CN1670042A - Process for preparing composite catalyst containing nickel bromide - Google Patents
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- CN1670042A CN1670042A CNA2004100991903A CN200410099190A CN1670042A CN 1670042 A CN1670042 A CN 1670042A CN A2004100991903 A CNA2004100991903 A CN A2004100991903A CN 200410099190 A CN200410099190 A CN 200410099190A CN 1670042 A CN1670042 A CN 1670042A
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Abstract
The invention relates to a process for preparing nickel bromide composite catalyst, wherein the nickel bromide-containing composite catalyst comprises nickel bromide supported catalyst and micromolecular deactivator, which is prepared by using high specific surface ion exchange resin powder as the loading carrier of the catalyst, forming nickel bromide supported catalyst through coordination complexing with waterless nickel bromide, and appending a small amount of micromolecular deactivator simultaneously. The composite catalyst can form solid-liquid reaction system along with initiating agent, monomer and dissolvent, and carry out controlled atom shift free radical aggregation. After the reaction finishes, the outcome yields can be separated in a simple manner, and the catalyst can be circulated for later use after being activated. The nickel bromide-containing composite catalyst can be employed for preparing designated molecular weight, designated chain structure, narrowly distributed homopolymer and copolymer, and has the advantages of easy isolation of supported catalyst after reaction and low residual.
Description
Technical field:
The present invention relates to a kind of Preparation of catalysts method, the preparation method and the application aspect controlled atom transfer radical polymerization thereof of the composite catalyst that particularly a kind of nickelous bromide supported catalyst and small molecules passivator are formed.
Background technology:
Controllable 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 in the controllable polymerization, the monomer of atom transfer radical polymerization newly developed (ATRP) need not harsh pre-treatment, easy to operate easily.U.S. Pat 5763548 has adopted cuprous halide/bipyridine to make catalyzer in atom transfer radical polymerization, 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.Hong SC, Matyjaszewski K Macromolecules 35 (20): 7592-7605 Sep 24 2002, the silica gel load cuprous bromide of employing functionalization; The crosslinked polystyrene particle load cuprous bromide of functionalization etc.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 at existing ATRP catalyzer the problem of separation difficulty, propose the composite catalyst that a kind of nickelous bromide supported catalyst and small molecules passivator are formed, its specific surface area is greater than 1000m
2/ g, use this catalyzer energy controlled polymerization, the homopolymer and the multipolymer of molecular weight, narrow distribution specified in preparation, molecular weight distribution (PDI) is 1.2～1.3, the maximum characteristics of this catalyzer are after its catalytic polymerization finishes, can be with its whole separation by simple filtering, and the catalyst residue amount is low, below 40ppm, residual small molecules passivator is very little to the influence of product.
For realizing such purpose, the present invention forms the nickelous bromide supported catalyst with the load carriers of high-ratio surface ion exchange resin powder as catalyzer with the nickelous bromide ligand complex, adds a small amount of small molecules passivator simultaneously and forms the nickelous bromide composite catalyst.Nickelous bromide composite 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 transition metal residual volume in the product is low; Can recycle after supported catalyst is activated, avoided the catalyst separating difficulty, can't reclaim and environment caused shortcomings such as serious harm; Use a small amount of anhydrous CuBr
2Perhaps anhydrous FeBr
3And part three-(N, N-dimethyl aminoethyl) amine (Me
6TREN) title complex of Xing Chenging plays the effect of bridge as small molecules passivator in reaction process, and the molecular weight of product is more controlled.
The concrete preparation method of nickelous bromide composite catalyst of the present invention is as follows:
(1) pre-treatment of carrier: make the carrier of spent ion exchange resin as catalyzer, with 1-5wt% sodium hydroxide or potassium hydroxide aqueous solution washing, change ion exchange resin into sodium or potassium type from Hydrogen, be washed till pH=9 with deionized water again, obtain the pre-treatment carrier in 80 ℃ of vacuum-dryings;
(2) preparation nickelous bromide supported catalyst: anhydrous Nickel Bromide and pre-treatment carrier 1: 50 in molar ratio～150 are mixed, the mole number of carrier is according to the cubage of the COO group that it comprised, be dissolved in the methyl alcohol of the deoxygenation that is five times in the pre-treatment carrier bulk, then to system implementation liquid nitrogen freezing-vacuum outgas-inflated with nitrogen-thaw-liquid nitrogen freezing, circulate after 5 times, in 70 ℃ of stirring and refluxing 1 hour, the nitrogen protection decompression steamed methyl alcohol and obtains the nickelous bromide supported catalyst;
(3) preparation small molecules passivator: get anhydrous iron bromide or anhydrous cupric bromide, three-(N, the N-dimethyl aminoethyl) amine 1: 0.9 in molar ratio～1.1 is dissolved in the dimethyl formamide of 500～1000 times of moles, mixes, and obtains small molecules passivator;
(4) preparation nickelous bromide composite catalyst: get nickelous bromide supported catalyst and small molecules passivator and mix at 1～3: 0.01～0.08 in molar ratio, form the nickelous bromide composite catalyst.
Wherein ion exchange resin has polyacrylic resin, the multipolymer of polymethacrylate resin or vinylformic acid and methacrylic acid, and its resin particle degree is 40～60 orders, contained COO group is 0.008～0.012molCOO
-/ g resin, specific surface area should be greater than 1000m
2/ g.
The regeneration of nickelous bromide supported catalyst: the toluene wash of used nickelous bromide composite catalyst drying deoxidation is removed polymkeric substance, dry back adds anhydrous methanol, handled in 3～5 hours through methanol eddy in 60 ℃, can use as the nickelous bromide supported catalyst once more after the drying again.
The concrete grammar that nickelous bromide composite catalyst of the present invention is applied to controllable polymerization is as follows:
Get initiator, nickelous bromide composite catalyst and monomer and mix and add 2～4 times of solvents to the monomer volume by 1: 1～3: 200 moles of proportionings, to system implementation liquid nitrogen freezing-vacuum outgas-inflated with nitrogen-thaw-liquid nitrogen freezing, circulate after 5 times, stir and 70-110 ℃ of reaction.When desire prepares multipolymer, can after transform substantially, first kind of monomer add 200 times of monomers of mol ratio again and continue reaction to the another kind of deoxygenation of initiator.After reaction finishes, with solvent cut and with the reaction solution cooling that reaction solution is centrifugal, separate clear liquid, can remove the nickelous bromide supported catalyst.Obtain polymkeric substance after solvent steamed.
Used methyl acrylic ester monomer can also be an esters of acrylic acid when nickelous bromide composite catalyst of the present invention's preparation was applied to prepare homopolymer and multipolymer, styrenic.
The nickelous bromide composite catalyst of the present invention preparation can catalyzed polymerization, makes predetermined chain end, the polymkeric substance that predetermined molecular weight and molecular weight distribution are narrower.The nickelous bromide composite catalyst that utilizes the present invention to prepare can be easy to prepare the clear and definite AB type of multiple structure or ABA type or the more complicated segmented copolymer of structure, and these polymkeric substance are widely used in polymer blending, modification and coatings industry; After polymerization finishes, can remove the nickelous bromide supported catalyst by centrifugal or filtration at an easy rate, the small molecules passivator residual volume in the polymkeric substance satisfies the requirement to foreign matter content in the polymkeric substance fully less than 10ppm; Nickelous bromide composite catalyst load carriers of the present invention---poly-(methyl) 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 nickelous bromide composite 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 nickelous bromide composite catalyst of the present invention preparation is through simple solvent wash, and drying can obtain the nickelous bromide supported catalyst after the deoxidation again, has avoided the catalyst separating difficulty, and power consumption is big, and catalyzer can't reclaim and environment caused shortcoming such as serious harm.
Embodiment:
Below in conjunction with specific embodiment technical scheme of the present invention is further described.
Embodiment 1
(1) pre-treatment of carrier: with high-ratio surface polyacrylic acid ion exchange resin (specific surface area＞=1000m
2/ g) through the sodium hydroxide solution washing of 1-5wt%, be washed till pH=9 with deionized water again, after 80 ℃ of vacuum-drying, obtain pretreated polyacrylic acid ion exchange resin carrier (PAA);
(2) preparation nickelous bromide supported catalyst: get 20 milligrams of anhydrous nickelous bromide (NiBr
2) be dissolved in the methyl alcohol of 4 milliliters of deoxygenations after; add 0.45 gram pre-treatment resin carrier according to 1: 50 mol ratio; to system implementation liquid nitrogen freezing-vacuum outgas-inflated with nitrogen-thaw-liquid nitrogen freezing; circulate after 5 times; after 1 hour, the nitrogen protection decompression gets nickelous bromide supported catalyst (PAA/NiBr after steaming methyl alcohol in 70 ℃ of stirring and refluxing
2);
(3) preparation small molecules passivator CuBr
2/ Me
6TREN: get the anhydrous cupric bromide (CuBr of 0.54mg at 1: 1 according to mol ratio
2), 1mg three-(N, N-dimethyl aminoethyl) amine (Me
6TREN) be dissolved in the dimethyl formamide of 0.5ml, mix, obtain small molecules passivator;
(4) preparation nickelous bromide composite catalyst: get above-mentioned nickelous bromide supported catalyst PAA/NiBr
2And small molecules passivator CuBr
2/ Me
6The TREN uniform mixing obtains the nickelous bromide composite catalyst;
Get initiator a-ethyl bromide, nickelous bromide composite catalyst and monomer methyl acrylate by initiator: NiBr
2: CuBr
2: monomer=0.8: 1: 0.04: 4 times of toluene solvants to the monomer volume are mixed and added to 90 quality proportionings, to system implementation liquid nitrogen freezing-vacuum outgas-inflated with nitrogen-thaw-liquid nitrogen freezing, circulate after 5 times, stir and 90 ℃ of reactions after 15 hours, add 200 times of butyl acrylate 260mg again and continue reaction 15 hours to initiator, 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=25600, theoretical molecular M
Th=23100, molecular weight distributing index PDI=1.25.
Embodiment 2
(1) pre-treatment of carrier: with high-ratio surface polyacrylic acid ion exchange resin (specific surface area＞=1000m
2/ g) through the sodium hydroxide solution washing of 1-5wt%, be washed till pH=9 with deionized water again, after 80 ℃ of vacuum-drying, obtain pretreated polyacrylic acid ion exchange resin carrier (PAA);
(2) preparation nickelous bromide supported catalyst: get 20 milligrams of anhydrous nickelous bromide (NiBr
2) be dissolved in the methyl alcohol of 4 milliliters of deoxygenations after; add 0.45 gram pre-treatment resin carrier according to 1: 50 mol ratio; to system implementation liquid nitrogen freezing-vacuum outgas-inflated with nitrogen-thaw-liquid nitrogen freezing; circulate after 5 times; after 1 hour, the nitrogen protection decompression gets nickelous bromide supported catalyst (PAA/NiBr after steaming methyl alcohol in 70 ℃ of stirring and refluxing
2);
(3) preparation small molecules passivator CuBr
2/ Me
6TREN: get the anhydrous cupric bromide (CuBr of 0.2mg at 1: 0.9 according to mol ratio
2), 0.21mg three-(N, N-dimethyl aminoethyl) amine (Me
6TREN) be dissolved in the dimethyl formamide of 0.5ml, mix, obtain small molecules passivator;
(4) preparation nickelous bromide composite catalyst: get above-mentioned nickelous bromide supported catalyst PAA/NiBr
2And small molecules passivator CuBr
2/ Me
6The TREN uniform mixing obtains the nickelous bromide composite catalyst;
Get initiator a-ethyl bromide, composite catalyst and monomer methyl acrylate by initiator: NiBr
2: CuBr
2: monomer=0.8: 3: 0.03: 4 times of m-xylene solvents to the monomer volume are mixed and added to 90 quality proportionings, to system implementation liquid nitrogen freezing-vacuum outgas-inflated with nitrogen-thaw-liquid nitrogen freezing, circulate after 5 times, stir and 120 ℃ of reactions after 25 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=16300, theoretical molecular M
Th=14100, molecular weight distributing index PDI=1.29.
Embodiment 3
(1) pre-treatment of carrier: with high-ratio surface polyacrylic acid ion exchange resin (specific surface area＞=1000m
2/ g) through the sodium hydroxide solution washing of 1-5wt%, be washed till pH=9 with deionized water again, after 80 ℃ of vacuum-drying, obtain pretreated polyacrylic acid ion exchange resin carrier (PAA);
(2) preparation nickelous bromide supported catalyst: get 20 milligrams of anhydrous nickelous bromide (NiBr
2) be dissolved in the methyl alcohol of 4 milliliters of deoxygenations after; add 1.5 gram pre-treatment resin carriers according to 1: 150 mol ratio; to system implementation liquid nitrogen freezing-vacuum outgas-inflated with nitrogen-thaw-liquid nitrogen freezing; circulate after 5 times; after 1 hour, the nitrogen protection decompression gets nickelous bromide supported catalyst (PAA/NiBr after steaming methyl alcohol in 70 ℃ of stirring and refluxing
2);
(3) preparation small molecules passivator CuBr
2/ Me
6TREN: get the anhydrous cupric bromide (CuBr of 1.34mg at 1: 1 according to mol ratio
2), 1.4mg three-(N, N-dimethyl aminoethyl) amine (Me
6TREN) be dissolved in the dimethyl formamide of 0.5ml,, mix, obtain small molecules passivator;
(4) preparation nickelous bromide composite catalyst: get above-mentioned nickelous bromide supported catalyst PAA/NiBr
2And small molecules passivator CuBr
2/ Me
6TREN presses mass ratio NiBr
2/ CuBr
2=1: 0.06 proportioning uniform mixing obtains the nickelous bromide composite catalyst;
Get initiator a-ethyl bromide, composite catalyst and monomer methyl acrylate by initiator: NiBr
2: CuBr
2: monomer=1.5: 1: 0.06: 4 times of m-xylene solvents to the monomer volume are mixed and added to 134 quality proportionings, to system implementation liquid nitrogen freezing-vacuum outgas-inflated with nitrogen-thaw-liquid nitrogen freezing, circulate after 5 times, stir and 80 ℃ of reactions after 20 hours, add 200 times of butyl acrylates again and continue reaction 20 hours to initiator, 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=23900, theoretical molecular M
Th=20600, molecular weight distributing index PDI=1.25.
Embodiment 4
(1) regeneration of nickelous bromide supported catalyst: after the toluene wash of above-mentioned supported catalyst drying deoxidation, add anhydrous methanol after drying, and handled in 3～5 hours through methanol eddy in 60 ℃, drying is promptly renewable again;
(2) preparation small molecules passivator FeBr
3/ Me
6TREN: get the anhydrous iron bromide (FeBr of 1.2mg at 1: 1 according to mol ratio
3), 0.92mg three-(N, N-dimethyl aminoethyl) amine (Me
6TREN) be dissolved in the dimethyl formamide of 0.5ml, mix, obtain small molecules passivator;
(3) preparation nickelous bromide composite catalyst: get above-mentioned nickelous bromide supported catalyst PAA/NiBr
2And small molecules passivator FeBr
3/ Me
6TREN presses mass ratio NiBr
2/ FeBr
3=1: 0.06 proportioning uniform mixing obtains the nickelous bromide composite catalyst;
Get initiator a-ethyl bromide, composite catalyst and monomer methyl acrylate by initiator: NiBr
2: FeBr
3: monomer=1.5: 1: 0.06: 4 times of m-xylene solvents to the monomer volume are mixed and added to 134 quality proportionings, to system implementation liquid nitrogen freezing-vacuum outgas-inflated with nitrogen-thaw-liquid nitrogen freezing, circulate after 5 times, stir and 80 ℃ of reactions after 20 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=15500, theoretical molecular M
Th=11600, molecular weight distributing index PDI=1.26.
Embodiment 5
(1) pre-treatment of carrier: with high-ratio surface polyacrylic acid ion exchange resin (specific surface area＞=1000m
2/ g) through the potassium hydroxide solution washing of 2wt%, be washed till pH=9 with deionized water again, after 80 ℃ of vacuum-drying, obtain pretreated polyacrylic acid ion exchange resin carrier (PAA);
(2) preparation nickelous bromide supported catalyst: get 20 milligrams of anhydrous nickelous bromide (NiBr
2) be dissolved in the methyl alcohol of 10 milliliters of deoxygenations after; add 0.45 gram pre-treatment resin carrier according to 1: 50 mol ratio; to system implementation liquid nitrogen freezing-vacuum outgas-inflated with nitrogen-thaw-liquid nitrogen freezing; circulate after 5 times; after 1 hour, the nitrogen protection decompression gets nickelous bromide supported catalyst (PAA/NiBr after steaming methyl alcohol in 70 ℃ of stirring and refluxing
2);
(3) preparation small molecules passivator CuBr
2/ Me
6TREN: get the anhydrous cupric bromide (CuBr of 1.8mg at 1: 1 according to mol ratio
2), 1.8mg three-(N, N-dimethyl aminoethyl) amine (Me
6TREN) be dissolved in the dimethyl formamide of 0.5ml, mix, obtain small molecules passivator;
(4) preparation nickelous bromide composite catalyst: get above-mentioned nickelous bromide supported catalyst PAA/NiBr
2And small molecules passivator CuBr
2/ Me
6TREN presses mass ratio NiBr
2/ CuBr
2=1: 0.08 proportioning uniform mixing obtains the nickelous bromide composite catalyst;
Get initiator a-ethyl bromide, composite catalyst and monomer methyl acrylate by initiator: NiBr
2: CuBr
2: monomer=1.5: 1: 0.08: 4 times of m-xylene solvents to the monomer volume are mixed and added to 134 quality proportionings, to system implementation liquid nitrogen freezing-vacuum outgas-inflated with nitrogen-thaw-liquid nitrogen freezing, circulate after 5 times, stir and 80 ℃ of reactions after 20 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=16900, theoretical molecular M
Th=13600, molecular weight distributing index PDI=1.21.
Embodiment 6
(1) pre-treatment of carrier: after the cleaning of high-ratio surface polyacrylic acid-styrol copolymer (8: 2) resin water,, when being washed till pH=9, obtain carrier in 80 ℃ of vacuum-dryings with deionized water again through excessive 2wt%NaOH solution;
(2) preparation supported catalyst: get 20 milligrams of anhydrous nickelous bromide (NiBr
2) be dissolved in the methyl alcohol of 4 milliliters of deoxygenations after, add 0.58 gram pre-treatment resin carrier according to 1: 50 mol ratio, to system implementation liquid nitrogen freezing-vacuum outgas-inflated with nitrogen-thaw-liquid nitrogen freezing, circulate after 5 times, after 1 hour, the nitrogen protection decompression gets supported catalyst after steaming methyl alcohol in 70 ℃ of stirring and refluxing;
(3) preparation small molecules passivator FeBr
3/ Me
6TREN: get the anhydrous iron bromide (FeBr of 1.2mg at 1: 1 according to mol ratio
3), 0.9mg three-(N, N-dimethyl aminoethyl) amine (Me
6TREN) be dissolved in the dimethyl formamide of 0.5ml, mix, obtain small molecules passivator;
(4) preparation nickelous bromide composite catalyst: get above-mentioned nickelous bromide supported catalyst PAA/NiBr
2And small molecules passivator FeBr
3/ Me
6TREN presses mass ratio NiBr
2/ FeBr
3=1: 0.06 proportioning uniform mixing obtains the nickelous bromide composite catalyst;
Get initiator a-ethyl bromide, composite catalyst and monomer methyl acrylate by initiator: NiBr
2: FeBr
3: monomer=1.5: 1: 0.06: 4 times of toluene solvants to the monomer volume are mixed and added to 134 quality proportionings, to system implementation liquid nitrogen freezing-vacuum outgas-inflated with nitrogen-thaw-liquid nitrogen freezing, circulate after 5 times, stir and 90 ℃ of reactions after 20 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=18900, theoretical molecular M
Th=16600, molecular weight distributing index PDI=1.27.
| Embodiment | Initiator: composite catalyst: monomer (mass ratio) | Composite catalyst | Theoretical molecular M n | Actual molecular weight M th | Molecular weight distributing index PDI |
| Supported catalyst: passivator (mass ratio) | |||||
| ????1 | ????1.5∶1∶134 | ????1∶0.04 | ????23100 | ????25600 | ?????1.25 |
| ????2 | ????1.5∶3∶134 | ????1∶0.01 | ????14100 | ????16300 | ?????1.29 |
| ????3 | ????1.5∶1∶134 | ????1∶0.06 | ????20600 | ????23900 | ?????1.25 |
| ????4 | ????1.5∶1∶134 | ????1∶0.06 | ????11600 | ????15500 | ?????1.26 |
| ????5 | ????1.5∶1∶134 | ????1∶0.08 | ????13600 | ????16900 | ?????1.21 |
| ????6 | ????1.5∶1∶134 | ????1∶0.06 | ????16600 | ????18900 | ?????1.27 |
Claims (1)
1, a kind of preparation method who contains the composite catalyst of nickelous bromide is characterized in that concrete preparation method is as follows:
(1) pre-treatment of carrier: make the carrier of spent ion exchange resin as catalyzer, with 1-5wt% sodium hydroxide or potassium hydroxide aqueous solution washing, change ion exchange resin into sodium or potassium type from Hydrogen, be washed till pH=9 with deionized water again, obtain the pre-treatment carrier in 80 ℃ of vacuum-dryings;
(2) preparation nickelous bromide supported catalyst: anhydrous Nickel Bromide and pre-treatment carrier 1: 240 in molar ratio～500 are mixed, the mole number of carrier is according to the cubage of the COO group that it comprised, be dissolved in the methyl alcohol of the deoxygenation that is five times in volume, then to system implementation liquid nitrogen freezing-vacuum outgas-inflated with nitrogen-thaw-liquid nitrogen freezing, circulate after 5 times, in 70 ℃ of stirring and refluxing 1 hour, the nitrogen protection decompression steamed methyl alcohol and obtains the nickelous bromide supported catalyst;
(3) preparation small molecules passivator: get anhydrous iron bromide or anhydrous cupric bromide, three-(N, the N-dimethyl aminoethyl) amine 1: 0.9 in molar ratio～1.1 is dissolved in the dimethyl formamide of 500～1000 times of moles, mixes, and obtains small molecules passivator;
(4) preparation composite catalyst containing nickel bromide: get nickelous bromide supported catalyst and small molecules passivator and mix at 1～3: 0.01～0.08 in molar ratio, obtain composite catalyst containing nickel bromide;
Wherein ion exchange resin has polyacrylic resin, the multipolymer of polymethacrylate resin or vinylformic acid and methacrylic acid, and its resin particle degree is 40～60 orders, contained COO group is 0.008～0.012molCOO
-/ g resin, specific surface area should be greater than 1000m
2/ g.
Priority Applications (1)
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|---|---|---|---|
| CNB2004100991903A CN1300182C (en) | 2004-12-29 | 2004-12-29 | Process for preparing composite catalyst containing nickel bromide |
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CNB2004100991903A CN1300182C (en) | 2004-12-29 | 2004-12-29 | Process for preparing composite catalyst containing nickel bromide |
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| Publication Number | Publication Date |
|---|---|
| CN1670042A true CN1670042A (en) | 2005-09-21 |
| CN1300182C CN1300182C (en) | 2007-02-14 |
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ID=35041505
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|---|---|---|---|---|
| CN1209381C (en) * | 2003-08-21 | 2005-07-06 | 上海交通大学 | Load catalyst containing ferric bromide and use thereof |
| CN1224633C (en) * | 2003-08-28 | 2005-10-26 | 上海交通大学 | Load catalyst containing nickel and iron and its application |
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Granted publication date: 20070214 Termination date: 20121229 |