Method for decomposing polyurethane acrylic resin material

Abstract

To provide a method for decomposing a polyurethane acrylic resin material.SOLUTION: A method for decomposing a polyurethane acrylic resin material performs a decomposition step of providing a polyurethane acrylic resin material having a carbon-carbon double bond, decomposing the polyurethane acrylic resin material with a decomposable compound, and producing a decomposition product, wherein the decomposition product contains an aromatic amine compound and ureido diol. A method for decomposing a polyurethane acrylic resin material performs a mixing step of providing a polyurethane acrylic resin material, providing a decomposition liquid containing at least a decomposable compound containing at least a reactive NH group or NH2 group or a reactive OH group, mixing the polyurethane acrylic resin material with the decomposition liquid and producing a decomposition mixture, and performs a decomposition step of maintaining the decomposition mixture at a decomposition temperature and decomposing the polyurethane acrylic resin material.SELECTED DRAWING: Figure 1

Description

[Technical Field]

[0001] The present invention relates to a method for decomposing polyurethane materials, and more particularly to a method for decomposing materials containing a network crosslinked polyurethane acrylic resin. [Background technology]

[0002] Polyurethane acrylic resins have a wide design range, allowing their rigidity and flexibility to be adjusted according to needs, and their molecular structure offers advantages such as good corrosion resistance, good abrasion resistance, good adhesion, good heat resistance, good mechanical properties, and good wettability with various fibers, making them suitable for the structural design of composite materials. However, because of these excellent properties, these composite materials are difficult to decompose and recover, ultimately causing problems such as a shortage of landfill sites and environmental pollution, making the decomposition and recovery of waste composite materials an important issue.

[0003] Polyurethane-acrylic resin composite materials are difficult to recover by melting or dissolving them because the polyurethane-acrylic resin is in a three-dimensional network-like crosslinked state. Conventional techniques have limited recovery to methods such as burial or incineration, which require significant amounts of energy and time and are expensive, and decomposition recovery technology is lacking. However, in the future, these two disposal methods, burial and incineration, will likely become impossible. Therefore, the only way to recover composite materials and achieve the goal of waste reduction is to develop a method that allows the resin to be decomposed.

[0004] Therefore, how to find a suitable decomposition solution to decompose polyurethane acrylic resin in order to achieve the purpose of recovery has become a goal of efforts by those skilled in the art. Summary of the Invention

[0005] One object of the present invention is to provide a method for decomposing polyurethane-acrylic resin materials by thermal decomposition using a decomposition solution containing reactive NH groups / NH groups and OH groups, in order to achieve the purpose of recovery and reuse.

[0006] Another object of the present invention is to provide a polyurethane acrylic resin, its composition and a method for preparing the same, which is prepared by reacting isocyanate with polyol to form a polyurethane acrylate and then adding a diluent monomer to synthesize a decomposable polyurethane acrylic resin.

[0007] One embodiment of the present invention provides a method for decomposing a polyurethane acrylic resin material, including the steps of: providing a polyurethane acrylic resin material obtained by curing a polyurethane acrylic resin; providing a decomposition liquid containing at least a decomposable compound having at least a reactive NH group / NH group and a reactive OH group; mixing the polyurethane acrylic resin material with the decomposition liquid to form a decomposition mixture; and heating the decomposition mixture to a decomposition temperature and maintaining the decomposition time to decompose the polyurethane acrylic resin material.

[0008] According to the method for decomposing a polyurethane acrylic resin material, the polyurethane acrylic resin material may be a cured polyurethane acrylic resin product or a composite material containing a cured polyurethane acrylic resin product.

[0009] According to the method for decomposing a polyurethane acrylic resin material, the composite material containing a cured polyurethane acrylic resin may contain polyurethane acrylic resin and fibers.

[0010] According to the method for decomposing polyurethane acrylic resin material, the fibers may be glass fibers, carbon fibers, polyamide fibers, or a combination thereof.

[0011] According to the method for decomposing a polyurethane acrylic resin material, the decomposable compound may have a structure shown in formula (i).

number

[0012] According to the method for decomposing a polyurethane acrylic resin material, the decomposition temperature may be from 135° C. to the boiling point of the decomposition liquid.

[0013] According to the method for decomposing a polyurethane acrylic resin material, the decomposition time may be 2 to 24 hours.

[0014] According to the method for decomposing a polyurethane acrylic resin material, 40% or more of the total weight of the polyurethane acrylic resin may be oligomers.

[0015] According to the method for decomposing a polyurethane acrylic resin material, the oligomer may have a structure shown in formula (I).

number

[0016] According to the method for decomposing a polyurethane acrylic resin material, the production of a polyurethane acrylic resin may include a polyurethane polymerization step of mixing an isocyanate compound, an inhibitor, and a catalyst with a diluted monomer, and raising the temperature to a first temperature to obtain a first mixture, adding a polyol compound to the first mixture, and reacting while maintaining the first temperature to obtain a second mixture, and a polyurethane acrylate step of adding a hydroxy-containing (meth)acrylate compound to the second mixture, and reacting while maintaining the first temperature to obtain a polyurethane acrylic resin.

[0017] According to the method for decomposing a polyurethane-acrylic resin material, the preparation of the polyurethane-acrylic resin may further include a dilution step of reacting the second mixture containing the hydroxy-containing (meth)acrylate compound at a first temperature, and then lowering the temperature and adding a diluent monomer to obtain the polyurethane-acrylic resin.

[0018] According to the method for decomposing a polyurethane acrylic resin material, the isocyanate compound may be a difunctional or polyfunctional isocyanate compound.

[0019] According to the method for decomposing a polyurethane acrylic resin material, the polyurethane acrylic resin may have an oligomer shown in formula (I).

number

[0020] According to the method for decomposing a polyurethane acrylic resin material, the equivalent ratio of the NCO group of the isocyanate compound to the OH group of the polyol compound may be 1.5:1 to 10:1.

[0021] According to the method for decomposing a polyurethane acrylic resin material, the equivalent ratio of the OH groups of the hydroxy-containing (meth)acrylate compound to the NCO groups of the isocyanate compound remaining after the reaction may be 1:1 to 1.05:1.

[0022] Another embodiment of the present invention provides a composition for producing a polyurethane acrylic resin, comprising an isocyanate compound, a polyol compound, a hydroxy-containing (meth)acrylate compound, and a diluent monomer.

[0023] Another embodiment of the present invention provides a method for producing a polyurethane acrylic resin, including a polyurethane polymerization step of mixing an isocyanate compound, an inhibitor, and a catalyst with a diluent monomer, and raising the temperature to a first temperature to obtain a first mixture, adding a polyol compound to the first mixture, and conducting a reaction while maintaining the first temperature to obtain a second mixture; a polyurethane acrylate step of adding a hydroxy-containing (meth)acrylate compound to the second mixture, and conducting a reaction while maintaining the first temperature to obtain a third mixture; and a dilution step of lowering the temperature of the third mixture, adding a diluent monomer, and obtaining a polyurethane acrylic resin.

[0024] A further embodiment of the present invention includes an oligomer according to formula (I):

number

[0025] Therefore, in the method for decomposing polyurethane acrylic resin materials of the present invention, a decomposition liquid containing mainly reactive NH groups / NH groups and OH groups is selected, the polyurethane acrylic resin material is decomposed by heating, and the decomposition liquid is separated by vacuum distillation so as to be repeatedly reused. [Brief explanation of the drawings]

[0026] To make the above and other objects, features, advantages and embodiments of the present invention more clear and understandable, the accompanying drawings are described below. [Figure 1] 1 is a step flow chart illustrating a method for decomposing a polyurethane acrylic resin material according to one embodiment of the present invention. [Figure 2] 2 is a step flow chart illustrating a method for making a polyurethane acrylic resin according to another embodiment of the present invention. [Figure 3] 2 is a step flowchart illustrating a method for manufacturing a polyurethane acrylic resin according to another embodiment of the present invention. DETAILED DESCRIPTION OF THE INVENTION

[0027] The following describes in more detail various embodiments of the present invention. However, these embodiments may be applications of various inventive concepts and may be specifically implemented within various specific scopes. The specific embodiments are for illustrative purposes only and are not intended to limit the scope of the disclosure.

[0028] <Method for decomposing polyurethane acrylic resin materials>

[0029] Please refer to Figure 1. It shows a step flowchart of a method 100 for decomposing polyurethane acrylic resin material according to one embodiment of the present invention. In Figure 1, the method 100 for decomposing polyurethane acrylic resin material includes steps 110, 120, 130, and 140.

[0030] Step 110 is a step of curing a polyurethane-acrylic resin to provide a polyurethane-acrylic resin material. Specifically, the polyurethane-acrylic resin material of the present invention may be a cured polyurethane-acrylic resin product or a composite material containing the cured polyurethane-acrylic resin product. The cured polyurethane-acrylic resin product can be cured at room temperature or at an elevated temperature with the addition of a known accelerator and free radical initiator to form a network-like crosslinked cured product. The composite material containing the cured polyurethane-acrylic resin product is formed by impregnating the polyurethane-acrylic resin with fibers at room temperature or at an elevated temperature. The fibers may be, but are not limited to, glass fibers, carbon fibers, polyamide fibers, or combinations thereof.

[0031] Step 120 is a step of providing a decomposition solution containing at least a decomposable compound having at least a reactive NH / NH group and a reactive OH group. Specifically, the reactive NH / NH group and the reactive OH group are functional groups that can react with the polyurethane acrylic resin, allowing ammonolysis and alcoholysis to be carried out without damaging the fibers in the composite material. Specifically, the decomposable compound may have a structure shown in formula (i):

number

[0032] Step 130 is a mixing step in which the polyurethane acrylic resin material and the decomposition liquid are mixed to form a decomposition mixture.

[0033] Step 140 is a heating step in which the decomposition mixture is heated to a decomposition temperature and maintained for a decomposition time to decompose the polyurethane acrylic resin material, the decomposition temperature may be from 135°C to the boiling point temperature of the decomposition liquid, and the decomposition time may be from 2 hours to 24 hours.

[0034] Thus, the present invention achieves efficient decomposition by reacting a network-shaped cross-linked polyurethane acrylic resin material with a decomposition solution containing at least reactive NH / NH2 groups and reactive OH groups through ammonolysis and alcoholysis, and then increasing the temperature. The maximum decomposition temperature can be the boiling point of the decomposition solution, and excess decomposition solution can be used as a solvent during the decomposition process to dilute and suspend the fibers. After decomposition is complete, volatile substances can be separated by vacuum distillation. This volatile substance is the decomposition solution containing reactive NH / NH2 groups and OH groups, and can be reused repeatedly. Furthermore, when a composite material containing a cured polyurethane acrylic resin is decomposed, the polyurethane acrylic resin is decomposed and removed, resulting in recovered fibers free of plastic, thereby realizing a recycling mechanism that separates the fibers from the organic materials.

[0035] According to the method 100 for decomposing a polyurethane acrylic resin material of the present invention, 40% or more of the total weight of the polyurethane acrylic resin is an oligomer, and has the structure shown in formula (I).

number

[0036] According to the method 100 for decomposing a polyurethane acrylic resin material of the present invention, the production of the polyurethane acrylic resin may refer to the following description of Fig. 2. Fig. 2 shows a step flow chart of a method 200 for producing a polyurethane acrylic resin according to another embodiment of the present invention. In Fig. 2, the method 200 for producing a polyurethane acrylic resin includes step 210 and step 220.

[0037] Step 210 is a polyurethane polymerization step in which an isocyanate compound, an inhibitor, and a catalyst are mixed with diluted monomer, and the mixture is heated to a first temperature to obtain a first mixture, and a polyol compound is added to the first mixture, and the reaction is carried out while maintaining the first temperature to obtain a second mixture.

[0038] Step 220 is a polyurethane acrylate step in which a hydroxy-containing (meth)acrylate compound is added to the second mixture and reacted while maintaining the first temperature to obtain a polyurethane acrylic resin.

[0039] The isocyanate compound may be a difunctional or polyfunctional isocyanate compound. The difunctional or polyfunctional isocyanate compound may be an aromatic ring isocyanate, and the aromatic ring isocyanate may be tolylene diisocyanate, polymethylene phenyl isocyanate, diphenylmethane diisocyanate, or a combination thereof. Specifically, the isocyanate compound may be one or more of MR200 (purchased from Dongcao), PM200 (purchased from Wanhua), M20S (purchased from BASF), 44V20 (purchased from Covestro), 5005 (purchased from Huntsman), NM (purchased from Dongcao), and MDI-50 (purchased from Wanhua), but is not limited thereto.

[0040] The inhibitor is an inhibitor that has been added to conventional free radical curing resins to ensure the storage stability (stability) of the resin, and an appropriate inhibitor may be selected from well-known inhibitors and added as needed, but a description thereof will be omitted here.

[0041] The catalyst may be organotin, organobismuth, or organozinc, and the amount of catalyst added may be 50 ppm to 200 ppm of the total content of the polyurethane acrylic resin.

[0042] The diluent monomer is a free radical curable diluent monomer and may be methyl (meth)acrylate, ethyl (meth)acrylate, hydroxyethyl (meth)acrylate, hydroxypropyl (meth)acrylate, isobornyl (meth)acrylate, (methyl)cyclohexyl acrylate, tetrahydrofuran (meth)acrylate, styrene, methylstyrene, vinyltoluene, or a combination thereof, and the first temperature may be 40°C to 80°C, preferably 50°C to 70°C.

[0043] The polyol compound may be a difunctional or multifunctional polyol compound, which may be polyoxyethylene ether, polyoxypropylene ether, polytetrahydrofuran, or a combination thereof. The number average molecular weight of the polyol compound is less than 2000. If the number average molecular weight of the polyol compound exceeds 2000, it is difficult to meet the requirements of high-rigidity composite materials.

[0044] The hydroxy-containing (meth)acrylate compound may be hydroxyethyl methacrylate (2-HEMA), hydroxyethyl acrylate (2-HEA), hydroxypropyl methacrylate (2-HPMA), hydroxypropyl acrylate (2-HPA), or a combination thereof.

[0045] The equivalent ratio of the NCO group of the isocyanate compound to the OH group of the polyol compound may be 1.5:1 to 10:1. If the NCO group / OH group ratio is less than 1.5, the polymerization molecular weight will be high and rigidity will be insufficient. If the NCO group / OH group ratio exceeds 10, the rigidity after curing will be too high and the decomposition efficiency will be low. Furthermore, in step 210, the NCO group of the isocyanate compound will remain, and the hydroxy-containing (meth)acrylate compound in step 220 will be able to react with it. Therefore, the equivalent ratio of the OH group of the hydroxy-containing (meth)acrylate compound to the NCO group of the isocyanate compound remaining after the reaction is 1:1 to 1.05:1.

[0046] The polyurethane acrylic resin contains an oligomer represented by formula (I). The oligomer has been described above, and therefore further description will be omitted here. Specifically, the polyurethane acrylic resin composition contains an isocyanate compound, a polyol compound, a hydroxy-containing (meth)acrylate compound, and a diluent monomer. The oligomer is synthesized from the isocyanate compound, the polyol compound, and the hydroxy-containing (meth)acrylate compound.

[0047] According to the method 100 for decomposing a polyurethane acrylic resin material of the present invention, the production of the polyurethane acrylic resin may refer to the following description of FIG. 3. FIG. 3 shows a step flow chart of a method 300 for producing a polyurethane acrylic resin according to another embodiment of the present invention. In FIG. 3, the method 300 for producing a polyurethane acrylic resin material includes steps 310, 320, and 330.

[0048] For details of steps 310 and 320, please refer to steps 210 and 220 above. Further explanation is omitted here. Specifically, step 330 is a dilution step in which the second mixture containing the hydroxy-containing (meth)acrylate compound is reacted at a first temperature (i.e., the third mixture), and then the temperature is lowered and a diluent monomer is added to obtain a polyurethane-acrylic resin. Specifically, step 330 relates to adjusting the working viscosity. The viscosity of the vacuum infusion resin is most preferably 100 cps to 250 cps, and the viscosity of the hand lay-up resin is most preferably 300 cps to 450 cps. Adding an appropriate amount of diluent monomer in step 330 controls the viscosity of the polyurethane-acrylic resin, thereby obtaining a polyurethane-acrylic resin suitable for subsequent applications of the polyurethane-acrylic resin material. The aforementioned applications refer to the manufacture of products using processes such as hand lay-up molding, compression molding, prepreg molding, pultrusion molding, fiber winding, resin transfer molding, and vacuum infusion molding. For details about the diluent monomer, please refer to the above, and further explanation is omitted here.

[0049] In addition, the dilution step in the polyurethane acrylic resin manufacturing method 300 of the present invention is determined according to the viscosity requirement of the working process. In the polyurethane acrylic resin manufacturing method 200 of the present invention, the polyurethane acrylic resin of the present invention can be obtained after the polyurethane acrylate step.

[0050] Thus, the polyurethane acrylic resin of the present invention is a degradable polyurethane acrylic resin obtained by subjecting a di- or higher functional isocyanate to a polyurethane chain extension reaction with a polyol, end-capping with a hydroxyl-containing acrylate compound, and further diluting with a free-radical curable diluent monomer according to the working viscosity.

[0051] Specifically, the reaction scheme for the preparation of polyurethane acrylic resin of the present invention is shown in Table 1 below, where M is a diluent monomer, which forms a network copolymer structure with the polyurethane acrylic resin after free radical curing.

[0052] [Table 1]

[0053] The decomposition reaction formula of polyurethane acrylic resin is shown in Table 2 below. The structure of polyurethane acrylic resin is presumed to form low molecular weight carbamate, low molecular weight ureido ester, polyol, and polyacrylic acid molecules through alcoholysis and ammonolysis, and the final decomposition products are aromatic amine compounds, oxazolidinone, carbamate alcohol amine, ureido diol, etc. through sustained action. [Table 2]

[0054] In another embodiment, 40% or more of the total weight of the polyurethane acrylic resin in the method for decomposing a polyurethane acrylic resin material of the present invention is an oligomer produced from the composition for producing a polyurethane acrylic resin of the present invention, and the oligomer has a structure represented by, but not limited to, formula (I) of the present invention.

[0055] The polyurethane acrylic resin material of the present invention can be applied to surface coatings, adhesives, 3D printing, or main body structure layers, and by adding fillers such as titanium white powder, silica, calcium carbonate, alumina, aluminum hydroxide, silicon carbide, or combinations thereof according to the function, it can be applied to the manufacture of automobile parts, marine parts, railway vehicle parts, sporting goods parts, aviation parts, wind turbine parts, furniture parts, and building parts.

[0056] The present invention is further illustrated by the following specific examples, so that those skilled in the art can fully utilize and practice the present invention without the need for undue interpretation. These examples are used to explain how to carry out the materials and methods of the present invention, but should not be construed as limiting the scope of the present invention.

[0057] <Synthesis example>

[0058] <Synthesis of polyurethane acrylic resin>

[0059] Synthesis Example 1: 280 g of polymethylene phenyl isocyanate, 0.318 g of 2,5-dihydroxytoluene, and 0.159 g of catalyst (DBTDL) were dispersed in 228 g of methyl methacrylate, mixed uniformly in a reactor, and heated to 45-60°C for preparation. Next, 138.9 g of polypropylene glycol (PPG400) was slowly added dropwise to the reactor for 40-60 minutes, with the temperature controlled below 60°C during the addition. After the addition, the temperature was maintained at 45-60°C for 2-4 hours. Then, 180.8 g of hydroxyethyl methacrylate (2-HEMA) was slowly added dropwise for 40-60 minutes, with the temperature controlled below 60°C during the addition. After the addition, the temperature was maintained at 45-60°C for 2-4 hours. When the NCO value is less than 0.5%, 228 g of methyl methacrylate is added to dilute the mixture, and the polyurethane acrylic resin of Synthesis Example 1 is obtained, with a viscosity of 130 cps.

[0060] Synthesis Example 2: 250 g of polymethylenephenyl isocyanate, 0.317 g of 2,5-dihydroxytoluene, and 0.159 g of catalyst (DBTDL) were dispersed in 227 g of methyl methacrylate, mixed uniformly in a reactor, and heated to 45-60°C for preparation. Next, 186 g of polyethylene glycol (PEG 600) was slowly added dropwise to the reactor over a period of 40-60 minutes, with the temperature controlled below 60°C during the addition period and maintained at 45-60°C for 2-4 hours after the addition. Then, 161.4 g of hydroxyethyl methacrylate (2-HEMA) was slowly added dropwise over a period of 40-60 minutes, with the temperature controlled below 60°C during the addition period and maintained at 45-60°C for 2-4 hours after the addition. When the NCO value is less than 0.5%, 227 g of methyl methacrylate is added to dilute the mixture, and the polyurethane acrylic resin of Synthesis Example 2 is obtained, with a viscosity of 320 cps.

[0061] Synthesis Example 3: 330 g of polymethylene phenyl isocyanate, 0.308 g of 2,5-dihydroxytoluene, and 0.179 g of catalyst (DBTDL) were dispersed in 169 g of methyl methacrylate, mixed uniformly in a reactor, and heated to 45-60°C for preparation. Next, 61.4 g of polypropylene glycol (PPG400) was slowly added dropwise to the reactor for 40-60 minutes, with the temperature controlled below 60°C during the addition. After the addition, the temperature was maintained at 45-60°C for 2-4 hours. Then, 293.6 g of hydroxyethyl methacrylate (2-HEMA) was slowly added dropwise for 40-60 minutes, with the temperature controlled below 60°C during the addition. After the addition, the temperature was maintained at 45-60°C for 2-4 hours. When the NCO value was less than 0.5%, 169 g of styrene was added to dilute the mixture, and a polyurethane acrylic resin of Synthesis Example 3 was obtained, with a viscosity of 300 cps.

[0062] Synthesis Example 4: 270 g of a mixture of 2,4-diphenylmethane diisocyanate and 4,4'-diphenylmethane diisocyanate, 0.287 g of 2,5-dihydroxytoluene, and 0.143 g of catalyst (DBTDL) were dispersed in 167 g of methyl methacrylate, mixed uniformly in a reactor, and heated to 45-60°C for preparation. Next, 143.6 g of polypropylene glycol (PPG400) was slowly added dropwise to the reactor for 40-60 minutes, with the temperature controlled below 60°C during the addition. After the addition was completed, the temperature was maintained at 45-60°C for 2-4 hours. Then, 206.7 g of hydroxypropyl methacrylate (2-HPMA) is slowly added dropwise for 40 to 60 minutes. The temperature is controlled to 60°C or less during the addition, and after the addition is completed, the temperature is maintained at 45 to 60°C for 2 to 4 hours. When the NCO value is less than 0.5%, 207 g of methyl methacrylate is added to dilute the mixture, and the polyurethane acrylic resin of Synthesis Example 4 is obtained, with a viscosity of 150 cps.

[0063] Synthesis Example 5: 150 g of polymethylene phenyl isocyanate, 0.309 g of 2,5-dihydroxytoluene, and 0.181 g of catalyst (DBTDL) were dispersed in 412 g of methyl methacrylate, mixed uniformly in a reactor, and heated to 45-60°C for preparation. Next, 372.0 g of polypropylene glycol (PPG2000) was slowly added dropwise to the reactor over a period of 40-60 minutes, with the temperature controlled below 60°C during the addition. After the addition, the temperature was maintained at 45-60°C for 2-4 hours. Then, 96.8 g of hydroxyethyl methacrylate (2-HEMA) was slowly added dropwise over a period of 40-60 minutes, with the temperature controlled below 60°C during the addition. After the addition, the temperature was maintained at 45-60°C for 2-4 hours. When the NCO value is less than 0.5%, the polyurethane acrylic resin of Synthesis Example 5 is obtained, and its viscosity is 400 cps.

[0064] <Production of polyurethane acrylic resin material>

[0065] The polyurethane acrylic resin material may be a cured polyurethane acrylic resin or a composite material containing the cured polyurethane acrylic resin. Specifically, cobalt isooctanoate (0.1% to 0.2%) and methyl ethyl ketone peroxide (1 to 2%) are added to the polyurethane acrylic resins of Synthesis Examples 1 to 5, and the mixture is cured at room temperature for 24 hours and then baked at 105°C for 2 hours to obtain the cured polyurethane acrylic resins of Synthesis Examples 6 to 10, respectively. Alternatively, depending on the operational needs of different processes, the polyurethane acrylic resin curing system can be adjusted to an appropriate gel time, and fiber impregnation molding can be performed at room temperature, followed by baking at 105°C for 2 hours to obtain a cured composite material containing fiber.

[0066] <Examples / Comparative Examples>

[0067] Example 1: 5 g of the cured polyurethane acrylic resin of Synthesis Example 6 and 2-aminoethanol were placed in a 1:5 weight ratio in a round-bottom flask equipped with a snake-shaped condenser, and the mixture was maintained at 135°C for 10 hours to obtain a clear solution, which indicates that the decomposition can be carried out smoothly.

[0068] Example 2: 5 g of the cured polyurethane acrylic resin of Synthesis Example 6 and 2-aminoethoxyethanol were placed in a round-bottom flask equipped with a snake-shaped condenser in a weight ratio of 1:5, and the mixture was maintained at 135°C for 24 hours to obtain a clear solution, which indicates that the decomposition can be carried out smoothly.

[0069] Comparative Example 1: 5 g of the cured polyurethane acrylic resin of Synthesis Example 6 and ethylene glycol were placed in a 1:5 weight ratio in a round-bottom flask equipped with a snake-shaped condenser and maintained at 135°C for 24 hours. As a result, some of the cured resin was not completely dissolved, indicating low decomposition efficiency.

[0070] Comparative Example 2: 5 g of the cured polyurethane acrylic resin of Synthesis Example 6 and triethylenetetramine were placed in a 1:5 weight ratio in a round-bottom flask equipped with a snake-shaped condenser, and the temperature was maintained at 135°C for 24 hours. As a result, some of the cured resin was not completely dissolved, indicating low decomposition efficiency.

[0071] The types of resin, types of cured products, types of decomposition liquids, decomposition times (h), and decomposition states for Examples 1, 2, Comparative Examples 1, and 2 are shown in Table 3 below. [Table 3]

[0072] As can be seen from the results in Table 3 above, in Examples 1 and 2, by selecting a decomposition liquid containing reactive NH2 groups and OH groups, the polyurethane acrylic resin can be reliably decomposed and a clear solution can be obtained.

[0073] Example 3: 5 g of the cured polyurethane acrylic resin of Synthesis Example 7 and 2-aminoethanol were placed in a 1:5 weight ratio in a round-bottom flask equipped with a snake-shaped condenser, and the mixture was maintained at 135°C for 10 hours to obtain a clear solution, which indicates that the decomposition can be carried out smoothly.

[0074] Example 4: 5 g of the cured polyurethane acrylic resin of Synthesis Example 8 and 2-aminoethanol were placed in a 1:5 weight ratio in a round-bottom flask equipped with a snake-shaped condenser, and the mixture was maintained at 135°C for 10 hours to obtain a clear solution, which indicates that the decomposition can be carried out smoothly.

[0075] Example 5: 5 g of the cured polyurethane acrylic resin of Synthesis Example 9 and 2-aminoethanol were placed in a 1:5 weight ratio in a round-bottom flask equipped with a snake-shaped condenser, and the mixture was maintained at 135°C for 10 hours to obtain a clear solution, which indicates that the decomposition can be carried out smoothly.

[0076] Example 6: 5 g of the cured polyurethane acrylic resin of Synthesis Example 10 and 2-aminoethanol were placed in a 1:5 weight ratio in a round-bottom flask equipped with a snake-shaped condenser, and the mixture was maintained at 135°C for 10 hours to obtain a powdery precipitate solution, which showed that the resin could be decomposed smoothly.

[0077] The types of resin, types of cured products, decomposition times (h), and decomposition states for Examples 3 to 6 are shown in Table 4 below. [Table 4]

[0078] Example 7: The glass fiber in Synthesis Example 1 is vacuum-infused to control the weight fiber content to 68%-75%. After complete hardening, it is cut into appropriate sizes and mixed with 2-aminoethanol in a weight ratio of 1:5, placed in a round-bottom flask equipped with a snake-shaped condenser, and maintained at 150°C for 2 hours to obtain a solution in which the fiber and polyurethane acrylic resin are separated. After washing the fiber with ethanol / water, the fiber can be easily recovered.

[0079] Example 8: The carbon fiber in Synthesis Example 1 is vacuum-infused to control its weight fiber content to 50%-55%. After complete curing, it is cut into appropriate sizes and mixed with 2-aminoethanol in a weight ratio of 1:5, placed in a round-bottom flask equipped with a snake-shaped condenser, and maintained at 150°C for 2 hours to obtain a solution in which the fiber and polyurethane acrylic resin are separated. After washing the fiber with ethanol / water, the fiber can be easily recovered.

[0080] Example 9: The aromatic polyamide fiber in Synthesis Example 1 was vacuum-infused to control its weight fiber content to 50%-55%. After complete hardening, it was cut to an appropriate size and mixed with 2-aminoethanol in a weight ratio of 1:5, placed in a round-bottom flask equipped with a snake-shaped condenser, and maintained at 150°C for 2 hours to obtain a solution in which the fiber and polyurethane acrylic resin separated. After washing the fiber with ethanol / water, the fiber could be easily recovered.

[0081] Example 10: The glass fiber in Synthesis Example 3 is hand-laid up, and its weight fiber content is controlled to 30% to 50%. After it is completely cured, it is cut into an appropriate size and mixed with 2-aminoethanol in a weight ratio of 1:5, placed in a round-bottom flask equipped with a snake-shaped condenser, and maintained at 150°C for 2.5 hours to obtain a solution in which the fiber and polyurethane acrylic resin are separated. After washing the fiber with ethanol / water, the fiber can be easily recovered.

[0082] The resin type, fiber type, decomposition time (h), and decomposition state for Examples 7 to 10 are shown in Table 5 below. [Table 5]

[0083] As can be seen from the results in Table 5 above, after the composite material containing polyurethane acrylic resin and fiber is decomposed by the decomposition liquid containing reactive NH2 groups and OH groups, the polyurethane acrylic resin is decomposed and removed, thereby separating the resin from the fiber and leaving the fiber without any plastic attached, which can achieve the purpose of recovering and reusing the fiber.

[0084] As described above, the present invention uses a decomposition solution containing reactive NH / NH2 groups and OH groups and decomposes polyurethane acrylic resin materials by heating, thereby achieving a highly efficient depolymerization effect, and the decomposition solution after decomposition can be recovered and reused, thereby achieving the purpose of reducing waste.

[0085] Although the present invention has been disclosed above based on the embodiments, it is not intended to limit the present invention, and a person skilled in the art can make various changes and modifications without departing from the spirit and scope of the present invention. Therefore, the scope of protection of the present invention is based on the scope defined in the appended claims. [Explanation of symbols]

[0086] 100 Decomposition method for polyurethane acrylic resin material 200, 300 Manufacturing method of polyurethane acrylic resin 110, 120, 130, 140, 210, 220, 310, 320, 330 steps

Claims

1. providing a polyurethane acrylic resin material having carbon-carbon double bonds; performing a decomposition step in which the polyurethane acrylic resin material is decomposed by a decomposable compound to generate a decomposition product; A method for decomposing a polyurethane acrylic resin material, wherein the decomposition products include an aromatic amine compound and a ureidodiol.

2. Provide a polyurethane acrylic resin material, At least a reactive NH group or NH ２ providing a decomposition liquid containing at least a decomposable compound containing a group or a reactive OH group; performing a mixing step of mixing the polyurethane acrylic resin material with the decomposition liquid to form a decomposition mixture; A method for decomposing a polyurethane acrylic resin material, comprising: performing a decomposition step by maintaining the decomposition mixture at a decomposition temperature to decompose the polyurethane acrylic resin material.

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