WO2020114049A1

WO2020114049A1 - Polymerizable deep eutectic solvent for self-repairing materials, electrically conductive elastomer, and preparation method thereof

Info

Publication number: WO2020114049A1
Application number: PCT/CN2019/108315
Authority: WO
Inventors: 何明辉; 李仁爱; 陈广学; 张凯丽; 田君飞
Original assignee: 华南理工大学
Priority date: 2018-12-03
Filing date: 2019-09-26
Publication date: 2020-06-11
Also published as: CN111253520A; CN111253520B

Abstract

Disclosed are a polymerizable deep eutectic solvent for self-repairing materials, an electrically conductive elastomer, and a preparation method thereof. The polymerizable deep eutectic solvent is obtained by reacting a hydrogen bond receptor with a hydrogen bond donor at 60°C to 100°C, the hydrogen bond donor comprising a double bond-containing carboxylic monomer and an acrylamide monomer, the hydrogen bond donor and the hydrogen bond receptor being in a molar ratio not lower than 1:1, and the acrylamide monomer and the double bond-containing carboxylic monomer being in a molar ratio not lower than 1:1. The electrically conductive elastomer is self-repairing and comprises the polymerizable deep eutectic solvent, a cross-linking agent and an initiating agent. A self-repairing electrically conductive elastomer prepared using the deep eutectic solvent has a transparent appearance, good electrical conductivity, excellent self-repairing performance at -30°C to 60°C, and good environmental stability. The preparation process does not require the addition of an electrically conductive nanomaterial.

Description

Polymerizable eutectic solvent, conductive elastomer and preparation method for self-healing materials

Technical field

The invention relates to the field of ionic liquids. In particular, the invention relates to a polymerizable eutectic solvent for self-healing materials, a conductive elastomer, and a preparation method thereof.

Background technique

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. At present, 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. However, the current research has relatively few reports on the preparation of polymerizable eutectic solvents in terms of polymer preparation, and there is no report that polymerizable eutectic solvents can be used to directly prepare self-healing elastomers.

Highly transparent, stretchable, conductive, fast self-repairing elastomer materials have strong plasticity, especially in the fields of conductive electrodes, brakes, sensors, speakers and flexible display films. In recent years, the rapid development of flexible electronic products that can be stretched and stretched has transparency, flexibility, tensile properties, electrical conductivity, and self-healing properties in various environments for transparent, stretchable, conductive, and fast self-healing elastomers. Put forward higher requirements. Currently reported self-healing conductive materials are generally prepared using nano-conductive particles (such as polypyrrole, PEDOT: PSS, graphene, carbon nanotubes, etc.) composite flexible polymers (such as polyurethane (PU), polydimethylsiloxane, etc. ( PDMS), etc.) method, but this method has major defects. First, the addition of nano-conductive particles in the preparation process greatly reduces the transparency of the self-healing material, limiting the use of self-healing materials; second, most of the current research focus In the exploration of self-healing conductive hydrogels, there is very little involved with moisture-free ionic gel elastomers, and it is well known that hydrogels have poor mechanical properties and cannot maintain their own moisture in natural environments, resulting in performance degradation The third is that the current preparation process of self-healing materials is complicated, most of which involve the use of organic solvents, and the cost is high, which has played a certain role in limiting the development of self-healing materials. Therefore, it is necessary to explore a new type of self-healing material, which can not only ensure high light transmittance, electrical conductivity, high tensile properties and fast self-healing performance, but also achieve lower cost and better environmental stability.

Summary of the invention

Based on this, 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.

The technical solution is as follows:

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 For monomers, the molar ratio of the hydrogen bond donor to the hydrogen bond acceptor is not less than 1:1, and 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. In the present invention, 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.

In one embodiment, 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.

In one embodiment, 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.

In one embodiment, the double bond-containing carboxylic acid monomer is acrylic acid or maleic acid.

In one embodiment, the acrylamide monomers are acrylamide, methacrylamide, diacetone acrylamide, N-isopropyl acrylamide, N-hydroxyethyl acrylamide, N,N-dimethyl Acrylamide, N-methylol acrylamide.

In one embodiment, the acrylamide monomer is acrylamide.

In one embodiment, 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.

In one embodiment, the crosslinking agent is tripropylene glycol diacrylate, polyethylene glycol diacrylate, dipropylene glycol diacrylate, 1,6-hexanediol diacrylate, neopentyl glycol One or more of diacrylate, diethylene glycol diphthalate, trimethylolpropane triacrylate, pentaerythritol tetraacrylate, etc.

In one of the embodiments, the initiator is a thermal initiator or a photoinitiator.

In one embodiment, the photoinitiator is one of benzoin and derivative photoinitiators, benzyl photoinitiators, alkyl benzophenone photoinitiators, and acylphosphine oxide photoinitiators. One or more. Specifically, 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, α,α-dimethoxy-α-phenylacetophenone and the like. The alkyl ketones may be α,α-diethoxyacetophenone, α-hydroxyalkyl ketone, α-aminoalkyl ketone, and the like. The acylphosphine oxide may be aroylphosphine oxide, bisbenzoylphenylphosphine oxide, or the like. More specifically, 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. Specifically, 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:

S1. Preparation of polymerizable eutectic solvent: the hydrogen bond acceptor and the hydrogen bond donor are reacted at 60 to 100°C for 3 to 5 hours to obtain a clear and transparent polymerizable eutectic solvent;

S2. Prepare a conductive elastomer prepolymer mixed solution: mix the crosslinking agent and initiator with the polymerizable eutectic solvent uniformly, and stir for 1 to 3 hours to obtain a conductive elastomer prepolymer mixed solution;

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.

In one of the embodiments, the curing energy of the ultraviolet light is 2Kw.

In one of the embodiments, 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. When mixed in a specific ratio, 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℃～60℃, and self-healing The conductive elastomer has good environmental stability, simple preparation method, low pollution and low cost.

BRIEF DESCRIPTION

FIG. 1 is a comparison diagram of a self-repairing conductive elastomer of Example 15 placed on a school badge sheet.

2 is a test chart of the self-repairing ability of the self-repairing conductive elastomer of Example 15. FIG.

FIG. 3 is a test chart of the conductive performance of the self-repairing conductive elastomer of Example 15. FIG.

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.

6 is an appearance view of the self-repairing conductive elastomer of Example 15 after being frozen for 7 days.

7 is a stress-strain curve diagram of the self-repairing conductive elastomer of Example 15 before and after freezing.

detailed description

In order to make the objectives, technical solutions and advantages of the present invention clearer, the present invention will be further described in detail below in conjunction with the accompanying drawings and specific embodiments. It should be understood that the specific embodiments described herein are only used to explain the present invention, and do not limit the protection scope of the present invention.

Example 1

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 3.554g hydrogen bond donor acrylamide at 60 The reaction was stirred at ℃ 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.

Example 2

A polymerizable eutectic solvent for self-healing materials, the preparation process 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℃ Stir the reaction for 4h to obtain a clear and transparent polymerizable eutectic solvent.

Example 3

A polymerizable eutectic solvent for self-healing materials, the preparation process 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 ℃ for 4h to obtain a clear and transparent polymerizable eutectic solvent.

Example 4

A polymerizable eutectic solvent for self-healing materials, the preparation process 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 ℃ for 4h to obtain a clear and transparent polymerizable eutectic solvent.

Example 5

A polymerizable eutectic solvent for self-healing materials, the preparation process 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 ℃ for 4h to obtain a clear and transparent polymerizable eutectic solvent.

Example 6

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 4.25g hydrogen bond donor methacrylamide The reaction was stirred at 60°C for 4h to obtain a clear and transparent polymerizable eutectic solvent.

Example 7

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 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.

Example 8

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.

Example 9

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.

Example 10

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.

Example 11

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.

Example 12

A polymerizable eutectic solvent for self-healing materials, the preparation process 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℃ The reaction was stirred for 4 hours to obtain a clear and transparent polymerizable eutectic solvent.

Example 13

A self-healing material polymerizable eutectic solvent, the preparation process 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 ℃ for 4h to obtain a clear and transparent polymerizable eutectic solvent.

Example 14

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 17.77g hydrogen bond donor acrylamide at 60 The reaction was stirred at ℃ for 4h to obtain a clear and transparent polymerizable eutectic solvent.

Add 0.25g of 2-hydroxy-4'-(2-hydroxyethoxy)-2-methylphenylacetone to the eutectic solvents prepared in Examples 1-10, Example 12, and Example 13, Stir for 2h, mix evenly, then pour into a polytetrafluoroethylene petri dish (radius 3cm), and cure under ultraviolet light (2Kw) for 5min to obtain an elastomer with transparent appearance. Add 0.35g of 2-hydroxy-4'-(2-hydroxyethoxy)-2-methylphenylacetone to the eutectic solvent prepared in Example 11 and Example 14, stir for 2h, mix evenly, It was then poured into a polytetrafluoroethylene petri dish (radius 3 cm) and cured under ultraviolet light (2Kw) for 5 minutes to obtain a transparent-looking elastomer.

Cut the above-prepared elastomer with a blade, cut it into two pieces, then piece together the two pieces of elastomer, and then take out the observation elastomer. As a result, it was found that the eutectic solvent prepared in Examples 1-14 was irradiated with initiator and ultraviolet light. After cutting, the elastomer immediately stuck together again, there were cracks at the joint, but the two pieces of elasticity The body does not separate. It can be seen that the polymerizable eutectic solvent described in this embodiment 1-14 has rapid self-healing ability after curing, and can be used to prepare self-healing materials.

Example 15

A self-repairing conductive elastomer, the preparation process is as follows:

S1. Preparation of polymerizable eutectic solvent: 13.96g hydrogen bond acceptor choline chloride, 5.8035g hydrogen bond donor maleic acid and 3.554g hydrogen bond donor acrylamide were stirred at 60°C for 4h to obtain clear and transparent Polymerizable eutectic solvent.

S2. Preparation of a mixed solution of conductive elastomer prepolymer: 0.17g of polyethylene glycol diacrylate, 0.23g of 2-hydroxy-4'-(2-hydroxyethoxy)-2-methylphenylacetone and The eutectic solvent is mixed evenly, and stirred and reacted for 2 hours to obtain a transparent conductive elastomer prepolymer mixed solution.

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.

Example 16

A self-repairing conductive elastomer, the preparation process is as follows:

S2. Preparation of a mixed solution of conductive elastomer prepolymer: 0.34g of polyethylene glycol diacrylate, 0.24g of 2-hydroxy-4'-(2-hydroxyethoxy)-2-methylphenylacetone and The eutectic solvent is mixed evenly, and stirred and reacted for 2 hours to obtain a transparent conductive elastomer prepolymer mixed solution.

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.

Example 17

A self-repairing conductive elastomer, the preparation process is as follows:

S2. Preparation of a mixed solution of conductive elastomer prepolymer: 0.51g of polyethylene glycol diacrylate, 0.24g of 2-hydroxy-4'-(2-hydroxyethoxy)-2-methylphenylacetone and The eutectic solvent is mixed evenly, and stirred and reacted for 2 hours to obtain a transparent conductive elastomer prepolymer mixed solution.

Example 18

A self-repairing conductive elastomer, the preparation process is as follows:

S2. Preparation of a mixed solution of conductive elastomer prepolymer: 0.68g of polyethylene glycol diacrylate, 0.24g of 2-hydroxy-4'-(2-hydroxyethoxy)-2-methylphenylacetone and The eutectic solvent is mixed evenly, and stirred and reacted for 2 hours to obtain a transparent conductive elastomer prepolymer mixed solution.

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.

Example 19

A self-repairing conductive elastomer, the preparation process is as follows:

S1. Preparation of polymerizable eutectic solvent: 13.96g hydrogen bond acceptor choline chloride, 5.8035g hydrogen bond donor maleic acid and 7.108g hydrogen bond donor acrylamide were stirred at 60℃ for 4h to obtain clear and transparent Polymerizable eutectic solvent.

S2. Preparation of a mixed solution of conductive elastomer prepolymer: 0.17g of polyethylene glycol diacrylate, 0.27g of 2-hydroxy-4'-(2-hydroxyethoxy)-2-methylphenylacetone and The eutectic solvent is mixed evenly, and stirred and reacted for 2 hours to obtain a transparent conductive elastomer prepolymer mixed solution.

Example 20

A self-repairing conductive elastomer, the preparation process is as follows:

S2. Preparation of mixed solution of conductive elastomer prepolymer: 0.21g of neopentyl glycol diacrylate, 0.23g of 2-hydroxy-4'-(2-hydroxyethoxy)-2-methylbenzeneacetone and The eutectic solvent is mixed evenly, and stirred and reacted for 2 hours to obtain a transparent conductive elastomer prepolymer mixed solution.

Example 21

A self-repairing conductive elastomer, the preparation process is as follows:

S2. Preparation of mixed solution of conductive elastomer prepolymer: 1.2g of dipropylene glycol diacrylate, 0.74g of 2-hydroxy-2-methyl-1-phenylacetone and the eutectic solvent are mixed evenly and stirred After 2 hours of reaction, a transparent conductive elastomer prepolymer mixed solution was obtained.

Example 22

A self-repairing conductive elastomer, the preparation process is as follows:

S2. Preparation of a conductive elastomer prepolymer mixed solution: 0.17g of polyethylene glycol diacrylate, 1.15g of 2-hydroxy-4'-(2-hydroxyethoxy)-2-methylphenylacetone and The eutectic solvent is mixed evenly, and stirred and reacted for 2 hours to obtain a transparent conductive elastomer prepolymer mixed solution.

In the present invention, all of Examples 15-22 can prepare transparent circular elastomers (transparent appearance and elasticity), which can be clearly seen on the school badge (South China University of Technology) drawings, and the badge pattern can be clearly seen. The transparency of the shaped elastomer is extremely high. 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. When 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.

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.

Differential scanning calorimetry analysis was performed on the self-healing conductive elastomer described in Example 15, and the graph is shown in FIG. 5. From FIG. 5, it can be seen that the glass transition temperature of the self-healing conductive elastomer obtained in the embodiment is -98.6°C. It can be seen that the self-healing conductive elastomer according to the present invention can maintain a high elasticity state at a very low temperature, the molecular chain can move in a wide temperature range, and can self-heal at a low temperature.

To further investigate the repair ability of the self-healing conductive elastomer of the present invention at low temperature, 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℃～-23℃ 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.

The technical features of the above-mentioned embodiments can be combined arbitrarily. To simplify the description, all possible combinations of the technical features in the above-mentioned embodiments are not described. However, as long as there is no contradiction in the combination of these technical features, All should be considered within the scope of this description.

The above examples only express several implementations of the present invention, and their descriptions are more specific and detailed, but they should not be construed as limiting the scope of the invention patent. It should be noted that, for a person of ordinary skill in the art, without departing from the concept of the present invention, several modifications and improvements can also be made, which all fall within the protection scope of the present invention. Therefore, the protection scope of the invention patent shall be subject to the appended claims.

Claims

A polymerizable eutectic solvent for self-healing materials, characterized in that it is 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 the acrylamide monomer, the molar ratio of the hydrogen bond donor to the hydrogen bond acceptor is not less than 1:1, and the molar ratio of the acrylamide monomer to the double bond-containing carboxylic acid monomer is not less than 1:1.
The polymerizable eutectic solvent for self-healing materials according to claim 1, wherein the molar ratio of the hydrogen bond acceptor to the double bond-containing carboxylic acid monomer and acrylamide monomer is 2:1 :1～2:1:5.
The polymerizable eutectic solvent for self-healing materials according to claim 1, wherein the double bond-containing carboxylic acid monomer is acrylic acid, methacrylic acid, maleic acid, itaconic acid, citraconic acid One or more of acid and aconitic acid.
The polymerizable eutectic solvent for self-healing materials according to claim 3, wherein the carboxylic acid monomer containing double bonds is acrylic acid or maleic acid.
The polymerizable eutectic solvent for self-healing materials according to claim 1, wherein the acrylamide monomer is acrylamide, methacrylamide, diacetone acrylamide, N-isopropyl acrylamide , N-hydroxyethylacrylamide, N,N-dimethylacrylamide, N-hydroxymethylacrylamide.
The polymerizable eutectic solvent for self-healing materials according to claim 5, wherein the acrylamide monomer is acrylamide.
The polymerizable eutectic solvent for self-healing materials according to claim 1, wherein the hydrogen bond acceptor is choline chloride, anhydrous betaine, betaine monohydrate, ammonium chloride, methyl group One or more of triphenylphosphonium bromide, benzyltriphenylphosphonium chloride, N,N-diethylethanolammonium chloride, etc.
A self-healing conductive elastomer, characterized by comprising: a polymerizable eutectic solvent for the self-healing material, a cross-linking agent and an initiator, and the molar ratio of the cross-linking agent to the hydrogen bond donor is 0.5: 100 to 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.
The self-healing conductive elastomer according to claim 8, wherein the initiator is a thermal initiator or a photoinitiator.
The method for preparing a self-healing conductive elastomer according to claim 8 or 9, characterized in that it comprises the following steps:

S1. Preparation of polymerizable eutectic solvent: the hydrogen bond acceptor and the hydrogen bond donor are reacted at 60 to 100°C for 3 to 5 hours to obtain a clear and transparent polymerizable eutectic solvent;

S2. Prepare a conductive elastomer prepolymer mixed solution: mix the crosslinking agent and initiator with the polymerizable eutectic solvent uniformly, and stir for 1 to 3 hours to obtain a conductive elastomer prepolymer mixed solution;

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.