CN103397443B - Halogen-free flame-retardant polyethylene plastic woven cloth and method for manufacturing same - Google Patents
Halogen-free flame-retardant polyethylene plastic woven cloth and method for manufacturing same Download PDFInfo
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Abstract
The invention discloses halogen-free flame-retardant polyethylene plastic woven cloth which comprises, by mass, 50%-85% of polyethylene, 10%-30% of ethylene-vinyl acetate elastomers and 20%-60% of nanometer inorganic flame retardant systems. The nanometer inorganic flame retardant systems comprise, by weight, 50%-85% of magnesium hydroxide, 1%-2% of silane coupling agents, 10%-30% of ethylene-vinyl acetate copolymers and 2%-8% of organic modified montmorillonite. The halogen-free flame-retardant polyethylene plastic woven cloth and a method for manufacturing the same have the advantages that the strength and the tenacity of the plastic woven cloth are improved, and accordingly requirements on the strength and the tenacity of the halogen-free flame-retardant polyethylene plastic woven cloth and the requirement on the flame-retardant property of the halogen-free flame-retardant polyethylene plastic woven cloth are met simultaneously.
Description
Technical field
The present invention relates to a kind of vinyon woven cloth, particularly a kind of halogen-free flame-retardant polyethylene plastic woven cloth and preparation method thereof.
Background technology
Polyethylene is widely used in the many aspects such as plastic package material, expanded material, woven cloth material, cable clad material.But its oxygen index (OI) only has 18.5, belongs to combustible material, which has limited their application.In order to improve the anti-flammability of polythene material, generally add the retardant synergist such as halogen containing flame-retardant and antimonous oxide traditionally, this fire retardant can discharge hydrogen halide poisonous in a large number when burning, and smog is large, causes great infringement can to environment and personal safety.Therefore; magnesium hydroxide, aluminium hydroxide as having filling concurrently, clean type inorganic combustion inhibitor that is fire-retardant, smoke elimination function is one and up-and-comingly substitutes; hydroxide can discharge moisture when burning; when fire burning met by material; burning liberated heat can be absorbed; produce water and oxide; certain the process of carbonization is had to polymer; form a protective layer; play fire retardation, suppress the generation of material combustion and smog simultaneously, and reach the object of Halogen, nontoxic, low cigarette; especially magnesium hydroxide is as fire retardant, has higher decomposition temperature.Because magnesium hydrate halogen-free fire retardant only can reach the effect of flame-retardant polymer when adding the amount of filling out and reaching more than 50%, this causes the mechanical property of polymeric material, and especially toughness and intensity significantly reduce (the patent document patent No.: 101012326).On the other hand, due to magnesium hydroxide surface hydrophilic oleophobic, polarity is large, causes it under high filler loading capacity condition, be difficult to be distributed in macromolecule matrix equably, thus affect processing characteristics and mechanical performance (the patent document patent No.: 101857692) of polymeric material.Therefore, need to add a small amount of retardant synergist to reduce magnesium hydroxide consumption, to improve material property.
Ethylene-vinyl acetate elastomer improves a kind of ideal material of pardon between matrix material and inorganic particle, the toughness of material can be improved simultaneously, and can by the extrusion plasticizing molding mode machine-shaping of plastics, this simplify moulding process, and production cost is reduced greatly, be used widely, but due to the mechanical strength of ethylene-vinyl acetate copolymer material, hardness lower, cause low (the patent document patent No.: 102952311) of the mechanical strength of material.
Summary of the invention
For the deficiencies in the prior art, the object of this invention is to provide a kind of halogen-free flame-retardant polyethylene plastic woven cloth and preparation method thereof, improve intensity and the toughness of woven cloth, thus solving Zero halogen flame resistance polyethylene woven cloth while reaching flame-retardancy requirements, intensity and toughness do not reach the problem of requirement.
Object of the present invention realizes by following technical proposal: a kind of halogen-free flame-retardant polyethylene plastic woven cloth, percent mass in described halogen-free flame-retardant polyethylene plastic woven cloth material consists of: polyethylene 50%-85%, ethylene-vinyl acetate elastomer 10%-30%, nanometer inorganic flame retardant system 20%-60%, in described nanometer inorganic flame retardant system, the percentage by weight of each composition is as follows: magnesium hydroxide 50%-85%, silane coupler 1%-2%, ethylene-vinyl acetate copolymer 10%-30%, organic modification montmonrillonite 2%-8%.
As preferably, the polyethylene in described halogen-free flame-retardant polyethylene plastic woven cloth material is metallocene linear-low density polyethylene.
Further, in the ethylene-vinyl acetate elastomer in described halogen-free flame-retardant polyethylene plastic woven cloth material, the content of vinylacetate is 15-35%.
Further, the particle diameter of described magnesium hydroxide is at 1-500nm.Described magnesium hydroxide particles has certain structure as bulk, needle-like, loose cavernous structure at least on one dimension within 100nm.The magnesium hydroxide particles choosing Nano grade is conducive to the decomposition completely when burning, and strengthens flame retardant effect, chooses the generation that the particle with definite shape and structure helps avoid reunion.
Further, described silane coupler is γ-glycidoxypropyl trimethoxy siloxanes.
Further, the spacing of described organic modification montmonrillonite layer is between 2-3nm, and particle diameter is 100-300nm.
The present invention also provides a kind of preparation method of above-mentioned halogen-free flame-retardant polyethylene plastic woven cloth, comprises the steps: 1) prepare nanometer inorganic flame retardant material; 2) flame-proof polyethylene blend composition is prepared; 3) wire drawing carried out to fire-retardant polyethylene material and weave cotton cloth, forming flame-proof polyethylene woven cloth;
Described step 1) in prepare nanometer inorganic flame retardant material method comprise: to be first the magnesium hydroxide of 50%-85% and mass fraction by mass fraction be silane coupler that 1%-2% diluent diluted is at 80-120 DEG C, high-speed stirred 0.5-2 hour, drying, obtains the magnesium hydroxide of modification; The magnesium hydroxide of described modification and mass fraction are the ethylene-vinyl acetate copolymer of 10%-50%, and mass fraction is that the organic modification montmonrillonite of 2%-8% is pre-mixed, extruding pelletization, prepare nanometer inorganic flame retardant pellet, described vinyl acetate content is 15-35%, and melt index is 3-10g/10min;
Described step 2) in prepare Zero halogen flame resistance polyethylene blend composition method comprise: first by described step 1) in the nanometer inorganic flame retardant material of preparation and mass fraction be 50%-85%, melt index is the polyethylene of 3-10g/10min, and mass fraction is
The ethylene-vinyl acetate of 10%-30% is elastomer blended, obtains Zero halogen flame resistance polyethylene blend composition;
Described step 3) in prepare Zero halogen flame resistance polyethylene woven cloth method comprise: first by described step 2) in the Zero halogen flame resistance polyethylene blend composition of preparation cool after extrusion film in extruding machine, cut, heating orientation stretching, after the pre-heat treatment sizing, wrapup procedure, be woven into halogen-free fire retardant plastic woven cloth through broadwise.
Further, the thread count of described flame retardant plastics woven cloth is 8 × 8-10 × 10, and thickness is 30-90g/m
2.
Compared with prior art, the present invention has the following advantages: (1) adopts organic nano imvite as synergistic fire retardant, improve the compatibility of halogen-free flame retardants and polyethylene group on the one hand, the intercalation configuration formed with polymeric matrix that adds of nanoclay has blocking effect on the other hand, utilize the draw ratio that nanoclay is high, form one deck enhancement layer when material combustion and effectively prevent subsiding of carburization zone, unburned polymer surfaces can effectively completely cut off by the existence of carburization zone, decrease the smoke which of combustible and distributing of flue gas, therefore, decrease the consumption of halogen-free flame retardants, obtain that there is better good flame retardation effect and mechanical property fire-retardant polyethylene material simultaneously, (2) the present invention adopts silane coupler to carry out surface polarity modification to nano-sized magnesium hydroxide particle simultaneously, strengthens itself and poly compatibility.Then the coating modification of ethylene-vinyl acetate elastomer is adopted, melt extrude prilling process, enhance the compatibility making inorganic nano-particle in polymeric matrix, make inorganic nano ion uniformly dispersed in polymeric matrix, avoid the agglomeration because nano effect causes; (3) in the preparation process in accordance with the present invention, the intensity of polymeric matrix metallocene PE is very high, adopts the metallocene PE of high strength can improve the intensity of woven polyethylene cloth, solves the problem of the intensity reduction that ethylene-vinyl acetate brings; (4) comparatively aluminium hydroxide is high for the heat decomposition temperature (about 340 DEG C) of magnesium hydroxide, is conducive to the raising of plastic processing temperature, applied widely; (5) by halogen-free flameproof woven cloth of the present invention, fire-retardant rank >=V-1 level, oxygen index (OI) >=28, TENSILE STRENGTH >=12MPa, elongation at break >=200%; (6) the flame-proof polyethylene woven cloth that prepared by the present invention is a kind of environmentally friendly fire proofing, not halogen-containing, poison gas is not discharged after burning, Environmental Safety, there is good fire resistance and mechanical property, this flame-proof polyethylene woven cloth technique is simple, cost reduces, performance improves, and has a wide range of applications.
Specific implementation method
Below in conjunction with embodiment, the present invention is further illustrated, but not as the foundation limited the present invention.
Embodiment 1: a kind of preparation method of halogen-free flame-retardant polyethylene plastic woven cloth, comprises the steps:
1. prepare nanometer inorganic flame retardant material;
2. prepare flame resistance polyethylene composite material;
3. pair fire-retardant polyethylene material carries out wire drawing and weaves cotton cloth, and forms flame-proof polyethylene woven cloth;
In the preparation method of above-mentioned flame-retardant high-molecular woven cloth, the method preparing nano inorganic fire proofing in described step 1 comprises: first by mass fraction be 80% magnesium hydroxide and mass fraction be that the silane coupler that diluted of 1% diluent is at 110 DEG C, high-speed stirred 0.5 hour, drying, stand-by.Then the magnesium hydroxide of above-mentioned modification and mass fraction be 50% ethylene-vinyl acetate copolymer and mass fraction be 5% nanometer organic modification montmonrillonite be pre-mixed, extruding pelletization, prepare the fire-retardant pellet of nano inorganic.
In described step 1, the average grain diameter of magnesium hydroxide is 300nm.
In described step 1, in ethylene-vinyl acetate copolymer, vinyl acetate content is 20%, and melt index is 6g/10min.
In described step 1, the average grain diameter of nanometer organic modification montmonrillonite is 200nm, and interlamellar spacing is 1.8nm.
In the preparation method of above-mentioned flame-retardant high-molecular woven cloth, the method preparing flame-proof polyethylene blend composition in described step 2 comprises: first by described step 1 preparation nanometer inorganic flame retardant material and mass fraction be 60%-85% metallocene PE, mass fraction is that the ethylene-vinyl acetate of 10%-30% is elastomer blended.
In described step 2, polyethylene is metallocene PE, and the melt index of described metallocene PE is 7.5g/10min.
In described step 2, in ethylene-vinyl acetate copolymer, vinyl acetate content is 20%, and melt index is 6g/10min.
In the preparation method of above-mentioned flame-retardant high-molecular woven cloth, the method preparing flame-proof polyethylene woven cloth in described step 3 comprises: first the flame-proof polyethylene blend composition of preparation in described step 2 is cooled after extrusion film, cut in extruding machine, heating orientation stretching, after the pre-heat treatment sizing, wrapup procedure, be woven into flame retardant plastics woven cloth through broadwise.
In described step 3, the surface density of woven cloth is 60g/m
2, thread count is 10 × 10.
By halogen-free flameproof woven cloth of the present invention, fire-retardant rank >=V-1 level, oxygen index (OI) >=28, TENSILE STRENGTH >=12MPa, elongation at break >=200%.
Embodiment 2: a kind of preparation method of halogen-free flame-retardant polyethylene plastic woven cloth, comprises the steps:
1. prepare nanometer inorganic flame retardant material;
2. prepare flame resistance polyethylene composite material;
3. pair fire-retardant polyethylene material carries out wire drawing and weaves cotton cloth, and forms flame-proof polyethylene woven cloth;
In the preparation method of above-mentioned flame-retardant high-molecular woven cloth, the method preparing nano inorganic fire proofing in described step 1 comprises: first by mass fraction be 80% magnesium hydroxide and mass fraction be that the silane coupler that diluted of 1% diluent is at 110 DEG C, high-speed stirred 0.5 hour, drying, stand-by.Then the magnesium hydroxide of above-mentioned modification and mass fraction be 50% ethylene-vinyl acetate copolymer and mass fraction be 5% nanometer organic modification montmonrillonite be pre-mixed, extruding pelletization, prepare the fire-retardant pellet of nano inorganic.
In described step 1, the average grain diameter of magnesium hydroxide is 300nm.
In described step 2, in ethylene-vinyl acetate copolymer, vinyl acetate content is 23%, and melt index is 8g/10min.
In described step 1, the average grain diameter of nanometer organic modification montmonrillonite is 200nm, and interlamellar spacing is 1.8nm.
In the preparation method of above-mentioned flame-retardant high-molecular woven cloth, the method preparing flame-proof polyethylene blend composition in described step 2 comprises: first by described step 1 preparation nanometer inorganic flame retardant material and mass fraction be 60%-85% metallocene PE, mass fraction is that the ethylene-vinyl acetate of 10%-30% is elastomer blended.
In described step 2, polyethylene is metallocene PE, and the melt index of described metallocene PE is 5g/10min.
In described step 2, in ethylene-vinyl acetate copolymer, vinyl acetate content is 23%, and melt index is 8g/10min.
In the preparation method of above-mentioned flame-retardant high-molecular woven cloth, the method preparing flame-proof polyethylene woven cloth in described step 3 comprises: first the flame-proof polyethylene blend composition of preparation in described step 2 is cooled after extrusion film, cut in extruding machine, heating orientation stretching, after the pre-heat treatment sizing, wrapup procedure, be woven into flame retardant plastics woven cloth through broadwise.
In described step 3, the surface density of woven cloth is 60g/m
2, thread count is 8 × 8.
By halogen-free flameproof woven cloth of the present invention, fire-retardant rank >=V-1 level, oxygen index (OI) >=28, TENSILE STRENGTH >=12MPa, elongation at break >=200%.
Embodiment 3: a kind of preparation method of halogen-free flame-retardant polyethylene plastic woven cloth, comprises the steps:
1. prepare nanometer inorganic flame retardant material;
2. prepare flame resistance polyethylene composite material;
3. pair fire-retardant polyethylene material carries out wire drawing and weaves cotton cloth, and forms flame-proof polyethylene woven cloth;
In the preparation method of above-mentioned flame-retardant high-molecular woven cloth, the method preparing nano inorganic fire proofing in described step 1 comprises: first by mass fraction be 80% magnesium hydroxide and mass fraction be that the silane coupler that diluted of 1% diluent is at 110 DEG C, high-speed stirred 0.5 hour, drying, stand-by.Then the magnesium hydroxide of above-mentioned modification and mass fraction be 50% ethylene-vinyl acetate copolymer and mass fraction be 5% nanometer organic modification montmonrillonite be pre-mixed, extruding pelletization, prepare the fire-retardant pellet of nano inorganic.
In described step 1, the average grain diameter of magnesium hydroxide is 300nm.
In described step 2, in ethylene-vinyl acetate copolymer, vinyl acetate content is 25%, and melt index is 10g/10min.
In described step 1, the average grain diameter of nanometer organic modification montmonrillonite is 200nm, and interlamellar spacing is 1.8nm.
In the preparation method of above-mentioned flame-retardant high-molecular woven cloth, the method preparing flame-proof polyethylene blend composition in described step 2 comprises: first by described step 1 preparation nanometer inorganic flame retardant material and mass fraction be 60%-85% metallocene PE, mass fraction is that the ethylene-vinyl acetate of 10%-30% is elastomer blended.
In described step 2, polyethylene is metallocene PE, and the melt index of described metallocene PE is 6g/10min.
In described step 2, in ethylene-vinyl acetate copolymer, vinyl acetate content is 25%, and melt index is 10g/10min.
In the preparation method of above-mentioned flame-retardant high-molecular woven cloth, the method preparing flame-proof polyethylene woven cloth in described step 3 comprises: first the flame-proof polyethylene blend composition of preparation in described step 2 is cooled after extrusion film, cut in extruding machine, heating orientation stretching, after the pre-heat treatment sizing, wrapup procedure, be woven into flame retardant plastics woven cloth through broadwise.
In described step 3, the surface density of woven cloth is 60g/m
2, thread count is 10 × 10.
By halogen-free flameproof woven cloth of the present invention, fire-retardant rank >=V-1 level, oxygen index (OI) >=28, TENSILE STRENGTH >=12MPa, elongation at break >=200%.
Claims (6)
1. a halogen-free flame-retardant polyethylene plastic woven cloth, it is characterized in that, the percent mass of described halogen-free flame-retardant polyethylene plastic woven cloth chemical composition consists of: polyethylene 50%-85%, ethylene-vinyl acetate elastomer 10%-30%, nanometer inorganic flame retardant system 20%-60%, described polyethylene is metallocene linear-low density polyethylene; In ethylene-vinyl acetate elastomer, the content of vinylacetate is 15-35%; In nanometer inorganic flame retardant system, the percentage by weight of each composition is as follows: magnesium hydroxide 50%-85%, silane coupler 1%-2%, ethylene-vinyl acetate copolymer 50%, organic modification montmonrillonite 2%-8%.
2. halogen-free flame-retardant polyethylene plastic woven cloth according to claim 1, is characterized in that, the particle diameter of described magnesium hydroxide is at 1-500nm.
3. halogen-free flame-retardant polyethylene plastic woven cloth according to claim 1, is characterized in that, described silane coupler is γ-glycidoxypropyl trimethoxy siloxanes.
4. halogen-free flame-retardant polyethylene plastic woven cloth according to claim 1, is characterized in that, the spacing of described organic modification montmonrillonite layer is 1.8nm, and particle diameter is 100-300nm.
5. a preparation method for the halogen-free flame-retardant polyethylene plastic woven cloth described in claim 1-4, is characterized in that, comprise the steps: 1) prepare nanometer inorganic flame retardant material; 2) Zero halogen flame resistance polyethylene blend composition is prepared; 3) wire drawing carried out to halogen-free fire-retardant polyethylene material and weave cotton cloth, forming Zero halogen flame resistance polyethylene woven cloth;
Described step 1) in prepare nanometer inorganic flame retardant material method comprise: to be first the magnesium hydroxide of 50%-85% and mass fraction by mass fraction be silane coupler that 1%-2% diluent diluted is at 80-120 DEG C, high-speed stirred 0.5-2 hour, drying, obtains the magnesium hydroxide of modification; The magnesium hydroxide of described modification, mass fraction are the ethylene-vinyl acetate copolymer of 50%, and mass fraction is that the organic modification montmonrillonite of 2%-8% is pre-mixed, extruding pelletization, prepare nanometer inorganic flame retardant pellet, in ethylene-vinyl acetate copolymer, vinyl acetate content is 15-35%, and melt index is 3-10g/10min; Described step 2) in prepare halogen-free flameproof flame-proof polyethylene blend composition method comprise: first by described step 1) in the nanometer inorganic flame retardant material of preparation and mass fraction be 50%-85%, melt index is the polyethylene of 3-10g/10min, mass fraction is that the ethylene-vinyl acetate of 10%-30% is elastomer blended, obtains Zero halogen flame resistance polyethylene blend composition;
Described step 3) in prepare Zero halogen flame resistance polyethylene woven cloth method comprise: first by described step 2) in the Zero halogen flame resistance polyethylene blend composition of preparation cool after extrusion film in extruding machine, cut, heating orientation stretching, after the pre-heat treatment sizing, wrapup procedure, be woven into halogen-free fire retardant plastic woven cloth through broadwise.
6. the preparation method of halogen-free flame-retardant polyethylene plastic woven cloth according to claim 5, is characterized in that, described halogen-free fire retardant plastic woven cloth surface density is 30-90g/m
2.
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| JP2849424B2 (en) * | 1990-01-16 | 1999-01-20 | 株式会社クラレ | Woven and knitted fabric |
| NL1010837C2 (en) * | 1997-12-18 | 1999-07-13 | Kyowa Kk | Flame retardant for netting and non-flammable netting material containing it. |
| CN1314778C (en) * | 2005-03-04 | 2007-05-09 | 北京化工大学 | Process for preparing nano inorganic compound flame retardant by transfer method |
| CN101230162B (en) * | 2008-02-27 | 2011-08-24 | 周宝茂 | Low-smoke bittern-free flame-retardant polyolefin material and braided fabric manufactured thereby |
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