Summary of the invention
In order to solve the problem that above-mentioned prior art exists, the invention provides a kind of preparation method of water-fast fiery ceramic silicon rubber composite belt, water-fast fiery ceramic silicon rubber composite belt with this method preparation can replace mica tape to be used for the around-packing technology of cable, the fire-resisting cable of preparation is through 650 ± 40 ℃ flame ablation and shower water acting in conjunction certain hour, still can holding circuit unimpeded, and test by vibration resistance.
The technical solution used in the present invention is:
A kind of preparation method of water-fast fiery ceramic silicon rubber composite belt, described water-fast fiery ceramic silicon rubber composite belt comprises glass cloth enhancement layer and silastic-layer, described silastic-layer is made by water-fast fiery ceramic silicon rubber composition, described water-fast fiery ceramic silicon rubber composition comprises organic silicon compounded rubber stock and composite ceramic, and described organosilicon elastomeric compound comprises ethenyl blocking methyl ethylene silicon raw rubber, methyl ethylene silicon raw rubber, containing hydrogen silicone oil and gas-phase silica; Described composite ceramic comprises ceramic idiosome material and ceramic glaze body material, and described ceramic idiosome material is counted by weight and comprised:
Described ceramic glaze body material comprises silica, potassium oxide, aluminium oxide, calcium oxide, zinc oxide and magnesia;
Described preparation method comprises the steps:
A, ethenyl blocking methyl ethylene silicon raw rubber and methyl ethylene silicon raw rubber, containing hydrogen silicone oil are mixed the back mediate with the part gas-phase silica, and then divide 2-4 adding to remain gas-phase silica, all mixing heats after agglomerating to 85 ℃-95 ℃ continued mixing 2-3 hour, be warming up to 145 ℃-155 ℃ then, pumping vacuum and mixing 0.5-1 hour, take out nature cool off the organosilicon elastomeric compound; Wherein the each addition of gas-phase silica is good with basic equivalent;
B, the ceramic idiosome material in the load weighted composite ceramic and ceramic glaze body material are mixed, are warming up to 120-130 ℃ and mix, grinds 0.5-1.5 hour must composite ceramic;
C, get organosilicon elastomeric compound, part composite ceramic and mix the back and mediate, divide then and add the residue composite ceramic for 2-4 time, heat after whole mixings are agglomerating to 65-75 ℃ of continuation mixing 2-3 hour, be warming up to 135-145 ℃ then, vacuumize and continued mixing 0.5-1 hour, taking-up is cooled off naturally, carries out thin-pass after the section for several times, adds vulcanizing agent and obtains water-fast fiery ceramic silicon rubber composition in mixing 0.5-1 hour; Wherein the each addition of composite ceramic is good with basic equivalent;
D, Silicone acrylic emulsion is mixed with the dilution that solid content is 3%-10%, handles glass cloth in the mode of dip-coating, brushing or spraying, under 70-90 ℃ temperature, dry;
E, with water-fast fiery ceramic silicon rubber composition with roll compoundly through the glass cloth that Silicone acrylic emulsion is handled, in 115-125 ℃ of baking sulfuration 10-20min down, cut and namely get water-fast fiery ceramic silicon rubber composite belt then.
The water-fast fiery ceramic silicon rubber composite belt of the present invention's preparation, consumption and composition by ceramic idiosome material and ceramic glaze body material in the adjustment composite ceramic, realization is to the adjusting of composite ceramic melting process and final porcelain rerum natura energy, wherein, ceramic glaze body material can be filled the space in the porcelain thing after high-temperature fusion, compactness and the intensity of porcelain thing are improved, thereby improve water-fast fire and anti-vibration performance after the water-fast fiery ceramic silicon rubber composite belt porcelainization, the while adjusting process, improve the dispersiveness of powder, make composite band have higher intensity and toughness, satisfy the performance requirement of fire-resisting cable opposing connection cladding crossed belt.
Preferably, described ceramic glaze body material is counted by weight and is comprised:
Preferably, in the described composite ceramic, the weight ratio of ceramic idiosome material and ceramic glaze body material is 1:(0.65~0.7).
Among the preparation method of the present invention the organosilicon elastomeric compound there is not particular restriction; composite ceramic is uniformly dispersed in the organosilicon elastomeric compound and gets final product; the composite band of composite ceramic and the preparation of organosilicon elastomeric compound is in the high temperature ablation process; silica dioxide granule takes place to decompose and produce in the organosilicon elastomeric compound; porcelain formation protective layer takes place with composite ceramic; realize water-and fire-proof; and in order to satisfy the requirement of wrapped cable, the pliability that composition that can be by adjusting the organosilicon elastomeric compound and ratio are regulated final composite band and intensity etc.
Preferably, described organosilicon elastomeric compound comprises in weight portion:
Preferably, the weight ratio of described organosilicon elastomeric compound and composite ceramic is (1.5~1): 1.Preferred, the weight ratio of described organosilicon elastomeric compound and composite ceramic is 1.2:1.
Further preferably, the contents of ethylene of ethenyl blocking methyl ethylene silicon raw rubber is 0.2%-0.4%, described methyl ethylene silicon raw rubber is that contents of ethylene is the methyl ethylene silicon raw rubber of 0.05%-0.07% and the mixture of the methyl ethylene silicon raw rubber that contents of ethylene is 0.4%-0.6%, and the hydrogen content of containing hydrogen silicone oil is 0.05%-0.15% in the described organosilicon elastomeric compound.
Based on this, preferred, described organosilicon elastomeric compound comprises in weight portion: 100 parts of ethenyl blocking methyl ethylene silicon raw rubbers, 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%, 25 parts of containing hydrogen silicone oils, 330 parts of gas-phase silicas.
Preferably, the silicone content of Silicone acrylic emulsion is 3%-15% among the described step D; Better, described Silicone acrylic emulsion silicone content is 8%.Wherein silicone content is the mass percent of silicon in solid part.
Preferably, glass cloth enhancement layer and the silastic-layer of described water-fast fiery ceramic silicon rubber composite belt are respectively single or multiple lift.
Beneficial technical effects of the present invention: method operation of the present invention is row easily, the yield rate height can be realized mass production, prepares water-fast fiery ceramic silicon rubber composite belt and has high intensity and good pliability, can replace mica tape and be used for the fire-resisting cable manufacturing, wrapped process does not produce dust pollution; Comprise composite ceramic in the water-fast fiery ceramic silicon rubber composite belt, comprise ceramic idiosome material and ceramic glaze body material, fusion takes place to fill the space of porcelain thing in ceramic glaze body material in the porcelain process, thereby improve compactness and the intensity of porcelain thing, the ceramic package that the ablated back of composite band is formed has excellent mechanical intensity, with its wrapped cable at high temperature ablation, applying still can operate as normal under the situation of shower water and high-intensity oscillation.
The specific embodiment
Water-fast fiery ceramic silicon rubber composite belt of the present invention is that glass cloth and high-intensity water-fast fiery ceramic silicon rubber composition is compound, makes the wrapped material of insulation, and concrete preparation process is preferably as follows:
A, ethenyl blocking methyl ethylene silicon raw rubber and methyl ethylene silicon raw rubber, containing hydrogen silicone oil and the part gas-phase silica of different contents of ethylene are mediated in kneader, and then divide several will remain in the gas-phase silica adding kneader, all mixing heats after agglomerating to 85 ℃-95 ℃ continued mixing 2-3 hour, be warming up to 145 ℃-155 ℃ then, vacuumized (vacuum 0.08-0.09Mpa) mixing 0.5-1 hour.Take out the nature cooling and namely get high strength organosilicon elastomeric compound.Guarantee the intensity of composite band, make it reach wrapped requirement continuously in the cables manufacturing process, the ceramic powder of the hot strength of elastomeric compound itself, tearing strength and follow-up adding dispersion and fitness therein is 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 is good with 60-80 ten thousand, and the viscosity of containing hydrogen silicone oil is good with 50-1000mPas.Also can add a spot of hydroxy silicon oil in the prescription with the hot strength of further raising elastomeric compound.(general 3-5 time) the evenly adding for several times of gas-phase silica average mark has guaranteed its even dispersion and reinforcing effect in silicon raw rubber in the mixing process.
Composite ceramic in B, the embodiment of the invention comprises ceramic idiosome material and ceramic glaze body material, described ceramic idiosome material comprises the following component of meter by weight: 00 part of silica 1, boron oxide 42-47 part, zirconia 25-30 part, aluminium oxide 16-21 part, strontium oxide strontia 2-5 part; Described ceramic glaze body material preferably includes following component according to the mass fraction: 00 part of silica 1, potassium oxide 22-25 part, aluminium oxide 53-58 part, calcium oxide 40-45 part, zinc oxide 6-8 part, magnesia 4-7 part.In composite ceramic, the weight ratio of ceramic idiosome material and ceramic glaze body material is 1:(0.65~0.7).
Wherein, partial oxide in the ceramic glaze body material can add by the raw mineral materials that contains described oxide, to reduce cost, for example silica adds by quartz sand, magnesia adds by talcum, and potassium oxide adds by potassic feldspar, and aluminium oxide is by kaolin adding etc., the described oxide consumption in back that converts satisfies described proportioning and gets final product, and specifically can adopt following preferred feed way:
Get 6-8 part ZnO, 40-45 part CaO adds 13-22 part talcum powder and (contains MgO 31.8%, SiO
263.2%, be mass fraction), be equivalent to add 4-7 part MgO, 8-14 part SiO
2Add 133-142 part potassic feldspar and (contain SiO
264.7%, Al
2O
318.4%, K
2O 16.9%, is mass fraction), be equivalent to add 22-24 part K
2O, 86-92 part SiO
2, 24-26 part Al
2O
3, and the SiO in talcum and the potassic feldspar
2Total umber is 100 parts, adds Al again
2O
3, make its umber reach 53-58 part, add again behind the described potassic feldspar pulverize, obtain ceramic glaze body material after the mixing, the small amount of crystalline water that contains in the described mineral can decompose to be removed, little to the material property influence.
Load weighted ceramic idiosome material and ceramic glaze body material are added high-speed mixer be warming up to 120-130 ℃ and under the emptying condition, mix, the small amount of crystalline water of introducing in the ceramic glaze body material is decomposed to be removed, then in grinding in ball grinder 0.5-1.5 hour, sieve, preferably get the composite ceramic that particle diameter is 10-30 μ m.The selection of ceramic powder is most important in the porcelain degree under the flame condition, hardness, compactness, anti-water washout characteristics and vibration resistance after the porcelainization for composite band.
C, get high strength organosilicon elastomeric compound, the part composite ceramic is mediated in kneader, and then divide for several times (2-4 time be advisable) will remain in the composite ceramic adding kneader, heat after whole mixings are agglomerating to 65-75 ℃ of continuation mixing 2-3 hour, be warming up to 135-145 ℃ then, vacuumizing (vacuum 0.08-0.09Mpa) continued mixing 0.5-1 hour, taking-up is cooled off naturally, the thin-pass of cutting into slices in mill is (general 3-5 time) for several times, and the adding vulcanizing agent obtained water-fast fiery ceramic silicon rubber composition in mixing 0.5-1 hour.Composite ceramic divides for several times evenly adding more to be conducive to its abundant dispersion in elastomeric compound by average magnitude when kneading, and can improve intensity and the toughness of final composite band.Vulcanizing agent selects 2 for use, 5-dimethyl-2,5-bis(t-butylperoxy) hexane, peroxidating two-(2, the 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, in the 1-bis(t-butylperoxy) cyclohexane one or several, it is just passable that convention amount is measured in adding.
D, Silicone acrylic emulsion is mixed with the dilution that solid content is 3%-10% (quality), handles glass cloth in the mode of dip-coating, brushing or spraying, under 70-90 ℃ temperature, dry.The silicone content of Silicone acrylic emulsion is good with 3%-15% (quality), 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 handling glass cloth.Handle hot strength and the tearing strength that glass cloth has further improved composite band with Silicone acrylic emulsion.
E, the glass cloth of handling with water-fast fiery ceramic silicon rubber composition with through Silicone acrylic emulsion are compound by calendering technology, compound tense silastic-layer and glass cloth enhancement layer can compoundly be that double-decker or alternatively laminated are sandwich construction, after lamination is good, toast sulfuration 10-20min under 115-125 ℃, cutting at last needs width namely to obtain water-fast fiery ceramic silicon rubber composite belt.
Example 1
The preparation of high strength organosilicon elastomeric compound
Taking by weighing contents of ethylene is that 0.28% (quality) molecular weight is 700,000 ethenyl blocking methyl ethylene silicon raw rubber 120g, contents of ethylene is that 0.06% (quality) molecular weight is 800,000 methyl vinyl silicone rubber 265g, contents of ethylene is that 0.50% (quality) molecular weight is 600,000 methyl vinyl silicone rubber 215g, hydrogen content is that 0.1% (quality) viscosity is the containing hydrogen silicone oil 30g of 100mPas, gas-phase silica 96g is in kneader, mediate and divide the each 100g of adding gas-phase silica after agglomerating again three times, after whole mixings are agglomerating, be warming up to 90 ℃ and continue to mediate 2.5h, be warming up to 150 ℃ then and vacuumized (vacuum 0.08-0.09MPa) mixing 0.5 hour, take out the nature cooling and namely get high strength organosilicon elastomeric compound.
Add vulcanizing agent and make sheet and the test of sulfuration back of 2mm thickness in high strength organosilicon elastomeric compound, hot strength is 11MPa, and elongation at break is 500%, and tearing strength is 63kN/m, and hardness is shoreA56.
Example 2
The preparation of composite ceramic
Composite ceramic in the present embodiment comprises ceramic idiosome material and ceramic glaze body material, takes by weighing silica 1 00g, boron oxide 45g, and zirconia 30g, aluminium oxide 20g and strontium oxide strontia 3g mix obtaining 198g pottery idiosome material.
Take by weighing 8g ZnO, add 42g CaO, add the 20g talcum powder and (contain MgO 31.8%, SiO
263.2%, be mass fraction), be equivalent to add 6g MgO and 13g SiO
2Add the 134g potassic feldspar and (contain SiO
264.7%, Al
2O
318.4%, K
2O 16.9%, is mass fraction), be equivalent to add 23g K
2O, 87g SiO
2, 24g Al
2O
3, the SiO in talcum powder and the potassic feldspar then
2Gross mass is 100g, adds 31g Al again
2O
3, make Al
2O
3Gross mass reach 55g, add again behind the described potassic feldspar pulverize, obtain 235g ceramic glaze body material after mixing, wherein the gross mass of oxide is 234g.
Getting 185g pottery idiosome material and 123g ceramic glaze body material (wherein the gross mass of oxide is 122.5g) places high-speed mixer to be warming up to 120 ℃ and mix and stir 1h under the emptying condition, to remove a spot of crystallization water, then in grinding in ball grinder 1h, sieve, obtain the composite ceramic that particle diameter is 10-30 μ m.
Example 3
The processing of glass cloth
Taking by weighing silicone content is that 8% (quality), solid content are the Silicone acrylic emulsion 110g of 45% (quality), with the dilution of 890g water, handles glass cloth with the Silicone acrylic emulsion that dilution is good in the dip-coating mode, then 80 ℃ of baking 8min in drying tunnel.
Example 4
The preparation of water-fast fiery ceramic silicon rubber composite belt
Take by weighing the high strength organosilicon elastomeric compound 900g that embodiment 1 makes, the composite ceramic 188g of embodiment 2 preparations, in kneader, mediate and divide three the each 188g of adding embodiment the composite ceramic of 2 preparations after agglomerating again, after whole mixings are agglomerating, be warming up to 70 ℃ and continue to mediate 2.5h, be warming up to 140 ℃ then and vacuumized (vacuum 0.08-0.09MPa) mixing 0.5 hour, taking-up is cooled off naturally, section back thin-pass 3-5 time in mill, add two (4-toluyl) 20g of peroxidating, mixing 0.5h namely gets water-fast fiery ceramic silicon rubber composition.
Water-fast fiery ceramic silicon rubber composition is placed on the calender, by calendering technology water-fast fiery ceramic silicon rubber composition single face is rolled on the glass cloth that embodiment 3 handled, through 120 ℃ of baking sulfurations of drying tunnel 15min, namely obtain the water-fast fiery ceramic silicon rubber composite belt that the single face glass cloth strengthens, the thickness of this composite band is 0.35mm.
Adopt this area universal testing method that the water-fast fiery ceramic silicon rubber composite belt of gained is carried out performance test, record the electrical strength of water-fast fiery ceramic silicon rubber composite belt more than or equal to 25kV/mm, specific insulation is more than or equal to 2 * 10
11Ω cm
3, hot strength reaches the around-packing technology requirement in the cables manufacturing process more than or equal to 60N/10mm.
Adopt the wrapped preparation fire-resisting cable of described water-fast fiery ceramic silicon rubber composite belt, concrete grammar is: on wrapped machine, towards copper conductor one side, making it is 38mm at area of section with the glass cloth of water-fast fiery ceramic silicon rubber composite belt one side
2Copper conductor on carry out 1/2 lap wound, behind 3 layers of the lap wounds, obtain flame retardant coating, extrude at flame retardant coating then and form the thick polyvinyl resin insulating barrier of 4.0mm, obtain insulated wire cores, it is stranded to get 3 strand insulation cores, extrudes external sheath layer again, obtains fire-resisting cable.
Carry out fire-resistant, water-fast fire and vibration resistance test according to the fire-resisting cable of British Standard BS6387:1994, particularly, in the test, fire-resisting cable energising voltage is 450/750V, in fire-resistant test, fire-resisting cable ablation 3h under 950 ± 40 ℃ of flame conditions still keeps the complete and energy normal power-up of circuit, satisfy C level refractory standard, and no pernicious gas discharges in the combustion process; In water-fast fire test, the fire-resisting cable of energising carried out near fire-resisting cable, add 0.25L/m behind 650 ± 40 ℃ the flame ablation 15min
2The shower water 15min of s, namely cable is through 650 ± 40 ℃ flame calcination and shower water acting in conjunction 15min, still can keep circuit complete and can normal power-up, by water-fast fire test; In the vibration resistance test, the fire-resisting cable of energising is standing 750 ± 40 ℃ flame ablation and is applying mechanical shock vibration 15min, and the complete nothing of circuit is damaged, and the energy normal power-up, meets Y level vibration resistance standard.
Above content be in conjunction with concrete preferred embodiment to further describing that the present invention does, can not assert that concrete enforcement of the present invention is confined to these explanations.For the 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.