CN115594836A - Preparation method of hard foam polyether polyol - Google Patents
Preparation method of hard foam polyether polyol Download PDFInfo
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- CN115594836A CN115594836A CN202211205577.7A CN202211205577A CN115594836A CN 115594836 A CN115594836 A CN 115594836A CN 202211205577 A CN202211205577 A CN 202211205577A CN 115594836 A CN115594836 A CN 115594836A
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- polyether polyol
- epoxide
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- foam polyether
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- 229920000570 polyether Polymers 0.000 title claims abstract description 68
- 239000004721 Polyphenylene oxide Substances 0.000 title claims abstract description 67
- 229920005862 polyol Polymers 0.000 title claims abstract description 60
- 150000003077 polyols Chemical class 0.000 title claims abstract description 60
- 239000006260 foam Substances 0.000 title claims abstract description 29
- 238000002360 preparation method Methods 0.000 title claims abstract description 25
- 238000006243 chemical reaction Methods 0.000 claims abstract description 73
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims abstract description 36
- 238000000034 method Methods 0.000 claims abstract description 31
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 27
- 239000003054 catalyst Substances 0.000 claims abstract description 22
- 150000001412 amines Chemical class 0.000 claims abstract description 21
- 229910052757 nitrogen Inorganic materials 0.000 claims abstract description 18
- 238000004519 manufacturing process Methods 0.000 claims abstract description 4
- 150000002924 oxiranes Chemical class 0.000 claims description 37
- ROSDSFDQCJNGOL-UHFFFAOYSA-N Dimethylamine Chemical compound CNC ROSDSFDQCJNGOL-UHFFFAOYSA-N 0.000 claims description 28
- GOOHAUXETOMSMM-UHFFFAOYSA-N Propylene oxide Chemical compound CC1CO1 GOOHAUXETOMSMM-UHFFFAOYSA-N 0.000 claims description 27
- 238000006116 polymerization reaction Methods 0.000 claims description 15
- 238000010438 heat treatment Methods 0.000 claims description 14
- PEDCQBHIVMGVHV-UHFFFAOYSA-N Glycerine Chemical compound OCC(O)CO PEDCQBHIVMGVHV-UHFFFAOYSA-N 0.000 claims description 12
- MTHSVFCYNBDYFN-UHFFFAOYSA-N diethylene glycol Chemical compound OCCOCCO MTHSVFCYNBDYFN-UHFFFAOYSA-N 0.000 claims description 12
- 239000004519 grease Substances 0.000 claims description 11
- 239000003999 initiator Substances 0.000 claims description 10
- 230000001681 protective effect Effects 0.000 claims description 9
- 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 7
- 229930006000 Sucrose Natural products 0.000 claims description 7
- 150000005846 sugar alcohols Polymers 0.000 claims description 7
- DNIAPMSPPWPWGF-UHFFFAOYSA-N Propylene glycol Chemical compound CC(O)CO DNIAPMSPPWPWGF-UHFFFAOYSA-N 0.000 claims description 6
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 claims description 6
- 238000002156 mixing Methods 0.000 claims description 6
- 239000000203 mixture Substances 0.000 claims description 6
- BAVYZALUXZFZLV-UHFFFAOYSA-N Methylamine Chemical compound NC BAVYZALUXZFZLV-UHFFFAOYSA-N 0.000 claims description 4
- GETQZCLCWQTVFV-UHFFFAOYSA-N trimethylamine Chemical compound CN(C)C GETQZCLCWQTVFV-UHFFFAOYSA-N 0.000 claims description 4
- 239000005720 sucrose Substances 0.000 claims description 3
- HZAXFHJVJLSVMW-UHFFFAOYSA-N 2-Aminoethan-1-ol Chemical compound NCCO HZAXFHJVJLSVMW-UHFFFAOYSA-N 0.000 claims description 2
- 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 2
- 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 2
- IAYPIBMASNFSPL-UHFFFAOYSA-N Ethylene oxide Chemical compound C1CO1 IAYPIBMASNFSPL-UHFFFAOYSA-N 0.000 claims description 2
- GSEJCLTVZPLZKY-UHFFFAOYSA-N Triethanolamine Chemical compound OCCN(CCO)CCO GSEJCLTVZPLZKY-UHFFFAOYSA-N 0.000 claims description 2
- SLINHMUFWFWBMU-UHFFFAOYSA-N Triisopropanolamine Chemical compound CC(O)CN(CC(C)O)CC(C)O SLINHMUFWFWBMU-UHFFFAOYSA-N 0.000 claims description 2
- NBZANZVJRKXVBH-GYDPHNCVSA-N alpha-Cryptoxanthin Natural products O[C@H]1CC(C)(C)C(/C=C/C(=C\C=C\C(=C/C=C/C=C(\C=C\C=C(/C=C/[C@H]2C(C)=CCCC2(C)C)\C)/C)\C)/C)=C(C)C1 NBZANZVJRKXVBH-GYDPHNCVSA-N 0.000 claims description 2
- 239000010775 animal oil Substances 0.000 claims description 2
- ZBCBWPMODOFKDW-UHFFFAOYSA-N diethanolamine Chemical compound OCCNCCO ZBCBWPMODOFKDW-UHFFFAOYSA-N 0.000 claims description 2
- LVTYICIALWPMFW-UHFFFAOYSA-N diisopropanolamine Chemical compound CC(O)CNCC(C)O LVTYICIALWPMFW-UHFFFAOYSA-N 0.000 claims description 2
- 229940043276 diisopropanolamine Drugs 0.000 claims description 2
- SZXQTJUDPRGNJN-UHFFFAOYSA-N dipropylene glycol Chemical compound OCCCOCCCO SZXQTJUDPRGNJN-UHFFFAOYSA-N 0.000 claims description 2
- 239000011259 mixed solution Substances 0.000 claims description 2
- WXZMFSXDPGVJKK-UHFFFAOYSA-N pentaerythritol Chemical compound OCC(CO)(CO)CO WXZMFSXDPGVJKK-UHFFFAOYSA-N 0.000 claims description 2
- 230000035484 reaction time Effects 0.000 claims description 2
- 239000000243 solution Substances 0.000 claims description 2
- 239000000600 sorbitol Substances 0.000 claims description 2
- ZIBGPFATKBEMQZ-UHFFFAOYSA-N triethylene glycol Chemical compound OCCOCCOCCO ZIBGPFATKBEMQZ-UHFFFAOYSA-N 0.000 claims description 2
- 235000015112 vegetable and seed oil Nutrition 0.000 claims description 2
- 239000008158 vegetable oil Substances 0.000 claims description 2
- 230000032683 aging Effects 0.000 claims 3
- 239000007858 starting material Substances 0.000 claims 1
- 230000015572 biosynthetic process Effects 0.000 abstract description 9
- 238000003786 synthesis reaction Methods 0.000 abstract description 9
- 230000008901 benefit Effects 0.000 abstract description 7
- 238000006555 catalytic reaction Methods 0.000 abstract description 5
- 230000007613 environmental effect Effects 0.000 abstract description 5
- 238000004134 energy conservation Methods 0.000 abstract description 2
- 150000002118 epoxides Chemical class 0.000 abstract 3
- 239000007864 aqueous solution Substances 0.000 description 12
- 239000000463 material Substances 0.000 description 12
- 230000000052 comparative effect Effects 0.000 description 10
- 238000012360 testing method Methods 0.000 description 8
- 238000001514 detection method Methods 0.000 description 7
- 229960004793 sucrose Drugs 0.000 description 6
- 235000019482 Palm oil Nutrition 0.000 description 4
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 4
- 239000001301 oxygen Substances 0.000 description 4
- 229910052760 oxygen Inorganic materials 0.000 description 4
- 239000002540 palm oil Substances 0.000 description 4
- 238000005086 pumping Methods 0.000 description 4
- 238000005070 sampling Methods 0.000 description 4
- 238000009413 insulation Methods 0.000 description 3
- 125000005702 oxyalkylene group Chemical group 0.000 description 3
- 238000005303 weighing Methods 0.000 description 3
- 239000002131 composite material Substances 0.000 description 2
- 150000001875 compounds Chemical class 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 238000005259 measurement Methods 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 239000002994 raw material Substances 0.000 description 2
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 1
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 1
- 238000003915 air pollution Methods 0.000 description 1
- 230000003197 catalytic effect Effects 0.000 description 1
- 238000000576 coating method Methods 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 238000003912 environmental pollution Methods 0.000 description 1
- 239000003822 epoxy resin Substances 0.000 description 1
- 150000002170 ethers Chemical class 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 229920000233 poly(alkylene oxides) Polymers 0.000 description 1
- 229920001281 polyalkylene Polymers 0.000 description 1
- 229920000647 polyepoxide Polymers 0.000 description 1
- 239000004814 polyurethane Substances 0.000 description 1
- 229920002635 polyurethane Polymers 0.000 description 1
- 238000007151 ring opening polymerisation reaction Methods 0.000 description 1
- -1 small molecule amine Chemical class 0.000 description 1
- 238000001308 synthesis method Methods 0.000 description 1
- 239000006188 syrup Substances 0.000 description 1
- 235000020357 syrup Nutrition 0.000 description 1
- 238000009489 vacuum treatment Methods 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
- C08G65/2696—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
- 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
- C08G18/4891—Polyethers modified with higher fatty oils or their acids or by resin acids
-
- 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
Abstract
The invention belongs to the technical field of polyether polyol synthesis, and particularly relates to a hard foam polyether polyol and a preparation method capable of effectively reducing the content of residual epoxide in the polyether polyol. In the preparation method of the hard foam polyether polyol, the applicant discovers that the catalyst can be effectively activated by adding water into a reaction system in the curing reaction process to improve the water content of the system on the basis of the traditional amine catalysis process, so that the catalytic reaction efficiency of the product is effectively improved, and the epoxide residue in the polyether product is reduced; and further, residual epoxide is further consumed in a mode of charging nitrogen into the reaction kettle for boosting, and the reaction efficiency of the product is effectively improved. The preparation method of the hard foam polyether polyol has the advantages of simplicity in operation, high production efficiency, energy conservation and environmental protection, meets increasingly severe environmental protection requirements, and has good economic benefits.
Description
Technical Field
The invention belongs to the technical field of polyether polyol synthesis, and particularly relates to a hard foam polyether polyol and a preparation method capable of effectively reducing the content of residual epoxide in the polyether polyol.
Background
Polyether polyols, referred to as polyethers, also known as polyalkylene ethers or polyalkylene oxides, are generally prepared by ring-opening polymerization of epoxides in the presence of active hydrogen-containing compounds as initiators and catalysts. Polyether polyol is an important raw material in the polyurethane industry, and is widely applied to the fields of household appliance heat insulation, pipeline heat insulation, sandwich boards, automotive interiors, coatings and the like, wherein the hard foam polyether polyol is mainly used for producing hard foam and is widely applied to the heat insulation fields of external walls, refrigerators, freezers, water heaters, pipelines, containers and the like.
In the prior art, in the industry of hard foam polyether polyol synthesis, two general production processes, namely a refined polyether process using KOH as a catalyst and an amine process using dimethylamine aqueous solution and the like as a catalyst, are generally adopted. The amine process has the problems that when polyether added with grease is catalyzed for synthesis, particularly when epoxide is fed till the curing is finished, the activity of a catalyst is greatly reduced, so that residual epoxide is high, the post-treatment needs to be vacuumized to remove the residual epoxide to enable the residual epoxide to reach the standard or below, but the problems of environmental pollution and the like are caused, and the yield of the product is seriously influenced. Therefore, the finding and solving of the problem of epoxide residue caused by polyether synthesis by amine process is of great significance.
For example, in the method for improving the propylene oxide conversion rate in the polyether polyol synthesis process disclosed in chinese patent CN107903387a, the small molecule amine is introduced at the later stage of the polyether polyol synthesis process to consume the residual PO and increase the reaction activity, thereby achieving the purpose of reducing the PO residue in the polyether. Also, for example, in the preparation method of the hard foam polyether polyol disclosed in chinese patent CN106810682a, the composite amine is used as the catalyst and the composite amine catalyst is added in stages in the reaction process, so as to achieve the purpose of high completeness of PO reaction and less residual PO amount in the later stage of the reaction, and have the advantage of high product yield, and the product does not need to be post-treated, so that the whole process has little air pollution. And as the preparation method of the sucrose polyether polyol disclosed in the Chinese patent CN107151318A, the liquid syrup is used as a raw material, the novel amine is used as a catalyst for reaction, the post-treatment process of the whole process is simple, the small molecular alcohol is added after the addition of the oxyalkylene reaches 20%, the removal of the oxyalkylene in the post-treatment is less, and the conversion rate of the oxyalkylene is high.
Therefore, the development of a synthesis method capable of improving the epoxide conversion rate in the polyether polyol synthesis process has positive significance.
Disclosure of Invention
Therefore, the technical problem to be solved by the invention is to provide a method for preparing hard-foam polyether polyol, which can improve the conversion rate of epoxide in the synthesis process of polyether polyol, and the method has the advantages of high economic benefit, environmental friendliness and simple operation;
the second technical problem to be solved by the present invention is to provide a hard foam polyether polyol product, which has a low residual epoxide content and can be prepared into a finished product polyether polyol without removing the residual epoxide in vacuum.
In order to solve the technical problem, the preparation method of the hard foam polyether polyol comprises the following steps:
(1) Under the protective atmosphere, taking an initiator and an amine catalyst, and continuously adding epoxide for polymerization reaction;
(2) And after the epoxide is added, continuing to perform a curing reaction, adding water in the curing reaction process for mixing, and continuing to react until the curing is finished to obtain the epoxy resin.
Specifically, in the step (2), the addition amount of the water accounts for 0.05-0.2 wt% of the total mass of the initiator, the amine catalyst and the epoxide in the reaction system.
Specifically, in the step (2), the water is added for 0.5 to 1 hour after the curing reaction is carried out.
Specifically, the step (2) further comprises the step of continuously introducing the protective atmosphere to increase the pressure of the reaction system after adding water;
preferably, the protective atmosphere is introduced to control the pressure of the reaction system to reach 0.3-0.8MPa. More preferably, the protective atmosphere is introduced to control the pressure of the reaction system to be 0.5-0.6MPa.
Specifically, in the step (2), the temperature of the curing reaction step is 90-125 ℃, and the curing reaction time is 2-6h.
Specifically, in the step (1), the step of continuously adding the epoxide comprises: heating the reaction system to 60-70 ℃, adding part of epoxide for polymerization, gradually heating to 90-125 ℃, and continuously adding the rest epoxide for polymerization;
preferably, the mass ratio of the two times of adding the epoxide is 1:15-1:30.
specifically, in the step (1), the molar ratio of the initiator to the epoxide is 1:3.5-1:8.0 of the total weight of the mixture;
the initiator comprises polyhydric alcohol and grease;
preferably, the mass ratio of the polyhydric alcohol to the grease is 1:0.08-1:1.3;
the epoxide comprises propylene oxide and/or ethylene oxide;
specifically, the polyalcohol is a compound or a mixture containing two or more hydroxyl groups; preferably, the polyhydric alcohol comprises one or a mixture of more of sucrose, sorbitol, pentaerythritol, glycerol, propylene glycol, dipropylene glycol, diethylene glycol, triethylene glycol, monoethanolamine, monoethylene diisopropanolamine, diethanolamine, diethylisopropanolamine, triethanolamine and triisopropanolamine;
preferably, the grease comprises one or a mixture of several of vegetable oil and/or grease, animal oil and/or grease.
Specifically, in the step (1), the amine catalyst comprises a mixed solution of one or more of monomethylamine, dimethylamine, trimethylamine, and triethylamine;
preferably, the adding amount of the amine catalyst accounts for 0.8-1.5wt% of the total amount of the initiator, the amine catalyst and the epoxide in the reaction system;
preferably, the concentration of the solution of the amine catalyst is 30 to 60wt%.
Specifically, the protective atmosphere comprises nitrogen.
The invention also discloses a hard foam polyether polyol product prepared by the method.
In the preparation method of the hard foam polyether polyol, the applicant discovers that the catalyst can be effectively activated by adding water into a reaction system in the curing reaction process to improve the water content of the system on the basis of the traditional amine catalysis process, so that the catalytic reaction efficiency of the product is effectively improved, and the epoxide residue in the polyether product is reduced; and further, residual epoxide is further consumed in a mode of charging nitrogen into the reaction kettle for boosting, so that the reaction efficiency of the product is effectively improved. According to the preparation method of the hard foam polyether polyol, the polyether polyol product which is directly applied can be obtained by adding water and inflating and pressurizing in the curing process, and after the curing reaction is finished, the obtained product does not need post-treatment procedures such as vacuum removal of residual epoxide and the like, so that the preparation method has the advantages of simplicity in operation, high production efficiency, energy conservation and environmental protection, meets increasingly severe environmental protection requirements, and has good economic benefits.
Detailed Description
Example 1
A2L polymerization reaction kettle is selected, 260g of cane sugar, 132g of glycerol and 469g of palm oil are added at room temperature, and sufficient nitrogen is introduced to replace the kettle so as to completely remove oxygen in the kettle. Weighing 18g of dimethylamine aqueous solution with the mass fraction of 40wt%, and adding the dimethylamine aqueous solution into a reaction kettle, wherein the mass of the dimethylamine aqueous solution is 1.2% of the total mass of the materials.
Heating the materials in the reaction kettle to 70 ℃, slowly and continuously dropwise adding 30g of propylene oxide to perform continuous polymerization reaction, and gradually heating the temperature in the reaction kettle to 80-90 ℃ in the reaction process; then, the temperature is raised to 95 ℃ while feeding by utilizing the reaction heat, then the reaction temperature is controlled to be 95-105 ℃, and 591g of propylene oxide is continuously added dropwise.
After the propylene oxide is dripped, keeping the temperature in the kettle for curing reaction for 0.5h, adding 0.75g of water (accounting for 0.05wt% of the total mass of the materials) for mixing, continuously introducing nitrogen for pressurizing until the pressure in the kettle reaches 0.5MPa, continuously maintaining the reaction temperature (at 95-105 ℃) for curing for 3.5h to obtain the finished polyether polyol, directly sampling the finished product to test the propylene oxide residue, and testing the index shown in the following table 1.
Comparative example 1
The preparation method of the hard foam polyether polyol in the comparative example is the same as that in example 1, the difference is that the curing step is not carried out by adding water and introducing nitrogen for pressurizing, the curing step is directly carried out at 95-105 ℃ for 4h, then vacuumizing is carried out to remove residual propylene oxide to obtain finished polyether polyol, product samples before and after vacuumizing (namely, cured samples and vacuumized samples) are respectively taken to detect the residual amount of the propylene oxide, and detection indexes are shown in the following table 1.
Example 2
A2L polymerization reaction kettle is selected, 322g of cane sugar, 82g of glycerol and 350g of palm oil are put into the polymerization reaction kettle at room temperature, and sufficient nitrogen is introduced to replace the interior of the kettle so as to completely remove oxygen in the kettle. 22.5g of dimethylamine aqueous solution with the mass fraction of 30 percent is weighed and added into a reaction kettle, and the mass of the dimethylamine aqueous solution is 1.5 percent of the total mass of the materials.
Heating the materials in the reaction kettle to 70 ℃, slowly and continuously dropwise adding 30g of propylene oxide to perform continuous polymerization reaction, and gradually heating the temperature in the reaction kettle to 80-90 ℃ in the reaction process; then utilizing reaction heat, heating to 105 ℃ while feeding, then controlling the reaction temperature to 105-115 ℃, and continuously dropwise adding 693.5g of propylene oxide.
After the propylene oxide is added, keeping the temperature in the kettle for curing reaction for 0.5h, adding 1.5g of water (accounting for 0.1wt% of the total mass of the materials) for mixing, continuously introducing nitrogen for pressurizing until the pressure in the kettle reaches 0.6MPa, continuously maintaining the reaction temperature (105-115 ℃) for curing for 2.5h to obtain the finished polyether polyol, directly sampling the finished product to test the propylene oxide residue, and testing the detection index shown in the following table 1.
Comparative example 2
The preparation method of the hard bubble polyether polyol in the comparative example is the same as that in example 2, the difference is that the curing step is carried out without adding water and introducing nitrogen for pressurizing, the curing step is directly carried out at 105-115 ℃ for 3h, then vacuumizing is carried out to remove residual propylene oxide to obtain finished polyether polyol, product samples before and after vacuumizing (namely cured samples and vacuumized samples) are respectively taken to detect the residual amount of the propylene oxide, and detection indexes are shown in the following table 1.
Example 3
A2L polymerization reaction kettle is selected, 370g of cane sugar, 174g of diethylene glycol and 194g of palm oil are added at room temperature, and sufficient nitrogen is introduced to replace the kettle so as to completely remove oxygen in the kettle. Weighing 15g of dimethylamine aqueous solution with the mass fraction of 50%, and adding the dimethylamine aqueous solution into a reaction kettle, wherein the mass of the dimethylamine aqueous solution is 1% of the total mass of the materials.
Heating the materials in the reaction kettle to 70 ℃, slowly and continuously dropwise adding 30g of propylene oxide to perform continuous polymerization reaction, and gradually heating the temperature in the reaction kettle to 80-90 ℃ in the reaction process; then utilizing reaction heat, raising the temperature to 115 ℃ while feeding, then controlling the reaction temperature to be 115-125 ℃, and continuously dropwise adding 717g of propylene oxide.
After the propylene oxide is dripped, maintaining the temperature in the kettle for curing reaction for 1h, adding 3g of water (accounting for 0.2wt% of the total mass of the materials) for mixing, continuously introducing nitrogen for pressurizing until the pressure in the kettle reaches 0.8MPa, continuously maintaining the reaction temperature (115-125 ℃) for curing for 5h to obtain the finished product polyether polyol, directly sampling the finished product to test the propylene oxide residue, and testing the indexes of the finished product shown in the following table 1.
Comparative example 3
The preparation method of the hard bubble polyether polyol in the comparative example is the same as that in example 3, the difference is that the curing step is performed without adding water and introducing nitrogen for pressurizing, the curing step is performed directly at 115-125 ℃ for 6 hours, then the vacuum pumping is performed to remove the residual propylene oxide, so as to obtain the finished polyether polyol, the product samples before and after the vacuum pumping (i.e. the cured sample and the sample after the vacuum pumping) are respectively taken to detect the residual amount of the propylene oxide, and the detection indexes are shown in the following table 1.
Example 4
A2L polymerization reaction kettle is selected, 330g of cane sugar, 155g of diethylene glycol and 75g of palm oil are added at room temperature, and sufficient nitrogen is introduced to replace the kettle so as to completely remove oxygen in the kettle. Weighing 12g of a dimethylamine aqueous solution with the mass fraction of 60 percent, and adding the dimethylamine aqueous solution into a reaction kettle, wherein the mass of the dimethylamine aqueous solution is 0.8 percent of the total mass of the materials.
Heating the materials in the reaction kettle to 70 ℃, slowly and continuously dropwise adding 30g of propylene oxide to perform continuous polymerization reaction, and gradually heating the temperature in the reaction kettle to 80-90 ℃ in the reaction process; then utilizing reaction heat, heating to 100 ℃ while feeding, then controlling the reaction temperature to be 100-110 ℃, and continuously dropwise adding 898g of propylene oxide.
After the propylene oxide is dripped, keeping the temperature in the kettle for curing reaction for 1h, adding 2.25g of water (accounting for 0.15 percent of the total mass of the materials) for mixing, continuously introducing nitrogen for pressurizing until the pressure in the kettle reaches 0.3MPa, continuously maintaining the reaction temperature (100-110 ℃) for curing for 4h to obtain the finished product polyether polyol, directly sampling the finished product to test the propylene oxide residue, and testing the index shown in the following table 1.
Comparative example 4
The preparation method of the hard bubble polyether polyol in the comparative example is the same as that in example 4, the difference is only that the curing step is not carried out by adding water and introducing nitrogen for pressurizing, the curing step is directly carried out at 100-110 ℃ for 5h, and then the vacuum pumping is carried out to remove the residual propylene oxide, so as to obtain the finished product polyether polyol. The product samples before and after the vacuum treatment (i.e. cured samples and vacuumized samples) were respectively taken to detect the residual amount of propylene oxide, and the detection indexes are shown in table 1 below.
Example 5
The preparation method of the hard bubble polyether polyol is the same as that of the hard bubble polyether polyol in the embodiment 1, and only the corresponding water adding treatment is carried out in the curing process, and the corresponding operation of introducing nitrogen for pressurizing is not carried out.
Example 6
The preparation of the rigid foam polyether polyol described in this example is the same as in example 2, except that the final controlled reaction temperature is adjusted from 105-115 ℃ to 90-100 ℃.
Example 7
The preparation method of the rigid foam polyether polyol in this example is the same as that in example 6, except that after water is added, the reaction temperature (90-100 ℃) is kept for curing for 1.5 hours.
Example 8
The hard foam polyether polyol of this example was prepared in the same manner as in example 7 except that the amount of water added was adjusted from 0.1% to 0.05%.
Example 9
The preparation method of the hard bubble polyether polyol is the same as that of the hard bubble polyether polyol in the embodiment 8, and the difference is only that the pressure of the introduced nitrogen is adjusted to 0.3MPa from 0.6MPa in the curing process.
Examples of the experiments
1. Product indicator detection
The indicators of the polyether polyol products obtained in the above examples 1 to 9 and comparative examples 1 to 4 were measured, respectively, and the measurement indicators include PO residue/ppm, and the measurement results are reported in table 1 below.
TABLE 1 results of product detection indexes of examples 1 to 9 and comparative examples 1 to 4
Therefore, the preparation method of the hard foam polyether polyol can effectively activate the catalyst and effectively improve the catalytic reaction efficiency of the product by adding water into the reaction system in the curing reaction process to improve the water content of the system on the basis of the traditional amine catalytic process, thereby reducing the epoxide residue in the polyether product, and obtaining the directly applied polyether polyol product without performing post-treatment procedures such as vacuum removal of residual epoxide and the like on the obtained product.
It should be understood that the above examples are only for clarity of illustration and are not intended to limit the embodiments. Other variations and modifications will be apparent to persons skilled in the art in light of the above description. This need not be, nor should it be exhaustive of all embodiments. And obvious variations or modifications therefrom are within the scope of the invention.
Claims (10)
1. A preparation method of hard foam polyether polyol is characterized by comprising the following steps:
(1) Under the protective atmosphere, taking an initiator and an amine catalyst, and continuously adding epoxide for polymerization reaction;
(2) And after the epoxide is added, continuing to perform a curing reaction, adding water in the curing reaction process for mixing, and continuing to react until the curing is finished, thus obtaining the epoxide.
2. The method for preparing the hard foam polyether polyol according to claim 1, wherein in the step (2), the water is added in an amount of 0.05 to 0.2wt% based on the total mass of the initiator, the amine catalyst and the epoxide in the reaction system.
3. The method for preparing a rigid foam polyether polyol according to claim 1 or 2, wherein in the step (2), the water is added for 0.5 to 1 hour after the aging reaction.
4. The method for preparing a hard bubble polyether polyol according to any one of claims 1 to 3, wherein the step (2) further comprises the step of continuing to introduce the protective atmosphere to increase the pressure of the reaction system after adding water;
preferably, the protective atmosphere is introduced to control the pressure of the reaction system to reach 0.3-0.8MPa.
5. The process for preparing a rigid foam polyether polyol according to any one of claims 1 to 4, wherein the temperature of the aging reaction step is 90 to 125 ℃ and the aging reaction time is 2 to 6 hours.
6. A process for the preparation of a rigid foam polyether polyol according to any one of claims 1-5, wherein in step (1), the step of continuously adding an epoxide comprises: heating the reaction system to 60-70 ℃, adding part of epoxide for polymerization, gradually heating to 90-125 ℃, and continuously adding the rest epoxide for polymerization;
preferably, the mass ratio of the two times of adding the epoxide is 1:15-1:30.
7. process for the preparation of a rigid foam polyether polyol according to any one of claims 1 to 6, wherein in step (1) the molar ratio of the starter to the epoxide is from 1:3.5-1:8.0;
the initiator comprises polyhydric alcohol and grease;
preferably, the mass ratio of the polyhydric alcohol to the grease is 1:0.08-1:1.3;
the epoxide comprises propylene oxide and/or ethylene oxide;
preferably, the polyhydric alcohol comprises one or a mixture of more of sucrose, sorbitol, pentaerythritol, glycerol, propylene glycol, dipropylene glycol, diethylene glycol, triethylene glycol, monoethanolamine, monoethylene diisopropanolamine, diethanolamine, diethylisopropanolamine, triethanolamine and triisopropanolamine;
preferably, the grease comprises one or a mixture of several of vegetable oil and/or grease, animal oil and/or grease.
8. The method for preparing a hard foam polyether polyol according to any one of claims 1 to 7, wherein in the step (1), the amine catalyst comprises a mixed solution of one or more of monomethylamine, dimethylamine, trimethylamine or triethylamine;
preferably, the adding amount of the amine catalyst accounts for 0.8-1.5wt% of the total amount of the initiator, the amine catalyst and the epoxide in the reaction system;
preferably, the concentration of the solution of the amine catalyst is 30 to 60wt%.
9. Process for the preparation of a hard bubble polyether polyol according to any one of claims 1-8, wherein the protective atmosphere comprises nitrogen.
10. A rigid foam polyether polyol product obtainable by the process of any one of claims 1 to 9.
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