CN1304459C - Bimetallic cyanide complex catalyst for silicon-containing carbon chain polymer - Google Patents
Bimetallic cyanide complex catalyst for silicon-containing carbon chain polymer Download PDFInfo
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Abstract
The present invention discloses a bimetallic cyanide complex catalyst in which a siloxane polymer containing silicon and carbon chains is used as a functional polymer (A), wherein the molecular weight of A is from 300 to 6000; a catalyst accounts for 2 to 70 wt%. The catalyst is easy to prepare, separate, dry and pulverize. The catalyst is used for polymerizing epoxides in a ring opening mode to prepare polyether polyhydric alcohol, and has high activity. The obtained polyether polyhydric alcohol has a very low unsaturation degree and low viscosity. The obtained polyether polyhydric alcohol is suitable for reaction temperature of 80 to 180 DEG C, and can bear reaction temperature which is as high as 210 DEG C.
Description
Technical field
The present invention relates to the bimetallic cyanide complex catalyst field
Background technology
AM General rubber for tire company discloses the patented technology that double metal cyanide (DMC) complex catalyst is used for epoxide ring-opening polymerization from nineteen seventies, 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 (DMC cat) composition is generally:
Ma
1[M
2(CN)
b(G)
c]
dXM
3(X)
eWH
2OyL
1ZL
2Formula I
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 ion 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), Ir
(III), Rh
(III), 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
-, A, X can be identical or different
A, b, c, d, e satisfy the positive and negative charge balance
L1 represents water-soluble heteroatoms organic complexing agent as alcohol, aldehyde, ketone, ether, ester, acid amides, nitrile, sulfide or its mixture, and wherein trimethyl carbinol TBA has been a known technology as complexing agent.
L2 represents the functional polymer
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]
2XZnCl
2WH
2OyL
1YL
2Formula II
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.
DMC cat does not have the functional polymer in the patent early, as L1 among the DMC cat of USP5158922 (Arco company) is Glyme (glycol dimethyl ether) or Diglyme (diethylene glycol dimethyl ether) substantially, active low, as the example: TriMethylolPropane(TMP) polyoxytrimethylene (M
n=470)) 21.5g makes initiator, and 145ml THF makes solvent, cat 530ppm (the finished product are as follows relatively), and 90 ℃ of following induction time 9h, total reaction time 12h gets product hydroxyl value 16mgKOH/g, degree of unsaturation＜0.02mol/kg; USP5470813 (Arco company) finds that two kinds of salts solutions react by intense mixing such as homogenizers, makes organic complexing agent with TBA, makes non-crystalline state cat, example: polyoxytrimethylene trivalent alcohol (M
n=700) 685g makes initiator, cat 250ppm, 105 ℃ of following induction time 85min, maximum speed of reaction 10.5g PO/min, degree of unsaturation＜0.006mol/kg, (not giving hydroxyl value, by the molecular weight that feeds intake about 6660); USP5482908 (Arco company) begins with the high-molecular weight functional polymer as L among the formula I
2, its DMC cat makes coordination agent with TBA, contains 5～80%wt polyethers (M
n＞500), activity is improved, and its polyethers end group can be hydroxyl, ammonia, ester, ether etc., preferentially uses the polyoxytrimethylene two or the trivalent alcohol of molecular weight 2000～4000.It contains polyoxytrimethylene dibasic alcohol (M for example (to be included in USP5536883)
n=4000) the DMC cat 100ppm of 45.8%wt, system polyoxytrimethylene triol (M
n=6000) time, speed of reaction 6.69kgPO/gCo/min in the time of 105 ℃ (pressure 0.07MPa during reaction), degree of unsaturation 0.0042mol/kg; Contain 5～80%wt band tert-hydroxyl group polyether glycol among USP5545601 (corresponding CN application number 96119923), its improved DMC cat of USP5637673 (Arco company), more high reactivity is arranged, obtained polyethers is low-unsaturation-degree more, and for example it contains 18%wt polyoxytrimethylene dibasic alcohol (M
n=4000) the cat activity of tert-hydroxyl end capped polyether and 9%wt TBA: system polyoxytrimethylene trivalent alcohol (M
n=6000), with 70g polyoxytrimethylene trivalent alcohol (M
n=700) make initiator, cat 100ppm, (reaction pressure 0.07MPa) maximum rate 29.4g PO/min makes polyoxytrimethylene trivalent alcohol (M during 105 ℃ of reactions
n=6000), degree of unsaturation 0.0043mol/kg.DMC cat contains functional polymer or certainly this functional polymer water-soluble salt of deriving out of 2～80%wt except that polyethers among the CN1228039A (Arco company), and described functional polymer is selected from polyester, polycarbonate, oxazoline polymkeric substance, poly (alkylenimines), toxilic acid-copolymer-maleic anhydride, Natvosol, starch and polyacetals.Its activity when for example containing the functional polymer among the cat: 70g polyoxytrimethylene trivalent alcohol (M for polyvinyl methyl ether
n=700) make initiator, cat 25ppm, 105 ℃ of following speed of reaction (reaction pressure 0.07MPa) 25.0g PO/min makes polyoxytrimethylene trivalent alcohol (M
n=6000).The made DMC cat of USP6204357 (Bayer company) makes complexing agent with TBA, contain functional polymer's cyclodextrin, its cyclodextrin that is suitable for has: unsubstituted ring dextrin or their ester, alkyl oxide, hydroxyalkyl ether, alkoxycarbonyl alkyl ether and carbonylic alkyl ether derivant.DMC cat contains 2 of 13.8%wt in the example preferably, 6-DM-, its activity: with 50g polyoxytrimethylene dibasic alcohol (M
n=1000) make initiator, cat 20ppm, induce in 105 ℃ of following stills and when reacting pressure keep 0.25MPa, induction time 197min, total reaction time 478min, making hydroxyl value is 29.9mgKOH/g (M
n=3800), degree of unsaturation is 0.008mol/kg, and viscosity (25 ℃) is the polyoxytrimethylene dibasic alcohol of 1022mpas; The made DMC cat of USP6291388 (Bayer company) makes complexing agent with TBA, contains the Polyethoxyolefin ether (M of 5～80%wt
n＞500) as the functional polymer, activity increases, and DMC cat contains Polyethoxyolefin ether 41.1%wt in the example preferably, its activity: with 50g polyoxytrimethylene dibasic alcohol (M
n=1000) make initiator, cat 15ppm, induce in 105 ℃ of following stills and when reacting pressure keep 0.25MPa, total reaction time 395min (not having concrete induction time), making hydroxyl value is 29.8mgKOH/g (M
n=3810), degree of unsaturation is 0.011mol/kg, and viscosity (25 ℃) is the polyoxytrimethylene dibasic alcohol of 935mpas; The obtained basic crystalline state type DMC cat of USP6323375 (Bayer company) makes complexing agent with TBA, moisture 1～10%wt among the cat, water-soluble salt (ZnCl
2) 5～25%wt, contained functional polymer is: polyethers, polyester, polycarbonate, poly-alkane alkene glycol, sorbitan ester, poly-alkane allyl diglycol ether, polyacrylamide, acrylamide and acrylic acid copolymer, polyacrylic acid, vinylformic acid-maleic acid, polyacrylonitrile, polyalkyl acrylate, polyalkyl methacrylate, polyvinyl methyl ethermaleic anhydride, Vinyl Acetate Copolymer, polyvinyl alcohol, poly-(N-V-Pyrol RC), N-V-Pyrol RC-maleic acid, polyethylene methyl ketone, poly-(4-vinylphenol), vinylformic acid-styrol copolymer oxazoline polymkeric substance, poly-alkane enamine, maleic acid and maleic anhydride copolymers, Natvosol, polyacetal.DMC cat contains M in its comparatively ideal example
n=2300 polydiethylene glycol adipate (by the slight collateralization of TriMethylolPropane(TMP)) 12.3%wt, its activity: with 50g polyoxytrimethylene dibasic alcohol (M
n=1000) make initiator, cat 15ppm, induce in 105 ℃ of following stills and when reacting pressure keep 0.25MPa, induction time 80min, total reaction time 335min, making hydroxyl value is 27.4mgKOH/g (M
n=4140), degree of unsaturation is 0.005mol/kg, and viscosity (25 ℃) is the polyoxytrimethylene dibasic alcohol of 1084mpas.
Best DMC cat activity also haves much room for improvement, and DMC cat performance shows reactive behavior in the above patent, and the degree of unsaturation of made polyether glycol, viscosity performances such as (the wide promotion viscosity that distributes increase) still remain to be improved.The high-molecular weight functional polymer does not mention in the above patent that use is a kind of to filtering the functional polymer of the favourable Action of Surfactant of having held concurrently because influences such as viscosity generally can be added to the difficulties to the cat filtration.When introducing its DMC cat in the past in the patent, used temperature of reaction is substantially at 90～105 ℃, the system higher molecular weight for example o'clock just has to adopt comparatively high temps for example about 130 ℃ in M6000～8000, reason is to think that obtained unsaturation in polyols obviously increased when temperature was high, molecular weight distribution obviously broadens, but low temperature is long following inductive phase, and speed of response is slow, can not fully reflect the advantage of DMC cat.
Summary of the invention
The object of the invention provides a kind of high reactivity DMC complex catalyst (being called for short cat) of the siloxane polymer with the silicon-carbon chain.Find among the cat in existing patent the used functional polymer, another kind of functional polymer's result of use, it can share with known functional polymer, also can use separately.This functional polymer has bigger promoter action to activity of such catalysts, and can tolerate higher reaction temperatures (140～180 ℃), and in the cat making processes, the slurry that is added with this functional polymer easily filters, and the wet cat of gained is easily dried, and easily pulverize the oven dry back.This type of functional polymer is a kind of siloxane polymer (being called for short A) of siliceous carbochain.
(1) bimetallic cyanide complex catalyst of the present invention, general formula is:
M
a 1[M
2(CN)
b]
d·xM
3(X)
c·wH
2O·yT·jP·zA
Wherein:
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)Preferentially be selected from Zn
(II), Fe
(III), Ni
(II)In one or more, and with Zn
(II)Be main.
M
2Be that at least a transition metal ion is selected from: Fe
(II), Fe
(III), Co
(II), Co
(III), Cr
(II), Cr
(III), Mn
(II), Mn
(III), V
(IV), V
(V), Ir
(III), Rh
(III), Ru
(II), Ni
IIPreferentially be selected from Fe
(III), Co
(III), and with Co
(III)Be main.
M
3Represent M
1And/or M
2In one or more, preferentially select Zn
(II)
X is for being selected from CN
-, F
-, Cl
-, Br
-, I
-, OH
-, NO
2 2-, CO
3 2-, NO
3 -, SO
4 2-, CNO
-, C
2O
4 2-, CNS
-, NCO
-, NCS
-And carboxylate radical RCOO
-, preferentially select Cl
-, SO
4 2-In one or two, preferential Cl when selecting one of them
-
A, b, c, d satisfy the positive and negative charge balance
T is selected from water-soluble heteroatoms organic complexing agent as alcohol, aldehyde, ketone, ether, ester, acid amides, nitrile, sulfide or its mixture, preferentially select the trimethyl carbinol (TBA), glycol dimethyl ether (Glyme), diethylene glycol dimethyl ether (Diglyme), tertiary amyl alcohol (TPA), preferably the trimethyl carbinol (TBA).
P is that polyether glycol comprises the poly-third oxygen alkene, the poly-third oxygen ethoxy copolymer polyols, 2～8 functionality, preferential 2～3 functionality, molecular weight 500～10000, preferential 1000～8000, best 2000～4000.
A is a kind of organo-siloxane that contains the Si-C chain:
R wherein
1, R
2, R
3, R
4Be methyl, ethyl, propyl group, butyl, R
1, R
2, R
3, R
4Can be identical or different.Molecular weight 300～6000, preferential 1000～4000.
X=0.1～5, w=0.1～1, y=0.1～1, (satisfy P content 0～5%wt) among the cat, A content 2～70%wt) among the cat (is satisfied in z=0.01～2.5 in j=0～0.15;
M, n, r, s value satisfy above-mentioned molecular weight.
Be surprised to find contain A among the DMC cat after, active and temperature tolerance obviously improves, made polyether glycol has utmost point low-unsaturation-degree, A contains 2～70%wt in cat, preferential 5～50%wt, best 10～40%wt.P content can be limited to 0～5%wt, best 2～5%wt.
(2) technological process
A. water distribution dissolubility salt M
3(X)
cSolution is typically used ZnCl
2, contain water-soluble heteroatoms organic complexing agent, use the trimethyl carbinol preferably, this organic complexing agent concentration range 10%～80%wt selectively contains P or A, and the concentration of P is 0.05～1%, and A is 0.1～5%, water-soluble salt M
3(X)
cConcentration range 10%～saturated.
B. join typically K of basic metal hexacyanocobaltate acid salt
3[Co (CN)
6] solution, selectively be added with and contain water-soluble heteroatoms organic complexing agent, use trimethyl carbinol TBA preferably, this organic complexing agent concentration range 10%～80%wt, K
3[Co (CN)
6] strength of solution scope 1%～saturated, and selectively be added with K
3[Fe (CN)
6], measure and be K
3[Co (CN)
6] 0～20%wt, best 0～10%wt.
C. can select in " a " solution be added in " b " solution or conversely in " b " solution be added in " a " M
3(X)
c/ K
3[Co (CN)
6] mass ratio is 1: 1～7: 1, material stirs at a high speed or circulates during reaction, generates M
a 1[M
2(CN)
b]
d, typically be Zn
3[Co (CN)
n]
2And water byproduct dissolubility sylvite, typically be KCl.
D. after reaction is finished, isolate especially an alkali metal salt of various water-soluble salts with the filtration in the common patent, method such as centrifugal, obtain DMC cat mashed prod, with the water-soluble heteroatoms organic complexing agent aqueous solution, wash with the trimethyl carbinol aqueous solution preferably, so-called washing is to add the organic complexing agent aqueous solution in the mashed prod to form the isolating again several repetitive process of slurry.Used organic complexing agent concentration range 10%～80%wt in the washing process selectively contains P and/or the 0.1～5%A of 0.1%～1%wt in the washings.
E. washing finishes the back (to detect in the parting liquid typically K of alkalimetal ion
+Concentration reaches below the 500ppm, 200ppm is following for indicating better), (to moisture content＜20%wt) add P and A, add-on should be greater than theoretical aequum, and excessive amount is slurry and isolates P and the A amount that is had in the coordination agent solution at last to replace in the slurries partly moisture content with pure organic complexing agent.Stir or the 0.5～5h that circulates, 1～3h better.
F. separate with spreading mass, can obtain the pasty state cat of solid content 10～30% by centrifugation or press filtration
G. mashed prod is through 40～80 ℃ of oven dry, or 0～80 ℃ of negative pressure drains to constant weight (solid content reaches 90% and is ground into powder when above), is the DMC complex catalyst (being called for short catalyzer of the present invention or cat) that has silicon-carbon chain polymerization thing of the present invention.
Effect of the present invention is when cat is used to make polyether glycol active high, for example 70g polyoxytrimethylene dibasic alcohol (M
n=416) make initiator, cat 15ppm, PO pressure 0.05MPa before the induced reaction keeps 0.07MPa during reaction, system polyoxytrimethylene dibasic alcohol (M
n=4000) test-results: inductive phase 40min, total reaction time 240min, maximum speed of reaction 12g PO/min.
The gained polyether glycol has ultralow degree of unsaturation, can reach 0.001～0.005mol/kg scope, and during higher molecular weight such as 6k～10k, below the cat 30ppm, degree of unsaturation still can satisfy this scope in system.
DMC cat of the present invention is used to make molecular weight 2000～10, cat consumption 8～30ppm when 000 polyoxytrimethylene two or trivalent alcohol, 80～180 ℃ of temperature of reaction, 105～150 ℃ of scopes are better, be surprised to find the polyether glycol that under comparatively high temps (140～180 ℃), makes, its performance (as degree of unsaturation, viscosity and molecular weight distribution) does not have variation, and significant reaction is accelerated, and being surprised to find can be high temperature resistant to 210 ℃ even higher in the certain hour in the reaction process.
Cat reaction induction time of the present invention is extremely short, be not more than 40ppm usage quantity (the finished product relatively), 130 ℃ of temperature of reaction, by the synthetic target polyvalent alcohol molecular weight of low molecular weight polycaprolactone propylene oxide two or trivalent alcohol (molecular weight 400～1000) 2000 when above, induction time 2～20min, speed of reaction test: 2 liters of autoclave pressures, 70g polyoxytrimethylene dibasic alcohol (M
n=416) make initiator, cat 10ppm, 130 ℃ of temperature of reaction, system polyoxytrimethylene dibasic alcohol (M
n=6000), maximum rate 60gPO/min or 50kgPO/gCo/min.
Cat slurry of the present invention easily filters, and the wet cat of gained is easily dried, and easily pulverize the oven dry back.
Embodiment
Embodiment 1 system cat Zn
3[Co (CN)
6]
2ZnCl
20.5H
2O0.15TBA0.015P0.092A
In the one batching still, with 24kg ZnCl
2Be dissolved in the 50L TBA/90L deionized water, in another batching still, 6kg K
3[Co (CN)
6] be dissolved in the 90L deionized water, two kinds of solution are added in the reactor in the 30min, and circulation simultaneously mixes, and enters the film circulation behind the 1.5h, and parting liquid distills through still kettle, and gained TBA and water are made into 50% TBA solution and wash 5h (detection K with 300L
+300ppm), displace part moisture content in the slurry with the pure TBA 3h of 200L again, continue membrane sepn, be concentrated into slurry 300L.Add 0.6kg polyoxytrimethylene trivalent alcohol (M
n=3000) and 1.8kg A (M
n=2000, R in the structural formula
1, R
2, R
3, R
4Be methyl, x/y is 1: 1 mol ratio) circulation 2h, till the solid content 18%, negative pressure drying is to constant weight with the slurry press filtration, pulverize cat A 8.5kg.
Through ultimate analysis, thermogravimetric analysis, extraction process and liquid-phase chromatographic analysis: Zn=27.1%, Co=12.2%, H
2O=0.93%, TBA=1.2%, P=4.7%, A=14.3%.
Comparative example 1 system cat Zn
3[Co (CN)
6]
2ZnCl
20.5H
2O0.15TBA0.06P
With embodiment 1 operation, do not add A, only add 2.4kg polyoxytrimethylene trivalent alcohol (M
n=3000) get cat B 8.3kg.
Zn＝27.2％，Co＝12.2％，H
2O＝0.91％，TBA＝1.2％，P＝19.2％。
Embodiment 2 system cat Zn
3[Co (CN)
6]
2ZnCl
20.5H
2O0.15TBA0.12A
With embodiment 1, but only add 2.4Kg A, get cat E 8.6kg.
Through ultimate analysis, thermogravimetric analysis, extraction process and liquid-phase chromatographic analysis: Zn=27.3%, Co=12.4%, H
2O=0.89%, TBA=1.2%, A=14.6%.
System polyether glycol (1)
70g polyoxypropyleneglycol (M
n=416) make initiator, cat 8-30ppm (polyvalent alcohol of made relatively theoretical molecular), place the 2L autoclave pressure, stir down, temperature vacuumizes 30min under 105 ℃, remove micro-moisture, adds propylene oxide 20g, pressure 0.05MPa, after pressure sharply descends, under the residual epoxide propane certain pressure, remain under certain temperature of reaction and add, the process afterreaction phase is to consume all propylene oxide in the still, take out volatile matter for 90 ℃, obtain polyvalent alcohol, carry out hydroxyl value, double bond content, mensuration such as viscosity.Example A is with cat A (15ppm) system polyoxytrimethylene dibasic alcohol (M
n=4000)
With above-mentioned steps, 105 ℃, make polyvalent alcohol under the 0.07MPa, the result is as follows:
Inductive phase (min): 55
Total reaction time (min): 300
Maximum speed of reaction (g PO/min): 10
Polyvalent alcohol:
Hydroxyl value (mg KOH/g): 29.1
Double bond content (mol/Kg): 0.0040
Viscosity (25 ℃, mpas): 950
B is with cat E 15ppm for example, system polyoxytrimethylene dibasic alcohol (M
n=4000), condition is the same, and the result is as follows:
Inductive phase (min): 40
Total reaction time (min): 320
Maximum speed of reaction (g PO/min): 10.5g/min
Polyvalent alcohol:
Hydroxyl value (mg KOH/g): 28.2
Double bond content (mol/Kg): 0.0020
Viscosity (25 ℃, mpas): 780
Comparative examples A
With Cat.B, condition is the same, and the result is as follows:
Inductive phase (min): 80min
Total reaction time (min): 400
Maximum speed of reaction (g PO/min): 8g/min
Polyvalent alcohol:
Hydroxyl value (mg KOH/g): 28.9
Double bond content (mol/Kg): 0.0060
Viscosity (25 ℃, mpas): 920
Comparative example B
With cat A, condition is the same, but after inducing end, temperature rises to 205 ℃ of reactions.
Reaction times (min): 15
Maximum speed of reaction (g PO/min): 60
Polyvalent alcohol: hydroxyl value (mg KOH/g): 28.40
Double bond content (mol/Kg): 0.0057
Viscosity (25 ℃, mpas): 780
Comparative example C
Cat A, cat E the same charging capacity respectively relatively, treat theoretical molecular to 4000 after, temperature rises to 130 ℃ and continues reaction, pressure＜0.15MPa stops when inlet amount is low to moderate 5gPO/min, the cat concentration of relative theory molecular weight.
With cat A result: do to M
n=6000, this moment cat concentration 10ppm.
With cat E result: do to M
n=5800, this moment cat concentration 10.3ppm
System polyether glycol (2)
70g polyoxypropyleneglycol (M
n=416), cat A30ppm (made relatively theoretical molecular M
n=2000), place the 2L autoclave pressure, stir down, vacuumize 30min at a certain temperature, remove micro-moisture, add propylene oxide to pressure 0.05MPa, after pressure sharply descended, residual epoxide propane kept adding under this certain temperature of reaction under 0.07MPa pressure, the process afterreaction phase is to consume all propylene oxide in the still, take out volatile matter for 90 ℃, obtain polyvalent alcohol, carry out hydroxyl value, double bond content, mensuration such as viscosity and molecular weight distribution.Example 1 is with above-mentioned steps, makes polyvalent alcohol under 105 ℃, and the result is as follows:
Inductive phase (min): 55
Total reaction time (min): 160
Maximum speed of reaction (g PO/min): 10
Polyvalent alcohol:
Hydroxyl value (mg KOH/g): 58.20
Double bond content (mol/Kg): 0.0018
Viscosity (25 ℃, mpas): 300
Molecular weight distribution (M
w/ M
n): 1.11
Example 2 is with above-mentioned steps, 140 ℃ induce finish after, make polyvalent alcohol under 190 ℃, the result is as follows:
Inductive phase (min):＜1
Total reaction time (min): 10
Maximum speed of reaction (g PO/min): 53
Polyvalent alcohol:
Hydroxyl value (mg KOH/g): 57.1
Double bond content (mol/Kg): 0.0050
Viscosity (25 ℃, mpas): 305
Molecular weight distribution (M
w/ M
n): 1.12
Catalyst performance relatively when used siloxane polymer was different molecular weight among example 3 the present invention
With embodiment 1 processing step, used A similar, the molecular weight difference is made polyoxytrimethylene dibasic alcohol (M with institute's controlling catalyst by routine A
n=4000) result is as follows:
Embodiment 3
With embodiment 1 processing step, with P of the same race and A, amount is different, makes polyoxytrimethylene dibasic alcohol (M with institute's controlling catalyst by routine A
n=4000) result is as follows:
| Catalyzer | A/% (dosage/kg) | 2.0(0.18) | 8.2(0.80) | 14.3(1.80) | 21.2(3.00) | 32.5(4.50) |
| P/% (dosage/kg) | 4.5(0.40) | 4.3(0.40) | 4.7(0.60) | 4.4(0.60) | 4.1(0.60) | |
| Zn/％ | 31.3 | 29.3 | 27.1 | 24.9 | 21.2 | |
| Co/％ | 14.1 | 13.2 | 12.2 | 11.2 | 9.5 | |
| H 2O/％ | 0.95 | 0.94 | 0.93 | 0.95 | 0.97 | |
| TBA/％ | 1.1 | 1.1 | 1.2 | 1.3 | 1.5 | |
| The system polyethers | Induce/min | 95 | 70 | 55 | 60 | 70 |
| Total reaction/min | 350±5 | 340±5 | 300±5 | 330±5 | 360±5 | |
| Hydroxyl value/mgKOHg -1 | 29.6 | 29.5 | 29.1 | 29.3 | 29.9 | |
| Two key/mol/Kg -1 | 0.0050 | 0.0049 | 0.0040 | 0.0052 | 0.0058 | |
| Distribution/M wM n -1 | 1.22 | 1.19 | 1.13 | 1.15 | 1.23 |
Claims (21)
1, a kind of bimetallic cyanide complex catalyst of siliceous carbochain siloxane polymer, its general formula is:
M
a 1[M
2(CN)
b]
d·xM
3(X)
c·wH
2O·yT·jP·zA
M wherein
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 ion is selected from: Fe
(II), Fe
(III), Co
(II), Co
(III), Cr
(II), Cr
(III), Mn
(II), Mn
(III), V
(IV), V
(V), Ir
(III), Rh
(III), Ru
(II)Or Ni
(II)
M
3Represent M
1And/or M
2In one or more;
X is for being selected from 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
-
A, b, c, d satisfy the positive and negative charge balance
T is selected from water-soluble heteroatoms organic complexing agent: alcohol, aldehyde, ketone, ether, ester, acid amides, nitrile, sulfide or its mixture;
P is that polyether glycol comprises the poly-third oxygen alkene, the poly-third oxygen ethoxy copolymer polyols, 2～8 functionality, molecular weight 500～10000;
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 polymer of siliceous carbochain:
R wherein
1, R
2, R
3, R
4Be methyl, ethyl, propyl group, butyl, R
1, R
2, R
3, R
4Can be identical or different; The A molecular weight is 300～6000, and m, n, r, s value satisfy above-mentioned molecular weight.
2, catalyzer according to claim 1 is characterized in that silicon-carbon chain siloxane polymer content accounts for 2～70% of catalyst weight in the general formula.
3,, it is characterized in that silicon-carbon chain siloxane polymer content accounts for 10～40% of catalyst weight in the general formula as catalyzer as described in the claim 2.
4, catalyzer according to claim 1 is characterized in that M
1Be selected from Zn
II, Fe
IIIOr Ni
IIIn one or more.
5, catalyzer according to claim 4 is characterized in that M
1Be Zn
II
6, catalyzer according to claim 1 is characterized in that M
2Be selected from Fe
III, Co
III.
7, catalyzer according to claim 6 is characterized in that M
2Be Co
III
8, catalyzer according to claim 1 is characterized in that X is selected from Cl
-, SO
4 2-
9, catalyzer according to claim 8 is characterized in that X is Cl
-
10, according to the described catalyzer of claim 1, the functionality that it is characterized in that P is 2～3.
11, catalyzer according to claim 10, the molecular weight that it is characterized in that P is 1000～8000.
12, catalyzer according to claim 11, the molecular weight that it is characterized in that P is 2000～4000.
13, catalyzer according to claim 1, the molecular weight of A are 1000～4000.
14, catalyzer according to claim 1, T is selected from the trimethyl carbinol, glycol dimethyl ether, diethylene glycol dimethyl ether or tertiary amyl alcohol.
15, according to the described catalyzer of claim 14, T is the trimethyl carbinol.
16, catalyzer according to claim 1 is characterized in that silicon-carbon chain siloxane polymer adds under the following three state: 1. prepare water-soluble salt M in this Preparation of Catalyst
3(X)
cSolution the time; When 2. washing this catalyst pulp; 3. replace water to water-content during at pure organic complexing agent less than 20%wt.
17,, it is characterized in that silicon-carbon chain siloxane polymer add-on in the process of this catalyzer of preparation is respectively: 1. prepare M as catalyzer as described in the claim 16
3(X)
cThe aqueous solution time be 0.1～5%; When 2. washing this catalyst pulp, in washings, add 0.1～5%; 3. moisture content adds after less than 20%wt in replacing slurry liquid, and add-on is in excess in the theoretical aequum of this catalyzer.
18, catalyzer as claimed in claim 1 is characterized in that the M in the general formula
3(X)
cBe ZnCl
2
19, catalyzer as claimed in claim 16 is characterized in that washings and pure organic complexing agent are respectively the trimethyl carbinol aqueous solution and the trimethyl carbinol.
20, catalyzer as claimed in claim 1 is characterized in that the A in the general formula can replace or partly replace P.
21, catalyzer as claimed in claim 1, the use temperature that it is characterized in that siliceous carbochain siloxane polymer bimetallic cyanide complex catalyst is 80～180 ℃, can be high temperature resistant to 210 ℃.
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| CNB021129509A CN1304459C (en) | 2002-04-29 | 2002-04-29 | Bimetallic cyanide complex catalyst for silicon-containing carbon chain polymer |
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|---|---|---|---|
| CNB021129509A CN1304459C (en) | 2002-04-29 | 2002-04-29 | Bimetallic cyanide complex catalyst for silicon-containing carbon chain polymer |
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| CN1304459C true CN1304459C (en) | 2007-03-14 |
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| CN100368460C (en) * | 2005-06-17 | 2008-02-13 | 中国科学院过程工程研究所 | Double metal cyanide catalyst and its preparation method |
| CN103638872B (en) * | 2013-12-16 | 2015-07-29 | 南京美思德新材料有限公司 | A kind of trisiloxanes polyether ester tensio-active agent and preparation method thereof |
| DE102014209408A1 (en) * | 2014-05-19 | 2015-11-19 | Evonik Degussa Gmbh | Ethoxylate preparation using highly active double metal cyanide catalysts |
| DE102014209407A1 (en) * | 2014-05-19 | 2015-11-19 | Evonik Degussa Gmbh | Highly active double metal cyanide catalysts and process for their preparation |
Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1229805A (en) * | 1993-12-23 | 1999-09-29 | 阿克奥化学技术公司 | Polyurethane foam-supported double metal cyanide catalysts for polyol synthesis |
| CN1304946A (en) * | 2000-08-16 | 2001-07-25 | 中国科学院山西煤炭化学研究所 | Composite catalyst bimetal cyanide and its preparing process and application |
| CN1305396A (en) * | 1998-06-08 | 2001-07-25 | 拜尔安特卫普有限公司 | Silylated double metal cyanide complex catalysts |
| CN1311716A (en) * | 1998-07-31 | 2001-09-05 | 拜尔公司 | Bimetallic-cyanide catalysts used for preparing polyether polyols |
| CN1340072A (en) * | 1999-02-11 | 2002-03-13 | 拜尔公司 | Double metal cyanide catalyst for producing polyether polyols |
-
2002
- 2002-04-29 CN CNB021129509A patent/CN1304459C/en not_active Expired - Fee Related
Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1229805A (en) * | 1993-12-23 | 1999-09-29 | 阿克奥化学技术公司 | Polyurethane foam-supported double metal cyanide catalysts for polyol synthesis |
| CN1305396A (en) * | 1998-06-08 | 2001-07-25 | 拜尔安特卫普有限公司 | Silylated double metal cyanide complex catalysts |
| CN1311716A (en) * | 1998-07-31 | 2001-09-05 | 拜尔公司 | Bimetallic-cyanide catalysts used for preparing polyether polyols |
| CN1340072A (en) * | 1999-02-11 | 2002-03-13 | 拜尔公司 | Double metal cyanide catalyst for producing polyether polyols |
| CN1304946A (en) * | 2000-08-16 | 2001-07-25 | 中国科学院山西煤炭化学研究所 | Composite catalyst bimetal cyanide and its preparing process and application |
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