CN1640544A - Cyanide complex catalyst, and its preparing method and use - Google Patents
Cyanide complex catalyst, and its preparing method and use Download PDFInfo
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Abstract
The present invention relates to a cyanide complex compound catalyst, its preparation method and application in polyether. Said catalyst is made up by means of common coordination of three ligands of organics small molecule, functional compound and functional polymer which are introduced into cyanide complex compound. Said organic small molecule ligand is one or several kinds of alcohol, ether, aldehyde, ketone, ester or acidamine, its molecular weight is less than 200; the functional compound is aromatic carboxylic acid ester compound, its molecular weight is less than 500, and the functional polymer is macromolecular compound containing oxygen, nitrogen, phosphorus and sulfur, and its molecular weight is greater than 500.
Description
Technical field
The present invention relates to a kind of cyanide complex catalyst (hereinafter to be referred as DMC) and preparation method thereof and its application in the preparation polyether glycol.
Background technology
Normally a kind of cyanogen root of dmc catalyst coordinate bimetal complex precipitation.The cyanide complex that bimetallic cyanide complex commonly used has six cyanogen cobalt zinc, six cyanogen iron (divalent or 3 valencys) zinc, four cyanogen nickel zinc, six cyanogen iridium zinc and zinc to be replaced by iron, cobalt, nickel etc.Activity was very low when this simple cyanide complex was used as catalyzer, added the dmc catalyst that water-soluble metal salt and other ligands are prepared, and its catalytic activity increases substantially.Its preparation technology adds organic ligand to carry out complex reaction in the suspension of newly-generated bimetallic cyanide complex, the aqueous solution or organic ligand with organic ligand disperses repeatedly, filters again, with final filtration cakes torrefaction, pulverize, sieve the solid catalyst powder.
The organic molecule ligand of Shi Yonging is glycol dimethyl ether, the trimethyl carbinol the earliest, the home and abroad does not stop other organic ligand catalyst researches always afterwards, and CN1273591A, WO01/83107A2 disclose all kinds hydroxyethyl alkyl oxide coordination catalyst; The applicant has submitted the compound coordination catalyst patent application of two alcohol-aziridine cpds (publication number: CN 1486788A) to; US6358877 discloses the dimethyl sulfoxide (DMSO) coordination catalyst; CN1233529A discloses the compound coordination catalyst of ethylene glycol diethyl ether-trimethyl carbinol; Use the trimethyl carbinol among the WO00/68295 and contained the acrylate group macromolecular cpd and made the part synthetic catalyst; The trimethyl carbinol and polyacrylic compounds synthetic catalyst have been used among the CN1360608A; Disclose the trimethyl carbinol among the CN1383919A, contained phosphorus compound, α, beta-unsaturated carboxylic acid ester, cyclodextrin, glycosides, tricaproin and glycidyl ether coordinate catalyzer; Disclose siliceous carbon chain polymer among the CN1454916A and made functional polymer's bimetallic cyanide complex catalyst; US5482908 discloses the trimethyl carbinol-polyethers coordination catalyst.
Take a broad view of domestic and foreign literature, ligand can be divided into organic molecule ligand, functional compound ligand and functional polymer's ligand three major types.In numerous researchs, only use wherein a class or two classes as ligand, do not see report with three's comprehensive utilization.
Summary of the invention
One of technical problem to be solved by this invention provides a kind of novel cyanide complex catalyst.
Two of technical problem to be solved by this invention provides a kind of method for preparing this catalyzer.
Three of technical problem to be solved by this invention is to introduce the application of this catalyzer in the preparation polyether glycol.
Catalyzer of the present invention is to make by introduce organic molecule, functional compound and the common coordination of functional polymer's three class ligands in cyanide complex.This catalyzer synthesis technique is stable, inductive phase short, use to such an extent that the polyethers degree of unsaturation is low under the high temperature; , pfpe molecule amount narrowly distributing low with its synthetic polyethers viscosity.
Discover, after the whole skeleton of dmc catalyst is determined, its organic ligand type decided catalyzer over-all properties.Molecular weight is that 200～500 functional compound can remedy small molecules ligand and macromole ligand deficiency as ligand.Usually the small molecules ligand is because sterically hindered little, be easy to and the active centre ion coordination, but since its molecular weight low, have volatility, be easy to break away from the active centre ion, powder catalyst standing storage activity reduces even can't induce, and reason causes thus usually; The macromole ligand is sterically hindered big, is not easy to and the active centre ion coordination, must by means of the small molecules ligand could and the active centre ionic bond, do not have the existence of small molecules ligand, only have macromole ligand catalyzer generally be do not have active.The present invention introduces aromatic carboxylic acid esters's functional compound ligand in small molecules and functional polymer's coordinate catalyzer, the catalyst performance that makes is greatly improved.
Its general formula of catalyzer of the present invention is as follows:
M
1 a[M
2(CN)
b]
c·xM
3(A)
d·yQ·zT·jB·hH
2O
Wherein
M
1Be metallic cation, be generally Zn
2+, Ni
2+, Fe
2+, Co
2+Or 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+, Ni
2+
A is F
1-, Cl
1-, Br
1-, I
1-, (PW
12O
40)
3-, (SO
4)
2-, sulfonate radical or carboxylate radical;
Q is the organic molecule ligand, is generally organic compound such as alcohol, ether, aldehyde, ketone, ester or amides, and molecular weight is less than 200, and boiling point is lower than 250 ℃ under the normal pressure, and the most frequently used is the trimethyl carbinol;
T is a functional compound, and molecular weight is 200～500, and certain volatility is arranged under the vacuum, comprises aromatic carboxylic acid esters's compound, phosphate compounds, nitrogen-containing heterocycle compound, polyethers etc.Be generally the ester derivative of phenylformic acid, phthalic acid, benzene tricarboxylic acid, benzene tetracarboxylic acid and biphenyl ether tetracarboxylic acid.Glycol dibenzoate ester, phenylformic acid binaryglycol ester, dibenzoic acid binaryglycol ester, dibenzoic acid dipropylene glycol ester, m-phthalic acid two (beta-hydroxyethyl) ester, terephthalic acid two (beta-hydroxyethyl) ester, phthalic acid dimethoxy-ethyl ester, phthalic acid two (diethylene glycol monomethyl ether) ester, phthalic acid two (diethylene glycol monoethyl ether) ester, trimellitic acid trimethoxy ethyl ester, benzene tetracarboxylic acid tetramethoxy ethyl ester or 3 are specifically arranged, 3 '-4,4 '-biphenyl ether tetracarboxylic acid tetramethoxy ethyl ester etc.
The massfraction of aromatic carboxylic acid esters's compound is 2%～65% in the catalyzer of the present invention.
B is the functional polymer, molecular weight is generally greater than 500, do not possess volatility, for containing the macromole class functional polymer of oxygen, nitrogen, phosphorus, carbon or sulphur, being generally (1) main chain is the carbochain high polymer, for example polyacrylamide, polyacrylic acid, polymethyl acrylic acid, polyacrylonitrile, polyvinyl alcohol, poly-ethyleneimine, Polyvinylpyrolidone (PVP), poly-hydroxyalkyl acrylates or poly-hydroxyalkyl-methacrylic ester; (2) heterochain high polymer is as polyethers, polyester, polycarbonate or polymeric amide etc.; (3) siliceous, phosphorus inorganic elements polymkeric substance is as polyphosphonitrile, polysiloxane compound etc.
A, b, c and d satisfy the valency balance of system; X, y, z, j and h form decision by concrete catalyzer, are generally the numerical value between 0～10.
Preparation of catalysts method of the present invention may further comprise the steps:
(a) aqueous solution of the aqueous solution of water-soluble prussiate metal-salt and water-soluble metal salt and organic molecule ligand reaction generates cyanide complex suspension;
(b) in above-mentioned suspension, add organic molecule ligand or its aqueous solution, aromatic carboxylic acid esters's compound and macromole functional polymer, be uniformly dispersed, filter;
(c) filter cake with (b) disperses with organic molecule ligand or its aqueous solution, adds aromatic carboxylic acid esters's compound and macromole functional polymer, is uniformly dispersed, filters;
(d) filter cake in dry (c) is prepared into cyanide complex catalyst.
Water-soluble prussiate metal-salt 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, NiCl
2Or FeCl
2Deng.
Cyanide complex catalyst of the present invention can be used for synthesizing polyether, polyester, polyether ester and polycarbonate etc., can adopt intermittence, semicontinuous and continuous processing.
Catalyzer of the present invention has following beneficial effect:
(1) good combination property;
(2) synthesis technique is stable;
(3) compare the shortening of catalyst inducement phase with small molecules coordination system, small molecules-functional polymer's coordination system;
(4) high temperature uses down, and gained polyethers degree of unsaturation is low;
(5) with low, the narrow molecular weight distribution of its synthetic polyethers viscosity.
Embodiment
Below if no special instructions, described concentration is all mass concentration.
Embodiment 1 trimethyl carbinol-dibenzoic acid binaryglycol ester-polyethers coordination catalyst
A solution: 20g zinc chloride, the 30ml trimethyl carbinol, 30ml water mix to dissolving fully.
B solution: 8gK
3Co (CN)
6, 150ml water mixes to fully dissolving.
In the 1000ml there-necked flask, add A solution, drip B solution down in 40 ℃.After dripping, add 250ml 50% trimethyl carbinol aqueous solution, add 2g dibenzoic acid binaryglycol ester, 2g two functionality molecular weight 4000 poly(propylene oxide) polyethers again, be uniformly dispersed, filter.Filter cake is scattered in 250ml 70% trimethyl carbinol aqueous solution again, adds 2g dibenzoic acid binaryglycol ester, 2g two functionality molecular weight 4000 poly(propylene oxide) polyethers, is uniformly dispersed, filters.The filter cake redispersion adds 1g dibenzoic acid binaryglycol ester, 1g two functionality molecular weight 4000 poly(propylene oxide) polyethers in the 250ml trimethyl carbinol, be uniformly dispersed, filter, and filter cake is in 50 ℃ of vacuum-drying 2h, pulverize the about 14g of catalyzer, this catalyzer is labeled as I.
Show that through ultimate analysis, heat analysis and chemical analysis this catalyzer consists of: Zn 22.1%; Co 9.3%; The trimethyl carbinol 3.7%, dibenzoic acid binaryglycol ester 14%, molecular weight 4000 poly(propylene oxide) polyethers 18% are 91.7% in cobalt catalyzer yield.
Calculating this catalyzer by above analytical results consists of: Zn
3[Co (CN)
6]
21.30ZnCl
20.63C
4H
10O0.54T10.056B14.05H
2O (T1 is the dibenzoic acid binaryglycol ester, and B1 is two functionality molecular weight, 4000 poly(propylene oxide) polyethers)
Embodiment 2 trimethyl carbinols-dibenzoic acid dipropylene glycol ester-polyethers coordination catalyst
A solution: 20g zinc chloride, the 30ml trimethyl carbinol, 30ml water mix to dissolving fully.
B solution: 8gK
3Co (CN)
6, 150ml water mixes to fully dissolving.
In the 1000ml there-necked flask, add A solution, drip B solution down in 40 ℃.After dripping, add 250ml 50% trimethyl carbinol aqueous solution, add 2g dibenzoic acid dipropylene glycol ester, 2g two functionality molecular weight 4000 poly(propylene oxide) polyethers again, be uniformly dispersed, filter.Filter cake is scattered in 250ml 70% trimethyl carbinol aqueous solution again, adds 2g dipropylene glycol dibenzoate, 2g two functionality molecular weight 4000 poly(propylene oxide) polyethers, is uniformly dispersed, filters.The filter cake redispersion is in the 250ml trimethyl carbinol, add 1g dipropylene glycol dibenzoate, 1g two functionality molecular weight 4000 poly(propylene oxide) polyethers, be uniformly dispersed, filter, filter cake is in 50 ℃ of vacuum-drying 2h, pulverize the about 13.5g of catalyzer, this catalyzer is labeled as II.
Show that through ultimate analysis, heat analysis and chemical analysis this catalyzer consists of: Zn 22.6%; Co 9.8%; The trimethyl carbinol 1.85%, dibenzoic acid dipropylene glycol ester 15%, molecular weight 4000 poly(propylene oxide) polyethers 14% are 93.2% in cobalt catalyzer yield.
Calculating this catalyzer by above analytical results consists of:
Zn
3[Co (CN)
6]
21.18ZnCl
20.32C
4H
10O0.51T20.044B22.71H
2O (T2 is a dibenzoic acid dipropylene glycol ester, and B2 is two functionality molecular weight, 4000 poly(propylene oxide) polyethers)
Embodiment 3 trimethyl carbinols-phthalic acid dimethoxy ethyl ester-polysiloxane compound coordination catalyst
Polysiloxane compound is U.S. Gao Shi Mitt USA Corporation product, and the trade mark is L-580, number-average molecular weight 3000.
A solution: 20g zinc chloride, the 30ml trimethyl carbinol, 30ml water mix to dissolving fully.
B solution: 8gK
3Co (CN)
6, 150ml water mixes to fully dissolving.
In the 1000ml there-necked flask, add A solution, drip B solution down in 40 ℃.After dripping, add 250ml 50% trimethyl carbinol aqueous solution, add 2g phthalic acid dimethoxy ethyl ester, 2g L-580 again, be uniformly dispersed, filter.Filter cake is scattered in 250ml 70% trimethyl carbinol aqueous solution again, adds 2g phthalic acid dimethoxy ethyl ester, 2g L-580, is uniformly dispersed, filters.The filter cake redispersion adds 1g phthalic acid dimethoxy ethyl ester, 1g L-580 in the 250ml trimethyl carbinol, be uniformly dispersed, filter, and filter cake is in 50 ℃ of vacuum-drying 2h, pulverize the about 15g of catalyzer, this catalyzer is labeled as III.
Show that through ultimate analysis, heat analysis and chemical analysis this catalyzer consists of: Zn 21.1%; Co 8.8%; The trimethyl carbinol 1.90%, phthalic acid dimethoxy ethyl ester 18%, L-580 14%, is 93.1% in cobalt catalyzer yield.
Calculating this catalyzer by above analytical results consists of: Zn
3[Co (CN)
6]
21.34ZnCl
20.34C
4H
10O0.85T30.062B33.05H
2O
(T3 is a phthalic acid dimethoxy ethyl ester, and B3 is L-580)
Embodiment 4
The trimethyl carbinol-phthalic acid two (diethylene glycol monomethyl ether) ester-polysiloxane compound coordination catalyst
Polysiloxane compound is U.S. Gao Shi Mitt USA Corporation product, and the trade mark is L-580, number-average molecular weight 3000.
A solution: 20g zinc chloride, the 30ml trimethyl carbinol, 30ml water mix to dissolving fully.
B solution: 8gK
3Co (CN)
6, 150ml water mixes to fully dissolving.
In the 1000ml there-necked flask, add A solution, drip B solution down in 40 ℃.After dripping, add 250ml 50% trimethyl carbinol aqueous solution, add 2g phthalic acid two (diethylene glycol monomethyl ether) ester, 2g L-580 again, be uniformly dispersed, filter.Filter cake is scattered in 250ml 70% trimethyl carbinol aqueous solution again, adds 2g phthalic acid two (diethylene glycol monomethyl ether) ester, 2g L-580, is uniformly dispersed, filters.The filter cake redispersion adds 1g phthalic acid two (diethylene glycol monomethyl ether) ester, 1g L-580 in the 250ml trimethyl carbinol, be uniformly dispersed, filter, and filter cake is in 50 ℃ of vacuum-drying 2h, pulverize the about 15g of catalyzer, this catalyzer is labeled as IV.
Show that through ultimate analysis, heat analysis and chemical analysis this catalyzer consists of: Zn 21.1%; Co 9.1%; The trimethyl carbinol 4.0%, phthalic acid two (diethylene glycol monomethyl ether) ester 20%, L-580 13%, is 96.2% in cobalt catalyzer yield.
Calculating this catalyzer by above analytical results consists of: Zn
3[Co (CN)
6]
21.20ZnCl
20.70C
4H
10O0.70T40.056B43.50H
2O
[T4 is phthalic acid two (diethylene glycol monomethyl ether), and B4 is L-580]
Embodiment 5
The trimethyl carbinol-m-phthalic acid two (beta-hydroxyethyl) ester-polysiloxane compound coordination catalyst
Polysiloxane compound is a Nanjing triumphant Sheng urethane auxiliary agent company limited product, and the trade mark is K-6840, number-average molecular weight 2500.
A solution: 20g zinc chloride, the 30ml trimethyl carbinol, 30ml water mix to dissolving fully.
B solution: 8gK
3Co (CN)
6, 150ml water mixes to fully dissolving.
In the 1000ml there-necked flask, add A solution, drip B solution down in 40 ℃.After dripping, add 250ml 50% trimethyl carbinol aqueous solution, add 2g m-phthalic acid two (beta-hydroxyethyl) ester, 2g K-6840 again, be uniformly dispersed, filter.Filter cake is scattered in 250ml 70% trimethyl carbinol aqueous solution again, adds 2g m-phthalic acid two (beta-hydroxyethyl) ester, 2g K-6840, is uniformly dispersed, filters.The filter cake redispersion adds 1g m-phthalic acid two (beta-hydroxyethyl) ester, 1g K-6840 in the 250ml trimethyl carbinol, be uniformly dispersed, filter, and filter cake is in 50 ℃ of vacuum-drying 2h, pulverize the about 15g of catalyzer, this catalyzer is labeled as V.
Show that through ultimate analysis, heat analysis and chemical analysis this catalyzer consists of: Zn 21.1%; Co 8.8%; The trimethyl carbinol 3.9%, m-phthalic acid two (beta-hydroxyethyl) ester 16%, K-6840 15%, is 93.1% in cobalt catalyzer yield.
Calculating this catalyzer by above analytical results consists of: Zn
3[Co (CN)
6]
21.34ZnCl
20.71C
4H
10O0.96T50.080B53.80H
2O
[T5 is m-phthalic acid two (beta-hydroxyethyl) ester, and B5 is K-6840]
Embodiment 6 trimethyl carbinols-m-phthalic acid two (beta-hydroxyethyl) ester-polyethers coordination catalyst
A solution: 4000g zinc chloride, the 6000ml trimethyl carbinol, 6000ml water mix to dissolving fully.
B solution: 1600g K
3Co (CN)
6, 30000ml water mixes to fully dissolving.
In the 100L reactor, add A solution, drip B solution down in 40 ℃.After dripping, add 50ml 50% trimethyl carbinol aqueous solution, add 400g m-phthalic acid two (beta-hydroxyethyl) ester, 400g two functionality molecular weight 4000 poly(propylene oxide) polyethers again, be uniformly dispersed, filter.Filter cake is scattered in 250ml 70% trimethyl carbinol aqueous solution again, adds 400g m-phthalic acid two (beta-hydroxyethyl) ester, 400g two functionality molecular weight 4000 poly(propylene oxide) polyethers, is uniformly dispersed, filters.The filter cake redispersion is in the 250ml trimethyl carbinol, add 200g m-phthalic acid two (beta-hydroxyethyl) ester, 200g two functionality molecular weight 4000 poly(propylene oxide) polyethers, be uniformly dispersed, filter, filter cake is in 50 ℃ of vacuum-drying 2h, pulverize the about 2725g of catalyzer, this catalyzer is labeled as VI.
Show that through ultimate analysis, heat analysis and chemical analysis this catalyzer consists of: Zn 23.4%; Co 10.2%; The trimethyl carbinol 1.1%, m-phthalic acid two (beta-hydroxyethyl) ester 12%, molecular weight 4000 poly(propylene oxide) polyethers 15% are 98.0% in cobalt catalyzer yield.
Calculating this catalyzer by above analytical results consists of: Zn
3[Co (CN)
6]
21.16ZnCl
20.17C
4H
10O0.62T60.043B61.35H
2O
[T6 is m-phthalic acid two (beta-hydroxyethyl) ester, and B6 is two functionality molecular weight, 4000 poly(propylene oxide) polyethers]
Comparative Examples 1 trimethyl carbinol coordination catalyst
A solution: 20g zinc chloride, the 30ml trimethyl carbinol, 30ml water mix to dissolving fully.
B solution: 8g K
3Co (CN)
6, 150ml water mixes to fully dissolving.
In the 1000ml there-necked flask, add A solution, drip B solution down in 40 ℃.After dripping, add 250ml 50% trimethyl carbinol aqueous solution, filter.Filter cake is scattered in 250ml 70% trimethyl carbinol aqueous solution again, is uniformly dispersed, filters.The filter cake redispersion is uniformly dispersed, filters in the 250ml trimethyl carbinol, and filter cake gets the 11.1g catalyzer in 50 ℃ of vacuum-drying 2h, and this catalyzer is labeled as VII.
Show that through ultimate analysis, heat analysis and chemical analysis this catalyzer consists of: Zn 26.1%; Co 11.1%; In cobalt catalyzer yield is 94.7%.
Comparative Examples 2 trimethyl carbinols-polyethers coordination catalyst
A solution: 20g zinc chloride, the 30ml trimethyl carbinol, 30ml water mix to dissolving fully.
B solution: 8g K
3Co (CN)
6, 150ml water mixes to fully dissolving.
In the 1000ml there-necked flask, add A solution, drip B solution down in 40 ℃.After dripping, add 250ml 50% trimethyl carbinol (C
4H
10O) aqueous solution adds 2g two functionality molecular weight 4000 poly(propylene oxide) polyethers again, is uniformly dispersed, filters.Filter cake is scattered in 250ml 70% trimethyl carbinol aqueous solution again, adds 2g two functionality molecular weight 4000 poly(propylene oxide) polyethers, is uniformly dispersed, filters.The filter cake redispersion adds 1g two functionality molecular weight 4000 poly(propylene oxide) polyethers (PPG) in the 250ml trimethyl carbinol, be uniformly dispersed, filter, and filter cake gets the 13g catalyzer in 50 ℃ of vacuum-drying 2h, and this catalyzer is labeled as VIII.
Show that through ultimate analysis, heat analysis and chemical analysis this catalyzer consists of: Zn 23.2%; Co 10.2%; The trimethyl carbinol 8.5%, polyethers 20% is 93.5% in cobalt catalyzer yield.
Calculating this catalyzer by above analytical results consists of: Zn
3[Co (CN)
6]
21.12ZnCl
21.33C
4H
10O0.058PPG1.34H
2O
7～12 liang of functionality molecular weight 2000 polyether glycols of embodiment are synthetic
In the 3L autoclave, add two functionality poly(propylene oxide) polyethers of 200g molecular weight 400, the 0.03g catalyzer, behind the nitrogen replacement, add propylene oxide 30g, carry out induced reaction at 140 ℃, after reacting kettle inner pressure descended fast, finishes inductive phase, constant temperature was at 140 ℃, add residue 770g propylene oxide in the 4h continuously, after the propylene oxide adding finishes, react 30min again, be cooled to 80 ℃, the a small amount of volatile matter of vacuum removal, the two key assignments of polyether product, molecular weight distribution and viscosity are analyzed in discharging.
3～4 liang of functionality molecular weight 2000 polyether glycols of Comparative Examples are synthetic
Synthesis step is with embodiment 7～12, and catalyzer is respectively VII and VIII.
The synthetic two functionality polyethers indexs of different catalysts see Table 1.
Table 1 different catalysts is synthesized two functionality polyethers indexs
| Test number | Embodiment 7 | Embodiment 8 | Embodiment 9 | Embodiment 10 | Embodiment 11 | Embodiment 12 | Comparative Examples 3 | Comparative Examples 4 |
| The catalyzer numbering | ??I | ??II | ??III | ??IV | ??V | ??VI | ??VII | ??VIII |
| Inductive phase, min | ??16 | ??13 | ??20 | ??20 | ??1 | ??1 | ??30 | ??25 |
| Two key assignments, mmol/g | ??0.0042 | ??0.0045 | ??0.0060 | ??0.0070 | ??0.0045 | ??0.0048 | ??0.0098 | ??0.0092 |
| Molecular weight distributing index (D) | ??1.09 | ??1.08 | ??1.11 | ??1.12 | ??1.10 | ??1.11 | ??1.18 | ??1.17 |
| Polyethers viscosity, mPa.s | ??340 | ??345 | ??350 | ??349 | ??348 | ??349 | ??380 | ??375 |
Embodiment 13～14 three-functionality-degree molecular weight 3000 polyethers are synthetic
In the 3L autoclave, add the three-functionality-degree poly(propylene oxide) polyethers of 200g molecular weight 500, the 0.06g catalyzer, behind the nitrogen replacement, add propylene oxide 30g, constant temperature carries out induced reaction at 130 ℃, after reacting kettle inner pressure descended fast, finishes inductive phase, constant temperature was at 130 ℃, add residue 970g propylene oxide in the 4h continuously, after propylene oxide adds, react 30min again, be cooled to 80 ℃, the a small amount of volatile matter of vacuum removal, the two key assignments of polyether product, molecular weight distribution and viscosity are analyzed in discharging.
5～6 liang of functionality molecular weight 3000 polyether glycols of Comparative Examples are synthetic
Synthesis step is with embodiment 13～14, and catalyzer is respectively VII and VIII.
The synthetic three-functionality-degree polyethers index of different catalysts sees Table 2.
Table 2 different catalysts is synthesized three-functionality-degree polyethers index
| Test number | Embodiment 13 | Embodiment 14 | Comparative Examples 5 | Comparative Examples 6 |
| The catalyzer numbering | ????I | ????VI | ???VII | ??VIII |
| Inductive phase, min | ????16 | ????5 | ???20 | ??30 |
| Two key assignments, mmol/g | ????0.0052 | ????0.0055 | ???0.0078 | ??0.0070 |
| Molecular weight distributing index (D) | ????1.09 | ????1.08 | ???1.15 | ??1.16 |
| Polyethers viscosity, mpa.s | ????580 | ????575 | ???630 | ??610 |
Claims (8)
1. cyanide complex catalyst, 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 metallic cation, be selected from Zn
2+, Ni
2+, Fe
2+, Co
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
1-, Cl
1-, Br
1-, I
1-, (PW
12O
40)
3-, (SO
4)
2-, sulfonate radical or carboxylate radical;
Q is the organic molecule ligand, is meant alcohol, ether, aldehyde, ketone, ester or acid amides, and molecular weight is less than 200;
T is aromatic carboxylic acid esters's compound, is meant the ester derivative of phenylformic acid, phthalic acid, benzene tricarboxylic acid, benzene tetracarboxylic acid or biphenyl ether tetracarboxylic acid, and molecular weight is 200～500;
B is the macromole functional polymer who contains oxygen, nitrogen, phosphorus, carbon or sulphur, refers to that main chain is carbochain high polymer, heterochain high polymer or siliceous, phosphorus inorganic elements polymkeric substance, and molecular weight is greater than 500;
A, b, c and d satisfy the valency balance of system;
X, y, z, j and h are the numerical value between 0～10.
2. according to the described catalyzer of claim 1, it is characterized in that M
3Be Zn
2+Or Ni
2+
3. according to the described catalyzer of claim 1, it is characterized in that described aromatic carboxylic acid esters's compound is selected from the glycol dibenzoate ester, the phenylformic acid binaryglycol ester, the dibenzoic acid binaryglycol ester, dibenzoic acid dipropylene glycol ester, m-phthalic acid two (beta-hydroxyethyl) ester, terephthalic acid two (beta-hydroxyethyl) ester, phthalic acid dimethoxy-ethyl ester, phthalic acid two (diethylene glycol monomethyl ether) ester, phthalic acid two (diethylene glycol monoethyl ether) ester, trimellitic acid trimethoxy ethyl ester, benzene tetracarboxylic acid tetramethoxy ethyl ester or 3,3 '-4,4 '-biphenyl ether tetracarboxylic acid tetramethoxy ethyl ester.
4. according to the described catalyzer of claim 1, the massfraction that it is characterized in that aromatic carboxylic acid esters's compound is 2%～65%.
5. according to the described catalyzer of claim 1, it is characterized in that wherein main chain is selected from polyacrylamide, polyacrylic acid, polymethyl acrylic acid, polyacrylonitrile, polyvinyl alcohol, poly-ethyleneimine, Polyvinylpyrolidone (PVP), poly-hydroxy acrylate or poly-hydroxyethyl-methacrylic ester for the carbochain high polymer; The heterochain high polymer is selected from polyethers, polyester, polycarbonate or polymeric amide; Siliceous, phosphorus inorganic elements polymkeric substance is selected from polyphosphonitrile or polysiloxane compound.
6. the described Preparation of catalysts method of claim 1 is characterized in that may further comprise the steps:
(a) aqueous solution of the aqueous solution of water-soluble prussiate metal-salt and water-soluble metal salt and organic molecule ligand reaction generates cyanide complex suspension;
(b) in above-mentioned suspension, add organic molecule ligand or its aqueous solution, aromatic carboxylic acid esters's compound and macromole functional polymer, be uniformly dispersed, filter;
(c) filter cake with (b) disperses with organic molecule ligand or its aqueous solution, adds aromatic carboxylic acid esters's compound and macromole palace energy polymkeric substance, is uniformly dispersed, filters;
(d) filter cake in dry (c) is prepared into cyanide complex catalyst.
7. according to the described Preparation of catalysts method of claim 6, it is characterized in that described water-soluble prussiate metal-salt is K
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; Described water-soluble metal salt is ZnCl
2, ZnBr
2, ZnSO
4, NiCl
2Or FeCl
2
8. the application of the described cyanide complex catalyst of claim 1 in the preparation polyether glycol.
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| CNB2004100917799A CN1308079C (en) | 2004-11-29 | 2004-11-29 | Cyanide complex catalyst, and its preparing method and use |
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| CNB2004100917799A CN1308079C (en) | 2004-11-29 | 2004-11-29 | Cyanide complex catalyst, and its preparing method and use |
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP1946839A3 (en) * | 2007-01-17 | 2008-12-31 | Bayer MaterialScience AG | Double metal cyanide catalysts for producing polyetherpolyols |
| JP2010501668A (en) * | 2006-08-24 | 2010-01-21 | コーネル・ユニバーシティー | Copolymerization of propylene oxide and carbon dioxide and homopolymerization of propylene oxide |
Family Cites Families (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5482908A (en) * | 1994-09-08 | 1996-01-09 | Arco Chemical Technology, L.P. | Highly active double metal cyanide catalysts |
| DE10122020A1 (en) * | 2001-05-07 | 2002-11-14 | Bayer Ag | Double metal cyanide catalysts for the production of polyether polyols |
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Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2010501668A (en) * | 2006-08-24 | 2010-01-21 | コーネル・ユニバーシティー | Copolymerization of propylene oxide and carbon dioxide and homopolymerization of propylene oxide |
| US9683077B2 (en) | 2006-08-24 | 2017-06-20 | Cornell Research Foundation, Inc. | Copolymerization of propylene oxide and carbon dioxide without production of propylene carbonate |
| EP1946839A3 (en) * | 2007-01-17 | 2008-12-31 | Bayer MaterialScience AG | Double metal cyanide catalysts for producing polyetherpolyols |
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| CN1308079C (en) | 2007-04-04 |
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