CN105086458A - Semi-conducting silicon rubber shielding material for cables - Google Patents
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Abstract
The invention provides a semi-conducting silicon rubber shielding material for cables and a preparation method thereof. The semi-conducting silicon rubber shielding material for cables is mainly prepared from the following materials: 80 to 95 parts by weight of silicon rubber, 5 to 18 parts by weight of conductive carbon black, 25 to 38 parts by weight of white carbon black, 3 to 5 parts by weight of dicumyl peroxide, 4 to 6 parts by weight of assistant vulcanizing agent, 16 to 20 parts by weight of diphenyl silanediol, 3 to 5 parts by weight of stearic acid, 1 to 3 parts by weight of zinc oxide and 1 to 1.8 parts by weight of ferric oxide. The radiation resistance of the semi-conducting silicon rubber shielding material disclosed by the invention is good, and the semi-conducting silicon rubber shielding material has good electrical and mechanical properties; when the semi-conducting silicon rubber shielding material is used as a wire and cable shielding layer, in a radiation place, the strength retention rate of the wire and cable shielding layer can be more than 80 percent and the elongation retention rate is about 45 percent for a long time, and the wire and cable shielding layer has excellent plasticity.
Description
Technical field
The invention belongs to cable material field, relate to a kind of cable semi-conductive silicone rubber shielding material.
Background technology
At wires and cables industry, conductor shielding and insulation shielding mainly adopt semi-conductive high polymer material, are namely to add conductive filler material in macromolecule matrix material, as Shawinigan black, electrically conductive graphite powder, conductive carbon fibre etc.These two kinds shield usual in power cable is matrix with EVA.EVA is thermoplastic elastomer, and its softness, not as good as rubber, is often applied in the cable fixedly laid, and for movable type cable, EVA seems awkward because its VA contains quantitative limitation.Reason is: VA content is higher, and EVA elasticity is more good more soft, but its price is more expensive and processing characteristics is poor (because of its to temperature sensitive easy roll banding).Therefore, the conductor shielding of movable type cable and insulation shielding adopt rubber as matrix usually.
At present, wires and cables industry commonly uses rubber chlorinated polyethylene rubber (CM), ethylene-propylene rubber(EPR) (EPDM) and silicon rubber.Conductive filler material is added the semi-conductive shielding material that chlorinated polyethylene rubber is made, bring difficulty to refining glue and crowded rubber because its hardness and mooney viscosity are comparatively large.For addressing this problem, usually conductive filler material being added in the low ethylene-propylene rubber(EPR) of mooney viscosity, or adding in silicon rubber.Due to conductive filler material and ethylene-propylene rubber(EPR) price all costly, therefore production cost increases severely.From the angle of this synergy of control, some producer silicon rubber produces semi-conductive screen sizing material as matrix, and achieves good effect.
But, although the performance of current cable semi-conductive shielding material in thermotolerance and electroconductibility increases, radiation hardness aspect is still needed to carry out exploring and studying, expects to obtain the cable semi-conductive shielding material with good radiation resistance.
CN102964841A discloses a kind of rdaiation resistant cable semi-conductive silicone rubber shielding material and preparation method thereof, belongs to cable shield field of material technology.Comprise the following feed composition according to weight parts: 100 parts, silicon rubber, graphitized carbon black 20 ~ 40 parts, white carbon black 40 ~ 50 parts, dicumyl peroxide 1.0 ~ 2.5 parts, cocuring agent 2.0 ~ 3.0 parts, Diphenylsilanediol 5 ~ 15 parts, stearic acid 1.0 ~ 2.0 parts, 4 ~ 6 parts, zinc oxide and ferric oxide 2 ~ 5 parts.The silicon rubber shielding material radiation resistance of this invention is good, during as electric wire screen layer, can play its predetermined function for a long time in radiation occasion.
Along with the progress of technology, in cable material field, exploitation is needed to have the rdaiation resistant cable shielding material of excellent properties more.
Summary of the invention
For the deficiencies in the prior art, the object of the present invention is to provide a kind of cable semi-conductive silicone rubber shielding material.
For reaching this object, the present invention by the following technical solutions:
The invention provides a kind of cable semi-conductive silicone rubber shielding material, described cable semi-conductive silicone rubber shielding material prepares primarily of following raw material:
In the raw material of cable semi-conductive silicone rubber shielding material of the present invention, described silicon rubber is phenylate support silicon rubber or phenylene silicone rubber; The consumption of described silicon rubber is 80-95 weight part, such as 80 weight parts, 80.5 weight parts, 81 weight parts, 81.5 weight parts, 82 weight parts, 83 weight parts, 84 weight parts, 85 weight parts, 86 weight parts, 87 weight parts, 88 weight parts, 89 weight parts, 90 weight parts, 91 weight parts, weight part, 92 weight parts, 93 weight parts, 94 weight parts or 95 weight parts.
In the raw material of cable semi-conductive silicone rubber shielding material of the present invention, the consumption of described graphitized carbon black is 5-18 weight part, such as 5 weight parts, 6 weight parts, 7 weight parts, 8 weight parts, 9 weight parts, 10 weight parts, 11 weight parts, 12 weight parts, 13 weight parts, 14 weight parts, 15 weight parts, 16 weight parts, 17 weight parts or 18 weight parts.
In the raw material of cable semi-conductive silicone rubber shielding material of the present invention, the consumption of described white carbon black is 25-38 weight part, such as 25 weight parts, 25.5 weight parts, 26 weight parts, 27 weight parts, 28 weight parts, 29 weight parts, 30 weight parts, 31 weight parts, 32 weight parts, 33 weight parts, 34 weight parts, 35 weight parts, 36 weight parts, 37 weight parts or 38 weight parts.
In the raw material of cable semi-conductive silicone rubber shielding material of the present invention, the consumption of described dicumyl peroxide is 3-5 weight part, such as 3 weight parts, 3.1 weight parts, 3.2 weight parts, 3.3 weight parts, 3.4 weight parts, 3.5 weight parts, 3.6 weight parts, 3.7 weight parts, 3.8 weight parts, 3.9 weight parts, 4 weight parts, 4.2 weight parts, 4.4 weight parts, 4.5 weight parts, 4.7 weight parts, 4.8 weight parts, 4.9 weight parts or 5 weight parts.
In the raw material of cable semi-conductive silicone rubber shielding material of the present invention, described cocuring agent is triallylcyanurate; The consumption of described cocuring agent is 4-6 weight part, such as 4 weight parts, 4.1 weight parts, 4.3 weight parts, 4.5 weight parts, 4.7 weight parts, 4.9 weight parts, 5 weight parts, 5.2 weight parts, weight part, 5.3 weight parts, 5.5 weight parts, 5.6 weight parts, 5.7 weight parts, 5.8 weight parts, 5.9 weight parts or 6 weight parts.
In the raw material of cable semi-conductive silicone rubber shielding material of the present invention, the consumption of described Diphenylsilanediol is 16-20 weight part, such as 16 weight parts, 16.2 weight parts, 16.4 weight parts, 16.6 weight parts, 16.8 weight parts, 17 weight parts, 17.3 weight parts, 17.5 weight parts, 17.7 weight parts, 18 weight parts, 18.2 weight parts, 18.4 weight parts, 18.6 weight parts, 18.8 weight parts, 19 weight parts, 19.2 weight parts, 19.4 weight parts, 19.6 weight parts, 19.8 weight parts or 20 weight parts.
In the raw material of cable semi-conductive silicone rubber shielding material of the present invention, described stearic consumption is 3-5 weight part, such as 3 weight parts, 3.1 weight parts, 3.2 weight parts, 3.3 weight parts, 3.4 weight parts, 3.5 weight parts, 3.6 weight parts, 3.7 weight parts, 3.8 weight parts, 3.9 weight parts, 4 weight parts, 4.2 weight parts, 4.4 weight parts, 4.5 weight parts, 4.7 weight parts, 4.8 weight parts, 4.9 weight parts or 5 weight parts.
In the raw material of cable semi-conductive silicone rubber shielding material of the present invention, the consumption of described zinc oxide is 1-3 weight part, such as 1 weight part, 1.1 weight parts, 1.2 weight parts, 1.3 weight parts, 1.4 weight parts, 1.5 weight parts, 1.6 weight parts, 1.7 weight parts, 1.8 weight parts, 1.9 weight parts, 2 weight parts, 2.1 weight parts, 2.2 weight parts, 2.3 weight parts, 2.4 weight parts, 2.5 weight parts, 2.6 weight parts, 2.7 weight parts, 2.8 weight parts, 2.9 weight parts or 3 weight parts.
In the raw material of cable semi-conductive silicone rubber shielding material of the present invention, the consumption of described ferric oxide is 1-1.8 weight part, such as 1 weight part, 1.1 weight parts, 1.2 weight parts, 1.3 weight parts, 1.4 weight parts, 1.5 weight parts, 1.6 weight parts, 1.7 weight parts or 1.8 weight parts.
Moisture≤1.75% of graphitized carbon black of the present invention, ash content≤1.75%, ratio resistance is 0.35 Ω cm, and pH value is 7.4.White carbon black of the present invention is thermal silica, dioxide-containing silica>=99%, pH value 3.7 ~ 4.5, and oil-absorption(number) is 3.46 ~ 3.60cm
3/ g, specific surface area is 350 ~ 410m
2/ g.
On the other hand, the invention provides the preparation method of described cable semi-conductive silicone rubber shielding material, said method comprising the steps of:
(1) baking oven graphitized carbon black being put into 95-100 DEG C heats 1-3h;
(2) in mill, adding silicon rubber, stearic acid, zinc oxide, ferric oxide, graphitized carbon black, white carbon black, Diphenylsilanediol, triallylcyanurate and dicumyl peroxide successively carries out mixing, and dicumyl peroxide adds rear thin-pass can play glue slice for 4-5 time;
(3) film after mixing, through parking, then at room temperature carries out back mixing, and back mixing adopts mill, treats sizing material deliquescing, after smooth surface is smooth, can play glue slice;
(4) the mould sulfuration that vulcanizing press put into by the film after back mixing obtains sulfuration sheet, is described cable semi-conductive silicone rubber shielding material.
In the preparation method of cable semi-conductive silicone rubber shielding material of the present invention, the roller speed ratio of step (2) described mill is 1:1.35-1:1.4, such as 1:1.35,1:1.36,1:1.37,1:1.38,1:1.39 or 1:1.4; Preferably, the mixing temperature described in step (2) is less than 38 DEG C, such as 38 DEG C, 37 DEG C, 36 DEG C, 35 DEG C, 34 DEG C, 33 DEG C, 32 DEG C, 31 DEG C or 30 DEG C.
In the preparation method of cable semi-conductive silicone rubber shielding material of the present invention, step (3) the described storage period is 24-36 hour, such as 24 hours, 25 hours, 26 hours, 27 hours, 28 hours, 29 hours, 30 hours, 31 hours, 32 hours, 33 hours, 34 hours, 35 hours or 36 hours.
In the preparation method of cable semi-conductive silicone rubber shielding material of the present invention, the thickness of step (3) gained film is 1.5-2.0mm, such as 1.5mm, 1.6mm, 1.7mm, 1.8mm, 1.9mm or 2mm.
In the preparation method of cable semi-conductive silicone rubber shielding material of the present invention, step (4), the temperature of described sulfuration is 170-175 DEG C, such as 170 DEG C, 171 DEG C, 172 DEG C, 173 DEG C, 174 DEG C or 175 DEG C, curing time is 8-10min, such as 8min, 8.5min, 9min, 9.5min or 10min, keep cavity pressure to be not less than 3MPa, such as 3MPa, 4MPa, 5MPa, 6MPa, 7MPa, 8MPa, 9MPa, 10MPa, 11MPa or 12MPa between curing time.
Relative to prior art, the present invention has following beneficial effect:
Silicon rubber shielding material radiation resistance of the present invention is good, there is good electricity and mechanical property, during as electric wire screen layer, can make its strength retention for a long time more than 80% in radiation occasion, percent retention of elongation about 45%, and has excellent plasticity.
Embodiment
Technical scheme of the present invention is further illustrated below by embodiment.Those skilled in the art should understand, described embodiment is only help to understand the present invention, should not be considered as concrete restriction of the present invention.
Embodiment 1
The cable semi-conductive silicone rubber shielding material of the present embodiment, is prepared by following raw material:
The preparation method of above-mentioned cable semi-conductive silicone rubber shielding material is as follows:
(1) baking oven graphitized carbon black being put into 95 DEG C heats 3h;
(2) in mill (the roller speed ratio of mill is 1:1.35), adding silicon rubber, stearic acid, zinc oxide, ferric oxide, graphitized carbon black, white carbon black, Diphenylsilanediol, triallylcyanurate and dicumyl peroxide successively carries out mixing, mixing temperature is 38 DEG C, and dicumyl peroxide adds rear thin-pass can play glue slice for 4-5 time;
(3) film after mixing is through parking, and the storage period is 24 hours, then at room temperature carries out back mixing, and back mixing adopts mill, and treat sizing material deliquescing, after smooth surface is smooth, can play glue slice, the thickness of gained film is about 2mm;
(4) the mould sulfuration of vulcanizing press put into by the film after back mixing, and (temperature of sulfuration is 175 DEG C, curing time is 8min, cavity pressure is kept to be 3MPa between curing time) obtain sulfuration sheet, be described cable semi-conductive silicone rubber shielding material.
Embodiment 2
The cable semi-conductive silicone rubber shielding material of the present embodiment, is prepared by following raw material:
The preparation method of above-mentioned cable semi-conductive silicone rubber shielding material is as follows:
(1) baking oven graphitized carbon black being put into 100 DEG C heats 1h;
(2) in mill (the roller speed ratio of mill is 1:1.4), adding silicon rubber, stearic acid, zinc oxide, ferric oxide, graphitized carbon black, white carbon black, Diphenylsilanediol, triallylcyanurate and dicumyl peroxide successively carries out mixing, mixing temperature is 30 DEG C, and dicumyl peroxide adds rear thin-pass can play glue slice for 4-5 time;
(3) film after mixing is through parking, and the storage period is 30 hours, then at room temperature carries out back mixing, and back mixing adopts mill, and treat sizing material deliquescing, after smooth surface is smooth, can play glue slice, the thickness of gained film is about 1.5mm;
(4) the mould sulfuration of vulcanizing press put into by the film after back mixing, and (temperature of sulfuration is 170 DEG C, curing time is 10min, cavity pressure is kept to be 10MPa between curing time) obtain sulfuration sheet, be described cable semi-conductive silicone rubber shielding material.
Embodiment 3
The cable semi-conductive silicone rubber shielding material of the present embodiment, is prepared by following raw material:
The preparation method of above-mentioned cable semi-conductive silicone rubber shielding material is as follows:
(1) baking oven graphitized carbon black being put into 100 DEG C heats 1.5h;
(2) in mill (the roller speed ratio of mill is 1:1.38), adding silicon rubber, stearic acid, zinc oxide, ferric oxide, graphitized carbon black, white carbon black, Diphenylsilanediol, triallylcyanurate and dicumyl peroxide successively carries out mixing, mixing temperature is 35 DEG C, and dicumyl peroxide adds rear thin-pass can play glue slice for 4-5 time;
(3) film after mixing is through parking, and the storage period is 36 hours, then at room temperature carries out back mixing, and back mixing adopts mill, and treat sizing material deliquescing, after smooth surface is smooth, can play glue slice, the thickness of gained film is about 2mm;
(4) the mould sulfuration of vulcanizing press put into by the film after back mixing, and (temperature of sulfuration is 175 DEG C, curing time is 10min, cavity pressure is kept to be 8MPa between curing time) obtain sulfuration sheet, be described cable semi-conductive silicone rubber shielding material.
Embodiment 4
The cable semi-conductive silicone rubber shielding material of the present embodiment, is prepared by following raw material:
The preparation method of above-mentioned cable semi-conductive silicone rubber shielding material is as follows:
(1) baking oven graphitized carbon black being put into 95 DEG C heats 2h;
(2) in mill (the roller speed ratio of mill is 1:1.38), adding silicon rubber, stearic acid, zinc oxide, ferric oxide, graphitized carbon black, white carbon black, Diphenylsilanediol, triallylcyanurate and dicumyl peroxide successively carries out mixing, mixing temperature is 35 DEG C, and dicumyl peroxide adds rear thin-pass can play glue slice for 4-5 time;
(3) film after mixing is through parking, and the storage period is 36 hours, then at room temperature carries out back mixing, and back mixing adopts mill, and treat sizing material deliquescing, after smooth surface is smooth, can play glue slice, the thickness of gained film is about 1.5mm;
(4) the mould sulfuration of vulcanizing press put into by the film after back mixing, and (temperature of sulfuration is 170 DEG C, curing time is 8min, cavity pressure is kept to be 7MPa between curing time) obtain sulfuration sheet, be described cable semi-conductive silicone rubber shielding material.
Comparative example 1
This comparative example difference from Example 1 is that the consumption of silicon rubber in the raw material of cable semi-conductive silicone rubber shielding material is 78 weight parts, in addition, the consumption of all the other raw materials and preparation method all identical with embodiment 1 with condition.
Comparative example 2
This comparative example difference from Example 2 is that the consumption of graphitized carbon black in the raw material of cable semi-conductive silicone rubber shielding material is 4 weight parts, in addition, the consumption of all the other raw materials and preparation method all identical with embodiment 2 with condition.
Comparative example 3
This comparative example difference from Example 3 is that the consumption of white carbon black in the raw material of cable semi-conductive silicone rubber shielding material is 24 weight parts, in addition, the consumption of all the other raw materials and preparation method all identical with embodiment 3 with condition.
Comparative example 4
This comparative example difference from Example 4 is that the consumption of Diphenylsilanediol in the raw material of cable semi-conductive silicone rubber shielding material is 22 weight parts, in addition, the consumption of all the other raw materials and preparation method all identical with embodiment 4 with condition.
Comparative example 5
The cable semi-conductive silicone rubber shielding material of the present embodiment, is prepared by following raw material:
Preparation method and condition are all identical with embodiment 1.
Carry out correlated performance test to cable semi-conductive silicone rubber shielding material prepared by embodiment 1-4 and comparative example 1-5, test result as shown in Table 1 and Table 2.
The cable of the table 1 embodiment 1-4 the performance test results of semi-conductive silicone rubber shielding material
The cable of the table 2 comparative example 1-4 the performance test results of semi-conductive silicone rubber shielding material
From the result of table 1 and table 2, semi-conductive silicone rubber shielding material prepared by embodiment of the present invention 1-4 has larger tensile strength and elongation at break, and has good aging resistance, gamma-rays 5 × 10
8after roentgen's irradiation, the conservation rate of performance is higher, there is radiation resistance, and there is preferably plasticity, these performances are much better than the performance of the semi-conductive silicone rubber shielding material of comparative example 1-4, this is that the consumption of some components in the raw material due to its semi-conductive silicone rubber shielding material exceeds the framework of the present definition, and the material property causing it to prepare declines; The consumption of each component is limited in CN102964841A scope of disclosure by comparative example 5, although make its performance increase, semi-conductive silicone rubber shielding material prepared by the embodiment of the present invention still has the performance being obviously better than comparative example 5.
Therefore, the radiation resistance of semi-conductive silicone rubber shielding material of the present invention is good, has good electricity and mechanical property, during as electric wire screen layer, can make its strength retention for a long time more than 80% in radiation occasion, percent retention of elongation about 45%, and has excellent plasticity.
Applicant states, the present invention illustrates semi-conductive silicone rubber shielding material of the present invention by above-described embodiment, but the present invention is not limited to above-described embodiment, does not namely mean that the present invention must rely on above-described embodiment and could implement.Person of ordinary skill in the field should understand, any improvement in the present invention, to equivalence replacement and the interpolation of ancillary component, the concrete way choice etc. of each raw material of product of the present invention, all drops within protection scope of the present invention and open scope.
Claims (10)
1. a cable semi-conductive silicone rubber shielding material, is characterized in that, described cable semi-conductive silicone rubber shielding material prepares primarily of following raw material:
2. cable semi-conductive silicone rubber shielding material according to claim 1, is characterized in that, described silicon rubber is phenylate support silicon rubber or phenylene silicone rubber.
3. cable semi-conductive silicone rubber shielding material according to claim 1 and 2, is characterized in that, described cocuring agent is triallylcyanurate.
4. the semi-conductive silicone rubber shielding material of the cable according to any one of claim 1-3, is characterized in that, moisture≤1.75% of described graphitized carbon black, ash content≤1.75%, and ratio resistance is 0.35 Ω cm, and pH value is 7.4.
5. the semi-conductive silicone rubber shielding material of the cable according to any one of claim 1-4, is characterized in that, described white carbon black is thermal silica, dioxide-containing silica>=99%, pH value 3.7 ~ 4.5, and oil-absorption(number) is 3.46 ~ 3.60cm
3/ g, specific surface area is 350 ~ 410m
2/ g.
6. the preparation method of semi-conductive silicone rubber shielding material of the cable according to any one of claim 1-5, is characterized in that, said method comprising the steps of:
(1) baking oven graphitized carbon black being put into 95-100 DEG C heats 1-3h;
(2) in mill, adding silicon rubber, stearic acid, zinc oxide, ferric oxide, graphitized carbon black, white carbon black, Diphenylsilanediol, triallylcyanurate and dicumyl peroxide successively carries out mixing, and dicumyl peroxide adds rear thin-pass can play glue slice for 4-5 time;
(3) film after mixing, through parking, then at room temperature carries out back mixing, and back mixing adopts mill, treats sizing material deliquescing, after smooth surface is smooth, can play glue slice;
(4) the mould sulfuration that vulcanizing press put into by the film after back mixing obtains sulfuration sheet, is described cable semi-conductive silicone rubber shielding material.
7. method according to claim 6, is characterized in that, the roller speed ratio of step (2) described mill is 1:1.35-1:1.4;
Preferably, the mixing temperature described in step (2) is less than 38 DEG C.
8. the method according to claim 6 or 7, is characterized in that, step (3) the described storage period is 24-36 hour.
9. the method according to any one of claim 6-8, is characterized in that, the thickness of step (3) gained film is 1.5-2.0mm.
10. the method according to any one of claim 6-9, is characterized in that, step (4), and the temperature of described sulfuration is 170-175 DEG C, and curing time is 8-10min, keeps cavity pressure to be not less than 3MPa between curing time.
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| CN105860528A (en) * | 2016-04-21 | 2016-08-17 | 苏州市双虎科技有限公司 | Semiconducting shielding material for high-strength cable |
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| CN106084790A (en) * | 2016-08-23 | 2016-11-09 | 陈建琴 | A kind of cable fire protection flame retarding silastic material |
| CN106280471A (en) * | 2016-08-23 | 2017-01-04 | 陈建琴 | A kind of corrosion-resistant silastic material of cable |
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| CN109467934A (en) * | 2018-10-29 | 2019-03-15 | 江苏宏鹏电气科技有限公司 | A kind of anti-aging cable insulation layer formula of high temperature resistant |
| CN115160789A (en) * | 2022-08-11 | 2022-10-11 | 湖北航聚科技有限公司 | Radiation-resistant phenylene ether foamed silicone rubber and preparation method thereof |
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