CN109517220B - Preparation method of nano tin-based intumescent flame retardant - Google Patents
Preparation method of nano tin-based intumescent flame retardant Download PDFInfo
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- CN109517220B CN109517220B CN201811344369.9A CN201811344369A CN109517220B CN 109517220 B CN109517220 B CN 109517220B CN 201811344369 A CN201811344369 A CN 201811344369A CN 109517220 B CN109517220 B CN 109517220B
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- flame retardant
- tin
- deionized water
- based intumescent
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- 239000003063 flame retardant Substances 0.000 title claims abstract description 73
- 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 68
- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical compound [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 title claims abstract description 44
- 238000002360 preparation method Methods 0.000 title claims abstract description 10
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 44
- 239000008367 deionised water Substances 0.000 claims abstract description 37
- 229910021641 deionized water Inorganic materials 0.000 claims abstract description 37
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims abstract description 18
- 238000001027 hydrothermal synthesis Methods 0.000 claims abstract description 17
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims abstract description 16
- 239000000047 product Substances 0.000 claims abstract description 16
- 239000002244 precipitate Substances 0.000 claims abstract description 15
- 229910052751 metal Inorganic materials 0.000 claims abstract description 10
- 239000002184 metal Substances 0.000 claims abstract description 10
- 239000006185 dispersion Substances 0.000 claims abstract description 9
- 238000000034 method Methods 0.000 claims abstract description 9
- 229910052757 nitrogen Inorganic materials 0.000 claims abstract description 9
- 239000004094 surface-active agent Substances 0.000 claims abstract description 9
- 239000000203 mixture Substances 0.000 claims description 30
- 238000009210 therapy by ultrasound Methods 0.000 claims description 21
- 229920001223 polyethylene glycol Polymers 0.000 claims description 13
- 239000002202 Polyethylene glycol Substances 0.000 claims description 12
- LZZYPRNAOMGNLH-UHFFFAOYSA-M Cetrimonium bromide Chemical compound [Br-].CCCCCCCCCCCCCCCC[N+](C)(C)C LZZYPRNAOMGNLH-UHFFFAOYSA-M 0.000 claims description 10
- 229920000877 Melamine resin Polymers 0.000 claims description 9
- JDSHMPZPIAZGSV-UHFFFAOYSA-N melamine Chemical compound NC1=NC(N)=NC(N)=N1 JDSHMPZPIAZGSV-UHFFFAOYSA-N 0.000 claims description 9
- 239000004114 Ammonium polyphosphate Substances 0.000 claims description 8
- 229910021627 Tin(IV) chloride Inorganic materials 0.000 claims description 8
- 235000019826 ammonium polyphosphate Nutrition 0.000 claims description 8
- 229920001276 ammonium polyphosphate Polymers 0.000 claims description 8
- 150000003839 salts Chemical class 0.000 claims description 8
- HPGGPRDJHPYFRM-UHFFFAOYSA-J tin(iv) chloride Chemical compound Cl[Sn](Cl)(Cl)Cl HPGGPRDJHPYFRM-UHFFFAOYSA-J 0.000 claims description 8
- TVQLLNFANZSCGY-UHFFFAOYSA-N disodium;dioxido(oxo)tin Chemical compound [Na+].[Na+].[O-][Sn]([O-])=O TVQLLNFANZSCGY-UHFFFAOYSA-N 0.000 claims description 7
- 238000001035 drying Methods 0.000 claims description 7
- -1 polytetrafluoroethylene Polymers 0.000 claims description 7
- 229920001343 polytetrafluoroethylene Polymers 0.000 claims description 7
- 239000004810 polytetrafluoroethylene Substances 0.000 claims description 7
- 229940079864 sodium stannate Drugs 0.000 claims description 7
- 238000005406 washing Methods 0.000 claims description 7
- 238000004321 preservation Methods 0.000 claims description 6
- TXUICONDJPYNPY-UHFFFAOYSA-N (1,10,13-trimethyl-3-oxo-4,5,6,7,8,9,11,12,14,15,16,17-dodecahydrocyclopenta[a]phenanthren-17-yl) heptanoate Chemical compound C1CC2CC(=O)C=C(C)C2(C)C2C1C1CCC(OC(=O)CCCCCC)C1(C)CC2 TXUICONDJPYNPY-UHFFFAOYSA-N 0.000 claims description 5
- 229910021626 Tin(II) chloride Inorganic materials 0.000 claims description 5
- MNNHAPBLZZVQHP-UHFFFAOYSA-N diammonium hydrogen phosphate Chemical compound [NH4+].[NH4+].OP([O-])([O-])=O MNNHAPBLZZVQHP-UHFFFAOYSA-N 0.000 claims description 5
- 239000001119 stannous chloride Substances 0.000 claims description 5
- 235000011150 stannous chloride Nutrition 0.000 claims description 5
- 235000021355 Stearic acid Nutrition 0.000 claims description 4
- QIQXTHQIDYTFRH-UHFFFAOYSA-N octadecanoic acid Chemical compound CCCCCCCCCCCCCCCCCC(O)=O QIQXTHQIDYTFRH-UHFFFAOYSA-N 0.000 claims description 4
- OQCDKBAXFALNLD-UHFFFAOYSA-N octadecanoic acid Natural products CCCCCCCC(C)CCCCCCCCC(O)=O OQCDKBAXFALNLD-UHFFFAOYSA-N 0.000 claims description 4
- 239000008117 stearic acid Substances 0.000 claims description 4
- 238000003756 stirring Methods 0.000 claims description 4
- GVGUFUZHNYFZLC-UHFFFAOYSA-N dodecyl benzenesulfonate;sodium Chemical compound [Na].CCCCCCCCCCCCOS(=O)(=O)C1=CC=CC=C1 GVGUFUZHNYFZLC-UHFFFAOYSA-N 0.000 claims description 3
- 229940080264 sodium dodecylbenzenesulfonate Drugs 0.000 claims description 3
- 159000000007 calcium salts Chemical class 0.000 claims description 2
- IOUCSUBTZWXKTA-UHFFFAOYSA-N dipotassium;dioxido(oxo)tin Chemical compound [K+].[K+].[O-][Sn]([O-])=O IOUCSUBTZWXKTA-UHFFFAOYSA-N 0.000 claims description 2
- 150000002505 iron Chemical class 0.000 claims description 2
- 159000000003 magnesium salts Chemical class 0.000 claims description 2
- 150000003751 zinc Chemical class 0.000 claims description 2
- 239000007788 liquid Substances 0.000 abstract description 3
- 239000012266 salt solution Substances 0.000 abstract 1
- 239000000243 solution Substances 0.000 abstract 1
- 239000000463 material Substances 0.000 description 14
- 238000003760 magnetic stirring Methods 0.000 description 10
- JIAARYAFYJHUJI-UHFFFAOYSA-L zinc dichloride Chemical compound [Cl-].[Cl-].[Zn+2] JIAARYAFYJHUJI-UHFFFAOYSA-L 0.000 description 8
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 6
- 239000001301 oxygen Substances 0.000 description 6
- 229910052760 oxygen Inorganic materials 0.000 description 6
- 238000002411 thermogravimetry Methods 0.000 description 6
- 239000012796 inorganic flame retardant Substances 0.000 description 5
- 238000012360 testing method Methods 0.000 description 5
- TWRXJAOTZQYOKJ-UHFFFAOYSA-L Magnesium chloride Chemical compound [Mg+2].[Cl-].[Cl-] TWRXJAOTZQYOKJ-UHFFFAOYSA-L 0.000 description 4
- 239000011592 zinc chloride Substances 0.000 description 4
- 235000005074 zinc chloride Nutrition 0.000 description 4
- UXVMQQNJUSDDNG-UHFFFAOYSA-L Calcium chloride Chemical compound [Cl-].[Cl-].[Ca+2] UXVMQQNJUSDDNG-UHFFFAOYSA-L 0.000 description 3
- 238000002441 X-ray diffraction Methods 0.000 description 3
- 239000001110 calcium chloride Substances 0.000 description 3
- 229910001628 calcium chloride Inorganic materials 0.000 description 3
- 239000002131 composite material Substances 0.000 description 3
- 238000011161 development Methods 0.000 description 3
- 229910021578 Iron(III) chloride Inorganic materials 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- RBTARNINKXHZNM-UHFFFAOYSA-K iron trichloride Chemical compound Cl[Fe](Cl)Cl RBTARNINKXHZNM-UHFFFAOYSA-K 0.000 description 2
- 230000002045 lasting effect Effects 0.000 description 2
- 229910001629 magnesium chloride Inorganic materials 0.000 description 2
- 229910000000 metal hydroxide Inorganic materials 0.000 description 2
- 150000004692 metal hydroxides Chemical class 0.000 description 2
- 239000000779 smoke Substances 0.000 description 2
- ZOXJGFHDIHLPTG-UHFFFAOYSA-N Boron Chemical compound [B] ZOXJGFHDIHLPTG-UHFFFAOYSA-N 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 230000000996 additive effect Effects 0.000 description 1
- 229910052787 antimony Inorganic materials 0.000 description 1
- WATWJIUSRGPENY-UHFFFAOYSA-N antimony atom Chemical compound [Sb] WATWJIUSRGPENY-UHFFFAOYSA-N 0.000 description 1
- 229910052796 boron Inorganic materials 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- 238000002485 combustion reaction Methods 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 238000010276 construction Methods 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 239000000945 filler Substances 0.000 description 1
- 238000011049 filling Methods 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 238000009776 industrial production Methods 0.000 description 1
- 231100000252 nontoxic Toxicity 0.000 description 1
- 230000003000 nontoxic effect Effects 0.000 description 1
- 231100000956 nontoxicity Toxicity 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- 238000000197 pyrolysis Methods 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 239000000758 substrate Substances 0.000 description 1
- 230000001629 suppression Effects 0.000 description 1
- 230000002195 synergetic effect Effects 0.000 description 1
- 231100000331 toxic Toxicity 0.000 description 1
- 230000002588 toxic effect Effects 0.000 description 1
- 239000002341 toxic gas Substances 0.000 description 1
- BHTBHKFULNTCHQ-UHFFFAOYSA-H zinc;tin(4+);hexahydroxide Chemical compound [OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[Zn+2].[Sn+4] BHTBHKFULNTCHQ-UHFFFAOYSA-H 0.000 description 1
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- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K13/00—Use of mixtures of ingredients not covered by one single of the preceding main groups, each of these compounds being essential
- C08K13/02—Organic and inorganic ingredients
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/16—Halogen-containing compounds
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/18—Oxygen-containing compounds, e.g. metal carbonyls
- C08K3/24—Acids; Salts thereof
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/32—Phosphorus-containing compounds
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K5/00—Use of organic ingredients
- C08K5/16—Nitrogen-containing compounds
- C08K5/34—Heterocyclic compounds having nitrogen in the ring
- C08K5/3467—Heterocyclic compounds having nitrogen in the ring having more than two nitrogen atoms in the ring
- C08K5/3477—Six-membered rings
- C08K5/3492—Triazines
- C08K5/34922—Melamine; Derivatives thereof
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- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L27/00—Compositions of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a halogen; Compositions of derivatives of such polymers
- C08L27/02—Compositions of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a halogen; Compositions of derivatives of such polymers not modified by chemical after-treatment
- C08L27/04—Compositions of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a halogen; Compositions of derivatives of such polymers not modified by chemical after-treatment containing chlorine atoms
- C08L27/06—Homopolymers or copolymers of vinyl chloride
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- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/32—Phosphorus-containing compounds
- C08K2003/321—Phosphates
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- C08K2003/323—Ammonium polyphosphate
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- C08L2201/02—Flame or fire retardant/resistant
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Abstract
The invention discloses a preparation method of a nano tin-based intumescent flame retardant; the method adopts a hydrothermal method, a tin source, a surfactant and deionized water are ultrasonically dissolved, a nitrogen-based flame retardant dispersion liquid is added into the solution, then a soluble metal salt solution is added, hydrothermal reaction is carried out at 120-150 ℃, the precipitate is taken out and then is sequentially washed by the deionized water and ethanol, and the washed product is dried to prepare the nano tin-based intumescent flame retardant.
Description
Technical Field
The invention relates to a preparation technology of a flame-retardant material and a flame-retardant and smoke-suppression technology, in particular to a preparation method of a nano tin-based intumescent flame retardant.
Background
Along with the development of society and the prosperity of economy, people pay more and more attention to fire safety in daily life; the common inorganic flame retardant has the advantages of simple process, high purity, good thermal stability, no toxicity, no volatilization, lasting effect and the like. 80% of the dead people in a fire are killed by inhalation of toxic gases and masked smoke from the combustion of polymeric materials.
The inorganic flame-retardant material does not generate toxic and corrosive gases, belongs to physiological harmless substances, has higher safety, and has the advantages of simple process, high purity, good thermal stability, lasting effect and the like. With the continuous development of social economy, the requirements of people on safety are higher and higher. Inorganic flame retardants already account for over 50% of flame retardant consumption in developed countries; inorganic flame retardants can be classified into metal hydroxides, antimony-based, tin-based, boron-based, and the like; wherein, the metal hydroxide is generally used as a flame retardant filler and can exert the flame retardant effect only by filling a large amount; under the background, development of a composite flame retardant which generates synergistic effect with other flame retardants is a great trend in the future.
The tin-based flame retardant has both flame retardant and smoke suppression effects, is nontoxic and harmless, and is an ideal flame retardant synergist; researchers explore and synthesize novel efficient flame retardants, and simultaneously compound flame retardants with good flame retardant effect so as to reduce the using amount of the flame retardants and reduce the attenuation degree of physical and mechanical properties of flame retardant materials, and inorganic flame retardants develop towards superfine, composite and multifunctional systems.
The same literature disclosures as the technical scheme of the invention are not found at present.
Disclosure of Invention
The invention aims to provide a preparation method of a nano tin-based intumescent flame retardant, which solves the defects of the existing tin-based flame retardant in practical application; tin is an important nonferrous metal, the added value of the material is improved through deep processing, the material has obvious significance for national economic construction, but the tin price is higher, and the tin-based flame retardant is not easy to popularize and apply for a large amount of high-performance flame retardants required in the market, so that how to reduce the cost and improve the composite performance of the flame retardant becomes one of the important research points of the tin-based flame retardant; the nano tin-based intumescent flame retardant is prepared by a simple hydrothermal method, and the tin-based intumescent flame retardant and intumescent flame retardant components are effectively combined together.
The preparation method of the nano tin-based intumescent flame retardant comprises the following steps:
(1) adding a tin source, a surfactant and deionized water into a two-neck flask, performing ultrasonic treatment until the tin source, the surfactant and the deionized water are completely dissolved, and then placing the mixture in a water bath at the temperature of 75-95 ℃ for heat preservation;
the surfactant is one of Cetyl Trimethyl Ammonium Bromide (CTAB), polyethylene glycol (PEG-6000) and Sodium Dodecyl Benzene Sulfonate (SDBS);
the tin source is one of sodium stannate, potassium stannate, stannous chloride and stannic chloride;
(2) dispersing a nitrogen flame retardant in deionized water, performing ultrasonic treatment until the nitrogen flame retardant is uniformly dispersed, dropwise adding the dispersion into the two-neck flask obtained in the step (1), stirring to uniformly mix the dispersion, and keeping the temperature for 4-8 hours;
the nitrogen flame retardant is one of melamine, ammonium polyphosphate and ammonium hydrogen phosphate;
(3) dissolving soluble metal salt in deionized water, performing ultrasonic treatment until the soluble metal salt is completely dissolved, dropwise adding the solution into the two-neck flask obtained in the step (2), stirring to uniformly mix the solution, and keeping the temperature for 4-8 hours;
the soluble metal salt is one of zinc salt, magnesium salt, iron salt and calcium salt;
(4) and (3) transferring the mixture obtained in the step (3) into a hydrothermal reaction kettle with a polytetrafluoroethylene lining, carrying out hydrothermal reaction for 4-12 h at 120-150 ℃, taking out the precipitate, sequentially washing the precipitate for 3-5 times by using deionized water and ethanol, and drying the washed product for 7-12 h at 70-90 ℃ to obtain the nano tin-based intumescent flame retardant.
The molar ratio of the tin source to the nitrogen-based flame retardant is 1: 4-4: 1, the molar ratio of the soluble metal salt to the tin source is 1: 1-1: 20, and the mass ratio of the tin source to the surfactant is 200: 1-500: 1.
The product prepared by the method is detected by X-ray diffraction (XRD), and the result shows that the product is the nano tin-based intumescent flame retardant; observing the appearance and size of the product by using a scanning electron microscope; the product was examined by thermogravimetric analysis (TGA) and showed a flame retardant temperature.
Compared with the prior art, the invention has the following advantages:
(1) the preparation method is simple, low in cost and mild in reaction condition;
(2) the addition amount of tin element is less, and the better flame retardant property is obtained;
(3) the product can be used as an additive in the preparation of flame-retardant materials, the oxygen index of the prepared product is more than 27, and the flame retardant starts to react at a lower temperature to play a role in protecting a base material;
(4) the raw materials adopted by the invention are environment-friendly, the process is simple, and the industrial production is easy to realize.
Drawings
FIG. 1 is an X-ray diffraction (XRD) pattern of a nano-tin-based flame retardant prepared in example 1;
FIG. 2 is a thermogravimetric analysis (TGA) plot of the nano-tin based flame retardant prepared in example 2;
FIG. 3 is a Scanning Electron Microscope (SEM) image of the nano-tin-based flame retardant prepared in example 3;
fig. 4 is a Scanning Electron Microscope (SEM) image of the nano tin-based flame retardant prepared in example 4.
Detailed Description
The invention is explained in more detail below with reference to the figures and examples, without limiting the scope of the invention.
Example 1:
(1) adding 0.01mol of sodium stannate, 0.01g of hexadecyl trimethyl ammonium bromide (CTAB) and 80mL of deionized water into a two-mouth flask, performing ultrasonic treatment for 20min until the sodium stannate, the CTAB and the deionized water are completely dissolved, and then placing the mixture into a water bath with the temperature of 80 ℃ for heat preservation;
(2) dispersing 0.01mol of melamine in 20mL of deionized water, carrying out ultrasonic treatment for 10min until the melamine is uniformly dispersed, dropwise adding the dispersion into the two-neck flask obtained in the step (1), carrying out magnetic stirring to uniformly mix the melamine and the dispersion, and keeping the temperature for 4 h;
(3) dissolving 0.002mol of zinc chloride in 20mL of deionized water, performing ultrasonic treatment for 10min until the zinc chloride is completely dissolved, dropwise adding the solution into the two-neck flask obtained in the step (2), performing magnetic stirring to uniformly mix the solution, and keeping the temperature for 4 hours;
(4) transferring the mixture obtained in the step (3) into a 150mL hydrothermal reaction kettle with a polytetrafluoroethylene lining, carrying out hydrothermal reaction for 12h at 120 ℃, taking out the precipitate, sequentially washing the precipitate for 3 times by using deionized water and ethanol, and drying the washed product for 12h at 70 ℃ to obtain the nano tin-based intumescent flame retardant; the X-ray diffraction (XRD) pattern of the nano-tin-based flame retardant prepared in the embodiment is shown in figure 1, and the product contains zinc hydroxystannate and melamine, and the grain size of the material is calculated to be less than 100nm according to the peak width in figure 1;
the flame retardant prepared in this example was used in flexible PVC to prepare a flame retardant test material (added in an amount of 5% by mass of the flexible PVC), resulting in an increase in the oxygen index of the flexible PVC from 23.7 to 27.5.
Example 2:
(1) adding 0.04mol of sodium stannate, polyethylene glycol (PEG-6000) and 80mL of deionized water into a two-neck flask, performing ultrasonic treatment for 20min until the sodium stannate, the polyethylene glycol and the polyethylene glycol are completely dissolved, and maintaining a water bath at 75 ℃, wherein the mass ratio of the sodium stannate to the polyethylene glycol is 500: 1;
(2) dispersing 0.04mol of melamine in 20mL of deionized water, carrying out ultrasonic treatment for 10min until the melamine is uniformly dispersed, dropwise adding the dispersion into the two-neck flask obtained in the step (1), carrying out magnetic stirring to uniformly mix the melamine and the dispersion, and keeping the temperature for 6 h;
(3) dissolving 0.01mol of zinc chloride in 20mL of deionized water, performing ultrasonic treatment for 10min until the zinc chloride is completely dissolved, dropwise adding the solution into the two-neck flask obtained in the step (2), performing magnetic stirring to uniformly mix the solution, and keeping the temperature for 6 h;
(4) transferring the mixture obtained in the step (3) into a 150mL hydrothermal reaction kettle with a polytetrafluoroethylene lining, carrying out hydrothermal reaction for 5h at 150 ℃, taking out the precipitate, sequentially washing the precipitate for 5 times by using deionized water and ethanol, and drying the washed product for 7h at 90 ℃ to obtain the nano tin-based intumescent flame retardant; the thermogravimetric analysis (TGA) of the nano-tin-based flame retardant prepared in this example is shown in FIG. 2, and FIG. 2 shows that the pyrolysis temperature of the prepared product is about 225 ℃, which indicates that the flame retardant component starts to react at a lower temperature to protect the substrate.
The flame retardant prepared in this example was used in flexible PVC to prepare a flame retardant test material (added in an amount of 5% by mass of the flexible PVC), resulting in an increase in the oxygen index of the flexible PVC from 23.7 to 27.6.
Example 3:
(1) adding 0.02mol of stannous chloride, Cetyl Trimethyl Ammonium Bromide (CTAB) and 80mL of deionized water into a two-mouth flask, performing ultrasonic treatment for 20min until the stannous chloride, the cetyl trimethyl ammonium bromide and the deionized water are completely dissolved, and then placing the mixture into a water bath at 85 ℃ for heat preservation, wherein the mass ratio of the stannous chloride to the cetyl trimethyl ammonium bromide is 300: 1;
(2) dispersing 0.03mol of ammonium hydrogen phosphate in 20mL of deionized water, carrying out ultrasonic treatment for 10min until the ammonium hydrogen phosphate is uniformly dispersed, dropwise adding the dispersed liquid into the two-neck flask obtained in the step (1), carrying out magnetic stirring to uniformly mix the ammonium hydrogen phosphate and the deionized water, and keeping the temperature for 8 h;
(3) dissolving 0.005mol of magnesium chloride in 20mL of deionized water, performing ultrasonic treatment for 10min until the magnesium chloride is completely dissolved, dropwise adding the solution into the two-neck flask obtained in the step (2), performing magnetic stirring to uniformly mix the solution, and keeping the temperature for 5 hours;
(4) transferring the mixture obtained in the step (3) into a hydrothermal reaction kettle with a polytetrafluoroethylene lining of 150mL, carrying out hydrothermal reaction for 10h at 130 ℃, taking out the precipitate, sequentially washing the precipitate for 4 times by using deionized water and ethanol, and drying the washed product for 10h at 80 ℃ to obtain the nano tin-based intumescent flame retardant; the microscopic morphology of the nano tin-based flame retardant prepared in the embodiment is shown in figure 3;
the flame retardant prepared in this example was used in flexible PVC to prepare a flame retardant test material (added in an amount of 5% by mass of the flexible PVC), resulting in an increase in the oxygen index of the flexible PVC from 23.7 to 27.4.
Example 4:
(1) adding 0.02mol of stannic chloride, polyethylene glycol (PEG-6000) and 80mL of deionized water into a two-neck flask, performing ultrasonic treatment for 20min to completely dissolve the stannic chloride, the polyethylene glycol and the PEG, and then placing the mixture into a water bath at 90 ℃ for heat preservation, wherein the mass ratio of the stannic chloride to the polyethylene glycol is 200: 1;
(2) dispersing 0.04mol of ammonium polyphosphate in 20mL of deionized water, carrying out ultrasonic treatment for 10min until the ammonium polyphosphate is uniformly dispersed, dropwise adding the dispersion into the two-neck flask obtained in the step (1), carrying out magnetic stirring to uniformly mix the ammonium polyphosphate and the deionized water, and keeping the temperature for 6 h;
(3) dissolving 0.008mol of ferric chloride in 20mL of deionized water, performing ultrasonic treatment for 10min until the ferric chloride is completely dissolved, dropwise adding the solution into the two-neck flask obtained in the step (2), performing magnetic stirring to uniformly mix the solution, and keeping the temperature for 4 hours;
(4) transferring the mixture obtained in the step (3) into a hydrothermal reaction kettle with a 150mL polytetrafluoroethylene lining, carrying out hydrothermal reaction for 8h at 140 ℃, taking out the precipitate, sequentially washing the precipitate for 4 times by using deionized water and ethanol, and drying the washed product for 8h at 85 ℃ to obtain the nano tin-based intumescent flame retardant; the microscopic morphology of the nano tin-based flame retardant prepared in the embodiment is shown in figure 4;
the flame retardant prepared in this example was used in flexible PVC to prepare a flame retardant test material (added in an amount of 5% by mass of the flexible PVC), resulting in an increase in the oxygen index of the flexible PVC from 23.7 to 27.1.
Example 5:
(1) adding 0.03mol of stannic chloride, stearic acid and 80mL of deionized water into a two-neck flask, performing ultrasonic treatment for 20min until the stannic chloride, the stearic acid and the deionized water are completely dissolved, and then placing the mixture into a water bath at 95 ℃ for heat preservation, wherein the mass ratio of the stannic chloride to the stearic acid is 400: 1;
(2) dispersing 0.03mol of ammonium polyphosphate in 20mL of deionized water, carrying out ultrasonic treatment for 10min until the ammonium polyphosphate is uniformly dispersed, dropwise adding the dispersed liquid into the two-neck flask obtained in the step (1), carrying out magnetic stirring to uniformly mix the ammonium polyphosphate and the deionized water, and keeping the temperature for 6 h;
(3) dissolving 0.004mol of calcium chloride in 20mL of deionized water, performing ultrasonic treatment for 10min until the calcium chloride is completely dissolved, dropwise adding the solution into the two-neck flask obtained in the step (2), performing magnetic stirring to uniformly mix the calcium chloride and the solution, and keeping the temperature for 4 h;
(4) transferring the mixture obtained in the step (3) into a 150mL hydrothermal reaction kettle with a polytetrafluoroethylene lining, carrying out hydrothermal reaction for 8h at 135 ℃, taking out the precipitate, sequentially washing the precipitate for 3 times by using deionized water and ethanol, and drying the washed product for 7h at 90 ℃ to obtain the nano tin-based intumescent flame retardant;
the flame retardant prepared in this example was used in flexible PVC to prepare a flame retardant test material (added in an amount of 5% by mass of the flexible PVC), resulting in an increase in the oxygen index of the flexible PVC from 23.7 to 27.2.
Claims (3)
1. A preparation method of a nano tin-based intumescent flame retardant is characterized by comprising the following specific steps:
(1) dissolving a tin source and a surfactant in deionized water, performing ultrasonic treatment until the tin source and the surfactant are completely dissolved, and then placing the mixture in a water bath at the temperature of 75-95 ℃ for heat preservation;
(2) dispersing a nitrogen flame retardant in deionized water, performing ultrasonic treatment until the nitrogen flame retardant is uniformly dispersed, dropwise adding the dispersion into the mixture obtained in the step (1), stirring to uniformly mix the mixture, and keeping the temperature for 4-8 hours;
(3) dissolving soluble metal salt in deionized water, performing ultrasonic treatment until the soluble metal salt is completely dissolved, dropwise adding the solution into the mixture obtained in the step (2), stirring to uniformly mix the solution, and keeping the temperature for 4-8 hours;
(4) transferring the mixture obtained in the step (3) into a hydrothermal reaction kettle with a polytetrafluoroethylene lining, carrying out hydrothermal reaction for 4-12 h at 120-150 ℃, taking out the precipitate, sequentially washing the precipitate for 3-5 times by using deionized water and ethanol, and drying the washed product for 7-12 h at 70-90 ℃ to obtain the nano tin-based intumescent flame retardant;
the tin source is one of sodium stannate, potassium stannate, stannous chloride and stannic chloride;
the nitrogen flame retardant is one of melamine, ammonium polyphosphate and ammonium hydrogen phosphate;
the soluble metal salt is one of zinc salt, magnesium salt, iron salt and calcium salt.
2. The method for preparing nano tin-based intumescent flame retardant of claim 1, wherein the method comprises the following steps: the surfactant is one of cetyl trimethyl ammonium bromide, polyethylene glycol, sodium dodecyl benzene sulfonate and stearic acid.
3. The method for preparing nano tin-based intumescent flame retardant of claim 1, wherein the method comprises the following steps: the molar ratio of the tin source to the nitrogen-based flame retardant is 1: 4-4: 1, the molar ratio of the soluble metal salt to the tin source is 1: 1-1: 20, and the mass ratio of the tin source to the surfactant is 200: 1-500: 1.
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Effective date of registration: 20240412 Address after: No. 2 Yunjing Road, Information Industry Base, Luoyang Street Office, Economic Development Zone, Kunming Area, China (Yunnan) Pilot Free Trade Zone, Kunming City, Yunnan Province, 650501 Patentee after: YUNNAN TIN NEW MATERIAL Co.,Ltd. Country or region after: China Address before: No. 650000, Changyuan Road, Kunming, Yunnan Province Patentee before: R & D Center of Yunnan Tin Industry Group (Holdings) Co.,Ltd. Country or region before: China |