CN116854900A - Tetraazapassion starting polyether polyol and preparation method thereof, and polyurethane rigid foam and preparation method thereof - Google Patents
Tetraazapassion starting polyether polyol and preparation method thereof, and polyurethane rigid foam and preparation method thereof Download PDFInfo
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- CN116854900A CN116854900A CN202210313090.4A CN202210313090A CN116854900A CN 116854900 A CN116854900 A CN 116854900A CN 202210313090 A CN202210313090 A CN 202210313090A CN 116854900 A CN116854900 A CN 116854900A
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- polyether polyol
- polyurethane
- foam
- polyether
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- 239000004721 Polyphenylene oxide Substances 0.000 title claims abstract description 114
- 229920000570 polyether Polymers 0.000 title claims abstract description 114
- 229920005862 polyol Polymers 0.000 title claims abstract description 94
- 150000003077 polyols Chemical class 0.000 title claims abstract description 94
- 239000006260 foam Substances 0.000 title claims abstract description 58
- 229920002635 polyurethane Polymers 0.000 title claims abstract description 39
- 239000004814 polyurethane Substances 0.000 title claims abstract description 39
- 238000002360 preparation method Methods 0.000 title abstract description 23
- 238000004917 polyol method Methods 0.000 title description 2
- 239000004088 foaming agent Substances 0.000 claims abstract description 29
- 239000003999 initiator Substances 0.000 claims abstract description 19
- 229920005830 Polyurethane Foam Polymers 0.000 claims abstract description 17
- 239000011496 polyurethane foam Substances 0.000 claims abstract description 17
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 claims description 58
- 239000003054 catalyst Substances 0.000 claims description 37
- RGSFGYAAUTVSQA-UHFFFAOYSA-N Cyclopentane Chemical compound C1CCCC1 RGSFGYAAUTVSQA-UHFFFAOYSA-N 0.000 claims description 34
- 239000001569 carbon dioxide Substances 0.000 claims description 29
- 229910002092 carbon dioxide Inorganic materials 0.000 claims description 29
- 238000002156 mixing Methods 0.000 claims description 22
- GOOHAUXETOMSMM-UHFFFAOYSA-N Propylene oxide Chemical compound CC1CO1 GOOHAUXETOMSMM-UHFFFAOYSA-N 0.000 claims description 21
- DMEGYFMYUHOHGS-UHFFFAOYSA-N heptamethylene Natural products C1CCCCCC1 DMEGYFMYUHOHGS-UHFFFAOYSA-N 0.000 claims description 18
- 125000002887 hydroxy group Chemical group [H]O* 0.000 claims description 18
- 239000012948 isocyanate Substances 0.000 claims description 18
- 150000002513 isocyanates Chemical class 0.000 claims description 18
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 18
- PEDCQBHIVMGVHV-UHFFFAOYSA-N Glycerine Chemical compound OCC(O)CO PEDCQBHIVMGVHV-UHFFFAOYSA-N 0.000 claims description 16
- 238000006243 chemical reaction Methods 0.000 claims description 13
- 239000004094 surface-active agent Substances 0.000 claims description 13
- 238000007259 addition reaction Methods 0.000 claims description 11
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 9
- IAYPIBMASNFSPL-UHFFFAOYSA-N Ethylene oxide Chemical compound C1CO1 IAYPIBMASNFSPL-UHFFFAOYSA-N 0.000 claims description 9
- 238000000034 method Methods 0.000 claims description 9
- 239000000203 mixture Substances 0.000 claims description 7
- CZMRCDWAGMRECN-UGDNZRGBSA-N Sucrose Chemical compound O[C@H]1[C@H](O)[C@@H](CO)O[C@@]1(CO)O[C@@H]1[C@H](O)[C@@H](O)[C@H](O)[C@@H](CO)O1 CZMRCDWAGMRECN-UGDNZRGBSA-N 0.000 claims description 6
- 229930006000 Sucrose Natural products 0.000 claims description 6
- 235000011187 glycerol Nutrition 0.000 claims description 6
- 239000005720 sucrose Substances 0.000 claims description 6
- 229910052757 nitrogen Inorganic materials 0.000 claims description 5
- 230000008569 process Effects 0.000 claims description 5
- 239000004604 Blowing Agent Substances 0.000 claims description 4
- 238000010438 heat treatment Methods 0.000 claims description 4
- VOZKAJLKRJDJLL-UHFFFAOYSA-N 2,4-diaminotoluene Chemical compound CC1=CC=C(N)C=C1N VOZKAJLKRJDJLL-UHFFFAOYSA-N 0.000 claims description 3
- 238000001035 drying Methods 0.000 claims description 3
- 238000001914 filtration Methods 0.000 claims description 3
- 238000004519 manufacturing process Methods 0.000 claims description 3
- 238000012644 addition polymerization Methods 0.000 claims description 2
- 238000006555 catalytic reaction Methods 0.000 claims description 2
- 125000001511 cyclopentyl group Chemical group [H]C1([H])C([H])([H])C([H])([H])C([H])(*)C1([H])[H] 0.000 claims description 2
- 239000002994 raw material Substances 0.000 abstract description 4
- 239000007858 starting material Substances 0.000 abstract description 4
- 229920001228 polyisocyanate Polymers 0.000 abstract description 2
- 239000005056 polyisocyanate Substances 0.000 abstract description 2
- 239000013256 coordination polymer Substances 0.000 abstract 1
- 239000000178 monomer Substances 0.000 abstract 1
- SCVFZCLFOSHCOH-UHFFFAOYSA-M potassium acetate Chemical compound [K+].CC([O-])=O SCVFZCLFOSHCOH-UHFFFAOYSA-M 0.000 description 22
- 238000005187 foaming Methods 0.000 description 15
- 235000011056 potassium acetate Nutrition 0.000 description 11
- UKODFQOELJFMII-UHFFFAOYSA-N pentamethyldiethylenetriamine Chemical compound CN(C)CCN(C)CCN(C)C UKODFQOELJFMII-UHFFFAOYSA-N 0.000 description 10
- 238000012360 testing method Methods 0.000 description 10
- SVYKKECYCPFKGB-UHFFFAOYSA-N N,N-dimethylcyclohexylamine Chemical group CN(C)C1CCCCC1 SVYKKECYCPFKGB-UHFFFAOYSA-N 0.000 description 9
- 210000004027 cell Anatomy 0.000 description 8
- 239000000463 material Substances 0.000 description 8
- 238000005829 trimerization reaction Methods 0.000 description 8
- 238000009835 boiling Methods 0.000 description 7
- 239000002131 composite material Substances 0.000 description 7
- 230000000052 comparative effect Effects 0.000 description 6
- IMNIMPAHZVJRPE-UHFFFAOYSA-N triethylenediamine Chemical compound C1CN2CCN1CC2 IMNIMPAHZVJRPE-UHFFFAOYSA-N 0.000 description 6
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical group [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 5
- 229910052710 silicon Inorganic materials 0.000 description 5
- 239000010703 silicon Substances 0.000 description 5
- 238000003756 stirring Methods 0.000 description 5
- 241000065675 Cyclops Species 0.000 description 4
- 238000011049 filling Methods 0.000 description 4
- 241000227653 Lycopersicon Species 0.000 description 3
- 235000007688 Lycopersicon esculentum Nutrition 0.000 description 3
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 description 3
- 210000000497 foam cell Anatomy 0.000 description 3
- 239000007789 gas Substances 0.000 description 3
- 239000011541 reaction mixture Substances 0.000 description 3
- RXYPXQSKLGGKOL-UHFFFAOYSA-N 1,4-dimethylpiperazine Chemical compound CN1CCN(C)CC1 RXYPXQSKLGGKOL-UHFFFAOYSA-N 0.000 description 2
- SNNYSJNYZJXIFE-UHFFFAOYSA-L 2-(benzenesulfinyl)ethylsulfinylbenzene;palladium(2+);diacetate Chemical compound [Pd+2].CC([O-])=O.CC([O-])=O.C=1C=CC=CC=1S(=O)CCS(=O)C1=CC=CC=C1 SNNYSJNYZJXIFE-UHFFFAOYSA-L 0.000 description 2
- YYROPELSRYBVMQ-UHFFFAOYSA-N 4-toluenesulfonyl chloride Chemical compound CC1=CC=C(S(Cl)(=O)=O)C=C1 YYROPELSRYBVMQ-UHFFFAOYSA-N 0.000 description 2
- KAKZBPTYRLMSJV-UHFFFAOYSA-N Butadiene Chemical group C=CC=C KAKZBPTYRLMSJV-UHFFFAOYSA-N 0.000 description 2
- LGRFSURHDFAFJT-UHFFFAOYSA-N Phthalic anhydride Natural products C1=CC=C2C(=O)OC(=O)C2=C1 LGRFSURHDFAFJT-UHFFFAOYSA-N 0.000 description 2
- 125000003118 aryl group Chemical group 0.000 description 2
- JHIWVOJDXOSYLW-UHFFFAOYSA-N butyl 2,2-difluorocyclopropane-1-carboxylate Chemical compound CCCCOC(=O)C1CC1(F)F JHIWVOJDXOSYLW-UHFFFAOYSA-N 0.000 description 2
- 230000008859 change Effects 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 239000006261 foam material Substances 0.000 description 2
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 2
- 229920005906 polyester polyol Polymers 0.000 description 2
- 238000004321 preservation Methods 0.000 description 2
- 239000011998 white catalyst Substances 0.000 description 2
- OYWRDHBGMCXGFY-UHFFFAOYSA-N 1,2,3-triazinane Chemical compound C1CNNNC1 OYWRDHBGMCXGFY-UHFFFAOYSA-N 0.000 description 1
- BXXWFOGWXLJPPA-UHFFFAOYSA-N 2,3-dibromobutane Chemical compound CC(Br)C(C)Br BXXWFOGWXLJPPA-UHFFFAOYSA-N 0.000 description 1
- GTEXIOINCJRBIO-UHFFFAOYSA-N 2-[2-(dimethylamino)ethoxy]-n,n-dimethylethanamine Chemical compound CN(C)CCOCCN(C)C GTEXIOINCJRBIO-UHFFFAOYSA-N 0.000 description 1
- WAPWXMDDHHWKNM-UHFFFAOYSA-N 3-[2,3-bis[3-(dimethylamino)propyl]triazinan-1-yl]-n,n-dimethylpropan-1-amine Chemical compound CN(C)CCCN1CCCN(CCCN(C)C)N1CCCN(C)C WAPWXMDDHHWKNM-UHFFFAOYSA-N 0.000 description 1
- SECXISVLQFMRJM-UHFFFAOYSA-N N-Methylpyrrolidone Chemical compound CN1CCCC1=O SECXISVLQFMRJM-UHFFFAOYSA-N 0.000 description 1
- UEEJHVSXFDXPFK-UHFFFAOYSA-N N-dimethylaminoethanol Chemical compound CN(C)CCO UEEJHVSXFDXPFK-UHFFFAOYSA-N 0.000 description 1
- CBENFWSGALASAD-UHFFFAOYSA-N Ozone Chemical compound [O-][O+]=O CBENFWSGALASAD-UHFFFAOYSA-N 0.000 description 1
- 230000009471 action Effects 0.000 description 1
- 125000003277 amino group Chemical group 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
- 239000012752 auxiliary agent Substances 0.000 description 1
- 239000002585 base Substances 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 210000003850 cellular structure Anatomy 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 230000006835 compression Effects 0.000 description 1
- 238000007906 compression Methods 0.000 description 1
- 150000001923 cyclic compounds Chemical class 0.000 description 1
- 229960002887 deanol Drugs 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000013461 design Methods 0.000 description 1
- XXBDWLFCJWSEKW-UHFFFAOYSA-N dimethylbenzylamine Chemical compound CN(C)CC1=CC=CC=C1 XXBDWLFCJWSEKW-UHFFFAOYSA-N 0.000 description 1
- 239000012972 dimethylethanolamine Substances 0.000 description 1
- ZZTCPWRAHWXWCH-UHFFFAOYSA-N diphenylmethanediamine Chemical compound C=1C=CC=CC=1C(N)(N)C1=CC=CC=C1 ZZTCPWRAHWXWCH-UHFFFAOYSA-N 0.000 description 1
- 230000002708 enhancing effect Effects 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 239000002360 explosive Substances 0.000 description 1
- 230000002209 hydrophobic effect Effects 0.000 description 1
- 238000009413 insulation Methods 0.000 description 1
- 230000007774 longterm Effects 0.000 description 1
- 230000021121 meiosis Effects 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 231100000252 nontoxic Toxicity 0.000 description 1
- 230000003000 nontoxic effect Effects 0.000 description 1
- 238000000655 nuclear magnetic resonance spectrum Methods 0.000 description 1
- 238000011056 performance test Methods 0.000 description 1
- -1 polymethylene Polymers 0.000 description 1
- 229920006389 polyphenyl polymer Polymers 0.000 description 1
- 239000011148 porous material Substances 0.000 description 1
- 230000008092 positive effect Effects 0.000 description 1
- SXWZSWLBMCNOPC-UHFFFAOYSA-M potassium;6-methylheptanoate Chemical compound [K+].CC(C)CCCCC([O-])=O SXWZSWLBMCNOPC-UHFFFAOYSA-M 0.000 description 1
- 150000003384 small molecules Chemical class 0.000 description 1
- 239000000243 solution Substances 0.000 description 1
- 238000001179 sorption measurement Methods 0.000 description 1
- 238000013112 stability test Methods 0.000 description 1
- 230000000087 stabilizing effect Effects 0.000 description 1
- 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 description 1
- XSQUKJJJFZCRTK-UHFFFAOYSA-N urea group Chemical group NC(=O)N XSQUKJJJFZCRTK-UHFFFAOYSA-N 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
- C08G65/2618—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 nitrogen
- C08G65/2621—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 nitrogen containing amine groups
- C08G65/263—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 nitrogen containing amine groups containing heterocyclic amine groups
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
- C08G18/40—High-molecular-weight compounds
- C08G18/48—Polyethers
- C08G18/4804—Two or more polyethers of different physical or chemical nature
- C08G18/482—Mixtures of polyethers containing at least one polyether containing nitrogen
-
- 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
- C08G18/50—Polyethers having heteroatoms other than oxygen
- C08G18/5021—Polyethers having heteroatoms other than oxygen having nitrogen
- C08G18/5054—Polyethers having heteroatoms other than oxygen having nitrogen containing heterocyclic rings having at least one nitrogen atom in the ring
-
- 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
- C08J9/122—Hydrogen, oxygen, CO2, nitrogen or noble gases
-
- 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
- C08J2203/06—CO2, N2 or noble gases
-
- 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
- C08J2203/182—Binary blends of expanding agents of physical blowing agents, e.g. acetone and butane
-
- 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
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)
- Polyurethanes Or Polyureas (AREA)
Abstract
The invention relates to a tetraazacyclo-starter polyether polyol and a preparation method thereof, and a polyurethane rigid foam and a preparation method thereof. In the present invention, a tetraazacyclotetramethylene polyether having rigidity and a hollow structure is introduced. The polyurethane hard foam comprises the following raw materials in percentage by mass: 5-30:110-160, a foaming agent and polyisocyanate, wherein the combined polyether comprises tetraazacyclo polyether and a foaming agent packageContains CP and CO 2 . The novel polyether monomer polyether using the tetraazacyclo initiator has good compatibility with the foaming agent, and the prepared polyurethane foam has the characteristics of low heat conduction, high strength, deformation resistance and low heat conduction attenuation.
Description
Technical Field
The invention belongs to the field of polyurethane foaming materials, and particularly relates to polyether polyol and a preparation method thereof, and a polyurethane rigid foam material.
Background
The rigid polyurethane foam is prepared by addition polymerization of isocyanate and polyol under the action of a catalyst and an auxiliary agent, has the advantages of high closed cell rate, low density, low heat conductivity, excellent processability and the like, and is widely applied to the field of heat preservation and heat insulation. In general, polyurethane foam is used as a main filling material for many home appliances such as refrigerator/freezer and water heater, and it is required to secure a certain strength to achieve a skeleton function, and at the same time, to secure a refrigerator not to shrink locally during a long-term use.
In recent years, due to the change of environmental protection policy and market demand, the performance requirements of the polyurethane rigid foam by the client manufacturers are also higher and higher. The pursuit of low thermal conductivity while ensuring the physical strength of the foam is one of the important directions pursuit of polyurethane foam.
CN201610966798.4 discloses a polyurethane foam with low density and low thermal conductivity and a preparation method thereof, wherein phthalic anhydride polyester polyol is adopted, and cyclopentane and 134A are used as physical foaming agents to prepare the polyurethane foam with low density, good dimensional stability and low thermal conductivity.
CN201610528413.6 discloses an environment-friendly foaming agent composition, polyurethane foam, a preparation method and application thereof, phthalic anhydride polyester polyol is adopted, and an environment-friendly low-boiling point foaming agent (one of 134a,152a and r600 a) is used for preparing the polyurethane foam with low density and good heat preservation effect.
In order to pursue low density performance, the prior art adopts a low-boiling point foaming agent, and foaming agent cannot be wrapped by foam materials in preparation, so that the foam closed-pore rate is reduced, foam surface bubbles are poor, and phenomena such as suction pits are caused in the use process.
Disclosure of Invention
The invention aims to provide a tetraazacyclo-starter polyether polyol and a preparation method thereof, wherein the structure of the polyether polyol can form a complex multi-benzene ring molecular structure in polyurethane molecules, so that the strength of the cell structure is greatly enhanced, the escape of a low-boiling point foaming agent is reduced in the early stage of reaction, and the exchange of the foaming agent and air in the later stage of reaction is reduced. The polyether polyol and the carbon dioxide have good compatibility, and carbon dioxide molecules can be adsorbed and enveloped in the cavity of the polyether polyol to prevent the carbon dioxide molecules from volatilizing.
The invention also provides a polyurethane rigid foam and a preparation method thereof, wherein the polyurethane rigid foam is prepared by using tetraazacyclo-starter polyether polyol and carbon dioxide as one of the physical foaming agents, and the foam has higher strength and lower heat conduction.
In order to solve the technical problems, the specific technical scheme of the invention is as follows:
a tetraazapassion starting polyether polyol having the structural formula:
wherein: a, b, c and d are each independently an integer not less than 1, preferably each independently an integer of 1 to 3; e, f, g and h are each independently an integer not less than 1, preferably each independently an integer of 1 to 5.
The hydroxyl number of the tetraazapassion starting polyether polyols according to the invention is from 200 to 280mg KOH/g (test standard GB/T12008.3-1989), and the functionality is from 3 to 4, preferably from 3 to 3.8.
A process for preparing said tetraazapassion starting polyether polyol comprising the steps of: the four nitrogen heterocycle tomato is used as an initiator, and ethylene oxide and/or propylene oxide are added and polymerized.
The tetraazacyclo-tomato is 1,6,20,25-tetraaza [6.1.6.1] pair-tomato.
Preferably, the preparation method of the tetraazapassion starting polyether polyol comprises the following steps: dissolving an initiator in water, replacing with nitrogen, heating to 80-140 ℃, adding ethylene oxide at the pressure of less than or equal to 0.6MPa, performing self-catalytic reaction for 1-4h, continuously adding propylene oxide, and stopping the reaction when the pressure is kept unchanged to obtain crude polyether; and drying and filtering the crude polyether to obtain the product.
In the preparation method of the tetraazacyclo-starting polyether polyol, the initiator 1,6,20,25-tetraaza [6.1.6.1] is 250-550 parts by mass of the cycloparaffin, the ethylene oxide is 250-600 parts by mass, and the propylene oxide is 400-1500 parts by mass.
The reaction equation is as follows:
a polyurethane rigid foam comprising the following composition: in terms of the parts by weight,
90-100 parts, preferably 90-95 parts, of a combined polyether polyol;
1.0 to 4.0 parts, preferably 2.0 to 3.5 parts, of surfactant;
1.5 to 5.0 parts, preferably 2.0 to 3.0 parts, of polyurethane catalyst;
1.0 to 3.0 parts, preferably 1.0 to 2.0 parts, of water;
5-30 parts, preferably 10-20 parts, of a physical foaming agent;
110 to 160 parts, preferably 130 to 155 parts, of isocyanate.
The combined polyether polyol disclosed by the invention comprises the following components:
(a) Polyether polyol a, the tetraazapassion starting polyether polyol according to the invention 5 to 30 parts, preferably 5 to 25 parts;
(b) 20-50 parts, preferably 30-45 parts, of polyether polyol B prepared by an addition reaction of sucrose serving as an initiator and propylene oxide;
(c) Polyether polyol C is prepared by an addition reaction of toluene diamine serving as an initiator and propylene oxide, wherein 10-40 parts, preferably 14-40 parts, of polyether polyol C are obtained;
(d) 10-30 parts, preferably 10-20 parts, of polyether polyol D is prepared by an addition reaction of sucrose and glycerol serving as an initiator and propylene oxide;
(e) Polyether polyol E is prepared by the addition reaction of glycerin serving as an initiator and propylene oxide, and 5-15 parts, preferably 7.5-14.0 parts, of polyether polyol E are prepared.
The hydroxyl value of the polyether polyol A is 200-280 mgKOH/g, and the functionality is 3.0-4.
The hydroxyl value of the polyether polyol B is 350-430mgKOH/g, and the functionality is 5.7-6.4.
The hydroxyl value of the polyether polyol C is 390-500mgKOH/g, and the functionality is 3.0-3.8.
The hydroxyl value of the polyether polyol D is 420-490mgKOH/g, and the functionality is 5.7-6.5.
The hydroxyl value of the polyether polyol E is 180-260mgKOH/g, and the functionality is 2.0-2.7.
The surfactant is a silicon surfactant. Suitable examples include, but are not limited to, at least one of AK8805, AK8830, B8525, B8545, etc. from Jiangsu Mei chemical Co., ltd. The surfactants have strong foam stabilizing effect and good stability, and are beneficial to preparing rigid polyurethane foam with uniform foam holes.
The polyurethane catalyst is one or more of pentamethyl diethylenetriamine, triethylenediamine, dimethylethanolamine, N-dimethylcyclohexylamine, triethylene diamine, triethylamine, N-methylpyrrolidone, 1, 4-dimethylpiperazine, N-dimethylbenzylamine, dimethylaminoethyl ether, tris (dimethylaminopropyl) hexahydrotriazine, potassium acetate, potassium isooctanoate and stannous octoate, and preferably one or more of triethylene diamine, N-dimethylcyclohexylamine, pentamethyl divinyl triamine, hexahydrotriazine and potassium acetate.
The polyurethane catalyst provided by the invention comprises a milky white catalyst, a gel catalyst and a trimerization catalyst, and the stable reaction can be ensured by reasonable collocation. Preferably, the milky white catalyst is pentamethyl diethylenetriamine with the mass part of 0.1-1.5; the gel catalyst is N, N-dimethylcyclohexylamine, and the mass fraction is 0.5-2.5; the trimerization catalyst is potassium acetate, and the mass fraction is 0.1-1.5.
The physical foaming agent comprises carbon dioxide and/or cyclopentane. Carbon dioxide has a relatively low boiling point, can still have good cell internal pressure at low temperature, is not inflammable and explosive per se, and is nontoxic.
Preferably, the physical foaming agent is cyclopentane and carbon dioxide, wherein the weight part of the cyclopentane is 5-20, and the weight part of the carbon dioxide is 1-5;
the isocyanate is polymeric MDI (polymethylene polyphenyl polyisocyanate) and the NCO content is 30-32%. Polymeric isocyanates that may be used include one or more of PM-200, PM-400, and PM-700 from Wanhua chemical groups Co., ltd.
The density of the polyurethane hard foam with low heat conduction and high strength is 25-35kg/m 3 The strength is more than or equal to 170kPa, and the heat conductivity coefficient is less than or equal to 18.50 mW/(m.K).
The preparation method of the polyurethane rigid foam comprises the following steps: according to the proportion, the components are mixed together,
1) Uniformly mixing the combined polyether polyol, the surfactant, the polyurethane catalyst and water, and uniformly mixing with cyclopentane;
2) Uniformly mixing carbon dioxide and the product of the step 1) at the pressure of 3-5bar and the temperature of 10-20 ℃;
3) And (3) mixing the product obtained in the step (2) with isocyanate through a high-pressure foaming agent to prepare the polyurethane rigid foam.
The other preparation method of the polyurethane rigid foam comprises the following steps: according to the proportion, the components are mixed together,
1') uniformly mixing the combined polyether polyol, the surfactant, the polyurethane catalyst and the water, and uniformly mixing with cyclopentane;
2') uniformly mixing carbon dioxide and isocyanate at the pressure of 3-5bar and the temperature of 10-20 ℃;
3 ') mixing the product of step 1 ') and the product of step 2 ') by a high-pressure foaming agent to prepare the polyurethane rigid foam.
In the step 3) or 3') according to the present invention, the operation conditions of the high pressure foaming machine are as follows: the temperature of the material is 17+/-4 ℃, and the operating pressure is 125+/-25 bar.
Further preferably, in the step 3) or 3') of the present invention, the high pressure foaming process has a filling factor of the reaction mixture in the mold of 1.05 to 1.35 and a demolding time of 80s to 180s.
In the preparation method of the polyurethane rigid foam, isocyanate reacts with the combined polyether and hydroxyl in water, and the isocyanate also reacts with the isocyanate through a trimerization catalyst under the condition that the trimerization catalyst exists.
In the prior art, carbon dioxide is selected as a physical foaming agent, and because the carbon dioxide has small molecules and low boiling points, the carbon dioxide can easily escape in the early stage of foaming to cause foam mixing or foam breaking in the formation of foam holes, thereby influencing heat conduction and strength to a certain extent. The invention adopts the tetraazacyclo-starting polyether polyol, and the special cavity structure thereof can absorb and envelop carbon dioxide in the cavity in the early stage of reaction, and the carbon dioxide and other foaming agents are uniformly distributed in the foam holes along with the reaction of the tetraazacyclo-starting polyether polyol and isocyanate and the release of heat by the reaction system, so that the foam holes are finer and finer, thereby achieving the optimal heat conduction. In addition, the benzene ring structure of the tetraazacyclo-starting polyether polyol itself enhances the rigidity of the foam, 4 active sites of the initiator itself react with ethylene oxide and propylene oxide, the steric configuration of molecules increases the steric hindrance among the molecules, the autocatalytic activity of the tetraazacyclo-starting polyether polyol is weakened, the flow of the foam is more gentle, and the fluidity is facilitated.
The pressure according to the invention is the relative pressure.
Tetraazacyclotene is an important class of compounds in cyclopolysaccharide which, structurally analyzed, is a cyclic compound linked by an azacarbon bridge through an aromatic ring, has a cavity structure within the molecule, and the aromatic ring on the cavity is laterally standing, has a certain depth, and has hydrophobic character. The thermal conductivity of polyurethane foam is determined by both the foam layer and the gas phase thermal conductivity of the gas in the cells. The cells of the polyurethane foam are predominantly polyhedral cellular structures, each polyhedron consisting of prisms and film windows. The physical structural strength of the prisms and films and the uniformity of the cells have a great impact on the physical strength of the foam. The invention introduces a novel tetraazacyclo polyether polyol, improves the physical strength of a base material and the adsorption envelope of a foaming agent from the molecular design perspective, thereby leading the foam to have higher strength and lower heat conduction.
The invention has the positive effects that:
the invention improves the physical structure strength of the foam cells mainly by introducing the tetraazapassion starting polyether polyol into the rigid polyurethane foam composite polyether, and the tetraazapassion starting polyether polyol can form a complex multi-benzene ring molecular structure in polyurethane molecules, thereby greatly enhancing the structure strength of the foam cells.
The invention uses tetraazacyclo-starter polyether polyol and low-boiling point foaming agent CO 2 The fluidity of the foam is greatly improved by matching. The self benzene ring can improve the skeleton strength of the foam layer, the cavity structure can firmly adsorb the foaming agent, the escape of the foaming agent is reduced, and the foam shrinkage caused by insufficient air pressure of the cells in the later stage is reduced.
The invention uses carbon dioxide as one of the foaming agents, and has no damage to ozone. The water content of the formula is reduced, so that the generation of urea structures which damage cells in the reaction process is reduced, and the curing performance of the surface of the foam is further improved; carbon dioxide has low boiling point, and is quickly nucleated in the early stage of foaming, so that foam cells are more and finer, and the heat conduction is reduced under the condition of making up for the higher gas phase heat conduction coefficient of the carbon dioxide.
Drawings
FIG. 1 is an NMR spectrum of polyether polyol A1 of example 1.
Detailed Description
The raw material sources are as follows:
polyether polyol B is prepared by adding sucrose as an initiator to propylene oxide (the hydroxyl value is 385mg KOH/g, and the functionality is 6.0);
polyether polyol C is prepared by an addition reaction of toluene diamine as an initiator and propylene oxide (the hydroxyl value is 430mg KOH/g, and the functionality is 3.4);
polyether polyol D is prepared by an addition reaction of sucrose and glycerol serving as an initiator and propylene oxide (the hydroxyl value is 460 mg KOH/g, and the functionality is 5.8);
polyether polyol E is prepared by an addition reaction of glycerol serving as an initiator and propylene oxide (with a hydroxyl value of 188mg KOH/g and a functionality of 2.3);
isocyanate: vanhua PM-200 (polymeric MDI);
silicon surfactant: AK8805 (meiosis);
silicon surfactant: b8525 (Evonik);
1,6,20,25-tetraaza [6.1.6.1]Pairing the tomato: in 4,4 ’ Starting from diaminodiphenylmethane, protecting the amino group with p-toluenesulfonyl chloride, cyclizing with dibromobutane under highly diluted conditions to give 1,6,20,25-tetraaza [6.1.6.1]]And (3) performing tomato pairing.
Embodiments of the present invention are further illustrated below with reference to examples. The invention is not limited to the embodiments listed but includes any other known modification within the scope of the claims that follow.
Example 1
Preparation of 1,6,20,25-tetraaza [6.1.6.1] polyether polyol A1 starting from cycloparaffin:
adding water (1140 g) and 1,6,20,25-tetraaza [6.1.6.1] pair of cyclop (260 g) into a reaction kettle, replacing nitrogen, starting stirring to heat to 100 ℃, maintaining for 1h to obtain 1,6,20,25-tetraaza [6.1.6.1] pair of cyclop aqueous solution, adding 600g of ethylene oxide according to the flow rate of 450g/h, controlling the pressure of 0.6MPa, autocatalyzing for 1h, adding 1300g of propylene oxide according to the flow rate of 700g/h, reacting until the pressure is unchanged, obtaining crude polyether, drying and press-filtering the crude polyether to obtain finished polyether, wherein the hydroxyl value is 210mgKOH/g, the functionality is 3.7, and the test standard GB/T12008.3-1989.
Polyether polyol A1 1 H NMR(400MHz,CDCl 3 )δ＝6.82(d,J＝7.1Hz,8H), 6.67(d,J＝7.2Hz,8H),5.37(s,4H),4.18(t,J＝7.8Hz,8H),3.58-3.64(m,28H), 3.36-3.38(m,8H),1.32(d,J＝6.8Hz,12H),1.11(d,J＝6.8Hz,12H)
Example 2
Preparation of 1,6,20,25-tetraaza [6.1.6.1] polyether polyol A2 starting from cycloparaffin:
adding water (1340 g) and 1,6,20,25-tetraaza [6.1.6.1] pair of cyclop (260 g) into a reaction kettle, replacing nitrogen, starting stirring and heating to 90 ℃, maintaining for 1h to obtain 1,6,20,25-tetraaza [6.1.6.1] pair of cyclop water solution, adding 500g of ethylene oxide according to the flow rate of 450g/h, controlling the pressure to 0.6MPa, autocatalyzing for 1h, heating to 120 ℃, adding 1200g of propylene oxide according to the flow rate of 700g/h, and reacting to obtain crude polyether when the reaction pressure is not changed; the crude polyether is dried and pressed to obtain the finished polyether with a hydroxyl value of 215mgKOH/g and a functionality of 3.5. Test Standard GB/T12008.3-1989.
Example 3
Composite catalyst: the foaming catalyst is pentamethyldiethylenetriamine, the gel catalyst is dimethylcyclohexylamine, the trimerization catalyst is potassium acetate, and the pentamethyldiethylenetriamine is used as the foaming catalyst: dimethylcyclohexylamine: potassium acetate=2:8:1 (mass ratio)
Preparation of polyurethane hard foam
(1) Adding 1.25 parts of polyether polyol A, 35 parts of polyether polyol B, 15 parts of polyether polyol C, 10 parts of polyether polyol D, 8.5 parts of polyether polyol E, 2.5 parts of composite catalyst, 2.5 parts of AK8805 and 1.5 parts of water into a mixing kettle, uniformly stirring, and adding 13 parts of CP for mixing;
(2) Under the condition of pressurizing 4bar, 2 parts of carbon dioxide and the product in the step (1) are conveyed to a mixer, and are uniformly mixed, and the material temperature is controlled below 20 ℃;
(3) Mixing the mixture obtained in the step 2) with 150 parts of PM-200, foaming at high pressure, wherein the material temperature is 19 ℃, the mold temperature is 45 ℃, the pressure is 130bar (gauge pressure), the filling coefficient of the reaction mixture in a mold is 1.15, and the demolding time is 150s, so that the low-conductivity high-strength polyurethane hard foam is prepared.
Example 4
Polyurethane rigid foam was prepared using the following raw materials, the preparation procedure is described in example 3:
the mass ratio of the combined polyether to the foaming agent to the isocyanate is 100:14:145, respectively;
1.55 parts of water;
physical blowing agent: 12 parts of Cyclopentane (CP) and 2 parts of carbon dioxide;
in the combined polyether polyol:
polyether polyol A2 20 parts,
30 parts of polyether polyol B,
14 parts of polyether polyol C,
15 parts of polyether polyol D,
13.75 parts of polyether polyol E;
isocyanate: PM-200 145 parts;
silicon surfactant: AK 8805.0 parts;
2.7 parts of composite catalyst: the foaming catalyst is pentamethyldiethylenetriamine, the gel catalyst is dimethylcyclohexylamine, the trimerization catalyst is potassium acetate, and the pentamethyldiethylenetriamine is used as the foaming catalyst: dimethylcyclohexylamine: potassium acetate=2:8:1 (mass ratio)
Example 5
Composite catalyst: the foaming catalyst is pentamethyldiethylenetriamine, the gel catalyst is dimethylcyclohexylamine, the trimerization catalyst is potassium acetate, and the pentamethyldiethylenetriamine is used as the foaming catalyst: dimethylcyclohexylamine: potassium acetate=1:5:1 (mass ratio)
Preparation of polyurethane hard foam
(1) Adding 15 parts of polyether polyol A, 45 parts of polyether polyol B, 15 parts of polyether polyol C, 20 parts of polyether polyol D, 8.5 parts of polyether polyol E, 2.5 parts of composite catalyst, 2.5 parts of B8525 and 1.5 parts of water into a mixing kettle, uniformly stirring, adding 13 parts of cyclopentane, and uniformly stirring;
(2) Under the condition of pressurizing 4bar, 2 parts of carbon dioxide and PM200 are conveyed to a mixer, and are uniformly mixed, and the material temperature is controlled below 20 ℃;
(3) Mixing the mixture obtained in the step 1) and the mixture obtained in the step 2), foaming at high pressure, wherein the material temperature is 19 ℃, the mold temperature is 45 ℃, the pressure is 130bar (gauge pressure), the filling coefficient of the reaction mixture in a mold is 1.15, and the demolding time is 150s, so that the low-conductivity high-strength polyurethane rigid foam is prepared.
Example 6
Polyurethane rigid foam was prepared using the following raw materials, the preparation procedure is described in example 5:
the mass ratio of the combined polyether to the foaming agent to the isocyanate is 100:15:145, respectively;
1.6 parts of water;
physical blowing agent: 14 parts of Cyclopentane (CP) and 1 part of carbon dioxide;
25 parts of polyether polyol A,
30 parts of polyether polyol B,
15 parts of polyether polyol C,
15 parts of polyether polyol D,
7.6 parts of polyether polyol E;
isocyanate: PM-200 145 parts;
silicon surfactant: b8525 3 parts;
2.8 parts of composite catalyst: the foaming catalyst is pentamethyldiethylenetriamine, the gel catalyst is dimethylcyclohexylamine, the trimerization catalyst is potassium acetate, and the pentamethyldiethylenetriamine is used as the foaming catalyst: dimethylcyclohexylamine: potassium acetate=1:4:1 (mass ratio)
Polyurethane foam performance test:
foam core density test was as per standard: GB/T6343-2009
Foam thermal conductivity test was as per standard: GB/T10295-2008
Foam compression strength test was as per standard: GB/T8813-2008
Foam dimensional stability test was as per standard: GB/T8811-2008
The example parameters and polyurethane foam properties are shown in Table 1.
Table 1 example parameters and polyurethane foam properties
The pressure tank testing method comprises the following steps: firstly, testing the volume by a foam drainage method, putting the foam into a sealed container, gradually adding the pressure to 1bar for 30min, testing the foam volume again, and comparing the change rate of the volume for 2 times.
Comparative example 1
The difference from example 3 is that the combined polyether does not comprise polyether polyol A1, the combined polyether polyol A1 is replaced by polyether polyol C in the same parts by weight, and the other conditions are the same as in example 3.
Comparative example 2
The difference from example 3 is that the moisture is increased from 1.5 parts to 1.65 parts, the physical blowing agent carbon dioxide is not used, the carbon dioxide is replaced by 2 parts of cyclopentane, and the other conditions are the same as in example 3.
Table 2 shows the properties of the comparative polyurethane rigid foam
Table 2 comparative polyurethane hard foam properties
| Comparative example 1 | Comparative example 2 | |
| Foam core Density/(kg/m) 3 ) | 32.46 | 32.78 |
| Flow index | 1.27 | 1.32 |
| Thermal conductivity/(mW/m.K) | 18.82 | 18.22 |
| Compressive Strength (vertical)/(KPa) | 154 | 170.5 |
| Pressure tank test 1bar/30min (%) | 2.7 | 1.5 |
| End of mouldNumber of foam surface defects (diameter>3cm) | 18 | 8 |
| High temperature dimensional stability 70 ℃/48h (%) | 0.6 | 0.9 |
| Closed porosity (%) | 89.3 | 95.2 |
The addition of the proper amount of tetraazacyclo polyether can obviously improve the physical strength of the foam and simultaneously improve the heat conductivity coefficient of the foam.
Claims (10)
1. A tetraazapassion starting polyether polyol having the structural formula:
wherein: a, b, c and d are each independently an integer not less than 1, preferably each independently an integer of 1 to 3; e, f, g and h are each independently an integer not less than 1, preferably each independently an integer of 1 to 5.
2. A tetraazapassion starting polyether polyol according to claim 1, characterized in that the hydroxyl number is 200-280mg KOH/g, the functionality is 3-4, preferably 3-3.8.
3. A process for preparing the tetraazacyclo-starting polyether polyol of claim 1 or 2, by addition polymerization of ethylene oxide and/or propylene oxide starting from 1,6,20,25-tetraaza [6.1.6.1] pair of cyclo-tomatoes.
4. A method according to claim 3, comprising the steps of: dissolving an initiator in water, replacing with nitrogen, adding ethylene oxide, heating to 80-140 ℃, and performing self-catalytic reaction for 1-4h under the pressure of less than or equal to 0.6MPa, continuing adding propylene oxide, and stopping the reaction when the pressure is kept unchanged to obtain crude polyether; and drying and filtering the crude polyether to obtain the product.
5. A process according to claim 3 or 4, wherein the initiator 1,6,20,25-tetraaza [6.1.6.1] is used in an amount of 250 to 550 parts by mass, ethylene oxide is used in an amount of 250 to 600 parts by mass and propylene oxide is used in an amount of 400 to 1500 parts by mass.
6. A polyurethane rigid foam comprising the following composition: in terms of the parts by weight,
90-100 parts, preferably 90-95 parts, of a combined polyether polyol;
1.0 to 4.0 parts, preferably 2.0 to 3.5 parts, of surfactant;
1.5 to 5.0 parts, preferably 2.0 to 3.0 parts, of polyurethane catalyst;
1.0 to 3.0 parts, preferably 1.0 to 2.0 parts, of water;
5-30 parts, preferably 10-20 parts, of a physical foaming agent;
110 to 160 parts, preferably 130 to 155 parts, of isocyanate;
the combination polyether polyol comprises the tetraazapassion starting polyether polyol of claim 1 or 2 or the tetraazapassion starting polyether polyol prepared by the process of any one of claims 3-5.
7. The polyurethane rigid foam according to claim 6, wherein the combined polyether polyol comprises the following composition:
(a) 5-30 parts, preferably 5-25 parts, of polyether polyol A, tetraazapassion starting polyether polyol;
(b) 20-50 parts, preferably 30-45 parts, of polyether polyol B prepared by an addition reaction of sucrose serving as an initiator and propylene oxide;
(c) Polyether polyol C is prepared by an addition reaction of toluene diamine serving as an initiator and propylene oxide, wherein 10-40 parts, preferably 14-40 parts, of polyether polyol C are prepared;
(d) 10-30 parts, preferably 10-20 parts, of polyether polyol D is prepared by an addition reaction of sucrose and glycerol serving as an initiator and propylene oxide;
(e) Polyether polyol E is prepared by the addition reaction of glycerin serving as an initiator and propylene oxide, and 5-15 parts, preferably 7.5-14.0 parts, of polyether polyol E are prepared.
8. A rigid polyurethane foam as claimed in claim 7, wherein,
the hydroxyl value of the polyether polyol B is 350-430mgKOH/g, and the functionality is 5.7-6.4;
the hydroxyl value of the polyether polyol C is 390-500mgKOH/g, and the functionality is 3.0-3.8;
the hydroxyl value of the polyether polyol D is 420-490mgKOH/g, and the functionality is 5.7-6.5;
the hydroxyl value of the polyether polyol E is 180-260mgKOH/g, and the functionality is 2.0-2.7.
9. A polyurethane rigid foam according to any of claims 6-8, characterized in that the physical blowing agent comprises carbon dioxide and/or cyclopentane; preferably, the physical foaming agent is cyclopentane and carbon dioxide, wherein the weight part of the cyclopentane is 5-20, and the weight part of the carbon dioxide is 1-5.
10. A process for preparing a rigid polyurethane foam as claimed in any one of claims 6 to 9, comprising the steps of: according to the proportion, 1) uniformly mixing the combined polyether polyol, the surfactant, the polyurethane catalyst and the water, and uniformly mixing with cyclopentane;
2) Uniformly mixing carbon dioxide and the product of the step 1) at the pressure of 3-5bar and the temperature of 10-20 ℃;
3) Mixing the product of the step 2) with isocyanate through a high-pressure foaming agent to prepare polyurethane rigid foam; or alternatively, the process may be performed,
1') uniformly mixing the combined polyether polyol, the surfactant, the polyurethane catalyst and the water, and uniformly mixing with cyclopentane;
2') uniformly mixing carbon dioxide and isocyanate at the pressure of 3-5bar and the temperature of 10-20 ℃;
3') mixing the products of the step 1) and the step 2) through a high-pressure foaming agent to prepare the polyurethane rigid foam.
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