CN100360640C - Paligorskite composite combustion inhibitor - Google Patents
Paligorskite composite combustion inhibitor Download PDFInfo
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- CN100360640C CN100360640C CNB2005100431696A CN200510043169A CN100360640C CN 100360640 C CN100360640 C CN 100360640C CN B2005100431696 A CNB2005100431696 A CN B2005100431696A CN 200510043169 A CN200510043169 A CN 200510043169A CN 100360640 C CN100360640 C CN 100360640C
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- palygorskite
- flame retardant
- polygorskite
- composite
- paligorskite
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Abstract
The present invention provides a palygorskite composite flame retardant which is prepared by mechanically mixing pulverized paligorskite powder of 100 to 5000 meshes and a composite agent of polyphosphoric acid amine and/or pentaerythritol according to a certain proportion. Palygorskite is an aqueous zeopan mineral, which is widely used in the industry field because of good physicochemistry properties. 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 favorable flame retardation action. The palygorskite composite flame retardant also has the performance of light weight, white color, sterilization, high adsorption force, etc. Compared with other flame retardants, the palygorskite composite flame retardant has the advantages of strong flame retardation effect, high temperature resistance, wear resistance, lasting effect, low price, little smoke and no toxicity. The palygorskite composite flame retardant is a nuisance-free flame retardant material, and can be applied to electric appliances, especially a heat insulation material of civil electric appliances.
Description
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, and the polygorskite mineral are generally at high basicity (PH=8 scholar), suitable salinity, certain temperature and medium SiO
2, Al
2O
3, the suitable environment of MgO three component ratios could generate down, and a handful of countries or such mineral deposit of regional output are only arranged at present in the world, owing to the formation condition harshness, thereby is worldwide rare environment mineral material.It not only only has a few countries (area) to find to have the mineral deposit of industrial significance in the world.But also have many good physical and chemical performances and industrial use, high economic worth is arranged.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.Palygorskite clay is divided by the output environment in the world the palygorskite clay of palygorskite clay, the Lu Yuan clastic sediment rock of palygorskite clay, the carbonate of evaporitic rock in building in building in building, the palygorskite clay in the palygorskite clay in the abyssal sediment, hypergene soil in palygorskite clay and carbonate crack or the solution cavity.Palygorskite clay has good adsorptivity, multiple properties such as colloidality and catalytic.Polygorskite is the magnesia silicate minerals of a kind of aqueous layer chain, and its basic structural unit is 2: 1 stratotypes, the octahedra component units layer of promptly two-layer silicon-oxy tetrahedron folder one deck magnesia.The tetrahedral sheet angle is pushed up at a certain distance direction and is put upside down and the form layers chain-like structure in each 2: 1 layers.At tetrahedron bar interband, form the duct parallel with the C direction of principal axis, be filled with zeolite water in the duct.Compare with other clay minerals, polygorskite has bigger specific surface area, and adsorptivity is stronger.Have four types water in the polygorskite, i.e. planar water (H
2O-), zeolite water (H
2O+), combination water (OH
2) and water of constitution (OH), it raises and dehydration successively with temperature, water of constitution dehydration temperaturre height wherein, and promptly resistance toheat is good.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 is that a class can stop macromolecular materials such as plastics to be ignited or suppresses the auxiliary agent of propagation of flame.Phase early 1950s, Hooker chemical company develops flameproof unsaturated polyester with the acid of reactive monomer chlorine mattress, and the new way of flame retardant area has been opened up in this research work, new subsequently brominated and (or) the reaction-type flame-retarding monomer of phosphorus constantly occurs.Developed the multiple packing type of thermoplastics that is applicable to the sixties in succession and added fire retardant, wherein most of is that bromine is.Early 1970s, the production of this based flame retardant and application obtained flourish to the mid-80.Since 1986, carried out the toxicity of polybromodiphenyl ether based flame retardant and the dispute of environmental problem in the flame retardant area, promoted the research and development of the novel substitute of decabrominated dipheny ethers (comprising expansion type flame retardant and halogen-free flame retardants).But along with to the raising of fire-retardant requirement and the enhancing of environmental consciousness, fire retardant non-halogen, press down cigarette and attenuation has become the frontier nature problem of fire-retardant research field at present and in the future, requirement develops that performance is more excellent, better effects if, the BACN of environmental protection more, has carried out a large amount of research in this field both at home and abroad at present.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 makes it to gas strong adsorption be arranged, and the heat insulation thermal insulation of hollow can be blocked the transmission of heat, and its suction and water retention property at high temperature can produce water vapour blocking-up oxygen, and good heat resistance.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 polyphosphoric acid amine and/or tetramethylolmethane.
When being the mixture of polyphosphoric acid amine and tetramethylolmethane for composite dose, the ratio of polyphosphoric acid amine and tetramethylolmethane is: 1: 0.1～1: 10.
The present invention compared with prior art has the following advantages:
1, the present invention mixes with natural polygorskite and the composite dose of mode with mechanical blending, because because the microvoid structure of polygorskite, gas there is strong adsorption, 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, the oxygen index height makes it have good fire retardation.
2, because non-volatile, the effect of polygorskite itself is lasting, stable performance, little, the nontoxicity of smog, having fire-retardant, as to press down cigarette and reduction toxic gas function concurrently, is a kind of non-environmental-pollution fire retardant material.
3, production technique of the present invention is simple, cost is low, can be applicable to the lagging material of electrical equipment, especially civil electric appliance.
Embodiment
Further specify brokenly the flame retardant effect of thread stone below by the flame-proof ethylene-acetate ethylene copolymer material that with natural slope thread masonry is the fire retardant preparation:
Embodiment 1: natural polygorskite is crushed to 100～5000 orders (granularity is 0.26-2.0um) after selected, again polygorskite powder and polyphosphoric acid amine 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 ethylene-vinyl acetate copolymer with 45%, 55% weight ratio thorough mixing and with Shooting Technique injection moulding on injection moulding machine of routine, flame-proof ethylene-acetate ethylene copolymer matrix material.It is as follows to measure its each performance index:
Oxygen index can reach 28; Combustionproperty is the UL94-0 level.
Embodiment 2: natural polygorskite is crushed to 100～5000 orders (granularity is 0.26-2.0um) after selected, again polygorskite powder and tetramethylolmethane 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 ethylene-vinyl acetate copolymer with 45%, 55% weight ratio thorough mixing and with Shooting Technique injection moulding on injection moulding machine of routine, flame-proof ethylene-acetate ethylene copolymer matrix material.It is as follows to measure its each performance index:
Oxygen index can reach 28; Combustionproperty is the UL94-1 level.
Embodiment 3: natural polygorskite is crushed to 100～5000 orders (granularity is 0.26-2.0um) after selected, again the mixture (ratio of polyphosphoric acid amine and tetramethylolmethane is 1: 0.1) of polygorskite powder and polyphosphoric acid amine and tetramethylolmethane 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 ethylene-vinyl acetate copolymer with 40%, 60% weight ratio thorough mixing and with Shooting Technique injection moulding on injection moulding machine of routine, flame-proof ethylene-acetate ethylene copolymer matrix 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 4: natural polygorskite is crushed to 100～5000 orders (granularity is 0.26-2.0um) after selected, again the mixture (ratio of polyphosphoric acid amine and tetramethylolmethane is 1: 0.4) of polygorskite powder and polyphosphoric acid amine and tetramethylolmethane 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 ethylene-vinyl acetate copolymer with 45%, 55% weight ratio thorough mixing and with Shooting Technique injection moulding on injection moulding machine of routine, flame-proof ethylene-acetate ethylene copolymer matrix 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 0.26-2.0um) after selected, again the mixture (ratio of polyphosphoric acid amine and tetramethylolmethane is 1: 0.6) of polygorskite powder and polyphosphoric acid amine and tetramethylolmethane 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 ethylene-vinyl acetate copolymer with 45%, 55% weight ratio thorough mixing, with Shooting Technique injection moulding on injection moulding machine of routine, flame-proof ethylene-acetate ethylene copolymer matrix material.It is as follows to measure its each performance index:
Oxygen index can reach 29; Combustionproperty is the UL94-1 level.
Embodiment 6: natural polygorskite is crushed to 100～5000 orders (granularity is 0.26-2.0um) after selected, again the mixture (ratio of polyphosphoric acid amine and tetramethylolmethane is 1: 0.8) of polygorskite powder and polyphosphoric acid amine and tetramethylolmethane 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 ethylene-vinyl acetate copolymer with 45%, 55% weight ratio thorough mixing, and with Shooting Technique injection moulding on injection moulding machine of routine, flame-proof ethylene-acetate ethylene copolymer matrix material.It is as follows to measure its each performance index:
Oxygen index can reach 30; Combustionproperty is the UL94-0 level.
Embodiment 7: natural polygorskite is crushed to 100～5000 orders (granularity is 0.26-2.0um) after selected, again the mixture (ratio of polyphosphoric acid amine and tetramethylolmethane is 1: 1) of polygorskite powder and polyphosphoric acid amine and tetramethylolmethane 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 ethylene-vinyl acetate copolymer with 45%, 55% weight ratio thorough mixing, and with Shooting Technique injection moulding on injection moulding machine of routine, flame-proof ethylene-acetate ethylene copolymer matrix material.It is as follows to measure its each performance index:
Oxygen index can reach 30; Combustionproperty is the UL94-0 level.
Embodiment 8: natural polygorskite is crushed to 100～5000 orders (granularity is 0.26-2.0um) after selected, again the mixture (ratio of polyphosphoric acid amine and tetramethylolmethane is 1: 3) of polygorskite powder and polyphosphoric acid amine and tetramethylolmethane 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 ethylene-vinyl acetate copolymer with 45%, 55% weight ratio thorough mixing, and with Shooting Technique injection moulding on injection moulding machine of routine, flame-proof ethylene-acetate ethylene copolymer matrix material.It is as follows to measure its each performance index:
Oxygen index can reach 29; Combustionproperty is the UL94-0 level.
Embodiment 9: natural polygorskite is crushed to 100～5000 orders (granularity is 0.26-2.0um) after selected, again the mixture (ratio of polyphosphoric acid amine and tetramethylolmethane is 1: 6) of polygorskite powder and polyphosphoric acid amine and tetramethylolmethane 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 ethylene-vinyl acetate copolymer with 45%, 55% weight ratio thorough mixing, and with Shooting Technique injection moulding on injection moulding machine of routine, flame-proof ethylene-acetate ethylene copolymer matrix 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: 9 ratio with the mode thorough mixing of mechanical blending.With gained polygorskite compound flame retardant and ethylene-vinyl acetate copolymer with 40%, 60% weight ratio thorough mixing, and with Shooting Technique injection moulding on injection moulding machine of routine, flame-proof ethylene-acetate ethylene copolymer matrix material.It is as follows to measure its each performance index:
Oxygen index can reach 28, and combustionproperty is the UL94-0 level.
Embodiment 11: natural polygorskite is crushed to 100～5000 orders (granularity is 0.26-2.0um) after selected, again polygorskite powder and polyphosphoric acid amine is promptly got paligorskite composite combustion inhibitor with 1: 10 ratio with the mode thorough mixing of mechanical blending.With above-mentioned gained polygorskite compound flame retardant and ethylene-vinyl acetate copolymer with 45%, 55% weight ratio thorough mixing and with Shooting Technique injection moulding on injection moulding machine of routine, flame-proof ethylene-acetate ethylene copolymer matrix material.It is as follows to measure its each performance index:
Oxygen index can reach 28; Combustionproperty is the UL94-0 level.
Embodiment 12: natural polygorskite is crushed to 100～5000 orders (granularity is 0.26-2.0um) after selected, again polygorskite powder and tetramethylolmethane is promptly got paligorskite composite combustion inhibitor with 1: 10 ratio with the mode thorough mixing of mechanical blending.With above-mentioned gained polygorskite compound flame retardant and ethylene-vinyl acetate copolymer with 45%, 55% weight ratio thorough mixing and with Shooting Technique injection moulding on injection moulding machine of routine, flame-proof ethylene-acetate ethylene copolymer matrix material.It is as follows to measure its each performance index:
Oxygen index can reach 28; Combustionproperty is the UL94-1 level.
Claims (2)
1, a kind of paligorskite composite combustion inhibitor, it is by being crushed to 100～5000 purpose polygorskite powders and the composite dose of mixed with 1: 1～1: 10 forms, it is characterized in that: described composite dose is polyphosphoric acid amine and/or tetramethylolmethane.
2, paligorskite composite combustion inhibitor as claimed in claim 1 is characterized in that: when being the mixture of polyphosphoric acid amine and tetramethylolmethane for composite dose, the ratio of polyphosphoric acid amine and tetramethylolmethane is: 1: 0.1～1: 10.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CNB2005100431696A CN100360640C (en) | 2005-08-27 | 2005-08-27 | Paligorskite composite combustion inhibitor |
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CNB2005100431696A CN100360640C (en) | 2005-08-27 | 2005-08-27 | Paligorskite composite combustion inhibitor |
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| Publication Number | Publication Date |
|---|---|
| CN1737083A CN1737083A (en) | 2006-02-22 |
| CN100360640C true CN100360640C (en) | 2008-01-09 |
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|---|---|---|---|
| CNB2005100431696A Expired - Fee Related CN100360640C (en) | 2005-08-27 | 2005-08-27 | Paligorskite composite combustion inhibitor |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN103172938B (en) * | 2013-04-17 | 2015-05-13 | 西北师范大学 | Preparation method of non-halogen flame-retardant ethylene propylene diene monomer-polypropylene composite material |
| CN105754238B (en) * | 2016-03-15 | 2018-11-02 | 常州塑金高分子科技有限公司 | Halogen-free flame-retardant polystyrene regenerated material for household electronic devices and preparation method thereof |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US3730890A (en) * | 1971-12-03 | 1973-05-01 | Early California Ind | Fire retardant composition and method of production |
| CN1424274A (en) * | 2001-12-10 | 2003-06-18 | 吕博 | Fireproof thermal insulating products and preparation thereof |
| CN1654599A (en) * | 2005-01-18 | 2005-08-17 | 西北师范大学 | Palygorskite compound flame retardant |
-
2005
- 2005-08-27 CN CNB2005100431696A patent/CN100360640C/en not_active Expired - Fee Related
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US3730890A (en) * | 1971-12-03 | 1973-05-01 | Early California Ind | Fire retardant composition and method of production |
| CN1424274A (en) * | 2001-12-10 | 2003-06-18 | 吕博 | Fireproof thermal insulating products and preparation thereof |
| CN1654599A (en) * | 2005-01-18 | 2005-08-17 | 西北师范大学 | Palygorskite compound flame retardant |
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| CN1737083A (en) | 2006-02-22 |
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| C14 | Grant of patent or utility model | ||
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| EE01 | Entry into force of recordation of patent licensing contract |
Assignee: Yangzhou Xin-Qi-Te Cable Material Co.,Ltd. Assignor: Northwest Normal University Contract record no.: 2011320000746 Denomination of invention: Palygorskite compound flame retardant Granted publication date: 20080109 License type: Exclusive License Open date: 20060222 Record date: 20110526 |
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Granted publication date: 20080109 Termination date: 20160827 |
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