WO2023160423A1 - 具有高透明导电性能的聚硅氧烷类弹性体及其制备方法 - Google Patents

具有高透明导电性能的聚硅氧烷类弹性体及其制备方法 Download PDF

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WO2023160423A1
WO2023160423A1 PCT/CN2023/075726 CN2023075726W WO2023160423A1 WO 2023160423 A1 WO2023160423 A1 WO 2023160423A1 CN 2023075726 W CN2023075726 W CN 2023075726W WO 2023160423 A1 WO2023160423 A1 WO 2023160423A1
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polysiloxane
molecules
polyethoxy
elastomer
lithium
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English (en)
French (fr)
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谢续明
韦一
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清华大学
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    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J3/00—Processes of treating or compounding macromolecular substances
    • C08J3/24—Crosslinking, e.g. vulcanising, of macromolecules
    • C08J3/246—Intercrosslinking of at least two polymers
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J2383/00—Characterised by the use 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; Derivatives of such polymers
    • C08J2383/04—Polysiloxanes
    • C08J2383/08—Polysiloxanes containing silicon bound to organic groups containing atoms other than carbon, hydrogen, and oxygen
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J2471/00—Characterised by the use of polyethers obtained by reactions forming an ether link in the main chain; Derivatives of such polymers
    • C08J2471/02—Polyalkylene oxides
    • 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
    • C08K3/32—Phosphorus-containing compounds
    • 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
    • C08K3/38—Boron-containing compounds
    • 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
    • C08K5/00—Use of organic ingredients
    • C08K5/36—Sulfur-, selenium-, or tellurium-containing compounds
    • C08K5/43—Compounds containing sulfur bound to nitrogen
    • C08K5/44—Sulfenamides
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
    • Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
    • Y02E60/10—Energy storage using batteries

Definitions

  • the disclosure relates to the technical field of conductive materials, in particular to a polysiloxane-based elastomer with high transparent conductive properties and a preparation method thereof.
  • Polysiloxane elastomer is a kind of polymer prepared by the cross-linking reaction of polysiloxane molecules (A component) and polyethoxy molecules (B component), and has intrinsic conductivity.
  • a component polysiloxane molecules
  • B component polyethoxy molecules
  • polyethoxy Due to the repeated ethoxy structure in the polyethoxy molecule, it can form a coordination structure with lithium ions, and carry out the transport and migration of lithium ions through the movement of the molecular chain, thereby achieving the conductive effect.
  • polyethoxy After molecular polymerization, there are problems of hard material and poor flexibility, so it is difficult to be directly applied to wearable electronic devices and flexible sensors.
  • an object of the present disclosure is to propose polysiloxane-based elastomers with high transparent conductive properties, so as to ensure that polysiloxane-based elastomers have good flexibility, high transparency and skin-friendly properties while having high electrical conductivity. Excellent advantages.
  • the present disclosure proposes a polysiloxane-based elastomer with transparent conductive properties.
  • polysiloxane-based molecules are used as the matrix, and polyethoxy-based molecules As a conductive phase, the polysiloxane molecules and the polyethoxy molecules are cross-linked and solidified to obtain the elastomer, and lithium salt is dispersed in the elastomer.
  • polysiloxane molecules such as flexible molecular chains, high transparency, and excellent skin affinity
  • polysiloxane molecules can be used as a matrix
  • polyethoxy Molecules are used as conductive molecules to cross-link and cure polysiloxane to obtain elastomers
  • lithium salts are dispersed in elastomers, so as to obtain high conductivity while maintaining the flexibility, skin affinity and transparency of polysiloxane molecules.
  • Polysiloxane-based elastomers in addition, polyethoxyl molecules serve as structural components and conductive phases, making polysiloxane-based elastomers intrinsically conductive elastomer materials, compared with traditional conductive filler-type materials Polymer elastomer, the polysiloxane-based elastomer avoids the problems of conductive filler and matrix modulus mismatch, filler dispersion, etc., and can maintain good conductive stability even under large deformation.
  • the polysiloxane-based elastomer has high electrical conductivity and electrical stability, good mechanical properties, better flexibility, skin affinity and transparency, and can be used in flexible touch screens, photovoltaic devices, flexible sensors, Wearable electronic devices and software robots have great application potential and broad application prospects.
  • polysiloxane-based elastomer with transparent conductive properties may also have the following additional technical features:
  • the polysiloxane-based molecules include mercapto groups and/or double bonds.
  • the polysiloxane molecules include mercaptopropyl polydimethylsiloxane, mercaptomethylsiloxane-dimethylsiloxane copolymer, mercapto-terminated polydimethicone At least one of methylsiloxane, double-bond-terminated polydimethylsiloxane, and double-bond methylsiloxane-dimethylsiloxane copolymer.
  • the molecular weight of the polyethoxy molecule is 100-20000, optionally, the molecular weight of the polyethoxy molecule is 130-1000; optionally, the polyethoxy The molecular weight of the base molecule is 400-600.
  • the polyethoxy-based molecules include 2-10 functionalities.
  • the polyethoxy molecules include polyethylene glycol diacrylate, polyethylene glycol monomethyl ether acrylate, 2-acrylate-2-methoxyethyl, polyethylene glycol At least one of diol methyl methacrylate, dimercapto-terminated polyethylene glycol, and monomercapto-terminated polyethylene glycol.
  • the lithium salt includes lithium bistrifluoromethanesulfonimide, lithium bisdifluorosulfonimide, lithium bisoxalate borate, lithium hexafluorophosphate, lithium chloride, and lithium tetrafluoroborate. at least one.
  • the mass ratio of the polysiloxane molecules, the polyethoxy molecules and the lithium salt is (4-8):(0.2-4.0):(0.05-1) .
  • the present disclosure proposes a method for preparing the aforementioned polysiloxane-based elastomer. According to an embodiment of the present disclosure, the method includes:
  • the method for preparing polysiloxane-based elastomer also meets one of the following three conditions:
  • Step (4) also includes: (4-1) soaking the standing reaction product with a mixture of lithium salt and the second compound solvent; (4-2) volatilizing the compound solvent after soaking;
  • step (4) also includes: (4-3) volatilizing the first compound solvent; (4-4) using the mixed solution of lithium salt and the second compound solvent to obtain The product is soaked; (4-5) after the soaking is completed, the second compound solvent is volatilized,
  • first compounded solvent and the second compounded solvent independently include a first component and a second component, and the first component is used to dissolve the polysiloxane molecules and the The polyethoxy molecule, the second component is used to dissolve the lithium salt.
  • the method for preparing polysiloxane-based elastomers according to the above-mentioned embodiments of the present disclosure is not only simple, convenient, repeatable, easy to realize and large-scale production, but also the polysiloxane-based elastomers prepared by this method have high Conductivity and conductivity stability, good mechanical properties, better flexibility, skin-friendly and transparency, have great application potential in flexible touch screens, photovoltaic devices, flexible sensors, wearable electronic devices and soft robots, etc. The prospects are bright.
  • the catalyst includes at least one selected from sodium ethoxide, sodium hydroxide, triethanolamine, triethylamine, azobisisobutyronitrile and diisopropylethylamine.
  • the first component includes at least one selected from dichloromethane, chloroform, tetrahydrofuran, and dimethyl sulfoxide
  • the second component includes at least one selected from glycerin, acetone, and At least one of methyl ethyl ketone, the volume ratio of the first component to the second component is (20-40):(0.5-5).
  • the mass ratio of the polysiloxane molecules, the polyethoxy molecules, the lithium salt and the catalyst is (4-8):(0.2-4.0):( 0.05 ⁇ 2): (0.05 ⁇ 1).
  • the temperature of the static reaction is 10-60° C.
  • the reaction time is 1-24 hours.
  • FIG. 1 is a schematic flow diagram of a method for preparing a polysiloxane-based elastomer according to an embodiment of the present disclosure.
  • FIG. 2 is a partial flow diagram of a method for preparing a polysiloxane-based elastomer according to another embodiment of the present disclosure.
  • FIG. 3 is a partial flow diagram of a method for preparing polysiloxane-based elastomers according to yet another embodiment of the present disclosure.
  • Fig. 4 is a schematic diagram of the transparency performance test of the polysiloxane-based elastomer prepared according to Example 7 of the present disclosure.
  • Fig. 5 is a graph comparing stress-strain curves of polysiloxane-based elastomers prepared according to Example 1 and Examples 4-7 of the present disclosure.
  • FIG. 6 is a comparison chart of electrical resistance tests of polysiloxane-based elastomers prepared according to Examples 1, 3-7 of the present disclosure.
  • Fig. 7 is a comparison chart of electrical conductivity tests of polysiloxane-based elastomers prepared according to Examples 1, 3-7 of the present disclosure.
  • Fig. 8 is a comparison chart of electrical conductivity tests of polysiloxane-based elastomers prepared according to Examples 2, 12, and 17 of the present disclosure.
  • Fig. 9 is a schematic diagram of a universal mechanical testing machine according to an embodiment of the present disclosure.
  • FIG. 10 is a schematic diagram of the contact angle test results of polysiloxane-based elastomers prepared according to Examples 1, 4, 6, and 7 of the present disclosure.
  • FIG. 11 is a schematic diagram of a sample prepared according to Comparative Example 1 of the present disclosure.
  • FIG. 12 is a schematic diagram of a sample prepared according to Comparative Example 2 of the present disclosure.
  • Embodiments of the present disclosure are described in detail below.
  • the embodiments described below are exemplary only for explaining the present disclosure and should not be construed as limiting the present disclosure. If no specific technique or condition is indicated in the examples, it shall be carried out according to the technique or condition described in the literature in this field or according to the product specification. The reagents or instruments used were not indicated by the manufacturer, and they were all commercially available conventional products.
  • first and second are used for description purposes only, and cannot be interpreted as indicating or implying relative importance or implicitly indicating the quantity of indicated technical features.
  • the features defined as “first” and “second” may explicitly or implicitly include at least one of these features.
  • “plurality” means at least two, such as two, three, etc., unless otherwise specifically defined.
  • the present disclosure proposes a polysiloxane-based elastomer with transparent conductive properties.
  • polysiloxane-based molecules are used as the matrix, and polyethoxy-based molecules It is a conductive phase, polysiloxane molecules are cross-linked and cured by polyethoxy molecules to obtain an elastomer, and lithium salt is dispersed in the elastomer.
  • polysiloxane molecules such as flexible molecular chains, high transparency, and excellent skin affinity
  • polysiloxane molecules can be used as a matrix
  • polyethoxy Molecules are used as conductive molecules to cross-link and cure polysiloxane to obtain elastomers
  • lithium salts are dispersed in elastomers, so as to obtain high conductivity while maintaining the flexibility, skin affinity and transparency of polysiloxane molecules.
  • Polysiloxane-based elastomers in addition, polyethoxyl molecules serve as structural components and conductive phases, making polysiloxane-based elastomers intrinsically conductive elastomer materials, compared with traditional conductive filler-type materials Polymer elastomer, the polysiloxane-based elastomer avoids the conductive filler and base Bulk modulus mismatch, filler dispersion and other issues, and can maintain good conductivity stability under large deformation.
  • the polysiloxane-based elastomer has high electrical conductivity and electrical stability, good mechanical properties, better flexibility, skin affinity and transparency, and can be used in flexible touch screens, photovoltaic devices, flexible sensors, Wearable electronic devices and software robots have great application potential and broad application prospects.
  • the polysiloxane-based molecule may include a mercapto group and/or a double bond.
  • the inventors have found that the transparency of polysiloxane elastomers made from polyethoxy molecules and polysiloxane molecules is closely related to the uniformity of dispersion of the two.
  • Matrix and through the way of cross-linking and curing, it is more conducive to the uniform dispersion of polysiloxane molecules and polyethoxy molecules, so that the final cross-linked elastomer has excellent transparency, and the use of mercapto and/or Or polysiloxane molecules with double bonds can provide cross-linking reaction sites to ensure that they can be cross-linked and cured with polyethoxy molecules to achieve polyethoxy molecules and polysilicon molecules with a large difference in polarity.
  • the uniform dispersion between oxane molecules and the construction of cross-linked elastomers meet the requirements of high transparency for the final polysiloxane elastomers; at the same time, compared with the addition of conductive fillers to improve electrical conductivity, polyethylene oxide
  • the uniform dispersion, cross-linking and curing of base molecules and polysiloxane molecules is also conducive to improving the conductive stability of the elastomer, ensuring that the obtained cross-linked polysiloxane elastomer has excellent transparency and electrical conductivity.
  • the transparency of the prepared polysiloxane elastomer can reach more than 90%.
  • the polysiloxane molecules may include mercaptopropyl polydimethylsiloxane, mercaptomethylsiloxane-dimethylsiloxane copolymer, mercapto-terminated polydimethylsiloxane At least one of base siloxane, double bond terminated polydimethylsiloxane and double bond methylsiloxane-dimethylsiloxane copolymer.
  • polysiloxane molecules and polyethoxy molecules are uniformly dispersed to construct a cross-linked elastomer, so that the final polysiloxane elastomer has excellent transparency and is also conducive to improving its conductive stability.
  • the molecular weight of polyethoxy molecules can be 100-20000, specifically 100, 300, 500, 700, 1000, 5000, 10000, 15000, 20000, etc.
  • the inventors found that if polyethylene If the molecular weight of the oxygen-based molecule is too small, it will affect the coordination between the polyethoxy-based molecule and lithium ions, which is not conducive to improving the conductivity of the polysiloxane-based elastomer; if the molecular weight of the polyethoxy-based molecule is too large , its hardness after cross-linking and curing is also relatively large, and it is difficult to effectively improve or significantly reduce its negative impact on the flexibility and skin-friendly properties of polysiloxane elastomers when used as a conductive phase and structural component; and through Controlling the molecular weight of polyethoxy molecules to 100-20,000 is more conducive to making polysiloxane elastomers have high conductivity, high flexibility and good skin affinity.
  • the molecular weight of the polyethoxy molecules can be 130-1000; more preferably, the molecular weight of the polyethoxy molecules can be 400-600, thus, it can further ensure that the obtained cross-linked polysiloxane Elastomers have excellent transparency, electrical conductivity as well as flexibility and skin-friendly properties.
  • polyethoxy molecules may include monofunctional polyethoxy molecules and/or multiple monofunctional polyethoxy molecules, for example, polyethoxy molecules may include 2 ⁇ 10 functionalities, in which polyethoxy molecules with multiple functionalities can be used to further promote the sufficient cross-linking and curing of polyethoxy molecules and polysiloxane molecules, so as to further ensure cross-linking High transparency of polysiloxane-based elastomers.
  • polyethoxy molecules are not particularly limited, and those skilled in the art can flexibly choose according to actual needs.
  • polyethoxy molecules can include polyethylene glycol Acrylate (PEGDA), polyethylene glycol monomethyl ether acrylate (PEGMA), 2-methoxyethyl acrylate (MEA), polyethylene glycol dimethacrylate, dimercapto terminated poly At least one of ethylene glycol and monomercapto-terminated polyethylene glycol, the inventors found that selecting the above-mentioned polyethoxy molecule is more conducive to making the obtained cross-linked polysiloxane elastomer have excellent transparency, Conductive properties as well as properties such as flexibility and skin-friendliness.
  • the addition of lithium salt can form a coordination effect with the ethoxy structure in the polyethoxy molecule, so that the transport and migration of lithium ions can be carried out through the movement of the molecular chain, and the conductive effect can be achieved.
  • lithium The salt may be an organic lithium salt or an inorganic lithium salt, and may include lithium bistrifluoromethanesulfonimide, lithium bisdifluorosulfonimide, lithium bisoxalate borate, lithium hexafluorophosphate, lithium chloride, and lithium tetrafluoroborate.
  • the lithium salt is preferably an organic lithium salt
  • the inventors have found that, compared to the inorganic lithium salt, the electrical conductivity of the organic lithium salt added to polysiloxane elastomers is higher, and the organic lithium salt can be more Lithium bistrifluoromethanesulfonylimide (LITFSI) is preferred.
  • LITFSI has the best electrical conductivity among the above-mentioned organic lithium salts. Thus, it can not only improve the compatibility of lithium salts and polysiloxanes, but also ensure the obtained
  • the cross-linked polysiloxane elastomer has excellent transparency and electrical conductivity.
  • the mass ratio of polysiloxane molecules, polyethoxy molecules and lithium salts may be (4-8):(0.2-4.0):(0.05-1), specifically 4 /0.2/0.05, 4/0.2/0.5, 4/0.2/1, 4/1.0/0.05, 4/4.0/0.05, 6/0.2/0.05, 6/4.0/1, 8/0.2/0.05, 8/4.0 /1 etc., the inventors have found that the higher the polyethoxy molecule content is, the more it is beneficial to improve the overall conductivity of the polysiloxane elastomer.
  • lithium salts and polyethoxy molecules have a certain coordination relationship, if the content of lithium salt is too small, the coordination with the ethoxy structure will be less, and it will be difficult to achieve a better conductive effect, and as the amount of lithium salt increases, the conductivity of the elastomer will also increase, but When the content of lithium salt exceeds its coordination relationship with polyethoxy molecules, the increase of lithium salt content will not further improve the conductive effect, but will also affect the adhesion performance of polysiloxane-based elastomers, causing its adhesion If the solubility is too high, it will increase the difficulty of subsequent desorption.
  • the mass ratio of polysiloxane molecules, polyethoxy molecules and lithium salts to (4-8): (0.2-4.0): (0.05-1)
  • the elasticity of polysiloxanes can be guaranteed.
  • the body has high electrical conductivity, conductive stability and good mechanical properties under the premise of high flexibility, skin affinity and transparency.
  • the transparency of the polysiloxane elastomer can reach more than 92%
  • the stress can reach 100KPa and above
  • the resistivity can reach 1.0 ⁇ 10 -2 S/m or even higher. level.
  • the present disclosure proposes a method for preparing the aforementioned polysiloxane-based elastomer. According to an embodiment of the present disclosure, referring to FIG. 1 , the method includes:
  • the polysiloxane molecules and polyethoxy molecules are fully mixed in the first compounding solvent, so that the polysiloxane molecules and polyethoxy molecules with greatly different polarities Uniform mixing is conducive to the progress of crosslinking reaction.
  • the first composite solvent includes a first component for dissolving polysiloxane molecules and polyethoxy molecules, and the first component may include but not limited to dichloromethane, chloroform, at least one of tetrahydrofuran and dimethylsulfoxide. It should be noted that the selection and proportion of raw materials for polysiloxane molecules and polyethoxy molecules have been described in detail above, and will not be repeated here.
  • the mass ratio of polysiloxane molecules, polyethoxy molecules and the first compounding solvent can be (4-8): (0.2-4.0): (20-40), the inventor It is found that if the amount of solvent is too much, the subsequent solvent will evaporate slowly and the curing time of the elastomer will be prolonged, and if the amount of solvent is too small, the concentration of polysiloxane molecules and polyoxyethyl molecules in the mixed solution will be too high It affects the dissolution, thereby affecting the progress of the cross-linking reaction.
  • polysiloxane molecules, polyethoxy molecules and the first compound solvent By controlling the polysiloxane molecules, polyethoxy molecules and the first compound solvent to the above mass ratio, it can ensure that each component is fully dissolved, which is more conducive to Ensure polysiloxane elastomers have excellent comprehensive properties such as transparency, flexibility, skin affinity, electrical conductivity and mechanical properties.
  • the catalyst is fully stirred and mixed with the first mixed liquid obtained in step S100 to obtain a second mixed liquid.
  • the addition of the catalyst is used to increase the rate and crosslinking density of the crosslinking reaction between the polysiloxane molecules and the polyethoxy molecules, thereby improving the preparation efficiency and yield.
  • the type of catalyst is not particularly limited, and can be flexibly selected in the field according to needs, as long as it can promote the cross-linking and curing of polysiloxane molecules and polyethoxy molecules to build elastomers,
  • it may be a thermal initiator, etc.
  • the catalyst may include at least one selected from sodium ethoxide, sodium hydroxide, triethanolamine, triethylamine, azobisisobutyronitrile and diisopropylethylamine.
  • the lithium salt may be directly mixed into the second mixed liquid.
  • the preparation process of polysiloxane-based elastomers also includes the addition of lithium salts, wherein the addition of lithium salts can be added in situ, that is, the lithium salts are uniformly mixed with each raw material component before crosslinking Curing reaction, for example, lithium salt can be mixed in the second mixed solution, or the catalyst, lithium salt and the first mixed solution can be mixed to obtain the second mixed solution; the lithium salt solution can also be used after the cross-linking curing reaction to prepare the elastic The body is soaked, so that the lithium salt is evenly dispersed in the elastomer.
  • the second mixed solution or lithium salt solution should include a second component for dissolving lithium salts, wherein the second component Can include glycerol, acetone and at least one of methyl ethyl ketone, in addition, the lithium salt solution should also include a first component for dissolving polysiloxane molecules and polyethoxy molecules.
  • step S200 the second mixed liquid obtained in step S200 is transferred to a mold for static reaction, under the catalytic action of the catalyst, the polyethoxy-based molecules and polysiloxane-based molecules undergo a cross-linking reaction.
  • the standing reaction temperature can be 10-60°C, specifically 10°C, 30°C, 40°C, 50°C, 60°C, etc.
  • the reaction time can be 1-24h, specifically 1h , 5h, 10h, 15h, 20h, 24h, etc.
  • the rise of the static reaction temperature will accelerate the rate of the crosslinking reaction, but if the reaction temperature is too high, it may cause the solvent to volatilize and affect the uniform mixing of each component.
  • each component can also make polyethoxy molecules and polysiloxane molecules form a dense cross-linked network structure, which is conducive to obtaining both high electrical conductivity and conductive stability, as well as high Transparency, polysiloxane elastomer with good flexibility, skin-friendly and mechanical properties.
  • the product obtained after the cross-linking reaction in step S300 can be placed in a vacuum oven to volatilize the compounding solvent to obtain a polysiloxane-based elastomer.
  • the temperature for volatilizing the compound solvent is not particularly limited, and those skilled in the art can choose flexibly according to actual needs, as long as the compound solvent can be completely volatilized, for example, the temperature can be 80°C, 90°C, etc. .
  • condition (a) when the second mixed liquid does not contain lithium salt, the preparation process of polysiloxane elastomer also needs to meet condition (a) or condition (b):
  • step S400 also includes:
  • step S400 may also include:
  • the inventors found that when the elastomer obtained by cross-linking and curing is soaked in a lithium salt solution, the elastomer can absorb the lithium salt solution and swell to realize the uniform diffusion of the lithium salt in the elastomer, thereby realizing polysiloxane-based elastomers. of high conductivity.
  • the process condition of (b) is preferably adopted, which is more conducive to the full absorption of the second compounding solvent by the elastomer, and ensures that the lithium salt can be uniformly diffused in the elastomer with the second compounding solvent.
  • adding lithium salt by immersion is more beneficial to improve the conductivity of polysiloxane-based elastomers than adding lithium salt in situ.
  • the first compounded solvent and the second compounded solvent may independently include a first component and a second component
  • the first component may include a compound selected from dichloromethane, chloroform, tetrahydrofuran and at least one of dimethyl sulfoxide
  • the second component can be Including at least one selected from glycerin, acetone and methyl ethyl ketone
  • the volume ratio of the first component and the second component may be (20-40): (0.5-5), specifically 20/0.5 , 20/1, 20/3.5, 20/5, 30/0.5, 30/3.5, 30/5, 40/0.5, 40/1.5, 40/5, etc.
  • the first component is used to dissolve polysiloxane molecules and polyethoxy molecules
  • the second component is used to dissolve lithium salts. If the volume ratio of the first component and the second component is too high, it is quite Because the amount of the second component is less, the solubility of lithium salt may be affected under the limited amount of solvent, and then it is difficult to improve the conductivity of the polysiloxane elastomer prepared; if the first component and the second component If the volume ratio is too low, it will make it difficult for the polysiloxane molecules and polyethoxy molecules to be completely dissolved in the compound solvent, thereby affecting the progress of the crosslinking reaction, and it is difficult to ensure the elasticity of the prepared polysiloxane
  • the mass ratio of polysiloxane molecules, polyethoxy molecules, lithium salts, and catalysts may be (4-8): (0.2-4.0): (0.05-2): (0.05 ⁇ 1), specifically 4/0.2/0.05/0.05, 4/0.2/0.5/0.05, 4/0.2/1/0.05, 4/1.0/0.05/0.05, 4/4.0/0.05/0.05, 6/0.2 /0.05/0.05, 6/4.0/1/0.05, 8/0.2/0.05/0.05, 8/4.0/1/0.05, 4/0.2/0.05/0.1, 4/0.2/0.05/1, etc.
  • the preparation efficiency and yield can be improved, and it is more conducive to making the prepared cross-linked polysiloxane elastomer have high electrical conductivity and conductive stability, as well as high transparency, flexibility, affinity Excellent skin and mechanical properties.
  • the method is not only simple, convenient, repeatable, and easy to realize and scale production, but also the polysiloxane-based elastomers prepared by this method It has high electrical conductivity and conductive stability, good mechanical properties, good flexibility, skin affinity and transparency, and has great potential in flexible touch screens, photovoltaic devices, flexible sensors, wearable electronic devices and software robots. application potential and broad application prospects. It should be noted that the features and effects described above for the polysiloxane-based elastomer with transparent conductive properties are also applicable to the method for preparing the polysiloxane-based elastomer, and will not be repeated here.
  • step (1) 0.9 g of polyethylene glycol diacrylate is dissolved in the above-mentioned chloroform solvent.
  • step (1) 1.0 g of polyethylene glycol diacrylate is dissolved in the above-mentioned chloroform solvent.
  • step (1) 1.25 g of polyethylene glycol diacrylate is dissolved in the above-mentioned chloroform solvent.
  • step (1) 1.5 g of polyethylene glycol diacrylate is dissolved in the above-mentioned chloroform solvent.
  • step (1) 1.75 g of polyethylene glycol diacrylate is dissolved in the above-mentioned chloroform solvent.
  • step (1) 2.25 g of polyethylene glycol diacrylate is dissolved in the above-mentioned chloroform solvent.
  • step (1) 9g of mercaptopropyl polydimethylsiloxane is dissolved in 30g of dichloromethane solvent, shaken up, and then 0.8g of polyethylene glycol diacrylate is dissolved. in the aforementioned dichloromethane solvent.
  • step (2) Pour the second mixed solution in the embodiment (step (2)) into a quartz cuvette with a light path of 10mm, let it stand for 12h to make mercaptopropyl polydimethylsiloxane and polyethylene glycol diacrylate cross Combined curing to obtain a polysiloxane-based elastomer; then placed in a vacuum oven at 80° C. to remove the remaining solvent. Then use an ultraviolet spectrometer to test, with a wavelength range of 400nm to 800nm (visible light), to observe the absorption of the polysiloxane elastomer in the visible light range.
  • an ultraviolet spectrometer to test, with a wavelength range of 400nm to 800nm (visible light), to observe the absorption of the polysiloxane elastomer in the visible light range.
  • the prepared polysiloxane-based elastomers were respectively prepared into 20mm ⁇ 10mm ⁇ 2mm sample strips, and glass was selected as the substrate for adhesion performance testing. Before the test, the specimen is sandwiched between two pieces of glass.
  • the tensile instrument is the Shimadzu AGS-X universal mechanical testing machine produced by Shimadzu Corporation of Japan.
  • the stress-strain curve of the test fixture after 10mm stretching was repeated 5 times, the integral area of the stress-strain curve was the peeling work, and the average value of the maximum peeling force of the 5 repeated experiments was taken as the peeling force.
  • the prepared polysiloxane elastomers were respectively prepared into 30mm ⁇ 10mm ⁇ 2mm sample strips, and were tested using a Tonghui TH2826LCR Meter digital bridge LCR tester. During the test, connect the positive and negative poles of the electric bridge to both ends of the spline, and read the resistance value when the display is stable.
  • the electrical conductivity of the polysiloxane-based elastomer is obtained according to Formula 3-1 and Formula 3-2.
  • R-resistance value, ⁇ -resistivity of the material used to make the resistor, l-the length of the wire wound to make the resistor, S-the cross-sectional area of the wire wound to make the resistor are examples of resistors.
  • the prepared polysiloxane-based elastomers were prepared into 30mm ⁇ 30mm samples respectively, and placed on glass substrates.
  • the contact angle tester used a TBU100 model machine from Dataphysics, Germany. Before the test, keep the surface of the sample clean and flat, and then drop water droplets in the middle of the sample, and measure the degree of contact angle through the contact angle analysis software.
  • the polysiloxane materials and the polysiloxane elastomers prepared in the examples were respectively prepared into circular films with a diameter of 90mm.
  • Rate tester the test method adopts GB/T 1037-1988 plastic film and sheet water vapor permeability test method cup method.
  • the film thickness is 1.5mm
  • the temperature is controlled at 38°C
  • the relative humidity is 90%. The test was terminated when the water vapor transmission reached a steady state.
  • Fig. 4 is a schematic diagram of the transparency performance test of the polysiloxane-based elastomer prepared in Example 7;
  • Fig. 5 is a comparison of the stress-strain curves of the polysiloxane-based elastomer prepared in Example 1 and Examples 4-7 Figure (the abscissa corresponds to the tensile strain of the elastic body, and the ordinate corresponds to stress);
  • Fig. 6 is the resistance test comparison chart of the polysiloxane elastomer prepared in embodiment 1, 3 ⁇ 7;
  • Fig. 7 is the conductance of the polysiloxane elastomer prepared in embodiment 1, 3 ⁇ 7 Rate test comparison chart (wherein in Fig.
  • Fig. 7 the mass fraction of polyethoxy molecule refers to the consumption of polyethoxy molecule relative to polysilane molecule);
  • Fig. 8 is prepared by embodiment 2, 12, 17 The electrical conductivity test contrast chart of polysiloxane elastomer;
  • Fig. 9 is the device schematic diagram of universal mechanical testing machine;
  • Fig. 10 is the contact angle of the polysiloxane elastomer prepared in embodiment 1, 4, 6, 7 Schematic diagram of the test results;
  • Figure 11 is a schematic diagram of the sample prepared in Comparative Example 1;
  • Figure 12 is a schematic diagram of the sample prepared in Comparative Example 2;
  • Table 1 is the polysiloxane materials and the polysiloxane prepared in Example 7 The test results of the water vapor transmission rate of the elastomer.
  • bifunctional polyethoxy molecules such as polyethylene glycol diacrylate in Examples 1 to 7, 9 to 12, and polyethylene glycol diacrylate in Examples 14 to 16 Dimercapto-terminated polyethylene glycol
  • polysiloxane elastomers compared to monofunctional polyethoxy molecules, bifunctional polyethoxy molecules (such as polyethylene glycol diacrylate in Examples 1 to 7, 9 to 12, and polyethylene glycol diacrylate in Examples 14 to 16 Dimercapto-terminated polyethylene glycol) is more tightly cross-linked with polysiloxane molecules, and microphase separation between polysiloxane molecules is not easy to affect the overall transparency of polysiloxane elastomers. , so that the prepared polysiloxane elastomer has excellent transparency, which can reach more than 90%.
  • the tensile properties of polysiloxane elastomers are closely related to the crosslink density of polyethoxy molecules and polysilane molecules, and the crosslink density of elastomers becomes larger, and the overall elongation The lower the rate.
  • the adhesion performance of polysiloxane-based elastomers is also closely related to the cross-linking density of polyethoxylated molecules and polysilane-based molecules. The force is mainly determined by the crosslink density of the elastomer.
  • Example 12 the electrical conductivity of the polysiloxane-based elastomer prepared in Example 12 is significantly higher than that of Example 2 and Example 17, which also shows that the electrical conductivity of the polysiloxane-based elastomer It is closely related to the way of adding lithium salt.
  • the way of absorbing lithium salt by soaking can further improve the conductivity of polysiloxane-based elastomers; in addition, in combination with other
  • the test results of the electrical conductivity of the polysiloxane elastomers obtained in the examples and related tests show that the electrical conductivity of the polysiloxane elastomers is also related to the cross-linking of polyethoxylate molecules and polysiloxane molecules.
  • the method, the type of lithium salt, and the amount of lithium salt added are closely related. In cross-linked polysiloxane elastomers, the faster the molecular chain moves, the higher the conductivity of polysiloxane elastomers.
  • the single The higher the ratio of the arm polyethoxy molecule (polyethylene glycol monomethyl acrylate, 2-methoxyethyl acrylate), the higher the mobility of the molecular chain, and the higher the conductivity of the elastomer; in addition, The conductivity of organolithium salts is significantly higher than that of inorganic lithium salts, among which lithium bistrifluoromethanesulfonylimide (LITFSI) has the best conductivity.
  • LITFSI lithium bistrifluoromethanesulfonylimide
  • polysiloxanes With the increase of polyethoxy molecules content, polysiloxanes The hydrophilicity of the elastomer becomes better; in addition, as can be seen from Table 1, the permeation amount of the polysiloxane material mercaptopropyl polydimethylsiloxane is 98.6725g/(m 2 ⁇ 24h), the embodiment 7 The penetration rate of the prepared polysiloxane elastomer is 185.5315g/(m 2 ⁇ 24h), which is significantly higher than that of polysiloxane materials. Adding it can effectively improve the water vapor permeability of polysiloxane elastomers.
  • Figure 11 is a schematic diagram of the sample prepared in Comparative Example 1. It can be seen from Figure 11 that when polyethoxy molecules are in excess relative to polysiloxane molecules, too many polyethoxy molecules cannot fully participate reaction, and the polyethoxyl molecules that have not participated in the reaction will attach to the surface of the polysiloxane elastomer formed by crosslinking and curing, seriously affecting the transparency, flexibility and skin-friendly properties of the elastomer.
  • Figure 12 is a schematic diagram of the sample prepared in Comparative Example 2.

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Abstract

公开了具有高透明导电性能的聚硅氧烷类弹性体及其制备方法。该聚硅氧烷类弹性体以聚硅氧烷类分子为基体，以聚乙氧基类分子为导电相，所述聚硅氧烷类分子和所述聚乙氧基类分子通过交联固化得到所述弹性体，所述弹性体中分散有锂盐。

Description

具有高透明导电性能的聚硅氧烷类弹性体及其制备方法
优先权信息
本申请请求2022年2月22日向中国国家知识产权局提交的、专利申请号为202210163290.6的专利申请的优先权和权益，并且通过参照将其全文并入此处。
技术领域
本公开涉及导电材料技术领域，尤其涉及具有高透明导电性能的聚硅氧烷类弹性体及其制备方法。
背景技术
聚硅氧烷类弹性体是由聚硅氧烷类分子(A组分)与聚乙氧基类分子(B组分)交联反应制备的一种聚合物，具有本征导电性。目前随着互联网和大数据时代的到来，人们越来越重视可穿戴设备、贴身健康检测设备的需求，但是传统外加石墨烯、碳纳米管、金属纳米线等制备导电弹性体的方法，在材料大变形的条件下会造成导电填料与基体的分散性不佳，导致模量失配问题的产生，引发导电网络不可逆滑移甚至断裂的风险，使得弹性体的导电性能急剧恶化。
公开内容
本公开主要是基于以下问题和发现提出的：
由于聚乙氧基类分子中具有重复的乙氧基结构，可以与锂离子形成配位结构，通过分子链的运动进行锂离子的运输和迁移，从而达到导电效果，但是，聚乙氧基类分子聚合后存在材质硬，柔韧性差的问题，很难直接应用到可穿戴电子器件、柔性传感器中。此外，聚硅氧烷类分子具有分子链柔顺(Tg＝-123℃)，透明度高(透光度100％)以及亲肤性优异的特点，本公开将聚硅氧烷类分子作为基体，聚乙氧基类分子作为导电相来制备透明导电弹性体具有很大的应用前景。
本公开旨在至少在一定程度上解决相关技术中的技术问题之一。为此，本公开的一个目的在于提出具有高透明导电性能的聚硅氧烷类弹性体，以保证聚硅氧烷类弹性体在具有高电导率的同时具有柔韧性好、透明性高和亲肤性优异的优点。
在本公开的一个方面，本公开提出了一种具有透明导电性能的聚硅氧烷类弹性体，根据本公开的实施例，以聚硅氧烷类分子为基体，以聚乙氧基类分子为导电相，所述聚硅氧烷类分子和所述聚乙氧基类分子通过交联固化得到所述弹性体，所述弹性体中分散有锂盐。
由于聚乙氧基类分子中具有重复的乙氧基结构，可以与锂离子形成配位结构，通过配位结构分子链的运动进行锂离子的运输和迁移，从而具有较好的导电效果，但其材质硬，柔韧性差，考虑到聚硅氧烷类分子的分子链柔顺、透明度高、亲肤性优异的特点，发明人设想，可以利用聚硅氧烷类分子作为基体，聚乙氧基类分子作为导电相对聚硅氧烷进行交联固化得到弹性体，并在弹性体中分散锂盐，从而在保持聚硅氧烷类分子柔韧性、亲肤性和透明度优异的同时获得高电导率的聚硅氧烷类弹性体；此外，聚乙氧基类分子兼作结构组分和导电相，使得聚硅氧烷类弹性体为本征型导电弹性体材料，相比传统的外加导电填料型的高分子弹性体，该聚硅氧烷类弹性体避免了导电填料与基体模量失配、填料分散等问题，且在大变形下也能保持较好的导电稳定性。由此，该聚硅氧烷类弹性体兼具较高的电导率和导电稳定性、良好的力学性能、较佳的柔韧性、亲肤性和透明度，在柔性触摸屏、光伏器件、柔性传感器、可穿戴电子器件及软体机器人等方面具有巨大的应用潜力，应用前景广。
另外，根据本公开上述实施例的具有透明导电性能的聚硅氧烷类弹性体还可以具有如下附加的技术特征：
根据本公开的实施例，所述聚硅氧烷类分子包括巯基和/或双键。
根据本公开的实施例，所述聚硅氧烷类分子包括选自巯丙基聚二甲基硅氧烷、巯基甲基硅氧烷-二甲基硅氧烷共聚物、巯基封端聚二甲基硅氧烷、双键封端聚二甲基硅氧烷和双键甲基硅氧烷-二甲基硅氧烷共聚物中的至少一种。
根据本公开的实施例，所述聚乙氧基类分子的分子量为100～20000，任选地，所述聚乙氧基类分子的分子量为130～1000；任选地，所述聚乙氧基类分子的分子量为400～600。
根据本公开的实施例，所述聚乙氧基类分子包括2～10个官能度。
根据本公开的实施例，所述聚乙氧基类分子包括选自聚乙二醇二丙烯酸酯、聚乙二醇单甲醚丙烯酸酯、2-丙烯酸-2-甲氧基乙酯、聚乙二醇二甲基丙烯酸甲酯、二巯基封端聚乙二醇和单巯基封端聚乙二醇中的至少一种。
根据本公开的实施例，所述锂盐包括选自双三氟甲烷磺酰亚胺锂、双二氟磺酰亚胺锂、双草酸硼酸锂、六氟磷酸锂、氯化锂和四氟硼酸锂中的至少一种。
根据本公开的实施例，所述聚硅氧烷类分子、所述聚乙氧基类分子和所述锂盐的质量比为(4～8)：(0.2～4.0)：(0.05～1)。
在本公开的另一个方面，本公开提出了一种制备前面所述的聚硅氧烷类弹性体的方法，根据本公开的实施例，该方法包括：
(1)将聚硅氧烷类分子、聚乙氧基类分子和第一复配溶剂混合，得到第一混合液；
(2)将催化剂与所述第一混合液混合，得到第二混合液；
(3)将所述第二混合液转移至模具中进行静置反应；
(4)使复配溶剂挥发，以便得到所述聚硅氧烷类弹性体，
其中，制备聚硅氧烷类弹性体的方法还满足以下3个条件之一：
(a)在进行步骤(3)之前在所述第二混合液中混入锂盐；
(b)步骤(4)还包括：(4-1)利用锂盐和第二复配溶剂的混合液对静置反应产物进行浸泡；(4-2)浸泡完成后使复配溶剂挥发；
(c)步骤(4)还包括：(4-3)使所述第一复配溶剂挥发；(4-4)利用锂盐和第二复配溶剂的混合液对步骤(4-3)得到的产物进行浸泡；(4-5)浸泡完成后使所述第二复配溶剂挥发，
另外，所述第一复配溶剂和所述第二复配溶剂分别独立地包括第一组分和第二组分，所述第一组分用于溶解所述聚硅氧烷类分子和所述聚乙氧基类分子，所述第二组分用于溶解所述锂盐。
本公开上述实施例的制备聚硅氧烷类弹性体的方法不仅操作简单、方便，可重复，易于实现和规模化生产，且采用该方法制备的聚硅氧烷类弹性体兼具较高的电导率及导电稳定性、良好的力学性能、较佳的柔韧性、亲肤性和透明度，在柔性触摸屏、光伏器件、柔性传感器、可穿戴电子器件及软体机器人等方面具有巨大的应用潜力，应用前景广。
根据本公开的实施例，所述催化剂包括选自乙醇钠、氢氧化钠、三乙醇胺、三乙胺、偶氮二异丁腈和二异丙基乙胺中的至少一种。
根据本公开的实施例，所述第一组分包括选自二氯甲烷、三氯甲烷、四氢呋喃和二甲基亚砜中的至少一种，所述第二组分包括选自甘油、丙酮和甲基乙基酮中的至少一种，所述第一组分和所述第二组分的体积比为(20～40)：(0.5～5)。
根据本公开的实施例，所述聚硅氧烷类分子、所述聚乙氧基类分子、所述锂盐和所述催化剂的质量比为(4～8)：(0.2～4.0)：(0.05～2)：(0.05～1)。
根据本公开的实施例，所述静置反应的温度为10～60℃，反应时间为1～24h。
本公开的附加方面和优点将在下面的描述中部分给出，部分将从下面的描述中变得明显，或通过本公开的实践了解到。
附图说明
本公开的上述和/或附加的方面和优点从结合下面附图对实施例的描述中将变得明显和容易理解，其中：
图1是根据本公开一个实施例的制备聚硅氧烷类弹性体的方法的流程示意图。
图2是根据本公开另一个实施例的制备聚硅氧烷类弹性体的方法的部分流程示意图。
图3是根据本公开又一个实施例的制备聚硅氧烷类弹性体的方法的部分流程示意图。
图4是根据本公开实施例7制备的聚硅氧烷类弹性体的透明性能测试示意图。
图5是根据本公开实施例1、实施例4～7制备的聚硅氧烷类弹性体的应力-应变曲线对比图。
图6是根据本公开实施例1、3～7制备的聚硅氧烷类弹性体的电阻测试对比图。
图7是根据本公开实施例1、3～7制备的聚硅氧烷类弹性体的电导率测试对比图。
图8是根据本公开实施例2、12、17制备的聚硅氧烷类弹性体的电导率测试对比图。
图9是根据本公开一个实施例的万用力学试验机的装置示意图。
图10是根据本公开实施例1、4、6、7制备的聚硅氧烷类弹性体的接触角测试结果示意图。
图11是根据本公开对比例1制得的样品的示意图。
图12是根据本公开对比例2制得的样品的示意图。
具体实施方式
下面详细描述本公开的实施例。下面描述的实施例是示例性的，仅用于解释本公开，而不能理解为对本公开的限制。实施例中未注明具体技术或条件的，按照本领域内的文献所描述的技术或条件或者按照产品说明书进行。所用试剂或仪器未注明生产厂商者，均为可以通过市购获得的常规产品。
在本公开的描述中，需要理解的是，术语“第一”、“第二”仅用于描述目的，而不能理解为指示或暗示相对重要性或者隐含指明所指示的技术特征的数量。由此，限定有“第一”、“第二”的特征可以明示或者隐含地包括至少一个该特征。在本公开的描述中，“多个”的含义是至少两个，例如两个，三个等，除非另有明确具体的限定。
在本公开的一个方面，本公开提出了一种具有透明导电性能的聚硅氧烷类弹性体，根据本公开的实施例，以聚硅氧烷类分子为基体，以聚乙氧基类分子为导电相，聚硅氧烷类分子由聚乙氧基类分子交联固化得到弹性体，弹性体中分散有锂盐。
由于聚乙氧基类分子中具有重复的乙氧基结构，可以与锂离子形成配位结构，通过配位结构分子链的运动进行锂离子的运输和迁移，从而具有较好的导电效果，但其材质硬，柔韧性差，考虑到聚硅氧烷类分子的分子链柔顺、透明度高、亲肤性优异的特点，发明人设想，可以利用聚硅氧烷类分子作为基体，聚乙氧基类分子作为导电相对聚硅氧烷进行交联固化得到弹性体，并在弹性体中分散锂盐，从而在保持聚硅氧烷类分子柔韧性、亲肤性和透明度优异的同时获得高电导率的聚硅氧烷类弹性体；此外，聚乙氧基类分子兼作结构组分和导电相，使得聚硅氧烷类弹性体为本征型导电弹性体材料，相比传统的外加导电填料型的高分子弹性体，该聚硅氧烷类弹性体避免了导电填料与基 体模量失配、填料分散等问题，且在大变形下也能保持较好的导电稳定性。由此，该聚硅氧烷类弹性体兼具较高的电导率和导电稳定性、良好的力学性能、较佳的柔韧性、亲肤性和透明度，在柔性触摸屏、光伏器件、柔性传感器、可穿戴电子器件及软体机器人等方面具有巨大的应用潜力，应用前景广。
根据本公开的实施例，聚硅氧烷类分子可以包括巯基和/或双键。发明人发现，由于聚乙氧基类分子和聚硅氧烷类分子制得的聚硅氧烷类弹性体的透明性能与二者的分散均匀程度密切相关，通过以聚硅氧烷类分子为基体，并通过交联固化的方式，更有利于聚硅氧烷类分子与聚乙氧基类分子的均匀分散，使最终制得的交联弹性体具有优异的透明度，而采用包括巯基和/或双键的聚硅氧烷类分子，可以提供交联反应位点，确保其能与聚乙氧基类分子进行交联固化，实现极性相差较大的聚乙氧基类分子和聚硅氧烷类分子之间的均匀分散并构建交联弹性体，满足最终制得的聚硅氧烷类弹性体具有较高的透明度的要求；同时，相对于添加导电填料改善导电性能，聚乙氧基类分子和聚硅氧烷类分子的均匀分散交联固化还有利于提高弹性体的导电稳定性，保证所得到的交联聚硅氧烷类弹性体具有优异的透明度和导电性能，其中，制得的聚硅氧烷类弹性体的透明度可达到90％以上。
根据本公开的实施例，聚硅氧烷类分子可以包括选自巯丙基聚二甲基硅氧烷、巯基甲基硅氧烷-二甲基硅氧烷共聚物、巯基封端聚二甲基硅氧烷、双键封端聚二甲基硅氧烷和双键甲基硅氧烷-二甲基硅氧烷共聚物中的至少一种。由此，可以进一步保证聚硅氧烷类分子与聚乙氧基类分子均匀分散构建交联弹性体，以使最终制得的聚硅氧烷类弹性体具有优异的透明度，同时也有利于提高其导电稳定性。
根据本公开的实施例，聚乙氧基类分子的分子量可以为100～20000，具体可以为100、300、500、700、1000、5000、10000、15000、20000等，发明人发现，若聚乙氧基类分子的分子量过小，会影响聚乙氧基类分子与锂离子的配位作用，不利于提高聚硅氧烷类弹性体的导电性；若聚乙氧基类分子的分子量过大，其进行交联固化后的硬度也较大，难以有效改善或显著降低其作为导电相和结构组分使用时对聚硅氧烷类弹性体柔韧性和亲肤性带来的负面影响；而通过控制聚乙氧基类分子的分子量为100～20000，更有利于使聚硅氧烷类弹性体兼具高导电性、高柔韧性和较好的亲肤性。优选地，聚乙氧基类分子的分子量可以为130～1000；更优选地，聚乙氧基类分子的分子量可以为400～600，由此，可以进一步保证所得到的交联聚硅氧烷类弹性体具有优异的透明度、导电性能以及柔韧性和亲肤性。
根据本公开的实施例，聚乙氧基类分子可以包括单官能度的聚乙氧基类分子和/或多单官能度的聚乙氧基类分子，例如聚乙氧基类分子可以包括2～10个官能度，其中可以利用多个官能度的聚乙氧基类分子来进一步促进聚乙氧基类分子和聚硅氧烷类分子的充分交联固化，以便进一步保证交联 聚硅氧烷类弹性体的高透明度。
根据本公开的实施例，聚乙氧基类分子的具体种类并不受特别限制，本领域技术人员可以根据实际需要灵活选择，例如，聚乙氧基类分子可以包括选自聚乙二醇二丙烯酸酯(PEGDA)、聚乙二醇单甲醚丙烯酸酯(PEGMA)、2-丙烯酸-2-甲氧基乙酯(MEA)、聚乙二醇二甲基丙烯酸甲酯、二巯基封端聚乙二醇和单巯基封端聚乙二醇中的至少一种，发明人发现，选用上述聚乙氧基分子更有利于使制得的交联聚硅氧烷类弹性体兼具优异的透明度、导电性能以及柔韧性和亲肤性等性能。
根据本公开的实施例，锂盐的加入可以与聚乙氧基分子中的乙氧基结构形成配位作用，从而通过分子链的运动进行锂离子的运输和迁移，达到导电效果，其中，锂盐可以为有机锂盐或无机锂盐，可以包括选自双三氟甲烷磺酰亚胺锂、双二氟磺酰亚胺锂、双草酸硼酸锂、六氟磷酸锂、氯化锂和四氟硼酸锂中的至少一种，其中，锂盐优选有机锂盐，发明人发现，相对于无机锂盐，在聚硅氧烷类弹性体中加入有机锂盐的电导率更高，其中，有机锂盐可以更优选为双三氟甲烷磺酰亚胺锂(LITFSI)，上述有机锂盐中LITFSI的导电性能最好，由此，不仅可以提高锂盐与聚硅氧烷的相容性，还能保证所得到的交联聚硅氧烷类弹性体具有优异的透明度和导电性能。
根据本公开的实施例，聚硅氧烷类分子、聚乙氧基类分子和锂盐的质量比可以为(4～8)：(0.2～4.0)：(0.05～1)，具体可以为4/0.2/0.05、4/0.2/0.5、4/0.2/1、4/1.0/0.05、4/4.0/0.05、6/0.2/0.05、6/4.0/1、8/0.2/0.05、8/4.0/1等，发明人发现，聚乙氧基类分子含量越高，越有利于提高聚硅氧烷类弹性体整体电导率，若聚乙氧基类分子的含量过少，一方面难以在弹性体中形成完整的导电通路进而有效提高聚硅氧烷类弹性体的导电性，另一方面，会导致聚硅氧烷类分子无法全部参与交联反应，进而导致交联固化产物过黏或无法固化，难以有效构建交联弹性体，影响聚硅氧烷类弹性体的制备；若聚乙氧基类分子的含量过多，又会导致弹性体的交联密度过大，使得聚硅氧烷类弹性体的材质过硬，影响聚硅氧烷类弹性体的柔韧性和亲肤性，总的来说，当聚乙氧基分子添加量相对于聚硅氧烷类分子过高或者过低时，相应会导致聚硅氧烷分子无法被完全交联或者交联密度过大，从而导致材料的力学性能和透明度等无法满足使用要求；另外，锂盐与聚乙氧基类分子具有一定的配位关系，若锂盐的含量过少，其与乙氧基结构形成的配位较少，难以实现较好的导电效果，而随锂盐用量的增加，弹性体的电导率也随之提升，但当锂盐的含量超过其与聚乙氧基分子的配位关系时，锂盐含量的增加并不会进一步改善导电效果，相反还会影响聚硅氧烷类弹性体的黏附性能，导致其黏附性过高，增加后续脱附的难度。而通过综合控制聚硅氧烷类分子、聚乙氧基类分子和锂盐的质量比为(4～8)：(0.2～4.0)：(0.05～1)，可以保证聚硅氧烷类弹性体在具有较高柔韧性、亲肤性和透明度的前提下具有较高的电导率、导电稳定性和较好的力学性能。例如，该聚硅氧烷类弹性体的透明度能够达到92％以上，应力可以达到100KPa及其以上的水平，电阻率可以达到1.0×10-2S/m甚至更高的 水平。
在本公开的另一个方面，本公开提出了一种制备前面的聚硅氧烷类弹性体的方法，根据本公开的实施例，参照图1，该方法包括：
S100：将聚硅氧烷类分子、聚乙氧基类分子和第一复配溶剂混合，得到第一混合液
该步骤中，将聚硅氧烷类分子、聚乙氧基类分子在第一复配溶剂中进行充分混合，可以使得极性相差较大的聚硅氧烷类分子和聚乙氧基类分子均匀混合，有利于交联反应的进行。其中，第一复配溶剂包括用于溶解聚硅氧烷类分子和聚乙氧基类分子的第一组分，该第一组分可以包括但不限于选自二氯甲烷、三氯甲烷、四氢呋喃和二甲基亚砜中的至少一种。需要说明的是，聚硅氧烷类分子和聚乙氧基类分子的原料选择及配比在前面已经做了详细说明，此处不再赘述。
根据本公开的实施例，聚硅氧烷类分子、聚乙氧基类分子和第一复配溶剂的质量比可以(4～8)：(0.2～4.0)：(20～40)，发明人发现，若溶剂用量过多，会导致后续溶剂挥发较慢从而使弹性体固化时间延长，而若溶剂用量过少，又会导致混合液中聚硅氧烷分子和聚氧乙基分子浓度过高而影响溶解，从而影响交联反应的进行，通过控制聚硅氧烷类分子、聚乙氧基类分子和第一复配溶剂为上述质量配比可以保证各组分充分溶解，从而更有利于保证聚硅氧烷类弹性体兼具优异的透明度、柔韧性、亲肤性、导电性和力学性能等综合性能。
S200：将催化剂与第一混合液混合，得到第二混合液
该步骤中，将催化剂与步骤S100得到的第一混合液充分搅拌混合，得到第二混合液。其中，催化剂的加入用于提高聚硅氧烷类分子和聚乙氧基类分子交联反应的速率及交联密度，进而提高制备效率及成品率。
根据本公开的实施例，催化剂的种类并不受特别限制，本领域可以根据需要灵活选择，只要能够促进聚硅氧烷类分子和聚乙氧基类分子的交联固化构建弹性体即可，例如可以为热引发剂等，具体地，催化剂可以包括选自乙醇钠、氢氧化钠、三乙醇胺、三乙胺、偶氮二异丁腈和二异丙基乙胺中的至少一种。由此，可以有效提高聚硅氧烷类分子和聚乙氧基类分子交联反应的速度，进而有利于提高聚硅氧烷类弹性体的产率。
根据本公开的实施例，可以直接在第二混合液中混入锂盐。需要说明的是，聚硅氧烷类弹性体的制备过程中还包括锂盐的加入，其中，锂盐的加入既可以原位加入，即将锂盐与各原料组分均匀混合后再进行交联固化反应，例如可以在第二混合液中混入锂盐，或将催化剂、锂盐和第一混合液混合得到第二混合液；也可以在交联固化反应后采用锂盐溶液对制得的弹性体进行浸泡，从而使锂盐均匀分散于弹性体中。另外，还需要说明的是，不管采用何种工艺，为实现锂盐的均匀分散，第二混合液或锂盐溶液中应包括用于溶解锂盐的第二组分，其中，第二组分可以包括选自甘油、丙酮 和甲基乙基酮中的至少一种，另外，锂盐溶液还应包括用于溶解聚硅氧烷类分子和聚乙氧基类分子的第一组分。
S300：将第二混合液转移至模具中进行静置反应
该步骤中，将步骤S200得到的第二混合液转移至模具中进行静置反应，在催化剂的催化作用下，聚乙氧基类分子、聚硅氧烷类分子进行交联反应。
根据本公开的实施例，静置反应的温度可以为10～60℃，具体可以为10℃、30℃、40℃、50℃、60℃等，反应时间可以为1～24h，具体可以为1h、5h、10h、15h、20h、24h等。其中，静置反应温度升高会加快交联反应的速率，但若反应温度过高可能会导致溶剂挥发，影响各组分的均匀混合，由此，控制静置反应为上述条件范围既可以保证各组分的均匀分散，还能使聚乙氧基类分子与聚硅氧烷类分子形成致密的交联网络结构，进而有利于获得兼具较高的电导率及导电稳定性，以及较高透明度，且柔韧性、亲肤性和力学性能好的聚硅氧烷类弹性体。
S400：使复配溶剂挥发，以便得到聚硅氧烷类弹性体
该步骤中，可以将步骤S300中交联反应后得到的产物放入真空烘箱中使复配溶剂挥发，得到聚硅氧烷类弹性体。需要说明的是，使复配溶剂挥发的温度并不受特别限制，本领域技术人员可以根据实际需要灵活选择，只要能使复配溶剂完全挥发即可，例如温度可以为80℃、90℃等。
其中，当第二混合液中不含锂盐时，聚硅氧烷类弹性体的制备工艺还需满足条件(a)或条件(b)：
(a)参照图2，步骤S400还包括：
S410：利用锂盐和第二复配溶剂的混合液对静置反应产物进行浸泡；
S420：浸泡完成后使复配溶剂挥发。
(b)参照图3，步骤S400还可以包括：
S430：使第一复配溶剂挥发；
S440：利用锂盐和第二复配溶剂的混合液对步骤S430得到的产物进行浸泡；
S450：浸泡完成后使第二复配溶剂挥发。
发明人发现，采用锂盐溶液对交联固化得到的弹性体进行浸泡时，使弹性体吸收锂盐溶液溶胀也能实现锂盐在弹性体中的均匀扩散，进而实现聚硅氧烷类弹性体的高导电性。优选采用(b)的工艺条件，由此更有利于弹性体对第二复配溶剂的充分吸收，确保锂盐能够随第二复配溶剂在弹性体中均匀扩散。另外，发明人还发现，相对于原位加入锂盐，采用浸泡的方式加入锂盐对聚硅氧烷类弹性体导电性的提升更有利。
根据本公开的实施例，第一复配溶剂和第二复配溶剂可以分别独立地包括第一组分和第二组分，第一组分可以包括选自二氯甲烷、三氯甲烷、四氢呋喃和二甲基亚砜中的至少一种，第二组分可以 包括选自甘油、丙酮和甲基乙基酮中的至少一种，第一组分和第二组分的体积比可以为(20～40)：(0.5～5)，具体可以为20/0.5、20/1、20/3.5、20/5、30/0.5、30/3.5、30/5、40/0.5、40/1.5、40/5等。其中，第一组分用于溶解聚硅氧烷类分子和聚乙氧基类分子，第二组分用于溶解锂盐，若第一组分和第二组分的体积比过高，相当于第二组分的用量较少，在有限溶剂用量下可能会影响锂盐的溶解性，进而难以改善制备的聚硅氧烷类弹性体的导电性；若第一组分和第二组分的体积比过低，又会使得聚硅氧烷类分子和聚乙氧基类分子难以完全溶解在复配溶剂中，从而影响交联反应的进行，难以保证制得的聚硅氧烷类弹性体的力学性能和透明度、亲肤性、柔韧性；而通过控制第一组分和第二组分的体积比为(20～40)：(0.5～5)，更有利于各原料组分的均匀分散和充分反应，使得制备的交联聚硅氧烷类弹性体兼具较高的电导率及导电稳定性，以及较高透明度，且柔韧性、亲肤性和力学性能优异。
根据本公开的实施例，聚硅氧烷类分子、聚乙氧基类分子、锂盐和催化剂的质量比可以为(4～8)：(0.2～4.0)：(0.05～2)：(0.05～1)，具体可以为4/0.2/0.05/0.05、4/0.2/0.5/0.05、4/0.2/1/0.05、4/1.0/0.05/0.05、4/4.0/0.05/0.05、6/0.2/0.05/0.05、6/4.0/1/0.05、8/0.2/0.05/0.05、8/4.0/1/0.05、4/0.2/0.05/0.1、4/0.2/0.05/1等。由此，既可以提高制备效率及成品率，还更有利于使得制备的交联聚硅氧烷类弹性体兼具较高的电导率及导电稳定性，以及较高透明度，且柔韧性、亲肤性和力学性能优异。
综上，根据本公开前面的制备聚硅氧烷类弹性体的方法，该方法不仅操作简单、方便，可重复，易于实现和规模化生产，且采用该方法制备的聚硅氧烷类弹性体兼具较高的电导率及导电稳定性、良好的力学性能、较佳的柔韧性、亲肤性和透明度，在柔性触摸屏、光伏器件、柔性传感器、可穿戴电子器件及软体机器人等方面具有巨大的应用潜力，应用前景广。需要说明的是，针对上述具有透明导电性能的聚硅氧烷类弹性体所描述的特征及效果同样适用于该制备聚硅氧烷类弹性体的方法，此处不再一一赘述。
下面参考具体实施例，对本公开进行描述，需要说明的是，这些实施例仅仅是描述性的，而不以任何方式限制本公开。
实施例1
(1)取5g巯丙基聚二甲基硅氧烷溶解于30g三氯甲烷溶剂中，振荡摇匀，再取0.75g聚乙二醇二丙烯酸酯(PEGDA)溶于上述三氯甲烷溶剂中，充分摇匀后得到第一混合液；
(2)取0.9g双三氟甲烷磺酰亚胺锂溶解于1g甲基乙基酮溶液中，充分溶解后，得到锂盐溶液，将锂盐溶液加入到第一混合液中，之后加入0.9g乙醇钠，振荡摇匀后得到第二混合液；
(3)将第二混合液倒入玻璃模具中，室温静置12h，得到静置反应产物；
(4)将上述得到的静置反应产物放入真空烘箱中，在温度为90℃的条件下进行溶剂挥发和干燥，得到聚硅氧烷类弹性体。
实施例2
与实施例1区别在于：步骤(1)中，取0.9g聚乙二醇二丙烯酸酯溶于上述三氯甲烷溶剂中。
实施例3
与实施例1区别在于：步骤(1)中，取1.0g聚乙二醇二丙烯酸酯溶于上述三氯甲烷溶剂中。
实施例4
与实施例1区别在于：步骤(1)中，取1.25g聚乙二醇二丙烯酸酯溶于上述三氯甲烷溶剂中。
实施例5
与实施例1区别在于：步骤(1)中，取1.5g聚乙二醇二丙烯酸酯溶于上述三氯甲烷溶剂中。
实施例6
与实施例1区别在于：步骤(1)中，取1.75g聚乙二醇二丙烯酸酯溶于上述三氯甲烷溶剂中。
实施例7
与实施例1区别在于：步骤(1)中，取2.25g聚乙二醇二丙烯酸酯溶于上述三氯甲烷溶剂中。
实施例8
(1)取5g巯丙基聚二甲基硅氧烷溶解于30g三氯甲烷溶剂中，振荡摇匀，再取1.2g聚乙二醇二丙烯酸酯、0.5g聚乙二醇单甲醚丙烯酸酯溶于上述三氯甲烷溶剂中，充分摇匀后得到第一混合液；
(2)取1.68g双三氟甲烷磺酰亚胺锂溶解于1g甘油溶液中，充分溶解后，得到锂盐溶液，将锂盐溶液加入到第一混合液中，之后加入0.9g三乙胺，振荡摇匀后得到第二混合液；
(3)将第二混合液倒入玻璃模具中，在温度为50℃的条件下静置4h，得到静置反应产物；
(4)将上述得到的静置反应产物放入真空烘箱中，在温度为90℃的条件下进行溶剂挥发和干燥，得到聚硅氧烷类弹性体。
实施例9
(1)取5g巯丙基聚二甲基硅氧烷溶解于30g二氯甲烷溶剂中，振荡摇匀，再取1.2g聚乙二醇二丙烯酸酯溶于上述二氯甲烷溶剂中，充分摇匀后得到第一混合液；
(2)取0.9g六氟磷酸锂溶解于1g丙酮溶液中，充分溶解后，得到锂盐溶液，将锂盐溶液加入到第一混合液中，之后加入0.9g三乙胺，振荡摇匀后得到第二混合液；
(3)将第二混合液倒入玻璃模具中，室温静置16h，得到静置反应产物；
(4)将上述得到的静置反应产物放入真空烘箱中，在温度为90℃的条件下进行溶剂挥发和干燥，得到聚硅氧烷类弹性体。
实施例10
(1)取5g巯丙基聚二甲基硅氧烷溶解于30g二甲基亚砜溶剂中，振荡摇匀，再取1.2g聚乙二醇二丙烯酸酯溶于上述二甲基亚砜溶剂中，充分摇匀后得到第一混合液；
(2)取0.9g双三氟甲烷磺酰亚胺锂溶解于1g丙酮溶液中，充分溶解后，得到锂盐溶液，将锂盐溶液加入到第一混合液中，之后加入0.9g三乙胺，振荡摇匀后得到第二混合液；
(3)将第二混合液倒入玻璃模具中，在温度为60℃的条件下静置2h，得到静置反应产物；
(4)将上述得到的静置反应产物放入真空烘箱中，在温度为90℃的条件下进行溶剂挥发和干燥，得到聚硅氧烷类弹性体。
实施例11
(1)取5g巯丙基聚二甲基硅氧烷溶解于30g二氯甲烷溶剂中，振荡摇匀，再取2g聚乙二醇二丙烯酸酯溶于上述二氯甲烷溶剂中，充分摇匀后得到第一混合液；
(2)取0.9g四氟硼酸锂溶解于1g甲基乙基酮溶液中，充分溶解后，得到锂盐溶液，将锂盐溶液加入到第一混合液中，之后加入0.9g乙醇钠，振荡摇匀后得到第二混合液；
(3)将第二混合液倒入玻璃模具中，室温静置12h，得到静置反应产物；
(4)将上述得到的静置反应产物放入真空烘箱中，在温度为90℃的条件下进行溶剂挥发和干燥，得到聚硅氧烷类弹性体。
实施例12
(1)取5g巯丙基聚二甲基硅氧烷溶解于30g二氯甲烷溶剂中，振荡摇匀，再取0.9g聚乙二醇丙烯酸酯溶于上述二氯甲烷溶剂中，充分摇匀后得到第一混合液；
(2)加入0.9g三乙胺，振荡摇匀后得到第二混合液；
(3)将第二混合液倒入玻璃模具中，室温静置10h，得到静置反应产物；
(4)将上述得到的静置反应产物放入真空烘箱中，在温度为90℃的条件下进行溶剂挥发和干燥，得到聚硅氧烷类弹性体。
(5)将0.9g双三氟甲烷磺酰亚胺锂溶解于30g二氯甲烷和1g丙酮溶液中，充分溶解后，得到锂盐溶液；将上述得到的聚硅氧烷弹性体浸泡到锂盐溶液中，浸泡5h，待锂盐溶液完全吸入聚硅氧烷类弹性体后放入烘箱中，在温度为50℃的条件下烘干，得到透明导电聚硅氧烷弹性体。
实施例13
(1)取5g巯丙基聚二甲基硅氧烷溶解于30g二氯甲烷溶剂中，振荡摇匀，再取1g 2-丙烯酸-2-甲氧基乙酯和1g聚乙二醇丙烯酸酯溶于上述二氯甲烷溶剂中，充分摇匀后得到第一混合液；
(2)取0.9g四氟硼酸锂溶解于1g丙酮溶液中，充分溶解后，得到锂盐溶液，将锂盐溶液加入 到第一混合液中，之后加入0.9g氢氧化钠，振荡摇匀后得到第二混合液；
(3)将第二混合液倒入玻璃模具中，室温静置20h，得到静置反应产物；
(4)将上述得到的静置反应产物放入真空烘箱中，在温度为90℃的条件下进行溶剂挥发和干燥，得到聚硅氧烷类弹性体。
实施例14
(1)取5g巯基甲基硅氧烷-二甲基硅氧烷共聚物溶解于30g二氯甲烷溶剂中，振荡摇匀，再取0.5g二巯基封端聚乙二醇溶于上述二氯甲烷溶剂中，充分摇匀后得到第一混合液；
(2)取0.9g双三氟甲烷磺酰亚胺锂溶解于1g丙酮溶液中，充分溶解后，得到锂盐溶液，将锂盐溶液加入到第一混合液中，之后加入0.9g三乙醇胺，振荡摇匀后得到第二混合液；
(3)将第二混合液倒入玻璃模具中，室温静置10h得到静置反应产物；
(4)将上述得到的静置反应产物放入真空烘箱中，在温度为90℃的条件下进行溶剂挥发和干燥，得到聚硅氧烷类弹性体。
实施例15
(1)取5g双键封端聚二甲基硅氧烷溶解于30g二甲基亚砜溶剂中，振荡摇匀，再取0.5g二巯基封端聚乙二醇溶于上述二甲基亚砜溶剂中，充分摇匀后得到第一混合液；
(2)取0.9g双三氟甲烷磺酰亚胺锂溶解于1g丙酮溶液中，充分溶解后，得到锂盐溶液，将锂盐溶液加入到第一混合液中，之后加入0.9g三乙醇胺，振荡摇匀后得到第二混合液；
(3)将第二混合液倒入玻璃模具中，在温度为60℃的条件下静置2h，得到静置反应产物；
(4)将上述得到的静置反应产物放入真空烘箱中，在温度为90℃的条件下进行溶剂挥发和干燥，得到聚硅氧烷类弹性体。
实施例16
(1)取5g双键封端聚二甲基硅氧烷溶解于30g二氯甲烷溶剂中，振荡摇匀，再取0.5g二巯基封端聚乙二醇溶于上述二氯甲烷溶剂中，充分摇匀后得到第一混合液；
(2)取0.9g双三氟甲烷磺酰亚胺锂溶解于1g丙酮溶液中，充分溶解后，得到锂盐溶液，将锂盐溶液加入到第一混合液中，之后加入0.9g三乙醇胺振荡摇匀后得到第二混合液；
(3)将第二混合液倒入玻璃模具中，在温度为40℃的条件下静置6h，得到静置反应产物；
(4)将上述得到的静置反应产物放入真空烘箱中，在温度为90℃的条件下进行溶剂挥发和干燥，得到聚硅氧烷类弹性体。
实施例17
(1)取5g巯丙基聚二甲基硅氧烷溶解于30g三氯甲烷溶剂中，振荡摇匀，再取0.75g聚乙二 醇二丙烯酸酯溶于上述三氯甲烷溶剂中，充分摇匀后得到第一混合液；
(2)取0.5g双三氟甲烷磺酰亚胺锂溶解于1g甲基乙基酮溶液中，充分溶解后，得到锂盐溶液，将锂盐溶液加入到第一混合液中，之后加入0.9g乙醇钠，振荡摇匀后得到第二混合液；
(3)将第二混合液倒入玻璃模具中，室温静置12h，得到静置反应产物；
(4)将上述得到的静置反应产物放入真空烘箱中，在温度为90℃的条件下进行溶剂挥发和干燥，得到弹性体；
(5)将0.4g双三氟甲烷磺酰亚胺锂溶解于30g二氯甲烷和1g丙酮溶液中，充分溶解后，得到第二锂盐溶液；将上述得到的聚硅氧烷弹性体浸泡到第二锂盐溶液中，浸泡5h，待第二锂盐溶液完全吸入聚硅氧烷类弹性体后放入烘箱中，在温度为50℃的条件下烘干，得到透明导电聚硅氧烷弹性体。
对比例1
(1)取5g巯丙基聚二甲基硅氧烷溶解于30g二氯甲烷溶剂中，振荡摇匀，再取5g聚乙二醇二丙烯酸酯溶于二氯甲烷溶剂中，充分摇匀后得到第一混合液；
(2)取0.9g双三氟甲烷磺酰亚胺锂溶解于1g丙酮溶液中，充分溶解后，得到锂盐溶液，将锂盐溶液加入到第一混合液中，之后加入0.9g三乙胺，振荡摇匀后得到第二混合液；
(3)将第二混合液倒入玻璃模具中，室温静置12h，得到静置反应产物；
(4)将上述得到的静置反应产物放入真空烘箱中，在温度为90℃的条件下进行溶剂挥发和干燥。
对比例2
与对比例1区别在于：步骤(1)中，取9g巯丙基聚二甲基硅氧烷溶解于30g二氯甲烷溶剂中，振荡摇匀，再取0.8g聚乙二醇二丙烯酸酯溶于上述二氯甲烷溶剂中。
性能测试：
(1)聚硅氧烷类弹性体的透明性能测试
将实施例(步骤(2))中的第二混合液倒入10mm光程的石英比色皿中，静置12h使巯丙基聚二甲基硅氧烷和聚乙二醇二丙烯酸酯交联固化得到聚硅氧烷类弹性体；之后放置在80℃的真空烘箱中去除剩余溶剂。然后使用紫外光谱仪进行测试，波长范围为400nm～800nm(可见光)，观察聚硅氧烷类弹性体在可见光范围的吸收情况。
(2)聚硅氧烷类弹性体的拉伸性能测试
将制得的聚硅氧烷类弹性体分别裁剪成40mm×5mm×1mm的样条，仪器采用日本岛津公司生产 的Shimadzu AGS-X万用力学试验机。拉伸条件如下所示：样条在夹具间的初始距离为10～15mm，拉伸速度为100mm/min，同一组样品进行五次平行实验并取平均值。记录拉伸测试开始到结束时的载荷F(N)和行程l(mm)，使用公式2-1和公式2-2分别计算应力σmax(MPa)和εmax应变。聚硅氧烷类弹性体的初始模量为应力-应变曲线最初10％部分的斜率。
σ＝F/A      (2-1)
ε＝l/l0×100％       (2-2)
(3)聚硅氧烷类弹性体的黏附性能测试
将制得的聚硅氧烷类弹性体分别制备成20mm×10mm×2mm的样条，粘附性能测试的基板选择玻璃材质。在测试前将样条夹在两块玻璃片中间，参照附图9，拉伸仪器采用日本岛津公司产的Shimadzu AGS-X万用力学试验机，测试夹具经过10mm拉伸后的应力应变曲线。每组重复5次，应力应变曲线的积分面积即为剥离功，取5次重复实验的最大剥离力平均值作为剥离力。
(4)聚硅氧烷类弹性体的导电性能测试
将制得的聚硅氧烷类弹性体分别制备成30mm×10mm×2mm的样条，使用Tonghui TH2826LCR Meter数字电桥LCR测试仪进行测试。测试过程中将电桥正负极接在样条两端，待示数稳定时读取电阻值。根据公式3-1和公式3-2得到聚硅氧烷类弹性体的电导率。
R＝ρl/S         (3-1)
σ＝ρ-1＝l/RS        (3-2)
其中，R-电阻值，ρ-制成电阻的材料的电阻率，l-绕制成电阻的导线长度，S-绕制成电阻的导线横截面积。
(5)聚硅氧烷类弹性体的接触角测试
将制得的聚硅氧烷类弹性体分别制备成30mm×30mm样品，放置在玻璃基板上，接触角测试仪采用德国Dataphysics的TBU100型号机。在测试前保持样品表面的整洁平整，之后将水滴滴在样品中间，通过接触角分析软件测得接触角的度数。
(6)聚硅氧烷类弹性体的水汽透过率测试
将聚硅氧烷类材料和实施例制得的聚硅氧烷类弹性体分别制备成直径90mm的圆形薄膜，水汽透过率测试仪器采用广州标际包装设备有限公司的GBPI W303水汽透过率测试仪，测试方法采用GB/T 1037-1988塑料薄膜和片材透水蒸气性试验方法杯式法。薄膜厚度为1.5mm，温度控制在38℃，相对湿度为90％。当水汽透过量达到稳定时结束测试。
其中，图4是实施例7制备的聚硅氧烷类弹性体的透明性能测试示意图；图5是实施例1、实施例4～7制备的聚硅氧烷类弹性体的应力-应变曲线对比图(横坐标对应弹性体拉伸应变，纵坐标对 应应力)；图6是实施例1、3～7制备的聚硅氧烷类弹性体的电阻测试对比图；图7是实施例1、3～7制备的聚硅氧烷类弹性体的电导率测试对比图(其中图7中，聚乙氧基类分子的质量分数指的是聚乙氧基类分子相对于聚硅烷类分子的用量)；图8是实施例2、12、17制备的聚硅氧烷类弹性体的电导率测试对比图；图9是万用力学试验机的装置示意图；图10是实施例1、4、6、7制备的聚硅氧烷类弹性体的接触角测试结果示意图；图11是对比例1制得的样品的示意图；图12是对比例2制得的样品的示意图；表1为聚硅氧烷类材料和实施例7制备的聚硅氧烷类弹性体的水汽透过率的测试结果。
表1 聚硅氧烷类材料与实施例7制备的聚硅氧烷类弹性体的水汽透过率的测试结果
结论：
由图4可知，采用实施例7的方法，可以清晰地透过制得的聚硅氧烷类弹性体产品观察到“清华大学”的标志(如图4中(A)图所示)和鲜花(B)的细节图像(如图4中(B)图所示)，说明制备的聚硅氧烷类弹性体的透明度高。另外，结合对本公开上述实施例1～6和8～17可知，聚硅氧烷类弹性体的透明度与聚硅氧烷类分子、聚乙氧基类分子之间的分散均匀程度密切相关，分散均匀程度越好，聚硅氧烷类弹性体的透明度越高。此外，相比于单官能团聚乙氧基类分子，双官能度聚乙氧基类分子(如实施例1～7、9～12中的聚乙二醇二丙烯酸酯、实施例14～16中的二巯基封端聚乙二醇)由于与聚硅氧烷类分子交联的更为紧密，聚硅氧烷类分子之间不容易发生微相分离影响聚硅氧烷类弹性体整体的透明度，使得制备的聚硅氧烷类弹性体具有优异的透明度，能达到90％以上。
从图5中可以看出，随着PEGDA相对于聚硅氧烷类分子的添加量由15％增加到45％时，弹性体交联点密度增大，从而使得弹性体拉伸模量增大，伸长率降低，其中，实施例7中的聚乙氧基类分子添加量最多，其制得的聚硅氧烷类弹性体的应力明显高于实施例1、4～6制得的聚硅氧烷类弹性体的应力。结合其它实施例的测试结果可知，聚硅氧烷类弹性体拉伸性能与聚乙氧基分子和聚硅烷类分子的交联密度密切相关，弹性体的交联密度变大，整体的伸长率越低。另外，结合本公开上述实施例的黏附性能测试结合可知，聚硅氧烷类弹性体的黏附性能与聚乙氧基分子和聚硅烷类分子的交联密度也密切相关，弹性体表面的粘附力主要由弹性体的交联密度决定，交联密度越高，弹性体表面的黏附性越差，例如，相对于单官能度的聚乙氧基分子，采用双官能度的聚乙氧基分子(如 聚乙二醇二丙烯酸酯、聚乙二醇二丙烯酸甲酯、双巯基封端聚乙二醇)或双官能度的聚乙氧基分子含量越高，弹性体整体的黏附性能越差。
从图6、图7中可以看出，随着聚乙氧基类分子的含量增多，聚硅氧烷类弹性体的电阻逐渐减少，电导率逐渐增大，实施例1制得的聚硅氧烷类弹性体的电阻为2.3×103Ω，电阻率为5.0×10-4S/m，其电阻率最低；实施例7制得的聚硅氧烷类弹性体的电阻为7.0×101Ω，电阻率为1.4×10-2S/m，其电阻率最高，结合其它实施例的导电性能测试结果可知，聚硅氧烷类弹性体的导电性与聚乙氧基类分子的含量密切相关，随着弹性体中聚乙氧基类分子的含量逐渐增加，聚乙氧基类分子导电相之间形成的导电通路逐渐形成，达到逾渗阈值，使得制得的聚硅氧烷类弹性体的电导率显著提高。
从图8可以看出，实施例12制得的聚硅氧烷类弹性体的电导率明显高于实施例2和实施例17，由此还可以说明，聚硅氧烷类弹性体的导电性与锂盐的加入方式密切相关，相比于实施例2中原位加入锂盐的方式，采用浸泡法吸收锂盐的方式可进一步提高聚硅氧烷类弹性体的电导率；此外，结合对其它实施例及相关试验制得的聚硅氧烷类弹性体的导电性能测试结果可知，聚硅氧烷类弹性体的导电性还与聚乙氧基类分子与聚硅氧烷类分子的交联方式、锂盐种类以及锂盐的加入量密切相关，交联聚硅氧烷类弹性体中，分子链运动越快，聚硅氧烷类弹性体的电导率越高，例如，弹性体中单臂聚乙氧基分子(聚乙二醇丙烯酸单甲醚、丙烯酸-2-甲氧基乙酯)的比例越高，分子链运功性越高，弹性体的电导率也越高；另外，有机锂盐的电导率明显高于无机锂盐，其中有机锂盐中双三氟甲烷磺酰亚胺锂(LITFSI)的导电性能最好。
从图10可以看出，随着聚乙氧基类分子含量的增加，聚硅氧烷类弹性体表面的极性增大，从而使得聚硅氧烷类弹性体的表面更加亲水，接触角减小，结合其它实施例的弹性体接触角测试结果可以说明，聚乙氧基类分子的极性高，亲水性强，随着聚乙氧基类分子含量的增加，聚硅氧烷类弹性体的亲水性变好；另外，从表1可以看出，聚硅氧烷类材料巯丙基聚二甲基硅氧烷的透过量为98.6725g/(m2·24h)，实施例7制备的聚硅氧烷类弹性体的透过量为185.5315g/(m2·24h)，显著高于聚硅氧烷类材料的透过量，由此还可以说明，聚乙氧基类分子的加入可以有效改善聚硅氧烷类弹性体的水汽透过能力。
图11是对比例1制得的样品的示意图，从图11可以看出，当聚乙氧基类分子相对于聚硅氧烷类分子过量时，过多的聚乙氧基类分子无法完全参与反应，而未参与反应的聚乙氧基类分子会附着在交联固化形成的聚硅氧烷类弹性体的表面上，严重影响弹性体的透明度、柔韧性和亲肤性。图12是对比例2制得的样品的示意图，从图12可以看出，聚硅氧烷类分子相对于聚乙氧基类分子过量时，聚硅氧烷类分子与聚乙氧基类分子难以交联固化，得到粘稠分相的反应液。由此可见，聚乙氧基类分子或聚硅氧烷类分子过量时，均会影响交联反应的进行，进而影响聚硅氧烷类弹性体的制备。
在本说明书的描述中，参考术语“一个实施例”、“一些实施例”、“示例”、“具体示例”、或“一些示例”等的描述意指结合该实施例或示例描述的具体特征、结构、材料或者特点包含于本公开的至少一个实施例或示例中。在本说明书中，对上述术语的示意性表述不必须针对的是相同的实施例或示例。而且，描述的具体特征、结构、材料或者特点可以在任一个或多个实施例或示例中以合适的方式结合。此外，在不相互矛盾的情况下，本领域的技术人员可以将本说明书中描述的不同实施例或示例以及不同实施例或示例的特征进行结合和组合。
尽管上面已经示出和描述了本公开的实施例，可以理解的是，上述实施例是示例性的，不能理解为对本公开的限制，本领域的普通技术人员在本公开的范围内可以对上述实施例进行变化、修改、替换和变型。

Claims (15)

  1. 一种具有透明导电性能的聚硅氧烷类弹性体，其中，以聚硅氧烷类分子为基体，以聚乙氧基类分子为导电相，所述聚硅氧烷类分子和所述聚乙氧基类分子通过交联固化得到所述弹性体，所述弹性体中分散有锂盐。
  2. 根据权利要求1所述的聚硅氧烷类弹性体，其中，所述聚硅氧烷类分子包括巯基和/或双键。
  3. 根据权利要求1或2所述的聚硅氧烷类弹性体，其中，所述聚硅氧烷类分子包括选自巯丙基聚二甲基硅氧烷、巯基甲基硅氧烷-二甲基硅氧烷共聚物、巯基封端聚二甲基硅氧烷、双键封端聚二甲基硅氧烷和双键甲基硅氧烷-二甲基硅氧烷共聚物中的至少一种。
  4. 根据权利要求1～3中任一项所述的聚硅氧烷类弹性体，其中，所述聚乙氧基类分子的分子量为100～20000。
  5. 根据权利要求1～4中任一项所述的聚硅氧烷类弹性体，其中，所述聚乙氧基类分子的分子量为130～1000。
  6. 根据权利要求1～5中任一项所述的聚硅氧烷类弹性体，其中，所述聚乙氧基类分子的分子量为400～600。
  7. 根据权利要求1～6中任一项所述的聚硅氧烷类弹性体，其中，所述聚乙氧基类分子包括2～10个官能度。
  8. 根据权利要求1～7中任一项所述的聚硅氧烷类弹性体，其中，所述聚乙氧基类分子包括选自聚乙二醇二丙烯酸酯、聚乙二醇单甲醚丙烯酸酯、2-丙烯酸-2-甲氧基乙酯、聚乙二醇二甲基丙烯酸甲酯、二巯基封端聚乙二醇和单巯基封端聚乙二醇中的至少一种。
  9. 根据权利要求1～8中任一项所述的聚硅氧烷类弹性体，其中，所述锂盐包括选自双三氟甲烷磺酰亚胺锂、双二氟磺酰亚胺锂、双草酸硼酸锂、六氟磷酸锂、氯化锂和四氟硼酸锂中的至少一种。
  10. 根据权利要求1～9中任一项所述的聚硅氧烷类弹性体，其中，所述聚硅氧烷类分子、所述聚乙氧基类分子和所述锂盐的质量比为(4～8)：(0.2～4.0)：(0.05～1)。
  11. 一种制备权利要求1～10中任一项所述的聚硅氧烷类弹性体的方法，其中，包括：
    (1)将聚硅氧烷类分子、聚乙氧基类分子和第一复配溶剂混合，得到第一混合液；
    (2)将催化剂与所述第一混合液混合，得到第二混合液；
    (3)将所述第二混合液转移至模具中进行静置反应；
    (4)使复配溶剂挥发，以便得到所述聚硅氧烷类弹性体，
    其中，还满足以下3个条件之一：
    (a)在进行步骤(3)之前在所述第二混合液中混入锂盐；
    (b)步骤(4)还包括：(4-1)利用锂盐和第二复配溶剂的混合液对静置反应产物进行浸泡；(4-2)浸泡完成后使复配溶剂挥发；
    (c)步骤(4)还包括：(4-3)使所述第一复配溶剂挥发；(4-4)利用锂盐和第二复配溶剂的混合液对步骤(4-3)得到的产物进行浸泡；(4-5)浸泡完成后使所述第二复配溶剂挥发，
    另外，所述第一复配溶剂和所述第二复配溶剂分别独立地包括第一组分和第二组分，所述第一组分用于溶解所述聚硅氧烷类分子和所述聚乙氧基类分子，所述第二组分用于溶解所述锂盐。
  12. 根据权利要求11所述的方法，其中，所述催化剂包括选自乙醇钠、氢氧化钠、三乙醇胺、三乙胺、偶氮二异丁腈和二异丙基乙胺中的至少一种。
  13. 根据权利要求11或12所述的方法，其中，所述第一组分包括选自二氯甲烷、三氯甲烷、四氢呋喃和二甲基亚砜中的至少一种，所述第二组分包括选自甘油、丙酮和甲基乙基酮中的至少一种，所述第一组分和所述第二组分的体积比为(20～40)：(0.5～5)。
  14. 根据权利要求11～13中任一项所述的方法，其中，所述聚硅氧烷类分子、所述聚乙氧基类分子、所述锂盐和所述催化剂的质量比为(4～8)：(0.2～4.0)：(0.05～2)：(0.05～1)。
  15. 根据权利要求11～14中任一项所述的方法，其中，所述静置反应的温度为10～60℃，反应时间为1～24h。
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