CN106832121A - Norborneol alkenes, cyclohexene and vinylene carbonate ternary polymerization catalyst and method for ternary polymerization - Google Patents
Norborneol alkenes, cyclohexene and vinylene carbonate ternary polymerization catalyst and method for ternary polymerization Download PDFInfo
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- CN106832121A CN106832121A CN201710089285.4A CN201710089285A CN106832121A CN 106832121 A CN106832121 A CN 106832121A CN 201710089285 A CN201710089285 A CN 201710089285A CN 106832121 A CN106832121 A CN 106832121A
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Abstract
The present invention relates to norborneol alkenes, cyclohexene and vinylene carbonate 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, three (cyclopentadiene) change gadolinium (III) and part is dissolved in the first solvent, under 300~500rpm, instill tetraisopropoxy titanium, constant temperature is stirred 30 60 minutes under same stir speed (S.S.) at 30 60 DEG C after dripping off, and obtains final product gadolinium titanium complex catalyst；According to mol ratio 1：1：1 takes norborneol alkenes, cyclohexene and vinylene carbonate ester monomer is added to and repeatedly vacuumizes, in nitrogen charging reactor, adds the dissolving of the second solvent；Described gadolinium titanium complex catalyst is subsequently adding, at 30~100 DEG C, is reacted 1~6 hour under 0.1 6MPa pressure；The product for obtaining will be reacted to pour into hydrochloric ethanol solution, the precipitates washed with EtOH for obtaining to neutrality obtains ENB class, cyclohexene and vinylene carbonate terpolymer after vacuum drying.
Description
Technical field
The present invention relates to high polymer field, a kind of norborneol alkenes, cyclohexene and vinylene carbonate ternary are referred specifically to
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.After in oxygenatedchemicals insertion polynorbornene main chain, the caking property and solubility of polymer can be improved, and reduce material
The absorptance of material itself.This copolymer can be applied to 193nm replica technologies as photoresist.And, microelectronics industry
The smaller composition of development need, to suitable for the exposure technique that line width is 1.3 μm and following line width, 193nm light may be selected
Lithography, 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
Type resist, the new material etc. for mask and its protective film await the problem for solving.Therefore, for the photoetching for obtaining
New material, has developed alternating copolymerization material, main development ENB and tetrafluoroethene or other component ternary polymerization materials, together
Shi Yingyong has the ENB of side base, it is therefore an objective to improve the resistance to corrosion of whole matrix, improves lithography performance, increases the viscous of material
Knot property, 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, cyclohexene 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, cyclohexene 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：The norborneol alkenes, cyclohexene and carbonic acid are sub-
Vinyl acetate 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, three (cyclopentadiene) change gadolinium (III) and part is dissolved in first
In solvent, under 300~500rpm, tetraisopropoxy titanium is instilled, constant temperature is stirred under same stir speed (S.S.) at 30-60 DEG C after dripping off
Mix 30-60 minutes, obtain final product gadolinium-titanium complex catalyst；
It is 1 that three (cyclopentadiene) change gadolinium (III) with the mol ratio of the part：16~16：1, the three (ring penta 2
Alkene) change gadolinium (III) and the tetraisopropoxy titanium mol ratio be 1：16~16：1；
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 consumption of the solvent changes gadolinium (III), tetraisopropoxy titanium and part three's total amount with described three (cyclopentadiene)
Ratio is 10 milliliters：0.010~0.040 mole.
The mol ratio that three (cyclopentadiene) change gadolinium (III), tetraisopropoxy titanium and part three is preferably 1：8：10.
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.
Use norborneol alkenes, the ring of above-mentioned norborneol alkenes, cyclohexene and vinylene carbonate ternary polymerization catalyst
Hexene and vinylene carbonate method for ternary polymerization, it is characterised in that comprise the steps：
According to mol ratio 1：1：1 take norborneol alkenes, cyclohexene and vinylene carbonate ester monomer be added to repeatedly vacuumize,
In nitrogen charging reactor, the dissolving of the second solvent is added；Described gadolinium-titanium complex catalyst is subsequently adding, at 20~100 DEG C,
Reacted 1~6 hour under 0.1-6MPa pressure；
The product for obtaining will be reacted to pour into the ethanol solution containing 4-5wt% hydrochloric acid, the precipitates washed with EtOH for obtaining
To neutral, ENB class, cyclohexene and vinylene carbonate terpolymer are obtained after vacuum drying；
The consumption of the gadolinium-titanium complex catalyst is calculated as dropping ice by the amount that in catalyst three (cyclopentadiene) change gadolinium (III)
The 0.01%-1.5% of piece alkenes, cyclohexene 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 gadolinium-titanium complex catalyst mixture, is urged
Agent raw material is cheap and easy to get, and catalysis activity, catalysis norborneol alkenes, cyclohexene and vinylene carbonate can be produced under compared with low temperature
Ternary polymerization, reaction temperature is relatively low, high catalytic efficiency, and product is easy to washing and separates, and copolymer yield is high；Prepared drop
The resistance to corrosion of borneol alkenes, cyclohexene and vinylene carbonate terpolymer matrix is high, and lithography performance is good, and material
Caking property, solubility and toughness are further enhanced.
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, 0.001 three (cyclopentadiene) that rub are changed into gadolinium (III) and 0.006
Mole 8-hydroxyquinoline is dissolved in 10 milliliters of benzene, at 300 rpm, 0.010 mole of tetraisopropoxy titanium is instilled into above-mentioned solution
In, constant temperature is stirred 40 minutes at 60 DEG C of same stir speed (S.S.) after dripping off, and obtains final product gadolinium-titanium complex catalyst.
0.01 mole of two ring [2,2,1] hept-2-ene", 0.01 mole of cyclohexene and 0.01 mole of vinylene carbonate are added
To repeatedly vacuumizing, in nitrogen charging autoclave, plus the dissolving of 20ml benzene.The amount for changing gadolinium (III) by catalyst three (cyclopentadiene) is calculated as
The 0.06% of two rings [2,2,1] hept-2-ene", cyclohexene and vinylene carbonate three's gross weight takes above-mentioned gadolinium-titanium complex and urges
Agent, is injected in above-mentioned mixture with syringe.Constant temperature reacts 6 hours at 90 DEG C under 5MPa pressure.Product is poured into containing 5wt%
Precipitate copolymer in the ethanol solution of hydrochloric acid, precipitates washed with EtOH to neutrality, vacuum drying, that is, obtain two rings [2,2,
1] hept-2-ene", cyclohexene and vinylene carbonate terpolymer.It is 62.2% 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, 0.001 three (cyclopentadiene) that rub are changed into gadolinium (III) and 0.007
Mole α, α '-bipyridyl is dissolved in 10 milliliters of toluene, under 400rpm, 0.016 mole of tetraisopropoxy titanium is instilled above-mentioned molten
In liquid, constant temperature is stirred 50 minutes at 30 DEG C of same stir speed (S.S.) after dripping off, and obtains final product gadolinium-titanium complex catalyst.
0.01 mole of two ring [2,2,1] hept-2-ene", 0.01 mole of cyclohexene and 0.01 mole of vinylene carbonate are added
To repeatedly vacuumizing, in nitrogen charging autoclave, plus the dissolving of 20ml toluene.Change the gauge of gadolinium (III) by catalyst three (cyclopentadiene)
For two rings [2,2,1] hept-2-ene", cyclohexene and vinylene carbonate three's gross weight 0.01% takes above-mentioned gadolinium-titanium complex
Catalyst, is injected in above-mentioned mixture with syringe.Constant temperature reacts 6 hours at 100 DEG C under 6MPa pressure.Product is poured into and contains
Copolymer is precipitated in the ethanol solution of 4wt% hydrochloric acid, precipitates washed with EtOH to neutrality, vacuum drying obtains two rings
[2,2,1] hept-2-ene", cyclohexene and vinylene carbonate terpolymer.It is 55.5% to calculate reaction yield.
Embodiment 3
In the there-necked flask of dry atmosphere of inert gases, 0.001 three (cyclopentadiene) that rub are changed into gadolinium (III) and 0.010
Mole Phen is dissolved in 10 milliliters of tetrahydrofurans, at 450 rpm, 0.008 mole of tetraisopropoxy titanium is instilled above-mentioned molten
In liquid, constant temperature is stirred 50 minutes at 60 DEG C of same stir speed (S.S.) after dripping off, and obtains final product gadolinium-titanium complex catalyst.
By 0.01 mole of 1- methyl bicyclics [2,2,1] hept-2-ene", 0.01 mole of cyclohexene and 0.01 mole of vinylene carbonate
Ester be added to repeatedly vacuumize, in nitrogen charging autoclave, plus 20ml tetrahydrofurans dissolving.Change gadolinium by catalyst three (cyclopentadiene)
(III) what amount was calculated as 1- methyl bicyclics [2,2,1] hept-2-ene", cyclohexene and vinylene carbonate three's gross weight 0.10% takes
Above-mentioned gadolinium-titanium complex catalyst, is injected in above-mentioned mixture with syringe.It is small that constant temperature reacts 5 at 90 DEG C, under 5MPa 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- methyl bicyclics [2,2,1] hept-2-ene", cyclohexene and vinylene carbonate terpolymer.Calculate reaction yield
It is 90.3%.
Embodiment 4
In the there-necked flask of dry atmosphere of inert gases, 0.001 three (cyclopentadiene) that rub are changed into gadolinium (III) and 0.012
Mole quinoline is dissolved in 10 milliliters of petroleum ethers, under 350rpm, during 0.010 mole of tetraisopropoxy titanium instilled into above-mentioned solution,
Constant temperature is stirred 60 minutes at 50 DEG C of same stir speed (S.S.) after dripping off, and obtains final product gadolinium-titanium complex catalyst.
By 0.01 mole of 5- methyl bicyclics [2,2,1] hept-2-ene", 0.01 mole of cyclohexene and 0.01 mole of vinylene carbonate
Ester be added to repeatedly vacuumize, in nitrogen charging autoclave, plus 20ml petroleum ether dissolutions.Change gadolinium by catalyst three (cyclopentadiene)
(III) what amount was calculated as 5- methyl bicyclics [2,2,1] hept-2-ene", cyclohexene and vinylene carbonate three's gross weight 0.08% takes
Above-mentioned gadolinium-titanium complex catalyst, is injected in above-mentioned mixture with syringe.It is small that constant temperature reacts 6 at 100 DEG C, under 6MPa 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 5- methyl bicyclics [2,2,1] hept-2-ene", cyclohexene and vinylene carbonate terpolymer.Calculate reaction yield
It is 87.7%
Embodiment 5
In the there-necked flask of dry atmosphere of inert gases, 0.001 three (cyclopentadiene) that rub are changed into gadolinium (III) and 0.008
Mole porphyrin is dissolved in 10 milliliters of methyl phenyl ethers anisoles, under 340rpm, during 0.006 mole of tetraisopropoxy titanium instilled into above-mentioned solution,
Constant temperature is stirred 30 minutes at 40 DEG C of same stir speed (S.S.) after dripping off, and obtains final product gadolinium-titanium complex catalyst.
By 0.01 mole of 7- methyl bicyclics [2,2,1] hept-2-ene", 0.01 mole of cyclohexene and 0.01 mole of vinylene carbonate
Ester be added to repeatedly vacuumize, in nitrogen charging autoclave, plus 20ml methyl phenyl ethers anisoles dissolving.Change gadolinium by catalyst three (cyclopentadiene)
(III) what amount was calculated as 7- methyl bicyclics [2,2,1] hept-2-ene", cyclohexene and vinylene carbonate three's gross weight 1.00% takes
Above-mentioned gadolinium-titanium complex catalyst, is injected in above-mentioned mixture with syringe.It is small that constant temperature reacts 1 at 90 DEG C, under 4MPa 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 7- methyl bicyclics [2,2,1] hept-2-ene", cyclohexene and vinylene carbonate terpolymer.Calculate reaction yield
It is 64.4%.
Embodiment 6
In the there-necked flask of dry atmosphere of inert gases, 0.016 three (cyclopentadiene) that rub are changed into gadolinium (III) and 0.001
Mole pentanedione is dissolved in 10 milliliters of Isosorbide-5-Nitrae-dioxane, under 360rpm, 0.016 mole of tetraisopropoxy titanium is instilled
In above-mentioned solution, constant temperature is stirred 50 minutes at 50 DEG C of same stir speed (S.S.) after dripping off, and obtains final product gadolinium-titanium complex catalyst.
By 0.01 mole of 1- ethyls two ring [2,2,1] hept-2-ene", 0.01 mole of cyclohexene and 0.01 mole of vinylene carbonate
Ester be added to repeatedly vacuumize, in nitrogen charging autoclave, plus 20ml1,4- dioxane dissolving.By in catalyst three (cyclopentadiene)
The amount for changing gadolinium (III) is calculated as 1- ethyls two ring [2,2,1] hept-2-ene", cyclohexene and vinylene carbonate three's gross weight
0.08% takes above-mentioned gadolinium-titanium complex catalyst, is injected in above-mentioned mixture with syringe.Constant temperature at 20 DEG C, under 3MPa pressure
Reaction 3 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 1- ethyls two ring [2,2,1] hept-2-ene", cyclohexene and vinylene carbonate terpolymer.Calculate anti-
It is 45.6% to answer yield.
Embodiment 7
In the there-necked flask of dry atmosphere of inert gases, 0.016 three (cyclopentadiene) that rub are changed into gadolinium (III) and 0.016
Mole 8-hydroxyquinoline is dissolved in 10 milliliters of Isosorbide-5-Nitrae-dioxane, under 470rpm, 0.001 mole of tetraisopropoxy titanium is instilled
In above-mentioned solution, constant temperature is stirred 50 minutes at 40 DEG C of same stir speed (S.S.) after dripping off, and obtains final product gadolinium-titanium complex catalyst.
By 0.01 mole of 5- ethyls two ring [2,2,1] hept-2-ene", 0.01 mole of cyclohexene and 0.01 mole of vinylene carbonate
Ester be added to repeatedly vacuumize, in nitrogen charging autoclave, plus 20ml1,4- dioxane dissolving.By in catalyst three (cyclopentadiene)
The amount for changing gadolinium (III) is calculated as 5- ethyls two ring [2,2,1] hept-2-ene", cyclohexene and vinylene carbonate three's gross weight
1.50% takes above-mentioned gadolinium-titanium complex catalyst, is injected in above-mentioned mixture with syringe.Constant temperature is in 100 DEG C, 0.1MPa 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- ethyls two ring [2,2,1] hept-2-ene", cyclohexene and vinylene carbonate terpolymer.Meter
It is 41.9% to calculate reaction yield.
Embodiment 8
In the there-necked flask of dry atmosphere of inert gases, 0.007 three (cyclopentadiene) that rub are changed into gadolinium (III) and 0.010
Mole isoquinolin is dissolved in 10 milliliters of 1,2- dichloroethanes, under 380rpm, 0.003 mole of tetraisopropoxy titanium is instilled above-mentioned
In solution, constant temperature is stirred 50 minutes at 60 DEG C of same stir speed (S.S.) after dripping off, and obtains final product gadolinium-titanium complex catalyst.
By 0.01 mole of 5,5- dimethyl two ring [2,2,1] hept-2-ene", 0.01 mole of cyclohexene and 0.01 mole of carbonic acid Asia
Vinyl acetate be added to repeatedly vacuumize, in nitrogen charging autoclave, plus 20ml1,2- dichloroethanes dissolving.By in catalyst three (rings penta
Diene) changing the amount of gadolinium (III), to be calculated as 5,5- dimethyl two ring [2,2,1] hept-2-ene", cyclohexene and vinylene carbonate three total
The 0.30% of weight takes above-mentioned gadolinium-titanium complex catalyst, is injected in above-mentioned mixture with syringe.Constant temperature is in 50 DEG C, 1MPa
Reacted 6 hours under pressure.Product is poured into the ethanol solution containing 5wt% hydrochloric acid precipitates copolymer, precipitates washed with EtOH
To neutral, vacuum drying, that is, obtain 5,5- dimethyl two ring [2,2,1] hept-2-ene", cyclohexene and vinylene carbonate ternary and be total to
Polymers.It is 48.8% to calculate reaction yield.
Embodiment 9
In the there-necked flask of dry atmosphere of inert gases, 0.001 three (cyclopentadiene) that rub are changed into gadolinium (III) and 0.012
Mole α, α '-bipyridyl is dissolved in 10 milliliters of hexamethylenes, under 330rpm, 0.016 mole of tetraisopropoxy titanium is instilled above-mentioned
In solution, constant temperature is stirred 50 minutes at 50 DEG C of same stir speed (S.S.) after dripping off, and obtains final product gadolinium-titanium complex catalyst.
By 0.01 mole of 1- phenyl two ring [2,2,1] hept-2-ene", 0.01 mole of cyclohexene and 0.01 mole of vinylene carbonate
Ester be added to repeatedly vacuumize, in nitrogen charging autoclave, plus 20ml hexamethylenes dissolving.Change gadolinium by catalyst three (cyclopentadiene)
(III) what amount was calculated as 1- phenyl two ring [2,2,1] hept-2-ene", cyclohexene and vinylene carbonate three's gross weight 0.60% takes
Above-mentioned gadolinium-titanium complex catalyst, is injected in above-mentioned mixture with syringe.It is small that constant temperature reacts 5 at 90 DEG C, under 3.5MPa 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- phenyl two ring [2,2,1] hept-2-ene", cyclohexene and vinylene carbonate terpolymer.Calculate reaction yield
It is 58.7%.
Embodiment 10
In the there-necked flask of dry atmosphere of inert gases, 0.001 three (cyclopentadiene) that rub are changed into gadolinium (III) and 0.011
Mole α, α '-bipyridyl is dissolved in 10 milliliters of cyclohexanone, under 380rpm, 0.09 mole of tetraisopropoxy titanium is instilled above-mentioned molten
In liquid, constant temperature is stirred 40 minutes at 50 DEG C of same stir speed (S.S.) after dripping off, and obtains final product gadolinium-titanium complex catalyst.
By 0.01 mole of 5- phenyl two ring [2,2,1] hept-2-ene", 0.01 mole of cyclohexene and 0.01 mole of vinylene carbonate
Ester be added to repeatedly vacuumize, in nitrogen charging autoclave, plus 20ml cyclohexanone dissolving.Change gadolinium by catalyst three (cyclopentadiene)
(III) what amount was calculated as 5- phenyl two ring [2,2,1] hept-2-ene", cyclohexene and vinylene carbonate three's gross weight 0.10% takes
Above-mentioned gadolinium-titanium complex catalyst, is injected in above-mentioned mixture with syringe.It is small that constant temperature reacts 5 at 70 DEG C, under 6MPa 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 5- phenyl two ring [2,2,1] hept-2-ene", cyclohexene and vinylene carbonate terpolymer.Calculate reaction yield
It is 76.8%.
Embodiment 11
In the there-necked flask of dry atmosphere of inert gases, 0.001 three (cyclopentadiene) that rub are changed into gadolinium (III) and 0.008
Mole Phen is dissolved in 10 milliliters of toluene, under 360rpm, 0.014 mole of tetraisopropoxy titanium is instilled into above-mentioned solution
In, constant temperature is stirred 30 minutes at 60 DEG C of same stir speed (S.S.) after dripping off, and obtains final product gadolinium-titanium complex catalyst.
By 0.01 mole of 5- vinyl two ring [2,2,1] hept-2-ene", 0.01 mole of cyclohexene and 0.01 mole of carbonic acid Asia second
Alkene ester be added to repeatedly vacuumize, in nitrogen charging autoclave, plus 20ml toluene dissolving.Change gadolinium by catalyst three (cyclopentadiene)
(III) amount is calculated as the 0.06% of 5- vinyl two ring [2,2,1] hept-2-ene", cyclohexene and vinylene carbonate three's gross weight
Above-mentioned gadolinium-titanium complex catalyst is taken, is injected in above-mentioned mixture with syringe.It is small that constant temperature reacts 6 at 80 DEG C, under 5MPa 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 5- vinyl two ring [2,2,1] hept-2-ene", cyclohexene and vinylene carbonate terpolymer.Reaction is calculated to receive
Rate is 65.4%.
Embodiment 12
In the there-necked flask of dry atmosphere of inert gases, 0.001 three (cyclopentadiene) that rub are changed into gadolinium (III) and 0.010
Mole isoquinolin is dissolved in 10 milliliters of tetrahydrofurans, under 370rpm, 0.011 mole of tetraisopropoxy titanium is instilled into above-mentioned solution
In, constant temperature is stirred 40 minutes at 50 DEG C of same stir speed (S.S.) after dripping off, and obtains final product gadolinium-titanium complex catalyst.
By 0.01 mole of two ring [2,2,1] hept-2-ene" -5- methyl formates, 0.01 mole of cyclohexene and 0.01 mole of carbonic acid
Vinylene be added to repeatedly vacuumize, in nitrogen charging autoclave, plus 20ml tetrahydrofurans dissolving.By in catalyst three (rings penta 2
Alkene) change gadolinium (III) amount be calculated as two rings [2,2,1] hept-2-ene" -5- methyl formates, cyclohexene and vinylene carbonate three's gross weight
The 0.08% of amount takes above-mentioned gadolinium-titanium complex catalyst, is injected in above-mentioned mixture with syringe.Constant temperature is in 90 DEG C, 3MPa pressures
Reacted 6 hours under power.Product is poured into the ethanol solution containing 5wt% hydrochloric acid precipitates copolymer, and precipitates washed with EtOH is extremely
Neutrality, vacuum drying obtains two rings [2,2,1] hept-2-ene" -5- methyl formates, cyclohexene and vinylene carbonate ternary and is total to
Polymers.It is 80.3% to calculate reaction yield.
Embodiment 13
In the there-necked flask of dry atmosphere of inert gases, 0.015 three (cyclopentadiene) that rub are changed into gadolinium (III) and 0.006
Mole quinoline is dissolved in 10 milliliters of petroleum ethers, under 490rpm, during 0.005 mole of tetraisopropoxy titanium instilled into above-mentioned solution,
Constant temperature is stirred 50 minutes at 50 DEG C of same stir speed (S.S.) after dripping off, and obtains final product gadolinium-titanium 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 cyclohexene and 0.01 mole of carbon
Sour vinylene be added to repeatedly vacuumize, in nitrogen charging autoclave, plus 20ml petroleum ether dissolutions.By in catalyst three (rings penta 2
Alkene) change gadolinium (III) amount be calculated as two rings [2,2,1] hept-2-ene" -5- formic acid spy butyl ester, cyclohexene and vinylene carbonate three it is total
The 1.30% of weight takes above-mentioned gadolinium-titanium complex catalyst, is injected in above-mentioned mixture with syringe.Constant temperature is in 100 DEG C, 6MPa
Reacted 2 hours under pressure.Product is poured into the ethanol solution containing 5wt% hydrochloric acid precipitates copolymer, precipitates washed with EtOH
To neutral, vacuum drying, that is, obtain two rings [2,2,1] hept-2-ene" -5- formic acid spy butyl ester, cyclohexene and vinylene carbonate three
Membered copolymer.It is 52.3% to calculate reaction yield.
Embodiment 14
In the there-necked flask of dry atmosphere of inert gases, 0.016 three (cyclopentadiene) that rub are changed into gadolinium (III) and 0.016
Mole porphyrin is dissolved in 10 milliliters of methyl phenyl ethers anisoles, under 290rpm, during 0.004 mole of tetraisopropoxy titanium instilled into above-mentioned solution,
Constant temperature is stirred 50 minutes at 40 DEG C of same stir speed (S.S.) after dripping off, and obtains final product gadolinium-titanium 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 cyclohexene and 0.01 mole of carbon
Sour vinylene be added to repeatedly vacuumize, in nitrogen charging autoclave, plus 20ml methyl phenyl ethers anisoles dissolving.By in catalyst three (rings penta 2
Alkene) change gadolinium (III) amount be calculated as two rings [2,2,1] hept-2-ene" -5- formic acid spy butyl ester, cyclohexene and vinylene carbonate three it is total
The 0.07% of weight takes above-mentioned gadolinium-titanium complex catalyst, is injected in above-mentioned mixture with syringe.Constant temperature is in 30 DEG C, 6MPa
Reacted 5 hours under pressure.Product is poured into the ethanol solution containing 5wt% hydrochloric acid precipitates copolymer, precipitates washed with EtOH
To neutral, vacuum drying, that is, obtain two rings [2,2,1] hept-2-ene" -5- formic acid spy butyl ester, cyclohexene and vinylene carbonate three
Membered copolymer.It is 44.7% to calculate reaction yield.
Embodiment 15
In the there-necked flask of dry atmosphere of inert gases, 0.001 three (cyclopentadiene) that rub are changed into gadolinium (III) and 0.006
Mole α, α '-bipyridyl is dissolved in 10 milliliters of hexamethylenes, under 440rpm, 0.007 mole of tetraisopropoxy titanium is instilled above-mentioned
In solution, constant temperature is stirred 60 minutes at 30 DEG C of same stir speed (S.S.) after dripping off, and obtains final product gadolinium-titanium complex catalyst.
0.01 mole of two ring [2,2,1] hept-2-ene", 0.01 mole of cyclohexene and 0.01 mole of vinylene carbonate are added
To repeatedly vacuumizing, in nitrogen charging autoclave, plus the dissolving of 20ml hexamethylenes.Change the amount of gadolinium (III) by catalyst three (cyclopentadiene)
It is calculated as the 1.50% of two rings [2,2,1] hept-2-ene", cyclohexene and vinylene carbonate three's gross weight and takes above-mentioned gadolinium-titanium complexing
Thing catalyst, is injected in above-mentioned mixture with syringe.Constant temperature reacts 6 hours at 70 DEG C under 6MPa pressure.Product is poured into and contains
Copolymer is precipitated in the ethanol solution of 5wt% hydrochloric acid, precipitates washed with EtOH to neutrality, vacuum drying obtains two rings
[2,2,1] hept-2-ene", cyclohexene and vinylene carbonate terpolymer.It is 65.1% to calculate reaction yield.
Embodiment 16
In the there-necked flask of dry atmosphere of inert gases, 0.001 three (cyclopentadiene) that rub are changed into gadolinium (III) and 0.001
Mole 8-hydroxyquinoline is dissolved in 10 milliliters of benzene, under 350rpm, 0.016 mole of tetraisopropoxy titanium is instilled into above-mentioned solution
In, constant temperature is stirred 50 minutes at 50 DEG C of same stir speed (S.S.) after dripping off, and obtains final product gadolinium-titanium complex catalyst.
By 0.01 mole of 1- methyl bicyclics [2,2,1] hept-2-ene", 0.01 mole of cyclohexene and 0.01 mole of vinylene carbonate
Ester be added to repeatedly vacuumize, in nitrogen charging autoclave, plus 20ml benzene dissolving.Change gadolinium (III) by catalyst three (cyclopentadiene)
Amount be calculated as the 0.80% of 1- methyl bicyclics [2,2,1] hept-2-ene", cyclohexene and vinylene carbonate three's gross weight take it is above-mentioned
Gadolinium-titanium complex catalyst, is injected in above-mentioned mixture with syringe.Constant temperature reacts 5 hours at 100 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 1- methyl bicyclics [2,2,1] hept-2-ene", cyclohexene and vinylene carbonate terpolymer.Calculating reaction yield is
53.4%.
Claims (5)
1. norborneol alkenes, cyclohexene and vinylene carbonate ternary polymerization catalyst, it is characterised in that the preparation of the catalyst
Method is as follows：
In the there-necked flask of dry atmosphere of inert gases, three (cyclopentadiene) change gadolinium (III) and part is dissolved in the first solvent
In, under 300~500rpm, tetraisopropoxy titanium is instilled, the constant temperature stirring under same stir speed (S.S.) at 30-60 DEG C after dripping off
30-60 minutes, obtain final product gadolinium-titanium complex catalyst；
It is 1 that three (cyclopentadiene) change gadolinium (III) with the mol ratio of the part：16~16：1, three (cyclopentadiene) are changed
Gadolinium (III) is 1 with the mol ratio of the tetraisopropoxy titanium：16~16：1；
The part is selected from 8-hydroxyquinoline, α, α '-bipyridyl, Phen, isoquinolin, quinoline, porphyrin or pentanedione；
First solvent be selected from benzene, toluene, tetrahydrofuran, petroleum ether, methyl phenyl ethers anisole, 1,4- dioxane, 1,2- dichloroethanes,
Hexamethylene or cyclohexanone；
The consumption of the solvent and three (cyclopentadiene) change the ratio of gadolinium (III), tetraisopropoxy titanium and part three's total amount
It is 10 milliliters：0.010~0.040 mole.
2. norborneol alkenes according to claim 1, cyclohexene and vinylene carbonate ternary polymerization catalyst, its feature
It is that the mol ratio that described three (cyclopentadiene) change gadolinium (III), tetraisopropoxy titanium and part three is 1：8：10.
3. norborneol alkenes according to claim 1 and 2, cyclohexene and vinylene carbonate ternary polymerization catalyst, its
It is characterised by that 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.
4. the norborneol alkenes as described in claims 1 to 3 any claim, cyclohexene and vinylene carbonate ternary are used
The norborneol alkenes of catalyst for copolymerization, cyclohexene and vinylene carbonate method for ternary polymerization, it is characterised in that including following steps
Suddenly：
According to mol ratio 1：1：1 take norborneol alkenes, cyclohexene and vinylene carbonate ester monomer be added to repeatedly vacuumize, nitrogen charging
In reactor, the dissolving of the second solvent is added；It is subsequently adding described gadolinium-titanium complex catalyst, at 30~100 DEG C, 0.1-
Reacted 1~6 hour under 6MPa pressure；
The product for obtaining will be reacted to pour into the ethanol solution containing 4-5wt% hydrochloric acid, the precipitates washed with EtOH for obtaining is into
Property, obtain ENB class, cyclohexene and vinylene carbonate terpolymer after vacuum drying；
The consumption of the gadolinium-titanium complex catalyst is calculated as ENB by the amount that in catalyst three (cyclopentadiene) change gadolinium (III)
The 0.01%-1.5% of class, cyclohexene and vinylene carbonate three's gross weight；
Second solvent be selected from benzene, toluene, tetrahydrofuran, petroleum ether, methyl phenyl ethers anisole, 1,4- dioxane, 1,2- dichloroethanes,
Hexamethylene or cyclohexanone；The molal quantity sum of each polymerized monomer is 0.03 mole with the amount ratio of second solvent：20 milliliters.
5. norborneol alkenes according to claim 4, cyclohexene and vinylene carbonate ternary polymerization catalyst, its feature
It is that the Norbornene derivative is selected from two rings [2,2,1] hept-2-ene", 1- methyl bicyclics [2,2,1] hept-2-ene", 5- methyl
Two rings [2,2,1] hept-2-ene", 7- methyl bicyclics [2,2,1] hept-2-ene", 1- ethyls two ring [2,2,1] hept-2-ene", 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-ene", 5- phenyl
Two rings [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.
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| CN103626919A (en) * | 2013-11-27 | 2014-03-12 | 宁波工程学院 | Norbornene, maleic anhydride and vinyl acetate ternary polymerization catalyst and ternary polymerization method |
| CN103864990A (en) * | 2014-03-11 | 2014-06-18 | 宁波工程学院 | Norbornene, norbornene and cyclohexene ternary polymerization catalyst and ternary polymerization method |
| CN105693929A (en) * | 2016-03-17 | 2016-06-22 | 宁波工程学院 | Norbornene, styrene and nikasol ternary polymerization catalyst and ternary polymerization method |
| CN105693928A (en) * | 2016-03-17 | 2016-06-22 | 宁波工程学院 | Norbornene, hexafluoropropylene and acrylonitrile ternary polymerization catalyst and ternary polymerization method |
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| CN103626919A (en) * | 2013-11-27 | 2014-03-12 | 宁波工程学院 | Norbornene, maleic anhydride and vinyl acetate ternary polymerization catalyst and ternary polymerization method |
| CN103864990A (en) * | 2014-03-11 | 2014-06-18 | 宁波工程学院 | Norbornene, norbornene and cyclohexene ternary polymerization catalyst and ternary polymerization method |
| CN105693929A (en) * | 2016-03-17 | 2016-06-22 | 宁波工程学院 | Norbornene, styrene and nikasol ternary polymerization catalyst and ternary polymerization method |
| CN105693928A (en) * | 2016-03-17 | 2016-06-22 | 宁波工程学院 | Norbornene, hexafluoropropylene and acrylonitrile ternary polymerization catalyst and ternary polymerization method |
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