CN105218709A - Norbornylene class, styrenic and maleic anhydride tercopolymer catalyst for copolymerization and method for ternary polymerization - Google Patents
Norbornylene class, styrenic and maleic anhydride tercopolymer catalyst for copolymerization and method for ternary polymerization Download PDFInfo
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Abstract
The present invention relates to a kind of norbornylene class, styrenic and maleic anhydride tercopolymer catalyst for copolymerization and method for ternary polymerization, it is characterized in that the preparation method of catalyzer is in the single port vial of the inert atmosphere of drying, Trichlororhodium, zinc ethyl and ligand compound are dissolved in the first solvent, bottle sealing, constant temperature 15-30 minute at 40-50 DEG C, obtains rhodium-zinc complex catalyzer; Method for ternary polymerization joins in the single port vial repeatedly vacuumizing dry inert atmosphere for getting Norbornene derivative, styrenic and maleic anhydride monomer according to mol ratio 1: 1: 1, then adds the second dissolution with solvents; Then add described rhodium-zinc complex catalyzer, react 1 ~ 8 hour at 20 ~ 90 DEG C.Catalyzer raw material provided by the invention is cheap and easy to get, and can produce catalytic activity under comparatively low temperature, polymeric reaction temperature is low, and catalytic efficiency is high, and product is easy to washing is separated, and copolymer yield is high.
Description
Technical field
The present invention relates to superpolymer synthetic catalyst and superpolymer synthesis, specifically refer to a kind of norbornylene class, styrenic and maleic anhydride tercopolymer catalyst for copolymerization and method for ternary polymerization.
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.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, alternating copolymerization material has been developed.
The method of current these materials of synthesis mainly contains the methods such as free radical, living radical, metal catalyst.If Eiji.Ihara and Q.Feng etc. is by norbornylene, vinylbenzene and acrylate free radical method carry out terpolymer, the synthesis of photoetching material disclosed in ProceedingsofSPIEVol.5039 (2003) 80th ~ 92 pages have employed the catalyzer of superoxide as radical polymerization, the synthesis of photoetching material disclosed in ProceedingsofSPIEVol.4690 (2002) 127th ~ 135 pages have employed the catalyzer of AINB (Diisopropyl azodicarboxylate) as radical polymerization, norbornylene and styrol copolymer photoetching material disclosed in PolymersVol.6 (2014) 565-582 page have employed the synthesis of free radical method.There is long reaction time, obtain the shortcomings such as copolymer yield is low, molecular weight of copolymer is little, multipolymer alternate degree is low in these synthetic methods of current application.
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, styrenic and maleic anhydride tercopolymer copolymerization catalyzer.
Another technical problem to be solved by this invention is to provide the method for a kind of temperature of reaction is lower, catalytic efficiency is high and copolymer yield is high norbornylene class, styrenic and maleic anhydride tercopolymer copolymerization.
The present invention solves the problems of the technologies described above adopted technical scheme: this norbornylene class, styrenic and maleic anhydride tercopolymer catalyst for copolymerization, it is characterized in that the preparation method of this catalyzer is as follows:
In the single port vial of the inert atmosphere of drying, Trichlororhodium, zinc ethyl and ligand compound are dissolved in the first solvent, bottleneck emulsion tube seals, and constant temperature 15-30 minute at 40-50 DEG C obtains rhodium-zinc complex catalyzer;
The mol ratio of described Trichlororhodium and described part is 1: 10 ~ 10: 1, and the mol ratio of described Trichlororhodium and described zinc ethyl is 1: 20 ~ 20: 1;
Described part is selected from oxine, α, α '-dipyridyl, phenanthroline, isoquinoline 99.9, quinoline, porphyrin or Acetyl Acetone;
Described first solvent is selected from benzene, toluene, tetrahydrofuran (THF), sherwood oil, methyl-phenoxide, Isosorbide-5-Nitrae-dioxane, 1,2-ethylene dichloride, hexanaphthene or pimelinketone; The ratio of the consumption of described solvent and described Trichlororhodium, part and zinc ethyl three total amount is 10 milliliters: 0.003 ~ 0.040 mole.
The mol ratio of described Trichlororhodium, zinc ethyl and part three is preferably 1: 10: 8.
Preferably, described first solvent first carries out drying before use; The drying of the solid-state part in wherein said part first purifies then vacuum-drying by recrystallization way; The drying of the liquid part in described part is that described solvent adopts calcium chloride or hydrolith drying with hydrolith or sodium Metal 99.5 drying.
Use above-mentioned norbornylene class, styrenic and maleic anhydride tercopolymer catalyst for copolymerization to carry out norbornylene class, styrenic and maleic anhydride tercopolymer copolymerization process, it is characterized in that comprising the steps:
Get Norbornene derivative, styrenic and maleic anhydride monomer according to mol ratio 1: 1: 1 to join in the single port vial repeatedly vacuumizing dry inert atmosphere, then add the second dissolution with solvents; Then add described rhodium-zinc complex catalyzer, react 1 ~ 8 hour at 20 ~ 90 DEG C;
Poured in the ethanolic soln containing 4-5wt% hydrochloric acid by the product be obtained by reacting, the precipitates washed with EtOH obtained, to neutral, namely obtains norbornylene class, styrenic and maleic anhydride terpolymer after vacuum-drying;
The consumption of described rhodium-zinc complex catalyzer is the 0.02%-2.0% of norbornylene class, styrenic and maleic anhydride three gross weight by the gauge of Trichlororhodium in catalyzer;
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 Norbornene derivative 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 styrene monomer is selected from vinylbenzene or alpha-methyl styrene.
Compared with prior art, catalyzer provided by the invention is a kind of new rhodium-zinc complex catalyst mixture, catalyzer raw material is cheap and easy to get, catalytic activity can be produced under comparatively low temperature, catalysis norbornylene class, vinylbenzene and maleic anhydride tercopolymer copolymerization, temperature of reaction is low, and catalytic efficiency is high, and product is easy to washing separation, copolymer yield is high.
Embodiment
Below in conjunction with embodiment, the present invention is described in further detail.
The preparation process of catalyzer in following embodiment, if no special instructions, has all carried out drying treatment to part wherein and solvent.Specifically: the drying of the solid ligand in part first purifies then vacuum-drying by recrystallization way; The drying of the liquid part in part is dry or dry with sodium Metal 99.5 with hydrolith.The drying of solvent is with calcium chloride or hydrolith drying.
Embodiment 1
Getting 0.001 mole of Trichlororhodium, 0.001 mole of zinc ethyl and 0.001 mole of oxine is dissolved in 10 milliliters of benzene, put into through repeatedly vacuumizing, single port vial that inflated with nitrogen baking is dry, bottleneck emulsion tube seals, put into Water Tank with Temp.-controlled at 40 DEG C 15 minutes, obtain rhodium-zinc complex catalyzer.
0.01 mole of two ring [2,2,1] hept-2-ene", 0.01 mole of vinylbenzene and 0.01 mol maleic anhydride are joined repeatedly vacuumize, in single port vial that inflated with nitrogen baking is dry, bottleneck emulsion tube seals, and adds 20ml benzene dissolve with syringe.By the gauge of Trichlororhodium in catalyzer be norbornylene, vinylbenzene, maleic anhydride three gross weight 0.02% get above-mentioned rhodium-zinc complex catalyzer, inject above-mentioned miscellany with syringe.Constant temperature, at 40 DEG C, reacts 5 hours.Product impouring makes multipolymer precipitate containing in the ethanolic soln of 5wt% hydrochloric acid, and precipitates washed with EtOH is to neutral, and vacuum-drying, namely obtains two rings [2,2,1] hept-2-ene", vinylbenzene, maleic anhydride terpolymer.Calculating reaction yield is 31.1%.
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 of Trichlororhodium, 0.020 mole of zinc ethyl and 0.002 mole of α, α '-dipyridyl is dissolved in 10 milliliters of toluene, put into through repeatedly vacuumizing, single port vial that inflated with nitrogen baking is dry, bottleneck emulsion tube seals, put into Water Tank with Temp.-controlled at 50 DEG C 30 minutes, obtain rhodium-zinc complex catalyzer.
By 0.01 mole of 1-methyl bicyclic [2,2,1] hept-2-ene", 0.01 mole of vinylbenzene and 0.01 mol maleic anhydride join repeatedly vacuumize, in single port vial that inflated with nitrogen baking is dry, bottleneck emulsion tube seals, and adds 20ml toluene dissolve with syringe.By the gauge of Trichlororhodium in catalyzer be norbornylene, vinylbenzene, maleic anhydride three gross weight 0.1% get above-mentioned rhodium-zinc complex catalyzer, inject above-mentioned miscellany with syringe.Constant temperature, at 20 DEG C, reacts 4 hours.Product impouring makes multipolymer precipitate containing in the ethanolic soln of 5wt% hydrochloric acid, and precipitates washed with EtOH is to neutral, and vacuum-drying, namely obtains 1-methyl bicyclic [2,2,1] hept-2-ene", vinylbenzene, maleic anhydride terpolymer.Calculating reaction yield is 38.3%.
Embodiment 3
Getting 0.001 mole of Trichlororhodium, 0.010 mole of zinc ethyl and 0.010 mole of phenanthroline is dissolved in 10 milliliters of tetrahydrofuran (THF)s, put into through repeatedly vacuumizing, single port vial that inflated with nitrogen baking is dry, bottleneck emulsion tube seals, put into Water Tank with Temp.-controlled at 50 DEG C 25 minutes, obtain rhodium-zinc complex catalyzer.
By 0.01 mole of 5-methyl bicyclic [2,2,1] hept-2-ene", 0.01 mole of vinylbenzene and 0.01 mol maleic anhydride join repeatedly vacuumize, in single port vial that inflated with nitrogen baking is dry, bottleneck emulsion tube seals, and adds 20ml tetrahydrofuran (THF) dissolve with syringe.By the gauge of Trichlororhodium in catalyzer be norbornylene, vinylbenzene, maleic anhydride three gross weight 0.8% get above-mentioned rhodium-zinc complex catalyzer, inject above-mentioned miscellany with syringe.Constant temperature, at 50 DEG C, reacts 2 hours.Product impouring makes multipolymer precipitate containing in the ethanolic soln of 5wt% hydrochloric acid, and precipitates washed with EtOH is to neutral, and vacuum-drying, namely obtains 5-methyl bicyclic [2,2,1] hept-2-ene", vinylbenzene and discipline and carry out acid anhydrides terpolymer.Calculating reaction yield is 41.8%.
Embodiment 4
Getting 0.001 mole of Trichlororhodium, 0.080 mole of zinc ethyl and 0.008 mole of isoquinoline 99.9 is dissolved in 10 milliliters of sherwood oils, put into through repeatedly vacuumizing, single port vial that inflated with nitrogen baking is dry, bottleneck emulsion tube seals, put into Water Tank with Temp.-controlled at 45 DEG C 30 minutes, obtain rhodium-zinc complex catalyzer.
By 0.01 mole of 7-methyl bicyclic [2,2,1] hept-2-ene", 0.01 mole of vinylbenzene and 0.01 mol maleic anhydride join repeatedly vacuumize, in single port vial that inflated with nitrogen baking is dry, bottleneck emulsion tube seals, and adds 20ml petroleum ether dissolution with syringe.By the gauge of Trichlororhodium in catalyzer be norbornylene, vinylbenzene, maleic anhydride three gross weight 1.0% get above-mentioned rhodium-zinc complex catalyzer, inject above-mentioned miscellany with syringe.Constant temperature, at 60 DEG C, reacts 3 hours.Product impouring makes multipolymer precipitate containing in the ethanolic soln of 5wt% hydrochloric acid, and precipitates washed with EtOH is to neutral, and vacuum-drying, namely obtains 7-methyl bicyclic [2,2,1] hept-2-ene", vinylbenzene and maleic anhydride terpolymer.Calculating reaction yield is 56.4%.
Embodiment 5
Getting 0.001 mole of Trichlororhodium, 0.004 mole of zinc ethyl and 0.006 mole of quinoline is dissolved in 10 milliliters of methyl-phenoxides, put into through repeatedly vacuumizing, single port vial that inflated with nitrogen baking is dry, bottleneck emulsion tube seals, put into Water Tank with Temp.-controlled at 40 DEG C 15 minutes, obtain rhodium-zinc complex catalyzer.
By 0.01 mole of 1-ethyl two ring [2,2,1] hept-2-ene", 0.01 mole of alpha-methyl styrene and 0.01 mol maleic anhydride join repeatedly vacuumize, in single port vial that inflated with nitrogen baking is dry, bottleneck emulsion tube seals, and adds 20ml methyl-phenoxide dissolve with syringe.By the gauge of Trichlororhodium in catalyzer be norbornylene, alpha-methyl styrene, maleic anhydride three gross weight 2.0% get above-mentioned rhodium-zinc complex catalyzer, inject above-mentioned miscellany with syringe.Constant temperature, at 70 DEG C, reacts 3 hours.Product impouring makes multipolymer precipitate containing in the ethanolic soln of 5wt% hydrochloric acid, and precipitates washed with EtOH is to neutral, and vacuum-drying, namely obtains 1-ethyl two ring [2,2,1] hept-2-ene", alpha-methyl styrene and maleic anhydride terpolymer.Calculating reaction yield is 55.3%.
Embodiment 6
Get 0.001 mole of Trichlororhodium, 0.010 mole of zinc ethyl and 0.008 mole of α, α '-dipyridyl is dissolved in 10 milliliter 1, in 4-dioxane, put into through repeatedly vacuumizing, single port vial that inflated with nitrogen baking is dry, bottleneck emulsion tube seals, put into Water Tank with Temp.-controlled at 45 DEG C 20 minutes, obtain rhodium-zinc complex catalyzer.
By 0.01 mole of two ring [2,2,1] hept-2-ene", 0.01 mole of vinylbenzene and 0.01 mol maleic anhydride join repeatedly vacuumize, in single port vial that inflated with nitrogen baking is dry, bottleneck emulsion tube seals, add 20ml1 with syringe, 4-dioxane dissolves.By the gauge of Trichlororhodium in catalyzer be norbornylene, vinylbenzene, maleic anhydride three gross weight 0.5% get above-mentioned rhodium-zinc complex catalyzer, inject above-mentioned miscellany with syringe.Constant temperature, at 80 DEG C, reacts 7 hours.Product impouring makes multipolymer precipitate containing in the ethanolic soln of 5wt% hydrochloric acid, and precipitates washed with EtOH is to neutral, and vacuum-drying, namely obtains two rings [2,2,1] hept-2-ene", vinylbenzene and maleic anhydride terpolymer.Calculating reaction yield is 89.9%.
Embodiment 7
Get 0.001 mole of Trichlororhodium, 0.015 mole of zinc ethyl and 0.008 mole of Acetyl Acetone and be dissolved in 10 milliliter 1; in 2-ethylene dichloride; put into through repeatedly vacuumizing, single port vial that inflated with nitrogen baking is dry; bottleneck emulsion tube seals; put into Water Tank with Temp.-controlled at 40 DEG C 30 minutes, obtain rhodium-zinc complex catalyzer.
By 0.01 mole of 5-vinyl two ring [2,2,1] hept-2-ene", 0.01 mole of vinylbenzene and 0.01 mol maleic anhydride join repeatedly vacuumize, in single port vial that inflated with nitrogen baking is dry, bottleneck emulsion tube seals, add 20ml1 with syringe, 2-ethylene dichloride dissolves.By the gauge of Trichlororhodium in catalyzer be norbornylene, vinylbenzene, maleic anhydride three gross weight 1.0% get above-mentioned rhodium-zinc complex catalyzer, inject above-mentioned miscellany with syringe.Constant temperature, at 90 DEG C, reacts 7 hours.Product impouring makes multipolymer precipitate containing in the ethanolic soln of 5wt% hydrochloric acid, and precipitates washed with EtOH is to neutral, and vacuum-drying, namely obtains 5-vinyl two ring [2,2,1] hept-2-ene", vinylbenzene and maleic anhydride terpolymer.Calculating reaction yield is 61.9%.
Embodiment 8
Getting 0.001 mole of Trichlororhodium, 0.010 mole of diethyl alkene and 0.006 mole of Acetyl Acetone is dissolved in 10 milliliters of hexanaphthenes; put into through repeatedly vacuumizing, single port vial that inflated with nitrogen baking is dry; bottleneck emulsion tube seals; put into Water Tank with Temp.-controlled at 40 DEG C 30 minutes, obtain rhodium-zinc complex catalyzer.
By 0.01 mole 5,5-dimethyl two ring [2,2,1] hept-2-ene", 0.01 mole of vinylbenzene and 0.01 mol maleic anhydride join and repeatedly vacuumize, in single port vial that inflated with nitrogen baking is dry, bottleneck emulsion tube seals, and adds 20ml hexanaphthene dissolve with syringe.By the gauge of Trichlororhodium in catalyzer be norbornylene, vinylbenzene, maleic anhydride three gross weight 0.60% get above-mentioned rhodium-zinc complex catalyzer, inject above-mentioned miscellany with syringe.Constant temperature, at 80 DEG C, reacts 6 hours.Product impouring makes multipolymer precipitate containing in the ethanolic soln of 5wt% hydrochloric acid, and precipitates washed with EtOH is to neutral, and vacuum-drying, namely obtains 5,5-dimethyl two ring [2,2,1] hept-2-ene", vinylbenzene and maleic anhydride terpolymer.Calculating reaction yield is 77.8%.
Embodiment 9
Getting 0.020 mole of Trichlororhodium, 0.001 mole of triethyl aluminum and 0.002 mole of benzoyl group acetone is dissolved in 10 milliliters of pimelinketone; put into through repeatedly vacuumizing, single port vial that inflated with nitrogen baking is dry; bottleneck emulsion tube seals; put into Water Tank with Temp.-controlled at 45 DEG C 20 minutes, obtain rhodium-zinc complex catalyzer.
By 0.01 mole 5,5-dimethyl two ring [2,2,1] hept-2-ene", 0.01 mole of vinylbenzene and 0.01 mol maleic anhydride join and repeatedly vacuumize, in single port vial that inflated with nitrogen baking is dry, bottleneck emulsion tube seals, and adds 20ml pimelinketone dissolve with syringe.By the gauge of Trichlororhodium in catalyzer be norbornylene, vinylbenzene, maleic anhydride three gross weight 0.7% get above-mentioned rhodium-zinc complex catalyzer, inject above-mentioned miscellany with syringe.Constant temperature, at 70 DEG C, reacts 4 hours.Product impouring makes multipolymer precipitate containing in the ethanolic soln of 5wt% hydrochloric acid, and precipitates washed with EtOH is to neutral, and vacuum-drying, namely obtains 5,5-dimethyl two ring [2,2,1] hept-2-ene", vinylbenzene and maleic anhydride terpolymer.Calculating reaction yield is 47.8%.
Embodiment 10
Getting 0.010 mole of Trichlororhodium, 0.001 mole of zinc ethyl and 0.004 mole of oxine is dissolved in 10 milliliters of hexanaphthenes, put into through repeatedly vacuumizing, single port vial that inflated with nitrogen baking is dry, bottleneck emulsion tube seals, put into Water Tank with Temp.-controlled at 50 DEG C 20 minutes, obtain rhodium-zinc complex catalyzer.
By 0.01 mole 5,5-dimethyl two ring [2,2,1] hept-2-ene", 0.01 mole of alpha-methyl styrene and 0.01 mol maleic anhydride join and repeatedly vacuumize, in single port vial that inflated with nitrogen baking is dry, bottleneck emulsion tube seals, and adds 20ml hexanaphthene dissolve with syringe.By the gauge of Trichlororhodium in catalyzer be norbornylene, alpha-methyl styrene, maleic anhydride three gross weight 1.70% get above-mentioned rhodium-zinc complex catalyzer, inject above-mentioned miscellany with syringe.Constant temperature, at 50 DEG C, reacts 4 hours.Product impouring makes multipolymer precipitate containing in the ethanolic soln of 5wt% hydrochloric acid, and precipitates washed with EtOH is to neutral, and vacuum-drying, namely obtains 5,5-dimethyl two ring [2,2,1] hept-2-ene", alpha-methyl styrene and maleic anhydride terpolymer.Calculating reaction yield is 58.5%.
Embodiment 11
Getting 0.008 mole of Trichlororhodium, 0.001 mole of zinc ethyl and 0.004 mole of phenanthroline is dissolved in 10 milliliters of pimelinketone, put into through repeatedly vacuumizing, single port vial that inflated with nitrogen baking is dry, bottleneck emulsion tube seals, put into Water Tank with Temp.-controlled at 45 DEG C 30 minutes, obtain rhodium-zinc complex catalyzer.
By 0.01 mole of 1-phenyl two ring [2,2,1] hept-2-ene", 0.01 mole of vinylbenzene and 0.01 mol maleic anhydride join repeatedly vacuumize, in single port vial that inflated with nitrogen baking is dry, bottleneck emulsion tube seals, and adds 20ml pimelinketone dissolve with syringe.By the gauge of Trichlororhodium in catalyzer be norbornylene, vinylbenzene, maleic anhydride three gross weight 1.0% get above-mentioned rhodium-zinc complex catalyzer, inject above-mentioned miscellany with syringe.Constant temperature, at 60 DEG C, reacts 2 hours.Product impouring makes multipolymer precipitate containing in the ethanolic soln of 5wt% hydrochloric acid, and precipitates washed with EtOH is to neutral, and vacuum-drying, namely obtains 1-phenyl two ring [2,2,1] hept-2-ene", vinylbenzene and maleic anhydride terpolymer.Calculating reaction yield is 51.6%.
Embodiment 12
Getting 0.006 mole of Trichlororhodium, 0.002 mole of zinc ethyl and 0.010 mole of quinoline is dissolved in 10 milliliters of sherwood oils, put into through repeatedly vacuumizing, single port vial that inflated with nitrogen baking is dry, bottleneck emulsion tube seals, put into Water Tank with Temp.-controlled at 50 DEG C 20 minutes, obtain rhodium-zinc complex catalyzer.
By 0.01 mole of 5-phenyl two ring [2,2,1] hept-2-ene", 0.01 mole of vinylbenzene and 0.01 mol maleic anhydride join repeatedly vacuumize, in single port vial that inflated with nitrogen baking is dry, bottleneck emulsion tube seals, and adds 20ml petroleum ether dissolution with syringe.By the gauge of Trichlororhodium in catalyzer be norbornylene, vinylbenzene, maleic anhydride three gross weight 1.2% get above-mentioned rhodium-zinc complex catalyzer, inject above-mentioned miscellany with syringe.Constant temperature, at 70 DEG C, reacts 7 hours.Product impouring makes multipolymer precipitate containing in the ethanolic soln of 5wt% hydrochloric acid, and precipitates washed with EtOH is to neutral, and vacuum-drying, namely obtains 5-phenyl two ring [2,2,1] hept-2-ene", vinylbenzene and maleic anhydride terpolymer.Calculating reaction yield is 63.3%.
Embodiment 13
Getting 0.004 mole of Trichlororhodium, 0.001 mole of zinc ethyl and 0.008 mole of porphyrin is dissolved in 10 milliliters of tetrahydrofuran (THF)s, put into through repeatedly vacuumizing, single port vial that inflated with nitrogen baking is dry, bottleneck emulsion tube seals, put into Water Tank with Temp.-controlled at 50 DEG C 30 minutes, obtain rhodium-zinc complex catalyzer.
By 0.01 mole of 5-vinyl two ring [2,2,1] hept-2-ene", 0.01 mole of vinylbenzene and 0.01 mol maleic anhydride join repeatedly vacuumize, in single port vial that inflated with nitrogen baking is dry, bottleneck emulsion tube seals, and adds 20ml tetrahydrofuran (THF) dissolve with syringe.By the gauge of Trichlororhodium in catalyzer be norbornylene, vinylbenzene, maleic anhydride three gross weight 1.00% get above-mentioned rhodium-zinc complex catalyzer, inject above-mentioned miscellany with syringe.Constant temperature, at 80 DEG C, reacts 4 hours.Product impouring makes multipolymer precipitate containing in the ethanolic soln of 4wt% hydrochloric acid, and precipitates washed with EtOH is to neutral, and vacuum-drying, namely obtains 5-vinyl two ring [2,2,1] hept-2-ene", vinylbenzene and maleic anhydride terpolymer.Calculating reaction yield is 66.1%.
Embodiment 14
Getting 0.001 mole of Trichlororhodium, 0.080 mole of zinc ethyl and 0.008 mole of Acetyl Acetone is dissolved in 10 milliliters of methyl-phenoxides; put into through repeatedly vacuumizing, single port vial that inflated with nitrogen baking is dry; bottleneck emulsion tube seals; put into Water Tank with Temp.-controlled at 40 DEG C 20 minutes, obtain rhodium-zinc complex catalyzer.
By 0.01 mole of two ring [2,2,1] hept-2-ene"-5-methyl-formiate, 0.01 mole of vinylbenzene and 0.01 mol maleic anhydride join repeatedly vacuumize, in single port vial that inflated with nitrogen baking is dry, bottleneck emulsion tube seals, and adds 20ml methyl-phenoxide dissolve with syringe.By the gauge of Trichlororhodium in catalyzer be norbornylene, vinylbenzene, maleic anhydride three gross weight 0.50% get above-mentioned rhodium-zinc complex catalyzer, inject above-mentioned miscellany with syringe.Constant temperature, at 90 DEG C, reacts 5 hours.Product impouring makes multipolymer precipitate containing in the ethanolic soln of 5wt% hydrochloric acid, and precipitates washed with EtOH is to neutral, and vacuum-drying, namely obtains two rings [2,2,1] hept-2-ene"-5-methyl-formiate, vinylbenzene and maleic anhydride terpolymer.Calculating reaction yield is 81.7%.
Embodiment 15
Getting 0.001 mole of Trichlororhodium, 0.010 mole of zinc ethyl and 0.005 mole of isoquinoline 99.9 is dissolved in 10 milliliters of pimelinketone, put into through repeatedly vacuumizing, single port vial that inflated with nitrogen baking is dry, bottleneck emulsion tube seals, put into Water Tank with Temp.-controlled at 50 DEG C 20 minutes, obtain rhodium-zinc complex catalyzer.
By 0.01 mole of two ring [2,2,1] hept-2-ene"-5-formic acid special butyl ester, 0.01 mole of vinylbenzene and 0.01 mol maleic anhydride join repeatedly vacuumize, in single port vial that inflated with nitrogen baking is dry, bottleneck emulsion tube seals, and adds 20ml pimelinketone dissolve with syringe.By the gauge of Trichlororhodium in catalyzer be norbornylene, vinylbenzene, maleic anhydride three gross weight 0.70% get above-mentioned rhodium-zinc complex catalyzer, inject above-mentioned miscellany with syringe.Constant temperature, at 80 DEG C, reacts 2 hours.Product impouring makes multipolymer precipitate containing in the ethanolic soln of 5wt% hydrochloric acid, and precipitates washed with EtOH is to neutral, and vacuum-drying, namely obtains two rings [2,2,1] hept-2-ene"-5-formic acid special butyl ester, vinylbenzene and maleic anhydride terpolymer.Calculating reaction yield is 68.9%.
Embodiment 16
Get 0.001 mole of Trichlororhodium, 0.008 mole of zinc ethyl and 0.007 mole of α, α '-dipyridyl is dissolved in 10 milliliters of toluene, put into through repeatedly vacuumizing, single port vial that inflated with nitrogen baking is dry, bottleneck emulsion tube seals, put into Water Tank with Temp.-controlled at 45 DEG C 30 minutes, obtain rhodium-zinc complex catalyzer.
0.01 mole of two ring [2,2,1] hept-2-ene", 0.01 mole of vinylbenzene and 0.01 mol maleic anhydride are joined repeatedly vacuumize, in single port vial that inflated with nitrogen baking is dry, bottleneck emulsion tube seals, and adds 20ml toluene dissolve with syringe.By the gauge of Trichlororhodium in catalyzer be norbornylene, vinylbenzene, maleic anhydride three gross weight 0.8% get above-mentioned rhodium-zinc complex catalyzer, inject above-mentioned miscellany with syringe.Constant temperature, at 90 DEG C, reacts 7 hours.Product impouring makes multipolymer precipitate containing in the ethanolic soln of 5wt% hydrochloric acid, and precipitates washed with EtOH is to neutral, and vacuum-drying, namely obtains two rings [2,2,1] hept-2-ene", vinylbenzene and maleic anhydride terpolymer.Calculating reaction yield is 75.8%.
Claims (5)
1. norbornylene class, styrenic and maleic anhydride tercopolymer catalyst for copolymerization, is characterized in that the preparation method of this catalyzer is as follows:
In the single port vial of the inert atmosphere of drying, Trichlororhodium, zinc ethyl and ligand compound are dissolved in the first solvent, bottleneck emulsion tube seals, and constant temperature 15-30 minute at 40-50 DEG C obtains rhodium-zinc complex catalyzer;
The mol ratio of described Trichlororhodium and described part is 1: 10 ~ 10: 1, and the mol ratio of described Trichlororhodium and described zinc ethyl is 1: 20 ~ 20: 1;
Described part is selected from oxine, α, α '-dipyridyl, phenanthroline, isoquinoline 99.9, quinoline, porphyrin or Acetyl Acetone;
Described first solvent is selected from benzene, toluene, tetrahydrofuran (THF), sherwood oil, methyl-phenoxide, Isosorbide-5-Nitrae-dioxane, 1,2-ethylene dichloride, hexanaphthene or pimelinketone; The ratio of the consumption of described solvent and described Trichlororhodium, part and zinc ethyl three total amount is 10 milliliters: 0.003 ~ 0.040 mole.
2. norbornylene class according to claim 1, styrenic and maleic anhydride tercopolymer catalyst for copolymerization, is characterized in that described Trichlororhodium, the mol ratio of zinc ethyl and part three is 1: 10: 8.
3. norbornylene class according to claim 1 and 2, styrenic and maleic anhydride tercopolymer catalyst for copolymerization, is characterized in that described first solvent first carries out drying before use; The drying of the solid-state part in wherein said part first purifies then vacuum-drying by recrystallization way; The drying of the liquid part in described part is that described solvent adopts calcium chloride or hydrolith drying with hydrolith or sodium Metal 99.5 drying.
4. use the method for ternary polymerization of norbornylene class, styrenic and maleic anhydride tercopolymer catalyst for copolymerization as described in claim as arbitrary in claims 1 to 3, it is characterized in that comprising the steps:
Get Norbornene derivative, styrenic and maleic anhydride monomer according to mol ratio 1: 1: 1 to join in the single port vial repeatedly vacuumizing dry inert atmosphere, then add the second dissolution with solvents; Then add described rhodium-zinc complex catalyzer, react 1 ~ 8 hour at 20 ~ 90 DEG C;
Poured in the ethanolic soln containing 4-5wt% hydrochloric acid by the product be obtained by reacting, the precipitates washed with EtOH obtained, to neutral, namely obtains norbornylene class, styrenic and maleic anhydride terpolymer after vacuum-drying;
The consumption of described rhodium-zinc complex catalyzer is the 0.02%-2.0% of norbornylene class, styrenic and maleic anhydride three gross weight by the gauge of Trichlororhodium in catalyzer;
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.
5. ternary tool method according to claim 4, it is characterized in that described Norbornene derivative 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 styrene monomer is selected from vinylbenzene or alpha-methyl styrene.
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| CN106832118A (en) * | 2017-02-17 | 2017-06-13 | 宁波工程学院 | Norborneol alkenes and vinylene carbonate binary copolymerization catalyst and binary copolymerization method |
| CN106832123A (en) * | 2017-02-28 | 2017-06-13 | 宁波工程学院 | Norborneol alkenes, vinyl ethyl ether and perfluoro methyl vinyl ether ternary polymerization catalyst and method for ternary polymerization |
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| CN102924658A (en) * | 2012-11-02 | 2013-02-13 | 宁波工程学院 | Catalyst for ternary polymerization of norbornene, derivative of norbornene, tetrafluoroethylene and cyclohexene and method of ternary polymerization |
| CN104817659A (en) * | 2015-05-04 | 2015-08-05 | 宁波工程学院 | Ternary polymerization catalyst of norbornene, octafluorocyclopentene and styrene and ternary polymerization method |
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| CN102924658A (en) * | 2012-11-02 | 2013-02-13 | 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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| CN106832118A (en) * | 2017-02-17 | 2017-06-13 | 宁波工程学院 | Norborneol alkenes and vinylene carbonate binary copolymerization catalyst and binary copolymerization method |
| CN106832118B (en) * | 2017-02-17 | 2019-05-07 | 宁波工程学院 | Norborneol alkenes and vinylene carbonate binary copolymerization catalyst and binary copolymerization method |
| CN106832123A (en) * | 2017-02-28 | 2017-06-13 | 宁波工程学院 | Norborneol alkenes, vinyl ethyl ether and perfluoro methyl vinyl ether ternary polymerization catalyst and method for ternary polymerization |
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