KR20090043726A - A self-healing conductive composite - Google Patents

Abstract

The present invention relates to the development of self-healing composites containing carbon nanotubes and their performance evaluation methods. Specifically, a polymer composite including a capsule containing a healing agent and a catalyst is synthesized, and when the capsule is damaged by cracking, the capsule is broken and the catalyst material flows out and reacts with the healing agent mixed in the support to recover the crack. will be.

In particular, by including carbon nanotubes in the support, the mechanical strength of the composite itself is increased and has electrical conductivity, and the self-healing is not only restored when the cracks generated by adding carbon nanotubes to the microcapsules are recovered. The electrical conductivity of the composite is also restored. In addition to the existing strength measurement methods, micro-cantilever microcrystals and crystal oscillators can be used to evaluate the recovery mechanism and recovery rate of self-healing composites.

Carbon nanotubes, self-healing

Description

Self-healing conductive composites {A SELF-HEALING CONDUCTIVE COMPOSITE}

The present invention relates to the development of self-healing composites containing carbon nanotubes and a method for evaluating the performance thereof, and includes microcapsules containing carbon nanotubes so as to restore mechanical and electrical properties of a support including carbon nanotubes. A self-healing complex and its recovery mechanism and methods for evaluating the rate of recovery are discussed.

In general, polymer composites are easily damaged by fine cracks. However, since micro cracks are difficult to detect, it is almost impossible to repair them externally whenever a crack occurs. In particular, in the case of polymer composites used in aircrafts or automobiles, the mechanical strength degradation caused by micro cracks causes enormous human loss and property loss, and thus self-healing composites have been developed as a way to solve these problems.

As an example, a way of changing the environment from the outside for self healing has been developed. Wang et al., For example, suggested adding solutions (P. Wang, S. Lee, JP Harmon, J. polym. Sci. B 32, 1217-1227 (1994), CB Lin, S. Lee, KS). Liu, Polym. Eng. Sci. 30, 1399-1406 (1990)), and Shen et al. (JS Shen, JP Harmon, S. Lee, J. Mater. Res. 17, 135-1440 (2002)). In addition, Li et al. Inject the healing material from the outside (VC Li, YM Lim, YW Chan, Composites Part B, 29,819827 (1998), J. Raghavan, RP Wool, J. Appl.Polym. Sci. 71, 775-785 (1999).

In recent years, microcapsules have been used to develop self-healing polymer complexes and repetitive self-healing systems, such as biological systems, when damaged by microcracks (SR White, NR Sottos, PH Geubelle). , JS Moore, MR Kessler, SR Sriram, EN Brown, S. Viswanathan, Nature 409, 794-797 (2001), SH Cho, HM Anderson, SR White, NR Sottos, PV Braun, Adv. Mater. 18, 997- 1000 (2006), KS Toohey, NR Sottos, JA Lewis, JJ Moore, SR White, Nature Mater. 6, 581-585 (2007))

Conventionally, in the case of self-healing complexes, the area of healing is related to the recovery of mechanical properties, and the main object is the development of a function that spontaneously recovers the mechanical strength when a crack occurs in the structure due to external factors.

However, with the development of supports having more diverse characteristics, there is a continuing need for a method capable of complementing various characteristics of the support, in addition to the mechanical properties of the support.

For example, the problem with plastic fuel containers used as lightweight materials for improving fuel efficiency of automobiles is static electricity. That is, the static electricity generated by the friction between the tumbling fuel and the plastic fuel container may cause a serious explosion by an external stimulus such as a crash accident. In order to solve this problem, when the electrically conductive polymer is used, the conductivity is not sufficient, so it does not help to prevent static electricity. Carbon nanotubes, on the other hand, are easily conductive (<3 wt. In particular, filling carbon nanotubes in a plastic fuel container material increases mechanical strength, which is a great help in securing fuel tank safety. However, plastic materials are more easily cracked and warped due to external forces (shocks, temperature changes, etc.) than metals, and it is very difficult to check the microcracks of the fuel tank inside the vehicle at any time. It is required.

However, in the case of such a composite, other properties such as electrical properties are important along with mechanical properties, and thus there is a continuing need for a method capable of restoring electrical properties in addition to the mechanical properties of the composite.

The present invention provides a self-healing complex capable of healing mechanical and electrical properties.

Another object of the present invention is to provide a material capable of healing the mechanical and electrical properties of the composite.

It is yet another object of the present invention to provide a new method for determining the self-healing mechanism and recovery rate of a complex.

Another object of the present invention is to provide a method for dispersing a material capable of healing the mechanical and electrical properties of the composite.

In order to achieve the above object, the conductive self-healing composite of the present invention is a capsule containing carbon nanotubes; Self-healing substances; And carbon nanotubes dispersed in a matrix.

In the present invention, the matrix of the self-healing composite is made of a conductive material, preferably a polymer composite having conductivity by carbon nanotubes dispersed in the matrix. The complex may be a hard rigid complex and may also be a flexible complex.

In the present invention, the capsule includes carbon nanotubes, but is not limited in theory, but if stress is applied to the composite and cracks occur, the carbon nanotubes contained therein are released while the capsule is broken, and the conductive composite It recovers by healing the electrical properties of.

In the present invention, the self-healing material refers to a material that is converted into a polymer by stress applied to the complex, for example, a matrix crack, so as to restore physical properties of the complex.

In the practice of the present invention, the self-healing material may be a material that can be polymerized by cracking of the matrix, for example, a monomer, a prepolymer, or a functional polymer including two or more reactive groups.

In a preferred embodiment of the present invention, the self-healing material may be a functional siloxane, for example a siloxane prepolymer or a polysiloxane having two or more reactive groups. Examples of functional siloxanes may be silanol-functional siloxanes, alkoxy-functional siloxanes, aryl or vinyl-functional siloxanes.

The polysiloxanes can be linear or branched, or crosslinked polymers. Examples of polysiloxanes are poly (dimethylsiloxane), poly (methylsiloxane), partially alkylated poly (methylsiloxane), poly (alkylmethylsiloxane), and poly (phenylmethylsiloxane), preferably poly (dimethylsiloxane) (PDMS).

In another preferred embodiment of the invention, the polymerizable materials include epoxy-functional monomers, prepolymers or polymers, and also include cyclic olefins, preferably 4-50 carbon atoms and optionally heteroatoms. And cyclic olefins, for example DCPD, substituted DCPD, noborene, substituted noboene, cyclooctadiene, and substituted cyclooctadiene.

In another preferred embodiment of the present invention, as the polymerizable material, two different materials can react to form a polymer. For example, polyethers, polyesters, polycarbonates, polyenehydrides, polyamides, formaldehyde polymers, and combinations of polyurethanes or polysiloxanes, for example polysiloxanes formed by the reaction of silanol functional polysiloxanes with alkoxy-functional polysiloxanes Can be. One example is a combination of hydroxyl terminated polydimethylsiloxane (HOPDMS) and polydiethylsiloxane (PEDS).

In the present invention, when self-healing occurs when a crack occurs in the complex and meets the self-healing material, the self-healing material may be polymerized by flowing to the cracked site. Thus, the self-healing material is preferably made of a liquid phase. Do.

The self-healing material may be present in phase separated form in the matrix, or in a protected state by the capsule. The manner of distribution of self-healing substances is disclosed in US 2006/0252852 A1, which is invented by Paul V. Braun et al.

In the practice of the present invention, the polymerization of the self-healing material may be induced by an activator included in the composite, for example, a polymerization initiator or a catalyst for polymerization. The activator may be present in a capsule that is separate from the self-healing material, as described in US Patent Publication No. US2007 / 0166542 A1 et al. Invented by Paul V. Braun et al., And also described in US Pat. No. 6,518,330. The catalyst may be present as solid particles.

In a preferred embodiment of the present invention, the activator may be included with the carbon nanotubes in a capsule containing carbon nanotubes, for example, the activator is hydroxyl-terminated polydimethylsiloxane (HOPDMS) and polydiethylsiloxane Di-n-butyltindi-laurate may be used to induce polymerisation of self-healing materials consisting of a combination of (PEDS).

In the present invention, the capsule is made of a dense structure so that the material in the capsule does not escape, it is preferably manufactured so that it can be broken when cracks occur. In the practice of the present invention, the capsule may be made of a capsule made of polyurethane.

In the present invention, the carbon nanotubes included in the capsule may use carbon nanotubes having a single wall or a multi-wall structure. The carbon nanotubes can be purchased commercially and used without further purification. The outer diameter and the length of the carbon nanotubes used in the present invention are not particularly limited, but may be preferably from several nanometers to several tens of nanometers.

In one embodiment of the present invention, the polyurethane capsule is prepared by reacting a polyol and diisocyanate, preferably 1,4-butanediol and TDI (toluene diisocyanate) at hexaone after mixing at 24 ℃ Reaction for time to produce a urethane precursor. After dissolving the prepared urethane precursor in chlorobenzene, the reaction catalyst was mixed with DBTL (di-n-butyltin di-laurate) and carbon nanotubes, mixed with distilled water and reacted at 70 ℃ for 2 hours and dried and the carbon nanotubes Microcapsules containing an activator are obtained.

In a preferred embodiment of the present invention, in order to properly disperse the carbon nanotubes, a surfactant may be added to the distilled water, and microwaves may be added during the reaction to control the size of the capsule from micro units to nano units. have. In addition, it is possible to sift to obtain a capsule of more uniform size.

In the practice of the present invention, the matrix can be made by the matrix precursor is solidified. The matrix precursor may be a monomer and / or prepolymer that polymerizes to form a matrix polymer. The matrix polymer may be polyester such as nylon, polyethylene terephthalate and polycaprolactone, polycarbonate, polyether, epoxy polymer, epoxy vinyl ester polymer, polyimide, phenol-formaldehyde polymer, amine-formaldehyde polymer such as melamine, Polysulfones, acrylonitrile-butadiene-styrene copolymers, polyurethanes, polyolefins, for example polyethylene, polystyrene, polyacrylonitrile, polyvinyl, polyvinylchloride, poly (DCPD), polyacrylates, polymethylmethacrylates Polysilanes such as polyalkylacrylates, polysilanes such as polycarbosiloxanes, and polyphosphazines.

In the practice of the present invention, the carbon nanotubes can be used in the range that can impart electrical conductivity to the composite, with respect to 100 parts by weight of the matrix 10 parts by weight or less, preferably 5 parts by weight or less, more preferably It may be included in 3 parts by weight or less.

In general, many methods are used to increase dispersibility by attaching functional groups to CNTs. However, these methods require a complicated process for pretreatment of CNTs prior to the production of CNT / polymer composites, and have a disadvantage of dealing with various harmful substances. To avoid this drawback and convenience in practical applications, a simpler CNT dispersion method is needed. Examples include acid treatment and ultrasound, or in-situ polymerization of polymer substrates.

In one aspect, the present invention provides a polymer composite healing capsule comprising an activator of a self-healing material, and carbon nanotubes.

In the present invention, the activator of the self-healing substance contained in the capsule is a substance capable of inducing the polymerization of the self-healing substance dispersed in the matrix of the polymer composite, for example, an initiator or polymerization catalyst of a polymer polymerization. Can be. The self-healing material may be a known self-healing material that can be polymerized, and may be present in a phase separated state in the matrix or protected and dispersed in another capsule.

In the present invention, the carbon nanotubes included in the capsule may be used commercially available commercial carbon nanotubes, and may be present to impart electrical conductivity to the matrix or to restore the electrical conductivity of the matrix.

In the present invention, the capsule may be prepared to be broken and release the carbon nanotubes and the activator contained therein when cracks are caused by physical or environmental effects on the matrix in which the capsule is dispersed, preferably May be made of polyurethane.

In the practice of the present invention, the capsule may include a liquid substance, preferably an organic solvent, so that the carbon nanotubes and the activating agent contained therein can flow along the cracks. The organic solvent may be a known organic solvent.

In the present invention, the capsule may be adjusted in size or shape so as not to adversely affect the physical properties of the polymer composite, it is possible to control the size from nano units to microns.

In the practice of the present invention, the matrix in which the capsule is dispersed may be a conductive matrix including carbon nanotubes, and may also be a non-conductive material containing no carbon nanotubes. When carbon nanotubes are included in the matrix, the electrical properties may be restored by the carbon nanotubes released when the capsule is broken. In addition, when the matrix is non-conductive, it may be converted into conductivity by the carbon nanotubes released when the capsule is broken. In this case, the capsule containing the carbon nanotubes may be used as a material informing the occurrence of the micro cracks formed in the matrix.

In one aspect, the present invention provides a method for producing a self-healing composite comprising: preparing a capsule comprising a carbon nanotube and an auto-healing activator; And preparing a matrix including the capsule, carbon nanotubes, and self-healing material.

In the present invention, the matrix can be prepared by solidifying the matrix precursor.

In the practice of the present invention, the capsule containing the carbon nanotubes and the self-healing material activator is made of a polyurethane so that it can be crushed when a crack occurs while forming a dense structure so that the material in the capsule does not escape. Do.

In one embodiment of the present invention, the activator of carbon nanotubes and self-healing materials is prepared by reacting a polyurethane capsule with a polyol and diisocyanate, preferably 1,4-butanediol and TDI (toluene diisocyanate) at hexaone ) Is mixed and then reacted at 80 ° C. for 24 hours to prepare a urethane precursor. After dissolving the prepared urethane precursor in chlorobenzene, the reaction catalyst was mixed with DBTL (di-n-butyltin di-laurate) and carbon nanotubes and mixed with distilled water containing a surfactant and reacted for 2 hours at 70 ℃ and dried In this case, microcapsules containing carbon nanotubes and an activator may be obtained.

In the present invention, the self-healing complex is prepared by solidifying a matrix precursor comprising a capsule, carbon nanotubes, and self-healing material.

In the practice of the present invention, the matrix precursor may be a monomer and / or prepolymer that polymerizes to form a matrix polymer. The matrix polymer may be polyester such as nylon, polyethylene terephthalate and polycaprolactone, polycarbonate, polyether, epoxy polymer, epoxy vinyl ester polymer, polyimide, phenol-formaldehyde polymer, amine-formaldehyde polymer such as melamine, Polysulfones, acrylonitrile-butadiene-styrene copolymers, polyurethanes, polyolefins, for example polyethylene, polystyrene, polyacrylonitrile, polyvinyl, polyvinylchloride, poly (DCPD), polyacrylates, polymethylmethacrylates Polysilanes such as polyalkylacrylates, polysilanes such as polycarbosiloxanes, and polyphosphazines.

In the present invention, the matrix precursor may proceed using a polymerization catalyst or a polymerization initiator of the matrix precursor. In one embodiment of the present invention, the methyl methacrylate precursor is converted to a polymethyl methacrylate matrix polymer using a peroxide compound.

In one preferred embodiment of the present invention, BPO (Benzoyl peroxide) is dissolved in MMA (methylmethacrylate), and then HOPDMS (hydroxyend-functionalized polydimethylsiloxane) and PDES (polydiethoxysiloxane) are mixed. The microcapsules containing DMA (dimethylanilne), carbon nanotubes, and self-healing activator are added to the mixed solution, and then the solution is placed in a mold of a desired form and dried for two days to form a polymer composite. At this time, when the carbon nanotubes are put together in the MMA solution during synthesis, PMMA matrix containing carbon nanotubes can be synthesized.

In one aspect, the present invention provides a self-healing composite test method using a cantilever or a crystal oscillator, characterized in that for measuring the vibration characteristics of the vibration piece coated with the self-healing composite.

In the present invention, the cantilever or crystal oscillator is a conventional cantilever or crystal oscillator configured to measure the vibration characteristics of the vibrating piece, and can be purchased and used commercially.

In one embodiment of the present invention, the crystal oscillator may use a conventional crystal oscillator as a device in which a thin crystal oscillation piece embedded by the piezoelectric effect exhibits specific vibration characteristics.

In the practice of the present invention, the quartz crystal oscillator may exhibit a vibration characteristic corresponding to the state of the self-healing composite coated on the surface. For example, before a crack occurs in a self-healing composite coated on the surface of a crystal oscillator, after a crack occurs, and as the self-healing is completed, the same crystal oscillator may exhibit respective vibration characteristics. . This change in vibration characteristics can be detected through an electrical signal.

In one aspect, the present invention provides a polymer composite including a capsule containing carbon nanotubes and a self-healing material.

In the present invention, the polymer composite may be conductive or nonconductive. In the practice of the invention, the polymer composite may be changed in electrical properties by the carbon nanotubes released when the capsule is broken.

In one embodiment of the present invention, the polymer composite may be a polymer containing a conductive material, the conductivity may be restored by the carbon nanotubes emitted. In another embodiment of the invention, the polymer composite may be a non-conductive material, and is converted into conductivity by the carbon nanotubes emitted.

The conductive polymer composite according to the present invention means an electrically conductive polymer composite. The conductive polymer composite includes a polymer having conductivity, including a polymer having high conductivity and / or a conductive material as the polymer itself.

The conductive polymer composite may be recovered by release of carbon nanotubes embedded in the capsule, the conductivity of which is broken by external stress or cracks.

In one aspect, the present invention provides a use of a conductive polymer composite including a capsule containing carbon nanotubes and a self-healing material.

In the present invention, the conductive polymer composite may be used in a part that requires recovery of electrical properties during self-healing, for example, an electric material, an electronic part, an automobile fuel container made of a conductive material, an aviation part, and the like.

According to the present invention, when a crack occurs in a composite due to physical or environmental stress, a self-healing composite which can restore not only its physical characteristics but also electrical characteristics has been provided. By using this, it is possible to manufacture electrical materials, electronic components, automobile and aircraft parts, etc., which require recovery of electrical properties in case of breakage.

In addition, the measurement method according to the present invention is capable of precise measurement using a crystal oscillator to provide a new tool for the study of the properties of the self-healing complex.

The present invention will be described in more detail with reference to the following examples.

Example 1 Preparation of Microcapsules

21.85 g of toluene-2,4-diisocyanate was stirred and mixed with 141.65 g of cyclohexanone. While stirring the mixture, 4.12 g of 1,4-butandiol was slowly added, reacted at 80 ° C. for 24 hours, and then cyclohexanone was evaporated under vacuum at 100 ° C. after the reaction mixture to synthesize a urethane precursor.

After dissolving 2.91 g of the synthesized urethane precursor in 12.5 g of chlorobenzene, 1 g of DBTL (di-n-butyltin di-laurate) was dissolved in 9 g of chlorobenzene, mixed with carbon nanotube g, and dispersed by ultrasonic wave. It was mixed with the solution, and again mixed with 25 g of distilled water mixed with 3.75 g of Gum Arabic and reacted at 70 ° C. for 2 hours to obtain a microcapsule. Surface photographs of the microcapsules were taken and shown in FIG. 1.

Example 2 Preparation of Self-Healing Complex

After injecting carbon nanotubes into MMA (methylmethacrylate) and dispersing by adding ultrasonic waves, 0.25 wt% of AIBN (2,2'-azobisisobutyronitrile) was completely dissolved to prepare a solution. Thereafter, PDES (polydiethoxy siloxane) / HOPDMS (hydroxyend-functionalized polydimethyl siloxane) mixed at a ratio of 1:35 was added to the prepared solution in an amount of 14% by weight of MMA.

 After degassing the prepared solution, the microcapsules prepared in Example 1 were placed, put in a desired mold, and dried for 48 hours to prepare a composite. The cross section of the prepared composite was cut out and a SEM photograph was taken, as shown in FIG. Half cut microcapsules are shown during the cutting process for cross-sectional observation of the healing complex.

The structural diagram of the prepared self-healing complex is shown in FIG. 3. As shown in FIG. 3, a microcapsule 100 including a catalyst and carbon nanotubes; Healing agent 200; And carbon nanotubes 300 are dispersed in the PMMA matrix 400. If a crack occurs in the composite, the stress causes the microcapsules to collapse. The catalyst (DBTL) dissolved in the solvent inside the capsule flows out and reacts with the healing agent (HOPDMS, PDES) to repair the crack. In addition, when the crack is restored, the electrical conductivity of the composite is also restored by the carbon nanotubes contained in the capsule.

Example 3 Measurement of Polymer Curing Process Using Cantilever

In order to check whether the characteristic change of polymer thin film can be observed using the cantilever, first, observe the change in the resonance frequency and curvature of the cantilever when the UV-cured polymer coated on the surface of the cantilever is exposed to ultraviolet rays and curing occurs. It was. 4 and 5 show the measurement results. It can be seen that the resonance frequency of the cantilever changes according to the degree of curing of the polymer thin film.

Example 4: Determination of Self-Healing Complexes

After injecting carbon nanotubes into MMA (methylmethacrylate) and dispersing by adding ultrasonic waves, 0.25 wt% of AIBN (2,2'-azobisisobutyronitrile) was completely dissolved to prepare a solution. Thereafter, PDES (polydiethoxy siloxane) / HOPDMS (hydroxyend-functionalized polydimethyl siloxane) mixed at a ratio of 1:35 was added to a solution prepared in an amount of 14% by weight of MMA, followed by stirring to coat the surface of the crystal oscillator.

The change of the fundamental resonance frequency and the 3rd, 5th, 7th, 9th, and 11th frequencies was measured while applying an external force to crack the coating surface. The measurement results are shown in FIGS. 6 and 7. When pressed with a cotton swab, the change in frequency appears and disappears immediately, but when the razor blade cracks, the change in the resonance frequency appears permanent.

Accordingly, the step of curing the polymer formed on the surface of the vibrating piece and the step of cracking are also shown as the vibration characteristics of the vibrating piece change depending on the healing.

The above examples are for illustrating the present invention and are not intended to limit the invention. The scope of the invention is defined by the claims set forth below.

1 is an electron micrograph of the polyurethane microcapsules according to the embodiment of the present invention.

Figure 2 is an electron micrograph of the cross section of the self-healing composite according to the practice of the present invention.

3 is a structural diagram of a self-healing composite containing carbon nanotubes according to the present invention.

4 is a graph showing a change in cantilever signal (change in resonance frequency) when the ultraviolet curable polymer according to the embodiment of the present invention is coated on the surface of the cantilever and then exposed to ultraviolet rays.

5 is a graph showing a change in cantilever signal (change in warpage) when the ultraviolet curable polymer according to the embodiment of the present invention is coated on the surface of the cantilever and exposed to ultraviolet rays.

Figure 6 is a graph showing the change in the fundamental resonance frequency and the 3, 5, 7, 9, 11th frequency after applying the external force with a cotton swab after the PMMA thin film coated on the crystal oscillator.

FIG. 7 is a graph showing changes in fundamental resonance frequencies and 3, 5, 7, 9, and 11th frequencies after coating PMMA thin films with quartz crystals and applying cracks. FIG.

Claims (31)

Capsules containing carbon nanotubes; Self-healing substances; And carbon nanotubes dispersed in a matrix. The self-healing conductive polymer composite according to claim 1, wherein the capsule releases carbon nanotubes upon fracture. The self-healing conductive polymer composite according to claim 1 or 2, wherein the capsule releases a self-healing agent activator upon fracture. The self-healing conductive polymer composite according to claim 1 or 2, wherein the self-healing material is hydroxy terminal functional polydimethylsiloxane (HOPDMS) and polydiethoxysiloxane (PDES). The self-healing conductive polymer composite according to claim 4, wherein the activating agent is di-n-butyltindi-laurate. The self-healing conductive polymer composite according to claim 1 or 2, wherein the capsule is a microcapsule or a nanocapsule. The self-healing conductive polymer composite according to claim 1 or 2, wherein the matrix is polymerized by the activator. Self-healing activator, polymer composite healing capsule containing carbon nanotubes. According to claim 1, wherein the capsule is a polymer composite healing capsule, characterized in that made of polyurethane. 10. The capsule of claim 8, wherein the capsule is a microcapsule or a nanocapsule. 10. The capsule of claim 8 or 9, wherein the capsule further comprises a solvent. 10. The capsule of claim 8 or 9, wherein the self-healing material is hydroxy terminal functional polydimethylsiloxane (HOPDMS) and polydiethoxysiloxane (PDES). The method of claim 8 or claim 9, wherein the polymer composite healing capsule is a polymer composite healing capsule, characterized in that broken by the crack of the matrix. 10. The capsule of claim 8 or 9, wherein the polymer composite healing capsule is for healing electrical properties of the composite. 10. The capsule of claim 8 or 9, wherein the capsule is dispersed in the polymer matrix together with a self-healing material. Preparing a capsule comprising carbon nanotubes and an activator; And Preparing a matrix in which the capsule and the carbon nanotubes and the self-healing material are dispersed Self-healing complex manufacturing method comprising a. The method of claim 16, wherein the activator is a polymerization initiator or polymerization catalyst of self-healing material. 18. The method of claim 16 or 17, wherein the self-healing material is hydroxy terminal functional polydimethylsiloxane (HOPDMS), polydiethoxysiloxane (PDES). 19. The method of claim 18, wherein the activator is di-n-butyltindi-laurate. 18. The method of claim 17, wherein the matrix is nylon, polyester, polycarbonate, polyether, epoxy polymer, epoxy vinyl ester polymer, polyimide, phenol-formaldehyde polymer, amine-formaldehyde polymer, polysulfone, acrylonitrile- Butadiene-styrene copolymer, polyurethane, polyethylene, polystyrene, polyacrylonitrile, polyvinyl, polyvinylchloride, poly (DCPD), polyacrylate, polyalkylacrylate, polysilane, polyphosphazine, or mixtures thereof Polymer composite manufacturing method characterized in that. 18. The method of claim 17, wherein the capsule is prepared by mixing a urethane precursor solution including an activator and carbon nanotubes with distilled water containing a surfactant. A polymer composite comprising a capsule containing carbon nanotubes and a self-healing material. The polymer composite of claim 22, wherein the polymer composite is conductive. The polymer composite of claim 22, wherein the polymer composite is a polymer including a conductive material. The polymer composite of claim 22, wherein the polymer composite is changed in electrical properties when the capsule is broken. The method of claim 22 or 23, wherein the polymer composite is nylon, polyester, polycarbonate, polyether, epoxy polymer, epoxy vinyl ester polymer, polyimide, phenol-formaldehyde polymer, amine-formaldehyde polymer, polysulfone , Acrylonitrile-butadiene-styrene copolymer, polyurethane, polyethylene, polystyrene, polyacrylonitrile, polyvinyl, polyvinylchloride, poly (DCPD), polyacrylate, polyalkylacrylate, polysilane, polyphosphazine Or a mixture thereof. Characteristic test method of the self-healing composite characterized by measuring the vibration characteristics change by coating a self-healing polymer on the vibrating piece. 28. The method of claim 27, wherein the vibrating piece is a vibrating piece of a cantilever or quartz crystal vibrator. 28. The method of claim 27, wherein after the cracks are formed in the polymer, the change in vibration characteristics is measured. A coating film made of the self-healing conductive polymer composite of claim 1. Injection or extrudates made of the self-healing conductive polymer composite of claim 1.

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