CN109467691A - A kind of preparation method of low unsaturation degree and high molecular weight polyoxyalkylene polyol - Google Patents
A kind of preparation method of low unsaturation degree and high molecular weight polyoxyalkylene polyol Download PDFInfo
- Publication number
- CN109467691A CN109467691A CN201811187400.2A CN201811187400A CN109467691A CN 109467691 A CN109467691 A CN 109467691A CN 201811187400 A CN201811187400 A CN 201811187400A CN 109467691 A CN109467691 A CN 109467691A
- Authority
- CN
- China
- Prior art keywords
- polyoxyalkylene polyol
- molecular weight
- polyol
- conditions
- ion exchange
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Pending
Links
Classifications
-
- 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
-
- 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
Landscapes
- Chemical & Material Sciences (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- Polyethers (AREA)
Abstract
The present invention relates to a kind of preparation methods of low unsaturation degree and high molecular weight polyoxyalkylene polyol, it the use of small molecular alcohol is first initiator, prepare the low molecular polyether intermediate that hydroxyl value is 300mgKOH/g~900mgKOH/g, 0.05%~0.5% phosphazene compound based on polyoxyalkylene polyol quality is added as catalyst, at 70~130 DEG C of temperature, reaction pressure is no more than under the conditions of 0.8MPa, continue open loop addition polymerization epoxide in polyether intermediate, obtain the high molecular weight polyoxyalkylene polyalcohol that hydroxyl value is 12mgKOH/g~120mgKOH/g, and alkali and phosphazene compound are removed by the method for absorption contact using ion exchange resin under the conditions of 50~150 DEG C, the low unsaturation degree and high molecular weight polyoxygenated refined Alkene polyalcohol.It can be widely used for the raw material of semi-rigid, flexible polyurethane foams and related fields.
Description
Technical field
The present invention relates to a kind of preparation methods of low unsaturation degree and high molecular weight polyoxyalkylene polyol.The present invention makes phosphonitrile
Compound is as the catalyst to prepare polyoxyalkylene polyol.It in detail, is that low molecular weight polyoxyalkylene polyol is first made,
Phosphazene compound is reused as the catalyst to the method for preparing low unsaturation degree and high molecular weight polyoxyalkylene polyol, phosphorus used
Nitrile compound structural formula is as follows.
Background technique
Epoxide ring-opening polymerization includes the catalysis such as cation ring-opening polymerization, anionic ring-opening polymerization and coordination ring-opening polymerisation
System.Cationic open loop catalysis mainly includes some Bronsted acids and Lweis acid, the polymer average molecular of this kind of catalyst synthesis
Quality is relatively small, and the by-product polyethylene glycol (PEG) and ring oxane that generate are more, are not easy to industrialize.Anion open loop is urged
Changing industrially most at present is KOH, and reaction condition is milder, and reaction is relatively easy to control, and catalyst cost is very low,
But it is easy to happen chain transfer reaction in catalytic process, leads to that relative molecular mass is lower, product distribution is wider, unsaturated
A series of high disadvantages are spent, product performance index is influenced, are restricted the application of product.
Coordination polymerization research also compare it is more, it is most successful at present to work as applied to polyoxyalkylene polyol is also industrialized
Belong to bimetallic catalyst, it has high catalytic activity, low, the average molecular matter with terminal unsaturation of the polyethers made of it
The advantages that amount is high and relative molecular mass distribution is narrow.However, there is also some problems in use for the catalyst, cannot such as use
Low molecule weight initiator, in the case where inactivating bimetallic catalyst from directly with ethylene oxide-capped with the primary hydroxyl of acquisition
Base, head-tail (H-T) selection rate of pfpe molecule is low, viscosity is bigger than normal etc..
From the viewpoint of industry, when manufacturing polyoxyalkylene polyol, it is desirable to use less amount of catalyst, while energy
The productive method of polyoxyalkylene polyol is greatly improved.
The present invention uses phosphazene compound as the catalyst to prepare polyoxyalkylene polyol, and the production cycle shortens, polyoxy
Changing alkene polyol product has the characteristics that low unsaturation degree and high molecular weight.
Summary of the invention
In order to solve problems in the prior art, it is polynary using phosphazene compound to prepare polyoxyalkylene as catalyst by the present invention
Alcohol, and phosphazene compound is removed by the method that adsorbent contacts, it can be used for manufacturing the polyoxyalkylene polyol of higher molecular weight,
Production cycle shortens, and product degree of unsaturation is low, has higher efficiency.
Technical scheme is as follows:
In the presence of 0.02%~0.2% KOH or NaOH based on polyoxyalkylene polyol quality, small molecular alcohol is used
For initiator, at 70~130 DEG C of temperature, reaction pressure is no more than under the conditions of 0.8MPa, and open loop addition polymerization epoxide obtains hydroxyl
Value is the low molecular polyether intermediate of 300mgKOH/g~900mgKOH/g, is added based on polyoxyalkylene polyol quality
0.05%~0.5% phosphazene compound is as catalyst, and at 70~130 DEG C of temperature, reaction pressure is no more than 0.8MPa condition
Under, in polyether intermediate continue open loop addition polymerization epoxide, obtain hydroxyl value be 12mgKOH/g~120mgKOH/g it is low not
Saturation degree high molecular weight polyoxyalkylene polyalcohol, and absorption contact is passed through using ion exchange resin under the conditions of 50~150 DEG C
Method removal alkali and phosphonitrile, the polyoxyalkylene polyol refined, wherein phosphazene compound structural formula is as follows:
Potassium hydroxide or sodium hydroxide quality are the 0.02%~0.2% of polyoxyalkylene polyol product quality.
The phosphazene compound quality is the 0.05%~0.5% of polyoxyalkylene polyol product quality.
The small molecular alcohol includes the monovalencies alcohols such as butanol, octanol, allyl alcohol；Ethylene glycol, diethylene glycol, propylene glycol, two
Propylene glycol, 1,3-PD, Isosorbide-5-Nitrae-cyclohexanediol, 1,3-BDO, 1,4-butanediol, 1,6- hexylene glycol, Isosorbide-5-Nitrae-cyclohexanediol,
Equal divalents alcohols；The polyvalent alcohols such as glycerol, trimethylolpropane, pentaerythrite, sorbierite.
The epoxide of the addition polymerization includes propylene oxide, ethylene oxide, epoxy butane, styrene oxide, epoxy
Hexamethylene, epoxychloropropane, epoxy bromopropane, methyl glycidyl ether, allyl glycidyl ether etc.；Or make two or more
Epoxides is used in combination；These, it is preferred to propylene oxide, ethylene oxide, epoxy butane, styrene oxide, more preferably ring
Ethylene Oxide, ethylene oxide.
Contact removal alkali and phosphazene compound are adsorbed using ion exchange resin.
It is described as follows:
In polyoxyalkylene polyol manufacturing method of the invention, since phosphazene compound exists, when propylene oxide, epoxy second
It, can be with the polyol product of high efficiency manufacture higher molecular weight, to reduce industrial polyoxy when alkane, epoxy butane etc. are used as monomer
Change production cycle and the manufacturing cost of alkene polyalcohol.Polyoxyalkylene polyol of the invention in semi-rigid, flexible polyurethane foams,
Coating, adhesive, bed material, waterproof material, elastomer, sealant, the polyurethane field and lubricant of sole etc., brake fluid,
It is a kind of extremely useful raw material in the wide range of areas of modifier etc..
Small molecular alcohol includes the 1 valence alcohols such as butanol, octanol, allyl alcohol；Ethylene glycol, diethylene glycol, propylene glycol, dipropyl two
Alcohol, 1,3-PD, Isosorbide-5-Nitrae-cyclohexanediol, 1,3-BDO, 1,4-butanediol, 1,6- hexylene glycol, Isosorbide-5-Nitrae-cyclohexanediol, etc. 2
Valence alcohols；The polyvalent alcohols such as glycerol, trimethylolpropane, pentaerythrite, sorbierite.
The epoxide of addition polymerization includes propylene oxide, ethylene oxide, epoxy butane, Oxybenzene second on small molecular alcohol
Alkene, 7-oxa-bicyclo[4.1.0, epoxychloropropane, epoxy bromopropane, methyl glycidyl ether, allyl glycidyl ether etc..2 can also be made
Kind or more epoxides be used in combination；These, it is preferred to which propylene oxide, ethylene oxide, epoxy butane, styrene oxide, more excellent
Choosing is propylene oxide, ethylene oxide.In the manufacture of low molecular polyether intermediate, most preferably with propylene oxide.
Phosphazene compound dosage based on polyoxyalkylene polyol quality 0.05%~0.5%.Catalyst amount is discontented
When 0.05%, the manufacturing time of polyoxyalkylene polyol is longer；On the other hand, when catalyst usage amount is more than 0.5%, polyoxygenated
Catalyst cost increases in the manufacturing cost of alkene polyalcohol.
In low molecular polyether intermediate and polyoxyalkylene polyol manufacture, the polymerization temperature of epoxides preferably 70~
130 DEG C, more preferably in the range of 90~120 DEG C.When the polyaddition temperature of epoxides is 70 DEG C discontented, the polymerization speed of epoxides
It spends lower；On the other hand, when polyaddition temperature is more than 130 DEG C, using the generation of aldehyde material, side reaction can be increase accordingly.
Maximum pressure when epoxides sudden reaction usually in voltage-resistant reactor preferably in 0.8MPa hereinafter, carry out ring
Sudden reaction of the oxide in active hydrogen compounds.The reaction of epoxide can be since decompression state, can also be from atmospheric pressure
State starts.In the occasion since under atmospheric pressure state, it is desirable to be reacted in the presence of the inert gases such as nitrogen, helium.
When the maximum pressure of epoxides is more than 0.8MPa, the content (total degree of unsaturation) of the cell alcohol of the by-product as propylene oxide
Increase.Maximum reaction pressure is preferably in 0.6MPa hereinafter, most preferably in 0.5MPa or less.
Adding manner of the epoxides into polymerization system exploits the mode that is added portionwise, or make whole epoxides with
Continuous mode is added.
The influence of speed, polymerization temperature, catalyst amount etc. is added in the called oxide of the maximum pressure of polymer reactor.Ring
The maximum reaction pressure that the addition speed of oxide is preferably able to control reactor is no more than 0.3MPa preferably.Epoxides adds
Afterwards, slow reduction is pushed back in polymer reactor, according to the variation of reactor internal pressure, on the basis of the hydroxyl value of polyoxyalkylene polyol
The progress of reaction is controlled, general carry out until hydroxyl value is in 12~120mgKOH/g is polymerize.
When manufacturing polyoxyalkylene polyol in aforementioned manners, after the completion of epoxide polymerization, obtain poly- containing catalyst
Oxyalkylene polyalcohol (hereinafter referred to as crude polyalcohol), it usually needs remove the catalyst in crude polyalcohol.
The present invention removes catalyst using strong-acid ion exchange resin.Crude polyalcohol and contacts ionic exchange resin temperature
Degree considers that Contact Temperature preferably exists from the length of processing time, raising of catalyst removal ability etc. preferably near room temperature
50~150 DEG C of range；In the big occasion of the molecular weight of polyoxyalkylene polyol, viscosity is high, it is preferable to use 50 DEG C or more connect
Touch temperature, but be higher than 150 DEG C after, crude polyalcohol has the tendency of coloring.
The way of contact of crude polyalcohol and ion exchange resin includes intermittent and 2 kinds of methods of continous way.Batch process packet
It includes, such as reactor, the method being stirred is added in crude polyalcohol and ion exchange resin.To prevent crude polyalcohol
For the purpose of coloring, deterioration, it is preferably stirred mixing in the presence of an inert gas.The usage amount of ion exchange resin is relative to thick
The 0.01%~5% of polyol quality processed.Time of contact depends on the scale of processing, and preferably processing 1~6 is small under the above conditions
When.Continuation mode is to be filled in ion exchange resin in tower, and crude polyalcohol is then made to lead to the method for liquid.Air speed depends on
The scale of processing, the preferably speed in 0.2~5 (L/h).After contacts ionic exchange resin, often using filtering, centrifuge separation etc.
Means recycle polyoxyalkylene polyol.
It can be thick in crude polyalcohol and contacts ionic exchange resin for the adsorption capacity for improving ion exchange resin
The polynary deionized water being added relative to crude polyalcohol 0.1%~10% middle out is made, can also be not added.Ion exchange resin with
The method that deionized water coexists preferably takes the mode that deionized water water is added to polyalcohol.In crude polyalcohol addition go from
Temperature when sub- water is preferably 50~150 DEG C, adds the occasion of deionized water, such as make crude polyalcohol and ion at 90 DEG C
After exchanger resin is stirred 5h, for example, 110 DEG C, 1.33kPa it is below under the conditions of carry out decompression dehydration operation, to remove water
Point.
The hydroxyl value of obtained polyoxyalkylene polyol is operated above preferably in 12~120mgKOH/g.
Known by above detailed description, in the manufacturing method of polyoxyalkylene polyol of the invention, Polymerization of Propylene Oxide
Efficiency improves.In turn, it can be widely used for semi-rigid with the polyoxyalkylene polyol that method of the invention manufactures, flexibel polyurethane steeps
Foam；Coating；Adhesive；Bed material；Waterproof material；Elastomer；Sealant；The polyurethane fields such as sole, furthermore in lubricant, braking
The fields such as liquid, modifier are also extremely useful raw material.
Specific embodiment
[embodiment 1] polyoxyalkylene polyol A
In separable flask (the following letter for having blender, temperature controller, nitrogen ingress pipe and water cooled condenser
Referred to as flask) in, sorbierite and the KOH relative to target polyoxyalkylene polyol 0.02% is added, 130 DEG C, 1.33kPa with
3h is operated under the conditions of lower, is modulated into initiator liquid；Then, by the initiator liquid importing one have blender, temperature controller,
In the pressure-resistant reaction kettle (hereinafter referred to as reaction kettle) of pressure gauge, nitrogen ingress pipe and monomer ingress pipe, wherein with nitrogen displacement
Air, then polyaddition temperature be 90 DEG C ± 5 DEG C, maximum reaction pressure be 0.3MPa (G) under the conditions of, investment make target product
Hydroxyl value (hereinafter referred to as OHV) reaches the propylene oxide of 450mgKOH/g；After propylene oxide addition, the maximum for controlling reaction kettle is anti-
Answering pressure is 0.3MPa (G), when final pressure no longer reduces, reaction terminating；Then at 90 DEG C, decompression step by step processing
30min recycles unreacted propylene oxide, obtains low molecular polyether intermediate I.
Low molecular polyether intermediate I is added in a kettle, is then added relative to polyoxyalkylene polyol quality
0.15% phosphazene compound carries out heating decompression operation 3h, is modulated into and polymerize under 110 DEG C, 1.33kPa the following conditions
Beginning agent；Then reaction kettle is added in the polymerization initiators, is 110 DEG C, most in polyaddition temperature after replacing air therein with nitrogen
Big reaction pressure adds ethylene oxide (EO) to be gradually added propylene oxide (PO) under the conditions of 0.3MPa (G), calculates epoxy third
The amount of alkane and ethylene oxide makes target product hydroxyl value 120mgKOH/g, and PO/EO molar ratio is 6/1, in propylene oxide and ring
After oxidative ethane is added, control reaction kettle maximum reaction pressure is 0.3MPa (G), when final pressure no longer reduces, reaction terminating；Ring
Oxygen compound total reaction time is 100min；Then under the conditions of 110 DEG C, 1.33kPa or less handles 30min, recycles unreacted
Propylene oxide, obtain crude polyalcohol A；Afterwards using batch process absorption contact, after crude polyalcohol A is adjusted to 80 DEG C, it is added
Relative to crude polyalcohol 5% ion exchange water and 5% ion exchange resin, handle 3h under the conditions of 80 DEG C, finally exist
110 DEG C, heating decompression operation 3h is carried out under the conditions of 1.33kPa；Later, it is filtered under diminished pressure with filter paper, what is refined is polynary
Alcohol；The OHV of the polyalcohol is 120mgKOH/g, C=C 0.01meq/g.
[embodiment 2] polyoxyalkylene polyol B
In flask, be added trimethylolpropane and relative to target polyoxyalkylene polyol 0.2% KOH 70 DEG C,
Heating, decompression operation 2h, are modulated into initiator liquid under 1.33kPa the following conditions.Then, which is imported into reaction kettle
In, air therein is replaced with nitrogen, is then 100 DEG C ± 5 DEG C in polyaddition temperature, maximum reaction pressure is 0.25MPa (G) item
Under part, the propylene oxide for making target product hydroxyl value (hereinafter referred to as OHV) reach 300mgKOH/g is put into.It is added in propylene oxide
Afterwards, control reaction kettle maximum reaction pressure is 0.25MPa (G), when final pressure no longer reduces, reaction terminating.Then 100
DEG C, 30min is handled under the conditions of 1.33kPa, recycles unreacted propylene oxide, obtains low molecular polyether intermediate II.
Low molecular polyether intermediate II is added in a kettle, is then added relative to polyoxyalkylene polyol quality
0.05% phosphazene compound is depressurized at 6.65kPa, is then 110 DEG C in polyaddition temperature, maximum reaction pressure is
The propylene oxide that target product hydroxyl value reaches 87mgKOH/g is gradually added under the conditions of 0.35MPa (G), after propylene oxide addition,
Controlling reaction kettle maximum reaction pressure is 0.35MPa (G), and reaction is terminated when final pressure no longer reduces.Epoxide is always anti-
It is 180min between seasonable.Later at 110 DEG C, 30min is operated under 6.65kPa, recycles unreacted propylene oxide, is obtained crude
Polyalcohol B.Afterwards using batch process absorption contact, after crude polyalcohol B is adjusted to 100 DEG C, it is added relative to the crude polyalcohol B
The ion exchange water of weight 10% and 0.1% ion exchange resin, in 100 DEG C of processing 6h.Finally 110 DEG C, 1.33kPa with
Heating decompression operation 2h is carried out under conditions of lower.Then it is filtered under diminished pressure with filter paper, the polyalcohol refined.The polyalcohol
OHV be 88.5mgKOH/g, C=C 0.02meq/g.
[embodiment 3] polyoxyalkylene polyol C
In flask, propylene glycol and the KOH relative to target polyoxyalkylene polyol 0.1% is added in 90 DEG C, 1.33kPa
Heating, decompression operation 1.5h, are modulated into initiator liquid under the following conditions.Then, which is imported in reaction kettle, uses nitrogen
Gas replaces air therein, is then 110 DEG C ± 5 DEG C in polyaddition temperature, and maximum reaction pressure is throwing under the conditions of 0.2MPa (G)
Enter to make target product hydroxyl value (hereinafter referred to as OHV) to reach the propylene oxide of 500 ± 3mgKOH/g,.After propylene oxide addition, control
Reaction kettle maximum reaction pressure processed is 0.2MPa (G), when final pressure no longer reduces, reaction terminating.Then 110 DEG C,
30min is handled under the conditions of 1.33kPa, recycles unreacted propylene oxide, obtains low molecular polyether intermediate III.
Low molecular polyether intermediate III is added in a kettle, is then added relative to polyoxyalkylene polyol quality
0.5% phosphazene compound is depressurized at 6.65kPa, is then 90 DEG C in polyaddition temperature, maximum reaction pressure is 0.5MPa
(G) it under the conditions of below, is gradually added the propylene oxide for making target product hydroxyl value reach 40mgKOH/g and epoxy butane (DO) is mixed
Close object, and PO/DO molar ratio 5/1.After propylene oxide and epoxy butane mixture are added, reaction kettle maximum reaction pressure is controlled
For 0.5MPa (G), when final pressure no longer reduces, reaction is terminated.Epoxide total reaction time is 240min.Later, 100
DEG C, 30min is operated under 6.65kPa, to recycle unreacted propylene oxide, obtains crude polyalcohol C.It is adsorbed afterwards using batch process
Contact, after crude polyalcohol C is adjusted to 140 DEG C, be added relative to the crude polyalcohol C weight 8% ion exchange water and
0.01% ion exchange resin, in 140 DEG C of processing 1h.Finally 150 DEG C, 1.33kPa it is below under the conditions of carry out heating subtract
Press operation 2h.Then it is filtered under diminished pressure with filter paper, the polyalcohol refined.The OHV of gained polyalcohol C is 40.1mgKOH/
G, C=C 0.014meq/g.
[embodiment 4] polyoxyalkylene polyol D
In flask, be added pentaerythrite and relative to target polyoxyalkylene polyol 0.05% KOH 110 DEG C,
Heating, decompression operation 2.5h, are modulated into initiator liquid under 1.33kPa the following conditions.Then, which is imported and is reacted
Kettle replaces air therein with nitrogen, is then 90 DEG C ± 5 DEG C in polyaddition temperature, maximum reaction pressure is 0.5MPa (G) condition
Under, put into the propylene oxide for making target product hydroxyl value (hereinafter referred to as OHV) reach 900mgKOH/g.After propylene oxide addition,
Controlling reaction kettle maximum reaction pressure is 0.25MPa (G), when final pressure no longer reduces, reaction terminating.100℃1.33kPa
Under the conditions of handle 30min, recycle unreacted propylene oxide, obtain low molecular polyether intermediate IV.
Low molecular polyether intermediate IV is added in a kettle, is then added relative to polyoxyalkylene polyol quality
0.2% phosphazene compound is depressurized at 6.65kPa, is then 120 DEG C in polyaddition temperature, maximum reaction pressure is 0.4MPa
(G) under the conditions of below, the propylene oxide and ethylene oxide for so that target product hydroxyl value is reached 28mgKOH/g are put into, and PO/EO rubs
You are than being 3/1.After propylene oxide and ethylene oxide are added, control reaction kettle maximum reaction pressure is 0.4MPa (G), most final pressure
Reaction is terminated when power no longer reduces.Epoxide total reaction time is 320min.Later at 120 DEG C, grasped under the conditions of 6.65kPa
Make 30min, recycle unreacted propylene oxide, obtains crude polyalcohol D.Afterwards using continuity method absorption contact, by ion exchange
Resin is filled in packed tower, then adjusts crude polyalcohol D to 50 DEG C, continues through packed tower, air speed 0.2L/h.Finally
120 DEG C, 1.33kPa it is below under the conditions of carry out heating decompression operation 3h.Then it is filtered under diminished pressure, is refined with filter paper
Polyalcohol.The OHV of gained polyalcohol D is 28.2mgKOH/g, C=C 0.021meq/g.
[embodiment 5] polyoxyalkylene polyol E
In flask, be added diethylene glycol and relative to target polyoxyalkylene polyol 0.03% NaOH 120 DEG C,
Heating, decompression operation 2h, are modulated into initiator liquid under 1.33kPa the following conditions.Then, which is imported into reaction kettle
In, air therein is replaced with nitrogen, is then 110 DEG C ± 5 DEG C in polyaddition temperature, maximum reaction pressure is 0.3MPa (G) item
Under part, the propylene oxide for making target product hydroxyl value (hereinafter referred to as OHV) reach 700 ± 3mgKOH/g is put into.In propylene oxide plus
After entering, control reaction kettle maximum reaction pressure is 0.3MPa (G), when final pressure no longer reduces, reaction terminating.Then exist
110 DEG C, handle 30min under the conditions of 1.33kPa, recycle unreacted propylene oxide, obtain low molecular polyether intermediate IV.
Low molecular polyether intermediate IV is added in a kettle, is then added relative to polyoxyalkylene polyol quality
0.4% phosphazene compound is depressurized at 6.65kPa, is then 100 DEG C in polyaddition temperature, maximum reaction pressure is 0.2MPa
(G) under the conditions of below, the propylene oxide for making target product hydroxyl value reach 20mgKOH/g is put into.After propylene oxide addition, control
Reaction kettle maximum reaction pressure processed is 0.2MPa (G), and reaction is terminated when final pressure no longer reduces.When epoxide overall reaction
Between be 450min.30min is operated under the conditions of 100 DEG C, 1.33kPa later, to recycle unreacted propylene oxide, is obtained crude
Polyol E.Afterwards using continuity method absorption contact, ion exchange resin is filled in packed tower, then by crude polyol E tune
Whole to 70 DEG C, continue through packed tower, air speed 5L/h.Finally 100 DEG C, 1.33kPa it is below under the conditions of carry out heating decompression
Operate 2.5h.The OHV of gained polyol E is 20.3mgKOH/g, C=C 0.022meq/g.
[embodiment 6] polyoxyalkylene polyol F
In flask, be added glycerol and relative to target polyoxyalkylene polyol 0.07% NaOH 100 DEG C,
Heating, decompression operation 2h, are modulated into initiator liquid under 1.33kPa the following conditions.Then, which is imported into reaction kettle
In, air therein is replaced with nitrogen, is then 100 DEG C ± 5 DEG C in polyaddition temperature, maximum reaction pressure is 0.15MPa (G) item
Under part, the propylene oxide for making target product hydroxyl value (hereinafter referred to as OHV) reach 800 ± 3mgKOH/g is put into.In propylene oxide plus
After entering, control reaction kettle maximum reaction pressure is 0.15MPa (G), when final pressure no longer reduces, reaction terminating.Then exist
110 DEG C, handle 30min under the conditions of 1.33kPa, recycle unreacted propylene oxide, obtain low molecular polyether intermediate V.
Low molecular polyether intermediate V is added in a kettle, is then added relative to polyoxyalkylene polyol quality
0.1% phosphazene compound is depressurized at 6.65kPa, is then 120 DEG C in polyaddition temperature, maximum reaction pressure is 0.25MPa
(G) under the conditions of below, the propylene oxide and ethylene oxide for so that target product hydroxyl value is reached 12mgKOH/g are put into, and PO/EO rubs
You are than being 4/1.After propylene oxide addition, control reaction kettle maximum reaction pressure is 0.25MPa (G), and final pressure no longer drops
Reaction is terminated when low.Epoxide total reaction time is 600min.30min is operated under the conditions of 100 DEG C, 1.33kPa later,
Unreacted propylene oxide is recycled, crude polyalcohol F is obtained.Afterwards using continuity method absorption contact, ion exchange resin is filled in
In packed tower, then crude polyalcohol F is adjusted to 130 DEG C, continues through packed tower, air speed 2L/h.Finally 100 DEG C,
Heating decompression operation 2.5h is carried out under the conditions of 1.33kPa is below.The OHV of gained polyalcohol F is 12.3mgKOH/g, and C=C is
0.024meq/g。
[comparative example] polyoxyalkylene polyol a, b, c, d, e, f
Using the prior art, use KOH as catalyst, the amount for calculating propylene oxide (PO) and ethylene oxide (EO) makes target
Product hydroxyl value is 120mgKOH/g, and PO/EO molar ratio is 6/1, and the practical hydroxyl value (OHV) of final obtained polyalcohol a is
120.5mgKOH/g, epoxide total reaction time are 200min, C=C 0.06meq/g.
Using the prior art, uses KOH as catalyst, calculate propylene oxide target product hydroxyl value and reach 87mgKOH/g, most
The practical hydroxyl value (OHV) of obtained polyalcohol b is 89.1mgKOH/g eventually, and epoxide total reaction time is 450min, and C=C is
0.08meq/g。
Using the prior art, use KOH as catalyst, calculating propylene oxide and epoxy butane (DO) mixture produces target
Object hydroxyl value reaches 40mgKOH/g, and PO/DO molar ratio 5/1, and the practical hydroxyl value (OHV) of gained polyalcohol c is 40.2mgKOH/
G, epoxide total reaction time are 600min, C=C 0.07meq/g.
Using the prior art, use KOH as catalyst, the amount for calculating propylene oxide (PO) and ethylene oxide (EO) makes target
Product hydroxyl value reaches 28mgKOH/g, and PO/EO molar ratio is 3/1, and polymerization reaction reacts stopping, raw material PO after carrying out 810min
It is complete with EO unreacted.
Using the prior art, use NaOH as catalyst, calculating propylene oxide (PO) reaches target product hydroxyl value
20mgKOH/g, epoxide total reaction time are 900min, and the practical hydroxyl value (OHV) of gained polyalcohol e is 21.2mgKOH/
G, C=C 0.08meq/g.
It using the prior art, uses NaOH as catalyst, calculates propylene oxide and ethylene oxide target product hydroxyl value reaches
12mgKOH/g's, and PO/EO molar ratio is 4/1, polymerization reaction reacts stopping, raw material PO and EO unreacted after carrying out 810min
Completely.
Embodiment and the result of comparative example see below table 1.
The statistical result of table 1 embodiment and comparative example
When preparing the polyoxyalkylene polyol of same target molecular weight (or hydroxyl value), hydrogen-oxygen is relatively used using phosphazene compound
Change potassium or sodium hydroxide, wherein epoxide total reaction time generally shortens 50% or more, and polyoxyalkylene obtained is polynary
Alcohol degree of unsaturation is lower.When preparing certain lower hydroxyl value products, potassium hydroxide or sodium hydroxide reactivity are inadequate, lead to raw material
Unreacted is completely (comparative example 4 and comparative example 6).Therefore use phosphazene compound can as catalyst preparation polyoxyalkylene polyol
The production cycle is effectively reduced, product has lower degree of unsaturation, and can be used for preparing potassium hydroxide or sodium hydroxide catalyst
The polyoxyalkylene polyol product for the higher molecular weight (i.e. lower hydroxyl value) that cannot be prepared.
Above-described embodiment only lists several small molecular alcohols as initiator, and target product hydroxyl value is respectively 120mgKOH/
G, the case where 87mgKOH/g, 40mgKOH/g, 28mgKOH/g, 20mgKOH/g, 12mgKOH/g, polyoxyalkylene of the present invention
The preparation of polyalcohol, which is used but is not limited to the above embodiments, enumerates situation.Using the 1 valence alcohols such as butanol, octanol, allyl alcohol, second two
Alcohol, diethylene glycol, propylene glycol, dipropylene glycol, 1,3-PD, Isosorbide-5-Nitrae-cyclohexanediol, 1,3-BDO, 1,4-butanediol, 1,
6- hexylene glycol, Isosorbide-5-Nitrae-cyclohexanediol, etc. divalents alcohols, the polyvalent alcohols conduct such as glycerol, trihydroxymethyl propane, pentaerythrite, sorbierite
Initiator；Using propylene oxide, ethylene oxide, epoxy butane, styrene oxide, 7-oxa-bicyclo[4.1.0, epoxychloropropane, epoxy bromine
Propane, methyl glycidyl ether, allyl glycidyl ether etc. are the epoxide of addition polymerization, and hydroxyl value obtained is 12mgKOH/
The low unsaturation degree and high molecular weight polyoxyalkylene polyol of g~120mgKOH/g is within the protection scope of the present invention.
Claims (9)
1. a kind of preparation method of low unsaturation degree and high molecular weight polyoxyalkylene polyol, it is characterised in that be based on polyoxyalkylene
It the use of small molecular alcohol is initiator, in temperature 70~130 in the presence of 0.02%~0.2% KOH or NaOH of polyol quality
DEG C, reaction pressure be no more than 0.8MPa under the conditions of, open loop addition polymerization epoxide, obtain hydroxyl value be 300mgKOH/g~
The low molecular polyether intermediate of 900mgKOH/g, adds 0.05%~0.5% based on polyoxyalkylene polyol quality
Phosphazene compound is as catalyst, and at 70~130 DEG C of temperature, reaction pressure is no more than under the conditions of 0.8MPa, in polyether intermediate
Upper continuation open loop addition polymerization epoxide obtains the low unsaturation degree and high molecular weight that hydroxyl value is 12mgKOH/g~120mgKOH/g
Polyoxyalkylene polyol, and under the conditions of 50~150 DEG C using ion exchange resin by absorption contact method remove alkali and
Phosphonitrile, the polyoxyalkylene polyol refined；Wherein phosphazene compound structural formula is as follows:
2. the method as described in claim 1, it is characterised in that phosphazene compound quality is low unsaturation degree and high molecular weight polyoxy
Change the 0.1~0.4% of alkene polyol product quality.
3. the method as described in claim 1, it is characterised in that phosphazene compound quality is low unsaturation degree and high molecular weight polyoxy
Change the 0.15~0.2% of alkene polyol product quality.
4. the method as described in claim 1, it is characterised in that small molecular alcohol includes 1 valence alcohols of butanol, octanol, allyl alcohol；
Ethylene glycol, diethylene glycol, propylene glycol, dipropylene glycol, 1,3-PD, Isosorbide-5-Nitrae-cyclohexanediol, 1,3-BDO, Isosorbide-5-Nitrae-fourth two
Alcohol, 1,6- hexylene glycol, Isosorbide-5-Nitrae-cyclohexanediol divalent alcohols；Glycerol, trihydroxymethyl propane, pentaerythrite, sorbierite multivalence alcohol
Class.
5. the method as described in claim 1, it is characterised in that the epoxide of addition polymerization include propylene oxide, ethylene oxide,
Epoxy butane, styrene oxide, 7-oxa-bicyclo[4.1.0, epoxychloropropane, epoxy bromopropane, methyl glycidyl ether or allyl contracting
Water glycerin ether.
6. the method as described in claim 1, it is characterised in that low molecular polyether intermediate and polyoxyalkylene polyol manufacture
In the process, the temperature of open loop addition polymerization epoxide is 90~120 DEG C.
7. the method as described in claim 1, it is characterised in that low molecular polyether intermediate and polyoxyalkylene polyol manufacture
In the process, the reaction pressure of open loop addition polymerization epoxide is no more than 0.5MPa.
8. the method as described in claim 1, it is characterised in that ion exchange resin, will be relative to using batch process absorption contact
The deionized water of polyoxyalkylene polyol 0.1%~10% is added in polyoxyalkylene polyol, common with ion exchange resin afterwards
It is added in the reactor with stirring and heating device, in the presence of an inert gas, mixing is stirred under the conditions of 50~150 DEG C,
Processing 1~6 hour, the polyoxyalkylene polyol after recycling absorption contact, ion exchange resin usage amount is relative to polyoxyalkylene
The 0.01%~5% of polyol product quality.
9. the method as described in claim 1, it is characterised in that ion exchange resin is handed over ion using continuity method absorption contact
It changes resin to be filled in tower, polyoxyalkylene polyol is adjusted to 50~150 DEG C, is passed through ion exchange resin and is recycled absorption contact
Polyoxyalkylene polyol afterwards, the speed of the flow control of polyoxyalkylene polyol in 0.2~5L/h.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201811187400.2A CN109467691A (en) | 2018-10-12 | 2018-10-12 | A kind of preparation method of low unsaturation degree and high molecular weight polyoxyalkylene polyol |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201811187400.2A CN109467691A (en) | 2018-10-12 | 2018-10-12 | A kind of preparation method of low unsaturation degree and high molecular weight polyoxyalkylene polyol |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN109467691A true CN109467691A (en) | 2019-03-15 |
Family
ID=65663762
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201811187400.2A Pending CN109467691A (en) | 2018-10-12 | 2018-10-12 | A kind of preparation method of low unsaturation degree and high molecular weight polyoxyalkylene polyol |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN109467691A (en) |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN110790916A (en) * | 2019-10-09 | 2020-02-14 | 万华化学集团股份有限公司 | Preparation method of low-odor polyether polyol |
| CN112759755A (en) * | 2020-12-28 | 2021-05-07 | 山东一诺威新材料有限公司 | Preparation method of polyether polyol for super-soft slow-rebound foam |
| WO2022068323A1 (en) * | 2020-09-30 | 2022-04-07 | 浙江皇马科技股份有限公司 | Process for preparing allyl alcohol polyether having low potassium and sodium contents |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1212970A (en) * | 1997-08-19 | 1999-04-07 | 三井化学株式会社 | Flexible polyurethane foam with high durability |
| CN1332186A (en) * | 1995-09-12 | 2002-01-23 | 三井化学株式会社 | Catalyst for producing poly(alkylene oxide) by polymerization of alkylene oxide |
| JP2018030980A (en) * | 2016-08-26 | 2018-03-01 | 東ソー株式会社 | Method for producing polyalkylene glycol |
-
2018
- 2018-10-12 CN CN201811187400.2A patent/CN109467691A/en active Pending
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1332186A (en) * | 1995-09-12 | 2002-01-23 | 三井化学株式会社 | Catalyst for producing poly(alkylene oxide) by polymerization of alkylene oxide |
| CN1212970A (en) * | 1997-08-19 | 1999-04-07 | 三井化学株式会社 | Flexible polyurethane foam with high durability |
| JP2018030980A (en) * | 2016-08-26 | 2018-03-01 | 東ソー株式会社 | Method for producing polyalkylene glycol |
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN110790916A (en) * | 2019-10-09 | 2020-02-14 | 万华化学集团股份有限公司 | Preparation method of low-odor polyether polyol |
| CN110790916B (en) * | 2019-10-09 | 2022-04-22 | 万华化学集团股份有限公司 | Preparation method of low-odor polyether polyol |
| WO2022068323A1 (en) * | 2020-09-30 | 2022-04-07 | 浙江皇马科技股份有限公司 | Process for preparing allyl alcohol polyether having low potassium and sodium contents |
| CN112759755A (en) * | 2020-12-28 | 2021-05-07 | 山东一诺威新材料有限公司 | Preparation method of polyether polyol for super-soft slow-rebound foam |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN101851329A (en) | Starter feed stream acidification in dmc-catalyzed process for the production of polyether polyols | |
| CN109467691A (en) | A kind of preparation method of low unsaturation degree and high molecular weight polyoxyalkylene polyol | |
| TW530070B (en) | Process for rapid activation of double metal cyanide catalysts | |
| CA2450785C (en) | Process for the production of polyol blends | |
| CN101928391B (en) | Short chain polyether polyols prepared from ultra-low water-content starters via DMC catalysis | |
| JPH093186A (en) | Production of ethylene-oxide-capped polyol | |
| CN108070082B (en) | Method for preparing low-viscosity high-molecular-weight polyether polyol | |
| KR20050042451A (en) | Single reactor synthesis of koh-capped polyols based on dmc-synthesized intermediates | |
| KR102069569B1 (en) | Improved process for the production of low molecular weight impact polyethers | |
| CN110790916B (en) | Preparation method of low-odor polyether polyol | |
| CN114230782B (en) | Preparation method of bio-based polyether polyol | |
| KR20140047109A (en) | Continuous method for the synthesis of polyols | |
| CN106589344A (en) | Preparation method of unsaturated polyether | |
| JP5624324B2 (en) | Process for producing polyalkylene oxide | |
| CN104968705A (en) | A method to increase the resistance of double metal cyanide catalysts to deactivation | |
| CN104497298B (en) | Method for preparing polyether polyol with low degree of unsaturation, high molecular weight and high activity | |
| KR20120056831A (en) | Improved polyether glycol manufacturing process | |
| CN103224621B (en) | The alcoholysis method improved and device | |
| KR20220137681A (en) | Alkylene oxide polymerization with aluminum compound and phosphorus-nitrogen base | |
| CN114133552B (en) | Hydrophobic polyether polyol and preparation method thereof | |
| CN104497046B (en) | Organic alkoxide and preparation method thereof | |
| CN111423574B (en) | Dispersant for polymer polyol having cyclohexane structure and preparation method thereof | |
| CN100430136C (en) | Double metal cyanide catalysts | |
| JP2023512188A (en) | Alkylene Oxide Polymerization Using Aluminum Compounds and Cyclic Amidines | |
| JP4128182B2 (en) | Process for producing polyoxyalkylene polyol |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| RJ01 | Rejection of invention patent application after publication |
Application publication date: 20190315 |
|
| RJ01 | Rejection of invention patent application after publication |