CN109517220A - A kind of preparation method of nanometer of tinbase expanding fire retardant - Google Patents
A kind of preparation method of nanometer of tinbase expanding fire retardant Download PDFInfo
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- CN109517220A CN109517220A CN201811344369.9A CN201811344369A CN109517220A CN 109517220 A CN109517220 A CN 109517220A CN 201811344369 A CN201811344369 A CN 201811344369A CN 109517220 A CN109517220 A CN 109517220A
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- China
- Prior art keywords
- tinbase
- nanometer
- fire retardant
- expanding fire
- deionized water
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- 239000003063 flame retardant Substances 0.000 title claims abstract description 57
- 238000002360 preparation method Methods 0.000 title claims abstract description 15
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 30
- 239000008367 deionised water Substances 0.000 claims abstract description 28
- 229910021641 deionized water Inorganic materials 0.000 claims abstract description 28
- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical compound [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 claims abstract description 22
- 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 claims abstract description 16
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims abstract description 16
- 238000001027 hydrothermal synthesis Methods 0.000 claims abstract description 10
- 235000019441 ethanol Nutrition 0.000 claims abstract description 8
- 239000007788 liquid Substances 0.000 claims abstract description 8
- 230000001376 precipitating effect Effects 0.000 claims abstract description 8
- 238000005406 washing Methods 0.000 claims abstract description 8
- 238000004090 dissolution Methods 0.000 claims abstract 2
- 239000000203 mixture Substances 0.000 claims description 14
- 239000003795 chemical substances by application Substances 0.000 claims description 12
- 239000002202 Polyethylene glycol Substances 0.000 claims description 11
- 229920001223 polyethylene glycol Polymers 0.000 claims description 11
- 238000002604 ultrasonography Methods 0.000 claims description 8
- 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 6
- 229910021626 Tin(II) chloride Inorganic materials 0.000 claims description 6
- 230000003213 activating effect Effects 0.000 claims description 6
- 150000003839 salts Chemical class 0.000 claims description 6
- 239000001119 stannous chloride Substances 0.000 claims description 6
- 235000011150 stannous chloride Nutrition 0.000 claims description 6
- 229920000877 Melamine resin Polymers 0.000 claims description 5
- JDSHMPZPIAZGSV-UHFFFAOYSA-N melamine Chemical compound NC1=NC(N)=NC(N)=N1 JDSHMPZPIAZGSV-UHFFFAOYSA-N 0.000 claims description 5
- 239000004114 Ammonium polyphosphate Substances 0.000 claims description 4
- 229910021627 Tin(IV) chloride Inorganic materials 0.000 claims description 4
- 235000019826 ammonium polyphosphate Nutrition 0.000 claims description 4
- 229920001276 ammonium polyphosphate Polymers 0.000 claims description 4
- 238000003756 stirring Methods 0.000 claims description 4
- HPGGPRDJHPYFRM-UHFFFAOYSA-J tin(iv) chloride Chemical compound Cl[Sn](Cl)(Cl)Cl HPGGPRDJHPYFRM-UHFFFAOYSA-J 0.000 claims description 4
- MNNHAPBLZZVQHP-UHFFFAOYSA-N diammonium hydrogen phosphate Chemical compound [NH4+].[NH4+].OP([O-])([O-])=O MNNHAPBLZZVQHP-UHFFFAOYSA-N 0.000 claims description 3
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 claims description 2
- 235000021355 Stearic acid Nutrition 0.000 claims description 2
- 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
- 239000002270 dispersing agent Substances 0.000 claims description 2
- RBTARNINKXHZNM-UHFFFAOYSA-K iron trichloride Chemical compound Cl[Fe](Cl)Cl RBTARNINKXHZNM-UHFFFAOYSA-K 0.000 claims description 2
- 159000000003 magnesium salts Chemical class 0.000 claims description 2
- QIQXTHQIDYTFRH-UHFFFAOYSA-N octadecanoic acid Chemical compound CCCCCCCCCCCCCCCCCC(O)=O QIQXTHQIDYTFRH-UHFFFAOYSA-N 0.000 claims description 2
- OQCDKBAXFALNLD-UHFFFAOYSA-N octadecanoic acid Natural products CCCCCCCC(C)CCCCCCCCC(O)=O OQCDKBAXFALNLD-UHFFFAOYSA-N 0.000 claims description 2
- 239000011734 sodium Substances 0.000 claims description 2
- 229910052708 sodium Inorganic materials 0.000 claims description 2
- 239000008117 stearic acid Substances 0.000 claims description 2
- 150000003751 zinc Chemical class 0.000 claims description 2
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims 2
- 239000002253 acid Substances 0.000 claims 1
- 125000005211 alkyl trimethyl ammonium group Chemical group 0.000 claims 1
- -1 neopelex Substances 0.000 claims 1
- 229910052757 nitrogen Inorganic materials 0.000 claims 1
- 238000000034 method Methods 0.000 abstract description 7
- 239000006185 dispersion Substances 0.000 abstract description 6
- 238000006243 chemical reaction Methods 0.000 abstract description 2
- 229910052751 metal Inorganic materials 0.000 abstract description 2
- 239000002184 metal Substances 0.000 abstract description 2
- 238000005265 energy consumption Methods 0.000 abstract 1
- 238000009776 industrial production Methods 0.000 abstract 1
- 239000012266 salt solution Substances 0.000 abstract 1
- 239000000243 solution Substances 0.000 abstract 1
- 239000004094 surface-active agent Substances 0.000 abstract 1
- 238000013019 agitation Methods 0.000 description 10
- 239000000463 material Substances 0.000 description 9
- 239000000654 additive Substances 0.000 description 7
- 230000000996 additive effect Effects 0.000 description 7
- LZZYPRNAOMGNLH-UHFFFAOYSA-M Cetrimonium bromide Chemical group [Br-].CCCCCCCCCCCCCCCC[N+](C)(C)C LZZYPRNAOMGNLH-UHFFFAOYSA-M 0.000 description 6
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 6
- 230000000694 effects Effects 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
- TVQLLNFANZSCGY-UHFFFAOYSA-N disodium;dioxido(oxo)tin Chemical compound [Na+].[Na+].[O-][Sn]([O-])=O TVQLLNFANZSCGY-UHFFFAOYSA-N 0.000 description 4
- 238000004079 fireproofing Methods 0.000 description 4
- 229940079864 sodium stannate Drugs 0.000 description 4
- JIAARYAFYJHUJI-UHFFFAOYSA-L zinc dichloride Chemical compound [Cl-].[Cl-].[Zn+2] JIAARYAFYJHUJI-UHFFFAOYSA-L 0.000 description 4
- 238000002441 X-ray diffraction Methods 0.000 description 3
- TWRXJAOTZQYOKJ-UHFFFAOYSA-L Magnesium chloride Chemical compound [Mg+2].[Cl-].[Cl-] TWRXJAOTZQYOKJ-UHFFFAOYSA-L 0.000 description 2
- 235000019504 cigarettes Nutrition 0.000 description 2
- 238000002485 combustion reaction Methods 0.000 description 2
- 239000002131 composite material Substances 0.000 description 2
- 150000001875 compounds Chemical class 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 239000012757 flame retardant agent Substances 0.000 description 2
- 230000002045 lasting effect Effects 0.000 description 2
- 229910000000 metal hydroxide Inorganic materials 0.000 description 2
- 150000004692 metal hydroxides Chemical class 0.000 description 2
- 231100000252 nontoxic Toxicity 0.000 description 2
- 230000003000 nontoxic effect Effects 0.000 description 2
- 239000000758 substrate Substances 0.000 description 2
- 230000001629 suppression Effects 0.000 description 2
- 239000011592 zinc chloride Substances 0.000 description 2
- 235000005074 zinc chloride Nutrition 0.000 description 2
- 206010003497 Asphyxia Diseases 0.000 description 1
- ZOXJGFHDIHLPTG-UHFFFAOYSA-N Boron Chemical compound [B] ZOXJGFHDIHLPTG-UHFFFAOYSA-N 0.000 description 1
- UXVMQQNJUSDDNG-UHFFFAOYSA-L Calcium chloride Chemical compound [Cl-].[Cl-].[Ca+2] UXVMQQNJUSDDNG-UHFFFAOYSA-L 0.000 description 1
- CWYNVVGOOAEACU-UHFFFAOYSA-N Fe2+ Chemical compound [Fe+2] CWYNVVGOOAEACU-UHFFFAOYSA-N 0.000 description 1
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 1
- 239000005864 Sulphur Substances 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
- 239000001110 calcium chloride Substances 0.000 description 1
- 229910001628 calcium chloride Inorganic materials 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 230000007812 deficiency Effects 0.000 description 1
- 238000002242 deionisation method Methods 0.000 description 1
- 238000001514 detection method Methods 0.000 description 1
- 239000003599 detergent Substances 0.000 description 1
- 239000000945 filler Substances 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 238000000227 grinding Methods 0.000 description 1
- 239000004615 ingredient Substances 0.000 description 1
- FBAFATDZDUQKNH-UHFFFAOYSA-M iron chloride Chemical compound [Cl-].[Fe] FBAFATDZDUQKNH-UHFFFAOYSA-M 0.000 description 1
- 231100000518 lethal Toxicity 0.000 description 1
- 230000001665 lethal effect Effects 0.000 description 1
- 229910001629 magnesium chloride Inorganic materials 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 238000000197 pyrolysis Methods 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 239000003340 retarding agent Substances 0.000 description 1
- HFQQZARZPUDIFP-UHFFFAOYSA-M sodium;2-dodecylbenzenesulfonate Chemical compound [Na+].CCCCCCCCCCCCC1=CC=CC=C1S([O-])(=O)=O HFQQZARZPUDIFP-UHFFFAOYSA-M 0.000 description 1
- 229940071182 stannate Drugs 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 230000002195 synergetic effect Effects 0.000 description 1
- 230000002194 synthesizing 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
- 229910052725 zinc Inorganic materials 0.000 description 1
- 239000011701 zinc Substances 0.000 description 1
Classifications
-
- 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
- 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
-
- 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
-
- 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
-
- 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
-
- C—CHEMISTRY; METALLURGY
- 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
-
- 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
- C08K2003/321—Phosphates
- C08K2003/322—Ammonium phosphate
- C08K2003/323—Ammonium polyphosphate
-
- 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
- C08K2201/00—Specific properties of additives
- C08K2201/011—Nanostructured additives
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2201/00—Properties
- C08L2201/02—Flame or fire retardant/resistant
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- Chemical & Material Sciences (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- Compositions Of Macromolecular Compounds (AREA)
- Fireproofing Substances (AREA)
Abstract
The invention discloses the preparation methods of a kind of nanometer of tinbase expanding fire retardant；Nitrogenated flame retardant dispersion liquid is added in above-mentioned solution after tin source, surfactant, deionized water ultrasonic dissolution by this method using hydro-thermal method, then soluble metal salt solution is added, the hydro-thermal reaction at 120 ~ 150 DEG C, after taking out precipitating, it is successively washed with deionized water and ethyl alcohol, the dry obtained nanometer tinbase expanding fire retardant of product after washing, the method for the present invention preparation flow is simple, and yield is high, low energy consumption, reaction condition is mild, has preferable development prospect, is easy to realize industrial production.
Description
Technical field
The present invention relates to fire proofing technology of preparing, fire-retardant and suppression cigarette technology, specifically a kind of nanometer of tinbase expandable flame retardants
The preparation method of agent.
Background technique
With the development and economic prosperity of society, people's daily life is also increasingly to pay attention to fire safety；Generally
Inorganic fire retardants all has many advantages, such as that simple process, purity is high, thermal stability are good, nontoxic, non-volatile, effect is lasting.In fire
80% the dead is lethal because sucking the toxic gas and shielding smog asphyxia that high molecular material burning generates.
Inorganic anti-flaming material does not generate toxic and corrosive gas, and it is higher to belong to physiological harmlessness substance, safety, while nothing
Machine fire proofing all has many advantages, such as that simple process, purity is high, thermal stability are good, effect is lasting.With continuing for social economy
Development, requirement of the people to safety are also higher and higher.Inorganic fire retardants has accounted for the 50% of fire retardant consumption figure in developed country
More than；Inorganic fire retardants can be divided into metal hydroxides, antimony system, tin system, boron system etc.；Wherein metal hydroxides generally as
Flame retardant filler needs largely to fill competence exertion flame retardant effect；In this context, develop a kind of composite flame-retardant agent, make its with
It is to develop main trend in the future that other fire retardants, which generate synergistic effect,.
Tinbase fire retardant had not only had fire retardation but also had had suppression cigarette effect, while nontoxic, was a kind of ideal fire-retardant
Synergist；Researcher also compounds the fire retardant of good flame retardation effect while exploring synthesizing new efficient flame-retarding agent,
To reach reduction amount of flame-retardant agent, reduce the attenuation degree of fire proofing physical and mechanical property, inorganic fire retardants towards it is ultra-fine,
Compound, multifunctional structures development.
Have no that document identical with technical solution of the present invention discloses at present.
Summary of the invention
The purpose of the present invention is to provide the preparation methods of a kind of nanometer of tinbase expanding fire retardant, and it is fire-retardant to solve current tinbase
The deficiency and defect of agent in practical applications；Tin is a kind of important non-ferrous metal, and the added value of material is promoted by deep processing,
There is significant meaning to national economic development, but tin valence is higher, a large amount of high-performance refractory agent for market demand, tinbase
Fire retardant is not easy to promote and apply, so composite performance the grinding as tinbase fire retardant for how reducing cost, improving fire retardant
Study carefully one of emphasis；The present invention has been prepared nanometer tinbase expanding fire retardant, has effectively been hindered tinbase by simple hydro-thermal method
Combustion agent and expandable flame retardant ingredient are combined together.
Steps are as follows for the preparation method of nanometer tinbase expanding fire retardant of the present invention:
(1) tin source, table activating agent are added in two mouth flask, in deionized water, then ultrasound sets mixture to being completely dissolved
It is kept the temperature in 75 ~ 95 DEG C of water-baths；
The table activating agent is cetyl trimethylammonium bromide (CTAB), polyethylene glycol (PEG-6000), detergent alkylate sulphur
One of sour sodium (SDBS)；
The tin source is one of sodium stannate, potassium stannate, stannous chloride, tin tetrachloride；
(2) it disperses nitrogenated flame retardant in deionized water, dispersant liquid drop is added to (1) two mouthful of step to being uniformly dispersed by ultrasound
In flask, stirring is uniformly mixed it, 4 ~ 8h of constant temperature；
The nitrogenated flame retardant is one of melamine, ammonium polyphosphate, ammonium hydrogen phosphate；
(3) soluble metallic salt is dissolved in deionized water, solution is added drop-wise to (2) two mouthfuls of step to being completely dissolved by ultrasound
In flask, stirring is uniformly mixed it, 4 ~ 8h of constant temperature；
The soluble metallic salt is one of zinc salt, magnesium salts, molysite, calcium salt；
(4) step (3) mixture is transferred in the hydrothermal reaction kettle of polytetrafluoroethyllining lining, hydro-thermal is anti-at 120 ~ 150 DEG C
Answer 4 ~ 12h, after taking out precipitating, successively washed 3 ~ 5 times with deionized water and ethyl alcohol, after washing product dry 7 at 70 ~ 90 DEG C ~
12h is to get nanometer tinbase expanding fire retardant.
The tin source and the molar ratio of nitrogenated flame retardant are 1:4 ~ 4:1, and the molar ratio of soluble metallic salt and tin source is 1:1
The mass ratio of ~ 1:20, tin source and table activating agent is 200:1 ~ 500:1.
The product made from X-ray diffraction (XRD) detection the method for the present invention, the product is the expansion of nanometer tinbase as the result is shown
Fire retardant；With the pattern of scanning electron microscopic observation product, size；Product is detected with thermogravimetric analysis (TGA), the product hinders as the result is shown
Fire operative temperature.
Compared with prior art, the present invention has the advantage that
(1) preparation method of the present invention is simple, cost is relatively low, and reaction condition is mild；
(2) less tin element additive amount obtains more preferably flame retardant property；
(3) product of the present invention can be used as additive in fire proofing preparation, product oxygen index (OI) obtained to be greater than 27, and hinders
Combustion agent begins to react in lower temperature, plays the effect of protection substrate；
(4) raw material of the present invention is environmental-friendly, simple process, easy to industrialized production.
Detailed description of the invention
Fig. 1 is the X-ray diffraction (XRD) figure of nanometer tin based flameproofing prepared by embodiment 1；
Fig. 2 is the thermogravimetric analysis of nanometer tin based flameproofing (TGA) figure prepared by embodiment 2；
Fig. 3 is scanning electron microscope (SEM) figure of nanometer tin based flameproofing prepared by embodiment 3；
Fig. 4 is scanning electron microscope (SEM) figure of nanometer tin based flameproofing prepared by embodiment 4.
Specific embodiment
Below by drawings and examples, invention is further described in detail, but protection scope of the present invention is not limited to
In the content.
Embodiment 1:
(1) 0.01mol sodium stannate is added in two mouth flask, cetyl trimethylammonium bromide (CTAB), the 80mL of 0.01g are gone
Then mixture is placed in 80 DEG C of water-baths and keeps the temperature to being completely dissolved by ionized water, ultrasonic 20min；
(2) 0.01mol melamine is dispersed in 20mL deionized water, dispersion liquid is added dropwise to being uniformly dispersed by ultrasonic 10min
Into step (1) two mouth flask, magnetic agitation is uniformly mixed it, constant temperature 4h；
(3) 0.002mol zinc chloride is dissolved in 20mL deionized water, solution is added drop-wise to by ultrasonic 10min to being completely dissolved
In step (2) two mouth flask, magnetic agitation is uniformly mixed it, constant temperature 4h；
(4) step (3) mixture is transferred in the hydrothermal reaction kettle of 150mL polytetrafluoroethyllining lining, hydro-thermal is anti-at 120 DEG C
12h is answered, after taking out precipitating, is successively washed 3 times with deionized water and ethyl alcohol, product dries 12h at 70 DEG C to get receiving after washing
Meter Xi Ji expanding fire retardant；The X-ray diffraction (XRD) figure of nanometer tin based flameproofing made from the present embodiment is shown in Fig. 1, from Fig. 1
It can be seen that containing zinc hydroxyl stannate and melamine in product, and material grains size is calculated according to peak width and is less than 100nm；
Being used in flexible PVC prepare flame retardant test material for fire retardant made from the present embodiment, (additive amount is flexible PVC quality
5%), as a result the oxygen index (OI) of flexible PVC increases to 27.5 from 23.7.
Embodiment 2:
(1) 0.04mol sodium stannate, polyethylene glycol (PEG-6000), 80mL deionized water, ultrasound are added in two mouth flask
20min is to being completely dissolved, and water-bath is maintained at 75 DEG C, and wherein the mass ratio of sodium stannate and polyethylene glycol is 500:1；
(2) 0.04mol melamine is dispersed in 20mL deionized water, dispersion liquid is added dropwise to being uniformly dispersed by ultrasonic 10min
Into step (1) two mouth flask, magnetic agitation is uniformly mixed it, constant temperature 6h；
(3) 0.01mol zinc chloride is dissolved in 20mL deionized water, ultrasonic 10min is added drop-wise to step to being completely dissolved, by solution
Suddenly in (2) two mouth flask, magnetic agitation is uniformly mixed it, constant temperature 6h；
(4) step (3) mixture is transferred in the hydrothermal reaction kettle of 150mL polytetrafluoroethyllining lining, hydro-thermal is anti-at 150 DEG C
5h is answered, after taking out precipitating, is successively washed 5 times with deionized water and ethyl alcohol, product dries 7h at 90 DEG C to get nanometer after washing
Tinbase expanding fire retardant；The thermogravimetric analysis of nanometer tin based flameproofing (TGA) figure made from the present embodiment is shown in that Fig. 2, Fig. 2 show to be prepared into
To the pyrolysis temperature of product be about 225 DEG C, illustrate that flame-retardant composition begins to react in lower temperature, to protect substrate.
Being used to prepare flame retardant test material in flexible PVC for fire retardant made from the present embodiment, (additive amount is flexible PVC matter
The 5% of amount), as a result the oxygen index (OI) of flexible PVC increases to 27.6 from 23.7.
Embodiment 3:
(1) 0.02mol stannous chloride, cetyl trimethylammonium bromide (CTAB), 80mL deionization are added in two mouth flask
Then mixture is placed in 85 DEG C of water-baths and keeps the temperature, wherein stannous chloride and polyethylene glycol to being completely dissolved by water, ultrasonic 20min
Mass ratio be 300:1；
(2) 0.03mol ammonium hydrogen phosphate is dispersed in 20mL deionized water, dispersion liquid is added dropwise to being uniformly dispersed by ultrasonic 10min
Into step (1) two mouth flask, magnetic agitation is uniformly mixed it, constant temperature 8h；
(3) 0.005mol magnesium chloride is dissolved in 20mL deionized water, solution is added drop-wise to by ultrasonic 10min to being completely dissolved
In step (2) two mouth flask, magnetic agitation is uniformly mixed it, constant temperature 5h；
(4) step (3) mixture is transferred in the hydrothermal reaction kettle of 150mL polytetrafluoroethyllining lining, hydro-thermal is anti-at 130 DEG C
10h is answered, after taking out precipitating, is successively washed 4 times with deionized water and ethyl alcohol, product dries 10h at 80 DEG C to get receiving after washing
Meter Xi Ji expanding fire retardant；The microscopic appearance figure of nanometer tin based flameproofing made from the present embodiment is shown in Fig. 3；
Being used in flexible PVC prepare flame retardant test material for fire retardant made from the present embodiment, (additive amount is flexible PVC quality
5%), as a result the oxygen index (OI) of flexible PVC increases to 27.4 from 23.7.
Embodiment 4:
(1) 0.02mol tin tetrachloride, polyethylene glycol (PEG-6000), 80mL deionized water, ultrasound are added in two mouth flask
Then mixture is placed in 90 DEG C of water-baths and keeps the temperature, wherein the mass ratio of stannous chloride and polyethylene glycol to being completely dissolved by 20min
For 200:1；
(2) 0.04mol ammonium polyphosphate is dispersed in 20mL deionized water, dispersion liquid is added dropwise to being uniformly dispersed by ultrasonic 10min
Into step (1) two mouth flask, magnetic agitation is uniformly mixed it, constant temperature 6h；
(3) 0.008mol iron chloride is dissolved in 20mL deionized water, solution is added drop-wise to by ultrasonic 10min to being completely dissolved
In step (2) two mouth flask, magnetic agitation is uniformly mixed it, constant temperature 4h；
(4) step (3) mixture is transferred in the hydrothermal reaction kettle of 150mL polytetrafluoroethyllining lining, hydro-thermal is anti-at 140 DEG C
8h is answered, after taking out precipitating, is successively washed 4 times with deionized water and ethyl alcohol, product dries 8h at 85 DEG C to get nanometer after washing
Tinbase expanding fire retardant；The microscopic appearance figure of nanometer tin based flameproofing made from the present embodiment is shown in Fig. 4；
Being used in flexible PVC prepare flame retardant test material for fire retardant made from the present embodiment, (additive amount is flexible PVC quality
5%), as a result the oxygen index (OI) of flexible PVC increases to 27.1 from 23.7.
Embodiment 5:
(1) in two mouth flask be added 0.03mol tin tetrachloride, stearic acid, 80mL deionized water, ultrasonic 20min to completely it is molten
Mixture, is then placed in 95 DEG C of water-baths and keeps the temperature by solution, and wherein the mass ratio of stannous chloride and polyethylene glycol is 400:1；
(2) 0.03mol ammonium polyphosphate is dispersed in 20mL deionized water, dispersion liquid is added dropwise to being uniformly dispersed by ultrasonic 10min
Into step (1) two mouth flask, magnetic agitation is uniformly mixed it, constant temperature 6h；
(3) 0.004mol calcium chloride is dissolved in 20mL deionized water, solution is added drop-wise to by ultrasonic 10min to being completely dissolved
In step (2) two mouth flask, magnetic agitation is uniformly mixed it, constant temperature 4h；
(4) step (3) mixture is transferred in the hydrothermal reaction kettle of 150mL polytetrafluoroethyllining lining, hydro-thermal is anti-at 135 DEG C
8h is answered, after taking out precipitating, is successively washed 3 times with deionized water and ethyl alcohol, product dries 7h at 90 DEG C to get nanometer after washing
Tinbase expanding fire retardant；
Being used in flexible PVC prepare flame retardant test material for fire retardant made from the present embodiment, (additive amount is flexible PVC quality
5%), as a result the oxygen index (OI) of flexible PVC increases to 27.2 from 23.7.
Claims (6)
1. the preparation method of a kind of nanometer of tinbase expanding fire retardant, which is characterized in that specific step is as follows:
(1) in deionized water by tin source and the dissolution of table activating agent, then mixture is placed in 75 ~ 95 to being completely dissolved by ultrasound
It is kept the temperature in DEG C water-bath；
(2) it disperses nitrogenated flame retardant in deionized water, dispersant liquid drop is added to step (1) and mixed by ultrasound to being uniformly dispersed
In object, stirring is uniformly mixed it, 4 ~ 8h of constant temperature；
(3) soluble metallic salt is dissolved in deionized water, solution is added drop-wise to step (2) and mixed by ultrasound to being completely dissolved
In object, stirring is uniformly mixed it, 4 ~ 8h of constant temperature；
(4) step (3) mixture is transferred in the hydrothermal reaction kettle of polytetrafluoroethyllining lining, hydro-thermal is anti-at 120 ~ 150 DEG C
Answer 4 ~ 12h, after taking out precipitating, successively washed 3 ~ 5 times with deionized water and ethyl alcohol, after washing product dry 7 at 70 ~ 90 DEG C ~
12h is to get nanometer tinbase expanding fire retardant.
2. the preparation method of according to claim 1 nanometer of tinbase expanding fire retardant, it is characterised in that: table activating agent is ten
One of six alkyl trimethyl ammonium bromides, polyethylene glycol, neopelex, stearic acid.
3. the preparation method of according to claim 1 nanometer of tinbase expanding fire retardant, it is characterised in that: tin source is stannic acid
One of sodium, potassium stannate, stannous chloride, tin tetrachloride.
4. the preparation method of according to claim 1 nanometer of tinbase expanding fire retardant, it is characterised in that: nitrogenated flame retardant is
One of melamine, ammonium polyphosphate, ammonium hydrogen phosphate.
5. the preparation method of according to claim 1 nanometer of tinbase expanding fire retardant, it is characterised in that: soluble metallic salt
For one of zinc salt, magnesium salts, molysite, calcium salt.
6. the preparation method of according to claim 1 nanometer of tinbase expanding fire retardant, it is characterised in that: tin source and nitrogen system hinder
The molar ratio of agent is fired for 1:4 ~ 4:1, and the molar ratio of soluble metallic salt and tin source is 1:1 ~ 1:20, the matter of tin source and table activating agent
Amount is than being 200:1 ~ 500:1.
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