CN1294178C - Process for producing polyether polyols with low degree of unsaturation - Google Patents
Process for producing polyether polyols with low degree of unsaturation Download PDFInfo
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Abstract
The present invention relates to a preparation method for polyether glycol with a low unsaturated degree, which mainly solves the problems that the induction period of a catalyst is long, and the influence of the metal ions of an initiator on the performance of the catalyst is great when polyether glycol with a low unsaturated degree is prepared in the past technology. The present invention favorably solves the problems by adopting the technical scheme that the components of the catalyst contain a bimetallic cyanide mixture, C4 to C10 organic alcohol having tertiary alcohol structures, and organic ester which is selected from silicic acid ester, the mixture thereof, or aliphatic ester, aromatic diester and the mixture thereof. The preparation method can be used in the industrial production of the polyether glycol with a low unsaturated degree.
Description
Technical field
The present invention relates to a kind of preparation method of low-unsaturated polyether polyatomic alcohol, particularly about a kind of in preparation low-unsaturated polyether polyatomic alcohol process, have high reactivity, inductive phase is short and the initiator metal ion to the little method of catalyst performance influence.
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.In addition, this class catalyzer is that the low molecular polyether polyvalent alcohol of Preparation of Catalyst is an initiator with alkali (KOH) usually, though this low-molecular-weight polyether glycol can be removed most of K through aftertreatments such as acid neutralization, absorption
+, but to reach its content below 5PPm, still have certain difficulty in the actual production.K
+Existence to DMC catalysts can produce very big influence, some in addition can make the DMC catalysts inactivation.The anti-K of DMC catalysts ubiquity of above-mentioned bibliographical information
+The characteristics that interference performance is more weak.
Summary of the invention
Technical problem to be solved by this invention is long problem of catalyst inducement phase when existing in the preparation low-unsaturated polyether polyatomic alcohol in the conventional art, and a kind of new method that is used to prepare low-unsaturated polyether polyatomic alcohol is provided.When this method is used for epoxide polymerization, have the catalytic activity height, inductive phase is short, K in the anti-initiator
+The polyether glycol that interference performance makes by force 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 300～1000 to contain at least that the polyvalent alcohol of two or more active hydrogen groups is an 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, wherein 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;
C) 0.1～30% organic ester that is selected from positive silicon ester and composition thereof or aromatic diester and composition thereof; Wherein positive silicon ester and composition thereof molecular structure is Si (OR)
4, wherein R is the alkyl of 1～20 carbon atom can be the same or different; Aromatic diester is a phthalic ester, and molecular structure is
Its R
1Or R
2Be respectively the alkyl of 1～20 carbon atom.
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, 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.
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- 4The 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 consumption preferable range that is selected from positive silicon ester and composition thereof or aromatic diester and composition thereof by weight percentage is 10～30%; Positive silicon ester molecular structure is Si (OR)
4, wherein the R preferred version is the alkyl of 1～4 carbon atom, more preferably scheme is for being selected from methyl, ethyl, butyl or the tertiary butyl simultaneously; The phthalic acid ester molecular structure is
, R
1Or R
2Preferred version is respectively the alkyl of 1～4 carbon atom, more preferably scheme R
1Or R
2Be methyl, ethyl, butyl or the tertiary butyl simultaneously respectively.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 complexing agent.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 the mixing organic complexing agent 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%; Catalyst consumption is 15～50PPm, is good with 20～25PPm, 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 polyether glycol is preferably between 2000～8000 at 500～50000.
We are surprised to find in the Preparation of catalysts process organic ester that adopts positive silicon ester or aliphatic ester, aromatic series monoesters or aromatic diester and composition thereof and the trimethyl carbinol as mixing organic complexing agent, ring-opening polymerization has higher activity to catalyzer to olefin oxide, shorten K in the anti-simultaneously initiator greatly the inductive phase of catalyzer simultaneously
+Interference performance is strong, has obtained better technical effect.
The invention will be 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 10.8 positive silicon ester of gram 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 7.8 gram methyl silicates 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 4.9 gram methyl silicates stir after 10 minutes centrifugation.Solid is got solid powder th-1 catalyst I 12.6 grams 60 ℃ of following vacuum-drying to constant weights.
By analysis: Co 8.6% (weight) Zn 22.4% (weight)
The trimethyl carbinol 15.7% (weight) methyl silicate 22.2% (weight)
B, propylene oxide polymerization
With 80 gram initiator (400Mn, K
+Content is the polyoxytrimethylene propylene glycol of 8.1PPm) and 0.020 gram catalyst I 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, vacuumize and remove the unreacted residual monomer, cool 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.
C, propylene oxide polymerization
With 80 gram initiator (400Mn, K
+Content is the polyoxytrimethylene propylene glycol of 4.8PPm) and 0.020 gram catalyst I 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, vacuumize and remove the unreacted residual monomer, cool 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.
D, propylene oxide polymerization
With 50 gram initiator (500Mn, K
+Content is the polyoxytrimethylene glycerol of 8.3PPm) and 0.0125 gram catalyst I 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, 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 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.
E, propylene oxide polymerization
With 50 gram initiator (500Mn, K
+Content is the polyoxytrimethylene glycerol of 4.9PPm) and 0.0125 gram catalyst I 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, 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 34.50 milligrams of KOH/ grams, and degree of unsaturation is 0.0048 mmole/gram, and water-content is 39PPm.
[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 tetraethoxy 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 tetraethoxys 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 tetraethoxys stir after 10 minutes centrifugation.Solid is got solid powder th-1 catalyst II 12.8 grams 60 ℃ of following vacuum-drying to constant weights.
By analysis: Co 8.5% (weight) Zn 22.0% (weight)
The trimethyl carbinol 15.1% (weight) tetraethoxy 21.2% (weight)
B, propylene oxide polymerization
With 80 gram initiator (400Mn, K
+Content is the polyoxytrimethylene propylene glycol of 8.1PPm) and 0.020 gram catalyst I I 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 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, 21 minutes total reaction times, vacuumize and remove the unreacted residual monomer, cool off to such an extent that polyether Glycols 797 restrains.
By analysis: the hydroxyl value of polyether Glycols is 28.50 milligrams of KOH/ grams, and degree of unsaturation is 0.0050 mmole/gram, and water-content is 40PPm.
The preparation of C, 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 tetraethoxy 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 tetraethoxys stir after 10 minutes centrifugation.The solid that obtains is added 200 milliliters of trimethyl carbinols again, be 8000 rev/mins at rotating speed and descend stirring after 20 minutes, centrifugation.Solid is got solid powder th-1 catalyst III 11.9 grams 60 ℃ of following vacuum-drying to constant weights.
By analysis: Co 8.9% (weight) Zn 23.7% (weight)
The trimethyl carbinol 16.0% (weight) tetraethoxy 18.1% (weight)
D, propylene oxide polymerization
With 80 gram initiator (400Mn, K
+Content is the polyoxytrimethylene propylene glycol of 8.1PPm) and 0.020 gram catalyst I II 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 50 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, 54 minutes total reaction times, vacuumize and remove the unreacted residual monomer, cool off to such an extent that polyether Glycols 796 restrains.
By analysis: the hydroxyl value of polyether Glycols is 29.70 milligrams of KOH/ grams, and degree of unsaturation is 0.0075 mmole/gram, and water-content is 41PPm.
The preparation of E, 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 tetraethoxy 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, be 8000 rev/mins at rotating speed and descend stirring after 20 minutes, centrifugation.The solid that obtains is added 200 milliliters of trimethyl carbinols again, be 8000 rev/mins at rotating speed and descend stirring after 20 minutes, centrifugation.Solid is got solid powder th-1 catalyst IV 11.3 grams 60 ℃ of following vacuum-drying to constant weights.
By analysis: Co 9.2% (weight) Zn 24.2% (weight)
The trimethyl carbinol 16.3% (weight) tetraethoxy 14.1% (weight)
F, propylene oxide polymerization
With 80 gram initiator (400Mn, K
+Content is the polyoxytrimethylene propylene glycol of 8.1PPm) and 0.040 gram catalyst I V 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, vacuumize and remove the unreacted residual monomer, cool 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 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 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 22.7 gram positive butyl ester of positive silicic acid 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 the positive butyl ester of the adding 16.2 positive silicic acid of gram stirs 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 the positive butyl ester of the adding 10.3 positive silicic acid of gram stirs after 10 minutes centrifugation.Solid is got solid powder th-1 catalyst V12.5 gram 60 ℃ of following vacuum-drying to constant weights.
By analysis: Co 8.7% (weight) Zn 22.5% (weight)
The trimethyl carbinol 15.3% (weight) butyl silicate 22.4% (weight)
B, propylene oxide polymerization
With 80 gram initiator (400Mn, K
+Content is the polyoxytrimethylene propylene glycol of 8.1PPm) and 0.020 gram catalyst V 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 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, 25 minutes total reaction times, vacuumize and remove the unreacted residual monomer, cool off to such an extent that polyether Glycols 796 restrains.
By analysis: the hydroxyl value of polyether Glycols is 29.00 milligrams of KOH/ grams, and degree of unsaturation is 0.0052 mmole/gram, and water-content is 38PPm.
[comparative example 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 30 minutes, with sand core funnel vacuumizing filtration.The solid that obtains is added 150 milliliters of trimethyl carbinols and 60 ml distilled waters, be 8000 rev/mins at rotating speed and descend stirring after 20 minutes, centrifugation.The solid that obtains is added 200 milliliters of trimethyl carbinols again, be 8000 rev/mins at rotating speed and descend stirring after 20 minutes, centrifugation.Solid is got solid powder th-1 catalyst VI 10.2 grams 60 ℃ of following vacuum-drying to constant weights.
By analysis: Co 10.9% (weight) Zn 29.2% (weight)
The trimethyl carbinol 10.9% (weight)
B, propylene oxide polymerization
With 80 gram initiator (400Mn, K
+Content is the polyoxytrimethylene propylene glycol of 4.8PPm) and 0.020 gram catalyst V I join in 2 liters the voltage-resistant reactor, vacuumize be warming up to 105 ℃ after, add 30 gram propylene oxide, reactor pressure rises to 0.22MPa rapidly, keep temperature of reactor between 105～110 ℃, (being considered as the inductive phase of catalyzer) post-reactor pressure obviously reduced in 120 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, 90 minutes total reaction times, vacuumize and remove the unreacted residual monomer, cool off to such an extent that polyether Glycols 794 restrains.
By analysis: the hydroxyl value of polyether Glycols is 30.90 milligrams of KOH/ grams, and degree of unsaturation is 0.0080 mmole/gram, and water-content is 41PPm.
C, propylene oxide polymerization
With 80 gram initiator (400Mn, K
+Content is the polyoxytrimethylene propylene glycol of 8.1PPm) and 0.020 gram catalyst V I join in 2 liters the voltage-resistant reactor, vacuumize be warming up to 105 ℃ after, add 30 gram propylene oxide, reactor pressure rises to 0.24MPa rapidly, keep temperature of reactor between 105～110 ℃, (being considered as the inductive phase of catalyzer) post-reactor pressure did not change in 180 minutes, showed catalyzer inactivation.
D, propylene oxide polymerization
With 50 gram initiator (500Mn, K
+Content is the polyoxytrimethylene glycerol of 4.9PPm) and 0.0125 gram catalyst V I join in 2 liters the voltage-resistant reactor, vacuumize be warming up to 105 ℃ after, add 30 gram propylene oxide, reactor pressure rises to 0.23MPa rapidly, keep temperature of reactor between 105～110 ℃, (being considered as the inductive phase of catalyzer) post-reactor pressure obviously reduced in 150 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, 150 minutes total reaction times, vacuumize and remove the unreacted residual monomer, cool off to such an extent that polyether-tribasic alcohol 490 restrains.
By analysis: the hydroxyl value of polyether-tribasic alcohol is 35.50 milligrams of KOH/ grams, and degree of unsaturation is 0.0078 mmole/gram, and water-content is 42PPm.
E, propylene oxide polymerization
With 50 gram initiator (500Mn, K
+Content is the polyoxytrimethylene glycerol of 8.3PPm) and 0.0125 gram catalyst V I join in 2 liters the voltage-resistant reactor, vacuumize be warming up to 105 ℃ after, add 30 gram propylene oxide, reactor pressure rises to 0.25MPa rapidly, keep temperature of reactor between 105～110 ℃, (being considered as the inductive phase of catalyzer) post-reactor pressure did not change in 180 minutes, showed catalyzer inactivation.
[embodiment 4]
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 VII 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, 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 V II 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.
C, 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 V II 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, when no longer changing, the pressure of reactor shows that reaction finishes, 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.
D, 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 V II 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.
E, propylene oxide polymerization
With 70 gram initiators (700 moles. weight. the polyoxytrimethylene glycerol) and 0.0125 restrain in the voltage-resistant reactor that catalyst V II 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, when no longer changing, the pressure of reactor shows that reaction finishes, 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 5]
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 VIII 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, 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 V III 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.
[embodiment 6]
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 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 IX 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, 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 X joins 2 liters, 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 18 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, 20 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 0.0050 mmole/gram, and water-content is 37PPm.
[comparative example 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 30 minutes, with sand core funnel vacuumizing filtration.The solid that obtains is added 150 milliliters of trimethyl carbinols and 60 ml distilled waters, be 8000 rev/mins at rotating speed and descend stirring after 20 minutes, centrifugation.The solid that obtains is added 200 milliliters of trimethyl carbinols again, be 8000 rev/mins at rotating speed and descend stirring after 20 minutes, centrifugation.Solid is got solid powder th-1 catalyst X 10.2 grams 60 ℃ of following vacuum-drying to constant weights.
By analysis: Co 10.9% (weight) Zn 29.2% (weight)
The trimethyl carbinol 10.9% (weight)
B, propylene oxide polymerization
With 70 gram initiators (700 moles. weight. the polyoxytrimethylene propylene glycol) and 0.010 restrain in the voltage-resistant reactor that catalyzer X 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 90 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, 80 minutes total reaction times, vacuumize and remove the unreacted residual monomer, cool off to such an extent that polyether Glycols 394 restrains.
By analysis: the hydroxyl value of polyether Glycols is 30.70 milligrams of KOH/ grams, and degree of unsaturation is 0.0083 mmole/gram, and water-content is 41PPm.
Claims (9)
1, a kind of preparation method of low-unsaturated polyether polyatomic alcohol, with molecular weight is 300～1000 to contain at least that the polyvalent alcohol of two or more active hydrogen groups is an 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, wherein 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;
C) 0.1～30% organic ester that is selected from positive silicon ester and composition thereof or aromatic diester and composition thereof; Wherein positive silicon ester and composition thereof molecular structure is Si (OR)
4, wherein R is the alkyl of 1～20 carbon atom can be the same or different; Aromatic diester is a phthalic ester, and molecular structure is
Its R
1Or R
2Be respectively the alkyl of 1～20 carbon atom.
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, [Bb (CN) respectively
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
1～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 consumption that it is characterized in that being selected from positive silicon ester and composition thereof or aromatic diester and composition thereof is 10～30%.
7,, it is characterized in that R, R according to the preparation method of the described low-unsaturated polyether polyatomic alcohol of claim 1
1Or R
2Be respectively the alkyl that is selected from 1～4 carbon atom.
8,, it is characterized in that R, R according to the preparation method of the described low-unsaturated polyether polyatomic alcohol of claim 7
1Or R
2Be respectively methyl, ethyl, butyl or the tertiary butyl.
9,, 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..
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| CN1320029C (en) * | 2005-05-31 | 2007-06-06 | 抚顺佳化聚氨酯有限公司 | Method for preparing polyether glycol |
| CN101302288B (en) * | 2008-05-09 | 2011-02-09 | 中国石油化工股份有限公司上海石油化工研究院 | Continuous preparation of low-unsaturated polyether polyatomic alcohol |
| CN104927040B (en) * | 2014-03-17 | 2016-09-07 | 中国石油化工股份有限公司 | The preparation method of the fatty poly-ester carbonate of dmc catalyst catalysis |
| CN103910865B (en) * | 2014-03-27 | 2017-02-01 | 上海应用技术学院 | Bimetallic cyanide catalyst containing micro-molecular polyether polyol and preparation method of bimetallic cyanide catalyst |
| CN105237757B (en) * | 2014-07-11 | 2017-10-27 | 中国石油化工股份有限公司 | For oxyalkylene and the catalyst of lactide ring opening copolymer |
| CN104497298B (en) * | 2015-01-16 | 2017-02-22 | 江苏长华聚氨酯科技有限公司 | Method for preparing polyether polyol with low degree of unsaturation, high molecular weight and high activity |
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| WO1999044739A1 (en) * | 1998-03-05 | 1999-09-10 | Basf Aktiengesellschaft | Supported double metal cyanide catalysts, method for producing them, and their use for producing polyether alcohols |
| WO2000007721A1 (en) * | 1998-07-31 | 2000-02-17 | Bayer Aktiengesellschaft | Bimetallic-cyanide catalysts used for preparing polyether polyols |
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| WO2000007721A1 (en) * | 1998-07-31 | 2000-02-17 | Bayer Aktiengesellschaft | Bimetallic-cyanide catalysts used for preparing polyether polyols |
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