CN103626919B - Norbornylene class, maleic anhydride and vinyl acetate terpolymer catalyzer and method for ternary polymerization - Google Patents
Norbornylene class, maleic anhydride and vinyl acetate terpolymer catalyzer and method for ternary polymerization Download PDFInfo
- Publication number
- CN103626919B CN103626919B CN201310613347.9A CN201310613347A CN103626919B CN 103626919 B CN103626919 B CN 103626919B CN 201310613347 A CN201310613347 A CN 201310613347A CN 103626919 B CN103626919 B CN 103626919B
- Authority
- CN
- China
- Prior art keywords
- maleic anhydride
- vinyl acetate
- catalyzer
- hept
- ene
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Expired - Fee Related
Links
Abstract
The present invention relates to a kind of norbornylene class, maleic anhydride and vinyl acetate terpolymer catalyzer 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, three (cyclopentadiene) are changed neodymium, titanium tetrachloride and ligand compound to be dissolved in solvent, bottleneck emulsion tube seals, and obtains titanium complex catalyzer.Compared with prior art, the invention provides a kind of Novel Titanium complex compound catalyst and use the method for ternary polymerization of this catalyzer, preparation method is simple, it can 40 ~ 90 DEG C time, catalytic activity is produced in nitrogen protection system, the terpolymer of catalysis norbornylene class, maleic anhydride and vinyl acetate, after methyl alcohol soaks, polymerisate is easy to washing and is 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 superpolymer synthesis field, specifically refer to a kind of norbornylene class, maleic anhydride and vinyl acetate terpolymer catalyzer 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.Maleic anhydride is inserted after in polynorbornene main chain, cohesiveness and the solubility of polymkeric substance can be improved, the toughness of gathering into multipolymer photoetching material can be increased of vinyl acetate.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.Disclosed in Proceedings of SPIE Vol.5039 (2003) 80th ~ 92 pages, the synthesis of photoetching material have employed the catalyzer of superoxide as radical polymerization, and the synthesis of photoetching material disclosed in Proceedings of SPIE Vol.4690 (2002) 127th ~ 135 pages have employed AINB(Diisopropyl azodicarboxylate) as the catalyzer of 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 domesticly carries out seldom norbornylene and maleic anhydride, vinyl acetate terpolymer research.
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 vinyl acetate terpolymer catalyzer.
Second 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 vinyl acetate terpolymer.
The present invention solves the problems of the technologies described above adopted technical scheme: this norbornylene class, maleic anhydride and vinyl acetate terpolymer catalyzer, is characterized in that this catalyzer is prepared by following method:
In the single port vial of the drying of atmosphere of inert gases, three (cyclopentadiene) are changed neodymium, titanium tetrachloride and ligand compound and is dissolved in solvent, bottleneck emulsion tube seals, and obtains titanium complex catalyzer;
The mol ratio of described titanium tetrachloride and described part is 1: 8 ~ 8: 8, and the mol ratio that described three (cyclopentadiene) change neodymium and described titanium tetrachloride is 1: 8 ~ 8: 1;
Described part is selected from oxine, α, α ,-dipyridyl, phenanthroline, pyridine, isoquinoline 99.9, quinoline, porphyrin, Acetyl Acetone or benzoyl group acetone;
Described solvent is selected from tetrahydrofuran (THF), methyl-phenoxide, Isosorbide-5-Nitrae-dioxane, pimelinketone or toluene; The ratio that the consumption of described solvent and described three (cyclopentadiene) change neodymium, part and titanium tetrachloride three total amount is 10 milliliters: 0.015 ~ 0.15 mole.
Neodymium changed by preferred described titanium tetrachloride, three (cyclopentadiene), the mol ratio of part three is 1: 1: 4.
In above-mentioned each scheme, described part, described solvent first can carry out drying before use; The drying of the solid-state part in wherein said part first purifies then vacuum-drying by recrystallization way; The drying of the liquid part in described part is that described solvent adopts calcium chloride or hydrolith drying with hydrolith or sodium Metal 99.5 drying.
Use above-mentioned norbornylene class, maleic anhydride and vinyl acetate terpolymer catalyzer to carry out the method for norbornylene class, maleic anhydride and vinyl acetate terpolymer, it is characterized in that comprising the steps:
Be get norbornylene class, maleic anhydride and Vinyl Acetate Monomer at 1: 1: 1 according to mol ratio, three joined in the single port vial of the drying of atmosphere of inert gases, then in this single port vial, add dissolution with solvents; Described titanium complex catalyzer is joined in described single port vial, isothermal reaction 0.5 ~ 3 hour at microwave heating to 40 ~ 90 DEG C;
The reaction product impouring obtained is contained in the methanol solution of 5wt% hydrochloric acid, obtain the throw out of norbornylene class, maleic anhydride and vinyl acetate terpolymer, after this throw out methanol wash to neutrality, vacuum-drying, namely obtains norbornylene class, maleic anhydride and vinyl acetate terpolymer;
The consumption of described titanium complex catalyzer is 0.03 ~ 1% (with titanium tetrachloride weighing scale) of norbornylene class, maleic anhydride and Vinyl Acetate Monomer gross weight;
The consumption of described solvent and the ratio of polymerization single polymerization monomer total amount are 10 milliliters: 0.045 mole.
Preferably, described heating can adopt MILESTONE microwave instrument to heat.Inert atmosphere can be carry out in nitrogen atmosphere, such as, operate in nitrogen glove box.
Described norbornylene class can be 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, the invention provides a kind of Novel Titanium complex compound catalyst, preparation method is simple, it can 40 ~ 90 DEG C time, catalytic activity is produced in nitrogen protection system, the terpolymer of catalysis norbornylene class, maleic anhydride and vinyl acetate, after methyl alcohol soaks, polymerisate is easy to washing and is 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, in the single port vial of inflated with nitrogen baking, adding 10 milliliters of tetrahydrofuran (THF)s respectively, 0.05 mole of titanium tetrachloride, 0.05 mole of oxine and 0.025 mole three (cyclopentadiene) change neodymium, obtaining titanium complex catalyzer.
0.015 mole of two ring [2,2,1] hept-2-ene", 0.015 mol maleic anhydride, 0.015 molar acetate vinyl acetate are added in single port vial in nitrogen atmosphere, adds 10ml tetrahydrofuran (THF) and dissolve.With titanium tetrachloride weighing scale, the consumption of above-mentioned titanium complex catalyzer is 1% of norbornylene, maleic anhydride and vinyl acetate three gross weight, and namely the weight of titanium tetrachloride is 1% of norbornylene, maleic anhydride and vinyl acetate three gross weight.In following each embodiment, the metering of titanium complex catalyst levels is identical therewith.
Above-mentioned miscellany is injected with syringe.Constant temperature, at 90 DEG C, reacts 0.5 hour.Containing in the methanol solution of 5% hydrochloric acid, norbornylene, maleic anhydride, vinyl acetate terpolymer are precipitated product impouring, throw out is by methanol wash to neutral, and vacuum-drying, recording reaction yield is 47.9%.
The calculating of reaction yield is the gross weight of products weight/(norbornene derivative+maleic anhydride+vinyl acetate).Following each embodiment is identical therewith.
Embodiment 2
Through repeatedly vacuumizing, in the single port vial of inflated with nitrogen baking, adding 10 milliliters of methyl-phenoxides respectively, 0.01 mole of titanium tetrachloride, 0.08 rubs α, α, neodymium changed by-dipyridyl and 0.01 three (cyclopentadiene) that rub, and obtains titanium complex catalyzer.
0.015 mole of two ring 1-methyl bicyclic [2,2,1] hept-2-ene", 0.015 mol maleic anhydride, 0.015 molar acetate vinyl acetate are added in single port vial in nitrogen atmosphere, adds 10ml methyl-phenoxide and dissolve.Get the above-mentioned catalyzer (with titanium tetrachloride weighing scale) of 0.3% by the total weight of norbornylene, maleic anhydride, vinyl acetate three, inject above-mentioned miscellany with syringe.Constant temperature, at 90 DEG C, reacts 3 hours.Product impouring makes norbornylene, maleic anhydride, vinyl acetate terpolymer precipitate containing in 5% methanol hydrochloride solution, and throw out is extremely neutral by methanol wash, vacuum-drying, reaction yield 61.1%.
Embodiment 3
Through repeatedly vacuumizing, in the single port vial of inflated with nitrogen baking, adding 10 milliliters of Isosorbide-5-Nitrae-dioxane respectively, 0.008 mole of titanium tetrachloride, 0.064 mole of phenanthroline and 0.001 mole three (cyclopentadiene) change neodymium, obtaining titanium complex catalyzer.
0.015 mole of 5-methyl bicyclic [2,2,1] hept-2-ene", 0.015 mol maleic anhydride, 0.015 molar acetate vinyl acetate are added in nitrogen atmosphere in single port vial, add 10ml1,4-dioxane dissolves.Get the above-mentioned catalyzer (with titanium tetrachloride weighing scale) of 0.05% by the total weight of norbornylene, maleic anhydride, vinyl acetate three, inject above-mentioned miscellany with syringe.Constant temperature, at 80 DEG C, reacts 2 hours.Product impouring makes norbornylene, maleic anhydride, vinyl acetate terpolymer precipitate containing in 5% methanol hydrochloride solution, and throw out is extremely neutral by methanol wash, vacuum-drying, reaction yield 53.2%.
Embodiment 4
Through repeatedly vacuumizing, in the single port vial of inflated with nitrogen baking, adding 10 milliliters of toluene respectively, 0.01 mole of titanium tetrachloride, 0.01 mole pyridine and 0.01 mole three (cyclopentadiene) change neodymium, obtaining titanium complex catalyzer.
0.015 mole of 7-methyl bicyclic [2,2,1] hept-2-ene", 0.015 mol maleic anhydride, 0.015 molar acetate vinyl acetate are added in single port vial in nitrogen atmosphere, adds 10ml toluene and dissolve.Get the above-mentioned catalyzer (with titanium tetrachloride weighing scale) of 1% by the total weight of norbornylene, maleic anhydride, vinyl acetate three, inject above-mentioned miscellany with syringe.Constant temperature, at 40 DEG C, reacts 2.5 hours.Product impouring makes norbornylene, maleic anhydride, vinyl acetate terpolymer precipitate containing in 5% methanol hydrochloride solution, and throw out is extremely neutral by methanol wash, vacuum-drying, reaction yield 68.7%.
Embodiment 5
Through repeatedly vacuumizing, inflated with nitrogen baking single port vial in, add 10 milliliters of pimelinketone, 0.01 mole of titanium tetrachloride, 0.04 mole of α, α respectively, neodymium changed by-dipyridyl and 0.01 mole three (cyclopentadiene), obtains titanium complex catalyzer.
0.015 mole of 1-ethyl two ring [2,2,1] hept-2-ene", 0.015 mol maleic anhydride, 0.015 molar acetate vinyl acetate are added in single port vial in nitrogen atmosphere, adds 10ml pimelinketone and dissolve.Get the above-mentioned catalyzer (with titanium tetrachloride weighing scale) of 0.5% by the total weight of norbornylene, maleic anhydride, vinyl acetate three, inject above-mentioned miscellany with syringe.Constant temperature, at 90 DEG C, reacts 3 hours.Product impouring makes norbornylene, maleic anhydride, vinyl acetate terpolymer precipitate containing in 5% methanol hydrochloride solution, and throw out is extremely neutral by methanol wash, vacuum-drying, reaction yield 92.3%.
Embodiment 6
Through repeatedly vacuumizing, in the single port vial of inflated with nitrogen baking, adding 10 milliliters of methyl-phenoxides respectively, 0.003 mole of titanium tetrachloride, 0.012 mole of Acetyl Acetone and 0.024 mole three (cyclopentadiene) change neodymium, obtaining titanium complex catalyzer.
0.015 mole of 5-ethyl two ring [2,2,1] hept-2-ene", 0.015 mol maleic anhydride, 0.015 molar acetate vinyl acetate are added in single port vial in nitrogen atmosphere, adds 10ml methyl-phenoxide and dissolve.Get the above-mentioned catalyzer (with titanium tetrachloride weighing scale) of 0.8% by the total weight of norbornylene, maleic anhydride, vinyl acetate three, inject above-mentioned miscellany with syringe.Constant temperature, at 60 DEG C, reacts 2 hours.Product impouring makes norbornylene, maleic anhydride, vinyl acetate terpolymer precipitate containing in 5% methanol hydrochloride solution, and throw out is extremely neutral by methanol wash, vacuum-drying, reaction yield 70.1%.
Embodiment 7
Through repeatedly vacuumizing, in the single port vial of inflated with nitrogen baking, adding 10 milliliters of tetrahydrofuran (THF)s respectively, 0.005 mole of titanium tetrachloride, 0.005 mole of quinoline and 0.020 mole three (cyclopentadiene) change neodymium, obtaining titanium complex catalyzer.
0.015 mole of 5,5-dimethyl two ring [2,2,1] hept-2-ene", 0.015 mol maleic anhydride, 0.015 molar acetate vinyl acetate are added in single port vial in nitrogen atmosphere, adds 10ml tetrahydrofuran (THF) and dissolve.Get the above-mentioned catalyzer (with titanium tetrachloride weighing scale) of 0.1% by the total weight of norbornylene, maleic anhydride, vinyl acetate three, inject above-mentioned miscellany with syringe.Constant temperature, at 70 DEG C, reacts 1.5 hours.Product impouring makes norbornylene, maleic anhydride, vinyl acetate terpolymer precipitate containing in 5% methanol hydrochloride solution, and throw out is extremely neutral by methanol wash, vacuum-drying, reaction yield 58.3%.
Embodiment 8
Through repeatedly vacuumizing, inflated with nitrogen baking single port vial in, add 10 milliliters of pimelinketone, 0.005 mole of titanium tetrachloride, 0.025 mole of α, α respectively, neodymium changed by-dipyridyl and 0.01 mole three (cyclopentadiene), obtains titanium complex catalyzer.
0.015 mole of 1-phenyl two ring [2,2,1] hept-2-ene", 0.015 mol maleic anhydride, 0.015 molar acetate vinyl acetate are added in single port vial in nitrogen atmosphere, adds 10ml pimelinketone and dissolve.Get the above-mentioned catalyzer (with titanium tetrachloride weighing scale) of 0.6% by the total weight of norbornylene, maleic anhydride, vinyl acetate three, inject above-mentioned miscellany with syringe.Constant temperature, at 80 DEG C, reacts 1 hour.Product impouring makes norbornylene, maleic anhydride, vinyl acetate terpolymer precipitate containing in 5% methanol hydrochloride solution, and throw out is extremely neutral by methanol wash, vacuum-drying, reaction yield 61.5%.
Embodiment 9
Through repeatedly vacuumizing, in the single port vial of inflated with nitrogen baking, adding 10 milliliters of pimelinketone respectively, 0.005 mole of titanium tetrachloride, 0.015 mole of porphyrin and 0.020 mole three (cyclopentadiene) change neodymium, obtaining titanium complex catalyzer.
0.015 mole of 1-phenyl two ring [2,2,1] hept-2-ene", 0.015 mol maleic anhydride, 0.015 molar acetate vinyl acetate are added in single port vial in nitrogen atmosphere, adds 10ml pimelinketone and dissolve.Get the above-mentioned catalyzer (with titanium tetrachloride weighing scale) of 0.2% by the total weight of norbornylene, maleic anhydride, vinyl acetate three, inject above-mentioned miscellany with syringe.Constant temperature, at 70 DEG C, reacts 3 hours.Product impouring makes norbornylene, maleic anhydride, vinyl acetate terpolymer precipitate containing in 5% methanol hydrochloride solution, and throw out is extremely neutral by methanol wash, vacuum-drying, reaction yield 75.4%.
Embodiment 10
Through repeatedly vacuumizing, in the single port vial of inflated with nitrogen baking, adding 10 milliliters of Isosorbide-5-Nitrae-dioxane respectively, 0.005 mole of titanium tetrachloride, 0.035 mole of benzoyl group acetone and 0.025 mole three (cyclopentadiene) change neodymium, obtaining titanium complex catalyzer.
0.015 mole of 5-phenyl two ring [2,2,1] hept-2-ene", 0.015 mol maleic anhydride, 0.015 molar acetate vinyl acetate are added in nitrogen atmosphere in single port vial, add 10ml1,4-dioxane dissolves.Get the above-mentioned catalyzer (with titanium tetrachloride weighing scale) of 0.5% by the total weight of norbornylene, maleic anhydride, vinyl acetate three, inject above-mentioned miscellany with syringe, constant temperature, at 60 DEG C, reacts 1 hour.Product impouring makes norbornylene, maleic anhydride, vinyl acetate terpolymer precipitate containing in 5% methanol hydrochloride solution, and throw out is extremely neutral by methanol wash, vacuum-drying, reaction yield 76.6%.
Embodiment 11
Through repeatedly vacuumizing, inflated with nitrogen baking single port vial in, add 10 milliliters of pimelinketone, 0.010 mole of titanium tetrachloride, 0.05 mole of α, α respectively, neodymium changed by-dipyridyl and 0.01 mole three (cyclopentadiene), obtains titanium complex catalyzer.
0.015 mole of 5-vinyl two ring [2,2,1] hept-2-ene", 0.015 mol maleic anhydride, 0.015 molar acetate vinyl acetate are added in single port vial in nitrogen atmosphere, adds 10ml pimelinketone and dissolve.Get the above-mentioned catalyzer (with titanium tetrachloride weighing scale) of 0.6% by the total weight of norbornylene, maleic anhydride, vinyl acetate three, inject above-mentioned miscellany with syringe.Constant temperature, at 90 DEG C, reacts 2.5 hours.Product impouring makes norbornylene, maleic anhydride, vinyl acetate terpolymer precipitate containing in 5% methanol hydrochloride solution, and throw out is extremely neutral by methanol wash, vacuum-drying, reaction yield 83.5%.
Embodiment 12
Through repeatedly vacuumizing, in the single port vial of inflated with nitrogen baking, adding 10 milliliters of pimelinketone respectively, 0.010 mole of titanium tetrachloride, 0.07 Acetyl Acetone and 0.06 three (cyclopentadiene) that rub that rub change neodymium, obtaining titanium complex catalyzer.
0.015 mole of two ring [2,2,1] hept-2-ene"-5-methyl-formiate, 0.015 mol maleic anhydride, 0.015 molar acetate vinyl acetate are added in single port vial in nitrogen atmosphere, adds 10ml pimelinketone and dissolve.Get the above-mentioned catalyzer (with titanium tetrachloride weighing scale) of 0.4% by the total weight of norbornylene, maleic anhydride, vinyl acetate three, inject above-mentioned miscellany with syringe.Constant temperature 70 DEG C, reacts 3 hours.Product impouring makes norbornylene, maleic anhydride, vinyl acetate terpolymer precipitate containing in 5% methanol hydrochloride solution, and throw out is extremely neutral by methanol wash, vacuum-drying, reaction yield 75.8%.
Embodiment 13
Through repeatedly vacuumizing, in the single port vial of inflated with nitrogen baking, adding 10 milliliters of tetrahydrofuran (THF)s respectively, 0.01 mole of titanium tetrachloride, 0.04 mole of benzoyl group acetone and 0.01 mole three (cyclopentadiene) change neodymium, obtaining titanium complex catalyzer.
Special for 0.015 two ring [2,2,1] hept-2-ene"-5-formic acid butyl ester, 0.015 mol maleic anhydride, 0.015 molar acetate vinyl acetate are added in single port vial in nitrogen atmosphere, adds 10ml tetrahydrofuran (THF) and dissolve.Get the above-mentioned catalyzer (with titanium tetrachloride weighing scale) of 1% by the total weight of norbornylene, maleic anhydride, vinyl acetate three, inject above-mentioned miscellany with syringe.Constant temperature, at 90 DEG C, reacts 0.5 hour.Containing in the methanol solution of 5% hydrochloric acid, norbornylene, maleic anhydride, vinyl acetate terpolymer are precipitated product impouring, throw out is by methanol wash to neutral, and vacuum-drying, recording reaction yield is 86.5%.
Embodiment 14
Through repeatedly vacuumizing, in the single port vial of inflated with nitrogen baking, adding 10 milliliters of tetrahydrofuran (THF)s respectively, 0.01 mole of titanium tetrachloride, 0.04 mole of isoquinoline 99.9 and 0.01 mole three (cyclopentadiene) change neodymium, obtaining titanium complex catalyzer.
0.015 mole of 5-phenyl two ring [2,2,1] hept-2-ene", 0.015 mol maleic anhydride, 0.015 molar acetate vinyl acetate are added in single port vial in nitrogen atmosphere, adds 10ml tetrahydrofuran (THF) and dissolve.Get the above-mentioned catalyzer (with titanium tetrachloride weighing scale) of 1% by the total weight of norbornylene, maleic anhydride, vinyl acetate three, inject above-mentioned miscellany with syringe.Constant temperature, at 90 DEG C, reacts 0.5 hour.Containing in the methanol solution of 5% hydrochloric acid, norbornylene, maleic anhydride, vinyl acetate terpolymer are precipitated product impouring, throw out is by methanol wash to neutral, and vacuum-drying, recording reaction yield is 83.4%.
Embodiment 15
Through repeatedly vacuumizing, in the single port vial of inflated with nitrogen baking, adding 10 milliliters of tetrahydrofuran (THF)s respectively, 0.01 mole of titanium tetrachloride, 0.04 mole of Acetyl Acetone and 0.01 mole three (cyclopentadiene) change neodymium, obtaining titanium complex catalyzer.
0.015 mole of 7-methyl bicyclic [2,2,1] hept-2-ene", 0.015 mol maleic anhydride, 0.015 molar acetate vinyl acetate are added in single port vial in nitrogen atmosphere, adds 10ml tetrahydrofuran (THF) and dissolve.Get the above-mentioned catalyzer (with titanium tetrachloride weighing scale) of 1% by the total weight of norbornylene, maleic anhydride, vinyl acetate three, inject above-mentioned miscellany with syringe.Constant temperature, at 90 DEG C, reacts 0.5 hour.Containing in the methanol solution of 5% hydrochloric acid, norbornylene, maleic anhydride, vinyl acetate terpolymer are precipitated product impouring, throw out is by methanol wash to neutral, and vacuum-drying, recording reaction yield is 87.5%.
Claims (4)
1. norbornylene class, maleic anhydride and a vinyl acetate terpolymer catalyzer, is characterized in that this catalyzer is prepared by following method:
In the single port vial of the drying of atmosphere of inert gases, three (cyclopentadiene) are changed neodymium, titanium tetrachloride and ligand compound and is dissolved in solvent, bottleneck emulsion tube seals, and obtains titanium complex catalyzer;
The mol ratio of described titanium tetrachloride and described part is 1: 8 ~ 8: 8, and the mol ratio that described three (cyclopentadiene) change neodymium and described titanium tetrachloride is 1: 8 ~ 8: 1;
Described part is selected from oxine, α, α ,-dipyridyl, phenanthroline, pyridine, isoquinoline 99.9, quinoline, porphyrin, Acetyl Acetone or benzoyl group acetone;
Described solvent is selected from tetrahydrofuran (THF), methyl-phenoxide, Isosorbide-5-Nitrae-dioxane, cyclohexanone or toluene; The ratio that the consumption of described solvent and described three (cyclopentadiene) change neodymium, part and titanium tetrachloride three sum is 10 milliliters: 0.015 ~ 0.15 mole;
Described part and 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.
2. norbornylene class according to claim 1, maleic anhydride and vinyl acetate terpolymer catalyzer, is characterized in that described titanium tetrachloride, neodymium is changed by three (cyclopentadiene), the mol ratio of part three is 1: 1: 4.
3. use norbornylene class as claimed in claim 1, maleic anhydride and vinyl acetate terpolymer catalyzer to carry out the method for norbornylene class, maleic anhydride and vinyl acetate terpolymer, it is characterized in that comprising the steps:
Be get norbornylene class, maleic anhydride and Vinyl Acetate Monomer at 1: 1: 1 according to mol ratio, three joined in the single port vial of the drying of atmosphere of inert gases, then in this single port vial, add dissolution with solvents; Joined by described titanium complex catalyzer in described single port vial, microwave heating was to isothermal reaction at 40 ~ 90 DEG C 0.5 ~ 3 hour;
The reaction product impouring obtained is contained in the methanol solution of 5wt% hydrochloric acid, obtain the throw out of norbornylene class, maleic anhydride and vinyl acetate terpolymer, after this throw out methanol wash to neutrality, vacuum-drying, namely obtains norbornylene class, maleic anhydride and vinyl acetate terpolymer;
With titanium tetrachloride weighing scale, the consumption of described titanium complex catalyzer is 0.03 ~ 1% of norbornylene class, maleic anhydride and Vinyl Acetate Monomer gross weight;
The consumption of described solvent and the ratio of polymerization single polymerization monomer total amount are 10 milliliters: 0.045 mole.
4. norbornylene class according to claim 3, the method of maleic anhydride and vinyl acetate terpolymer, 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.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201310613347.9A CN103626919B (en) | 2013-11-27 | 2013-11-27 | Norbornylene class, maleic anhydride and vinyl acetate terpolymer catalyzer and method for ternary polymerization |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201310613347.9A CN103626919B (en) | 2013-11-27 | 2013-11-27 | Norbornylene class, maleic anhydride and vinyl acetate terpolymer catalyzer and method for ternary polymerization |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN103626919A CN103626919A (en) | 2014-03-12 |
| CN103626919B true CN103626919B (en) | 2015-10-28 |
Family
ID=50208392
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201310613347.9A Expired - Fee Related CN103626919B (en) | 2013-11-27 | 2013-11-27 | Norbornylene class, maleic anhydride and vinyl acetate terpolymer catalyzer and method for ternary polymerization |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN103626919B (en) |
Families Citing this family (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104140496B (en) * | 2014-08-06 | 2016-08-17 | 宁波工程学院 | Norborneol alkenes, vinylacetate and esters of acrylic acid method for ternary polymerization |
| CN104140495B (en) * | 2014-08-06 | 2016-04-06 | 宁波工程学院 | Norbornylene class, esters of acrylic acid and octafluoro cyclopentenes terpolymer catalyzer and method for ternary polymerization |
| CN104262513B (en) * | 2014-10-14 | 2016-04-27 | 宁波工程学院 | Norbornylene class, vinyl acetate and octafluoro cyclopentenes terpolymer catalyzer and method for ternary polymerization |
| CN104311738B (en) * | 2014-10-14 | 2016-04-27 | 宁波工程学院 | Norbornylene class, maleic anhydride and octafluoro cyclopentenes terpolymer catalyzer and method for ternary polymerization |
| CN104817659B (en) * | 2015-05-04 | 2017-04-12 | 宁波工程学院 | Ternary polymerization catalyst of norbornene, octafluorocyclopentene and styrene and ternary polymerization method |
| CN105524218B (en) * | 2016-03-10 | 2018-04-03 | 宁波工程学院 | Norborneol alkenes, hexafluoropropene and 1 hexene ternary polymerization catalyst and method for ternary polymerization |
| CN105693928B (en) * | 2016-03-17 | 2017-08-08 | 宁波工程学院 | Norborneol alkenes, hexafluoropropene and acrylonitrile ternary polymerization catalyst and method for ternary polymerization |
| CN106832121B (en) * | 2017-02-20 | 2019-07-30 | 宁波工程学院 | Norborneol alkenes, cyclohexene and vinylene carbonate ternary polymerization catalyst and method for ternary polymerization |
Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5792824A (en) * | 1993-05-21 | 1998-08-11 | Asahi Kasei Kogyo Kabushiki Kaisha | Cyclic conjugated diene polymer and method of producing same |
| CN101328244A (en) * | 2008-07-31 | 2008-12-24 | 宁波工程学院 | Preparation of copolymer of norbornene and maleic anhydride |
| CN101691414A (en) * | 2009-06-15 | 2010-04-07 | 宁波工程学院 | Catalyst for norbornene, maleic anhydride and acrylic ester ternary polymerization and preparation method of catalyst and ternary polymerization method |
| CN103396514A (en) * | 2013-08-01 | 2013-11-20 | 宁波工程学院 | Catalyst for ternary polymerization of norbornene, maleic anhydride and pentene, and ternary polymerization method |
-
2013
- 2013-11-27 CN CN201310613347.9A patent/CN103626919B/en not_active Expired - Fee Related
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5792824A (en) * | 1993-05-21 | 1998-08-11 | Asahi Kasei Kogyo Kabushiki Kaisha | Cyclic conjugated diene polymer and method of producing same |
| CN101328244A (en) * | 2008-07-31 | 2008-12-24 | 宁波工程学院 | Preparation of copolymer of norbornene and maleic anhydride |
| CN101691414A (en) * | 2009-06-15 | 2010-04-07 | 宁波工程学院 | Catalyst for norbornene, maleic anhydride and acrylic ester ternary polymerization and preparation method of catalyst and ternary polymerization method |
| CN103396514A (en) * | 2013-08-01 | 2013-11-20 | 宁波工程学院 | Catalyst for ternary polymerization of norbornene, maleic anhydride and pentene, and ternary polymerization method |
Also Published As
| Publication number | Publication date |
|---|---|
| CN103626919A (en) | 2014-03-12 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN103626919B (en) | Norbornylene class, maleic anhydride and vinyl acetate terpolymer catalyzer and method for ternary polymerization | |
| CN103396514B (en) | Norbornylene class, maleic anhydride and amylene class terpolymer catalyzer and method for ternary polymerization | |
| CN102702432B (en) | Catalyst for use in ternary polymerization of norbornene, maleic anhydride and cyclohexene and ternary polymerization method | |
| CN102924658B (en) | Catalyst for ternary polymerization of norbornene, derivative of norbornene, tetrafluoroethylene and cyclohexene and method of ternary polymerization | |
| CN103254358B (en) | For catalyzer and the method for ternary polymerization of norbornylene class, tetrafluoroethylene and the terpolymer of amylene class | |
| CN101328244B (en) | Preparation of copolymer of norbornene and maleic anhydride | |
| CN105111372A (en) | Norbornene, octafluorocyclopentene and cyclohexene ternary polymerization catalyst and ternary polymerization method | |
| CN103864990B (en) | Norbornylene class, vinyl acetate and tetrahydrobenzene class terpolymer catalyzer and method for ternary polymerization | |
| CN103360544B (en) | Catalyst for norbornene, acrylate and pentene copolymerization, and copolymerization method | |
| CN101691414B (en) | Catalyst for norbornene, maleic anhydride and acrylic ester ternary polymerization and preparation method of catalyst and ternary polymerization method | |
| CN104140496B (en) | Norborneol alkenes, vinylacetate and esters of acrylic acid method for ternary polymerization | |
| CN104817659A (en) | Ternary polymerization catalyst of norbornene, octafluorocyclopentene and styrene and ternary polymerization method | |
| CN101684168B (en) | Catalyst used in ternary polymerization of norbornene, acrylate and tetrafluoroethylene, preparation method thereof and method for ternary polymerization | |
| CN104788615B (en) | Ternary copolymerization catalyst and ternary copolymerization method for norbornenes, styrene and N-phenyl maleimide | |
| CN105524218B (en) | Norborneol alkenes, hexafluoropropene and 1 hexene ternary polymerization catalyst and method for ternary polymerization | |
| CN104262513B (en) | Norbornylene class, vinyl acetate and octafluoro cyclopentenes terpolymer catalyzer and method for ternary polymerization | |
| CN101319028A (en) | Method for preparing norbornene and acrylic ester copolymer | |
| CN104311738B (en) | Norbornylene class, maleic anhydride and octafluoro cyclopentenes terpolymer catalyzer and method for ternary polymerization | |
| CN104140495B (en) | Norbornylene class, esters of acrylic acid and octafluoro cyclopentenes terpolymer catalyzer and method for ternary polymerization | |
| CN105218709B (en) | Norborneol alkenes, phenylethylene and maleic anhydride tercopolymer catalyst for copolymerization and method for ternary polymerization | |
| CN106832122B (en) | Norborneol alkenes, amylene class and vinylene carbonate ternary polymerization catalyst and method for ternary polymerization | |
| CN106832120B (en) | Norborneol alkenes, hexafluoropropene and vinylene carbonate ternary polymerization catalyst and method for ternary polymerization | |
| CN106749915B (en) | Norborneol alkenes, esters of acrylic acid and vinylene carbonate ternary polymerization catalyst and method for ternary polymerization | |
| CN106749912B (en) | Norborneol alkenes, vinylacetate and N-phenylmaleimide ternary polymerization catalyst and method for ternary polymerization | |
| CN106749913B (en) | Norborneol alkenes, octafluoro cyclopentene and N-phenylmaleimide ternary polymerization catalyst and method for ternary polymerization |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| C14 | Grant of patent or utility model | ||
| GR01 | Patent grant | ||
| CF01 | Termination of patent right due to non-payment of annual fee | ||
| CF01 | Termination of patent right due to non-payment of annual fee |
Granted publication date: 20151028 Termination date: 20161127 |