CN106543724A - A kind of fire-resistant silicon rubber cable material - Google Patents

Abstract

The invention discloses a kind of fire-resistant silicon rubber cable material, is made up of the raw material of following weight portion：MVQ silicone rubber 60 70, poly- phthalein polyimide resin 28 35, poly epihydric alcohol vinegar 45, light trigger benzophenone 0.1 0.2, cross-linking agent TAIC0.1 0.2, ferrous chloride 3.6 4, ferric chloride 6 6.8, Muscovitum 20 25, glass powder with low melting point 10 14, Polyethylene Glycol 1.6 2, ferrous sulfate 1.8 2.2, ammonium hydrogen carbonate 2.5 3, brucite 9 13, magnesia powder 57, Sodium Polystyrene Sulfonate 4.5 5, polyacrylic acid 3.3 5, appropriate deionized water；Preparation method of the present invention is simple, and excellent electrical property, fire retardant performance are excellent, and burning shelling performance is good, with good physical and mechanical propertiess, meets the requirement of varying environment temperature change, is worthy to be popularized.

Description

A kind of fire-resistant silicon rubber cable material

Technical field

The present invention relates to field of cable technology, more particularly to a kind of fire-resistant silicon rubber cable material.

Background technology

Silicone rubber is a class with the Si-O keys that repeat as main chain, and side chain is the height of the organic groups such as methyl, vinyl, phenyl Molecular compound.Due to the particularity of structure, determine that silicone rubber has excellent performance, such as ageing-resistant, high and low temperature resistance, Weather-proof, solvent resistance, electrical insulation capability, the inertia to outside hot-fluid and relatively low HRR etc..Pure silicone rubber The gas produced during burning does not have poison, will not produce the phenomenon of drippage, and the residue after burning is silicon dioxide, and it is covered in poly- The surface of compound, plays a part of to intercept heat transfer and mass transfer.These excellent performances due to silicone rubber so as to be widely applied to The fields such as cable, electric wire, space flight and aviation, automobile and chemical industry.But silicone rubber has oxygen index (OI) in itself much smaller than 30, and according to Industry standard, the material for manufacturing cable will have higher anti-flammability, in addition, silicone rubber is inflammable, once catch fire to continue , there is potential burning risk, so as to limit its application in wires and cables industry to a certain extent in burning.Ceramic Silicone rubber is a kind of refractory material for just receiving publicity in recent years, and which is the silicone rubber material of general flexibility in normal state Material, after naked light calcination is run into, silicone rubber can form one layer of continuation for being similar to ceramic material to keep out flame and invade, this Material is wrapped in copper core the insulating barrier as cable, excellent insulating property, and protection circuit is not short-circuited and situations such as open circuit. But the molecular flexibility of silicone rubber is big, and the interaction force between strand is weaker, causes mechanical strength poor, it is necessary to by having The cross-linking method of effect improves its mechanical property, widens range of application.

《The preparation and its performance study of fire protection flame retarding silicone rubber and photo-crosslinking silicone rubber/polyolefin composite cable material》One In text, author is to add Muscovitum, glass powder with low melting point and fire retardant in silicone rubber system first, is prepared for the silicon of fire-retardant fireproof Rubber, when as a result showing that vulcanizing agent DCP is 1wt%, cross-linking effect is optimal, and the addition of Muscovitum is most widely suited when being 40wt%, addition Glass powder with low melting point to after silicone rubber system, mechanical property deteriorate, but into porcelain temperature drop, the size of porcelain compound after sintering Tendencies toward shrinkage increases, and after sintering at a higher temperature, the intensity of porcelain compound increases, and heat shock resistance effect strengthens, but compactness Difference, but low-melting glass powder content it is certain when, temperature is raised has certain to the intensity of porcelain compound after heat shock resistance and sintering Castering action, so the content of glass dust is best when being 30wt%.Secondly under conditions of light trigger and cross-linking agent are present, profit With ultraviolet light to MVQ（Silicone rubber）/LLDPE（Linear low density polyethylene）Thermoplastic elastomer is crosslinked, and as a result shows addition , in system, reinforcing effect is good for the white carbon of 45wt%；In MVQ/LLDPE composites, the mass ratio of double-component is 60：40 timeliness Preferably, as effect during both compatilizers preferably, addition is most widely suited when being 4wt% for LDPE-MA, antioxidant 1010 addition for fruit Measure for 0.5wt% when system combination property preferably, after ultraviolet light irradiation, the tensile strength of sample is significantly improved, but extension at break Rate declines, and ageing properties test shows, with the prolongation of ultraviolet light irradiation time, the ageing resistance of material is improved.Make herein Person separately elaborates to add Muscovitum, the performance of the glass powder with low melting point and fire retardant silicone rubber in silicone rubber system, and addition is mended The impact of strong resin material overall mechanical properties in silicone rubber, it is with application diversification and extensiveization of cable material, residing Requirement of the abominable of geographical environment to cable material is very high, and fire-retardant is one of necessary problem that silicone rubber for cable considers, for Other performances are also intended to the index as reference, institute in practice such as cold-resistant, freeze proof, high temperature resistant, anticorrosive and intensity The Important Problems of current research are remained how to improve the overall performance of silicone rubber with its demand for meeting diversification cable.

The content of the invention

The object of the invention is exactly for the defect for making up prior art, there is provided a kind of fire-resistant silicon rubber cable material.

The present invention is achieved by the following technical solutions：

A kind of fire-resistant silicon rubber cable material, is made up of the raw material of following weight portion：MVQ silicone rubber 60-70, poly- phthalein amine tree Fat 28-35, poly epihydric alcohol vinegar 4-5, light trigger benzophenone 0.1-0.2, cross-linking agent TAIC0.1-0.2, ferrous chloride 3.6-4, ferric chloride 6-6.8, Muscovitum 20-25, glass powder with low melting point 10-14, Polyethylene Glycol 1.6-2, ferrous sulfate 1.8- 2.2nd, ammonium hydrogen carbonate 2.5-3, brucite 9-13, magnesia powder 5-7, Sodium Polystyrene Sulfonate 4.5-5, polyacrylic acid 3.3-5, go Ion appropriate amount of water.

A kind of fire-resistant silicon rubber cable material, is made up of step in detail below：

（1）Ferrous chloride and ferric chloride are dissolved in deionized water, are placed in 50 DEG C of waters bath with thermostatic control, stirring is until solution mixes Uniformly, add Muscovitum to stir with the rotating speed of 1600-1800r/min, be slowly added dropwise with the speed of 1d/s afterwards mole dense The sodium hydroxide solution for 1.34mol/L is spent, until system pH is to 12, is stood, crystallization 2-4h, is filtered, precipitation is carried out into magnetic Separate, repeatedly washing, up to into neutrality, is vacuum dried and obtains modified magnetic Muscovitum deionized water；

（2）Glass powder with low melting point is added in the 11-13 times of dehydrated alcohol measured, Polyethylene Glycol ultrasonic disperse is stirring evenly and then adding into Uniformly, it is standby；By ferrous sulfate and ammonium hydrogen carbonate, deionized water dissolving makes concentration for 0.2mol/L and 0.4mol/L respectively Solution, is continuously fed into constant flow pump in the above-mentioned standby mixed solution being stirred vigorously, and after completion of dropping, control ph is 6.5, Continue reaction 50-70min under room temperature, filter after ageing 30min, precipitate with deionized water is cleaned to neutral post-drying；

（3）Brucite being added in deionized water and high-temperature being risen to 80-100 DEG C, magnetic agitation forms emulsion, wherein quality hundred Divide specific concentration to be 60-75%, add magnesia powder and continue magnetic agitation 30-40min, be cooled to 40-50 DEG C afterwards, add Sodium Polystyrene Sulfonate and polyacrylic acid are stirred continuously and heat temperature raising, 3-4h are reacted when temperature is increased to 70-90 DEG C, instead Room temperature should be cooled to after terminating, be filtered, washing, drying；

（4）By step（1）The product and step of preparation（2）The product of preparation is according to mass ratio 40-65wt%：35-60wt% grinds MVQ silicone rubber, poly- phthalein polyimide resin and poly epihydric alcohol vinegar are added to banbury according to mass ratio and are kneaded by mix homogeneously, are mixed The refining time is 10-20min, and melting temperature is 180 DEG C, and rotating speed is 100r/min, is gone out after fused mass taking-up in two-roll mill Itself and above-mentioned preliminary mixture are added to banburying in banbury and uniformly, are added in two orthogonal direction alternating by piece afterwards again jointly Plus magnetic field, finally add light trigger, cross-linking agent TAIC, step（3）The product of preparation and other leftover materials are melted Blending, melting temperature are 130 DEG C, knead 5-8min, discharging, you can obtain.

It is an advantage of the invention that：The present invention thermal degradation after is generating silicon dioxide under oxygen and hot conditionss using silicone rubber Residue layer, Muscovitum can occur " eutectic " reaction with residue silicon dioxide at high temperature, form continuous structure at high temperature, When this structure is in 5-10 μ m-thicks just can effective strengthen burning residual ceramic layer intensity, thus anti-flammability can be improved, but Residue intensity after sintering at a lower temperature is not high, needs to add the sintering temperature that filler reduces reacting, and ferrum oxide changes Property Muscovitum and glass powder with low melting point so as to area load ferrum oxide simultaneously has magnetic, can be dispersed under the influence of a magnetic field In matrix material, and the glass powder with low melting point of ferrum oxide load can promote silicone rubber residue to be formed under cryogenic Mobile phase, quickening form continuous residue, and form ceramic layer with some strength with mica-bond on surface, so Modified glass dust can not only reduce the temperature for generating ceramics, it is also possible to quickly promote silicone rubber fast decoupled production dioxy SiClx residue, while also improving the intensity of ceramic layer, it also avoid addition excessively causes the problem of processing difficulties, also profit There is unrivaled advantage as fire-proof packing with brucite and magnesia powder compounding, fireproof anti-cracking performance is good, in order to solve Bad dispersibility of the filler in silicone rubber matrix utilizes Sodium Polystyrene Sulfonate and polyacrylic acid modified to which, improves and matrix The compatibility of material, and fire-retardant, suppression cigarette, fireproof performance are improve, preparation method of the present invention is simple, and excellent electrical property is prevented Fiery excellent fireproof performance, burning shelling performance are good, with good physical and mechanical propertiess, meet wanting for varying environment temperature change Ask, be worthy to be popularized.

Specific embodiment

A kind of fire-resistant silicon rubber cable material, by following weight portion（Kilogram）Raw material make：MVQ silicone rubber 60, Poly- phthalein polyimide resin 28, poly epihydric alcohol vinegar 4, light trigger benzophenone 0.1, cross-linking agent TAIC0.1, ferrous chloride 3.6, trichlorine Change ferrum 6, Muscovitum 20, glass powder with low melting point 10, Polyethylene Glycol 1.6, ferrous sulfate 1.8, ammonium hydrogen carbonate 2.5, brucite 9, magnesia Fine powder 5, Sodium Polystyrene Sulfonate 4.5, polyacrylic acid 3.3, appropriate deionized water.

A kind of fire-resistant silicon rubber cable material, is made up of step in detail below：

（1）Ferrous chloride and ferric chloride are dissolved in deionized water, are placed in 50 DEG C of waters bath with thermostatic control, stirring is until solution mixes Uniformly, add Muscovitum to stir with the rotating speed of 1600r/min, being slowly added dropwise molar concentration with the speed of 1d/s afterwards is The sodium hydroxide solution of 1.34mol/L, until system pH is to 12, stands, crystallization 2h, filters, precipitation is carried out Magneto separate, use Repeatedly washing, up to into neutrality, is vacuum dried and obtains modified magnetic Muscovitum deionized water；

（2）Glass powder with low melting point is added in the dehydrated alcohol of 11 times of amounts, Polyethylene Glycol ultrasonic disperse is stirring evenly and then adding into equal It is even, it is standby；By ferrous sulfate and ammonium hydrogen carbonate respectively deionized water dissolving make concentration for 0.2mol/L and 0.4mol/L it is molten Liquid, is continuously fed into constant flow pump in the above-mentioned standby mixed solution being stirred vigorously, and after completion of dropping, control ph is 6.5, in room Temperature is lower to continue reaction 50min, filters after ageing 30min, and precipitate with deionized water is cleaned to neutral post-drying；

（3）Brucite being added in deionized water and high-temperature being risen to 80 DEG C, magnetic agitation forms emulsion, wherein mass percent Concentration is 60%, adds magnesia powder and continues magnetic agitation 30min, is cooled to 40 DEG C afterwards, adds Sodium Polystyrene Sulfonate It is stirred continuously with polyacrylic acid and heat temperature raising, 3h is reacted when temperature is increased to 70 DEG C, reaction is cooled to room temperature after terminating, Filter, washing, drying；

（4）By step（1）The product and step of preparation（2）The product of preparation is according to mass ratio 40wt%：35wt% ground and mixeds are equal It is even, MVQ silicone rubber, poly- phthalein polyimide resin and poly epihydric alcohol vinegar are added to banbury according to mass ratio and are kneaded, mixing time For 10min, melting temperature is 180 DEG C, and rotating speed is 100r/min, fused mass take out after in two-roll mill slice, Zhi Houzai Itself and above-mentioned preliminary mixture are added to into banburying in banbury jointly and uniformly, alternately add magnetic field in two orthogonal direction, most After add light trigger, cross-linking agent TAIC, step（3）The product of preparation and other leftover materials carry out melt blending, knead Temperature is 130 DEG C, kneads 5min, discharging, you can obtain.

Preparation method according to embodiment prepares silicone rubber for cable material, and performance test is carried out to which, as a result as follows：

Tensile strength（MPa）：13.3；Elongation at break（%）：633；Heat ageing coefficient：0.93；Anti-flammability（UL94V）：V0；Pole Limited oxygen index：32.5；Solvent resistance（Mass loss rate %）：3.2.

Claims (2)

1. a kind of fire-resistant silicon rubber cable material, it is characterised in that be made up of the raw material of following weight portion：MVQ silicone rubber 60-70, poly- phthalein polyimide resin 28-35, poly epihydric alcohol vinegar 4-5, light trigger benzophenone 0.1-0.2, cross-linking agent TAIC0.1- 0.2nd, ferrous chloride 3.6-4, ferric chloride 6-6.8, Muscovitum 20-25, glass powder with low melting point 10-14, Polyethylene Glycol 1.6-2, sulfur Sour ferrous iron 1.8-2.2, ammonium hydrogen carbonate 2.5-3, brucite 9-13, magnesia powder 5-7, Sodium Polystyrene Sulfonate 4.5-5, polypropylene Sour 3.3-5, appropriate deionized water.

2. a kind of fire-resistant silicon rubber cable material according to claim 1, it is characterised in that prepared by step in detail below and made Into：

（1）Ferrous chloride and ferric chloride are dissolved in deionized water, are placed in 50 DEG C of waters bath with thermostatic control, stirring is until solution mixes Uniformly, add Muscovitum to stir with the rotating speed of 1600-1800r/min, be slowly added dropwise with the speed of 1d/s afterwards mole dense The sodium hydroxide solution for 1.34mol/L is spent, until system pH is to 12, is stood, crystallization 2-4h, is filtered, precipitation is carried out into magnetic Separate, repeatedly washing, up to into neutrality, is vacuum dried and obtains modified magnetic Muscovitum deionized water；

（2）Glass powder with low melting point is added in the 11-13 times of dehydrated alcohol measured, Polyethylene Glycol ultrasonic disperse is stirring evenly and then adding into Uniformly, it is standby；By ferrous sulfate and ammonium hydrogen carbonate, deionized water dissolving makes concentration for 0.2mol/L and 0.4mol/L respectively Solution, is continuously fed into constant flow pump in the above-mentioned standby mixed solution being stirred vigorously, and after completion of dropping, control ph is 6.5, Continue reaction 50-70min under room temperature, filter after ageing 30min, precipitate with deionized water is cleaned to neutral post-drying；

（3）Brucite being added in deionized water and high-temperature being risen to 80-100 DEG C, magnetic agitation forms emulsion, wherein quality hundred Divide specific concentration to be 60-75%, add magnesia powder and continue magnetic agitation 30-40min, be cooled to 40-50 DEG C afterwards, add Sodium Polystyrene Sulfonate and polyacrylic acid are stirred continuously and heat temperature raising, 3-4h are reacted when temperature is increased to 70-90 DEG C, instead Room temperature should be cooled to after terminating, be filtered, washing, drying；

（4）By step（1）The product and step of preparation（2）The product of preparation is according to mass ratio 40-65wt%：35-60wt% grinds MVQ silicone rubber, poly- phthalein polyimide resin and poly epihydric alcohol vinegar are added to banbury according to mass ratio and are kneaded by mix homogeneously, are mixed The refining time is 10-20min, and melting temperature is 180 DEG C, and rotating speed is 100r/min, is gone out after fused mass taking-up in two-roll mill Itself and above-mentioned preliminary mixture are added to banburying in banbury and uniformly, are added in two orthogonal direction alternating by piece afterwards again jointly Plus magnetic field, finally add light trigger, cross-linking agent TAIC, step（3）The product of preparation and other leftover materials are melted Blending, melting temperature are 130 DEG C, knead 5-8min, discharging, you can obtain.