CN106566248A - Magnetic polyester resin-based silicone rubber cable material - Google Patents
Magnetic polyester resin-based silicone rubber cable material Download PDFInfo
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- CN106566248A CN106566248A CN201610905106.5A CN201610905106A CN106566248A CN 106566248 A CN106566248 A CN 106566248A CN 201610905106 A CN201610905106 A CN 201610905106A CN 106566248 A CN106566248 A CN 106566248A
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L83/00—Compositions of macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing silicon with or without sulfur, nitrogen, oxygen or carbon only; Compositions of derivatives of such polymers
- C08L83/04—Polysiloxanes
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01B—CABLES; CONDUCTORS; INSULATORS; SELECTION OF MATERIALS FOR THEIR CONDUCTIVE, INSULATING OR DIELECTRIC PROPERTIES
- H01B3/00—Insulators or insulating bodies characterised by the insulating materials; Selection of materials for their insulating or dielectric properties
- H01B3/18—Insulators or insulating bodies characterised by the insulating materials; Selection of materials for their insulating or dielectric properties mainly consisting of organic substances
- H01B3/28—Insulators or insulating bodies characterised by the insulating materials; Selection of materials for their insulating or dielectric properties mainly consisting of organic substances natural or synthetic rubbers
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2201/00—Properties
- C08L2201/02—Flame or fire retardant/resistant
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2203/00—Applications
- C08L2203/20—Applications use in electrical or conductive gadgets
- C08L2203/202—Applications use in electrical or conductive gadgets use in electrical wires or wirecoating
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2205/00—Polymer mixtures characterised by other features
- C08L2205/03—Polymer mixtures characterised by other features containing three or more polymers in a blend
- C08L2205/035—Polymer mixtures characterised by other features containing three or more polymers in a blend containing four or more polymers in a blend
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2312/00—Crosslinking
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- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- Compositions Of Macromolecular Compounds (AREA)
Abstract
The invention discloses a magnetic polyester resin-based silicone rubber cable material. The cable material is prepared from raw materials in parts by weight as follows: 60-70 parts of MVQ silicone rubber, 30-38 parts of polyester resin, 4-5 parts of poly glycidyl ester, 0.1-0.2 parts of photoinitiator benzophenone, 0.1-0.2 parts of a cross-linking agent TAIC, 3.6-4 parts of ferrous chloride, 6-6.8 parts of ferric trichloride, 20-25 parts of mica, 10-14 parts of low-melting-point glass powder, 1.6-2 parts of polyethylene glycol, 1.8-2.2 parts of ferrous sulfate, 2.5-3 parts of ammonium bicarbonate, 8-11 parts of soft magnetic ferrite, 4-5 parts of zinc oxide, 2-3 parts of paraffin oil, 0.2-0.3 parts of an antioxidant 168, 1.5-2 parts of carboxymethylcellulose, 2.8-3.5 parts of maleic anhydride and a proper amount of deionized water. The technology is reasonable, and the material is high in strength, resistant to acid and alkali corrosion, non-flammable, free of dripping, good in production and processing performance and worthy of popularization.
Description
Technical field
The present invention relates to field of cable technology, more particularly to a kind of magnetic poly-vinegar resin base silicone rubber for 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 will not produce the phenomenon of drippage without poison, 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 in itself oxygen index (OI) 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 it is in normal state general flexible silicone rubber material
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
Author is to add Muscovitum, glass powder with low melting point and fire retardant in silicone rubber system first in text, is prepared for the silicon of fire-retardant fireproof
Rubber, cross-linking effect is optimal when as a result showing that vulcanizing agent DCP is 1wt%, 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 the intensity of porcelain compound increases after sintering at a higher temperature, 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
The white carbon of 45wt% is in system, and reinforcing effect is good；The mass ratio of double-component is 60 in MVQ/LLDPE composites：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, the tensile strength of sample is significantly improved after ultraviolet light irradiation, 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, glass powder with low melting point and fire retardant to the performance of silicone rubber in silicone rubber system, and addition is mended
Strong resin material is to the impact of overall mechanical properties in silicone rubber, and the application diversification and extensiveization with cable material be 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 such as cold-resistant, freeze proof, high temperature resistant, anticorrosive and intensity in practice
With the Important Problems for how improving the overall performance of silicone rubber and remaining current research with its demand for meeting diversification cable.
The content of the invention
The object of the invention is exactly to make up the defect of prior art, there is provided a kind of magnetic poly-vinegar resin base silicone rubber for cable
Material.
The present invention is achieved by the following technical solutions：
A kind of magnetic poly-vinegar resin base silicone rubber for cable material, is made up of the raw material of following weight portion：MVQ silicone rubber 60-
70th, poly-vinegar resin 30-38, poly epihydric alcohol vinegar 4-5, light trigger benzophenone 0.1-0.2, cross-linking agent TAIC0.1-0.2, two
Iron 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, soft magnetic ferrite 8-11, Zinc Oxide 4-5, paraffin oil 2-3, the 0.2-0.3 of antioxidant 168,
Carboxymethyl cellulose 1.5-2, cis-butenedioic anhydride 2.8-3.5, appropriate deionized water.
A kind of magnetic poly-vinegar resin base silicone rubber for cable material, is made up of step in detail below：
（1）Ferrous chloride and ferric chloride are dissolved in deionized water, in being placed in 50 DEG C of waters bath with thermostatic control, stirring is until solution mixing
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, 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, respectively deionized water dissolving makes concentration for 0.2mol/L and 0.4mol/L
Solution, during the above-mentioned standby mixed solution being stirred vigorously is continuously fed into constant flow pump, control ph is 6.5 after completion of dropping,
Continue to react 50-70min under room temperature, filter after ageing 30min, precipitate with deionized water is cleaned to neutral post-drying；
（3）Carboxymethyl cellulose is added in the 9-11 times of deionized water measured, heated and stirred to sticky shape, add Zinc Oxide and
Cis-butenedioic anhydride stirring reaction 3-4h in the case where temperature is for 85-100 DEG C, then by soft magnetic ferrite and polyacrylic acid according to mass ratio 1:0.5 mixes
Close and suspension is obtained in ultrasonic disperse deionized water, wherein the concentration of magnetic powder is 0.01-0.03mol/L, then is changed above-mentioned
Property cmc soln be added in suspension, supersound process again, power 300W, time 30-40min are filtered, 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
Mix homogeneously, is added to MVQ silicone rubber, poly-vinegar resin and poly epihydric alcohol vinegar banbury and is kneaded according to mass ratio, mixing
Time is 10-20min, and melting temperature is 180 DEG C, and rotating speed is 100r/min, fused mass take out after in two-roll mill slice,
Again itself and above-mentioned preliminary mixture are added to into banburying in banbury jointly afterwards and uniformly, in two orthogonal direction magnetic are alternately added
, finally add light trigger, cross-linking agent TAIC, step（3）The product of preparation and other leftover materials carry out melt blending,
Melting temperature is 130 DEG C, kneads 5-8min, discharging, you can obtain.
It is an advantage of the invention that：The present invention generates silicon dioxide using silicone rubber after thermal degradation under oxygen and hot conditionss
Residue layer, Muscovitum can occur " eutectic " reaction with residue silicon dioxide at high temperature, and continuous structure is formed 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 under cryogenic promote silicone rubber residue to be formed
Mobile phase, quickening forms continuous residue, and forms the ceramic layer with some strength on surface and mica-bond, so
Modified glass dust can not only reduce generating the temperature of 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, utilizes
Soft magnetic ferrite is attached to its surface as magnetic medium by the carboxymethyl cellulose being modified, and improves in matrix resin
The compatibility and dispersibility, and improve the performances such as magnetic, anti-shielding, the fire-retardant and antibacterial of rubber cable, work of the present invention
Skill rationally, overcome that existing silicone rubber for cable is inflammable, intensity is not high, etc. aspect performance, high-strength, acid-alkali-corrosive-resisting, do not fire, nothing
Dropping, production and processing performance is good, and preparation process is simple is worthy to be popularized.
Specific embodiment
A kind of magnetic poly-vinegar resin base silicone rubber for cable material, by following weight portion（Kilogram）Raw material make：MVQ
Silicone rubber 60, poly-vinegar resin 30, poly epihydric alcohol vinegar 4, light trigger benzophenone 0.1, cross-linking agent TAIC0.1, ferrous chloride
3.6th, ferric chloride 6, Muscovitum 20, glass powder with low melting point 10, Polyethylene Glycol 1.6, ferrous sulfate 1.8, ammonium hydrogen carbonate 2.5, soft magnetism
Ferrite 8, Zinc Oxide 4, paraffin oil 2, antioxidant 168 0.2, carboxymethyl cellulose 1.5, cis-butenedioic anhydride 2.8, appropriate deionized water.
A kind of magnetic poly-vinegar resin base silicone rubber for cable material, is made up of step in detail below：
（1）Ferrous chloride and ferric chloride are dissolved in deionized water, in being placed in 50 DEG C of waters bath with thermostatic control, stirring is until solution mixing
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, and precipitation is carried out into Magneto separate, uses
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；It is that 0.2mol/L and 0.4mol/L is molten that by ferrous sulfate and ammonium hydrogen carbonate, respectively concentration is made in deionized water dissolving
Liquid, during the above-mentioned standby mixed solution being stirred vigorously is continuously fed into constant flow pump, control ph is 6.5 after completion of dropping, in room
Temperature is lower to be continued to react 50min, is filtered after ageing 30min, and precipitate with deionized water is cleaned to neutral post-drying；
（3）Carboxymethyl cellulose is added in the deionized waters of 9 times of amounts, heated and stirred adds Zinc Oxide and suitable to sticky shape
Acid anhydride stirring reaction 3h in the case where temperature is for 85 DEG C, then by soft magnetic ferrite and polyacrylic acid according to mass ratio 1:0.5 mixing ultrasound point
Disperse and obtain in ionized water suspension, wherein the concentration of magnetic powder is 0.01mol/L, then by above-mentioned modified carboxy methyl cellulose
Solution is added in suspension, again supersound process, power 300W, time 30min, is filtered, 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-vinegar resin and poly epihydric alcohol vinegar are added to into banbury according to mass ratio and are kneaded, mixing time is
10min, melting temperature is 180 DEG C, and rotating speed is 100r/min, fused mass take out after in two-roll mill slice, again will afterwards
Itself and above-mentioned preliminary mixture are added to banburying in banbury and uniformly, alternately add magnetic field in two orthogonal direction, finally jointly
Add light trigger, cross-linking agent TAIC, step（3）The product of preparation and other leftover materials carry out melt blending, mixing temperature
Spend for 130 DEG C, knead 5min, discharging, you can obtain.
Preparation method according to embodiment prepares silicone rubber for cable material, and performance test is carried out to it, as a result as follows：
Tensile strength（MPa）：14.5；Elongation at break（%）：627；Heat ageing coefficient：0.93；Anti-flammability（UL94V）：V0；Pole
Limited oxygen index：33.5；Solvent resistance（Mass loss rate %）：3.3.
Claims (2)
1. a kind of magnetic poly-vinegar resin base silicone rubber for cable material, it is characterised in that be made up of the raw material of following weight portion：
MVQ silicone rubber 60-70, poly-vinegar resin 30-38, 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 1.8-2.2, ammonium hydrogen carbonate 2.5-3, soft magnetic ferrite 8-11, Zinc Oxide 4-5, paraffin oil 2-3, antioxidation
The 0.2-0.3 of agent 168, carboxymethyl cellulose 1.5-2, cis-butenedioic anhydride 2.8-3.5, appropriate deionized water.
2. a kind of magnetic poly-vinegar resin base silicone rubber for cable material according to claim 1, it is characterised in that by detail below
Step is made：
（1）Ferrous chloride and ferric chloride are dissolved in deionized water, in being placed in 50 DEG C of waters bath with thermostatic control, stirring is until solution mixing
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, 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, respectively deionized water dissolving makes concentration for 0.2mol/L and 0.4mol/L
Solution, during the above-mentioned standby mixed solution being stirred vigorously is continuously fed into constant flow pump, control ph is 6.5 after completion of dropping,
Continue to react 50-70min under room temperature, filter after ageing 30min, precipitate with deionized water is cleaned to neutral post-drying；
（3）Carboxymethyl cellulose is added in the 9-11 times of deionized water measured, heated and stirred to sticky shape, add Zinc Oxide and
Cis-butenedioic anhydride stirring reaction 3-4h in the case where temperature is for 85-100 DEG C, then by soft magnetic ferrite and polyacrylic acid according to mass ratio 1:0.5 mixes
Close and suspension is obtained in ultrasonic disperse deionized water, wherein the concentration of magnetic powder is 0.01-0.03mol/L, then is changed above-mentioned
Property cmc soln be added in suspension, supersound process again, power 300W, time 30-40min are filtered, 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
Mix homogeneously, is added to MVQ silicone rubber, poly-vinegar resin and poly epihydric alcohol vinegar banbury and is kneaded according to mass ratio, mixing
Time is 10-20min, and melting temperature is 180 DEG C, and rotating speed is 100r/min, fused mass take out after in two-roll mill slice,
Again itself and above-mentioned preliminary mixture are added to into banburying in banbury jointly afterwards and uniformly, in two orthogonal direction magnetic are alternately added
, finally add light trigger, cross-linking agent TAIC, step（3）The product of preparation and other leftover materials carry out melt blending,
Melting temperature is 130 DEG C, kneads 5-8min, discharging, you can obtain.
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201610905106.5A CN106566248A (en) | 2016-10-17 | 2016-10-17 | Magnetic polyester resin-based silicone rubber cable material |
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201610905106.5A CN106566248A (en) | 2016-10-17 | 2016-10-17 | Magnetic polyester resin-based silicone rubber cable material |
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| CN106566248A true CN106566248A (en) | 2017-04-19 |
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN110494030A (en) * | 2019-08-28 | 2019-11-22 | 合肥工业大学 | A kind of preparation method for the ferrite solid waste sound stage width band electromagnetic wave absorber that resin is strengthened |
| CN110915317A (en) * | 2017-07-20 | 2020-03-24 | 麦克赛尔控股株式会社 | Electromagnetic wave absorbing composition and electromagnetic wave absorber |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105885428A (en) * | 2016-05-10 | 2016-08-24 | 安徽华海特种电缆集团有限公司 | High-fire-retardant and wear-resistant modified silicone rubber cable material |
| CN105924968A (en) * | 2016-05-10 | 2016-09-07 | 安徽华海特种电缆集团有限公司 | High-flame-retardance anti-corrosion modified silicone rubber cable material |
-
2016
- 2016-10-17 CN CN201610905106.5A patent/CN106566248A/en active Pending
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105885428A (en) * | 2016-05-10 | 2016-08-24 | 安徽华海特种电缆集团有限公司 | High-fire-retardant and wear-resistant modified silicone rubber cable material |
| CN105924968A (en) * | 2016-05-10 | 2016-09-07 | 安徽华海特种电缆集团有限公司 | High-flame-retardance anti-corrosion modified silicone rubber cable material |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN110915317A (en) * | 2017-07-20 | 2020-03-24 | 麦克赛尔控股株式会社 | Electromagnetic wave absorbing composition and electromagnetic wave absorber |
| CN110494030A (en) * | 2019-08-28 | 2019-11-22 | 合肥工业大学 | A kind of preparation method for the ferrite solid waste sound stage width band electromagnetic wave absorber that resin is strengthened |
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Application publication date: 20170419 |