A regenerated bis-2-hydroxyethyl terephthalate acrylate oligomer prepared from waste PET depolymerization product and a cured composition comprising the same

Abstract

The present disclosure provides a recycled BHET acrylate oligomer prepared by including a waste PET depolymer comprising recycled bis-2-hydroxyethyl terephthalate (r-BHET), a recycled BHET epoxy adduct prepared by including a bis-terminal epoxy telechelic compound and a tetravalent ammonium salt, and one or more acrylate capping agents selected from (meth)acrylates having hydroxyl groups and (meth)acrylic acids, and a method for preparing the same, and provides a cured composition having commercially viable physical properties comprising the recycled BHET acrylate oligomer.

Description

Technology Field

[0001] The present disclosure provides a recycled BHET acrylate oligomer comprising a waste PET depolymer containing recycled bis-2-hydroxyethyl terephthalate and a method for producing the same, and provides a cured composition that is practically usable comprising the recycled BHET acrylate oligomer. Background Technology

[0002] Plastics are widely used in various industrial and technological fields due to their excellent flexibility, productivity, impact resistance, handling, and moldability; however, because of their low density and, in particular, very low biodegradability, environmental pollution is caused by waste plastics.

[0003] Therefore, in order to solve the environmental pollution problem caused by the aforementioned waste plastics, various technological developments are underway, such as replacing them with eco-friendly materials or developing plastics with improved biodegradability.

[0004] However, the aforementioned eco-friendly materials and biodegradable plastics are expensive to produce, and because their physical properties are inferior to those of the aforementioned conventional virgin plastics, their applications are limited.

[0005] For the reasons mentioned above, among the methods to solve the environmental pollution problems caused by the aforementioned waste plastics, waste plastic recycling technology is attracting attention as it can consume large quantities of waste plastic and fundamentally reduce the production of new plastics.

[0006] Among the aforementioned conventional plastics, PET (polyethylene terephthalate) has excellent durability, processability, and thermal stability, and is used in various fields such as clothing, packaging containers, home appliances, automobiles, and films; therefore, various waste PET recycling technologies have been developed since the past.

[0007] Conventional waste PET recycling technologies can be broadly classified into physical and chemical processes depending on the process method.

[0008] The aforementioned conventional physical waste PET recycling process is a method of manufacturing recycled PET by subjecting waste PET flakes to various impurity removal processes. Compared to the chemical waste PET recycling process, the aforementioned conventional physical waste PET recycling process has the advantage of being simpler.

[0009] However, since the aforementioned conventional physical waste PET recycling process involves waste PET containing various impurities and degradation occurring during the process, the physical properties of recycled PET produced by this process are inevitably inferior compared to virgin PET.

[0010] Therefore, recycled PET produced by the conventional physical waste PET recycling process has inferior physical properties compared to virgin PET, and in particular, since the optical properties of PET are significantly degraded, it is still not at a level to compete with virgin PET.

[0011] Furthermore, while the aforementioned conventional chemical waste PET recycling process has the advantage of producing recycled PET with higher physical properties than the conventional physical waste PET recycling process described above, as mentioned, it inevitably consumes a significant amount of processing time and cost.

[0012] The above conventional chemical waste PET recycling process uses a glycol-based compound and a catalyst on waste PET to depolymerize the waste PET into an oligomer or bis(2-hydroxyethyl)terephthalate.

[0013] Conventional chemical waste PET recycling processes have widely known technologies for using waste PET depolymers, such as bis(2-hydroxyethyl)terephthalate, terephthalic acid diester compounds, and oligomers produced by depolymerizing waste PET, as plasticizers or lubricants. However, technology for using these as monomers to produce recycled resins has not yet been actively developed and has not been commercialized.

[0014] For this reason, conventional waste PET makes it difficult to achieve a uniform degree of depolymerization, so the manufactured waste PET depolymer contains various compounds unevenly. Consequently, the recycled resin produced from the waste PET depolymer is not easy to commercialize due to its uneven physical properties.

[0015] In addition, recycled resins manufactured including conventional waste PET depolymers must have decent physical properties to replace conventional virgin plastics, but since several complex processes must be carried out step by step to achieve decent physical properties, there are still limitations in productivity.

[0016] Therefore, there is a need to develop a new resin using waste PET depolymers that can be used for various applications with only a simple process. The problem to be solved

[0017] The present disclosure provides a resin component of a cured composition having properties suitable for commercialization through a simple process including waste PET depolymerization, and a method for manufacturing the same.

[0018] The present disclosure provides a cured composition having excellent alkali resistance, comprising a resin component prepared including the above-mentioned waste PET depolymer.

[0019] The present disclosure provides a method for manufacturing a resin component capable of preventing high reactivity and self-polymerization characteristics even when the waste PET depolymer contains high impurities. means of solving the problem

[0020] The present disclosure provides a recycled BHET acrylate oligomer prepared by comprising (A) a recycled BHET epoxy adduct prepared by including a waste PET depolymer comprising recycled bis-2-hydroxyethyl terephthalate (r-BHET), a biterminal epoxy telechelic compound, and a tetravalent ammonium salt, and (B) one or more acrylate capping agents selected from (meth)acrylates and (meth)acrylic acids having hydroxyl groups.

[0021] In one embodiment of the present disclosure, the tetravalent ammonium salt may be benzyltriethylammonium chloride (BTEAC).

[0022] In one embodiment of the present disclosure, the waste PET depolymer may contain 80% by weight or more of recycled bis-2-hydroxyethyl terephthalate (r-BHET) based on the total weight.

[0023] In one embodiment of the present disclosure, the regenerated BHET acrylate oligomer may be represented by the following chemical formula 1.

[0024] [Chemical Formula 1]

[0025]

[0026] (In the above chemical formula 1, is a divalent organic group derived from a biterminal epoxy telechelic compound, R1, R2, R3, R4, and R6 are independently hydrogen or C1-C7 alkyl, A1 and A2 are independently single bonds or *-AO-*, wherein A in *-AO-* is a C1-C12 alkylene, a, b, c, and d are independently integers from 1 to 7, and n is a real number of 1 or more.)

[0027] As one embodiment of the present disclosure, in the above formula 1, It may be represented by the following chemical formula 2.

[0028] [Chemical Formula 2]

[0029]

[0030] (In the above chemical formula 2, R7, R8, R9 and R 10 They are independently hydrogen or C1-C7 alkyl, and e1 and e2 are independently integers from 1 to 4.

[0031] In one embodiment of the present disclosure, in Formula 1, R1, R2, R3, R4, and R6 are independently hydrogen, methyl, or ethyl, A1 and A2 are independently a single bond or *-AO-*, in which A is a C1-C4 alkylene, a, b, c, and d are independently integers from 1 to 3, and n may be a real number of 1 or more.

[0032] In one embodiment of the present disclosure, the regenerated BHET acrylate oligomer may be represented by the following chemical formula 3.

[0033] [Chemical Formula 3]

[0034]

[0035] (In the above Chemical Formula 3, n is an integer from 2 to 20.)

[0036] In one embodiment of the present disclosure, the regenerated BHET acrylate oligomer may have a weight-average molecular weight of 1,000 to 10,000 g / mol.

[0037] The present disclosure may provide a regenerated BHET acrylate subject comprising the regenerated BHET acrylate oligomer and diluted monomer described above.

[0038] In one embodiment of the present disclosure, the regenerated BHET acrylate component may comprise 30 to 70 weight percent of a regenerated BHET acrylate oligomer based on the total weight.

[0039] In one embodiment of the present disclosure, the diluted monomer may be one or more selected from α-styrene, vinyl toluene, and acrylic monomers.

[0040] In one embodiment of the present disclosure, the recycled BHET acrylate subject may further comprise one or more additives selected from plasticizers, heat stabilizers, flame retardants, viscosity enhancers, fillers, UV stabilizers, lubricants, antistatic agents, oxidation stabilizers, and polymerization promoters.

[0041] In one embodiment of the present disclosure, the regenerated BHET acrylate subject may further comprise an unreacted two-end epoxy telechelic compound, an unreacted regenerated BHET epoxy adduct, and a residual additive.

[0042] The present disclosure may provide a curing composition comprising the regenerated BHET acrylate base and curing agent described above.

[0043] In one embodiment of the present disclosure, the curing agent may be a pearl oxide-based curing agent.

[0044] In one embodiment of the present disclosure, the curing composition may further comprise a metal salt accelerator.

[0045] In one embodiment of the present disclosure, the cured composition may have a tensile strength of 40 MPa or more and a bending strength of 100 MPa or more, as measured by KS M ISO 527-4, after full curing.

[0046] In one embodiment of the present disclosure, the cured composition may have a weight change rate of 1.0% or less in the alkali resistance measurement measured according to KS F ISO 10406-1 after complete curing.

[0047] The present disclosure may provide a method for producing a recycled BHET acrylate oligomer comprising the steps of: producing a recycled BHET epoxy adduct represented by the following formula 4, comprising a waste PET depolymer containing recycled bis-2-hydroxyethyl terephthalate (r-BHET), a bi-terminal epoxy telechelic compound, and a tetravalent ammonium salt; and producing a recycled BHET acrylate oligomer comprising the product of the step of producing the recycled BHET epoxy adduct and an acrylate capping agent represented by the following formula 5.

[0048] [Chemical Formula 4]

[0049]

[0050] [Chemical Formula 5]

[0051]

[0052] (In the above Chemical Formulas 4 and 5, is a divalent organic group derived from bilateral epoxy telechelic compounds, and R 11 , R 12 , R 13 and R 14 is independently hydrogen or a C1-C7 alkyl, A3 is a single bond or *-AO-*, wherein A is a C1-C7 alkylene, f, g, h, and i are independently integers from 1 to 7, and n is a real number of 1 or more.)

[0053] In one embodiment of the present disclosure, the step of producing the recycled BHET epoxy adduct may involve reacting a waste PET depolymer and a bilateral epoxy telechelic compound in a weight ratio of 1:1 to 1:5.

[0054] In one embodiment of the present disclosure, the step of preparing the recycled BHET epoxy compound may comprise 0.1 to 5 parts by weight of a tetravalent ammonium salt with respect to 100 parts by weight of waste PET depolymer. Effects of the invention

[0055] In one aspect of the present disclosure, the regenerated BHET acrylate oligomer can be manufactured by a very simple method even though a waste PET depolymer containing regenerated bis-2-hydroxyethyl terephthalate (r-BHET) is used.

[0056] In one embodiment of the present disclosure, a curing composition comprising the regenerated BHET acrylate oligomer can produce a cured product having a tensile strength of 40 MPa or more and a bending strength of 100 MPa or more as measured by KS M ISO 527-4, and thus can replace a cured product made with general bisphenol A and bisphenol A epoxy.

[0057] In one embodiment of the present disclosure, the curing composition has excellent alkali resistance with a weight change rate of 1.0% or less in the alkali resistance measurement measured by KS F ISO 10406-1 after complete curing, so it can be used in materials exposed to strong alkali.

[0058] Accordingly, one aspect of the present disclosure allows for the production of a recycled BHET acrylate oligomer using a simple method with waste PET depolymerization, and a cured composition comprising the recycled BHET acrylate oligomer can produce a cured product having excellent durability with excellent chemical resistance and high Barcol hardness, while having decent mechanical strength and decent storage stability, and thus has excellent compatibility, thereby fundamentally solving the problem of environmental pollution caused by waste PET. Brief explanation of the drawing

[0059] Figure 1 shows the results of measuring the components of the waste PET depolymer used in Example 1. Figure 2 shows the GPC measurement results of (a) the pre-reaction mixture of waste PET depolymer and Bisphenol A diglycidyl ether in Example 1, (b) the GPC measurement results of the product containing the recycled BHET acrylate oligomer prepared in Example 1, and (c) the GPC measurement results of the product of Comparative Example 4. Figure 3 shows photographs of the curing compositions prepared in Example 4 and Comparative Examples 6 to 8 after an alkali resistance test. Specific details for implementing the invention

[0060] Unless otherwise defined in this specification, all technical and scientific terms have the same meaning as generally understood by those skilled in the art to which this disclosure pertains.

[0061] The terms used in the description herein are merely for the purpose of effectively describing specific embodiments and are not intended to limit the disclosure.

[0062] The singular form used in this specification is intended to include the plural form unless specifically indicated otherwise in the context.

[0063] Additionally, units used in this specification without special mention are based on weight, for example, the unit of % or ratio is weight %, and temperature means °C unless specifically defined otherwise.

[0064] The numerical ranges used herein include lower and upper limits and all values ​​within the range, increments logically derived from the form and width of the defined range, all of which are limited, and all possible combinations of upper and lower limits of the numerical range defined in different forms. Unless otherwise specifically defined in this specification, values ​​outside the numerical range that may occur due to experimental error or rounding are also included in the defined numerical range.

[0065] Throughout this specification, the terms “comprising,” “having,” “containing,” or “having” any component mean that, unless specifically stated otherwise, other components are not excluded but may be included, and do not exclude elements, materials, or processes not additionally listed.

[0066] The term "divalent organic group" in this specification may refer to an organic structure having two reactive bonding sites capable of forming covalent bonds with other components within a molecular structure. Examples of such a divalent organic group may be a substituted or unsubstituted aliphatic or alicyclic divalent organic group having 1 to 30 carbon atoms, a substituted or unsubstituted aromatic divalent organic group having 6 to 30 carbon atoms, or a substituted or unsubstituted heteroaromatic divalent organic group having 2 to 30 carbon atoms, or at least two of the aliphatic, alicyclic aromatic, and heteroaromatic divalent organic groups connected directly or through a linker.

[0067] The “divalent organic group” in this specification is derived from biterminal epoxy telechelic compounds and may be a structure derived from biterminal epoxy compounds such as non-limiting bisphenol-type epoxy, dicyclopentadiene-type epoxy, trisphenol-type epoxy, naphthol-novolak-type epoxy, phenol-novolak-type epoxy, tert-butyl-catechol-type epoxy, naphthalene-type epoxy, naphthol-type epoxy, anthracene-type epoxy, glycidylamine-type epoxy, glycidyl ester-type epoxy, cresol-novolak-type epoxy, biphenyl-type epoxy, linear aliphatic epoxy, epoxy having a butadiene structure, alicyclic epoxy, heterocyclic epoxy, spiro-ring containing epoxy, cyclohexane-type epoxy, cyclohexanedimethanol-type epoxy, naphthylene ether-type epoxy, trimethylol-type epoxy resin, tetraphenylethane-type epoxy, etc.

[0068] Polyethylene terephthalate (PET) is used in various fields such as clothing, packaging containers, home appliances, automobiles, and films due to its excellent durability, processability, and thermal stability. As such, since PET is used in various technological fields, environmental pollution caused by used waste PET has become an issue.

[0069] Therefore, various waste PET recycling technologies have been developed since the past, and the aforementioned conventional waste PET recycling technologies are broadly classified into physical waste PET recycling and chemical waste PET recycling technologies.

[0070] Conventional physical waste PET recycling technology involves treating waste PET for impurities and reprocessing it to produce recycled PET. While this technology offers the advantage of recycling waste PET through a simple process, the resulting recycled PET exhibits degraded physical properties compared to virgin PET, particularly optical properties. Furthermore, due to high production costs, it remains unable to compete with virgin PET.

[0071] Conventional chemical waste PET recycling technology involves depolymerizing waste PET to reuse the depolymerized product as a lubricant and monomer. While this technology offers the advantages of producing recycled PET with higher physical properties and superior commercial viability compared to the conventional physical waste PET recycling process described above, it has poor economic feasibility due to the inevitable consumption of significant processing time and costs.

[0072] In particular, the above-mentioned conventional chemical waste PET recycling process uses a glycol-based compound and a catalyst to depolymerize waste PET into an oligomer or bis(2-hydroxyethyl)terephthalate. While many technologies have been disclosed for using waste PET depolymers, such as bis(2-hydroxyethyl)terephthalate, terephthalic acid diester compounds, and oligomers produced by depolymerizing waste PET, as plasticizers or lubricants, the technology for using these as monomers to produce recycled resins has not yet been commercialized.

[0073] The first reason why the above-mentioned conventional waste PET depolymers cannot be used as monomers is that the waste PET depolymers have low reactivity, making the repolymerization process into usable monomers or oligomers very complex and resulting in increased production costs.

[0074] In addition, the second reason why conventional waste PET depolymers cannot be used as monomers is that the monomers and oligomers produced by repolymerizing waste PET depolymers still have poor physical properties.

[0075] For the reasons mentioned above, the technology for manufacturing recycled resin using conventional waste PET depolymers has not yet been commercialized because the process is very complex and the physical properties of the produced recycled resin are inferior to those of new resin.

[0076] The inventors of the present disclosure have completed the present disclosure by discovering a curing composition capable of producing a cured product with excellent physical properties by manufacturing an oligomer through a simple manufacturing process to resolve the problem that the waste PET depolymer described above cannot be used as a monomer.

[0077] The present disclosure will be explained below.

[0078] One aspect of the present disclosure may provide a recycled BHET acrylate oligomer prepared by comprising (A) a waste PET depolymer comprising recycled bis-2-hydroxyethyl terephthalate (r-BHET), a biterminal epoxy telechelic compound, and a tetravalent ammonium salt, and (B) one or more acrylate capping agents selected from (meth)acrylates and (meth)acrylic acids having hydroxyl groups.

[0079] Compared to conventional technology, the above recycled BHET acrylate oligomer can be manufactured using only a simple process by including waste PET depolymers, and since a cured composition containing it can have excellent physical properties, it can be used in various technical fields.

[0080] Therefore, the above-mentioned recycled BHET acrylate oligomer solves the technical problem of using it as a monomer for the depolymerization of waste PET, which is still in short supply in the past, and thus can increase the consumption of waste PET, thereby solving the problem of environmental pollution caused by waste PET.

[0081] The present disclosure may provide a subject comprising the regenerated BHET acrylate oligomer and the diluted monomer, and may provide a curing composition comprising the subject and a curing agent.

[0082] As described above, the curing composition can produce a cured product having mechanical properties similar to those of a general bisphenol-based curing composition, and in particular, since it has excellent alkali resistance and high Barcol hardness, it can be applied to technical fields such as construction, machinery, electronics, and automobiles.

[0083] In one embodiment of the present disclosure, the cured composition may have a tensile strength measured according to KS M ISO 527-4 of 40 MPa or more, 45 MPa or more, 50 MPa or more, or 60 MPa or less, and a tensile modulus of 3.0 GPa or more, 3.5 GPa or more, 4.0 GPa or more, or 5.0 GPa or less after full curing.

[0084] A cured product having tensile strength and tensile modulus within the above range can be similar to or superior to a cured product prepared by polymerizing conventional bisphenol A and bisphenol A-based epoxy, and thus can have excellent compatibility.

[0085] In addition, as one embodiment of the present disclosure, the cured composition may have a bending strength measured by KS M ISO 527-4 after complete curing of 100 MPa or more, 110 MPa or more, 120 MPa or more, 130 MPa or more, or 140 MPa or less, and may have high bending strength properties such as a bending modulus of 3.0 GPa or more, 3.5 GPa or more, 4.0 GPa or more, or 5.0 GPa or less, so it may be applicable to a wider variety of technical fields.

[0086] In one embodiment of the present disclosure, the cured composition may have a weight change rate of 1.0% or less, 0.9% or less, 0.8% or less, or 0.5% or less in the alkali resistance measurement measured according to KS F ISO 10406-1 after complete curing.

[0087] As shown in Figure 3 below, the cured product obtained by curing the above curing composition does not show any swelling phenomenon and shows almost no change in appearance even when exposed to an alkaline solution, so it may be used as a material in fields exposed to alkali.

[0088] In addition, since the above-mentioned curing composition exhibits the following curing behavior and the cured product obtained by fully curing it has the following physical properties, it can have superior compatibility compared to conventional curing compositions and cured products prepared including waste PET depolymers, thereby resolving the environmental pollution problem caused by waste PET.

[0089] In one embodiment of the present disclosure, the curing composition has a gelation time of 30 minutes or less at 25°C, a minimum curing time of 40 minutes or less, and a maximum exothermic temperature of 160°C or less, so as the curing composition, it can have excellent workability.

[0090] In one embodiment of the present disclosure, the recycled BHET acrylate main component, excluding the curing agent in the curing composition, has storage stability of 4 hours or more in an environment of 105°C, so long-term storage is easy.

[0091] In one embodiment of the present disclosure, the curing composition is after complete curing , Since the heat distortion temperature measured by KS M ISO 75-2 can be 90°C or higher, 91°C or higher, 92°C or higher, or 95°C or lower, it can be used in materials that require high heat resistance.

[0092] In one embodiment of the present disclosure, the cured composition, after complete curing, has a Barcol hardness measured by KS M 3387 of 30 or more, 35 or more, 40 or more, or 50 or less, so it can be usefully used as a material requiring high surface hardness and high wear resistance resulting therefrom.

[0093] As such, according to one embodiment of the present disclosure, the curing composition has the excellent properties described above and can be usefully applied to various materials, thereby providing excellent compatibility compared to conventional technology and solving the problem of environmental pollution caused by waste PET.

[0094] The following describes in detail the regenerated BHET acrylate oligomer of the present disclosure and the method for manufacturing the same.

[0095] The present disclosure may provide (A) a waste PET depolymer comprising regenerated bis-2-hydroxyethyl terephthalate (r-BHET), a regenerated BHET epoxy adduct prepared by including a biterminal epoxy telechelic compound and a tetravalent ammonium salt, and a regenerated BHET acrylate oligomer prepared by including one or more acrylate capping agents selected from (meth)acrylates and (meth)acrylic acids having hydroxyl groups.

[0096] As described above, the recycled BHET acrylate oligomer can be manufactured very simply compared to conventional technology by reacting a low-reactivity waste PET depolymer with a bilateral end epoxy telechelic compound using a tetravalent ammonium salt as a catalyst to produce a recycled BHET epoxy adduct, and reacting the produced recycled BHET epoxy adduct with an acrylate capping agent.

[0097] In one embodiment of the present disclosure, the regenerated BHET acrylate oligomer may be represented by the following chemical formula 1.

[0098] [Chemical Formula 1]

[0099]

[0100] (In the above chemical formula 1, is a divalent organic group derived from a biterminal epoxy telechelic compound, R1, R2, R3, R4, and R6 are independently hydrogen or C1-C7 alkyl, A1 and A2 are independently single bonds or *-AO-*, wherein A in *-AO-* is a C1-C12 alkylene, a, b, c, and d are independently integers from 1 to 7, and n is a real number of 1 or more.)

[0101] At this time, the above The is a divalent organic group derived from a biterminal epoxy telechelic compound, which may be hydrocarbylene or heterohydrocarbylene, and as a non-limiting example, biterminals of bisphenol-type epoxy resin, dicyclopentadiene-type epoxy resin, trisphenol-type epoxy resin, naphthol-novolak-type epoxy resin, phenol-novolak-type epoxy resin, tert-butyl-catechol-type epoxy resin, naphthalene-type epoxy resin, naphthol-type epoxy resin, anthracene-type epoxy resin, glycidylamine-type epoxy resin, glycidyl ester-type epoxy resin, cresol-novolak-type epoxy resin, biphenyl-type epoxy resin, linear aliphatic epoxy resin, epoxy resin having a butadiene structure, alicyclic epoxy resin, heterocyclic epoxy resin, spiro-ring containing epoxy resin, cyclohexane-type epoxy resin, cyclohexanedimethanol-type epoxy resin, naphthylene ether-type epoxy resin, trimethylol-type epoxy resin, and tetraphenylethane-type epoxy resin, etc. It may be a structure derived from epoxy telechelic compounds, but is not necessarily limited to this.

[0102] Also, in the above chemical formula 1, It may be derived from a bisphenol-type epoxy telechelic compound, and as a non-limiting example, it may be a bisphenol A-type epoxy telechelic compound, a bisphenol F-type epoxy telechelic compound, a bisphenol epoxy telechelic compound or a bisphenol epoxy telechelic compound, but is not necessarily limited thereto.

[0103] As one embodiment of the present disclosure, in the above formula 1, It may be represented by the following chemical formula 2.

[0104] [Chemical Formula 2]

[0105]

[0106] (In the above chemical formula 2, R7, R8, R9 and R 10They are independently hydrogen or C1-C7 alkyl, and e1 and e2 are independently integers from 1 to 4.

[0107] A regenerated BHET acrylate oligomer comprising the structure represented by Chemical Formula 2 above may be preferred as it can provide a curing composition capable of producing a cured product having further improved mechanical properties and excellent alkali resistance, but is not necessarily limited thereto.

[0108] In one embodiment of the present disclosure, the regenerated BHET acrylate oligomer may be represented by the following formula 3, wherein R1, R2, R3, R4, and R6 in Formula 1 described above are independently hydrogen, methyl, or ethyl, A1 and A2 are independently single bonds or *-AO-*, A in *-AO-* is a C1-C4 alkylene, a, b, c, and d are independently integers from 1 to 3, and n may be a real number of 1 or more.

[0109] [Chemical Formula 3]

[0110]

[0111] (In the above Chemical Formula 3, n is an integer from 2 to 20.)

[0112] The regenerated BHET acrylate oligomer represented by the above chemical formula 3 has excellent polymerization reactivity and excellent polymerization processability, and a curing composition containing it can provide a cured product having further improved physical properties, but it is not necessarily limited to this as long as it does not impair the physical properties of the curing composition.

[0113] In one embodiment of the present disclosure, the regenerated BHET acrylate oligomer may have a weight-average molecular weight of 1,000 to 10,000 g / mol, 1,000 to 5,000 g / mol, or 2,000 to 4,000 g / mol.

[0114] A regenerated BHET acrylate oligomer having a weight-average molecular weight within the above range can provide a cured product having excellent physical properties without increasing the viscosity of the cured composition prepared including it.

[0115] In addition, since the regenerated BHET acrylate oligomer having a weight-average molecular weight in the above range may suggest that the regenerated bis-2-hydroxyethyl terephthalate (r-BHET) does not self-polymerize, it may be a property that demonstrates excellent polymerization reactivity.

[0116] In one embodiment of the present disclosure, the regenerated BHET acrylate oligomer may be prepared by a step of preparing a regenerated BHET epoxy adduct represented by the following formula 4, comprising a waste PET depolymer containing regenerated bis-2-hydroxyethyl terephthalate (r-BHET), a bi-terminal epoxy telechelic compound, and a tetravalent ammonium salt, and a step of preparing a regenerated BHET acrylate oligomer comprising the product of the step of preparing the regenerated BHET epoxy adduct and an acrylate capping agent represented by the following formula 5.

[0117] [Chemical Formula 4]

[0118]

[0119] [Chemical Formula 5]

[0120]

[0121] (In the above Chemical Formulas 4 and 5, is a divalent organic group derived from telechelic epoxy compounds, and R 11 , R 12 , R 13 and R 14 is independently hydrogen or a C1-C7 alkyl, A3 is a single bond or *-AO-*, wherein A is a C1-C7 alkylene, f, g, h, and i are independently integers from 1 to 7, and n is a real number of 1 or more.)

[0122] The above recycled BHET acrylate oligomer can be preferred because it can be prepared by a very simple reaction comprising a waste PET depolymer, a bilateral epoxy telechelic compound and a tetravalent ammonium salt to produce a recycled BHET epoxy adduct represented by Chemical Formula 4 described above, and capping the recycled BHET epoxy adduct with an acrylate capping agent represented by Chemical Formula 5.

[0123] In addition, the above-mentioned regenerated BHET acrylate oligomer is preferred because both ends of the acrylate capping agent represented by Chemical Formula 5 described above are capped with acrylate groups, so a curing composition containing it can have excellent curing behavior even at room temperature.

[0124] The regenerated BHET epoxy adduct represented by Chemical Formula 4 and the acrylate capping agent represented by Chemical Formula 5 are materials derived from the regenerated BHET acrylate oligomer structure of Chemical Formula 1 described above, and since they correspond to Chemical Formula 1, a detailed description will be omitted.

[0125] In one embodiment of the present disclosure, the waste PET depolymer may contain recycled bis-2-hydroxyethyl terephthalate (r-BHET) in an amount of 80% or more, 85% or more, 90% or more, less than 100%, 99% or less, or 95% or less with respect to the total weight, in terms of having excellent reactivity, but is not necessarily limited thereto.

[0126] The above method for manufacturing recycled BHET acrylate oligomer may involve applying waste PET depolymerized material containing recycled bis-2-hydroxyethyl terephthalate (r-BHET) within the above range directly to the polymerization reaction, rather than using pure bis-2-hydroxyethyl terephthalate (r-BHET).

[0127] Therefore, since the above method for producing recycled BHET acrylate oligomer uses impure waste PET depolymer, it may be preferred to use a tetravalent ammonium salt as a catalyst in the step of producing recycled BHET epoxy adduct.

[0128] In one embodiment of the present disclosure, the tetravalent ammonium salt may be one or more selected from triethylbenzylammonium salt, tetramethylammonium salt, benzyltriethylammonium salt, alkyltrimethylammonium salt, triphenylmethyltriphenylphosphonium salt, allyltrimethylammonium salt, hexadecyltrimethylammonium bromide and trimethylbenzylammonium salt, and in another embodiment of the present disclosure, it may be benzyltriethylammonium chloride (BTEAC).

[0129] The above-mentioned benzyltriethylammonium chloride (BTEAC) may be preferred as it improves the reactivity of the waste PET depolymers and bi-terminal epoxy telechelic compounds described above, thereby further enhancing the polymerization of recycled BHET epoxy adducts; however, it is not necessarily limited to any material capable of producing recycled BHET epoxy adducts.

[0130] In one embodiment of the present disclosure, the step of preparing the recycled BHET epoxy adduct may comprise 0.1 to 5 parts by weight, 0.5 to 3 parts by weight, or 1 to 3 parts by weight of a tetravalent ammonium salt with respect to 100 parts by weight of waste PET depolymer.

[0131] When the tetravalent ammonium salt is included in the above range, the processability of the recycled BHET epoxy adduct is excellent, and the use of excessive tetravalent ammonium salt can be prevented, and the finally produced recycled BHET acrylate oligomer can have the target molecular weight, which may be preferred, but this is not necessarily limited.

[0132] In one embodiment of the present disclosure, the step of preparing the recycled BHET epoxy adduct involves reacting the waste PET depolymer and the two-end epoxy telechelic compound in a weight ratio of 1:1 to 1:5, 1:2 to 1:5, or 1:2 to 1:4, which may result in excellent reactivity and excellent physical properties of the finally prepared recycled BHET acrylate oligomer, but is not necessarily limited thereto.

[0133] In one aspect of the present disclosure, the method for producing a regenerated BHET acrylate oligomer may include the step of producing a regenerated BHET acrylate oligomer comprising a product containing a regenerated BHET epoxy adduct and an acrylate capping agent, wherein the regenerated BHET epoxy adduct is produced as described above.

[0134] The step of manufacturing the above recycled BHET acrylate oligomer may involve adding an acrylate capping agent in an amount of 100 to 500 parts by weight, 100 to 400 parts by weight, 200 to 400 parts by weight, or 300 to 400 parts by weight with respect to 100 parts by weight of waste PET depolymerized material introduced in the manufacturing step, but this is not necessarily limited as long as it satisfies the acid value of the recycled BHET acrylate oligomer targeted in the present disclosure.

[0135] Therefore, the recycled BHET acrylate oligomer described above may be preferred because it can be manufactured through a simple process even though waste PET depolymerization is used directly as a monomer, and a recycled BHET acrylate main component and a curing composition can be provided including it.

[0136] The regenerated BHET acrylate main component of the present disclosure and the curing agent containing the same will be described in detail below.

[0137] In one aspect of the present disclosure, a regenerated BHET acrylate subject comprising a regenerated BHET acrylate oligomer and a dilute monomer may be provided.

[0138] In this case, the regenerated BHET acrylate oligomer may refer to a product containing the regenerated BHET acrylate oligomer finally produced in the method for producing the regenerated BHET acrylate oligomer described above.

[0139] Accordingly, in one embodiment of the present disclosure, the regenerated BHET acrylate subject may further comprise an unreacted two-end epoxy telechelic compound, an unreacted regenerated BHET epoxy adduct, and a residual additive.

[0140] A recycled BHET acrylate subject containing the above unreacted compounds may be preferred as the cured composition prepared including it can have surprisingly improved curing reactivity and mechanical strength, but it is not necessarily limited to this as long as it does not impair the physical properties of the cured composition being prepared.

[0141] In one embodiment of the present disclosure, the recycled BHET acrylate component may comprise a recycled BHET acrylate oligomer in an amount of 30 to 70 weight%, 40 to 70 weight%, or 50 to 70 weight% with respect to the total weight.

[0142] When a regenerated BHET acrylate oligomer is included in the weight percent of the above range, the curability of the curing composition containing it may be improved, and since the concentration of the diluent monomer included in addition is suitable, it may be preferred to provide a viscosity with excellent workability, but this is not a limitation.

[0143] In one embodiment of the present disclosure, the diluent monomer may be one or more selected from α-styrene, vinyl toluene, and acrylic monomers, and in another embodiment, it may include α-styrene or use α-styrene alone.

[0144] When the above α-styrene is used alone as a diluted monomer, the cured composition containing it may be preferred as it may have improved mechanical strength, alkali resistance, and surface hardness, but this is not necessarily limited.

[0145] The above diluted monomers are not particularly limited as long as they are recognizable by a person skilled in the art, and as a non-limiting example, the acrylate diluted monomer may be one or more selected from methyl (meth)acrylate, ethyl (meth)acrylate, butyl (meth)acrylate, ethylhexyl (meth)acrylate, isooctyl (meth)acrylate, phenol (EO) (meth)acrylate, methoxyethoxyethyl (meth)acrylate, phenylthioethyl (meth)acrylate, isodecyl (meth)acrylate, lauryl (meth)acrylate, cetyl (meth)acrylate, stearyl (meth)acrylate, isobornyl (meth)acrylate, tetrahydrofurfuryl (meth)acrylate, benzyl (meth)acrylate, and cyclohexyl (meth)acrylate, and the like, and the urethane acrylate diluted monomer 2-hydroxyethyl methacrylate (HEMA) and urethane diacrylate (UDA) may be used, glycidyl methacrylate (GMA) may be included as an epoxy-based diluent monomer, and styrene and divinylbenzene may be included as vinyl-based monomers.

[0146] In one embodiment of the present disclosure, the recycled BHET acrylate subject may further comprise one or more additives selected from plasticizers, heat stabilizers, flame retardants, viscosity enhancers, fillers, UV stabilizers, lubricants, antistatic agents, oxidation stabilizers, and polymerization promoters.

[0147] Regenerated BHET acrylate materials further containing the above additives may be preferred as they possess properties corresponding to each industrial field and can improve resistance to external environments such as UV rays, humidity, and temperature; however, this is merely an example and is not necessarily a limitation.

[0148] One aspect of the present disclosure may provide a curing composition comprising the regenerated BHET acrylate base and a curing agent.

[0149] The above curing composition may be preferred when it is based on recycled BHET acrylate, as it possesses excellent storage stability and, as a result of adding a curing agent, can have very excellent curability to the extent that curing is possible even at room temperature.

[0150] In one embodiment of the present disclosure, the curing agent may be a peroxide-based curing agent, and in another embodiment, it may be methyl ethyl ketone peroxide.

[0151] The above-mentioned peroxide-based curing agent may have excellent curing reactivity with the regenerated BHET acrylate oligomer and dilute monomer included in the curing composition, and in particular, Methyl Ethyl Ketone Peroxide may be preferred as it may have even better curing reactivity, but it is not necessarily limited as long as it does not impair the physical properties of the cured product being produced.

[0152] The above-mentioned peroxide-based curing agent may be used without limitation as long as it is a radical-forming substance as recognized by a person skilled in the art, and as a non-limiting example, it may be one or more selected from benzoyl peroxide (BPO), methyl ethyl ketone peroxide (MEKP), diperoxide hexane (DCP), and tertiary butyl peroxybenzoate (TBPB).

[0153] In one embodiment of the present disclosure, the curing composition may further include a metal salt accelerator in terms of uniform curing, improved curing rate, improved heat resistance, and improved chemical resistance.

[0154] The above metal salt promoter may include one or more selected from copper salts, zinc salts, manganese salts, and iron salts, provided that it is recognizable by a person skilled in the art, although it is not particularly limited, or it may be a copper salt.

[0155] Accordingly, the present disclosure can provide a cured composition having properties similar to or different from those of a conventional cured product made by including the recycled BHET acrylate oligomer, by using waste PET depolymers to produce a recycled BHET acrylate oligomer.

[0156] The present disclosure is explained through the following examples. However, the following examples are merely references for the detailed explanation of the present disclosure and are not limited thereto, and the present disclosure may be implemented in various forms. Furthermore, unless otherwise defined, all technical and scientific terms have the same meaning as generally understood by one of the art to which the present disclosure pertains. Additionally, the terms used in the description herein are merely for the purpose of effectively describing specific embodiments and are not intended to limit the present invention.

[0158] [measurement method]

[0159] 1. Measurement of purity of waste PET depolymerization

[0160] Qualitative analysis of trace impurities in waste PET depolymers was performed using a gas chromatography system (GC, Agilent 8890). Quantitative analysis was performed using GC / FID (Agilent 8890), and during quantitative analysis, cyclohexane was used as an internal standard to ensure accurate weight percentage measurements.

[0162] 2. GPC (gel permeation chromatography) measurement

[0163] After dissolving the measurement sample in tetrahydrofuhan (THF), the weight-average molecular weight and polydispersity index were measured using Gel Permeation Chromatography (GPC, Shimadzu, LC-20AD series).

[0165] 3. Gardner viscosity measurement

[0166] A measurement sample (subject) prepared with a solid content of 70% by diluting with styrene monomer was measured using a Gardner bubble viscometer (BYK) in accordance with ASTM D154.

[0168] 4. Acid value measurement

[0169] 1.0 g of the sample to be measured was placed in an Erlenmeyer flask, and 25 ml of M·T solution (a mixture of methanol and toluene in a 3:7 volume ratio) was added to dissolve it. Then, 2 to 3 drops of 1 wt% phenolphthalein indicator were added to the solution, and titration was performed using a 0.1 N KOH solution; the titration was stopped when the color turned red. Subsequently, the acid value was calculated by determining the volume (ml) of the KOH solution used during the titration using the following formula.

[0170] [ceremony]

[0171]

[0173] Synthesis of regenerated BHET acrylate oligomers

[0174] [Example 1]

[0175] (Manufacture of recycled BHET epoxy adducts)

[0176]

[0177] 100 parts by weight of waste PET depolymer (SK Chemicals, ECOREOL®) were introduced into a reactor. As a result of the purity measurement of the waste PET depolymer described above, it was confirmed that the waste PET depolymer contained 93.2 wt% recycled bis-2-hydroxyethyl terephthalate (r-BHET), 0.6 wt% ethylene glycol, and 6.2 wt% high-grade components, as shown in Fig. 1 below. Subsequently, 375 parts by weight of Bisphenol A diglycidyl ether (Bisphenol-A Epoxy, Kukdo Chemical, YD-128) and 2 parts by weight of Benzyltriethylammonium chloride (BTEAC) were added to the reactor relative to 100 parts by weight of the waste PET depolymer, and the mixture was stirred at 160 °C for 4 hours to produce a product containing a recycled BHET epoxy adduct (Compound A).

[0178] (Preparation of Regenerated BHET Acrylate Oligomer)

[0179]

[0180] Afterwards, 102 parts by weight of methacrylic acid, 0.09 parts by weight of toluhydroquinone, 0.3 parts by weight of triphenylstibine, and 1 part by weight of Ancamine k54 were added to 100 parts by weight of waste PET depolymer to the reactor, and the reaction was stopped when the acid value of the reaction product reached 11 mg / g KOH, thereby obtaining a product containing regenerated BHET acrylate oligomer.

[0182] [Example 2]

[0183]

[0184] In the above Example 1, a product containing an epoxy adduct (compound B) and a product containing a regenerated BHET acrylate oligomer were prepared in the same manner as in Example 1, except that 1,4-butanediol diglycidyl ether (BDGE) was used instead of Bisphenol A diglycidyl ether (Bisphenol-A Epoxy, Kukdo Chemical Co., YD-128).

[0185] The results of measuring the product containing the above-mentioned epoxy adduct (compound B) and the product containing the regenerated BHET acrylate oligomer using the measurement method described above are listed in Table 2 below.

[0187] [Example 3]

[0188]

[0189] In the above Example 1, a product containing an epoxy adduct (compound C) and a product containing a regenerated BHET acrylate oligomer were prepared in the same manner as in Example 1, except that 1,4-Cyclohexanedimethanol diglycidyl ether (CHDM-DGE) was used instead of Bisphenol A diglycidyl ether (Bisphenol-A Epoxy, Kukdo Chemical Co., YD-128).

[0190] The results of measuring the product containing the above-mentioned epoxy adduct (compound C) and the product containing the regenerated BHET acrylate oligomer using the measurement method described above are listed in Table 2 below.

[0192] [Comparative Example 1]

[0193] In the above Example 1, the same procedure was carried out except that, for 100 parts by weight of waste PET depolymer, 0.9 parts by weight of Triphenylphosphine (TPP) was added instead of 2 parts by weight of Benzyltriethylammonium chloride (BTEAC), and a product containing an epoxy adduct and a product containing a recycled BHET acrylate oligomer were prepared.

[0194] The results of measuring the product containing the above-mentioned epoxy adduct and the product containing the regenerated BHET acrylate oligomer using the measurement method described above are listed in Table 2 below.

[0196] [Comparative Example 2]

[0197] In the above Example 1, the same procedure was carried out except that, for 100 parts by weight of waste PET depolymer, Benzyltriethylammonium chloride (BTEAC) was used, and instead 2 parts by weight of Tris-2,4,6-(dimethylaminomethyl) phenol (HI-54K) was added, and a product containing an epoxy adduct and a product containing a recycled BHET acrylate oligomer were prepared.

[0198] The results of measuring the product containing the above-mentioned epoxy adduct and the product containing the regenerated BHET acrylate oligomer using the measurement method described above are listed in Table 2 below.

[0200] [Comparative Example 3]

[0201] In the above Example 1, the procedure was carried out in the same manner except that 0.005 parts by weight of Phosphoric acid (H3PO4) was added instead of 2 parts by weight of Benzyltriethylammonium chloride (BTEAC) for 100 parts by weight of waste PET depolymer, thereby producing a product containing an epoxy adduct and a product containing a recycled BHET acrylate oligomer.

[0202] The results of measuring the product containing the above-mentioned epoxy adduct and the product containing the regenerated BHET acrylate oligomer using the measurement method described above are listed in Table 2 below.

[0204] [Comparative Example 4]

[0205] In the above Example 1, the procedure was carried out in the same manner except that, for 100 parts by weight of waste PET depolymer, 2 parts by weight of Benzyltriethylammonium chloride (BTEAC) was used instead of 1.4 parts by weight of Potassium acetate (KOAc) was added, thereby producing a product containing an epoxy adduct and a product containing a recycled BHET acrylate oligomer.

[0206] The results of measuring the product containing the above-mentioned epoxy adduct and the product containing the regenerated BHET acrylate oligomer using the measurement method described above are listed in Table 2 below.

[0208] [Comparative Example 5]

[0209] In the above Example 1, the procedure was carried out in the same manner except that 1.0 part by weight of Ethyltriphenylphosphonium iodide (ETPPI) was added instead of 2 parts by weight of Benzyltriethylammonium chloride (BTEAC) for 100 parts by weight of waste PET depolymer, thereby producing a product containing an epoxy adduct and a product containing a recycled BHET acrylate oligomer.

[0210] The results of measuring the product containing the above-mentioned epoxy adduct and the product containing the regenerated BHET acrylate oligomer using the measurement method described above are listed in Table 2 below.

[0212] Diol compounds Sock-shaped epoxy telechiliic compound catalyst Example 1 r-BHET Bisphenol-A Epoxy BTEAC Example 2 BDGE BTEAC Example 3 CHDM-DGE BTEAC Comparative Example 1 Bisphenol-A Epoxy TPP Comparative Example 2 Bisphenol-A Epoxy HI-54K Comparative Example 3 Bisphenol-A Epoxy H3PO4 Comparative Example 4 Bisphenol-A Epoxy KOAc Comparative Example 5 Bisphenol-A Epoxy ETPPI BHET: Bis-2-hydroxyethyl terephthalateBisphenol-A Epoxy: Bisphenol A diglycidyl etherBDGE: 1,4-Butanediol diglycidyl etherCHDM-DGE: 1,4-Cyclohexanedimethanol diglycidyl etherBTEAC: Benzyltriethylammonium chlorideTPP: TriphenylphosphineHI-54K: Tris-2,4,6-(dimethylaminomethyl)phenolETPPI: Ethyltriphenylphosphonium iodide

[0214] Epoxy additives Regenerated BHET Acrylate Oligomer Presence or absence of epoxy adduct polymerization reaction appearance Gardner viscosity Gardner viscosity Acid value (KOH mg / g) Example 1 pale yellow transparent ST XY 11 Excellent polymerization reaction Example 2 pale yellow transparent ST XY 12 Excellent polymerization reaction Example 3 pale yellow transparent ST XY 11 Excellent polymerization reaction Comparative Example 1 pale yellow transparent AB AB 30 weak polymerization reaction Comparative Example 2 pale yellow transparent AB AB Unmeasurable Polymerization failed Comparative Example 3 pale yellow transparent AB AB Unmeasurable Polymerization failed Comparative Example 4 Yellow turbidity Z Z Unmeasurable Self-polymerization reaction (polymerization failure) Comparative Example 5 pale yellow transparent AB AB Unmeasurable Polymerization failed

[0215] Upon checking Table 2 above, it was confirmed that the polymerization of the products containing the epoxy adducts of Examples 1 to 3 has excellent polymerization reactivity, and that the reactivity for producing a regenerated BHET acrylate oligomer by reacting the produced epoxy adduct with methacrylic acid is also excellent.

[0216] In contrast, regarding the reactivity of the epoxy adducts of Comparative Examples 1 to 5, when checking the Gardner viscosity and acid value results of the product containing the epoxy adduct and the product containing the regenerated BHET acrylate oligomer in Table 2, it was confirmed that the reactivity between the regenerated bis-2-hydroxyethyl terephthalate and the two-terminal epoxy telechelic compounds was poor.

[0217] In particular, regarding Comparative Example 4 above, when checking the GPC measurement results of Fig. 2 below, it was confirmed that in the reaction between regenerated bis-2-hydroxyethyl terephthalate and a bilateral epoxy telechelic compound, regenerated bis-2-hydroxyethyl terephthalate self-polymerizes to produce a regenerated BHET epoxy adduct with a weight-average molecular weight of 11,000 g / mol, thus confirming that the regenerated BHET acrylate oligomer targeted in the present disclosure cannot be produced.

[0219] Preparation of curing composition

[0220] [Example 4]

[0221] A recycled BHET acrylate main component was prepared by mixing the product containing the recycled BHET acrylate oligomer prepared in Example 1 above with styrene in a weight ratio of 2:1. It was confirmed that the recycled BHET acrylate main component contains 0.007 parts by weight of toluhydroquinone, 0.007 parts by weight of a mixture of copper and sodium hydroxide (containing 5 wt% Cu), and 0.007 parts by weight of an oxidation stabilizer (Tempoxy LO) with respect to 100 parts by weight of recycled BHET acrylate oligomer.

[0222] Subsequently, a curing composition was prepared by adding 0.002 parts by weight of an aqueous solution of Cobalt octoate with a concentration of 8% by weight as a metal salt accelerator and 1 part by weight of Methyl ethyl ketone peroxide as a curing agent to 100 parts by weight of the above-mentioned recycled BHET acrylate main component.

[0224] [Example 5]

[0225] In the above Example 4, a curing composition was prepared in the same way, except that the product containing the regenerated BHET acrylate oligomer prepared in Example 2 was used instead of the product containing the regenerated BHET acrylate oligomer prepared in Example 1.

[0227] [Example 6]

[0228] In the above Example 4, a curing composition was prepared in the same manner, except that the product containing the regenerated BHET acrylate oligomer prepared in Example 3 was used instead of the product containing the regenerated BHET acrylate oligomer prepared in Example 1.

[0230] [Comparative Example 6]

[0231]

[0232] 100 parts by weight of bisphenol A were added to a reactor, and 400 parts by weight of bisphenol A diglycidyl ether (Bisphenol-A Epoxy, Kukdo Chemical Co., YD-128) and 1 part by weight of triphenylphosphine (TPP) were added to the 100 parts by weight of bisphenol A, and then stirred at 160°C for 4 hours to prepare a product containing an epoxy adduct (compound D).

[0233] Subsequently, 100 parts by weight of methacrylic acid were added to 100 parts by weight of bisphenol A in the reactor, and the mixture was stirred at 110°C for 3 hours to produce a product containing a bisphenol A-based acrylate compound. Afterward, the product containing the bisphenol A-based acrylate compound and styrene were diluted in the reactor to a weight ratio of 2:1 to produce a main component.

[0234] Subsequently, a curing composition was prepared by adding 0.002% by weight of an aqueous solution of 8% by weight of Cobalt octoate as a metal salt accelerator and 1% by weight of Methyl ethyl ketone peroxide as a curing agent to 100 parts by weight of the above subject.

[0236] [Comparative Example 7]

[0237] After adding 100 parts by weight of glycol-modified polyethylene tephthalate to a reactor, 0.3 parts by weight of zinc acetate, which acts as a catalyst, was added to 100 parts by weight of a glycol-based mixture of diethylene glycol, neopentyl glycol, and propylene glycol mixed in a ratio of 40:24.5:7 and a polybasic acid mixture of maleic anhydride and phthalic anhydride mixed in a ratio of 39:8.6. Then, the reaction was carried out for 4 hours while stirring and gradually increasing the temperature from 175°C to 215°C.

[0238] Subsequently, while maintaining the reactor temperature, when the acid value of the reaction mixture reached 30 KOH mg / g or less and the hydroxyl value reached 150 KOH mg / g or less, the mixture was cooled to 110 ℃. Then, 55 parts by weight of hydroxymethyl methacrylate (2-HEMA), 65 parts by weight of maleic anhydride, and 2 parts by weight of toluhydroquinone (T-HQ) were additionally added to 100 parts by weight of the glycol-modified polyethylenetephthalate, and the mixture was diluted at 100 ℃ or below. Once dilution was complete, the diluted solution was heated to 105 ℃ and reacted for 1 hour while maintaining the temperature until the acid value reached 160 or less, thereby producing an unsaturated polyester oligomer.

[0239] Next, while maintaining the temperature at 105 ℃, 0.1 parts by weight of triphenylphosphine (TPP) and 200 parts by weight of bisphenol A-based epoxy (YD-128 (Kukdo Chemical) and YD-011 (Kukdo Chemical) in a weight ratio of 1:0.68) were added to the reactor in four portions over a period of 2 hours to 100 parts by weight of glycol-modified polyethylene tephthalate, and the reaction was carried out at 105 ℃ for 2 hours to measure the acid value and make it 15 or less, thereby producing a product containing an epoxy resin-modified vinyl ester resin oligomer.

[0240] Subsequently, a main component was prepared by diluting the product containing the above-prepared epoxy resin-modified vinyl ester resin oligomer and styrene in a weight ratio of 2:1, and a curing composition was prepared by adding 0.002 wt% of an 8 wt% aqueous solution of Cobalt octoate as a metal salt accelerator and 1 wt% of Methyl ethyl ketone peroxide as a curing agent to 100 wt% of the prepared main component.

[0242] [Comparative Example 8]

[0243] After adding 100 parts by weight of PET flakes to a reactor, 400 parts by weight of a glycol-based mixture comprising diethylene glycol, neopentyl glycol, and propylene glycol mixed in an expansion ratio of 16:10.5:2.4, and 300 parts by weight of an acid catalyst comprising maleic anhydride and zinc acetate mixed in an expansion ratio of 282:0.14 were added to the 100 parts by weight of the PET flakes. Subsequently, the reactor was stirred while gradually increasing the temperature from 175 ℃ to 215 ℃ for 4 hours, and when the acid value of the reaction product was 30 KOH mg / g or less and the hydroxyl value was 130 KOH mg / g or less, it was cooled to 100 ℃ to produce a reaction product containing PET oligomers.

[0244] Afterwards, 15 parts by weight of 2-hydroxyethyl acrylate, 20 parts by weight of maleic anhydride, 2 parts by weight of triphenylphosphine (TPP), and 0.1 parts by weight of toluhydroquinone were mixed with 100 parts by weight of the PET flakes in a reactor, and the temperature was raised to 105 ℃ and maintained for 1 hour to react until the acid value became 140 KOH mg / g or less.

[0245] Subsequently, while maintaining the temperature of the reactor at 105°C, 300 parts by weight of bisphenol A-based epoxy (mixture of YD-128 (Kukdo Chemical) and YD-011 (Kukdo Chemical) in a weight ratio of 1:0.68) was added in two portions over a period of 2 hours to 100 parts by weight of the PET flakes, and the reaction was carried out for 2 hours while maintaining the temperature at 105°C. When the acid value was 15 KOH mg / g or less, the reaction was terminated to produce a product containing an epoxy resin-modified vinyl ester resin oligomer.

[0246] Subsequently, a main component was prepared by diluting the product containing the above-prepared epoxy resin-modified vinyl ester resin oligomer and styrene in a weight ratio of 2:1, and a curing composition was prepared by adding 0.002 wt% of an 8 wt% aqueous solution of Cobalt octoate as a metal salt accelerator and 1 wt% of Methyl ethyl ketone peroxide as a curing agent to 100 wt% of the prepared main component.

[0248] Experimental Example 1: Measurement of Curability

[0249] After curing the cured compositions prepared in the above examples and comparative examples at 25°C, the gelation time, minimum curing time, and maximum exothermic temperature were determined, and the results are shown in Table 3 below.

[0251] Experimental Example 2: Viscosity Measurement

[0252] The cured compositions prepared in the above examples and comparative examples were measured in accordance with ISO 2555 at an environment of 25°C, specifically using a rotational viscometer (BROOKFIELD, DV2T LV). The measured viscosity is shown in Table 3 below.

[0254] Experimental Example 3: Measurement of Storage Life

[0255] After leaving the subject prepared in the above examples and comparative examples in an oven at a temperature of 105°C, the time for gelation to proceed was measured, and the results are shown in Table 3 below.

[0257] Experimental Example 4: Measurement of Mechanical Properties of Cured Product of Cured Composition

[0258] The curing composition prepared in the above examples and comparative examples was filled into a mold (300 mm X 300 mm X 3 mm) made of a glass plate and cured by leaving it at 25°C for 24 hours. Afterwards, the cured product was cured in a hot air oven at 80°C for 2 hours, and then cured at 100°C for 2 hours to produce a fully cured product.

[0259] Subsequently, the tensile strength, tensile modulus, bending strength, and bending modulus of the above-mentioned cured material were measured in accordance with KS M ISO 527-4. Specifically, the above-mentioned cured material was cut into specimens measuring 250 mm X 25 mm X 3 mm, and then measured using a Universal Testing Machine (UTM).

[0261] Experimental Example 5: Measurement of Alkali Resistance

[0262] The curing composition prepared in the above examples and comparative examples was filled into a mold (300 mm X 300 mm X 3 mm) made of a glass plate and cured by leaving it at 25°C for 24 hours. Afterwards, the cured product was cured in a hot air oven at 80°C for 2 hours, and then cured at 100°C for 2 hours to produce a fully cured product.

[0263] Subsequently, the alkali resistance of the above-mentioned cured material was measured in accordance with KS M ISO 10406-1. Specifically, the above-mentioned cured material was cut into specimens measuring 50 mm X 50 mm X 3 mm, and the specimens were immersed in an alkaline solution with a pH of 13.2. After being left at 60°C for 30 days, the alkali resistance was determined by measuring the rate of change in mass and the appearance. The measured rate of change in mass is listed in Table 3 below, and photographs taken after leaving the cured material of Example 1 and Comparative Examples 1 to 3 for 5 and 30 days are shown in Figure 3 below.

[0265] Experimental Example 6: Heat Resistance Measurement

[0266] The above cured product was measured in accordance with KS M ISO 75-2, and the results are shown in Table 3 below.

[0268] Experimental Example 7: Barcol Hardness Measurement

[0269] The above cured material Measurements were taken in accordance with KS M 3387, and the results are shown in Table 3 below.

[0271] Curable Storage life (hr) Viscosity (poise) mechanical strength Alkali resistance (weight%) Heat distortion temperature (°C) Gelation time (min) Minimum curing time (min) Maximum heating temperature (°C) Tensile strength (MPa) Tensile modulus (GPa) Bending strength (MPa) Bending modulus (GPa) Barcol hardness Examples 4 20 40 160 4 4-5 50 3.0 130 3.5 40 0.8 92 5 20 40 160 4 3-4 42 4.2 100 4.5 32 1.0 90 6 20 40 160 4 3-4 45 3.8 110 4.3 35 0.9 91 Comparative example 6 20 42 156 5 4-5 64 3.1 152 3.3 34 2.0 90 7 20 35 170 2 4-5 50 2.8 100 2.8 35 3.5 90 8 23 37 165 5 4-5 60 3.0 100 2.8 35 5.0 75

[0272] In Table 3 above, the measurement results of the main components and curing compositions of Examples 4 to 6 show that they possess decent storage stability and viscosity, and thus have properties similar to those of the curing composition of Comparative Example 1, which is polymerized with general bisphenol A and bisphenol A epoxy, confirming that they possess properties of a commercially viable level. This suggests that, compared to conventional waste PET recycling technology, the main component of the curing composition can be manufactured with only a very simple reaction, and that the curing composition containing this can possess commercially viable moisture storage stability, curability, and mechanical strength.

[0273] In particular, it was confirmed that the cured products of Examples 4 to 6 in Table 3 above possess excellent wear resistance with high Barcol hardness and excellent alkali resistance, thus exhibiting very remarkable durability. This can be seen in Figure 3 below, where the cured product prepared in Example 1 is shown in a photograph after being left in an alkali solution; this is significantly more pronounced compared to Comparative Examples 7 and 8, which are conventional cured compositions using waste PET depolymers as raw materials.

[0274] As described above, the present invention has been explained by specific details, limited embodiments, and comparative examples; however, these are provided merely to aid in a more comprehensive understanding of the invention, and the invention is not limited to the above embodiments. Those skilled in the art can make various modifications and variations from this description.

[0275] Accordingly, the scope of the present invention is not limited to the described embodiments, and all things equivalent to or having equivalent variations to the claims set forth below, as well as the claims set forth below, shall be considered to fall within the scope of the concept of the present invention.

Claims

Claim 1 (A) a recycled BHET epoxy adduct prepared by including a waste PET depolymer comprising recycled bis-2-hydroxyethyl terephthalate (r-BHET), a biterminal epoxy telechelic compound, and a tetravalent ammonium salt; and (B) one or more acrylate capping agents selected from (meth)acrylates and (meth)acrylic acids having hydroxyl groups; a recycled BHET acrylate oligomer prepared by including Claim 2 In claim 1, the tetravalent ammonium salt is a regenerated BHET acrylate oligomer, which is benzyltriethylammonium chloride (BTEAC). Claim 3 The recycled BHET acrylate oligomer according to claim 1, wherein the waste PET depolymer comprises 80% by weight or more of recycled bis-2-hydroxyethyl terephthalate (r-BHET) based on the total weight. Claim 4 In claim 1, the regenerated BHET acrylate oligomer is a regenerated BHET acrylate oligomer represented by the following chemical formula 1. [Chemical Formula 1] In the above chemical formula 1, R1, R2, R3, R4, and R6 are independently hydrogen or C1-C7 alkyl, A1 and A2 are independently single bonds or *-AO-*, where A in *-AO-* is C1-C12 alkylene, a, b, c, and d are independently integers from 1 to 7, and n is a real number of 1 or more. Claim 5 In claim 4, in the above chemical formula 1, [Formula 2] is a regenerated BHET acrylate oligomer represented by the following chemical formula 2. In the above chemical formula 2, R7, R8, R9 and R 10 They are independently hydrogen or C1-C7 alkyl, and e1 and e2 are independently integers from 1 to 4. Claim 6 In claim 4, the regenerated BHET acrylate oligomer wherein in the above formula 1, R1, R2, R3, R4, and R6 are independently hydrogen, methyl, or ethyl, A1 and A2 are independently a single bond or *-AO-*, in the above *-AO-* A is a C1-C4 alkylene, a, b, c, and d are independently integers from 1 to 3, and n is a real number of 1 or more. Claim 7 In claim 1, the regenerated BHET acrylate oligomer is a regenerated BHET acrylate oligomer represented by the following chemical formula 3. [Chemical Formula 3] In the above chemical formula 3, n is an integer from 2 to 20. Claim 8 In claim 1, the regenerated BHET acrylate oligomer is a regenerated BHET acrylate oligomer having a weight-average molecular weight of 1,000 to 10,000 g / mol. Claim 9 A subject comprising a regenerated BHET acrylate oligomer and a diluted monomer selected from any one of claims 1 to 8. Claim 10 In claim 9, the recycled BHET acrylate subject comprises 30 to 70 weight% of recycled BHET acrylate oligomer based on the total weight. Claim 11 In claim 9, the diluted monomer is one or more selected from α-styrene, vinyl toluene, and acrylic monomers, a regenerated BHET acrylate subject. Claim 12 In claim 9, the recycled BHET acrylate subject further comprises one or more additives selected from plasticizers, heat stabilizers, flame retardants, viscosity enhancers, fillers, UV stabilizers, lubricants, antistatic agents, oxidation stabilizers, and polymerization promoters. Claim 13 In claim 9, the regenerated BHET acrylate subject is, as one aspect of the present disclosure, a regenerated BHET acrylate subject further comprising an unreacted two-terminal epoxy telechelic compound, an unreacted regenerated BHET epoxy adduct, and a residual additive. Claim 14 A curing composition comprising a recycled BHET acrylate base and a curing agent according to claim 9. Claim 15 In claim 14, the curing composition is a pearl oxide-based curing agent. Claim 16 In claim 14, the curing composition further comprises a metal salt accelerator. Claim 17 In claim 14, the cured composition is a cured composition having a tensile strength of 40 MPa or more and a flexural strength of 100 MPa or more as measured by KS M ISO 527-4 after full curing. Claim 18 In claim 14, the curing composition is a curing composition having a weight change rate of 1.0% or less in the alkali resistance measurement measured according to KS F ISO 10406-1 after complete curing. Claim 19 A method for preparing a recycled BHET acrylate oligomer comprising: a step of preparing a recycled BHET epoxy adduct represented by the following chemical formula 4, comprising a waste PET depolymer containing recycled bis-2-hydroxyethyl terephthalate (r-BHET), a bi-terminal epoxy telechelic compound, and a tetravalent ammonium salt; and a step of preparing a recycled BHET acrylate oligomer comprising the product of the step of preparing the recycled BHET epoxy adduct and an acrylate capping agent represented by the following chemical formula 5. [Chemical Formula 4] [Chemical Formula 5] In the above chemical formulas 4 and 5, is a divalent organic group derived from bispecific epoxy telechelic compounds, and R 11 , R 12 , R 13 and R 14 A3 is independently hydrogen or C1-C7 alkyl, A3 is a single bond or *-AO-*, where A is a C1-C7 alkylene, f, g, h and i are independently integers from 1 to 7, and n is a real number of 1 or more. Claim 20 A method for producing a recycled BHET acrylate oligomer according to claim 19, wherein the step of producing the recycled BHET epoxy adduct is to react a waste PET depolymer and a bilateral epoxy telechelic compound in a weight ratio of 1:1 to 1:

5. Claim 21 A method for manufacturing a recycled BHET acrylate oligomer according to claim 19, wherein the step of manufacturing the recycled BHET epoxy compound comprises 0.1 to 5 parts by weight of a tetravalent ammonium salt per 100 parts by weight of waste PET depolymer.

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