CN1763129A - Thermoplastic halogen-free few-smoke flame-proof cable sheath material and machining process - Google Patents
Thermoplastic halogen-free few-smoke flame-proof cable sheath material and machining process Download PDFInfo
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- CN1763129A CN1763129A CN 200410050640 CN200410050640A CN1763129A CN 1763129 A CN1763129 A CN 1763129A CN 200410050640 CN200410050640 CN 200410050640 CN 200410050640 A CN200410050640 A CN 200410050640A CN 1763129 A CN1763129 A CN 1763129A
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Abstract
The present invention relates to the recipe design and making process of thermoplastic halogen-free low-smoke flame-retarding cable sheath material. Into polyolefin resin as base material, non-toxic halogen-free fire retardant, reinforcing inorganic whisker and proper assistant are added, and through compounding, mixing, plasticizing and pelletizing, the thermoplastic halogen-free low-smoke flame-retarding cable sheath material is prepared. Technologically, the present invention features no halogen, P, Pb and other heavy metal, excellent mechanical performance, machining performance and fire retarding performance, and excellent thermal deforming, thermal ageing and heat shock performance. The material may be used in making cable with high safety and high reliability.
Description
Technical field
The present invention relates to a technological invention in the electric wire industrial circle, be specially a kind of thermoplastic non-halogen low fume fire resistant cable sheath material and complete processing, be applied to the oversheath of electric wire, have fire-retardant, press down cigarette, Halogen, functional characteristics such as nontoxic.Also can be used for fields such as household electrical appliance, electronics, building, is a kind of novel environment-friendly polymer-function material.
Technical background
Macromolecular material is seen everywhere in our daily life, all adopts this type of material as electric wire, electric switch, telepilot, televisor, washing machine shell etc.Plastics are easy firing all, produces a large amount of obnoxious flavour and cigarette during burning, and the disaster hidden-trouble that brings has thus become the problem that the whole world is paid close attention to.The U.S. is the smog of generation when limiting the macromolecular material burning the earliest and the country of toxic gas, but does not put into practice for various reasons.Enter the late nineteen eighties, worldwide, caused the great attention of national governments owing to a large amount of disaster hidden-troubles that use macromolecular material to cause become serious social concern day by day.The industrial used fire retardant of China nearly 80% is a halogen containing flame-retardant at present, be that brominated flame-retardant efficient height, the consumption of representative is few particularly with polybromodiphenyl ether and polybrominated biphenyl material, performance impact to material is little, and it is moderate, its usefulness/price can be equal to than non-other fire retardants, so 70%～80% all uses this based flame retardant in the electric for export series products of China.But it is reported that with polybromodiphenyl ether fire-retardant plastics, can produce many bromos cumarone (PBDF) when burning, this material has strong carcinogenesis, therefore Here it is the alleged ＂ Dioxin Is-sue ＂ of western countries uses to be restricted.Use its (bromo-antimony system) fire-retardant macromolecular material when thermo-cracking and burning, can generate a large amount of flue dust and corrosive gases simultaneously, use halogen-free flame retardants that it is substituted at present abroad in a large number.China must greatly develop the development trend that halogen-free flame retardants could adapt to the world market, and the particularly appearance of this ban of European Union certainly will be accelerated the application process of halogen-free flame retardants in China.If on July 1st, 2006, still use polybromodiphenyl ether and Polybrominated biphenyl based flame retardant in the used macromolecular materials of parts such as the TV of China, refrigerator, washing machine shell, will be kept outside of the door by European Union market from the household appliances of China so.
China studies in this respect and starts late, and also has a certain distance on output and breed structure compared with developed countries.At present, the emphasis of the research and development of domestic halogen-free flame retardants concentrates on fields such as inorganic combustion inhibitor, red phosphorus microcapsuleization, expansion type flame retardant, and has obtained certain achievement.
The halogen gas escaped quantity that fire retardant material produces when using fire retardant kind and burning by it and the amount of being fuming can be divided into GENERAL TYPE fire retardant material, low bittern type flame-retarded material, the low cigarette type fire retardant material of low halogen and halide-free smokeless type fire retardant material.
Current in the China and even the whole world, to various flame retardant of plastic technology, mainly be based on brominated flame retardant, what stand in the breach is decabromodiphynly oxide, is called for short DBDPO.The brominated amount height of this fire retardant has excellent thermostability.Because its decomposition temperature is greater than 350 ℃, be complementary with the decomposition temperature of various superpolymer, thereby can in the best time at gas phase and condensed phase fire retardation simultaneously, not only addition is little, and good flame retardation effect.But when burning, can produce hazardous and noxious substances, suffer that in recent years some countries resist use.
Halide-free smokeless type fire retardant material does not produce corrosive obnoxious flavour when burning, the amount of being fuming is also minimum, in fire failure, disaster and the loss that is caused by material combustion can be dropped to bottom line, the what is called that has caused when promptly having solved material combustion " secondary disaster ".Has above-mentioned superiority just because of halide-free smokeless type series material, fire-retardant and the flame resistant cable of using in some important places of industrially developed country just progressively trends towards the development of halide-free smokeless type, as: naval vessel, oil drilling platform, subway, undergrond street, airport, large hospital, Highrise buildings and nuclear (fire) power station etc.Engineerings such as the Up for Qinshan Nuclear Power Plant of China, Daya Bay Nuclear Power Plant, line of Shanghai Underground, market, Xin Dong An, Beijing and industrial and commercial head office mansion have also all adopted halide-free smokeless type cable.
Use inorganic combustion inhibitor will reach the flame-retardant smoke inhibition effect, often need high addition (more than 50%), mechanical property influence to material is bigger, because of the technical elements reason, China is lagging far behind abroad aspect the use inorganic combustion inhibitor, the halide-free smokeless material that existing important events are used has also limited the LSOH anti-flaming Development of Materials mainly by import.
The technology of the present invention has been used the whisker strongthener at influencing this key of the mechanical property of materials, for the LSOH anti-flaming Development of Materials has been opened up a new way.
Summary of the invention
The object of the present invention is to provide a kind of thermoplastic non-halogen low fume fire resistant cable sheath material and complete processing, by selecting inorganic combustion inhibitor and inorganic crystal whisker material to set out, through surface treatment to inorganic powder, improve surfactivity, and science design to filling a prescription, determine suitable complete processing and method, synthetic thermoplastic halide-free low-smoke fireproof cable sheath material.
Technical scheme of the present invention is:
A kind of thermoplastic non-halogen low fume fire resistant cable sheath material, base material is selected polyolefin resin for use, and inorganic combustion inhibitor is selected super fine magnesium hydroxide or aluminium hydroxide for use, selects magnesium salt whisker simultaneously for use, counts 100 parts of polyolefin resins by weight; 70-100 part magnesium hydroxide or aluminium hydroxide; 30-60 part magnesium salt whisker, other auxiliary agent 3-8 part.
Described polyolefin resin comprises one of EVA, PP, PVC, PC or is mixed.
Described magnesium salt whisker is an alkali magnesium sulfate salt whisker, the length-to-diameter ratio of crystal whisker materials 〉=20 (20-130), commercial product.
Described auxiliary agent adopts conventional auxiliary agent, comprises surface treatment agent 1-5 part, tinting material 1-3 part, lubricant 1-3 part.
Described surface treatment agent is silane coupling agent, titante coupling agent or stearic acid coupling agent.
Described silane coupling agent comprises silane 172,171 or 55H coupling agent, and titanate ester comprises titanic acid ester or aluminium titanium composite coupler, and stearic acid comprises stearic acid, Zinic stearas, calcium stearate, Magnesium Stearate or sodium stearate.
Described tinting material is carbon black, white carbon black or ultramarine; Lubricant is a stone vinegar.
The complete processing of described cable jacket material, material is mixed in high-speed stirring mixer, temperature is 100～120 ℃, and its rotating speed is 100～200rpm, after the mixing fully, use twin screw extruder, each distinguishes temperature 130-150 ℃, processes at one time, pelletizing after the air-cooled or water-cooled, powder surface is through the processing that organises (surface treatment agent processing), and smooth surface is smooth.
Beneficial effect of the present invention is as follows:
1, the present invention is base-material with the polyolefin resin, and adding Halogen, nontoxic fire retardant (magnesium hydroxide or aluminium hydroxide) and inorganic crystal whisker strongthener is main constituent element, and adds proper assistant, makes through proportioning, mixing, plasticizing, granulation.Its technical characterstic is: not halogen-containing, phosphorus, lead and other heavy metal, have the favorable mechanical performance, and processing characteristics and superior flame retardant properties have excellent thermal distortion, thermal ageing and thermal shock resistance properties simultaneously.The cable of making has the security and the reliability of height, can pass through the above combustion test of category-A smoothly.Be applicable to that naval vessel cable, cables of nuclear power, Highrise buildings are with electric power and umbilical cable etc.
2, gordian technique of the present invention is inorganic crystal whisker strongthener and the technological method for processing that adds in the component design.
(1) formula technique
It is base material that this technology adopts homemade polyolefin resin, selects China's superior resources inorganic combustion inhibitor (magnesium hydroxide, aluminium hydroxide) for use, adds the magnesium salt whisker strongthener, synthetic thermoplastic non-halogen low fume fire resistant cable sheath material.When Formula Design,, reach the purpose of outstanding a certain performance by adjusting the proportioning of differing materials.Synthetic materials Halogen, nontoxic has favorable mechanical performance, processing characteristics and superior flame retardant properties, has excellent thermal distortion, thermal ageing and thermal shock resistance properties simultaneously.This technology is not seen bibliographical information up till now.
(2) processing technology
Adjust by screw combinations twin screw extruder, guarantee length-to-diameter ratio 〉=20 of crystal whisker materials, determine processing temperature at 130-150 ℃, material grain smooth surface is smooth, the cable of making has the security and the reliability of height, can pass through the above combustion test of category-A smoothly.
3, the present invention rationally selects base material and inorganic combustion inhibitor for use, and inorganic combustion inhibitor is carried out surface organic handle, and improves compatibleness, adds magnesium salt whisker in right amount, improves the mechanical property of material.Fire-retardant, the low cigarette of integral formula embodiment, Halogen, nontoxic.Choose the best processing technology condition, the product time processing reaches every index, outward appearance φ 4 * 4 particles, color tunable; Tensile strength＞12MPa; Elongation at break 200-400%, oxygen index＞40%.
Description of drawings
Fig. 1 is a process flow diagram of the present invention.
Embodiment
Process flow diagram of the present invention as shown in Figure 1, with the polyolefin resin is base-material, adding Halogen, nontoxic fire retardant (magnesium hydroxide or aluminium hydroxide) and inorganic crystal whisker strongthener is main constituent element, and adds proper assistant, makes through proportioning, mixing, plasticizing, granulation.
Embodiment 1
Step 1: formulating of recipe
A: polyolefin resin (EVA) 100 grams;
B: aluminium hydroxide 90 grams, magnesium salt whisker 30 grams, the length-to-diameter ratio of crystal whisker materials is 80;
C: silane 172 coupling agents 2 grams, Zinic stearas 3 grams;
D: carbon black 2 grams, paraffin 1 gram.
A, B, C, D are put into high-speed stirring mixer and stir, and temperature is 100～120 ℃, and its rotating speed is 100～200rpm, mixes fully.
Step 2: processing
Twin screw extruder heating zone temperature is controlled at 140 ℃, and the material that step 1 is mixed adds, and processes at one time, and extrudes pelletizing after the air-cooled or water-cooled in back.
Step 3: test result
To expect that grain extrudes compressing tablet, by the test of standard method of test such as national standard or IEC and reach following technology properties index:
Tensile strength: 12MPa elongation at break: 260%
Heat aging performance (136 ℃ * 168h): tensile strength velocity of variation+5
Elongation at break velocity of variation-5
Low-temperature impact failure number: 0/15
Volume specific resistance: 20 ℃ 9.0 * 10
13Ω m; 90 ℃ 3.5 * 10
12Ω m
Dielectric strength: 27KV/mm oxygen index: 40
Density: 1.20g/cm
3
Embodiment 2
Step 1: formulating of recipe
A: polyolefin resin (EVA) 80 grams, (PC) 20 grams;
B: aluminium hydroxide 80 grams, magnesium salt whisker 40 grams, the length-to-diameter ratio of crystal whisker materials is 70;
C: silane 171 coupling agents 2 grams;
D: carbon black 2 grams, paraffin 1 gram.
A, B, C, D are put into high-speed stirring mixer and stir, and temperature is 100～120 ℃, and its rotating speed is 100～200rpm, mixes fully.
Step 2: processing
Twin screw extruder heating zone temperature is controlled at 150 ℃, and the material that step 1 is mixed adds, and processes at one time, and extrudes pelletizing after the air-cooled or water-cooled in back.
Step 3: test result
To expect that grain extrudes compressing tablet, by the test of standard method of test such as national standard or IEC and reach following technology properties index:
Tensile strength: 12.5MPa elongation at break: 200%
Heat aging performance (136 ℃ * 168h): tensile strength velocity of variation+5
Elongation at break velocity of variation-5
Low-temperature impact failure number: 0/15
Volume specific resistance: 20 ℃ 9.0 * 10
13Ω m; 90 ℃ 3.5 * 10
12Ω m
Dielectric strength: 27KV/mm oxygen index: 42
Density: 1.22g/cm
3
Embodiment 3
Step 1: formulating of recipe
A: polyolefin resin (EVA) 50 grams, (PC) 50 grams;
B: magnesium hydroxide 70 grams, magnesium salt whisker 40 grams, the length-to-diameter ratio of crystal whisker materials is 30;
C: silane 55H coupling agent 2 grams, titanic acid ester 1 gram;
D: white carbon black 3 grams, paraffin 2 grams.
A, B, C, D are put into high-speed stirring mixer and stir, and temperature is 100～120 ℃, and its rotating speed is 100～200rpm, mixes fully.
Step 2: processing
Twin screw extruder heating zone temperature is controlled at 150 ℃, and the material that step 1 is mixed adds, and processes at one time, and extrudes pelletizing after the air-cooled or water-cooled in back.
Step 3: test result
To expect that grain extrudes compressing tablet, by the test of standard method of test such as national standard or IEC and reach following technology properties index:
Tensile strength: 13MPa elongation at break: 190%
Heat aging performance (136 ℃ * 168h): tensile strength velocity of variation+5
Elongation at break velocity of variation-5
Low-temperature impact failure number: 0/15
Volume specific resistance: 20 ℃ 9.0 * 10
13Ω m; 90 ℃ 3.5 * 10
12Ω m
Dielectric strength: 27KV/mm oxygen index: 44
Density: 1.25g/cm
3
Embodiment 4
Step 1: formulating of recipe
A: polyolefin resin (EVA) 100 grams;
B: magnesium hydroxide 60 grams, magnesium salt whisker 60 grams, the length-to-diameter ratio of crystal whisker materials is 100;
C: Zinic stearas 3 grams;
D: ultramarine 1 gram, paraffin 3 grams.
A, B, C, D are put into high-speed stirring mixer and stir, and temperature is 100～120 ℃, and its rotating speed is 100～200rpm, mixes fully.
Step 2: processing
Twin screw extruder heating zone temperature is controlled at 145 ℃, and the material that step 1 is mixed adds, and processes at one time, and extrudes pelletizing after the air-cooled or water-cooled in back.
Step 3: test result
To expect that grain extrudes compressing tablet, by the test of standard method of test such as national standard or IEC and reach following technology properties index:
Tensile strength: 13.5MPa elongation at break: 170%
Heat aging performance (136 ℃ * 168h): tensile strength velocity of variation+5
Elongation at break velocity of variation-5
Low-temperature impact failure number: 0/15
Volume specific resistance: 20 ℃ 9.0 * 10
13Ω m; 90 ℃ 3.5 * 10
12Ω m
Dielectric strength: 27KV/mm oxygen index: 41
Density: 1.28g/cm
3
Claims (8)
1, a kind of thermoplastic non-halogen low fume fire resistant cable sheath material, it is characterized in that: base material is selected polyolefin resin for use, and inorganic combustion inhibitor is selected super fine magnesium hydroxide or aluminium hydroxide for use, selects magnesium salt whisker simultaneously for use, counts 100 parts of polyolefin resins by weight; 70-100 part magnesium hydroxide or aluminium hydroxide; 30-60 part magnesium salt whisker, other auxiliary agent 3-8 part.
2, by the described cable jacket material of claim 1, it is characterized in that: described polyolefin resin comprises one of EVA, PP, PVC, PC or is mixed.
3, by the described cable jacket material of claim 1, it is characterized in that: described magnesium salt whisker is an alkali magnesium sulfate salt whisker, and the length-to-diameter ratio of crystal whisker materials is 20-130.
4, by the described cable jacket material of claim 1, it is characterized in that: described auxiliary agent comprises surface treatment agent 1-5 part, tinting material 1-3 part, lubricant 1-3 part.
5, by the described cable jacket material of claim 1, it is characterized in that: described surface treatment agent is silane coupling agent, titante coupling agent or stearic acid.
6, by the described cable jacket material of claim 5, it is characterized in that: described silane coupling agent comprises silane 172,171 or 55H coupling agent, titante coupling agent comprises titanic acid ester or aluminium titanium composite coupler, and stearic acid comprises stearic acid, Zinic stearas, calcium stearate, Magnesium Stearate or sodium stearate.
7, by the described cable jacket material of claim 4, it is characterized in that: described tinting material is carbon black, white carbon black or ultramarine; Lubricant is a stone vinegar.
8, press the complete processing of the described cable jacket material of claim 1, it is characterized in that: material is mixed in high-speed stirring mixer, temperature is 100～120 ℃, its rotating speed is 100～200rpm, after mixing fully, use twin screw extruder, each distinguishes temperature 130-150 ℃, process at one time pelletizing after the air-cooled or water-cooled.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CNB200410050640XA CN1322049C (en) | 2004-10-20 | 2004-10-20 | Thermoplastic halogen-free few-smoke flame-proof cable sheath material and machining process |
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CNB200410050640XA CN1322049C (en) | 2004-10-20 | 2004-10-20 | Thermoplastic halogen-free few-smoke flame-proof cable sheath material and machining process |
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| Publication Number | Publication Date |
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| CN1763129A true CN1763129A (en) | 2006-04-26 |
| CN1322049C CN1322049C (en) | 2007-06-20 |
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| JPH039937A (en) * | 1989-06-06 | 1991-01-17 | Hitachi Cable Ltd | Flame-retardant electrical insulating composition |
| JP3009937B2 (en) * | 1991-03-16 | 2000-02-14 | 泉 舟越 | Method for selective atomization and separation of aromatic polymer in coal and method for modifying surface of coal fine particles |
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| CN1228476C (en) * | 2003-04-15 | 2005-11-23 | 清华大学 | New method of rapid synthesis of basic bitter salt |
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