CN116786389B - Flame-retardant heat-insulating composite material and preparation method thereof - Google Patents
Flame-retardant heat-insulating composite material and preparation method thereof Download PDFInfo
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- CN116786389B CN116786389B CN202311062192.4A CN202311062192A CN116786389B CN 116786389 B CN116786389 B CN 116786389B CN 202311062192 A CN202311062192 A CN 202311062192A CN 116786389 B CN116786389 B CN 116786389B
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- retardant
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- intumescent flame
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- 239000003063 flame retardant Substances 0.000 title claims abstract description 248
- 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 compound 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 title claims abstract description 242
- 239000002131 composite material Substances 0.000 title claims abstract description 56
- 238000002360 preparation method Methods 0.000 title claims abstract description 34
- 238000000576 coating method Methods 0.000 claims abstract description 168
- 239000011248 coating agent Substances 0.000 claims abstract description 165
- 229920003987 resole Polymers 0.000 claims abstract description 70
- 239000003292 glue Substances 0.000 claims abstract description 69
- 239000004964 aerogel Substances 0.000 claims abstract description 65
- 239000004114 Ammonium polyphosphate Substances 0.000 claims abstract description 53
- 229920001276 ammonium polyphosphate Polymers 0.000 claims abstract description 53
- WXZMFSXDPGVJKK-UHFFFAOYSA-N pentaerythritol Chemical compound OCC(CO)(CO)CO WXZMFSXDPGVJKK-UHFFFAOYSA-N 0.000 claims abstract description 53
- 235000019826 ammonium polyphosphate Nutrition 0.000 claims abstract description 51
- 239000011324 bead Substances 0.000 claims abstract description 50
- 239000011521 glass Substances 0.000 claims abstract description 49
- 229920000877 Melamine resin Polymers 0.000 claims abstract description 42
- JDSHMPZPIAZGSV-UHFFFAOYSA-N melamine Chemical compound NC1=NC(N)=NC(N)=N1 JDSHMPZPIAZGSV-UHFFFAOYSA-N 0.000 claims abstract description 42
- 239000003973 paint Substances 0.000 claims abstract description 33
- 239000002994 raw material Substances 0.000 claims abstract description 13
- 239000000243 solution Substances 0.000 claims description 88
- 229940059574 pentaerithrityl Drugs 0.000 claims description 51
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 43
- 238000009413 insulation Methods 0.000 claims description 41
- 238000003756 stirring Methods 0.000 claims description 29
- 238000000034 method Methods 0.000 claims description 26
- 238000002156 mixing Methods 0.000 claims description 25
- FXSGDOZPBLGOIN-UHFFFAOYSA-N trihydroxy(methoxy)silane Chemical compound CO[Si](O)(O)O FXSGDOZPBLGOIN-UHFFFAOYSA-N 0.000 claims description 23
- 239000000835 fiber Substances 0.000 claims description 19
- 239000000843 powder Substances 0.000 claims description 19
- OUPZKGBUJRBPGC-UHFFFAOYSA-N 1,3,5-tris(oxiran-2-ylmethyl)-1,3,5-triazinane-2,4,6-trione Chemical compound O=C1N(CC2OC2)C(=O)N(CC2OC2)C(=O)N1CC1CO1 OUPZKGBUJRBPGC-UHFFFAOYSA-N 0.000 claims description 18
- 239000000203 mixture Substances 0.000 claims description 18
- 238000005507 spraying Methods 0.000 claims description 18
- 238000001132 ultrasonic dispersion Methods 0.000 claims description 15
- 235000011114 ammonium hydroxide Nutrition 0.000 claims description 13
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 claims description 12
- KZHJGOXRZJKJNY-UHFFFAOYSA-N dioxosilane;oxo(oxoalumanyloxy)alumane Chemical compound O=[Si]=O.O=[Si]=O.O=[Al]O[Al]=O.O=[Al]O[Al]=O.O=[Al]O[Al]=O KZHJGOXRZJKJNY-UHFFFAOYSA-N 0.000 claims description 12
- 229910052863 mullite Inorganic materials 0.000 claims description 12
- RMAQACBXLXPBSY-UHFFFAOYSA-N silicic acid Chemical compound O[Si](O)(O)O RMAQACBXLXPBSY-UHFFFAOYSA-N 0.000 claims description 12
- 239000002245 particle Substances 0.000 claims description 11
- 238000006116 polymerization reaction Methods 0.000 claims description 11
- HBMJWWWQQXIZIP-UHFFFAOYSA-N silicon carbide Chemical group [Si+]#[C-] HBMJWWWQQXIZIP-UHFFFAOYSA-N 0.000 claims description 11
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 claims description 10
- 238000006243 chemical reaction Methods 0.000 claims description 8
- 238000004821 distillation Methods 0.000 claims description 8
- MGJURKDLIJVDEO-UHFFFAOYSA-N formaldehyde;hydrate Chemical compound O.O=C MGJURKDLIJVDEO-UHFFFAOYSA-N 0.000 claims description 8
- 229910010271 silicon carbide Inorganic materials 0.000 claims description 8
- BOTDANWDWHJENH-UHFFFAOYSA-N Tetraethyl orthosilicate Chemical compound CCO[Si](OCC)(OCC)OCC BOTDANWDWHJENH-UHFFFAOYSA-N 0.000 claims description 7
- YKTSYUJCYHOUJP-UHFFFAOYSA-N [O--].[Al+3].[Al+3].[O-][Si]([O-])([O-])[O-] Chemical group [O--].[Al+3].[Al+3].[O-][Si]([O-])([O-])[O-] YKTSYUJCYHOUJP-UHFFFAOYSA-N 0.000 claims description 6
- 239000007864 aqueous solution Substances 0.000 claims description 6
- 238000009835 boiling Methods 0.000 claims description 6
- 238000001816 cooling Methods 0.000 claims description 6
- HUAUNKAZQWMVFY-UHFFFAOYSA-M sodium;oxocalcium;hydroxide Chemical compound [OH-].[Na+].[Ca]=O HUAUNKAZQWMVFY-UHFFFAOYSA-M 0.000 claims description 6
- 238000000352 supercritical drying Methods 0.000 claims description 6
- NWUYHJFMYQTDRP-UHFFFAOYSA-N 1,2-bis(ethenyl)benzene;1-ethenyl-2-ethylbenzene;styrene Chemical compound C=CC1=CC=CC=C1.CCC1=CC=CC=C1C=C.C=CC1=CC=CC=C1C=C NWUYHJFMYQTDRP-UHFFFAOYSA-N 0.000 claims description 5
- TXBCBTDQIULDIA-UHFFFAOYSA-N 2-[[3-hydroxy-2,2-bis(hydroxymethyl)propoxy]methyl]-2-(hydroxymethyl)propane-1,3-diol Chemical compound OCC(CO)(CO)COCC(CO)(CO)CO TXBCBTDQIULDIA-UHFFFAOYSA-N 0.000 claims description 5
- CAQWNKXTMBFBGI-UHFFFAOYSA-N C.[Na] Chemical compound C.[Na] CAQWNKXTMBFBGI-UHFFFAOYSA-N 0.000 claims description 5
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims description 5
- 239000004115 Sodium Silicate Substances 0.000 claims description 5
- 239000002253 acid Substances 0.000 claims description 5
- 239000003729 cation exchange resin Substances 0.000 claims description 5
- 229910052739 hydrogen Inorganic materials 0.000 claims description 5
- 239000001257 hydrogen Substances 0.000 claims description 5
- 229910001415 sodium ion Inorganic materials 0.000 claims description 5
- 229910052911 sodium silicate Inorganic materials 0.000 claims description 5
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 4
- 230000007062 hydrolysis Effects 0.000 claims description 3
- 238000006460 hydrolysis reaction Methods 0.000 claims description 3
- 238000002791 soaking Methods 0.000 claims description 3
- TWNQGVIAIRXVLR-UHFFFAOYSA-N oxo(oxoalumanyloxy)alumane Chemical compound O=[Al]O[Al]=O TWNQGVIAIRXVLR-UHFFFAOYSA-N 0.000 claims description 2
- 230000035484 reaction time Effects 0.000 claims description 2
- 239000000377 silicon dioxide Substances 0.000 claims description 2
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- 239000008199 coating composition Substances 0.000 abstract description 2
- 239000010410 layer Substances 0.000 description 220
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- -1 fatty acid ethylene oxide Chemical class 0.000 description 17
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- 229920001343 polytetrafluoroethylene Polymers 0.000 description 15
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- 229910000831 Steel Inorganic materials 0.000 description 12
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- 238000003860 storage Methods 0.000 description 11
- 239000011325 microbead Substances 0.000 description 10
- 239000007788 liquid Substances 0.000 description 9
- 239000000463 material Substances 0.000 description 9
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 8
- 239000004615 ingredient Substances 0.000 description 8
- 238000010992 reflux Methods 0.000 description 8
- 229920005989 resin Polymers 0.000 description 8
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- 239000000779 smoke Substances 0.000 description 8
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- 238000002679 ablation Methods 0.000 description 7
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- 238000010276 construction Methods 0.000 description 6
- 238000007599 discharging Methods 0.000 description 6
- 238000001035 drying Methods 0.000 description 6
- 238000005204 segregation Methods 0.000 description 6
- 238000007711 solidification Methods 0.000 description 6
- 230000008023 solidification Effects 0.000 description 6
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical class [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 5
- 239000012895 dilution Substances 0.000 description 5
- 238000010790 dilution Methods 0.000 description 5
- 238000002844 melting Methods 0.000 description 5
- 230000008018 melting Effects 0.000 description 5
- 239000004005 microsphere Substances 0.000 description 5
- 239000011134 resol-type phenolic resin Substances 0.000 description 5
- 238000010345 tape casting Methods 0.000 description 5
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 4
- XLOMVQKBTHCTTD-UHFFFAOYSA-N Zinc monoxide Chemical compound [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 description 4
- 229910021529 ammonia Inorganic materials 0.000 description 4
- 230000008859 change Effects 0.000 description 4
- 239000000084 colloidal system Substances 0.000 description 4
- 238000009833 condensation Methods 0.000 description 4
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- 239000003822 epoxy resin Substances 0.000 description 4
- 230000009970 fire resistant effect Effects 0.000 description 4
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- 230000009974 thixotropic effect Effects 0.000 description 4
- BIKXLKXABVUSMH-UHFFFAOYSA-N trizinc;diborate Chemical compound [Zn+2].[Zn+2].[Zn+2].[O-]B([O-])[O-].[O-]B([O-])[O-] BIKXLKXABVUSMH-UHFFFAOYSA-N 0.000 description 4
- 239000000908 ammonium hydroxide Substances 0.000 description 3
- 230000015572 biosynthetic process Effects 0.000 description 3
- 239000012141 concentrate Substances 0.000 description 3
- 239000012774 insulation material Substances 0.000 description 3
- 229920002689 polyvinyl acetate Polymers 0.000 description 3
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- 125000001453 quaternary ammonium group Chemical group 0.000 description 3
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- KXGFMDJXCMQABM-UHFFFAOYSA-N 2-methoxy-6-methylphenol Chemical class [CH]OC1=CC=CC([CH])=C1O KXGFMDJXCMQABM-UHFFFAOYSA-N 0.000 description 2
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 2
- JJEJDZONIFQNHG-UHFFFAOYSA-N [C+4].N Chemical compound [C+4].N JJEJDZONIFQNHG-UHFFFAOYSA-N 0.000 description 2
- 230000009471 action Effects 0.000 description 2
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 2
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- 239000010439 graphite Substances 0.000 description 2
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- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 2
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- JYEUMXHLPRZUAT-UHFFFAOYSA-N 1,2,3-triazine Chemical group C1=CN=NN=C1 JYEUMXHLPRZUAT-UHFFFAOYSA-N 0.000 description 1
- KIAMPLQEZAMORJ-UHFFFAOYSA-N 1-ethoxy-2-[2-(2-ethoxyethoxy)ethoxy]ethane Chemical compound CCOCCOCCOCCOCC KIAMPLQEZAMORJ-UHFFFAOYSA-N 0.000 description 1
- COBPKKZHLDDMTB-UHFFFAOYSA-N 2-[2-(2-butoxyethoxy)ethoxy]ethanol Chemical compound CCCCOCCOCCOCCO COBPKKZHLDDMTB-UHFFFAOYSA-N 0.000 description 1
- JDSQBDGCMUXRBM-UHFFFAOYSA-N 2-[2-(2-butoxypropoxy)propoxy]propan-1-ol Chemical compound CCCCOC(C)COC(C)COC(C)CO JDSQBDGCMUXRBM-UHFFFAOYSA-N 0.000 description 1
- LQJBNNIYVWPHFW-UHFFFAOYSA-N 20:1omega9c fatty acid Natural products CCCCCCCCCCC=CCCCCCCCC(O)=O LQJBNNIYVWPHFW-UHFFFAOYSA-N 0.000 description 1
- QSBYPNXLFMSGKH-UHFFFAOYSA-N 9-Heptadecensaeure Natural products CCCCCCCC=CCCCCCCCC(O)=O QSBYPNXLFMSGKH-UHFFFAOYSA-N 0.000 description 1
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- 239000005696 Diammonium phosphate Substances 0.000 description 1
- IMQLKJBTEOYOSI-GPIVLXJGSA-N Inositol-hexakisphosphate Chemical compound OP(O)(=O)O[C@H]1[C@H](OP(O)(O)=O)[C@@H](OP(O)(O)=O)[C@H](OP(O)(O)=O)[C@H](OP(O)(O)=O)[C@@H]1OP(O)(O)=O IMQLKJBTEOYOSI-GPIVLXJGSA-N 0.000 description 1
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Abstract
The invention belongs to the technical field of coating compositions, and particularly relates to a flame-retardant heat-insulating composite material and a preparation method thereof. The flame-retardant heat-insulating composite material comprises an aerogel heat-insulating felt layer, an intumescent flame-retardant inner layer and an intumescent flame-retardant outer layer, wherein the intumescent flame-retardant outer layer, the intumescent flame-retardant inner layer and the aerogel heat-insulating felt layer are sequentially connected from top to bottom; the expansion flame-retardant inner layer is prepared by coating and curing expansion flame-retardant inner layer paint; the raw materials of the intumescent flame retardant inner layer coating comprise ammonium polyphosphate, pentaerythritol, melamine, modified resol glue solution and hollow glass beads; the intumescent flame retardant outer layer is prepared by coating and curing an intumescent flame retardant outer layer coating; the raw materials of the intumescent flame-retardant outer coating comprise ammonium polyphosphate, pentaerythritol, melamine, modified resol glue solution and whiskers. The invention is suitable for certain demanding fireproof application scenes, and can reliably reach the fire resistance limit of longer than 5 hours under the condition of proper thickness.
Description
Technical Field
The invention belongs to the technical field of coating compositions, and particularly relates to a flame-retardant heat-insulating composite material and a preparation method thereof.
Background
The fire disaster is easy to cause great economic and personnel loss and serious consequences, and the prevention and control responsibility of the fire disaster is heavier than that of Taishan mountain; the adoption of the flame-retardant heat-insulating composite material with proper performance is one of key measures for preventing fire and reducing fire loss. With the enhancement of safety consciousness, the national requirement on flame retardant performance is stringent, the demand and application of novel flame retardant products are continuously and rapidly increased, and the annual growth rate is more than 5%.
Flame retardant and heat insulating composites are the most important fire resistant materials. When a fire disaster occurs, the flame-retardant heat-insulating composite material can play roles in isolating a fire source and reducing heat transfer capacity, so that important facilities and equipment are protected, the performance influence and structural damage of flame and high temperature on a fireproof object are avoided and delayed, and the influence range, the spreading range and the loss caused by the fire disaster are controlled. If the protection of proper flame-retardant heat-insulating composite materials is lacking, obvious strength reduction can occur when a fire disaster occurs and after the fire disaster occurs, the risk of secondary disasters such as structural collapse exists, and more serious consequences are easily caused.
The steel structure fireproof paint of GB 14007-2018, the facing fireproof paint of GB12441-2018, the concrete structure fireproof paint of GB28375-2012 and the cable fireproof paint of GB28374-2012 are all fireproof paint with flame-retardant and heat-insulating effects. The dispersion medium of the water-based expansion type fireproof paint is water and water-containing feed liquid, and the coating expands and foams and forms a fireproof heat insulation protective layer when encountering high temperature after drying, so that the coating has a dominant market position due to low application amount, high construction speed and low engineering cost. In addition, rock wool, slag wool and products thereof for heat insulation, such as GB/T11835-2016, are fireproof materials with main heat insulation effect, and have the performances of incombustibility, high temperature resistance and the like.
In the prior art, as disclosed in Chinese patent CN112708316A, the water-based indoor expansion type steel structure fireproof coating comprises the following components in parts by weight: 22-23 parts of aqueous polyvinyl acetate emulsion, 24-26 parts of ammonium polyphosphate, 8-10 parts of pentaerythritol, 8-10 parts of melamine, 5-10 parts of polyvinyl acetate modified carbon nanotubes, 8-10 parts of titanium dioxide, 0.5-1 part of sepiolite, 1-2 parts of ceramic fiber, 1-2 parts of film forming additive (at least one of triethylene glycol diethyl ether, triethylene glycol monobutyl ether and tripropylene glycol monobutyl ether), 1-2 parts of wetting dispersant (at least one of fatty acid ethylene oxide adduct, polyethylene glycol type polyhydric alcohol and polyethylene imide derivative), 0.1-0.3 part of mildew preventive, 0.1-0.3 part of defoamer, 0.1-0.5 part of pH regulator, 0.1-0.5 part of thickener and 10-15 parts of water. All technical indexes of the fireproof coating reach the indexes specified in GB 14007-2018 fire-retardant coating for steel structures, and the fireproof coating has excellent film forming property, high bonding strength and excellent fire resistance, can be rapidly expanded under the action of high temperature, forms a compact carbon layer, and is high in fire resistance limit and environment-friendly.
Chinese patent CN111592813A discloses an intumescent fire-retardant coating and a preparation method thereof, wherein the components comprise 13-17 parts of organosilicon modified epoxy resin, 2-4 parts of epoxy resin curing agent, 0.5-1.5 parts of smoke suppressant, 0.2-0.5 parts of dispersing agent, 1-3 parts of nano zinc oxide, 4-7 parts of hollow glass microsphere, 2-4 parts of nano silicon aerogel, 8-11 parts of zinc borate, 4-6 parts of expanded graphite, 20-30 parts of ammonium polyphosphate, 5-9 parts of melamine, 5-9 parts of pentaerythritol and 14-18 parts of solvent (such as mixed solution of xylene and acetone). The patent uses organosilicon modified epoxy resin as a matrix, ammonium polyphosphate, pentaerythritol and melamine as an intumescent flame-retardant system, zinc borate and nano zinc oxide as flame-retardant smoke-suppressing synergists, and hollow glass beads and expanded graphite as flame-retardant heat-insulating fillers, so that the prepared coating has excellent fireproof performance and smoke-suppressing performance, and can be used for fireproof protection of steel structures.
Chinese patent CN116218300A discloses a water-based smoke-suppressing and waterproof multifunctional fireproof paint and preparation and application thereof, wherein the multifunctional fireproof paint comprises 40-50 parts of acrylic emulsion, 15-25 parts of a dehydration and char formation catalyst (such as one or more of ammonium polyphosphate, diammonium phosphate and organic phosphate), 5-10 parts of a char formation agent (such as one or more of corn starch, pentaerythritol and organic resin), 10-20 parts of a foaming agent (such as one or more of melamine, dicyandiamide and chlorinated paraffin), 1-5 parts of kaolin, 15-25 parts of titanium dioxide, 1-5 parts of aluminum hydroxide and 1-5 parts of modified zinc borate (modified by oleic acid and phytic acid). The paint can simultaneously meet the basic requirements of smoke suppression, water resistance and fire resistance of the functional paint, and is environment-friendly and nontoxic.
The fireproof materials in the prior art are all used for flame retarding, heat insulating and protecting through a single-proportion coating, and the required fireproof effect is generally realized through controlling the thickness of the coating. However, due to the limitation of the composition, even if a thicker coating is obtained through multiple coating, the severe fireproof requirements of certain application scenes are still difficult to be met, for example, the fireproof limit measured according to the method of GB 1407-2018 is difficult to reach 3 hours, wherein the fireproof limit of the Chinese patent CN116218300A fireproof coating is lower than 1 hour; the Chinese patent CN112708316A, CN111592813A paint is tried to prepare composite coatings with various thickness combinations, and the fire resistance limit is difficult to exceed 3 hours. The Chinese patent CN111592813A fireproof paint has the segregation problem of hollow glass beads in the storage process and the solidification process after dilution and coating, and reduces the use effect value.
Therefore, it is necessary to develop a flame retardant and heat insulating composite material suitable for certain demanding fire-proof application scenarios, and capable of reaching a fire resistance limit longer than 5 hours under the condition of acceptable thickness.
Disclosure of Invention
The invention aims to provide a flame-retardant heat-insulating composite material which is suitable for certain fireproof application scenes with harsh requirements and can reliably reach the fire-resistant limit longer than 5 hours under the condition of proper thickness; the invention also provides a preparation method of the flame-retardant heat-insulating composite material.
The flame-retardant and heat-insulating composite material comprises an aerogel heat-insulating felt layer, an intumescent flame-retardant inner layer and an intumescent flame-retardant outer layer, wherein the intumescent flame-retardant outer layer, the intumescent flame-retardant inner layer and the aerogel heat-insulating felt layer are sequentially connected from top to bottom;
the aerogel heat insulation felt layer is prepared by compositing silicon dioxide in a fiber felt in an aerogel form by a sol-gel method;
the expansion flame-retardant inner layer is prepared by coating and curing expansion flame-retardant inner layer paint; the raw materials of the intumescent flame retardant inner layer coating comprise ammonium polyphosphate, pentaerythritol, melamine, modified resol glue solution and hollow glass beads;
the intumescent flame retardant outer layer is prepared by coating and curing an intumescent flame retardant outer layer coating; the raw materials of the intumescent flame-retardant outer coating comprise ammonium polyphosphate, pentaerythritol, melamine, modified resol glue solution and whiskers.
The thickness ratio of the aerogel heat insulation felt layer to the expansion flame retardant inner layer to the expansion flame retardant outer layer is (3-5): (2-3): (2-3), and the thickness is expressed in mm.
The heat conductivity coefficient of the aerogel heat insulation felt layer is 0.012-0.019W/m.k; the fiber felt is aluminum silicate fiber felt or aluminum oxide fiber felt.
The aerogel heat insulation felt layer is attached to the back fire surface of the fireproof object.
The weight ratio of the ammonium polyphosphate, the pentaerythritol, the melamine and the modified resol glue solution in the raw materials of the intumescent flame retardant inner layer coating is (4-5) 1 (2-3) 9-12, and the total volume of the mixture of the ammonium polyphosphate, the pentaerythritol, the melamine and the modified resol glue solutionThe ratio of the net volume of the hollow glass beads is (90-95): 100; the hollow glass beads are made of soda lime borosilicate, and have a true density of 0.15-0.25g/cm 3 The water pressure resistance is 8-10MPa, and the average particle diameter (outer diameter) is 50-80 μm.
The hollow glass beads are subjected to hydraulic pressure sorting of nominal pressure resistance grade, the beads in the floating layer are collected and dried, and then the hollow glass beads are used for preparing the intumescent flame retardant inner layer coating.
The weight ratio of the ammonium polyphosphate, pentaerythritol, melamine, modified resol glue solution and whisker in the raw materials of the intumescent flame-retardant outer layer coating is (5-7) 1 (2-3) 12-15 and (5-7); the whisker is silicon carbide whisker or mullite whisker, the average diameter of the whisker is 0.4-0.6 mu m, and the length-diameter ratio is 18-25.
The preparation method of the modified resol glue solution comprises the steps of stirring water, ammonia water, methyl silicic acid solution, formaldehyde water solution and phenol for reaction, distilling under reduced pressure, cooling to room temperature, adding triglycidyl isocyanurate, and continuing stirring to obtain the modified resol glue solution.
The concentration of the ammonia water is 20-25 wt%, the concentration of the methyl silicic acid solution is 3-6 wt%, the concentration of the formaldehyde water solution is 33-35 wt%, the reaction temperature is 75-90 ℃, the reaction time is 3.5-5h, the reduced pressure distillation time is 1-2h, and the continuous stirring time is 10-15h; the weight ratio of water, ammonia water, methyl silicic acid solution, formaldehyde water solution, phenol and triglycidyl isocyanurate is (1.1-1.3) (0.2-0.4) (0.15-0.2) (1.3-1.6) (1) (0.15-0.2); triglycidyl isocyanurate is a powder having a mean particle diameter (outer diameter) of 5 to 10. Mu.m.
The methyl silicic acid solution is prepared by removing sodium ions from 3.8-7.6wt.% methyl sodium silicate aqueous solution through hydrogen type macroporous strong acid cation exchange resin exchange, and the methyl silicic acid solution is used for feeding the modified resol glue solution within 5 hours after preparation so as to reduce the influence of dimerization and multimerization of methyl silicic acid on the performance of the modified resol glue solution.
The preparation method of the modified resol glue solution comprises the steps of adding water, ammonia water, methyl silicic acid solution, formaldehyde aqueous solution and phenol into a reactor, starting condensation reflux, stirring for reaction, then performing reduced pressure distillation until the solid concentration of the feed liquid is 30-33wt.%, cooling to room temperature, adding triglycidyl isocyanurate, and continuing stirring to obtain the modified resol glue solution; wherein the condensing temperature is controlled below 15 ℃ during condensing reflux, the temperature of feed liquid is controlled between 73 ℃ and 80 ℃ during reduced pressure distillation, and the air suction vacuum degree (absolute pressure) is 30 to 42kPa.
The ammonium polyphosphate, pentaerythritol and melamine are all powder with the average particle diameter (outer diameter) of 5-20 mu m, and the polymerization degree of the ammonium polyphosphate is 500-650; in pentaerythritol, the content of monopentaerythritol is more than or equal to 80wt.%, and the content of dipentaerythritol is more than or equal to 8wt.%.
The preparation method of the flame-retardant heat-insulating composite material comprises the following steps:
(1) Adding tetraethyl silicate into boiling water for hydrolysis to obtain silica sol; soaking silica sol in a fiber felt, and performing supercritical drying to obtain an aerogel heat insulation felt layer;
(2) Firstly adding ammonium polyphosphate, pentaerythritol and melamine into modified resol glue solution, uniformly mixing, performing ultrasonic dispersion, spraying into hollow glass beads, and uniformly mixing to obtain an intumescent flame retardant inner layer coating;
(3) Adding the whisker into the modified resol glue solution, uniformly mixing, performing ultrasonic dispersion, adding ammonium polyphosphate, pentaerythritol and melamine, uniformly mixing, and performing ultrasonic dispersion to obtain the intumescent flame-retardant outer layer coating;
(4) Coating the expansion flame-retardant inner layer coating on the aerogel heat-insulating felt layer, and curing to obtain an expansion flame-retardant inner layer composite aerogel heat-insulating felt layer;
(5) And (3) coating the intumescent flame-retardant outer coating on the intumescent flame-retardant inner layer, and curing to obtain the flame-retardant heat-insulating composite material.
The preparation method of the flame-retardant heat-insulating composite material comprises the following specific steps:
(1) Adding tetraethyl silicate (TEOS) into boiling water for hydrolysis to obtain silica sol; soaking silica sol in a fiber felt, and performing supercritical drying to obtain an aerogel heat insulation felt layer;
(2) Firstly adding ammonium polyphosphate, pentaerythritol and melamine into modified resol glue solution, uniformly mixing, performing ultrasonic dispersion for 20-30min, gradually spraying into hollow glass beads, and uniformly mixing to obtain an intumescent flame retardant inner layer coating;
(3) Adding the whisker into the modified resol glue solution, uniformly mixing, performing ultrasonic dispersion for 20-40min, adding ammonium polyphosphate, pentaerythritol and melamine, uniformly mixing, and performing ultrasonic dispersion for 20-60min to obtain the intumescent flame retardant outer coating;
(4) Coating the expansion flame-retardant inner layer coating on the aerogel heat-insulating felt layer, and curing to obtain an expansion flame-retardant inner layer composite aerogel heat-insulating felt layer;
(5) And (3) coating the intumescent flame-retardant outer coating on the intumescent flame-retardant inner layer, and curing to obtain the flame-retardant heat-insulating composite material.
The modified resol glue solution is reddish brown semitransparent, can penetrate laser beams, has clear light path, has the viscosity of 500-800 mPa.s, is colloid, has the quality of more than 3 months in a stable period (the light transmittance, the viscosity and the use effect basically have no change after being stored for 3 months in a sealed shading way), has light smell, has the formaldehyde and phenol content of lower than 0.1wt.%, basically does not contain ammonia (one of the functions of reduced pressure distillation), is solidified after being added with quaternary ammonium hydroxide (strong base) at normal temperature or being directly heated to 180 ℃, and forms a solid with certain strength and easy hot melting (different from the characteristic that the conventional resol glue solution cannot be hot melted after being solidified). From these properties and the performance conditions described later, it is known that, in the preparation process of the modified resol glue solution, both the added methyl silicic acid and triglycidyl isocyanurate are grafted into the long molecular chains of the resol more uniformly, and the performance of the resol, especially the further polymerization performance, is significantly changed; if the resol glue solution prepared without triglycidyl isocyanurate is not cured when the temperature is raised to 240 ℃, the cured product after adding quaternary amine base at normal temperature cannot be melted; when methyl silicic acid is not added, or when a considerable amount of organic silicon is directly added into the glue solution without adding methyl silicic acid, the light transmittance of the glue solution is obviously reduced and the viscosity is increased by more than one time after the glue solution is stored for 1 month in a sealed and shading way.
The preparation of the intumescent flame retardant inner layer coating and the intumescent flame retardant outer layer coating can adopt a conventional method, and other auxiliary agents can be added, but the ingredients and the preparation method have good technical effects.
The intumescent flame retardant inner layer coating has certain storage stability, and after being sealed, shaded, stood and stored for 3 months, only slight segregation of hollow glass beads occurs, namely, a mixture consisting of ammonium polyphosphate, pentaerythritol, melamine and modified resol glue solution only sinks a little and concentrates on a coating bottom layer, and the coating returns to a normal state after being stirred again or shaken uniformly, so that the use effect is basically unchanged; in the process of airtight non-shading standing storage for 3 days, segregation of the hollow glass beads and sinking and concentration of the mixture to the paint bottom layer are not seen, the paint is tested after storage for 3 days without stirring or shaking again, the paint is judged to be very uniform according to the paint effect, and segregation of the hollow glass beads does not occur. In the inner layer coating, the volume of the hollow glass beads is obviously higher than that of the mixture, and the hollow glass beads have moderate viscosity and fluidity, and do not need to be diluted when being constructed in modes of spraying, roller coating, knife coating and the like. The Chinese patent CN111592813A fireproof paint has the obvious segregation problem of hollow glass beads in the storage process and the solidification process after dilution and coating, has higher viscosity, has general fluidity and thixotropy, needs dilution when being constructed by means of spraying, roller coating and the like, and has lower hollow glass bead content.
The intumescent flame retardant outer layer coating has good storage stability, silicon carbide whiskers or mullite whiskers sink and concentrate on a coating bottom layer after being stored for 3 months in a closed shading and standing way, and the coating is restored to a normal state after being stirred uniformly again or shaken uniformly, so that the use effect is not changed; in the process of airtight non-shading standing storage for 3 days, the silicon carbide whisker or mullite whisker cannot be seen to sink or concentrate to the paint bottom layer, the paint is tested after storage for 3 days without stirring again or shaking uniformly, and the paint is judged to be very uniform according to the paint effect.
The intumescent flame retardant inner layer coating and the intumescent flame retardant outer layer coating have good storage stability, moderate viscosity, thixotropic property and mobility, can be constructed by spraying, roller coating, knife coating and other modes (can be diluted by adding water), and have the surface fixing time of less than 10 hours in an air environment with the temperature of 10-30 ℃ below 75% of relative humidity. Under the condition of the thickness proportion, the expansion flame-retardant inner layer coating is easy to adhere and bond with the aerogel heat insulation felt layer, the expansion flame-retardant outer layer coating is easy to adhere and bond with the surface of the cured expansion flame-retardant inner layer, and the construction process is convenient and reliable; after coating, the surface layer gradually solidifies as the contained moisture gradually volatilizes, after which the entire coating gradually loses water and solidifies.
The expansion flame-retardant inner layer and the expansion flame-retardant outer layer mainly complete foaming and carbonization at the temperature of below 750 ℃ and form carbon foam at the temperature of 850 ℃; in the ingredients, pentaerythritol and modified resol glue are all char-forming raw materials, melamine has about 20% of carbon nitrogen compound residues besides most of gasification and foaming agent functions, and the thermal decomposition products of ammonium polyphosphate play an important role in the char-forming process and the ablation resistance and heat insulation effects of an expansion layer.
The wall thickness of the hollow glass beads corresponding to the expansion flame-retardant inner layer coating ranges from 3 mu m to 5 mu m, and the hollow glass beads have certain tolerance to the product of ammonium polyphosphate at high temperature; the melting point of the hollow glass beads is lower than 950 ℃, and the hollow glass beads and the composite of the carbon-ammonium polyphosphate thermal decomposition product formed by foaming form an ablation-resistant heat insulation material together, so that the ablation-resistant heat insulation material has an ablation-resistant effect, and plays a key role in prolonging the flame-retardant heat insulation time of the flame-retardant inner layer after expanding and carbonizing and the fire-resistant limit time of the flame-retardant heat insulation composite material. It is generally considered that the hollow glass beads made of the soda lime borosilicate are not easy to be compounded with the carbon material after being melted; in the invention, the inner layer is expanded and heated to 850 ℃ to be melted and compounded with the ammonium polyphosphate thermal decomposition product and the carbon foam, so that the inner layer expansion layer has stable ablation-resistant and heat-insulating effects within a few hours.
The hollow glass beads usually contain about 10% of beads with low pressure resistance and shell damage after preparation, storage and transportation, the beads with low pressure resistance and shell damage are firstly subjected to hydraulic pressure sorting of nominal pressure resistance level, the beads with low pressure resistance and shell damage are selected and not used (sink to the water bottom), and the beads in a floating layer are collected and dried and then used for preparing the intumescent flame retardant inner layer coating. The sorting operation can improve the heat insulation effect of the expanded inner layer. The net volume of the hollow glass beads refers to the net total volume of the beads in the hollow glass bead powder, and is measured by a drainage method.
The silicon carbide whisker or mullite whisker contained in the intumescent flame retardant outer layer coating has high temperature resistance and high temperature strength, can resist high temperature below 1300 ℃, can limit excessive expansion and uneven expansion of the coating, is favorable for forming a compact and even expansion layer, thereby improving the strength and expansion uniformity of the cured coating and the expanded outer layer, has obvious synergistic flame retardant effect, forms an ablation-resistant flame-proof material together with a compound of carbon-ammonium polyphosphate thermal decomposition products formed by foaming, plays a key role in prolonging the flame-proof time of the flame-retardant outer layer after the carbon is expanded and the fire-proof limit time of the flame-retardant heat-proof composite material. Silicon carbide whiskers or mullite whiskers having an average diameter of 0.4 to 0.6 μm and an aspect ratio of 18 to 25 are preferably used to obtain better expansion uniformity and synergistic flame retardant effect.
In the process of preparing and storing the mixture, the main components of the intumescent flame retardant inner layer coating and the intumescent flame retardant outer layer coating are almost free from chemical action between ammonium polyphosphate, pentaerythritol, melamine and modified resol glue; in the room temperature water loss, solidification and coating normal low temperature service process after coating construction, certain resin polymerization reaction can occur, and the resin polymerization reaction is limited between a part of reaction points and groups with higher activity, but the resin contained in the resin polymerization reaction can occur to a greater extent in the heating process when meeting fire, thereby not only ensuring the strength of the coating, but also not influencing the expansion effect and flame retardant effect of the coating when meeting fire or at high temperature. The flame-retardant heat-insulating composite material disclosed by the invention is free from smoke suppression components such as antimony oxide and zinc borate, but is less in smoke generation, slower in smoke generation and free from concentrated release of dense smoke in the fire-resistant limit test process, and is considered to have a larger relation with the expansion flame-retardant inner layer and the expansion flame-retardant outer layer by taking the modified resol resin as a bonding component, and the resin has unconventional polymerization performance, heated melting performance and carbonization performance.
The aerogel heat insulation felt layer has great effects of prolonging the fire resistance limit and stably maintaining the longer fire resistance limit, and is a final protective barrier for attached fireproof objects, and the heat insulation performance and the heat resistance performance of the aerogel heat insulation felt layer are balanced. The aerogel heat insulation felt layer is used as a novel heat insulation material, can resist the high temperature below 1300 ℃, and can basically keep the heat insulation performance in a limited period of hours under the condition of high temperature of fire; the waterproof material has higher hydrophobicity and waterproof performance, has certain compression resistance, tensile resistance and crack resistance, can be attached and bonded on the outer surface of a fireproof object, and has higher application value.
The modified resol glue solution is solidified to form a solid with certain strength after being heated to 180 ℃ and has the characteristic of easy hot melting, can prevent the problems of dripping, uneven expansion and the like of the intumescent flame-retardant outer layer and the intumescent flame-retardant inner layer in the gradual heating process after meeting fire or contacting a high-temperature heat source, has high char yield, is superior to polyvinyl acetate (CN 112708316A) in char yield and flame retardant effect, and is superior to epoxy resin (CN 111592813A) which is easy to solidify but cannot be hot melted in expansion uniformity and cost.
The polymerization degree of the ammonium polyphosphate is preferably 500-650, so that the inner and outer coatings have better expansion flame retardant property.
The triglycidyl isocyanurate has three epoxy groups and a triazine ring structure, and the triglycidyl isocyanurate is grafted to a long chain of the resol during the preparation process of the modified resol glue solution, so that the epoxy groups can be crosslinked with the resol at the temperature of more than 160 ℃ to improve the expansion effects and flame retardant effects of foaming, char formation and the like of the inner and outer coatings to a certain extent.
The beneficial effects of the invention are as follows:
(1) The flame-retardant heat-insulating composite material is made of flame-retardant materials, and the problems of burning or molten drops in a fire scene can be avoided;
(2) The three-layer progressive flame-retardant heat-insulating structure ensures excellent flame-retardant heat-insulating effect, and when the thickness ratio of the aerogel heat-insulating felt layer to the intumescent flame-retardant inner layer to the intumescent flame-retardant outer layer is (3-5): 2-3, the fire-retardant limit of more than 5 hours can be reliably reached, and meanwhile, the surface of a protection object can be maintained at the temperature below 80 ℃ for a longer time, so that important equipment and equipment can be well protected;
(3) The cost for realizing the same flame-retardant protection effect is lower than that of the prior art.
Drawings
FIG. 1 is a schematic structural view of a flame retardant and thermally insulating composite of the present invention;
in the figure: 1. an aerogel insulation blanket; 2. an intumescent flame retardant inner layer; 3. an intumescent flame retardant outer layer.
Detailed Description
The invention is further described below with reference to examples.
Example 1
The flame-retardant and heat-insulating composite material comprises an aerogel heat-insulating felt layer, an intumescent flame-retardant inner layer and an intumescent flame-retardant outer layer, wherein the thickness ratio of the three layers is 3:2:2, the thickness is measured in mm, and the intumescent flame-retardant outer layer, the intumescent flame-retardant inner layer and the aerogel heat-insulating felt layer are sequentially connected from top to bottom; wherein, the aerogel heat insulation felt layer is attached to the back fire surface of the fireproof test piece.
Aerogel insulation blanket (commercially available) having a thermal conductivity of 0.019W/m·k; the preparation process of the aerogel heat insulation felt layer is that tetraethyl silicate is hydrolyzed in boiling water for 1h by a sol-gel method, firstly, 0.8wt.% silica sol is prepared, the silica sol is immersed in aluminum silicate fiber felt, and then, the aluminum silicate fiber felt is subjected to supercritical drying to obtain the aerogel heat insulation felt layer.
The intumescent flame retardant inner layer is formed by coating, naturally drying and curing at room temperature (indoor air environment, relative humidity 70-75%, temperature 24-26 ℃, surface curing time 8.3h, and integral curing time 25 h); the ingredients of the intumescent flame retardant inner layer coating are400g of ammonium polyphosphate, 100g of pentaerythritol, 200g of melamine, 900g of modified resol glue solution and 1379mL of hollow glass beads with net volume; the preparation process of the intumescent flame retardant inner layer coating comprises the following steps: adding ammonium polyphosphate, pentaerythritol and melamine into modified phenolic resin glue solution, uniformly mixing, ultrasonically dispersing for 20min, discharging to obtain a mixture with a volume of 1310mL (a polytetrafluoroethylene plastic lining is not adhered), adding hollow glass bead powder with a net volume of 1379mL into the 5L stirring mixer with polytetrafluoroethylene plastic lining, spraying and uniformly mixing 1310mL of the mixture into the hollow glass bead powder, spraying for 21min, and continuously stirring for 10min to be uniform to obtain the intumescent flame-retardant inner layer coating with the polytetrafluoroethylene plastic lining; the hollow glass beads are made of soda lime borosilicate, and have a true density of 0.15g/cm 3 The water pressure resistance strength is 8MPa, the average grain diameter (outer diameter) is 50 mu m (the average value of the wall thickness of the microbeads is estimated to be 3.5 mu m), the microbeads on the floating layer are firstly subjected to 8MPa water pressure separation (water pressure time is 15 min) before use, the microbeads on the floating layer are filtered out, compressed air is blown out to remove water, and are dried at 150 ℃, and the softening temperature is measured to be 760 ℃ or so and melted at 850 ℃; the ratio of the total volume of the mixture to the net volume of the hollow glass bead powder is 95:100.
The intumescent flame-retardant outer layer is formed by coating and curing an intumescent flame-retardant outer layer coating (the outer layer is coated after the inner layer is cured for 25 hours, the indoor air environment has the relative humidity of 70-75 percent, the temperature is 24-26 ℃, the surface curing time is 9 hours, and the integral curing time is 24 hours); the intumescent flame-retardant outer layer coating comprises 700g of ammonium polyphosphate, 100g of pentaerythritol, 300g of melamine, 1500g of modified resol glue solution and 500g of silicon carbide whisker; the average diameter of the silicon carbide whisker is 0.4 mu m, and the length-diameter ratio is 25; the preparation process of the intumescent flame-retardant outer layer coating comprises the following steps: adding modified resol-type phenolic resin glue solution, adding silicon carbide whiskers, uniformly mixing, performing ultrasonic dispersion for 40min, adding ammonium polyphosphate, pentaerythritol and melamine, uniformly mixing, performing ultrasonic dispersion for 30min, and discharging (without adhering to a polytetrafluoroethylene plastic lining) to obtain the intumescent flame-retardant outer layer coating.
The modified resol glue solution is prepared by the following steps: adding 1.1kg of water, 0.4kg of 20wt.% ammonia water, 0.2kg of 6wt.% methyl silicic acid solution, 1.6kg of 35wt.% formaldehyde solution and 1.0kg of phenol into a 5L stirring reactor, starting condensation reflux, stirring and reacting for 4 hours at 80 ℃, then distilling for 1 hour under reduced pressure until the solid concentration of the feed liquid is 33wt.%, cooling to room temperature, adding 0.2kg of triglycidyl isocyanurate, and continuing stirring for 10 hours to obtain modified resol glue solution; the condensing temperature is controlled to be 15 ℃ during condensing reflux, the temperature of feed liquid is controlled to be 80 ℃ during reduced pressure distillation, and the air suction vacuum degree (absolute pressure) is 42kPa; the added methyl silicic acid solution is prepared by removing sodium ions from 7.6wt.% methyl sodium silicate aqueous solution through hydrogen type macroporous strong acid cation exchange resin exchange, and is used for feeding modified resol glue solution 3h after preparation.
The average particle diameters (outer diameters) of the ammonium polyphosphate, pentaerythritol and melamine powders were 12 μm, 18 μm and 6 μm, respectively, the average particle diameter (outer diameter) of the triglycidyl isocyanurate powder was 5 μm, and the polymerization degree of the ammonium polyphosphate was 650; in pentaerythritol, the content of monopentaerythritol was 83wt.%, and the content of dipentaerythritol was 10wt.%.
The prepared modified resol glue solution is reddish brown semitransparent, can transmit blue laser beams, has clear light path, has the viscosity of 700 mPa.s, is a colloid, has the quality of more than 3 months in a stable period (the light transmittance and the viscosity basically do not change after being stored for 3 months in a sealed shading manner), has light smell, has the formaldehyde and phenol contents of less than 0.1wt.%, and does not contain ammonia basically; the solid formed by directly heating to 180 ℃ and preserving heat for 0.5h is strong, is easy to melt and thermoplastic, and is different from the conventional resol type phenolic resin which cannot be melt after being cured.
Coating the expansion flame-retardant inner layer coating on the aerogel heat-insulating felt layer, and curing to obtain an expansion flame-retardant inner layer composite aerogel heat-insulating felt layer; and (3) coating the intumescent flame-retardant outer coating on the intumescent flame-retardant inner layer, and curing to obtain the flame-retardant heat-insulating composite material.
The aerogel heat insulation felt layer has certain hydrophobicity and is easy to adhere to the expansion flame-retardant inner layer coating.
The viscosity, thixotropic property and fluidity of the intumescent flame retardant inner layer coating and the intumescent flame retardant outer layer coating are moderate, the intumescent flame retardant inner layer coating and the intumescent flame retardant outer layer coating can be constructed by spraying, roller coating, knife coating and the like, can be diluted by adding water, and the surface fixing time in an air environment with the temperature of 10-30 ℃ below 75% of relative humidity is lower than 10 hours. Under the condition of the thickness proportion, the expansion flame-retardant inner layer coating is easy to adhere and bond with the aerogel heat insulation felt layer, the expansion flame-retardant outer layer coating is easy to adhere and bond with the surface of the cured expansion flame-retardant inner layer, and the construction process is convenient and reliable; after coating, the inner layer coating and the outer layer coating are gradually volatilized along with the contained moisture, the surface layer is gradually solidified, and then the whole coating is gradually dehydrated and solidified.
Example 2
The flame-retardant and heat-insulating composite material comprises an aerogel heat-insulating felt layer, an intumescent flame-retardant inner layer and an intumescent flame-retardant outer layer, wherein the thickness ratio of the three layers is 4:2.5:2.5, the thickness is measured in mm, and the intumescent flame-retardant outer layer, the intumescent flame-retardant inner layer and the aerogel heat-insulating felt layer are sequentially connected from top to bottom; wherein, the aerogel heat insulation felt layer is attached to the back fire surface of the fireproof test piece.
Aerogel insulation blanket (commercially available) having a thermal conductivity of 0.012W/m·k; the preparation process of the aerogel heat insulation felt layer is that tetraethyl silicate is hydrolyzed in boiling water for 1h by a sol-gel method, firstly, 0.8wt.% silica sol is prepared, the silica sol is immersed in alumina fiber felt, and then, the alumina fiber felt is subjected to supercritical drying to obtain the aerogel heat insulation felt layer.
The expansion flame-retardant inner layer is formed by spraying, naturally drying and solidifying the expansion flame-retardant inner layer coating at room temperature (the indoor air environment, the relative humidity is 70-75 percent, the temperature is 24-26 ℃, the surface curing time is 8 hours, and the integral curing time is 24 hours); the ingredients of the intumescent flame retardant inner layer coating are 500g of ammonium polyphosphate, 100g of pentaerythritol, 300g of melamine, 1200g of modified resol glue solution and hollow glass beads with a net volume of 1867 mL; the preparation process of the intumescent flame retardant inner layer coating comprises the following steps: ammonium polyphosphate, pentaerythritol and trimerization were first mixed in a 5L stirring mixer lined with polytetrafluoroethylene plastic with a 0.5kW ultrasonic disperser Adding cyanamide into the modified resol glue solution, uniformly mixing, ultrasonically dispersing for 30min, discharging to obtain a mixed material (a polytetrafluoroethylene plastic lining is not adhered) with a volume of 1680mL, adding hollow glass bead powder with a net volume of 1867mL into a 5L stirring mixer of polytetrafluoroethylene plastic lining, spraying and uniformly mixing 1680mL of the mixed material into the hollow glass bead powder, spraying for 26min, and continuously stirring for 15min until uniformity to obtain the intumescent flame-retardant inner layer coating of the polytetrafluoroethylene plastic lining; the hollow glass beads are made of soda lime borosilicate, and have a true density of 0.25g/cm 3 The water pressure resistance strength is 9MPa, the average grain diameter (outer diameter) is 80 mu m (the average value of the wall thickness of the microbeads is estimated to be 5 mu m), the microbeads on the floating layer are filtered out by the water pressure of 9MPa before use (the water pressure time is 15 min), the water is blown by compressed air, the microbeads are dried at 150 ℃, and the softening temperature is measured to be 760 ℃ or so and melted at 850 ℃; the ratio of the total volume of the mixture to the net volume of the hollow glass bead powder is 90:100.
The intumescent flame-retardant outer layer is formed by coating and curing an intumescent flame-retardant outer layer coating (the outer layer is coated after the inner layer is cured for 24 hours, the indoor air environment has the relative humidity of 70-75 percent, the temperature is 24-26 ℃, the surface curing time is 11 hours, and the integral curing time is 22 hours); the intumescent flame-retardant outer layer coating comprises 500g of ammonium polyphosphate, 100g of pentaerythritol, 200g of melamine, 1200g of modified resol glue solution and 700g of mullite whisker; the average diameter of the mullite whisker is 0.5 mu m, and the length-diameter ratio is 20; the preparation process of the intumescent flame-retardant outer layer coating comprises the following steps: adding modified resol type phenolic resin glue solution, adding mullite whisker, uniformly mixing, performing ultrasonic dispersion for 20min, adding ammonium polyphosphate, pentaerythritol and melamine, uniformly mixing, performing ultrasonic dispersion for 30min, and discharging (without adhering to a polytetrafluoroethylene plastic lining) to obtain the intumescent flame-retardant outer layer coating.
The modified resol glue solution is prepared by the following steps: adding 1.3kg of water, 0.2kg of 22wt.% ammonia water, 0.15kg of 3wt.% methyl silicic acid solution, 1.3kg of 33wt.% formaldehyde water solution and 1.0kg of phenol into a 5L stirring reactor, starting condensation reflux, stirring at 90 ℃ for reaction for 3.5 hours, then distilling under reduced pressure for 2 hours until the concentration of solid material liquid is 30wt.%, cooling to room temperature, adding 0.15kg of triglycidyl isocyanurate, and continuing stirring for 15 hours to obtain modified resol glue solution; the condensing temperature is controlled to be 15 ℃ during condensing reflux, the feed liquid temperature is controlled to be 73 ℃ during reduced pressure distillation, and the air suction vacuum degree (absolute pressure) is 30kPa; the added methyl silicic acid solution is prepared by removing sodium ions from 3.8wt.% methyl sodium silicate aqueous solution through hydrogen type macroporous strong acid cation exchange resin exchange, and is used for feeding modified resol glue solution 2h after preparation.
The average particle diameters (outer diameters) of the ammonium polyphosphate, pentaerythritol and melamine powders were 10 μm, 15 μm and 8 μm, respectively, the average particle diameter (outer diameter) of the triglycidyl isocyanurate powder was 8 μm, and the polymerization degree of the ammonium polyphosphate was 600; in pentaerythritol, the content of monopentaerythritol was 80wt.%, and the content of dipentaerythritol was 12wt.%.
The prepared modified resol glue solution is reddish brown semitransparent, can transmit blue laser beams, has clear light path, has the viscosity of 600 mPa.s, is a colloid, has the quality of more than 3 months in a stable period (the light transmittance and the viscosity basically do not change after being stored for 3 months in a sealed shading manner), has light smell, has the formaldehyde and phenol contents of less than 0.1wt.%, and does not contain ammonia basically; at normal temperature, adding 1wt.% of quaternary ammonium hydroxide, stirring, standing for 1.4h, and solidifying to obtain solid with certain strength, easy hot melting, and thermoplastic property, which is different from conventional resol resin which can not be hot melted after solidification.
Coating the expansion flame-retardant inner layer coating on the aerogel heat-insulating felt layer, and curing to obtain an expansion flame-retardant inner layer composite aerogel heat-insulating felt layer; and (3) coating the intumescent flame-retardant outer coating on the intumescent flame-retardant inner layer, and curing to obtain the flame-retardant heat-insulating composite material.
The aerogel heat insulation felt layer has certain hydrophobicity and is easy to adhere to the expansion flame-retardant inner layer coating.
The viscosity, thixotropic property and fluidity of the intumescent flame retardant inner layer coating and the intumescent flame retardant outer layer coating are moderate, the intumescent flame retardant inner layer coating and the intumescent flame retardant outer layer coating can be constructed by spraying, roller coating, knife coating and the like, can be diluted by adding water, and the surface fixing time in an air environment with the temperature of 10-30 ℃ below 75% of relative humidity is lower than 10 hours. Under the condition of the thickness proportion, the expansion flame-retardant inner layer coating is easy to adhere and bond with the aerogel heat insulation felt layer, the expansion flame-retardant outer layer coating is easy to adhere and bond with the surface of the cured expansion flame-retardant inner layer, and the construction process is convenient and reliable; after coating, the inner layer coating and the outer layer coating are gradually volatilized along with the contained moisture, the surface layer is gradually solidified, and then the whole coating is gradually dehydrated and solidified.
Example 3
The flame-retardant and heat-insulating composite material comprises an aerogel heat-insulating felt layer, an intumescent flame-retardant inner layer and an intumescent flame-retardant outer layer, wherein the thickness ratio of the three layers is 5:3:3, the thickness is measured in mm, and the intumescent flame-retardant outer layer, the intumescent flame-retardant inner layer and the aerogel heat-insulating felt layer are sequentially connected from top to bottom; wherein, the aerogel heat insulation felt layer is attached to the back fire surface of the fireproof test piece.
Aerogel insulation blanket (commercially available) having a thermal conductivity of 0.016W/m·k; the preparation process of the aerogel heat insulation felt layer is that tetraethyl silicate is hydrolyzed in boiling water for 1h by a sol-gel method, firstly, 0.8wt.% silica sol is prepared, the silica sol is immersed in aluminum silicate fiber felt, and then, the aluminum silicate fiber felt is subjected to supercritical drying to obtain the aerogel heat insulation felt layer.
The expansion flame-retardant inner layer is formed by spraying, naturally drying and solidifying the expansion flame-retardant inner layer coating at room temperature (indoor air environment, relative humidity 70-75%, temperature 24-26 ℃, surface fixation time 8.5h, and integral solidification time 26 h); the ingredients of the intumescent flame retardant inner layer coating are 450g of ammonium polyphosphate, 100g of pentaerythritol, 250g of melamine, 1050g of modified resol glue solution and 1627mL of hollow glass beads with net volume; the preparation process of the intumescent flame retardant inner layer coating comprises the following steps: in a 5L stirring mixer with a 0.5kW ultrasonic disperser and a polytetrafluoroethylene plastic lining, adding ammonium polyphosphate, pentaerythritol and melamine into modified phenolic resin glue solution, uniformly mixing, ultrasonically dispersing for 25min, discharging to obtain a mixture (a polytetrafluoroethylene plastic lining which is not adhered) with a volume of 1505mL, adding hollow glass microsphere powder with a clean volume of 1627mL into the 5L stirring mixer with polytetrafluoroethylene plastic lining In a material machine, spraying and uniformly mixing 1505mL of the mixture into the hollow glass microsphere powder, wherein the spraying time is 24min, and continuously stirring for 15min until the mixture is uniform, so as to obtain the intumescent flame retardant inner coating which is not adhered to the polytetrafluoroethylene plastic lining; the hollow glass beads are made of soda lime borosilicate, and have a true density of 0.20g/cm 3 The water pressure resistance strength is 10MPa, the average particle diameter (outer diameter) is 64 mu m (the average wall thickness of the microbeads is estimated to be 4.2 mu m), the microbeads on the floating layer are firstly subjected to water pressure separation (water pressure time is 15 min) under 10MPa before use, the microbeads on the floating layer are filtered out, water is blown by compressed air, the microbeads are dried at 150 ℃, and the softening temperature is measured to be 760 ℃ or so and melted at 850 ℃; the ratio of the total volume of the mixture to the net volume of the hollow glass bead powder was 92.5:100.
The intumescent flame-retardant outer layer is formed by coating and curing an intumescent flame-retardant outer layer coating (the outer layer is coated after the inner layer is cured for 26 hours, the indoor air environment has the relative humidity of 70-75 percent, the temperature is 24-26 ℃, the surface curing time is 10 hours, and the integral curing time is 23 hours); the ingredients of the intumescent flame-retardant outer layer coating comprise 600g of ammonium polyphosphate, 100g of pentaerythritol, 250g of melamine, 1350g of modified resol glue solution and 600g of mullite whisker; the average diameter of the mullite whisker is 0.6 mu m, and the length-diameter ratio is 18; the preparation process of the intumescent flame-retardant outer layer coating comprises the following steps: adding modified resol type phenolic resin glue solution, adding mullite whisker, uniformly mixing, performing ultrasonic dispersion for 25min, adding ammonium polyphosphate, pentaerythritol and melamine, uniformly mixing, performing ultrasonic dispersion for 30min, and discharging (without adhering to a polytetrafluoroethylene plastic lining) to obtain the intumescent flame-retardant outer layer coating.
The modified resol glue solution is prepared by the following steps: adding 1.2kg of water, 0.3kg of 25wt.% ammonia water, 0.175kg of 4.5wt.% methyl silicic acid solution, 1.45kg of 34wt.% formaldehyde water solution and 1.0kg of phenol into a 5L stirring reactor, starting condensation reflux, stirring at 75 ℃ for reaction for 5 hours, then distilling under reduced pressure for 1.5 hours until the solid concentration of the feed liquid is 31.7wt.%, cooling to room temperature, adding 0.175kg of triglycidyl isocyanurate, and continuing stirring for 12.5 hours to obtain modified resol glue; the condensing temperature is controlled to be 15 ℃ during condensing reflux, the feed liquid temperature is controlled to be 73 ℃ during reduced pressure distillation, and the air suction vacuum degree (absolute pressure) is 30kPa; the added methyl silicic acid solution is prepared by removing sodium ions from 5.7wt.% methyl sodium silicate aqueous solution through hydrogen type macroporous strong acid cation exchange resin exchange, and is used for feeding modified resol glue solution 2h after preparation.
The average particle diameters (outer diameters) of the ammonium polyphosphate, pentaerythritol and melamine powders were 5 μm, 11 μm and 20 μm, respectively, the average particle diameter (outer diameter) of the triglycidyl isocyanurate powder was 10 μm, and the polymerization degree of the ammonium polyphosphate was 500; in pentaerythritol, the content of monopentaerythritol was 85wt.%, and the content of dipentaerythritol was 8wt.%.
The prepared modified resol glue solution is reddish brown semitransparent, can transmit blue laser beams, has clear light path, has the viscosity of 640 mPa.s, is a colloid, has the quality of more than 3 months in a stable period (the light transmittance and the viscosity basically do not change after being stored for 3 months in a sealed shading way), has light smell, has the formaldehyde and phenol contents of lower than 0.1w.t percent, and basically does not contain ammonia; the solid formed by directly heating to 180 ℃ and preserving heat for 0.6h is strong, is easy to melt and thermoplastic, and is different from the conventional resol type phenolic resin which cannot be melt after being cured.
Coating the expansion flame-retardant inner layer coating on the aerogel heat-insulating felt layer, and curing to obtain an expansion flame-retardant inner layer composite aerogel heat-insulating felt layer; and (3) coating the intumescent flame-retardant outer coating on the intumescent flame-retardant inner layer, and curing to obtain the flame-retardant heat-insulating composite material.
The aerogel heat insulation felt layer has certain hydrophobicity and is easy to adhere to the expansion flame-retardant inner layer coating.
The viscosity, thixotropic property and fluidity of the intumescent flame retardant inner layer coating and the intumescent flame retardant outer layer coating are moderate, the intumescent flame retardant inner layer coating and the intumescent flame retardant outer layer coating can be constructed by spraying, roller coating, knife coating and the like, can be diluted by adding water, and the surface fixing time in an air environment with the temperature of 10-30 ℃ below 75% of relative humidity is lower than 10 hours. Under the condition of the thickness proportion, the expansion flame-retardant inner layer coating is easy to adhere and bond with the aerogel heat insulation felt layer, the expansion flame-retardant outer layer coating is easy to adhere and bond with the surface of the cured expansion flame-retardant inner layer, and the construction process is convenient and reliable; after coating, the inner layer coating and the outer layer coating are gradually volatilized along with the contained moisture, the surface layer is gradually solidified, and then the whole coating is gradually dehydrated and solidified.
Comparative example 1
The modified resol gum of this comparative example was prepared as in example 1 except that triglycidyl isocyanurate was not added.
The modified resol glue prepared in this comparative example was not curable when the temperature was raised to 240 c, and 1wt.% of the quaternary ammonium hydroxide was added at normal temperature and stirred and left to stand for 1.2 hours for curing but the cured product was not hot-melt.
Comparative example 2
The modified resol gum of this comparative example was prepared as in example 1 except that no methyl silicic acid solution was added.
The modified resol glue solution prepared in the comparative example has obviously reduced light transmittance and increased viscosity by more than one time after being stored for 1 month in a closed shading way; and adding a silane coupling agent kh550 with a corresponding molar ratio into the glue solution, so that the light transmittance of the glue solution after uniform mixing is obviously reduced and the viscosity is improved by more than two times after the glue solution is stored for 1 month in a sealed shading way.
Comparative example 3
The modified resol gum of this comparative example was prepared as in the preparation of the modified resol gum of example 1, except that the added methyl silicic acid solution was stored for 10 hours after the ion exchange preparation and was then used for the dosing of the modified resol gum.
The modified resol glue solution prepared in the comparative example has obviously reduced light transmittance and improved viscosity by more than two times after being stored for 2 months in a closed shading way. This demonstrates that dimerization and multimerization of methyl silicic acid have a greater impact on the properties of the modified resol gum.
Comparative example 4
The fire retardant coating of this comparative example was prepared as a control for the intumescent flame retardant inner coating of example 1 according to the formulation and method of example 2 of CN111592813 a. The hollow glass beads, ammonium polyphosphate, pentaerythritol and melamine used in the example 1 are adopted in the preparation, and other ingredients adopt raw materials which can be purchased and have better performance.
The fireproof paint prepared in the comparative example has obvious segregation problem of hollow glass beads in the storage process and the solidification process after dilution and coating; the paint has higher viscosity, general fluidity and thixotropy, needs dilution when being constructed in modes of spraying, roller coating and the like, and has lower hollow glass microsphere content.
Comparative example 5
The fire retardant coating of this comparative example was prepared as a control for the intumescent flame retardant outer coating of example 1 according to the formulation and method of example 3 of CN112708316 a. The preparation adopts ammonium polyphosphate, pentaerythritol and melamine used in the example 1, the ceramic fiber is replaced by equal parts of silicon carbide whisker (silicon carbide whisker used in the example 1), and other ingredients adopt raw materials which can be purchased and have better performance.
Comparative example 6
500g of each of the intumescent flame retardant inner layer coating and the intumescent flame retardant outer layer coating prepared in example 1 was uniformly mixed in a 5L stirring mixer of polytetrafluoroethylene plastic lined with a 0.5kW ultrasonic disperser, and discharged to obtain the fireproof coating of the comparative example.
Comparative example 7
The intumescent flame retardant outer coating prepared in example 1 was used as a flame retardant coating for this comparative example.
Product performance test:
the determination of the fire resistance limit adopts GB 14007-2018; the temperature conditions were according to the HC temperature rise curve of the GA/T714-2007 tunnel fire test, i.e. the temperature was raised to 1100℃at 30min and maintained thereafter until the temperature of the backfire surface of the test piece reached 500 ℃.
According to the method of GB 14907-2018.5.2.1 indoor steel structure fireproof paint, the indexes such as drying time, initial drying crack resistance, bonding strength, heat insulation efficiency deviation, pH value, water resistance, cold and heat cycle resistance and the like of the intumescent flame retardant inner layer paint and the intumescent flame retardant outer layer paint prepared in examples 1-3 are measured, and the results show that the indexes all meet the requirements of GB 14007-2018.
According to the method of GB 14907-2018.5 special steel structure fireproof paint, the flame-retardant and heat-insulating composite material of the example 1 and the fireproof paint of the comparative examples 4-7 are respectively manufactured into test pieces (Q235 steel plates with the size of 500x500x6mm, the thickness of a composite material layer or a coating layer is 8mm, wherein the thickness ratio of an aerogel heat-insulating felt layer, an intumescent flame-retardant inner layer and an intumescent flame-retardant outer layer of the flame-retardant and heat-insulating composite material of the example 1 is 4:2:2, the thickness is measured in mm), the fireproof limit is measured, and the temperature condition is according to the HC heating curve of a GA/T714-2007 tunnel fireproof test, namely, the temperature is heated to 1100 ℃ at 30min and is maintained until the backfire surface temperature of the test pieces reaches 500 ℃. The results show that the fire resistance limit of the flame-retardant and heat-insulating composite material of the example 1 is 5.2 hours (the time for the temperature of the back fire surface of the test piece to reach 80 ℃ is 1.1 hour), and the fire resistance limit of the fire-retardant coating of the comparative examples 4-7 is lower than 3 hours (the time for the temperature of the back fire surface of the test piece to reach 80 ℃ is lower than 25 minutes).
According to the method of GB 14907-2018.5 special steel structure fireproof paint, the flame-retardant and heat-insulating composite material of the example 2 is manufactured into a test piece (Q235 steel plate with the size of 500x500x6mm, wherein the thickness ratio of an aerogel heat-insulating felt layer to an intumescent flame-retardant inner layer to an intumescent flame-retardant outer layer is 3:3:2, the thickness is measured in mm), the fire resistance limit is measured, the temperature condition is according to a HC heating curve of a GA/T714-2007 tunnel fire resistance test, namely, the temperature is heated to 1100 ℃ at 30min and maintained later until the temperature of the backfire surface of the test piece reaches 500 ℃. The results show that the fire resistance limit of the flame-retardant and heat-insulating composite material of the example 2 is 6.6 hours, and the time for the temperature of the back surface of the test piece to reach 80 ℃ is 1.3 hours.
According to the method of GB 14907-2018.5 special steel structure fireproof paint, the flame-retardant and heat-insulating composite material of the embodiment 3 is manufactured into a test piece (a Q235 steel plate with the size of 500x500x6mm, wherein the thickness ratio of an aerogel heat-insulating felt layer to an intumescent flame-retardant inner layer to an intumescent flame-retardant outer layer is 3:2:3, the thickness is measured in mm), the fire resistance limit is measured, the temperature condition is according to a HC heating curve of a GA/T714-2007 tunnel fire resistance test, namely, the temperature is heated to 1100 ℃ in 30min and is maintained later until the temperature of the backfire surface of the test piece reaches 500 ℃. The results show that the fire resistance limit of the flame-retardant and heat-insulating composite material of the example 2 is 7.1 hours, and the time for the temperature of the back surface of the test piece to reach 80 ℃ is 1.6 hours.
In the fire-proof limit test process, the expansion and ablation conditions of the flame-retardant heat-insulating composite materials in the embodiments 1-3 are uniform, the problems of burning or dripping do not occur, the smoke generation is less and slower, and the dense smoke is not intensively released; the flame retardant and heat insulating composite materials of examples 1-3 have better overall effect.
As shown by the product performance test results, the composite material has longer fire resistance limit and good flame-retardant and heat-insulating performance, and the three-layer progressive flame-retardant and heat-insulating structure of the aerogel heat-insulating felt layer, the expansion flame-retardant inner layer and the expansion flame-retardant outer layer ensures excellent flame-retardant and heat-insulating effects; the performance of the inner coating and the outer coating meets the requirements of the indoor special steel structure expansion type fireproof coating, wherein the hollow glass microspheres, the whiskers and the ammonium polyphosphate-pentaerythritol-melamine-modified resol glue solution mixture show remarkable synergistic effect on realizing the technical effects.
Claims (8)
1. The flame-retardant heat-insulating composite material is characterized by comprising an aerogel heat-insulating felt layer, an intumescent flame-retardant inner layer and an intumescent flame-retardant outer layer, wherein the intumescent flame-retardant outer layer, the intumescent flame-retardant inner layer and the aerogel heat-insulating felt layer are sequentially connected from top to bottom;
the aerogel heat insulation felt layer is prepared by compositing silicon dioxide in a fiber felt in an aerogel form;
The expansion flame-retardant inner layer is prepared by coating and curing expansion flame-retardant inner layer paint; the raw materials of the intumescent flame retardant inner layer coating comprise ammonium polyphosphate, pentaerythritol, melamine, modified resol glue solution and hollow glass beads;
the intumescent flame retardant outer layer is prepared by coating and curing an intumescent flame retardant outer layer coating; the raw materials of the intumescent flame-retardant outer coating comprise ammonium polyphosphate, pentaerythritol, melamine, modified resol glue solution and whiskers;
the preparation method of the modified resol glue solution comprises the steps of stirring water, ammonia water, methyl silicic acid solution, formaldehyde water solution and phenol for reaction, distilling under reduced pressure, cooling to room temperature, adding triglycidyl isocyanurate, and continuing stirring to obtain the modified resol glue solution;
the concentration of the ammonia water is 20-25 wt%, the concentration of the methyl silicic acid solution is 3-6 wt%, the concentration of the formaldehyde water solution is 33-35 wt%, the reaction temperature is 75-90 ℃, the reaction time is 3.5-5h, the reduced pressure distillation time is 1-2h, and the continuous stirring time is 10-15h; the weight ratio of water, ammonia water, methyl silicic acid solution, formaldehyde water solution, phenol and triglycidyl isocyanurate is (1.1-1.3) (0.2-0.4) (0.15-0.2) (1.3-1.6) (1) (0.15-0.2); triglycidyl isocyanurate is a powder having a mean particle size of 5-10. Mu.m.
2. The flame retardant and heat insulating composite material of claim 1, wherein the aerogel heat insulating felt layer, the intumescent flame retardant inner layer and the intumescent flame retardant outer layer have a thickness ratio of (3-5): 2-3, the thickness being in mm.
3. The flame retardant and heat insulating composite material according to claim 1, wherein the heat conductivity coefficient of the aerogel heat insulating felt layer is 0.012-0.019W/m-k, and the fiber felt is an aluminum silicate fiber felt or an aluminum oxide fiber felt.
4. The flame-retardant and heat-insulating composite material according to claim 1, wherein the weight ratio of ammonium polyphosphate, pentaerythritol, melamine and modified resol glue solution in the raw materials of the intumescent flame-retardant inner layer coating is (4-5) 1 (2-3) 9-12, and the ratio of the total volume of the mixture of the ammonium polyphosphate, pentaerythritol, melamine and modified resol glue solution to the net volume of the hollow glass beads is (90-95) 100; the hollow glass beads are made of soda lime borosilicate, and have a true density of 0.15-0.25g/cm 3 The water pressure resistance strength is 8-10MPa, and the average grain diameter is 50-80 μm.
5. The flame-retardant and heat-insulating composite material according to claim 1, wherein the weight ratio of ammonium polyphosphate, pentaerythritol, melamine, modified resol glue solution and whisker in the raw materials of the intumescent flame-retardant outer coating is (5-7) 1 (2-3) 12-15) 5-7; the whisker is silicon carbide whisker or mullite whisker, the average diameter of the whisker is 0.4-0.6 mu m, and the length-diameter ratio is 18-25.
6. The flame-retardant and heat-insulating composite material according to claim 1, wherein the methyl silicic acid solution is prepared by removing sodium ions from a methyl sodium silicate aqueous solution with a concentration of 3.8-7.6wt.% through the exchange of a hydrogen type macroporous strong acid cation exchange resin.
7. The flame-retardant and heat-insulating composite material according to claim 1, wherein the polymerization degree of the ammonium polyphosphate is 500-650; in pentaerythritol, the content of monopentaerythritol is more than or equal to 80wt.%, and the content of dipentaerythritol is more than or equal to 8wt.%.
8. A method for preparing the flame retardant and heat insulating composite material according to any one of claims 1 to 7, comprising the steps of:
(1) Adding tetraethyl silicate into boiling water for hydrolysis to obtain silica sol; soaking silica sol in a fiber felt, and performing supercritical drying to obtain an aerogel heat insulation felt layer;
(2) Firstly adding ammonium polyphosphate, pentaerythritol and melamine into modified resol glue solution, uniformly mixing, performing ultrasonic dispersion, spraying into hollow glass beads, and uniformly mixing to obtain an intumescent flame retardant inner layer coating;
(3) Adding the whisker into the modified resol glue solution, uniformly mixing, performing ultrasonic dispersion, adding ammonium polyphosphate, pentaerythritol and melamine, uniformly mixing, and performing ultrasonic dispersion to obtain the intumescent flame-retardant outer layer coating;
(4) Coating the expansion flame-retardant inner layer coating on the aerogel heat-insulating felt layer, and curing to obtain an expansion flame-retardant inner layer composite aerogel heat-insulating felt layer;
(5) And (3) coating the intumescent flame-retardant outer coating on the intumescent flame-retardant inner layer, and curing to obtain the flame-retardant heat-insulating composite material.
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Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US20070219299A1 (en) * | 2004-05-07 | 2007-09-20 | Kaneka Corporation | Curable Composition |
| CN111592813A (en) * | 2020-06-22 | 2020-08-28 | 河南宣和钧釉环保材料有限公司 | Intumescent fire-retardant coating and preparation method thereof |
| CN114752272A (en) * | 2022-05-25 | 2022-07-15 | 潍坊工程职业学院 | External waterproof and antirust coating composition for automobile exhaust system and application method thereof |
| CN115506238A (en) * | 2022-09-28 | 2022-12-23 | 江苏卓奇新材料科技有限公司 | Expansion type bridge cable with sealing fireproof composite structure |
-
2023
- 2023-08-23 CN CN202311062192.4A patent/CN116786389B/en active Active
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US20070219299A1 (en) * | 2004-05-07 | 2007-09-20 | Kaneka Corporation | Curable Composition |
| CN111592813A (en) * | 2020-06-22 | 2020-08-28 | 河南宣和钧釉环保材料有限公司 | Intumescent fire-retardant coating and preparation method thereof |
| CN114752272A (en) * | 2022-05-25 | 2022-07-15 | 潍坊工程职业学院 | External waterproof and antirust coating composition for automobile exhaust system and application method thereof |
| CN115506238A (en) * | 2022-09-28 | 2022-12-23 | 江苏卓奇新材料科技有限公司 | Expansion type bridge cable with sealing fireproof composite structure |
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| CN116786389A (en) | 2023-09-22 |
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