CN109485844A - The preparation method of high activity high molecular polyether polyol polyalcohol - Google Patents
The preparation method of high activity high molecular polyether polyol polyalcohol Download PDFInfo
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- CN109485844A CN109485844A CN201811422628.5A CN201811422628A CN109485844A CN 109485844 A CN109485844 A CN 109485844A CN 201811422628 A CN201811422628 A CN 201811422628A CN 109485844 A CN109485844 A CN 109485844A
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G65/00—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule
- C08G65/02—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule from cyclic ethers by opening of the heterocyclic ring
- C08G65/26—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule from cyclic ethers by opening of the heterocyclic ring from cyclic ethers and other compounds
- C08G65/2603—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule from cyclic ethers by opening of the heterocyclic ring from cyclic ethers and other compounds the other compounds containing oxygen
- C08G65/2606—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule from cyclic ethers by opening of the heterocyclic ring from cyclic ethers and other compounds the other compounds containing oxygen containing hydroxyl groups
- C08G65/2609—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule from cyclic ethers by opening of the heterocyclic ring from cyclic ethers and other compounds the other compounds containing oxygen containing hydroxyl groups containing aliphatic hydroxyl groups
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
- C08G18/40—High-molecular-weight compounds
- C08G18/48—Polyethers
- C08G18/4833—Polyethers containing oxyethylene units
- C08G18/4837—Polyethers containing oxyethylene units and other oxyalkylene units
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- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G65/00—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule
- C08G65/02—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule from cyclic ethers by opening of the heterocyclic ring
- C08G65/26—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule from cyclic ethers by opening of the heterocyclic ring from cyclic ethers and other compounds
- C08G65/2642—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule from cyclic ethers by opening of the heterocyclic ring from cyclic ethers and other compounds characterised by the catalyst used
- C08G65/2645—Metals or compounds thereof, e.g. salts
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G65/00—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule
- C08G65/02—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule from cyclic ethers by opening of the heterocyclic ring
- C08G65/26—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule from cyclic ethers by opening of the heterocyclic ring from cyclic ethers and other compounds
- C08G65/2642—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule from cyclic ethers by opening of the heterocyclic ring from cyclic ethers and other compounds characterised by the catalyst used
- C08G65/2669—Non-metals or compounds thereof
- C08G65/2675—Phosphorus or compounds thereof
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G2101/00—Manufacture of cellular products
Abstract
The present invention relates to a kind of preparation methods of polyether polyol, and in particular to a kind of preparation method of high activity high molecular polyether polyol polyalcohol.Include the following steps: that (1), as initiator, using phosphorus nitrile compounds as catalyst, carries out polymerization reaction, synthesizing polyether glycol oligomer with propylene oxide using the mixture of glycerol ether compound and small molecule compound composition；(2) using polyether polyol oligomer as basic polyethers, in -0.1~0.3MPa pressure, at a temperature of 90~130 DEG C, propylene oxide is added to react with the mixture of ethylene oxide progress polymerization reaction and internal pressure, it then adds ethylene oxide and carries out dead-end polymerization reaction and internal pressure reaction, the thick polymers of polyether polyol is made；(3) refine to get.The active height of polyether polyol produced by the present invention, volatile organic content is few, the feature that smell is small, to collapse intensity high.
Description
Technical field
The present invention relates to a kind of preparation methods of polyether polyol, and in particular to a kind of low unsaturation of high activity high molecular weight
Spend the preparation method of polyether polyol.
Background technique
It is using small molecule polyol as initiator, under the action of catalyst and epoxy that polyether polyol, which produces usual method,
Propane (PO) carries out anionic ring-opening polymerization.Currently, the most common anion ring opening catalyst of application is hydrogen-oxygen in industrial circle
Change potassium, this is because it does not need too fierce reaction condition (pressure 0.2-0.5MPa, 100-130 DEG C of temperature), and urges
Agent cost is small, and reaction process is easily controlled.But using potassium hydroxide as catalyst, it is also easy to produce in polymerization process
Chain transfer reaction, so as to cause a series of defects of its product, as degree of unsaturation is high, product molecular weight distribution is wider, average molecular
Of low quality etc., therefore product performance index is affected, to limit the application of its product.
Based on the above issues, several new catalysts come out in foreign countries, and the bimetallic cyaniding of industrialized production
Object complex catalyst (DMC) is the most typical.DMC catalytic activity is extremely prominent, the polyether polyol tool for using DMC to produce for raw material
There are the advantages such as narrow molecular weight distribution, relative molecular mass are high, terminal unsaturation is low.But dmc catalyst equally exists some answer
With defect, it is not available small molecule compound such as its initiator.In addition, if not allowing dmc catalyst to inactivate, then can not lead to
Ethylene oxide (EO) directly sealing end is crossed to improve its product proportion of primary OH groups, increases Product Activity.Dmc catalyst include metal at
Point, if remaining DMC in polyether polyol, product service performance, degree of unsaturation and stability, which will receive, to be significantly affected,
And the removing sulfuldioxide of such catalyst is extremely many and diverse.
Summary of the invention
In view of the deficiencies of the prior art, the object of the present invention is to provide a kind of high activity high molecular polyether polyols
The preparation method of polyalcohol, the active height of polyether polyol obtained, volatile organic content is few, and smell is small, it is strong to collapse
Spend high feature.
The preparation method of high activity high molecular polyether polyol polyalcohol of the present invention, including walk as follows
It is rapid:
(1) mixture formed using glycerol ether compound and small molecule compound is as initiator, with phosphonitrile class
Object is closed as catalyst, carries out polymerization reaction, synthesizing polyether glycol oligomer with propylene oxide；
(2) using polyether polyol oligomer made from step (1) as basic polyethers, in -0.1~0.3MPa pressure, 90
At a temperature of~130 DEG C, propylene oxide is added and is reacted with the mixture of ethylene oxide progress polymerization reaction and internal pressure, then adds
Ethylene oxide carries out dead-end polymerization reaction and internal pressure reaction, and the thick polymers of polyether polyol is made；
(3) by the thick polymers of polyether polyol made from step (2) through refinement treatment to get the low insatiable hunger of high activity high molecular weight
With degree polyether polyol；
Wherein, the glycerol ether compound is the polyethers that number-average molecular weight is 400~600 using glycerol as initiator
Polyol compound；The small molecule compound is one of propylene glycol, glycerol, sorbierite or sucrose, small molecule chemical combination
The dosage of object is the 0.5-5wt% of initiator.
In step (1), initiator and propylene oxide mass ratio are 0.082~0.132:1.
In step (1), in the polyether polyol oligomer, the content of catalyst is 0.05~1wt%.Phosphonitrile class is urged
Agent is a kind of strong alkali catalyst, can be used for catalytic epoxy compound and carries out ring-opening polymerisation.With potassium hydroxide catalyst series
It compares, phosphonitrile class catalyst has catalytic activity high, and polymerization process by-product is few, and products therefrom unsaturated value is low, and volatility has
The advantages that machine object content is small；Compared with the dmc catalyst of high activity, small molecule compound can be used to be used as phosphonitrile class catalyst
EO sealing end can be used in polymerization process for beginning agent.
In step (1), polymeric reaction temperature is 100~140 DEG C, and pressure is -0.1~0.3MPa.
In step (2), the mass ratio of basic polyether and epoxide is 1.86~3.25:1, wherein epoxide
Refer to the summation of ethylene oxide and propylene oxide.
In step (2), in the mixture of the propylene oxide and ethylene oxide, the quality of propylene oxide and ethylene oxide
Than for 6~9:1, the content of ethylene oxide is the total amount of the mixture of polyether polyol oligomer and propylene oxide and ethylene oxide
2~5wt%；When ethylene oxide progress dead-end polymerization reaction is added, the content of ethylene oxide is the thick polymers of polyether polyol
10~20wt%.
In step (2), polymerization reaction and internal pressure reaction temperature are 90~130 DEG C, and pressure is -0.1~0.3MPa.
In step (3), the refinement treatment is neutralization, absorption, dry and filtering.
The acid that the neutralization uses forms for one or more of sulfuric acid, phosphoric acid, hydrochloric acid according to arbitrary proportion mixed
Object is closed, sour additional amount is the 0.01-0.05wt% of the thick polymers of polyether polyol.
The adsorbent that the absorption uses is one or more of magnesium silicate, alumina silicate, aluminium-magnesium silicate according to any
The mixture of ratio composition, the additional amount of adsorbent are 0.05~0.5wt% of the thick polymers of polyether polyol.
Compared with prior art, beneficial effects of the present invention are as follows:
1, the high activity high molecular polyether polyol polyalcohol prepared by the present invention is used for the system of polyurethane foam
When standby, not only have compared with high reaction activity, and the mechanical performance of material can be obviously improved.High activity prepared by the present invention is high
The features such as molecular weight low-unsaturated polyether polyatomic alcohol also has volatile organic content few, and product odour is small, can meet
Related request of the superior automobile seat product to polyurethane foam.
2, when the present invention carries out the preparation of high molecular weight polyether using phosphonitrile class catalyst, side reaction can be reduced
It generates, to be conducive to the preparation of high activity high molecular polyether polyol polyalcohol.
3, the present invention uses compound initiator, the preparation for high activity high molecular polyether polyol polyalcohol
When, the degree of functionality of product can be adjusted, improves product reactivity, product different activities is wanted when meeting client's downstream application
It asks, further, it is possible to substantially reduce volatile organic content.
4, in the preparation process of polyether polyol, propylene oxide is mixed with ethylene oxide according to certain mass ratio the present invention
It is added, is conducive to the reactivity for further increasing final product polyether polyol.
5, preparation method of the present invention, it is scientific and reasonable, simple and easy.
Specific embodiment
The present invention is further elaborated combined with specific embodiments below, but the present invention is not limited to following embodiments.
The method is conventional method unless otherwise instructed.
The raw material can be gotten from open business unless otherwise instructed.
Embodiment 1
(1) preparation of polyether polyol oligomer
In 15m3Stainless steel cauldron in 576kg glycerin ether (400 molecular weight), 28.8kg propylene glycol and 4kg tetra- is added
(tetramethyl guanidine radicals) phosphonitrile chloride carries out nitrogen displacement, surveys oxygen content in reaction kettle and is lower than 80ppm.100 DEG C are warming up to, into
Row nitrogen is bubbled decompression dehydration.Keeping temperature in the kettle is 102 ± 2 DEG C, and pressure is -0.1~0.3MPa, is continuously added to 7461kg ring
Ethylene Oxide, internal pressure are reacted 60 minutes, and reaction temperature is 102 ± 2 DEG C, subsequent demonomerization 30 minutes, be can be prepared by having and efficiently be urged
Change active polyether polyol oligomer.
(2) preparation of the thick polymers of high-activity high molecular weight polyether polyol
Using the above-mentioned polyether polyol oligomer with high-efficiency catalytic activity as basic polyethers, keeping temperature in the kettle is 92
± 2 DEG C, pressure is -0.1~0.3MPa, and 1308kg propylene oxide and 218kg epoxy is added in Xiang Shangshu polyether polyol oligomer
The mixture of ethane composition, subsequent internal pressure are reacted 30 minutes, and internal pressure reaction temperature is 92 ± 2 DEG C.Keeping temperature in the kettle is 92 ± 2
DEG C, pressure is 0.18~0.3MPa, and 1186kg ethylene oxide is added into reaction kettle and carries out dead-end polymerization reaction, then in progress
Pressure reaction, internal pressure reaction temperature are 92 ± 2 DEG C, and it is polynary to can be prepared by high activity high molecular weight polyether for subsequent demonomerization 30 minutes
The thick polymers of alcohol.
(3) purification of the thick polymers of polyether polyol
1.37kg70% phosphoric acid is added into the thick polymers of above-mentioned polyether polyol, neutralizes 1 hour, 7.17kg silicon is then added
Sour aluminium stirs 30 minutes, then through drying, filtering, obtains high-activity high molecular weight polyether polyol.
Analysis indexes are as follows, hydroxyl value: 24.1mgKOH/g, viscosity: 1410mPa.s, unsaturated value: 0.021mol/kg, water
Point: 0.019wt%, color value (APHA): 9, acid value: 0.02mgKOH/g.
Embodiment 2
(1) preparation of polyether polyol oligomer
In 15m3Stainless steel cauldron in 752kg glycerin ether (600 molecular weight), 15kg glycerol and 66kg tetra- (four is added
Methyl guanidine radicals) phosphonitrile hydroxide, nitrogen displacement is carried out, oxygen content in reaction kettle is surveyed and is lower than 80ppm.100 DEG C are warming up to, is carried out
Nitrogen is bubbled decompression dehydration.Keeping temperature in the kettle is 138 ± 2 DEG C, and pressure is -0.1~0.3MPa, is continuously added to 5828kg epoxy
Propane, internal pressure are reacted 60 minutes, and reaction temperature is 138 ± 2 DEG C, and subsequent demonomerization 30 minutes can be prepared by with efficient catalytic
Active polyether polyol oligomer.
(2) preparation of the thick polymers of high-activity high molecular weight polyether polyol
Using the above-mentioned polyether polyol oligomer with high-efficiency catalytic activity as basic polyethers, holding temperature in the kettle is
128 ± 2 DEG C, pressure is -0.1~0.3MPa, and 1674kg propylene oxide and 186kg ring is added in Xiang Shangshu polyether polyol oligomer
The mixture of oxidative ethane composition, subsequent internal pressure are reacted 30 minutes, and internal pressure reaction temperature is 128 ± 2 DEG C.Keep temperature in the kettle be
128 ± 2 DEG C, pressure is 0.18~0.3MPa, and 1688kg ethylene oxide is added into reaction kettle and carries out dead-end polymerization reaction, then
Internal pressure reaction is carried out, internal pressure reaction temperature is 128 ± 2 DEG C, and subsequent demonomerization 30 minutes can be prepared by high activity high-molecular-weight poly
The thick polymers of ethoxylated polyhydric alcohol.
(3) purification of the thick polymers of polyether polyol
4.22kg sulfuric acid is added into the thick polymers of above-mentioned polyether polyol, neutralizes 1 hour, 42.2kg magnesium silicate is then added
Aluminium stirs 30 minutes, then through drying, filtering, obtains high-activity high molecular weight polyether polyol.
Analysis indexes are as follows, hydroxyl value: 24.99mgKOH/g, viscosity: 1330mPa.s, unsaturated value: 0.023mol/kg, water
Point: 0.023wt%, color value (APHA): 12, acid value: 0.03mgKOH/g.
Embodiment 3
(1) preparation of polyether polyol oligomer
In 15m3Stainless steel cauldron in 479kg glycerin ether (550 molecular weight), 4.79kg sorbierite and 28kg tetra- is added
(tetramethyl guanidine radicals) phosphonitrile bicarbonate carries out nitrogen displacement, surveys oxygen content in reaction kettle and is lower than 80ppm.100 DEG C are warming up to,
It carries out nitrogen and is bubbled decompression dehydration.Keeping temperature in the kettle is 110 ± 2 DEG C, and pressure is -0.1~0.3MPa, is continuously added to 4249kg
Propylene oxide, internal pressure are reacted 60 minutes, and reaction temperature is 110 ± 2 DEG C, subsequent demonomerization 30 minutes, can be prepared by having efficient
The polyether polyol oligomer of catalytic activity.
(2) preparation of the thick polymers of high-activity high molecular weight polyether polyol
Using the above-mentioned polyether polyol oligomer with high-efficiency catalytic activity as basic polyethers, holding temperature in the kettle is
110 ± 2 DEG C, pressure is -0.1~0.3MPa, and 1017kg propylene oxide and 117kg ring is added in Xiang Shangshu polyether polyol oligomer
The mixture of oxidative ethane composition, subsequent internal pressure are reacted 30 minutes, and internal pressure reaction temperature is 110 ± 2 DEG C.Keep temperature in the kettle be
110 ± 2 DEG C, pressure is 0.18~0.3MPa, and 763kg ethylene oxide is added into reaction kettle and carries out dead-end polymerization reaction, then
Internal pressure reaction is carried out, internal pressure reaction temperature is 110 ± 2 DEG C, and subsequent demonomerization 30 minutes can be prepared by high activity high-molecular-weight poly
The thick polymers of ethoxylated polyhydric alcohol.
(3) purification of the thick polymers of polyether polyol
1.17kg hydrochloric acid is added into the thick polymers of above-mentioned polyether polyol, neutralizes 1 hour, 5.86kg alumina silicate is then added
With the mixture of aluminium-magnesium silicate, stirs 30 minutes, then through drying, filtering, obtain high-activity high molecular weight polyether polyol.
Analysis indexes are as follows, hydroxyl value: 25.1mgKOH/g, viscosity: 1360mPa.s, unsaturated value: 0.025mol/kg, water
Point: 0.031wt%, color value (APHA): 17, acid value: 0.02mgKOH/g.
Embodiment 4
(1) preparation of polyether polyol oligomer
In 15m3Stainless steel cauldron in be added 590kg glycerin ether (500 molecular weight), 2.95kg sucrose and 31kg oxidation
Phosphazene compound carries out nitrogen displacement, surveys oxygen content in reaction kettle and is lower than 80ppm.100 DEG C are warming up to, nitrogen bubbling is carried out and subtracts
Press-dehydrating.Keeping temperature in the kettle is 115 ± 2 DEG C, and pressure is -0.1~0.3MPa, is continuously added to 5816kg propylene oxide, internal pressure
Reaction 60 minutes, reaction temperature are 115 ± 2 DEG C, and subsequent demonomerization 30 minutes can be prepared by the polyethers with high-efficiency catalytic activity
Polyol oligomer.
(2) preparation of the thick polymers of high-activity high molecular weight polyether polyol
Using the above-mentioned polyether polyol oligomer with high-efficiency catalytic activity as basic polyethers, holding temperature in the kettle is
120 ± 2 DEG C, pressure is -0.1~0.3MPa, and 1160kg propylene oxide and 187kg ring is added in Xiang Shangshu polyether polyol oligomer
The mixture of oxidative ethane composition, subsequent internal pressure are reacted 30 minutes, and internal pressure reaction temperature is 120 ± 2 DEG C.Keep temperature in the kettle be
120 ± 2 DEG C, pressure is 0.18~0.3MPa, and 1191kg ethylene oxide is added into reaction kettle and carries out dead-end polymerization reaction, then
Internal pressure reaction is carried out, internal pressure reaction temperature is 120 ± 2 DEG C, and subsequent demonomerization 30 minutes can be prepared by high activity high-molecular-weight poly
The thick polymers of ethoxylated polyhydric alcohol.
(3) purification of the thick polymers of polyether polyol
Into the thick polymers of above-mentioned polyether polyol be added 2.38kg hydrochloric acid and sulfuric acid mixture, neutralize 1 hour, then plus
Enter 15.89kg magnesium silicate, stirs 30 minutes, then through drying, filtering, obtain high-activity high molecular weight polyether polyol.
Analysis indexes are as follows, hydroxyl value: 25.0mgKOH/g, viscosity: 1350mPa.s, unsaturated value: 0.026mol/kg, water
Point: 0.028wt%, color value (APHA): 16, acid value: 0.03mgKOH/g.
Comparative example 1
(1) preparation of polyether polyol oligomer
In 15m3Stainless steel cauldron in be added 576kg glycerin ether (400 molecular weight) 4kg phosphazenium catalyst, carry out
Nitrogen displacement surveys oxygen content in reaction kettle and is lower than 80ppm.100 DEG C are warming up to, nitrogen is carried out and is bubbled decompression dehydration.It keeps in kettle
Temperature is 102 ± 2 DEG C, and pressure is -0.1~0.3MPa, is continuously added to 7461kg propylene oxide, and internal pressure is reacted 60 minutes, reaction
Temperature is 102 ± 2 DEG C, and subsequent demonomerization 30 minutes can be prepared by the polyether polyol oligomer with high-efficiency catalytic activity.
(2) preparation of the thick polymers of high-activity high molecular weight polyether polyol
Using the above-mentioned polyether polyol oligomer with high-efficiency catalytic activity as basic polyethers, keeping temperature in the kettle is 92
± 2 DEG C, pressure is -0.1~0.3MPa, and 1308kg propylene oxide and 218kg epoxy is added in Xiang Shangshu polyether polyol oligomer
The mixture of ethane composition, subsequent internal pressure are reacted 30 minutes, and internal pressure reaction temperature is 92 ± 2 DEG C.Keeping temperature in the kettle is 92 ± 2
DEG C, pressure is 0.18~0.3MPa, and 957kg ethylene oxide is added into reaction kettle and carries out dead-end polymerization reaction, then in progress
Pressure reaction, internal pressure reaction temperature are 92 ± 2 DEG C, and it is polynary to can be prepared by high activity high molecular weight polyether for subsequent demonomerization 30 minutes
The thick polymers of alcohol.
(3) purification of the thick polymers of polyether polyol
1.37kg70% phosphoric acid is added into the thick polymers of above-mentioned polyether polyol, neutralizes 1 hour, 4.78kg silicon is then added
Sour aluminium stirs 30 minutes, then through drying, filtering, obtains high-activity high molecular weight polyether polyol.
Analysis indexes are as follows, hydroxyl value: 25.3mgKOH/g, viscosity: 1380mPa.s, unsaturated value: 0.037mol/kg, water
Point: 0.025wt%, color value (APHA): 25, acid value: 0.03mgKOH/g.
Comparative example 2
(1) preparation of polyether polyol oligomer
In 15m3Stainless steel cauldron in 576kg propylene glycol and 4kg phosphazenium catalyst is added, carry out nitrogen displacement,
It surveys oxygen content in reaction kettle and is lower than 80ppm.100 DEG C are warming up to, nitrogen is carried out and is bubbled decompression dehydration.Keeping temperature in the kettle is 102
± 2 DEG C, pressure is -0.1~0.3MPa, is continuously added to 7461kg propylene oxide, and internal pressure is reacted 60 minutes, reaction temperature 102
± 2 DEG C, subsequent demonomerization 30 minutes can be prepared by the polyether polyol oligomer with high-efficiency catalytic activity.
(2) preparation of the thick polymers of high-activity high molecular weight polyether polyol
Using the above-mentioned polyether polyol oligomer with high-efficiency catalytic activity as basic polyethers, keeping temperature in the kettle is 92
± 2 DEG C, pressure is -0.1~0.3MPa, and 1308kg propylene oxide and 218kg epoxy is added in Xiang Shangshu polyether polyol oligomer
The mixture of ethane composition, subsequent internal pressure are reacted 30 minutes, and internal pressure reaction temperature is 92 ± 2 DEG C.Keeping temperature in the kettle is 92 ± 2
DEG C, pressure is 0.18~0.3MPa, and 957kg ethylene oxide is added into reaction kettle and carries out dead-end polymerization reaction, then in progress
Pressure reaction, internal pressure reaction temperature are 92 ± 2 DEG C, and it is polynary to can be prepared by high activity high molecular weight polyether for subsequent demonomerization 30 minutes
The thick polymers of alcohol.
(3) purification of the thick polymers of polyether polyol
70% phosphoric acid of 1.37kg is added into the thick polymers of above-mentioned polyether polyol, neutralizes 1 hour, 4.78kg is then added
Alumina silicate stirs 30 minutes, then through drying, filtering, obtains high-activity high molecular weight polyether polyol.
Analysis indexes are as follows, hydroxyl value: 80mgKOH/g, viscosity: 420mPa.s, unsaturated value: 0.072mol/kg, moisture:
0.021wt%, color value (APHA): 23, acid value: 0.03mgKOH/g.
Comparative example 3
(1) preparation of comparative example polyether polyol oligomer
In 15m3Stainless steel cauldron in 479kg glycerin ether (550 molecular weight) and 14kg potassium hydroxide catalyst is added,
Nitrogen displacement is carried out, oxygen content in reaction kettle is surveyed and is lower than 80ppm.100 DEG C are warming up to, nitrogen is carried out and is bubbled decompression dehydration.It keeps
Temperature in the kettle is 110 ± 2 DEG C, and pressure is -0.1~0.3MPa, is continuously added to 4249kg propylene oxide, and internal pressure is reacted 60 minutes,
Reaction temperature is 110 ± 2 DEG C, and subsequent demonomerization 30 minutes can be prepared by having the polyether polyol of high-efficiency catalytic activity oligomeric
Object.
(2) preparation of the thick polymers of comparative example polyether polyol
Using the above-mentioned polyether polyol oligomer with high-efficiency catalytic activity as basic polyethers, holding temperature in the kettle is
110 ± 2 DEG C, pressure is -0.1~0.3MPa, and 1017kg propylene oxide and 117kg ring is added in Xiang Shangshu polyether polyol oligomer
The mixture of oxidative ethane composition, subsequent internal pressure are reacted 30 minutes, and internal pressure reaction temperature is 110 ± 2 DEG C.Keep temperature in the kettle be
110 ± 2 DEG C, pressure is 0.18~0.3MPa, and 763kg ethylene oxide is added into reaction kettle and carries out dead-end polymerization reaction, then
Internal pressure reaction is carried out, internal pressure reaction temperature is 110 ± 2 DEG C, and subsequent demonomerization 30 minutes can be prepared by high activity high-molecular-weight poly
The thick polymers of ethoxylated polyhydric alcohol.
(3) purification of the thick polymers of comparative example polyether polyol
1.17kg phosphoric acid is added into the thick polymers of above-mentioned polyether polyol, neutralizes 1 hour, 5.86kg alumina silicate is then added
With the mixture of aluminium-magnesium silicate, stirs 30 minutes, then through drying, filtering, obtain high-activity high molecular weight polyether polyol.
Analysis indexes are as follows, hydroxyl value: 28.5mgKOH/g, viscosity: 1350mPa.s, unsaturated value: 0.076mol/kg, water
Point: 0.028wt%, color value (APHA): 16, acid value: 0.03mgKOH/g.
Distinguish polyethers made from high-activity high molecular weight polyether polyol made from testing example 1-4 and comparative example 1-3
Number-average molecular weight, content of formaldehyde, acetaldehyde, level of acrolein and the proportion of primary OH groups of polyalcohol, test result are shown in Table 1.
1 polyether polyol test result of table
High-activity high molecular weight polyether polyol made from embodiment 1-4 and comparative example 1-3 polyether polyol is respectively adopted
For one of raw material, polyurethane foam is prepared using same process, the test index of polyurethane foam obtained is shown in Table 2.
2 polyurethane foam test result of table
Claims (10)
1. a kind of preparation method of high activity high molecular polyether polyol polyalcohol, it is characterised in that: including walking as follows
It is rapid:
(1) mixture formed using glycerol ether compound and small molecule compound is as initiator, with phosphorus nitrile compounds
As catalyst, polymerization reaction, synthesizing polyether glycol oligomer are carried out with propylene oxide；
(2) using polyether polyol oligomer made from step (1) as basic polyethers, in -0.1~0.3MPa pressure, 90~130
At a temperature of DEG C, propylene oxide is added and is reacted with the mixture of ethylene oxide progress polymerization reaction and internal pressure, then adds epoxy
Ethane carries out dead-end polymerization reaction and internal pressure reaction, and the thick polymers of polyether polyol is made；
(3) by the thick polymers of polyether polyol made from step (2) through refinement treatment to get high activity high molecular weight low-unsaturation-degree
Polyether polyol；
Wherein, the glycerol ether compound is the polyether polyols that number-average molecular weight is 400~600 using glycerol as initiator
Alcoholic compound；The small molecule compound is one of propylene glycol, glycerol, sorbierite or sucrose, small molecule compound
Dosage is 0.5~5wt% of initiator.
2. the preparation method of high activity high molecular polyether polyol polyalcohol according to claim 1, feature
Be: in step (1), initiator and propylene oxide mass ratio are 0.082~0.132:1.
3. the preparation method of high activity high molecular polyether polyol polyalcohol according to claim 1, feature
Be: in step (1), in the polyether polyol oligomer, the content of catalyst is 0.05~1wt%.
4. the preparation method of high activity high molecular polyether polyol polyalcohol according to claim 1, feature
Be: in step (1), polymeric reaction temperature is 100~140 DEG C, and pressure is -0.1~0.3MPa.
5. the preparation method of high activity high molecular polyether polyol polyalcohol according to claim 1, feature
Be: in step (2), the mass ratio of basic polyether and epoxide is 1.86~3.25:1, wherein epoxide refers to
The summation of ethylene oxide and propylene oxide.
6. the preparation method of high activity high molecular polyether polyol polyalcohol according to claim 1, feature
It is: in step (2), in the mixture of the propylene oxide and ethylene oxide, the mass ratio of propylene oxide and ethylene oxide
For 6~9:1, the content of ethylene oxide is the total amount of the mixture of polyether polyol oligomer and propylene oxide and ethylene oxide
2~5wt%；When ethylene oxide progress dead-end polymerization reaction is added, the content of ethylene oxide is the 10 of the thick polymers of polyether polyol
~20wt%.
7. the preparation method of high activity high molecular polyether polyol polyalcohol according to claim 1, feature
Be: in step (2), polymerization reaction and internal pressure reaction temperature are 90~130 DEG C, and pressure is -0.1~0.3MPa.
8. the preparation method of high activity high molecular polyether polyol polyalcohol according to claim 1, feature
Be: in step (3), the refinement treatment is neutralization, absorption, dry and filtering.
9. the preparation method of high activity high molecular polyether polyol polyalcohol according to claim 8, feature
It is: the mixing that the acid that the neutralization uses forms for one or more of sulfuric acid, phosphoric acid, hydrochloric acid according to arbitrary proportion
Object, sour additional amount are 0.01~0.05wt% of the thick polymers of polyether polyol.
10. the preparation method of high activity high molecular polyether polyol polyalcohol according to claim 8, feature
Be: the adsorbent that the absorption uses is one or more of magnesium silicate, alumina silicate, aluminium-magnesium silicate according to arbitrary proportion
The mixture of composition, the additional amount of adsorbent are 0.05~0.5wt% of the thick polymers of polyether polyol.
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