A bio-based hyperbranched epoxy resin- bisphenol a type epoxy resin composite resin containing a hexahydro-s-triazine structure and a preparation method thereof

Abstract

The application discloses a preparation method of a bio-based hyperbranched epoxy resin-bisphenol A type epoxy resin composite resin containing a hexahydro-sym-triazine structure. The preparation process comprises the following steps: (1) synthesizing a terminal mercapto hexahydro-sym-triazine by performing a chemical reaction on an aldehyde compound, a bio-based hydroxyl amine compound and a mercapto alkyl acid; (2) synthesizing a bio-based maleimide monomer by performing a chemical reaction on maleic anhydride, an aniline compound, 2,5-furan dimethyl amine and an alkyl mercaptan; (3) obtaining a bio-based hyperbranched epoxy resin by performing a click reaction on the terminal mercapto hexahydro-sym-triazine, the bio-based maleimide monomer and an alkenyl epoxy compound; and (4) obtaining the bio-based hyperbranched epoxy resin / bisphenol A type epoxy resin composite resin by stirring the bio-based hyperbranched epoxy resin, a bisphenol A type epoxy resin and a curing agent and then heat curing. The application has the advantages of simple process, remarkable advantages of the composite resin in green preparation, high performance and reduction of environmental pollution and the like.

Description

TECHNICAL FIELD

[0001] The present application relates to the technical field of degradable hyperbranched epoxy resin, and particularly relates to a bio-based hyperbranched epoxy resin containing a hexahydro-sym-triazine structure and a bisphenol A type epoxy resin composite resin and a preparation method thereof. BACKGROUND

[0002] Epoxy resin has excellent physical and mechanical properties, electrical insulation properties, heat resistance and bonding properties with various materials, and thus is widely used in the fields of coatings, adhesives, electronics and electrical appliances, aerospace, automobiles and medical treatment. However, the common epoxy resin has the disadvantages of poor crack resistance, low toughness, easy decomposition to produce toxic gases at high temperatures, and use of toxic curing agents in the curing process, which limits the application of the epoxy resin in many fields. As a thermosetting material, a three-dimensional irreversible crosslinked network structure is formed in the curing process, and the raw materials for processing are highly dependent on non-renewable biomass, which leads to waste of resources and pollution of the environment.

[0003] The hyperbranched epoxy resin is a kind of thermosetting hyperbranched polymer, which has the advantages of unique topological structure, multiple active end groups, high reactivity and good compatibility, and can enhance and toughen the traditional bisphenol A type epoxy resin. The prepared hyperbranched epoxy resin is blended with the ordinary bisphenol A type epoxy resin, which is not only beneficial to the enhancement and toughening of the bisphenol A type epoxy resin, but also helps to realize the functionalization of the epoxy resin composite resin by structure regulation of the hyperbranched epoxy resin. Therefore, the present inventors (Zhang Daohong) introduce the hexahydro-sym-triazine structure to invent the degradable hyperbranched epoxy resin (ZL201810386063.3; Nature Sustainability, 2020, 3, 29-34; Composites Part B, 2020, 196, 108109), and study the process technology of the influence of topological structure on the mechanical properties of renewable bio-based hyperbranched chain epoxy / carbon fiber composite (Chemical Engineering Journal 471 (2023): 144329.).

[0004] However, the thermosetting hyperbranched epoxy resin composite resin is usually prepared from non-biomass raw materials. The production process of non-biomass materials usually accompanies a large amount of greenhouse gas emission, which has a negative impact on the environment, is not sustainable in resources, and aggravates global climate change. Therefore, it is necessary to develop a preparation technology of hyperbranched epoxy resin / bisphenol A type epoxy resin composite resin with simple process, good biocompatibility and renewable raw materials, which is a fundamental way to solve the existing problems in the field, and thus reduces carbon emission and environmental load. SUMMARY

[0005] In order to solve the problems in the prior art, the application provides a bio-based hyperbranched epoxy resin containing a hexahydro-sym-triazine structure and a bisphenol A type epoxy resin composite resin and a preparation method thereof.

[0006] The application solves the above technical problems by the following technical scheme:

[0007] One of the technical schemes is a bio-based hyperbranched epoxy resin containing a hexahydro-sym-triazine structure, and the structural formula is as follows:

[0008]

[0009] R', R'', R''' are the same or different and are independently represented by the structures shown in general formula (2), general formula (3) or general formula (4).

[0010]

[0011] X is one or more of the following structures:

[0012]

[0013] The structure of R is as follows:

[0014]

[0015] R2 is one or more of the following structures:

[0016]

[0017] The mercaptoalkyl acid and the alcohol are connected by esterification reaction to form -COO- by connecting -C-O- in the structure with -CO- in -R4, and the other end in the structure is connected with -N in the structure R to form -CN-.

[0018] The structure of R1 is as follows:

[0019]

[0020] R3 is one or more of the following structures:

[0021]

[0022] R4 is the following structure:

[0023] n is a natural number of 1-5

[0024] Wherein, the mercaptoalkyl acid and the alcohol are connected by esterification reaction to form -COO- in the structure, and the thiol and the olefin compound are connected by thiol-olefin click reaction to form -C-S-C- in the structure;

[0025] Wherein, R5 is a fatty alkyl group with 5-18 carbon atoms, C5H 11 ~ -C 18 H 37 ;

[0026] The number average molecular weight of the bio-based hyperbranched epoxy resin containing a hexahydro-s-triazine structure is 11000-36000 g / mol, and the epoxy value is 0.06-0.10 mol / 100g.

[0027] Technical solution two: a preparation method of a bio-based hyperbranched epoxy resin containing a hexahydro-s-triazine structure, comprising the following steps:

[0028] (1) Put the aldehyde compound, the bio-based hydroxyl amine compound and the organic solvent into the reaction bottle, stir and react at 40-100℃ for 5-15 hours, then cool to 10-30℃, add the mercaptoalkyl acid and the catalyst, and stir and react for 12-18 hours to obtain the terminal mercapto hexahydro-s-triazine monomer (A3);

[0029] (2) Put the maleic anhydride, the aniline compound and the organic solvent into the reaction bottle, stir and react at 2-10℃ for 1-7 hours, then warm to 50-80℃, stir and react for 5-15 hours to obtain the maleimide monomer;

[0030] (3) Put the maleimide monomer, 2,5-furandimethylamine, alkyl mercaptan, maleic anhydride and organic solvent into the reaction bottle, stir and react at 45-160℃ for 15-20 hours to obtain the bio-based maleimide monomer (B2);

[0031] (4) Put the terminal mercapto hexahydro-s-triazine monomer (A3) obtained in step (1), the bio-based maleimide monomer (B2) obtained in step (3), the alkenyl epoxy compound, the organic solvent and the photoinitiator into the reaction bottle, and irradiate with ultraviolet light with power of 400-800W for 10-60 minutes to carry out thiol-olefin click reaction, thereby obtaining the bio-based hyperbranched epoxy resin containing a hexahydro-s-triazine structure, with number average molecular weight of 11000-36000 g / mol and epoxy value of 0.06-0.10 mol / 100g.

[0032] Further, the bio-based hydroxyl amine compound is 1-amino-2-indanol 4-hydroxybutylamine and L-phenylglycinol One or more of them.

[0033] Furthermore, the aldehyde compound is one or more of paraformaldehyde, paraformaldehyde, and aqueous formaldehyde solution;

[0034] Furthermore, the catalyst is one or more of p-toluenesulfonic acid, trifluoromethanesulfonic acid, and 4-dimethylaminopyridine;

[0035] Furthermore, the mercaptoalkyl acid is

[0036]

[0037] Furthermore, the aniline compound is one or more of aniline, β-naphthylamine, and 1-aminopyrene.

[0038] Furthermore, the alkyl carbon number in the alkylthiol RSH is C5 to C6. 18 One of them.

[0039] Furthermore, the alkenyl epoxy compound is one or more of allyl glycidyl ether, 2,3-epoxypropyl acrylate, and 1,2-epoxy-5-hexene.

[0040] Furthermore, the photoinitiator is one or more of 1,1-dimethoxy-1-phenylacetophenone (photo 651), 1-hydroxycyclohexylphenyl methyl ketone (photo 184), 2-methyl-1-(4-methylthiophenyl)-2-morpholino-1-propanone (photo 907), and 2-phenylbenzyl-2-dimethylamine-1-(4-morpholinobenzylphenyl)butanone (photo 369).

[0041] Furthermore, the organic solvents used in steps (1) to (4) may be the same or different, and each may be one or more of tetrahydrofuran, 1,4-dioxane, ethyl acetate, acetone, anhydrous ethanol, chloroform, N,N-dimethylformamide and dichloromethane. The mass of the organic solvent added is 1 to 10 times the total mass of the monomers added in this step.

[0042] Furthermore, in step (1), the molar ratio of the bio-based hydroxylamine compound, aldehyde compound, and mercaptoalkyl acid is 1:(1-1.2):(1-1.2);

[0043] Furthermore, in step (1), the mass ratio of the bio-based hydroxylamine compound to the catalyst is 1:(0.01~0.1);

[0044] Furthermore, in step (2), the molar ratio of maleic anhydride to aniline compounds is 1:(1-1.2);

[0045] Further, the molar ratio of the maleimide monomer, 2,5-furan dimethylamine, alkyl mercaptan and maleic anhydride in step (3) is 1:(1-1.2):(1-1.3):(2-2.2).

[0046] Further, the molar ratio of the terminal mercaptohexahydro-s-triazine monomer (A3), the bio-based maleimide monomer (B2) and the alkenyl epoxy compound in step (4) is 1:(0.75-0.95):(1.09-1.2); the mass ratio of the terminal mercaptohexahydro-s-triazine monomer and the photoinitiator is 1:(0.01-0.02).

[0047] Technical solution three: a bio-based hyperbranched epoxy resin containing hexahydro-s-triazine structure and bisphenol A type epoxy resin composite resin, the composite resin comprises the bio-based hyperbranched epoxy resin containing hexahydro-s-triazine structure or the bio-based hyperbranched epoxy resin containing hexahydro-s-triazine structure prepared by the above method. The preparation steps of the composite resin comprise: uniformly mixing the bio-based hyperbranched epoxy resin containing hexahydro-s-triazine structure, bisphenol A type epoxy resin and curing agent, pouring into a mold for heat curing to obtain the composite resin; the heat curing temperature is 50-180 DEG C, and the heat curing time is 3-15 hours; the curing agent is one or more of 4,4'-diamino diphenyl methane, 4,4'-diamino diphenyl sulfone and m-phenylenediamine.

[0048] Further, the bisphenol A type epoxy resin model is E51.

[0049] Further, the mass ratio of the bio-based hyperbranched epoxy resin, the bisphenol A type epoxy resin and the curing agent is 1:(4-9):(1-3).

[0050] Technical solution four: application of the bio-based hyperbranched epoxy resin containing hexahydro-s-triazine structure in linear epoxy resin reinforcement and toughening.

[0051] Compared with the prior art, the technical solution of the present application has the following advantages and beneficial effects:

[0052] 1. The bio-based hyperbranched epoxy resin containing hexahydro-s-triazine structure is prepared by using thiol-olefin click reaction, and a hyperbranched epoxy resin with efficient and environmentally friendly preparation method is obtained.

[0053] 2. The preparation process of the bio-based hyperbranched epoxy resin / bisphenol A type epoxy resin composite resin is simple, the reaction conditions are relatively mild, the reaction time is relatively short, and the raw material cost is relatively low.

[0054] 3、The bio-based hyperbranched epoxy resin of the present application not only has the unique advantages of hyperbranched polymers itself, but also exhibits extremely significant toughening and reinforcing efficiency when interacting with linear epoxy resin, which can effectively improve the comprehensive performance of the material, expand its application range and potential, and is expected to be widely used in the field of toughening and reinforcing of epoxy resin;

[0055] 4、The bio-based hyperbranched epoxy resin of the present application can be greenly degraded under relatively mild conditions due to the presence of hexahydro-s-triazine structure;

[0056] 5、The bio-based hyperbranched epoxy resin containing hexahydro-s-triazine structure of the present application has simple preparation process, mild reaction conditions, short reaction time, and small environmental pollution during the reaction process. BRIEF DESCRIPTION OF DRAWINGS

[0057] Figure 1 The FT-IR spectrum of the bio-based hyperbranched epoxy resin containing hexahydro-s-triazine structure synthesized in Example 1 is shown in the figure. As shown in the figure, the vibration absorption peak at 2572 cm -1 The absorption peak at 1640 cm -1 disappears, and the peak at 912 cm -1 belongs to the absorption peak of epoxy group, indicating the successful synthesis of the bio-based hyperbranched epoxy resin. DETAILED DESCRIPTION

[0058] The method of the present application will be further described below in combination with specific examples, but these examples should not limit the protection scope of the present application in any way.

[0059] The raw materials used in the following examples are as follows:

[0060] The type of bisphenol A epoxy resin is E51;

[0061] The mass concentration of formaldehyde aqueous solution is 37wt%;

[0062] The polymerization degree n of paraformaldehyde is 2.

[0063] Example 1 A bio-based hyperbranched epoxy resin containing hexahydro-s-triazine structure-bisphenol A epoxy resin composite resin and a preparation method thereof, the steps are as follows:

[0064] (1) 2.35 g (0.029 mol) of formaldehyde aqueous solution, 3.97 g (0.029 mol) of L-phenylalaninol and 50 ml of anhydrous ethanol were added to a reaction bottle, stirred at 85°C for 15 hours, then cooled to 10°C, 3.07 g (0.029 mol) of mercaptopropionic acid and 0.08 g of p-toluenesulfonic acid were added, and stirring was continued for 18 hours. The solvent was removed by rotary evaporation to obtain a terminal mercapto hexahydro-s-triazine (A3);

[0065] (2) 4.11 g (0.042 mol) of maleic anhydride, 6.00 g (0.042 mol) of β-naphthylamine and 50 ml of N,N-dimethylformamide were added to a reaction bottle, stirred at 2°C for 7 hours, then warmed to 50°C, and stirring was continued for 15 hours. The solvent was removed by rotary evaporation to obtain a maleimide monomer;

[0066] (3) 12.05 g (0.05 mol) of the maleimide monomer, 6.3 g (0.05 mol) of 2,5-furandimethylamine, 5.2 g (0.05 mol) of pentanethiol, 9.8 g (0.1 mol) of maleic anhydride and 50 ml of N,N-dimethylformamide were added to a reaction bottle, first reacted at 45°C for 8 hours, then warmed to 100°C, and stirring was continued for 10 hours. The solvent was removed by rotary evaporation to obtain a bio-based maleimide monomer (B2);

[0067] (4) 5.54 g (0.0078 mol) of A3, 4.30 g (0.0070 mol) of B2, 1.03 g

[0068] (0.009 mol) of allyl glycidyl ether, 0.06 g of 1-hydroxycyclohexyl phenyl ketone (Irgacure 184) and 50 ml of ethyl acetate were added to a reaction bottle, and a click reaction was performed by irradiation with ultraviolet light at a power of 400 W for 30 minutes. The solvent was removed by rotary evaporation to obtain a bio-based hyperbranched epoxy resin containing a hexahydro-s-triazine structure (HBEP-12), and the number average molecular weight and the epoxy value thereof are shown in Table 1.

[0069] (5) A mixture of 1 g of the bio-based hyperbranched epoxy resin containing a hexahydro-s-triazine structure in step (4), 9 g of a bisphenol A type epoxy resin and 2.77 g of 4,4'-diaminodiphenylmethane was stirred uniformly and then placed in a mold. Thermal curing was performed according to a curing program of 50°C for 1 hour, 80°C for 2 hours, 100°C for 3 hours and 140°C for 2 hours to obtain a bio-based hyperbranched epoxy resin containing a hexahydro-s-triazine structure / bisphenol A type epoxy resin composite resin, and the mechanical strength thereof is shown in Table 2.

[0070] Example 2 A bio-based hyperbranched epoxy resin containing a hexahydro-s-triazine structure / bisphenol A type epoxy resin composite resin and a method for preparing the same, the steps of which are as follows:

[0071] (1) 4.86 g (0.054 mol) of trioxane, 4.00 g (0.045 mol) of 4-hydroxybutylamine and 50 ml of 1,4-dioxane were added to a reaction bottle, stirred at 100°C for 5 hours, then cooled to 15°C, 5.72 g (0.054 mol) of mercaptopropionic acid and 0.4 g of 4-dimethylaminopyridine were added, and the stirring reaction was continued for 12 hours. The solvent was removed by rotary evaporation to obtain a terminal mercaptohexahydro-s-triazine (A3);

[0072] (2) 4.21 g (0.043 mol) of maleic anhydride, 6.15 g (0.043 mol) of β-naphthylamine and 50 ml of ethyl acetate were added to a reaction bottle, stirred at 5°C for 5 hours, then warmed to 70°C, and the stirring reaction was continued for 5 hours. The solvent was removed by rotary evaporation to obtain a maleimide monomer;

[0073] (3) 12.05 g (0.05 mol) of the maleimide monomer, 6.30 g (0.05 mol) of 2,5-furandimethylamine, 9.32 g (0.05 mol) of octadecanethiol, 9.8 g (0.1 mol) of maleic anhydride and 50 ml of N,N-dimethylformamide were added to a reaction bottle, first reacted at 60°C for 10 hours, then warmed to 160°C, and the reaction was continued for 10 hours. The solvent was removed by rotary evaporation to obtain a bio-based maleimide monomer (B2);

[0074] (4) 5.82 g (0.0078 mol) of A3, 5.62 g (0.0070 mol) of B2, 1.06 g

[0075] (0.0093 mol) of allyl glycidyl ether, 0.06 g of 1-hydroxycyclohexyl phenyl ketone (Irgacure 184) and 50 ml of tetrahydrofuran were added to a reaction bottle, and a click reaction was performed by irradiation with ultraviolet light at a power of 800 W for 10 min. The solvent was removed by rotary evaporation to obtain a bio-based hyperbranched epoxy resin containing a hexahydro-s-triazine structure (DBEP-12), and the number average molecular weight and the epoxy value thereof are shown in Table 1.

[0076] (5) A mixture of 1 g of the bio-based hyperbranched epoxy resin containing a hexahydro-s-triazine structure in step (4), 9 g of a bisphenol A type epoxy resin and 2.76 g of 4,4'-diaminodiphenylmethane was stirred uniformly and then placed in a mold. Thermal curing was performed according to a curing program of 50°C for 1 hour, 80°C for 2 hours, 100°C for 3 hours and 140°C for 2 hours to obtain a bio-based hyperbranched epoxy resin containing a hexahydro-s-triazine structure / bisphenol A type epoxy resin composite resin, and the mechanical strength thereof is shown in Table 2.

[0077] Example 3 A bio-based hyperbranched epoxy resin containing hexahydro-s-triazine structure / bisphenol A type epoxy resin composite resin and a preparation method thereof, the steps of which are as follows:

[0078] (1) 3.0 g (0.05 mol) of paraformaldehyde, 7.45 g (0.05 mol) of 1-amino-2-indanol and 50 ml of tetrahydrofuran were added to a reaction bottle, stirred at 40°C for 7 hours, then cooled to 20°C, 4.6 g (0.05 mol) of mercaptoacetic acid and 0.3 g of trifluoromethanesulfonic acid were added, and stirring was continued for 15 hours. The solvent was removed by rotary evaporation to obtain a terminal mercapto hexahydro-s-triazine (A3);

[0079] (2) 6.86 g (0.07 mol) of maleic anhydride, 15.19 g (0.07 mol) of 1-aminopyrene and 50 ml of ethyl acetate were added to a reaction bottle, stirred at 10°C for 1 hour, then warmed to 55°C, and stirring was continued for 5 hours. The solvent was removed by rotary evaporation to obtain a maleimide monomer;

[0080] (3) 14.85 g (0.05 mol) of the maleimide monomer, 6.3 g (0.05 mol) of 2,5-furandimethylamine, 5.2 g (0.05 mol) of pentanethiol, 9.8 g (0.1 mol) of maleic anhydride and 50 ml of N,N-dimethylformamide were added to a reaction bottle, first reacted at 45°C for 8 hours, then warmed to 100°C, and stirring was continued for 10 hours. The solvent was removed by rotary evaporation to obtain a bio-based maleimide monomer (B2);

[0081] (4) 6.21 g (0.0080 mol) of A3, 5.60 g (0.0076 mol) of B2, 0.99 g

[0082] (0.0087 mol) of allyl glycidyl ether, 0.12 g of 1,1-dimethoxy-1-phenylphenyl ethanone (light 651) and 50 ml of N,N-dimethylformamide were added to a reaction bottle, irradiated with ultraviolet light at a power of 400 W for 60 minutes, and the solvent was removed by rotary evaporation to obtain a bio-based hyperbranched epoxy resin containing hexahydro-s-triazine structure (BBEP-24), the number average molecular weight and epoxy value of which are shown in Table 1;

[0083] (5) A mixture of 1 g of the bio-based hyperbranched epoxy resin containing hexahydro-s-triazine structure in step (4), 9 g of a bisphenol A type epoxy resin and 2.76 g of 4,4'-diaminodiphenylmethane was stirred uniformly and then placed in a mold, and heat curing was performed according to a curing program of 50°C for 1 hour, 80°C for 2 hours, 100°C for 3 hours and 140°C for 2 hours to obtain a bio-based hyperbranched epoxy resin containing hexahydro-s-triazine structure / bisphenol A type epoxy resin composite resin, the mechanical strength of which is shown in Table 2.

[0084] Example 4 A bio-based hyperbranched epoxy resin containing hexahydro-s-triazine structure / bisphenol A type epoxy resin composite resin and its preparation method, the steps of which are as follows:

[0085] (1) 4.05 g (0.05 mol) of formaldehyde aqueous solution, 6.85 g (0.05 mol) of L-phenylglycinol and 50 ml of anhydrous ethanol were added to a reaction bottle, and stirred at 85°C for 5 hours, then cooled to 10°C, 4.6 g (0.05 mol) of mercaptoacetic acid and 0.13 g of p-toluenesulfonic acid were added, and the stirring reaction was continued for 12 hours, and the solvent was removed by rotary evaporation to obtain a terminal mercapto hexahydro-s-triazine (A3);

[0086] (2) 4.2 g (0.05 mol) of maleic anhydride, 7.16 g (0.05 mol) of β-naphthylamine and 50 ml of N,N-dimethylformamide were added to a reaction bottle, and stirred at 5°C for 2 hours, then warmed to 80°C, and the stirring reaction was continued for 6 hours, and the solvent was removed by rotary evaporation to obtain a maleimide monomer;

[0087] (3) 5 g (0.05 mol) of the maleimide monomer, 7.56 g (0.06 mol) of 2,5-furandimethylamine, 5.20 g (0.05 mol) of pentanethiol, 10.78 g (0.11 mol) of maleic anhydride and 50 ml of N,N-dimethylformamide were added to a reaction bottle, first reacted at 45°C for 8 hours, then warmed to 100°C, and the reaction was continued for 10 hours, and the solvent was removed by rotary evaporation to obtain a bio-based maleimide monomer (B2);

[0088] (4) 5.35 g (0.008 mol) of A3, 4.42 g (0.0072 mol) of B2, 1.09 g

[0089] (0.0096 mol) of allyl glycidyl ether, 0.11 g of 1,1-dimethoxy-1-phenylphenyl ethanone (light 651) and 50 ml of acetone were added to a reaction bottle, and a click reaction was carried out by irradiation with ultraviolet light with a power of 400 W for 30 min, and the solvent was removed by rotary evaporation to obtain a bio-based hyperbranched epoxy resin containing hexahydro-s-triazine structure (LBEP-12), and the number average molecular weight and epoxy value are shown in Table 1;

[0090] (5) A mixture of 1 g of the bio-based hyperbranched epoxy resin containing hexahydro-s-triazine structure in step (4), 9 g of a bisphenol A type epoxy resin and 2.77 g of 4,4'-diaminodiphenylmethane was stirred uniformly and then placed in a mold, and heat curing was carried out according to a curing program of 60°C for 1 hour, 80°C for 3 hours, 120°C for 3 hours and 160°C for 2 hours to obtain a bio-based hyperbranched epoxy resin containing hexahydro-s-triazine structure / bisphenol A type epoxy resin composite resin, and the mechanical strength is shown in Table 2.

[0091] Example 5 A bio-based hyperbranched epoxy resin containing hexahydro-s-triazine structure / bisphenol A type epoxy resin composite resin and its preparation method, the steps of which are as follows:

[0092] (1) 2.43 g (0.03 mol) of formaldehyde aqueous solution, 2.67 g (0.03 mol) of 4-hydroxybutylamine and 50 ml of 1,4-dioxane were added to a reaction bottle, stirred at 75°C for 5 hours, then cooled to 15°C, 3.39 g (0.03 mol) of mercaptopropionic acid and 0.05 g of 4-dimethylaminopyridine were added, and the stirring reaction was continued for 12 hours. The solvent was removed by rotary evaporation to obtain a terminal mercapto hexahydro-s-triazine (A3);

[0093] (2) 5.88 g (0.06 mol) of maleic anhydride, 5.58 g (0.06 mol) of aniline and 50 ml of ethyl acetate were added to a reaction bottle, stirred at 5°C for 2 hours, then warmed to 55°C, and the stirring reaction was continued for 5 hours. The solvent was removed by rotary evaporation to obtain a maleimide monomer;

[0094] (3) 8.5 g (0.05 mol) of maleimide monomer, 6.3 g (0.05 mol) of 2,5-furandimethylamine, 5.2 g (0.05 mol) of pentanethiol, 9.8 g (0.1 mol) of maleic anhydride and 50 ml of N,N-dimethylformamide were added to a reaction bottle, first reacted at 45°C for 8 hours, then warmed to 100°C for reaction, and the reaction was continued for 10 hours. The solvent was removed by rotary evaporation to obtain a bio-based maleimide monomer (B2);

[0095] (4) 5.67 g (0.01 mol) of A3, 4.94 g (0.009 mol) of B2, 1.37 g (0.012 mol) of allyl glycidyl ether, 0.11 g of 1,1-dimethoxy-1-phenylphenyl ethanone (light 651) and 50 ml of chloroform were added to a reaction bottle, and a click reaction was carried out by irradiation with ultraviolet light of power 400 W for 30 min. The solvent was removed by rotary evaporation to obtain a bio-based hyperbranched epoxy resin containing hexahydro-s-triazine structure (SBEP-12), and the number average molecular weight and epoxy value are shown in Table 1;

[0096] (5) A mixture of 1 g of the bio-based hyperbranched epoxy resin containing hexahydro-s-triazine structure in step (4), 9 g of bisphenol A type epoxy resin and 2.78 g of 4,4'-diaminodiphenylmethane was stirred uniformly and placed in a mold. Heat curing was carried out according to the curing program of 60°C for 1 hour, 80°C for 3 hours, 120°C for 3 hours and 160°C for 2 hours to obtain a bio-based hyperbranched epoxy resin containing hexahydro-s-triazine structure / bisphenol A type epoxy resin composite resin, and the mechanical strength is shown in Table 2.

[0097] Example 6 A bio-based hyperbranched epoxy resin containing hexahydro-s-triazine structure and a bisphenol-A type epoxy resin composite resin and a preparation method thereof, the steps of which are as follows:

[0098] (1) 0.97 g (0.012 mol) of formaldehyde aqueous solution, 1.79 g (0.012 mol) of 1-amino-2-indanol and 50 ml of anhydrous ethanol were added to a reaction bottle, and the reaction was stirred at 90°C for 6 hours, and then the temperature was lowered to 8°C, 1.77 g (0.012 mol) of mercaptohexanoic acid and 0.11 g of p-toluenesulfonic acid were added, and the reaction was continuously stirred for 15 hours, and the solvent was removed by rotary evaporation to obtain a terminal mercapto hexahydro-s-triazine (A3);

[0099] (2) 4.2 g (0.021 mol) of maleic anhydride, 3.0 g (0.021 mol) of β-naphthylamine and 50 ml of ethyl acetate were added to a reaction bottle, and the reaction was stirred at 5°C for 2 hours, and then the temperature was raised to 55°C, and the reaction was continuously stirred for 5 hours, and the solvent was removed by rotary evaporation to obtain a maleimide monomer;

[0100] (3) 11.15 g (0.05 mol) of the maleimide monomer, 5.92 g (0.05 mol) of 2,5-furandimethylamine, 11.5 g (0.05 mol) of tetradecanethiol, 9.8 g (0.1 mol) of maleic anhydride and 50 ml of N,N-dimethylformamide were added to a reaction bottle, and the reaction was first carried out at 45°C for 8 hours, and then the temperature was raised to 100°C, and the reaction was continuously carried out for 10 hours, and the solvent was removed by rotary evaporation to obtain a bio-based maleimide monomer (B2);

[0101] (4) 5.97 g (0.008 mol) of A3, 5.10 g (0.0072 mol) of B2, 1.23 g

[0102] (0.0096 mol) of 2,3-epoxypropyl acrylate, 0.11 g of 1,1-dimethoxy-1-phenyl phenyl ethanone (light 651) and 50 ml of N,N-dimethylformamide were added to a reaction bottle, and the click reaction was carried out by irradiation with ultraviolet light with a power of 400 W for 30 min, and the solvent was removed by rotary evaporation to obtain a bio-based hyperbranched epoxy resin containing hexahydro-s-triazine structure (YBEP-12), and the number average molecular weight and the epoxy value thereof are shown in Table 1;

[0103] (5) The mixture of 1 g of the bio-based hyperbranched epoxy resin containing hexahydro-s-triazine structure in step (4), 9 g of bisphenol A type epoxy resin and 2.76 g of 4,4'-diaminodiphenyl methane was stirred uniformly and then put into a mold, and heat curing was performed according to a curing procedure of 60°C for 1 hour, 80°C for 3 hours, 120°C for 3 hours and 160°C for 2 hours to obtain a bio-based hyperbranched epoxy resin containing hexahydro-s-triazine structure / bisphenol A type epoxy resin composite resin, and the mechanical strength thereof is shown in Table 2.

[0104] Example 7 A bio-based hyperbranched epoxy resin containing hexahydro-s-triazine structure / bisphenol A type epoxy resin composite resin and a preparation method thereof, and the steps thereof are as follows:

[0105] The mixture of 1 g of the bio-based hyperbranched epoxy resin containing hexahydro-s-triazine structure in step (4), 9 g of bisphenol A type epoxy resin and 2.76 g of 4,4'-diaminodiphenyl methane was stirred uniformly and then put into a mold, and heat curing was performed according to a curing procedure of 60°C for 1 hour, 80°C for 3 hours, 120°C for 3 hours and 160°C for 2 hours to obtain a bio-based hyperbranched epoxy resin containing hexahydro-s-triazine structure / bisphenol A type epoxy resin composite resin, and the mechanical strength thereof is shown in Table 2.

[0106] (2) The mixture of 1 g of the bio-based hyperbranched epoxy resin containing hexahydro-s-triazine structure in step (1), 9 g of bisphenol A type epoxy resin and 2.77 g of 4,4'-diaminodiphenyl methane was stirred uniformly and then put into a mold, and heat curing was performed according to a curing procedure of 50°C for 1 hour, 80°C for 2 hours, 100°C for 3 hours and 140°C for 2 hours to obtain a bio-based hyperbranched epoxy resin containing hexahydro-s-triazine structure / bisphenol A type epoxy resin composite resin, and the mechanical strength thereof is shown in Table 2.

[0107] Example 8-1 A bio-based hyperbranched epoxy resin containing hexahydro-s-triazine structure / bisphenol A type epoxy resin composite resin and a preparation method thereof, and the steps thereof are as follows:

[0108] The mixture of 1 g of the bio-based hyperbranched epoxy resin containing hexahydro-s-triazine structure in step (4), 9 g of bisphenol A type epoxy resin and 2.76 g of 4,4'-diaminodiphenyl methane was stirred uniformly and then put into a mold, and heat curing was performed according to a curing procedure of 60°C for 1 hour, 80°C for 3 hours, 120°C for 3 hours and 160°C for 2 hours to obtain a bio-based hyperbranched epoxy resin containing hexahydro-s-triazine structure / bisphenol A type epoxy resin composite resin, and the mechanical strength thereof is shown in Table 2.

[0109] Example 8-2 A bio-based hyperbranched epoxy resin containing hexahydro-s-triazine structure-bisphenol A type epoxy resin composite resin and its preparation method, the steps of which are as follows:

[0110] The mixture of 1 g of the bio-based hyperbranched epoxy resin containing hexahydro-s-triazine structure HBEP-12 prepared in Example 1, 9 g of bisphenol A type epoxy resin and 2.68 g of polyetheramine was stirred uniformly and then placed in a mold, and heat curing was performed according to a curing program of 50°C for 1 hour, 80°C for 2 hours, 100°C for 3 hours and 140°C for 2 hours, to obtain a bio-based hyperbranched epoxy resin containing hexahydro-s-triazine structure / bisphenol A type epoxy resin composite resin, the mechanical strength of which is shown in Table 2.

[0111] Example 8-3 A bio-based hyperbranched epoxy resin containing hexahydro-s-triazine structure-bisphenol A type epoxy resin composite resin and its preparation method, the steps of which are as follows:

[0112] The mixture of 1 g of the bio-based hyperbranched epoxy resin containing hexahydro-s-triazine structure HBEP-12 prepared in Example 1, 9 g of bisphenol A type epoxy resin and 1.20 g of diethylenetriamine was stirred uniformly and then placed in a mold, and heat curing was performed according to a curing program of 50°C for 1 hour, 80°C for 2 hours, 100°C for 3 hours and 140°C for 2 hours, to obtain a bio-based hyperbranched epoxy resin containing hexahydro-s-triazine structure / bisphenol A type epoxy resin composite resin, the mechanical strength of which is shown in Table 2.

[0113] Example 8-4 A bio-based hyperbranched epoxy resin containing hexahydro-s-triazine structure-bisphenol A type epoxy resin composite resin and its preparation method, the steps of which are as follows:

[0114] The mixture of 1 g of the bio-based hyperbranched epoxy resin containing hexahydro-s-triazine structure HBEP-12 prepared in Example 1, 9 g of bisphenol A type epoxy resin and 1.26 g of m-phenylenediamine was stirred uniformly and then placed in a mold, and heat curing was performed according to a curing program of 50°C for 1 hour, 80°C for 2 hours, 100°C for 3 hours and 140°C for 2 hours, to obtain a bio-based hyperbranched epoxy resin containing hexahydro-s-triazine structure / bisphenol A type epoxy resin composite resin, the mechanical strength of which is shown in Table 2.

[0115] Example 9 A bio-based hyperbranched epoxy resin containing hexahydro-s-triazine structure-bisphenol A type epoxy resin composite resin and its preparation method, the steps of which are as follows:

[0116] A mixture of the bio-based hyperbranched epoxy resin containing hexahydro-s-triazine structure HBEP-122g, bisphenol A type epoxy resin 8g and 2.77g 4,4'-diaminodiphenyl methane prepared in Example 1 was stirred uniformly and then put into a mold, and heat curing was performed according to a curing program of 50℃ for 1 hour, 80℃ for 2 hours, 100℃ for 3 hours, and 140℃ for 2 hours, to obtain a bio-based hyperbranched epoxy resin / bisphenol A type epoxy resin composite resin containing hexahydro-s-triazine structure, the mechanical strength of which is shown in Table 2.

[0117] Example 10 A bio-based hyperbranched epoxy resin containing hexahydro-s-triazine structure / bisphenol A type epoxy resin composite resin and a method for preparing the same, the steps of which are as follows:

[0118] (1) 2.35g (0.029mol) of formaldehyde aqueous solution, 4.32g (0.029mol) of 1-amino-2-indanol and 50ml of anhydrous ethanol were added to a reaction bottle, and stirring reaction was performed at 85℃ for 15 hours, after which the temperature was lowered to 10℃, 3.07g (0.029mol) of mercaptopropionic acid and 0.08g of p-toluenesulfonic acid were added, and stirring reaction was continued for 18 hours, after which the solvent was removed by rotary evaporation to obtain a terminal mercapto hexahydro-s-triazine (A3);

[0119] (2) 4.11g (0.042mol) of maleic anhydride, 6.00g (0.042mol) of β-naphthylamine and 50ml of N,N-dimethylformamide were added to a reaction bottle, and stirring reaction was performed at 2℃ for 7 hours, after which the temperature was raised to 50℃, and stirring reaction was continued for 15 hours, after which the solvent was removed by rotary evaporation to obtain a maleimide monomer;

[0120] (3) 12.05g (0.05mol) of the maleimide monomer, 6.3g (0.05mol)

[0121] 2,5-furandimethylamine, 5.2g (0.05mol) of pentanethiol, 9.8g (0.1mol) of maleic anhydride and 50ml of N,N-dimethylformamide were added to a reaction bottle, and reaction was performed at 45℃ for 8 hours, after which the temperature was raised to 100℃, and reaction was continued for 10 hours, after which the solvent was removed by rotary evaporation to obtain a bio-based maleimide monomer (B2);

[0122] (4) 5.83 g (0.0078 mol) of A3, 4.30 g (0.0070 mol) of B2, 1.03 g (0.009 mol) of allyl glycidyl ether, 0.06 g of 1-hydroxycyclohexyl phenyl ketone (light 184), and 50 ml of ethyl acetate were added to a reaction bottle, and a click reaction was performed by irradiation with ultraviolet light of 400 W power for 30 min, and the solvent was removed by rotary evaporation to obtain a bio-based hyperbranched epoxy resin containing hexahydro-s-triazine structure (ABEP-12), and the number average molecular weight and the epoxy value thereof are shown in Table 1;

[0123] (5) A mixture of 1 g of the bio-based hyperbranched epoxy resin containing hexahydro-s-triazine structure in step (4), 9 g of bisphenol A type epoxy resin, and 2.77 g of 4,4'-diaminodiphenyl methane was stirred uniformly and then placed in a mold, and heat curing was performed according to a curing program of 50°C for 1 hour, 80°C for 2 hours, 100°C for 3 hours, and 140°C for 2 hours to obtain a bio-based hyperbranched epoxy resin / bisphenol A type epoxy resin composite resin containing hexahydro-s-triazine structure, and the mechanical strength thereof is shown in Table 2.

[0124] Example 11 A bio-based hyperbranched epoxy resin containing hexahydro-s-triazine structure / bisphenol A type epoxy resin composite resin and a method for preparing the same, the steps of which are as follows:

[0125] (1) 2.35 g (0.029 mol) of formaldehyde aqueous solution, 2.58 g (0.029 mol) of 4-hydroxybutylamine, and 50 ml of anhydrous ethanol were added to a reaction bottle, and stirring was performed at 85°C for 15 hours, and then the temperature was lowered to 10°C, 3.07 g (0.029 mol) of mercaptopropionic acid and 0.08 g of p-toluenesulfonic acid were added, and stirring was continued for 18 hours, and the solvent was removed by rotary evaporation to obtain a terminal mercapto hexahydro-s-triazine (A3);

[0126] (2) 4.11 g (0.042 mol) of maleic anhydride, 6.00 g (0.042 mol) of β-naphthylamine, and 50 ml of N,N-dimethylformamide were added to a reaction bottle, and stirring was performed at 2°C for 7 hours, and then the temperature was raised to 50°C, and stirring was continued for 15 hours, and the solvent was removed by rotary evaporation to obtain a maleimide monomer;

[0127] (3) 12.05 g (0.05 mol) of the maleimide monomer, 6.3 g (0.05 mol) of 2,5-furandimethylamine, 5.2 g (0.05 mol) of pentanethiol, 9.8 g (0.1 mol) of maleic anhydride, and 50 ml of N,N-dimethylformamide were added to a reaction bottle, and first, a reaction was performed at 45°C for 8 hours, and then the temperature was raised to 100°C, and a reaction was continued for 10 hours, and the solvent was removed by rotary evaporation to obtain a bio-based maleimide monomer (B2);

[0128] 2,5-furandimethylamine, 5.2 g (0.05 mol) of pentanethiol, 9.8 g (0.1 mol) of maleic anhydride, and 50 ml of N,N-dimethylformamide were added to a reaction bottle, and first, a reaction was performed at 45°C for 8 hours, and then the temperature was raised to 100°C, and a reaction was continued for 10 hours, and the solvent was removed by rotary evaporation to obtain a bio-based maleimide monomer (B2);

[0129] (4) 4.42 g (0.0078 mol) of A3, 4.30 g (0.0070 mol) of B2, 1.03 g (0.009 mol) of allyl glycidyl ether, 0.06 g of 1-hydroxycyclohexyl phenyl ketone (photo 184), and 50 ml of ethyl acetate were added to a reaction bottle, and a click reaction was performed by irradiation with ultraviolet light of 400 W power for 30 min, and the solvent was removed by rotary evaporation to obtain a bio-based hyperbranched epoxy resin containing hexahydro-s-triazine structure (IBEP-12), and the number average molecular weight and the epoxy value thereof are shown in Table 1;

[0130] (5) A mixture of 1 g of the bio-based hyperbranched epoxy resin containing hexahydro-s-triazine structure in step (4), 9 g of bisphenol A type epoxy resin, and 2.78 g of 4,4'-diaminodiphenyl methane was stirred uniformly and then placed in a mold, and heat curing was performed according to a curing program of 50°C for 1 hour, 80°C for 2 hours, 100°C for 3 hours, and 140°C for 2 hours to obtain a bio-based hyperbranched epoxy resin / bisphenol A type epoxy resin composite resin containing hexahydro-s-triazine structure, and the mechanical strength thereof is shown in Table 2.

[0131] Example 12 A bio-based hyperbranched epoxy resin containing hexahydro-s-triazine structure / bisphenol A type epoxy resin composite resin and a method for preparing the same, the steps of which are as follows:

[0132] (1) 0.97 g (0.012 mol) of formaldehyde aqueous solution, 1.79 g (0.012 mol) of 1-amino-2-indanol, and 50 ml of anhydrous ethanol were added to a reaction bottle, and stirring was performed at 90°C for 6 hours, and then the temperature was lowered to 8°C, 1.77 g (0.012 mol) of mercaptohexanoic acid and 0.11 g of p-toluenesulfonic acid were added, and stirring was continued for 15 hours, and the solvent was removed by rotary evaporation to obtain a terminal mercapto hexahydro-s-triazine (A3);

[0133] (2) 4.2 g (0.021 mol) of maleic anhydride, 4.5 g (0.021 mol) of 1-amino pyrene, and 50 ml of ethyl acetate were added to a reaction bottle, and stirring was performed at 5°C for 2 hours, and then the temperature was raised to 55°C, and stirring was continued for 5 hours, and the solvent was removed by rotary evaporation to obtain a maleimide monomer;

[0134] (3) 14.85 g (0.05 mol) of the maleimide monomer, 5.92 g (0.05 mol) of 2,5-furandimethylamine, 11.5 g (0.05 mol) of tetradecanethiol, 9.8 g (0.1 mol) of maleic anhydride, and 50 ml of N,N-dimethylformamide were added to a reaction bottle, and first, reaction was performed at 45°C for 8 hours, and then the temperature was raised to 100°C, and reaction was continued for 10 hours, and the solvent was removed by rotary evaporation to obtain a bio-based maleimide monomer (B2);

[0135] (4) 5.97 g (0.008 mol) of A3, 5.85 g (0.0072 mol) of B2, 1.23 g (0.0096 mol) of 2,3-epoxypropyl acrylate, 0.12 g of 1,1-dimethoxy-1-phenyl ethanone (light 651) and 50 ml of N,N-dimethylformamide were added to a reaction bottle, and a click reaction was performed under irradiation with ultraviolet light of 400 W for 30 min, and the solvent was removed by rotary evaporation to obtain a bio-based hyperbranched epoxy resin containing hexahydro-s-triazine structure (FBEP-12), the number average molecular weight and epoxy value of which are shown in Table 1.

[0136] (0.0096 mol) of 2,3-epoxypropyl acrylate, 0.12 g of 1,1-dimethoxy-1-phenyl ethanone (light 651) and 50 ml of N,N-dimethylformamide were added to a reaction bottle, and a click reaction was performed under irradiation with ultraviolet light of 400 W for 30 min, and the solvent was removed by rotary evaporation to obtain a bio-based hyperbranched epoxy resin containing hexahydro-s-triazine structure (FBEP-12), the number average molecular weight and epoxy value of which are shown in Table 1.

[0137] (5) A mixture of 1 g of the bio-based hyperbranched epoxy resin containing hexahydro-s-triazine structure in step (4), 9 g of bisphenol A type epoxy resin and 2.76 g of 4,4'-diaminodiphenyl methane was stirred uniformly and then placed in a mold, and heat curing was performed according to a curing program of 60°C for 1 hour, 80°C for 3 hours, 120°C for 3 hours and 160°C for 2 hours to obtain a bio-based hyperbranched epoxy resin containing hexahydro-s-triazine structure / bisphenol A type epoxy resin composite resin, the mechanical strength of which is shown in Table 2.

[0138] Example 13 A bio-based hyperbranched epoxy resin containing hexahydro-s-triazine structure / bisphenol A type epoxy resin composite resin and a method for preparing the same, the steps of which are as follows:

[0139] (1) 6.21 g (0.0080 mol) of the terminal mercapto hexahydro-s-triazine (A3) prepared in step (1) of Example 3, 5.31 g (0.0072 mol) of the bio-based maleimide monomer (B2) prepared in step (3) of Example 3, 1.03 g (0.009 mol) of allyl glycidyl ether, 0.12 g of 1,1-dimethoxy-1-phenyl ethanone (light 651) and 50 ml of N,N-dimethylformamide were added to a reaction bottle, and a click reaction was performed under irradiation with ultraviolet light of 400 W for 60 min, and the solvent was removed by rotary evaporation to obtain a bio-based hyperbranched epoxy resin containing hexahydro-s-triazine structure (BBEP-12), the number average molecular weight and epoxy value of which are shown in Table 1.

[0140] (2) A mixture of 1 g of the bio-based hyperbranched epoxy resin in step (1), 9 g of bisphenol A type epoxy resin and 2.77 g of 4,4'-diaminodiphenyl methane was stirred uniformly and then placed in a mold, and heat curing was performed according to a curing program of 50°C for 1 hour, 80°C for 2 hours, 100°C for 3 hours and 140°C for 2 hours to obtain a bio-based hyperbranched epoxy resin containing hexahydro-s-triazine structure / bisphenol A type epoxy resin composite resin, the mechanical strength of which is shown in Table 2.

[0141] Comparative Example 1

[0142] A mixture of 10 g of the bio-based hyperbranched epoxy resin containing hexahydro-s-triazine structure (HBEP-12) prepared in Example 1 and 3.96 g of 4,4'-diaminodiphenyl methane was stirred uniformly and then put into a mold, and heat-cured according to a curing program of 50°C for 1 hour, 80°C for 2 hours, 100°C for 3 hours, and 140°C for 2 hours, to obtain a pure bio-based hyperbranched epoxy resin material, the mechanical strength of which is shown in Table 3.

[0143] Comparative Example 2

[0144] A mixture of 10 g of the bio-based hyperbranched epoxy resin containing hexahydro-s-triazine structure (DBEP-12) prepared in Example 2 and 3.46 g of 4,4'-diaminodiphenyl methane was stirred uniformly and then put into a mold, and heat-cured according to a curing program of 50°C for 1 hour, 80°C for 2 hours, 100°C for 3 hours, and 140°C for 2 hours, to obtain a pure bio-based hyperbranched epoxy resin material, the mechanical strength of which is shown in Table 3.

[0145] Comparative Example 3

[0146] A mixture of 10 g of the bio-based hyperbranched epoxy resin containing hexahydro-s-triazine structure (BBEP-24) prepared in Example 3 and 2.97 g of 4,4'-diaminodiphenyl methane was stirred uniformly and then put into a mold, and heat-cured according to a curing program of 50°C for 1 hour, 80°C for 2 hours, 100°C for 3 hours, and 140°C for 2 hours, to obtain a pure bio-based hyperbranched epoxy resin material, the mechanical strength of which is shown in Table 3.

[0147] Comparative Example 4

[0148] A mixture of 10 g of the bio-based hyperbranched epoxy resin containing hexahydro-s-triazine structure (LBEP-12) prepared in Example 4 and 4.46 g of 4,4'-diaminodiphenyl methane was stirred uniformly and then put into a mold, and heat-cured according to a curing program of 50°C for 1 hour, 80°C for 2 hours, 100°C for 3 hours, and 140°C for 2 hours, to obtain a pure bio-based hyperbranched epoxy resin material, the mechanical strength of which is shown in Table 3.

[0149] Comparative Example 5

[0150] A mixture of 10 g of the bio-based hyperbranched epoxy resin containing hexahydro-s-triazine structure (SBEP-12) prepared in Example 5 and 4.95 g of 4,4'-diaminodiphenyl methane was stirred uniformly and then put into a mold, and heat-cured according to a curing program of 50°C for 1 hour, 80°C for 2 hours, 100°C for 3 hours, and 140°C for 2 hours, to obtain a pure bio-based hyperbranched epoxy resin material, the mechanical strength of which is shown in Table 3.

[0151] Comparative Example 6

[0152] A mixture of 10 g of bio-based hyperbranched epoxy resin containing hexahydro-s-triazine structure (YBEP-12) prepared in Example 6 and 3.47 g of 4,4'-diaminodiphenyl methane was stirred uniformly and placed in a mold, and heat cured according to a curing program of 50°C for 1 hour, 80°C for 2 hours, 100°C for 3 hours, and 140°C for 2 hours, to obtain a pure bio-based hyperbranched epoxy resin material, the mechanical strength of which is shown in Table 3.

[0153] Comparative Example 7

[0154] A mixture of 10 g of bio-based hyperbranched epoxy resin containing hexahydro-s-triazine structure (HBEP-24) prepared in Example 7 and 3.96 g of 4,4'-diaminodiphenyl methane was stirred uniformly and placed in a mold, and heat cured according to a curing program of 50°C for 1 hour, 80°C for 2 hours, 100°C for 3 hours, and 140°C for 2 hours, to obtain a pure bio-based hyperbranched epoxy resin material, the mechanical strength of which is shown in Table 3.

[0155] Comparative Example 10

[0156] A mixture of 10 g of bio-based hyperbranched epoxy resin containing hexahydro-s-triazine structure (ABEP-12) prepared in Example 10 and 3.96 g of 4,4'-diaminodiphenyl methane was stirred uniformly and placed in a mold, and heat cured according to a curing program of 50°C for 1 hour, 80°C for 2 hours, 100°C for 3 hours, and 140°C for 2 hours, to obtain a pure bio-based hyperbranched epoxy resin material, the mechanical strength of which is shown in Table 3.

[0157] Comparative Example 11

[0158] A mixture of 10 g of bio-based hyperbranched epoxy resin containing hexahydro-s-triazine structure (IBEP-12) prepared in Example 11 and 4.95 g of 4,4'-diaminodiphenyl methane was stirred uniformly and placed in a mold, and heat cured according to a curing program of 50°C for 1 hour, 80°C for 2 hours, 100°C for 3 hours, and 140°C for 2 hours, to obtain a pure bio-based hyperbranched epoxy resin material, the mechanical strength of which is shown in Table 3.

[0159] Comparative Example 12

[0160] A mixture of 10 g of bio-based hyperbranched epoxy resin containing hexahydro-s-triazine structure (FBEP-12) prepared in Example 12 and 3.47 g of 4,4'-diaminodiphenyl methane was stirred uniformly and placed in a mold, and heat cured according to a curing program of 50°C for 1 hour, 80°C for 2 hours, 100°C for 3 hours, and 140°C for 2 hours, to obtain a pure bio-based hyperbranched epoxy resin material, the mechanical strength of which is shown in Table 3.

[0161] Comparative Example 13

[0162] A mixture of 10 g of the bio-based hyperbranched epoxy resin containing hexahydro-s-triazine structure (BBEP-12) prepared in Example 13 and 3.96 g of 4,4'-diaminodiphenyl methane was stirred uniformly and then placed in a mold, and heat-cured according to a curing program of 50°C for 1 hour, 80°C for 2 hours, 100°C for 3 hours, and 140°C for 2 hours, to obtain a pure bio-based hyperbranched epoxy resin material, the mechanical strength of which is shown in Table 3.

[0163] Comparative Example 14

[0164] A mixture of 10 g of a bisphenol A type epoxy resin and 3.03 g of 4,4'-diaminodiphenyl methane was stirred uniformly and then placed in a mold, and heat-cured according to a curing program of 50°C for 1 hour, 80°C for 2 hours, 100°C for 3 hours, and 140°C for 2 hours, to obtain a pure bisphenol A type epoxy resin material, the mechanical strength of which is shown in Table 3.

[0165] Table 1 Properties of bio-based hyperbranched epoxy resin containing hexahydro-s-triazine structure

[0166]

[0167]

[0168] Table 2 Mechanical properties of bio-based hyperbranched epoxy resin containing hexahydro-s-triazine structure / bisphenol A epoxy resin composite resin

[0169]

[0170] Table 3 Mechanical properties of pure bio-based hyperbranched epoxy resin or pure bisphenol A type epoxy resin after curing

[0171]

[0172]

[0173] Note: The measurement method of "tensile strength" in Table 2 and Table 3 is to use a universal material testing machine (Instron 5943) to test according to the ASTM standard ASTM D638-14 "Standard Test Methods for Tensile Properties of Polymer Matrix Composite Resins"; the measurement method of "flexural strength" is to use a universal material testing machine (Instron 5943) to test according to the ASTM standard D790M-92 "Flexural Test Method", and the test temperature is 25°C.

[0174] 1. From the test results in Table 1, it can be seen that:

[0175] The number average molecular weight of the bio-based hyperbranched epoxy resin containing hexahydro-s-triazine structure obtained by the application gradually increases with the increase of the number of terminal epoxy groups; when the number of terminal epoxy groups is 24, the number average molecular weight reaches a maximum value of 35290 g / mol.

[0176] The bio-based hyperbranched epoxy resin containing hexahydro-s-triazine structure obtained in examples 1-2, 4-6 of the application has different structures and different epoxy values, and the greater the number average molecular weight, the smaller the epoxy value.

[0177] 2, It can be seen from the test results in Table 2 and Table 3 that:

[0178] The bio-based hyperbranched epoxy resin containing hexahydro-s-triazine structure obtained by the application has obvious toughening effect on linear epoxy resin such as bisphenol A type epoxy resin.

[0179] In examples 1, 8-1, 8-2, 8-3 and 8-4 of the application, changing the type of curing agent will result in different tensile strength and bending strength of the bio-based hyperbranched epoxy resin containing hexahydro-s-triazine structure / bisphenol A epoxy resin composite resin. Considering the application range of curing temperature and the influence of the molecular structure of the curing agent on the mechanical properties of the composite resin, 4,4'-diaminodiphenyl methane, 4,4'-diaminodiphenyl sulfone and m-phenylenediamine are more preferred curing agents, and 4,4'-diaminodiphenyl methane is the most preferred curing agent.

[0180] In examples 1, 2, 3 and 4, 5, 6 of the application, changing the structure of the terminal mercapto hexahydro-s-triazine monomer will result in different tensile strength and bending strength of the composite resin. A large number of cavities reduce the crosslinking density, and the mechanical properties are also reduced. The smaller the cavity volume in the structure, the smaller the free volume of the molecule, and the greater the tensile strength and bending strength.

[0181] In examples 1, 7 and 3, 13 of the application, (by adjusting the ratio of terminal mercapto hexahydro-s-triazine monomer to bio-based maleimide monomer) changing the number of terminal epoxy groups of the bio-based hyperbranched epoxy resin containing hexahydro-s-triazine structure in the bio-based hyperbranched epoxy resin / bisphenol A epoxy resin composite resin will result in different tensile strength and bending strength of the composite resin. When the number of terminal epoxy groups of the bio-based hyperbranched epoxy resin is 12, the crosslinking density of the composite resin is the largest, so the tensile strength and bending strength reach the maximum value; when the number of terminal epoxy groups of the bio-based hyperbranched epoxy resin is 24, a large number of cavities reduce the crosslinking density, and the mechanical properties are also reduced.

[0182] In the embodiment 1, the embodiment 10 and the embodiment 11 of the present application, by changing the bio-based hydroxylamine compound, the tensile strength and the bending strength of the bio-based hyperbranched epoxy resin / bisphenol A epoxy resin composite resin are different, and when the rigid structure in the structure increases, the tensile strength and the bending strength increase.

[0183] In the embodiment 6 and the embodiment 12 of the present application, by changing the structure of the bio-based maleimide monomer, the tensile strength and the bending strength of the bio-based hyperbranched epoxy resin / bisphenol A epoxy resin composite resin are different, the more the benzene ring content is, the stronger the rigidity of the composite resin is, and the stronger the mechanical property is. Therefore, the performance of the embodiment 12 with more benzene ring structure is better.

[0184] In the embodiment 1 and the embodiment 9 of the present application, by changing the mass fraction of the bio-based hyperbranched epoxy resin, the tensile strength and the bending strength of the bio-based hyperbranched epoxy resin / bisphenol A epoxy resin composite resin are different, when the mass fraction of the bio-based hyperbranched epoxy resin added is 10%, the tensile strength and the bending strength reach the maximum value, which are 96±5 MPa and 178±6 MPa respectively; when the mass fraction of the bio-based hyperbranched epoxy resin added reaches 20%, the tensile strength and the bending strength are 88±5 MPa and 165±7 MPa respectively, and the proportion of the bio-based hyperbranched epoxy resin increases from 10% to 20%, the crosslinking density of the composite resin decreases, and the mechanical property also decreases accordingly.

[0185] The above only describes the preferred embodiments of the present application, and is not used to limit the present application, any modification, equivalent replacement, improvement, etc. made within the spirit and principle of the present application should be included in the protection scope of the present application.

Claims

1. A biobased hyperbranched epoxy resin containing a hexahydro-s-triazine structure, characterized in that, The structural formula is as follows general formula (1): Wherein, R', R'', R''' are the same or different, and respectively represent the structure of general formula (2), general formula (3) or general formula (4): Wherein, X is one or more of the following structures: The structure of R is as follows: R2 is one or more of the following structures: In the structure of R2, -C-O- is connected with -CO- in R4 to form -COO-, and the other end of the structure of R2 is connected with -N in the structure of R to form -CN-; The structure of R1 is as follows: Wherein, R3 is one or more of the following structures: Wherein, R4 is the following structure: n is a natural number from 1 to 5; Wherein, R5 is an aliphatic alkyl group with 5-18 carbon atoms; The number average molecular weight of the bio-based hyperbranched epoxy resin containing hexahydro-s-triazine structure is 11000-36000 g / mol, and the epoxy value is 0.06-0.10 mol / 100g.

2. The process for the preparation of a biobased hyperbranched epoxy resin containing hexahydro-s-triazine structure according to claim 1, characterized in that, Comprise the following steps: (1) add aldehyde compound, bio-based hydroxylamine compound and organic solvent into the reaction bottle, stir at 40-100℃ for 5-15 hours, then cool to 10-30℃, add mercaptoalkyl acid and catalyst, continue to stir for 12-18 hours, To obtain a terminal mercapto hexahydro-s-triazine monomer; (2) add maleic anhydride, aniline compound and organic solvent into the reaction bottle, stir at 2-10℃ for 1-7 hours, then warm to 50-80℃, Continue to stir for 5-15 hours to obtain maleimide monomer; (3) add maleimide monomer, 2,5-furandimethylamine, alkyl mercaptan, maleic anhydride and organic solvent into the reaction bottle, stir at 45-160℃ for 15-20 hours to obtain bio-based maleimide monomer; (4) add the terminal mercapto hexahydro-s-triazine monomer obtained in step (1), the bio-based maleimide monomer obtained in step (3) Add alkenyl epoxy compound, organic solvent and photoinitiator into the reaction bottle, and carry out thiol-alkene click reaction under the irradiation of ultraviolet light with power of 400-800W for 10-60 minutes to obtain bio-based hyperbranched epoxy resin containing hexahydro-s-triazine structure, the number average molecular weight is 11000-36000 g / mol, and the epoxy value is 0.06-0.1 mol / 100g.

3. The method of claim 2, wherein: said bio-based hydroxylamine compound is 1-amino-2-indanol 4-hydroxybutylamine and L-phenylglycinol one or more of The aniline compound is one or more of aniline, β-naphthylamine and 1-aminopyrene.

4. The method of claim 2, wherein: The aldehyde compound is one or more of trioxymethylene, polyoxymethylene and formaldehyde aqueous solution; the mercaptoalkyl acid is n＝1～5； The alkyl carbon number in the alkyl mercaptan RSH is C5-C 18 one of the following: The alkenyl epoxy compound is one or more of allyl glycidyl ether, 2,3-epoxypropyl acrylate and 1,2-epoxy-5-hexene.

5. The method of claim 2, wherein: The catalyst is one or more of p-toluenesulfonic acid, trifluoromethanesulfonic acid, and 4-dimethylaminopyridine; the photoinitiator is one or more of 1,1-dimethoxy-1-phenyl ethanone, 1-hydroxycyclohexyl phenyl ketone, 2-methyl-1-(4-methylthiophenyl)-2-morpholinyl-1-propanone, and 2-phenyl benz-2-dimethylamine-1-(4-morpholinobenzyl) butanone; the organic solvents in steps (1)-(4) are the same or different, and each independently is one or two or more of tetrahydrofuran, 1,4-dioxane, ethyl acetate, acetone, anhydrous ethanol, chloroform, N,N-dimethylformamide, and dichloromethane.

6. The method of claim 2, wherein: In step (1), the molar ratio of the bio-based hydroxylamine compound, the aldehyde compound, and the mercaptoalkyl acid is 1:(1-1.2):(1-1.2), and the mass ratio of the bio-based hydroxylamine compound and the catalyst is 1:(0.01-0.1); In step (2), the molar ratio of the maleic anhydride and the aniline compound is 1:(1-1.2); In step (3), the molar ratio of the maleimide monomer, 2,5-furandimethylamine, alkyl mercaptan, and maleic anhydride is 1:(1-1.2):(1-1.3):(2-2.2); In step (4), the molar ratio of the terminal mercaptohexahydro-s-triazine monomer, the bio-based maleimide monomer, and the alkenyl epoxy compound is 1:(0.75-0.95):(1.09-1.2), and the mass ratio of the terminal mercaptohexahydro-s-triazine monomer and the photoinitiator is 1:(0.01-0.02); In steps (1)-(4), the mass of the organic solvent added is 1-10 times the total mass of the monomers added in the step.

7. A bio-based hyperbranched epoxy resin- Bisphenol-A type epoxy resin hybrid resin containing hexahydro-s-triazine structure, characterized by, The composite resin comprises the bio-based hyperbranched epoxy resin containing a hexahydro-s-triazine structure according to claim 1 or the bio-based hyperbranched epoxy resin containing a hexahydro-s-triazine structure prepared by the method according to any one of claims 2-6.

8. The bio-based hyperbranched epoxy-diphenylpropane epoxy hybrid resin according to claim 7, characterized in that, The bio-based hyperbranched epoxy resin containing a hexahydro-s-triazine structure, the bisphenol A type epoxy resin, and the curing agent are thoroughly mixed and uniformly, and then poured into a mold for thermal curing; the curing agent is one or more of 4,4'-diaminodiphenyl methane, 4,4'-diaminodiphenyl sulfone, and m-phenylenediamine.

9. The bio-based hyperbranched epoxy-diphenyl A epoxy hybrid resin according to claim 8, characterized in that, The mass ratio of the bio-based hyperbranched epoxy resin, the bisphenol A type epoxy resin, and the curing agent is 1:(4-9):(1-3).

10. Use of the bio-based hyperbranched epoxy resin containing a hexahydro-s-triazine structure according to claim 1 or the bio-based hyperbranched epoxy resin containing a hexahydro-s-triazine structure prepared by the method according to any one of claims 2-6 in reinforcing and toughening a linear epoxy resin.

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