A multifunctional terpene resin composite material and its application in the field of high-end coatings

Abstract

The present invention relates to the technical field of resin materials, and discloses a multifunctional terpene resin composite material and its application in the field of high-end coatings. The present invention obtains a multifunctional terpene resin composite material by extruding terpene resin, boron-modified benzoxazine, modified epoxy resin, and calcium carbonate in a twin-screw extruder for granulation, and then molding the granules in a flat vulcanizer. The three-dimensional network structure formed by the boron-oxygen bond in the boron-modified benzoxazine has high flame retardancy with high oxygen index, low toxicity, low smoke and low calorific value; the sulfur element therein also has a good flame retardant effect; and the benzoxazine will form a heat-resistant phenolic resin structure at high temperature, so that it has a good flame retardant effect; the silicon element contained in the modified epoxy resin has a good flame retardant effect. At the same time, the multifunctional terpene resin composite material also has a good antibacterial effect.

Description

Technical Field

[0001] The present invention relates to the technical field of resin materials, and in particular to a multifunctional terpene resin composite material and its application in the field of high-end coatings. Background Art

[0002] Terpene resin is a thermoplastic solid polymerized from a terpene mixture. Terpene resin is mainly formed by cationic polymerization of α-pinene or β-pinene in turpentine oil under the action of Falk's catalyst. It has properties such as non-toxicity, radiation resistance, and anti-crystallization. However, its flame retardant effect has not been improved, which limits its application in the field of coatings. For example, patent CN104151467A discloses a method for preparing terpene resin, and the invention of preparing terpene resin from 3-carene not only broadens the application range of 3-carene, but also provides a method for preparing terpene resin with lower cost, but its flame retardant effect has not been improved. Summary of the invention

[0003] 1. Technical issues to be resolved

[0004] In view of the deficiencies in the prior art, the present invention provides a multifunctional terpene resin composite material and its application in the field of high-end coatings, which has good antibacterial and flame retardant effects.

[0005] (II) Technical solution

[0006] To achieve the above object, the present invention provides the following technical solution: a multifunctional terpene resin composite material, comprising the following weight components: 35-50 parts by weight of terpene resin, 6-10 parts by weight of boron-modified benzoxazine, 4-7 parts by weight of modified epoxy resin, and 0.6-1 parts by weight of calcium carbonate;

[0007] The preparation method of the boron-modified benzoxazine is as follows:

[0008] (1) adding ferrocene boric acid to toluene solvent, stirring and dispersing, and then adding 4-methyl-5-thiazoleethanol thereto, reacting at 110-125° C. for 8-13 hours. After the reaction is completed, distilling under reduced pressure, filtering and drying to obtain ferrocene-modified thiazole;

[0009] (2) adding ferrocene-modified thiazole and 3-chloropropylene to N,N-dimethylformamide solvent, stirring and dispersing, reacting at 70-95° C. for 7-11 hours, and then distilling under reduced pressure and filtering to obtain olefinated ferrocene-modified thiazole;

[0010] (3) adding olefinated ferrocene-modified thiazole to N,N-dimethylformamide solvent, stirring and dispersing, adding mercaptoethylamine and benzoin dimethyl ether photoinitiators, irradiating with ultraviolet light at 25-40° C. for 3-6 hours, centrifuging after the end, washing and drying to obtain olefinated ferrocene-modified thiazole;

[0011] (4) Adding the amino ferrocene modified thiazole, the aqueous solution of formaldehyde, and cardanol into toluene solvent, fully dissolving them, and carrying out a cyclization reaction at 75-95° C. for 5-8 hours. After the reaction, distilling under reduced pressure, washing, and drying are performed to obtain a boron-modified benzoxazine.

[0012] In the above reaction process, the boric acid group in ferrocenylboric acid reacts with the hydroxyl group in 4-methyl-5-thiazoleethanol to introduce a tertiary amine group, thereby obtaining ferrocenyl modified thiazole; the tertiary amine group in ferrocenyl modified thiazole reacts with the chlorine in 3-chloropropylene to generate a quaternary ammonium salt group and introduces an alkenyl group, thereby obtaining alkenylated ferrocenyl modified thiazole; the alkenyl group in alkenylated ferrocenyl modified thiazole reacts with the thiol group in mercaptoethylamine to introduce an amino group, thereby obtaining aminoated ferrocenyl modified thiazole; the aminoated ferrocenyl modified thiazole, an aqueous solution of formaldehyde, and cardanol are subjected to a cyclization reaction, thereby obtaining a boron-modified benzoxazine.

[0013] Preferably, the mass ratio of ferrocenylboric acid to 4-methyl-5-thiazoleethanol in (1) is (1-1.2):(2.1-2.3).

[0014] Preferably, the mass ratio of ferrocene-modified thiazole and 3-chloropropylene in (2) is (0.8-1):(1.4-1.8).

[0015] Preferably, the mass ratio of olefinated ferrocene-modified thiazole, mercaptoethylamine, and benzoin dimethyl ether photoinitiator in (3) is (1.5-1.84):(1-2.1):(0.01-0.03).

[0016] Preferably, the mass ratio of the aminoferrocene-modified thiazole, the aqueous solution of formaldehyde, and cardanol in (4) is (1.2-1.3):(2.2-2.8):(0.9-1.25).

[0017] Preferably, the preparation method of the modified epoxy resin is:

[0018] S1. Add terpene-based epoxy resin and p-aminobenzoic acid into a stirrer, stir and reflux at 85-95°C for 3-5h, and after the reaction, remove the solvent by distillation under reduced pressure, then add N,N-dimethylethanolamine aqueous solution for neutralization, stir for 15-20min, and then add distilled water for dispersion and dilution to obtain an epoxy resin-based polyol aqueous dispersion;

[0019] S2. Add pentaerythritol methyl silicate to N,N-dimethylformamide solvent, stir and disperse, then add epoxy resin-based polyol aqueous dispersion thereto, react at 95-110°C for 10-17h, filter after reaction, distill the filtrate under reduced pressure, wash with deionized water, and dry to obtain modified epoxy resin.

[0020] In the above reaction process, the epoxy group in the terpene-based epoxy resin and the amino group in the p-aminobenzoic acid undergo a ring-opening reaction to generate a hydroxyl group, and at the same time, a carboxyl group is introduced to obtain an epoxy resin-based polyol aqueous dispersion; the carboxyl group in the epoxy resin-based polyol aqueous dispersion and the hydroxyl group in pentaerythritol methyl silicate undergo an esterification reaction to obtain a modified epoxy resin.

[0021] Preferably, the mass ratio of the terpene-based epoxy resin, p-aminobenzoic acid, and N,N-dimethylethanolamine aqueous solution in S1 is (0.7-1.1):(1.22-1.35):(0.2-0.44).

[0022] Preferably, the mass ratio of pentaerythritol methyl silicate to epoxy resin-based polyol aqueous dispersion in S2 is (2.15-2.46):(1.23-1.56).

[0023] Preferably, the preparation method of the multifunctional terpene resin composite material is: terpene resin, boron-modified benzoxazine, modified epoxy resin, and calcium carbonate are extruded and granulated at 180-190° C. in a twin-screw extruder, and then the granules are compression molded in a flat vulcanizer at a pressure of 8-9 MPa and 185-190° C. to obtain a multifunctional terpene resin composite material.

[0024] Preferably, the multifunctional terpene resin composite material is used in the field of high-end coatings.

[0025] (III) Beneficial technical effects

[0026] In the technical scheme of the present invention, a multifunctional terpene resin composite material is obtained by extruding terpene resin, boron-modified benzoxazine, modified epoxy resin and calcium carbonate in a twin-screw extruder to form granules, and then molding the granules in a flat vulcanizer.

[0027] The three-dimensional network structure formed by the boron-oxygen bonds in the boron-modified benzoxazine has high flame retardancy with high oxygen index, low toxicity, low smoke and low calorific value; the sulfur element therein also has a good flame retardant effect; and benzoxazine will form a heat-resistant phenolic resin structure at high temperature, giving it a good flame retardant effect; the silicon element contained in the modified epoxy resin can form a glass-like substance on the surface of the material when burning, which hinders the material transfer and energy transport between the air and the substrate, and has a flame retardant effect.

[0028] The quaternary ammonium salt group, thiazole group, ferrocenyl group and cardanol structure in boron-modified benzoxazine all have good antibacterial effects. The terpene group in modified epoxy resin also has good antibacterial activity. DETAILED DESCRIPTION

[0029] The following will be combined with the embodiments of the present invention to clearly and completely describe the technical solutions in the embodiments of the present invention. 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.

[0030] The preparation of terpene-based epoxy resin refers to the journal "Forest Products Chemistry and Industry" document "Preparation and Solution Properties of Anionic Terpene-Based Epoxy Resin Polyol Aqueous Dispersion", Vol. 33, No. 5, DOI: 10.3969 / j.issn0253-2417.2013.05.001.

[0031] Preparation of epoxy resin-based polyol aqueous dispersion: same as the above document.

[0032] Terpene-based epoxy resin: Epoxy value: 3.2-3.8mmol / g, Shanghai Yuyu New Material Technology Co., Ltd.

[0033] Calcium carbonate: Manufacturer: Southeast New Materials Co., Ltd., particle size 15-60nm.

[0034] The aqueous solution of N,N-dimethylethanolamine was chemically pure.

[0035] The mass fraction of the aqueous solution of formaldehyde is 36%.

[0036] Example 1

[0037] A multifunctional terpene resin composite material, the preparation method of which comprises the following steps:

[0038] (1) Add 1 g of ferrocenylboric acid to 30 mL of toluene solvent, stir and disperse, then add 2.1 g of 4-methyl-5-thiazoleethanol, react at 110° C. for 8 h, and after the reaction is completed, distill under reduced pressure, filter and dry to obtain ferrocenyl modified thiazole;

[0039] (2) Add 0.8 g of ferrocene-modified thiazole and 1.4 g of 3-chloropropylene to 45 mL of N,N-dimethylformamide solvent, stir and disperse, react at 70° C. for 7 h, and then perform vacuum distillation and filtration to obtain olefinated ferrocene-modified thiazole;

[0040] (3) Add 1.5 g of olefinated ferrocene-modified thiazole to 40 mL of N,N-dimethylformamide solvent, stir and disperse, then add 1 g of mercaptoethylamine and 0.01 g of benzoin dimethyl ether photoinitiator, irradiate with 365 nm ultraviolet light at 25 ° C for 3 h, centrifuge, wash and dry to obtain olefinated ferrocene-modified thiazole;

[0041] (4) 1.2 g of aminoferrocene-modified thiazole, 2.2 g of formaldehyde aqueous solution, and 0.9 g of cardanol were added to toluene solvent, fully dissolved, and subjected to cyclization reaction at 75 ° C. for 5 h. After the reaction, the reaction was distilled under reduced pressure, washed, and dried to obtain a boron-modified benzoxazine;

[0042] (5) 0.7 g of terpene-based epoxy resin and 1.22 g of p-aminobenzoic acid were added to a stirrer, and the mixture was stirred and refluxed at 85° C. for 3 h. After the reaction was completed, the solvent was removed by distillation under reduced pressure, and then 0.2 g of N,N-dimethylethanolamine aqueous solution was added for neutralization. After stirring for 15 min, distilled water was added for dispersion and dilution to obtain an epoxy resin-based polyol aqueous dispersion;

[0043] (6) Add 2.15 g of pentaerythritol methyl silicate to 50 mL of N,N-dimethylformamide solvent, stir and disperse, then add 1.23 g of epoxy resin-based polyol aqueous dispersion, react at 95° C. for 10 h, filter after reaction, distill the filtrate under reduced pressure, wash with deionized water, and dry to obtain a modified epoxy resin;

[0044] (7) 35 parts by weight of terpene resin, 6 parts by weight of boron-modified benzoxazine, 4 parts by weight of modified epoxy resin, and 0.6 parts by weight of calcium carbonate are extruded and granulated at 180° C. in a twin-screw extruder, and then the granules are compression molded in a flat vulcanizer at a pressure of 8 MPa and 185° C. to obtain a multifunctional terpene resin composite material.

[0045] Example 2

[0046] A multifunctional terpene resin composite material, the preparation method of which comprises the following steps:

[0047] (1) Add 1.2 g of ferrocene boric acid to 60 mL of toluene solvent, stir and disperse, then add 2.3 g of 4-methyl-5-thiazoleethanol, react at 125° C. for 13 h. After the reaction is completed, vacuum distillation is performed, and the mixture is filtered and dried to obtain ferrocene-modified thiazole;

[0048] (2) Add 1 g of ferrocene-modified thiazole and 1.8 g of 3-chloropropylene to 55 mL of N,N-dimethylformamide solvent, stir and disperse, react at 95° C. for 11 h, and then perform vacuum distillation and filter to obtain olefinated ferrocene-modified thiazole;

[0049] (3) Add 1.84 g of olefinated ferrocene-modified thiazole to 60 mL of N,N-dimethylformamide solvent, stir and disperse, then add 2.1 g of mercaptoethylamine and 0.03 g of benzoin dimethyl ether photoinitiator, irradiate with 365 nm ultraviolet light at 40 ° C for 6 h, centrifuge, wash and dry to obtain olefinated ferrocene-modified thiazole;

[0050] (4) 1.3 g of amino ferrocene modified thiazole, 2.8 g of formaldehyde aqueous solution, and 1.25 g of cardanol were added to toluene solvent, fully dissolved, and cyclized at 95 ° C for 8 h. After the reaction, the reaction was distilled under reduced pressure, washed, and dried to obtain a boron-modified benzoxazine;

[0051] (5) 1.1 g of terpene-based epoxy resin and 1.35 g of p-aminobenzoic acid were added to a stirrer, and the mixture was stirred and refluxed at 95° C. for 5 h. After the reaction was completed, the solvent was removed by distillation under reduced pressure, and then 0.44 g of N,N-dimethylethanolamine aqueous solution was added for neutralization. After stirring for 20 min, distilled water was added for dispersion and dilution to obtain an epoxy resin-based polyol aqueous dispersion;

[0052] (6) Add 2.46 g of pentaerythritol methyl silicate to 65 mL of N,N-dimethylformamide solvent, stir and disperse, then add 1.56 g of epoxy resin-based polyol aqueous dispersion, react at 110° C. for 17 h, filter after completion, distill the filtrate under reduced pressure, wash with deionized water, and dry to obtain a modified epoxy resin;

[0053] (7) 50 parts by weight of terpene resin, 10 parts by weight of boron-modified benzoxazine, 7 parts by weight of modified epoxy resin, and 1 part by weight of calcium carbonate are extruded and granulated in a twin-screw extruder at 190° C., and then the granules are compression molded in a flat vulcanizer at a pressure of 9 MPa and 190° C. to obtain a multifunctional terpene resin composite material.

[0054] Example 3

[0055] A multifunctional terpene resin composite material, the preparation method of which comprises the following steps:

[0056] (1) Add 1.1 g of ferrocene boric acid to 40 mL of toluene solvent, stir and disperse, then add 2.2 g of 4-methyl-5-thiazoleethanol, react at 115° C. for 12 h. After the reaction is completed, vacuum distillation is performed, and the mixture is filtered and dried to obtain ferrocene-modified thiazole;

[0057] (2) Add 0.9 g of ferrocene-modified thiazole and 1.6 g of 3-chloropropylene to 50 mL of N,N-dimethylformamide solvent, stir and disperse, react at 85° C. for 10 h, and then perform vacuum distillation and filtration to obtain olefinated ferrocene-modified thiazole;

[0058] (3) Add 1.64 g of olefinated ferrocene-modified thiazole to 50 mL of N,N-dimethylformamide solvent, stir and disperse, then add 1.8 g of mercaptoethylamine and 0.02 g of benzoin dimethyl ether photoinitiator, irradiate with 365 nm ultraviolet light at 35° C. for 5 h, centrifuge, wash and dry to obtain olefinated ferrocene-modified thiazole;

[0059] (4) 1.2 g of aminoferrocene-modified thiazole, 2.5 g of formaldehyde aqueous solution, and 1.21 g of cardanol were added to toluene solvent, fully dissolved, and subjected to cyclization reaction at 85 ° C. for 7 h. After completion, the reaction was distilled under reduced pressure, washed, and dried to obtain boron-modified benzoxazine;

[0060] (5) 0.9 g of terpene-based epoxy resin and 1.26 g of p-aminobenzoic acid were added to a stirrer, and the mixture was stirred and refluxed at 90° C. for 4 h. After the reaction was completed, the solvent was removed by distillation under reduced pressure, and then 0.32 g of N,N-dimethylethanolamine aqueous solution was added for neutralization. After stirring for 18 min, distilled water was added for dispersion and dilution to obtain an epoxy resin-based polyol aqueous dispersion;

[0061] (6) Add 2.37 g of pentaerythritol methyl silicate to 60 mL of N,N-dimethylformamide solvent, stir and disperse, then add 1.28 g of epoxy resin-based polyol aqueous dispersion, react at 100° C. for 16 h, filter after reaction, distill the filtrate under reduced pressure, wash with deionized water, and dry to obtain a modified epoxy resin;

[0062] (7) 32 parts by weight of terpene resin, 8 parts by weight of boron-modified benzoxazine, 5 parts by weight of modified epoxy resin, and 0.8 parts by weight of calcium carbonate are extruded and granulated at 185° C. in a twin-screw extruder, and the granules are then compression molded in a flat vulcanizer at a pressure of 8 MPa and 187° C. to obtain a multifunctional terpene resin composite material.

[0063] Example 4

[0064] A multifunctional terpene resin composite material, the preparation method of which comprises the following steps:

[0065] (1) Add 1 g of ferrocenylboric acid to 30 mL of toluene solvent, stir and disperse, then add 2.1 g of 4-methyl-5-thiazoleethanol, react at 110° C. for 8 h, and after the reaction is completed, distill under reduced pressure, filter and dry to obtain ferrocenyl modified thiazole;

[0066] (2) Add 0.8 g of ferrocene-modified thiazole and 1.4 g of 3-chloropropylene to 45 mL of N,N-dimethylformamide solvent, stir and disperse, react at 70° C. for 7 h, and then perform vacuum distillation and filtration to obtain olefinated ferrocene-modified thiazole;

[0067] (3) Add 1.84 g of olefinated ferrocene-modified thiazole to 60 mL of N,N-dimethylformamide solvent, stir and disperse, then add 2.1 g of mercaptoethylamine and 0.03 g of benzoin dimethyl ether photoinitiator, irradiate with 365 nm ultraviolet light at 40 ° C for 6 h, centrifuge, wash and dry to obtain olefinated ferrocene-modified thiazole;

[0068] (4) 1.3 g of amino ferrocene modified thiazole, 2.8 g of formaldehyde aqueous solution, and 1.25 g of cardanol were added to toluene solvent, fully dissolved, and cyclized at 95 ° C for 8 h. After the reaction, the reaction was distilled under reduced pressure, washed, and dried to obtain a boron-modified benzoxazine;

[0069] (5) 0.9 g of terpene-based epoxy resin and 1.26 g of p-aminobenzoic acid were added to a stirrer, and the mixture was stirred and refluxed at 90° C. for 4 h. After the reaction was completed, the solvent was removed by distillation under reduced pressure, and then 0.32 g of N,N-dimethylethanolamine aqueous solution was added for neutralization. After stirring for 18 min, distilled water was added for dispersion and dilution to obtain an epoxy resin-based polyol aqueous dispersion;

[0070] (6) Add 2.37 g of pentaerythritol methyl silicate to 60 mL of N,N-dimethylformamide solvent, stir and disperse, then add 1.28 g of epoxy resin-based polyol aqueous dispersion, react at 100° C. for 16 h, filter after reaction, distill the filtrate under reduced pressure, wash with deionized water, and dry to obtain a modified epoxy resin;

[0071] (7) 32 parts by weight of terpene resin, 8 parts by weight of boron-modified benzoxazine, 5 parts by weight of modified epoxy resin, and 0.8 parts by weight of calcium carbonate are extruded and granulated at 185° C. in a twin-screw extruder, and the granules are then compression molded in a flat vulcanizer at a pressure of 8 MPa and 187° C. to obtain a multifunctional terpene resin composite material.

[0072] Example 5

[0073] A multifunctional terpene resin composite material, the preparation method of which comprises the following steps:

[0074] (1) Add 1.2 g of ferrocene boric acid to 60 mL of toluene solvent, stir and disperse, then add 2.3 g of 4-methyl-5-thiazoleethanol, react at 125° C. for 13 h. After the reaction is completed, vacuum distillation is performed, and the mixture is filtered and dried to obtain ferrocene-modified thiazole;

[0075] (2) Add 1 g of ferrocene-modified thiazole and 1.8 g of 3-chloropropylene to 55 mL of N,N-dimethylformamide solvent, stir and disperse, react at 95° C. for 11 h, and then perform vacuum distillation and filter to obtain olefinated ferrocene-modified thiazole;

[0076] (3) Add 1.64 g of olefinated ferrocene-modified thiazole to 50 mL of N,N-dimethylformamide solvent, stir and disperse, then add 1.8 g of mercaptoethylamine and 0.02 g of benzoin dimethyl ether photoinitiator, irradiate with 365 nm ultraviolet light at 35° C. for 5 h, centrifuge, wash and dry to obtain olefinated ferrocene-modified thiazole;

[0077] (4) 1.2 g of aminoferrocene-modified thiazole, 2.5 g of formaldehyde aqueous solution, and 1.21 g of cardanol were added to toluene solvent, fully dissolved, and subjected to cyclization reaction at 85 ° C. for 7 h. After completion, the reaction was distilled under reduced pressure, washed, and dried to obtain boron-modified benzoxazine;

[0078] (5) 0.7 g of terpene-based epoxy resin and 1.22 g of p-aminobenzoic acid were added to a stirrer, and the mixture was stirred and refluxed at 85° C. for 3 h. After the reaction was completed, the solvent was removed by distillation under reduced pressure, and then 0.2 g of N,N-dimethylethanolamine aqueous solution was added for neutralization. After stirring for 15 min, distilled water was added for dispersion and dilution to obtain an epoxy resin-based polyol aqueous dispersion;

[0079] (6) Add 2.15 g of pentaerythritol methyl silicate to 50 mL of N,N-dimethylformamide solvent, stir and disperse, then add 1.23 g of epoxy resin-based polyol aqueous dispersion, react at 95° C. for 10 h, filter after reaction, distill the filtrate under reduced pressure, wash with deionized water, and dry to obtain a modified epoxy resin;

[0080] (7) 35 parts by weight of terpene resin, 6 parts by weight of boron-modified benzoxazine, 4 parts by weight of modified epoxy resin, and 0.6 parts by weight of calcium carbonate are extruded and granulated at 180° C. in a twin-screw extruder, and then the granules are compression molded in a flat vulcanizer at a pressure of 8 MPa and 185° C. to obtain a multifunctional terpene resin composite material.

[0081] Comparative Example 1

[0082] Compared with Example 5, this comparative example is different in that benzoxazine is used instead of boron-modified benzoxazine.

[0083] Comparative Example 2

[0084] Compared with Example 5, this comparative example differs in that an epoxy resin-based polyol aqueous dispersion is used instead of the modified epoxy resin.

[0085] The concentration is 2×10 8 CFU / mL of Staphylococcus aureus liquid was added to a sterilized culture dish as the test strain, and then solid agar medium was added and dissolved, cooled to 45°C, and then poured into the culture dish, 20mL was poured into each plate with an inner diameter of 10cm, and then the antibacterial materials of the embodiments of the present invention and the comparative example (with a diameter of 3cm and a thickness of 1mm) were placed on the culture plate, and cultured in a constant temperature incubator for 12h at a temperature of 37°C. After culture, the diameter of the inhibition zone was measured. The test results are shown in Table 1.

[0086] Table 1: Antimicrobial testing.

[0087] project Diameter of inhibition zone (mm) Example 1 15.4 Example 2 16.7 Example 3 16.4 Example 4 16.3 Example 5 15.9 Comparative Example 1 11.3 Comparative Example 2 11.8

[0088] It can be seen from Table 1 that the multifunctional terpene resin composite material Examples 1-5 of the present invention have better antibacterial effects than Comparative Examples 1-2.

[0089] Use an oxygen index meter to test the limiting oxygen index of the material; use a horizontal and vertical combustion instrument to test the combustion level of the material.

[0090] Table 2: Flame retardancy test.

[0091] project Limiting oxygen index (%) Combustion level Example 1 30 V-0 Example 2 32 V-0 Example 3 32 V-0 Example 4 31 V-0 Example 5 30 V-0 Comparative Example 1 20 V-1 Comparative Example 2 21 V-1

[0092] It can be seen from Table 2 that the flame retardant effect of Examples 1-5 is better than that of Comparative Examples 1-2, which indicates that the multifunctional terpene resin composite material prepared by the present invention has a good flame retardant effect.

[0093] In the description of the specification, the description with reference to the terms "one embodiment", "example", "specific example", etc. means that the specific features, structures, materials or characteristics described in conjunction with the embodiment or example are included in at least one embodiment or example of the present invention. In this specification, the schematic representation of the above terms does not necessarily refer to the same embodiment or example. Moreover, the specific features, structures, materials or characteristics described can be combined in any one or more embodiments or examples in a suitable manner.

[0094] The above contents are merely examples and explanations of the present invention. Those skilled in the art may make various modifications or additions to the specific embodiments described or replace them in a similar manner. As long as they do not deviate from the invention or exceed the scope defined by the claims, they shall all fall within the protection scope of the present invention.

Claims

1. A multifunctional terpene resin composite material, characterized in that: The invention comprises the following components by weight: 35-50 parts by weight of terpene resin, 6-10 parts by weight of boron-modified benzoxazine, 4-7 parts by weight of modified epoxy resin, and 0.6-1 parts by weight of calcium carbonate; The preparation method of the boron-modified benzoxazine is as follows: (1) adding ferrocene boric acid to toluene solvent, stirring and dispersing, and then adding 4-methyl-5-thiazoleethanol thereto, reacting at 110-125° C. for 8-13 hours. After the reaction is completed, distilling under reduced pressure, filtering and drying to obtain ferrocene-modified thiazole; (2) adding ferrocene-modified thiazole and 3-chloropropylene to N,N-dimethylformamide solvent, stirring and dispersing, reacting at 70-95° C. for 7-11 hours, and then performing reduced pressure distillation after the reaction, filtering, and obtaining olefinated ferrocene-modified thiazole; (3) adding olefinated ferrocene-modified thiazole to N,N-dimethylformamide solvent, stirring and dispersing, adding mercaptoethylamine and benzoin dimethyl ether photoinitiators, irradiating with ultraviolet light at 25-40° C. for 3-6 hours, centrifuging after the end, washing and drying to obtain olefinated ferrocene-modified thiazole; (4) Adding the amino ferrocene modified thiazole, the aqueous solution of formaldehyde, and cardanol into toluene solvent, fully dissolving them, and carrying out a cyclization reaction at 75-95° C. for 5-8 hours. After the reaction, distilling under reduced pressure, washing, and drying are performed to obtain a boron-modified benzoxazine.

2. The multifunctional terpene resin composite material according to claim 1, characterized in that: The mass ratio of ferrocenylboric acid to 4-methyl-5-thiazoleethanol in (1) is (1-1.2):(2.1-2.3).

3. The multifunctional terpene resin composite material according to claim 1, characterized in that: The mass ratio of ferrocene-modified thiazole and 3-chloropropylene in (2) is (0.8-1):(1.4-1.8).

4. The multifunctional terpene resin composite material according to claim 1, characterized in that: The mass ratio of olefinated ferrocene-modified thiazole, mercaptoethylamine, and benzoin dimethyl ether photoinitiator in (3) is (1.5-1.84):(1-2.1):(0.01-0.03).

5. The multifunctional terpene resin composite material according to claim 1, characterized in that: The mass ratio of the aminoferrocene-modified thiazole, the formaldehyde aqueous solution, and the cardanol in (4) is (1.2-1.3):(2.2-2.8):(0.9-1.25).

6. The multifunctional terpene resin composite material according to claim 1, characterized in that: The preparation method of the modified epoxy resin is: S1. Add terpene-based epoxy resin and p-aminobenzoic acid into a stirrer, stir and reflux at 85-95°C for 3-5h, and after the reaction, remove the solvent by distillation under reduced pressure, then add N,N-dimethylethanolamine aqueous solution for neutralization, stir for 15-20min, and then add distilled water for dispersion and dilution to obtain an epoxy resin-based polyol aqueous dispersion; S2. Add pentaerythritol methyl silicate to N,N-dimethylformamide solvent, stir and disperse, then add epoxy resin-based polyol aqueous dispersion thereto, react at 95-110°C for 10-17h, filter after reaction, distill the filtrate under reduced pressure, wash with deionized water, and dry to obtain modified epoxy resin.

7. The multifunctional terpene resin composite material according to claim 6, characterized in that: The mass ratio of terpene epoxy resin, p-aminobenzoic acid and N,N-dimethylethanolamine aqueous solution in S1 is (0.7-1.1):(1.22-1.35):(0.2-0.44).

8. The multifunctional terpene resin composite material according to claim 6, characterized in that: The mass ratio of pentaerythritol methyl silicate to epoxy resin-based polyol aqueous dispersion in S2 is (2.15-2.46):(1.23-1.56).

9. A method for preparing a multifunctional terpene resin composite material according to any one of claims 1 to 8, characterized in that: The preparation method of the multifunctional terpene resin composite material is as follows: terpene resin, boron-modified benzoxazine, modified epoxy resin and calcium carbonate are extruded and granulated at 180-190° C. in a twin-screw extruder, and then the granules are compression molded in a flat vulcanizer at a pressure of 8-9 MPa and a temperature of 185-190° C. to obtain the multifunctional terpene resin composite material.

10. An application of a multifunctional terpene resin composite material, characterized in that: The application of the multifunctional terpene resin composite material in the field of high-end coatings.