CN100487036C - Paligorskite-linear low density polyethylene composite flame-proof material - Google Patents
Paligorskite-linear low density polyethylene composite flame-proof material Download PDFInfo
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- CN100487036C CN100487036C CNB2006101045359A CN200610104535A CN100487036C CN 100487036 C CN100487036 C CN 100487036C CN B2006101045359 A CNB2006101045359 A CN B2006101045359A CN 200610104535 A CN200610104535 A CN 200610104535A CN 100487036 C CN100487036 C CN 100487036C
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Abstract
The present invention provides one kind of composite flame retardant material, which is prepared with 100-5000 mesh palygorskite powder, no-halogen fire retardant and linear low density polyethylene in the weight ratio of 1 to 1 to 1-1 to 15 to 100 and through conventional plasticating process. The composite flame retardant material has excellent flame retarding performance, and is measured to have oxygen index up to 28 and combustion performance of UL94-1 to UL94-0 level. The composite flame retardant material with palygorskite and no-halogen fire retardant as composite flame retardant has no combustion produced gas, and is pollution-less. During combustion, it will form one layer of glass-like covering on the surface of polymer and with four functions of retarding flame, isolating oxygen, eliminating smoke and preventing dropping. The composite flame retardant material has simple production process, wide material source and low cost.
Description
Technical field
The invention belongs to technical field of polymer materials, being specifically related to a kind of is the linear low density polyethylene composite flame-proof material of fire retardant preparation with the polygorskite.
Background technology
Fire retardant 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.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%～70% of all flame retardant products, mainly is Al (OH)
3And Mg (OH)
2Be the fire retardant material of additive, but the addition of these additives is big, worsens material physical property, apply being unfavorable in some cases.
At present, the conventional flame retardants that uses in the macromolecular material, prevailing still halogen is (as decabromodiphenyl oxide), phosphorus--halogen system (halogen-containing phosphoric acid ester) fire retardant.The flame retardant macromolecular material that employing contains halogen increases the generation of cigarette, poison gas and corrosive gases when burning greatly, in use, must add weisspiessglanz or sodium antimonate as synergist, but the antimony resource is also limited.Halogen phosphorus-nitrogen flame retardant is the present popular domain of research and development, and its advantage is low cigarette, low toxicity, and has the highly effective flame-retardant effect, successfully has been applied in the macromolecular materials such as some polypropylene of not tying charcoal of being heated, polyethylene, polystyrene.
Halogen phosphorus-nitrogen flame retardant is to be the fire retardant of major ingredient with phosphorus, nitrogen, and it is not halogen-containing, and also not adopting weisspiessglanz is synergist.When the superpolymer that contains this based flame retardant was heated, the depolymerization of red phosphorus elder generation was P
4, and then absorption polygorskite powder steam aquation becomes phosphoric acid.Phosphoric acid further is condensed into poly-metaphosphoric acid, forms glassy coverture at polymer surfaces, and emits the nitrogen G﹠W, has reduced the oxygen concentration in the gas phase, has suppressed burning, thereby has brought into play the condensed phase fire retardation of red phosphorus.The generation existence of polygorskite in addition of poly-metaphosphoric acid making burning form charring layer, and the small molecules inflammable gas that has stoped entering of heat and oxygen also to stop pyrolysis to produce enters gas phase, from and reached the fire-retardant purpose of gas phase.
It is the micropore of 0.32 * 0.73nm that the aperture consistent with its length direction arranged in the polygorskite crystal, the hole contains a large amount of ignition-proof element magnesium, aluminium and water of different nature, as crystal water, hydroxyl structure water, zeolite molecules water and inclusion water etc., the water vapour that these water at high temperature produce is favourable to phosphorus flame retardant especially, and the porous of polygorskite and hollow structure have strong adsorption to gas, and the heat insulation thermal insulation of hollow can be blocked the transmission of heat, and these characteristics make it have good flame retardancy.That polygorskite has is non-volatile, cheap, it is fire-retardant to have concurrently, press down cigarette and reduce the function of toxic gas, so be the nuisanceless fire retardant of ideal.
Linear low density polyethylene is called for short LLDPE, and it is the good thermoplastic plastics.LLDPE have good snappiness, the transparency, weathering resistance, chemical proofing and with the consistency of filler, colorant.Be mainly used in rotomoulded articles: the medium-sized or large-scale heavy wall hollow and the parts with complicated shape of opening; Make wire cable material, film, tubing (combustion gas pipe arrangement), sheet material, household electrical appliance parts and compound.The demand of LLDPE is huge ascendant trend all over the world in recent years, with regard to China, the demand ascendant trend is obvious, increases to 896kt in 1998 from 3kt in 1988.But LLDPE very easily fires, and has limited its application at aspects such as household electrical appliances, building, building materials, cable insulations, so the flame retardant resistance of LLDPE more and more causes people's attention aborning.Paligorskite-linear low density polyethylene composite flame-proof material is because to have when burning smog few, and the charcoal layer of generation can effectively prevent the advantages such as molten drop of polymkeric substance, so be a kind of ideal fire retardant material.
Summary of the invention
The 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.
Paligorskite-linear low density polyethylene composite flame-proof material of the present invention, be to be crushed to 100～5000 purpose polygorskite powders, halogen-free flame retardants, linear low density polyethylene weight ratio thorough mixing, mould with the refining of routine that technology is mixing to form with 1:1:1～1:15:100.
Wherein halogen-free flame retardants is at least a in trimeric cyanamide, red phosphorus, the magnesium hydroxide.
When halogen-free flame retardants was the mixture of red phosphorus and trimeric cyanamide, the weight ratio of red phosphorus and trimeric cyanamide was 1:0.1～1:15.
When halogen-free flame retardants was the mixture of red phosphorus and magnesium hydroxide, the weight ratio of red phosphorus and magnesium hydroxide was 1:0.1～1:15.
When halogen-free flame retardants is the mixture of trimeric cyanamide and magnesium hydroxide, the weight ratio of trimeric cyanamide and magnesium hydroxide is 1:0.1～1:15.
When halogen-free flame retardants was red phosphorus, trimeric cyanamide, magnesium hydroxide three's mixture, the weight ratio of red phosphorus, trimeric cyanamide, magnesium hydroxide was 1:0.1:0.1～1:15:15.
The present invention compared with prior art has the following advantages:
1, composite flame-proof material of the present invention is a composite flame-retardant agent with natural polygorskite and halogen-free flame retardants, forms with the linear low density polyethylene mixing banburying with good thermoplastic property, has good flame retardancy.The oxygen index of composite flame-proof material of the present invention can reach more than 28 after measured, and combustionproperty is UL94-1～UL94-0 level.
2, the present invention is a composite flame-retardant agent with natural polygorskite and halogen-free flame retardants, does not produce toxic gas, environmental protection, pollution-free when burning; Simultaneously, in halogen-free flame retardants when burning, form the glassy coverture of one deck at polymer surfaces, and the carbonaceous foam layer of enclosed construction is arranged, and that this layer has is fire-retardant, oxygen barrier, smoke elimination and anti-drippage quadruple effect.
3, composite flame-proof material production technique of the present invention is simple, and raw material sources are extensive, and are cheap, thereby greatly reduces the cost of fire retardant material, and the suitability for industrialized production of fire retardant material is had huge pushing effect.
Embodiment
Further specify linear low density polyethylene fire retardant material flame retardant effect below by specific examples:
Embodiment 1: (granularity is 0.26-2.00um earlier natural polygorskite to be crushed to 100～5000 orders after selected, down together), again polygorskite powder, trimeric cyanamide, linear low density polyethylene are pressed the mode thorough mixing of the weight ratio of 1:1:1 with mechanical blending, with Shooting Technique injection moulding on injection moulding machine of routine, get paligorskite-linear low density polyethylene composite flame-proof material.After measured, its oxygen index can reach 28, and combustionproperty is the UL94-1 level.
Embodiment 2: earlier natural polygorskite is crushed to 100～5000 orders (granularity is 0.26-2.00um) after selected, again polygorskite powder, red phosphorus, linear low density polyethylene are pressed the mode thorough mixing of the weight ratio of 1:10:50 with mechanical blending, with Shooting Technique injection moulding on injection moulding machine of routine, get paligorskite-linear low density polyethylene composite flame-proof material.After measured, its oxygen index can reach 28, and combustionproperty is the UL94-1 level.
Embodiment 3: earlier natural polygorskite is crushed to 100～5000 orders (granularity is 0.26-2.00um) after selected, again polygorskite powder, magnesium hydroxide, linear low density polyethylene are pressed the mode thorough mixing of the weight ratio of 1:15:100 with mechanical blending, with Shooting Technique injection moulding on injection moulding machine of routine, get paligorskite-linear low density polyethylene composite flame-proof material.After measured, its oxygen index can reach 28, and combustionproperty is the UL94-1 level.
Embodiment 4: earlier natural polygorskite is crushed to 100～5000 orders (granularity is 0.26-2.00um) after selected, again mixture (wherein the weight ratio of red phosphorus and trimeric cyanamide is 1:0.1), the linear low density polyethylene of polygorskite powder, red phosphorus and trimeric cyanamide are pressed the mode thorough mixing of the weight ratio of 1:1:1 with mechanical blending, with Shooting Technique injection moulding on injection moulding machine of routine, get paligorskite-linear low density polyethylene composite flame-proof material.After measured, its oxygen index can reach 28, and combustionproperty is the UL94-1 level.
Embodiment 5: earlier natural polygorskite is crushed to 100～5000 orders (granularity is 0.26-2.00um) after selected, again mixture (wherein the weight ratio of red phosphorus and trimeric cyanamide is 1:1), the linear low density polyethylene of polygorskite powder, red phosphorus and trimeric cyanamide are pressed the mode thorough mixing of the weight ratio of 1:5:10 with mechanical blending, with Shooting Technique injection moulding on injection moulding machine of routine, get paligorskite-linear low density polyethylene composite flame-proof material.After measured, its oxygen index can reach 28, and combustionproperty is the UL94-1 level.
Embodiment 6: earlier natural polygorskite is crushed to 100～5000 orders (granularity is 0.26-2.00um) after selected, again mixture (wherein the weight ratio of red phosphorus and trimeric cyanamide is 1:15), the linear low density polyethylene of polygorskite powder, red phosphorus and trimeric cyanamide are pressed the mode thorough mixing of the weight ratio of 1:8:80 with mechanical blending, with Shooting Technique injection moulding on injection moulding machine of routine, get paligorskite-linear low density polyethylene composite flame-proof material.After measured, its oxygen index can reach 28, and combustionproperty is the UL94-1 level.
Embodiment 7: earlier natural polygorskite is crushed to 100～5000 orders (granularity is 0.26-2.00um) after selected, again mixture (wherein the weight ratio of red phosphorus and magnesium hydroxide is 1:0.1), the linear low density polyethylene of polygorskite powder, red phosphorus and magnesium hydroxide are pressed the mode thorough mixing of the weight ratio of 1:1:1 with mechanical blending, with Shooting Technique injection moulding on injection moulding machine of routine, get paligorskite-linear low density polyethylene composite flame-proof material.After measured, its oxygen index can reach 28, and combustionproperty is the UL94-1 level.
Embodiment 8: earlier natural polygorskite is crushed to 100～5000 orders (granularity is 0.26-2.00um) after selected, again mixture (wherein the weight ratio of red phosphorus and magnesium hydroxide is 1:1), the linear low density polyethylene of polygorskite powder, red phosphorus and magnesium hydroxide are pressed the mode thorough mixing of the weight ratio of 1:10:20 with mechanical blending, with Shooting Technique injection moulding on injection moulding machine of routine, get paligorskite-linear low density polyethylene composite flame-proof material.After measured, its oxygen index can reach 28, and combustionproperty is the UL94-1 level.
Embodiment 9: earlier natural polygorskite is crushed to 100～5000 orders (granularity is 0.26-2.00um) after selected, again mixture (wherein the weight ratio of red phosphorus and magnesium hydroxide is 1:15), the linear low density polyethylene of polygorskite powder, red phosphorus and magnesium hydroxide are pressed the mode thorough mixing of the weight ratio of 1:15:10 with mechanical blending, with Shooting Technique injection moulding on injection moulding machine of routine, get paligorskite-linear low density polyethylene composite flame-proof material.After measured, its oxygen index can reach 28, and combustionproperty is the UL94-1 level.
Embodiment 10: earlier natural polygorskite is crushed to 100～5000 orders (granularity is 0.26-2.00um) after selected, again the mixture in polygorskite powder, trimeric cyanamide and the magnesium hydroxide (wherein the weight ratio in trimeric cyanamide and the magnesium hydroxide is 1:0.1), linear low density polyethylene are pressed the mode thorough mixing of the weight ratio of 1:1:10 with mechanical blending, with Shooting Technique injection moulding on injection moulding machine of routine, get paligorskite-linear low density polyethylene composite flame-proof material.After measured, its oxygen index can reach 28, and combustionproperty is the UL94-1 level.
Embodiment 11: earlier natural polygorskite is crushed to 100～5000 orders (granularity is 0.26-2.00um) after selected, again the mixture in polygorskite powder, trimeric cyanamide and the magnesium hydroxide (wherein the weight ratio in trimeric cyanamide and the magnesium hydroxide is 1:8), linear low density polyethylene are pressed the mode thorough mixing of the weight ratio of 1:6:60 with mechanical blending, with Shooting Technique injection moulding on injection moulding machine of routine, get paligorskite-linear low density polyethylene composite flame-proof material.After measured, its oxygen index can reach 28, and combustionproperty is the UL94-1 level.
Embodiment 12: earlier natural polygorskite is crushed to 100～5000 orders (granularity is 0.26-2.00um) after selected, again the mixture in polygorskite powder, trimeric cyanamide and the magnesium hydroxide (wherein the weight ratio in trimeric cyanamide and the magnesium hydroxide is 1:15), linear low density polyethylene are pressed the mode thorough mixing of the weight ratio of 1:15:100 with mechanical blending, with Shooting Technique injection moulding on injection moulding machine of routine, get paligorskite-linear low density polyethylene composite flame-proof material.After measured, its oxygen index can reach 28, and combustionproperty is the UL94-1 level.
Embodiment 13: the powder that earlier natural polygorskite is crushed to 100～5000 orders (granularity is 0.26-2.00um) after selected; Again red phosphorus, trimeric cyanamide, magnesium hydroxide are become composite flame-retardant agent by the weight ratio of 1:0.1:0.1 with the mode thorough mixing of mechanical blending; Polygorskite powder, gained composite flame-retardant agent, linear low density polyethylene are pressed the mode thorough mixing of the weight ratio of 1:1:1 with mechanical blending then, and with Shooting Technique injection moulding on injection moulding machine of routine, paligorskite-linear low density polyethylene composite flame-proof material.After measured, its oxygen index can reach 28, and combustionproperty is the UL94-1 level.
Embodiment 14: the powder that earlier natural polygorskite is crushed to 100～5000 orders (granularity is 0.26-2.00um) after selected; Again red phosphorus, trimeric cyanamide, magnesium hydroxide are become composite flame-retardant agent by the weight ratio of 1:1:5 with the mode thorough mixing of mechanical blending; Polygorskite powder, gained composite flame-retardant agent, linear low density polyethylene are pressed the mode thorough mixing of the weight ratio of 1:10:20 with mechanical blending then, and with Shooting Technique injection moulding on injection moulding machine of routine, paligorskite-linear low density polyethylene composite flame-proof material.After measured, its oxygen index can reach 28, and combustionproperty is the UL94-1 level.
Embodiment 15: the powder that earlier natural polygorskite is crushed to 100～5000 orders (granularity is 0.26-2.00um) after selected; Again red phosphorus, trimeric cyanamide, magnesium hydroxide are become composite flame-retardant agent by the weight ratio of 1:15:15 with the mode thorough mixing of mechanical blending; Polygorskite powder, gained composite flame-retardant agent, linear low density polyethylene are pressed the mode thorough mixing of the weight ratio of 1:15:100 with mechanical blending then, and with Shooting Technique injection moulding on injection moulding machine of routine, paligorskite-linear low density polyethylene composite flame-proof material.After measured, its oxygen index can reach 28, and combustionproperty is the UL94-1 level.
Claims (5)
1, a kind of paligorskite-linear low density polyethylene composite flame-proof material, it is characterized in that: be to be crushed to 100～5000 purpose polygorskite powders, halogen-free flame retardants, linear low density polyethylene weight ratio thorough mixing, mould with the refining of routine that technology is mixing to form with 1:1:1～1:15:100; Described halogen-free flame retardants is at least a in trimeric cyanamide, red phosphorus, the magnesium hydroxide.
2, paligorskite-linear low density polyethylene composite flame-proof material according to claim 1, it is characterized in that: described halogen-free flame retardants is the mixture of red phosphorus and trimeric cyanamide, and the weight ratio of red phosphorus and trimeric cyanamide is 1:0.1～1:15.
3, paligorskite-linear low density polyethylene composite flame-proof material according to claim 1, it is characterized in that: described halogen-free flame retardants is the mixture of red phosphorus and magnesium hydroxide, and the weight ratio of red phosphorus and magnesium hydroxide is 1:0.1～1:15.
4, paligorskite-linear low density polyethylene composite flame-proof material according to claim 1, it is characterized in that: described halogen-free flame retardants is the mixture of trimeric cyanamide and magnesium hydroxide, and the weight ratio of trimeric cyanamide and magnesium hydroxide is 1:0.1～1:15.
5, polygorskite-linear low density polyethylene composite flame-retardant agent according to claim 1, it is characterized in that: described halogen-free flame retardants is the mixture of red phosphorus, trimeric cyanamide, magnesium hydroxide, and the weight ratio of red phosphorus, trimeric cyanamide, magnesium hydroxide is 1:0.1:0.1～1:15:15.
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| CNB2006101045359A CN100487036C (en) | 2006-09-01 | 2006-09-01 | Paligorskite-linear low density polyethylene composite flame-proof material |
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| CNB2006101045359A CN100487036C (en) | 2006-09-01 | 2006-09-01 | Paligorskite-linear low density polyethylene composite flame-proof material |
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| CN100487036C true CN100487036C (en) | 2009-05-13 |
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| CN102344602A (en) * | 2011-08-09 | 2012-02-08 | 常熟市慧丰塑料制品有限公司 | Method for processing plastic |
| 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 |
| CN116102817B (en) * | 2023-03-15 | 2024-08-16 | 上海凯波电缆特材股份有限公司 | High-light-transmittance halogen-free flame-retardant polyolefin sheath material and preparation method thereof |
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