CN104530701A - Low-temperature self-repairing conductive composite material and preparation method thereof - Google Patents
Low-temperature self-repairing conductive composite material and preparation method thereof Download PDFInfo
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- CN104530701A CN104530701A CN201510023081.1A CN201510023081A CN104530701A CN 104530701 A CN104530701 A CN 104530701A CN 201510023081 A CN201510023081 A CN 201510023081A CN 104530701 A CN104530701 A CN 104530701A
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K7/00—Use of ingredients characterised by shape
- C08K7/22—Expanded, porous or hollow particles
- C08K7/24—Expanded, porous or hollow particles inorganic
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G69/00—Macromolecular compounds obtained by reactions forming a carboxylic amide link in the main chain of the macromolecule
- C08G69/02—Polyamides derived from amino-carboxylic acids or from polyamines and polycarboxylic acids
- C08G69/26—Polyamides derived from amino-carboxylic acids or from polyamines and polycarboxylic acids derived from polyamines and polycarboxylic acids
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- H—ELECTRICITY
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- H01B—CABLES; CONDUCTORS; INSULATORS; SELECTION OF MATERIALS FOR THEIR CONDUCTIVE, INSULATING OR DIELECTRIC PROPERTIES
- H01B1/00—Conductors or conductive bodies characterised by the conductive materials; Selection of materials as conductors
- H01B1/20—Conductive material dispersed in non-conductive organic material
- H01B1/24—Conductive material dispersed in non-conductive organic material the conductive material comprising carbon-silicon compounds, carbon or silicon
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K2201/00—Specific properties of additives
- C08K2201/001—Conductive additives
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Abstract
The invention discloses a low-temperature self-repairing conductive composite material and a preparation method thereof. The composite material is characterized by being prepared by physically blending carbon nanotubes and supramolecular polymer at a mass ratio of 1: 1-19, wherein the supramolecular polymer is obtained by carrying out protonation reaction on small-molecule polycarboxylic acid and small-molecule polyamine at a molar ratio of (0.2-5): 1. The composite material disclosed by the invention has the capacities of spontaneously repairing the self structure and conducting electrical energy at a temperature below 0 DEG C.
Description
Technical field
The present invention relates to low temperature self-repair type electro-conductive material technical field, be specifically related to a kind of supramolecule matrix material with low temperature structure self-healing properties and low-temperature conductive self-healing properties and preparation method thereof.
Background technology
Conduction self-repair material is popular research topic in recent years.General selfreparing electro-conductive material is all be made up of conducting medium and polymeric matrix, and the self-reparing capability of polymkeric substance is often depended in the recovery of conductivity.Be subject to the restriction of polymkeric substance used, these materials just will can complete structure repair mostly under room temperature even high temperature, and recover its conductive capability.Qingbin Pei group [Qingbin Pei, et al, Adv.Mater.2013,25,4186 – 4191] attempt nano silver wire to stick to can there is Diels-Alder reaction polymeric matrix on, utilize the selfreparing of film matrix to realize the reconstruction of conductive path, but the reparation of this material need to be warming up to 110 DEG C and just can complete.The group that Michael D.Dickey teaches is at self-healing polymers [Michael D.Dickey, et al., Adv.Mater.2013,25,1589-1592.] in penetrate a liquid metal wire, successfully prepared selfreparing electro-conductive material, but the repair process of this material at room temperature completes, and the recovery of its conductivity depends on the strict docking of liquid wire, strongly limit the using value of this conduction repair materials.Metallic nickel particle is mixed in self-healing polymers matrix and obtains selfreparing conducing composite material by Zhenan Bao professor [Zhenan Bao, et al., Nat.Nanotech.2012,7,825-832.] group.Although the reparation of conductivity does not rely on strict docking, owing to being mixed into a large amount of inorganic particles, the selfreparing character of polymeric matrix is affected, and this material could be repaired under often needing to be heated to the condition of 50 DEG C completely.Junqi Sun group attempts nano silver wire to stick to polymine/Ju Bing Xi Suan – hyaluronic acid [Junqi Sun, et al., Adv.Mater.2012,24,4578-4582.] multilayer component film surface, utilize the selfreparing of film matrix to realize the reconstruction of conductive path.But, in this course, need on film matrix, drip a small amount of water.Because water can freeze under lower than the condition of 0 DEG C, this makes it to be applied to low temperature and repairs electro-conductive material field.In sum, above selfreparing electro-conductive material all can not be applicable to some temperature lower than the climatope of 0 DEG C.But in many areas of north of China, the temperature in winter is often low to moderate-20 DEG C even lower.Because temperature is low, wire and antenna often lose its snappiness at room temperature.Accidental collision or displacement just may cause wire or sky thread breakage.In some cases, this can cause serious consequence.Such as, in Emergency relief process, therefore the contact between the people be in trouble and rescue personnel can be interrupted.In electron device, application of cold temperature selfreparing electro-conductive material is the effective way solving the unsafe condition that may occur.Thus, exploitation has the electro-conductive material of low temperature self-reparing capability is very valuable.
Summary of the invention
The object of this invention is to provide a kind of low temperature selfreparing conducing composite material and preparation method thereof, be intended to solve electro-conductive material reparation problem at low ambient temperatures.
Technical solution problem of the present invention adopts following technical scheme:
Low temperature selfreparing conducing composite material of the present invention, its feature is: described low temperature selfreparing conducing composite material is obtained through physical blending 1:1 ~ 19 in mass ratio by carbon nanotube and supermolecule polymer; Described supermolecule polymer is that the small molecules polycarboxylic acid of 0.2 ~ 5:1 and small molecules polyamine obtain through protonation reaction by mol ratio.
The preparation method of above-mentioned low temperature selfreparing conducing composite material is: be that the small molecules polycarboxylic acid of 0.2 ~ 5:1 mixes in a solvent with small molecules polyamine by mol ratio, then at 15-30 DEG C, 5-60min is stirred, make small molecules polycarboxylic acid and small molecules polyamine generation protonation reaction, solvent is removed in product vacuum drying, obtains supermolecule polymer; The ratio of the molar weight of described small molecules polyamine and the volume of described solvent is 0.02mol:10 ~ 20mL;
Carbon nanotube is mixed 1:1 ~ 19 in mass ratio with described supermolecule polymer, obtains low temperature selfreparing conducing composite material.
Wherein: described small molecules polycarboxylic acid is at least one in succinic acid, hexanodioic acid, citric acid, tartrate, ethylenediamine tetraacetic acid (EDTA) and terephthalic acid;
Described small molecules polyamine is N, N, N ', N '-tetramethyl-1,3-propane diamine, N, N, N ', at least one in N '-tetraethyl--1,3-propylene diamine, propylene diamine and hexanediamine.
Described solvent is at least one in water and methyl alcohol.
Different from traditional polymer, the supermolecule polymer adopted in matrix material of the present invention is formed by the combination of weak non covalent bond by small molecules.Weak non covalent bond (such as electrostatic forcing) can relatively easily rupture restructuring, does not need very high energy; And small molecules still has higher locomotor activity at low temperatures, be convenient to fracture and the restructuring of non covalent bond.Thus, through the supermolecule polymer that non covalent bond is formed by connecting, there is low temperature self-reparing capability by small molecules.The principle of this conductivity of composite material is because supermolecule polymer is interacted by ionic linkage to form, and itself have weak electroconductibility, and the material of this high conductivity of carbon nanotube adds, can increase the electroconductibility of system.
Compared with the prior art, beneficial effect of the present invention is embodied in:
1, the conduction self-repair procedure of selfreparing conducing composite material of the present invention can complete under cryogenic, overcomes the difficult problem completing conduction reparation under conventional conductive repair materials needs room temperature or higher temperature;
2, the conduction repair process of selfreparing conducing composite material of the present invention can spontaneously carry out without the need to any external stimulus, overcomes the difficult problem that traditional material needs the outside stimuluss such as heating, solvent to repair;
3, selfreparing conducing composite material repair process of the present invention is without the need to close alignment, overcomes the problem that conventional conductive repair materials needs close alignment;
4, material therefor of the present invention is that supermolecule polymer and carbon nanotube physical mixed form, and preparation process is simple.
Accompanying drawing explanation
Fig. 1 is means of differential scanning calorimetry (DSC) curve of embodiment 1 gained supermolecule polymer, and this test result shows, supermolecule polymer has very low second-order transition temperature;
Fig. 2 is the low temperature repairing performance taking the mode testing example 1 gained matrix material supporting counterweight, Fig. 3 is the low temperature repairing performance taking the mode testing example 1 gained matrix material hanging counterweight, test condition is all-24 DEG C, and test result shows that matrix material can complete selfreparing at low temperatures;
Fig. 4 is embodiment 1 gained matrix material conductivity return curve under low temperature environment and room temperature environment, and this test result shows, the conductivity of matrix material is able to good recovery after cut-out-docking.
Specific embodiment
Below in conjunction with specific embodiment, the present invention will be further described, but the present invention is not limited thereto.
Embodiment 1
The present embodiment prepares low temperature selfreparing electro-conductive material as follows.
(1) by Citric Acid, usp, Anhydrous Powder (3.842g, 0.02mol) and N, N, N ', N '-tetramethyl-1,3-propane diamine (2.604g, 0.02mol) joins in 10mL methanol solvate, vigorous stirring 30min under room temperature, makes small molecules polycarboxylic acid and small molecules polyamine generation protonation reaction;
(2) reaction mixture that step (1) obtains is put in 60 DEG C of dryings in vacuum drying oven and removes methyl alcohol in 4 days, obtain dry supermolecule polymer;
(3) by carbon nanotube and supermolecule polymer in mass ratio 1:19 mix, obtain target product low temperature selfreparing conducing composite material.
For characterizing the self-healing properties of the present embodiment gained selfreparing electro-conductive material, test as follows:
The low temperature DSC of step (2) gained supermolecule polymer is as Fig. 1, can find out that its second-order transition temperature is near-32 DEG C, show that the segment of this polymkeric substance still has mobility in low temperature environment, be beneficial to the low temperature selfreparing realizing matrix material.
The low temperature self-healing properties test of target product is as follows:
First take the repairing performance of the mode test material supported, result as shown in Figure 2.The low temperature selfreparing conducing composite material that Fig. 2 (a) obtains for the present embodiment, after being disconnected (as Suo Shi Fig. 2 (b)), under the low temperature environment of-24 DEG C, material merges (as Suo Shi Fig. 2 (c)) again through the docking reparation of 2h, and material can support 50g counterweight and breaking part destroyed (as Suo Shi Fig. 2 (d)).
Then the repairing performance of the mode test material hung is taked, result as shown in Figure 3, the low temperature selfreparing conducing composite material that Fig. 3 (a) obtains for the present embodiment, after being disconnected (as Suo Shi Fig. 3 (b)), under the low temperature environment of-24 DEG C, material merges (as shown in Fig. 3 (c) and Fig. 3 (d)) again through the docking reparation of 2h, and material can hang 50g counterweight and breaking part destroyed (as Suo Shi Fig. 3 (e)).
Above result shows, the low temperature selfreparing conducing composite material in the present invention can complete structure repair under the condition of-24 DEG C, and the material after selfreparing has good mechanical strength.
The conductivity return curve of the sample of the present embodiment gained as shown in Figure 4.Sample is placed and is disconnected after (1h) for 1 hour under-24 DEG C of conditions, and again docks.As can be seen from the figure, after disconnecting, the electrical resistance of restructuring sample extends continuous decline repair time, and after repairing through 4 hours, its resistance stabilization is at 6k Ω, and the electroconductibility of matrix material is recovered preferably.
This fully shows that the low temperature selfreparing conducing composite material in the present invention can complete the selfreparing of conductivity under-24 DEG C of conditions, and the matrix material after selfreparing still has good conductivity.
In sum, the low temperature selfreparing conducing composite material in the present invention can complete structure repair and conductivity reparation under-24 DEG C of conditions.
Embodiment 2:
The present embodiment adopts the method identical with embodiment 1 to prepare low temperature selfreparing conducing composite material, and difference is only: " 3.842g Citric Acid, usp, Anhydrous Powder " in step (1) be changed to " 7.648g Citric Acid, usp, Anhydrous Powder ".
Test can obtain through the self-healing properties identical with embodiment 1: can support and dangle after the reparation of the present embodiment gained matrix material low temperature 50g counterweight; Initial resistance under the present embodiment gained matrix material room temperature is 2.7 kilo-ohms, repairs 30min after cut-out, and its resistance is 3 kilo-ohms; Under low temperature, initial resistance is 3.6 kilo-ohms, and after cutting off, low temperature repairs 4h, and resistance value is stabilized in 10 kilo-ohms thereupon.
Embodiment 3:
The present embodiment adopts the method identical with embodiment 1 to prepare low temperature selfreparing conducing composite material, distinguishes and is only: by step (1) " 2.604g N, N, N '; N '-tetramethyl-1,3-propane diamine " be changed to " 5.208g N, N; N ', N '-tetramethyl-1,3-propane diamine ".
Test can obtain through the self-healing properties identical with embodiment 1: can support and dangle after the reparation of the present embodiment gained matrix material low temperature 50g counterweight; Under the present embodiment gained matrix material room temperature, initial resistance is 2.5 kilo-ohms, repairs 30min after cut-out, and its resistance is 2.8 kilo-ohms; Under low temperature, initial resistance is 3.2 kilo-ohms, and after cutting off, low temperature repairs 4h, and resistance value is stabilized in 9 kilo-ohms thereupon.
Embodiment 4:
The present embodiment adopts the method identical with embodiment 1 to prepare low temperature selfreparing conducing composite material, and difference is only: " 3.842g Citric Acid, usp, Anhydrous Powder " in step 1 be changed to " 3.002g tartrate ".
Test can obtain through the self-healing properties identical with embodiment 1: can support and dangle after the reparation of the present embodiment gained matrix material low temperature 50g counterweight; Under the present embodiment gained matrix material room temperature, initial resistance is 5 kilo-ohms, repairs 30min after cut-out, and its resistance is 6 kilo-ohms; Under low temperature, initial resistance is 8 kilo-ohms, and after cutting off, low temperature repairs 4h, and resistance value is stabilized in 15 kilo-ohms thereupon.
Embodiment 5:
The present embodiment adopt the method identical with embodiment 1 prepare low temperature selfreparing conducing composite material, distinguish only be: by step 1 " 2.604g N, N, N, ' N '-tetramethyl-1,3-propane diamine " be changed to " 1.482g propylene diamine ".
Test can obtain through the self-healing properties identical with embodiment 1: can support and dangle after the reparation of the present embodiment gained matrix material low temperature 50g counterweight; Under the present embodiment gained matrix material room temperature, initial resistance is 3.8 kilo-ohms, repairs 30min after cut-out, and its resistance is 5 kilo-ohms; Under low temperature, initial resistance is 6 kilo-ohms, and after cutting off, low temperature repairs 4h, and resistance value is stabilized in 11 kilo-ohms thereupon.
Embodiment 6:
The present embodiment adopts the method identical with embodiment 1 to prepare low temperature selfreparing conducing composite material, and difference is only: " carbon nanotube and supermolecule polymer in mass ratio 1:19 mix " in step (3) be changed to " carbon nanotube and supermolecule polymer in mass ratio 3:17 mix ".
Test can obtain through the self-healing properties identical with embodiment 1: cannot support and dangle after the reparation of the present embodiment gained matrix material low temperature 50g counterweight; Under the present embodiment gained matrix material room temperature, initial resistance is 1.1 kilo-ohms, repairs 30min after cut-out, and its resistance is 6 kilo-ohms; Under low temperature, initial resistance is 1.6 kilo-ohms, and after cutting off, low temperature repairs 4h, and resistance value is stabilized in 16 kilo-ohms thereupon.
Claims (6)
1. a low temperature selfreparing conducing composite material, is characterized in that: described low temperature selfreparing conducing composite material is obtained through physical blending 1:1 ~ 19 in mass ratio by carbon nanotube and supermolecule polymer; Described supermolecule polymer is that the small molecules polycarboxylic acid of 0.2 ~ 5:1 and small molecules polyamine obtain through protonation reaction by mol ratio.
2. low temperature selfreparing conducing composite material according to claim 1, is characterized in that:
Described small molecules polycarboxylic acid is at least one in succinic acid, hexanodioic acid, citric acid, tartrate, ethylenediamine tetraacetic acid (EDTA) and terephthalic acid;
Described small molecules polyamine is N, N, N ', N '-tetramethyl-1,3-propane diamine, N, N, N ', at least one in N '-tetraethyl--1,3-propylene diamine, propylene diamine and hexanediamine.
3. the preparation method of a low temperature selfreparing conducing composite material according to claim 1, it is characterized in that: be that the small molecules polycarboxylic acid of 0.2 ~ 5:1 mixes in a solvent with small molecules polyamine by mol ratio, then at 15-30 DEG C, 5-60min is stirred, make small molecules polycarboxylic acid and small molecules polyamine generation protonation reaction, solvent is removed in product vacuum drying, obtains supermolecule polymer;
Carbon nanotube is mixed 1:1 ~ 19 in mass ratio with described supermolecule polymer, obtains low temperature selfreparing conducing composite material.
4. preparation method according to claim 3, is characterized in that: the ratio of the molar weight of described small molecules polyamine and the volume of described solvent is 0.02mol:10 ~ 20mL.
5. the preparation method according to claim 3 or 4, is characterized in that:
Described small molecules polycarboxylic acid is at least one in succinic acid, hexanodioic acid, citric acid, tartrate, ethylenediamine tetraacetic acid (EDTA) and terephthalic acid;
Described small molecules polyamine is N, N, N ', N '-tetramethyl-1,3-propane diamine, N, N, N ', at least one in N '-tetraethyl--1,3-propylene diamine, propylene diamine and hexanediamine.
6. the preparation method according to claim 3 or 4, is characterized in that: described solvent is at least one in water and methyl alcohol.
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN106969860A (en) * | 2017-05-01 | 2017-07-21 | 苏州科技大学 | Intelligent Magnetic driving selfreparing flexible pressure-sensitive sensor and preparation method thereof |
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| US5348686A (en) * | 1992-06-22 | 1994-09-20 | The Whitaker Corporation | Electrically conductive gel |
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Granted publication date: 20170811 Termination date: 20200115 |