CN1765507A - Cyanide complex catalyst and its preparation method - Google Patents
Cyanide complex catalyst and its preparation method Download PDFInfo
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Abstract
The invention discloses a bimetallic cyanide complex catalyst and it's preparing method. The invention adds the compound ligands with special functional group as aziridine compound, alkanolamine compound, hydantoin compound, melamine compound, oxosilane or titanic acid ester coupling agent into traditional bimetallic cyanide complex compound which contains micro-molecule ligand and functional polymer ligand. Wherein, the compound containing special functional groups is in the 5-65% weight proportion of catalyst. Compared to common cyanide complex compound, said inventive catalyst has higher activity, short induction period, easy filtration, drying and milling in the preparing process. And the polyether polyatomic alcohol prepared by said catalyst has lower degree of unsaturation, which can apply the soft foam production.
Description
Technical field
The present invention relates to open loop of epoxy compound catalyst for polymerization and preparation method thereof.
Background technology
The bimetal complex precipitation of normally a kind of cyanogen root of bimetallic cyanide complex catalyst (hereinafter to be referred as dmc catalyst) coordination.The cyanide complex precipitation that bimetallic cyanide complex commonly used has zinc hexacyanocobaltate, the sour zinc of six cyanogen iron (divalent or 3 valencys), four cyanogen nickel acid zinc, six cyanogen iridium acid zinc and zinc to be replaced by iron, cobalt, nickel etc.Activity was very low when this simple DMC complex compound was used as catalyst, the dmc catalyst of when adding organic ligand, preparing, and catalytic activity increases substantially.Its preparation technology adds organic ligand to carry out complex reaction in the suspension of newly-generated bimetallic cyanide complex, disperse repeatedly, filter with organic ligand or its aqueous solution again, with final filtration cakes torrefaction, pulverize, sieve the solid catalyst powder.
After the dmc catalyst integral skeleton structure was determined, the organic ligand type influenced the catalyst combination property.After glycol dimethyl ether, tert-butyl alcohol complex catalyst suitability for industrialized production, both at home and abroad other organic ligand catalyst researches are not stopped always, use the tert-butyl alcohol among the Patent data WO00/68295 and contain the acrylate group macromolecular compound and make the part synthetic catalyst; Disclose tert-butyl alcohol coordination among the CN1383919, contained phosphorus compound, α, beta-unsaturated carboxylic acid ester, cyclodextrin, glycosides, tricaproin and glycidol ether catalyst; CN1273591 has prepared hydroxyalkyl uncle butyl ether compounds complex catalyst; WO01/83107A2 discloses all kinds ethoxy alkyl ether complex catalyst; US6358877 discloses the dimethyl sulfoxide (DMSO) complex catalyst; The tert-butyl alcohol and polyacrylic compounds synthetic catalyst have been used among the CN1360608; CN14886788 discloses the compound complex catalyst of two alcohol-aziridine cpds; CN1233529 discloses ethylene glycol diethyl ether-tert-butyl alcohol complex catalyst.CN14886788 discloses two alcohol-aziridine cpd complex catalyst, has improved tert-butyl alcohol complex catalyst performance.At present, still need to study and adopt suitable ligand, synthesize the better dmc catalyst of performance, to satisfy the demand in market.
Summary of the invention
The technical problem to be solved in the present invention provides a kind of novel cyanide complex catalyst.
Another technical problem that the present invention will solve provides a kind of method for preparing this catalyst.
Catalyst of the present invention is to introduce the compound ligand that aziridines compound, alkanolamine compounds, hydantoin-based compound, isocyanuric acid ester type compound, siloxanes and titanate coupling agent etc. contain specific functional groups in the dmc catalyst that contains little molecule organic ligand, functional polymer's ligand, and the compound mass fraction in catalyst that wherein contains specific functional groups is 5%～65%.Catalyst preparation process and serviceability are greatly improved.
Cyanide complex catalyst provided by the invention, general formula is as follows:
M
1 a[M
2(CN)
b]
c·xM
3(A)
d·yQ·zT·jB·hH
2O
Wherein: M
1Be metal cation, be generally Zn
2+, Mn
2+, Ni
2+, Fe
2+, Co
2+, Sr
2+, Cu
2+In one or more;
M
2Be Co
3+, Fe
3+, Ni
2+Or Cr
3+
M
3Be M
1, M
2In one or more, preferred Zn
2+Or Mn
2+
A is F
-, Cl
-, Br
-, I
-, PW
12O
40 3-, SO
4 2-, sulfonate radical or carboxylate radical;
A, b, c and d satisfy the chemical valence balance of system; X, y, z, j and h are generally the numerical value between 0～10;
Q is little molecule organic ligand, is molecular weight less than 200 alcohol, ether, aldehyde, ketone, ester, acid amides or sulfide, and the most frequently used is the tert-butyl alcohol;
T is a functional compound, is to contain the specific functional groups molecular weight less than 500 compound, following several classes commonly used: aziridines compound, alkanolamine compounds, hydantoin-based compound, isocyanuric acid ester type compound, silane or titanate coupling agent;
B is the functional polymer, be molecular weight greater than 500 the polymer that contains oxygen, nitrogen, phosphorus or sulphur, being generally (1) main chain is the carbochain macromolecule polyalcohol, for example polyacrylamide, polyacrylic acid, polyacrylonitrile, polyvinyl alcohol, poly-Ethylenimine, PVP or poly-hydroxy acrylate etc.; (2) heterochain macromolecule polyalcohol is as polyethers, polyester, Merlon or polyamide etc.; (3) siliceous, P elements polymer is as polyphosphazene, polysiloxane compound etc.
Aziridines compound comprises in the catalyst of the present invention: aziridine polyvalent carboxylic acid condensate thing, aziridine polyisocyanic acid ester condensates, three-(2-methylaziridine base phosphine oxide) are with condensation product of carboxylic acid etc.
The alkanolamine compounds mainly contains in the catalyst of the present invention: aniline epoxides condensation product, diethanol amine or triethanolamine are with aliphatic acid or lewis acid condensation product, diethanol amine and hard ester acid reaction with same mole product or triethanolamine boron trifluoride complex etc.
Hydantoin-based compound is the material with following structure in the catalyst of the present invention:
In the formula, R is-CH
2CH
2OH ,-CH
2CH=CH
2Or
Deng.
The isocyanuric acid ester type compound is the material with following structure in the catalyst of the present invention:
In the formula, R is-CH
2CH
2OH ,-CH
2CH=CH
2Or
Deng.
Preparation of catalysts method of the present invention, contain following steps:
(a) aqueous solution of water-soluble cyanide slaine and water-soluble metal saline solution and little molecule organic ligand hybrid reaction generate cyanide complex catalyst suspension;
(b) in above-mentioned suspension, add little molecule organic ligand or its aqueous solution, functional compound and functional polymer, be uniformly dispersed, filter;
(c) filter cake with (b) disperses with little molecule organic ligand or its aqueous solution, adds functional compound and functional polymer then, is uniformly dispersed, filters;
(d) filter cake in dry (c) is prepared into the cyanide complex catalyst powder;
Water-soluble cyanide slaine is K in the above-mentioned steps
3Co (CN)
6, K
2Ni (CN)
4, Na
3Co (CN)
6, Na
2Ni (CN)
4, K
3Fe (CN)
6Or Ca
3[Co (CN)
6]
2And composition thereof.
Water-soluble metal salt is ZnCl in the above-mentioned steps
2, ZnBr
2, ZnSO
4, MnCl
2Or FeCl
2Deng.
Catalyst of the present invention is compared with traditional catalyst has following advantage:
(1) Preparation of Catalyst is easy to filtration, dry and pulverizing;
(2) the catalyst inducement phase is short;
(3) with the catalyst of little molecule ligand-functional polymer's coordination system specific activity height mutually;
(4) low with the synthetic PPG degree of unsaturation of catalyst of the present invention.
Catalyst of the present invention can be used for synthesizing polyether, polyester, polyether ester and Merlon etc., can adopt intermittence, semicontinuous and continuous processing.PPG synthetic among the embodiment 7-12 is through using, and effect is fine, especially is fit to soft bubble production.
The specific embodiment
Except as otherwise noted, following material concentration is mass fraction.
Embodiment 1 tert-butyl alcohol-aziridine functional compound-polyethers complex catalyst
A solution: 20g zinc chloride, the 30ml tert-butyl alcohol, 30ml deionized water, stirring is dissolved solid fully.
B solution: 8g Cobalt Potassium Cyanide, 150ml deionized water, stirring is dissolved solid fully.
In the 1000ml there-necked flask, add A solution, drip B solution down in 40 ℃.After dripping, adding 250ml concentration is 50% tert-butyl alcohol aqueous solution, be warmed up to 70 ℃ and keep 1h then, be cooled to 35 ℃, add 2g succinic acid-trimethyl aziridine phosphine oxide condensation product (number-average molecular weight 400) and 2g molecular weight 4,000 two degree of functionality PPOX polyethers, be uniformly dispersed, filter.It is in 70% tert-butyl alcohol aqueous solution that filter cake is scattered in 250ml concentration again, adds 2g succinic acid-trimethyl aziridine phosphine oxide condensation product and 2g molecular weight 4,000 two degree of functionality PPOX polyethers, is uniformly dispersed, filters.Filter cake is scattered in the 250ml tert-butyl alcohol again, adds 1g succinic acid-trimethyl aziridine phosphine oxide condensation product and 1g molecular weight 4,000 two degree of functionality PPOX polyethers, is uniformly dispersed, filters.Filter cake is dry under 50 ℃ of vacuum, pulverize the about 14.0g of catalyst.This catalyst is labeled as I.
Show that through elementary analysis, heat analysis and chemical analysis this catalyst consists of: Zn, 22.1%; Co, 9.3%; The tert-butyl alcohol, 5%; Water, 2.7%; Succinic acid-trimethyl aziridine phosphine oxide condensation product, 14%; Polyethers, 15%.In cobalt content catalyst yield is 91.8%.
Calculating this catalyst by above analysis result consists of: Zn
3[Co (CN)
6]
21.31ZnCl
20.86C
4H
10O0.44T0.048PPG1.90H
2O (T is the succinic acid-trimethyl aziridine phosphine oxide condensation product of mean molecule quantity 400, and PPG is molecular weight 4,000 two degree of functionality PPOX polyethers)
Embodiment 2 tert-butyl alcohols-N, N-two (2-ethoxy) aniline-polyethers complex catalyst
A solution: 20g zinc chloride, the 30ml tert-butyl alcohol, 30ml deionized water, stirring is dissolved solid fully.
B solution: 8g Cobalt Potassium Cyanide, 150ml deionized water, stirring is dissolved solid fully.
In the 1000ml there-necked flask, add A solution, drip B solution down in 40 ℃.After dripping, add 250ml concentration again and be 50% the tert-butyl alcohol aqueous solution, be warmed up to 70 ℃ and keep 1h then, be cooled to 35 ℃, add 2gN, N-two (2-ethoxy) aniline and 2g molecular weight 4,000 two degree of functionality PolyTHF-oxirane polyethers (mol ratio 50/50) are uniformly dispersed, filter.It is in 70% tert-butyl alcohol aqueous solution that filter cake is scattered in 250ml concentration again, adds 2gN, and N-two (2-ethoxy) aniline and 2g molecular weight 4,000 two degree of functionality PolyTHF-oxirane polyethers are uniformly dispersed, filter.Filter cake is scattered in the 250ml tert-butyl alcohol again, adds 1gN, and N-two (2-ethoxy) aniline and 1g molecular weight 4,000 two degree of functionality PolyTHF-oxirane polyethers are uniformly dispersed, filter, and filter cake is dry under 50 ℃ of vacuum, pulverize catalyst 15.0g.This catalyst is labeled as II.
Show that through elementary analysis, heat analysis and chemical analysis this catalyst consists of: Zn, 21.1%; Co, 8.8%; The tert-butyl alcohol, 4%; Water, 3.7%; N, N-two (2-ethoxy) aniline, 16%; Polyethers 15%.In cobalt content catalyst yield is 93.1%.
Calculating this catalyst by above analysis result consists of: Zn
3[Co (CN)
6]
21.34ZnCl
20.72C
4H
10O1.02T0.05PET2.75H
2O (T is N, and N-two (2-ethoxy) aniline, PET are molecular weight 4,000 two degree of functionality PolyTHF-oxirane polyethers)
Embodiment 3 tert-butyl alcohols-1,3 dihydroxy ethyl DMH (DMH ethylene oxide condensate)-polyethers complex catalyst
A solution: 20g zinc chloride, the 30ml tert-butyl alcohol, 30ml deionized water, stirring is dissolved solid fully.
B solution: 8g Cobalt Potassium Cyanide, 150ml deionized water, stirring is dissolved solid fully.
In the 1000ml there-necked flask, add A solution, drip B solution down in 40 ℃.After dripping, adding 250ml concentration is 50% the tert-butyl alcohol aqueous solution, be warmed up to 70 ℃ and keep 1h then, be cooled to 35 ℃, add 2gl, 3-dihydroxy ethyl DMH and 2g molecular weight 4,000 two degree of functionality PolyTHF-oxirane polyethers (mol ratio 50/50) are uniformly dispersed, filter.Filter cake is scattered in 250ml 70% tert-butyl alcohol aqueous solution again, adds 2gl, and 3-dihydroxy ethyl DMH and 2g molecular weight 4,000 two degree of functionality PolyTHF-oxirane polyethers are uniformly dispersed, filter.Filter cake is scattered in the 250ml tert-butyl alcohol again, adds 1gl, and 3-dihydroxy ethyl DMH and 1g molecular weight 4,000 two degree of functionality PolyTHF-oxirane polyethers are uniformly dispersed, filter, and filter cake is dry under 50 ℃ of vacuum, pulverize the about 14.5g of catalyst.This catalyst is labeled as III.
Show that through elementary analysis, heat analysis and chemical analysis this catalyst consists of: Zn, 22.9%; Co, 9.5%; The tert-butyl alcohol, 3%; Water, 2.5%; 1,3-dihydroxy ethyl DMH, 16%; Polyethers, 14%.In cobalt content catalyst yield is 97.1%.
Calculating this catalyst by above analysis result consists of: Zn
3[Co (CN)
6]
21.36ZnCl
20.50C
4H
10O0.81T0.043PET1.72H
2O (T is 1, and 3-dihydroxy ethyl DMH, PET are molecular weight 4,000 two degree of functionality PolyTHF-oxirane polyethers)
Embodiment 4 tert-butyl alcohols-tris(2-hydroxy ethyl)isocyanurate-polyethers complex catalyst
A solution: 20g zinc chloride, the 30ml tert-butyl alcohol, 30ml deionized water, stirring is dissolved solid fully.
B solution: 8g Cobalt Potassium Cyanide, 150ml deionized water, stirring is dissolved solid fully.
In the 1000ml there-necked flask, add A solution, drip B solution down in 40 ℃.After dripping, add 250ml concentration again and be 50% the tert-butyl alcohol aqueous solution, be warmed up to 70 ℃ and keep 1h then, be cooled to 35 ℃, add 2g tris(2-hydroxy ethyl)isocyanurate and 2g molecular weight 4,000 two degree of functionality PolyTHF-oxirane polyethers (mol ratio 50/50), be uniformly dispersed, filter.It is in 70% the tert-butyl alcohol aqueous solution that filter cake is scattered in 250ml concentration again, adds 2g tris(2-hydroxy ethyl)isocyanurate and 2g molecular weight 4,000 two degree of functionality PolyTHF-oxirane polyethers, is uniformly dispersed, filters.Filter cake is scattered in the 250ml tert-butyl alcohol again, adds 1g tris(2-hydroxy ethyl)isocyanurate and 1g molecular weight 4,000 two degree of functionality PolyTHF-oxirane polyethers, is uniformly dispersed, filters, and filter cake is dry under 50 ℃ of vacuum, pulverize the about 14.8g of catalyst.This catalyst is labeled as IV.
Show that through elementary analysis, heat analysis and chemical analysis this catalyst consists of: Zn, 21.7%; Co, 9.4%; The tert-butyl alcohol, 5.4%; Water, 2.9%; Tris(2-hydroxy ethyl)isocyanurate, 13%; Polyethers, 16%.In cobalt content catalyst yield is 98.7%.
Calculating this catalyst by above analysis result consists of: Zn
3[Co (CN)
6]
21.18ZnCl
20.91C
4H
10O0.62T0.05PET2.02H
2O (T is a tris(2-hydroxy ethyl)isocyanurate, and PET is molecular weight 4,000 two degree of functionality PolyTHF-oxirane polyethers)
Embodiment 5 tert-butyl alcohols-KH560 (silane coupler)-polyethers complex catalyst
A solution: 20g zinc chloride, the 30ml tert-butyl alcohol, 30ml deionized water, stirring is dissolved solid fully.
B solution: 8g Cobalt Potassium Cyanide, 150ml deionized water, stirring is dissolved solid fully.
In the 1000ml there-necked flask, add A solution, drip B solution down in 40 ℃.After dripping, adding 250ml concentration is 50% tert-butyl alcohol aqueous solution, is warmed up to 70 ℃ and keep 1h then, is cooled to 35 ℃, add 2gKH-560 and 2g molecular weight 4,000 two degree of functionality PolyTHF-oxirane (mol ratio 50/50) polyethers, be uniformly dispersed, filter.It is in 70% the tert-butyl alcohol aqueous solution that filter cake is scattered in 250ml concentration again, adds 2gKH-560 and 2g molecular weight 4,000 two degree of functionality PolyTHF-oxirane polyethers, is uniformly dispersed, filters.Filter cake is scattered in the 250ml tert-butyl alcohol again, adds 1g KH-560 and 1g molecular weight 4,000 two degree of functionality PolyTHF-oxirane polyethers, is uniformly dispersed, filters, and filter cake is dry under 50 ℃ of vacuum, pulverize catalyst 18.2g.This catalyst is labeled as V.
Show that through elementary analysis, heat analysis and chemical analysis this catalyst consists of: Zn, 20.1%; Co, 7.7%; The tert-butyl alcohol, 1.7%; Water, 1.0%; KH-560 (converting) according to silicone content, 26%; Polyethers, 15%.In cobalt content catalyst yield is 98.8%.
Calculating this catalyst by above analysis result consists of: Zn
3[Co (CN)
6]
21.74ZnCl
20.35C
4H
10O1.71T0.057PET0.85H
2O (T is KH-560, and PET is molecular weight 4,000 two degree of functionality PolyTHF-oxirane polyethers)
Embodiment 6 tert-butyl alcohols-butyl titanate-polyethers complex catalyst
A solution: 20g zinc chloride, the 30ml tert-butyl alcohol, 30ml deionized water, stirring is dissolved solid fully.
B solution: 8g Cobalt Potassium Cyanide, 150ml deionized water, stirring is dissolved solid fully.
In the 1000ml there-necked flask, add A solution, drip B solution down in 40 ℃.After dripping, add 250ml concentration and be 50% the tert-butyl alcohol aqueous solution, be warmed up to 70 ℃ and keep 1h then, be cooled to 35 ℃, add 2g butyl titanate and 2g molecular weight 4,000 two degree of functionality PolyTHF-oxirane polyethers (mol ratio 50/50), be uniformly dispersed, filter.Filter cake is scattered in 250ml 70% tert-butyl alcohol aqueous solution again, adds 2g butyl titanate 2g molecular weight 4,000 two degree of functionality PolyTHF-oxirane polyethers, is uniformly dispersed, filters.Filter cake is scattered in the 250ml tert-butyl alcohol again, adds 1g butyl titanate and 2g molecular weight 4,000 two degree of functionality PolyTHF-oxirane polyethers, is uniformly dispersed, filters, and filter cake is dry under 50 ℃ of vacuum, pulverize catalyst 18.0g.This catalyst is labeled as VI.
Show that through elementary analysis, heat analysis and chemical analysis this catalyst consists of: Zn, 21.4%; Co, 7.8%; The tert-butyl alcohol, 1.8%; Water, 1.0%; Butyl titanate, 23%; Polyethers, 15%.In cobalt content catalyst yield is 98.9%.
Calculate this catalyst by above analysis result and consist of Zn
3[Co (CN)
6]
21.98ZnCl
20.37C
4H
10O1.02T0.057PET0.84H
2O (T is a butyl titanate, and PET is molecular weight 4,000 two degree of functionality PolyTHF-oxirane polyethers)
Comparative Examples 1 tert-butyl alcohol complex catalyst
A solution: 20g zinc chloride, the 30ml tert-butyl alcohol, 30ml deionized water, stirring is dissolved solid fully.
B solution: 8g Cobalt Potassium Cyanide, 150ml deionized water, stirring is dissolved solid fully.
In the 1000ml there-necked flask, add A solution, drip B solution down in 40 ℃.After dripping, add 250ml concentration and be 50% the tert-butyl alcohol aqueous solution, be warmed up to 70 ℃ and keep 1h then, be cooled to 35 ℃, filter.It is in 70% the tert-butyl alcohol aqueous solution, to be uniformly dispersed, to filter that filter cake is scattered in 250ml concentration again.Filter cake is scattered in the 250ml tert-butyl alcohol again, is uniformly dispersed, filters, and filter cake is dry under 50 ℃ of vacuum, pulverize catalyst 11.1g.This catalyst is labeled as VII.
Show that through elementary analysis, heat analysis and chemical analysis this catalyst consists of: Zn, 26.1%; Co, 12.1%.In cobalt content catalyst yield is 94.7%.
Comparative Examples 2 tert-butyl alcohols-polyethers complex catalyst
A solution: 20g zinc chloride, the 30ml tert-butyl alcohol, 30ml deionized water, stirring is dissolved solid fully.
B solution: 8g Cobalt Potassium Cyanide, 150ml deionized water, stirring is dissolved solid fully.
In the 1000ml there-necked flask, add A solution, drip B solution down in 40 ℃.After dripping, add 250ml concentration again and be 50% the tert-butyl alcohol aqueous solution, be warmed up to 70 ℃ and keep 1h then, be cooled to 35 ℃, add 2g two degree of functionality molecular weight 4000 PPOX polyethers, be uniformly dispersed, filter.It is in 70% tert-butyl alcohol aqueous solution that filter cake is scattered in 250ml concentration again, adds 2g two degree of functionality molecular weight 4000 PPOX polyethers, is uniformly dispersed, filters.Filter cake is scattered in the 250ml tert-butyl alcohol again, adds 1g two degree of functionality molecular weight 4000 PPOX polyethers, is uniformly dispersed, filters, and filter cake is dry under 50 ℃ of vacuum, pulverize catalyst 13g, this catalyst is labeled as VIII.
Show that through elementary analysis, heat analysis and chemical analysis catalyst consists of: Zn, 23.2%; Co, 10.2%; Polyethers 20%; In cobalt content catalyst yield is 93.5%.
Embodiment 7～12 PPG synthetic tests
In the 3L autoclave, add the three-functionality-degree PPOX polyethers of 200g molecular weight 500,0.06g catalyst (being respectively one of I～VI) behind the nitrogen replacement, adds expoxy propane 30g, carries out induced reaction under 130 ℃.When reacting kettle inner pressure descends fast, after finishing induction period, under 130 ℃ of temperature, add residue 970g expoxy propane in the 4h continuously, after expoxy propane adds, slaking reaction 30min is cooled to 80 ℃, removes a small amount of fugitive constituent under the vacuum, discharging, two key assignments, molecular weight distribution and the viscosity of analysis PPG.
Comparative Examples 3,4 PPG synthetic tests
Synthesis step is with embodiment 7～12, use be respectively VII, VIII with catalyst.
The synthetic three-functionality-degree polyethers analysis result of each batch catalyst sees Table 1.
Table 1 is with the analysis result of the synthetic three-functionality-degree polyethers of different catalysts
| Test number | 7 | 8 | 9 | 10 | 11 | 12 | Comparative Examples 3 | Comparative Examples 4 |
| The catalyst numbering | I | II | III | IV | V | VI | VII | VIII |
| Induction period, min | 20 | 10 | 15 | 13 | 8 | 6 | 20 | 30 |
| Two key assignments mmol/g | 0.0068 | 0.0054 | 0.0056 | 0.0049 | 0.0064 | 0.0066 | 0.0078 | 0.0070 |
| Molecular weight distribution | 1.12 | 1.14 | 1.07 | 1.06 | 1.14 | 1.15 | 1.15 | 1.16 |
| Viscosity (25 ℃), Pa.s | 0.600 | 0.580 | 0.570 | 0.584 | 0.605 | 0.595 | 0.630 | 0.610 |
Claims (6)
1. cyanide complex catalyst, its general formula is as follows:
M
1 a[M
2(CN)
b]
C·xM
3(A)
d·yQ·zT·jB·hH
2O
Wherein: M
1Be metal cation, be Zn
2+, Mn
2+, Ni
2+, Fe
2+, Co
2+, Sr
2+, Cu
2+In one or more;
M
2Be Co
3+, Fe
3+, Ni
2+Or Cr
3+
M
3Be M
1, M
2In one or more;
A is F
-, Cl
-, Br
-, I
-, PW
12O
40 3-, SO
4 2-, sulfonate radical or carboxylate radical;
A, b, c and d satisfy the chemical valence balance of system; X, y, z, j and h are the numerical value between 0～10;
Q is little molecule organic ligand, is molecular weight less than 200 alcohol, ether, aldehyde, ketone, ester, acid amides or sulfide;
T is a functional compound, is molecular weight less than 500 aziridines compound, alkanolamine compounds, hydantoin-based compound, isocyanuric acid ester type compound, silane or titanate coupling agent;
B is the functional polymer, be molecular weight greater than 500 main chain is carbochain macromolecule polyalcohol, heterochain macromolecule polyalcohol or siliceous, P elements polymer.
2. catalyst according to claim 1 is characterized in that M
3Be Zn
2+Or Mn
2+
3. catalyst according to claim 1 is characterized in that:
Aziridines compound is meant aziridine polyvalent carboxylic acid condensate thing, aziridine polyisocyanic acid ester condensates, three-(the 2-methylaziridine base phosphine oxide) condensation product with carboxylic acid;
The alkanolamine compounds is meant that aniline epoxides condensation product, diethanol amine or triethanolamine are with aliphatic acid or lewis acid condensation product, diethanol amine and hard ester acid reaction with same mole product or triethanolamine boron trifluoride complex;
Hydantoin-based compound is meant the material with following structure:
In the formula, R is-CH
2CH
2OH ,-CH
2CH=CH
2Or
The isocyanuric acid ester type compound is meant the compound with following structure:
In the formula, R is-CH
2CH
2OH ,-CH
2CH=CH
2Or
4. catalyst according to claim 1 is characterized in that:
Main chain is meant polyacrylamide, polyacrylic acid, polypropylene cyanogen, polyvinyl alcohol, poly-Ethylenimine, PVP or poly-hydroxy acrylate for the carbochain macromolecule polyalcohol;
The heterochain macromolecule polyalcohol is meant polyethers, polyester, Merlon or polyamide;
Siliceous, P elements polymer is meant polyphosphazene or polysiloxane compound.
5. catalyst according to claim 1 is characterized in that the functional compound mass fraction is 5%-65%.
6. the described Preparation of catalysts method of claim 1, contain following steps:
(a) aqueous solution of water-soluble cyanide slaine and water-soluble metal saline solution and little molecule organic ligand hybrid reaction generate cyanide complex catalyst suspension;
(b) in above-mentioned suspension, add little molecule organic ligand or its aqueous solution, functional compound and functional polymer, be uniformly dispersed, filter;
(c) filter cake with (b) disperses with little molecule organic ligand or its aqueous solution, adds functional compound and functional polymer then, is uniformly dispersed, filters;
(d) filter cake in dry (c) is prepared into the cyanide complex catalyst powder;
Water-soluble cyanide slaine is K in the above-mentioned steps
3Co (CN)
6, K
2Ni (CN)
4, Na
3Co (CN)
6, Na
2Ni (CN)
4, K
3Fe (CN)
6Or Ca
3[Co (CN)
6]
2And composition thereof;
Water-soluble metal salt is ZnCl in the above-mentioned steps
2, ZnBr
2, ZnSO
4, MnCl
2Or FeCl
2
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN107523424A (en) * | 2017-10-16 | 2017-12-29 | 西南林业大学 | A kind of method of amino-compound inclusion method separation unrighted acid |
| CN116410454A (en) * | 2023-02-13 | 2023-07-11 | 杭州宏聚材科技有限公司 | Surface-organized double metal cyanide catalyst, preparation method and application thereof |
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| AU2003220309B2 (en) * | 2002-03-19 | 2008-09-25 | Dow Global Technologies, Inc. | Method for preparing metal cyanide catalysts using insoluble metal salts |
| AU2003225864B2 (en) * | 2002-03-21 | 2008-08-21 | Dow Global Technologies, Inc. | Method for preparing metal cyanide catalysts using zero valent metals |
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2005
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Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN107523424A (en) * | 2017-10-16 | 2017-12-29 | 西南林业大学 | A kind of method of amino-compound inclusion method separation unrighted acid |
| CN116410454A (en) * | 2023-02-13 | 2023-07-11 | 杭州宏聚材科技有限公司 | Surface-organized double metal cyanide catalyst, preparation method and application thereof |
| CN116410454B (en) * | 2023-02-13 | 2024-03-22 | 杭州合材科技有限公司 | Surface-organized double metal cyanide catalyst, preparation method and application thereof |
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