Patent Application
20240199806
This application claims priority to Taiwan Application Serial Number 111145723, filed Nov. 29, 2022, which is herein incorporated by reference.
The present disclosure relates to an oligomer, a manufacturing method thereof and a crosslinked product. More particularly, the present disclosure relates to a carbonate-containing oligomer derived from an epoxy resin, a manufacturing method thereof and a crosslinked product.
Nowadays, driven by the rapid development of the electronic technology, the information processing of the electronic products such as mobile communications, servers and cloud storages are developing toward the high-frequency transmission. Furthermore, with the surge in the amount of information communication in recent years, the demand for the high-frequency printed circuit board is getting higher and higher. In order to reduce transmission losses in the high-frequency band, the materials with excellent electrical performance have become the focus of research in the related fields, and to maintain the normal operation of the electronic components in the high-temperature and high-humidity environments, the circuit boards must be heat-resistant, flame-retardant, and low water absorption.
Currently, in the field of the circuit boards, the epoxy resin is often used with the phenolic resin or dicyandiamide for curing as insulation and adhesive materials. However, although this type of material has good processing characteristic and copper foil adhesion, it has the disadvantage of polar functional groups generated after curing to cause the decrease of the electrical performance, which is difficult to meet the needs of the high-frequency and the high-speed circuit boards. In response to the above disadvantages, some technologies have directed the use of epoxy resin with active ester or styrene-maleic anhydride copolymer (SMA) to overcome the generation of the highly polar group after curing. However, even if the electrical performance is improved, it is still insufficient for use in the high-frequency and low-loss application.
Therefore, how to synthesize a new type of resin, so that it can be introduced into the high-frequency and low-loss application, which is the goal of the relevant industry.
According to one aspect of the present disclosure, a carbonate-containing oligomer is provided. The carbonate-containing oligomer includes a structure represented by formula (I):
wherein R1, R2 and X are each independently an aromatic ring group, and n is an integer from 1 to 5.
According to another aspect of the present disclosure, a manufacturing method for a carbonate-containing oligomer includes steps as follows. A mixing step is performed, wherein a purified bifunctional epoxy resin represented by formula (i) is mixed with a carbonate-containing compound represented by formula (ii), and a first mixture is obtained by heating to a first temperature to accelerate a dissolution:
A first active transesterification step is performed, wherein a catalyst is added to the first mixture and maintained at the first temperature to react, so as to obtain a second mixture. A dilution mixing step is performed, wherein an aromatic ring solvent and a methacrylic acid active ester represented by formula (iii) are added to the second mixture and mixed to obtain a third mixture:
A second active transesterification step is performed, wherein the third mixture is heated to a second temperature and maintained at the second temperature to react, so as to obtain a fourth mixture. A filtering step is performed, wherein the fourth mixture is cooled and filtered to obtain the carbonate-containing oligomer represented by formula (I):
wherein R1, R2 and X are each independently an aromatic ring group, and n is an integer from 1 to 5.
According to further another aspect of the present disclosure, a crosslinked product is provided. The crosslinked product is obtained by mixing the carbonate-containing oligomer according to the foregoing aspect with a modified polyphenylene ether resin, and adding a peroxide to perform a curing reaction.
The present disclosure can be more fully understood by reading the following detailed description of the embodiment, with reference made to the accompanying drawings as follows:
The FIGURE is a flow chart of a manufacturing method for a carbonate-containing oligomer according to one embodiment of the present disclosure.
The present disclosure will be further exemplified by the following specific embodiments. However, the embodiments can be applied to various inventive concepts and can be embodied in various specific ranges. The specific embodiments are only for the purposes of description, and are not limited to these practical details thereof.
In the present disclosure, the compound structure can be represented by a skeleton formula, and the representation can omit the carbon atom, the hydrogen atom and the carbon-hydrogen bond. In the case that the functional group is depicted clearly in the structural formula, the depicted one is preferred.
In the present disclosure, in order to concise and smooth, “a carbonate-containing oligomer, including a structure represented by formula (I)” can be represented as a carbonate-containing oligomer represented by formula (I) or a carbonate-containing oligomer (I) in some cases, and the other compounds or groups can be represented in the same manner.
In the present disclosure, if a group is not indicated specifically which is substituted or not, the group can be represented the substituted or unsubstituted group. For example, “alkyl group” can be represented the substituted or unsubstituted alkyl group.
A carbonate-containing oligomer is provided of the present disclosure, which includes a structure represented by formula (I):
wherein R1, R2 and X are each independently an aromatic ring group, and n is an integer from 1 to 5.
Specifically, the present disclosure uses the transesterification reaction between the epoxy resin and the bis-aryl carbonate to introduce the carbonate group and the free radical curable functional group into the epoxy resin for modification. At the same time, the electrical performance advantage of the free radical curing that does not produce the polar functional group can be retained, and the good nucleophilic property of the carbonate structure towards the metal and the fiber can be satisfied. Therefore, the carbonate-containing oligomer of the present disclosure has a great potential in the field of glass fiber prepreg and the high-frequency and low-loss substrate.
Reference is made to the Figure, which is a flow chart of a manufacturing method for a carbonate-containing oligomer 100 according to one embodiment of the present disclosure. In the Figure, the manufacturing method for the carbonate-containing oligomer 100 includes a step 110, a step 120, a step 130, a step 140 and a step 150.
In the step 110, a mixing step is performed, wherein a purified bifunctional epoxy resin represented by formula (i) is mixed with a carbonate-containing compound represented by formula (ii), and a first mixture is obtained by heating to a first temperature to accelerate a dissolution:
wherein X and R1 is an aromatic ring group. The first temperature of the present disclosure is for accelerating the bifunctional epoxy resin and the carbonate-containing compound to achieve the complete dissolution. The first temperature is not higher than 130° C. to prevent the bifunctional epoxy resin from self-polymerizing and increasing the viscosity. If the first temperature is too low, the reaction rate will be low, so that the reaction time will be prolonged. Therefore, in the present disclosure, the first temperature preferably can be 80ºC to 120° C., but is not limited thereto.
Specifically, “purified” in the purified bifunctional epoxy resin of the present disclosure represents that the bifunctional epoxy resin does not contain the OH functional group, and can be various types of the epoxy resin commonly known in the art. Commonly used bifunctional epoxy resin can be but not limited to the commercially available epoxy resin product such as bisphenol A epoxy resin, bisphenol F epoxy resin, biphenyl epoxy resin or naphthol epoxy resin. Preferably, the purified bifunctional epoxy resin of the present disclosure can be bisphenol A epoxy resin, which has a structure represented by formula (i-1):
Furthermore, R1 can be but not limited to phenyl group, monofluorophenyl group, perfluorophenyl group or 4-tert-butylphenyl group, preferably, R1 of the present disclosure is phenyl group, which has a structure represented by formula (ii-1):
In the step 120, a first active transesterification step is performed, wherein a catalyst is added to the first mixture and maintained at the first temperature to react, so as to obtain a second mixture. Specifically, the catalyst is preferably a pyridine derivative, an imidazole derivative or a quaternary alkylammonium salt derivative, which can be but not limited to 4-dimethylaminopyridine (DMAP), 1-alkylimidazole, 1-acetylimidazole, 1-benzylimidazole, 2-alkylimidazole, 2-ethyl-4-methylimidazole, 2,4-dimethylimidazole, 2-phenylimidazole, n-tetrabutylammonium bromide or the derivative thereof, etc., and an added amount of the catalyst can be 500 ppm to 5000 ppm.
In the step 130, a dilution mixing step is performed, wherein an aromatic ring solvent and a methacrylic acid active ester represented by formula (iii) are added to the second mixture and mixed to obtain a third mixture:
wherein R2 is the aromatic ring group, which can be but not limited to phenyl group, 1-naphthyl group, 2-naphthyl group or perfluorophenyl group, preferably, R2 of the present disclosure is phenyl group, which has a structure represented by formula (iii-1):
Furthermore, the aromatic ring solvent can be benzene, toluene or xylene.
In the step 140, a second active transesterification step is performed, wherein the third mixture is heated to a second temperature and maintained at the second temperature to react, so as to obtain a fourth mixture. Specifically, the second temperature is not higher than 130° C. to prevent the bifunctional epoxy resin from self-polymerizing. If the second temperature is too low, the reaction rate will be low, so that the reaction time will be prolonged. Therefore, in the present disclosure, the second temperature preferably can be 110° C. to 130° C., and is maintained at the second temperature for 2 hours to 6 hours. During the process, the epoxy group can be monitored by the fourier transform infrared spectrometer (FTIR), and the reaction is completed when the epoxy group completely disappear.
In the step 150, a filtering step is performed, wherein the fourth mixture is cooled and filtered to obtain the carbonate-containing oligomer represented by formula (I):
wherein R1, R2 and X are each independently the aromatic ring group, and n is an integer from 1 to 5. In detail, the n value of the product of formula (I) obtained in the step 150 is a normal distribution, so n may be an integer of 0, 1, 2, 3, 4 or 5. However, when the oligomer obtained from n is 0 lacks the carbonate structure, so n in the present disclosure is limited to an integer from 1 to 5.
Therefore, the manufacturing method for the carbonate-containing oligomer of the present disclosure uses the first-stage active ester reaction mechanism of the bis-aryl carbonate and the epoxy resin to perform the transesterification and chain extension of the epoxy resin. The molecular weight can be adjusted according to the molecular structure and the fiber impregnation requirement. Further, using the second-stage active ester reaction mechanism to modify the free radical curable functional group to the main structure, so that it can be introduced and used without special purification step to provide the feasibility of commercial mass production.
A crosslinked product is further provided of the present disclosure, which is obtained by mixing the aforementioned carbonate-containing oligomer represented by formula (I) with a modified polyphenylene ether resin, and adding a peroxide to perform a curing reaction. Specifically, a solid content ratio of the carbonate-containing oligomer represented by formula (I) and the modified polyphenylene ether resin can be 50:50 to 10:90, and the curing reaction can be performed by a staged heating method, but is not limited thereto. The modified polyphenylene ether resin can be methacrylate-modified polyphenylene ether or vinyl benzyl-modified polyphenylene ether, but is not limited thereto.
The present disclosure will be further exemplified by the following specific embodiments so as to facilitate utilizing and practicing the present disclosure completely by the people skilled in the art without over-interpreting and over-experimenting. However, the readers should understand that the present disclosure should not be limited to these practical details thereof, that is, these practical details are used to describe how to implement the materials and methods of the present disclosure and are not necessary.
The manufacturing method for the carbonate-containing oligomer of the present disclosure is shown as follow Synthesis Example 1 and Synthesis Example 2. Synthesis Example 1: 136 parts by weight of the purified bisphenol A epoxy resin (epoxy equivalent is 170 g/eq to 172 g/eq) and 43 parts by weight of the diphenyl carbonate are placed in the reaction chamber equipped with the stirrer, the thermometer and the air tube, and the dry air is ventilated in the reaction chamber to heat to 90ºC for 1 hour. Next, 1.25 parts by weight of 4-dimethylaminopyridine is added as the catalyst and maintained at 90ºC for 2 hours, and the process is monitored by the fourier transform infrared spectrometer. Then, 166 parts by weight of toluene and 68 parts by weight of phenyl methacrylate are added to heat to 110ºC for 6 hours to perform the reaction, and the process is monitored by the fourier transform infrared spectrometer. When the signal of the wave number of 915 cm−1 is completely disappeared, indicating that the reaction is completed, and the mixture is cooled and filtered to obtain the carbonate-containing oligomer of Synthesis Example 1. Specifically, the data of the FTIR spectrum of Synthesis Example 1 is 1741 cm−1 (C═O), 1720 cm−1 (C═O), and 1637 cm−1 (C═C). Furthermore, the carbonate-containing oligomer of Synthesis Example 1 is measured by gel chromatography permeability (GPC), the number average molecular weight (Mn) is 1511, and the weight average molecular weight (Mw) is 2549. The reaction equation of Synthesis Example 1 is shown in Table 1.
Synthesis Example 2: 136 parts by weight of the purified bisphenol A epoxy resin (epoxy equivalent is 170 g/eq to 172 g/eq) and 57 parts by weight of the diphenyl carbonate are placed in the reaction chamber equipped with the stirrer, the thermometer and the air tube, and the dry air is ventilated in the reaction chamber to heat to 110ºC for 1 hour. Next, 1.16 parts by weight of 1-methylimidazole is added as the catalyst and maintained at 110ºC for 2 hours, and the process is monitored by the fourier transform infrared spectrometer. Then, 196 parts by weight of xylene and 45 parts by weight of phenyl methacrylate are added to heat to 130° C. for 6 hours to perform the reaction, and the process is monitored by the fourier transform infrared spectrometer. When the signal of the wave number of 915 cm−1 is completely disappeared, indicating that the reaction is completed, and the mixture is cooled and filtered to obtain the carbonate-containing oligomer of Synthesis Example 2. Specifically, the data of the FTIR spectrum of Synthesis Example 2 is 1748 cm−1 (C═O), 1721 cm−1 (C═O), and 1637 cm−1 (C═C). Furthermore, the carbonate-containing oligomer of Synthesis Example 2 is measured by gel chromatography permeability (GPC), the number average molecular weight (Mn) is 2089, and the weight average molecular weight (Mw) is 3802. The reaction equation of Synthesis Example 2 is shown in Table 2.
The manufacturing method for the carbonate-containing oligomer of the present disclosure is suitable for the ester with the epoxy structure, such as glycidyl methacrylate (GMA), which has both the epoxy group and the methacrylic acid functional group. After the modification by the above synthesis method, the structure has both the carbonate group and the methacrylic acid functional group also can be completed, as shown in Synthesis Comparative Example 1.
Synthesis Comparative Example 1: 142 parts by weight of the glycidyl methacrylate and 107 parts by weight of the diphenyl carbonate are placed in the reaction chamber equipped with the stirrer, the thermometer and the air tube, and the dry air is ventilated in the reaction chamber to heat to 120ºC. Next, 0.5 parts by weight of n-tetrabutylammonium is added as the catalyst and maintained at 120ºC for 6 hours, and the process is monitored by the fourier transform infrared spectrometer. When the signal of the wave number of 915 cm−1 is completely disappeared, indicating that the reaction is completed, and the mixture is cooled and filtered to obtain the carbonate-containing compound of Synthesis Comparative Example 1. Specifically, the data of the FTIR spectrum of Synthesis Comparative Example 1 is 1756 cm−1 (C═O), 1719 cm−1 (C═O), and 1637 cm−1 (C═C). The reaction equation of Synthesis Comparative Example 1 is shown in Table 3.
Example 1: 8 parts by weight of methacrylate-modified polyphenylene ether resin (model SA9000, purchased from Sabic) is mixed with 3.3 parts by weight of Synthesis Example 1 (solid content is 60%), and 0.2 parts by weight of dicumyl peroxide is added therein. Next, the appropriate amount of butanone is added to adjust to the appropriate viscosity, and then pour into the aluminum plate that is treated by the release treatment with the appropriate amount. The aluminum plate is placed in the oven to cure to form the film in the nitrogen environment, and the curing temperature is raised in stages to obtain the sheet-shaped crosslinked product of Example 1.
Example 2: 5 parts by weight of methacrylate-modified polyphenylene ether resin is mixed with 8.3 parts by weight of Synthesis Example 1 (solid content is 60%), and 0.2 parts by weight of dicumyl peroxide is added therein. Next, the appropriate amount of butanone is added to adjust to the appropriate viscosity, and then pour into the aluminum plate that is treated by the release treatment with the appropriate amount. The aluminum plate is placed in the oven to cure to form the film in the nitrogen environment, and the curing temperature is raised in stages to obtain the sheet-shaped crosslinked product of Example 2.
Example 3: 8 parts by weight of methacrylate-modified polyphenylene ether resin is mixed with 3.6 parts by weight of Synthesis Example 2 (solid content is 55%), and 0.2 parts by weight of dicumyl peroxide is added therein. Next, the appropriate amount of butanone is added to adjust to the appropriate viscosity, and then pour into the aluminum plate that is treated by the release treatment with the appropriate amount. The aluminum plate is placed in the oven to cure to form the film in the nitrogen environment, and the curing temperature is raised in stages to obtain the sheet-shaped crosslinked product of Example 3.
Example 4: 5 parts by weight of methacrylate-modified polyphenylene ether resin is mixed with 9.1 parts by weight of Synthesis Example 2 (solid content is 55%), and 0.2 parts by weight of dicumyl peroxide is added therein. Next, the appropriate amount of butanone is added to adjust to the appropriate viscosity, and then pour into the aluminum plate that is treated by the release treatment with the appropriate amount. The aluminum plate is placed in the oven to cure to form the film in the nitrogen environment, and the curing temperature is raised in stages to obtain the sheet-shaped crosslinked product of Example 4. Furthermore, as the addition of Synthesis Example 2 increased, the surface of the crosslinked product thereof showed the slight phase separation.
Example 5: 60 parts by weight of methacrylate-modified polyphenylene ether resin is mixed with 16.7 parts by weight of Synthesis Example 1 (solid content is 60%), 10 parts by weight of butadiene-styrene copolymer (model Ricon 100, purchased from Total Cray Valley) and 20 parts by weight of tribally isocyanurate (TAIC), and 2 parts by weight of dicumyl peroxide is added therein. Next, the appropriate amount of butanone is added to adjust to the appropriate viscosity, and then pour into the aluminum plate that is treated by the release treatment with the appropriate amount. The aluminum plate is placed in the oven to cure to form the film in the nitrogen environment, and the curing temperature is raised in stages to obtain the sheet-shaped crosslinked product of Example 5.
Comparative Example 1: 8 parts by weight of methacrylate-modified polyphenylene ether resin is mixed with 2 parts by weight of Synthesis Comparative Example 1, and 0.2 parts by weight of dicumyl peroxide is added therein. Next, the appropriate amount of butanone is added to adjust to the appropriate viscosity, and then pour into the aluminum plate that is treated by the release treatment with the appropriate amount. The aluminum plate is placed in the oven to cure to form the film in the nitrogen environment, and the curing temperature is raised in stages to obtain the sheet-shaped crosslinked product of Comparative Example 1.
Comparative Example 2: 5 parts by weight of methacrylate-modified polyphenylene ether resin is mixed with 5 parts by weight of Synthesis Comparative Example 1, and 0.2 parts by weight of dicumyl peroxide is added therein. Next, the appropriate amount of butanone is added to adjust to the appropriate viscosity, and then pour into the aluminum plate that is treated by the release treatment with the appropriate amount. The aluminum plate is placed in the oven to cure to form the film in the nitrogen environment, and the curing temperature is raised in stages. In the end, the curing shrinkage is too severe and the complete cured film cannot be produced.
Comparative Example 3: 10 parts by weight of methacrylate-modified polyphenylene ether resin is dissolved in the toluene, and 0.2 parts by weight of dicumyl peroxide is added therein. Next, the appropriate amount of butanone is added to adjust to the appropriate viscosity, and then pour into the aluminum plate that is treated by the release treatment with the appropriate amount. The aluminum plate is placed in the oven to cure to form the film in the nitrogen environment, and the curing temperature is raised in stages to obtain the sheet-shaped crosslinked product of Comparative Example 3.
In the high-speed circuit, the propagation delay of signal depends on the dielectric constant (Dk). The substrate of the low dielectric constant material can reduce the propagation delay of the signal, and another factor that affects the signal transmission quality is the dissipation factor (Dt). The smaller the dissipation factor, the smaller the signal loss, so that the high-frequency and low-loss substrate material usually has the electrical performance of the low dielectric constant and the low dissipation factor. Further, in order to understand the electrical performance of the carbonate-containing oligomer of the present disclosure, the glass transition temperature (Tg), 5% thermogravimetric loss temperature (Td5), 800° C. Char yield, dielectric constant (Dk) and dissipation factor (Df) of the crosslinked product of Example 1 to Example 5 and Comparative Example 1 to Comparative Example 3 are measured as follows.
Dielectric analysis method: the dielectric constant (Dk) and the dissipation factor (Df) of the crosslinked product are measured at 10 GHz.
Glass transition temperature (Tg): the glass transition temperature of the crosslinked product is measured by differential scanning calorimetry (DSC), and the condition is detected at the heating rate of 10° C./min.
5% thermogravimetric loss temperature (Td5) and Char yield: 5% thermogravimetric loss temperature and 800° ° C. Char yield of the crosslinked product are measured by thermo-gravimetric analysis (TGA), and the condition is detected at the heating rate of 10° C./min under the nitrogen atmosphere.
Example 1 to Example 5 and Comparative Example 1 to Comparative Example 3 are measured by the aforementioned evaluation test method, and the results are shown in Table 4.
As shown in Table 4, compared with Comparative Example 3, the carbonate-containing oligomer of the present disclosure added in Example 1 to Example 4 at the glass transition temperature (Tg), 5% thermogravimetric loss temperature (Td5) and Char yield are shown the decreasing trend. Furthermore, the electrical performance of Example 1 and Example 3 still maintain the certain level, while the surface of the crosslinked product of Example 4 shows the slight phase separation state, indicating that the molecular weight of the carbonate-containing oligomer of the present disclosure needs to be controlled and should not be too large. In addition, the glue of Example 5 is homogeneous before curing, which shows that the compatibility between Synthesis Example 1 of the present disclosure and the ingredients SA9000, Ricon 100 and TAIC commonly used in the industry is high, and there is no phase separation after curing. Moreover, Comparative Example 1 is cured by using Synthesis Comparative Example 1, the structure of Synthesis Comparative Example 1 has the smaller molecular weight and the glass transfer temperature after curing has the small decrease, but it lacks rigid structure such as aromatic ring, resulting in the significant decrease in the 5% thermogravimetric loss temperature and the electrical performance is also significant decrease. Further, in Comparative Example 2, the addition ratio of Synthesis Comparative Example 1 is increased, even causing the curing shrinkage and failure to form the film. Therefore, it can be proved that the carbonate-containing oligomer of the present disclosure has the great development potential in the production of the high-frequency and low-loss substrate.
In conclusion, compared with the prior art, the carbonate-containing oligomer of the present disclosure uses the reaction mechanism of epoxy resin and active ester to achieve the process that can be used without specific purification. Furthermore, the carbonate-containing oligomer of the present disclosure can be used with the commercially modified polyphenylene ether resin to create the more balanced formula application value.
Although the present disclosure has been described in considerable detail with reference to certain embodiments thereof, other embodiments are possible. Therefore, the spirit and scope of the appended claims should not be limited to the description of the embodiments contained herein.
It will be apparent to those skilled in the art that various modifications and variations can be made to the structure of the present disclosure without departing from the scope or spirit of the disclosure. In view of the foregoing, it is intended that the present disclosure cover modifications and variations of this disclosure provided they fall within the scope of the following claims.
| Number | Date | Country | Kind |
|---|---|---|---|
| 111145723 | Nov 2022 | TW | national |
