CN112111159A - High-temperature vulcanized silicone rubber with conductivity and ceramic property and preparation method thereof - Google Patents
High-temperature vulcanized silicone rubber with conductivity and ceramic property and preparation method thereof Download PDFInfo
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- C08L83/00—Compositions of macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing silicon with or without sulfur, nitrogen, oxygen or carbon only; Compositions of derivatives of such polymers
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Abstract
The invention discloses a high-temperature vulcanized silicone rubber with conductivity and ceramic property and a preparation method thereof, wherein the high-temperature vulcanized silicone rubber comprises the following components: raw methyl vinyl silicone rubber, raw methyl phenyl vinyl silicone rubber, a reinforcing filler, a conductive medium, a structural control agent, a fluxing agent, a porcelain forming filler, a coupling agent, a release agent and a vulcanizing agent; the method comprises the following steps: putting the heat vulcanized silicone rubber raw rubber, the reinforcing filler fumed silica and the silicone oil into an internal mixer for stirring; uniformly blending the ceramic filler and the fluxing agent, and carrying out surface treatment on the coupling agent; carrying out surface activation pretreatment on the conductive medium; the materials are blended in a kneader to prepare the high-temperature vulcanized ceramic silicon rubber which has both conductivity and ceramic property. The invention has the advantages of good mechanical properties on the premise of ensuring good electrical properties, and the prepared product is easy to process, good in weather resistance and aging resistance, good in low temperature resistance and has important significance for widening the application field of the silicon rubber.
Description
The technical field is as follows:
the invention relates to the technical field of hot vulcanized silicone rubber materials, in particular to a high-temperature vulcanized silicone rubber which has semiconductive property and can be ceramized and a preparation method thereof.
Background art:
statistical data indicate that electrical wiring is a significant cause of building fires. Along with the continuous promotion of urban construction in China, the degree of urban building densification is increased rapidly, so that the population is highly concentrated, and the places with highly dense personnel, such as stations, airports, ports, movie theaters, office buildings, large shopping malls and hospitals, can cause great loss once a fire accident occurs. Under the condition of fire, the smoothness of electric power and communication is guaranteed within a certain time, and the reduction of financial loss and casualties is important.
The ceramic silicon rubber material is used as a novel high-molecular fireproof material and is widely applied to the wire and cable industry. At present, a magnesium oxide mineral insulation fireproof cable and a mica tape wrapped fireproof cable are mostly adopted at home and abroad, and the research and development of the ceramic silicon rubber fireproof cable provides a novel, safe and economical fireproof cable for fire control and fire prevention, and particularly develops a new idea and a new method for manufacturing fireproof electric wires and cables, so that the cost is greatly reduced compared with the traditional fireproof cable. General polymer materials are burned into ash after combustion, and even flame retardant materials are burned into powder; the ceramic fireproof and fireproof silicon rubber begins to harden and sinter at the temperature of more than 500 ℃ to become a ceramic-like hard shell, and the higher the temperature is, the longer the ablation time is, the harder the formed ceramic shell is, and the ceramic shell is not melted even at the temperature of more than 1300 ℃. The silicone rubber has the characteristics of common silicone rubber at normal temperature, has good flexibility and elasticity, good high and low temperature resistance, excellent electrical insulation performance, ozone aging resistance, weather aging resistance, no toxicity, no harm and no pollution, and conforms to the EU ROHS instruction.
The fire-resistant wire and cable produced by the ceramic silicon rubber can not generate gas and smoke harmful to human bodies during combustion, meets the environment-friendly requirement of low smoke and no toxicity, and has certain fire resistance. Therefore, when the material is applied to fire-resistant wires and cables, the ceramic glue is quickly converted into a hard ceramic layer under the condition that the wires and cables are burnt by fire, so that the wires and cables are well protected, and the integrity of electric power or communication lines is ensured. The ceramic hard shell can even resist water spray and indirect vibration on a fire scene, and a plurality of foreign manufacturers use ceramic glue (also called as special silicon rubber mixture and high-performance silicon rubber meeting fire resistance requirements) to produce products meeting British BS6387 standards. For example, a ceramic silicone rubber and a preparation method thereof are disclosed in Chinese patent with application number CN103525092A, Chinese patent with application number CN103554918A and Chinese patent with application number CN 107141811A.
At present, the voltage class of the existing fireproof power cable in China is 0.6/1kV or below, no 6-35kV fireproof power cable exists, the existing fireproof power cable cannot meet the fireproof requirement, the existing fireproof power cable cannot meet the requirement in an ultra-large, ultra-high or comprehensive building, the existing fireproof power cable class cannot meet the requirement, the 6-35kV fireproof cable does not exist, and currently, a plurality of low-voltage fireproof power cables, a plurality of transformers and a power distribution room are combined for use, so that the cost is greatly increased, a lot of space is occupied, a lot of non-renewable resources are wasted, the safety risk is increased, and inconvenience is brought to the design and layout. Therefore, the ceramic raw material can be made into ceramic, and the conductivity of the material is also considered.
Because the ceramic silicon rubber is an insulating material, when the ceramic silicon rubber is used in the actual production process, no matter in the rubber mixing process or when the ceramic silicon rubber is used as a cable sheath material, friction is generated between the ceramic silicon rubber and other products, an electrostatic phenomenon can occur, when electrostatic charges are accumulated to a certain degree, sparks can be emitted, and fire explosion can be caused by the ceramic silicon rubber and combustible substances in the air in danger. In addition, when the silicon rubber is applied to a part of precision device processing operation tables, the generation of static electricity can damage the interior of precision devices, and the precision and the service life of the devices are influenced. The method for modifying the antistatic silicon rubber shoe with the mixed rubber is to add a conductive medium into the material. The current mechanisms for the conduction of elastomeric materials are mainly classified into three types, namely: the theory of seepage, the theory of tunneling and the theory of field emission, wherein the theory of seepage is the conduction mechanism which is the main basis of the current production and processing, and the theory considers that conductive media contact with each other in a non-conductive elastomer to form a continuous conductive path so as to generate a conductive network to make the material conductive.
The volume resistivity of the vulcanized silicone rubber product can reach 1-103Omega cm. The method is mainly applied to the aspects of high-voltage cable sheaths, contacts of silicon rubber keys and the like. Fillers capable of imparting conductivity to silicone rubber can be classified into two major classes according to the form of electron movement, i.e., pi electron movement type conductive fillers such as carbon black, graphite, carbon fiber, and the like; free electron moving type conductive fillers, such as silver powder, nickel powder, copper powder, zinc powder, aluminum powder and non-metal powder surface plated metal fillers. Obtaining a volume resistivity of 10-1The conductive silicone rubber below omega.cm needs to use metal powder, namely free electron moving conductive filler. The silver powder and the gold powder are expensive and have high manufacturing cost; the filler for plating metal on the surface of the non-metal powder is cheap, but has the defect that the surface is easy to oxidize to slowly reduce the conductivity. The conductive carbon black (such as acetylene black and conductive furnace black) is low in price, and the filling amount can be adjusted according to requirements, so that conductive silicone rubber with different conductive grades can be prepared, and the conductive carbon black is a commonly adopted conductive filler. However, in the formulation of conductive compounded silicone rubber, the following problems also occur: firstly, preparing a high conductivityThe filling amount of carbon black is increased continuously in the electrical mixing silicone rubber, so that the viscosity of the silicone rubber is increased, and the processing performance of the material is poor; secondly, the surface activity of the selected carbon black is too strong, so that the action of a vulcanizing agent is reduced, and a vulcanized product is unstable; thirdly, the carbon black contains trace sulfur and volatile impurities, which can hinder the vulcanization and reduce the vulcanization performance; the compatibility of the selected carbon black and the sizing material is not good, and the prepared rubber compound silicon rubber has internal elastic distortion and deviation of conductivity due to the rheological result under the forming pressure.
The invention content is as follows:
in order to solve the existing problems, the invention discloses a high-temperature vulcanized silicone rubber with both conductivity and ceramic property and a preparation method thereof, the prepared high-temperature vulcanized silicone rubber has the advantages of both mechanical property and good electrical property, and the prepared product is easy to process, good in weather resistance and aging resistance, good in low-temperature resistance, good in antistatic property, good in processability and mechanical property, low in production cost, environment-friendly and has great market potential in the aspects of high-voltage fire-resistant cables and the like. The specific technical scheme is as follows:
a high-temperature vulcanized silicone rubber with both conductivity and ceramic property is prepared from the following raw materials in parts by weight:
80-130 parts of heat-vulcanized silicone rubber raw rubber,
20-50 parts of reinforcing filler fumed silica,
10-20 parts of a conductive medium,
0-10 parts of a structural control agent,
20-50 parts of a fluxing agent,
20-60 parts of a porcelain-forming filler,
0-5 parts of a coupling agent,
0-5 parts of heat stabilizer
0-5 parts of a release agent,
0-5 parts of a vulcanizing agent.
Preferably, the raw heat-vulcanized silicone rubber is one or any combination of dimethyl silicone rubber, methyl-terminated methyl vinyl silicone rubber, vinyl-terminated methyl vinyl silicone rubber and methyl phenyl vinyl silicone rubber.
Furthermore, the heat-vulcanized silicone rubber raw rubber adopts one or any combination of dimethyl silicone rubber, methyl-terminated methyl vinyl silicone rubber, vinyl-terminated methyl vinyl silicone rubber and methyl phenyl vinyl silicone rubber with the molecular weight of 600000-900000 and the vinyl content of 0.01% -0.3%.
Preferably, the reinforcing filler is one or a combination of two of fumed silica and precipitated silica.
Preferably, the conductive medium is one or any combination of carbon black, graphite and carbon fiber. The selection of carbon black in the conductive medium is particularly important for its properties, such as: specific surface area, DBP oil absorption, primary particle size and secondary particle size, iodine adsorption, hydrochloric acid adsorption, toluene coloring transmittance or UV absorbance, and the like; the specific surface area is generally 25-50m2The concentration of the catalyst is 1.0-1.5ml/g, the DBP oil absorption is 1.0-1.5ml/g, the primary particle size is 60-120nm, the iodine adsorption value is less than 50mg/g, the hydrochloric acid adsorption is 0.60-6ml/g, and the toluene coloring transmittance is 90-100%.
Preferably, the structural control agent is hydroxyl silicone oil with the mass fraction of hydroxyl groups of 0.06% -0.12%.
Preferably, the fluxing agent is one or any combination of glass powder with a softening point of 300-800 ℃, zinc borate and zinc oxide.
Preferably, the porcelain forming filler is one or any combination of mica, wollastonite and kaolin.
Preferably, the coupling agent is a titanate coupling agent, a silane coupling agent or one of the titanate coupling agent and the silane coupling agent.
The other auxiliary materials are common auxiliary materials.
The invention also discloses a preparation method of the high-temperature vulcanized silicone rubber capable of realizing both conductivity and ceramic formation, which is characterized by comprising the following steps:
A) uniformly mixing the raw heat vulcanized silicone rubber, the reinforcing filler white carbon black and the structural control agent in an internal mixer to prepare a granular mixture capable of flowing freely;
B) uniformly mixing and heating the ceramic filler and the fluxing agent in an internal mixer, and then adding a coupling agent for surface treatment;
C) adding a coupling agent into a conductive medium for surface activation treatment;
D) conveying the raw materials obtained in the steps A), B) and C) into a kneading machine by an internal mixer, kneading and mixing at high temperature, vacuumizing, and filtering to obtain rubber compound and silicon rubber;
E) adding a vulcanizing agent into the prepared rubber compound silicone rubber, repeatedly thinly passing the rubber compound silicone rubber on a double-roll rubber mixing mill, vulcanizing the rubber compound silicone rubber for 15min at the temperature of 130 ℃ and under the pressure of 22MPa to prepare a test piece with the thickness of 2mm, and measuring various properties of the test piece;
wherein the high temperature in the internal mixer is 100-200 ℃; the temperature in the kneader is 100-200 ℃, the rotating speed is 30 +/-5 r/min, and the nitrogen flow is 5m3The kneading time is 2 hours, the single-screw basic filtration is carried out, and the filtration mesh number is 150-200 meshes; plasticating and sampling the rubber and silicon rubber of the rubber compound on a double-roll rubber mixing mill, adding a vulcanizing agent, uniformly mixing on the double-roll mixing mill, vulcanizing at 130 ℃ and 22MPa for 15min to prepare a test piece with the thickness of 2mm, and then carrying out secondary vulcanization at 200 ℃ for 4h to test various properties of the test piece; the method comprises the steps of testing the tensile strength, the elongation at break and the tearing strength of a sample by using a universal tensile testing machine, testing the Shore hardness of the sample by using a hardness tester, testing the volume resistance of the sample by using a resistance tester, testing the smoke density of the sample by using a smoke density tester, testing the oxygen index of the sample by using an oxygen index tester, observing the sintering condition by using a muffle furnace, testing the thermal property change of the sample in the process of room temperature to 1000 ℃ by using TG-DSC, and analyzing the composition and the change of combustion products of the sample at different temperatures by using FTIR and XRD.
First, from the standpoint of achieving good antistatic properties, there are five factors associated with the volume resistivity, namely: (1) the self-resistivity and polarity of the silicone rubber, (2) the resistivity of the filler particles, (3) the resistivity between the filler particles, (4) the number of particles in the conductive loop, (5) the number of conductive paths. Therefore, for the silicone rubber itself, it is necessary to ensure that the internal Mooney viscosity and molecular weight are not too high, so as to prevent the conductive particles from being dispersed in the system and from being agglomerated. In order to realize that the specific resistance between the filler particles and the particles can realize lower specific resistance in the elastomer, the conductive carbon black with lower DBP value and iodine absorption value is selected for the filler particles, and the particles are activated on the surface in the initial stage to increase the polarity and the specific surface area. As excessive carbon black particles can damage the toughness of a silicon rubber matrix, and for a particle-filled conductive composite material, the conductive performance is generally divided into an insulating region, a percolation region and a conductive region, wherein the percolation region refers to that the conductive performance of a system is mutated and the addition amount of conductive carbon black is added to the surface region of the particles at the initial stage, the volume resistivity of the silicon rubber is obviously reduced along with the increase of the addition amount of the carbon black and then gradually becomes gentle until the conductive performance is not greatly improved along with the increase of the addition amount of the carbon black, so that the optimal proportion of the addition amount of the carbon black is selected. In addition, in order to further reduce the resistivity, rodlike fiber carbon fibers can be additionally added, on one hand, the resistivity of the carbon fibers is lower than that of carbon black, and on the other hand, the rodlike fibers are used as bridges in one-dimensional orientation to connect and disperse conductive carbon black in a system, so that more conductive paths are formed, the overall resistivity is reduced, better electron transfer is realized, and the electrostatic phenomenon of the material is avoided.
Secondly, from the perspective of realizing ceramization, it needs to be linked with the mechanism of ceramization of the ceramizable polymer material. The traditional high molecular material can be incinerated and combusted when meeting flame or high-temperature environment, and the generated residues are non-condensed particles and powder, cannot play a supporting role and are easy to fall off. If the supporting filler, the ceramic forming filler, the fluxing agent and the like are added into the high polymer material matrix, so that the ceramic forming filler and the fluxing agent are synergistic with the high polymer matrix and the cracking products thereof when the high polymer material is subjected to flame ablation or high temperature, transformation occurs inside the material, namely, the fluxing agent is gradually melted when the high polymer material is subjected to flame ablation or high temperature, a eutectic mixture is formed at the boundary of the supporting filler, a bridging effect is formed with amorphous residues generated by cracking of the high polymer matrix, the temperature is gradually increased along with the passage of time, the eutectic mixture is more fully permeated between the supporting filler and the amorphous residues, the filler boundary gradually disappears, new inorganic phases are generated, and a complete ceramic body is formed. Therefore, the ceramic system is a core component in the ceramic silicon rubber formula, and mainly comprises a ceramic filler and a fluxing agent.
At present, the filler for ceramic silicon rubber porcelain is generally a phyllosilicate mineral filler, has a crystal structure, and has a high melting point (high refractoriness) and a high sintering degree. The following ceramic forming fillers are mainly used: 1) mica. Mica is a complex silicate, many kinds of which are layered crystals, and has various crystal systems, and the melting point of about 1800 ℃ or even higher. The mica used for the ceramicized silicone rubber mainly includes muscovite (muscovite) and phlogopite (phlogopite). Muscovite is a dioctahedral alkali aluminum silicate (aluminum silicate) having a layered structure of aluminum silicate sheets weakly bonded to each other through a potassium ion layer, and has a KAl content3Si3O10(OH)2. Phlogopite is a trioctahedral alkali aluminum silicate (trioctahedral alkali aluminum silicate) and has a layered structure of aluminum magnesium silicate sheets weakly bonded to each other by potassium ions, and the component is KMg3AlSi3O10(OH)2. The selection of the appropriate mica species, average particle size and amount will depend on the intended use of the article, the processability of the compound, the physical properties of the vulcanizate and the desired strength and dimensional retention after conversion to ceramic. Mica powder is added into general ceramic silicon rubber, and the particle size distribution and the average particle size of the mica powder have important influence on the dimensional stability and the physical properties of a ceramic sintered body generated at high temperature. Generally, mica having an average particle size of 50 to 200 μm is preferably used for cables and other products requiring high shape retention, and if the average particle size of mica is too small, the physical strength of the sintered body is large, but the shrinkage is large, which may cause cracking. If the average particle size of the mica is too large or the content is too high, the resulting compound is difficult to process into the desired shape. In addition, the physical properties of the crosslinked siloxane polymers containing coarse mica fractions or high levels of mica are poor, and the coarse mica particles are preferentially oriented along their crystalline basal planes when the composition is extruded or molded, resulting in tear strengthThe mica can be pretreated by a coupling agent, so that the mechanical strength before combustion is improved. 2) Wollastonite. Calcium silicate filler is also one of important porcelain forming fillers of silicone rubber, and mainly comprises wollastonite, xonotlite, tobermorite, conite, manganesite and the like, wherein the wollastonite is most used. Wollastonite is natural calcium metasilicate (CaSiO)3) Triclinic system, melting point 1540 ℃. The wollastonite used for ceramic silicon rubber is alpha-CaSiO3The wollastonite powder is needle-like particles, and the aspect ratio is preferably 2:1 to 5:1, and the average particle length is preferably 5 to 50 μm. The sizing material containing the wollastonite has relatively stable performance and small mass loss rate after combustion. 3) Kaolin. Kaolin is clay containing natural kaolinite as main ingredient, and its chemical component is hydrated aluminum silicate (Al)2O3.2SiO2.2H2O) in the form of pseudo hexagonal platelets with a melting point of about 1735 c. It is more advantageous to use surface treated calcined kaolin to improve physical strength.
Another important component of the ceramifying system is the fluxing agent. Because the ceramic fillers used by the ceramic silicon rubber have high melting points and correspondingly have high ceramic temperature after combustion, in order to be fired at low temperature, namely the silicon rubber can be ceramized at lower temperature to obtain a ceramic body with certain strength, and better exert the fireproof and fireproof functions of the ceramic silicon rubber, a fluxing agent (flux) is required to be added into a rubber compound formula. Flux generally refers to a substance that lowers the softening, melting, or liquefaction temperature of other substances. At present, the fluxing agent of the ceramic silicon rubber ceramic filler mainly comprises a glass additive, a boron-containing compound and zinc oxide. 1) A glass additive. The glass additive used as a fluxing agent is preferably a powdered glass frit (also known as glass frit) or may be glass fibers. A suitable softening point range is 300-800 ℃. 2) A boron-containing compound. Certain boron-containing compounds, such as borax, zinc borate, etc., whose chemical composition boron oxide is a fluxing agent for glass, aid in the formation of the glassy phase at low temperatures. The zinc borate is used as a flame retardant and a low-temperature glass forming agent, the softening point of the zinc borate is 300-700 ℃, and the zinc borate is used as a low-melting-point fluxing agent, so that the fire resistance of the ceramic silicon rubber can be improved, and the ceramic silicon rubber has higher rigidity and good shape retention. 3) And (3) zinc oxide. There are patents which use zinc oxide as a fluxing agent, with mica and silicone rubber to form a ceramicized system.
In addition, when more fillers are added into the system, the product performance is easy to decline, and in order to reduce the decline range, the fillers can be pretreated to be surface modified and the compatibility of each component can be improved besides selecting proper filler types and addition amounts. And the principle of 'similar compatibility' has universality for high-molecular weight and low-molecular weight compounds. I.e., where chemical compositions and structurally similar compounds are compatible; chemical compositions and structurally different compounds may be partially or completely incompatible depending on the degree of difference. The compatibility level of each component in the system determines the quality of the prepared silicone rubber material, and the components can be properly compatible with each other, so that the size of a dispersed phase is reduced, the particles are uniformly distributed, a phase interface can generate good adhesion, and the mechanical property can achieve the expected effect. The fillers added in the process of preparing the high-temperature vulcanized silicone rubber which has both conductivity and ceramic property are mostly natural mineral inorganic salts or oxides, mostly ionic compounds, and have the advantages of large polarity, large surface energy, low affinity with most polymers and poor compatibility, so the fillers need to be subjected to surface modification treatment. The surface modification aims to change the inherent polar surface of the filler into a non-polar surface, namely, the original hydrophilic surface is changed into a lipophilic surface, so that the surface tension of the filler is reduced, and the purposes of improving the compatibility between the filler and a silicon rubber matrix and other organic auxiliary agent components and improving the infiltration and adhesion effects between the filler surface and the organic components are achieved. Such as treating mica with a silane coupling agent to improve mechanical strength before and after burning, surface-treating kaolin with an aminosilane coupling agent to improve physical properties of silicone rubber, and the like.
In order to realize the consideration of conductivity, ceramic property and mechanical property, the invention firstly mixes the heat vulcanized silicon rubber crude rubber, the reinforcing filler, the structure control agent and the like in an internal mixer uniformly; secondly, the coupling agent carries out surface modification treatment on the ceramic-forming filler and the conductive medium, and the mixture is uniformly mixed in an internal mixer at high temperature so as to reduce the phase interface tension of the filler and the other components, wet the surface of the filler and provide the dispersity of the filler, and the components can be better compatible; the fluxing agents in the ceramic filler can be selected from fluxing agents with different melting points, and are matched with each other at different heights, and the ceramic forming temperature is adjusted to adapt to different application occasions. Then kneading the components uniformly at high temperature by a kneader, removing part of volatile matters after high temperature, and improving the infiltration and dispersion effects among the components; and finally, filtering and extruding to obtain the high-temperature silicon sulfide rubber which has both conductivity and ceramic property.
The invention has the beneficial effects that: the high-temperature vulcanized silicone rubber with both conductivity and ceramic property provided by the invention adopts the raw hot vulcanized silicone rubber as the base material, preferentially adds the reinforcing filler with high purity and proper specific surface area, then adds the proper ceramic system, puts in the conductive medium with low iodine adsorption value and high specific surface area, controls the processing property and mechanical property of the product by adjusting the proportion of the raw hot vulcanized silicone rubber, the reinforcing filler, the ceramic-forming filler and the conductive medium and selecting proper auxiliary agent, and finally prepares the composite functional material with simple process, easy processing, electrical property, ceramic property and mechanical property. Has good application prospect in the aspect of high-voltage fire-resistant cable sheath material.
The specific implementation mode is as follows:
the following detailed description of the preferred embodiments of the present invention is provided to enable those skilled in the art to more readily understand the advantages and features of the present invention and to clearly define the scope of the invention.
Example 1
The preparation method of the high-temperature vulcanized silicone rubber with both conductivity and ceramic property comprises the following specific processes:
a) weighing two molecular terminals (CH) according to the weight ratio2＝CH)(CH3)2SiO1/2Chain link end capping, (CH)2＝CH)(CH3) The mole fraction of SiO chain link is 0.1%, (CH)3)2Methyl vinyl silicone rubber having a molar fraction of SiO units of 99.9% and an average degree of polymerization of about 7000100 parts of crude rubber, 40 parts of fumed silica and 4 parts of hydroxy silicone oil (the mass fraction of hydroxy groups is 0.08%), and the crude rubber, the fumed silica and the hydroxy silicone oil are put into an internal mixer to be uniformly mixed, the temperature in the internal mixer is set to be 130 ℃, and the internal mixing time is 1 hour, so that a granular mixture 1 capable of flowing freely is prepared;
b) weighing 50 parts of muscovite with the particle size of 50 mu m and 20 parts of glass powder with the melting point of about 545 ℃, uniformly mixing the muscovite and the glass powder at a high temperature in an internal mixer, adding 3 parts of silane coupling agent, and carrying out surface modification treatment on the porcelainous filler and the fluxing agent, wherein the temperature in the internal mixer is set to 150 ℃, and the internal mixing time is 1h, thus preparing powder 1;
c) weighing 12 parts of conductive medium, wherein the specific surface area of the conductive medium is 42m2Putting conductive carbon black with the oil absorption of 1.1ml/g DBP, the primary particle size of 70nm, the iodine adsorption value of 45mg/g, the hydrochloric acid adsorption amount of 3.2ml/g and the coloring transmittance of toluene of 95% into an internal mixer, adding 1 part of coupling agent, carrying out heat treatment for 1 hour in the internal mixer at the temperature of 190 ℃ to obtain a surface treatment conductive medium 1;
d) continuously feeding the raw materials obtained in the steps a), b) and c) into a kneader through a single-screw extruder, adding 0.2 part of heat stabilizer selenium oxide and 0.2 part of release agent fatty acid metal salt, and stirring the mixture in the kneader by 5m3Introducing nitrogen at a flow rate of/h, mixing for about 1h at 60-100 ℃, then heating to 180 ℃, carrying out heat treatment for 1h, cooling, extruding and filtering the rubber material prepared in the internal mixer by using a single screw rod, and preparing rubber compound and silicon rubber 1;
taking 100 parts of the prepared rubber compound silicone rubber, adding 0.7 part of vulcanizing agent, repeatedly thinly passing on a double-roll rubber mixing mill, vulcanizing the rubber compound silicone rubber at 130 ℃ and 22MPa for 15min to prepare a high-temperature vulcanized silicone rubber test piece with the thickness of 2mm, and measuring the material hardness of 63Shore A, the tensile strength of 7.8MPa, the elongation at break of 298%, the tear strength of 29kN/mm, and the volume resistivity of 7.4 multiplied by 107And omega.cm, observing the sintering condition in a muffle furnace, and finding that the sample is compact in appearance and small in shrinkage rate after being sintered.
Example 2
The preparation method of the high-temperature vulcanized silicone rubber with both conductivity and ceramic property comprises the following specific processes:
a) weighing two molecular terminals (CH) according to the weight ratio2＝CH)(CH3)2SiO1/2Chain link end capping, (CH)2＝CH)(CH3) The mole fraction of SiO chain link is 0.1%, (CH)3)2100 parts of methyl vinyl silicone rubber raw rubber with the SiO chain link molar fraction of 99.9 percent and the average polymerization degree of 7000, 40 parts of precipitated silica white and 4 parts of hydroxyl silicone oil (the hydroxyl mass fraction is 0.08 percent) are put into an internal mixer to be uniformly mixed, the temperature in the internal mixer is set to be 130 ℃, and the internal mixing time is 1 hour, so as to prepare a granular mixture 1 capable of flowing freely;
b) weighing 50 parts of muscovite with the particle size of 50 mu m and 20 parts of glass powder with the melting point of about 545 ℃, uniformly mixing the muscovite and the glass powder at a high temperature in an internal mixer, adding 3 parts of silane coupling agent, and carrying out surface modification treatment on the porcelainous filler and the fluxing agent, wherein the temperature in the internal mixer is set to 150 ℃, and the internal mixing time is 1h, thus preparing powder 1;
c) weighing 12 parts of conductive medium, wherein the specific surface area of the conductive medium is 42m2Putting conductive carbon black with the oil absorption of 1.1ml/g DBP, the primary particle size of 70nm, the iodine adsorption value of 45mg/g, the hydrochloric acid adsorption amount of 3.2ml/g and the coloring transmittance of toluene of 95% into an internal mixer, adding 1 part of coupling agent, carrying out heat treatment for 1 hour in the internal mixer at the temperature of 190 ℃ to obtain a surface treatment conductive medium 1;
d) continuously feeding the raw materials obtained in the steps a), b) and c) into a kneader through a single-screw extruder, adding 0.2 part of heat stabilizer selenium oxide and 0.2 part of release agent fatty acid metal salt, and stirring the mixture in the kneader by 5m3Introducing nitrogen at a flow rate of/h, mixing for about 1h at 60-100 ℃, then heating to 180 ℃, carrying out heat treatment for 1h, cooling, extruding and filtering the rubber material prepared in the internal mixer by using a single screw rod, and preparing rubber compound and silicon rubber 1;
taking 100 parts of the prepared rubber compound silicon rubber, adding 0.7 part of vulcanizing agent into 0 part of the prepared rubber compound silicon rubber, repeatedly thinly passing the rubber compound silicon rubber on a double-roll rubber mixing mill, vulcanizing the rubber compound silicon rubber for 15min at the temperature of 130 ℃ and under the pressure of 22MPa to prepare a high-temperature vulcanized silicon rubber test piece with the thickness of 2mm, and measuring the material hardness of 64Shore A, the tensile strength of 6.5MPa, the elongation at break of 202 percent and the tearing strength of 20kN/mmVolume resistivity of 5.2X 107And omega cm, observing the sintering condition in a muffle furnace, and finding that the sintered sample has loose appearance and small shrinkage.
In example 2, based on example 1, the type of the reinforcing material is mainly changed, the fumed silica used in example 1 has a nano-scale particle size, and the precipitated silica used in example 2 has a micro-scale particle size, so that compared with example 1, the mechanical properties of the system are reduced, the conductivity is increased, and the sintered appearance is inferior to example 1, which indicates that the particle size of the reinforcing material is increased, and the mechanical properties and the ceramifiable property of the product are adversely affected.
Example 3
The preparation method of the high-temperature vulcanized silicone rubber with both conductivity and ceramic property comprises the following specific processes:
a) weighing two molecular terminals (CH) according to the weight ratio2＝CH)(CH3)2SiO1/2Chain link end capping, (CH)2＝CH)(CH3) The mole fraction of SiO chain link is 0.1%, (CH)3)2100 parts of methyl vinyl silicone rubber raw rubber with the SiO chain link molar fraction of 99.9 percent and the average polymerization degree of 7000, 40 parts of fumed silica and 4 parts of hydroxyl silicone oil (the hydroxyl mass fraction is 0.08 percent) are put into an internal mixer to be uniformly mixed, the temperature in the internal mixer is set to be 130 ℃, and the internal mixing time is 1 hour, so that a granular mixture 1 capable of flowing freely is prepared;
b) weighing 30 parts of muscovite with the particle size of 50 microns, wollastonite with the particle size of 55 microns and the length-diameter ratio of 3.1 and 20 parts of glass powder with the melting point of about 545 ℃, putting the mixture into an internal mixer, uniformly mixing the mixture at high temperature, adding 3 parts of silane coupling agent, carrying out surface modification treatment on the ceramic filler and the fluxing agent, setting the temperature in the internal mixer at 150 ℃, and carrying out internal mixing for 1 hour to prepare powder 1;
c) weighing 12 parts of conductive medium, wherein the specific surface area of the conductive medium is 42m2Conductive carbon black with the oil absorption of 1.1ml/g DBP, the primary particle diameter of 70nm, the iodine adsorption value of 45mg/g, the hydrochloric acid adsorption amount of 3.2ml/g and the toluene coloring light transmittance of 95 percent is put into an internal mixer, 1 part of coupling agent is added, and the mixture is subjected to heat treatment for 1 hour in the internal mixer at the temperature of 190 ℃ under the condition that the temperature is higher than the melting point of the conductive carbon blackObtaining a surface treatment conductive medium 1 at the temperature of DEG C;
d) continuously feeding the raw materials obtained in the steps a), b) and c) into a kneader through a single-screw extruder, adding 0.2 part of heat stabilizer selenium oxide and 0.2 part of release agent fatty acid metal salt, and stirring the mixture in the kneader by 5m3Introducing nitrogen at a flow rate of/h, mixing for about 1h at 60-100 ℃, then heating to 180 ℃, carrying out heat treatment for 1h, cooling, extruding and filtering the rubber material prepared in the internal mixer by using a single screw rod, and preparing rubber compound and silicon rubber 1;
taking 100 parts of the prepared rubber compound silicone rubber, adding 0.7 part of vulcanizing agent into the rubber compound silicone rubber, repeatedly thinly passing the rubber compound silicone rubber on a double-roll rubber mixing mill, vulcanizing the rubber compound silicone rubber at 130 ℃ and 22MPa for 15min to prepare a high-temperature vulcanized silicone rubber test piece with the thickness of 2mm, and measuring the material hardness of 63Shore A, the tensile strength of 7.5MPa, the elongation at break of 285%, the tear strength of 28kN/mm and the volume resistivity of 8.2 multiplied by 107And omega cm, observing the sintering condition in a muffle furnace, and finding that the sintered sample has compact appearance and small shrinkage rate and basically keeps the original shape.
Example 4
The preparation method of the high-temperature vulcanized silicone rubber with both conductivity and ceramic property comprises the following specific processes:
a) weighing two molecular terminals (CH) according to the weight ratio2＝CH)(CH3)2SiO1/2Chain link end capping, (CH)2＝CH)(CH3) The mole fraction of SiO chain link is 0.1%, (CH)3)2100 parts of methyl vinyl silicone rubber raw rubber with the SiO chain link molar fraction of 99.9 percent and the average polymerization degree of 7000, 40 parts of fumed silica and 4 parts of hydroxyl silicone oil (the hydroxyl mass fraction is 0.08 percent) are put into an internal mixer to be uniformly mixed, the temperature in the internal mixer is set to be 130 ℃, and the internal mixing time is 1 hour, so that a granular mixture 1 capable of flowing freely is prepared;
b) weighing 30 parts of muscovite with the particle size of 50 microns of the ceramic filler, wollastonite with the particle size of 55 microns and the length-diameter ratio of 3.1 and 10 parts of glass powder with the melting point of about 650 ℃, putting the mixture into an internal mixer, uniformly mixing the mixture at high temperature, adding 3 parts of silane coupling agent, carrying out surface modification treatment on the ceramic filler and the fluxing agent, setting the temperature in the internal mixer to be 150 ℃, and carrying out internal mixing for 1 hour to prepare powder 1;
c) weighing 12 parts of conductive medium, wherein the specific surface area of the conductive medium is 42m2Putting conductive carbon black with the oil absorption of 1.1ml/g DBP, the primary particle size of 70nm, the iodine adsorption value of 45mg/g, the hydrochloric acid adsorption amount of 3.2ml/g and the coloring transmittance of toluene of 95% into an internal mixer, adding 1 part of coupling agent, carrying out heat treatment for 1 hour in the internal mixer at the temperature of 190 ℃ to obtain a surface treatment conductive medium 1;
d) continuously feeding the raw materials obtained in the steps a), b) and c) into a kneader through a single-screw extruder, adding 0.2 part of heat stabilizer selenium oxide and 0.2 part of release agent fatty acid metal salt, and stirring the mixture in the kneader by 5m3Introducing nitrogen at a flow rate of/h, mixing for about 1h at 60-100 ℃, then heating to 180 ℃, carrying out heat treatment for 1h, cooling, extruding and filtering the rubber material prepared in the internal mixer by using a single screw rod, and preparing rubber compound and silicon rubber 1;
taking 100 parts of the prepared rubber compound silicon rubber, adding 0.7 part of vulcanizing agent into 0 part, repeatedly thinly passing on a double-roll rubber mixing mill, vulcanizing the rubber compound silicon rubber at 130 ℃ and 22MPa for 15min to prepare a high-temperature vulcanized silicon rubber test piece with the thickness of 2mm, and measuring the material hardness of 63Shore A, the tensile strength of 7MPa, the elongation at break of 249 percent, the tear strength of 22kN/mm, the volume resistivity of 4.2 multiplied by 107And omega cm, observing the sintering condition in a muffle furnace, and finding that the sintered sample has a compact appearance but a large shrinkage rate.
Examples 3 and 4 based on example 1, the ceramization system was changed, including the weight and ratio of the ceramic filler, and the softening point selection and ratio of the flux, and it was found that the mechanical properties and conductivity of the two ceramic fillers are reduced in combination compared with the single ceramic filler, but the ceramic formation is better; the fluxing agent with high melting point and low proportion is used, the mechanical property of the product is reduced, the sintering porcelain forming condition is poor, but the conductivity is increased, which shows that the variety and proportion of the porcelain forming filler, the variety and the dosage of the fluxing agent have obvious influence on various properties of the product.
Example 5
The preparation method of the high-temperature vulcanized silicone rubber with both conductivity and ceramic property comprises the following specific processes:
a) weighing two molecular terminals (CH) according to the weight ratio2＝CH)(CH3)2SiO1/2Chain link end capping, (CH)2＝CH)(CH3) The mole fraction of SiO chain link is 0.1%, (CH)3)2100 parts of methyl vinyl silicone rubber raw rubber with the SiO chain link molar fraction of 99.9 percent and the average polymerization degree of 7000, 40 parts of fumed silica and 4 parts of hydroxyl silicone oil (the hydroxyl mass fraction is 0.08 percent) are put into an internal mixer to be uniformly mixed, the temperature in the internal mixer is set to be 130 ℃, and the internal mixing time is 1 hour, so that a granular mixture 1 capable of flowing freely is prepared;
b) weighing 50 parts of muscovite with the particle size of 50 mu m and 20 parts of glass powder with the melting point of about 545 ℃, uniformly mixing the muscovite and the glass powder at a high temperature in an internal mixer, adding 3 parts of silane coupling agent, and carrying out surface modification treatment on the porcelainous filler and the fluxing agent, wherein the temperature in the internal mixer is set to 150 ℃, and the internal mixing time is 1h, thus preparing powder 1;
c) weighing 12 parts of conductive medium, wherein the specific surface area of the conductive medium is 50m2Putting conductive carbon black with the oil absorption of 1.1ml/g DBP, the primary particle size of 100nm, the iodine adsorption value of 45mg/g, the hydrochloric acid adsorption amount of 3.2ml/g and the coloring transmittance of toluene of 92% into an internal mixer, adding 1 part of coupling agent, carrying out heat treatment for 1 hour in the internal mixer at the temperature of 190 ℃ to obtain a surface treatment conductive medium 1;
d) continuously feeding the raw materials obtained in the steps a), b) and c) into a kneader through a single-screw extruder, adding 0.2 part of heat stabilizer selenium oxide and 0.2 part of release agent fatty acid metal salt, and stirring the mixture in the kneader by 5m3Introducing nitrogen at a flow rate of/h, mixing for about 1h at 60-100 ℃, then heating to 180 ℃, carrying out heat treatment for 1h, cooling, extruding and filtering the rubber material prepared in the internal mixer by using a single screw rod, and preparing rubber compound and silicon rubber 1;
taking 100 parts of the prepared rubber compound silicon rubber, adding 0.7 part of vulcanizing agent into the rubber compound silicon rubber, repeatedly thinly passing the rubber compound silicon rubber on a double-roll rubber mixing mill, vulcanizing the rubber compound silicon rubber for 15min at the temperature of 130 ℃ and under the pressure of 22MPa to prepare a high-temperature vulcanized silicon rubber test piece with the thickness of 2mm, and measuring the material hardness to be 63Shore A and the tensile strength to be 63Shore AThe degree is 6.9MPa, the elongation at break is 287 percent, the tear strength is 27kN/mm, and the volume resistivity is 8.9 multiplied by 107Omega cm, the processability is poor, and the sintered condition is observed in a muffle furnace, so that the sintered sample has a compact appearance and a small shrinkage rate.
Embodiment 5 mainly changes the type selection of the conductive carbon black based on embodiment 1, and compared with embodiment 1, the mechanical properties of embodiment 5 are reduced, especially the tensile strength is reduced obviously, the elongation at break is not changed greatly, the volume resistivity is increased, the sintering in a muffle furnace and the porcelain forming are not changed obviously, and the processability is reduced, which shows that the mechanical properties, the conductivity (antistatic property) and the processability of the product are adversely affected by selecting the conductive carbon black with large specific surface and large particle size.
Finally, it should be noted that: the above embodiments are only used to illustrate the present invention and do not limit the technical solutions described in the present invention; thus, while the present invention has been described in detail with reference to the foregoing embodiments, it will be understood by those skilled in the art that various changes may be made and equivalents may be substituted; all such modifications and variations are intended to be included herein within the scope of this disclosure and the present invention and protected by the following claims.
Claims (10)
1. The high-temperature vulcanized silicone rubber with both conductivity and ceramic property is characterized by being prepared from the following raw materials in parts by weight:
80-130 parts of heat-vulcanized silicone rubber raw rubber,
20-50 parts of reinforcing filler fumed silica,
10-20 parts of a conductive medium,
0-10 parts of a structural control agent,
20-50 parts of a fluxing agent,
20-60 parts of a porcelain-forming filler,
0-5 parts of a coupling agent,
0-5 parts of heat stabilizer
0-5 parts of a release agent,
0-5 parts of a vulcanizing agent.
2. The high-temperature silicon sulfide rubber with both conductivity and ceramifiable property as claimed in claim 1, wherein the raw heat-curable silicon rubber is one or any combination of dimethyl silicon rubber, methyl-terminated methyl vinyl silicon rubber, vinyl-terminated methyl vinyl silicon rubber and methyl phenyl vinyl silicon rubber.
3. The high-temperature vulcanized silicone rubber with both conductivity and ceramifiable property as claimed in claim 2, wherein the raw material of the hot vulcanized silicone rubber is one or any combination of a dimethyl silicone rubber, a methyl-terminated methyl vinyl silicone rubber, a vinyl-terminated methyl vinyl silicone rubber, and a methyl phenyl vinyl silicone rubber with a molecular weight of 600000-900000 and a vinyl content of 0.01% -0.3%.
4. The high-temperature vulcanized silicone rubber with both conductivity and ceramifiable property as defined in claim 1, wherein the reinforcing filler is one or a combination of fumed silica and precipitated silica.
5. The high-temperature vulcanized silicone rubber compatible with electrical conductivity and ceramifiable according to claim 1, wherein the conductive medium is one or any combination of carbon black, graphite and carbon fiber; the specific surface area of carbon black in the conductive medium is 25-50m2The concentration of the catalyst is 1.0-1.5ml/g, the DBP oil absorption is 1.0-1.5ml/g, the primary particle size is 60-120nm, the iodine adsorption value is less than 50mg/g, the hydrochloric acid adsorption is 0.60-6.0ml/g, and the toluene coloring transmittance is 90-100%.
6. The high-temperature vulcanized silicone rubber with both conductivity and ceramifiable property as claimed in claim 1, wherein the structural control agent is hydroxyl silicone oil with a hydroxyl group mass fraction of 0.06% -0.12%.
7. The high-temperature vulcanized silicone rubber with both conductivity and ceramifiable property as claimed in claim 1, wherein the fluxing agent is one or any combination of glass powder with a softening point of 300-800 ℃, zinc borate and zinc oxide.
8. The high-temperature vulcanized silicone rubber compatible with electrical conductivity and ceramifiable according to claim 1, wherein the porcelain-forming filler is one or any combination of mica, wollastonite and kaolin.
9. The high-temperature vulcanized silicone rubber compatible with electrical conductivity and ceramifiable according to claim 1, wherein the coupling agent is a titanate coupling agent, a silane coupling agent or one of the titanate coupling agent and the silane coupling agent.
10. A method for preparing a compatible electrically conductive and ceramifiable high-temperature vulcanized silicone rubber according to any one of claims 1 to 9, comprising the steps of:
A) uniformly mixing the raw heat vulcanized silicone rubber, the reinforcing filler white carbon black and the structural control agent in an internal mixer to prepare a granular mixture capable of flowing freely;
B) uniformly mixing and heating the ceramic filler and the fluxing agent in an internal mixer, and then adding a coupling agent for surface treatment;
C) adding a coupling agent into a conductive medium for surface activation treatment;
D) conveying the raw materials obtained in the steps A), B) and C) into a kneading machine by an internal mixer, kneading and mixing at high temperature, vacuumizing, and filtering to obtain rubber compound and silicon rubber;
E) adding a vulcanizing agent into the prepared rubber compound silicone rubber, repeatedly thinly passing the rubber compound silicone rubber on a double-roll rubber mixing mill, vulcanizing the rubber compound silicone rubber for 15min at the temperature of 130 ℃ and under the pressure of 22MPa to prepare a test piece with the thickness of 2mm, and measuring various properties of the test piece;
wherein the high temperature in the internal mixer is 100-200 ℃; the temperature in the kneader is 100-200 ℃, the rotating speed is 30 +/-5 r/min, and the nitrogen flow is 5m3The kneading time is 2 hours, the single-screw basic filtration is carried out, and the filtration mesh number is 150-200 meshes; plasticating and sampling the rubber compound and the silicon rubber on a double-roll rubber mixing mill, adding a vulcanizing agent into the rubber compound and the silicon rubber, and mixing the mixture and the silicon rubber in a double-roll mixing millMixing uniformly, vulcanizing at 130 deg.C and 22MPa for 15min to obtain test piece with thickness of 2mm, and vulcanizing at 200 deg.C for 4 hr to measure various properties;
the method comprises the steps of testing the tensile strength, the elongation at break and the tearing strength of a sample by using a universal tensile testing machine, testing the Shore hardness of the sample by using a hardness tester, testing the volume resistance of the sample by using a resistance tester, testing the smoke density of the sample by using a smoke density tester, testing the oxygen index of the sample by using an oxygen index tester, observing the sintering condition by using a muffle furnace, testing the thermal property change of the sample in the process of room temperature to 1000 ℃ by using TG-DSC, and analyzing the composition and the change of combustion products of the sample at different temperatures by using FTIR and XRD.
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