CN110885435B - Process for preparing high functionality polyether polyols - Google Patents
Process for preparing high functionality polyether polyols Download PDFInfo
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- CN110885435B CN110885435B CN201911127607.5A CN201911127607A CN110885435B CN 110885435 B CN110885435 B CN 110885435B CN 201911127607 A CN201911127607 A CN 201911127607A CN 110885435 B CN110885435 B CN 110885435B
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- polyether polyol
- initiator
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- alkylene oxide
- catalyst
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- 239000004721 Polyphenylene oxide Substances 0.000 title claims abstract description 61
- 229920000570 polyether Polymers 0.000 title claims abstract description 61
- 229920005862 polyol Polymers 0.000 title claims abstract description 59
- 150000003077 polyols Chemical class 0.000 title claims abstract description 59
- 238000004519 manufacturing process Methods 0.000 title claims description 9
- 239000003999 initiator Substances 0.000 claims abstract description 52
- 125000002947 alkylene group Chemical group 0.000 claims abstract description 22
- 239000003054 catalyst Substances 0.000 claims abstract description 19
- 238000006116 polymerization reaction Methods 0.000 claims abstract description 13
- 238000000034 method Methods 0.000 claims abstract description 8
- 238000002360 preparation method Methods 0.000 claims abstract description 7
- 230000009471 action Effects 0.000 claims abstract description 4
- 238000006243 chemical reaction Methods 0.000 claims description 34
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 30
- PEDCQBHIVMGVHV-UHFFFAOYSA-N Glycerine Chemical compound OCC(O)CO PEDCQBHIVMGVHV-UHFFFAOYSA-N 0.000 claims description 27
- 238000003860 storage Methods 0.000 claims description 17
- GOOHAUXETOMSMM-UHFFFAOYSA-N Propylene oxide Chemical compound CC1CO1 GOOHAUXETOMSMM-UHFFFAOYSA-N 0.000 claims description 16
- 229910052757 nitrogen Inorganic materials 0.000 claims description 15
- 238000010438 heat treatment Methods 0.000 claims description 9
- 238000003756 stirring Methods 0.000 claims description 9
- 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 description 8
- 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 claims description 8
- 239000000600 sorbitol Substances 0.000 claims description 8
- FBPFZTCFMRRESA-KVTDHHQDSA-N D-Mannitol Chemical compound OC[C@@H](O)[C@@H](O)[C@H](O)[C@H](O)CO FBPFZTCFMRRESA-KVTDHHQDSA-N 0.000 claims description 6
- 229930195725 Mannitol Natural products 0.000 claims description 6
- 239000000594 mannitol Substances 0.000 claims description 6
- 235000010355 mannitol Nutrition 0.000 claims description 6
- IMNIMPAHZVJRPE-UHFFFAOYSA-N triethylenediamine Chemical compound C1CN2CCN1CC2 IMNIMPAHZVJRPE-UHFFFAOYSA-N 0.000 claims description 6
- IAYPIBMASNFSPL-UHFFFAOYSA-N Ethylene oxide Chemical compound C1CO1 IAYPIBMASNFSPL-UHFFFAOYSA-N 0.000 claims description 5
- 239000000203 mixture Substances 0.000 claims description 5
- 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 claims description 4
- 229930006000 Sucrose Natural products 0.000 claims description 4
- IISBACLAFKSPIT-UHFFFAOYSA-N bisphenol A Chemical compound C=1C=C(O)C=CC=1C(C)(C)C1=CC=C(O)C=C1 IISBACLAFKSPIT-UHFFFAOYSA-N 0.000 claims description 4
- 239000005720 sucrose Substances 0.000 claims description 4
- VOZKAJLKRJDJLL-UHFFFAOYSA-N 2,4-diaminotoluene Chemical compound CC1=CC=C(N)C=C1N VOZKAJLKRJDJLL-UHFFFAOYSA-N 0.000 claims description 3
- VPWNQTHUCYMVMZ-UHFFFAOYSA-N 4,4'-sulfonyldiphenol Chemical compound C1=CC(O)=CC=C1S(=O)(=O)C1=CC=C(O)C=C1 VPWNQTHUCYMVMZ-UHFFFAOYSA-N 0.000 claims description 3
- PIICEJLVQHRZGT-UHFFFAOYSA-N Ethylenediamine Chemical compound NCCN PIICEJLVQHRZGT-UHFFFAOYSA-N 0.000 claims description 3
- GSEJCLTVZPLZKY-UHFFFAOYSA-N Triethanolamine Chemical compound OCCN(CCO)CCO GSEJCLTVZPLZKY-UHFFFAOYSA-N 0.000 claims description 3
- ZJCCRDAZUWHFQH-UHFFFAOYSA-N Trimethylolpropane Chemical compound CCC(CO)(CO)CO ZJCCRDAZUWHFQH-UHFFFAOYSA-N 0.000 claims description 3
- TVXBFESIOXBWNM-UHFFFAOYSA-N Xylitol Natural products OCCC(O)C(O)C(O)CCO TVXBFESIOXBWNM-UHFFFAOYSA-N 0.000 claims description 3
- 150000001412 amines Chemical class 0.000 claims description 3
- 229930182478 glucoside Natural products 0.000 claims description 3
- 150000008131 glucosides Chemical class 0.000 claims description 3
- HEBKCHPVOIAQTA-UHFFFAOYSA-N meso ribitol Natural products OCC(O)C(O)C(O)CO HEBKCHPVOIAQTA-UHFFFAOYSA-N 0.000 claims description 3
- WXZMFSXDPGVJKK-UHFFFAOYSA-N pentaerythritol Chemical compound OCC(CO)(CO)CO WXZMFSXDPGVJKK-UHFFFAOYSA-N 0.000 claims description 3
- 239000000811 xylitol Substances 0.000 claims description 3
- HEBKCHPVOIAQTA-SCDXWVJYSA-N xylitol Chemical compound OC[C@H](O)[C@@H](O)[C@H](O)CO HEBKCHPVOIAQTA-SCDXWVJYSA-N 0.000 claims description 3
- 235000010447 xylitol Nutrition 0.000 claims description 3
- 229960002675 xylitol Drugs 0.000 claims description 3
- 125000002887 hydroxy group Chemical group [H]O* 0.000 abstract description 12
- 230000000977 initiatory effect Effects 0.000 abstract description 11
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 abstract description 4
- 230000015572 biosynthetic process Effects 0.000 abstract description 4
- 238000003786 synthesis reaction Methods 0.000 abstract description 4
- 238000007259 addition reaction Methods 0.000 abstract description 2
- WGCNASOHLSPBMP-UHFFFAOYSA-N hydroxyacetaldehyde Natural products OCC=O WGCNASOHLSPBMP-UHFFFAOYSA-N 0.000 abstract description 2
- 125000005702 oxyalkylene group Chemical group 0.000 abstract description 2
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 description 21
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 description 6
- 230000005587 bubbling Effects 0.000 description 6
- 239000007788 liquid Substances 0.000 description 5
- 229910001220 stainless steel Inorganic materials 0.000 description 5
- 239000010935 stainless steel Substances 0.000 description 5
- 230000000052 comparative effect Effects 0.000 description 4
- 239000007858 starting material Substances 0.000 description 4
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 4
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 3
- DNIAPMSPPWPWGF-UHFFFAOYSA-N Propylene glycol Chemical compound CC(O)CO DNIAPMSPPWPWGF-UHFFFAOYSA-N 0.000 description 3
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 3
- 150000001336 alkenes Chemical class 0.000 description 3
- 229910000147 aluminium phosphate Inorganic materials 0.000 description 3
- 150000001875 compounds Chemical class 0.000 description 3
- 238000001914 filtration Methods 0.000 description 3
- HCWCAKKEBCNQJP-UHFFFAOYSA-N magnesium orthosilicate Chemical compound [Mg+2].[Mg+2].[O-][Si]([O-])([O-])[O-] HCWCAKKEBCNQJP-UHFFFAOYSA-N 0.000 description 3
- 239000000391 magnesium silicate Substances 0.000 description 3
- 229910052919 magnesium silicate Inorganic materials 0.000 description 3
- 235000019792 magnesium silicate Nutrition 0.000 description 3
- JRZJOMJEPLMPRA-UHFFFAOYSA-N olefin Natural products CCCCCCCC=C JRZJOMJEPLMPRA-UHFFFAOYSA-N 0.000 description 3
- 229910001414 potassium ion Inorganic materials 0.000 description 3
- 238000012360 testing method Methods 0.000 description 3
- ROSDSFDQCJNGOL-UHFFFAOYSA-N Dimethylamine Chemical compound CNC ROSDSFDQCJNGOL-UHFFFAOYSA-N 0.000 description 2
- -1 alcohol amine Chemical class 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 239000004814 polyurethane Substances 0.000 description 2
- 125000002924 primary amino group Chemical group [H]N([H])* 0.000 description 2
- 238000007151 ring opening polymerisation reaction Methods 0.000 description 2
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 1
- 150000001450 anions Chemical class 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 238000010276 construction Methods 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 239000003814 drug Substances 0.000 description 1
- 230000036541 health Effects 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 125000004435 hydrogen atom Chemical group [H]* 0.000 description 1
- 238000009776 industrial production Methods 0.000 description 1
- BRMYZIKAHFEUFJ-UHFFFAOYSA-L mercury diacetate Chemical compound CC(=O)O[Hg]OC(C)=O BRMYZIKAHFEUFJ-UHFFFAOYSA-L 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 239000000178 monomer Substances 0.000 description 1
- 238000006386 neutralization reaction Methods 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 229920001451 polypropylene glycol Polymers 0.000 description 1
- 229920002635 polyurethane Polymers 0.000 description 1
- CASUWPDYGGAUQV-UHFFFAOYSA-M potassium;methanol;hydroxide Chemical compound [OH-].[K+].OC CASUWPDYGGAUQV-UHFFFAOYSA-M 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 230000009257 reactivity Effects 0.000 description 1
- 238000007670 refining Methods 0.000 description 1
- 238000007086 side reaction Methods 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 230000002194 synthesizing effect Effects 0.000 description 1
Classifications
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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
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
- C08G18/40—High-molecular-weight compounds
- C08G18/48—Polyethers
- C08G18/4829—Polyethers containing at least three hydroxy 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
- C08G65/2696—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 process or apparatus used
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G2101/00—Manufacture of cellular products
Abstract
The invention belongs to the technical field of polyether polyol synthesis, and particularly relates to a preparation method of high-functionality polyether polyol, which comprises the following steps: (1) taking a high-functionality initiator or a mixed initiator containing the high-functionality initiator as an initiator, and adding alkylene oxide to carry out polymerization reaction under the action of a catalyst to obtain oligomer polyether glycol; (2) and (2) adding the initiator, the catalyst and the alkylene oxide which are the same as those in the step (1) into the oligomer polyether polyol obtained in the step (1) to carry out polymerization reaction to obtain the high-functionality polyether polyol. The invention adopts a way of secondary feeding by a step method, so that an initiator system with high viscosity is diluted to a certain extent, the addition reaction of the oxyalkylene is easier to start, the problems of long initiation time and uneven polymerization are solved, the unsaturated value index of a polyether polyol product is lower, the hydroxyl value of an actual product is closer to the theoretical hydroxyl value, and the product can meet higher use requirements.
Description
Technical Field
The invention belongs to the technical field of polyether polyol synthesis, and particularly relates to a preparation method of high-functionality polyether polyol.
Background
Polyether Polyols (PPG) and polymer polyols (POP) are important raw materials for the Polyurethane (PU) industry. The polyurethane product has excellent physical and mechanical performance, easy processing, various products and wide application. The application field relates to the industries of automobiles, trains, steamships, airplanes, aerospace, furniture, household appliances, construction, medicine and health, mines, water power, electric power, electronics, agriculture and the like.
The industrial production of general polyether polyol is mainly based on anion catalyzed ring-opening polymerization, usually potassium hydroxide (or sodium hydroxide) or dimethylamine is used as a catalyst, micromolecular 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 (PO) or a mixture of the PO and Ethylene Oxide (EO) is used as a monomer, ring-opening polymerization is carried out at a certain temperature and pressure to obtain crude polyether polyol, and then steps such as neutralization and refining are carried out to obtain the finished polyether polyol.
The properties of polyether polyols are closely related to the initiator and also to the oxyalkylene chain length and arrangement in the molecule. The functionality of the polyether polyols depends on the type of initiator chosen for the synthesis and the number of its active hydrogens. The initiator for synthesizing polyether polyol is distinguished according to the nature of active groups and mainly comprises low molecular compounds containing hydroxyl and low molecular compounds containing amino or hydroxyl and amino. The most commonly used initiators are propylene glycol, trimethylolpropane, glycerol, mannitol, pentaerythritol, sorbitol, sucrose, xylitol, mannitol, glucoside, bisphenol A, bisphenol S, ethylenediamine, triethanolamine, triethylenediamine, toluenediamine, and the like. In order to obtain polyether polyols having suitable properties, such as functionality and viscosity, it is sometimes also possible to use mixed starters to produce the polyether. However, in any case, when the content of the high-functional, high-viscosity initiator is too high, there is a difficulty in initiating the initiator, and the uniformity of the reaction in the polymerization reaction of propylene oxide and ethylene oxide is affected.
The initiator for polyether polyol synthesis has different reactivity in addition of alkylene oxide due to differences in functionality, molecular weight, viscosity, etc., and the initiator with high functionality tends to have relatively high viscosity, and when polyether is prepared using the initiator with high functionality, initiation tends to be very difficult, and a large proportion of olefin is likely to be added to one or several branches after initiation, and thus cannot grow uniformly on all the branches.
Disclosure of Invention
The technical problem to be solved by the invention is as follows: the method overcomes the defects of the prior art, and provides a preparation method of the polyether polyol with high functionality, so that the high-viscosity initiator with high functionality can better and uniformly participate in the polymerization reaction with alkylene oxide in the reaction, the product functionality can be freely mastered, the reaction addition effect is better, the unsaturated value index of the polyether polyol product is lower, the actual product hydroxyl value is closer to the theoretical hydroxyl value, and more different use requirements can be met.
The preparation method of the high-functionality polyether polyol comprises the steps of firstly, adding alkylene oxide into a high-functionality initiator or a mixed initiator containing the high-functionality initiator under the action of a catalyst for polymerization reaction to prepare oligomer polyether polyol with a certain molecular weight. Then, carrying out secondary feeding, and adding a certain proportion of synthesized oligomer polyether polyol with a certain molecular weight as a reaction initiator while using the same high-functionality initiator or the mixed initiator containing the high-functionality initiator as the first time so as to shorten the initiation time of the reaction and help the uniform chain growth of the polymerization reaction, specifically comprising the following steps:
(1) taking a high-functionality initiator or a mixed initiator containing the high-functionality initiator as an initiator, and adding alkylene oxide to carry out polymerization reaction under the action of a catalyst to obtain oligomer polyether polyol;
(2) and (2) adding the initiator, the catalyst and the alkylene oxide which are the same as those in the step (1) into the oligomer polyether polyol obtained in the step (1) to carry out polymerization reaction to obtain the high-functionality polyether polyol.
Preferably, the mixed starter containing high-functionality starter in the step (1) contains the high-functionality starter in an amount of 10 to 100 percent by mass.
Preferably, the initiator used in step (1) is one or more selected from trimethylolpropane, glycerol, mannitol, pentaerythritol, sorbitol, sucrose, xylitol, mannitol, glucoside, bisphenol a, bisphenol S, ethylenediamine, triethanolamine, triethylenediamine, and toluenediamine.
Preferably, the catalyst in step (1) is one of a KOH system, an organic amine system, or a bimetallic system catalyst.
Preferably, the catalyst used in step (1) accounts for 1-5%, preferably 2-4% of the total feeding mass of step (1).
Preferably, the mass ratio of the initiator to the alkylene oxide in the step (1) is 10:90-70: 30.
Preferably, the alkylene oxide in step (1) is one or a mixture of propylene oxide and ethylene oxide in any proportion.
Preferably, the oligomer polyether polyol in the step (2) accounts for 2-15% of the total feeding mass of the step (2), the mass ratio of the initiator to the alkylene oxide is 5:95-60:40, and the catalyst accounts for 0-5% of the total feeding mass of the step (2).
Preferably, the oligomer polyether polyol obtained in step (1) has a molecular weight of 200-; the molecular weight of the high functionality polyether polyol product obtained in step (2) is 200-.
Preferably, the preparation method of the high-functionality polyether polyol comprises the following steps: the method comprises the following steps:
(1) adding a high-functionality initiator or a mixed initiator containing the high-functionality initiator and a catalyst into a reaction kettle, adding alkylene oxide into a storage tank at the temperature of less than or equal to 40 ℃, starting stirring the reaction kettle, replacing the mixture with nitrogen for 2-3 times, vacuumizing, heating to 100-; then dropping alkylene oxide into the reaction kettle through a storage tank for reaction, controlling the pressure to be 0.1-0.4MPa and the temperature to be 110-;
(2) adding the oligomer polyether glycol obtained in the step (1), an initiator and a catalyst which are the same as those in the step (1) into a reaction kettle, adding alkylene oxide into a storage tank at the temperature of less than or equal to 40 ℃, starting stirring the reaction kettle, replacing the mixture with nitrogen for 2-3 times, vacuumizing, heating to 100 ℃ and 120 ℃, and bubbling the nitrogen for 4 hours; then dropping alkylene oxide into the reaction kettle through a storage tank for reaction, controlling the pressure to be 0.1-0.4MPa and the temperature to be 110-.
Compared with the prior art, the invention has the following beneficial effects:
1. the method adopts a step-by-step method for secondary feeding, firstly uses the synthesized oligomer polyether polyol product with a certain molecular weight as a solvent, so that an initiator system with high viscosity is diluted to a certain extent, the addition reaction of the olefin oxide is easier to start, the problems of long initiation time and uneven polymerization are well solved, the polyether polyol product with higher functionality and higher molecular weight can be prepared, meanwhile, the functionality of the product can be freely mastered, the reaction addition effect is better, the index of the unsaturated value of the polyether polyol product is lower, and the hydroxyl value of the actual product is closer to the theoretical hydroxyl value, so that the product can meet the higher use requirement.
2. The invention adopts a step-by-step secondary feeding mode, so that the polymerization reaction is easier to carry out, the probability of side reaction of the olefin oxide is reduced, and the unsaturated value of the polyether polyol product is also reduced.
Detailed Description
The present invention will be further described with reference to the following examples.
Example 1
Adding 1140 parts of liquid sorbitol, 240 parts of glycerol and 18 parts of potassium hydroxide into a 5L stainless steel reaction kettle, and adding 2200 parts of propylene oxide into a storage tank at the temperature of less than or equal to 40 ℃; stirring the reaction kettle, replacing the nitrogen for 2-3 times, vacuumizing, heating to 110 ℃, and bubbling the nitrogen for 4 hours; adding 2200 parts of propylene oxide into a storage tank, initiating for about 5h, finishing the subsequent addition for about 10h, controlling the pressure to be 0.1-0.4MPa, the temperature to be 110-;
adding 190 parts of liquid sorbitol, 40 parts of glycerol, 215 parts of oligomer polyether polyol and 4.5 parts of potassium hydroxide into a 5L stainless steel reaction kettle, adding 3100 parts of propylene oxide into a storage tank, and keeping the temperature to be less than or equal to 40 ℃; stirring the reaction kettle, replacing the nitrogen for 2-3 times, vacuumizing, heating to 110 ℃, and bubbling the nitrogen for 4 hours; adding 3100 parts of propylene oxide into a storage tank, wherein the initiation time is less than 0.5h, finishing the subsequent addition of about 10h, controlling the pressure to be 0.1-0.4MPa and the temperature to be 110-; after the reaction is finished, adding phosphoric acid and water, adsorbing and crystallizing potassium ions by using magnesium silicate, decompressing and dehydrating, and filtering to obtain the polyether polyol product with high functionality.
Example 2
Adding 570 parts of liquid sorbitol, 120 parts of glycerol and 9 parts of potassium hydroxide into a 5L stainless steel reaction kettle, and adding 2200 parts of propylene oxide into a storage tank at the temperature of less than or equal to 40 ℃; stirring the reaction kettle, replacing the nitrogen for 2-3 times, vacuumizing, heating to 110 ℃, and bubbling the nitrogen for 4 hours; adding 2200 parts of propylene oxide into a storage tank, initiating for about 5h, finishing the subsequent addition for about 10h, controlling the pressure to be 0.1-0.4MPa, the temperature to be 110-;
adding 190 parts of liquid sorbitol, 40 parts of glycerol, 444 parts of oligomer polyether polyol and 4.5 parts of potassium hydroxide into a 5L stainless steel reaction kettle, adding 3100 parts of propylene oxide into a storage tank, and keeping the temperature to be less than or equal to 40 ℃; stirring the reaction kettle, replacing the nitrogen for 2-3 times, vacuumizing, heating to 110 ℃, and bubbling the nitrogen for 4 hours; adding 3100 parts of propylene oxide into a storage tank, wherein the initiation time is less than 0.5h, finishing the subsequent addition of about 10h, controlling the pressure to be 0.1-0.4MPa and the temperature to be 110-; after the reaction is finished, adding phosphoric acid and water, adsorbing the crystallized potassium ions by using magnesium silicate, decompressing, dehydrating and filtering to obtain the polyether polyol product with high functionality.
Comparative example 1
Adding 190 parts of liquid sorbitol, 40 parts of glycerol and 4.5 parts of potassium hydroxide into a 5L stainless steel reaction kettle, and adding 2325 parts of propylene oxide into a storage tank at a temperature of less than or equal to 40 ℃; stirring the reaction kettle, replacing the nitrogen for 2-3 times, vacuumizing, heating to 110 ℃, and bubbling the nitrogen for 4 hours; adding 2325 parts of propylene oxide into the storage tank, wherein the initiation time is about 5 hours, the subsequent addition is finished for about 10 hours, the pressure is controlled to be 0.1-0.4MPa, the temperature is 110-; after the reaction is finished, adding phosphoric acid and water, adsorbing and crystallizing potassium ions by using magnesium silicate, decompressing and dehydrating, and filtering to obtain the polyether polyol product.
Performance testing
The polyether polyol products prepared in examples 1-2 and comparative example 1 were subjected to performance testing, the test data are shown in table 1.
Note: the unsaturation value is determined by the principle that the unsaturated bond reacts with mercuric acetate and then free acetic acid is titrated with potassium hydroxide-methanol solution.
As can be seen from table 1 above: the actual hydroxyl numbers of the products in examples 1 and 2 are closer to the theoretical hydroxyl number (the theoretical hydroxyl number is 127.7mgKOH/g) and the unsaturation numbers are lower than those in comparative example 1; example 2, which used a greater amount of oligomer, had a lower hydroxyl number and unsaturation number than example 1. Also, examples 1 and 2, while adding one step to the preparation of the oligomer polyether polyol, are indeed more efficient overall than comparative example 1.
Of course, the foregoing is only a preferred embodiment of the invention and should not be taken as limiting the scope of the embodiments of the invention. The present invention is not limited to the above examples, and equivalent changes and modifications made by those skilled in the art within the spirit and scope of the present invention should be construed as being included in the scope of the present invention.
Claims (8)
1. A process for the preparation of a high functionality polyether polyol, characterized in that: the method comprises the following steps:
(1) taking a high-functionality initiator or a mixed initiator containing the high-functionality initiator as an initiator, and adding alkylene oxide to carry out polymerization reaction under the action of a catalyst to obtain oligomer polyether polyol;
(2) adding the initiator, the catalyst and the alkylene oxide which are the same as those in the step (1) into the oligomer polyether polyol obtained in the step (1) to carry out polymerization reaction to obtain high-functionality polyether polyol;
the initiator in the step (1) is one or more of trimethylolpropane, glycerol, mannitol, pentaerythritol, sorbitol, sucrose, xylitol, mannitol, glucoside, bisphenol A, bisphenol S, ethylenediamine, triethanolamine, triethylenediamine or toluenediamine;
the dosage of the catalyst in the step (1) accounts for 2-4% of the total feeding mass in the step (1), and the mass ratio of the initiator to the alkylene oxide is 10:90-70: 30.
2. The process for preparing a high functionality polyether polyol according to claim 1, characterized in that: the mass percentage of the high-functionality initiator in the mixed initiator containing the high-functionality initiator in the step (1) is 10-100%.
3. The process for preparing a high functionality polyether polyol according to claim 1, characterized in that: the catalyst in the step (1) is one of a KOH system, an organic amine system or a bimetallic system catalyst.
4. The process for preparing a high functionality polyether polyol according to claim 1, characterized in that: in the step (1), the alkylene oxide is one or a mixture of two of propylene oxide and ethylene oxide according to any proportion.
5. The process for preparing a high functionality polyether polyol according to claim 1, characterized in that: the oligomer polyether polyol in the step (2) accounts for 2-15% of the total feeding mass in the step (2).
6. The process for preparing a high functionality polyether polyol according to claim 1, characterized in that: the mass ratio of the initiator to the alkylene oxide in the step (2) is 5:95-60: 40.
7. The process for preparing a high functionality polyether polyol according to claim 1, characterized in that: the molecular weight of the oligomer polyether polyol obtained in the step (1) is 200-; the molecular weight of the high-functionality polyether polyol product obtained in the step (2) is 200-10000.
8. The process for preparing a high functionality polyether polyol according to claim 1, characterized in that: the method comprises the following steps:
(1) adding a high-functionality initiator or a mixed initiator containing the high-functionality initiator and a catalyst into a reaction kettle, adding alkylene oxide into a storage tank, starting stirring the reaction kettle, simultaneously heating to 100-plus-one temperature after nitrogen replacement, dropwise adding the alkylene oxide into the reaction kettle through the storage tank for reaction, controlling the pressure to be 0.1-0.4MPa and the temperature to be 110-plus-one temperature to be 115 ℃ after dropwise adding, and then carrying out internal pressure reaction for 2 hours to obtain oligomer polyether polyol;
(2) adding the oligomer polyether polyol obtained in the step (1) and an initiator and a catalyst which are the same as those in the step (1) into a reaction kettle, adding alkylene oxide into a storage tank, starting stirring the reaction kettle, simultaneously performing nitrogen replacement, heating to the temperature of 100-.
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| WO2022056687A1 (en) * | 2020-09-15 | 2022-03-24 | 万华化学（烟台）容威聚氨酯有限公司 | High-functionality polyether polyol and preparation method therefor |
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| CN112661952B (en) * | 2020-12-14 | 2023-09-22 | 山东一诺威新材料有限公司 | Preparation method of low-reaction heat 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 |
| CN113667111A (en) * | 2021-08-31 | 2021-11-19 | 山东一诺威新材料有限公司 | Preparation method of sorbitol-based high molecular weight polyether polyol |
| CN114230782A (en) * | 2021-12-21 | 2022-03-25 | 山东蓝星东大有限公司 | Preparation method of bio-based polyether polyol |
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