High-heat-resistance full-bio-based benzoxazine resin, preparation method thereof and resin composition for copper-clad plate

Abstract

The preparation method comprises the following steps: adding bio-based phenol, bio-based amine and bio-based aldehyde into a reactor provided with a stirrer, a thermometer, a condenser pipe and a water segregator, adding toluene and a catalyst, uniformly stirring, heating, separating out water generated by a system by using the water segregator while heating, and adding a catalyst into the reactor, so as to obtain the high-heat-resistance full-bio-based benzoxazine resin. And when the temperature is raised to 120-140 DEG C, maintaining the reaction for 3-5 hours, washing and layering the obtained resin by using a 1mol / L NaOH solution, taking the lower resin layer, washing and layering by using deionized water, taking the lower resin layer, and removing methylbenzene and water by using a rotary evaporator to obtain the high-heat-resistance full-bio-based benzoxazine resin. The invention also relates to a resin composition for the copper-clad plate. According to the high-heat-resistance full-bio-based benzoxazine resin disclosed by the invention, the bio-based phenol, the bio-based amine and the bio-based aldehyde react, all raw materials participating in the reaction are bio-based raw materials, and the synthesized benzoxazine resin is the full-bio-based benzoxazine resin.

Description

Technical Field

[0001] The present invention relates to the field of copper clad laminates, specifically to a high heat-resistant all-bio-based benzoxazine resin and its preparation method, and also to a resin composition for copper clad laminates. Background Art

[0002] In today's era when the problems of global warming and air pollution are becoming increasingly serious, climate change has become the focus of attention in all sectors of society. Against this background, China promotes carbon peak and carbon neutrality to achieve sustainable development. Bio-based resins use renewable resources such as plant oils, starches, and cellulose as raw materials. The carbon emissions during the production process are much lower than those of traditional petroleum-based resins, which can effectively reduce greenhouse gas emissions, lower the carbon footprint in the industrial field, and contribute to the transformation of the national energy structure and green and low-carbon development.

[0003] Benzoxazine resin is a six-membered heterocyclic compound containing C, N, and O formed by the condensation of phenol, primary amine, and formaldehyde. Under the action of heat or a catalyst, it undergoes ring-opening polymerization to form a nitrogen-containing network structure similar to phenolic resin. The cured product has characteristics such as a low dielectric constant and dielectric loss, low water absorption, high heat resistance, processing dimensional stability, and good flame retardancy, and is one of the suitable raw materials for preparing copper clad laminates. The synthesis raw materials of benzoxazine are usually phenol, bisphenol A, bisphenol F, aniline, diaminodiphenylmethane, diaminodiphenyl ether, paraformaldehyde, etc., and these are basically all from petroleum cracking products. The synthesized benzoxazine belongs to petroleum-based resin and cannot meet the requirements of green development. In order to achieve China's carbon peak and carbon neutrality goals, researchers have begun to develop bio-based benzoxazine resins. For example, in patent CN111057050A, phloretic acid and furfurylamine are used as the phenol source and amine source, and react with paraformaldehyde to generate a bio-based benzoxazine resin; in patent CN114195803A, dihydroxycoumarin, an amine compound, and paraformaldehyde react to generate a coumarin-based bio-based bifunctional benzoxazine resin; in patent CN118562127A, bisphenolic acid is first synthesized with an alcohol substance to form bisphenolic acid ester, and then it reacts with paraformaldehyde and bis(trifluoromethyl diaminobiphenyl) to synthesize a bio-based benzoxazine resin with high Tg and intrinsic flame retardancy. In CN115260489A, a bio-based monophenol, a bio-based diamine (Priamine1074), and paraformaldehyde are used to synthesize a bio-based bifunctional benzoxazine resin. Similar patents also include CN113845638A, CN115260425A, etc. However, in such reports, only the phenol source and amine source use bio-based raw materials, but most of the aldehyde substances use paraformaldehyde, and paraformaldehyde still belongs to petroleum-based compounds. Therefore, such benzoxazine resins are not all-bio-based benzoxazine resins. Summary of the Invention

[0004] The technical problem to be solved by the present invention is to provide a highly heat-resistant all-bio-based benzoxazine resin, a preparation method thereof, and a resin composition for a copper clad laminate.

[0005] To solve the above technical problem, the technical solution of the present invention is: a highly heat-resistant all-bio-based benzoxazine resin, and its innovation lies in: the benzoxazine resin has a chemical structural general formula shown in formula (1): In formula (1): R1 is any one of -COCH3, -OCH3, -CH2CH3.

[0006] A preparation method of the above-mentioned highly heat-resistant all-bio-based benzoxazine resin, and its innovation lies in: including the following steps: First, take a reactor, and install a stirrer, a thermometer, a condenser and a water separator in the reactor; Then, add bio-based phenol, bio-based amine and bio-based aldehyde with a molar ratio of 1:1.1 - 1.5:2.5 - 3 to the reactor, and then add toluene with a weight 1 - 3 times the total mass of the mixture in the reactor and a catalyst with a weight of 1‰ - 1% of the total weight of the reaction materials. After stirring evenly, heat up, and use the water separator to separate the water generated in the system while heating up. When the temperature rises to 120 - 140 °C, maintain the reaction for 3 - 5 h to obtain a resin mixture; Finally, wash the obtained resin mixture with 1 mol / L NaOH solution, layer it, and take out the lower resin layer after layering. Then, wash the lower resin layer with deionized water for a second time, layer it, and also take out the lower resin layer after the second layering. Then, use a rotary evaporator to remove toluene and water in the lower resin layer after the second layering, and the required highly heat-resistant all-bio-based benzoxazine resin is obtained.

[0007] Further, the bio-based phenol is any one or a mixture of several of p-hydroxyacetophenone, guaiacol, 4-ethylphenol; the bio-based amine is 2-phenylethylamine; the bio-based aldehyde is benzaldehyde; the catalyst is any one or a mixture of several of zinc chloride, indium trihalide, ferric trichloride, antimony pentachloride, trifluoromethanesulfonate, morpholine trifluoroacetate, sodium hydroxide.

[0008] A resin composition for a copper clad laminate, and its innovation lies in: the resin composition for a copper clad laminate is prepared by mixing 50 parts by mass of naphthalene ring epoxy resin, 20 - 30 parts by mass of the above-mentioned highly heat-resistant all-bio-based benzoxazine resin, 10 - 20 parts by mass of maleimide resin, 0.1 - 0.5 parts by mass of an imidazole catalyst, 60 - 80 parts by mass of a filler and 60 - 100 parts by mass of a solvent evenly at 30 - 50 °C.

[0009] Further, the solid content of the resin composition for the copper clad laminate is 58% to 75%.

[0010] Further, the naphthalene ring epoxy resin has the chemical structural formula shown in Formula (2): The maleimide resin has the general chemical structural formula shown in Formula (3): In Formula (3): R2 and R3 are any one of -H, -CH3, and -C2H5; The imidazole catalyst is any one or a mixture of two or more of imidazole, 2-methylimidazole, 1-methylimidazole, 1,2-dimethylimidazole, 1,3-dimethylimidazole, and 2,4-dimethylimidazole; The filler is any one or a mixture of two or more of montmorillonite, calcium carbonate, magnesium hydroxide, zinc borate, talc, aluminum hydroxide, kaolin, barium sulfate, silicon dioxide, silica powder, mica powder, hollow glass microspheres, and fumed silica; The solvent is any one or a mixture of two or more of methyl ethyl ketone, toluene, xylene, cyclohexanone, propylene glycol monomethyl ether, propylene glycol methyl ether acetate, N,N-dimethylformamide, N,N-dimethylacetamide, and methyl isobutyl ketone.

[0011] The advantages of the present invention are as follows: The high heat-resistant all-bio-based benzoxazine resin of the present invention is prepared by reacting bio-based phenol, bio-based amine, and bio-based aldehyde. All raw materials participating in the reaction are bio-based raw materials, and the synthesized benzoxazine resin is an all-bio-based benzoxazine resin.

[0012] For the high heat-resistant all-bio-based benzoxazine resin of the present invention, whether the synthesis raw material is a phenol source or an amine source, its chemical structure contains a rigid benzene ring structure, and the synthesized all-bio-based benzoxazine resin has good heat resistance, with a glass transition temperature Tg≥190°C; the thermal weight loss Td5%≥315°C.

[0013] The resin composition for the copper clad laminate of the present invention is formed by mixing a high heat-resistant all-bio-based benzoxazine resin, a naphthalene ring epoxy resin, and a maleimide resin to form a resin composition. The phenolic hydroxyl group formed by the ring-opening of the benzoxazine resin undergoes a ternary polymerization reaction with the epoxy group of the naphthalene ring epoxy and the imide ring of the maleimide resin to form a crosslinked network structure containing high heat-resistant naphthalene rings and imide rings. This composition has good heat resistance: Tg≥215°C, Td5%≥395°C.

[0014] The resin composition for the copper clad laminate of the present invention can replace the existing petroleum-based benzoxazine resin for formulating the resin composition for high-performance copper clad laminates. Specific embodiments

[0015] To further elaborate on the technical means and effects adopted by the present invention to achieve the predetermined invention purpose, the following preferred embodiments will detail the specific implementation manners, structures, features, and their effects according to the present invention as follows.

[0016] A high heat-resistant all-bio-based benzoxazine resin of the present invention has a general chemical structure formula shown in Formula (1): In Formula (1): R1 is any one of -COCH3, -OCH3, and -CH2CH3.

[0017] The above-mentioned high heat-resistant all-bio-based benzoxazine resin is prepared through the following steps: First, take a reactor, and install a stirrer, a thermometer, a condenser, and a water separator in the reactor.

[0018] Then, add bio-based phenol, bio-based amine, and bio-based aldehyde with a molar ratio of 1:1.1 - 1.5:2.5 - 3 to the reactor. Among them, the bio-based phenol is any one or a mixture of several of p-hydroxyacetophenone, guaiacol, and 4-ethylphenol, the bio-based amine is 2-phenylethylamine, and the bio-based aldehyde is benzaldehyde.

[0019] Then add toluene with a weight 1 - 3 times the total mass of the mixture in the reactor and a catalyst with a weight of 1‰ - 1% of the total weight of the reaction materials. The catalyst is any one or a mixture of several of zinc chloride, indium trihalide, ferric trichloride, antimony pentachloride, trifluoromethanesulfonate, morpholine trifluoroacetate, and sodium hydroxide. After stirring evenly, heat up, and use the water separator to separate the water generated in the system while heating up. When the temperature rises to 120 - 140 °C, maintain the reaction for 3 - 5 h to obtain a resin mixture.

[0020] Finally, wash the obtained resin mixture with 1 mol / L NaOH solution, layer it, and take out the lower resin layer after layering. Then wash the lower resin layer with deionized water for a second time, layer it, and also take out the lower resin layer after the second layering. Then use a rotary evaporator to remove toluene and water in the lower resin layer after the second layering, and the required high heat-resistant all-bio-based benzoxazine resin is obtained.

[0021] Table 1 is a data comparison table of the high heat-resistant all-bio-based benzoxazine resin prepared by the method of the present invention and the benzoxazine resin prepared by the traditional method: In Table 1, Examples 1-1, 1-2, 1-3 and 1-4 are highly heat-resistant all-biobased benzoxazine resins prepared by the preparation method of the present invention, and the comparative example is a benzoxazine resin prepared by a traditional method. The polyformaldehyde used in the comparative example is analytically pure granular polyformaldehyde from Merck Chemical with a purity of 92%.

[0022] The highly heat-resistant all-biobased benzoxazine resin prepared in the embodiment of the present invention and the benzoxazine resin of the comparative example were cured at 140°C for 1h, 160°C for 1h, 180°C for 1h, and 200°C for 2h to form a 50mm×50mm×0.8mm casting, and the Tg and Td were tested. 5% .

[0023] The above-mentioned high heat-resistant all-bio-based benzoxazine resin is used to prepare a resin composition for copper-clad laminates. The resin composition for copper-clad laminates is prepared by mixing and stirring 50 parts by mass of naphthalene epoxy resin, 20 to 30 parts by mass of high heat-resistant all-bio-based benzoxazine resin, 10 to 20 parts by mass of maleimide resin, 0.1 to 0.5 parts by mass of imidazole catalyst, 60 to 80 parts by mass of filler and 60 to 100 parts by mass of solvent at 30 to 50°C.

[0024] The solid content of the resin composition for copper clad laminate is 58% to 75%, and the solid content is defined as the weight percentage of the solid content in the solution to the total solution.

[0025] Naphthalene epoxy resin has the chemical structure shown in formula (2): Specifically, the naphthalene ring epoxy resin is selected from one of DFE225 and DFE226 of Sichuan Dongcai Technology Group Co., Ltd. or a mixture of two of them.

[0026] Maleimide resin has the general chemical structure shown in formula (3): In formula (3), R2 and R3 are any one of -H, -CH3 and -C2H5.

[0027] Specifically, the maleimide resin is selected from one of DFE930, DFE936, and DFE939 of Sichuan Dongcai Technology Group Co., Ltd., or a mixture of two or more thereof.

[0028] The imidazole catalyst is any one of imidazole, 2-methylimidazole, 1-methylimidazole, 1,2-dimethylimidazole, 1,3-dimethylimidazole, and 2,4-dimethylimidazole, or a mixture of two or more thereof; The filler is any one or a mixture of two or more of montmorillonite, calcium carbonate, magnesium hydroxide, zinc borate, talc, aluminum hydroxide, kaolin, barium sulfate, silicon dioxide, silica powder, mica powder, hollow glass microspheres, and fumed silica; The solvent is any one or a mixture of two or more of methyl ethyl ketone, toluene, xylene, cyclohexanone, propylene glycol monomethyl ether, propylene glycol methyl ether acetate, N,N-dimethylformamide, N,N-dimethylacetamide, and methyl isobutyl ketone.

[0029] Table 2 shows the dosage of the formula raw materials and the technical performance of the resin composition for the copper clad laminate of the present invention. In Table 2, the resin compositions for the copper clad laminate prepared in Examples 2-1, 2-2, 2-3, and 2-4 were cured according to the procedure of 140°C for 1 h, 160°C for 1 h, 180°C for 1 h, and 200°C for 2 h to make a casting body of 50 mm × 50 mm × 0.8 mm, and the Tg and Td were measured. 5% 。

[0030] The test methods in Table 1 and Table 2 are as follows: (1) Glass transition temperature (Tg) According to differential scanning calorimetry, it was measured according to the DSC method specified in IPC-TM-650 2.4.25.

[0031] (2) Thermal decomposition temperature (Td) It was measured according to the method specified in IPC-TM-650 2.4.26.

[0032] As can be seen from Table 1, the fully bio-based benzoxazine resin (using benzaldehyde as the aldehyde source) obtained by applying the examples of the present invention has higher heat resistance than the benzoxazine resin synthesized using petroleum-based paraformaldehyde as the aldehyde source.

[0033] As can be seen from Table 2, the resin composition for the copper clad laminate obtained by applying the examples of the present invention has excellent heat resistance. The resin composition for the copper clad laminate of the present invention can be used in fields such as laminates, integrated circuit packaging, high-performance copper clad laminates, high-density Internet, and artificial intelligence, and has broad application prospects.

[0034] In the above examples: Among the percentage ratios used, if not specifically noted, they are all mass (weight) percentage ratios or percentage ratios well-known to those skilled in the art; among the ratios used, if not specifically noted, they are all mass (weight) ratios; the weight parts can all be grams or kilograms.

[0035] In the above examples: For the process parameters (temperature, time, pressure, etc.) and the numerical values of the dosages of each component in each step that are in a range, any point can be applicable.

[0036] The content of the present invention and the technical content not specifically described in the above embodiments are the same as those of the prior art, and the raw materials are all commercially available products.

[0037] The high heat-resistant all-bio-based benzoxazine resin of the present invention is prepared by reacting bio-based phenols (p-hydroxyacetophenone is obtained from the stems and leaves of Artemisia scoparia Waldst. & Kit., which belongs to the Compositae family; guaiacol is the main component of wood tar oil and is obtained from guaiac resin, pine oil, etc.; 4-ethylphenol is derived from eggs, European cranberries, pork, whisky, coffee, etc.), bio-based amines (2-phenylethylamine comes from chocolate and after microbial fermentation), and bio-based aldehydes (benzaldehyde comes from hyacinth, citronella, cinnamon, iris, cistus). All raw materials participating in the reaction are bio-based raw materials, and the synthesized benzoxazine resin is an all-bio-based benzoxazine resin.

[0038] For the high heat-resistant all-bio-based benzoxazine resin of the present invention, whether the synthesis raw materials are phenol sources or amine sources, their chemical structures contain rigid benzene ring structures, and the synthesized all-bio-based benzoxazine resin has good heat resistance, with a glass transition temperature Tg≥190°C; the thermal weight loss Td5%≥315°C.

[0039] The resin composition for a copper clad laminate of the present invention is formed by mixing a high heat-resistant all-bio-based benzoxazine resin with a naphthalene ring epoxy resin and a maleimide resin. The phenolic hydroxyl group formed by the ring-opening of the benzoxazine resin undergoes a ternary polymerization reaction with the epoxy group of the naphthalene ring epoxy and the imide ring of the maleimide resin to form a cross-linked network structure containing high heat-resistant naphthalene rings and imide rings. This composition has good heat resistance: Tg≥215°C, Td5%≥395°C.

[0040] The resin composition for a copper clad laminate of the present invention can replace the existing petroleum-based benzoxazine resin for formulating a resin composition for high-performance copper clad laminates.

[0041] The above are only the preferred embodiments of the present invention, and do not impose any form of limitation on the present invention. Although the present invention has been disclosed above with preferred embodiments, it is not intended to limit the present invention. Any person skilled in the art can make some modifications or equivalent changes within the scope of the technical solution of the present invention by using the disclosed technical content. However, as long as it does not depart from the content of the technical solution of the present invention, any brief modifications, equivalent changes, and modifications made to the above embodiments based on the technical essence of the present invention still fall within the scope of the technical solution of the present invention.

Claims

1. A high heat-resistant all-bio-based benzoxazine resin, characterized in that: The benzoxazine resin has the general chemical structure formula shown in formula (1): In formula (1): R1 is any one of -COCH3, -OCH3, -CH2CH3.

2. The preparation method of the highly heat-resistant all-bio-based benzoxazine resin according to claim 1, characterized in that: It includes the following steps: First, take a reactor, and install a stirrer, a thermometer, a condenser and a water separator in the reactor; Then, add bio-based phenol, bio-based amine and bio-based aldehyde with a molar ratio of 1:1.1 - 1.5:2.5 - 3 into the reactor, and then add toluene with a weight 1 - 3 times that of the total mass of the mixture in the reactor and a catalyst with a weight of 1‰ - 1% of the total weight of the reaction materials. After stirring evenly, heat up, and while heating up, use the water separator to separate the water generated in the system. When the temperature rises to 120 - 140 °C, maintain the reaction for 3 - 5 h to obtain a resin mixture; Finally, wash the obtained resin mixture with 1 mol / L NaOH solution, layer it, and take out the lower resin layer after layering. Then, wash the lower resin layer with deionized water for a second time, layer it, and also take out the lower resin layer after the second layering. Then, use a rotary evaporator to remove toluene and water in the lower resin layer after the second layering, and the required high heat-resistant all-bio-based benzoxazine resin is obtained.

3. The high heat-resistant all-bio-based benzoxazine resin according to claim 2, wherein: The bio-based phenol is any one or a mixture of several of p-hydroxyacetophenone, guaiacol, 4-ethylphenol; the bio-based amine is 2-phenylethylamine; the bio-based aldehyde is benzaldehyde; the catalyst is any one or a mixture of several of zinc chloride, indium trihalide, ferric trichloride, antimony pentachloride, trifluoromethanesulfonate, morpholine trifluoroacetate, sodium hydroxide.

4. A resin composition for a copper clad laminate, characterized in that: The resin composition for a copper clad laminate is prepared by uniformly mixing 50 parts by mass of naphthalene ring epoxy resin, 20 - 30 parts by mass of the high heat-resistant all-bio-based benzoxazine resin described in claim 1, 10 - 20 parts by mass of maleimide resin, 0.1 - 0.5 parts by mass of imidazole catalyst, 60 - 80 parts by mass of filler and 60 - 100 parts by mass of solvent at 30 - 50 °C.

5. The resin composition for a copper clad laminate according to claim 4, wherein: The solid content of the resin composition for a copper clad laminate is 58% - 75%.

6. The resin composition for a copper clad laminate according to claim 4, wherein: The naphthalene ring epoxy resin has the chemical structural formula shown in formula (2): The maleimide resin has the general chemical structure formula shown in formula (3): In formula (3): R2, R3 are any one of -H, -CH3, -C2H5; The imidazole catalyst is any one or a mixture of two or more of imidazole, 2-methylimidazole, 1-methylimidazole, 1,2-dimethylimidazole, 1,3-dimethylimidazole, 2,4-dimethylimidazole; The filler is any one or a mixture of two or more of montmorillonite, calcium carbonate, magnesium hydroxide, zinc borate, talc, aluminum hydroxide, kaolin, barium sulfate, silica, silica powder, mica powder, hollow glass microspheres, fumed silica; The solvent is any one or a mixture of two or more of methyl ethyl ketone, toluene, xylene, cyclohexanone, propylene glycol monomethyl ether, propylene glycol methyl ether acetate, N,N-dimethylformamide, N,N-dimethylacetamide, methyl isobutyl ketone.

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