CN116444758A - Polyurethane heat-insulating material for building and manufacturing process thereof - Google Patents
Polyurethane heat-insulating material for building and manufacturing process thereof Download PDFInfo
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- CN116444758A CN116444758A CN202310590621.9A CN202310590621A CN116444758A CN 116444758 A CN116444758 A CN 116444758A CN 202310590621 A CN202310590621 A CN 202310590621A CN 116444758 A CN116444758 A CN 116444758A
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- 229920002635 polyurethane Polymers 0.000 title claims abstract description 39
- 239000004814 polyurethane Substances 0.000 title claims abstract description 39
- 238000004519 manufacturing process Methods 0.000 title claims abstract description 11
- 239000011810 insulating material Substances 0.000 title description 35
- 239000012774 insulation material Substances 0.000 claims abstract description 27
- 238000003756 stirring Methods 0.000 claims description 39
- RNFJDJUURJAICM-UHFFFAOYSA-N 2,2,4,4,6,6-hexaphenoxy-1,3,5-triaza-2$l^{5},4$l^{5},6$l^{5}-triphosphacyclohexa-1,3,5-triene Chemical group N=1P(OC=2C=CC=CC=2)(OC=2C=CC=CC=2)=NP(OC=2C=CC=CC=2)(OC=2C=CC=CC=2)=NP=1(OC=1C=CC=CC=1)OC1=CC=CC=C1 RNFJDJUURJAICM-UHFFFAOYSA-N 0.000 claims description 37
- 239000000203 mixture Substances 0.000 claims description 28
- 239000004970 Chain extender Substances 0.000 claims description 27
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 26
- 229920005862 polyol Polymers 0.000 claims description 19
- 150000003077 polyols Chemical class 0.000 claims description 19
- 239000003054 catalyst Substances 0.000 claims description 17
- 239000000463 material Substances 0.000 claims description 17
- 239000004721 Polyphenylene oxide Substances 0.000 claims description 14
- 229920000570 polyether Polymers 0.000 claims description 14
- 229910052757 nitrogen Inorganic materials 0.000 claims description 13
- OFBQJSOFQDEBGM-UHFFFAOYSA-N Pentane Chemical compound CCCCC OFBQJSOFQDEBGM-UHFFFAOYSA-N 0.000 claims description 12
- 238000002156 mixing Methods 0.000 claims description 12
- 239000011521 glass Substances 0.000 claims description 10
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 claims description 9
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical group [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 claims description 9
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 claims description 9
- 125000002887 hydroxy group Chemical group [H]O* 0.000 claims description 9
- 239000011324 bead Substances 0.000 claims description 8
- 238000005187 foaming Methods 0.000 claims description 8
- 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 claims description 6
- XDTMQSROBMDMFD-UHFFFAOYSA-N Cyclohexane Chemical compound C1CCCCC1 XDTMQSROBMDMFD-UHFFFAOYSA-N 0.000 claims description 6
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 6
- KXBFLNPZHXDQLV-UHFFFAOYSA-N [cyclohexyl(diisocyanato)methyl]cyclohexane Chemical compound C1CCCCC1C(N=C=O)(N=C=O)C1CCCCC1 KXBFLNPZHXDQLV-UHFFFAOYSA-N 0.000 claims description 6
- UKLDJPRMSDWDSL-UHFFFAOYSA-L [dibutyl(dodecanoyloxy)stannyl] dodecanoate Chemical compound CCCCCCCCCCCC(=O)O[Sn](CCCC)(CCCC)OC(=O)CCCCCCCCCCC UKLDJPRMSDWDSL-UHFFFAOYSA-L 0.000 claims description 6
- 238000001816 cooling Methods 0.000 claims description 6
- 239000012975 dibutyltin dilaurate Substances 0.000 claims description 6
- 125000005442 diisocyanate group Chemical group 0.000 claims description 6
- 238000007599 discharging Methods 0.000 claims description 6
- 239000000945 filler Substances 0.000 claims description 6
- 239000004088 foaming agent Substances 0.000 claims description 6
- 239000013067 intermediate product Substances 0.000 claims description 6
- 238000000034 method Methods 0.000 claims description 6
- 239000002994 raw material Substances 0.000 claims description 6
- KSBAEPSJVUENNK-UHFFFAOYSA-L tin(ii) 2-ethylhexanoate Chemical compound [Sn+2].CCCCC(CC)C([O-])=O.CCCCC(CC)C([O-])=O KSBAEPSJVUENNK-UHFFFAOYSA-L 0.000 claims description 6
- 238000005406 washing Methods 0.000 claims description 6
- 238000001035 drying Methods 0.000 claims description 5
- 239000002253 acid Substances 0.000 claims description 4
- 125000005336 allyloxy group Chemical group 0.000 claims description 4
- 125000000325 methylidene group Chemical group [H]C([H])=* 0.000 claims description 4
- 230000008569 process Effects 0.000 claims description 4
- RYHBNJHYFVUHQT-UHFFFAOYSA-N 1,4-Dioxane Chemical compound C1COCCO1 RYHBNJHYFVUHQT-UHFFFAOYSA-N 0.000 claims description 3
- CZHYKKAKFWLGJO-UHFFFAOYSA-N dimethyl phosphite Chemical compound COP([O-])OC CZHYKKAKFWLGJO-UHFFFAOYSA-N 0.000 claims description 3
- 238000010438 heat treatment Methods 0.000 claims description 3
- 239000002244 precipitate Substances 0.000 claims description 3
- 238000001556 precipitation Methods 0.000 claims description 3
- 238000002360 preparation method Methods 0.000 claims description 3
- 239000011343 solid material Substances 0.000 claims description 3
- 239000002904 solvent Substances 0.000 claims description 3
- GIRKRMUMWJFNRI-UHFFFAOYSA-N tris(dimethylamino)silicon Chemical compound CN(C)[Si](N(C)C)N(C)C GIRKRMUMWJFNRI-UHFFFAOYSA-N 0.000 claims description 3
- 238000004821 distillation Methods 0.000 claims description 2
- 150000005846 sugar alcohols Polymers 0.000 claims description 2
- 238000010276 construction Methods 0.000 claims 7
- 239000003063 flame retardant Substances 0.000 description 10
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 9
- 230000000694 effects Effects 0.000 description 9
- 238000010521 absorption reaction Methods 0.000 description 7
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 7
- 229910052760 oxygen Inorganic materials 0.000 description 7
- 239000001301 oxygen Substances 0.000 description 7
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 6
- 229910052799 carbon Inorganic materials 0.000 description 6
- 238000002485 combustion reaction Methods 0.000 description 6
- 229920005830 Polyurethane Foam Polymers 0.000 description 5
- 239000011496 polyurethane foam Substances 0.000 description 5
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 description 4
- 239000006260 foam Substances 0.000 description 4
- 238000009413 insulation Methods 0.000 description 4
- 230000004048 modification Effects 0.000 description 4
- 238000012986 modification Methods 0.000 description 4
- 229910052698 phosphorus Inorganic materials 0.000 description 4
- 239000011574 phosphorus Substances 0.000 description 4
- 229920000642 polymer Polymers 0.000 description 4
- 230000000052 comparative effect Effects 0.000 description 3
- 230000006835 compression Effects 0.000 description 3
- 238000007906 compression 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
- 238000005033 Fourier transform infrared spectroscopy Methods 0.000 description 2
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 description 2
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 2
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 2
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 2
- 230000009471 action Effects 0.000 description 2
- 238000007792 addition Methods 0.000 description 2
- 239000004566 building material Substances 0.000 description 2
- IQPQWNKOIGAROB-UHFFFAOYSA-N isocyanate group Chemical group [N-]=C=O IQPQWNKOIGAROB-UHFFFAOYSA-N 0.000 description 2
- 239000004005 microsphere Substances 0.000 description 2
- 229920003023 plastic Polymers 0.000 description 2
- 239000004033 plastic Substances 0.000 description 2
- 238000007142 ring opening reaction Methods 0.000 description 2
- 229910052710 silicon Inorganic materials 0.000 description 2
- 239000010703 silicon Substances 0.000 description 2
- 229910052717 sulfur Inorganic materials 0.000 description 2
- 239000011593 sulfur Substances 0.000 description 2
- KXGFMDJXCMQABM-UHFFFAOYSA-N 2-methoxy-6-methylphenol Chemical compound [CH]OC1=CC=CC([CH])=C1O KXGFMDJXCMQABM-UHFFFAOYSA-N 0.000 description 1
- IAYPIBMASNFSPL-UHFFFAOYSA-N Ethylene oxide Chemical compound C1CO1 IAYPIBMASNFSPL-UHFFFAOYSA-N 0.000 description 1
- 239000004793 Polystyrene Substances 0.000 description 1
- 229910018540 Si C Inorganic materials 0.000 description 1
- 229910007991 Si-N Inorganic materials 0.000 description 1
- 229910006294 Si—N Inorganic materials 0.000 description 1
- 230000002411 adverse Effects 0.000 description 1
- 125000003342 alkenyl group Chemical group 0.000 description 1
- 229910000147 aluminium phosphate Inorganic materials 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 239000011449 brick Substances 0.000 description 1
- 230000003197 catalytic effect Effects 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000001514 detection method Methods 0.000 description 1
- DLQDGVZAEYZNTG-UHFFFAOYSA-N dimethyl hydrogen phosphite Chemical group COP(O)OC DLQDGVZAEYZNTG-UHFFFAOYSA-N 0.000 description 1
- 125000003700 epoxy group Chemical group 0.000 description 1
- 230000001747 exhibiting effect Effects 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 238000006459 hydrosilylation reaction Methods 0.000 description 1
- 239000011256 inorganic filler Substances 0.000 description 1
- 229910003475 inorganic filler Inorganic materials 0.000 description 1
- 239000012796 inorganic flame retardant Substances 0.000 description 1
- 239000012948 isocyanate Substances 0.000 description 1
- 150000002513 isocyanates Chemical class 0.000 description 1
- 239000011490 mineral wool Substances 0.000 description 1
- TWVSWDVJBJKDAA-UHFFFAOYSA-N n-[bis(dimethylamino)silyl]-n-methylmethanamine Chemical group CN(C)[SiH](N(C)C)N(C)C TWVSWDVJBJKDAA-UHFFFAOYSA-N 0.000 description 1
- 239000012466 permeate Substances 0.000 description 1
- 238000005191 phase separation Methods 0.000 description 1
- 229920001568 phenolic resin Polymers 0.000 description 1
- 239000005011 phenolic resin Substances 0.000 description 1
- 239000002861 polymer material Substances 0.000 description 1
- 229920002223 polystyrene Polymers 0.000 description 1
- 239000000047 product Substances 0.000 description 1
- 239000013049 sediment Substances 0.000 description 1
- 229910010271 silicon carbide Inorganic materials 0.000 description 1
- 239000000377 silicon dioxide Substances 0.000 description 1
- 235000012239 silicon dioxide Nutrition 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 239000000243 solution Substances 0.000 description 1
- 238000010998 test method Methods 0.000 description 1
- 229930195735 unsaturated hydrocarbon Natural products 0.000 description 1
- 238000001291 vacuum drying Methods 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- 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
- C08G18/65—Low-molecular-weight compounds having active hydrogen with high-molecular-weight compounds having active hydrogen
- C08G18/66—Compounds of groups C08G18/42, C08G18/48, or C08G18/52
- C08G18/6666—Compounds of group C08G18/48 or C08G18/52
-
- 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
- C08G18/30—Low-molecular-weight compounds
- C08G18/38—Low-molecular-weight compounds having heteroatoms other than oxygen
- C08G18/3893—Low-molecular-weight compounds having heteroatoms other than oxygen containing silicon
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
- C08G18/40—High-molecular-weight compounds
- C08G18/48—Polyethers
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J9/00—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof
- C08J9/04—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
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K7/00—Use of ingredients characterised by shape
- C08K7/22—Expanded, porous or hollow particles
- C08K7/24—Expanded, porous or hollow particles inorganic
- C08K7/28—Glass
-
- 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
- C08J2375/00—Characterised by the use of polyureas or polyurethanes; Derivatives of such polymers
- C08J2375/04—Polyurethanes
- C08J2375/08—Polyurethanes from polyethers
Landscapes
- Chemical & Material Sciences (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Polyurethanes Or Polyureas (AREA)
Abstract
The invention relates to the technical field of heat insulation materials, and discloses a polyurethane heat insulation material for building and a manufacturing process thereof.
Description
Technical Field
The invention relates to the technical field of heat insulation materials, in particular to a polyurethane heat insulation material for buildings and a manufacturing process thereof.
Background
The heat insulating material is a novel building material with heat insulating and decorating functions, and has lower heat conductivity coefficient than the building material such as solid bricks and the like because the inside of the heat insulating material contains a large number of closed hole structures, so that the heat insulating material has more excellent heat insulating effect and gradually becomes the main stream choice of modern buildings. The heat insulating materials used in the market at present mainly comprise organic heat insulating materials and inorganic heat insulating materials, wherein the inorganic heat insulating materials are mainly rock wool heat insulating materials, and the inorganic heat insulating materials are high in hygroscopicity, easy to permeate water and difficult to keep good heat insulating effect in a moist environment for a long time. The organic heat insulating material has light texture, excellent heat insulating effect, sound absorption and other advantages, so that the organic heat insulating material is gradually different from the building heat insulating material. At present, the organic heat-insulating material is usually made of high polymer materials such as phenolic resin, polystyrene or polyurethane and the like as base materials, and the foamed heat-insulating material is formed after foaming, but the high polymer foamed heat-insulating material also has larger defects, wherein the problem of poor flame retardance is most serious, so that in the actual use process, the organic heat-insulating material is mostly required to be improved, and the flame retardance of the organic heat-insulating material is enhanced.
At present, the flame retardant modification is often carried out on the polymer foam heat-insulating material by adding a large amount of inorganic filler or flame retardant into a base material, and the mode can improve the flame retardant property of the polymer foam heat-insulating material, but has poor compatibility, is easy to generate phase separation, and can also have adverse effect on other properties of the polymer foam heat-insulating material, so that a conventional physical addition type modification mode cannot obtain good modification effect.
Disclosure of Invention
The invention aims to provide a polyurethane heat-insulating material for building and a manufacturing process thereof, which solve the problem of poor flame retardant property of polyurethane foam heat-insulating materials.
The aim of the invention can be achieved by the following technical scheme:
the polyurethane heat insulation material for the building comprises the following raw materials in parts by weight: 50-70 parts of polyalcohol, 25-40 parts of diisocyanate, 1-3 parts of flame-retardant chain extender, 1-5 parts of filler, 2-4 parts of foaming agent and 2-6 parts of organotin catalyst;
the preparation method of the flame-retardant chain extender comprises the following steps:
step one: dissolving tris (dimethylamino) silane and 2,2' - [ [2- (allyloxy) -1, 3-phenylene ] di (methylene) ] di (ethylene oxide) in toluene, stirring uniformly, introducing nitrogen for protection, heating the system to 70-80 ℃ under stirring, adding a catalyst, stirring at constant temperature for 4-8h after adding, pouring the materials into ethanol for precipitation, taking the precipitate, washing and drying to obtain an intermediate product;
step two: dissolving the intermediate product and the dimethyl phosphite in N, N-dimethylformamide, adding an alkaline catalyst under stirring, introducing nitrogen for protection, raising the temperature of the system to 120-135 ℃, stirring for 6-18h, removing the solvent by reduced pressure distillation, taking a solid material, washing and drying in vacuum to obtain the flame-retardant chain extender.
Through the technical scheme, under the action of a catalyst, si-H bond in a tri (dimethylamino) silane structure can undergo hydrosilylation reaction with unsaturated alkenyl in a 2,2' - [ [2- (allyloxy) -1, 3-phenylene ] di (methylene) ] di (ethylene oxide) structure to obtain an intermediate, and because the intermediate structure contains two equivalents of epoxy groups, the intermediate structure can further undergo ring-opening reaction with P-H bond in a dimethyl phosphite structure under the conditions of an alkaline catalyst and high temperature to obtain the flame-retardant chain extender, wherein the flame-retardant chain extender not only contains three flame retardant elements of nitrogen, phosphorus and silicon, but also generates active hydroxyl in the structure due to the ring-opening reaction.
Further, the polyol is a polyether polyol, the number average molecular weight is 400-500, and the hydroxyl value is 350-500mgKOH/g.
Further, the diisocyanate is any one of diphenylmethane diisocyanate or dicyclohexylmethane diisocyanate.
Further, the filler is hollow glass beads.
Further, the foaming agent is any one of n-pentane or cyclohexane.
Further, the organotin catalyst is any one of stannous octoate or dibutyltin dilaurate.
Further, in the first step, the catalyst is chloroplatinic acid.
Further, in the second step, the alkaline catalyst is potassium hydroxide.
A manufacturing process of a polyurethane heat-insulating material for a building comprises the following steps:
the first step: pouring polyol, diisocyanate and an organotin catalyst in parts by weight into a reactor, stirring and mixing for 20-40min, then raising the temperature of the system to 50-60 ℃, and stirring for 1-2h to obtain a mixture (1);
and a second step of: pouring the flame-retardant chain extender in parts by weight into the mixture (1), and continuously stirring for 1-2h to obtain the mixture (2);
and a third step of: pouring filler and foaming agent in parts by weight into the mixture (2), stirring and mixing uniformly, pouring the materials into a mold, foaming for 10-20min at 50-55 ℃, cooling to room temperature, curing for 30-60min, then placing the materials into a temperature environment of 70-80 ℃ for curing for 1-3h, and discharging to obtain the polyurethane heat insulation material.
According to the technical scheme, polyol and binary isocyanate are subjected to prepolymerization reaction under the action of an organotin catalyst to obtain a mixture (1) of isocyanate groups at the end positions, and the flame-retardant chain extender structure contains active hydroxyl groups and can react with the isocyanate groups at the end parts of the mixture (1) to form a mixture (2), and then the mixture is subjected to foaming, curing and curing processes to obtain the polyurethane heat-insulating material.
The invention has the beneficial effects that:
according to the invention, a flame-retardant chain extender is prepared by starting from a polyurethane structure, ternary flame-retardant elements of nitrogen, phosphorus and sulfur are introduced into a polyurethane molecular chain, wherein oxygen acid such as phosphoric acid formed after combustion of the phosphorus element has a catalytic carbon forming effect, a carbon layer with higher density can be formed on the surface of the polyurethane foam heat insulation material, a combustion object can be separated from oxygen and heat, the combustion of the polyurethane foam heat insulation material is difficult to continue, the nitrogen element can burn to generate non-combustible gas such as nitrogen, the oxygen concentration around the polyurethane foam heat insulation material can be rapidly reduced after the nitrogen element is diffused, the nitrogen element is in an anaerobic environment, the combustion is further interrupted, silicon dioxide generated by the combustion of the silicon element can be attached to the carbon layer structure in a sediment form, the strength of the carbon layer is enhanced, the compactness of the carbon layer is improved, the carbon layer has a stronger heat insulation effect, and three flame-retardant elements are mutually coordinated, so that the flame retardant performance of the polyurethane heat insulation material can be greatly improved. In addition, the flame-retardant chain extender structure contains a rigid benzene ring structure, so that the strength of the polyurethane foam heat-insulating material can be effectively improved.
Of course, it is not necessary for any one product to practice the invention to achieve all of the advantages set forth above at the same time.
Drawings
In order to more clearly illustrate the technical solutions of the embodiments of the present invention, the drawings that are needed for the description of the embodiments will be briefly described below, and it is obvious that the drawings in the following description are only some embodiments of the present invention, and that other drawings may be obtained according to these drawings without inventive effort for a person skilled in the art.
FIG. 1 is a FTIR chart of a flame retardant chain extender in an embodiment of the present invention.
Detailed Description
The following description of the embodiments of the present invention will be made clearly and completely with reference to the accompanying drawings, in which it is apparent that the embodiments described are only some embodiments of the present invention, but not all embodiments. All other embodiments, which can be made by those skilled in the art based on the embodiments of the invention without making any inventive effort, are intended to be within the scope of the invention.
In the following examples, the preparation method of the flame retardant chain extender comprises the following steps:
step one: dissolving 1.5g of tris (dimethylamino) silane and 2.3g of 2,2' - [ [2- (allyloxy) -1, 3-phenylene ] bis (methylene) ] bis (ethylene oxide) in toluene, stirring uniformly, introducing nitrogen for protection, heating the system to 75 ℃ under stirring, adding 0.01g of chloroplatinic acid, stirring at constant temperature for 6 hours, pouring the materials into ethanol for precipitation, taking the precipitate, washing and drying to obtain an intermediate product;
step two: 1.2g of intermediate product and 1.4g of dimethyl phosphite are dissolved in N, N-dimethylformamide, 0.2g of potassium hydroxide is added under the stirring condition, nitrogen is introduced for protection, the temperature of the system is increased to 130 ℃, after stirring for 12 hours, the solvent is distilled off under reduced pressure, the solid material is taken out, and the flame-retardant chain extender is obtained after washing and vacuum drying.
The flame-retardant chain extender is subjected to 4000-500 cm by using an AVATAR360 type Fourier transform infrared spectrometer -1 The result of scanning is shown in FIG. 1, and as can be seen from FIG. 1, the flame retardant chain extender is used at 3421cm -1 The absorption peak of hydroxyl appears at 3058cm -1 An unsaturated hydrocarbon bond absorption peak of benzene ring appears at 1280-1350 cm -1 The absorption peak of P=O appears at 1200-1260 cm -1 The Si-C absorption peak appears at the position of 1000-1050 cm -1 The absorption peak of P-O-C appears at 800-1000 cm -1 An absorption peak of Si-N appears at the site.
Example 1
The polyurethane heat insulation material for the building comprises the following raw materials in parts by weight: 50 parts of polyether polyol, 25 parts of diphenylmethane diisocyanate, 1 part of flame-retardant chain extender, 1 part of hollow glass microsphere, 2 parts of n-pentane and 2 parts of stannous octoate;
the manufacturing process of the polyurethane heat-insulating material comprises the following steps:
the first step: pouring polyether polyol, diphenylmethane diisocyanate and stannous octoate in parts by weight into a reactor, stirring and mixing for 20min, then raising the temperature of the system to 50 ℃, and stirring for 1h to obtain a mixture (1), wherein the number average molecular weight of the polyether polyol is 440, and the hydroxyl value is 380mgKOH/g;
and a second step of: pouring the flame-retardant chain extender in parts by weight into the mixture (1), and continuously stirring for 1h to obtain a mixture (2);
and a third step of: pouring the hollow glass beads and n-pentane into the mixture (2) according to the weight parts, stirring and mixing uniformly, pouring the materials into a mold, foaming for 10min at the temperature of 50 ℃, cooling to room temperature, curing for 30min, then placing the materials into the temperature environment of 70 ℃ for curing for 1h, and discharging to obtain the polyurethane heat-insulating material.
Example 2
The polyurethane heat insulation material for the building comprises the following raw materials in parts by weight: 60 parts of polyether polyol, 35 parts of dicyclohexylmethane diisocyanate, 2 parts of flame-retardant chain extender, 4 parts of hollow glass beads, 3 parts of cyclohexane and 4.5 parts of dibutyl tin dilaurate;
the manufacturing process of the polyurethane heat-insulating material comprises the following steps:
the first step: pouring polyether polyol, dicyclohexylmethane diisocyanate and dibutyltin dilaurate in parts by weight into a reactor, stirring and mixing for 30min, then raising the system temperature to 55 ℃, and stirring for 2h to obtain a mixture (1), wherein the number average molecular weight of the polyether polyol is 440, and the hydroxyl value is 380mgKOH/g;
and a second step of: pouring the flame-retardant chain extender in parts by weight into the mixture (1), and continuously stirring for 2 hours to obtain the mixture (2);
and a third step of: pouring the hollow glass beads and cyclohexane in parts by weight into a mixture (2), stirring and mixing uniformly, pouring the materials into a mold, foaming for 15min at the temperature of 55 ℃, cooling to room temperature, curing for 40min, placing the materials in the temperature of 75 ℃ for curing for 2h, and discharging to obtain the polyurethane heat-insulating material.
Example 3
The polyurethane heat insulation material for the building comprises the following raw materials in parts by weight: 70 parts of polyether polyol, 40 parts of diphenylmethane diisocyanate, 3 parts of flame-retardant chain extender, 5 parts of hollow glass microsphere, 4 parts of n-pentane and 6 parts of stannous octoate;
the manufacturing process of the polyurethane heat-insulating material comprises the following steps:
the first step: pouring polyether polyol, diphenylmethane diisocyanate and stannous octoate in parts by weight into a reactor, stirring and mixing for 40min, then raising the temperature of the system to 60 ℃, and stirring for 2h to obtain a mixture (1), wherein the number average molecular weight of the polyether polyol is 440, and the hydroxyl value is 380mgKOH/g;
and a second step of: pouring the flame-retardant chain extender in parts by weight into the mixture (1), and continuously stirring for 2 hours to obtain the mixture (2);
and a third step of: pouring the hollow glass beads and n-pentane into the mixture (2) according to the weight parts, stirring and mixing uniformly, pouring the materials into a mold, foaming for 20min at the temperature of 55 ℃, cooling to room temperature, curing for 60min, then placing the materials into the temperature environment of 80 ℃ for curing for 3h, and discharging to obtain the polyurethane heat-insulating material.
Comparative example 1
The polyurethane heat insulation material for the building comprises the following raw materials in parts by weight: 60 parts of polyether polyol, 35 parts of dicyclohexylmethane diisocyanate, 2 parts of ethylene glycol, 4 parts of hollow glass beads, 3 parts of cyclohexane and 4.5 parts of dibutyl tin dilaurate;
the manufacturing process of the polyurethane heat-insulating material comprises the following steps:
the first step: pouring polyether polyol, dicyclohexylmethane diisocyanate and dibutyltin dilaurate in parts by weight into a reactor, stirring and mixing for 30min, then raising the system temperature to 55 ℃, and stirring for 2h to obtain a mixture (1), wherein the number average molecular weight of the polyether polyol is 420, and the hydroxyl value is 380mgKOH/g;
and a second step of: pouring the ethylene glycol in parts by weight into the mixture (1), and continuously stirring for 2 hours to obtain the mixture (2);
and a third step of: pouring the hollow glass beads and cyclohexane in parts by weight into a mixture (2), stirring and mixing uniformly, pouring the materials into a mold, foaming for 15min at the temperature of 55 ℃, cooling to room temperature, curing for 40min, placing the materials in the temperature of 75 ℃ for curing for 2h, and discharging to obtain the polyurethane heat-insulating material.
Performance detection
The polyurethane thermal insulation materials prepared in the examples 1 to 3 of the present invention were cut into test samples meeting the specification, and the combustion behavior was measured in part 2 by the oxygen index method for plastics with reference to the national standard GB/T2406.2-2009: room temperature test, in which limiting oxygen index test is carried out on the sample to evaluate the flame retardant property of the sample; the compression strength of a sample is tested by referring to national standard GB/T8813-2020, determination of compression Property of rigid foam; referring to national standard GB/T3399-1982 "thermal plate method for test method for Plastic thermal conductivity", the thermal conductivity of the sample is tested, the thermal insulation performance of the sample is evaluated, and the test results are shown in the following table:
| example 1 | Example 2 | Example 3 | Comparative example 1 | |
| Limiting oxygen index (%) | 32.8 | 33.4 | 33.3 | 21.1 |
| Compressive Strength (kPa) | 151.9 | 153.1 | 152.6 | 134.8 |
| Coefficient of thermal conductivity (W/m.K) | 0.0245 | 0.0240 | 0.0242 | 0.0249 |
As can be seen from the above table, the polyurethane thermal insulation materials prepared in the examples 1 to 3 of the present invention have higher limiting oxygen index values, thus exhibiting excellent flame retardant properties, and simultaneously have high compressive strength and low thermal conductivity, thus also having higher strength and thermal insulation effects. The polyurethane thermal insulation material prepared in comparative example 1 uses conventional ethylene glycol as a chain extender, so the structure does not contain a flame-retardant chain extender, and although still has good thermal insulation effect, nitrogen, phosphorus and sulfur flame retardant elements in the flame-retardant chain extender cannot be utilized for flame retardance, and additional rigid benzene ring structures cannot be introduced into polyurethane molecular chains, so the flame retardance and the compression strength are obviously poor.
The foregoing is merely illustrative and explanatory of the principles of the invention, as various modifications and additions may be made to the specific embodiments described, or similar thereto, by those skilled in the art, without departing from the principles of the invention or beyond the scope of the appended claims.
Claims (9)
1. The polyurethane heat insulation material for the building is characterized by comprising the following raw materials in parts by weight: 50-70 parts of polyalcohol, 25-40 parts of diisocyanate, 1-3 parts of flame-retardant chain extender, 1-5 parts of filler, 2-4 parts of foaming agent and 2-6 parts of organotin catalyst;
the preparation method of the flame-retardant chain extender comprises the following steps:
step one: dissolving tris (dimethylamino) silane and 2,2' - [ [2- (allyloxy) -1, 3-phenylene ] di (methylene) ] di (ethylene oxide) in toluene, stirring uniformly, introducing nitrogen for protection, heating the system to 70-80 ℃ under stirring, adding a catalyst, stirring at constant temperature for 4-8h after adding, pouring the materials into ethanol for precipitation, taking the precipitate, washing and drying to obtain an intermediate product;
step two: dissolving the intermediate product and the dimethyl phosphite in N, N-dimethylformamide, adding an alkaline catalyst under stirring, introducing nitrogen for protection, raising the temperature of the system to 120-135 ℃, stirring for 6-18h, removing the solvent by reduced pressure distillation, taking a solid material, washing and drying in vacuum to obtain the flame-retardant chain extender.
2. The polyurethane insulation material for construction according to claim 1, wherein the polyol is a polyether polyol, has a number average molecular weight of 400 to 500, and has a hydroxyl value of 350 to 500mgKOH/g.
3. The polyurethane insulation material for construction according to claim 1, wherein the diisocyanate is any one of diphenylmethane diisocyanate or dicyclohexylmethane diisocyanate.
4. The polyurethane insulation material for construction according to claim 1, wherein the filler is hollow glass beads.
5. The polyurethane thermal insulation material for building according to claim 1, wherein the foaming agent is any one of n-pentane and cyclohexane.
6. The polyurethane insulation material for construction according to claim 1, wherein the organotin catalyst is any one of stannous octoate or dibutyltin dilaurate.
7. The polyurethane insulation material for construction according to claim 1, wherein in the first step, the catalyst is chloroplatinic acid.
8. The polyurethane insulation material for construction according to claim 1, wherein in the second step, the alkaline catalyst is potassium hydroxide.
9. A process for manufacturing a polyurethane insulation material for construction according to claim 1, wherein the process comprises the steps of:
the first step: pouring polyol, diisocyanate and an organotin catalyst in parts by weight into a reactor, stirring and mixing for 20-40min, then raising the temperature of the system to 50-60 ℃, and stirring for 1-2h to obtain a mixture (1);
and a second step of: pouring the flame-retardant chain extender in parts by weight into the mixture (1), and continuously stirring for 1-2h to obtain the mixture (2);
and a third step of: pouring filler and foaming agent in parts by weight into the mixture (2), stirring and mixing uniformly, pouring the materials into a mold, foaming for 10-20min at 50-55 ℃, cooling to room temperature, curing for 30-60min, then placing the materials into a temperature environment of 70-80 ℃ for curing for 1-3h, and discharging to obtain the polyurethane heat insulation material.
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