CN104788615A - Ternary copolymerization catalyst and ternary copolymerization method for norbornenes, styrene and N-phenyl maleimide - Google Patents
Ternary copolymerization catalyst and ternary copolymerization method for norbornenes, styrene and N-phenyl maleimide Download PDFInfo
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Abstract
The invention relates to a ternary copolymerization catalyst and ternary copolymerization method for norbornenes, N-phenyl maleimide and styrene. The ternary copolymerization catalyst is characterized in that a preparation method for the catalyst comprises the following steps of dissolving anhydrous nickel chloride, butyl lithium and a ligand compound into a first solvent in a single-opening glass bottle dried in an inert gas atmosphere, sealing a bottle opening with a latex tube, and maintaining temperature constant for 15-30 minutes at the temperature of 30-60 DEG C, thereby obtaining a nickel-lithium complex catalyst. The ternary copolymerization method comprises the steps: weighing a norbornene monomer, an N-phenyl maleimide monomer and a styrene monomer according to the mole ratio of 1 to 1 to 1, adding the weighed norborneol alkene monomer, the weighed N-phenyl maleimide monomer and the weighed styrene monomer into a vacuum and single-opening glass bottle dried by baking under nitrogen introducing condition, and adding a second solvent to dissolve; then, adding the nickel-lithium complex catalyst, and reacting for 1-5 hours at the temperature of 30-90 DEG C. The catalyst disclosed by the invention can generate activity at low temperature and has the advantages of high catalysis efficiency, low-temperature polymerization and high copolymer yield.
Description
Technical field
The present invention relates to superpolymer field, specifically refer to that a kind of norbornylene class, N-phenyl maleoyl carry out the copolymerization process of amine and polystyrene ternary polymkeric substance catalyzer and norbornylene class, N-phenylmaleimide and polystyrene ternary polymkeric substance.
Background technology
Polynorbornene is a kind of special polymkeric substance, has excellent mechanical property, thermotolerance, solubility in organic solvent and the transparency, can be used for the photoetching of 193nm UV-light.This material main drawback is that fragility, viscosity difference and molecular weight are low etc.N-phenylmaleimide is inserted after in polynorbornene main chain, thermotolerance and the solubility of polymkeric substance can be improved, insert after in polynorbornene main chain containing vinylbenzene, cohesiveness and the solubility of polymkeric substance can be improved.This terpolymer can be used as photoresist and is applied to 193nm replica technology.And; the composition that the development need size of microelectronics industry is less; to being applicable to the exposure technique that live width is 1.3 μm and following live width; 193nm photoetching technique can be selected; these technology relate to all respects of photoetching process, propose new optical material and manufacture and coating technique, novel resist, await the problem of solution for the novel material etc. of mask and protective film thereof.Therefore, in order to the photoetching novel material obtained, develop alternating copolymerization material, main development norbornylene and maleic anhydride class two component copolymerization and norbornylene and maleic anhydride, acrylic acid ester or other component terpolymer materials, application simultaneously has the norbornylene of side base, object improves the resistance to corrosion of whole matrix, improves lithography performance, increases the cohesiveness of material, solubility and toughness.
The method of current these materials of synthesis mainly contains the methods such as free radical, living radical, metal catalyst.If A.E.Feiring and M.Toriumi etc. is by norbornylene, tetrafluoroethylene and acrylate free radical method carry out terpolymer, the synthesis of photoetching material disclosed in Proceedings of SPIE Vol.5039 (2003) 80th ~ 92 pages have employed the catalyzer of superoxide as radical polymerization, the synthesis of photoetching material disclosed in Proceedings of SPIE Vol.4690 (2002) 127th ~ 135 pages have employed the catalyzer of AINB (Diisopropyl azodicarboxylate) as radical polymerization, norbornylene and styrol copolymer photoetching material disclosed in PolymersVol.6 (2014) 565-582 page have employed the synthesis of free radical method.There is long reaction time, obtain the shortcomings such as copolymer yield is low, molecular weight of copolymer is little, multipolymer alternate degree is low in these synthetic methods of current application, and carries out seldom the research of norbornylene, N-phenylmaleimide and styrene terpolymer both at home and abroad.
Summary of the invention
Technical problem to be solved by this invention provides a kind of for the present situation of prior art can reduce temperature of reaction, the norbornylene class improving catalytic efficiency and copolymer yield, N-phenylmaleimide and styrene terpolymer catalyzer.
Another technical problem to be solved by this invention is to provide the method for a kind of temperature of reaction is low, catalytic efficiency is high and copolymer yield is high norbornylene class, N-phenylmaleimide and the terpolymer of benzene second.
The present invention solves the problems of the technologies described above adopted technical scheme: this norbornylene class, N-phenylmaleimide and styrene terpolymer catalyzer, it is characterized in that the preparation method of this catalyzer is as follows:
In the single port vial of the drying of atmosphere of inert gases, be dissolved in solvent by Dehydrated nickel chloride, butyllithium and ligand compound, bottleneck emulsion tube seals, constant temperature 15-30 minute at 30-60 DEG C, obtains nickel-lithium complex catalyzer;
The mol ratio of described Dehydrated nickel chloride and described part is 1: 5 ~ 5: 1, and the mol ratio of described Dehydrated nickel chloride and described butyllithium is 1: 16 ~ 16: 1;
Described part is selected from oxine, α, α ,-dipyridyl, phenanthroline, isoquinoline 99.9, quinoline, porphyrin, Acetyl Acetone or benzoyl group acetone;
Described first solvent is selected from benzene, toluene, tetrahydrofuran (THF), sherwood oil, methyl-phenoxide, Isosorbide-5-Nitrae-dioxane, 1,2-ethylene dichloride, hexanaphthene or pimelinketone; The ratio of the consumption of described solvent and described Dehydrated nickel chloride, part and butyllithium three total amount is 10 milliliters: 0.003 ~ 0.022 mole.
The mol ratio of preferred described Dehydrated nickel chloride, butyllithium and part three is 1: 10: 6.
Described part, described solvent first carry out drying before use; The drying of the solid-state part in wherein said part first purifies then vacuum-drying by recrystallization way; The drying of the liquid part in described part is that described solvent adopts calcium chloride or hydrolith drying with hydrolith or sodium Metal 99.5 drying.
Use above-mentioned norbornylene class, N-phenylmaleimide and styrene terpolymer catalyzer to carry out the method for norbornylene class, N-phenylmaleimide and styrene terpolymer, it is characterized in that comprising the steps:
Be get Norbornene derivative, N-phenylmaleimide monomer and styrene monomer join repeatedly vacuumize, fill in nitrogen baking dry single port vial at 1: 1: 1 according to mol ratio, add the second dissolution with solvents; Then add described terpolymer complex compound catalyst, at 30 ~ 90 DEG C, react 1 ~ 5 hour; The consumption of described terpolymer complex compound catalyst is the 0.05%-2% of norbornylene, N-phenylmaleimide, vinylbenzene three gross weight by the gauge of Dehydrated nickel chloride in catalyzer;
Poured in the ethanolic soln containing 4.5-5.5wt% hydrochloric acid by the product be obtained by reacting, the precipitates washed with EtOH obtained, to neutral, namely obtains norbornylene class, N-phenylmaleimide and styrene copolymer after vacuum-drying;
Described second solvent is selected from benzene, toluene, tetrahydrofuran (THF), sherwood oil, methyl-phenoxide, Isosorbide-5-Nitrae-dioxane, 1,2-ethylene dichloride, hexanaphthene or pimelinketone; The mole number sum of each polymerization single polymerization monomer and the amount ratio of described second solvent are 0.03 mole: 20 milliliters.
Described norbornylene class is 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", 1-ethyl two ring [2, 2, 1] hept-2-ene", 5-ethyl two ring [2, 2, 1] hept-2-ene", 5, 5-dimethyl two ring [2, 2, 1] hept-2-ene", 1-phenyl two ring [2, 2, 1] hept-2-ene", 5-phenyl two ring [2, 2, 1] hept-2-ene", 5-vinyl two ring [2, 2, 1] hept-2-ene", two rings [2, 2, 1] hept-2-ene"-5-methyl-formiate or two rings [2, 2, 1] the special butyl ester of hept-2-ene"-5-formic acid.
Compared with prior art, catalyzer provided by the invention is a kind of New Nickel-lithium complex catalyzer, it can at 30 ~ 90 DEG C of temperature time, react 1 ~ 5 hour, catalytic activity is produced in nitrogen protection system, catalysis norbornylene class, N-phenylmaleimide and styrene terpolymer, and product is easy to washing separation; Copolymer yield is higher, and temperature of reaction is low, and catalyzer raw material is easy to get, catalytic efficiency is high.
Embodiment
Below in conjunction with embodiment, the present invention is described in further detail.
For the preparation process of catalyzer in following examples, if no special instructions, all drying treatment has been carried out to part wherein and solvent.Specifically: the drying of the solid ligand in part first purifies then vacuum-drying by recrystallization way; The drying of the liquid part in part is dry or dry with sodium Metal 99.5 with hydrolith.The drying of solvent is with calcium chloride or hydrolith drying.
Embodiment 1
Getting 0.001 mole of Dehydrated nickel chloride, 0.001 mole of butyllithium and 0.001 mole of isoquinoline 99.9 is dissolved in 10 milliliters of benzene, put into through repeatedly vacuumizing, single port vial that inflated with nitrogen baking is dry, bottleneck emulsion tube seals, put into Water Tank with Temp.-controlled at 30 DEG C 20 minutes, obtain nickel-lithium complex catalyzer.
0.01 mole of two ring [2,2,1] hept-2-ene", 0.01 mole of N-phenylmaleimide and 0.01 mole of vinylbenzene being added through repeatedly vacuumizing, in single port vial that inflated with nitrogen baking is dry, adding 20ml benzene and dissolving.By the gauge of Dehydrated nickel chloride in catalyzer be norbornylene, N-phenylmaleimide, vinylbenzene three gross weight 0.05% get above-mentioned nickel-lithium complex catalyzer, inject above-mentioned miscellany with syringe.Constant temperature, at 30 DEG C, reacts 5 hours.Product impouring makes multipolymer precipitate containing in 5.5wt% ethanol solution hydrochloride, and precipitates washed with EtOH is to neutral, and vacuum-drying, namely obtains two rings [2,2,1] hept-2-ene", N-phenylmaleimide and styrene copolymer.Calculating reaction yield is 26.7%.
The method of calculation of reaction yield are terpolymer weight/comonomer gross weight × 100%.Yield method of calculation in following each embodiment are identical therewith.
Embodiment 2
Getting 0.001 mole of Dehydrated nickel chloride, 0.0016 mole of butyllithium and 0.001 mole of phenanthroline is dissolved in 10 milliliters of toluene, put into through repeatedly vacuumizing, single port vial that inflated with nitrogen baking is dry, bottleneck emulsion tube seals, put into Water Tank with Temp.-controlled at 60 DEG C 15 minutes, obtain nickel-lithium complex catalyzer.
0.01 mole, 0.01 mole 1-methyl bicyclic [2,2,1] hept-2-ene", N-phenylmaleimide and 0.01 mole of vinylbenzene being added through repeatedly vacuumizing, in single port vial that inflated with nitrogen baking is dry, adding 20ml toluene and dissolving.By the gauge of Dehydrated nickel chloride in catalyzer be norbornylene, N-phenylmaleimide, vinylbenzene three gross weight 0.06% get above-mentioned nickel-lithium complex catalyzer, inject above-mentioned miscellany with syringe.Constant temperature, at 90 DEG C, reacts 1 hour.Product impouring makes multipolymer precipitate containing in 5wt% ethanol solution hydrochloride, and precipitates washed with EtOH is to neutral, and vacuum-drying, namely obtains 1-methyl bicyclic [2,2,1] hept-2-ene", N-phenylmaleimide and styrene copolymer.Calculating reaction yield is 52.8%.
Embodiment 3
Get 0.001 mole of Dehydrated nickel chloride, 0.010 mole of butyllithium and 0.005 mole of α, α,-dipyridyl is dissolved in 10 milliliters of toluene, put into through repeatedly vacuumizing, single port vial that inflated with nitrogen baking is dry, bottleneck emulsion tube seals, put into Water Tank with Temp.-controlled at 50 DEG C 20 minutes, obtain nickel-lithium complex catalyzer.
0.01 mole of two ring [2,2,1] hept-2-ene", 0.01 mole of N-phenylmaleimide and 0.01 mole of vinylbenzene being added through repeatedly vacuumizing, in single port vial that inflated with nitrogen baking is dry, adding 20ml toluene and dissolving.By the gauge of Dehydrated nickel chloride in catalyzer be norbornylene, N-phenylmaleimide, vinylbenzene three gross weight 0.20% get above-mentioned nickel-lithium complex catalyzer, inject above-mentioned miscellany with syringe.Constant temperature, at 80 DEG C, reacts 4.5 hours.Product impouring makes multipolymer precipitate containing in 5wt% ethanol solution hydrochloride, and precipitates washed with EtOH is to neutral, and vacuum-drying, namely obtains two rings [2,2,1] hept-2-ene", N-phenylmaleimide and styrene copolymer.Calculating reaction yield is 82.3%.
Embodiment 4
Getting 0.001 mole of Dehydrated nickel chloride, 0.004 mole of butyllithium and 0.003 mole of oxine is dissolved in 10 milliliters of tetrahydrofuran (THF)s, put into through repeatedly vacuumizing, single port vial that inflated with nitrogen baking is dry, bottleneck emulsion tube seals, put into Water Tank with Temp.-controlled at 40 DEG C 25 minutes, obtain nickel-lithium complex catalyzer.
0.01 mole of 5-methyl bicyclic [2,2,1] hept-2-ene", 0.01 mole of N-phenylmaleimide and 0.01 mole of vinylbenzene being added through repeatedly vacuumizing, in single port vial that inflated with nitrogen baking is dry, adding 20ml tetrahydrofuran (THF) and dissolving.By the gauge of Dehydrated nickel chloride in catalyzer be norbornylene, N-phenylmaleimide, vinylbenzene three gross weight 0.09% get above-mentioned nickel-lithium complex catalyzer, inject above-mentioned miscellany with syringe.Constant temperature, at 70 DEG C, reacts 3 hours.Product impouring makes multipolymer precipitate containing in 5wt% ethanol solution hydrochloride, and precipitates washed with EtOH is to neutral, and vacuum-drying, namely obtains 5-methyl bicyclic [2,2,1] hept-2-ene", N-phenylmaleimide and styrene copolymer.Calculating reaction yield is 56.4%.
Embodiment 5
Getting 0.001 mole of Dehydrated nickel chloride, 0.006 mole of butyllithium and 0.004 mole of quinoline is dissolved in 10 milliliters of sherwood oils, put into through repeatedly vacuumizing, single port vial that inflated with nitrogen baking is dry, bottleneck emulsion tube seals, put into Water Tank with Temp.-controlled at 40 DEG C 25 minutes, obtain nickel-lithium complex catalyzer.
0.01 mole of 7-methyl bicyclic [2,2,1] hept-2-ene", 0.01 mole of N-phenylmaleimide and 0.01 mole of vinylbenzene being added through repeatedly vacuumizing, in single port vial that inflated with nitrogen baking is dry, adding 20ml petroleum ether dissolution.By the gauge of Dehydrated nickel chloride in catalyzer be norbornylene, N-phenylmaleimide, vinylbenzene three gross weight 0.12% get above-mentioned nickel-lithium complex catalyzer, inject above-mentioned miscellany with syringe.Constant temperature, at 60 DEG C, reacts 4 hours.Product impouring makes multipolymer precipitate containing in 4.5wt% ethanol solution hydrochloride, and precipitates washed with EtOH is to neutral, and vacuum-drying, namely obtains 7-methyl bicyclic [2,2,1] hept-2-ene", N-phenylmaleimide and styrene copolymer.Calculating reaction yield is 63.7%.
Embodiment 6
Getting 0.001 mole of Dehydrated nickel chloride, 0.008 mole of butyllithium and 0.005 mole of porphyrin is dissolved in 10 milliliters of methyl-phenoxides, put into through repeatedly vacuumizing, single port vial that inflated with nitrogen baking is dry, bottleneck emulsion tube seals, put into Water Tank with Temp.-controlled at 35 DEG C 28 minutes, obtain nickel-lithium complex catalyzer.
0.01 mole of 1-ethyl two ring [2,2,1] hept-2-ene", 0.01 mole of N-phenylmaleimide and 0.01 mole of vinylbenzene being added through repeatedly vacuumizing, in single port vial that inflated with nitrogen baking is dry, adding 20ml methyl-phenoxide and dissolving.By the gauge of Dehydrated nickel chloride in catalyzer be norbornylene, N-phenylmaleimide, vinylbenzene three gross weight 0.15% get above-mentioned nickel-lithium complex catalyzer, inject above-mentioned miscellany with syringe.Constant temperature, at 70 DEG C, reacts 3 hours.Product impouring makes multipolymer precipitate containing in 4.5wt% ethanol solution hydrochloride, and precipitates washed with EtOH is to neutral, and vacuum-drying, namely obtains 1-ethyl two ring [2,2,1] hept-2-ene", N-phenylmaleimide and styrene copolymer.Calculating reaction yield is 71.9%.
Embodiment 7
Get 0.001 mole of Dehydrated nickel chloride, 0.012 mole of butyllithium and 0.002 mole of porphyrin and be dissolved in 10 milliliter 1, in 4-dioxane, put into through repeatedly vacuumizing, single port vial that inflated with nitrogen baking is dry, bottleneck emulsion tube seals, put into Water Tank with Temp.-controlled at 60 DEG C 15 minutes, obtain nickel-lithium complex catalyzer.
0.01 mole of 5-ethyl two ring [2,2,1] hept-2-ene", 0.01 mole of N-phenylmaleimide and 0.01 mole of vinylbenzene are added through repeatedly vacuumizing, in single port vial that inflated with nitrogen baking is dry, add 20ml1,4-dioxane dissolves.By the gauge of Dehydrated nickel chloride in catalyzer be norbornylene, N-phenylmaleimide, vinylbenzene three gross weight 0.30% get above-mentioned nickel-lithium complex catalyzer, inject above-mentioned miscellany with syringe.Constant temperature, at 50 DEG C, reacts 2 hours.Product impouring makes multipolymer precipitate containing in 5wt% ethanol solution hydrochloride, and precipitates washed with EtOH is to neutral, and vacuum-drying, namely obtains 5-ethyl two ring [2,2,1] hept-2-ene", N-phenylmaleimide and styrene copolymer.Calculating reaction yield is 58.3%.
Embodiment 8
Get 0.001 mole of Dehydrated nickel chloride, 0.014 mole of butyllithium and 0.003 mole of Acetyl Acetone and be dissolved in 10 milliliter 1; in 2-ethylene dichloride; put into through repeatedly vacuumizing, single port vial that inflated with nitrogen baking is dry; bottleneck emulsion tube seals; put into Water Tank with Temp.-controlled at 45 DEG C 30 minutes, obtain nickel-lithium complex catalyzer.
0.01 mole of 5,5-dimethyl two ring [2,2,1] hept-2-ene", 0.01 mole of N-phenylmaleimide and 0.01 mole of vinylbenzene are added through repeatedly vacuumizing, in single port vial that inflated with nitrogen baking is dry, add 20ml1,2-ethylene dichloride dissolves.By the gauge of Dehydrated nickel chloride in catalyzer be norbornylene, N-phenylmaleimide, vinylbenzene three gross weight 0.40% get above-mentioned nickel-lithium complex catalyzer, inject above-mentioned miscellany with syringe.Constant temperature, at 40 DEG C, reacts 4 hours.Product impouring makes multipolymer precipitate containing in 5wt% ethanol solution hydrochloride, and precipitates washed with EtOH is to neutral, and vacuum-drying, namely obtains 5,5-dimethyl two ring [2,2,1] hept-2-ene", N-phenylmaleimide and styrene copolymer.Calculating reaction yield is 56.6%.
Embodiment 9
Getting 0.016 mole of Dehydrated nickel chloride, 0.001 mole of butyllithium and 0.004 mole of benzoyl group acetone is dissolved in 10 milliliters of hexanaphthenes; put into through repeatedly vacuumizing, single port vial that inflated with nitrogen baking is dry; bottleneck emulsion tube seals; put into Water Tank with Temp.-controlled at 55 DEG C 30 minutes, obtain nickel-lithium complex catalyzer.
0.01 mole of 1-phenyl two ring [2,2,1] hept-2-ene", 0.01 mole of N-phenylmaleimide and 0.01 mole of vinylbenzene being added through repeatedly vacuumizing, in single port vial that inflated with nitrogen baking is dry, adding 20ml hexanaphthene and dissolving.By the gauge of Dehydrated nickel chloride in catalyzer be norbornylene, N-phenylmaleimide, vinylbenzene three gross weight 0.60% get above-mentioned nickel-lithium complex catalyzer, inject above-mentioned miscellany with syringe.Constant temperature, at 30 DEG C, reacts 5 hours.Product impouring makes multipolymer precipitate containing in 5wt% ethanol solution hydrochloride, and precipitates washed with EtOH is to neutral, and vacuum-drying, namely obtains 1-phenyl two ring [2,2,1] hept-2-ene", N-phenylmaleimide and styrene copolymer.Calculating reaction yield is 47.4%.
Embodiment 9
Getting 0.015 mole of Dehydrated nickel chloride, 0.003 mole of butyllithium and 0.003 mole of phenanthroline is dissolved in 10 milliliters of pimelinketone, put into through repeatedly vacuumizing, single port vial that inflated with nitrogen baking is dry, bottleneck emulsion tube seals, put into Water Tank with Temp.-controlled at 35 DEG C 15 minutes, obtain nickel-lithium complex catalyzer.
0.01 mole of 5-phenyl two ring [2,2,1] hept-2-ene", 0.01 mole of N-phenylmaleimide and 0.01 mole of vinylbenzene being added through repeatedly vacuumizing, in single port vial that inflated with nitrogen baking is dry, adding 20ml pimelinketone and dissolving.By the gauge of Dehydrated nickel chloride in catalyzer be norbornylene, N-phenylmaleimide, vinylbenzene three gross weight 0.80% get above-mentioned nickel-lithium complex catalyzer, inject above-mentioned miscellany with syringe.Constant temperature, at 60 DEG C, reacts 3 hours.Product impouring makes multipolymer precipitate containing in 5wt% ethanol solution hydrochloride, and precipitates washed with EtOH is to neutral, and vacuum-drying, namely obtains 5-phenyl two ring [2,2,1] hept-2-ene", N-phenylmaleimide and styrene copolymer.Calculating reaction yield is 57.7%.
Embodiment 10
Getting 0.010 mole of Dehydrated nickel chloride, 0.001 mole of butyllithium and 0.004 mole of oxine is dissolved in 10 milliliters of sherwood oils, put into through repeatedly vacuumizing, single port vial that inflated with nitrogen baking is dry, bottleneck emulsion tube seals, put into Water Tank with Temp.-controlled at 35 DEG C 15 minutes, obtain nickel-lithium complex catalyzer.
0.01 mole of 5-vinyl two ring [2,2,1] hept-2-ene", 0.01 mole of N-phenylmaleimide and 0.01 mole of vinylbenzene being added through repeatedly vacuumizing, in single port vial that inflated with nitrogen baking is dry, adding 20ml petroleum ether dissolution.By the gauge of Dehydrated nickel chloride in catalyzer be norbornylene, N-phenylmaleimide, vinylbenzene three gross weight 1.00% get above-mentioned nickel-lithium complex catalyzer, inject above-mentioned miscellany with syringe.Constant temperature, at 70 DEG C, reacts 2 hours.Product impouring makes multipolymer precipitate containing in 5wt% ethanol solution hydrochloride, and precipitates washed with EtOH is to neutral, and vacuum-drying, namely obtains 5-vinyl two ring [2,2,1] hept-2-ene", N-phenylmaleimide and styrene copolymer.Calculating reaction yield is 61.1%.
Embodiment 11
Getting 0.006 mole of Dehydrated nickel chloride, 0.001 mole of butyllithium and 0.002 mole of quinoline is dissolved in 10 milliliters of methyl-phenoxides, put into through repeatedly vacuumizing, single port vial that inflated with nitrogen baking is dry, bottleneck emulsion tube seals, put into Water Tank with Temp.-controlled at 40 DEG C 20 minutes, obtain nickel-lithium complex catalyzer.
0.01 mole of two ring [2,2,1] hept-2-ene"-5-methyl-formiate, 0.01 mole of N-phenylmaleimide and 0.01 mole of vinylbenzene being added through repeatedly vacuumizing, in single port vial that inflated with nitrogen baking is dry, adding 20ml methyl-phenoxide and dissolving.By the gauge of Dehydrated nickel chloride in catalyzer be norbornylene, N-phenylmaleimide, vinylbenzene three gross weight 1.50% get above-mentioned nickel-lithium complex catalyzer, inject above-mentioned miscellany with syringe.Constant temperature, at 50 DEG C, reacts 3 hours.Product impouring makes multipolymer precipitate containing in 5wt% ethanol solution hydrochloride, and precipitates washed with EtOH is to neutral, and vacuum-drying, namely obtains two rings [2,2,1] hept-2-ene"-5-methyl-formiate, N-phenylmaleimide and styrene copolymer.Calculating reaction yield is 54.3%.
Embodiment 12
Getting 0.002 mole of Dehydrated nickel chloride, 0.001 mole of butyllithium and 0.001 mole of Acetyl Acetone is dissolved in 10 milliliters of hexanaphthenes; put into through repeatedly vacuumizing, single port vial that inflated with nitrogen baking is dry; bottleneck emulsion tube seals; put into Water Tank with Temp.-controlled at 40 DEG C 30 minutes, obtain nickel-lithium complex catalyzer.
Special for 0.01 mole of two ring [2,2,1] hept-2-ene"-5-formic acid butyl ester, 0.01 mole of N-phenylmaleimide and 0.01 mole of vinylbenzene being added through repeatedly vacuumizing, in single port vial that inflated with nitrogen baking is dry, adding 20ml hexanaphthene and dissolving.By the gauge of Dehydrated nickel chloride in catalyzer be norbornylene, N-phenylmaleimide, vinylbenzene three gross weight 2.00% get above-mentioned nickel-lithium complex catalyzer, inject above-mentioned miscellany with syringe.Constant temperature, at 80 DEG C, reacts 4.5 hours.Product impouring makes multipolymer precipitate containing in 5wt% ethanol solution hydrochloride, and precipitates washed with EtOH is to neutral, and vacuum-drying, namely obtains two rings [2,2,1] hept-2-ene"-5-formic acid special butyl ester, N-phenylmaleimide and styrene copolymer.Calculating reaction yield is 63.3%.
Embodiment 13
Getting 0.001 mole of Dehydrated nickel chloride, 0.009 mole of butyllithium and 0.005 mole of phenanthroline is dissolved in 10 milliliters of toluene, put into through repeatedly vacuumizing, single port vial that inflated with nitrogen baking is dry, bottleneck emulsion tube seals, put into Water Tank with Temp.-controlled at 50 DEG C 20 minutes, obtain nickel-lithium complex catalyzer.
0.01 mole of 1-methyl bicyclic [2,2,1] hept-2-ene", 0.01 mole of N-phenylmaleimide and 0.01 mole of vinylbenzene being added through repeatedly vacuumizing, in single port vial that inflated with nitrogen baking is dry, adding 20ml toluene and dissolving.By the gauge of Dehydrated nickel chloride in catalyzer be norbornylene, N-phenylmaleimide, vinylbenzene three gross weight 0.30% get above-mentioned nickel-lithium complex catalyzer, inject above-mentioned miscellany with syringe.Constant temperature, at 90 DEG C, reacts 1 hour.Product impouring makes multipolymer precipitate containing in 5wt% ethanol solution hydrochloride, and precipitates washed with EtOH is to neutral, and vacuum-drying, namely obtains 1-methyl bicyclic [2,2,1] hept-2-ene", N-phenylmaleimide and styrene copolymer.Calculating reaction yield is 75.1%.
Embodiment 14
Getting 0.001 mole of Dehydrated nickel chloride, 0.002 mole of butyllithium and 0.002 mole of porphyrin is dissolved in 10 milliliters of benzene, put into through repeatedly vacuumizing, single port vial that inflated with nitrogen baking is dry, bottleneck emulsion tube seals, put into Water Tank with Temp.-controlled at 40 DEG C 15 minutes, obtain nickel-lithium complex catalyzer.
0.01 mole of 7-methyl bicyclic [2,2,1] hept-2-ene", 0.01 mole of N-phenylmaleimide and 0.01 mole of vinylbenzene being added through repeatedly vacuumizing, in single port vial that inflated with nitrogen baking is dry, adding 20ml benzene and dissolving.By the gauge of Dehydrated nickel chloride in catalyzer be norbornylene, N-phenylmaleimide, vinylbenzene three gross weight 0.50% get above-mentioned nickel-lithium complex catalyzer, inject above-mentioned miscellany with syringe.Constant temperature, at 30 DEG C, reacts 5 hours.Product impouring makes multipolymer precipitate containing in 5wt% ethanol solution hydrochloride, and precipitates washed with EtOH is to neutral, and vacuum-drying, namely obtains 7-methyl bicyclic [2,2,1] hept-2-ene", N-phenylmaleimide and styrene copolymer.Calculating reaction yield is 55.9%.
Embodiment 15
Getting 0.001 mole of Dehydrated nickel chloride, 0.005 mole of butyllithium and 0.005 mole of porphyrin is dissolved in 10 milliliters of tetrahydrofuran (THF)s, put into through repeatedly vacuumizing, single port vial that inflated with nitrogen baking is dry, bottleneck emulsion tube seals, put into Water Tank with Temp.-controlled at 30 DEG C 30 minutes, obtain nickel-lithium complex catalyzer.
0.01 mole of 5-ethyl two ring [2,2,1] hept-2-ene", 0.01 mole of N-phenylmaleimide and 0.01 mole of vinylbenzene being added through repeatedly vacuumizing, in single port vial that inflated with nitrogen baking is dry, adding 20ml tetrahydrofuran (THF) and dissolving.By the gauge of Dehydrated nickel chloride in catalyzer be norbornylene, N-phenylmaleimide, vinylbenzene three gross weight 0.70% get above-mentioned nickel-lithium complex catalyzer, inject above-mentioned miscellany with syringe.Constant temperature, at 60 DEG C, reacts 3 hours.Product impouring makes multipolymer precipitate containing in 5wt% ethanol solution hydrochloride, and precipitates washed with EtOH is to neutral, and vacuum-drying, namely obtains 5-ethyl two ring [2,2,1] hept-2-ene", N-phenylmaleimide and styrene copolymer.Calculating reaction yield is 68.5%.
Embodiment 16
Getting 0.001 mole of Dehydrated nickel chloride, 0.007 mole of butyllithium and 0.003 mole of isoquinoline 99.9 is dissolved in 10 milliliters of hexanaphthenes, put into through repeatedly vacuumizing, single port vial that inflated with nitrogen baking is dry, bottleneck emulsion tube seals, put into Water Tank with Temp.-controlled at 55 DEG C 25 minutes, obtain nickel-lithium complex catalyzer.
0.01 mole of two ring [2,2,1] hept-2-ene"-5-methyl-formiate, 0.01 mole of N-phenylmaleimide and 0.01 mole of vinylbenzene being added through repeatedly vacuumizing, in single port vial that inflated with nitrogen baking is dry, adding 20ml hexanaphthene and dissolving.By the gauge of Dehydrated nickel chloride in catalyzer be norbornylene, N-phenylmaleimide, vinylbenzene three gross weight 0.90% get above-mentioned nickel-lithium complex catalyzer, inject above-mentioned miscellany with syringe.Constant temperature, at 70 DEG C, reacts 2 hours.Product impouring makes multipolymer precipitate containing in 5wt% ethanol solution hydrochloride, and precipitates washed with EtOH is to neutral, and vacuum-drying, namely obtains two rings [2,2,1] hept-2-ene"-5-methyl-formiate, N-phenylmaleimide and styrene copolymer.Calculating reaction yield is 71.9%.
Embodiment 17
Getting 0.015 mole of Dehydrated nickel chloride, 0.001 mole of butyllithium and 0.003 mole of isoquinoline 99.9 is dissolved in 10 milliliters of hexanaphthenes, put into through repeatedly vacuumizing, single port vial that inflated with nitrogen baking is dry, bottleneck emulsion tube seals, put into Water Tank with Temp.-controlled at 55 DEG C 25 minutes, obtain nickel-lithium complex catalyzer.
0.01 mole of two ring [2,2,1] hept-2-ene"-5-methyl-formiate, 0.01 mole of N-phenylmaleimide and 0.01 mole of vinylbenzene being added through repeatedly vacuumizing, in single port vial that inflated with nitrogen baking is dry, adding 20ml hexanaphthene and dissolving.By the gauge of Dehydrated nickel chloride in catalyzer be norbornylene, N-phenylmaleimide, vinylbenzene three gross weight 1.80% get above-mentioned nickel-lithium complex catalyzer, inject above-mentioned miscellany with syringe.Constant temperature, at 70 DEG C, reacts 2 hours.Product impouring makes multipolymer precipitate containing in the ethanolic soln of 5wt% hydrochloric acid, and precipitates washed with EtOH is to neutral, and vacuum-drying, namely obtains two rings [2,2,1] hept-2-ene"-5-methyl-formiate, N-phenylmaleimide and styrene copolymer.Calculating reaction yield is 71.9%.
Claims (5)
1. norbornylene class, N-phenylmaleimide and a styrene terpolymer catalyzer, is characterized in that the preparation method of this catalyzer is as follows:
In the single port vial of the drying of atmosphere of inert gases, Dehydrated nickel chloride, butyllithium and ligand compound are dissolved in the first solvent, bottleneck emulsion tube seals, and constant temperature 15-30 minute at 30-60 DEG C obtains nickel-lithium complex catalyzer;
The mol ratio of described Dehydrated nickel chloride and described part is 1: 5 ~ 5: 1, and the mol ratio of described Dehydrated nickel chloride and described butyllithium is 1: 16 ~ 16: 1;
Described part is selected from oxine, α, α ,-dipyridyl, phenanthroline, isoquinoline 99.9, quinoline, porphyrin, Acetyl Acetone or benzoyl group acetone;
Described first solvent is selected from benzene, toluene, tetrahydrofuran (THF), sherwood oil, methyl-phenoxide, Isosorbide-5-Nitrae-dioxane, 1,2-ethylene dichloride, hexanaphthene or pimelinketone; The ratio of the consumption of described solvent and described Dehydrated nickel chloride, part and butyllithium three total amount is 10 milliliters: 0.003 ~ 0.022 mole.
2. terpolymer catalyzer according to claim 1, is characterized in that described Dehydrated nickel chloride, the mol ratio of butyllithium and part three is 1: 10: 6.
3. terpolymer catalyzer according to claim 1 and 2, is characterized in that described part, described first solvent first carries out drying before use; The drying of the solid-state part in wherein said part first purifies then vacuum-drying by recrystallization way; The drying of the liquid part in described part is that described first solvent adopts calcium chloride or hydrolith drying with hydrolith or sodium Metal 99.5 drying.
4. use above-mentioned norbornylene class, N-phenylmaleimide and styrene terpolymer catalyzer to carry out the method for norbornylene class, N-phenylmaleimide and styrene terpolymer, it is characterized in that comprising the steps:
Be get Norbornene derivative, N-phenylmaleimide monomer and styrene monomer join in vacuum, inflated with nitrogen baking dry single port vial at 1: 1: 1 according to mol ratio, add the second dissolution with solvents; Then add described nickel-lithium complex catalyzer, at 30 ~ 90 DEG C, react 1 ~ 5 hour; The consumption of described terpolymer complex compound catalyst is the 0.05%-2% of norbornylene, N-phenylmaleimide, vinylbenzene three gross weight by the gauge of Dehydrated nickel chloride in catalyzer;
Poured in the ethanolic soln containing 4.5-5.5wt% hydrochloric acid by the product be obtained by reacting, the precipitates washed with EtOH obtained, to neutral, namely obtains norbornylene class, N-phenylmaleimide and styrene copolymer after vacuum-drying;
Described second solvent is selected from benzene, toluene, tetrahydrofuran (THF), sherwood oil, methyl-phenoxide, Isosorbide-5-Nitrae-dioxane, 1,2-ethylene dichloride, hexanaphthene or pimelinketone; The amount ratio of described Norbornene derivative, N-phenylmaleimide monomer and styrene monomer mole number sum and described second solvent is 0.03 mole: 20 milliliters.
5. method for ternary polymerization according to claim 4, it is characterized in that described norbornylene class is 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", 1-ethyl two ring [2, 2, 1] hept-2-ene", 5-ethyl two ring [2, 2, 1] hept-2-ene", 5, 5-dimethyl two ring [2, 2, 1] hept-2-ene", 1-phenyl two ring [2, 2, 1] hept-2-ene", 5-phenyl two ring [2, 2, 1] hept-2-ene", 5-vinyl two ring [2, 2, 1] hept-2-ene", two rings [2, 2, 1] hept-2-ene"-5-methyl-formiate or two rings [2, 2, 1] the special butyl ester of hept-2-ene"-5-formic acid.
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