CN1224633C - Load catalyst containing nickel and iron and its application - Google Patents
Load catalyst containing nickel and iron and its application Download PDFInfo
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- CN1224633C CN1224633C CNB031506232A CN03150623A CN1224633C CN 1224633 C CN1224633 C CN 1224633C CN B031506232 A CNB031506232 A CN B031506232A CN 03150623 A CN03150623 A CN 03150623A CN 1224633 C CN1224633 C CN 1224633C
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
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- Y02P20/52—Improvements relating to the production of bulk chemicals using catalysts, e.g. selective catalysts
Abstract
The present invention relates to a load catalyst containing nickel and iron and the application thereof. High specific surface crosslinking polyacrylic acid ion-exchange resin powder is used as a load carrier of the catalyst and is matched with nickel halogenide and iron trihalide for complexation to prepare the load catalyst. The load catalyst forms a solid-liquid reaction system with an initiator, a monomer and a solvent according to certain proportion to catalyze the controllable free radical polymerization. After the reaction is finished, products and the catalyst can be simply separated, and the residual quantity of the metal catalyst in the products is low. Compared with other load catalysts in the same type, the catalyst can be circularly used through simple washing; besides, the catalyst has no oxygen sensitive defect, simplifies catalyst regeneration steps and avoids environment damage caused by that catalyst can not be recycled.
Description
Technical field:
The present invention relates to a kind of supported catalyst that contains ferronickel that is used for activity/controllable polymerization, utilize this catalyzer to make and have the narrow distribution homopolymer and the multipolymer of specifying molecular weight, only the simple centrifugation of need can be with catalyst removal for reaction system.Compare with other supported catalyst of the same type, supported catalyst manipulation of regeneration of the present invention is simple, and environmental pollution is avoided in the energy recycle.Belong to the polymkeric substance synthesis technical field.
Background technology:
Living polymerization is to realize molecular designing, synthesizes to have the important means of ad hoc structure and performance polymkeric substance.Because living polymerisation process commonly used, as severe reaction conditions such as anionoid polymerization, cationoid polymerisation, group transfer polymerizations, suitable monomers is less.Relatively radical polymerization is because the monomer that adapts to is very extensive with it, and mild condition requires not sternly to small amount of impurities, and as moisture etc., application prospect is extremely wide.
Atom transfer radical polymerization (ATRP) is meant as the halogenide of initiator and is captured (activation step) behind the halogen atom by the transition metal complex of lower valency, forms free radical.Elementary free radical can be captured halogen atom rapidly from the transition metal halide of high valence state behind the some monomer molecules of polymerization, form halogenide dormancy kind (passivation step), and transition metal complex then becomes lower valency from high valence state.The dormancy kind can not the trigger monomer polymerization, but it can be captured halogen atom by the transition metal complex of lower valency and activate, and forms spike.Come to this repeatedly by " activation-passivation " process, halogen atom constantly shifts between the transition metal complex of dormancy kind and high valence state, net result be all polymer chain along with the time evenly increases, thereby the realization controllable polymerization.
Atom transfer radical polymerization is because the reaction conditions gentleness, and it is extensive to adapt to monomer, can make molecular weight distribution very narrow (disperseing near single), specify the polymkeric substance of molecular weight, can prepare the clear and definite segmented copolymer of structure and receives much attention.Compare with traditional active cloudy (sun) ionic polymerization, the monomer of atom transfer radical polymerization must harsh pre-treatment, easy to operate easily.Typical atom transfer radical polymerization adopts cuprous halide/bipyridine to make catalyzer usually, its disadvantage is the separation difficulty of reaction after product and catalyzer, normally reaction solution is diluted, by aluminum oxide (alumina) post, make cuprous halide/bipyridine catalyzer be adsorbed on it again.This catalyst removal mode treatment capacity is little, and power consumption is big, can't realize the industrialization operation.Because cuprous halide and coordinate complex compound thereof all have bigger toxicity, will cause serious harm to environment, so the atom transfer radical polymerization product are to restrict one of its industrialized major obstacle in recent years with separating of catalyzer.
For improving separating of catalyzer and reaction solution, people load on the effective constituent of catalyzer on the solid phase carrier, carry out the out-phase reaction, and reaction can direct filtration can separate solid-phase catalyst after finishing.External bibliographical information (Hong SC, Matyjaszewski K Macromolecules35 (20): 7592-7605SEP 24 2002.) is arranged, as adopting the silica gel load cuprous bromide of functionalization; Crosslinked polystyrene particle load cuprous bromide of functionalization or the like.But such catalyst preparation process complexity, some operation is difficult to mass-producing, so cost is higher.
Summary of the invention:
The objective of the invention is to exist the problem of separation difficulty at existing ATRP catalyzer, a kind of segregative ferronickel loaded catalyst that contains is proposed, use this catalyzer energy controlled polymerization, the polymkeric substance of molecular weight, narrow distribution is specified in preparation, the maximum characteristics of this catalyzer are after its catalytic polymerization finishes, can can be with its whole separation by simple filtering, the catalyst residue amount is low.
For realizing such purpose, the present invention forms supported catalyst with the load carriers of high-ratio surface cross linked polyacrylate ion exchange resin powder as catalyzer with dihalide nickel, three iron halide ligand complexes.Supported catalyst and initiator, monomer, solvent are formed the solid-liquid reaction system by a certain percentage, can the catalysis controllable free-radical polymerisation.Reaction can be simply with product and catalyst separating after finishing, and the metal catalyst residual volume in the product is low; Catalyzer is a reusable edible after simple washing, does not have oxysensible shortcoming, has avoided catalyzer to reclaim and environment is caused serious harm.
The present invention can carry out as follows:
(1) the complexing load carriers of preparation catalyzer.Utilize the load carriers of cross linked polyacrylate ion exchange resin as the catalyzer iron halide, through the 1-5% alkali liquid washing, change ion exchange resin into sodium type or potassium type from Hydrogen, be washed till pH=9 with deionized water again, after 80 ℃ of vacuum-drying, pulverize through ball mill, vacuum-drying gets cross linked polyacrylate ion exchange resin PAA powder again.
(2) preparation loading type passivator.Get after 1 part of three iron halide be dissolved in 10 parts of methyl alcohol, add 3 parts of cross linked polyacrylate ion exchange resin powders, in 70 ℃ of stirring and refluxing after 3 hours, deviate from after methyl alcohol and the vacuum-drying PAA-FeX
3Crude product.This crude product till colourless, makes PAA-FeX again through methanol-eluted fractions after the vacuum-drying
3Wherein FeX3 is three iron halide, comprises iron trichloride FeCl
3, ferric bromide FeBr
3
(3) preparation loading type activator.After getting 1 part of dihalide nickel and placing 10 parts of methyl alcohol, after fully stirring, adds 30 parts of cross linked polyacrylate ion exchange resin powders, in 90 ℃ of stirring and refluxing after 3 hours, deviating from must PAA-NiX after methyl alcohol and the vacuum-drying
2NiX wherein
2Be dihalide nickel, comprise Nickel Chloride NiCl
2, Nickel Bromide NiBr
2
(4) supported catalyst of preparation controllable free-radical polymerisation.Get PAA-NiX
2, PAA-FeX
3And cross linked polyacrylate ion exchange resin powder, 1: 20 in molar ratio～40: 200～4000 proportionings are mixed, and can form the supported catalyst that contains ferronickel.Wherein, the consumption of cross linked polyacrylate ion exchange resin powder is by the cubage of carboxyl in the dry weight resin, PAA-FeX
3Consumption with the cubage of Fe, PAA-NiX
2Consumption with the cubage of Ni.
The supported catalyst that the present invention contains ferronickel can be applicable to prepare homopolymer and multipolymer, and concrete method is as follows:
Get initiator and by PAA-NiX
2, PAA-FeX
3Supported catalyst with cross linked polyacrylate ion exchange resin powder formation, mix by mole proportioning 1: 1: 20～40: 300～4000, to system implementation vacuum outgas-inflated with nitrogen, circulate after 5 times, add 200 parts of methyl acrylic ester monomers of drying, deoxidation and 2～4 times again to the solvent of monomer volume, stir and 70-110 ℃ of reaction.When desire prepares multipolymer, can after transform substantially, first kind of monomer add 200 parts of another kind of monomers again and continue reaction.After reaction finishes, with solvent cut and with the reaction solution cooling that reaction solution is centrifugal, separate clear liquid, can remove catalyzer.Can obtain polymkeric substance after solvent steamed.
The consumption of catalyzer complexing load carriers cross linked polyacrylate ion exchange resin powder is relevant with used solvent, and to weak polar solvent, consumption is 300-500 part, and to intensive polar solvent, consumption is 2000-4000 part.
After the toluene wash of supported catalyst drying of the present invention deoxidation, promptly renewable.Compare with other supported catalyst of the same type, this supported catalyst manipulation of regeneration is simple, does not have the shortcoming of micro amount of oxygen general lower valency transition metal halide oxidation wherein in the system, and the system amount of attitude transition metal halide at a middle or low price will remain unchanged.
The ion exchange resin material that the present invention is used, except the crosslinked polypropylene acid resin, can also adopt the cross-linked poly-methyl methacrylate resin and comprise the polyacrylic acid unit, the polymethyl acid unit replaces at interior various multipolymers.
Used initiator can be p-methyl benzene sulfonic chloride, a-chloropropionate when the supported catalyst of the present invention's preparation was applied to prepare polymkeric substance, a-ethyl bromide or a-bromine ethylbenzene.
Used methyl acrylic ester monomer can also be used esters of acrylic acid when the supported catalyst of the present invention's preparation was applied to prepare homopolymer and multipolymer, styrenic, and the alkyl vinyl ethers is equivalent to be replaced.
The catalyzer of the present invention preparation can the catalyzing atom transfer free radical polymerization, makes molecular weight distribution near monodispersed (PDI is less than 1.3) polymkeric substance; The catalyzer that utilizes the present invention to prepare can prepare the clear and definite AB type of multiple structure or ABA type or the more complicated segmented copolymer of structure easily, and these polymkeric substance are widely used in polymer blending, modification and coatings industry; After the catalyst atom transfer radical polymerization of the present invention's preparation finishes, catalyzer can be at an easy rate by centrifugal or filter with catalyst separating, metal catalyst residual volume in the polymkeric substance satisfies the requirement to foreign matter content in the polymkeric substance fully less than 20ppm; Catalyst cupport carrier of the present invention---crosslinked acrylic resin has no to poison, and the purification that is widely used in bio-pharmaceuticals separates, and is sophisticated industrialization product, and the source is abundant, and is cheap and easy to get, has excellent industrial application foreground.Utilize the approaching monodispersed various multipolymers that catalyzer that the present invention prepares not only can the processability excellence, but also developed new purposes, have high economic benefit and social benefit for existing Industrial products; The catalyzer of the present invention's preparation is through simple solvent wash, dry, promptly renewable after the deoxidation, avoided traditional atom transfer radical polymerization catalyst separating difficulty, power consumption is big, catalyzer can't reclaim and environment is caused shortcomings such as serious harm, is the green product that meets the 21st century environmental protection concept.
Embodiment:
Below in conjunction with specific embodiment technical scheme of the present invention is further described.
Embodiment 1
(1) the complexing load carriers of preparation catalyzer.Utilize the load carriers of cross linked polyacrylate ion exchange resin as the catalyzer iron halide, through 5% alkali liquid washing, change ion exchange resin into the sodium type from Hydrogen, be washed till pH=9 with deionized water again, after 80 ℃ of vacuum-drying, pulverize through ball mill, vacuum-drying gets cross linked polyacrylate ion exchange resin powder PAA (Na) again.
(2) preparation loading type passivator.Get 1 part of iron trichloride FeCl
3After being dissolved in 10 parts of methyl alcohol, add 3 parts of cross linked polyacrylate ion exchange resin powders, in 70 ℃ of stirring and refluxing after 3 hours, deviate from after methyl alcohol and the vacuum-drying PAA-FeCl
3Crude product.This crude product till colourless, makes PAA-FeCl again through methanol-eluted fractions after the vacuum-drying
3
(3) preparation loading type activator.Get 1 part of NiCl
2After placing 10 parts of methyl alcohol, after fully stirring, adds 30 parts of cross linked polyacrylate ion exchange resin powders, in 90 ℃ of stirring and refluxing after 3 hours, deviating from must PAA-NiCl after methyl alcohol and the vacuum-drying
2
(4) supported catalyst of preparation controllable free-radical polymerisation.Get Nickel Chloride PAA-NiCl
2, PAA-FeCl
3And cross linked polyacrylate ion exchange resin powder, proportioning was mixed in 1: 30: 300 in molar ratio, can form the supported catalyst that contains ferronickel.Wherein, the consumption of cross linked polyacrylate ion exchange resin powder is by the cubage of carboxyl in the dry weight resin, and the consumption of PAA-FeC13 is with the cubage of Fe, PAA-NiCl
2Consumption with the cubage of Ni.
(5) get p-methyl benzene sulfonic chloride, PAA-NiCl
2, PAA-FeCl
3And PAA (Na) powder, pressed the mole proportioning 1: 1: 30: 300 mix, to system implementation vacuum outgas-inflated with nitrogen, circulate after 5 times, add 200 parts of methyl methacrylates (with respect to p-methyl benzene sulfonic chloride) of drying, deoxidation and 4 times again to the toluene of monomer volume, stir after 1 hour, 90 ℃ of reactions after 15 hours, cooling also adds the dilution with toluene of 3 times of volumes, can remove catalyzer with reaction solution is centrifugal.The molecular weight M of the polymkeric substance that obtains after solvent steamed
n=17300, theoretical molecular M
Th=15000, molecular weight distributing index PDI=1.46.
Embodiment 2
(1) the complexing load carriers of preparation catalyzer.Utilize the load carriers of cross linked polyacrylate ion exchange resin as the catalyzer iron halide, through 3% alkali liquid washing, change ion exchange resin into the sodium type from Hydrogen, be washed till pH=9 with deionized water again, after 80 ℃ of vacuum-drying, pulverize through ball mill, vacuum-drying gets cross linked polyacrylate ion exchange resin powder PAA (Na) again.
(2) preparation loading type passivator.Get 1 part of ferric bromide FeBr
3After being dissolved in 10 parts of methyl alcohol, add 3 parts of cross linked polyacrylate ion exchange resin powders, in 70 ℃ of stirring and refluxing after 3 hours, deviate from after methyl alcohol and the vacuum-drying PAA-FeBr
3Crude product.This crude product till colourless, makes PAA-FeBr again through methanol-eluted fractions after the vacuum-drying
3
(3) preparation loading type activator.Get 1 part of NiBr
2After placing 10 parts of methyl alcohol, after fully stirring, adds 30 parts of cross linked polyacrylate ion exchange resin powders, in 90 ℃ of stirring and refluxing after 3 hours, deviating from must PAA-NiBr after methyl alcohol and the vacuum-drying
2
(4) supported catalyst of preparation controllable free-radical polymerisation.Get PAA-NiBr
2, PAA-FeBr
3And cross linked polyacrylate ion exchange resin powder, proportioning was mixed in 1: 30: 500 in molar ratio, can form the supported catalyst that contains ferronickel.Wherein, the consumption of cross linked polyacrylate ion exchange resin powder is by the cubage of carboxyl in the dry weight resin, PAA-FeBr
3Consumption with the cubage of Fe, PAA-NiBr
2Consumption with the cubage of Ni.
(5) get p-methyl benzene sulfonic chloride, PAA-NiBr
2, PAA-FeBr
3And PAA (Na) powder, pressed the mole proportioning 1: 1: 30: 500 mix, to system implementation vacuum outgas-inflated with nitrogen, circulate after 5 times, add 200 parts of methyl methacrylates (with respect to p-methyl benzene sulfonic chloride) of drying, deoxidation and 4 times again to the toluene of monomer volume, stir after 1 hour, 90 ℃ of reactions after 13 hours, cooling also adds the dilution with toluene of 3 times of volumes, can remove catalyzer with reaction solution is centrifugal.The molecular weight M of the polymkeric substance that obtains after solvent steamed
n=15300, theoretical molecular M
Th=12300, molecular weight distributing index PDI=1.53.
Embodiment 3
(1) the complexing load carriers of preparation catalyzer.Utilize the load carriers of cross linked polyacrylate ion exchange resin as the catalyzer iron halide, through 4% alkali liquid washing, change ion exchange resin into the sodium type from Hydrogen, be washed till pH=9 with deionized water again, after 80 ℃ of vacuum-drying, pulverize through ball mill, vacuum-drying gets cross linked polyacrylate ion exchange resin powder PAA (Na) again.
(2) preparation loading type passivator.Get 1 part of ferric bromide FeBr
3After being dissolved in 10 parts of methyl alcohol, add 3 parts of cross linked polyacrylate ion exchange resin powders, in 70 ℃ of stirring and refluxing after 3 hours, deviate from after methyl alcohol and the vacuum-drying PAA-FeBr
3Crude product.This crude product till colourless, makes PAA-FeBr again through methanol-eluted fractions after the vacuum-drying
3
(3) preparation loading type activator.Get 1 part of NiCl
2After placing 10 parts of methyl alcohol, after fully stirring, adds 30 parts of cross linked polyacrylate ion exchange resin powders, in 90 ℃ of stirring and refluxing after 3 hours, deviating from must PAA-NiCl after methyl alcohol and the vacuum-drying
2
(4) supported catalyst of preparation controllable free-radical polymerisation.Get PAA-NiCl
2, PAA-FeBr
3And cross linked polyacrylate ion exchange resin powder, proportioning was mixed in 1: 30: 500 in molar ratio, can form the supported catalyst that contains ferronickel.Wherein, the consumption of cross linked polyacrylate ion exchange resin powder is by the cubage of carboxyl in the dry weight resin, and the consumption of PAA-FeC13 is with the cubage of Fe, PAA-NiCl
2Consumption with the cubage of Ni.
(5) get p-methyl benzene sulfonic chloride, PAA-NiCl
2, PAA-FeBr
3And PAA (Na) powder, pressed the mole proportioning 1: 1: 30: 500 mix, to system implementation vacuum outgas-inflated with nitrogen, circulate after 5 times, add 200 parts of methyl methacrylates (with respect to p-methyl benzene sulfonic chloride) of drying, deoxidation and 4 times again to the toluene of monomer volume, stir after 1 hour, 90 ℃ the reaction 13 hours after, add 200 parts of butyl acrylates (with respect to the a-ethyl bromide) again and continue reaction 15 hours, cooling also adds the dilution with toluene of 6 times of volumes, can remove catalyzer with reaction solution is centrifugal.The molecular weight M of the polymkeric substance that obtains after solvent steamed
n=25600, theoretical molecular M
Th=23000, molecular weight distributing index PDI=1.62.
Embodiment 4
(1) regeneration of catalyzer
After the toluene wash with the supported catalyst drying deoxidation of embodiment 1, promptly can be recycled.
(2) get above-mentioned regeneration supported catalyst, vacuum outgas-inflated with nitrogen, circulate after 5 times, add a initiator by the proportioning among the embodiment 1, the methyl methacrylate (with respect to the a-ethyl bromide) of 200 parts of dryings, deoxidation and 4 times are to the toluene of monomer volume, stir after 1 hour, reacted 10 hours down at 90 ℃.Cooling also adds the dilution with toluene of 3 times of volumes, can remove catalyzer with reaction solution is centrifugal.The molecular weight M of the polymkeric substance that obtains after solvent steamed
n=18000, theoretical molecular M
Th=15500, molecular weight distributing index PDI=1.50.
Embodiment 6
(1) the complexing load carriers of preparation catalyzer.After the cleaning of high-ratio surface crosslinked polypropylene acid resin water, through excessive 2%KOH solution, change ion exchange resin into the potassium type from Hydrogen again, when being washed till pH=9 with deionized water, after 80 ℃ of vacuum-drying, pulverize through ball mill, vacuum-drying gets PAA (K) powder again.
(2) preparation loading type passivator.With 1 part of iron trichloride FeCl
3After being dissolved in 10 parts of methyl alcohol, add 3 parts of cross-linked acrylic acid ion exchange resin powders, in 70 ℃ of stirring and refluxing after 3 hours, deviate from after methyl alcohol and the vacuum-drying PAA-FeCl
3Crude product.This crude product till colourless, makes PAA-FeCl again through methanol-eluted fractions after the vacuum-drying
3
(3) preparation loading type activator.Get 1 part of NiCl
2After placing 10 parts of methyl alcohol, after fully stirring, adds 30 parts of cross linked polyacrylate ion exchange resin powders, in 90 ℃ of stirring and refluxing after 3 hours, deviating from must PAA-NiCl after methyl alcohol and the vacuum-drying
2
(4) supported catalyst of preparation controllable free-radical polymerisation.Get PAA-NiCl
2, PAA-FeCl
3And cross linked polyacrylate ion exchange resin powder, proportioning was mixed in 1: 30: 500 in molar ratio, can form the supported catalyst that contains ferronickel.Wherein, the consumption of cross linked polyacrylate ion exchange resin powder is by the cubage of carboxyl in the dry weight resin, PAA-FeCl
3Consumption with the cubage of Fe, PAA-NiCl
2Consumption with the cubage of Ni.
(5) get a-bromine ethylbenzene, PAA-NiCl
2, PAA-FeCl
3PAA (K), pressed the mole proportioning 1: 1: 30: 500 mix, to system implementation liquid nitrogen freezing-vacuum outgas-inflated with nitrogen, circulate after 5 times, add 200 parts of vinylbenzene (with respect to the a-ethyl bromide) of drying, deoxidation and 4 times again to the toluene of monomer volume, stir after 1 hour, 110 ℃ of reactions 15 hours down.Cooling also adds the dilution with toluene of 3 times of volumes, can remove catalyzer with reaction solution is centrifugal.The molecular weight M of the polymkeric substance that obtains after solvent steamed
n=12100, theoretical molecular M
Th=10300, molecular weight distributing index PDI=1.62.
Claims (6)
1, a kind of preparation method who contains the supported catalyst of ferronickel is characterized in that comprising:
(1) the complexing load carriers of preparation catalyzer: utilize the load carriers of cross linked polyacrylate ion exchange resin as the catalyzer iron halide, through the 1-5% alkali liquid washing, change ion exchange resin into sodium type or potassium type from Hydrogen, be washed till pH=9 with deionized water again, after 80 ℃ of vacuum-drying, pulverize through ball mill, vacuum-drying gets cross linked polyacrylate ion exchange resin powder PAA again;
(2) preparation loading type passivator: get after 1 part of three iron halide be dissolved in 10 parts of methyl alcohol, adds 3 parts of cross linked polyacrylate ion exchange resin powders, in 70 ℃ of stirring and refluxing after 3 hours, deviating from must PAA-FeX after methyl alcohol and the vacuum-drying
3Crude product, this crude product again through methanol-eluted fractions until colourless, make PAA-FeX after the vacuum-drying
3, FeX wherein
3Be three iron halide, be selected from iron trichloride FeCl
3, ferric bromide FeBr
3
(3) preparation loading type activator: after getting 1 part of dihalide nickel and placing 10 parts of methyl alcohol, after fully stirring, adds 30 parts of cross linked polyacrylate ion exchange resin powders, in 90 ℃ of stirring and refluxing after 3 hours, deviating from must PAA-NiX after methyl alcohol and the vacuum-drying
2, NiX wherein
2Be dihalide nickel, be selected from Nickel Chloride NiCl
2, Nickel Bromide NiBr
2
(4) supported catalyst of preparation controllable free-radical polymerisation: get PAA-NiX
2, PAA-FeX
3And cross linked polyacrylate ion exchange resin powder, 1: 20 in molar ratio～40: 300～4000 proportionings are mixed, and can form the supported catalyst that contains ferronickel, wherein, the consumption of cross linked polyacrylate ion exchange resin powder is by the cubage of carboxyl in the dry weight resin, PAA-FeX
3Consumption with the cubage of Fe, PAA-NiX
2Consumption with the cubage of Ni.
2, the supported catalyst preparation method who contains ferronickel as claimed in claim 1, it is characterized in that described crosslinked polypropylene acid resin with the cross-linked poly-methyl methacrylate resin and comprise the polyacrylic acid unit, the polymethyl acid unit replaces at interior various copolymer resins.
3, a kind of supported catalyst that contains ferronickel that utilizes claim 1 prepares the method for polymkeric substance, it is characterized in that: get initiator and by PAA-NiX
2, PAA-FeX
3The supported catalyst that cross linked polyacrylate ion exchange resin powder constitutes, mix by mole proportioning 1: 1: 20～40: 300～4000, freezing and to system implementation vacuum outgas-inflated with nitrogen, circulate after 5 times, add drying again, 200 parts of methyl acrylic ester monomers of deoxidation and 2～4 times are to the solvent of monomer volume, stir and 70-110 ℃ of reaction, or after first kind of monomer transforms substantially, add 200 parts of another kind of monomers again and continue reaction, reaction is cooled off with solvent cut and with reaction solution after finishing, reaction solution is centrifugal, separate clear liquid, can remove catalyzer, can obtain polymkeric substance after solvent is steamed.
4, the method for preparing polymkeric substance as claimed in claim 3 is characterized in that: in the prescription of supported catalyst, the consumption of cross linked polyacrylate ion exchange resin powder is relevant with used solvent, to weak polar solvent, consumption is 300-500 part, and to intensive polar solvent, consumption is 2000-4000 part.
5, the method for preparing polymkeric substance as claimed in claim 3 is characterized in that used initiator is p-methyl benzene sulfonic chloride, a-chloropropionate, a-ethyl bromide or a-bromine ethylbenzene.
6, the method for preparing polymkeric substance as claimed in claim 3, used methyl acrylic ester monomer esters of acrylic acid when it is characterized in that being used to prepare homopolymer and multipolymer, styrenic, the alkyl vinyl ethers replaces.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CNB031506232A CN1224633C (en) | 2003-08-28 | 2003-08-28 | Load catalyst containing nickel and iron and its application |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CNB031506232A CN1224633C (en) | 2003-08-28 | 2003-08-28 | Load catalyst containing nickel and iron and its application |
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|---|---|
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| CN1224633C true CN1224633C (en) | 2005-10-26 |
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| CN1300181C (en) * | 2004-12-29 | 2007-02-14 | 上海交通大学 | Process for preparing composite catalyst containing nickel chloride |
| CN1300182C (en) * | 2004-12-29 | 2007-02-14 | 上海交通大学 | Process for preparing composite catalyst containing nickel bromide |
| CN1296394C (en) * | 2004-12-29 | 2007-01-24 | 上海交通大学 | Process for preparing composite catalyst containing ferrous bromide |
| CN1314713C (en) * | 2004-12-29 | 2007-05-09 | 上海交通大学 | Process for preparing composite catalyst containing ferrous chloride |
| CN102335628B (en) * | 2011-07-21 | 2013-04-10 | 南京大学 | Load-type nanometer duplex metal composite catalyst and preparation method thereof |
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