CN1709939A - Method for preparing low-unsaturation-degree polyether polylol - Google Patents
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- CN1709939A CN1709939A CN 200510027011 CN200510027011A CN1709939A CN 1709939 A CN1709939 A CN 1709939A CN 200510027011 CN200510027011 CN 200510027011 CN 200510027011 A CN200510027011 A CN 200510027011A CN 1709939 A CN1709939 A CN 1709939A
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Abstract
The invention relates to the preparation of a kind of low unsaturation polyether polyols. It's mainly used to solve the problem in previous technology that it has long catalyst inductive period and the concentration of catalyst in initiator is high, which is that it has a high catalyst cost in the preparation of unsaturation polyether polyols. The invention excellently solves the said problem through adopting catalyst components containing double metal cyanide (DMC) mixture, C4 - C10 organic mellow with tertiary alcohol structure, adding bronsted acid, and adopting the technology project of inert gas frothing to degasificate. So it can be used in the industrial production of low unsaturation polyether polyols.
Description
Technical field
The present invention relates to a kind of preparation method of low-unsaturated polyether polyatomic alcohol.
Background technology
As everyone knows, with alkali catalyzer (being mainly KOH) when being used for epoxide polymerization and preparing polyether glycol, because catalytic activity is low, thick product needed is through postprocessing working procedures such as peracid neutralization, dehydration part and decolourings.The polyether glycol degree of unsaturation height that obtains can produce adverse influence to polyurethane product, and is also very difficult with alkalescence (KOH) Preparation of Catalyst high-molecular weight polyether glycol simultaneously.
DMC catalysts can be used for epoxide polymerization and prepares low-unsaturated polyether polyatomic alcohol, and this polyether glycol can be used for preparing products such as polyurethane coating, elastomerics, foam, seal gum and tackiness agent.
DMC catalysts is a kind of throw out that the reactant aqueous solution by metal-salt and metal cyanide salt obtains.In order to prepare active DMC catalysts, in preparation process, need to add organic complexing agent, for example alcohol or ether etc. usually.It is the technology that complexing agent prepares DMC catalysts that document US 3427256, US3427334, US5158922 have reported with diethylene glycol dimethyl ether, diethylene glycol diethyl ether, triethylene glycol dme etc. in succession.Though its performance of polyether glycol that this class catalyzer makes has had bigger improvement, the degree of unsaturation that mainly shows polyether glycol is low than what make with alkalescence (KOH) catalyzer, but because activity of such catalysts is not high enough, far can not reach the requirement that does not need the process aftertreatment to slough catalyzer, catalyzer is comparatively expensive simultaneously, and its application is subjected to certain restriction.The mixed solution of having reported among document US 5470813, US5482908, US5627120, EP6755716, the CN1233529A with the trimethyl carbinol or the trimethyl carbinol and glycol dimethyl ether is the technology that complexing agent prepares DMC catalysts.Improve though this its activity of class catalyzer has had largely, some still needs to remove the last handling process of catalyzer in the polymkeric substance.This class catalyzer ubiquity is longer inductive phase, when the content of catalyzer in the polyether glycol that finally makes when 25PPm is following, its inductive phase is more than 2 hours.Promptly before epoxy compounds added reactor continuously, DMC (double metal cyanide) catalyzer must be activated earlier.Common induced reaction is: initiator (low-molecular-weight polyvalent alcohol) is mixed with dmc catalyst, while the vacuum outgas that heats up adds epoxy compounds (add-on of epoxy compounds is 3～30% weight of initial dose) then and carries out induced reaction.On this process nature the reactivation process of catalyzer, the length that this process is consuming time, promptly the length of inductive phase will directly have influence on the inner quality and the production cycle of polyether glycol.Usually, people adopt following method to shorten the inductive phase of dmc catalyst:
(1) increases catalyst concentration.The main drawback of this method is: because dmc catalyst than the KOH costliness, increases the corresponding production cost that increased of catalyst concentration; The increase of catalyst concn makes the temperature control of initial action become difficult; Adopt one of great advantage of dmc catalyst synthesizing polyether, can save aftertreatment exactly, in case catalyst concentration increases, the kish ion increases in the polyethers, can influence the processing of urethane subsequent product;
(2) concentration of increase initiator epoxy compounds.The main drawback of this method is: when catalyzer is activated, the concentration of too high initial epoxy compounds can cause the violent temperature of scurrying, and makes temperature of reaction be difficult to control, and causes the potential safety hazard; Simultaneously, the concuss of temperature produces negative influence to the quality of polyethers;
(3) improve the induced reaction temperature.The main drawback of this method is: if the dmc catalyst long period is under the condition of high temperature, can cause catalyst activity reduction, even inactivation.
Summary of the invention
Technical problem to be solved by this invention be exist in the conventional art preparation during low-unsaturated polyether polyatomic alcohol catalyst inducement phase longer, catalyzer concentration in initiator is higher, the problem that production cost is high provides a kind of new method that is used to prepare low-unsaturated polyether polyatomic alcohol.When this method was used for epoxide polymerization, it was lower to have bimetallic catalyst concentration in initiator, and inductive phase is short, and the polyether glycol that makes simultaneously has the characteristics of low-unsaturation-degree.
For solving the problems of the technologies described above, the technical solution used in the present invention is as follows: a kind of preparation method of low-unsaturated polyether polyatomic alcohol, with molecular weight is that 200～1000 polyvalent alcohols that contain 2～8 active hydrogen groups are initiator, with the monocycle oxycompound is raw material, in the presence of catalyzer, under 90～150 ℃ temperature of reaction, react the generation low-unsaturated polyether polyatomic alcohol, used catalyzer is double metal cyanide (DMC) catalyzer, and catalyzer comprises following component by weight percentage:
A) 40～99.8% double metal cyanide mixture;
B) 0.1～30% C with tertiary alcohol structure
4～C
10Organic alcohol;
Wherein in the mixture of initiator and DMC catalysts, add to be selected from and contain at least a protonic acid in Phosphorus oxygen acid, sulfur-bearing class oxygen acid, nitrogenous class oxygen acid or the carboxylic acid, and 90～150 ℃ of temperature, vacuum tightness is-0.097～-the 0.070MPa condition under, use reaction mass is the inert gasses bubbling degassing 5～120 minutes.
In the technique scheme, the double metal cyanide mixture has following general formula: A
a[B
b(CN)
c]
dEC
n(X)
m,
In the formula: A or C are selected from Zn, Fe, Ni, Mn, Co, Sn, Pb, Mo, Al, V, Sr, W, Cu or Cr;
B is selected from Fe, Co, Cr, Mn, Ir, Ni, Rh, Ru or V;
X is selected from halide-ions, OH
-, NO
- 3, CO
2- 3, SO
2 4 -Or ClO
2- 3
A, b, c, d and n represent A, B, CN, [B respectively
b(CN)
c], the number of C and negatively charged ion X;
The span of e is 0.05～1.0.
The preferred version of A is for being selected from Zn, Ni or Co; The preferred version of B is for being selected from Fe or Co; The preferred version of C is for being selected from Zn or Fe; The preferred version of X is for being selected from Cl
-, Br
-, NO
- 3Or SO
2 4 -The value preferable range of e is 0.5～1.0.By weight percentage, the C that has tertiary alcohol structure
4～C
10The consumption preferable range of organic alcohol is 10～20%; C with tertiary alcohol structure
4～C
10Organic pure preferred version is the trimethyl carbinol or tertiary amyl alcohol; The molecular weight preferable range of initiator is 200～700, and active hydrogen group is 2 or 3; Monocycle oxycompound preferred version is to add in the reaction system in bubbling degassing back.The protonic acid preferred version is selected from phosphoric acid, and the concentration preferable range of protonic acid in initiator is 5～300PPm; More preferably scope is 10～100PPm; The concentration preferable range of catalyzer in initiator is 25～300PPm; Be the inert gasses preferred version and be selected from least a in nitrogen, air, carbonic acid gas, argon gas, the helium, more preferably scheme is for being selected from nitrogen; The temperature preferable range of the bubbling degassing is 110～120 ℃, and more preferably scope is 110～115 ℃; The vacuum tightness preferable range of the bubbling degassing is-0.095～-0.080MPa; Bubbling degassing time preferable range is 20～80 minutes, and more preferably scope is 40～65 minutes.The initiator preferred version is polyoxytrimethylene propylene glycol or polyoxytrimethylene glycerol; Monocycle oxycompound preferred version is to be selected from least a in oxyethane, propylene oxide, butylene oxide ring or the Styrene oxide 98min..
The preparation method of the DMC catalysts of using in the inventive method is as follows: with metal cyanide salt [K for example
3Co (CN)
6] be dissolved in water and get the solution first, metal-salt [ZnCl for example
2] be dissolved in water and get solution second.Mix organic complexing agent and can be added in the solution first, also can be added in the solution second, perhaps all add in solution first and the solution second and mix organic alcohol.Is to join more than 300 rev/mins in the solution first solution second at rotating speed, after reaction for some time under 0～50 ℃, adopts the vacuum filtration method to obtain solid catalyst.Also can adopt the method that after solution first and the reaction of solution second, adds organic alcohol immediately to prepare catalyzer.
The DMC catalysts of using in the inventive method can be used for the olefin oxide ring-opening polymerization and prepares polyether glycol.Olefin oxide comprises oxyethane, propylene oxide, butylene oxide ring and their mixture, with the amount of the monocycle oxycompound of initiator for reaction be 45～100% of initiator weight, be good with 50～70%; The concentration of catalyst consumption in initiator is 25～300PPm, is good with 25～50PPm, and the temperature of reaction preferable range is 100～110 ℃.The polyether glycol that obtains has average functionality between 2～8, is preferably 2～3.The number-average molecular weight of the polyether glycol that obtains is preferably between 2000～8000 at 500～50000.
We be surprised to find catalyzer to olefin oxide ring-opening polymerization process in, in initiator, add micro-phosphoric acid, simultaneously initial mixture system is carried out the bubbling degassing, can make bimetallic catalyst under extremely low catalyst concn, finish activation, and effectively finish the ring-opening polymerization of epoxy compounds, shorten greatly the inductive phase of catalyzer simultaneously, obtained better technical effect.
The invention will be further elaborated below by embodiment.
Embodiment
[embodiment 1]
The preparation of 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, with sand core funnel vacuumizing filtration.Solid is got solid powder th-1 catalyst I12.6 gram 60 ℃ of following vacuum-drying to constant weights.
By analysis: Co 8.6% (weight)
Zn 22.4% (weight)
The trimethyl carbinol 15.7% (weight)
[embodiment 2]
The propylene oxide polymerization
With 80 gram initiator (400Mn, the polyoxytrimethylene propylene glycol) and 0.020 catalyst I that makes of gram embodiment 1 join in 2 liters the voltage-resistant reactor, vacuumize be warming up to 105 ℃ after, add 30 gram propylene oxide, reactor pressure rises to 0.20MPa rapidly, keep temperature of reactor between 105～110 ℃, (being considered as the inductive phase of catalyzer) post-reactor pressure obviously reduced in 15 minutes, the temperature of keeping reactor adds 690 gram propylene oxide continuously under 105～110 ℃ situation, make reactor pressure be no more than 0.20MPa, after propylene oxide adds, when no longer changing, the pressure of reactor shows that reaction finishes, 22 minutes total reaction times vacuumized and removes the unreacted residual monomer, cooled off to such an extent that polyether Glycols 796 restrains.
By analysis: the hydroxyl value of polyether Glycols is 28.70 milligrams of KOH/ grams, and degree of unsaturation is 0.0053 mmole/gram, and water-content is 36PPm.
[embodiment 3]
The propylene oxide polymerization
With 80 gram initiator (400Mn, the polyoxytrimethylene propylene glycol) and 0.020 catalyst I that makes of gram embodiment 1 join in 2 liters the voltage-resistant reactor, vacuumize be warming up to 105 ℃ after, add 30 gram propylene oxide, reactor pressure rises to 0.19MPa rapidly, keep temperature of reactor between 105～110 ℃, (being considered as the inductive phase of catalyzer) post-reactor pressure obviously reduced in 10 minutes, the temperature of keeping reactor adds 690 gram propylene oxide continuously under 105～110 ℃ situation, make reactor pressure be no more than 0.20MPa, after propylene oxide adds, when no longer changing, the pressure of reactor shows that reaction finishes, 18 minutes total reaction times vacuumized and removes the unreacted residual monomer, cooled off to such an extent that polyether Glycols 795 restrains.
By analysis: the hydroxyl value of polyether Glycols is 28.40 milligrams of KOH/ grams, and degree of unsaturation is 0.0047 mmole/gram, and water-content is 37PPm.
[embodiment 4]
The propylene oxide polymerization
With 50 gram initiator (500Mn, the polyoxytrimethylene glycerol) and 0.0125 catalyst I that makes of gram embodiment 1 join in 2 liters the voltage-resistant reactor, vacuumize be warming up to 105 ℃ after, add 30 gram propylene oxide, reactor pressure rises to 0.20MPa rapidly, keep temperature of reactor between 105～110 ℃, (being considered as the inductive phase of catalyzer) post-reactor pressure obviously reduced in 30 minutes, the temperature of keeping reactor adds 420 gram propylene oxide continuously under 105～110 ℃ situation, make reactor pressure be no more than 0.20MPa, after propylene oxide adds, oneself finishes to show reaction when the pressure of reactor no longer changes, 30 minutes total reaction times vacuumized and removes the unreacted residual monomer, cooled off to such an extent that polyether Glycols 496 restrains.
By analysis: the hydroxyl value of polyether-tribasic alcohol is 34.80 milligrams of KOH/ grams, and degree of unsaturation is 0.0065 mmole/gram, and water-content is 38PPm.
[embodiment 5]
The propylene oxide polymerization
With 50 gram initiator (500Mn, the polyoxytrimethylene glycerol) and 0.0125 catalyst I that makes of gram embodiment 1 join in 2 liters the voltage-resistant reactor, vacuumize be warming up to 105 ℃ after, add 30 gram propylene oxide, reactor pressure rises to 0.18MPa rapidly, keep temperature of reactor between 105～110 ℃, (being considered as the inductive phase of catalyzer) post-reactor pressure obviously reduced in 25 minutes, the temperature of keeping reactor adds 420 gram propylene oxide continuously under 105～110 ℃ situation, make reactor pressure be no more than 0.20MPa, after propylene oxide adds, when no longer changing, the pressure of reactor shows that reaction finishes, 22 minutes total reaction times vacuumized and removes the unreacted residual monomer, cooled off to such an extent that polyether-tribasic alcohol 497 restrains.
By analysis: the hydroxyl value of polyether-tribasic alcohol is 34.50 milligrams of KOH/ grams, and degree of unsaturation is 0.0048 mmole/gram, and water-content is 39PPm.
[embodiment 6]
The propylene oxide polymerization
With 80 gram initiator (400Mn, the polyoxytrimethylene propylene glycol) and 0.040 catalyst I that makes of gram embodiment 1 join in 2 liters the voltage-resistant reactor, vacuumize be warming up to 105 ℃ after, add 30 gram propylene oxide, reactor pressure rises to 0.21MPa rapidly, keep temperature of reactor between 105～110 ℃, (being considered as the inductive phase of catalyzer) post-reactor pressure obviously reduced in 30 minutes, the temperature of keeping reactor adds 690 gram propylene oxide continuously under 105～110 ℃ situation, make reactor pressure be no more than 0.20MPa, after propylene oxide adds, when no longer changing, the pressure of reactor shows that reaction finishes, 50 minutes total reaction times vacuumized and removes the unreacted residual monomer, cooled off to such an extent that polyether Glycols 795 restrains.
By analysis: the hydroxyl value of polyether Glycols is 29.90 milligrams of KOH/ grams, and degree of unsaturation is 0.0082 mmole/gram, and water-content is 42PPm.
[embodiment 7]
The propylene oxide polymerization
With 70 gram initiators (700 moles. weight. the polyoxytrimethylene propylene glycol) and 0.010 restrain in the voltage-resistant reactor that catalyst I that embodiment 1 makes joins 2 liters, vacuumize be warming up to 105 ℃ after, add 30 gram propylene oxide, reactor pressure rises to 0.19MPa rapidly, keep temperature of reactor between 105～110 ℃, (being considered as the inductive phase of catalyzer) post-reactor pressure obviously reduced in 20 minutes, the temperature of keeping reactor adds 300 gram propylene oxide continuously under 105～110 ℃ situation, make reactor pressure be no more than 0.20MPa, after propylene oxide adds, when no longer changing, the pressure of reactor shows that reaction finishes, 18 minutes total reaction times, vacuumize and remove the unreacted residual monomer, cool off to such an extent that polyether Glycols 397 restrains.
By analysis: the hydroxyl value of polyether Glycols is 28.30 milligrams of KOH/ grams, and degree of unsaturation is 0.0056 mmole/gram, and water-content is 38PPm.
[embodiment 8]
The propylene oxide polymerization
With 70 gram initiators (700 moles. weight. the polyoxytrimethylene propylene glycol) and 0.015 restrain in the voltage-resistant reactor that catalyst I that embodiment 1 makes joins 2 liters, vacuumize be warming up to 105 ℃ after, add 30 gram propylene oxide, reactor pressure rises to 0.19MPa rapidly, keep temperature of reactor between 105～110 ℃, (being considered as the inductive phase of catalyzer) post-reactor pressure obviously reduced in 20 minutes, the temperature of keeping reactor adds 500 gram propylene oxide continuously under 105～110 ℃ situation, make reactor pressure be no more than 0.20MPa, after propylene oxide adds, oneself finishes to show reaction when the pressure of reactor no longer changes, 25 minutes total reaction times, vacuumize and remove the unreacted residual monomer, cool off to such an extent that polyether Glycols 595 restrains.
By analysis: the hydroxyl value of polyether Glycols is 19.21 milligrams of KOH/ grams, and degree of unsaturation is 0.0048 mmole/gram, and water-content is 36PPm.
[embodiment 9]
The propylene oxide polymerization
With 100 gram initiators (1000 moles. weight. the polyoxytrimethylene propylene glycol) and 0.020 restrain in the voltage-resistant reactor that catalyst I that embodiment 1 makes joins 2 liters, vacuumize be warming up to 105 ℃ after, add 30 gram propylene oxide, reactor pressure rises to 0.20MPa rapidly, keep temperature of reactor between 105～110 ℃, (being considered as the inductive phase of catalyzer) post-reactor pressure obviously reduced in 15 minutes, the temperature of keeping reactor adds 670 gram propylene oxide continuously under 105～110 ℃ situation, make reactor pressure be no more than 0.20MPa, after propylene oxide adds, when no longer changing, the pressure of reactor shows that reaction finishes, 30 minutes total reaction times, vacuumize and remove the unreacted residual monomer, cool off to such an extent that polyether Glycols 792 restrains.
By analysis: the hydroxyl value of polyether Glycols is 14.21 milligrams of KOH/ grams, and degree of unsaturation is 0.0074 mmole/gram, and water-content is 38PPm.
[embodiment 10]
The propylene oxide polymerization
With 70 gram initiators (700 moles. weight. the polyoxytrimethylene glycerol) and 0.0125 restrain in the voltage-resistant reactor that catalyst I that embodiment 1 makes joins 2 liters, vacuumize be warming up to 105 ℃ after, add 30 gram propylene oxide, reactor pressure rises to 0.16MPa rapidly, keep temperature of reactor between 105～110 ℃, (being considered as the inductive phase of catalyzer) post-reactor pressure obviously reduced in 25 minutes, the temperature of keeping reactor adds 400 gram propylene oxide continuously under 105～110 ℃ situation, make reactor pressure be no more than 0.20MPa, after propylene oxide adds, oneself finishes to show reaction when the pressure of reactor no longer changes, 22 minutes total reaction times, vacuumize and remove the unreacted residual monomer, cool off to such an extent that polyether-tribasic alcohol 497 restrains.
By analysis: the hydroxyl value of polyether-tribasic alcohol is 34.20 milligrams of KOH/ grams, and degree of unsaturation is 0.0050 mmole/gram, and water-content is 39PPm.
[embodiment 11]
The propylene oxide polymerization
With 70 gram initiators (700 moles. weight. the polyoxytrimethylene propylene glycol) and 0.020 restrain in the voltage-resistant reactor that catalyst I that embodiment 1 makes joins 2 liters, vacuumize be warming up to 105 ℃ after, add 30 gram propylene oxide, reactor pressure rises to 0.24MPa rapidly, keep temperature of reactor between 105～110 ℃, (being considered as the inductive phase of catalyzer) post-reactor pressure obviously reduced in 35 minutes, the temperature of keeping reactor adds 300 gram propylene oxide continuously under 105～110 ℃ situation, make reactor pressure be no more than 0.20MPa, after propylene oxide adds, when no longer changing, the pressure of reactor shows that reaction finishes, 50 minutes total reaction times, vacuumize and remove the unreacted residual monomer, cool off to such an extent that polyether Glycols 395 restrains.
By analysis: the hydroxyl value of polyether Glycols is 30.32 milligrams of KOH/ grams, and degree of unsaturation is 0.0085 mmole/gram, and water-content is 40PPm.
Claims (9)
1, a kind of preparation method of low-unsaturated polyether polyatomic alcohol, with molecular weight is that 200～1000 polyvalent alcohols that contain 2～8 active hydrogen groups are initiator, with the monocycle oxycompound is raw material, in the presence of catalyzer, under 90～150 ℃ temperature of reaction, react the generation low-unsaturated polyether polyatomic alcohol, used catalyzer is a DMC catalysts, and catalyzer comprises following component by weight percentage:
A) 40～99.8% double metal cyanide mixture;
B) 0.1～30% C with tertiary alcohol structure
4～C
10Organic alcohol;
It is characterized in that in the mixture of initiator and DMC catalysts, adding to be selected from containing at least a protonic acid in Phosphorus oxygen acid, sulfur-bearing class oxygen acid, nitrogenous class oxygen acid or the carboxylic acid, and 90～150 ℃ of temperature, vacuum tightness is-0.097～-the 0.070MPa condition under, use reaction mass is the inert gasses bubbling degassing 5～120 minutes.
2,, it is characterized in that the double metal cyanide mixture has following general formula according to the preparation method of the described low-unsaturated polyether polyatomic alcohol of claim 1:
A
a[B
b(CN)
c]
d·eC
n(X)
m
In the formula: A or C are selected from Zn, Fe, Ni, Mn, Co, Sn, Pb, Mo, Al, V, Sr, W, Cu or Cr;
B is selected from Fe, Co, Cr, Mn, Ir, Ni, Rh, Ru or V;
X is selected from halide-ions, OH
-, NO
- 3, CO
2- 3, SO
2- 4Or ClO
2- 3
A, b, c, d, n and m represent A, B, CN, [B respectively
b(CN)
c], the number of C and negatively charged ion X;
The span of e is 0.05～1.0.
3,, it is characterized in that A is selected from Zn, Ni or Co according to the preparation method of the described low-unsaturated polyether polyatomic alcohol of claim 2; B is selected from Fe or Co; C is selected from Zn or Fe; X is selected from Cl
-, Br
-, NO
- 3Or SO
2- 4The span of e is 0.5～1.0.
4,, it is characterized in that having by weight percentage the C of tertiary alcohol structure according to the preparation method of the described low-unsaturated polyether polyatomic alcohol of claim 1
4～C
10The consumption of organic alcohol is 10～20%.
5,, it is characterized in that having the C of tertiary alcohol structure according to the preparation method of the described low-unsaturated polyether polyatomic alcohol of claim 1
4～C
10Organic alcohol is the trimethyl carbinol or tertiary amyl alcohol.
6, according to the preparation method of the described low-unsaturated polyether polyatomic alcohol of claim 1, the molecular weight that it is characterized in that initiator is 200～700, and active hydrogen group is 2 or 3; The monocycle oxycompound adds in the reaction system in bubbling degassing back.
7,, it is characterized in that initiator is polyoxytrimethylene propylene glycol or polyoxytrimethylene glycerol according to the preparation method of the described low-unsaturated polyether polyatomic alcohol of claim 1; The monocycle oxycompound is selected from least a in oxyethane, propylene oxide, butylene oxide ring or the Styrene oxide 98min..
8, according to the preparation method of the described low-unsaturated polyether polyatomic alcohol of claim 1, it is characterized in that protonic acid is selected from phosphoric acid, the concentration of protonic acid in initiator is 5～300PPm; The concentration of catalyzer in initiator is 25～300PPm; Rare gas element is selected from least a in nitrogen, air, carbonic acid gas, argon gas, the helium; The temperature of the bubbling degassing is 110～120 ℃, vacuum tightness is-0.095～-0.080MPa, the bubbling degassing time is 20～80 minutes.
9, the preparation method of described low-unsaturated polyether polyatomic alcohol according to Claim 8 is characterized in that the concentration of protonic acid in initiator is 10～100PPm; Rare gas element is selected from nitrogen; The temperature of the bubbling degassing is 110～115 ℃, and the bubbling degassing time is 40～65 minutes.
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| CN101161700B (en) * | 2007-08-17 | 2010-05-19 | 胡冰 | Method for producing polyether |
| CN102040731B (en) * | 2009-10-23 | 2012-07-25 | 中国石油化工集团公司 | Method for preparing polyether polyol |
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| CN103154084A (en) * | 2010-08-20 | 2013-06-12 | 巴斯夫欧洲公司 | Process for the preparation of polyetherester polyols |
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| US5545601A (en) * | 1995-08-22 | 1996-08-13 | Arco Chemical Technology, L.P. | Polyether-containing double metal cyanide catalysts |
| US5627120A (en) * | 1996-04-19 | 1997-05-06 | Arco Chemical Technology, L.P. | Highly active double metal cyanide catalysts |
| DE19953546A1 (en) * | 1999-11-08 | 2001-05-10 | Bayer Ag | Double metal cyanide catalysts for the production of polyether polyols |
| CN100430136C (en) * | 2002-11-13 | 2008-11-05 | 中国石油化工股份有限公司 | Double metal cyanide catalysts |
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| CN101161700B (en) * | 2007-08-17 | 2010-05-19 | 胡冰 | Method for producing polyether |
| CN102040731B (en) * | 2009-10-23 | 2012-07-25 | 中国石油化工集团公司 | Method for preparing polyether polyol |
| CN102040732B (en) * | 2009-10-23 | 2012-09-26 | 中国石油化工集团公司 | Preparation method of polyether polyol cross-coupling agent |
| CN103154084B (en) * | 2010-08-20 | 2015-06-10 | 巴斯夫欧洲公司 | Process for the preparation of polyetherester polyols |
| CN103154084A (en) * | 2010-08-20 | 2013-06-12 | 巴斯夫欧洲公司 | Process for the preparation of polyetherester polyols |
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| CN105237756B (en) * | 2014-07-11 | 2017-11-21 | 中国石油化工股份有限公司 | The preparation method of lactide modified polyether polylol |
| CN110804168A (en) * | 2019-11-05 | 2020-02-18 | 上海东大化学有限公司 | High molecular weight polyether polyol for adding lubricating oil and preparation method thereof |
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| CN115785435A (en) * | 2022-12-29 | 2023-03-14 | 杭州普力材料科技有限公司 | Method for preparing polyether polyol by one-step method |
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