CN101691414B - Catalyst for norbornene, maleic anhydride and acrylic ester ternary polymerization and preparation method of catalyst and ternary polymerization method - Google Patents
Catalyst for norbornene, maleic anhydride and acrylic ester ternary polymerization and preparation method of catalyst and ternary polymerization method Download PDFInfo
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- CN101691414B CN101691414B CN2009100998430A CN200910099843A CN101691414B CN 101691414 B CN101691414 B CN 101691414B CN 2009100998430 A CN2009100998430 A CN 2009100998430A CN 200910099843 A CN200910099843 A CN 200910099843A CN 101691414 B CN101691414 B CN 101691414B
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Abstract
The invention relates to a catalyst for norbornene, maleic anhydride and acrylic ester ternary polymerization and a preparation method of the catalyst and a ternary polymerization method; the catalyst is prepared by rare-earth complex and halogenated hydrocarbon and can generate catalytic activity in a nitrogen protection system at normal pressure and at the temperature of 0-150 DEG C for catalyzing norbornene, maleic anhydride and acrylic ester ternary polymerization, and the products are soaked by methanol for easy washing and separation; the invention has the characteristics of high copolymer yield, low reaction temperature, cheap and easy-obtaining catalyst and high catalyst efficiency.
Description
Technical field
The present invention relates to the Polymer Synthesizing field, the method that specifically refers to a kind of catalyzer that is used for norbornylene and maleic anhydride, acrylic ester ternary polymerization and this Preparation of catalysts method and carry out norbornylene and maleic anhydride, acrylic ester ternary polymerization with this catalyzer.
Background technology
Polynorbornene is a kind of specific polymers, has excellent mechanical property, thermotolerance, the solubility in organic solvent and the transparency, can be used for the photoetching of 193nm UV-light.This material main drawback is that fragility, viscosity difference and molecular weight are low etc.After inserting maleic anhydride in the polynorbornene main chain, can improve the cohesiveness and the solubility of polymkeric substance, the gathering of propenoate into the toughness that can increase the multipolymer photoetching material.This terpolymer can be used as photoresist and is applied to the 193nm replica technology.And; The littler composition of development need size of microelectronics industry; To being applicable to that live width is the exposal technology of 1.3 μ m and following live width; Can select the 193nm photoetching technique, these technology relate to all respects of photoetching process, the problem that novel material that proposed new optical material and manufacturing thereof and coating technique, novel resist, is used for mask and protective film thereof etc. awaits solving.Therefore; Photoetching novel material in order to obtain has developed the alternating copolymerization material, mainly develops norbornylene and the two component copolymerization of maleic anhydride class and norbornylene and maleic anhydride, acrylic ester ternary polymerization material; Use the norbornylene that side group is arranged simultaneously; Purpose is to improve the resistance to corrosion of whole matrix, improves lithography performance, increases cohesiveness, solubility and the toughness of material.
The method of at present synthetic these materials mainly contains methods such as radical, living radical, metal catalyst.Like the synthetic catalyzer of superoxide that adopted of the 80th～92 page of disclosed photoetching material of Proceedings of SPIE Vol.5039 (2003) as radical polymerization, the synthetic catalyzer of AINB (Diisopropyl azodicarboxylate) that adopted of the 127th～135 page of disclosed photoetching material of Proceedings of SPIE Vol.4690 (2002) as radical polymerization.There is long reaction time in these compound methods of using at present, obtains shortcomings such as copolymer yield is low, molecular weight of copolymer is little, the multipolymer alternate degree is low, and domestic norbornylene and propenoate, tetrafluoroethylene triple copolymerization research are carried out seldom.
Summary of the invention
First technical problem to be solved by this invention is the present situation to prior art, a kind of catalyzer that is used for norbornylene and maleic anhydride, acrylic ester ternary polymerization is provided, to reduce temperature of reaction, raising catalytic efficiency (and copolymer yield.
Second technical problem to be solved by this invention is the present situation to prior art, and above-mentioned Preparation of catalysts method is provided.
The 3rd technical problem to be solved by this invention is the present situation to prior art, the method that provides the above-mentioned catalyst norbornylene of a kind of usefulness and maleic anhydride, propenoate to carry out terpolymer.
The present invention solves the problems of the technologies described above the technical scheme that is adopted:
The present invention is used for the catalyzer of norbornylene and maleic anhydride, acrylic ester ternary polymerization, it is characterized in that it is processed by rare-earth complex and halohydrocarbon, and wherein the mol ratio of rare-earth complex and halohydrocarbon is 1: 1～30; Described rare-earth complex is selected from any one in benzoyl group acetone yttrium, P 204 yttriums, P 507 yttriums, naphthenic acid yttrium, benzoyl group acetone neodymium, P 204 neodymiums, P 507 neodymiums, neodymium naphthenate, methyl ethyl diketone neodymium, benzoyl group acetone praseodymium, P 204 praseodymiums, P 507 praseodymiums, naphthenic acid praseodymium and the methyl ethyl diketone praseodymium; Said halohydrocarbon is selected from benzyl bromine, benzyl chlorine, 1-bromo-1-diphenylphosphino ethane, 1-chloro-1-diphenylphosphino ethane, 1-bromo-1-phenyl-propane, 1-chloro-1-phenyl-propane, bromo trimethyl-methane, chloro trimethyl-methane, bromo trimethylammonium ethane, chloro trimethylammonium ethane, the alpha-halogen alkene any one.Wherein, said alpha-halogen alkene is 3-bromo propylene or 3-bromo-1-butylene.The mol ratio of said rare-earth complex and halohydrocarbon is preferably 1: 15.
The method for preparing catalyzer of the present invention may further comprise the steps:
Dry halohydrocarbon of elder generation and solvent, dry back airtight storage is subsequent use; Then rare-earth complex is put into through the single port vial that repeatedly vacuumizes, inflated with nitrogen toasts; Bottleneck seals with emulsion tube; Inject dissolution with solvents with syringe, inject halohydrocarbon with syringe then, vial is put into constant temperature water bath; 20～60 ℃ of constant temperature 15～60 minutes, promptly get rare earth complex catalyst after the cooling.Wherein, said solvent is benzene, toluene, THF, sherwood oil, methyl-phenoxide, 1,4-dioxane, 1,2-ethylene dichloride, hexanaphthene, methylcyclohexane or pimelinketone; The drying of said halohydrocarbon and solvent all is dry with calcium chloride or hydrolith.This preparation method has advantage simply and easily.
Method with catalyst norbornylene of the present invention and propenoate, tetrafluoroethylene triple copolymerization may further comprise the steps:
According to mol ratio is to get norbornylene, maleic anhydride, propenoate at 1: 1: 1 to add in the inflated with nitrogen single port polymerization bottle, adds dissolution with solvents; By rare-earth complex is that 0.01～0.50% of norbornylene, maleic anhydride, propenoate three gross weight injected polymerization bottle with catalyzer with syringe; Put into Water Tank with Temp.-controlled or oil bath; 0～150 ℃ of reaction 6～8 hours, the product impouring contains 5% methanol hydrochloride solution, and (5% referred to mass content.) in make the terpolymer deposition of norbornylene and maleic anhydride, propenoate, throw out with methanol wash to neutral, vacuum-drying.Described norbornylene is selected from two ring [2,2,1] hept-2-ene"s, 1-methyl bicyclic [2,2,1] hept-2-ene", 5-methyl bicyclic [2,2; 1] hept-2-ene", 7-methyl bicyclic [2,2,1] hept-2-ene", 1-ethyl two ring [2,2,1] hept-2-ene"s, 5-ethyl two rings [2; 2,1] hept-2-ene", 5,5-dimethyl-two ring [2,2,1] hept-2-ene"s, 1-phenyl two rings [2; 2,1] hept-2-ene", 5-phenyl two ring [2,2,1] hept-2-ene"s, 5-vinyl two rings [2,2; 1] in hept-2-ene", two ring [2,2,1] hept-2-ene"-5-methyl-formiates, the special butyl ester of two ring [2,2,1] hept-2-ene"s-5-formic acid any one.Said propenoate is selected from methyl acrylate; Ethyl propenoate; Propyl acrylate; N-butyl acrylate; NSC 20949; The special butyl ester of vinylformic acid; The special n-pentyl ester of vinylformic acid; The special pentyl ester of vinylformic acid; Octadecyl acrylate; TEB 3K; Jia Jibingxisuanyizhi; Propyl methacrylate; N-BMA; Propenoic acid, 2-methyl, isobutyl ester; Tert-butyl methacrylate; The special n-pentyl ester of methylacrylic acid; The special pentyl ester of methylacrylic acid; In the stearyl methacrylate any one.Said solvent is benzene, toluene, THF, sherwood oil, methyl-phenoxide, 1,4-dioxane, 1,2-ethylene dichloride, hexanaphthene, methylcyclohexane or pimelinketone.
Catalyzer provided by the invention is a kind of novel rare-earth complex compound catalyst; This rare earth complex catalyst can be under normal pressure; Temperature is in the time of 0～150 ℃; In nitrogen protection system, produce catalytic activity, catalysis norbornylene and maleic anhydride, acrylic ester ternary polymerization soak product through methyl alcohol and are easy to the washing separation.Have the copolymer yield height, temperature of reaction is low, characteristics such as catalyzer is cheap, be easy to get, catalytic efficiency (height.And find to adopt rare-earth complex at home in document periodical and the Chinese patent as yet as norbornylene and maleic anhydride, acrylic ester ternary polymerization catalyzer.
Embodiment
Below in conjunction with embodiment the present invention is described in further detail.
For Preparation of catalysts process in following examples, if no special instructions, all wherein halohydrocarbon and solvent carried out drying treatment.Particularly be: the drying of halohydrocarbon and solvent is all dry with calcium chloride or hydrolith.
One, Preparation of Catalyst:
Embodiment 1: get 0.01 mole of neodymium naphthenate and be dissolved in 20 milliliters of toluene, in above-mentioned solution, add the 0.30 1-bromo-1-diphenylphosphino ethane that rubs, constant temperature is 30 minutes in 50 ℃ of water-baths, promptly gets rare earth complex catalyst after the cooling.
Embodiment 2: get 0.01 mole of neodymium naphthenate and be dissolved in 20 milliliters of hexanaphthenes, in above-mentioned solution, add 0.30 mole of 1-chloro-1-diphenylphosphino ethane, constant temperature is 30 minutes in 50 ℃ of water-baths, promptly gets rare earth complex catalyst after the cooling.
Embodiment 3: get 0.01 mole of neodymium naphthenate and be dissolved in 20 milliliters of benzene, in above-mentioned solution, add 0.20 mole of benzyl bromine, constant temperature is 30 minutes in 50 ℃ of water-baths, promptly gets rare earth complex catalyst after the cooling.
Embodiment 4: get 0.03 mole of neodymium naphthenate and be dissolved in 30 milliliters of toluene, in above-mentioned solution, add 0.90 mole of 1-bromo-1-diphenylphosphino ethane, constant temperature is 40 minutes in 50 ℃ of water-baths, promptly gets rare earth complex catalyst after the cooling.
Embodiment 5: get 0.01 mole of neodymium naphthenate and be dissolved in 20 milliliters of toluene, in above-mentioned solution, add 0.20 mole of 3-bromo propylene, constant temperature is 30 minutes in 50 ℃ of water-baths, promptly gets rare earth complex catalyst after the cooling.
Embodiment 6: get 0.01 mole of neodymium naphthenate and be dissolved in 30 milliliters of pimelinketone, in above-mentioned solution, add 0.15 mole of benzyl chlorine, constant temperature is 30 minutes in 50 ℃ of water-baths, promptly gets rare earth complex catalyst after the cooling.
Embodiment 7: get 0.01 mole of neodymium naphthenate and be dissolved in 30 milliliters of pimelinketone, in above-mentioned solution, add 0.10 mole of 1-bromo-1-diphenylphosphino ethane, constant temperature is 30 minutes in 50 ℃ of water-baths, promptly gets rare earth complex catalyst after the cooling.
Embodiment 8: get 0.01 mole of neodymium naphthenate and be dissolved in 30 milliliters of pimelinketone, in above-mentioned solution, add 0.05 mole of 1-bromo-1-diphenylphosphino ethane, constant temperature is 30 minutes in 50 ℃ of water-baths, promptly gets rare earth complex catalyst after the cooling.
Embodiment 9: get 0.01 mole of neodymium naphthenate and be dissolved in 30 milliliters of pimelinketone, in above-mentioned solution, add 0.15 mole of 1-bromo-1-diphenylphosphino ethane, constant temperature is 30 minutes in 50 ℃ of water-baths, promptly gets rare earth complex catalyst after the cooling.
Embodiment 10: get 0.01 mole of neodymium naphthenate and be dissolved in 30 milliliters of pimelinketone, in above-mentioned solution, add 0.07 mole of 1-bromo-1-diphenylphosphino ethane, constant temperature is 30 minutes in 50 ℃ of water-baths, promptly gets rare earth complex catalyst after the cooling.
Embodiment 11: get 0.01 mole of benzoyl group acetone yttrium and be dissolved in 30 milliliters of THFs, in above-mentioned solution, add 0.10 mole of 1-bromo-1-phenyl-propane, constant temperature is 60 minutes in 20 ℃ of water-baths, promptly gets rare earth complex catalyst after the cooling.
Embodiment 12: get 0.01 mole of P 204 yttrium and be dissolved in 30 milliliters of sherwood oils, in above-mentioned solution, add 0.03 mole of 1-chloro-1-phenyl-propane, constant temperature is 50 minutes in 30 ℃ of water-baths, promptly gets rare earth complex catalyst after the cooling.
Embodiment 13: get 0.01 mole of P 507 yttrium and be dissolved in 30 milliliters of methyl-phenoxides, in above-mentioned solution, add 0.08 mole bromine for trimethyl-methane, constant temperature is 40 minutes in 40 ℃ of water-baths, promptly gets rare earth complex catalyst after the cooling.
Embodiment 14: get 0.01 mole of naphthenic acid yttrium and be dissolved in 30 milliliter 1, in the 4-dioxane, in above-mentioned solution, add 0.03 mole of chloro trimethyl-methane, constant temperature is 15 minutes in 60 ℃ of water-baths, promptly gets rare earth complex catalyst after the cooling.
Embodiment 15: get 0.01 mole of benzoyl group acetone neodymium and be dissolved in 30 milliliter 1, in the 2-ethylene dichloride, in above-mentioned solution, add 0.20 mole bromine for trimethylammonium ethane, constant temperature is 30 minutes in 50 ℃ of water-baths, promptly gets rare earth complex catalyst after the cooling.
Embodiment 16: get 0.01 mole of P 204 neodymium and be dissolved in 30 milliliters of methylcyclohexanes, in above-mentioned solution, add 0.30 mole of chloro trimethylammonium ethane, constant temperature is 30 minutes in 50 ℃ of water-baths, promptly gets rare earth complex catalyst after the cooling.
Embodiment 17: get 0.01 mole of P 507 neodymium and be dissolved in 30 milliliters of methylcyclohexanes, in above-mentioned solution, add 0.25 mole of 3-bromo-1-butylene, constant temperature is 30 minutes in 50 ℃ of water-baths, promptly gets rare earth complex catalyst after the cooling.
Embodiment 18: get 0.01 mole of methyl ethyl diketone neodymium and be dissolved in 30 milliliters of methylcyclohexanes, in above-mentioned solution, add 0.10 mole of 1-chloro-1-diphenylphosphino ethane, constant temperature is 30 minutes in 50 ℃ of water-baths, promptly gets rare earth complex catalyst after the cooling.
Embodiment 19: get 0.01 mole of benzoyl group acetone praseodymium and be dissolved in 30 milliliters of methylcyclohexanes, in above-mentioned solution, add 0.15 mole of 1-chloro-1-diphenylphosphino ethane, constant temperature is 30 minutes in 50 ℃ of water-baths, promptly gets rare earth complex catalyst after the cooling.
Embodiment 20: get 0.01 mole of P 204 praseodymium and be dissolved in 30 milliliters of methylcyclohexanes, in above-mentioned solution, add 0.05 mole of 1-chloro-1-diphenylphosphino ethane, constant temperature is 30 minutes in 50 ℃ of water-baths, promptly gets rare earth complex catalyst after the cooling.
Embodiment 21: get 0.01 mole of P 507 praseodymium and be dissolved in 30 milliliters of methylcyclohexanes, in above-mentioned solution, add 0.03 mole of 1-chloro-1-diphenylphosphino ethane, constant temperature is 30 minutes in 50 ℃ of water-baths, promptly gets rare earth complex catalyst after the cooling.
Embodiment 22: get 0.01 mole of naphthenic acid praseodymium and be dissolved in 30 milliliters of methylcyclohexanes, in above-mentioned solution, add 0.12 mole of 1-chloro-1-diphenylphosphino ethane, constant temperature is 30 minutes in 50 ℃ of water-baths, promptly gets rare earth complex catalyst after the cooling.
Embodiment 23: get 0.01 mole of methyl ethyl diketone praseodymium and be dissolved in 30 milliliters of methylcyclohexanes, in above-mentioned solution, add 0.20 mole of 1-chloro-1-diphenylphosphino ethane, constant temperature is 30 minutes in 50 ℃ of water-baths, promptly gets rare earth complex catalyst after the cooling.
Two, applications catalyst prepares norbornylene, maleic anhydride, acrylate terpolymer:
Embodiment 1: 0.024 mole of two ring [2,2,1] hept-2-ene", 0.024 mole of maleic anhydride, the special butyl ester of 0.024 mol propylene acid are added 25ml in the inflated with nitrogen single port polymerization bottle, add the dissolving of 5ml toluene.By rare-earth complex is that 0.10% of norbornylene, maleic anhydride, propenoate three gross weight got catalyzer (catalyzer instance 2) and injected above-mentioned miscellany with syringe.Put into Water Tank with Temp.-controlled, 80 ℃ of reactions 6 hours.The product impouring contains makes norbornylene, maleic anhydride, acrylate terpolymer deposition in 5% methanol hydrochloride solution, throw out with methanol wash to the center, vacuum-drying, reaction yield (in norbornylene, maleic anhydride, propenoate total amount) 89.0%.
Embodiment 2: 0.024 mole of 1-methyl bicyclic [2,2,1] hept-2-ene", 0.024 mole of maleic anhydride, 0.024 mole of tert-butyl methacrylate are added 25ml in the inflated with nitrogen single port polymerization bottle, add the dissolving of 5ml toluene.By rare-earth complex is that 0.10% of norbornylene, maleic anhydride, propenoate three gross weight got catalyzer (catalyzer instance 1) and injected above-mentioned miscellany with syringe.Put into Water Tank with Temp.-controlled, 90 ℃ of reactions 7 hours.The product impouring contains makes norbornylene, maleic anhydride, acrylate terpolymer deposition in 5% methanol hydrochloride solution, throw out with methanol wash to the center, vacuum-drying, reaction yield (in norbornylene, maleic anhydride, propenoate total amount) 90.1%.
Embodiment 3: 0.024 mole of 5-methyl bicyclic [2,2,1] hept-2-ene", 0.024 mole of maleic anhydride, 0.024 mole of TEB 3K are added 25ml in the inflated with nitrogen single port polymerization bottle, add the dissolving of 5ml toluene.By rare-earth complex is that 0.20% of norbornylene, maleic anhydride, propenoate three gross weight got catalyzer (catalyzer instance 5) and injected above-mentioned miscellany with syringe.Put into Water Tank with Temp.-controlled, 70 ℃ of reactions 7 hours.The product impouring contains makes norbornylene, maleic anhydride, acrylate terpolymer deposition in 5% methanol hydrochloride solution, throw out with methanol wash to the center, vacuum-drying, reaction yield (in norbornylene, maleic anhydride, propenoate total amount) 71.2%.
Embodiment 4: 0.024 mole of 7-methyl bicyclic [2,2,1] hept-2-ene", 0.024 mole of maleic anhydride, 0.024 mol propylene acid methyl esters are added 25ml in the inflated with nitrogen single port polymerization bottle, add the dissolving of 5ml toluene.By rare-earth complex is that 0.20% of norbornylene, maleic anhydride, propenoate three gross weight got catalyzer (catalyzer instance 6) and injected above-mentioned miscellany with syringe.Put into Water Tank with Temp.-controlled, 70 ℃ of reactions 8 hours.The product impouring contains makes norbornylene, maleic anhydride, acrylate terpolymer deposition in 5% methanol hydrochloride solution, throw out with methanol wash to the center, vacuum-drying, reaction yield (in norbornylene, maleic anhydride, propenoate total amount) 93.5%.
Embodiment 5: 0.024 mole of 1-ethyl two ring [2,2,1] hept-2-ene"s, 0.024 mole of maleic anhydride, 0.024 mol propylene acetoacetic ester are added 25ml in the inflated with nitrogen single port polymerization bottle, add the dissolving of 5ml toluene.By rare-earth complex is that 0.50% of norbornylene, maleic anhydride, propenoate three gross weight got catalyzer (catalyzer instance 3) and injected above-mentioned miscellany with syringe.Put into Water Tank with Temp.-controlled, 70 ℃ of reactions 8 hours.The product impouring contains makes norbornylene, maleic anhydride, acrylate terpolymer deposition in 5% methanol hydrochloride solution, throw out with methanol wash to the center, vacuum-drying, reaction yield (in norbornylene, maleic anhydride, propenoate total amount) 76.5%.
Embodiment 6: 0.024 mole of 5-ethyl two ring [2,2,1] hept-2-ene"s, 0.024 mole of maleic anhydride, 0.024 mol propylene propyl propionate are added 25ml in the inflated with nitrogen single port polymerization bottle, add the dissolving of 5ml benzene.By rare-earth complex is that 0.02% of norbornylene, maleic anhydride, propenoate three gross weight got catalyzer (catalyzer instance 4) and injected above-mentioned miscellany with syringe.Put into Water Tank with Temp.-controlled, 0 ℃ of reaction 8 hours.The product impouring contains makes norbornylene, maleic anhydride, acrylate terpolymer deposition in 5% methanol hydrochloride solution, throw out with methanol wash to the center, vacuum-drying, reaction yield (in norbornylene, maleic anhydride, propenoate total amount) 53.5%.
Embodiment 7: with 0.024 mole 5,5-dimethyl-two ring [2,2,1] hept-2-ene"s, 0.024 mole of maleic anhydride, the positive butyl ester of 0.024 mol propylene acid add 25ml in the inflated with nitrogen single port polymerization bottle, add the dissolving of 5ml THF.By rare-earth complex is that 0.15% of norbornylene, maleic anhydride, propenoate three gross weight got catalyzer (catalyzer instance 7) and injected above-mentioned miscellany with syringe.Put into constant temperature oil bath, 150 ℃ of reactions 6 hours.The product impouring contains makes norbornylene, maleic anhydride, acrylate terpolymer deposition in 5% methanol hydrochloride solution, throw out with methanol wash to the center, vacuum-drying, reaction yield (in norbornylene, maleic anhydride, propenoate total amount) 87.1%.
Embodiment 8: 0.024 mole of 1-phenyl two ring [2,2,1] hept-2-ene"s, 0.024 mole of maleic anhydride, 0.024 mol propylene acid isobutylate are added 25ml in the inflated with nitrogen single port polymerization bottle, add the 5ml petroleum ether dissolution.By rare-earth complex is that 0.05% of norbornylene, maleic anhydride, propenoate three gross weight got catalyzer (catalyzer instance 8) and injected above-mentioned miscellany with syringe.Put into Water Tank with Temp.-controlled, 30 ℃ of reactions 8 hours.The product impouring contains makes norbornylene, maleic anhydride, acrylate terpolymer deposition in 5% methanol hydrochloride solution, throw out with methanol wash to the center, vacuum-drying, reaction yield (in norbornylene, maleic anhydride, propenoate total amount) 43.5%.
Embodiment 9: 0.024 mole of 5-phenyl two ring [2,2,1] hept-2-ene"s, 0.024 mole of maleic anhydride, the special n-pentyl ester of 0.024 mol propylene acid are added 25ml in the inflated with nitrogen single port polymerization bottle, add the dissolving of 5ml methyl-phenoxide.By rare-earth complex is that 0.16% of norbornylene, maleic anhydride, propenoate three gross weight got catalyzer (catalyzer instance 9) and injected above-mentioned miscellany with syringe.Put into Water Tank with Temp.-controlled, 80 ℃ of reactions 7 hours.The product impouring contains makes norbornylene, maleic anhydride, acrylate terpolymer deposition in 5% methanol hydrochloride solution, throw out with methanol wash to the center, vacuum-drying, reaction yield (in norbornylene, maleic anhydride, propenoate total amount) 83.4%.
Embodiment 10: 0.024 mole of 5-vinyl two ring [2,2,1] hept-2-ene"s, 0.024 mole of maleic anhydride, the special pentyl ester of 0.024 mol propylene acid are added 25ml in the inflated with nitrogen single port polymerization bottle, add 5ml 1, the dissolving of 4-dioxane.By rare-earth complex is that 0.15% of norbornylene, maleic anhydride, propenoate three gross weight got catalyzer (catalyzer instance 10) and injected above-mentioned miscellany with syringe.Put into Water Tank with Temp.-controlled, 60 ℃ of reactions 7 hours.The product impouring contains makes norbornylene, maleic anhydride, acrylate terpolymer deposition in 5% methanol hydrochloride solution, throw out with methanol wash to the center, vacuum-drying, reaction yield (in norbornylene, maleic anhydride, propenoate total amount) 73.9%.
Embodiment 11: 0.024 mole of two ring [2,2,1] hept-2-ene"-5-methyl-formiate, 0.024 mole of maleic anhydride, 0.024 mol propylene acid octadecyl ester are added 25ml in the inflated with nitrogen single port polymerization bottle, add 5ml 1, the dissolving of 2-ethylene dichloride.By rare-earth complex is that 0.40% of norbornylene, maleic anhydride, propenoate three gross weight got catalyzer (catalyzer instance 11) and injected above-mentioned miscellany with syringe.Put into Water Tank with Temp.-controlled, 90 ℃ of reactions 7 hours.The product impouring contains makes norbornylene, maleic anhydride, acrylate terpolymer deposition in 5% methanol hydrochloride solution, throw out with methanol wash to the center, vacuum-drying, reaction yield (in norbornylene, maleic anhydride, propenoate total amount) 81.5%.
Embodiment 12: the special butyl ester of 0.024 mole of two ring [2,2,1] hept-2-ene"-5-formic acid, 0.024 mole of maleic anhydride, 0.024 mole of Jia Jibingxisuanyizhi are added 25ml in the inflated with nitrogen single port polymerization bottle, add the dissolving of 5ml hexanaphthene.By rare-earth complex is that 0.30% of norbornylene, maleic anhydride, propenoate three gross weight got catalyzer (catalyzer instance 12) and injected above-mentioned miscellany with syringe.Put into Water Tank with Temp.-controlled, 50 ℃ of reactions 6 hours.The product impouring contains makes norbornylene, maleic anhydride, acrylate terpolymer deposition in 5% methanol hydrochloride solution, throw out with methanol wash to the center, vacuum-drying, reaction yield (in norbornylene, maleic anhydride, propenoate total amount) 56.4%.
Embodiment 13: 0.024 mole of two ring [2,2,1] hept-2-ene", 0.024 mole of maleic anhydride, 0.024 mole of propyl methacrylate are added 25ml in the inflated with nitrogen single port polymerization bottle, add the dissolving of 5ml methylcyclohexane.By rare-earth complex is that 0.20% of norbornylene, maleic anhydride, propenoate three gross weight got catalyzer (catalyzer instance 13) and injected above-mentioned miscellany with syringe.Put into Water Tank with Temp.-controlled, 70 ℃ of reactions 8 hours.The product impouring contains makes norbornylene, maleic anhydride, acrylate terpolymer deposition in 5% methanol hydrochloride solution, throw out with methanol wash to the center, vacuum-drying, reaction yield (in norbornylene, maleic anhydride, propenoate total amount) 57.3%.
Embodiment 14: 0.024 mole of two ring [2,2,1] hept-2-ene", 0.024 mole of maleic anhydride, 0.024 mole of n-BMA are added 25ml in the inflated with nitrogen single port polymerization bottle, add the dissolving of 5ml pimelinketone.By rare-earth complex is that 0.10% of norbornylene, maleic anhydride, propenoate three gross weight got catalyzer (catalyzer instance 14) and injected above-mentioned miscellany with syringe.Put into Water Tank with Temp.-controlled, 80 ℃ of reactions 8 hours.The product impouring contains makes norbornylene, maleic anhydride, acrylate terpolymer deposition in 5% methanol hydrochloride solution, throw out with methanol wash to the center, vacuum-drying, reaction yield (in norbornylene, maleic anhydride, propenoate total amount) 43.2%.
Embodiment 14: 0.024 mole of two ring [2,2,1] hept-2-ene", 0.024 mole of maleic anhydride, 0.024 mole of Propenoic acid, 2-methyl, isobutyl ester are added 25ml in the inflated with nitrogen single port polymerization bottle, add the dissolving of 5ml hexanaphthene.By rare-earth complex is that 0.05% of norbornylene, maleic anhydride, propenoate three gross weight got catalyzer (catalyzer instance 14) and injected above-mentioned miscellany with syringe.Put into constant temperature oil bath, 140 ℃ of reactions 6 hours.The product impouring contains makes norbornylene, maleic anhydride, acrylate terpolymer deposition in 5% methanol hydrochloride solution, throw out with methanol wash to the center, vacuum-drying, reaction yield (in norbornylene, maleic anhydride, propenoate total amount) 49.5%.
Embodiment 15: 0.024 mole of two ring [2,2,1] hept-2-ene", 0.024 mole of maleic anhydride, 0.024 mole of special n-pentyl ester of methylacrylic acid are added 25ml in the inflated with nitrogen single port polymerization bottle, add the dissolving of 5ml hexanaphthene.By rare-earth complex is that 0.15% of norbornylene, maleic anhydride, propenoate three gross weight got catalyzer (catalyzer instance 15) and injected above-mentioned miscellany with syringe.Put into Water Tank with Temp.-controlled, 90 ℃ of reactions 8 hours.The product impouring contains makes norbornylene, maleic anhydride, acrylate terpolymer deposition in 5% methanol hydrochloride solution, throw out with methanol wash to the center, vacuum-drying, reaction yield (in norbornylene, maleic anhydride, propenoate total amount) 83.3%.
Embodiment 16: 0.024 mole of two ring [2,2,1] hept-2-ene", 0.024 mole of maleic anhydride, 0.024 mole of special pentyl ester of methylacrylic acid are added 25ml in the inflated with nitrogen single port polymerization bottle, add the dissolving of 5ml hexanaphthene.By rare-earth complex is that 0.25% of norbornylene, maleic anhydride, propenoate three gross weight got catalyzer (catalyzer instance 16) and injected above-mentioned miscellany with syringe.Put into Water Tank with Temp.-controlled, 70 ℃ of reactions 7 hours.The product impouring contains makes norbornylene, maleic anhydride, acrylate terpolymer deposition in 5% methanol hydrochloride solution, throw out with methanol wash to the center, vacuum-drying, reaction yield (in norbornylene, maleic anhydride, propenoate total amount) 75.5%.
Embodiment 17: 0.024 mole of two ring [2,2,1] hept-2-ene", 0.024 mole of maleic anhydride, 0.024 mole of stearyl methacrylate are added 25ml in the inflated with nitrogen single port polymerization bottle, add the dissolving of 5ml hexanaphthene.By rare-earth complex is that 0.13% of norbornylene, maleic anhydride, propenoate three gross weight got catalyzer (catalyzer instance 17) and injected above-mentioned miscellany with syringe.Put into Water Tank with Temp.-controlled, 60 ℃ of reactions 6 hours.The product impouring contains makes norbornylene, maleic anhydride, acrylate terpolymer deposition in 5% methanol hydrochloride solution, throw out with methanol wash to the center, vacuum-drying, reaction yield (in norbornylene, maleic anhydride, propenoate total amount) 62.2%.
Embodiment 17: 0.024 mole of two ring [2,2,1] hept-2-ene", 0.024 mole of maleic anhydride, the special butyl ester of 0.024 mol propylene acid are added 25ml in the inflated with nitrogen single port polymerization bottle, add the dissolving of 5ml hexanaphthene.By rare-earth complex is that 0.03% of norbornylene, maleic anhydride, propenoate three gross weight got catalyzer (catalyzer instance 17) and injected above-mentioned miscellany with syringe.Put into Water Tank with Temp.-controlled, 80 ℃ of reactions 7 hours.The product impouring contains makes norbornylene, maleic anhydride, acrylate terpolymer deposition in 5% methanol hydrochloride solution, throw out with methanol wash to the center, vacuum-drying, reaction yield (in norbornylene, maleic anhydride, propenoate total amount) 69.5%.
Embodiment 18: 0.024 mole of two ring [2,2,1] hept-2-ene", 0.024 mole of maleic anhydride, the special butyl ester of 0.024 mol propylene acid are added 25ml and filled in the ammonia single port polymerization bottle, add the dissolving of 5ml hexanaphthene.By rare-earth complex is that 0.15% of norbornylene, maleic anhydride, propenoate three gross weight got catalyzer (catalyzer instance 18) and injected above-mentioned miscellany with syringe.Put into Water Tank with Temp.-controlled, 60 ℃ of reactions 7 hours.The product impouring contains makes norbornylene, maleic anhydride, acrylate terpolymer deposition in 5% methanol hydrochloride solution, throw out with methanol wash to the center, vacuum-drying, reaction yield (in norbornylene, maleic anhydride, propenoate total amount) 73.8%.
Embodiment 19: 0.024 mole of two ring [2,2,1] hept-2-ene", 0.024 mole of maleic anhydride, the special butyl ester of 0.024 mol propylene acid are added 25ml in the inflated with nitrogen single port polymerization bottle, add the dissolving of 5ml hexanaphthene.By rare-earth complex is that 0.20% of norbornylene, maleic anhydride, propenoate three gross weight got catalyzer (catalyzer instance 19) and injected above-mentioned miscellany with syringe.Put into Water Tank with Temp.-controlled, 70 ℃ of reactions 8 hours.The product impouring contains makes norbornylene, maleic anhydride, acrylate terpolymer deposition in 5% methanol hydrochloride solution, throw out with methanol wash to the center, vacuum-drying, reaction yield (in norbornylene, maleic anhydride, propenoate total amount) 90.5%.
Embodiment 20: 0.024 mole of two ring [2,2,1] hept-2-ene", 0.024 mole of maleic anhydride, the special butyl ester of 0.024 mol propylene acid are added 25ml in the inflated with nitrogen single port polymerization bottle, add the dissolving of 5ml hexanaphthene.By rare-earth complex is that 0.10% of norbornylene, maleic anhydride, propenoate three gross weight got catalyzer (catalyzer instance 20) and injected above-mentioned miscellany with syringe.Put into Water Tank with Temp.-controlled, 80 ℃ of reactions 8 hours.The product impouring contains makes norbornylene, maleic anhydride, acrylate terpolymer deposition in 5% methanol hydrochloride solution, throw out with methanol wash to the center, vacuum-drying, reaction yield (in norbornylene, maleic anhydride, propenoate total amount) 64.4%.
Embodiment 21: 0.024 mole of two ring [2,2,1] hept-2-ene", 0.024 mole of maleic anhydride, the special butyl ester of 0.024 mol propylene acid are added 25ml in the inflated with nitrogen single port polymerization bottle, add the dissolving of 5ml hexanaphthene.By rare-earth complex is that 0.30% of norbornylene, maleic anhydride, propenoate three gross weight got catalyzer (catalyzer instance 21) and injected above-mentioned miscellany with syringe.Put into Water Tank with Temp.-controlled, 80 ℃ of reactions 8 hours.The product impouring contains makes norbornylene, maleic anhydride, acrylate terpolymer deposition in 5% methanol hydrochloride solution, throw out with methanol wash to the center, vacuum-drying, reaction yield (in norbornylene, maleic anhydride, propenoate total amount) 52.5%.
Embodiment 22: 0.024 mole of two ring [2,2,1] hept-2-ene", 0.024 mole of maleic anhydride, the special butyl ester of 0.024 mol propylene acid are added 25ml in the inflated with nitrogen single port polymerization bottle, add the dissolving of 5ml hexanaphthene.By rare-earth complex is that 0.10% of norbornylene, maleic anhydride, propenoate three gross weight got catalyzer (catalyzer instance 22) and injected above-mentioned miscellany with syringe.Put into Water Tank with Temp.-controlled, 70 ℃ of reactions 7 hours.The product impouring contains makes norbornylene, maleic anhydride, acrylate terpolymer deposition in 5% methanol hydrochloride solution, throw out with methanol wash to the center, vacuum-drying, reaction yield (in norbornylene, maleic anhydride, propenoate total amount) 77.5%.
Embodiment 23: 0.024 mole of two ring [2,2,1] hept-2-ene", 0.024 mole of maleic anhydride, the special butyl ester of 0.024 mol propylene acid are added 25ml in the inflated with nitrogen single port polymerization bottle, add the dissolving of 5ml hexanaphthene.By rare-earth complex is that 0.15% of norbornylene, maleic anhydride, propenoate three gross weight got catalyzer (catalyzer instance 23) and injected above-mentioned miscellany with syringe.Put into Water Tank with Temp.-controlled, 20 ℃ of reactions 7 hours.The product impouring contains makes norbornylene, maleic anhydride, acrylate terpolymer deposition in 5% methanol hydrochloride solution, throw out with methanol wash to the center, vacuum-drying, reaction yield (in norbornylene, maleic anhydride, propenoate total amount) 43.5%.
Claims (9)
1. catalyzer that is used for norbornylene and maleic anhydride, acrylic ester ternary polymerization is characterized in that it is processed by rare-earth complex and halohydrocarbon, and wherein the mol ratio of rare-earth complex and halohydrocarbon is 1: 1～30; Described rare-earth complex is selected from any one in naphthenic acid yttrium, neodymium naphthenate, methyl ethyl diketone neodymium, naphthenic acid praseodymium and the methyl ethyl diketone praseodymium; Said halohydrocarbon is selected from benzyl bromine, benzyl chlorine, 1-bromo-1-diphenylphosphino ethane, 1-chloro-1-diphenylphosphino ethane, 1-bromo-1-phenyl-propane, 1-chloro-1-phenyl-propane, bromo trimethyl-methane, chloro trimethyl-methane, bromo trimethylammonium ethane, chloro trimethylammonium ethane, the alpha-halogen alkene any one.
2. catalyzer according to claim 1 is characterized in that said alpha-halogen alkene is 3-bromo propylene or 3-bromo-1-butylene.
3. method of making catalyzer as claimed in claim 1 is characterized in that may further comprise the steps:
Dry halohydrocarbon of elder generation and solvent, dry back airtight storage is subsequent use; Then rare-earth complex is put into through the single port vial that repeatedly vacuumizes, inflated with nitrogen toasts; Bottleneck seals with emulsion tube; Inject dissolution with solvents with syringe, inject halohydrocarbon with syringe then, vial is put into constant temperature water bath; 20～60 ℃ of constant temperature 15～60 minutes, promptly get rare earth complex catalyst after the cooling.
4. method according to claim 3 is characterized in that said solvent is benzene, toluene, THF, sherwood oil, methyl-phenoxide, 1,4-oxygen six rings, 1,2-ethylene dichloride, hexanaphthene, methylcyclohexane or pimelinketone.
5. according to claim 3 or 4 described methods, the drying that it is characterized in that said halohydrocarbon and solvent all is dry with calcium chloride or hydrolith.
6. method of utilizing the described catalyst norbornylene of claim 1 and maleic anhydride, acrylic ester ternary polymerization is characterized in that may further comprise the steps:
According to mol ratio is to get norbornylene, maleic anhydride, propenoate at 1: 1: 1 to add in the inflated with nitrogen single port polymerization bottle, adds dissolution with solvents; By rare-earth complex is that 0.01～0.50% of norbornylene, maleic anhydride, propenoate three gross weight injected polymerization bottle with catalyzer with syringe; Put into Water Tank with Temp.-controlled; 0～150 ℃ of reaction 6～8 hours; The product impouring contains the terpolymer deposition that makes norbornylene and maleic anhydride, propenoate in 5% methanol hydrochloride solution, throw out with methanol wash to neutral, vacuum-drying.
7. method according to claim 6 is characterized in that described norbornylene is selected from two ring [2,2,1] hept-2-ene"s, 1-methyl bicyclic [2,2,1] hept-2-ene", 5-methyl bicyclic [2; 2,1] hept-2-ene", 7-methyl bicyclic [2,2,1] hept-2-ene", 1-ethyl two ring [2,2,1] hept-2-ene"s, 5-ethyl two rings [2; 2,1] hept-2-ene", 5,5-dimethyl-two ring [2,2,1] hept-2-ene"s, 1-phenyl two rings [2; 2,1] hept-2-ene", 5-phenyl two ring [2,2,1] hept-2-ene"s, 5-vinyl two rings [2,2; 1] in hept-2-ene", two ring [2,2,1] hept-2-ene"-5-methyl-formiates, the special butyl ester of two ring [2,2,1] hept-2-ene"s-5-formic acid any one.
8. method according to claim 6 is characterized in that said propenoate is selected from the special butyl ester of methyl acrylate, ethyl propenoate, propyl acrylate, n-butyl acrylate, NSC 20949, vinylformic acid, the special n-pentyl ester of vinylformic acid, the special pentyl ester of vinylformic acid, octadecyl acrylate, TEB 3K, Jia Jibingxisuanyizhi, propyl methacrylate, n-BMA, Propenoic acid, 2-methyl, isobutyl ester, tert-butyl methacrylate, the special n-pentyl ester of methylacrylic acid, the special pentyl ester of methylacrylic acid, the stearyl methacrylate any one.
9. according to claim 6 or 7 or 8 described methods, it is characterized in that said solvent is benzene, toluene, THF, sherwood oil, methyl-phenoxide, 1,4-dioxane, 1,2-ethylene dichloride, hexanaphthene, methylcyclohexane or pimelinketone.
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| CN103864990B (en) * | 2014-03-11 | 2016-02-24 | 宁波工程学院 | Norbornylene class, vinyl acetate and tetrahydrobenzene class 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 |
| CN106749912B (en) * | 2016-12-06 | 2019-03-29 | 宁波工程学院 | Norborneol alkenes, vinylacetate and N-phenylmaleimide ternary polymerization catalyst and method for ternary polymerization |
| CN108424680A (en) * | 2018-03-28 | 2018-08-21 | 东莞市同丰高分子材料有限公司 | A kind of high-performance self-crosslinking acrylic resin Cathode Electrophoretic Paint of Environment Protection and preparation method |
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