CN100350015C - Palygorskite compound flame retardant - Google Patents

Palygorskite compound flame retardant Download PDF

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Publication number
CN100350015C
CN100350015C CNB2005100416554A CN200510041655A CN100350015C CN 100350015 C CN100350015 C CN 100350015C CN B2005100416554 A CNB2005100416554 A CN B2005100416554A CN 200510041655 A CN200510041655 A CN 200510041655A CN 100350015 C CN100350015 C CN 100350015C
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China
Prior art keywords
flame retardant
polygorskite
palygorskite
composite
paligorskite
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CNB2005100416554A
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CN1654599A (en
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雷自强
罗居杰
杨志旺
白雁斌
马恒昌
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Northwest Normal University
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Northwest Normal University
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Abstract

The present invention provides a paligorskite composite flame retardant which is prepared by mixing pulverized paligorskite powder of 100 to 5000 meshes and a composite agent according to a certain proportion. Due to the cellular structure of palygorskite, the palygorskite composite flame retardant has a strong adsorption effect on gas, and can isolate and insulate heat and block heat transfer. Simultaneously, due to favorable water absorption performance and water retention performance, palygorskite can generate water vapor at high temperature to block oxygen, and the palygorskite composite flame retardant has a favorable flame retardant effect. Compared with other flame retardants, the palygorskite composite flame retardant has the advantages of no volatilization, lasting effect, low price, little smoke and no toxicity, and is an ideal nuisance-free flame retardant material.

Description

A kind of paligorskite composite combustion inhibitor
Technical field
The present invention relates to a kind of additive, relate in particular to a kind of fire retardant, be specifically related to a kind of paligorskite composite combustion inhibitor.
Background technology
Palygorskite clay is to be the silicate clay mineral of main component with the polygorskite, because the formation condition harshness, thereby be worldwide rare environment mineral material.The world has the polygorskite of extraction value mainly to be distributed in a few countries such as China, the U.S., Spain, Senegal, France, Australia, Mexico, Russia.China's polygorskite reserves account for more than 95% of world saving, and wherein the polygorskite distant view reserves of Linze county, Gansu Province slab bridge township's recent findings are about 1,100,000,000 tons, account for more than 85% of world's distant view reserves.Show through quantitative analysis of X-ray diffraction and TEM (transmission electron microscope) analysis, polygorskite content is 25%~51%, its monocrystalline mostly is needle-like, fibrous, about 20~the 80nm of crystal diameter, be about 0.5~5 micron, it is the micropore of 0.32 * 0.73nm that the aperture consistent with its length direction arranged in the crystal, and out-of-shape nano-micrometre level micropore is arranged between the crystal, belongs to typical natural nano-submicron mineral fibre.Polygorskite density low (2.31-2.37), paler colour can not have a strong impact on its weight and the transparency with polymer after compound; Polygorskite hardness 2-2.5 is processed into the nano-micrometre grade particles easily; Its porous and hollow structure are the compound condition of having created of chemical modification and material.
Polygorskite is mainly used in water technology and the fertilizer synthetic technology as a kind of additive, and it does not at home and abroad appear in the newspapers as yet as the application of fire retardant.
Fire retardant material is a kind of auxiliary agent that can stop material to ignite or suppress propagation of flame, and it is that the needs with macromolecular material grow up in later stage the 1950's.Traditional fire retardant is as the still widely used bromide fire retardant of China, though have good flame retardant resistance, in case but presence of fire, because thermolysis and burning will produce a large amount of smog and deleterious corrosive gases, thereby hinder fire fighting and personnel's evacuation, and corrosion instrument and equipment.Though phosphorus flame retardant toxicity and cigarette amount are all less, it requires to be contained a large amount of H, O element in the fire retardant material structure, and could dewater forms charring layer, thereby its application also is restricted.The amount of being fuming is low during the inorganic combustion inhibitor burning, and does not produce poisonous, corrosive gases, is the optimal fire retardant of studying and using at present.American-European and Japanese, inorganic fire-retardant material has accounted for 50%~64% of all flame retardant products, mainly is Al (OH) 3And Mg (OH) 2Be the material of additive, but these interpolation prices are high, are unfavorable for applying.
The microvoid structure of polygorskite, make it strong adsorption be arranged to gas, the heat insulation thermal insulation of hollow can be blocked the transmission of heat, its suction and water retention property, at high temperature can produce water vapour blocking-up oxygen, polygorskite itself is non-volatile, and effect is lasting, cheap, smog is little, has fire-retardant, as to press down cigarette and reduction toxic gas function concurrently.So polygorskite nuisanceless fire retardant material that is ideal.
Summary of the invention
The paligorskite composite combustion inhibitor that the purpose of this invention is to provide a kind of efficient, inexpensive, low toxicity, low cigarette, non-environmental-pollution
Purpose of the present invention can realize by following measure:
A kind of paligorskite composite combustion inhibitor is by being crushed to 100~5000 purpose polygorskite powders and the composite dose of mixed with 1: 1~1: 10 forms.
Described composite dose is magnesium hydroxide and/or trimeric cyanamide; When being the mixture of magnesium hydroxide and trimeric cyanamide for composite dose, the ratio of magnesium hydroxide and trimeric cyanamide is: 1: 0.1~1: 10.
The present invention compared with prior art has the following advantages:
1, the present invention mixes with natural broken thread stone and the composite dose of mode with mechanical blending, because the microvoid structure of polygorskite has strong adsorption to gas, and the heat insulation thermal insulation of energy, the transmission of blocking-up heat is simultaneously because its good suction and water retention property at high temperature can produce water vapour blocking-up oxygen, make it have good flame-retardant effect, compare with other fire retardants, polygorskite itself is non-volatile, and effect is lasting, cheap, smog is little, nontoxic, be the nuisanceless fire retardant material of ideal.
2, technology of the present invention is simple, cost is low, is the perfect additive of producing flame retardant products such as plastics, rubber.
Embodiment
Further specify the preparation method of paligorskite composite combustion inhibitor below in conjunction with embodiment, and by with natural broken thread masonry being the flame retardant effect of the broken thread of the anti-flaming polypropylene material explanation stone of fire retardant preparation:
Embodiment 1: natural polygorskite is crushed to 100~5000 orders (granularity is 0.26-2.um) after selected, again polygorskite powder and magnesium hydroxide is promptly got paligorskite composite combustion inhibitor with 1: 1 ratio with the mode thorough mixing of mechanical blending.With above-mentioned gained polygorskite compound flame retardant and polypropylene with 45%, 55% weight ratio thorough mixing and with Shooting Technique injection moulding on injection moulding machine of routine, flame-retardant polypropylene composite material.It is as follows to measure its each performance index:
Oxygen index can reach 28; Combustionproperty is the UL94-1 level
Embodiment 2: natural polygorskite is crushed to 100~5000 orders (granularity is 0.26-2.um) after selected, again polygorskite powder and trimeric cyanamide is promptly got paligorskite composite combustion inhibitor with 1: 2 ratio with the mode thorough mixing of mechanical blending.With above-mentioned gained polygorskite compound flame retardant and polypropylene with 40%, 60% weight ratio thorough mixing and with Shooting Technique injection moulding on injection moulding machine of routine, flame-retardant polypropylene composite material.It is as follows to measure its each performance index:
Oxygen index can reach 30; Combustionproperty is the UL94-0 level
Embodiment 3: natural polygorskite is crushed to 100~5000 orders (granularity is 0.26-2.um) after selected, again the mixture (ratio of magnesium hydroxide and trimeric cyanamide is 1: 0.1) of polygorskite powder and magnesium hydroxide and trimeric cyanamide is promptly got paligorskite composite combustion inhibitor with 1: 3 ratio with the mode thorough mixing of mechanical blending.With above-mentioned gained polygorskite compound flame retardant and polypropylene with 30%, 70% weight ratio thorough mixing and with Shooting Technique injection moulding on injection moulding machine of routine, flame-retardant polypropylene composite material.It is as follows to measure its each performance index:
It is the UL94-0 level that oxygen index can reach 31 combustionproperties
Embodiment 4: natural polygorskite is crushed to 100~5000 orders (granularity is 0.26-2.um) after selected, again polygorskite powder and trimeric cyanamide is promptly got paligorskite composite combustion inhibitor with 1: 4 ratio with the mode thorough mixing of mechanical blending.With above-mentioned gained polygorskite compound flame retardant and polypropylene with 20%, 80% weight ratio thorough mixing, with Shooting Technique injection moulding on injection moulding machine of routine, flame-retardant polypropylene composite material.It is as follows to measure its each performance index:
It is the UL94-0 level that oxygen index can reach 28 combustionproperties
Embodiment 5: natural polygorskite is crushed to 100~5000 orders (granularity is 0.26-2.um) after selected, again the mixture (ratio of magnesium hydroxide and trimeric cyanamide is 1: 0.5) of polygorskite powder and magnesium hydroxide and trimeric cyanamide is promptly got paligorskite composite combustion inhibitor with 1: 5 ratio with the mode thorough mixing of mechanical blending.With above-mentioned gained polygorskite compound flame retardant and polypropylene with 10%, 90% weight ratio thorough mixing, and with Shooting Technique injection moulding on injection moulding machine of routine, flame-retardant polypropylene composite material.It is as follows to measure its each performance index:
It is the UL94-0 level that oxygen index can reach 28 combustionproperties
Embodiment 6: natural polygorskite is crushed to 100~5000 orders (granularity is 0.26-2.um) after selected, again the mixture (ratio of magnesium hydroxide and trimeric cyanamide is 1: 1) of polygorskite powder and magnesium hydroxide and trimeric cyanamide is promptly got paligorskite composite combustion inhibitor with 1: 6 ratio with the mode thorough mixing of mechanical blending.With above-mentioned gained polygorskite compound flame retardant and polypropylene with 5%, 95% weight ratio thorough mixing, and with Shooting Technique injection moulding on injection moulding machine of routine, flame-retardant polypropylene composite material.It is as follows to measure its each performance index:
It is the UL94-0 level that oxygen index can reach 28 combustionproperties
Embodiment 7: natural polygorskite is crushed to 100~5000 orders (granularity is 0.26-2.um) after selected, again the mixture (ratio of magnesium hydroxide and trimeric cyanamide is 1: 3) of polygorskite powder and magnesium hydroxide and trimeric cyanamide is promptly got paligorskite composite combustion inhibitor with 1: 7 ratio with the mode thorough mixing of mechanical blending; With gained polygorskite compound flame retardant and polypropylene with 40%, 60% weight ratio thorough mixing, and with Shooting Technique injection moulding on injection moulding machine of routine, flame-retardant polypropylene composite material.It is as follows to measure its each performance index:
It is the UL94-0 level that oxygen index can reach 28 combustionproperties
Embodiment 8: natural polygorskite is crushed to 100~5000 orders (granularity is 0.26-2.um) after selected, again the mixture (ratio of magnesium hydroxide and trimeric cyanamide is 1: 5) of polygorskite powder and magnesium hydroxide and trimeric cyanamide is promptly got paligorskite composite combustion inhibitor with 1: 8 ratio with the mode thorough mixing of mechanical blending.With gained polygorskite compound flame retardant and polypropylene with 40%, 60% weight ratio thorough mixing, and with Shooting Technique injection moulding on injection moulding machine of routine, flame-retardant polypropylene composite material.It is as follows to measure its each performance index:
Oxygen index can reach 28, and combustionproperty is the UL94-0 level
Embodiment 9: natural polygorskite is crushed to 100~5000 orders (granularity is 0.26-2.um) after selected, again the mixture (ratio of magnesium hydroxide and trimeric cyanamide is 1: 8) of polygorskite powder and magnesium hydroxide and trimeric cyanamide is promptly got paligorskite composite combustion inhibitor with 1: 9 ratio with the mode thorough mixing of mechanical blending.With gained polygorskite compound flame retardant and polypropylene with 40%, 60% weight ratio thorough mixing, and with Shooting Technique injection moulding on injection moulding machine of routine, flame-retardant polypropylene composite material.It is as follows to measure its each performance index:
Oxygen index can reach 28, and combustionproperty is the UL94-0 level
Embodiment 10: natural polygorskite is crushed to 100~5000 orders (granularity is 0.26-2.um) after selected, again the mixture (ratio of magnesium hydroxide and trimeric cyanamide is 1: 10) of polygorskite powder and magnesium hydroxide and trimeric cyanamide is promptly got paligorskite composite combustion inhibitor with 1: 10 ratio with the mode thorough mixing of mechanical blending.With polygorskite compound flame retardant and polypropylene with 40%, 60% weight ratio thorough mixing, and with Shooting Technique injection moulding on injection moulding machine of routine, flame-retardant polypropylene composite material.It is as follows to measure its each performance index:
Oxygen index can reach 28, and combustionproperty is the UL94-0 level.

Claims (2)

1, a kind of paligorskite composite combustion inhibitor is characterized in that: it is by being crushed to 100~5000 purpose polygorskite powders and the composite dose of mixed with 1: 1~1: 10 forms; Described composite dose is magnesium hydroxide and/or trimeric cyanamide.
2, paligorskite composite combustion inhibitor as claimed in claim 1 is characterized in that: during described composite dose of mixture for magnesium hydroxide and trimeric cyanamide, the ratio of magnesium hydroxide and trimeric cyanamide is: 1: 0.1~1: 10.
CNB2005100416554A 2005-01-18 2005-01-18 Palygorskite compound flame retardant Expired - Fee Related CN100350015C (en)

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Families Citing this family (9)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN100360640C (en) * 2005-08-27 2008-01-09 西北师范大学 Paligorskite composite combustion inhibitor
CN100335551C (en) * 2005-08-27 2007-09-05 西北师范大学 Paligorskite ethene-vinyl acetate composite flame-proof material
CN101195694B (en) * 2007-12-22 2011-01-19 西北师范大学 Degradable composite plastics and method for producing the same
CN102010585B (en) * 2010-11-16 2012-04-04 淮阴师范学院 Preparation method of efficient and environment-friendly composite fire retardant
CN102352057B (en) * 2011-09-08 2013-05-08 西北师范大学 Non-halogen composite flame retardant and application thereof in preparation of flame retardant thermoplastic elastomer composite
CN103483878B (en) * 2013-09-09 2015-04-01 中国地质科学院郑州矿产综合利用研究所 Dolomite attapulgite composite reinforced flame retardant and preparation method thereof
CN104119614B (en) * 2014-08-12 2016-04-13 西北师范大学 The Synthesis and applications of zinc hydroxyl stannate-polygorskite-trithiocyanuric acid compound smoke inhibition fire retardant
CN105385036A (en) * 2015-12-17 2016-03-09 西北师范大学 Halogen-free smoke suppression fire retardant used for preparation of polypropylene material
CN105542230B (en) * 2016-02-02 2018-01-09 中国地质科学院郑州矿产综合利用研究所 Halogen-free flame retardant and preparation method thereof

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JPS5921799A (en) * 1982-07-21 1984-02-03 株式会社大阪パツキング製造所 Incombustible and fire retardant paper
JPS6166764A (en) * 1984-09-11 1986-04-05 Toyota Central Res & Dev Lab Inc Corrosion-proofing paint
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