Curable carbonate composition, method for preparing the same, and cured carbonate product

Abstract

To provide a curable carbonate composition, a manufacturing method thereof and a carbonate-cured product.SOLUTION: There is provided a curable carbonate composition comprising: a carbonate-epoxy copolymer including a structure represented by formula (I), of which each symbol is defined in the specification; a solvent; a first catalyst; a second catalyst; and an epoxy component. This makes it possible to improve mixing uniformity and solvent solubility during the curing process, thereby simplifying the process and reducing energy consumption and by-product generation during the curing proces.SELECTED DRAWING: Figure 1

Description

[Technical Field] 【0001】 The present invention relates to a curable carbonate composition, a method for preparing the same, and a cured carbonate product, and more particularly to a curable carbonate composition containing a carbonate epoxy copolymer that has good storage stability and whose cured carbonate product has good material properties. [Background technology] 【0002】 Polycarbonate (PC) is a thermoplastic polymer material formed by the high-temperature transesterification reaction of materials such as bisphenol A and diphenyl carbonate. Polycarbonate is one of the five major engineering plastics and, due to its good transparency, impact resistance, and heat resistance, is widely used in consumer products such as eyeglass lenses, optical discs, data access devices, and automotive lampshades. [Overview of the Initiative] [Problems that the invention aims to solve] 【0003】 Under the action of an N,N-dimethylbenzylamine (BDMA) catalyst, an aromatic carbonate structure and an epoxy structure undergo transesterification at high temperatures. In this reaction, the aromatic carbonate structure is replaced by an aliphatic carbonate structure, and at the same time, a cyclization side reaction occurs, forming an ethylene carbonate structure. This cyclization side reaction cleaves the molecular chains of the cured product and destroys the integrity of the network structure. Therefore, when attempting to prepare a cured product with high heat resistance using the carbonate and epoxy structures, it is necessary to first resolve the problems caused by the cyclization side reaction. 【0004】 Furthermore, when using diphenol monomers, which have a more complex chemical structure than bisphenol A, as raw materials to synthesize carbonate oligomers, the resulting product can be melt-mixed with epoxy resin and cured at high temperatures. Compared to carbonate oligomers prepared using bisphenol A as a raw material, cured products obtained using diphenol monomers have good heat resistance. However, the drawback of this synthesis method is that the carbonate oligomers must be synthesized from monomers at high temperatures of 200°C or higher, and the by-product phenol must be separated by vacuum distillation, resulting in a large amount of energy consumption. 【0005】 Furthermore, when waste polycarbonate is used directly as a curing agent for epoxy resin, the cured product after curing and molding has high heat resistance and decomposability. When the cured product decomposes, high molecular weight phenoxy resin can be obtained, which can be applied to other fields such as paints as a chemical additive, providing a more environmentally friendly and effective treatment method for waste polycarbonate. However, the drawback of the above treatment method is that the melting point of waste polycarbonate is too high, making it difficult to directly perform high-temperature melt mixing with epoxy resin. Also, the molecular weight of waste polycarbonate is too large, resulting in poor solubility in organic solvents. Therefore, the solid content of the waste polycarbonate solution can only reach 10% to 30% by weight, which severely limits its practical application. 【0006】 As can be seen from the above, with currently known technologies, carbonate oligomers must be obtained by monomer polymerization, and the energy consumption of high-temperature processes and the problem of by-product disposal remain significant challenges that need to be overcome. Furthermore, although carbonate oligomers and epoxy resins can co-cure, there are still considerable shortcomings in terms of mixing uniformity during the curing process, solvent solubility, and storage stability. [Means for solving the problem] 【0007】 The object of the present invention is to provide a curable carbonate composition in which the cured product can maintain good heat resistance, solve problems such as high energy consumption and by-products in the process, and improve properties such as mixing uniformity, solvent solubility, and storage stability in the process. 【0008】 One embodiment of the present invention has a structure represented by formula (I), [ka] However, R1 and R2 are each independently a hydrogen atom, a C1-C6 alkyl group, an allyl group, a C1-C6 alkoxy group, a C6-C12 aromatic group, or a halogen atom; a and b are each independently an integer from 0 to 4, and n is an integer from 7 to 24; Y is a chemical structure having at least one epoxy group; and X and Z are each independently a single bond, for example, a structure represented by formula (1), formula (2), formula (3), formula (4), formula (5), formula (6), formula (7), formula (8), formula (9), formula (10), or formula (11). [ka] However, X1 and X2 each independently provide a curable carbonate composition comprising a carbonate epoxy copolymer which is a hydrogen atom, a C1-C6 alkyl group, or a C6-C12 aromatic group; a solvent selected from the group consisting of N,N-dimethylacetamide, N-methylpyrrolidone, dimethylformamide, anisole, dimethyl sulfoxide, propylene glycol methyl ether acetate, propylene glycol methyl ether propionate, and cyclohexanone; a first catalyst selected from the group consisting of 1,8-diazabicyclo[5.4.0]undeca-7-ene, 1,5,7-triazabicyclo[4.4.0]deca-5-ene, imidazole compounds, pyridine compounds, tertiary amine compounds, and quaternary amine salts; a second catalyst selected from the group consisting of triphenylphosphine, triphenylphosphonium chloride derivatives, triphenylphosphonium bromide derivatives, triphenylphosphonium iodide derivatives, and quaternary amine salts; and an epoxy component. 【0009】 As a result, the curable carbonate composition of the present invention has properties such as high solid content and high storage stability, can improve mixing uniformity and solvent solubility during the curing process, can simplify the process steps, can reduce energy consumption and by-product generation during the curing process, and the cured product can have good heat resistance, making it advantageous for use as a base compound in epoxy resin varnish. 【0010】 Another embodiment of the present invention is an alcohol decomposition reaction step in which polycarbonate and a first component are added to a solvent, heated to a first heating temperature and stirred to dissolve the polycarbonate and the first component, and then a first catalyst is added and the reaction is maintained at the first heating temperature to form a first mixture containing a carbonate oligomer, wherein the first component has the structure shown in formula (i), and the carbonate oligomer has the structure shown in formula (ii), and the alcohol decomposition reaction step is carried out. [ka] Adding a second component having at least two epoxy groups to the first mixture, and maintaining the temperature at a second heating temperature and stirring to form a second mixture, and adding a second catalyst to the second mixture, and maintaining the temperature at a third heating temperature and stirring to form a prepolymerization reaction step of forming a curable carbonate composition, and providing a method for preparing the curable carbonate composition including the above steps. 【0011】 According to the preparation method, the number average molecular weight of the first mixture is 1000 g / mol ~ 5000 g / mol in and may be such. 【0012】 According to the preparation method, the molar ratio of the first component to the polycarbonate may be 6 to 20. 【0013】 According to the preparation method, the addition amount of the first catalyst may be 0.1 mol% to 1.0 mol% of the content of the first component in the first mixture. 【0014】 According to the preparation method, the first heating temperature may be 110°C to 170°C. 【0015】 According to the preparation method, the second component may contain at least one epoxy compound, the at least one epoxy compound has at least two epoxy groups, and when the number of epoxy compounds is two or more, each epoxy compound may have a different chemical structure. 【0016】 According to the preparation method, the addition amount of the second component may be 15 wt% to 65 wt% of the total amount of the second mixture. 【0017】 According to the preparation method, the addition amount of the second component may be 25 wt% to 50 wt% of the total amount of the second mixture. 【0018】 According to the preparation method, the second heating temperature may be 60°C to 150°C. 【0019】 According to the preparation method, the third heating temperature may be 130°C to 160°C. 【0020】 According to the preparation method, the addition amount of the second catalyst may be 0.05 wt% to 1.50 wt% of the content of the second component in the second mixture. 【0021】 According to the preparation method, the solid content of the curable carbonate composition may be 40 wt% to 80 wt%. 【0022】 Another embodiment of the present invention provides a carbonate cured product obtained by adding an accelerator to the curable carbonate composition and then heating it to a curing temperature to cause a reaction. 【0023】 According to the carbonate cured product, the accelerator may be selected from the group consisting of 1,8-diazabicyclo[5.4.0]undec-7-ene, 1,5,7-triazabicyclo[4.4.0]dec-5-ene, imidazole-based compounds, pyridine-based compounds, and tertiary amine compounds. 【0024】 According to the carbonate cured product, the addition amount of the accelerator may be 0.05 wt% to 1.50 wt% of the total amount of the curable carbonate composition. 【0025】 According to the carbonate cured product, the curing temperature may be 150°C to 240°C. 【Brief Description of the Drawings】 【0026】 For the purpose of making the above and other objects, features, advantages and embodiments of the present invention clearer and easier to understand, the description of the accompanying drawings is as follows. [Figure 1] It is a process flowchart of the preparation method of the curable carbonate composition of the present invention. 【Embodiments for Carrying out the Invention】 【0027】 The embodiments of the present invention will be described in more detail below. However, these embodiments may be applications of various inventive concepts and may be specifically implemented within various different specific scopes. Specific embodiments are for illustrative purposes only and are not limited to the scope disclosed. 【0028】 In this invention, the structure of a compound may be represented by a skeleton formula, which allows for the omission of carbon atoms, hydrogen atoms, and carbon-hydrogen bonds. If functional groups are clearly depicted in the structural formula, those depicted shall be used as the basis. 【0029】 In this invention, for the sake of brevity and ease of use, the statement "the first component has the structure shown in formula (i)" may be expressed as "the first component shown in formula (i)" or "first component (i)," and the expression of other compounds or groups can be inferred in this manner. 【0030】 <Cureable Carbonate Composition> 【0031】 One embodiment of the present invention provides a curable carbonate composition comprising a carbonate epoxy copolymer, a solvent, a first catalyst, a second catalyst, and an epoxy component. The carbonate epoxy copolymer has a structure represented by formula (I), [ka] However, R1 and R2 are each independently a hydrogen atom, a C1-C6 alkyl group, an allyl group, a C1-C6 alkoxy group, a C6-C12 aromatic group, or a halogen atom; a and b are each independently an integer from 0 to 4, and n represents the degree of polymerization and is an integer from 7 to 24; Y is a chemical structure having at least one epoxy group; and X and Z are each independently a single bond, for example, a structure represented by formula (1), formula (2), formula (3), formula (4), formula (5), formula (6), formula (7), formula (8), formula (9), formula (10), or formula (11). [ka] However, X1 and X2 are independently a hydrogen atom, an alkyl group having 1 to 6 carbon atoms, or an aromatic group having 6 to 12 carbon atoms. The solvent, first catalyst, second catalyst, and epoxy component will be explained in subsequent paragraphs, and a detailed explanation is omitted here. 【0032】 <Method for preparing a curable carbonate composition> 【0033】 Please refer to Figure 1. Figure 1 is a step flowchart of the method 100 for preparing the curable carbonate composition of the present invention. The method 100 for preparing the curable carbonate composition includes steps 110, 120, and 130. 【0034】 Step 110 involves adding polycarbonate and the first component to a solvent, raising the temperature to a first heating temperature and stirring to dissolve the polycarbonate and the first component, then adding the first catalyst and maintaining the temperature at the first heating temperature to react and form a first mixture containing a carbonate oligomer, wherein the first component has the structure shown in formula (i), and the carbonate oligomer has the structure shown in formula (ii). [ka] 【0035】 The molar ratio of the first component to the polycarbonate may be 6 to 20, and the number of moles of polycarbonate is calculated using its number average molecular weight (Mn). The solvent may be selected from the group consisting of N,N-dimethylacetamide (DMAc), N-methylpyrrolidone (NMP), dimethylformamide (DMF), anisole, dimethyl sulfoxide (DMSO), propylene glycol methyl ether acetate, propylene glycol methyl ether propionate, and cyclohexanone. The first heating temperature may be 110°C to 170°C. 【0036】 The amount of the first catalyst added may be 0.1 to 1.0 mole percent of the content of the first component in the first mixture. The first catalyst may be selected from the group consisting of 1,8-Diazabicyclo[5.4.0]undec-7-ene (DBU), 1,5,7-Triazabicyclo[4.4.0]dec-5-ene (TBD), imidazole compounds, pyridine compounds, tertiary amine compounds, and quaternary amine salts. 【0037】 The number-average molecular weight of the first mixture is 1000 g / mol. ~ 5000 g / mol in It may be present, preferably 2000 g / mol ~ 4000 g / mol in It's okay to have it. 【0038】 Step 120 is a mixing step in which a second component having at least two epoxy groups is added to the first mixture and stirred while maintaining the temperature at a second heating temperature to form a second mixture. 【0039】 The second component may include at least one epoxy compound, the epoxy compound having at least two epoxy groups, and when there are two or more epoxy compounds, each epoxy compound may have a different chemical structure, for example, a combination of an epoxy compound having multiple epoxy groups and an epoxy compound having two epoxy groups, a combination of an epoxy compound having two epoxy groups and an epoxy compound having two epoxy groups, a combination of an epoxy compound having multiple epoxy groups and an epoxy compound having multiple epoxy groups, or a combination of other epoxy compounds, and the present invention is not limited to the combinations listed above. The epoxy compound may be a bisphenol A type epoxy resin, a phenol novolac type polyfunctional epoxy resin, or another type of epoxy resin. The amount of the second component added may be 15% to 65% by weight of the total amount of the second mixture, preferably 25% to 50% by weight of the total amount of the second mixture. The second heating temperature may be 60°C to 150°C. 【0040】 Step 130 is a preliminary reaction step to form a curable carbonate composition by adding a second catalyst to the second mixture and stirring while maintaining the temperature at a third heating temperature. The solid content of the curable carbonate composition may be 40% to 80% by weight, and the solid content is the weight ratio of the curable carbonate composition before and after solvent removal. 【0041】 The third heating temperature may be 130°C to 160°C. The second catalyst may be selected from the group consisting of triphenylphosphine, triphenylphosphonium chloride derivatives, triphenylphosphonium bromide derivatives, triphenylphosphonium iodide derivatives, and quaternary amine salts. The amount of the second catalyst added may be 0.05% to 1.50% by weight of the content of the second component in the second mixture. 【0042】 One point that particularly needs to be explained is that the above preparation method 100 allows for obtaining the curable carbonate composition of this embodiment even when the reaction is complete and has not been purified. Therefore, subsequent applications can be carried out directly without purification of the curable carbonate composition, further improving the convenience of application and reducing manufacturing costs. 【0043】 <Carbonate cured product> 【0044】 A further embodiment of the present invention provides a cured carbonate product obtained by adding an accelerator to the above-mentioned curable carbonate composition and then heating it to a curing temperature to allow the reaction to proceed. 【0045】 The accelerator may be selected from the group consisting of 1,8-diazabicyclo[5.4.0]undeca-7-ene, 1,5,7-triazabicyclo[4.4.0]deca-5-ene, imidazole compounds, pyridine compounds, and tertiary amine compounds. The amount of accelerator added may be 0.05 to 1.50 by weight of the total amount of the curable carbonate composition. The curing temperature may be 150°C to 240°C. 【0046】 The present invention will be further illustrated by the following specific examples so that those skilled in the art can fully utilize and practice it without over-interpretation. These examples are not intended to limit the scope of the present invention, but rather to illustrate how the materials and methods of the present invention are put into practice. 【0047】 <Preparation of curable carbonate composition> 【0048】 <Example 1> 【0049】 100 grams (5 x 10 -3 Recovered polycarbonate pulverized material (purchased from Jiuxuan Technology Co., Ltd., product code RPC-y) and 12.35 grams of bisphenol A (5.5 × 10) -2A mole of bisphenol A is taken, 100 grams of cyclohexanone solvent is added, the mixture is heated to 150°C and then stirred while maintaining the temperature, and then 0.016 grams (0.2 mol% of bisphenol A) of 1,8-diazabicyclo[5.4.0]undeca-7-ene is added and the mixture is reacted for 6 hours to form a first mixture, the first mixture containing a carbonate oligomer, the carbonate oligomer having the structure shown in formula (ii-a). [ka] 【0050】 After the first mixture was cooled, 150.39 grams of bisphenol A type epoxy resin (Diglycidyl ether of bisphenol A; DGEBA) was added, and the mixture was heated and stirred at 140°C to form the second mixture. Subsequently, 1.2 grams of triphenylphosphine (0.8 wt% of the epoxy resin) was added, and a preliminary reaction was carried out at 140°C for 2.5 hours to obtain a curable carbonate composition f1 containing the carbonate epoxy copolymer represented by formula (Ia), and the solution of the curable carbonate composition f1 was a clear pale yellow. [ka] 【0051】 Specifically, the number-average molecular weight (RPC-y) of the recovered polycarbonate pulverized material was 18491, and its weight-average molecular weight (Mw) was 40990. When the first mixture from Example 1 was measured by gel permeation chromatography (GPC), its number-average molecular weight was 2872, and its weight-average molecular weight was 5490. 【0052】 <Example 2> 【0053】 The method for preparing the first mixture in Example 2 was the same as in Example 1, except that the subsequent process was modified to add 172.51 grams of phenol novolac type polyfunctional epoxy resin (purchased from Changchun Group, product code CNE-195) after cooling the first mixture, and then heat and stir at 120°C to form the second mixture. Subsequently, 1.38 grams of triphenylphosphine (0.8 wt% of the epoxy resin) was added and a preliminary reaction was carried out at 140°C for 2.5 hours to obtain a curable carbonate composition f2 containing the carbonate epoxy copolymer represented by formula (Ib), and the solution of the curable carbonate composition f2 was a clear pale yellow. [ka] 【0054】 Specifically, when the first mixture of Example 2 was measured by gel permeation chromatography, its number-average molecular weight was 2585 and its weight-average molecular weight was 5351. 【0055】 <Example 3> 【0056】 The method for preparing the first mixture in Example 3 was the same as in Example 1, except that the subsequent process was modified to add 101.73 grams of 4,4'-methylenebis(N,N-diglycidylaniline; TGDDM) after cooling the first mixture, and then heat and stir at 120°C to form the second mixture. Subsequently, 0.81 grams of triphenylphosphine (0.8 wt% of the epoxy resin) was added and a preliminary reaction was carried out at 140°C for 4 hours to obtain a curable carbonate composition f3 containing the carbonate epoxy copolymer represented by formula (Ic), and the solution of the curable carbonate composition f3 was a clear orange-red color. [ka] 【0057】 Specifically, when the first mixture of Example 3 was measured by gel permeation chromatography, its number-average molecular weight was 2378 and its weight-average molecular weight was 4883. 【0058】 <Example 4> 【0059】 The preparation method for Example 4 involves using 8.64 grams (3.8 × 10) of bisphenol A. -2 The procedure was the same as in Example 1 except that the molecular weight was changed to (mol). Ultimately, a curable carbonate composition f4 containing the carbonate epoxy copolymer represented by formula (Ia) was obtained, and the solution of curable carbonate composition f4 was a clear pale yellow. When the first mixture of Example 4 was measured by gel permeation chromatography, its number average molecular weight was 3238 and its weight average molecular weight was 6877. 【0060】 <Comparative Example 1> 【0061】 100 grams (5 x 10 -3 The recovered polycarbonate pulverized material RPC-y (mol) and 10.61 grams of furfuryl alcohol (1.08 × 10⁶) -1 A mole of furfuryl alcohol is taken, 100 grams of cyclohexanone solvent is added, the mixture is heated to 150°C and then stirred while maintaining the temperature, and then 0.032 grams (0.2 mol%) of 1,8-diazabicyclo[5.4.0]undeca-7-ene is added and the mixture is reacted for 6 hours to form a first mixture, the first mixture containing a carbonate oligomer, the carbonate oligomer having the structure shown in formula (C-1). [ka] 【0062】 After the first mixture was cooled, 148.06 grams of bisphenol A type epoxy resin was added, and the mixture was heated and stirred at 110°C to form the second mixture. Subsequently, 1.2 grams of triphenylphosphine (0.8 wt% of the epoxy resin) was added, and a preliminary reaction was carried out at 140°C for 5 hours to obtain curable carbonate composition c1. 【0063】 Specifically, when the first mixture of Comparative Example 1 was measured by gel permeation chromatography, its number-average molecular weight was 2847 and its weight-average molecular weight was 5481. 【0064】 <Comparative Example 2> 【0065】 The preparation method for Comparative Example 2 was the same as in Example 1, except that triphenylphosphine was replaced with 2-phenylimidazole, the amount used was 0.6 grams (0.4 wt% of the epoxy resin), and the preliminary reaction temperature was changed to 100°C. A curable carbonate composition c2 was obtained, and the solution of curable carbonate composition c2 was a transparent reddish-brown color. 【0066】 Specifically, when the first mixture of Comparative Example 2 was measured by gel permeation chromatography, its number-average molecular weight was 2687 and its weight-average molecular weight was 5307. 【0067】 <Comparative Example 3> 【0068】 The preparation method for Comparative Example 3 was the same as for Comparative Example 2, except that the amount of 2-phenylimidazole used was changed to 0.15 grams (0.1 wt% of the epoxy resin). A curable carbonate composition c3 was obtained, and the solution of curable carbonate composition c3 was a transparent reddish-brown color. 【0069】 Specifically, when the first mixture of Comparative Example 3 was measured by gel permeation chromatography, its number-average molecular weight was 2817 and its weight-average molecular weight was 5421. 【0070】 <Comparative Example 4> 【0071】 The preparation method for Comparative Example 4 involved using 6.17 grams (2.7 × 10) of bisphenol A. -2 The procedure is the same as in Example 1, except that the molecular weight was changed to (mol). When the first mixture obtained in Comparative Example 4 was measured by gel permeation chromatography, its number-average molecular weight was 5559 and its weight-average molecular weight was 9729. Furthermore, a large amount of suspended insoluble matter was generated in the subsequent process, making it impossible to smoothly obtain the final composition. 【0072】 <Comparative Example 5> 【0073】 100 grams (5 x 10 -3 The recovered polycarbonate pulverized material RPC-y (mol) and 16.23 grams of p-tert-butylphenol (PTBP, 1.08 × 10) -1 A mole of 1,8-diazabicyclo[5.4.0]undec-7-ene is added to 1,8-diazabicyclo[5.4.0]undec-7-ene, and the mixture is reacted for 6 hours to form a first mixture, which contains a carbonate oligomer, and the carbonate oligomer has the structure shown in formula (C-2). [ka] 【0074】 After the first mixture was cooled, 155.58 grams of bisphenol A type epoxy resin were added, and the mixture was heated and stirred at 110°C to form the second mixture. Subsequently, 1.2 grams of triphenylphosphine (0.8 wt% of the epoxy resin) were added, and a preliminary reaction was carried out at 140°C for 5 hours to obtain curable carbonate composition c4. 【0075】 Specifically, when the first mixture of Comparative Example 5 was measured by gel permeation chromatography, its number-average molecular weight was 2847 and its weight-average molecular weight was 5481. 【0076】 <Preparation of carbonate cured products> 【0077】 <Examples 5-8> 【0078】 The curable carbonate compositions f1 to f4 prepared in Examples 1 to 4 were each taken, 0.2% by weight of 4-dimethylaminopyridine was added to each, and after uniform stirring, they were coated onto an aluminum plate, baked at 150°C for 30 minutes, dried, and then heated to 180°C for 2 hours to cure, thereby obtaining cured carbonate products C-f1, C-f2, C-f3, and C-f4, respectively. 【0079】 <Comparative Example 6 to Comparative Example 9> 【0080】 The specific procedure was the same as in Examples 5 to 8, except that curable carbonate compositions f1 to f4 were replaced with curable carbonate compositions c1 to c4, and cured carbonate products C-c1, C-c2, C-c3, and C-c4 were obtained, respectively. 【0081】 <Stability evaluation of curable carbonate compositions> 【0082】 Conventional carbonate oligomers and epoxy resins are prone to precipitation and other issues after being mixed in solution, making stable storage difficult. The curable carbonate composition formed by the preliminary reaction with epoxy resin of the present invention contains a carbonate-epoxy copolymer represented by formula (I), has good solubility in solvents, and avoids precipitation at room temperature. However, factors such as the molecular weight of the carbonate oligomer and the selection of the catalyst are all important influencing factors in improving stability, which will be further explained below by the above examples and comparative examples. 【0083】 Table 1 below shows the stability of curable carbonate compositions f1 to f4 and curable carbonate compositions c1 to c4 at 78°C, 60°C, and room temperature (25°C). The endpoint is determined when the curable carbonate composition precipitates, settles, or gels. [Table 1] 【0084】 As can be seen from Table 1 above, the curable carbonate compositions f1 to f4 prepared in Examples 1 to 4 could be stored at room temperature for more than 30 days, and no precipitation or other adverse events occurred. In comparison, the amount of bisphenol A added to Comparative Example 4 was small, resulting in a larger molecular weight of the carbonate oligomer after alcohol decomposition. Even though the subsequent steps were the same as in Example 1, it was not possible to smoothly prepare a transparent and stable curable carbonate composition. 【0085】 Furthermore, in Comparative Examples 1 and 5, curable carbonate compositions c1 and c4 were prepared using monofunctional alcohols in the alcohol decomposition step. As a result, the carbonate oligomers after alcohol decomposition had only one alcohol functional group at their ends. Experimental results showed that even if the subsequent preliminary reaction method was the same as in Example 1, the final product had fewer reaction sites and therefore had poorer stability. Consequently, curable carbonate compositions c1 and c4 precipitated in less than 10 days at room temperature, and in an environment of 60°C, curable carbonate compositions c1 and c4 precipitated in less than 15 days. As can be seen from the above, the presence of diol functional groups in carbonate oligomers can have a very significant impact on the stability of the resulting curable carbonate compositions. 【0086】 The curable carbonate compositions f1 to f4 prepared in Examples 1 to 4 have good stability even in a relatively high-temperature environment, and can all be stored stably for 10 days or more at 78°C and for 20 days or more at 60°C. The above results are because the second catalyst used in the preliminary reaction stage has a weak catalytic effect, making it difficult for the curable carbonate composition to gel even at high temperatures. 【0087】 On the other hand, for the curable carbonate composition c2 of Comparative Example 2, although the amount of catalyst used in the preliminary reaction stage is similar to that of Example 1, the second catalyst is replaced from triphenylphosphine with weak catalytic ability to 2-phenylimidazole with high catalytic ability. As a result, the curable carbonate composition c2 gels in about 1 day at 78°C, and the reaction proceeds slowly even when left at room temperature and gels in about 28 days, so its storage stability is not good. For the curable carbonate composition c3, based on the curable carbonate composition c2, the usage amount of the second catalyst is significantly reduced. Therefore, gelation does not occur even after more than 30 days at room temperature, but gelation occurs just by maintaining it at 78°C for 2 days, and gelation occurs in less than 30 days at 60°C, showing a significant difference compared with Examples 1 to 4. 【0088】 As can be seen from the above results, the storage stability of the curable carbonate composition is very relevant to the end groups, molecular weight of the carbonate oligomer, and the catalyst added during the preliminary reaction, and has a considerable impact on actual applications. 【0089】 <Physical Property Evaluation of Carbonate Hardened Product> 【0090】 Thermal property evaluation was performed on the carbonate hardened products of Examples 5 to 8 and Comparative Examples 6 to 9, and the glass transition temperature (T g ) was measured at a heating rate of 10°C / min using a differential scanning calorimeter (DSC), and the measurement results of T g are shown in Table 2 below. 【Table 2】 【0091】 As can be seen from Table 2 above, carbonate cured products C-f1 to C-f4 are all T g It exhibits excellent heat resistance, with a temperature greater than 110°C, and in the circuit board industry where varnish products are commonly used, T g The fact that the temperature is greater than 110°C means that it can already comply with the IPC-4101 / 122 specifications for FR-4 rigid circuit boards, and as the number of functional groups in the epoxy resin increases, the resulting carbonate cured product can exhibit better heat resistance, demonstrating that the curable carbonate composition prepared in this invention has applicability as a basic compound for electronic products. 【0092】 As can be seen from the physical property tests of carbonate cured product C-c2 and carbonate cured product C-c3, when different catalysts are used in the preliminary reaction step, T g Although the impact on expression was minimal, significant differences were observed in the stability expression of the curable carbonate compositions (shown in Table 1 above). In carbonate cured product C-c1 and carbonate cured product C-c4, a monofunctional alcohol was used as the alcohol decomposition reagent in the alcohol decomposition process. As a result, the obtained carbonate oligomers had only a single alcohol functional group, leading to significant differences in the stability experiments. In addition, the obtained carbonate cured products also exhibited poor heat resistance, resulting in reduced application value. 【0093】 As described above, the curable carbonate composition of the present invention has properties such as high solid content and high storage stability, can improve mixing uniformity and solvent solubility during the curing process, can simplify the process steps, can reduce energy consumption and by-product generation during the curing process, and the cured product can have good heat resistance, making it advantageous for use as a base compound for epoxy resin varnish. Furthermore, the preparation method of the present invention allows for the direct preparation of a curable carbonate composition by subjecting waste polycarbonate to an alcohol decomposition reaction to form a carbonate oligomer, without performing a purification step, thereby achieving objectives such as increasing the value and recycling of waste polycarbonate. 【0094】 Although the present invention has been disclosed in the examples above, this is not intended to limit the invention, and any person skilled in the art can make various changes and modifications without departing from the spirit and scope of the invention. Therefore, the scope of protection of the present invention should be based on the claims that are appended later. [Explanation of Symbols] 【0095】 100: Preparation method 110, 120, 130: Process f1, f2, f3, f4, c1, c2, c3, c4: Curable carbonate composition C-f1, C-f2, C-f3, C-f4, C-c1, C-c2, C-c3, C-c4: Carbonate cured product

Claims

[Claim 1] A curable carbonate composition, Having the structure shown in formula (I), 【Chemistry 1】 However, R １ and R ２ Each of these is independently a hydrogen atom, a C1-C6 alkyl group, an allyl group, a C1-C6 alkoxy group, a C6-C12 aromatic group, or a halogen atom, and each of a and b is independently an integer from 0 to 4, and n is an integer from 7 to 11. However, Y is a chemical structure having at least one epoxy group, and X and Z are each independently a single bond, a structure represented by formula (1), formula (2), formula (3), formula (4), formula (5), formula (6), formula (7), formula (8), formula (9), formula (10), or formula (11), 【Chemistry 2】 However, X １ and X ２ Each of these is independently a carbonate epoxy copolymer which is a hydrogen atom, an alkyl group having 1 to 6 carbon atoms, or an aromatic group having 6 to 12 carbon atoms. A solvent selected from the group consisting of N,N-dimethylacetamide, N-methylpyrrolidone, dimethylformamide, anisole, dimethyl sulfoxide, propylene glycol methyl ether acetate, propylene glycol methyl ether propionate, and cyclohexanone, A first catalyst selected from the group consisting of 1,8-diazabicyclo[5.4.0]undeca-7-ene, 1,5,7-triazabicyclo[4.4.0]deca-5-ene, imidazole compounds, pyridine compounds, tertiary amine compounds, and quaternary amine salts, A second catalyst selected from the group consisting of triphenylphosphine, triphenylphosphonium chloride derivatives, triphenylphosphonium bromide derivatives, triphenylphosphonium iodide derivatives, and quaternary amine salts, Epoxy components, A curable carbonate composition containing [a specific substance]. [Claim 2] A method for preparing a curable carbonate composition according to claim 1, An alcohol decomposition reaction step is performed in which polycarbonate and a first component are added to the solvent, the temperature is raised to a first heating temperature and stirred to dissolve the polycarbonate and the first component, and then the first catalyst is added and the temperature is maintained at the first heating temperature to react and form a first mixture containing a carbonate oligomer, wherein the first component has the structure shown in formula (i), and the carbonate oligomer has the structure shown in formula (ii). 【Transformation 3】 A mixing step is performed in which a second component having at least two epoxy groups is added to the first mixture, and the mixture is stirred while maintaining a second heating temperature to form a second mixture. The second catalyst is added to the second mixture, and the mixture is stirred while maintaining the temperature at a third heating temperature to perform a preliminary reaction step to form the curable carbonate composition. A method for preparing a curable carbonate composition according to claim 1, comprising: [Claim 3] The preparation method according to claim 2, wherein the number-average molecular weight of the first mixture is 1000 g / mol to 5000 g / mol. [Claim 4] The preparation method according to claim 2, wherein the molar ratio of the first component to the polycarbonate is 6 to 20. [Claim 5] The preparation method according to claim 2, wherein the amount of the first catalyst added is 0.1 mole percent to 1.0 mole percent of the content of the first component in the first mixture. [Claim 6] The preparation method according to claim 2, wherein the first heating temperature is 110°C to 170°C. [Claim 7] The preparation method according to claim 2, wherein the second component comprises at least one epoxy compound, the at least one epoxy compound has at least two epoxy groups, and when there are two or more of the at least one epoxy compounds, each of the at least one epoxy compounds has a different chemical structure. [Claim 8] The preparation method according to claim 2, wherein the amount of the second component added is 15% to 65% by weight of the total amount of the second mixture. [Claim 9] The preparation method according to claim 8, wherein the amount of the second component added is 25% to 50% by weight of the total amount of the second mixture. [Claim 10] The preparation method according to claim 2, wherein the second heating temperature is 60°C to 150°C. [Claim 11] The preparation method according to claim 2, wherein the third heating temperature is 130°C to 160°C. [Claim 12] The preparation method according to claim 2, wherein the amount of the second catalyst added is 0.05 to 1.50 by weight of the content of the second component in the second mixture. [Claim 13] The preparation method according to claim 2, wherein the solid content of the curable carbonate composition is 40% by weight to 80% by weight. [Claim 14] A cured carbonate product, obtained by adding an accelerator to the curable carbonate composition described in claim 1 and then heating it to a curing temperature to allow the reaction to proceed. [Claim 15] The carbonate cured product according to claim 14, wherein the accelerator is selected from the group consisting of 1,8-diazabicyclo[5.4.0]undeca-7-ene, 1,5,7-triazabicyclo[4.4.0]deca-5-ene, imidazole compounds, pyridine compounds, and tertiary amine compounds. [Claim 16] The carbonate cured product according to claim 14, wherein the amount of accelerator added is 0.05% by weight to 1.50% by weight of the total amount of the curable carbonate composition. [Claim 17] The cured carbonate product according to claim 14, wherein the curing temperature is 150°C to 240°C.

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