CN115850799A - Tubular kaolin modified ammonium polyphosphate functional monomer and preparation method thereof - Google Patents
Tubular kaolin modified ammonium polyphosphate functional monomer and preparation method thereof Download PDFInfo
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- 229920001276 ammonium polyphosphate Polymers 0.000 title claims abstract description 84
- 239000005995 Aluminium silicate Substances 0.000 title claims abstract description 74
- 235000012211 aluminium silicate Nutrition 0.000 title claims abstract description 74
- 239000004114 Ammonium polyphosphate Substances 0.000 title claims abstract description 66
- 235000019826 ammonium polyphosphate Nutrition 0.000 title claims abstract description 66
- 239000000178 monomer Substances 0.000 title claims abstract description 29
- -1 kaolin modified ammonium Chemical class 0.000 title claims abstract description 28
- 238000002360 preparation method Methods 0.000 title description 3
- NLYAJNPCOHFWQQ-UHFFFAOYSA-N kaolin Chemical compound O.O.O=[Al]O[Si](=O)O[Si](=O)O[Al]=O NLYAJNPCOHFWQQ-UHFFFAOYSA-N 0.000 claims abstract description 46
- 238000006243 chemical reaction Methods 0.000 claims abstract description 37
- 229920000877 Melamine resin Polymers 0.000 claims abstract description 16
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- 230000000694 effects Effects 0.000 claims abstract description 6
- 229910004298 SiO 2 Inorganic materials 0.000 claims abstract description 3
- 229920006334 epoxy coating Polymers 0.000 claims abstract description 3
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 41
- 238000004321 preservation Methods 0.000 claims description 26
- WSFSSNUMVMOOMR-UHFFFAOYSA-N Formaldehyde Chemical compound O=C WSFSSNUMVMOOMR-UHFFFAOYSA-N 0.000 claims description 21
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 16
- 239000007787 solid Substances 0.000 claims description 14
- 239000007864 aqueous solution Substances 0.000 claims description 12
- 239000007788 liquid Substances 0.000 claims description 12
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- 238000001035 drying Methods 0.000 claims description 9
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- 238000000926 separation method Methods 0.000 claims description 9
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- 238000005406 washing Methods 0.000 claims description 9
- IVJISJACKSSFGE-UHFFFAOYSA-N formaldehyde;1,3,5-triazine-2,4,6-triamine Chemical compound O=C.NC1=NC(N)=NC(N)=N1 IVJISJACKSSFGE-UHFFFAOYSA-N 0.000 claims description 8
- 239000002245 particle Substances 0.000 claims description 8
- 239000003822 epoxy resin Substances 0.000 claims description 7
- 229920000647 polyepoxide Polymers 0.000 claims description 7
- RMAQACBXLXPBSY-UHFFFAOYSA-N silicic acid Chemical compound O[Si](O)(O)O RMAQACBXLXPBSY-UHFFFAOYSA-N 0.000 claims description 7
- GSEJCLTVZPLZKY-UHFFFAOYSA-N Triethanolamine Chemical compound OCCN(CCO)CCO GSEJCLTVZPLZKY-UHFFFAOYSA-N 0.000 claims description 5
- 150000001450 anions Chemical class 0.000 claims description 3
- 150000001768 cations Chemical group 0.000 claims description 3
- 230000001105 regulatory effect Effects 0.000 claims description 2
- 239000003063 flame retardant Substances 0.000 abstract description 39
- RNFJDJUURJAICM-UHFFFAOYSA-N 2,2,4,4,6,6-hexaphenoxy-1,3,5-triaza-2$l^{5},4$l^{5},6$l^{5}-triphosphacyclohexa-1,3,5-triene Chemical 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 abstract description 34
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 abstract description 22
- 239000000463 material Substances 0.000 abstract description 5
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 abstract description 4
- 229910052799 carbon Inorganic materials 0.000 abstract description 4
- 238000000034 method Methods 0.000 abstract description 3
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- 239000002689 soil Substances 0.000 abstract 1
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- 239000000853 adhesive Substances 0.000 description 6
- 230000001070 adhesive effect Effects 0.000 description 6
- 239000000839 emulsion Substances 0.000 description 5
- 101000609219 Homo sapiens Polyadenylate-binding protein 4 Proteins 0.000 description 4
- 102100039424 Polyadenylate-binding protein 4 Human genes 0.000 description 4
- HOHPOKYCMNKQJS-UHFFFAOYSA-N [P].[Br] Chemical compound [P].[Br] HOHPOKYCMNKQJS-UHFFFAOYSA-N 0.000 description 4
- 239000000203 mixture Substances 0.000 description 4
- DXZMANYCMVCPIM-UHFFFAOYSA-L zinc;diethylphosphinate Chemical compound [Zn+2].CCP([O-])(=O)CC.CCP([O-])(=O)CC DXZMANYCMVCPIM-UHFFFAOYSA-L 0.000 description 4
- NIXOWILDQLNWCW-UHFFFAOYSA-M Acrylate Chemical compound [O-]C(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-M 0.000 description 3
- 230000009970 fire resistant effect Effects 0.000 description 3
- 239000002861 polymer material Substances 0.000 description 3
- 239000000779 smoke Substances 0.000 description 3
- 230000002195 synergetic effect Effects 0.000 description 3
- JYEUMXHLPRZUAT-UHFFFAOYSA-N 1,2,3-triazine Chemical compound C1=CN=NN=C1 JYEUMXHLPRZUAT-UHFFFAOYSA-N 0.000 description 2
- WKBOTKDWSSQWDR-UHFFFAOYSA-N Bromine atom Chemical compound [Br] WKBOTKDWSSQWDR-UHFFFAOYSA-N 0.000 description 2
- 229920004933 Terylene® Polymers 0.000 description 2
- BQPNUOYXSVUVMY-UHFFFAOYSA-N [4-[2-(4-diphenoxyphosphoryloxyphenyl)propan-2-yl]phenyl] diphenyl phosphate Chemical compound C=1C=C(OP(=O)(OC=2C=CC=CC=2)OC=2C=CC=CC=2)C=CC=1C(C)(C)C(C=C1)=CC=C1OP(=O)(OC=1C=CC=CC=1)OC1=CC=CC=C1 BQPNUOYXSVUVMY-UHFFFAOYSA-N 0.000 description 2
- 239000002253 acid Substances 0.000 description 2
- GDTBXPJZTBHREO-UHFFFAOYSA-N bromine Substances BrBr GDTBXPJZTBHREO-UHFFFAOYSA-N 0.000 description 2
- 229910052794 bromium Inorganic materials 0.000 description 2
- 239000003795 chemical substances by application Substances 0.000 description 2
- 239000008199 coating composition Substances 0.000 description 2
- 239000013530 defoamer Substances 0.000 description 2
- 239000006185 dispersion Substances 0.000 description 2
- 239000003995 emulsifying agent Substances 0.000 description 2
- 239000004033 plastic Substances 0.000 description 2
- 229920003023 plastic Polymers 0.000 description 2
- 239000005020 polyethylene terephthalate Substances 0.000 description 2
- 239000000047 product Substances 0.000 description 2
- 239000004753 textile Substances 0.000 description 2
- 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 2
- BZQKBFHEWDPQHD-UHFFFAOYSA-N 1,2,3,4,5-pentabromo-6-[2-(2,3,4,5,6-pentabromophenyl)ethyl]benzene Chemical compound BrC1=C(Br)C(Br)=C(Br)C(Br)=C1CCC1=C(Br)C(Br)=C(Br)C(Br)=C1Br BZQKBFHEWDPQHD-UHFFFAOYSA-N 0.000 description 1
- 239000004254 Ammonium phosphate Substances 0.000 description 1
- 239000004793 Polystyrene Substances 0.000 description 1
- 101710140186 Xaa-Pro aminopeptidase Proteins 0.000 description 1
- 229910000148 ammonium phosphate Inorganic materials 0.000 description 1
- 235000019289 ammonium phosphates Nutrition 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 239000001273 butane Substances 0.000 description 1
- 238000013329 compounding Methods 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- MNNHAPBLZZVQHP-UHFFFAOYSA-N diammonium hydrogen phosphate Chemical compound [NH4+].[NH4+].OP([O-])([O-])=O MNNHAPBLZZVQHP-UHFFFAOYSA-N 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 230000002349 favourable effect Effects 0.000 description 1
- 239000006260 foam Substances 0.000 description 1
- 229910052736 halogen Inorganic materials 0.000 description 1
- 150000002367 halogens Chemical class 0.000 description 1
- 238000003837 high-temperature calcination Methods 0.000 description 1
- 231100000053 low toxicity Toxicity 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- ZQKXQUJXLSSJCH-UHFFFAOYSA-N melamine cyanurate Chemical compound NC1=NC(N)=NC(N)=N1.O=C1NC(=O)NC(=O)N1 ZQKXQUJXLSSJCH-UHFFFAOYSA-N 0.000 description 1
- IJDNQMDRQITEOD-UHFFFAOYSA-N n-butane Chemical compound CCCC IJDNQMDRQITEOD-UHFFFAOYSA-N 0.000 description 1
- OFBQJSOFQDEBGM-UHFFFAOYSA-N n-pentane Natural products CCCCC OFBQJSOFQDEBGM-UHFFFAOYSA-N 0.000 description 1
- 231100000956 nontoxicity Toxicity 0.000 description 1
- 230000000704 physical effect Effects 0.000 description 1
- 229920000728 polyester Polymers 0.000 description 1
- 229920002223 polystyrene Polymers 0.000 description 1
- 229920002635 polyurethane Polymers 0.000 description 1
- 239000004814 polyurethane Substances 0.000 description 1
- 239000002244 precipitate Substances 0.000 description 1
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- 230000000087 stabilizing effect Effects 0.000 description 1
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Images
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- Compositions Of Macromolecular Compounds (AREA)
Abstract
The invention discloses a tubular kaolin modified ammonium polyphosphate functional monomer, which is prepared by mixing nano SiO 2 Ammonium polyphosphate embedded tubular high through grafting modification treatment, epoxy coating modification treatment or melamine coating modification treatmentPrepared from the interior of Ling soil. The functional monomer of ammonium polyphosphate and tubular kaolin formed by organic-inorganic hybridization reaction enables the advantages of ammonium polyphosphate and tubular kaolin to be cooperated to the greatest extent, obviously improves the water resistance of the ammonium polyphosphate and tubular kaolin, greatly improves the carbon forming effect and the flame retardant efficiency of the ammonium polyphosphate and tubular kaolin, and can be directly applied to flame retardant of related materials. The method has the advantages of simple reaction process, easily obtained raw materials, convenient and safe operation, convenient popularization and application, and better industrial popularization and application values.
Description
Technical Field
The invention relates to a tubular kaolin modified ammonium polyphosphate functional monomer and a preparation method thereof.
Background
With the increasing development of society, high molecular materials have been widely applied to various fields of production and life. Meanwhile, most high polymer materials are combustible or inflammable, which brings potential fire hazard. Flame retardancy of polymer materials is also an important aspect of material modification.
At present, most commonly and most effective bromine flame retardant systems and P/N halogen-free flame retardant systems are taken as main systems in the aspects of fabric and plastic flame retardance, the flame retardant mechanism of the bromine flame retardant is mainly gas-phase flame retardant, the P/N flame retardant system plays a role through flame retardant char formation, and no matter which system has a larger probability of generating a synergistic effect with ammonium polyphosphate. The ammonium polyphosphate is also called ammonium polyphosphate or condensed ammonium phosphate (APP for short), has the characteristics of excellent performance, no toxicity, no odor, no generation of corrosive gas, small hygroscopicity and high thermal stability, and can be widely used in the fields related to flame retardance of plastics and coatings. The ammonium polyphosphate, the decabromodiphenylethane and other brominated flame retardants can perform phosphorus-bromine synergy, so that the flame retardant efficiency is effectively improved, and the cost is reduced; the halogen-free flame retardant synergistic agent can form a classical intumescent flame retardant system together with relevant halogen-free flame retardants such as appropriate carbon sources and gas sources.
However, APP has the corresponding disadvantages that the APP is used as the main acid source of the intumescent flame retardant, but the application and development of the APP are limited due to the defects of poor water resistance, poor compatibility with a substrate and the like, and after the APP is placed for a long time, the flame retardant can migrate, precipitate or seep out from a polymer system to the surface of a polymer, so that a 'white frost' phenomenon occurs, and the physical properties of a flame-retarded material are influenced. Therefore, the method effectively modifies APP and has important significance for the use and development of intumescent flame retardants.
Disclosure of Invention
The invention aims to provide a novel modified water-resistant ammonium polyphosphate with a tubular structure, which not only has greatly improved water resistance, but also has the advantages of strong thermal stability, no halogen, environmental protection, flame retardance, high efficiency, low toxicity, low smoke and the like, and in addition, has good compatibility with high polymer materials. The modified APP can form phosphorus-bromine synergy with a brominated flame retardant, and can also be used in a classical intumescent flame retardant system as an acid source and a carbon source.
In order to achieve the aim, the invention provides a tubular kaolin modified ammonium polyphosphate functional monomer prepared by mixing nano SiO 2 Graft modification treatment the ammonium polyphosphate which is subjected to epoxy coating modification treatment or melamine coating modification treatment is embedded into the tubular kaolin to obtain the modified tubular kaolin.
The tubular kaolin modified ammonium polyphosphate functional monomer is prepared by the following steps (1), (2) or (3):
(1) Uniformly mixing ammonium polyphosphate and ethanol, then dropwise adding silica sol at 40-70 ℃ under the stirring condition, continuing to perform heat preservation reaction for 2-5h after dropwise adding is finished, adding tubular kaolin after the heat preservation reaction is finished, continuing to perform heat preservation reaction for 3-5h, performing solid-liquid separation after the heat preservation reaction is finished, and washing and drying the separated solid to obtain a tubular kaolin modified ammonium polyphosphate functional monomer;
(2) Mixing melamine and formaldehyde aqueous solution, adjusting the pH value to 7-9 by triethanolamine aqueous solution, heating to 60-85 ℃, reacting for 20-60min, and performing solid-liquid separation after the reaction to obtain melamine-formaldehyde polymer; uniformly mixing ammonium polyphosphate and ethanol, regulating the pH value to 4-6 by using hydrochloric acid, heating to 70-80 ℃, adding a melamine-formaldehyde polymer, performing heat preservation reaction for 1.5-3h, then adding tubular kaolin, continuing the heat preservation reaction for 3-5h, performing solid-liquid separation after the heat preservation reaction is continued, and washing and drying the separated solid to obtain a tubular kaolin modified ammonium polyphosphate functional monomer;
(3) Uniformly mixing ammonium polyphosphate and ethanol, adjusting the pH value to 4-6 by using hydrochloric acid, heating to 70-80 ℃, adding epoxy resin, and reacting for 1.5-3 hours in a heat preservation manner; and adding tubular kaolin after the heat preservation reaction is finished, continuing to perform the heat preservation reaction for 3-5 hours, performing solid-liquid separation after the heat preservation reaction is finished, and washing and drying the separated solid to obtain the tubular kaolin modified ammonium polyphosphate functional monomer.
In the step (1), the mass ratio of the silica sol to the ammonium polyphosphate is 1:3-2:3, the mass ratio of the tubular kaolin to the ammonium polyphosphate is 1:3-2:3, and the dosage of the ethanol is 4-12 times of the mass of the ammonium polyphosphate.
In the step (2), the mass ratio of the melamine to the formaldehyde aqueous solution is 1:3-2:1, the mass ratio of the ammonium polyphosphate to the melamine-formaldehyde polymer is 3:1-3:2, the mass ratio of the tubular kaolin to the ammonium polyphosphate is 1:3-2:3, and the dosage of the ethanol is 4-12 times of the mass of the ammonium polyphosphate.
In the step (3), the mass ratio of the epoxy resin to the ammonium polyphosphate is 1:5-1:2, the mass ratio of the tubular kaolin to the ammonium polyphosphate is 1:3-2:3, and the dosage of the ethanol is 4-12 times of the mass of the ammonium polyphosphate.
In the step (3), the concentration of the formaldehyde aqueous solution is 20-40%, and the concentration of the triethanolamine aqueous solution is 5-20%; in the step (2) and the step (3), the concentration of the hydrochloric acid is 5-20%.
In the step (1), the dropping speed of the silica sol is 1-2 drops per second.
The tubular kaolin is tubular refractory kaolin, the average particle diameter of the tubular refractory kaolin particles is 0.2-2.0 mu m, the inner diameter of the tubular refractory kaolin particles is 15-30nm, and the inner surface of the tubular refractory kaolin is rich in anion and cation groups and has high-activity reactive sites.
The tubular fire-resistant kaolin is produced by FMT corporation of Japan and has the product name DRAGONITE, the internal structure of the tubular fire-resistant kaolin contains abundant active anion and cation groups, and the tubular fire-resistant kaolin has dense high-activity reaction points and is beneficial to subsequent coating reaction. The tubular refractory kaolin has small particles, the average particle diameter of the tubular refractory kaolin is 0.2-2.0 mu m, and the inner diameter of the tubular refractory kaolin is 15-30nm, so that the tubular refractory kaolin is favorable for dispersion. In addition, the self-charring and auxiliary charring performances are good during high-temperature calcination.
The tubular kaolin modified ammonium polyphosphate functional monomer provided by the invention is prepared by carrying out organic-inorganic hybridization reaction on ammonium polyphosphate and tubular refractory kaolin, so that the advantages of the ammonium polyphosphate and the tubular refractory kaolin are cooperated to the greatest extent, the water resistance of the tubular refractory kaolin is obviously improved, the carbon forming effect and the flame retardant efficiency of the tubular refractory kaolin are greatly improved, and the tubular kaolin modified ammonium polyphosphate functional monomer can be directly applied to flame retardant of related materials. The method has the advantages of simple reaction process, easily obtained raw materials, convenient and safe operation, convenient popularization and application, and better industrial popularization and application values.
Drawings
FIG. 1 is a schematic structural diagram of a tubular kaolin modified ammonium polyphosphate functional monomer.
Detailed Description
Example 1
Adding 50g of APP and 300ml of ethanol into a 500ml three-neck flask, mixing the APP and the 300ml of ethanol uniformly, dripping 25g of silica sol into the three-neck flask at the temperature of 50 ℃ under the stirring condition, wherein the dripping speed is 1-2 drops per second, continuing to perform heat preservation reaction for 2 hours after the dripping is finished, adding 30g of tubular kaolin into the three-neck flask after the heat preservation reaction is finished, continuing to perform the heat preservation reaction for 3-5 hours, after the reaction is finished, performing centrifugal treatment to separate solid and liquid, washing the obtained solid twice with absolute ethyl alcohol, and drying at the temperature of 60 ℃ to obtain a tubular kaolin modified ammonium polyphosphate functional monomer, which is recorded as APP-1.
Example 2
Mixing 20g of melamine with a formaldehyde aqueous solution with the concentration of 37% of 40 ml, adjusting the pH to 7.5 by using a triethanolamine aqueous solution with the concentration of 10%, slowly heating to 70 ℃, then carrying out heat preservation reaction for 30min, and carrying out solid-liquid separation after the reaction is finished to obtain a melamine-formaldehyde polymer; adding 40g of APP into 200ml absolute ethyl alcohol for uniform dispersion, adjusting the pH to be about =5 by using hydrochloric acid with the concentration of 10%, slowly heating to 78 ℃, adding 20g of melamine-formaldehyde polymer, keeping the temperature at 78 ℃, continuously stirring for reaction for 2 hours, then adding 20g of tubular kaolin, continuously reacting for 4 hours at 78 ℃ under the stirring condition, after the reaction is finished, performing centrifugal treatment to separate solid and liquid, washing the obtained solid twice by using the absolute ethyl alcohol, and then drying at the temperature of 60 ℃ to obtain a tubular kaolin modified ammonium polyphosphate functional monomer, which is marked as APP-2.
Example 3
Adding 40g of APP into 200ml of absolute ethyl alcohol, uniformly dispersing, adjusting the pH to be about =5 by using hydrochloric acid with the concentration of 10%, slowly heating to 78 ℃, adding 10g of epoxy resin, keeping the temperature at 78 ℃, continuously stirring for 2 hours, then adding 20g of tubular kaolin, continuously stirring, keeping the temperature and reacting for 4 hours, after the reaction is finished, performing centrifugal treatment to separate solid from liquid, washing the obtained solid with absolute ethyl alcohol twice, and then drying at the temperature of 60 ℃ to obtain a tubular kaolin modified ammonium polyphosphate functional monomer, which is recorded as APP-3.
In another aspect of the invention, an environment-friendly halogen-free fabric flame-retardant coating adhesive is provided, which comprises the tubular kaolin modified ammonium polyphosphate, and is prepared by compounding the tubular kaolin modified ammonium polyphosphate with other brominated or halogen-free flame retardants and acrylate emulsion.
Example 4
Bisphenol A bis (diphenyl phosphate) (BDP for short), APP-1, brominated polystyrene, zinc borate, triazine charring agent (CFA) and epoxy resin are mixed according to the proportion of 1.5:5.0:2.0:2.0:2.5:2.0, preparing the material mixture with the total mass of 15.0g, adding the material mixture into a mixing container, adding 26g of acrylate emulsion (the solid content of the emulsion is 50%), 15g of water, 0.5g of emulsifier and 0.5g of defoamer, and uniformly stirring and dispersing to obtain the flame-retardant coating adhesive.
The flame-retardant coating adhesive is blade-coated on the back of the fabric (the fabric is unbleached terylene fabric, the gram weight is 200g, namely the weight of each square meter of fabric is 200 g), and the fabric is baked (150 ℃ and 180 s) to obtain the low-smoke high-efficiency flame-retardant terylene sofa textile fabric (sample 1), and the gram weight is 98.6g (namely the coating adhesive with the coating mass of 98.6g per square meter of fabric).
Sample 1 was soaked in 500ml of water at 45 ℃ for 30min, dried and weighed to 93.7g, to name sample 1-1.
Example 5
The APP-1 in example 4 was replaced with a conventional commercially available type II APP, the remainder was unchanged, the fabric (sample 2) was coated, the gram weight was 99.8g, sample 2 was soaked in 500ml of water at 45 ℃ for 30min, dried and weighed 88.6g, and sample 2-1 was named.
Example 6 bisphenol a bis (diphenyl phosphate) (BDP), APP-2, melamine cyanurate, zinc borate, triazine char-forming agent (CFA), epoxy resin were mixed in the following ratio of 1.5:5.0:2.0:2.0:2.5:2.0, preparing the material mixture with the total mass of 15.0g, adding the material mixture into a mixing container, adding 26g of acrylate emulsion (the solid content of the emulsion is 50%), 15g of water, 0.5g of emulsifier and 0.5g of defoamer, and uniformly stirring and dispersing to obtain the flame-retardant coating adhesive.
The flame-retardant coating adhesive is blade-coated on the back of the fabric to obtain the low-smoke high-efficiency flame-retardant polyester sofa textile fabric (sample 3), and the gram weight is 100.2g. Sample 3 was soaked in 500ml of water at 45 ℃ for 30min, dried and weighed to 95.2g, to name sample 3-1.
Example 7
APP-2 in example 6 was replaced with a conventional commercially available type II APP, the remainder was unchanged, the fabric (sample 4) was coated, the gram weight was 99.8g, sample 2 was soaked in 500ml of water at 45 ℃ for 30min, oven dried and weighed 89.1g, and sample 4-1 was named.
Example 8
APP-2 in example 6 was replaced with APP-3, the remainder was unchanged, the fabric (sample 5) was coated, the gram weight was 99.5g, sample 5 was soaked in 500ml of water at 45 ℃ for 30min, oven dried and weighed 93.9g, and sample 5-1 was named.
According to the flame retardant property, the flame retardant property of the test sample is tested by respectively covering the test sample after being soaked in water on specified polyurethane sponge, placing the test sample under a specified combustor for ignition, keeping the butane flame height at 35mm, stabilizing the flame for 30s, and continuously combusting the test sample for 20s with the flame; the test results are shown in Table 1.
TABLE 1
| Type of flame-retardant System | Test specimen | Percent weight loss | Experimental phenomena | BS5852 standard |
| Bromine-phosphorus synergistic system (APP-1) | 1-1 | 5.0 | 20s later, the fire is released and the fire is self-extinguished | By passing |
| Bromine-phosphorus synergistic system (II type APP) | 2-1 | 11.2 | Breaking the hole after 15-18s, the flame does not extinguish | Do not pass through |
| Halogen-free flame-retardant system (APP-2) | 3-1 | 5.0 | 20s later, the fire is released and the fire is self-extinguished | By passing |
| Halogen-free flame-retardant system (II type APP) | 4-1 | 10.7 | Breaking the hole after 13-16s, the flame does not extinguish | Do not pass through |
| Halogen-free flame-retardant system (APP-3) | 5-1 | 5.6 | 20s later, the fire is released and the fire is self-extinguished | By passing |
The water loss rate represents the water resistance of the flame-retardant coating composition, and the larger the water loss rate of the foam is, the poorer the water resistance of the flame-retardant coating composition is. As can be seen from the table above, the APP modified by the tubular kaolin has improved water resistance, and the APP-II sold in the traditional market has poorer water resistance.
As can be seen from the results of table 1 above: example 5,7 a commercially available conventional type II APP was used because the mass loss after soaking in water was too great and the flame retardant performance could not meet the flame retardant standard of BS 5852. Example 4,6,8 using the kaolin modified APP of the present invention, water loss can be reduced, water resistance can be improved, and the self-extinguishing effect of the product can be improved. Can reach the relevant flame retardant standard of BS 5852.
The above description is only a preferred embodiment of the present invention, and is not intended to limit the technical solutions of the present invention in any way. Any equivalent substitutions or partial modifications made under the technical spirit of the present invention will be considered to be within the scope of the present invention.
Claims (8)
1. A tubular kaolin modified ammonium polyphosphate functional monomer is characterized in that: the functional monomer is prepared by mixing nano SiO 2 Graft modification treatment the ammonium polyphosphate which is subjected to epoxy coating modification treatment or melamine coating modification treatment is embedded into the tubular kaolin to obtain the modified tubular kaolin.
2. The tubular kaolin modified ammonium polyphosphate functional monomer of claim 1, wherein: the functional monomer is prepared by the following steps (1), (2) or (3):
(1) Uniformly mixing ammonium polyphosphate and ethanol, then dropwise adding silica sol at 40-70 ℃ under the stirring condition, continuing to perform heat preservation reaction for 2-5h after dropwise adding is finished, adding tubular kaolin after the heat preservation reaction is finished, continuing to perform heat preservation reaction for 3-5h, performing solid-liquid separation after the heat preservation reaction is finished, and washing and drying the separated solid to obtain a tubular kaolin modified ammonium polyphosphate functional monomer;
(2) Mixing melamine and formaldehyde aqueous solution, adjusting the pH value to 7-9 by triethanolamine aqueous solution, heating to 60-85 ℃, reacting for 20-60min, and performing solid-liquid separation after the reaction to obtain melamine-formaldehyde polymer; uniformly mixing ammonium polyphosphate and ethanol, regulating the pH value to 4-6 by using hydrochloric acid, heating to 70-80 ℃, adding a melamine-formaldehyde polymer, performing heat preservation reaction for 1.5-3h, then adding tubular kaolin, continuing the heat preservation reaction for 3-5h, performing solid-liquid separation after the heat preservation reaction is continued, and washing and drying the separated solid to obtain a tubular kaolin modified ammonium polyphosphate functional monomer;
(3) Uniformly mixing ammonium polyphosphate and ethanol, adjusting the pH value to 4-6 by using hydrochloric acid, heating to 70-80 ℃, adding epoxy resin, and reacting for 1.5-3 hours in a heat preservation manner; and adding tubular kaolin after the heat preservation reaction is finished, continuing to perform the heat preservation reaction for 3-5 hours, performing solid-liquid separation after the heat preservation reaction is finished, and washing and drying the separated solid to obtain the tubular kaolin modified ammonium polyphosphate functional monomer.
3. The tubular kaolin modified ammonium polyphosphate functional monomer of claim 2, wherein: in the step (1), the mass ratio of the silica sol to the ammonium polyphosphate is 1:3-2:3, the mass ratio of the tubular kaolin to the ammonium polyphosphate is 1:3-2:3, and the dosage of the ethanol is 4-12 times of the mass of the ammonium polyphosphate.
4. The tubular kaolin modified ammonium polyphosphate functional monomer of claim 2, wherein: in the step (2), the mass ratio of the melamine to the formaldehyde aqueous solution is 1:3-2:1, the mass ratio of the ammonium polyphosphate to the melamine-formaldehyde polymer is 3:1-3:2, the mass ratio of the tubular kaolin to the ammonium polyphosphate is 1:3-2:3, and the dosage of the ethanol is 4-12 times of the mass of the ammonium polyphosphate.
5. The tubular kaolin modified ammonium polyphosphate functional monomer of claim 2, wherein: in the step (3), the mass ratio of the epoxy resin to the ammonium polyphosphate is 1:5-1:2, the mass ratio of the tubular kaolin to the ammonium polyphosphate is 1:3-2:3, and the dosage of the ethanol is 4-12 times of the mass of the ammonium polyphosphate.
6. The tubular kaolin modified ammonium polyphosphate functional monomer of claim 2, wherein: in the step (3), the concentration of the formaldehyde aqueous solution is 20-40%, and the concentration of the triethanolamine aqueous solution is 5-20%; in the step (2) and the step (3), the concentration of the hydrochloric acid is 5-20%.
7. The tubular kaolin modified ammonium polyphosphate functional monomer of claim 2, wherein: in the step (1), the dropping speed of the silica sol is 1-2 drops per second.
8. The tubular kaolin modified ammonium polyphosphate functional monomer of any one of claims 1 to 7, wherein: the tubular kaolin is tubular refractory kaolin, the average particle diameter of the tubular refractory kaolin particles is 0.2-2.0 mu m, the inner diameter of the tubular refractory kaolin particles is 15-30nm, and the inner surface of the tubular refractory kaolin is rich in anion and cation groups and has high-activity reactive sites.
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