CN103881203A - Low-smoke halogen-free flame-retardant polyethylene composite material and preparation method thereof - Google Patents
Low-smoke halogen-free flame-retardant polyethylene composite material and preparation method thereof Download PDFInfo
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- CN103881203A CN103881203A CN201210561444.3A CN201210561444A CN103881203A CN 103881203 A CN103881203 A CN 103881203A CN 201210561444 A CN201210561444 A CN 201210561444A CN 103881203 A CN103881203 A CN 103881203A
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L23/00—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers
- C08L23/02—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers not modified by chemical after-treatment
- C08L23/04—Homopolymers or copolymers of ethene
- C08L23/06—Polyethene
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2201/00—Properties
- C08L2201/02—Flame or fire retardant/resistant
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2201/00—Properties
- C08L2201/22—Halogen free composition
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2205/00—Polymer mixtures characterised by other features
- C08L2205/02—Polymer mixtures characterised by other features containing two or more polymers of the same C08L -group
- C08L2205/025—Polymer mixtures characterised by other features containing two or more polymers of the same C08L -group containing two or more polymers of the same hierarchy C08L, and differing only in parameters such as density, comonomer content, molecular weight, structure
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2205/00—Polymer mixtures characterised by other features
- C08L2205/03—Polymer mixtures characterised by other features containing three or more polymers in a blend
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- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- Compositions Of Macromolecular Compounds (AREA)
Abstract
The invention discloses a low-smoke halogen-free flame-retardant polyethylene composite material and a preparation method thereof. The composite material comprises following components by weight: 50-70% of polyethylene, 20-40% of an inorganic flame retardant, 5-10% of a flame retardant synergist, 3-8% of a compatibilizer, 0.5-2% of a lubricant, 0.1-1% of a coupling agent, 0.1-1% of an antioxidant and 0-1% of a pigment. Beneficial effects of the composite material and the preparation method thereof are that: compared with the prior art, the composite material is good in flame retardant property (with the oxygen index being higher than 28), low in fuming amount, nontoxic, free of molten droplets, and the like, and is high in tensile strength, stable in mechanical performance and is further improved and enhanced in heat stability and hydrolytic stability.
Description
Technical field
The present invention relates to technical field of polymer materials, specifically a kind of low-smoke non-halogen flame-retardant composite polyethylene material and preparation method thereof.
Background technology
Polyethylene (PE) is that a kind of light weight is nontoxic, there is good electrical insulation capability, the thermoplastics of resistance to chemical corrosion, its intensity is higher, winter hardiness is good, and forming process is convenient, is widely used in the industries such as building, communications and transportation, electric wire, chemical machinery, wherein be applied to electricly, cable industry more so.But polyethylene has the poor shortcoming of flame resistivity, it is a kind of inflammable macromolecular material, and oxygen index is 17.5.In the time making electric wire, under the condition such as high pressure, heating, be easy to burning and cause fire, so people usually adopt fire-retardant finish to vinyon, make it to reach the object of difficult combustion.
Plastic flame technology can be summarized as two kinds of flame resistant methods according to the type of fire retardant: the one, and the method for adding fire retardant is added effective fire retardant (comprising uninflammability filler and base material) in polymkeric substance, makes polymkeric substance have flame retardant resistance; Another kind is the method that uses flame-retardant polymer, changes the chemical structure of polymkeric substance itself with reactive flame retardant, makes polymkeric substance itself have flame retardant resistance.Poly flame-retarded technology is mainly taking addition manner as main.The external early stage halogen containing flame-retardant that adopts, add synergist antimonous oxide simultaneously, its flame retardant effect is relatively good, but the amount of being fuming is large, also can produce some obnoxious flavoures, this smog and corrodibility obnoxious flavour not only corrode various plant and instrument, particularly precision instrument, and overslaugh fire-fighting work and evacuating personnel, thereby cause so-called " secondary disaster ".Therefore, this class flame-proof polyethylene output reduces year by year in recent years.In order to reach the object of low cigarette, low-poison and combustion-resisting, greatly develop at present addition type Non-halogen Flame Retardant Technology abroad, add aluminium hydroxide, flame retardant of magnesium hydroxide etc., when being heated, aluminium hydroxide and flame retardant of magnesium hydroxide can discharge crystal water, absorb a large amount of heat energy, rise thereby suppress polymer temperature, delay thermolysis, reduce combustionvelocity.In addition, the water vapour that kinetics produces, can dilute inflammable gas, thereby plays flame retardant effect.Consumption at this class inorganic combustion inhibitor of the U.S. accounts for greatly the over half of fire retardant total amount, they have nontoxic, non-volatile, do not separate out, inexpensive, aboundresources, do not produce the advantages such as corrosive gases, the amount of being fuming are few, but they also exist some shortcomings, the one, the consistency between this based flame retardant and polyethylene is poor, does not have enhancement; The 2nd, their decomposition temperature is relatively low, and complete processing is subject to certain limitation; The 3rd, loading level is higher, can reduce poly processing characteristics and various physical index.
Summary of the invention
The object of the present invention is to provide and a kind ofly there is better flame retardant properties and compared with low-smoke non-halogen flame-retardant composite polyethylene material of high tensile and preparation method thereof.
The technical solution adopted for the present invention to solve the technical problems is: low-smoke non-halogen flame-retardant composite polyethylene material, its component by mass percent proportioning is: polyethylene 50%～70%, inorganic combustion inhibitor 20%～40%, retardant synergist 5%～10%, compatilizer 3%～8%, lubricant 0.5%～2%, coupling agent 0.1%～1%, oxidation inhibitor 0.1%～1%, colorant 0～1%.
Described inorganic combustion inhibitor is aluminium hydroxide or magnesium hydroxide.
Described retardant synergist is micro encapsulation red phosphorus.
Described compatilizer is the one in ethylene-methyl acrylate-glyceryl methacrylate terpolymer (E-MA-GMA), maleic anhydride grafted polyethylene (PE-g-MAH), maleic anhydride extension bar ethylene-octene copolymer (POE-g-MAH), terpolymer EP rubber-maleic anhydride grafts (EPDM-g-MAH).
Described lubricant is the one in polyethylene wax, EVA wax, OP wax, TAS-2A, ethylene bis stearic amide (EBS).
Described coupling agent is the one in silane coupling agent, titanate coupling agent, aluminium titanium composite coupler.
Described oxidation inhibitor is the compound of hindered phenol antioxygen 1010 and phosphite ester kind antioxidant 168.
The preparation method of above-mentioned low-smoke non-halogen flame-retardant composite polyethylene material, comprises the following steps:
(1) take by weight ratio inorganic combustion inhibitor and coupling agent, add in super mixer and mix, temperature is 100 DEG C～120 DEG C, mixing time is 10～30 minutes, obtain the inorganic combustion inhibitor that surface activation process is good, then add the polyethylene, retardant synergist, compatilizer, lubricant, oxidation inhibitor and the colorant that take by weight ratio, at 100 DEG C～120 DEG C temperature, continue to mix 15～20 minutes;
(2) add twin screw extruder to carry out melting mixing the above-mentioned material mixing, then extrude, cooling, granulation, dry, obtain low-smoke non-halogen flame-retardant composite polyethylene material of the present invention.
The invention has the beneficial effects as follows, compared with prior art, the low-smoke non-halogen flame-retardant composite polyethylene material that the present invention makes not only has good flame retardant resistance (oxygen index reaches more than 28), the amount of being fuming is little, nontoxic, without molten drop phenomenon etc., but also there is higher tensile strength, stable mechanical performance, its thermostability and stability to hydrolysis are further improved.
Embodiment
Further illustrate technical scheme of the present invention below in conjunction with specific embodiment.
Embodiment 1:
A kind of low-smoke non-halogen flame-retardant composite polyethylene material, its component by mass percent proportioning is: compound 0.6%, the colorant 0.4% of polyethylene 54%, aluminium hydroxide 30%, micro encapsulation red phosphorus 8%, ethylene-methyl acrylate-glyceryl methacrylate terpolymer (E-MA-GMA) 5%, polyethylene wax 1.5%, silane coupling agent 0.5%, hindered phenol antioxygen 1010 and phosphite ester kind antioxidant 168.
Preparation method: (1) takes aluminium hydroxide and silane coupling agent by weight ratio, add in super mixer and mix, temperature is 100 DEG C～120 DEG C, mixing time is 10～30 minutes, obtain the aluminium hydroxide that surface activation process is good, then add the polyethylene taking by weight ratio, micro encapsulation red phosphorus, ethylene-methyl acrylate-glyceryl methacrylate terpolymer (E-MA-GMA), polyethylene wax, compound and the colorant of hindered phenol antioxygen 1010 and phosphite ester kind antioxidant 168, at 100 DEG C～120 DEG C temperature, continue to mix 15～20 minutes, (2) add twin screw extruder to carry out melting mixing the above-mentioned material mixing, then extrude, cooling, granulation, dry, obtain low-smoke non-halogen flame-retardant composite polyethylene material of the present invention.
Embodiment 2:
A kind of low-smoke non-halogen flame-retardant composite polyethylene material, its component by mass percent proportioning is: compound 0.2%, the colorant 0.3% of polyethylene 70%, magnesium hydroxide 20%, micro encapsulation red phosphorus 5%, maleic anhydride grafted polyethylene (PE-g-MAH) 3%, OP wax 1%, titanate coupling agent 0.5%, hindered phenol antioxygen 1010 and phosphite ester kind antioxidant 168.
Preparation method: (1) takes magnesium hydroxide and titanate coupling agent by weight ratio, add in super mixer and mix, temperature is 100 DEG C～120 DEG C, mixing time is 10～30 minutes, obtain the magnesium hydroxide that surface activation process is good, then add compound and the colorant of the polyethylene, micro encapsulation red phosphorus, maleic anhydride grafted polyethylene (PE-g-MAH), OP wax, hindered phenol antioxygen 1010 and the phosphite ester kind antioxidant 168 that take by weight ratio, at 100 DEG C～120 DEG C temperature, continue to mix 15～20 minutes; (2) add twin screw extruder to carry out melting mixing the above-mentioned material mixing, then extrude, cooling, granulation, dry, obtain low-smoke non-halogen flame-retardant composite polyethylene material of the present invention.
Claims (8)
1. a low-smoke non-halogen flame-retardant composite polyethylene material, it is characterized in that, its component by mass percent proportioning is: polyethylene 50%～70%, inorganic combustion inhibitor 20%～40%, retardant synergist 5%～10%, compatilizer 3%～8%, lubricant 0.5%～2%, coupling agent 0.1%～1%, oxidation inhibitor 0.1%～1%, colorant 0～1%.
2. low-smoke non-halogen flame-retardant composite polyethylene material according to claim 1, is characterized in that, described inorganic combustion inhibitor is aluminium hydroxide or magnesium hydroxide.
3. low-smoke non-halogen flame-retardant composite polyethylene material according to claim 1, is characterized in that, described retardant synergist is micro encapsulation red phosphorus.
4. low-smoke non-halogen flame-retardant composite polyethylene material according to claim 1, it is characterized in that, described compatilizer is the one in ethylene-methyl acrylate-glyceryl methacrylate terpolymer (E-MA-GMA), maleic anhydride grafted polyethylene (PE-g-MAH), maleic anhydride extension bar ethylene-octene copolymer (POE-g-MAH), terpolymer EP rubber-maleic anhydride grafts (EPDM-g-MAH).
5. low-smoke non-halogen flame-retardant composite polyethylene material according to claim 1, is characterized in that, described lubricant is the one in polyethylene wax, EVA wax, OP wax, TAS-2A, ethylene bis stearic amide (EBS).
6. low-smoke non-halogen flame-retardant composite polyethylene material according to claim 1, is characterized in that, described coupling agent is the one in silane coupling agent, titanate coupling agent, aluminium titanium composite coupler.
7. low-smoke non-halogen flame-retardant composite polyethylene material according to claim 1, is characterized in that, described oxidation inhibitor is the compound of hindered phenol antioxygen 1010 and phosphite ester kind antioxidant 168.
8. the preparation method of low-smoke non-halogen flame-retardant composite polyethylene material according to claim 1, is characterized in that, comprises the following steps:
(1) take by weight ratio inorganic combustion inhibitor and coupling agent, add in super mixer and mix, temperature is 100 DEG C～120 DEG C, mixing time is 10～30 minutes, obtain the inorganic combustion inhibitor that surface activation process is good, then add the polyethylene, retardant synergist, compatilizer, lubricant, oxidation inhibitor and the colorant that take by weight ratio, at 100 DEG C～120 DEG C temperature, continue to mix 15～20 minutes;
(2) add twin screw extruder to carry out melting mixing the above-mentioned material mixing, then extrude, cooling, granulation, dry, obtain low-smoke non-halogen flame-retardant composite polyethylene material of the present invention.
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| Application Number | Priority Date | Filing Date | Title |
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| CN201210561444.3A CN103881203A (en) | 2012-12-21 | 2012-12-21 | Low-smoke halogen-free flame-retardant polyethylene composite material and preparation method thereof |
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| CN201210561444.3A CN103881203A (en) | 2012-12-21 | 2012-12-21 | Low-smoke halogen-free flame-retardant polyethylene composite material and preparation method thereof |
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Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104233569A (en) * | 2014-08-19 | 2014-12-24 | 宁波先锋新材料股份有限公司 | Halogen-free flame-retardant environment-friendly covered polyolefin yarn fabric and preparation method thereof |
| CN105419199A (en) * | 2016-01-21 | 2016-03-23 | 长园电子（东莞）有限公司 | Diesel-resistant flame-retardant heat-shrink tube and preparation method thereof |
| CN106479036A (en) * | 2015-08-27 | 2017-03-08 | 合肥杰事杰新材料股份有限公司 | A kind of composite polyolefine material for melting lamination rapid shaping and preparation method thereof |
| CN109749199A (en) * | 2018-12-27 | 2019-05-14 | 上海至正道化高分子材料股份有限公司 | A kind of heating cable low-smoke halogen-free flame-retardant sheath material and preparation method thereof |
| CN114656706A (en) * | 2021-11-30 | 2022-06-24 | 中广核拓普（湖北）新材料有限公司 | Halogen-free flame-retardant polyethylene sheath material and preparation method thereof |
-
2012
- 2012-12-21 CN CN201210561444.3A patent/CN103881203A/en active Pending
Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104233569A (en) * | 2014-08-19 | 2014-12-24 | 宁波先锋新材料股份有限公司 | Halogen-free flame-retardant environment-friendly covered polyolefin yarn fabric and preparation method thereof |
| CN106479036A (en) * | 2015-08-27 | 2017-03-08 | 合肥杰事杰新材料股份有限公司 | A kind of composite polyolefine material for melting lamination rapid shaping and preparation method thereof |
| CN106479036B (en) * | 2015-08-27 | 2020-10-30 | 合肥杰事杰新材料股份有限公司 | Polyolefin composite material for melt lamination rapid molding and preparation method thereof |
| CN105419199A (en) * | 2016-01-21 | 2016-03-23 | 长园电子（东莞）有限公司 | Diesel-resistant flame-retardant heat-shrink tube and preparation method thereof |
| CN109749199A (en) * | 2018-12-27 | 2019-05-14 | 上海至正道化高分子材料股份有限公司 | A kind of heating cable low-smoke halogen-free flame-retardant sheath material and preparation method thereof |
| CN114656706A (en) * | 2021-11-30 | 2022-06-24 | 中广核拓普（湖北）新材料有限公司 | Halogen-free flame-retardant polyethylene sheath material and preparation method thereof |
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Application publication date: 20140625 |