catalyzer and promotor is 1: 2)
5-norbornylene-2-butyl carboxylate polymkeric substance is by the same procedure described in the embodiment 12 preparation, except use chlorobenzene as solvent to replace methylene dichloride, polymerization temperature is as shown in table 3 to become 90,100 and 110 ℃.The result is shown in following table 3.
Table 3
| The embodiment numbering | Monomer (mL) | Temperature (℃) | Time (h) | Productive rate | Mw | ?Mw/Mn | |
| Embodiment 15 | BENB(20) | 90 | 18 | 12.86 | 66.1 | 149,400 | 2.02 |
| Embodiment 16 | BENB(20) | 100 | 18 | 14.37 | 73.9 | 138,700 | 2.00 |
| Embodiment 17 | BENB(20) | 110 | 18 | 17.28 | 88.9 | 13,800 | 1.96 |
Embodiment 18 and 19: under various polymerization temperatures in toluene 5-norbornylene-2-butyl carboxylate's polymerization (catalyzer: Pd (acac)
2, the boratory mol ratio of catalyzer and promotor is 1: 2)
5-norbornylene-2-butyl carboxylate polymkeric substance is by the same procedure described in the embodiment 12 preparation, except use toluene as solvent to replace methylene dichloride, polymerization temperature is as shown in table 4 to become 90 ℃ and 100 ℃.The result is shown in following table 4.
Table 4
| The embodiment numbering | Monomer (mL) | Monomer/benzene | Temperature (℃) | Time (h) | Productive rate | Mw | ?Mw/Mn | |
| Embodiment 18 | ?BENB(20) | 2/1 | 90 | 18 | ?11.66 | ?60.0 | ?128,100 | 1.94 |
| Embodiment 19 | ?BENB(20) | 2/1 | 100 | 18 | ?15.69 | ?80.7 | ?120,300 | 1.93 |
Embodiment 20: under 90 ℃ of temperature in methylene dichloride 5-norbornylene-2-butyl carboxylate
Polymerization (catalyzer: palladium, the boratory mol ratio of catalyzer and promotor is 1: 2)
Palladium (4.5mg, 20 μ mol), xylidine four (pentafluorophenyl group) borate (32.0mg, 40 μ mol) and tricyclohexyl phosphine (5.6mg, 20 μ mol) be enclosed in 250mL Schlenk flask in the loft drier as catalyzer, then to wherein adding the 5ml methylene dichloride.(20mL 100mmol) at room temperature joins in the flask 5-norbornylene-2-butyl carboxylate who prepares in preparation embodiment 3.When temperature of reaction was raised to 90 ℃, methylene dichloride was removed under partial vacuum.This reaction mixture reacted 18 hours down at 90 ℃.Along with the disappearance of time, this reaction mixture thickness that becomes, finally hardening after 10 hours.After this reaction was finished, 50ml toluene was added in this viscous soln to dilute it.This solution is injected into and is settled out white polymer in the excess ethanol, this white polymer is filtered by glass funnel, use washing with alcohol, under 80 ℃ dry in a vacuum 24 hours with the polymkeric substance of producing 10.02g 5-norbornylene-2-butyl carboxylate (monomeric gross weight 51.5%).The molecular weight of this polymkeric substance (Mw) is 153,033, and Mw/Mn is 2.4.
Embodiment 21: under 100 ℃ of temperature in methylene dichloride 5-norbornylene-2-butyl carboxylate
Polymerization (catalyzer: palladium, the boratory mol ratio of catalyzer and promotor is 1: 2)
18.4g (monomeric gross weight 92.8%) 5-norbornylene-2-butyl carboxylate polymkeric substance is by the preparation of the same procedure described in the embodiment 20, except polymerization temperature becomes 100 ℃.The molecular weight of this polymkeric substance (Mw) is 148,200, and Mw/Mn is 2.2.
Embodiment 22: 5-norbornylene-2-butyl carboxylate's polymerization in methylene dichloride (catalyzer:
(allyl group) Pd (acac), the boratory mol ratio of catalyzer and promotor is 1: 2)
12.06g (monomeric gross weight 62.0%) 5-norbornylene-2-butyl carboxylate polymkeric substance is by the preparation of the same procedure described in the embodiment 20, except using (allyl group) Pd (acac) (2.7mg, 11 μ mol) to replace palladium.The molecular weight of this polymkeric substance (Mw) is 142,000, and Mw/Mn is 2.5.
Embodiment 23: 5-norbornylene-2-carboxylate methyl ester and 5-norbornylene-2-butyl carboxylate's copolymerization (catalyzer: Pd (acac) in methylene dichloride
2, produce in batches)
Pd (acac)
2(1.39g), xylidine four (pentafluorophenyl group) borate (1.28g) and tricyclohexyl phosphine (1.28g) are enclosed in 500mL Schlenk flask in the loft drier as catalyzer, then to wherein adding the 300ml methylene dichloride.5-norbornylene-2-the carboxylate methyl ester (1046g) of preparation among the preparation embodiment 1,5-norbornylene-2-the butyl carboxylate (3082g) and the toluene (8300g) of preparation at room temperature join in a large amount of reactors among the preparation embodiment 3, and the temperature of mixture is raised to 80 ℃.Under this temperature, catalyst mixture joins in a large amount of reactors, and polyreaction was carried out 90 hours continuously, and the viscosity of reaction mixture increases during this period.After polyreaction was finished, 10kg toluene joined in the solution of viscosity to dilute it.This solution is injected into and is settled out white polymer in the excess ethanol, this white polymer is filtered by glass funnel, use washing with alcohol, under 80 ℃ dry in a vacuum 24 hours with the multipolymer of producing 2.2kg 5-norbornylene-2-carboxylate methyl ester and 5-norbornylene-2-butyl carboxylate (monomeric gross weight 53.8%).The molecular weight of this polymkeric substance (Mw) is 115,000, and Mw/Mn is 1.6.
Embodiment 24: 5-norbornylene-2-carboxylate methyl ester and 5-norbornylene-2-butyl carboxylate's copolymerization (catalyzer: Pd (acac) in methylene dichloride
2, the boratory mol ratio of catalyzer and promotor is 1: 2)
Pd (acac)
2(6.0mg, 20 μ mol), xylidine four (pentafluorophenyl group) borate (32.0mg, 40 μ mol) and tricyclohexyl phosphine (5.6mg, 20 μ mol) be enclosed in 250mL Schlenk flask in the loft drier as catalyzer, then to wherein adding the 5ml methylene dichloride.5-norbornylene-2-carboxylate methyl ester (the 9ml of preparation among the preparation embodiment 1,50mmol), 5-norbornylene-2-butyl carboxylate (the 10ml of preparation among the preparation embodiment 3,50mmol) He at room temperature join in the flask, the temperature of mixture is raised to 100 ℃, and methylene dichloride is removed under partial vacuum during this period.Carry out 18 hours therebetween under this temperature in polyreaction, the viscosity of reaction mixture increases.After polyreaction was finished, 50ml toluene joined in the solution of viscosity to dilute it.This solution is injected into and is settled out white polymer in the excess ethanol, this white polymer is filtered by glass funnel, use washing with alcohol, under 80 ℃ dry in a vacuum 24 hours with the multipolymer of producing 16.02g 5-norbornylene-2-carboxylate methyl ester and 5-norbornylene-2-butyl carboxylate (monomeric gross weight 83.7%).The molecular weight of this polymkeric substance (Mw) is 182,300, and Mw/Mn is 2.13.
Embodiment 25: under 110 ℃ of temperature in methylene dichloride 5-norbornylene-2-carboxylate methyl ester and 5-norbornylene-2-butyl carboxylate's copolymerization (catalyzer: Pd (acac)
2, the boratory mol ratio of catalyzer and promotor is 1: 2)
17.8g (92.8 weight % of monomeric gross weight) 5-norbornylene-2-carboxylate methyl ester and 5-norbornylene-2-butyl carboxylate's polymkeric substance is by the preparation of the same procedure described in the embodiment 24, except polymerization temperature becomes 110 ℃.The molecular weight of this polymkeric substance (Mw) is 164,600, and Mw/Mn is 2.43.
Embodiment 26: polymerization (catalyzer: the Pd (acac) of 5-norbornylene in toluene-2-acetic acid allyl ester
2)
5-norbornylene-2-acetic acid the allyl ester of preparation among the preparation embodiment 5 (5.0g, 30.1mmol) and toluene (10ml) pack in the 250mL Schlenk flask.Catalyst solution (methylene dichloride: 3ml) comprise Pd (acac)
2(1.83mg, 6.0 μ mol), tricyclohexyl phosphine (1.69mg, 6.0 μ mol) and xylidine four (pentafluorophenyl group) borate (9.64mg, 12.0 μ mol) join in this flask.Reaction mixture stirring reaction 18 hours under 90 ℃ of temperature.After polyreaction was finished, 50ml toluene joined in the viscous soln to dilute it.This solution is injected into and is settled out white polymer in the excess ethanol, this white polymer is filtered by glass funnel, use washing with alcohol, under 80 ℃ dry in a vacuum 24 hours to produce 4.79g 5-norbornylene-2-acetic acid allyl ester polymkeric substance (monomeric gross weight 95.8%).The molecular weight of this polymkeric substance (Mw) is 203,000, and Mw/Mn is 2.6.
Embodiment 27: the polymerization of 5-norbornylene in toluene-2-acetic acid allyl ester (catalyzer:
Palladium)
5-norbornylene-2-acetic acid the allyl ester of preparation among the preparation embodiment 5 (5.0ml, 30.9mmol) and toluene (10ml) pack in the 250mL Schlenk flask.Catalyst solution (methylene dichloride: 1ml) comprise Pd (acac)
2(1.4mg, 6.2 μ mol), tricyclohexyl phosphine (1.9mg, 6.8 μ mol) and xylidine four (pentafluorophenyl group) borate (10.0mg, 13.6 μ mol) join in this flask.Reaction mixture stirring reaction 4 hours under 90 ℃ of temperature.After polyreaction is finished, this reaction mixture is injected into and is settled out white polymer in the excess ethanol, this white polymer is filtered by glass funnel, use washing with alcohol, dry in a vacuum 24 hours polymkeric substance (86.7 weight % of monomeric gross weight) under 65 ℃ to produce 4.45g 5-norbornylene-2-acetic acid allyl ester.The molecular weight of this polymkeric substance (Mw) is 279,618, and Mw/Mn is 3.23.
Embodiment 28: the polymerization of 5-norbornylene in toluene-2-acetic acid allyl ester (catalyzer:
Palladium)
5-norbornylene-2-acetic acid the allyl ester of preparation among the preparation embodiment 5 (5.0ml, 30.9mmol) and toluene (15ml) pack in the 250mL Schlenk flask.(methylene dichloride: 1ml) comprise palladium (0.7mg, 3.1 μ mol), tricyclohexyl phosphine (1.0mg, 3.4 μ mol) and xylidine four (pentafluorophenyl group) borate (5.4mg, 6.8 μ mol) join in this flask catalyst solution.Reaction mixture stirring reaction 6 hours under 90 ℃ of temperature.After polyreaction is finished, this reaction mixture is injected into and is settled out white polymer in the excess ethanol, this white polymer is filtered by glass funnel, use washing with alcohol, under 65 ℃ dry in a vacuum 24 hours with the polymkeric substance of producing 4.70g 5-norbornylene-2-acetic acid allyl ester (monomeric gross weight 91.6%).The molecular weight of this polymkeric substance (Mw) is 484,033, and Mw/Mn is 3.11.
Embodiment 29: the polymerization of 5-norbornylene in toluene-2-acetic acid allyl ester (catalyzer:
Palladium)
5-norbornylene-2-acetic acid the allyl ester of preparation among the preparation embodiment 5 (5.0ml, 30.9mmol) and toluene (15ml) pack in the 250mL Schlenk flask.(methylene dichloride: 1ml) comprise palladium (0.46mg, 2.1 μ mol), tricyclohexyl phosphine (0.64mg, 2.3 μ mol) and xylidine four (pentafluorophenyl group) borate (3.6mg, 4.5 μ mol) join in this flask catalyst solution.Reaction mixture stirring reaction 8 hours under 80 ℃ of temperature.After polyreaction is finished, this reaction mixture is injected into and is settled out white polymer in the excess ethanol, this white polymer is filtered by glass funnel, use washing with alcohol, under 65 ℃ dry in a vacuum 24 hours with the polymkeric substance of producing 4.44g 5-norbornylene-2-acetic acid allyl ester (monomeric gross weight 86.5%).The molecular weight of this polymkeric substance (Mw) is 472,666, and Mw/Mn is 3.03.
Embodiment 30: the polymerization of 5-norbornylene in high-pressure reactor-2-acetic acid allyl ester (is urged
Change agent: palladium)
5-norbornylene-2-acetic acid the allyl ester of preparation among the preparation embodiment 5 (5.0ml, 30.9mmol) and toluene (15ml) pack into and have in the high-pressure reactor of agitator.(methylene dichloride: 1ml) comprise palladium (0.7mg, 3.1 μ mol), tricyclohexyl phosphine (1.0mg, 3.4 μ mol) and xylidine four (pentafluorophenyl group) borate (5.4mg, 6.8 μ mol) join in this reactor catalyst solution.Reaction mixture stirring reaction 6 hours under 130 ℃ of temperature.After polyreaction is finished, this reaction mixture is injected into and is settled out white polymer in the excess ethanol, this white polymer is filtered by glass funnel, use washing with alcohol, under 65 ℃ dry in a vacuum 24 hours with the polymkeric substance of producing 4.51g 5-norbornylene-2-acetic acid allyl ester (monomeric gross weight 87.9%).The molecular weight of this polymkeric substance (Mw) is 368,200, and Mw/Mn is 3.11.
Embodiment 31: the polymerization of 5-norbornylene in high-pressure reactor-2-acetic acid allyl ester (is urged
Change the agent palladium)
5-norbornylene-2-acetic acid the allyl ester of preparation among the preparation embodiment 5 (5.0ml, 30.9mmol) and toluene (15ml) pack into and have in the high-pressure reactor of agitator.(methylene dichloride: 1ml) comprise palladium (0.7mg, 3.1 μ mol), tricyclohexyl phosphine (1.0mg, 3.4 μ mol) and xylidine four (pentafluorophenyl group) borate (5.4mg, 6.8 μ mol) join in this reactor catalyst solution.Reaction mixture stirring reaction 6 hours under 150 ℃ of temperature.After polyreaction is finished, this reaction mixture is injected into and is settled out white polymer in the excess ethanol, this white polymer is filtered by glass funnel, use washing with alcohol, under 65 ℃ dry in a vacuum 24 hours with the polymkeric substance of producing 4.17g 5-norbornylene-2-acetic acid allyl ester (monomeric gross weight 81.2%).The molecular weight of this polymkeric substance (Mw) is 273,500, and Mw/Mn is 3.42.
Embodiment 32: the polymerization of 5-norbornylene in high-pressure reactor-2-acetic acid allyl ester (is urged
Change agent: palladium)
5-norbornylene-2-acetic acid the allyl ester of preparation among the preparation embodiment 5 (5.0ml, 30.9mmol) and toluene (15ml) pack into and have in the high-pressure reactor of agitator.(methylene dichloride: 1ml) comprise palladium (0.7mg, 3.1 μ mol), tricyclohexyl phosphine (1.0mg, 3.4 μ mol) and xylidine four (pentafluorophenyl group) borate (5.4mg, 6.8 μ mol) join in this reaction mixer catalyst solution.Reaction mixture stirring reaction 6 hours under 170 ℃ of temperature.After polyreaction is finished, this reaction mixture is injected into and is settled out white polymer in the excess ethanol, this white polymer is filtered by glass funnel, use washing with alcohol, dry in a vacuum 24 hours polymkeric substance (74.4 weight % of monomeric gross weight) under 65 ℃ to produce 3.82g 5-norbornylene-2-acetic acid allyl ester.The molecular weight of this polymkeric substance (Mw) is 175,400, and Mw/Mn is 3.52.
Embodiment 33: under 90 ℃ of temperature in methylene dichloride 5-norbornylene-2-acetic acid allyl group
The polymerization of ester (catalyzer (allyl group) Pd (acac))
5.6g (monomeric gross weight 56.0%) 5-norbornylene-2-acetic acid allyl ester polymkeric substance is by the preparation of the same procedure described in the embodiment 28, except (allyl group) Pd (acac) replaces palladium as catalyzer.The molecular weight of this polymkeric substance (Mw) is 141,000, and Mw/Mn is 2.3.
Embodiment 34: 5-norbornylene-2-carboxylate methyl ester and 5-norbornylene-2-acetic acid in toluene
The copolymerization of allyl ester (catalyzer: palladium, 5-norbornylene-2-carboxylate methyl ester/5-norborneol
Alkene-2-acetic acid allyl ester=1/2)
5-norbornylene-2-the carboxylate methyl ester of preparation among the preparation embodiment 1 (5.89g, 38.7mmol), the 5-norbornylene-2-acetic acid allyl ester of preparation among the preparation embodiment 5 (15.0g, 90.2mmol) and toluene (41ml) pack in the 250mL Schlenk flask.(methylene dichloride: 5ml) comprise palladium (2.89mg, 13.0 μ mol), tricyclohexyl phosphine (3.62mg, 13.0 μ mol) and xylidine four (pentafluorophenyl group) borate (20.66mg, 26.0 μ mol) join in this flask catalyst solution.Reaction mixture stirring reaction 18 hours under 90 ℃ of temperature.After polyreaction is finished, this reaction mixture is injected into and is settled out white polymer in the excess ethanol, this white polymer is filtered by glass funnel, use washing with alcohol, under 65 ℃ dry in a vacuum 24 hours with the multipolymer of producing 10.48g 5-norbornylene-2-carboxylate methyl ester and 5-norbornylene-2-acetic acid allyl ester (monomeric gross weight 50.2%).The molecular weight of this polymkeric substance (Mw) is 144,000, and Mw/Mn is 2.4.
The copolymerization of embodiment 35:5-norbornylene-2-carboxylate methyl ester and norbornylene (catalyzer: Pd (acac)
2)
5-norbornylene-2-the carboxylate methyl ester (16.74g) of preparation among the preparation embodiment 1, norbornylene (4.44g) and toluene (37mL) are packed in the 250mL Schlenk flask.Xylidine four (pentafluorophenyl group) borate (25.2mg) that is dissolved in palladium (4.79mg) and the tricyclohexyl phosphine (4.41mg) in the toluene (5mL) and is dissolved in the methylene dichloride (2mL) joins in the flask.Reaction mixture stirring reaction 18 hours under 90 ℃ of temperature.After polyreaction is finished, this reaction mixture is injected into and is settled out white polymer in the excess ethanol, this white polymer is filtered by glass funnel, use washing with alcohol, under 65 ℃ dry in a vacuum 24 hours with the multipolymer of producing 12.96g 5-norbornylene-2-carboxylate methyl ester and norbornylene (monomeric gross weight 61.2%).The molecular weight of this polymkeric substance (Mw) is 164,000, and Mw/Mn is 2.02.
The copolymerization of embodiment 36:5-norbornylene-2-carboxylate methyl ester and butyl norbornylene (catalyzer: Pd (acac)
2)
5-norbornylene-2-the carboxylate methyl ester (14.64g) of preparation among the preparation embodiment 1, butyl norbornylene (6.14g) and toluene (37mL) are packed in the 250mL Schlenk flask.Be dissolved in the Pd (acac) in the toluene (5mL)
2(4.19mg) and tricyclohexyl phosphine (4.41mg) and xylidine four (pentafluorophenyl group) borate (25.2mg) that is dissolved in the methylene dichloride (2mL) join in the flask.Reaction mixture stirring reaction 18 hours under 90 ℃ of temperature.After polyreaction is finished, this reaction mixture is injected into and is settled out white polymer in the excess ethanol, this white polymer is filtered by glass funnel, use washing with alcohol, under 65 ℃ dry in a vacuum 24 hours with the multipolymer of producing 12.08g 5-norbornylene-2-carboxylate methyl ester and butyl norbornylene (monomeric gross weight 58.1%).The molecular weight of this polymkeric substance (Mw) is 116,000, and Mw/Mn is 1.97.
The copolymerization of embodiment 37:5-norbornylene-2-acetate and hexyl norbornylene (catalyzer: Pd (acac)
2)
5-norbornylene-2-acetate (13.57g), hexyl norbornylene (6.82g) and toluene (42mL) are packed in the 250mL Schlenk flask.Be dissolved in the Pd (acac) in the toluene (5mL)
2(3.9mg) and tricyclohexyl phosphine (3.6mg) and xylidine four (pentafluorophenyl group) borate (20.4mg) that is dissolved in the methylene dichloride (2mL) join in the flask.Reaction mixture stirring reaction 18 hours under 90 ℃ of temperature.After polyreaction is finished, this reaction mixture is injected into and is settled out white polymer in the excess ethanol, this white polymer is filtered by glass funnel, use washing with alcohol, under 65 ℃ dry in a vacuum 24 hours with the multipolymer of producing 10.4g 5-norbornylene-2-acetate and hexyl norbornylene (monomeric gross weight 51.0%).The molecular weight of this polymkeric substance (Mw) is 231,000, and Mw/Mn is 2.11.
The copolymerization of embodiment 38:5-norbornylene-2-acetic acid allyl ester and butyl norbornylene (catalyzer: Pd (acac)
2)
5-norbornylene-2-acetic acid the allyl ester (8.2g) of preparation among the preparation embodiment 1, butyl norbornylene (3.2g) and toluene (47mL) are packed in the 250mL Schlenk flask.Catalyst solution (methylene dichloride: 5ml) comprise Pd (acac)
2(3.2mg), tricyclohexyl phosphine (4.0mg) and xylidine four (pentafluorophenyl group) borate (40.0mg) join in this flask.Reaction mixture stirring reaction 18 hours under 90 ℃ of temperature.After polyreaction is finished, this reaction mixture is injected into and is settled out white polymer in the excess ethanol, this white polymer is filtered by glass funnel, use washing with alcohol, dry in a vacuum 24 hours multipolymers (77.8 weight % are based on monomeric gross weight) under 65 ℃ to produce 8.85g 5-norbornylene-2-acetic acid allyl ester and butyl norbornylene.The molecular weight of this polymkeric substance (Mw) is 198,300, and Mw/Mn is 3.44.
Copolymerization (the catalysis of embodiment 39:5-norbornylene-2-butyl carboxylate and phenyl norbornylene
Agent: palladium)
5-norbornylene-2-the butyl carboxylate (9.19g) of preparation among the preparation embodiment 3, phenyl norbornylene (4.5g) and toluene (30mL) are packed in the 250mL Schlenk flask.Catalyst solution (methylene dichloride: 3ml) comprise Pd (acac)
2(1.98mg), tricyclohexyl phosphine (2.47mg) and xylidine four (pentafluorophenyl group) borate (14.1mg) join in this flask.Reaction mixture stirring reaction 18 hours under 90 ℃ of temperature.After polyreaction is finished, this reaction mixture is injected into and is settled out white polymer in the excess ethanol, this white polymer is filtered by glass funnel, use washing with alcohol, under 65 ℃ dry in a vacuum 24 hours with the multipolymer of producing 8.28g 5-norbornylene-2-butyl carboxylate and phenyl norbornylene (monomeric gross weight 60.5%).The molecular weight of this polymkeric substance (Mw) is 132,000, and Mw/Mn is 2.69.
The comparative example 1: 5-norbornylene-2-butyl carboxylate's copolymerization (catalyzer: Pd (acac) in methylene dichloride
2)
1.23g (monomeric gross weight 6.4%) 5-norbornylene-2-butyl carboxylate polymkeric substance is by the preparation of the same procedure described in the embodiment 11, except polymerization temperature becomes 60 ℃.
The comparative example 2～4: under various polymerization temperatures in methylene dichloride 5-norbornylene-2-butyl carboxylate's polymerization (catalyzer: Pd (acac)
2)
5-norbornylene-2-butyl carboxylate polymkeric substance is by the preparation of the same procedure described in the embodiment 11, except polymerization temperature becomes as shown in table 5 65,70 and 75 ℃ respectively.The result is shown in following table 5.
Table 5
| Comparative example's numbering | Monomer (mL) | Temperature (℃) | Time (h) | Productive rate | Mw | Mw/Mn | |
| ?[g] | ?[％] | ||||||
| The comparative example 1 | BENB(20) | 60 | 18 | ?1.23 | ?6.4 | ?124,600 | 1.54 |
| The comparative example 2 | BENB(20) | 65 | 18 | ?1.30 | ?6.7 | ?134,200 | 1.67 |
| The comparative example 3 | BENB(20) | 70 | 18 | ?1.52 | ?7.8 | ?137,100 | 1.68 |
| The comparative example 4 | BENB(20) | 75 | 18 | ?2.15 | ?11.1 | ?146,100 | 1.88 |
The polymerization of comparative example 5:5-norbornylene-2-carboxylate methyl ester (catalyzer: [(allyl group) PdCl]
2)], the mol ratio of monomer and catalyzer is 4000: 1)
[(allyl group) PdCl]
2)] (6.0mg) and four (pentafluorophenyl group) lithium tetraborate (22.5mg) and tricyclohexyl phosphine (12.0mg) be enclosed in 100mL Schlenk flask in the loft drier as catalyzer, then to wherein adding the 5ml methylene dichloride.5-norbornylene-2-carboxylate methyl ester (10mL) and toluene (20ml) join in the 250ml Schlenk flask.Catalyst mixture at room temperature joins in the monomer solution, and temperature of reaction is raised to 90 ℃ then, and this reaction mixture reacted 18 hours down at 90 ℃.Then, this reaction mixture is injected in the excess ethanol.Do not detect the polymer precipitation thing.
Comparative example 6:5-norbornylene-2-butyl carboxylate's polymerization (rubbing of monomer and catalyzer
You are than being 500: 1)
[(allyl group) PdCl]
2)] (18.8mg) and four (pentafluorophenyl group) lithium tetraborate (70.6mg) and tricyclohexyl phosphine (36.1mg) be enclosed in 100mL Schlenk flask in the loft drier as catalyzer, then to wherein adding the 5ml methylene dichloride.Join in the 250ml Schlenk flask under 5-norbornylene-2-butyl carboxylate (5mL) and the toluene (20ml).Catalyst mixture at room temperature joins in the monomer solution, and temperature of reaction is raised to 90 ℃ then, and this reaction mixture reacted 18 hours down at 90 ℃.Then, this reaction mixture is injected in the excess ethanol.Do not detect the polymer precipitation thing.
Comparative example 7:5-norbornylene-2-butyl carboxylate's polymerization (rubbing of monomer and catalyzer
You are than being 100: 1)
[(allyl group) PdCl])]
2(188mg) and four (pentafluorophenyl group) lithium tetraborate (1.06g) and tricyclohexyl phosphine (361mg) be enclosed in 100mL Schlenk flask in the loft drier as catalyzer, then to wherein adding the 10ml methylene dichloride.Join in the 250ml Schlenk flask under 5-norbornylene-2-butyl carboxylate (10mL) and the toluene (20ml).Catalyst mixture at room temperature joins in the monomer solution, and temperature of reaction is raised to 90 ℃ then, and this reaction mixture reacted 18 hours down at 90 ℃.Then, this reaction mixture is injected in the excess ethanol.Do not detect the polymer precipitation thing.
Can find out that from comparative example 1～4 polyreaction is lower than 80 ℃, can obtain molecular weight and be 100,000 or higher polymkeric substance, but polymerization yield rate be very low.In comparative example 5～7, from the ester norborneol polymerization in the presence of the catalyzer that has with its coordinate alkyl ligand, do not obtain polymkeric substance.Thinking does not have at comparative example's 5～7 used this catalyzer that used in an embodiment to have a catalyzer that contains the oxygen ligand thermally-stabilised, thus at high temperature the used catalyzer of this comparing embodiment 5～7 by the passivation of monomeric functional group.Therefore, according to the present invention, having the catalyzer that contains the oxygen ligand is stable under 80 ℃ or higher high temperature, and this catalyzer is by functional group's passivation of cycloolefin monomers, and the cyclenes that allows to produce has 100,000 or higher high molecular.
Embodiment 40～42: use the cyclic olefin polymer that contains polar functional group to prepare film
Each polymkeric substance of embodiment 4,19 and 25 preparations and solvent are to form coating solution as shown in table 6.This coating solution uses knife coater or scraping strip coating machine to cast on the substrate of glass.Then, this substrate at room temperature dry 1 hour, further following dry 18 hours then at 100 ℃.This sheet glass kept for 10 seconds under-10 ℃ of temperature, and the film on this sheet glass uses pocket knife to peel off and obtains thickness error and be lower than 2% transparent film.The optical transmittance of this film and thickness are as shown in table 6 when 400～800nm.
Optical anisotropy
The specific refractory power of each transparent film (n) is measured with the Abbe refractometer.The differing of film inside (Re) with automatic double refraction instrument (Wang Ja Instruments; KOBRA-21 ADH) measures.Measure angle (R when incident light and thin film planar
θ) after the differing when being 50 °, at film internal membrane thickness direction and the axial phase differential (R of x-
Th) calculate by following equation 2.
[equation 2]
(n
x-n
y) and (n
y-n
z) the difference of specific refractory power pass through R
eAnd R
ThValue is calculated divided by film thickness and is drawn.(the n of each transparent film
x-n
y), R
θ, R
Th(n
y-n
z) value as shown in table 6.
Table 6
| Classification | The component of film solution | The physical property of film | ||||||
| Polymkeric substance (weight part) | Solvent (weight part) | Thickness (μ m) | Optical transmittance (%) | N (specific refractory power) | (n x-n y)×10 3 | R th(nm/μm) | (n y-n z)×10 3 | |
| Embodiment 40 | Polymkeric substance (embodiment 4) 100 | THF，560 | ?114 | 92 | 1.52 | 0.008 | 5.78 | 5.78 |
| Embodiment 41 | Polymkeric substance (embodiment 19) 100 | MC：360TL：200 | ?120 | 92 | 1.50 | 0.009 | 2.13 | 2.13 |
| Embodiment 42 | Polymkeric substance (embodiment 25) 100 | TL：560 | ?103 | 91 | 1.51 | 0.012 | 3.29 | 3.29 |
In table 6, THF represents tetrahydrofuran (THF), and MC represents methylene dichloride, and TL represents toluene.
As triacetate fiber membrane (n
y＞n
z) be that eclipsed is with measure R
θDuring value, all R of each film
θValue has all increased.This shows that this film has negative birefringence rate (n in the film thickness direction
y＞n
z).
Equation 3 below this optically anisotropic specific refractory power satisfies.
(equation 3)
In equation 3, n
xBe specific refractory power at the plane slow-axis direction, n
yBe specific refractory power at the plane quick shaft direction, and n
zIt is specific refractory power at thickness direction.
The specific refractory power of the anisotropy optics film thickness direction that polymkeric substance of the present invention is made can be according to the control of the type of the functional group that introduces in polymkeric substance and content and is different.Therefore, this anisotropy optics film can be used as the optical compensating film of the various display equipments that comprise liquid-crystal display.
Embodiment 43: butyl ester norbornylene homopolymer thin films is to the sticking property of PVA light polarizing film
Polymeric film is formed by the 5-norbornylene-2-butyl carboxylate's of embodiment 19 preparations polymer manufacture.Polymeric film then, is measured contact angle with linear speed 6m/min 80mA corona treatment three times.For water, contact angle is 20.7 °, and for methylene iodide, contact angle is 20 °.Surface tension is calculated and is 76.9mN/m.
In 30 minutes after the corona treatment, the PVA light polarizing film of thorough drying (iodine type, transmissivity: 44%) with the roll-in of 10wt%PVA solution.Then, following dry 10 minutes 80 ℃ of temperature.Have thereon and demonstrated extraordinary sticking property by the PVA Polarizer of the butyl ester norbornene polymer film of roll-in.
According to the present invention, temperature of reaction and the reaction times contained greater than the monomeric Diels-Alder reaction of the monomeric exo-rich norbornene-ester group of external form norbornylene-ester of 50mol% by control can obtain high yield.When being aggregated in the presence of exo-rich norbornene-ester monomer has the X group 4 transition metal catalyst system of specific ligand, having the high-molecular weight norbornene based addition polymer can be produced with high yield.Prepared norbornylene-ester group addition polymer has good optical characteristics so that is used for protective membrane, retardation films or the glass substrate of the polarizer, and tool has good adhesivity to various substrates.
Industrial applicibility
The method according to this invention can be avoided owing to contain the reduction of the catalyst activity that the endo isomer of polar functional group causes.In addition, cyclic olefin polymer can use a spot of catalyzer with high yield production.And, because the polar functional group cyclic olefin polymer that contains according to method preparation of the present invention is transparent, and have the thermostability and the intensity that adhere to metal or contain the abundant adhesive power of opposed polarity functional polymer and strengthened, so it can be as the insulation electronic material.And, can be by isotropic optical thin film of making by the polar functional cyclic olefin polymer that present method is produced as the compensation film of various display equipments, because type and content that its reflectivity at thickness direction can rely on the functional group that introduces in the polymkeric substance are controlled.
Though the present invention is described in detail with reference to its specific embodiments, the present invention is not subjected to the restriction of embodiment, and only is subjected to the restriction of appended claim.One skilled in the art will understand that and to carry out various modifications and replacement to the present invention and do not break away from the spirit and scope of the invention.
Claims (5)
1. optical anisotropic film, comprise according to method preparation as described below and have 100,000 or the cyclic olefin polymer that contains polar functional group of higher molecular weight,
Described method comprises:
The preparation catalyst mixture, catalyst mixture comprises
I) be Pd (acac)
2, palladium or (allyl group) Pd (acac) pre-catalyst, this pre-catalyst contains the 10th group 4 transition metal that has with the part of the oxygen-carrying ion of the 10th group 4 transition metal bonding;
It ii) is first promotor that contains the organic compound of the 15th family's element; With
Iii) can provide negatively charged ion and can with coordinate second promotor a little less than the metal of this pre-catalyst; With
Under 80～200 ℃ of temperature, in the presence of organic solvent and catalyst mixture, make the monomer solution that comprises the norbornylene based compound that contains polar functional group carry out polyaddition reaction, the total amount of this organic solvent be by weight in the monomer solution contained total monomer weight 50～800%, and the productive rate of polymkeric substance be by weight total monomer weight 50% or more
Wherein, described cyclic olefin polymer is to contain polar functional group and by the polymkeric substance of the norbornylene based compound of following chemical formula 5 expressions:
Chemical formula 5
Wherein
M is 0～4 integer;
R
7, R
8, R
9And R
10In at least one is a polar functional group, other be non-polar functional group, and R
7, R
8, R
9And R
10Can be combined together to form saturated or undersaturated C
1-20Cyclic group or C
6-24Aromatic nucleus;
Described nonpolar functional group is selected from the following groups: hydrogen; Halogen; Linear or dendritic C
1-20Alkyl; Linear or dendritic C
1-20Alkylhalide group; Linear or dendritic C
1-20Thiazolinyl; Linear or dendritic C
1-20Haloalkenyl; Linear or dendritic C
3-20Alkynyl; Linear or dendritic C
3-20Alkynyl halide; Replace or unsubstituted C with alkyl, thiazolinyl, alkynyl, halogen, alkylhalide group, haloalkenyl or alkynyl halide
3-12Cycloalkyl; Replace or unsubstituted C with alkyl, thiazolinyl, alkynyl, halogen, alkylhalide group, haloalkenyl or alkynyl halide
6-40Aryl; Replace or unsubstituted C with usefulness alkyl, thiazolinyl, alkynyl, halogen, alkylhalide group, haloalkenyl or alkynyl halide
7-15Aralkyl;
Described polar functional group is the nonhydrocarbon polar group that contains at least one O, N, P, S, Si and B, and is selected from the following groups: OR
12, OC (O) OR
12, R
11OC (O) OR
12, C (O) R
12, R
11C (O) R
12, OC (O) R
12, R
11OC (O) R
12, (R
11O) pOR
12, (OR
11) pOR
12, C (O) OC (O) R
12, R
11C (O) OC (O) R
12, SR
12, R
11SR
12, SSR
12, R
11SSR
12, S (=O) R
12, R
11S (=O) R
12, R
11C (=S) R
12, R
11C (=S) SR
12, R
11SO
3R
12, SO
3R
12, R
11N=C=S, NCO, R
11NCO, CN, R
11CN, NNC (=S) R
12, R
11NNC (=S) R
12, NO
2, R
11NO
2,
R wherein
11Be linear or dendritic C
1-20Alkyl; Linear or dendritic C
1-20Alkylhalide group; Linear or dendritic C
1-20Thiazolinyl; Linear or dendritic C
1-20Haloalkenyl; Linear or dendritic C
3-20Alkynyl; Linear or dendritic C
3-20Alkynyl halide; Replace or unsubstituted C with alkyl, thiazolinyl, alkynyl, halogen, alkylhalide group, haloalkenyl or alkynyl halide
3-12Cycloalkyl; Replace or unsubstituted C with alkyl, thiazolinyl, alkynyl, halogen, alkylhalide group, haloalkenyl or alkynyl halide
6-40Aryl; Replace or unsubstituted C with alkyl, thiazolinyl, alkynyl, halogen, alkylhalide group, haloalkenyl or alkynyl halide
7-15Aralkyl;
R
12, R
13And R
14Be hydrogen independently of one another; Halogen; Linear or dendritic C
1-20Alkyl; Linear or dendritic C
1-20Alkylhalide group; Linear or dendritic C
1-20Thiazolinyl; Linear or dendritic C
1-20Haloalkenyl; Linear or dendritic C
3-20Alkynyl; Linear or dendritic C
3-20Alkynyl halide; Replace or unsubstituted C with alkyl, thiazolinyl, alkynyl, halogen, alkylhalide group, haloalkenyl or alkynyl halide
3-12Cycloalkyl; Replace or unsubstituted C with alkyl, thiazolinyl, alkynyl, halogen, alkylhalide group, haloalkenyl or alkynyl halide
6-40Aryl; Replace or unsubstituted C with alkyl, thiazolinyl, alkynyl, halogen, alkylhalide group, haloalkenyl or alkynyl halide
7-15Aralkyl; Or alkoxyl group, halogen alkoxyl group, carbonyl oxygen base, halogen carbonyl oxygen base; With
P is 1～10 integer.
2. optical anisotropic film according to claim 1, wherein this optical anisotropic film has the length of delay R of 70～1000nm
Th, length of delay such as following equation 1 definition:
Equation 1
R
th＝Δ(n
y-n
z)×d
Wherein, n
yBe the specific refractory power of quick shaft direction in the plane, under wavelength 550nm, measure;
n
zBe specific refractory power, under wavelength 550nm, measure along thickness direction; With
D is a film thickness.
3. optical anisotropic film according to claim 1, the equation 3 below the specific refractory power of this optical anisotropic film satisfies:
Equation 3
Wherein, n
xBe the specific refractory power of slow-axis direction in the plane, n
yBe the specific refractory power of quick shaft direction in the plane, n
zIt is specific refractory power along thickness direction.
4. optical anisotropic film according to claim 3, wherein this optical anisotropic film is used as the negative C template optical compensating film of liquid-crystal display.
5. a display equipment comprises optical anisotropic film as claimed in claim 1.
Applications Claiming Priority (6)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| KR1020020076925 | 2002-12-05 | ||
| KR10-2002-0076925A KR100477943B1 (en) | 2002-12-05 | 2002-12-05 | Method for polymerizing cyclic olefins containing polar functional groups |
| KR10-2002-0076925 | 2002-12-05 | ||
| KR10-2003-0086705 | 2003-12-02 | ||
| KR1020030086705 | 2003-12-02 | ||
| KR10-2003-0086705A KR100515595B1 (en) | 2003-12-02 | 2003-12-02 | Method for polymerizing cyclic olefins containing polar functional groups and electrnic devices employing polymerized cyclic olefins |
Related Parent Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CNB2003801001800A Division CN100347207C (en) | 2002-12-05 | 2003-12-03 | Method for polymerizing cycloolefin polymer containing polar functional groups and electronic devices employing the polymerized cycloolefins |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN101012314A CN101012314A (en) | 2007-08-08 |
| CN101012314B true CN101012314B (en) | 2011-12-28 |
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| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN2007100004500A Expired - Lifetime CN101012314B (en) | 2002-12-05 | 2003-12-03 | Optical anisotropy thin film and display device containing same |
| CNB2003801001800A Expired - Lifetime CN100347207C (en) | 2002-12-05 | 2003-12-03 | Method for polymerizing cycloolefin polymer containing polar functional groups and electronic devices employing the polymerized cycloolefins |
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| CNB2003801001800A Expired - Lifetime CN100347207C (en) | 2002-12-05 | 2003-12-03 | Method for polymerizing cycloolefin polymer containing polar functional groups and electronic devices employing the polymerized cycloolefins |
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| CN1910210B (en) * | 2004-07-07 | 2010-12-08 | Lg化学株式会社 | Method of producing cyclic olefin polymers having polar functional groups, olefin polymer produced using the method and optical anisotropic film comprising the same |
| KR100733923B1 (en) | 2004-07-07 | 2007-07-02 | 주식회사 엘지화학 | Catalysts for polymerizing cyclic olefin having polar funtional group, polymerizing methods using the catalysts, olefin polymer produced by the methods and optical anisotropic film comprising the same |
| WO2006031067A1 (en) | 2004-09-16 | 2006-03-23 | Lg Chem, Ltd. | Catalyst system for polymerizing cyclic olefin having polar functional group, polymerizing method using the catalyst system, olefin polymer produced by the method and optical anisotropic film comprising the olefin polymer |
| WO2006052116A1 (en) | 2004-11-15 | 2006-05-18 | Lg Chem, Ltd. | Biaxial-optical polynorbornene-based film and method of manufacturing the same, integrated optical compensation polarizer having the film and method of manufacturing the polarizer, and liquid crystal display panel containing the film and/or polarizer |
| KR100804822B1 (en) * | 2005-10-17 | 2008-02-20 | 주식회사 엘지화학 | Polymerzation methods using the catalysts |
| KR101257412B1 (en) | 2009-08-19 | 2013-04-23 | 주식회사 엘지화학 | Method for preparing cyclic olefin-based polymer |
| KR101101186B1 (en) | 2010-07-27 | 2012-01-03 | 고려대학교 산학협력단 | Catalyst for dehydrogenation of metal hydride and method for generating hydrogen using the same |
| KR20160038096A (en) * | 2014-09-27 | 2016-04-07 | 주식회사 효성 | Optical anisotropic film of norbornene, and manufacturing the same |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1330098A (en) * | 2000-07-05 | 2002-01-09 | 东丽株式会社 | Thermoplastic resin film, manufacture method thereof and optical thin film |
| WO2002088784A2 (en) * | 2001-04-27 | 2002-11-07 | Jsr Corporation | Thermoplastic norbornene resin based optical film |
| WO2002088783A1 (en) * | 2001-04-27 | 2002-11-07 | Jsr Corporation | Thermoplastic norbornene resin based optical film |
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| US5527752A (en) * | 1995-03-29 | 1996-06-18 | Union Carbide Chemicals & Plastics Technology Corporation | Catalysts for the production of polyolefins |
| CZ291970B6 (en) * | 1995-03-29 | 2003-06-18 | Univation Technologies Llc | Ethylene polymer, process of its preparation and use of such ethylene polymer |
| KR100561068B1 (en) * | 2002-07-10 | 2006-03-15 | 주식회사 엘지화학 | Norbornene-ester based addition polymer and method for preparing the same |
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2002
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1330098A (en) * | 2000-07-05 | 2002-01-09 | 东丽株式会社 | Thermoplastic resin film, manufacture method thereof and optical thin film |
| WO2002088784A2 (en) * | 2001-04-27 | 2002-11-07 | Jsr Corporation | Thermoplastic norbornene resin based optical film |
| WO2002088783A1 (en) * | 2001-04-27 | 2002-11-07 | Jsr Corporation | Thermoplastic norbornene resin based optical film |
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| Publication number | Publication date |
|---|---|
| CN101012314A (en) | 2007-08-08 |
| KR20040049946A (en) | 2004-06-14 |
| CN100347207C (en) | 2007-11-07 |
| KR100477943B1 (en) | 2005-03-21 |
| CN1692131A (en) | 2005-11-02 |
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