Bisphenol type benzoxazine resin and preparation method thereof

Abstract

The invention provides bisphenol type benzoxazine resin and a preparation method thereof, and relates to the field of materials, the benzoxazine resin is diallyl bisphenol F type benzoxazine resin, and the benzoxazine resin is terminated by a phenolic group to form a benzoxazine group or terminated by an amino group to form a benzoxazine group. According to the bisphenol type benzoxazine resin provided by the technical scheme provided by the invention, bisphenol F is used as a phenol raw material, but the bisphenol type benzoxazine resin which is good in stability and better in dielectric property, strength and elongation at break is accidentally obtained.

Description

Technical Field

[0001] The present invention relates to the field of material technology, and in particular to a bisphenol-type benzoxazine resin and a preparation method thereof. Background Art

[0002] Benzoxazine is a six-membered heterocyclic compound prepared by the Mannich shrinkage reaction of phenolic compounds, amine compounds and formaldehyde (or polyformaldehyde). Under heating or catalyst conditions, it can open the ring to form a new type of thermosetting resin with a network structure. Compared with traditional phenolic resins, this new type of thermosetting resin has considerable high temperature resistance, corrosion resistance, aging resistance, flame retardancy, and good mechanical properties. In addition, it overcomes the shortcomings of traditional phenolic resins in the preparation and curing process, such as small molecule release and large system shrinkage or micro-expansion, and has the excellent properties of no small molecule organic matter release during curing and low thermal shrinkage.

[0003] Introducing allyl groups into benzoxazine molecules can provide additional cross-linking points to achieve the purpose of toughening and improving thermal stability. Currently, the common allyl benzoxazine resins on the market are mainly allyl phenol, allyl bisphenol A and allyl amine. Summary of the invention

[0004] The object of the present invention is to provide a novel bisphenol-type benzoxazine resin and a preparation method thereof; the bisphenol-type benzoxazine resin uses bisphenol F as a phenol raw material, but unexpectedly obtains a bisphenol-type benzoxazine resin with good stability and better dielectric properties, strength and elongation at break.

[0005] In a first aspect, an embodiment of the present invention provides a bisphenol-type benzoxazine resin, wherein the benzoxazine resin is a diallyl bisphenol F-type benzoxazine resin, and the benzoxazine resin is end-capped with a group containing a phenol group to form a benzoxazine group or is end-capped with a group containing an amine group to form a benzoxazine group.

[0006] Further, in some embodiments of the present application, the benzoxazine resin is terminated by a group containing a phenol group.

[0007] Further, in some embodiments of the present application, the structural formula of the benzoxazine resin terminated by a group containing a phenol group is as shown in Formula I: Wherein, the R1 is selected from , , , Any one of; R2 is selected from H, , , Any of; natural number n1≥1; The structural formula of the benzoxazine resin terminated by an amine-containing group is shown in Formula II: Wherein, said R4 is selected from , , , Any one of; R3 is selected from , Any one of; n2≥0 natural number. Further, in some embodiments of the present application, R2 is selected from H, , , Any one of; or R3 is , .

[0008] In a second aspect, the present application also provides a method for preparing the bisphenol-type benzoxazine resin according to the first aspect, comprising the following steps: Add a first solvent, a first bisphenol raw material and a first aldehyde into a reaction container, add a raw material amine into the reaction container after heating, react for 3 to 8 hours, and after the reaction is completed, distill off the first solvent and water to obtain a bisphenol-type benzoxazine resin monomer; The bisphenol-type benzoxazine resin monomer is the benzoxazine resin terminated by an amino group; Wherein, the first bisphenol raw material is o-diallyl bisphenol F.

[0009] Further, the first solvent is one or more mixed solvents of ethanol, toluene, xylene, 1'4-dioxane, N'N-dimethylformamide; and / or The first aldehyde is any one of paraformaldehyde and formaldehyde aqueous solution; and / or The raw material amine is one or more of aniline, furfurylamine and allylamine; and / or The reaction temperature is 70-120°C; the heating rate is 0.1-10°C / min; the reaction time is 3-8h; and / or The raw material amine is added in multiple portions or continuously at a uniform speed within a time range of 30 to 90 minutes; and / or In the reaction system formed by the first solvent, the first bisphenol raw material, the first aldehyde and the raw material amine, the concentration of the first bisphenol raw material is 0.2-8.4 mol / L in terms of mass fraction; and / or The concentration of the first aldehyde is 0.8-18 mol / L by mass fraction; and / or The concentration mass fraction of the raw material amine is 0.4-16.8 mol / L.

[0010] In a third aspect, the present application further provides a method for preparing the bisphenol-type benzoxazine resin according to the first aspect, comprising the following steps: A second solvent, a second bisphenol raw material, and a second aldehyde are added to a reaction container, and after heating, a diamine raw material is added to the reaction container, and a first reaction is carried out for 0.5 to 3 hours, and then a monoamine raw material is added to carry out a second reaction for 3 to 8 hours. After the reaction is completed, the second solvent and water are removed by distillation to obtain a bisphenol-type benzoxazine resin monomer; the bisphenol-type benzoxazine resin monomer is the benzoxazine resin terminated by an amino group; Wherein, the second bisphenol raw material is o-diallyl bisphenol F.

[0011] Further, in some embodiments of the present application, the second solvent is one or more mixed solvents of ethanol, toluene, xylene, 1'4-dioxane, N'N-dimethylformamide; and / or The second aldehyde is any one of paraformaldehyde and formaldehyde aqueous solution; and / or The monoamine raw material is one or more of aniline, furfurylamine, and allylamine; the diamine is one or more of hexamethylenediamine, polyetheramine, 4'4-diaminodiphenyl ether, 4'4-diaminodiphenylmethane, and meta-xylylenediamine; and / or In the reaction system formed by the second solvent, the second bisphenol raw material, the second aldehyde and the diamine raw material, the concentration of the second bisphenol raw material is 0.2-8.4 mol / L in terms of mass fraction; and / or The concentration of the second aldehyde is 0.8-18 mol / L by mass fraction; and / or The concentration of the diamine raw material is 0.06-7.64 mol / L by mass fraction; and / or The concentration of the monoamine raw material is 0.02-5.6 mol / L by mass fraction; and / or The molar ratio of the diamine raw material to the monoamine raw material is 1:2 to 5:1; and / or The reaction temperature of the first reaction is 70-120°C; the heating rate is 0.1-10°C / min, and the reaction time is 0.5-3h; and / or The monoamine raw material is added in multiple times or continuously at a uniform speed within a time range of 30 to 90 minutes; and / or The reaction temperature of the second reaction is 70-120° C.; the heating rate is 0.1-10° C.; and the reaction time is 3-8 hours.

[0012] In a fourth aspect, the present application also provides a method for preparing the bisphenol-type benzoxazine resin according to the first aspect, comprising the following steps: Adding a solvent, a bisphenol raw material, a monophenol raw material and an aldehyde into a reaction container, adding a diamine raw material into the reaction container after heating, stirring and heating to a reflux state, and reacting for 3 to 8 hours; after the reaction is completed, distilling off the solvent and water to obtain a bisphenol-type benzoxazine resin monomer; the bisphenol-type benzoxazine resin monomer is the benzoxazine resin terminated by a group containing a phenol group; Wherein, the bisphenol raw material is o-diallyl bisphenol F.

[0013] Further, in some embodiments of the present application, the solvent is one or more mixed solvents of ethanol, toluene, xylene, 1'4-dioxane, N'N-dimethylformamide; and / or The aldehyde is any one of paraformaldehyde and formaldehyde aqueous solution; The diamine raw materials include but are not limited to one or more of hexamethylenediamine, polyetheramine, 4'4-diaminodiphenyl ether, 4'4-diaminodiphenylmethane, and meta-xylylenediamine; The monophenol raw material includes one or more selected from phenol, p-tert-butylphenol, p-maleimidephenol and allylphenol.

[0014] Further, in some embodiments of the present application, in the reaction system formed by the solvent, the bisphenol raw material, the monophenol raw material, the aldehyde and the raw material amine, the concentration of the bisphenol raw material is 0.08-5.6 mol / L in terms of mass fraction; and / or The concentration of the aldehyde is 0.8-18 mol / L by mass fraction; and / or The concentration of the raw material amine is 0.2-16.8 mol / L by mass fraction; and / or The concentration of the monophenol raw material is 0.16-5.6 mol / L in terms of mass fraction. The reaction temperature is 70-120°C; the heating rate is 0.1-10°C / min; and / or The raw material amine is added in multiple times or continuously at a uniform speed within a time range of 30 to 90 minutes.

[0015] The bisphenol-type benzoxazine resin provided in the present application uses diallyl bisphenol F, a specific phenol, as a raw material to prepare the benzoxazine resin. When the structural formula of the benzoxazine resin prepared is as shown in the above formula I or formula II, the benzoxazine resin obtained not only exhibits better dielectric properties and strength, but also excels in its stability and elongation at break.

[0016] The present application also provides a method for preparing the bisphenol-type benzoxazine resin, which is simple and easy to promote and apply. BRIEF DESCRIPTION OF THE DRAWINGS

[0017] Figure 1This is the DSC graph of the bisphenol-type benzoxazine resin provided in Example 2 of the present application; Figure 2 The DSC graph of the control resin provided in Comparative Example 1 of the present application; Figure 3 This is the infrared spectrum of the bisphenol-type benzoxazine resin provided in Example 2 of the present application. DETAILED DESCRIPTION

[0018] In order to make the purpose, technical solution and advantages of the embodiments of the present application clearer, the technical solution in the embodiments of the present application will be clearly and completely described below in conjunction with the drawings in the embodiments of the present application. Obviously, the described embodiments are only part of the embodiments of the present invention, not all of the embodiments. Based on the embodiments of the present invention, all other embodiments obtained by ordinary technicians in this field without creative work are within the scope of protection of the present invention.

[0019] In a first aspect, an embodiment of the present invention provides a bisphenol-type benzoxazine resin, wherein the benzoxazine resin is a diallyl bisphenol F-type benzoxazine resin, and the benzoxazine resin is end-capped with a group containing a phenol group to form a benzoxazine group or is end-capped with a group containing an amine group to form a benzoxazine group.

[0020] The structural formula of the benzoxazine resin terminated by a group containing a phenol group is shown in Formula I: Wherein, the R1 is selected from , , , Any one of; R2 is selected from H, , , Any of; natural number n1≥1; The structural formula of the benzoxazine resin terminated by an amine-containing group is shown in Formula II: Wherein, said R4 is selected from , , , Any one of; R3 is selected from , Any of ; natural number n2≥0.

[0021] During the experiment, the applicant unexpectedly discovered that when diallyl bisphenol F is used as the raw material phenol to prepare the benzoxazine resin, and when the structural formula of the prepared benzoxazine resin is as shown in Formula I or Formula II above, the obtained benzoxazine resin does not have worse stability than the benzoxazine resin prepared using diallyl bisphenol A as the raw material phenol as expected, nor does it have worse strength than the benzoxazine resin prepared using diallyl bisphenol A as the raw material phenol. In addition, when testing its elongation at break, it was found that its elongation at break was also better than that of the benzoxazine resin prepared using diallyl bisphenol A as the raw material phenol, showing better toughness, and its dielectric properties are also better. The possible reasons are speculated to be: the methylene bond of diallyl bisphenol F has less steric hindrance than the isopropyl bond of diallyl bisphenol A, so the finished resin will have better toughness, and compared with diallyl bisphenol A, the spatial structure of diallyl bisphenol F molecules is more compact, the distribution of electron clouds is relatively uniform, and the degree of polarization is relatively small, which makes its dielectric properties better than o-diallyl bisphenol A.

[0022] Preferably, the benzoxazine resin is terminated by a group containing a phenol group. During the experiment, the applicant also found that when diallyl bisphenol F is used as the raw material phenol to prepare the benzoxazine resin and when the structural formula of the benzoxazine resin prepared is as shown in the above formula I or formula II, different structures are used to terminate the benzoxazine resin, and the benzoxazine resin obtained will show different properties. When benzoxazine is terminated with phenol, that is, when the structural formula is as shown in the above formula I, the benzoxazine obtained shows better dielectric properties. The possible reason is speculated: through the molecular design of the benzoxazine resin, groups with better dielectric properties, such as low-polarity p-tert-butyl groups, are introduced, which increases the free volume inside the molecule, and therefore, the dielectric properties are more excellent.

[0023] When the applicant uses phenol or aniline with different substituents to end-cap benzoxazine, the applicant also found that when the benzoxazine resin of formula I uses tert-butyl as a substituent, the dielectric properties of the obtained benzoxazine resin will be further enhanced; when the benzoxazine resin of formula I uses tert-butyl as a substituent When the benzoxazine resin of formula II is used as a substituent, the heat resistance and mechanical properties of the obtained benzoxazine resin will be further enhanced; , When used as a substituent, the glass transition temperature of the resulting benzoxazine resin will be further increased.

[0024] It should be noted that the benzoxazine resin monomer described in the present application should be understood as a benzoxazine resin monomer or a benzoxazine resin oligomer.

[0025] In a second aspect, the present application also provides a method for preparing the bisphenol-type benzoxazine resin according to the first aspect, comprising the following steps: Add a first solvent, a first bisphenol raw material and a first aldehyde into a reaction container, add a raw material amine into the reaction container after heating, react for 3 to 8 hours, and after the reaction is completed, distill off the first solvent and water to obtain a bisphenol-type benzoxazine resin monomer; The bisphenol-type benzoxazine resin is a benzoxazine resin terminated by an amino group; Wherein, the first bisphenol raw material is o-diallyl bisphenol F.

[0026] In some embodiments, the first solvent is one or more mixed solvents of ethanol, toluene, xylene, 1'4-dioxane, N'N-dimethylformamide; and / or The first aldehyde is any one of paraformaldehyde and formaldehyde aqueous solution; and / or The raw material amine is one or more of aniline, furfurylamine and allylamine.

[0027] In some embodiments, in the reaction system formed by the first solvent, the first bisphenol raw material, the first aldehyde and the raw material amine, the concentration of the first bisphenol raw material is 0.2-8.4 mol / L by mass fraction; preferably, the concentration of the first bisphenol raw material is 1.6-4.2 mol / L by mass fraction, and / or The concentration of the first aldehyde is 0.8-18 mol / L; preferably, the concentration of the first aldehyde is 1.68-9 mol / L, and / or The mass fraction concentration of the raw material amine is 0.4-16.8 mol / L; preferably, the mass fraction concentration of the raw material amine is 3.2-8.4 mol / L.

[0028] The reaction temperature is 70-120°C, the heating rate is 0.1-10°C / min; preferably, the reaction temperature is 80-90°C, the heating rate is 0.5-3°C / min, and the reaction time is 3-8h.

[0029] The raw material amine is added in multiple times or continuously at a uniform speed within a time range of 30 to 90 minutes; preferably, the total time for adding the raw material amine is 50 to 60 minutes. In the actual preparation process, the raw material amine can be added dropwise or continuously and slowly.

[0030] In a third aspect, the present application also provides a method for preparing the bisphenol-type benzoxazine resin described in the first aspect. In the preparation method, two or more amines with different amine group equivalents (such as a combination of monoamine and diamine) are used as raw material amines for reaction. The bisphenol-type benzoxazine resin prepared by the method exhibits more excellent properties according to different R4 groups in formula II. For example, in formula II, R4= The finished product will have better thermal stability; R4= When the dielectric properties of the finished product are further improved.

[0031] The specific preparation method comprises the following steps: Adding a second solvent, a second bisphenol raw material, and a second aldehyde into a reaction container, adding a diamine raw material into the reaction container after heating, carrying out a first reaction for 0.5 to 3 hours, adding a monoamine raw material, carrying out a second reaction for 3 to 8 hours, and removing the second solvent and water by distillation after the reaction is completed to obtain a bisphenol-type benzoxazine resin monomer; the bisphenol-type benzoxazine resin is the benzoxazine resin terminated by an amino group; Wherein, the second bisphenol raw material is o-diallyl bisphenol F.

[0032] Wherein, the second solvent is one or more mixed solvents of ethanol, toluene, xylene, 1'4-dioxane, N'N-dimethylformamide; and / or The second aldehyde is any one of paraformaldehyde and formaldehyde aqueous solution; and / or The monoamine raw material is one or more of aniline, furfurylamine, and allylamine; the diamine is one or more of hexamethylenediamine, polyetheramine, 4'4-diaminodiphenyl ether, 4'4-diaminodiphenylmethane, and meta-xylylenediamine; and / or In the reaction system formed by the second solvent, the second bisphenol raw material, the second aldehyde and the diamine raw material, the concentration of the second bisphenol raw material is 0.2-8.4 mol / L by mass fraction; preferably, the concentration of the second bisphenol raw material is 1.6-4.2 mol / L by mass fraction, and / or The concentration of the second aldehyde is 0.8-18 mol / L; preferably, the concentration of the second aldehyde is 1.68-9 mol / L, and / or The concentration of the diamine raw material is 0.06-7.64 mol / L; preferably, the concentration of the diamine raw material is 0.48-3.82 mol / L, and / or The concentration of the monoamine raw material is 0.02-5.6 mol / L; preferably, the concentration of the monoamine raw material is 0.16-2.8 mol / L; and / or The molar ratio of the diamine raw material to the monoamine raw material is 1:2 to 5:1; and / or The reaction temperature of the first reaction is 70-120°C; the heating rate is 0.1-10°C / min, and the reaction time is 0.5-3h; preferably, the reaction temperature of the first reaction is 80-90°C; the heating rate is 0.5-3°C / min, and the reaction time is 0.5-1h; and / or The monoamine raw material is added in multiple times or continuously at a constant speed within a time range of 15 to 45 minutes; preferably, the total time for adding the monoamine raw material is 20 to 30 minutes. In the actual preparation process, the monoamine raw material can be added dropwise or continuously and slowly.

[0033] The diamine raw material is added in multiple times or continuously at a uniform speed within a time range of 15 to 80 minutes; preferably, the total time for adding the monoamine raw material is 30 to 50 minutes. In the actual preparation process, the monoamine raw material can be added dropwise or continuously and slowly.

[0034] The reaction temperature of the second reaction is 70-120°C; the heating rate is 0.1-10°C / min; and the reaction time is 3-8h. Preferably, the reaction temperature of the second reaction is 80-90°C; the heating rate is 0.5-3°C / min, and the reaction time is 3-5h.

[0035] In a fourth aspect, the present application also provides a method for preparing the bisphenol-type benzoxazine resin according to the first aspect, comprising the following steps: Adding a solvent, a bisphenol raw material, a monophenol raw material and an aldehyde into a reaction container, adding a diamine raw material into the reaction container after heating, stirring and heating to a suitable temperature, and reacting for 3 to 8 hours; after the reaction is completed, distilling off the solvent and water to obtain a bisphenol-type benzoxazine resin monomer; the bisphenol-type benzoxazine resin is the benzoxazine resin terminated by a group containing a phenol group; Wherein, the bisphenol raw material is o-diallyl bisphenol F.

[0036] In some embodiments, the solvent is one or more mixed solvents of ethanol, toluene, xylene, 1'4-dioxane, N'N-dimethylformamide; and / or The aldehyde is any one of paraformaldehyde and formaldehyde aqueous solution; The diamine raw materials include but are not limited to one or more of hexamethylenediamine, polyetheramine, 4'4-diaminodiphenyl ether, 4'4-diaminodiphenylmethane, and meta-xylylenediamine; The monophenol raw material includes one or more selected from phenol, p-tert-butylphenol, p-maleimidephenol and allylphenol.

[0037] In some embodiments, in the reaction system formed by the solvent, the bisphenol raw material, the monophenol raw material, the aldehyde and the raw material amine, the concentration of the bisphenol raw material is 0.08-5.6 mol / L by mass fraction; preferably, the concentration of the bisphenol raw material is 0.16-2.8 mol / L by mass fraction and / or The concentration of the aldehyde is 0.8-18 mol / L; preferably, the concentration of the aldehyde is 1.68-9 mol / L, and / or The concentration of the raw material amine is 0.2-16.8 mol / L; preferably, the concentration of the raw material amine is 0.4-8.4 mol / L, and / or The concentration of the monophenol raw material is 0.16-5.6 mol / L by mass fraction; preferably, the concentration of the monophenol raw material is 0.16-2.8 mol / L by mass fraction; The reaction temperature is 70-120°C; the heating rate is 0.1-10°C / min; preferably, the reaction temperature is 80-90°C; the heating rate is 0.5-3°C / min; and / or The raw material amine is added in multiple times or continuously at a uniform speed within a time range of 30 to 90 minutes; preferably, the total time for adding the raw material amine is 50 to 60 minutes. In the actual preparation process, the raw material amine can be added dropwise or continuously and slowly.

[0038] The above-mentioned bisphenol-type benzoxazine resin and its preparation method and plate of the present application will be described below in conjunction with specific examples. Those skilled in the art should understand that the examples are only to help understand the present invention and should not be regarded as specific limitations of the present application. If no specific technology or conditions are specified in the examples, the conventional technology or conditions in the art or the product instructions are used. If the manufacturer of the reagents or instruments is not specified, they are all conventional products that can be purchased commercially.

[0039] Example 1 This embodiment provides a method for preparing a bisphenol-type benzoxazine resin, and the reaction path is as follows:

[0040] The specific preparation method is: 62.67g of phenol, 61.5g of paraformaldehyde (Spanish ERCROS Company, industrial grade), 102g of toluene (purchased from Tianjin Damao Chemical Co., Ltd., analytical grade), and 46.67g of o-diallyl bisphenol F (Alfa Chemistry) were mixed, heated to 75°C at a constant temperature, and then 68g of m-xylylenediamine was slowly added dropwise within 60min. After the addition of m-xylylenediamine, the temperature was raised to 80°C and the reaction was carried out for 3h. The reaction system was distilled to remove the solvent and water. The reaction system was distilled under negative pressure and the temperature was raised to about 130°C at a heating rate of 1°C / min to stop distillation. The distilled system was placed in a vacuum oven for drying for 24h (60°C) to obtain 193.01g of bisphenol-type benzoxazine resin monomer with a yield of 95.57%.

[0041] Example 2 A method for preparing a bisphenol-type benzoxazine resin, the reaction path is as follows:

[0042] The specific preparation method is as follows: 100 g of p-tert-butylphenol, 61.5 g of paraformaldehyde (Spanish ERCROS Company, industrial grade), 124 g of toluene (purchased from Tianjin Damao Chemical Co., Ltd., analytical grade), and 46.67 g of o-diallyl bisphenol F (Alfa Chemistry) were mixed, heated to 75°C at a constant temperature, and then 68 g of m-phenylenediamine was slowly added dropwise within 60 min. After the addition of m-phenylenediamine, the temperature was raised to 80°C and the reaction was continued for 3 h. The reaction system was distilled to remove a large amount of solvent and water. The system was distilled under negative pressure and the temperature was raised to about 130°C at a heating rate of 1°C / min to stop distillation. The distilled system was placed in a vacuum oven for drying for 24 h (60°C) to obtain 235.13 g of bisphenol-type low dielectric benzoxazine resin monomer with a yield of 98.27%. The DSC graph is shown in FIG. Figure 1 shown.

[0043] Example 3 A bisphenol-type benzoxazine resin, the reaction path is as follows:

[0044] The preparation method is as follows: 81.9 g of o-diallyl bisphenol F (Alfa Chemistry), 37.5 g of paraformaldehyde (Spanish ERCROS, industrial grade), and 100 g of toluene (purchased from Tianjin Damao Chemical Co., Ltd., analytical grade) were mixed and heated to 75°C at a constant temperature. Then, 52.84 g of aniline was slowly added dropwise within 60 min. After the addition of aniline, the temperature was raised to 80°C and the reaction was continued for 3 h. The reaction system was distilled to remove a large amount of solvent and water. The system was distilled under negative pressure and the temperature was raised to about 130°C at a heating rate of 1°C / min to stop distillation. The distilled system was placed in a vacuum oven for drying for 24 h (60°C) to obtain 145.44 g of bisphenol-type benzoxazine resin monomer with a yield of 97.13%.

[0045] Example 4 A bisphenol-type benzoxazine resin, the reaction path is as follows:

[0046] The specific preparation method is as follows: 94.5 g of p-maleimide phenol (Shanghai Tuojing New Materials Technology Co., Ltd.), 61.5 g of paraformaldehyde (Spanish ERCROS, industrial grade), 130 g of toluene (purchased from Tianjin Damao Chemical Co., Ltd., analytical grade), and 70 g of o-diallyl bisphenol F (Alfa Chemistry) were mixed, heated to 75 ° C at a constant temperature, and then 68 g of m-xylylenediamine was slowly added dropwise within 60 min. After the addition of m-xylylenediamine, the temperature was raised to 80 ° C and reacted for 3 h. The reaction system was distilled to remove a large amount of solvent and water. The reaction system was distilled under negative pressure and the temperature was raised to about 130 ° C at a heating rate of 2 ° C / min to stop distillation. The solid material obtained was 246.6 g of bisphenol-type benzoxazine resin monomer with a yield of 95.7%.

[0047] Example 5 A bisphenol-type benzoxazine resin, the reaction path is as follows:

[0048] The preparation method is as follows: 70g of o-diallyl bisphenol F (Alfa Chemistry), 31.5g of paraformaldehyde (Spanish ERCROS, industrial grade), and 56g of toluene (purchased from Tianjin Damao Chemical Co., Ltd., analytical grade) were mixed and heated to 75°C at a constant temperature. 48.5g of furfural amine was slowly added dropwise within 40 minutes. After the addition of furfural amine, the temperature was raised to 80°C and the reaction was carried out for 3 hours. The reaction system was distilled to remove a large amount of solvent and water. The system was distilled under negative pressure and the temperature was raised to about 130°C at a heating rate of 2°C / min to stop distillation. The distilled system was placed in a vacuum oven for drying for 24 hours (60°C) to obtain 125.6g of bisphenol-type benzoxazine resin monomer with a yield of 95.83%.

[0049] Comparative Example 1 Compared with Example 2, except that o-diallyl bisphenol F is replaced by o-diallyl bisphenol A, the other raw materials and processes are exactly the same. The DSC graph of the obtained monomer is as follows Figure 2 Its chemical structure is shown below:

[0050] Comparative Example 2 Compared with Example 3, except that o-diallyl bisphenol F is replaced by o-diallyl bisphenol A, the other raw materials and processes are exactly the same, and the monomer structure obtained is shown below:

[0051] The monomers obtained in Examples 1 to 3, Comparative Examples 1 and 2 were placed in molds prepared in advance, respectively, and cured in stages in a forced air drying oven. The curing method was: 135° C. / 9 h, 150° C. / 9 h, 180° C. / 5 h, 210° C. / 1 h to obtain the corresponding benzoxazine resins after curing, and resin 1, resin 2, resin 3, comparative resin 1 and comparative resin 2 were obtained accordingly.

[0052] The monomer obtained in Example 2 was subjected to infrared detection, and the detection results are as follows: Figure 3 As shown, from Figure 3 It can be seen that at 926cm -1 The characteristic peak of the oxazine ring appeared at 1487 cm -1 The characteristic peak of benzene ring tri-substitution is 1022cm -1 、1220cm -1 The absorption peaks near 1636 cm correspond to the symmetric and antisymmetric stretching vibrations of the Ar-OC ether bond, indicating that the phenolic hydroxyl group participates in the reaction to form the ether bond in the oxazine ring structure. -1 The C=C double bond stretching vibration peak on the allyl group is 859 cm -1 and 993cm -1It is the out-of-plane bending vibration peak of CH on the allylic double bond.

[0053] The resin 1, resin 2, resin 3, comparative resin 1 and comparative resin 2 obtained above were subjected to thermal decomposition at temperature T d5% , dielectric properties, strength, and elongation at break testing, the testing methods are as follows: (1) Thermal decomposition temperature detection The thermal decomposition temperature T of each material in this application d5% Passed the standard test recorded in ASTM E2550-2007 (2) Dielectric properties The dielectric properties of the materials in this application are tested according to the standard GB / T 12636-1990 (3) Strength The tensile strength of each material in this application is tested by the standard described in ASTM D3039-76 (4) Elongation at break The elongation at break of each material in the present application is tested according to the standard described in GB1040-79.

[0054] The test results are shown in Table 1

[0055] From the data in Table 1, it can be seen that the finished resin prepared with o-diallyl bisphenol F as the raw material not only has better dielectric properties than that with o-diallyl bisphenol A, but also unexpectedly shows better strength and elongation at break, and its heat resistance is also good. In addition, the dielectric properties of o-diallyl bisphenol F benzoxazine resin terminated with phenol are even better than those of o-diallyl bisphenol F benzoxazine resin terminated with amine.

[0056] The above are only specific embodiments of the present invention, but the protection scope of the present invention is not limited thereto. Any changes or substitutions that can be easily thought of by a person skilled in the art within the technical scope disclosed by the present invention should be included in the protection scope of the present invention. Therefore, the protection scope of the present invention should be based on the protection scope of the claims.

Claims

1. A bisphenol-type benzoxazine resin, characterized in that: The benzoxazine resin is a diallyl bisphenol F type benzoxazine resin, and the benzoxazine resin is end-capped with a group containing a phenol group to form a benzoxazine group or is end-capped with a group containing an amine group to form a benzoxazine group.

2. The bisphenol-type benzoxazine resin according to claim 1, characterized in that: The benzoxazine resin is terminated with a group containing a phenolic group.

3. The bisphenol-type benzoxazine resin according to claim 1, characterized in that: The structural formula of the benzoxazine resin terminated by a group containing a phenol group is shown in Formula I: Wherein, the R1 is selected from , , , Any one of; R2 is selected from H, , , Any of; natural number n1≥1; The structural formula of the benzoxazine resin terminated by an amine-containing group is shown in Formula II: Wherein, said R4 is selected from , , , Any one of; R3 is selected from , Any of ; natural number n2≥0.

4. The bisphenol-type benzoxazine resin according to claim 3, characterized in that: R2 is selected from H, , , any of; or R3 is selected from , Any of .

5. The method for preparing the bisphenol-type benzoxazine resin according to any one of claims 1 to 4, characterized in that: The following steps are involved: Adding a first solvent, a first bisphenol raw material and a first aldehyde into a reaction container, heating and adding a raw material amine into the reaction container to react for 3 to 8 hours, and removing the first solvent and water by distillation after the reaction is completed to obtain a bisphenol-type benzoxazine resin monomer; the bisphenol-type benzoxazine resin monomer is the benzoxazine resin terminated by an amino group; Wherein, the first bisphenol raw material is o-diallyl bisphenol F.

6. The method for preparing a bisphenol-type benzoxazine resin according to claim 5, characterized in that: The first solvent is one or more mixed solvents of ethanol, toluene, xylene, 1'4-dioxane, N'N-dimethylformamide; and / or The first aldehyde is any one of paraformaldehyde and formaldehyde aqueous solution; and / or The raw material amine is one or more of aniline, furfurylamine and allylamine; and / or The reaction temperature is 70-120°C; the heating rate is 0.1-10°C / min; the reaction time is 3-8h; and / or The raw material amine is added in multiple portions or continuously at a uniform speed within a time range of 30 to 90 minutes; and / or In the reaction system formed by the first solvent, the first bisphenol raw material, the first aldehyde and the raw material amine, the concentration of the first bisphenol raw material is 0.2-8.4 mol / L in terms of mass fraction; and / or The concentration of the first aldehyde is 0.8-18 mol / L by mass fraction; and / or The concentration mass fraction of the raw material amine is 0.4-16.8 mol / L.

7. The method for preparing a bisphenol-type benzoxazine resin according to any one of claims 1 to 4, characterized in that: The following steps are included: A second solvent, a second bisphenol raw material, and a second aldehyde are added to a reaction container, and after heating, a diamine raw material is added to the reaction container, and a first reaction is carried out for 0.5 to 3 hours, and then a monoamine raw material is added to carry out a second reaction for 3 to 8 hours. After the reaction is completed, the second solvent and water are removed by distillation to obtain a bisphenol-type benzoxazine resin monomer; the bisphenol-type benzoxazine resin monomer is the benzoxazine resin terminated by an amino group; Wherein, the second bisphenol raw material is o-diallyl bisphenol F.

8. The method for preparing a bisphenol-type benzoxazine resin according to claim 7, characterized in that: The second solvent is one or more mixed solvents of ethanol, toluene, xylene, 1'4-dioxane, N'N-dimethylformamide; and / or The second aldehyde is any one of paraformaldehyde and formaldehyde aqueous solution; and / or The monoamine raw material is one or more of aniline, furfurylamine, and allylamine; the diamine is one or more of hexamethylenediamine, polyetheramine, 4'4-diaminodiphenyl ether, 4'4-diaminodiphenylmethane, and meta-xylylenediamine; and / or In the reaction system formed by the second solvent, the second bisphenol raw material, the second aldehyde and the diamine raw material, the concentration of the second bisphenol raw material is 0.2-8.4 mol / L in terms of mass fraction; and / or The concentration of the second aldehyde is 0.8-18 mol / L by mass fraction; and / or The concentration of the diamine raw material is 0.06-7.64 mol / L by mass fraction; and / or The concentration of the monoamine raw material is 0.02-5.6 mol / L by mass fraction; and / or The molar ratio of the diamine raw material to the monoamine raw material is 1:2 to 5:1; and / or The reaction temperature of the first reaction is 70-120°C; the heating rate is 0.1-10°C / min, and the reaction time is 0.5-3h; and / or The monoamine raw material is added in multiple times or continuously at a uniform speed within a time range of 30 to 90 minutes; and / or The reaction temperature of the second reaction is 70-120° C.; the heating rate is 0.1-10° C. / min; and the reaction time is 3-8 h.

9. The method for preparing a bisphenol-type benzoxazine resin according to any one of claims 1 to 4, characterized in that: The following steps are involved: Adding a solvent, a bisphenol raw material, a monophenol raw material and an aldehyde into a reaction container, adding a diamine raw material into the reaction container after heating, stirring and heating, and reacting for 3 to 8 hours; after the reaction is completed, distilling off the solvent and water to obtain a bisphenol-type benzoxazine resin monomer; the bisphenol-type benzoxazine resin monomer is the benzoxazine resin terminated by a phenolic group; Wherein, the bisphenol raw material is o-diallyl bisphenol F.

10. The method for preparing a bisphenol-type benzoxazine resin according to claim 9, characterized in that: The solvent is one or more mixed solvents of ethanol, toluene, xylene, 1'4-dioxane, N'N-dimethylformamide; and / or The aldehyde is any one of paraformaldehyde and formaldehyde aqueous solution; The diamine raw material includes one or more of hexamethylenediamine, polyetheramine, 4'4-diaminodiphenyl ether, 4'4-diaminodiphenylmethane, and meta-xylylenediamine; The monophenol raw material includes one or more selected from phenol, p-tert-butylphenol, p-maleimidephenol and allylphenol.

11. The method for preparing a bisphenol-type benzoxazine resin according to claim 9, characterized in that: In the reaction system formed by the solvent, the bisphenol raw material, the monophenol raw material, the aldehyde and the raw material amine, the concentration of the bisphenol raw material is 0.08-5.6 mol / L in terms of mass fraction; and / or The concentration of the aldehyde is 0.8-18 mol / L by mass fraction; and / or The concentration of the raw material amine is 0.2-16.8 mol / L by mass fraction; and / or The concentration of the monophenol raw material is 0.16-5.6 mol / L by mass fraction; and / or The reaction temperature is 70-120°C; the heating rate is 0.1-10°C / min; and / or The raw material amine is added in multiple times or continuously at a uniform speed within a time range of 30 to 90 minutes.

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