CN103397443A - 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, and this has limited their application.In order to improve the anti-flammability of polythene material, generally add traditionally the retardant synergists such as halogen containing flame-retardant and antimonous oxide, this fire retardant can discharge a large amount of poisonous hydrogen halides when burning, smog is large, causes great infringement can for environment and personal safety.Therefore; magnesium hydroxide, aluminium hydroxide as having filling concurrently, clean type inorganic combustion inhibitor fire-retardant, the smoke elimination function is up-and-coming substituting; hydroxide can discharge moisture when burning; when material is met the fire burning; can absorb the burning liberated heat; produce water and oxide; polymer is had to certain the process of carbonization; form a protective layer; play fire retardation, suppress simultaneously the generation of material combustion and smog, and reach the purpose of Halogen, nontoxic, low cigarette; especially magnesium hydroxide, as fire retardant, has higher decomposition temperature.Because the magnesium hydrate halogen-free fire retardant only reaches 50% effect that can reach flame-retardant polymer when above adding the amount of filling out, this causes the mechanical property of polymeric material, especially toughness and intensity decrease (the patent documentation patent No.: 101012326).On the other hand, due to magnesium hydroxide surface hydrophilic oleophobic, polarity is large, causes it under the high filler loading capacity condition, be difficult to be distributed in macromolecule matrix equably, thereby affect processing characteristics and mechanical performance (the patent documentation patent No.: 101857692) of polymeric material.Therefore, need to add a small amount of retardant synergist and reduce the magnesium hydroxide consumption, to improve material property.
The ethylene-vinyl acetate elastomer is to improve a kind of comparatively desirable material of pardon between matrix material and inorganic particle, can improve simultaneously the toughness of material, and can pass through the extrusion plasticizing molding mode machine-shaping of plastics, this has simplified moulding process, and production cost is reduced greatly, be used widely, but because mechanical strength, the hardness of ethylene-vinyl acetate copolymer material are lower (the patent documentation patent No.: 102952311) that causes the mechanical strength of material low.
Summary of the invention
For the deficiencies in the prior art, the purpose of this invention is to provide a kind of halogen-free flame-retardant polyethylene plastic woven cloth and preparation method thereof, intensity and the toughness of woven cloth have been improved, thereby solve the Zero halogen flame resistance polyethylene woven cloth when reaching fire-retardant requirement, intensity and toughness do not reach the problem of requirement.
Purpose of the present invention can realize by following technical proposal: a kind of halogen-free flame-retardant polyethylene plastic woven cloth, quality percentage composition in described halogen-free flame-retardant polyethylene plastic woven cloth material is: polyethylene 50%-85%, ethylene-vinyl acetate elastomer 10%-30%, nanometer inorganic flame retardant system 20%-60%, in described nanometer inorganic flame retardant system, each percentage by weight that forms 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 such as bulk, needle-like, loose cavernous structure at least on one dimension in 100nm.Decomposition fully when the magnesium hydroxide particles of choosing Nano grade is conducive to burn, strengthen flame retardant effect, chooses the generation that the particle with definite shape and structure helps avoid reunion.
Further, described silane coupler is γ-glycidol oxygen propyl 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 the nanometer inorganic flame retardant material; 2) prepare the flame-proof polyethylene blend composition; 3) to fire-retardant polyethylene material, carry out wire drawing and weave cotton cloth, forming the flame-proof polyethylene woven cloth;
The method for preparing the nanometer inorganic flame retardant material in described step 1) comprises: by mass fraction, be at first that the magnesium hydroxide of 50%-85% and mass fraction are that the silane coupler that diluted of 1%-2% diluent is under 80-120 ℃, high-speed stirred 0.5-2 hour, drying, obtain the magnesium hydroxide of modification; Then by the magnesium hydroxide of above-mentioned modification, mass fraction, be the ethylene-vinyl acetate of 20%-60%, wherein vinyl acetate content is 15-35%, melt index is 3-10, and mass fraction is that the nanometer organic modification montmonrillonite of 3%-10% is pre-mixed, extruding pelletization, prepares the nanometer inorganic flame retardant pellet;
Described step 2) method for preparing the flame-proof polyethylene blend composition in comprises: by nanometer inorganic flame retardant material and the mass fraction of preparation in described step 1, be at first the polyethylene of 60%-85%, (melt index is 3-10), mass fraction is the ethylene-vinyl acetate blend of 10%-30%, obtains the flame-proof polyethylene blend composition; The method for preparing the flame-proof polyethylene woven cloth in described step 3) comprises: at first by in described step 2 preparation the flame-proof polyethylene blend composition cooling after extrusion film in extruding machine, cut, the heating orientation stretching, after the pre-heat treatment typing, wrapup procedure, through broadwise, be woven into the flame retardant plastics woven cloth.
Further, the thread count of described flame retardant plastics woven cloth is 8 * 8-10 * 10, and thickness is 30-90 g/m
2.
compared with prior art, the present invention has the following advantages: (1) adopts organic nano imvite as synergistic fire retardant, improved on the one hand the compatibility of halogen-free flame retardants and polyethylene group, the intercalation configuration that forms with polymeric matrix that adds of nanoclay has blocking effect on the other hand, utilize the draw ratio that nanoclay is high, when material combustion, form one deck enhancement layer and effectively stoped subsiding of carburization zone, the existence of carburization zone can be effectively isolated by unburned polymer surfaces, the cigarette amount of combustible and distributing of flue gas have been reduced, therefore, reduced the consumption of halogen-free flame retardants, obtain simultaneously having better good flame retardation effect and mechanical property fire-retardant polyethylene material, (2) the present invention adopts silane coupler to carry out the surface polarity modification to the nano-sized magnesium hydroxide particle simultaneously, strengthens itself and poly compatibility.Then adopt the ethylene-vinyl acetate elastomer to coat modification, melt extrude prilling process, strengthened and made the compatibility of inorganic nano-particle in polymeric matrix, made the inorganic nano ion uniformly dispersed in polymeric matrix, avoided the agglomeration that causes due to nano effect; (3) in preparation method of the present invention, the intensity of polymeric matrix metallocene PE is very high, adopt high-intensity metallocene PE can improve the intensity of woven polyethylene cloth, has solved the problem of the strength decreased that ethylene-vinyl acetate brings; (4) heat decomposition temperature of magnesium hydroxide (340 ℃ of left and right) is high than aluminium hydroxide, is conducive to the raising of plastic processing temperature, and is 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 for preparing of the present invention is a kind of environmentally friendly fire proofing, not halogen-containing, after burning, do not discharge poison gas, Environmental Safety, have good fire resistance and mechanical property, this flame-proof polyethylene woven cloth technique is simple, cost, performance improve, and has a wide range of applications.
Specific implementation method
The present invention is further illustrated below in conjunction with embodiment, but not as the foundation to the present invention's restriction.
Embodiment 1: a kind of preparation method of halogen-free flame-retardant polyethylene plastic woven cloth comprises the steps:
1. prepare the nanometer inorganic flame retardant material;
2. prepare flame resistance polyethylene composite material;
3. to fire-retardant polyethylene material, carry out wire drawing and weave cotton cloth, forming the flame-proof polyethylene woven cloth;
In the preparation method of above-mentioned flame-retardant high-molecular woven cloth, the method for preparing the nano inorganic fire proofing in described step 1 comprises: by mass fraction, be at first that 80% magnesium hydroxide and mass fraction are that the silane coupler that diluted of 1% diluent is under 110 ℃, high-speed stirred 0.5 hour, drying, stand-by.Then the magnesium hydroxide of above-mentioned modification and mass fraction are that 50% ethylene-vinyl acetate and mass fraction are that 5% nanometer organic modification montmonrillonite is 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 be 20%, melt index is 6.
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 for preparing the flame-proof polyethylene blend composition in described step 2 comprises: by nanometer inorganic flame retardant material and the mass fraction of preparation in described step 1, be at first the 60%-85% metallocene PE, mass fraction is the ethylene-vinyl acetate blend of 10%-30%.
In described step 2, polyethylene is metallocene PE, and the melt index of described metallocene PE is 7.5.
In described step 2 in ethylene-vinyl acetate copolymer vinyl acetate content be 20%, melt index is 6.
In the preparation method of above-mentioned flame-retardant high-molecular woven cloth, the method for preparing the flame-proof polyethylene woven cloth in described step 3 comprises: at first by in described step 2 preparation the flame-proof polyethylene blend composition cooling after extrusion film in extruding machine, cut, the heating orientation stretching, after the pre-heat treatment typing, wrapup procedure, through broadwise, be woven into the flame retardant plastics woven cloth.
In described step 3, the thread count of woven cloth is 10 * 10, and thickness is 60g/m
2.
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 the nanometer inorganic flame retardant material;
2. prepare flame resistance polyethylene composite material;
3. to fire-retardant polyethylene material, carry out wire drawing and weave cotton cloth, forming the flame-proof polyethylene woven cloth;
In the preparation method of above-mentioned flame-retardant high-molecular woven cloth, the method for preparing the nano inorganic fire proofing in described step 1 comprises: by mass fraction, be at first that 80% magnesium hydroxide and mass fraction are that the silane coupler that diluted of 1% diluent is under 110 ℃, high-speed stirred 0.5 hour, drying, stand-by.Then the magnesium hydroxide of above-mentioned modification and mass fraction are that 50% ethylene-vinyl acetate and mass fraction are that 5% nanometer organic modification montmonrillonite is 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 be 23%, melt index is 8.
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 for preparing the flame-proof polyethylene blend composition in described step 2 comprises: by nanometer inorganic flame retardant material and the mass fraction of preparation in described step 1, be at first the 60%-85% metallocene PE, mass fraction is the ethylene-vinyl acetate blend of 10%-30%.
In described step 2, polyethylene is metallocene PE, and the melt index of described metallocene PE is 5.
In described step 2 in ethylene-vinyl acetate copolymer vinyl acetate content be 23%, melt index is 8.
In the preparation method of above-mentioned flame-retardant high-molecular woven cloth, the method for preparing the flame-proof polyethylene woven cloth in described step 3 comprises: at first by in described step 2 preparation the flame-proof polyethylene blend composition cooling after extrusion film in extruding machine, cut, the heating orientation stretching, after the pre-heat treatment typing, wrapup procedure, through broadwise, be woven into the flame retardant plastics woven cloth.
In described step 3, the thread count of woven cloth is 8 * 8, and thickness is 60g/m
2.
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 the nanometer inorganic flame retardant material;
2. prepare flame resistance polyethylene composite material;
3. to fire-retardant polyethylene material, carry out wire drawing and weave cotton cloth, forming the flame-proof polyethylene woven cloth;
In the preparation method of above-mentioned flame-retardant high-molecular woven cloth, the method for preparing the nano inorganic fire proofing in described step 1 comprises: by mass fraction, be at first that 80% magnesium hydroxide and mass fraction are that the silane coupler that diluted of 1% diluent is under 110 ℃, high-speed stirred 0.5 hour, drying, stand-by.Then the magnesium hydroxide of above-mentioned modification and mass fraction are that 50% ethylene-vinyl acetate and mass fraction are that 5% nanometer organic modification montmonrillonite is 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 be 25%, melt index is 10.
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 for preparing the flame-proof polyethylene blend composition in described step 2 comprises: by nanometer inorganic flame retardant material and the mass fraction of preparation in described step 1, be at first the 60%-85% metallocene PE, mass fraction is the ethylene-vinyl acetate blend of 10%-30%.
In described step 2, polyethylene is metallocene PE, and the melt index of described metallocene PE is 6.
In described step 2 in ethylene-vinyl acetate copolymer vinyl acetate content be 25%, melt index is 10.
In the preparation method of above-mentioned flame-retardant high-molecular woven cloth, the method for preparing the flame-proof polyethylene woven cloth in described step 3 comprises: at first by in described step 2 preparation the flame-proof polyethylene blend composition cooling after extrusion film in extruding machine, cut, the heating orientation stretching, after the pre-heat treatment typing, wrapup procedure, through broadwise, be woven into the flame retardant plastics woven cloth.
In described step 3, the thread count of woven cloth is 10 * 10, and thickness is 60g/m
2.
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 (8)
1. halogen-free flame-retardant polyethylene plastic woven cloth, it is characterized in that, the quality percentage composition of described halogen-free flame-retardant polyethylene plastic woven cloth chemical composition is: polyethylene 50%-85%, ethylene-vinyl acetate elastomer 10%-30%, nanometer inorganic flame retardant system 20%-60%, in described nanometer inorganic flame retardant system, each percentage by weight that forms is as follows: magnesium hydroxide 50%-85%, silane coupler 1%-2%, ethylene-vinyl acetate copolymer 10%-30%, organic modification montmonrillonite 2%-8%.
2. halogen-free flame-retardant polyethylene plastic woven cloth according to claim 1, is characterized in that, described polyethylene is metallocene linear-low density polyethylene.
3. halogen-free flame-retardant polyethylene plastic woven cloth according to claim 1, is characterized in that, in described ethylene-vinyl acetate elastomer, the content of vinylacetate is 15-35%.
4. 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.
5. halogen-free flame-retardant polyethylene plastic woven cloth according to claim 1, is characterized in that, described silane coupler is γ-glycidol oxygen propyl trimethoxy siloxanes.
6. 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 between 2-3nm, and particle diameter is 100-300nm.
7. the preparation method of the described halogen-free flame-retardant polyethylene plastic woven cloth of claim 1-6, is characterized in that, comprises the steps: 1) prepare the nanometer inorganic flame retardant material; 2) prepare the Zero halogen flame resistance polyethylene blend composition; 3) to halogen-free fire-retardant polyethylene material, carry out wire drawing and weave cotton cloth, forming the Zero halogen flame resistance polyethylene woven cloth;
The method for preparing the nanometer inorganic flame retardant material in described step 1) comprises: by mass fraction, be at first that the magnesium hydroxide of 50%-85% and mass fraction are that the silane coupler that diluted of 1%-2% diluent is under 80-120 ℃, high-speed stirred 0.5-2 hour, drying, obtain the magnesium hydroxide of modification; Then by the magnesium hydroxide of above-mentioned modification, mass fraction, be the ethylene-vinyl acetate of 20%-60%, wherein vinyl acetate content is 15-35%, melt index is 3-10, and mass fraction is that the nanometer organic modification montmonrillonite of 3%-10% is pre-mixed, extruding pelletization, prepares the nanometer inorganic flame retardant pellet;
Described step 2) method for preparing the flame-proof polyethylene blend composition in comprises: by nanometer inorganic flame retardant material and the mass fraction of preparation in described step 1, be at first the polyethylene of 60%-85%, (melt index is 3-10), mass fraction is the ethylene-vinyl acetate blend of 10%-30%, obtains the flame-proof polyethylene blend composition;
The method for preparing the flame-proof polyethylene woven cloth in described step 3) comprises: at first by in described step 2 preparation the flame-proof polyethylene blend composition cooling after extrusion film in extruding machine, cut, the heating orientation stretching, after the pre-heat treatment typing, wrapup procedure, through broadwise, be woven into the halogen-free fire retardant plastic woven cloth.
8. the preparation method of halogen-free flame-retardant polyethylene plastic woven cloth according to claim 7, is characterized in that, the thread count of described halogen-free fire retardant plastic woven cloth is 8 * 8-10 * 10, and thickness is 30-90g/m
2.
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| CN104179018A (en) * | 2014-08-14 | 2014-12-03 | 浙江辰鸿纺织品科技有限公司 | Preparation method of coating window decoration |
| CN104195670A (en) * | 2014-08-16 | 2014-12-10 | 青岛供八方塑料有限公司 | Agricultural plastic woven fabric for greenhouses and preparation method thereof |
| CN107151539A (en) * | 2017-04-20 | 2017-09-12 | 临安福斯特热熔网膜有限公司 | A kind of automotive upholstery environment-friendly hot-melt glued membrane and preparation method and purposes |
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| CN111074536A (en) * | 2019-12-25 | 2020-04-28 | 江苏领瑞新材料科技有限公司 | Preparation method of fire-resistant flame-retardant polyethylene fiber UD cloth |
| CN113667207A (en) * | 2021-09-13 | 2021-11-19 | 浦江盛茂新材料有限公司 | Preparation method of Polyethylene (PE) composite material |
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