CN103236309B - Preparation method of ceramifiable silicon rubber composite belt for fire-resistant cable - Google Patents

Preparation method of ceramifiable silicon rubber composite belt for fire-resistant cable Download PDF

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CN103236309B
CN103236309B CN201310137914.8A CN201310137914A CN103236309B CN 103236309 B CN103236309 B CN 103236309B CN 201310137914 A CN201310137914 A CN 201310137914A CN 103236309 B CN103236309 B CN 103236309B
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fire
preparation
composite belt
composite
porcelain siclx
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CN103236309A (en
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丁小卫
陈小丹
许家琳
唐建振
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Guangdong Andy New Material Technology Co.,Ltd.
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ANPIN ORGANIC SILICON MATERIAL Co Ltd SHENZHEN CITY
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Abstract

The invention belongs to the technical field of an insulating material for a cable, and discloses a preparation method of a ceramifiable silicon rubber composite belt for a fire-resistant cable. The composite belt comprises a glass cloth reinforcing layer and a silicon rubber layer, wherein the silicon rubber layer is prepared from a ceramifiable silicon rubber composition which comprises organosilicon rubber compound and composite ceramic powder; and the weight ratio of the organosilicon rubber compound to the composite ceramic powder is 1:1-1.2. The preparation method comprises the following steps: preparing high-strength organosilicon rubber compound; preparing composite ceramic powder; performing silicone-acrylate emulsion treatment of glass cloth; and calendering the composite belt. The ceramifiable silicon rubber composite belt for the fire-resistant cable prepared by the method has extremely high strength and good flexibility and can be used for manufacturing the fire-resistant cable in place of a mica tape; after a cable lapped by using the ceramifiable silicon rubber composite belt is ablated for 180 minutes in flame of 650-950 DEG C, the circuit can still work normally; and the method is easy to operate, has high yield and can realize batch production.

Description

Preparation method that can porcelain SiClx rubber composite belt for fire-resisting cable
Technical field
The present invention relates to the preparation method of insulating material for a kind of cable, especially a kind ofly for fire-resisting cable, can form in porcelainization under flame condition the preparation method of the lapped insulation material of skelteon.
Background technology
In recent years, China's public place fire incident took place frequently, and according to interrelated data, showed, since entering 21 century, China is total to approximately 90.9 ten thousand of breaking out of fires, dead 10059 people, approximately 60.3 hundred million yuan of direct economic losses, wherein fire incident quantity in public place has accounted for the more than 50% of national fire incident total amount.During breaking out of fire accident in public places, cable safe and smooth most important to fire prevention fire fighting, can not only win valuable rescue time to greatest extent, can also greatly reduce personnel's injures and deaths and property loss.Fire-resisting cable refers to the fire resistance with regulation, can guarantee that circuit continues stable operation a period of time under flame condition, and electric power system and whistle control system are normally worked under flame condition, and the loss that fire is caused drops to bottom line.At present, domestic and international fire-resisting cable mainly contains the fire-resisting cable of magnesium oxide mineral insulated fireproof cable and Mica tape inorganic insulation.Though mineral insulated cable has good fire resistance, its manufacturing process is complicated, production cost is high, factory length is limited, and cable is stone cannot be crooked, joint is complicated, difficulty of construction is very high, is difficult to extensive use.Although Mica tape fire-resisting cable work technique is simple, factory length is unrestricted, shortcoming of mica tape ubiquity, after high-temp combustion, the mechanical strength of mica tape significantly reduces, become fragile, be subject to after strenuous vibration easily powder of detached, cause fire-resistant poor effect.And easy dry linting while rubbing because of mica tape, cause a large amount of dust in wrapped scene to bring threat to operating personnel's health.There is in recent years scientific research personnel's exploratory development ceramic silicon rubber insulating flame-resistant cable, but because of in cables manufacturing process, need special mixing, extrude and vulcanizing equipment, complex process, and be difficult to average out between isolation layer intensity and fire resistance, ceramic degree is difficult to the water-fast fire test by fire-resisting cable.
Summary of the invention
The problem existing in order to solve above-mentioned prior art, the invention provides a kind of preparation method of lapped insulation material, the silicon rubber composite band of preparing by the method can replace mica tape for the around-packing technology of cable, the fire-resisting cable of preparation 3 hours energy holding circuits of ablation under 950 ℃ of flame conditions are unimpeded.
The technical solution used in the present invention is: preparation method that can porcelain SiClx rubber composite belt for a kind of fire-resisting cable, described fire-resisting cable is with comprising glass cloth enhancement layer and silastic-layer by porcelain SiClx rubber composite belt, described silastic-layer is by making by porcelain SiClx rubber composition, describedly can comprise organic silicon compounded rubber stock and composite ceramic by porcelain SiClx rubber composition, the weight ratio of described organosilicon elastomeric compound and composite ceramic is 1:1-1.2, described organosilicon elastomeric compound comprises that contents of ethylene is the ethenyl blocking methyl ethylene silicon raw rubber of 0.2%-0.4%, contents of ethylene is the methyl ethylene silicon raw rubber of 0.05%-0.07%, contents of ethylene is the methyl ethylene silicon raw rubber of 0.4%-0.6%, hydrogen content is containing hydrogen silicone oil and the gas-phase silica of 0.05%-0.15%, described composite ceramic comprises carborundum, aluminium oxide, zirconia, boron oxide and imvite, described preparation method comprises the steps:
A, ethenyl blocking methyl ethylene silicon raw rubber and methyl ethylene silicon raw rubber, containing hydrogen silicone oil and part gas-phase silica are mediated in kneader, and then minute 2-4 time residue gas-phase silica is added in kneader, wherein the each addition of gas-phase silica be take basic equivalent as good, all mixing heats after agglomerating to 85 ℃-95 ℃ continues mixing 2-3 hour, then be warming up to 145 ℃-155 ℃, pumping vacuum and mixing 0.5-1 hour, takes out the cooling organosilicon elastomeric compound that obtains of nature;
B, add high-speed mixer to stir load weighted each ceramic powder, then in grinding in ball grinder 0.5-1.5 hour composite ceramic;
C, get high strength organosilicon elastomeric compound, part composite ceramic is mediated in kneader, and then minute 2-4 time residue composite ceramic is added in kneader, wherein the each addition of composite ceramic be take basic equivalent as good, all mixing heats after agglomerating to 65-75 ℃ continues mixing 2-3 hour, then be warming up to 135-145 ℃, vacuumize and continue mixing 0.5-1 hour, taking-up is naturally cooling, for several times, adding vulcanizing agent mixing 0.5-1 hour to obtain can porcelain SiClx rubber composition for the thin-pass of cutting into slices in mill;
D, Silicone acrylic emulsion is mixed with to the dilution that solid content is 3%-10%, in the mode of dip-coating, brushing or spraying, processes glass cloth, at the temperature of 70-90 ℃, dry;
E, can porcelain SiClx rubber composition and the glass cloth processed through Silicone acrylic emulsion compound by calendering technology, then through baking sulfuration 10-20min at 115-125 ℃, finally cut into and need width to obtain fire-resisting cable with can porcelain SiClx rubber composite belt.
Preferably, described organosilicon elastomeric compound be take weight portion and is comprised: 100 parts of the ethenyl blocking methyl ethylene silicon raw rubbers that contents of ethylene is 0.2%-0.4%, contents of ethylene is methyl ethylene silicon raw rubber 200-250 part of 0.05%-0.07%, contents of ethylene is methyl ethylene silicon raw rubber 150-200 part of 0.4%-0.6%, hydrogen content is containing hydrogen silicone oil 20-30 part of 0.05%-0.15%, gas-phase silica 300-360 part;
Preferably, described composite ceramic comprises in weight portion: 100 parts, carborundum, aluminium oxide 28-38 part, zirconia 25-33 part, boron oxide 14-20 part, imvite 62-72 part.
Preferably, the weight ratio of described organosilicon elastomeric compound and composite ceramic is 1:1.1; Described organosilicon elastomeric compound be take weight portion and is comprised: 100 parts of the ethenyl blocking methyl ethylene silicon raw rubbers that contents of ethylene is 0.2%-0.4%, contents of ethylene is 221 parts of the methyl ethylene silicon raw rubbers of 0.05%-0.07%, contents of ethylene is 179 parts of the methyl ethylene silicon raw rubbers of 0.4%-0.6%, hydrogen content is 25 parts of the containing hydrogen silicone oils of 0.05%-0.15%, 330 parts of gas-phase silicas; Described composite ceramic comprises in weight portion: 100 parts, carborundum, 33 parts, aluminium oxide, 29 parts of zirconias, 17 parts of boron oxides, 67 parts of imvites.
Preferably, in described step D, the silicone content of Silicone acrylic emulsion is 3%-15%; Better, described Silicone acrylic emulsion silicone content is 8%.Wherein silicone content is the mass percent of silicon in solid part.
Preferably, described fire-resisting cable is respectively single or multiple lift with glass cloth enhancement layer and silastic-layer that can porcelain SiClx rubber composite belt
The technique effect that the present invention is useful: fire-resisting cable prepared by the inventive method, with having very high intensity and good pliability by porcelain SiClx rubber composite belt, can directly replace mica tape for fire-resisting cable manufacture, and can not produce dust pollution in wrapped process; With its wrapped cable in 650-950 ℃ of flame, ablation 180 minutes, circuit still can normally be worked, and after ablation, forms ceramic-like rigid shell, shell has good electrical property and mechanical strength, highly vibrations and water pouring situation under circuit still can normally work; The inventive method operation is row easily, and rate of finished products is high, can realize mass production.
Embodiment
Of the present invention can porcelain SiClx rubber composite belt, be by glass cloth and high-intensity can porcelain SiClx rubber composition compound, make the wrapped material of insulation, concrete preparation process is as follows:
A, the ethenyl blocking methyl ethylene silicon raw rubber of different contents of ethylene and methyl ethylene silicon raw rubber, containing hydrogen silicone oil and part gas-phase silica are mediated in kneader, and then a minute several adds residue gas-phase silica in kneader, all mixing heats after agglomerating to 85 ℃-95 ℃ continues mixing 2-3 hour, then be warming up to 145 ℃-155 ℃, vacuumize (vacuum degree 0.08-0.09Mpa) mixing 0.5-1 hour.Take out the cooling high strength organosilicon elastomeric compound that obtains of nature.Guarantee the intensity of composite band, make it reach wrapped requirement continuously in cables manufacturing process, the hot strength of elastomeric compound itself, tearing strength and the follow-up ceramic powder adding dispersion and fitness is therein key factor.The preferred weight proportion of each composition of elastomeric compound of the present invention is that 100 parts of contents of ethylene are the ethenyl blocking methyl ethylene silicon raw rubber of 0.2%-0.4% (quality): 200-250 part contents of ethylene is the methyl ethylene silicon raw rubber of 0.05%-0.07% (quality): 150-200 part contents of ethylene is the methyl ethylene silicon raw rubber of 0.4%-0.6% (quality): 20-30 part hydrogen content is the containing hydrogen silicone oil of 0.05%-0.15% (quality): 300-360 part gas-phase silica; The molecular weight of ethenyl blocking methyl ethylene silicon raw rubber and methyl ethylene silicon raw rubber be take 60-80 ten thousand as good, and Silicon Containing Hydrogen oil viscosity be take 50-1000 mPas as good.In formula, also can add a small amount of hydroxy silicon oil further to improve the hot strength of elastomeric compound.In mixing process, gas-phase silica average mark several (general 3-5 time) evenly adds, and has guaranteed its dispersed and reinforcing effect in silicon raw rubber.
B, add high-speed mixer to stir load weighted each ceramic powder, then in grinding in ball grinder 0.5-1.5 hour composite ceramic.For composite band, the porcelain degree under flame condition, the hardness after porcelain, compactness, resistance to water washout characteristics and vibration resistance are most important in the selection of ceramic powder, and the preferred weight proportion of composite ceramic of the present invention is 100 parts of carborundum: 28-38 part aluminium oxide: 25-33 part zirconia: 14-20 part boron oxide: the imvite of 62-72 part; For further improving compactness and the vibration resistance after composite band porcelain, also can add appropriate glass dust.
C, the composite ceramic of getting high strength organosilicon elastomeric compound, part milled are mediated in kneader, and then a minute several (being advisable for 2-4 time) adds residue composite ceramic in kneader, all mixing heats after agglomerating to 65-75 ℃ continues mixing 2-3 hour, then be warming up to 135-145 ℃, vacuumize (vacuum degree 0.08-0.09Mpa) and continue mixing 0.5-1 hour, taking-up is naturally cooling, the thin-pass of cutting into slices in mill is (general 3-5 time) for several times, and adding vulcanizing agent mixing 0.5-1 hour to obtain can porcelain SiClx rubber composition.While kneading, composite ceramic divides evenly to add for several times by average magnitude and is more conducive to its abundant dispersion in elastomeric compound, can improve intensity and the toughness of final composite band.Vulcanizing agent selects 2,5-dimethyl-2,5-bis(t-butylperoxy) hexane, peroxidating two-(2,4-dichloro-benzoyl), two (4-toluyl), dibenzoyl peroxides of peroxidating, peroxidized t-butyl perbenzoate, 1,1-bis(t-butylperoxy)-3,3,5-trimethyl-cyclohexane, 1, one or several in 1-bis(t-butylperoxy) cyclohexane, add that to measure convention amount just passable.
D, Silicone acrylic emulsion is mixed with to the dilution that solid content is 3%-10% (quality), in the mode of dip-coating, brushing or spraying, processes glass cloth, at the temperature of 70-90 ℃, dry.The silicone content of Silicone acrylic emulsion be take 3%-15% (quality) as good, and the silicone content of evidence the best is 8%, and certain silicone content has improved hydrophobicity, resistance to water, electric insulating quality and the ageing-resistant performance of processing glass cloth.With Silicone acrylic emulsion, process hot strength and the tearing strength that glass cloth has further improved composite band.
E, can porcelain SiClx rubber composition and the glass cloth processed through Silicone acrylic emulsion compound by calendering technology, compound tense silastic-layer and glass cloth enhancement layer can be complex as double-decker or alternatively laminated is sandwich construction, after lamination is good, through baking sulfuration 10-20min at 115-125 ℃, finally cut into need width to obtain can porcelain SiClx rubber composite belt.
example 1
the preparation of high strength organosilicon elastomeric compound
Taking contents of ethylene is the ethenyl blocking methyl ethylene silicon raw rubber 120g that 0.28% (quality) molecular weight is 700,000, contents of ethylene is the methyl vinyl silicone rubber 265g that 0.06% (quality) molecular weight is 800,000, contents of ethylene is the methyl vinyl silicone rubber 215g that 0.50% (quality) molecular weight is 600,000, hydrogen content is the containing hydrogen silicone oil 30g that 0.1% (quality) viscosity is 100mPas, gas-phase silica 96g is in kneader, mediate and divide again three times after agglomerating to add 100g gas-phase silica at every turn, all mix agglomerating after, be warming up to 90 ℃ and continue to mediate 2.5h, then be warming up to 150 ℃ and vacuumize (vacuum degree 0.08-0.09MPa) mixing 0.5 hour, take out the cooling high strength organosilicon elastomeric compound that obtains of nature.
In high strength organosilicon elastomeric compound, add vulcanizing agent to make sheet the rear test of sulfuration of 2mm thickness, hot strength is 11MPa, and elongation at break is 500%, and tearing strength is 63kN/m, and hardness is shoreA 56.
example 2
the preparation of composite ceramic
Take carborundum 412g, aluminium oxide 136g, zirconia 120g, boron oxide 70g, nano imvite 276g is placed in high-speed mixer and stirs 0.5h, mixes, and then, in grinding in ball grinder 1h, obtains composite ceramic.
example 3
the processing of glass cloth
Taking silicone content is that 8% (quality), solid content are the Silicone acrylic emulsion 110g of 45% (quality), with the dilution of 890g water, with the Silicone acrylic emulsion having diluted, in dip-coating mode, processes glass cloth, then 80 ℃ of baking 8min in drying tunnel.
example 4
preparation that can porcelain SiClx rubber composite belt for fire-resisting cable
Take the high strength organosilicon elastomeric compound 900g that embodiment 1 makes, the composite ceramic 240g of embodiment 2 preparations, in kneader, mediate and divide again the composite ceramic that at every turn adds 250g embodiment 2 preparations for three times after agglomerating, all mix agglomerating after, be warming up to 70 ℃ and continue to mediate 2.5h, then be warming up to 140 ℃ and vacuumize (vacuum degree 0.08-0.09MPa) mixing 0.5 hour, taking-up is naturally cooling, after section in mill thin-pass 3-5 time, add two (4-toluyl) 20g of peroxidating, mixing 0.5h, obtaining can porcelain SiClx rubber composition.
Can be placed on calender by porcelain SiClx rubber composition, by calendering technology, can roll on the glass cloth of processing in embodiment 3 by porcelain SiClx rubber composition one side, through 120 ℃ of drying tunnels baking sulfuration 15min, obtain fire-resisting cable that one side glass cloth strengthens with can porcelain SiClx rubber composite belt.
Gained can porcelain SiClx rubber composite belt electrical strength be more than or equal to 25kV/mm, specific insulation is more than or equal to 2 * 10 11Ω cm 3, hot strength is more than or equal to 60 N/10mm, reaches the around-packing technology requirement in cables manufacturing process.According to British Standard BS 6387:1994, carry out fire resistance test test, energising voltage 450/750V, under 950 ℃ of flame conditions, ablation is 180 minutes, keeps circuit complete and can normal power-up, and without pernicious gas, discharges in combustion process.
Above content is in conjunction with concrete preferred implementation further description made for the present invention, can not assert that specific embodiment of the invention is confined to these explanations.For general technical staff of the technical field of the invention, without departing from the inventive concept of the premise, can also make some simple deduction or replace, all should be considered as belonging to protection scope of the present invention.

Claims (5)

1. preparation method that can porcelain SiClx rubber composite belt for a fire-resisting cable, described fire-resisting cable is with comprising glass cloth enhancement layer and silastic-layer by porcelain SiClx rubber composite belt, described silastic-layer is by making by porcelain SiClx rubber composition, describedly can comprise organic silicon compounded rubber stock and composite ceramic by porcelain SiClx rubber composition, the weight ratio of described organosilicon elastomeric compound and composite ceramic is 1:(1-1.2), described organosilicon elastomeric compound comprises that contents of ethylene is the ethenyl blocking methyl ethylene silicon raw rubber of 0.2%-0.4%, contents of ethylene is the methyl ethylene silicon raw rubber of 0.05%-0.07%, contents of ethylene is the methyl ethylene silicon raw rubber of 0.5%-0.6%, hydrogen content is containing hydrogen silicone oil and the gas-phase silica of 0.05%-0.15%, described composite ceramic comprises carborundum, aluminium oxide, zirconia, boron oxide and imvite, described preparation method comprises the steps:
A, ethenyl blocking methyl ethylene silicon raw rubber and methyl ethylene silicon raw rubber, containing hydrogen silicone oil and part gas-phase silica are mediated in kneader, and then minute 2-4 time residue gas-phase silica is added in kneader, all mixing heats after agglomerating to 85 ℃-95 ℃ continues mixing 2-3 hour, then be warming up to 145 ℃-155 ℃, pumping vacuum and mixing 0.5-1 hour, takes out the cooling organosilicon elastomeric compound that obtains of nature;
B, add high-speed mixer to stir load weighted each ceramic powder, then in grinding in ball grinder 0.5-1.5 hour composite ceramic;
C, get high strength organosilicon elastomeric compound, part composite ceramic is mediated in kneader, and then minute 2-4 time residue composite ceramic is added in kneader, all mixing heats after agglomerating to 65-75 ℃ continues mixing 2-3 hour, then be warming up to 135-145 ℃, vacuumize and continue mixing 0.5-1 hour, taking-up is naturally cooling, and for several times, adding vulcanizing agent mixing 0.5-1 hour to obtain can porcelain SiClx rubber composition for the thin-pass of cutting into slices in mill;
D, Silicone acrylic emulsion is mixed with to the dilution that solid content is 3%-10%, in the mode of dip-coating, brushing or spraying, processes glass cloth, at the temperature of 70-90 ℃, dry;
E, can porcelain SiClx rubber composition and the glass cloth processed through Silicone acrylic emulsion compound by calendering technology, then through baking sulfuration 10-20min at 115-125 ℃, finally cut into and need width to obtain fire-resisting cable with can porcelain SiClx rubber composite belt.
2. preparation method that can porcelain SiClx rubber composite belt for fire-resisting cable according to claim 1, is characterized in that: described organosilicon elastomeric compound comprises in weight portion:
3. preparation method that can porcelain SiClx rubber composite belt for fire-resisting cable according to claim 1 and 2, is characterized in that: described composite ceramic comprises in weight portion:
4. preparation method that can porcelain SiClx rubber composite belt for fire-resisting cable according to claim 3, is characterized in that: the weight ratio of described organosilicon elastomeric compound and composite ceramic is 1:1.1;
Described organosilicon elastomeric compound comprises in weight portion:
Described composite ceramic comprises in weight portion:
5. preparation method that can porcelain SiClx rubber composite belt for fire-resisting cable according to claim 1 and 2, is characterized in that: in described step D, the silicone content of Silicone acrylic emulsion is 3%-15%.
6. preparation method that can porcelain SiClx rubber composite belt for fire-resisting cable according to claim 1 and 2, is characterized in that: described fire-resisting cable is respectively single or multiple lift with glass cloth enhancement layer and silastic-layer that can porcelain SiClx rubber composite belt.
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CN104629375B (en) * 2015-02-11 2017-05-10 深圳市安品有机硅材料有限公司 Ceramizable fireproof fire-resistant silicone rubber
CN104650597B (en) * 2015-02-11 2017-12-29 深圳市安品有机硅材料有限公司 Can ceramic fireproof silicon rubber preparation method
CN107057365B (en) * 2016-12-29 2020-07-28 深圳市安品有机硅材料有限公司 Flame-retardant ceramifiable silicon rubber for fire-resistant cable and preparation method thereof
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