CN106832118A - Norborneol alkenes and vinylene carbonate binary copolymerization catalyst and binary copolymerization method - Google Patents
Norborneol alkenes and vinylene carbonate binary copolymerization catalyst and binary copolymerization method Download PDFInfo
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- CN106832118A CN106832118A CN201710086962.7A CN201710086962A CN106832118A CN 106832118 A CN106832118 A CN 106832118A CN 201710086962 A CN201710086962 A CN 201710086962A CN 106832118 A CN106832118 A CN 106832118A
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- 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
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- C08F218/00—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 acyloxy radical of a saturated carboxylic acid, of carbonic acid or of a haloformic acid
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- 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
- C08F4/52—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 selected from boron, aluminium, gallium, indium, thallium or rare earths
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- C08F4/00—Polymerisation catalysts
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- 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
- C08F4/54—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 other compounds thereof
- C08F4/545—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 other compounds thereof rare earths being present, e.g. triethylaluminium + neodymium octanoate
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- C08F218/00—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 acyloxy radical of a saturated carboxylic acid, of carbonic acid or of a haloformic acid
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Abstract
The present invention relates to norborneol alkenes and vinylene carbonate binary copolymerization 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 (butyl cyclopentadiene) are changed into scandium and part is dissolved in the first solvent, under 150~300rpm, instill diethyl zinc, 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 scandium zinc complex catalyst；Norborneol alkenes are taken according to mol ratio 1: 1 and vinylene carbonate ester monomer is added to and repeatedly vacuumizes, in nitrogen charging reactor, adds the dissolving of the second solvent；Described scandium-zinc complex catalyst is subsequently adding, at 20~130 DEG C, is reacted 1~6 hour under 0.1 8MPa pressure；The product for obtaining will be reacted to pour into the ethanol solution containing 4.5 5.5wt% hydrochloric acid, the precipitates washed with EtOH for obtaining to neutrality obtains ENB class and vinylene carbonate bipolymer after vacuum drying.
Description
Technical field
The present invention relates to high polymer field, a kind of norborneol alkenes and the catalysis of vinylene carbonate binary copolymerization are referred specifically to
Agent and binary copolymerization method.
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 oxygen-containing alkene insertion polynorbornene main chain, the caking property and solubility of polymer can be improved, and reduce material
The absorptance of itself.This copolymer can be applied to 193nm replica technologies as photoresist.And, the hair of microelectronics industry
Exhibition needs smaller composition, to suitable for the exposure technique that line width is 1.3 μm and following line width, 193nm photoetching may be selected
Technology, these technologies are related to the various aspects of photoetching process, it is proposed that new optical material and its manufacture and coating technique, new
Resist, the new material etc. for mask and its protective film await the problem for solving.Therefore, in order to the photoetching for obtaining is new
Material, has developed alternating copolymerization material, main development ENB and maleic anhydride, tetrafluoroethene or other component ternary polymerizations
Material, while using the ENB for having side base, it is therefore an objective to improve the resistance to corrosion of whole matrix, improves lithography performance, increases
The caking property of material, soluble and toughness.
The method for synthesizing these materials at present mainly has the methods such as free radical, living radical, metallic catalyst.Such as
The synthesis of photoetching material disclosed in Proceedings of SPIE Vol.5039 (2003) pages 80~92 employs peroxidating
Thing as radical polymerization catalyst, disclosed in Proceedings of SPIE Vol.4690 (2002) pages 127~135
The synthesis of photoetching material employs catalyst of the AINB (azodiisobutyronitrile) as radical polymerization.A.E.Feiring and
M.Toriumi etc. is by ENB, tetrafluoroethene and free radical acrylate ternary polymerization etc..These the synthesis sides for applying at present
Method exist the reaction time it is long, obtain copolymer yield it is low, molecular weight of copolymer is small, the low shortcoming of copolymer alternate degree.
The content of the invention
The technical problems to be solved by the invention be directed to prior art present situation provide one kind can reduce reaction temperature,
Improve the norborneol alkenes and vinylene carbonate binary copolymerization 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 norborneol alkenes of thing high income and the method for vinylene carbonate binary copolymerization.
The present invention solve the technical scheme that is used of above-mentioned technical problem for：The norborneol alkenes and vinylene carbonate two
First catalyst for copolymerization, 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 (butyl cyclopentadiene) are changed into scandium and part and is dissolved in the
In one solvent, under 150~300rpm, diethyl zinc 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 scandium-zinc complex catalyst；
It is 1: 15~15: 1, three (the butyl ring that three (the butyl cyclopentadiene) change scandium with the mol ratio of the part
Pentadiene) mol ratio of changing scandium and the diethyl zinc is 1: 15~15: 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 and three (the butyl cyclopentadiene) change the ratio of scandium, diethyl zinc and part three's total amount
It is 10 milliliters：0.005~0.035 mole.
It is preferred that the mol ratio that three (the butyl cyclopentadiene) change scandium, diethyl zinc and part three is preferably 1: 10: 6.
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 above-mentioned norborneol alkenes and norborneol alkenes and carbonic acid the Asia second of vinylene carbonate binary copolymerization catalyst
Alkene ester binary copolymerization method, it is characterised in that comprise the steps：
Take norborneol alkenes according to mol ratio 1: 1 and vinylene carbonate ester monomer be added to repeatedly vacuumize, nitrogen charging is reacted
In kettle, the dissolving of the second solvent is added；It is subsequently adding described scandium-zinc complex catalyst, at 20~130 DEG C, 0.1-8MPa
Reacted 1~6 hour under pressure；
The product for obtaining will be reacted to pour into the ethanol solution containing 4.5-5.5wt% hydrochloric acid, the sediment ethanol for obtaining
Washing obtains ENB class and vinylene carbonate bipolymer to neutrality after vacuum drying；
The consumption of the scandium-zinc complex catalyst is calculated as drop by the amount that in catalyst three (butyl cyclopentadiene) change scandium
The 0.01%-1.5% of both borneol alkenes and vinylene carbonate 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 scandium-zinc complex catalyst complex,
Catalyst raw material is cheap and easy to get, and catalysis activity can be produced under compared with low temperature, is catalyzed norborneol alkenes and vinylene carbonate binary
Copolymerization, reaction temperature is relatively low, high catalytic efficiency, and product is easy to washing and separates, and copolymer yield is high；Prepared norborneol
Alkenes and vinylene carbonate bipolymer resistance to corrosion are high, and lithography performance is good, and the caking property of material, soluble and tough
Property is 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, by 0.001 mole three (butyl cyclopentadiene) change scandium and
0.001 mole of 8-hydroxyquinoline is dissolved in 10 milliliters of benzene, under 150rpm, 0.015 mole of diethyl zinc is instilled into above-mentioned solution
In, constant temperature is stirred 30 minutes at 30 DEG C of same stir speed (S.S.) after dripping off, and obtains final product scandium-zinc complex catalyst.
0.01 mole of two ring [2,2,1] hept-2-ene", 0.01 mole of vinylene carbonate are added to and are repeatedly vacuumized, filled
In nitrogen autoclave, plus the dissolving of 20ml benzene.The amount for changing scandium by catalyst three (butyl cyclopentadiene) is calculated as two rings [2,2,1] hept-
2- alkene, the 0.01% of both vinylene carbonates gross weight take above-mentioned scandium-zinc complex catalyst, inject above-mentioned with syringe
In mixture.Constant temperature reacts 6 hours at 80 DEG C under 5MPa pressure.Product is poured into the ethanol solution containing 5wt% hydrochloric acid makes copolymerization
Thing is precipitated, precipitates washed with EtOH to neutrality, vacuum drying, that is, obtain two rings [2,2,1] hept-2-ene", vinylene carbonate
Bipolymer.It is 43.3% to calculate reaction yield.
The computational methods of reaction yield are bipolymer 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 three (butyl cyclopentadiene) change scandium and
0.015 mole of α, α '-bipyridyl is dissolved in 10 milliliters of toluene, under 180rpm, 0.008 mole of diethyl zinc is instilled above-mentioned molten
In liquid, constant temperature is stirred 50 minutes at 50 DEG C of same stir speed (S.S.) after dripping off, and obtains final product scandium-zinc complex catalyst.
0.01 mole of two ring [2,2,1] hept-2-ene", 0.01 mole of vinylene carbonate are added to and are repeatedly vacuumized, filled
In nitrogen autoclave, plus the dissolving of 20ml toluene.The amount for changing scandium by catalyst three (butyl cyclopentadiene) is calculated as two rings [2,2,1]
Hept-2-ene", the 0.09% of both vinylene carbonates gross weight take above-mentioned scandium-zinc complex catalyst, are injected with syringe
In stating mixture.Constant temperature reacts 6 hours at 100 DEG C under 4MPa pressure.Product is poured into the ethanol solution containing 5wt% hydrochloric acid to be made
Copolymer is precipitated, precipitates washed with EtOH to neutrality, vacuum drying, that is, obtain two rings [2,2,1] hept-2-ene", carbonic acid Asia second
Alkene ester bipolymer.It is 70.6% to calculate reaction yield.
Embodiment 3
In the there-necked flask of dry atmosphere of inert gases, by 0.001 mole three (butyl cyclopentadiene) change scandium and
0.006 mole of Phen is dissolved in 10 milliliters of tetrahydrofurans, under 250rpm, 0.010 mole of diethyl zinc is instilled above-mentioned
In solution, constant temperature is stirred 50 minutes at 45 DEG C of same stir speed (S.S.) after dripping off, and obtains final product scandium-zinc complex catalyst.
0.01 mole of 1- methyl bicyclics [2,2,1] hept-2-ene", 0.01 mole of vinylene carbonate are added to and repeatedly take out very
In empty, nitrogen charging autoclave, plus the dissolving of 20ml tetrahydrofurans.The amount for changing scandium by catalyst three (butyl cyclopentadiene) is calculated as 1- first
Base two ring [2,2,1] hept-2-ene", the 0.08% of both vinylene carbonates gross weight take above-mentioned scandium-zinc complex catalyst,
Injected in above-mentioned mixture with syringe.Constant temperature reacts 5 hours at 120 DEG C under 6MPa pressure.Product is poured into hydrochloric acid containing 5wt%
Ethanol solution in precipitate copolymer, precipitates washed with EtOH to neutrality, vacuum drying, that is, obtain 1- methyl bicyclics [2,
2,1] hept-2-ene", vinylene carbonate bipolymer.It is 88.6% to calculate reaction yield.
Embodiment 4
In the there-necked flask of dry atmosphere of inert gases, by 0.001 mole three (butyl cyclopentadiene) change scandium and
0.007 mole of quinoline is dissolved in 10 milliliters of petroleum ethers, at 300 rpm, during 0.012 mole of diethyl zinc 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 scandium-zinc complex catalyst.
0.01 mole of 5- methyl bicyclics [2,2,1] hept-2-ene", 0.01 mole of vinylene carbonate are added to and repeatedly take out very
In empty, nitrogen charging autoclave, plus 20ml petroleum ether dissolutions.The amount for changing scandium by catalyst three (butyl cyclopentadiene) is calculated as 5- methyl
Two rings [2,2,1] hept-2-ene", the 0.10% of both vinylene carbonates gross weight take above-mentioned scandium-zinc complex catalyst, use
Syringe is injected in above-mentioned mixture.Constant temperature reacts 4 hours at 130 DEG C under 8MPa pressure.Product is poured into containing 5wt% hydrochloric acid
Precipitate copolymer in ethanol solution, precipitates washed with EtOH to neutrality, vacuum drying, that is, obtain 5- methyl bicyclics [2,2,
1] hept-2-ene", vinylene carbonate bipolymer.It is 82.2% to calculate reaction yield.
Embodiment 5
In the there-necked flask of dry atmosphere of inert gases, by 0.001 mole three (butyl cyclopentadiene) change scandium and
0.006 mole of porphyrin is dissolved in 10 milliliters of methyl phenyl ethers anisoles, at 200 rpm, during 0.015 mole of diethyl zinc instilled into above-mentioned solution,
Constant temperature is stirred 40 minutes at 60 DEG C of same stir speed (S.S.) after dripping off, and obtains final product scandium-zinc complex catalyst.
0.01 mole of 7- methyl bicyclics [2,2,1] hept-2-ene", 0.01 mole of vinylene carbonate are added to and repeatedly take out very
In empty, nitrogen charging autoclave, plus the dissolving of 20ml methyl phenyl ethers anisoles.The amount for changing scandium by catalyst three (butyl cyclopentadiene) is calculated as 7- methyl
Two rings [2,2,1] hept-2-ene", the 0.07% of both vinylene carbonates gross weight take above-mentioned scandium-zinc complex catalyst, use
Syringe is injected in above-mentioned mixture.Constant temperature reacts 5 hours at 90 DEG C under 3MPa pressure.Product is poured into the second containing 5wt% hydrochloric acid
Precipitate copolymer in alcoholic solution, precipitates washed with EtOH to neutrality, vacuum drying obtains 7- methyl bicyclics [2,2,1]
Hept-2-ene", vinylene carbonate bipolymer.It is 74.2% to calculate reaction yield.
Embodiment 6
In the there-necked flask of dry atmosphere of inert gases, by 0.015 mole three (butyl cyclopentadiene) change scandium and
0.001 mole of pentanedione is dissolved in 10 milliliters of Isosorbide-5-Nitrae-dioxane, under 160rpm, 0.006 mole of diethyl zinc is dripped
In entering above-mentioned solution, constant temperature is stirred 40 minutes at 30 DEG C of same stir speed (S.S.) after dripping off, and obtains final product scandium-zinc complex catalyst.
0.01 mole of 1- ethyls two ring [2,2,1] hept-2-ene", 0.01 mole of vinylene carbonate are added to and repeatedly take out very
In empty, nitrogen charging autoclave, plus the dissolving of 20ml1,4- dioxane.The amount for changing scandium by catalyst three (butyl cyclopentadiene) is calculated as
1- ethyls two ring [2,2,1] hept-2-ene", the 1.00% of both vinylene carbonates gross weight take above-mentioned scandium-zinc complex catalysis
Agent, is injected in above-mentioned mixture with syringe.Constant temperature reacts 3 hours at 20 DEG C under 1MPa pressure.Product is poured into salt containing 5wt%
Copolymer is precipitated in the ethanol solution of acid, precipitates washed with EtOH to neutrality, vacuum drying obtains the ring of 1- ethyls two
[2,2,1] hept-2-ene", vinylene carbonate bipolymer.It is 49.2% to calculate reaction yield.
Embodiment 7
In the there-necked flask of dry atmosphere of inert gases, by 0.015 mole three (butyl cyclopentadiene) change scandium and
0.008 mole of 8-hydroxyquinoline is dissolved in 10 milliliters of Isosorbide-5-Nitrae-dioxane, under 270rpm, 0.001 mole of diethyl zinc is dripped
In entering above-mentioned solution, constant temperature is stirred 40 minutes at 40 DEG C of same stir speed (S.S.) after dripping off, and obtains final product scandium-zinc complex catalyst.
0.01 mole of 5- ethyls two ring [2,2,1] hept-2-ene", 0.01 mole of vinylene carbonate are added to and repeatedly take out very
In empty, nitrogen charging autoclave, plus the dissolving of 20ml1,4- dioxane.The amount for changing scandium by catalyst three (butyl cyclopentadiene) is calculated as
5- ethyls two ring [2,2,1] hept-2-ene", the 1.50% of both vinylene carbonates gross weight take above-mentioned scandium-zinc complex catalysis
Agent, is injected in above-mentioned mixture with syringe.Constant temperature reacts 4 hours at 60 DEG C under 0.1MPa pressure.Product is poured into containing 5wt%
Copolymer is precipitated in the ethanol solution of hydrochloric acid, precipitates washed with EtOH to neutrality, vacuum drying obtains the ring of 5- ethyls two
[2,2,1] hept-2-ene", vinylene carbonate bipolymer.It is 42.3% to calculate reaction yield.
Embodiment 8
In the there-necked flask of dry atmosphere of inert gases, by 0.006 mole three (butyl cyclopentadiene) change scandium and
0.010 mole of isoquinolin is dissolved in 10 milliliters of 1,2- dichloroethanes, under 250rpm, 0.001 mole of diethyl zinc is instilled
In stating solution, constant temperature is stirred 60 minutes at 40 DEG C of same stir speed (S.S.) after dripping off, and obtains final product scandium-zinc complex catalyst.
0.01 mole of 5,5- dimethyl two ring [2,2,1] hept-2-ene", 0.01 mole of vinylene carbonate are added to repeatedly
Vacuumize, in nitrogen charging autoclave, plus 20ml1,2- dichloroethanes dissolving.Change the amount of scandium by catalyst three (butyl cyclopentadiene)
It is calculated as 5,5- dimethyl two ring [2,2,1] hept-2-ene", the 0.30% of both vinylene carbonates gross weight takes above-mentioned scandium-zinc network
Mixture catalyst, is injected in above-mentioned mixture with syringe.Constant temperature reacts 4 hours at 50 DEG C under 0.9MPa pressure.Product is poured into
Copolymer is precipitated in ethanol solution containing 5wt% hydrochloric acid, precipitates washed with EtOH to neutrality, vacuum drying obtains 5,
5- dimethyl two ring [2,2,1] hept-2-ene", vinylene carbonate bipolymer.It is 45.1% to calculate reaction yield.
Embodiment 9
In the there-necked flask of dry atmosphere of inert gases, by 0.001 mole three (butyl cyclopentadiene) change scandium and
0.008 mole of α, α '-bipyridyl is dissolved in 10 milliliters of hexamethylenes, under 280rpm, 0.008 mole of diethyl zinc is instilled above-mentioned
In solution, constant temperature is stirred 60 minutes at 60 DEG C of same stir speed (S.S.) after dripping off, and obtains final product scandium-zinc complex catalyst.
0.01 mole of 1- phenyl two ring [2,2,1] hept-2-ene", 0.01 mole of vinylene carbonate are added to and repeatedly take out very
In empty, nitrogen charging autoclave, plus the dissolving of 20ml hexamethylenes.The amount for changing scandium by catalyst three (butyl cyclopentadiene) is calculated as 1- phenyl
Two rings [2,2,1] hept-2-ene", the 0.60% of both vinylene carbonates gross weight take above-mentioned scandium-zinc complex catalyst, use
Syringe is injected in above-mentioned mixture.Constant temperature reacts 6 hours at 70 DEG C under 1.5MPa pressure.Product is poured into containing 5wt% hydrochloric acid
Precipitate copolymer in ethanol solution, precipitates washed with EtOH to neutrality, vacuum drying, that is, obtain the ring of 1- phenyl two [2,2,
1] hept-2-ene", vinylene carbonate bipolymer.It is 71.6% to calculate reaction yield.
Embodiment 10
In the there-necked flask of dry atmosphere of inert gases, by 0.001 mole three (butyl cyclopentadiene) change scandium and
0.005 mole of α, α '-bipyridyl is dissolved in 10 milliliters of cyclohexanone, under 220rpm, 0.007 mole of diethyl zinc is instilled above-mentioned
In solution, constant temperature is stirred 60 minutes at 45 DEG C of same stir speed (S.S.) after dripping off, and obtains final product scandium-zinc complex catalyst.
0.01 mole of 5- phenyl two ring [2,2,1] hept-2-ene", 0.01 mole of vinylene carbonate are added to and repeatedly take out very
In empty, nitrogen charging autoclave, plus the dissolving of 20ml cyclohexanone.The amount for changing scandium by catalyst three (butyl cyclopentadiene) is calculated as 5- phenyl
Two rings [2,2,1] hept-2-ene", the 0.8% of both vinylene carbonates gross weight take above-mentioned scandium-zinc complex catalyst, with note
Emitter is injected in above-mentioned mixture.Constant temperature reacts 3 hours at 60 DEG C under 2MPa pressure.Product is poured into the ethanol containing 5wt% hydrochloric acid
Precipitate copolymer in solution, precipitates washed with EtOH to neutrality, vacuum drying obtains 5- phenyl two ring [2,2,1] hept-
2- alkene, vinylene carbonate bipolymer.It is 65.6% to calculate reaction yield.
Embodiment 11
In the there-necked flask of dry atmosphere of inert gases, by 0.001 mole three (butyl cyclopentadiene) change scandium and
0.006 mole of Phen is dissolved in 10 milliliters of toluene, under 190rpm, 0.009 mole of diethyl zinc is instilled into above-mentioned solution
In, constant temperature is stirred 60 minutes at 60 DEG C of same stir speed (S.S.) after dripping off, and obtains final product scandium-zinc complex catalyst.
0.01 mole of 5- vinyl two ring [2,2,1] hept-2-ene", 0.01 mole of vinylene carbonate are added to and repeatedly taken out
In vacuum, nitrogen charging autoclave, plus the dissolving of 20ml toluene.The amount for changing scandium by catalyst three (butyl cyclopentadiene) is calculated as 5- ethene
Base two ring [2,2,1] hept-2-ene", the 0.06% of both vinylene carbonates gross weight take above-mentioned scandium-zinc complex catalyst,
Injected in above-mentioned mixture with syringe.Constant temperature reacts 4 hours at 100 DEG C under 7MPa pressure.Product is poured into hydrochloric acid containing 5wt%
Ethanol solution in precipitate copolymer, precipitates washed with EtOH to neutrality, vacuum drying, that is, obtain the ring of 5- vinyl two
[2,2,1] hept-2-ene", vinylene carbonate bipolymer.It is 76.3% to calculate reaction yield.
Embodiment 12
In the there-necked flask of dry atmosphere of inert gases, by 0.001 mole three (butyl cyclopentadiene) change scandium and
0.005 mole of isoquinolin is dissolved in 10 milliliters of tetrahydrofurans, under 160rpm, 0.006 mole of diethyl zinc is instilled above-mentioned molten
In liquid, constant temperature is stirred 40 minutes at 40 DEG C of same stir speed (S.S.) after dripping off, and obtains final product scandium-zinc complex catalyst.
0.01 mole of two ring [2,2,1] hept-2-ene" -5- methyl formate, 0.01 mole of vinylene carbonate are added to many
It is secondary vacuumize, in nitrogen charging autoclave, plus 20ml tetrahydrofurans dissolving.Change the gauge of scandium by catalyst three (butyl cyclopentadiene)
For two rings [2,2,1] hept-2-ene" -5- methyl formates, both vinylene carbonates gross weight 0.04% take above-mentioned scandium-zinc network
Mixture catalyst, is injected in above-mentioned mixture with syringe.Constant temperature reacts 1 hour at 90 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" -5- methyl formates, vinylene carbonate bipolymer.It is 55.2% to calculate reaction yield.
Embodiment 13
In the there-necked flask of dry atmosphere of inert gases, by 0.010 mole three (butyl cyclopentadiene) change scandium and
0.004 mole of quinoline is dissolved in 10 milliliters of petroleum ethers, under 280rpm, during 0.003 mole of diethyl zinc 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 scandium-zinc complex catalyst.
0.01 mole of two ring [2,2,1] hept-2-ene" -5- formic acid spy butyl ester, 0.01 mole of vinylene carbonate are added to
Repeatedly vacuumize, in nitrogen charging autoclave, plus 20ml petroleum ether dissolutions.Change the gauge of scandium by catalyst three (butyl cyclopentadiene)
For two rings [2,2,1] hept-2-ene" -5- formic acid spy butyl ester, both vinylene carbonates gross weight 0.06% take above-mentioned scandium-zinc
Complex compound catalyst, is injected in above-mentioned mixture with syringe.Constant temperature reacts 2 hours at 130 DEG C under 3MPa pressure.Product inclines
Entering precipitate copolymer in the ethanol solution containing 5wt% hydrochloric acid, precipitates washed with EtOH to neutrality, vacuum drying, that is, obtain
Two rings [2,2,1] hept-2-ene" -5- formic acid spy butyl ester, vinylene carbonate bipolymer.It is 50.5% to calculate reaction yield.
Embodiment 14
In the there-necked flask of dry atmosphere of inert gases, by 0.010 mole three (butyl cyclopentadiene) change scandium and
0.006 mole of porphyrin is dissolved in 10 milliliters of methyl phenyl ethers anisoles, under 240rpm, during 0.002 mole of diethyl zinc instilled into above-mentioned solution,
Constant temperature is stirred 30 minutes at 50 DEG C of same stir speed (S.S.) after dripping off, and obtains final product scandium-zinc complex catalyst.
0.01 mole of two ring [2,2,1] hept-2-ene" -5- formic acid spy butyl ester, 0.01 mole of vinylene carbonate are added to
Repeatedly vacuumize, in nitrogen charging autoclave, plus 20ml methyl phenyl ethers anisoles dissolving.Change the gauge of scandium by catalyst three (butyl cyclopentadiene)
For two rings [2,2,1] hept-2-ene" -5- formic acid spy butyl ester, both vinylene carbonates gross weight 0.07% take above-mentioned scandium-zinc
Complex compound catalyst, is injected in above-mentioned mixture with syringe.Constant temperature reacts 5 hours at 50 DEG C under 5MPa pressure.Product is poured into
Copolymer is precipitated in ethanol solution containing 5wt% hydrochloric acid, precipitates washed with EtOH to neutrality, vacuum drying obtains two
Ring [2,2,1] hept-2-ene" -5- formic acid spy butyl ester, vinylene carbonate bipolymer.It is 48.3% to calculate reaction yield.
Embodiment 15
In the there-necked flask of dry atmosphere of inert gases, by 0.003 mole three (butyl cyclopentadiene) change scandium and
0.013 mole of α, α '-bipyridyl is dissolved in 10 milliliters of hexamethylenes, under 250rpm, 0.018 mole of diethyl zinc is instilled above-mentioned
In solution, constant temperature is stirred 60 minutes at 40 DEG C of same stir speed (S.S.) after dripping off, and obtains final product scandium-zinc complex catalyst.
0.01 mole of two ring [2,2,1] hept-2-ene", 0.01 mole of vinylene carbonate are added to and are repeatedly vacuumized, filled
In nitrogen autoclave, plus the dissolving of 20ml hexamethylenes.The amount for changing scandium by catalyst three (butyl cyclopentadiene) is calculated as two rings [2,2,1]
Hept-2-ene", the 0.10% of both vinylene carbonates gross weight take above-mentioned scandium-zinc complex catalyst, are injected with syringe
In stating mixture.Constant temperature reacts 6 hours at 70 DEG C under 6MPa pressure.Product is poured into the ethanol solution containing 5wt% hydrochloric acid to be made altogether
Polymers is precipitated, precipitates washed with EtOH to neutrality, vacuum drying, that is, obtain two rings [2,2,1] hept-2-ene", vinylene carbonate
Ester bipolymer.It is 71.9% to calculate reaction yield.
Embodiment 16
In the there-necked flask of dry atmosphere of inert gases, by 0.001 mole three (butyl cyclopentadiene) change scandium and
0.003 mole of 8-hydroxyquinoline is dissolved in 10 milliliters of benzene, under 260rpm, 0.004 mole of diethyl zinc 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 scandium-zinc complex catalyst.
0.01 mole of 1- methyl bicyclics [2,2,1] hept-2-ene", 0.01 mole of vinylene carbonate are added to and repeatedly take out very
In empty, nitrogen charging autoclave, plus the dissolving of 20ml benzene.The amount for changing scandium by catalyst three (butyl cyclopentadiene) is calculated as 1- methyl bicyclics
[2,2,1] hept-2-ene", the 1.20% of both vinylene carbonates gross weight take above-mentioned scandium-zinc complex catalyst, with injection
Device is injected in above-mentioned mixture.Constant temperature reacts 5 hours at 130 DEG C under 5MPa pressure.Product is poured into the ethanol containing 5wt% hydrochloric acid
Precipitate copolymer in solution, precipitates washed with EtOH to neutrality, vacuum drying obtains 1- methyl bicyclics [2,2,1] hept-
2- alkene, vinylene carbonate bipolymer.It is 57.6% to calculate reaction yield.
Claims (5)
1. norborneol alkenes and vinylene carbonate binary copolymerization catalyst, it is characterised in that the preparation method of the catalyst is such as
Under：
In the there-necked flask of dry atmosphere of inert gases, three (butyl cyclopentadiene) change scandium and part are dissolved in first molten
In agent, under 150~300rpm, diethyl zinc is instilled, constant temperature stirs 30- under same stir speed (S.S.) at 30-60 DEG C after dripping off
60 minutes, obtain final product scandium-zinc complex catalyst；
It is 1: 15~15: 1, three (the butyl ring penta 2 that three (the butyl cyclopentadiene) change scandium with the mol ratio of the part
Alkene) mol ratio of changing scandium and the diethyl zinc is 1: 15~15: 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 ratio that the consumption of the solvent and three (the butyl cyclopentadiene) change scandium, diethyl zinc and part three's total amount is 10
Milliliter：0.005~0.035 mole.
2. norborneol alkenes according to claim 1 and vinylene carbonate binary copolymerization catalyst, it is characterised in that institute
The mol ratio for stating three (butyl cyclopentadiene) change scandium, diethyl zinc and part three is 1: 10: 6.
3. norborneol alkenes according to claim 1 and 2 and vinylene carbonate binary copolymerization catalyst, it is characterised in that
The part and first solvent are first dried using preceding；The drying of the solid-state part in wherein described part is first to use
The purifying of recrystallization method and then vacuum drying；The drying of the liquid part in the part is dried with calcium hydride or metallic sodium,
The solvent is dried using calcium chloride or calcium hydride.
4. urged using the norborneol alkenes and vinylene carbonate binary copolymerization as described in claims 1 to 3 any claim
The norborneol alkenes and vinylene carbonate binary copolymerization method of agent, it is characterised in that comprise the steps：
Take norborneol alkenes according to mol ratio 1: 1 and vinylene carbonate ester monomer be added to repeatedly vacuumize, in nitrogen charging reactor,
The second solvent is added to dissolve；It is subsequently adding described scandium-zinc complex catalyst, at 20~130 DEG C, 0.1-8MPa pressure
Lower reaction 1~6 hour；
The product for obtaining will be reacted to pour into the ethanol solution containing 4.5-5.5wt% hydrochloric acid, the precipitates washed with EtOH for obtaining
To neutral, ENB class and vinylene carbonate bipolymer are obtained after vacuum drying；
The consumption of the scandium-zinc complex catalyst is calculated as norborneol by the amount that in catalyst three (butyl cyclopentadiene) change scandium
The 0.01%-1.5% of both alkenes and vinylene carbonate 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 and vinylene carbonate binary copolymerization method, it is characterised in that described
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", the ring of 5- ethyls two [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", the ring of 5- phenyl two [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 butyl ester.
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Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2007126263A1 (en) * | 2006-04-28 | 2007-11-08 | Lg Chem, Ltd. | Alkene-acrylate-norbornene terpolymer and method for preparing the same |
| WO2009069973A2 (en) * | 2007-11-28 | 2009-06-04 | Lg Chem, Ltd. | Catalytic composition for producing 1-alkene and acrylates copolymer and method for producing 1-alkene and acrylates copolymer |
| CN104140495A (en) * | 2014-08-06 | 2014-11-12 | 宁波工程学院 | Norbornene, acrylics and octafluorocyclopentene ternary polymerization catalyst 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 |
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Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2007126263A1 (en) * | 2006-04-28 | 2007-11-08 | Lg Chem, Ltd. | Alkene-acrylate-norbornene terpolymer and method for preparing the same |
| WO2009069973A2 (en) * | 2007-11-28 | 2009-06-04 | Lg Chem, Ltd. | Catalytic composition for producing 1-alkene and acrylates copolymer and method for producing 1-alkene and acrylates copolymer |
| CN104140495A (en) * | 2014-08-06 | 2014-11-12 | 宁波工程学院 | Norbornene, acrylics and octafluorocyclopentene ternary polymerization catalyst 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 |
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