CN100335551C - Paligorskite ethene-vinyl acetate composite flame-proof material - Google Patents
Paligorskite ethene-vinyl acetate composite flame-proof material Download PDFInfo
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- CN100335551C CN100335551C CNB2005100431709A CN200510043170A CN100335551C CN 100335551 C CN100335551 C CN 100335551C CN B2005100431709 A CNB2005100431709 A CN B2005100431709A CN 200510043170 A CN200510043170 A CN 200510043170A CN 100335551 C CN100335551 C CN 100335551C
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- vinyl acetate
- fire retardant
- polygorskite
- ethene
- ethylene
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Abstract
The present invention provides a palygorskite ethene-vinyl acetate composite fire retardant material. A paligorskite composite fire retardant is prepared by mechanically mixing pulverized natural paligorskite powder of 100 to 5000 meshes and a composite agent of polyphosphoric acid amine and/or pentaerythritol according to a certain proportion, and then the paligorskite composite fire retardant is mixed with an ethylene-vinyl acetate copolymer to form the palygorskite ethene-vinyl acetate composite fire retardant material. The ethylene-vinyl acetate copolymer is one of the most important ethene copolymers with good performance and wide application, and the ethylene-vinyl acetate copolymer can be used for producing hot-melt adhesives, injection products, films, foaming products, pipe materials, electric wires, cables, plate materials, etc. and can also be used in the production of chemical building materials, printing ink, paint, etc. The palygorskite ethene-vinyl acetate composite fire retardant material has the advantages of stable performance, high oxygen index, favorable fire retardant effect, lasting effect and low price. Because palygorskite has the characteristics of no volatilization, little smoke and no toxicity, the composite fire retardant material also has the functions of fire retardation, smoke suppression and toxic gas reduction. The palygorskite ethene-vinyl acetate composite fire retardant material does not have environmental pollution.
Description
Technical field
The invention belongs to technical field of polymer materials, relate to a kind of flame-proof ethylene-vinyl acetate between to for plastic matrix material, relating in particular to a kind of is the flame-proof ethylene-vinyl acetate between to for plastic matrix material of fire retardant preparation with the polygorskite.
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 ethene-vinyl acetate composite flame-proof material 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 ethene-vinyl acetate composite flame-proof material is by the polygorskite compound flame retardant with ethylene-vinyl acetate copolymer is mixing forms.
Described polygorskite compound flame retardant is to form by being crushed to 100～5000 purpose polygorskite powders and the composite dose ratio machinery blending with 1: 1～1: 10.
Described polygorskite compound flame retardant and ethylene-vinyl acetate copolymer blended weight percent are:
Polygorskite compound flame retardant: 5%～45%;
Ethylene-vinyl acetate copolymer: 55%～95%.
Described composite dose is ammonium polyphosphate and/or tetramethylolmethane; When being the mixture of ammonium polyphosphate and tetramethylolmethane for composite dose, the ratio of ammonium polyphosphate and tetramethylolmethane is: 1: 0.1～1: 10.
The present invention compared with prior art has the following advantages:
1, to adopt with stable performance, natural polygorskite that flame retardant properties is good be fire retardant in the present invention, and its good flame retardation effect, effect are lasting.
2, because polygorskite itself is non-volatile, smog is little, nontoxicity, so be that fire retardant is made composite flame-proof material with it, have concurrently fire-retardant, but the function of cigarette and reduction toxic gas.
3, because polygorskite has good suction and water retention property, at high temperature can produce water vapour blocking-up oxygen, improved oxygen index of the present invention greatly.
4, technology of the present invention is simple, cost is low, is a kind of non-environmental-pollution fire retardant material.
Embodiment
Further specify the flame retardant effect of paligorskite ethene-vinyl acetate composite flame-proof material below in conjunction with embodiment.
Embodiment 1: natural polygorskite is crushed to 100～5000 orders (granularity is 0.26-2.0um) after selected, again polygorskite powder and ammonium polyphosphate 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 ammonium polyphosphate and tetramethylolmethane is 1: 0.1) of polygorskite powder and ammonium polyphosphate 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 ammonium polyphosphate and tetramethylolmethane is 1: 0.2) of polygorskite powder and ammonium polyphosphate 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 35%, 65% 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 ammonium polyphosphate and tetramethylolmethane is 1: 0.5) of polygorskite powder and ammonium polyphosphate 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 30%, 70% 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:
It is the UL94-1 level that oxygen index can reach 29 combustionproperties
Embodiment 6: natural polygorskite is crushed to 100～5000 orders (granularity is 0.26-2.0um) after selected, again the mixture (ratio of ammonium polyphosphate and tetramethylolmethane is 1: 0.8) of polygorskite powder and ammonium polyphosphate 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 25%, 75% 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 30 combustionproperties
Embodiment 7: natural polygorskite is crushed to 100～5000 orders (granularity is 0.26-2.0um) after selected, again the mixture (ratio of ammonium polyphosphate and tetramethylolmethane is 1: 1) of polygorskite powder and ammonium polyphosphate 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 20%, 80% 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 30 combustionproperties
Embodiment 8: natural polygorskite is crushed to 100～5000 orders (granularity is 0.26-2.0um) after selected, again the mixture (ratio of ammonium polyphosphate and tetramethylolmethane is 1: 5) of polygorskite powder and ammonium polyphosphate 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 15%, 85% 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 29 combustionproperties
Embodiment 9: natural polygorskite is crushed to 100～5000 orders (granularity is 0.26-2.0um) after selected, again the mixture (ratio of ammonium polyphosphate and tetramethylolmethane is 1: 8) of polygorskite powder and ammonium polyphosphate 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 10%, 90% 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 0.26-2.0um) after selected, again the mixture (ratio of ammonium polyphosphate and tetramethylolmethane is 1: 10) of polygorskite powder and magnesium hydroxide and melamine 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 5%, 95% 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 ammonium polyphosphate 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 30%, 70% 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 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; Combustionproperty is the UL94-1 level.
Claims (3)
1, a kind of paligorskite ethene-vinyl acetate composite flame-proof material, by fire retardant with ethylene-vinyl acetate copolymer is mixing forms, it is characterized in that: described fire retardant is by being crushed to the polygorskite compound flame retardant that the ratio machinery blending with 1: 1～1: 10 of 100～5000 purpose polygorskite powders and composite dose of ammonium polyphosphate and/or tetramethylolmethane forms.
2, paligorskite ethene-vinyl acetate composite flame-proof material as claimed in claim 1 is characterized in that: described polygorskite compound flame retardant and ethylene-vinyl acetate copolymer blended weight percent are:
Polygorskite compound flame retardant: 5%～45%;
Ethylene-vinyl acetate copolymer: 55%～95%.
3, paligorskite ethene-vinyl acetate composite flame-proof material as claimed in claim 2 is characterized in that: during described composite dose of mixture for ammonium polyphosphate and tetramethylolmethane, the ratio of ammonium polyphosphate and tetramethylolmethane is: 1: 0.1～1: 10.
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CNB2005100431709A CN100335551C (en) | 2005-08-27 | 2005-08-27 | Paligorskite ethene-vinyl acetate composite flame-proof material |
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|---|---|---|---|
| CNB2005100431709A CN100335551C (en) | 2005-08-27 | 2005-08-27 | Paligorskite ethene-vinyl acetate composite flame-proof material |
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| CN100335551C true CN100335551C (en) | 2007-09-05 |
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| 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 |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO1998036022A1 (en) * | 1997-02-17 | 1998-08-20 | Basf Aktiengesellschaft | Flameproof thermoplastic molding materials |
| CN1259601A (en) * | 1999-01-04 | 2000-07-12 | 北京市建筑材料科学研究院 | Asbestos free fire protection flame retarding paper |
| CN1654599A (en) * | 2005-01-18 | 2005-08-17 | 西北师范大学 | Palygorskite compound flame retardant |
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2005
- 2005-08-27 CN CNB2005100431709A patent/CN100335551C/en not_active Expired - Fee Related
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO1998036022A1 (en) * | 1997-02-17 | 1998-08-20 | Basf Aktiengesellschaft | Flameproof thermoplastic molding materials |
| CN1259601A (en) * | 1999-01-04 | 2000-07-12 | 北京市建筑材料科学研究院 | Asbestos free fire protection flame retarding paper |
| CN1654599A (en) * | 2005-01-18 | 2005-08-17 | 西北师范大学 | Palygorskite compound flame retardant |
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| CN1737045A (en) | 2006-02-22 |
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Application publication date: 20060222 Assignee: ZHEJIANG SINOPONT TECHNOLOGY CO., LTD. Assignor: Northwest Normal University Contract record no.: 2012330000463 Denomination of invention: Paligorskite ethene-vinyl acetate composite flame-proof material Granted publication date: 20070905 License type: Exclusive License Record date: 20120809 |
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Application publication date: 20060222 Assignee: ZHEJIANG SINOPONT TECHNOLOGY CO., LTD. Assignor: Northwest Normal University Contract record no.: 2012330000463 Denomination of invention: Paligorskite ethene-vinyl acetate composite flame-proof material Granted publication date: 20070905 License type: Exclusive License Record date: 20120809 |
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