CN113150230B - Thermal insulation polyurethane plastic and preparation method thereof - Google Patents
Thermal insulation polyurethane plastic and preparation method thereof Download PDFInfo
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- CN113150230B CN113150230B CN202110235296.5A CN202110235296A CN113150230B CN 113150230 B CN113150230 B CN 113150230B CN 202110235296 A CN202110235296 A CN 202110235296A CN 113150230 B CN113150230 B CN 113150230B
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- 229920003023 plastic Polymers 0.000 title claims abstract description 48
- 239000004033 plastic Substances 0.000 title claims abstract description 48
- 229920002635 polyurethane Polymers 0.000 title claims abstract description 46
- 239000004814 polyurethane Substances 0.000 title claims abstract description 46
- 238000002360 preparation method Methods 0.000 title claims abstract description 22
- 238000009413 insulation Methods 0.000 title claims abstract description 19
- 229920005862 polyol Polymers 0.000 claims abstract description 114
- 150000003077 polyols Chemical class 0.000 claims abstract description 111
- 235000019482 Palm oil Nutrition 0.000 claims abstract description 47
- 239000002540 palm oil Substances 0.000 claims abstract description 47
- 239000006260 foam Substances 0.000 claims abstract description 45
- 239000004970 Chain extender Substances 0.000 claims abstract description 29
- 239000003381 stabilizer Substances 0.000 claims abstract description 29
- 239000004721 Polyphenylene oxide Substances 0.000 claims abstract description 28
- 229920000570 polyether Polymers 0.000 claims abstract description 28
- 239000003963 antioxidant agent Substances 0.000 claims abstract description 26
- 239000003054 catalyst Substances 0.000 claims abstract description 24
- 230000003078 antioxidant effect Effects 0.000 claims abstract description 22
- 239000004088 foaming agent Substances 0.000 claims abstract description 19
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 18
- 239000002798 polar solvent Substances 0.000 claims abstract description 16
- 238000004321 preservation Methods 0.000 claims abstract description 15
- LIOBPVZSSVYQSS-UHFFFAOYSA-N 2-(3,4-diaminophenyl)acetic acid Chemical compound NC1=CC=C(CC(O)=O)C=C1N LIOBPVZSSVYQSS-UHFFFAOYSA-N 0.000 claims abstract description 14
- XEZNGIUYQVAUSS-UHFFFAOYSA-N 18-crown-6 Chemical compound C1COCCOCCOCCOCCOCCO1 XEZNGIUYQVAUSS-UHFFFAOYSA-N 0.000 claims abstract description 11
- 239000002994 raw material Substances 0.000 claims abstract description 5
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 claims description 60
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 40
- 238000003756 stirring Methods 0.000 claims description 36
- PEDCQBHIVMGVHV-UHFFFAOYSA-N Glycerine Chemical compound OCC(O)CO PEDCQBHIVMGVHV-UHFFFAOYSA-N 0.000 claims description 32
- 238000002156 mixing Methods 0.000 claims description 25
- 238000010438 heat treatment Methods 0.000 claims description 22
- 238000005187 foaming Methods 0.000 claims description 20
- 229910052757 nitrogen Inorganic materials 0.000 claims description 20
- 229920001730 Moisture cure polyurethane Polymers 0.000 claims description 16
- 230000032683 aging Effects 0.000 claims description 15
- 238000001816 cooling Methods 0.000 claims description 15
- 125000002887 hydroxy group Chemical group [H]O* 0.000 claims description 14
- 239000012948 isocyanate Substances 0.000 claims description 14
- 150000002513 isocyanates Chemical class 0.000 claims description 14
- GOOHAUXETOMSMM-UHFFFAOYSA-N Propylene oxide Chemical compound CC1CO1 GOOHAUXETOMSMM-UHFFFAOYSA-N 0.000 claims description 11
- ROSDSFDQCJNGOL-UHFFFAOYSA-N Dimethylamine Chemical compound CNC ROSDSFDQCJNGOL-UHFFFAOYSA-N 0.000 claims description 10
- IAYPIBMASNFSPL-UHFFFAOYSA-N Ethylene oxide Chemical compound C1CO1 IAYPIBMASNFSPL-UHFFFAOYSA-N 0.000 claims description 10
- 238000007789 sealing Methods 0.000 claims description 10
- 239000007787 solid Substances 0.000 claims description 10
- 239000000203 mixture Substances 0.000 claims description 9
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 claims description 9
- 235000021552 granulated sugar Nutrition 0.000 claims description 8
- 238000006243 chemical reaction Methods 0.000 claims description 7
- OFBQJSOFQDEBGM-UHFFFAOYSA-N Pentane Chemical compound CCCCC OFBQJSOFQDEBGM-UHFFFAOYSA-N 0.000 claims description 6
- QWTDNUCVQCZILF-UHFFFAOYSA-N isopentane Chemical compound CCC(C)C QWTDNUCVQCZILF-UHFFFAOYSA-N 0.000 claims description 6
- 238000000034 method Methods 0.000 claims description 6
- IMNIMPAHZVJRPE-UHFFFAOYSA-N triethylenediamine Chemical compound C1CN2CCN1CC2 IMNIMPAHZVJRPE-UHFFFAOYSA-N 0.000 claims description 6
- RGSFGYAAUTVSQA-UHFFFAOYSA-N Cyclopentane Chemical compound C1CCCC1 RGSFGYAAUTVSQA-UHFFFAOYSA-N 0.000 claims description 5
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 claims description 5
- 239000002253 acid Substances 0.000 claims description 5
- 238000005554 pickling Methods 0.000 claims description 5
- 238000002390 rotary evaporation Methods 0.000 claims description 5
- 238000005406 washing Methods 0.000 claims description 5
- OJMIONKXNSYLSR-UHFFFAOYSA-N phosphorous acid Chemical compound OP(O)O OJMIONKXNSYLSR-UHFFFAOYSA-N 0.000 claims description 4
- UKLDJPRMSDWDSL-UHFFFAOYSA-L [dibutyl(dodecanoyloxy)stannyl] dodecanoate Chemical compound CCCCCCCCCCCC(=O)O[Sn](CCCC)(CCCC)OC(=O)CCCCCCCCCCC UKLDJPRMSDWDSL-UHFFFAOYSA-L 0.000 claims description 3
- 239000012975 dibutyltin dilaurate Substances 0.000 claims description 3
- AFABGHUZZDYHJO-UHFFFAOYSA-N dimethyl butane Natural products CCCC(C)C AFABGHUZZDYHJO-UHFFFAOYSA-N 0.000 claims description 3
- DMEGYFMYUHOHGS-UHFFFAOYSA-N heptamethylene Natural products C1CCCCCC1 DMEGYFMYUHOHGS-UHFFFAOYSA-N 0.000 claims description 3
- KSBAEPSJVUENNK-UHFFFAOYSA-L tin(ii) 2-ethylhexanoate Chemical compound [Sn+2].CCCCC(CC)C([O-])=O.CCCCC(CC)C([O-])=O KSBAEPSJVUENNK-UHFFFAOYSA-L 0.000 claims description 3
- 230000006835 compression Effects 0.000 abstract description 2
- 238000007906 compression Methods 0.000 abstract description 2
- 230000000052 comparative effect Effects 0.000 description 13
- 235000011187 glycerol Nutrition 0.000 description 9
- 239000011810 insulating material Substances 0.000 description 9
- 210000004027 cell Anatomy 0.000 description 5
- 230000000694 effects Effects 0.000 description 5
- 229910001414 potassium ion Inorganic materials 0.000 description 5
- ZBCBWPMODOFKDW-UHFFFAOYSA-N diethanolamine Chemical compound OCCNCCO ZBCBWPMODOFKDW-UHFFFAOYSA-N 0.000 description 4
- 229920005906 polyester polyol Polymers 0.000 description 4
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 description 3
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 3
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 3
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 3
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 2
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 2
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 2
- 229920005830 Polyurethane Foam Polymers 0.000 description 2
- 238000010521 absorption reaction Methods 0.000 description 2
- 125000003277 amino group Chemical group 0.000 description 2
- 125000004122 cyclic group Chemical group 0.000 description 2
- 210000000497 foam cell Anatomy 0.000 description 2
- 230000006872 improvement Effects 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 239000003208 petroleum Substances 0.000 description 2
- 230000000379 polymerizing effect Effects 0.000 description 2
- 239000011496 polyurethane foam Substances 0.000 description 2
- 230000008569 process Effects 0.000 description 2
- 241001391944 Commicarpus scandens Species 0.000 description 1
- 229920000742 Cotton Polymers 0.000 description 1
- XDTMQSROBMDMFD-UHFFFAOYSA-N Cyclohexane Chemical compound C1CCCCC1 XDTMQSROBMDMFD-UHFFFAOYSA-N 0.000 description 1
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 description 1
- 239000004793 Polystyrene Substances 0.000 description 1
- NPYPAHLBTDXSSS-UHFFFAOYSA-N Potassium ion Chemical compound [K+] NPYPAHLBTDXSSS-UHFFFAOYSA-N 0.000 description 1
- 239000004113 Sepiolite Substances 0.000 description 1
- GSEJCLTVZPLZKY-UHFFFAOYSA-N Triethanolamine Chemical compound OCCN(CCO)CCO GSEJCLTVZPLZKY-UHFFFAOYSA-N 0.000 description 1
- 230000002776 aggregation Effects 0.000 description 1
- 238000004220 aggregation Methods 0.000 description 1
- 239000012752 auxiliary agent Substances 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 description 1
- 210000002421 cell wall Anatomy 0.000 description 1
- 238000010276 construction Methods 0.000 description 1
- 125000001511 cyclopentyl group Chemical group [H]C1([H])C([H])([H])C([H])([H])C([H])(*)C1([H])[H] 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000009826 distribution Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 239000011381 foam concrete Substances 0.000 description 1
- 239000011491 glass wool Substances 0.000 description 1
- 239000003999 initiator Substances 0.000 description 1
- IQPQWNKOIGAROB-UHFFFAOYSA-N isocyanate group Chemical group [N-]=C=O IQPQWNKOIGAROB-UHFFFAOYSA-N 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 239000011490 mineral wool Substances 0.000 description 1
- 239000003921 oil Substances 0.000 description 1
- 235000019198 oils Nutrition 0.000 description 1
- 239000010451 perlite Substances 0.000 description 1
- 235000019362 perlite Nutrition 0.000 description 1
- 239000002861 polymer material Substances 0.000 description 1
- 229920005903 polyol mixture Polymers 0.000 description 1
- 229920002223 polystyrene Polymers 0.000 description 1
- 239000011148 porous material Substances 0.000 description 1
- 230000036632 reaction speed Effects 0.000 description 1
- 230000009257 reactivity Effects 0.000 description 1
- 239000011435 rock Substances 0.000 description 1
- 235000019355 sepiolite Nutrition 0.000 description 1
- 229910052624 sepiolite Inorganic materials 0.000 description 1
- 238000007086 side reaction Methods 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 239000002344 surface layer Substances 0.000 description 1
- 239000008096 xylene Substances 0.000 description 1
Classifications
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
- C08G18/40—High-molecular-weight compounds
- C08G18/48—Polyethers
- C08G18/4829—Polyethers containing at least three hydroxy groups
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/08—Processes
- C08G18/0838—Manufacture of polymers in the presence of non-reactive compounds
-
- 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
- C08G18/30—Low-molecular-weight compounds
- C08G18/38—Low-molecular-weight compounds having heteroatoms other than oxygen
- C08G18/3819—Low-molecular-weight compounds having heteroatoms other than oxygen having nitrogen
- C08G18/3821—Carboxylic acids; Esters thereof with monohydroxyl compounds
-
- 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
- C08G18/4804—Two or more polyethers of different physical or chemical nature
-
- 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
- C08G18/4833—Polyethers containing oxyethylene units
- C08G18/4837—Polyethers containing oxyethylene units and other oxyalkylene units
-
- 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
- C08G18/65—Low-molecular-weight compounds having active hydrogen with high-molecular-weight compounds having active hydrogen
- C08G18/66—Compounds of groups C08G18/42, C08G18/48, or C08G18/52
- C08G18/6666—Compounds of group C08G18/48 or C08G18/52
-
- 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
- C08J9/06—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 chemical blowing agent
- C08J9/08—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 chemical blowing agent developing carbon dioxide
-
- 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
- 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
- C08J2203/00—Foams characterized by the expanding agent
- C08J2203/18—Binary blends of expanding agents
- C08J2203/184—Binary blends of expanding agents of chemical foaming agent and physical blowing agent, e.g. azodicarbonamide and fluorocarbon
Landscapes
- Chemical & Material Sciences (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Manufacturing & Machinery (AREA)
- General Chemical & Material Sciences (AREA)
- Polyurethanes Or Polyureas (AREA)
Abstract
The invention discloses a heat-preservation and heat-insulation polyurethane plastic and a preparation method thereof. The polyurethane plastic comprises the following raw materials, by weight, 60-75 parts of polyether polyol, 10-15 parts of a chain extender, 2-5 parts of a foam stabilizer, 1-3 parts of a catalyst, 15-20 parts of a foaming agent, 1-3 parts of water and 0.1-0.3 part of an antioxidant. Wherein the polyether polyol is a complex of palm oil polyol and high EO content polyol, and the mass ratio of the palm oil polyol to the high EO content polyol is 2-4:1. The chain extender mainly comprises 3, 4-diaminophenylacetic acid, 18-crown-6 and a polar solvent. The polyurethane plastic prepared by the invention has good heat preservation performance, heat insulation performance and compression strength; can be widely applied to the fields of refrigerators, solar energy, water heaters, buildings, pipelines, containers and the like.
Description
Technical Field
The invention relates to the technical field of high polymer materials, in particular to heat-preservation and heat-insulation polyurethane plastic and a preparation method thereof.
Background
At present, the heat-insulating materials circulated in domestic markets are mainly divided into organic foam heat-insulating materials and inorganic foam heat-insulating materials. The organic foam heat-insulating material mainly comprises phenolic foam, polyurethane plastic, polystyrene and the like; the inorganic foam heat-insulating material mainly comprises foam concrete, rock face, glass wool, sepiolite cotton, perlite and rock wool.
Most of inorganic foam heat-insulating materials are nonflammable materials, and the safety performance is high, but the inorganic foam heat-insulating materials have the defects of poor heat-insulating effect, high density, high water absorption, inconvenient construction and the like. The organic foam heat-insulating material has the advantages of light weight, low density, low water absorption, low heat conductivity and good heat-insulating effect, so that the organic foam heat-insulating material is widely applied; polyurethane plastics are of great interest to the market due to their excellent heat-insulating properties.
Polyurethane plastics, also called polyurethane foam plastics, are obtained by polymerizing hydroxyl compounds and isocyanate to form polyurethane prepolymers, and foaming the polyurethane prepolymers by a foaming agent. The polyurethane plastic has good heat preservation and insulation properties, and also has excellent processability, good chemical stability, and resistance to a plurality of solvents, oils, wear resistance and the like, so that the polyurethane plastic is widely applied to the fields of household appliances such as refrigerators, solar energy, water heaters and the like, buildings, pipelines, containers and the like.
In the prior published patents, polyester polyols are mostly used to prepare polyurethane plastics; the benzene ring content in the common polyester polyol is low, the improvement effect on the compressive strength of the foamed foam is not great, and the heat resistance cannot be expected; the viscosity of the common polyester polyol is relatively low, so that the demolding performance of the foam is poor, the foam is easy to break in the initial foaming stage, and the foam strength and the apparent mass of a foam product are reduced. Therefore, there is a need to find more optimal polyester polyol combinations or polyether polyol combinations for improving the overall properties of polyurethane foams.
Disclosure of Invention
The invention aims to provide a heat-preservation and heat-insulation polyurethane plastic and a preparation method thereof, which are used for solving the problems in the background technology.
In order to solve the technical problems, the invention provides the following technical scheme: the heat-insulating polyurethane plastic comprises, by weight, 60-75 parts of polyether polyol, 10-15 parts of a chain extender, 2-5 parts of a foam stabilizer, 1-3 parts of a catalyst, 15-20 parts of a foaming agent, 1-3 parts of water and 0.1-0.3 part of an antioxidant.
Further, the polyether polyol is a complex of palm oil polyol and a high EO content polyol; the mass ratio of the palm oil polyol to the polyol with high EO content is 2-4:1.
Further, the chain extender mainly comprises 3, 4-diaminophenylacetic acid, 18-crown-6 and a polar solvent. Wherein the polar solvent can be any one of ethanol, methanol, petroleum ether, hexane, cyclohexane, toluene, xylene, acetone and dichloromethane.
Further, the E0 content of the high EO content polyol is 73-75%; the high EO content polyol has a hydroxyl value of 40 to 44mg KOH/g.
Further, the palm oil polyol has a hydroxyl value of 380 to 440mg KOH/g and a viscosity of 5000 to 8000 mPas (25 ℃).
Further, the foam stabilizer is any one or more of a foam stabilizer AK8801, a foam stabilizer AK8805, a foam stabilizer B8870 and a foam stabilizer L6950;
the catalyst is any one of dibutyl tin dilaurate, stannous octoate and triethylenediamine;
the foaming agent is any one of cyclopentane, n-pentane, isopentane and hexane;
the antioxidant is one or two of hindered phenol antioxidants and phosphite antioxidants.
A preparation method of heat-preservation and heat-insulation polyurethane plastic comprises the following steps:
(1) Dissolving 18-crown-6 in a polar solvent, adding 3, 4-diaminophenylacetic acid, and uniformly stirring to obtain a chain extender;
(2) Mixing to obtain polyether polyol, adding isocyanate and a catalyst, heating to react, dripping a chain extender after the reaction is completed, and reacting to obtain a polyurethane prepolymer after the dripping is completed;
(3) Mixing the polyurethane prepolymer with a foam stabilizer, an antioxidant, water and a catalyst, uniformly stirring, adding a foaming agent, stirring, pouring into a foaming mold, foaming, and curing to obtain the polyurethane plastic.
Further, a preparation method of the heat-preservation and heat-insulation polyurethane plastic comprises the following steps of;
(1) Dissolving 18-crown-6 in a polar solvent, adding 3, 4-diaminophenylacetic acid, and uniformly stirring to obtain a chain extender;
(2) Mixing palm oil polyol and high EO content polyol in a mass ratio of 2-4:1, stirring uniformly to obtain polyether polyol, cooling to 20-25 ℃, adding isocyanate and a catalyst, heating to 80-90 ℃ under the protection of nitrogen seal, reacting for 1-2 h, and cooling to 60-70 ℃; dropwise adding the chain extender prepared in the step (1), and reacting for 2-3 hours under the nitrogen seal protection condition after the completion of dropwise adding, and removing the polar solvent by rotary evaporation to obtain a polyurethane prepolymer;
(3) Mixing the polyurethane prepolymer prepared in the step (2) with a foam stabilizer, an antioxidant, water and a catalyst, uniformly stirring, adding a foaming agent, stirring for 7-10 s at a stirring speed of 1000-1200 r/min, pouring into a foaming mold, foaming, and curing to obtain the polyurethane plastic.
Further, the preparation method of the palm oil polyol comprises the following steps:
mixing palm oil, glycerol and white granulated sugar, heating to 95-105 ℃, adding dimethylamine and solid potassium hydroxide under a nitrogen sealing piece, and stirring for 10-15 min; and (3) dropwise adding propylene oxide, reacting for 10-12 h, heating to 115-125 ℃, preserving heat and aging for 0.5-1 h, dehydrating in vacuum, pickling, and standing to obtain the palm oil polyol.
Further, the preparation method of the high EO content polyol comprises the following steps:
mixing glycerol and solid potassium hydroxide, heating to 115-125 ℃ under a nitrogen sealing piece, dropwise adding a mixture of propylene oxide and ethylene oxide EO, reacting for 10-12 h, preserving heat and aging for 0.5-1 h, and cooling to 110-115 ℃; dripping ethylene oxide EO, reacting for 4-6 h, vacuum dehydrating, heat-preserving aging for 0.5-1 h, vacuum dehydrating, acid washing and standing to obtain the polyol with high EO content.
Compared with the prior art, the invention has the beneficial effects that:
the invention provides a preparation method of polyurethane plastic, which selects polyether polyol obtained by mixing palm oil polyol and polyol with high EO content in a mass ratio of 2-4:1, wherein the palm oil polyol is formed by polymerizing palm oil, a small amount of white granulated sugar and glycerin serving as an initiator with propylene oxide; the white granulated sugar molecule contains hydroxyl groups, a large number of hydroxyl groups can be introduced into a polyol molecular chain, the prepared polyol has high functionality and high hydroxyl value, the hydroxyl value content is high, the full reaction of the polyol and isocyanate can be promoted, and the compatibility of other auxiliary agents in a reaction system can be improved by a large number of hydroxyl groups; and the production of uniformly distributed and fine foam cells is realized, and meanwhile, the white granulated sugar and the palm oil are renewable resources, so that the consumption of petroleum resources is reduced.
However, due to the higher viscosity of the palm oil polyol, closed cells are generated at the initial stage of foaming due to the stronger elasticity of cell walls, and the continuous closed cells can lead to shrinkage of the cells; to solve this problem, the present invention adds a high EO content polyol having a relatively low viscosity to properly neutralize the viscosity of the polyether polyol mixture and reduce cell shrinkage; the high EO content polyol has EO content as high as 73-75%, high primary hydroxyl content, high reaction activity, high reaction speed with isocyanate, short-time heat aggregation, sufficient foaming and approximate density of the surface layer and the core of the foam cells; thereby making up for the closed pore phenomenon of the palm oil polyether caused by high viscosity; in addition, the polyol with high EO content has low unsaturation degree, narrow molecular mass distribution, less side reaction, high density, good uniformity and good heat insulation effect.
Although the reactivity and the reaction degree of the polyol and isocyanate are improved from different aspects, a small amount of unreacted isocyanate still exists in the system, and at the moment, a chain extender is added, wherein the molecular structure of 3, 4-diaminophenylacetic acid in the chain extender contains two active amino groups, and the amino groups can react with isocyanate groups rapidly to remove a small amount of unreacted isocyanate; after the 3, 4-diaminophenylacetic acid reacts with isocyanate, a carboxyl group is exposed, so that the compatibility of the 3, 4-diaminophenylacetic acid with a reaction system is improved; in addition, the molecular structure of the 3, 4-diaminophenylacetic acid contains a rigid benzene ring structure, and compared with the linear structure of diethanolamine and triethanolamine, the strength and the heat resistance of polyurethane plastics are not reduced, but are improved.
Because the polyether polyol generally contains potassium ions, especially because of higher viscosity and higher post-treatment difficulty, the potassium ion content in the product is higher and is about 10 PPm; the existence of potassium ions can lead the polyether to gel in advance, and the phenomenon of caking and foam collapse is easy to occur in the foaming process; in order to solve the problem, in the end capping process, the component 18-crown-6 in the chain extender can coordinate with potassium ions to form a stable cyclic complex, so that on one hand, the potassium ions in the polyether polyol are removed, and on the other hand, the stable cyclic structure brings a rigid structure to the system, and the strength and the heat resistance of polyurethane plastics are enhanced.
The polyurethane plastic prepared by the invention has good heat preservation performance, heat insulation performance and compression strength; can be applied to the fields of refrigerators, solar energy, water heaters, buildings, pipelines, containers and the like.
Detailed Description
The following description of the embodiments of the present invention will be made clearly and completely, and it is apparent that the described embodiments are only some embodiments of the present invention, but not all embodiments. All other embodiments, which can be made by those skilled in the art based on the embodiments of the invention without making any inventive effort, are intended to be within the scope of the invention.
Example 1
The heat-insulating polyurethane plastic comprises the following raw materials in parts by weight, 60 parts of polyether polyol, 10 parts of a chain extender, 2 parts of a foam stabilizer, 1 part of a catalyst, 15 parts of a foaming agent, 1 part of water and 0.1 part of an antioxidant.
The polyether polyol is a complex of palm oil polyol and high EO content polyol; the mass ratio of palm oil polyol to high EO content polyol is 2:1.
The E0 content of the high EO polyol was 73%; the high EO content polyol hydroxyl number was 40mg KOH/g.
The palm oil polyol has a hydroxyl number of 380mg KOH/g and a viscosity of 5050 mPa.s (25 ℃).
The foam stabilizer is a foam stabilizer AK8801, the catalyst is dibutyl tin dilaurate, the foaming agent is cyclopentane, and the antioxidant is a hindered phenol antioxidant.
A preparation method of heat-insulating polyurethane plastic comprises the following steps;
(1) Dissolving 18-crown-6 in a polar solvent, adding 3, 4-diaminophenylacetic acid, and uniformly stirring to obtain a chain extender;
(2) Mixing palm oil polyol and high EO content polyol in a mass ratio of 2:1, stirring uniformly to obtain polyether polyol, cooling to 20 ℃, adding isocyanate and a catalyst, heating to 80 ℃ under the protection of nitrogen seal, reacting for 1h, and cooling to 60 ℃; dropwise adding the chain extender prepared in the step (1), and reacting for 2 hours under the nitrogen seal protection condition after the completion of dropwise adding, and removing the polar solvent by rotary evaporation to obtain a polyurethane prepolymer;
(3) And (3) mixing the polyurethane prepolymer prepared in the step (2) with a foam stabilizer, an antioxidant, water and a catalyst, uniformly stirring, adding a foaming agent, stirring for 7s, pouring the mixture into a foaming mold at the stirring speed of 1000r/min, foaming and curing to prepare the polyurethane plastic.
The preparation method of the palm oil polyol comprises the following steps:
mixing palm oil, glycerol and white granulated sugar, heating to 95deg.C, adding dimethylamine and solid potassium hydroxide under nitrogen sealing, and stirring for 10min; and (3) dropwise adding propylene oxide, reacting for 10 hours, heating to 115 ℃, preserving heat and ageing for 0.5 hour, dehydrating in vacuum, pickling, and standing to obtain the palm oil polyol.
The preparation method of the high EO content polyol comprises the following steps:
mixing glycerol and solid potassium hydroxide, heating to 115 ℃ under a nitrogen sealing condition, dropwise adding a mixture of propylene oxide and ethylene oxide EO, reacting for 10 hours, preserving heat and ageing for 0.5 hour, and cooling to 110 ℃; dripping ethylene oxide EO, reacting for 4 hours, vacuum dehydrating, heat-preserving aging for 0.5 hour, vacuum dehydrating, acid washing and standing to obtain the polyol with high EO content.
Example 2
The heat-insulating polyurethane plastic comprises the following raw materials in parts by weight, 68 parts of polyether polyol, 12 parts of a chain extender, 3 parts of a foam stabilizer, 2 parts of a catalyst, 16 parts of a foaming agent, 1.5 parts of water and 0.2 part of an antioxidant.
The polyether polyol is a complex of palm oil polyol and high EO content polyol; the mass ratio of palm oil polyol to high EO content polyol is 3:1.
The E0 content of the high EO content polyol was 74%; the high EO content polyol hydroxyl number was 42mg KOH/g.
Palm oil polyol has a hydroxyl number of 400mg KOH/g and a viscosity of 6700 mPas (25 ℃).
The foam stabilizer is a foam stabilizer AK8805, stannous octoate, the foaming agent is n-pentane, and the antioxidant is phosphite antioxidant.
A preparation method of heat-insulating polyurethane plastic comprises the following steps;
(1) Dissolving 18-crown-6 in a polar solvent, adding 3, 4-diaminophenylacetic acid, and uniformly stirring to obtain a chain extender;
(2) Mixing palm oil polyol and high EO content polyol in a mass ratio of 3:1, stirring uniformly to obtain polyether polyol, cooling to 22 ℃, adding isocyanate and a catalyst, heating to 85 ℃ under the protection of nitrogen seal, reacting for 1.5h, and cooling to 64 ℃; dropwise adding the chain extender prepared in the step (1), and reacting for 2.5 hours under the nitrogen seal protection condition after the completion of dropwise adding, and removing the polar solvent by rotary evaporation to obtain a polyurethane prepolymer;
(3) And (3) mixing the polyurethane prepolymer prepared in the step (2) with a foam stabilizer, an antioxidant, water and a catalyst, uniformly stirring, adding a foaming agent, stirring for 8s, pouring the mixture into a foaming mold at the stirring speed of 1100r/min, foaming and curing to prepare the polyurethane plastic.
The preparation method of the palm oil polyol comprises the following steps:
mixing palm oil, glycerol and white granulated sugar, heating to 100deg.C, adding dimethylamine and solid potassium hydroxide under nitrogen seal, and stirring for 12min; and (3) dropwise adding propylene oxide, reacting for 11 hours, heating to 118 ℃, preserving heat and ageing for 0.7 hour, dehydrating in vacuum, pickling, and standing to obtain the palm oil polyol.
The preparation method of the high EO content polyol comprises the following steps:
mixing glycerol and solid potassium hydroxide, heating to 118 ℃ under a nitrogen sealing condition, dropwise adding a mixture of propylene oxide and ethylene oxide EO, reacting for 11 hours, preserving heat and ageing for 0.6 hour, and cooling to 112 ℃; dripping ethylene oxide EO, reacting for 5h, vacuum dehydrating, heat-preserving aging for 0.7h, vacuum dehydrating, acid washing, and standing to obtain the polyol with high EO content.
Example 3
The heat-insulating polyurethane plastic comprises the following raw materials in parts by weight, 75 parts of polyether polyol, 15 parts of a chain extender, 5 parts of a foam stabilizer, 3 parts of a catalyst, 20 parts of a foaming agent, 3 parts of water and 0.3 part of an antioxidant.
The polyether polyol is a complex of palm oil polyol and high EO content polyol; the mass ratio of palm oil polyol to high EO content polyol was 4:1.
The E0 content of the high EO polyol is 75%; the high EO content polyol hydroxyl number was 44mg KOH/g.
The palm oil polyol has a hydroxyl number of 440mg KOH/g and a viscosity of 8000 mPas (25 ℃).
The foam stabilizer is a composition of a foam stabilizer B8870, a catalyst is triethylenediamine, a foaming agent is isopentane, and an antioxidant is a hindered phenol antioxidant and a phosphite antioxidant.
A preparation method of heat-insulating polyurethane plastic comprises the following steps;
(1) Dissolving 18-crown-6 in a polar solvent, adding 3, 4-diaminophenylacetic acid, and uniformly stirring to obtain a chain extender;
(2) Mixing palm oil polyol and high EO content polyol in a mass ratio of 4:1, stirring uniformly to obtain polyether polyol, cooling to 25 ℃, adding isocyanate and a catalyst, heating to 90 ℃ under the protection of nitrogen seal, reacting for 2h, and cooling to 70 ℃; dropwise adding the chain extender prepared in the step (1), and reacting for 3 hours under the nitrogen seal protection condition after the completion of dropwise adding, and removing the polar solvent by rotary evaporation to obtain a polyurethane prepolymer;
(3) And (3) mixing the polyurethane prepolymer prepared in the step (2) with a foam stabilizer, an antioxidant, water and a catalyst, uniformly stirring, adding a foaming agent, stirring for 10s, pouring the mixture into a foaming mold at the stirring speed of 1200r/min, foaming and curing to prepare the polyurethane plastic.
The preparation method of the palm oil polyol comprises the following steps:
mixing palm oil, glycerol and white granulated sugar, heating to 105deg.C, adding dimethylamine and solid potassium hydroxide under nitrogen sealing, and stirring for 15min; and (3) dropwise adding propylene oxide, reacting for 12 hours, heating to 125 ℃, preserving heat and aging for 1 hour, dehydrating in vacuum, pickling, and standing to obtain the palm oil polyol.
The preparation method of the high EO content polyol comprises the following steps:
mixing glycerol and solid potassium hydroxide, heating to 125 ℃ under a nitrogen sealing condition, dropwise adding a mixture of propylene oxide and ethylene oxide EO, reacting for 12 hours, preserving heat and ageing for 1 hour, and cooling to 115 ℃; dripping ethylene oxide EO, reacting for 6h, vacuum dehydrating, heat-preserving aging for 1h, vacuum dehydrating, acid washing, and standing to obtain the polyol with high EO content.
Comparative example 1
The mass ratio of palm oil polyol to high EO content polyol was 1:3, the remainder being the same as in example 2.
Comparative example 2
The polyether polyol was only palm oil polyol, the remainder being the same as in example 2.
Comparative example 3
The polyether polyol is only a high EO content polyol, the remainder being the same as in example 2.
Comparative example 4
The chain extender was diethanolamine and the remainder was the same as in example 2.
Experimental example
The polyurethane plastics prepared in examples 1 to 3 and comparative examples 1 to 3 were tested for heat conductivity and compressive strength, and the test results are shown in Table 1:
thermal conductivity coefficient 10 ℃, mW/m.K | Average compressive strength, KPa | Foam core density, g/cm3 | |
Example 1 | 18.1 | 213.5 | 34.0 |
Example 2 | 17.8 | 213.9 | 34.0 |
Example 3 | 18.2 | 213.6 | 34.1 |
Comparative example 1 | 18.2 | 211.7 | 34.0 |
Comparative example 2 | 18.5 | 205.6 | 34.6 |
Comparative example 3 | 18.7 | 202.3 | 33.8 |
Comparative example 4 | 18.4 | 201.5 | 34.1 |
TABLE 1
As is clear from the data in table 1, the polyurethane plastics prepared in examples 1 to 3 have the characteristics of low heat conductivity and high compressive strength; in comparative example 1, the mass ratio of palm oil polyol to high EO content polyol was 1:3, the low viscosity high EO content polyol content was higher than in example 2, and the thermal conductivity and compressive strength of the plastic were reduced due to partial cell breakage at the initial stage of foaming; the palm oil polyol alone and the polyol having a high EO content in comparative examples 2 and 3 produced polyurethane plastics having a lower thermal conductivity and a lower compressive strength than those of example 2, and diethanolamine was used in comparative example 4 instead of the chain extender in this embodiment, and the chain extender in example 2 contained a rigid benzene ring structure due to the linear structure of diethanolamine, thus resulting in the polyurethane plastics of comparative example 4 having a lower compressive strength than that of example 2.
Finally, it should be noted that: the foregoing description is only a preferred embodiment of the present invention, and the present invention is not limited thereto, but it is to be understood that modifications and equivalents of some of the technical features described in the foregoing embodiments may be made by those skilled in the art, although the present invention has been described in detail with reference to the foregoing embodiments. Any modification, equivalent replacement, improvement, etc. made within the spirit and principle of the present invention should be included in the protection scope of the present invention.
Claims (7)
1. A thermal insulation polyurethane plastic, which is characterized in that; the polyurethane plastic comprises the following raw materials, by weight, 60-75 parts of polyether polyol, 10-15 parts of a chain extender, 2-5 parts of a foam stabilizer, 1-3 parts of a catalyst, 15-20 parts of a foaming agent, 1-3 parts of water and 0.1-0.3 part of an antioxidant;
the heat-preservation and heat-insulation polyurethane plastic is characterized in that: the polyether polyol is a complex of palm oil polyol and high EO content polyol; the EO content of the high EO content polyol is 73-75%; the mass ratio of the palm oil polyol to the polyol with high EO content is 2-4:1;
the chain extender mainly comprises 3, 4-diaminophenylacetic acid, 18-crown-6 and a polar solvent;
the foam stabilizer is any one or more of a foam stabilizer AK8801, a foam stabilizer AK8805, a foam stabilizer B8870 and a foam stabilizer L6950;
the catalyst is any one of dibutyl tin dilaurate, stannous octoate and triethylenediamine;
the foaming agent is any one of cyclopentane, n-pentane, isopentane and hexane;
the antioxidant is one or two of hindered phenol antioxidants and phosphite antioxidants.
2. The heat preservation and insulation polyurethane plastic according to claim 1, wherein: the high EO content polyol has a hydroxyl value of 40 to 44mg KOH/g.
3. The heat preservation and insulation polyurethane plastic according to claim 1, wherein: the palm oil polyol has a hydroxyl value of 380-440 mg KOH/g and a viscosity of 5000-8000 mPa.s.
4. A preparation method of heat-preservation and heat-insulation polyurethane plastic is characterized by comprising the following steps: the method comprises the following steps:
(1) Dissolving 18-crown-6 in a polar solvent, adding 3, 4-diaminophenylacetic acid, and uniformly stirring to obtain a chain extender;
(2) Mixing to obtain polyether polyol, adding isocyanate and a catalyst, heating to react, dripping a chain extender after the reaction is completed, and reacting to obtain a polyurethane prepolymer after the dripping is completed;
(3) Mixing the polyurethane prepolymer with a foam stabilizer, an antioxidant, water and a catalyst, uniformly stirring, adding a foaming agent, stirring, pouring into a foaming mold, foaming, and curing to obtain the polyurethane plastic.
5. The method for preparing the heat-preservation and heat-insulation polyurethane plastic according to claim 4, which is characterized in that: comprises the following steps of;
(1) Dissolving 18-crown-6 in a polar solvent, adding 3, 4-diaminophenylacetic acid, and uniformly stirring to obtain a chain extender;
(2) Mixing palm oil polyol and high EO content polyol with EO content of 73-75% in a mass ratio of 2-4:1, stirring uniformly to obtain polyether polyol, cooling to 20-25 ℃, adding isocyanate and a catalyst, heating to 80-90 ℃ under nitrogen sealing protection, reacting for 1-2 h, and cooling to 60-70 ℃; dropwise adding the chain extender prepared in the step (1), and reacting for 2-3 hours under the nitrogen seal protection condition after the completion of dropwise adding, and removing the polar solvent by rotary evaporation to obtain a polyurethane prepolymer;
(3) Mixing the polyurethane prepolymer prepared in the step (2) with a foam stabilizer, an antioxidant, water and a catalyst, uniformly stirring, adding a foaming agent, stirring for 7-10 s at a stirring speed of 1000-1200 r/min, pouring into a foaming mold, foaming, and curing to obtain the polyurethane plastic.
6. The method for preparing the heat-preservation and heat-insulation polyurethane plastic according to claim 5, which is characterized in that: the preparation method of the palm oil polyol comprises the following steps:
mixing palm oil, glycerol and white granulated sugar, heating to 95-105 ℃, adding dimethylamine and solid potassium hydroxide under a nitrogen sealing piece, and stirring for 10-15 min; and (3) dropwise adding propylene oxide, reacting for 10-12 h, heating to 115-125 ℃, preserving heat and aging for 0.5-1 h, dehydrating in vacuum, pickling, and standing to obtain the palm oil polyol.
7. The method for preparing the heat-preservation and heat-insulation polyurethane plastic according to claim 5, which is characterized in that: the preparation method of the high EO content polyol comprises the following steps:
mixing glycerol and solid potassium hydroxide, heating to 115-125 ℃ under a nitrogen sealing piece, dropwise adding a mixture of propylene oxide and ethylene oxide EO, reacting for 10-12 h, preserving heat and aging for 0.5-1 h, and cooling to 110-115 ℃; dripping ethylene oxide EO, reacting for 4-6 h, vacuum dehydrating, heat-preserving aging for 0.5-1 h, vacuum dehydrating, acid washing and standing to obtain the polyol with high EO content.
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