CN104119614B - The Synthesis and applications of zinc hydroxyl stannate-polygorskite-trithiocyanuric acid compound smoke inhibition fire retardant - Google Patents

The Synthesis and applications of zinc hydroxyl stannate-polygorskite-trithiocyanuric acid compound smoke inhibition fire retardant Download PDF

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CN104119614B
CN104119614B CN201410394534.7A CN201410394534A CN104119614B CN 104119614 B CN104119614 B CN 104119614B CN 201410394534 A CN201410394534 A CN 201410394534A CN 104119614 B CN104119614 B CN 104119614B
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polygorskite
trithiocyanuric acid
hydroxyl stannate
zinc hydroxyl
retardant
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CN104119614A (en
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雷自强
罗鑫圣
张哲�
武广瑞
赵睿
蔡文婧
雷蕾
周鹏鑫
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Northwest Normal University
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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
    • C08K3/34—Silicon-containing compounds
    • C08K3/346—Clay
    • 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
    • C08K5/00—Use of organic ingredients
    • C08K5/36—Sulfur-, selenium-, or tellurium-containing compounds
    • C08K5/37—Thiols
    • 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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  • Health & Medical Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
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Abstract

Does is the invention provides a kind of zinc hydroxyl stannate-polygorskite-trithiocyanuric acid compound smoke inhibition fire retardant with good smoke-inhibiting flame retardant performance, that (its properity is see CN102515185 by zinc hydroxyl stannate-palygorskite mixture? A) carry out composite with the mass ratio of 20:1 ~ 1:1 with trithiocyanuric acid and obtain.Experiment shows, trithiocyanuric acid and zinc hydroxyl stannate-palygorskite mixture have good synergy, with it for fire retardant material prepared by additive becomes carbon respond well, can be widely used in the modification of plastics and all kinds of rubber.

Description

The Synthesis and applications of zinc hydroxyl stannate-polygorskite-trithiocyanuric acid compound smoke inhibition fire retardant
Technical field
The present invention relates to a kind of composite flame-retardant agent, particularly relate to the preparation method of a kind of zinc hydroxyl stannate-polygorskite-trithiocyanuric acid compound smoke inhibition fire retardant; What the present invention also related to this compound smoke inhibition fire retardant simultaneously is preparing the application in flame retardant type macromolecular material.
Background technology
In recent decades, the macromolecular materials such as plastics, rubber, synthon and goods thereof have obtained vigorous growth, they replace traditional steel, metal products, cement and the natural polymer such as timber, cotton rapidly, are widely used in each department of the national economy such as industry, agricultural, military affairs.2013 turnout being only plastics just reach 2.99 hundred million tons, and its volume substantially exceeds the steel volume produced the same year, has been that people's everyday life is necessary.But, because most of macromolecular material is inflammable, increasing use macromolecular material, it is very severe that it applies the fire hazard situation caused in the world, and not only release a large amount of heat during superpolymer burning, and be usually attended by a large amount of cigarettes and toxic gas and produce, serious infringement is caused to the life security of people and property.Therefore, preparing high performance fire retardant material has been problem social in the urgent need to address.
At present, the method preparing the macromolecular material of high property flame retardant properties adds fire retardant to carry out modification to it.In numerous fire retardant additive without halogen, zinc hydroxyl stannate [ZnSn (OH) 6, ZHS] and there is nontoxic, fire-retardant, to press down cigarette advantage, meet the requirement of current Green Flammability agent, the researchdevelopment of researcher to it is very fast, likely becomes the substitute of antimonous oxide.Palygorskite clay, due to special crystalline structure and character, as a kind of nanometer inorganic filler, can play good flame-retardant smoke inhibition effect, extensively be studied by researcher.CN102515185A provides a kind of Zinc hydroxystannate-palygorskite clay compound, and it for raw material with three chloride hydrate zinc, tin chloride and palygorskite clay, adopts coprecipitation method preparation and obtain.This mixture has high flame resistance and high smoke suppressing, for the preparation of flame-proof polyvinyl chloride material material, can replace the anti-flaming smoke-inhibiting agent of current antimony series, obtain the macromolecular material of flame retardant properties, smoke suppressing and good mechanical properties.But zinc hydroxyl stannate crystal formation prepared by the method is complete, but crystal particle diameter is comparatively large, there is consumption large, destroy the problems such as serious to material mechanical performance as anti-flaming smoke-inhibiting agent.
Compound in triazine class, due to nitrogen content high (51.83%), has the advantages such as density is high, Heat stability is good, can be used as gas-evolution agent, excellent fire retardant material char-forming agent.In numerous compound in triazine class, (chemical name is 1 to trithiocyanuric acid, 3,5-triazine-2,4,6-(1H.3H.5H) three mercaptan) because self nontoxic, easy dispersion, consumption are little and the technological operation feature such as safely, be widely used in polymer modification, and have no the report that document had the flame retardant properties research about trithiocyanuric acid but it is used alone does not contribute the flame retardant resistance of matrix material, therefore.
Summary of the invention
The object of the invention is for problems of the prior art, and utilize the feature of trithiocyanuric acid, a kind of preparation method with the zinc hydroxyl stannate-polygorskite-trithiocyanuric acid compound smoke inhibition fire retardant of good smoke-inhibiting flame retardant performance is provided;
Another object of the present invention is to provide a kind of zinc hydroxyl stannate-polygorskite-trithiocyanuric acid compound smoke inhibition fire retardant and is preparing the application in flame retardant type macromolecular material.
(1) preparation of compound smoke inhibition fire retardant
1, the preparation of Zinc hydroxystannate-palygorskite clay compound: by ZnCl 23H 2o is soluble in water, adds ZnCl 23H 2the palygorskite clay that O quality is 5 ~ 20 times, is heated to 80 ~ 95 DEG C, stirs 20 ~ 40min; PH=5.0 ~ 6.4 of regulation system; Add ZnCl 23H 2the SnCl that O quality is 2 ~ 5 times 45H 2o, stirs 10 ~ 25min; Regulate final pH=9.0 ~ 9.4 of reaction system, room temperature crystallization 3 ~ 5h, filtering precipitate, washing, dry, grinding, obtain Zinc hydroxystannate-palygorskite clay compound, its properity is see CN102515185A.
2, the preparation of compound smoke inhibition fire retardant: zinc hydroxyl stannate-palygorskite and trithiocyanuric acid are carried out composite with the mass ratio of 20:1 ~ 1:1 and get final product.
In compound smoke inhibition fire retardant, zinc hydroxyl stannate-palygorskite mainly plays and presses down cigarette effect, trithiocyanuric acid mainly plays the effect of carbon forming agent, produces well synergy, make the flame retardant properties of compound smoke inhibition fire retardant and smoke suppressing effect have great raising after the two compound, and, the one-tenth carbon of fire retardant material is respond well, plastics can be widely used in as polypropylene (PP), polyethylene (PE), polyvinyl chloride (PVC), acrylonitrile-butadiene-styrene copolymer (ABS), polystyrene (PS), polyethylene terephthalate (PET), polyamide (PA), in the modification of the general-purpose plastics such as polycarbonate (PC), also all kinds of rubber can be widely used in, as natural rubber (NR), styrene-butadiene rubber(SBR) (SBR), cis-1,4-polybutadiene rubber (BR), polyisoprene rubber (IR), paracril (NBR), isoprene-isobutylene rubber (IIR), chloroprene rubber (CR), in the modification of ethylene-propylene rubber(EPR) (EPDM) and acrylic elastomer (ACM) etc.
(2) preparation of flame retardant type macromolecular material and performance test
1, the preparation of flame retardant type macromolecular material: zinc hydroxyl stannate-polygorskite-trithiocyanuric acid compound smoke inhibition fire retardant is added in macromolecular material matrix, obtains flame retardant type macromolecular material by the method for melting mixing; Described macromolecular material matrix is plastics or rubber; The addition of described zinc hydroxyl stannate-polygorskite-mercaptan composite flame-retardant agent is 20% ~ 45% of macromolecular material substrate quality.
2, the test of performance index: for modified polypropene, is described the flame retardant properties of the flame retardant type macromolecular material prepared for additive with zinc hydroxyl stannate-polygorskite-trithiocyanuric acid composite flame-retardant agent, smoke suppressing and mechanical property.
(1) flame retardant properties: according to the limiting oxygen index(LOI) of GB/T2406.2-2009 test sample; According to the horizontal vertical combustionproperty of GB/T2408-2008 test sample.Result is as follows: more than 34, and horizontal firing reaches HB-a level, and vertical combustion reaches UL94V-0 level.Meet completely in GB/T8624-1997 and reach B about structure material burning rank 1regulation and YD/T1113-2001 in about electric wire skin material burning regulation.
(2) smoke density: according to the smoke density of GB/T8323.2-2008 test sample.Under nonflame condition, smoke density is less than 120.
(3) mechanical property: the test carrying out tensile strength and elongation at break according to GB1040, test result is: tensile strength is all at more than 11.5MPa, and elongation at break is all more than 125%.Material properties meets the regulation about electric wire coating material mechanical property in industry standard YD/T1113-2001.
In sum, the composite flame-proof hinge structure that prepared by the present invention has better flame retardant properties, smoke suppressing.With it for additive, the modified polymer material of preparation has good flame retardant properties, smoke suppressing and mechanical property.
Embodiment
Below by specific embodiment, the preparation of composite flame-retardant agent of the present invention and flame retarded polymeric material and performance are described further.
embodiment 1
(1) preparation of zinc hydroxyl stannate-polygorskite mixture: by the ZnCl of 10g 23H 2o is dissolved in 100ml distilled water, adds 50g palygorskite clay (attapulgite), is heated to 80 DEG C, stirs 20min.With HCl regulation system pH=5.0; Add 20gSnCl 45H 2o, violent stirring 10min, regulate final pH=9.0 of reaction system, crystallization 3h under room temperature, filtering precipitate with NaOH, washing, then puts into baking oven and dry, and ground 300m sieve, obtains zinc hydroxyl stannate-polygorskite mixture;
(2) preparation of composite flame-retardant agent: zinc hydroxyl stannate-polygorskite mixture and trithiocyanuric acid are carried out composite with the mass ratio of 1:1 and get final product;
(3) preparation of modified polypropene: added to by the hydroxyl composite flame-retardant agent of above-mentioned preparation (addition is 20% of polypropylene quality) in polypropylene matrix, obtains flame-retardant polypropelene material by the common process of melting mixing and auxiliary agent;
(4) performance index of flame-retardant polypropelene: oxygen index is 38, and horizontal firing reaches HB-a level, and vertical combustion reaches UL94V-0 level, under nonflame condition, smoke density is 110, and tensile strength is 13MPa, and elongation at break is 140%.
Embodiment 2
(1) preparation of zinc hydroxyl stannate-polygorskite mixture: with embodiment 1;
(2) preparation of composite flame-retardant agent: zinc hydroxyl stannate-polygorskite mixture and trithiocyanuric acid are carried out composite with the mass ratio of 5:1 and get final product;
(3) preparation of modified polypropene: added to by the hydroxyl composite flame-retardant agent of above-mentioned preparation (addition is 30% of polypropylene quality) in polypropylene matrix, obtains flame-retardant polypropelene material by the common process of melting mixing and auxiliary agent;
(4) performance index of flame-retardant polypropelene: oxygen index is 37, and horizontal firing reaches HB-a level, and vertical combustion reaches UL94V-0 level, under nonflame condition, smoke density is 105, and tensile strength is 12.3MPa, and elongation at break is 141%.
Embodiment 3
(1) preparation of zinc hydroxyl stannate-polygorskite mixture: with embodiment 1;
(2) preparation of composite flame-retardant agent: zinc hydroxyl stannate-polygorskite mixture and trithiocyanuric acid are carried out composite with the mass ratio of 10:1 and get final product;
(3) preparation of modified polypropene: added to by the hydroxyl composite flame-retardant agent of above-mentioned preparation (addition is 40% of polypropylene quality) in polypropylene matrix, obtains flame-retardant polypropelene material by the common process of melting mixing and auxiliary agent;
(4) performance index of flame-retardant polypropelene: oxygen index is 39, and horizontal firing reaches HB-a level, and vertical combustion reaches UL94V-0 level, under nonflame condition, smoke density is 98, and tensile strength is 12MPa, and elongation at break is 135%.
Embodiment 4
(1) preparation of zinc hydroxyl stannate-polygorskite mixture: with embodiment 1;
(2) preparation of composite flame-retardant agent: zinc hydroxyl stannate-polygorskite mixture and trithiocyanuric acid are carried out composite with the mass ratio of 15:1 and get final product;
(3) preparation of modified polypropene: added to by the hydroxyl composite flame-retardant agent of above-mentioned preparation (addition is 45% of polypropylene quality) in polypropylene matrix, obtains flame-retardant polypropelene material by the common process of melting mixing and auxiliary agent;
(4) performance index of flame-retardant polypropelene: oxygen index is 40, and horizontal firing reaches HB-a level, and vertical combustion reaches UL94V-0 level, under nonflame condition, smoke density is 87, and tensile strength is 11.5MPa, and elongation at break is 125%.
Embodiment 5
(1) preparation of zinc hydroxyl stannate-polygorskite mixture: with embodiment 1;
(2) preparation of composite flame-retardant agent: zinc hydroxyl stannate-polygorskite mixture and trithiocyanuric acid are carried out composite with the mass ratio of 20:1 and get final product;
(3) preparation of modified polypropene: added to by the hydroxyl composite flame-retardant agent of above-mentioned preparation (addition is 30% of polypropylene quality) in polypropylene matrix, obtains flame-retardant polypropelene material by the common process of melting mixing and auxiliary agent;
(4) performance index of flame-retardant polypropelene: oxygen index is 34, and horizontal firing reaches HB-a level, and vertical combustion reaches UL94V-0 level, under nonflame condition, smoke density is 120, and tensile strength is 13.6MPa, and elongation at break is 131%.

Claims (2)

1. a preparation method for zinc hydroxyl stannate-polygorskite-trithiocyanuric acid compound smoke inhibition fire retardant, bezinc hydroxyl stannate-palygorskite mixture and trithiocyanuric acid are carried out composite with the mass ratio of 20:1 ~ 1:1 and obtain;
The preparation technology of described Zinc hydroxystannate-palygorskite clay compound is: by ZnCl 23H 2o is soluble in water, adds ZnCl 23H 2the palygorskite clay that O quality is 5 ~ 20 times, is heated to 80 ~ 95 DEG C, stirs 20 ~ 40min; PH=5.0 ~ 6.4 of regulation system; Add ZnCl 23H 2the SnCl that O quality is 2 ~ 5 times 45H 2o, stirs 10 ~ 25min; Regulate final pH=9.0 ~ 9.4 of reaction system, room temperature crystallization 3 ~ 5h, filtering precipitate, washing, dry, grinding, obtains Zinc hydroxystannate-palygorskite clay compound.
2. zinc hydroxyl stannate-polygorskite-trithiocyanuric acid compound smoke inhibition fire retardant that as claimed in claim 1 prepared by method is preparing the application in flame retardant type macromolecular material, it is characterized in that: zinc hydroxyl stannate-polygorskite-trithiocyanuric acid compound smoke inhibition fire retardant is added in macromolecular material matrix, obtains flame retardant type macromolecular material by the method for melting mixing;
The addition of described zinc hydroxyl stannate-polygorskite-trithiocyanuric acid composite flame-retardant agent is 20% ~ 45% of macromolecular material substrate quality; Described macromolecular material matrix is plastics.
CN201410394534.7A 2014-08-12 2014-08-12 The Synthesis and applications of zinc hydroxyl stannate-polygorskite-trithiocyanuric acid compound smoke inhibition fire retardant Active CN104119614B (en)

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CN107868281B (en) * 2017-11-28 2019-05-24 西北师范大学 A kind of preparation of hypo-aluminum orthophosphate doping vario-property palygorskite and application as fire retardant
CN113185754A (en) * 2021-05-07 2021-07-30 西北师范大学 Attapulgite/antimony trioxide hybrid material, preparation method thereof and application thereof in producing flame-retardant polymer composite material
CN113930029B (en) * 2021-10-25 2023-06-20 云南锡业集团（控股）有限责任公司研发中心 Halogen-free nano composite flame retardant and preparation method thereof
CN114702769B (en) * 2022-04-15 2023-06-09 上海大学 Reinforced flame-retardant microcapsule composite material and preparation method thereof

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