CN106832118B - 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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- CN106832118B CN106832118B CN201710086962.7A CN201710086962A CN106832118B CN 106832118 B CN106832118 B CN 106832118B CN 201710086962 A CN201710086962 A CN 201710086962A CN 106832118 B CN106832118 B CN 106832118B
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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
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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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- C08F4/44—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 characterized in that the catalyst the preparation method is as follows: in the three-necked flask of dry atmosphere of inert gases, three (butyl cyclopentadiene) are changed into scandium and ligand is dissolved in the first solvent, at 150~300rpm, instill diethyl zinc, constant temperature stirs 30-60 minutes to get scandium-zinc complex catalyst under same stirring rate at 30-60 DEG C after dripping off；It takes norborneol alkenes and vinylene carbonate ester monomer to be added to according to molar ratio 1: 1 repeatedly to vacuumize, in nitrogen charging reaction kettle, the dissolution of the second solvent is added；Then scandium-zinc complex the catalyst is added to react 1~6 hour under 0.1-8MPa pressure at 20~130 DEG C；The product that reaction obtains is poured into the ethanol solution of the hydrochloric acid containing 4.5-5.5wt%, obtained precipitates washed with EtOH to neutrality, norbornene class and vinylene carbonate bipolymer are obtained 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 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 oxygen-containing alkene is inserted into polynorbornene main chain, the caking property and solubility of polymer can be improved, and reduce material
The absorptance of itself.This copolymer can be used as photoresist applied to 193nm replica technology.Moreover, the hair of microelectronics industry
Exhibition needs smaller ingredient, and to the exposure technique that line width is 1.3 μm and following line width is suitable for, 193nm photoetching may be selected
Technology, these technologies are related to the various aspects of photoetching process, propose new optical material and its manufacture and coating technique, novel
Resist, for new material of mask and its protective film etc. up for solving the problems, such as.Therefore, in order to which the photoetching obtained is new
Material has developed alternating copolymerization material, main development norbornene and maleic anhydride, tetrafluoroethene or other component ternary polymerizations
Material, while application has the norbornene of side group, it is therefore an objective to the resistance to corrosion of entire matrix is improved, lithography performance is improved, is increased
Caking property, solubility and the toughness of material.
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 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 lower reaction temperature, high catalytic efficiency and copolymerization
The method of the norborneol alkenes and vinylene carbonate binary copolymerization of object high income.
The technical scheme of the invention to solve the technical problem is: the norborneol alkenes and vinylene carbonate two
First catalyst for copolymerization, 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 (butyl cyclopentadiene) are changed into scandium and ligand and are dissolved in the
In one solvent, at 150~300rpm, diethyl zinc is instilled, constant temperature stirs under same stirring rate at 30-60 DEG C after dripping off
30-60 minutes to get scandium-zinc complex catalyst；
It is 1: 15~15: 1 that three (the butyl cyclopentadiene), which change scandium and the molar ratio of the ligand, three (the butyl ring
Pentadiene) to change the molar ratio of scandium and the diethyl zinc be 1: 15~15: 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 three (the butyl cyclopentadiene) change the ratio of scandium, diethyl zinc and ligand three's total amount
It is 10 milliliters: 0.005~0.035 moles.
It is preferred that it is preferably 1: 10: 6 that three (the butyl cyclopentadiene), which change scandium, diethyl zinc and the molar ratio of ligand three,.
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 the norborneol alkenes and carbonic acid Asia second of above-mentioned norborneol alkenes and vinylene carbonate binary copolymerization catalyst
Enester binary copolymerization method, it is characterised in that include the following steps:
According to molar ratio 1: 1 take norborneol alkenes and vinylene carbonate ester monomer be added to repeatedly vacuumize, nitrogen charging reaction
In kettle, the dissolution of the second solvent is added；Then scandium-zinc complex the catalyst, at 20~130 DEG C, 0.1-8MPa is added
It is reacted 1~6 hour under pressure；
The product that reaction obtains is poured into the ethanol solution of the hydrochloric acid containing 4.5-5.5wt%, obtained sediment ethyl alcohol
Washing obtains norbornene class and vinylene carbonate bipolymer to neutrality after vacuum drying；
The scandium-zinc complex catalyst dosage is calculated as dropping by the amount that in catalyst three (butyl cyclopentadiene) change scandium
The 0.01%-1.5% of both borneol alkenes and vinylene carbonate 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 scandium-zinc complex catalyst complex,
Catalyst raw material is cheap and easy to get, can generate catalytic activity at relatively low temperatures, is catalyzed norborneol alkenes and vinylene carbonate binary
Copolymerization, reaction temperature is lower, high catalytic efficiency, and product is easy to washing separation, 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, solubility and tough
Property is 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 mole three (butyl cyclopentadiene) change scandium and
0.001 mole of 8-hydroxyquinoline is dissolved in 10 milliliters of benzene, and at 150rpm, 0.015 mole of diethyl zinc is instilled above-mentioned solution
In, constant temperature stirs 30 minutes to get scandium-zinc 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 vinylene carbonate are added to and repeatedly vacuumizes, fill
In nitrogen autoclave, 20ml benzene is added to dissolve.Two rings [2,2,1] hept- is calculated as by the amount that in catalyst three (butyl cyclopentadiene) change scandium
The 0.01% of both 2- alkene, vinylene carbonates total weight takes above-mentioned scandium-zinc complex catalyst, is injected with syringe above-mentioned
In mixture.Constant temperature reacts 6 hours under 80 DEG C, 5MPa pressure.Product, which is poured into the ethanol solution of the hydrochloric acid containing 5wt%, to be made to be copolymerized
Object precipitating, precipitates washed with EtOH to neutrality, vacuum drying is to get to two rings [2,2,1] hept-2-ene", vinylene carbonate
Bipolymer.Calculating reaction yield is 43.3%.
The calculation method of reaction yield is bipolymer 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 mole three (butyl cyclopentadiene) change scandium and
0.015 mole of α, α '-bipyridyl is dissolved in 10 milliliters of toluene, at 180rpm, 0.008 mole of diethyl zinc is instilled above-mentioned molten
In liquid, constant temperature stirs 50 minutes to get scandium-zinc complex catalyst at 50 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 vinylene carbonate are added to and repeatedly vacuumizes, fill
In nitrogen autoclave, 20ml toluene is added to dissolve.Two rings [2,2,1] are calculated as by the amount that in catalyst three (butyl cyclopentadiene) change scandium
The 0.09% of both hept-2-ene", vinylene carbonates total weight takes above-mentioned scandium-zinc complex catalyst, is injected with syringe
It states in mixture.Constant temperature reacts 6 hours under 100 DEG C, 4MPa pressure.Product, which is poured into the ethanol solution of the hydrochloric acid containing 5wt%, to be made
Copolymer precipitating, precipitates washed with EtOH to neutrality, vacuum drying is to get to two rings [2,2,1] hept-2-ene", carbonic acid Asia second
Enester bipolymer.Calculating reaction yield is 70.6%.
Embodiment 3
In the three-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, at 250rpm, 0.010 mole of diethyl zinc is instilled above-mentioned
In solution, constant temperature stirs 50 minutes to get scandium-zinc complex catalyst at 45 DEG C of same stirring rate after dripping off.
0.01 mole of 1- methyl bicyclic [2,2,1] hept-2-ene", 0.01 mole of vinylene carbonate are added to and repeatedly taken out very
In empty, nitrogen charging autoclave, 20ml tetrahydrofuran is added to dissolve.1- first is calculated as by the amount that in catalyst three (butyl cyclopentadiene) change scandium
The 0.08% of both two ring of base [2,2,1] hept-2-ene", vinylene carbonates total weight takes above-mentioned scandium-zinc complex catalyst,
It is injected in above-mentioned mixture with syringe.Constant temperature reacts 5 hours under 120 DEG C, 6MPa pressure.Product is poured into hydrochloric acid containing 5wt%
Ethanol solution in precipitate copolymer, precipitates washed with EtOH to neutrality, vacuum drying to get to 1- methyl bicyclic [2,
2,1] hept-2-ene", vinylene carbonate bipolymer.Calculating reaction yield is 88.6%.
Embodiment 4
In the three-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, and at 300 rpm, 0.012 mole of diethyl zinc is instilled in above-mentioned solution,
Constant temperature stirs 60 minutes to get scandium-zinc complex catalyst at 50 DEG C of same stirring rate after dripping off.
0.01 mole of 5- methyl bicyclic [2,2,1] hept-2-ene", 0.01 mole of vinylene carbonate are added to and repeatedly taken out very
In empty, nitrogen charging autoclave, add 20ml petroleum ether dissolution.5- methyl is calculated as by the amount that in catalyst three (butyl cyclopentadiene) change scandium
The 0.10% of both two rings [2,2,1] hept-2-ene", vinylene carbonates total weight takes above-mentioned scandium-zinc complex catalyst, uses
Syringe injects in above-mentioned mixture.Constant temperature reacts 4 hours under 130 DEG C, 8MPa pressure.Product is poured into the hydrochloric acid containing 5wt%
Precipitate copolymer in ethanol solution, precipitates washed with EtOH to neutrality, vacuum drying to get to 5- methyl bicyclic [2,2,
1] hept-2-ene", vinylene carbonate bipolymer.Calculating reaction yield is 82.2%.
Embodiment 5
In the three-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, and at 200 rpm, 0.015 mole of diethyl zinc is instilled in above-mentioned solution,
Constant temperature stirs 40 minutes to get scandium-zinc complex catalyst at 60 DEG C of same stirring rate after dripping off.
0.01 mole of 7- methyl bicyclic [2,2,1] hept-2-ene", 0.01 mole of vinylene carbonate are added to and repeatedly taken out very
In empty, nitrogen charging autoclave, 20ml methyl phenyl ethers anisole is added to dissolve.7- methyl is calculated as by the amount that in catalyst three (butyl cyclopentadiene) change scandium
The 0.07% of both two rings [2,2,1] hept-2-ene", vinylene carbonates total weight takes above-mentioned scandium-zinc complex catalyst, uses
Syringe injects in above-mentioned mixture.Constant temperature reacts 5 hours under 90 DEG C, 3MPa pressure.Product is poured into the second of the hydrochloric acid containing 5wt%
Precipitate copolymer in alcoholic solution, precipitates washed with EtOH to neutrality is dried in vacuo to get 7- methyl bicyclic [2,2,1] are arrived
Hept-2-ene", vinylene carbonate bipolymer.Calculating reaction yield is 74.2%.
Embodiment 6
In the three-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, and at 160rpm, 0.006 mole of diethyl zinc is dripped
Enter in above-mentioned solution, constant temperature stirs 40 minutes to get scandium-zinc complex catalyst at 30 DEG C of same stirring rate after dripping off.
0.01 mole of two ring of 1- ethyl [2,2,1] hept-2-ene", 0.01 mole of vinylene carbonate are added to and repeatedly taken out very
In empty, nitrogen charging autoclave, add 20ml1, the dissolution of 4- dioxane.It is calculated as by the amount that in catalyst three (butyl cyclopentadiene) change scandium
The 1.00% of both two ring of 1- ethyl [2,2,1] hept-2-ene", vinylene carbonates total weight takes above-mentioned scandium-zinc complex catalysis
Agent is injected in above-mentioned mixture with syringe.Constant temperature reacts 3 hours under 20 DEG C, 1MPa pressure.Product is poured into salt containing 5wt%
Precipitate copolymer in the ethanol solution of acid, precipitates washed with EtOH to neutrality is dried in vacuo to get two ring of 1- ethyl is arrived
[2,2,1] hept-2-ene", vinylene carbonate bipolymer.Calculating reaction yield is 49.2%.
Embodiment 7
In the three-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, and at 270rpm, 0.001 mole of diethyl zinc is dripped
Enter in above-mentioned solution, constant temperature stirs 40 minutes to get scandium-zinc complex catalyst at 40 DEG C of same stirring rate after dripping off.
0.01 mole of two ring of 5- ethyl [2,2,1] hept-2-ene", 0.01 mole of vinylene carbonate are added to and repeatedly taken out very
In empty, nitrogen charging autoclave, add 20ml1, the dissolution of 4- dioxane.It is calculated as by the amount that in catalyst three (butyl cyclopentadiene) change scandium
The 1.50% of both two ring of 5- ethyl [2,2,1] hept-2-ene", vinylene carbonates total weight takes above-mentioned scandium-zinc complex catalysis
Agent is injected in above-mentioned mixture with syringe.Constant temperature reacts 4 hours under 60 DEG C, 0.1MPa pressure.Product is poured into containing 5wt%
Precipitate copolymer in the ethanol solution of hydrochloric acid, precipitates washed with EtOH to neutrality is dried in vacuo to get two ring of 5- ethyl is arrived
[2,2,1] hept-2-ene", vinylene carbonate bipolymer.Calculating reaction yield is 42.3%.
Embodiment 8
In the three-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, and at 250rpm, 0.001 mole of diethyl zinc is instilled
It states in solution, constant temperature stirs 60 minutes to get scandium-zinc complex catalyst at 40 DEG C of same stirring rate after dripping off.
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
It vacuumizes, in nitrogen charging autoclave, adds 20ml1, the dissolution of 2- dichloroethanes.Change the amount of scandium by catalyst three (butyl cyclopentadiene)
Be calculated as both 5,5- dimethyl, two ring [2,2,1] hept-2-ene", vinylene carbonates total weight 0.30% takes above-mentioned scandium-zinc network
Mixture catalyst is injected in above-mentioned mixture with syringe.Constant temperature reacts 4 hours under 50 DEG C, 0.9MPa pressure.Product is poured into
Precipitate copolymer in the ethanol solution of the hydrochloric acid containing 5wt%, precipitates washed with EtOH to neutrality, vacuum drying to get to 5,
Two ring of 5- dimethyl [2,2,1] hept-2-ene", vinylene carbonate bipolymer.Calculating reaction yield is 45.1%.
Embodiment 9
In the three-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, at 280rpm, 0.008 mole of diethyl zinc is instilled above-mentioned
In solution, constant temperature stirs 60 minutes to get scandium-zinc complex catalyst at 60 DEG C of same stirring rate after dripping off.
0.01 mole of two ring of 1- phenyl [2,2,1] hept-2-ene", 0.01 mole of vinylene carbonate are added to and repeatedly taken out very
In empty, nitrogen charging autoclave, 20ml hexamethylene is added to dissolve.1- phenyl is calculated as by the amount that in catalyst three (butyl cyclopentadiene) change scandium
The 0.60% of both two rings [2,2,1] hept-2-ene", vinylene carbonates total weight takes above-mentioned scandium-zinc complex catalyst, uses
Syringe injects in above-mentioned mixture.Constant temperature reacts 6 hours under 70 DEG C, 1.5MPa pressure.Product is poured into the hydrochloric acid containing 5wt%
Precipitate copolymer in ethanol solution, precipitates washed with EtOH to neutrality, vacuum drying to get to two ring of 1- phenyl [2,2,
1] hept-2-ene", vinylene carbonate bipolymer.Calculating reaction yield is 71.6%.
Embodiment 10
In the three-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, at 220rpm, 0.007 mole of diethyl zinc is instilled above-mentioned
In solution, constant temperature stirs 60 minutes to get scandium-zinc complex catalyst at 45 DEG C of same stirring rate after dripping off.
0.01 mole of two ring of 5- phenyl [2,2,1] hept-2-ene", 0.01 mole of vinylene carbonate are added to and repeatedly taken out very
In empty, nitrogen charging autoclave, 20ml cyclohexanone is added to dissolve.5- phenyl is calculated as by the amount that in catalyst three (butyl cyclopentadiene) change scandium
The 0.8% of both two rings [2,2,1] hept-2-ene", vinylene carbonates total weight takes above-mentioned scandium-zinc complex catalyst, with note
Emitter is injected in above-mentioned mixture.Constant temperature reacts 3 hours under 60 DEG C, 2MPa pressure.Product is poured into the ethyl alcohol of the hydrochloric acid containing 5wt%
Precipitate copolymer in solution, precipitates washed with EtOH to neutrality is dried in vacuo to get two ring of 5- phenyl [2,2,1] hept- is arrived
2- alkene, vinylene carbonate bipolymer.Calculating reaction yield is 65.6%.
Embodiment 11
In the three-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, and at 190rpm, 0.009 mole of diethyl zinc is instilled above-mentioned solution
In, constant temperature stirs 60 minutes to get scandium-zinc complex catalyst at 60 DEG C of same stirring rate after dripping off.
0.01 mole of two ring of 5- vinyl [2,2,1] hept-2-ene", 0.01 mole of vinylene carbonate are added to multiple pumping
In vacuum, nitrogen charging autoclave, 20ml toluene is added to dissolve.5- ethylene is calculated as by the amount that in catalyst three (butyl cyclopentadiene) change scandium
The 0.06% of both two ring of base [2,2,1] hept-2-ene", vinylene carbonates total weight takes above-mentioned scandium-zinc complex catalyst,
It is injected in above-mentioned mixture with syringe.Constant temperature reacts 4 hours under 100 DEG C, 7MPa pressure.Product is poured into hydrochloric acid containing 5wt%
Ethanol solution in precipitate copolymer, precipitates washed with EtOH to neutrality, vacuum drying to get arrive two ring of 5- vinyl
[2,2,1] hept-2-ene", vinylene carbonate bipolymer.Calculating reaction yield is 76.3%.
Embodiment 12
In the three-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, at 160rpm, 0.006 mole of diethyl zinc is instilled above-mentioned molten
In liquid, constant temperature stirs 40 minutes to get scandium-zinc complex catalyst at 40 DEG C of same stirring rate after dripping off.
0.01 mole of two ring [2,2,1] hept-2-ene" -5- methyl formate, 0.01 mole of vinylene carbonate are added to more
It is secondary to vacuumize, in nitrogen charging autoclave, add 20ml tetrahydrofuran to dissolve.Change the meter of scandium by catalyst three (butyl cyclopentadiene)
0.04% for both two rings [2,2,1] hept-2-ene" -5- methyl formate, vinylene carbonate total weight takes above-mentioned scandium-zinc network
Mixture catalyst is injected in above-mentioned mixture with syringe.Constant temperature reacts 1 hour under 90 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" -5- methyl formate, vinylene carbonate bipolymer.Calculating reaction yield is 55.2%.
Embodiment 13
In the three-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, and at 280rpm, 0.003 mole of diethyl zinc is instilled in above-mentioned solution,
Constant temperature stirs 50 minutes to get scandium-zinc complex catalyst at 50 DEG C of same stirring rate after dripping off.
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
It repeatedly vacuumizes, in nitrogen charging autoclave, adds 20ml petroleum ether dissolution.Change the meter of scandium by catalyst three (butyl cyclopentadiene)
0.06% for both two rings [2,2,1] hept-2-ene" -5- formic acid spy butyl ester, vinylene carbonate total weight takes above-mentioned scandium-zinc
Complex compound catalyst is injected in above-mentioned mixture with syringe.Constant temperature reacts 2 hours under 130 DEG C, 3MPa pressure.Product inclines
Entering in the ethanol solution of the hydrochloric acid containing 5wt% precipitates copolymer, precipitates washed with EtOH to neutrality, is dried in vacuo to get arriving
Two rings [2,2,1] hept-2-ene" -5- formic acid spy butyl ester, vinylene carbonate bipolymer.Calculating reaction yield is 50.5%.
Embodiment 14
In the three-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, and at 240rpm, 0.002 mole of diethyl zinc is instilled in above-mentioned solution,
Constant temperature stirs 30 minutes to get scandium-zinc complex catalyst at 50 DEG C of same stirring rate after dripping off.
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
It repeatedly vacuumizes, in nitrogen charging autoclave, 20ml methyl phenyl ethers anisole is added to dissolve.Change the meter of scandium by catalyst three (butyl cyclopentadiene)
0.07% for both two rings [2,2,1] hept-2-ene" -5- formic acid spy butyl ester, vinylene carbonate total weight takes above-mentioned scandium-zinc
Complex compound catalyst is injected in above-mentioned mixture with syringe.Constant temperature reacts 5 hours under 50 DEG C, 5MPa pressure.Product is poured into
Precipitate copolymer in the ethanol solution of the hydrochloric acid containing 5wt%, precipitates washed with EtOH to neutrality, vacuum drying is to get to two
Ring [2,2,1] hept-2-ene" -5- formic acid spy butyl ester, vinylene carbonate bipolymer.Calculating reaction yield is 48.3%.
Embodiment 15
In the three-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, at 250rpm, 0.018 mole of diethyl zinc is instilled above-mentioned
In solution, constant temperature stirs 60 minutes to get scandium-zinc complex catalyst at 40 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 vinylene carbonate are added to and repeatedly vacuumizes, fill
In nitrogen autoclave, 20ml hexamethylene is added to dissolve.Two rings [2,2,1] are calculated as by the amount that in catalyst three (butyl cyclopentadiene) change scandium
The 0.10% of both hept-2-ene", vinylene carbonates total weight takes above-mentioned scandium-zinc complex catalyst, is injected with syringe
It states in mixture.Constant temperature reacts 6 hours under 70 DEG C, 6MPa pressure.Product, which is poured into the ethanol solution of the hydrochloric acid containing 5wt%, to be made altogether
Polymers precipitating, precipitates washed with EtOH to neutrality, vacuum drying is to get to two rings [2,2,1] hept-2-ene", vinylene carbonate
Ester bipolymer.Calculating reaction yield is 71.9%.
Embodiment 16
In the three-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, and at 260rpm, 0.004 mole of diethyl zinc is instilled above-mentioned solution
In, constant temperature stirs 50 minutes to get scandium-zinc complex catalyst at 50 DEG C of same stirring rate after dripping off.
0.01 mole of 1- methyl bicyclic [2,2,1] hept-2-ene", 0.01 mole of vinylene carbonate are added to and repeatedly taken out very
In empty, nitrogen charging autoclave, 20ml benzene is added to dissolve.1- methyl bicyclic is calculated as by the amount that in catalyst three (butyl cyclopentadiene) change scandium
The 1.20% of both [2,2,1] hept-2-ene", vinylene carbonates total weight takes above-mentioned scandium-zinc complex catalyst, with injection
Device injects in above-mentioned mixture.Constant temperature reacts 5 hours under 130 DEG C, 5MPa pressure.Product is poured into the ethyl alcohol of the hydrochloric acid containing 5wt%
Precipitate copolymer in solution, precipitates washed with EtOH to neutrality is dried in vacuo to get 1- methyl bicyclic [2,2,1] hept- is arrived
2- alkene, vinylene carbonate bipolymer.Calculating reaction yield is 57.6%.
Claims (4)
1. norborneol alkenes and vinylene carbonate binary copolymerization method, it is characterised in that the preparation method of used catalyst is such as
Under:
In the three-necked flask of dry atmosphere of inert gases, it is molten that three (butyl cyclopentadiene) change scandium and ligand are dissolved in first
In agent, at 150~300rpm, diethyl zinc is instilled, constant temperature stirs 30- under same stirring rate at 30-60 DEG C after dripping off
60 minutes to get scandium-zinc complex catalyst；
It is 1: 15~15: 1 that three (the butyl cyclopentadiene), which change scandium and the molar ratio of the ligand, three (the butyl ring penta 2
Alkene) to change the molar ratio of scandium and the diethyl zinc be 1: 15~15: 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 ratio that the dosage of the solvent and three (the butyl cyclopentadiene) change scandium, diethyl zinc and ligand three's total amount is 10
Milliliter: 0.005~0.035 mole；
Norborneol alkenes and vinylene carbonate binary copolymerization method include the following steps:
It takes norborneol alkenes and vinylene carbonate ester monomer to be added to according to molar ratio 1: 1 repeatedly to vacuumize, in nitrogen charging reaction kettle,
The dissolution of the second solvent is added；Then scandium-zinc complex the catalyst, at 20~130 DEG C, 0.1-8MPa pressure is added
Lower reaction 1~6 hour；
The product that reaction obtains is poured into the ethanol solution of the hydrochloric acid containing 4.5-5.5wt%, obtained precipitates washed with EtOH
To neutrality, norbornene class and vinylene carbonate bipolymer are obtained after vacuum drying；
The scandium-zinc complex catalyst dosage 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 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 and vinylene carbonate binary copolymerization method, it is characterised in that described
It is 1: 10: 6 that three (butyl cyclopentadiene), which change scandium, diethyl zinc and the molar ratio of ligand three,.
3. norborneol alkenes according to claim 1 or 2 and vinylene carbonate binary copolymerization method, it is characterised in that institute
Ligand and first solvent is stated first to be dried using preceding；Wherein the drying of the solid-state ligand in the ligand is first with weight
Then the purifying of crystallization method is dried in vacuo；The drying of liquid ligand in the ligand is, institute dry with calcium hydride or metallic sodium
It is dry using calcium chloride or calcium hydride to state solvent.
4. norborneol alkenes according to claim 1 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 bicyclic [2,2,1] hept-2-ene", 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-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", 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.
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|---|---|---|---|---|
| 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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