CN114752092A - Production process of aerogel polyurethane thermal insulation material - Google Patents
Production process of aerogel polyurethane thermal insulation material Download PDFInfo
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- CN114752092A CN114752092A CN202210388717.2A CN202210388717A CN114752092A CN 114752092 A CN114752092 A CN 114752092A CN 202210388717 A CN202210388717 A CN 202210388717A CN 114752092 A CN114752092 A CN 114752092A
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- aerogel
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- 239000004964 aerogel Substances 0.000 title claims abstract description 89
- 229920002635 polyurethane Polymers 0.000 title claims abstract description 24
- 239000004814 polyurethane Substances 0.000 title claims abstract description 24
- 239000012774 insulation material Substances 0.000 title claims abstract description 16
- 238000004519 manufacturing process Methods 0.000 title claims abstract description 12
- 239000003054 catalyst Substances 0.000 claims abstract description 32
- 238000011049 filling Methods 0.000 claims abstract description 19
- 239000004594 Masterbatch (MB) Substances 0.000 claims abstract description 17
- 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
- 230000002194 synthesizing effect Effects 0.000 claims abstract description 6
- WEVYAHXRMPXWCK-UHFFFAOYSA-N Acetonitrile Chemical compound CC#N WEVYAHXRMPXWCK-UHFFFAOYSA-N 0.000 claims description 48
- 239000000243 solution Substances 0.000 claims description 39
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 claims description 32
- 238000002156 mixing Methods 0.000 claims description 20
- 238000000034 method 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
- 238000003756 stirring Methods 0.000 claims description 12
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 11
- 238000001125 extrusion Methods 0.000 claims description 10
- 238000006243 chemical reaction Methods 0.000 claims description 9
- 238000006116 polymerization reaction 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
- IMNIMPAHZVJRPE-UHFFFAOYSA-N triethylenediamine Chemical compound C1CN2CCN1CC2 IMNIMPAHZVJRPE-UHFFFAOYSA-N 0.000 claims description 8
- 238000001035 drying Methods 0.000 claims description 7
- 239000011240 wet gel 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
- 239000000463 material Substances 0.000 claims description 6
- 229920001451 polypropylene glycol Polymers 0.000 claims description 6
- 239000000499 gel Substances 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
- OEOIWYCWCDBOPA-UHFFFAOYSA-N 6-methyl-heptanoic acid Chemical compound CC(C)CCCCC(O)=O OEOIWYCWCDBOPA-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
- 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 4
- 230000032683 aging Effects 0.000 claims description 4
- 229910052797 bismuth Inorganic materials 0.000 claims description 4
- JCXGWMGPZLAOME-UHFFFAOYSA-N bismuth atom Chemical compound [Bi] JCXGWMGPZLAOME-UHFFFAOYSA-N 0.000 claims description 4
- 238000001354 calcination Methods 0.000 claims description 4
- 239000008367 deionised water Substances 0.000 claims description 4
- 229910021641 deionized water Inorganic materials 0.000 claims description 4
- 239000012975 dibutyltin dilaurate Substances 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
- 238000010992 reflux Methods 0.000 claims description 4
- 239000000377 silicon dioxide Substances 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
- ADJMNWKZSCQHPS-UHFFFAOYSA-L zinc;6-methylheptanoate Chemical compound [Zn+2].CC(C)CCCCC([O-])=O.CC(C)CCCCC([O-])=O ADJMNWKZSCQHPS-UHFFFAOYSA-L 0.000 claims description 4
- 235000012239 silicon dioxide Nutrition 0.000 claims description 3
- 238000002791 soaking Methods 0.000 claims description 3
- 229920006264 polyurethane film Polymers 0.000 abstract description 6
- 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
- 238000009413 insulation Methods 0.000 abstract description 3
- 238000012545 processing Methods 0.000 abstract description 3
- 238000011084 recovery Methods 0.000 abstract 1
- 229920001169 thermoplastic Polymers 0.000 abstract 1
- 239000004416 thermosoftening plastic Substances 0.000 abstract 1
- 239000002245 particle Substances 0.000 description 8
- 239000002131 composite material Substances 0.000 description 5
- 230000000052 comparative effect Effects 0.000 description 4
- 238000004132 cross linking Methods 0.000 description 4
- 230000000694 effects Effects 0.000 description 4
- 239000010410 layer Substances 0.000 description 4
- 238000012360 testing method Methods 0.000 description 4
- 238000002834 transmittance Methods 0.000 description 4
- 239000004965 Silica aerogel Substances 0.000 description 3
- 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
- 239000000203 mixture Substances 0.000 description 3
- 229910052710 silicon Inorganic materials 0.000 description 3
- 239000010703 silicon Substances 0.000 description 3
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 description 2
- 229920005830 Polyurethane Foam Polymers 0.000 description 2
- 125000003277 amino group Chemical group 0.000 description 2
- 230000009286 beneficial effect Effects 0.000 description 2
- 238000007906 compression Methods 0.000 description 2
- 230000006835 compression Effects 0.000 description 2
- 230000007547 defect Effects 0.000 description 2
- 238000010096 film blowing Methods 0.000 description 2
- 239000008187 granular material Substances 0.000 description 2
- 238000004806 packaging method and process Methods 0.000 description 2
- 238000011056 performance test Methods 0.000 description 2
- 229920003023 plastic Polymers 0.000 description 2
- 229920003225 polyurethane elastomer Polymers 0.000 description 2
- 239000011496 polyurethane foam Substances 0.000 description 2
- 238000004321 preservation Methods 0.000 description 2
- 239000004721 Polyphenylene oxide Substances 0.000 description 1
- 238000005054 agglomeration Methods 0.000 description 1
- 230000005540 biological transmission Effects 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 239000001569 carbon dioxide Substances 0.000 description 1
- 229910002092 carbon dioxide Inorganic materials 0.000 description 1
- 238000006555 catalytic reaction Methods 0.000 description 1
- 238000007036 catalytic synthesis reaction Methods 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
- 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
- 238000005187 foaming 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
- 239000005022 packaging material Substances 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
- 239000002985 plastic film Substances 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
- 238000002360 preparation method Methods 0.000 description 1
- 230000035484 reaction time Effects 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
- 238000003786 synthesis reaction Methods 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
-
- 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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- 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
- C08G18/18—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
-
- 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
- C08G18/22—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
- C08G18/22—Catalysts containing metal compounds
- 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
- 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
- C08G18/24—Catalysts containing metal compounds of tin
- C08G18/242—Catalysts containing metal compounds of tin organometallic compounds containing tin-carbon bonds
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- 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
- 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
-
- 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
-
- 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
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- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Engineering & Computer Science (AREA)
- Manufacturing & Machinery (AREA)
- Materials Engineering (AREA)
- Inorganic Chemistry (AREA)
- Polyurethanes Or Polyureas (AREA)
Abstract
The invention provides a production process of an aerogel polyurethane thermal insulation material, belongs to the technical field of polyurethane films, has low heat conductivity coefficient and good thermal insulation performance, is unfoamed and flexible, can be repeatedly subjected to thermoplastic recovery processing, and can be blown into a film. The aerogel catalyst is adopted, the aerogel is used as the catalyst to adjust the gel speed, the aerogel is just hydrophobic and does not contain hydroxyl and water, the aerogel catalyst is used for synthesizing the filling masterbatch and is added into the thermoplastic polyurethane film, the film is transparent when the addition amount is 10%, the film transparency is reduced when 15% of the aerogel catalyst is added, but the performance of the film is not greatly influenced, the aerogel is directly added into the thermoplastic polyurethane blown film, the transparency of the film added by 10% is influenced, the dispersion is not uniform, and the aerogel is agglomerated.
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 thermal insulation material.
Background
Aerogel, which is called "solid smoke", is a typical nanoporous material, which is a highly dispersed three-dimensional porous solid material formed by colloidal particles or macromolecules aggregated with each other and using gas as a dispersion medium. CN104452987A discloses a composite polyurethane heat-insulating board which has a good heat-insulating effect because an aerogel layer is arranged between polyurethane layers. CN102173147A aerogel materials are added in the rigid foam polyurethane thermal insulation layer, CN103951966A rigid polyurethane-aerogel silicon dioxide composite foam plastics and other technologies are prepared by foaming, and polyether/polyester polyol, a composite catalyst, a foam stabilizer, water, a mixed foaming agent, polyisocyanate and a hydroxyl-containing silicon dioxide aerogel solution are foamed to prepare the polyurethane foam. The polyurethane foam and polyurethane composite board cannot be bent, is large in thickness and extremely poor in flexibility. The application of the aerogel polyurethane thermal insulation material is greatly limited, and the method can not be used for preparing thin polyurethane films and sheets with good flexibility. Therefore, the technical personnel in the field need to develop a preparation method of a production process of aerogel polyurethane thermal insulation materials to solve the defects of the prior art, and further meet the existing market demand and performance requirement.
Disclosure of Invention
In view of the defects of the prior art, the invention mainly aims to provide a production process of an aerogel polyurethane thermal insulation material.
In order to achieve the purpose, the invention adopts the following technical scheme:
a production process of an aerogel polyurethane thermal insulation material comprises the following steps:
(1) impregnating the aerogel with a catalyst to prepare an aerogel catalyst; (2) synthesizing aerogel filling masterbatch by using an aerogel catalyst; (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 extruded and molded by a double-screw extruder to obtain the aerogel filling material.
Further, the aerogel catalyst in the step (1) is prepared by stirring and mixing 2.8-3 parts by weight of tetramethyl orthosilicate, 0.8-1 part by weight of 3-aminopropyltriethoxysilane 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 to form a gel, wherein the aging time is 1-2 h, exchanging the acetonitrile at room temperature for 3 times, 12h each time, placing the wet gel after solvent exchange into an isophorone diisocyanate solution with the mass fraction of 10% prepared from the acetonitrile solution, crosslinking for 36-48 h in a water bath kettle at 50-60 ℃, drying at constant temperature of 70-80 ℃ for 8-10 h, calcining for 3-5 h at 650-700 ℃ in a muffle furnace to obtain blocky aerogel, and then reducing the solution at 700 ℃ for 1h in a tubular furnace hydrogen atmosphere to obtain aerogel, and soaking the aerogel according to the bath ratio of 1: 10, wherein the catalyst is one or more of triethylene diamine, dibutyltin dilaurate, zinc isooctanoate and bismuth isooctanoate.
Further, the filling masterbatch synthesized in the step (2) is as follows: a. adding 8-10 parts of diphenylmethane diisocyanate and 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 while stirring, obtaining a pre-polymerization solution after dropping, and continuously keeping at 60 ℃; b. continuously dropwise adding 15 parts of dimethylformamide solution dissolved with 1.8 parts of 1, 4-butanediol into the pre-polymerization solution, and after dropwise adding is finished, heating to 80 ℃ to react for 3 hours; c. after the reaction is finished, the dimethyl formamide is removed by devolatilization and drying.
Further, the extrusion process parameters of the step (3) are that a high-speed-low-speed mixing unit is adopted to mix materials, hot mixing is carried out at 80 ℃ for 5-8 min, cold mixing is carried out at 40 ℃ for 10-20 min, and the extrusion temperature of the double screw is as follows: the temperatures of the first section, the second section, the third section, the fourth section, the fifth section and the sixth section are respectively 190 ℃, 200, 205, 210 and 210 ℃, and the temperature of the flange is 190 ℃. Head temperature, first stage 210 ℃, second stage 215 ℃.
The invention has the beneficial effects that:
according to the invention, the aerogel catalyst is adopted and used for catalyzing and preparing the polyurethane elastomer aerogel filling masterbatch, the particle size of the conventional aerogel has a great influence on the filling effect, and generally, the finer the particle size of the aerogel is, the better the dispersibility is, but the too fine the particle size of the aerogel is, the aerogel is easy to agglomerate and is not beneficial to dispersion. The invention adopts aerogel catalyst, the aerogel is used as the catalyst to adjust the gelling speed and shorten the reaction time, 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, and are not agglomerated any more in processing, and are adsorbed on the inner surface of polyurethane to form a coating layer, so that the aerogel particles are wetted, the surface free energy is reduced, the re-agglomeration is prevented, a stable structure is formed, the viscosity of a synthetic resin melt can be reduced, the dispersity of aerogel is improved, the processing performance is improved, and a product can obtain good performance. When the master batch is filled for granulation production and is extruded with the polyurethane elastomer to form a film, the air and moisture do not need to be exhausted, the aerogel polyurethane thermal insulation material product does not have air holes, the quality is not influenced when the product is further processed, and an exhaust section or an exhaust port does not need to be arranged for vacuumizing. The silica aerogel is a peripheral particle with a nano structure obtained by a sol-gel method, is composed of nano particles which are mutually connected in a porous three-dimensional silica network, has hydrophobic property, can fully impregnate a catalyst, can be used as a catalyst carrier to catalyze the synthesis of polyurethane master gel, further increases the dispersity of the aerogel, improves the chemical stability, the mechanical property and the heat preservation property, 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 antirust packaging material can meet the requirements of metal antirust packaging.
Compared with the prior art, the invention has the following advantages:
according to the process method disclosed by the invention, the aerogel plays a role in catalysis and filling, 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 are generated in the reaction process, and a layer of uniform polymer is finally formed to cover the surface of the aerogel silicon-based wet gel. The aerogel catalytic synthesis filling masterbatch is added into a thermoplastic polyurethane film blowing process in a form of catalyzing and synthesizing the filling masterbatch, when the addition amount is 10%, the transparency and the performance of a produced film are greatly influenced, when the addition amount is 15%, the transparency of the film is reduced, but the performance of the film is not greatly influenced, the aerogel is directly added into the thermoplastic polyurethane film blowing, the transparency of the film is influenced, the dispersion is uneven, the aerogel is agglomerated, the stress is easily concentrated, the actual application effect is poor, the heat conductivity coefficient of the aerogel 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 the embodiments of the present invention are not limited thereto.
Example 1
Firstly, preparing an aerogel catalyst: stirring and mixing 3 parts by weight of tetramethyl orthosilicate, 1 part by weight of 3-aminopropyltriethoxysilane and 5 parts by weight of acetonitrile for 10min to obtain a solution A, stirring 2 parts by weight of deionized water and 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 aging time is 1h, exchanging acetonitrile at room temperature for 3 times, 12h each time, placing the wet gel after solvent exchange into an isophorone diisocyanate solution with the mass fraction of 10% prepared by the acetonitrile solution, crosslinking in a 60 ℃ water bath kettle for 48h, drying at the constant temperature of 70 ℃ for 10h, calcining at the temperature of 700 ℃ in an MF-0612P muffle furnace for 5h to obtain blocky silica aerogel, then reducing at the temperature of 700 ℃ for 1h in the hydrogen atmosphere of an QSH-VTF-1200T tubular furnace to obtain the aerogel, dipping the aerogel according to the bath ratio of 1: 10, soaking aerogel into a catalyst according to a bath ratio of 1: 10, wherein the catalyst is a mixture of triethylene diamine and dibutyltin dilaurate according to a mass ratio of 1: 1. The triethylene diamine is selected from NiaxA-33 and dibutyl tin dilaurate Cao DabcoT-12.
Secondly, synthesizing filling masterbatch: a. adding 10 parts of diphenylmethane diisocyanate (MDI-100) and 10 parts of DMF (dimethyl formamide) and 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 dropwise adding 20 parts of polypropylene glycol (PPG-2000) dried to the water content of 0.05% while stirring, obtaining a pre-polymerization solution after the dropwise addition is finished, and continuously keeping the pre-polymerization solution at 60 ℃; b. continuously dropwise adding 15 parts of DMF solution dissolved with 1.8 parts of 1, 4-butanediol into the pre-polymerization solution, and after dropwise adding, heating to 80 ℃ to react for 3 hours; c. after the reaction is finished, the DMF is removed by devolatilization and drying.
And thirdly, according to the mass fraction, 80% of thermoplastic polyurethane elastomer, 10% of aerogel filling masterbatch and the balance calcium carbonate are extruded and molded by a double-screw extruder to obtain the composite material. The Bayer thermoplastic polyurethane elastomer DP1485A and the Jian Guangyuan calcium carbonate CC-2500 are mixed by a high-speed mixer SRL-Z500 high-speed-low-speed mixing unit, the mixture is subjected to hot mixing at 80 ℃ for 20min and cold mixing at 40 ℃ for 20min, and is placed into a double-screw extruder for extrusion, and the extrusion temperature of the double screws is as follows: the temperatures of the first section, the second section, the third section, the fourth section, the fifth section and the sixth section are respectively 190 ℃, 200, 205, 210 and 210 ℃, and the temperature of the flange is 190 ℃. The temperature of the machine head is 210 ℃ in the first section and 215 ℃ in the second section, and the aerogel polyurethane heat-preservation granules are prepared. The process temperature of the Jinweil GWS120 cast film extrusion line from the feeding section to the neck mold is respectively 180 ℃, 185 ℃, 190 ℃, 195 ℃, 190 ℃ and 200 ℃, and the rotating speed of an extruder motor is 60rpm, so that the 0.025mm aerogel polyurethane film is obtained. The light transmittance is 78.1%, the thickness is measured according to ASTM D1777, the hydrostatic pressure is measured according to method B of JIS L1092, 3 points are taken from one film, and the hydrostatic pressure resistance is 8000mmH 2O。
Comparative example 1
Compared with the embodiment 1, the comparison example omits aerogel filling masterbatch, directly adds the aerogel with the same quantity as the embodiment 1, namely the aerogel obtained in the first step is direct, and the rest process conditions are the same as the embodiment 1.
The process temperature of the Jinweil GWS120 cast film extrusion line from a feeding section to a mouth die is respectively 180 ℃, 185 ℃, 190 ℃, 195 ℃, 190 ℃, 200 ℃, and the rotation speed of an extruder motor is 60rpm, so that the 0.025mm aerogel polyurethane film with the hydrostatic pressure resistance of 6000mmH is obtained2O, light transmittance 69%.
Example 2
Firstly, preparing an aerogel catalyst: stirring and mixing 2.8 parts by weight of tetramethyl orthosilicate, 0.8 part by weight of 3-aminopropyltriethoxysilane and 4 parts by weight of acetonitrile for 8min to obtain a solution A, stirring 1.8 parts by weight of deionized water and 4 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 aging time is 1h, the acetonitrile is exchanged for 3 times at room temperature, 12h each time, the wet gel after solvent exchange is placed in an isophorone diisocyanate solution with the mass fraction of 10% prepared by the acetonitrile solution, crosslinking in a 50 ℃ water bath kettle for 36h, drying at constant temperature of 70 ℃ for 8h, calcining at 650 ℃ in an MF-0612P muffle furnace for 3h to obtain blocky silica aerogel, then reducing at 700 ℃ for 1h in a QSH-VTF-1200T tubular furnace in hydrogen atmosphere to obtain aerogel, impregnating the aerogel according to the ratio of 1: 10, the aerogel is dipped into a catalyst according to the bath ratio of 1: 10, wherein the catalyst is a mixture of zinc isooctanoate and bismuth isooctanoate according to the mass ratio of 1: 1, and the catalyst comprises bismuth isooctanoate BiCAT8124 and zinc isooctanoate 825-4 of Jiangsu Handson.
Secondly, synthesizing filling masterbatch: a. adding 10 parts of diphenylmethane diisocyanate (MDI-100), 10 parts of DMF (dimethyl formamide) and 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 dropwise adding 16 parts of polypropylene glycol (PPG-2000) dried to the water content of 0.05% while stirring, obtaining a pre-polymerization solution after dropwise adding is finished, and continuously keeping at 60 ℃; b. continuously dropwise adding 15 parts of DMF solution dissolved with 1.8 parts of 1, 4-butanediol into the pre-polymerization solution, and after dropwise adding, heating to 80 ℃ to react for 3 hours; c. after the reaction is finished, the DMF is removed by devolatilization and drying.
And thirdly, according to the mass fraction, the Bayer thermoplastic polyurethane elastomer DP1485A and the Ji' an Guangyuan calcium carbonate CC-2500 are obtained by extruding and molding 85% of the thermoplastic polyurethane elastomer, 15% of aerogel filling masterbatch and the balance of calcium carbonate by a double-screw extruder. Mixing materials by adopting a high-speed mixer SRL-Z500 high-speed-low-speed mixing unit, carrying out hot mixing at 80 ℃ for 8min, carrying out cold mixing at 40 ℃ for 10min, putting into a double-screw extruder, and extruding at the double-screw extrusion temperature: the temperature of the flange is 190 ℃, the temperature of the head is 210 ℃ in the first section, and the temperature of the second section is 215 ℃ in the second section, and the aerogel polyurethane thermal insulation material granules are prepared.
Tape extrusion according to the procedure of example 1 gave a 0.025mm aerogel polyurethane film having a water vapor transmission of 5000g/m224h, light transmittance 77.4%,
the aerogel polyurethane thermal insulation material prepared in the embodiment 1-2 and the comparative example 1 is subjected to performance test, and the test results are shown in table 1
Table 1 results of performance test of aerogel polyurethane insulation materials of each example and comparative example 1
| Item | 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 at 70 ℃ for 24 h% | 13.2 | 11.0 | 10.9 |
| Coefficient of thermal conductivity W/m.K | 0.22 | 0.17 | 0.18 |
Note: GB/T531.1-2008 vulcanized rubber or thermoplastic rubber indentation hardness test method part 1: county durometer (shore hardness); GB/T6672-2001 plastic film and slice thickness measuring mechanical measurement method; testing the light transmittance and haze of the transparent plastic in GB/T2410-2008; 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; a DRL3 type thermal conductivity tester adopting a 'heat flow method' is adopted, a thermal resistance test mode is adopted, the constant temperature of a heat pole is 70 ℃, the test pressure is 200N, the impact resilience ISO4682, the tensile strength fracture and crack elongation DIN 53504 and 2017 are 200mm/min, and the compression permanent deformation ISO815-1-2014 is adopted.
Claims (4)
1. The production process of the aerogel polyurethane thermal insulation material is characterized by comprising the following steps of:
(1) impregnating the aerogel with a catalyst to prepare an aerogel catalyst; (2) synthesizing aerogel filling masterbatch by using an aerogel catalyst; (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 extruded and molded by a double-screw extruder to obtain the aerogel filling masterbatch.
2. The production process of the aerogel polyurethane thermal insulation material according to claim 1, characterized in that the aerogel catalyst in the step (1) is prepared by stirring and mixing 2.8-3 parts by weight of tetramethyl orthosilicate, 0.8-1 part by weight of 3-aminopropyltriethoxysilane 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 aging time is 1-2 h, the acetonitrile is exchanged at room temperature for 3 times, each time for 12h, the wet gel after solvent exchange is placed in an isophorone diisocyanate solution prepared from the acetonitrile solution with a mass fraction of 10%, cross-linked in a 50-60 ℃ water bath for 36-48 h, and then dried at a constant temperature of 70-80 ℃ for 8-10 h, calcining for 3-5 h at 650-700 ℃ in a muffle furnace to obtain blocky silicon dioxide aerogel, then reducing for 1h at 700 ℃ in a tubular furnace hydrogen atmosphere to obtain aerogel, and soaking the aerogel according to the bath ratio of 1: 10, wherein the catalyst is one or more of triethylene diamine, dibutyltin dilaurate, zinc isooctanoate and bismuth isooctanoate.
3. The production process of the aerogel polyurethane thermal insulation material as claimed in claim 1, wherein the filling masterbatch synthesized in the step (2) is: a. adding 8-10 parts of diphenylmethane diisocyanate and 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 while stirring, obtaining a pre-polymerization solution after dropping, and continuously keeping at 60 ℃; b. continuously dropwise adding 15 parts of dimethylformamide solution dissolved with 1.8 parts of 1, 4-butanediol into the pre-polymerization solution, and after dropwise adding, heating to 80 ℃ for reacting for 3 hours; c. after the reaction is finished, devolatilizing and drying to remove the dimethylformamide to obtain the finished product.
4. The production process of the aerogel polyurethane thermal insulation material as claimed in claim 1, wherein the mixing and extrusion process parameters of the step (3) are that a high-speed-low-speed mixing unit is adopted to mix materials, the hot mixing is carried out for 80 ℃, the hot mixing is carried out for 5-8 min, the cold mixing is carried out for 40 ℃, the cold mixing is carried out for 10-20 min, and the extrusion temperature of the double screws is as follows: the first to the fifth sections are 190 ℃, 200 ℃, 205 ℃, 210 ℃, the flange temperature is 190 ℃, the head temperature is 210 ℃ in the first section and 215 ℃ in the second section.
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Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| 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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Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| 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 |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN115304739A (en) * | 2022-08-29 | 2022-11-08 | 山东北理华海复合材料有限公司 | Preparation method of aerogel polyurethane composite thermal insulation material |
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