Norborneol alkenes, hexafluoropropene and vinylene carbonate ternary polymerization catalyst and
Method for ternary polymerization
Technical field
The present invention relates to high polymer field, a kind of norborneol alkenes, hexafluoropropene and vinylene carbonate three are referred specifically to
First catalyst for copolymerization and method for ternary polymerization.
Background technology
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 is that fragility, viscosity difference and molecular weight are low
Deng.The smaller composition of the development need of microelectronics industry, to suitable for exposure skill that line width is 1.3 μm and following line width
Art, may be selected 193nm photoetching techniques, and these technologies are related to the various aspects of photoetching process, it is proposed that new optical material and its
Manufacture and coating technique, new resist, the new material etc. for mask and its protective film await the problem for solving.Cause
This, for the photoetching new material for obtaining, has developed alternating copolymerization material, main development ENB and tetrafluoroethene or other
Component ternary polymerization material, while using the ENB for having side base, it is therefore an objective to improve the resistance to corrosion of whole matrix, improves light
Performance is carved, increases the caking property of material, soluble and toughness.
The method for synthesizing these materials at present mainly has the methods such as free radical, living radical, metallic catalyst.Such as
The synthesis of photoetching material disclosed in Proceedings of SPIE Vol.5039 (2003) pages 80~92 employs peroxidating
Thing as radical polymerization catalyst, disclosed in Proceedings of SPIE Vol.4690 (2002) pages 127~135
The synthesis of photoetching material employs catalyst of the AINB (azodiisobutyronitrile) as radical polymerization.A.E.Feiring and
M.Toriumi etc. is by ENB, tetrafluoroethene and free radical acrylate ternary polymerization etc..These the synthesis sides for applying at present
Method exist the reaction time it is long, obtain copolymer yield it is low, molecular weight of copolymer is small, the low shortcoming of copolymer alternate degree.
The content of the invention
The technical problems to be solved by the invention be directed to prior art present situation provide one kind can reduce reaction temperature,
Improve norborneol alkenes, hexafluoropropene and the vinylene carbonate ternary polymerization catalyst of catalytic efficiency and copolymer yield.
Another technical problem to be solved by this invention is to provide a kind of relatively low reaction temperature, high catalytic efficiency and copolymerization
The method of the norborneol alkenes, hexafluoropropene and vinylene carbonate ternary polymerization of thing high income.
The present invention solve the technical scheme that is used of above-mentioned technical problem for:Norborneol alkenes, hexafluoropropene and the carbonic acid
Vinylene ternary polymerization catalyst, it is characterised in that the preparation method of the catalyst is as follows:
In the there-necked flask of dry atmosphere of inert gases, anhydrous cerium chloride and part are dissolved in the first solvent,
Under 250~400rpm, alkyl aluminum is instilled, constant temperature stirs 40-70 minutes under same stir speed (S.S.) at 40-70 DEG C after dripping off, i.e.,
Obtain cerium-aluminum complex catalyst;
The mol ratio of the anhydrous cerium chloride and the part is 1: 20~20: 1, the anhydrous cerium chloride and the alkyl
The mol ratio of aluminium is 1: 20~20: 1;
The part is selected from 8-hydroxyquinoline, α, α '-bipyridyl, Phen, isoquinolin, quinoline, porphyrin or acetyl group
Acetone;
First solvent is selected from benzene, toluene, tetrahydrofuran, petroleum ether, methyl phenyl ethers anisole, 1,4- dioxane, 1,2- dichloros
Ethane, hexamethylene or cyclohexanone;
The alkyl aluminum is selected from triisobutyl aluminium or triethyl aluminum;
The ratio of the consumption of the solvent and the anhydrous cerium chloride, alkyl aluminum and part three's total amount is 10 milliliters:
0.010~0.040 mole.
It is preferred that the mol ratio of the anhydrous cerium chloride, alkyl aluminum and part three is preferably 1:12:12.
The part and first solvent are first dried using preceding;Solid-state part in wherein described part it is dry
Dry is first to be purified with recrystallization method and then vacuum drying;The drying of the liquid part in the part is with calcium hydride or metal
Sodium is dried, and the solvent is dried using calcium chloride or calcium hydride.
Using above-mentioned norborneol alkenes, the norborneol alkenes of hexafluoropropene and vinylene carbonate ternary polymerization catalyst,
Hexafluoropropene and vinylene carbonate method for ternary polymerization, it is characterised in that comprise the steps:
Norborneol alkenes, hexafluoropropene and vinylene carbonate ester monomer are taken according to mol ratio 1: 1: 1 be added to multiple taking out very
In empty, nitrogen charging reactor, the dissolving of the second solvent is added;Described cerium-aluminum complex catalyst is subsequently adding, at 30~120 DEG C
Under, reacted 1~6 hour under 0.1-6MPa pressure;
The product for obtaining will be reacted to pour into the ethanol solution containing 4.5-5.5wt% hydrochloric acid, the sediment ethanol for obtaining
Washing obtains ENB class, hexafluoropropene and vinylene carbonate terpolymer to neutrality after vacuum drying;
The consumption of the cerium-aluminum complex catalyst is calculated as norborneol alkenes, six by the amount of anhydrous cerium chloride in catalyst
The 0.01%-1.5% of fluoropropene and vinylene carbonate three's gross weight;
Second solvent is selected from benzene, toluene, tetrahydrofuran, petroleum ether, methyl phenyl ethers anisole, 1,4- dioxane, 1,2- dichloros
Ethane, hexamethylene or cyclohexanone;The molal quantity sum of each polymerized monomer is 0.03 mole with the amount ratio of second solvent:20
Milliliter.
The Norbornene derivative can be selected from two rings [2,2,1] hept-2-ene", 1- methyl bicyclics [2,2,1] hept- 2-
Alkene, 5- methyl bicyclics [2,2,1] hept-2-ene", 7- methyl bicyclics [2,2,1] hept-2-ene", 1- ethyls two ring [2,2,1] hept- 2-
Alkene, 5- ethyls two ring [2,2,1] hept-2-ene", 5,5- dimethyl two ring [2,2,1] hept-2-ene", 1- phenyl two ring [2,2,1] hept-
2- alkene, 5- phenyl two ring [2,2,1] hept-2-ene", 5- vinyl two ring [2,2,1] hept-2-ene", two rings [2,2,1] hept-2-ene"-
5- methyl formates or two rings [2,2,1] hept-2-ene" -5- formic acid spy's butyl ester.
Compared with prior art, the catalyst that the present invention is provided is a kind of new cerium-aluminum complex catalyst mixture, is urged
Agent raw material is cheap and easy to get, and catalysis activity, catalysis norborneol alkenes, hexafluoropropene and vinylene carbonate can be produced under compared with low temperature
Ester ternary polymerization, reaction temperature is relatively low, high catalytic efficiency, and product is easy to washing and separates, and copolymer yield is high;Prepared
The resistance to corrosion of norborneol alkenes, hexafluoropropene and vinylene carbonate terpolymer matrix is high, and lithography performance is good, and material
The caking property of material, soluble and toughness are high.
Specific embodiment
The present invention is described in further detail with reference to embodiments.
The preparation process of catalyst in following embodiment, unless otherwise instructed, is carried out to part therein and solvent
Dried process.Specifically:The drying of the solid ligand in part is first to be purified with recrystallization method and then vacuum drying;
The drying of the liquid part in part is to be dried with calcium hydride or dried with metallic sodium.The drying of solvent is with calcium chloride or hydrogen
Change calcium to dry.
Embodiment 1
In the there-necked flask of dry atmosphere of inert gases, by 0.001 mole of anhydrous cerium chloride and 0.004 mole of 8- hydroxyl
Base quinoline is dissolved in 10 milliliters of benzene, under 250rpm, during 0.012 mole of triisobutyl aluminium instilled into above-mentioned solution, after dripping off
Constant temperature is stirred 40 minutes at same 40 DEG C of stir speed (S.S.), obtains final product cerium-aluminum complex catalyst.
0.01 mole of two ring [2,2,1] hept-2-ene", 0.01 mole of hexafluoropropene and 0.01 mole of vinylene carbonate are added
Enter to repeatedly vacuumizing, in nitrogen charging autoclave, plus 20ml benzene dissolving.By the amount of anhydrous cerium chloride in catalyst be calculated as two rings [2,
2,1] the 0.01% of hept-2-ene", hexafluoropropene and vinylene carbonate three's gross weight takes above-mentioned cerium-aluminum complex catalyst,
Injected in above-mentioned mixture with syringe.Constant temperature reacts 6 hours at 80 DEG C under 4MPa pressure.Product is poured into containing 5wt% hydrochloric acid
Precipitate copolymer in ethanol solution, precipitates washed with EtOH to neutrality, vacuum drying obtains two rings [2,2,1] hept- 2-
Alkene, hexafluoropropene and vinylene carbonate terpolymer.It is 41.2% to calculate reaction yield.
The computational methods of reaction yield are terpolymer weight/comonomer gross weight × 100%.Following each embodiments
In yield computational methods it is identical with this.
Embodiment 2
In the there-necked flask of dry atmosphere of inert gases, by 0.001 mole of anhydrous cerium chloride and 0.006 mole of α,
α '-bipyridyl is dissolved in 10 milliliters of toluene, at 300 rpm, by 0.020 mole of triisobutyl aluminium above-mentioned solution of instillation, is dripped off
Constant temperature is stirred 50 minutes at 50 DEG C of same stir speed (S.S.) afterwards, obtains final product cerium-aluminum complex catalyst.
0.01 mole of two ring [2,2,1] hept-2-ene", 0.01 mole of hexafluoropropene and 0.01 mole of vinylene carbonate are added
Enter to repeatedly vacuumizing, in nitrogen charging autoclave, plus 20ml toluene dissolving.Two rings are calculated as by the amount of anhydrous cerium chloride in catalyst
The 0.05% of [2,2,1] hept-2-ene", hexafluoropropene and vinylene carbonate three's gross weight takes above-mentioned cerium-aluminium complex catalysis
Agent, is injected in above-mentioned mixture with syringe.Constant temperature reacts 6 hours at 120 DEG C under 6MPa pressure.Product is poured into salt containing 5wt%
Copolymer is precipitated in the ethanol solution of acid, precipitates washed with EtOH to neutrality, vacuum drying obtains two rings [2,2,1]
Hept-2-ene", hexafluoropropene and vinylene carbonate terpolymer.It is 56.5% to calculate reaction yield.
Embodiment 3
In the there-necked flask of dry atmosphere of inert gases, by 0.001 mole of anhydrous cerium chloride and 0.010 mole of neighbour two
Nitrogen phenanthrene is dissolved in 10 milliliters of tetrahydrofurans, under 400rpm, during 0.014 mole of triethyl aluminum instilled into above-mentioned solution, after dripping off
Constant temperature is stirred 50 minutes at 60 DEG C of same stir speed (S.S.), obtains final product cerium-aluminum complex catalyst.
By 0.01 mole of 1- methyl bicyclics [2,2,1] hept-2-ene", 0.01 mole of hexafluoropropene and 0.01 mole of carbonic acid Asia second
Alkene ester be added to repeatedly vacuumize, in nitrogen charging autoclave, plus 20ml tetrahydrofurans dissolving.By the amount of anhydrous cerium chloride in catalyst
Be calculated as the 0.10% of 1- methyl bicyclics [2,2,1] hept-2-ene", hexafluoropropene and vinylene carbonate three's gross weight take it is above-mentioned
Cerium-aluminum complex catalyst, is injected in above-mentioned mixture with syringe.Constant temperature reacts 4 hours at 110 DEG C under 6MPa pressure.Produce
Thing is poured into the ethanol solution containing 5wt% hydrochloric acid precipitates copolymer, precipitates washed with EtOH to neutrality, vacuum drying, i.e.,
Obtain 1- methyl bicyclics [2,2,1] hept-2-ene", hexafluoropropene and vinylene carbonate terpolymer.Calculating reaction yield is
83.8%.
Embodiment 4
In the there-necked flask of dry atmosphere of inert gases, by 0.001 mole of anhydrous cerium chloride and 0.012 mole of quinoline
It is dissolved in 10 milliliters of petroleum ethers, under 350rpm, during 0.012 mole of triethyl aluminum instilled into above-mentioned solution, same after dripping off
Constant temperature is stirred 60 minutes at 50 DEG C of stir speed (S.S.), obtains final product cerium-aluminum complex catalyst.
By 0.01 mole of 5- methyl bicyclics [2,2,1] hept-2-ene", 0.01 mole of hexafluoropropene and 0.01 mole of carbonic acid Asia second
Alkene ester be added to repeatedly vacuumize, in nitrogen charging autoclave, plus 20ml petroleum ether dissolutions.By the gauge of anhydrous cerium chloride in catalyst
For the 0.09% of 5- methyl bicyclics [2,2,1] hept-2-ene", hexafluoropropene and vinylene carbonate three's gross weight take above-mentioned cerium-
Aluminum complex catalyst, is injected in above-mentioned mixture with syringe.Constant temperature reacts 5 hours at 120 DEG C under 5MPa pressure.Product
Being poured into the ethanol solution containing 5wt% hydrochloric acid precipitates copolymer, precipitates washed with EtOH to neutrality, vacuum drying, obtains final product
To 5- methyl bicyclics [2,2,1] hept-2-ene", hexafluoropropene and vinylene carbonate terpolymer.Calculating reaction yield is
89.4%.
Embodiment 5
In the there-necked flask of dry atmosphere of inert gases, by 0.001 mole of anhydrous cerium chloride and 0.008 mole of porphyrin
It is dissolved in 10 milliliters of methyl phenyl ethers anisoles, under 340rpm, during 0.006 mole of triisobutyl aluminium instilled into above-mentioned solution, same after dripping off
Constant temperature is stirred 40 minutes at 70 DEG C of sample stir speed (S.S.), obtains final product cerium-aluminum complex catalyst.
By 0.01 mole of 7- methyl bicyclics [2,2,1] hept-2-ene", 0.01 mole of hexafluoropropene and 0.01 mole of carbonic acid Asia second
Alkene ester be added to repeatedly vacuumize, in nitrogen charging autoclave, plus 20ml methyl phenyl ethers anisoles dissolving.By the gauge of anhydrous cerium chloride in catalyst
For the 1.00% of 7- methyl bicyclics [2,2,1] hept-2-ene", hexafluoropropene and vinylene carbonate three's gross weight take above-mentioned cerium-
Aluminum complex catalyst, is injected in above-mentioned mixture with syringe.Constant temperature reacts 1 hour at 90 DEG C under 4MPa pressure.Product inclines
Entering precipitate copolymer in the ethanol solution containing 5wt% hydrochloric acid, precipitates washed with EtOH to neutrality, vacuum drying, that is, obtain
7- methyl bicyclics [2,2,1] hept-2-ene", hexafluoropropene and vinylene carbonate terpolymer.Calculating reaction yield is
57.7%.
Embodiment 6
In the there-necked flask of dry atmosphere of inert gases, by 0.020 mole of anhydrous cerium chloride and 0.001 mole of acetyl
Benzylacetone is dissolved in 10 milliliters of Isosorbide-5-Nitrae-dioxane, under 260rpm, during 0.016 mole of triethyl aluminum instilled into above-mentioned solution,
Constant temperature is stirred 70 minutes at 50 DEG C of same stir speed (S.S.) after dripping off, and obtains final product cerium-aluminum complex catalyst.
By 0.01 mole of 1- ethyls two ring [2,2,1] hept-2-ene", 0.01 mole of hexafluoropropene and 0.01 mole of carbonic acid Asia second
Alkene ester be added to repeatedly vacuumize, in nitrogen charging autoclave, plus 20ml Isosorbide-5-Nitraes-dioxane dissolving.By anhydrous chlorination in catalyst
What the amount of cerium was calculated as 1- ethyls two ring [2,2,1] hept-2-ene", hexafluoropropene and vinylene carbonate three's gross weight 0.06% takes
Above-mentioned cerium-aluminum complex catalyst, is injected in above-mentioned mixture with syringe.It is small that constant temperature reacts 3 at 30 DEG C, under 2MPa pressure
When.Product is poured into the ethanol solution containing 5wt% hydrochloric acid precipitates copolymer, precipitates washed with EtOH to neutrality, and vacuum is done
It is dry, that is, obtain 1- ethyls two ring [2,2,1] hept-2-ene", hexafluoropropene and vinylene carbonate terpolymer.Reaction is calculated to receive
Rate is 43.3%.
Embodiment 7
In the there-necked flask of dry atmosphere of inert gases, by 0.020 mole of anhydrous cerium chloride and 0.016 mole of 8- hydroxyl
Base quinoline is dissolved in 10 milliliters of Isosorbide-5-Nitrae-dioxane, under 400rpm, during 0.001 mole of triethyl aluminum instilled into above-mentioned solution,
Constant temperature is stirred 40 minutes at 40 DEG C of same stir speed (S.S.) after dripping off, and obtains final product cerium-aluminum complex catalyst.
By 0.01 mole of 5- ethyls two ring [2,2,1] hept-2-ene", 0.01 mole of hexafluoropropene and 0.01 mole of carbonic acid Asia second
Alkene ester be added to repeatedly vacuumize, in nitrogen charging autoclave, plus 20ml Isosorbide-5-Nitraes-dioxane dissolving.By anhydrous chlorination in catalyst
What the amount of cerium was calculated as 5- ethyls two ring [2,2,1] hept-2-ene", hexafluoropropene and vinylene carbonate three's gross weight 1.50% takes
Above-mentioned cerium-aluminum complex catalyst, is injected in above-mentioned mixture with syringe.Constant temperature reacts 4 at 110 DEG C under 0.1MPa pressure
Hour.Product is poured into the ethanol solution containing 5wt% hydrochloric acid precipitates copolymer, precipitates washed with EtOH to neutrality, vacuum
Dry, that is, obtain 5- ethyls two ring [2,2,1] hept-2-ene", hexafluoropropene and vinylene carbonate terpolymer.Calculate reaction
Yield is 40.3%.
Embodiment 8
In the there-necked flask of dry atmosphere of inert gases, by 0.006 mole of anhydrous cerium chloride and 0.010 mole of isoquinoline
Quinoline is dissolved in 10 milliliters of 1,2- dichloroethanes, under 280rpm, by 0.003 mole of triethyl aluminum above-mentioned solution of instillation, is dripped off
Constant temperature is stirred 60 minutes at 40 DEG C of same stir speed (S.S.) afterwards, obtains final product cerium-aluminum complex catalyst.
By 0.01 mole of 5,5- dimethyl two ring [2,2,1] hept-2-ene", 0.01 mole of hexafluoropropene and 0.01 mole of carbonic acid
Vinylene be added to repeatedly vacuumize, in nitrogen charging autoclave, plus 20ml1,2- dichloroethanes dissolving.By anhydrous chlorine in catalyst
The amount for changing cerium is calculated as 5,5- dimethyl two ring [2,2,1] hept-2-ene", hexafluoropropene and vinylene carbonate three's gross weight
0.30% takes above-mentioned cerium-aluminum complex catalyst, is injected in above-mentioned mixture with syringe.Constant temperature is in 50 DEG C, 0.8MPa pressure
Lower reaction 4 hours.Product is poured into the ethanol solution containing 5wt% hydrochloric acid precipitates copolymer, and precipitates washed with EtOH is into
Property, vacuum drying obtains 5,5- dimethyl two ring [2,2,1] hept-2-ene", hexafluoropropene and vinylene carbonate ternary polymerization
Thing.It is 46.5% to calculate reaction yield.
Embodiment 9
In the there-necked flask of dry atmosphere of inert gases, by 0.001 mole of anhydrous cerium chloride and 0.012 mole of α,
α '-bipyridyl is dissolved in 10 milliliters of hexamethylenes, under 330rpm, by 0.016 mole of triisobutyl aluminium above-mentioned solution of instillation, is dripped
Constant temperature is stirred 50 minutes at 60 DEG C of same stir speed (S.S.) after complete, obtains final product cerium-aluminum complex catalyst.
By 0.01 mole of 1- phenyl two ring [2,2,1] hept-2-ene", 0.01 mole of hexafluoropropene and 0.01 mole of carbonic acid Asia second
Alkene ester be added to repeatedly vacuumize, in nitrogen charging autoclave, plus 20ml hexamethylenes dissolving.By the gauge of anhydrous cerium chloride in catalyst
For the 0.20% of 1- phenyl two ring [2,2,1] hept-2-ene", hexafluoropropene and vinylene carbonate three's gross weight take above-mentioned cerium-
Aluminum complex catalyst, is injected in above-mentioned mixture with syringe.Constant temperature reacts 6 hours at 90 DEG C under 3.5MPa pressure.Product
Being poured into the ethanol solution containing 5wt% hydrochloric acid precipitates copolymer, precipitates washed with EtOH to neutrality, vacuum drying, obtains final product
To 1- phenyl two ring [2,2,1] hept-2-ene", hexafluoropropene and vinylene carbonate terpolymer.Calculating reaction yield is
78.7%.
Embodiment 10
In the there-necked flask of dry atmosphere of inert gases, by 0.001 mole of anhydrous cerium chloride and 0.011 mole of α,
α '-bipyridyl is dissolved in 10 milliliters of cyclohexanone, under 320rpm, by 0.015 mole of triisobutyl aluminium above-mentioned solution of instillation, is dripped
Constant temperature is stirred 60 minutes at 50 DEG C of same stir speed (S.S.) after complete, obtains final product cerium-aluminum complex catalyst.
By 0.01 mole of 5- phenyl two ring [2,2,1] hept-2-ene", 0.01 mole of hexafluoropropene and 0.01 mole of carbonic acid Asia second
Alkene ester be added to repeatedly vacuumize, in nitrogen charging autoclave, plus 20ml cyclohexanone dissolving.By the gauge of anhydrous cerium chloride in catalyst
For the 0.70% of 5- phenyl two ring [2,2,1] hept-2-ene", hexafluoropropene and vinylene carbonate three's gross weight take above-mentioned cerium-
Aluminum complex catalyst, is injected in above-mentioned mixture with syringe.Constant temperature reacts 5 hours at 50 DEG C under 1MPa pressure.Product inclines
Entering precipitate copolymer in the ethanol solution containing 5wt% hydrochloric acid, precipitates washed with EtOH to neutrality, vacuum drying, that is, obtain
5- phenyl two ring [2,2,1] hept-2-ene", hexafluoropropene and vinylene carbonate terpolymer.Calculating reaction yield is
69.8%.
Embodiment 11
In the there-necked flask of dry atmosphere of inert gases, by 0.001 mole of anhydrous cerium chloride and 0.008 mole of neighbour two
Nitrogen phenanthrene is dissolved in 10 milliliters of toluene, under 360rpm, during 0.016 mole of triethyl aluminum instilled into above-mentioned solution, same after dripping off
Constant temperature is stirred 70 minutes at 70 DEG C of sample stir speed (S.S.), obtains final product cerium-aluminum complex catalyst.
By 0.01 mole of 5- vinyl two ring [2,2,1] hept-2-ene", 0.01 mole of hexafluoropropene and 0.01 mole of carbonic acid Asia
Vinyl acetate be added to repeatedly vacuumize, in nitrogen charging autoclave, plus 20ml toluene dissolving.By the gauge of anhydrous cerium chloride in catalyst
For the 0.06% of 5- vinyl two ring [2,2,1] hept-2-ene", hexafluoropropene and vinylene carbonate three's gross weight take it is above-mentioned
Cerium-aluminum complex catalyst, is injected in above-mentioned mixture with syringe.Constant temperature reacts 4 hours at 90 DEG C under 5MPa pressure.Produce
Thing is poured into the ethanol solution containing 5wt% hydrochloric acid precipitates copolymer, precipitates washed with EtOH to neutrality, vacuum drying, i.e.,
Obtain 5- vinyl two ring [2,2,1] hept-2-ene", hexafluoropropene and vinylene carbonate terpolymer.Calculate reaction yield
It is 67.4%.
Embodiment 12
In the there-necked flask of dry atmosphere of inert gases, by 0.001 mole of anhydrous cerium chloride and 0.010 mole of isoquinoline
Quinoline is dissolved in 10 milliliters of tetrahydrofurans, under 370rpm, during 0.017 mole of triethyl aluminum instilled into above-mentioned solution, after dripping off
Constant temperature is stirred 40 minutes at same 40 DEG C of stir speed (S.S.), obtains final product cerium-aluminum complex catalyst.
By 0.01 mole of two ring [2,2,1] hept-2-ene" -5- methyl formates, 0.01 mole of hexafluoropropene and 0.01 mole of carbon
Sour vinylene be added to repeatedly vacuumize, in nitrogen charging autoclave, plus 20ml tetrahydrofurans dissolving.By anhydrous chlorination in catalyst
The amount of cerium is calculated as two rings [2,2,1] hept-2-ene" -5- methyl formates, hexafluoropropene and vinylene carbonate three's gross weight
0.08% takes above-mentioned cerium-aluminum complex catalyst, is injected in above-mentioned mixture with syringe.Constant temperature at 90 DEG C, under 4MPa pressure
Reaction 6 hours.Product is poured into the ethanol solution containing 5wt% hydrochloric acid precipitates copolymer, precipitates washed with EtOH to neutrality,
Vacuum drying, that is, obtain two rings [2,2,1] hept-2-ene" -5- methyl formates, hexafluoropropene and vinylene carbonate ternary polymerization
Thing.It is 71.3% to calculate reaction yield.
Embodiment 13
In the there-necked flask of dry atmosphere of inert gases, by 0.015 mole of anhydrous cerium chloride and 0.006 mole of quinoline
It is dissolved in 10 milliliters of petroleum ethers, under 250rpm, during 0.005 mole of triisobutyl aluminium instilled into above-mentioned solution, same after dripping off
Constant temperature is stirred 50 minutes at 50 DEG C of sample stir speed (S.S.), obtains final product cerium-aluminum complex catalyst.
By 0.01 mole of two ring [2,2,1] hept-2-ene" -5- formic acid spy butyl ester, 0.01 mole of hexafluoropropene and 0.01 mole
Vinylene carbonate be added to repeatedly vacuumize, in nitrogen charging autoclave, plus 20ml petroleum ether dissolutions.By anhydrous chlorination in catalyst
The amount of cerium is calculated as two rings [2,2,1] hept-2-ene" -5- formic acid spy butyl ester, hexafluoropropene and vinylene carbonate three's gross weight
1.30% takes above-mentioned cerium-aluminum complex catalyst, is injected in above-mentioned mixture with syringe.Constant temperature at 120 DEG C, under 6MPa pressure
Reaction 2 hours.Product is poured into the ethanol solution containing 5wt% hydrochloric acid precipitates copolymer, precipitates washed with EtOH to neutrality,
Vacuum drying, that is, obtain two rings [2,2,1] hept-2-ene" -5- formic acid spy butyl ester, hexafluoropropene and vinylene carbonate ternary polymerization
Thing.It is 55.7% to calculate reaction yield.
Embodiment 14
In the there-necked flask of dry atmosphere of inert gases, by 0.016 mole of anhydrous cerium chloride and 0.016 mole of porphyrin
It is dissolved in 10 milliliters of methyl phenyl ethers anisoles, under 290rpm, during 0.003 mole of triethyl aluminum instilled into above-mentioned solution, same after dripping off
Constant temperature is stirred 50 minutes at 40 DEG C of stir speed (S.S.), obtains final product cerium-aluminum complex catalyst.
By 0.01 mole of two ring [2,2,1] hept-2-ene" -5- formic acid spy butyl ester, 0.01 mole of hexafluoropropene and 0.01 mole
Vinylene carbonate be added to repeatedly vacuumize, in nitrogen charging autoclave, plus 20ml methyl phenyl ethers anisoles dissolving.By anhydrous chlorination in catalyst
The amount of cerium is calculated as two rings [2,2,1] hept-2-ene" -5- formic acid spy butyl ester, hexafluoropropene and vinylene carbonate three's gross weight
0.07% takes above-mentioned cerium-aluminum complex catalyst, is injected in above-mentioned mixture with syringe.Constant temperature at 40 DEG C, under 6MPa pressure
Reaction 5 hours.Product is poured into the ethanol solution containing 5wt% hydrochloric acid precipitates copolymer, precipitates washed with EtOH to neutrality,
Vacuum drying, that is, obtain two rings [2,2,1] hept-2-ene" -5- formic acid spy butyl ester, hexafluoropropene and vinylene carbonate ternary polymerization
Thing.It is 43.7% to calculate reaction yield.
Embodiment 15
In the there-necked flask of dry atmosphere of inert gases, by 0.001 mole of anhydrous cerium chloride and 0.006 mole of α,
α '-bipyridyl is dissolved in 10 milliliters of hexamethylenes, under 280rpm, by 0.007 mole of triisobutyl aluminium above-mentioned solution of instillation, is dripped
Constant temperature is stirred 60 minutes at 40 DEG C of same stir speed (S.S.) after complete, obtains final product cerium-aluminum complex catalyst.
0.01 mole of two ring [2,2,1] hept-2-ene", 0.01 mole of hexafluoropropene and 0.01 mole of vinylene carbonate are added
Enter to repeatedly vacuumizing, in nitrogen charging autoclave, plus 20ml hexamethylenes dissolving.Two rings are calculated as by the amount of anhydrous cerium chloride in catalyst
The 0.20% of [2,2,1] hept-2-ene", hexafluoropropene and vinylene carbonate three's gross weight takes above-mentioned cerium-aluminium complex catalysis
Agent, is injected in above-mentioned mixture with syringe.Constant temperature reacts 5 hours at 70 DEG C under 6MPa pressure.Product is poured into salt containing 5wt%
Copolymer is precipitated in the ethanol solution of acid, precipitates washed with EtOH to neutrality, vacuum drying obtains two rings [2,2,1]
Hept-2-ene", hexafluoropropene and vinylene carbonate terpolymer.It is 56.9% to calculate reaction yield.
Embodiment 16
In the there-necked flask of dry atmosphere of inert gases, by 0.001 mole of anhydrous cerium chloride and 0.001 mole of 8- hydroxyl
Base quinoline is dissolved in 10 milliliters of benzene, under 350rpm, during 0.020 mole of triisobutyl aluminium instilled into above-mentioned solution, after dripping off
Constant temperature is stirred 40 minutes at same 50 DEG C of stir speed (S.S.), obtains final product cerium-aluminum complex catalyst.
By 0.01 mole of 1- methyl bicyclics [2,2,1] hept-2-ene", 0.01 mole of hexafluoropropene and 0.01 mole of carbonic acid Asia second
Alkene ester be added to repeatedly vacuumize, in nitrogen charging autoclave, plus 20ml benzene dissolving.1- is calculated as by the amount of anhydrous cerium chloride in catalyst
The 0.80% of methyl bicyclic [2,2,1] hept-2-ene", hexafluoropropene and vinylene carbonate three's gross weight takes above-mentioned cerium-aluminium network
Mixture catalyst, is injected in above-mentioned mixture with syringe.Constant temperature reacts 4 hours at 120 DEG C under 5MPa pressure.Product is poured into
Copolymer is precipitated in ethanol solution containing 5wt% hydrochloric acid, precipitates washed with EtOH to neutrality, vacuum drying obtains 1-
Methyl bicyclic [2,2,1] hept-2-ene", hexafluoropropene and vinylene carbonate terpolymer.It is 57.6% to calculate reaction yield.
Embodiment 17
In the there-necked flask of dry atmosphere of inert gases, by 0.001 mole of anhydrous cerium chloride and 0.020 mole of α,
α '-bipyridyl is dissolved in 10 milliliters of benzene, under 270rpm, during 0.001 mole of triisobutyl aluminium instilled into above-mentioned solution, after dripping off
Constant temperature is stirred 50 minutes at 50 DEG C of same stir speed (S.S.), obtains final product cerium-aluminum complex catalyst.
By 0.01 mole of 1- methyl bicyclics [2,2,1] hept-2-ene", 0.01 mole of hexafluoropropene and 0.01 mole of carbonic acid Asia second
Alkene ester be added to repeatedly vacuumize, in nitrogen charging autoclave, plus 20ml benzene dissolving.1- is calculated as by the amount of anhydrous cerium chloride in catalyst
The 0.60% of methyl bicyclic [2,2,1] hept-2-ene", hexafluoropropene and vinylene carbonate three's gross weight takes above-mentioned cerium-aluminium network
Mixture catalyst, is injected in above-mentioned mixture with syringe.Constant temperature reacts 3 hours at 100 DEG C under 5MPa pressure.Product is poured into
Copolymer is precipitated in ethanol solution containing 5wt% hydrochloric acid, precipitates washed with EtOH to neutrality, vacuum drying obtains 1-
Methyl bicyclic [2,2,1] hept-2-ene", hexafluoropropene and vinylene carbonate terpolymer.It is 44.6% to calculate reaction yield.
Embodiment 18
In the there-necked flask of dry atmosphere of inert gases, by 0.001 mole of anhydrous cerium chloride and 0.001 mole of porphyrin
It is dissolved in 10 milliliters of methyl phenyl ethers anisoles, under 330rpm, during 0.012 mole of triisobutyl aluminium instilled into above-mentioned solution, same after dripping off
Constant temperature is stirred 50 minutes at 70 DEG C of sample stir speed (S.S.), obtains final product cerium-aluminum complex catalyst.
By 0.01 mole of two ring [2,2,1] hept-2-ene" -5- formic acid spy butyl ester, 0.01 mole of hexafluoropropene and 0.01 mole
Vinylene carbonate be added to repeatedly vacuumize, in nitrogen charging autoclave, plus 20ml methyl phenyl ethers anisoles dissolving.By anhydrous chlorination in catalyst
The amount of cerium is calculated as two rings [2,2,1] hept-2-ene" -5- formic acid spy butyl ester, hexafluoropropene and vinylene carbonate three's gross weight
0.70% takes above-mentioned cerium-aluminum complex catalyst, is injected in above-mentioned mixture with syringe.Constant temperature at 70 DEG C, under 6MPa pressure
Reaction 5 hours.Product is poured into the ethanol solution containing 5wt% hydrochloric acid precipitates copolymer, precipitates washed with EtOH to neutrality,
Vacuum drying, that is, obtain two rings [2,2,1] hept-2-ene" -5- formic acid spy butyl ester, hexafluoropropene and vinylene carbonate ternary polymerization
Thing.It is 45.5% to calculate reaction yield.