WO2020025025A1 - Conductive liquid silicone rubber and preparation method and use thereof - Google Patents

Conductive liquid silicone rubber and preparation method and use thereof Download PDF

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Publication number
WO2020025025A1
WO2020025025A1 PCT/CN2019/098881 CN2019098881W WO2020025025A1 WO 2020025025 A1 WO2020025025 A1 WO 2020025025A1 CN 2019098881 W CN2019098881 W CN 2019098881W WO 2020025025 A1 WO2020025025 A1 WO 2020025025A1
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Prior art keywords
component
parts
walled carbon
silicone oil
carbon nanotubes
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PCT/CN2019/098881
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French (fr)
Chinese (zh)
Inventor
雷丽娟
郭鹏
史行知
黎哲辉
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江西蓝星星火有机硅有限公司
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Priority claimed from CN201810963080.9A external-priority patent/CN110791103B/en
Application filed by 江西蓝星星火有机硅有限公司 filed Critical 江西蓝星星火有机硅有限公司
Priority to US17/265,186 priority Critical patent/US20210253857A1/en
Priority to EP19844482.0A priority patent/EP3835362A4/en
Publication of WO2020025025A1 publication Critical patent/WO2020025025A1/en

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    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K3/00—Use of inorganic substances as compounding ingredients
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • 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

Definitions

  • the invention relates to the technical field of silicone rubber, in particular to a conductive liquid silicone rubber.
  • the electrical stress control material needs to have an even distribution of the electrical stress at the shield cutoff and the terminal shield cutoff of the cable's middle joint.
  • conductive silicone rubber has a series of excellent characteristics such as high temperature resistance, low pressure change, and high rebound due to its unique "organic-inorganic" co-existing main chain structure. Silicone rubber material has good electrical conductivity.
  • the shrinkage is extremely small, deep vulcanization can be achieved, and rapid vulcanization can be achieved under heating. It has excellent physical and mechanical properties and electrical properties. Because of its low energy consumption, less material consumption and high production efficiency, it can realize the advantages of automated production, making it widely used in the power industry.
  • the conductive fillers such as conductive carbon black, conductive montmorillonite, metal powder, etc.
  • the conductive fillers used in the conductive liquid silicone rubber used as cable accessories in the market currently need to be added in large quantities to meet the conductive needs, leading to the rubber's superior performance. Such as mechanical strength, toughness, elasticity and viscosity are greatly affected. Previous studies have shown that conductive carbon black with a high added amount is often used as a conductive filler, and decarburization may occur during long-term use, resulting in unstable resistivity, which makes the electrical stress control of cable accessories risky.
  • Chinese patent CN1605604A uses silver-plated glass powder, silver-plated nickel powder, silver-plated copper powder, silver-plated aluminum powder, and silver powder as conductive fillers to prepare highly conductive rubber, but the amount of conductive filler added is as high as 200 to 600 parts by mass, resulting in The mechanical properties of the material are poor.
  • the conductive fillers used in the Chinese patents CN 104327509A and CN103665875A are acetylene carbon black or other fillers. They all have the disadvantages of large amounts of acetylene carbon black addition, poor mechanical properties of conductive silicone rubber, and complicated processes.
  • Chinese patent CN106589953A adopts the conductive powder composite system with different particle sizes and shapes and the matching of conductive powders of different sizes to achieve the ideal powder accumulation effect, and then obtain highly conductive liquid silicon at a low filling amount. rubber.
  • the conductive powders used are gold powder, graphite powder, etc., and they are all micron-level, which is not conducive to environmental protection and physical health.
  • Cisenotubes have been used in conductive rubbers because of their high electrical conductivity and excellent mechanical properties.
  • Chinese patent CN103937258A discloses a method for preparing conductive silicone rubber with high resilience. The method uses modified multi-wall carbon nanotubes or conductive carbon black as a conductive filler to prepare a conductive silicone rubber with high resilience.
  • the modified conductive filler is added to the raw silicone rubber before vulcanization, rather than to the raw materials for rubber preparation, and the added amount is 5 to 40 parts, so that the tensile strength is mostly 4 to 6 MPa.
  • the elongation at break is mostly below 200%, which greatly limits its application.
  • Single-walled carbon nanotube is a kind of one-dimensional quantum material with a special structure. It consists of several layers to dozens of layers of coaxial circular tubes, mainly composed of carbon atoms arranged in hexagons. A fixed distance is maintained between layers. It is about 0.34 nm, the diameter is 1-50 nm, and the length is more than 5 ⁇ m.
  • Single-walled carbon nanotubes have good electrical conductivity, high elasticity and strength, thermal stability and weather resistance. Even a small amount of filling can meet the requirements of the material's conductive properties. In addition, the small amount of filling can maintain the strength and toughness of the silicone rubber itself. And viscosity, while maintaining stability in complex environments.
  • single-walled carbon nanotubes are an ideal conductive filler for liquid glue.
  • the use of single-walled carbon nanotubes to prepare conductive liquid silicone rubber materials, especially for cable accessory applications, is still blank at home and abroad.
  • how to ensure that the single-walled carbon nanotubes are sufficiently uniformly dispersed in the rubber system with a low filling amount is also an urgent problem to be solved.
  • the purpose of the present invention is to overcome the shortcomings of the prior art and provide a single-walled carbon nanotube polyorganosiloxane low-filling conductive liquid silicone rubber material.
  • the conductive liquid silicone rubber material provided by the present invention not only has good electrical conductivity, but also has high mechanical strength, good processability, and strong weather resistance. It can be rapidly cured and molded at high temperatures without any by-products.
  • the present invention provides a conductive liquid silicone rubber, and the conductive filler used in the conductive liquid silicone rubber includes single-walled carbon nanotubes.
  • the conductive liquid silicone rubber provided by the present invention uses single-walled carbon nanotubes as a conductive filler.
  • liquid silicone rubber has good electrical conductivity
  • a low-filled single-walled carbon nanotube with a mass percentage of 0.1 to 10% (relative to the total mass of the liquid silicone rubber) is added to the liquid silicone Conductive filler.
  • the single-walled carbon nanotube according to the present invention is a one-dimensional quantum material with a special structure, which is mainly composed of carbon atoms arranged in hexagons to form a coaxial circular tube of several layers to dozens of layers, between layers.
  • the fixed distance is about 0.34 nm
  • the diameter is 1 nm to 50 nm (preferably 1.2 to 50 nm or 2 to 50 nm)
  • the length is greater than 5 ⁇ m.
  • the present invention has been found through a large number of practices that when the single-walled carbon nanotubes have a specific diameter and length, for example, a diameter of 1 nm to 50 nm and a length of more than 5 ⁇ m, preferably a diameter of 1.2 nm to 2 nm and a length of more than 10 ⁇ m, further preferably a diameter of 1.2 nm
  • the length is ⁇ 2nm and the length is 12 ⁇ m, it has sufficient aspect ratio and specific surface area. Dispersing it in liquid silicone rubber can ensure that the final product has good electrical conductivity, and then it is used in cable accessories and other fields.
  • the present invention preferably adopts a two-step premixing method.
  • single-walled carbon nanotubes and polyorganosiloxane are mixed in advance to obtain a premix.
  • the mass percentage of the single-walled carbon nanotubes in the premix is 5-20%.
  • the premix of single-walled carbon nanotubes and polyorganosiloxane is mixed with a base rubber to prepare a masterbatch.
  • the mass ratio of the premix of the single-walled carbon nanotubes to the base rubber contained in the masterbatch of the present invention is (1-10): 100, and more preferably (3.8-10): 100.
  • the masterbatch is mixed with other components and vulcanized to prepare a rubber.
  • the type of polyorganosiloxane mixed with carbon nanotubes to obtain a premix can be determined by those skilled in the art according to actual needs.
  • the base rubber according to the present invention is a basic component for preparing conductive liquid silicone rubber, and can be prepared by using existing materials and processes in the art.
  • the base rubber of the present invention preferably includes a vinyl silicone oil, white carbon black, silazane, and deionization that are thoroughly mixed uniformly.
  • the base gum includes 30 to 70 parts of vinyl silicone oil, 15 to 40 parts of white carbon black, 5 to 15 parts of silazane, and 1 to 10 parts of deionized water; further preferably, the The base rubber includes 50 to 65 parts of vinyl silicone oil, 25 to 30 parts of white carbon black, 7 to 9 parts of silazane, and 3 to 6 parts of deionized water.
  • the base rubber of the present invention is preferably prepared by a method including the following steps: taking methyl vinyl silicone oil, white carbon black, silazane, and deionized water at 60-90 ° C, Mix well under the protection of an inert atmosphere, then raise the temperature to 130-180 ° C and begin to evacuate for 2 to 4 hours. Keep the temperature at 130-180 ° C when evacuating, and then reduce the temperature to 120-140 ° C after adding the vacuum. Vinyl silicone oil, stir well to obtain.
  • the vinyl silicone oil used for preparing the base rubber is preferably a mixture of one or two of a terminal vinyl silicone oil and a polyvinyl silicone oil.
  • the viscosity of the terminal vinyl silicone oil used in the present invention does not exceed 150,000 mPa ⁇ s, preferably 60,000 to 100,000 mPa ⁇ s.
  • the terminal vinyl silicone oil according to the present invention is preferably an alkyl vinyl silicone oil, and more preferably a methyl vinyl silicone oil. The present invention has found through a lot of practice that the mechanical properties of the conductive liquid silicone rubber can be improved by optimizing the specific component selection, combination mode, and viscosity of the vinyl silicone oil.
  • the silica used in the preparation of the base rubber is preferably gas-phase silica which is grafted in situ through a treatment agent such as silazane, and has a specific surface area of not less than 200 m 2 / g, and preferably 280 to 320 m 2 / g.
  • the silazane used for preparing the base rubber is preferably at least one of hexamethylsilazane, tetramethyldivinylsilazane, heptamethyldisilazane, vinyl mono-terminated silazane, or the like, or A mixture of the two is more preferably hexamethylsilazane and / or tetramethyldivinylsilazane.
  • the solution provided by the present invention preferably comprises a base rubber prepared from a premix of single-walled carbon nanotubes and polyorganosiloxane and the above parts by weight of raw materials at a mass ratio of 1 to 10: 100 in Mix on a three-roll mill, preferably until the particle diameter of the resulting mixture is 0.1 ⁇ m to 20 ⁇ m to obtain a conductive liquid silicone rubber masterbatch.
  • the present invention has found through a large number of practices that mixing the premix of the single-walled carbon nanotubes and the base rubber on a three-roll mill according to the above ratio can ensure that the single-walled carbon nanotubes are uniformly and fully dispersed in the masterbatch, and then ensure that Evenly and fully dispersed in the final product, making liquid silicone rubber have excellent electrical conductivity and excellent mechanical properties.
  • the present invention preferably includes, in addition to the masterbatch, raw materials for preparing the liquid silicone rubber including: component A, component B, catalyst, and Inhibitor.
  • the raw materials for preparing the liquid silicone rubber include: 100 parts of the masterbatch, component A is 10 to 100 parts, preferably 10 to 65 parts, more preferably 10 to 35 parts, and component B is 0.4 to 10 parts, preferably 0.4 to 5 parts, the catalyst is 0.002 to 0.02 parts, preferably 0.003 to 0.01 parts, and the inhibitor is 0.02 to 1 part, preferably 0.02 to 0.5 parts.
  • the component A is a mixture of one or more of the compounds represented by the general formula (1):
  • n represents an integer of 0 to 100, preferably an integer of 20 to 50; m represents an integer of 70 to 4000, preferably an integer of 150 to 2000; R is a saturated hydrocarbon group such as methyl, Ethyl, propyl, butyl, etc .; R 1 is an unsaturated hydrocarbon group, such as vinyl, allyl, allyl, etc .; R 2 is a saturated or unsaturated hydrocarbon group, which may be methyl, ethyl, vinyl, Any of propyl, allyl, butyl, allyl and the like.
  • the component A is preferably selected from the group consisting of: a vinyl-terminated silicone oil in which R 1 is a vinyl group and R 2 is a saturated hydrocarbon group; and / or a side chain vinyl silicone oil in which R 1 is a saturated hydrocarbon group and R 2 is a vinyl , And / or R 1 and R 2 are both vinyl end-side vinyl silicone oils.
  • the mass content of the vinyl group in the component A is preferably 0.05 to 5% of the total amount of the component A.
  • the component B is a mixture of one or more of the compounds represented by the general formulae (2) and (3):
  • x is an integer of 8 to 200, preferably an integer of 10 to 100;
  • y is an integer of 0 to 60, preferably an integer of 0 to 20;
  • R 3 may be a methyl group or a hydrogen group Or silyl;
  • R 4 may be methyl, ethyl, propyl or phenyl.
  • a is an integer of 1 to 300;
  • R 5 may be a methyl group, an ethyl group, or a hydrogen group.
  • R 5 is a hydrogen group.
  • the B component is a mixture of one or more of the compounds of the general formulae (2) and (3), at least one of the compounds of the general formulae (2) and (3) has a SiH bond.
  • Part B of the present invention is preferably selected from the following components: R 3 is a hydrogen group and y is greater than 1 and the side chain ends are SiH-containing silicone oil, and / or R 3 is a hydrogen end group and y is equal to 0 A hydrogen-containing silicone oil, and / or a side-chain hydrogen-containing silicone oil in which R 3 is a saturated hydrocarbon group and y is greater than 1, and / or a hydrogen-containing silicone resin in which R 5 is a hydrogen group.
  • the mass content of the Si-H group in the component B is 3% -50% of the total amount of the component B, and more preferably, at least one of the component B contains three Si-H functional groups thus form a three-dimensional network structure with a certain cross-link density.
  • the catalyst is preferably a Custer catalyst.
  • the inhibitor may be selected from 1-ethynyl-1-cyclohexanol, 2-methyl-3-butyn-ol, and 3,5-dimethyl-1-hexyn-3-ol and 3-methyl-1 -At least one of dodecyn-3-ol.
  • the invention also provides a method for preparing the liquid silicone rubber.
  • the preparation method includes the following steps: first, pre-mixing the single-walled carbon nanotubes and the polyorganosiloxane to obtain a premix, preferably, the single-walled carbon nanotubes occupy the premix
  • the mass percentage is 5 to 20%.
  • the premix is mixed with a base rubber to prepare a masterbatch, and the masterbatch is mixed with other raw materials to prepare a conductive liquid silicone rubber through vulcanization.
  • the mass ratio of the premix contained in the masterbatch to the base rubber is (1 to 10): 100, more preferably (3.8 to 10): 100.
  • other raw materials include: a component , B component, catalyst and inhibitor.
  • the preparation method includes the following steps: mixing a masterbatch containing single-walled carbon nanotubes, a catalyst, and at least one component A, and vacuuming and defoaming to obtain component A; and containing single-walled carbon nanotubes
  • the masterbatch, at least one component A, at least one component B, and at least one inhibitor of the tube are mixed uniformly, and degassed under vacuum to obtain component B; the components A and B are mixed in equal proportions Uniform, cured to obtain test pieces, vulcanized, that is.
  • the curing temperature is preferably 130 to 170 ° C; the curing temperature is preferably 180 to 220 ° C.
  • the preparation method includes the following specific steps:
  • Preparation and vulcanization of component AB mixing the masterbatch, catalyst and at least one component A uniformly, degassing under vacuum to obtain component A; the masterbatch, at least one component A , At least one component B and at least one inhibitor are mixed uniformly, and degassed under vacuum to obtain component B; the components A and B are mixed in equal proportions, cured to obtain test pieces, and vulcanized to obtain .
  • the liquid silicone rubber provided by the invention has excellent comprehensive properties, including physical and mechanical properties such as electrical conductivity, tensile strength, elongation at break and the like.
  • the invention also protects the application of the liquid silicone rubber in preparing power grids and / or cable accessories.
  • the present invention for the first time uses a single-walled carbon nanotube as a conductive filler to prepare a single-walled carbon nanotube conductive liquid silicone rubber composite material.
  • it uses two steps of pre-mixing and formula design to achieve Effectively disperse single-walled carbon nanotubes in the entire system with a very small amount of addition. While reducing product viscosity and improving processing performance, it also prevents problems such as agglomeration, sedimentation, and precipitation, thereby forming an effective conductive network path.
  • a conductive material having a volume resistivity of less than 100 ⁇ ⁇ cm was prepared.
  • the conductive liquid silicone rubber provided by the invention not only has a low amount of conductive filler, excellent electrical properties, but also excellent physical and mechanical properties and weather resistance, and has no pollutants generated during the vulcanization process, the production process is simple and free of pollution, and the operation is convenient.
  • the single-walled carbon nanotubes used in the following examples are commercially available, with a diameter of about 1.5 nm (in the range of 1.2 nm to 2 nm) and a length of 12 ⁇ m.
  • This embodiment provides a single-walled carbon nanotube conductive liquid silicone rubber, which is prepared by the following method:
  • premix premixing the single-walled carbon nanotubes and polyorganosiloxane to obtain a premix, wherein the mass percentage of the single-walled carbon nanotubes to the premix is 10 %.
  • component AB 100 parts of the above-mentioned masterbatch, 1,18 parts of vinyl-terminated silicone oil having a viscosity of 20,000 mPa ⁇ s, 5 parts of side-chain vinyl silicone oil having a viscosity of 1000 mPa ⁇ s, and 0.02 parts of card
  • This type of catalyst is stirred and dispersed in a planetary mixer for 35 minutes, mixed evenly, and then evacuated and degassed to obtain a conductive liquid silicone rubber component A.
  • the equal proportion of component A and the proportion of component B are mixed uniformly, and then cured at 150 ° C for 10 minutes to prepare a 2mm test piece.
  • the test piece is secondarily vulcanized at 200 ° C for 4 hours to obtain single-walled carbon nanotubes.
  • Conductive liquid silicone rubber
  • This embodiment provides a single-walled carbon nanotube conductive liquid silicone rubber, which is prepared by the following method:
  • This embodiment provides a single-walled carbon nanotube conductive liquid silicone rubber, which is prepared by the following method:
  • component AB 100 parts of the above-mentioned masterbatch 3, 11 parts of the terminal vinyl silicone oil having a viscosity of 100,000 mPa ⁇ s, 3.5 parts of the side chain vinyl silicone oil having a viscosity of 1000 mPa ⁇ s, and 0.015 parts of card Stir catalyst, stir and disperse in a planetary mixer for 30-40min, mix well and then vacuum degassing to obtain conductive liquid silicone rubber A component 1.
  • This embodiment provides a single-walled carbon nanotube conductive liquid silicone rubber, which is prepared by the following method:
  • component AB 100 parts of the above-mentioned masterbatch 4, 20 parts of the vinyl-terminated silicone oil having a viscosity of 20,000 mPa ⁇ s, 2 parts of the side-chain vinyl silicone oil having a viscosity of 1000 mPa ⁇ s, and 0.025 parts of card
  • This type of catalyst is stirred and dispersed in a planetary mixer for 30-40 minutes, mixed evenly, and then evacuated and degassed to obtain conductive liquid silicone rubber component A 4.
  • This embodiment provides a single-walled carbon nanotube conductive liquid silicone rubber, which is prepared by the following method:
  • component AB 100 parts of the above-mentioned masterbatch 5, 15 parts of the terminal vinyl silicone oil having a viscosity of 20,000 mPa ⁇ s, 6 parts of the vinyl vinyl end oil having a mass content of 2.36%, 0.018 Part of Custer catalyst, stir and disperse in a planetary mixer for 30-40min, and mix and then vacuum degassing to obtain conductive liquid silicone rubber component A5.
  • This embodiment provides a single-walled carbon nanotube conductive liquid silicone rubber. Compared with Example 4, the only difference is that: when preparing a master batch, a planetary mixer is used instead of mixing on a three-roll mill;
  • component AB 100 parts of masterbatch 7, 20 parts of vinyl-terminated silicone oil having a viscosity of 20,000 mPa ⁇ s, 2 parts of side-chain vinyl silicone oil having a viscosity of 1000 mPa ⁇ s, and 0.025 parts of card
  • This type of catalyst is stirred and dispersed in a planetary mixer for 30-40 minutes, mixed evenly, and then evacuated and degassed to obtain conductive liquid silicone rubber A component 7.
  • a single-walled carbon nanotube conductive liquid silicone rubber is provided. Compared with Example 1, the only difference is that a single-walled carbon nanotube is used to replace the premix of the single-walled carbon nanotube and polyorganosiloxane. Single-walled carbon nanotubes are directly mixed with the base glue to prepare a masterbatch.
  • a single-walled carbon nanotube conductive liquid silicone rubber is provided. Compared with Example 1, the only difference is that a premix of polyorganosiloxane and single-walled carbon nanotubes is not prepared, and the premix and base are not prepared. The glue is mixed to obtain a master batch, and the untreated single-walled carbon nanotubes are directly mixed with the A and B components.
  • Example 2 Provide a single-walled carbon nanotube conductive liquid silicone rubber. Compared with Example 1, the only difference is that after preparing a premix of single-walled carbon nanotubes, the premix is not mixed with the base rubber to prepare a masterbatch. Instead, the premix is directly mixed with the A and B components.
  • GB / T2439-2001 is used as the test method for volume resistance and calculated volume resistivity; ASTM D412-1998a (2002) e1 is used for the test method for tensile strength and elongation at break; ASTM D2240 is used for the test method for hardness; The test method adopts ASTM D624; the test method of rebound rate adopts ASTM D7121-2005 (2012).
  • the two-step premixing method of preparing a premix and mixing the premix with a base rubber to obtain a masterbatch achieves effective dispersion of single-walled carbon nanotubes in a small amount of addition.
  • the obtained liquid silicone rubber not only has good electrical conductivity, but also has excellent mechanical properties, including electrical conductivity, tensile strength, elongation at break, and the like. No meaningful volume resistivity measurement results can be obtained without the two-step premixing method described above (as shown in Comparative Example 3), and there is no step to prepare a premix by mixing single-walled carbon nanotubes with polyorganosiloxane.
  • the conductive liquid silica gel provided by the invention has good electrical conductivity and excellent mechanical strength, at the same time has the characteristics of low viscosity, good fluidity and easy injection molding.
  • Increasing the addition ratio of single-walled carbon nanotubes in a certain range increases the conductivity of the product and has little impact on the mechanical properties, which fully meets the application needs of the power industry.
  • the same proportion of single-walled carbon nanotube powder filler is directly added, the carbon nanotubes are unevenly dispersed, the product appearance is uneven, and the tensile properties are poor.
  • the premix is added on the one hand, which is environmentally friendly and clean, on the other hand, the nanotubes are uniformly dispersed, the mechanical properties are excellent, and the electrical properties are good.

Abstract

Disclosed is a conductive liquid silicone rubber employing a conductive filler comprising single-walled carbon nanotubes. Single-walled carbon nanotubes are used herein for the first time as a conductive filler to prepare a conductive liquid silicone rubber complex material comprising the single-walled carbon nanotubes. By means of a two-step pre-mixing operation and a specific formula design, dispersion of single-walled carbon nanotubes, which have been added in the smallest quantity, throughout a system is effectively achieved, enabling a reduction in product viscosity and and enhancing workability, while preventing problems such as agglomeration, sedimentation, precipitation etc. Accordingly, an effective conductive network pathway is formed, allowing preparation of a conductive material having a volume resistivity of less than 100 Ω⋅cm. The resulting conductive liquid silicone rubber has excellent electrical performance for a small quantity of conductive filler added, good mechanical performance and good weather resistance. Moreover, the production process thereof is simple, pollution-free, and easy to carry out, and does not generate pollutants during a curing process.

Description

一种导电液体硅橡胶及其制备方法与应用Conductive liquid silicone rubber and preparation method and application thereof 技术领域Technical field
本发明涉及硅橡胶技术领域，具体涉及一种导电液体硅橡胶。The invention relates to the technical field of silicone rubber, in particular to a conductive liquid silicone rubber.
背景技术Background technique
随着科技和生活水平的提高，工业自动化机械化生产、电子仪器和设备使用频繁、大型家用电器增多，电力的稳定传输是现阶段面临的重大挑战。要使电缆长期运行，需要电应力控制材料在电缆中间接头的屏蔽切断处和末端屏蔽切断处电应力分布均匀。导电硅橡胶作为一种特种硅橡胶材料，由于其独特的“有机-无机”共同存在的主链结构，使其具有耐高温、低压变、高回弹等一系列的优异特性，同时又赋予了硅橡胶材料良好的导电性。尤其是导电液体硅橡胶，交联固化过程中无副产物产生，收缩性极小，能深层硫化，在加热下可实现快速硫化，具有优良的物理机械性能和电性能。由于其使用时能耗低、物耗少、生产效率高，可实现自动化生产的优势，使其在电力行业得到广泛的应用。但是目前市场上用作电缆附件的导电液体硅橡胶所采用的导电填料(如导电炭黑、导电蒙脱土、金属粉末等)，须大量加入才能满足导电需求，从而导致橡胶本身的优势性能，如机械强度、韧性、弹性和粘度等受到很大影响。已有研究表明，常用高添加量的导电炭黑作为导电填料，长期使用可能会出现脱碳的问题，造成电阻率不稳定，从而使得电缆附件的电应力控制有风险。With the improvement of technology and living standards, industrial automation mechanized production, frequent use of electronic instruments and equipment, and increased use of large household appliances, stable transmission of power is a major challenge at this stage. In order to make the cable run for a long time, the electrical stress control material needs to have an even distribution of the electrical stress at the shield cutoff and the terminal shield cutoff of the cable's middle joint. As a special silicone rubber material, conductive silicone rubber has a series of excellent characteristics such as high temperature resistance, low pressure change, and high rebound due to its unique "organic-inorganic" co-existing main chain structure. Silicone rubber material has good electrical conductivity. Especially for conductive liquid silicone rubber, no by-products are generated during the cross-linking and curing process, the shrinkage is extremely small, deep vulcanization can be achieved, and rapid vulcanization can be achieved under heating. It has excellent physical and mechanical properties and electrical properties. Because of its low energy consumption, less material consumption and high production efficiency, it can realize the advantages of automated production, making it widely used in the power industry. However, the conductive fillers (such as conductive carbon black, conductive montmorillonite, metal powder, etc.) used in the conductive liquid silicone rubber used as cable accessories in the market currently need to be added in large quantities to meet the conductive needs, leading to the rubber's superior performance. Such as mechanical strength, toughness, elasticity and viscosity are greatly affected. Previous studies have shown that conductive carbon black with a high added amount is often used as a conductive filler, and decarburization may occur during long-term use, resulting in unstable resistivity, which makes the electrical stress control of cable accessories risky.
中国专利CN1605604A分别以镀银玻璃粉、镀银镍粉、镀银铜粉、镀银铝粉和银粉为导电填料，制备了高导电橡胶，但导电填料的添加量高达200～600质量份，导致材料的机械性能较差。中国专利CN 104327509A和CN103665875A等专利中所用导电填料为乙炔炭黑或其他填料，都存在乙炔炭黑添加量较大，导电硅橡胶机械性能较差，工艺较复杂等缺点。中国专利CN106589953A通过采用不同粒径、不同形状的导电粉体复合体系以及大小粒径的导电粉体搭配，实现了理想的粉体堆积效果，进而在低填充量下获得了高导电性的液体硅橡胶。但是其所采用的导电粉体为金粉、石墨粉等，且均为微米级，不利于环境保护和身体健康。Chinese patent CN1605604A uses silver-plated glass powder, silver-plated nickel powder, silver-plated copper powder, silver-plated aluminum powder, and silver powder as conductive fillers to prepare highly conductive rubber, but the amount of conductive filler added is as high as 200 to 600 parts by mass, resulting in The mechanical properties of the material are poor. The conductive fillers used in the Chinese patents CN 104327509A and CN103665875A are acetylene carbon black or other fillers. They all have the disadvantages of large amounts of acetylene carbon black addition, poor mechanical properties of conductive silicone rubber, and complicated processes. Chinese patent CN106589953A adopts the conductive powder composite system with different particle sizes and shapes and the matching of conductive powders of different sizes to achieve the ideal powder accumulation effect, and then obtain highly conductive liquid silicon at a low filling amount. rubber. However, the conductive powders used are gold powder, graphite powder, etc., and they are all micron-level, which is not conducive to environmental protection and physical health.
碳纳米管因其高导电性以及优异的力学性能，已经被用于导电橡胶中。中国专利CN103937258A公开了一种具有高回弹性的导电硅橡胶的制备方法，该方法将多壁碳纳米 管或导电炭黑进行改性后作为导电填料，制得具有高回弹性的导电硅橡胶，但是该改性后的导电填料是加入到硫化前的硅橡胶生胶中，而不是加入到制备橡胶的原料中，且其添加量为5～40份，致使拉伸强度大多在4～6MPa，断裂伸长率大多低于200％，极大地限制了其应用。Carbon nanotubes have been used in conductive rubbers because of their high electrical conductivity and excellent mechanical properties. Chinese patent CN103937258A discloses a method for preparing conductive silicone rubber with high resilience. The method uses modified multi-wall carbon nanotubes or conductive carbon black as a conductive filler to prepare a conductive silicone rubber with high resilience. However, the modified conductive filler is added to the raw silicone rubber before vulcanization, rather than to the raw materials for rubber preparation, and the added amount is 5 to 40 parts, so that the tensile strength is mostly 4 to 6 MPa. The elongation at break is mostly below 200%, which greatly limits its application.
单壁碳纳米管是一种具有特殊结构的一维量子材料，主要由呈六边形排列的碳原子构成数层到数十层的同轴圆管，层与层之间保持固定的距离，约0.34nm，直径为1～50nm，长度大于5μm。单壁碳纳米管具有良好的导电性能、极高的弹性和强度、热稳定性和耐候性，即使微量填充，亦可满足材料的导电性能要求，另外微量填充能保持硅橡胶本身的强度、韧性及粘度，同时能在复杂的环境中保持稳定。因此单壁碳纳米管是一种理想的液体胶导电填料。在已知范围内，采用单壁碳纳米管制备导电液体硅橡胶材料，尤其是用于电缆附件应用，在国内外尚属空白。同时，如何以低填充量保证单壁碳纳米管在橡胶体系中充分均匀分散也是亟待解决的问题。Single-walled carbon nanotube is a kind of one-dimensional quantum material with a special structure. It consists of several layers to dozens of layers of coaxial circular tubes, mainly composed of carbon atoms arranged in hexagons. A fixed distance is maintained between layers. It is about 0.34 nm, the diameter is 1-50 nm, and the length is more than 5 μm. Single-walled carbon nanotubes have good electrical conductivity, high elasticity and strength, thermal stability and weather resistance. Even a small amount of filling can meet the requirements of the material's conductive properties. In addition, the small amount of filling can maintain the strength and toughness of the silicone rubber itself. And viscosity, while maintaining stability in complex environments. Therefore, single-walled carbon nanotubes are an ideal conductive filler for liquid glue. Within the known scope, the use of single-walled carbon nanotubes to prepare conductive liquid silicone rubber materials, especially for cable accessory applications, is still blank at home and abroad. At the same time, how to ensure that the single-walled carbon nanotubes are sufficiently uniformly dispersed in the rubber system with a low filling amount is also an urgent problem to be solved.
发明内容Summary of the invention
本发明的目的在于克服现有技术的缺陷，提供一种单壁碳纳米管聚有机硅氧烷低填充的导电液体硅橡胶材料。本发明提供的导电液体硅橡胶材料不仅导电性能好、而且机械强度高、可加工性能好、耐候性强，高温下可以快速固化成型，无副产物产生。The purpose of the present invention is to overcome the shortcomings of the prior art and provide a single-walled carbon nanotube polyorganosiloxane low-filling conductive liquid silicone rubber material. The conductive liquid silicone rubber material provided by the present invention not only has good electrical conductivity, but also has high mechanical strength, good processability, and strong weather resistance. It can be rapidly cured and molded at high temperatures without any by-products.
具体而言，本发明提供了一种导电液体硅橡胶，所述导电液体硅橡胶采用的导电填料包括单壁碳纳米管。Specifically, the present invention provides a conductive liquid silicone rubber, and the conductive filler used in the conductive liquid silicone rubber includes single-walled carbon nanotubes.
优选地，本发明提供的导电液体硅橡胶以单壁碳纳米管作为导电填料。Preferably, the conductive liquid silicone rubber provided by the present invention uses single-walled carbon nanotubes as a conductive filler.
为了确保液体硅橡胶具有良好的导电性能，本发明优选所述液体硅胶中添加质量百分比为0.1～10％(相对于该液体硅橡胶的总质量计)的低填充量的单壁碳纳米管作为导电填料。In order to ensure that the liquid silicone rubber has good electrical conductivity, it is preferred in the present invention that a low-filled single-walled carbon nanotube with a mass percentage of 0.1 to 10% (relative to the total mass of the liquid silicone rubber) is added to the liquid silicone Conductive filler.
本发明所述单壁碳纳米管是一种具有特殊结构的一维量子材料，其主要由呈六边形排列的碳原子构成数层到数十层的同轴圆管，层与层之间保持固定的距离约0.34nm，直径为1nm～50nm(优选1.2～50nm或2～50nm)，长度大于5μm。本发明通过大量实践发现，当所述单壁碳纳米管具有特定直径和长度，例如直径为1nm～50nm且长度大于5μm，优选直径为1.2nm～2nm且长度大于10μm，进一步优选直径为1.2nm～2nm且长度为12μm时，具有足够的长径比和比表面积，将其分散于液体硅橡胶中，可以确保最终产品具有良 好的导电性能，继而应用于电缆附件等领域。The single-walled carbon nanotube according to the present invention is a one-dimensional quantum material with a special structure, which is mainly composed of carbon atoms arranged in hexagons to form a coaxial circular tube of several layers to dozens of layers, between layers. The fixed distance is about 0.34 nm, the diameter is 1 nm to 50 nm (preferably 1.2 to 50 nm or 2 to 50 nm), and the length is greater than 5 μm. The present invention has been found through a large number of practices that when the single-walled carbon nanotubes have a specific diameter and length, for example, a diameter of 1 nm to 50 nm and a length of more than 5 μm, preferably a diameter of 1.2 nm to 2 nm and a length of more than 10 μm, further preferably a diameter of 1.2 nm When the length is ～ 2nm and the length is 12μm, it has sufficient aspect ratio and specific surface area. Dispersing it in liquid silicone rubber can ensure that the final product has good electrical conductivity, and then it is used in cable accessories and other fields.
为了将单壁碳纳米管充分均匀分散于液体硅橡胶中，本发明优选采用两步骤的预先混合方式。In order to fully disperse the single-walled carbon nanotubes in the liquid silicone rubber, the present invention preferably adopts a two-step premixing method.
首先，将单壁碳纳米管与聚有机硅氧烷进行预先混合，得到预混物。作为本发明的一种优选方案，所述单壁碳纳米管占所述预混物的质量百分比为5～20％。First, single-walled carbon nanotubes and polyorganosiloxane are mixed in advance to obtain a premix. As a preferred solution of the present invention, the mass percentage of the single-walled carbon nanotubes in the premix is 5-20%.
其次，将单壁碳纳米管与聚有机硅氧烷的所述预混物与基胶混合，制备得到母胶。优选的，本发明所述母胶中含有的单壁碳纳米管的所述预混物与基胶的质量比为(1～10):100，更优选(3.8～10):100。再将所述母胶与其它组分混合、硫化制备橡胶。Secondly, the premix of single-walled carbon nanotubes and polyorganosiloxane is mixed with a base rubber to prepare a masterbatch. Preferably, the mass ratio of the premix of the single-walled carbon nanotubes to the base rubber contained in the masterbatch of the present invention is (1-10): 100, and more preferably (3.8-10): 100. The masterbatch is mixed with other components and vulcanized to prepare a rubber.
其中，与碳纳米管混合以获得预混物的聚有机硅氧烷的种类可由本领域技术人员根据实际需要确定。The type of polyorganosiloxane mixed with carbon nanotubes to obtain a premix can be determined by those skilled in the art according to actual needs.
本发明所述的基胶是制备导电液体硅橡胶的基础成分，可采用本领域现有的原料和工艺制备而成。为了确保成为单壁碳纳米管的良好分散介质进而确保所得终产品具有优异的导电性能，本发明优选所述基胶中包括充分混合均匀的乙烯基硅油、白炭黑、硅氮烷和去离子水；更优选地，所述基胶中包括30～70份乙烯基硅油、15～40份白炭黑、5～15份硅氮烷和1～10份去离子水；进一步优选地，所述基胶中包括50～65份乙烯基硅油、25～30份白炭黑、7～9份硅氮烷和3～6份去离子水。The base rubber according to the present invention is a basic component for preparing conductive liquid silicone rubber, and can be prepared by using existing materials and processes in the art. In order to ensure that it becomes a good dispersion medium for single-walled carbon nanotubes and further ensures that the resulting final product has excellent electrical conductivity, the base rubber of the present invention preferably includes a vinyl silicone oil, white carbon black, silazane, and deionization that are thoroughly mixed uniformly. Water; more preferably, the base gum includes 30 to 70 parts of vinyl silicone oil, 15 to 40 parts of white carbon black, 5 to 15 parts of silazane, and 1 to 10 parts of deionized water; further preferably, the The base rubber includes 50 to 65 parts of vinyl silicone oil, 25 to 30 parts of white carbon black, 7 to 9 parts of silazane, and 3 to 6 parts of deionized water.
为了使各组分之间充分混合，优选本发明所述基胶由包括如下步骤的方法制备：取甲基乙烯基硅油、白炭黑、硅氮烷和去离子水，在60～90℃、惰性气氛保护下充分混合，然后升温到130～180℃后开始抽真空2～4h,抽真空时保持温度在130～180℃，抽真空结束后降温到120～140℃，再加入稀释用甲基乙烯基硅油，搅拌均匀，即得。In order to fully mix the components, the base rubber of the present invention is preferably prepared by a method including the following steps: taking methyl vinyl silicone oil, white carbon black, silazane, and deionized water at 60-90 ° C, Mix well under the protection of an inert atmosphere, then raise the temperature to 130-180 ° C and begin to evacuate for 2 to 4 hours. Keep the temperature at 130-180 ° C when evacuating, and then reduce the temperature to 120-140 ° C after adding the vacuum. Vinyl silicone oil, stir well to obtain.
制备基胶采用的乙烯基硅油优选为端基乙烯基硅油、多乙烯基硅油中的一种或两种的混合。为了确保单壁碳纳米管在液体硅橡胶中更好的分散，本发明采用的端基乙烯基硅油粘度不超过150000mPa·s，优选为60000～100000mPa·s。本发明所述端基乙烯基硅油优选为烷基乙烯基硅油，更优选为甲基乙烯基硅油。本发明通过大量实践发现，通过对乙烯基硅油的具体组分选择、组合方式以及粘度进行优化，可以提高导电液体硅橡胶的机械性能。The vinyl silicone oil used for preparing the base rubber is preferably a mixture of one or two of a terminal vinyl silicone oil and a polyvinyl silicone oil. In order to ensure better dispersion of the single-walled carbon nanotubes in the liquid silicone rubber, the viscosity of the terminal vinyl silicone oil used in the present invention does not exceed 150,000 mPa · s, preferably 60,000 to 100,000 mPa · s. The terminal vinyl silicone oil according to the present invention is preferably an alkyl vinyl silicone oil, and more preferably a methyl vinyl silicone oil. The present invention has found through a lot of practice that the mechanical properties of the conductive liquid silicone rubber can be improved by optimizing the specific component selection, combination mode, and viscosity of the vinyl silicone oil.
制备基胶采用的白炭黑优选为经过硅氮烷等处理剂原位接枝的气相白炭黑，其比表面积不少于200m 2/g，优选为280～320m 2/g。 The silica used in the preparation of the base rubber is preferably gas-phase silica which is grafted in situ through a treatment agent such as silazane, and has a specific surface area of not less than 200 m 2 / g, and preferably 280 to 320 m 2 / g.
制备基胶采用的硅氮烷优选为六甲基硅氮烷、四甲基二乙烯基硅氮烷、七甲基二硅氮 烷、乙烯基单封端硅氮烷等中的至少一种或者两种的混合物，更优选为六甲基硅氮烷和/或四甲基二乙烯基硅氮烷。The silazane used for preparing the base rubber is preferably at least one of hexamethylsilazane, tetramethyldivinylsilazane, heptamethyldisilazane, vinyl mono-terminated silazane, or the like, or A mixture of the two is more preferably hexamethylsilazane and / or tetramethyldivinylsilazane.
在获得所述母胶时，本发明提供的方案优选将单壁碳纳米管与聚有机硅氧烷的预混物以及上述重量份原料制备而成的基胶以质量比1～10:100在三辊研磨机上混合，优选混合至所得混合物粒径为0.1μm～20μm，得到导电液体硅橡胶母胶。本发明通过大量实践发现，将单壁碳纳米管的预混物与基胶按照上述比例在三辊研磨机上混合，可以确保单壁碳纳米管均匀、充分地分散于母胶中，继而确保其均匀、充分地分散于终产品中，使得液体硅橡胶具有优异的导电效果以及优异的力学性能。When the masterbatch is obtained, the solution provided by the present invention preferably comprises a base rubber prepared from a premix of single-walled carbon nanotubes and polyorganosiloxane and the above parts by weight of raw materials at a mass ratio of 1 to 10: 100 in Mix on a three-roll mill, preferably until the particle diameter of the resulting mixture is 0.1 μm to 20 μm to obtain a conductive liquid silicone rubber masterbatch. The present invention has found through a large number of practices that mixing the premix of the single-walled carbon nanotubes and the base rubber on a three-roll mill according to the above ratio can ensure that the single-walled carbon nanotubes are uniformly and fully dispersed in the masterbatch, and then ensure that Evenly and fully dispersed in the final product, making liquid silicone rubber have excellent electrical conductivity and excellent mechanical properties.
为了进一步提高所述导电液体硅橡胶包括导电性在内的综合性能，本发明优选除了所述母胶之外，制备所述液体硅橡胶的原料还包括：甲组份、乙组分、催化剂以及抑制剂。In order to further improve the comprehensive performance of the conductive liquid silicone rubber including conductivity, the present invention preferably includes, in addition to the masterbatch, raw materials for preparing the liquid silicone rubber including: component A, component B, catalyst, and Inhibitor.
作为本发明的优选方案，制备所述液体硅橡胶的原料包括：100份所述母胶，甲组份为10～100份、优选10～65份、更优选10-35份，乙组份为0.4～10份、优选0.4～5份，催化剂为0.002～0.02份、优选0.003～0.01份以及抑制剂为0.02～1份、优选0.02～0.5份。As a preferred solution of the present invention, the raw materials for preparing the liquid silicone rubber include: 100 parts of the masterbatch, component A is 10 to 100 parts, preferably 10 to 65 parts, more preferably 10 to 35 parts, and component B is 0.4 to 10 parts, preferably 0.4 to 5 parts, the catalyst is 0.002 to 0.02 parts, preferably 0.003 to 0.01 parts, and the inhibitor is 0.02 to 1 part, preferably 0.02 to 0.5 parts.
所述甲组分是通式(1)所示化合物中的一种或几种的混合：The component A is a mixture of one or more of the compounds represented by the general formula (1):
Figure PCTCN2019098881-appb-000001
Figure PCTCN2019098881-appb-000001
所述通式(1)中，n代表0～100的整数，优选为20～50的整数；m代表70～4000的整数，优选为150～2000的整数；R为饱和烃基，如甲基、乙基、丙基、丁基等；R 1为不饱和烃基，如乙烯基、烯丙基、烯丁基等；R 2为饱和或不饱和烃基，可以是甲基、乙基、乙烯基、丙基、烯丙基、丁基、烯丁基等中的任意一种。本发明优选所述甲组份选自如下成分：R 1为乙烯基且R 2为饱和烃基的端乙烯基硅油，和/或R 1为饱和烃基且R 2为乙烯基的侧链乙烯基硅油，和/或R 1和R 2均为乙烯基的端侧乙烯基硅油。 In the general formula (1), n represents an integer of 0 to 100, preferably an integer of 20 to 50; m represents an integer of 70 to 4000, preferably an integer of 150 to 2000; R is a saturated hydrocarbon group such as methyl, Ethyl, propyl, butyl, etc .; R 1 is an unsaturated hydrocarbon group, such as vinyl, allyl, allyl, etc .; R 2 is a saturated or unsaturated hydrocarbon group, which may be methyl, ethyl, vinyl, Any of propyl, allyl, butyl, allyl and the like. In the present invention, the component A is preferably selected from the group consisting of: a vinyl-terminated silicone oil in which R 1 is a vinyl group and R 2 is a saturated hydrocarbon group; and / or a side chain vinyl silicone oil in which R 1 is a saturated hydrocarbon group and R 2 is a vinyl , And / or R 1 and R 2 are both vinyl end-side vinyl silicone oils.
为了提高终产品的综合性能，本发明优选所述甲组份中乙烯基的质量含量为甲组份总量的0.05～5％。In order to improve the overall performance of the final product, in the present invention, the mass content of the vinyl group in the component A is preferably 0.05 to 5% of the total amount of the component A.
所述乙组份是通式(2)、(3)所示化合物中的一种或几种的混合：The component B is a mixture of one or more of the compounds represented by the general formulae (2) and (3):
Figure PCTCN2019098881-appb-000002
Figure PCTCN2019098881-appb-000002
所述通式(2)中，x为8～200的整数，优选为10～100的整数；y为0～60的整数，优选为0～20的整数；R 3可以是甲基、氢基或硅氢基；R 4可以是甲基、乙基、丙基或苯基。 In the general formula (2), x is an integer of 8 to 200, preferably an integer of 10 to 100; y is an integer of 0 to 60, preferably an integer of 0 to 20; R 3 may be a methyl group or a hydrogen group Or silyl; R 4 may be methyl, ethyl, propyl or phenyl.
Figure PCTCN2019098881-appb-000003
Figure PCTCN2019098881-appb-000003
所述通式(3)中，a为1～300的整数；R 5可以是甲基、乙基或者氢基。 In the general formula (3), a is an integer of 1 to 300; R 5 may be a methyl group, an ethyl group, or a hydrogen group.
当乙组分仅由通式(2)的化合物构成时，y＝0和R 3是甲基这两个条件不同时存在。当乙组分仅由通式(3)的化合物构成时，R 5是氢基。当乙组分是通式(2)、(3)的化合物中的一种或多种的混合时，通式(2)、(3)的化合物中的至少之一具有SiH键。 When the B component is composed of only the compound of the general formula (2), the two conditions that y = 0 and R 3 are methyl are not present at the same time. When the B component is composed only of a compound of the general formula (3), R 5 is a hydrogen group. When the B component is a mixture of one or more of the compounds of the general formulae (2) and (3), at least one of the compounds of the general formulae (2) and (3) has a SiH bond.
本发明优选所述乙组分选自如下成分：R 3为氢基且y大于1的两端和侧链均含有SiH的含氢硅油，和/或R 3为氢基且y等于0的端含氢硅油，和/或R 3为饱和烃基且y大于1的侧链含氢硅油，和/或R 5为氢基的含氢硅树脂。 Part B of the present invention is preferably selected from the following components: R 3 is a hydrogen group and y is greater than 1 and the side chain ends are SiH-containing silicone oil, and / or R 3 is a hydrogen end group and y is equal to 0 A hydrogen-containing silicone oil, and / or a side-chain hydrogen-containing silicone oil in which R 3 is a saturated hydrocarbon group and y is greater than 1, and / or a hydrogen-containing silicone resin in which R 5 is a hydrogen group.
为了提高终产品的综合性能，本发明优选所述乙组份中Si-H基团的质量含量为乙组份总量的3％-50％，更优选乙组分中的至少一种含有三个Si-H官能团从而形成一定交联密度的三维网络结构。In order to improve the overall performance of the final product, in the present invention, it is preferred that the mass content of the Si-H group in the component B is 3% -50% of the total amount of the component B, and more preferably, at least one of the component B contains three Si-H functional groups thus form a three-dimensional network structure with a certain cross-link density.
所述催化剂优选采用卡斯特催化剂。The catalyst is preferably a Custer catalyst.
所述抑制剂可选用1-乙炔基-1-环己醇、2-甲基-3-丁炔-醇和3,5-二甲基-1-己炔-3-醇和3-甲基-1-十二炔-3-醇中的至少一种。The inhibitor may be selected from 1-ethynyl-1-cyclohexanol, 2-methyl-3-butyn-ol, and 3,5-dimethyl-1-hexyn-3-ol and 3-methyl-1 -At least one of dodecyn-3-ol.
本发明同时提供了所述液体硅橡胶的制备方法。The invention also provides a method for preparing the liquid silicone rubber.
优选地，所述制备方法包括如下步骤：首先，将单壁碳纳米管与聚有机硅氧烷进行预先混合，得到预混物，优选地，所述单壁碳纳米管占所述预混物的质量百分比为5～20％，其次，将所述预混物与基胶混合，制备得到母胶，再将所述母胶与其它原料混合，经硫化制备得到导电液体硅橡胶，优选地，所述母胶中所含的所述预混物与所述基胶的质量比为(1～10):100、更优选(3.8～10):100，优选地，其他原料包括：甲组分、乙组分、催化剂以及抑制剂。Preferably, the preparation method includes the following steps: first, pre-mixing the single-walled carbon nanotubes and the polyorganosiloxane to obtain a premix, preferably, the single-walled carbon nanotubes occupy the premix The mass percentage is 5 to 20%. Secondly, the premix is mixed with a base rubber to prepare a masterbatch, and the masterbatch is mixed with other raw materials to prepare a conductive liquid silicone rubber through vulcanization. Preferably, The mass ratio of the premix contained in the masterbatch to the base rubber is (1 to 10): 100, more preferably (3.8 to 10): 100. Preferably, other raw materials include: a component , B component, catalyst and inhibitor.
具体而言，所述制备方法包括如下步骤：将含有单壁碳纳米管的母胶、催化剂以及至少一种甲组份混合均匀，抽真空脱泡，得到A组分；将含有单壁碳纳米管的母胶、至少一种甲组份、至少一种乙组分以及至少一种抑制剂混合均匀，抽真空脱泡，得到B组分；将所述A组分和B组分等比例混合均匀，固化得试片，硫化，即得。其中，优选所述固化的温度为130～170℃；优选所述硫化的温度为180～220℃。Specifically, the preparation method includes the following steps: mixing a masterbatch containing single-walled carbon nanotubes, a catalyst, and at least one component A, and vacuuming and defoaming to obtain component A; and containing single-walled carbon nanotubes The masterbatch, at least one component A, at least one component B, and at least one inhibitor of the tube are mixed uniformly, and degassed under vacuum to obtain component B; the components A and B are mixed in equal proportions Uniform, cured to obtain test pieces, vulcanized, that is. Among them, the curing temperature is preferably 130 to 170 ° C; the curing temperature is preferably 180 to 220 ° C.
作为本发明的优选方案，所述制备方法包括如下具体步骤：As a preferred solution of the present invention, the preparation method includes the following specific steps:
(1)预混物的制备：将所述单壁碳纳米管与聚有机硅氧烷预先混合得到预混物，其中，所述单壁碳纳米管占所述预混物的质量百分比为5～20％；(1) Preparation of premix: premixing the single-walled carbon nanotubes and polyorganosiloxane to obtain a premix, wherein the mass percentage of the single-walled carbon nanotubes to the premix is 5 -20%;
(2)基胶的制备：取甲基乙烯基硅油、白炭黑、硅氮烷和去离子水，在60～90℃、惰性气氛保护下充分混合，然后升温到130～180℃后开始抽真空,抽真空时保持温度在130～180℃，抽真空结束后降温到120～140℃，再加入稀释用甲基乙烯基硅油，搅拌均匀，得基胶；(2) Preparation of base rubber: Take methyl vinyl silicone oil, white carbon black, silazane and deionized water, mix thoroughly under the protection of an inert atmosphere at 60-90 ° C, then raise the temperature to 130-180 ° C and start pumping Vacuum, keep the temperature at 130 ～ 180 ℃ when evacuating, and reduce the temperature to 120 ～ 140 ℃ after evacuating, then add methyl vinyl silicone oil for dilution and stir well to obtain base glue;
(3)母胶的制备：将含有单壁碳纳米管的预混物以及基胶在三辊研磨机上充分混合，即得母胶；(3) Preparation of masterbatch: the premix containing single-walled carbon nanotubes and the base rubber are thoroughly mixed on a three-roll mill to obtain a masterbatch;
(4)AB组份的制备及硫化：将所述母胶、催化剂以及至少一种甲组份混合均匀，抽真空脱泡，得到A组分；将所述母胶、至少一种甲组份、至少一种乙组分以及至少一种抑制剂混合均匀，抽真空脱泡，得到B组分；将所述A组分和B组分等比例混合均匀，固化得试片，硫化，即得。(4) Preparation and vulcanization of component AB: mixing the masterbatch, catalyst and at least one component A uniformly, degassing under vacuum to obtain component A; the masterbatch, at least one component A , At least one component B and at least one inhibitor are mixed uniformly, and degassed under vacuum to obtain component B; the components A and B are mixed in equal proportions, cured to obtain test pieces, and vulcanized to obtain .
本发明所述的温度、时间等工艺条件均为优选范围，但本发明的保护范围不限于此。The process conditions such as temperature and time described in the present invention are all preferred ranges, but the protection scope of the present invention is not limited thereto.
本发明提供的液体硅橡胶具有优异的综合性能，包括导电性、拉伸强度、断裂伸长率等物理机械性能。本发明同时保护所述液体硅橡胶在制备电网和/或电缆附件中的应用。The liquid silicone rubber provided by the invention has excellent comprehensive properties, including physical and mechanical properties such as electrical conductivity, tensile strength, elongation at break and the like. The invention also protects the application of the liquid silicone rubber in preparing power grids and / or cable accessories.
与现有技术相比，本发明首次采用单壁碳纳米管为导电填充物制得一种单壁碳纳米管导电液体硅橡胶复合材料，同时通过采用两步骤的预先混合以及配方设计，实现了在极少 的添加量下有效地将单壁碳纳米管分散在整个体系中，在降低产品粘度提高加工性能的同时，又防止了团聚、沉降、析出等问题出现，从而形成有效的导电网络通路，制备出体积电阻率小于100Ω·cm的导电材料。本发明提供的导电液体硅橡胶不仅导电填料添加量低、电性能优良，而且物理机械性能和耐候性优异，且硫化过程中无污染物产生、生产工艺简单无污染、操作方便。Compared with the prior art, the present invention for the first time uses a single-walled carbon nanotube as a conductive filler to prepare a single-walled carbon nanotube conductive liquid silicone rubber composite material. At the same time, it uses two steps of pre-mixing and formula design to achieve Effectively disperse single-walled carbon nanotubes in the entire system with a very small amount of addition. While reducing product viscosity and improving processing performance, it also prevents problems such as agglomeration, sedimentation, and precipitation, thereby forming an effective conductive network path. , A conductive material having a volume resistivity of less than 100Ω · cm was prepared. The conductive liquid silicone rubber provided by the invention not only has a low amount of conductive filler, excellent electrical properties, but also excellent physical and mechanical properties and weather resistance, and has no pollutants generated during the vulcanization process, the production process is simple and free of pollution, and the operation is convenient.
具体实施方式detailed description
下面结合实施例对本发明技术方案做进一步详细、完整的说明。The technical solution of the present invention will be further described in detail and in combination with the following embodiments.
以下各实施例中采用的单壁碳纳米管为市售购得，其直径为1.5nm左右(在1.2nm～2nm的范围内)，长度为12μm。The single-walled carbon nanotubes used in the following examples are commercially available, with a diameter of about 1.5 nm (in the range of 1.2 nm to 2 nm) and a length of 12 μm.
液体导电硅橡胶的制备Preparation of liquid conductive silicone rubber
实施例1Example 1
本实施例提供了一种单壁碳纳米管导电液体硅橡胶，其由如下方法制备而成：This embodiment provides a single-walled carbon nanotube conductive liquid silicone rubber, which is prepared by the following method:
(1)预混物的制备：将所述单壁碳纳米管与聚有机硅氧烷预先混合得到预混物，其中，所述单壁碳纳米管占所述预混物的质量百分比为10％。(1) Preparation of premix: premixing the single-walled carbon nanotubes and polyorganosiloxane to obtain a premix, wherein the mass percentage of the single-walled carbon nanotubes to the premix is 10 %.
(2)基胶的制备：在捏合机或者行星搅拌机中将重量占比为42份粘度为60000mPa·s的甲基乙烯基硅油、26份比表面积为300m 2/g的BET气相白炭黑以及7份六甲基二硅氮烷、0.05份四甲基二乙烯基硅氮烷和3.5份的去离子水，在80℃以下惰性气氛保护下充分混合1.5小时，然后升温到140℃后开始抽真空3h,抽真空时保持温度在160℃，然后降温到125℃，加入21.5份粘度为60000mPa·s的甲基乙烯基硅油，搅拌均匀，即得到液体硅橡胶基胶1。 (2) Preparation of base rubber: In a kneader or planetary mixer, 42 parts by weight of methyl vinyl silicone oil with a viscosity of 60,000 mPa · s, 26 parts of BET gas phase white carbon black with a specific surface area of 300 m 2 / g, and 7 parts of hexamethyldisilazane, 0.05 parts of tetramethyldivinylsilazane, and 3.5 parts of deionized water are mixed thoroughly under the protection of an inert atmosphere below 80 ° C for 1.5 hours, and then the temperature is raised to 140 ° C and the pumping is started. Vacuum for 3h, keep the temperature at 160 ° C during evacuation, then lower the temperature to 125 ° C, add 21.5 parts of methyl vinyl silicone oil with a viscosity of 60,000 mPa · s, and stir evenly to obtain liquid silicone rubber base rubber 1.
(3)母胶的制备：将3.8份步骤(1)中获得的所述预混物、100份基胶1在三辊研磨机上混合10遍(混合物粒径为0.1-20微米)，制备出导电液体硅橡胶母胶1；(3) Preparation of masterbatch: 3.8 parts of the premix obtained in step (1) and 100 parts of base rubber 1 are mixed 10 times on a three-roll mill (the particle diameter of the mixture is 0.1-20 microns) to prepare Conductive liquid silicone rubber masterbatch 1;
(4)AB组份的制备及硫化：将上述100份的母胶1，18份粘度为20000mPa·s的端乙烯基硅油，5份粘度为1000mPa·s的侧链乙烯基硅油，0.02份卡斯特型催化剂，在行星搅拌机中搅拌分散35min，混合均匀再抽真空脱泡即得到导电液体硅橡胶A组分1。将上述100份的母胶1，20份粘度为20000mPa·s的端乙烯基硅油，3份粘度为1000mPa·s的侧链乙烯基硅油，1.5份含氢量为0.7％的两端和侧链均含有SiH的含氢硅油，1.5份含氢量为0.2％的端含氢硅油，0.1份3-甲基-1-十二炔-3-醇，在行星搅拌机中搅拌分散35min， 混合均匀再抽真空脱泡即得到导电液体硅橡胶B组分1。将等比例的A组分1和等比例的B组分1混合均匀，然后在150℃下固化10min制得2mm试片，试片在200℃下二次硫化4小时，得到单壁碳纳米管导电液体硅橡胶。(4) Preparation and vulcanization of component AB: 100 parts of the above-mentioned masterbatch, 1,18 parts of vinyl-terminated silicone oil having a viscosity of 20,000 mPa · s, 5 parts of side-chain vinyl silicone oil having a viscosity of 1000 mPa · s, and 0.02 parts of card This type of catalyst is stirred and dispersed in a planetary mixer for 35 minutes, mixed evenly, and then evacuated and degassed to obtain a conductive liquid silicone rubber component A. 100 parts of the above-mentioned masterbatch 1, 20 parts of a vinyl-terminated silicone oil having a viscosity of 20,000 mPa · s, 3 parts of a side-chain vinyl silicone oil having a viscosity of 1000 mPa · s, and 1.5 parts of both ends and side chains having a hydrogen content of 0.7% Hydrogen-containing silicone oils that all contain SiH, 1.5 parts of hydrogen-containing silicone oils with a hydrogen content of 0.2%, and 0.1 parts of 3-methyl-1-dodecyn-3-ol, stir and disperse in a planetary mixer for 35 minutes, mix well and then Vacuum degassing to obtain conductive liquid silicone rubber B component 1. The equal proportion of component A and the proportion of component B are mixed uniformly, and then cured at 150 ° C for 10 minutes to prepare a 2mm test piece. The test piece is secondarily vulcanized at 200 ° C for 4 hours to obtain single-walled carbon nanotubes. Conductive liquid silicone rubber.
实施例2Example 2
本实施例提供了一种单壁碳纳米管导电液体硅橡胶，其由如下方法制备而成：This embodiment provides a single-walled carbon nanotube conductive liquid silicone rubber, which is prepared by the following method:
(1)预混物的制备：同实施例1；。(1) Preparation of premix: same as in Example 1 ;.
(2)基胶的准备：在捏合机或者行星搅拌机中将重量占比为40份粘度为60000mPa·s的甲基乙烯基硅油、25份BET比表面积为300m 2/g的气相白炭黑以及7份六甲基二硅氮烷、0.1份四甲基二乙烯基硅氮烷和4份去离子水在80℃以下惰性气氛保护下充分混合1.5小时，然后升温到140℃后开始抽真空3h,抽真空时保持温度在160℃，然后降温到125℃，加入23.9份粘度为60000mPa·s的甲基乙烯基硅油，搅拌均匀，即得到液体硅橡胶基胶2。 (2) Preparation of base rubber: In a kneader or planetary mixer, 40 parts by weight of methyl vinyl silicone oil with a viscosity of 60,000 mPa · s, 25 parts of fumed silica with a BET specific surface area of 300 m 2 / g, and 7 parts of hexamethyldisilazane, 0.1 part of tetramethyldivinylsilazane and 4 parts of deionized water were mixed thoroughly under the protection of an inert atmosphere below 80 ° C for 1.5 hours, and then the temperature was raised to 140 ° C and vacuum was started for 3 hours Keep the temperature at 160 ° C during evacuation, and then reduce the temperature to 125 ° C. Add 23.9 parts of methyl vinyl silicone oil with a viscosity of 60,000 mPa · s and stir well to obtain liquid silicone rubber base rubber 2.
(3)母胶的制备：将5份步骤(1)中获得的所述预混物、100份基胶2在三辊研磨机上混合5遍(混合物粒径为0.1-20微米)，制备出导电液体硅橡胶母胶2；(3) Preparation of masterbatch: 5 parts of the premix obtained in step (1) and 100 parts of base rubber 2 are mixed 5 times on a three-roll mill (the particle diameter of the mixture is 0.1-20 microns) to prepare Conductive liquid silicone rubber masterbatch 2;
(4)AB组份的制备及硫化：将上述100份的母胶2，10份粘度为3500mPa·s的端乙烯基硅油，3份粘度为1000mPa·s的侧链乙烯基硅油，0.02份卡斯特催化剂，在行星搅拌机中搅拌分散30-40min，混合均匀再抽真空脱泡即得到导电液体硅橡胶A组分2。将上述100份的母胶2，7份粘度为3500mPa·s的端乙烯基硅油，1份粘度为1000mPa·s的侧链乙烯基硅油，3份含氢量为0.7％的两端和侧链均含有SiH的含氢硅油，0.1份3-甲基-1-十二炔-3-醇，在行星搅拌机中搅拌分散30-40min，混合均匀再抽真空脱泡即得到导电液体硅橡胶B组分2。将等比例的A组分2和等比例的B组分2混合均匀，然后在150℃下固化10min制得2mm试片，试片在200℃下二次硫化4小时，得到单壁碳纳米管导电液体硅橡胶。(4) Preparation and vulcanization of the AB component: 100 parts of the above-mentioned masterbatch 2, 10 parts of the terminal vinyl silicone oil having a viscosity of 3500 mPa · s, 3 parts of the side chain vinyl silicone oil having a viscosity of 1000 mPa · s, and 0.02 parts of card Stir catalyst, stir and disperse in a planetary mixer for 30-40 minutes, mix well and then vacuum degassing to obtain conductive liquid silicone rubber component A 2. 100 parts of the above-mentioned masterbatch 2, 7 parts of a terminal vinyl silicone oil having a viscosity of 3500 mPa · s, 1 part of a side chain vinyl silicone oil having a viscosity of 1000 mPa · s, and 3 parts of both ends and side chains having a hydrogen content of 0.7% Hydrogen-containing silicone oil containing SiH, 0.1 part of 3-methyl-1-dodecyne-3-ol, stir and disperse in a planetary mixer for 30-40 minutes, mix well and then vacuum degassing to obtain conductive liquid silicone rubber group B Points 2. The same proportion of A component 2 and the equal proportion of B component 2 were mixed uniformly, and then cured at 150 ° C. for 10 minutes to prepare a 2 mm test piece. The test piece was secondarily vulcanized at 200 ° C. for 4 hours to obtain single-walled carbon nanotubes. Conductive liquid silicone rubber.
实施例3Example 3
本实施例提供了一种单壁碳纳米管导电液体硅橡胶，其由如下方法制备而成：This embodiment provides a single-walled carbon nanotube conductive liquid silicone rubber, which is prepared by the following method:
(1)预混物的制备：同实施例1；。(1) Preparation of premix: same as in Example 1 ;.
(2)基胶的准备：在捏合机或者行星搅拌机中将重量占比为38份粘度为100000mPa·s的甲基乙烯基硅油、7份粘度为60000mPa·s的甲基乙烯基硅油、25份BET比表面积为300m 2/g的气相白炭黑以及7份六甲基二硅氮烷、0.15份四甲基二乙烯基硅氮烷 和6份去离子水，在80℃以下惰性气氛保护下充分混合1.5小时，然后升温到140℃后开始抽真空3h,抽真空时保持温度在160℃，然后降温到125℃，加入16.8份粘度为20000mPa·s的甲基乙烯基硅油，搅拌均匀，即得到液体硅橡胶基胶3。 (2) Preparation of base rubber: In a kneader or planetary mixer, 38 parts by weight of methyl vinyl silicone oil having a viscosity of 100,000 mPa · s, 7 parts of methyl vinyl silicone oil having a viscosity of 60,000 mPa · s, and 25 parts Gaseous silica with a BET specific surface area of 300 m 2 / g and 7 parts of hexamethyldisilazane, 0.15 parts of tetramethyldivinylsilazane and 6 parts of deionized water, protected under an inert atmosphere below 80 ° C Thoroughly mix for 1.5 hours, then raise the temperature to 140 ° C and start to evacuate for 3h. Keep the temperature at 160 ° C while evacuating, and then reduce the temperature to 125 ° C. Add 16.8 parts of methyl vinyl silicone oil with a viscosity of 20000mPa · s and stir well, that is, A liquid silicone rubber base rubber 3 was obtained.
(3)母胶的制备：将4份步骤(1)中获得的所述预混物、100份基胶3在三辊研磨机上混合10遍(混合物粒径为0.1-20微米)，制备出导电液体硅橡胶母胶3；(3) Preparation of masterbatch: 4 parts of the premix obtained in step (1) and 100 parts of base rubber 3 are mixed 10 times on a three-roll mill (the particle diameter of the mixture is 0.1-20 microns) to prepare Conductive liquid silicone rubber masterbatch 3;
(4)AB组份的制备及硫化：将上述100份的母胶3，11份粘度为100000mPa·s的端乙烯基硅油，3.5份粘度为1000mPa·s的侧链乙烯基硅油，0.015份卡斯特催化剂，在行星搅拌机中搅拌分散30-40min，混合均匀再抽真空脱泡即得到导电液体硅橡胶A组分1。将上述100份的母胶3，12份粘度为100000mPa·s的端乙烯基硅油，1.7份含氢量为0.7％的两端和侧链均含有SiH的含氢硅油，0.5份两端含有SiH的含氢硅油，0.08份1-乙炔基-1-环己醇，在行星搅拌机中搅拌分散30-40min，混合均匀再抽真空脱泡即得到导电液体硅橡胶B组分3。将等比例的A组分3和等比例的B组分3混合均匀，然后在150℃下固化10min制得2mm试片，试片在200℃下二次硫化4小时，得到单壁碳纳米管导电液体硅橡胶。(4) Preparation and vulcanization of component AB: 100 parts of the above-mentioned masterbatch 3, 11 parts of the terminal vinyl silicone oil having a viscosity of 100,000 mPa · s, 3.5 parts of the side chain vinyl silicone oil having a viscosity of 1000 mPa · s, and 0.015 parts of card Stir catalyst, stir and disperse in a planetary mixer for 30-40min, mix well and then vacuum degassing to obtain conductive liquid silicone rubber A component 1. 100 parts of the above-mentioned masterbatch 3, 12 parts of a terminal vinyl silicone oil having a viscosity of 100,000 mPa · s, 1.7 parts of a hydrogen-containing silicone oil having SiH at both ends and side chains of 0.5%, and 0.5 parts of SiH at both ends Hydrogen-containing silicone oil, 0.08 parts of 1-ethynyl-1-cyclohexanol, stir and disperse in a planetary mixer for 30-40 minutes, mix well and then vacuum degassing to obtain conductive liquid silicone rubber component B 3. The same proportion of A component 3 and the equal proportion of B component 3 are mixed uniformly, and then cured at 150 ° C for 10 minutes to obtain a 2mm test piece. The test piece is secondarily vulcanized at 200 ° C for 4 hours to obtain single-walled carbon nanotubes. Conductive liquid silicone rubber.
实施例4Example 4
本实施例提供了一种单壁碳纳米管导电液体硅橡胶，其由如下方法制备而成：This embodiment provides a single-walled carbon nanotube conductive liquid silicone rubber, which is prepared by the following method:
(1)预混物的制备：同实施例1；(1) Preparation of premix: same as in Example 1;
(2)基胶的制备：同实施例3；(2) Preparation of base glue: same as in Example 3;
(3)母胶的制备：将3.5份步骤(1)中获得的所述预混物和100份基胶3在三辊研磨机中混合10-20遍(混合物粒径为0.1-20微米)，制备出导电液体硅橡胶母胶4；(3) Preparation of masterbatch: 3.5 parts of the premix obtained in step (1) and 100 parts of base rubber 3 are mixed 10-20 times in a three-roll mill (the particle diameter of the mixture is 0.1-20 microns) To prepare a conductive liquid silicone rubber masterbatch 4;
(4)AB组份的制备及硫化：将上述100份的母胶4，20份粘度为20000mPa·s的端乙烯基硅油，2份粘度为1000mPa·s的侧链乙烯基硅油，0.025份卡斯特型催化剂，在行星搅拌机中搅拌分散30-40min，混合均匀再抽真空脱泡即得到导电液体硅橡胶A组分4。将上述100份的母胶4，15份粘度为20000mPa·s的端乙烯基硅油，1份粘度为1000mPa·s的侧链乙烯基硅油，1份含氢量为0.7％的两端和侧链均含有SiH的含氢硅油，0.13份3-甲基-1-十二炔-3-醇，在行星搅拌机中搅拌分散30-40min，混合均匀再抽真空脱泡即得到导电液体硅橡胶B组分4。将等比例的A组分4和等比例的B组分4混合均匀，然后在150℃下固化10min制得2mm试片，试片在200℃下二次硫化4小时，得到单壁碳纳米管导电液体硅橡胶。(4) Preparation and vulcanization of component AB: 100 parts of the above-mentioned masterbatch 4, 20 parts of the vinyl-terminated silicone oil having a viscosity of 20,000 mPa · s, 2 parts of the side-chain vinyl silicone oil having a viscosity of 1000 mPa · s, and 0.025 parts of card This type of catalyst is stirred and dispersed in a planetary mixer for 30-40 minutes, mixed evenly, and then evacuated and degassed to obtain conductive liquid silicone rubber component A 4. 100 parts of the above-mentioned masterbatch 4, 15 parts of a terminal vinyl silicone oil having a viscosity of 20,000 mPa · s, 1 part of a side chain vinyl silicone oil having a viscosity of 1000 mPa · s, and 1 part of both ends and side chains having a hydrogen content of 0.7% Hydrogen-containing silicone oil containing SiH, 0.13 parts of 3-methyl-1-dodecyn-3-ol, stir and disperse in a planetary mixer for 30-40 minutes, mix well and then vacuum degassing to obtain conductive liquid silicone rubber group B Points 4. The equal proportion of A component 4 and the equal proportion of B component 4 were mixed uniformly, and then cured at 150 ° C. for 10 minutes to obtain a 2 mm test piece. The test piece was subjected to secondary vulcanization at 200 ° C. for 4 hours to obtain single-walled carbon nanotubes. Conductive liquid silicone rubber.
实施例5Example 5
本实施例提供了一种单壁碳纳米管导电液体硅橡胶，其由如下方法制备而成：This embodiment provides a single-walled carbon nanotube conductive liquid silicone rubber, which is prepared by the following method:
(1)预混物的制备：同实施例1；。(1) Preparation of premix: same as in Example 1 ;.
(2)基胶的准备：在捏合机或者行星搅拌机中将重量占比为40份粘度为60000mPa·s的甲基乙烯基硅油、2.5份粘度200000mPa·s的多乙烯基硅油、27.5份BET比表面积为300m 2/g的气相白炭黑以及8份六甲基二硅氮烷、0.7份四甲基二乙烯基硅氮烷和4.5份去离子水，在80℃以下惰性气氛保护下充分混合1.5小时，然后升温到140℃后开始抽真空3h,抽真空时保持温度在160℃，然后降温到125℃，加入16.8份粘度60000mPa·s甲基乙烯基硅油，搅拌均匀，即得到液体硅橡胶基胶5。 (2) Preparation of base rubber: In a kneader or planetary mixer, the weight ratio is 40 parts of methyl vinyl silicone oil having a viscosity of 60,000 mPa · s, 2.5 parts of polyvinyl silicone oil having a viscosity of 200,000 mPa · s, and 27.5 parts of BET ratio. Gaseous silica with a surface area of 300 m 2 / g, 8 parts of hexamethyldisilazane, 0.7 part of tetramethyldivinylsilazane, and 4.5 parts of deionized water are mixed well under the protection of an inert atmosphere below 80 ° C 1.5 hours, then raised the temperature to 140 ° C and started to evacuate for 3h. Keep the temperature at 160 ° C when evacuating, and then reduce the temperature to 125 ° C. Add 16.8 parts of 60,000 mPa · s methyl vinyl silicone oil and stir well to obtain liquid silicone rubber. Base rubber 5.
(3)母胶的制备：将6份步骤(1)中获得的所述预混物、100份基胶5在三辊研磨机上混合20遍(混合物粒径为0.1-20微米)，制备出导电液体硅橡胶母胶5；(3) Preparation of masterbatch: 6 parts of the premix obtained in step (1) and 100 parts of base rubber 5 are mixed 20 times on a three-roll mill (the particle diameter of the mixture is 0.1-20 microns) to prepare Conductive liquid silicone rubber masterbatch 5;
(4)AB组份的制备及硫化：将上述100份的母胶5，15份粘度为20000mPa·s的端乙烯基硅油，6份乙烯基质量含量为2.36％的端侧乙烯基硅油，0.018份卡斯特催化剂，在行星搅拌机中搅拌分散30-40min，混合均匀后再抽真空脱泡即得到导电液体硅橡胶A组分5。将上述100份的母胶5，14.5份粘度为100000mPa·s的端乙烯基硅油，6.5份质量含量为0.7％的两端和侧链均含有SiH的含氢硅油，0.13份3-甲基-1-十二炔-3-醇，在行星搅拌机中搅拌分散30-40min，混合均匀再抽真空脱泡即得到导电液体硅橡胶B组分5。将等比例的A组分5和等比例的B组分5混合均匀，然后在150℃下固化10min制得2mm试片，试片在200℃下二次硫化4小时，得到单壁碳纳米管导电液体硅橡胶。(4) Preparation and vulcanization of component AB: 100 parts of the above-mentioned masterbatch 5, 15 parts of the terminal vinyl silicone oil having a viscosity of 20,000 mPa · s, 6 parts of the vinyl vinyl end oil having a mass content of 2.36%, 0.018 Part of Custer catalyst, stir and disperse in a planetary mixer for 30-40min, and mix and then vacuum degassing to obtain conductive liquid silicone rubber component A5. 100 parts of the above-mentioned masterbatch 5, 14.5 parts of a vinyl-terminated silicone oil having a viscosity of 100,000 mPa · s, 6.5 parts of a hydrogen-containing silicone oil having SiH at both ends and side chains of 0.1% by mass, and 0.13 parts of 3-methyl- 1-Dodecyne-3-ol, stir and disperse in a planetary mixer for 30-40 minutes, mix well and then vacuum degassing to obtain conductive liquid silicone rubber component B 5. The equal proportion of A component 5 and the equal proportion of B component 5 are mixed uniformly, and then cured at 150 ° C for 10 minutes to prepare a 2mm test piece. The test piece is secondarily vulcanized at 200 ° C for 4 hours to obtain single-walled carbon nanotubes. Conductive liquid silicone rubber.
实施例6Example 6
本实施例提供了一种单壁碳纳米管导电液体硅橡胶，与实施例4相比，区别仅在于：制备母胶时，用行星搅拌器的混合方式代替在三辊研磨机上混合；This embodiment provides a single-walled carbon nanotube conductive liquid silicone rubber. Compared with Example 4, the only difference is that: when preparing a master batch, a planetary mixer is used instead of mixing on a three-roll mill;
具体步骤为：The specific steps are:
(1)预混物的制备：同实施例1；(1) Preparation of premix: same as in Example 1;
(2)基胶的制备：同实施例3；(2) Preparation of base glue: same as in Example 3;
(3)母胶的制备：将3.5份步骤(1)中获得的所述预混物和100份基胶3放入行星搅拌机中，转速1200r/min，分散30min，制备出导电液体硅橡胶母胶7；(3) Preparation of masterbatch: Put 3.5 parts of the premix obtained in step (1) and 100 parts of base rubber 3 into a planetary mixer, rotate at 1200r / min, and disperse for 30min to prepare a conductive liquid silicone rubber masterbatch. Glue 7
(4)AB组份的制备及硫化：将上述100份的母胶7，20份粘度为20000mPa·s的 端乙烯基硅油，2份粘度为1000mPa·s的侧链乙烯基硅油，0.025份卡斯特型催化剂，在行星搅拌机中搅拌分散30-40min，混合均匀再抽真空脱泡即得到导电液体硅橡胶A组分7。将上述100份的母胶7，15份粘度为20000mPa·s的端乙烯基硅油，1份粘度为1000mPa·s的侧链乙烯基硅油，1份含氢量为0.7％的两端和侧链均含有SiH的含氢硅油，0.13份3-甲基-1-十二炔-3-醇，在行星搅拌机中搅拌分散30-40min，混合均匀再抽真空脱泡即得到导电液体硅橡胶B组分7。将等比例的A组分7和等比例的B组分7混合均匀，然后在150℃下固化10min制得2mm试片，试片在200℃下二次硫化4小时，得到单壁碳纳米管导电液体硅橡胶。(4) Preparation and vulcanization of component AB: 100 parts of masterbatch 7, 20 parts of vinyl-terminated silicone oil having a viscosity of 20,000 mPa · s, 2 parts of side-chain vinyl silicone oil having a viscosity of 1000 mPa · s, and 0.025 parts of card This type of catalyst is stirred and dispersed in a planetary mixer for 30-40 minutes, mixed evenly, and then evacuated and degassed to obtain conductive liquid silicone rubber A component 7. 100 parts of the above-mentioned masterbatch 7, 15 parts of a terminal vinyl silicone oil having a viscosity of 20,000 mPa · s, 1 part of a side chain vinyl silicone oil having a viscosity of 1000 mPa · s, and 1 part of both ends and side chains having a hydrogen content of 0.7% Hydrogen-containing silicone oil containing SiH, 0.13 parts of 3-methyl-1-dodecyn-3-ol, stir and disperse in a planetary mixer for 30-40 minutes, mix well and then vacuum degassing to obtain conductive liquid silicone rubber group B Points 7. The equal proportion of A component 7 and the equal proportion of B component 7 are mixed uniformly, and then cured at 150 ° C. for 10 minutes to obtain a 2 mm test piece. The test piece is secondarily vulcanized at 200 ° C. for 4 hours to obtain single-walled carbon nanotubes. Conductive liquid silicone rubber.
对比例1：Comparative Example 1:
在制备过程中不加入单壁碳纳米管聚有机硅氧烷混合物，其余原料以及操作步骤与实施例1完全相同。In the preparation process, the single-walled carbon nanotube polyorganosiloxane mixture was not added, and the remaining raw materials and operation steps were exactly the same as those in Example 1.
对比例2：Comparative Example 2:
提供一种单壁碳纳米管导电液体硅橡胶，与实施例1相比，区别仅在于：用单壁碳纳米管代替所述单壁碳纳米管与聚有机硅氧烷的预混物，即将单壁碳纳米管直接与基胶混合，制备母胶。A single-walled carbon nanotube conductive liquid silicone rubber is provided. Compared with Example 1, the only difference is that a single-walled carbon nanotube is used to replace the premix of the single-walled carbon nanotube and polyorganosiloxane. Single-walled carbon nanotubes are directly mixed with the base glue to prepare a masterbatch.
对比例3：Comparative Example 3:
提供一种单壁碳纳米管导电液体硅橡胶，与实施例1相比，区别仅在于：没有制备聚有机硅氧烷与单壁碳纳米管的预混物，也没有将预混物与基胶混合得到母胶，而是直接将未经处理的单壁碳纳米管与A、B组分混合。A single-walled carbon nanotube conductive liquid silicone rubber is provided. Compared with Example 1, the only difference is that a premix of polyorganosiloxane and single-walled carbon nanotubes is not prepared, and the premix and base are not prepared. The glue is mixed to obtain a master batch, and the untreated single-walled carbon nanotubes are directly mixed with the A and B components.
对比例4：Comparative Example 4:
提供一种单壁碳纳米管导电液体硅橡胶，与实施例1相比，区别仅在于：制备单壁碳纳米管的预混物之后，没有将该预混物与基胶混合制备母胶，而是直接将所述预混物与A、B组分混合。Provide a single-walled carbon nanotube conductive liquid silicone rubber. Compared with Example 1, the only difference is that after preparing a premix of single-walled carbon nanotubes, the premix is not mixed with the base rubber to prepare a masterbatch. Instead, the premix is directly mixed with the A and B components.
液体导电硅橡胶的检测Testing of liquid conductive silicone rubber
对实施例1～7提供的导电液体硅胶性能进行检测。The properties of the conductive liquid silica gel provided in Examples 1 to 7 were tested.
体积电阻以及计算体积电阻率的检测方法采用GB/T2439-2001；拉伸强度和断裂伸长率的检测方法采用ASTM D412-1998a(2002)e1；硬度的检测方法采ASTM D2240；撕裂强度的检测方法采用ASTM D624；回弹率的检测方法采用ASTM D7121-2005(2012)。GB / T2439-2001 is used as the test method for volume resistance and calculated volume resistivity; ASTM D412-1998a (2002) e1 is used for the test method for tensile strength and elongation at break; ASTM D2240 is used for the test method for hardness; The test method adopts ASTM D624; the test method of rebound rate adopts ASTM D7121-2005 (2012).
检测结果如表1所示。The test results are shown in Table 1.
表1：导电液体硅橡胶制品试片性能Table 1: Properties of conductive liquid silicone rubber products
Figure PCTCN2019098881-appb-000004
Figure PCTCN2019098881-appb-000004
* a由于制片不均匀，导致测量结果偏差较大 * a Due to the uneven production, the deviation of the measurement results is large
* b由于制片不均匀，导致测量结果偏差较大。 * b Due to uneven production, the deviation of measurement results is large.
由表1结果可知，采用制备预混物以及将预混物与基胶混合得到母胶的两步骤的预先混合方式，实现了在极少的添加量下有效的将单壁碳纳米管分散在整个体系中，所得液体硅橡胶不仅导电性能好，而且具有优异的机械性能，包括导电性、拉伸强度、断裂伸长率等。没有采用上述两步骤的预先混合方式不能得到有意义的体积电阻率的测量结果(如对比例3所示)，没有采用将单壁碳纳米管与聚有机硅氧烷混合制备预混物的步骤，也不能得到有意义的体积电阻率的测量结果(如对比例2所示)。即使采用了单壁碳纳米管与聚有机硅氧烷的预混物，如果没有与基胶混合进而得到母胶的步骤，则所获得的体积电阻率不能 满足电网附件或电缆附件的应用要求(如对比例4所示)。From the results in Table 1, it can be seen that the two-step premixing method of preparing a premix and mixing the premix with a base rubber to obtain a masterbatch achieves effective dispersion of single-walled carbon nanotubes in a small amount of addition. In the entire system, the obtained liquid silicone rubber not only has good electrical conductivity, but also has excellent mechanical properties, including electrical conductivity, tensile strength, elongation at break, and the like. No meaningful volume resistivity measurement results can be obtained without the two-step premixing method described above (as shown in Comparative Example 3), and there is no step to prepare a premix by mixing single-walled carbon nanotubes with polyorganosiloxane. , Can not get meaningful volume resistivity measurement results (as shown in Comparative Example 2). Even if a premix of single-walled carbon nanotubes and polyorganosiloxane is used, if there is no step of mixing with the base glue to obtain a masterbatch, the obtained volume resistivity cannot meet the application requirements of grid accessories or cable accessories ( (As shown in Comparative Example 4).
本发明提供的导电液体硅胶具有良好的导电性能和优异的机械强度，同时具有粘度低的特点，流动性好易注射成型。在一定范围内增加单壁碳纳米管的预混物添加比例，产品的导电性能提高，并且力学性能受影响很小，完全满足电力行业应用需求。同时，直接添加同样比例的单壁碳纳米管粉体填料，碳纳米管分散不均匀，产品外观不均一、拉伸性能差。采用预混物的添加方式，一方面环保干净，另一方面纳米管分散均匀、机械性能优异、电性能良好。The conductive liquid silica gel provided by the invention has good electrical conductivity and excellent mechanical strength, at the same time has the characteristics of low viscosity, good fluidity and easy injection molding. Increasing the addition ratio of single-walled carbon nanotubes in a certain range increases the conductivity of the product and has little impact on the mechanical properties, which fully meets the application needs of the power industry. At the same time, the same proportion of single-walled carbon nanotube powder filler is directly added, the carbon nanotubes are unevenly dispersed, the product appearance is uneven, and the tensile properties are poor. The premix is added on the one hand, which is environmentally friendly and clean, on the other hand, the nanotubes are uniformly dispersed, the mechanical properties are excellent, and the electrical properties are good.
虽然，上文中已经用一般性说明、具体实施方式及试验，对本发明作了详尽的描述，但在本发明基础上，可以对之作一些修改或改进，这对本领域技术人员而言是显而易见的。因此，在不偏离本发明精神的基础上所做的这些修改或改进，均属于本发明要求保护的范围。Although the present invention has been described in detail with the general description, specific embodiments, and tests, it is obvious to those skilled in the art that some modifications or improvements can be made based on the present invention. . Therefore, these modifications or improvements made without departing from the spirit of the present invention belong to the scope of protection of the present invention.

Claims (10)

  1. 一种导电液体硅橡胶，其特征在于，所述导电液体硅橡胶采用的导电填料包括单壁碳纳米管，A conductive liquid silicone rubber, characterized in that the conductive filler used in the conductive liquid silicone rubber includes single-walled carbon nanotubes,
    优选地，所述单壁碳纳米管的用量占所述液体硅橡胶总质量的0.1～10％；Preferably, the amount of the single-walled carbon nanotubes accounts for 0.1 to 10% of the total mass of the liquid silicone rubber;
    所述单壁碳纳米管是以预混物的形式使用；所述预混物是由所述单壁碳纳米管与聚有机硅氧烷预先混合而成，The single-walled carbon nanotubes are used in the form of a premix; the premix is prepared by mixing the single-walled carbon nanotubes and polyorganosiloxane in advance,
    优选地，所述单壁碳纳米管占所述预混物的质量百分比为5～20％。Preferably, the mass percentage of the single-walled carbon nanotubes to the premix is 5-20%.
  2. 根据权利要求1所述的导电液体硅橡胶，其特征在于，所述单壁碳纳米管直径为1nm～50nm，长度大于5μm；The conductive liquid silicone rubber according to claim 1, wherein the single-walled carbon nanotubes have a diameter of 1 nm to 50 nm and a length of more than 5 μm;
    优选地，所述单壁碳纳米管的直径为1.2nm～2nm，长度大于10μm。Preferably, the single-walled carbon nanotube has a diameter of 1.2 nm to 2 nm and a length greater than 10 μm.
  3. 根据权利要求2所述的导电液体硅橡胶，其特征在于，所述导电液体硅橡胶的母胶是由含有单壁碳纳米管的所述预混物与基胶混合而成，二者优选以(1～10):100、更优选(3.8～10):100的质量比混合而成；The conductive liquid silicone rubber according to claim 2, wherein the master batch of the conductive liquid silicone rubber is made by mixing the premix containing single-walled carbon nanotubes with a base rubber, and the two are preferably mixed with (1 ~ 10): 100, more preferably (3.8 ~ 10): 100 is mixed by mass ratio;
    优选地，所述母胶采用包括如下步骤的方法制备而成：将单壁碳纳米管的所述预混物以及基胶在三辊研磨机上充分混合，优选混合至所得混合物粒径为0.1μm～20μm，即得母胶。Preferably, the masterbatch is prepared by a method including the following steps: the premix of the single-walled carbon nanotubes and the base rubber are thoroughly mixed on a three-roll mill, preferably until the particle diameter of the obtained mixture is 0.1 μm ~ 20μm, that is to obtain a masterbatch.
  4. 根据权利要求3所述的导电液体硅橡胶，其特征在于，所述基胶中包括充分混合均匀的乙烯基硅油、白炭黑、硅氮烷以及去离子水；The conductive liquid silicone rubber according to claim 3, wherein the base rubber comprises a vinyl silicone oil, white carbon black, silazane, and deionized water which are sufficiently mixed uniformly;
    优选地，所述基胶中包括30～70份乙烯基硅油、15～40份白炭黑、5～15份硅氮烷和1～10份去离子水；Preferably, the base rubber includes 30 to 70 parts of vinyl silicone oil, 15 to 40 parts of white carbon black, 5 to 15 parts of silazane, and 1 to 10 parts of deionized water;
    更优选地，所述基胶采用包括如下步骤的方法制备而成：取甲基乙烯基硅油、白炭黑、硅氮烷和去离子水，在60～90℃、惰性气氛保护下充分混合，然后升温到130～180℃后开始抽真空2～4h,抽真空时保持温度在130～180℃，抽真空结束后降温到120～140℃，再加入稀释用甲基乙烯基硅油，搅拌均匀，即得。More preferably, the base rubber is prepared by a method including the following steps: taking methyl vinyl silicone oil, white carbon black, silazane, and deionized water, and mixing them thoroughly at 60-90 ° C under the protection of an inert atmosphere, Then raise the temperature to 130 ～ 180 ℃ and start vacuuming for 2 ～ 4h. Keep the temperature at 130 ～ 180 ℃ during vacuuming. After the vacuuming is completed, reduce the temperature to 120 ～ 140 ℃. Add methyl vinyl silicone oil for dilution and stir well. That's it.
  5. 根据权利要求4所述的导电液体硅橡胶，其特征在于，所述乙烯基硅油为端基乙烯基硅油和/或多乙烯基硅油，所述端基乙烯基硅油优选为烷基乙烯基硅油、更优选为甲基乙烯基硅油；The conductive liquid silicone rubber according to claim 4, wherein the vinyl silicone oil is a terminal vinyl silicone oil and / or a polyvinyl silicone oil, and the terminal vinyl silicone oil is preferably an alkyl vinyl silicone oil, More preferred is methyl vinyl silicone oil;
    和/或，所述白炭黑为经过硅氮烷等处理剂原位接枝处理的气相白炭黑，其比表面积不 少于200m 2/g，优选所述白炭黑的比表面积为280～320m 2/g； And / or, the white carbon black is a gas-phase white carbon that is subjected to in-situ grafting treatment with a treating agent such as silazane, and has a specific surface area of not less than 200 m 2 / g, and the specific surface area of the white carbon black is preferably 280 ~ 320m 2 / g;
    和/或，所述硅氮烷为六甲基硅氮烷、四甲基二乙烯基硅氮烷、七甲基二硅氮烷、乙烯基单封端硅氮烷等中的至少一种或者两种的混合物，优选为六甲基硅氮烷和/或四甲基二乙烯基硅氮烷。And / or, the silazane is at least one of hexamethylsilazane, tetramethyldivinylsilazane, heptamethyldisilazane, vinyl mono-terminated silazane, or the like; or A mixture of the two is preferably hexamethylsilazane and / or tetramethyldivinylsilazane.
  6. 根据权利要求3～5中任一项所述的导电液体硅橡胶，其特征在于，除所述母胶外，制备所述液体硅橡胶的原料还包括：甲组份、乙组分、催化剂以及抑制剂；The conductive liquid silicone rubber according to any one of claims 3 to 5, characterized in that, in addition to the masterbatch, raw materials for preparing the liquid silicone rubber further include: component A, component B, a catalyst, and Inhibitor
    所述甲组分是通式(1)所示化合物中的一种或几种的混合：The component A is a mixture of one or more of the compounds represented by the general formula (1):
    Figure PCTCN2019098881-appb-100001
    Figure PCTCN2019098881-appb-100001
    所述通式(1)中，n代表0～100的整数；m代表70～4000的整数；R为饱和烃基；R 1为不饱和烃基；R 2为饱和或不饱和烃基；优选地，所述甲组份为R 1为乙烯基且R 2为饱和烃基的端乙烯基硅油，和/或R 1为饱和烃基且R 2为乙烯基的侧链乙烯基硅油，和/或R 1和R 2均为乙烯基的端侧乙烯基硅油； In the general formula (1), n represents an integer from 0 to 100; m represents an integer from 70 to 4000; R is a saturated hydrocarbon group; R 1 is an unsaturated hydrocarbon group; R 2 is a saturated or unsaturated hydrocarbon group; preferably, all The component A is a vinyl-terminated silicone oil in which R 1 is a vinyl group and R 2 is a saturated hydrocarbon group, and / or a side chain vinyl silicone oil in which R 1 is a saturated hydrocarbon group and R 2 is a vinyl group, and / or R 1 and R 2 are vinyl end-side vinyl silicone oils;
    所述乙组份是通式(2)、(3)所示化合物中的一种或几种的混合：The component B is a mixture of one or more of the compounds represented by the general formulae (2) and (3):
    Figure PCTCN2019098881-appb-100002
    Figure PCTCN2019098881-appb-100002
    所述通式(2)中，x为8～200的整数；y为0～60的整数；R 3是甲基、氢基或硅氢基；R 4是甲基、乙基、丙基或苯基； In the general formula (2), x is an integer of 8 to 200; y is an integer of 0 to 60; R 3 is a methyl group, a hydrogen group, or a hydrosilyl group; R 4 is a methyl group, an ethyl group, a propyl group, or Phenyl
    Figure PCTCN2019098881-appb-100003
    Figure PCTCN2019098881-appb-100003
    所述通式(3)中，a为1～300的整数；R 5为甲基、乙基或者氢基； In the general formula (3), a is an integer of 1 to 300; R 5 is a methyl group, an ethyl group, or a hydrogen group;
    优选地，所述乙组分为R 3为氢基且y大于1的两端和侧链均含有SiH的含氢硅油，和/或R 3为氢基且y等于0的端含氢硅油，和/或R 3为饱和烃基且y大于1的侧链含氢硅油，和/或R 5为氢基的含氢硅树脂； Preferably, group B into the group R 3 is hydrogen and y is greater than 1 and the side chain ends are SiH-containing silicone oil and / or R 3 is a hydrogen end group and y is equal to 0 the silicone oil, And / or R 3 is a saturated hydrocarbon group and a side chain hydrogen-containing silicone oil having y greater than 1; and / or R 5 is a hydrogen-containing silicone resin having a hydrogen group;
    其中，当乙组分仅由通式(2)的化合物构成时，y＝0和R 3是甲基这两个条件不同时存在，当乙组分仅由通式(3)的化合物构成时，R 5是氢基，当乙组分是通式(2)、(3)的化合物中的一种或多种的混合时，通式(2)、(3)的化合物中的至少之一具有SiH键， Wherein, when the component B is only composed of the compound of the general formula (2), the two conditions that y = 0 and R 3 are methyl are different. The component B is composed of only the compound of the general formula (3). R 5 is a hydrogen group. When the component B is a mixture of one or more of the compounds of the general formulae (2) and (3), at least one of the compounds of the general formulae (2) and (3) With SiH bond,
    所述催化剂为卡斯特催化剂；The catalyst is a caster catalyst;
    所述抑制剂为1-乙炔基-1-环己醇、2-甲基-3-丁炔-醇和3,5-二甲基-1-己炔-3-醇和3-甲基-1-十二炔-3-醇中的至少一种。The inhibitors are 1-ethynyl-1-cyclohexanol, 2-methyl-3-butyn-ol and 3,5-dimethyl-1-hexyn-3-ol and 3-methyl-1- At least one of dodecyne-3-ols.
  7. 根据权利要求6所述的液体硅橡胶，其特征在于，制备所述液体硅橡胶的原料包括：100份所述母胶，甲组份为10～100份、优选10～65份、更优选10-35份，乙组份为0.4～10份、优选0.4～5份，催化剂为0.002～0.02份、优选0.003～0.01份以及抑制剂为0.02～1份、优选0.02～0.5份；The liquid silicone rubber according to claim 6, wherein the raw material for preparing the liquid silicone rubber comprises: 100 parts of the masterbatch, and the component A is 10 to 100 parts, preferably 10 to 65 parts, more preferably 10 parts. -35 parts, component B is 0.4 to 10 parts, preferably 0.4 to 5 parts, catalyst is 0.002 to 0.02 parts, preferably 0.003 to 0.01 parts and inhibitor is 0.02 to 1 part, preferably 0.02 to 0.5 parts;
    优选地，所述甲组份为端乙烯基硅油、侧链乙烯基硅油和/或端侧乙烯基硅油；所述乙组分为两端和侧链均含有SiH的含氢硅油和/或端基含氢硅油。Preferably, the component A is a vinyl-terminated silicone oil, a side-chain vinyl silicone oil and / or a vinyl-end silicone oil; and the ethyl component is a hydrogen-containing silicone oil and / or a terminal containing SiH at both ends and side chains. Hydrogen-containing silicone oil.
  8. 一种权利要求1-7中任一项的导电液体硅橡胶的制备方法，其特征在于，包括如下步骤：A method for preparing a conductive liquid silicone rubber according to any one of claims 1 to 7, characterized in that it comprises the following steps:
    首先，将单壁碳纳米管与聚有机硅氧烷进行预先混合，得到预混物，优选地，所述单壁碳纳米管占所述预混物的质量百分比为5～20％，First, pre-mix single-walled carbon nanotubes and polyorganosiloxane to obtain a premix. Preferably, the mass percentage of the single-walled carbon nanotubes to the premix is 5-20%.
    其次，将所述预混物与基胶混合，制备得到母胶，再将所述母胶与其它原料混合，经硫化制备得到导电液体硅橡胶，优选地，所述母胶中所含的所述预混物与所述基胶的质量比为(1～10):100、更优选(3.8～10):100，优选地，其他原料包括：甲组分、乙组分、催化剂以及抑制剂。Secondly, the premix is mixed with a base rubber to prepare a masterbatch, and the masterbatch is mixed with other raw materials to prepare a conductive liquid silicone rubber through vulcanization. Preferably, the masterbatch contained in the masterbatch contains The mass ratio of the premix to the base rubber is (1 to 10): 100, more preferably (3.8 to 10): 100. Preferably, other raw materials include: component A, component B, catalyst, and inhibitor .
  9. 权利要求8所述的制备方法，其特征在于，包括如下步骤：The method of claim 8, further comprising the following steps:
    将含有单壁碳纳米管的母胶、催化剂以及至少一种甲组份混合均匀，抽真空脱泡，得到A组分；将含有单壁碳纳米管的母胶、至少一种甲组份、至少一种乙组分以及至少一种抑制剂混合均匀，抽真空脱泡，得到B组分；将所述A组分和B组分等比例混合均匀，固化得试片，硫化，即得；Mix the masterbatch containing single-walled carbon nanotubes, the catalyst, and at least one component A, and then degas under vacuum to obtain component A. The masterbatch containing single-walled carbon nanotubes, at least one component A, At least one component B and at least one inhibitor are mixed uniformly, and degassed under vacuum to obtain component B; the components A and B are mixed in equal proportions, and cured to obtain a test piece, which is obtained by vulcanization;
    优选地，所述方法包括如下步骤：Preferably, the method includes the following steps:
    (1)预混物的制备：将所述单壁碳纳米管与聚有机硅氧烷预先混合得到预混物，其中，所述单壁碳纳米管占所述预混物的质量百分比为5～20％,(1) Preparation of premix: premixing the single-walled carbon nanotubes and polyorganosiloxane to obtain a premix, wherein the mass percentage of the single-walled carbon nanotubes to the premix is 5 ～ 20%,
    (2)基胶的制备：取甲基乙烯基硅油、白炭黑、硅氮烷和去离子水，在60～90℃、惰性气氛保护下充分混合，然后升温到130～180℃后开始抽真空,抽真空时保持温度在130～180℃，抽真空结束后降温到120～140℃，再加入稀释用甲基乙烯基硅油，搅拌均匀，得基胶；(2) Preparation of base rubber: Take methyl vinyl silicone oil, white carbon black, silazane and deionized water, mix thoroughly under the protection of an inert atmosphere at 60-90 ° C, then raise the temperature to 130-180 ° C and start pumping Vacuum, keep the temperature at 130 ～ 180 ℃ when evacuating, and reduce the temperature to 120 ～ 140 ℃ after evacuating, then add methyl vinyl silicone oil for dilution and stir well to obtain base glue;
    (3)母胶的制备：将含有单壁碳纳米管的预混物以及基胶在三辊研磨机上充分混合，即得母胶；(3) Preparation of masterbatch: the premix containing single-walled carbon nanotubes and the base rubber are thoroughly mixed on a three-roll mill to obtain a masterbatch;
    (4)AB组份的制备及硫化：将所述母胶、催化剂以及至少一种甲组份混合均匀，抽真空脱泡，得到A组分；将所述母胶、至少一种甲组份、至少一种乙组分以及至少一种抑制剂混合均匀，抽真空脱泡，得到B组分；将所述A组分和B组分等比例混合均匀，固化得试片，硫化，即得；(4) Preparation and vulcanization of component AB: mixing the masterbatch, catalyst and at least one component A uniformly, degassing under vacuum to obtain component A; the masterbatch, at least one component A , At least one component B and at least one inhibitor are mixed uniformly, and degassed under vacuum to obtain component B; the components A and B are mixed in equal proportions, cured to obtain test pieces, and vulcanized to obtain ;
    更优选地，所述固化的温度为130～170℃；和/或，所述硫化的温度为180～220℃。More preferably, the curing temperature is 130-170 ° C; and / or the curing temperature is 180-220 ° C.
  10. 权利要求1～7中任一项所述的导电液体硅橡胶或权利要求8-9中任一项所述的制备方法获得的导电液体硅橡胶在制备电网附件或电缆附件中的应用。The application of the conductive liquid silicone rubber according to any one of claims 1 to 7 or the conductive liquid silicone rubber obtained by the preparation method according to any one of claims 8 to 9 in the preparation of power network accessories or cable accessories.
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