CN104311738B - Norbornylene class, maleic anhydride and octafluoro cyclopentenes terpolymer catalyzer and method for ternary polymerization - Google Patents
Norbornylene class, maleic anhydride and octafluoro cyclopentenes terpolymer catalyzer and method for ternary polymerization Download PDFInfo
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- CN104311738B CN104311738B CN201410542612.3A CN201410542612A CN104311738B CN 104311738 B CN104311738 B CN 104311738B CN 201410542612 A CN201410542612 A CN 201410542612A CN 104311738 B CN104311738 B CN 104311738B
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Abstract
The present invention relates to a kind of norbornylene class, maleic anhydride and octafluoro cyclopentenes terpolymer catalyzer and method for ternary polymerization, catalyzer is in the single port vial of the drying of atmosphere of inert gases, three (isopropylcyclopentadiene) are changed terbium, tributyl cyclopentadienyl tin and ligand compound to be dissolved in the first solvent, bottleneck emulsion tube seals, constant temperature 8-12 minute at 35-45 DEG C, namely obtains terbium-Xi terpolymer complex compound catalyst.Get reaction monomers and catalyzer in proportion, react under certain temperature and pressure and namely obtain terpolymer.Catalyzer provided by the invention can produce catalytic activity in nitrogen protection system, catalysis norbornylene class, maleic anhydride and the terpolymer of octafluoro cyclopentenes, and product is easy to washing separation; Copolymer yield is high, and temperature of reaction is low, and catalyzer raw material is cheap and easy to get, catalytic efficiency is high.
Description
Technical field
The present invention relates to superpolymer field, specifically refer to the copolymerization process of a kind of norbornene polymer catalyzer and norbornene polymer.
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.Maleic anhydride is inserted after in polynorbornene main chain, cohesiveness and the solubility of polymkeric substance can be improved, after in fluorine-containing ethylene insertion polynorbornene main chain, cohesiveness and the solubility of polymkeric substance can be improved, and reduce the light absorption ratio of material itself.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.As norbornylene, tetrafluoroethylene and acrylate free radical method are carried out terpolymer by A.E.Feiring and M.Toriumi etc., the synthesis of photoetching material disclosed in ProceedingsofSPIEVol.5039 (2003) 80th ~ 92 pages have employed the catalyzer of superoxide as radical polymerization, and the synthesis of photoetching material disclosed in ProceedingsofSPIEVol.4690 (2002) 127th ~ 135 pages have employed the catalyzer of AINB (Diisopropyl azodicarboxylate) as radical polymerization.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 domestic research norbornylene and maleic anhydride, the terpolymer of octafluoro cyclopentenes is carried out seldom.
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, maleic anhydride and octafluoro cyclopentenes 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, maleic anhydride and the terpolymer of octafluoro cyclopentenes.
The present invention solves the problems of the technologies described above adopted technical scheme: this norbornylene class, maleic anhydride and octafluoro cyclopentenes 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, three (isopropylcyclopentadiene) are changed terbium, tributyl cyclopentadienyl tin and ligand compound to be dissolved in the first solvent, bottleneck emulsion tube seals, constant temperature 8-12 minute at 35-45 DEG C, obtains terbium-Xi terpolymer complex compound catalyst;
The mol ratio that described three (isopropylcyclopentadiene) change terbium and described part is 1: 8 ~ 8: 1, and the mol ratio that described three (isopropylcyclopentadiene) change terbium and described tributyl cyclopentadienyl tin is 1: 8 ~ 8: 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 that the consumption of described first solvent and described three (isopropylcyclopentadiene) change terbium, part and tributyl cyclopentadienyl tin three total amount is 10 milliliters: 0.003 ~ 0.017 mole.
Preferably described three (isopropylcyclopentadiene) change terbium, the mol ratio of tributyl cyclopentadienyl tin and part three is 1: 2: 4.
Preferably, described part, described first 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 first solvent adopts calcium chloride or hydrolith drying with hydrolith or sodium Metal 99.5 drying.
Use above-mentioned norbornylene class, maleic anhydride and octafluoro cyclopentenes terpolymer catalyzer to carry out the method for norbornylene class, maleic anhydride and the terpolymer of octafluoro cyclopentenes, it is characterized in that comprising the steps:
Be get Norbornene derivative, maleic anhydride and octafluoro cyclopentenes monomer join in the autoclave of inertia drying at 1: 1: 1 according to mol ratio, add the second dissolution with solvents; Then add described terpolymer complex compound catalyst, at 40 ~ 160 DEG C, react 1 ~ 6 hour under 0.1-7MPa pressure; The consumption of described terpolymer complex compound catalyst is the 0.05%-3% of norbornylene class, maleic anhydride, octafluoro cyclopentenes three gross weight by the gauge that three (isopropylcyclopentadiene) in catalyzer change terbium;
Poured in the methanol solution containing 4.5-5.5wt% hydrochloric acid by the product be obtained by reacting, the throw out methanol wash obtained, to neutral, namely obtains norbornylene class, maleic anhydride and octafluoro cyclopentenes terpolymer 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.
Preferably, 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 novel rare-earth complex compound catalyst, it can at 40 ~ 160 DEG C of temperature time, under 0.1-7MPa pressure, react 1 ~ 6 hour, in nitrogen protection system, produce catalytic activity, catalysis norbornylene class, maleic anhydride and the terpolymer of octafluoro cyclopentenes, and product is easy to washing separation; Copolymer yield is high, and temperature of reaction is low, and catalyzer raw material is cheap and 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 the first 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 the first solvent is with calcium chloride or hydrolith drying.
Embodiment 1
Get 0.001 mole three (isopropylcyclopentadiene) to change terbium, 0.001 mole of tributyl cyclopentadienyl tin and 0.008 mole of oxine and be dissolved in 10 milliliters of benzene, put into through repeatedly vacuumizing, inflated with nitrogen baking single port vial, bottleneck emulsion tube seals, put into Water Tank with Temp.-controlled at 35 DEG C 8 minutes, obtain terbium-Xi terpolymer complex compound catalyst.
0.01 mole of two ring [2,2,1] hept-2-ene", 0.01 mol maleic anhydride and 0.01 mole of octafluoro cyclopentenes are added in the autoclave of inflated with nitrogen drying, adds 20ml benzene and dissolve.The gauge changing terbium by three (isopropylcyclopentadiene) in catalyzer is norbornylene, maleic anhydride, octafluoro cyclopentenes three gross weight 0.05% get above-mentioned terbium-Xi terpolymer complex compound catalyst, inject above-mentioned miscellany with syringe.Constant temperature is at 40 DEG C, and 0.1MPa pressure, reacts 1 hour.Product impouring makes multipolymer precipitate containing in 5% methanol hydrochloride solution, and throw out is by methanol wash to neutral, and vacuum-drying, namely obtains two rings [2,2,1] hept-2-ene", maleic anhydride and octafluoro cyclopentenes terpolymer.Calculating reaction yield is 31.3%.
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
Get 0.001 mole three (isopropylcyclopentadiene) and change terbium, 0.008 mole of tributyl cyclopentadienyl tin and 0.001 mole of α, α '-dipyridyl is dissolved in 10 milliliters of toluene, put into through repeatedly vacuumizing, inflated with nitrogen baking single port vial, bottleneck emulsion tube seals, put into Water Tank with Temp.-controlled at 40 DEG C 10 minutes, obtain terbium-Xi terpolymer complex compound catalyst.
0.01 mole of 1-methyl bicyclic [2,2,1] hept-2-ene", 0.01 mol maleic anhydride and 0.01 mole of octafluoro cyclopentenes are added in the autoclave of inflated with nitrogen drying, adds 20ml toluene and dissolve.The gauge changing terbium by three (isopropylcyclopentadiene) in catalyzer is norbornylene, maleic anhydride, octafluoro cyclopentenes three gross weight 3% get above-mentioned terbium-Xi terpolymer complex compound catalyst, inject above-mentioned miscellany with syringe.Constant temperature is at 160 DEG C, and 7MPa pressure, reacts 6 hours.Product impouring makes multipolymer precipitate containing in 5% methanol hydrochloride solution, and throw out is by methanol wash to neutral, and vacuum-drying, namely obtains 1-methyl bicyclic [2,2,1] hept-2-ene", maleic anhydride and octafluoro cyclopentenes terpolymer.Calculating reaction yield is 64.5%.
Embodiment 3
Get 0.001 mole three (isopropylcyclopentadiene) and change terbium, 0.002 mole of tributyl cyclopentadienyl tin and 0.004 mole of α, α '-dipyridyl is dissolved in 10 milliliters of toluene, put into through repeatedly vacuumizing, inflated with nitrogen baking single port vial, bottleneck emulsion tube seals, put into Water Tank with Temp.-controlled at 40 DEG C 10 minutes, obtain terbium-Xi terpolymer complex compound catalyst.
0.01 mole of two ring [2,2,1] hept-2-ene", 0.01 mol maleic anhydride and 0.01 mole of octafluoro cyclopentenes are added in the autoclave of inflated with nitrogen drying, adds 20ml toluene and dissolve.The gauge changing terbium by three (isopropylcyclopentadiene) in catalyzer is norbornylene, maleic anhydride, octafluoro cyclopentenes three gross weight 1% get above-mentioned terbium-Xi terpolymer complex compound catalyst, inject above-mentioned miscellany with syringe.Constant temperature is at 150 DEG C, and 5MPa pressure, reacts 6 hours.Product impouring makes multipolymer precipitate containing in 5% methanol hydrochloride solution, and throw out is by methanol wash to neutral, and vacuum-drying, namely obtains two rings [2,2,1] hept-2-ene", maleic anhydride and octafluoro cyclopentenes terpolymer.Calculating reaction yield is 84.5%.
Embodiment 4
Get 0.001 mole three (isopropylcyclopentadiene) to change terbium, 0.003 mole of tributyl cyclopentadienyl tin and 0.005 mole of phenanthroline and be dissolved in 10 milliliters of tetrahydrofuran (THF)s, put into through repeatedly vacuumizing, inflated with nitrogen baking single port vial, bottleneck emulsion tube seals, put into Water Tank with Temp.-controlled at 45 DEG C 12 minutes, obtain terbium-Xi terpolymer complex compound catalyst.
0.01 mole of 5-methyl bicyclic [2,2,1] hept-2-ene", 0.01 mol maleic anhydride and 0.01 mole of octafluoro cyclopentenes are added in the autoclave of inflated with nitrogen drying, adds 20ml tetrahydrofuran (THF) and dissolve.The gauge changing terbium by three (isopropylcyclopentadiene) in catalyzer is norbornylene, maleic anhydride, octafluoro cyclopentenes three gross weight 2% get above-mentioned terbium-Xi terpolymer complex compound catalyst, inject above-mentioned miscellany with syringe.Constant temperature is at 50 DEG C, and 1MPa pressure, reacts 2 hours.Product impouring makes multipolymer precipitate containing in 5% methanol hydrochloride solution, and throw out is by methanol wash to neutral, and vacuum-drying, namely obtains 5-methyl bicyclic [2,2,1] hept-2-ene", maleic anhydride and octafluoro cyclopentenes terpolymer.Calculating reaction yield is 44.1%.
Embodiment 5
Get 0.001 mole three (isopropylcyclopentadiene) to change terbium, 0.004 mole of tributyl cyclopentadienyl tin and 0.006 mole of isoquinoline 99.9 and be dissolved in 10 milliliters of sherwood oils, put into through repeatedly vacuumizing, inflated with nitrogen baking single port vial, bottleneck emulsion tube seals, put into Water Tank with Temp.-controlled at 40 DEG C 10 minutes, obtain terbium-Xi terpolymer complex compound catalyst.
0.01 mole of 7-methyl bicyclic [2,2,1] hept-2-ene", 0.01 mol maleic anhydride and 0.01 mole of octafluoro cyclopentenes are added in the autoclave of inflated with nitrogen drying, adds 20ml petroleum ether dissolution.The gauge changing terbium by three (isopropylcyclopentadiene) in catalyzer is norbornylene, maleic anhydride, octafluoro cyclopentenes three gross weight 0.1% get above-mentioned terbium-Xi terpolymer complex compound catalyst, inject above-mentioned miscellany with syringe.Constant temperature is at 60 DEG C, and 2MPa pressure, reacts 3 hours.Product impouring makes multipolymer precipitate containing in 5% methanol hydrochloride solution, and throw out is by methanol wash to neutral, and vacuum-drying, namely obtains 7-methyl bicyclic [2,2,1] hept-2-ene", maleic anhydride and octafluoro cyclopentenes terpolymer.Calculating reaction yield is 41.3%.
Embodiment 6
Get 0.001 mole three (isopropylcyclopentadiene) to change terbium, 0.005 mole of tributyl cyclopentadienyl tin and 0.007 mole of quinoline and be dissolved in 10 milliliters of methyl-phenoxides, put into through repeatedly vacuumizing, inflated with nitrogen baking single port vial, bottleneck emulsion tube seals, put into Water Tank with Temp.-controlled at 40 DEG C 10 minutes, obtain terbium-Xi terpolymer complex compound catalyst.
0.01 mole of 1-ethyl two ring [2,2,1] hept-2-ene", 0.01 mol maleic anhydride and 0.01 mole of octafluoro cyclopentenes are added in the autoclave of inflated with nitrogen drying, adds 20ml methyl-phenoxide and dissolve.The gauge changing terbium by three (isopropylcyclopentadiene) in catalyzer is norbornylene, maleic anhydride, octafluoro cyclopentenes three gross weight 0.3% get above-mentioned terbium-Xi terpolymer complex compound catalyst, inject above-mentioned miscellany with syringe.Constant temperature is at 70 DEG C, and 3MPa pressure, reacts 4 hours.Product impouring makes multipolymer precipitate containing in 5% methanol hydrochloride solution, and throw out is by methanol wash to neutral, and vacuum-drying, namely obtains 1-ethyl two ring [2,2,1] hept-2-ene", maleic anhydride and octafluoro cyclopentenes terpolymer.Calculating reaction yield is 51.3%.
Embodiment 7
Get 0.001 mole three (isopropylcyclopentadiene) to change terbium, 0.006 mole of tributyl cyclopentadienyl tin and 0.001 mole of porphyrin and be dissolved in 10 milliliter 1, in 4-dioxane, put into through repeatedly vacuumizing, inflated with nitrogen baking single port vial, bottleneck emulsion tube seals, put into Water Tank with Temp.-controlled at 40 DEG C 10 minutes, obtain terbium-Xi terpolymer complex compound catalyst.
0.01 mole of 5-ethyl two ring [2,2,1] hept-2-ene", 0.01 mol maleic anhydride and 0.01 mole of octafluoro cyclopentenes are added in the autoclave of inflated with nitrogen drying, add 20ml1,4-dioxane dissolves.The gauge changing terbium by three (isopropylcyclopentadiene) in catalyzer is norbornylene, maleic anhydride, octafluoro cyclopentenes three gross weight 0.4% get above-mentioned terbium-Xi terpolymer complex compound catalyst, inject above-mentioned miscellany with syringe.Constant temperature is at 80 DEG C, and 4MPa pressure, reacts 5 hours.Product impouring makes multipolymer precipitate containing in 5% methanol hydrochloride solution, and throw out is by methanol wash to neutral, and vacuum-drying, namely obtains 5-ethyl two ring [2,2,1] hept-2-ene", maleic anhydride and octafluoro cyclopentenes terpolymer.Calculating reaction yield is 58.8%.
Embodiment 8
Get 0.001 mole three (isopropylcyclopentadiene) to change terbium, 0.007 mole of tributyl cyclopentadienyl tin and 0.002 mole of Acetyl Acetone and be dissolved in 10 milliliter 1; in 2-ethylene dichloride; put into through repeatedly vacuumizing, inflated with nitrogen baking single port vial; bottleneck emulsion tube seals; put into Water Tank with Temp.-controlled at 40 DEG C 10 minutes, obtain terbium-Xi terpolymer complex compound catalyst.
0.01 mole of 5,5-dimethyl two ring [2,2,1] hept-2-ene", 0.01 mol maleic anhydride and 0.01 mole of octafluoro cyclopentenes are added in the autoclave of inflated with nitrogen drying, add 20ml1,2-ethylene dichloride dissolves.The gauge changing terbium by three (isopropylcyclopentadiene) in catalyzer is norbornylene, maleic anhydride, octafluoro cyclopentenes three gross weight 0.5% get above-mentioned terbium-Xi terpolymer complex compound catalyst, inject above-mentioned miscellany with syringe.Constant temperature is at 90 DEG C, and 0.9MPa pressure, reacts 5 hours.Product impouring makes multipolymer precipitate containing in 5% methanol hydrochloride solution, and throw out is by methanol wash to neutral, and vacuum-drying, namely obtains 5,5-dimethyl two ring [2,2,1] hept-2-ene", maleic anhydride and octafluoro cyclopentenes terpolymer.Calculating reaction yield is 55.5%.
Embodiment 9
Get 0.002 mole three (isopropylcyclopentadiene) to change terbium, 0.001 mole of tributyl cyclopentadienyl tin and 0.002 mole of benzoyl group acetone and be dissolved in 10 milliliters of hexanaphthenes; put into through repeatedly vacuumizing, inflated with nitrogen baking single port vial; bottleneck emulsion tube seals; put into Water Tank with Temp.-controlled at 40 DEG C 10 minutes, obtain terbium-Xi terpolymer complex compound catalyst.
0.01 mole of 1-phenyl two ring [2,2,1] hept-2-ene", 0.01 mol maleic anhydride and 0.01 mole of octafluoro cyclopentenes are added in the autoclave of inflated with nitrogen drying, adds 20ml hexanaphthene and dissolve.The gauge changing terbium by three (isopropylcyclopentadiene) in catalyzer is norbornylene, maleic anhydride, octafluoro cyclopentenes three gross weight 0.6% get above-mentioned terbium-Xi terpolymer complex compound catalyst, inject above-mentioned miscellany with syringe.Constant temperature is at 100 DEG C, and 0.8MPa pressure, reacts 7 hours.Product impouring makes multipolymer precipitate containing in 5% methanol hydrochloride solution, and throw out is by methanol wash to neutral, and vacuum-drying, namely obtains 1-phenyl two ring [2,2,1] hept-2-ene", maleic anhydride and octafluoro cyclopentenes terpolymer.Calculating reaction yield is 62.4%.
Embodiment 10
Get 0.003 mole three (isopropylcyclopentadiene) to change terbium, 0.001 mole of tributyl cyclopentadienyl tin and 0.008 mole of benzoyl group acetone and be dissolved in 10 milliliters of pimelinketone; put into through repeatedly vacuumizing, inflated with nitrogen baking single port vial; bottleneck emulsion tube seals; put into Water Tank with Temp.-controlled at 40 DEG C 10 minutes, obtain terbium-Xi terpolymer complex compound catalyst.
0.01 mole of 5-phenyl two ring [2,2,1] hept-2-ene", 0.01 mol maleic anhydride and 0.01 mole of octafluoro cyclopentenes are added in the autoclave of inflated with nitrogen drying, adds 20ml pimelinketone and dissolve.The gauge changing terbium by three (isopropylcyclopentadiene) in catalyzer is norbornylene, maleic anhydride, octafluoro cyclopentenes three gross weight 0.7% get above-mentioned terbium-Xi terpolymer complex compound catalyst, inject above-mentioned miscellany with syringe.Constant temperature is at 110 DEG C, and 0.7MPa pressure, reacts 6 hours.Product impouring makes multipolymer precipitate containing in 5% methanol hydrochloride solution, and throw out is by methanol wash to neutral, and vacuum-drying, namely obtains 5-phenyl two ring [2,2,1] hept-2-ene", maleic anhydride and octafluoro cyclopentenes terpolymer.Calculating reaction yield is 59.6%.
Embodiment 11
Get 0.004 mole three (isopropylcyclopentadiene) to change terbium, 0.001 mole of tributyl cyclopentadienyl tin and 0.007 mole of isoquinoline 99.9 and be dissolved in 10 milliliters of pimelinketone, put into through repeatedly vacuumizing, inflated with nitrogen baking single port vial, bottleneck emulsion tube seals, put into Water Tank with Temp.-controlled at 40 DEG C 10 minutes, obtain terbium-Xi terpolymer complex compound catalyst.
0.01 mole of 5-vinyl two ring [2,2,1] hept-2-ene", 0.01 mol maleic anhydride and 0.01 mole of octafluoro cyclopentenes are added in the autoclave of inflated with nitrogen drying, adds 20ml pimelinketone and dissolve.The gauge changing terbium by three (isopropylcyclopentadiene) in catalyzer is norbornylene, maleic anhydride, octafluoro cyclopentenes three gross weight 0.8% get above-mentioned terbium-Xi terpolymer complex compound catalyst, inject above-mentioned miscellany with syringe.Constant temperature is at 120 DEG C, and 0.6MPa pressure, reacts 4 hours.Product impouring makes multipolymer precipitate containing in 5% methanol hydrochloride solution, and throw out is by methanol wash to neutral, and vacuum-drying, namely obtains 5-vinyl two ring [2,2,1] hept-2-ene", maleic anhydride and octafluoro cyclopentenes terpolymer.Calculating reaction yield is 55.6%.
Embodiment 12
Get 0.005 mole three (isopropylcyclopentadiene) to change terbium, 0.001 mole of tributyl cyclopentadienyl tin and 0.006 mole of oxine and be dissolved in 10 milliliters of sherwood oils, put into through repeatedly vacuumizing, inflated with nitrogen baking single port vial, bottleneck emulsion tube seals, put into Water Tank with Temp.-controlled at 40 DEG C 10 minutes, obtain terbium-Xi terpolymer complex compound catalyst.
0.01 mole of two ring [2,2,1] hept-2-ene"-5-methyl-formiate, 0.01 mol maleic anhydride and 0.01 mole of octafluoro cyclopentenes are added in the autoclave of inflated with nitrogen drying, adds 20ml benzene and dissolve.The gauge changing terbium by three (isopropylcyclopentadiene) in catalyzer is norbornylene, maleic anhydride, octafluoro cyclopentenes three gross weight 0.9% get above-mentioned terbium-Xi terpolymer complex compound catalyst, inject above-mentioned miscellany with syringe.Constant temperature is at 130 DEG C, and 0.5MPa pressure, reacts 3 hours.Product impouring makes multipolymer precipitate containing in 5% methanol hydrochloride solution, and throw out is by methanol wash to neutral, and vacuum-drying, namely obtains two rings [2,2,1] hept-2-ene"-5-methyl-formiate, maleic anhydride and octafluoro cyclopentenes terpolymer.Calculating reaction yield is 56.3%.
Embodiment 13
Get 0.006 mole three (isopropylcyclopentadiene) and change terbium, 0.001 mole of tributyl cyclopentadienyl tin and 0.001 mole of α, α '-dipyridyl is dissolved in 10 milliliters of toluene, put into through repeatedly vacuumizing, inflated with nitrogen baking single port vial, bottleneck emulsion tube seals, put into Water Tank with Temp.-controlled at 40 DEG C 10 minutes, obtain terbium-Xi terpolymer complex compound catalyst.
Special for 0.01 mole of two ring [2,2,1] hept-2-ene"-5-formic acid butyl ester, 0.01 mol maleic anhydride and 0.01 mole of octafluoro cyclopentenes are added in the autoclave of inflated with nitrogen drying, adds 20ml toluene and dissolve.The gauge changing terbium by three (isopropylcyclopentadiene) in catalyzer is norbornylene, maleic anhydride, octafluoro cyclopentenes three gross weight 0.06% get above-mentioned terbium-Xi terpolymer complex compound catalyst, inject above-mentioned miscellany with syringe.Constant temperature is at 140 DEG C, and 0.4MPa pressure, reacts 2 hours.Product impouring makes multipolymer precipitate containing in 5% methanol hydrochloride solution, and throw out is by methanol wash to neutral, and vacuum-drying, namely obtains two rings [2,2,1] hept-2-ene"-5-formic acid special butyl ester, maleic anhydride and octafluoro cyclopentenes terpolymer.Calculating reaction yield is 42.5%.
Embodiment 14
Get 0.007 mole three (isopropylcyclopentadiene) to change terbium, 0.001 mole of tributyl cyclopentadienyl tin and 0.001 mole of oxine and be dissolved in 10 milliliters of methyl-phenoxides, put into through repeatedly vacuumizing, inflated with nitrogen baking single port vial, bottleneck emulsion tube seals, put into Water Tank with Temp.-controlled at 40 DEG C 10 minutes, obtain terbium-Xi terpolymer complex compound catalyst.
0.01 mole of 7-methyl bicyclic [2,2,1] hept-2-ene", 0.01 mol maleic anhydride and 0.01 mole of octafluoro cyclopentenes are added in the autoclave of inflated with nitrogen drying, adds 20ml methyl-phenoxide and dissolve.The gauge changing terbium by three (isopropylcyclopentadiene) in catalyzer is norbornylene, maleic anhydride, octafluoro cyclopentenes three gross weight 0.07% get above-mentioned terbium-Xi terpolymer complex compound catalyst, inject above-mentioned miscellany with syringe.Constant temperature is at 150 DEG C, and 0.3MPa pressure, reacts 7 hours.Product impouring makes multipolymer precipitate containing in 5% methanol hydrochloride solution, and throw out is by methanol wash to neutral, and vacuum-drying, namely obtains 7-methyl bicyclic [2,2,1] hept-2-ene", maleic anhydride and octafluoro cyclopentenes terpolymer.Calculating reaction yield is 50.3%.
Embodiment 15
Get 0.008 mole three (isopropylcyclopentadiene) to change terbium, 0.001 mole of tributyl cyclopentadienyl tin and 0.001 mole of quinoline and be dissolved in 10 milliliters of methyl-phenoxides, put into through repeatedly vacuumizing, inflated with nitrogen baking single port vial, bottleneck emulsion tube seals, put into Water Tank with Temp.-controlled at 40 DEG C 10 minutes, obtain terbium-Xi terpolymer complex compound catalyst.
0.01 mole of 7-methyl bicyclic [2,2,1] hept-2-ene", 0.01 mol maleic anhydride and 0.01 mole of octafluoro cyclopentenes are added in the autoclave of inflated with nitrogen drying, adds 20ml methyl-phenoxide and dissolve.The gauge changing terbium by three (isopropylcyclopentadiene) in catalyzer is norbornylene, maleic anhydride, octafluoro cyclopentenes three gross weight 0.08% get above-mentioned terbium-Xi terpolymer complex compound catalyst, inject above-mentioned miscellany with syringe.Constant temperature is at 150 DEG C, and 0.2MPa pressure, reacts 5 hours.Product impouring makes multipolymer precipitate containing in 5% methanol hydrochloride solution, and throw out is by methanol wash to neutral, and vacuum-drying, namely obtains 7-methyl bicyclic [2,2,1] hept-2-ene", maleic anhydride and octafluoro cyclopentenes terpolymer.Calculating reaction yield is 48.7%.
Embodiment 16
Get 0.001 mole three (isopropylcyclopentadiene) and change terbium, 0.003 mole of tributyl cyclopentadienyl tin and 0.004 mole of α, α '-dipyridyl is dissolved in 10 milliliters of toluene, put into through repeatedly vacuumizing, inflated with nitrogen baking single port vial, bottleneck emulsion tube seals, put into Water Tank with Temp.-controlled at 40 DEG C 10 minutes, obtain terbium-Xi terpolymer complex compound catalyst.
0.01 mole of two ring [2,2,1] hept-2-ene", 0.01 mol maleic anhydride and 0.01 mole of octafluoro cyclopentenes are added in the autoclave of inflated with nitrogen drying, adds 20ml toluene and dissolve.The gauge changing terbium by three (isopropylcyclopentadiene) in catalyzer is norbornylene, maleic anhydride, octafluoro cyclopentenes three gross weight 1% get above-mentioned terbium-Xi terpolymer complex compound catalyst, inject above-mentioned miscellany with syringe.Constant temperature is at 150 DEG C, and 6MPa pressure, reacts 6 hours.Product impouring makes multipolymer precipitate containing in 5% methanol hydrochloride solution, and throw out is by methanol wash to neutral, and vacuum-drying, namely obtains two rings [2,2,1] hept-2-ene", maleic anhydride and octafluoro cyclopentenes terpolymer.Calculating reaction yield is 78.6%.
Embodiment 17
Get 0.001 mole three (isopropylcyclopentadiene) to change terbium, 0.001 mole of tributyl cyclopentadienyl tin and 0.001 mole of oxine and be dissolved in 10 milliliters of benzene, put into through repeatedly vacuumizing, inflated with nitrogen baking single port vial, bottleneck emulsion tube seals, put into Water Tank with Temp.-controlled at 40 DEG C 10 minutes, obtain terbium-Xi terpolymer complex compound catalyst.
0.01 mole of two ring [2,2,1] hept-2-ene", 0.01 mol maleic anhydride and 0.01 mole of octafluoro cyclopentenes are added in the autoclave of inflated with nitrogen drying, adds 20ml benzene and dissolve.The gauge changing terbium by three (isopropylcyclopentadiene) in catalyzer is norbornylene, maleic anhydride, octafluoro cyclopentenes three gross weight 0.15% get above-mentioned terbium-Xi terpolymer complex compound catalyst, inject above-mentioned miscellany with syringe.Constant temperature is at 40 DEG C, and 0.1MPa pressure, reacts 1 hour.Product impouring makes multipolymer precipitate containing in 5% methanol hydrochloride solution, and throw out is by methanol wash to neutral, and vacuum-drying, namely obtains two rings [2,2,1] hept-2-ene", maleic anhydride and octafluoro cyclopentenes terpolymer.Calculating reaction yield is 35.3%.
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.
Claims (4)
1. norbornylene class, maleic anhydride and an octafluoro cyclopentenes 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, three (isopropylcyclopentadiene) are changed terbium, tributyl cyclopentadienyl tin and ligand compound to be dissolved in the first solvent, bottleneck emulsion tube seals, constant temperature 8-12 minute at 35-45 DEG C, namely obtains terbium-Xi terpolymer complex compound catalyst;
The mol ratio that described three (isopropylcyclopentadiene) change terbium and described part is 1: 8 ~ 8: 1, and the mol ratio that described three (isopropylcyclopentadiene) change terbium and described tributyl cyclopentadienyl tin is 1: 8 ~ 8: 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 that the consumption of described first solvent and described three (isopropylcyclopentadiene) change terbium, part and tributyl cyclopentadienyl tin three total amount is 10 milliliters: 0.003 ~ 0.017 mole;
Described part, described first 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 first solvent adopts calcium chloride or hydrolith drying with hydrolith or sodium Metal 99.5 drying.
2. norbornylene class according to claim 1, maleic anhydride and octafluoro cyclopentenes terpolymer catalyzer, is characterized in that described three (isopropylcyclopentadiene) change terbium, the mol ratio of tributyl cyclopentadienyl tin and part three is 1: 2: 4.
3. use norbornylene class as claimed in claim 1, maleic anhydride and octafluoro cyclopentenes terpolymer catalyzer to carry out the method for norbornylene class, maleic anhydride and the terpolymer of octafluoro cyclopentenes, it is characterized in that comprising the steps:
Be get Norbornene derivative, maleic anhydride and octafluoro cyclopentenes monomer join in the autoclave of inertia drying at 1: 1: 1 according to mol ratio, add the second dissolution with solvents; Then add described terpolymer complex compound catalyst, at 40 ~ 160 DEG C, react 1 ~ 6 hour under 0.1-7MPa pressure; The consumption of described terpolymer complex compound catalyst is the 0.05%-3% of norbornylene class, maleic anhydride, octafluoro cyclopentenes three gross weight by the gauge that three (isopropylcyclopentadiene) in catalyzer change terbium;
Poured in the methanol solution containing 4.5-5.5wt% hydrochloric acid by the product be obtained by reacting, the throw out methanol wash obtained, to neutral, namely obtains norbornylene class, maleic anhydride and octafluoro cyclopentenes terpolymer 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.
4. norbornylene class according to claim 3, the method of maleic anhydride and the terpolymer of octafluoro cyclopentenes, 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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