CN117304471A - Preparation method of hard foam polyether polyol - Google Patents
Preparation method of hard foam polyether polyol Download PDFInfo
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- CN117304471A CN117304471A CN202311058101.XA CN202311058101A CN117304471A CN 117304471 A CN117304471 A CN 117304471A CN 202311058101 A CN202311058101 A CN 202311058101A CN 117304471 A CN117304471 A CN 117304471A
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- Prior art keywords
- polyether polyol
- sorbitol
- reaction kettle
- propylene oxide
- functionality
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- 229920000570 polyether Polymers 0.000 title claims abstract description 62
- 239000004721 Polyphenylene oxide Substances 0.000 title claims abstract description 60
- 229920005862 polyol Polymers 0.000 title claims abstract description 52
- 150000003077 polyols Chemical class 0.000 title claims abstract description 52
- 239000006260 foam Substances 0.000 title claims abstract description 24
- 238000002360 preparation method Methods 0.000 title claims abstract description 13
- FBPFZTCFMRRESA-FSIIMWSLSA-N D-Glucitol Natural products OC[C@H](O)[C@H](O)[C@@H](O)[C@H](O)CO FBPFZTCFMRRESA-FSIIMWSLSA-N 0.000 claims abstract description 60
- 239000000600 sorbitol Substances 0.000 claims abstract description 60
- GOOHAUXETOMSMM-UHFFFAOYSA-N Propylene oxide Chemical compound CC1CO1 GOOHAUXETOMSMM-UHFFFAOYSA-N 0.000 claims abstract description 35
- 238000006243 chemical reaction Methods 0.000 claims abstract description 33
- 239000003999 initiator Substances 0.000 claims abstract description 26
- IJGRMHOSHXDMSA-UHFFFAOYSA-N nitrogen Substances N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims abstract description 19
- 238000003756 stirring Methods 0.000 claims abstract description 15
- 238000011282 treatment Methods 0.000 claims abstract description 13
- 208000005156 Dehydration Diseases 0.000 claims abstract description 12
- 239000002131 composite material Substances 0.000 claims abstract description 12
- 230000018044 dehydration Effects 0.000 claims abstract description 12
- 238000006297 dehydration reaction Methods 0.000 claims abstract description 12
- 239000003054 catalyst Substances 0.000 claims abstract description 11
- 229910052757 nitrogen Inorganic materials 0.000 claims abstract description 10
- 239000012043 crude product Substances 0.000 claims abstract description 7
- 238000010438 heat treatment Methods 0.000 claims abstract description 7
- 238000006116 polymerization reaction Methods 0.000 claims abstract description 7
- 239000000047 product Substances 0.000 claims abstract description 7
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 20
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical group [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 claims description 19
- PEDCQBHIVMGVHV-UHFFFAOYSA-N Glycerine Chemical compound OCC(O)CO PEDCQBHIVMGVHV-UHFFFAOYSA-N 0.000 claims description 15
- DNIAPMSPPWPWGF-UHFFFAOYSA-N Propylene glycol Chemical compound CC(O)CO DNIAPMSPPWPWGF-UHFFFAOYSA-N 0.000 claims description 12
- MTHSVFCYNBDYFN-UHFFFAOYSA-N diethylene glycol Chemical compound OCCOCCO MTHSVFCYNBDYFN-UHFFFAOYSA-N 0.000 claims description 12
- 238000000034 method Methods 0.000 claims description 10
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 claims description 9
- 238000006386 neutralization reaction Methods 0.000 claims description 7
- 238000001914 filtration Methods 0.000 claims description 6
- 235000011187 glycerol Nutrition 0.000 claims description 6
- 230000007062 hydrolysis Effects 0.000 claims description 6
- 238000006460 hydrolysis reaction Methods 0.000 claims description 6
- 238000001179 sorption measurement Methods 0.000 claims description 6
- ZJCCRDAZUWHFQH-UHFFFAOYSA-N Trimethylolpropane Chemical compound CCC(CO)(CO)CO ZJCCRDAZUWHFQH-UHFFFAOYSA-N 0.000 claims description 3
- WGCNASOHLSPBMP-UHFFFAOYSA-N hydroxyacetaldehyde Natural products OCC=O WGCNASOHLSPBMP-UHFFFAOYSA-N 0.000 claims description 3
- QXJQHYBHAIHNGG-UHFFFAOYSA-N trimethylolethane Chemical compound OCC(C)(CO)CO QXJQHYBHAIHNGG-UHFFFAOYSA-N 0.000 claims description 3
- RGSFGYAAUTVSQA-UHFFFAOYSA-N Cyclopentane Chemical compound C1CCCC1 RGSFGYAAUTVSQA-UHFFFAOYSA-N 0.000 abstract description 6
- 238000009413 insulation Methods 0.000 abstract description 6
- 230000036632 reaction speed Effects 0.000 abstract description 6
- 238000005187 foaming Methods 0.000 abstract description 5
- 239000000463 material Substances 0.000 abstract description 4
- DMEGYFMYUHOHGS-UHFFFAOYSA-N heptamethylene Natural products C1CCCCCC1 DMEGYFMYUHOHGS-UHFFFAOYSA-N 0.000 abstract description 3
- 238000004519 manufacturing process Methods 0.000 abstract description 3
- 238000006467 substitution reaction Methods 0.000 abstract description 2
- QJGQUHMNIGDVPM-UHFFFAOYSA-N nitrogen group Chemical group [N] QJGQUHMNIGDVPM-UHFFFAOYSA-N 0.000 abstract 1
- FBPFZTCFMRRESA-JGWLITMVSA-N D-glucitol Chemical compound OC[C@H](O)[C@@H](O)[C@H](O)[C@H](O)CO FBPFZTCFMRRESA-JGWLITMVSA-N 0.000 description 47
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 3
- NPYPAHLBTDXSSS-UHFFFAOYSA-N Potassium ion Chemical compound [K+] NPYPAHLBTDXSSS-UHFFFAOYSA-N 0.000 description 3
- 239000007864 aqueous solution Substances 0.000 description 3
- 230000001276 controlling effect Effects 0.000 description 3
- 239000001257 hydrogen Substances 0.000 description 3
- 229910052739 hydrogen Inorganic materials 0.000 description 3
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 3
- 229910001414 potassium ion Inorganic materials 0.000 description 3
- 239000002994 raw material Substances 0.000 description 3
- ROSDSFDQCJNGOL-UHFFFAOYSA-N Dimethylamine Chemical compound CNC ROSDSFDQCJNGOL-UHFFFAOYSA-N 0.000 description 2
- IAYPIBMASNFSPL-UHFFFAOYSA-N Ethylene oxide Chemical compound C1CO1 IAYPIBMASNFSPL-UHFFFAOYSA-N 0.000 description 2
- 229920005830 Polyurethane Foam Polymers 0.000 description 2
- CZMRCDWAGMRECN-UGDNZRGBSA-N Sucrose Chemical compound O[C@H]1[C@H](O)[C@@H](CO)O[C@@]1(CO)O[C@@H]1[C@H](O)[C@@H](O)[C@H](O)[C@@H](CO)O1 CZMRCDWAGMRECN-UGDNZRGBSA-N 0.000 description 2
- 229930006000 Sucrose Natural products 0.000 description 2
- 230000009471 action Effects 0.000 description 2
- 230000000052 comparative effect Effects 0.000 description 2
- 239000000203 mixture Substances 0.000 description 2
- 239000011496 polyurethane foam Substances 0.000 description 2
- 239000007787 solid Substances 0.000 description 2
- 239000000243 solution Substances 0.000 description 2
- 239000005720 sucrose Substances 0.000 description 2
- TVXBFESIOXBWNM-UHFFFAOYSA-N Xylitol Natural products OCCC(O)C(O)C(O)CCO TVXBFESIOXBWNM-UHFFFAOYSA-N 0.000 description 1
- 238000005054 agglomeration Methods 0.000 description 1
- 230000002776 aggregation Effects 0.000 description 1
- -1 alcohol amine Chemical class 0.000 description 1
- 150000001298 alcohols Chemical class 0.000 description 1
- 229910052783 alkali metal Inorganic materials 0.000 description 1
- 150000001340 alkali metals Chemical class 0.000 description 1
- 150000001412 amines Chemical class 0.000 description 1
- 150000001450 anions Chemical group 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000003197 catalytic effect Effects 0.000 description 1
- 238000013329 compounding Methods 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 229920001971 elastomer Polymers 0.000 description 1
- 239000000806 elastomer Substances 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 238000009472 formulation Methods 0.000 description 1
- 230000006698 induction Effects 0.000 description 1
- 238000009776 industrial production Methods 0.000 description 1
- 239000012774 insulation material Substances 0.000 description 1
- HEBKCHPVOIAQTA-UHFFFAOYSA-N meso ribitol Natural products OCC(O)C(O)C(O)CO HEBKCHPVOIAQTA-UHFFFAOYSA-N 0.000 description 1
- 239000000178 monomer Substances 0.000 description 1
- WXZMFSXDPGVJKK-UHFFFAOYSA-N pentaerythritol Chemical compound OCC(CO)(CO)CO WXZMFSXDPGVJKK-UHFFFAOYSA-N 0.000 description 1
- 230000008569 process Effects 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- 238000007670 refining Methods 0.000 description 1
- 230000001105 regulatory effect Effects 0.000 description 1
- 238000007151 ring opening polymerisation reaction Methods 0.000 description 1
- 238000007142 ring opening reaction Methods 0.000 description 1
- 238000003860 storage Methods 0.000 description 1
- 230000001502 supplementing effect Effects 0.000 description 1
- 239000000811 xylitol Substances 0.000 description 1
- HEBKCHPVOIAQTA-SCDXWVJYSA-N xylitol Chemical compound OC[C@H](O)[C@@H](O)[C@H](O)CO HEBKCHPVOIAQTA-SCDXWVJYSA-N 0.000 description 1
- 235000010447 xylitol Nutrition 0.000 description 1
- 229960002675 xylitol Drugs 0.000 description 1
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
- 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
-
- 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
-
- 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
-
- 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
-
- 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
- C08G2110/00—Foam properties
- C08G2110/0025—Foam properties rigid
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 invention relates to the technical field of polyether polyol preparation, in particular to a preparation method of rigid foam polyether polyol, which comprises the steps of adding sorbitol serving as an initiator and a catalyst into a reaction kettle, carrying out nitrogen substitution, stirring, heating and dehydration treatment, adding a functionality regulator into the reaction kettle, and obtaining a composite initiator after stirring uniformly; adding propylene oxide into a reaction kettle, carrying out polymerization reaction with the composite initiator, and curing to obtain a sorbitol polyether polyol crude product; post-treating the sorbitol polyether polyol crude product to obtain the sorbitol polyether polyol product; the polyether polyol synthesized by the invention meets the index requirements of the hard foam polyether polyol, has lower viscosity, better fluidity and better compatibility with cyclopentane, is suitable for being used as a cold insulation foaming material of a refrigerator, increases the intersolubility of an initiator and propylene oxide, improves the reaction speed and improves the production efficiency.
Description
Technical Field
The invention relates to the technical field of polyether polyol preparation, in particular to a preparation method of hard foam polyether polyol.
Background
The industrial production of polyether polyol generally takes anion ring-opening catalytic polymerization as a main process, potassium hydroxide or dimethylamine is generally used as a catalyst, small molecular polyol such as glycerol or sucrose or other active hydrogen-containing compounds such as amine and alcohol amine are used as an initiator, propylene oxide (propylene oxide for short, PO) or a mixture of propylene oxide and ethylene oxide (ethylene oxide for short, EO) is used as a monomer, ring-opening polymerization is carried out at a certain temperature and under a certain pressure to obtain crude polyether, and then the steps of neutralization, refining and the like are carried out to obtain a polyether product. Such polyether polyols, including long chain polyethers for soft foams and elastomers, short chain polyfunctional polyethers for hard foams, have been widely used in polyurethane foams and in small amounts in elastomeric articles.
The rigid foam polyether polyol product is mainly applied to heat insulation materials, such as pipeline heat insulation, storage tank heat insulation, building heat insulation, boards, refrigerators, freezers, water heaters and the like, and has the advantages of light weight, small heat conductivity coefficient, high mechanical strength, good bonding performance and the like.
The hard foam polyether polyol is produced by taking active hydrogen-containing active hydrogen as an initiator, such as propylene glycol, diethylene glycol, glycerol, pentaerythritol, xylitol, sorbitol, sucrose and the like, and carrying out polymerization reaction with propylene oxide under the action of a catalyst.
Sorbitol is used as a 6-functionality initiator, and the synthesized hard foam polyether has superior dimensional stability, mechanical property, softening temperature and oil resistance to the traditional 3-functionality polyether when applied to polyurethane foam. Sorbitol is a solid at normal temperature and has poor compatibility with propylene oxide, so that the feeding speed is slow in the initial stage of reaction and the pressure is high, so that a proper regulator is required to be added to control and improve the early reaction speed, and the functionality of polyether can be regulated.
Through searching, chinese patent publication number: CN102617848A discloses a method for preparing sorbitol polyether polyol, which takes crystalline sorbitol and propylene oxide as raw materials, and prepares the sorbitol polyether polyol through polymerization under the action of a catalyst and a regulator. However, the regulator used in this scheme is ethylene glycol or glycerol, which has a limited solubility for sorbitol, and thus the reaction rate in the early stage is still slow.
For another example, chinese patent publication No. CN106146823a discloses a method for preparing a pure crystalline sorbitol polyether polyol, in which pure crystalline sorbitol is used as an initiator, alkali metal is used as a catalyst, and propylene oxide is polymerized in three stages at a certain temperature and pressure to obtain the pure crystalline sorbitol polyether polyol. However, in the scheme, sorbitol is solid at normal temperature, after the temperature rises, the sorbitol is melted and stirred, so that the phenomenon of agglomeration can occur, stirring is easy to damage, and the intersolubility with propylene oxide is poor in a melted state, so that the initial reaction speed is very slow, and a long induction period is required; the functionality of the rigid foam polyether is usually between 4 and 4.5, and a high functionality initiator and a low functionality are usually required for compounding, so that the pure sorbitol polyether polyol has high viscosity and poor flowability, and directly affects downstream application.
Disclosure of Invention
(1) Technical problem to be solved
Aiming at the defects of the prior art, the invention aims to provide a preparation method of rigid foam polyether polyol, which solves the problem of poor compatibility of sorbitol and propylene oxide in the prior art, improves the early reaction speed of sorbitol and propylene oxide, and improves the production efficiency.
(2) Technical proposal
In order to solve the technical problems, the invention provides a preparation method of the hard foam polyether polyol, which comprises the following preparation steps:
s1, adding sorbitol serving as an initiator and a catalyst into a reaction kettle, and performing nitrogen replacement, stirring, heating and dehydration treatment, adding a functionality regulator into the reaction kettle, and uniformly stirring to obtain a composite initiator;
s2, adding propylene oxide into a reaction kettle, carrying out polymerization reaction with the composite initiator, and curing to obtain a sorbitol polyether polyol crude product;
s3, carrying out post-treatment on the sorbitol polyether polyol crude product to obtain the sorbitol polyether polyol product;
the functionality regulator in the step S1 is one or two of water, glycol, propylene glycol, diglycol or trifunctional glycerin, trimethylolpropane and trimethylolethane, the average functionality of the functionality regulator after being compounded with sorbitol is between 4 and 4.5, and water is preferably used as the functionality regulator.
Preferably, the catalyst is potassium hydroxide.
Preferably, the propylene oxide in the step S2 is added in two stages, firstly, the propylene oxide is slowly added dropwise, and the dropping speed of the propylene oxide is accelerated when the pressure of the reaction kettle begins to drop.
Preferably, the temperature in the reaction kettle is 105-120 ℃, and the pressure in the reaction kettle is less than 0.40Mpa.
Preferably, the sorbitol in step S1 is 70% aqueous sorbitol or a combination of 70% aqueous sorbitol and partially crystalline sorbitol.
Preferably, in step S3, the post-treatment includes hydrolysis, neutralization, adsorption, dehydration, and filtration in this order.
(3) Advantageous effects
Compared with the prior art, the invention has the beneficial effects that:
the invention adopts water with low price as an initiator to be compounded with sorbitol to synthesize the hard foam polyether polyol, the functionality of the polyether is controlled to be between 4.0 and 4.5, the sorbitol is extremely soluble in water, the reaction speed of the initiator and propylene oxide can be accelerated, the reaction temperature is controlled to be 105-115 ℃, the pressure is less than 0.4Mpa, the index of the synthesized polyether polyol meets the index requirement of the hard foam polyether polyol, the viscosity is lower, the fluidity is better, the compatibility with cyclopentane is better, the polyether polyol is suitable for being used as a foaming material for cold insulation of a refrigerator, the raw materials in the preparation method are easy to obtain, the cost is lower, the reaction operation is simple, the polyether polyol is safe and environment-friendly, no special reaction equipment is needed, the viscosity is lower, the polyether polyol has better fluidity, has better compatibility with cyclopentane, is suitable for cold insulation foaming materials of a refrigerator, the intersolubility of the initiator and the propylene oxide is increased, and the reaction speed is improved, and meanwhile the production efficiency is improved.
Detailed Description
In order to make the objects, technical solutions and advantages of the present invention more apparent, the technical solutions of the present invention will be described in detail below. It will be apparent that the described embodiments are only some, but not all, embodiments of the invention. All other embodiments, based on the examples herein, which are within the scope of the invention as defined by the claims, will be within the scope of the invention as defined by the claims.
The raw materials used in examples and comparative examples, if not particularly limited, are all as disclosed in the prior art, and are, for example, available directly or prepared according to the preparation methods disclosed in the prior art.
The invention provides a technical scheme that:
a method for preparing a hard foam polyether polyol, comprising the following preparation steps:
adding sorbitol serving as an initiator and a catalyst into a reaction kettle, and performing nitrogen replacement, stirring, heating and dehydration treatment, adding a functionality regulator into the reaction kettle, and uniformly stirring to obtain a composite initiator;
step two, adding propylene oxide into a reaction kettle, carrying out polymerization reaction with a composite initiator, and curing to obtain a sorbitol polyether polyol crude product;
step three, carrying out post-treatment on the crude sorbitol polyether polyol product to obtain a sorbitol polyether polyol product;
in the first step, the functionality regulator is one or two of water, glycol, propylene glycol, diglycol or trifunctional glycerin, trimethylolpropane and trimethylolethane, the average functionality of the functionality regulator and sorbitol is between 4 and 4.5 after being compounded, and water is preferably used as the functionality regulator.
It should be noted that, because water is used as an inexpensive initiator, the use is very convenient, the solubility of sorbitol in water is better than that of other alcohols, water is not completely involved in the reaction as a functionality regulator, and only about 50% of water is involved in the reaction, so that the amount of water involved in the reaction is calculated only when the formulation is designed.
Further, the catalyst is potassium hydroxide (KOH).
Further, in the second step, the epoxypropane is added in two stages, firstly, the epoxypropane is slowly added dropwise, and the dripping speed of the epoxypropane is accelerated when the pressure of the reaction kettle begins to drop.
Further, the temperature in the reaction kettle is 105-120 ℃, and the pressure in the reaction kettle is less than 0.40Mpa.
Further, in step one, sorbitol is 70% aqueous sorbitol or a combination of 70% aqueous sorbitol and partially crystalline sorbitol.
Further, in the third step, the post-treatment sequentially comprises hydrolysis, neutralization, adsorption, dehydration and filtration.
Description of the preferred embodiments
Example 1
241g of 70% sorbitol aqueous solution and 3g of KOH are added into a 2L reaction kettle, nitrogen is replaced for 3 times, stirring and heating are carried out, the temperature is controlled at 110-120 ℃ for dehydration for 3 hours, water is added for 24.6g, after stirring is carried out uniformly, 819g of propylene oxide is slowly dripped into the kettle at 105-115 ℃ under control of the temperature, the pressure begins to drop after 20 minutes, the propylene oxide begins to react, at this time, the dripping speed of the propylene oxide can be accelerated, the pressure is controlled to be less than 0.40Mpa, the pressure is maintained for 3 hours after the dripping is finished, nitrogen can be supplemented after the pressure drop, post treatments such as hydrolysis, neutralization, adsorption, dehydration, filtration and the like are needed after the curing is finished, so that the sorbitol and water composite initiator polyether polyol, the hydroxyl value of 391.3mgKOH/g, the viscosity of 2563 mpa.s, the PH value of 6.1, the potassium ion of 8ppm and the moisture content of 0.05% can be met.
Example 2
82g of 70% sorbitol aqueous solution, 111.3g of crystalline sorbitol and 3g of KOH are added into a 2L reaction kettle, nitrogen is replaced for 3 times, stirring and heating are carried out, after uniform stirring, 819g of propylene oxide is slowly dripped under the condition that the temperature in the kettle is controlled to be 105-115, the pressure begins to drop after 18 minutes, the propylene oxide begins to react, the dripping speed of the propylene oxide can be accelerated, the pressure is controlled to be less than 0.40Mpa, the pressure maintaining reaction is carried out for 3 hours after the dripping is finished, nitrogen can be supplemented after the pressure drop, post treatments such as hydrolysis, neutralization, adsorption, dehydration and filtration are needed after the curing is finished, the sorbitol and water composite initiator polyether polyol can be obtained, the hydroxyl value is 390.8mgKOH/g, the viscosity is 2539 mpa.s, the PH value is 6.0, the potassium ion is 8ppm, and the moisture is 0.05%, and the index requirement of the sorbitol polyether polyol is met.
Example 3
Adding 240g of 70% sorbitol aqueous solution and 3g of KOH into a 2L reaction kettle, replacing 3 times with nitrogen, stirring, heating, controlling the temperature to be between 110 and 120 ℃, adding 73.2g of diethylene glycol after dehydration for 3 hours, after stirring uniformly, controlling the temperature in the kettle to be between 105 and 115, slowly dropwise adding 759g of propylene oxide, starting to reduce the pressure after 40 minutes, starting to react the propylene oxide, accelerating the dropwise adding speed of the propylene oxide at the moment, controlling the pressure to be less than 0.40Mpa, maintaining the pressure for 3 hours after dropwise adding is finished, supplementing nitrogen for pressure reduction, and after curing is finished, carrying out post treatments such as hydrolysis, neutralization, adsorption, dehydration, filtration and the like to obtain the polyether polyol serving as the sorbitol and water composite initiator, wherein the hydroxyl value is 391.3mgKOH/g, the viscosity is 3245 mpa.s, the PH value is 5.9, the potassium ion is 7ppm, and the water content is 0.06%.
The sorbitol polyether polyol manufactured in the above examples 1 to 3 was subjected to a foaming comparison experiment, and the room temperature was controlled to 25+ -2deg.C, and the material temperature was controlled to 25+ -1deg.C;
the test results are shown in table 1:
table 1 shows the results of comparative test of foaming of sorbitol polyether polyol
From the above, it can be seen from the above examples that the hard foam polyether polyol prepared by using sorbitol and water as the composite initiator has a qualified index, meets the index requirements of the hard foam polyether, has a viscosity lower than that of polyether using diethylene glycol as the functionality regulator, has better fluidity, and has a better operation space for downstream clients.
All technical features in the embodiment can be freely combined according to actual needs.
The foregoing embodiments are preferred embodiments of the present invention, and in addition, the present invention may be implemented in other ways, and any obvious substitution is within the scope of the present invention without departing from the concept of the present invention.
Claims (6)
1. A method for preparing a rigid foam polyether polyol, which is characterized by comprising the following preparation steps:
s1, adding sorbitol serving as an initiator and a catalyst into a reaction kettle, and performing nitrogen replacement, stirring, heating and dehydration treatment, adding a functionality regulator into the reaction kettle, and uniformly stirring to obtain a composite initiator;
s2, adding propylene oxide into a reaction kettle, carrying out polymerization reaction with the composite initiator, and curing to obtain a sorbitol polyether polyol crude product;
s3, carrying out post-treatment on the sorbitol polyether polyol crude product to obtain the sorbitol polyether polyol product;
the functionality regulator in the step S1 is one or two of water, glycol, propylene glycol, diglycol or trifunctional glycerin, trimethylolpropane and trimethylolethane, the average functionality of the functionality regulator after being compounded with sorbitol is between 4 and 4.5, and water is preferably used as the functionality regulator.
2. The method for preparing a rigid foam polyether polyol according to claim 1, wherein the catalyst is potassium hydroxide.
3. The method for preparing the rigid foam polyether polyol according to claim 1, wherein in the step S2, the propylene oxide is added in two stages, and the propylene oxide is slowly added dropwise, and the dropping speed of the propylene oxide is accelerated when the pressure of the reaction kettle begins to drop.
4. The method for preparing a rigid foam polyether polyol according to claim 1, wherein the temperature in the reaction kettle is 105-120 ℃, and the pressure in the reaction kettle is less than 0.40Mpa.
5. The method of preparing a rigid foam polyether polyol according to claim 1, wherein the sorbitol in step S1 is 70% aqueous sorbitol or a combination of 70% aqueous sorbitol and partially crystalline sorbitol.
6. The method for preparing a rigid foam polyether polyol according to claim 1, wherein in the step S3, the post-treatment comprises hydrolysis, neutralization, adsorption, dehydration, and filtration in this order.
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