CN1515356A - 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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- CN1515356A CN1515356A CNA031506232A CN03150623A CN1515356A CN 1515356 A CN1515356 A CN 1515356A CN A031506232 A CNA031506232 A CN A031506232A CN 03150623 A CN03150623 A CN 03150623A CN 1515356 A CN1515356 A CN 1515356A
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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
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P20/00—Technologies relating to chemical industry
- Y02P20/50—Improvements relating to the production of bulk chemicals
- Y02P20/52—Improvements relating to the production of bulk chemicals using catalysts, e.g. selective catalysts
Abstract
The present invention relates to a load type catalyst containing nickel and iron and its application. It uses high specific area cross-linked polyacrylic ion-exchange resin powder body as load carrier of catalyst, and makes it and nickel dihalide and iron trihalide undergo the process of coordinative complexation reaction to form the load catalyst. The load catalyst can be mixed with initiator, monomer and solvent according to a certain ratio, and formed into a solid-liquid reaction systm which can be used for catalyzing controllable free radical polymerization. After the reaction is completed, then reaction product and catalyst can be simply separated, and the metal catalyst residue in the product is less, and said catalyst can be recovered and reused.
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 catalyst to make and have the narrow distribution homopolymers and the copolymer 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 regeneration of the present invention is handled simple, can be recycling, avoid environmental pollution.Belong to the polymer synthesis technical field.
Background technology:
Living polymerization is to realize MOLECULE DESIGN, synthesizes to have the important means of ad hoc structure and performance polymer.Because living polymerisation process commonly used, as severe reaction conditions such as anionic polymerisation, cationic polymerization, GTPs, 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.
ATRP (ATRP) is meant as the halide of initator 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 halide 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.
ATRP is because the reaction condition gentleness, and it is extensive to adapt to monomer, can make molecular weight distribution very narrow (disperseing near single), specify the polymer of molecular weight, can prepare the clear and definite block copolymer of structure and receives much attention.Compare with traditional active cloudy (sun) ionic polymerization, the monomer of ATRP must harsh preliminary treatment, easy to operate easily.Typical ATRP adopts cuprous halide/bipyridine to make catalyst usually, its disadvantage is the separation difficulty of reaction afterproduct and catalyst, normally reactant liquor is diluted, by aluminium oxide (alumina) post, make cuprous halide/bipyridine catalyst be adsorbed on it again.This catalyst removal mode treating capacity is little, and power consumption is big, can't realize the industrialization operation.Because the complex compound of cuprous halide and coordination thereof all has bigger toxicity, will cause serious harm to environment, so the ATRP product is to restrict one of its industrialized major obstacle in recent years with separating of catalyst.
For improving separating of catalyst and reactant liquor, people load on the active ingredient of catalyst on the solid phase carrier, carry out the out-phase reaction, and reaction can directly be filtered and solid-phase catalyst can be separated after being finished.External bibliographical information (Hong SC, Matyjaszewski K Macromolecules 35 (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 scale, so cost is higher.
Summary of the invention:
The objective of the invention is to exist the problem of separation difficulty at existing ATRP catalyst, a kind of segregative ferronickel loaded catalyst that contains is proposed, use this catalyst can control polymerization, the polymer of molecular weight, narrow distribution is specified in preparation, the maximum characteristics of this catalyst 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 catalyst with dihalide nickel, three iron halide ligand complexes.Supported catalyst and initator, 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 separation after finishing, and the metallic catalyst residual volume in the product is low; Catalyst is a reusable edible after simple washing, does not have oxysensible shortcoming, has avoided catalyst to reclaim and environment is caused serious harm.
The present invention can carry out as follows:
(1) the complexing load carriers of preparation catalyst.Utilize the load carriers of cross linked polyacrylate ion exchange resin as the catalyst 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 support 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 ferric trichloride FeCl
3, ferric bromide FeBr
3
(3) preparation support 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 homopolymers and copolymer, and concrete method is as follows:
Get initator 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 copolymer, 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 dilution and with the reactant liquor cooling that reactant liquor is centrifugal, separate clear liquid, can remove catalyst.Can obtain polymer after solvent steamed.
The consumption of catalyst 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, the regeneration of this supported catalyst is handled simple, does not have the shortcoming of the lower valency transition metal halide oxidation that micro amount of oxygen in the system will be wherein, 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 copolymers.
Used initator can be p-methyl benzene sulfonic chloride, a-chloropropionate when the supported catalyst of the present invention's preparation was applied to prepare polymer, 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 homopolymers and copolymer, phenylethylene, and the alkyl vinyl ethers is equivalent to be replaced.
The catalyst 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) polymer; The catalyst 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 block copolymer of structure easily, and these polymer are widely used in polyblend, modification and coatings industry; After the catalyst ATRP of the present invention's preparation finishes, catalyst can be at an easy rate by centrifugal or filter with catalyst separation, metallic catalyst residual volume in the polymer satisfies the requirement to impurity content in the polymer 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 ripe industrialization product, and the source is abundant, and is cheap and easy to get, has excellent industrial application foreground.Utilize the approaching monodispersed various copolymers that catalyst 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 catalyst of the present invention's preparation is through simple solvent wash, dry, promptly renewable after the deoxidation, avoided traditional ATRP catalyst separation difficulty, power consumption is big, catalyst can't reclaim and environment is caused shortcomings such as serious harm, is the green product that meets the 21st century environmental protection concept.
The specific 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 catalyst.Utilize the load carriers of cross linked polyacrylate ion exchange resin as the catalyst 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 support type passivator.Get 1 part of ferric 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 support 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-FeCl3 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 catalyst with reactant liquor is centrifugal.The molecular weight M of the polymer 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 catalyst.Utilize the load carriers of cross linked polyacrylate ion exchange resin as the catalyst 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 support 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 support 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 catalyst with reactant liquor is centrifugal.The molecular weight M of the polymer 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 catalyst.Utilize the load carriers of cross linked polyacrylate ion exchange resin as the catalyst 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 support 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 support 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-FeCl3 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 catalyst with reactant liquor is centrifugal.The molecular weight M of the polymer that obtains after solvent steamed
n=25600, theoretical molecular M
Th=23000, molecular weight distributing index PDI=1.62.
Embodiment 4
(1) regeneration of catalyst
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 initator 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 catalyst with reactant liquor is centrifugal.The molecular weight M of the polymer 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 catalyst.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 support type passivator.With 1 part of ferric trichloride FeCl
3After being dissolved in 10 parts of methyl alcohol, add 3 parts of cross-linked acrylic acid ion exchange resin powders, in the 70C 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 support 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 frozen-vacuum outgas-inflated with nitrogen, circulate after 5 times, add 200 parts of styrene (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 catalyst with reactant liquor is centrifugal.The molecular weight M of the polymer 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 catalyst: utilize the load carriers of cross linked polyacrylate ion exchange resin as the catalyst 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 support 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, get the PAA-FeX3 crude product after deviating from methyl alcohol and vacuum drying, this crude product again through methanol-eluted fractions until colourless, make PAA-FeX3 after the vacuum drying, wherein FeX3 is three iron halide, comprises ferric trichloride FeCl
3, ferric bromide FeBr
3
(3) preparation support 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, 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.
2, the supported catalyst preparation method who contains ferronickel as claimed in claim 1 is characterized in that described crosslinked polypropylene acid resin can and comprise the polyacrylic acid unit with the cross-linked poly-methyl methacrylate resin, 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 polymer, it is characterized in that: get initator 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 one 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 dilution and with reactant liquor after finishing, reactant liquor is centrifugal, separate clear liquid, can remove catalyst, can obtain polymer after solvent is steamed.
4, the method for preparing polymer 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 polymer as claimed in claim 3 is characterized in that used initator can be p-methyl benzene sulfonic chloride, a-chloropropionate, a-ethyl bromide or a-bromine ethylbenzene.
6, the method for preparing polymer as claimed in claim 3, methyl acrylic ester monomer used when it is characterized in that being used to prepare homopolymers and copolymer can also be used esters of acrylic acid, phenylethylene, the alkyl vinyl ethers replaces.
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| 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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| 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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| CN1224633C CN1224633C (en) | 2005-10-26 |
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|---|---|---|---|
| CNB031506232A Expired - Fee Related CN1224633C (en) | 2003-08-28 | 2003-08-28 | Load catalyst containing nickel and iron and its application |
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Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1296394C (en) * | 2004-12-29 | 2007-01-24 | 上海交通大学 | Process for preparing composite catalyst containing ferrous bromide |
| CN1300182C (en) * | 2004-12-29 | 2007-02-14 | 上海交通大学 | Process for preparing composite catalyst containing nickel bromide |
| CN1300181C (en) * | 2004-12-29 | 2007-02-14 | 上海交通大学 | Process for preparing composite catalyst containing nickel chloride |
| CN1314713C (en) * | 2004-12-29 | 2007-05-09 | 上海交通大学 | Process for preparing composite catalyst containing ferrous chloride |
| WO2013010357A1 (en) * | 2011-07-21 | 2013-01-24 | 南京大学 | Supported nanoscale bimetallic composite catalyst and preparation method thereof |
-
2003
- 2003-08-28 CN CNB031506232A patent/CN1224633C/en not_active Expired - Fee Related
Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1296394C (en) * | 2004-12-29 | 2007-01-24 | 上海交通大学 | Process for preparing composite catalyst containing ferrous bromide |
| CN1300182C (en) * | 2004-12-29 | 2007-02-14 | 上海交通大学 | Process for preparing composite catalyst containing nickel bromide |
| CN1300181C (en) * | 2004-12-29 | 2007-02-14 | 上海交通大学 | Process for preparing composite catalyst containing nickel chloride |
| CN1314713C (en) * | 2004-12-29 | 2007-05-09 | 上海交通大学 | Process for preparing composite catalyst containing ferrous chloride |
| WO2013010357A1 (en) * | 2011-07-21 | 2013-01-24 | 南京大学 | Supported nanoscale bimetallic composite catalyst and preparation method thereof |
| US9259724B2 (en) | 2011-07-21 | 2016-02-16 | Nanjing University | Supported bimetallic nanocomposite catalyst and the preparation method thereof |
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| Publication number | Publication date |
|---|---|
| CN1224633C (en) | 2005-10-26 |
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