CN104987644A - Precipitation-resistant halogen-free flame-retardant wire and cable material free of phosphine and preparation method therefor - Google Patents

Precipitation-resistant halogen-free flame-retardant wire and cable material free of phosphine and preparation method therefor Download PDF

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Publication number
CN104987644A
CN104987644A CN201510435888.6A CN201510435888A CN104987644A CN 104987644 A CN104987644 A CN 104987644A CN 201510435888 A CN201510435888 A CN 201510435888A CN 104987644 A CN104987644 A CN 104987644A
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halogen
precipitation
retardant
wire
free flame
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CN201510435888.6A
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王超
金绪刚
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Shenzhen Ryd Sci&tech Co Ltd
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Shenzhen Ryd Sci&tech Co Ltd
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Abstract

The invention relates to the technical field of wiring materials and particularly relates to a precipitation-resistant halogen-free flame-retardant wire and cable material free of phosphine and a preparation method therefor. The wire and cable material contains the ingredients in percentage by weight: 20-40% of styrene-ethylene-butadiene-styrene copolymer (SEBS), 5-15% of ester polymer, 5-20% of polypropylene, 10-30% of paraffin oil, 10-30% of hypophosphorous acid flame retardant, 5-15% of synergist, 4-10% of compatibilizer, 0.5-3% of lubricant and 0.1-0.5% of antioxidant. According to the halogen-free flame-retardant TPE (Thermoplastic Elastomer) wire and cable material adopting SEBS as matrix resin, prepared by the preparation method, a higher carbonizing speed can be obtained while guaranteeing the primary characteristics and mechanical properties of the material, and good flame-retardant effect and migration resisting effect are achieved through the compounding among the ingredients; and the wire and cable material is free of halogen and heavy metal and does not generate phosphine, thereby meeting environment-friendly requirements of ROHS, Reach and the like.

Description

The halogen-free flame-retardant wire of resistance to precipitation CABLE MATERIALS of a kind of not phosphine containing and preparation method thereof
Technical field
The present invention relates to wiring material technical field, the halogen-free flame-retardant wire of resistance to precipitation CABLE MATERIALS of especially a kind of not phosphine containing and preparation method thereof.
Background technology
Traditional fire-retardant class wire cable material mainly with polyvinyl chloride (PVC) for base material, coordinate halogen-containing bromo-antimony fire retardant and other auxiliary agents to obtain.Along with the development of wire cable material flame-retarded technology and countries in the world are to the pay attention to day by day of environmental protection, PVC cable is replaced by the Halogen TPE electric wire being base material with SEBS (SIS/SEBS) just gradually.Existing halogen-free flameproof TPE wire cable material forms primarily of SEBS, white oil, fire retardant, thermoplastic resin and other additive compounds, usually can carry out fire-retardant with magnesium hydroxide (MH), P-N type (as MCA) or high ammonium polyphosphate (APP) based flame retardant in industry.
But the flame retarding efficiency of single mineral-type fire retardant (as MH) is lower, higher addition seriously can reduce the mechanical property of material; Then there is poor, the easy precipitation of thermostability, easily produce the problems such as phosphine gas in traditional P-N type fire retardant.Because phosphuret-(t)ed hydrogen is highly toxic substance, along with the development of wires and cables industry, the phosphuret-(t)ed hydrogen produced by fire retardant in sizing material has also been put into objectionable impurities management and control scope.
Therefore, find a kind of while guarantee material primary characteristic and mechanical property, can obtain one-tenth carbon speed faster and resistance to migration, the fire retardant material that do not produce phosphine gas become technical problem urgently to be resolved hurrily in industry.
Summary of the invention
For the deficiency that above-mentioned prior art exists, one object of the present invention be to provide a kind of flame retardant properties significantly, become carbon speed soon, not halogen-containing and heavy metal, meet the halogen-free flame-retardant wire of the resistance to precipitation CABLE MATERIALS of the not phosphine containing of environmental requirement; Another object of the present invention is the preparation method of the halogen-free flame-retardant wire of the resistance to precipitation CABLE MATERIALS providing a kind of not phosphine containing, and it has technical process feature simple, with low cost.
To achieve these goals, the present invention adopts following technical scheme:
The not halogen-free flame-retardant wire of a resistance to precipitation CABLE MATERIALS for phosphine containing, its component and weight proportion as follows:
Preferably, the cinnamic weight content in described SIS/SEBS is 30% ~ 40%.
Preferably, described esters polymer is the one in ethylene ethyl acrylate, ethylene methyl acrylate, ethylene butyl acrylate, Polyurethane Thermoplastic Elastomer rubber, and the melting index of described esters polymer is 1-5g/10min.
Preferably, the weight content of the phosphorus in described hypophosphite based flame retardant is greater than 30%, and the heat decomposition temperature of described hypophosphite based flame retardant is greater than 250 DEG C.
Preferably, described synergist is at least one in expansible black lead, zinc borate, nano imvite, silicon oxide, melamine cyanurate.
Preferably, described compatilizer is the one in maleic anhydride inoculated polypropylene, maleic anhydride stem grafting polyolefin elastomerics, maleic anhydride-g-SBS.
Preferably, described lubricant is at least one in silicone master batch, Zinic stearas, polyethylene wax.
Preferably, described oxidation inhibitor is the mixture of Hinered phenols antioxidant and phosphorous acid kind antioxidant.
Prepare a preparation method for the halogen-free flame-retardant wire of the resistance to precipitation CABLE MATERIALS of above-mentioned not phosphine containing, it comprises the following steps:
Each component weighs for subsequent use by S1, foundation weight ratio;
S2, SIS/SEBS and paraffin oil are stirred 40min in mixing machine;
S3, add esters polymer, polypropylene, Hypophosporous Acid, 50 based flame retardant, synergist, compatilizer, lubricant and oxidation inhibitor stir 15min again after discharging for subsequent use;
S4, utilize twin screw extruder to carry out extruding pelletization and drying treatment to the discharging raw material in step S3, namely obtain wire cable material.
Preferably, in step s 4 which, arrange as follows to the temperature of twin screw extruder: feeding section 160 DEG C ~ 170 DEG C, mixing section 180 DEG C ~ 200 DEG C, metering zone 180 DEG C ~ 190 DEG C, head 170 DEG C-190 DEG C.
Owing to have employed such scheme, it take SEBS as the halogen-free flameproof TPE wire cable material of matrix resin that the present invention is formed a kind of, while guarantee material primary characteristic and mechanical property, can obtain and become carbon speed faster, good flame retardant effect and resistance to migration effect is reached by composite between component, it is not halogen-containing, heavy metal, produces, meet the environmental requirements such as ROHS, Reach without phosphine gas; And the preparation method adopted, not only can ensure the performance of final discharging, and technical process is simple, is conducive to reducing production cost.
Embodiment
Be described in detail below in conjunction with to embodiments of the invention, but the multitude of different ways that the present invention can be defined by the claims and cover is implemented.
The halogen-free flame-retardant wire of the resistance to precipitation CABLE MATERIALS of a kind of not phosphine containing that the present embodiment provides, its component and weight proportion as follows:
As a preferred version, the cinnamic weight content in the SIS/SEBS of the present embodiment is 30% ~ 40%; One in G-1651, G-1650, G-1654 that its Ke Teng company of preferred U.S. produces.
As a preferred version, the esters polymer of the present embodiment is the one in ethylene ethyl acrylate (that is: EEA), ethylene methyl acrylate (that is: EMA), ethylene butyl acrylate (that is: EBA), Polyurethane Thermoplastic Elastomer rubber (that is: TPU), and its melting index (MI) controls at 1-5g/10min.
As a preferred version, the weight content of the phosphorus in the hypophosphite based flame retardant of the present embodiment is greater than 30%, and the heat decomposition temperature of hypophosphite based flame retardant is greater than 250 DEG C.
As a preferred version, the synergist of the present embodiment is at least one in expansible black lead (that is: EG), zinc borate (that is: ZnB), nano imvite, silicon oxide, melamine cyanurate.
As a preferred version, the compatilizer of the present embodiment is maleic anhydride inoculated polypropylene (as PP-g-MH) or maleic anhydride stem grafting polyolefin elastomerics (as POE-g-MH, EVA-g-MH) or maleic anhydride-g-SBS (i.e. SEBS-G-MH).
As a preferred version, the lubricant of the present embodiment is at least one in silicone master batch, Zinic stearas, polyethylene wax.
As a preferred version, the oxidation inhibitor of the present embodiment is the mixture of Hinered phenols antioxidant and phosphorous acid kind antioxidant, preferably the mixture of 1010 type oxidation inhibitor and 168 type oxidation inhibitor, and both optimum mixture ratio examples are 1:2.
In addition, the polyacrylic melting index (MI) of the present embodiment controls at 3-8g/10min, and paraffin oil selected parameter is: kinematic viscosity when 40 DEG C is 45mm2/S.
Based on said wires CABLE MATERIALS, the present embodiment additionally provides a kind of preparation method preparing the halogen-free flame-retardant wire of the resistance to precipitation CABLE MATERIALS of above-mentioned not phosphine containing, and it comprises the following steps:
Each component weighs for subsequent use by S1, foundation weight ratio;
S2, SIS/SEBS and paraffin oil are stirred 40min in mixing machine;
S3, add esters polymer, polypropylene, Hypophosporous Acid, 50 based flame retardant, synergist, compatilizer, lubricant and oxidation inhibitor stir 15min again after discharging for subsequent use;
S4, utilize twin screw extruder to carry out extruding pelletization and drying treatment to the discharging raw material in step S3, namely obtain wire cable material.
For ensureing the effect of extruding pelletization and drying, in step s 4 which, arrange as follows to the temperature of twin screw extruder: feeding section 160 DEG C ~ 170 DEG C, mixing section 180 DEG C ~ 200 DEG C, metering zone 180 DEG C ~ 190 DEG C, head 170 DEG C-190 DEG C.
Specific embodiment 1-2 is as shown in the table:
Embodiment 1 and the wire cable material of embodiment 2 obtained by foundation aforesaid method, the protective layer of the wire rods such as cellular phone data line, charger line, telecommunication cable, control cables or signal optical cable can be widely used in, through detecting, two kinds of embodiments all not phosphine containing, protective layer is smooth, without particle, mechanical property can reach 10Mpa, elongation can reach more than 300%; Wherein, the wire rod protection layer formed by embodiment 1 is by UL1581 VW-1 flame retardant test, and the wire rod protection layer that embodiment 2 is formed is by UL1581 FT-2 flame retardant test; And the wire rod protection layer that two embodiments are formed is when poach (standard is 75 DEG C of X5 days) detects after compression, surface without fuel-displaced, without abnormal problems such as powder delivery.
The foregoing is only the preferred embodiments of the present invention; not thereby the scope of the claims of the present invention is limited; every utilize specification sheets of the present invention and content to do equivalent structure or equivalent flow process conversion; or be directly or indirectly used in other relevant technical fields, be all in like manner included in scope of patent protection of the present invention.

Claims (10)

1. the halogen-free flame-retardant wire of a resistance to precipitation CABLE MATERIALS for not phosphine containing, is characterized in that: its component and weight proportion as follows:
2. the halogen-free flame-retardant wire of the resistance to precipitation CABLE MATERIALS of a kind of not phosphine containing as claimed in claim 1, is characterized in that: the cinnamic weight content in described SIS/SEBS is 30% ~ 40%.
3. the halogen-free flame-retardant wire of the resistance to precipitation CABLE MATERIALS of a kind of not phosphine containing as claimed in claim 1, it is characterized in that: described esters polymer is the one in ethylene ethyl acrylate, ethylene methyl acrylate, ethylene butyl acrylate, Polyurethane Thermoplastic Elastomer rubber, the melting index of described esters polymer is 1-5g/10min.
4. the halogen-free flame-retardant wire of the resistance to precipitation CABLE MATERIALS of a kind of not phosphine containing as claimed in claim 1, it is characterized in that: the weight content of the phosphorus in described hypophosphite based flame retardant is greater than 30%, the heat decomposition temperature of described hypophosphite based flame retardant is greater than 250 DEG C.
5. the halogen-free flame-retardant wire of the resistance to precipitation CABLE MATERIALS of a kind of not phosphine containing as claimed in claim 1, is characterized in that: described synergist is at least one in expansible black lead, zinc borate, nano imvite, silicon oxide, melamine cyanurate.
6. the halogen-free flame-retardant wire of the resistance to precipitation CABLE MATERIALS of a kind of not phosphine containing as claimed in claim 1, is characterized in that: described compatilizer is the one in maleic anhydride inoculated polypropylene, maleic anhydride stem grafting polyolefin elastomerics, maleic anhydride-g-SBS.
7. the halogen-free flame-retardant wire of the resistance to precipitation CABLE MATERIALS of a kind of not phosphine containing as claimed in claim 1, is characterized in that: described lubricant is at least one in silicone master batch, Zinic stearas, polyethylene wax.
8. the halogen-free flame-retardant wire of the resistance to precipitation CABLE MATERIALS of a kind of not phosphine containing as claimed in claim 1, is characterized in that: described oxidation inhibitor is the mixture of Hinered phenols antioxidant and phosphorous acid kind antioxidant.
9. prepare a preparation method for the halogen-free flame-retardant wire of the resistance to precipitation CABLE MATERIALS of the not phosphine containing according to any one of claim 1-8, it is characterized in that: it comprises the following steps:
Each component weighs for subsequent use by S1, foundation weight ratio;
S2, SIS/SEBS and paraffin oil are stirred 40min in mixing machine;
S3, add esters polymer, polypropylene, Hypophosporous Acid, 50 based flame retardant, synergist, compatilizer, lubricant and oxidation inhibitor stir 15min again after discharging for subsequent use;
S4, utilize twin screw extruder to carry out extruding pelletization and drying treatment to the discharging raw material in step S3, namely obtain wire cable material.
10. the preparation method of a kind of halogen-free flame-retardant wire of resistance to precipitation CABLE MATERIALS of not phosphine containing as claimed in claim 9, it is characterized in that: in step s 4 which, arrange as follows to the temperature of twin screw extruder: feeding section 160 DEG C ~ 170 DEG C, mixing section 180 DEG C ~ 200 DEG C, metering zone 180 DEG C ~ 190 DEG C, head 170 DEG C-190 DEG C.
CN201510435888.6A 2015-07-22 2015-07-22 Precipitation-resistant halogen-free flame-retardant wire and cable material free of phosphine and preparation method therefor Pending CN104987644A (en)

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Cited By (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN106633787A (en) * 2016-09-12 2017-05-10 国家电网公司 Cable
CN106751373A (en) * 2017-02-09 2017-05-31 厦门港沅塑胶工业有限公司 A kind of high-strength halogen-free flame-retardant thermoplastic elastomer and preparation method thereof
CN107936439A (en) * 2017-10-17 2018-04-20 国网江苏省电力公司盐城供电公司 A kind of high tenacity flame retardant cable and its preparation process for power circuit
CN110441289A (en) * 2019-08-12 2019-11-12 北京理工大学 A kind of evaluation method and its application of phosphorus flame retardant phosphine release amount
CN112375295A (en) * 2020-11-26 2021-02-19 湖南科森高分子材料科技有限公司 Formula of heat-resistant low-smoke halogen-free cable material

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CN104629183A (en) * 2015-02-12 2015-05-20 常熟市中联光电新材料有限责任公司 Oil-resistant, high-temperature-resistant and flame-retardant thermoplastic elastomer cable material and preparation method thereof

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CN104629183A (en) * 2015-02-12 2015-05-20 常熟市中联光电新材料有限责任公司 Oil-resistant, high-temperature-resistant and flame-retardant thermoplastic elastomer cable material and preparation method thereof

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Cited By (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN106633787A (en) * 2016-09-12 2017-05-10 国家电网公司 Cable
CN106751373A (en) * 2017-02-09 2017-05-31 厦门港沅塑胶工业有限公司 A kind of high-strength halogen-free flame-retardant thermoplastic elastomer and preparation method thereof
CN107936439A (en) * 2017-10-17 2018-04-20 国网江苏省电力公司盐城供电公司 A kind of high tenacity flame retardant cable and its preparation process for power circuit
CN110441289A (en) * 2019-08-12 2019-11-12 北京理工大学 A kind of evaluation method and its application of phosphorus flame retardant phosphine release amount
CN110441289B (en) * 2019-08-12 2020-07-14 北京理工大学 Evaluation method of phosphorus flame retardant hydrogen phosphide release amount and application thereof
CN112375295A (en) * 2020-11-26 2021-02-19 湖南科森高分子材料科技有限公司 Formula of heat-resistant low-smoke halogen-free cable material

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Application publication date: 20151021