CN114752092B - Production process of aerogel polyurethane thermal insulation material - Google Patents
Production process of aerogel polyurethane thermal insulation material Download PDFInfo
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- CN114752092B CN114752092B CN202210388717.2A CN202210388717A CN114752092B CN 114752092 B CN114752092 B CN 114752092B CN 202210388717 A CN202210388717 A CN 202210388717A CN 114752092 B CN114752092 B CN 114752092B
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- 239000004964 aerogel Substances 0.000 title claims abstract description 80
- 229920002635 polyurethane Polymers 0.000 title claims abstract description 23
- 239000004814 polyurethane Substances 0.000 title claims abstract description 23
- 239000012774 insulation material Substances 0.000 title claims abstract description 13
- 238000004519 manufacturing process Methods 0.000 title claims abstract description 8
- 239000003054 catalyst Substances 0.000 claims abstract description 28
- 239000004594 Masterbatch (MB) Substances 0.000 claims abstract description 17
- 238000011049 filling Methods 0.000 claims abstract description 15
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 15
- 239000004433 Thermoplastic polyurethane Substances 0.000 claims abstract description 10
- 229920002803 thermoplastic polyurethane Polymers 0.000 claims abstract description 10
- WEVYAHXRMPXWCK-UHFFFAOYSA-N Acetonitrile Chemical compound CC#N WEVYAHXRMPXWCK-UHFFFAOYSA-N 0.000 claims description 48
- 239000000243 solution Substances 0.000 claims description 31
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 claims description 30
- 238000000034 method Methods 0.000 claims description 14
- 238000006243 chemical reaction Methods 0.000 claims description 13
- VTYYLEPIZMXCLO-UHFFFAOYSA-L Calcium carbonate Chemical compound [Ca+2].[O-]C([O-])=O VTYYLEPIZMXCLO-UHFFFAOYSA-L 0.000 claims description 12
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 10
- 238000001125 extrusion Methods 0.000 claims description 9
- 238000002156 mixing Methods 0.000 claims description 9
- WERYXYBDKMZEQL-UHFFFAOYSA-N butane-1,4-diol Chemical compound OCCCCO WERYXYBDKMZEQL-UHFFFAOYSA-N 0.000 claims description 8
- 238000010438 heat treatment Methods 0.000 claims description 8
- 239000000463 material Substances 0.000 claims description 7
- 229910000019 calcium carbonate Inorganic materials 0.000 claims description 6
- 229920001971 elastomer Polymers 0.000 claims description 6
- 239000000806 elastomer Substances 0.000 claims description 6
- 239000011240 wet gel Substances 0.000 claims description 6
- 239000000499 gel Substances 0.000 claims description 5
- 238000003756 stirring Methods 0.000 claims description 5
- 230000002194 synthesizing effect Effects 0.000 claims description 5
- WYTZZXDRDKSJID-UHFFFAOYSA-N (3-aminopropyl)triethoxysilane Chemical compound CCO[Si](OCC)(OCC)CCCN WYTZZXDRDKSJID-UHFFFAOYSA-N 0.000 claims description 4
- 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 4
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims description 4
- 239000005058 Isophorone diisocyanate Substances 0.000 claims description 4
- 239000004965 Silica aerogel Substances 0.000 claims description 4
- 230000032683 aging Effects 0.000 claims description 4
- 229910052797 bismuth Inorganic materials 0.000 claims description 4
- 239000008367 deionised water Substances 0.000 claims description 4
- 229910021641 deionized water Inorganic materials 0.000 claims description 4
- 238000001035 drying Methods 0.000 claims description 4
- 229910052739 hydrogen Inorganic materials 0.000 claims description 4
- 239000001257 hydrogen Substances 0.000 claims description 4
- NIMLQBUJDJZYEJ-UHFFFAOYSA-N isophorone diisocyanate Chemical compound CC1(C)CC(N=C=O)CC(C)(CN=C=O)C1 NIMLQBUJDJZYEJ-UHFFFAOYSA-N 0.000 claims description 4
- 239000011259 mixed solution Substances 0.000 claims description 4
- 229920001451 polypropylene glycol Polymers 0.000 claims description 4
- 238000010992 reflux Methods 0.000 claims description 4
- 239000002904 solvent Substances 0.000 claims description 4
- LFQCEHFDDXELDD-UHFFFAOYSA-N tetramethyl orthosilicate Chemical compound CO[Si](OC)(OC)OC LFQCEHFDDXELDD-UHFFFAOYSA-N 0.000 claims description 4
- 229920005830 Polyurethane Foam Polymers 0.000 claims description 3
- 230000015572 biosynthetic process Effects 0.000 claims description 3
- 239000011496 polyurethane foam Substances 0.000 claims description 3
- 238000003786 synthesis reaction Methods 0.000 claims description 3
- 239000000203 mixture Substances 0.000 claims description 2
- AYOHIQLKSOJJQH-UHFFFAOYSA-N dibutyltin Chemical compound CCCC[Sn]CCCC AYOHIQLKSOJJQH-UHFFFAOYSA-N 0.000 claims 1
- 125000003916 ethylene diamine group Chemical group 0.000 claims 1
- 238000009413 insulation Methods 0.000 abstract description 7
- 229920006264 polyurethane film Polymers 0.000 abstract description 6
- 238000012545 processing Methods 0.000 abstract description 4
- 239000006185 dispersion Substances 0.000 abstract description 3
- 230000002209 hydrophobic effect Effects 0.000 abstract description 3
- 125000002887 hydroxy group Chemical group [H]O* 0.000 abstract description 3
- 238000005054 agglomeration Methods 0.000 abstract description 2
- 230000002776 aggregation Effects 0.000 abstract description 2
- 238000011084 recovery Methods 0.000 abstract description 2
- 229920001169 thermoplastic Polymers 0.000 abstract description 2
- 239000004416 thermosoftening plastic Substances 0.000 abstract description 2
- 238000007036 catalytic synthesis reaction Methods 0.000 abstract 1
- 238000012360 testing method Methods 0.000 description 6
- 230000000052 comparative effect Effects 0.000 description 5
- 239000002245 particle Substances 0.000 description 5
- 239000002131 composite material Substances 0.000 description 4
- 230000000694 effects Effects 0.000 description 4
- 239000010410 layer Substances 0.000 description 4
- 229920003225 polyurethane elastomer Polymers 0.000 description 4
- 238000002834 transmittance Methods 0.000 description 4
- IMNIMPAHZVJRPE-UHFFFAOYSA-N triethylenediamine Chemical group C1CN2CCN1CC2 IMNIMPAHZVJRPE-UHFFFAOYSA-N 0.000 description 4
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 3
- 239000006260 foam Substances 0.000 description 3
- 230000002706 hydrostatic effect Effects 0.000 description 3
- 238000002360 preparation method Methods 0.000 description 3
- 229910052710 silicon Inorganic materials 0.000 description 3
- 239000010703 silicon Substances 0.000 description 3
- 239000000377 silicon dioxide Substances 0.000 description 3
- 235000012239 silicon dioxide Nutrition 0.000 description 3
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 description 2
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical group [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 description 2
- UKLDJPRMSDWDSL-UHFFFAOYSA-L [dibutyl(dodecanoyloxy)stannyl] dodecanoate Chemical compound CCCCCCCCCCCC(=O)O[Sn](CCCC)(CCCC)OC(=O)CCCCCCCCCCC UKLDJPRMSDWDSL-UHFFFAOYSA-L 0.000 description 2
- 125000003277 amino group Chemical group 0.000 description 2
- JCXGWMGPZLAOME-UHFFFAOYSA-N bismuth atom Chemical compound [Bi] JCXGWMGPZLAOME-UHFFFAOYSA-N 0.000 description 2
- 238000007906 compression Methods 0.000 description 2
- 230000006835 compression Effects 0.000 description 2
- 239000012975 dibutyltin dilaurate Substances 0.000 description 2
- 238000010096 film blowing Methods 0.000 description 2
- 238000005187 foaming Methods 0.000 description 2
- 239000008187 granular material Substances 0.000 description 2
- 238000004806 packaging method and process Methods 0.000 description 2
- 229920003023 plastic Polymers 0.000 description 2
- 239000002985 plastic film Substances 0.000 description 2
- 229910052725 zinc Inorganic materials 0.000 description 2
- 239000011701 zinc Substances 0.000 description 2
- PIICEJLVQHRZGT-UHFFFAOYSA-N Ethylenediamine Chemical compound NCCN PIICEJLVQHRZGT-UHFFFAOYSA-N 0.000 description 1
- 102000020897 Formins Human genes 0.000 description 1
- 108091022623 Formins Proteins 0.000 description 1
- 239000004721 Polyphenylene oxide Substances 0.000 description 1
- 230000004931 aggregating effect Effects 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000005540 biological transmission Effects 0.000 description 1
- 239000001569 carbon dioxide Substances 0.000 description 1
- 229910002092 carbon dioxide Inorganic materials 0.000 description 1
- 230000003197 catalytic effect Effects 0.000 description 1
- 239000011248 coating agent Substances 0.000 description 1
- 239000011247 coating layer Substances 0.000 description 1
- 238000000576 coating method Methods 0.000 description 1
- 239000000084 colloidal system Substances 0.000 description 1
- 238000004132 cross linking Methods 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 125000005442 diisocyanate group Chemical group 0.000 description 1
- 238000007598 dipping method Methods 0.000 description 1
- 239000002612 dispersion medium Substances 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 239000004088 foaming agent Substances 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 238000005469 granulation Methods 0.000 description 1
- 230000003179 granulation Effects 0.000 description 1
- 239000004519 grease Substances 0.000 description 1
- 238000007541 indentation hardness test Methods 0.000 description 1
- 229920002521 macromolecule Polymers 0.000 description 1
- 238000011326 mechanical measurement Methods 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 238000000465 moulding Methods 0.000 description 1
- 239000002086 nanomaterial Substances 0.000 description 1
- 239000002105 nanoparticle Substances 0.000 description 1
- 239000007783 nanoporous material Substances 0.000 description 1
- 238000011056 performance test Methods 0.000 description 1
- 230000002093 peripheral effect Effects 0.000 description 1
- 239000004033 plastic Substances 0.000 description 1
- 229920006255 plastic film Polymers 0.000 description 1
- 229920005906 polyester polyol Polymers 0.000 description 1
- 229920000570 polyether Polymers 0.000 description 1
- 239000005056 polyisocyanate Substances 0.000 description 1
- 229920001228 polyisocyanate Polymers 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 238000004321 preservation Methods 0.000 description 1
- 230000035484 reaction time Effects 0.000 description 1
- 238000007789 sealing Methods 0.000 description 1
- 229920002545 silicone oil Polymers 0.000 description 1
- 239000000779 smoke Substances 0.000 description 1
- 238000003980 solgel method Methods 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 239000011343 solid material Substances 0.000 description 1
- 239000003381 stabilizer Substances 0.000 description 1
- 230000035882 stress Effects 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 229920003002 synthetic resin Polymers 0.000 description 1
- 239000000057 synthetic resin Substances 0.000 description 1
- 229920002725 thermoplastic elastomer Polymers 0.000 description 1
- 239000004636 vulcanized rubber Substances 0.000 description 1
Classifications
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J5/00—Manufacture of articles or shaped materials containing macromolecular substances
- C08J5/18—Manufacture of films or sheets
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/08—Processes
- C08G18/16—Catalysts
- C08G18/161—Catalysts containing two or more components to be covered by at least two of the groups C08G18/166, C08G18/18 or C08G18/22
- C08G18/163—Catalysts containing two or more components to be covered by at least two of the groups C08G18/166, C08G18/18 or C08G18/22 covered by C08G18/18 and C08G18/22
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- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/08—Processes
- C08G18/16—Catalysts
- C08G18/18—Catalysts containing secondary or tertiary amines or salts thereof
- C08G18/20—Heterocyclic amines; Salts thereof
- C08G18/2045—Heterocyclic amines; Salts thereof containing condensed heterocyclic rings
- C08G18/2063—Heterocyclic amines; Salts thereof containing condensed heterocyclic rings having two nitrogen atoms in the condensed ring system
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- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/08—Processes
- C08G18/16—Catalysts
- C08G18/22—Catalysts containing metal compounds
- C08G18/222—Catalysts containing metal compounds metal compounds not provided for in groups C08G18/225 - C08G18/26
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/08—Processes
- C08G18/16—Catalysts
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- C08G18/227—Catalysts containing metal compounds of antimony, bismuth or arsenic
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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
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- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/08—Processes
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- C08G18/22—Catalysts containing metal compounds
- C08G18/24—Catalysts containing metal compounds of tin
- C08G18/242—Catalysts containing metal compounds of tin organometallic compounds containing tin-carbon bonds
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- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J3/00—Processes of treating or compounding macromolecular substances
- C08J3/20—Compounding polymers with additives, e.g. colouring
- C08J3/22—Compounding polymers with additives, e.g. colouring using masterbatch techniques
- C08J3/226—Compounding polymers with additives, e.g. colouring using masterbatch techniques using a polymer as a carrier
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J2375/00—Characterised by the use of polyureas or polyurethanes; Derivatives of such polymers
- C08J2375/04—Polyurethanes
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J2475/00—Characterised by the use of polyureas or polyurethanes; Derivatives of such polymers
- C08J2475/04—Polyurethanes
- C08J2475/08—Polyurethanes from polyethers
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/18—Oxygen-containing compounds, e.g. metal carbonyls
- C08K3/24—Acids; Salts thereof
- C08K3/26—Carbonates; Bicarbonates
- C08K2003/265—Calcium, strontium or barium carbonate
-
- 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
- C08K7/26—Silicon- containing compounds
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K9/00—Use of pretreated ingredients
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Abstract
The invention provides a production process of an aerogel polyurethane thermal insulation material, which belongs to the technical field of polyurethane films, has low heat conductivity and good thermal insulation performance, is not foamed and has softness, can be repeatedly subjected to thermoplastic recovery processing, and can be blown into films. The invention adopts aerogel catalyst, aerogel is used as catalyst to regulate gel speed, the aerogel is just hydrophobic, does not contain hydroxyl and water, the form of filling master batch is added to the film of thermoplastic polyurethane by using the catalytic synthesis of aerogel, the added amount is transparent to the produced film when 10 percent, the transparency of the film is reduced when 15 percent is added, but the film performance is not greatly affected, and the transparency of the film when 10 percent is added is affected when the aerogel is directly added to the blown film of thermoplastic polyurethane, and the dispersion is uneven and the agglomeration of the aerogel occurs.
Description
Technical Field
The invention belongs to the technical field of polyurethane film materials, and particularly relates to a production process of an aerogel polyurethane heat insulation material.
Background
Aerogel is called as "solid smoke", and is a typical nano porous material, which is a highly dispersed three-dimensional porous solid material formed by mutually aggregating colloid particles or macromolecules and taking gas as a dispersion medium. CN104452987a discloses a composite polyurethane insulation board, which has good insulation effect because an aerogel layer is arranged between polyurethane layers. The technology of adding aerogel materials into a hard foam polyurethane heat-insulating layer of CN102173147A, preparing CN103951966A hard polyurethane-aerogel silicon dioxide composite foam plastic by adopting foaming, and the like, and foaming polyether/polyester polyol, a composite catalyst, a foam stabilizer, water, a mixed foaming agent, polyisocyanate and a silicon dioxide aerogel solution containing hydroxyl groups. The polyurethane foam and the polyurethane composite board cannot be bent, and have large thickness and extremely poor flexibility. The application of the aerogel polyurethane thermal insulation material is greatly limited, and polyurethane films and sheets with good flexibility and thinner can not be prepared by adopting the method. Therefore, those skilled in the art have been required to develop a preparation method for producing aerogel polyurethane thermal insulation materials, which solves the defects of the prior art, and further meets the existing market demands and performance requirements.
Disclosure of Invention
In view of the above shortcomings of the prior art, the main object of the present invention is to provide a process for producing aerogel polyurethane insulation materials.
In order to achieve the above purpose, the present invention adopts the following technical scheme:
the production process of the aerogel polyurethane thermal insulation material comprises the following steps:
(1) Impregnating the aerogel with a catalyst to prepare an aerogel catalyst; (2) synthesizing aerogel-filled masterbatch with aerogel catalyst; (3) And (3) according to mass percentage, extruding and molding 80-85% of thermoplastic polyurethane elastomer, 10-15% of aerogel filling masterbatch and the balance of calcium carbonate by a double screw extruder to obtain the polyurethane elastomer.
Further, the aerogel catalyst in the step (1) is prepared by mixing 2.8-3 parts by weight of tetramethyl orthosilicate, 0.8-1 part by weight of 3-aminopropyl triethoxysilane and 4-5 parts by weight of acetonitrile for 8-10 min to obtain a solution A, stirring 1.8-2 parts by weight of deionized water and 4-5 parts by weight of acetonitrile for 10min to obtain a solution B, slowly adding the solution B into the solution A, pouring the mixed solution into a mold, standing until gel is formed, wherein the ageing time is 1-2 h, acetonitrile is exchanged for 3 times at room temperature, each time is 12h, the wet gel after solvent exchange is placed in a 10% isophorone diisocyanate solution prepared by acetonitrile solution, crosslinked in a water bath pot at 50-60 ℃ for 36-48 h, then dried at constant temperature for 8-10 h at 70-80 ℃, calcined at 650-700 ℃ for 3h in a muffle furnace to obtain massive silica aerogel, then reducing the silica aerogel at 700 ℃ for 1h in a tubular furnace hydrogen atmosphere, and dipping the aerogel according to a bath ratio of 1:10, wherein the catalyst is one or more of ethylenediamine, diisobutyltin octoate and bismuth octoate.
Further, the step (2) of synthesizing the filling masterbatch is as follows: a. adding 8-10 parts of diphenylmethane diisocyanate, 10 parts of dimethylformamide and 8-10 parts of aerogel catalyst into a clean and dry reaction kettle provided with a reflux condenser tube, a dropping funnel and a thermometer, heating to 60 ℃, slowly dropping 16-20 parts of dried polypropylene glycol under stirring, obtaining a prepolymer solution after dropping, and continuously maintaining at 60 ℃; b. continuously dropwise adding 15 parts of dimethylformamide solution in which 1.8 parts of 1, 4-butanediol are dissolved into the prepolymer, and heating to 80 ℃ for reaction for 3 hours after the dropwise adding is finished; c. after the reaction, dimethylformamide was removed by devolatilization and drying.
Further, the extrusion process parameters of the step (3) are that materials are mixed by a high-speed-low-speed mixer unit, hot mixing is carried out at 80 ℃, 5-8 min, cold mixing is carried out at 40 ℃ for 10-20 min, and the extrusion temperature of a twin screw is formed: the flange temperature is 190 ℃ at 190, 200, 205, 210 and 210 ℃ at one to five stages. The temperature of the machine head is 210 ℃ in the first section and 215 ℃ in the second section.
The invention has the beneficial effects that:
according to the invention, the aerogel catalyst is adopted, and the aerogel catalyst is used for preparing the polyurethane elastomer aerogel filling master batch, so that the granularity of the aerogel has a great influence on the filling effect in the past, and generally, the finer the granularity of the aerogel is, the better the dispersibility is, but the finer the granularity of the aerogel is, the easy agglomeration is generated, and the dispersion is unfavorable. According to the invention, an aerogel catalyst is adopted, the aerogel is used as the catalyst to regulate the gel speed, the reaction time is shortened, and the aerogel is just hydrophobic and does not contain hydroxyl and water. The aerogel particles are dispersed into tiny, stable and uniform particles as a catalyst, do not agglomerate in the processing, are adsorbed on the inner surface of polyurethane to form a coating layer, moisten the aerogel particles, reduce the free energy of the surface, prevent reagglomeration, form a stable structure, reduce the viscosity of a synthetic resin melt, improve the dispersity of aerogel to improve the processing performance, and further enable the product to obtain good performance. When the invention is used for filling masterbatch granulation production and extruding a film with polyurethane elastomer, no exhaust is needed, no air and moisture are needed to be discharged, the aerogel polyurethane heat insulation material product does not have air holes, the quality is not affected when the product is further processed, and no exhaust section or exhaust port is needed to be arranged for vacuumizing. The silicon aerogel is nano-structure peripheral particles obtained by a sol-gel method, is composed of nano-particles connected with each other in a porous three-dimensional silicon dioxide network, has the hydrophobic property, can fully impregnate a catalyst, can be used as a catalyst carrier to catalyze polyurethane masterbatch synthesis, further increases the dispersibility of the aerogel, improves the chemical stability, the mechanical property and the heat preservation performance, has good thermoplasticity, high strength, high elongation and good rebound resilience, and can be used for food packaging. Because of high strength and grease resistance, the metal antirust packaging requirements can be met.
Compared with the prior art, the invention has the following advantages:
according to the process method disclosed by the invention, the aerogel plays a catalytic role and a filling role, the surface of the aerogel silicon-based wet gel is rich in amino groups, diisocyanate is used for reacting and crosslinking with the amino groups on the surface of the silicon-based wet gel, water and carbon dioxide can be generated in the reaction process, a layer of uniform polymer can be finally formed to cover the surface of the aerogel, the catalyst is impregnated into the aerogel to further catalyze the synthesis of polyurethane masterbatch, the aerogel is further uniformly dispersed in a polyurethane elastomer finished product, the aerogel has a lower heat conductivity coefficient and good heat insulation performance, is not foamed and has softness, can be repeatedly subjected to thermoplastic recovery processing, can be blown into a film, and has the advantages of good sealing performance, firmness and durability, high toughness, high wear resistance, low heat conductivity coefficient and the like. The form of filling masterbatch is added to the thermoplastic polyurethane film blowing process, the transparency and the performance of the produced film are greatly influenced when the addition amount is 10%, the transparency of the film is reduced when the film is 15%, but the film performance is not greatly influenced when the aerogel is directly added to the thermoplastic polyurethane film blowing process, the transparency of the film is influenced, the dispersion is uneven, the aerogel is agglomerated, the stress concentration is easy, the practical application effect is poor, the heat conductivity coefficient is close to that of pure polyurethane, and the heat insulation effect is not obvious.
Detailed Description
The present invention will be described in further detail with reference to examples, but embodiments of the present invention are not limited thereto.
Example 1
1. Preparation of aerogel catalyst: 3 parts of tetramethyl orthosilicate, 1 part of 3-aminopropyl triethoxysilane and 5 parts of acetonitrile are stirred and mixed for 10min to obtain a solution A, 2 parts of deionized water and 5 parts of acetonitrile are stirred for 10min to obtain a solution B, the solution B is slowly added into the solution A, the mixed solution is poured into a mould and stands until gel is formed, wherein the ageing time is 1h, the acetonitrile is exchanged for 3 times at room temperature, each time for 12h, the wet gel after solvent exchange is placed in 10% isophorone diisocyanate solution prepared by acetonitrile solution, crosslinked for 48h in a water bath kettle at 60 ℃, then dried at constant temperature for 10h at 70 ℃, calcined for 5h at 700 ℃ in a MF-0612P muffle furnace, and then reduced for 1h at 700 ℃ in a QSH-VTF-1200T tubular furnace hydrogen atmosphere to obtain aerogel, the aerogel is impregnated according to a bath ratio of 1:10, the aerogel is impregnated with a catalyst according to a bath ratio of 1:10, the catalyst is triethylenediamine, and the dibutyl tin dilaurate is a mixture according to a mass ratio of 1:1. The triethylenediamine is selected from NiaxA-33, dibutyl tin dilaurate DabcoT-12.
2. Synthesizing filling masterbatch: a. adding 10 parts of diphenylmethane diisocyanate MDI-100 and 10 parts of DMF and aerogel catalyst 10 parts into a clean and dry reaction kettle provided with a reflux condenser tube, a dropping funnel and a thermometer, heating to 60 ℃, slowly dropping 20 parts of polypropylene glycol PPG-2000 dried to a water content of 0.05% under stirring, obtaining a prepolymer after dropping, and continuously maintaining at 60 ℃; b. continuously dropwise adding 15 parts of DMF solution in which 1.8 parts of 1, 4-butanediol are dissolved into the prepolymer, and heating to 80 ℃ for reaction for 3 hours after the dropwise adding is finished; c. after the reaction, DMF was removed by devolatilization and drying.
3. According to mass fraction, 80% of thermoplastic polyurethane elastomer, 10% of aerogel filling masterbatch and the balance of calcium carbonate are extruded and molded by a double screw extruder, thus obtaining the polyurethane foam. Bayer thermoplastic polyurethane elastomer DP1485A, ji Anan source calcium carbonate CC-2500, adopting high-speed mixer SRL-Z500 high-speed-low-speed mixer to mix materials, hot mixing at 80 ℃ for min, cold mixing at 40 ℃ for 20min, extruding in a twin-screw extruder, and extruding at twin-screw extrusion temperature: the flange temperature is 190 ℃ at 190, 200, 205, 210 and 210 ℃ at one to five stages. The temperature of the machine head is 210 ℃ in the first section and 215 ℃ in the second section, and the aerogel polyurethane thermal insulation granules are prepared. Jin Weier GWS120 type cast film extrusion line, the process temperature from the feeding section to the die is 180 ℃, 185 ℃, 190 ℃, 195 ℃, 190 ℃, 200 ℃ and the extruder motor rotation speed is 60rpm, respectively, to obtain 0.025mm aerogel polyurethane film. Light transmittance of 78.1%, thickness measured in accordance with ASTM D1777, hydrostatic pressure test in accordance with method B in JIS L1092 specification, 3 points of one film were measured, hydrostatic pressure resistance of 8000mmH 2 O。
Comparative example 1
In this comparative example, compared with example 1, the aerogel-filled masterbatch was omitted, and the aerogel equivalent to example 1 was directly added, i.e., the aerogel obtained in step one was directly added, and the remaining process conditions were the same as in example 1.
Jin Weier GWS120 type cast film extrusion line, wherein the process temperature from a feeding section to a die is 180 ℃, 185 ℃, 190 ℃, 195 ℃, 190 ℃, 200 ℃ and 60rpm of extruder motor rotation speed, thus obtaining 0.025mm aerogel polyurethane film with hydrostatic pressure resistance of 6000mmH 2 O, light transmittance is 69%.
Example 2
1. Preparation of aerogel catalyst: 2.8 parts of tetramethyl orthosilicate, 0.8 part of 3-aminopropyl triethoxysilane and 4 parts of acetonitrile are stirred and mixed for 8min to obtain a solution A, 1.8 parts of deionized water and 4 parts of acetonitrile are stirred for 10min to obtain a solution B, the solution B is slowly added into the solution A, the mixed solution is poured into a mould, standing until gel is formed, wherein ageing time is 1h, acetonitrile is exchanged for 3 times at room temperature, each time for 12h, the wet gel after solvent exchange is placed in 10% isophorone diisocyanate solution prepared by acetonitrile solution, crosslinked in a water bath kettle at 50 ℃ for 36h, then dried at constant temperature for 8h at 70 ℃, and calcined at 650 ℃ in an MF-0612P muffle furnace for 3h to obtain massive silica aerogel, then the aerogel is reduced at 700 ℃ for 1h in a QSH-VTF-1200T tubular furnace hydrogen atmosphere, the aerogel is obtained, the aerogel is impregnated according to a bath ratio of 1:10, the catalyst is zinc isooctoate and bismuth isozincate and bismuth isooctoate according to a mass ratio of 1:1, wherein Bijiang zinc is used for 24-Kadson-4.
2. Synthesizing filling masterbatch: a. adding 10 parts of diphenylmethane diisocyanate MDI-100 and 10 parts of DMF and aerogel catalyst 10 parts into a clean and dry reaction kettle provided with a reflux condenser tube, a dropping funnel and a thermometer, heating to 60 ℃, slowly dropping 16 parts of polypropylene glycol PPG-2000 dried to a water content of 0.05% under stirring, obtaining a prepolymer after dropping, and continuously maintaining at 60 ℃; b. continuously dropwise adding 15 parts of DMF solution in which 1.8 parts of 1, 4-butanediol are dissolved into the prepolymer, and heating to 80 ℃ for reaction for 3 hours after the dropwise adding is finished; c. after the reaction, DMF was removed by devolatilization and drying.
3. According to mass fraction, 85% of the thermoplastic polyurethane elastomer, 15% of aerogel filling masterbatch and the balance of calcium carbonate are extruded and molded by a double screw extruder to obtain the Bayer thermoplastic polyurethane elastomer DP1485A and Ji Anan source calcium carbonate CC-2500. Mixing materials by adopting a high-speed mixer SRL-Z500 high-speed-low-speed mixer unit, hot mixing at 80 ℃, 8min, cold mixing at 40 ℃ for 10min, extruding by a double-screw extruder, and extruding at the double-screw extrusion temperature: 190, 200, 205, 210 and 210 ℃ respectively, the flange temperature is 190 ℃, the machine head temperature is 210 ℃ in one section, and 215 ℃ in two sections, so as to prepare the aerogel polyurethane thermal insulation material granules.
Cast extrusion according to the procedure of example 1 gave a 0.025mm aerogel polyurethane film having a water vapor transmission capacity of 5000g/m 2 24h, light transmittance 77.4%,
the aerogel polyurethane thermal insulation materials prepared in examples 1-2 and comparative example 1 were subjected to performance test, and the test results are shown in Table 1
Table 1 results of performance testing of aerogel polyurethane insulation for each of the examples and comparative example 1
| Project | Comparative example 1 | Example 1 | Example 2 |
| Tensile strength MPa | 44.3 | 47.1 | 47.7 |
| Elongation at break% | 553 | 520 | 513 |
| Tear strength kN/m | 73 | 76.4 | 77.1 |
| Hardness Shore A | 86.6 | 87.3 | 87.5 |
| Compression set% | 13.2 | 11.0 | 10.9 |
| Thermal conductivity W/m.K | 0.22 | 0.17 | 0.18 |
Note that: GB/T531.1-2008 vulcanized rubber or thermoplastic rubber indentation hardness test method part 1: county durometer (shore hardness); GB/T6672-2001 mechanical measurement method for measuring thickness of plastic films and sheets; GB/T2410-2008 transparent plastic light transmittance and haze test; uniformly coating a small amount of silicone oil on the surface of the film sample to ensure good thermal contact between the upper surface and the lower surface; the thermal resistance test mode is adopted by a 'thermal flow method' DRL3 type thermal conductivity tester, the thermal pole constant temperature is 70 ℃, the test pressure is 200N, the impact resilience is ISO4682, the tensile strength breaking and breaking elongation DIN 53504-2017 is 200mm/min, and the compression set is ISO815-1-2014.
Claims (2)
1. The production process of the aerogel polyurethane thermal insulation material is characterized by comprising the following steps of:
(1) 2.8-3 parts of tetramethyl orthosilicate, 0.8-1 part of 3-aminopropyl triethoxysilane and 4-5 parts of acetonitrile are stirred and mixed for 8-10 min to obtain a solution A, 1.8-2 parts of deionized water and 4-5 parts of acetonitrile are stirred for 10min to obtain a solution B, the solution B is slowly added into the solution A, the mixed solution is poured into a mould and stands until gel is formed, wherein the ageing time is 1-2 h, acetonitrile is exchanged for 3 times at room temperature, each time for 12h, wet gel after solvent exchange is placed in 10% isophorone diisocyanate solution prepared by acetonitrile solution, crosslinked for 36-48 h in a water bath kettle at 50-60 ℃, then dried at constant temperature for 8-10 h at 70-80 ℃, calcined for 3-5 h at 650-700 ℃ in a muffle furnace to obtain massive silica aerogel, and then the aerogel is obtained by reduction for 1h at 700 ℃ in a tubular furnace hydrogen atmosphere, the aerogel is impregnated according to a bath ratio of 1:10, and the catalyst is ethylenediamine, dibutyl tin octoate, one or more of bismuth octoates are prepared; (2) Synthesizing aerogel filling masterbatch by using an aerogel catalyst, wherein the synthesis filling masterbatch is as follows: a. adding 8-10 parts of diphenylmethane diisocyanate, 10 parts of dimethylformamide and 8-10 parts of aerogel catalyst into a clean and dry reaction kettle provided with a reflux condenser tube, a dropping funnel and a thermometer, heating to 60 ℃, slowly dropping 16-20 parts of dried polypropylene glycol under stirring, obtaining a prepolymer solution after dropping, and continuously maintaining at 60 ℃; b. continuously dropwise adding 15 parts of dimethylformamide solution in which 1.8 parts of 1, 4-butanediol are dissolved into the prepolymer, and heating to 80 ℃ for reaction for 3 hours after the dropwise adding is finished; c. after the reaction is finished, removing dimethylformamide by devolatilization and drying to obtain the catalyst; (3) And (3) according to the mass percentage, 80-85% of thermoplastic polyurethane elastomer, 10-15% of aerogel filling masterbatch and the balance of calcium carbonate are uniformly mixed, and then the mixture is extruded and molded by a double-screw extruder, so that the polyurethane foam is obtained.
2. The production process of the aerogel polyurethane thermal insulation material according to claim 1, wherein the mixing and extrusion process parameters in the step (3) are that materials are mixed by a high-speed-low-speed mixer unit, the materials are mixed at 80 ℃ under heat for 5-8 min, mixed at 40 ℃ under cold for 10-20 min, and the double screw extrusion temperature is as follows: the first to the fifth sections are 190 ℃, 200 ℃, 205 ℃, 210 ℃, flange temperature 190 ℃, machine head temperature, 210 ℃ and 215 ℃.
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| KR100666110B1 (en) * | 2006-02-28 | 2007-01-09 | 한국생산기술연구원 | Aerogel composite foam and method of preparing the same |
| CN106008907A (en) * | 2016-03-16 | 2016-10-12 | 当涂县科辉商贸有限公司 | High-toughness silica aerogel polyurethane composite thermal insulation wall board and preparation method thereof |
| CN109232850A (en) * | 2018-08-08 | 2019-01-18 | 山东新朗华科技有限公司 | A kind of fire-retardant low thermal conductivity rigid polyurethane foam of aeroge modified heat resistant and preparation method thereof |
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| KR100666110B1 (en) * | 2006-02-28 | 2007-01-09 | 한국생산기술연구원 | Aerogel composite foam and method of preparing the same |
| CN106008907A (en) * | 2016-03-16 | 2016-10-12 | 当涂县科辉商贸有限公司 | High-toughness silica aerogel polyurethane composite thermal insulation wall board and preparation method thereof |
| CN109232850A (en) * | 2018-08-08 | 2019-01-18 | 山东新朗华科技有限公司 | A kind of fire-retardant low thermal conductivity rigid polyurethane foam of aeroge modified heat resistant and preparation method thereof |
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