CN117467107A - Polyurethane rigid foam with ultralow heat conductivity coefficient and preparation method thereof - Google Patents
Polyurethane rigid foam with ultralow heat conductivity coefficient and preparation method thereof Download PDFInfo
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- CN117467107A CN117467107A CN202311423397.0A CN202311423397A CN117467107A CN 117467107 A CN117467107 A CN 117467107A CN 202311423397 A CN202311423397 A CN 202311423397A CN 117467107 A CN117467107 A CN 117467107A
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- prepolymer
- polyether
- isocyanate
- component
- combined polyether
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- 239000006260 foam Substances 0.000 title claims abstract description 108
- 229920002635 polyurethane Polymers 0.000 title claims abstract description 76
- 239000004814 polyurethane Substances 0.000 title claims abstract description 76
- 238000002360 preparation method Methods 0.000 title abstract description 19
- 239000004721 Polyphenylene oxide Substances 0.000 claims abstract description 171
- 229920000570 polyether Polymers 0.000 claims abstract description 171
- 239000012948 isocyanate Substances 0.000 claims abstract description 113
- 150000002513 isocyanates Chemical class 0.000 claims abstract description 113
- 239000002994 raw material Substances 0.000 claims abstract description 11
- 239000000203 mixture Substances 0.000 claims description 66
- RLYCRLGLCUXUPO-UHFFFAOYSA-N 2,6-diaminotoluene Chemical compound CC1=C(N)C=CC=C1N RLYCRLGLCUXUPO-UHFFFAOYSA-N 0.000 claims description 40
- 239000004088 foaming agent Substances 0.000 claims description 29
- 229920005862 polyol Polymers 0.000 claims description 21
- 150000003077 polyols Chemical class 0.000 claims description 21
- 229920001046 Nanocellulose Polymers 0.000 claims description 15
- 238000000034 method Methods 0.000 claims description 15
- 238000005187 foaming Methods 0.000 claims description 13
- 239000003054 catalyst Substances 0.000 claims description 8
- 229920005906 polyester polyol Polymers 0.000 claims description 8
- -1 1-butyl-3-methylimidazole hexafluorophosphate Chemical compound 0.000 claims description 6
- 238000006116 polymerization reaction Methods 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 4
- 238000006243 chemical reaction Methods 0.000 description 34
- 230000000694 effects Effects 0.000 description 15
- 239000000463 material Substances 0.000 description 13
- 230000015572 biosynthetic process Effects 0.000 description 10
- 239000004604 Blowing Agent Substances 0.000 description 9
- 210000004027 cell Anatomy 0.000 description 9
- 230000008569 process Effects 0.000 description 9
- 238000012360 testing method Methods 0.000 description 8
- 239000007789 gas Substances 0.000 description 6
- 238000009826 distribution Methods 0.000 description 5
- OFBQJSOFQDEBGM-UHFFFAOYSA-N Pentane Chemical compound CCCCC OFBQJSOFQDEBGM-UHFFFAOYSA-N 0.000 description 4
- 229920005830 Polyurethane Foam Polymers 0.000 description 4
- 239000011496 polyurethane foam Substances 0.000 description 4
- 230000000630 rising effect Effects 0.000 description 4
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 description 3
- 239000002253 acid Substances 0.000 description 3
- 230000009286 beneficial effect Effects 0.000 description 3
- 238000005516 engineering process Methods 0.000 description 3
- 230000002349 favourable effect Effects 0.000 description 3
- 210000000497 foam cell Anatomy 0.000 description 3
- 239000002608 ionic liquid Substances 0.000 description 3
- 238000005259 measurement Methods 0.000 description 3
- 230000006911 nucleation Effects 0.000 description 3
- 238000010899 nucleation Methods 0.000 description 3
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 3
- 229920003023 plastic Polymers 0.000 description 3
- 239000004033 plastic Substances 0.000 description 3
- 230000005855 radiation Effects 0.000 description 3
- 230000036632 reaction speed Effects 0.000 description 3
- 230000009467 reduction Effects 0.000 description 3
- 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 2
- 241001391944 Commicarpus scandens Species 0.000 description 2
- QUSNBJAOOMFDIB-UHFFFAOYSA-N Ethylamine Chemical compound CCN QUSNBJAOOMFDIB-UHFFFAOYSA-N 0.000 description 2
- 238000005054 agglomeration Methods 0.000 description 2
- 230000002776 aggregation Effects 0.000 description 2
- 238000013459 approach Methods 0.000 description 2
- 239000003999 initiator Substances 0.000 description 2
- TZIHFWKZFHZASV-UHFFFAOYSA-N methyl formate Chemical compound COC=O TZIHFWKZFHZASV-UHFFFAOYSA-N 0.000 description 2
- 238000013112 stability test Methods 0.000 description 2
- 239000007858 starting material Substances 0.000 description 2
- ZESKRVSPQJVIMH-UHFFFAOYSA-N 1,3-dimethoxypropan-2-ol Chemical compound COCC(O)COC ZESKRVSPQJVIMH-UHFFFAOYSA-N 0.000 description 1
- FXRLMCRCYDHQFW-UHFFFAOYSA-N 2,3,3,3-tetrafluoropropene Chemical compound FC(=C)C(F)(F)F FXRLMCRCYDHQFW-UHFFFAOYSA-N 0.000 description 1
- ZLBFMYQIKPWYBC-UHFFFAOYSA-N 2-benzofuran-1,3-dione;2-(2-hydroxyethoxy)ethanol Chemical compound OCCOCCO.C1=CC=C2C(=O)OC(=O)C2=C1 ZLBFMYQIKPWYBC-UHFFFAOYSA-N 0.000 description 1
- 229910019142 PO4 Inorganic materials 0.000 description 1
- 229920002334 Spandex Polymers 0.000 description 1
- CZMRCDWAGMRECN-UGDNZRGBSA-N Sucrose Chemical compound O[C@H]1[C@H](O)[C@@H](CO)O[C@@]1(CO)O[C@@H]1[C@H](O)[C@@H](O)[C@H](O)[C@@H](CO)O1 CZMRCDWAGMRECN-UGDNZRGBSA-N 0.000 description 1
- 229930006000 Sucrose Natural products 0.000 description 1
- 238000010669 acid-base reaction Methods 0.000 description 1
- 230000002378 acidificating effect Effects 0.000 description 1
- 230000009471 action Effects 0.000 description 1
- 150000001412 amines Chemical class 0.000 description 1
- 125000003277 amino group Chemical group 0.000 description 1
- 239000012752 auxiliary agent Substances 0.000 description 1
- 238000006555 catalytic reaction Methods 0.000 description 1
- 229920002678 cellulose Polymers 0.000 description 1
- 239000001913 cellulose Substances 0.000 description 1
- 230000000052 comparative effect Effects 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 125000004122 cyclic group Chemical group 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 239000006261 foam material Substances 0.000 description 1
- 230000017525 heat dissipation Effects 0.000 description 1
- 230000020169 heat generation Effects 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 238000009413 insulation Methods 0.000 description 1
- IQPQWNKOIGAROB-UHFFFAOYSA-N isocyanate group Chemical group [N-]=C=O IQPQWNKOIGAROB-UHFFFAOYSA-N 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 230000007246 mechanism Effects 0.000 description 1
- 239000002086 nanomaterial Substances 0.000 description 1
- 239000002667 nucleating agent Substances 0.000 description 1
- 238000005457 optimization Methods 0.000 description 1
- MSSNHSVIGIHOJA-UHFFFAOYSA-N pentafluoropropane Chemical compound FC(F)CC(F)(F)F MSSNHSVIGIHOJA-UHFFFAOYSA-N 0.000 description 1
- NBIIXXVUZAFLBC-UHFFFAOYSA-K phosphate Chemical compound [O-]P([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-K 0.000 description 1
- 239000010452 phosphate Substances 0.000 description 1
- 230000000379 polymerizing effect Effects 0.000 description 1
- 230000002035 prolonged effect Effects 0.000 description 1
- 230000001737 promoting effect Effects 0.000 description 1
- 230000001105 regulatory effect Effects 0.000 description 1
- 238000005096 rolling process Methods 0.000 description 1
- 239000000523 sample Substances 0.000 description 1
- 238000004904 shortening Methods 0.000 description 1
- 239000000377 silicon dioxide Substances 0.000 description 1
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N silicon dioxide Inorganic materials O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 239000004759 spandex Substances 0.000 description 1
- 238000003860 storage Methods 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 239000005720 sucrose Substances 0.000 description 1
- 230000002195 synergetic effect Effects 0.000 description 1
- 238000010998 test method Methods 0.000 description 1
- 238000011282 treatment Methods 0.000 description 1
- 238000009827 uniform distribution Methods 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- 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
- C08G18/4009—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
- C08G18/28—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
- C08G18/48—Polyethers
- C08G18/4804—Two or more polyethers of different physical or chemical nature
- C08G18/482—Mixtures of polyethers containing at least one polyether containing nitrogen
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
- C08G18/40—High-molecular-weight compounds
- C08G18/48—Polyethers
- C08G18/50—Polyethers having heteroatoms other than oxygen
- C08G18/5021—Polyethers having heteroatoms other than oxygen having nitrogen
- C08G18/5024—Polyethers having heteroatoms other than oxygen having nitrogen containing primary and/or secondary amino groups
- C08G18/5027—Polyethers having heteroatoms other than oxygen having nitrogen containing primary and/or secondary amino groups directly linked to carbocyclic groups
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- 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
- 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
-
- 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
Landscapes
- Chemical & Material Sciences (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Polyurethanes Or Polyureas (AREA)
Abstract
The invention belongs to the technical field of polyurethane hard foam, and in particular relates to an ultra-low thermal conductivity polyurethane hard foam and a preparation method thereof, wherein the raw materials of the ultra-low thermal conductivity polyurethane hard foam comprise a first component and a second component, the first component comprises an isocyanate prepolymer, the second component comprises a combined polyether prepolymer, the isocyanate prepolymer contains 70-95% of-NCO groups, the combined polyether prepolymer contains 70-95% of-OH groups, and the mass ratio of-NCO groups in the isocyanate prepolymer to-OH groups in the combined polyether prepolymer is (0.9-1.1): 1. the polyurethane hard foam has ultralow heat conductivity coefficient below 0.015 w/m.k, shorter demolding time and better dimensional stability.
Description
Technical Field
The invention belongs to the technical field of polyurethane hard foam, and particularly relates to an ultra-low thermal conductivity polyurethane hard foam and a preparation method thereof.
Background
The technology of polyurethane hard foam is continuously improved, and in the prior art, the heat conductivity coefficient is reduced by adopting a method of adding auxiliary agents, nucleating agents, nano-silica, nano-cellulose and other nano-materials, foaming agents and the like into white materials or black materials, so that the level of low heat conductivity coefficient (0.016-0.019 w/m.k 0) can be basically achieved. 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: lambda (lambda) Foam ＝λ Gas and its preparation method (50％)+λ Plastic material (25％)+λ Radiation of (25%) wherein lambda Foam : foam thermal conductivity; lambda (lambda) Gas and its preparation method : heat conducted through the gas within the cells; lambda (lambda) Plastic material : heat conducted through the solid plastic; lambda (lambda) Radiation of : heat conducted by heat radiation through the cells. Thus, the influence of the heat conductivity coefficient of the hard bubble systemMainly determined by the fine density of cells in the foam, the cell diameter, the heat conducting gas in the foam, etc.
In order to reduce the thermal conductivity of polyurethane rigid foams, the current approach is, on the one hand, to improve the corresponding treatments which lead to earlier formation of cells in the foam, to lower thermal conductivity of gases contained in the cells or to smaller cell diameters.
On the other hand, in order to reduce the heat conductivity coefficient, better mixing is realized, and the reaction is controlled in a direction more favorable for reducing the heat conductivity coefficient, for example, the black material containing isocyanate and the white material containing combined polyether are respectively formed by mixing corresponding raw materials at different reaction temperatures, and then the black material and the white material with similar viscosity are mixed and foamed to prepare the hard foam. However, the preparation temperature of the raw materials is different, so that the production control is complicated, the foaming of the raw materials is required to be performed under strict high and low temperature conditions, and the control of the high and low temperature conditions cannot be realized due to the application of field conditions of part of products, so that the use of hard foam materials is limited; and the black materials containing isocyanate and the white materials containing combined polyether are respectively formed by mixing corresponding raw materials at different reaction temperatures, and then the black materials and the white materials with similar viscosity are mixed and foamed to prepare hard bubbles, wherein the temperature is higher in the foaming process, so that the reaction speed is too high, the uniform reaction is affected, the rising process of the foam is caused, the bubble generation and the like are caused, the air inclusion of the foam is increased, the heat dissipation is not in time due to the higher temperature, the bubbles are relatively easy to break, and the like, and the formation of the bubbles and the reduction of the diameters of the bubbles are all affected.
However, the prior art still cannot realize the preparation of polyurethane rigid foam with ultra-low heat conductivity coefficient (below 0.015 w/m.k), and cannot meet the application scene requirement of specific products.
It should be noted that this section of the disclosure only provides a background related to the present disclosure, and does not necessarily constitute prior art or known technology.
Disclosure of Invention
The invention aims to overcome the defect that the polyurethane hard foam cannot reach the ultralow heat conductivity coefficient below 0.015 w/m.k in the prior art, and provides the polyurethane hard foam with the ultralow heat conductivity coefficient below 0.015 w/m.k, and the preparation method thereof.
In order to achieve the above object, in a first aspect, the present invention provides an ultra-low thermal conductivity polyurethane hard foam, the raw materials of which include a first component and a second component, the first component includes an isocyanate prepolymer, the second component includes a combined polyether prepolymer, the isocyanate prepolymer contains-NCO groups in an amount of 70% to 95% by mass, the combined polyether prepolymer contains-OH groups in an amount of 70% to 95% by mass, and the ratio of-NCO groups in the isocyanate prepolymer to-OH groups in the combined polyether prepolymer is (0.9 to 1.1): 1.
in some preferred embodiments of the invention, the isocyanate prepolymer has a viscosity of 5000 to 11000 mPas, preferably 5000 to 9000 mPas, at 10-30℃and the combined polyether prepolymer has a viscosity of 6000 to 12000 mPas, preferably 6000 to 10000 mPas, at 10-30 ℃.
In some preferred embodiments of the present invention, the first component and the second component each further comprise a foaming agent, wherein the foaming agent accounts for 5wt% to 30wt% of the total amount of the respective components, the viscosity of the first component is controlled to be 800 to 1400 mPas, preferably 800 to 1200 mPas, at 10 to 30 ℃, and the viscosity of the second component is controlled to be 800 to 1400 mPas, preferably 800 to 1200 mPas, at 10 to 30 ℃.
In some preferred embodiments of the present invention, the prepolymer starting material of the isocyanate prepolymer comprises a first isocyanate and a first o-toluenediamine type polyether having a pH of 4.5 to 6, the first o-toluenediamine type polyether comprising 5% to 30% by weight of the total amount of the first isocyanate and the first o-toluenediamine type polyether.
In some preferred embodiments of the present invention, the pre-polymerization feed for the combination polyether prepolymer comprises the combination polyether and a second isocyanate, the second isocyanate comprising 5wt% to 35wt% of the total amount of the combination polyether and the second isocyanate.
Further preferably, the composition of the combined polyether comprises, based on the total amount of the combined polyether: 46 to 81.35 weight percent of polyether polyol, 15 to 30 weight percent of polyester polyol, 1.5 to 4 weight percent of silicone oil, 1 to 5 weight percent of catalyst, 1 to 8 weight percent of water, 0.05 to 3.5 weight percent of nanocellulose and 0.1 to 3.5 weight percent of 1-butyl-3-methylimidazole hexafluorophosphate.
Further preferably, the polyether polyol comprises a second o-toluenediamine type polyether having a pH of 4.5 to 6, the second o-toluenediamine type polyether comprising 35wt% to 55wt% of the polyether polyol.
In a second aspect, the invention provides a preparation method of an ultra-low thermal conductivity polyurethane hard foam, wherein the ultra-low thermal conductivity polyurethane hard foam is the ultra-low thermal conductivity polyurethane hard foam of the first aspect.
The preparation method of the polyurethane hard foam with the ultra-low heat conductivity coefficient comprises the following steps: and mixing and foaming the first component containing the isocyanate prepolymer and the second component containing the combined polyether prepolymer to obtain polyurethane hard foam, wherein the heat conductivity coefficient of the obtained polyurethane hard foam is below 0.015 w/m.k.
In some preferred embodiments of the present invention, the preparation method of the polyurethane rigid foam with ultra-low thermal conductivity further comprises: firstly, carrying out first mixing on isocyanate prepolymer and foaming agent to obtain a first component; and performing second mixing on the combined polyether prepolymer and the foaming agent to obtain a second component; the first component and the second component are then subjected to the mixing foaming.
In some preferred embodiments of the present invention, the preparation method of the polyurethane rigid foam with ultra-low thermal conductivity further comprises:
first prepolymerizing first isocyanate and first o-toluenediamine type polyether with pH of 4.5-6 to obtain isocyanate prepolymer;
and carrying out second prepolymerization on the combined polyether and second isocyanate to obtain the combined polyether prepolymer.
Further preferably, the conditions of the first prepolymerization comprise: the temperature is 50-70 ℃ and the time is 1-3h; the conditions for the second prepolymerization include: the temperature is 50-70 ℃ and the time is 1-3h.
The beneficial effects are that:
the invention adopts specific isocyanate prepolymer and combined polyether prepolymer to respectively pre-polymerize partial-NCO groups contained in isocyanate and partial-OH groups contained in combined polyether in advance, release heat in advance, control the pre-polymerization reaction and the pre-polymerization reaction to a proper range, and control the-NCO groups/-OH groups= (0.9-1.1) in a matching way: 1, the deviation of the residual-NCO groups of isocyanate/residual-OH groups of the combined polyether is reduced as much as possible, so that the heat generation is less when two prepolymers are reacted, the reaction speed is better regulated, the uniform reaction can be realized at a lower temperature (the maximum temperature of the foam center in the whole reaction process is not more than 120 ℃ through actual measurement of the reaction) in the foaming process (in the reaction in the prior art, the temperature of the foam center in the whole reaction process can reach 185 ℃ through actual measurement of the reaction, namely, the reaction in the foaming process can be ensured to be uniformly carried out under the condition of higher temperature in the prior art), the temperature is reduced, the reaction speed is further reduced, meanwhile, the high reaction uniformity under the condition of low temperature is realized through proper control of the prepolymerization degree, and the possibility of bubble formation and the like in the rising process of foam is further reduced, so that the gas inclusion of the foam is increased. And under low reaction temperature, the heat is difficult to gather, even gather also obviously lightens the influence to bubble formation, and the bubble is less easy to break the bubble, further improves the formation of bubble and bubble diameter reduction to further reduce thermal conductivity, realize ultralow thermal conductivity, and can obtain better foam size, more even cell distribution, the time of drawing of patterns is shorter simultaneously, dimensional stability improves. Under the same conditions, if the-NCO group/-OH group is greater or less than the above range, the deviation of the-NCO group/-OH group is large, which is disadvantageous for uniform reaction at a relatively low temperature (e.g., 120 ℃ C.) during foaming.
In addition, the invention controls the respective contents of the-NCO groups contained in isocyanate and the-OH groups contained in the combined polyether in the proper ranges, and the proportion of the-NCO groups and the-OH groups is in the proper ranges, so that the viscosity of the two prepolymers is increased, the viscosities of the two prepolymers in the same temperature range can be very easy to approach, the viscosities of the two prepolymers in different temperature ranges (for example, 10 ℃ to 30 ℃) are also more similar, the mixing is more uniform, the uniform reaction is promoted, the possibility of bubble inclusion of the foam is further reduced by rolling up in the rising process of the foam, the formation of the bubble is further improved, the bubble diameter is further reduced, the heat conductivity coefficient is further reduced, the ultralow heat conductivity coefficient is realized, the influence of the raw materials in use is reduced, the use temperature range is wider, the environmental requirement of product preparation is reduced, and the application scene of the product is greatly increased.
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. 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 the present invention, o-toluenediamine type polyether means polyether polyol synthesized by using o-toluenediamine (OTDA) as an initiator.
In the present invention, the mass content of-NCO groups contained in the isocyanate prepolymer is measured according to GB/T/2009.4-2016, and the mass content of-OH groups in the polyether prepolymer is measured according to GB/T/2008.3-2009.
The viscosity is measured according to the national standard related to the to-be-measured object at a preset temperature, wherein the national standard of viscosity test of polyether to-be-measured objects (such as a combined polyether prepolymer or a mixture of the combined polyether prepolymer and other components) is GB/T/2008.7-2010, and the national standard of viscosity test of isocyanate to-be-measured objects (such as an isocyanate prepolymer or a mixture of the isocyanate prepolymer and other components) is GB/T/2009.3-2009.
In a first aspect, the invention provides an ultra-low thermal conductivity polyurethane hard foam, which comprises a first component and a second component, wherein the first component comprises an isocyanate prepolymer, the second component comprises a combined polyether prepolymer, the isocyanate prepolymer contains 70% -95% of-NCO groups by mass, the combined polyether prepolymer contains 70% -95% of-OH groups by mass, and the ratio of the-NCO groups in the isocyanate prepolymer to the-OH groups in the combined polyether prepolymer is (0.9-1.1): 1.
in some preferred embodiments of the invention, the isocyanate prepolymer has a viscosity of 5000 to 11000 mPas, preferably 5000 to 9000 mPas, at 10-30℃and the combined polyether prepolymer has a viscosity of 6000 to 12000 mPas, preferably 6000 to 10000 mPas, at 10-30 ℃. By adopting the preferable scheme of the invention, the viscosities of the specific isocyanate prepolymer and the combined polyether prepolymer are respectively controlled in proper ranges, so that the uniform reaction at lower temperature (the temperature of the foam center in the whole reaction process is not more than 120 ℃ in the highest through actual measurement of the reaction) is facilitated, the reaction uniformity under the low-temperature condition can be further optimized, the possibility of bubble inclusion of the foam caused by bubble formation and the like in the rising process of the foam is reduced, the heat conductivity coefficient is further reduced, the better foam size is obtained, the more uniform foam distribution is obtained, the demolding time is shorter, and the dimensional stability is improved.
It is understood that the isocyanate prepolymer is obtained by prepolymerizing isocyanate, and the combined polyether prepolymer is obtained by prepolymerizing the combined polyether, and the viscosity after prepolymerization is increased compared with the viscosity before prepolymerization. For example, the viscosity of the unpolymerized isocyanate at 10-30℃is 100-300 mPas, which is significantly lower than the viscosity of the isocyanate prepolymer.
In some preferred embodiments of the present invention, the first component and the second component each further comprise a foaming agent, wherein the foaming agent accounts for 5wt% to 30wt% of the total amount of the respective components, the viscosity of the first component is controlled to be 800 to 1400 mPas, preferably 800 to 1200 mPas, at 10 to 30 ℃, and the viscosity of the second component is controlled to be 800 to 1400 mPas, preferably 800 to 1200 mPas, at 10 to 30 ℃. By adopting the preferable scheme of the invention, the viscosity of the foaming agent is more similar at the same or different temperatures by adopting the proper amount of the foaming agent; the foaming agent can reduce the viscosity, is more beneficial to realizing uniform reaction at low temperature, obtains better foam size, more uniform foam distribution, and has shorter demolding time and improved dimensional stability.
It is understood that the first component and the second component are each added with a foaming agent. The foaming agent accounts for 5-30wt% of the total amount of the first component, and the foaming agent accounts for 5-30wt% of the total amount of the second component.
The blowing agent of the present invention may be of a type conventional in the art, and may achieve the effects of the present invention, and for example, the blowing agent may be at least one selected from pentane, methyl formate, R245fa, LBA blowing agent, R600a blowing agent, R-152a blowing agent, R-1234yf, kemu Opteon 1100, kemu Opteon 1150, HCFO-1224yd, HCFO-1234ze, HCFO-1243zf, and HCFO-1233 xf.
In some preferred embodiments of the present invention, the prepolymer starting material of the isocyanate prepolymer comprises a first isocyanate and a first o-toluenediamine type polyether having a pH of 4.5 to 6, the first o-toluenediamine type polyether comprising 5% to 30% by weight of the total amount of the first isocyanate and the first o-toluenediamine type polyether. By adopting the preferable scheme of the invention, the first o-toluenediamine polyether (namely OTDA polyether) with weak acid pH of 4.5-6 is selected as the raw material for the prepolymerization of the isocyanate prepolymer, so that the prepolymerization reaction of the first o-toluenediamine polyether and the weak acid isocyanate is facilitated, and the severe acid-base reaction is reduced, wherein the OTDA contains benzene ring structures and the isocyanate also contains benzene ring structures, and the prepolymerization is carried out by the first o-toluenediamine polyether and the second o-toluenediamine polyether which also have benzene ring structures and are weak acid, so that the reaction uniformity is better, the reaction tends to be more balanced and gentle, and the obtained prepolymerization structure is more uniform.
In some preferred embodiments of the present invention, the pre-polymerization feed for the combination polyether prepolymer comprises the combination polyether and a second isocyanate, the second isocyanate comprising 5wt% to 35wt% of the total amount of the combination polyether and the second isocyanate. The combined polyether accounts for 65-95 wt% of the combined polyether and the second isocyanate.
Further preferably, the composition of the combined polyether comprises, based on the total amount of the combined polyether: 46 to 81.35 weight percent of polyether polyol, 15 to 30 weight percent of polyester polyol, 1.5 to 4 weight percent of silicone oil, 1 to 5 weight percent of catalyst, 1 to 8 weight percent of water, 0.05 to 3.5 weight percent of nanocellulose and 0.1 to 3.5 weight percent of 1-butyl-3-methylimidazole hexafluorophosphate. By adopting the preferred scheme of the invention, the ionic liquid 1-butyl-3-methylimidazole hexafluorophosphate with proper amount is added into the combined polyether containing proper amount of nanocellulose, so that the agglomeration of nanocellulose in polyether polyol can be reduced, the mixing of nanocellulose is promoted, the capability of nanocellulose for reducing the local stress effect of polyol interface in the combined polyether is improved, the viscosity of the combined polyether is reduced under the action of the proper amount of 1-butyl-3-methylimidazole hexafluorophosphate, and meanwhile, the ionic liquid dispersing effect is added, so that the agglomeration of nanocellulose in polyether polyol is greatly reduced, the enhanced nucleation effect is facilitated to be obtained, and the storage time of the combined polyether is prolonged; the combined polyether containing the nanocellulose, which can enhance nucleation and exist uniformly, and the second isocyanate are prepolymerized, so that the content of-OH groups in the combined polyether is controlled, the effect of the nanocellulose on promoting nucleation can be fully utilized under the low-temperature condition, the reaction uniformity is promoted, the nanocellulose is added to cooperate with the prepolymerization reaction under the low temperature, the formation of bubbles and the reduction of the diameters of the bubbles are further improved by cooperation, the heat conductivity is further reduced, the ultralow heat conductivity is realized, the better foam size is obtained, the uniform foam distribution is realized, the demolding time is shorter, and the dimensional stability is improved.
Under the above composition conditions of the combined polyether, the viscosity of the combined polyether at 10-30 ℃ is 2300-5100 mPas and is obviously lower than that of the combined polyether prepolymer, specifically, the viscosity at 10 ℃ is 2850-5100 mPas, the viscosity at 20 ℃ is 2600-4700 mPas and the viscosity at 30 ℃ is 2300-4300 mPas. The mixture of the combined polyether and the foaming agent has a viscosity of 300-900 mPas at 10-30 ℃.
Further preferably, the polyether polyol comprises a second o-toluenediamine type polyether (or OTDA type polyether) having a pH of 4.5 to 6, the second o-toluenediamine type polyether comprising 35wt% to 55wt% of the polyether polyol; it is understood that the other polyether polyols are non-OTDA type polyether polyols. By adopting the preferred scheme of the invention, the components after the non-OTDA polyether is mixed are usually alkaline, and a proper amount of slightly acidic OTDA polyether is partially introduced, so that the stable exertion of the strong hydrogen bond of the nanocellulose to the enhancement effect of polyether polyol in the prepolymerization process is very beneficial, thereby reducing the influence of the prepolymerization on the nanocellulose in the combined polyether, further improving the formation of bubbles and reducing the diameters of the bubbles, further reducing the heat conductivity coefficient, realizing the ultralow heat conductivity coefficient, obtaining better foam size, more uniform foam distribution, and simultaneously shortening the demolding time and improving the dimensional stability. In addition, the OTDA polyether contains amine groups, so that the catalysis effect similar to an amine catalyst can be achieved, the reaction activity of the combined polyether is greatly improved, the intersolubility with the second isocyanate and the foaming agent is better than that of other polyether polyols, the synergistic effect can be achieved with common polyether, the effective balance effect on the viscosity of a reaction system is achieved, the uniform distribution of polyurethane foam cells, the cell diameters and the like are promoted under the comprehensive effect, and the heat conductivity coefficient is further reduced.
The o-toluenediamine type polyether of the present invention may be commercially available or prepared so long as the desired pH is satisfied, and may be, for example, an OTDA type polyether product of general polyurethane products Co., ltd.
In the invention, the non-OTDA polyether polyol, polyester polyol, catalyst and silicone oil can all achieve the aim of the invention on the basis of meeting the conditions, and can be of the existing corresponding types. For example, the non-OTDA polyether polyol may be a polyether using a compound such as sucrose as an initiator. For example, the polyester polyol may be a diethylene glycol-phthalic anhydride based polyester polyol. For example, the catalyst may be a cyclic ethylamine.
The isocyanate according to the invention may be crude MDI (basf M20S).
In a second aspect, the invention provides a preparation method of an ultra-low thermal conductivity polyurethane hard foam, wherein the ultra-low thermal conductivity polyurethane hard foam is the ultra-low thermal conductivity polyurethane hard foam of the first aspect.
The preparation method of the polyurethane hard foam with the ultra-low heat conductivity coefficient comprises the following steps: and mixing and foaming the first component containing the isocyanate prepolymer and the second component containing the combined polyether prepolymer to obtain polyurethane hard foam, wherein the heat conductivity coefficient of the obtained polyurethane hard foam is below 0.015 w/m.k. The polyurethane hard foam has shorter demolding time and better dimensional stability.
The first component and the second component can be mixed according to the conventional mixing ratio, for example, the mass ratio of the first component to the second component can be 1-3:1.
in some preferred embodiments of the present invention, the preparation method of the polyurethane rigid foam with ultra-low thermal conductivity further comprises: firstly, carrying out first mixing on isocyanate prepolymer and foaming agent to obtain a first component; and performing second mixing on the combined polyether prepolymer and the foaming agent to obtain a second component; the first component and the second component are then subjected to the mixing foaming. According to the invention, the preferable scheme is adopted, isocyanate or combined polyether is pre-polymerized and then mixed with the foaming agent, so that compared with the mode of mixing with the foaming agent and then pre-polymerizing, the reaction is more sufficient, and the proportion control of-OH groups or-NCO groups is facilitated.
In some preferred embodiments of the present invention, the preparation method of the polyurethane rigid foam with ultra-low thermal conductivity further comprises: first prepolymerizing first isocyanate and first o-toluenediamine type polyether with pH of 4.5-6 to obtain isocyanate prepolymer; and carrying out second prepolymerization on the combined polyether and the second isocyanate to obtain the combined polyether prepolymer.
Further preferably, the conditions of the first prepolymerization comprise: the temperature is 50-70 ℃ and the time is 1-3h; the conditions for the second prepolymerization include: the temperature is 50-70 ℃ and the time is 1-3h.
The following examples of the present invention are illustrative only and are not to be construed as limiting the invention. Wherein, each raw material adopted is: polyether polyol 4110A was purchased from optimization chemistry (Shanghai) limited, polyester polyol 3152 was purchased from spandex (Nanj) chemistry limited, silicone oil was purchased from Jiangsu meisi chemical Co., ltd, catalyst triethylamine was purchased from Ying-Chuang specialty chemistry (Shanghai) limited, nanocellulose was purchased from Shanghai Chen Ji Chen Jie Chen Co., ltd, ionic liquid 1-butyl-3-methylimidazoliu phosphate was purchased from kuer chemical technology (Beijing) limited, and isocyanate was crude MDI (basf M20S).
Preparation of the composition
Combination polyether a:72.5wt% of polyether polyol, 20wt% of polyester polyol, 2wt% of silicone oil, 1wt% of catalyst, 2wt% of water, 1wt% of nanocellulose, 1.5wt% of 1-butyl-3-methylimidazole hexafluorophosphate.
Component B: an isocyanate.
Component C: the blowing agent pentane.
Composition F: 90% by weight of the combined polyether A and 10% by weight of the component C were mixed to obtain a composition F containing a foaming agent and the combined polyether A.
A combined polyether prepolymer D: and (3) carrying out second prepolymerization on 90wt% of the combined polyether A and 10wt% of isocyanate for 2 hours at 60 ℃ to obtain a combined polyether prepolymer D, wherein the mass content of-OH groups in the combined polyether prepolymer D is 88% -91%.
Isocyanate prepolymer E: the method comprises the steps of carrying out first prepolymerization on 90wt% of isocyanate and 10wt% of o-toluenediamine type polyether with pH of 4.5-6 at 60 ℃ for 2 hours to obtain isocyanate prepolymer E, wherein the mass content of-NCO groups in the isocyanate prepolymer E is 89% -92%.
Composition G: 90% by weight of the combined polyether prepolymer D and 10% by weight of the component C were mixed to obtain a composition G containing a blowing agent and the combined polyether prepolymer D.
Composition H: 90% by weight of the isocyanate prepolymer E and 10% by weight of the component C were mixed to give a composition H containing a blowing agent and an isocyanate prepolymer E.
Combined polyether prepolymer D-1: the composition of the polyether prepolymer is referred to as a combined polyether prepolymer D, and the components are different in content, specifically 80wt% of combined polyether A and 20wt% of isocyanate are adopted, and the mass content of-OH groups in the obtained combined polyether prepolymer D-1 is 82% -86%.
Combined polyether prepolymer D-2: the composition of the polyether prepolymer is referred to as a combined polyether prepolymer D, and the components are different in content, specifically, 75wt% of combined polyether A and 25wt% of isocyanate are adopted, and the mass content of-OH groups in the obtained combined polyether prepolymer D-2 is 76% -80%.
Combined polyether prepolymer D-3: the composition of the polyether prepolymer is referred to as a combined polyether prepolymer D, and the components are different in content, specifically 65wt% of combined polyether A and 35wt% of isocyanate are adopted, and the mass content of-OH groups in the obtained combined polyether prepolymer D-3 is 70% -75%.
Isocyanate prepolymer E-1: the composition is shown in an isocyanate prepolymer E, and the difference is that the components are different, specifically, 85wt% of isocyanate and 15wt% of o-toluenediamine polyether are adopted, and the mass content of-NCO groups in the obtained isocyanate prepolymer E-1 is 83% -85%.
Isocyanate prepolymer E-2: the composition is shown in an isocyanate prepolymer E, and the difference is that the components are different, specifically 80wt% of isocyanate and 20wt% of o-toluenediamine polyether are adopted, and the mass content of-NCO groups in the obtained isocyanate prepolymer E-2 is 78-80%.
Isocyanate prepolymer E-3: the composition is shown in an isocyanate prepolymer E, and the difference is that the components are different, specifically, 70wt% of isocyanate and 30wt% of o-toluenediamine polyether are adopted, and the mass content of-NCO groups in the obtained isocyanate prepolymer E-3 is 72% -85%.
Composition G-1: see composition G for its composition, except that the combination polyether prepolymer D-1 was used instead of combination polyether prepolymer D.
Composition G-2: see composition G for its composition, except that the combination polyether prepolymer D-2 was used instead of combination polyether prepolymer D.
Composition G-3: see composition G for its composition, except that the combination polyether prepolymer D-3 was used instead of combination polyether prepolymer D.
Composition H-1: see composition H for its composition, except that isocyanate prepolymer E-1 was used instead of isocyanate prepolymer E.
Composition H-2: see composition H for its composition, except that isocyanate prepolymer E-2 was used instead of isocyanate prepolymer E.
Composition H-3: see composition H for its composition, except that isocyanate prepolymer E-3 was used instead of isocyanate prepolymer E.
Composition G-4: 70wt% of the combined polyether prepolymer D and 30wt% of the component C were mixed to obtain a composition G-4 containing a foaming agent and the combined polyether prepolymer D.
Composition H-4: 70% by weight of the isocyanate prepolymer E and 30% by weight of the component C were mixed to obtain a composition H-4 containing a blowing agent and an isocyanate prepolymer E.
Viscosity test example 1
The above compositions were subjected to viscosity tests at different temperatures, and the test results are shown in Table 1.
TABLE 1
Through a plurality of experiments of the inventor, the viscosity of the first component containing isocyanate and the second component containing combined polyether is closer to each other, and the mixing effect is better; meanwhile, the viscosity of the two components cannot be too low or too high, the reaction is too fast and uneven when the viscosity is too low, and partial reaction cannot be caused when the rotating speed is too high. The reaction effect is best when the viscosity of both the two is about 1000 MPa.S.
As can be seen from Table 1, the compositions after prepolymerization, such as composition G and composition H, have viscosities close to and within the range of about 1000 MPa.S at different temperature ranges, which is more advantageous for improving the mixing effect. The viscosities of the composition G-1 and the composition H-1, the viscosities of the composition G-2 and the composition H-2 are close to and also close to about 1000 MPa.S in different temperature ranges, but the degree of the close is inferior to that of the composition G and the composition H.
And, the pre-polymerized isocyanate prepolymer E and the combined polyether prepolymer D are relatively significantly closer than the isocyanate and the combined polyether A.
Compared with the composition F containing the foaming agent and the combined polyether A, the viscosity of the composition G containing the foaming agent and the combined polyether prepolymer D is in the range of about 1000 MPa.S, and the mixing effect is improved.
Foaming test example 2
Polyurethane hard foam DK (i.e., comparative polyurethane hard foam K): the composition comprises the following components: composition F mass ratio=1.2, and the obtained foam was mixed and foamed to give a rigid polyurethane foam DK having a density of 32kg/m 3 。
Polyurethane rigid foam L: in composition H: the composition g=1.2 was mixed and foamed to give a rigid polyurethane foam L having a density of 31.5kg/m 3 . Wherein the mass ratio of-NCO groups in isocyanate prepolymer E to-OH groups in said combined polyether prepolymer D is in the range of (0.98-1.05): 1.
in the process of preparing the polyurethane hard foam DK and the polyurethane hard foam L, a temperature sensing probe is placed in the middle of a corresponding pressure foam to perform temperature test, wherein the highest temperature measured in the polyurethane hard foam DK is 185 ℃, and the highest temperature measured in the polyurethane hard foam L is 120 ℃. It can be seen that the reaction temperature of the polyurethane rigid foam L is far lower than that of the polyurethane rigid foam DK, the reaction control of the polyurethane rigid foam L on the foam is more favorable, the reaction heat is obviously reduced, the formation of foam cells is more favorable, the diameter of the foam cells is smaller, and the demolding property of the foam is better.
Each polyurethane hard foam was subjected to thermal conductivity and dimensional stability test, the thermal conductivity test method is referred to GB/T10294-2008, the dimensional stability test method is referred to GB/T6342-1996, and the demolding time is recorded for comparison, and the results are shown in Table 2.
Foaming test example 3
Polyurethane rigid foam L-1: in composition H-1: composition G-1=1.2 was mixed and foamed to give a pressure foam which was polyurethane hard foam L-1. Wherein the mass ratio of-NCO groups in the isocyanate prepolymer contained to-OH groups in the polyether prepolymer combined contained is in the range of (0.97 to 1.04): 1.
polyurethane rigid foam L-2: in composition H-2: composition G-2=1.2 was mixed and foamed to give a pressure foam which was polyurethane hard foam L-2. Wherein the mass ratio of-NCO groups in the isocyanate prepolymer contained to-OH groups in the polyether prepolymer combined contained is in the range of (0.98-1.05): 1.
polyurethane rigid foam DL-3: in composition H-3: composition G-3=1.2 was mixed and foamed to give a pressure foam which was polyurethane hard foam DL-3. Wherein the mass ratio of-NCO groups in the isocyanate prepolymer contained to-OH groups in the polyether prepolymer combined contained is in the range of (0.96-1.21): 1.
polyurethane rigid foam L-4: in composition H-4: composition G-4=1.2 was mixed and foamed to give a pressure foam which was polyurethane hard foam L-4. Wherein the mass ratio of-NCO groups in the isocyanate prepolymer contained to-OH groups in the polyether prepolymer combined contained is in the range of (0.98-1.05): 1.
the same thermal conductivity and dimensional stability were measured for each polyurethane hard foam, and the results are shown in table 2.
TABLE 2
As can be seen from table 2 above, the polyurethane hard foam (including polyurethane hard foam L, polyurethane hard foam L-1, polyurethane hard foam L-2) obtained by reacting the isocyanate prepolymer with the combined polyether prepolymer according to the present invention can obtain a lower thermal conductivity, a shorter demolding time, and a better dimensional stability than the polyurethane hard foam DK formed from the non-prepolymerized isocyanate and the combined polyether. And under the same conditions, even though the polyurethane rigid foam DL-3 is prepolymerized, the mass ratio of the-NCO group and the-OH group of the invention is not satisfied, and the comprehensive effect of the invention cannot be achieved.
Further, as can be seen from the combination of tables 1 and 2, compared with the polyurethane rigid foam L-1 and the polyurethane rigid foam L-2, the polyurethane rigid foam L scheme adopting the preferable viscosity ranges of the isocyanate prepolymer and the combined polyether prepolymer and the viscosity range adjusted after the foaming agent is added can further reduce the heat conductivity, has shorter demolding time and better dimensional stability.
Further, it can be seen from the combination of tables 1 and 2 that the thermal conductivity can be further reduced by adopting the preferred polyurethane rigid foam L scheme of the present invention, which is adjusted to a specific viscosity range by the foaming agent, compared with the polyurethane rigid foam L-4, and the demolding time is shorter and the dimensional stability is better.
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 (10)
1. The polyurethane hard foam with the ultralow heat conductivity coefficient is characterized in that the first component comprises isocyanate prepolymer, the second component comprises combined polyether prepolymer, the isocyanate prepolymer contains-NCO groups with the mass content of 70% -95%, the combined polyether prepolymer contains-OH groups with the mass content of 70% -95%, and the ratio of-NCO groups in the isocyanate prepolymer to-OH groups in the combined polyether prepolymer is (0.9-1.1): 1.
2. the ultra-low thermal conductivity polyurethane rigid foam according to claim 1, wherein the viscosity of the isocyanate prepolymer at 10-30 ℃ is 5000-11000 mPa-s and the viscosity of the combined polyether prepolymer at 10-30 ℃ is 6000-12000 mPa-s.
3. The polyurethane hard foam with ultralow heat conductivity according to claim 1, wherein the first component and the second component respectively further comprise a foaming agent, the foaming agent accounts for 5-30wt% of the total amount of the corresponding components, the viscosity of the first component is controlled to be 800-1400 mPa.s at 10-30 ℃, and the viscosity of the second component is controlled to be 800-1400 mPa.s at 10-30 ℃.
4. The ultra-low thermal conductivity polyurethane rigid foam according to claim 1, wherein the pre-polymerization raw material of the isocyanate prepolymer comprises a first isocyanate and a first o-toluenediamine type polyether with a pH of 4.5-6, wherein the first o-toluenediamine type polyether accounts for 5-30 wt% of the total amount of the first isocyanate and the first o-toluenediamine type polyether.
5. The ultra-low thermal conductivity polyurethane rigid foam according to claim 1, wherein the pre-polymerization raw material of the combined polyether prepolymer comprises combined polyether and second isocyanate, and the second isocyanate accounts for 5-35 wt% of the total amount of the combined polyether and the second isocyanate.
6. The ultra-low thermal conductivity polyurethane rigid foam according to claim 5, wherein the composition of the combined polyether comprises, based on the total amount of the combined polyether: 46 to 81.35 weight percent of polyether polyol, 15 to 30 weight percent of polyester polyol, 1.5 to 4 weight percent of silicone oil, 1 to 5 weight percent of catalyst, 1 to 8 weight percent of water, 0.05 to 3.5 weight percent of nanocellulose and 0.1 to 3.5 weight percent of 1-butyl-3-methylimidazole hexafluorophosphate.
7. The ultra-low thermal conductivity polyurethane rigid foam according to claim 6, wherein said polyether polyol comprises a second o-toluenediamine type polyether having a pH of 4.5-6, said second o-toluenediamine type polyether comprising 35wt% to 55wt% of polyether polyol.
8. A method for preparing an ultra-low thermal conductivity polyurethane rigid foam according to any one of claims 1 to 7, comprising: and mixing and foaming the first component containing the isocyanate prepolymer and the second component containing the combined polyether prepolymer to obtain polyurethane hard foam, wherein the heat conductivity coefficient of the obtained polyurethane hard foam is below 0.015 w/m.k.
9. The method for preparing an ultra-low thermal conductivity polyurethane rigid foam according to claim 8, further comprising: firstly, carrying out first mixing on isocyanate prepolymer and foaming agent to obtain a first component; and performing second mixing on the combined polyether prepolymer and the foaming agent to obtain a second component; the first component and the second component are then subjected to the mixing foaming.
10. The method for preparing an ultra-low thermal conductivity polyurethane rigid foam according to claim 8 or 9, further comprising:
first prepolymerizing first isocyanate and first o-toluenediamine type polyether with pH of 4.5-6 to obtain isocyanate prepolymer; wherein the conditions of the first prepolymerization comprise: the temperature is 50-70 ℃ and the time is 1-3h;
firstly, carrying out second prepolymerization on combined polyether and second isocyanate to obtain a combined polyether prepolymer; wherein the conditions of the second prepolymerization comprise: the temperature is 50-70 ℃ and the time is 1-3h.
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| CN202311423397.0A Pending CN117467107A (en) | 2023-10-31 | 2023-10-31 | Polyurethane rigid foam with ultralow heat conductivity coefficient and preparation method thereof |
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