CN106832121B - 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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- CN106832121B CN106832121B CN201710089285.4A CN201710089285A CN106832121B CN 106832121 B CN106832121 B CN 106832121B CN 201710089285 A CN201710089285 A CN 201710089285A CN 106832121 B CN106832121 B CN 106832121B
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Abstract
The present invention relates to norborneol alkenes, cyclohexene and vinylene carbonate ternary polymerization catalyst, it is characterized in that the catalyst the preparation method is as follows: in the three-necked flask of dry atmosphere of inert gases, three (cyclopentadiene) change gadolinium (III) and ligand is dissolved in the first solvent, at 300~500rpm, instill tetraisopropoxy titanium, constant temperature stirs 30-60 minutes to get gadolinium-titanium complex catalyst under same stirring rate at 30-60 DEG C after dripping off；It takes norborneol alkenes, cyclohexene and vinylene carbonate ester monomer to be added to according to molar ratio 1:1:1 repeatedly to vacuumize, in nitrogen charging reaction kettle, the dissolution of the second solvent is added；Then gadolinium-titanium complex the catalyst is added to react 1~6 hour under 0.1-6MPa pressure at 30~100 DEG C；The product that reaction obtains is poured into hydrochloric ethanol solution, obtained precipitates washed with EtOH to neutrality, norbornene class, cyclohexene and vinylene carbonate terpolymer are obtained 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 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 oxygenatedchemicals is inserted into polynorbornene main chain, the caking property and solubility of polymer can be improved, and reduce material
Expect the absorptance of itself.This copolymer can be used as photoresist applied to 193nm replica technology.Moreover, microelectronics industry
193nm light may be selected to the exposure technique that line width is 1.3 μm and following line width is suitable in the smaller ingredient of development need
Lithography, these technologies are related to the various aspects of photoetching process, propose new optical material and its manufacture with coating technique, newly
Type resist, for new material of mask and its protective film etc. up for solving the problems, such as.Therefore, the photoetching in order to obtain
New material has developed alternating copolymerization material, main development norbornene and tetrafluoroethene or other component ternary polymerization materials, together
Shi Yingyong has the norbornene of side group, it is therefore an objective to improve the resistance to corrosion of entire matrix, improve lithography performance, increase the viscous of material
Knot property, solubility and toughness.
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, 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 lower reaction temperature, high catalytic efficiency and copolymerization
Norborneol alkenes, the method for cyclohexene and vinylene carbonate ternary polymerization of object high income.
The technical scheme of the invention to solve the technical problem is: the norborneol alkenes, cyclohexene and carbonic acid are sub-
Vinyl acetate ternary polymerization catalyst, it is characterised in that the catalyst the preparation method is as follows:
In the three-necked flask of dry atmosphere of inert gases, three (cyclopentadiene) change gadolinium (III) and ligand is dissolved in first
In solvent, at 300~500rpm, tetraisopropoxy titanium is instilled, constant temperature stirs under same stirring rate at 30-60 DEG C after dripping off
30-60 minutes are mixed to get gadolinium-titanium complex catalyst；
It is 1:16~16:1, the three (ring penta 2 that three (cyclopentadiene), which change gadolinium (III) and the molar ratio of the ligand,
Alkene) change the molar ratio of gadolinium (III) and the tetraisopropoxy titanium as 1:16~16:1；
The ligand 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- dichloro
Ethane, hexamethylene or cyclohexanone；
The dosage of the solvent and described three (cyclopentadiene) change gadolinium (III), tetraisopropoxy titanium and ligand three's total amount
Ratio is 10 milliliters: 0.010~0.040 moles.
The molar ratio that three (cyclopentadiene) change gadolinium (III), tetraisopropoxy titanium and ligand three is preferably 1:8:10.
The ligand and first solvent are first dried using preceding；Wherein the solid-state ligand in the ligand is dry
Dry is first to be purified then to be dried in vacuo with recrystallization method；The drying of liquid ligand in the ligand is with calcium hydride or metal
Sodium is dry, and the solvent is dry using calcium chloride or calcium hydride.
Use above-mentioned norborneol alkenes, the norborneol alkenes of cyclohexene and vinylene carbonate ternary polymerization catalyst, ring
Hexene and vinylene carbonate method for ternary polymerization, it is characterised in that include the following steps:
According to molar ratio 1:1:1 take norborneol alkenes, cyclohexene and vinylene carbonate ester monomer be added to repeatedly vacuumize,
In nitrogen charging reaction kettle, the dissolution of the second solvent is added；Then gadolinium-titanium complex the catalyst is added, at 20~100 DEG C,
It is reacted 1~6 hour under 0.1-6MPa 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, cyclohexene and vinylene carbonate terpolymer are obtained after vacuum drying；
The gadolinium-titanium complex catalyst dosage is calculated as drop 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 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 Norbornene derivative can be selected from two rings [2,2,1] hept-2-ene", 1- methyl bicyclic [2,2,1] hept- 2-
Alkene, 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-
Alkene, two ring of 5- ethyl [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- alkene, two ring of 5- 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- methyl formate or two rings [2,2,1] hept-2-ene" -5- formic acid spy's butyl ester.
Compared with prior art, catalyst provided by the invention is a kind of novel gadolinium-titanium complex catalyst mixture, is urged
Agent raw material is cheap and easy to get, can generate catalytic activity, catalysis norborneol alkenes, cyclohexene and vinylene carbonate at relatively low temperatures
Ternary polymerization, reaction temperature is lower, high catalytic efficiency, and product is easy to washing separation, 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
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, by 0.001 rub three (cyclopentadiene) change 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 above-mentioned solution
In, constant temperature stirs 40 minutes to get gadolinium-titanium complex catalyst at 60 DEG C of same stirring rate after dripping off.
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, 20ml benzene is added to dissolve.It is calculated as by the amount that in catalyst three (cyclopentadiene) change gadolinium (III)
Two rings [2,2,1] hept-2-ene", cyclohexene and vinylene carbonate three's total weight 0.06% take above-mentioned gadolinium-titanium complex to urge
Agent is injected in above-mentioned mixture with syringe.Constant temperature reacts 6 hours under 90 DEG C, 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 to get to two rings [2,2,
1] hept-2-ene", cyclohexene and vinylene carbonate terpolymer.Calculating reaction yield is 62.2%.
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, by 0.001 rub three (cyclopentadiene) change gadolinium (III) and 0.007
Mole α, α '-bipyridyl is dissolved in 10 milliliters of toluene, at 400rpm, 0.016 mole of tetraisopropoxy titanium is instilled above-mentioned molten
In liquid, constant temperature stirs 50 minutes to get gadolinium-titanium complex catalyst at 30 DEG C of same stirring rate after dripping off.
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, 20ml toluene is added to dissolve.Change the meter of gadolinium (III) by catalyst three (cyclopentadiene)
0.01% for two rings [2,2,1] hept-2-ene", cyclohexene and vinylene carbonate three's total weight takes above-mentioned gadolinium-titanium complex
Catalyst is injected in above-mentioned mixture with syringe.Constant temperature reacts 6 hours under 100 DEG C, 6MPa pressure.Product, which is poured into, to be contained
Precipitate copolymer in the ethanol solution of 4wt% hydrochloric acid, precipitates washed with EtOH to neutrality, vacuum drying is to get to two rings
[2,2,1] hept-2-ene", cyclohexene and vinylene carbonate terpolymer.Calculating reaction yield is 55.5%.
Embodiment 3
In the three-necked flask of dry atmosphere of inert gases, by 0.001 rub three (cyclopentadiene) change 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 stirs 50 minutes to get gadolinium-titanium complex catalyst at 60 DEG C of same stirring rate after dripping off.
By 0.01 mole of 1- methyl bicyclic [2,2,1] hept-2-ene", 0.01 mole of cyclohexene and 0.01 mole of vinylene carbonate
Ester, which is added to, repeatedly to be vacuumized, in nitrogen charging autoclave, and 20ml tetrahydrofuran is added to dissolve.Change gadolinium by catalyst three (cyclopentadiene)
(III) what amount was calculated as 1- methyl bicyclic [2,2,1] hept-2-ene", cyclohexene and vinylene carbonate three's total 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 under 90 DEG C, 5MPa 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 1- methyl bicyclic [2,2,1] hept-2-ene", cyclohexene and vinylene carbonate terpolymer.Calculate reaction yield
It is 90.3%.
Embodiment 4
In the three-necked flask of dry atmosphere of inert gases, by 0.001 rub three (cyclopentadiene) change gadolinium (III) and 0.012
Mole quinoline is dissolved in 10 milliliters of petroleum ethers, and at 350rpm, 0.010 mole of tetraisopropoxy titanium is instilled in above-mentioned solution,
Constant temperature stirs 60 minutes to get gadolinium-titanium complex catalyst at 50 DEG C of same stirring rate after dripping off.
By 0.01 mole of 5- methyl bicyclic [2,2,1] hept-2-ene", 0.01 mole of cyclohexene and 0.01 mole of vinylene carbonate
Ester, which is added to, repeatedly to be vacuumized, in nitrogen charging autoclave, and 20ml petroleum ether dissolution is added.Change gadolinium by catalyst three (cyclopentadiene)
(III) what amount was calculated as 5- methyl bicyclic [2,2,1] hept-2-ene", cyclohexene and vinylene carbonate three's total 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 under 100 DEG C, 6MPa 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 5- methyl bicyclic [2,2,1] hept-2-ene", cyclohexene and vinylene carbonate terpolymer.Calculate reaction yield
It is 87.7%
Embodiment 5
In the three-necked flask of dry atmosphere of inert gases, by 0.001 rub three (cyclopentadiene) change gadolinium (III) and 0.008
Mole porphyrin is dissolved in 10 milliliters of methyl phenyl ethers anisoles, and at 340rpm, 0.006 mole of tetraisopropoxy titanium is instilled in above-mentioned solution,
Constant temperature stirs 30 minutes to get gadolinium-titanium complex catalyst at 40 DEG C of same stirring rate after dripping off.
By 0.01 mole of 7- methyl bicyclic [2,2,1] hept-2-ene", 0.01 mole of cyclohexene and 0.01 mole of vinylene carbonate
Ester, which is added to, repeatedly to be vacuumized, in nitrogen charging autoclave, and 20ml methyl phenyl ethers anisole is added to dissolve.Change gadolinium by catalyst three (cyclopentadiene)
(III) what amount was calculated as 7- methyl bicyclic [2,2,1] hept-2-ene", cyclohexene and vinylene carbonate three's total 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 under 90 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 7- methyl bicyclic [2,2,1] hept-2-ene", cyclohexene and vinylene carbonate terpolymer.Calculate reaction yield
It is 64.4%.
Embodiment 6
In the three-necked flask of dry atmosphere of inert gases, by 0.016 rub three (cyclopentadiene) change gadolinium (III) and 0.001
Mole pentanedione is dissolved in 10 milliliters of Isosorbide-5-Nitrae-dioxane, and at 360rpm, 0.016 mole of tetraisopropoxy titanium is instilled
In above-mentioned solution, constant temperature stirs 50 minutes to get gadolinium-titanium 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 of cyclohexene and 0.01 mole of vinylene carbonate
Ester, which is added to, repeatedly to be vacuumized, in nitrogen charging autoclave, and 20ml1, the dissolution of 4- dioxane are added.By in catalyst three (cyclopentadiene)
The amount for changing gadolinium (III) is calculated as two ring of 1- ethyl [2,2,1] hept-2-ene", cyclohexene and vinylene carbonate three's total weight
0.08% takes above-mentioned gadolinium-titanium complex catalyst, is injected in above-mentioned mixture with syringe.Constant temperature is under 20 DEG C, 3MPa pressure
Reaction 3 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 two ring of 1- ethyl [2,2,1] hept-2-ene", cyclohexene and vinylene carbonate terpolymer is arrived.It calculates anti-
Answering yield is 45.6%.
Embodiment 7
In the three-necked flask of dry atmosphere of inert gases, by 0.016 rub three (cyclopentadiene) change gadolinium (III) and 0.016
Mole 8-hydroxyquinoline is dissolved in 10 milliliters of Isosorbide-5-Nitrae-dioxane, and at 470rpm, 0.001 mole of tetraisopropoxy titanium is instilled
In above-mentioned solution, constant temperature stirs 50 minutes to get gadolinium-titanium 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 of cyclohexene and 0.01 mole of vinylene carbonate
Ester, which is added to, repeatedly to be vacuumized, in nitrogen charging autoclave, and 20ml1, the dissolution of 4- dioxane are added.By in catalyst three (cyclopentadiene)
The amount for changing gadolinium (III) is calculated as two ring of 5- ethyl [2,2,1] hept-2-ene", cyclohexene and vinylene carbonate three's total weight
1.50% takes above-mentioned gadolinium-titanium complex catalyst, is injected in above-mentioned mixture with syringe.Constant temperature is at 100 DEG C, 0.1MPa pressure
Lower reaction 4 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, it is dried in vacuo to get two ring of 5- ethyl [2,2,1] hept-2-ene", cyclohexene and vinylene carbonate terpolymer is arrived.Meter
Calculating reaction yield is 41.9%.
Embodiment 8
In the three-necked flask of dry atmosphere of inert gases, by 0.007 rub three (cyclopentadiene) change gadolinium (III) and 0.010
Mole isoquinolin is dissolved in 10 milliliters of 1,2- dichloroethanes, at 380rpm, 0.003 mole of tetraisopropoxy titanium is instilled above-mentioned
In solution, constant temperature stirs 50 minutes to get gadolinium-titanium complex catalyst at 60 DEG C of same stirring rate after dripping off.
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, which is added to, repeatedly to be vacuumized, in nitrogen charging autoclave, and 20ml1, the dissolution of 2- dichloroethanes are added.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 at 50 DEG C, 1MPa
It is reacted 6 hours under pressure.Product, which is poured into the ethanol solution of the hydrochloric acid containing 5wt%, precipitates copolymer, precipitates washed with EtOH
To neutrality, vacuum drying is to get total to 5,5- dimethyl, two ring [2,2,1] hept-2-ene", cyclohexene and vinylene carbonate ternary
Polymers.Calculating reaction yield is 48.8%.
Embodiment 9
In the three-necked flask of dry atmosphere of inert gases, by 0.001 rub three (cyclopentadiene) change gadolinium (III) and 0.012
Mole α, α '-bipyridyl is dissolved in 10 milliliters of hexamethylenes, at 330rpm, 0.016 mole of tetraisopropoxy titanium is instilled above-mentioned
In solution, constant temperature stirs 50 minutes to get gadolinium-titanium complex catalyst at 50 DEG C of same stirring rate after dripping off.
By 0.01 mole of two ring of 1- phenyl [2,2,1] hept-2-ene", 0.01 mole of cyclohexene and 0.01 mole of vinylene carbonate
Ester, which is added to, repeatedly to be vacuumized, in nitrogen charging autoclave, and 20ml hexamethylene is added to dissolve.Change gadolinium by catalyst three (cyclopentadiene)
(III) what amount was calculated as two ring of 1- phenyl [2,2,1] hept-2-ene", cyclohexene and vinylene carbonate three's total 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 under 90 DEG C, 3.5MPa 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", cyclohexene and vinylene carbonate terpolymer.Calculate reaction yield
It is 58.7%.
Embodiment 10
In the three-necked flask of dry atmosphere of inert gases, by 0.001 rub three (cyclopentadiene) change gadolinium (III) and 0.011
Mole α, α '-bipyridyl is dissolved in 10 milliliters of cyclohexanone, at 380rpm, 0.09 mole of tetraisopropoxy titanium is instilled above-mentioned molten
In liquid, constant temperature stirs 40 minutes to get gadolinium-titanium complex catalyst at 50 DEG C of same stirring rate after dripping off.
By 0.01 mole of two ring of 5- phenyl [2,2,1] hept-2-ene", 0.01 mole of cyclohexene and 0.01 mole of vinylene carbonate
Ester, which is added to, repeatedly to be vacuumized, in nitrogen charging autoclave, and 20ml cyclohexanone is added to dissolve.Change gadolinium by catalyst three (cyclopentadiene)
(III) what amount was calculated as two ring of 5- phenyl [2,2,1] hept-2-ene", cyclohexene and vinylene carbonate three's total 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 under 70 DEG C, 6MPa 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", cyclohexene and vinylene carbonate terpolymer.Calculate reaction yield
It is 76.8%.
Embodiment 11
In the three-necked flask of dry atmosphere of inert gases, by 0.001 rub three (cyclopentadiene) change gadolinium (III) and 0.008
Mole Phen is dissolved in 10 milliliters of toluene, and at 360rpm, 0.014 mole of tetraisopropoxy titanium is instilled above-mentioned solution
In, constant temperature stirs 30 minutes to get gadolinium-titanium complex catalyst at 60 DEG C of same stirring rate after dripping off.
By 0.01 mole of two ring of 5- vinyl [2,2,1] hept-2-ene", 0.01 mole of cyclohexene and 0.01 mole of carbonic acid Asia second
Enester, which is added to, repeatedly to be vacuumized, in nitrogen charging autoclave, and 20ml toluene is added to dissolve.Change gadolinium by catalyst three (cyclopentadiene)
(III) amount is calculated as the 0.06% of two ring of 5- vinyl [2,2,1] hept-2-ene", cyclohexene and vinylene carbonate three's total 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 under 80 DEG C, 5MPa 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- vinyl [2,2,1] hept-2-ene", cyclohexene and vinylene carbonate terpolymer.Reaction is calculated to receive
Rate is 65.4%.
Embodiment 12
In the three-necked flask of dry atmosphere of inert gases, by 0.001 rub three (cyclopentadiene) change gadolinium (III) and 0.010
Mole isoquinolin is dissolved in 10 milliliters of tetrahydrofurans, and at 370rpm, 0.011 mole of tetraisopropoxy titanium is instilled above-mentioned solution
In, constant temperature stirs 40 minutes to get gadolinium-titanium complex catalyst at 50 DEG C of same stirring rate after dripping off.
By 0.01 mole of two ring [2,2,1] hept-2-ene" -5- methyl formate, 0.01 mole of cyclohexene and 0.01 mole of carbonic acid
Vinylene, which is added to, repeatedly to be vacuumized, in nitrogen charging autoclave, and 20ml tetrahydrofuran is added to dissolve.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 formate, 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.At 90 DEG C, 3MPa is pressed constant temperature
It is reacted 6 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, vacuum drying is to get total to two rings [2,2,1] hept-2-ene" -5- methyl formate, cyclohexene and vinylene carbonate ternary
Polymers.Calculating reaction yield is 80.3%.
Embodiment 13
In the three-necked flask of dry atmosphere of inert gases, by 0.015 rub three (cyclopentadiene) change gadolinium (III) and 0.006
Mole quinoline is dissolved in 10 milliliters of petroleum ethers, and at 490rpm, 0.005 mole of tetraisopropoxy titanium is instilled in above-mentioned solution,
Constant temperature stirs 50 minutes to get gadolinium-titanium complex catalyst at 50 DEG C of same stirring rate after dripping off.
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, which is added to, repeatedly to be vacuumized, in nitrogen charging autoclave, and 20ml petroleum ether dissolution is added.By in catalyst three (rings penta 2
Alkene) changing the amount of gadolinium (III), to be calculated as two rings [2,2,1] hept-2-ene" -5- formic acid spy butyl ester, cyclohexene and vinylene carbonate three total
The 1.30% of weight takes above-mentioned gadolinium-titanium complex catalyst, is injected in above-mentioned mixture with syringe.Constant temperature is at 100 DEG C, 6MPa
It is reacted 2 hours under pressure.Product, which is poured into the ethanol solution of the hydrochloric acid containing 5wt%, precipitates copolymer, precipitates washed with EtOH
To neutrality, vacuum drying is to get to two rings [2,2,1] hept-2-ene" -5- formic acid spy butyl ester, cyclohexene and vinylene carbonate three
Membered copolymer.Calculating reaction yield is 52.3%.
Embodiment 14
In the three-necked flask of dry atmosphere of inert gases, by 0.016 rub three (cyclopentadiene) change gadolinium (III) and 0.016
Mole porphyrin is dissolved in 10 milliliters of methyl phenyl ethers anisoles, and at 290rpm, 0.004 mole of tetraisopropoxy titanium is instilled in above-mentioned solution,
Constant temperature stirs 50 minutes to get gadolinium-titanium complex catalyst at 40 DEG C of same stirring rate after dripping off.
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, 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 three (rings penta 2
Alkene) changing the amount of gadolinium (III), to be calculated as two rings [2,2,1] hept-2-ene" -5- formic acid spy butyl ester, cyclohexene and vinylene carbonate three total
The 0.07% of weight takes above-mentioned gadolinium-titanium complex catalyst, is injected in above-mentioned mixture with syringe.Constant temperature is at 30 DEG C, 6MPa
It is reacted 5 hours under pressure.Product, which is poured into the ethanol solution of the hydrochloric acid containing 5wt%, precipitates copolymer, precipitates washed with EtOH
To neutrality, vacuum drying is to get to two rings [2,2,1] hept-2-ene" -5- formic acid spy butyl ester, cyclohexene and vinylene carbonate three
Membered copolymer.Calculating reaction yield is 44.7%.
Embodiment 15
In the three-necked flask of dry atmosphere of inert gases, by 0.001 rub three (cyclopentadiene) change gadolinium (III) and 0.006
Mole α, α '-bipyridyl is dissolved in 10 milliliters of hexamethylenes, at 440rpm, 0.007 mole of tetraisopropoxy titanium is instilled above-mentioned
In solution, constant temperature stirs 60 minutes to get gadolinium-titanium complex catalyst at 30 DEG C of same stirring rate after dripping off.
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, 20ml hexamethylene is added to dissolve.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 total weight and takes above-mentioned gadolinium-titanium complexing
Object catalyst is injected in above-mentioned mixture with syringe.Constant temperature reacts 6 hours under 70 DEG C, 6MPa 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", cyclohexene and vinylene carbonate terpolymer.Calculating reaction yield is 65.1%.
Embodiment 16
In the three-necked flask of dry atmosphere of inert gases, by 0.001 rub three (cyclopentadiene) change gadolinium (III) and 0.001
Mole 8-hydroxyquinoline is dissolved in 10 milliliters of benzene, and at 350rpm, 0.016 mole of tetraisopropoxy titanium is instilled above-mentioned solution
In, constant temperature stirs 50 minutes to get gadolinium-titanium complex catalyst at 50 DEG C of same stirring rate after dripping off.
By 0.01 mole of 1- methyl bicyclic [2,2,1] hept-2-ene", 0.01 mole of cyclohexene and 0.01 mole of vinylene carbonate
Ester, which is added to, repeatedly to be vacuumized, in nitrogen charging autoclave, and 20ml benzene is added to dissolve.Change gadolinium (III) by catalyst three (cyclopentadiene)
Amount be calculated as the 0.80% of 1- methyl bicyclic [2,2,1] hept-2-ene", cyclohexene and vinylene carbonate three's total weight take it is above-mentioned
Gadolinium-titanium complex catalyst is injected in above-mentioned mixture with syringe.Constant temperature reacts 5 hours under 100 DEG C, 5MPa pressure.It produces
Object, which is poured into the ethanol solution of the hydrochloric acid containing 5wt%, precipitates copolymer, precipitates washed with EtOH to neutrality, vacuum drying, i.e.,
Obtain 1- methyl bicyclic [2,2,1] hept-2-ene", cyclohexene and vinylene carbonate terpolymer.Calculating reaction yield is
53.4%.
Claims (4)
1. norborneol alkenes, cyclohexene and vinylene carbonate method for ternary polymerization, it is characterised in that the system of used catalyst
Preparation Method is as follows:
In the three-necked flask of dry atmosphere of inert gases, three (cyclopentadiene) change gadolinium (III) and ligand is dissolved in the first solvent
In, at 300~500rpm, tetraisopropoxy titanium is instilled, constant temperature stirs under same stirring rate at 30-60 DEG C after dripping off
30-60 minutes to get gadolinium-titanium complex catalyst；
It is 1:16~16:1 that three (cyclopentadiene), which change gadolinium (III) and the molar ratio of the ligand, and three (cyclopentadiene) are changed
The molar ratio of gadolinium (III) and the tetraisopropoxy titanium is 1:16~16:1；
The ligand 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 dosage of the solvent and three (cyclopentadiene) change the ratio of gadolinium (III), tetraisopropoxy titanium and ligand three's total amount
It is 10 milliliters: 0.010~0.040 moles；
According to molar ratio 1:1:1 take norborneol alkenes, cyclohexene and vinylene carbonate ester monomer be added to repeatedly vacuumize, nitrogen charging
In reaction kettle, the dissolution of the second solvent is added；Then gadolinium-titanium complex the catalyst, at 30~100 DEG C, 0.1- is added
It is reacted 1~6 hour under 6MPa pressure；
The product that reaction obtains is poured into the ethanol solution of the hydrochloric acid containing 4-5wt%, obtained precipitates washed with EtOH is into
Property, norbornene class, cyclohexene and vinylene carbonate terpolymer are obtained after vacuum drying；
The gadolinium-titanium complex catalyst dosage is calculated as norbornene by the amount that in catalyst three (cyclopentadiene) change gadolinium (III)
The 0.01%-1.5% of class, cyclohexene and vinylene carbonate three's total 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 amount ratio of the sum of molal quantity of each polymerized monomer and second solvent is 0.03 mole: 20 milliliter.
2. norborneol alkenes according to claim 1, cyclohexene and vinylene carbonate method for ternary polymerization, feature exist
Change the molar ratio of gadolinium (III), tetraisopropoxy titanium and ligand three in described three (cyclopentadiene) as 1:8:10.
3. norborneol alkenes according to claim 1 or 2, cyclohexene and vinylene carbonate method for ternary polymerization, special
Sign is that the ligand and first solvent are first dried using preceding；The wherein drying of the solid-state ligand in the ligand
It is first to be purified then to be dried in vacuo with recrystallization method；The drying of liquid ligand in the ligand is with calcium hydride or metallic sodium
Dry, the solvent is dry using calcium chloride or calcium hydride.
4. norborneol alkenes according to claim 1, cyclohexene and vinylene carbonate method for ternary polymerization, feature exist
Two rings [2,2,1] hept-2-ene", 1- methyl bicyclic [2,2,1] hept-2-ene", 5- methyl two are selected from the Norbornene derivative
Ring [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", two ring of 5- ethyl
[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- phenyl two
Ring [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- methyl formate or two
Ring [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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