CN111286019A - Preparation method of high-bonding-force rigid polyether polyol for foaming - Google Patents
Preparation method of high-bonding-force rigid polyether polyol for foaming Download PDFInfo
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- CN111286019A CN111286019A CN202010111858.0A CN202010111858A CN111286019A CN 111286019 A CN111286019 A CN 111286019A CN 202010111858 A CN202010111858 A CN 202010111858A CN 111286019 A CN111286019 A CN 111286019A
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- polyether polyol
- polyol
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- foaming
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- 229920005862 polyol Polymers 0.000 title claims abstract description 79
- 150000003077 polyols Chemical class 0.000 title claims abstract description 79
- 239000004721 Polyphenylene oxide Substances 0.000 title claims abstract description 67
- 229920000570 polyether Polymers 0.000 title claims abstract description 67
- 238000005187 foaming Methods 0.000 title claims abstract description 34
- 238000002360 preparation method Methods 0.000 title claims abstract description 12
- 238000006243 chemical reaction Methods 0.000 claims abstract description 67
- GOOHAUXETOMSMM-UHFFFAOYSA-N Propylene oxide Chemical compound CC1CO1 GOOHAUXETOMSMM-UHFFFAOYSA-N 0.000 claims abstract description 58
- ROSDSFDQCJNGOL-UHFFFAOYSA-N Dimethylamine Chemical compound CNC ROSDSFDQCJNGOL-UHFFFAOYSA-N 0.000 claims abstract description 32
- 229920000728 polyester Polymers 0.000 claims abstract description 25
- 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 abstract description 20
- 229930006000 Sucrose Natural products 0.000 claims abstract description 20
- 239000003054 catalyst Substances 0.000 claims abstract description 19
- IAYPIBMASNFSPL-UHFFFAOYSA-N Ethylene oxide Chemical compound C1CO1 IAYPIBMASNFSPL-UHFFFAOYSA-N 0.000 claims abstract description 18
- 239000005720 sucrose Substances 0.000 claims abstract description 14
- 239000004519 grease Substances 0.000 claims abstract description 13
- 125000002887 hydroxy group Chemical group [H]O* 0.000 claims abstract description 11
- 229910052783 alkali metal Inorganic materials 0.000 claims abstract description 9
- 150000001340 alkali metals Chemical class 0.000 claims abstract description 6
- MTHSVFCYNBDYFN-UHFFFAOYSA-N diethylene glycol Chemical compound OCCOCCO MTHSVFCYNBDYFN-UHFFFAOYSA-N 0.000 claims description 33
- 238000006116 polymerization reaction Methods 0.000 claims description 30
- 238000000034 method Methods 0.000 claims description 29
- 229920005906 polyester polyol Polymers 0.000 claims description 27
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 26
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical group [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 claims description 24
- LGRFSURHDFAFJT-UHFFFAOYSA-N Phthalic anhydride Natural products C1=CC=C2C(=O)OC(=O)C2=C1 LGRFSURHDFAFJT-UHFFFAOYSA-N 0.000 claims description 19
- JHIWVOJDXOSYLW-UHFFFAOYSA-N butyl 2,2-difluorocyclopropane-1-carboxylate Chemical compound CCCCOC(=O)C1CC1(F)F JHIWVOJDXOSYLW-UHFFFAOYSA-N 0.000 claims description 19
- 239000007864 aqueous solution Substances 0.000 claims description 14
- 239000000463 material Substances 0.000 claims description 14
- 229910052757 nitrogen Inorganic materials 0.000 claims description 13
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 13
- 238000004519 manufacturing process Methods 0.000 claims description 12
- 235000019482 Palm oil Nutrition 0.000 claims description 11
- 125000003118 aryl group Chemical group 0.000 claims description 11
- 239000002540 palm oil Substances 0.000 claims description 11
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 claims description 9
- PEDCQBHIVMGVHV-UHFFFAOYSA-N Glycerine Chemical compound OCC(O)CO PEDCQBHIVMGVHV-UHFFFAOYSA-N 0.000 claims description 9
- DNIAPMSPPWPWGF-UHFFFAOYSA-N Propylene glycol Chemical compound CC(O)CO DNIAPMSPPWPWGF-UHFFFAOYSA-N 0.000 claims description 9
- 230000018044 dehydration Effects 0.000 claims description 8
- 238000006297 dehydration reaction Methods 0.000 claims description 8
- 239000002253 acid Substances 0.000 claims description 7
- 239000003463 adsorbent Substances 0.000 claims description 7
- 238000006386 neutralization reaction Methods 0.000 claims description 7
- 238000007872 degassing Methods 0.000 claims description 6
- 238000003825 pressing Methods 0.000 claims description 5
- SZXQTJUDPRGNJN-UHFFFAOYSA-N dipropylene glycol Chemical compound OCCCOCCCO SZXQTJUDPRGNJN-UHFFFAOYSA-N 0.000 claims description 3
- ZIBGPFATKBEMQZ-UHFFFAOYSA-N triethylene glycol Chemical compound OCCOCCOCCO ZIBGPFATKBEMQZ-UHFFFAOYSA-N 0.000 claims description 2
- 239000003921 oil Substances 0.000 claims 1
- 235000019198 oils Nutrition 0.000 claims 1
- 239000006260 foam Substances 0.000 abstract description 52
- RNFJDJUURJAICM-UHFFFAOYSA-N 2,2,4,4,6,6-hexaphenoxy-1,3,5-triaza-2$l^{5},4$l^{5},6$l^{5}-triphosphacyclohexa-1,3,5-triene Chemical compound N=1P(OC=2C=CC=CC=2)(OC=2C=CC=CC=2)=NP(OC=2C=CC=CC=2)(OC=2C=CC=CC=2)=NP=1(OC=1C=CC=CC=1)OC1=CC=CC=C1 RNFJDJUURJAICM-UHFFFAOYSA-N 0.000 abstract description 14
- 239000003063 flame retardant Substances 0.000 abstract description 14
- 229920002635 polyurethane Polymers 0.000 abstract description 8
- 239000004814 polyurethane Substances 0.000 abstract description 8
- 230000000694 effects Effects 0.000 abstract description 6
- 238000004321 preservation Methods 0.000 abstract description 4
- 229920005830 Polyurethane Foam Polymers 0.000 abstract description 3
- 230000015572 biosynthetic process Effects 0.000 abstract description 3
- 239000011496 polyurethane foam Substances 0.000 abstract description 3
- 238000003786 synthesis reaction Methods 0.000 abstract description 3
- 238000009826 distribution Methods 0.000 abstract description 2
- 229920003023 plastic Polymers 0.000 abstract description 2
- 239000004033 plastic Substances 0.000 abstract description 2
- 238000011112 process operation Methods 0.000 abstract 1
- 238000007670 refining Methods 0.000 abstract 1
- RGSFGYAAUTVSQA-UHFFFAOYSA-N Cyclopentane Chemical compound C1CCCC1 RGSFGYAAUTVSQA-UHFFFAOYSA-N 0.000 description 44
- DMEGYFMYUHOHGS-UHFFFAOYSA-N heptamethylene Natural products C1CCCCCC1 DMEGYFMYUHOHGS-UHFFFAOYSA-N 0.000 description 22
- 229960004793 sucrose Drugs 0.000 description 16
- 230000000052 comparative effect Effects 0.000 description 14
- 238000001816 cooling Methods 0.000 description 10
- 238000010438 heat treatment Methods 0.000 description 10
- 238000009489 vacuum treatment Methods 0.000 description 6
- 239000002131 composite material Substances 0.000 description 5
- 230000007547 defect Effects 0.000 description 5
- 238000010276 construction Methods 0.000 description 4
- 239000003999 initiator Substances 0.000 description 4
- 239000000203 mixture Substances 0.000 description 4
- 238000005507 spraying Methods 0.000 description 4
- -1 alkali metal salt Chemical class 0.000 description 3
- 230000006835 compression Effects 0.000 description 3
- 238000007906 compression Methods 0.000 description 3
- 238000001746 injection moulding Methods 0.000 description 3
- 230000004048 modification Effects 0.000 description 3
- 238000012986 modification Methods 0.000 description 3
- 238000012545 processing Methods 0.000 description 3
- 239000000853 adhesive Substances 0.000 description 2
- 230000001070 adhesive effect Effects 0.000 description 2
- 230000000903 blocking effect Effects 0.000 description 2
- 239000011521 glass Substances 0.000 description 2
- 238000009413 insulation Methods 0.000 description 2
- 150000002924 oxiranes Chemical class 0.000 description 2
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 2
- 239000002994 raw material Substances 0.000 description 2
- 238000000926 separation method Methods 0.000 description 2
- 239000000243 solution Substances 0.000 description 2
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 1
- SVYKKECYCPFKGB-UHFFFAOYSA-N N,N-dimethylcyclohexylamine Chemical compound CN(C)C1CCCCC1 SVYKKECYCPFKGB-UHFFFAOYSA-N 0.000 description 1
- 125000003636 chemical group Chemical group 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 238000007599 discharging Methods 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 238000010348 incorporation Methods 0.000 description 1
- 239000011810 insulating material Substances 0.000 description 1
- 239000005022 packaging material Substances 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- 238000005086 pumping Methods 0.000 description 1
- 230000000979 retarding effect Effects 0.000 description 1
- 238000007151 ring opening polymerisation reaction Methods 0.000 description 1
- 238000007789 sealing Methods 0.000 description 1
- 239000003381 stabilizer Substances 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 238000007039 two-step reaction 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
- C08G65/2603—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
- 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
-
- 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
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J9/00—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof
- C08J9/04—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof using blowing gases generated by a previously added blowing agent
- C08J9/12—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof using blowing gases generated by a previously added blowing agent by a physical blowing agent
- C08J9/14—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof using blowing gases generated by a previously added blowing agent by a physical blowing agent organic
- C08J9/141—Hydrocarbons
-
- 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
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J2203/00—Foams characterized by the expanding agent
- C08J2203/14—Saturated hydrocarbons, e.g. butane; Unspecified hydrocarbons
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J2205/00—Foams characterised by their properties
- C08J2205/10—Rigid foams
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J2375/00—Characterised by the use of polyureas or polyurethanes; Derivatives of such polymers
- C08J2375/04—Polyurethanes
- C08J2375/08—Polyurethanes from polyethers
Abstract
The invention belongs to the technical field of polyurethane synthesis, and particularly relates to a preparation method of high-adhesion rigid polyether polyol for foaming, which is completed in two steps, wherein in the first step, sucrose, low-molecular-weight polyol and dimethylamine are used as catalysts, and a section of propylene oxide is introduced for reaction; and secondly, adding polyester, grease and an alkali metal catalyst on the basis of the first step, introducing a section of propylene oxide, introducing a proper amount of ethylene oxide after the reaction is finished, and performing post-treatment and refining to obtain a finished product. The preparation method has simple process operation, the obtained rigid foam polyether product has moderate viscosity and hydroxyl value, the prepared polyurethane foam plastic product can obviously improve the bonding strength between the foam product and attachments, has narrower density distribution, higher strength, good toughness, good dimensional stability, stronger bonding strength and lower heat conductivity coefficient, has certain flame retardant effect, and is particularly suitable for the heat preservation in the fields of pipeline heat preservation, plates and cold chains.
Description
Technical Field
The invention belongs to the technical field of polyurethane synthesis, and particularly relates to a preparation method of high-bonding-force rigid polyether polyol for foaming.
Background
Rigid polyurethane foams (polyurethane rigid foams) are widely used as various heat insulating, vibration preventing, sound insulating, and packaging materials because of their excellent heat insulating properties and their ease of application. The polyols for preparing the polyurethane rigid foam are polyether polyol and polyester polyol. The polyether polyol is widely applied to polyurethane rigid foam processing due to the advantages of wide raw material source, relatively low price, low viscosity, good intersolubility with auxiliaries, excellent processing performance and the like. However, the foam products prepared by the common polyether polyol have poor flame retardant property. The polyester polyol, especially aromatic polyester polyol, has large benzene ring structure in its molecular structure, and the foamed product has high strength, high toughness, high fire retarding performance, high mechanical performance and other advantages. But it has a high viscosity and is not easy to process. In recent years, with the enhancement of environmental protection requirements of national departments, higher requirements are put on flame retardance, heat insulation, mechanical properties and the like of polyurethane rigid foams. At present, many hard foam manufacturers want to compound polyester polyol into polyether polyol so as to reduce the dosage of a flame retardant and reduce the cost, and simultaneously, foam products have the advantages of polyether polyol and polyester polyol foam products. However, the compatibility between polyester polyol and polyether polyol is very poor, and a stable combined material cannot be prepared, so that the practical application and the sale are influenced. In addition, in the industries of processing the polyurethane rigid foam products into plates, spraying, pipe-in-pipe, refrigerators and the like, the bonding strength between the foam products and attachments is not enough, the foam products are easy to fall off, and the heat insulation performance is seriously influenced.
Disclosure of Invention
The invention aims to provide a preparation method of high-bonding-force rigid polyether polyol for foaming, and the rigid foam polyether product obtained by the method has the advantages of polyether polyol and polyester polyol, has a hydroxyl value of 400-460 mgKOH, is moderate in viscosity, good in compatibility with cyclopentane and low in cost; the foamed product has high compression strength, good dimensional stability and strong adhesive force with attachments; has certain flame retardant effect; the foam has low heat conductivity coefficient and good toughness.
In order to achieve the purpose, the invention adopts the following technical scheme:
a preparation method of high-bonding-force rigid polyether polyol for foaming comprises the following steps:
(1) a first polymerization step: feeding and pretreating: adding sucrose and low molecular weight polyol into a reaction kettle, adding dimethylamine (40% aqueous solution) serving as a catalyst, and replacing with nitrogen for 3-5 times. Controlling the temperature in the reaction kettle to be 80-85 ℃, then starting to dropwise add the epoxypropane, and controlling the temperature in the reaction kettle to be 80-110 ℃ and the pressure to be 0.1-0.4 MPa in the process of dropwise adding the epoxypropane; dropwise adding the epoxypropane until the weight accounts for 40-50% of the total weight of the epoxypropane, stopping dropwise adding, controlling the temperature in the kettle to be 80-110 ℃ and the pressure to be 0.1-0.4 MPa in the dropwise adding process, and curing for 1.5-3.5 hours after dropwise adding;
(2) a second step of polymerization: on the basis of the first step, polyester, grease and alkali metal catalyst are added, and vacuum dehydration is carried out until the water content of the materials in the kettle is within 0.5 percent (wt); and dropwise adding the rest of epoxy propane accounting for 50-60% of the total addition of the epoxy propane, and dropwise adding a proper amount of ethylene oxide after the reaction is finished. Controlling the temperature in the kettle to be 80-110 ℃ and the pressure to be 0.1-0.4 MPa in the dripping process, and curing for 1.5-3.5 hours after the dripping is finished;
(3) and (3) post-treatment: and adding water and acid into the cured product for neutralization, adding an adsorbent, vacuumizing, dehydrating, degassing, and performing filter pressing to obtain the high-adhesion rigid polyether polyol for foaming.
Aiming at the defects of polyether polyol foam products in the current market application, namely the defects of poor flame retardant property and insufficient mechanical property, and the defects of separation of the foam products and attachments and reduction of heat preservation property caused by poor bonding strength of the foam products and the attachments, the mechanical property and the flame retardant property of the foam products are improved, the addition amount of a flame retardant is reduced, and the foaming cost is reduced; meanwhile, grease is added, so that the compatibility of the polyether polyol and a cyclopentane system is better, the combined material is stable, and the polyether polyol and cyclopentane composite material is suitable for production and sale; by introducing polyester into the molecular structure and blocking the ethylene oxide block, the bonding strength between the foam product and an attachment is increased, the heat-insulating efficiency is ensured, and the cost is reduced. Therefore, the invention has obvious economic and social benefits and wide application prospect.
Preferably, the low molecular weight polyol is one or more of glycerol, propylene glycol, diethylene glycol, ethylene glycol, dipropylene glycol or triethylene glycol.
Preferably, the low molecular weight polyol is diethylene glycol.
Preferably, the alkali metal salt catalyst is potassium hydroxide, and the mass percentage of the added catalyst in the whole reaction system is 2.0-4.0%.
Preferably, in the first step of the polymerization reaction, the mass ratio of the sucrose to the low molecular weight polyol is 250: 50-80.
Preferably, in the first step of the polymerization reaction, the amount of dimethylamine (40% aqueous solution) added is 0.8 to 1.0% by mass in the first-step reaction system.
Preferably, in the second polymerization step, the polyester is an aromatic polyester polyol. The grease is palm oil, and the mass percentage of the palm oil in the whole reaction system is 14-21%.
Preferably, in the second polymerization step, the aromatic polyester polyol is a phthalic anhydride polyester polyol.
Preferably, in the second step of the polymerization reaction, the hydroxyl value of the phthalic anhydride polyester polyol is 350-400 mgKOH/g, the viscosity is 3000-5000 mPa.s, and the addition amount of the phthalic anhydride polyester polyol is 80-120% of the sucrose amount.
Preferably, the mass percentage of the propylene oxide in the whole reaction system is 45-55%.
Preferably, the ethylene oxide accounts for 2-10% by mass of the whole reaction system.
The process can obtain a hard foam polyether polyol product with a hydroxyl value of 400-460 mgKOH/g and a viscosity (25 ℃) of 3000-4000 mPa.s, the prepared product has moderate viscosity of the prepared composite material, good compatibility with cyclopentane, good mold filling property when foaming a foam product, and easy construction; the prepared foam product has good mechanical property, certain flame retardant effect and high bonding strength with attachments, ensures the heat-insulating property and is suitable for the construction processes of plate, pipe-in-pipe, spraying, injection molding and the like.
Advantageous effects
Aiming at the defects of polyether polyol foam products in the current market application, namely the defects of poor flame retardant property, insufficient mechanical property, poor bonding strength of the foam products and attachments, separation of the foam products and the attachments, reduction of heat preservation performance and the like, the invention prepares a brand-new high-bonding-force rigid polyether polyol for foaming by optimizing an initiator formula and simultaneously capping with a proper amount of EO (ethylene oxide) blocks. By adding aromatic polyester and the benzene ring structure of the polyester into the initiator, the mechanical property and the flame retardant property of the foam product are improved, the addition amount of the flame retardant is reduced, and the foaming cost is reduced; meanwhile, grease is added, so that the compatibility of the polyether polyol and a cyclopentane system is better, the combined material is stable, and the polyether polyol and cyclopentane composite material is suitable for production and sale; by introducing polyester into the molecular structure and blocking the ethylene oxide block, the bonding strength between the foam product and an attachment is increased, the heat-insulating efficiency is ensured, and the cost is reduced. Therefore, the invention has obvious economic and social benefits and wide application prospect. The hydroxyl value of the prepared high-bonding-force rigid polyether polyol product for foaming is 400-460 m gKOH/g, and the viscosity (25 ℃) is 3000-4000 mPa.s.
The high-binding-force foaming hard-foam polyether polyol prepared by the method has moderate viscosity, is good in compatibility with cyclopentane, and is suitable for a cyclopentane foaming process. Because the polyether polyol is synthesized by adopting a two-step method in the synthesis process, the aromatic polyester is added in the second step of reaction, the rigidity and the flame retardant property of a molecular chain are improved, and meanwhile, the bonding property of a foam product and an attachment is also enhanced; the addition of polyester and grease increases the compatibility of polyether polyol and a cyclopentane system, and reduces the cost of raw materials; meanwhile, in the second step of reaction, propylene oxide is firstly block polymerized, and then end capping polymerization is carried out by using a small proportion of ethylene oxide, so that the bonding strength between the foam product and the attachment is increased, the cost is reduced (the price of ethylene oxide is lower than that of propylene oxide), the HLB value (hydrophilic-lipophilic balance value) of polyether polyol is adjusted, and the stability of the prepared composition is facilitated.
The preparation method has the advantages of simple operation of the process and high production efficiency; the high-binding-force foaming hard foam polyether product obtained by the preparation method has moderate hydroxyl value and viscosity and low cost; the foamed product has high compression strength, good dimensional stability, strong binding power with attachments, low foam heat conductivity coefficient and good toughness; the polyurethane foam plastic prepared by the method has narrower density distribution, higher strength, good dimensional stability and bonding strength and lower heat conductivity coefficient; has certain flame retardant effect, and is particularly suitable for construction processes of plates, pipe-in-pipe, spraying, injection molding and the like of a cyclopentane system.
Detailed Description
Hereinafter, the present invention will be described in detail. Before the description is made, it should be understood that the terms used in the present specification and the appended claims should not be construed as limited to general and dictionary meanings, but interpreted based on the meanings and concepts corresponding to technical aspects of the present invention on the basis of the principle that the inventor is allowed to define terms appropriately for the best explanation. Accordingly, the description proposed herein is just a preferable example for the purpose of illustrations only, not intended to limit the scope of the invention, so it should be understood that other equivalents and modifications could be made thereto without departing from the spirit and scope of the invention.
The following examples are given by way of illustration of embodiments of the invention and are not to be construed as limiting the invention, and it will be understood by those skilled in the art that modifications may be made without departing from the spirit and scope of the invention. Unless otherwise specified, reagents and equipment used in the following examples are commercially available products.
Comparative example 1
Adding 500g of cane sugar, 120g of diethylene glycol and 20.3g of dimethylamine (40% aqueous solution) into a 5L high-pressure kettle provided with a stirrer, a meter, a heating temperature control device, a cooling device (comprising an outer jacket and an inner coil) and a pressure sensor, filling high-purity nitrogen to 0.25-0.3 MPa, then emptying to normal pressure, replacing for 3 times, finally keeping slight positive pressure, slowly heating to 50 ℃, starting to continuously dropwise add epoxypropane, controlling the feeding speed of epoxypropane and the temperature control device to keep the reaction temperature in the kettle at 80-110 ℃, keeping the pressure within the range of 0.1-0.4 MPa until the epoxypropane is added to 1400g, and curing for 3 hours after the reaction after the feeding is finished. And (3) carrying out vacuum treatment on the cured material at 100-110 ℃ for 3 hours to obtain the hard foam polyether polyol.
The performance indexes of the synthesized hard foam polyether polyol are shown in a table 1.
Example 1
Adding 500g of cane sugar, 120g of diethylene glycol, 200g of palm oil and 21.3g of dimethylamine (40% aqueous solution) into a 5L autoclave provided with a stirrer, a meter, a heating temperature control device, a cooling device (comprising an outer jacket and an inner coil) and a pressure sensor, filling high-purity nitrogen to 0.25-0.3 MPa, then emptying to normal pressure, replacing for 3 times, finally keeping micro-positive pressure, slowly raising the temperature to 50 ℃, starting to continuously dropwise add propylene oxide, keeping the reaction temperature in the autoclave at 80-110 ℃ by controlling the feeding speed of the propylene oxide and the temperature control device, keeping the pressure at 0.1-0.4 MPa, dropwise adding 1400g of the propylene oxide, and carrying out curing reaction for 3 hours after feeding. And (3) carrying out vacuum treatment on the cured material at 100-110 ℃ for 3 hours to obtain the hard foam polyether polyol.
The performance indexes of the synthesized hard foam polyether polyol are shown in a table 1.
Comparative example 2
Adding 500g of cane sugar, 120g of diethylene glycol, 500g of phthalic anhydride polyester and 20.3g of dimethylamine (40% aqueous solution) into a 5L autoclave provided with a stirrer, a meter, a heating temperature control device, a cooling device (comprising an outer jacket and an inner coil) and a pressure sensor, filling high-purity nitrogen to 0.25-0.3 MPa, then emptying to normal pressure, replacing for 3 times, finally keeping micro-positive pressure, slowly raising the temperature to 50 ℃, starting to continuously dropwise add propylene oxide, keeping the reaction temperature in the autoclave at 80-110 ℃ by controlling the feeding speed of the propylene oxide and the temperature control device, keeping the pressure at 0.1-0.4 MPa, dropwise adding 1400g of the propylene oxide, and carrying out curing reaction for 3 hours after feeding. And (3) carrying out vacuum treatment on the cured material at 100-110 ℃ for 3 hours, cooling to 50-60 ℃, and discharging.
The performance indexes of the synthesized hard foam polyether polyol are shown in a table 1.
Example 2
The first step is as follows: adding 500g of cane sugar, 120g of diethylene glycol and 20.3g of dimethylamine (40% aqueous solution) into a 5L autoclave provided with a stirrer, a meter, a heating temperature control device, a cooling device (comprising an outer jacket and an inner coil) and a pressure sensor, filling high-purity nitrogen to 0.25-0.3 MPa, then emptying to normal pressure, replacing for 3 times, finally keeping slight positive pressure, slowly heating to 50 ℃, starting to continuously dropwise add propylene oxide, controlling the feeding speed of the propylene oxide and the temperature control device to keep the reaction temperature in the autoclave at 80-110 ℃, keeping the pressure within the range of 0.1-0.4 MPa, dropwise adding 550g of propylene oxide, and carrying out curing reaction for 3 hours after feeding. And (3) carrying out vacuum treatment on the cured material at 100-110 ℃ for 3 hours, and cooling to 50-60 ℃ for later use.
The second step is that: on the basis of the first-step reaction, 500g of potassium hydroxide 8.8g of phthalic anhydride polyester is added into a kettle, nitrogen is replaced for 3 times, the temperature is raised, a vacuum pump is started to perform vacuum dehydration at 100-105 ℃ for 3 hours, then the temperature is reduced to 80 ℃, propylene oxide is continuously dripped, the reaction temperature in the kettle is maintained at 80-110 ℃ by controlling the feeding speed of the propylene oxide and a temperature control device, the pressure is in the range of 0.1-0.4 MPa, 660g of propylene oxide is dripped, and the curing reaction is performed for 3 hours after the feeding is finished. And adding water and acid into the kettle for neutralization, adding an adsorbent, vacuumizing, dehydrating, degassing, and performing filter pressing to obtain the hard foam polyether polyol.
The performance indexes of the synthesized hard foam polyether polyol are shown in a table 1.
Comparative example 3
The first step is as follows: adding 500g of cane sugar, 120g of diethylene glycol and 20.3g of dimethylamine (40% aqueous solution) into a 5L autoclave provided with a stirrer, a meter, a heating temperature control device, a cooling device (comprising an outer jacket and an inner coil) and a pressure sensor, filling high-purity nitrogen to 0.25-0.3 MPa, then emptying to normal pressure, replacing for 3 times, finally keeping slight positive pressure, slowly heating to 50 ℃, starting to continuously dropwise add propylene oxide, controlling the feeding speed of the propylene oxide and the temperature control device to keep the reaction temperature in the autoclave at 80-110 ℃, keeping the pressure within the range of 0.1-0.4 MPa, dropwise adding 550g of propylene oxide, and carrying out curing reaction for 3 hours after feeding. And (3) carrying out vacuum treatment on the cured material at 100-110 ℃ for 3 hours, and cooling to 50-60 ℃ for later use.
The second step is that: on the basis of the first-step reaction, 500g of phthalic anhydride polyester, 200g of palm oil and 9.3g of potassium hydroxide are added into a kettle, nitrogen is replaced for 3 times, the temperature is increased, a vacuum pump is started to carry out vacuum dehydration at 100-105 ℃ for 3 hours, then the temperature is reduced to 80 ℃, propylene oxide is continuously dripped, the reaction temperature in the kettle is maintained at 80-110 ℃ by controlling the charging speed and the temperature control device of the propylene oxide, the pressure is in the range of 0.1-0.4 MPa, 860g of propylene oxide is dripped, the curing reaction is carried out for 3 hours after the feeding is finished, then water and acid are added into the kettle for neutralization, an adsorbent is added, and after the vacuum pumping, the dehydration and the degassing are carried out, and the hard bubble polyether.
The performance indexes of the synthesized hard foam polyether polyol are shown in a table 1.
Example 3
The first step is as follows: adding 500g of cane sugar, 120g of diethylene glycol and 20.3g of dimethylamine (40% aqueous solution) into a 5L autoclave provided with a stirrer, a meter, a heating temperature control device, a cooling device (comprising an outer jacket and an inner coil) and a pressure sensor, filling high-purity nitrogen to 0.25-0.3 MPa, then emptying to normal pressure, replacing for 3 times, finally keeping slight positive pressure, slowly heating to 50 ℃, starting to continuously dropwise add propylene oxide, controlling the feeding speed of the propylene oxide and the temperature control device to keep the reaction temperature in the autoclave at 80-110 ℃, keeping the pressure within the range of 0.1-0.4 MPa, dropwise adding 550g of propylene oxide, and carrying out curing reaction for 3 hours after feeding. And (3) carrying out vacuum treatment on the cured material at 100-110 ℃ for 3 hours, and cooling to 50-60 ℃ for later use.
The second step is that: on the basis of the first-step reaction, 500g of phthalic anhydride polyester, 200g of palm oil and 8.7g of potassium hydroxide are added into a kettle, nitrogen is replaced for 3 times, the temperature is increased, a vacuum pump is started to carry out vacuum dehydration at 100-105 ℃ for 3 hours, then the temperature is reduced to 80 ℃, propylene oxide is continuously dripped, the reaction temperature in the kettle is maintained at 80-110 ℃ by controlling the charging speed and the temperature control device of the propylene oxide, the pressure is within the range of 0.1-0.4 MPa, 660g of propylene oxide is dripped, after the feeding is finished, the curing reaction is carried out for 1 hour, then 200g of ethylene oxide is continuously dripped at 80-110 ℃ and the pressure is within the range of 0.1-0.4 MPa, after the feeding is finished, the curing reaction is carried out for 3 hours, then water and acid are added into the kettle for neutralization, an adsorbent is added, and after the vacuum.
The performance indexes of the synthesized hard foam polyether polyol are shown in a table 1.
TABLE 1 hard foam polyether polyol Performance index
As can be seen from Table 1, the reaction in comparative example 1 and comparative example 2 adopts a one-step method, and the product contains suspended particles; in comparative example 2 and example 2, the phthalic anhydride polyester is added, the product appearance is turbid in the comparative example 2 by adopting a one-step method, the product appearance is transparent in the example 2 by adopting a two-step method, the first step is catalyzed by dimethylamine, and the second step is catalyzed by potassium hydroxide; the two-step method ensures that the sucrose reaction is more thorough and has obvious advantages compared with the one-step method; in comparative example 3 and example 3, the viscosity of the product is reduced in example 3 due to the incorporation of a small amount of ethylene oxide. The rigid polyether polyol product for high-adhesion foaming, prepared by the embodiment of the invention, is moderate in hydroxyl value and viscosity and transparent in appearance.
Example 4
A preparation method of high-bonding-force rigid polyether polyol for foaming comprises the following steps:
(1) a first polymerization step: feeding and pretreating: adding sucrose and low molecular weight polyol into a reaction kettle, adding dimethylamine (40% aqueous solution) serving as a catalyst, and replacing with nitrogen for 3-5 times. Controlling the temperature in the reaction kettle to be 80-85 ℃, then starting to dropwise add the epoxypropane, and controlling the temperature in the reaction kettle to be 80-110 ℃ and the pressure to be 0.1-0.4 MPa in the process of dropwise adding the epoxypropane; dropwise adding the epoxypropane until the weight accounts for 40-50% of the total weight of the epoxypropane, stopping dropwise adding, controlling the temperature in the kettle to be 80-110 ℃ and the pressure to be 0.1-0.4 MPa in the dropwise adding process, and curing for 1.5-3.5 hours after dropwise adding;
(2) a second step of polymerization: on the basis of the first step, polyester, grease and alkali metal catalyst are added, and vacuum dehydration is carried out until the water content of the materials in the kettle is within 0.5 percent (wt); and dropwise adding the rest of epoxy propane accounting for 50-60% of the total addition of the epoxy propane, and dropwise adding a proper amount of ethylene oxide after the reaction is finished. Controlling the temperature in the kettle to be 80-110 ℃ and the pressure to be 0.1-0.4 MPa in the dripping process, and curing for 1.5-3.5 hours after the dripping is finished;
(3) and (3) post-treatment: and adding water and acid into the cured product for neutralization, adding an adsorbent, vacuumizing, dehydrating, degassing, and performing filter pressing to obtain the high-adhesion rigid polyether polyol for foaming.
The low molecular weight polyol is ethylene glycol and dipropylene glycol. The alkali metal salt catalyst is potassium hydroxide, and the mass percentage of the catalyst addition in the whole reaction system is 2.0%. In the first step of polymerization, the mass ratio of the sucrose to the low molecular weight polyol is 250: 50.
In the first polymerization step, dimethylamine (40% aqueous solution) was added in an amount of 0.8% by mass in the first reaction system. In the second step of the polymerization reaction, the polyester is an aromatic polyester polyol. The grease is palm oil, and the mass percentage of the palm oil in the whole reaction system is 14%. In the second step of the polymerization reaction, the aromatic polyester polyol is phthalic anhydride polyester polyol.
In the second step of the polymerization reaction, the hydroxyl value of the phthalic anhydride polyester polyol is 350mgKOH/g, the viscosity is 3000mPa.s, and the addition amount of the phthalic anhydride polyester polyol is 80 percent of the sucrose amount. The mass percentage of the propylene oxide in the whole reaction system is 45%. The mass percentage of the ethylene oxide in the whole reaction system is 2%.
Example 5
A preparation method of high-bonding-force rigid polyether polyol for foaming comprises the following steps:
(1) a first polymerization step: feeding and pretreating: adding sucrose and low molecular weight polyol into a reaction kettle, adding dimethylamine (40% aqueous solution) serving as a catalyst, and replacing with nitrogen for 3-5 times. Controlling the temperature in the reaction kettle to be 80-85 ℃, then starting to dropwise add the epoxypropane, and controlling the temperature in the reaction kettle to be 80-110 ℃ and the pressure to be 0.1-0.4 MPa in the process of dropwise adding the epoxypropane; dropwise adding the epoxypropane until the weight accounts for 40-50% of the total weight of the epoxypropane, stopping dropwise adding, controlling the temperature in the kettle to be 80-110 ℃ and the pressure to be 0.1-0.4 MPa in the dropwise adding process, and curing for 1.5-3.5 hours after dropwise adding;
(2) a second step of polymerization: on the basis of the first step, polyester, grease and alkali metal catalyst are added, and vacuum dehydration is carried out until the water content of the materials in the kettle is within 0.5 percent (wt); and dropwise adding the rest of epoxy propane accounting for 50-60% of the total addition of the epoxy propane, and dropwise adding a proper amount of ethylene oxide after the reaction is finished. Controlling the temperature in the kettle to be 80-110 ℃ and the pressure to be 0.1-0.4 MPa in the dripping process, and curing for 1.5-3.5 hours after the dripping is finished;
(3) and (3) post-treatment: and adding water and acid into the cured product for neutralization, adding an adsorbent, vacuumizing, dehydrating, degassing, and performing filter pressing to obtain the high-adhesion rigid polyether polyol for foaming.
The low molecular weight polyol is a mixture of glycerol, propylene glycol, and diethylene glycol. The alkali metal salt catalyst is potassium hydroxide, and the mass percentage of the catalyst addition in the whole reaction system is 4.0%.
In the first step of polymerization, the mass ratio of the sucrose to the low molecular weight polyol is 250: 80. In the first polymerization step, dimethylamine (40% aqueous solution) was added in an amount of 1.0% by mass in the first reaction system.
In the second step of the polymerization reaction, the polyester is an aromatic polyester polyol. The grease is palm oil, and the mass percentage of the palm oil in the whole reaction system is 21%. The aromatic polyester polyol is phthalic anhydride polyester polyol.
In the second step of the polymerization reaction, the hydroxyl value of the phthalic anhydride polyester polyol is 400mgKOH/g, the viscosity is 5000mPa.s, and the addition amount of the phthalic anhydride polyester polyol is 120 percent of the sucrose amount. The mass percentage of the propylene oxide in the whole reaction system is 55%. The mass percentage of the ethylene oxide in the whole reaction system is 10%.
Compatibility experiment of the synthesized hard foam polyether polyol and cyclopentane:
placing 100g of polyether polyol into a transparent glass bottle at room temperature, adding corresponding cyclopentane, covering the glass bottle with a bottle cap, sealing, shaking for 200 times to uniformly mix the materials in the bottle, standing for 24 hours at room temperature, and observing the appearance. The maximum amount of cyclopentane added to keep the mixture clear is the cyclopentane solubility.
TABLE II cyclopentane solubility of rigid foam polyether polyols
| Comparative example 1 | Example 1 | Comparative example 2 | Example 2 | Comparative example 3 | Example 3 | |
| Solubility in water | 9.6 | 13.3 | ---- | 23.6 | 30.4 | 32.6 |
As can be seen from Table II, the grease added to the reaction initiator in comparative example 1 and example 1 can increase the solubility of cyclopentane; in the embodiment 2, polyester is added, and active hydrogen on the polyester and epoxide are subjected to ring-opening polymerization, so that the solubility of cyclopentane is obviously improved; in comparative example 3 and example 3, the two-step reaction is carried out, grease and polyester are added in the second step reaction simultaneously, so that the solubility of cyclopentane is improved by one step, and the solubility of cyclopentane is improved by adding a small amount of ethylene oxide in example 3, so that the HLB value of the system is adjusted.
Properties of rigid foam polyurethane articles
100 parts by mass of the polyether polyol prepared in the examples and the comparative examples, 2.5 parts by mass of a DC-193 foam stabilizer from American gas company, 1.5 parts by mass of an N, N dimethylcyclohexylamine catalyst, 1.0 part by mass of water and 9 parts by mass of cyclopentane were mixed uniformly to prepare a composite material, and the composite material was further mixed with PM200 from Wanhua chemical group Limited in a mass ratio of 1:1.10 to prepare a foam having the properties shown in Table 3
TABLE 3 foam Properties
As can be seen from the data in Table 3, the foam product foamed from the rigid polyether polyol for high adhesion foaming prepared in example 3 of the present invention has improved mechanical properties and flame retardancy due to the addition of the phthalic anhydride polyester in the polyether polyol initiator.
As can be seen from the data in Table 3, the foamed article foamed from the rigid polyether polyol for high adhesion foaming prepared in example 3 of the present invention has improved adhesion strength due to the addition of the phthalic anhydride polyester in the polymerization reaction, and the adhesive strength of the foamed article is greatly improved due to the capping of the polyether polyol polymerization end with a small amount of epoxide.
As can be seen from the data in tables 1, 2 and 3, the high-adhesion rigid polyether polyol for foaming, prepared by the embodiment of the invention, has the advantages of uniform and transparent appearance, moderate hydroxyl value and viscosity, low cost and good compatibility with cyclopentane; the foam product prepared by using the polyether polyol has high compression strength, good dimensional stability, strong bonding force with attachments, low foam heat conductivity coefficient and good toughness; has certain flame retardant effect, and is particularly suitable for construction processes of plates, pipe-in-pipe, spraying, injection molding and the like of a cyclopentane system.
The above examples are only intended to illustrate the technical solution of the present invention, but not to limit it; although the present invention has been described in detail with reference to the foregoing embodiments, it will be apparent to those skilled in the art that various changes may be made and equivalents may be substituted for elements thereof; and such modifications or substitutions do not depart from the spirit and scope of the corresponding technical solutions.
Claims (10)
1. A preparation method of high-adhesion rigid polyether polyol for foaming is characterized by comprising the following steps:
a first polymerization step: feeding and pretreating: adding sucrose and low molecular weight polyol into a reaction kettle, adding dimethylamine (40% aqueous solution) as a catalyst, replacing 3-5 times with nitrogen, controlling the temperature in the reaction kettle to be 80-85 ℃, then starting to dropwise add epoxypropane, and controlling the temperature in the reaction kettle to be 80-110 ℃ and the pressure to be 0.1-0.4 MPa in the process of dropwise adding epoxypropane; dropwise adding the epoxypropane until the weight accounts for 40-50% of the total weight of the epoxypropane, stopping dropwise adding, controlling the temperature in the kettle to be 80-110 ℃ and the pressure to be 0.1-0.4 MPa in the dropwise adding process, and curing for 1.5-3.5 hours after dropwise adding;
a second step of polymerization: on the basis of the first step, polyester, grease and alkali metal catalyst are added, and vacuum dehydration is carried out until the water content of the materials in the kettle is within 0.5 percent (wt); dropwise adding the rest 50-60% of the total addition of the propylene oxide, dropwise adding ethylene oxide after the reaction is finished, controlling the temperature in the kettle to be 80-110 ℃ and the pressure to be 0.1-0.4 MPa in the dropwise adding process, and curing for 1.5-3.5 hours after the dropwise adding is finished;
and (3) post-treatment: and adding water and acid into the cured product for neutralization, adding an adsorbent, vacuumizing, dehydrating, degassing, and performing filter pressing to obtain the high-adhesion rigid polyether polyol for foaming.
2. The method for producing a high-adhesion rigid polyether polyol for foaming according to claim 1, wherein: the low molecular weight polyol is one or more of glycerol, propylene glycol, diethylene glycol, ethylene glycol, dipropylene glycol or triethylene glycol.
3. The method for producing a high-adhesion rigid polyether polyol for foaming according to claim 2, wherein: the low molecular weight polyol is diethylene glycol.
4. The method for producing a high-adhesion rigid polyether polyol for foaming according to claim 1, wherein: in the second step of reaction, the alkali metal catalyst is potassium hydroxide, and the mass percentage of the added catalyst in the whole reaction system is 2.0-4.0%.
5. The method for producing a high-adhesion rigid polyether polyol for foaming according to claim 1, wherein: in the first step of the polymerization reaction, the mass ratio of the sucrose to the low-molecular-weight polyol is 250: 50-80.
6. The method for producing a high-adhesion rigid polyether polyol for foaming according to claim 1, wherein: in the first step of the polymerization reaction, the mass percentage of the addition amount of dimethylamine (40% aqueous solution) in the reaction system in the first step is 0.8-1.0%.
7. The method for producing a high-adhesion rigid polyether polyol for foaming according to claim 1, wherein: in the second step of polymerization reaction, the polyester is aromatic polyester polyol; the oil is palm oil, and the mass percentage of the palm oil in the whole reaction system is 14-21%.
8. The method for producing a high-adhesion rigid polyether polyol for foaming according to claim 7, wherein: in the second step of the polymerization reaction, the aromatic polyester polyol is phthalic anhydride polyester polyol.
9. The method for producing a high-adhesion rigid polyether polyol for foaming according to claim 8, wherein: in the second step of the polymerization reaction, the hydroxyl value of the phthalic anhydride polyester polyol is 350-400 mgKOH/g, the viscosity is 3000-5000 mPa.s, and the addition amount of the phthalic anhydride polyester polyol is 80-120% of the sucrose amount.
10. The method for producing a high-adhesion rigid polyether polyol for foaming according to claim 1, wherein: the mass percentage of the propylene oxide in the whole reaction system is 45-55%; the mass percentage of the ethylene oxide in the whole reaction system is 2-10%.
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Application publication date: 20200616 |