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CN103627074B - A kind of low-smoke bittern-free highly fire-proof Oil-resistant cold-resistant CABLE MATERIALS and preparation method and cable - Google Patents

A kind of low-smoke bittern-free highly fire-proof Oil-resistant cold-resistant CABLE MATERIALS and preparation method and cable
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Publication number
CN103627074B
CN103627074BCN201310654876.3ACN201310654876ACN103627074BCN 103627074 BCN103627074 BCN 103627074BCN 201310654876 ACN201310654876 ACN 201310654876ACN 103627074 BCN103627074 BCN 103627074B
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cable materials
resistant
cable
combination
low
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CN103627074A (en
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兰乔波
宋刚
翁文彪
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Shanghai Zhizheng New Material Co., Ltd
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SHANGHAI ZHIZHENG DAOHUA POLYMER MATERIALS Co Ltd
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Abstract

The invention provides a kind of low-smoke bittern-free highly fire-proof Oil-resistant cold-resistant CABLE MATERIALS and preparation method, each component of CABLE MATERIALS and parts by weight as follows: base mateiral 100 parts; Fire retardant A80 ~ 100 part; Fire retardant B10 ~ 20 part; 0.8 ~ 2 part, oxidation inhibitor; Lubricant 0.4 ~ 2 part; Coupling agent 0.8 ~ 3 part; Strengthening agent 25 ~ 40 parts; Vulcanizing agent 0.4 ~ 0.6 part; Base mateiral is the combination of ethylene-vinyl acetate (EVA) and methyl vinyl silicone rubber; Fire retardant A is the combination of magnesium hydroxide and antimonous oxide; Fire retardant B is the combination of zinc oxide, molybdic oxide; Oxidation inhibitor is the combination of four [β-(3,5-di-tert-butyl-hydroxy phenyl) propionic acid] pentaerythritol ester (antioxidant 1010), tricresyl phosphite (2,4-di-tert-butyl-phenyl) ester (irgasfos 168); Strengthening agent is gas-phase silica.Cable material provided by the invention has following characteristic: wear resistance is good, and flame retardant properties is good, and also have good oil-proofness and chemical resistance, low temperature resistant ageing-resistant, mechanical property is superior.Present invention also offers the preparation method of this CABLE MATERIALS.

Description

A kind of low-smoke bittern-free highly fire-proof Oil-resistant cold-resistant CABLE MATERIALS and preparation method and cable
Technical field
The present invention relates to a kind of non-halogen flame-retardant cable and preparation method thereof, relate more specifically to a kind of low-smoke bittern-free highly fire-proof Oil-resistant cold-resistant CABLE MATERIALS and preparation method and cable.
Background technology
Along with quick growth and the developing rapidly of economy of electric wire application, each field to the requirement of the quality and performance of wire cable material all in raising, particularly to the high temperature resistant lower temperature resistance of CABLE MATERIALS, the requirement of weathering resistance and oil-proofness.
At present, oil resistant cable is at the oil of China, and chemical industry, has extensive application in oceanographic engineering and field of track traffic, but along with the common requirements of oil resistant cable, the accident caused because of cable oil resistance difference every year is also being upper body trend.
In field of track traffic, the cable insulation material of existing vehicles, its base mateiral is all polyethylene or polypropylene substantially, such material, and under normal temperature, its weather-resistant property is all undesirable, and oil-proofness also needs to improve very much, and resistance to low temperature neither be fine.And high temperature resistant poor performance at low temperatures and oil-proofness poor, cable can be made aging very soon in oil, aging after its electric property be difficult to meet national standard.
There is certain defect with selecting of material because of it in Oil-resistant cold-resistant cable, be never well solved in the design of formula.
In sum, this area lacks a kind of halogen-free high flame-retardant Oil-resistant cold-resistant CABLE MATERIALS and the preparation method that can meet the requirement of above-mentioned over-all properties.
For this reason, this area overcomes the deficiencies in the prior art in the urgent need to one, and cable material is wear-resisting and oil resistance good, and flame retardant properties is good, and mechanical property is superior, the fireproofing cable material without halide of high-low temperature resistant and preparation method.
Summary of the invention
The first object of the present invention is that obtaining one overcomes the deficiencies in the prior art, and low-smoke halogen-free flame-proof cable material is cold-resistant and oil resistance is good, and flame retardant properties is good, the CABLE MATERIALS that mechanical property is superior.
The second object of the present invention is that obtaining one overcomes the deficiencies in the prior art, and low-smoke halogen-free flame-proof cable material is cold-resistant and oil resistance is good, and flame retardant properties is good, the cable that mechanical property is superior.
The third object of the present invention is that obtaining one overcomes the deficiencies in the prior art, and low-smoke halogen-free flame-proof cable material is cold-resistant and oil resistance is good, and flame retardant properties is good, the preparation method of the CABLE MATERIALS that mechanical property is superior.
In a first aspect of the present invention, provide a kind of low-smoke bittern-free highly fire-proof Oil-resistant cold-resistant CABLE MATERIALS, each component of described CABLE MATERIALS and parts by weight as follows:
Wherein, described base mateiral is the combination of ethylene-vinyl acetate (EVA) and methyl vinyl silicone rubber, and its components by weight percent ratio is 50 ~ 60:40 ~ 50.
In a specific embodiment of the present invention, the VA content of described ethylene-vinyl acetate (EVA) is 28%.
In a specific embodiment of the present invention, described fire retardant A is the combination of magnesium hydroxide and antimonous oxide, and its components by weight percent ratio is 60 ~ 70:20 ~ 30.
In a specific embodiment of the present invention, described fire retardant B is the combination of zinc oxide, molybdic oxide, and its components by weight percent ratio is 8 ~ 12:2 ~ 8.
In a specific embodiment of the present invention, described oxidation inhibitor is four [β-(3,5-di-tert-butyl-hydroxy phenyl) propionic acid] pentaerythritol ester (antioxidant 1010), tricresyl phosphite (2,4-di-tert-butyl-phenyl) combination of ester (irgasfos 168), its components by weight percent ratio is 0.4 ~ 1:0.4 ~ 1.
In a specific embodiment of the present invention, described lubricant is one or more the combination in calcium stearate, Zinic stearas, Magnesium Stearate, polyethylene wax.
In a specific embodiment of the present invention, described coupling agent is the one in silane coupling agent, aluminate coupling agent, phosphate coupling agent, boric acid ester coupler.
In a specific embodiment of the present invention, described strengthening agent is gas-phase silica.
In a specific embodiment of the present invention, described vulcanizing agent is two (tert-butyl peroxy base) hexanes of 2,5-dimethyl-2,5-, namely two 2, and 5 vulcanizing agents.This vulcanizing agent fusing point 8 DEG C, decomposition temperature is 140-150 DEG C.
A second aspect of the present invention, provides the cable that a kind of low-smoke bittern-free highly fire-proof Oil-resistant cold-resistant CABLE MATERIALS of the present invention is obtained.
A third aspect of the present invention provides a kind of preparation method of low-smoke bittern-free highly fire-proof Oil-resistant cold-resistant CABLE MATERIALS of the present invention, and described preparation method comprises the following steps:
1) methyl vinyl silicone rubber of formula ratio and EVA are dropped in Banbury mixer, banburying 3-4min;
2) material of remaining all formula ratios is also dropped in Banbury mixer, continue banburying 5-6min with the methyl vinyl silicone rubber dropped into before together with EVA; Whole internal mixing pass 8-10min obtains the good work in-process of banburying;
3) work in-process that banburying is good are extruded stretching and granulation through Dual-cone feeding device and twin-screw extrusion unit and are obtained described low-smoke bittern-free highly fire-proof Oil-resistant cold-resistant CABLE MATERIALS; Each section of temperature of described twin screw controls from charging opening, and be followed successively by 90 ~ 100 DEG C, 90 ~ 100 DEG C, 90 ~ 95 DEG C, 85 ~ 90 DEG C, 85 ~ 90 DEG C, 75 ~ 85 DEG C, 85 ~ 90 DEG C, twin screw head temperature is 90 ~ 95 DEG C.
Embodiment
The present inventor is through extensive and deep research, and by improving formula, obtain that a kind of cable material is low temperature resistant and oil resistance good, flame retardant properties is good, the fireproofing cable material without halide that mechanical property is superior and preparation method.Complete the present invention on this basis.
In the present invention, term " contains " or " comprising " represents that various composition can be applied in mixture of the present invention or composition together.Therefore, term " primarily of ... composition " and " by ... form " be included in term and " contain " or in " comprising ".
Below describe in detail to various aspects of the present invention:
As no specific instructions, various raw material of the present invention all can be obtained by commercially available; Or prepare according to the ordinary method of this area.Unless otherwise defined or described herein, all specialties used herein and scientific words and those skilled in the art the same meaning be familiar with.In addition any method similar or impartial to described content and material all can be applicable in the inventive method.
Low-smoke non-halogen flame-retardant Oil-resistant cold-resistant CABLE MATERIALS
In a first aspect of the present invention, provide a kind of low-smoke bittern-free highly fire-proof Oil-resistant cold-resistant CABLE MATERIALS, each component of described CABLE MATERIALS and parts by weight as follows:
Described base mateiral is the combination of ethylene-vinyl acetate (EVA) and methyl vinyl silicone rubber.
Described fire retardant A is the combination of magnesium hydroxide and antimonous oxide, and its components by weight percent ratio is 60 ~ 70:20 ~ 30.
Described fire retardant B is the combination of zinc oxide, molybdic oxide, and its components by weight percent ratio is 8 ~ 12:2 ~ 8.
ethylene-vinyl acetate (EVA)
In a specific embodiment of the present invention, the VA content of described ethylene-vinyl acetate (EVA) is 28%.
methyl vinyl silicone rubber
In a specific embodiment of the present invention, described methyl vinyl silicone rubber, its vinyl molar percentage is 0.13-0.22.
oxidation inhibitor
Oxidation inhibitor of the present invention is not specifically limited, and can adopt various available oxidation inhibitor, only otherwise to goal of the invention of the present invention produces and limits.Such as Hinered phenols antioxidant, arylamine kind antioxidant.
In a specific embodiment of the present invention, described oxidation inhibitor is four [β-(3,5-di-tert-butyl-hydroxy phenyl) propionic acid] pentaerythritol ester (antioxidant 1010), tricresyl phosphite (2,4-di-tert-butyl-phenyl) combination of ester (irgasfos 168), its components by weight percent ratio is 0.4 ~ 1:0.4 ~ 1.
lubricant
Lubricant of the present invention is not specifically limited, and can adopt various available lubricant, only otherwise to goal of the invention of the present invention produces and limits.Such as stearate, polyethylene wax, silicone resin.
In a specific embodiment of the present invention, described lubricant is one in calcium stearate, Zinic stearas, Magnesium Stearate, polyethylene wax or some combination.
coupling agent
Coupling agent of the present invention is not specifically limited, and can adopt various available coupling agent, only otherwise to goal of the invention of the present invention produces and limits.Such as titanate coupling agent, aluminate coupling agent.
In a specific embodiment of the present invention, described coupling agent is the one in silane coupling agent, aluminate coupling agent, phosphate coupling agent, boric acid ester coupler.
vulcanizing agent
In a specific embodiment of the present invention, described vulcanizing agent is two 2,5 vulcanizing agents, and its fusing point is 8 DEG C, and decomposition temperature is 140-150 DEG C.Curing temperature is 150-160 DEG C.
Cable
The cable that a second aspect of the present invention provides a kind of low-smoke bittern-free highly fire-proof Oil-resistant cold-resistant CABLE MATERIALS of the present invention obtained.
The preparation method of described cable can adopt the ordinary skill in the art.
Preparation method
A third aspect of the present invention provides a kind of preparation method of low-smoke bittern-free highly fire-proof Oil-resistant cold-resistant CABLE MATERIALS of the present invention, and described preparation method comprises the following steps:
1) methyl vinyl silicone rubber of formula ratio and EVA are dropped in Banbury mixer, banburying 3-4min;
2) material of remaining all formula ratios is also dropped in Banbury mixer, continue banburying 5-6min with the methyl vinyl silicone rubber dropped into before together with EVA; Whole internal mixing pass 8-10min obtains the good work in-process of banburying;
3) work in-process that banburying is good are extruded stretching and granulation through Dual-cone feeding device and twin-screw extrusion unit and are obtained described low-smoke bittern-free highly fire-proof Oil-resistant cold-resistant CABLE MATERIALS; Each section of temperature of described twin screw controls from charging opening, and be followed successively by 90 ~ 100 DEG C, 90 ~ 100 DEG C, 90 ~ 95 DEG C, 85 ~ 90 DEG C, 85 ~ 90 DEG C, 75 ~ 85 DEG C, 85 ~ 90 DEG C, twin screw head temperature is 90 ~ 95 DEG C.
Advantage
A kind of low-smoke bittern-free highly fire-proof Oil-resistant cold-resistant CABLE MATERIALS of the present invention and preparation method's tool have the following advantages:
1. the present invention adopts material based on ethylene-vinyl acetate (EVA) and methyl vinyl silicone rubber, and has added strengthening agent gas-phase silica and two 2,5 vulcanizing agents, and the CABLE MATERIALS of preparation has the splendid feature of Cold-proof oilproof performance; In addition, owing to also having the characteristic of rubber, so the CABLE MATERIALS mechanical property also comparative superiority of preparation, wear resisting property weather resistance is also very good.
2. the fire retardant that the present invention adopts is magnesium hydroxide, antimonous oxide, zinc oxide, molybdic oxide, and the CABLE MATERIALS of preparation has high flame-retardant property.CABLE MATERIALS vertical combustion is by FV-0 level.
Other aspects of the present invention, due to disclosure herein, are apparent to those skilled in the art.
Below in conjunction with specific embodiment, set forth the present invention further.Should be understood that these embodiments are only not used in for illustration of the present invention to limit the scope of the invention.The experimental technique of unreceipted actual conditions in the following example, measures according to national standard usually.If there is no corresponding national standard, then according to general international standard, normal condition or carry out according to the condition that manufacturer advises.Unless otherwise indicated, otherwise all numbers are weight part, and all per-cent is weight percentage, and described polymericular weight is number-average molecular weight.
Unless otherwise defined or described herein, all specialties used herein and scientific words and those skilled in the art the same meaning be familiar with.In addition any method similar or impartial to described content and material all can be applicable in the inventive method.
Embodiment 1.
Each ingredient names and each composition weight number as follows:
The preparation method of foregoing invention, it comprises following processing step:
1) methyl vinyl silicone rubber of formula ratio and EVA are dropped in Banbury mixer, banburying 3-4min;
2) material of remaining all formula ratios is also dropped in Banbury mixer, continue banburying 5-6min with the methyl vinyl silicone rubber dropped into before together with EVA; Whole internal mixing pass 8-10min obtains the good work in-process of banburying;
3) work in-process that banburying is good are extruded stretching and granulation through Dual-cone feeding device and twin-screw extrusion unit and are obtained described low-smoke bittern-free highly fire-proof Oil-resistant cold-resistant CABLE MATERIALS; Each section of temperature of described twin screw controls from charging opening, and be followed successively by 90 ~ 100 DEG C, 90 ~ 100 DEG C, 90 ~ 95 DEG C, 85 ~ 90 DEG C, 85 ~ 90 DEG C, 75 ~ 85 DEG C, 85 ~ 90 DEG C, twin screw head temperature is 90 ~ 95 DEG C.
Carry out performance detection experiment to the product in embodiment 1, each performance value is as shown in PERFORMANCE EXAMPLES 1.
Embodiment 2.
Each ingredient names and each composition weight number as follows:
The preparation method of above-mentioned CABLE MATERIALS is identical with embodiment 1
Carry out performance detection experiment to the product in embodiment 2, each performance value is as shown in PERFORMANCE EXAMPLES 2.
Embodiment 3.
Each ingredient names and each composition weight number as follows:
The preparation method of above-mentioned CABLE MATERIALS is identical with embodiment 1.
Carry out performance detection experiment to the product in embodiment 3, each performance value is as shown in PERFORMANCE EXAMPLES 3
Embodiment 4.
Each ingredient names and each composition weight number as follows:
The preparation method of above-mentioned CABLE MATERIALS is identical with embodiment 1.
Carry out performance detection experiment to the product in embodiment 4, each performance value is as shown in PERFORMANCE EXAMPLES 4
PERFORMANCE EXAMPLES
Table 1 embodiment product performance test result
Resistance to mineral oiliness (IRM902 oil) 100 DEG C × 70h
Fuel-resistant oiliness (IRM903 oil) 70 DEG C × 168h
Conclusion
The present invention overcomes the deficiencies in the prior art, the CABLE MATERIALS produced, and flame retardant properties is good, and mechanical property is superior, and oil resistance wear resisting property is splendid, impacts brittle by low temperature-60 DEG C.
The foregoing is only preferred embodiment of the present invention, and be not used to limit substantial technological context of the present invention, substantial technological content of the present invention is broadly defined in the right of application, any technology entities that other people complete or method, if with application right define identical, also or a kind of change of equivalence, be all covered by being regarded as among this right.
The all documents mentioned in the present invention are quoted as a reference all in this application, are just quoted separately as a reference as each section of document.In addition should be understood that those skilled in the art can make various changes or modifications the present invention after having read foregoing of the present invention, these equivalent form of values fall within the application's appended claims limited range equally.

Claims (12)

CN201310654876.3A2013-12-052013-12-05A kind of low-smoke bittern-free highly fire-proof Oil-resistant cold-resistant CABLE MATERIALS and preparation method and cableActiveCN103627074B (en)

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CN104151690A (en)*2014-07-252014-11-19宁国新博能电子有限公司Halogen-free flame-retardant cable sheath material
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CN105482462B (en)*2015-12-142019-04-09湖南工业大学 A kind of high temperature resistant low smoke halogen free cable material and preparation method
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Patentee before:SHANGHAI ORIGINALDOW ADVANCED COMPOUNDS Co.,Ltd.


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