Curable carbonate composition, manufacturing method thereof and carbonate-cured 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 carbonate cured product, and more particularly to a curable carbonate composition containing a carbonate epoxy copolymer, which has good storage stability and the carbonate cured product has good material properties.

Background Art

[0002] Polycarbonate (PC) is a thermoplastic polymer material formed by a transesterification reaction of materials such as bisphenol A and diphenyl carbonate at high temperature. Polycarbonate belongs to one of the five major engineering plastic materials and has good transparency, impact resistance and heat resistance, so it is widely applied to consumer products such as spectacle lenses, optical discs, data access devices or automotive lamp shades.

Summary of the Invention

Problems to be Solved by the Invention

[0003] When the aromatic carbonate structure and the epoxy structure undergo a transesterification reaction at high temperature under the action of a Benzyldimethylamine (BDMA) catalyst, the aromatic carbonate structure is substituted by an aliphatic carbonate structure, and at the same time, a cyclization side reaction occurs to form an ethylene carbonate structure. The above cyclization side reaction cuts the molecular chain of the cured product and destroys the integrity of the network structure of the cured product. Therefore, when trying to prepare a cured product with high heat resistance using a carbonate structure and an epoxy structure, it is first necessary to solve the problems caused by the cyclization side reaction.

[0004] In addition, when synthesizing a carbonate oligomer using a diphenol monomer with a chemical structure more complex than bisphenol A as a raw material, the resulting product can be melt-mixed with an epoxy resin and cured at a high temperature. Compared with the carbonate oligomer prepared using bisphenol A as a raw material, the cured product obtained using a diphenol monomer as a raw material has good heat resistance. However, the defect of this synthesis method is that the carbonate oligomer must be synthesized with a monomer at a high temperature of 200 °C or higher, and furthermore, the by-product phenol must be separated by vacuum distillation, which results in a large amount of energy consumption.

[0005] In addition, when waste polycarbonate is directly used as a curing agent for an epoxy resin, the cured product after curing and molding has high heat resistance and decomposability. When the cured product is decomposed, a high molecular weight phenoxy resin can be obtained, which can be applied to other fields such as paints as a chemical aid, providing a more environmentally friendly and effective treatment means for waste polycarbonate. However, the defect of the above treatment means is that due to the too high melting point of waste polycarbonate, it is difficult to directly perform high-temperature melt mixing with the epoxy resin, and due to the too large molecular weight of waste polycarbonate and its poor solubility in organic solvents, the solid content of the waste polycarbonate solution can only reach 10 wt% to 30 wt%, which has extremely large limitations in actual applications.

[0006] As can be seen from the above, in the currently known technologies, it is necessary for the carbonate oligomer to be obtained by monomer polymerization, and the problems of energy consumption in the high-temperature process and the treatment of by-products are still difficult problems to be solved. In addition, although the carbonate oligomer and the epoxy resin can be co-cured, there are still quite deficiencies in the mixing uniformity, solvent solubility or storage stability during the curing process.

Means for Solving the Problems

[0007] The object of the present invention is to provide a curable carbonate composition whose cured product can maintain good heat resistance, further solve problems such as high energy consumption and by-products in the process, and at the same time improve properties such as mixing uniformity, solvent solubility or storage stability in the process.

[0008] One embodiment of the present invention has a structure represented by the formula (I),

Chemical formula

Chemical formula

[0009] Thereby, the curable carbonate composition of the present invention has characteristics such as a high solid content and high storage stability, can improve the mixing uniformity and solvent solubility in the curing process, further simplifies the process steps, can reduce the energy consumption and by-product generation in the curing process, and the cured product can have good heat resistance, which is advantageous for use as a basic formulation of an epoxy resin varnish.

[0010] Another embodiment of the present invention is an alcoholysis reaction step of adding a polycarbonate and a 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 a first catalyst and maintaining the first heating temperature to react to form a first mixture containing a carbonate oligomer, wherein the first component has a structure represented by formula (i) and the carbonate oligomer has a structure represented by formula (ii), and performing the alcoholysis reaction step.

Chemical formula

[0011] According to the preparation method, the number average molecular weight of the first mixture may be 1000 g / mole to 5000 g / mole.

[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 mole percentage to 1.0 mole percentage 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 weight percentage to 65 weight percentage of the total amount of the second mixture.

[0017] According to the preparation method, the addition amount of the second component may be 25 weight percentage to 50 weight percentage 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] In order to make 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

Modes for Carrying Out the Invention

[0027] Hereinafter, each embodiment of the present invention will be examined in more detail. However, this embodiment may be an application of various inventive concepts and may be specifically implemented within various different specific ranges. The specific embodiments are for illustrative purposes only and are not limited to the disclosed range.

[0028] In the present invention, when representing the structure of a compound by a Skeleton formula, such a representation method can omit carbon atoms, hydrogen atoms, and carbon-hydrogen bonds. When a functional group is clearly depicted in the structural formula, the depicted one shall be the criterion.

[0029] In the present invention, for the sake of brevity and smoothness, "the first component has the structure represented by formula (i)" may be expressed as "the first component represented by formula (i)" or "the first component (i)", and the representation methods of other compounds or groups are analogized in this way.

[0030] <Curable 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),

Chemical formula

Chemical formula

[0032] <Method for Preparing Curable Carbonate Composition>

[0033] Please refer to FIG. 1. FIG. 1 is a process flowchart of a method 100 for preparing a curable carbonate composition for preparing the curable carbonate composition of the present invention. The method 100 for preparing a curable carbonate composition includes a step 110, a step 120, and a step 130.

[0034] In step 110, a polycarbonate and a first component are added to a solvent, and the temperature is raised to a first heating temperature and stirred to dissolve the polycarbonate and the first component. Then, a first catalyst is added and maintained at the first heating temperature for reaction to form a first mixture containing a carbonate oligomer through an alcoholysis reaction step. The first component has a structure represented by formula (i), and the carbonate oligomer has a structure represented by formula (ii).

Chemical formula

[0035] The molar ratio of the first component to the polycarbonate may be 6 to 20, and the number of moles of the polycarbonate is calculated based on its number average molecular weight (Mn). The solvent may be selected from the group consisting of N,N-dimethylacetamide (DMAc), N-methyl-2-pyrrolidone (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 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. 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-based compounds, pyridine-based compounds, tertiary amine compounds, and quaternary amine salts.

[0037] The number average molecular weight of the first mixture may be 1000 g / mole to 5000 g / mole, preferably 2000 g / mole to 4000 g / mole.

[0038] Step 120 is to perform a mixing step of adding a second component having at least two epoxy groups to the first mixture, maintaining the second heating temperature, and stirring to form a second mixture.

[0039] The second component may contain at least one epoxy compound. The epoxy compound has at least two epoxy groups. When the number of epoxy compounds is two or more, each epoxy compound may have a different chemical structure. For example, it may be a combination of an epoxy compound having a plurality of 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 a plurality of epoxy groups and an epoxy compound having a plurality of epoxy groups, or a combination of other epoxy compounds. 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 other types of epoxy resins. The addition amount of the second component may be 15 wt% to 65 wt% of the total amount of the second mixture, preferably 25 wt% to 50 wt% of the total amount of the second mixture. The second heating temperature may be 60°C to 150°C.

[0040] Step 130 is to perform a preliminary reaction step of adding a second catalyst to the second mixture and maintaining and stirring at a third heating temperature to form a curable carbonate composition. The solid content of the curable carbonate composition may be 40 wt% to 80 wt%. 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 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.

[0042] As a point that needs to be particularly explained, since the above preparation method 100 can obtain the curable carbonate composition of the present embodiment when the reaction is completed and not purified, subsequent applications can be directly carried out without purifying the curable carbonate composition, further improving the convenience of application and reducing the manufacturing cost.

[0043] <Carbonate cured product>

[0044] Still another embodiment of the present invention provides a carbonate cured product obtained by adding an accelerator to the above curable carbonate composition and then heating to a curing temperature to cause a reaction.

[0045] 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. The addition amount of the accelerator may be 0.05 weight percentage to 1.50 weight percentage of the total amount of the curable carbonate composition. The curing temperature may be 150°C to 240°C.

[0046] In order for those skilled in the art to fully utilize and practice the present invention without excessive interpretation, the present invention will be further illustratively described by the following specific examples. However, these examples do not limit the scope of the present invention and are for explaining how to implement the materials and methods of the present invention.

[0047] <Preparation of curable carbonate composition>

[0048] <Example 1>

[0049] 100 grams (5×10 -3 mole) of recovered polycarbonate grinding material (purchased from Jiuxuan Technology Co., Ltd., product code RPC-y) and 12.35 grams of bisphenol A (5.5×10 -2Take [mole], add 100 grams of cyclohexanone solvent, heat up to 150 °C and then maintain the temperature while stirring. Subsequently, add 0.016 grams (0.2 mol% of bisphenol A) of 1,8-diazabicyclo[5.4.0]undec-7-ene, and react for 6 hours to form a first mixture. The first mixture contains a carbonate oligomer, and the carbonate oligomer has a structure represented by formula (ii-a). [Chemical formula]

[0050] After cooling the first mixture, add 150.39 grams of bisphenol A type epoxy resin (Diglycidyl ether of bisphenol A; DGEBA), and heat and stir at 140 °C to form a second mixture. Subsequently, add 1.2 grams of triphenylphosphine (0.8 wt% of the epoxy resin), and pre-react at 140 °C for 2.5 hours to obtain a curable carbonate composition f1 containing a carbonate epoxy copolymer represented by formula (I-a), and the solution of the curable carbonate composition f1 was transparent and light yellow. [Chemical formula]

[0051] Specifically, the number average molecular weight of the recovered polycarbonate pulverized material RPC-y is 18491, and the weight average molecular weight (Weight average molecular weight; Mw) is 40990. When the first mixture of Example 1 was measured by gel permeation chromatograph (GPC), its number average molecular weight was 2872 and the weight average molecular weight was 5490.

[0052] [Example 2]

[0053] The preparation method of the first mixture in Example 2 is the same as that in Example 1, except that the subsequent process is changed to adding 172.51 grams of phenol novolak type polyfunctional epoxy resin (purchased from Changchun Group, product code CNE-195) after cooling the first mixture, and heating and stirring at 120 °C to form a second mixture. Subsequently, 1.38 grams of triphenylphosphine (0.8 wt% of the epoxy resin) is added, and pre-reacted at 140 °C for 2.5 hours to obtain a curable carbonate composition f2 containing a carbonate epoxy copolymer represented by formula (I-b), and the solution of the curable carbonate composition f2 was transparent and light yellow.

Chemical formula

[0054] Specifically, when the first mixture in 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 preparation method of the first mixture in Example 3 is the same as that in Example 1, except that the subsequent process is changed to adding 101.73 grams of 4,4'-methylenebis(N,N-diglycidylaniline) (Tetraglycidyl methylenedianiline; TGDDM) after cooling the first mixture, and heating and stirring at 120 °C to form a second mixture. Subsequently, 0.81 grams of triphenylphosphine (0.8 wt% of the epoxy resin) is added, and pre-reacted at 140 °C for 4 hours to obtain a curable carbonate composition f3 containing a carbonate epoxy copolymer represented by formula (I-c), and the solution of the curable carbonate composition f3 was transparent and orange-red.

Chemical formula

[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 of Example 4 was the same as that of Example 1 except that the usage amount of bisphenol A was changed to 8.64 grams (3.8×10 -2 mole). Finally, a curable carbonate composition f4 containing a carbonate epoxy copolymer represented by the formula (I-a) could be obtained, and the solution of the curable carbonate composition f4 was a transparent light yellow color. 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 (5×10 -3 mole) of the recovered polycarbonate pulverized material RPC-y and 10.61 grams of furfuryl alcohol (1.08×10 -1 mole) were taken, 100 grams of cyclohexanone solvent was added, the temperature was raised to 150 °C and then maintained with stirring. Subsequently, 0.032 grams (0.2 mol% of furfuryl alcohol) of 1,8-diazabicyclo[5.4.0]undec-7-ene was added and reacted for 6 hours to form a first mixture. The first mixture contained a carbonate oligomer, and the carbonate oligomer had a structure represented by the formula (C-1).

Chemical formula

[0062] After cooling the first mixture, 148.06 grams of bisphenol A type epoxy resin was added, and the mixture was heated and stirred at 110 °C to form a 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 a 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 of Comparative Example 2 was the same as that of Example 1 except that triphenylphosphine was replaced with 2-phenylimidazole, the usage amount was 0.6 grams (0.4 wt% of the epoxy resin), and the preliminary reaction temperature was replaced with 100 °C. A curable carbonate composition c2 could be obtained, and the solution of the curable carbonate composition c2 was transparently dark red-brown.

[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 of Comparative Example 3 was the same as that of Comparative Example 2 except that the usage amount of 2-phenylimidazole was changed to 0.15 grams (0.1 wt% of the epoxy resin). A curable carbonate composition c3 could be obtained, and the solution of the curable carbonate composition c3 was transparently dark red-brown.

[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 of Comparative Example 4 is the same as that of Example 1 except that the amount of bisphenol A used is changed to 6.17 grams (2.7×10 -2 mole). When the first mixture obtained in Comparative Example 4 was measured by gel permeation chromatography, its number average molecular weight was 5559, its weight average molecular weight was 9729, and a large amount of floating insoluble matter was generated in the subsequent process, so the final composition could not be obtained smoothly.

[0072] <Comparative Example 5>

[0073] 100 grams (5×10 -3 mole) of recovered polycarbonate pulverized material RPC-y and 16.23 grams of p-tert-butylphenol (p-tert-butylphenol; PTBP, 1.08×10 -1 mole) were taken, 100 grams of cyclohexanone solvent was added, the temperature was raised to 150 °C and then maintained with stirring. Subsequently, 0.032 grams (0.2 mol% of p-tert-butylphenol) of 1,8-diazabicyclo[5.4.0]undec-7-ene was added and reacted for 6 hours to form a first mixture. The first mixture contains carbonate oligomers, and the carbonate oligomers have a structure represented by the formula (C-2).

Chemical formula

[0074] After cooling the first mixture, 155.58 grams of bisphenol A type epoxy resin was added, and the mixture was heated and stirred at 110 °C to form a second mixture. Subsequently, 1.2 grams of triphenylphosphine (0.8 wt% of the epoxy resin) was added and pre-reacted at 140 °C for 5 hours to obtain a 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 Product>

[0077] <Examples 5 to 8>

[0078] The curable carbonate compositions f1 to f4 prepared in Examples 1 to 4 were each taken, 4-dimethylaminopyridine at 0.2 weight percentage was added to each, and after uniformly stirring, they were applied onto an aluminum plate, baked at 150 °C for 30 minutes, dried, and then heated up to 180 °C and cured for 2 hours to obtain carbonate cured products C-f1, carbonate cured products C-f2, carbonate cured products C-f3, and carbonate cured products C-f4, respectively.

[0079] <Comparative Examples 6 to 9>

[0080] The specific procedure was the same as that of Examples 5 to 8 except that the curable carbonate compositions f1 to f4 were replaced with the curable carbonate compositions c1 to c4, and carbonate cured products C-c1, carbonate cured products C-c2, carbonate cured products C-c3, and carbonate cured products C-c4 were obtained, respectively.

[0081] <Stability Evaluation of Curable Carbonate Composition>

[0082] After preparing a conventional carbonate oligomer and an epoxy resin in a solution, precipitation and sedimentation are likely to occur, so stable storage is not easy. The curable carbonate composition formed by the preliminary reaction with an epoxy resin of the present invention contains a carbonate epoxy copolymer represented by the formula (I), has good solubility in a solvent, and avoids the occurrence of 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 for improving stability, and will be further described below with the above examples and comparative examples.

[0083] Table 1 below shows the stability status of curable carbonate compositions f1 to f4 and curable carbonate compositions c1 to c4 at 78 °C, 60 °C, and room temperature (25 °C), respectively. The endpoint is determined when the curable carbonate composition reaches a state such as precipitation, sedimentation, or gelation. [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 30 days or more without any precipitation or sedimentation. In comparison, the amount of bisphenol A added in Comparative Example 4 was small, and the molecular weight of the carbonate oligomer after alcoholysis was large. Even though all subsequent procedures were the same as in Example 1, a transparent and stable curable carbonate composition could not be prepared smoothly.

[0085] Also, for the curable carbonate compositions c1 and c4 prepared in Comparative Example 1 and Comparative Example 5, since a monofunctional alcohol was used in the alcoholysis step, there was only one alcohol functional group at the end of the carbonate oligomer after alcoholysis. From the experimental results, even if all subsequent preliminary reaction methods were the same as in Example 1, the finally obtained product had fewer reaction sites, resulting in poor stability. Therefore, the curable carbonate compositions c1 and c4 precipitated and sedimented in less than 10 days at room temperature, and in an environment of 60 °C, the curable carbonate compositions c1 and c4 sedimented in less than 15 days. As can be seen from the above, the carbonate oligomer can have a very significant impact on the stability of the resulting curable carbonate composition when it has a diol functional group.

[0086] The curable carbonate compositions f1 to f4 prepared in Examples 1 to 4 have relatively good stability even in a relatively high-temperature environment, and can all be stored stably for more than 10 days at 78°C, and can all be stored stably for more than 20 days at 60°C. The above results are because the second catalyst used in the preliminary reaction stage has a weak catalytic effect, and the curable carbonate composition is less likely to gel even at high temperatures.

[0087] On the other hand, for the curable carbonate composition c2 of Comparative Example 2, the amount of the catalyst used in the preliminary reaction stage is similar to that of Example 1, but 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 the storage stability is not good. For the curable carbonate composition c3, based on the curable carbonate composition c2, the amount of the second catalyst used is significantly reduced. Therefore, gelation does not occur even after more than 30 days at room temperature, but gelation occurs only after maintaining 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 Cured Product>

[0090] Thermal property evaluation was performed on the carbonate cured 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, all of the carbonate cured products C-f1 to C-f4 exhibit excellent heat resistance with T g being greater than 110°C. In the circuit board industry where varnish products are frequently used, a T g greater than 110°C can already meet the IPC-4101 / 122 specification for FR-4 rigid circuit boards. Moreover, as the number of functional groups of the epoxy resin increases, the obtained carbonate cured product can exhibit better heat resistance. It has been shown that the curable carbonate composition prepared in the present invention has the potential to be used as a basic formulation for electronic products.

[0092] As can be seen from the physical property tests of the carbonate cured product C-c2 and the carbonate cured product C-c3, when different catalysts are used in the preliminary reaction step, the T g has little influence on the expression, but significant differences occur in the stability expression of the curable carbonate composition (shown in Table 1 above). In the case of the carbonate cured product C-c1 and the carbonate cured product C-c4, in the alcoholysis process, a monofunctional alcohol is used as the alcoholysis reagent, so the obtained carbonate oligomer has only a single alcohol functional group. In addition to the significant differences that occurred in the above stability experiment, the obtained carbonate cured product also exhibits poor heat resistance, resulting in a decrease in its application value.

[0093] As described above, the curable carbonate composition of the present invention has characteristics such as a high solid content and high storage stability, can improve the mixing uniformity and solvent solubility during the curing process, further simplifies the process steps, can reduce the energy consumption and by-product generation during the curing process, and the cured product can have good heat resistance, which is advantageous for use as a basic formulation of an epoxy resin varnish. In addition, the preparation method of the present invention can directly prepare a curable carbonate composition by subjecting waste polycarbonate to an alcoholysis reaction to form a carbonate oligomer without performing a purification step, and can achieve purposes such as increasing the value and reusing waste polycarbonate.

[0094] The present invention has been disclosed as above in the examples, but this is not for limiting the present invention. Any person skilled in the art can make various changes and modifications without departing from the spirit and scope of the present invention. Therefore, the protection scope of the present invention should be based on what is defined by the claims attached later.

Explanation of Reference Signs

[0095] 100: Preparation method 110, 120, 130: Steps 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

1. A curable carbonate composition, having a structure represented by formula (I), 【Chemical 1】 However, R １ and R ２ are each independently a hydrogen atom, an alkyl group having 1 to 6 carbon atoms, an allyl group, an alkoxy group having 1 to 6 carbon atoms, an aromatic group having 6 to 12 carbon atoms, or a halogen atom, a and b are each independently an integer of 0 to 4, and n is an integer of 7 to 24, wherein 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), 【Chemical 2】 However, X １ and X ２ are each independently a hydrogen atom, an alkyl group having 1 to 6 carbon atoms, or an aromatic group having 6 to 12 carbon atoms, and a carbonate epoxy copolymer 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]undec-7-ene, 1,5,7-triazabicyclo[4.4.0]dec-5-ene, imidazole-based compounds, pyridine-based 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, an epoxy component, and a curable carbonate composition containing the same.

2. A method for preparing the curable carbonate composition according to Claim 1, comprising adding a polycarbonate and a first component to the solvent, heating to a first heating temperature and stirring to dissolve the polycarbonate and the first component, then adding the first catalyst and maintaining the first heating temperature for reaction to form a first mixture containing a carbonate oligomer, which is an alcoholysis reaction step, wherein the first component has a structure represented by formula (i) and the carbonate oligomer has a structure represented by formula (ii), 【Chemical 3】 adding a second component having at least two epoxy groups to the first mixture, maintaining at a second heating temperature and stirring to form a second mixture, which is a mixing step, adding the second catalyst to the second mixture, maintaining at a third heating temperature and stirring to form the curable carbonate composition, which is a preliminary reaction step, and a method for preparing the curable carbonate composition according to Claim 1, comprising the above steps.

3. The preparation method according to Claim 2, wherein the number average molecular weight of the first mixture is 1000 g / mole to 5000 g / mole.

4. The preparation method according to claim 2, wherein the molar ratio of the first component to the polycarbonate is 6 to 20.

5. The preparation method according to claim 2, wherein the addition amount of the first catalyst is 0.1 mol% to 1.0 mol% of the content of the first component in the first mixture.

6. The preparation method according to claim 2, wherein the first heating temperature is 110°C to 170°C.

7. The second component contains at least one epoxy compound, the at least one epoxy compound has at least two epoxy groups, and when the number of the at least one epoxy compound is two or more, each of the at least one epoxy compound has a different chemical structure. The preparation method according to claim 2.

8. The preparation method according to claim 2, wherein the addition amount of the second component is 15 wt% to 65 wt% of the total amount of the second mixture.

9. The preparation method according to claim 8, wherein the addition amount of the second component is 25 wt% to 50 wt% of the total amount of the second mixture.

10. The preparation method according to claim 2, wherein the second heating temperature is 60°C to 150°C.

11. The preparation method according to claim 2, wherein the third heating temperature is 130°C to 160°C.

12. The preparation method according to claim 2, wherein the addition amount of the second catalyst is 0.05 wt% to 1.50 wt% of the content of the second component in the second mixture.

13. The preparation method according to claim 2, wherein the solid content of the curable carbonate composition is 40 wt% to 80 wt%.

14. A carbonate cured product obtained by adding an accelerator to the curable carbonate composition according to claim 1 and then heating to a curing temperature to cause a reaction.

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]undec-7-ene, 1,5,7-triazabicyclo[4.4.0]dec-5-ene, imidazole-based compounds, pyridine-based compounds, and tertiary amine compounds.

16. The carbonate cured product according to claim 14, wherein the addition amount of the accelerator is 0.05 wt% to 1.50 wt% of the total amount of the curable carbonate composition.

17. The carbonate cured product according to claim 14, wherein the curing temperature is 150°C to 240°C.

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