CN106832123A - Norborneol alkenes, vinyl ethyl ether and perfluoro methyl vinyl ether ternary polymerization catalyst and method for ternary polymerization - Google Patents
Norborneol alkenes, vinyl ethyl ether and perfluoro methyl vinyl ether ternary polymerization catalyst and method for ternary polymerization Download PDFInfo
- Publication number
- CN106832123A CN106832123A CN201710111622.5A CN201710111622A CN106832123A CN 106832123 A CN106832123 A CN 106832123A CN 201710111622 A CN201710111622 A CN 201710111622A CN 106832123 A CN106832123 A CN 106832123A
- Authority
- CN
- China
- Prior art keywords
- ether
- vanadium
- hept
- ene
- ethyl ether
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
Classifications
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F232/00—Copolymers of cyclic compounds containing no unsaturated aliphatic radicals in a side chain, and having one or more carbon-to-carbon double bonds in a carbocyclic ring system
- C08F232/08—Copolymers of cyclic compounds containing no unsaturated aliphatic radicals in a side chain, and having one or more carbon-to-carbon double bonds in a carbocyclic ring system having condensed rings
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F216/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by an alcohol, ether, aldehydo, ketonic, acetal or ketal radical
- C08F216/12—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by an alcohol, ether, aldehydo, ketonic, acetal or ketal radical by an ether radical
- C08F216/14—Monomers containing only one unsaturated aliphatic radical
- C08F216/1408—Monomers containing halogen
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F216/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by an alcohol, ether, aldehydo, ketonic, acetal or ketal radical
- C08F216/12—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by an alcohol, ether, aldehydo, ketonic, acetal or ketal radical by an ether radical
- C08F216/14—Monomers containing only one unsaturated aliphatic radical
- C08F216/16—Monomers containing no hetero atoms other than the ether oxygen
- C08F216/18—Acyclic compounds
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F4/00—Polymerisation catalysts
- C08F4/42—Metals; Metal hydrides; Metallo-organic compounds; Use thereof as catalyst precursors
- C08F4/44—Metals; Metal hydrides; Metallo-organic compounds; Use thereof as catalyst precursors selected from light metals, zinc, cadmium, mercury, copper, silver, gold, boron, gallium, indium, thallium, rare earths or actinides
- C08F4/60—Metals; Metal hydrides; Metallo-organic compounds; Use thereof as catalyst precursors selected from light metals, zinc, cadmium, mercury, copper, silver, gold, boron, gallium, indium, thallium, rare earths or actinides together with refractory metals, iron group metals, platinum group metals, manganese, rhenium technetium or compounds thereof
- C08F4/62—Refractory metals or compounds thereof
- C08F4/64—Titanium, zirconium, hafnium or compounds thereof
- C08F4/659—Component covered by group C08F4/64 containing a transition metal-carbon bond
- C08F4/6592—Component covered by group C08F4/64 containing a transition metal-carbon bond containing at least one cyclopentadienyl ring, condensed or not, e.g. an indenyl or a fluorenyl ring
- C08F4/65922—Component covered by group C08F4/64 containing a transition metal-carbon bond containing at least one cyclopentadienyl ring, condensed or not, e.g. an indenyl or a fluorenyl ring containing at least two cyclopentadienyl rings, fused or not
- C08F4/65925—Component covered by group C08F4/64 containing a transition metal-carbon bond containing at least one cyclopentadienyl ring, condensed or not, e.g. an indenyl or a fluorenyl ring containing at least two cyclopentadienyl rings, fused or not two cyclopentadienyl rings being mutually non-bridged
Landscapes
- Chemical & Material Sciences (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- Crystallography & Structural Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)
- Transition And Organic Metals Composition Catalysts For Addition Polymerization (AREA)
Abstract
The present invention relates to norborneol alkenes, vinyl ethyl ether and perfluoro methyl vinyl ether ternary polymerization catalyst and method for ternary polymerization, it is characterised in that the preparation method of the catalyst is as follows：In the container of dry atmosphere of inert gases, double (cyclopentadiene) vanadium and part are dissolved in the first solvent, obtain mixed solution；During diethyl zinc instilled into the mixed solution, stirred 30 60 minutes at 30 60 DEG C after dripping off, obtain final product vanadium zinc complex catalyst；Take Norbornene derivative, vinyl ethyl ether and perfluoro methyl vinyl ether monomer and be added to and repeatedly vacuumize, in nitrogen charging autoclave, add the dissolving of the second solvent；Described vanadium zinc complex catalyst is subsequently adding, is reacted 16 hours under uniform temperature and 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, vinyl ethyl ether and perfluoro methyl vinyl ether terpolymer after vacuum drying.
Description
Technical field
The present invention relates to high polymer field, a kind of norborneol alkenes, vinyl ethyl ether and perfluoromethylvinyl are referred specifically to
Base ether ternary polymerization catalyst 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 157nm ultraviolet light photoetching.This material major defect is that fragility, viscosity difference and molecular weight are low
Deng.After containing in PVF and oxygen-containing ethylene insertion polynorbornene main chain, the caking property and solubility of polymer can be improved, and
And material absorptance in itself is reduced, this copolymer can be applied to 157nm replica technologies as photoresist, such as
ENB, tetrafluoroethene and acrylate copolymer are used as photoetching material, performance by A.E.Feiring and M.Toriumi etc.
Improve a lot.And, the smaller composition of the development need of microelectronics industry, to being 1.3 μm and less suitable for line width
The exposure technique of line width, may be selected 157nm F2 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 of solution.Therefore, for the photoetching new material for obtaining, alternating copolymerization material has been developed, wherein mainly there is ENB
With Class C acid esters, the component copolymeric material of Fluorine containing olefine three, while using the ENB for having side base, it is therefore an objective to improve whole matrix
Resistance to corrosion, reduce material absorptance, improve lithography performance.
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 the 80-92 pages of Proceedings of SPIE Vol.5039 (2003) employs peroxide
As the catalyst of radical polymerization, light disclosed in the 127-135 pages of Proceedings of SPIE Vol.4690 (2002)
The synthesis for carving material employs catalyst of the AINB (azodiisobutyronitrile) as radical polymerization.A.E.Feiring and
M.Toriumi etc. by ENB, tetrafluoroethene and free radical acrylate ternary polymerization etc., the generally existing reaction time is long,
Acquisition copolymer yield 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,
Norborneol alkenes, vinyl ethyl ether and the perfluoro methyl vinyl ether ternary polymerization of catalytic efficiency and copolymer yield are improved with urging
Agent.
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, vinyl ethyl ether and perfluoro methyl vinyl ether 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, vinyl ethyl ether and complete
Methyl fluoride vinyl ethers ternary polymerization catalyst, it is characterised in that the preparation method of the catalyst is as follows：
In the container of dry atmosphere of inert gases, double (cyclopentadiene) vanadium and part are dissolved in the first solvent,
Obtain mixed solution；Then under 200-400rpm, during diethyl zinc instilled into the mixed solution, at 30-60 DEG C after dripping off
It is lower to continue to stir 30-60 minutes, obtain final product vanadium-zinc complex catalyst；
Double (cyclopentadiene) vanadium and the mol ratio of the part are 1：16-16：1, double (cyclopentadiene) vanadium with
The mol ratio of the diethyl zinc is 1：16-16：1；
The part is selected from 8-hydroxyquinoline, α, α '-bipyridyl, Phen, isoquinolin, quinoline, porphyrin, acetyl group third
Ketone；
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 ratio of the consumption of the solvent and described double (cyclopentadiene) vanadium, diethyl zinc and part three's total amount is 10 millis
Rise：0.005~0.030 mole.
The mol ratio of double (cyclopentadiene) vanadium, diethyl zinc and the part threes is preferably 1：10：10.
The part and first solvent can first be dried before；Solid-state part in wherein described part
Drying be first with recrystallization method purify then vacuum drying；The drying of the liquid part in the part be with calcium hydride or
Metallic sodium is dried, and the solvent is dried using calcium chloride or calcium hydride.
Use the norborneol of above-mentioned norborneol alkenes, vinyl ethyl ether and perfluoro methyl vinyl ether ternary polymerization catalyst
Alkenes, vinyl ethyl ether and perfluoro methyl vinyl ether method for ternary polymerization, it is characterised in that comprise the steps：
According to mol ratio 1：1：1 takes Norbornene derivative, vinyl ethyl ether and perfluoro methyl vinyl ether monomer adds
To repeatedly vacuumizing, in nitrogen charging autoclave, the dissolving of the second solvent is added；Described vanadium-zinc complex catalyst is subsequently adding,
At 30-120 DEG C, reacted 1-6 hours under 0.1-8MPa 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, vinyl ethyl ether and perfluoro methyl vinyl ether terpolymer are obtained after vacuum drying；
The consumption of the vanadium-zinc complex catalyst is calculated as ENB by the amount of double (cyclopentadiene) vanadium in catalyst
The 0.01%-1.50% of class, vinyl ethyl ether and perfluoro methyl vinyl ether 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 is selected from two rings [2,2,1] hept-2-ene", 1- methyl bicyclics [2,2,1] hept-2-ene", 5-
Methyl bicyclic [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- second
Base 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 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- formic acid first
Ester or two rings [2,2,1] hept-2-ene" -5- formic acid spy's butyl ester.
Compared with prior art, the invention provides a kind of new norbornene copolymer and the catalysis of the copolymer is prepared
Agent, there is provided copolymer resistance to corrosion it is good, material absorptance is low, and lithography performance is excellent；The catalyst for being used is a kind of new
Vanadium-zinc complex catalyst, catalyst raw material is cheap and easy to get, and catalysis activity, norborneol alkenes, ethene can be produced under compared with low temperature
Base ether and perfluoro methyl vinyl ether ternary polymerization, polymeric reaction temperature are low, high catalytic efficiency, and product is easy to washing point
From copolymer yield is 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 double (cyclopentadiene) vanadium and 0.001 mole
8-hydroxyquinoline is dissolved in 10 milliliters of benzene, obtains mixed solution；Electric blender stirring is loaded onto, 0.006 rubs under 250rpm
Your diethyl zinc is instilled in mixed solution, and constant temperature is stirred 60 minutes at 30 DEG C after dripping off, and obtains final product vanadium-zinc complex catalyst.
By 0.01 mole of two ring [2,2,1] hept-2-ene", 0.01 molar ethylene base ether and 0.01 mole of perfluoromethylvinyl
Base ether be added to repeatedly vacuumize, in nitrogen charging autoclave, plus 20ml benzene dissolving.By the gauge of double (cyclopentadiene) vanadium in catalyst
For the 0.07% of two rings [2,2,1] hept-2-ene", vinyl ethyl ether and perfluoro methyl vinyl ether three's gross weight take above-mentioned vanadium-
Zinc complex catalyst, is injected in above-mentioned mixture with syringe.Constant temperature reacts 6 hours at 120 DEG C under 1MPa 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 two rings [2,2,1] hept-2-ene", vinyl ethyl ether and perfluoro methyl vinyl ether terpolymer.Calculating reaction yield is
63.3%.
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 double (cyclopentadiene) vanadium and 0.006 mole
α, α '-bipyridyl is dissolved in 10 milliliters of toluene, obtains mixed solution；Electric blender stirring is loaded onto, by 0.001 under 350rpm
Mole diethyl zinc is instilled in mixed solution, and constant temperature is stirred 40 minutes at 40 DEG C after dripping off, and obtains final product vanadium-zinc complex catalysis
Agent.
By 0.01 mole of two ring [2,2,1] hept-2-ene", 0.01 molar ethylene base ether and 0.01 mole of perfluoromethylvinyl
Base ether be added to repeatedly vacuumize, in nitrogen charging autoclave, plus 20ml toluene dissolving.By the amount of double (cyclopentadiene) vanadium in catalyst
Be calculated as the 1.00% of two rings [2,2,1] hept-2-ene", vinyl ethyl ether and perfluoro methyl vinyl ether three's gross weight take it is above-mentioned
Vanadium-zinc complex catalyst, is injected in above-mentioned mixture with syringe.Constant temperature reacts 5 hours at 90 DEG C under 6MPa pressure.Produce
Thing is poured into the ethanol solution containing 4wt% hydrochloric acid precipitates copolymer, precipitates washed with EtOH to neutrality, vacuum drying, i.e.,
Obtain two rings [2,2,1] hept-2-ene", vinyl ethyl ether and perfluoro methyl vinyl ether terpolymer.Calculating reaction yield is
43.7%.
Embodiment 3
In the there-necked flask of dry atmosphere of inert gases, by 0.001 mole of double (cyclopentadiene) vanadium and 0.012 mole
Phen is dissolved in 10 milliliters of tetrahydrofurans, obtains mixed solution；Electric blender stirring is loaded onto, at 300 rpm will
0.010 mole of diethyl zinc is instilled in mixed solution, and constant temperature is stirred 60 minutes at 60 DEG C after dripping off, and obtains final product vanadium-zinc complex
Catalyst.
By 0.01 mole of 1- methyl bicyclics [2,2,1] hept-2-ene", 0.01 molar ethylene base ether and 0.01 mole of perfluor first
Base vinyl ethers be added to repeatedly vacuumize, in nitrogen charging autoclave, plus 20ml tetrahydrofurans dissolving.By double (rings penta in catalyst
Diene) amount of vanadium is calculated as 1- methyl bicyclics [2,2,1] hept-2-ene", vinyl ethyl ether and perfluoro methyl vinyl ether three's gross weight
The 0.08% of amount takes above-mentioned vanadium-zinc complex catalyst, is injected in above-mentioned mixture with syringe.Constant temperature is in 90 DEG C, 5MPa 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, that is, obtain 1- methyl bicyclics [2,2,1] hept-2-ene", vinyl ethyl ether and perfluoro methyl vinyl ether ternary
Copolymer.It is 88.1% to calculate reaction yield.
Embodiment 4
In the there-necked flask of dry atmosphere of inert gases, by 0.001 mole of double (cyclopentadiene) vanadium and 0.010 mole
Quinoline is dissolved in 10 milliliters of petroleum ethers, obtains mixed solution；Electric blender stirring is loaded onto, by 0.010 mole under 330rpm
Diethyl zinc is instilled in mixed solution, and constant temperature is stirred 50 minutes at 50 DEG C after dripping off, and obtains final product vanadium-zinc complex catalyst.
By 0.01 mole of 5- methyl bicyclics [2,2,1] hept-2-ene", 0.01 molar ethylene base ether and 0.01 mole of perfluor first
Base vinyl ethers be added to repeatedly vacuumize, in nitrogen charging autoclave, plus 20ml petroleum ether dissolutions.By double (rings penta 2 in catalyst
Alkene) amount of vanadium is calculated as 5- methyl bicyclics [2,2,1] hept-2-ene", vinyl ethyl ether and perfluoro methyl vinyl ether three's gross weight
0.09% take above-mentioned vanadium-zinc complex catalyst, injected in above-mentioned mixture with syringe.Constant temperature is in 100 DEG C, 7MPa pressure
Lower reaction 6 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- methyl bicyclics [2,2,1] hept-2-ene", vinyl ethyl ether and perfluoro methyl vinyl ether ternary and is total to
Polymers.It is 92.2% to calculate reaction yield.
Embodiment 5
In the there-necked flask of dry atmosphere of inert gases, by 0.001 mole of double (cyclopentadiene) vanadium and 0.007 mole
Porphyrin is dissolved in 10 milliliters of methyl phenyl ethers anisoles, obtains mixed solution；Electric blender stirring is loaded onto, by 0.008 mole under 400rpm
Diethyl zinc is instilled in mixed solution, and constant temperature is stirred 60 minutes at 40 DEG C after dripping off, and obtains final product vanadium-zinc complex catalyst.
By 0.01 mole of 7- methyl bicyclics [2,2,1] hept-2-ene", 0.01 molar ethylene base ether and 0.01 mole of perfluor first
Base vinyl ethers be added to repeatedly vacuumize, in nitrogen charging autoclave, plus 20ml methyl phenyl ethers anisoles dissolving.By double (rings penta 2 in catalyst
Alkene) amount of vanadium is calculated as 7- methyl bicyclics [2,2,1] hept-2-ene", vinyl ethyl ether and perfluoro methyl vinyl ether three's gross weight
0.10% take above-mentioned vanadium-zinc complex catalyst, injected in above-mentioned mixture with syringe.Constant temperature is in 80 DEG C, 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 7- methyl bicyclics [2,2,1] hept-2-ene", vinyl ethyl ether and perfluoro methyl vinyl ether ternary and is total to
Polymers.It is 71.3% to calculate reaction yield.
Embodiment 6
In the there-necked flask of dry atmosphere of inert gases, by 0.016 mole of double (cyclopentadiene) vanadium and 0.001 mole
Pentanedione is dissolved in 10 milliliters of Isosorbide-5-Nitrae-dioxane, obtains mixed solution；Electric blender stirring is loaded onto, at 200 rpm
By in 0.008 mole of diethyl zinc instillation mixed solution, constant temperature is stirred 30 minutes at 60 DEG C after dripping off, and obtains final product vanadium-zinc complexing
Thing catalyst.
By 0.01 mole of 1- ethyls two ring [2,2,1] hept-2-ene", 0.01 molar ethylene base ether and 0.01 mole of perfluor first
Base vinyl ethers be added to repeatedly vacuumize, in nitrogen charging autoclave, plus 20ml1,4- dioxane dissolving.By double in catalyst
The amount of (cyclopentadiene) vanadium is calculated as 1- ethyls two ring [2,2,1] hept-2-ene", vinyl ethyl ether and perfluoro methyl vinyl ether three
The 1.50% of gross weight takes above-mentioned vanadium-zinc complex catalyst, is injected in above-mentioned mixture with syringe.Constant temperature at 80 DEG C,
Reacted 3 hours under 0.1MPa pressure.Product is poured into the ethanol solution containing 5wt% hydrochloric acid precipitates copolymer, sediment second
Alcohol is washed to neutrality, and vacuum drying obtains 1- ethyls two ring [2,2,1] hept-2-ene", vinyl ethyl ether and perfluoromethylvinyl
Base ether terpolymer.It is 45.2% to calculate reaction yield.
Embodiment 7
In the there-necked flask of dry atmosphere of inert gases, by 0.016 mole of double (cyclopentadiene) vanadium and 0.012 mole
8-hydroxyquinoline is dissolved in 10 milliliters of Isosorbide-5-Nitrae-dioxane, obtains mixed solution；Electric blender stirring is loaded onto, under 280rpm
By in 0.001 mole of diethyl zinc instillation mixed solution, constant temperature is stirred 50 minutes at 60 DEG C after dripping off, and obtains final product vanadium-zinc complexing
Thing catalyst.
By 0.01 mole of 5- ethyls two ring [2,2,1] hept-2-ene", 0.01 molar ethylene base ether and 0.01 mole of perfluor first
Base vinyl ethers be added to repeatedly vacuumize, in nitrogen charging autoclave, plus 20ml1,4- dioxane dissolving.By double in catalyst
The amount of (cyclopentadiene) vanadium is calculated as 5- ethyls two ring [2,2,1] hept-2-ene", vinyl ethyl ether and perfluoro methyl vinyl ether three
The 0.50% of gross weight takes above-mentioned vanadium-zinc complex catalyst, is injected in above-mentioned mixture with syringe.Constant temperature at 30 DEG C,
Reacted 3 hours under 0.8MPa pressure.Product is poured into the ethanol solution containing 5wt% hydrochloric acid precipitates copolymer, sediment second
Alcohol is washed to neutrality, and vacuum drying obtains 5- ethyls two ring [2,2,1] hept-2-ene", vinyl ethyl ether and perfluoromethylvinyl
Base ether terpolymer.It is 40.9% to calculate reaction yield.
Embodiment 8
In the there-necked flask of dry atmosphere of inert gases, by 0.006 mole of double (cyclopentadiene) vanadium and 0.016 mole
Isoquinolin is dissolved in 10 milliliters of 1,2- dichloroethanes, obtains mixed solution；Electric blender stirring is loaded onto, will under 260rpm
0.001 mole of diethyl zinc is instilled in mixed solution, and constant temperature is stirred 50 minutes at 40 DEG C after dripping off, and obtains final product vanadium-zinc complex
Catalyst.
0.01 mole of 5,5- dimethyl two ring [2,2,1] hept-2-ene", 0.01 molar ethylene base ether and 0.01 mole is complete
Methyl fluoride vinyl ethers be added to repeatedly vacuumize, in nitrogen charging autoclave, plus 20ml1,2- dichloroethanes dissolving.By in catalyst
The amount of double (cyclopentadiene) vanadium is calculated as 5,5- dimethyl two ring [2,2,1] hept-2-ene", vinyl ethyl ether and perfluoromethylvinyl base
The 1.10% of ether three's gross weight takes above-mentioned vanadium-zinc complex catalyst, is injected in above-mentioned mixture with syringe.Constant temperature is 50
DEG C, reacted 3 hours under 2MPa pressure.Product is poured into the ethanol solution containing 5wt% hydrochloric acid precipitates copolymer, sediment second
Alcohol is washed to neutrality, and vacuum drying obtains 5,5- dimethyl two ring [2,2,1] hept-2-ene", vinyl ethyl ether and perfluoro-methyl
Vinyl ethers terpolymer.It is 46.6% to calculate reaction yield.
Embodiment 9
In the there-necked flask of dry atmosphere of inert gases, by 0.001 mole of double (cyclopentadiene) vanadium and 0.016 mole
α, α '-bipyridyl is dissolved in 10 milliliters of hexamethylenes, obtains mixed solution；Electric blender stirring is loaded onto, will under 340rpm
0.008 mole of diethyl zinc is instilled in mixed solution, and constant temperature is stirred 60 minutes at 50 DEG C after dripping off, and obtains final product vanadium-zinc complex
Catalyst.
By 0.01 mole of 1- phenyl two ring [2,2,1] hept-2-ene", 0.01 molar ethylene base ether and 0.01 mole of perfluor first
Base vinyl ethers be added to repeatedly vacuumize, in nitrogen charging autoclave, plus 20ml hexamethylenes dissolving.By double (rings penta 2 in catalyst
Alkene) amount of vanadium is calculated as 1- phenyl two ring [2,2,1] hept-2-ene", vinyl ethyl ether and perfluoro methyl vinyl ether three's gross weight
0.80% take above-mentioned vanadium-zinc complex catalyst, injected in above-mentioned mixture with syringe.Constant temperature is in 120 DEG C, 3MPa pressure
Lower reaction 2 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 1- phenyl two ring [2,2,1] hept-2-ene", vinyl ethyl ether and perfluoro methyl vinyl ether ternary and is total to
Polymers.It is 53.8% to calculate reaction yield.
Embodiment 10
In the there-necked flask of dry atmosphere of inert gases, by 0.001 mole of double (cyclopentadiene) vanadium and 0.008 mole
α, α '-bipyridyl is dissolved in 10 milliliters of cyclohexanone, obtains mixed solution；Electric blender stirring is loaded onto, will under 290rpm
0.016 mole of diethyl zinc is instilled in mixed solution, and constant temperature is stirred 50 minutes at 60 DEG C after dripping off, and obtains final product vanadium-zinc complex
Catalyst.
By 0.01 mole of 5- phenyl two ring [2,2,1] hept-2-ene", 0.01 molar ethylene base ether and 0.01 mole of perfluor first
Base vinyl ethers be added to repeatedly vacuumize, in nitrogen charging autoclave, plus 20ml cyclohexanone dissolving.By double (rings penta 2 in catalyst
Alkene) amount of vanadium is calculated as 5- phenyl two ring [2,2,1] hept-2-ene", vinyl ethyl ether and perfluoro methyl vinyl ether three's gross weight
0.05% take above-mentioned vanadium-zinc complex catalyst, injected in above-mentioned mixture with syringe.Constant temperature is in 90 DEG C, 5MPa pressure
Lower reaction 5 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- phenyl two ring [2,2,1] hept-2-ene", vinyl ethyl ether and perfluoro methyl vinyl ether ternary and is total to
Polymers.It is 67.1% to calculate reaction yield.
Embodiment 11
In the there-necked flask of dry atmosphere of inert gases, by 0.001 mole of double (cyclopentadiene) vanadium and 0.009 mole
Phen is dissolved in 10 milliliters of toluene, obtains mixed solution；Electric blender stirring is loaded onto, 0.012 rubs under 370rpm
Your diethyl zinc is instilled in mixed solution, and constant temperature is stirred 40 minutes at 50 DEG C after dripping off, and obtains final product vanadium-zinc complex catalyst.
By 0.01 mole of 5- vinyl two ring [2,2,1] hept-2-ene", 0.01 molar ethylene base ether and 0.01 mole of perfluor
Methyl vinyl ether be added to repeatedly vacuumize, in nitrogen charging autoclave, plus 20ml toluene dissolving.By double (rings penta 2 in catalyst
Alkene) amount of vanadium is calculated as 5- vinyl two ring [2,2,1] hept-2-ene", vinyl ethyl ether and perfluoro methyl vinyl ether three's gross weight
The 0.10% of amount takes above-mentioned vanadium-zinc complex catalyst, is injected in above-mentioned mixture with syringe.Constant temperature is in 100 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, that is, obtain 5- vinyl two ring [2,2,1] hept-2-ene", vinyl ethyl ether and perfluoro methyl vinyl ether three
Membered copolymer.It is 74.3% to calculate reaction yield.
Embodiment 12
In the there-necked flask of dry atmosphere of inert gases, by 0.001 mole of double (cyclopentadiene) vanadium and 0.009 mole
Isoquinolin is dissolved in 10 milliliters of tetrahydrofurans, obtains mixed solution；Electric blender stirring is loaded onto, by 0.013 under 280rpm
Mole diethyl zinc is instilled in mixed solution, and constant temperature is stirred 30 minutes at 50 DEG C after dripping off, and obtains final product vanadium-zinc complex catalysis
Agent.
By 0.01 mole of two ring [2,2,1] hept-2-ene" -5- methyl formate, 0.01 molar ethylene base ether and 0.01 mole
Perfluoro methyl vinyl ether be added to repeatedly vacuumize, in nitrogen charging autoclave, plus 20ml tetrahydrofurans dissolving.By double in catalyst
The amount of (cyclopentadiene) vanadium is calculated as two rings [2,2,1] hept-2-ene" -5- methyl formates, vinyl ethyl ether and perfluoromethylvinyl base
The 0.07% of ether three's gross weight takes above-mentioned vanadium-zinc complex catalyst, is injected in above-mentioned mixture with syringe.Constant temperature is 80
DEG C, reacted 5 hours under 5MP pressure.Product is poured into the ethanol solution containing 5wt% hydrochloric acid precipitates copolymer, sediment second
Alcohol is washed to neutrality, and vacuum drying obtains two rings [2,2,1] hept-2-ene" -5- methyl formates, vinyl ethyl ether and perfluor first
Base vinyl ethers terpolymer.It is 76.4% to calculate reaction yield.
Embodiment 13
In the there-necked flask of dry atmosphere of inert gases, by 0.012 mole of double (cyclopentadiene) vanadium and 0.010 mole
Quinoline is dissolved in 10 milliliters of petroleum ethers, obtains mixed solution；Electric blender stirring is loaded onto, by 0.003 mole under 360rpm
Diethyl zinc is instilled in mixed solution, and constant temperature is stirred 40 minutes at 40 DEG C after dripping off, and obtains final product vanadium-zinc complex catalyst.
0.01 mole of two ring [2,2,1] hept-2-ene" -5- formic acid spy butyl ester, 0.01 molar ethylene base ether and 0.01 are rubbed
Your perfluoro methyl vinyl ether be added to repeatedly vacuumize, in nitrogen charging autoclave, plus 20ml petroleum ether dissolutions.By double in catalyst
The amount of (cyclopentadiene) vanadium is calculated as two rings [2,2,1] hept-2-ene" -5- formic acid spy butyl ester, vinyl ethyl ether and perfluoromethylvinyl
The 0.01% of base ether three's gross weight takes above-mentioned vanadium-zinc complex catalyst, is injected in above-mentioned mixture with syringe.Constant temperature exists
40 DEG C, reacted 6 hours under 5MPa pressure.Product is poured into the ethanol solution containing 5wt% hydrochloric acid precipitates copolymer, and sediment is used
Ethanol is washed to neutrality, vacuum drying, that is, obtain two rings [2,2,1] hept-2-ene" -5- formic acid spy butyl ester, vinyl ethyl ether and complete
Methyl fluoride vinyl ethers terpolymer.It is 44.4% to calculate reaction yield.
Embodiment 14
In the there-necked flask of dry atmosphere of inert gases, by 0.014 mole of double (cyclopentadiene) vanadium and 0.007 mole
Porphyrin is dissolved in 10 milliliters of methyl phenyl ethers anisoles, obtains mixed solution；Electric blender stirring is loaded onto, by 0.001 mole under 290rpm
Diethyl zinc is instilled in mixed solution, and constant temperature is stirred 60 minutes at 60 DEG C after dripping off, and obtains final product vanadium-zinc complex catalyst.
0.01 mole of two ring [2,2,1] hept-2-ene" -5- formic acid spy butyl ester, 0.01 molar ethylene base ether and 0.01 are rubbed
Your perfluoro methyl vinyl ether be added to repeatedly vacuumize, in nitrogen charging autoclave, plus 20ml methyl phenyl ethers anisoles dissolve.By double in catalyst
The amount of (cyclopentadiene) vanadium is calculated as two rings [2,2,1] hept-2-ene" -5- formic acid spy butyl ester, vinyl ethyl ether and perfluoromethylvinyl
The 1.20% of base ether three's gross weight takes above-mentioned vanadium-zinc complex catalyst, is injected in above-mentioned mixture with syringe.Constant temperature exists
100 DEG C, reacted 5 hours under 2MPa pressure.Product is poured into the ethanol solution containing 5wt% hydrochloric acid precipitates copolymer, sediment
Washed with ethanol to neutrality, vacuum drying, that is, obtain two rings [2,2,1] hept-2-ene" -5- formic acid spy butyl ester, vinyl ethyl ether and
Perfluoro methyl vinyl ether terpolymer.It is 49.5% to calculate reaction yield.
Embodiment 15
In the there-necked flask of dry atmosphere of inert gases, by 0.001 mole of double (cyclopentadiene) vanadium and 0.008 mole
α, α '-bipyridyl is dissolved in 10 milliliters of hexamethylenes, obtains mixed solution；Electric blender stirring is loaded onto, will under 340rpm
0.008 mole of diethyl zinc is instilled in mixed solution, and constant temperature is stirred 50 minutes at 40 DEG C after dripping off, and obtains final product vanadium-zinc complex
Catalyst.
By 0.01 mole of two ring [2,2,1] hept-2-ene", 0.01 molar ethylene base ether and 0.01 mole of perfluoromethylvinyl
Base ether be added to repeatedly vacuumize, in nitrogen charging autoclave, plus 20ml hexamethylenes dissolving.By double (cyclopentadiene) vanadium in catalyst
Amount be calculated as the 0.10% of two rings [2,2,1] hept-2-ene", vinyl ethyl ether and perfluoro methyl vinyl ether three's gross weight take it is above-mentioned
Vanadium-zinc complex catalyst, is injected in above-mentioned mixture with syringe.Constant temperature reacts 4 hours at 90 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 two rings [2,2,1] hept-2-ene", vinyl ethyl ether and perfluoro methyl vinyl ether terpolymer.Calculating reaction yield is
81.2%.
Embodiment 16
In the there-necked flask of dry atmosphere of inert gases, by 0.001 mole of double (cyclopentadiene) vanadium and 0.003 mole
8-hydroxyquinoline is dissolved in 10 milliliters of benzene, obtains mixed solution；Electric blender stirring is loaded onto, 0.005 rubs at 300 rpm
Your diethyl zinc is instilled in mixed solution, and constant temperature is stirred 50 minutes at 40 DEG C after dripping off, and obtains final product vanadium-zinc complex catalyst.
By 0.01 mole of 1- methyl bicyclics [2,2,1] hept-2-ene", 0.01 molar ethylene base ether and 0.01 mole of perfluor first
Base vinyl ethers be added to repeatedly vacuumize, in nitrogen charging autoclave, plus 20ml benzene dissolving.By double (cyclopentadiene) vanadium in catalyst
Amount be calculated as 1- methyl bicyclics [2,2,1] hept-2-ene", vinyl ethyl ether and perfluoro methyl vinyl ether three's gross weight
0.40% takes above-mentioned vanadium-zinc complex catalyst, is injected in above-mentioned mixture with syringe.Constant temperature at 70 DEG C, under 3MPa pressure
Reaction 4 hours.Product is poured into the ethanol solution containing 4wt% hydrochloric acid precipitates copolymer, precipitates washed with EtOH to neutrality,
Vacuum drying, that is, obtain 1- methyl bicyclics [2,2,1] hept-2-ene", vinyl ethyl ether and perfluoro methyl vinyl ether ternary polymerization
Thing.It is 56.2% to calculate reaction yield.
Claims (5)
1. norborneol alkenes, vinyl ethyl ether and perfluoro methyl vinyl ether ternary polymerization catalyst, it is characterised in that the catalysis
The preparation method of agent is as follows：
In the container of dry atmosphere of inert gases, double (cyclopentadiene) vanadium and part are dissolved in the first solvent, obtained
Mixed solution；Then under 200-400rpm, during diethyl zinc instilled into the mixed solution, after dripping off at 30-60 DEG C after
Continuous stirring 30-60 minutes, obtains final product vanadium-zinc complex catalyst；
Double (cyclopentadiene) vanadium and the mol ratio of the part are 1：16-16：1, double (cyclopentadiene) vanadium with it is described
The mol ratio of diethyl zinc is 1：16-16：1；
The part is selected from 8-hydroxyquinoline, α, α '-bipyridyl, Phen, isoquinolin, quinoline, porphyrin, 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 ratio of the consumption of the solvent and described double (cyclopentadiene) vanadium, diethyl zinc and part three's total amount is 10 milliliters：
0.005~0.030 mole.
2. norborneol alkenes according to claim 1, vinyl ethyl ether and perfluoro methyl vinyl ether ternary polymerization catalysis
Agent, it is characterised in that the mol ratio of double (cyclopentadiene) vanadium, diethyl zinc and the part threes is 1：10：10.
3. norborneol alkenes according to claim 1 and 2, vinyl ethyl ether and perfluoro methyl vinyl ether ternary polymerization is urged
Agent, it is characterised in that the part and first solvent are first dried using preceding；Solid-state in wherein described part
The drying of part is first to be purified with recrystallization method and then vacuum drying；The drying of the liquid part in the part is with hydrogenation
Calcium or metallic sodium are 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, vinyl ethyl ether and perfluoromethylvinyl are used
The norborneol alkenes of base ether ternary polymerization catalyst, vinyl ethyl ether and perfluoro methyl vinyl ether method for ternary polymerization, it is special
Levy is to comprise the steps：
According to mol ratio 1：1：1 take Norbornene derivative, vinyl ethyl ether and perfluoro methyl vinyl ether monomer be added to it is many
It is secondary to vacuumize, in nitrogen charging autoclave, add the dissolving of the second solvent；Described vanadium-zinc complex catalyst is subsequently adding, in 30-
At 120 DEG C, reacted 1-6 hours under 0.1-8MPa 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, vinyl ethyl ether and perfluoro methyl vinyl ether terpolymer after vacuum drying；
The consumption of the vanadium-zinc complex catalyst is calculated as norborneol alkenes, second by the amount of double (cyclopentadiene) vanadium in catalyst
The 0.01%-1.50% of vinyl ethyl ether and perfluoro methyl vinyl ether 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, vinyl ethyl ether and perfluoro methyl vinyl ether method for ternary polymerization,
It is characterized in that the Norbornene derivative be selected from two rings [2,2,1] hept-2-ene", 1- methyl bicyclics [2,2,1] hept-2-ene",
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-ene", 5-
Ethyl 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 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- formic acid
Methyl esters or two rings [2,2,1] hept-2-ene" -5- formic acid spy's butyl ester.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201710111622.5A CN106832123B (en) | 2017-02-28 | 2017-02-28 | Norborneol alkenes, vinyl ethyl ether and perfluoro methyl vinyl ether ternary polymerization catalyst and method for ternary polymerization |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201710111622.5A CN106832123B (en) | 2017-02-28 | 2017-02-28 | Norborneol alkenes, vinyl ethyl ether and perfluoro methyl vinyl ether ternary polymerization catalyst and method for ternary polymerization |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN106832123A true CN106832123A (en) | 2017-06-13 |
| CN106832123B CN106832123B (en) | 2019-02-15 |
Family
ID=59134752
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201710111622.5A Active CN106832123B (en) | 2017-02-28 | 2017-02-28 | Norborneol alkenes, vinyl ethyl ether and perfluoro methyl vinyl ether ternary polymerization catalyst and method for ternary polymerization |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN106832123B (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN107189014A (en) * | 2017-07-05 | 2017-09-22 | 宁波工程学院 | Norborneol alkenes, styrene and perfluoro methyl vinyl ether ternary polymerization catalyst and method for ternary polymerization |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103396514A (en) * | 2013-08-01 | 2013-11-20 | 宁波工程学院 | Catalyst for ternary polymerization of norbornene, maleic anhydride and pentene, and ternary polymerization method |
| CN105218709A (en) * | 2015-11-17 | 2016-01-06 | 宁波工程学院 | Norbornylene class, styrenic and maleic anhydride tercopolymer catalyst for copolymerization and method for ternary polymerization |
-
2017
- 2017-02-28 CN CN201710111622.5A patent/CN106832123B/en active Active
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103396514A (en) * | 2013-08-01 | 2013-11-20 | 宁波工程学院 | Catalyst for ternary polymerization of norbornene, maleic anhydride and pentene, and ternary polymerization method |
| CN105218709A (en) * | 2015-11-17 | 2016-01-06 | 宁波工程学院 | Norbornylene class, styrenic and maleic anhydride tercopolymer catalyst for copolymerization and method for ternary polymerization |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN107189014A (en) * | 2017-07-05 | 2017-09-22 | 宁波工程学院 | Norborneol alkenes, styrene and perfluoro methyl vinyl ether ternary polymerization catalyst and method for ternary polymerization |
Also Published As
| Publication number | Publication date |
|---|---|
| CN106832123B (en) | 2019-02-15 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN105111372B (en) | Norborneol alkenes, octafluoro cyclopentene and hexamethylene alkenes ternary polymerization catalyst and method for ternary polymerization | |
| CN101328244B (en) | Preparation of copolymer of norbornene and maleic anhydride | |
| CN105693928B (en) | Norborneol alkenes, hexafluoropropene and acrylonitrile ternary polymerization catalyst and method for ternary polymerization | |
| CN104140496B (en) | Norborneol alkenes, vinylacetate and esters of acrylic acid method for ternary polymerization | |
| CN106832123B (en) | Norborneol alkenes, vinyl ethyl ether and perfluoro methyl vinyl ether ternary polymerization catalyst and method for ternary polymerization | |
| CN106832122B (en) | Norborneol alkenes, amylene class and vinylene carbonate ternary polymerization catalyst and method for ternary polymerization | |
| CN105524218B (en) | Norborneol alkenes, hexafluoropropene and 1 hexene ternary polymerization catalyst and method for ternary polymerization | |
| CN106832120B (en) | Norborneol alkenes, hexafluoropropene and vinylene carbonate ternary polymerization catalyst and method for ternary polymerization | |
| CN104262513B (en) | Norbornylene class, vinyl acetate and octafluoro cyclopentenes terpolymer catalyzer and method for ternary polymerization | |
| CN106832119B (en) | Norborneol alkenes, tetrafluoroethene and perfluoro methyl vinyl ether ternary polymerization catalyst and method for ternary polymerization | |
| CN106749915B (en) | Norborneol alkenes, esters of acrylic acid and vinylene carbonate ternary polymerization catalyst and method for ternary polymerization | |
| CN106749911B (en) | Norborneol alkenes, tetrafluoroethene and N-phenylmaleimide ternary polymerization catalyst and method for ternary polymerization | |
| CN104311738B (en) | Norbornylene class, maleic anhydride and octafluoro cyclopentenes terpolymer catalyzer and method for ternary polymerization | |
| CN106632852B (en) | Norborneol alkenes, vinylacetate and perfluoro methyl vinyl ether ternary polymerization catalyst and method for ternary polymerization | |
| CN106749912B (en) | Norborneol alkenes, vinylacetate and N-phenylmaleimide ternary polymerization catalyst and method for ternary polymerization | |
| CN106832121B (en) | Norborneol alkenes, cyclohexene and vinylene carbonate ternary polymerization catalyst and method for ternary polymerization | |
| CN106832124B (en) | Norborneol alkenes, acrylonitrile and N-phenylmaleimide ternary polymerization catalyst and method for ternary polymerization | |
| CN106749913B (en) | Norborneol alkenes, octafluoro cyclopentene and N-phenylmaleimide ternary polymerization catalyst and method for ternary polymerization | |
| CN106866884A (en) | Norborneol alkenes, vinyl cyclohexane and perfluoro methyl vinyl ether ternary polymerization catalyst and method for ternary polymerization | |
| CN105218709A (en) | Norbornylene class, styrenic and maleic anhydride tercopolymer catalyst for copolymerization and method for ternary polymerization | |
| CN106496417B (en) | Norborneol alkenes, styrene and acrylonitrile ternary polymerization catalyst and method for ternary polymerization | |
| CN106749781B (en) | Norborneol alkenes and perfluoro methyl vinyl ether binary copolymerization catalyst and binary copolymerization method | |
| CN106832118A (en) | Norborneol alkenes and vinylene carbonate binary copolymerization catalyst and binary copolymerization method | |
| CN106632851B (en) | Norborneol alkenes, hexafluoropropene and N-phenylmaleimide ternary polymerization catalyst and method for ternary polymerization | |
| CN106432609B (en) | The preparation method of norborneol alkenes, styrene and cyclohexene terpolymer |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| CB02 | Change of applicant information |
Address after: 315211 Zhejiang Province, Ningbo Jiangbei District Fenghua Road No. 201 Applicant after: Ningbo University of Technology Address before: 315300 Zhejiang Province, Ningbo city Haishu District cypress Road No. 89 Applicant before: Ningbo University of Technology |
|
| CB02 | Change of applicant information | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant |