CN107141411A - Norborneol alkenes, maleic anhydride and N phenyl maleimide ternary polymerization catalyst and method for ternary polymerization - Google Patents
Norborneol alkenes, maleic anhydride and N phenyl maleimide ternary polymerization catalyst and method for ternary polymerization Download PDFInfo
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- CN107141411A CN107141411A CN201710543303.1A CN201710543303A CN107141411A CN 107141411 A CN107141411 A CN 107141411A CN 201710543303 A CN201710543303 A CN 201710543303A CN 107141411 A CN107141411 A CN 107141411A
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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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- C08F222/00—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 a carboxyl radical and containing at least one other carboxyl radical in the molecule; Salts, anhydrides, esters, amides, imides, or nitriles thereof
- C08F222/04—Anhydrides, e.g. cyclic anhydrides
- C08F222/06—Maleic anhydride
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Abstract
The present invention relates to norborneol alkenes, maleic anhydride and N phenyl maleimide ternary polymerization catalyst and method for ternary polymerization, it is characterised in that the preparation method of the catalyst is as follows：In the glove box of nitrogen atmosphere, by [1,1 ' double (diphenylphosphino) ferrocene] palladium chloride and part be dissolved in the first solvent in conical flask, under magnetic stirring, tetraisopropoxy titanium is instilled, constant temperature is stirred under same stir speed (S.S.) at 20~50 DEG C after dripping off, and boils off the first solvent described in part, 2~5 hours are stood, it is palladium titanium complex catalyst to filter to take solid crystal.Take norborneol alkenes, maleic anhydride and N phenyl maleimide monomers to be added to by 1: 1: 1 repeatedly to vacuumize, in the single port glass polymerization bottle of nitrogen charging baking, add the dissolving of the second solvent；Then described palladium titanium complex catalyst reaction is added, taking precipitate is norborneol alkenes, maleic anhydride and N phenyl maleimide terpolymers after product washing.
Description
Technical field
The present invention relates to high polymer field, a kind of norborneol alkenes, maleic anhydride and N- benzyl maleimides are referred specifically to
Amine ternary polymerization catalyst and method for ternary polymerization.
Background technology
Polynorbornene is a kind of special polymer, with excellent mechanical property, heat resistance, in organic solvent
The soluble and transparency, available for 193nm ultraviolet light photoetching.This material major defect is that fragility, viscosity difference and molecular weight are low
Deng.After oxygenatedchemicals is inserted in polynorbornene main chain, the caking property and solubility of polymer can be improved, and reduce material
The absorptance of material itself.This copolymer can be applied to 193nm replica technologies as photoresist.Moreover, microelectronics industry
The smaller composition of development need, to suitable for the exposure technique that line width is 1.3 μm and following line width, 193nm light may be selected
Lithography, 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
Type resist, for new material of mask and its protective film etc. await solve the problem of.Therefore, for the photoetching obtained
New material, has developed alternating copolymerization material, main development ENB and acrylate or other component ternary polymerization materials, together
Shi Yingyong has the ENB of side base, it is therefore an objective to improve the resistance to corrosion of whole matrix, improves lithography performance, increases the viscous of material
Knot property, soluble and toughness.
Synthesizing the method for these materials at present mainly has the methods such as free radical, living radical, metallic catalyst.Such as
The synthesis of photoetching material employs peroxidating disclosed in Proceedings of SPIE Vol.5039 (2003) pages 80~92
Thing as radical polymerization catalyst, disclosed in Proceedings of SPIE Vol.4690 (2002) pages 127~135
The synthesis of photoetching material employs AINB (azodiisobutyronitrile) as the catalyst of radical polymerization.A.E.Feiring and
M.Toriumi etc. is by ENB, tetrafluoroethene and free radical acrylate ternary polymerization etc..These the synthesis sides applied at present
There is reaction time length in method, acquisition copolymer yield is low, molecular weight of copolymer is small, the low shortcoming of copolymer alternate degree.
The content of the invention
The technical problems to be solved by the invention be for prior art present situation provide one kind can reduce reaction temperature,
Improve norborneol alkenes, maleic anhydride and the N-phenylmaleimide ternary polymerization catalysis of catalytic efficiency and copolymer yield
Agent.
Another technical problem to be solved by this invention is to provide a kind of relatively low reaction temperature, high catalytic efficiency and copolymerization
Norborneol alkenes, maleic anhydride and the method for N-phenylmaleimide ternary polymerization of thing high income.
The present invention solve the technical scheme that is used of above-mentioned technical problem for：The norborneol alkenes, maleic anhydride and N- benzene
Base maleimide ternary polymerization catalyst, it is characterised in that the preparation method of the catalyst is as follows：
In the glove box of nitrogen atmosphere, will [1,1 '-bis- (diphenylphosphino) ferrocene] palladium chloride and part three
The first solvent is dissolved in the flask of angle, under 250~400rpm magnetic agitations, tetraisopropoxy titanium is instilled, after dripping off 20~
Constant temperature is stirred 20-50 minutes under same stir speed (S.S.) at 50 DEG C, boils off the first solvent of 1/2~3/4 volume, stands 2~5 small
When, solid crystal is obtained, filtering produces palladium-titanium complex catalyst；
The mol ratio of [1,1 '-bis- (diphenylphosphino) ferrocene] palladium chloride and the part is 1: 10~10:
1, the mol ratio of [1,1 '-bis- (diphenylphosphino) ferrocene] palladium chloride and the tetraisopropoxy titanium is 1: 10~10
∶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 first solvent and [1,1 '-bis- (diphenylphosphino) ferrocene] palladium chloride, part and four
The ratio of titanium isopropoxide three's total amount is 10 milliliters：0.003~0.020 mole.
[1,1 '-bis- (diphenylphosphino) ferrocene] palladium chloride, tetraisopropoxy titanium and part three it is preferred that described
Mol ratio is preferably 1: 5: 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 and then be dried in vacuo with recrystallization method；The drying of liquid part in the part is to use calcium hydride or metal
Sodium is dried, and first solvent is dried using calcium chloride or calcium hydride.
Use the ENB of above-mentioned norborneol alkenes, maleic anhydride and N-phenylmaleimide ternary polymerization catalyst
Class, maleic anhydride and N-phenylmaleimide method for ternary polymerization, it is characterised in that comprise the steps：
Norborneol alkenes, maleic anhydride and N-phenylmaleimide monomer is taken to be added to repeatedly according to mol ratio 1: 1: 1
Vacuumize, in the single port glass polymerization bottle of nitrogen charging baking, add the dissolving of the second solvent；Then described palladium-titanium complex is added
Catalyst, at 20~90 DEG C, reacts 1~6 hour；
The product that reaction is obtained is poured into the ethanol solution of the hydrochloric acid containing 4-5wt%, obtained precipitates washed with EtOH
To neutral, ENB class, maleic anhydride and N-phenylmaleimide terpolymer are obtained after vacuum drying；
The consumption of the palladium-titanium complex catalyst is norborneol alkenes, maleic anhydride and N-phenylmaleimide three
The 0.01%-1.0% of person's total monomer 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 amount ratio of the molal quantity sum 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 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", the ring of 1- ethyls two [2,2,1] hept- 2-
Alkene, the ring of 5- ethyls two [2,2,1] hept-2-ene", the ring of 5,5- dimethyl two [2,2,1] hept-2-ene", the ring of 1- phenyl two [2,2,1] hept-
2- alkene, the ring of 5- phenyl two [2,2,1] hept-2-ene", the ring of 5- vinyl two [2,2,1] hept-2-ene", two rings [2,2,1] hept-2-ene"-
5- methyl formates or the special butyl ester of two rings [2,2,1] hept-2-ene" -5- formic acid.
Compared with prior art, the catalyst that the present invention is provided is a kind of Novel Palladium-titanium complex catalyst, catalysagen
Material is cheap and easy to get, can be catalyzed norborneol alkenes, maleic anhydride and N-phenylmaleimide compared with catalytic activity is produced under low temperature
Ternary polymerization, reaction temperature is relatively low, high catalytic efficiency, and product is easy to washing separation, and copolymer yield is high；Prepared drop
The resistance to corrosion of borneol alkenes, maleic anhydride and N-phenylmaleimide terpolymer matrix is high, and lithography performance is good, material
Caking property, soluble and toughness is further enhanced.
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
Drying process.Specifically：The drying of solid ligand in part is first to be purified and then be dried in vacuo with recrystallization method；
The drying of liquid part in part is to be dried or dried with metallic sodium with calcium hydride.The drying of solvent is to use calcium chloride or hydrogen
Change calcium to dry.
Embodiment 1
In the glove box of nitrogen atmosphere, by 0.001 mole of [1,1 '-bis- (diphenylphosphino) ferrocene] palladium chloride and
0.001 mole of 8-hydroxyquinoline is dissolved in 10 milliliters of benzene in conical flask, under 250rpm, with magnetic stirrer, incites somebody to action
0.003 mole of tetraisopropoxy titanium is instilled in above-mentioned solution, and constant temperature is stirred 30 minutes at same 20 DEG C of stir speed (S.S.) after dripping off,
5ml benzene is boiled off, 5 hours are stood, solid crystal is obtained, filtering produces palladium-titanium complex catalyst.
By 0.01 mole of two ring [2,2,1] hept-2-ene", 0.01 mol maleic anhydride and 0.01 mole of N- benzyl maleimide
Amine, which is added to, repeatedly to be vacuumized, in the single port glass polymerization bottle of nitrogen charging baking, plus the dissolving of 20ml benzene.By two rings [2,2,1] hept- 2-
Alkene, the 0.09% of maleic anhydride and N-phenylmaleimide three's gross weight take above-mentioned palladium-titanium complex catalyst, are put into
State in mixture.Constant temperature reacts 6 hours at 80 DEG C.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 two rings [2,2,1] hept-2-ene", maleic anhydride and N- phenyl Malaysia
Imide terpolymer.It is 41.1% to calculate reaction yield.
The computational methods of reaction yield are terpolymer weight/comonomer gross weight × 100%.Following each embodiments
In yield computational methods it is identical with this.
Embodiment 2
In the glove box of nitrogen atmosphere, by 0.001 mole of [1,1 '-bis- (diphenylphosphino) ferrocene] palladium chloride and
0.006 mole of α, α '-bipyridyl is dissolved in 10 milliliters of toluene in conical flask, at 300 rpm, with magnetic stirrer,
0.005 mole of tetraisopropoxy titanium is instilled in above-mentioned solution, constant temperature stirs 40 points at same 40 DEG C of stir speed (S.S.) after dripping off
Clock, boils off 7.5ml toluene, stands 2 hours, obtains solid crystal, and filtering produces palladium-titanium complex catalyst.
By 0.01 mole of two ring [2,2,1] hept-2-ene", 0.01 mol maleic anhydride and 0.01 mole of N- benzyl maleimide
Amine, which is added to, repeatedly to be vacuumized, in the single port glass polymerization bottle of nitrogen charging baking, plus the dissolving of 20ml toluene.By two rings [2,2,1] hept-
2- alkene, the 0.08% of maleic anhydride and N-phenylmaleimide three's gross weight take above-mentioned palladium-titanium complex catalyst, add
In above-mentioned mixture.Constant temperature reacts 5 hours at 90 DEG C.Product, which is poured into the ethanol solution of the hydrochloric acid containing 5wt%, makes copolymer sink
Form sediment, precipitates washed with EtOH to neutrality, vacuum drying obtains two rings [2,2,1] hept-2-ene", maleic anhydride and N- phenyl
Maleimide terpolymer.It is 94.5% to calculate reaction yield.
Embodiment 3
In the glove box of nitrogen atmosphere, by 0.001 mole of [1,1 '-bis- (diphenylphosphino) ferrocene] palladium chloride and
0.010 mole of Phen is dissolved in 10 milliliters of tetrahydrofurans in conical flask, under 400rpm, uses magnetic stirrer
Under, 0.004 mole of tetraisopropoxy titanium is instilled in above-mentioned solution, the constant temperature stirring 50 at same 30 DEG C of stir speed (S.S.) after dripping off
Minute, 7.5ml tetrahydrofurans are boiled off, 3 hours are stood, solid crystal is obtained, filtering produces palladium-titanium complex catalyst.
By 0.01 mole of 1- methyl bicyclics [2,2,1] hept-2-ene", 0.01 mol maleic anhydride and 0.01 mole of N- phenyl horse
Carry out acid imide and be added to repeatedly to vacuumize, in the single port glass polymerization bottle of nitrogen charging baking, plus the dissolving of 20ml tetrahydrofurans.By 1- first
The ring of base two [2,2,1] hept-2-ene", the 0.07% of maleic anhydride and N-phenylmaleimide three's gross weight take above-mentioned palladium-titanium
Complex compound catalyst, is added in above-mentioned mixture.Constant temperature reacts 1 hour at 20 DEG C.Product is poured into the ethanol of the hydrochloric acid containing 5wt%
Copolymer is precipitated in solution, precipitates washed with EtOH to neutrality, vacuum drying obtains 1- methyl bicyclics [2,2,1] hept-
2- alkene, maleic anhydride and N-phenylmaleimide terpolymer.It is 58.1% to calculate reaction yield.
Embodiment 4
In the glove box of nitrogen atmosphere, by 0.001 mole of [1,1 '-bis- (diphenylphosphino) ferrocene] palladium chloride and
0.005 mole of quinoline is dissolved in 10 milliliters of petroleum ethers in conical flask, under 280rpm, with magnetic stirrer, incites somebody to action
0.010 mole of tetraisopropoxy titanium is instilled in above-mentioned solution, and constant temperature is stirred 50 minutes at same 50 DEG C of stir speed (S.S.) after dripping off,
7.5ml petroleum ethers are boiled off, 4 hours are stood, solid crystal is obtained, filtering produces palladium-titanium complex catalyst.
By 0.01 mole of 5- methyl bicyclics [2,2,1] hept-2-ene", 0.01 mol maleic anhydride and 0.01 mole of N- phenyl horse
Carry out acid imide and be added to repeatedly to vacuumize, in the single port glass polymerization bottle of nitrogen charging baking, plus 20ml petroleum ether dissolutions.By 5- methyl
Two rings [2,2,1] hept-2-ene", the 1.00% of maleic anhydride and N-phenylmaleimide three's gross weight take above-mentioned palladium-titanium network
Mixture catalyst, is added in above-mentioned mixture.Constant temperature reacts 5 hours at 50 DEG C.The ethanol that product is poured into the hydrochloric acid containing 5wt% is molten
Copolymer is precipitated in liquid, precipitates washed with EtOH to neutrality, vacuum drying obtains 5- methyl bicyclics [2,2,1] hept- 2-
Alkene, maleic anhydride and N-phenylmaleimide terpolymer.It is 63.1% to calculate reaction yield.
Embodiment 5
In the glove box of nitrogen atmosphere, by 0.001 mole of [1,1 '-bis- (diphenylphosphino) ferrocene] palladium chloride and
0.006 mole of porphyrin is dissolved in 10 milliliters of methyl phenyl ethers anisoles in conical flask, under 350rpm, with magnetic stirrer, incites somebody to action
0.007 mole of tetraisopropoxy titanium is instilled in above-mentioned solution, and constant temperature is stirred 40 minutes at same 50 DEG C of stir speed (S.S.) after dripping off,
5ml methyl phenyl ethers anisoles are boiled off, 4 hours are stood, solid crystal is obtained, filtering produces palladium-titanium complex catalyst.
By 0.01 mole of 7- methyl bicyclics [2,2,1] hept-2-ene", 0.01 mol maleic anhydride and 0.01 mole of N- phenyl horse
Carry out acid imide and be added to repeatedly to vacuumize, in the single port glass polymerization bottle of nitrogen charging baking, plus the dissolving of 20ml methyl phenyl ethers anisoles.By 7- methyl
Two rings [2,2,1] hept-2-ene", the 0.09% of maleic anhydride and N-phenylmaleimide three's gross weight take above-mentioned palladium-titanium network
Mixture catalyst, is added in above-mentioned mixture.Constant temperature reacts 6 hours at 80 DEG C.The ethanol that product is poured into the hydrochloric acid containing 5wt% is molten
Copolymer is precipitated in liquid, precipitates washed with EtOH to neutrality, vacuum drying obtains 7- methyl bicyclics [2,2,1] hept- 2-
Alkene, maleic anhydride and N-phenylmaleimide terpolymer.It is 90.2% to calculate reaction yield.
Embodiment 6
In the glove box of nitrogen atmosphere, by 0.010 mole of [1,1 '-bis- (diphenylphosphino) ferrocene] palladium chloride and
0.001 mole of pentanedione is dissolved in 10 milliliters of Isosorbide-5-Nitrae-dioxane in conical flask, under 380rpm, uses magnetic stirring apparatus
Under stirring, 0.006 mole of tetraisopropoxy titanium is instilled in above-mentioned solution, constant temperature is stirred at same 30 DEG C of stir speed (S.S.) after dripping off
Mix 40 minutes, boil off 5ml1,4- dioxane stands 4 hours, obtain solid crystal, filtering produces palladium-titanium complex catalysis
Agent.
By the 0.01 mole of ring of 1- ethyls two [2,2,1] hept-2-ene", 0.01 mol maleic anhydride and 0.01 mole of N- phenyl horse
Carry out acid imide and be added to repeatedly to vacuumize, in the single port glass polymerization bottle of nitrogen charging baking, plus the dissolving of 20ml1,4- dioxane.Press
The ring of 1- ethyls two [2,2,1] hept-2-ene", the 0.06% of maleic anhydride and N-phenylmaleimide three's gross weight take it is above-mentioned
Palladium-titanium complex catalyst, is added in above-mentioned mixture.Constant temperature reacts 3 hours at 90 DEG C.Product is poured into the hydrochloric acid containing 5wt%
Precipitate copolymer in ethanol solution, precipitates washed with EtOH to neutrality, vacuum drying, that is, obtain the ring of 1- ethyls two [2,2,
1] hept-2-ene", maleic anhydride and N-phenylmaleimide terpolymer.It is 44.4% to calculate reaction yield.
Embodiment 7
In the glove box of nitrogen atmosphere, by 0.010 mole of [1,1 '-bis- (diphenylphosphino) ferrocene] palladium chloride and
0.002 mole of 8-hydroxyquinoline is dissolved in 10 milliliters of Isosorbide-5-Nitrae-dioxane in conical flask, under 270rpm, uses magnetic stirring apparatus
Under stirring, 0.001 mole of tetraisopropoxy titanium is instilled in above-mentioned solution, constant temperature is stirred at same 40 DEG C of stir speed (S.S.) after dripping off
Mix 30 minutes, boil off 5ml1,4- dioxane stands 3 hours, obtain solid crystal, filtering produces palladium-titanium complex catalysis
Agent.
The 0.01 mole of ring of 5- ethyls two [2,2,1] hept-2-ene", 0.01 are rubbed maleic anhydride and 0.01 mole of N- phenyl Malaysia
Acid imide, which is added to, repeatedly to be vacuumized, in the single port glass polymerization bottle of nitrogen charging baking, plus the dissolving of 20ml1,4- dioxane.By 5-
The ring of ethyl two [2,2,1] hept-2-ene", the 0.10% of maleic anhydride and N-phenylmaleimide three's gross weight take above-mentioned palladium-
Titanium complex catalyst, is added in above-mentioned mixture.Constant temperature reacts 4 hours at 30 DEG C.Product is poured into the second of the hydrochloric acid containing 5wt%
Copolymer is precipitated in alcoholic solution, precipitates washed with EtOH to neutrality, vacuum drying obtains the ring of 5- ethyls two [2,2,1]
Hept-2-ene", maleic anhydride and N-phenylmaleimide terpolymer.It is 41.4% to calculate reaction yield.
Embodiment 8
In the glove box of nitrogen atmosphere, by 0.006 mole of [1,1 '-bis- (diphenylphosphino) ferrocene] palladium chloride and
0.010 mole of isoquinolin is dissolved in 10 milliliters of 1,2- dichloroethanes in conical flask, under 330rpm, uses magnetic stirrer
Under, 0.001 mole of tetraisopropoxy titanium is instilled in above-mentioned solution, the constant temperature stirring 50 at same 40 DEG C of stir speed (S.S.) after dripping off
Minute, boil off 5ml1,2- dichloroethanes, 5 hours are stood, solid crystal is obtained, filtering produces palladium-titanium complex catalyst.
By the 0.01 mole of ring of 5,5- dimethyl two [2,2,1] hept-2-ene", 0.01 mol maleic anhydride and 0.01 mole of N- benzene
Base maleimide, which is added to, repeatedly to be vacuumized, in the single port glass polymerization bottle of nitrogen charging baking, plus 20ml1,2- dichloroethanes are molten
Solution.By the ring of 5,5- dimethyl two [2,2,1] hept-2-ene", maleic anhydride and N-phenylmaleimide three's gross weight
0.30% takes above-mentioned palladium-titanium complex catalyst, adds in above-mentioned mixture.Constant temperature reacts 4 hours at 70 DEG C.Product is poured into
Copolymer is precipitated in the ethanol solution of the hydrochloric acid containing 5wt%, precipitates washed with EtOH to neutrality, vacuum drying obtains 5,
The ring of 5- dimethyl two [2,2,1] hept-2-ene", maleic anhydride and N-phenylmaleimide terpolymer.Calculate reaction yield
For 45.2%.
Embodiment 9
In the glove box of nitrogen atmosphere, by 0.001 mole of [1,1 '-bis- (diphenylphosphino) ferrocene] palladium chloride and
0.008 mole of α, α '-bipyridyl is dissolved in 10 milliliters of hexamethylenes in conical flask, under 260rpm, uses magnetic stirrer
Under, 0.003 mole of tetraisopropoxy titanium is instilled in above-mentioned solution, the constant temperature stirring 20 at same 50 DEG C of stir speed (S.S.) after dripping off
Minute, 6ml hexamethylenes are boiled off, 2 hours are stood, solid crystal is obtained, filtering produces palladium-titanium complex catalyst.
By the 0.01 mole of ring of 1- phenyl two [2,2,1] hept-2-ene", 0.01 mol maleic anhydride and 0.01 mole of N- phenyl horse
Carry out acid imide and be added to repeatedly to vacuumize, in the single port glass polymerization bottle of nitrogen charging baking, plus the dissolving of 20ml hexamethylenes.By 1- phenyl
Two rings [2,2,1] hept-2-ene", the 0.06% of maleic anhydride and N-phenylmaleimide three's gross weight take above-mentioned palladium-titanium network
Mixture catalyst, is added in above-mentioned mixture.Constant temperature reacts 6 hours at 80 DEG C.The ethanol that product is poured into the hydrochloric acid containing 5wt% is molten
Copolymer is precipitated in liquid, precipitates washed with EtOH to neutrality, vacuum drying obtains the ring of 1- phenyl two [2,2,1] hept- 2-
Alkene, maleic anhydride and N-phenylmaleimide terpolymer.It is 75.4% to calculate reaction yield.
Embodiment 10
In the glove box of nitrogen atmosphere, by 0.001 mole of [1,1 '-bis- (diphenylphosphino) ferrocene] palladium chloride and
0.005 mole of α, α '-bipyridyl is dissolved in 10 milliliters of cyclohexanone in conical flask, under 380rpm, uses magnetic stirrer
Under, 0.007 mole of tetraisopropoxy titanium is instilled in above-mentioned solution, the constant temperature stirring 30 at same 50 DEG C of stir speed (S.S.) after dripping off
Minute, 5ml cyclohexanone is boiled off, 2 hours are stood, solid crystal is obtained, filtering produces palladium-titanium complex catalyst.
By the 0.01 mole of ring of 5- phenyl two [2,2,1] hept-2-ene", 0.01 mol maleic anhydride and 0.01 mole of N- phenyl horse
Carry out acid imide and be added to repeatedly to vacuumize, in the single port glass polymerization bottle of nitrogen charging baking, plus the dissolving of 20ml cyclohexanone.By 5- phenyl
Two rings [2,2,1] hept-2-ene", the 0.07% of maleic anhydride and N-phenylmaleimide three's gross weight take above-mentioned palladium-titanium network
Mixture catalyst, is added in above-mentioned mixture.Constant temperature reacts 5 hours at 60 DEG C.The ethanol that product is poured into the hydrochloric acid containing 5wt% is molten
Copolymer is precipitated in liquid, precipitates washed with EtOH to neutrality, vacuum drying obtains the ring of 5- phenyl two [2,2,1] hept- 2-
Alkene, maleic anhydride and N-phenylmaleimide terpolymer.It is 86.7% to calculate reaction yield.
Embodiment 11
In the glove box of nitrogen atmosphere, by 0.001 mole of [1,1 '-bis- (diphenylphosphino) ferrocene] palladium chloride and
0.007 mole of Phen is dissolved in 10 milliliters of toluene in conical flask, at 300 rpm, with magnetic stirrer, incites somebody to action
0.005 mole of tetraisopropoxy titanium is instilled in above-mentioned solution, and constant temperature is stirred 50 minutes at same 50 DEG C of stir speed (S.S.) after dripping off,
5ml toluene is boiled off, 4 hours are stood, solid crystal is obtained, filtering produces palladium-titanium complex catalyst.
By the 0.01 mole of ring of 5- vinyl two [2,2,1] hept-2-ene", 0.01 mol maleic anhydride and 0.01 mole of N- phenyl
Maleimide, which is added to, repeatedly to be vacuumized, in the single port glass polymerization bottle of nitrogen charging baking, plus the dissolving of 20ml toluene.By 5- ethene
The ring of base two [2,2,1] hept-2-ene", the 0.05% of maleic anhydride and N-phenylmaleimide three's gross weight take above-mentioned palladium-titanium
Complex compound catalyst, is added in above-mentioned mixture.Constant temperature reacts 5 hours at 90 DEG C.Product is poured into the ethanol of the hydrochloric acid containing 5wt%
Copolymer is precipitated in solution, precipitates washed with EtOH to neutrality, vacuum drying obtains the ring of 5- vinyl two [2,2,1]
Hept-2-ene", maleic anhydride and N-phenylmaleimide terpolymer.It is 85.5% to calculate reaction yield.
Embodiment 12
In the glove box of nitrogen atmosphere, by 0.001 mole of [1,1 '-bis- (diphenylphosphino) ferrocene] palladium chloride and
0.005 mole of isoquinolin is dissolved in 10 milliliters of tetrahydrofurans in conical flask, under 400rpm, with magnetic stirrer,
0.007 mole of tetraisopropoxy titanium is instilled in above-mentioned solution, constant temperature stirs 30 points at same 40 DEG C of stir speed (S.S.) after dripping off
Clock, boils off 5ml tetrahydrofurans, stands 5 hours, obtains solid crystal, and filtering produces palladium-titanium complex catalyst.
By 0.01 mole of two ring [2,2,1] hept-2-ene" -5- methyl formate, 0.01 mol maleic anhydride and 0.01 mole of N-
Phenyl maleimide, which is added to, repeatedly to be vacuumized, in the single port glass polymerization bottle of nitrogen charging baking, plus the dissolving of 20ml tetrahydrofurans.
By the 0.04% of two rings [2,2,1] hept-2-ene" -5- methyl formates, maleic anhydride and N-phenylmaleimide three's gross weight
Above-mentioned palladium-titanium complex catalyst is taken, is added in above-mentioned mixture.Constant temperature reacts 6 hours at 60 DEG C.Product is poured into containing 5wt%
Precipitate copolymer in the ethanol solution of hydrochloric acid, precipitates washed with EtOH to neutrality, vacuum drying, that is, obtain two rings [2,2,
1] hept-2-ene" -5- methyl formates, maleic anhydride and N-phenylmaleimide terpolymer.Calculating reaction yield is
73.2%.
Embodiment 13
In the glove box of nitrogen atmosphere, by 0.010 mole of [1,1 '-bis- (diphenylphosphino) ferrocene] palladium chloride and
0.004 mole of quinoline is dissolved in 10 milliliters of petroleum ethers in conical flask, under 340rpm, with magnetic stirrer, incites somebody to action
0.003 mole of tetraisopropoxy titanium is instilled in above-mentioned solution, and constant temperature is stirred 50 minutes at same 50 DEG C of stir speed (S.S.) after dripping off,
6ml petroleum ethers are boiled off, 5 hours are stood, solid crystal is obtained, filtering produces palladium-titanium complex catalyst.
By the special butyl ester of 0.01 mole of two ring [2,2,1] hept-2-ene" -5- formic acid, 0.01 mol maleic anhydride and 0.01 mole
N-phenylmaleimide, which is added to, repeatedly to be vacuumized, in the single port glass polymerization bottle of nitrogen charging baking, plus 20ml petroleum ether dissolutions.
By the special butyl ester of two rings [2,2,1] hept-2-ene" -5- formic acid, maleic anhydride and N-phenylmaleimide three's gross weight
0.06% takes above-mentioned palladium-titanium complex catalyst, adds in above-mentioned mixture.Constant temperature reacts 2 hours at 40 DEG C.Product is poured into
Copolymer is precipitated in the ethanol solution of the hydrochloric acid containing 5wt%, precipitates washed with EtOH to neutrality, vacuum drying obtains two
Ring [2,2,1] hept-2-ene" -5- formic acid spy butyl ester, maleic anhydride and N-phenylmaleimide terpolymer.Reaction is calculated to receive
Rate is 58.7%.
Embodiment 14
In the glove box of nitrogen atmosphere, by 0.010 mole of [1,1 '-bis- (diphenylphosphino) ferrocene] palladium chloride and
0.006 mole of porphyrin is dissolved in 10 milliliters of methyl phenyl ethers anisoles in conical flask, at 300 rpm, with magnetic stirrer, incites somebody to action
0.002 mole of tetraisopropoxy titanium is instilled in above-mentioned solution, and constant temperature is stirred 30 minutes at same 40 DEG C of stir speed (S.S.) after dripping off,
7ml methyl phenyl ethers anisoles are boiled off, 5 hours are stood, solid crystal is obtained, filtering produces palladium-titanium complex catalyst.
By the special butyl ester of 0.01 mole of two ring [2,2,1] hept-2-ene" -5- formic acid, 0.01 mol maleic anhydride and 0.01 mole
N-phenylmaleimide, which is added to, repeatedly to be vacuumized, in the single port glass polymerization bottle of nitrogen charging baking, plus the dissolving of 20ml methyl phenyl ethers anisoles.
By the special butyl ester of two rings [2,2,1] hept-2-ene" -5- formic acid, maleic anhydride and N-phenylmaleimide three's gross weight
0.80% takes above-mentioned palladium-titanium complex catalyst, adds in above-mentioned mixture.Constant temperature reacts 1 hour at 50 DEG C.Product is poured into
Copolymer is precipitated in the ethanol solution of the hydrochloric acid containing 5wt%, precipitates washed with EtOH to neutrality, vacuum drying obtains two
Ring [2,2,1] hept-2-ene" -5- formic acid spy butyl ester, maleic anhydride and N-phenylmaleimide terpolymer.Reaction is calculated to receive
Rate is 51.1%.
Embodiment 15
In the glove box of nitrogen atmosphere, by 0.001 mole of [1,1 '-bis- (diphenylphosphino) ferrocene] palladium chloride and
0.004 mole of α, α '-bipyridyl is dissolved in 10 milliliters of hexamethylenes in conical flask, under 360rpm, uses magnetic stirrer
Under, 0.009 mole of tetraisopropoxy titanium is instilled in above-mentioned solution, the constant temperature stirring 50 at same 40 DEG C of stir speed (S.S.) after dripping off
Minute, 7.5ml hexamethylenes are boiled off, 4 hours are stood, solid crystal is obtained, filtering produces palladium-titanium complex catalyst.
By 0.01 mole of two ring [2,2,1] hept-2-ene", 0.01 mol maleic anhydride and 0.01 mole of N- benzyl maleimide
Amine, which is added to, repeatedly to be vacuumized, in the single port glass polymerization bottle of nitrogen charging baking, plus the dissolving of 20ml hexamethylenes.By two rings [2,2,1]
Hept-2-ene", the 0.20% of maleic anhydride and N-phenylmaleimide three's gross weight take above-mentioned palladium-titanium complex catalyst,
Add in above-mentioned mixture.Constant temperature reacts 5 hours at 70 DEG C.Product, which is poured into the ethanol solution of the hydrochloric acid containing 5wt%, makes copolymer
Precipitation, precipitates washed with EtOH to neutrality, vacuum drying obtains two rings [2,2,1] hept-2-ene", maleic anhydride and N- benzene
Base maleimide terpolymer.It is 66.6% to calculate reaction yield.
Embodiment 16
In the glove box of nitrogen atmosphere, by 0.001 mole of [1,1 '-bis- (diphenylphosphino) ferrocene] palladium chloride and
0.003 mole of 8-hydroxyquinoline is dissolved in conical flask in 10 milliliters of benzene, under 290rpm, with magnetic stirrer,
0.004 mole of tetraisopropoxy titanium is instilled in above-mentioned solution, constant temperature stirs 40 points at same 20 DEG C of stir speed (S.S.) after dripping off
Clock, boils off 7.5ml benzene, stands 3 hours, obtains solid crystal, and filtering produces palladium-titanium complex catalyst.
By 0.01 mole of 1- methyl bicyclics [2,2,1] hept-2-ene", 0.01 mol maleic anhydride and 0.01 mole of N- phenyl horse
Carry out acid imide and be added to repeatedly to vacuumize, in the single port glass polymerization bottle of nitrogen charging baking, plus the dissolving of 20ml benzene.By 1- methyl bicyclics
[2,2,1] hept-2-ene", the 0.50% of maleic anhydride and N-phenylmaleimide three's gross weight take above-mentioned palladium-titanium complex
Catalyst, is added in above-mentioned mixture.Constant temperature reacts 6 hours at 90 DEG C.Product is poured into the ethanol solution of the hydrochloric acid containing 5wt%
Precipitate copolymer, precipitates washed with EtOH to neutrality, vacuum drying, that is, obtain 1- methyl bicyclics [2,2,1] hept-2-ene",
Maleic anhydride and N-phenylmaleimide terpolymer.It is 64.7% to calculate reaction yield.
Claims (5)
1. norborneol alkenes, maleic anhydride and N-phenylmaleimide ternary polymerization catalyst, it is characterised in that the catalyst
Preparation method it is as follows：
In the glove box of nitrogen atmosphere, [1,1 '-bis- (diphenylphosphino) ferrocene] palladium chloride and part are burnt in triangle
The first solvent is dissolved in bottle, under 250~400rpm magnetic agitations, tetraisopropoxy titanium is instilled, at 20~50 DEG C after dripping off
Constant temperature is stirred 20~50 minutes under same stir speed (S.S.) down, boils off the first solvent of 1/2~3/4 volume, stands 2~5 hours, mistake
Leaching solid crystal is palladium-titanium complex catalyst；
The mol ratio of [1,1 '-bis- (diphenylphosphino) ferrocene] palladium chloride and the part is 1: 10~10: 1, institute
The mol ratio for stating [1,1 '-bis- (diphenylphosphino) ferrocene] palladium chloride and the tetraisopropoxy titanium is 1: 10~10: 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 consumption of first solvent and [1,1 '-bis- (diphenylphosphino) ferrocene] palladium chloride, part and four isopropyls
The ratio of epoxide titanium three's total amount is 10 milliliters：0.003~0.020 mole.
2. norborneol alkenes according to claim 1, maleic anhydride and N-phenylmaleimide ternary polymerization catalyst,
[1,1 '-bis- (diphenylphosphino) ferrocene] palladium chloride, tetraisopropoxy titanium and part three rub it is characterized in that described
You are than being 1: 5: 6.
3. norborneol alkenes according to claim 1 or 2, maleic anhydride and N-phenylmaleimide ternary polymerization catalysis
Agent, it is characterised in that the part and first solvent are first dried using preceding；Solid-state in wherein described part is matched somebody with somebody
The drying of body is first to be purified and then be dried in vacuo with recrystallization method；The drying of liquid part in the part is to use calcium hydride
Or metallic sodium is dried, first solvent is dried using calcium chloride or calcium hydride.
4. use norborneol alkenes, maleic anhydride and N- benzyl maleimides as described in claims 1 to 3 any claim
Norborneol alkenes, maleic anhydride and the N-phenylmaleimide method for ternary polymerization of amine ternary polymerization catalyst, its feature exist
In comprising the steps：
Take norborneol alkenes, maleic anhydride and N-phenylmaleimide monomer to be added to according to mol ratio 1: 1: 1 and repeatedly take out true
In empty, nitrogen charging baking single port glass polymerization bottle, the dissolving of the second solvent is added；Then described palladium-titanium complex catalysis is added
Agent, at 20~90 DEG C, reacts 1~6 hour；
The product that reaction is obtained is poured into the ethanol solution of the hydrochloric acid containing 4-5wt%, and obtained precipitates washed with EtOH is into
Property, obtain ENB class, maleic anhydride and N-phenylmaleimide terpolymer after vacuum drying；
The consumption of the palladium-titanium complex catalyst is that norborneol alkenes, maleic anhydride and N-phenylmaleimide three are single
The 0.01%-1.0% of body 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 amount ratio of the molal quantity sum of each polymerized monomer and second solvent is 0.03 mole：20 milliliters.
5. method for ternary polymerization according to claim 4, it is characterised in that the Norbornene derivative be selected from two rings [2,
2,1] hept-2-ene", 1- methyl bicyclics [2,2,1] hept-2-ene", 5- methyl bicyclics [2,2,1] hept-2-ene", 7- methyl bicyclics [2,2,
1] hept-2-ene", the ring of 1- ethyls two [2,2,1] hept-2-ene", the ring of 5- ethyls two [2,2,1] hept-2-ene", the ring of 5,5- dimethyl two [2,
2,1] hept-2-ene", the ring of 1- phenyl two [2,2,1] hept-2-ene", the ring of 5- phenyl two [2,2,1] hept-2-ene", the ring of 5- vinyl two [2,
2,1] the special butyl ester of 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.
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| 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 |
| CN106749912A (en) * | 2016-12-06 | 2017-05-31 | 宁波工程学院 | Norborneol alkenes, vinylacetate and N phenyl maleimide ternary polymerization catalyst and method for ternary polymerization |
| CN106749911A (en) * | 2016-12-06 | 2017-05-31 | 宁波工程学院 | Norborneol alkenes, tetrafluoroethene and N phenyl maleimide ternary polymerization catalyst and method for ternary polymerization |
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| CN106749912A (en) * | 2016-12-06 | 2017-05-31 | 宁波工程学院 | Norborneol alkenes, vinylacetate and N phenyl maleimide ternary polymerization catalyst and method for ternary polymerization |
| CN106749911A (en) * | 2016-12-06 | 2017-05-31 | 宁波工程学院 | Norborneol alkenes, tetrafluoroethene and N phenyl maleimide ternary polymerization catalyst and method for ternary polymerization |
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| CN107540788A (en) * | 2017-09-11 | 2018-01-05 | 宁波工程学院 | Norborneol alkenes, cyclohexene and N phenyl maleimide ternary polymerization catalyst and method for ternary polymerization |
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