CN1459332A - Complex catalyst contg. two or more than two kinds of bimetal cyanide, prepn. method and application thereof - Google Patents
Complex catalyst contg. two or more than two kinds of bimetal cyanide, prepn. method and application thereof Download PDFInfo
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- CN1459332A CN1459332A CN 02113051 CN02113051A CN1459332A CN 1459332 A CN1459332 A CN 1459332A CN 02113051 CN02113051 CN 02113051 CN 02113051 A CN02113051 A CN 02113051A CN 1459332 A CN1459332 A CN 1459332A
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Abstract
A complexing catalyst contains two or more than two bimetallic cyanides (BMC), organic coordination agent, soluble metallic salt, polyether polyol, and organic siloxane. Its advantages are storage stability, high reaction activity, and high resistance to high reaction temp. up to 210 deg.C, and short inducing time.
Description
Technical field
The present invention relates to a kind of double metal cyanide complex catalyst of (being called for short DMC down) that contains, particularly contain complex catalyst and its preparation method and the application on the production polyether polyol of two or more double metal cyanide.
Background technology
PPG is the primary raw material in the polyurethane production, and it is to be formed with epoxyalkane reaction ring-opening polymerisation under catalyst action by low molecular polylol.Be used for epoxide ring-opening polymerization from nineteen seventies AM General rubber for tire company invention bimetallic cyanide complex catalyst (being called for short DMC cat down), the patent documentation report is constantly arranged over nearly 40 years, especially since the nineties, Arco company has more patent in this respect, and DMC complex catalyst composition is generally:
M
a 1[M
2(CN)
b(G)
c]
d·xM
3(X)
e·wH
2O·yL
1·zL
2
M
1Be that at least a metal ion is selected from: Zn
(II), Fe
(II), Fe
(III), Co
(II), Ni
(II), Mo
(IV), Sn
(II), Cu
(II), Pb
(II), Mo
(VI), Al
(III), V
(IV), V
(V), Sr
(II), W
(IV), W
(VI), Mn
(II)And Cr
(III)
M
2Be that at least a transition metal ions is selected from: Fe
(II), Fe
(III), Co
(II), Co
(III), Cr
(II), Cr
(III), Mn
(II), Mn
(III), Ni
(III), V
(IV), V
(V), I
(III), Rh
(1II), Ru
(II)
M
3Represent M
1And/or M
2
G, X are CN
-, F
-, Cl
-, Br
-, I
-, OH
-, NO
2 -, CO
3 2-, NO
3 -, SO
4 2-, CNO
-, C
2O
4 2-, CNS
-, NCO
-, NCS
-And carboxylate radical RCOO
-, G, X can identical or different a, b, c, d, e are satisfied with positive and negative charge and equate
L
IRepresent water-soluble hetero atom organic complexing agent as: alcohol, aldehyde, ketone, ether, ester, acid amides, nitrile, sulfide or its mixture, typically using the tert-butyl alcohol (TBA) to make complexing agent has been known technology.
L
2Represent the functional polymer, patent early is useless uses polyethers at first to it, and Near Range enlarges.
Nearly all DMC cat patent will state that all metal ion, acid ion etc. come from all being fit to of above-mentioned scope among its DMC cat, but embodiment meets following formula substantially:
Zn
3[Co(CN)
6]
2·xZnCl
2·wH
2O·yL
1·yL
2
L wherein
1Basic is organic alcohol, L
2Be the functional polymer
Zn wherein
3[Co (CN)
6]
2Be by ZnCl
2With alkali metal cyanide, be generally K
3[Co (CN)
6] reaction.
Raising approach to DMC cat activity relies in crystalline state and the amorphous control substantially, and crystalline state and amorphous state are contradiction to not reaching unified on the activity influence understanding sometimes.
With USP5158922 (Arco company) is the line of demarcation, is L among representative and the DMC cat in the past with it
1Basic is Glyme (dimethoxy-ethane) or Diglyme (diethylene glycol dimethyl ether), and their characteristics are cat crystalline state content height,＞35%, and active low, be called as traditional DMC cat.USP5470813 (Arco company) finds that two kinds of salting liquids are by strong hybrid reactions such as homogenizers, destroy the one-tenth crystal bar spare of catalyst, make organic complexing agent with TBA, make amorphous state cat, (crystalline state DMC compound＜1%wt), (crystalline state DMC compound＞35wt%) is at same 100ppm (final products relatively than the prepared high crystalline state cat of simple agitation, as follows) time active big by 200% during active big 65%, 130～250ppm.Example: PPOX trihydroxylic alcohol (M
n=700) 685g makes initiator, cat250ppm, 105 ℃ of reaction temperatures, induction time 85min, maximum reaction rate (reaction pressure keeps＜0.28MPa) 10.5g PO/min, and polyethers degree of unsaturation＜0.006mol/kg (to hydroxyl value, by the molecular weight that feeds intake about 6660) with ing.Improve a lot with the high crystalline state cat phase specific activity among the USPS158922, draw thus that amorphous part is an active matter among the DMC cat, crystalline state partly is non-active matter, even it is poisonous to amorphous state, this idea keeps so far substantially, reduces ZnCl although adopt among USP5627122 (corresponding CN application number 96108898) and the USP5780854
2Amount makes x among the formula II＜0.2, thereby makes basic crystalline state DMC cat, when for example making hydroxyl value 29.8mg KOH/g PPOX trihydroxylic alcohol, and PPOX trihydroxylic alcohol (M
n=700) 70g makes initiator, cat100ppm, 105 ℃ of reaction temperatures, maximum reaction rate (reaction pressure keeps 0.07MPa) 10.9g PO/min, product degree of unsaturation 0.0026mol/kg.But many patents afterwards though the cat composition is different, think all that as USP5783513,5789626 amorphous state is active high, and USP6018217 thought again that crystalline state DMC compound was diluent even the denaturant of amorphous state cat especially afterwards.The cat activity is in the comparatively ideal example: PPOX trihydroxylic alcohol (M
n=700) 70g makes initiator, 105 ℃ of following induction time 140min of cat100ppm (target molecule dish about 5600 relatively), and maximum rate (reaction pressure keeps 0.07MPa) reaches 26.3gPO/min.Bayer company may want to change crystalline state and amorphous understanding recently, the made DMC cat of USP6204357 (Bayer company) makes complexant with TBA, contain functional polymer's cyclodextrin, its cat comprises crystalline state, amorphous state or part crystalline state, preferably PPOX dihydroxylic alcohols (M in the example
n=1000) 50g makes initiator, cat20ppm, and 105 ℃ of following induction times (PO amount 5g induction period) 197min, total reaction time 478min (reaction pressure keeps 0.25MPa) makes M
n=3800 polyether Glycols, its degree of unsaturation 0.008mol/kg, viscosity (25 ℃) 1022mpas.
Made DMC cat makes complexant with TBA among the USP6291388 (Bayer company), contains functional polymer's polyethylene glycol oxide polyalcohol (M
n＞500), activity increases, and its cat comprises crystalline state, amorphous state, part crystalline state again, and its cat15ppm system hydroxyl value is the PPOX dihydroxylic alcohols (M of 29.8mgKOH/g in the example preferably
n=3810) time, 105 ℃ of reaction temperatures are with 50g PPOX dihydroxylic alcohols (M
n=1000) make initiator, total reaction time 395min (reaction pressure keeps 0.25MPa) products obtained therefrom degree of unsaturation 0.011mol/kg, viscosity (25 ℃) 935mpas.
USP6323375 (Bayer company) makes basic crystalline state type DMC cat organic complex TBA and makes part, contains a kind of functional polymer (being selected from polyethers, polyester, Merlon etc.) among the cat, water 1～10%wt, water soluble salt (ZnCl
2) 5～25%wt, gained cat active testing in the comparatively ideal example: PPOX dihydroxylic alcohols (M
n=1000) 50g makes initiator, cat15ppm, 105 ℃ of following induction time 80min, reaction time 335min (reaction pressure keeps 0.25MPa), hydroxyl value 27.4mgKOH/g, viscosity 1084mpas (25 ℃).
M among the formula I
1, M
2Though most of patent statement is selected from above-mentioned many ions, it is Zn that best DMC is known as
3[Co (CN)
6]
2, do not have patent mention with other as, Fe
(III)And Ni
(II)As M
1, Fe
(III)As M
2Cooperation is to the active raising effect of cat.
The subject matter that dmc catalyst exists at present is its activity and stability problem, activity shows two aspects: reaction time (particularly induction time) and catalyst amount, in the past DMC cat slowly to a few hours even tens of hours ability begin the reaction, this is uneconomic in industrial application; Consumption requires low, be to consider its expensive price on the one hand, be that to avoid post processing with made polyethers be purpose (DMC cat30ppm following) on the other hand, stability is the range of reaction temperature that requires to adapt to broad when depositing stable and use, especially high temperature resistant reaction, the DMC cat of poor stability can make troubles even massive losses to the user.Those requirements are that the DMC cat activity of basic amorphous state or basic crystalline state is difficult to be guaranteed, and shelf stability is also relatively poor.
Best DMC cat activity also haves much room for improvement, and the active situation that can avoid post processing that reaches also is system higher molecular weight M in the above patent
nNear 4000 o'clock, just can accomplish, be difficult to generally promote.
Summary of the invention
The purpose of this invention is to provide a kind of complex catalyst that contains two or more double metal cyanide, with the activity of the complex catalyst of further raising double metal cyanide, thereby induction time is shortened, consumption reduces; The method that another purpose provides this catalyst of preparation comprises the preparation of system of two or more DMC and the method for adding.
The complex catalyst that contains two or more double metal cyanide of the present invention, it comprises: a) metal cyanides (DMC), b) soluble metallic salt, c) a kind of organic complexing agent and functional polymer, a) in said DMC with Zn
3[Co (CN)
6]
2Be main, and contain Ni
3[Co (CN)
6]
2, Fe[Co (CN)
6], Ni
3[Fe (CN)
6]
2, Zn
3[Fe (CN)
6]
2In one or more, the latter's amount is Zn
3[Co (CN)
6]
21～20%wt, best 4～6%wt.
Catalyst general formula of the present invention is: M
a 1[M
2(CN)
b]
dXM
3(X)
cWH
2OyTjPzA
Wherein: M
1And M
3Can be identical or different, be selected from Zn
(II), Fe
(III), Ni
(II)In one or more, with Zn
(II)Be main.
M
2Be Co
(III)Or Fe
(III)And Co
(III), with Co
(III)Be main.
X is for being selected from Cl
-, SO
4 2-In one or two, preferred Cl when selecting one of them
-
T is selected from the tert-butyl alcohol (TBA), dimethoxy-ethane (Glyme), diethylene glycol dimethyl ether (Diglyme), tert-pentyl alcohol (TPA).Preferred tertiary butanols (TBA).
P is a PPG, comprises PPOX, PPOX ethylene oxide copolymer polyalcohol, its 2～8 degree of functionality 2～8, preferred 2～3 degrees of functionality, molecular weight 500～10000, preferred 1000～8000, best 2000～4000.
A, b, c, d meet and are satisfied with positive and negative charge and equate x=0.1～10, w=0.1～1, y=0.1～1, j=0～0.15, z=0.01～2.5
A is a kind of organosiloxane that contains the Si-C chain, and its general molecular formula is:
R wherein
1, R
2, R
3, R
4Be alkyl, be selected from methyl, ethyl, propyl group, butyl, R
1, R
2, R
3, R
4Can be identical or different.Molecular weight is 300～6000, preferred 1000～4000.
Be surprised to find: Zn
3[Co (CN)
6]
2Among the cat for main body, when containing Ni
3[Co (CN)
6]
2, Fe[Co (CN)
6], Zn
3[Fe (CN)
6]
2In one or more the time, the cat activity is significantly improved, especially to contain Ni simultaneously
3[Co (CN)
6]
2, Fe[Co (CN)
6] be good, and select Ni
3[Co (CN)
6]
2/ Fe[Co (CN)
6] mass ratio 3: 1～1: 3 is better, best 2: 3～3: 2.M in the general formula
3(X)
cRepresentative remove ZnCl
2Contain NiCl outward,
2, FeCl
3, NiSO
4, Fe
2(SO
4)
3In one or more, the relative ZnCl of content
20～30%wt, preferred 0～10%wt.
Technical process
The preparation process of complex catalyst that the present invention contains two or more double metal cyanide is as follows:
A. join ZnCl
2Solution adds NiCl
2, FeCl
3, NiSO
4, Fe
2(SO
4)
3In one or more, addition is ZnCl
20～20%wt, preferred 0～10%wt.Contain complexant T, use the tert-butyl alcohol (TBA) preferably.Selectively contain P and/or A, P is 0～1%, and A is 0.～5%, ZnCl
2Concentration range 10%～saturated.
B. join K
3[Co (CN)
6] solution, add K
3[Fe (CN)
6], measure into the former 20% in, in 10%, selectively be added with complexant T preferably, use TBA preferably.K
3[Co (CN)
6] solution concentration scope 1%～saturated.
C. selectively in " a " solution be added to " b " on the contrary in solution or, ZnCl
2/ K
3[Co (CN)
6] mass ratio is 1: 1～8: 1, preferential 3: 1～6: 1, material circulated at a high speed or through stirring, fully mixes in the reactor, and this process produces reaction, generates Zn
3[Co (CN)
6]
2And accessory substance KCl.If do not have NiCl in " a "
2, FeCl
3, NiSO
4, Fe
2(SO
4)
3, do not have K in " b "
3[Fe (CN)
6] selectively add Ni simultaneously this moment
3[Co (CN)
6]
2, Fe[Co (CN)
6], Ni
3[Fe (CN)
6]
2, Zn
3[Fe (CN)
6] wherein one or more, addition is Zn
3[Co (CN)
6]
21～20%wt, preferred 4～6%wt, wherein Ni
3[Co (CN)
6]
2, Fe[Co (CN)
6] add better simultaneously, and select Ni
3[Co (CN)
6]
2/ Fe[Co (CN)
6] mass ratio 3: 1～1: 3 is better, preferred 2: 3～3: 2, selectively adds NiCl simultaneously
2, FeCl
3, NiSO
4, Fe
2(SO
4)
3One of them or more than one, the relative ZnCl of addition
20～30%wt, preferred 0～20%wt, best 0～10%wt.
D. carry out washing process after reaction and reinforced the finishing, washing process is to add after slurry is separated with modes such as centrifugal, filtrations that cleaning solution forms the multiple intermittent mode of slurry again or by film (membrane aperture 0.1～50 μ m) device continuous washing, water-soluble accessory substance such as KCl and excessive ZnCl again
2Remove Deng the water soluble salt separation, selectively be added with P and/or A in the cleaning solution, P is 0～1%, and A is 0～5%.
E. washing finishes the back (to detect K in the parting liquid
+Concentration reaches below the 500ppm, and 300ppm is following for indicating better), with pure organic complexing agent washing replacement moisture content wherein,, in 3～6% the slurries, add P and A better at solid content 1.5～10%, its total amount is theoretical amount Zn
3[Co (CN)
6]
25～200%wt, preferred 15～50%wt, P/A mass ratio 0～1: 1, preferred 1: 10～1: 3, to circulate at a high speed or to stir 0.5～5h, preferred 1～3h.
F. carry out Separation of Solid and Liquid with spreading mass, available centrifugation, modes such as press filtration obtain the pasty state cat of solid content 10～30%.
G. pasty state cat is through 35～80 ℃ of oven dry, or 0～80 ℃ of vacuum drains to constant weight, pulverizes in this process and finishes.The invention effect
(1) the present invention at first finds and makes the cat of two or more specific DMC.Confirmed that DMC is with Zn among the DMC cat
3[Co (CN)
6]
2Be main, fit into Ni
3[Co (CN)
6]
2, Fe[Co (CN)
6], Zn
3[Fe (CN)
6]
2In one or more the time, the cat activity is significantly improved.
(2) product is active high, in being applied to PPG production, DMC cat of the present invention is used to make molecular weight 2000～10, when 000 PPOX two or trihydroxylic alcohol, the cat consumption only needs 8～30ppm, gained polyethers degree of unsaturation is extremely low, can reach 0.001～0.005mol/Kg, 90～180 ℃ of reaction temperatures, different catalysts amount (being not more than 40ppm), make initiator with common than low molecular weight polycaprolactone propylene oxide two or trihydroxylic alcohol (such as molecular weight 400～1000), when the PPOX two of system molecular weight 2000～10,000 or trihydroxylic alcohol, the more common DMC cat of induction time is short, especially under the higher temperatures as 135～145 ℃, the most in short-term＜1min.Reaction rate test: in 2 liters of stills with 70g PPOX dihydroxylic alcohols (M
n=400) initial, cat10ppm, 130 ℃ of system M
nDuring=6000 polyethers, maximum rate (reaction pressure 0.07MPa) 60gPO/min or 50kgP0/gCo/min.
(3) broad application temperature range, 80～210 ℃ of reaction temperatures, 105～150 ℃ of scopes are better, catalyst ability higher temperature in the course of reaction, during the system PPG, the polyethers performance is basic no change in higher reaction temperatures scope (as 130～160 ℃).
Specific embodiment embodiment 1 system { Zn
3[Co (CN)
6]
2+ 0.06Ni
3[Co (CN)
6]
2+ 0.06Fe[Co (CN)
6] ZnCl
20.5H
2In the O0.15TBA0.015P0.092A one batching still, with 22kg ZnCl
3Be dissolved in the 50L TBA/90L deionized water, in another batching still, 5.5kg K
3[Co (CN)
6] be dissolved in the 50L TBA/90L deionized water, two kinds of solution are added in the reactor in the 30min, and circulation (660L/min) mixes at a high speed simultaneously, continues to add 0.33Kg Ni behind the circulation 1.5h
3[Co (CN)
6]
2And 0.15Kg Fe[Co (CN)
6] enter in the built-in diffusion barrier pipeline and circulate, the TBA solution with 50% (0.5% concentration A) 300L washes, and again to displace part moisture content in the slurry in the pure TBA 3h of 200L, continues film and separates behind the 5h, is concentrated into slurry 300L.Add 0.6kg PPOX trihydroxylic alcohol (Mn=3000) and 1.8kg A, circulation 2h is pressed into slurry or suck pressure filter, and press filtration is till the solid content 16～20%, and 0～80 ℃ of following vacuum drying is to constant weight, pulverize cat (I) 8.4kg.Through elementary analysis, thermogravimetric analysis, extraction and liquid-phase chromatographic analysis: Zn=25.7%, Co=12.6%, Ni=1.0%, Fe=0.33%, H
2O=0.88%, TBA=1.1%, P=4.4%, A=13.6%.Comparative example 1 system cat Zn
3[Co (CN)
6]
2ZnCl
20.5H
2O0.15TBA0.015P0.092A is with embodiment 1 operation, but ZnCl
2Be 24kg, K
3[Co (CN)
6] be 6.0kg, get cat (II) 8.5kg.Through elementary analysis, thermogravimetric analysis, extraction and liquid-phase chromatographic analysis: Zn=27.1%, Co=12.2%, H
2O=0.93%, TBA=1.2%, P=4.7%, A=14.3%.Embodiment 2 system { Zn
3[Co (CN)
6]
2+ 0.10Zn
3[Fe (CN)
6]
2ZnCl
20.5H
2O0.15TBA0.015P0.092A operates with embodiment 1, but adds 24kg ZnCl in the batching still
2, add 5.5kg K in another batching still
3[Co (CN)
6] and 0.5kg K
3[Fe (CN)
6].Get cat (III) 8.5kg.Through elementary analysis, thermogravimetric analysis, extraction and liquid-phase chromatographic analysis: Zn=27.4%, Co=11.5%, H
2O=0.88%, TBA=1.1%, P=4.4%, A=13.4%.Embodiment 3 system { Zn
3[Co (CN)
6]
2+ 0.06Ni
3[Co (CN)
6]
2+ 0.06Fe[Co (CN)
6] ZnCl
20.5H
2O0.15TBA0.015P0.092A
With the operation of embodiment 1, but replace displacing part moisture content in the slurry in the pure TBA 3h of 200L with 200L 90%TBA,
Get cat (IV) 8.4kg.
Through elementary analysis, thermogravimetric analysis, extraction and liquid-phase chromatographic analysis: Zn=25.3%, Co=12.7%, Ni=1.0%,
Fe＝0.34％，H
2O＝0.87％，TBA＝1.0％，P＝4.4％，A＝13.5％。Embodiment 4 system { Zn
3[Co (CN)
6]
2+ xNi
3[Co (CN)
6]
2+ yFe[Co (CN)
6] fZnCl
2ZNiCl
2GFeCl
3HNiSO
4MFe
2(SO
4)
3TZnSO
40.5H
2O0.15TBA0.015P0.092A
Operation is with embodiment 1, but in the batching still, with 21kg ZnCl
2, 1.8kg FeCl
3, 1.2kgNiSO
4Be dissolved in the 50LTBA/90L deionized water, in another batching still, 5.9kg K
3[Co (CN)]
6Be dissolved in the 50L TBA/90L deionized water.Get cat (V) 8.4kg
Through elementary analysis, thermogravimetric analysis, extraction and liquid-phase chromatographic analysis: Zn=22.5%, Co=12.7%, Fe=1.5%, Ni=1.1%, H
2O=0.91%, TBA=1.2%, p=4.6%, A=14.0%.Application examples: system PPG
70g polyoxypropyleneglycol (M
n=416), cat 8-30ppm (polyalcohol of made relatively theoretical molecular), place the 2L autoclave pressure, stir down, temperature vacuumizes 30min under 105 ℃, remove micro-moisture, adds expoxy propane 15g, pressure 0.05MPa, after pressure sharply descended, residual epoxide propane 605g added down for 105 ℃ in reaction temperature, keep-ups pressure＜0.07MPa, the process afterreaction phase is to consume all expoxy propane in the still, take out volatile matter for 90 ℃, obtain PPG, carry out hydroxyl value, double bond content, viscosity etc. are measured as following each example.Example A (15ppm) makes polyoxypropyleneglycol (M with cat (I)
n=4000)
With above-mentioned steps, 105 ℃ make PPG, and the result is as follows:
Induction period (min): 40
Total reaction time (min): 240
Maximum reaction rate (g PO/min): 12
Polyalcohol:
Hydroxyl value (mg KOH/g): 28.1
Double bond content (mol/Kg): 0.0015
Viscosity (25 ℃, mpas): 757 routine B are with cat (III), and condition is the same, and the result is as follows:
Induction period (min): 42min
Total reaction time (min): 250
Maximum reaction rate (g PO/min): 11g/min
Polyalcohol:
Hydroxyl value (mg KOH/g): 28.4
Double bond content (mol/Kg): 0.0020
Viscosity (25 ℃, mpas): 820 routine C are with cat (IV), and condition is the same, and the result is as follows;
Induction period (min): 45
Total reaction time (min): 280
Maximum reaction rate (g PO/min): 10.5g/min
Polyalcohol:
Hydroxyl value (mg KOH/g): 28.8
Double bond content (mol/Kg): 0.0030
Viscosity (25 ℃, mpas): 890 routine D are with cat (V), and condition is the same, and the result is as follows:
Induction period (min): 40
Total reaction time (min): 250
Maximum reaction rate (g PO/min): 12g/min
PPG:
Hydroxyl value (mg KOH/g): 28.2
Double bond content (mol/Kg): 0.0030
Viscosity (25 ℃, mpas): 780 routine E system higher molecular weight polyether Glycols
Feed intake with routine A respectively with cat (I), cat (III), cat (IV), treat theoretical molecular to 4000 after, temperature rises to 130 ℃, continue reaction, keep-up pressure below the 0.15MPa, when inlet amount is low to moderate 5gPO/min, stop, the cat concentration of relative theory molecular weight.
With cat (I) result: do to M
n=8000, this moment cat concentration 7.5ppm.
With cat (III) result: do to M
n=7500, this moment cat concentration 8.0ppm.
With cat (IV) result: do to M
n=6500, this moment cat concentration 9.2ppm.
With cat (V) result: do to M
n=8000, this moment cat concentration 7.5ppm comparative example
With Cat. (II), condition is the same, and the result is as follows:
Induction period (min): 55min
Total reaction time (min): 300
Maximum reaction rate (g PO/min): 10g/min
PPG:
Hydroxyl value (mg KOH/g): 29.1
Double bond content (mol/Kg): 0.0040
Viscosity (25 ℃, mpas): 950
Claims (8)
1. contain the complex catalyst of two or more double metal cyanide, comprise: a) double metal cyanide (DMC); B) soluble metallic salt; C) a kind of organic complexing agent; D) functional polymer is characterized in that DMC is with Zn
3[Co (CN)
6]
2Be main, and contain Ni
3[Co (CN)
6]
2, Fe[Co (CN)
6], Ni
3[Fe (CN)
6]
2, Zn
3[Fe (CN)
6]
2In one or more, the above-mentioned Zn that removes
3[Co (CN)
6]
2The amount of other DMC in addition is Zn
3[Co (CN)
6]
21～20%wt, preferred 4～6%wt.
The catalyst general formula is:
M
a 1[M
2(CN)
b]
dXM
3(X)
cWH
2OyTjPzA is wherein: M
1And M
3Can be identical or different, for being selected from Zn
(II), Fe
(III), Ni
(II)In one or more, with Zn
(II)Be main; M
2Be Co
(III)Or Co
(III)And Fe
(III), with Co
(III)Be main; Amount 1～20%wt of being; X is for being selected from Cl
-, SO
4 2-In one or two; T is the tert-butyl alcohol (TBA); P is that PPG comprises PPOX, PPOX oxidation ethoxy copolymer polyols, its degree of functionality 2～8, its molecular weight 500～10000; A, b, c, d meet and are satisfied with positive and negative charge and equate x=0.1～10, w=0.1～1, y=0.1～1, j=0～0.15, z=0.01～2.5.A is a kind of organosiloxane that contains the Si-C chain, and its general molecular formula is:
R wherein
1, R
2, R
3, R
4Alkyl is selected from methyl, ethyl, propyl group, butyl, R
1, R
2, R
3, R
4Can be identical or different, the molecular weight of A is 300～6000.
2. catalyst as claimed in claim 1 is characterized in that DMC contains Ni simultaneously
3[Co (CN)
6]
2, Fe[Co (CN)
6], both mass ratioes are Ni
3[Co (CN)
6]
2: Fe[Co (CN)
6]=3: 1～1: 3.
3. catalyst as claimed in claim 1 or 2 is characterized in that M in the general formula
3(X)
cRepresentative remove ZnCl
2Contain NiCl outward,
2, FeCl
3, NiSO
4, Fe
2(SO
4)
3In one or more, the relative ZnCl of content
20～30%wt, preferred 0～10%wt.
4. the Preparation of catalysts method of a claim 1 comprises step: a) preparation ZnCl
2Solution; B) preparation K
3[Co (CN)
6Solution; C) a solution is mixed with b solution; D) material to the reaction gained repeatedly washs and filters; E) K in the parting liquid
+When concentration reaches 300ppm～500ppm, replace wherein moisture content with pure organic complexing agent washing; F) in the slurry of solid content 1.5～10%, adds P and A; G) pulp separation, press filtration, drying, pulverizing, its preparation of two or more DMC and the adding method that it is characterized in that in the catalyst being comprised are selected from one of following three kinds of methods: 1. at preparation ZnCl
2During solution, add NiCl selectively
2, FeCl
3, NiSO
4, Fe
2(SO
4)
3In one or more common and K
3[Co (CN)
6] solution reaction and obtain removing Zn
3[Co (CN)
6]
2Outer Ni
3[Co (CN)
6]
2, Fe[Co (CN)
6] in one or both; 2. at preparation K
3[Co (CN)
6] be added with K during solution
3[Fe (CN)
6] common and ZnCl
2Solution (selectively is added with NiCl
2Or NiSO
4) reaction and obtain removing Zn
3[Co (CN)
6]
2Outer Zn
3[Fe (CN)
6]
2Or also has Ni
3[Fe (CN)
6]
23. ZnCl
2Solution and K
3[Co (CN)
6] solution reaction obtains Zn
3[Co (CN)
6]
2The back adds Ni
3[Co (CN)
6]
2, Fe[Co (CN)
6],, Ni
3[Fe (CN)
6]
2,, Zn
3[Fe (CN)
6]
2In one or more.
5. Preparation of catalysts method as claimed in claim 4 is characterized in that ZnCl
2Solution and K
3[Co (CN)
6] solution is that 1: 1～8: 1 ratio reaction obtains Zn with its solute mass ratio
3[Co (CN)
6]
2
6. Preparation of catalysts method as claimed in claim 4 is characterized in that: Ni among its DMC
3[Co (CN)
6]
2, Fe[Co (CN)
6], Ni
3[Fe (CN)
6]
2, Zn
3[Fe (CN)
6]
2Amount be Zn
3[Co (CN)
6]
22～10%wt of amount; NiCl in the soluble metallic salt
2, FeCl
3, NiSO
4, Fe
2(SO
4)
3Total amount be ZnCl
20～20%wt of amount.
7. Preparation of catalysts method as claimed in claim 4 is characterized in that P, the A introducing in catalyst preparation process: selectively respectively at ZnCl
2Add in solution and the cleaning solution, addition P is 0～1%, and A is 0～5%; Major part adds after organic complexing agent replaces catalyst pulp moisture content, and its total amount is Zn
3[Co (CN)
6]
25～100%wt of amount; P: A (mass ratio) is 0～1: 3.
8. the catalyst of a claim 1 is used to produce the PPOX two or the trihydroxylic alcohol polyether polyol of molecular weight 2000～10000, it is characterized in that: with lower molecular weight is that PPOX two or trihydroxylic alcohol between 400～1000 made initiator, the catalyst use amount is 8～30ppm, and the polymeric reaction temperature scope is 80～210 ℃.
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN 02113051 CN1459332A (en) | 2002-05-24 | 2002-05-24 | Complex catalyst contg. two or more than two kinds of bimetal cyanide, prepn. method and application thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN 02113051 CN1459332A (en) | 2002-05-24 | 2002-05-24 | Complex catalyst contg. two or more than two kinds of bimetal cyanide, prepn. method and application thereof |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN1459332A true CN1459332A (en) | 2003-12-03 |
Family
ID=29426423
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| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
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| Country | Link |
|---|---|
| CN (1) | CN1459332A (en) |
Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN100358634C (en) * | 2005-08-29 | 2008-01-02 | 武汉理工大学 | Catalyst of complexes of polymetal and multiple ligand, and preparation method |
| DE102008020980A1 (en) | 2008-04-25 | 2009-10-29 | Henkel Ag & Co. Kgaa | Curable compositions containing silylated polyurethanes based on polyether block polymers |
| WO2011051491A1 (en) | 2009-10-30 | 2011-05-05 | Henkel Ag & Co. Kgaa | Urea-bonded alkoxysilanes for use in sealants and adhesives |
| CN102059134A (en) * | 2010-12-09 | 2011-05-18 | 海南大学 | Method for preparing double metal cyanide catalyst |
| WO2012136658A1 (en) | 2011-04-04 | 2012-10-11 | Henkel Ag & Co. Kgaa | Catalyst for epoxide polymerisation and for the copolymerisation of epoxide with carbon dioxide |
| TWI671115B (en) * | 2018-05-25 | 2019-09-11 | 精遠科技有限公司 | Ion exchange waste gas treatment apparatus and method therefor |
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2002
- 2002-05-24 CN CN 02113051 patent/CN1459332A/en active Pending
Cited By (10)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN100358634C (en) * | 2005-08-29 | 2008-01-02 | 武汉理工大学 | Catalyst of complexes of polymetal and multiple ligand, and preparation method |
| DE102008020980A1 (en) | 2008-04-25 | 2009-10-29 | Henkel Ag & Co. Kgaa | Curable compositions containing silylated polyurethanes based on polyether block polymers |
| WO2011051491A1 (en) | 2009-10-30 | 2011-05-05 | Henkel Ag & Co. Kgaa | Urea-bonded alkoxysilanes for use in sealants and adhesives |
| DE102009046269A1 (en) | 2009-10-30 | 2011-05-05 | Henkel Ag & Co. Kgaa | Urea-bound alkoxysilanes for use in sealants and adhesives |
| US8501903B2 (en) | 2009-10-30 | 2013-08-06 | Henkel Ag & Co. Kgaa | Urea-bonded alkoxysilanes for use in sealants and adhesives |
| CN102059134A (en) * | 2010-12-09 | 2011-05-18 | 海南大学 | Method for preparing double metal cyanide catalyst |
| CN102059134B (en) * | 2010-12-09 | 2012-10-31 | 海南大学 | Method for preparing double metal cyanide catalyst |
| WO2012136658A1 (en) | 2011-04-04 | 2012-10-11 | Henkel Ag & Co. Kgaa | Catalyst for epoxide polymerisation and for the copolymerisation of epoxide with carbon dioxide |
| US9458286B2 (en) | 2011-04-04 | 2016-10-04 | Henkel Ag & Co. Kgaa | Catalyst for epoxide polymerisation and for the copolymerisation of epoxide with carbon dioxide |
| TWI671115B (en) * | 2018-05-25 | 2019-09-11 | 精遠科技有限公司 | Ion exchange waste gas treatment apparatus and method therefor |
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