Magnolol fluorine-containing active ester compound, hydrophobic low-dielectric property resin condensate and preparation method and application thereof

Abstract

The invention belongs to the field of bio-based new materials, and discloses a magnolol fluorine-containing active ester compound, a hydrophobic low-dielectric property resin condensate, and a preparation method and application thereof. The preparation method comprises the following steps: dissolving magnolol in a solvent, adding an acid-binding agent, then adding fluorine-containing substituted benzoyl chloride, carrying out an esterification reaction, pouring the mixture into water after the reaction is finished to obtain a precipitate, collecting the precipitate, washing, and drying to obtain the magnolol fluorine-containing active ester compound. And the compound is introduced into the epoxy resin, so that low dielectric, hydrophobicity and greenization of the thermosetting epoxy resin are realized. The bio-based fluorine-containing active ester curing agent and multifunctional epoxy resin can form a three-dimensional network structure, secondary hydroxyl is not generated after curing, carbon-fluorine bonds difficult to polarize are introduced, the dielectric constant and dielectric loss of the epoxy resin can be remarkably reduced, and hydrophobicity is improved; a large number of biphenyl structures are introduced into the epoxy resin as a curing agent, so that the mechanical property of the epoxy resin can be greatly improved.

Description

Technical Field

[0001] The present invention belongs to the field of bio-based new materials, and particularly relates to a magnolol fluorinated active ester compound, a hydrophobic low dielectric property resin cured product, and a preparation method and application thereof. Background Art

[0002] Epoxy resin is a very common high-performance thermosetting resin, having many excellent properties such as high strength, heat resistance, corrosion resistance, and electrical insulation. It also has good adhesion and anti-aging properties, and can be used to make composite materials, coatings, adhesives, electronic packaging materials, etc. It is widely used in the fields of aviation, automobile, construction, electronics, etc. The curing agent is an important part of epoxy resin, and its selection plays an important role in various properties of epoxy resin materials.

[0003] Traditional polyamine epoxy curing agents will produce highly polar secondary hydroxyl groups after curing epoxy, which results in the cured product having high polarity and high hygroscopicity. For example, the dielectric constant of fr-4 copper clad laminate at 1MHz is 4.7 - 5.0, and the dielectric loss is 0.015 - 0.019 (Tian Yong, Pi Pihui, Wen Xiufang, Cheng Jiang, Yang Zhuoru. Polyphenylene ether / epoxy resin system for high-performance copper clad laminate [J]. Plastics Science and Technology, 2006(02): 1 - 4.), and its dielectric properties cannot meet the performance requirements of current electronic products such as low dielectric and high heat resistance. Therefore, there is an urgent need to develop epoxy curing agents that do not produce secondary hydroxyl groups. The active ester curing agent produces ester groups and ether bonds after curing epoxy resin, and can be used to prepare materials with low dielectric constants. In addition, polymers with low dielectric constants can be mainly achieved in two ways: one is to increase the molar volume by introducing bulky pendant groups, and the other is to reduce the molar polarizability by incorporating groups that are difficult to polarize (such as fluorine groups). Therefore, starting from the design of epoxy resin curing agents, designing new low dielectric epoxy resin curing agents is of great significance for microelectronic signal transmission.

[0004] Traditional epoxy resin curing agents usually come from non-renewable petroleum resources, causing waste of resources and environmental pollution. In contrast, using biomass to prepare epoxy resin curing agents has a wider source, is more environmentally friendly, has lower costs, and will obtain epoxy resins with different properties. Magnolol is an extract of the plant Magnolia officinalis, and due to its unique structure, it can be used to modify and prepare epoxy curing agents and epoxy resins. Currently, CN113999191A has disclosed a novel magnolol epoxy resin with active ester side groups, mainly optimizing the mechanical enhancement and flame retardant properties of the resin. However, in the prior art, there is no design of a fluorinated active ester polymer curing agent based on magnolol to prepare an epoxy resin material with low dielectric properties and hydrophobic properties. Summary of the Invention

[0005] In order to overcome the disadvantages and deficiencies of the prior art, the primary object of the present invention is to provide a magnolol fluorinated active ester compound.

[0006] Another object of the present invention is to provide a method for preparing a magnolol fluorinated active ester compound. The preparation method is to directly prepare a modified bio-based magnolol containing an active ester structure through a simple esterification reaction of biomass magnolol with fluorinated substituted benzoyl chloride.

[0007] Another object of the present invention is to provide a method for preparing a hydrophobic low-dielectric resin cured product, by introducing a fluorinated active ester compound based on magnolol into an epoxy resin to achieve low dielectric, hydrophobic, and green properties of the thermosetting epoxy resin.

[0008] Another object of the present invention is to provide a hydrophobic low-dielectric resin cured product.

[0009] Another object of the present invention is to provide an application of a hydrophobic low-dielectric resin cured product.

[0010] The object of the present invention is achieved by the following technical solutions:

[0011] A magnolol fluorinated active ester compound, characterized in that the structural formula of the compound is as follows:

[0012]

[0013] Among them, R is selected from any one of the following structures:

[0014]

[0015] Among them, R 1 , R 2 , R 3 are selected from any one or two of -F, -CF 3 , and * represents the connection position.

[0016] A method for preparing a magnolol fluorinated active ester compound, comprising the following steps:

[0017] (1) Dissolve magnolol in a solvent, add an acid-binding agent, and then add fluorinated substituted benzoyl chloride for an esterification reaction;

[0018] (2) After the reaction is completed, pour the mixture into water to obtain a precipitate, collect the precipitate, wash, and dry to obtain the magnolol fluorinated active ester compound.

[0019] Preferably, the solvent in step (1) is any one or a combination of two of tetrahydrofuran, toluene, and N,N-dimethylformamide;

[0020] The acid-binding agent is any one of triethylamine and pyridine;

[0021] The fluorine-substituted benzoyl chloride described in step (1) is any one of the following structures:

[0022]

[0023] wherein, R 1 , R 2 , R 3 is selected from any one or two of -F and -CF 3 .

[0024] Preferably, the molar ratio of magnolol, acid-binding agent, and fluorine-substituted benzoyl chloride in step (1) is 1:2 to 3.5:2 to 3, and more preferably 1:2.2 to 3.5:2.2 to 3.

[0025] Preferably, the reaction in step (1) is carried out at room temperature, the reaction time is 10 to 48 h, preferably 12 h;

[0026] Preferably, the fluorine-substituted benzoyl chloride in step (1) is the fluorine-substituted benzoyl chloride diluted with a solvent to prevent splashing caused by too fast reaction due to too high concentration. The solvent is any one or a combination of two of tetrahydrofuran, toluene, and N,N-dimethylformamide.

[0027] The washing in step (2) is washing with water 1 to 5 times, and the drying is vacuum drying. The drying temperature is 60 to 80 °C, preferably 70 °C, and the drying time is 10 to 48 h, preferably 24 h.

[0028] A method for preparing a hydrophobic low dielectric constant resin cured product, comprising the following steps:

[0029] Using the above magnolol fluorine-containing active ester compound as a curing agent, dissolving it in a solvent with epoxy resin and a catalyst according to a certain ratio, stirring to form a homogeneous viscous solution, and performing a curing treatment after the solvent volatilizes to obtain a hydrophobic low dielectric constant resin cured product.

[0030] Preferably, the solvent is any one or a combination of two of tetrahydrofuran, toluene, N,N-dimethylformamide, xylene, and N-methylpyrrolidone;

[0031] The epoxy resin refers to an epoxy resin having three or more epoxy groups in one molecule, specifically at least one of polyfunctional bisphenol A epoxy resin, bisphenol F epoxy resin, biphenyl epoxy resin, dicyclopentadiene phenol epoxy resin, naphthalene epoxy resin, alicyclic epoxy resin, resorcinol epoxy resin, polyethylene glycol epoxy resin, brominated epoxy resin, N,N,N,N,-tetraglycidyl-4,4-diaminodiphenylmethane, and phenolic epoxy resin;

[0032] The catalyst is at least one of 4-dimethylaminopyridine (DMAP), triphenylphosphine (TPP), and 2-methylimidazole (MI).

[0033] Preferably, the molar ratio of the active ester group in the magnolol fluorinated active ester compound to the epoxy group in the epoxy resin is 1 - 1.25:1, more preferably 1:1;

[0034] The mass ratio of the epoxy resin to the catalyst is 1:0.005 - 0.03; the solid content of the system is 25% - 50%, and the solid content is the proportion of the mass of the remaining part after solvent evaporation to the total mass of the system;

[0035] The curing treatment is to pre-cure at 80 - 130 °C (preferably 130 °C) for 2 - 4 h (preferably 3 h), then cure at 130 - 160 °C (preferably 150 °C) for 3 - 6 h (preferably 3 h), and then cure at 160 - 220 °C (preferably 200 °C) for 1 - 3 h (preferably 2 h).

[0036] A hydrophobic low dielectric performance resin cured product is prepared by the above method.

[0037] Preferably, the dielectric constant of the hydrophobic low dielectric performance resin cured product is 2.65 - 2.87, the dielectric loss is 0.005 - 0.0074, and the contact angle is greater than 97°.

[0038] Preferably, the mass fraction composition of the hydrophobic low dielectric performance resin cured product is as follows:

[0039] Epoxy resin 10 - 100

[0040] Catalyst 0.1 - 1

[0041] Curing agent 20 - 40.

[0042] The application of the above hydrophobic low dielectric performance resin cured product in high-speed high-frequency copper clad laminates and / or electronic packaging fields.

[0043] Compared with the prior art, the present invention has the following advantages and beneficial effects:

[0044] (1) The present invention first proposes a bio-based green curing agent for epoxy resin materials based on magnolol-based fluorinated active ester curing agent, which has low cost, is environmentally friendly, does not involve cumbersome processing techniques, and can reduce the consumption of petroleum-derived resources during the production and use of epoxy resin.

[0045] (2) The magnolol-based fluorinated active ester curing agent obtained in the present invention can form a three-dimensional network structure with multifunctional epoxy resin. After curing, no secondary hydroxyl groups are generated and carbon-fluorine bonds that are difficult to polarize are introduced, which can significantly reduce the dielectric constant and dielectric loss of epoxy resin and improve hydrophobicity. The water contact angle is greater than 98°. And as a curing agent, a large number of biphenyl structures are introduced into epoxy resin, which can greatly improve the mechanical properties of epoxy resin. BRIEF DESCRIPTION OF THE DRAWINGS

[0046] Figure 1 It is a schematic diagram of the synthesis route of the magnolol-based fluorinated active ester curing agent prepared in Example 1 of the present invention. DETAILED DESCRIPTION OF THE EMBODIMENTS

[0047] The present invention will be further described in detail below with reference to the embodiments, but the embodiments of the present invention are not limited thereto. The raw materials involved in the present invention can be directly purchased from the market. For the process parameters not specifically mentioned, conventional techniques can be referred to.

[0048] Example 1:

[0049] First, the preparation of the magnolol-based fluorinated active ester curing agent is carried out, which specifically includes the following steps:

[0050] Under a nitrogen atmosphere, 11.3 g (0.05 mol) of magnolol is dissolved in 50 mL of tetrahydrofuran, 11.1 g (0.11 mol) of triethylamine is added, and then 17.4 g (0.11 mol) of m-fluorobenzoyl chloride diluted with 30 mL of tetrahydrofuran is added at 0 °C. After stirring vigorously for 60 min, the reaction is carried out at room temperature for 12 h. After the reaction is completed, the mixture is poured into 1 L of deionized water to obtain a white precipitate. The precipitate is filtered and collected, washed three times with deionized water, and dried in a vacuum oven at 70 °C to obtain the magnolol bio-based curing agent, named MFAE-1. The synthesis route is as Figure 1 shown. After structural confirmation, its structural formula is:

[0051]

[0052] Further, the hydrophobic low-dielectric performance resin cured product is prepared by using the above-prepared magnolol-based fluorinated active ester curing agent, which specifically includes the following steps:

[0053] In parts by mass, 10 parts of N,N,N,N,-tetraglycidyl-4,4'-diaminodiphenylmethane (TGDDM), 22.3 parts of MFAE-1, and 0.1 part of 4-dimethylaminopyridine (DMAP) are dissolved in 32.4 parts of N-methylpyrrolidone. After the solvent is volatilized, it is cured at 130 °C for 3 h, at 150 °C for 3 h, and at 200 °C for 2 h.

[0054] Example 2:

[0055] First, the preparation of a fluorinated active ester curing agent based on magnolol is carried out, which specifically includes the following steps:

[0056] Under a nitrogen atmosphere, 11.3 g (0.05 mol) of magnolol is dissolved in 50 mL of tetrahydrofuran, 11.1 g (0.11 mol) of triethylamine is added, and then 17.4 g (0.11 mol) of p-fluorobenzoyl chloride diluted with 30 mL of tetrahydrofuran is added at 0 °C. After vigorous stirring for 60 min, the reaction is carried out at room temperature for 12 h. After the reaction is completed, the mixture is poured into 1 L of deionized water to obtain a white precipitate. The precipitate is filtered and collected, washed three times with deionized water, and dried in a vacuum oven at 70 °C to obtain a magnolol-based bio-based curing agent, named MFAE-2. After structural confirmation, its structural formula is:

[0057]

[0058] Furthermore, the preparation of a hydrophobic low-dielectric resin cured product is carried out using the above-prepared fluorinated active ester curing agent based on magnolol, which specifically includes the following steps:

[0059] In parts by mass, 10 parts of TGDDM, 22.3 parts of MFAE-2, and 0.1 part of DMAP are dissolved in 32.4 parts of N-methylpyrrolidone. After the solvent is volatilized, it is cured at 130 °C for 3 h, at 150 °C for 3 h, and at 200 °C for 2 h.

[0060] Example 3:

[0061] First, the preparation of a fluorinated active ester curing agent based on magnolol is carried out, which specifically includes the following steps:

[0062] Under a nitrogen atmosphere, 11.3 g (0.05 mol) of magnolol is dissolved in 50 mL of tetrahydrofuran, 11.1 g (0.11 mol) of triethylamine is added, and then 17.4 g (0.11 mol) of o-fluorobenzoyl chloride diluted with 30 mL of tetrahydrofuran is added at 0 °C. After vigorous stirring for 60 min, the reaction is carried out at room temperature for 12 h. After the reaction is completed, the mixture is poured into 1 L of deionized water to obtain a white precipitate. The precipitate is filtered and collected, washed three times with deionized water, and dried in a vacuum oven at 70 °C to obtain a magnolol-based bio-based curing agent, named MFAE-3. After structural confirmation, its structural formula is:

[0063]

[0064] Further, the hydrophobic low-dielectric resin cured product is prepared by using the fluorinated active ester curing agent based on magnolol prepared above, and the specific steps are as follows:

[0065] By mass, 10 parts of TGDDM, 22.3 parts of MFAE-3, and 0.1 part of DMAP are dissolved in 32.4 parts of N-methylpyrrolidone. After the solvent is volatilized, it is cured at 130 °C for 3 h, 150 °C for 3 h, and 200 °C for 2 h.

[0066] Example 4:

[0067] First, the fluorinated active ester curing agent based on magnolol is prepared, and the specific steps are as follows:

[0068] Under a nitrogen atmosphere, 11.3 g (0.05 mol) of magnolol is dissolved in 50 mL of tetrahydrofuran, 11.1 g (0.11 mol) of triethylamine is added, and then 22.9 g (0.11 mol) of 3-trifluoromethylbenzoyl chloride diluted with 30 mL of tetrahydrofuran is added at 0 °C. After vigorous stirring for 60 min, the reaction is continued at room temperature for 12 h. After the reaction is completed, the mixture is poured into 1 L of deionized water to obtain a white precipitate. The precipitate is collected by filtration, washed three times with deionized water, and dried in a vacuum oven at 70 °C to obtain the magnolol-based bio-based curing agent, named MFAE-4. After structural confirmation, its structural formula is:

[0069]

[0070] Further, the hydrophobic low-dielectric resin cured product is prepared by using the fluorinated active ester curing agent based on magnolol prepared above, and the specific steps are as follows:

[0071] By mass, 10 parts of TGDDM, 27 parts of MFAE-4, and 0.1 part of DMAP are dissolved in 37.1 parts of N-methylpyrrolidone. After the solvent is volatilized, it is cured at 130 °C for 3 h, 150 °C for 3 h, and 200 °C for 2 h.

[0072] Example 5:

[0073] First, the fluorinated active ester curing agent based on magnolol is prepared, and the specific steps are as follows:

[0074] Under a nitrogen atmosphere, 11.3 g (0.05 mol) of magnolol was dissolved in 50 mL of tetrahydrofuran, 11.1 g (0.11 mol) of triethylamine was added, and then 22.9 g (0.11 mol) of 4-trifluoromethylbenzoyl chloride diluted with 30 mL of tetrahydrofuran was added at 0 °C. After vigorously stirring for 60 min, the reaction was carried out at room temperature for 12 h. After the reaction was completed, the mixture was poured into 1 L of deionized water to obtain a white precipitate. The precipitate was collected by filtration, washed three times with deionized water, and dried in a vacuum oven at 70 °C to obtain a magnolol-based bio-based curing agent named MFAE-5. After structural confirmation, its structural formula is:

[0075]

[0076] Furthermore, the hydrophobic low-dielectric resin cured product was prepared using the fluorinated active ester curing agent based on magnolol prepared above, and the specific steps are as follows:

[0077] By mass, 10 parts of TGDDM, 27 parts of MFAE-5, and 0.1 part of DMAP were dissolved in 37.1 parts of N-methylpyrrolidone. After the solvent was volatilized, it was cured at 130 °C for 3 h, 150 °C for 3 h, and 200 °C for 2 h.

[0078] Example 6:

[0079] First, the fluorinated active ester curing agent based on magnolol was prepared, and the specific steps are as follows:

[0080] Under a nitrogen atmosphere, 11.3 g (0.05 mol) of magnolol was dissolved in 50 mL of tetrahydrofuran, 11.1 g (0.11 mol) of triethylamine was added, and then 22.9 g (0.11 mol) of 2-trifluoromethylbenzoyl chloride diluted with 30 mL of tetrahydrofuran was added at 0 °C. After vigorously stirring for 60 min, the reaction was carried out at room temperature for 12 h. After the reaction was completed, the mixture was poured into 1 L of deionized water to obtain a white precipitate. The precipitate was collected by filtration, washed three times with deionized water, and dried in a vacuum oven at 70 °C to obtain a magnolol-based bio-based curing agent named MFAE-6. After structural confirmation, its structural formula is:

[0081]

[0082] Furthermore, the hydrophobic low-dielectric resin cured product was prepared using the fluorinated active ester curing agent based on magnolol prepared above, and the specific steps are as follows:

[0083] By mass, 10 parts of TGDDM, MFAE-6, and 0.1 part of DMAP were dissolved in 37.1 parts of N-methylpyrrolidone. After the solvent was volatilized, it was cured at 130 °C for 3 h, 150 °C for 3 h, and 200 °C for 2 h. Comparative Example 1:

[0084] Under a nitrogen atmosphere, 11.3 g (0.05 mol) of magnolol was dissolved in 50 mL of tetrahydrofuran, 11.1 g (0.11 mol) of triethylamine was added, and then 8.6 g (0.11 mol) of acetyl chloride diluted with 30 mL of tetrahydrofuran was added at 0 °C. After vigorously stirring for 60 min, the reaction was carried out at room temperature for 12 h. After the reaction was completed, the mixture was poured into 1 L of deionized water to obtain a white precipitate. The precipitate was collected by filtration, washed three times with deionized water, and dried in a vacuum oven at 70 °C to obtain a magnolol-based curing agent, named MAE-1.

[0085] By mass, 10 parts of TGDDM, 14.7 parts of MAE-1, and 0.1 part of DMAP were dissolved in 34.8 parts of N-methylpyrrolidone. After the solvent was evaporated, it was cured at 130 °C for 3 h, 150 °C for 3 h, and 200 °C for 2 h.

[0086] Comparative Example 2:

[0087] Under a nitrogen atmosphere, 11.3 g (0.05 mol) of magnolol was dissolved in 50 mL of tetrahydrofuran, 11.1 g (0.11 mol) of triethylamine was added, and then 15.5 g (0.11 mol) of benzoyl chloride diluted with 30 mL of tetrahydrofuran was added at 0 °C. After vigorously stirring for 60 min, the reaction was carried out at room temperature for 12 h. After the reaction was completed, the mixture was poured into 1 L of deionized water to obtain a white precipitate. The precipitate was collected by filtration, washed three times with deionized water, and dried in a vacuum oven at 70 °C to obtain a magnolol-based curing agent, named MAE-2.

[0088] By mass, 10 parts of TGDDM, 21.9 parts of MAE-2, and 0.1 part of DMAP were dissolved in 32 parts of N-methylpyrrolidone. After the solvent was evaporated, it was cured at 130 °C for 3 h, 150 °C for 3 h, and 200 °C for 2 h. Comparative Example 3:

[0089] Under a nitrogen atmosphere, 11.3 g (0.05 mol) of magnolol was dissolved in 50 mL of tetrahydrofuran, 11.1 g (0.11 mol) of triethylamine was added, and then 17 g (0.11 mol) of m-methylbenzoyl chloride diluted with 30 mL of tetrahydrofuran was added at 0 °C. After vigorously stirring for 60 min, the reaction was carried out at room temperature for 12 h. After the reaction was completed, the mixture was poured into 1 L of deionized water to obtain a white precipitate. The precipitate was collected by filtration, washed three times with deionized water, and dried in a vacuum oven at 70 °C to obtain a magnolol-based curing agent, named MAE-3.

[0090] In parts by mass, 10 parts of TGDDM, 21.9 parts of MAE-3, and 0.1 part of DMAP are dissolved in 32 parts of N-methylpyrrolidone. After volatilizing the solvent, it is cured at 130 °C for 3 h, at 150 °C for 3 h, and at 200 °C for 2 h. Comparative Example 4:

[0091] Under a nitrogen atmosphere, 11.3 g (0.05 mol) of magnolol is dissolved in 50 mL of tetrahydrofuran, 11.1 g (0.11 mol) of triethylamine is added, and then 17 g (0.11 mol) of p-methylbenzoyl chloride diluted with 30 mL of tetrahydrofuran is added at 0 °C. After vigorously stirring for 60 min, the reaction is carried out at room temperature for 12 h. After the reaction is completed, the mixture is poured into 1 L of deionized water to obtain a white precipitate. The precipitate is collected by filtration, washed three times with deionized water, and dried in a vacuum oven at 70 °C to obtain a magnolol-based curing agent, named MAE-4.

[0092] In parts by mass, 10 parts of TGDDM, 21.9 parts of MAE-4, and 0.1 part of DMAP are dissolved in 32 parts of N-methylpyrrolidone. After volatilizing the solvent, it is cured at 130 °C for 3 h, at 150 °C for 3 h, and at 200 °C for 2 h. Comparative Example 5:

[0093] Under a nitrogen atmosphere, 11.3 g (0.05 mol) of magnolol is dissolved in 50 mL of tetrahydrofuran, 11.1 g (0.11 mol) of triethylamine is added, and then 17 g (0.11 mol) of o-methylbenzoyl chloride diluted with 30 mL of tetrahydrofuran is added at 0 °C. After vigorously stirring for 60 min, the reaction is carried out at room temperature for 12 h. After the reaction is completed, the mixture is poured into 1 L of deionized water to obtain a white precipitate. The precipitate is collected by filtration, washed three times with deionized water, and dried in a vacuum oven at 70 °C to obtain a magnolol-based curing agent, named MAE-5.

[0094] In parts by mass, 10 parts of TGDDM, 21.9 parts of MAE-5, and 0.1 part of DMAP are dissolved in 32 parts of N-methylpyrrolidone. After volatilizing the solvent, it is cured at 130 °C for 3 h, at 150 °C for 3 h, and at 200 °C for 2 h. Comparative Example 6:

[0095] In parts by mass, 10 parts of TGDDM, 4.7 parts of 4,4'-diaminodiphenylmethane, and 0.1 part of DMAP are dissolved in 14.8 parts of N-methylpyrrolidone. After volatilizing the solvent, it is cured at 130 °C for 3 h, at 150 °C for 3 h, and at 200 °C for 2 h.

[0096] Comparative Example 7:

[0097] Different from Example 1, the preparation of a fluorine-containing active ester curing agent based on 4-(2-allyl)-catechol is carried out first, which specifically includes the following steps:

[0098] Under a nitrogen atmosphere, 6.8 g (0.05 mol) of 4-(2-allyl)-catechol was dissolved in 50 mL of tetrahydrofuran, 11.1 g (0.11 mol) of triethylamine was added, and then 17.4 g (0.11 mol) of m-fluorobenzoyl chloride diluted in 30 mL of tetrahydrofuran was added at 0°C. After vigorous stirring for 60 min, the mixture was reacted at room temperature for 12 h. After the reaction was completed, the mixture was poured into 1 L of deionized water to obtain a white precipitate. The precipitate was collected by filtration, washed three times with deionized water, and dried in a vacuum oven at 70°C to obtain a fluorine-containing active ester curing agent of 4-(2-allyl)-catechol.

[0099] In terms of mass, 10 parts of N,N,N,N,-tetracyclyl-4,4-diaminodiphenylmethane (TGDDM), 18 parts of fluorine-containing active ester curing agent of 4-(2-allyl)-catechol, and 0.1 part of DMAP were dissolved in 28.1 parts of N-methylpyrrolidone. After the solvent was evaporated, the mixture was cured at 130°C for 3h, 150°C for 3h, and 200°C for 2h.

[0100] The dielectric properties and hydrophobic properties of the epoxy thermosetting resins prepared in Examples 1 to 6 and Comparative Examples 1 to 7 were tested using conventional methods in the art. The results are shown in Table 1.

[0101] Table 1 Dielectric constant, dielectric loss and water absorption

[0102]

[0103] The results show that the epoxy thermosetting resin prepared by curing with a traditional active hydrogen curing agent in Comparative Example 6 has a higher dielectric constant, dielectric loss and water absorption rate due to the increased crosslinking density and the high polarity hydroxyl groups generated after curing. The epoxy thermosetting resin prepared by curing with bio-based magnolol active ester in Comparative Examples 1 to 5 has a reduced dielectric constant, dielectric loss and water absorption rate because the active ester does not produce high polarity hydroxyl groups after curing, but generates ester groups and ether bonds with lower polarity, but it is still difficult to meet the market requirements for low dielectric materials. In contrast, Examples 1 to 6 in the present invention further introduce a carbon-fluorine bond that is difficult to polarize on the basis of Comparative Examples 1 to 5, so the dielectric constant and dielectric loss are further reduced, and the water contact angle is further improved. Compared with the fluorine-containing active ester curing agent based on 4-(2-allyl)-catechol in Comparative Example 7, magnolol has a large biphenyl structure, which gives the cured resin a conjugated hydrophobic structure, and therefore has a more excellent hydrophobic property.

[0104] The above embodiments are preferred embodiments of the present invention, but the embodiments of the present invention are not limited to the above embodiments. Any other changes, modifications, substitutions, combinations, and simplifications made without departing from the spirit and principle of the present invention shall be equivalent replacement methods and are all included in the protection scope of the present invention.

Claims

1. A fluorine-containing active ester compound of magnolol, characterized in that The structural formula of the compound is as follows: Wherein, R is selected from any one of the following structures: Wherein, R1, R2, and R3 are selected from any one or two of -F and -CF3, and * represents the connection position.

2. The method for preparing the fluorinated active ester compound of magnolol according to claim 1, characterized in that: The following steps are involved: (1) dissolving magnolol in a solvent, adding an acid binding agent, and then adding fluorinated substituted benzoyl chloride to carry out an esterification reaction; (2) After the reaction is completed, the mixture is poured into water to obtain a precipitate, and the precipitate is collected, washed, and dried to obtain a fluorine-containing active ester compound of magnolol.

3. The method for preparing the fluorinated active ester compound of magnolol according to claim 2, wherein: The solvent in step (1) is any one of tetrahydrofuran, toluene, and N,N-dimethylformamide or a combination of any two of them; The acid binding agent is any one of triethylamine and pyridine; The fluorinated substituted benzoyl chloride described in step (1) is any one of the following structures: Wherein, R1, R2, and R3 are selected from any one or two of -F and -CF3.

4. The method for preparing the fluorinated active ester compound of magnolol according to claim 2, wherein: The molar ratio of magnolol, acid-binding agent and fluorine-containing substituted benzoyl chloride in step (1) is 1:2-3.5:2-3.

5. The method for preparing the fluorinated active ester compound of magnolol according to claim 2, wherein: The reaction time in step (1) is 10 to 48 hours; The washing in step (2) is water washing for 1 to 5 times, and the drying is vacuum drying at a drying temperature of 60 to 80° C. for a drying time of 10 to 48 hours.

6. A method for preparing a hydrophobic low dielectric resin cured product, characterized in that: The steps include: The magnolol fluorine-containing active ester compound of claim 1 is used as a curing agent, dissolved in a solvent with an epoxy resin and a catalyst in a certain ratio, stirred to form a uniform viscous solution, and cured after the solvent evaporates to obtain a hydrophobic low dielectric resin cured product.

7. The method for preparing a hydrophobic low dielectric property resin cured product according to claim 6, characterized in that: The solvent is any one of tetrahydrofuran, toluene, N,N-dimethylformamide, xylene, and N-methylpyrrolidone, or a combination of any two of them; The epoxy resin refers to an epoxy resin having three or more epoxy groups in one molecule, specifically at least one of a multifunctional bisphenol A epoxy resin, a bisphenol F epoxy resin, a biphenyl epoxy resin, a dicyclopentadiene phenol epoxy resin, a naphthalene epoxy resin, an alicyclic epoxy resin, a resorcinol epoxy resin, a polyethylene glycol epoxy resin, a brominated epoxy resin, N,N,N,N,-tetraepoxypropyl-4,4-diaminodiphenylmethane and a phenolic epoxy resin; The catalyst is at least one of 4-dimethylaminopyridine, triphenylphosphine and 2-methylimidazole.

8. The method for preparing a hydrophobic low dielectric property resin cured product according to claim 6, characterized in that: The molar ratio of the active ester group in the magnolol fluorine-containing active ester compound to the epoxy group in the epoxy resin is 1-1.25:1; The mass ratio of the epoxy resin to the catalyst is 1:0.005-0.03; The solid content of the system is 25% to 50%; The curing treatment is pre-curing at 80-130° C. for 2-4 hours, then curing at 130-160° C. for 3-6 hours, and then curing at 160-220° C. for 1-3 hours.

9. A hydrophobic low dielectric resin cured product, characterized in that: Prepared by the method described in claim 7 or 8.

10. Use of the hydrophobic low dielectric resin cured product according to claim 9 in the field of high-speed and high-frequency copper-clad laminates and / or electronic packaging.

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