CN106749912B - Norborneol alkenes, vinylacetate and N-phenylmaleimide ternary polymerization catalyst and method for ternary polymerization - Google Patents
Norborneol alkenes, vinylacetate and N-phenylmaleimide ternary polymerization catalyst and method for ternary polymerization Download PDFInfo
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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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- C08F4/42—Metals; Metal hydrides; Metallo-organic compounds; Use thereof as catalyst precursors
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- 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
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Abstract
The present invention relates to a kind of norborneol alkenes, vinylacetate and N-phenylmaleimide ternary polymerization catalyst and method for ternary polymerization, it is characterized in that the catalyst the preparation method is as follows: in the three-necked flask of dry inert atmosphere, dicyclopentadienyl nickel and ligand are dissolved in the first solvent, at 190~210rpm, instill tetraisopropoxy titanium, constant temperature stirs 20-50 minutes to get Ni-Ti complex compound catalyst under same stirring rate at 20-50 DEG C after dripping off；It takes norborneol alkenes, vinylacetate and N-phenylmaleimide monomer to be added to repeatedly to vacuumize, in the reaction kettle of nitrogen charging, the dissolution of the second solvent is added；Then the Ni-Ti complex compound catalyst is added, is reacted under certain temperature and pressure；The product that reaction obtains is poured into the ethanol solution of the hydrochloric acid containing 4-5wt%, obtained precipitates washed with EtOH to neutrality, norbornene class, vinylacetate and N-phenylmaleimide terpolymer are obtained after vacuum drying.
Description
Technical field
The present invention relates to high polymer field, a kind of norborneol alkenes, vinylacetate and N- phenyl Malaysia acyl are referred specifically to
Imines ternary polymerization catalyst and method for ternary polymerization.
Background technique
Polynorbornene is a kind of special polymer, with excellent mechanical property, heat resistance, in organic solvent
The soluble and transparency, can be used for 193nm ultraviolet light photoetching.This material major defect be brittleness, viscosity difference it is low with molecular weight
Deng.After oxygenatedchemicals is inserted into polynorbornene main chain, the caking property and solubility of polymer can be improved, and reduce material
Expect the absorptance of itself.This copolymer can be used as photoresist applied to 193nm replica technology.Moreover, microelectronics industry
193nm light may be selected to the exposure technique that line width is 1.3 μm and following line width is suitable in the smaller ingredient of development need
Lithography, these technologies are related to the various aspects of photoetching process, propose new optical material and its manufacture with coating technique, newly
Type resist, for new material of mask and its protective film etc. up for solving the problems, such as.Therefore, the photoetching in order to obtain
New material has developed alternating copolymerization material, main development norbornene and acrylate or other component ternary polymerization materials, together
Shi Yingyong has the norbornene of side group, it is therefore an objective to improve the resistance to corrosion of entire matrix, improve lithography performance, increase the viscous of material
Knot property, solubility and toughness.
The method for synthesizing these materials at present mainly has the methods of free radical, living radical, metallic catalyst.Such as
The synthesis of photoetching material disclosed in Vol.5039 (2003) page 80~92 of Proceedings of SPIE uses peroxidating
Catalyst of the object as free radical polymerization, disclosed in Vol.4690 (2002) page 127~135 of Proceedings of SPIE
The synthesis of photoetching material uses the catalyst of AINB (azodiisobutyronitrile) as free radical polymerization.A.E.Feiring and
M.Toriumi etc. is by norbornene, tetrafluoroethene and free radical acrylate ternary polymerization etc..These the synthesis sides applied at present
Method is long there are the reaction time, obtains the disadvantages such as copolymer yield is low, molecular weight of copolymer is small, copolymer alternate degree is low.
Summary of the invention
The technical problem to be solved by the present invention is to for the prior art status provide one kind can reduce reaction temperature,
Norborneol alkenes, vinylacetate and the N-phenylmaleimide 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 lower reaction temperature, high catalytic efficiency and copolymerization
Norborneol alkenes, the method for vinylacetate and N-phenylmaleimide ternary polymerization of object high income.
The technical scheme of the invention to solve the technical problem is: norborneol alkenes, vinylacetate and the N-
Phenyl maleimide ternary polymerization catalyst, it is characterised in that the catalyst the preparation method is as follows:
In the three-necked flask of dry inert atmosphere, dicyclopentadienyl nickel and ligand are dissolved in the first solvent, 190~
Under 210rpm, instill tetraisopropoxy titanium, after dripping off at 20-50 DEG C under same stirring rate constant temperature stirring 20-50 minutes, i.e.,
Obtain Ni-Ti complex compound catalyst；
The molar ratio of the dicyclopentadienyl nickel and the ligand is 1: 10~10: 1, the dicyclopentadienyl nickel and the tetraisopropoxy titanium
Molar ratio be 1: 10~10: 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 first solvent and the ratio of the dicyclopentadienyl nickel, tetraisopropoxy titanium and ligand three's total amount are 10 millis
It rises: 0.003~0.030 mole.
It is preferred that the molar ratio of the dicyclopentadienyl nickel, tetraisopropoxy titanium and ligand three is preferably 1: 4: 6.
Preferably, the ligand and first solvent are first dried using preceding；The wherein solid-state in the ligand
The drying of ligand is first to be purified then to be dried in vacuo with recrystallization method；The drying of liquid ligand in the ligand is with hydrogenation
Calcium or metallic sodium are dry, and the solvent is dry using calcium chloride or calcium hydride.
Use above-mentioned norborneol alkenes, the norborneol of vinylacetate and N-phenylmaleimide ternary polymerization catalyst
Alkenes, vinylacetate and N-phenylmaleimide method for ternary polymerization, it is characterised in that include the following steps:
Norborneol alkenes, vinylacetate and N-phenylmaleimide monomer is taken to be added to according to molar ratio 1: 1: 1 more
It is secondary to vacuumize, in the reaction kettle of nitrogen charging, the dissolution of the second solvent is added；Then the Ni-Ti complex compound catalyst is added, 30
At~100 DEG C, reacted 1~6 hour under 0.1-2MPa pressure；
The product that reaction obtains is poured into the ethanol solution of the hydrochloric acid containing 4-5wt%, obtained precipitates washed with EtOH
To neutrality, norbornene class, vinylacetate and N-phenylmaleimide terpolymer are obtained after vacuum drying；
The dosage of the Ni-Ti complex compound catalyst is calculated as norborneol alkenes, acetic acid second by the amount of dicyclopentadienyl nickel in catalyst
The 0.01%-1.0% of enester and N-phenylmaleimide three's total weight；
Second solvent is selected from benzene, toluene, tetrahydrofuran, petroleum ether, methyl phenyl ethers anisole, 1,4- dioxane, 1,2- dichloro
Ethane, hexamethylene or cyclohexanone；The amount ratio of the sum of molal quantity of each polymerized monomer and second solvent is 0.03 mole: 20
Milliliter.
The Norbornene derivative can be selected from two rings [2,2,1] hept-2-ene", 1- methyl bicyclic [2,2,1] hept- 2-
Alkene, 5- methyl bicyclic [2,2,1] hept-2-ene", 7- methyl bicyclic [2,2,1] hept-2-ene", two ring of 1- ethyl [2,2,1] hept- 2-
Alkene, two ring of 5- ethyl [2,2,1] hept-2-ene", 5,5- dimethyl, two ring [2,2,1] hept-2-ene", two ring of 1- phenyl [2,2,1] hept-
2- alkene, two ring of 5- phenyl [2,2,1] hept-2-ene", two ring of 5- vinyl [2,2,1] hept-2-ene", two rings [2,2,1] hept-2-ene"-
5- methyl formate or two rings [2,2,1] hept-2-ene" -5- formic acid spy's butyl ester.
Compared with prior art, catalyst provided by the invention is a kind of New Nickel-titanium complex catalyst mixture, is urged
Agent raw material is cheap and easy to get, can generate catalytic activity, catalysis norborneol alkenes, vinylacetate and N- phenyl horse at relatively low temperatures
Carry out acid imide ternary polymerization, reaction temperature is lower, high catalytic efficiency, and product is easy to washing separation, and copolymer yield is high；Institute
The resistance to corrosion of the norborneol alkenes of preparation, vinylacetate and N-phenylmaleimide terpolymer matrix is high, photoetching
Performance is good, and caking property, solubility and the toughness of material are further enhanced.
Specific embodiment
Present invention is further described in detail with reference to embodiments.
The preparation process of catalyst in following embodiment unless otherwise instructed carries out ligand therein and solvent
It is dried.Specifically: the drying of the solid ligand in ligand is first to be purified then to be dried in vacuo with recrystallization method；
The drying of liquid ligand in ligand is dried with calcium hydride drying or with metallic sodium.The drying of solvent is with calcium chloride or hydrogen
It is dry to change calcium.
Embodiment 1
In the three-necked flask of dry atmosphere of inert gases, 0.001 is rubbed dicyclopentadienyl nickel and 0.001 mole of 8-hydroxyquinoline
It is dissolved in 10 milliliters of benzene, at 200 rpm, 0.001 mole of tetraisopropoxy titanium is instilled in above-mentioned solution, same after dripping off
Constant temperature stirs 30 minutes to get Ni-Ti complex compound catalyst at 20 DEG C of stirring rate.
By 0.01 mole of two ring [2,2,1] hept-2-ene", 0.01 molar acetate vinyl acetate and 0.01 mole of N- phenyl Malaysia acyl
Imines, which is added to, repeatedly to be vacuumized, in nitrogen charging autoclave, and 20ml benzene is added to dissolve.Two rings are calculated as by the amount of dicyclopentadienyl nickel in catalyst
[2,2,1] hept-2-ene", vinylacetate and N-phenylmaleimide three's total weight 0.01% take above-mentioned Ni-Ti to be complexed
Object catalyst is injected in above-mentioned mixture with syringe.Constant temperature reacts 6 hours under 80 DEG C, 0.1MPa 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", vinylacetate and N-phenylmaleimide terpolymer.Calculating reaction yield is 41.5%.
The calculation method of reaction yield is terpolymer weight/total comonomer weight × 100%.Following each embodiments
In yield calculation method be identical with this.
Embodiment 2
In the three-necked flask of dry atmosphere of inert gases, 0.001 rub dicyclopentadienyl nickel and 0.006 mole of α, α '-is joined into pyrrole
Pyridine is dissolved in 10 milliliters of toluene, and at 210rpm, 0.004 mole of tetraisopropoxy titanium is instilled in above-mentioned solution, after dripping off
Constant temperature stirs 40 minutes to get Ni-Ti complex compound catalyst at same 40 DEG C of stirring rate.
By 0.01 mole of two ring [2,2,1] hept-2-ene", 0.01 molar acetate vinyl acetate and 0.01 mole of N- phenyl Malaysia acyl
Imines, which is added to, repeatedly to be vacuumized, in nitrogen charging autoclave, and 20ml toluene is added to dissolve.Two rings are calculated as by the amount of dicyclopentadienyl nickel in catalyst
[2,2,1] hept-2-ene", vinylacetate and N-phenylmaleimide three's total weight 0.08% take above-mentioned Ni-Ti to be complexed
Object catalyst is injected in above-mentioned mixture with syringe.Constant temperature reacts 5 hours under 90 DEG C, 1MPa 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", vinylacetate and N-phenylmaleimide terpolymer.Calculating reaction yield is 90.7%.
Embodiment 3
In the three-necked flask of dry atmosphere of inert gases, by 0.001 rub dicyclopentadienyl nickel and 0.010 mole of Phen it is molten
In 10 milliliters of tetrahydrofurans, at 190rpm, 0.004 mole of tetraisopropoxy titanium is instilled in above-mentioned solution, after dripping off
Constant temperature stirs 50 minutes to get Ni-Ti complex compound catalyst at same 30 DEG C of stirring rate.
By 0.01 mole of 1- methyl bicyclic [2,2,1] hept-2-ene", 0.01 molar acetate vinyl acetate and 0.01 mole of N- phenyl
Maleimide, which is added to, repeatedly to be vacuumized, in nitrogen charging autoclave, and 20ml tetrahydrofuran is added to dissolve.By dicyclopentadienyl nickel in catalyst
Amount is calculated as the 0.07% of 1- methyl bicyclic [2,2,1] hept-2-ene", vinylacetate and N-phenylmaleimide three's total weight
Above-mentioned Ni-Ti complex compound catalyst is taken, is injected in above-mentioned mixture with syringe.It is small that constant temperature reacts 1 under 80 DEG C, 2MPa pressure
When.Product, which is poured into the ethanol solution of the hydrochloric acid containing 5wt%, precipitates copolymer, precipitates washed with EtOH to neutrality, and vacuum is dry
It is dry to get arrive 1- methyl bicyclic [2,2,1] hept-2-ene", vinylacetate and N-phenylmaleimide terpolymer.It calculates
Reaction yield is 68.1%.
Embodiment 4
In the three-necked flask of dry atmosphere of inert gases, dicyclopentadienyl nickel is rubbed by 0.001 and 0.005 mole of quinoline is dissolved in 10
In milliliter petroleum ether, at 200 rpm, 0.010 mole of tetraisopropoxy titanium is instilled in above-mentioned solution, is equally being stirred after dripping off
It mixes constant temperature at 50 DEG C of rate and stirs 50 minutes to get Ni-Ti complex compound catalyst.
By 0.01 mole of 5- methyl bicyclic [2,2,1] hept-2-ene", 0.01 molar acetate vinyl acetate and 0.01 mole of N- phenyl
Maleimide, which is added to, repeatedly to be vacuumized, in nitrogen charging autoclave, and 20ml petroleum ether dissolution is added.By the amount of dicyclopentadienyl nickel in catalyst
Be calculated as 5- methyl bicyclic [2,2,1] hept-2-ene", vinylacetate and N-phenylmaleimide three's total weight 1.00% takes
Above-mentioned Ni-Ti complex compound catalyst is injected in above-mentioned mixture with syringe.It is small that constant temperature reacts 5 under 100 DEG C, 2MPa pressure
When.Product, which is poured into the ethanol solution of the hydrochloric acid containing 5wt%, precipitates copolymer, precipitates washed with EtOH to neutrality, and vacuum is dry
It is dry to get arrive 5- methyl bicyclic [2,2,1] hept-2-ene", vinylacetate and N-phenylmaleimide terpolymer.It calculates
Reaction yield is 62.1%.
Embodiment 5
In the three-necked flask of dry atmosphere of inert gases, dicyclopentadienyl nickel is rubbed by 0.001 and 0.006 mole of porphyrin is dissolved in 10
In milliliter methyl phenyl ethers anisole, at 200 rpm, 0.005 mole of tetraisopropoxy titanium is instilled in above-mentioned solution, is equally being stirred after dripping off
It mixes constant temperature at 50 DEG C of rate and stirs 40 minutes to get Ni-Ti complex compound catalyst.
By 0.01 mole of 7- methyl bicyclic [2,2,1] hept-2-ene", 0.01 molar acetate vinyl acetate and 0.01 mole of N- phenyl
Maleimide, which is added to, repeatedly to be vacuumized, in nitrogen charging autoclave, and 20ml methyl phenyl ethers anisole is added to dissolve.By the amount of dicyclopentadienyl nickel in catalyst
Be calculated as 7- methyl bicyclic [2,2,1] hept-2-ene", vinylacetate and N-phenylmaleimide three's total weight 0.09% takes
Above-mentioned Ni-Ti complex compound catalyst is injected in above-mentioned mixture with syringe.It is small that constant temperature reacts 6 under 80 DEG C, 1MPa pressure
When.Product, which is poured into the ethanol solution of the hydrochloric acid containing 5wt%, precipitates copolymer, precipitates washed with EtOH to neutrality, and vacuum is dry
It is dry to get arrive 7- methyl bicyclic [2,2,1] hept-2-ene", vinylacetate and N-phenylmaleimide terpolymer.It calculates
Reaction yield is 84.2%.
Embodiment 6
In the three-necked flask of dry atmosphere of inert gases, 0.010 is rubbed dicyclopentadienyl nickel and 0.001 mole of pentanedione
It is dissolved in 10 milliliters of Isosorbide-5-Nitrae-dioxane, at 200 rpm, 0.006 mole of tetraisopropoxy titanium is instilled in above-mentioned solution, drop
Constant temperature stirs 40 minutes to get Ni-Ti complex compound catalyst at 30 DEG C of same stirring rate after complete.
By 0.01 mole of two ring of 1- ethyl [2,2,1] hept-2-ene", 0.01 molar acetate vinyl acetate and 0.01 mole of N- phenyl
Maleimide, which is added to, repeatedly to be vacuumized, in nitrogen charging autoclave, and 20ml1, the dissolution of 4- dioxane are added.By two cyclopentadienyl in catalyst
The amount of nickel is calculated as two ring of 1- ethyl [2,2,1] hept-2-ene", vinylacetate and N-phenylmaleimide three's total weight
0.06% takes above-mentioned Ni-Ti complex compound catalyst, is injected in above-mentioned mixture with syringe.Constant temperature is at 50 DEG C, 0.3MPa pressure
Lower reaction 3 hours.Product, which is poured into the ethanol solution of the hydrochloric acid containing 5wt%, precipitates copolymer, and precipitates washed with EtOH is into
Property, vacuum drying is to get total to two ring of 1- ethyl [2,2,1] hept-2-ene", vinylacetate and N-phenylmaleimide ternary
Polymers.Calculating reaction yield is 43.4%.
Embodiment 7
In the three-necked flask of dry atmosphere of inert gases, 0.010 is rubbed dicyclopentadienyl nickel and 0.002 mole of 8-hydroxyquinoline
It is dissolved in 10 milliliters of Isosorbide-5-Nitrae-dioxane, at 200 rpm, 0.001 mole of tetraisopropoxy titanium is instilled in above-mentioned solution, drop
Constant temperature stirs 30 minutes to get Ni-Ti complex compound catalyst at 40 DEG C of same stirring rate after complete.
0.01 mole of two ring of 5- ethyl [2,2,1] hept-2-ene", 0.01 are rubbed vinylacetate and 0.01 mole of N- phenyl horse
Carry out acid imide and be added to repeatedly to vacuumize, in nitrogen charging autoclave, adds 20ml1, the dissolution of 4- dioxane.By dicyclopentadienyl nickel in catalyst
Amount be calculated as two ring of 5- ethyl [2,2,1] hept-2-ene", vinylacetate and N-phenylmaleimide three's total weight
0.10% takes above-mentioned Ni-Ti complex compound catalyst, is injected in above-mentioned mixture with syringe.Constant temperature is at 30 DEG C, 0.6MPa pressure
Lower reaction 4 hours.Product, which is poured into the ethanol solution of the hydrochloric acid containing 5wt%, precipitates copolymer, and precipitates washed with EtOH is into
Property, vacuum drying is to get total to two ring of 5- ethyl [2,2,1] hept-2-ene", vinylacetate and N-phenylmaleimide ternary
Polymers.Calculating reaction yield is 41.3%.
Embodiment 8
In the three-necked flask of dry atmosphere of inert gases, dicyclopentadienyl nickel is rubbed by 0.006 and 0.010 mole of isoquinolin is dissolved in
In 10 milliliters of 1,2- dichloroethanes, at 200 rpm, 0.001 mole of tetraisopropoxy titanium is instilled in above-mentioned solution, after dripping off
Constant temperature stirs 50 minutes to get Ni-Ti complex compound catalyst at 40 DEG C of same stirring rate.
By 0.01 mole of 5,5- dimethyl, two ring [2,2,1] hept-2-ene", 0.01 molar acetate vinyl acetate and 0.01 mole of N-
Phenyl maleimide, which is added to, repeatedly to be vacuumized, in nitrogen charging autoclave, and 20ml1, the dissolution of 2- dichloroethanes are added.By in catalyst
It is total that the amount of dicyclopentadienyl nickel is calculated as 5,5- dimethyl, two ring [2,2,1] hept-2-ene", vinylacetate and N-phenylmaleimide three
The 0.30% of weight takes above-mentioned Ni-Ti complex compound catalyst, is injected in above-mentioned mixture with syringe.Constant temperature at 50 DEG C,
It is reacted 4 hours under 0.8MPa pressure.Product, which is poured into the ethanol solution of the hydrochloric acid containing 5wt%, precipitates copolymer, sediment second
Alcohol is washed to neutrality, and vacuum drying is to get to 5,5- dimethyl, two ring [2,2,1] hept-2-ene", vinylacetate and N- phenyl horse
Carry out imide terpolymer.Calculating reaction yield is 45.1%.
Embodiment 9
In the three-necked flask of dry atmosphere of inert gases, 0.001 rub dicyclopentadienyl nickel and 0.008 mole of α, α '-is joined into pyrrole
Pyridine is dissolved in 10 milliliters of hexamethylenes, at 200 rpm, 0.003 mole of tetraisopropoxy titanium is instilled in above-mentioned solution, after dripping off
Constant temperature stirs 20 minutes to get Ni-Ti complex compound catalyst at 50 DEG C of same stirring rate.
By 0.01 mole of two ring of 1- phenyl [2,2,1] hept-2-ene", 0.01 molar acetate vinyl acetate and 0.01 mole of N- phenyl
Maleimide, which is added to, repeatedly to be vacuumized, in nitrogen charging autoclave, and 20ml hexamethylene is added to dissolve.By the amount of dicyclopentadienyl nickel in catalyst
Be calculated as two ring of 1- phenyl [2,2,1] hept-2-ene", vinylacetate and N-phenylmaleimide three's total weight 0.06% takes
Above-mentioned Ni-Ti complex compound catalyst is injected in above-mentioned mixture with syringe.It is small that constant temperature reacts 6 under 80 DEG C, 1.5MPa pressure
When.Product, which is poured into the ethanol solution of the hydrochloric acid containing 5wt%, precipitates copolymer, precipitates washed with EtOH to neutrality, and vacuum is dry
It is dry to get arrive two ring of 1- phenyl [2,2,1] hept-2-ene", vinylacetate and N-phenylmaleimide terpolymer.It calculates
Reaction yield is 75.6%.
Embodiment 10
In the three-necked flask of dry atmosphere of inert gases, 0.001 rub dicyclopentadienyl nickel and 0.005 mole of α, α '-is joined into pyrrole
Pyridine is dissolved in 10 milliliters of cyclohexanone, at 200 rpm, 0.007 mole of tetraisopropoxy titanium is instilled in above-mentioned solution, after dripping off
Constant temperature stirs 30 minutes to get Ni-Ti complex compound catalyst at 50 DEG C of same stirring rate.
By 0.01 mole of two ring of 5- phenyl [2,2,1] hept-2-ene", 0.01 molar acetate vinyl acetate and 0.01 mole of N- phenyl
Maleimide, which is added to, repeatedly to be vacuumized, in nitrogen charging autoclave, and 20ml cyclohexanone is added to dissolve.By the amount of dicyclopentadienyl nickel in catalyst
Be calculated as two ring of 5- phenyl [2,2,1] hept-2-ene", vinylacetate and N-phenylmaleimide three's total weight 0.07% takes
Above-mentioned Ni-Ti complex compound catalyst is injected in above-mentioned mixture with syringe.It is small that constant temperature reacts 5 under 60 DEG C, 1MPa pressure
When.Product, which is poured into the ethanol solution of the hydrochloric acid containing 5wt%, precipitates copolymer, precipitates washed with EtOH to neutrality, and vacuum is dry
It is dry to get arrive two ring of 5- phenyl [2,2,1] hept-2-ene", vinylacetate and N-phenylmaleimide terpolymer.It calculates
Reaction yield is 71.9%.
Embodiment 11
In the three-necked flask of dry atmosphere of inert gases, by 0.001 rub dicyclopentadienyl nickel and 0.007 mole of Phen it is molten
In 10 milliliters of toluene, at 200 rpm, 0.005 mole of tetraisopropoxy titanium is instilled in above-mentioned solution, same after dripping off
Constant temperature stirs 50 minutes to get Ni-Ti complex compound catalyst at 50 DEG C of stirring rate.
By 0.01 mole of two ring of 5- vinyl [2,2,1] hept-2-ene", 0.01 molar acetate vinyl acetate and 0.01 mole of N- benzene
Base maleimide, which is added to, repeatedly to be vacuumized, in nitrogen charging autoclave, and 20ml toluene is added to dissolve.By the amount of dicyclopentadienyl nickel in catalyst
It is calculated as the 0.05% of two ring of 5- vinyl [2,2,1] hept-2-ene", vinylacetate and N-phenylmaleimide three's total weight
Above-mentioned Ni-Ti complex compound catalyst is taken, is injected in above-mentioned mixture with syringe.Constant temperature reacts 5 under 100 DEG C, 2MPa pressure
Hour.Product, which is poured into the ethanol solution of the hydrochloric acid containing 5wt%, precipitates copolymer, precipitates washed with EtOH to neutrality, vacuum
It dries to get two ring of 5- vinyl [2,2,1] hept-2-ene", vinylacetate and N-phenylmaleimide terpolymer is arrived.
Calculating reaction yield is 81.1%.
Embodiment 12
In the three-necked flask of dry atmosphere of inert gases, dicyclopentadienyl nickel is rubbed by 0.001 and 0.005 mole of isoquinolin is dissolved in
In 10 milliliters of tetrahydrofurans, at 200 rpm, 0.007 mole of tetraisopropoxy titanium is instilled in above-mentioned solution, same after dripping off
Constant temperature stirs 30 minutes to get Ni-Ti complex compound catalyst at 40 DEG C of sample stirring rate.
By 0.01 mole of two ring [2,2,1] hept-2-ene" -5- methyl formate, 0.01 molar acetate vinyl acetate and 0.01 mole
N-phenylmaleimide, which is added to, repeatedly to be vacuumized, in nitrogen charging autoclave, and 20ml tetrahydrofuran is added to dissolve.By in catalyst two
It is total that the amount of luxuriant nickel is calculated as two rings [2,2,1] hept-2-ene" -5- methyl formate, vinylacetate and N-phenylmaleimide three
The 0.04% of weight takes above-mentioned Ni-Ti complex compound catalyst, is injected in above-mentioned mixture with syringe.Constant temperature is at 90 DEG C, 1MPa
It is reacted 6 hours under pressure.Product, which is poured into the ethanol solution of the hydrochloric acid containing 5wt%, precipitates copolymer, precipitates washed with EtOH
To neutrality, vacuum drying is to get to two rings [2,2,1] hept-2-ene" -5- methyl formate, vinylacetate and N- phenyl Malaysia acyl
Imines terpolymer.Calculating reaction yield is 70.2%.
Embodiment 13
In the three-necked flask of dry atmosphere of inert gases, dicyclopentadienyl nickel is rubbed by 0.010 and 0.004 mole of quinoline is dissolved in 10
In milliliter petroleum ether, at 200 rpm, 0.003 mole of tetraisopropoxy titanium is instilled in above-mentioned solution, is equally being stirred after dripping off
It mixes constant temperature at 50 DEG C of rate and stirs 50 minutes to get Ni-Ti complex compound catalyst.
0.01 mole of two ring [2,2,1] hept-2-ene" -5- formic acid spy butyl ester, 0.01 molar acetate vinyl acetate and 0.01 are rubbed
Your N-phenylmaleimide, which is added to, repeatedly to be vacuumized, in nitrogen charging autoclave, and 20ml petroleum ether dissolution is added.By in catalyst two
The amount of luxuriant nickel is calculated as two rings [2,2,1] hept-2-ene" -5- formic acid spy butyl ester, vinylacetate and N-phenylmaleimide three
The 0.06% of total weight takes above-mentioned Ni-Ti complex compound catalyst, is injected in above-mentioned mixture with syringe.Constant temperature at 80 DEG C,
It is reacted 2 hours under 1.3MPa pressure.Product, which is poured into the ethanol solution of the hydrochloric acid containing 5wt%, precipitates copolymer, sediment second
Alcohol is washed to neutrality, and vacuum drying is to get to two rings [2,2,1] hept-2-ene" -5- formic acid spy butyl ester, vinylacetate and N- benzene
Base maleimide terpolymer.Calculating reaction yield is 55.7%.
Embodiment 14
In the three-necked flask of dry atmosphere of inert gases, dicyclopentadienyl nickel is rubbed by 0.010 and 0.006 mole of porphyrin is dissolved in 10
In milliliter methyl phenyl ethers anisole, at 200 rpm, 0.002 mole of tetraisopropoxy titanium is instilled in above-mentioned solution, is equally being stirred after dripping off
It mixes constant temperature at 40 DEG C of rate and stirs 30 minutes to get Ni-Ti complex compound catalyst.
0.01 mole of two ring [2,2,1] hept-2-ene" -5- formic acid spy butyl ester, 0.01 molar acetate vinyl acetate and 0.01 are rubbed
Your N-phenylmaleimide, which is added to, repeatedly to be vacuumized, in nitrogen charging autoclave, and 20ml methyl phenyl ethers anisole is added to dissolve.By in catalyst two
The amount of luxuriant nickel is calculated as two rings [2,2,1] hept-2-ene" -5- formic acid spy butyl ester, vinylacetate and N-phenylmaleimide three
The 0.80% of total weight takes above-mentioned Ni-Ti complex compound catalyst, is injected in above-mentioned mixture with syringe.Constant temperature at 50 DEG C,
It is reacted 5 hours under 1.7MPa pressure.Product, which is poured into the ethanol solution of the hydrochloric acid containing 5wt%, precipitates copolymer, sediment second
Alcohol is washed to neutrality, and vacuum drying is to get to two rings [2,2,1] hept-2-ene" -5- formic acid spy butyl ester, vinylacetate and N- benzene
Base maleimide terpolymer.Calculating reaction yield is 50.6%.
Embodiment 15
In the three-necked flask of dry atmosphere of inert gases, 0.001 rub dicyclopentadienyl nickel and 0.006 mole of α, α '-is joined into pyrrole
Pyridine is dissolved in 10 milliliters of hexamethylenes, at 200 rpm, 0.007 mole of tetraisopropoxy titanium is instilled in above-mentioned solution, after dripping off
Constant temperature stirs 50 minutes to get Ni-Ti complex compound catalyst at 40 DEG C of same stirring rate.
By 0.01 mole of two ring [2,2,1] hept-2-ene", 0.01 molar acetate vinyl acetate and 0.01 mole of N- phenyl Malaysia acyl
Imines, which is added to, repeatedly to be vacuumized, in nitrogen charging autoclave, and 20ml hexamethylene is added to dissolve.Two are calculated as by the amount of dicyclopentadienyl nickel in catalyst
Ring [2,2,1] hept-2-ene", vinylacetate and N-phenylmaleimide three's total weight 0.09% take above-mentioned Ni-Ti network
Mixture catalyst is injected in above-mentioned mixture with syringe.Constant temperature reacts 5 hours under 70 DEG C, 1.8MPa 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", vinylacetate and N-phenylmaleimide terpolymer.Calculating reaction yield is 65.6%.
Embodiment 16
In the three-necked flask of dry atmosphere of inert gases, 0.001 is rubbed dicyclopentadienyl nickel and 0.003 mole of 8-hydroxyquinoline
It is dissolved in 10 milliliters of benzene, at 200 rpm, 0.004 mole of tetraisopropoxy titanium is instilled in above-mentioned solution, same after dripping off
Constant temperature stirs 40 minutes to get Ni-Ti complex compound catalyst at 20 DEG C of stirring rate.
By 0.01 mole of 1- methyl bicyclic [2,2,1] hept-2-ene", 0.01 molar acetate vinyl acetate and 0.01 mole of N- phenyl
Maleimide, which is added to, repeatedly to be vacuumized, in nitrogen charging autoclave, and 20ml benzene is added to dissolve.It is calculated as by the amount of dicyclopentadienyl nickel in catalyst
1- methyl bicyclic [2,2,1] hept-2-ene", vinylacetate and N-phenylmaleimide three's total weight 1.00% take it is above-mentioned
Ni-Ti complex compound catalyst is injected in above-mentioned mixture with syringe.Constant temperature reacts 4 hours under 100 DEG C, 0.5MPa pressure.
Product, which is poured into the ethanol solution of the hydrochloric acid containing 5wt%, precipitates copolymer, precipitates washed with EtOH to neutrality, vacuum drying,
Obtain 1- methyl bicyclic [2,2,1] hept-2-ene", vinylacetate and N-phenylmaleimide terpolymer.It calculates anti-
Answering yield is 67.6%.
Claims (4)
1. norborneol alkenes, vinylacetate and N-phenylmaleimide method for ternary polymerization, it is characterised in that use and urge
Agent the preparation method is as follows:
In the three-necked flask of dry inert atmosphere, dicyclopentadienyl nickel and ligand are dissolved in the first solvent, in 190 ~ 210rpm
Under, tetraisopropoxy titanium is instilled, constant temperature stirs 20-50 minutes to get nickel-under same stirring rate at 20-50 DEG C after dripping off
Titanium complex catalyst；
The molar ratio of the dicyclopentadienyl nickel and the ligand is 1: 10 ~ 10: 1, and the dicyclopentadienyl nickel rubs with the tetraisopropoxy titanium
You are than being 1: 10 ~ 10: 1；
The ligand is selected from 8-hydroxyquinoline, α, α '-bipyridyl, Phen, isoquinolin, quinoline, porphyrin or pentanedione；
First solvent be selected from benzene, toluene, tetrahydrofuran, petroleum ether, methyl phenyl ethers anisole, 1,4- dioxane, 1,2- dichloroethanes,
Hexamethylene or cyclohexanone；
The dosage of first solvent and the ratio of the dicyclopentadienyl nickel, tetraisopropoxy titanium and ligand three's total amount are 10 milliliters:
0.003~0.030 mole；
Norborneol alkenes, vinylacetate and N-phenylmaleimide monomer is taken to be added to multiple pumping according to molar ratio 1: 1: 1
Vacuum, nitrogen charging reaction kettle in, be added the second solvent dissolution；Then the Ni-Ti complex compound catalyst is added, 30 ~ 100
At DEG C, reacted 1 ~ 6 hour under 0.1-2MPa pressure；
The product that reaction obtains is poured into the ethanol solution of the hydrochloric acid containing 4-5wt%, obtained precipitates washed with EtOH is into
Property, norbornene class, vinylacetate and N-phenylmaleimide terpolymer are obtained after vacuum drying；
The dosage of the Ni-Ti complex compound catalyst is calculated as norborneol alkenes, vinylacetate by the amount of dicyclopentadienyl nickel in catalyst
With the 0.01%-1.0% of N-phenylmaleimide three's total weight；
Second solvent be selected from benzene, toluene, tetrahydrofuran, petroleum ether, methyl phenyl ethers anisole, 1,4- dioxane, 1,2- dichloroethanes,
Hexamethylene or cyclohexanone；The amount ratio of the sum of molal quantity of each polymerized monomer and second solvent is 0.03 mole: 20 milliliter.
2. norborneol alkenes according to claim 1, vinylacetate and N-phenylmaleimide method for ternary polymerization,
It is characterized in that the molar ratio of the dicyclopentadienyl nickel, tetraisopropoxy titanium and ligand three is preferably 1: 4: 6.
3. according to claim 1 or 2 norborneol alkenes, vinylacetate and N-phenylmaleimide method for ternary polymerization,
It is characterized in that 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.
4. norborneol alkenes according to claim 3, vinylacetate and N-phenylmaleimide 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 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", 5-
Two ring of 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- formic acid
Methyl esters or two rings [2,2,1] hept-2-ene" -5- formic acid spy's butyl ester.
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| CN104788615A (en) * | 2015-04-30 | 2015-07-22 | 宁波工程学院 | Ternary copolymerization catalyst and ternary copolymerization method for norbornenes, styrene and N-phenyl maleimide |
| CN105693929A (en) * | 2016-03-17 | 2016-06-22 | 宁波工程学院 | Norbornene, styrene and nikasol ternary polymerization catalyst and ternary polymerization method |
| CN105924548A (en) * | 2016-05-10 | 2016-09-07 | 宁波工程学院 | Norbornene, acrylonitrile and vinyl acetate ternary polymerization catalyst and ternary polymerization method |
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| CN104788615A (en) * | 2015-04-30 | 2015-07-22 | 宁波工程学院 | Ternary copolymerization catalyst and ternary copolymerization method for norbornenes, styrene and N-phenyl maleimide |
| CN105693929A (en) * | 2016-03-17 | 2016-06-22 | 宁波工程学院 | Norbornene, styrene and nikasol ternary polymerization catalyst and ternary polymerization method |
| CN105924548A (en) * | 2016-05-10 | 2016-09-07 | 宁波工程学院 | Norbornene, acrylonitrile and vinyl acetate ternary polymerization catalyst and ternary polymerization method |
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