WO2020114049A1 - Solvant eutectique profond polymérisable pour matériaux auto-réparables, élastomère conducteur d'électricité et procédé de préparation correspondant - Google Patents

Solvant eutectique profond polymérisable pour matériaux auto-réparables, élastomère conducteur d'électricité et procédé de préparation correspondant Download PDF

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WO2020114049A1
WO2020114049A1 PCT/CN2019/108315 CN2019108315W WO2020114049A1 WO 2020114049 A1 WO2020114049 A1 WO 2020114049A1 CN 2019108315 W CN2019108315 W CN 2019108315W WO 2020114049 A1 WO2020114049 A1 WO 2020114049A1
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self
eutectic solvent
hydrogen bond
conductive elastomer
healing
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PCT/CN2019/108315
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English (en)
Chinese (zh)
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何明辉
李仁爱
陈广学
张凯丽
田君飞
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华南理工大学
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    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F222/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a carboxyl radical and containing at least one other carboxyl radical in the molecule; Salts, anhydrides, esters, amides, imides, or nitriles thereof
    • C08F222/02—Acids; Metal salts or ammonium salts thereof, e.g. maleic acid or itaconic acid
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F120/00—Homopolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical or a salt, anhydride, ester, amide, imide or nitrile thereof
    • C08F120/02—Monocarboxylic acids having less than ten carbon atoms; Derivatives thereof
    • C08F120/52—Amides or imides
    • C08F120/54—Amides, e.g. N,N-dimethylacrylamide or N-isopropylacrylamide
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F120/00—Homopolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical or a salt, anhydride, ester, amide, imide or nitrile thereof
    • C08F120/02—Monocarboxylic acids having less than ten carbon atoms; Derivatives thereof
    • C08F120/52—Amides or imides
    • C08F120/54—Amides, e.g. N,N-dimethylacrylamide or N-isopropylacrylamide
    • C08F120/56—Acrylamide; Methacrylamide
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F220/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical or a salt, anhydride ester, amide, imide or nitrile thereof
    • C08F220/02—Monocarboxylic acids having less than ten carbon atoms; Derivatives thereof
    • C08F220/04—Acids; Metal salts or ammonium salts thereof
    • C08F220/06—Acrylic acid; Methacrylic acid; Metal salts or ammonium salts thereof
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F220/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical or a salt, anhydride ester, amide, imide or nitrile thereof
    • C08F220/02—Monocarboxylic acids having less than ten carbon atoms; Derivatives thereof
    • C08F220/52—Amides or imides
    • C08F220/54—Amides, e.g. N,N-dimethylacrylamide or N-isopropylacrylamide
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F220/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical or a salt, anhydride ester, amide, imide or nitrile thereof
    • C08F220/02—Monocarboxylic acids having less than ten carbon atoms; Derivatives thereof
    • C08F220/52—Amides or imides
    • C08F220/54—Amides, e.g. N,N-dimethylacrylamide or N-isopropylacrylamide
    • C08F220/56—Acrylamide; Methacrylamide
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F220/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical or a salt, anhydride ester, amide, imide or nitrile thereof
    • C08F220/02—Monocarboxylic acids having less than ten carbon atoms; Derivatives thereof
    • C08F220/52—Amides or imides
    • C08F220/54—Amides, e.g. N,N-dimethylacrylamide or N-isopropylacrylamide
    • C08F220/58—Amides, e.g. N,N-dimethylacrylamide or N-isopropylacrylamide containing oxygen in addition to the carbonamido oxygen, e.g. N-methylolacrylamide, N-(meth)acryloylmorpholine
    • 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
    • C08K3/28—Nitrogen-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
    • C08K5/16—Nitrogen-containing compounds
    • C08K5/17—Amines; Quaternary ammonium compounds
    • C08K5/19—Quaternary ammonium 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
    • C08K5/49—Phosphorus-containing compounds
    • C08K5/50—Phosphorus bound to carbon only

Definitions

  • the invention relates to the field of ionic liquids.
  • the invention relates to a polymerizable eutectic solvent for self-healing materials, a conductive elastomer, and a preparation method thereof.
  • the eutectic solvent is a subset of ionic liquids. It has the advantages of low vapor pressure, non-aqueous biocompatibility, non-combustibility, chemical stability, and high solubility of ionic liquids. It also has low cost and low toxicity. , 100% atomic utilization rate and environmental friendliness in the preparation process, and is expected to replace ionic liquids in the future.
  • eutectic solvents are mainly used in areas such as capturing carbon dioxide, dissolving metal oxides, dissolving drugs and purification, catalysts, electrodeposition, material preparation, and processing biopolymers.
  • the present invention is to overcome the defects of the prior art and provide a polymerizable eutectic solvent for self-healing materials.
  • Another object of the present invention is to provide a self-healing conductive elastomer.
  • the self-repairing conductive elastomer prepared by the invention has high light transmittance, conductivity, high tensile performance and fast self-repairing performance, and its self-repairing ability is excellent at -30°C to 60°C.
  • Another object of the present invention is to provide a method for preparing the self-healing conductive elastomer.
  • a polymerizable eutectic solvent for self-healing materials obtained by reacting a hydrogen bond acceptor with a hydrogen bond donor at 60 to 100°C.
  • the hydrogen bond donor includes a double bond-containing carboxylic acid monomer and acrylamide
  • the molar ratio of the hydrogen bond donor to the hydrogen bond acceptor is not less than 1:1
  • the molar ratio of the acrylamide monomer to double bond-containing carboxylic acid monomer is not less than 1:1.
  • the inventor found through experiments that when the hydrogen bond donor is a double bond-containing carboxylic acid monomer and acrylamide monomer and the molar ratio of the hydrogen bond donor to the hydrogen bond acceptor is not less than 1:1, the When the molar ratio of acrylamide monomer to double bond-containing carboxylic acid monomer is not less than 1:1, the polymerizable eutectic solvent prepared from the hydrogen bond acceptor and hydrogen bond donor can be used to prepare self-healing Functional material, which can be cured under the action of an initiator to obtain a transparent elastomer, which has a self-healing function.
  • the molar ratio of acrylamide monomers, double bond-containing carboxylic acid monomers and hydrogen bond acceptors is crucial for the formation of polymerizable eutectic solvents that can be used to prepare self-healing materials. If the amount of the body or the hydrogen bond acceptor is not suitable, it is difficult to form a eutectic solvent, and if the ratio of acrylamide and double bond-containing carboxylic acid monomer is inappropriate, there is no self-repairing function.
  • the molar ratio of the hydrogen bond acceptor to the double bond-containing carboxylic acid monomer and acrylamide monomer is 2:1:1 to 2:1:5.
  • the double bond-containing carboxylic acid monomer is one or more of acrylic acid, methacrylic acid, maleic acid, itaconic acid, citraconic acid, and aconitic acid.
  • the double bond-containing carboxylic acid monomer is acrylic acid or maleic acid.
  • the acrylamide monomers are acrylamide, methacrylamide, diacetone acrylamide, N-isopropyl acrylamide, N-hydroxyethyl acrylamide, N,N-dimethyl Acrylamide, N-methylol acrylamide.
  • the acrylamide monomer is acrylamide.
  • the hydrogen bond acceptor is choline chloride, anhydrous betaine, betaine monohydrate, ammonium chloride, methyltriphenylphosphonium bromide, benzyltriphenylphosphonium chloride , N, N-diethyl ethanol ammonium chloride and one or more.
  • a self-healing conductive elastomer comprising: a polymerizable eutectic solvent for the self-healing material, a cross-linking agent and an initiator, the molar ratio of the cross-linking agent to the hydrogen bond donor is 0.5:100-5: 100; the amount of the initiator is 0.5% to 5% of the total mass of the polymerizable eutectic solvent and the crosslinking agent, and the crosslinking agent is a multifunctional acrylate monomer or resin.
  • Self-healing conductive elastomer can be prepared by mixing the eutectic solvent and cross-linking agent, and there is no need to add conductive nano-materials during the preparation process.
  • the addition of an appropriate amount of cross-linking agent can further improve the flexibility of the self-repairing conductive elastomer.
  • the repairing conductive elastomer has transparent appearance, good conductivity, excellent self-repairing performance and good environmental stability.
  • the crosslinking agent is tripropylene glycol diacrylate, polyethylene glycol diacrylate, dipropylene glycol diacrylate, 1,6-hexanediol diacrylate, neopentyl glycol
  • diacrylate diethylene glycol diphthalate, trimethylolpropane triacrylate, pentaerythritol tetraacrylate, etc.
  • the initiator is a thermal initiator or a photoinitiator.
  • the photoinitiator is one of benzoin and derivative photoinitiators, benzyl photoinitiators, alkyl benzophenone photoinitiators, and acylphosphine oxide photoinitiators.
  • the benzoin and derivative photoinitiator may be benzoin, benzoin dimethyl ether, benzoin ether, benzoin isopropyl ether, benzoin butyl ether, and the like.
  • the benzyl initiator may be diphenylethanone, ⁇ , ⁇ -dimethoxy- ⁇ -phenylacetophenone and the like.
  • the alkyl ketones may be ⁇ , ⁇ -diethoxyacetophenone, ⁇ -hydroxyalkyl ketone, ⁇ -aminoalkyl ketone, and the like.
  • the acylphosphine oxide may be aroylphosphine oxide, bisbenzoylphenylphosphine oxide, or the like.
  • the photoinitiator may be 1173 (2-hydroxy-2-methyl-1-phenylacetone), 184 (1-hydroxycyclohexylphenyl ketone), TPO-L (2,4, 6-trimethylbenzoylphenylphosphonic acid ethyl ester), 819DW (phenylbis(2,4,6-trimethylbenzoyl)phosphine oxide), 2959(2-hydroxy-4'-(2 -One or more of hydroxyethoxy)-2-methylphenylacetone).
  • the thermal initiator is an organic peroxide initiator or an azo initiator.
  • the organic peroxide initiator is benzoyl peroxide, lauroyl peroxide, cumene hydrogen peroxide, tert-butyl hydroperoxide, di-tert-butyl peroxide, dicumyl peroxide , One or more of tert-butyl peroxybenzoate, tert-butyl peroxypivalate.
  • the azo initiator is azobisisobutyronitrile or azobisisoheptanonitrile.
  • the preparation method of the self-repairing conductive elastomer includes the following steps:
  • Step S3 Preparation of self-repairing conductive elastomer: Pour the mixed solution of conductive elastomer prepolymer described in step S2 into a vessel, and cure or thermally cure under ultraviolet light irradiation to obtain a self-repairing conductive elastomer.
  • the curing energy of the ultraviolet light is 2Kw.
  • the curing time of the ultraviolet light is 5-30 minutes.
  • the beneficial effect of the present invention is that the present invention discovers and selects carboxylic acid monomers and acrylamide monomers containing double bonds as hydrogen bond donors and hydrogen bond acceptors by exploring and screening hydrogen bond donors.
  • a polymerizable eutectic solvent that can be used to prepare self-healing materials can be obtained; a polymerizable eutectic solvent is mixed with a crosslinking agent and an initiator in a specific ratio to obtain conductive with self-healing function Elastomer, the obtained conductive elastomer has high light transmittance, better conductivity, stretchability, flexibility and excellent self-healing performance, and has excellent self-healing ability at -30°C ⁇ 60°C, and self-healing
  • the conductive elastomer has good environmental stability, simple preparation method, low pollution and low cost.
  • FIG. 1 is a comparison diagram of a self-repairing conductive elastomer of Example 15 placed on a school badge sheet.
  • FIG. 2 is a test chart of the self-repairing ability of the self-repairing conductive elastomer of Example 15.
  • FIG. 3 is a test chart of the conductive performance of the self-repairing conductive elastomer of Example 15.
  • FIG. 4 is a stress-strain curve diagram of the self-repairing conductive elastomer of Examples 15-19.
  • FIG. 5 is a differential scanning calorimetry analysis diagram of the self-healing conductive elastomer of Example 15.
  • FIG. 5 is a differential scanning calorimetry analysis diagram of the self-healing conductive elastomer of Example 15.
  • Example 6 is an appearance view of the self-repairing conductive elastomer of Example 15 after being frozen for 7 days.
  • Example 7 is a stress-strain curve diagram of the self-repairing conductive elastomer of Example 15 before and after freezing.
  • a polymerizable eutectic solvent for self-healing materials is as follows: 13.96g hydrogen bond acceptor choline chloride, 5.8035g hydrogen bond donor maleic acid and 3.554g hydrogen bond donor acrylamide at 60 The reaction was stirred at °C for 4h to obtain a clear and transparent polymerizable eutectic solvent.
  • the glass transition temperature of the polymerizable eutectic solvent measured by differential scanning calorimetry is -104.2°C.
  • a polymerizable eutectic solvent for self-healing materials is as follows: 13.96g hydrogen bond acceptor choline chloride, 3.6g hydrogen bond donor acrylic acid and 3.554g hydrogen bond donor acrylamide at 60°C Stir the reaction for 4h to obtain a clear and transparent polymerizable eutectic solvent.
  • a polymerizable eutectic solvent for self-healing materials is as follows: 13.96g hydrogen bond acceptor choline chloride and 4.3g hydrogen bond donor methacrylic acid and 3.554g hydrogen bond donor acrylamide at 60 The reaction was stirred at °C for 4h to obtain a clear and transparent polymerizable eutectic solvent.
  • a polymerizable eutectic solvent for self-healing materials is as follows: 13.96g hydrogen bond acceptor choline chloride and 6.5g hydrogen bond donor citraconic acid and 3.554g hydrogen bond donor acrylamide at 60 The reaction was stirred at °C for 4h to obtain a clear and transparent polymerizable eutectic solvent.
  • a polymerizable eutectic solvent for self-healing materials is as follows: 13.96g hydrogen bond acceptor choline chloride and 8.7g hydrogen bond donor aconitic acid and 3.554g hydrogen bond donor acrylamide at 60 The reaction was stirred at °C for 4h to obtain a clear and transparent polymerizable eutectic solvent.
  • a polymerizable eutectic solvent for self-healing materials is as follows: 13.96g hydrogen bond acceptor choline chloride, 5.8035g hydrogen bond donor maleic acid and 4.25g hydrogen bond donor methacrylamide The reaction was stirred at 60°C for 4h to obtain a clear and transparent polymerizable eutectic solvent.
  • a polymerizable eutectic solvent for self-healing materials is as follows: 13.96g hydrogen bond acceptor choline chloride, 5.8035g hydrogen bond donor maleic acid and 8.45g hydrogen bond donor diacetone acrylamide The reaction was stirred at 60°C for 4h to obtain a clear and transparent polymerizable eutectic solvent.
  • a polymerizable eutectic solvent for self-healing materials the preparation process is as follows: 13.96g hydrogen bond acceptor choline chloride, 5.8035g hydrogen bond donor maleic acid and 5.65g hydrogen bond donor N-isopropyl The acrylamide was stirred at 60°C for 4 h to obtain a clear and transparent polymerizable eutectic solvent.
  • a polymerizable eutectic solvent for self-healing materials the preparation process is as follows: 13.96g hydrogen bond acceptor choline chloride, 5.8035g hydrogen bond donor maleic acid and 5.75g hydrogen bond donor N-hydroxyethyl The acrylamide was stirred at 60°C for 4 h to obtain a clear and transparent polymerizable eutectic solvent.
  • a polymerizable eutectic solvent for self-healing materials the preparation process is as follows: 13.96g hydrogen bond acceptor choline chloride, 5.8035g hydrogen bond donor maleic acid and 4.95g hydrogen bond donor N,N- The dimethyl acrylamide was stirred at 60°C for 4 hours to obtain a clear and transparent polymerizable eutectic solvent.
  • a polymerizable eutectic solvent for self-healing materials the preparation process is as follows: 25.7g hydrogen bond acceptor methyltriphenylphosphonium bromide and 5.8035g hydrogen bond donor maleic acid and 3.554g hydrogen bond donor Acrylamide was stirred at 60°C for 4 h to obtain a clear and transparent polymerizable eutectic solvent.
  • a polymerizable eutectic solvent for self-healing materials is as follows: 5.35g hydrogen bond acceptor ammonium chloride, 5.8035g hydrogen bond donor maleic acid and 3.554g hydrogen bond donor acrylamide at 60°C The reaction was stirred for 4 hours to obtain a clear and transparent polymerizable eutectic solvent.
  • a self-healing material polymerizable eutectic solvent is as follows: 13.96g hydrogen bond acceptor choline chloride and 5.8035g hydrogen bond donor maleic acid and 7.108g hydrogen bond donor acrylamide at 60 The reaction was stirred at °C for 4h to obtain a clear and transparent polymerizable eutectic solvent.
  • a polymerizable eutectic solvent for self-healing materials is as follows: 13.96g hydrogen bond acceptor choline chloride, 5.8035g hydrogen bond donor maleic acid and 17.77g hydrogen bond donor acrylamide at 60 The reaction was stirred at °C for 4h to obtain a clear and transparent polymerizable eutectic solvent.
  • a self-repairing conductive elastomer the preparation process is as follows:
  • step S3 Preparation of self-repairing conductive elastomer: take 4.83 g of the transparent conductive elastomer prepolymer mixed solution described in step S2, pour it into a polytetrafluoroethylene petri dish (radius 3 cm), and cure under ultraviolet light (2Kw) for 5 min, A transparent self-healing conductive elastomer is obtained.
  • a self-repairing conductive elastomer the preparation process is as follows:
  • step S3 Preparation of self-repairing conductive elastomer: take 4.83 g of the transparent conductive elastomer prepolymer mixed solution described in step S2, pour it into a polytetrafluoroethylene petri dish (radius 3 cm), and cure under ultraviolet light (2Kw) for 5 min, A self-healing conductive elastomer is obtained.
  • a self-repairing conductive elastomer the preparation process is as follows:
  • step S3 Preparation of self-repairing conductive elastomer: take 4.83 g of the transparent conductive elastomer prepolymer mixed solution described in step S2, pour it into a polytetrafluoroethylene petri dish (radius 3 cm), and cure under ultraviolet light (2Kw) for 5 min, A transparent self-healing conductive elastomer is obtained.
  • a self-repairing conductive elastomer the preparation process is as follows:
  • step S3 Preparation of self-healing conductive elastomer: take 4.83 g of the transparent conductive elastomer prepolymer mixed solution described in step S2, pour it into a polytetrafluoroethylene petri dish (radius 3 cm), and cure under ultraviolet light (2Kw) for 5 min. A transparent self-healing conductive elastomer is obtained.
  • a self-repairing conductive elastomer the preparation process is as follows:
  • step S3 Preparation of self-repairing conductive elastomer: take 4.83 g of the transparent conductive elastomer prepolymer mixed solution described in step S2, pour it into a polytetrafluoroethylene petri dish (radius 3 cm), and cure under ultraviolet light (2Kw) for 5 min, A transparent self-healing conductive elastomer is obtained.
  • a self-repairing conductive elastomer the preparation process is as follows:
  • step S3 Preparation of self-repairing conductive elastomer: take 4.83 g of the transparent conductive elastomer prepolymer mixed solution described in step S2, pour it into a polytetrafluoroethylene petri dish (radius 3 cm), and cure under ultraviolet light (2Kw) for 5 min, A transparent self-healing conductive elastomer is obtained.
  • a self-repairing conductive elastomer the preparation process is as follows:
  • step S3 Preparation of self-repairing conductive elastomer: take 4.83 g of the transparent conductive elastomer prepolymer mixed solution described in step S2, pour it into a polytetrafluoroethylene petri dish (radius 3 cm), and cure under ultraviolet light (2Kw) for 5 min, A transparent self-healing conductive elastomer is obtained.
  • a self-repairing conductive elastomer the preparation process is as follows:
  • step S3 Preparation of self-healing conductive elastomer: take 4.83 g of the transparent conductive elastomer prepolymer mixed solution described in step S2, pour it into a polytetrafluoroethylene petri dish (radius 3 cm), and cure under ultraviolet light (2Kw) for 5 min. A transparent self-healing conductive elastomer is obtained.
  • FIG. 1 is a comparison diagram of the self-healing conductive elastomer prepared in Example 15 placed on the school badge sheet.
  • the self-healing conductive elastomer prepared in Examples 15-22 was cut with a blade and cut into two pieces, and then the two pieces of self-healing conductive elastomer after cutting were pieced together.
  • the experimental results showed that the pieced together 2
  • the self-repairing conductive elastomer will immediately bond itself, and it will not break when it is stretched after standing for a period of time. After standing for 48h, the mechanical properties are equivalent to the raw materials.
  • 2 is a self-repairing conductive elastomer self-repairing ability test chart of Example 15,
  • FIG. 2a is a self-repairing conductive elastomer prepared in Example 15;
  • FIG. 2b is two separate self-repairing conductive elastomers obtained by cutting the self-repairing conductive elastomer Repair the conductive elastomer;
  • Figure 2c shows the state of two separate self-repairing conductive elastomers put together, and then immediately clamp one of the self-repairing conductive elastomers with tweezers, and make the other self-repairing conductive elastomer in the air
  • Figure 2d shows the state of the self-repairing conductive elastomer when two pieces of self-repairing conductive elastomer are left standing for 48h, and then the two sides of the self-repairing conductive elastomer are clamped with two tweezers and pulled.
  • the self-repairing conductive elastomer prepared in Examples 15-22 was cut into long strips, and the two ends were connected to wires. A small electric light bulb was installed on the wire, and the light was glowing, indicating that the self-repairing conductive elastomer prepared by the present invention has conductive properties.
  • the elongated self-repairing conductive elastomer is stretched, the brightness of the light bulb will be slightly darkened, but it still emits light. After rebound, the brightness of the light bulb becomes brighter again, indicating that the self-repairing conductive elastomer described in the present invention can achieve flexible stretching. And it still has conductivity during stretching.
  • FIG. 3 is a test chart of the conductive performance of the self-repairing conductive elastomer of Example 15.
  • FIG. 3 is a test chart of the conductive performance of the self-repairing conductive elastomer of Example 15.
  • the self-repairing conductive elastomer prepared in Examples 15-19 was subjected to a stress-strain test, and the stress-strain curve is shown in FIG. 4. It can be seen from FIG. 4 that the self-healing conductive elastomer prepared by the present invention is an elastomer with better resilience.
  • the self-healing conductive elastomer prepared according to the method described in Example 15 was cut into two pieces, and then the two self-healing conductive pieces cut off After putting together the elastomers, put them in the freezing layer of the refrigerator at a temperature of -25°C ⁇ -23°C and freeze them for 7 days. After 7 days, take them out.
  • the two self-healing conductive elastomers cut off are bonded together again, and the cracks are not very strong. Obviously, as shown in Figure 6.
  • the stress-strain test of the self-repairing conductive elastomer was carried out, as shown in Figure 7, and it was found that the stress-strain curve of the self-repairing conductive elastomer after 7 days of freezing treatment and the stress-strain of the original self-repairing conductive elastomer
  • the graphs are substantially the same, indicating that the self-healing conductive elastomer prepared by the present invention still has good self-healing ability at extremely low temperature, and the mechanical properties after self-healing are equivalent to the raw materials.

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Abstract

L'invention concerne un solvant eutectique profond polymérisable pour des matériaux auto-réparables, un élastomère conducteur de l'électricité et un procédé de préparation correspondant. Le solvant eutectique profond polymérisable est obtenu par réaction d'un récepteur de liaison hydrogène avec un donneur de liaison hydrogène à 60 °C à 100 °C, le donneur de liaison hydrogène comprenant un monomère carboxylique contenant une double liaison et un monomère acrylamide, le donneur de liaison hydrogène et le récepteur de liaison hydrogène étant dans un rapport molaire non inférieur à 1:1, et le monomère acrylamide et le monomère carboxylique contenant une double liaison étant dans un rapport molaire non inférieur à 1:1. L'élastomère conducteur de l'électricité est auto-réparable et comprend le solvant eutectique profond polymérisable, un agent de réticulation et un agent d'initiation. Un élastomère conducteur de l'électricité auto-réparable préparé à l'aide du solvant eutectique profond présente un aspect transparent, une bonne conductivité électrique, une excellente performance d'auto-réparation à -30 °C à 60 °C et une bonne stabilité environnementale. Le procédé de production ne nécessite pas l'addition d'un nanomatériau conducteur de l'électricité.
PCT/CN2019/108315 2018-12-03 2019-09-26 Solvant eutectique profond polymérisable pour matériaux auto-réparables, élastomère conducteur d'électricité et procédé de préparation correspondant WO2020114049A1 (fr)

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