Norborneol alkenes, esters of acrylic acid and vinylene carbonate ternary polymerization catalyst with
And method for ternary polymerization
Technical field
The present invention relates to high polymer field, a kind of norborneol alkenes, esters of acrylic acid and vinylene carbonate are referred specifically to
Ternary polymerization catalyst and method for ternary polymerization.
Background technique
Polynorbornene is a kind of special polymer, with excellent mechanical property, heat resistance, in organic solvent
The soluble and transparency, can be used for 193nm ultraviolet light photoetching.This material major defect be brittleness, viscosity difference it is low with molecular weight
Deng.After oxygen-containing alkene is inserted into polynorbornene main chain, the caking property and solubility of polymer can be improved, and reduce material
The absorptance of itself.This copolymer can be used as photoresist applied to 193nm replica technology.Moreover, the hair of microelectronics industry
Exhibition needs smaller ingredient, and to the exposure technique that line width is 1.3 μm and following line width is suitable for, 193nm photoetching may be selected
Technology, these technologies are related to the various aspects of photoetching process, propose new optical material and its manufacture and coating technique, novel
Resist, for new material of mask and its protective film etc. up for solving the problems, such as.Therefore, in order to which the photoetching obtained is new
Material has developed alternating copolymerization material, main development norbornene and maleic anhydride, tetrafluoroethene or other component ternary polymerizations
Material, while application has the norbornene of side group, it is therefore an objective to the resistance to corrosion of entire matrix is improved, lithography performance is improved, is increased
Caking property, solubility and the toughness of material.
The method for synthesizing these materials at present mainly has the methods of free radical, living radical, metallic catalyst.Such as
The synthesis of photoetching material disclosed in Vol.5039 (2003) page 80~92 of Proceedings of SPIE uses peroxidating
Catalyst of the object as free radical polymerization, disclosed in Vol.4690 (2002) page 127~135 of Proceedings of SPIE
The synthesis of photoetching material uses the catalyst of AINB (azodiisobutyronitrile) as free radical polymerization.A.E.Feiring and
M.Toriumi etc. is by norbornene, tetrafluoroethene and free radical acrylate ternary polymerization etc..These the synthesis sides applied at present
Method is long there are the reaction time, obtains the disadvantages such as copolymer yield is low, molecular weight of copolymer is small, copolymer alternate degree is low.
Summary of the invention
The technical problem to be solved by the present invention is to for the prior art status provide one kind can reduce reaction temperature,
Improve norborneol alkenes, esters of acrylic acid and the vinylene carbonate ternary polymerization catalysis of catalytic efficiency and copolymer yield
Agent.
Another technical problem to be solved by this invention is to provide a kind of lower reaction temperature, high catalytic efficiency and copolymerization
Norborneol alkenes, the method for esters of acrylic acid and vinylene carbonate ternary polymerization of object high income.
The technical scheme of the invention to solve the technical problem is: norborneol alkenes, esters of acrylic acid and the carbon
Sour vinylene ternary polymerization catalyst, it is characterised in that the catalyst the preparation method is as follows:
In the container of dry atmosphere of inert gases, will be bis- (cyclopentadiene) magnesium and ligand be dissolved in the first solvent,
Obtain mixed solution;Then at 200-500rpm, alkyl aluminum is instilled in the mixed solution, after dripping off at 30-60 DEG C
Continue stirring 30-60 minutes to get magnesium-aluminum complex catalyst;
The molar ratio of bis- (cyclopentadiene) magnesium and the ligand is 1: 15~15: 1, bis- (cyclopentadiene) magnesium and
The molar ratio of the alkyl aluminum is 1: 15~15: 1;
The ligand is selected from 8-hydroxyquinoline, α, α '-bipyridyl, Phen, isoquinolin, quinoline, porphyrin, acetyl group third
Ketone;
The alkyl aluminum is selected from triisobutyl aluminium or triethyl aluminum.
First solvent is selected from benzene, toluene, tetrahydrofuran, petroleum ether, methyl phenyl ethers anisole, 1,4- dioxane, 1,2- dichloro
Ethane, hexamethylene or cyclohexanone;The dosage of the solvent and bis- (cyclopentadiene) magnesium, alkyl aluminum and ligand three's total amount
Ratio is 10 milliliters: 0.010~0.035 moles.
Bis- (cyclopentadiene) magnesium, alkyl aluminum and the molar ratio of ligand three are preferably 1: 10: 8.
The ligand and first solvent can first be dried before use;The wherein solid-state ligand in the ligand
Drying be first with recrystallization method purify then be dried in vacuo;The drying of liquid ligand in the ligand be with calcium hydride or
Metallic sodium is dry, and the solvent is dry using calcium chloride or calcium hydride.
Use above-mentioned norborneol alkenes, the norbornene of esters of acrylic acid and vinylene carbonate ternary polymerization catalyst
Class, esters of acrylic acid and vinylene carbonate method for ternary polymerization, it is characterised in that include the following steps:
Norbornene derivative, esters of acrylic acid and vinylene carbonate ester monomer is taken to be added to according to molar ratio 1: 1:1 more
It is secondary to vacuumize, in nitrogen charging autoclave, the dissolution of the second solvent is added;Then magnesium-the aluminum complex catalyst is added, 30~
At 110 DEG C, reacted 1~6 hour under 0.1-8MPa pressure;
The product that reaction obtains is poured into the ethanol solution of the hydrochloric acid containing 4-5wt%, obtained precipitates washed with EtOH
To neutrality, norbornene class, esters of acrylic acid and vinylene carbonate terpolymer are obtained after vacuum drying;
The dosage of the magnesium-aluminum complex catalyst is calculated as norbornene by the amount of (cyclopentadiene) bis- in catalyst magnesium
The 0.01%-1.50% of class, esters of acrylic acid and vinylene carbonate total weight;
Second solvent is selected from benzene, toluene, tetrahydrofuran, petroleum ether, methyl phenyl ethers anisole, 1,4- dioxane, 1,2- dichloro
Ethane, hexamethylene or cyclohexanone;The amount ratio of the sum of molal quantity of each polymerized monomer and second solvent is 0.03 mole: 20
Milliliter.
The acrylic ester monomer is selected from methyl acrylate, ethyl acrylate, butyl acrylate, methyl methacrylate
Ester, ethyl methacrylate, butyl methacrylate or tert-butyl methacrylate.
The Norbornene derivative is selected from two rings [2,2,1] hept-2-ene", 1- methyl bicyclic [2,2,1] hept-2-ene", 5-
Methyl bicyclic [2,2,1] hept-2-ene", 7- methyl bicyclic [2,2,1] hept-2-ene", two ring of 1- ethyl [2,2,1] hept-2-ene", 5- second
Two ring of base [2,2,1] hept-2-ene", 5,5- dimethyl, two ring [2,2,1] hept-2-ene", two ring of 1- phenyl [2,2,1] hept-2-ene", 5-
Two ring of phenyl [2,2,1] hept-2-ene", two ring of 5- vinyl [2,2,1] hept-2-ene", two rings [2,2,1] hept-2-ene" -5- formic acid first
Ester or two rings [2,2,1] hept-2-ene" -5- formic acid spy's butyl ester.
Compared with prior art, the present invention provides a kind of new norbornene copolymer and the catalysis of the copolymer is prepared
Agent, the copolymer resistance to corrosion provided is good, and material absorptance is low, and lithography performance is excellent;Used catalyst is a kind of novel
Magnesium-aluminum complex catalyst, catalyst raw material is cheap and easy to get, can generate catalytic activity, norborneol alkenes, propylene at relatively low temperatures
Esters of gallic acid and vinylene carbonate ternary polymerization, polymeric reaction temperature is low, high catalytic efficiency, and product is easy to washing separation,
Copolymer yield is high.
Specific embodiment
Present invention is further described in detail with reference to embodiments.
The preparation process of catalyst in following embodiment unless otherwise instructed carries out ligand therein and solvent
It is dried.Specifically: the drying of the solid ligand in ligand is first to be purified then to be dried in vacuo with recrystallization method;
The drying of liquid ligand in ligand is dried with calcium hydride drying or with metallic sodium.The drying of solvent is with calcium chloride or hydrogen
It is dry to change calcium.
Embodiment 1
In the three-necked flask of dry atmosphere of inert gases, 0.001 is rubbed bis- (cyclopentadiene) magnesium and 0.004 mole of 8-
Oxyquinoline is dissolved in 10 milliliters of benzene, at 250rpm, 0.012 mole of triisobutyl aluminium is instilled in above-mentioned solution, after dripping off
Constant temperature stirs 40 minutes to get magnesium-aluminum complex catalyst at 40 DEG C of same stirring rate.
By 0.01 mole of two ring [2,2,1] hept-2-ene", 0.01 mol propylene acid methyl esters and 0.01 mole of vinylene carbonate
It is added to and repeatedly vacuumizes, in nitrogen charging autoclave, 20ml benzene is added to dissolve.Two are calculated as by the amount of (cyclopentadiene) bis- in catalyst magnesium
Ring [2,2,1] hept-2-ene", methyl acrylate and vinylene carbonate three's total weight 0.01% take above-mentioned magnesium-aluminium complex
Catalyst is injected in above-mentioned mixture with syringe.Constant temperature reacts 6 hours under 80 DEG C, 4MPa pressure.Product, which is poured into, to be contained
Precipitate copolymer in the ethanol solution of 5wt% hydrochloric acid, precipitates washed with EtOH to neutrality, vacuum drying is to get to two rings
[2,2,1] hept-2-ene", methyl acrylate and vinylene carbonate terpolymer.Calculating reaction yield is 42.4%.
The calculation method of reaction yield is terpolymer weight/total comonomer weight × 100%.Following each embodiments
In yield calculation method be identical with this.
Embodiment 2
In the three-necked flask of dry atmosphere of inert gases, 0.001 is rubbed bis- (cyclopentadiene) magnesium and 0.006 mole of α,
α '-bipyridyl is dissolved in 10 milliliters of toluene, at 200 rpm, 0.015 mole of triisobutyl aluminium is instilled in above-mentioned solution, is dripped off
Constant temperature stirs 60 minutes to get magnesium-aluminum complex catalyst at 50 DEG C of same stirring rate afterwards.
By 0.01 mole of two ring [2,2,1] hept-2-ene", 0.01 mol propylene acetoacetic ester and 0.01 mole of vinylene carbonate
It is added to and repeatedly vacuumizes, in nitrogen charging autoclave, 20ml toluene is added to dissolve.It is calculated as by the amount of (cyclopentadiene) bis- in catalyst magnesium
Two rings [2,2,1] hept-2-ene", ethyl acrylate and vinylene carbonate three's total weight 0.05% take above-mentioned magnesium-aluminium complexing
Object catalyst is injected in above-mentioned mixture with syringe.Constant temperature reacts 6 hours under 110 DEG C, 8MPa pressure.Product, which is poured into, to be contained
Precipitate copolymer in the ethanol solution of 5wt% hydrochloric acid, precipitates washed with EtOH to neutrality, vacuum drying is to get to two rings
[2,2,1] hept-2-ene", ethyl acrylate and vinylene carbonate terpolymer.Calculating reaction yield is 66.5%.
Embodiment 3
In the three-necked flask of dry atmosphere of inert gases, 0.001 is rubbed bis- (cyclopentadiene) magnesium and 0.010 mole of neighbour
Ferrosin is dissolved in 10 milliliters of tetrahydrofurans, at 500 rpm, 0.012 mole of triethyl aluminum is instilled in above-mentioned solution, is dripped off
Constant temperature stirs 30 minutes to get magnesium-aluminum complex catalyst at 60 DEG C of same stirring rate afterwards.
By 0.01 mole of 1- methyl bicyclic [2,2,1] hept-2-ene", 0.01 mol propylene acid butyl ester and 0.01 mole of carbonic acid Asia
Vinyl acetate, which is added to, repeatedly to be vacuumized, in nitrogen charging autoclave, and 20ml tetrahydrofuran is added to dissolve.By (cyclopentadiene) bis- in catalyst
The amount of magnesium is calculated as the 0.10% of 1- methyl bicyclic [2,2,1] hept-2-ene", butyl acrylate and vinylene carbonate three's total weight
Above-mentioned magnesium-aluminum complex catalyst is taken, is injected in above-mentioned mixture with syringe.Constant temperature reacts 4 under 100 DEG C, 6MPa pressure
Hour.Product, which is poured into the ethanol solution of the hydrochloric acid containing 4wt%, precipitates copolymer, precipitates washed with EtOH to neutrality, vacuum
It dries to get 1- methyl bicyclic [2,2,1] hept-2-ene", butyl acrylate and vinylene carbonate terpolymer is arrived.It calculates anti-
Answering yield is 86.1%.
Embodiment 4
In the three-necked flask of dry atmosphere of inert gases, 0.001 is rubbed bis- (cyclopentadiene) magnesium and 0.008 mole of quinoline
Quinoline is dissolved in 10 milliliters of petroleum ethers, at 350rpm, 0.010 mole of triethyl aluminum is instilled in above-mentioned solution, same after dripping off
Constant temperature stirs 60 minutes to get magnesium-aluminum complex catalyst at 50 DEG C of sample stirring rate.
By 0.01 mole of 5- methyl bicyclic [2,2,1] hept-2-ene", 0.01 mole methyl esters and 0.01 mole of carbon
Sour vinylene, which is added to, repeatedly to be vacuumized, in nitrogen charging autoclave, and 20ml petroleum ether dissolution is added.By (rings penta 2 bis- in catalyst
Alkene) amount of magnesium is calculated as 5- methyl bicyclic [2,2,1] hept-2-ene", methyl methacrylate and vinylene carbonate three's total weight
0.08% take above-mentioned magnesium-aluminum complex catalyst, injected in above-mentioned mixture with syringe.Constant temperature is at 110 DEG C, 7MPa pressure
Lower reaction 5 hours.Product, which is poured into the ethanol solution of the hydrochloric acid containing 5wt%, precipitates copolymer, and precipitates washed with EtOH is into
Property, vacuum drying is to get total to 5- methyl bicyclic [2,2,1] hept-2-ene", methyl methacrylate and vinylene carbonate ternary
Polymers.Calculating reaction yield is 88.4%.
Embodiment 5
In the three-necked flask of dry atmosphere of inert gases, 0.001 is rubbed bis- (cyclopentadiene) magnesium and 0.008 mole of porphin
Quinoline is dissolved in 10 milliliters of methyl phenyl ethers anisoles, and at 340rpm, 0.006 mole of triisobutyl aluminium is instilled in above-mentioned solution, after dripping off
Constant temperature stirs 60 minutes to get magnesium-aluminum complex catalyst at same 30 DEG C of stirring rate.
By 0.01 mole of 7- methyl bicyclic [2,2,1] hept-2-ene", 0.01 mole ethyl ester and 0.01 mole of carbon
Sour vinylene, which is added to, repeatedly to be vacuumized, in nitrogen charging autoclave, and 20ml methyl phenyl ethers anisole is added to dissolve.By (rings penta 2 bis- in catalyst
Alkene) amount of magnesium is calculated as 7- methyl bicyclic [2,2,1] hept-2-ene", ethyl methacrylate and vinylene carbonate three's total weight
1.00% take above-mentioned magnesium-aluminum complex catalyst, injected in above-mentioned mixture with syringe.Constant temperature is at 90 DEG C, 5MPa pressure
Lower reaction 1 hour.Product, which is poured into the ethanol solution of the hydrochloric acid containing 5wt%, precipitates copolymer, and precipitates washed with EtOH is into
Property, vacuum drying is to get total to 7- methyl bicyclic [2,2,1] hept-2-ene", ethyl methacrylate and vinylene carbonate ternary
Polymers.Calculating reaction yield is 67.9%.
Embodiment 6
In the three-necked flask of dry atmosphere of inert gases, 0.015 is rubbed bis- (cyclopentadiene) magnesium and 0.001 mole of second
Acyl group acetone is dissolved in 10 milliliters of Isosorbide-5-Nitrae-dioxane, at 500 rpm, 0.015 mole of triethyl aluminum is instilled above-mentioned solution
In, constant temperature stirs 60 minutes to get magnesium-aluminum complex catalyst at 50 DEG C of same stirring rate after dripping off.
By 0.01 mole of two ring of 1- ethyl [2,2,1] hept-2-ene", 0.01 mole butyl ester and 0.01 mole of carbon
Sour vinylene, which is added to, repeatedly to be vacuumized, in nitrogen charging autoclave, and 20ml1, the dissolution of 4- dioxane are added.By double in catalyst
The amount of (cyclopentadiene) magnesium is calculated as two ring of 1- ethyl [2,2,1] hept-2-ene", butyl methacrylate and vinylene carbonate three
The 0.07% of total weight takes above-mentioned magnesium-aluminum complex catalyst, is injected in above-mentioned mixture with syringe.Constant temperature at 30 DEG C,
It is reacted 3 hours under 3MPa pressure.Product, which is poured into the ethanol solution of the hydrochloric acid containing 5wt%, precipitates copolymer, sediment ethyl alcohol
Washing is dried in vacuo to neutrality to get two ring of 1- ethyl [2,2,1] hept-2-ene", butyl methacrylate and vinylene carbonate is arrived
Ester terpolymer.Calculating reaction yield is 53.2%.
Embodiment 7
In the three-necked flask of dry atmosphere of inert gases, 0.015 is rubbed bis- (cyclopentadiene) magnesium and 0.014 mole of 8-
Oxyquinoline is dissolved in 10 milliliters of Isosorbide-5-Nitrae-dioxane, and at 400rpm, 0.001 mole of triethyl aluminum is instilled above-mentioned solution
In, constant temperature stirs 40 minutes to get magnesium-aluminum complex catalyst at 40 DEG C of same stirring rate after dripping off.
By 0.01 mole of two ring of 5- ethyl [2,2,1] hept-2-ene", 0.01 mole spy butyl ester and 0.01 mole
Vinylene carbonate, which is added to, repeatedly to be vacuumized, in nitrogen charging autoclave, and 20ml1, the dissolution of 4- dioxane are added.By double in catalyst
The amount of (cyclopentadiene) magnesium is calculated as two ring of 5- ethyl [2,2,1] hept-2-ene", tert-butyl methacrylate and vinylene carbonate three
The 1.50% of person's total weight takes above-mentioned magnesium-aluminum complex catalyst, is injected in above-mentioned mixture with syringe.Constant temperature at 110 DEG C,
It is reacted 4 hours under 0.1MPa pressure.Product, which is poured into the ethanol solution of the hydrochloric acid containing 5wt%, precipitates copolymer, sediment second
Alcohol is washed to neutrality, and vacuum drying is to get sub- to two ring of 5- ethyl [2,2,1] hept-2-ene", tert-butyl methacrylate and carbonic acid
Vinyl acetate terpolymer.Calculating reaction yield is 43.9%.
Embodiment 8
In the three-necked flask of dry atmosphere of inert gases, by 0.006 rub bis- (cyclopentadiene) magnesium and 0.010 mole it is different
Quinoline is dissolved in 10 milliliters of 1,2- dichloroethanes, at 280rpm, 0.005 mole of triethyl aluminum is instilled in above-mentioned solution, drop
Constant temperature stirs 60 minutes to get magnesium-aluminum complex catalyst at 40 DEG C of same stirring rate after complete.
By 0.01 mole of 5,5- dimethyl, two ring [2,2,1] hept-2-ene", 0.01 mol propylene acid methyl esters and 0.01 mole of carbon
Sour vinylene, which is added to, repeatedly to be vacuumized, in nitrogen charging autoclave, and 20ml1, the dissolution of 2- dichloroethanes are added.By double in catalyst
The amount of (cyclopentadiene) magnesium is calculated as 5,5- dimethyl, two ring [2,2,1] hept-2-ene", methyl acrylate and vinylene carbonate three
The 0.40% of total weight takes above-mentioned magnesium-aluminum complex catalyst, is injected in above-mentioned mixture with syringe.Constant temperature at 50 DEG C,
It is reacted 5 hours under 0.8MPa pressure.Product, which is poured into the ethanol solution of the hydrochloric acid containing 5wt%, precipitates copolymer, sediment second
Alcohol is washed to neutrality, and vacuum drying is to get to 5,5- dimethyl, two ring [2,2,1] hept-2-ene", methyl acrylate and carbonic acid Asia second
Enester terpolymer.Calculating reaction yield is 48.8%.
Embodiment 9
In the three-necked flask of dry atmosphere of inert gases, 0.001 is rubbed bis- (cyclopentadiene) magnesium and 0.010 mole of α,
α '-bipyridyl is dissolved in 10 milliliters of hexamethylenes, at 350rpm, 0.012 mole of triisobutyl aluminium is instilled in above-mentioned solution, drop
Constant temperature stirs 50 minutes to get magnesium-aluminum complex catalyst at 60 DEG C of same stirring rate after complete.
By 0.01 mole of two ring of 1- phenyl [2,2,1] hept-2-ene", 0.01 mol propylene acetoacetic ester and 0.01 mole of carbonic acid Asia
Vinyl acetate, which is added to, repeatedly to be vacuumized, in nitrogen charging autoclave, and 20ml hexamethylene is added to dissolve.By (cyclopentadiene) bis- in catalyst magnesium
Amount be calculated as the 0.20% of two ring of 1- phenyl [2,2,1] hept-2-ene", ethyl acrylate and vinylene carbonate three's total weight and take
Above-mentioned magnesium-aluminum complex catalyst is injected in above-mentioned mixture with syringe.It is small that constant temperature reacts 6 under 80 DEG C, 4MPa pressure
When.Product, which is poured into the ethanol solution of the hydrochloric acid containing 5wt%, precipitates copolymer, precipitates washed with EtOH to neutrality, and vacuum is dry
It is dry to get arrive two ring of 1- phenyl [2,2,1] hept-2-ene", ethyl acrylate and vinylene carbonate terpolymer.Calculate reaction
Yield is 74.6%.
Embodiment 10
In the three-necked flask of dry atmosphere of inert gases, 0.001 is rubbed bis- (cyclopentadiene) magnesium and 0.011 mole of α,
α '-bipyridyl is dissolved in 10 milliliters of cyclohexanone, at 450 rpm, 0.008 mole of triisobutyl aluminium is instilled in above-mentioned solution, drop
Constant temperature stirs 60 minutes to get magnesium-aluminum complex catalyst at 50 DEG C of same stirring rate after complete.
By 0.01 mole of two ring of 5- phenyl [2,2,1] hept-2-ene", 0.01 mol propylene acid butyl ester and 0.01 mole of carbonic acid Asia
Vinyl acetate, which is added to, repeatedly to be vacuumized, in nitrogen charging autoclave, and 20ml cyclohexanone is added to dissolve.By (cyclopentadiene) bis- in catalyst magnesium
Amount be calculated as the 0.70% of two ring of 5- phenyl [2,2,1] hept-2-ene", butyl acrylate and vinylene carbonate three's total weight and take
Above-mentioned magnesium-aluminum complex catalyst is injected in above-mentioned mixture with syringe.It is small that constant temperature reacts 4 under 70 DEG C, 1MPa pressure
When.Product, which is poured into the ethanol solution of the hydrochloric acid containing 5wt%, precipitates copolymer, precipitates washed with EtOH to neutrality, and vacuum is dry
It is dry to get arrive two ring of 5- phenyl [2,2,1] hept-2-ene", butyl acrylate and vinylene carbonate terpolymer.Calculate reaction
Yield is 68.1%.
Embodiment 11
In the three-necked flask of dry atmosphere of inert gases, 0.001 is rubbed bis- (cyclopentadiene) magnesium and 0.008 mole of neighbour
Ferrosin is dissolved in 10 milliliters of toluene, and at 360rpm, 0.015 mole of triethyl aluminum is instilled in above-mentioned solution, after dripping off
Constant temperature stirs 60 minutes to get magnesium-aluminum complex catalyst at same 60 DEG C of stirring rate.
By 0.01 mole of two ring of 5- vinyl [2,2,1] hept-2-ene", 0.01 mole methyl esters and 0.01 mole
Vinylene carbonate, which is added to, repeatedly to be vacuumized, in nitrogen charging autoclave, and 20ml toluene is added to dissolve.By (rings penta 2 bis- in catalyst
Alkene) amount of magnesium is calculated as two ring of 5- vinyl [2,2,1] hept-2-ene", methyl methacrylate and vinylene carbonate three's gross weight
The 0.06% of amount takes above-mentioned magnesium-aluminum complex catalyst, is injected in above-mentioned mixture with syringe.At 90 DEG C, 5MPa is pressed constant temperature
It is reacted 5 hours under power.Product, which is poured into the ethanol solution of the hydrochloric acid containing 5wt%, precipitates copolymer, and precipitates washed with EtOH is extremely
Neutrality is dried in vacuo to get two ring of 5- vinyl [2,2,1] hept-2-ene", methyl methacrylate and vinylene carbonate three is arrived
Membered copolymer.Calculating reaction yield is 61.4%.
Embodiment 12
In the three-necked flask of dry atmosphere of inert gases, by 0.001 rub bis- (cyclopentadiene) magnesium and 0.010 mole it is different
Quinoline is dissolved in 10 milliliters of tetrahydrofurans, at 470rpm, 0.014 mole of triethyl aluminum is instilled in above-mentioned solution, after dripping off
Constant temperature stirs 40 minutes to get magnesium-aluminum complex catalyst at 40 DEG C of same stirring rate.
By 0.01 mole of two ring [2,2,1] hept-2-ene" -5- methyl formate, 0.01 mole ethyl ester and 0.01
Mole vinylene carbonate, which is added to, repeatedly to be vacuumized, in nitrogen charging autoclave, and 20ml tetrahydrofuran is added to dissolve.By double in catalyst
The amount of (cyclopentadiene) magnesium is calculated as two rings [2,2,1] hept-2-ene" -5- methyl formate, ethyl methacrylate and vinylene carbonate
The 0.09% of ester three's total weight takes above-mentioned magnesium-aluminum complex catalyst, is injected in above-mentioned mixture with syringe.Constant temperature is 50
DEG C, it is reacted 6 hours under 7MPa pressure.Product, which is poured into the ethanol solution of the hydrochloric acid containing 5wt%, precipitates copolymer, sediment second
Alcohol is washed to neutrality, and vacuum drying is to get to two rings [2,2,1] hept-2-ene" -5- methyl formate, ethyl methacrylate and carbon
Sour vinylene terpolymer.Calculating reaction yield is 72.3%.
Embodiment 13
In the three-necked flask of dry atmosphere of inert gases, 0.015 is rubbed bis- (cyclopentadiene) magnesium and 0.006 mole of quinoline
Quinoline is dissolved in 10 milliliters of petroleum ethers, and at 250rpm, 0.006 mole of triisobutyl aluminium is instilled in above-mentioned solution, after dripping off
Constant temperature stirs 40 minutes to get magnesium-aluminum complex catalyst at same 60 DEG C of stirring rate.
By 0.01 mole of two ring [2,2,1] hept-2-ene" -5- formic acid spy butyl ester, 0.01 mole butyl ester and
0.01 mole of vinylene carbonate, which is added to, repeatedly to be vacuumized, in nitrogen charging autoclave, and 20ml petroleum ether dissolution is added.By in catalyst
It is sub- that the amount of bis- (cyclopentadiene) magnesium is calculated as two rings [2,2,1] hept-2-ene" -5- formic acid spy butyl ester, butyl methacrylate and carbonic acid
The 1.30% of vinyl acetate three's total weight takes above-mentioned magnesium-aluminum complex catalyst, is injected in above-mentioned mixture with syringe.Constant temperature
It is reacted 2 hours under 110 DEG C, 0.8MPa pressure.Product, which is poured into the ethanol solution of the hydrochloric acid containing 5wt%, precipitates copolymer, sinks
Starch ethanol washing is to neutrality, and vacuum drying is to get to two rings [2,2,1] hept-2-ene" -5- formic acid spy butyl ester, metering system
Acid butyl ester and vinylene carbonate terpolymer.Calculating reaction yield is 52.7%.
Embodiment 14
In the three-necked flask of dry atmosphere of inert gases, 0.015 is rubbed bis- (cyclopentadiene) magnesium and 0.015 mole of porphin
Quinoline is dissolved in 10 milliliters of methyl phenyl ethers anisoles, at 280rpm, 0.004 mole of triethyl aluminum is instilled in above-mentioned solution, same after dripping off
Constant temperature stirs 50 minutes to get magnesium-aluminum complex catalyst at 50 DEG C of sample stirring rate.
By 0.01 mole of two ring [2,2,1] hept-2-ene" -5- formic acid spy butyl ester, 0.01 mole spy butyl ester and
0.01 mole of vinylene carbonate, which is added to, repeatedly to be vacuumized, in nitrogen charging autoclave, and 20ml methyl phenyl ethers anisole is added to dissolve.By in catalyst
The amount of bis- (cyclopentadiene) magnesium is calculated as two rings [2,2,1] hept-2-ene" -5- formic acid spy butyl ester, tert-butyl methacrylate and carbonic acid
The 1.10% of vinylene three's total weight takes above-mentioned magnesium-aluminum complex catalyst, is injected in above-mentioned mixture with syringe.It is permanent
Temperature is reacted 5 hours under 40 DEG C, 0.6MPa pressure.Product, which is poured into the ethanol solution of the hydrochloric acid containing 5wt%, precipitates copolymer, sinks
Starch ethanol washing is to neutrality, and vacuum drying is to get to two rings [2,2,1] hept-2-ene" -5- formic acid spy butyl ester, metering system
Sour spy's butyl ester and vinylene carbonate terpolymer.Calculating reaction yield is 44.4%.
Embodiment 15
In the three-necked flask of dry atmosphere of inert gases, 0.001 is rubbed bis- (cyclopentadiene) magnesium and 0.007 mole of α,
α '-bipyridyl is dissolved in 10 milliliters of hexamethylenes, at 380rpm, 0.008 mole of triisobutyl aluminium is instilled in above-mentioned solution, drop
Constant temperature stirs 60 minutes to get magnesium-aluminum complex catalyst at 50 DEG C of same stirring rate after complete.
By 0.01 mole of two ring [2,2,1] hept-2-ene", 0.01 mole spy butyl ester and 0.01 mole of carbonic acid Asia
Vinyl acetate, which is added to, repeatedly to be vacuumized, in nitrogen charging autoclave, and 20ml hexamethylene is added to dissolve.By (cyclopentadiene) bis- in catalyst magnesium
Amount be calculated as the 0.10% of two rings [2,2,1] hept-2-ene", tert-butyl methacrylate and vinylene carbonate three's total weight and take
Above-mentioned magnesium-aluminum complex catalyst is injected in above-mentioned mixture with syringe.It is small that constant temperature reacts 6 under 70 DEG C, 7MPa pressure
When.Product, which is poured into the ethanol solution of the hydrochloric acid containing 5wt%, precipitates copolymer, precipitates washed with EtOH to neutrality, and vacuum is dry
It is dry to get to two rings [2,2,1] hept-2-ene", tert-butyl methacrylate and vinylene carbonate terpolymer.Calculate reaction
Yield is 76.9%.
Embodiment 16
In the three-necked flask of dry atmosphere of inert gases, 0.001 is rubbed bis- (cyclopentadiene) magnesium and 0.001 mole of 8-
Oxyquinoline is dissolved in 10 milliliters of benzene, at 440rpm, 0.015 mole of triisobutyl aluminium is instilled in above-mentioned solution, after dripping off
Constant temperature stirs 40 minutes to get magnesium-aluminum complex catalyst at 50 DEG C of same stirring rate.
By 0.01 mole of 1- methyl bicyclic [2,2,1] hept-2-ene", 0.01 mole methyl esters and 0.01 mole of carbon
Sour vinylene, which is added to, repeatedly to be vacuumized, in nitrogen charging autoclave, and 20ml benzene is added to dissolve.By (cyclopentadiene) bis- in catalyst magnesium
Amount be calculated as 1- methyl bicyclic [2,2,1] hept-2-ene", methyl methacrylate and vinylene carbonate three's total weight
0.80% takes above-mentioned magnesium-aluminum complex catalyst, is injected in above-mentioned mixture with syringe.Constant temperature is under 100 DEG C, 5MPa pressure
Reaction 4 hours.Product, which is poured into the ethanol solution of the hydrochloric acid containing 5wt%, precipitates copolymer, precipitates washed with EtOH to neutrality,
It is dried in vacuo to get 1- methyl bicyclic [2,2,1] hept-2-ene", methyl methacrylate and vinylene carbonate ternary polymerization is arrived
Object.Calculating reaction yield is 51.2%.