CN103333382B - Containing the composite fire resistance cable material and preparation method thereof of polycyclic three phosphonitriles-sulfone microballoon - Google Patents
Containing the composite fire resistance cable material and preparation method thereof of polycyclic three phosphonitriles-sulfone microballoon Download PDFInfo
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- CN103333382B CN103333382B CN201310121516.7A CN201310121516A CN103333382B CN 103333382 B CN103333382 B CN 103333382B CN 201310121516 A CN201310121516 A CN 201310121516A CN 103333382 B CN103333382 B CN 103333382B
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Abstract
The present invention relates to a kind of composite fire resistance cable material containing polycyclic three phosphonitriles-sulfone microballoon and preparation method thereof. CABLE MATERIALS of the present invention adopts polycyclic three phosphonitriles of high-crosslinking-degree-sulfone microballoon, magnesium hydroxide and aluminium hydroxide to make fire retardant, the residual rate under CABLE MATERIALS high temperature can be increased, improve thermostability and the flame retardant properties of CABLE MATERIALS; Due to CABLE MATERIALS, to have the amount of being fuming low, and not containing toxic substances such as lead, antimony, be a kind of environmental type CABLE MATERIALS; Adding of polyphosphazene microspheres, the loading level of magnesium hydroxide and aluminium hydroxide can be reduced, while raising Flame Retardancy energy, the mechanical property of material can be increased; Adding of lubricant, Drawing abillity can be improved.This CABLE MATERIALS is a kind of new and effective fire-resistant cable material.
Description
Technical field
The present invention relates to a kind of fire-resistant cable material and preparation method thereof, particularly one belongs to polymeric material field, relates to polymkeric substance CABLE MATERIALS, especially a kind of composite fire resistance cable material containing polycyclic three phosphonitriles-sulfone microballoon and preparation method thereof.
Background technology
Electric wire has the effect of power transmission and information conveyance, plays an important role in people's life and production.Design and prepare low cigarette, low toxicity, possessing again the CABLE MATERIALS of excellent fire-retardancy and insulating property simultaneously, become the focus of current fire-retardant research.
Traditional magnesium hydroxide and aluminium hydroxide based flame retardant, although the flame retardant properties that material is good can be given, but, matrix resin due to most of CABLE MATERIALS is nonpolar polyolefins polymer, poor with the consistency of the magnesium hydroxide of polarity, aluminium hydroxide, often reduce mechanical property and the processing characteristics of material.
Phosphonitrile compounds is so that main chain to be alternately arranged with phosphorus nitrogen-atoms, and side chain is a class novel organic-inorganic compound of different organic substituent, and it has the incomparable superiority of traditional polymer.And by polycyclic three phosphonitriles-sulfone microballoon that precipitation polymerization method obtains, due to highly cross-linked chemical structure, there is excellent thermostability, the residual rate in atmosphere at 600 DEG C reaches more than 50%; The phosphorus nitrogen of high-content forms collaboration system simultaneously, has superior flame retardant effect, is a kind of BACN efficiently.
Summary of the invention
An object of the present invention is to provide a kind of composite fire resistance cable material containing polycyclic three phosphonitriles-sulfone microballoon.By adding polycyclic three phosphonitriles-sulfone microballoon, magnesium hydroxide and aluminium hydroxide simultaneously, give the flame retardant properties of material excellence, good machinability, preferably insulating property.
Two of object of the present invention is the preparation method providing this CABLE MATERIALS.
For achieving the above object, the present invention adopts following technical scheme:
Containing a composite fire resistance cable material for polycyclic three phosphonitriles-sulfone microballoon, it is characterized in that this CABLE MATERIALS mainly containing following component, the mass percent of each component is:
Low Density Polyethylene 30% ~ 35%;
Ethylene-vinyl acetate copolymer 18% ~ 25%;
Polycyclic three phosphonitriles-sulfone microballoon 1% ~ 10%;
Magnesium hydroxide 25% ~ 35%;
Aluminium hydroxide 12% ~ 18%;
Each constituent mass percentage composition sum is 100% above.
Above-mentioned polycyclic three phosphonitriles-sulfone microballoon is ring three phosphonitrile-(4,4 '-dihydroxy diphenylsulphone) multipolymer, and its chemical structural formula is as follows:
。
Above-mentioned polycyclic three phosphonitriles-sulfone microballoon is the median size 0.1 ~ 3 μm of ring three phosphonitrile-(4,4 '-dihydroxy diphenylsulphone) multipolymer,
Prepare a method for the above-mentioned composite fire resistance cable material containing polycyclic three phosphonitriles-sulfone microballoon, it is characterized in that the concrete steps of the method are:
(1) mixing of materials except magnesium hydroxide and aluminium hydroxide is even, obtain mixture A.
(2) by magnesium hydroxide, aluminium hydroxide Homogeneous phase mixing, mixture B is obtained;
(3) the mixture A of step (1) is added Banbury mixer and carry out banburying, material temperature is set to 160 ~ 180 DEG C; After banburying 5 ~ 10min, the mixture B that step (2) obtains is added Banbury mixer and proceeds banburying, material temperature is set to 160 ~ 180 DEG C, banburying time 5 ~ 12min, obtained blend.
(4) blend obtained for step (3) is put into open type plastic purificating set and carry out out refining, material temperature is set to 170 ~ 190 DEG C, carry out 5 ~ 20 times mixing, namely obtain the composite fire resistance cable material containing polycyclic three phosphonitriles-sulfone microballoon.
Can be according to actual needs in fire-resistant cable material of the present invention, add various additive, such as antioxidant: four [β-(3,5-di-tert-butyl-hydroxy phenyl) propionic acid] pentaerythritol ester (antioxidant 1010), three (2,4-di-tert-butyl-phenyl) phosphorous acid ester (irgasfos 168s) etc.; Lubricant comprises PE wax, calcium stearate, Zinic stearas etc.
Compared with existing technology, product of the present invention has the following advantages:
1. high flame retardant, because polycyclic three phosphonitriles-sulfone microballoon elevated chemical is cross-linked, has higher carbon yield, containing-P=N-the structure be alternately arranged in structure, composite with magnesium hydroxide, aluminium hydroxide, the residual rate under CABLE MATERIALS high temperature can be improved, obtain the CABLE MATERIALS of excellent flame retardancy.
2. environmental protection, this CABLE MATERIALS is burnt at relatively high temperatures, no matter is flaming combustion or flameless combustion, has the advantage that the amount of being fuming is little, and the toxicants such as meanwhile, cable is not leaded, antimony are a kind of environmental type CABLE MATERIALS.
3. long service life, selecting of oxidation inhibitor, gives the heat resistanceheat resistant of material excellence, ageing resistance, and the CABLE MATERIALS of preparation has longer work-ing life.
4. excellent machinery and processing characteristics, because polycyclic three phosphonitriles-sulfone microballoon and magnesium hydroxide, aluminium hydroxide have cooperative flame retardant effect, can reduce the add-on of magnesium hydroxide, aluminium hydroxide, improves mechanical property and the processing characteristics of CABLE MATERIALS.Meanwhile, the lubricant in formula can increase the mobility of material, improves the processing characteristics of CABLE MATERIALS.
Embodiment
Embodiment one: each component and mass percent as follows:
The sheet material of above-mentioned CABLE MATERIALS or plate moulding preparation method, its preparation methods steps is as follows:
Prepare burden by gross weight 200g, by 60gLDPE, 40g ethylene-vinyl acetate copolymer, 2g polycyclic three phosphonitriles-sulfone microballoon, obtain mixture A.
Magnesium hydroxide 66g and aluminium hydroxide 32g is mixed, obtains mixture B.
Mixture A is added Banbury mixer and carries out banburying, material temperature is set to 160 DEG C; After banburying 5min, mixture B is added Banbury mixer and proceeds banburying, material temperature is set to 160 DEG C, banburying time 10min, obtained blend.
Above-mentioned obtained blend is put into open type plastic purificating set and carries out out refining, material temperature is set to 180 DEG C, carry out 20 times mixing, slice.
Sheet material after mixing is shredded, gets and put into mould in right amount, the mould that sample is housed is put into vulcanizing press at 180 DEG C, heats 4min, then maintain the temperature at 180 DEG C, with 15MPa pressure hot pressing 6min.Remove pressure, the mould that sample is housed is transferred to rapidly the vulcanizing press that temperature is room temperature, to cold pressing 5min with 15MPa pressure, depanning, obtains LDPE/ polycyclic three phosphonitriles-sulfone microballoon CABLE MATERIALS sheet material or sheet material.Then, performance detection experiment is carried out to this CABLE MATERIALS sheet material or sheet material, the results are shown in Table 1.
Embodiment two: contained component and mass percent as follows:
The preparation method of above-mentioned CABLE MATERIALS is identical with embodiment 1, carries out performance detection experiment, the results are shown in Table 1.
Embodiment three: contained component and mass percent as follows:
The preparation method of above-mentioned CABLE MATERIALS is identical with embodiment 1, carries out performance detection experiment, the results are shown in Table 1.
Table 1:
。
Claims (3)
1., containing a composite fire resistance cable material for polycyclic three phosphonitriles-sulfone microballoon, it is characterized in that this CABLE MATERIALS mainly containing following component, the mass percent of each component is:
Low Density Polyethylene 30% ~ 35%;
Ethylene-vinyl acetate copolymer 18% ~ 25%;
Polycyclic three phosphonitriles-sulfone microballoon 1% ~ 10%;
Magnesium hydroxide 25% ~ 35%;
Aluminium hydroxide 12% ~ 18%;
Each constituent mass percentage composition sum is 100% above;
Polycyclic three phosphonitriles-sulfone microballoon is ring three phosphonitrile-(4,4 '-dihydroxy diphenylsulphone) multipolymer, and its chemical structural formula is as follows:
。
2. the composite fire resistance cable material containing polycyclic three phosphonitriles-sulfone microballoon according to claim 1, is characterized in that the median size 0.1 ~ 3 μm of described polycyclic three phosphonitriles-sulfone microballoon.
3. prepare a method for the composite fire resistance cable material containing polycyclic three phosphonitriles-sulfone microballoon according to claim 1 and 2, it is characterized in that the concrete steps of the method are:
(1) mixing of materials except magnesium hydroxide and aluminium hydroxide is even, obtain mixture A;
(2) by magnesium hydroxide, aluminium hydroxide Homogeneous phase mixing, mixture B is obtained;
(3) the mixture A of step (1) is added Banbury mixer and carry out banburying, material temperature is set to 160 ~ 180 DEG C; After banburying 5 ~ 10min, the mixture B that step (2) obtains is added Banbury mixer and proceeds banburying, material temperature is set to 160 ~ 180 DEG C, banburying time 5 ~ 12min, obtained blend;
(4) blend obtained for step (3) is put into open type plastic purificating set and carry out out refining, material temperature is set to 170 ~ 190 DEG C, carry out 5 ~ 20 times mixing, namely obtain the composite fire resistance cable material containing polycyclic three phosphonitriles-sulfone microballoon.
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| CN103804748A (en) * | 2013-10-16 | 2014-05-21 | 上海大学 | Hexaphenoxy cyclotriphosphazene-containing composite flame-retardant cable material and preparation method thereof |
| CN104628997B (en) * | 2015-02-10 | 2017-03-01 | 广东广山新材料有限公司 | Flame retardant with bisphenol S base, fire-retarded epoxy resin and flame-retardant composition |
| CN107200894A (en) * | 2017-06-06 | 2017-09-26 | 合肥励仙电力工程有限公司 | A kind of novel cable material and preparation method thereof |
| CN110423354B (en) * | 2019-08-26 | 2020-06-30 | 北京理工大学 | ZIF-67@ ZIF-8 doped polycyclotriphosphazene flame retardant and preparation method thereof |
| CN111269266B (en) * | 2020-04-01 | 2021-11-16 | 吉林大学 | Cyano-containing aryl ether phosphazene type halogen-free flame retardant, preparation method and application in irradiation crosslinking cable insulation material |
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| CN1908033A (en) * | 2006-08-17 | 2007-02-07 | 上海交通大学 | Crosslinking poly(organophosphazenes) microsphere and preparation method thereof |
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| JP2009227872A (en) * | 2008-03-24 | 2009-10-08 | Furukawa Electric Co Ltd:The | Insulating resin composition, and insulated electric wire |
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