CN106554628A - A kind of extraordinary freeze proof silicone rubber for cable material that resists cold - Google Patents
A kind of extraordinary freeze proof silicone rubber for cable material that resists cold Download PDFInfo
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- CN106554628A CN106554628A CN201610905631.7A CN201610905631A CN106554628A CN 106554628 A CN106554628 A CN 106554628A CN 201610905631 A CN201610905631 A CN 201610905631A CN 106554628 A CN106554628 A CN 106554628A
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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
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K2201/00—Specific properties of additives
- C08K2201/01—Magnetic additives
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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
- C08L2201/00—Properties
- C08L2201/08—Stabilised against heat, light or radiation or oxydation
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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
- C08L2205/02—Polymer mixtures characterised by other features containing two or more polymers of the same C08L -group
- C08L2205/025—Polymer mixtures characterised by other features containing two or more polymers of the same C08L -group containing two or more polymers of the same hierarchy C08L, and differing only in parameters such as density, comonomer content, molecular weight, structure
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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
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Abstract
The invention discloses a kind of extraordinary freeze proof silicone rubber for cable material that resists cold, is made up of the raw material of following weight portion：MVQ silicon rubber 60 70, polyimides 27 33, vinyl silicone oil 45, light trigger benzophenone 0.1 0.2, crosslinking agent TAIC0.1 0.2, ferrous chloride 3.6 4, ferric trichloride 6 6.8, mica 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, octyl ester of epoxy fatty acid 23, antimony oxide 35, blanc fixe 46, macromolecule organic calcium 34, mono laurate butanediol ester 0.5 0.7, organic silicon polyether copolymer 2.8 3.5, zinc stearate 0.3 0.5, appropriate deionized water；CABLE MATERIALS good mechanical performance of the present invention, strong shock resistance be not easy to crack, and resist cold freeze proof, economic and environment-friendly, safety durable.
Description
Technical field
The present invention relates to field of cable technology, more particularly to a kind of extraordinary freeze proof silicone rubber for cable material that resists cold.
Background technology
Silicon 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 silicon 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 silicon rubber
The gas produced during burning does not have poison, will not produce the phenomenon of drippage, and the residue after burning is silica, 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 silicon rubber so as to be widely applied to
The fields such as cable, electric wire, space flight and aviation, automobile and chemical industry.But silicon rubber has oxygen index (OI) in itself much smaller than 30, and according to
Professional standard, the material for manufacturing cable will have higher anti-flammability, in addition, silicon 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
Silicon rubber is a kind of refractory material for just receiving publicity in recent years, and which is the silicon rubber material of general flexibility in normal state
Material, after naked light calcination is run into, silicon 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 silicon 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 of fire protection flame retarding silicon rubber and photo-crosslinking silicon rubber/polyolefin composite cable material and its performance study》One
In text, author is to add mica, glass powder with low melting point and fire retardant in silicon 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 mica is most widely suited when being 40wt%, addition
Glass powder with low melting point to after silicon 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 crosslinking agent are present, profit
With ultraviolet light to MVQ（Silicon rubber）/LLDPE（LLDPE）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 mica, the performance of the glass powder with low melting point and fire retardant silicon rubber in silicon rubber system, and addition is mended
The impact of strong resin material overall mechanical properties in silicon 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 silicon 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 extraordinary freeze proof silicone rubber for cable material that resists cold
Material.
The present invention is achieved by the following technical solutions：
A kind of extraordinary freeze proof silicone rubber for cable material that resists cold, is made up of the raw material of following weight portion：MVQ silicon rubber 60-70,
Polyimides 27-33, vinyl silicone oil 4-5, light trigger benzophenone 0.1-0.2, crosslinking agent TAIC0.1-0.2, dichloride
Iron 3.6-4, ferric trichloride 6-6.8, mica 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, octyl ester of epoxy fatty acid 2-3, antimony oxide 3-5, blanc fixe 4-6, macromolecule organic calcium 3-
4th, mono laurate butanediol ester 0.5-0.7, organic silicon polyether copolymer 2.8-3.5, zinc stearate 0.3-0.5, deionized water are fitted
Amount.
A kind of extraordinary freeze proof silicone rubber for cable material that resists cold, is made up of step in detail below：
（1）Ferrous chloride and ferric trichloride are dissolved in deionized water, are placed in 50 DEG C of waters bath with thermostatic control, stirring is until solution mixes
Uniformly, add mica 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 mica deionized water；
（2）Glass powder with low melting point is added in the 11-13 times of absolute ethyl 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）Dry antimony oxide and blanc fixe are added in container, temperature are controlled for 40-50 DEG C, are added mono laurate
Butanediol ester terminates follow-up high-temperature of continuing rising to 90-110 DEG C with the rotating speed stirring 15-25min of 1600-1800r/min, stirring,
Add organic silicon polyether copolymer and zinc stearate continues stirring 20-30min, naturally cool to room temperature；
（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
It is well mixed, MVQ silicon rubber, polyimides and vinyl silicone oil is added to into banbury according to mass ratio and is kneaded, during mixing
Between be 10-20min, melting temperature is 180 DEG C, and rotating speed is 100r/min, fused mass take out after in two-roll mill slice, it
Itself and above-mentioned preliminary mixture are added to into banburying in banbury jointly again afterwards and uniformly, alternately add magnetic in two orthogonal direction
, finally add light trigger, crosslinking 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 thermal degradation after is generating silica under oxygen and hot conditions using silicon rubber
Residue layer, mica can occur " eutectic " reaction with residue silica 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 iron oxide changes
Property mica and glass powder with low melting point so as to area load iron 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 iron oxide load can promote silicon 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 silicon 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
Laurate and organic silicon polyether copolymer are respectively provided with good polar group, can preferably improve the surface property of filler, carry
High dispersiveness and compatibility in silicon rubber, greatly improves rubber cable using blanc fixe and antimony oxide compounding
Cold-resistant, freeze proof, toughness reinforcing and the performance such as oil resistant, CABLE MATERIALS good mechanical performance of the present invention, form stable, strong shock resistance,
Not easy to crack, resist cold freeze proof, economic and environment-friendly, safety durable.
Specific embodiment
A kind of extraordinary freeze proof silicone rubber for cable material that resists cold, by following weight portion（Kilogram）Raw material make：MVQ silicon
Rubber 60, polyimides 27, vinyl silicone oil 4, light trigger benzophenone 0.1, crosslinking agent TAIC0.1, ferrous chloride 3.6,
Ferric trichloride 6, mica 20, glass powder with low melting point 10, polyethylene glycol 1.6, ferrous sulfate 1.8, ammonium hydrogen carbonate 2.5, epoxidised fatty
Misery ester 2, antimony oxide 3, blanc fixe 4, macromolecule organic calcium 3, mono laurate butanediol ester 0.5, organic silicon polyether are common
Polymers 2.8, zinc stearate 0.3, appropriate deionized water.
A kind of extraordinary freeze proof silicone rubber for cable material that resists cold, is made up of step in detail below：
（1）Ferrous chloride and ferric trichloride are dissolved in deionized water, are placed in 50 DEG C of waters bath with thermostatic control, stirring is until solution mixes
Uniformly, add mica 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 mica deionized water；
（2）Glass powder with low melting point is added in the absolute ethyl 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）Dry antimony oxide and blanc fixe are added in container, temperature are controlled for 40 DEG C, are added mono laurate fourth two
Alcohol ester is terminated follow-up high-temperature of continuing rising to 90 DEG C, is added organic silicon polyether with the rotating speed stirring 15min of 1600r/min, stirring
Copolymer and zinc stearate continue stirring 20min, naturally cool to room temperature；
（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 silicon rubber, polyimides and vinyl silicone oil are added to into banbury according to mass ratio and are kneaded, mixing time is
10min, melting temperature are 180 DEG C, and rotating speed is 100r/min, fused mass take out after in two-roll mill slice, again will afterwards
During itself and above-mentioned preliminary mixture are added to banbury jointly, banburying is uniform, alternately adds magnetic field in two orthogonal direction, finally
Add light trigger, crosslinking 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 which, as a result as follows：
Tensile strength（MPa）：14；Elongation at break（%）：632；Heat ageing coefficient：0.92；Anti-flammability（UL94V）：V0；The limit
Oxygen index (OI)：31.5；Solvent resistance（Mass loss rate %）：3.3.
Claims (2)
1. a kind of extraordinary freeze proof silicone rubber for cable material that resists cold, it is characterised in that be made up of the raw material of following weight portion：
MVQ silicon rubber 60-70, polyimides 27-33, vinyl silicone oil 4-5, light trigger benzophenone 0.1-0.2, crosslinking agent
TAIC0.1-0.2, ferrous chloride 3.6-4, ferric trichloride 6-6.8, mica 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, octyl ester of epoxy fatty acid 2-3, antimony oxide 3-5, blanc fixe
4-6, macromolecule organic calcium 3-4, mono laurate butanediol ester 0.5-0.7, organic silicon polyether copolymer 2.8-3.5, zinc stearate
0.3-0.5, appropriate deionized water.
2. a kind of extraordinary freeze proof silicone rubber for cable material that resists cold according to claim 1, it is characterised in that by walking in detail below
Suddenly make：
（1）Ferrous chloride and ferric trichloride are dissolved in deionized water, are placed in 50 DEG C of waters bath with thermostatic control, stirring is until solution mixes
Uniformly, add mica 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 mica deionized water；
（2）Glass powder with low melting point is added in the 11-13 times of absolute ethyl 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）Dry antimony oxide and blanc fixe are added in container, temperature are controlled for 40-50 DEG C, are added mono laurate
Butanediol ester terminates follow-up high-temperature of continuing rising to 90-110 DEG C with the rotating speed stirring 15-25min of 1600-1800r/min, stirring,
Add organic silicon polyether copolymer and zinc stearate continues stirring 20-30min, naturally cool to room temperature；
（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
It is well mixed, MVQ silicon rubber, polyimides and vinyl silicone oil is added to into banbury according to mass ratio and is kneaded, during mixing
Between be 10-20min, melting temperature is 180 DEG C, and rotating speed is 100r/min, fused mass take out after in two-roll mill slice, it
Itself and above-mentioned preliminary mixture are added to into banburying in banbury jointly again afterwards and uniformly, alternately add magnetic in two orthogonal direction
, finally add light trigger, crosslinking 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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Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN107286396A (en) * | 2017-06-30 | 2017-10-24 | 上海蓝昊电气江苏有限公司 | A kind of super low-temperature resistant oil resistant flame retardant jacket materials and its preparation technology |
| CN107286406A (en) * | 2017-06-30 | 2017-10-24 | 上海蓝昊电气有限公司 | A kind of super low-temperature resistant cable semiconductive material |
| CN108892931A (en) * | 2018-07-11 | 2018-11-27 | 合肥尚强电气科技有限公司 | A kind of high pressure resistant cable jacking and preparation method thereof |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102838803A (en) * | 2012-08-28 | 2012-12-26 | 安徽双荣电器电缆有限公司 | Silicon rubber insulation and heat resisting control cable material and preparation method thereof |
| CN104200881A (en) * | 2014-09-03 | 2014-12-10 | 太仓苏晟电气技术科技有限公司 | Insulation compound halogen-free flame retardant wire and cable and manufacturing method thereof |
| CN105913957A (en) * | 2016-07-10 | 2016-08-31 | 李保集 | High-reliability mine cable |
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2016
- 2016-10-17 CN CN201610905631.7A patent/CN106554628A/en active Pending
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102838803A (en) * | 2012-08-28 | 2012-12-26 | 安徽双荣电器电缆有限公司 | Silicon rubber insulation and heat resisting control cable material and preparation method thereof |
| CN104200881A (en) * | 2014-09-03 | 2014-12-10 | 太仓苏晟电气技术科技有限公司 | Insulation compound halogen-free flame retardant wire and cable and manufacturing method thereof |
| CN105913957A (en) * | 2016-07-10 | 2016-08-31 | 李保集 | High-reliability mine cable |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN107286396A (en) * | 2017-06-30 | 2017-10-24 | 上海蓝昊电气江苏有限公司 | A kind of super low-temperature resistant oil resistant flame retardant jacket materials and its preparation technology |
| CN107286406A (en) * | 2017-06-30 | 2017-10-24 | 上海蓝昊电气有限公司 | A kind of super low-temperature resistant cable semiconductive material |
| CN108892931A (en) * | 2018-07-11 | 2018-11-27 | 合肥尚强电气科技有限公司 | A kind of high pressure resistant cable jacking and preparation method thereof |
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Application publication date: 20170405 |