Tetravinyl benzyl indene derivative, preparation method of tetravinyl benzyl indene derivative, tetravinyl benzyl indene derivative thermosetting hydrocarbon resin and application of tetravinyl benzyl indene derivative thermosetting hydrocarbon resin

Abstract

The invention provides a tetravinyl benzyl indene derivative, a preparation method of the tetravinyl benzyl indene derivative, tetravinyl benzyl indene derivative thermosetting hydrocarbon resin and application of the tetravinyl benzyl indene derivative thermosetting hydrocarbon resin, and relates to the technical field of thermosetting resin. The tetravinyl benzyl indene derivative provided by the invention contains four vinyl groups, the crosslinking density of the thermosetting hydrocarbon resin is high, the dielectric loss tangent and dielectric constant of the tetravinyl benzyl indene derivative thermosetting hydrocarbon resin are remarkably reduced, and the heat resistance of the tetravinyl benzyl indene derivative thermosetting hydrocarbon resin is remarkably improved. Compared with trivinyl benzyl indene hydrocarbon resin and 1, 2-bis (4-vinylphenyl) ethane hydrocarbon resin, the tetravinyl benzyl indene derivative thermosetting hydrocarbon resin provided by the invention has the advantages of lower dielectric loss tangent, higher glass transition temperature, higher thermal stability, higher thermal stability and higher thermal stability. The method has a good application prospect in preparation of high-frequency and high-speed resin, bonding sheets, metal foil-coated plates, insulating substrates, resin-coated metal foils, insulating films, circuit substrates or electronic devices.

Description

Technical Field

[0001] This invention relates to the field of thermosetting resin technology, specifically to a tetravinylbenzylindene derivative and its preparation method, and a tetravinylbenzylindene derivative thermosetting hydrocarbon resin and its applications. Background Technology

[0002] In recent years, the rapid development of 5G / 6G communications, satellite navigation, autonomous driving, and artificial intelligence has necessitated that printed circuit boards (PCBs), the core components of electronic products, meet the requirements of high frequency, high speed, integration, lightweight design, and high reliability. Therefore, the base resin of the copper-clad laminate (CCL), which performs conductive, insulating, and supporting functions on the PCB, and the encapsulation materials for electronic devices must possess lower dielectric constants (D). k Lower dielectric loss tangent (D) f (and higher heat resistance)

[0003] In the field of high-frequency and high-speed substrates, commonly used resins include epoxy resins, polytetrafluoroethylene resins, modified polyphenylene ether resins, and hydrocarbon resins. Among them, hydrocarbon resins, due to their extremely low dielectric constant and dielectric loss tangent, are expected to serve as a new generation of high-performance electronic materials for use in high-end microelectronics. Commonly used hydrocarbon resins include polybutadiene, butadiene-styrene copolymers, cyclopentadiene-styrene copolymers, and polyfunctional ethylene compounds. However, existing hydrocarbon resins generally suffer from the problem of not being able to simultaneously achieve dielectric properties and heat resistance. Summary of the Invention

[0004] In view of this, the purpose of this invention is to provide a tetravinylbenzylindene derivative, its preparation method, and a tetravinylbenzylindene derivative thermosetting hydrocarbon resin and its applications. The tetravinylbenzylindene derivative thermosetting hydrocarbon resin obtained by melt thermosetting of the tetravinylbenzylindene derivative provided by this invention has a small dielectric loss tangent, a low dielectric constant, and excellent heat resistance.

[0005] To achieve the above-mentioned objectives, the present invention provides the following technical solution: This invention provides a tetravinylbenzylindene derivative having the structure shown in Formula I: Formula I; R1, R2, R3 and R4 independently include hydrogen, C1~C10 alkyl or C6~C18 aryl; or, one or two of R1+R2, R2+R3, R3+R4 are independently benzene ring, cyclohexane or cyclopentane.

[0006] The present invention also provides a method for preparing the tetravinylbenzylindene derivative described in the above technical solution, comprising the following steps: mixing compound II, compound III, a strong base, a polymerization inhibitor and a polar aprotic solvent, and carrying out a nucleophilic substitution reaction to obtain the tetravinylbenzylindene derivative; ; R5 includes halogens, -OMs, -OTs, or -OTf.

[0007] Preferably, the molar ratio of compound II to compound III is 1:3.8~6.

[0008] Preferably, the strong base includes organic strong bases and / or inorganic strong bases; the organic strong base includes alkali metal alkoxides; the inorganic strong base includes alkali metal amines and / or alkali metal hydrides. The molar ratio of compound II to the strong base is 1:4 to 6.5.

[0009] Preferably, the polymerization inhibitor comprises one or more of nitromethane, o-nitrophenol, 2,4-dinitrophenol, phenothiazine, 2-phenylnaphthylamine, hydroquinone, catechol, p-methoxyphenol, 2,6-di-tert-butyl-p-cresol, p-tert-butyl-catechol, 2,2,6,6-tetramethylpiperidine nitroxide, and 2,2,6,6-tetramethyl-4-hydroxypiperidine nitroxide. The mass of the polymerization inhibitor is 0.01 to 0.5% of the mass of compound III.

[0010] Preferably, the polar aprotic solvent includes one or more of sulfone solvents, amide solvents, and ketone solvents.

[0011] Preferably, the nucleophilic substitution reaction is carried out at a temperature of 0-50°C for a time of 1-8 hours.

[0012] Preferably, the nucleophilic substitution reaction is followed by a post-processing step, which includes concentration and crystallization of the resulting concentrate. The recrystallization includes: pulping the concentrate to obtain a pulp; dissolving a portion of the pulp in a low-boiling-point solvent and evaporating to precipitate microcrystals; heating the remaining pulp in a mixed solvent, cooling it until turbidity begins to appear, adding the microcrystals, and continuing to cool to precipitate crystals; the pulping solvent includes C1-C3 alcohol solvents; the low-boiling-point solvent has a boiling point ≤100℃; the mixed solvent includes C5-C10 hydrocarbon solvents and C1-C3 alcohol solvents.

[0013] The present invention also provides a thermosetting hydrocarbon resin of tetravinylbenzylindene derivative, which is obtained by melt thermosetting of tetravinylbenzylindene derivative prepared by the above-described technical solution or the preparation method described in the above-described technical solution.

[0014] The present invention also provides the application of the tetravinylbenzylindene derivative thermosetting hydrocarbon resin described above in the preparation of high-frequency and high-speed resins, adhesive sheets, metal-coated foils, insulating substrates, resin-coated metal foils, insulating films, circuit boards or electronic devices.

[0015] The tetravinylbenzylindene derivative provided by this invention has a molecular backbone composed of only C and H elements, without any polar groups, and can be easily prepared into hydrocarbon resins through melt thermosetting. The tetravinylbenzylindene derivative provided by this invention contains four vinyl groups, resulting in a high crosslinking density in its thermosetting hydrocarbon resin, which significantly reduces the dielectric loss tangent (Dt) of the tetravinylbenzylindene derivative thermosetting hydrocarbon resin. f ) and dielectric constant (D k This invention significantly improves the thermosetting hydrocarbon resin's heat resistance. Compared to trivinylbenzylindene hydrocarbon resin and 1,2-bis(4-vinylphenyl)ethane (BVPE) hydrocarbon resin, the tetravinylbenzylindene derivative thermosetting hydrocarbon resin provided by this invention has a lower dielectric loss tangent and a higher glass transition temperature, showing great promise for the preparation of high-frequency and high-speed resins, adhesive sheets, metal-coated foils, insulating substrates, resin-coated metal foils, insulating films, circuit boards, or electronic devices. As shown in the test results of the examples, the dielectric constant D of the tetravinylbenzylindene thermosetting hydrocarbon resin prepared by melt thermosetting of the tetravinylbenzylindene derivative provided by this invention is... k (10GHz) is 2.6, dielectric loss tangent D f (10GHz) is 0.00040~0.00050, glass transition temperature T g With a operating temperature range of 320-330℃, tetravinylbenzylindene derivative thermosetting hydrocarbon resins exhibit low dielectric constant, small dielectric loss angle, and excellent thermal stability. They show great promise for applications in the preparation of high-frequency and high-speed resins, adhesive sheets, metal-coated foils, insulating substrates, resin-coated metal foils, insulating films, circuit boards, and electronic devices.

[0016] The method for preparing tetravinylbenzylindene derivatives provided by this invention is a single-step reaction, with simple process and operation. The obtained product is a solid, and high-purity tetravinylbenzylindene derivatives can be easily obtained by recrystallization. The production cost is low and it is suitable for industrial production. Attached Figure Description

[0017] Figure 1 The HPLC chromatogram shows the tetravinylbenzylindene derivative (Ia) prepared in Example 1. Figure 2 The tetravinylbenzylindene derivative (Ia) prepared in Example 1 1 H NMR spectrum; Figure 3The tetravinylbenzylindene derivative (Ia) prepared in Example 1 13 C NMR spectrum; Figure 4 The image shows the single-crystal structure of the tetravinylbenzylindene derivative (Ia) prepared in Example 1, where hollow circles represent H atoms. Figure 5 The cell packing diagram is of the tetravinylbenzylindene derivative (Ia) prepared in Example 1. Detailed Implementation

[0018] This invention provides a tetravinylbenzylindene derivative having the structure shown in Formula I: Formula I; Wherein, R1, R2, R3, and R4 independently include hydrogen, C1-C10 alkyl, or C6-C18 aryl; or, one or two of R1+R2, R2+R3, and R3+R4 independently consist of a benzene ring, cyclohexane, or cyclopentane, that is, in the tetravinylbenzylindene derivative, R1 and R2 may be cyclic or acyclic, R2 and R3 may be cyclic or acyclic, and R3 and R4 may be cyclic or acyclic; when acyclic, R1, R2, R3, and R4 independently include hydrogen, C1-C10 alkyl, or C6-C18 aryl; when cyclic, each ring independently consists of a benzene ring, a cyclohexane ring, or a cyclopentane ring.

[0019] In this invention, the C1-C10 alkyl group may include straight-chain C1-C10 alkyl group or branched C1-C10 alkyl group; the number of carbons in the C1-C10 alkyl group may specifically be 1, 2, 3, 4, 5, 6, 7, 8, 9 or 10.

[0020] In this invention, the number of carbons in the C6-C18 aryl group can be specifically 6, 7, 8, 9, 10, 11, 12, 13, 14, 15, 16, 17 or 18; the C6-C18 aryl group can be specifically phenyl, alkylphenyl, biphenyl, alkylbiphenyl, naphthyl or alkylnaphthyl.

[0021] In this invention, the position of the vinyl group on the benzene ring in Formula I can be independently ortho, meta, or para.

[0022] In this invention, the tetravinylbenzyl indene derivative may have the structure shown in Formula Ia, Formula Ib, or Formula Ic, wherein Formula Ia: 3-(1,2-bis(4-vinylphenyl)ethyl)-1,1-bis(4-vinylbenzyl)-1H-indene (3-(1,2-bis(4-vinylphenyl)ethyl)-1,1-bis(4-vinylbenzyl)-1H-indene), Formula Ib: 3-(1,2-bis(2-vinylphenyl)ethyl)-1,1-bis(2- Vinylbenzyl)-1H-indene(3-(1,2-bis(2-vinylphenyl)ethyl)-1,1-bis(2-vinylbenzyl)-1H-indene); Formula Ic: 3-(1,2-bis(3-vinylphenyl)ethyl)-1,1-bis(3-vinylbenzyl)-1H-indene(3-(1,2-bis(3-vinylphenyl)ethyl)-1,1-bis(3-vinylbenzyl)-1H-indene).

[0023] .

[0024] The present invention also provides a method for preparing the tetravinylbenzylindene derivative described in the above technical solution, comprising the following steps: mixing compound II, compound III, a strong base, a polymerization inhibitor and a polar aprotic solvent, and carrying out a nucleophilic substitution reaction to obtain the tetravinylbenzylindene derivative; ; Wherein, R5 includes halogens, -OMs, -OTs or -OTf; the halogens may include chlorine, bromine or iodine; the definitions of R1 to R4 in compound II are the same as the definitions of R1 to R4 in formula I.

[0025] In this invention, the reaction route of the tetravinylbenzylindene derivative is as follows: .

[0026] Unless otherwise specified, the materials and equipment used in this invention are all commercially available products in the field.

[0027] In this invention, the molar ratio of compound II to compound III can be 1:3.8 to 6, or 1:4 to 5.5, or even 1:4.5 to 5, specifically 1:3.8, 1:4, 1:4.5, 1:4.8, 1:5, 1:5.5 or 1:6.

[0028] In this invention, compound III may specifically include one or more of o-vinylbenzyl chloride, m-vinylbenzyl chloride, and p-vinylbenzyl chloride, and may specifically be a single vinylbenzyl chloride, a mixture of two vinylbenzyl chlorides, or a mixture of three vinylbenzyl chlorides; the single vinylbenzyl chloride is p-vinylbenzyl chloride, o-vinylbenzyl chloride, or m-vinylbenzyl chloride; the mixture of two vinylbenzyl chlorides may include a mixture of o-vinylbenzyl chloride and p-vinylbenzyl chloride (the product is an o / p-tetravinylbenzylindene derivative, denoted as Id), m-vinylbenzyl chloride, etc. A mixture of chlorine and p-vinylbenzyl chloride (the product is an m / p-tetravinylbenzylindene derivative, denoted as Ie), a mixture of m-vinylbenzyl chloride and o-vinylbenzyl chloride (the product is an o / m-tetravinylbenzylindene derivative, denoted as If); the mixture of the three vinylbenzyl chlorides can be a mixture of o-vinylbenzyl chloride, m-vinylbenzyl chloride and p-vinylbenzyl chloride (the product is an o / m / p-tetravinylbenzylindene derivative, denoted as Ig); the structural formulas of p-vinylbenzyl chloride, o-vinylbenzyl chloride and m-vinylbenzyl chloride are as follows: .

[0029] In this invention, the strong base may include organic strong bases and / or inorganic strong bases; the organic strong base may include alkali metal alkoxides, specifically including one or more of potassium tert-butoxide, sodium tert-butoxide, potassium isopropoxide, sodium isopropoxide, potassium ethoxide, sodium ethoxide, sodium methoxide, and potassium methoxide; the inorganic strong base may include alkali metal amines and / or alkali metal hydrides; the alkali metal amines may include potassium amine and / or sodium amine; the alkali metal hydrides may include potassium hydride and / or sodium hydride; the strong base may specifically be one or more of potassium tert-butoxide, sodium tert-butoxide, potassium hydride, and sodium hydride. In this invention, the molar ratio of compound II to the strong base may be 1:4 to 6.5, or 1:4.5 to 6, or further 1:5 to 5.5, specifically 1:4, 1:4.5, 1:4.8, 1:5, 1:5.5, 1:6, or 1:6.5.

[0030] In this invention, the polymerization inhibitor may include one or more of nitromethane, o-nitrophenol, 2,4-dinitrophenol, phenothiazine, 2-phenylnaphthylamine, hydroquinone, catechol, p-methoxyphenol, 2,6-di-tert-butyl-p-cresol, p-tert-butyl-catechol, 2,2,6,6-tetramethylpiperidine nitroxide, and 2,2,6,6-tetramethyl-4-hydroxypiperidine nitroxide (polymerization inhibitor 701). In this invention, the mass of the polymerization inhibitor is 0.01-0.5% of the mass of compound III, and may also be 0.05-0.4%, further 0.08-0.3%, specifically 0.01%, 0.05%, 0.08%, 0.1%, 0.15%, 0.2%, 0.25%, 0.3%, 0.35%, 0.4%, 0.45%, or 0.5%.

[0031] In this invention, the polar aprotic solvent may include one or more of sulfone solvents, amide solvents and ketone solvents, and may specifically include one or more of dimethyl sulfoxide, sulfolane, N,N-dimethylformamide, N,N-diethylformamide, hexamethylphosphoramide and N-methylpyrrolidone.

[0032] In this invention, the temperature of the nucleophilic substitution reaction is 0~50℃, or 10~40℃, specifically 0℃, 5℃, 10℃, 15℃, 20℃, 25℃, 30℃, 35℃, 40℃, 45℃ or 50℃; the time of the nucleophilic substitution reaction is 1~8h, or 2~5h, specifically 1h, 2h, 3h, 4h, 5h, 6h, 7h or 8h.

[0033] After the nucleophilic substitution reaction is completed, the present invention may further include a post-processing step, which includes concentration and recrystallization of the resulting concentrate. The present invention does not have any particular limitation on the concentration step; any concentration method well known to those skilled in the art can be used, such as vacuum distillation.

[0034] In this invention, the process before concentration may further include: adding the nucleophilic substitution reaction solution obtained from the nucleophilic substitution reaction to ice water for extraction, and then sequentially washing the resulting organic phase with acid and water until neutral. In this invention, the extraction solvent may include toluene and / or ethyl acetate; the number of extractions may be 1-5 times, or 2-4 times, specifically 3 times. In this invention, the acid solution may include dilute hydrochloric acid, and the mass concentration of the dilute hydrochloric acid may be 1-10%, or 3-8%, specifically 1%, 2%, 3%, 4%, 5%, 6%, 7%, 8%, 9%, or 10%; the number of acid washings may be 1-3 times, specifically 2 times.

[0035] In this invention, the recrystallization includes: pulping the concentrate to obtain a pulp; dissolving a portion of the pulp in a low-boiling-point solvent and evaporating to precipitate microcrystals; heating the remaining pulp in a mixed solvent, cooling it until turbidity begins to appear, adding the microcrystals, and continuing to cool and precipitate crystals.

[0036] In this invention, the solvent used for pulping includes C1-C3 alcohol solvents, specifically one or more of methanol, ethanol, n-propanol, and isopropanol. In this invention, the pulping temperature can be 0-40°C, or 10-30°C, specifically 0°C, 10°C, 20°C, 25°C, 30°C, or 40°C. This invention does not have a particular limitation on the amount of pulping solvent used; any amount of pulping solvent well-known to those skilled in the art can be used. In this invention, the number of pulping cycles can be 1-4 times, or 2-3 times. After pulping, the resulting pulping system is desaturated to remove the solvent, yielding a pulped product (a pale yellow viscous substance).

[0037] In this invention, the boiling point of the low-boiling solvent can be ≤100℃ or ≤85℃; the low-boiling solvent can include one or more of tetrahydrofuran, acetonitrile, n-hexane, n-heptane, cyclohexane, dichloromethane, chloroform and benzene, and can specifically be one or two.

[0038] In this invention, the mixed solvent may include a mixture of C5-C10 hydrocarbon solvents and C1-C3 alcohol solvents. The C5-C10 hydrocarbon solvents may include one or more of toluene, ethylbenzene, xylene, cumene, n-hexane, cyclohexane, n-heptane, and petroleum ether. In this invention, the C1-C3 alcohol solvents may include one or more of methanol, ethanol, n-propanol, and isopropanol. In this invention, the volume ratio of the C5-C10 hydrocarbon solvents to the C1-C3 alcohol solvents may be 1:0.2-0.4, specifically 1:0.3.

[0039] In this invention, the conditions for cooling and crystallization may include: a cooling rate of 0.2~0.6℃ / min, which may be 0.3~0.5℃ / min, which may be further 0.4~0.5℃ / min; a temperature after cooling of -5~5℃, which may be -2~2℃, which may be specifically 0℃; and a holding time of 20~100min, which may be 30~80min, which may be further 45~70min, which may be specifically 60min.

[0040] In this invention, the recrystallization process may further include drying the resulting crystals to obtain a tetravinylbenzylindene derivative. In this invention, the drying temperature can be 70-80°C, or even 75°C; the drying time is not particularly limited, as long as constant weight is achieved; the drying may include vacuum drying.

[0041] The present invention also provides a thermosetting hydrocarbon resin of tetravinylbenzylindene derivative, which is obtained by melt thermosetting of tetravinylbenzylindene derivative prepared by the above-described technical solution or the preparation method described in the above-described technical solution. In this invention, the temperature of the melt thermosetting can be 180~250℃, or 190~230℃, specifically 180℃, 190℃, 200℃, 210℃, 220℃, 230℃, 240℃, or 250℃; the pressure of the melt thermosetting can be 50~100mmHg, or 60~90mmHg, or further 70~80mmHg; the time of the melt thermosetting can be 160~250min, or 160~220min, specifically 160min, 170min, 180min, 190min, 200min, 210min, 220min, 230min, 240min, or 250min; the melt thermosetting can be carried out under a protective atmosphere, which may include nitrogen, argon, or helium.

[0042] This invention also provides the application of the tetravinylbenzylindene derivative thermosetting hydrocarbon resin described above in the preparation of high-frequency and high-speed resins, adhesive sheets, metal-coated foils, insulating substrates, resin-coated metal foils, insulating films, circuit boards, or electronic devices. In this invention, the tetravinylbenzylindene derivative thermosetting hydrocarbon resin can be used for the encapsulation of electronic devices.

[0043] To further illustrate the present invention, the following detailed description, in conjunction with embodiments, provides a tetravinylbenzylindene derivative, its preparation method, and a thermosetting hydrocarbon resin based on the tetravinylbenzylindene derivative, as well as its applications. However, these descriptions should not be construed as limiting the scope of protection of the present invention.

[0044] Analytical instruments and testing methods used: Purity determination method (HPLC): Agilent 1260 high-performance liquid chromatograph (USA); column type: Kromasil 100-5C18 250cm×4.6mm; mobile phase: acetonitrile; flow rate: 0.8mL / min; detection wavelength: 254nm; injection volume: 2μL; pump mode: binary high-pressure gradient.

[0045] Thermal analysis method: DSC was measured using a Pyris1 thermal analyzer (Perkin Elemer), with a heating range of 50~200℃ and a heating rate of 10℃ / min.

[0046] Nuclear magnetic resonance spectroscopy determination: Bruker AV 400 nuclear magnetic resonance spectrometer, DMSO-d6 as solvent, TMS as internal standard.

[0047] Single crystal structure determination: Bruker D8 Venture single crystal diffractometer, JY / T0588-2020 General Rules for Molecular Structure Analysis.

[0048] Dielectric constant D k (10GHz) and dielectric loss tangent D f (10GHz) Measurement: Molten sample casting method was used (thermosetting conditions: temperature 200℃, pressure 70~80mmHg, time 180min). Resin sheets of 80mm×80mm×0.4mm were prepared and measured at 10GHz using an Agilent N5230A vector network analyzer (SPDR).

[0049] Optical rotation was measured using a JH-P200 polarimeter with chloroform as the solvent.

[0050] Polymer glass transition temperature determination: Perkin Elemer Differential Scanning Calorimeter dsc 4000 instrument.

[0051] Mass spectrometry measurements: Agilent LC / MS Q 6460 instrument, ESI ion source.

[0052] The 2-vinylbenzyl chloride (HPLC purity 99.0%), 4-vinylbenzyl chloride (HPLC purity 99.5%), 3-vinylbenzyl chloride (HPLC purity 99.0%), and 1,2-bis(4-vinylphenyl)ethane (BVPE) (HPLC purity 99.5%) in the examples were all produced by Shandong Xingshun New Material Co., Ltd.

[0053] Example 1 Add 600 mL of anhydrous dimethyl sulfoxide, 2.4 mol of potassium tert-butoxide, and 0.3 g of 701 polymerization inhibitor to a reaction flask. Stir under a nitrogen stream for 30 min, then add 0.5 mol of indene. After stirring and dissolving, add 2.4 mol of 4-chloromethylstyrene dropwise, controlling the temperature to not exceed 40 °C. React at 30–35 °C and 350 rpm for 3.0 h. Add the reaction solution to 1200 mL of ice water and extract three times with toluene (600 mL each time). Wash the organic phase twice with 5 wt% dilute hydrochloric acid (800 mL each time), then wash with water until neutral. Evaporate the toluene under reduced pressure, and slurry twice with methanol at room temperature (150 mL each time). Decant to remove the methanol, obtaining a viscous substance. Dissolve 0.2–0.5 g of the viscous substance in 2–4 mL of chloroform solvent and slowly evaporate to precipitate microcrystals. The remaining viscous substance was heated (60-80℃) and dissolved in a heptane / methanol mixed solvent (volume ratio 1:0.3) to obtain a hot saturated solution. The solution was cooled at a rate of 0.5℃ / min, and when turbidity was observed, the obtained microcrystals were added. The solution was then cooled to 0℃ at a rate of 0.5℃ / min and held at this temperature for 60 min to allow crystallization. The resulting crystals were vacuum dried at 80℃ to constant weight to obtain 213.4 g of tetrakis(4-vinylbenzyl)indene (Ia). HPLC purity (…). Figure 1 (Table 1) shows a purity of 98.4%, a melting point of 116~120℃ (DSC), and [α] 25 D (CHCl3)=0, yield is 73.5%.

[0054] Table 1. HPLC peak information of tetra(4-vinylbenzyl)indene Ia

[0055] Figure 2 For tetra(4-vinylbenzyl)indene (Ia) 1 H NMR spectrum. 1¹H NMR (400 MHz, DMSO-d6) δ: 2.86–2.94 (m, 2H, CH₂), 3.10–3.19 (m, 4H, 2×CH₂), 4.01 (t, 1H, CH), 5.12–5.28 (m, 4H, 4×olefin hydrogen), 5.59–5.88 (m, 4H, 4×olefin hydrogen), 6.30 (s, 1H, indene ring 2-position H). The following data represent 16×benzene ring hydrogen, 4×olefin hydrogen, and H at positions 4, 5, 6, and 7 of the indene ring: 6.47–6.49 (m, 2H), 6.51–6.61 (m, 3H), 6.63–6.72 (m, 4H), 6.73–6.75 (m, 2H). 6.92(t,1H), 7.00(d, 2H),7.08(d, 2H),7.11-7.16(m, 5H).7.37(d,2H),7.63(d,1H).

[0056] Figure 3 For tetra(4-vinylbenzyl)indene (Ia) 13 C10 NMR spectrum. 13 C NMR (100 MHz, DMSO-d6)δ:40.8, 42.1, 43.6, 44.1(CH2, CH2, CH 2, CH), 57.4 (carbon at position 2 of the indene ring), 113.1, 113.2, 113.3, 114.2 (4× vinyl-terminal carbon), 119.8, 122.5, 124.3, 125.0, 125.2, 125.7, 125.9, 126.1, 126.5, 126.7, 127.9, 129.0, 130.0, 130.1, 134.5, 134.8, 136.3, 136.4, 136.5, 136.7, 136.9, 137.4, 137.6, 140.0, 142.6, 143.2, 144.0, 149.3 (Benzene ring C, Indene ring C, 4× Vinyl non-terminal carbon).

[0057] MS (m / z): M+1, 581.4 (100%), M+2, 582.4 (56.1%).

[0058] 1 H NMR and 13 The C NMR spectrum and MS data are in perfect agreement with the structure of tetra(4-vinylbenzyl)indene (Ia).

[0059] The 1H NMR spectrum of tetra(4-vinylbenzyl)indene Ia revealed that a vinyl benzyl group was not directly connected to the indene ring, but was connected to the benzyl carbon atom at the 3-position of indene, resulting in the formation of a chiral center. The specific rotation was measured to be 0. Single crystal structure analysis confirmed that the obtained tetra(4-vinylbenzyl)indene Ia was a racemic mixture.

[0060] Figure 4 This is a single-crystal structure diagram of tetra(4-vinylbenzyl)indene derivative (Ia), where hollow circles represent H atoms; Figure 5 The unit cell packing diagram of tetra(4-vinylbenzyl)indene derivative (Ia) is shown. The crystallographic parameters of tetra(4-vinylbenzyl)indene derivative (Ia) are shown in Table 2, and the bond lengths and bond angles are shown in Tables 3 and 4. Single-crystal structure determination further confirms the molecular structure of tetra(4-vinylbenzyl)indene derivative (Ia). Tetra(4-vinylbenzyl)indene derivative (Ia) 3-(1,2-di(4-vinylphenyl)ethyl)-1,1-di(4-vinylbenzyl)-1H-indene is an enantiomer with zero specific rotation, and is a racemic mixture. The chiral carbons C15A and C15B were determined to be… R "and" S Configuration (see carbon atom numbering) Figure 5 The crystal structure diagram is shown in the following formula: .

[0061] Table 2. Crystallographic parameters of tetra(4-vinylbenzyl)indene Ia

[0062] Table 3. Bond lengths of tetra(4-vinylbenzyl)indene Ia [Å]

[0063] Table 4 Bond angles of tetra(4-vinylbenzyl)indene Ia [°]

[0064] Example 2 Add 600 mL of anhydrous dimethyl sulfoxide, 3.2 mol of potassium tert-butoxide, and 0.3 g of 701 polymerization inhibitor to a reaction flask. Stir under a nitrogen stream for 30 min, then add 0.5 mol of indene. After stirring and dissolving, add 3.0 mol of 4-chloromethylstyrene dropwise, controlling the temperature to not exceed 40 °C. React at 30–35 °C and 350 rpm for 3.0 h. Add the reaction solution to 1200 mL of ice water and extract three times with toluene (600 mL each time). Wash the organic phase twice with 5 wt% dilute hydrochloric acid (1000 mL each time), then wash with water until neutral. Evaporate the toluene under reduced pressure. At room temperature, slurry the remaining viscous material twice with methanol (150 mL each time), decanting to remove the methanol, obtaining a viscous substance. Dissolve 0.2–0.5 g of the viscous substance in 2–4 mL of chloroform solvent and slowly evaporate to precipitate microcrystals. The viscous substance was heated (60-80℃) and dissolved in a heptane / methanol mixed solvent (volume ratio 1:0.3). The solution was cooled at a rate of 0.5℃ / min, and the obtained microcrystals were added when turbidity was observed. The solution was then cooled to 0℃ at a rate of 0.5℃ / min and maintained at this temperature for 60 min to allow crystallization. The resulting crystals were dried under vacuum at 80℃ to constant weight to obtain 216.3 g of tetrakis(4-vinylbenzyl)indene derivative (Ia), with an HPLC purity of 97.5% and a yield of 74.5%.

[0065] Example 3 Add 600 mL of anhydrous dimethyl sulfoxide, 2.4 mol of sodium hydride (after removing paraffin oil), and 0.3 g of 701 polymerization inhibitor to a reaction flask. Stir under a nitrogen atmosphere for 30 min, then add 0.5 mol of indene. After stirring and dissolving, add 2.4 mol of 4-chloromethylstyrene dropwise, controlling the temperature to not exceed 40 °C. React at 30–35 °C and 350 rpm for 3.0 h. Add the resulting solution to 1200 mL of ice water and extract three times with toluene (600 mL each time). Wash the organic phase twice with 5 wt% dilute hydrochloric acid (800 mL each time), then wash with water until neutral. Evaporate the toluene under reduced pressure. At room temperature, slurry the remaining viscous substance twice with methanol (150 mL each time), decanting to remove the methanol, yielding a pale yellow viscous substance. Dissolve 0.2–0.5 g of the viscous substance in 2–4 mL of chloroform and slowly evaporate to precipitate microcrystals. The viscous substance was heated (60-80℃) and dissolved in a heptane / methanol mixed solvent (volume ratio 1:0.3). The solution was cooled at a rate of 0.5℃ / min, and when turbidity was observed, the obtained microcrystals were added. The solution was then cooled to 0℃ at a rate of 0.5℃ / min and maintained at this temperature for 60 min to allow crystallization. The resulting crystals were dried under vacuum at 80℃ to constant weight, yielding 204.7 g of tetrakis(4-vinylbenzyl)indene derivative (Ia) with an HPLC purity of 97.7% and a yield of 70.5%.

[0066] Example 4 Add 600 mL of anhydrous sulfolane, 2.4 mol of potassium tert-butoxide, and 0.3 g of 701 polymerization inhibitor to a reaction flask. Stir under a nitrogen stream for 30 min, then add 0.5 mol of indene. After stirring and dissolving, add 2.4 mol of 4-chloromethylstyrene dropwise, controlling the temperature to not exceed 40 °C. React at 30–35 °C and 350 rpm for 3.0 h. Add the reaction solution to 1200 mL of ice water and extract three times with toluene (600 mL each time). Wash the organic phase twice with 5 wt% dilute hydrochloric acid (800 mL each time), then wash with water until neutral. Evaporate the toluene under reduced pressure. At room temperature, slurry the remaining viscous substance twice with methanol (150 mL each time), decanting to remove the methanol, yielding a pale yellow viscous substance. Dissolve 0.2–0.5 g of the viscous substance in 2–4 mL of chloroform solvent and slowly evaporate to precipitate microcrystals. The viscous substance was heated (60-80℃) and dissolved in a heptane / methanol mixed solvent (volume ratio 1:0.3). The solution was cooled at a rate of 0.5℃ / min, and when turbidity was observed, the obtained microcrystals were added. The solution was then cooled to 0℃ at a rate of 0.5℃ / min and maintained at this temperature for 60 min to allow crystallization. The resulting crystals were dried under vacuum at 80℃ to constant weight to obtain 207.0 g of tetrakis(4-vinylbenzyl)indene derivative (Ia). The product was a solid with an HPLC purity of 97.3% and a yield of 71.3%.

[0067] Example 5 Add 300 mL of dimethyl sulfoxide, 300 mL of LDM, 2.4 mol of potassium tert-butoxide, and 0.3 g of 701 polymerization inhibitor to a reaction flask. Stir under a nitrogen stream for 30 min, then add 0.5 mol of indene. After stirring and dissolving, add 2.4 mol of 4-chloromethylstyrene dropwise, controlling the temperature to not exceed 40 °C. React at 30–35 °C and 350 rpm for 3.0 h. Add the reaction solution to 1200 mL of ice water and extract three times with toluene (600 mL each time). Wash the organic phase twice with 5 wt% dilute hydrochloric acid (800 mL each time), then wash with water until neutral. Evaporate the toluene under reduced pressure. At room temperature, slurry the remaining viscous substance twice with methanol (150 mL each time), decanting to remove the methanol, yielding a pale yellow viscous substance. Dissolve 0.2–0.5 g of the viscous substance in 2–4 mL of chloroform and slowly evaporate to precipitate microcrystals. The viscous substance was heated (60-80℃) and dissolved in a heptane / methanol mixed solvent (volume ratio 1:0.3). The solution was cooled at a rate of 0.5℃ / min, and when turbidity was observed, the obtained microcrystals were added. The solution was then cooled to 0℃ at a rate of 0.5℃ / min and maintained at this temperature for 60 min to allow crystallization. The resulting crystals were dried under vacuum at 80℃ to constant weight to obtain 210.2 g of tetrakis(4-vinylbenzyl)indene (Ia). The product was a solid with an HPLC purity of 97.8% and a yield of 72.4%.

[0068] Example 6 The only difference from Example 1 was that 4-chloromethylstyrene was replaced with 2-chloromethylstyrene, yielding 189.9 g of tetrakis(2-vinylbenzyl)indene (Ib). The product was a solid with an HPLC purity of 97.5%. [α] 25 D (CHCl3)=0, yield is 65.4%. 1 ¹H NMR (400 MHz, DMSO-d6) δ: 2.95–3.05 (m, 2H, CH₂), 3.12–3.20 (m, 4H, 2×CH₂), 4.12 (t, 1H, CH), 5.13–5.27 (m, 4H), 5.60–5.87 (m, 4H), 6.31 (s, 1H, H at position 2 of indene ring), 6.40–6.48 (m, 2H), 6.55–6.68 (m, 3H), 6.66–6.82 (m, 4H), 6.83–6.95 (m, 2H), 6.92–7.00 (m, 3H), 7.08–7.16 (m, 7H), 7.47–7.58 (3H).

[0069] Example 7 The only difference from Example 1 was that 4-chloromethylstyrene was replaced with 3-chloromethylstyrene, yielding 202.1 g of tetrakis(3-vinylbenzyl)indene (Ic). The product was a solid with an HPLC purity of 97.0%. [α] 25 D (CHCl3)=0, yield is 69.6%. 1 ¹H NMR (400 MHz, DMSO-d6) δ: 2.76–2.98 (m, 2H, CH₂), 3.12–3.20 (m, 4H, 2×CH₂), 4.05 (t, 1H, CH), 5.11–5.26 (m, 4H), 5.61–5.85 (m, 4H), 6.25 (s, 1H, H at position 2 of indene ring), 6.45–6.45 (m, 2H), 6.41–6.50 (m, 3H), 6.60–6.73 (m, 4H). 6.78-6.85(m,2H),6.92-7.00(3H),7.08(s,3H),7.13-7.20(m,5H).7.35-7.62(m,3H).

[0070] Example 8 The only difference from Example 1 was that 2.4 mol of 4-chloromethylstyrene was replaced with a mixture of 1.2 mol of 2-chloromethylstyrene and 1.2 mol of 4-chloromethylstyrene, yielding 190.2 g of tetrakis(2 / 4-vinylbenzyl)indene (Id). The product was a solid with an HPLC purity of 97.2%. [α] 25 D (CHCl3)=0, yield is 65.5%. 1 ¹H NMR (400 MHz, DMSO-d6) δ: 2.90–3.01 (m, 2H, CH₂), 3.10–3.18 (m, 4H, 2×CH₂), 4.06 (t, 1H, CH), 5.13–5.25 (m, 4H), 5.58–5.77 (m, 4H), 6.30 (s, 1H, H at position 2 of indene ring), 6.41–6.47 (m, 2H), 6.45–6.58 (m, 3H), 6.63–6.80 (m, 4H), 6.87–6.94 (m, 2H), 6.97–7.00 (m, 3H), 7.05–7.17 (m, 7H), 7.38–7.55 (3H).

[0071] Example 9 Preparation of tetravinylbenzylindenyl derivative thermosetting hydrocarbon resin The tetra(4-vinylbenzyl)indenene (Ia, monomer) prepared in Example 1 was used to prepare a tetravinylbenzylindenene derivative thermosetting hydrocarbon resin by melt casting. The melt thermosetting conditions were: temperature 220°C, pressure 70~80 mmHg, and time 180 min. The glass transition temperature (Tg) was measured. g Thermosetting hydrocarbon resin containing tetravinylbenzylindene derivative was prepared into 80mm × 80mm × 0.4mm resin sheets. The dielectric constant and dielectric loss tangent of the samples at a frequency of 10GHz were determined using an Agilent N5230A vector network analyzer. The results are shown in Table 5.

[0072] Example 10 Preparation of tetravinylbenzylindenyl derivative thermosetting hydrocarbon resin The only difference from Example 9 is that the monomer is tetra(2-vinylbenzyl)indene (Ib) prepared in Example 6.

[0073] Example 11 Preparation of tetravinylbenzylindenyl derivative thermosetting hydrocarbon resin The only difference from Example 9 is that the monomer is tetra(3-vinylbenzyl)indene (Ic) prepared in Example 7.

[0074] Example 12 Preparation of tetravinylbenzylindenyl derivative thermosetting hydrocarbon resin The only difference from Example 9 is that the monomer is tetra(2 / 4-vinylbenzyl)indene (Id) prepared in Example 8.

[0075] Comparative Example 1 Preparation of 1,1,3-tris(4-vinylbenzyl)indene: 600 mL of anhydrous dimethyl sulfoxide, 1.6 mol of potassium tert-butoxide, and 0.3 g of 701 polymerization inhibitor were added. After stirring under a nitrogen atmosphere for 30 min, 0.5 mol of indene was added and stirred until dissolved. Then, 1.6 mol of 4-chloromethylstyrene was added dropwise, controlling the temperature to not exceed 40 °C. The reaction was carried out at 30–35 °C and 350 rpm for 3.0 h. The resulting solution was added to 1200 mL of ice water and extracted three times with toluene (600 mL each time). The organic phase was washed twice with 5 wt% dilute hydrochloric acid (800 mL each time), and then washed with water until neutral. Toluene was removed by vacuum distillation. The remaining viscous substance was slurried twice with methanol at room temperature, and the methanol was removed by decantation, yielding an orange-yellow viscous liquid. Recrystallization was performed using the same method as in Example 1, but no solid was obtained. The proton NMR spectrum showed that the viscous liquid was 1,1,3-tris(4-vinylbenzyl)indene.

[0076] Preparation of 1,1,3-tris(4-vinylbenzyl)indene thermosetting hydrocarbon resin: The only difference from Example 9 is that the monomer is 1,1,3-tris(4-vinylbenzyl)indene, and 1,1,3-tris(4-vinylbenzyl)indene thermosetting hydrocarbon resin is obtained.

[0077] Comparative Example 2 Synthesis of 1,1,3-tris(3 / 4-vinylbenzyl)indene: The synthesis was performed according to the method disclosed in publication number JP2003277440A: 200 mL of toluene, 0.3 mol of indene, 0.027 mol of tetra-n-butylammonium bromide, 0.009 mol of phenothiazine, and 50 wt% sodium hydroxide aqueous solution (1.8 mol sodium hydroxide) were added to a reaction flask, and the mixture was heated to 50 °C while stirring. Vinylbenzyl chloride (3-vinylbenzyl chloride: 4-vinylbenzyl chloride mass ratio = 1:1) was added dropwise over 15 min. The reaction was carried out at 50–52 °C with stirring for 10 h. The mixture was then neutralized to neutral with 2 mol / L dilute hydrochloric acid, washed twice with water, and the toluene was evaporated under reduced pressure. The final product was washed with methanol to obtain 1,1,3-tris(3 / 4-vinylbenzyl)indene (containing m / p-vinylbenzyl units, an orange-yellow viscous liquid).

[0078] Preparation of 1,1,3-tris(3 / 4-vinylbenzyl)indene thermosetting hydrocarbon resin: The only difference from Example 9 is that the monomer is 1,1,3-tris(3 / 4-vinylbenzyl)indene, and 1,1,3-tris(3 / 4-vinylbenzyl)indene thermosetting hydrocarbon resin is obtained.

[0079] Comparative Example 3 The only difference from Example 9 is that the monomer is 1,2-bis(4-vinylphenyl)ethane (BVPE), resulting in a 1,2-bis(4-vinylphenyl)ethane thermosetting hydrocarbon resin.

[0080] Table 5. Dielectric constants D of the thermosetting hydrocarbon resins prepared in Examples 9-12 and Comparative Examples 1-3 at 10 GHz k and dielectric loss tangent D f and glass transition temperature T g

[0081] Table 5 shows that the D of the trivinylbenzyl indene thermosetting hydrocarbon resins prepared in Comparative Examples 1-2 is... k (10GHz) is 2.7, D f (10GHz) was 0.00085~0.00095, compared to the D of 1,2-bis(4-vinylphenyl)ethane thermosetting hydrocarbon resin in Comparative Example 3. k (10GHz) is 2.8, D f The dielectric constant D of the tetravinylbenzylindene thermosetting hydrocarbon resin (Examples 9-12) prepared by melt thermosetting of the tetravinylbenzylindene derivative prepared in this invention is 0.00080. k (10GHz) is 2.6, dielectric loss tangent D f (10GHz) is 0.00040~0.00050, glass transition temperature T g The temperature range is 320~330℃. This indicates that the tetravinylbenzylindene thermosetting hydrocarbon resin provided by this invention has a lower dielectric constant and dielectric loss tangent, and an increased glass transition temperature, making it suitable as a resin material for next-generation high-frequency and high-speed substrates and as a packaging material for electronic devices. Furthermore, the synthesis method of the tetravinylbenzylindene derivative provided by this invention is simple, involving only one step, and the resulting product is a solid. High-purity products can be easily obtained through recrystallization, facilitating industrial production.

[0082] The above description is only a preferred embodiment of the present invention. It should be noted that for those skilled in the art, several improvements and modifications can be made without departing from the principle of the present invention, and these improvements and modifications should also be considered within the scope of protection of the present invention.

Claims

1. A tetravinylbenzylindene derivative having the structure shown in Formula I: Equation I; in, R1, R2, R3, and R4 independently include hydrogen, C1-C10 alkyl, or C6-C18 aryl; or, one or two of R1+R2, R2+R3, and R3+R4 independently consist of a benzene ring, cyclohexane, or cyclopentane.

2. The method for preparing the tetravinylbenzylindene derivative according to claim 1, characterized in that, Includes the following steps: Compound II, Compound III, a strong base, a polymerization inhibitor, and a polar aprotic solvent were mixed and subjected to a nucleophilic substitution reaction to obtain the tetravinylbenzylindene derivative. ； R5 includes halogens, -OMs, -OTs, or -OTf.

3. The preparation method according to claim 2, characterized in that, The molar ratio of compound II to compound III is 1:3.8~6.

4. The preparation method according to claim 2, characterized in that, The strong base includes organic strong bases and / or inorganic strong bases; the organic strong base includes alkali metal alkoxides; the inorganic strong base includes alkali metal amines and / or alkali metal hydrides. The molar ratio of compound II to the strong base is 1:4 to 6.

5.

5. The preparation method according to claim 2, characterized in that, The polymerization inhibitor includes one or more of nitromethane, o-nitrophenol, 2,4-dinitrophenol, phenothiazine, 2-phenylnaphthylamine, hydroquinone, catechol, p-methoxyphenol, 2,6-di-tert-butyl-p-cresol, p-tert-butyl-catechol, 2,2,6,6-tetramethylpiperidine nitroxide, and 2,2,6,6-tetramethyl-4-hydroxypiperidine nitroxide. The mass of the polymerization inhibitor is 0.01 to 0.5% of the mass of compound III.

6. The preparation method according to claim 2, characterized in that, The polar aprotic solvent includes one or more of sulfone solvents, amide solvents, and ketone solvents.

7. The preparation method according to any one of claims 2 to 6, characterized in that, The nucleophilic substitution reaction is carried out at a temperature of 0-50°C for a time of 1-8 hours.

8. The preparation method according to claim 7, characterized in that, The nucleophilic substitution reaction is followed by a post-processing step, which includes concentration and crystallization of the resulting concentrate. The recrystallization includes: pulping the concentrate to obtain a pulp; dissolving a portion of the pulp in a low-boiling-point solvent and evaporating to precipitate microcrystals; heating the remaining pulp in a mixed solvent, cooling it until turbidity begins to appear, adding the microcrystals, and continuing to cool to precipitate crystals; the pulping solvent includes C1-C3 alcohol solvents; the low-boiling-point solvent has a boiling point ≤100℃; the mixed solvent includes C5-C10 hydrocarbon solvents and C1-C3 alcohol solvents.

9. A thermosetting hydrocarbon resin of tetravinylbenzylindene derivative, obtained by melt thermosetting of the tetravinylbenzylindene derivative as described in claim 1 or the tetravinylbenzylindene derivative prepared by any one of claims 2 to 8.

10. The application of the tetravinylbenzylindene derivative thermosetting hydrocarbon resin of claim 9 in the preparation of high-frequency high-speed resins, adhesive sheets, metal-coated foils, insulating substrates, resin-coated metal foils, insulating films, circuit boards or electronic devices.

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