KR20190112462A - Non-linear supramolecular for self-healing supramolecular network and self-healing supramolecular network comprising the same - Google Patents

Abstract

The present invention relates to a nonlinear supramolecular body having a large number of crosslinking points while having improved chain mobility by controlling branch length, and a self-healing supramolecular network having excellent self-healing performance including the same. Particularly, the present invention relates to a self-healing supramolecular network capable of fast and efficient self-healing by having high fluidity even with a simple stimulus and maintaining the natural mechanical properties of the material even after healing.

Description

Non-linear supramolecular for self-healing supramolecular network and self-healing supramolecular network comprising the same}

The present invention relates to a non-linear supramolecular body having a large number of crosslinking points and a self-healing supramolecular network having excellent self-healing performance including the same. The present invention relates to a self-healing supramolecular network which enables high and fast self-healing and maintains the material mechanical properties after healing.

Self-healing materials are materials that can be repaired and restored to their original state when damage occurs on the surface or inside of a material. It is a core technology that can be used in various fields such as automobiles, aerospace, ships, and construction. This technology is classified according to mechanisms and materials, and is composed of polymers that disperse microcapsules containing therapeutic substances in polymers of large molecular size or give therapeutic functions as materials themselves. In particular, supramolecular self-healing material is a system that exhibits healing properties through reversible coupling using secondary bonds, and is a material that is well received in that it can compensate for the disadvantages of conventional self-healing materials using microcapsules. Unlike conventional materials, which have a limited number of healings, these supramolecular self-healing materials are suitable for use in various fields of industry in that they undergo perfect and continuous healing even after several damages through the thermoreversible reaction of polyhydrogen bonds. Do.

Two important factors that determine healing efficiency in self-healing supramolecular networks are known as chain motility and supramolecular bond strength. These two factors are in opposition to each other, and the supramolecular network with good healing efficiency has low mechanical properties, and the higher the mechanical properties, the slower the healing speed.

Korea Patent Registration No. 10-1724796

The present invention has been devised in view of the above, and includes a nonlinear supramolecular body having a large number of crosslinking points and a nonlinear supramolecular body and controlling the length of the branch to improve the chain motion, and the fluidity is simple even with a simple stimulus. The purpose is to provide a self-healing supramolecular network that has high self-healing performance, which enables higher, faster and more efficient self-healing and maintains the mechanical properties of the material after healing.

In order to solve the above problems, the present invention provides a self-healing hypermolecular network comprising a non-linear polymer including at least three branches having a number average molecular weight of 5000 g / mol or more and a polyhydrogen bondable single molecule provided at each end of the branch. Provide nonlinear supramolecular bodies.

According to one embodiment of the present invention, the multi-hydrogen bondable single molecule may be a compound including at least one ureido group.

In addition, according to an embodiment of the present invention, the number average molecular weight of the branch may be 5000 ~ 15000g / mol.

In addition, according to one embodiment of the present invention, the nonlinear supramolecular body may have a glass transition temperature of 0 ° C. or less.

In addition, according to a preferred embodiment of the present invention, the number average molecular weight of the branch may be 8500 ~ 15000g / mol.

In addition, the present invention provides a self-healing supramolecular network including a nonlinear supramolecular body according to the present invention to form supramolecular crosslinks by hydrogen bonds between monomolecules provided at branch ends of the nonlinear supramolecular bodies.

According to an embodiment of the present invention, the self-healing supramolecular network may not further include a linear supramolecular body having self-healing ability.

In addition, according to one embodiment of the present invention, the self-healing network may have a supramolecular bond lifetime (τ _b ) of 0.003 to 0.010 seconds.

In addition, the present invention is a single molecule provided at the branch end of the non-linear supramolecular body by supplying heat at a predetermined temperature and time to the self-healing supramolecular network according to the present invention damaged or applying a microwave having a predetermined frequency It provides a self-healing method that heals the damage through hydrogen bonding between them.

The present invention also provides a coating composition comprising the nonlinear supramolecular body according to the invention.

According to the present invention, by controlling the branch length of the nonlinear supramolecular body can improve the chain movement and at the same time have a large number of crosslinking points, the self-healing supramolecular network composed of such nonlinear supramolecular body has a network structure based on multiple hydrogen bonds Because of the excellent mechanical properties and at the same time it is possible to repeat the complete healing of the fine level unit can be widely used by applying coatings in the field of transportation, such as automobiles, ships in terms of maintenance, durability.

1 is a schematic diagram of a self-healing supramolecular network including a nonlinear supramolecular body according to an embodiment of the present invention.
Figure 2a is a graph showing the number average molecular weight analysis results of the nonlinear polymer branch prepared in Examples 1 to 5, Comparative Example 1 and Comparative Example 2.
FIG. 2B is a graph showing the results of NMR analysis of nonlinear supramolecular bodies according to Examples 1 to 5, Comparative Examples 1 and 2. FIG.
3 is a graph showing the results of DSC analysis of nonlinear supramolecular bodies and UPy-NCO according to Examples 1 to 5, Comparative Example 1 and Comparative Example 2.
Figure 4a is an optical micrograph before and after the heat supply for 40 minutes at 40 ℃ for the self-healing supramolecular network according to Examples 1 to 4 where the damage occurred.
Figure 4b is an optical micrograph before and after the heat supply for 40 minutes at 40 ℃ for the self-healing supramolecular network according to Comparative Examples 1 to 2 where the damage occurs.
Figure 5a is an optical micrograph before and after the heat supply for 40 minutes at 60 ℃ for the self-healing supramolecular network according to Examples 1 to 4 where the damage occurred.
Figure 5b is an optical micrograph before and after the heat supply for 40 minutes at 60 ℃ for the self-healing supramolecular network according to Comparative Examples 1 to 2 where the damage occurs.
Figure 6a is an optical micrograph before and after the heat supply for 40 minutes at 80 ℃ for the self-healing supramolecular network according to Examples 1 to 4 where the damage occurred.
Figure 6b is an optical micrograph before and after the heat supply for 40 minutes at 80 ℃ for the self-healing supramolecular network according to Comparative Examples 1 to 2 where the damage occurs.
Figure 6c is an optical micrograph before and after the heat supply for 5 minutes at 80 ℃ for the self-healing supramolecular network according to Examples 1 to 4 where the damage occurred.
Figure 6d is an optical micrograph before and after the heat supply for 5 minutes at 80 ℃ for the self-healing supramolecular network according to Comparative Examples 1 to 2 where the damage occurs.
Figure 7a is an optical micrograph before and after the heat supply for 40 minutes at 100 ℃ for the self-healing supramolecular network according to Examples 1 to 4 where the damage occurred.
Figure 7b is an optical micrograph before and after the heat supply for 2 minutes at 100 ℃ for the self-healing supramolecular network according to Examples 1 to 4 where the damage occurred.
Figure 7c is an optical micrograph before and after the heat supply for 2 minutes at 100 ℃ for the self-healing supramolecular network according to Comparative Examples 1 to 2 where the damage occurs.
8 is a graph showing the results of measuring the rheological properties of nonlinear supramolecular bodies according to Comparative Examples 1, 3 and 4 by the time-temperature superposition principle.

Hereinafter, exemplary embodiments of the present invention will be described in detail with reference to the accompanying drawings so that those skilled in the art may easily implement the present invention. As those skilled in the art would realize, the described embodiments may be modified in various different ways, all without departing from the spirit or scope of the present invention.

Self-healing networks using conventional supramolecular bodies have been prepared in a mixture of linear supramolecular and nonlinear supramolecular bodies. Since linear supramolecular bodies have high chain motility but few crosslinking points, they are mixed with nonlinear supramolecular bodies with high crosslinking points to form supramolecular complex networks. This required mixing of linear and nonlinear supramolecules in appropriate proportions. In addition, when using a conventional linear and nonlinear supramolecular complex network, there is a complicated problem of the self-healing phenomenon.

As shown in FIG. 1, the nonlinear supramolecular sieve according to the present invention can implement a nonlinear supramolecular sieve having a large number of crosslinking points while improving chain mobility by controlling branch length. In addition, the self-healing supramolecular network including such a nonlinear supramolecular body has a high fluidity even with a simple stimulus, thereby enabling fast and efficient self-healing and maintaining the natural mechanical properties of the material after healing.

Hereinafter, the nonlinear supramolecular body of the present invention will be described in detail.

The nonlinear supramolecular body according to the present invention includes a nonlinear polymer including at least three branches having a number average molecular weight of 5000 g / mol or more and a polyhydrogen bondable single molecule provided at each end of the branch.

When the number of branches is less than three, it may be difficult to achieve the object of the present invention, such as the cross-linking point of the non-linear supramolecular body may not be able to express the desired level of self-healing performance.

The number of branches depends on the number of functional groups that can be the polymerization initiation point of the coordination insertion polymerization of the core compound used in the preparation of the nonlinear polymer, and the core compound is a core that can be used for coordination polymerization in the art. The compound may be used without limitation. For example, if dipentaerythritol is used, the number of branches may be six.

In addition, the branch may be formed through coordination polymerization of the core compound and the monomer.

The monomer may be used without limitation so long as it is a monomer known in the art capable of coordinating polymerization with the core compound. For example, trimethyl carbonate, L-lactide, ε-decaractone (ε-decalactone), ε-caprolactone (ε-caprolactone), may be preferably ε-caprolactone (ε-caprolactone).

It is possible to control the branch length, that is, the number average molecular weight of the nonlinear polymer prepared by adjusting the polymerization ratio of the core compound and the monomer.

When the number average molecular weight of the branch is less than 5000g / mol, it may be difficult to achieve the object of the present invention, such as the chain mobility of the non-linear supramolecular body is lowered and the self-healing performance is lowered.

Referring to FIG. 7C, when the number average molecular weight of the branch is less than 5000 g / mol, it may be confirmed that damage to the supramolecular network is not self-healed even when high heat is supplied due to deterioration in the chain mobility of the nonlinear supramolecular body. On the other hand, referring to Figure 7b, when the number average molecular weight of the branch is more than 5000g / mol, it can be seen that the damage caused to the supramolecular network is excellent due to the excellent chain mobility of the nonlinear supramolecular.

According to a preferred embodiment of the present invention, the number average molecular weight of the branch is 5000-15000 g / mol, more preferably 6000-15000 g / mol, even more preferably 8500-15000 g / mol, most preferably 9600- May be 15000 g / mol.

When the number average molecular weight of the branch exceeds 15000g / mol, there may be a problem such as not suitable for use as a coating composition, such as crystallinity is generated in the prepared non-linear supramolecular body, opaque, reduced flexibility, etc. .

In addition, the nonlinear supramolecular sieve having a number average molecular weight of 6000 to 15000 g / mol may have better chain mobility and further improve self-healing performance, as shown in FIG. 4A by supplying heat at a lower temperature. Self-healing properties can also be expressed.

In addition, the nonlinear supramolecular body having a number average molecular weight of 8500 to 15000 g / mol of the branch may have better chain motility and thus further improve self-healing performance, as shown in FIG. 6A. In addition, self-healing characteristics may be expressed.

In addition, the nonlinear supramolecular sieve having a number average molecular weight of 9600 to 15000 g / mol is very excellent in chain mobility and further improves self-healing performance, as shown in FIG. 5A. Even if supplied, self-healing characteristics can be expressed.

According to one embodiment of the present invention, the nonlinear supramolecular body may have a glass transition temperature of 0 ° C. or less, and thus may have excellent chain segment mobility of the nonlinear polymer.

When the glass transition temperature of the non-linear polymer exceeds 0 ℃, there is a problem in that the rigid chain characteristics are expressed due to the restriction of the chain segment motility, there is a problem that can not give sufficient chain motility to self-healing, etc. It can be difficult to do.

According to one embodiment of the invention, the polyhydrogen bondable monomolecule can be used without limitation the polyhydrogen bond compound known in the art, preferably a compound comprising at least one ureido group (ureido), more Preferably, at least one selected from fatty acid ureidoamides, barbituric acid / Hamilton receptor, and UPy (ureidopyrimidinone), most preferably UPy (ureidopyrimidinone).

The self-healing supramolecular network can be formed by hydrogen bonding between the single molecules, and the higher the chain mobility of the non-linear polymer branch, the better the self-healing performance.

Next, the coating composition containing the nonlinear supramolecular body which concerns on this invention is demonstrated.

The nonlinear supramolecular body according to the present invention can be used in various fields such as automobiles, aerospace, ships, constructions, etc. because of its high fluidity even with a simple stimulus, which enables fast and efficient self-healing, and its inherent mechanical properties even after healing. There is an advantage.

Nonlinear supramolecular sieve included in the coating composition may preferably have a number average molecular weight of 5000 to 15000 g / mol, and when the number average molecular weight of the branch is less than 5000 g / mol, the chain mobility of the nonlinear supramolecular sieve decreases. When the self-healing performance is lowered, and when it exceeds 15000 g / mol, there is a problem that it is not suitable for use as a coating composition, such as crystallinity in the prepared nonlinear supramolecular body, opacity, and low flexibility. There may be.

The coating composition may further include a coating solvent commonly used in the art, in addition to the nonlinear supramolecular body. For example, the coating composition may be chloroform or dimethylformamide, but is not limited thereto.

Next, the self-healing supramolecular network according to the present invention will be described.

The self-healing supramolecular network of the present invention includes a nonlinear supramolecular body according to the present invention to form supramolecular crosslinks by hydrogen bonding between single molecules provided at branch ends of the nonlinear supramolecular bodies.

According to an embodiment of the present invention, the self-healing supramolecular network may not further include heterogeneous supramolecular bodies having self-healing ability.

For example, the heterogeneous supramolecular body may be a linear supramolecular body. In the conventional self-healing supramolecular complex network, linear supramolecular and nonlinear supramolecular bodies were prepared in a mixed form, but in order to secure high chain mobility and a large number of crosslinking points, the linear and nonlinear supramolecular bodies had to be mixed at a predetermined ratio. If the mixing ratio is out of a predetermined range, the self-healing performance is significantly reduced, and the analysis of the self-healing phenomenon by the mixed use of linear and nonlinear supramolecular bodies is complicated.

On the other hand, the self-healing supramolecular network of the present invention has an advantage of obtaining excellent chain motility and a large number of crosslinking points even when including nonlinear supramolecules alone.

In addition, according to an embodiment of the present invention, the self-healing supramolecular network may have a supramolecular bond lifetime (τ _b ) of 0.003 to 0.010 sec.

If τ _b is less than 0.003 seconds, the chain motion of the nonlinear supramolecular body may be very excellent, but may not be suitable for use as a coating composition such as crystallinity, opacity, and flexibility.

If it exceeds 0.010 seconds, it takes longer to equilibrate the bond-dissociation of the nonlinear supramolecular against the damage given to the self-healing supramolecular network, resulting in no desired level of self-healing performance. There may be a problem.

Referring to FIG. 8, it can be seen that the higher the number average molecular weight of the nonlinear supramolecular branch is, the lower the value of τ _b , that is, the faster self-healing rate.

Next, the self-healing method according to the present invention will be described.

In the self-healing method of the present invention, the damaged self-healing supramolecular network supplies heat at a predetermined temperature and time, or applies a microwave having a predetermined frequency to the monomolecular molecules provided at the branch ends of the nonlinear supramolecular bodies. Hydrogen bonds heal the damage. Since the self-healing supramolecular network includes the nonlinear supramolecular body according to the present invention, it has excellent chain motility and has a large number of crosslinking points.

Although one embodiment of the present invention has been described above, the spirit of the present invention is not limited to the embodiments set forth herein, and those skilled in the art who understand the spirit of the present invention, within the scope of the same idea, the addition of components Other embodiments may be easily proposed by changing, deleting, adding, and the like, but this will also fall within the spirit of the present invention.

Preparation Example 1

2-amino-4 hydroxy-6-methyl pyrimidine to synthesize ureidopyrimidinone (UPy-NCO), a terminally functionalized polyhydrogenated organism with isocyanate Hexamethylene diisocyanate was added to a pyridine catalyst and stirred for 16 hours at 100 ° C. under a nitrogen stream. In order to remove the unreacted product, heptane was washed with water to obtain a white solid, washed several times with acetone, filtered, and vacuum dried at 60 ° C. for 24 hours to obtain UPy-NCO.

Example 1

[epsilon] -caprolactone and dipentaerythritol were mixed but stirred until clear at 150 [deg.] C. under a nitrogen stream for uniform miscibility. After becoming a clear liquid, a catalyst was added and stirred for 18 hours at 110 ° C. under a nitrogen stream to synthesize a nonlinear polymer having six branches. The branch of the prepared nonlinear polymer had a number average molecular weight of 6415.78 g / mol.

In order to introduce UPy-NCO at the branch end of the prepared nonlinear polymer, UPy-NCO and nonlinear polymer were dissolved in chloroform. At this time, UPy-NCO was added at a molar equivalence ratio of 2 times per hydroxyl group (-OH) at the branch terminal of the nonlinear polymer. After adding the catalyst, the mixture was stirred for 16 hours at 65 ° C. under a nitrogen stream, and then silica gel was added to remove unreacted UPy-NCO and stirred at 65 ° C. for 4 hours. After filtering the silica gel, the filtrate was concentrated and added to methanol to precipitate a nonlinear supramolecular body with UPy-NCO at the end of each branch. The precipitated nonlinear supermolecular sieve was filtered and dried under vacuum at room temperature for 24 hours to obtain a nonlinear supermolecular sieve.

Example 2

In the same manner as in Example 1, a nonlinear supramolecular body including six branches having a number average molecular weight of 8616.86 g / mol was prepared by adjusting the polymerization ratio of the core compound and the monomer.

Example 3

In the same manner as in Example 1, the polymerization ratio of the core compound and the monomer was adjusted to prepare a nonlinear supramolecular body including 6 branches having a number average molecular weight of 9824.69 g / mol.

Example 4

In the same manner as in Example 1, a nonlinear supramolecular body including six branches having a number average molecular weight of 14038.51 g / mol was prepared by adjusting the polymerization ratio of the core compound and the monomer.

Example 5

In the same manner as in Example 1, a nonlinear supramolecular body including six branches having a number average molecular weight of 16656.42 g / mol was prepared by adjusting the polymerization ratio of the core compound and the monomer.

(Comparative Example 1)

In the same manner as in Example 1, by adjusting the polymerization ratio of the core compound and the monomer to prepare a non-linear supramolecular body including six branches having a number average molecular weight of 2019.57g / mol.

(Comparative Example 2)

In the same manner as in Example 1, by adjusting the polymerization ratio of the core compound and the monomer to prepare a non-linear supramolecular body including six branches having a number average molecular weight of 3800.83g / mol.

Experimental Example 1

The number average molecular weights of the branches included in the nonlinear polymers of Examples 1 to 5 and Comparative Examples 1 and 2 were measured by NMR analysis, and the results are shown in FIG. 2A.

In addition, the structure of the nonlinear supramolecular bodies prepared in Examples 1 to 5 and Comparative Examples 1 and 2 were analyzed using an NMR analyzer. Referring to FIG. 2B, it can be seen that a single molecule capable of polyhydrogen bonding is bonded to each nonlinear supramolecular body.

Experimental Example 2

Glass transition temperatures of the nonlinear supramolecular bodies prepared in Examples 1 to 5 and Comparative Examples 1 and 2 were measured using a DSC analyzer, and the results are shown in FIG. 3.

Referring to FIG. 3, the glass transition temperature tends to decrease as the number average molecular weight of the branch increases, and as a result, the chain mobility of the branch increases as the number average molecular weight increases. In addition, when the number average molecular weight is higher than a certain level it can be seen that the decrease in the glass transition temperature decreases.

Experimental Example 3

After melting each of the nonlinear supramolecular bodies prepared in Examples 1 to 4 and Comparative Examples 1 to 2 to form a supramolecular network, a 0.2 mm thick aluminum plate was placed on both ends of the substrate, and a sample (0.8 mm thickness) was applied. Cracks were generated in the supramolecular network using a crack generator.

In order to compare the self-healing performance of the supramolecular network according to the length of the branches, that is, the molecular weight of the basin and the heat supply temperature, the degree of self-healing of the supramolecular networks was measured by supplying heat at 40 ° C, 60 ° C, 80 ° C and 100 ° C for 40 minutes. Observation was carried out with an optical microscope.

The nonlinear supramolecular bodies prepared in Example 5 were opaque and easily crumbled so that the self-healing properties could not be evaluated, which was attributed to the increase in crystallinity of the nonlinear polymer main chain due to the number average molecular weight of the branches exceeding 15000 g / mol. do.

4A and 4B, when heat is supplied at 40 ° C. for 40 minutes, it is confirmed that the supramolecular networks according to Examples 1 to 4 and Comparative Examples 1 and 2 are not self-healing.

5A and 5B, when supplying heat for 40 minutes at 60 ° C., the supramolecular networks according to Examples 3 and 4 were found to have self-healing. Examples 1, 2, and Comparative Examples It can be seen that supramolecular networks according to 1 and Comparative Example 2 are not self-healing. That is, the supramolecular networks according to the third and fourth embodiments may be capable of self-healing even when a relatively small amount of heat is supplied.

6A and 6B, when heat was supplied at 80 ° C. for 40 minutes, the supramolecular network according to Examples 2 to 4 was found to have self-healing, but Example 1, Comparative Example 1 and Comparative Example It can be seen that supramolecular networks according to 2 are not self-healing. That is, the supramolecular network according to Example 2 may generate self-healing only when a relatively large amount of heat is supplied to the supramolecular networks according to Examples 3 and 4, but in Examples 1, Comparative Examples 1 and 2, It is thought that self-healing can occur even if a relatively small amount of heat is supplied rather than the supramolecular network.

Referring to FIG. 7A, when the heat was supplied at 100 ° C. for 40 minutes, the supramolecular networks according to Examples 1 to 4 were all self-healing.

As a result, the higher the number average molecular weight of the nonlinear supramolecular basin, the self-healing occurs even when a small amount of heat is supplied, and the number average molecular weight of the nonlinear supramolecular basin is relatively low as in Comparative Examples 1 and 2. It can be seen that no self-healing occurred.

Experimental Example 4

After melting each of the nonlinear supramolecular bodies prepared in Examples 1 to 4 and Comparative Examples 1 to 2 to form a supramolecular network, a 0.2 mm thick aluminum plate was placed on both ends of the substrate, and a sample (0.8 mm thickness) was applied. Cracks were generated in the supramolecular network using a crack generator.

In order to compare the self-healing performance of the supramolecular networks according to the length of the branches, that is, the molecular weight of the branches and the heat supply time, heat was applied at 80 ° C for 5 minutes or at 100 ° C for 2 minutes. Observed.

6C and 6D, when the heat is supplied at 80 ° C. for 5 minutes, the supramolecular networks according to Examples 3 and 4 have been found to have self-healing. Examples 1, 2, and Comparative Examples It can be seen that supramolecular networks according to 1 and Comparative Example 2 are not self-healing. Also, referring to FIG. 6A, the supramolecular network according to Example 2 generates self-healing when heat is supplied at 80 ° C. for 40 minutes, but does not generate self-healing when heat is supplied for 5 minutes at the same temperature. You can check it. The supramolecular networks according to the third and fourth embodiments may be capable of self-healing even when a relatively small amount of heat is supplied.

7B and 7C, when supplying heat at 100 ° C. for 2 minutes, the supramolecular network according to Examples 1 to 4 was found to have self-healing, but supramolecules according to Comparative Examples 1 and 2 You can see that the networks are not self-healing. In addition, referring to FIG. 7A, the supramolecular network according to Example 2 generated self-healing when heat was supplied at 100 ° C. for 40 minutes, and self-healing occurred even when heat was supplied for 2 minutes at the same temperature. have. In other words, when heat is supplied at a temperature of 100 ° C., self-healing may occur even in a short time.

Experimental Example 5

Each of the nonlinear supramolecular bodies prepared in Examples 3, 4 and Comparative Example 1 was measured for rheological properties using a rheometer in a molten state. The measurement sample was made into a circular sample having a diameter of 25 mm and a thickness of 1 mm using a thermocompression press method. Rheological properties used parallel plate steel type (ETC) and storage modulus in the linear viscoelastic behavior region (LVE) at four temperature ranges from 90 ° C to 110, 130 and 150 ° C. Loss modulus was measured according to the frequency (0.01 ~ 100 Hz). The results of each measured temperature range are plotted by the time-temperature superposition principle, and the molecular dynamics measure, supramolecular bond lifetime (τ), is used to conduct a quantitative analysis of supramolecular bond-dissociation equilibrium. _b ).

Referring to FIG. 8, τ _b of the supramolecular network according to Comparative Example 1 was 0.013 s, and the self-healing rate was lower than that of the supramolecular networks of Examples 3 and 4.

Thus, the longer the number-average molecular weight of the nonlinear supramolecular branch, i.e., the longer the branch, the shorter the time it takes to equilibrate the bond-dissociation for the damage given to the self-healing network, and the faster the post-dissociation equilibrium It can be seen that excellent self-healing properties are expressed.

Claims (10)

A nonlinear supramolecular body for self-healing supramolecular networks comprising a nonlinear polymer comprising at least three branches having a number average molecular weight of 5000 g / mol or more and a polyhydrogenable single molecule provided at each end of the branch.
The method of claim 1,
The multi-hydrogen bondable single molecule is a compound containing at least one ureido (ureido) non-linear hypermolecular sieve for self-healing supramolecular network.
The method of claim 1,
Nonlinear supramolecular body for self-healing supramolecular networks wherein the number average molecular weight of the branches is 5000-15000 g / mol.
The method of claim 1,
The nonlinear supramolecular body is a nonlinear supramolecular body for self-healing supramolecular networks having a glass transition temperature of 0 ° C. or less.
The method of claim 1,
Nonlinear supramolecular sieve for self-healing supramolecular networks wherein the number average molecular weight of the branches is 8500-15000 g / mol.
A self-healing supramolecular network comprising the nonlinear supramolecular body according to any one of claims 1 to 5 and forming a supramolecular crosslinked body by hydrogen bonding between the single molecules provided at the branch end of the nonlinear supramolecular body.
The method of claim 6,
The self-healing supramolecular network further comprises a self-healing linear supramolecular network.
The method of claim 6,
The self-healing supramolecular network is a self-healing supramolecular network having supramolecular bond lifetime (τ _b ) of 0.003 to 0.010 seconds.
Hydrogen bonds between single molecules provided at branch ends of nonlinear supramolecular bodies by supplying heat at a predetermined temperature and time to the self-healing supramolecular network according to claim 6 or applying a microwave having a predetermined frequency Self-healing method of supramolecular network to heal the damage through.
A coating composition comprising the nonlinear supramolecular body according to any one of claims 1 to 5.

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