CN1053675C - Removal of catalyst from polymer by atom transferred free radical polymerization - Google Patents
Removal of catalyst from polymer by atom transferred free radical polymerization Download PDFInfo
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- CN1053675C CN1053675C CN97106590A CN97106590A CN1053675C CN 1053675 C CN1053675 C CN 1053675C CN 97106590 A CN97106590 A CN 97106590A CN 97106590 A CN97106590 A CN 97106590A CN 1053675 C CN1053675 C CN 1053675C
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Abstract
The present invention discloses a method for adsorbing and removing a catalyst in a polymer prepared by atom transferred free radical polymerizationat an original position. In the method, the catalyst in the polymer can be effectively removed, i.e. a coordination compound of a transition metal compound and trialkylamine. The method comprises the steps that an adsorbing agent and a solvent (without the solvent) are filled in a terminated atom transferred free radical polymerizationat system on the spot; the adsorbing agent and the catalyst carry out physical and chemical adsorption reaction, a product is filtered and dried to obtain a purified polymer, and the adsorbing agent is silicate, active carbon, alumina, etc. The original position adsorbing method of the present invention is the effective and practical method and has favorable industrial application prospects.
Description
The present invention relates to remove by the catalyzer in the prepared polymkeric substance of atom transition free radical polymerization reaction with the original position absorption method, this method uses porous materials such as silicate, gac, aluminum oxide as sorbent material terminated polymerization system to be carried out original position absorption.The polymkeric substance of being handled is white or faint yellow solid particulate matter, and content of copper ion is not more than 10ppm.
Can synthesize multiple polymkeric substance, segmented copolymer, graft copolymer and star-type polymer with the atom transfer radical polymerization technology with expected structure, but institute's synthetic polymkeric substance contains catalyzer, therefore, the color and luster that this not only can influence product more seriously may influence its use properties.Document Seong Mu Jo, Hyun-Jong Paik, and Krzysztof Matyjaszewski, Polymer Preprints, 1997, Vol.38, No.1,697; Seong Mu Jo, Hyun-Jong Paik, and Krzysztof Matyjaszewski, Polymer Preprints, 1997, Vol.38, No.1,699; Kathryn L.Beers, Alison Kern and Krzysztof Matyjaszewski, Polymer Preprints, 1997, Vol.38, No.1,695 and Yoshiki Nakagawa, Peter Miller, Cristina Pacis and Krzysztof Matyjaszewski, Polymer Preprints, 1997, Vol.38, No.1, the 701 usefulness precipitator method and alumina column chromatography method are removed the catalyzer in this kind polymerization system, and these two kinds of methods can only be used in the laboratory, have no industrial application value, the former need expend a large amount of solvents and increase the facility investment expense.And the latter also will usually change filler in the pillar except that will increasing the facility investment expense, and this produces obviously for the industrialization of atom transfer radical polymerization technology from now on continuously greatly and has caused very big difficulty.
The present invention but is a kind of method of removing catalyzer of economy, and the advantage of original position absorption is that the facility investment expense is low, the industrialization operate continuously easy to implement of its technological process, adsorption efficiency height, free from environmental pollution etc.Be industrial comparatively effective, practical method of removing, for the industrialization basis has been established in the widespread use of this polymerization technique from now on by catalyzer in the prepared polymkeric substance of atom transfer radical polymerization.
Design of the present invention is such:
Utilize sorbent material have than some composition in large specific surface and porous characteristics and the sorbent material can with the character of the tertiary amine title complex generation chemical reaction of transistion metal compound, the catalyzer of atom transfer radical polymerization system is produced physics and chemisorption simultaneously.Thereby reach the purpose of removing catalyzer in the polymkeric substance, make polymkeric substance be able to purifying.
The present invention realizes according to such design:
Sorbent material, solvent (or not solubilizing agent) are added in the terminated atom transfer radical polymerization system on the spot, feed the airborne oxygen of inert gas replacement, stir and be warming up to adsorption temp, adsorption number ten minutes is to a few hours.Pressure filtration in pressure filter is then reclaimed solvent with distillation or steam distillation, and polymkeric substance is dried to constant weight with boulton process.Promptly obtain purified polymer.
Described sorbent material is silicate (as: acidic white earth, kaolin, diatomite, a molecular sieve); Gac (as: acid gac); Aluminum oxide (as: active aluminium sesquioxide).Its consumption is the 2-10% of system gross weight
Described solvent can be single solvent, also can be mixed solvent, and these solvents comprise aromatic hydrocarbon solvent, ether solvent and ketones solvent.Be generally: toluene, dimethylbenzene, tetrahydrofuran (THF), acetone or their mixture etc.
Described atom transfer radical polymerization system is halide-containing/transistion metal compound/tertiary amine coordination agent/vinyl monomer.
Halide-containing is that initiator is meant: benzyl chlorine or bromine and derivative thereof, the polymkeric substance that contains the end group chlorine or bromine and multipolymer, bromination SBS thermoplastic elastomer, chlorine or bromine acetic ester etc.
Transistion metal compound/tertiary amine coordination agent is a catalyzer, and transistion metal compound is meant: the halogenide of elements such as Cu, Co, Fe, Ni, Ru, Ti, rare earth, vitriol, nitrate etc.; The tertiary amine coordination agent is meant: 2,2 '-bipyridine and derivative thereof, N, N '-Tetramethyl Ethylene Diamine and other many methyl polyamines, two N, N '-dimethyl aminoethyl ether and other N, the amino Soxylat A 25-7 of N '-tetramethyl-, triethylene diamine, hexamethylphosphoramide etc.
Vinyl monomer is meant: vinylbenzene, (methyl) acrylate, divinyl, isoprene, vinyl cyanide etc.
Described rare gas element is nitrogen, argon gas.
Described adsorption temp is the reflux temperature of room temperature to solvent.
Described adsorption time is 30 minutes to 7 hours.
Described filter-press is a plate and frame(type)filter press.
The technology of removing of catalyzer is such in the prepared polymkeric substance of atom transfer radical polymerization:
Sorbent material, solvent (if solution polymerization also not solubilizing agent) are directly added in the reactor of the terminated atom transfer radical polymerization system of filling, feed the air in the inert gas replacement reactor, stirring is warming up to adsorption temp stoichiometric number ten minutes to a few hours, press filtration while hot, filtrate places the distiller distillation or reclaims solvent with steam distillation, places the polymkeric substance in the distiller vacuum drier to be dried to constant weight at last.
The polymkeric substance of atom transfer radical polymerization system preparation generally contains hundreds of catalyzer to thousands of ppm, and these catalyzer are dispersed in the polymkeric substance with the form of coordination compound, bring color and luster to polymkeric substance.The existence meeting of catalytic active center simultaneously brings serious side reaction to polymkeric substance, as the degraded of polymkeric substance and coupling, branching etc. again, thus the performance of impact polymer.The method of removing that is used for atom transfer radical polymerization system institute synthetic polymkeric substance catalyzer at present is the precipitator method and Al
2O
3The column chromatography for separation method, these two kinds of methods only are used for the separation of laboratory small amount of polymer because the shortcoming of itself can not be used in industrial acquisition.Absorption method proposed by the invention has above-mentioned two kinds of unrivaled advantages of method: the processing condition gentleness is fit to industrial flow; Can realize original position absorption, be convenient to reclaim solvent; The polymkeric substance loss is few, the yield height; The ratio height of throughput and investment cost has reduced production cost.Therefore, method of the present invention is to realize atom transfer radical polymerization skilled industry essential important component.
Embodiment 1
With the benzyl chloride is initiator, CuCl/2, and 2 '-bipyridine title complex is that catalyzer causes cinnamic atom transferred free radical mass polymerization, the heavy 141.5g of monomer.After polyreaction stops, record polymericular weight Mn=17486, molecular weight distribution D=1.48 with GPC.In filling the polymerization reactor of above-mentioned system, add tetrahydrofuran (THF) 140g and acidic white earth 14.0g (consumption is 5.0%), stirring is warming up to the reflux temperature of tetrahydrofuran (THF), in reaction pressure filtration after 4 hours under this temperature, filtrate put in the dry distillation device distill out partial solvent, in distiller, add 100g water, the adularescent polymer precipitation is separated out, the mixture of redistillation water outlet and tetrahydrofuran (THF), the polymer precipitation of separating out is placed enamel tray, vacuum-drying gets faint yellow polymkeric substance 130.0g to constant weight.Polymer yield is 92.8% (per-cent of the weight of polymkeric substance and monomeric charge amount, down together), and atomic absorption spectrochemical analysis Cu ion content is 4.43ppm.
Embodiment 2
With the benzyl chloride is initiator, CuCl/2, and 2 '-bipyridine title complex is that catalyzer causes cinnamic atom transferred free radical solution polymerization, the heavy 130.0g of monomer, and solvent is the 150g tetrahydrofuran (THF).After polyreaction stops, record polymericular weight Mn=15738, molecular weight distribution D=1.51 with GPC.In filling the polymerization reactor of above-mentioned system, add acidic white earth 7.0g (consumption is 2.5%), stirring is warming up to the reflux temperature of tetrahydrofuran (THF), in reaction pressure filtration after 4 hours under this temperature, place distiller to distill out partial solvent filtrate, add 100g water in distiller, the adularescent polymer precipitation is separated out, the mixture of redistillation water outlet and tetrahydrofuran (THF), the polymer precipitation of separating out is placed enamel tray, and vacuum-drying gets light yellow polymkeric substance 105.0g to constant weight.Polymer yield is 80.7%, and the Cu ion content is 4.55ppm.
Embodiment 3
With the benzyl chloride is initiator, CuCl/2, and 2 '-bipyridine title complex is that catalyzer causes cinnamic atom transferred free radical mass polymerization, the heavy 60.0g of monomer.After polyreaction stops, record polymericular weight Mn=42303, molecular weight distribution D=1.39 with GPC.In filling the polymerization reactor of above-mentioned system, add the dimethylbenzene of 120g and the acidic white earth (consumption is 3.3%) of 6.0g, stir and be warming up to 90 ℃,, reclaim dimethylbenzene with wet distillation in reaction pressure filtration after 4 hours under this temperature.The polymer precipitation of separating out is placed enamel tray, and vacuum-drying gets white polymer 52.0g to constant weight, and yield is 86.7%, and the Cu ion content is 4.22ppm.
Embodiment 4
With the benzyl chloride is initiator, CuCl/2, and 2 '-bipyridine title complex is that catalyzer causes cinnamic atom transferred free radical mass polymerization, the heavy 60.0g of monomer.After polyreaction stops, record polymericular weight Mn=42987, molecular weight distribution D=1.40 with GPC.In filling the polymerization reactor of above-mentioned system, add acidic white earth 6.0g (consumption is 3.3%), toluene 120g.Stirring is warming up to 90 ℃, in reaction pressure filtration after 4 hours under this temperature, reclaims toluene with wet distillation.The polymer precipitation of separating out is placed enamel tray, and vacuum-drying gets white polymer 55.0g to constant weight, and yield is 91.7%, and the Cu ion content is 2.53ppm.
Embodiment 5
With the benzyl chloride is initiator, CuCl/2, and 2 '-bipyridine title complex is that catalyzer causes cinnamic atom transferred free radical mass polymerization, the heavy 60.0g of monomer.After polyreaction stops, record polymericular weight Mn=42987, molecular weight distribution D=1.40 with GPC.In filling the polymerization reactor of above-mentioned system, add acidic white earth 9.0g (consumption is 5.0%), toluene 120g.Stirring is warming up to 90 ℃, in reaction pressure filtration after 4 hours under this temperature, reclaims toluene with wet distillation.The polymer precipitation of separating out is placed enamel tray, and vacuum-drying gets white polymer 56.0g to constant weight, and yield is 93.3%, and the Cu ion content is 0.72ppm.
Embodiment 6
With the benzyl chloride is initiator, CuCl/2, and 2 '-bipyridine title complex is that catalyzer causes cinnamic atom transferred free radical mass polymerization, the heavy 60.0g of monomer.After polyreaction stops, record polymericular weight Mn=42987, molecular weight distribution D=1.40 with GPC.In filling the polymerization reactor of above-mentioned system, add acidic white earth 12.0g (consumption is 6.7%), toluene 120g.Stirring is warming up to 90 ℃, in reaction pressure filtration after 4 hours under this temperature, reclaims toluene with wet distillation.The polymer precipitation of separating out is placed enamel tray, and vacuum-drying gets white polymer 56.0g to constant weight, and yield is 93.3%, and the Cu ion content is 6.27ppm.
Embodiment 7
With the benzyl chloride is initiator, CuCl/2, and 2 '-bipyridine title complex is that catalyzer causes cinnamic atom transferred free radical mass polymerization, the heavy 38.0g of monomer styrene.After polyreaction stops, record polymericular weight Mn=44943, molecular weight distribution D=1.40 with GPC.In filling the polymerization reactor of above-mentioned system, add acidic white earth 7.6g (consumption is 6.7%), dimethylbenzene 76g.Stirring is warming up to 90 ℃, in reaction pressure filtration after 4 hours under this temperature, reclaims dimethylbenzene with wet distillation.The polymer precipitation of separating out is placed enamel tray, and vacuum-drying gets white polymer 36.0g to constant weight, and yield is 94.7%, and the Cu ion content is 4.72ppm.
Embodiment 8
With the benzyl chloride is initiator, CuCl/2, and 2 '-bipyridine title complex is that catalyzer causes the solution polymerization of methyl methacrylate monomer atom transferred free radical, the heavy 38.0g of monomer, solvent xylene 30g.When polyreaction stops, record polymericular weight Mn=28563, molecular weight distribution D=1.55 with GPC.In filling the polymerization reactor of above-mentioned system, add toluene 50g, dimethylbenzene 50g and acidic white earth 6.0g (consumption is 4.3%).Stirring is warming up to 130 ℃, in reaction pressure filtration after 4 hours under this temperature, reclaims toluene and dimethylbenzene with wet distillation.The polymer precipitation of separating out is placed enamel tray, and vacuum-drying gets light yellow polymkeric substance 35.5g to constant weight, and yield is 93.4%, and the Cu ion content is 2.01ppm.
Embodiment 9
With end group chlorine polystyrene (Mn=43000, weight is 80.0g) is initiator, CuCl/2, and 2 '-bipyridine title complex is that catalyzer causes the solution polymerization of methyl methacrylate monomer atom transferred free radical, the heavy 30.0g of monomer, solvent xylene 50g.When polyreaction stops, record the molecular weight Mn=61816 of block polymer, molecular weight distribution D=1.27 with GPC.In filling the polymerization reactor of above-mentioned system, add dimethylbenzene 250g, acidic white earth 12.5g (consumption is 3.0%).Stirring is warming up to 90 ℃, in reaction pressure filtration after 4 hours under this temperature, reclaims dimethylbenzene with wet distillation.The polymer precipitation of separating out is placed enamel tray, and vacuum-drying gets light yellow polymkeric substance 102.0g to constant weight, and yield is 92.7%, and the Cu ion content is 7.19ppm.
Embodiment 10
With end group chlorine polystyrene (Mn=17500, weight is 34.0g) is initiator, CuCl/2, and 2 '-bipyridine title complex is that catalyzer causes the solution polymerization of methyl methacrylate monomer atom transferred free radical, the heavy 60.0g of monomer, solvent xylene 50g.When polyreaction stops, record the molecular weight Mn=49844 of block polymer, molecular weight distribution D=2.00 with GPC.In filling the polymerization reactor of above-mentioned system, add dimethylbenzene 150g, tetrahydrofuran (THF) 100g, toluene 100g, acidic white earth 12.5g (consumption is 2.5%).Stirring is warming up to 60 ℃, in reaction pressure filtration after 4 hours under this temperature, reclaims dimethylbenzene, toluene equal solvent with wet distillation.The polymer precipitation of separating out is placed enamel tray, and vacuum-drying gets light yellow polymkeric substance 90.5g to constant weight, and yield is 96.3%, and the Cu ion content is 0.33ppm.
Embodiment 11
With the tetracol phenixin is that initiator, CuCl/ phenanthroline title complex are that catalyzer causes the mass polymerization of styrene monomer atom transferred free radical, the heavy 27.0g of monomer.When polyreaction stops, record the molecular weight Mn=30555 of polymkeric substance, molecular weight distribution D=2.16 with GPC.In filling the polymerization reactor of above-mentioned system, add dimethylbenzene 100g, acidic white earth 6.0g (consumption is 4.7%).Stirring is warming up to 60 ℃, in reaction pressure filtration after 4 hours under this temperature, reclaims the dimethylbenzene equal solvent with wet distillation.The polymer precipitation of separating out is placed enamel tray, and vacuum-drying gets light yellow polymkeric substance 24.0g to constant weight, and yield is 88.0%, and the Cu ion content is 4.85ppm.
Embodiment 12
With the benzyl chloride is initiator, CuCl/N, and N '-Tetramethyl Ethylene Diamine title complex is that catalyzer causes cinnamic atom transferred free radical solution polymerization, the heavy 26.3g of monomer, solvent xylene 24g.After polyreaction stops, record polymericular weight Mn=80611, molecular weight distribution D=1.80 with GPC.In filling the polymerization reactor of above-mentioned system, add the dimethylbenzene of 50g and the diatomite (consumption is 5.0%) of 5.0g, stir and be warming up to 90 ℃,, reclaim dimethylbenzene with wet distillation in reaction pressure filtration after 2.5 hours under this temperature.The polymer precipitation of separating out is placed enamel tray, and vacuum-drying gets white polymer 24.0g to constant weight, and yield is 91.3%, and the Cu ion content is 4.19ppm.
Embodiment 13
With the benzyl chloride is initiator, CuCl/N, and N '-Tetramethyl Ethylene Diamine title complex is that catalyzer causes cinnamic atom transferred free radical solution polymerization, the heavy 26.3g of monomer, solvent xylene 24g.After polyreaction stops, record polymericular weight Mn=80611, molecular weight distribution D=1.80 with GPC.In filling the polymerization reactor of above-mentioned system, add the dimethylbenzene of 50g and the acid gac (consumption is 5.0%) of 5.0g, stir and be warming up to 90 ℃,, reclaim dimethylbenzene with wet distillation in reaction pressure filtration after 1 hour 50 minutes under this temperature.The polymer precipitation of separating out is placed enamel tray, and vacuum-drying gets white polymer 23.5g to constant weight, and yield is 89.4%, and the Cu ion content is 1.27ppm.
Embodiment 14
Yi Benzyl base chlorine is initiator, CuCl/N, and N '-Tetramethyl Ethylene Diamine title complex is that catalyzer causes cinnamic atom transferred free radical solution polymerization, the heavy 26.3g of monomer, solvent xylene 24g.After polyreaction stops, record polymericular weight Mn=80611, molecular weight distribution D=1.80 with GPC.In filling the polymerization reactor of above-mentioned system, add the dimethylbenzene of 50g and the Magnesium Trisilicate (consumption is 5.0%) of 5.0g, stir and be warming up to 90 ℃,, reclaim dimethylbenzene with wet distillation in reaction pressure filtration after 30 minutes under this temperature.The polymer precipitation of separating out is placed enamel tray, and vacuum-drying gets white polymer 24.5g to constant weight, and yield is 93.2%, and the Cu ion content is 5.85ppm.
Embodiment 15
With bromination SBS (weight is 10g) is initiator, CuCl/2, and 2 '-bipyridine title complex is that catalyzer causes cinnamic atom transferred free radical solution polymerization, the heavy 50.0g of monomer, solvent xylene 200g.After polyreaction stops, record polymericular weight Mn=71666, molecular weight distribution D=1.94 with GPC.In filling the polymerization reactor of above-mentioned system, add 12.5g acidic white earth (consumption is 4.8%), stir and be warming up to 80 ℃,, reclaim dimethylbenzene with wet distillation in reaction pressure filtration after 1.5 hours under this temperature.The polymer precipitation of separating out is placed enamel tray, and vacuum-drying gets faint yellow polymkeric substance 14.0g to constant weight, and yield is 23.3%, and the Cu ion content is 5.64ppm.
Embodiment 16
With the benzyl chloride is the two N of initiator, CuCl/, and N '-dimethyl aminoethyl ether title complex is that catalyzer causes cinnamic atom transferred free radical solution polymerization, the heavy 26.6g of monomer, solvent xylene 23g.After polyreaction stops, record polymericular weight Mn=68417, molecular weight distribution D=1.45 with GPC.In filling the polymerization reactor of above-mentioned system, add the dimethylbenzene of 100g and the acidic white earth (consumption is 5.0%) of 7.5g, at room temperature stir, react pressure filtration after 7 hours, reclaim dimethylbenzene with wet distillation.The polymer precipitation of separating out is placed enamel tray, and vacuum-drying gets white polymer 24.5g to constant weight, and yield is 92.1%, and the Cu ion content is 1.98ppm.
Embodiment 17
With the benzyl chloride is the two N of initiator, CuCl/, and N '-dimethyl aminoethyl ether title complex is that catalyzer causes cinnamic atom transferred free radical solution polymerization, the heavy 26.6g of monomer, solvent xylene 23g.After polyreaction stops, record polymericular weight Mn=68417, molecular weight distribution D=1.45 with GPC.The aluminum oxide (consumption is 5.0%) that in filling the polymerization reactor of above-mentioned system, adds dimethylbenzene, the 0.5g vitriol oil and the 7.5g of 100g, stirring is warming up to the refluxing xylene temperature, in reaction pressure filtration after 1 hour 30 minutes under this temperature, reclaim dimethylbenzene with wet distillation.The polymer precipitation of separating out is placed enamel tray, and vacuum-drying gets white polymer 23.0g to constant weight, and yield is 86.5%, and the Cu ion content is 0.87ppm.
Embodiment 18
With the benzyl chloride is the two N of initiator, CuCl/, and N '-dimethyl aminoethyl ether title complex is that catalyzer causes cinnamic atom transferred free radical solution polymerization, the heavy 26.6g of monomer, solvent xylene 23g.After polyreaction stops, record polymericular weight Mn=68417, molecular weight distribution D=1.45 with GPC.The molecular sieve (consumption is 5.0%) that in filling the polymerization reactor of above-mentioned system, adds dimethylbenzene, the 0.5g vitriol oil and the 7.5g of 100g, stirring is warming up to the refluxing xylene temperature, in reaction pressure filtration after 1 hour 30 minutes under this temperature, reclaim dimethylbenzene with wet distillation.The polymer precipitation of separating out is placed enamel tray, and vacuum-drying gets white polymer 22.0g to constant weight, and yield is 82.7%, and the Cu ion content is 10.00ppm.
Embodiment 19
With tetramethylolmethane tetrachloro acetic ester is initiator, CuCl/2, and 2 '-bipyridine title complex is that catalyzer causes cinnamic atom transferred free radical mass polymerization, the heavy 4.5g of monomer.After polyreaction stops, record polymericular weight Mn=7482, molecular weight distribution D=1.52 with GPC.In filling the polymerization reactor of above-mentioned system, add acetone 50g, acidic white earth 2.0g (consumption is 3.7%), stirring is warming up to the acetone reflux temperature, in reaction pressure filtration after 1 hour under this temperature, filtrate is placed enamel tray, after treating the acetone volatilization, vacuum-drying gets white polymer 3.0g to constant weight, yield is 66.7%, and the Cu ion content is 5.46ppm.
Embodiment 20
With the tetracol phenixin is that initiator, CuCl/ phenylbenzene phenanthroline title complex are that catalyzer causes the mass polymerization of styrene monomer atom transferred free radical, the heavy 24.5g of monomer.When polyreaction stops, record the molecular weight Mn=22635 of polymkeric substance, molecular weight distribution D=1.51 with GPC.In filling the polymerization reactor of above-mentioned system, add dimethylbenzene 100g, kaolin 6.0g (consumption is 4.8%).Stirring is warming up to reflux temperature, in reaction pressure filtration after 4 hours under this temperature, reclaims solvent with wet distillation.The polymer precipitation of separating out is placed enamel tray, and vacuum-drying gets light yellow polymkeric substance 23.0g to constant weight, and yield is 93.9%, and the Cu ion content is 4.55ppm.
Claims (10)
1. the method for the removing-original position absorption method of catalyzer in the prepared polymkeric substance of atom transfer radical polymerization, it is characterized in that sorbent material or sorbent material and solvent are placed terminated atom transfer radical polymerization system on the spot, in the rare gas element atmosphere, carry out absorption reaction to remove the catalyzer in the atom transfer radical polymerization thing in abundant down stirring of adsorption temp, pressure filtration then, drying obtains purified polymer, and described catalyzer is the coordination compound that transistion metal compound and tertiary amine form.
2. method according to claim 1, it is characterized in that described tertiary amine is selected from 2,2 '-bipyridine and derivative thereof, N, N '-Tetramethyl Ethylene Diamine and other many methyl polyamines, two N, N '-dimethyl aminoethyl ether and other N, the amino Soxylat A 25-7 of N '-tetramethyl-, triethylene diamine or hexamethylphosphoramide.
3. method according to claim 1 is characterized in that described transistion metal compound is selected from the halogenide of Cu, Co, Fe, Ni, Ru, Ti or rare earth element, vitriol or nitrate.
4. method according to claim 1 is characterized in that sorbent material is silicate compound, gac or aluminum oxide.
5. method according to claim 1 is characterized in that solvent is single solvent or double solvents, and these solvents comprise aromatic hydrocarbon solvent, ether solvent and ketones solvent.
6. method according to claim 5 is characterized in that solvent is toluene, dimethylbenzene, tetrahydrofuran (THF) or acetone.
7. method according to claim 1 is characterized in that adsorption temp is the reflux temperature of room temperature to solvent.
8. method according to claim 1 is characterized in that adsorption time is 30 minutes to 7 hours.
9. method according to claim 1 is characterized in that drying process carries out in two steps, and the first step reclaims solvent with distillation method or steam distillation, the second step vacuum-drying.
10. method according to claim 1 is characterized in that the polymkeric substance behind the purifying has following feature: (a) the polymkeric substance color and luster is white or light yellow; (b) residual catalyst content is in copper: be not more than 10ppm.
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| US5462995A (en) * | 1991-06-11 | 1995-10-31 | Nippon Zeon Co., Ltd. | Hydrogenated products of thermoplastic norbornene polymers, their production, substrates for optical elements obtained by molding them, optical elements and lenses |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101389664B (en) * | 2006-04-03 | 2011-09-07 | 赢创罗姆有限责任公司 | Copper removal from ATRP products by means of addition of sulfur compounds |
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