CN115572361A - Acidic polyurethane rigid foam and preparation method thereof - Google Patents
Acidic polyurethane rigid foam and preparation method thereof Download PDFInfo
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- CN115572361A CN115572361A CN202110683707.7A CN202110683707A CN115572361A CN 115572361 A CN115572361 A CN 115572361A CN 202110683707 A CN202110683707 A CN 202110683707A CN 115572361 A CN115572361 A CN 115572361A
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- organic acid
- catalyst
- polyether polyol
- foam
- polyurethane foam
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- 239000006260 foam Substances 0.000 title claims abstract description 67
- 229920002635 polyurethane Polymers 0.000 title claims abstract description 36
- 239000004814 polyurethane Substances 0.000 title claims abstract description 36
- 238000002360 preparation method Methods 0.000 title abstract description 15
- 230000002378 acidificating effect Effects 0.000 title abstract description 8
- 239000003054 catalyst Substances 0.000 claims abstract description 62
- 150000007524 organic acids Chemical class 0.000 claims abstract description 47
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 15
- 238000006243 chemical reaction Methods 0.000 claims abstract description 7
- 239000012948 isocyanate Substances 0.000 claims abstract description 5
- 150000002513 isocyanates Chemical class 0.000 claims abstract description 5
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 claims abstract description 4
- 239000004721 Polyphenylene oxide Substances 0.000 claims description 80
- 229920000570 polyether Polymers 0.000 claims description 80
- 229920005862 polyol Polymers 0.000 claims description 50
- 150000003077 polyols Chemical class 0.000 claims description 50
- 239000000203 mixture Substances 0.000 claims description 35
- 125000002887 hydroxy group Chemical group [H]O* 0.000 claims description 32
- 229920001228 polyisocyanate Polymers 0.000 claims description 28
- 239000005056 polyisocyanate Substances 0.000 claims description 28
- 238000005187 foaming Methods 0.000 claims description 24
- 239000004088 foaming agent Substances 0.000 claims description 24
- 229920005830 Polyurethane Foam Polymers 0.000 claims description 18
- 239000011496 polyurethane foam Substances 0.000 claims description 18
- 239000002131 composite material Substances 0.000 claims description 16
- 239000002994 raw material Substances 0.000 claims description 14
- 239000004094 surface-active agent Substances 0.000 claims description 13
- 239000000463 material Substances 0.000 claims description 11
- 238000007259 addition reaction Methods 0.000 claims description 10
- 238000001816 cooling Methods 0.000 claims description 10
- 239000013256 coordination polymer Substances 0.000 claims description 10
- GOOHAUXETOMSMM-UHFFFAOYSA-N Propylene oxide Chemical compound CC1CO1 GOOHAUXETOMSMM-UHFFFAOYSA-N 0.000 claims description 8
- 239000003999 initiator Substances 0.000 claims description 8
- 239000004604 Blowing Agent Substances 0.000 claims description 7
- PEDCQBHIVMGVHV-UHFFFAOYSA-N Glycerine Chemical compound OCC(O)CO PEDCQBHIVMGVHV-UHFFFAOYSA-N 0.000 claims description 6
- MTHSVFCYNBDYFN-UHFFFAOYSA-N diethylene glycol Chemical compound OCCOCCO MTHSVFCYNBDYFN-UHFFFAOYSA-N 0.000 claims description 6
- 238000000034 method Methods 0.000 claims description 5
- RLYCRLGLCUXUPO-UHFFFAOYSA-N 2,6-diaminotoluene Chemical compound CC1=C(N)C=CC=C1N RLYCRLGLCUXUPO-UHFFFAOYSA-N 0.000 claims description 2
- FBPFZTCFMRRESA-FSIIMWSLSA-N D-Glucitol Natural products OC[C@H](O)[C@H](O)[C@@H](O)[C@H](O)CO FBPFZTCFMRRESA-FSIIMWSLSA-N 0.000 claims description 2
- IAYPIBMASNFSPL-UHFFFAOYSA-N Ethylene oxide Chemical compound C1CO1 IAYPIBMASNFSPL-UHFFFAOYSA-N 0.000 claims description 2
- 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 2
- 229930006000 Sucrose Natural products 0.000 claims description 2
- 230000002596 correlated effect Effects 0.000 claims description 2
- 238000004519 manufacturing process Methods 0.000 claims description 2
- 239000000600 sorbitol Substances 0.000 claims description 2
- 239000005720 sucrose Substances 0.000 claims description 2
- 230000009257 reactivity Effects 0.000 abstract description 3
- SCVFZCLFOSHCOH-UHFFFAOYSA-M potassium acetate Chemical compound [K+].CC([O-])=O SCVFZCLFOSHCOH-UHFFFAOYSA-M 0.000 description 20
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 15
- UKODFQOELJFMII-UHFFFAOYSA-N pentamethyldiethylenetriamine Chemical compound CN(C)CCN(C)CCN(C)C UKODFQOELJFMII-UHFFFAOYSA-N 0.000 description 13
- SVYKKECYCPFKGB-UHFFFAOYSA-N N,N-dimethylcyclohexylamine Chemical compound CN(C)C1CCCCC1 SVYKKECYCPFKGB-UHFFFAOYSA-N 0.000 description 12
- 235000011056 potassium acetate Nutrition 0.000 description 10
- 238000012360 testing method Methods 0.000 description 10
- WLJVXDMOQOGPHL-UHFFFAOYSA-N phenylacetic acid Chemical compound OC(=O)CC1=CC=CC=C1 WLJVXDMOQOGPHL-UHFFFAOYSA-N 0.000 description 8
- 238000005829 trimerization reaction Methods 0.000 description 7
- 230000000052 comparative effect Effects 0.000 description 5
- 230000000694 effects Effects 0.000 description 5
- OYWRDHBGMCXGFY-UHFFFAOYSA-N 1,2,3-triazinane Chemical compound C1CNNNC1 OYWRDHBGMCXGFY-UHFFFAOYSA-N 0.000 description 4
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 4
- 239000000654 additive Substances 0.000 description 4
- 230000000996 additive effect Effects 0.000 description 4
- 229960003424 phenylacetic acid Drugs 0.000 description 4
- 239000003279 phenylacetic acid Substances 0.000 description 4
- 229920002545 silicone oil Polymers 0.000 description 4
- YCKRFDGAMUMZLT-UHFFFAOYSA-N Fluorine atom Chemical compound [F] YCKRFDGAMUMZLT-UHFFFAOYSA-N 0.000 description 3
- 230000006835 compression Effects 0.000 description 3
- 238000007906 compression Methods 0.000 description 3
- 239000011737 fluorine Substances 0.000 description 3
- 229910052731 fluorine Inorganic materials 0.000 description 3
- QEGNUYASOUJEHD-UHFFFAOYSA-N 1,1-dimethylcyclohexane Chemical compound CC1(C)CCCCC1 QEGNUYASOUJEHD-UHFFFAOYSA-N 0.000 description 2
- CBENFWSGALASAD-UHFFFAOYSA-N Ozone Chemical compound [O-][O+]=O CBENFWSGALASAD-UHFFFAOYSA-N 0.000 description 2
- 230000006978 adaptation Effects 0.000 description 2
- 238000011161 development Methods 0.000 description 2
- 238000005265 energy consumption Methods 0.000 description 2
- 238000002474 experimental method Methods 0.000 description 2
- 229910052742 iron Inorganic materials 0.000 description 2
- 239000007788 liquid Substances 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 238000005457 optimization Methods 0.000 description 2
- 229920003023 plastic Polymers 0.000 description 2
- 239000004033 plastic Substances 0.000 description 2
- 229920000728 polyester Polymers 0.000 description 2
- IMNIMPAHZVJRPE-UHFFFAOYSA-N triethylenediamine Chemical compound C1CN2CCN1CC2 IMNIMPAHZVJRPE-UHFFFAOYSA-N 0.000 description 2
- 238000010792 warming Methods 0.000 description 2
- 238000005303 weighing Methods 0.000 description 2
- 238000005491 wire drawing Methods 0.000 description 2
- AQZABFSNDJQNDC-UHFFFAOYSA-N 2-[2,2-bis(dimethylamino)ethoxy]-1-n,1-n,1-n',1-n'-tetramethylethane-1,1-diamine Chemical compound CN(C)C(N(C)C)COCC(N(C)C)N(C)C AQZABFSNDJQNDC-UHFFFAOYSA-N 0.000 description 1
- LXBGSDVWAMZHDD-UHFFFAOYSA-N 2-methyl-1h-imidazole Chemical compound CC1=NC=CN1 LXBGSDVWAMZHDD-UHFFFAOYSA-N 0.000 description 1
- WLJVXDMOQOGPHL-PPJXEINESA-N 2-phenylacetic acid Chemical compound O[14C](=O)CC1=CC=CC=C1 WLJVXDMOQOGPHL-PPJXEINESA-N 0.000 description 1
- ONIBWKKTOPOVIA-BYPYZUCNSA-N L-Proline Chemical compound OC(=O)[C@@H]1CCCN1 ONIBWKKTOPOVIA-BYPYZUCNSA-N 0.000 description 1
- 239000004677 Nylon Substances 0.000 description 1
- 239000004743 Polypropylene Substances 0.000 description 1
- 229920002396 Polyurea Polymers 0.000 description 1
- ONIBWKKTOPOVIA-UHFFFAOYSA-N Proline Natural products OC(=O)C1CCCN1 ONIBWKKTOPOVIA-UHFFFAOYSA-N 0.000 description 1
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical group [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 230000000875 corresponding effect Effects 0.000 description 1
- XXBDWLFCJWSEKW-UHFFFAOYSA-N dimethylbenzylamine Chemical compound CN(C)CC1=CC=CC=C1 XXBDWLFCJWSEKW-UHFFFAOYSA-N 0.000 description 1
- 239000000835 fiber Substances 0.000 description 1
- 238000009413 insulation Methods 0.000 description 1
- XLSZMDLNRCVEIJ-UHFFFAOYSA-N methylimidazole Natural products CC1=CNC=N1 XLSZMDLNRCVEIJ-UHFFFAOYSA-N 0.000 description 1
- 238000000465 moulding Methods 0.000 description 1
- TXXWBTOATXBWDR-UHFFFAOYSA-N n,n,n',n'-tetramethylhexane-1,6-diamine Chemical compound CN(C)CCCCCCN(C)C TXXWBTOATXBWDR-UHFFFAOYSA-N 0.000 description 1
- 229920001778 nylon Polymers 0.000 description 1
- 239000011022 opal Substances 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- -1 polypropylene Polymers 0.000 description 1
- 229920001155 polypropylene Polymers 0.000 description 1
- 229920001296 polysiloxane Polymers 0.000 description 1
- 230000008092 positive effect Effects 0.000 description 1
- 238000004321 preservation Methods 0.000 description 1
- 230000002035 prolonged effect Effects 0.000 description 1
- 150000003242 quaternary ammonium salts Chemical class 0.000 description 1
- 229920005989 resin Polymers 0.000 description 1
- 239000011347 resin Substances 0.000 description 1
- 229910052710 silicon Inorganic materials 0.000 description 1
- 239000010703 silicon Substances 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 238000007711 solidification Methods 0.000 description 1
- 230000008023 solidification Effects 0.000 description 1
- 238000013112 stability test Methods 0.000 description 1
- 238000006467 substitution reaction Methods 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
- C08G18/4804—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
- C08G18/487—Polyethers containing cyclic groups
- C08G18/4883—Polyethers containing cyclic groups containing cyclic groups having at least one oxygen atom in the ring
-
- 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
- C08G18/5024—Polyethers having heteroatoms other than oxygen having nitrogen containing primary and/or secondary amino groups
- C08G18/5027—Polyethers having heteroatoms other than oxygen having nitrogen containing primary and/or secondary amino groups directly linked to carbocyclic groups
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J9/00—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof
- C08J9/04—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof using blowing gases generated by a previously added blowing agent
- C08J9/12—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof using blowing gases generated by a previously added blowing agent by a physical blowing agent
- C08J9/14—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof using blowing gases generated by a previously added blowing agent by a physical blowing agent organic
- C08J9/141—Hydrocarbons
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- 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
- C08J9/143—Halogen containing compounds
- C08J9/144—Halogen containing compounds containing carbon, halogen and hydrogen only
-
- 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
- C08J9/149—Mixtures of blowing agents covered by more than one of the groups C08J9/141 - C08J9/143
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G2101/00—Manufacture of cellular products
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G2110/00—Foam properties
- C08G2110/0025—Foam properties rigid
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G2110/00—Foam properties
- C08G2110/0041—Foam properties having specified density
- C08G2110/005—< 50kg/m3
-
- 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
- C08J2203/14—Saturated hydrocarbons, e.g. butane; Unspecified hydrocarbons
- C08J2203/142—Halogenated saturated hydrocarbons, e.g. H3C-CF3
-
- 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
Abstract
The invention provides a polyurethane rigid foam based on an acidic condition and a preparation method thereof. The polyurethane rigid foam is added with an organic acid in the preparation process, the reactivity of the polyurethane catalyst can be reduced under the acidic condition, so that the content of the catalyst can be increased, and carboxyl in the organic acid can react with isocyanate to generate CO 2 Therefore, the water content in the formula can be reduced, the adhesion of the foam skin is improved, the foam starts to gel and the acidity disappears at the later reaction stage, the foam skin can be rapidly solidified by high catalyst content, and the skin bubbles are reduced, so that more excellent comprehensive performance is embodied.
Description
Technical Field
The invention belongs to the field of polyurethane materials, and particularly relates to acidic polyurethane rigid foam and a preparation method thereof.
Background
Polyurethane rigid foam is widely used in the fields of refrigerators, freezers, containers and the like due to the advantages of light weight, high strength and easy molding. Has developed rapidly and has undergone many technological updates.
Rigid polyurethane foams have a very low density. The density is about 10-300kg/m 3 Corresponding to a fraction, even a few tenths, of the density of ordinary foamed plastics. The polyurethane rigid foam has excellent heat insulation performance, and the heat conductivity coefficient is far lower than that of high polymer plastics such as nylon, resin, polypropylene and the like. Due to the excellence of the performance, the novel composite material has vigorous development at home and abroad in recent years, makes a plurality of technical breakthroughs and meets the requirements of different fields.
The foaming agent CFC is replaced in the polyurethane industry in order to protect the atmospheric ozone layer, and the appearance of the foaming agent replacement finds a new way for the polyurethane industry. The criteria for a blowing agent replacement product is that the ozone depletion potential is equal to zero and the global warming potential is as low as possible. However, the CFC substitutes for the foaming agent, the gaseous thermal conductivity coefficient is high, the gaseous thermal conductivity coefficient occupies more than 50% of the thermal conductivity coefficient of the polyurethane rigid foam, the increase of the gaseous thermal conductivity coefficient leads to the increase of the thermal conductivity coefficient of the polyurethane integral foam, and the energy consumption value of heat preservation equipment, such as refrigerators, freezers, water heaters and the like, can not reach the national standard, so that how to apply the environment-friendly foaming agent without losing the foam thermal conductivity coefficient or the energy consumption of household appliances becomes a difficult problem in the development of polyurethane.
The mode of using polyester as a main raw material is selected by factories, but the demoulding performance of the polyester is poor, the surface curing of the foam is poor, and the central foam fiber framework is cured slowly, so that the curing time can only be prolonged on site, and the production efficiency is influenced, and the labor cost is increased. The method that a small amount of fluorine-containing additive is added in a factory is adopted, but the price of the fluorine-containing additive is several times or even dozens of times of that of a basic polyether material, the fluorine-containing additive is used, the cost of raw materials of a formula rises greatly, the profit of a single refrigerator per se is limited, and the cost and the pressure of the factory greatly rise after the additive is used, so that the technical difficulty that the heat conductivity coefficient of the formula is optimized on the basis of reducing the cost rise becomes a polyurethane material is achieved.
Disclosure of Invention
The invention aims to provide a polyurethane rigid foam, which has little increase of the cost of raw materials, meets the requirement of a foaming agent with high thermal conductivity in the global warming potential, does not increase the thermal conductivity, reduces the size of cells, increases the curing of the surface of the foam, and improves the strength of the foam.
In order to achieve the purpose, the invention adopts the following technical scheme:
a rigid polyurethane foam, wherein the raw material of the rigid polyurethane foam contains organic acid, and the raw material of the rigid polyurethane foam comprises the following components:
in the present invention, the conjugate polyether comprises: 89.5-94 parts of mixed polyether polyol, 3.5-5.5 parts of combined catalyst, 1.5-3.5 parts of surfactant and 1.0-2.5 parts of water.
In the invention, the polyether polyol is mixed in the combined polyether, and comprises one or more of the following polyols:
polyether polyol A: sorbitol is used as an initiator and is prepared by addition reaction with propylene oxide, the viscosity is 25,000-35,000mPa.s, the hydroxyl value is 350-550mgKOH/g, and the functionality is 5.5-6.0;
polyether polyol B: sucrose and glycerol are used as initiator to carry out addition reaction with propylene oxide, the viscosity is 8,000-15,000mPa.s, the hydroxyl value is 450-600mgKOH/g, and the functionality is 4.6-5.8;
polyether polyol C: o-toluenediamine is used as an initiator, and is subjected to addition reaction with ethylene oxide, propylene oxide is added after the reaction is finished, and the addition reaction is carried out, wherein the viscosity is 35,000-55,000mPa.s, the hydroxyl value is 340-460mgKOH/g, and the functionality is 3.4-3.9;
polyether polyol D: diethylene glycol is used as an initiator to carry out addition reaction with propylene oxide, the viscosity is 50-100mPa.s, the hydroxyl value is 200-300mgKOH/g, and the functionality is 2.0.
In the invention, the content of the combined catalyst in the combined polyether is positively correlated with the content of the organic acid, and preferably the content of the catalyst and the content of the organic acid have the following relationship:
wherein m is 0 Combined catalyst mass in the absence of organic acid, m e For combined catalyst masses, m c Is the mass of the organic acid.
In the invention, the composite catalyst in the composite polyether is as follows: one or more of opal pentamethyldiethylenetriamine, tetramethylhexamethylenediamine and bis-dimethylaminoethylether; one or more of dimethylbenzylamine, dimethylcyclohexane, triethylene diamine and methylimidazole serving as gel catalysts; trimerization catalyst potassium acetate, hexahydrotriazine and one or more of quaternary ammonium salt.
In the invention, the surfactant in the combined polyether is a silicon surfactant, preferably a silicone surfactant, and more preferably one or more of silicone oil L6861, silicone oil B8481, silicone oil RW-E, Y16368 and silicone oil B84813.
In the invention, the polyisocyanate is polymeric MDI, preferably polymeric MDI with NCO content of 30-32 wt%, more preferably one or more of Wanhua PM-200, wanhua PM-2010 and Wanhua PM-400; preferably, the mass content of the polyisocyanate has the following formula:
wherein m is b Is the mass of isocyanate, m a M is the mass of the combined polyether d M is the mass of the blowing agent c Is mass of organic acid, M c Is the organic acid molecular weight.
In the present invention, the organic acid has the following structural formula:
wherein n is an integer of not less than 0, preferably an integer of 0 to 3, and R is-CH 3 or-Ph; preferably, the organic acid contains-COOH groups which react with isocyanate to produce CO 2 Remains in the cell and has the following reaction formula:
above-mentioned organic acid is acidity in the combined material, can reduce catalyst activity, under guaranteeing the same wire drawing time, can increase the content of catalyst by a wide margin, and the reaction later stage, the foam is by the liquid quick wire drawing, turns into solid-state, and at this in-process, acidity disappears, and catalyst activity promotes in the twinkling of an eye, reduces the foam and moves to there is better surface bubble after the foam solidification. The acidity increases the catalyst content, and when the later acidity disappears, the catalyst content is increased, which is equivalent to that of a common system, so that the foam curing and demolding performance can be greatly improved. Although the activity of the catalyst is reduced, more active sites are formed at the early stage, so that the size of the foam is finer, the thermal conductivity of the foam is lower, and the strength is higher.
In the invention, the foaming agent is a single foaming agent or a mixed foaming agent, and at least a CP foaming agent is contained in the foaming agent.
Another object of the present invention is to provide a method for preparing the rigid polyurethane foam.
A preparation method of polyurethane rigid foam, wherein the rigid foam is the polyurethane rigid foam, and the preparation method comprises the following steps:
s1: uniformly mixing the mixed polyether polyol, the surfactant, the composite catalyst and water, and cooling to obtain a combined polyether mixture A;
s2: adding organic acid into the mixture A, shaking up, standing and cooling to obtain a mixture B;
s3: uniformly mixing the mixture B and the foaming agent to obtain a mixture C;
s4: and respectively adding the mixture C and the polyisocyanate into independent foaming machine charging pots, mixing and foaming under high pressure, and striking into a mold to obtain the polyurethane rigid foam.
In the invention, the cooling in the steps S1 and S2 is below 15 ℃; the conditions of high-pressure foaming in the step S4 are that the material temperature is 15-20 ℃, the material temperature is preferably 17-18 ℃, and the pressure is 100-150barG, and the pressure is preferably 125-130barG.
In the invention, the die in the step S4 is a horizontal die and/or a vertical die, the size of the horizontal die is 70 × 40 × 10cm, and the size of the vertical die is 110 × 30 × 5cm; the mold temperature is 35-50 ℃, the overfilling rate is 15-25%, and the demolding time is 150-300s.
Compared with the prior art, the invention has the following positive effects:
1) The organic acid is acidic, the content of the catalyst can be increased under the same reaction activity, in the later reaction period, the foam begins to be drawn, the liquid state is converted into the solid state, the acidity disappears in the process, the high-content catalyst begins to play a role, the foam curing performance and the demolding performance are improved, the foam curing is performed from 240s to 240s, the foam curing is performed from 180s after the organic acid is added, and the curing performance is optimized for 60s; the average value of the demoulding expansion of the original formula for 240s is 4.21%, after the organic acid is added, the average value of the demoulding expansion of 210s is 4.24%, and the demoulding performance is optimized to be nearly 30s.
2) After the organic acid is added, the later stage acidity disappears, the foam gel is accelerated due to the high catalyst content, and the movement at the later stage of foam is influenced, so that the foam has better surface bubbles, and the number of the A-type bubbles is reduced to 8 from 15.
3) After the organic acid is added, the catalyst content is high, although the activity is lower, the active sites are more, the foam is more fine, and the size of the foam hole is reduced from 325nm to 172nm through the test of a scanning electron microscope.
4) The organic acid contains carboxyl, so that the consumption of water in the composite polyether can be reduced, the generation of polyurea is reduced, the curing and surface adhesion of foam can be improved, and the average adhesion of the foam is improved from 12kg.f to 17kg.f.
Detailed Description
The technical solutions of the present invention are further described by the following specific examples, but the scope of the present invention is not limited thereto, and variations or substitutions of the same or similar technical features within the technical scope of the present invention are included.
The main materials and reagents of the embodiment of the invention are as follows:
the main instrument manufacturers and models in the examples and comparative examples of the present invention are as follows:
| name of instrument | Type number | Manufacturer of the product |
| Heat conduction instrument | HC-074 | EKO Equipment Inc |
| Compression strength machine | 5Kn Proline | Zwick/Roell |
| High-pressure foaming machine | HK650 | Hennecke |
| Electron microscope | SIGMA 500 | Caishi |
| Tension meter | SH-B | Mountain degree instrument |
| Micrometer | 468-174 | Mitutoyo |
Example 1
The organic acid-containing polyurethane rigid foam comprises the following raw materials in a mass ratio of the composite polyether, the polyisocyanate, the organic acid and the foaming agent of 100:
the composite polyether comprises the following components: 35.4kg of polyether polyol A (hydroxyl value of 465 mgKOH/g), 30kg of polyether polyol B (hydroxyl value of 498 mgKOH/g), 20kg of polyether polyol C (hydroxyl value of 362 mgKOH/g), 7kg of polyether polyol D (hydroxyl value of 251 mgKOH/g), 8481 kg of surfactant, 3.5kg of combined catalyst and 2.1kg of water;
wherein, the combined catalyst: the foaming catalyst is 0.625kg of pentamethyl diethylenetriamine, the gel catalyst is 2.125kg of dimethyl cyclohexylamine, the trimerization catalyst is 0.75kg of potassium acetate, and the mass ratio of pentamethyl diethylenetriamine to dimethyl cyclohexylamine to potassium acetate is 1.2.
Polyisocyanate: wanhua PM 200.1 kg;
organic acid: 1kg of anhydrous acetic acid;
foaming agent: CP 12kg.
The preparation method of the polyurethane hard foam comprises the following steps:
s1: weighing 35.4kg of polyether polyol A, 30kg of polyether polyol B, 20kg of polyether polyol C, 7kg of polyether polyol D, 2kg of B8481, 3.5kg of combined catalyst and 2.1kg of water, uniformly mixing, and cooling to 14 ℃ to obtain a mixture A;
s2: adding 2kg of anhydrous acetic acid into the mixture A, shaking uniformly, standing for 4h, defoaming, and cooling for 14 ℃ to obtain a mixture B;
s3: the mixture B and 12kg of CP are uniformly mixed by rotating through a closed pressure-bearing iron bucket, and then the mixture is kept stand for 8 hours to obtain a mixture C;
s4: and respectively adding the mixture C and polyisocyanate into independent charging pots, and mixing and foaming under high pressure to obtain the rigid polyurethane foam. The high-pressure foaming material temperature is 18 ℃, the ratio of the polyether mixture to the polyisocyanate high-pressure foaming is 1.34, the gun head pressure is 125bar, the flow rate is 500g/s, and the mold temperature is 45 ℃. The following die experiments were performed, respectively, with a vertical die size of 1100 × 300 × 50mm, a demolding time of 240s, for testing foam adhesion, thermal conductivity, compressive strength, core density, pressure pot strength, and dimensional stability; horizontal die size 700 x 400 x 100mm, demold time 150s, 180s, 210s, 240s, for testing foam demold performance and surface cure performance; l-die demold time 240s for testing foam surface bubbles.
Example 2
The organic acid-containing polyurethane rigid foam comprises the following raw materials in mass ratio of (combined polyether, polyisocyanate, organic acid and foaming agent) 100:
the composite polyether comprises the following components: 35.2kg of polyether polyol A (hydroxyl value of 465 mgKOH/g), 30kg of polyether polyol B (hydroxyl value of 498 mgKOH/g), 20kg of polyether polyol C (hydroxyl value of 362 mgKOH/g), 7kg of polyether polyol D (hydroxyl value of 251 mgKOH/g), 8481 kg of surfactant, 4.0kg of combined catalyst and 1.8kg of water;
wherein, the combination catalyst: the foaming catalyst is 0.714kg of pentamethyldiethylenetriamine, the gel catalyst is 2.429kg of dimethylcyclohexylamine, the trimerization catalyst is 0.857kg of potassium acetate, and the mass ratio of pentamethyldiethylenetriamine to dimethylcyclohexylamine to potassium acetate is 1.2.
Polyisocyanate: wanhua PM 200.6 kg;
organic acid: 2kg of anhydrous acetic acid;
foaming agent: CP 12kg.
The preparation method of the polyurethane rigid foam is the same as that of the example 1, and the ratio of the polyether mixture to the polyisocyanate high-pressure foaming is 1.
Example 3
The organic acid-containing polyurethane rigid foam comprises the following raw materials in a mass ratio of composite polyether, polyisocyanate, organic acid and foaming agent of 100:
the composite polyether comprises the following components: 35.1kg of polyether polyol A (hydroxyl value of 465 mgKOH/g), 30kg of polyether polyol B (hydroxyl value of 498 mgKOH/g), 20kg of polyether polyol C (hydroxyl value of 362 mgKOH/g), 7kg of polyether polyol D (hydroxyl value of 251 mgKOH/g), 8481 kg of surfactant, 4.4kg of combined catalyst and 1.5kg of water;
wherein, the combination catalyst: the foaming catalyst is 0.786kg of pentamethyldiethylenetriamine, the gel catalyst is 2.671kg of dimethylcyclohexylamine, the trimerization catalyst is 0.943kg of potassium acetate, and the mass ratio of the pentamethyldiethylenetriamine to the dimethylcyclohexylamine to the potassium acetate is 1.2.
Polyisocyanate: 200.1 kg of Wanhua PM;
organic acid: 3kg of anhydrous acetic acid;
foaming agent: CP 12kg.
The preparation method of the polyurethane rigid foam is the same as the example 1, and the ratio of the polyether mixture to the polyisocyanate high-pressure foaming is 1.
Example 4
The organic acid-containing polyurethane rigid foam comprises the following raw materials in a mass ratio of composite polyether, polyisocyanate, organic acid and foaming agent of 100:
the composition of the combined polyether is as follows: 37.1kg of polyether polyol A (hydroxyl value of 465 mgKOH/g), 20kg of polyether polyol B (hydroxyl value of 498 mgKOH/g), 30kg of polyether polyol C (hydroxyl value of 362 mgKOH/g), 4kg of polyether polyol D (hydroxyl value of 251 mgKOH/g), 12369 kg of surfactant Y, 4.4kg of combined catalyst and 1.5kg of water;
wherein, the combination catalyst: the foaming catalyst is 0.88kg of pentamethyl diethylenetriamine, the gel catalyst is 2.55kg of dimethylcyclohexylamine, the trimerization catalyst is 0.97kg of hexahydrotriazine, and the mass ratio of pentamethyl diethylenetriamine to dimethylcyclohexylamine to potassium acetate = 1.1.
Polyisocyanate: wanhua PM 200.1 kg;
organic acid: 1kg of phenylacetic acid;
foaming agent: CP 12kg, LBA 5kg.
The preparation method of the polyurethane hard foam comprises the following steps:
s1: weighing 37kg of polyether polyol A, 20kg of polyether polyol B, 30kg of polyether polyol C, 4kg of polyether polyol D, 3kg of Y16368, 4.5kg of combined catalyst and 1.5kg of water, uniformly mixing, and cooling to 14 ℃ to obtain a mixture A;
s2: adding 1kg of phenylacetic acid into the mixture A, shaking uniformly, standing for 4h, defoaming, and cooling to 14 ℃ to obtain a mixture B;
s3: uniformly mixing the mixture B, 12kg of CP and 5kg of LBA through rotation of a closed pressure-bearing iron bucket, and standing for 8 hours to obtain a mixture C;
s4: and respectively adding the mixture C and polyisocyanate into independent charging pots, and mixing and foaming under high pressure to obtain the rigid polyurethane foam. The high-pressure foaming material temperature is 17 ℃, the high-pressure foaming proportion of the polyether mixture and the polyisocyanate is 1.32, the gun head pressure is 125bar, the flow rate is 500g/s, and the mold temperature is 45 ℃. The following die experiments were performed, respectively, with a vertical die size of 1100 × 300 × 50mm, a demolding time of 240s, for testing foam adhesion, thermal conductivity, compressive strength, core density, pressure pot strength, and dimensional stability; horizontal die size 700 x 400 x 100mm, demold time 150s, 180s, 210s, 240s, for testing foam demold performance and surface cure performance; l-die demold time 240s for testing foam surface bubbles.
Example 5
The organic acid-containing polyurethane rigid foam comprises the following raw materials in a mass ratio of composite polyether, polyisocyanate, organic acid and foaming agent of 100:
the composite polyether comprises the following components: 36.8kg of polyether polyol A (hydroxyl value of 465 mgKOH/g), 20kg of polyether polyol B (hydroxyl value of 498 mgKOH/g), 30kg of polyether polyol C (hydroxyl value of 362 mgKOH/g), 4kg of polyether polyol D (hydroxyl value of 251 mgKOH/g), 12369 kg of surfactant Y, 4.9kg of combined catalyst and 1.3kg of water;
wherein, the combined catalyst: the foaming catalyst is 0.98kg of pentamethyl diethylenetriamine, the gel catalyst is 2.84kg of dimethylcyclohexylamine, the trimerization catalyst is 1.08kg of hexahydrotriazine, and the mass ratio of pentamethyl diethylenetriamine to dimethylcyclohexylamine to potassium acetate = 1.1.
Polyisocyanate: wanhua PM 200.4 kg;
organic acid: 2kg of phenylacetic acid;
foaming agent: CP 10kg, LBA 8kg.
The preparation method of the polyurethane rigid foam is the same as the example 1, and the ratio of the polyether mixture to the polyisocyanate high-pressure foaming is 1.
Example 6
The organic acid-containing polyurethane rigid foam comprises the following raw materials in a mass ratio of composite polyether, polyisocyanate, organic acid and foaming agent of 100:
the composite polyether comprises the following components: 36.2kg of polyether polyol A (hydroxyl value of 465 mgKOH/g), 20kg of polyether polyol B (hydroxyl value of 498 mgKOH/g), 30kg of polyether polyol C (hydroxyl value of 362 mgKOH/g), 4kg of polyether polyol D (hydroxyl value of 251 mgKOH/g), 3.5kg of surfactant Y12369, 5.3kg of combined catalyst and 1.0kg of water;
wherein, the combination catalyst: the foaming catalyst is 1.06kg of pentamethyldiethylenetriamine, the gel catalyst is 3.07kg of dimethylcyclohexylamine, the trimerization catalyst is 1.17kg of hexahydrotriazine, and the mass ratio of the pentamethyldiethylenetriamine to the dimethylcyclohexylamine to the potassium acetate is 1.1.
Polyisocyanate: 200.4 kg of Wanhua PM;
organic acid: 3kg of phenylacetic acid;
foaming agent: CP 10kg, LBA 8kg.
The preparation method of the polyurethane rigid foam is the same as the example 1, and the ratio of the polyether mixture to the polyisocyanate high-pressure foaming is 1.
Table 1 examples 1-6 raw materials composition (weight, unit kg) and performance parameters of polyurethane rigid foam
Note: the foam density, the compressive strength, the thermal conductivity and the dimensional stability are determined according to the national standard:
foam core density test according to standard: GB/T6343-2009;
foam thermal conductivity test according to standard: GB/T10295-2008;
foam compression strength test according to the standard: GB/T8813-2008;
foam dimensional stability test according to the standard: GB/T8811-2008.
Surface bubble standard: the diameter is more than or equal to 2cm.
Comparative example 1
In example 1, the removal of 1kg of anhydrous acetic acid, the reactivity was faster under non-acidic conditions, less combined catalyst content was required, the weight was 2.3kg, the density was higher, the moisture was increased to 2.5kg and the polyether polyol A was increased to 36.2g. The other components are in accordance with example 1.
The polyurethane rigid foam was prepared in the same manner as in example 1, the polyether mixture and the polyisocyanate were foamed at a high pressure ratio of 1.
Comparative example 2
In example 4, eliminating 1kg of phenylacetic acid, the reactivity was faster under non-acidic conditions, requiring less combined catalyst content, a weight of 3.2kg, a higher density, requiring an increase in moisture to 1.9kg, and an increase in polyether polyol A to 37.9g. The other components are in accordance with example 4.
The preparation method of the polyurethane rigid foam is the same as the preparation method of the example 4, and the ratio of the polyether mixture to the polyisocyanate high-pressure foaming is 1.
TABLE 2 hard polyurethane foam Properties obtained in comparative examples 1-2
From the comparison between the above examples and comparative examples, it can be found that the polyurethane rigid foam prepared by the scheme of the invention has higher compression strength, smaller deformation rate of the pressure tank, lower thermal conductivity, approximately 60s of curing optimization, 30s of demolding performance optimization and lower thermal conductivity under the condition of the same core density, thereby showing more excellent comprehensiveness.
It will be appreciated by those skilled in the art that modifications or adaptations to the invention may be made in light of the teachings of the present specification. Such modifications or adaptations are intended to be within the scope of the present invention as defined in the claims.
Claims (9)
1. A rigid polyurethane foam is characterized in that the raw materials of the rigid polyurethane foam contain organic acid, and the raw materials of the rigid polyurethane foam comprise the following components:
2. the rigid polyurethane foam according to claim 1, wherein the conjugate polyether comprises: 89.5-94 parts of mixed polyether polyol, 3.5-5.5 parts of combined catalyst, 1.5-3.5 parts of surfactant and 1.0-2.5 parts of water.
3. The rigid polyurethane foam according to claim 2, wherein the mixed polyether polyol comprises one or more of the following polyols:
polyether polyol A: sorbitol is used as an initiator and is prepared by addition reaction with propylene oxide, the viscosity is 25,000-35,000mPa.s, the hydroxyl value is 350-550mgKOH/g, and the functionality is 5.5-6.0;
polyether polyol B: sucrose and glycerol are used as initiator to carry out addition reaction with propylene oxide, the viscosity is 8,000-15,000mPa.s, the hydroxyl value is 450-600mgKOH/g, and the functionality is 4.6-5.8;
polyether polyol C: o-toluenediamine is used as an initiator, and is subjected to addition reaction with ethylene oxide, propylene oxide is added after the reaction is finished, and the addition reaction is carried out, wherein the viscosity is 35,000-55,000mPa.s, the hydroxyl value is 340-460mgKOH/g, and the functionality is 3.4-3.9;
polyether polyol D: diethylene glycol is used as an initiator to carry out addition reaction with propylene oxide, the viscosity is 50-100mPa.s, the hydroxyl value is 200-300mgKOH/g, and the functionality is 2.0.
4. The rigid polyurethane foam according to claim 2, wherein the combined catalyst content is positively correlated to the organic acid content, preferably the catalyst content has the following relationship to the organic acid content:
wherein m is 0 Combined catalyst mass in the absence of organic acid, m e For combined catalyst masses, m c Is the mass of the organic acid.
5. The rigid polyurethane foam according to claim 1, wherein the polyisocyanate is polymeric MDI, preferably polymeric MDI having an NCO content of 30 to 32wt%, more preferably one or more of wanhua PM-200, wanhua PM-2010 and wanhua PM-400;
preferably, the mass content of the polyisocyanate has the following formula:
wherein m is b Is the mass of isocyanate, m a Is the combined polyether mass, m d M is the mass of the blowing agent c Is the mass of the organic acid, M c Is organic acid molecular weight。
6. The rigid polyurethane foam according to claim 1, wherein the organic acid has a general structural formula as follows:
wherein n is an integer of not less than 0, preferably an integer of 0 to 3, and R is-CH 3 or-Ph;
preferably, the organic acid contains-COOH groups capable of reacting with isocyanate to produce CO 2 Remaining in the cells.
7. The rigid polyurethane foam according to claim 1, wherein the blowing agent is a single blowing agent or a mixed blowing agent containing at least a CP blowing agent.
8. A production method of a rigid polyurethane foam according to any one of claims 1 to 7, comprising the steps of:
s1: uniformly mixing the mixed polyether polyol, the surfactant, the composite catalyst and water, and cooling to obtain a combined polyether mixture A;
s2: adding organic acid into the mixture A, shaking up, standing and cooling to obtain a mixture B;
s3: uniformly mixing the mixture B and the foaming agent to obtain a mixture C;
s4: and respectively adding the mixture C and the polyisocyanate into independent foaming machine charging pots, mixing and foaming under high pressure, and striking into a mold to obtain the polyurethane rigid foam.
9. The method according to claim 8, wherein the cooling in steps S1, S2 is below 15 ℃; the conditions of high-pressure foaming in the step S4 are that the material temperature is 15-20 ℃, the material temperature is preferably 17-18 ℃, and the pressure is 100-150barG, and the pressure is preferably 125-130barG.
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Citations (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4617286A (en) * | 1983-09-08 | 1986-10-14 | Toyo Soda Manufacturing Co., Ltd. | Catalyst for polyurethane having delay property |
| DK128188D0 (en) * | 1987-03-12 | 1988-03-09 | Dow Chemical Co | REACTIVITY STABILIZATION OF POLYESTER POLYOL-BASED POLYURETHAN FOOD COMPONENTS |
| US5489618A (en) * | 1993-11-29 | 1996-02-06 | Osi Specialties, Inc. | Process for preparing polyurethane foam |
| JPH09104734A (en) * | 1995-08-04 | 1997-04-22 | Tosoh Corp | Polyurethane foam and catalyst for production of isocyanurate foam |
| JPH11310622A (en) * | 1998-04-28 | 1999-11-09 | Dainippon Ink & Chem Inc | Moisture curing urethane resin composition, coating material and sealing material |
| CN1235617A (en) * | 1996-11-04 | 1999-11-17 | 帝国化学工业公司 | Rigid polyurethane foams |
| CA2294561A1 (en) * | 1999-01-05 | 2000-07-05 | Ck Witco Corporation | Process for using polyurethane foam |
| US20070197760A1 (en) * | 1999-09-20 | 2007-08-23 | Tosoh Corporation | Catalyst for production of polyurethane |
| CN110023844A (en) * | 2017-09-19 | 2019-07-16 | Nok株式会社 | Polyurethane elastomeric compositions, the manufacturing method of cleaning blade and cleaning blade |
-
2021
- 2021-06-21 CN CN202110683707.7A patent/CN115572361A/en active Pending
Patent Citations (10)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4617286A (en) * | 1983-09-08 | 1986-10-14 | Toyo Soda Manufacturing Co., Ltd. | Catalyst for polyurethane having delay property |
| DK128188D0 (en) * | 1987-03-12 | 1988-03-09 | Dow Chemical Co | REACTIVITY STABILIZATION OF POLYESTER POLYOL-BASED POLYURETHAN FOOD COMPONENTS |
| US4758605A (en) * | 1987-03-12 | 1988-07-19 | The Dow Chemical Company | Stabilization of reactivity of polyester polyol based polyurethane foam components |
| US5489618A (en) * | 1993-11-29 | 1996-02-06 | Osi Specialties, Inc. | Process for preparing polyurethane foam |
| JPH09104734A (en) * | 1995-08-04 | 1997-04-22 | Tosoh Corp | Polyurethane foam and catalyst for production of isocyanurate foam |
| CN1235617A (en) * | 1996-11-04 | 1999-11-17 | 帝国化学工业公司 | Rigid polyurethane foams |
| JPH11310622A (en) * | 1998-04-28 | 1999-11-09 | Dainippon Ink & Chem Inc | Moisture curing urethane resin composition, coating material and sealing material |
| CA2294561A1 (en) * | 1999-01-05 | 2000-07-05 | Ck Witco Corporation | Process for using polyurethane foam |
| US20070197760A1 (en) * | 1999-09-20 | 2007-08-23 | Tosoh Corporation | Catalyst for production of polyurethane |
| CN110023844A (en) * | 2017-09-19 | 2019-07-16 | Nok株式会社 | Polyurethane elastomeric compositions, the manufacturing method of cleaning blade and cleaning blade |
Non-Patent Citations (1)
| Title |
|---|
| 高民生: "聚氨酯反应中有机酸对叔胺催化性能的影响", 《聚氨酯工业》, no. 4, pages 19 - 23 * |
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