CN101429302A - Halogen free flame-proof composite material of polythene and preparation method thereof - Google Patents
Halogen free flame-proof composite material of polythene and preparation method thereof Download PDFInfo
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- CN101429302A CN101429302A CNA2008102037912A CN200810203791A CN101429302A CN 101429302 A CN101429302 A CN 101429302A CN A2008102037912 A CNA2008102037912 A CN A2008102037912A CN 200810203791 A CN200810203791 A CN 200810203791A CN 101429302 A CN101429302 A CN 101429302A
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
- B29C48/00—Extrusion moulding, i.e. expressing the moulding material through a die or nozzle which imparts the desired form; Apparatus therefor
- B29C48/25—Component parts, details or accessories; Auxiliary operations
- B29C48/36—Means for plasticising or homogenising the moulding material or forcing it through the nozzle or die
- B29C48/395—Means for plasticising or homogenising the moulding material or forcing it through the nozzle or die using screws surrounded by a cooperating barrel, e.g. single screw extruders
- B29C48/40—Means for plasticising or homogenising the moulding material or forcing it through the nozzle or die using screws surrounded by a cooperating barrel, e.g. single screw extruders using two or more parallel screws or at least two parallel non-intermeshing screws, e.g. twin screw extruders
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
- B29C48/00—Extrusion moulding, i.e. expressing the moulding material through a die or nozzle which imparts the desired form; Apparatus therefor
- B29C48/03—Extrusion moulding, i.e. expressing the moulding material through a die or nozzle which imparts the desired form; Apparatus therefor characterised by the shape of the extruded material at extrusion
- B29C48/04—Particle-shaped
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
- B29C48/00—Extrusion moulding, i.e. expressing the moulding material through a die or nozzle which imparts the desired form; Apparatus therefor
- B29C48/25—Component parts, details or accessories; Auxiliary operations
- B29C48/92—Measuring, controlling or regulating
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
- B29C2948/00—Indexing scheme relating to extrusion moulding
- B29C2948/92—Measuring, controlling or regulating
- B29C2948/92504—Controlled parameter
- B29C2948/92704—Temperature
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
- B29C2948/00—Indexing scheme relating to extrusion moulding
- B29C2948/92—Measuring, controlling or regulating
- B29C2948/92819—Location or phase of control
- B29C2948/92857—Extrusion unit
- B29C2948/92876—Feeding, melting, plasticising or pumping zones, e.g. the melt itself
- B29C2948/92895—Barrel or housing
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Abstract
The invention provides a halogen-free flame retardant polyethylene composite material, which is characterized by consisting of the following raw materials in weight portion: 74.3 to 41.5 portions of polyethylene; 0.2 to 1.5 portions of heat stabilizer; 0.3 to 1 portion of light stabilizer; 0.2 to 1 portion of processing aid; 23 to 50 portions of halogen-free flame retardant; and 2 to 5 portions of nanometer addition agent. The invention also provides a method for preparing the composite material. Compared with the prior halogen-free flame retardant polyethylene, the composite material greatly improves the flame retardant performance of polyethylene due to the addition of the nanometer addition agent, and reduces the usage of the halogen-free flame retardant; besides, the obtained polyethylene has better mechanical properties, smoother surface and faster extrusion.
Description
Technical field
The present invention relates to a kind of halogen-free polythene flame redardant composite material and preparation method thereof, belong to technical field of polymer materials.
Background technology
Polyethylene (PE) is the thermoplastics of consumption maximum, has the chemical stability and the dielectric properties of excellent electric insulation, lower temperature resistance, easily machine-shaping, excellence, is widely used in film, daily necessities, tubing, electric wire.The poly tempo of China is very fast, and average annual increase of production rate reaches 11.55%.Along with the raising of people to the plastic prod performance requriements, A Study of Flame-retardant Polyethylene and application are also developed by leaps and bounds.The halogenous fire retardant of the many employings of early stage A Study of Flame-retardant Polyethylene, this based flame retardant has good flame retardation effect, the advantage that addition is low, but the amount of being fuming is big in fire-retardant process, and emit poisonous, mordant hydrogen halide, cause secondary disaster easily, so raising along with fire-fighting and safety and environmental protection notion, in use receive restriction, in order to reduce the hazardness of flame-proof polyethylene, begin both at home and abroad low cigarette, the polyethylene of low toxicity is studied, this just makes that halogen-free flame retardants comes into one's own again, and its flame retardant effect and and poly consistency aspect carried out serial research.It is expanding fire retardant and inorganic hydroxide etc. that halogen-free flame retardants commonly used has red phosphorus, phosphorus-nitrogen, and is applied in many important fields such as electric wire, building penetration pipe, colliery tubing, shaft building engineering, subway, tunnel, offshore oil production and nuclear power stations.
Al (OH) is adopted in domestic research to Zero halogen flame resistance polyethylene
3, Mg (OH)
2A lot of as Study of Flame Retardant, Al (OH)
3, Mg (OH)
2Be current generally acknowledged have fire-retardant, press down cigarette, fill three big functions fire retardant, it has the advantage that does not produce toxic gas under nontoxic, no burn into good stability, non-volatile, the high temperature, and it is cheap, wide material sources, but as fire retardant, it also has loading level big, the shortcoming of mechanical properties decrease, processibility variation.Use Al (OH) separately
3, Mg (OH)
2As the fire retardant filled polyethylene, the oxygen index of flame-proof polyethylene is along with Al (OH)
3, Mg (OH)
2Loading level increase and improve, but at low loading level (less than 50% part), flame retardant effect is also not obvious, has only a large amount of fillings just can reach certain flame retardant effect.From present domestic A Study of Flame-retardant Polyethylene present situation, its flame retardant resistance of independent Zero halogen flame resistance polyethylene and mechanical property are difficult to satisfy simultaneously the requirement of product, and the fire retardant of import costs an arm and a leg, thus in recent years to Al (OH)
3, Mg (OH)
2There is the research of the fire-resistant synergistic system of synergistic effect more and more to come into one's own.Study more polyethylene anti-flaming synergist and be mainly red phosphorus and phosphide, but in use effect not very remarkable.
Summary of the invention
The purpose of this invention is to provide a kind of halogen-free polythene flame redardant composite material and preparation method thereof,, satisfy the industrial needs that Zero halogen flame resistance polyethylene is constantly developed to overcome the defective that prior art exists.
In order to achieve the above object, technical scheme of the present invention provides a kind of halogen-free polythene flame redardant composite material, it is characterized in that, is made up of following raw material in weight part:
Polyethylene 74.3-41.5;
Thermo-stabilizer 0.2-1.5;
Photostabilizer 0.3-1;
Processing aid 0.2-1;
Halogen-free flame retardants 23-50;
Nano assistant 2-5;
Wherein, described thermo-stabilizer is the mixture class of phenols, amine, phosphorous acid esters, acryl functional group and monothioester or a kind of or its mixture in the calixarene kind thermo-stabilizer;
Described photostabilizer is a hindered amine light stabilizer;
Described processing aid is a kind of or its mixture in low molecule ester class, metallic soap class, stearic acid complex ester class and the amides processing aid;
Described halogen-free flame retardants is one or more the mixture in magnesium hydroxide, aluminium hydroxide and the stannic oxide;
Described nano assistant is one or both a mixture of nanoclay and multi-walled carbon nano-tubes.
Further, described polyethylene is that molecular weight is preferably 10-20 ten thousand polyethylene.
Described phenols thermo-stabilizer is preferably 2,4-DI-tert-butylphenol compounds or 1,3,5-trimethylammonium-2,4,6-three (3, the 5-di-tert-butyl-4-hydroxyl benzyl) benzene.
Described amine thermo-stabilizer is preferably 4-N-butyl amino-2,2,6,6-tetramethyl piperidine.
Described phosphorous acid ester type thermal stabilizing agent is preferably triphenyl phosphite.
The mixture type thermal stabilizing agent of described acryl functional group and monothioester is preferably CT-50A.
Described calixarene kind thermo-stabilizer is preferably tertiary butyl cup [4] aromatic hydrocarbons.
Described hindered amine light stabilizer is preferably poly-{ [6-[(1,1,3, the 3-tetramethyl butyl) amino]]-1,3,5-triazines-2,4-[(2,2,6,6,-tetramethyl-4-piperidyl) imino-]-1,6-oneself two the support [(2,2,6,6-tetramethyl--4-piperidyl) imino-] } (HS-944), one or more the mixture in N-alkylation class hindered amine as light stabilizer, piperazine ketone structurizing class hindered amine as light stabilizer or the hindered amines UV light absorber.
Described N-alkylation class hindered amine as light stabilizer is preferably two (2,2,6, the 6-tetramethyl-piperidyl) sebates.
Described piperazine ketone structurizing class hindered amine as light stabilizer is preferably Good-rite 3159.
Described hindered amines UV light absorber is preferably 2-(4, two (2, the 4-3,5-dimethylphenyl)-1,3,5-triazines-2-yls of 6-)-5-octyloxy phenol.
Described low molecule ester class processing aid is preferably acrylate.
Described metallic soap class processing aid is preferably sodium palmitate.
Described stearic acid complex ester class processing aid is preferably pentaerythritol stearate.
Described amides processing aid is preferably ethylene bis stearamide.
Described nanoclay is preferably layered silicate, and its particle diameter is 10-200nm, and median size is 60-80nm.
The mean outside diameter of described multi-walled carbon nano-tubes is preferably 10-20nm, and mean length is preferably 5-15m.
The present invention also provides the preparation method of above-mentioned a kind of halogen-free polythene flame redardant composite material, it is characterized in that, concrete steps are:
The first step: in proportion 3/10-1/2 polyethylene, nano assistant and 3/10-1/2 processing aid are mixed, under 150-190 ℃ of condition, extrude in forcing machine, prepare the polyethylene master batch that contains nano assistant;
Second step: in proportion 3/10-1/2 polyethylene, halogen-free flame retardants and 3/10-1/2 processing aid are mixed, under 150-190 ℃ of condition, extrude in forcing machine, prepare the polyethylene master batch that contains fire retardant;
The 3rd step: the polyethylene master batch that contains nano assistant that will obtain, the polyethylene master batch and thermo-stabilizer, photostabilizer and remaining polyethylene and the processing aid that contain fire retardant, in length-to-diameter ratio is to disperse extruding pelletization in the twin screw extruder of 35-45:1 150-190 ℃ of melting mixing.
The present invention mainly is that the adding nanoclay had both improved the consistency between halogen-free flame retardants and the polyvinyl resin, the adding of nanoclay simultaneously has blocking effect and nano effect with the intercalation configuration of polyvinyl body formation, and the flame retardant properties of bittern-free flame-proof material is had synergism; Utilize the length-to-diameter ratio of carbon nanotube excellence, form one deck enhancement layer and effectively stoped subsiding of carburization zone when material combustion, the existence of carburization zone can be effectively isolated with unburned polymer surfaces, therefore reduced the amount of combustiblematerials and distributing of flue gas.
Compare with traditional Zero halogen flame resistance polyethylene, the adding of nano assistant has improved poly flame retardant properties greatly, has reduced the consumption of halogen-free flame retardants, and the polyethylene that obtains has better mechanical property, more slick surface and extruded velocity faster.
Embodiment
The present invention will be further described below in conjunction with embodiment.
Embodiment 1
A kind of halogen-free polythene flame redardant composite material, be made up of following raw material in weight part: molecular weight is 100,000 polyethylene 74.3, thermo-stabilizer 2,4-DI-tert-butylphenol compounds 0.2, photostabilizer gathers { [6-[(1,1,3, the 3-tetramethyl butyl) amino]]-1,3,5-triazines-2,4-[(2,2,6,6,-tetramethyl-4-piperidyl) imino-]-1,6-oneself two the support [(2,2,6,6-tetramethyl--4-piperidyl) imino-] } (HS-944) 0.3, processing aid acrylate 0.2, halogen-free flame retardants magnesium hydroxide 23 and nano assistant nanoclay (layered silicate, particle diameter 10-200nm, median size 60nm) 2.Its preparation method is as follows:
Contain the preparation of the polyethylene master batch of nano assistant: in proportion 3/10 polyethylene, nano assistant and 3/10 processing aid are mixed, under 150 ℃ of conditions, extrude in forcing machine, prepare the polyethylene master batch that contains nano assistant;
Contain the preparation of the polyethylene master batch of fire retardant: in proportion 3/10 polyethylene, halogen-free flame retardants and 3/10 processing aid are mixed, under 150 ℃ of conditions, extrude in forcing machine, prepare the polyethylene master batch that contains fire retardant;
With the polyethylene master batch that contains nano assistant that obtains, contain polyethylene master batch and thermo-stabilizer, photostabilizer and the remaining polyethylene and the processing aid of fire retardant, be to disperse extruding pelletization in the twin screw extruder of 35:1 150 ℃ of melting mixing in length-to-diameter ratio.
Embodiment 2
A kind of halogen-free polythene flame redardant composite material, be made up of following raw material in weight part: molecular weight is 200,000 polyethylene 41.5, thermo-stabilizer 1,3,5-trimethylammonium-2,4,6-three (3, the 5-di-tert-butyl-4-hydroxyl benzyl) (Irganox 1010 for benzene, vapour Bagong department produces) 1.5, photostabilizer two (2,2,6, the 6-tetramethyl-piperidyl) sebate 1, processing aid sodium palmitate 1, halogen-free flame retardants aluminium hydroxide 50 and nano assistant nanoclay (layered silicate, particle diameter 10-200nm, median size 80nm) 2 and multi-walled carbon nano-tubes (mean outside diameter 10-20nm, mean length 5nm) 3.Its preparation method is as follows:
Contain the preparation of the polyethylene master batch of nano assistant: in proportion 1/2 polyethylene, nano assistant and 1/2 processing aid are mixed, under 190 ℃ of conditions, extrude in forcing machine, prepare the polyethylene master batch that contains nano assistant;
Contain the preparation of the polyethylene master batch of fire retardant: in proportion 1/2 polyethylene, halogen-free flame retardants and 1/2 processing aid are mixed, under 190 ℃ of conditions, extrude in forcing machine, prepare the polyethylene master batch that contains fire retardant;
With the polyethylene master batch that contains nano assistant that obtains, contain polyethylene master batch and thermo-stabilizer, photostabilizer and the remaining polyethylene and the processing aid of fire retardant, be to disperse extruding pelletization in the twin screw extruder of 45:1 190 ℃ of melting mixing in length-to-diameter ratio.
Embodiment 3
A kind of halogen-free polythene flame redardant composite material, be made up of following raw material in weight part: molecular weight is 150,000 polyethylene 60, thermo-stabilizer 4-N-butyl amino-2,2,6,6-tetramethyl piperidine 0.5, photostabilizer Good-rite 3159 (producing) 1 by BFGoodrich BF Goodrich company, processing aid pentaerythritol stearate 0.5, halogen-free flame retardants stannic oxide 35 and nano assistant multi-walled carbon nano-tubes (mean outside diameter 10-20nm, mean length 5nm) 3.Its preparation method is as follows:
Contain the preparation of the polyethylene master batch of nano assistant: in proportion 2/5 polyethylene, nano assistant and 2/5 processing aid are mixed, under 180 ℃ of conditions, extrude in forcing machine, prepare the polyethylene master batch that contains nano assistant;
Contain the preparation of the polyethylene master batch of fire retardant: in proportion 2/5 polyethylene, halogen-free flame retardants and 2/5 processing aid are mixed, under 180 ℃ of conditions, extrude in forcing machine, prepare the polyethylene master batch that contains fire retardant;
With the polyethylene master batch that contains nano assistant that obtains, contain polyethylene master batch and thermo-stabilizer, photostabilizer and the remaining polyethylene and the processing aid of fire retardant, be to disperse extruding pelletization in the twin screw extruder of 40:1 180 ℃ of melting mixing in length-to-diameter ratio.
Embodiment 4
A kind of halogen-free polythene flame redardant composite material, be made up of following raw material in weight part: molecular weight is 150,000 polyethylene 60, thermo-stabilizer triphenyl phosphite 0.5, (4,6-two (2 for photostabilizer 2-, the 4-3,5-dimethylphenyl)-1,3,5-triazine-2-yl)-5-octyloxy phenol 1, processing aid dispersion agent EBS (reaching the production of chemical industry company limited) 0.5 by giving birth to, halogen-free flame retardants stannic oxide 20 and magnesium hydroxide 15 and nano assistant multi-walled carbon nano-tubes (mean outside diameter 10-20nm, mean length 15nm) 3.Its preparation method is as follows:
Contain the preparation of the polyethylene master batch of nano assistant: in proportion 2/5 polyethylene, nano assistant and 2/5 processing aid are mixed, under 180 ℃ of conditions, extrude in forcing machine, prepare the polyethylene master batch that contains nano assistant;
Contain the preparation of the polyethylene master batch of fire retardant: in proportion 2/5 polyethylene, halogen-free flame retardants and 2/5 processing aid are mixed, under 180 ℃ of conditions, extrude in forcing machine, prepare the polyethylene master batch that contains fire retardant;
With the polyethylene master batch that contains nano assistant that obtains, contain polyethylene master batch and thermo-stabilizer, photostabilizer and the remaining polyethylene and the processing aid of fire retardant, be to disperse extruding pelletization in the twin screw extruder of 40:1 180 ℃ of melting mixing in length-to-diameter ratio.
Embodiment 5
A kind of halogen-free polythene flame redardant composite material, be made up of following raw material in weight part: molecular weight is 150,000 polyethylene 55, thermo-stabilizer CT-50A (the strong additives for plastics of Shanghai intelligence company limited) 0.2, photostabilizer TINUV 770 (is a kind of hindered amine as light stabilizer, two (2,2,6, the 6-tetramethyl-piperidyl) sebate) (produces) 0.3 by Ciba company, processing aid dispersion agent EBS (reaching the production of chemical industry company limited) 0.5 by giving birth to, halogen-free flame retardants aluminium hydroxide 27 and magnesium hydroxide 15 and nano assistant multi-walled carbon nano-tubes (mean outside diameter 10-20nm, mean length 10nm) 2.Its preparation method is as follows:
Contain the preparation of the polyethylene master batch of nano assistant: in proportion 2/5 polyethylene, nano assistant and 2/5 processing aid are mixed, under 180 ℃ of conditions, extrude in forcing machine, prepare the polyethylene master batch that contains nano assistant;
Contain the preparation of the polyethylene master batch of fire retardant: in proportion 2/5 polyethylene, halogen-free flame retardants and 2/5 processing aid are mixed, under 180 ℃ of conditions, extrude in forcing machine, prepare the polyethylene master batch that contains fire retardant;
With the polyethylene master batch that contains nano assistant that obtains, contain polyethylene master batch and thermo-stabilizer, photostabilizer and the remaining polyethylene and the processing aid of fire retardant, be to disperse extruding pelletization in the twin screw extruder of 40:1 180 ℃ of melting mixing in length-to-diameter ratio.
Embodiment 6
A kind of halogen-free polythene flame redardant composite material, be made up of following raw material in weight part: molecular weight is 150,000 polyethylene 55, thermo-stabilizer is to tertiary butyl cup [4] aromatic hydrocarbons 0.5, photostabilizer TINUV 770 (is a kind of hindered amine as light stabilizer, two (2,2,6, the 6-tetramethyl-piperidyl) sebate) (produces) 1 by Ciba company, processing aid dispersion agent EBS (reaching the production of chemical industry company limited) 0.5 by giving birth to, halogen-free flame retardants aluminium hydroxide 20 and magnesium hydroxide 20 and nano assistant multi-walled carbon nano-tubes (mean outside diameter 10-20nm, mean length 10nm) 3.Its preparation method is as follows:
Contain the preparation of the polyethylene master batch of nano assistant: in proportion 2/5 polyethylene, nano assistant and 2/5 processing aid are mixed, under 180 ℃ of conditions, extrude in forcing machine, prepare the polyethylene master batch that contains nano assistant;
Contain the preparation of the polyethylene master batch of fire retardant: in proportion 2/5 polyethylene, halogen-free flame retardants and 2/5 processing aid are mixed, under 180 ℃ of conditions, extrude in forcing machine, prepare the polyethylene master batch that contains fire retardant;
With the polyethylene master batch that contains nano assistant that obtains, contain polyethylene master batch and thermo-stabilizer, photostabilizer and the remaining polyethylene and the processing aid of fire retardant, be to disperse extruding pelletization in the twin screw extruder of 40:1 180 ℃ of melting mixing in length-to-diameter ratio.
Embodiment 7
A kind of halogen-free polythene flame redardant composite material, be made up of following raw material in weight part: molecular weight is 150,000 polyethylene 60, thermo-stabilizer is to tertiary butyl cup [4] aromatic hydrocarbons 0.25 and triphenyl phosphite 0.25, photostabilizer two (2,2,6, the 6-tetramethyl-piperidyl) sebate 0.5 and 2-(4,6-two (2, the 4-3,5-dimethylphenyl)-1,3,5-triazine-2-yl)-and 5-octyloxy phenol 0.5, processing aid dispersion agent EBS (reaching the production of chemical industry company limited) 0.25 and pentaerythritol stearate 0.25, halogen-free flame retardants aluminium hydroxide 20 and magnesium hydroxide 15 and nano assistant multi-walled carbon nano-tubes (mean outside diameter 10-20nm by giving birth to, mean length 10nm) 1.5 and nanoclay (layered silicate, particle diameter 10-200nm, median size 60nm) 1.5.Its preparation method is as follows:
Contain the preparation of the polyethylene master batch of nano assistant: in proportion 2/5 polyethylene, nano assistant and 2/5 processing aid are mixed, under 180 ℃ of conditions, extrude in forcing machine, prepare the polyethylene master batch that contains nano assistant;
Contain the preparation of the polyethylene master batch of fire retardant: in proportion 2/5 polyethylene, halogen-free flame retardants and 2/5 processing aid are mixed, under 180 ℃ of conditions, extrude in forcing machine, prepare the polyethylene master batch that contains fire retardant;
With the polyethylene master batch that contains nano assistant that obtains, contain polyethylene master batch and thermo-stabilizer, photostabilizer and the remaining polyethylene and the processing aid of fire retardant, be to disperse extruding pelletization in the twin screw extruder of 40:1 180 ℃ of melting mixing in length-to-diameter ratio.
Each embodiment specific performance data is as shown in the table:
| Embodiment 1 | Embodiment 2 | Embodiment 3 | Embodiment 4 | Embodiment 5 | Embodiment 6 | Embodiment 7 | |
| Flame retardant properties UL-94 | V-0 3mm | V-0 2mm | V-0 2mm | V-0 2mm | V-0 2mm | V-0 2mm | V-0 2mm |
| Tensile strength (MPa) | 26.7 | 27.4 | 29.6 | 29.8 | 28.2 | 29.0 | 30.6 |
| Modulus in flexure (Mpa) | 1035 | 1150 | 1280 | 1283 | 1270 | 1279 | 1316 |
| Notched Izod impact strength (KJ/m 2) | 16.4 | 15.8 | 16.3 | 16.1 | 15.7 | 17.2 | 17.5 |
Claims (18)
1. a halogen-free polythene flame redardant composite material is characterized in that, is made up of following raw material in weight part:
Polyethylene 74.3-41.5;
Thermo-stabilizer 0.2-1.5;
Photostabilizer 0.3-1;
Processing aid 0.2-1;
Halogen-free flame retardants 23-50;
Nano assistant 2-5;
Wherein, described thermo-stabilizer is the mixture class of phenols, amine, phosphorous acid esters, acryl functional group and monothioester or a kind of or its mixture in the calixarene kind thermo-stabilizer;
Described photostabilizer is a hindered amine light stabilizer;
Described processing aid is a kind of or its mixture in low molecule ester class, metallic soap class, stearic acid complex ester class and the amides processing aid;
Described halogen-free flame retardants is one or more the mixture in magnesium hydroxide, aluminium hydroxide and the stannic oxide;
Described nano assistant is one or both a mixture of nanoclay and multi-walled carbon nano-tubes.
2. a kind of halogen-free polythene flame redardant composite material as claimed in claim 1 is characterized in that, described polyethylene is that molecular weight is 10-20 ten thousand polyethylene.
3. a kind of halogen-free polythene flame redardant composite material as claimed in claim 1 is characterized in that, described phenols thermo-stabilizer is 2,4-DI-tert-butylphenol compounds or 1,3,5-trimethylammonium-2,4,6-three (3, the 5-di-tert-butyl-4-hydroxyl benzyl) benzene.
4. a kind of halogen-free polythene flame redardant composite material as claimed in claim 1 is characterized in that, described amine thermo-stabilizer is a 4-N-butyl amino-2,2,6, the 6-tetramethyl piperidine.
5. a kind of halogen-free polythene flame redardant composite material as claimed in claim 1 is characterized in that, described phosphorous acid ester type thermal stabilizing agent is a triphenyl phosphite.
6. a kind of halogen-free polythene flame redardant composite material as claimed in claim 1 is characterized in that, the mixture type thermal stabilizing agent of described acryl functional group and monothioester is CT-50A.
7. a kind of halogen-free polythene flame redardant composite material as claimed in claim 1 is characterized in that, described calixarene kind thermo-stabilizer is to tertiary butyl cup [4] aromatic hydrocarbons.
8. a kind of halogen-free polythene flame redardant composite material as claimed in claim 1, it is characterized in that, described hindered amine light stabilizer is poly-{ [6-[(1,1,3, the 3-tetramethyl butyl) amino]]-1,3,5-triazine-2,4-[(2,2,6,6,-tetramethyl-4-piperidyl) imino-]-1,6-oneself two the support [(2,2,6,6-tetramethyl--4-piperidyl) imino-] }, one or more the mixture in N-alkylation class hindered amine as light stabilizer, piperazine ketone structurizing class hindered amine as light stabilizer or the hindered amines UV light absorber.
9. a kind of halogen-free polythene flame redardant composite material as claimed in claim 8 is characterized in that, described N-alkylation class hindered amine as light stabilizer is two (2,2,6, the 6-tetramethyl-piperidyl) sebates.
10. a kind of halogen-free polythene flame redardant composite material as claimed in claim 8 is characterized in that, described piperazine ketone structurizing class hindered amine as light stabilizer is Good-rite 3159.
11. a kind of halogen-free polythene flame redardant composite material as claimed in claim 8 is characterized in that, described hindered amines UV light absorber is 2-(4, two (2, the 4-3,5-dimethylphenyl)-1,3,5-triazines-2-yls of 6-)-5-octyloxy phenol.
12. a kind of halogen-free polythene flame redardant composite material as claimed in claim 1 is characterized in that, described low molecule ester class processing aid is an acrylate.
13. a kind of halogen-free polythene flame redardant composite material as claimed in claim 1 is characterized in that, described metallic soap class processing aid is a sodium palmitate.
14. a kind of halogen-free polythene flame redardant composite material as claimed in claim 1 is characterized in that, described stearic acid complex ester class processing aid is a pentaerythritol stearate.
15. a kind of halogen-free polythene flame redardant composite material as claimed in claim 1 is characterized in that, described amides processing aid is an ethylene bis stearamide.
16. a kind of halogen-free polythene flame redardant composite material as claimed in claim 1 is characterized in that, described nanoclay is a layered silicate, and its particle diameter is 10-200nm, and median size is 60-80nm.
17. a kind of halogen-free polythene flame redardant composite material as claimed in claim 1 is characterized in that, the mean outside diameter of described multi-walled carbon nano-tubes is 10-20nm, and mean length is 5-15m.
18. the preparation method of a kind of halogen-free polythene flame redardant composite material as claimed in claim 1 is characterized in that, concrete steps are:
The first step: in proportion 3/10-1/2 polyethylene, nano assistant and 3/10-1/2 processing aid are mixed, under 175-185 ℃ of condition, extrude in forcing machine, prepare the polyethylene master batch that contains nano assistant;
Second step: in proportion 3/10-1/2 polyethylene, halogen-free flame retardants and 3/10-1/2 processing aid are mixed, under 175-185 ℃ of condition, extrude in forcing machine, prepare the polyethylene master batch that contains fire retardant;
The 3rd step: the polyethylene master batch that contains nano assistant that will obtain, the polyethylene master batch and thermo-stabilizer, photostabilizer and remaining polyethylene and the processing aid that contain fire retardant, in length-to-diameter ratio is to disperse extruding pelletization in the twin screw extruder of 35-45:1 150-190 ℃ of melting mixing.
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