CN109438691A - A kind of preparation method of low-odor polyether polyol - Google Patents
A kind of preparation method of low-odor polyether polyol Download PDFInfo
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- CN109438691A CN109438691A CN201811040671.5A CN201811040671A CN109438691A CN 109438691 A CN109438691 A CN 109438691A CN 201811040671 A CN201811040671 A CN 201811040671A CN 109438691 A CN109438691 A CN 109438691A
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- propylene oxide
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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
- 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
- C08G65/2648—Alkali metals 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
- 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
- C08G65/30—Post-polymerisation treatment, e.g. recovery, purification, drying
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Abstract
The invention discloses a kind of preparation methods of low-odor polyether polyol, use multicomponent alcoholics compound for initiator, at a temperature of 0-0.4MPa pressure, 80-140 DEG C, are reacted by catalyst of potassium hydroxide, and in 20~25h of air speed‑1It is lower to adsorb drop aldehyde treated propylene oxide step-by-step polymerization through molecular sieve tank, with ethylene oxide-capped, obtain thick polyethers, thick polyethers is after neutralizing absorption, isopropanol water solution is added, is reacted 30 minutes at 60~80 DEG C, obtains low-odor polyether polyol through vacuum distillation；Wherein, the quality of multicomponent alcoholics compound accounts for the 1-16% of total amount of feeding, the quality of propylene oxide accounts for the 67.5-90.8% of total amount of feeding, and the quality of ethylene oxide accounts for the 8-16% of total amount of feeding, the quality of alkali metal hydroxide accounts for total amount of feeding 0.2-0.5%.Obtained Contents In Polyether Polyol oder levels≤2.5, environmental-protecting performance are preferable.
Description
Technical field
The invention belongs to chemical fields, and in particular to a kind of preparation method of low-odor polyether polyol.
Background technique
Polyurethane (PU) flex foam is widely used in aviation, automobile and furniture industry.With China's aviation and automobile
Industrial expansion, the physical mechanical property such as resilience and load of common PU foam have been far from satisfying aviation, advanced
The requirement of car and vehicles running on expressway to foam seat cushions comfortableness and security.Currently, many industrially developed country
The dosage of the vehicles of production, height rebound PU foam is rising year by year, according to reports, american car seat cushion 95% is all with height
Spring back PU foam.In recent years, development of automobile industry was rapid, in addition the fast development of civil aviaton and high-speed rail, develops and production was both relaxed
Suitable and safety high rebound PU foam seat cushions are very urgent.
The continuous promotion of Environmental Protection in China theory in recent years, 2014, Ministry of Industry and Information carried out " interior volatile organic contaminant
(VOC) control technology policy ", to clear vehicle, components, material enterprise tripartite's responsibility.Chinese Ministry of Environmental Protection's publication in 2017 is " riding
In-car air quality evaluation guide " increasingly complicated interior Quality link how is effectively improved, it is healthy to consumer one
Multiply and drive environment, it has also become each Automobile Enterprises problem in the urgent need to address.Therefore client also increasingly closes the smell of polyethers
Note will be puted forth effort to promote product quality, meet ecological requirements in polyether polyol synthetic technology.
Domestic and international major manufacturing enterprise and scientific research institution surround Contents In Polyether Polyol smell problem and a large amount of work have also been made
Make.US6504062 reports the preparation method of obour-lean polyether polyols.From by making that there are multiple active hydrogen atoms
The polyethers that beginning compound and one or more alkylene oxide reactions polyether polyol initial product obtained prepare obour-lean is more
The method of first alcohol, method includes the following steps: (a) allow in and/or unneutralized polyether polyol product and excessive pKa value
Acid lower than 5 contacts under hydrolysising condition, and reaction mixture (b) is allowed to contact under hydrolysising condition with water, and (c) recycling smell is dilute
Few polyether polyol.
CN 104130389 reports the method for reducing polyether polyol VOC content.The invention, will in closed reactor
Oxide is added it in polyether polyol by protruding into the feeding line of bottom, certain pressure and at a temperature of mixed
It closes, then mixture is post-processed to obtain the low Contents In Polyether Polyol of VOC content.
US5672768 reports low smell, high molecular weight polyether, Its Preparation Method And Use.The invention is logical
It crosses certain method and is prepared for low smell, high molecular weight polyether；At 110-150 DEG C of temperature and 10-70hPa pressure,
The water that 5-30% is added purifies polyether polyol, and wherein water measures addition 1-5 hours in the form of dispersion fine crushing.
CN101240055 reports a kind of Preparation method and use of low VOC content polyurethane foam.Relate generally to low wave
The Preparation method and use of the polyurethane foam of hair property organic compound content, method is: raw material is that the polyethers that handles again is more
First alcohol, the polymer polyatomic alcohol of low volatile content, foaming agent, low smell catalyst, crosslinking agent, low fogging silicone oil and low volatilization
Object content isocyanates, mixes in proportion, enters swage tool, 45-50 DEG C of temperature, demoulding is old after the foam sample placement after depanning
Chemical conversion type, detection.
Contents In Polyether Polyol technical maturity is stablized at present, but with people's increasing emphasis on environmental protection, how effective
Reducing Contents In Polyether Polyol smell becomes the problem of everybody very pays close attention to and polyether polyol future development emphasis.
Summary of the invention
In order to solve the problems, such as that Contents In Polyether Polyol smell is being effectively reduced, the present invention provides a kind of low-odor polyethers
The preparation method of polyalcohol.
Specific technical solution of the present invention is as follows:
A kind of preparation method of low-odor polyether polyol, it is characterized in that including the following steps:
1) raw material propylene oxide is in 20~25h of air speed-1Down by molecular sieve tank, drop aldehyde processing is adsorbed through molecular sieve tank, is obtained
To low aldehyde propylene oxide；
2) use multicomponent alcoholics compound for initiator, at a temperature of 0-0.4MPa pressure, 80-140 DEG C, in alkali metal hydrogen
Oxide catalyst is reacted under participating in, and first disposably put into the low total dosage of aldehyde propylene oxide 5%~10% carries out pre-polymerization
It closes, is lower than 0.05MPa to reaction pressure, remaining low aldehyde propylene oxide is continuously put into reaction, vacuumizing after the reaction was completed will not
Reaction monomers abjection obtains thick polyethers finally with ethylene oxide-capped；
3) for thick polyethers after neutralizing purification, pH value 4.8-6.5 adds isopropanol water solution, anti-at 60~80 DEG C
It answers 30 minutes~180 minutes, is finally evaporated under reduced pressure to obtain low-odor polyether polyol.
The low aldehyde propylene oxide aldehyde 0.0001~0.0006% that the step 1) obtains.
Step 2) the material component and percentage composition are as follows:
Total amount of feeding is total for said components, in terms of 100%.
The multicomponent alcoholics compound is glycerol, ethylene glycol, diethylene glycol, propylene glycol, dipropylene glycol or trihydroxy methyl third
Alkane it is one or more.
The alkali metal hydroxide catalyst is potassium hydroxide or sodium hydroxide.
The molecular sieve be aluminium oxide, silica type molecular sieve or other have the molecular sieve of aldehyde material adsorption capacity.
The dosage of the isopropanol water solution is the 5-20% of polyether polyol quality.Isopropanol water solution composition are as follows: different
Propyl alcohol 30-50%, water 50-70%.
Gained low-odor polyether polyol oder levels 1~2.5.
Compared with prior art, advantages of the present invention is as follows:
Raw material propylene oxide is pre-processed using analysis sieve suction type, and Contents In Polyether Polyol has been carried out into one
Step post-processing, makes Contents In Polyether Polyol smell be reduced to 1~2.5 from grade 3, product performance index is excellent.
Specific embodiment
General description has been carried out to the present invention, the present invention has been done combined with specific embodiments below further detailed
Description.
Embodiment 1
By 5000g propylene oxide with air speed 20h-1By 200ml molecular sieve tank, drop aldehyde processing is adsorbed through molecular sieve tank, is obtained
To low aldehyde propylene oxide, surveying propylene oxide aldehyde is 0.0005%；
Glycerol 92g, potassium hydroxide 10g are put into stainless steel cauldron, nitrogen displacement by the polyether polyol for synthesizing 5000g
Three times, it at a temperature of 0.4MPa pressure, 140 DEG C, first disposably puts into low aldehyde propylene oxide 214.9g and carries out prepolymerization, wait react
Pressure is lower than 0.05MPa, and the low aldehyde propylene oxide of remaining 4083.1g is continuously put into reaction, and vacuumizing after the reaction was completed will be not anti-
Monomer is answered to deviate from；It is ethylene oxide-capped with the rate investment 600g of 1g/min, obtain thick polyethers；Wherein, glycerol matter in thick polyethers
Amount accounts for the 1.8% of the total amount of feeding, quality of propylene oxide and accounts for the 86% of total amount of feeding, and the quality of ethylene oxide accounts for total amount of feeding
12%, the quality of alkali metal hydroxide accounts for total amount of feeding 0.2%；Wherein the quality of prepolymerization propylene oxide accounts for low aldehyde epoxy third
The 5% of the total dosage of alkane；
After the neutralized adsorption treatment of crude polyoxyalkylene polyol, pH value 4.8 adds aqueous isopropanol 250g, anti-at 80 DEG C
30min is answered, vacuum distillation obtains low-odor polyether polyol A at -0.1MPa；(dosage of isopropanol water solution is that polyethers is more
The 5% of first alcohol quality；The composition of isopropanol water solution are as follows: isopropanol 30%, water 70%.
Embodiment 2
By 5000g propylene oxide with air speed 25h-1By 200ml adsorption tanks, the propylene oxide after adsorbing is collected, surveys epoxy
Propane aldehyde is 0.0001%.
Glycerol 50g, potassium hydroxide 10g are put into stainless steel cauldron, nitrogen displacement by the polyether polyol for synthesizing 5000g
Three times, it at a temperature of 0MPa pressure, 80 DEG C, first disposably puts into low aldehyde propylene oxide 272.4g and carries out prepolymerization, to reaction pressure
Power is lower than 0.05MPa, and the low aldehyde propylene oxide of remaining 4267.6g is continuously put into reaction, is vacuumized after the reaction was completed by unreacted
Monomer abjection.It is ethylene oxide-capped with the rate investment 400g of 1g/min, obtain thick polyethers.(wherein, qualities of glycerin in thick polyethers
Account for total amount of feeding 1%, the quality of propylene oxide account for the 90.8% of total amount of feeding, the quality of ethylene oxide accounts for total amount of feeding
8%, the quality of alkali metal hydroxide accounts for total amount of feeding 0.2%.Wherein the quality of prepolymerization propylene oxide accounts for low aldehyde epoxy third
The 6% of the total dosage of alkane)
After the neutralized adsorption treatment of crude polyoxyalkylene polyol, pH value 5.0 adds aqueous isopropanol 1000g, anti-at 60 DEG C
30min is answered, vacuum distillation obtains low-odor polyether polyol B at -0.1MPa；(dosage of isopropanol water solution is that polyethers is more
The 20% of first alcohol quality；The composition of isopropanol water solution are as follows: isopropanol 40%, water 60%.)
Embodiment 3
By 5000g propylene oxide with air speed 21h-1By 200ml adsorption tanks, the propylene oxide after adsorbing is collected, surveys epoxy
Propane aldehyde is 0.0002%.
Glycerol 150g, potassium hydroxide 15g are put into stainless steel cauldron by the polyether polyol for synthesizing 5000g, and nitrogen is set
It changes three times, at a temperature of 0.1MPa pressure, 90 DEG C, first disposably puts into low aldehyde propylene oxide 307g and carry out prepolymerization, wait react
Pressure is lower than 0.05MPa, and the low aldehyde propylene oxide of remaining 4078g is continuously put into reaction, is vacuumized after the reaction was completed by unreacted
Monomer abjection.It is ethylene oxide-capped with the rate investment 450g of 1g/min, obtain thick polyethers.(wherein, qualities of glycerin in thick polyethers
Account for total amount of feeding 3%, the quality of propylene oxide account for the 87.7% of total amount of feeding, the quality of ethylene oxide accounts for total amount of feeding
9%, the quality of alkali metal hydroxide accounts for total amount of feeding 0.3%.Wherein the quality of prepolymerization propylene oxide accounts for low aldehyde epoxy third
The 7% of the total dosage of alkane)
After the neutralized adsorption treatment of crude polyoxyalkylene polyol, pH value 5.2 adds aqueous isopropanol 500g, anti-at 70 DEG C
30min is answered, vacuum distillation obtains low-odor polyether polyol C at -0.1MPa；(dosage of isopropanol water solution is that polyethers is more
The 10% of first alcohol quality；The composition of isopropanol water solution are as follows: isopropanol 50%, water 50%.)
Embodiment 4
By 5000g propylene oxide with air speed 22h-1By 200ml adsorption tanks, the propylene oxide after adsorbing is collected, surveys epoxy
Propane aldehyde is 0.0003%.
Glycerol 250g, potassium hydroxide 20g are put into stainless steel cauldron by the polyether polyol for synthesizing 5000g, and nitrogen is set
It changes three times, at a temperature of 0.2MPa pressure, 100 DEG C, first disposably puts into low aldehyde propylene oxide 338.4g and carry out prepolymerization, to anti-
It answers pressure lower than 0.05MPa, the low aldehyde propylene oxide of remaining 3891.6g is continuously put into reaction, vacuumizing after the reaction was completed will not
Reaction monomers abjection.It is ethylene oxide-capped with the rate investment 500g of 1g/min, obtain thick polyethers.(wherein, glycerol in thick polyethers
The quality that quality accounts for the 5% of total amount of feeding, propylene oxide accounts for the 84.6% of total amount of feeding, and the quality of ethylene oxide accounts for total amount of feeding
10%, the quality of alkali metal hydroxide account for total amount of feeding 0.4%.Wherein the quality of prepolymerization propylene oxide accounts for low aldehyde epoxy
The 8% of the total dosage of propane)
After the neutralized adsorption treatment of crude polyoxyalkylene polyol, pH value 5.4 adds aqueous isopropanol 750g, anti-at 65 DEG C
30min is answered, vacuum distillation obtains low-odor polyether polyol D at -0.1MPa；(dosage of isopropanol water solution is that polyethers is more
The 15% of first alcohol quality；The composition of isopropanol water solution are as follows: isopropanol 50%, water 50%.)
Embodiment 5
By 5000g propylene oxide with air speed 23h-1By 200ml adsorption tanks, the propylene oxide after adsorbing is collected, surveys epoxy
Propane aldehyde is 0.0004%.
Glycerol 350g, potassium hydroxide 12.5g are put into stainless steel cauldron, nitrogen by the polyether polyol for synthesizing 5000g
Displacement three times, at a temperature of 0.3MPa pressure, 110 DEG C, first disposably puts into low aldehyde propylene oxide 367.9g and carries out prepolymerization, to
Reaction pressure be lower than 0.05MPa, the low aldehyde propylene oxide of remaining 3719.6g is continuously put into reaction, vacuumize after the reaction was completed by
Unreacted monomer abjection.It is ethylene oxide-capped with the rate investment 550g of 1g/min, obtain thick polyethers.It is (wherein, sweet in thick polyethers
The quality that oil quality accounts for the 7% of total amount of feeding, propylene oxide accounts for the 81.75% of total amount of feeding, and the quality Zhan of ethylene oxide is always thrown
The 11% of doses, the quality of alkali metal hydroxide accounts for total amount of feeding 0.25%.Wherein the quality of prepolymerization propylene oxide accounts for low
The 9% of the total dosage of aldehyde propylene oxide)
After the neutralized adsorption treatment of crude polyoxyalkylene polyol, pH value 5.6 adds aqueous isopropanol 350g, anti-at 75 DEG C
30min is answered, vacuum distillation obtains low-odor polyether polyol E at -0.1MPa；(dosage of isopropanol water solution is that polyethers is more
The 7% of first alcohol quality；The composition of isopropanol water solution are as follows: isopropanol 35%, water 65%.)
Embodiment 6
For 24 hours with air speed by 5000g propylene oxide-1By 200ml adsorption tanks, the propylene oxide after adsorbing is collected, surveys epoxy
Propane aldehyde is 0.0005%.
Glycerol 450g, potassium hydroxide 17.5g are put into stainless steel cauldron, nitrogen by the polyether polyol for synthesizing 5000g
Displacement three times, at a temperature of 0.35MPa pressure, 120 DEG C, first disposably puts into low aldehyde propylene oxide 388.25g and carries out prepolymerization,
It is lower than 0.05MPa to reaction pressure, the low aldehyde propylene oxide of remaining 3494.25g is continuously put into reaction, is vacuumized after the reaction was completed
Unreacted monomer is deviate from.It is ethylene oxide-capped with the rate investment 650g of 1g/min, obtain thick polyethers.(wherein, in thick polyethers
The quality that qualities of glycerin accounts for the 9% of total amount of feeding, propylene oxide accounts for the 77.65% of total amount of feeding, and the quality Zhan of ethylene oxide is total
The 13% of inventory, the quality of alkali metal hydroxide accounts for total amount of feeding 0.35%.Wherein the quality of prepolymerization propylene oxide accounts for
The 10% of the low total dosage of aldehyde propylene oxide)
After the neutralized adsorption treatment of crude polyoxyalkylene polyol, pH value 5.8 adds aqueous isopropanol 450g, anti-at 60 DEG C
30min is answered, vacuum distillation obtains low-odor polyether polyol F at -0.1MPa；(dosage of isopropanol water solution is that polyethers is more
The 9% of first alcohol quality；The composition of isopropanol water solution are as follows: isopropanol 45%, water 55%.)
Embodiment 7
By 5000g propylene oxide with air speed 25h-1By 200ml adsorption tanks, the propylene oxide after adsorbing is collected, surveys epoxy
Propane aldehyde is 0.0006%.
Glycerol 550g, potassium hydroxide 12.5g are put into stainless steel cauldron, nitrogen by the polyether polyol for synthesizing 5000g
Displacement three times, at a temperature of 0.35MPa pressure, 120 DEG C, first disposably puts into low aldehyde propylene oxide 223.65g and carries out prepolymerization,
It is lower than 0.05MPa to reaction pressure, the low aldehyde propylene oxide of remaining 3503.85g is continuously put into reaction, is vacuumized after the reaction was completed
Unreacted monomer is deviate from.It is ethylene oxide-capped with the rate investment 700g of 1g/min, obtain thick polyethers.(wherein, in thick polyethers
The quality that qualities of glycerin accounts for the 11% of total amount of feeding, propylene oxide accounts for the 74.55% of total amount of feeding, and the quality Zhan of ethylene oxide is total
The 14% of inventory, the quality of alkali metal hydroxide accounts for total amount of feeding 0.45%.Wherein the quality of prepolymerization propylene oxide accounts for
The 6% of the low total dosage of aldehyde propylene oxide)
After the neutralized adsorption treatment of crude polyoxyalkylene polyol, pH value 6.0 adds aqueous isopropanol 600g, anti-at 62 DEG C
30min is answered, vacuum distillation obtains low-odor polyether polyol G at -0.1MPa；(dosage of isopropanol water solution is that polyethers is more
The 12% of first alcohol quality；The composition of isopropanol water solution are as follows: isopropanol 32%, water 68%.)
Embodiment 8
By 5000g propylene oxide with air speed 21h-1By 200ml adsorption tanks, the propylene oxide after adsorbing is collected, surveys epoxy
Propane aldehyde is 0.0001%.
Glycerol 650g, potassium hydroxide 14g are put into stainless steel cauldron by the polyether polyol for synthesizing 5000g, and nitrogen is set
It changes three times, at a temperature of 0.15MPa pressure, 85 DEG C, first disposably puts into low aldehyde propylene oxide 179.3g and carry out prepolymerization, to anti-
It answers pressure lower than 0.05MPa, the low aldehyde propylene oxide of remaining 3406.7g is continuously put into reaction, vacuumizing after the reaction was completed will not
Reaction monomers abjection.It is ethylene oxide-capped with the rate investment 750g of 1g/min, obtain thick polyethers.(wherein, glycerol in thick polyethers
The quality that quality accounts for the 13% of total amount of feeding, propylene oxide accounts for the 71.72% of total amount of feeding, and the quality Zhan of ethylene oxide always feeds intake
The 15% of amount, the quality of alkali metal hydroxide accounts for total amount of feeding 0.28%.Wherein the quality of prepolymerization propylene oxide accounts for low aldehyde
The 5% of the total dosage of propylene oxide)
After the neutralized adsorption treatment of crude polyoxyalkylene polyol, pH value 6.2 adds aqueous isopropanol 850g, anti-at 68 DEG C
30min is answered, vacuum distillation obtains low-odor polyether polyol H at -0.1MPa；(dosage of isopropanol water solution is that polyethers is more
The 17% of first alcohol quality；The composition of isopropanol water solution are as follows: isopropanol 48%, water 52%.)
Embodiment 9
By 5000g propylene oxide with air speed 20h-1By 200ml adsorption tanks, the propylene oxide after adsorbing is collected, surveys epoxy
Propane aldehyde is 0.0003%.
Glycerol 750g, potassium hydroxide 21.5g are put into stainless steel cauldron, nitrogen by the polyether polyol for synthesizing 5000g
Displacement three times, at a temperature of 0.05MPa pressure, 95 DEG C, first disposably puts into low aldehyde propylene oxide 240.7g and carries out prepolymerization, to
Reaction pressure be lower than 0.05MPa, the low aldehyde propylene oxide of remaining 3197.8g is continuously put into reaction, vacuumize after the reaction was completed by
Unreacted monomer abjection.It is ethylene oxide-capped with the rate investment 790g of 1g/min, obtain thick polyethers.It is (wherein, sweet in thick polyethers
The quality that oil quality accounts for the 15% of total amount of feeding, propylene oxide accounts for the 68.77% of total amount of feeding, and the quality Zhan of ethylene oxide is always thrown
The 15.8% of doses, the quality of alkali metal hydroxide accounts for total amount of feeding 0.43%.Wherein the quality of prepolymerization propylene oxide accounts for
The 7% of the low total dosage of aldehyde propylene oxide)
After the neutralized adsorption treatment of crude polyoxyalkylene polyol, pH value 6.4 adds aqueous isopropanol 950g, anti-at 73 DEG C
30min is answered, vacuum distillation obtains low-odor polyether polyol I at -0.1MPa；(dosage of isopropanol water solution is that polyethers is more
The 19% of first alcohol quality；The composition of isopropanol water solution are as follows: isopropanol 32%, water 68%.)
Embodiment 10
By 5000g propylene oxide with air speed 20h-1By 200ml adsorption tanks, the propylene oxide after adsorbing is collected, surveys epoxy
Propane aldehyde is 0.0004%.
Glycerol 800g, potassium hydroxide 25g are put into stainless steel cauldron by the polyether polyol for synthesizing 5000g, and nitrogen is set
It changes three times, at a temperature of 0MPa pressure, 125 DEG C, first disposably puts into low aldehyde propylene oxide 337.5g and carry out prepolymerization, wait react
Pressure is lower than 0.05MPa, and the low aldehyde propylene oxide of remaining 3037.5g is continuously put into reaction, and vacuumizing after the reaction was completed will be not anti-
Monomer is answered to deviate from.It is ethylene oxide-capped with the rate investment 800g of 1g/min, obtain thick polyethers.(wherein, glycerol matter in thick polyethers
Amount accounts for the 16% of the total amount of feeding, quality of propylene oxide and accounts for the 67.5% of total amount of feeding, and the quality of ethylene oxide accounts for total amount of feeding
16%, the quality of alkali metal hydroxide account for total amount of feeding 0.5%.Wherein the quality of prepolymerization propylene oxide accounts for low aldehyde epoxy
The 10% of the total dosage of propane)
After the neutralized adsorption treatment of crude polyoxyalkylene polyol, pH value 6.5 adds aqueous isopropanol 300g, anti-at 73 DEG C
30min is answered, vacuum distillation obtains low-odor polyether polyol J at -0.1MPa；(dosage of isopropanol water solution is that polyethers is more
The 6% of first alcohol quality；The composition of isopropanol water solution are as follows: isopropanol 42%, water 58%.)
The quality index of polyether polyol A~J is listed in table 1.
1 polyether polyol index analysis result of table
Result can be seen that from table, and the preparation method of low-odor polyether polyol proposed by the invention can synthesize outlet
The low-odor polyether polyol product of taste grade 1~2.5, and other performance indicators of product are excellent.
Claims (9)
1. a kind of preparation method of low-odor polyether polyol, it is characterized in that including the following steps:
1) raw material propylene oxide is in 20~25h of air speed-1Down by molecular sieve tank, drop aldehyde processing is adsorbed through molecular sieve tank, is obtained low
Aldehyde propylene oxide；
2) use multicomponent alcoholics compound for initiator, at a temperature of 0-0.4MPa pressure, 80-140 DEG C, in alkali metal hydroxide
Object catalyst is reacted under participating in, and first disposably put into the low total dosage of aldehyde propylene oxide 5%~10% carries out prepolymerization, to
Reaction pressure is lower than 0.05MPa, remaining low aldehyde propylene oxide is continuously put into reaction, is vacuumized after the reaction was completed by unreacted list
Body abjection obtains thick polyethers finally with ethylene oxide-capped；
3) for thick polyethers after neutralizing purification, pH value 4.8-6.5 adds isopropanol water solution, reacts 30 at 60~80 DEG C
Minute~180 minutes, it is finally evaporated under reduced pressure to obtain low-odor polyether polyol.
2. the method as described in claim 1, it is characterized in that step 1) obtain low aldehyde propylene oxide aldehyde 0.0001~
0.0006%.
3. the method as described in claim 1, it is characterized in that step 2) material component and percentage composition are as follows:
Total amount of feeding is total for said components, in terms of 100%.
4. the method as described in claim 1, it is characterized in that multicomponent alcoholics compound is glycerol, ethylene glycol, diethylene glycol, the third two
Alcohol, dipropylene glycol or trimethylolpropane it is one or more.
5. the method as described in claim 1, it is characterized in that alkali metal hydroxide catalyst is potassium hydroxide or sodium hydroxide.
6. the method as described in claim 1, it is characterized in that molecular sieve be aluminium oxide, silica type molecular sieve or other have aldehydes
The molecular sieve of substance adsorption capacity.
7. the method as described in claim 1, it is characterized in that the dosage of isopropanol water solution is the 5- of polyether polyol quality
20%.
8. the method for claim 7, it is characterized in that the isopropanol water solution forms are as follows: isopropanol 30-50%, water
50-70%.
9. the method as described in claim 1, it is characterized in that gained low-odor polyether polyol oder levels 1~2.5.
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| CN111318311A (en) * | 2020-04-22 | 2020-06-23 | 上海多纶化工有限公司 | Cocatalyst, catalyst and application thereof |
| WO2020253297A1 (en) | 2019-06-12 | 2020-12-24 | 佳化化学科技发展（上海）有限公司 | Process and system for producing low-odor polyether polyol |
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