Ketone-containing bifuran monomer compound, preparation method thereof, electronic packaging adhesive and application thereof

Abstract

The application relates to a ketone-containing bifuran monomer compound, a preparation method thereof, an electronic packaging adhesive and application, and belongs to the technical field of chemical synthesis. The ketone-containing bifuran monomer compound has a structural formula shown in formula I or formula II: R1 is selected from any one of the following structural formulas: wherein n1=0-10, n2=0-10, n3=1-10, n4=0-7, n5=0-4, R2 and R3 are independently selected from hydrogen, C6-C10 aryl, C1-C4 alkyl, and the like. 12 10 The application introduces a ketone-containing group into a bifuran group, utilizes electrophilicity of the ketone-containing group, makes the ketone-containing bifuran monomer compound have high curing activity, forms a high polymer network structure or a crosslinking structure, enhances the strength and rigidity of the ketone-containing bifuran monomer compound, and due to the influence of the ketone group on the molecular chain movement of the ketone-containing bifuran monomer compound, the ketone-containing bifuran monomer compound has a high glass transition temperature.​

Description

Technical Field

[0001] This invention relates to the field of chemical synthesis technology, specifically to a ketone-containing difuranyl monomer compound and its preparation method, as well as an electronic encapsulation adhesive and its applications. Background Technology

[0002] Epoxy resins are widely used in aerospace, coatings, adhesives, and composite materials due to their excellent properties. Epoxy resins contain active epoxy groups and possess advantages such as good mechanical properties, good adhesion, corrosion resistance, high temperature resistance, high strength, and simple processing, making them the main component responsible for adhesive strength.

[0003] Currently, the most common epoxy resin is bisphenol A diester ether, which belongs to the bisphenol A class of monomers. It has a certain degree of toxicity and is harmful to the environment and human health. Furthermore, due to the rigidity of the benzene ring, bisphenol A type epoxy resins have high internal stress after curing, are brittle, and prone to cracking, thus limiting their application in certain technical fields.

[0004] Furan-based epoxy resins are green and renewable bio-based products with good toughness, but they typically have a low glass transition temperature, poor mechanical properties, and a slow curing reaction, making them difficult to promote in practical applications. Summary of the Invention

[0005] To address the aforementioned technical problems, this invention provides a ketone-containing bisfuranyl monomer compound, its preparation method, an electronic encapsulation adhesive, and its application, aiming to at least partially solve at least one of the aforementioned technical problems.

[0006] According to one aspect of the present invention, a ketone-containing difuranyl monomer compound of formula I or formula II is provided.

[0007]

[0008] R1 is selected from any of the following structural formulas:

[0009]

[0010] Where n1 = 0–10, n2 = 0–10, n3 = 1–10, n4 = 0–7, n5 = 0–4, and R2 and R3 are independently selected from hydrogen, C6–C6, and C4, respectively. 12 aryl, C1-C 10 Alkyl groups.

[0011] According to some embodiments of the present invention, n1 = 0 to 3, n2 = 0 to 3, n3 = 1 to 4, n4 = 0 to 5, and R2 and R3 are independently selected from hydrogen, methyl and ethyl, respectively.

[0012] According to some embodiments of the present invention, the above-mentioned ketone-containing difuranyl monomer compounds include compounds with structures shown in Formulas I1 to I6 or Formulas II1 to II6:

[0013]

[0014]

[0015] According to another aspect of the present invention, a method for preparing the above-mentioned ketone-containing difuranyl monomer compound is provided, the ketone-containing difuranyl monomer compound having the structure of Formula II, the preparation method comprising: mixing epichlorohydrin, an aqueous sodium hydroxide solution and a phase transfer catalyst under an inert gas atmosphere, and then adding the compound shown in Formula I dropwise and stirring to prepare a reaction solution containing the compound shown in Formula II.

[0016] According to some embodiments of the present invention, the molar ratio of epichlorohydrin and the compound shown in Formula I is 2:1 to 20:1; preferably 14:1; the phase transfer catalyst is a quaternary ammonium salt catalyst; preferably, the quaternary ammonium salt catalyst specifically includes at least one of tetrabutylammonium hydrogen sulfate, benzyltriethylammonium chloride, tetrabutylammonium bromide, tetrabutylammonium chloride, tetrabutylammonium hydroxide, hexadecyltrimethylammonium chloride, benzyltriethyltetrafluoroborate, tributylmethylammonium chloride, and methyltrioctylammonium chloride; the stirring time is 2 to 24 hours, and the stirring temperature is 50 to 100°C; preferably, the stirring time is 5 hours.

[0017] According to another aspect of the present invention, an electronic encapsulating adhesive is provided, comprising a ketone-containing difuranyl monomer compound as described above, the ketone-containing difuranyl monomer compound having the structure shown in Formula II.

[0018] According to some embodiments of the present invention, the electronic encapsulating adhesive is composed of a compound represented by Formula II and a curing agent, wherein the curing agent is a diamine compound.

[0019] According to some embodiments of the present invention, the mass ratio of the compound represented by Formula II to the curing agent is 2:1.

[0020] According to some embodiments of the present invention, the curing conditions for the electronic encapsulation adhesive are as follows: first, curing at 70-90°C for 2-4 hours; then curing at 120-140°C for 2-4 hours.

[0021] According to another aspect of the present invention, an application of the electronic encapsulating adhesive as described above is provided in the fields of conductive encapsulation and insulating encapsulation.

[0022] Based on the above technical solutions, the ketone-containing difuranyl monomer compound, its preparation method, electronic encapsulating adhesive, and its application of the present invention have at least one or more of the following beneficial effects:

[0023] This invention introduces a ketone-containing group into the middle of a bisfuran group. Utilizing the stability of the ketone-containing group structure, the ketone-containing bisfuran monomer compound of this application exhibits high rigidity in the solid state. Furthermore, the electrophilicity of the ketone-containing group facilitates reaction, resulting in good curing activity during subsequent curing, forming a polymeric network structure or cross-linked structure, thereby enhancing the strength and rigidity of the prepared electronic encapsulation adhesive. During subsequent curing, the movement between molecular chains in the ketone-containing bisfuran monomer compound of this application is restricted, resulting in a high glass transition temperature. Therefore, the electronic encapsulation adhesive prepared at higher temperatures exhibits high stability. Attached Figure Description

[0024] Figure 1 The 1H NMR spectrum of the ketone-containing difuranyl epoxy monomer 1B prepared in Example 1 of this invention;

[0025] Figure 2 The 1H NMR spectrum of the ketone-containing difuranyl epoxy monomer 2B prepared in Example 22 of this invention;

[0026] Figure 3 The 1H NMR spectrum of the ketone-containing difuranyl epoxy monomer 3B prepared in Example 23 of this invention;

[0027] Figure 4 The 1H NMR spectrum of the ketone-containing difuranyl epoxy monomer 4B prepared in Example 24 of this invention;

[0028] Figure 5 The 1H NMR spectrum of the ketone-containing difuranyl epoxy monomer 5B prepared in Example 25 of this invention; and

[0029] Figure 6 The image shows the 1H NMR spectrum of the ketone-containing difuranyl epoxy monomer 6B prepared in Example 26 of this invention. Detailed Implementation

[0030] To make the objectives, technical solutions, and advantages of the present invention clearer, the present invention will be further described in detail below with reference to specific embodiments and accompanying drawings.

[0031] The endpoints and any values ​​of the ranges invented in this invention are not limited to the precise ranges or values, and these ranges or values ​​should be understood to include values ​​close to these ranges or values. For numerical ranges, the endpoint values ​​of the various ranges, the endpoint values ​​of the various ranges and individual point values, and individual point values ​​can be combined with each other to obtain one or more new numerical ranges, which should be considered as specifically invented in this invention.

[0032] The terminology used herein is for the purpose of describing particular embodiments only and is not intended to limit the invention. The terms “comprising,” “including,” etc., as used herein indicate the presence of the stated features, steps, operations, and / or components, but do not exclude the presence or addition of one or more other features, steps, operations, or components.

[0033] All terms used herein (including technical and scientific terms) have the meanings commonly understood by those skilled in the art, unless otherwise defined. It should be noted that the terms used herein are to be interpreted in a manner consistent with the context of this specification, and not in an idealized or overly rigid way.

[0034] Similarly, to simplify the invention and aid in understanding one or more aspects of the invention, in the above description of exemplary embodiments of the invention, various features of the invention are sometimes grouped together in a single embodiment, figure, or description thereof. The use of terms such as "one embodiment," "some embodiments," "example," "specific example," or "some examples" indicates that a specific feature, structure, material, or characteristic described in connection with that embodiment or example is included in at least one embodiment or example of the invention. In this specification, illustrative expressions of the above terms do not necessarily refer to the same embodiment or example. Furthermore, the specific features, structures, materials, or characteristics described may be combined in any suitable manner in one or more embodiments or examples.

[0035] Furthermore, the technical solutions of the various embodiments can be combined with each other, but only if they are feasible for those skilled in the art. If the combination of technical solutions is contradictory or cannot be implemented, it should be considered that such combination of technical solutions does not exist and is not within the scope of protection claimed by this invention.

[0036] When furan-based epoxy resins are used as bio-based products in related technologies, they have excellent flow properties and a low coefficient of thermal expansion. However, due to structural defects in bio-based compounds, they have low glass transition temperatures, poor mechanical properties, and slow curing reaction performance, which affect the material properties of furan-based epoxy resins.

[0037] In the process of developing this invention, it was discovered that by introducing ketone-containing groups onto the bisfuran backbone, the stability of the ketone-containing groups is utilized to give the monomer compound high rigidity after curing. Furthermore, the electrophilicity of the ketone-containing groups gives it high curing activity during subsequent curing, which is beneficial for forming a polymer network structure or cross-linked structure. This enhances the strength and rigidity of the monomer compound after curing, giving it a high glass transition temperature.

[0038] Specifically, according to some embodiments of the present invention, a ketone-containing difuranyl monomer compound having a structure of Formula I or Formula II is provided:

[0039]

[0040] R1 is selected from any of the following structural formulas:

[0041]

[0042] Where n1 = 0–10, n2 = 0–10, n3 = 1–10, n4 = 0–7, n5 = 0–4, and R2 and R3 are independently selected from hydrogen, C6–C6, and C4, respectively. 12 aryl, C1-C 10 Alkyl groups.

[0043] According to some embodiments of the present invention, n1 can be, for example, 0, 1, 2, 3, 4, 5, 6, 7, 8, 9 or 10; n2 can be, for example, 0, 1, 2, 3, 4, 5, 6, 7, 8, 9 or 10; n3 can be, for example, 0, 1, 2, 3, 4, 5, 6, 7, 8, 9 or 10; n4 can be, for example, 0, 1, 2, 3, 4, 5, 6 or 7; n5 can be, for example, 0, 1, 2, 3 or 4, but is not limited thereto.

[0044] C6~C 12 The aryl group includes, but is not limited to, phenyl and biphenyl.

[0045] According to some embodiments of the present invention, the monomeric compounds represented by Formula I or Formula II have a bisfuran backbone. The introduction of bisfuran groups forms a stable ring structure, improving the thermal stability of the monomeric compounds and facilitating the subsequent preparation of electronic encapsulation adhesives with a lower coefficient of thermal expansion and better toughness. By introducing ketone-containing groups between the bisfuran groups, the stability of the ketone-containing groups is utilized, resulting in high rigidity of the ketone-containing bisfuran monomeric compounds in the solid state. Furthermore, the electrophilicity of the ketone-containing groups facilitates their reaction with other compounds, resulting in better curing activity during subsequent curing reactions with curing agents, forming a polymeric network structure or cross-linked structure, thereby enhancing the strength and rigidity of the prepared electronic encapsulation adhesive. During subsequent curing, the movement between molecular chains in the ketone-containing bisfuran monomeric compounds of the present invention is restricted, resulting in a higher glass transition temperature. Therefore, at higher temperatures, the prepared electronic encapsulation adhesive exhibits higher stability.

[0046] Preferably, n1 = 0–3, n2 = 0–3, n3 = 1–4, n4 = 0–5, and R2 and R3 are independently selected from hydrogen, methyl, and ethyl, respectively. When R2 and R3 are selected from methyl or ethyl chain alkanes, a higher glass transition temperature and better curing activity are ensured while reducing the introduction of rigid groups on the benzene ring. This reduces stress during the preparation of electronic encapsulation adhesive, reduces crack formation, and results in better stability.

[0047] According to some embodiments of the present invention, the above-mentioned ketone-containing difuranyl monomer compounds include compounds with structures shown in Formulas I1 to I6 or Formulas II1 to II6:

[0048]

[0049]

[0050] According to some embodiments of the present invention, the compounds of formulas II1 to II6 have high glass transition temperatures, good mechanical properties and good curing activity when the electronic encapsulation adhesive is subsequently prepared.

[0051] According to some embodiments of the present invention, a method for preparing the compound of Formula II is provided, comprising: mixing epichlorohydrin, an aqueous sodium hydroxide solution and a phase transfer catalyst under an inert gas atmosphere, and then adding dropwise an organic solution of the compound of Formula I and stirring to prepare a reaction solution containing the compound of Formula II.

[0052] The specific reaction process is as follows:

[0053]

[0054] According to some embodiments of the present invention, epichlorohydrin contains epoxy groups. During stirring, epichlorohydrin undergoes a ring-opening reaction with the compound shown in Formula I, introducing epoxy groups to form the framework structure of the epoxy resin. An aqueous solution of sodium hydroxide acts as a basic catalyst for the condensation reaction, facilitating the condensation reaction between the compound shown in Formula I and epichlorohydrin, thereby increasing the reaction rate and selectivity. A phase transfer catalyst facilitates the transfer of sodium hydroxide from the aqueous phase to the organic phase, promoting the reaction.

[0055] According to an embodiment of the present invention, the organic solvent added to the organic solution of the compound represented by Formula I is tetrahydrofuran or methanol, preferably tetrahydrofuran.

[0056] According to some embodiments of the present invention, the inert gas atmosphere is nitrogen or argon, preferably nitrogen.

[0057] According to some embodiments of the present invention, the molar ratio of epichlorohydrin and the compound represented by Formula I is 2:1 to 20:1, for example, it can be 2:1, 3:1, 4:1, 5:1, 6:1, 7:1, 8:1, 9:1, 10:1, 11:1, 12:1, 13:1, 14:1, 15:1, 16:1, 17:1, 18:1, 19:1 or 20:1, preferably 14:1. Preliminary experiments related to the invention have shown that when the molar ratio of the two is 14:1, the yield of the compound of Formula II is higher. The phase transfer catalyst is a quaternary ammonium salt catalyst; preferably, the quaternary ammonium salt catalyst specifically includes at least one of the following: tetrabutylammonium hydrogen sulfate, benzyltriethylammonium chloride, tetrabutylammonium bromide, tetrabutylammonium chloride, tetrabutylammonium hydroxide, hexadecyltrimethylammonium chloride, benzyltriethyltetrafluoroborate ammonium, tributylmethylammonium chloride, and methyltrioctylammonium chloride; the stirring time is 2 to 24 hours, for example, 2 hours, 4 hours, 6 hours, 8 hours, 10 hours, 12 hours, 14 hours, 16 hours, 18 hours, 20 hours, 22 hours, or 24 hours, preferably 5 hours. The stirring temperature is 50 to 100°C, for example, 50°C, 60°C, 70°C, 80°C, 90°C, or 100°C, preferably 50°C.

[0058] In a 250 mL round-bottom flask, 100 mmol of 5-hydroxymethylfurfural, 50 mmol of ketones, 1 mL of acid (hydrochloric acid, sulfuric acid, formic acid, or levonordiic acid), and 100 mL of anhydrous methanol were added, followed by a certain amount of sodium hydroxide aqueous solution. The mixture was stirred at 475 rpm in an oil bath at 308 K for a certain period of time. After the reaction was cooled to room temperature, the product solution was neutralized with 0.5 M hydrochloric acid solution, diluted with methanol, and analyzed by high-performance liquid chromatography (HPLC). After rotary evaporation of methanol, the structure of the product was determined by 1H NMR spectroscopy.

[0059] The reaction process is as follows:

[0060]

[0061] According to some embodiments of the present invention, the method for preparing the compound of formula II further includes: quenching with ice water, followed by extraction, drying, rotary evaporation and drying in sequence to prepare the compound shown in formula II.

[0062] Specifically, after quenching with ice water, a large amount of ethyl acetate was poured in to extract the product into the organic phase. Anhydrous sodium sulfate was added to dry the organic phase, and then the organic phase was rotary evaporated to obtain the compound of formula II.

[0063] According to some embodiments of the present invention, an electronic encapsulating adhesive is provided, comprising a ketone-containing bisfuranyl monomer compound as described above, the ketone-containing bisfuranyl monomer compound having the structure shown in Formula II.

[0064] According to some embodiments of the present invention, the electronic encapsulating adhesive using this structure has excellent high temperature resistance and chemical stability, as well as low swelling and good electrical insulation, thereby ensuring the safe and reliable operation of electronic equipment.

[0065] According to some embodiments of the present invention, the electronic encapsulating adhesive is composed of a compound represented by Formula II and a curing agent. Through curing, a relatively stable cured network structure can be formed, which helps to improve the sealing performance of the electronic encapsulating adhesive. The curing agent is a diamine compound, such as an aliphatic diamine or furanyl diamine, preferably furanyl diamine.

[0066] According to some embodiments of the present invention, the mass ratio of the compound represented by Formula II to the curing agent is 2:1. During the relevant experiments of the present invention, it was found that when the mass ratio of the two is controlled at the above ratio, the resulting electronic encapsulation adhesive exhibits better bonding and sealing effects.

[0067] According to some embodiments of the present invention, electronic components are subject to adverse factors such as high humidity, impact, and mechanical vibration during operation. Therefore, electronic encapsulation adhesives are required to have good mechanical properties, high toughness, and good water absorption reliability. The bonding and sealing effects of the electronic encapsulation adhesives obtained by the present invention can meet the requirements of electronic encapsulation.

[0068] According to some embodiments of the present invention, the curing conditions for the electronic encapsulation adhesive are as follows: first, curing at 70-90°C for 2-4 hours, for example, 70°C, 75°C, 80°C, 85°C or 90°C, for example, 2 hours, 3 hours or 4 hours; then curing at 120-140°C for 2-4 hours, for example, 120°C, 125°C, 130°C, 135°C or 140°C, for example, 2 hours, 3 hours or 4 hours.

[0069] According to some embodiments of the present invention, electronic encapsulating adhesives as described above are used in the fields of conductive encapsulation and insulating encapsulation.

[0070] According to some embodiments of the present invention, a structure containing ketone difuran groups helps to form good bond strength while having a high glass transition temperature, which can be used to facilitate application and promotion in conductive and insulating packaging.

[0071] Specifically, the steps for preparing the compound represented by Formula II are as follows:

[0072] Epichlorohydrin, 50 wt% sodium hydroxide aqueous solution, and phase transfer catalyst were added to a three-necked flask. The mixture was stirred for 30 min at room temperature under an inert atmosphere. The compound of Formula I was dissolved in 10 mL of tetrahydrofuran and then added dropwise to the reaction flask. The mixture was reacted at 50 °C for 5 h, where n(epicochlorohydrin):n(diol monomer) = 2:1 to 20:1. After the reaction was complete, ice water was added to the mixture to terminate the reaction. The obtained product was extracted with ethyl acetate, dried with anhydrous magnesium sulfate, purified by vacuum distillation, and then dried in a vacuum oven at 35 °C for 24 h to obtain a crude product containing the compound of Formula II.

[0073] Specifically, the process for preparing the electronic encapsulation adhesive is as follows:

[0074] The epoxy monomer and curing agent (furanyl diamine) were mixed in a mass ratio of 2:1. After mixing, the mixture was stirred at room temperature for 5 minutes and then degassed under ultrasound for 15 minutes. The mixture was then transferred to a heated mold (preheating required). The mold was first cured at 80°C for 3 hours, followed by curing at 130°C for 3 hours.

[0075] The present invention will be further illustrated by the following embodiments. In the detailed description below, numerous specific details are set forth for ease of explanation to provide a comprehensive explanation of the embodiments of the present invention. However, it will be apparent that one or more embodiments may be practiced without these specific details. Moreover, the details in the following embodiments can be arbitrarily combined to form other feasible embodiments without conflict.

[0076] It should be noted that the following embodiments are illustrative of the specific content of the present invention. Unless otherwise specified, all raw materials are used directly after purchase. The methods used in the following embodiments are all well-known in the art and can be performed as described in textbooks or related literature, and will not be repeated here. The NMR detection in the embodiments of the present invention uses a Bruker 400MHz NMR instrument.

[0077] Examples 1 to 4:

[0078] In a 250 mL round-bottom flask, furfuryl alcohol (100 mmol), formaldehyde (50 mmol), 1 mL hydrochloric acid, and 100 mL acetonitrile were added, and the mixture was stirred at 475 rpm for 2 hours in an oil bath at 308 K. After cooling to room temperature, the mixture was rotary evaporated and dried. A 50 mL acetonitrile solution of the solid intermediate (50 mmol) and KMnO4 (50 mmol) was reacted for 12 hours to give the compound shown in 1A. The structure of the product was determined by 1H NMR spectroscopy.

[0079]

[0080] 140 mmol of epichlorohydrin, 120 mmol of 50 wt% sodium hydroxide aqueous solution, and 0.32 g of tetrabutylammonium hydrogen sulfate were added to a three-necked flask. The solution was stirred for 30 min at room temperature under a nitrogen atmosphere. Compound 1A was dissolved in 10 mL of tetrahydrofuran and then added dropwise to the reaction flask, where n(epicochlorohydrin):n(compound 1A) = 2:1 to 20:1. The reaction was carried out at 50 °C for 5 h. After the reaction was completed, ice water was added to the mixture to terminate the reaction. The product was extracted with ethyl acetate, dried with anhydrous magnesium sulfate, purified by vacuum distillation, and then dried in a vacuum oven at 35 °C for 24 h to obtain a viscous ketone-containing difuran-based epoxy monomer 1B. Figure 1 The above is the 1H NMR spectrum of the ketone-containing difuranyl epoxy monomer 1B prepared in Example 1 of this invention, as shown below. Figure 1 As shown, the structure of the prepared product is confirmed. The molar yield of the crude product is shown in Table 1 below.

[0081] The reaction preparation process is shown in the figure below:

[0082]

[0083] Examples 5 to 6:

[0084] The preparation process of Examples 5 and 6 is basically the same as that of Example 1. The difference is that the reaction parameters are changed according to Table 1 below, including fixing n (epimycochloropropane):n (compound 1A) at 14:1, and then replacing the nitrogen atmosphere with argon and air respectively. The yields obtained are shown in Table 1 below.

[0085] Examples 7 to 14:

[0086] The preparation processes of Examples 7 to 14 are basically the same as those of Example 1, except that the reaction parameters are fixed according to Table 1 below, including: fixing n (epoxychloropropane):n (compound 1A) to 14:1, and then replacing tetrabutylammonium bisulfate with benzyltriethylammonium chloride, tetrabutylammonium bromide, tetrabutylammonium chloride, tetrabutylammonium hydroxide, hexadecyltrimethylammonium chloride, benzyltriethyltetrafluoroborate, tributylmethylammonium chloride, and methyltrioctylammonium chloride, respectively. The yields obtained are shown in Table 1 below.

[0087] Example 15:

[0088] The preparation process of Example 15 is basically the same as that of Example 1, except that the reaction parameters are fixed according to Table 1 below, including: fixing n (epimycochloropropane):n (compound 1A) to 14:1, and then replacing the solvent with tetrahydrofuran instead of methanol. The yields obtained are shown in Table 1 below.

[0089] Examples 16-19:

[0090] The preparation process of Examples 16-19 is basically the same as that of Example 1, except that the reaction parameters are fixed according to Table 1 below, including fixing n(epimchlorohydrin):n(compound 1A) to 14:1, and then replacing the reaction time with 2 hours, 10 hours, 15 hours and 24 hours respectively, and the yields obtained are shown in Table 1 below.

[0091] Examples 20-21:

[0092] The preparation process of Examples 20 and 21 is basically the same as that of Example 1. The difference is that the reaction parameters are fixed according to Table 1 below, including fixing n (epimycochloropropane):n (compound 1A) to 14:1, and then adjusting the reaction temperature to 75℃ and 100℃ respectively. The yields obtained are shown in Table 1 below.

[0093] Example 22:

[0094] 100 mmol of 5-hydroxymethylfurfural, 50 mmol of 5-methoxy-1,3,4-triphenyl-4,5-dihydro-1H-1,2,4-triazolline, and 100 mL of dichloromethane were added to a 250 mL reaction vessel, and the mixture was heated at 40 °C for 30 minutes under a nitrogen atmosphere. After the reaction was cooled to room temperature, the solid was separated by filtration and dried to obtain the compound shown in Formula 2A.

[0095]

[0096] The subsequent reaction steps are basically the same as in Example 1, except that the reaction parameters are fixed as shown in Table 1 below, including: fixing n(epimyl chloride):n(compound 2A) to 14:1, and then replacing the added compound 1A with compound 2A. The yield of the compound represented by formula 2B is shown in Table 1 below. Figure 2 The above is the 1H NMR spectrum of the ketone-containing difuranyl epoxy monomer 2B prepared in Example 22 of this invention. Figure 2 Its structure can be verified.

[0097]

[0098] Example 23:

[0099] Compound 2A (100 mmol), acetonitrile (50 mL), vanadium oxysulfate (2 mol%, representing 2% of the molar amount of substrate 2A), and copper nitrate (2 mol%, representing 2% of the molar amount of substrate 2A) were added to a 250 mL round-bottom flask, with oxygen continuously bubbled in. The mixture was stirred at 475 rpm for a certain period of time in an oil bath at 353.15 K. After the reaction was cooled to room temperature, the product solution was directly rotary evaporated and subjected to rapid column chromatography (petroleum ether: ethyl acetate = 3:5) to obtain the compound shown in formula 3A.

[0100]

[0101] The subsequent reaction steps are basically the same as in Example 1, except that the reaction parameters are fixed as shown in Table 1 below, including: fixing n (epimycochloropropane):n (compound 3A) to 14:1, and then replacing the added compound 1A with compound 3A, and the yield of the compound shown in Formula 3B is shown in Table 1 below. Figure 3 The above is the 1H NMR spectrum of the ketone-containing difuranyl epoxy monomer 3B prepared in Example 23 of this invention. Figure 3 Its structure can be verified.

[0102]

[0103] Example 24:

[0104] In a 250 mL round-bottom flask, 100 mmol of 5-hydroxymethylfurfural, 50 mmol of acetone, 1 mL of sulfuric acid, and 100 mL of anhydrous methanol were added, followed by 20 mL of sodium hydroxide aqueous solution. The mixture was stirred at 475 rpm in an oil bath at 308 K for a certain period of time. After the reaction was cooled to room temperature, the product solution was neutralized with 0.5 M hydrochloric acid solution, diluted with methanol, and then analyzed by HPLC. Rotary evaporation of methanol yielded the compound shown in formula 4A.

[0105]

[0106] The subsequent reaction steps are basically the same as in Example 1, except that the reaction parameters are fixed as shown in Table 1 below, including: fixing n (epimycochloropropane):n (compound 4A) to 14:1, and then replacing the added compound 1A with compound 4A. The yield of the compound represented by formula 4B is shown in Table 1 below. Figure 4 The above is the 1H NMR spectrum of the ketone-containing difuranyl epoxy monomer 4B prepared in Example 24 of this invention. Figure 4 Its structure can be verified.

[0107]

[0108] Example 25:

[0109] In a 250 mL round-bottom flask, 100 mmol of 5-hydroxymethylfurfural, 50 mmol of cyclopentanone, 1 mL of sulfuric acid, and 100 mL of anhydrous methanol were added, followed by 20 mL of sodium hydroxide aqueous solution. The mixture was stirred at 475 rpm in an oil bath at 308 K for a certain period of time. After the reaction was cooled to room temperature, the product solution was neutralized with 0.5 M hydrochloric acid solution, diluted with methanol, and analyzed by HPLC. Rotary evaporation of methanol yielded the compound shown in formula 5A.

[0110]

[0111] The subsequent reaction steps are basically the same as in Example 1, except that the reaction parameters are fixed as shown in Table 1 below, including: fixing n (epimycochloropropane):n (compound 5A) to 14:1, and then replacing the added compound 1A with compound 5A. The yield of the compound represented by formula 5B is shown in Table 1 below. Figure 5 The above is the 1H NMR spectrum of the ketone-containing difuranyl epoxy monomer 5B prepared in Example 25 of this invention. Figure 5 Its structure can be verified.

[0112]

[0113] Example 26:

[0114] The preparation process of Example 26 is basically the same as that of Example 25, except that the reaction parameters are fixed according to Table 1 below, including: fixing n (epimycochloropropane):n (compound 6A) to 14:1, and then replacing the added compound 1A with compound 6A respectively. The yield of the compound represented by formula 6B is shown in Table 1 below. Figure 6 The above is the 1H NMR spectrum of the ketone-containing difuranyl epoxy monomer 6B prepared in Example 26 of this invention. Figure 6 Its structure can be verified.

[0115]

[0116] Table 1. Reaction parameters and yields for the preparation of ketone-containing difuranyl compounds in Examples 1-26

[0117]

[0118] A comparison between Examples 1 to 26 shows that the ketone-containing difuranyl compound 1B prepared in Example 3 has the highest yield of 99.9%. In other words, the best yield of the ketone-containing difuranyl compound is obtained when the diol monomer used is compound 1A, the ratio of n(epimchlorohydrin):n(monomer) is 14:1, the catalyst used is tetrabutylammonium hydrogen sulfate, the reaction is carried out under a nitrogen atmosphere, the reaction temperature is 50°C, the reaction time is 5 h, and the organic solvent is tetrahydrofuran.

[0119] Examples 27 to 30:

[0120] Ketone-containing bisfuranyl compound 1B was used as the electronic encapsulating adhesive, with 4,4'-diaminodiphenyl sulfone (DDS), diaminodiphenylmethane (DDM), 2,5-furandimethylamine (BAMF), or 5',5-(oxybis(methylene))bis(furan-2-methylamine) (OBMFDM) as curing agents. The mass ratio of ketone-containing bisfuranyl compound 1B to curing agent was 2:1. After mixing, the mixture was stirred at room temperature for 5 minutes, then degassed ultrasonically for 15 minutes, and transferred to a heated mold (preheating required). The mixture was first cured at 80°C for 3 hours, followed by curing at 130°C for 3 hours. The thermal properties of the prepared electronic encapsulating adhesive are shown in Table 2 below.

[0121] Examples 31 to 35:

[0122] The preparation processes of Examples 31 to 35 are basically the same as those of Example 27. The difference is that, according to Table 1 below, the reaction parameters are fixed, the curing agent is fixed as BAMF, and the ketone-containing bisfuran epoxy monomer 1B is replaced with ketone-containing bisfuran epoxy monomer 2B, ketone-containing bisfuran epoxy monomer 2B, ketone-containing bisfuran epoxy monomer 3B, ketone-containing bisfuran epoxy monomer 4B, ketone-containing bisfuran epoxy monomer 5B and ketone-containing bisfuran epoxy monomer 6B respectively. The yields obtained are shown in Table 2 below.

[0123] Table 2. Reaction parameters and glass transition temperatures for the preparation of electronic encapsulating adhesives in Examples 27–35

[0124] Example Epoxy monomers curing agent <![CDATA[T dmax / ℃]]> 27 1B DDS 320 28 1B DDM 331 29 1B BAMF 345 30 1B OBMFDM 312 31 2B BAMF 298 32 3B BAMF 319 33 4B BAMF 365 34 5B BAMF 354 35 6B BAMF 370

[0125] A comparison between Examples 27 to 35 shows that the ketone-containing bisfuran-based epoxy monomer 6B prepared in Example 35 has the highest glass transition temperature. In other words, when the epoxy monomer used is 6B and the curing agent is 2,5-furandimethylamine, the prepared electronic encapsulation adhesive has a higher glass transition temperature and relatively better stability at high temperatures.

[0126] The specific embodiments described above further illustrate the purpose, technical solution, and beneficial effects of the present invention. It should be understood that the above descriptions are merely specific embodiments of the present invention and are not intended to limit the present invention. Any modifications, equivalent substitutions, improvements, etc., made within the spirit and principles of the present invention should be included within the protection scope of the present invention.

Claims

1. A ketone-containing difuranyl monomer compound having the structural formula shown in formula (I) or formula (II): Equation (I) Formula (II) R1 is selected from any of the following structural formulas: in, n1=0~3, n2=0~3, n3=1~4, n5=0~4.

2. The ketone-containing difuranyl monomer compound according to claim 1, wherein, The ketone-containing difuranyl monomer compounds have the structures shown in formulas (I1) to (I6) or (II1) to (II6): Equation (I1) Equation (I3) Equation (I6) Formula (Ⅱ1) Formula (Ⅱ3) Formula (Ⅱ6).

3. A method for preparing a ketone-containing difuranyl monomer compound as described in claim 1 or 2, wherein the ketone-containing difuranyl monomer compound has the structure shown in formula (II), the preparation method comprising: Under an inert gas atmosphere, epichlorohydrin, sodium hydroxide aqueous solution and phase transfer catalyst are mixed, and then the compound shown in formula (I) is added dropwise and stirred to prepare a reaction solution containing the compound shown in formula (II).

4. The preparation method according to claim 3, wherein, The molar ratio of epichlorohydrin and the compound shown in formula (I) is 2:1 to 20:1; The phase transfer catalyst is a quaternary ammonium salt catalyst; The stirring treatment time is 2 to 24 hours, and the stirring treatment temperature is 50 to 100°C.

5. The preparation method according to claim 4, wherein, The ratio of the amount of epichlorohydrin and the compound shown in formula (I) added is 14:1; The quaternary ammonium salt catalyst is selected from at least one of tetrabutylammonium bisulfate, benzyltriethylammonium chloride, tetrabutylammonium bromide, tetrabutylammonium chloride, tetrabutylammonium hydroxide, hexadecyltrimethylammonium chloride, benzyltriethyltetrafluoroborate amine, tributylmethylammonium chloride, and methyltrioctylammonium chloride; The stirring process takes 5 hours.

6. An electronic encapsulating adhesive comprising a ketone-containing difuranyl monomer compound as described in claim 1 or 2, the ketone-containing difuranyl monomer compound having the structure shown in formula (II).

7. The electronic encapsulating adhesive according to claim 6, wherein, The electronic encapsulation adhesive is composed of a compound represented by formula (II) and a curing agent, wherein the curing agent is a diamine compound.

8. The electronic encapsulating adhesive according to claim 7, wherein, The mass ratio of the compound shown in formula (II) to the curing agent is 2:

1.

9. The electronic encapsulating adhesive according to claim 7, wherein, The curing conditions for the electronic encapsulation adhesive are as follows: first, cure at 70~90℃ for 2~4 hours; then cure at 120~140℃ for 2~4 hours.

10. The application of an electronic encapsulating adhesive as described in any one of claims 6 to 9 in the field of conductive encapsulation and insulating encapsulation technology.

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