CN103666249A - Single-component room temperature vulcanization type ceramic fireproof silicon rubber coating material as well as preparation method and application thereof - Google Patents
Single-component room temperature vulcanization type ceramic fireproof silicon rubber coating material as well as preparation method and application thereof Download PDFInfo
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Abstract
The invention discloses a single-component room temperature vulcanization type ceramic fireproof silicon rubber coating material as well as a preparation method and an application thereof. The coating material comprises the following components in parts by weight: 100 parts of alpha, omega-dihydroxy polydimethylsiloxane, 10-20 parts of fumed silica, 5-10 parts of aluminum oxide, 0.5-2 parts of a sintering additive, 5-15 parts of a cross-linking agent, 0.1-0.5 part of a catalyst, 20-60 parts of a plasticizer, 0.5-1.5 parts of a tackifier and 0.1-0.5 part of a surface treating agent. The coating material does not need to be extruded at high temperature, can be vulcanized at room temperature after being applied, has the characteristics of a dense ceramic body, a stable structure, stable fireproof performance, good insulation performance and the like, and is applied to electric wires and cables; the thickness of a conventional silicon rubber fireproof layer is greatly reduced.
Description
Technical field
The present invention relates to electric wire polymeric material field, specifically refer to a kind of single-component room temperature vulcanized type fire-resisting ceramic silicone rubber coating material, preparation method and application thereof.
Background technology
Along with taking place frequently of fire failure, people constantly deepen electric wire fire hazard understanding, and relevant department is also more and more higher to the requirement of the performances such as electric wire fire protection flame retarding.Features such as spreading fast, the difficulty of putting out a fire to save life and property because cable fire has, produce secondary harm, time of recovery is long can be brought huge loss to national economy and the people's lives and properties.Therefore people have proposed harsher operational conditions to the fire performance of electric wire, safe reliability.As fire prevention, explosion-proof, overload capacity is strong, long service life, under Fire Conditions, Fire lift, fire pump need keep the normal operation in certain hour, cable has low-smoke low-halogen low toxicity characteristic after burning, even reaches the particular requirements such as smokeless halogen-free is nontoxic.Cable fire-proof measure is to reduce the important means that ignition of cable prolongs combustion, crucial relying mainly on prevention, and according to this thinking, all kinds of flame resistant cables, fireproof cable are used widely.
At present, in this field, adopted is both at home and abroad flame resistant cable and the magnesium oxide mineral insulated fireproof cable of Mica tape more.The flame resistant cable of Mica tape, during cable fire, the hardening of mica sintering can continue to play the effect of insulation, thereby reach fire-resistant effect, but, no matter be that synthetic mica tape, gold mica tape, white clouds master tape or other mica tapes all have following main drawback: (1) mica water-absorbent is strong, after water suction, easily lost efficacy; (2) working method of mica tape is to utilize tackiness agent to paste mica powder, therefore harder, and in wrapped and processing and use procedure subsequently, mica powder very easily peels off, as long as exist, peels off the function of having lost insulation, does not reach service requirements; Also be difficult for wrapped smooth, even subsides, tight, easily wrinkling, particularly small cross-section flexible conductor difficulty of processing is larger simultaneously; (3) after meeting fire burning, organic materials macromolecular material is burnt after mistake, can cause cable internal structure loosening, cause the fragmentation of mica insulation layer to come off, the effect of especially all kinds of vibrations, thereby forfeiture insulating property, cannot continue to remain on the function of supplying power in flame, so its application is subject to certain limitation.
Magnesium oxide mineral insulated fireproof cable is to adopt the copper of high conductivity to make conductor, and inorganics magnesium oxide insulate, and seamless copper pipe is made sheath, and the modern architecture wiring cable being made through special process and special industry (metallurgy, chemical industry, oil etc.) are used cable.Although mineral insulated cable has high use temperature, after catching fire, keep long power supply capacity also fine, it is complicated that but its manufacturing process of this cable falls behind, conductor adopts real core copper bar, and sheath is drawing copper tubes, therefore, cable is rigidity, flexibility is poor, is difficult to bending, processes, lays difficulty larger.Because adopting drawing copper tubes, oversheath forms, limited by plant area, drum length of cable is limited, during use, need increase intermediate head, contact resistance increases, the efficiency that has reduced transmission of electricity, has increased power transmission failure hidden danger point, is difficult to meet the related specifications requirements such as < < Code for design of cables of electric works > >.In addition, magnesium oxide mineral insulated cable is processed external diameter and is limited, and is difficult to adopt split conductor cable.
Silicon rubber has good electrical insulating property, is widely used as insulation, sheath etc. in cable, and its molecular backbone chain alternately consists of silicon and Sauerstoffatom, becomes SiO after burning
2, there is certain fire-resistant effect.The disclosed a kind of Silastic fire resistance cable of Chinese patent CN2586226 adopts conventional silastic material as flame retardant coating and insulation layer; Chinese patent CN101673586A discloses a kind of bus with flame resistant cable and for cable, has extruded the silastic mixture of silastic-layer, silastic mixture flame retardant coating adopt single-component room temperature vulcanized silicon and silicone oil by volume the ratio of 9:2 after mixing, extrude and make.Although become SiO after burning
2there is fire performance, but burning after SiO
2present powdery, there is no sticking power, easily come off, therefore fire-resistant effect still has larger distance.
Chinese patent CN 101503573 B disclose a kind of refractory insulation material for cable of Gong extruding, raw material comprises following component and content weight part: 100 parts of methyl vinyl silicone rubbers, 0.15～2 part of coupling agent, 30～40 parts of thermal silicas, 40～50 parts of ultra tiny mica powders, 2～4 parts of constitution controllers, 0.5～2 part of vulcanizing agent.Although overcome the shortcoming of Mica tape, but mica is lamination shape or book shape crystal formation, even ultramicrofine mica powder, remains the peelable structure of a kind of sheet, between this structure and rubber, consistency is poor, be difficult to disperse, the performance that can reduce insulating material, mica powder is a kind of natural mineral raw simultaneously, complex shape, unstable properties, also can cause the unstable of insulating material performance.
Chinese patent CN 101781463 B disclose a kind of fire-resistant silicon rubber and preparation method thereof and cable, and fire-resistant silicon rubber is mainly prepared by following weight part raw material: silicon rubber 100, containing hydrogen silicone oil 0.1-3, hydroxy silicon oil 2-15, gas-phase silica 10-30, silicon powder 10-30, nano imvite 20-50, silicon carbide 10-30, vulcanizing agent 1, compare with silicon rubber by the platinic compound < 50ppm of platinum amount.This material is a kind of fire retardant glue and difficult combustion glue, nano imvite is a kind of inorganic combustion inhibitor, gas-phase silica, silicon powder, silicon carbide etc. also have flame retardant effect, in the process that is added in burning by fire retardant, the material generating can make flame extinguish gradually, thereby reach fire-retardant effect, improved the activation energy in silastic material thermooxidative degradation simultaneously, make the combustion degradation of material become difficult.But, after being burnt, this material still can become powder, there is no sticking power, easily come off, and do not have fire-fighting, fp effect.
The 35th the 1st phase of volume of < < world rubber industry > >, beam Zhe, youngest brother Peng, Zhao Yuan " exploratory study of new ceramics fire-resistant silicon rubber ", a kind of fire-resisting ceramic silicone rubber is disclosed in the document, in methyl vinyl silicone rubber, to add white carbon black, silicone oil, Vitrified powder and other auxiliary agents, this fire-resisting ceramic silicone rubber is to utilize its organosilicon chain combination silicon oxide family, 500 ℃ of flame temperatures, start to occur catalyticcombustion crust, " porcelain " becomes the very little thermal insulation of specific heat capacity to keep off fiery solid, utilize this solid to complete fire-resistant mission.Single " ceramic " structural instability of utilizing its sintering of organosilicon chain combination silicon oxide family to form, the ceramic silicon rubber after burning is more crisp, easily cracks, and forms conductive channel, causes the unstable of fire performance.
At some special occasions, as engine, rail transit train, offshore oil platform large ship, precision equipment etc., belong to high fire hazard area, must guarantee to have fire performance.Meanwhile, these occasion mounting and installation narrow spaces, have strict restriction to the scantlings of the structure of cable, and prior art can not meet these requirements simultaneously.Adopt the processing mode of aforesaid way, outside the deficiency of mentioning, also all can not meet the restriction of the scantlings of the structure of cable is required: the flame resistant cable that adopts Mica tape, guarantee to have fire performance mica and must reach certain thickness, and after wrapped, must have sheath, around-packing technology and sheath processing have all increased the outside diameter of cable; Adopt the flame resistant cable of magnesium oxide mineral insulation, inorganics magnesium oxide insulate, the thickness of seamless copper pipe is all large and be rigidity, cannot be practical at small space, and the silicon rubber extruding, ceramic silicon rubber, smooth, round and smooth for what guarantee to extrude, also need the larger thickness of extruding.
Summary of the invention
The present invention overcomes the shortcoming that prior art exists, a kind of single-component room temperature vulcanized type fire-resisting ceramic silicone rubber coating material is provided, this coating material does not need high temperature to extrude, at room temperature sulfuration after can applying, significantly reduce the thickness of traditional silicon rubber flame retardant coating, there is the features such as ceramic body densification, Stability Analysis of Structures, fire performance are stable, good insulation preformance simultaneously.
In addition the present invention also provides the preparation method of this silastic material and the application in electric wire.
To achieve these goals, a kind of single-component room temperature vulcanized type fire-resisting ceramic silicone rubber coating material of the present invention, it mainly comprises following component and parts by weight: α, 100 parts of alpha, omega-dihydroxy polydimethyl siloxanes, thermal silica 10-20 part, aluminum oxide 5-10 part, sinter additives 0.5-2 part, linking agent 5-15 part, catalyzer 0.1-0.5 part, softening agent 20-60 part, tackifier 0.5-1.5 part, surface treatment agent 0.1-0.5 part.
Preferably, described thermal silica is vapor phase process ultra-fine white carbon black (fumed nano silicon-dioxide).
Preferably, described aluminum oxide is electric filler aluminum oxide or used in electronic ceramic aluminum oxide, the used in electronic ceramic aluminum oxide that described used in electronic ceramic aluminum oxide better selects aluminium sesquioxide content to be greater than 99.7%, more preferably ultra-fine alumina (nano aluminium oxide).
Preferably, described sinter additives is Fe
2o
3, MnO
2, Cr
2o
3or TiO
2, that the most frequently used is Fe
2o
3.
Preferably, described linking agent is trifunctional organoalkoxysilane.
Preferably, described catalyzer is two organotins two (beta-diketo-esters).
Preferably, described softening agent is α, ω-dimethoxy polydimethylsiloxane.
Preferably, described tackifier are cyano alkoxy silane.
Preferably, described surface treatment agent is the conventional surface treatment agent of silicon rubber or silane coupling agent, its silane coupling agent is vinyltrimethoxy silane (A171), vinyltriethoxysilane (A151), γ mercaptopropyitrimethoxy silane (A189) or γ-(1,2-encircles propoxy-) propyl trimethoxy silicane (A187).
A preparation method for single-component room temperature vulcanized type fire-resisting ceramic silicone rubber coating material described above, it mainly comprises the following steps:
1) first in thermal silica, aluminum oxide, sinter additives, by umber, add respectively surface treatment agent, then in kneader, process respectively, handle rear stand-by;
2) by α, thermal silica after alpha, omega-dihydroxy polydimethyl siloxane, surface treatment, the aluminum oxide after surface treatment, the sinter additives after surface treatment, softening agent and tackifier are mixed into after paste or thick liquid on rubber mixing machine or three-roller, then carry out drying treatment;
3) after cooling under drying regime, add linking agent, catalyzer, after fully mixing under the condition of moisture in isolated air, be encapsulated in airtight container and store;
4) while using, take out from container, the steam in ingress of air, solidifies and can obtain this coating material under room temperature.
The application of single-component room temperature vulcanized type fire-resisting ceramic silicone rubber coating material of the present invention in electric wire, is specially: single-component room temperature vulcanized type fire-resisting ceramic silicone rubber coating material can be used as insulation layer, sheath or restrictive coating; Also can be at internal layer or the single-component room temperature vulcanized type fire-resisting ceramic silicone rubber coating material of outer coating of insulation layer, sheath, restrictive coating.
Compared with prior art, tool of the present invention has the following advantages:
1, easy to use: when curing, not absorb heat, not heat release, solidify post-shrinkage ratio little.Cementability to institute's contact material is good, corrosion-free.To the not restriction of the scantlings of the structure of cable, can mounting and installation in narrow space occasion.This coating material does not need high temperature to extrude, at room temperature sulfuration after can applying,
2, within the scope of-60 ~ 200 ℃, can keep for a long time elasticity, the fundamental characteristics that possesses at normal temperatures silicon rubber, as soft, nontoxic, tasteless, high-low temperature resistant, resistance to ozone ageing, weather-proof aging, good electrical insulation capability and good processing characteristics etc., electric wire still possesses the characteristic of silicon rubber under normal conditions.
While 3, burning, can not produce toxic gas and smog; can be by fire-resistant test; at 400 ℃, ignite; under flame ablation; the common sintering of white carbon black, aluminum oxide, sinter additives makes silicon rubber form ceramic protective layer; ceramic body Stability Analysis of Structures; strong adhesion; hard, difficult drop-off, compactness is good; thereby what be difficult for to form passage plays isolated flame, fp effect; burn after 2h reaching as high as under 1100 ℃ of flames, 1000 volts of voltages of sustainable conduction and can not being short-circuited have still guaranteed the unimpeded of electric power, communication under fire condition.
4, aluminum oxide, white carbon black, sinter additives carry out surface treatment, and consistency is good, and the amplitude that physical and mechanical properties declines when increasing consumption is little.
Embodiment
Embodiment 1:
A single-component room temperature vulcanized type fire-resisting ceramic silicone rubber coating material, it mainly comprises following component and mass fraction:
α, 100 parts of alpha, omega-dihydroxy polydimethyl siloxanes
20 parts of vapor phase process ultra-fine white carbon blacks
10 parts of ultra-fine aluminas
Fe
2o
32 parts
15 parts of trifunctional organoalkoxysilanes
Two (beta-diketo-esters) 0.5 part of two organotins
α, 60 parts of ω-dimethoxy polydimethylsiloxanes
1.5 parts, cyano alkoxy silane
0.5 part of vinyltrimethoxy silane (A171).
A single-component room temperature vulcanized type fire-resisting ceramic silicone rubber coating material preparation method described above, mainly comprises the following steps:
(1) first at vapor phase process ultra-fine white carbon black, ultra-fine alumina, Fe
2o
3in by umber, add respectively vinyltrimethoxy silane, then in kneader, stir respectively after 10 minutes, stand-by;
(2) again by α, the vapor phase process ultra-fine white carbon black after alpha, omega-dihydroxy polydimethyl siloxane, surface treatment, the ultra-fine alumina after surface treatment, the Fe after surface treatment
2o
3, α, ω-dimethoxy polydimethylsiloxane, cyano alkoxy silane are mixed into after paste or thick liquid on rubber mixing machine or three-roller, then carry out drying treatment;
(3) after cooling under drying regime, add trifunctional organoalkoxysilane, two organotins two (beta-diketo-ester), after fully mixing under the condition of moisture in isolated air, be encapsulated in airtight container and store;
(4) while using, take out from container, the steam in ingress of air, solidifies and can obtain single-component room temperature vulcanized type fire-resisting ceramic silicone rubber coating material of the present invention under room temperature.
This material is applied in electric wire, below for preparing the step of electric wire, cable:
1) the single-component room temperature vulcanized type fire-resisting ceramic silicone rubber coating material obtaining in above-mentioned steps (4) is applied to processing, obtain core, cable core;
2) the coating core, the cable core that step 1) are obtained spray, dry, and obtain single-component room temperature vulcanized type fire-resisting ceramic silicone rubber coated wire, cable.
Embodiment 2
A single-component room temperature vulcanized type fire-resisting ceramic silicone rubber coating material, it comprises following component and mass fraction:
α, 100 parts of alpha, omega-dihydroxy polydimethyl siloxanes
10 parts of thermal silicas
5 parts, electric filler aluminum oxide
MnO
20.5 part
5 parts of trifunctional organoalkoxysilanes
Two (beta-diketo-esters) 0.1 part of two organotins
α, 20 parts of ω-dimethoxy polydimethylsiloxanes
0.5 part, cyano alkoxy silane
0.1 part of vinyltriethoxysilane (A151).
A single-component room temperature vulcanized type fire-resisting ceramic silicone rubber coating material preparation method described above, mainly comprises the following steps:
(1) first at thermal silica, electric filler aluminum oxide, MnO
2in by umber, add respectively vinyltriethoxysilane (A151), then in kneader, stir respectively after 15 minutes, stand-by;
(2) again by α, the MnO after the thermal silica after alpha, omega-dihydroxy polydimethyl siloxane, surface treatment, the electric filler aluminum oxide after surface treatment, surface treatment
2, α, ω-dimethoxy polydimethylsiloxane and cyano alkoxy silane are mixed into after paste or thick liquid on rubber mixing machine or three-roller, then carry out drying treatment;
(3) after cooling under drying regime, add trifunctional organoalkoxysilane, two organotins two (beta-diketo-ester), after fully mixing under the condition of moisture in isolated air, be encapsulated in airtight container and store;
(4) while using, take out from container, the steam in ingress of air, solidifies and can obtain single-component room temperature vulcanized type fire-resisting ceramic silicone rubber coating material of the present invention under room temperature.
This material is applied in electric wire, below for preparing the step of electric wire, cable:
1) the single-component room temperature vulcanized type fire-resisting ceramic silicone rubber coating material obtaining in above-mentioned steps (4) is applied to processing, obtain core, cable core;
2) the coating core, the cable core that step 1) are obtained spray, dry, and obtain the single-component room temperature vulcanized type fire-resisting ceramic silicone rubber of the present invention coated wire, cable.
Embodiment 3
A single-component room temperature vulcanized type fire-resisting ceramic silicone rubber coating material, it mainly comprises following component and mass fraction:
α, 100 parts of alpha, omega-dihydroxy polydimethyl siloxanes
15 parts of vapor phase process ultra-fine white carbon blacks
7 parts, used in electronic ceramic aluminum oxide (aluminium sesquioxide content is greater than 99.7%)
Cr
2o
31.2 part
10 parts of trifunctional organoalkoxysilanes
Two (beta-diketo-esters) 0.3 part of two organotins
α, 40 parts of ω-dimethoxy polydimethylsiloxanes
1 part, cyano alkoxy silane
0.3 part of γ mercaptopropyitrimethoxy silane (A189).
A preparation method for single-component room temperature vulcanized type fire-resisting ceramic silicone rubber coating material described above, mainly comprises the following steps:
(1) the used in electronic ceramic aluminum oxide and the Cr that first at vapor phase process ultra-fine white carbon black, aluminium sesquioxide content, are greater than 99.7%
2o
3in by umber, add respectively γ mercaptopropyitrimethoxy silane (A189), then in kneader, stir respectively after 10 minutes, stand-by;
(2) again by α, the Cr after the vapor phase process ultra-fine white carbon black after alpha, omega-dihydroxy polydimethyl siloxane, surface treatment, the used in electronic ceramic aluminum oxide after surface treatment (aluminium sesquioxide content is greater than 99.7%), surface treatment
2o
3, α, ω-dimethoxy polydimethylsiloxane and cyano alkoxy silane are mixed into after paste or thick liquid on rubber mixing machine or three-roller, then carry out drying treatment;
(3) after cooling under drying regime, add trifunctional organoalkoxysilane, two organotins two (beta-diketo-ester), after fully mixing under the condition of moisture in isolated air, be encapsulated in airtight container and store.
(4) while using, take out from container, the steam in ingress of air, solidifies and can obtain single-component room temperature vulcanized type fire-resisting ceramic silicone rubber coating material of the present invention under room temperature.
This material is applied in electric wire, below for preparing the step of electric wire, cable:
1) the single-component room temperature vulcanized type fire-resisting ceramic silicone rubber coating material obtaining in above-mentioned steps (4) is applied to processing, obtain core, cable core;
2) the coating core, the cable core that step 1) are obtained spray, dry, and obtain the single-component room temperature vulcanized type fire-resisting ceramic silicone rubber of the present invention coated wire, cable.
Embodiment 4
A single-component room temperature vulcanized type fire-resisting ceramic silicone rubber coating material, it mainly comprises following component and mass fraction:
α, 100 parts of alpha, omega-dihydroxy polydimethyl siloxanes
12 parts of vapor phase process ultra-fine white carbon blacks
6 parts of ultra-fine aluminas
TiO
20.8 part
12 parts of trifunctional organoalkoxysilanes
Two (beta-diketo-esters) 0.4 part of two organotins
α, 30 parts of ω-dimethoxy polydimethylsiloxanes
1.2 parts, cyano alkoxy silane
γ-0.2 part of (1,2-encircles propoxy-) propyl trimethoxy silicane (A187).
A preparation method for single-component room temperature vulcanized type fire-resisting ceramic silicone rubber coating material described above, mainly comprises the following steps:
(1) first at vapor phase process ultra-fine white carbon black, ultra-fine alumina and TiO
2in by umber, add respectively vinyltrimethoxy silane, then in kneader, stir respectively after 10 minutes stand-by;
(2) again by α, the vapor phase process ultra-fine white carbon black after alpha, omega-dihydroxy polydimethyl siloxane, surface treatment, the ultra-fine alumina after surface treatment, the TiO after surface treatment
2, α, ω-dimethoxy polydimethylsiloxane and cyano alkoxy silane are mixed into after paste or thick liquid on rubber mixing machine or three-roller, then carry out drying treatment;
(3) after cooling under drying regime, add trifunctional organoalkoxysilane, two organotins two (beta-diketo-ester), after fully mixing under the condition of moisture in isolated air, be encapsulated in airtight container and store;
(4) while using, take out from container, the steam in ingress of air, solidifies and can obtain single-component room temperature vulcanized type fire-resisting ceramic silicone rubber coating material of the present invention under room temperature.
This material is applied in electric wire, below for preparing the step of electric wire, cable:
1) the single-component room temperature vulcanized type fire-resisting ceramic silicone rubber coating material obtaining in above-mentioned steps (4) is applied to processing, obtain core, cable core;
2) the coating core, the cable core that step 1) are obtained spray, dry, and obtain the single-component room temperature vulcanized type fire-resisting ceramic silicone rubber of the present invention coated wire, cable.
Embodiment 5
A single-component room temperature vulcanized type fire-resisting ceramic silicone rubber coating material, it mainly comprises following component and mass fraction:
α, 100 parts of alpha, omega-dihydroxy polydimethyl siloxanes
18 parts of vapor phase process ultra-fine white carbon blacks
6 parts of ultra-fine aluminas
Fe
2o
31.6 part
7 parts of trifunctional organoalkoxysilanes
Two (beta-diketo-esters) 0.2 part of two organotins
α, 50 parts of ω-dimethoxy polydimethylsiloxanes
0.6 part, cyano alkoxy silane
0.4 part of vinyltrimethoxy silane (A171).
A preparation method for single-component room temperature vulcanized type fire-resisting ceramic silicone rubber coating material described above, mainly comprises the following steps:
(1) first at vapor phase process ultra-fine white carbon black, ultra-fine alumina, Fe
2o
3in by umber, add respectively vinyltrimethoxy silane, then in kneader, stir respectively after 10 minutes, stand-by;
(2) again by α, the vapor phase process ultra-fine white carbon black after alpha, omega-dihydroxy polydimethyl siloxane, surface treatment, the ultra-fine alumina after surface treatment, the Fe after surface treatment
2o
3, α, ω-dimethoxy polydimethylsiloxane, cyano alkoxy silane are mixed into after paste or thick liquid on rubber mixing machine or three-roller, then carry out drying treatment;
(3) after cooling under drying regime, add trifunctional organoalkoxysilane, two organotins two (beta-diketo-ester), after fully mixing under the condition of moisture in isolated air, be encapsulated in airtight container and store;
(4) while using, take out from container, the steam in ingress of air, solidifies and can obtain single-component room temperature vulcanized type fire-resisting ceramic silicone rubber coating material of the present invention under room temperature.
This material is applied in electric wire, below for preparing the step of electric wire, cable:
1) the single-component room temperature vulcanized type fire-resisting ceramic silicone rubber coating material obtaining in above-mentioned steps (4) is applied to processing, obtain core, cable core;
2) the coating core, the cable core that step 1) are obtained spray, dry, and obtain the single-component room temperature vulcanized type fire-resisting ceramic silicone rubber of the present invention coated wire, cable.
In the present invention:
Described α, alpha, omega-dihydroxy polydimethyl siloxane is the main base glue using in single-component room temperature vulcanized silicone rubber products, is conventionally called 107 glue for short.The size of 107 glue molar masss directly impact is with elastomeric performance.Generally be chosen for (1-10) * 104g/mol, use the large and 107 little epoxy glues of molar mass of molar mass to make base glue, can guarantee the mobility of epoxy glue, the elastomerics intensity after simultaneously curing greatly improves.Meanwhile, control low molecule organo-siloxane content, to avoid the abrasion in high-temperature closed system; Major measure is the D3-D20 strictly removing in base glue, even D3-D40.
Described thermal silica is one of the most frequently used strengthening agent of silicon rubber, can play reinforcement, (so-called thixotropy is exactly to solidify front blend glue stuff easily deformable flowing under external force to improve dielectric properties and thixotropic property, once external force disappears, can stop again deformation and mobile performance) vapor phase process ultra-fine white carbon black (fumed nano silicon-dioxide), because its particle diameter is less, therefore specific surface area is large, surface adsorption power is strong, surface can be large, active strong, chemical purity is high, dispersing property is good, thermal resistance, the aspects such as resistance have excellent performance, stability and reinforcement are superior.Through surface active, the thermal silica of hydrophobic treatment, less on the impact of compound viscosity, reinforcing effect is good.
Described aluminum oxide, claims again aluminium sesquioxide, is commonly referred to " alumina ", is commonly called as alumina.Thermotolerance is strong, good moldability, and crystalline phase is stable, hardness is high, good stability of the dimension, and silicon rubber is had to reinforcing effect equally.After sintering, have good mechanical property, insulating property, can improve compactness, intensity, the toughness of sintered ceramic body, improve the performances such as consistency and elasticity modulus of material.Select electric filler aluminum oxide or used in electronic ceramic aluminum oxide, the used in electronic ceramic aluminum oxide of better selecting aluminium sesquioxide content to be greater than 99.7%, its stable chemical performance, has good sintering character.Better select ultra-fine alumina (nano aluminium oxide), particle dispersion is good, has more excellent physics-chem characteristic, and high dielectric strength, the low electrical loss factor and high resistivity can be provided.
White carbon black and aluminum oxide have synergy, generate binary, ternary or the more complicated low fused matter of liquid phase with other additives, these liquid phases have wetting action to solid phase, the surface tension of phase interface make solid phase particles mutually near and fill pore, thereby acceleration of sintering.
Described sinter additives is the oxide compound that appraises at the current rate, and has Fe
2o
3/ MnO
2/ Cr
2o
3/ TiO
2deng, the most frequently used is ferric oxide.Because its lattice parameter and aluminum oxide approach, conventionally can form sosoloid with aluminum oxide.Due to the effect of appraising at the current rate, make alumina ceramics produce defect, activation lattice, acceleration of sintering, adds the TiO of 0.5-1%
2just can make the sintering temperature of alumina ceramics reduce 100-200 ℃.This type oxide add the thermal aging property that also can greatly improve silicon rubber.Meanwhile, silicon rubber is also had to weak strengthening action, can, to regulate the hardness of silicon rubber, improve the processing performance of sizing material and the oil resistance of cross-linked rubber and solvent resistance.
Described surface treatment agent, also claims coupling agent, can improve bonding force between supporting material or filler and polymer interface.Surface treatment agent of the present invention is the conventional surface treatment agent of silicon rubber, better selects silane coupling agent, as vinyltrimethoxy silane (A171), vinyltriethoxysilane (A151) etc.; First white carbon black, aluminum oxide, sinter additives are carried out to surface treatment, after processing, the physical strength of sizing material is higher, and mixing good with back mixing processing performance, the transparency of cross-linked rubber also improves.
Described white carbon black, aluminum oxide, sinter additives, for improving the physical strength of sizing material, the processing performance after mixing and back mixing, the transparency of cross-linked rubber, can first with surface treatment agent, process, surface treatment agent is same as the prior art, also claim coupling agent, can improve bonding force between supporting material or filler and polymer interface.Surface treatment agent of the present invention is the conventional surface treatment agent of silicon rubber, better selects silane coupling agent, as vinyltrimethoxy silane (A171), vinyltriethoxysilane (A151) etc.
Described linking agent, same as the prior art; α, the Si-OH end group of alpha, omega-dihydroxy polydimethyl siloxane reacts, and makes sizing material become elastomerics; Trifunctional organoalkoxysilane, containing hydrolysable group, is the linking agent of Dealcoholized one-component room temperature vulcanized silicone rubber, and general formula is RSi(OR1)
3; That the most frequently used is MeSi(OMe)
3, MeSi(OEt)
3.
Described catalyzer, same as the prior art, play katalysis, accelerated reaction; Organotin, is the compound of tin, as: stannous octoate, dibutyl tin laurate etc. are the conventional catalyzer of single group room temperature vulcanized silicone rubber; Two organotins two (beta-diketo-ester), can not produce corrosion to metals such as copper, aluminium, there is no the stink of general organo-tin compound yet, can improve package stability, the nondiscoloration of sizing material, and can improve cementability.
Linking agent under the initiation of catalyzer with the Si-OH base generation condensation reaction of 107 glue, thereby cause the curing cross-linked of single-component room temperature vulcanized silicon rubber, form three-dimensional net structure, elastomer-forming.Curing cross-linking reaction at room temperature can occur.Dealcoholizing-type linking agent is to copper conductor material non-corrosiveness.
Described softening agent, same as the prior art, effect is the hardness of silicon rubber after reducing compound viscosity, increase mobility and reducing sulfuration; а, ω-dimethoxy polydimethylsiloxane is the softening agent that dealcoholizing-type double component room temperature vulcanization silicon rubber is conventional, in sulfidation, will participate in crosslinking reaction, wants to regulate preferably modulus, should select the а of viscosity (25 ℃) 5 ~ 80MPa, ω-dimethoxy polydimethylsiloxane.
Described tackifier are the tackifier that single-component room temperature vulcanized silicon rubber is conventional, improve the mobility of sizing material, increase viscosity and the cohesiveness that adds man-hour, make it be unlikely to lose from adhesive portion bit stream because viscosity is too low, or because viscosity is high, are difficult for coating construction.Cyano alkoxy silane, when having viscosifying action, can also seal Si-OH base on white carbon black surface, and the tendency of condensation reaction occurs suppressing between white carbon black and white carbon black, between white carbon black and base glue, makes the extruded velocity of sizing material stable; Meanwhile, the NC base on white carbon black surface can form hydrogen bond, improves the thixotropy of sizing material.
The single-component room temperature vulcanized type fire-resisting ceramic silicone rubber of the present invention coating material can require to add according to cable the pigment of appropriate amount.When using in cable, also can use the single-component room temperature vulcanized type fire-resisting ceramic silicone rubber of true qualities coating material, in coating material, drag colour band to set, these are all same as the prior art.
The single-component room temperature vulcanized type fire-resisting ceramic silicone rubber of the present invention coating material, in process for preparation, must strictly be controlled the water content of various compositions, and carry out in dry environment.The major equipment using in industrial production has kneader, high speed agitator, planetary stirrer, three-roll grinder, mixing extruder and wrapping machine etc.Can adopt interrupter method to produce, but adopt continuous processings more in scale operation.The major equipment that interrupter method is produced is planetary stirrer or dish-like dispersion machine.The major equipment that continuous processing is produced is twin-screw mixer forcing machine or static mixer.
Although the single-component room temperature vulcanized type fire-resisting ceramic silicone rubber of the present invention coating material is easy to use, because its sulfuration is according to the moisture in lazy atmosphere, the thickness of cross-linked rubber is restricted, can only be for the occasion of 6 millimeters of following thickness of needs.The vulcanization reaction of single-component room temperature vulcanized silicon rubber carries out toward depths gradually from surface, and glue-line is thicker, solidifies slower.When fast setting is also wanted in the large thickness of needs or deep, can adopt stratified watering progressively to vulcanize method, can add some sizing materials at every turn, wait after sulfuration reinforcedly again, can reduce total curing time like this.In manufacturing processed, can improve the temperature and humidity of environment, can make sulfidation accelerate.
Can also be same as the prior art in the single-component room temperature vulcanized type fire-resisting ceramic silicone rubber of the present invention coating material, add hydroxyl and moisture scavenger, remove the moisture that hydroxyl remaining in base glue and filler etc. are brought into, can improve the package stability of sizing material; Add alcohol scavenging agent or sequestrant, can avoid free alcohol in sizing material to form the (CH without crosslinked function with polysiloxane generation equilibration reaction under organo-metallic catalyst exists
30) (CH
3) 2SiOl/2 end group.
The invention provides thinking and method that a kind of single-component room temperature vulcanized type fire-resisting ceramic silicone rubber coating material is made, method and the approach of this technical scheme of specific implementation are a lot, and the above is only the preferred embodiment of the present invention.
Claims (12)
1. a single-component room temperature vulcanized type fire-resisting ceramic silicone rubber coating material, it is characterized in that, it mainly comprises following component and parts by weight: α, 100 parts of alpha, omega-dihydroxy polydimethyl siloxanes, thermal silica 10-20 part, aluminum oxide 5-10 part, sinter additives 0.5-2 part, linking agent 5-15 part, catalyzer 0.1-0.5 part, softening agent 20-60 part, tackifier 0.5-1.5 part, surface treatment agent 0.1-0.5 part.
2. single-component room temperature vulcanized type fire-resisting ceramic silicone rubber coating material according to claim 1, is characterized in that, described thermal silica is vapor phase process ultra-fine white carbon black.
3. single-component room temperature vulcanized type fire-resisting ceramic silicone rubber coating material according to claim 1, is characterized in that, described aluminum oxide is electric filler aluminum oxide or used in electronic ceramic aluminum oxide.
4. single-component room temperature vulcanized type fire-resisting ceramic silicone rubber coating material according to claim 1, is characterized in that, described sinter additives is Fe
2o
3, MnO
2, Cr
2o
3or TiO
2.
5. single-component room temperature vulcanized type fire-resisting ceramic silicone rubber coating material according to claim 1, is characterized in that, described linking agent is trifunctional organoalkoxysilane.
6. single-component room temperature vulcanized type fire-resisting ceramic silicone rubber coating material according to claim 1, is characterized in that, described catalyzer is that two organotins are two.
7. single-component room temperature vulcanized type fire-resisting ceramic silicone rubber coating material according to claim 1, is characterized in that, described softening agent is α, ω-dimethoxy polydimethylsiloxane.
8. single-component room temperature vulcanized type fire-resisting ceramic silicone rubber coating material according to claim 1, is characterized in that, described tackifier are cyano alkoxy silane.
9. single-component room temperature vulcanized type fire-resisting ceramic silicone rubber coating material according to claim 1, is characterized in that, described surface treatment agent is silastic surface treatment agent or silane coupling agent.
10. single-component room temperature vulcanized type fire-resisting ceramic silicone rubber coating material according to claim 9, it is characterized in that, described silane coupling agent is vinyltrimethoxy silane, vinyltriethoxysilane, γ mercaptopropyitrimethoxy silane or γ-(1,2-encircles propoxy-) propyl trimethoxy silicane.
The preparation method of 11. 1 kinds of single-component room temperature vulcanized type fire-resisting ceramic silicone rubber coating materials as described in claim 1-10 any one, is characterized in that: mainly comprise the following steps:
1) first in thermal silica, aluminum oxide, sinter additives, by umber, add respectively surface treatment agent, then in kneader, process respectively, handle rear stand-by;
2) again by α, the thermal silica after alpha, omega-dihydroxy polydimethyl siloxane, surface treatment, surface treatment
After aluminum oxide, the sinter additives after surface treatment, softening agent and tackifier on rubber mixing machine or three-roller, be mixed into after paste or thick liquid, then carry out drying treatment;
3) after cooling under drying regime, add linking agent, catalyzer, after fully mixing under the condition of moisture in isolated air, be encapsulated in airtight container and store;
4) while using, take out from container, the steam in ingress of air, solidifies and can obtain this coating material under room temperature.
12. 1 kinds of single-component room temperature vulcanized type fire-resisting ceramic silicone rubber coating materials as described in claim 1-10 any one, is characterized in that, this material is applied in electric wire.
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| CN106893146A (en) * | 2017-03-30 | 2017-06-27 | 中国热带农业科学院农产品加工研究所 | Supporting material and preparation method thereof, natural rubber material |
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| CN111019516A (en) * | 2019-12-25 | 2020-04-17 | 湖南航天三丰科工有限公司 | Light self-curing electric power insulation coating material, preparation method and power line |
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