CN116693936B - Polyurethane hard foam additive, preparation method thereof, polyurethane hard foam and application thereof - Google Patents
Polyurethane hard foam additive, preparation method thereof, polyurethane hard foam and application thereof Download PDFInfo
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- CN116693936B CN116693936B CN202310654287.9A CN202310654287A CN116693936B CN 116693936 B CN116693936 B CN 116693936B CN 202310654287 A CN202310654287 A CN 202310654287A CN 116693936 B CN116693936 B CN 116693936B
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- hard foam
- polyurethane hard
- polyurethane
- additive
- foam additive
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- 239000006260 foam Substances 0.000 title claims abstract description 132
- 229920002635 polyurethane Polymers 0.000 title claims abstract description 119
- 239000004814 polyurethane Substances 0.000 title claims abstract description 119
- 239000000654 additive Substances 0.000 title claims abstract description 71
- 230000000996 additive effect Effects 0.000 title claims abstract description 70
- 238000002360 preparation method Methods 0.000 title claims abstract description 29
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims abstract description 53
- 239000000203 mixture Substances 0.000 claims abstract description 50
- SAPOZTRFWJZUFT-UHFFFAOYSA-N 1,1,1,2,3,4,5,5,5-nonafluoro-4-(trifluoromethyl)pent-2-ene Chemical compound FC(F)(F)C(F)=C(F)C(F)(C(F)(F)F)C(F)(F)F SAPOZTRFWJZUFT-UHFFFAOYSA-N 0.000 claims abstract description 27
- 239000005543 nano-size silicon particle Substances 0.000 claims abstract description 19
- 235000012239 silicon dioxide Nutrition 0.000 claims abstract description 19
- 239000004088 foaming agent Substances 0.000 claims abstract description 17
- 238000000034 method Methods 0.000 claims abstract description 14
- 238000004945 emulsification Methods 0.000 claims abstract description 12
- 239000004721 Polyphenylene oxide Substances 0.000 claims description 47
- 229920000570 polyether Polymers 0.000 claims description 47
- 230000001804 emulsifying effect Effects 0.000 claims description 23
- 239000003054 catalyst Substances 0.000 claims description 18
- -1 polyoxyethylene Polymers 0.000 claims description 17
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 12
- 229920003171 Poly (ethylene oxide) Polymers 0.000 claims description 12
- 229920005862 polyol Polymers 0.000 claims description 11
- 150000003077 polyols Chemical class 0.000 claims description 11
- 229920005906 polyester polyol Polymers 0.000 claims description 9
- OFBQJSOFQDEBGM-UHFFFAOYSA-N Pentane Chemical compound CCCCC OFBQJSOFQDEBGM-UHFFFAOYSA-N 0.000 claims description 8
- 239000002994 raw material Substances 0.000 claims description 6
- 229920002545 silicone oil Polymers 0.000 claims description 6
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 6
- SVYKKECYCPFKGB-UHFFFAOYSA-N N,N-dimethylcyclohexylamine Chemical compound CN(C)C1CCCCC1 SVYKKECYCPFKGB-UHFFFAOYSA-N 0.000 claims description 4
- 150000001412 amines Chemical class 0.000 claims description 4
- 238000005187 foaming Methods 0.000 claims description 4
- 239000002184 metal Substances 0.000 claims description 4
- TZIHFWKZFHZASV-UHFFFAOYSA-N methyl formate Chemical compound COC=O TZIHFWKZFHZASV-UHFFFAOYSA-N 0.000 claims description 4
- IMNIMPAHZVJRPE-UHFFFAOYSA-N triethylenediamine Chemical compound C1CN2CCN1CC2 IMNIMPAHZVJRPE-UHFFFAOYSA-N 0.000 claims description 4
- 239000004604 Blowing Agent Substances 0.000 claims description 3
- 238000005507 spraying Methods 0.000 claims description 3
- ZESKRVSPQJVIMH-UHFFFAOYSA-N 1,3-dimethoxypropan-2-ol Chemical compound COCC(O)COC ZESKRVSPQJVIMH-UHFFFAOYSA-N 0.000 claims description 2
- FXRLMCRCYDHQFW-UHFFFAOYSA-N 2,3,3,3-tetrafluoropropene Chemical compound FC(=C)C(F)(F)F FXRLMCRCYDHQFW-UHFFFAOYSA-N 0.000 claims description 2
- GTEXIOINCJRBIO-UHFFFAOYSA-N 2-[2-(dimethylamino)ethoxy]-n,n-dimethylethanamine Chemical compound CN(C)CCOCCN(C)C GTEXIOINCJRBIO-UHFFFAOYSA-N 0.000 claims description 2
- DPXFJZGPVUNVOT-UHFFFAOYSA-N 3-[1,3-bis[3-(dimethylamino)propyl]triazinan-5-yl]-n,n-dimethylpropan-1-amine Chemical compound CN(C)CCCC1CN(CCCN(C)C)NN(CCCN(C)C)C1 DPXFJZGPVUNVOT-UHFFFAOYSA-N 0.000 claims description 2
- 229920005830 Polyurethane Foam Polymers 0.000 claims description 2
- 150000001875 compounds Chemical class 0.000 claims description 2
- XXBDWLFCJWSEKW-UHFFFAOYSA-N dimethylbenzylamine Chemical compound CN(C)CC1=CC=CC=C1 XXBDWLFCJWSEKW-UHFFFAOYSA-N 0.000 claims description 2
- MSSNHSVIGIHOJA-UHFFFAOYSA-N pentafluoropropane Chemical compound FC(F)CC(F)(F)F MSSNHSVIGIHOJA-UHFFFAOYSA-N 0.000 claims description 2
- UKODFQOELJFMII-UHFFFAOYSA-N pentamethyldiethylenetriamine Chemical compound CN(C)CCN(C)CCN(C)C UKODFQOELJFMII-UHFFFAOYSA-N 0.000 claims description 2
- 239000011496 polyurethane foam Substances 0.000 claims description 2
- 238000010276 construction Methods 0.000 claims 1
- 239000003995 emulsifying agent Substances 0.000 abstract description 8
- 239000012752 auxiliary agent Substances 0.000 abstract description 5
- 230000000694 effects Effects 0.000 abstract description 3
- 238000004134 energy conservation Methods 0.000 abstract description 2
- 230000000052 comparative effect Effects 0.000 description 43
- UPMLOUAZCHDJJD-UHFFFAOYSA-N 4,4'-Diphenylmethane Diisocyanate Chemical compound C1=CC(N=C=O)=CC=C1CC1=CC=C(N=C=O)C=C1 UPMLOUAZCHDJJD-UHFFFAOYSA-N 0.000 description 28
- 230000032798 delamination Effects 0.000 description 9
- 239000000377 silicon dioxide Substances 0.000 description 8
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 6
- 239000000463 material Substances 0.000 description 6
- 239000000126 substance Substances 0.000 description 6
- 238000010998 test method Methods 0.000 description 4
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 description 3
- WGCNASOHLSPBMP-UHFFFAOYSA-N hydroxyacetaldehyde Natural products OCC=O WGCNASOHLSPBMP-UHFFFAOYSA-N 0.000 description 3
- 238000003860 storage Methods 0.000 description 3
- OQISUJXQFPPARX-UHFFFAOYSA-N 2-chloro-3,3,3-trifluoroprop-1-ene Chemical compound FC(F)(F)C(Cl)=C OQISUJXQFPPARX-UHFFFAOYSA-N 0.000 description 2
- 241001391944 Commicarpus scandens Species 0.000 description 2
- CBENFWSGALASAD-UHFFFAOYSA-N Ozone Chemical compound [O-][O+]=O CBENFWSGALASAD-UHFFFAOYSA-N 0.000 description 2
- 238000004090 dissolution Methods 0.000 description 2
- 230000007613 environmental effect Effects 0.000 description 2
- 238000010438 heat treatment Methods 0.000 description 2
- 230000006911 nucleation Effects 0.000 description 2
- 238000010899 nucleation Methods 0.000 description 2
- 239000002245 particle Substances 0.000 description 2
- 230000004224 protection Effects 0.000 description 2
- YRTNMMLRBJMGJJ-UHFFFAOYSA-N 2,2-dimethylpropane-1,3-diol;hexanedioic acid Chemical compound OCC(C)(C)CO.OC(=O)CCCCC(O)=O YRTNMMLRBJMGJJ-UHFFFAOYSA-N 0.000 description 1
- SECXISVLQFMRJM-UHFFFAOYSA-N N-Methylpyrrolidone Chemical compound CN1CCCC1=O SECXISVLQFMRJM-UHFFFAOYSA-N 0.000 description 1
- 239000002202 Polyethylene glycol Substances 0.000 description 1
- 230000006750 UV protection Effects 0.000 description 1
- 230000032683 aging Effects 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 239000006229 carbon black Substances 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- PUUOOWSPWTVMDS-UHFFFAOYSA-N difluorosilane Chemical compound F[SiH2]F PUUOOWSPWTVMDS-UHFFFAOYSA-N 0.000 description 1
- 210000000497 foam cell Anatomy 0.000 description 1
- 239000012535 impurity Substances 0.000 description 1
- 230000014759 maintenance of location Effects 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 231100000252 nontoxic Toxicity 0.000 description 1
- 230000003000 nontoxic effect Effects 0.000 description 1
- 230000009965 odorless effect Effects 0.000 description 1
- 230000003287 optical effect Effects 0.000 description 1
- 229920003023 plastic Polymers 0.000 description 1
- 239000004033 plastic Substances 0.000 description 1
- 229920000921 polyethylene adipate Polymers 0.000 description 1
- 229920001223 polyethylene glycol Polymers 0.000 description 1
- 229920001228 polyisocyanate Polymers 0.000 description 1
- 239000005056 polyisocyanate Substances 0.000 description 1
- 229920006389 polyphenyl polymer Polymers 0.000 description 1
- 229920001451 polypropylene glycol Polymers 0.000 description 1
- 229920000909 polytetrahydrofuran Polymers 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 238000010792 warming 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
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K5/00—Use of organic ingredients
- C08K5/02—Halogenated hydrocarbons
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- 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
- C08G18/4009—Two or more macromolecular compounds not provided for in one single group of groups C08G18/42 - C08G18/64
- C08G18/4018—Mixtures of compounds of group C08G18/42 with compounds of group C08G18/48
-
- 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
- C08G18/42—Polycondensates having carboxylic or carbonic ester groups in the main chain
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
- C08G18/40—High-molecular-weight compounds
- C08G18/48—Polyethers
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- 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
- C08J9/0014—Use of organic additives
- C08J9/0019—Use of organic additives halogenated
-
- 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
- C08J9/0066—Use of inorganic compounding ingredients
- C08J9/0071—Nanosized fillers, i.e. having at least one dimension below 100 nanometers
-
- 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
- C08J9/0095—Mixtures of at least two compounding ingredients belonging to different one-dot groups
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- 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
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- 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
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- 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
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- 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
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/34—Silicon-containing compounds
- C08K3/36—Silica
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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
- C08G2101/00—Manufacture of cellular products
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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
- C08G2110/00—Foam properties
- C08G2110/0025—Foam properties rigid
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- 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
- C08J2203/16—Unsaturated hydrocarbons
- C08J2203/162—Halogenated unsaturated hydrocarbons, e.g. H2C=CF2
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- 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
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K2201/00—Specific properties of additives
- C08K2201/011—Nanostructured additives
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P20/00—Technologies relating to chemical industry
- Y02P20/10—Process efficiency
Abstract
The application provides a polyurethane hard foam additive, a preparation method thereof, polyurethane hard foam and application thereof, and relates to the technical field of polyurethane hard foam. According to the polyurethane hard foam additive, perfluoro-4-methyl-2-pentene and nano silicon dioxide are mixed with an emulsifier, and the mixture is effectively dissolved and is not layered through vacuum, emulsification and ultrasonic processes, so that the mixture can be used as an auxiliary agent to be added into polyurethane hard foam, the obtained polyurethane hard foam can greatly improve the quantity of foam, nucleate in advance, the rate of a foaming agent entering into foam holes is improved to be more than 90%, the foam holes of the foam are more uniform, and even if the environment-friendly foaming agent is adopted, the heat conductivity coefficient can reach about 0.016w/m.k, so that the environment-friendly purpose is achieved, and the effect of energy conservation is also achieved.
Description
Technical Field
The application relates to the technical field of polyurethane hard foam, in particular to a polyurethane hard foam additive, a preparation method thereof, polyurethane hard foam and application.
Background
The polyurethane hard foam is prepared by reacting hard foam polyether polyol with polymeric MDI, is mainly used for preparing hard polyurethane foam plastic, and is widely applied to the fields of refrigerators, cold storage, spraying, solar energy, heating pipelines, buildings and the like. With the improvement of environmental protection requirements, an environment-friendly foaming agent (ozone depletion potential value is 0, global warming potential value is close to 0) is gradually adopted in the preparation process of the polyurethane hard foam, so that the earth ozone layer is protected, the greenhouse effect is reduced, and the purpose of environmental protection is achieved.
However, the thermal conductivity of the environment-friendly foaming agent is higher than 0.018w/m.k, so that the thermal conductivity of the polyurethane hard foam prepared by the original non-environment-friendly foaming agent cannot reach the level of about 0.016w/m.k, and energy conservation cannot be better achieved.
Disclosure of Invention
The purpose of the application is to provide a polyurethane hard foam additive, a preparation method thereof, polyurethane hard foam and application, so as to solve the problems.
In order to achieve the above purpose, the present application adopts the following technical scheme:
the application firstly provides a polyurethane hard foam additive, which comprises the following components in percentage by mass:
70% -80% of perfluoro-4-methyl-2-pentene;
5% -10% of emulsifying agent;
10 to 25 percent of nano silicon dioxide.
The perfluoro-4-methyl-2-pentene may be used in an amount of, for example, 70%, 71%, 72%, 73%, 74%, 75%, 76%, 77%, 78%, 79% or 80%.
Wherein, the emulsifier mainly plays a role of emulsification and dissolution, and the dosage of the emulsifier can be 5%, 6%, 7%, 8%, 9% or 10%, for example. Preferably, the emulsifier comprises any one or more of polyoxyethylene alcohol, N-methylpyrrolidone and dimethylformamide.
Wherein, the nano silicon dioxide is an inorganic chemical material commonly called white carbon black. The size of the material is in the range of 1-100 nm due to the ultra-fine nano-scale, so that the material has a plurality of unique properties, such as optical performance for ultraviolet resistance, can improve the ageing resistance, strength and chemical resistance of other materials, and has very wide application. The nano silicon dioxide is amorphous white powder, is nontoxic, odorless and pollution-free, has a spherical microstructure and is in a flocculent and net quasi-particle structure. The nano-silica may be used in an amount of, for example, 10%, 11%, 12%, 13%, 14%, 15%, 16%, 17%, 18%, 19%, 20%, 21%, 22%, 23%, 24% or 25%. The particle size of the nanosilica is preferably 5 to 50nm, and may be, for example, 5nm, 6nm, 8nm, 10nm, 12nm, 13nm, 15nm, 17nm, 19nm, 20nm, 22nm, 25nm, 26nm, 28nm, 30nm, 32nm, 33nm, 35nm, 37nm, 40nm, 43nm, 45nm, 47nm, 48nm or 50nm.
The application also provides a preparation method of the polyurethane hard foam additive, which comprises the steps of mixing the raw materials according to the proportion under the conditions of vacuum and ultrasonic wave in an emulsifying way to obtain the polyurethane hard foam additive.
Perfluoro-4-methyl-2-pentene and nano silicon dioxide are directly used as auxiliary agents to be added into polyurethane rigid foam, so that the problems of poor storage property, poor dissolution and layering are solved, and the effective popularization is difficult. According to the preparation method, perfluoro-4-methyl-2-pentene and nano silicon dioxide are mixed with an emulsifying agent, and are effectively dissolved and not layered through vacuum, emulsification and ultrasonic processes, so that the perfluoro-4-methyl-2-pentene and nano silicon dioxide can be used as an auxiliary agent to be added into polyurethane hard foam. Perfluoro-4-methyl-2-pentene can promote nucleation, reduce the surface tension of bubbles and enable the thickness of the bubbles to be thickConsistent, and is not easy to break. The addition of silicon difluoride has the effect of more easily reaching the balance of surface tension and increasing the bubble wallIt is not easy to break foam.
Preferably, the preparation method of the polyurethane hard foam additive meets at least one of the following conditions A to D:
A. the vacuum degree of the vacuum is 1 to 1000pa, and may be (1, 10, 20, 30, 40, 50, 60, 70, 80, 90, 100, 110, 120, 130, 140, 150, 160, 170, 180, 190, 200, 210, 220, 230, 240, 250, 260, 270, 280, 290, 300, 320, 350, 360, 380, 400, 420, 450, 470, 480, 500, 520, 550, 570, 590, 600, 620, 650, 680, 700, 750, 800, 850, 900, 950 or 1000) pa;
B. the power of the ultrasonic wave is 50 to 500W, for example, (50, 60, 70, 80, 90, 100, 110, 120, 130, 140, 150, 160, 170, 180, 190, 200, 210, 220, 230, 240, 250, 260, 270, 280, 290, 300, 310, 320, 330, 340, 350, 360, 370, 380, 390, 400, 410, 420, 430, 440, 450, 460, 470, 480, 490, or 500) W, and the frequency of the ultrasonic wave is 20 to 40HZ, for example, (20, 21, 22, 23, 24, 25, 26, 27, 28, 29, 30, 31, 32, 33, 34, 35, 36, 37, 38, 39, or 40) HZ; the ultrasonic wave is continuously performed for 5-15 s, for example, the ultrasonic wave can be continuously performed for 5, 6, 7, 8, 9, 10, 11, 12, 13, 14 or 15) s (5, 6, 7, 8, 9, 10, 11, 12, 13, 14 or 15) s;
C. the emulsifying machine power is 1.5-100 kilowatts, for example, (1.5, 5, 10, 15, 20, 25, 30, 35, 40, 45, 50, 55, 60, 65, 70, 75, 80, 85, 90, 95 or 100) kilowatts, the emulsifying machine rotating speed is 5000-50000 rpm, for example, (5000, 5500, 6000, 6500, 7000, 7500, 8000, 8500, 9000, 9500, 10000, 11000, 12000, 13000, 140000, 15000, 16000, 17000, 18000, 19000, 20000, 25000, 30000, 35000, 40000, 45000 or 50000) rpm;
D. the time for the emulsification is 20 to 40min, and may be, for example, (20, 21, 22, 23, 24, 25, 26, 27, 28, 29, 30, 31, 32, 33, 34, 35, 36, 37, 38, 39 or 40) min.
The application also provides a polyurethane hard foam, and the raw materials of the polyurethane hard foam comprise the polyurethane hard foam additive.
The mixture obtained by mixing perfluoro-4-methyl-2-pentene, nano silicon dioxide and an emulsifier is used as an auxiliary agent to be added into polyurethane hard foam, so that the quantity of the foam can be greatly increased, the nucleation is advanced, the rate of the foaming agent entering the foam is increased to more than 90%, the foam cells of the foam are more uniform, and the heat conductivity coefficient can reach about 0.016w/m.k, so that the energy is saved more effectively.
Preferably, the polyurethane hard foam is obtained by mixing and foaming a polyether composition and a polymeric MDI, and the polyurethane hard foam additive is added to the polyether composition and/or to the polymeric MDI. That is, the polyurethane hard foam additive may be added to the polyether composition alone, to the polymeric MDI alone, or to both the polyether composition and the polymeric MDI at the same time, as long as the total amount of the polyurethane hard foam additive added is not changed.
Wherein the polyether composition is also called white material and is a mixture of polyether polyol; polymeric MDI, also known as crude MDI or black feed, is a mixture containing a proportion of pure MDI and polyphenyl polymethylene polyisocyanate.
Preferably, the mass ratio of the polyether composition and the polymeric MDI is 1: (1 to 1.5), for example, may be 1:1, or 1:1.1, or 1:1.2, or 1:1.3, or 1:1.4, or 1:1.5.
Preferably, when the polyurethane hard foam additive is added to the polyether composition, the polyurethane hard foam additive may be 1% to 5% by mass in the polyether composition, for example, 1%, 1.5%, 2%, 2.5%, 3%, 3.5%, 4%, 4.5% or 5%; when the polyurethane hard foam additive is added to the polymeric MDI, the mass percentage of the polyurethane hard foam additive in the polymeric MDI is 1% to 5%, for example, may be 1%, 1.5%, 2%, 2.5%, 3%, 3.5%, 4%, 4.5% or 5%.
Preferably, when the polyurethane hard foam additive is added to the polyether composition, the polyether composition comprises, in mass percent:
the polyether polyol may be any one or more of polytetramethylene ether glycol, polypropylene glycol, and polyethylene glycol, and the polyether polyol may be used in an amount of 45%, 46%, 47%, 48%, 49%, 50%, 51%, 52%, 53%, 54%, or 55%, for example.
The polyester polyol may be any one or more of, for example, polypropylene adipate glycol, neopentyl glycol adipate glycol, and polyethylene adipate glycol, and the amount of the polyester polyol may be, for example, 14%, 15%, 16%, 17%, 18%, 19%, 20%, 21%, 22%, 23%, 24%, 25%, 26%, 27%, 28%, 29%, 30%, 31%, 32%, 33%, 34%, 35%, 36%, 37%, or 38%.
Wherein the catalyst comprises an amine catalyst and/or a metal catalyst, and the amine catalyst comprises one or more of N, N-dimethyl cyclohexylamine, pentamethyl diethylenetriamine, N-dimethyl benzylamine, 1,3, 5-tri (dimethylaminopropyl) hexahydrotriazine, bis (2-dimethylaminoethyl) ether and triethylene diamine; the metal catalyst comprises one or more of organotin, organobismuth or organozinc compounds; the catalyst may be used in an amount of, for example, 1%, 1.5%, 2%, 2.5% or 3%.
The silicone oil may be used in an amount of, for example, 1%, 1.5%, 2%, 2.5% or 3%; the water may be used in an amount of, for example, 1%, 1.5%, 2%, 2.5% or 3%.
Wherein the blowing agent may be used in an amount of, for example, 10%, 11%, 12%, 13%, 14%, 15%, 16%, 17%, 18%, 19% or 20% and the blowing agent is selected from one or more of pentane, methyl formate, 245fa, LBA, R600a, R-152a, R-134a, R-1234yf, kemu opteon1100, kemu opteon1150, HCFO-1224yd, HCFO-1234ze, HCFO-1243zf and HCFO-1233 xf.
The application finally provides the application of the polyurethane hard foam, for example, the application in the fields of refrigerators, cold storages, spraying, solar energy, heating pipelines, buildings and the like.
Compared with the prior art, the beneficial effects of this application include:
according to the polyurethane hard foam additive, perfluoro-4-methyl-2-pentene, nano silicon dioxide and an emulsifier are mixed, and the mixture is effectively dissolved and is not layered through vacuum, emulsification and ultrasonic processes, so that the mixture can be used as an auxiliary agent to be added into polyurethane hard foam, the obtained polyurethane hard foam can greatly improve the quantity of foam, nucleate in advance, the rate of a foaming agent entering into foam holes is improved to be more than 90%, the foam holes of the foam are more uniform, the heat conductivity coefficient can reach about 0.016w/m.k even if an environment-friendly foaming agent is adopted, the environment-friendly purpose is achieved, and the energy is effectively saved.
Drawings
In order to more clearly illustrate the technical solutions of the embodiments of the present application, the drawings that are needed in the embodiments will be briefly described below, it being understood that the following drawings only illustrate certain embodiments of the present application and therefore should not be considered as limiting the scope of the present application.
Fig. 1 and 2 are physical views of polyurethane hard foam prepared in example 1 of the present application.
Detailed Description
The term as used herein:
"prepared from … …" is synonymous with "comprising". The terms "comprising," "including," "having," "containing," or any other variation thereof, as used herein, are intended to cover a non-exclusive inclusion. For example, a composition, step, method, article, or apparatus that comprises a list of elements is not necessarily limited to only those elements but may include other elements not expressly listed or inherent to such composition, step, method, article, or apparatus.
The conjunction "consisting of … …" excludes any unspecified element, step or component. If used in a claim, such phrase will cause the claim to be closed, such that it does not include materials other than those described, except for conventional impurities associated therewith. When the phrase "consisting of … …" appears in a clause of the claim body, rather than immediately following the subject, it is limited to only the elements described in that clause; other elements are not excluded from the stated claims as a whole.
When an equivalent, concentration, or other value or parameter is expressed as a range, preferred range, or a range bounded by a list of upper preferable values and lower preferable values, this is to be understood as specifically disclosing all ranges formed from any pair of any upper range limit or preferred value and any lower range limit or preferred value, regardless of whether ranges are separately disclosed. For example, when ranges of "1 to 5" are disclosed, the described ranges should be construed to include ranges of "1 to 4", "1 to 3", "1 to 2 and 4 to 5", "1 to 3 and 5", and the like. When a numerical range is described herein, unless otherwise indicated, the range is intended to include its endpoints and all integers and fractions within the range.
In these examples, the parts and percentages are by mass unless otherwise indicated.
"parts by mass" means a basic unit of measurement showing the mass ratio of a plurality of components, and 1 part may be any unit mass, for example, 1g may be expressed, 2.689g may be expressed, and the like. If we say that the mass part of the a component is a part and the mass part of the B component is B part, the ratio a of the mass of the a component to the mass of the B component is represented as: b. alternatively, the mass of the A component is aK, and the mass of the B component is bK (K is an arbitrary number and represents a multiple factor). It is not misunderstood that the sum of the parts by mass of all the components is not limited to 100 parts, unlike the parts by mass.
"and/or" is used to indicate that one or both of the illustrated cases may occur, e.g., a and/or B include (a and B) and (a or B).
Embodiments of the present application will be described in detail below with reference to specific examples, but it will be understood by those skilled in the art that the following examples are only for illustration of the present application and should not be construed as limiting the scope of the present application. The specific conditions are not noted in the examples and are carried out according to conventional conditions or conditions recommended by the manufacturer. The reagents or apparatus used were conventional products commercially available without the manufacturer's attention.
Example 1
Example 1 first provides a polyurethane hard foam additive comprising, in mass percent: 75% of perfluoro-4-methyl-2-pentene; 7% of polyoxyethylene alcohol; 18% of nano silicon dioxide.
Example 1 also provides a method for preparing a polyurethane hard foam additive comprising the steps of:
adding perfluoro-4-methyl-2-pentene, polyoxyethylene alcohol and nano silicon dioxide into an emulsifying machine according to the proportion;
emulsifying and mixing the raw materials under the conditions of 800pa of vacuum degree, 400W of ultrasonic power and 30HZ of ultrasonic frequency to obtain the polyurethane hard foam additive of the embodiment 1;
wherein, the power of the emulsifying machine is 80 kilowatts, and the rotating speed of the emulsifying machine is 30000rpm; the emulsification time is 30min, and the ultrasonic wave is continuously carried out for 10s at 10 s.
Example 1 also provides a polyurethane rigid foam obtained by mixing and foaming a polyether composition and a polymeric MDI, the mass ratio of the polyether composition to the polymeric MDI being 1:1.2, the polymeric MDI is BASF M20S, the polyether composition comprising, in mass percent: 54.5% of polyether polyol; 20% of polyester polyol; 2% of a catalyst; 2% of silicone oil; 15% of a foaming agent; 2.5% of water; 4% of the polyurethane hard foam additive of example 1. Wherein the polyether polyol is 4110 product purchased from Hebei eastern chemical industry, the polyester polyol is 3152 product purchased from Spanish chemical industry, the catalyst is N, N-dimethylcyclohexylamine purchased from winning, and the foaming agent comprises pentane 5%, LBA 3%, HCFO-1233xf 5% and R600%. The polyurethane rigid foam prepared in example 1 is shown in fig. 1 and 2.
The polyurethane hard foam of example 1 was tested three times for heat conductivity, and the test method was tested according to GB/T10294-2008 method, and the results were 0.0162w/m.k, 0.0158w/m.k, 0.0159w/m.k, respectively, and it was found that the heat conductivity of the polyurethane hard foam of example 1 was about 0.016w/m.k, which is equivalent to the heat conductivity of the polyurethane hard foam prepared by using the existing non-environment-friendly foaming agent.
Example 2
The polyurethane hard foam additive provided in example 2 and the preparation method thereof are the same as those in example 1, and are not described herein.
Example 2 also provides a polyurethane rigid foam obtained by mixing and foaming a polyether composition and a polymeric MDI, the mass ratio of the polyether composition to the polymeric MDI mixture being 1:1.2, the polyether composition comprises the following components in percentage by mass: 56.5% of polyether polyol, 20% of polyester polyol, 3% of catalyst, 3% of silicone oil, 15% of foaming agent and 2.5% of water; wherein the polyether polyol is 4110 product purchased from Hebei eastern chemical industry, the polyester polyol is 3152 product purchased from Spanish chemical industry, the catalyst is N, N-dimethylcyclohexylamine purchased from winning, and the foaming agent comprises pentane 5%, LBA 3%, HCFO-1233xf 5% and R6002%; the polymeric MDI mixture comprises, in mass percent, BASF M20S 97%, the polyurethane hard foam additive of example 2 3%.
The polyurethane hard foam of example 2 was tested three times for heat conductivity, and the results were 0.0160w/m.k, 0.0158w/m.k, and 0.0157w/m.k, respectively, and it was found that the heat conductivity of the polyurethane hard foam of example 2 was also about 0.016w/m.k, which is equivalent to the heat conductivity of the polyurethane hard foam prepared by using the existing non-environment-friendly foaming agent. From examples 1 and 2, it is clear that the addition of polyurethane hard foam additives can be achieved in either polyether compositions or polymeric MDI.
Example 3
The polyurethane hard foam additive provided in the embodiment 3 comprises the following components in percentage by mass: 70% of perfluoro-4-methyl-2-pentene; polyoxyethylene alcohol 8%; 22% of nano silicon dioxide.
The preparation method of the polyurethane hard foam additive provided in example 3 is the same as that in example 1, and will not be described here again.
The addition amount and the preparation method of the polyurethane hard foam of example 3 were carried out with reference to example 1, except that the polyurethane hard foam additive was prepared in example 3.
The polyurethane hard foam of the embodiment 3 is tested for heat conductivity coefficient, and the test method is tested according to the GB/T10294-2008 method, and the result is 0.0159w/m.k, which shows that the polyurethane hard foam additive of the scheme can play a role in reducing the heat conductivity coefficient of the polyurethane hard foam within a certain proportioning range.
Comparative example 1
Comparative example 1 perfluoro-4-methyl-2-pentene was not prepared in advance as a polyurethane hard foam additive, but perfluoro-4-methyl-2-pentene was directly added to a polyether composition, and the polyether composition of comparative example 1 included in mass percent: 45% -55% of polyether polyol; 14% -38% of polyester polyol; 1% -3% of a catalyst; 1% -3% of silicone oil; 10% -20% of foaming agent; 1-3% of water; 1 to 5 percent of perfluoro-4-methyl-2-pentene.
The delamination of the polyether composition of comparative example 1 was observed, and it was found that although the polyether composition was clear and transparent and not delaminated on the 1 st day of the preparation, delamination occurred due to turbidity of the polyether composition on the 5 th day of the preparation. Indicating that perfluoro-4-methyl-2-pentene cannot be added directly to polyether compositions without phacoemulsification, and that it will delaminate and not be stored.
Comparative example 2
The polyether composition of comparative example 2 was not added with the polyurethane hard foam additive of the present application, but nano silica was directly added to the polyether composition, and the polyether composition of comparative example 2 comprises, in mass percent: 45% -55% of polyether polyol; 14% -38% of polyester polyol; 1% -3% of a catalyst; 1% -3% of silicone oil; 10% -20% of foaming agent; 1-3% of water; 1 to 5 percent of nano silicon dioxide.
The delamination of the polyether composition of comparative example 2 was observed, and it was found that although the polyether composition was clear and transparent and not delaminated on the 1 st day of the preparation, the delamination occurred due to turbidity of the polyether composition on the 5 th day of the preparation. Indicating that the nanosilica cannot be added directly to the polyether composition without phacoemulsification, which would delaminate and not be stored.
Comparative example 3
The polymeric MDI of comparative example 3 was not added with the polyurethane hard foam additive of the present application, but perfluoro-4-methyl-2-pentene was directly added to the polymeric MDI, which included, in mass%, BASF M20S 95-99% and polymeric MDI1% -5%.
Observing delamination of the polymeric MDI of comparative example 3, it was found that delamination occurred on day 5 of the preparation while the polymeric MDI was clear and transparent and not delaminated on day 1 of the preparation. Indicating that perfluoro-4-methyl-2-pentene, which is not directly incorporated into polymeric MDI during processing without phacoemulsification, will delaminate and not be stored.
Comparative example 4
The polymeric MDI of comparative example 4 was not added with the polyurethane hard foam additive of the present application, but nano silica was directly added to the polymeric MDI, which included, in mass%, BASF M20S 95-99%, nano silica 1% -5%.
Observing delamination of the polymeric MDI of comparative example 4, it was found that delamination occurred on day 5 of the preparation while the polymeric MDI was clear and transparent and not delaminated on day 1 of the preparation. It is shown that nano-silica cannot be directly added to polymeric MDI without phacoemulsification process, and it delaminates and does not have a satisfactory storability.
Comparative example 5
Comparative example 5 differs from example 1 in that the polyurethane hard foam additive of comparative example 5 comprises, in mass percent: perfluoro-4-methyl-2-pentene 85%; 15% of polyoxyethylene alcohol. The preparation of the polyurethane hard foam additive of comparative example 5 was carried out with reference to example 1.
Both the addition amount and the preparation method of the polyurethane hard foam of comparative example 5 were carried out with reference to example 1, except that the polyurethane hard foam additive was prepared in comparative example 5.
The polyurethane hard foam of comparative example 5 was tested for thermal conductivity, and the test method was tested according to GB/T10294-2008 and found to be 0.0195w/m.k, indicating that the polyurethane hard foam additive prepared from perfluoro-4-methyl-2-pentene and polyoxyethylene alcohol alone cannot function to reduce the thermal conductivity of the polyurethane hard foam.
Comparative example 6
Comparative example 6 differs from example 1 in that the polyurethane hard foam additive of comparative example 6 comprises, in mass percent: 80% of nano silicon dioxide; 20% of polyoxyethylene alcohol. The preparation of the polyurethane hard foam additive of comparative example 6 was carried out with reference to example 1.
The addition amount and the preparation method of the polyurethane hard foam of comparative example 6 were both carried out with reference to example 1, except that the polyurethane hard foam additive was prepared in comparative example 6.
The polyurethane hard foam of comparative example 6 is tested for heat conductivity coefficient, and the test method is tested according to GB/T10294-2008 method, and the result is 0.0198w/m.k, which shows that the polyurethane hard foam additive prepared from nano silicon dioxide and polyoxyethylene alcohol can not reduce the heat conductivity coefficient of the polyurethane hard foam.
Comparative example 7
The composition of the polyurethane hard foam additive of comparative example 7 is the same as that of example 1, and the preparation method of the polyurethane hard foam additive of comparative example 7 comprises the following steps:
adding perfluoro-4-methyl-2-pentene, polyoxyethylene alcohol and nano silicon dioxide into an emulsifying machine according to a proportion, and emulsifying and mixing to obtain a polyurethane hard foam additive of comparative example 7;
wherein, the power of the emulsifying machine is 80 kilowatts, and the rotating speed of the emulsifying machine is 30000rpm; the emulsification time was 30min.
The polyurethane hard foam additive obtained in comparative example 7 was layered, which indicates that perfluoro-4-methyl-2-pentene and nano silica could not be well dissolved by the emulsification process alone, and the polyurethane hard foam additive of the present application could not be obtained.
Comparative example 8
The composition of the polyurethane hard foam additive of comparative example 8 is the same as that of example 1, and the preparation method of the polyurethane hard foam additive of comparative example 8 comprises the following steps:
adding perfluoro-4-methyl-2-pentene, polyoxyethylene alcohol and nano silicon dioxide into an emulsifying machine according to the proportion;
emulsifying and mixing under the condition of 800pa of vacuum degree to obtain the polyurethane hard foam additive of the comparative example 8;
wherein, the power of the emulsifying machine is 80 kilowatts, and the rotating speed of the emulsifying machine is 30000rpm; the emulsification time was 30min.
The polyurethane hard foam additive obtained in comparative example 8 was layered, which means that perfluoro-4-methyl-2-pentene and nano silica could not be well dissolved even if emulsified under vacuum, and the polyurethane hard foam additive of the present application could not be obtained.
Comparative example 9
The composition of the polyurethane hard foam additive of comparative example 9 is the same as that of example 1, and the preparation method of the polyurethane hard foam additive of comparative example 9 comprises the following steps:
adding perfluoro-4-methyl-2-pentene, polyoxyethylene alcohol and nano silicon dioxide into an emulsifying machine according to the proportion;
emulsifying and mixing under the conditions that the ultrasonic power is 400W and the ultrasonic frequency is 30HZ to obtain the polyurethane hard foam additive of the comparative example 9;
wherein, the power of the emulsifying machine is 80 kilowatts, and the rotating speed of the emulsifying machine is 30000rpm; the emulsification time is 30min, and the ultrasonic wave is continuously carried out for 10s at 10 s.
The polyurethane hard foam additive obtained in comparative example 9 also had delamination, which indicates that perfluoro-4-methyl-2-pentene and nano silica could not be well dissolved by the ultrasonic emulsification process alone, and the polyurethane hard foam additive of the present application could not be obtained.
Finally, it should be noted that: the above embodiments are only for illustrating the technical solution of the present application, and not for limiting the same; although the present application has been described in detail with reference to the foregoing embodiments, it should be understood by those of ordinary skill in the art that: the technical scheme described in the foregoing embodiments can be modified or some or all of the technical features thereof can be replaced by equivalents; such modifications and substitutions do not depart from the spirit of the corresponding technical solutions from the scope of the technical solutions of the embodiments of the present application.
Furthermore, those skilled in the art will appreciate that while some embodiments herein include some features but not others included in other embodiments, combinations of features of different embodiments are meant to be within the scope of the present application and form different embodiments. For example, in the claims below, any of the claimed embodiments may be used in any combination. The information disclosed in this background section is only for enhancement of understanding of the general background of the application and should not be taken as an acknowledgement or any form of suggestion that this information forms the prior art already known to a person skilled in the art.
Claims (11)
1. The polyurethane hard foam additive is characterized by comprising the following components in percentage by mass:
70% -80% of perfluoro-4-methyl-2-pentene;
5% -10% of polyoxyethylene alcohol;
10% -25% of nano silicon dioxide;
the preparation method of the polyurethane hard foam additive comprises the following steps:
and emulsifying and mixing the raw materials according to the proportion under the vacuum and ultrasonic conditions to obtain the polyurethane hard foam additive.
2. The method for preparing the polyurethane hard foam additive according to claim 1, wherein the polyurethane hard foam additive is obtained by emulsifying and mixing raw materials according to a proportion under vacuum and ultrasonic conditions.
3. The method for preparing a polyurethane hard foam additive according to claim 2, wherein the preparation method satisfies at least one of the following conditions a to D:
A. the vacuum degree of the vacuum is 1-1000 pa;
B. the power of the ultrasonic wave is 50-500W, the frequency of the ultrasonic wave is 20-40 HZ, and the ultrasonic wave is continuously carried out for 5-15 s after 5-15 s;
C. the power of the emulsifying machine is 1.5-100 kilowatts, and the rotating speed of the emulsifying machine is 5000-50000 rpm;
D. the emulsification time is 20-40 min.
4. A polyurethane hard foam, characterized in that the raw materials thereof comprise the polyurethane hard foam additive as claimed in claim 1.
5. The polyurethane hard foam according to claim 4, characterized in that the polyurethane hard foam is obtained by mixing and foaming a polyether composition and a polymeric MDI, and the polyurethane hard foam additive is added in the polyether composition and/or in the polymeric MDI.
6. The rigid polyurethane foam according to claim 5, wherein the mass ratio of the polyether composition to the polymeric MDI is 1: (1-1.5).
7. The polyurethane hard foam according to claim 5, wherein when the polyurethane hard foam additive is added to the polyether composition, the polyurethane hard foam additive is 1% -5% by mass in the polyether composition; when the polyurethane hard foam additive is added into the polymeric MDI, the mass percentage of the polyurethane hard foam additive in the polymeric MDI is 1% -5%.
8. The polyurethane rigid foam according to claim 7, wherein the polyether composition comprises, in mass percent:
45% -55% of polyether polyol;
14% -38% of polyester polyol;
1% -3% of a catalyst;
1% -3% of silicone oil;
10% -20% of foaming agent;
1% -3% of water;
1% -5% of polyurethane hard foam additive.
9. The polyurethane rigid foam according to claim 8, wherein the blowing agent is selected from the group consisting of one or more of pentane, methyl formate, 245fa, LBA, R600a, R-152a, R-134a, R-1234yf, komu opteon1100, komu opteon1150, HCFO-1224yd, HCFO-1234ze, HCFO-1243zf, and HCFO-1233 xf.
10. The polyurethane rigid foam according to claim 8, wherein the catalyst comprises an amine-based catalyst and/or a metal-based catalyst, the amine-based catalyst comprising one or more of N, N-dimethylcyclohexylamine, pentamethyldiethylenetriamine, N-dimethylbenzylamine, 1,3, 5-tris (dimethylaminopropyl) hexahydrotriazine, bis (2-dimethylaminoethyl) ether, and triethylenediamine; the metal catalyst comprises one or more of organotin, organobismuth or organozinc compounds.
11. Use of the polyurethane rigid foam according to any of claims 4-10 in refrigerators, freezers, spraying, solar, thermal pipelines, construction applications.
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| CN111471210A (en) * | 2020-05-26 | 2020-07-31 | 南京红宝丽聚氨酯有限公司 | Polyurethane composition of pentane co-foaming system and preparation method of polyurethane rigid foam |
| CN112175158A (en) * | 2020-09-25 | 2021-01-05 | 海信容声(广东)冰箱有限公司 | Refrigerator, hard polyurethane foam and preparation method of hard polyurethane foam |
| WO2022142553A1 (en) * | 2021-01-04 | 2022-07-07 | 海信容声(广东)冰箱有限公司 | Rigid polyurethane foam and preparation method therefor |
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