CN103254358B - For catalyzer and the method for ternary polymerization of norbornylene class, tetrafluoroethylene and the terpolymer of amylene class - Google Patents
For catalyzer and the method for ternary polymerization of norbornylene class, tetrafluoroethylene and the terpolymer of amylene class Download PDFInfo
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Abstract
The present invention relates to a kind of catalyzer for norbornylene class, tetrafluoroethylene and the terpolymer of amylene class and method for ternary polymerization, it 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 solvent, bottleneck emulsion tube seals, constant temperature 10-30 minute in 40-50 DEG C of water-bath, namely obtains iron complex catalyzer after cooling.Compared with prior art; catalyzer provided by the invention is a kind of Novel iron complex compound catalyst; it can certain pressure, temperature at 20 ~ 120 DEG C time; catalytic activity is produced in nitrogen protection system; catalysis norbornylene and tetrafluoroethylene, amylene, terpolymer, soak product through methyl alcohol and be easy to washing and be separated.Have copolymer yield high, temperature of reaction is low, and catalyzer is cheap, be easy to get, catalytic efficiency high.
Description
Technical field
The present invention relates to 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 special polymkeric substance, has excellent mechanical property, thermotolerance, 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.Tetrafluoroethylene and amylene are inserted after in polynorbornene main chain, cohesiveness and the solubility of polymkeric substance can be improved, thus 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 157nm replica technology.Along with 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, can select 157nm photoetching technique, these technology relate to all respects of photoetching process.This preparation for photoetching material, photoetching material, coating technique, novel resist, to have higher requirement for the novel material etc. of mask and protective film thereof.In order to obtain the good photoetching novel material of performance, develop alternating copolymerization photoetching material, the terpolymer material of such as norbornylene, tetrafluoroethylene and amylene, application simultaneously has the norbornylene of side base, object improves the resistance to corrosion of whole matrix, reduces the light absorption ratio of material, improves lithography performance.
The preparation method of current these materials of synthesis mainly contains the methods such as free radical, living radical, metal catalyst.Disclosed in ProceedingsofSPIEVol.5039 (2003) 80th ~ 92 pages, the synthesis of photoetching material have employed the catalyzer of superoxide as radical polymerization, and ProceedingsofSPIEVol.4690 (2002) 127th ~ 135 pages discloses and adopts AINB (Diisopropyl azodicarboxylate) as the catalyzer of radical polymerization to synthesize photoetching material.Existing norbornylene, mainly adopt free radical polymerisation process with the synthesis of maleic anhydride, acrylate, tetrafluoroethylene or styrol copolymer, with all there is long reaction time in the metal complex to catalyze side of synthesis technique, obtaining the shortcomings such as copolymer yield is low.As adopted Ni/Al metal complex to catalyze norbornylene and tert-butyl methacrylate copolymerization, at polymerization 8 hours, its productive rate does not reach 10%.
Summary of the invention
Technical problem to be solved by this invention provides a kind of catalyzer for norbornylene, tetrafluoroethylene, amylene terpolymer for the present situation of prior art, and this catalyzer can catalyzed reaction at a lower temperature, and catalytic efficiency is high, and copolymer yield is high.
Second technical problem to be solved by this invention provides a kind of for the present situation of prior art to utilize the method that above-mentioned catalyzer carries out norbornylene, tetrafluoroethylene, amylene carry out terpolymer.
The present invention solves the problems of the technologies described above adopted technical scheme: this is used for the catalyzer of norbornylene class, tetrafluoroethylene and the terpolymer of amylene class, it is characterized in that this catalyzer is prepared by following method:
In the single port vial of the drying of atmosphere of inert gases, be dissolved in solvent by ferrous chloride, part and alkyl metal cpd, bottleneck emulsion tube seals, and constant temperature 10-30 minute in 40-50 DEG C of water-bath, namely obtains iron complex catalyzer after 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 to be selected from triethyl aluminum, triisobutyl aluminium, triethyl zinc, n-Butyl Lithium and ethyl aluminum dichloride any one;
Described solvent is selected from tetrahydrofuran (THF), methyl-phenoxide, Isosorbide-5-Nitrae-dioxane, cyclohexanone 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.
The mol ratio of described ferrous chloride, part, alkyl metal cpd three is 1: 2: 8.
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 the above-mentioned catalyzer for norbornylene class, tetrafluoroethylene and the terpolymer of amylene class to carry out the method for norbornylene class, tetrafluoroethylene and the terpolymer of amylene class, it is characterized in that comprising the steps:
Be get norbornylene class, tetrafluoroethylene and amylene class at 1: 1: 1 according to mol ratio, norbornylene class and tetrafluoroethylene, amylene class added in the autoclave of the drying of atmosphere of inert gases, then in this autoclave, adds solvent, dissolve; Described iron complex catalyzer is joined in described autoclave, reacts 1 ~ 6 hour under constant temperature, 0.1-6MP pressure at 20 ~ 120 DEG C;
By reaction product impouring containing in the methanol solution of 5wt% hydrochloric acid, obtain the multipolymer precipitation of norbornylene class, tetrafluoroethylene, amylene based terpolymers; After throw out methanol wash to neutrality, vacuum-drying, namely obtains norbornylene class, tetrafluoroethylene, amylene based terpolymers;
The consumption of described iron complex catalyzer is 0.05 ~ 1% of norbornylene class, tetrafluoroethylene and amylene class three gross weight;
Described solvent is selected from tetrahydrofuran (THF), methyl-phenoxide, Isosorbide-5-Nitrae-dioxane, cyclohexanone or toluene; The consumption of described solvent is 10 milliliters: 0.05 ~ 0.15 mole of polymerized monomer consumption sum.
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,
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 compound catalyst; it can certain pressure, temperature at 20 ~ 120 DEG C time; catalytic activity is produced in nitrogen protection system; catalysis norbornylene and tetrafluoroethylene, amylene, terpolymer, soak product through methyl alcohol and be easy to washing and be separated.Have copolymer yield high, temperature of reaction is low, and catalyzer is cheap, be easy to get, catalytic efficiency high.
Embodiment
Below in conjunction with embodiment, the present invention is described in further detail.
In the catalyst preparation process of following each embodiment, if no special instructions, all drying treatment has been carried out to part wherein and solvent before use.Concrete drying means is: first purify and then vacuum-drying by recrystallization way to the drying of solid ligand; To liquid part be dry with hydrolith or sodium Metal 99.5 is dry; The drying of solvent is with calcium chloride or hydrolith drying.
Embodiment 1
Through repeatedly vacuumizing, inflated with nitrogen baking single port vial in, add 20 milliliters of tetrahydrofuran (THF)s respectively, 0.01 mole of ferrous chloride, 0.10 oxine and 0.10 that rubs rubs triethyl aluminum, in 50 DEG C of water-baths, constant temperature 30 minutes, namely obtains iron complex catalyzer after cooling.
0.03 mole of two ring [2,2,1] hept-2-ene", 0.03 mol of tetrafluoroethylene, 0.03 mole of 1-amylene add in the autoclave of inflated with nitrogen by embodiment, add 10ml tetrahydrofuran (THF) and dissolve.Get the above-mentioned catalyzer of 1% by the total weight of norbornylene, tetrafluoroethylene, 1-amylene three, inject above-mentioned miscellany with syringe.Constant temperature is at 80 DEG C, and 0.1MP pressure, reacts 2 hours.Containing in the methanol solution of 5% hydrochloric acid, norbornylene, tetrafluoroethylene, 1-amylene terpolymer are precipitated product impouring, throw out is by methanol wash to neutral, and vacuum-drying, recording reaction yield is 41.5%.
The calculating of reaction yield is the gross weight of products weight/(norbornene derivative+tetrafluoroethylene+cyclohexene).Following each embodiment is identical therewith.
Embodiment 2
Through repeatedly vacuumizing, inflated with nitrogen baking single port vial in, add 20 milliliters of methyl-phenoxides respectively, 0.01 mole of ferrous chloride, 0.08 rubs α, α ,-dipyridyl and 0.10 rubs triisobutyl aluminium, in 40 DEG C of water-baths, constant temperature 30 minutes, namely obtains ruthenium complex catalyst after 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, adds 10ml methyl-phenoxide and dissolve.Get the above-mentioned catalyzer of 0.9% by the total weight of norbornylene, tetrafluoroethylene, 3-Methyl-1-pentene three, inject above-mentioned miscellany with syringe.Constant temperature is at 20 DEG C, and 0.2MP pressure, reacts 3 hours.Product impouring makes norbornylene, tetrafluoroethylene, 3-Methyl-1-pentene terpolymer precipitate containing in 5% methanol hydrochloride solution, and throw out is extremely neutral by methanol wash, vacuum-drying, reaction yield 45.5%.
Embodiment 3
Through repeatedly vacuumizing, inflated with nitrogen baking single port vial in, add 20 milliliter 1 respectively, 4-dioxane, 0.01 mole of ferrous chloride, 0.07 mole of phenanthroline and 0.08 rub triethyl zinc, and in 45 DEG C of water-baths, constant temperature 15 minutes, namely obtains iron complex catalyzer after 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 10ml1,4-dioxane dissolves.Get the above-mentioned catalyzer of 0.02% by the total weight of norbornylene, tetrafluoroethylene, 2-amylene three, inject above-mentioned miscellany with syringe.Constant temperature is at 100 DEG C, and 1MP pressure, reacts 4 hours.Product impouring makes norbornylene, tetrafluoroethylene, 2-amylene terpolymer precipitate containing in 5% methanol hydrochloride solution, and throw out is extremely neutral by methanol wash, vacuum-drying, reaction yield 51.3%.
Embodiment 4
Through repeatedly vacuumizing, in the single port vial of inflated with nitrogen baking, add 20 milliliters of toluene respectively, 0.01 mole of ferrous chloride, 0.06 pyridine and 0.08 that rubs rubs n-Butyl Lithium, in 40 DEG C of water-baths, constant temperature 20 minutes, namely obtains ruthenium complex catalyst after 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, adds 1ml toluene and dissolve.Get the above-mentioned catalyzer of 0.4% by the total weight of norbornylene, tetrafluoroethylene, 4-methyl-1-pentene three, inject above-mentioned miscellany with syringe.Constant temperature is at 120 DEG C, and 2MP pressure, reacts 4 hours.Product impouring makes norbornylene, tetrafluoroethylene, cyclohexene terpolymer precipitate containing in 5% methanol hydrochloride solution, and throw out is extremely neutral by methanol wash, vacuum-drying, reaction yield 64.7%.
Embodiment 5
Through repeatedly vacuumizing, inflated with nitrogen baking single port vial in, add 20 milliliters of cyclohexanones respectively, 0.01 mole of ferrous chloride, 0.04 isoquinoline 99.9 and 0.06 that rubs rubs ethyl aluminum dichloride, in 50 DEG C of water-baths, constant temperature 25 minutes, namely obtains iron complex catalyzer after cooling.
0.03 mole of 1-ethyl two ring [2,2,1] hept-2-ene", 0.03 mol of tetrafluoroethylene, 0.03 mole of 3-methyl-2-amylene are added in the autoclave of inflated with nitrogen, adds 10ml cyclohexanone and dissolve.Get the above-mentioned catalyzer of 0.5% by the total weight of norbornylene, tetrafluoroethylene, 3-methyl-2-amylene three, inject above-mentioned miscellany with syringe.Constant temperature is at 90 DEG C, and 3MP pressure, reacts 5 hours.Product impouring makes norbornylene, tetrafluoroethylene, 3-methyl-2-amylene terpolymer precipitate containing in 5% methanol hydrochloride solution, and throw out is extremely neutral by methanol wash, vacuum-drying, reaction yield 68.3%.
Embodiment 6
Through repeatedly vacuumizing, inflated with nitrogen baking single port vial in; add 20 milliliters of methyl-phenoxides respectively, 0.01 mole of ferrous chloride, 0.02 Acetyl Acetone and 0.04 that rubs rubs triisobutyl aluminium; in 45 DEG C of water-baths, constant temperature 15 minutes, namely obtains iron complex catalyzer after cooling.
0.03 mole of two ring 5-ethyl two ring [2,2,1] hept-2-ene", 0.03 mol of tetrafluoroethylene, 0.03 mole of 5-cyclohexyl-1-amylene are added in the autoclave of inflated with nitrogen, adds 10ml methyl-phenoxide and dissolve.Get the above-mentioned catalyzer of 0.08% by the total weight of norbornylene, tetrafluoroethylene, 5-cyclohexyl-1-amylene three, inject above-mentioned miscellany with syringe.Constant temperature is at 90 DEG C, and 4MP pressure, reacts 6 hours.Product impouring makes norbornylene, tetrafluoroethylene, 5-cyclohexyl-1-amylene terpolymer precipitate containing in 5% methanol hydrochloride solution, and throw out is extremely neutral by methanol wash, vacuum-drying, reaction yield 77.8%.
Embodiment 7
Through repeatedly vacuumizing, inflated with nitrogen baking single port vial in, add 20 milliliters of tetrahydrofuran (THF)s respectively, 0.01 mole of ferrous chloride, 0.01 quadrol and 0.03 that rubs rubs triisobutyl aluminium, in 50 DEG C of water-baths, constant temperature 30 minutes, namely obtains iron complex catalyzer after cooling.
0.03 mole of 5,5-dimethyl two ring [2,2,1] hept-2-ene", 0.03 mol of tetrafluoroethylene, 0.03 mole of 5-cyclohexyl-2-amylene are added in the autoclave of inflated with nitrogen, adds 10ml tetrahydrofuran (THF) and dissolve.Get the above-mentioned catalyzer of 0.07% by the total weight of norbornylene, tetrafluoroethylene, tetrahydrobenzene three, inject above-mentioned miscellany with syringe.Constant temperature is at 100 DEG C, and 4MP pressure, reacts 5 hours.Product impouring makes norbornylene, tetrafluoroethylene, 5-cyclohexyl-2-amylene terpolymer precipitate containing in 5% methanol hydrochloride solution, and throw out is extremely neutral by methanol wash, vacuum-drying, reaction yield 78.9%.
Embodiment 8
Through repeatedly vacuumizing, inflated with nitrogen baking single port vial in, add 20 milliliters of cyclohexanones respectively, 0.01 mole of ferrous chloride, 0.02 rubs α, α ,-dipyridyl and 0.05 rubs triisobutyl aluminium, in 50 DEG C of water-baths, constant temperature 25 minutes, namely obtains iron complex catalyzer after cooling.
0.03 mole of 1-phenyl two ring [2,2,1] hept-2-ene", 0.03 mol of tetrafluoroethylene, 0.03 mole of 5-cyclohexyl-2-amylene are added in the autoclave of inflated with nitrogen, adds 10ml cyclohexanone and dissolve.Get the above-mentioned catalyzer of 0.06% by the total weight of norbornylene, tetrafluoroethylene, 5-cyclohexyl-2-amylene three, inject above-mentioned miscellany with syringe.Constant temperature is at 115 DEG C, and 5MP pressure, reacts 4 hours.Product impouring makes norbornylene, tetrafluoroethylene, 5-cyclohexyl-2-amylene terpolymer precipitate containing in 5% methanol hydrochloride solution, and throw out is extremely neutral by methanol wash, vacuum-drying, reaction yield 84.2%.
Embodiment 9
Through repeatedly vacuumizing, inflated with nitrogen baking single port vial in, add 20 milliliters of cyclohexanones respectively, 0.02 mole of ferrous chloride, 0.02 porphyrin and 0.05 that rubs rubs triisobutyl aluminium, in 50 DEG C of water-baths, constant temperature 30 minutes, namely obtains iron complex catalyzer after cooling.
0.03 mole of 1-phenyl two ring [2,2,1] hept-2-ene", 0.03 mol of tetrafluoroethylene, 0.03 mole of 1-amylene are added in the autoclave of inflated with nitrogen, adds 10ml cyclohexanone and dissolve.Get the above-mentioned catalyzer of 0.5% by the total weight of norbornylene, tetrafluoroethylene, 1-amylene three, inject above-mentioned miscellany with syringe.Constant temperature is at 120 DEG C, and 5MP pressure, reacts 6 hours.Product impouring makes norbornylene, tetrafluoroethylene, 1-amylene terpolymer precipitate containing in 5% methanol hydrochloride solution, and throw out is extremely neutral by methanol wash, vacuum-drying, reaction yield 83.4%.
Embodiment 10
Through repeatedly vacuumizing, inflated with nitrogen baking single port vial in, add 20 milliliter 1 respectively, 4-dioxane, 0.01 mole of ferrous chloride, 0.03 diethylamine and 0.07 that rubs rubs triethyl aluminum, and in 45 DEG C of water-baths, constant temperature 30 minutes, namely obtains iron complex catalyzer after cooling.
0.03 mole of 5-phenyl two ring [2,2,1] hept-2-ene", 0.03 mol of tetrafluoroethylene, 0.03 mole of 5-cyclohexyl-2-amylene are added in the autoclave of inflated with nitrogen, add 10ml1,4-dioxane dissolves.Get the above-mentioned catalyzer of 0.2% by the total weight of norbornylene, tetrafluoroethylene, 5-cyclohexyl-2-amylene three, inject above-mentioned miscellany with syringe, constant temperature is at 60 DEG C, and 4MP pressure, reacts 2 hours.Product impouring makes norbornylene, tetrafluoroethylene, cyclohexene terpolymer precipitate containing in 5% methanol hydrochloride solution, and throw out is extremely neutral by methanol wash, vacuum-drying, reaction yield 56.6%.
Embodiment 11
Through repeatedly vacuumizing, inflated with nitrogen baking single port vial in, add 20 milliliters of cyclohexanones respectively, 0.08 mole of ferrous chloride, 0.05 rubs α, α ,-dipyridyl and 0.06 rubs triethyl zinc, in 50 DEG C of water-baths, constant temperature 15 minutes, namely obtains iron complex catalyzer after cooling.
0.03 mole of 5-vinyl two ring [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, adds 10ml cyclohexanone and dissolve.Get the above-mentioned catalyzer of 0.02% by the total weight of norbornylene, tetrafluoroethylene, 2-amylene three, inject above-mentioned miscellany with syringe.Constant temperature is at 50 DEG C, and 0.5MP pressure, reacts 1 hour.Product impouring makes norbornylene, tetrafluoroethylene, 2-amylene terpolymer precipitate containing in 5% methanol hydrochloride solution, and throw out is extremely neutral by methanol wash, vacuum-drying, reaction yield 40.7%.
Embodiment 12
Through repeatedly vacuumizing, inflated with nitrogen baking single port vial in, add 20 milliliters of cyclohexanones respectively, 0.10 mole of ferrous chloride, 0.07 rubs α, α ,-dipyridyl and 0.03 rubs triethyl zinc, in 50 DEG C of water-baths, constant temperature 25 minutes, namely obtains iron complex catalyzer after cooling.
By 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 adds in the autoclave of inflated with nitrogen, add 10ml cyclohexanone and dissolve.Get the above-mentioned catalyzer of 0.04% by the total weight of norbornylene, tetrafluoroethylene, 4-cyclohexyl-1-amylene three, inject above-mentioned miscellany with syringe.Constant temperature 70 DEG C, 3MP pressure, reacts 4 hours.Product impouring makes norbornylene, tetrafluoroethylene, 4-cyclohexyl-1-amylene terpolymer precipitate containing in 5% methanol hydrochloride solution, and throw out is extremely neutral by methanol wash, vacuum-drying, reaction yield 55.5%.
Embodiment 13
Through repeatedly vacuumizing, inflated with nitrogen baking single port vial in, add 20 milliliters of cyclohexanones respectively, 0.10 mole of ruthenium trichloride, 0.01 rubs α, α ,-dipyridyl and 0.10 rubs triethyl zinc, in 40 DEG C of water-baths, constant temperature 30 minutes, namely obtains iron complex catalyzer after cooling.
By special for 0.03 mole of two ring [2,2,1] hept-2-ene"-5-formic acid butyl ester, 0.03 mol of tetrafluoroethylene, 0.03 mole, 3-methyl-2-amylene adds in the autoclave of inflated with nitrogen, add 10ml cyclohexanone and dissolve.Get the above-mentioned catalyzer of 0.09% by the total weight of norbornylene, tetrafluoroethylene, 3-methyl-2-amylene three, inject above-mentioned miscellany with syringe.Constant temperature is at 80 DEG C, and 3.5MP pressure, reacts 4 hours.Product impouring makes norbornylene, tetrafluoroethylene, 3-methyl-2-amylene terpolymer precipitate containing in 5% methanol hydrochloride solution, and throw out is extremely neutral by methanol wash, vacuum-drying, reaction yield 63.5%.
Embodiment 14
Through repeatedly vacuumizing, in the single port vial of inflated with nitrogen baking, adding 20 milliliters of Isosorbide-5-Nitrae-dioxane respectively, 0.10 mole of ferrous chloride, 0.10 rubs α, α,-dipyridyl and 0.03 rubs n-Butyl Lithium, and in 45 DEG C of water-baths, constant temperature 20 minutes, namely obtains iron complex catalyzer after cooling.
By 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 adds in the autoclave of inflated with nitrogen, adds 10ml1,4-dioxane dissolves.Get the above-mentioned catalyzer of 0.07% by the total weight of norbornylene, tetrafluoroethylene, 4-methyl-1-pentene three, inject above-mentioned miscellany with syringe.Constant temperature is at 90 DEG C, and 5MP pressure, reacts 5 hours.Product impouring makes norbornylene, tetrafluoroethylene, cyclohexene terpolymer precipitate containing in 5% methanol hydrochloride solution, and throw out is extremely neutral by methanol wash, vacuum-drying, reaction yield 73.5%.
Embodiment 15
Through repeatedly vacuumizing, inflated with nitrogen baking single port vial in, add 20 milliliters of methyl-phenoxides respectively, 0.10 mole of ferrous chloride, 0.08 rubs α, α ,-dipyridyl and 0.01 rubs triisobutyl aluminium, in 50 DEG C of water-baths, constant temperature 15 minutes, namely obtains iron complex catalyzer after cooling.
By 0.03 mole of 5,5-dimethyl two ring [2,2,1] hept-2-ene", 0.03 mol of tetrafluoroethylene, 0.03 mole, 3-Methyl-1-pentene adds in the autoclave of inflated with nitrogen, add 10ml methyl-phenoxide and dissolve.Get the above-mentioned catalyzer of 0.03% by the total weight of norbornylene, tetrafluoroethylene, 3-Methyl-1-pentene three, inject above-mentioned miscellany with syringe.Constant temperature is at 100 DEG C, and 6MP pressure, reacts 6 hours.Product impouring makes norbornylene, tetrafluoroethylene, 3-Methyl-1-pentene terpolymer precipitate containing in 5% methanol hydrochloride solution, and throw out is extremely neutral by methanol wash, vacuum-drying, reaction yield 71.7%.
Embodiment 16
Through repeatedly vacuumizing, inflated with nitrogen baking single port vial in, add 20 milliliters of cyclohexanones respectively, 0.05 mole of ferrous chloride, 0.02 phenanthroline and 0.01 that rubs rubs triisobutyl aluminium, in 40 DEG C of water-baths, constant temperature 25 minutes, namely obtains iron complex catalyzer after cooling.
By 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 adds in the autoclave of inflated with nitrogen, add 10ml cyclohexanone and dissolve.Get the above-mentioned catalyzer of 0.05% by the total weight of norbornylene, tetrafluoroethylene, 4-methyl-1-pentene three, inject above-mentioned miscellany with syringe.Constant temperature 110 DEG C is anti-, and 5MP pressure, reacts 3 hours.Product impouring makes norbornylene, tetrafluoroethylene, 4-methyl-1-pentene terpolymer precipitate containing in 5% methanol hydrochloride solution, and throw out is extremely neutral by methanol wash, vacuum-drying, reaction yield 68.3%.
Embodiment 17
Through repeatedly vacuumizing, inflated with nitrogen baking single port vial in, add 20 milliliters of cyclohexanones respectively, 0.01 mole of ferrous chloride, 0.02 phenanthroline and 0.08 that rubs rubs triisobutyl aluminium, in 50 DEG C of water-baths, constant temperature 25 minutes, namely obtains iron complex catalyzer after cooling.
By 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 adds in the autoclave of inflated with nitrogen, add 10ml cyclohexanone and dissolve.Get the above-mentioned catalyzer of 0.08% by the total weight of norbornylene, tetrafluoroethylene, 4-methyl-1-pentene three, inject above-mentioned miscellany with syringe.Constant temperature 110 DEG C is anti-, and 6MP pressure, reacts 6 hours.Product impouring makes norbornylene, tetrafluoroethylene, 4-methyl-1-pentene terpolymer precipitate containing in 5% methanol hydrochloride solution, and throw out is extremely neutral by methanol wash, vacuum-drying, reaction yield 88.7%.
Embodiment 18
Through repeatedly vacuumizing, inflated with nitrogen baking single port vial in, add 20 milliliters of cyclohexanones respectively, 0.01 mole of ferrous chloride, 0.02 rubs α, α ,-dipyridyl and 0.08 rubs triisobutyl aluminium, in 50 DEG C of water-baths, constant temperature 25 minutes, namely obtains iron complex catalyzer after cooling.
By 0.03 mole of two ring [2,2,1] hept-2-ene", 0.03 mol of tetrafluoroethylene, 0.03 mole, 1-amylene adds in the autoclave of inflated with nitrogen, add 10ml cyclohexanone and dissolve.Get the above-mentioned catalyzer of 0.08% by the total weight of norbornylene, tetrafluoroethylene, 1-amylene three, inject above-mentioned miscellany with syringe.Constant temperature 120 DEG C is anti-, and 5MP pressure, reacts 6 hours.Product impouring makes norbornylene, tetrafluoroethylene, 1-amylene terpolymer precipitate containing in 5% methanol hydrochloride solution, and throw out is extremely neutral by methanol wash, vacuum-drying, reaction yield 86.9%.
Claims (5)
1., for a catalyzer for norbornylene class, tetrafluoroethylene and the terpolymer of amylene class, it is characterized in that this catalyzer is prepared by following method:
In the single port vial of the drying of atmosphere of inert gases, be dissolved in solvent by ferrous chloride, part and alkyl metal cpd, bottleneck emulsion tube seals, and constant temperature 10-30 minute in 40-50 DEG C of water-bath, namely obtains iron complex catalyzer after 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, Isosorbide-5-Nitrae-dioxane, cyclohexanone 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, is characterized in that described ferrous chloride, part, the mol ratio of 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 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 solvent adopts calcium chloride or hydrolith drying with hydrolith or sodium Metal 99.5 drying.
4. use the catalyzer for norbornylene class, tetrafluoroethylene and the terpolymer of amylene class as described in claim as arbitrary in claims 1 to 3 to carry out the method for norbornylene class, tetrafluoroethylene and the terpolymer of amylene class, it is characterized in that comprising the steps:
Be get norbornylene class, tetrafluoroethylene and amylene class at 1: 1: 1 according to mol ratio, norbornylene class and tetrafluoroethylene, amylene class added in the autoclave of the drying of atmosphere of inert gases, then in this autoclave, adds solvent, dissolve; Described iron complex catalyzer is joined in described autoclave, reacts 1 ~ 6 hour under constant temperature, 0.1-6MPa pressure at 20 ~ 120 DEG C;
By reaction product impouring containing in the methanol solution of 5wt% hydrochloric acid, obtain the multipolymer precipitation of norbornylene class, tetrafluoroethylene, amylene based terpolymers; After throw out methanol wash to neutrality, vacuum-drying, namely obtains norbornylene class, tetrafluoroethylene, amylene based terpolymers;
The consumption of described iron complex catalyzer is 0.05 ~ 1% of norbornylene class, tetrafluoroethylene and amylene class three gross weight;
Described solvent is selected from tetrahydrofuran (THF), methyl-phenoxide, Isosorbide-5-Nitrae-dioxane, pimelinketone or toluene; The consumption of described solvent is 10 milliliters: 0.05 ~ 0.15 mole of polymerized monomer consumption sum.
5. norbornylene class according to claim 4, the method of tetrafluoroethylene and the terpolymer of amylene class, 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,
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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| CN106632851B (en) * | 2016-09-26 | 2019-02-15 | 宁波工程学院 | Norborneol alkenes, hexafluoropropene and N-phenylmaleimide ternary polymerization catalyst and method for ternary polymerization |
| CN106749911B (en) * | 2016-12-06 | 2019-03-29 | 宁波工程学院 | Norborneol alkenes, tetrafluoroethene and N-phenylmaleimide ternary polymerization catalyst and method for ternary polymerization |
| CN106749913B (en) * | 2016-12-06 | 2019-03-29 | 宁波工程学院 | Norborneol alkenes, octafluoro cyclopentene and N-phenylmaleimide ternary polymerization catalyst and method for ternary polymerization |
| CN106832120B (en) * | 2017-02-17 | 2019-03-29 | 宁波工程学院 | Norborneol alkenes, hexafluoropropene and vinylene carbonate ternary polymerization catalyst and method for ternary polymerization |
| CN106749915B (en) * | 2017-02-20 | 2019-05-07 | 宁波工程学院 | Norborneol alkenes, esters of acrylic acid and vinylene carbonate ternary polymerization catalyst and method for ternary polymerization |
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| CN101684168B (en) * | 2009-06-15 | 2011-05-11 | 宁波工程学院 | Catalyst used in ternary polymerization of norbornene, acrylate and tetrafluoroethylene, preparation method thereof and method for ternary polymerization |
| CN102702432B (en) * | 2012-05-30 | 2014-06-18 | 宁波工程学院 | Catalyst for use in ternary polymerization of norbornene, maleic anhydride and cyclohexene and ternary polymerization method |
| CN102924658B (en) * | 2012-11-02 | 2014-05-07 | 宁波工程学院 | Catalyst for ternary polymerization of norbornene, derivative of norbornene, tetrafluoroethylene and cyclohexene and method of ternary polymerization |
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