Polymer composite material with self-repairing conductive function as well as preparation method and application thereof

Abstract

The invention relates to a polymer composite material with a self-repairing conductive function as well as a preparation method and application of the polymer composite material. Polymer raw materials comprise the following components: polymer polyol, diisocyanate, 2-aminomethyl furan, bismaleimide and conductive filler. The polymer composite material contains dynamic reversible covalent bonds, has self-repairing capability, can be used for 3D printing, and has conductivity. The limitation of a traditional material in specific application can be solved, huge potential and value can be shown in multiple fields such as the Internet of Things, smart home and wearable equipment, and powerful support is provided for intelligence and convenience of the human society.

Description

Technical Field

[0001] The present invention belongs to the technical field of conductive polymers, and in particular relates to a polymer composite material with a self-repairing conductive function, and a preparation method and application thereof. Background Art

[0002] In modern materials science, developing a polymer composite material that integrates self-healing and conductive functions is of great significance for improving the versatility and durability of materials. As a new technology for polymer preparation, the advantage of the solvent-free method is that it avoids the use of solvents in the traditional solvent method, reduces environmental impact and production costs, and improves the performance and stability of the material. 3D printable polymer composites have unique advantages, which can realize the manufacture of complex shapes, improve production efficiency and reduce costs. Combining self-healing, conductive, and electromagnetic shielding functions with 3D printing technology can provide more possibilities for the application of materials. The self-healing function can enable the material to automatically repair itself after being damaged, restore its original performance, and extend its service life. The conductive function allows the material to be used in the manufacture of electronic devices, such as circuit boards, sensors, etc.

[0003] Although traditional conductive materials have excellent conductive properties, they will oxidize during use, causing their performance to rapidly deteriorate, and cannot meet the application requirements of flexible devices. This is extremely unfavorable for the development of sophisticated electronic devices. At the same time, with the increasing demand for wearable and smart nano / micro devices, a new generation of conductive functional materials with excellent flexibility and self-healing properties have good application prospects in recent years. Summary of the invention

[0004] The technical problem to be solved by the present invention is to provide a polymer composite material with self-repairing conductive function and its preparation method and application. The polymer composite material contains dynamic reversible covalent bonds, has self-repairing ability and can be 3D printed, and the polymer composite material has conductive properties.

[0005] The present invention provides a polymer composite material with a self-repairing conductive function, wherein the polymer raw materials include the following components in parts by mass:

[0006]

[0007] Preferably, the polymer polyol is selected from at least one of polyethylene adipate diol, polybutylene adipate diol, polyhexane adipate diol, polycarbonate diol, polyphthalate diol, polyneopentyl adipate diol, polycaprolactone diol, polyethylene adipate monopropylene glycol diol, polyethylene adipate ether diol, and polyethylene adipate diethylene glycol ether diol.

[0008] Preferably, the diisocyanate is selected from at least one of 4,4'-methylenebis(phenyl isocyanate), toluene diisocyanate, isophorone diisocyanate, 4,4'-dicyclohexylmethane-diisocyanate, naphthalene diisocyanate, p-phenylene diisocyanate, 1,4-cyclohexane diisocyanate, xylene diisocyanate, cyclohexane dimethylene diisocyanate, trimethyl-1,6-hexamethylene diisocyanate, tetramethyl meta-xylene diisocyanate, norbornane diisocyanate, dimethyl biphenyl diisocyanate, methylcyclohexyl diisocyanate, polymethylene polyphenyl isocyanate, 1,6-hexamethylene diisocyanate, and modified diisocyanates.

[0009] Preferably, the bismaleimide is selected from at least one of 4,4'-bismaleimide diphenylmethane, 1,2-bis(maleimidoethoxy)ethane, N,N'-m-phenylene bismaleimide, bismaleimide-polyvinyl alcohol-6, bismaleimide-polyvinyl alcohol-2, 1,2-bismaleimidoethane, N,N'-m-phenylene bismaleimide, and N,N-(4-methyl-1,3-phenylene)bismaleimide.

[0010] Preferably, the conductive filler is selected from at least one of carbon nanotubes, carbon black, silver nanosheets, copper powder, aluminum powder, and carbon fiber.

[0011] The present invention also provides a method for preparing a polymer composite material with a self-repairing conductive function, comprising the following steps:

[0012] (1) reacting polymer polyol, diisocyanate and bismaleimide at 50-100° C. for 1-5 hours according to the ratio;

[0013] (2) after the reaction is completed, 2-aminomethylfuran and an initiator are added and reacted at 50-100° C. for 10-30 minutes;

[0014] (3) After the reaction is completed, the product obtained in step (2) is poured into a mold, and then transferred to an oven to continue the reaction at 100-150° C. for 5-10 hours;

[0015] (4) After the reaction is completed, the product obtained in step (3) and the conductive filler are placed in a mixer and kneaded at 100-150° C. for 10-30 min to obtain a polymer composite material with self-repairing conductive function.

[0016] Preferably, the initiator in step (2) is selected from at least one of dibutyltin dilaurate, dioctyltin dilaurate, dibutyltin oxide, stannous isooctanoate, dibutyltin diacetate, zinc isooctanoate, zinc neodecanoate, bismuth isooctanoate, pentamethyldiethylenetriamine, triethylamine, N,N'-dimethylcyclohexylamine, triethanolamine and pyridine; the added amount is 0.1 parts.

[0017] The present invention also provides an application of a polymer composite material with self-repairing conductive function in the Internet of Things, smart homes or wearable devices.

[0018] Beneficial Effects

[0019] The polymer composite material of the present invention contains dynamic reversible covalent bonds, has self-repairing ability and can be 3D printed, and has conductive properties. It can not only solve the limitations of traditional materials in specific applications, but also show great potential and value in multiple fields such as the Internet of Things, smart homes, wearable devices, etc., providing strong support for the intelligence and convenience of human society. BRIEF DESCRIPTION OF THE DRAWINGS

[0020] Figure 1 It is the solid-liquid transition temperature of the polymer composite material prepared in Example 1 before adding conductive filler.

[0021] Figure 2 This is a self-healing ability test of the polymer composite material prepared in Example 1 before adding conductive fillers.

[0022] Figure 3 Mechanical properties test of the polymer composite material prepared in Example 1 before and after remodeling without adding conductive filler.

[0023] Figure 4 The flexibility of the polymer composite material prepared in Example 1 after adding conductive fillers is demonstrated.

[0024] Figure 5 The conductivity of the polymer composite material prepared in Example 1 after adding conductive fillers is demonstrated.

[0025] Figure 6 The mechanical properties of the polymer composite material prepared in Example 1 before and after remodeling after adding conductive fillers were tested. DETAILED DESCRIPTION

[0026] The present invention will be further described below in conjunction with specific embodiments. It should be understood that these embodiments are only used to illustrate the present invention and are not intended to limit the scope of the present invention. In addition, it should be understood that after reading the content taught by the present invention, those skilled in the art can make various changes or modifications to the present invention, and these equivalent forms fall within the scope limited by the appended claims of the application equally.

[0027] Example 1

[0028] S1. Add 50 g of dehydrated polybutylene glycol, 22.23 g of isophorone diisocyanate and 8.959 g of 4,4'-bismaleimide diphenylmethane into a flask and stir to react at 60° C. for 2 h.

[0029] S2. After the reaction is completed, 4.856 g of 22-aminomethylfuran and 0.1 g of dibutyltin dilaurate are added to the flask and stirred at 60° C. for 20 min.

[0030] S3. After the reaction is completed, pour it into a polytetrafluoroethylene mold and then transfer it to an oven to continue reacting at 130°C for 8 hours.

[0031] S4. After the reaction is completed, the product, 4.969 g of carbon nanotubes, 33.133 g of carbon black, and 41.416 g of silver nanosheets are put into a mixer and kneaded at 140° C. for 10 min to obtain a polymer composite material with self-repairing conductive function.

[0032] Example 2

[0033] S1. Add 50 g of dehydrated polybutylene glycol, 22.23 g of isophorone diisocyanate and 8.959 g of 4,4'-bismaleimide diphenylmethane into a flask and stir to react at 60° C. for 2 h.

[0034] S2. After the reaction is completed, 4.856 g of 2-aminomethylfuran and 0.1 g of dibutyltin dilaurate are added to the flask and stirred at 60° C. for 20 min.

[0035] S3. After the reaction is completed, pour it into a polytetrafluoroethylene mold and then transfer it to an oven to continue reacting at 130°C for 8 hours.

[0036] S4. After the reaction is completed, the product, 3.299 g of carbon nanotubes, 21.999 g of carbon black, and 27.499 g of silver nanosheets are put into a mixer and kneaded at 140° C. for 10 min to obtain a polymer composite material with self-repairing conductive function.

[0037] Example 3

[0038] S1. Add 50 g of dehydrated polybutylene glycol, 22.23 g of isophorone diisocyanate and 8.959 g of 4,4'-bismaleimide diphenylmethane into a flask and stir to react at 60° C. for 2 h.

[0039] S2. After the reaction is completed, 4.856 g of 2-aminomethylfuran and 0.1 g of dibutyltin dilaurate are added to the flask and stirred at 60° C. for 20 min.

[0040] S3. After the reaction is completed, pour it into a polytetrafluoroethylene mold and then transfer it to an oven to continue reacting at 130°C for 8 hours.

[0041] S4. After the reaction is completed, the product, 2.094 g of carbon nanotubes, 13.959 g of carbon black, and 17.448 g of silver nanosheets are put into a mixer and kneaded at 140° C. for 10 min to obtain a polymer composite material with self-repairing conductive function.

[0042] Performance test results:

[0043] (1) By Figure 1 As shown, the solid-liquid transition temperature of the polymer composite material prepared in Example 1 before adding conductive filler is 138° C., and has good processability.

[0044] (2) By Figure 2 As shown, the polymer composite material prepared in Example 1 has good thermal remodeling performance before adding conductive fillers. Figure 3 As shown, the mechanical properties of the polymer composite material prepared in Example 1 before and after remodeling were characterized by tensile strength test. The test results showed that the tensile strength of the polymer composite material before remodeling was 37.3MPa; the tensile strength of the polymer composite material after the first hot pressing remodeling was 36.6MPa; and the tensile strength of the polymer composite material after the second hot pressing remodeling was 34.1MPa. This shows that after hot pressing remodeling, the mechanical properties of the polymer material did not change significantly, and it has good remodeling properties.

[0045] (4) By Figure 4 As shown, the polymer composite material prepared in Example 1 has good flexibility after adding conductive fillers.

[0046] (5) By Figure 5 As shown, the polymer composite material prepared in Example 1 has good conductivity after adding conductive fillers.

[0047] (6) By Figure 6 As shown, the mechanical properties of the polymer composite material prepared in Example 1 after adding the conductive filler were characterized by the tensile strength test. The test results showed that the tensile strength of the polymer composite material before reshaping was 17.2Mpa; the tensile strength of the polymer composite material after the first hot pressing reshaping was 16.7Mpa; the tensile strength of the polymer composite material after the second hot pressing reshaping was 16.1Mpa; and the tensile strength of the polymer composite material after the third hot pressing reshaping was 16.1Mpa. This shows that after hot pressing reshaping, the mechanical properties of the polymer composite material have not changed significantly, and it has good reshaping properties.

[0048] (7) The polymer composite materials prepared in Examples 2 and 3 have similar properties to those prepared in Example 1.

Claims

1. A polymer composite material with self-repairing conductive function, characterized in that: The polymer raw materials include the following components by mass:

2. The polymer composite material according to claim 1, characterized in that: The polymer polyol is selected from at least one of polyethylene adipate diol, polybutylene adipate diol, polyhexane adipate diol, polycarbonate diol, polyphthalate diol, polyneopentyl adipate diol, polycaprolactone diol, polyethylene adipate monopropylene glycol diol, polyethylene adipate ether diol, and polyethylene adipate diethylene glycol ether diol.

3. The polymer composite material according to claim 1, characterized in that: The diisocyanate is selected from at least one of 4,4'-methylenebis(phenyl isocyanate), toluene diisocyanate, isophorone diisocyanate, 4,4'-dicyclohexylmethane-diisocyanate, naphthalene diisocyanate, p-phenylene diisocyanate, 1,4-cyclohexane diisocyanate, xylylene diisocyanate, cyclohexane dimethylene diisocyanate, trimethyl-1,6-hexamethylene diisocyanate, tetramethyl meta-xylylene diisocyanate, norbornane diisocyanate, dimethyl biphenyl diisocyanate, methylcyclohexyl diisocyanate, polymethylene polyphenyl isocyanate, 1,6-hexamethylene diisocyanate, and modified diisocyanates.

4. The polymer composite material according to claim 1, characterized in that: The bismaleimide is selected from at least one of 4,4'-bismaleimide diphenylmethane, 1,2-bis(maleimidoethoxy)ethane, N,N'-m-phenylene bismaleimide, bismaleimide-polyvinyl alcohol-6, bismaleimide-polyvinyl alcohol-2, 1,2-bismaleimidoethane, N,N'-m-phenylene bismaleimide, and N,N-(4-methyl-1,3-phenylene) bismaleimide.

5. The polymer composite material according to claim 1, characterized in that: The conductive filler is selected from at least one of carbon nanotubes, carbon black, silver nanosheets, copper powder, aluminum powder, and carbon fiber.

6. A method for preparing a polymer composite material with self-repairing conductive function according to any one of claims 1 to 5, comprising the following steps: (1) reacting polymer polyol, diisocyanate and bismaleimide at 50-100° C. for 1-5 hours according to the ratio; (2) after the reaction is completed, 2-aminomethylfuran and an initiator are added and reacted at 50-100° C. for 10-30 minutes; (3) After the reaction is completed, the product obtained in step (2) is poured into a mold, and then transferred to an oven to continue the reaction at 100-150° C. for 5-10 hours; (4) After the reaction is completed, the product obtained in step (3) and the conductive filler are placed in a mixer and kneaded at 100-150° C. for 10-30 minutes to obtain a polymer composite material with self-repairing conductive function.

7. The preparation method according to claim 6, characterized in that: The initiator in step (2) is selected from at least one of dibutyltin dilaurate, dioctyltin dilaurate, dibutyltin oxide, stannous isooctanoate, dibutyltin diacetate, zinc isooctanoate, zinc neodecanoate, bismuth isooctanoate, pentamethyldiethylenetriamine, triethylamine, N,N'-dimethylcyclohexylamine, triethanolamine, and pyridine; the added amount is 0.1 parts.

8. Application of the polymer composite material with self-repairing conductive function as claimed in any one of claims 1 to 5 in the Internet of Things, smart home or wearable devices.

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