CN101302288A - Continuous preparation of low-unsaturated polyether polyatomic alcohol - Google Patents
Continuous preparation of low-unsaturated polyether polyatomic alcohol Download PDFInfo
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- CN101302288A CN101302288A CNA2008100371608A CN200810037160A CN101302288A CN 101302288 A CN101302288 A CN 101302288A CN A2008100371608 A CNA2008100371608 A CN A2008100371608A CN 200810037160 A CN200810037160 A CN 200810037160A CN 101302288 A CN101302288 A CN 101302288A
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Abstract
The invention relates to a method for preparing unsaturated polyether polyols by utilizing a continuous method and a bi-metallic cyanide complex as the ring opening polymerization catalyst of oxyalkylene. The method mainly resolves the problems exiting in prior art that the catalyst needs the pre-activation when the catalyst is used to continuously prepare the polyether polyols, and the process is complicated and the conversion rate of monomer is relatively low. In the invention, the technical proposal which better resolves the problems is as follows: the bi-metallic cyanide complex catalyst, an initiator and the oxyalkylene are continuously added in a reactor for preparing the unsaturated polyether polyols, and the polyether polyols obtained are continuously taken out of the reactor. The method is applied to the industrial preparation of polyether polyols by the continuous method.
Description
Technical field
The present invention relates to a kind of method of preparing polyether polyol by continuous process, particularly a kind of employing high reactivity double metal cyanide catalyst continuous processing prepares low-unsaturation-degree, the polyether glycol of narrow molecular weight distributions, and can make the transformation efficiency of olefin oxide reach 99.998% method at short notice.
Background technology
Polyether glycol is a kind of important intermediate of preparation urethane, is widely used in preparing urethane foam, elastomerics, coating, tackiness agent, fiber, kinds such as synthetic leather and surfacing material.Usually adopt alkali (KOH) to prepare polyether glycol for catalyzer is used for the olefin oxide ring-opening polymerization.Isomerization easily takes place and generates vinyl carbinol in propylene oxide under alkali (KOH) effect, vinyl carbinol carries out the propylene oxide ring-opening polymerization as initiator and obtains the monohydroxy unsaturated polyether, and the functionality of polyether glycol is diminished, and molecular weight distribution broadens.This monohydroxy unsaturated polyether can influence the performance of polyether glycol, is considered to be in preparation and causes during polyurethane foam crosslinkedly too early, causes overtime crosslinked and change the performance of goods in polyurethane elastomer.In order to reduce the content of monohydroxy unsaturated polyether in the polyether glycol, many patent reports were once arranged (as US3393243, US5010187, US5114619, the US4282387) oxyhydroxide of employing rubidium, caesium, the oxide compound of barium, lithium and oxyhydroxide, the carboxylate salt of alkaline-earth metal etc. is a catalyzer, but all there is DeGrain, catalyzer costliness, the problem of all many-sides such as toxic.
Bimetallic cyaniding complex is a kind of catalyzer of efficient production polyether glycol.Such catalyzer has active high, and consumption is ppm (10
-6) level, therefore, do not need to remove the loaded down with trivial details last handling process of catalyzer; Such catalyzer can not make propylene oxide generation isomerization generate vinyl carbinol; Simultaneously, such catalyzer can also prepare high molecular, the polyether glycol of narrow molecular weight distributions.But, double metal cyanide catalyst prepares in the process of polyether glycol at interrupter method, require a great deal of time and energy consumption removes that lower boiling compound just can make catalyst performance unaffected in the initiator, long phenomenons such as (more than the several hrs) of poisoning of catalyst and inductive phase even so also can occur; In addition, it is wayward that initial reaction stage is prone in short-term (or local) reaction heat, not only increased the operation easier of reaction unit, also can influence the quality of product simultaneously.U.S. Arco Chemical Technology, Inc had once reported (US5689012, CN1176969C) technology of employing double metal cyanide catalyst preparing polyether polyol by continuous process.Be characterized in directly adopting low-molecular-weight polyvalent alcohol (for example propylene glycol, glycerol) to improve single reaction vessel " constructing ratio " for initiator.But a whole set of technology is very complicated, not only need to adopt independent reaction to carry out " the pre-activation " of catalyzer (here " pre-activation " is meant double metal cyanide catalyst, initiator and olefin oxide monomer are carried out induced reaction in batch reactor), defectives such as also existing the monomer multiple spot to feed in raw material increases number of devices, and catalyst consumption monomeric transformation efficiency under situation about not removing is on the low side probably.
Summary of the invention
Technical problem to be solved by this invention is that catalyzer needs pre-activation when having the continuous production polyether glycol in the conventional art, make complex process, and the problem that monomer conversion is on the low side provides a kind of new employing double metal cyanide catalyst continuous processing to prepare the method for low-unsaturated polyether polyatomic alcohol.It is simple that this method has technical process, do not need to carry out " the pre-activation " of catalyzer, olefin oxide only need add and can react rapidly at single inlet, and can reach in next slaking reaction device and transform fully and do not need to remove the advantage of residual monomer.
In order to solve the problems of the technologies described above, the technical solution used in the present invention is as follows: a kind of method of preparing polyether polyol by continuous process comprises:
A) a kind of double metal cyanide catalyst;
B) continuously double metal cyanide catalyst, initiator and olefin oxide are joined reactor;
C) continuously polyether glycol is taken out from reactor;
Wherein double metal cyanide catalyst must have sufficiently high activity, makes olefin oxide be higher than 50% at the interim transformation efficiency of polyreaction, reaches more than 99.998% at the interim transformation efficiency of slaking reaction; The double metal cyanide catalyst of selecting for use comprises following component:
1. a kind of bimetallic cyaniding complex, its weight percent are 40～99.8%;
2. a kind of C with tertiary alcohol structure
4～C
10Organic alcohol, its weight percent are 0.1～30%;
3. a kind of organic ligand that is selected from aliphatic ester, aromatic series monoesters or aromatic diester and composition thereof of surplus.
In the technique scheme, bimetallic cyaniding complex has following general formula:
M
1 a[M
2 b(CN)
c]
d·hM
4 i(X)
j
In the formula: M
1, M
4Be selected from Zn, Fe, Ni, Mn, Co, Sn, Ph, Mo, Al, V, Sr, W, Cu or Cr;
M
2Be selected from Fe, Co, Cr, Mn, Ir, Ni, Rh, Ru or V;
X is selected from halogens, OH
-, NO
3 -, CO
3 2-, SO
4 2-, or ClO
3 2-
A, b, c, d, i and j represent M respectively
1, M
2, CN, [M
2 b(CN)
c], M
4Ion number with X;
The span of h is 0.05～1.0.
M
1Preferred version for being selected from Zn, Ni or Co; M
2Preferred version for being selected from Fe or Co; M
4Preferred version for being selected from Zn or Fe, the preferred version of X is for being selected from Cl
-, Br
-, NO
3 -Or SO
4 2-The span of h is 0.5～1.0.By weight percentage, the C that has tertiary alcohol structure
4～C
10The preferable range of organic alcohol is 10～20%; C with tertiary alcohol structure
4～C
10The preferred version of organic alcohol is the trimethyl carbinol or tertiary amyl alcohol; The organic ligand consumption preferred version that is selected from aliphatic ester, aromatic series monoesters or aromatic diester and composition thereof by weight percentage is 0.1～30%.More preferably scheme is 10～30%; The organic ligand preferred version is for being selected from aromatic diesters, and preferred scheme is for being selected from phthalic ester, and molecular structure is
R in the formula
1Or R
2Be respectively the alkyl of 1～20 carbon atom, R
1Or R
2Preferred version be respectively the alkyl of 1～4 carbon atom, more preferably scheme R
1And R
2Be methyl, ethyl, butyl or the tertiary butyl simultaneously.
The initiator that adds is low-molecular-weight polyether glycol continuously, preferably the polyether glycol of 200～1000 molecular weight, the most preferably polyether glycol of 200～500 molecular weight.For example: hydroxyl value is the polyether Glycols about 280mgKOH/g, and hydroxyl value is the polyether-tribasic alcohol about 360mgKOH/g.
The olefin oxide that adds comprises oxyethane, propylene oxide, butylene oxide ring and their mixture continuously.
The average functionality that the polyether glycol that takes out from reactor continuously has is between 2～8, be preferably 2～3, the molecular weight of polyether glycol is between 500～50000, is preferably between 1000～8000, and the degree of unsaturation of polyether glycol is between 0.002～0.010.
The reactor that the present invention adopts is a still formula stirred reactor, and tubular reactor preferably has the tank reactor of high speed outer circulation device interchanger.The polyether glycol that takes out from reactor can stay for some time in having another reactor of lagging facility, monomeric transformation efficiency is reached more than 99.98%, because catalyzer has very high initial activity, therefore can save pre-activation step, simplify technology, obtained better technical effect.
The present invention is further elaborated below by embodiment.
Embodiment
[embodiment 1]
The preparation of A, bimetallic cyanide complex catalyst
8 gram Cobalt Potassium Cyanides are added 140 ml distilled waters make its dissolving.At rotating speed is the ZnCl that slowly adds 38.5% (weight) under 8000 rev/mins
2The aqueous solution 65 restrains, and adds the mixed solution of 100 milliliters of trimethyl carbinols and 100 ml distilled waters subsequently, stirs after 20 minutes, adds 14.7 gram dimethyl phthalate and 200 ml distilled waters, stirs after 10 minutes, with sand core funnel vacuumizing filtration.The solid that obtains is added 150 milliliters of trimethyl carbinols and 60 ml distilled waters, and stirring is after 10 minutes down to be 8000 rev/mins at rotating speed, and adding 10.6 gram dimethyl phthalates stir after 10 minutes centrifugation.The solid that obtains is added 200 milliliters of trimethyl carbinols again, and stirring is after 10 minutes down to be 8000 rev/mins at rotating speed, and adding 6.7 gram dimethyl phthalates stir after 10 minutes centrifugation.Solid is got solid powder th-1 catalyst I 12.9 grams 60 ℃ of following vacuum-drying to constant weights.
By analysis: Co 8.4% (weight) Zn 22.1% (weight)
The trimethyl carbinol 15.2% (weight) dimethyl phthalate 21.4% (weight)
B. olefin oxide successive polymerization
A. 40 gram initiators (hydroxyl value is the polyoxytrimethylene propylene glycol about 280.0 milligrams of KOH/ gram) and 0.0060 are restrained in the voltage-resistant reactor that catalyst I joins 1 liter, vacuumize and be warming up to more than 120 ℃, slowly add 160 gram propylene oxide, open the continuous discharging of top discharge valve after question response is complete, be 160: 40: 0.006 adding reactants with propylene oxide/initiator/catalyst I continuously in proportion, keeping reaction volume is 1 liter, mean residence time is 50 minutes, temperature of reaction is 140～145 ℃, the pressure of reactor is at 0.14～0.16MPa, after three mean residence times, sampling analysis, its result is as follows:
Hydroxyl value: 55.6 milligrams of KOH/ gram degrees of unsaturation: 0.0070 mmole/gram
Molecular weight distribution (Mw/Mn): 1.25 residual monomer contents: 38ppm
B. 50 gram initiators (hydroxyl value is the polyoxytrimethylene glycerol about 336.0 milligrams of KOH/ gram) and 0.010 are restrained in the voltage-resistant reactor that catalyst I joins 1 liter, vacuumize and be warming up to more than 120 ℃, slowly add 250 gram propylene oxide, open the continuous discharging of top discharge valve after question response is complete, be 250: 50: 0.010 adding reactants with propylene oxide/initiator/catalyst I continuously in proportion, keeping reaction volume is 1 liter, mean residence time is 70 minutes, temperature of reaction is 140～145 ℃, the pressure of reactor is between 0.15～0.17MPa, after three mean residence times, sampling analysis, its result is as follows:
Hydroxyl value: 55.7 milligrams of KOH/ gram degrees of unsaturation: 0.0075 mmole/gram
Molecular weight distribution (Mw/Mn): 1.27 residual monomer contents: 36ppm
C. 50 gram initiators (hydroxyl value is the polyoxytrimethylene glycerol about 336.0 milligrams of KOH/ gram) and 0.0090 are restrained in the voltage-resistant reactor that catalyst I joins 1 liter, vacuumize and be warming up to more than 120 ℃, the mixture (weight percent of oxyethane is 6～12%) that slowly adds 250 gram propylene oxide and oxyethane, open the continuous discharging of top discharge valve after question response is complete, be 250: 50: 0.0090 adding reactants with mixture/initiator/catalyst I continuously in proportion, keeping reaction volume is 1 liter, mean residence time is 60 minutes, temperature of reaction is 140～145 ℃, the pressure of reactor is between 0.12～0.14MPa, after three mean residence times, sampling analysis, its result is as follows:
Hydroxyl value: 55.6 milligrams of KOH/ gram degrees of unsaturation: 0.0060 mmole/gram
Molecular weight distribution (Mw/Mn): 1.15 residual monomer contents: 35ppm
[embodiment 2]
The preparation of A, bimetallic cyanide complex catalyst
8 gram Cobalt Potassium Cyanides are added 140 ml distilled waters make its dissolving.At rotating speed is the ZnCl that slowly adds 38.5% (weight) under 8000 rev/mins
2The aqueous solution 65 restrains, and adds the mixed solution of 100 milliliters of trimethyl carbinols and 100 ml distilled waters subsequently, stirs after 20 minutes, adds 14.7 gram diethyl phthalate and 200 ml distilled waters, stirs after 10 minutes, with sand core funnel vacuumizing filtration.The solid that obtains is added 150 milliliters of trimethyl carbinols and 60 ml distilled waters, and stirring is after 10 minutes down to be 8000 rev/mins at rotating speed, and adding 10.6 gram diethyl phthalates stir after 10 minutes centrifugation.The solid that obtains is added 200 milliliters of trimethyl carbinols again, and stirring is after 10 minutes down to be 8000 rev/mins at rotating speed, and adding 6.7 gram diethyl phthalates stir after 10 minutes centrifugation.Solid is got solid powder th-1 catalyst II 11.2 grams 60 ℃ of following vacuum-drying to constant weights.
By analysis: Co 9.1% (weight) Zn 14.5% (weight)
The trimethyl carbinol 23.2% (weight) diethyl phthalate 20.8% (weight)
B. olefin oxide successive polymerization
A. 40 gram initiators (hydroxyl value is the polyoxytrimethylene propylene glycol about 280.0 milligrams of KOH/ gram) and 0.0060 are restrained in the voltage-resistant reactor that catalyst I I joins 1 liter, vacuumize and be warming up to more than 120 ℃, slowly add 160 gram propylene oxide, open the continuous discharging of top discharge valve after question response is complete, be 160: 40: 0.006 adding reactants with propylene oxide/initiator/catalyst I I continuously in proportion, keeping reaction volume is 1 liter, mean residence time is 50 minutes, temperature of reaction is 140～145 ℃, the pressure of reactor is at 0.14～0.16MPa, after three mean residence times, sampling analysis, its result is as follows:
Hydroxyl value: 56.8 milligrams of KOH/ gram degrees of unsaturation: 0.0084 mmole/gram
Molecular weight distribution (Mw/Mn): 1.18 residual monomer contents: 39ppm
B. 50 gram initiators (hydroxyl value is the polyoxytrimethylene glycerol about 336.0 milligrams of KOH/ gram) and 0.010 are restrained in the voltage-resistant reactor that catalyst I I joins 1 liter, vacuumize and be warming up to more than 120 ℃, slowly add 250 gram propylene oxide, open the continuous discharging of top discharge valve after question response is complete, be 250: 50: 0.010 adding reactants with propylene oxide/initiator/catalyst I I continuously in proportion, keeping reaction volume is 1 liter, mean residence time is 70 minutes, temperature of reaction is 140～145 ℃, the pressure of reactor is between 0.15～0.17MPa, after three mean residence times, sampling analysis, its result is as follows:
Hydroxyl value: 56.9 milligrams of KOH/ gram degrees of unsaturation: 0.0088 mmole/gram
Molecular weight distribution (Mw/Mn): 1.20 residual monomer contents: 37ppm
C. 50 gram initiators (hydroxyl value is the polyoxytrimethylene glycerol about 336.0 milligrams of KOH/ gram) and 0.0090 are restrained in the voltage-resistant reactor that catalyst I I joins 1 liter, vacuumize and be warming up to more than 120 ℃, the mixture (weight percent of oxyethane is 6～12%) that slowly adds 250 gram propylene oxide and oxyethane, open the continuous discharging of top discharge valve after question response is complete, be 250: 50: 0.0090 adding reactants with mixture/initiator/catalyst I I continuously in proportion, keeping reaction volume is 1 liter, mean residence time is 60 minutes, temperature of reaction is 140～145 ℃, the pressure of reactor is between 0.12～0.14MPa, after three mean residence times, sampling analysis, its result is as follows:
Hydroxyl value: 56.8 milligrams of KOH/ gram degrees of unsaturation: 0.0074 mmole/gram
Molecular weight distribution (Mw/Mn): 1.17 residual monomer contents: 36ppm
[embodiment 3]
The preparation of A, bimetallic cyanide complex catalyst
8 gram Cobalt Potassium Cyanides are added 140 ml distilled waters make its dissolving.At rotating speed is the ZnC liter that slowly adds 38.5% (weight) under 8000 rev/mins
2The aqueous solution 65 restrains, and adds the mixed solution of 100 milliliters of trimethyl carbinols and 100 ml distilled waters subsequently, stirs after 20 minutes, adds 14.7 gram dibutyl phthalate and 200 ml distilled waters, stirs after 10 minutes, with sand core funnel vacuumizing filtration.The solid that obtains is added 150 milliliters of trimethyl carbinols and 60 ml distilled waters, and stirring is after 10 minutes down to be 8000 rev/mins at rotating speed, and adding 10.6 gram dibutyl phthalates stir after 10 minutes centrifugation.The solid that obtains is added 200 milliliters of trimethyl carbinols again, and stirring is after 10 minutes down to be 8000 rev/mins at rotating speed, and adding 6.7 gram dibutyl phthalates stir after 10 minutes centrifugation.Solid is got solid powder th-1 catalyst III 12.4 grams 60 ℃ of following vacuum-drying to constant weights.
By analysis: Co 8.2% (weight) Zn 22.9% (weight)
The trimethyl carbinol 15.7% (weight) dibutyl phthalate 21.0% (weight)
B. olefin oxide successive polymerization
A. 40 gram initiators (hydroxyl value is the polyoxytrimethylene propylene glycol about 280.0 milligrams of KOH/ gram) and 0.0060 are restrained in the voltage-resistant reactor that catalyst I II joins 1 liter, vacuumize and be warming up to more than 120 ℃, slowly add 160 gram propylene oxide, open the continuous discharging of top discharge valve after question response is complete, be 160: 40: 0.006 adding reactants with propylene oxide/initiator/catalyst I II continuously in proportion, keeping reaction volume is 1 liter, mean residence time is 50 minutes, temperature of reaction is 140～145 ℃, the pressure of reactor is at 0.14～0.16MPa, after three mean residence times, sampling analysis, its result is as follows:
Hydroxyl value: 57.2 milligrams of KOH/ gram degrees of unsaturation: 0.0086 mmole/gram
Molecular weight distribution (Mw/Mn): 1.28 residual monomer contents: 40ppm
B. 50 gram initiators (hydroxyl value is the polyoxytrimethylene glycerol about 336.0 milligrams of KOH/ gram) and 0.010 are restrained in the voltage-resistant reactor that catalyst I II joins 1 liter, vacuumize and be warming up to more than 120 ℃, slowly add 250 gram propylene oxide, open the continuous discharging of top discharge valve after question response is complete, be 250: 50: 0.010 adding reactants with propylene oxide/initiator/catalyst I II continuously in proportion, keeping reaction volume is 1 liter, mean residence time is 70 minutes, temperature of reaction is 140～145 ℃, the pressure of reactor is between 0.15～0.17MPa, after three mean residence times, sampling analysis, its result is as follows:
Hydroxyl value: 57.4 milligrams of KOH/ gram degrees of unsaturation: 0.0091 mmole/gram
Molecular weight distribution (Mw/Mn): 1.30 residual monomer contents: 38ppm
C. 50 gram initiators (hydroxyl value is the polyoxytrimethylene glycerol about 336.0 milligrams of KOH/ gram) and 0.0090 are restrained in the voltage-resistant reactor that catalyst I II joins 1 liter, vacuumize and be warming up to more than 120 ℃, the mixture (weight percent of oxyethane is 6～12%) that slowly adds 250 gram propylene oxide and oxyethane, open the continuous discharging of top discharge valve after question response is complete, be 250: 50: 0.0090 adding reactants with mixture/initiator/catalyst I II continuously in proportion, keeping reaction volume is 1 liter, mean residence time is 60 minutes, temperature of reaction is 140～145 ℃, the pressure of reactor is between 0.12～0.14MPa, after three mean residence times, sampling analysis, its result is as follows:
Hydroxyl value: 57.3 milligrams of KOH/ gram degrees of unsaturation: 0.00760 mmole/gram
Molecular weight distribution (Mw/Mn): 1.18 residual monomer contents: 37ppm
Claims (7)
1, a kind of method of preparing polyether polyol by continuous process comprises:
A) a kind of double metal cyanide catalyst;
B) continuously double metal cyanide catalyst, initiator and olefin oxide are joined reactor;
C) continuously polyether glycol is taken out from reactor;
Double metal cyanide catalyst wherein comprises:
1. a kind of bimetallic cyaniding complex, its weight percent are 40～99.8%;
2. a kind of C with tertiary alcohol structure
4～C
10Organic alcohol, its weight percent are 0.1～30%;
3. a kind of organic ligand that is selected from aliphatic ester, aromatic series monoesters or aromatic diester and composition thereof of surplus.
2,, it is characterized in that bimetallic cyaniding complex has following general formula according to the method for the described preparing polyether polyol by continuous process of claim 1:
M
1 a[M
2 b(CN)
c]
d·hM
4 i(X)
j
In the formula: M
1, M
4Be selected from Zn, Fe, Ni, Mn, Co, Sn, Ph, Mo, Al, V, Sr, W, Cu or Cr;
M
2Be selected from Fe, Co, Cr, Mn, Ir, Ni, Rh, Ru or V;
X is selected from halogens, OH
-, NO
3 -, CO
3 2-, SO
4 2-Or ClO
3 2-
A, b, c, d, i and j represent M respectively
1, M
2, CN, [M
2 b(CN)
c], M
4Ion number with X;
The span of h is 0.05～1.0;
The C that has tertiary alcohol structure by weight percentage
4～C
10The amount of organic alcohol is 10～20%; The organic coordination scale of construction that is selected from Fatty Alcohol(C12-C14 and C12-C18), aromatic series monoesters or aromatic diester and composition thereof is 10～30%; Organic ligand is selected from aromatic diester.
3, according to the method for the described preparing polyether polyol by continuous process of claim 2, it is characterized in that M
1Be selected from Zn, Ni or Co; M
2Be selected from Fe or Co; M
4Be selected from Zn or Fe, X is selected from Cl
-, Br
-, NO
3 -Or SO
4 2-The span of h is 0.5～1.0; C with tertiary alcohol structure
4～C
10Organic alcohol is the trimethyl carbinol or tertiary amyl alcohol; Aromatic diester is a phthalic ester, and molecular structure is
R wherein
1Or R
2Be respectively the alkyl of 1～20 carbon atom.
4, according to the method for the described preparing polyether polyol by continuous process of claim 3, it is characterized in that R
1Or R
2Be methyl, ethyl, butyl or the tertiary butyl simultaneously.
5,, it is characterized in that catalyzer, initiator and olefin oxide can add separately in the reactor continuously, also can adopt mutual blended method to join in the reactor according to the method for the described preparing polyether polyol by continuous process of claim 1; Wherein said initiator is low-molecular-weight polyvalent alcohol; Wherein said olefin oxide can be a single-component, also can be the mixture of many components.
6, according to the method for the described preparing polyether polyol by continuous process of claim 1, it is characterized in that described reactor is a still formula stirred reactor, if preparation multi-block polyether polyvalent alcohol, its block number is identical with the number of tandem reactor.
7, according to the method for the described preparing polyether polyol by continuous process of claim 1, the molecular weight that it is characterized in that described polyether glycol is greater than 1000.
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|---|---|---|---|
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ID=40112401
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2017141358A (en) * | 2016-02-10 | 2017-08-17 | 東ソー株式会社 | Polyalkylene oxide |
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|---|---|---|---|---|
| US5689012A (en) * | 1996-07-18 | 1997-11-18 | Arco Chemical Technology, L.P. | Continuous preparation of low unsaturation polyoxyalkylene polyether polyols with continuous additon of starter |
| CN100430136C (en) * | 2002-11-13 | 2008-11-05 | 中国石油化工股份有限公司 | Double metal cyanide catalysts |
| CN1235940C (en) * | 2003-07-09 | 2006-01-11 | 中国石油化工股份有限公司 | Double metal cyanide catalysts for producing polyether polyols |
| CN1294178C (en) * | 2003-07-09 | 2007-01-10 | 中国石油化工股份有限公司 | Process for producing polyether polyols with low degree of unsaturation |
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Cited By (1)
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|---|---|---|---|---|
| JP2017141358A (en) * | 2016-02-10 | 2017-08-17 | 東ソー株式会社 | Polyalkylene oxide |
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