CN103254358A - Catalyst for ternary copolymerization of norbornenes, tetrafluoroethylene and pentenes and ternary copolymerization method - Google Patents
Catalyst for ternary copolymerization of norbornenes, tetrafluoroethylene and pentenes and ternary copolymerization method Download PDFInfo
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- CN103254358A CN103254358A CN2013102097755A CN201310209775A CN103254358A CN 103254358 A CN103254358 A CN 103254358A CN 2013102097755 A CN2013102097755 A CN 2013102097755A CN 201310209775 A CN201310209775 A CN 201310209775A CN 103254358 A CN103254358 A CN 103254358A
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Abstract
The invention relates to a catalyst for ternary copolymerization of norbornenes, tetrafluoroethylene and pentenes and a ternary copolymerization method. The catalyst is characterized in that the catalyst is prepared through the following method comprising the steps of: dissolving iron dichloride, a ligand and an alkyl metal compound in a solvent in a dry single-neck glass bottle in an inert gas atmosphere, sealing a bottle mouth through an emulsion pipe, keeping the constant temperature in a water bath at the temperature of 40-50 DEG C for 10-30min, and cooling to obtain an iron complex catalyst. Compared with the prior art, the catalyst provided by the invention is a novel iron complex catalyst which can produce catalytic activity in an nitrogen-protected system at a certain pressure and the temperature of 20-120 DEG C so as to catalyze the ternary copolymerization of the norbornenes with the tetrafluoroethylene and the pentenes, and a product after soaking in methanol is very easy to wash and separate. The catalyst has the characteristics of high copolymer yield, low reaction temperature, low price, easiness in obtainment, high catalytic efficiency and the like.
Description
Technical field
The present invention relates to the Polymer Synthesizing field, specifically refer to a kind of catalyzer for norbornylene, tetrafluoroethylene and amylene terpolymer and use this catalyzer to carry out the method for norbornylene, tetrafluoroethylene and amylene terpolymer.
Background technology
Polynorbornene is a kind of specific polymers, has excellent mechanical property, thermotolerance, the solubility in organic solvent and the transparency, can be used for the photoetching of 157nm UV-light.The main drawback of polynorbornene is that fragility is poor, viscosity is poor, molecular weight is low.After in tetrafluoroethylene and the amylene insertion polynorbornene main chain, can improve cohesiveness and the solubility of polymkeric substance, thereby make it have high second-order transition temperature, improve its breakable performance in film forming, and can reduce the light absorption ratio of material itself, this multipolymer can be used as photoetching material and is applied to the 157nm replica technology.Along with the littler composition of the development need size of microelectronics industry, be the exposure technique of 1.3 μ m and following live width to being applicable to live width, can select the 157nm photoetching technique, these technology relate to all respects of photoetching process.This preparation for photoetching material, photoetching material, coating technique, novel resist, the novel material etc. that is used for mask and protective film thereof are had higher requirement.For the good photoetching novel material of obtained performance, developed the alternating copolymerization photoetching material, for example the terpolymer material of norbornylene, tetrafluoroethylene and amylene, use the norbornylene that side group is arranged simultaneously, purpose is to improve the resistance to corrosion of whole matrix, reduces the light absorption ratio of material, improves lithography performance.
At present synthetic these preparation methods mainly contain methods such as free radical, living radical, metal catalyst.As the synthetic catalyzer of superoxide as radical polymerization that adopted of the 80th～92 page of disclosed photoetching material of Proceedings of SPIE Vol.5039 (2003), Proceedings of SPIE Vol.4690 (2002) discloses employing AINB(Diisopropyl azodicarboxylate for the 127th～135 page) synthesize photoetching material as the catalyzer of radical polymerization.Existing norbornylene, with the synthetic main free radical polymerisation process that adopts of maleic anhydride, acrylate, tetrafluoroethylene or styrol copolymer, with all having long reaction time in the synthetic square technology of metal complex to catalyze, obtaining shortcomings such as copolymer yield is low.As adopt Ni/Al metal complex to catalyze norbornylene and tert-butyl methacrylate copolymerization, about 8 hours, its productive rate does not reach 10% in polymerization.
Summary of the invention
Technical problem to be solved by this invention is that the present situation at prior art provides a kind of catalyzer for norbornylene, tetrafluoroethylene, amylene terpolymer, and this catalyzer is catalyzed reaction at a lower temperature, and the catalytic efficiency height, the copolymer yield height.
Second technical problem to be solved by this invention is that the present situation at prior art provides a kind of and utilizes above-mentioned catalyzer to carry out the method that norbornylene, tetrafluoroethylene, amylene carry out terpolymer.
The present invention solves the problems of the technologies described above the technical scheme that adopts: should be used for the catalyzer of norbornylene class, tetrafluoroethylene and the terpolymer of amylene class, and it is characterized in that this catalyzer was prepared by following method:
In the single port vial of the drying of atmosphere of inert gases, ferrous chloride, part and alkyl metal cpd are dissolved in the solvent, bottleneck seals with emulsion tube, in 40-50 ℃ of water-bath constant temperature 10-30 minute, namely gets the iron complex catalyzer after the cooling;
The mol ratio of described ferrous chloride and described part is 1: 10～10: 1, and the mol ratio of described ferrous chloride and described alkyl metal cpd is 1: 10～10: 1;
Described part is selected from oxine, α, α '-dipyridyl, phenanthroline, pyridine, isoquinoline 99.9, quinoline, porphyrin, Acetyl Acetone or benzoyl group acetone;
Described alkyl metal cpd is selected from triethyl aluminum, triisobutyl aluminium, triethyl zinc, n-Butyl Lithium and the ethyl aluminum dichloride any one;
Described solvent is selected from tetrahydrofuran (THF), methyl-phenoxide, 1,4-dioxane, pimelinketone or toluene; The ratio of the consumption of described solvent and described ferrous chloride, part and metal alkylide total amount is 20 milliliters: 0.03～0.23 mole.
Described ferrous chloride, part, alkyl metal cpd three's mol ratio is 1: 2: 8.
Described part, described solvent carry out drying before use earlier; The drying of the solid-state part in the wherein said part is earlier with the vacuum-drying then of recrystallization way purifying; The drying of the liquid part in the described part is with hydrolith or sodium Metal 99.5 drying, and described solvent adopts calcium chloride or hydrolith drying.
Use above-mentioned catalyzer for norbornylene class, tetrafluoroethylene and the terpolymer of amylene class to fall the method for norbornylene class, tetrafluoroethylene and the terpolymer of amylene class, it is characterized in that comprising the steps:
Be to get norbornylene, tetrafluoroethylene and amylene at 1: 1: 1 according to mol ratio, norbornylene and tetrafluoroethylene, amylene added in the autoclave of drying of atmosphere of inert gases, in this autoclave, add solvent then, dissolving; Described iron complex catalyzer is joined in the described autoclave, under 20～120 ℃ of following constant temperature, 0.1-6MP pressure, reacted 1～6 hour;
The reaction product impouring is contained in the methanol solution of 5wt% hydrochloric acid, obtain the multipolymer precipitation of norbornylene, tetrafluoroethylene, amylene terpolymer; To neutrality, vacuum-drying namely obtains norbornylene, tetrafluoroethylene, amylene terpolymer to throw out with methanol wash;
Described iron complex catalyst consumption is 0.05～1% of norbornylene, tetrafluoroethylene and amylene three gross weight;
Described solvent is selected from tetrahydrofuran (THF), methyl-phenoxide, 1,4-dioxane, pimelinketone or toluene; The consumption of described solvent is 10 milliliters: 0.05～0.15 mole.
Described norbornylene class is selected from two ring [2,2,1] hept-2-ene"s, 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 rings [2,2,1] hept-2-ene", 5-ethyl two rings [2,2,1] hept-2-ene", 5,5-dimethyl, two rings [2,2,1] hept-2-ene", 1-phenyl two ring [2,2,1] hept-2-ene"s, 5-phenyl two rings [2,2,1] hept-2-ene", 5-vinyl two ring [2,2,1] hept-2-ene"s, two rings [2,2,1] hept-2-ene"-5-methyl-formiate or the special butyl ester of two ring [2,2,1] hept-2-ene"-5-formic acid;
Described amylene class material is selected from 1-amylene, 2-amylene, 3-Methyl-1-pentene, 4-methyl-1-pentene, 3-methyl-2-amylene, 5-cyclohexyl-1-amylene or 5-cyclohexyl-2-amylene.
Compared with prior art; catalyzer provided by the invention is a kind of novel iron complex catalyzer; it can be in certain pressure, temperature during at 20～120 ℃; in nitrogen protection system, produce catalytic activity; catalysis norbornylene and tetrafluoroethylene, amylene, terpolymer are soaked product through methyl alcohol and are easy to the washing separation.Have the copolymer yield height, temperature of reaction is low, the catalyzer cheapness, be easy to get, characteristics such as catalytic efficiency height.
Embodiment
Describe in further detail below in conjunction with the present invention of embodiment.
In the catalyst preparation process of following each embodiment, if no special instructions, all wherein part and solvent carried out drying treatment before use.Concrete drying means is: to dry elder generation recrystallization way purifying and then the vacuum-drying of solid ligand; Be with hydrolith drying or sodium Metal 99.5 drying to the liquid part; The drying of solvent is with calcium chloride or hydrolith drying.
Embodiment 1
Through repeatedly vacuumize, in the single port vial of inflated with nitrogen baking, add 20 milliliters of tetrahydrofuran (THF)s, 0.01 mole of ferrous chloride, 0.10 oxine and 0.10 triethyl aluminum that rubs that rubs respectively, constant temperature is 30 minutes in 50 ℃ of water-baths, namely gets the iron complex catalyzer after the cooling.
Embodiment adds 0.03 mole of two ring [2,2,1] hept-2-ene", 0.03 mol of tetrafluoroethylene, 0.03 mole of 1-amylene in the autoclave of inflated with nitrogen, adds the dissolving of 10ml tetrahydrofuran (THF).Get 1% above-mentioned catalyzer by norbornylene, tetrafluoroethylene, 1-amylene three's gross weight, inject above-mentioned miscellany with syringe.Constant temperature is at 80 ℃, and 0.1MP pressure reacted 2 hours.The product impouring contained make norbornylene, tetrafluoroethylene, 1-amylene terpolymer precipitation in the methanol solution of 5% hydrochloric acid, throw out with methanol wash to neutral, vacuum-drying, recording reaction yield is 41.5%.
The calculating of reaction yield is the gross weight of product weight/(norbornene derivative+tetrafluoroethylene+tetrahydrobenzene).Following each embodiment is identical therewith.
Embodiment 2
Through repeatedly vacuumize, in the single port vial of inflated with nitrogen baking, add 20 milliliters of methyl-phenoxides, 0.01 mole of ferrous chloride, 0.08 α that rubs respectively, α ,-dipyridyl and 0.10 triisobutyl aluminium that rubs, constant temperature is 30 minutes in 40 ℃ of water-baths, namely gets ruthenium complex catalyst after the cooling.
0.03 mole of two ring 1-methyl bicyclic [2,2,1] hept-2-ene", 0.03 mol of tetrafluoroethylene, 0.03 mole of 3-Methyl-1-pentene are added in the autoclave of inflated with nitrogen, add the dissolving of 10ml methyl-phenoxide.Get 0.9% above-mentioned catalyzer by norbornylene, tetrafluoroethylene, 3-Methyl-1-pentene three's gross weight, inject above-mentioned miscellany with syringe.Constant temperature is at 20 ℃, and 0.2MP pressure reacted 3 hours.The product impouring contains makes norbornylene, tetrafluoroethylene, 3-Methyl-1-pentene terpolymer precipitation in 5% methanol hydrochloride solution, throw out is extremely neutral with methanol wash, vacuum-drying, reaction yield 45.5%.
Embodiment 3
Through repeatedly vacuumize, in the single port vial of inflated with nitrogen baking, add 20 milliliter 1 respectively, 4-dioxane, 0.01 mole of ferrous chloride, 0.07 mole of phenanthroline and the 0.08 triethyl zinc that rubs, constant temperature is 15 minutes in 45 ℃ of water-baths, namely gets the iron complex catalyzer after the cooling.
0.03 mole of two ring 5-methyl bicyclic [2,2,1] hept-2-ene", 0.03 mol of tetrafluoroethylene, 0.03 mole of 2-amylene are added in the autoclave of inflated with nitrogen, add 10ml1, the dissolving of 4-dioxane.Get 0.02% above-mentioned catalyzer by norbornylene, tetrafluoroethylene, 2-amylene three's gross weight, inject above-mentioned miscellany with syringe.Constant temperature is at 100 ℃, and 1MP pressure reacted 4 hours.The product impouring contains makes norbornylene, tetrafluoroethylene, 2-amylene terpolymer precipitation in 5% methanol hydrochloride solution, throw out is extremely neutral with methanol wash, vacuum-drying, reaction yield 51.3%.
Embodiment 4
Through repeatedly vacuumizing, in the single port vial of inflated with nitrogen baking, adding 20 milliliters of toluene, 0.01 mole of ferrous chloride, 0.06 pyridine and 0.08 n-Butyl Lithium that rubs that rubs respectively, constant temperature is 20 minutes in 40 ℃ of water-baths, namely gets ruthenium complex catalyst after the cooling.
0.03 mole of two ring 7-methyl bicyclic [2,2,1] hept-2-ene", 0.03 mol of tetrafluoroethylene, 0.03 mole of 4-methyl-1-pentene are added in the autoclave of inflated with nitrogen, add the dissolving of 1ml toluene.Get 0.4% above-mentioned catalyzer by norbornylene, tetrafluoroethylene, 4-methyl-1-pentene three's gross weight, inject above-mentioned miscellany with syringe.Constant temperature is at 120 ℃, and 2MP pressure reacted 4 hours.The product impouring contains makes norbornylene, tetrafluoroethylene, tetrahydrobenzene terpolymer precipitation in 5% methanol hydrochloride solution, throw out is extremely neutral with methanol wash, vacuum-drying, reaction yield 64.7%.
Embodiment 5
Through repeatedly vacuumize, in the single port vial of inflated with nitrogen baking, add 20 milliliters of pimelinketone, 0.01 mole of ferrous chloride, 0.04 isoquinoline 99.9 and 0.06 ethyl aluminum dichloride that rubs that rubs respectively, constant temperature is 25 minutes in 50 ℃ of water-baths, namely gets the iron complex catalyzer after the cooling.
0.03 mole of 1-ethyl two ring [2,2,1] hept-2-ene"s, 0.03 mol of tetrafluoroethylene, 0.03 mole of 3-methyl-2-amylene are added in the autoclave of inflated with nitrogen, add the dissolving of 10ml pimelinketone.Gross weight by norbornylene, tetrafluoroethylene, 3-methyl-2-amylene three is got 0.5% above-mentioned catalyzer, injects above-mentioned miscellany with syringe.Constant temperature is at 90 ℃, and 3MP pressure reacted 5 hours.The product impouring contains makes norbornylene, tetrafluoroethylene, 3-methyl-2-amylene terpolymer precipitation in 5% methanol hydrochloride solution, throw out is extremely neutral with methanol wash, vacuum-drying, reaction yield 68.3%.
Embodiment 6
Through repeatedly vacuumize, in the single port vial of inflated with nitrogen baking; add 20 milliliters of methyl-phenoxides, 0.01 mole of ferrous chloride, 0.02 Acetyl Acetone and 0.04 triisobutyl aluminium that rubs that rubs respectively; constant temperature is 15 minutes in 45 ℃ of water-baths, namely gets the iron complex catalyzer after the cooling.
0.03 mole of two ring 5-ethyl, two ring [2,2,1] hept-2-ene"s, 0.03 mol of tetrafluoroethylene, 0.03 mole of 5-cyclohexyl-1-amylene are added in the autoclave of inflated with nitrogen, add the dissolving of 10ml methyl-phenoxide.Gross weight by norbornylene, tetrafluoroethylene, 5-cyclohexyl-1-amylene three is got 0.08% above-mentioned catalyzer, injects above-mentioned miscellany with syringe.Constant temperature is at 90 ℃, and 4MP pressure reacted 6 hours.The product impouring contains makes norbornylene, tetrafluoroethylene, 5-cyclohexyl-1-amylene terpolymer precipitation in 5% methanol hydrochloride solution, throw out is extremely neutral with methanol wash, vacuum-drying, reaction yield 77.8%.
Embodiment 7
Through repeatedly vacuumize, in the single port vial of inflated with nitrogen baking, add 20 milliliters of tetrahydrofuran (THF)s, 0.01 mole of ferrous chloride, 0.01 quadrol and 0.03 triisobutyl aluminium that rubs that rubs respectively, constant temperature is 30 minutes in 50 ℃ of water-baths, namely gets the iron complex catalyzer after the cooling.
With 0.03 mole 5,5-dimethyl two ring [2,2,1] hept-2-ene"s, 0.03 mol of tetrafluoroethylene, 0.03 mole of 5-cyclohexyl-2-amylene add in the autoclave of inflated with nitrogen, add the dissolving of 10ml tetrahydrofuran (THF).Get 0.07% above-mentioned catalyzer by norbornylene, tetrafluoroethylene, tetrahydrobenzene three's gross weight, inject above-mentioned miscellany with syringe.Constant temperature is at 100 ℃, and 4MP pressure reacted 5 hours.The product impouring contains makes norbornylene, tetrafluoroethylene, 5-cyclohexyl-2-amylene terpolymer precipitation in 5% methanol hydrochloride solution, throw out is extremely neutral with methanol wash, vacuum-drying, reaction yield 78.9%.
Embodiment 8
Through repeatedly vacuumize, in the single port vial of inflated with nitrogen baking, add 20 milliliters of pimelinketone, 0.01 mole of ferrous chloride, 0.02 α that rubs respectively, α ,-dipyridyl and 0.05 triisobutyl aluminium that rubs, constant temperature is 25 minutes in 50 ℃ of water-baths, namely gets the iron complex catalyzer after the cooling.
0.03 mole of 1-phenyl two ring [2,2,1] hept-2-ene"s, 0.03 mol of tetrafluoroethylene, 0.03 mole of 5-cyclohexyl-2-amylene are added in the autoclave of inflated with nitrogen, add the dissolving of 10ml pimelinketone.Gross weight by norbornylene, tetrafluoroethylene, 5-cyclohexyl-2-amylene three is got 0.06% above-mentioned catalyzer, injects above-mentioned miscellany with syringe.Constant temperature is at 115 ℃, and 5MP pressure reacted 4 hours.The product impouring contains makes norbornylene, tetrafluoroethylene, 5-cyclohexyl-2-amylene terpolymer precipitation in 5% methanol hydrochloride solution, throw out is extremely neutral with methanol wash, vacuum-drying, reaction yield 84.2%.
Embodiment 9
Through repeatedly vacuumize, in the single port vial of inflated with nitrogen baking, add 20 milliliters of pimelinketone, 0.02 mole of ferrous chloride, 0.02 porphyrin and 0.05 triisobutyl aluminium that rubs that rubs respectively, constant temperature is 30 minutes in 50 ℃ of water-baths, namely gets the iron complex catalyzer after the cooling.
0.03 mole of 1-phenyl two ring [2,2,1] hept-2-ene"s, 0.03 mol of tetrafluoroethylene, 0.03 mole of 1-amylene are added in the autoclave of inflated with nitrogen, add the dissolving of 10ml pimelinketone.Get 0.5% above-mentioned catalyzer by norbornylene, tetrafluoroethylene, 1-amylene three's gross weight, inject above-mentioned miscellany with syringe.Constant temperature is at 120 ℃, and 5MP pressure reacted 6 hours.The product impouring contains makes norbornylene, tetrafluoroethylene, 1-amylene terpolymer precipitation in 5% methanol hydrochloride solution, throw out is extremely neutral with methanol wash, vacuum-drying, reaction yield 83.4%.
Embodiment 10
Through repeatedly vacuumize, in the single port vial of inflated with nitrogen baking, add 20 milliliter 1 respectively, 4-dioxane, 0.01 mole of ferrous chloride, 0.03 diethylamine and 0.07 triethyl aluminum that rubs that rubs, constant temperature is 30 minutes in 45 ℃ of water-baths, namely gets the iron complex catalyzer after the cooling.
0.03 mole of 5-phenyl two ring [2,2,1] hept-2-ene"s, 0.03 mol of tetrafluoroethylene, 0.03 mole of 5-cyclohexyl-2-amylene are added in the autoclave of inflated with nitrogen, add 10ml1, the dissolving of 4-dioxane.Gross weight by norbornylene, tetrafluoroethylene, 5-cyclohexyl-2-amylene three is got 0.2% above-mentioned catalyzer, injects above-mentioned miscellany with syringe, and constant temperature is at 60 ℃, and 4MP pressure reacted 2 hours.The product impouring contains makes norbornylene, tetrafluoroethylene, tetrahydrobenzene terpolymer precipitation in 5% methanol hydrochloride solution, throw out is extremely neutral with methanol wash, vacuum-drying, reaction yield 56.6%.
Embodiment 11
Through repeatedly vacuumize, in the single port vial of inflated with nitrogen baking, add 20 milliliters of pimelinketone, 0.08 mole of ferrous chloride, 0.05 α that rubs respectively, α ,-dipyridyl and the 0.06 triethyl zinc that rubs, constant temperature is 15 minutes in 50 ℃ of water-baths, namely gets the iron complex catalyzer after the cooling.
0.03 mole of 5-vinyl two ring [2,2,1] hept-2-ene"s, 0.03 mol of tetrafluoroethylene, 0.03 mole of 2-amylene are added in the autoclave of inflated with nitrogen, add the dissolving of 10ml pimelinketone.Get 0.02% above-mentioned catalyzer by norbornylene, tetrafluoroethylene, 2-amylene three's gross weight, inject above-mentioned miscellany with syringe.Constant temperature is at 50 ℃, and 0.5MP pressure reacted 1 hour.The product impouring contains makes norbornylene, tetrafluoroethylene, 2-amylene terpolymer precipitation in 5% methanol hydrochloride solution, throw out is extremely neutral with methanol wash, vacuum-drying, reaction yield 40.7%.
Embodiment 12
Through repeatedly vacuumize, in the single port vial of inflated with nitrogen baking, add 20 milliliters of pimelinketone, 0.10 mole of ferrous chloride, 0.07 α that rubs respectively, α ,-dipyridyl and the 0.03 triethyl zinc that rubs, constant temperature is 25 minutes in 50 ℃ of water-baths, namely gets the iron complex catalyzer after the cooling.
0.03 mole of two ring [2,2,1] hept-2-ene"-5-methyl-formiate, 0.03 mol of tetrafluoroethylene, 0.03 mole, 4-cyclohexyl-1-amylene are added in the autoclave of inflated with nitrogen, add the dissolving of 10ml pimelinketone.Gross weight by norbornylene, tetrafluoroethylene, 4-cyclohexyl-1-amylene three is got 0.04% above-mentioned catalyzer, injects above-mentioned miscellany with syringe.70 ℃ of constant temperature, 3MP pressure reacted 4 hours.The product impouring contains makes norbornylene, tetrafluoroethylene, 4-cyclohexyl-1-amylene terpolymer precipitation in 5% methanol hydrochloride solution, throw out is extremely neutral with methanol wash, vacuum-drying, reaction yield 55.5%.
Embodiment 13
Through repeatedly vacuumize, in the single port vial of inflated with nitrogen baking, add 20 milliliters of pimelinketone, 0.10 mole of ruthenium trichloride, 0.01 α that rubs respectively, α ,-dipyridyl and the 0.10 triethyl zinc that rubs, constant temperature is 30 minutes in 40 ℃ of water-baths, namely gets the iron complex catalyzer after the cooling.
The special butyl ester of 0.03 mole of two ring [2,2,1] hept-2-ene"-5-formic acid, 0.03 mol of tetrafluoroethylene, 0.03 mole, 3-methyl-2-amylene are added in the autoclave of inflated with nitrogen, add the dissolving of 10ml pimelinketone.Gross weight by norbornylene, tetrafluoroethylene, 3-methyl-2-amylene three is got 0.09% above-mentioned catalyzer, injects above-mentioned miscellany with syringe.Constant temperature is at 80 ℃, and 3.5MP pressure reacted 4 hours.The product impouring contains makes norbornylene, tetrafluoroethylene, 3-methyl-2-amylene terpolymer precipitation in 5% methanol hydrochloride solution, throw out is extremely neutral with methanol wash, vacuum-drying, reaction yield 63.5%.
Embodiment 14
Through repeatedly vacuumizing, in the single port vial of inflated with nitrogen baking, add 20 milliliter 1 respectively, 4-dioxane, 0.10 mole of ferrous chloride, 0.10 α that rubs, α,-dipyridyl and 0.03 n-Butyl Lithium that rubs, constant temperature is 20 minutes in 45 ℃ of water-baths, namely gets the iron complex catalyzer after the cooling.
0.03 mole of 7-methyl bicyclic [2,2,1] hept-2-ene", 0.03 mol of tetrafluoroethylene, 0.03 mole, 4-methyl-1-pentene are added in the autoclave of inflated with nitrogen, add 10ml1, the dissolving of 4-dioxane.Get 0.07% above-mentioned catalyzer by norbornylene, tetrafluoroethylene, 4-methyl-1-pentene three's gross weight, inject above-mentioned miscellany with syringe.Constant temperature is at 90 ℃, and 5MP pressure reacted 5 hours.The product impouring contains makes norbornylene, tetrafluoroethylene, tetrahydrobenzene terpolymer precipitation in 5% methanol hydrochloride solution, throw out is extremely neutral with methanol wash, vacuum-drying, reaction yield 73.5%.
Embodiment 15
Through repeatedly vacuumize, in the single port vial of inflated with nitrogen baking, add 20 milliliters of methyl-phenoxides, 0.10 mole of ferrous chloride, 0.08 α that rubs respectively, α ,-dipyridyl and 0.01 triisobutyl aluminium that rubs, constant temperature is 15 minutes in 50 ℃ of water-baths, namely gets the iron complex catalyzer after the cooling.
With 0.03 mole 5,5-dimethyl two ring [2,2,1] hept-2-ene"s, 0.03 mol of tetrafluoroethylene, 0.03 mole, 3-Methyl-1-pentene add in the autoclave of inflated with nitrogen, add the dissolving of 10ml methyl-phenoxide.Get 0.03% above-mentioned catalyzer by norbornylene, tetrafluoroethylene, 3-Methyl-1-pentene three's gross weight, inject above-mentioned miscellany with syringe.Constant temperature is at 100 ℃, and 6MP pressure reacted 6 hours.The product impouring contains makes norbornylene, tetrafluoroethylene, 3-Methyl-1-pentene terpolymer precipitation in 5% methanol hydrochloride solution, throw out is extremely neutral with methanol wash, vacuum-drying, reaction yield 71.7%.
Embodiment 16
Through repeatedly vacuumize, in the single port vial of inflated with nitrogen baking, add 20 milliliters of pimelinketone, 0.05 mole of ferrous chloride, 0.02 phenanthroline and 0.01 triisobutyl aluminium that rubs that rubs respectively, constant temperature is 25 minutes in 40 ℃ of water-baths, namely gets the iron complex catalyzer after the cooling.
0.03 mole of two ring [2,2,1] hept-2-ene"-5-methyl-formiate, 0.03 mol of tetrafluoroethylene, 0.03 mole, 4-methyl-1-pentene are added in the autoclave of inflated with nitrogen, add the dissolving of 10ml pimelinketone.Get 0.05% above-mentioned catalyzer by norbornylene, tetrafluoroethylene, 4-methyl-1-pentene three's gross weight, inject above-mentioned miscellany with syringe.110 ℃ of constant temperature are anti-, and 5MP pressure reacted 3 hours.The product impouring contains makes norbornylene, tetrafluoroethylene, 4-methyl-1-pentene terpolymer precipitation in 5% methanol hydrochloride solution, throw out is extremely neutral with methanol wash, vacuum-drying, reaction yield 68.3%.
Embodiment 17
Through repeatedly vacuumize, in the single port vial of inflated with nitrogen baking, add 20 milliliters of pimelinketone, 0.01 mole of ferrous chloride, 0.02 phenanthroline and 0.08 triisobutyl aluminium that rubs that rubs respectively, constant temperature is 25 minutes in 50 ℃ of water-baths, namely gets the iron complex catalyzer after the cooling.
0.03 mole of 1-methyl bicyclic [2,2,1] hept-2-ene", 0.03 mol of tetrafluoroethylene, 0.03 mole, 4-methyl-1-pentene are added in the autoclave of inflated with nitrogen, add the dissolving of 10ml pimelinketone.Get 0.08% above-mentioned catalyzer by norbornylene, tetrafluoroethylene, 4-methyl-1-pentene three's gross weight, inject above-mentioned miscellany with syringe.110 ℃ of constant temperature are anti-, and 6MP pressure reacted 6 hours.The product impouring contains makes norbornylene, tetrafluoroethylene, 4-methyl-1-pentene terpolymer precipitation in 5% methanol hydrochloride solution, throw out is extremely neutral with methanol wash, vacuum-drying, reaction yield 88.7%.
Embodiment 18
Through repeatedly vacuumize, in the single port vial of inflated with nitrogen baking, add 20 milliliters of pimelinketone, 0.01 mole of ferrous chloride, 0.02 α that rubs respectively, α ,-dipyridyl and 0.08 triisobutyl aluminium that rubs, constant temperature is 25 minutes in 50 ℃ of water-baths, namely gets the iron complex catalyzer after the cooling.
0.03 mole of two ring [2,2,1] hept-2-ene", 0.03 mol of tetrafluoroethylene, 0.03 mole, 1-amylene are added in the autoclave of inflated with nitrogen, add the dissolving of 10ml pimelinketone.Get 0.08% above-mentioned catalyzer by norbornylene, tetrafluoroethylene, 1-amylene three's gross weight, inject above-mentioned miscellany with syringe.120 ℃ of constant temperature are anti-, and 5MP pressure reacted 6 hours.The product impouring contains makes norbornylene, tetrafluoroethylene, 1-amylene terpolymer precipitation in 5% methanol hydrochloride solution, throw out is extremely neutral with methanol wash, vacuum-drying, reaction yield 86.9%.
Claims (5)
1. catalyzer that is used for norbornylene class, tetrafluoroethylene and the terpolymer of amylene class is characterized in that this catalyzer is prepared by following method:
In the single port vial of the drying of atmosphere of inert gases, ferrous chloride, part and alkyl metal cpd are dissolved in the solvent, bottleneck seals with emulsion tube, in 40-50 ℃ of water-bath constant temperature 10-30 minute, namely gets the iron complex catalyzer after the cooling;
The mol ratio of described ferrous chloride and described part is 1: 10～10: 1, and the mol ratio of described ferrous chloride and described alkyl metal cpd is 1: 10～10: 1;
Described part is selected from oxine, α, α ,-dipyridyl, phenanthroline, pyridine, isoquinoline 99.9, quinoline, porphyrin, Acetyl Acetone or benzoyl group acetone;
Described alkyl metal cpd is selected from triethyl aluminum, triisobutyl aluminium, triethyl zinc, n-Butyl Lithium or ethyl aluminum dichloride;
Described solvent is selected from tetrahydrofuran (THF), methyl-phenoxide, 1,4-dioxane, pimelinketone or toluene; The ratio of the consumption of described solvent and described ferrous chloride, part and metal alkylide total amount is 20 milliliters: 0.03～0.23 mole.
2. the catalyzer for norbornylene class, tetrafluoroethylene and the terpolymer of amylene class according to claim 1, the mol ratio that it is characterized in that described ferrous chloride, part, alkyl metal cpd three is 1: 2: 8.
3. the catalyzer for norbornylene class, tetrafluoroethylene and the terpolymer of amylene class according to claim 1 and 2 is characterized in that described part, described solvent carry out drying before use earlier; The drying of the solid-state part in the wherein said part is earlier with the vacuum-drying then of recrystallization way purifying; The drying of the liquid part in the described part is with hydrolith or sodium Metal 99.5 drying, and described solvent adopts calcium chloride or hydrolith drying.
4. use above-mentioned catalyzer for norbornylene class, tetrafluoroethylene and the terpolymer of amylene class to fall the method for norbornylene class, tetrafluoroethylene and the terpolymer of amylene class, it is characterized in that comprising the steps:
Be to get norbornylene, tetrafluoroethylene and amylene at 1: 1: 1 according to mol ratio, norbornylene and tetrafluoroethylene, amylene added in the autoclave of drying of atmosphere of inert gases, in this autoclave, add solvent then, dissolving; Described iron complex catalyzer is joined in the described autoclave, under 20～120 ℃ of following constant temperature, 0.1-6MP pressure, reacted 1～6 hour;
The reaction product impouring is contained in the methanol solution of 5wt% hydrochloric acid, obtain the multipolymer precipitation of norbornylene, tetrafluoroethylene, amylene terpolymer; To neutrality, vacuum-drying namely obtains norbornylene, tetrafluoroethylene, amylene terpolymer to throw out with methanol wash;
Described iron complex catalyst consumption is 0.05～1% of norbornylene, tetrafluoroethylene and amylene three gross weight;
Described solvent is selected from tetrahydrofuran (THF), methyl-phenoxide, 1,4-dioxane, pimelinketone or toluene; The consumption of described solvent is 10 milliliters: 0.05～0.15 mole.
5. norbornylene class according to claim 4, the method of tetrafluoroethylene and the terpolymer of amylene class 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 rings [2,2,1] hept-2-ene", 5-ethyl two rings [2,2,1] hept-2-ene", 5,5-dimethyl two ring [2,2,1] hept-2-ene"s, 1-phenyl two rings [2,2,1] hept-2-ene", 5-phenyl two ring [2,2,1] hept-2-ene"s, 5-vinyl two rings [2,2,1] hept-2-ene", two ring [2,2,1] hept-2-ene"-5-methyl-formiates or two rings [2,2,1] the special butyl ester of hept-2-ene"-5-formic acid;
Described amylene class material is selected from 1-amylene, 2-amylene, 3-Methyl-1-pentene, 4-methyl-1-pentene, 3-methyl-2-amylene, 5-cyclohexyl-1-amylene or 5-cyclohexyl-2-amylene.
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