CN117024696A - Polyurethane rigid foam with low heat conductivity coefficient and preparation method thereof - Google Patents
Polyurethane rigid foam with low heat conductivity coefficient and preparation method thereof Download PDFInfo
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- CN117024696A CN117024696A CN202310874943.6A CN202310874943A CN117024696A CN 117024696 A CN117024696 A CN 117024696A CN 202310874943 A CN202310874943 A CN 202310874943A CN 117024696 A CN117024696 A CN 117024696A
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- white
- foaming agent
- nanocellulose
- catalyst
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- 239000006260 foam Substances 0.000 title claims abstract description 63
- 229920002635 polyurethane Polymers 0.000 title claims abstract description 47
- 239000004814 polyurethane Substances 0.000 title claims abstract description 47
- 238000002360 preparation method Methods 0.000 title claims abstract description 16
- 239000000463 material Substances 0.000 claims abstract description 170
- 239000004088 foaming agent Substances 0.000 claims abstract description 66
- 239000004721 Polyphenylene oxide Substances 0.000 claims abstract description 60
- 229920000570 polyether Polymers 0.000 claims abstract description 60
- 229920001046 Nanocellulose Polymers 0.000 claims abstract description 53
- 239000012948 isocyanate Substances 0.000 claims abstract description 45
- 229920005862 polyol Polymers 0.000 claims abstract description 42
- 150000003077 polyols Chemical class 0.000 claims abstract description 42
- 239000003054 catalyst Substances 0.000 claims abstract description 38
- -1 isocyanate compounds Chemical class 0.000 claims abstract description 36
- 229920005906 polyester polyol Polymers 0.000 claims abstract description 25
- 229920002545 silicone oil Polymers 0.000 claims abstract description 25
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 25
- 239000002994 raw material Substances 0.000 claims abstract description 10
- 239000000203 mixture Substances 0.000 claims description 52
- 150000002513 isocyanates Chemical class 0.000 claims description 41
- 238000002156 mixing Methods 0.000 claims description 33
- 238000006243 chemical reaction Methods 0.000 claims description 30
- 238000003756 stirring Methods 0.000 claims description 25
- OFBQJSOFQDEBGM-UHFFFAOYSA-N Pentane Chemical compound CCCCC OFBQJSOFQDEBGM-UHFFFAOYSA-N 0.000 claims description 22
- 238000000034 method Methods 0.000 claims description 22
- 238000009835 boiling Methods 0.000 claims description 17
- 239000004604 Blowing Agent Substances 0.000 claims description 14
- 238000005187 foaming Methods 0.000 claims description 12
- NNPPMTNAJDCUHE-UHFFFAOYSA-N isobutane Chemical compound CC(C)C NNPPMTNAJDCUHE-UHFFFAOYSA-N 0.000 claims description 12
- TZIHFWKZFHZASV-UHFFFAOYSA-N methyl formate Chemical compound COC=O TZIHFWKZFHZASV-UHFFFAOYSA-N 0.000 claims description 12
- 230000008569 process Effects 0.000 claims description 12
- 238000001132 ultrasonic dispersion Methods 0.000 claims description 10
- MSSNHSVIGIHOJA-UHFFFAOYSA-N pentafluoropropane Chemical compound FC(F)CC(F)(F)F MSSNHSVIGIHOJA-UHFFFAOYSA-N 0.000 claims description 9
- FFTOUVYEKNGDCM-OWOJBTEDSA-N (e)-1,3,3-trifluoroprop-1-ene Chemical compound F\C=C\C(F)F FFTOUVYEKNGDCM-OWOJBTEDSA-N 0.000 claims description 6
- LVGUZGTVOIAKKC-UHFFFAOYSA-N 1,1,1,2-tetrafluoroethane Chemical compound FCC(F)(F)F LVGUZGTVOIAKKC-UHFFFAOYSA-N 0.000 claims description 6
- SXKNYNUXUHCUHX-UHFFFAOYSA-N 1,1,2,3,3,4-hexafluorobut-1-ene Chemical compound FCC(F)(F)C(F)=C(F)F SXKNYNUXUHCUHX-UHFFFAOYSA-N 0.000 claims description 6
- ZXRJUEKCPLLSJP-UHFFFAOYSA-N 1,1-difluoroethane 1,1,1,2-tetrafluoroethane Chemical compound FC(C)F.FC(CF)(F)F ZXRJUEKCPLLSJP-UHFFFAOYSA-N 0.000 claims description 6
- 239000001282 iso-butane Substances 0.000 claims description 6
- IJDNQMDRQITEOD-UHFFFAOYSA-N n-butane Chemical compound CCCC IJDNQMDRQITEOD-UHFFFAOYSA-N 0.000 claims description 6
- 230000035484 reaction time Effects 0.000 claims description 4
- 229920005830 Polyurethane Foam Polymers 0.000 claims description 3
- 150000001875 compounds Chemical class 0.000 claims description 3
- 239000011496 polyurethane foam Substances 0.000 claims description 3
- 238000004519 manufacturing process Methods 0.000 claims 2
- 230000000694 effects Effects 0.000 description 16
- 230000002776 aggregation Effects 0.000 description 10
- 238000010899 nucleation Methods 0.000 description 9
- 230000006911 nucleation Effects 0.000 description 9
- 210000004027 cell Anatomy 0.000 description 7
- 239000007789 gas Substances 0.000 description 7
- 238000005054 agglomeration Methods 0.000 description 6
- 238000003860 storage Methods 0.000 description 5
- 238000004220 aggregation Methods 0.000 description 4
- 238000011160 research Methods 0.000 description 4
- 238000012360 testing method Methods 0.000 description 4
- GSEJCLTVZPLZKY-UHFFFAOYSA-N Triethanolamine Chemical compound OCCN(CCO)CCO GSEJCLTVZPLZKY-UHFFFAOYSA-N 0.000 description 3
- 230000009286 beneficial effect Effects 0.000 description 3
- 230000015572 biosynthetic process Effects 0.000 description 3
- 229920002678 cellulose Polymers 0.000 description 3
- 239000001913 cellulose Substances 0.000 description 3
- 239000006185 dispersion Substances 0.000 description 3
- 230000007613 environmental effect Effects 0.000 description 3
- 210000000497 foam cell Anatomy 0.000 description 3
- 229920003023 plastic Polymers 0.000 description 3
- 239000004033 plastic Substances 0.000 description 3
- 230000001737 promoting effect Effects 0.000 description 3
- 230000005855 radiation Effects 0.000 description 3
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 description 2
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 2
- 238000010521 absorption reaction Methods 0.000 description 2
- 230000009471 action Effects 0.000 description 2
- 239000012752 auxiliary agent Substances 0.000 description 2
- 230000000052 comparative effect Effects 0.000 description 2
- 230000003111 delayed effect Effects 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 238000002309 gasification Methods 0.000 description 2
- 230000017525 heat dissipation Effects 0.000 description 2
- 239000001257 hydrogen Substances 0.000 description 2
- 229910052739 hydrogen Inorganic materials 0.000 description 2
- 239000002608 ionic liquid Substances 0.000 description 2
- 238000005457 optimization Methods 0.000 description 2
- 238000006116 polymerization reaction Methods 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- IMNIMPAHZVJRPE-UHFFFAOYSA-N triethylenediamine Chemical compound C1CN2CCN1CC2 IMNIMPAHZVJRPE-UHFFFAOYSA-N 0.000 description 2
- NWIICCMMNLMQMY-UHFFFAOYSA-K 1-butyl-3-methylimidazol-3-ium phosphate Chemical compound [O-]P([O-])([O-])=O.CCCCn1cc[n+](C)c1.CCCCn1cc[n+](C)c1.CCCCn1cc[n+](C)c1 NWIICCMMNLMQMY-UHFFFAOYSA-K 0.000 description 1
- 241000186809 Kurthia Species 0.000 description 1
- CBENFWSGALASAD-UHFFFAOYSA-N Ozone Chemical compound [O-][O+]=O CBENFWSGALASAD-UHFFFAOYSA-N 0.000 description 1
- 238000009825 accumulation Methods 0.000 description 1
- 229910002092 carbon dioxide Inorganic materials 0.000 description 1
- 239000001569 carbon dioxide Substances 0.000 description 1
- 239000000460 chlorine Substances 0.000 description 1
- 229910052801 chlorine Inorganic materials 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 230000032798 delamination Effects 0.000 description 1
- 230000002349 favourable effect Effects 0.000 description 1
- 238000009413 insulation Methods 0.000 description 1
- 230000007246 mechanism Effects 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 239000005543 nano-size silicon particle Substances 0.000 description 1
- 239000002159 nanocrystal Substances 0.000 description 1
- 239000002667 nucleating agent Substances 0.000 description 1
- UKODFQOELJFMII-UHFFFAOYSA-N pentamethyldiethylenetriamine Chemical compound CN(C)CCN(C)CCN(C)C UKODFQOELJFMII-UHFFFAOYSA-N 0.000 description 1
- 239000011148 porous material Substances 0.000 description 1
- 230000002035 prolonged effect Effects 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- 235000012239 silicon dioxide Nutrition 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 238000012546 transfer 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
- 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
- C08G18/4081—Mixtures of compounds of group C08G18/64 with other macromolecular compounds
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/08—Processes
- C08G18/0838—Manufacture of polymers in the presence of non-reactive compounds
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/08—Processes
- C08G18/10—Prepolymer processes involving reaction of isocyanates or isothiocyanates with compounds having active hydrogen in a first reaction step
-
- 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
- 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
- C08G18/64—Macromolecular compounds not provided for by groups C08G18/42 - C08G18/63
- C08G18/6484—Polysaccharides and derivatives thereof
-
- 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
- C08J9/146—Halogen containing compounds containing carbon, halogen and hydrogen only only fluorine as halogen atoms
-
- 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
- C08K5/16—Nitrogen-containing compounds
- C08K5/34—Heterocyclic compounds having nitrogen in the ring
- C08K5/3442—Heterocyclic compounds having nitrogen in the ring having two nitrogen atoms in the ring
- C08K5/3445—Five-membered rings
-
- 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
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J2205/00—Foams characterised by their properties
- C08J2205/10—Rigid foams
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J2375/00—Characterised by the use of polyureas or polyurethanes; Derivatives of such polymers
- C08J2375/04—Polyurethanes
- C08J2375/06—Polyurethanes from polyesters
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J2375/00—Characterised by the use of polyureas or polyurethanes; Derivatives of such polymers
- C08J2375/04—Polyurethanes
- C08J2375/08—Polyurethanes from polyethers
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- Chemical & Material Sciences (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Manufacturing & Machinery (AREA)
- Polyurethanes Or Polyureas (AREA)
Abstract
The invention belongs to the technical field of polyurethane hard foam, and particularly relates to a polyurethane hard foam with low heat conductivity coefficient and a preparation method thereof, wherein raw materials comprise black materials and white materials, the black materials comprise isocyanate compounds, the white materials comprise polyether polyol, polyester polyol, silicone oil, a first catalyst, water, nanocellulose, 1-butyl-3-methylimidazole hexafluorophosphate and a first foaming agent, the mass of the first foaming agent accounts for 8% -15% of the total mass of the white materials, and the mass of the first foaming agent accounts for the sum of the mass of polyether polyol, polyester polyol, silicone oil, the first catalyst, water, nanocellulose and 1-butyl-3-methylimidazole hexafluorophosphate, the mass of the nanocellulose accounts for 0.02% -3%, and the mass of the 1-butyl-3-methylimidazole hexafluorophosphate accounts for 0.05% -3%; and controlling the viscosity of the white material at 20 ℃ to be 500-800 MPa.S. The heat conductivity coefficient of the polyurethane hard foam reaches below 0.018 w/m.k, and the white material can be stored for a long time.
Description
Technical Field
The invention belongs to the technical field of polyurethane hard foam, and particularly relates to a polyurethane hard foam with a low heat conductivity coefficient and a preparation method thereof.
Background
The technology of polyurethane hard foam is continuously advanced, the environmental protection performance of the adopted environmental protection foaming agent can reach ODP (ozone depletion potential value) =0 and GWP (global warming potential value) ≡0, and the heat conductivity coefficient of the hard polyurethane foam is increased due to the use of the environmental protection foaming agent. In the prior art, the heat conductivity coefficient is reduced by adopting a method of adding an auxiliary agent, a nucleating agent and nano silicon dioxide or adding an auxiliary agent or a foaming agent into the black material, and the heat conductivity coefficient can basically reach the level of 0.019 w/m.k. However, the thermal conductivity is still reduced, which is not possible with the state of the art.
The heat conductivity of the polyurethane foam material is an important reason for influencing the heat insulation performance of the foamed product, and the main mechanism of influencing the heat conductivity of the foam is as follows: ג Foam = ג Gas and its preparation method （50%）+ ג Plastic material （25%）+ ג Radiation of (25%) in which ג Gas and its preparation method : heat conducted through the gas within the cells; ג Plastic material : heat conducted through the solid plastic; ג Radiation of : heat transfer through the cells by thermal radiation. Thus, the thermal conductivity of the rigid foam system is primarily determined by the fine density of cells in the foam, cell diameter, thermally conductive gas within the foam, and the like.
In order to reduce the heat conductivity of polyurethane rigid foam, the current method is to make the foam cells form earlier, the gas with lower heat conductivity in the foam cells and the diameter of the foam cells smaller. However, the decrease in thermal conductivity of polyurethane rigid foam is limited, and it is difficult to break through the level of 0.019 w/m.k.
Disclosure of Invention
The invention aims to overcome the defect that the heat conductivity coefficient of polyurethane hard foam needs to be further reduced in the prior art, and provides a polyurethane hard foam with low heat conductivity coefficient and a preparation method thereof, wherein the heat conductivity coefficient of the polyurethane hard foam is less than 0.018 w/m.k, and white materials can be stored for a long time.
In order to achieve the above object, in a first aspect, the present invention provides a polyurethane hard foam with a low thermal conductivity, the raw materials of the polyurethane hard foam comprise black materials and white materials, the black materials comprise isocyanate compounds, the white materials comprise polyether polyol, polyester polyol, silicone oil, a first catalyst and water, the white materials further comprise nanocellulose, 1-butyl-3-methylimidazole hexafluorophosphate and a first foaming agent, wherein the mass of the first foaming agent accounts for 8% -15% of the total mass of the white materials, and the sum of the masses of the polyether polyol, the polyester polyol, the silicone oil, the first catalyst and water and nanocellulose, 1-butyl-3-methylimidazole hexafluorophosphate accounts for 85% -92% of the total mass of the white materials; and the amount of the nanocellulose accounts for 0.02-3 percent and the amount of the 1-butyl-3-methylimidazole hexafluorophosphate accounts for 0.05-3 percent based on the sum of the mass of polyether polyol, polyester polyol, silicone oil, a first catalyst, water, nanocellulose and 1-butyl-3-methylimidazole hexafluorophosphate; and controlling the viscosity of the white material at 20 ℃ to be 500-800 MPa.S.
Preferably, the first foaming agent is selected from pentane, methyl formate, 1-chlorine, 3,3 trifluoropropene, hexafluorobutene, pentafluoropropane, n-butane, isobutane, difluoroethane tetrafluoroethane, 2, 3-tetrafluoropropene, trans-1, 4-hexafluoro-2-butene tetrafluoroethane, 2, 3-tetrafluoropropene trans-1, 4-hexafluoro-2-butene.
In some preferred embodiments of the invention, the isocyanate-based compound is a polyether modified isocyanate prepolymer and the viscosity of the black material is controlled to be 500-2700 mpa.s at 20 ℃.
More preferably, the pre-polymerization raw material of the polyether modified isocyanate prepolymer comprises the following components in percentage by mass: based on the total mass of the raw materials, 68-89.95% of isocyanate, 10-30% of polyether polyol and 0.05-2% of second catalyst.
More preferably, the black material further comprises a second foaming agent with a boiling point not higher than 15 ℃, wherein the mass of the second foaming agent accounts for 5% -10% of the total amount of the black material, the mass of the polyether modified isocyanate prepolymer accounts for 90% -95% of the total amount of the black material, and the viscosity of the black material at 20 ℃ is controlled to be 500-600MPa & S.
Further preferably, the boiling point of the first foaming agent is higher than 15 ℃, the mass of the first foaming agent accounts for 8-10% of the total mass of the white material, and the sum of the masses of the polyether polyol, the polyester polyol, the silicone oil, the first catalyst, the water, the nanocellulose and the 1-butyl-3-methylimidazole hexafluorophosphate accounts for 90-92% of the total mass of the white material; and the viscosity of the white material at 20 ℃ is controlled to be 700-800 MPa.S.
Further preferably, the first blowing agent is at least one selected from pentane, methyl formate, 1-chloro, 3 trifluoropropene, hexafluorobutene, the second foaming agent is selected from the group consisting of pentafluoropropane, n-butane, isobutane, difluoroethane tetrafluoroethane, 2, 3-tetrafluoropropene, trans-1, 4-hexafluoro-2-butene tetrafluoroethane, 2, 3-tetrafluoropropene trans-1, 4-hexafluoro-2-butene.
In some preferred embodiments of the invention, the mass ratio of the black material to the white material is 1.1-1.5:1.
In some preferred embodiments of the present invention, the white material comprises, based on the sum of the mass of polyether polyol, polyester polyol, silicone oil, first catalyst and water, and nanocellulose, 1-butyl-3-methylimidazole hexafluorophosphate, the amount of polyether polyol is 52% -85.9%, the amount of polyester polyol is 10% -30%, the amount of silicone oil is 1.5% -4%, the amount of first catalyst is 1.5% -4%, and the amount of water is 1% -4%.
In some preferred embodiments of the invention, the polyurethane rigid foam has a thermal conductivity of less than 0.018W/m.k.
In a second aspect, the present invention provides a method for preparing a polyurethane hard foam with a low thermal conductivity, where the polyurethane hard foam is the polyurethane hard foam according to the first aspect, and the method includes: and mixing and foaming the white material and the black material.
The preparation process of the white material comprises the following steps:
mixing polyether polyol, polyester polyol, silicone oil, a first catalyst, water, nanocellulose, 1-butyl-3-methylimidazole hexafluorophosphate and a first foaming agent, and then sequentially stirring and dispersing and ultrasonic dispersing; wherein the conditions for stirring and dispersing comprise: stirring speed is 1800-2200rpm, and stirring time is 25-35min; the conditions for the ultrasonic dispersion include: the ultrasonic frequency is 20-40Hz, the power is 800-1200W, the amplitude is 70% -90%, and the ultrasonic time is 30-50min.
In some preferred embodiments of the present invention, the preparation method further comprises a process of preparing a black material:
carrying out a first prepolymerization reaction on isocyanate, polyether polyol and a second catalyst to obtain polyether modified isocyanate prepolymer; wherein the conditions of the first prepolymerization reaction comprise: the reaction temperature is 50-70 ℃ and the reaction time is 1-3h;
and then performing a second mixing with a second blowing agent, the conditions of the second mixing comprising: the mixing temperature is 5-12 ℃, and the mixing time is 20-40min.
In some preferred embodiments of the present invention, in the mixed foaming, the feeding temperature of the black material is controlled to 5-12 ℃, and the feeding temperature of the white material is controlled to 25-35 ℃.
The beneficial effects are that:
according to research, the nano-cellulose is adopted in the white material, although nucleation can be promoted, because the single nano-crystal contained in the nano-cellulose has special mechanical properties, surface modification is easy to carry out and the like, the strong hydrogen bond of the nano-cellulose has natural affinity to polyether polyol, the effect of reducing the local stress of the polyol interface in the white material is achieved, the nucleation effect of energy aggregation can be obtained under the mechanical action of the strong hydrogen bond, and meanwhile, the cell size is obviously reduced. However, the added nanocellulose is easy to agglomerate, the nucleation effect of the nanocellulose is affected, and white materials are easy to delaminate and difficult to store. Moreover, it is particularly important to research and find that too great a viscosity difference between the black material and the white material affects the mixing effect in the case of adopting nano cellulose in the white material, further affects the exothermic reaction process, affects the formation of bubbles, and finally affects the heat conductivity coefficient. Based on this, the present invention has been further proposed.
According to the technical scheme, particularly, the ionic liquid 1-butyl-3-methylimidazole hexafluorophosphate with proper amount is added into the white material containing the nanocellulose, so that the agglomeration of the nanocellulose in polyether polyol can be reduced, the mixing of the nanocellulose is promoted, the capability of the nanocellulose for reducing the local stress effect of the polyol interface in the white material is improved, the viscosity of the white material is reduced under the action of the 1-butyl-3-methylimidazole hexafluorophosphate, meanwhile, the ionic liquid dispersing effect is added, the agglomeration of the nanocellulose in the polyether polyol is greatly reduced, the enhanced nucleation effect is facilitated to be obtained, and meanwhile, the storage time of the white material is prolonged; and the viscosity is further adjusted by adding the first foaming agent, the viscosity of the white material is reduced in a proper range, the viscosity difference between the white material and the black material is reduced, and the best mixing effect is obtained.
The invention can obtain more bubbles on the formation of the bubbles, the formed bubbles have smaller pore diameter and tighter arrangement, and the heat in the later treatment period is uniformly dispersed, so that the problem of bubble breaking caused by excessive heat is avoided, and the heat conductivity coefficient is lower than 0.018 w/m.k.
Further research shows that the foaming process is a comprehensive process of chemical and physical reaction, the initial reaction stage is exothermic reaction of isocyanate and water to generate carbon dioxide, and then the physical foaming agent absorbs heat to volatilize to form bubbles. The foam is formed by the surging of bubbles in the later reaction period, so that heat cannot be emitted, and a large amount of heat is accumulated to raise the heat of gas in the foam so as to destroy the cell structure. Therefore, the formation of bubbles at the early stage cannot be pursued only in the reaction coordination, and the situation that bubbles are broken due to the accumulation of heat at the later stage cannot be solved. In the preferred scheme of the invention, foaming agents with different boiling points and proper proportions are respectively adopted in the black material and the white material, and the polyether modified isocyanate prepolymer is preferably adopted in the black material, so that the process of heat dissipation can be combined, the characteristics of low-to-high initial heat quantity in the foaming process, the characteristic of heat absorption and gasification by each foaming agent in the middle stage and strong heat absorption and heat reduction by each foaming agent in the later stage are met, the heat is respectively released in different stages, the heat aggregation in the later reaction stage is reduced, the foam breaking is reduced, and the heat conductivity of the polyurethane hard foam is further reduced. Moreover, in a preferred class of blowing agents, the gas in the cells it produces is an environmentally friendly blowing agent that meets odp=0, gwp≡0.
Detailed Description
In the present disclosure, the terms "first," "second," and "second" are used for descriptive purposes only and are not to be construed as indicating or implying a relative importance or implying a number of technical features being indicated. Thus, a feature defining "a first" or "a second" may explicitly or implicitly include one or more such feature. In the description of the present invention, the meaning of "a plurality" is two or more, unless explicitly defined otherwise.
The endpoints and any values of the ranges disclosed herein are not limited to the precise range or value, and are understood to encompass values approaching those ranges or values. For numerical ranges, one or more new numerical ranges may be found between the endpoints of each range, between the endpoint of each range and the individual point value, and between the individual point value, in combination with each other, and are to be considered as specifically disclosed herein. Wherein the terms "optional" and "optionally" mean either comprising or not comprising (or may not be present).
In a first aspect, the invention provides a polyurethane hard foam with a low heat conductivity coefficient, which comprises raw materials including black materials and white materials, wherein the black materials comprise isocyanate compounds, the white materials comprise polyether polyol, polyester polyol, silicone oil, a first catalyst and water, the white materials further comprise nanocellulose, 1-butyl-3-methylimidazole hexafluorophosphate and a first foaming agent, the mass of the first foaming agent accounts for 8% -15% of the total mass of the white materials, and the sum of the mass of the polyether polyol, the polyester polyol, the silicone oil, the first catalyst and water and the mass of nanocellulose, 1-butyl-3-methylimidazole hexafluorophosphate accounts for 85% -92% of the total mass of the white materials; and the amount of the nanocellulose accounts for 0.02-3 percent and the amount of the 1-butyl-3-methylimidazole hexafluorophosphate accounts for 0.05-3 percent based on the sum of the mass of polyether polyol, polyester polyol, silicone oil, a first catalyst, water, nanocellulose and 1-butyl-3-methylimidazole hexafluorophosphate; and controlling the viscosity of the white material at 20 ℃ to be 500-800 MPa.S.
In some embodiments, the first blowing agent may have a boiling point above 15℃or not above 15℃for example the first blowing agent may be selected from pentane, methyl formate, 1-chloro, 3,3 trifluoropropene, hexafluorobutene, pentafluoropropane, n-butane, isobutane, difluoroethane tetrafluoroethane, 2, 3-tetrafluoropropene, trans-1, 4-hexafluoro-2-butene tetrafluoroethane, 2, 3-tetrafluoropropene trans-1, 4-hexafluoro-2-butene.
Further researches show that the viscosity of the isocyanate at 20 ℃ is 150-250MPa.S, the viscosity is lower, the viscosity difference between the isocyanate and the white material is larger, the possibility of uneven material mixing can occur, the mixing time is delayed, the nucleation of nanocellulose is reduced, and when the isocyanate is directly reacted, heat is delayed, so that the heat is increased in the later period of the reaction, the heat is accumulated, the problems of foam breaking and the like are aggravated, and the heat conductivity coefficient is difficult to be further greatly reduced. In some preferred embodiments of the invention, the isocyanate-based compound is a polyether modified isocyanate prepolymer and the viscosity of the black material is controlled to be 500-2700mpa.s at 20 ℃. In the preferred scheme, the polyether modified isocyanate prepolymer is adopted, so that part of reaction heat is released in advance in the prepolymerization process, the reaction heat is reduced in the later stage due to the advanced release of the heat, foam breaking is also reduced, the viscosity of the polyether modified isocyanate prepolymer is improved through prepolymerization, the viscosity deviation of the black material and the white material is reduced, the uniform mixing with the white material containing nano cellulose can be promoted, the agglomeration of the nano cellulose is further reduced, the capability of the nano cellulose for reducing the local stress effect of a polyol interface in the white material is further enhanced, the nucleation effect of the nano cellulose is improved, the later reaction heat is reduced, foam breaking is reduced, and the heat conductivity is further reduced.
More preferably, the pre-polymerization raw material of the polyether modified isocyanate prepolymer comprises the following components in percentage by mass: based on the total mass of the raw materials, 68-89.95% of isocyanate, 10-30% of polyether polyol and 0.05-2% of second catalyst.
More preferably, the black material further comprises a second foaming agent with a boiling point not higher than 15 ℃, wherein the mass of the second foaming agent accounts for 5% -10% of the total amount of the black material, the mass of the polyether modified isocyanate prepolymer accounts for 90% -95% of the total amount of the black material, and the viscosity of the black material at 20 ℃ is controlled to be 500-600MPa & S. According to the preferred scheme, the second foaming agent with the boiling point not higher than 15 ℃ is added, so that the viscosity of the black material containing the polyether modified isocyanate prepolymer is further reduced, the corresponding foaming agents are respectively added into the black material and the white material to form double foaming agents, the viscosity of the black material and the white material are respectively added, the viscosity of the black material is enabled to be closer to that of the white material containing the nanocellulose, the viscosity is improved and controlled to be in a proper range, the viscosity deviation of the black material and the white material containing the nanocellulose is further reduced, the mixing with the white material containing the nanocellulose can be promoted, the possibility of nanocellulose agglomeration is further reduced, the nucleation effect of the nanocellulose is further improved, the later reaction heat is reduced, foam breaking is reduced, and the heat conductivity is further reduced.
Further preferably, the boiling point of the first blowing agent is higher than 15 ℃. In the preferred scheme, the white material is selected to be a first foaming agent with the boiling point higher than 15 ℃, the black material is selected to be a second foaming agent with the boiling point not higher than 15 ℃, and the viscosity of the white material and the viscosity of the black material are close to each other through the blending temperature in the using process, so that the viscosity deviation of the white material and the black material is further reduced, the mixture of the white material and the white material containing nano cellulose can be promoted, the agglomeration of the nano cellulose is reduced, the crystal nucleus effect of the nano cellulose is improved, the later reaction heat is reduced, the foam breaking is reduced, and the heat conductivity coefficient is further reduced.
In the scheme that the boiling point of the first foaming agent is higher than 15 ℃, preferably, the mass of the first foaming agent accounts for 8-10% of the total mass of the white material, and the sum of the mass of the polyether polyol, the polyester polyol, the silicone oil, the first catalyst, the water and the nanocellulose, and the 1-butyl-3-methylimidazole hexafluorophosphate accounts for 90-92% of the total mass of the white material; and the viscosity of the white material at 20 ℃ is controlled to be 700-800 MPa.S. This preferred solution further reduces the thermal conductivity.
In the present invention, the first catalyst or the second catalyst may be any catalyst that is conventionally used to catalyze the reaction between isocyanate and each polyol, and for example, each of the first catalyst or the second catalyst may be at least one of triethanolamine, N-dimethylcyclohexylamine, triethylenediamine, pentamethyldiethylenetriamine, and the like, independently of the other. The first catalyst and the second catalyst may be the same or different.
The first foaming agent can be any foaming agent with a boiling point higher than 15 ℃, and the second foaming agent can be any foaming agent with a boiling point not higher than 15 ℃, so that the purpose of the preferable scheme of the invention can be achieved. Further preferably, the first blowing agent is at least one selected from pentane, methyl formate, 1-chloro, 3 trifluoropropene, hexafluorobutene, the second foaming agent is selected from the group consisting of pentafluoropropane, n-butane, isobutane, difluoroethane tetrafluoroethane, 2, 3-tetrafluoropropene, trans-1, 4-hexafluoro-2-butene tetrafluoroethane, 2, 3-tetrafluoropropene trans-1, 4-hexafluoro-2-butene. According to the preferable scheme, foaming agents with different boiling points are adopted in the black materials and the white materials, and the polyether modified isocyanate prepolymer is adopted in the black materials, so that the heat dissipation process can be combined, the characteristics that the initial heat quantity is low to high in the foaming process, the first foaming agent absorbs heat for gasification in the middle period, the later foaming agent absorbs heat strongly and reduces heat are met, the heat is released respectively in different stages, the heat aggregation in the later reaction period is reduced, foam breaking is reduced, and the heat conductivity coefficient of the polyurethane rigid foam is further reduced.
In some preferred embodiments of the invention, the mass ratio of the black material to the white material is 1.1-1.5:1.
In some preferred embodiments of the present invention, the white material comprises, based on the sum of the mass of polyether polyol, polyester polyol, silicone oil, first catalyst and water, and nanocellulose, 1-butyl-3-methylimidazole hexafluorophosphate, the amount of polyether polyol is 52% -85.9%, the amount of polyester polyol is 10% -30%, the amount of silicone oil is 1.5% -4%, the amount of first catalyst is 1.5% -4%, and the amount of water is 1% -4%.
In some preferred embodiments of the invention, the polyurethane rigid foam has a thermal conductivity of less than 0.018W/m.k.
The polyether polyol, the polyester polyol and the silicone oil can be selected from the corresponding types existing in the preparation field of polyurethane hard foam, can be used for the invention, can achieve the aim of the invention, and are not repeated here. The nanocellulose of the present invention may be any commercially available nanocellulose in the art that is capable of performing the aforementioned nucleation.
In a second aspect, the present invention provides a method for preparing a polyurethane hard foam with a low thermal conductivity, where the polyurethane hard foam is the polyurethane hard foam according to the first aspect, and the method includes: and mixing and foaming the white material and the black material.
The preparation process of the white material comprises the following steps: polyether polyol, polyester polyol, silicone oil, a first catalyst, water, nanocellulose, 1-butyl-3-methylimidazole hexafluorophosphate and a first foaming agent are mixed, and then stirring dispersion and ultrasonic dispersion are sequentially carried out.
Wherein, preferably, the conditions of stirring and dispersing include: stirring speed is 1800-2200rpm, and stirring time is 25-35min; the conditions for the ultrasonic dispersion include: the ultrasonic frequency is 20-40Hz, the power is 800-1200W, the amplitude is 70% -90%, and the ultrasonic time is 30-50min. Compared with the simple mixing of the raw materials of the white material, the preparation process, particularly stirring dispersion and ultrasonic dispersion under specific conditions, can be used for remarkably reducing the agglomeration of the nanocellulose in the polyether polyol, so that the white material is stored for a long time, the mixing and nucleation of the nanocellulose are facilitated, and the heat conductivity coefficient of the polyurethane rigid foam is reduced.
In some preferred embodiments of the present invention, the preparation method further comprises a process of preparing a black material: and (3) carrying out a first prepolymerization reaction on isocyanate, polyether polyol and a second catalyst to obtain polyether modified isocyanate prepolymer.
Wherein preferably, the conditions of the first prepolymerization reaction comprise: the reaction temperature is 50-70 ℃ and the reaction time is 1-3h.
More preferably, the process of preparing the black material further includes: the polyether modified isocyanate prepolymer is then second mixed with a second blowing agent.
Preferably, the conditions of the second mixing include: the mixing temperature is 5-12 ℃, and the mixing time is 20-40min.
In some preferred embodiments of the present invention, in the mixed foaming, the feeding temperature of the black material is controlled to 5-12 ℃, and the feeding temperature of the white material is controlled to 25-35 ℃. In the preferred scheme, the black material and the white material are added with the corresponding foaming agents, and the feeding temperatures of the black material and the white material are controlled to be equal to the feeding temperatures of the black material and the white material, so that the viscosity of the black material and the white material is close to the viscosity of the black material and the white material to the maximum extent, and the heat conductivity coefficient is reduced to the maximum extent. In addition, as the low-boiling point second foaming agent is easy to gasify and quick in reaction, the polyether modified isocyanate prepolymer is adopted in the black material to be mixed with the low-boiling point second foaming agent in a proper proportion under the low-temperature condition of 5-12 ℃, so that the loss of the low-temperature second foaming agent can be avoided, when the low-temperature second foaming agent is mixed, part of the low-temperature second foaming agent is reacted in advance to release heat when foaming is performed at an early stage, and the heat is released at different stages of the high-temperature first foaming agent and the low-temperature second foaming agent respectively, so that heat aggregation at the later stage of reaction is reduced, foam breaking is reduced, and the heat conductivity of the polyurethane rigid foam is further reduced.
Of course, in the mixed foaming of the present invention, the feed temperatures of the black material and the white material may be the same, and may be, for example, 10 to 20 ℃.
The following detailed description of the embodiments of the invention is exemplary and is merely illustrative of the invention and not to be construed as limiting the invention.
Preparation example
The following materials (all by mass) were prepared:
composition A: based on the total mass A, 81% of polyether polyol (purchased from Shanghai optimization chemical Co., ltd.), 10% of polyester polyol (purchased from Spanish chemical Co., ltd.), 3% of silicone oil (purchased from Jiangsu Mei Si De chemical Co., ltd.), 2% of catalyst triethanolamine (purchased from Ying-Chuang industries, shanghai Co., ltd.), and 4% of water.
Composition B: unlike A, nanocellulose (purchased from Shanghai Chen Co., ltd.) was also added 1%, and the amount of polyether polyol was adjusted to 80% to meet 100% by weight of the total.
C: the foaming agent is pentane or pentafluoropropane (HC-245 fa);
composition D: unlike B, 1-butyl-3-methylimidazolium phosphate (available from Kurthia chemical technology (Beijing)) was also added at 2%, and the amount of polyether polyol was adjusted accordingly to 79% to meet 100% by weight of the total.
Composition E: the preparation method comprises the steps of (1) performing a first prepolymerization reaction on 79% of isocyanate M20S (purchased from Shanghai Seikovia (China) Co., ltd.), 20% of polyether polyol (purchased from Shanghai optimization chemical Co., ltd.) and 1% of a second catalyst (triethanolamine) by weight percent to obtain a polyether modified isocyanate prepolymer; wherein the conditions of the first prepolymerization reaction: the reaction temperature was 60℃and the reaction time was 2h.
F: isocyanate M20S (available from basf (china) limited, division).
Composition R: the compositions E and C blowing agent pentafluoropropane (HFC-245 fa) were mixed at a mass ratio of 93:7 at 10℃to give composition R.
Composition T: mixing the composition D and the foaming agent C with pentane according to the mass ratio of 92:8, and then sequentially stirring and dispersing and ultrasonically dispersing; wherein, the stirring and dispersing conditions are as follows: the stirring speed is 2000rpm, and the stirring time is 30min; conditions for the ultrasonic dispersion: the ultrasonic frequency was 30Hz, the power was 1000W, the amplitude was 80%, and the ultrasonic time was 40min, to obtain composition T.
Composition G: the pentane foaming agent of the composition A and the pentane foaming agent of the composition C are mixed according to the mass ratio of 85:15, and the composition G is obtained.
Composition H: and mixing the composition B and the foaming agent C with pentane in a mass ratio of 85:15 to obtain a composition H.
Composition M: stirring and dispersing the composition H, and performing ultrasonic dispersion; wherein, the stirring and dispersing conditions are as follows: the stirring speed is 2000rpm, and the stirring time is 30min; conditions for the ultrasonic dispersion: the ultrasonic frequency was 30Hz, the power was 1000W, the amplitude was 80%, and the ultrasonic time was 40min, to obtain composition M.
Composition K: and mixing the composition D and the foaming agent C, namely pentafluoropropane in a mass ratio of 85:15 to obtain a composition K.
Composition N: stirring and dispersing the composition K, and performing ultrasonic dispersion; wherein, the stirring and dispersing conditions are as follows: the stirring speed is 2000rpm, and the stirring time is 30min; conditions for the ultrasonic dispersion: the ultrasonic frequency is 30Hz, the power is 1000W, the amplitude is 80%, and the ultrasonic time is 40min, so that the composition N is obtained.
Storability test example 1
The above-mentioned partial compositions were subjected to a storability test, and the results are shown in Table 1 below.
TABLE 1
As can be seen from Table 1, composition H containing nanocellulose delaminates, and the white stock storage time becomes longer with the white stock composition K containing 1-butyl-3-methylimidazolium hexafluorophosphate according to the present invention.
Furthermore, for the white material composition K, after the white material composition K is treated by adopting the preferable specific two-step dispersion method, the composition N can achieve the effect of no layering in 180 days, and the storage performance is obviously improved. Similarly, the composition T of the invention can achieve the effect of 180 days without layering, and has the same excellent storage effect.
Viscosity test example 2
The above part of the composition was subjected to a viscosity test, and the results are shown in Table 2 below.
TABLE 2
As can be seen from table 2, the difference between the viscosities of the composition N and the composition T using the nanocellulose, the 1-butyl-3-methylimidazolium hexafluorophosphate and the first foaming agent according to the present invention and the viscosity of the black material F is significantly reduced compared to the composition D without the foaming agent, which is advantageous for promoting the mixing of the black material and the white material, which is advantageous for promoting the reaction exotherm, reducing the foam breaking, and thus reducing the thermal conductivity of the polyurethane rigid foam.
Further, the composition R employing the preferred polyether modified isocyanate prepolymer and the second blowing agent of the present invention, which is more significantly shorter in viscosity deviation of the black and white materials than the composition E or isocyanate F employing the polyether modified isocyanate prepolymer, is more advantageous in promoting the mixing of the black and white materials, thereby reducing the thermal conductivity of the polyurethane rigid foam.
Further, the viscosity of the composition R at 10 ℃ is closest to or overlaps with the viscosity of the composition T at 30 ℃, so that the black material and the white material can be controlled to be mixed at different feed material temperatures, thereby being beneficial to obtain the optimal mixing effect.
Example 1
And (3) mixing and foaming the black material and the white material on a machine, wherein the feeding temperature of the black material and the white material is 20 ℃, the black material is F, the white material is a composition N, and the mass ratio of F to the composition N is=1.2:1, so as to obtain the polyurethane hard foam. The thermal conductivity was then tested and shown in table 3.
Example 2
Reference example 1 was made except that the black material was composition E and the thermal conductivity was as shown in table 3.
Example 3
Reference example 1 was made, except that the black material was composition R, the material temperature was the same, and the thermal conductivity was as shown in table 3.
Example 4
With reference to example 3, except that composition R: composition N mass ratio = 1.1:1, the feed temperature of composition R was controlled to 10 ℃, and the feed temperature of composition N was controlled to 30 ℃, the thermal conductivity was measured as shown in table 3.
Comparative example 1
With reference to example 1, except that the white stock was composition G, the thermal conductivity was measured as shown in table 3.
TABLE 3 Table 3
As can be seen from table 3, the use of the embodiment of the present invention, in which nanocellulose, 1-butyl-3-methylimidazolium hexafluorophosphate and the first foaming agent were added, was able to reduce the thermal conductivity of the polyurethane rigid foam to 0.018W/m·k or less, compared to comparative example 1, for a white stock having a certain storage time without delamination.
Further, according to the invention of example 2 and example 1, the black material of the polyether modified isocyanate prepolymer of the invention is more beneficial to reducing the heat conductivity coefficient of the polyurethane hard foam.
Further, according to the invention of example 3 and example 1, the black material containing the polyether modified isocyanate prepolymer and the second foaming agent of the invention is more favorable for reducing the heat conductivity coefficient of the polyurethane rigid foam.
Further, according to the embodiments 4 and 3 of the present invention, the thermal conductivity of the polyurethane rigid foam is reduced by adopting the preferred schemes of the present invention for controlling the material temperature of the black material and the white material.
The preferred embodiments of the present invention have been described in detail above, but the present invention is not limited thereto. Within the scope of the technical idea of the invention, a number of simple variants of the technical solution of the invention are possible, including combinations of the individual technical features in any other suitable way, which simple variants and combinations should likewise be regarded as being disclosed by the invention, all falling within the scope of protection of the invention.
Claims (11)
1. The polyurethane hard foam with the low thermal conductivity coefficient comprises a black material and a white material, wherein the black material comprises isocyanate compounds, and the white material comprises polyether polyol, polyester polyol, silicone oil, a first catalyst and water, and is characterized by further comprising nanocellulose, 1-butyl-3-methylimidazole hexafluorophosphate and a first foaming agent, wherein the mass of the first foaming agent accounts for 8% -15% of the total mass of the white material, and the sum of the mass of the polyether polyol, the polyester polyol, the silicone oil, the first catalyst and water and the mass of nanocellulose, 1-butyl-3-methylimidazole hexafluorophosphate accounts for 85% -92% of the total mass of the white material; and the amount of the nanocellulose accounts for 0.02-3 percent and the amount of the 1-butyl-3-methylimidazole hexafluorophosphate accounts for 0.05-3 percent based on the sum of the mass of polyether polyol, polyester polyol, silicone oil, a first catalyst, water, nanocellulose and 1-butyl-3-methylimidazole hexafluorophosphate; and controlling the viscosity of the white material at 20 ℃ to be 500-800 MPa.S.
2. The polyurethane rigid foam according to claim 1, wherein the isocyanate-based compound is a polyether-modified isocyanate prepolymer, and the viscosity of the black material at 20 ℃ is controlled to be 500-2700 MPa-S.
3. The polyurethane rigid foam according to claim 2, wherein the prepolymer raw material of the polyether modified isocyanate prepolymer comprises the following composition in mass ratio: based on the total mass of the raw materials, 68-89.95% of isocyanate, 10-30% of polyether polyol and 0.05-2% of second catalyst.
4. The polyurethane hard foam according to claim 2, wherein the black material further comprises a second foaming agent having a boiling point of not higher than 15 ℃, the mass of the second foaming agent is 5% to 10% of the total amount of the black material, the mass of the polyether-modified isocyanate prepolymer is 90% to 95% of the total amount of the black material, and the viscosity of the black material at 20 ℃ is controlled to 500 to 600 mpa.s.
5. The polyurethane hard foam according to claim 4, wherein the boiling point of the first foaming agent is higher than 15 ℃, the mass of the first foaming agent accounts for 8-10% of the total mass of the white material, and the sum of the masses of the polyether polyol, the polyester polyol, the silicone oil, the first catalyst and water as well as the nanocellulose, the 1-butyl-3-methylimidazole hexafluorophosphate accounts for 90-92% of the total mass of the white material; and the viscosity of the white material at 20 ℃ is controlled to be 700-800 MPa.S.
6. The hard polyurethane foam according to claim 5, wherein the first blowing agent is at least one selected from the group consisting of pentane, methyl formate, 1-chloro, 3 trifluoropropene, hexafluorobutene, the second foaming agent is selected from the group consisting of pentafluoropropane, n-butane, isobutane, difluoroethane tetrafluoroethane, 2, 3-tetrafluoropropene, trans-1, 4-hexafluoro-2-butene tetrafluoroethane, 2, 3-tetrafluoropropene trans-1, 4-hexafluoro-2-butene.
7. The polyurethane rigid foam according to claim 1, wherein the mass ratio of the black material to the white material is 1.1-1.5:1; in the white material, the weight of polyether polyol is 52-85.9%, the weight of polyester polyol is 10-30%, the weight of silicone oil is 1.5-4%, the weight of first catalyst is 1.5-4%, and the weight of water is 1-4% based on the sum of the weight of polyether polyol, polyester polyol, silicone oil, first catalyst, water and nanocellulose and 1-butyl-3-methylimidazole hexafluorophosphate;
and/or the thermal conductivity of the polyurethane hard foam is below 0.018W/m.k.
8. A polyurethane rigid foam according to claim 1, characterized in that the first blowing agent is selected from pentane, methyl formate, 1-chloro, 3,3 trifluoropropene, hexafluorobutene, pentafluoropropane, n-butane, isobutane, difluoroethane tetrafluoroethane, 2, 3-tetrafluoropropene, trans-1, 4-hexafluoro-2-butene tetrafluoroethane, 2, 3-tetrafluoropropene trans-1, 4-hexafluoro-2-butene.
9. A method for preparing a polyurethane hard foam having a low thermal conductivity, wherein the polyurethane hard foam is the polyurethane hard foam according to any one of claims 1 to 8, and the method comprises: mixing and foaming white materials and black materials, wherein the preparation process of the white materials comprises the following steps:
mixing polyether polyol, polyester polyol, silicone oil, a first catalyst, water, nanocellulose, 1-butyl-3-methylimidazole hexafluorophosphate and a first foaming agent, and then sequentially stirring and dispersing and ultrasonic dispersing; wherein the conditions for stirring and dispersing comprise: stirring speed is 1800-2200rpm, and stirring time is 25-35min; the conditions for the ultrasonic dispersion include: the ultrasonic frequency is 20-40Hz, the power is 800-1200W, the amplitude is 70% -90%, and the ultrasonic time is 30-50min.
10. The method of manufacturing according to claim 9, further comprising the process of manufacturing black material:
carrying out a first prepolymerization reaction on isocyanate, polyether polyol and a second catalyst to obtain polyether modified isocyanate prepolymer; wherein the conditions of the first prepolymerization reaction comprise: the reaction temperature is 50-70 ℃ and the reaction time is 1-3h;
and then performing a second mixing with a second blowing agent, the conditions of the second mixing comprising: the mixing temperature is 5-12 ℃, and the mixing time is 20-40min.
11. The method according to claim 10, wherein in the mixed foaming, the feeding temperature of the black material is controlled to 5 to 12 ℃ and the feeding temperature of the white material is controlled to 25 to 35 ℃.
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