KR102608307B1 - A diol-based crosslinker with controlled steric hindrance, and a thermoset polyurethane that can be self-healed/recycled under low-temperature and non-catalytic conditions including it - Google Patents

Abstract

The present invention relates to self-healing and recycling technology through reversible carbamate exchange in the polymer network structure and to polyurethane materials containing the same. More specifically, carbamate exchange by changing the steric hindrance properties in the diol structure. It is about controlling the reaction temperature and speed, polyurethane materials in combination with various alcohols, isocyanates, cross-linking agents and catalysts, their rheological properties, self-healing/recycling properties and manufacturing methods. Polyurethane containing a diol monomer with steric hindrance according to the present invention is capable of self-healing and recycling, unlike existing thermosetting materials, and at a lower temperature compared to polyurethane containing previously reported dynamic covalent bonds. It has the advantage of being able to realize self-healing and recycling in stone-based catalyst and non-catalyst reaction systems.

Description

A diol-based crosslinker with controlled steric hindrance, and a thermoset polyurethane that can be self-healed/containing diol with controlled steric hindrance properties and capable of self-healing/recycling under low-temperature and non-catalytic conditions. recycled under low-temperature and non-catalytic conditions including it}

The present invention relates to a thermosetting polyurethane material capable of self-healing under low temperature and non-catalytic conditions and a method for manufacturing the same. Specifically, the present invention relates to a thermosetting polyurethane resin containing a hindered alcohol with controlled steric hindrance properties, which can be used at low temperatures without a catalyst. It relates to a self-healing or recyclable thermosetting polyurethane material and its manufacturing method.

More specifically, the thermosetting polyurethane material capable of self-healing/recycling below the melting temperature of the thermosetting polyurethane by controlling the carbamate exchange reaction temperature and speed by changing the steric hindrance properties in the hindered alcohol structure and its manufacturing method. will be.

Polyurethane is used in various fields such as coatings, adhesives, electrical insulators, structural materials, foam insulation, and elastic fibers. The polyurethane can be divided into thermoplastic polyurethane and thermosetting polyurethane. In the case of the thermoplastic polyurethane, it is easy to melt and recycle at high temperature, but it has the disadvantage of low mechanical properties and heat resistance.

On the other hand, thermosetting polyurethane has high heat resistance and mechanical properties, but its melting temperature is very high. In particular, covalent bonds are also decomposed at this melting temperature, which may lead to the problem that it cannot be recycled. In addition, as recycling of the thermosetting polyurethane is not smooth, problems regarding environmental pollution may also occur.

Since thermosetting polyurethane accounts for a large proportion of about 31% of thermosetting plastic materials, self-healing and recycling technology for thermosetting polyurethane is environmentally and economically significant. In general, thermosetting plastic materials cannot be recycled, but thermosetting polyurethane containing dynamic covalent bonds undergoes a carbamate exchange reaction with a catalyst under high temperature conditions and exhibits mechanical properties similar to thermosetting plastics.

Recently, in this regard, research on self-healing and recycling of polyurethane containing dynamic covalent bonds has been actively conducted, and prior technology for controlling the temperature and speed of carbamate exchange reaction is required to increase self-healing and recycling efficiency.

In addition, currently reported self-healing and recyclable polyurethanes generally use a tin-based catalyst called dibutyltin dilaurate (DBTDL), but not only does it require high heat energy, but it is also subject to environmental regulations due to its high toxicity. Accordingly, there is a need to develop chemical materials capable of controlling activation energy related to non-tin-based catalysts or catalyst-free reaction systems and dynamic behavior.

In order to solve the above-mentioned problems, the purpose of the present invention is to synthesize a thermosetting polyurethane resin that is capable of self-healing or recycling even at low temperatures.

In addition, the purpose of the present invention is to synthesize self-healing or recyclable thermosetting polyurethane materials with various rheological properties through a non-catalytic reaction system.

In addition, the purpose of the present invention is to synthesize a thermosetting polyurethane material capable of self-healing and recycling even at low temperatures by controlling rheological properties and carbamate exchange reactivity.

In order to solve the above-mentioned problems, the present invention is prepared from a polymerizable composition containing an alcohol compound containing a hindered phenol group, a C ₁ -C ₂₀ linear or branched polyol, a polyfunctional isocyanate-based compound, and a crosslinking agent. Phosphorus, self-healing thermosetting polyurethane resin is provided.

According to one aspect of the present invention, the hindered phenol group may be represented by the following structure.

[structure]

(In the above structure, A is hydrogen, a linear or branched hydrocarbyl, and B is a linear or branched hydrocarbyl.)

According to one aspect of the present invention, the alcohol compound containing the hindered phenol group may be represented by Formula 1 or Formula 2 below.

[Formula 1]

[Formula 2]

In Formula 1, R ₁ and R ₃ is independently hydrogen, C ₁ to C ₂₀ alkyl, C ₃ -C ₂₀ cycloalkyl, C ₆ -C ₂₀ aryl and halogen, R ₂ and R ₄ is independently C ₁ to C ₂₀ alkyl, C ₃ -C ₂₀ cycloalkyl, C ₆ -C ₂₀ aryl and halogen, n is an integer from 1 to 100,

In Formula 2, R ₅ and R ₇ are independently hydrogen, C ₁ to C ₂₀ alkyl, C ₃ -C ₂₀ cycloalkyl, C ₆ -C ₂₀ aryl, and halogen, and R ₆ and R ₈ are independently C ₁ to C ₂₀ alkyl, C ₃ -C ₂₀ cycloalkyl, C ₆ -C ₂₀ aryl and halogen, and n may be an integer from 1 to 100.

According to one aspect of the present invention, the alcohol compound containing the hindered phenol group may be represented by the following formula (2).

[Formula 2]

In Formula 2, R ₅ and R ₇ are independently hydrogen, C ₁ to C ₂₀ linear or branched alkyl, R ₆ and R ₇ are independently C ₁ to C ₂₀ linear or branched alkyl, and n is It may be an integer from 1 to 50.

According to one aspect of the present invention, the alcohol compound containing a hindered phenol group may include any one or two or more of the alcohol compounds containing a hindered phenol group represented by the following formulas 3 to 6.

[Formula 3]

[Formula 4]

[Formula 5]

[Formula 6]

According to one aspect of the present invention, in Formula 2, at least one of R ₅ to R ₈ may include C ₃ to C ₂₀ branched alkyl.

According to one aspect of the present invention, the alcohol compound containing a hindered phenol group may include any one or two or more of the alcohol compounds containing a hindered phenol group represented by the following formulas 3 to 4.

[Formula 3]

[Formula 4]

delete

According to one aspect of the present invention, the C ₁ -C ₂₀ linear or branched diol is one or two selected from polyethylene glycol, polypropylene glycol, polytetramethylene ether glycol, polydecalactone diol, and polycarbonate diol. It may include more than one.

According to one aspect of the present invention, the polyfunctional isocyanate-based compound may include an aliphatic or aromatic isocyanate-based compound containing two isocyanate functional groups.

According to one aspect of the present invention, the polyfunctional isocyanate compound may have a molecular weight of 10 to 700 g/mol.

According to one aspect of the present invention, the crosslinking agent may include a polyol containing three or more hydroxy groups or an isocyanate-based compound containing three or more isocyanate groups.

According to one aspect of the present invention, the cross-linking agent may include one or more cross-linking agents selected from triol and tetraol.

According to one aspect of the present invention, the crosslinking agent may include one or more crosslinking agents selected from triisocyanate and tetraisocyanate.

According to one aspect of the present invention, the polymerizable composition contains 1 to 100 parts by weight of an alcohol compound containing a hindered phenol group, and 1 polyfunctional isocyanate-based compound, based on 100 parts by weight of a C ₁ -C ₂₀ linear or branched polyol. It may be included in an amount of from 100 parts by weight and a crosslinking agent of 0.1 to 50 parts by weight.

An isocyanate functional group of the polyfunctional isocyanate compound included in the polymerizable composition according to one aspect of the present invention; and the alcohol compound containing the hindered phenol group, the hydroxy functional group of the polyol and the crosslinking agent; may satisfy an equivalence ratio of 1:0.5 to 1.

According to one aspect of the present invention, the polymerizable composition may further include a tin-based catalyst.

According to one aspect of the present invention, the self-healing thermosetting polyurethane resin may be self-healing through carbamate exchange below the decomposition temperature.

According to one aspect of the present invention, the self-healing thermosetting polyurethane resin may be self-healing through carbamate exchange at 150°C or lower.

According to one aspect of the present invention, the tensile strength of the self-healing thermosetting polyurethane resin may satisfy Equation 1 below.

[Equation 1]

TSr/TSi ≥ 0.7

(In Equation 1, TSr is the tensile strength measured after remolding the self-healing thermosetting polyurethane resin at a temperature of 150°C or higher and a pressure of 60 bar or lower, and TSi is the initial tensile strength of the self-healing thermosetting polyurethane resin. It can be.)

The present invention is a self-healing method using the self-healing thermosetting polyurethane resin, wherein the self-healing thermosetting polyurethane resin is an alcohol compound containing a hindered phenol group, a C ₁ -C ₂₀ linear or branched polyol, and a multifunctional It is manufactured from a polymerizable composition containing an isocyanate-based compound and a cross-linking agent, and the self-healing is performed by controlling the self-healing temperature by controlling the degree of steric hindrance of the alcohol compound containing a hindered phenol group. You can.

According to one aspect of the present invention, preparing a mixed solution by dissolving a C ₁ -C ₂₀ linear or branched polyol in an organic solvent; Preparing a polymerizable composition containing an alcohol compound containing a hindered phenol group, a polyfunctional isocyanate-based compound, and a crosslinking agent in the mixed solution; and thermosetting the polymerizable composition to produce a self-healing thermosetting polyurethane resin.

According to one aspect of the present invention, the thermal curing is divided into a first curing step and a second curing step and proceeds sequentially. In the first curing step, curing is performed at room temperature, and the second curing step is performed at 60 to 150 ° C. It can happen.

According to one aspect of the present invention, preparing a method for producing a self-healing thermosetting polyurethane resin; It is possible to provide a recycling method of the manufacturing method of the self-healing thermosetting polyurethane resin, including the step of re-molding the manufacturing method of the self-healing thermosetting polyurethane resin.

According to one aspect of the present invention, the remolding temperature may be 100 to 200°C.

The thermosetting polyurethane according to the present invention is capable of self-healing and recycling, unlike existing thermosetting materials.

In addition, the thermosetting polyurethane according to the present invention can realize self-healing and recycling in non-tin-based catalysts and catalyst-free reaction systems at lower temperatures compared to polyurethanes containing conventional dynamic covalent bonds.

Figure 1 shows a schematic diagram of the change in carbamate exchange reaction due to diol steric hindrance in thermosetting polyurethane according to an aspect of the present invention.
Figure 2 is a thermogravimetric analysis (TGA) graph of the self-healing thermosetting polyurethane resin of Examples 1 and 3 according to an aspect of the present invention.
Figure 3 shows analysis through differential scanning calorimetry (DSC) of the self-healing thermosetting polyurethane resins of Examples 1 and 3 according to an aspect of the present invention.
Figure 4 is a graph analyzing the storage modulus values of the self-healing thermosetting polyurethane resins of Examples 1 and 3 according to an aspect of the present invention.
Figure 5 is a graph analyzing the tan delta value (tan δ) of the self-healing thermosetting polyurethane resins of Examples 1 and 3 according to an aspect of the present invention.
Figure 6 is a graph analyzing the rheological properties of the self-healing thermosetting polyurethane resin of Example 1 according to an aspect of the present invention using a rheometer.
Figure 7 is a graph showing complex viscosity measurement results analyzing the rheological properties of the self-healing thermosetting polyurethane resin of Example 1 according to an aspect of the present invention.
Figure 8 is a graph analyzing the tensile strength of the self-healing thermosetting polyurethane resin of Example 1 according to an aspect of the present invention using a universal testing machine (UTM).
Figure 9 is a photograph of the specimen of Example 1 before the tensile strength test (a), before the tensile strength test (b), immediately after the tensile strength test (c), and 2 minutes after the tensile strength test (d).
Figure 10 shows the self-healing thermosetting polyurethane resin piece of Example 1 according to an aspect of the present invention before heat compression (a), the specimen after heat compression (b), and before the tensile test of the heat compression specimen (c). ) and a photo of a heat-compressed specimen undergoing a tensile test.
Figure 11 compares the tensile test results of polyurethane specimens before and after remolding with a thermocompressor to confirm the self-healing and recyclability of the self-healing thermosetting polyurethane resin of Example 1 according to an aspect of the present invention. will be.
Figures 12 to 14 are ¹ H-NMR analysis spectra for Preparation Examples 1 to 3 prepared.

Hereinafter, the present invention will be described in more detail through specific examples or examples including the attached drawings. However, the following examples are only for reference to explain the present invention in detail, and the present invention is not limited thereto, and may be implemented in various forms.

Additionally, unless otherwise defined, all technical and scientific terms have the same meaning as commonly understood by one of ordinary skill in the art to which the present invention pertains. The terminology used in the description herein is merely to effectively describe particular embodiments and is not intended to limit the invention.

In the present invention, when a part "includes" a certain component, this means that it may further include other components rather than excluding other components, unless specifically stated to the contrary.

Additionally, as used in the specification and the appended claims, the singular forms “a,” “an,” and “the” are intended to also include the plural forms, unless the context clearly dictates otherwise.

Unless otherwise defined, the technical and scientific terms used in this specification have the meanings commonly understood by those skilled in the art to which this invention pertains, and the gist of the present invention is summarized in the following description and accompanying drawings. Descriptions of known functions and configurations that may unnecessarily obscure are omitted.

In addition, units used in this specification without special mention are based on weight, and as an example, units of % or ratio mean weight % or weight ratio, and weight % refers to the composition of any one component of the entire composition unless otherwise defined. It refers to the weight % occupied within.

In addition, the numerical range used in this specification includes the lower limit and upper limit and all values within the range, increments logically derived from the shape and width of the defined range, all double-defined values, and the upper limit of the numerical range defined in different forms. and all possible combinations of lower limits. Unless otherwise specified in the specification of the present invention, values outside the numerical range that may occur due to experimental error or rounding of values are also included in the defined numerical range.

The term "dynamic covalent bond" used throughout this specification refers to a covalent bond that exhibits reversibility under controlled equilibrium conditions, and the thermodynamic equilibrium state can be reversibly converted by external stimuli such as temperature or catalyst. It is a combination that exists. Polymers containing dynamic covalent bonds can be applied as self-healing and recyclable polymer systems because their composition and structure can be reorganized. In the present invention, in particular, the urethane bond is broken (debonding) and the formed hydroxy group and the isocyanate group form a urethane bond with the adjacent hydroxy group and the isocyanate group, or a carbamate exchange reaction in which the substituents connected to the crosslinking point are exchanged while maintaining the crosslinking density. Includes.

Additionally, the term “polymer” herein refers to a polymer or copolymer prepared by polymerizing one or more polymerizable monomers.

In addition, the term “hindered phenol group” herein refers to a phenol group that causes steric hindrance by substituting a hydrocarbon group in a portion adjacent to the hydroxy functional group of phenol, but is not limited thereto.

The low temperature presented in the present invention means a temperature of 300°C or lower, which is lower than the melting temperature of a general thermosetting polyurethane resin, and specifically means a temperature of 50 to 250°C.

Hereinafter, the self-healing thermosetting polyurethane resin according to an embodiment of the present invention will be described in more detail.

The present invention provides a self-healing thermosetting polyurethane resin prepared from a polymerizable composition containing an alcohol compound containing a hindered phenol group, a C ₁ -C ₂₀ linear or branched polyol, a polyfunctional isocyanate-based compound, and a crosslinking agent. do.

According to one aspect of the present invention, the hindered phenol group may be represented by the following structure.

[structure]

(In the above structure, A is hydrogen, a linear or branched hydrocarbyl, and B is a linear or branched hydrocarbyl.)

The present invention includes an alcohol compound containing the hindered phenol group in a self-healing thermosetting polyurethane resin, thereby enabling self-healing or recycling at a relatively low temperature while maintaining the unique heat resistance and mechanical strength of thermosetting polyurethane. A new type of self-healing or recyclable thermosetting polyurethane resin can be provided.

The alcohol compound containing the hindered phenol group may include a phenol group at the terminal of the alcohol compound.

Specifically, according to one aspect of the present invention, the alcohol compound containing the hindered phenol group may be represented by Formula 1 or Formula 2 below.

[Formula 1]

[Formula 2]

In Formula 1, R ₁ and R ₃ is independently hydrogen, C ₁ to C ₂₀ alkyl, C ₃ -C ₂₀ cycloalkyl, C ₆ -C ₂₀ aryl and halogen, R ₂ and R ₄ are independently C ₁ to C ₂₀ alkyl, C ₃ -C ₂₀ cycloalkyl, C ₆ -C ₂₀ aryl, and halogen, and n may be an integer from 1 to 100,

In Formula 2, R ₅ and R ₇ are independently hydrogen, C ₁ to C ₂₀ alkyl, C ₃ -C ₂₀ cycloalkyl, C ₆ -C ₂₀ aryl, and halogen, and R ₆ and R ₈ are independently C ₁ to C ₂₀ alkyl, C ₃ -C ₂₀ cycloalkyl, C ₆ -C ₂₀ aryl and halogen, and n may be an integer from 1 to 100.

According to one aspect of the present invention, the alcohol compound containing the hindered phenol group may be represented by the following formula (2).

[Formula 2]

In Formula 2, R ₅ and R ₇ are independently hydrogen, C ₁ to C ₂₀ linear or branched alkyl, and R ₆ and R ₈ are independently C ₁ to C ₂₀ linear or branched alkyl, specifically methyl, It may be any one selected from ethyl, propyl, n-butyl, s-butyl, i-butyl, t-butyl and 2-ethylhexyl, and n may be an integer from 1 to 50.

Specifically, according to one aspect of the present invention, the alcohol compound containing a hindered phenol group may be any one or two or more of the alcohol compounds containing a hindered phenol group represented by the following formulas 3 to 6.

[Formula 3]

[Formula 4]

[Formula 5]

[Formula 6]

According to one aspect of the present invention, in Formula 2, at least one of R ₅ to R ₈ may be C ₃ to C ₂₀ branched alkyl, specifically s-butyl, i-butyl, t-butyl. and 2-ethylhexyl.

Alcohol compounds containing hindered phenol groups of Formulas 2 to 6 include aromatic substituents at the terminals of the alcohol compounds, and may exhibit steric effects caused by bulking of the aromatic substituents. Due to the steric hindrance, a phenomenon in which the carbamate covalent bond between the hydroxy group and the isocyanate group is broken may occur even at low temperatures. As the covalent bonds are partially broken, the thermosetting polyurethane resin has rheological properties similar to those of thermoplastic polyurethane resin, and thus can be self-healing or recycling.

That is, the present invention can provide a new type of self-healing thermosetting polyurethane resin that has the mechanical properties and heat resistance of a thermosetting polyurethane resin and at the same time has the processability of a thermoplastic polyurethane resin.

Accordingly, the present invention can control the temperature at which the carbamate covalent bond is broken by controlling the degree of steric hindrance, and thus self-healing or recycling is possible at a desired temperature.

More specifically, according to one aspect of the present invention, the alcohol compound containing a hindered phenol group may be any one or two or more of the alcohol compounds containing a hindered phenol group represented by the following formulas 3 to 4.

[Formula 3]

[Formula 4]

In the case of self-healing thermosetting polyurethane resins containing any one or two or more compounds from the alcohol compounds containing hindered phenol groups represented by formulas 3 to 4, self-healing or recycling is possible at lower temperatures and even after re-curing. It can have better mechanical properties and heat resistance.

delete

According to one aspect of the present invention, the C ₁ -C ₂₀ linear or branched polyol is not greatly limited as long as it is a commonly used polyol, but may be any selected from ether-based polyol compounds, ester-based polyol compounds, carbonate-based polyol compounds, etc. One or a mixture of two or more may be used. Alternatively, the linear or branched polyol may be diol. As a non-limiting example, the diol may be a dihydric alcohol, polyesterdiol, and polyesterdiol. Specifically, ethylene glycol, 1,2-propanediol, 1,3-propanediol, 1,3-butanediol, 1,4-butanediol, 1,4-butenediol, 1,4-butynediol, 1,5-pentane. Diol, neopentyl glycol, bis(hydroxymethyl)cyclohexane, 2-methyl-1,3-propanediol, methylpentanediol, diethylene glycol, triethylene glycol, tetraethylene glycol, polyethylene glycol, dipropylene glycol, poly Examples include, but are not limited to, propylene glycol, dibutylene glycol, polybutylene glycol, polytetrahydrofuran, polycarbonate diol, polycaprolactone diol, and polytetramethylene ether glycol (PTMEG), and the like, and the desired mechanical strength The polyol compound can be easily selected and used to implement physical properties such as, but is not limited to this.

According to one aspect of the present invention, the polyfunctional isocyanate compound may be any one or a mixture of two or more selected from a cycloaliphatic isocyanate compound, an aliphatic isocyanate compound, and an aromatic isocyanate compound, and the polyfunctional isocyanate compound may have two isocyanate functional groups. Any compound containing can be used without significant restrictions. In addition, the polyfunctional isocyanate compound may have a molecular weight of 10 to 1,000 g/mol, specifically 10 to 700 g/mol, and more specifically 50 to 500 g/mol, provided it does not impair the physical properties targeted by the present invention. It is not limited to this.

Non-limiting examples of the polyfunctional isocyanate compound include methylenediphenyl diisocyanate (MDI), 4,4'-dicyclohexylmethane diisocyanate (H12-MDI), toluene diisocyanate (TDI), and methylcyclohexylene diisocyanate ( It may be one or a combination of two or more selected from (H12-TDI), tetramethylxylene diisocyanate (TMXDI), hexamethylene diisocyanate (HDI), cyclohexylene diisocyanate, and isophorone diisocyanate (IPDI), but two Any compound containing an isocyanate functional group can be used without significant restrictions.

According to one aspect of the present invention, the functional group of the crosslinking agent may be a hydroxy group or an isocyanate group, or a complex thereof, but is not limited thereto.

Specifically, the crosslinking agent may be a polyol containing three or more hydroxy groups, or an isocyanate-based compound containing three or more isocyanate groups, but is not limited thereto.

A thermosetting polyurethane resin having a network structure can be provided by combining three or more hydroxy groups with an isocyanate group or combining three or more isocyanate groups with a hydroxy group.

According to one aspect of the present invention, an example of the polyol containing three or more hydroxy groups in the crosslinking agent may be any one or more polyols selected from triol and tetraol, but is not limited thereto.

The triol may include a C ₃ to C ₁₀ alkyl triol, and the tetraol may include a C ₄ to C ₁₀ alkyl tetraol.

The C ₃ to C ₁₀ alkyl triol is, for example, selected from propane triol (glycerol), butanetriol, pentanetriol, hexanetriol, heptanetriol, octanetriol, nonantriol, and decantriol. It may be any one or a mixture of two or more, but is not limited thereto.

The C ₄ to C ₁₀ alkyl tetraol is, for example, selected from n-butane tetraol, n-pentane tetraol, n-hexane tetraol, n-heptane tetraol, n-octane tetraol, and n-decane tetraol. There may be one or more than one, but it is not limited thereto.

According to one aspect of the present invention, the crosslinking agent is an example of an isocyanate-based compound containing three or more isocyanate groups, such as 4-isocyanatomethyl-1,8-octane diisocyanate and lysine triisocyanate. , and three or more isocyanate groups such as 4,4',4"-triphenylmethane triisocyanate, 1,3,5-triisocyanate benzene, and polyphenyl polymethylene polyisocyanate obtained by phosgenating aniline/formaldehyde condensate. It may include aromatic polyisocyanate and mixtures thereof, but is not limited thereto.

According to one aspect of the present invention, an isocyanate functional group of the polyfunctional isocyanate compound included in the polymerizable composition; and the alcohol compound containing the hindered phenol group, the hydroxy functional group of the polyol and the crosslinking agent; may satisfy an equivalence ratio of 1:0.5 to 1, specifically 1:0.5 to 1, more specifically 1:0.7 to 1. The equivalence ratio can be satisfied.

In addition, according to another aspect of the present invention, a crosslinking agent containing an isocyanate functional group and an isocyanate group of the polyfunctional isocyanate compound included in the polymerizable composition; and the alcohol compound containing the hindered phenol group, the hydroxy functional group of the polyol; may satisfy an equivalence ratio of 1:0.5 to 1, specifically 1:0.5 to 1, more specifically 1:0.7 to 1. You can be satisfied.

According to one aspect of the present invention, the polymerizable composition may not contain a catalyst or may further contain a catalyst. The catalyst may be a tin-based catalyst or a non-tin-based catalyst. Non-limiting examples of the tin-based catalyst include SnCl ₄ , butyltin trichloride, dibutyltin oxide, DBTDL, and dibutyltin bis(2-ethylhexanoate), and non-limiting examples of the non-tin-based catalyst include manganese (III) acetylaceto. Manganese(III) acetylacetonate, Mn(acac) ₃ ), Cobalt(III) acetylacetonate, Co(acac) ₃ ), Aluminum acetylacetonate (Al(acac) ₃ ) , iron(III) acetylacetonate (Fe(acac) ₃ ) and zinc acetylacetonate (Zn(acac) ₂ ), etc., but are not limited thereto.

By further including the above catalysts, the activation energy for the reaction is lowered, making it possible to provide a self-healing thermosetting polyurethane resin capable of self-healing under milder conditions.

According to one aspect of the present invention, the self-healing thermosetting polyurethane resin can be self-healed through carbamate exchange at 150°C or lower. In the past, carbamate exchange was possible at a temperature higher than the thermal decomposition temperature of polyurethane, so there was a problem that it was difficult to utilize self-healing. In order to solve this problem, the self-healing thermosetting polyurethane resin according to an embodiment of the present invention was designed to enable carbamate exchange at 150 ℃ or less, specifically 100 to 150 ℃, and using these characteristics, It has the advantage of being able to implement self-healing and recycling characteristics.

According to one aspect of the present invention, the tensile strength of the self-healing thermosetting polyurethane resin may satisfy the following equation 1, specifically, may satisfy the following equation 2, and more specifically, the following equation It may satisfy 3, but is not limited thereto.

[Equation 1]

TSr/TSi ≥ 0.7

[Equation 2]

TSr/TSi ≥ 0.8

[Equation 3]

TSr/TSi ≥ 0.9

In Equations 1 to 3, TSr is the tensile strength measured after remolding the self-healing thermosetting polyurethane resin at a temperature of 100°C or higher, and TSi is the initial tensile strength of the self-healing thermosetting polyurethane resin.

Satisfying the above equations 1 to 3 means that the self-healing thermosetting polyurethane resin can be recycled or remolded, and above all, it can maintain excellent mechanical properties even after remolding. The self-healing thermosetting polyurethane resin that satisfies the above formulas 1 to 3 has the advantage of realizing excellent recyclability in that it is capable of not only self-healing but also remoulding and shows an excellent physical property recovery rate even after remoulding.

In particular, the self-healing thermosetting polyurethane resin that satisfies Equation 2 rather than Equation 1 may have superior physical property recovery rate and mechanical properties, and the self-healing thermosetting polyurethane resin that satisfies Equation 3 rather than Equation 2 has better physical properties. It can have recovery rate and mechanical properties.

The present invention is a self-healing method using the self-healing thermosetting polyurethane resin, wherein the self-healing thermosetting polyurethane resin is an alcohol compound containing a hindered phenol group, a C ₁ -C ₂₀ linear or branched polyol, and a multifunctional It is manufactured from a polymerizable composition containing an isocyanate-based compound and a cross-linking agent, and the self-healing is performed by controlling the self-healing temperature by controlling the degree of steric hindrance of the alcohol compound containing a hindered phenol group. .

The present invention is a self-healing method using the self-healing thermosetting polyurethane resin described above, wherein the self-healing thermosetting polyurethane resin is an alcohol compound containing a hindered phenol group, a C ₁ -C ₂₀ linear or branched polyol, It is manufactured from a polymerizable composition containing a functional isocyanate-based compound and a cross-linking agent, and as described above, the self-healing method provides a self-healing method that can control the self-healing temperature by controlling the degree of steric hindrance of the hindered phenol group. You can.

According to one embodiment of the present invention, the self-healing temperature may be 150°C or less, specifically 100 to 150°C. In the above temperature range, the self-healing thermosetting polyurethane resin described above can implement self-healing ability, which is the ability to self-recover from damage formed from the outside. The self-healing thermosetting polyurethane resin described above has the advantage of being able to self-heal at a temperature significantly lower than the conventional self-healing temperature, and can be used to manufacture remolded or recyclable materials.

According to one embodiment of the present invention, the self-healing temperature may be 150°C or less, specifically 100 to 150°C. In the above temperature range, the self-healing thermosetting polyurethane resin described above can implement self-healing ability, which is the ability to self-recover from damage formed from the outside. The self-healing thermosetting polyurethane resin described above has the advantage of being able to self-heal at a temperature significantly lower than the conventional self-healing temperature, and can be used to manufacture remolded or recyclable materials.

The present invention includes the steps of dissolving a C ₁ -C ₂₀ linear or branched polyol in an organic solvent to prepare a mixed solution; Preparing a polymerizable composition containing an alcohol compound containing a hindered phenol group, a polyfunctional isocyanate-based compound, and a crosslinking agent in the mixed solution; and producing a self-healing thermosetting polyurethane resin by thermosetting the polymerizable composition.

The thermal curing may be performed at 30 to 150 °C. Specifically, thermal curing may be performed in stages. Specifically, the thermal curing may be divided into a first curing step and a second curing step and proceed sequentially. In the first curing step, the curing may be performed at room temperature, and the second curing step may be performed sequentially. The curing step may be carried out at 30 to 150° C., but is not limited thereto.

Preparing a method for producing the self-healing thermosetting polyurethane resin according to one aspect of the present invention; It is possible to provide a recycling method of the manufacturing method of the self-healing thermosetting polyurethane resin, including the step of re-molding the manufacturing method of the self-healing thermosetting polyurethane resin.

According to one aspect of the present invention, the self-healing thermosetting polyurethane resin is capable of self-healing in a wide range of temperatures. In other words, by significantly lowering the temperature of the carbamate exchange reaction that was carried out at a conventional high temperature, a self-healing thermosetting polyurethane resin capable of self-healing even at a temperature below the point where polyurethane bonds begin to decompose was manufactured, and these characteristics were produced. Materials with have the great advantage of being recyclable. After manufacturing various molded products using the self-healing thermosetting polyurethane resin, it can be recycled into another molded product with a different appearance by collecting and re-molding. Furthermore, the self-healing thermosetting polyurethane resin has physical properties even after recycling. Because the recovery rate is excellent, the recycled molded product has the advantage of being able to realize excellent mechanical properties.

According to one embodiment of the present invention, the re-molding temperature may be 100 to 200 °C, specifically 110 to 180 °C, and more specifically 130 to 170 °C. If the above range is satisfied, it can be preferred in that the recovery rate of physical properties is excellent even after re-molding and recycling efficiency can be further improved.

The present invention will be described in more detail below based on examples and comparative examples. However, the following Examples and Comparative Examples are only one example to explain the present invention in more detail, and the present invention is not limited by the following Examples and Comparative Examples.

[Physical property measurement method]

1) Thermal decomposition temperature (5% T _d )

The thermal decomposition temperature of the self-healing thermosetting polyurethane resin prepared in Example 1 was measured using thermogravimetric analysis (TGA, Perkin Elmer, Pyris 1 TGA), and the measurement conditions were a temperature range of 800 ℃ from room temperature, 10 ℃/10 ℃. It was measured under a nitrogen atmosphere at a temperature increase rate of min, and the temperature at which 5% mass loss occurred was recorded as the thermal decomposition temperature. The measured thermogravimetric analysis is shown in Figure 2.

2) Glass transition temperature (T _g )

The glass transition temperature of the prepared self-healing thermosetting polyurethane resin was measured using differential scanning analysis (DSC, TA instruments, Discovery DSC 2500) at a temperature range of -20 to 200 °C at 10 °C/min. Isothermal differential scanning analysis was performed while increasing the temperature at a heating rate. The differential scanning analysis measured above is shown in Figure 3.

3) Dynamic mechanical analysis

For dynamic mechanical analysis (DMA), polyurethane samples according to Examples 1 and 4 were prepared using a Teflon mold with dimensions of 60 mm × 15 mm × 1.5 mm (width × length × height). The storage modulus, loss modulus, and ratio of storage modulus and loss modulus (tan δ) according to the temperature of each polyurethane sample were analyzed using dynamic mechanical analysis equipment (Perkin Elmer, DMA 8000). It was measured using a standard force of 0.1 N, strain of 0.1%, temperature range of -80 ℃ to 200 ℃, and temperature increase rate of 3 ℃/min. A graph of the measured storage modulus is shown in FIG. 3, and a graph of the ratio (tan δ) of the storage modulus and loss modulus is shown in FIG. 4.

4) Complex viscosity

The self-healing thermosetting polyurethane resin prepared in Example 1 was cured in a circular Teflon mold of 25 mm × 1.5 mm (diameter × height) and measured using a rheometer (Anton Parr, MCR102). The viscosity was measured using . The measurement conditions were standard force 0.1 N, strain 0.05%, temperature range -50 to 200 ℃, and temperature increase rate of 5 ℃/min. The measured graph is shown in Figure 7.

5) Tensile strength

A 60×5×2 mm polyurethane sample according to Example 1 was prepared to analyze the tensile properties of the sample. The tensile strength of each polyurethane sample was measured using a universal testing machine (UTM, INSTRON, UTM 5982) at a grip distance of 10 mm and 60 mm/min. The measured graph is shown in Figure 8.

5) Tensile strength and tensile strength recovery rate: The self-healing thermosetting polyurethane resin of Example 1 was cut with scissors and pressed using a heat press (Hot press [Table-top Platen Press] Collin, P200E) at 150°C, 60 bar. It was reshaped for 2 hours.

The reforming process is depicted in Figure 10. The tensile properties of the remolded polyurethane resin were analyzed and compared with the tensile properties of the initial polyurethane resin. The measured tensile strength graph is shown in Figure 11.

[Production Example 1]

In a 1 L reactor, 425.3 g of methyl 3-(3-(tert-butyl)-4-hydroxy-5-methylphenyl)propanoate and 124.4 g of triethylene glycol were dissolved in the base catalyst solvent and then refluxed at 100°C. The solvent was removed by distillation, neutralization was performed, and then recrystallization was performed to obtain Preparation Example 2 of a white solid phase. The ¹ H-NMR analysis spectrum of Preparation Example 2 prepared above is shown in Figure 13.

[Production Example 2]

In a 250 mL round bottom flask, 5.58 g of 3-(3,5-di-tert-butyl-4-hydroxyphenyl)propionic acid was dissolved in 100 mL of dichloromethane (DCM) and cooled to 0°C. After adding dimethylformamide (DMF), 3.43 mL of oxalyl chloride was added. The composition was gradually raised to room temperature, stirred and reacted for 18 hours, then the solvent and remaining oxalyl chloride were removed using a rotary evaporator, and 1.37 mL of triethylene glycol (TEG) was dissolved in 40 mL of dichloromethane. was slowly added and stirred at room temperature for an additional 18 hours. A saturated aqueous solution of sodium bicarbonate (NaHCO ₃ ) was added to the stirred solution, and the mixture was further stirred for 30 minutes, and then the organic layer was extracted using dichloromethane and a saturated aqueous sodium chloride solution. The extracted organic layer was concentrated using a rotary evaporator, and Preparation Example 1 was obtained with a yield of 56% using column chromatography and recrystallization. The ¹ H-NMR analysis spectrum of Preparation Example 1 prepared above is shown in Figure 12.

[Production Example 3]

To synthesize the precursor of Preparation Example 3, 3.32 g of 3-(4-hydroxyphenyl)propionic acid was first dissolved in 20 mL of dimethylformamide (DMF) in a 250 mL round bottom flask and cooled to 0°C. Afterwards, 6.62 g of tert-butyldimethylsilyl chloride (TBSCl) and 4.5 g of imidazole were added together with 20 mL of dimethylformamide, the temperature was gradually raised to room temperature and stirred for 18 hours, and the organic layer was mixed with distilled water and hexane. Extracted. The extracted organic layer was dissolved in a mixed solvent of tetrahydrofuran (THF) and methanol, an aqueous solution of potassium carbonate (K ₂ CO ₃ ) was added and stirred at room temperature for 18 hours, then diluted hydrochloric acid was added until the solution reached pH 3, and diethyl ether was added. The organic layer was extracted using . The extracted organic layer was concentrated using a rotary evaporator, and a precursor with a TBS protecting group introduced was obtained with a yield of 80% using column chromatography.

Add 2.80 g of the above precursor, 0.86 mL of triethylene glycol, and 1.47 g of 4-dimethylaminopyridine (DMAP) to a 250 mL round bottom flask, add 100 mL of dichloromethane to completely dissolve, and then add N3-(ethylcarbonimidoyl)- 2.11 g of N1,N1-dimethyl-1,3-propanediamine hydrochloride (1:1) (EDC·HCl) was added and stirred at room temperature for 18 hours. After stirring, the organic layer was extracted using diethyl ether, and then the structure of Preparation Example 3 with a TBS protecting group introduced was obtained using column chromatography with a yield of 71%.

0.63 g of the above material was dissolved in 7 mL of tetrahydrofuran in a 100 mL round bottom flask and then cooled to 0°C. 2.4 mL of tetrabutylammonium fluoride (TBAF in 1 M THF) solution was slowly added and stirred at room temperature for 18 hours. The organic layer was extracted using a saturated aqueous sodium bicarbonate solution and dichloromethane and recrystallized to obtain Preparation Example 3 with a yield of 50%. The ¹ H-NMR analysis spectrum of Preparation Example 3 prepared above is shown in FIG. 14.

[Example 1]

A mixed solvent was prepared by mixing 0.68 g of toluene and 0.63 g of ethyl acetate in a 20 mL vial, and then 1 g of polytetramethylene ether glycol (PTMEG, Mn=2,000) was added to the mixed solvent. After dissolution, 0.147 g of the compound of Preparation Example 1, 0.209 g of methylene diphenyl diisocyanate, and 0.017 g of caprolactone triol, a cross-linking agent, were further added to prepare a mixed solution. The mixed solution was mixed for 10 minutes using an ultrasonicator to remove gas in the mixed solution. The mixed solution was measured in a Teflon mold, and after initial curing at room temperature for 1 hour, it was cured in a vacuum oven at 70°C for 20 hours, in a reflux oven at 80°C for 2 hours, and further cured at 120°C for 2 hours.

[Example 2]

The same procedure as in Example 1 was carried out, except that the alcohol compound containing a hindered phenol group in Preparation Example 2 was used instead of Preparation Example 1 as the alcohol compound containing a hindered phenol group.

[Example 3]

A mixed solvent was prepared by mixing 0.68 g of toluene and 0.63 g of ethyl acetate in a 20 mL vial, and then 1 g of polytetramethylene ether glycol (PTMEG, Mn=2,000) was added to the mixed solvent. After dissolution, 0.147 g of the compound of Preparation Example 1, 0.209 g of methylene diphenyl diisocyanate, and 0.017 g of caprolactone triol, a cross-linking agent, were further added to prepare a mixed solution. The mixed solution was mixed for 10 minutes using an ultrasonicator to remove gas in the mixed solution. Add 0.013 g of DBTDL catalyst to the above mixed solution, weigh it in a Teflon mold, initial cure at room temperature for 1 hour, then cure in a vacuum oven at 70°C for 20 hours, in a reflux oven at 80°C for 2 hours, and then at 120°C for an additional 2 hours. cured.

[Comparative Example 1]

A mixed solvent was prepared by mixing 0.68 g of toluene and 0.63 g of ethyl acetate in a 20 mL vial, and then 1.5 g of polytetramethylene ether glycol (PTMEG, Mn=2,000) was added to the mixed solvent. After dissolution, 0.209 g of methylene diphenyl diisocyanate and 0.017 g of caprolactone triol, a cross-linking agent, were additionally added to prepare a mixed solution. The mixed solution was mixed for 10 minutes using an ultrasonicator to remove gas in the mixed solution. The mixed solution was measured in a Teflon mold, and after initial curing at room temperature for 1 hour, it was cured in a vacuum oven at 70°C for 20 hours, in a reflux oven at 80°C for 2 hours, and further cured at 120°C for 2 hours.

[Comparative Example 2]

The same procedure as in Example 1 was carried out, except that the alcohol compound containing a hindered phenol group of Preparation Example 3 was used instead of triethylene glycol bis.

First, in the case of Comparative Example 1, there was no temperature range showing the same thermoplastic resin behavior as in the examples when measuring thermal decomposition, and all decomposition occurred at a high temperature of 400 ° C. or higher.

Figures 2 and 3 are graphs showing the thermal decomposition temperature by thermogravimetric analysis and the glass transition temperature by differential scanning analysis of Examples 1 to 3. The measured thermal decomposition temperature was 325°C for Example 1, 314°C for Example 2, and 305°C for Example 3, and the glass transition temperature was 14°C for Example 1 and 10°C for Example 2. In Example 3, similar values were confirmed at 17°C regardless of the presence of a catalyst.

Figure 4 shows the results of the viscoelastic properties of the measured polyurethane samples, and Examples 1 to 3 can promote carbamate exchange by steric hindrance by introducing a bulky tert-butyl group into a diol monomer containing a hydroxy group. . Therefore, unlike Comparative Example 1, which is a conventional thermosetting polyurethane sample, it was confirmed that Examples 1 and 2 showed thermoplastic properties at about 150 ° C. and Example 3 at about 75 ° C. This is due to the diol containing a hydroxy group. This indicates that it is possible to produce thermosetting polyurethane that can self-heal/recycle above a certain temperature depending on the monomer.

Figure 6 is a graph analyzing the rheological properties of the self-healing thermosetting polyurethane resin of Example 1 using a rheometer, and it can be seen that the complex viscosity of the material decreases as the temperature increases.

Figure 7 is a graph showing complex viscosity results according to temperature and time of the polyurethane sample of Example 1. The polyurethane sample of Example 1 can promote carbamate exchange by steric hindrance by containing a bulky tert-butyl group in a diol monomer containing a hydroxy group. That is, in Example 1, it was confirmed that the complex viscosity decreased as the temperature increased. In addition, the maximum and minimum complex viscosity remained constant even after repeated heating and cooling, which also indicates that it is possible to manufacture thermosetting polyurethane with excellent self-healing/recycling efficiency.

Figure 8 is a graph showing the tensile strength test results of the polyurethane sample of Example 1, and similar tensile strength performance was confirmed when repeated measurements were performed three times.

Photographs and performance recovery rates of the remolded polyurethane samples are shown in Figures 9 and 10. In the case of Figure 9, it was confirmed that the thermosetting polyurethane resin of Example 1, which had been modified through a tensile strength test, recovered again.

In addition, Figures 10 (a) and (b) are photographs showing the process of thermosetting the thermosetting polyurethane sample of Example 1 cut into small pieces with scissors and then re-molding it according to the mold shape.

In addition, Figure 10 (d) is a photograph of the tensile test measurement of the remolded sample of Example 1, and as shown in Figure 11, the recovery rate of more than 90% in performance such as elongation, tensile strength, and Young's modulus compared to before remolding. showed.

The present invention described above is merely illustrative, and those skilled in the art will appreciate that various modifications and other equivalent embodiments are possible therefrom. Therefore, it will be understood that the present invention is not limited to the forms mentioned in the detailed description above. Therefore, the true scope of technical protection of the present invention should be determined by the technical spirit of the attached patent claims.

Accordingly, the spirit of the present invention should not be limited to the described embodiments, and the scope of the patent claims described below as well as all modifications that are equivalent or equivalent to the scope of this patent claim shall fall within the scope of the spirit of the present invention. .

Claims (24)

A self-healing thermosetting polyurethane resin prepared from a polymerizable composition containing an alcohol compound containing a hindered phenol group, a diol, a polyfunctional isocyanate-based compound, and a crosslinking agent. According to clause 1,
According to one aspect of the present invention, the hindered phenol group is represented by the following structure, a self-healing thermosetting polyurethane resin.
[structure]

(In the above structure, A is hydrogen, a linear or branched hydrocarbyl, and B is a linear or branched hydrocarbyl.) According to clause 1,
The alcohol compound containing the hindered phenol group is a self-healing thermosetting polyurethane resin represented by Formula 1 or Formula 2 below.
[Formula 1]

[Formula 2]

In Formula 1, R ₁ and R ₃ is independently hydrogen, C ₁ to C ₂₀ alkyl, C ₃ -C ₂₀ cycloalkyl, C ₆ -C ₂₀ aryl and halogen, R ₂ and R ₄ is independently C ₁ to C ₂₀ alkyl, C ₃ -C ₂₀ cycloalkyl, C ₆ -C ₂₀ aryl and halogen, n is an integer from 1 to 100,
In Formula 2, R ₅ and R ₇ are independently hydrogen, C ₁ to C ₂₀ alkyl, C ₃ -C ₂₀ cycloalkyl, C ₆ -C ₂₀ aryl, and halogen, and R ₆ and R ₈ are independently C ₁ to C ₂₀ alkyl, C ₃ -C ₂₀ cycloalkyl, C ₆ -C ₂₀ aryl and halogen, and n is an integer from 1 to 100. According to clause 3,
The alcohol compound containing the hindered phenol group is a self-healing thermosetting polyurethane resin represented by the following formula (2).
[Formula 2]

In Formula 2, R ₅ and R ₇ are independently hydrogen, C ₁ to C ₂₀ linear or branched alkyl, R ₆ and R ₇ are independently C ₁ to C ₂₀ linear or branched alkyl, and n is It is an integer from 1 to 50. According to clause 4,
The alcohol compound containing a hindered phenol group is any one or two or more of the alcohol compounds containing a hindered phenol group represented by the following formulas 3 to 6, a self-healing thermosetting polyurethane resin.
[Formula 3]

[Formula 4]

[Formula 5]

[Formula 6]
According to clause 4,
In Formula 2, at least one of R ₅ to R ₈ is a C ₃ to C ₂₀ branched alkyl self-healing thermosetting polyurethane resin. According to clause 4,
The alcohol compound containing a hindered phenol group is any one or two or more of the alcohol compounds containing a hindered phenol group represented by the following formulas 3 to 4, a self-healing thermosetting polyurethane resin.
[Formula 3]

[Formula 4]

delete According to clause 1,
The diol is a self-healing thermosetting polyurethane resin, wherein the diol is any one or two or more selected from polyethylene glycol, polypropylene glycol, polytetramethylene ether glycol, polydecalactone diol, and polycarbonate diol. According to clause 1,
The polyfunctional isocyanate-based compound is a self-healing thermosetting polyurethane resin that is an aliphatic or aromatic isocyanate-based compound containing two isocyanate functional groups. According to clause 1,
The multifunctional isocyanate compound is a self-healing thermosetting polyurethane resin having a molecular weight of 84 to 700 g/mol. According to clause 1,
The cross-linking agent is a self-healing thermosetting polyurethane resin, which is a polyol containing three or more hydroxy groups or an isocyanate-based compound containing three or more isocyanate groups. According to clause 12,
A self-healing thermosetting polyurethane resin wherein the crosslinking agent is one or more crosslinking agents selected from triol and tetraol. According to clause 1,
The polymerizable composition is a self-healing thermosetting poly containing 1 to 100 parts by weight of an alcohol compound containing a hindered phenol group, 1 to 100 parts by weight of a polyfunctional isocyanate compound, and 0.1 to 50 parts by weight of a crosslinking agent, based on 100 parts by weight of diol. Urethane resin. According to clause 12,
an isocyanate functional group of the polyfunctional isocyanate compound included in the polymerizable composition; and the alcohol compound containing the hindered phenol group, the hydroxy functional group of the polyol and the cross-linking agent; a self-healing thermosetting polyurethane resin satisfying an equivalence ratio of 1:0.5 to 1. According to clause 1,
The polymerizable composition is a self-healing thermosetting polyurethane resin further comprising a tin-based catalyst. According to clause 1,
The self-healing thermosetting polyurethane resin is a self-healing thermosetting polyurethane resin that self-heals through carbamate exchange at or below the melting temperature. According to clause 17,
The self-healing thermosetting polyurethane resin is a self-healing thermosetting polyurethane resin that self-heals through carbamate exchange at temperatures below 150°C. According to clause 1,
The tensile strength of the self-healing thermosetting polyurethane resin satisfies the following equation 1.
[Equation 1]
TSr/TSi ≥ 0.7
(In Equation 1, TSr is the tensile strength measured after remolding the self-healing thermosetting polyurethane resin at a temperature of 150 ℃ or higher and a pressure of 60 bar or lower, and TSi is the initial tensile strength of the self-healing thermosetting polyurethane resin. It is a robbery.) A self-healing method using any one of the self-healing thermosetting polyurethane resins selected from claims 1 to 7 and 9 to 19,
The self-healing thermosetting polyurethane resin is manufactured from a polymerizable composition containing an alcohol compound containing a hindered phenol group, a diol, a polyfunctional isocyanate-based compound, and a crosslinking agent,
The self-healing method is performed by controlling the self-healing temperature by controlling the degree of steric hindrance of the alcohol compound containing a hindered phenol group. Preparing a mixed solution by dissolving diol in an organic solvent;
Preparing a polymerizable composition containing an alcohol compound containing a hindered phenol group, a polyfunctional isocyanate-based compound, and a crosslinking agent in the mixed solution; and
A method for producing a self-healing thermosetting polyurethane resin, comprising the step of thermosetting the polymerizable composition to produce a self-healing thermosetting polyurethane resin. According to clause 21,
The thermal curing is divided into a first curing step and a second curing step and proceeds sequentially,
A method for producing a self-healing thermosetting polyurethane resin, wherein the first curing step is cured at room temperature, and the second curing step is performed at 60 to 150 ° C. Preparing a self-healing thermosetting polyurethane resin by the manufacturing method according to claim 21; and re-molding the self-healing thermosetting polyurethane resin. According to clause 23,
A method of recycling a self-healing thermosetting polyurethane resin wherein the remolding temperature is 100 to 200°C.