A poly(methyl methacrylate)-containing composite material and a method for producing the same

Abstract

The application relates to the technical field of high polymer composite materials, and discloses a poly(methyl methacrylate)-containing composite material and a preparation method thereof, the preparation method being as follows: poly(methyl methacrylate), modified carbon nanotubes, modified imidazole, zinc stearate and antioxidant 1010 are placed in a high-speed mixer, melt blending is carried out for 20-30 minutes, the melt blending temperature is 175-185 DEG C, then extrusion granulation is carried out in a double-screw extruder, and the poly(methyl methacrylate)-containing composite material is obtained. The composite material has good mechanical properties, flame-retardant properties and antibacterial properties.

Description

TECHNICAL FIELD

[0001] The present application relates to the technical field of high polymer composite materials, in particular to a composite material containing polymethyl methacrylate and a preparation method thereof. BACKGROUND

[0002] Polymethyl methacrylate, commonly known as organic glass, is a thermoplastic polymer with excellent transparency, high gloss, strong weather resistance and easy processing, which is widely used in optical lenses, lighting fixtures, building boards, automobile tail lights and other fields. However, pure polymethyl methacrylate has low tensile strength and poor impact toughness, and is prone to brittle fracture due to stress concentration, which limits its application in load-bearing structural parts, and also has the problem of insufficient functionality. Therefore, how to avoid this phenomenon is the key to solving the problem. For example, the patent with publication number CN120248534A discloses a polymethyl methacrylate composite material and a preparation method and application thereof. The polymethyl methacrylate composite material has high wear resistance, high toughness and is not easy to absorb moisture and stick on the surface, but the flame retardant performance and antibacterial performance need to be improved. SUMMARY

[0003] (I) Technical problems to be solved

[0004] In view of the deficiencies of the prior art, the present application provides a composite material containing polymethyl methacrylate and a preparation method thereof. The composite material of the present application has good mechanical properties, flame retardant performance and antibacterial performance.

[0005] (II) Technical solutions

[0006] To achieve the above-mentioned purpose, the present application provides the following technical solutions: a composite material containing polymethyl methacrylate, characterized in that it comprises the following weight components: 70-85 parts by weight of polymethyl methacrylate, 1-1.5 parts by weight of modified carbon nanotubes, 1-2 parts by weight of modified imidazole, 0.5-0.8 parts by weight of zinc stearate, and 0.2-0.3 parts by weight of antioxidant 1010.

[0007] Further, the preparation method of the modified carbon nanotubes is as follows:

[0008] Step one: add cardanol, triethylamine and melamine to chloroform solvent, stir and reflux, cool to 0-5℃, react for 3-5h, then warm to 80-90℃ and continue to react for 2-4h, after the reaction is completed, cool to room temperature naturally, filter, remove the solvent by rotary evaporation, wash with deionized water and dry to obtain tri-(3-pentadecenyl phenoxy) triazine;

[0009] Step two: add tri-(3-pentadecenylphenoxy) triazine, 3-chloro peroxybenzoic acid into tetrahydrofuran solvent, react for 4-6h under ice water bath, after the reaction is completed, filter, wash the filtrate with 10% sodium carbonate solution, remove the solvent by rotary evaporation, dry to obtain epoxidized tri-(3-pentadecenylphenoxy) triazine;

[0010] Step three: first, put 0.1-0.2g of hydroxyl carbon nanotubes into a digestion tube, add 25-28mL of N,N-dimethylformamide, ultrasonic treat for 30-60min to disperse, to obtain a suspension, then add 8.02-8.06g of hexamethylene diisocyanate, 15-20mL of N,N-dimethylformamide into the reactor, stir uniformly, heat to 50-60℃, then slowly drop the suspension into the reactor, add 0.13-0.17g of dibutyltin dilaurate catalyst, keep 50-60℃, stir for 8-10h, after the reaction is completed, centrifuge, wash, dry at 45-55℃ under vacuum for 4-6h, to obtain isocyanate functionalized carbon nanotubes;

[0011] Step four: under nitrogen gas protection, add isocyanate functionalized carbon nanotubes into N,N-dimethylformamide solvent, ultrasonic treat for 30-40min, then add epoxidized tri-(3-pentadecenylphenoxy) triazine, tetramethylammonium chloride catalyst, stir and mix, react at 140-150℃ for 8-12h, after the reaction is completed, centrifuge, wash and dry, to obtain modified carbon nanotubes.

[0012] Further, the amount ratio of chloroform, cardanol, triethylamine, melamine in step one is 15-20mL:7.08-7.12g:4.04-4.08g:1.84-1.88g.

[0013] Further, the amount ratio of tetrahydrofuran, tri-(3-pentadecenylphenoxy) triazine, 3-chloro peroxybenzoic acid in step two is 10-12mL:3.68-3.72g:3.45-3.5g.

[0014] Further, the amount ratio of N,N-dimethylformamide, isocyanate functionalized carbon nanotubes, epoxidized tri-(3-pentadecenylphenoxy) triazine, tetramethylammonium chloride in step four is 50-60mL:1.2-1.5mmol:0.6-0.8mmol:0.01-0.02mmol.

[0015] Further, the preparation method of the modified imidazole is:

[0016] S1: adding acetone, 4-hydroxyethyl imidazole and 2,2-bis(bromomethyl)-1,3-propanediol into a reactor, stirring and mixing, then adding dropwise a sodium hydroxide aqueous solution with a molar concentration of 2-6 mol / L, stirring and reacting at 50-70 DEG C for 5-8 h, after the reaction is completed, neutralizing by adding dropwise 5% dilute hydrochloric acid, removing acetone by concentration, pumping the remaining aqueous solution, washing the precipitate with water, and drying to obtain intermediate 1;

[0017] S2: adding intermediate 1, fumaric acid, p-toluenesulfonic acid into a reactor, mixing uniformly, then adding cyclohexane as a water-carrying agent, stirring and refluxing at 160-180 DEG C for 2-4 h, after the reaction is completed, removing cyclohexane by distillation under reduced pressure, washing and drying to obtain modified imidazole.

[0018] Further, in S1, the amount ratio of acetone, 4-hydroxyethyl imidazole and 2,2-bis(bromomethyl)-1,3-propanediol is 35-40 mL: 35-45 mmol: 15-18 mmol.

[0019] Further, in S2, the amount ratio of intermediate 1, fumaric acid, p-toluenesulfonic acid and cyclohexane is 10-12 mmol: 4-6 mmol: 0.01-0.02 g: 12-15 mL.

[0020] Further, the preparation method of the poly(methyl methacrylate)-containing composite material is as follows: poly(methyl methacrylate), modified carbon nanotubes, modified imidazole, zinc stearate and antioxidant 1010 are placed in a high-speed mixer, melt blended for 20-30 min, the melt blending temperature is 175-185 DEG C, then extruded and granulated in a twin-screw extruder to obtain the poly(methyl methacrylate)-containing composite material.

[0021] (Three) Beneficial technical effects

[0022] The poly(methyl methacrylate)-containing composite material is obtained by placing poly(methyl methacrylate), modified carbon nanotubes, modified imidazole, zinc stearate and antioxidant 1010 in a high-speed mixer, melt blending, then extruding and granulating in a twin-screw extruder.

[0023] The cashew phenol is reacted with melamine to obtain tri-(3-pentadecenyl phenoxy) triazine. The molecular structure of cashew phenol includes rigid benzene ring and carbon chain containing unsaturated double bond, which can increase the toughness of the composite material, improve the mechanical properties, and the nitrogen element in the triazine group releases non-combustible gas after thermal decomposition, dilutes the concentration of combustible gas and reduces the surface temperature of the material, thereby improving the flame retardant properties of the composite material. The subsequent introduction of epoxy group and ring-opening reaction of the epoxy group with hexamethylene diisocyanate enable the tri-(3-pentadecenyl phenoxy) triazine to be grafted onto the hydroxyl carbon nanotube. The carbon nanotube has extremely high specific surface area and excellent mechanical properties, which can hinder the diffusion of heat and combustible volatile substances, and can be used in the composite material to significantly enhance the strength, stiffness and flame retardant properties of the material. The imidazole group of 4-hydroxyethyl imidazole can inhibit the synthesis of key components of the fungal cell membrane, leading to increased membrane permeability and content leakage, thereby achieving antibacterial effect. The subsequent esterification reaction with fumaric acid can effectively permeabilize the outer cell membrane, increase the osmotic pressure of the cell membrane and inhibit biosynthesis, thereby achieving antibacterial effect and enhancing the antibacterial properties of the composite material. The carbon long chain of the modified carbon nanotube cashew phenol can be intertwined and crosslinked with polymethyl methacrylate and modified imidazole, forming a molecular crosslinking network, thereby further enhancing the mechanical properties of the composite material. BRIEF DESCRIPTION OF DRAWINGS

[0024] Figure 1 The synthesis route of tri-(3-pentadecenyl phenoxy) triazine in the embodiment 1 of the present application is shown in the following figure. DETAILED DESCRIPTION

[0025] In order to make the purpose, technical scheme and advantages of the embodiments of the present application more clear, the technical scheme of the embodiments of the present application is described clearly and completely. Obviously, the described embodiments are part of the embodiments of the present application, not all the embodiments. Based on the embodiments in the present application, all other embodiments obtained by those skilled in the art without creative labor are within the scope of protection of the present application.

[0026] In order to better understand the above technical scheme, the above technical scheme will be described in detail in combination with the drawings and specific embodiments in the specification.

[0027] The reagents used in the following specific embodiments are analytical pure, and the other reagents are commercially available or synthesized according to the known method.

[0028] Polymethyl methacrylate: melt mass flow rate is 2 g / 10 min, manufacturer is Suzhou Shuangxiang, model PPMASX-304;

[0029] Hydroxyl carbon nanotube: tube diameter is less than 8 nm, length is 10 μm, purity is > 95%, manufacturer is Beijing Dekedaojin Technology Co., Ltd.

[0030] Embodiment 1

[0031] (1) 7.08 g of cardanol, 4.04 g of triethylamine, 1.84 g of melamine were added into 15 mL of chloroform solvent, stirred and refluxed, reacted for 3 h at 0 ℃, then warmed to 80 ℃ and continued to react for 2 h, after the reaction was completed, naturally cooled to room temperature, filtered, rotary evaporated to remove the solvent, washed with deionized water, and dried to obtain tri-(3-pentadecenylphenoxy) triazine; as shown in Figure 1 ;

[0032] (2) 3.68 g of tri-(3-pentadecenylphenoxy) triazine, 3.45 g of 3-chloroperbenzoic acid were added into 10 mL of tetrahydrofuran solvent, reacted for 4 h under ice water bath, after the reaction was completed, filtered, the filtrate was washed with 10% sodium carbonate solution, rotary evaporated to remove the solvent, and dried to obtain epoxidized tri-(3-pentadecenylphenoxy) triazine;

[0033] (3) 0.1 g of hydroxyl carbon nanotube was first loaded into a digestion tube, 25 mL of N,N-dimethylformamide was added, ultrasonic treatment was performed for 30 min to disperse, to obtain a suspension, then 8.02 g of hexamethylene diisocyanate, 15 mL of N,N-dimethylformamide was added into the reactor, stirred uniformly, heated to 50 ℃, then the suspension was slowly added dropwise into the reactor, 0.13 g of dibutyltin dilaurate catalyst was added, kept stirring at 50 ℃ for 8 h, after the reaction was completed, centrifuged, washed, and vacuum dried at 45 ℃ for 4 h to obtain isocyanate functionalized carbon nanotube;

[0034] (4) 1.2 mmol of isocyanate functionalized carbon nanotube was added into 50 mL of N,N-dimethylformamide solvent under nitrogen gas protection, ultrasonic treatment was performed for 30 min, then 0.6 mmol of epoxidized tri-(3-pentadecenylphenoxy) triazine, 0.01 mmol of tetramethylammonium chloride catalyst was added, stirred and mixed, reacted for 8 h at 140 ℃, after the reaction was completed, centrifuged, washed and dried to obtain modified carbon nanotube;

[0035] (5) 35 mL of acetone, 35 mmol of 4-hydroxyethyl imidazole and 15 mmol of 2,2-bis(bromomethyl)-1,3-propanediol were added into a reactor, stirred and mixed, then 3 mL of 2 mol / L sodium hydroxide aqueous solution was added dropwise, stirred and reacted for 5 h at 50 ℃, after the reaction was completed, neutralized by adding 5% dilute hydrochloric acid, concentrated to remove acetone, the remaining aqueous solution was suction filtered, the precipitate was washed with water, and dried to obtain intermediate 1;

[0036] (6) 10 mmol of intermediate 1, 4 mmol of fumaric acid, 0.01 g of p-toluenesulfonic acid were added into a reactor, mixed uniformly, then 12 mL of cyclohexane was added as a water-carrying agent, stirred at 160°C under reflux for 2 h, after the reaction was completed, the cyclohexane was removed by distillation under reduced pressure, washed and dried to obtain a modified imidazole;

[0037] (7) 70 parts by weight of polymethyl methacrylate, 1 part by weight of modified carbon nanotubes, 1 part by weight of modified imidazole, 0.5 parts by weight of zinc stearate, and 0.2 parts by weight of antioxidant 1010 were placed in a high-speed mixer, melt blended for 20 min, the melt blending temperature was 175°C, then extruded and granulated in a twin-screw extruder to obtain a composite material containing polymethyl methacrylate.

[0038] Example 2

[0039] (1) 7.12 g of cardanol, 4.08 g of triethylamine, and 1.88 g of melamine were added into 20 mL of chloroform solvent, stirred and refluxed, reacted at 5°C for 5 h, then the temperature was increased to 90°C and the reaction was continued for 4 h, after the reaction was completed, the temperature was naturally cooled to room temperature, filtered, rotary evaporated to remove the solvent, washed with deionized water, and dried to obtain tri-(3-pentadecenylphenoxy) triazine;

[0040] (2) 3.72 g of tri-(3-pentadecenylphenoxy) triazine and 3.5 g of 3-chloroperbenzoic acid were added into 12 mL of tetrahydrofuran solvent, reacted under ice water bath for 6 h, after the reaction was completed, filtered, the filtrate was washed with 10% sodium carbonate solution, rotary evaporated to remove the solvent, and dried to obtain epoxidized tri-(3-pentadecenylphenoxy) triazine;

[0041] (3) 0.2 g of hydroxyl carbon nanotubes was first loaded into a digestion tube, 28 mL of N,N-dimethylformamide was added, ultrasonic treatment was performed for 60 min to disperse, a suspension was obtained, then 8.06 g of hexamethylene diisocyanate and 20 mL of N,N-dimethylformamide were added into the reactor, stirred uniformly, heated to 60°C, then the suspension was slowly added into the reactor, 0.17 g of dibutyltin dilaurate catalyst was added, and the stirring reaction was maintained at 60°C for 10 h, after the reaction was completed, centrifuged, washed, and vacuum dried at 55°C for 6 h to obtain isocyanate functionalized carbon nanotubes;

[0042] (4) Under the protection of nitrogen gas, 1.5 mmol of isocyanate functionalized carbon nanotubes was added into 60 mL of N,N-dimethylformamide solvent, and ultrasonic treatment was performed for 40 min, then 0.8 mmol of epoxidized tris-(3-pentadecenylphenoxy) triazine, 0.02 mmol of tetramethylammonium chloride catalyst were added, the mixture was stirred and reacted at 150℃ for 12 h, after the reaction was completed, centrifugation, washing and drying were performed to obtain modified carbon nanotubes;

[0043] (5) 40 mL of acetone, 45 mmol of 4-hydroxyethyl imidazole and 18 mmol of 2,2-bis(bromomethyl)-1,3-propanediol were added into a reactor, the mixture was stirred and mixed, then 4 mL of 6 mol / L sodium hydroxide aqueous solution was added dropwise, the mixture was stirred and reacted at 70℃ for 8 h, after the reaction was completed, neutralization was performed by dropwise adding 5% dilute hydrochloric acid, acetone was removed by concentration, the remaining aqueous solution was suction filtered, the precipitate was washed with water and dried to obtain intermediate 1;

[0044] (6) 12 mmol of intermediate 1, 6 mmol of fumaric acid and 0.02 g of p-toluenesulfonic acid were added into a reactor, mixed uniformly, then 15 mL of cyclohexane was added as a water-carrying agent, the mixture was stirred and refluxed at 180℃ for 4 h, after the reaction was completed, cyclohexane was removed by distillation under reduced pressure, and the mixture was washed and dried to obtain modified imidazole;

[0045] (7) 85 parts by weight of polymethyl methacrylate, 1.5 parts by weight of modified carbon nanotubes, 2 parts by weight of modified imidazole, 0.8 parts by weight of zinc stearate and 0.3 parts by weight of antioxidant 1010 were placed in a high-speed mixer, melt blended for 30 min, the melt blending temperature was 185℃, then extrusion granulation was performed in a twin-screw extruder to obtain a composite material containing polymethyl methacrylate.

[0046] Example 3

[0047] (1) 7.1 g of cardanol, 4.06 g of triethylamine and 1.86 g of melamine were added into 18 mL of chloroform solvent, stirred and refluxed, the mixture was reacted at 2℃ for 4 h, then the temperature was increased to 85℃ and the reaction was continued for 3 h, after the reaction was completed, the mixture was naturally cooled to room temperature, filtered, the solvent was removed by rotary evaporation, washed with deionized water and dried to obtain tris-(3-pentadecenylphenoxy) triazine;

[0048] (2) 3.7 g of tris-(3-pentadecenylphenoxy) triazine and 3.48 g of 3-chloroperbenzoic acid were added into 11 mL of tetrahydrofuran solvent, and the mixture was reacted under ice water bath for 5 h, after the reaction was completed, the mixture was filtered, the filtrate was washed with 10% sodium carbonate solution, the solvent was removed by rotary evaporation, and the mixture was dried to obtain epoxidized tris-(3-pentadecenylphenoxy) triazine;

[0049] (3) 0.15 g of hydroxyl carbon nanotubes was first loaded into a digestion tube, 26 mL of N,N-dimethylformamide was added, and ultrasonic treatment was performed for 45 min to disperse it, to obtain a suspension, then 8.04 g of hexamethylene diisocyanate, 18 mL of N,N-dimethylformamide was added to the reactor, and stirring was performed until uniform, and heating was performed to 55°C, then the suspension was slowly added dropwise to the reactor, 0.15 g of dibutyltin dilaurate catalyst was added, and stirring was performed at 55°C for 9 h, after the reaction was completed, centrifugation, washing, and vacuum drying at 50°C for 5 h were performed, to obtain isocyanate functionalized carbon nanotubes;

[0050] (4) Under nitrogen gas protection, 1.3 mmol of isocyanate functionalized carbon nanotubes was added to 55 mL of N,N-dimethylformamide solvent, ultrasonic treatment was performed for 35 min, then 0.7 mmol of epoxidized tris-(3-pentadecenylphenoxy) triazine, 0.01 mmol of tetramethylammonium chloride catalyst was added, stirring was performed for mixing, and reaction was performed at 145°C for 10 h, after the reaction was completed, centrifugation, washing, and drying were performed, to obtain modified carbon nanotubes;

[0051] (5) 38 mL of acetone, 40 mmol of 4-hydroxyethyl imidazole, and 16 mmol of 2,2-bis(bromomethyl)-1,3-propanediol were added to a reactor, stirring was performed for mixing, then 3 mL of a 4 mol / L molar concentration sodium hydroxide aqueous solution was added dropwise, stirring was performed at 60°C for 6 h, after the reaction was completed, neutralization was performed by dropwise addition of 5% by mass dilute hydrochloric acid, acetone was removed by concentration, the remaining aqueous solution was suction filtered, the precipitate was washed with water, and drying was performed, to obtain intermediate 1;

[0052] (6) 11 mmol of intermediate 1, 5 mmol of fumaric acid, and 0.01 g of p-toluenesulfonic acid were added to a reactor, uniform mixing was performed, then 13 mL of cyclohexane was added as a water-carrying agent, stirring was performed at 170°C for 3 h, after the reaction was completed, cyclohexane was removed by distillation under reduced pressure, and washing and drying were performed, to obtain modified imidazole;

[0053] (7) 77 parts by weight of polymethyl methacrylate, 1.2 parts by weight of modified carbon nanotubes, 1.5 parts by weight of modified imidazole, 0.6 parts by weight of zinc stearate, and 0.2 parts by weight of antioxidant 1010 were placed in a high-speed mixer, melt blending was performed for 25 min, the melt blending temperature was 180°C, then melt extrusion granulation was performed in a twin-screw extruder, to obtain a polymethyl methacrylate-containing composite material.

[0054] Example 4

[0055] (1) 7.09 g of cardanol, 4.05 g of triethylamine, 1.85 g of melamine were added into 16 mL of chloroform solvent, stirred and refluxed, reacted for 3 h at 1 ℃, then warmed up to 82 ℃ and continued to react for 2 h, after the reaction was completed, naturally cooled to room temperature, filtered, rotary evaporated to remove the solvent, washed with deionized water, and dried to obtain tri-(3-pentadecenylphenoxy) triazine;

[0056] (2) 3.69 g of tri-(3-pentadecenylphenoxy) triazine, 3.46 g of 3-chloroperbenzoic acid were added into 10 mL of tetrahydrofuran solvent, reacted for 4 h under ice water bath, after the reaction was completed, filtered, the filtrate was washed with 10% by mass sodium carbonate solution, rotary evaporated to remove the solvent, and dried to obtain epoxidized tri-(3-pentadecenylphenoxy) triazine;

[0057] (3) 0.12 g of hydroxyl carbon nanotube was first loaded into a digestion tube, 26 mL of N,N-dimethylformamide was added, ultrasonic treatment was performed for 35 min to disperse, to obtain a suspension, then 8.03 g of hexamethylene diisocyanate, 16 mL of N,N-dimethylformamide was added into the reactor, stirred uniformly, heated to 52 ℃, then the suspension was slowly added dropwise into the reactor, 0.14 g of dibutyltin dilaurate catalyst was added, kept stirring at 52 ℃ for 8 h, after the reaction was completed, centrifuged, washed, and vacuum dried at 48 ℃ for 4 h to obtain isocyanate functionalized carbon nanotube;

[0058] (4) 1.3 mmol of isocyanate functionalized carbon nanotube was added into 52 mL of N,N-dimethylformamide solvent under nitrogen gas protection, ultrasonic treatment was performed for 32 min, then 0.6 mmol of epoxidized tri-(3-pentadecenylphenoxy) triazine, 0.01 mmol of tetramethylammonium chloride catalyst was added, stirred and mixed, reacted for 9 h at 142 ℃, after the reaction was completed, centrifuged, washed and dried to obtain modified carbon nanotube;

[0059] (5) 36 mL of acetone, 38 mmol of 4-hydroxyethyl imidazole and 16 mmol of 2,2-bis(bromomethyl)-1,3-propanediol were added into a reactor, stirred and mixed, then 3 mL of 3 mol / L sodium hydroxide aqueous solution was added dropwise, stirred and reacted for 6 h at 55 ℃, after the reaction was completed, neutralized by adding 5% by mass dilute hydrochloric acid dropwise, concentrated to remove acetone, the remaining aqueous solution was suction filtered, the precipitate was washed with water, and dried to obtain intermediate 1;

[0060] (6) 10 mmol of intermediate 1, 5 mmol of fumaric acid, 0.01 g of p-toluenesulfonic acid were added into a reactor, mixed uniformly, then 13 mL of cyclohexane was added as a water-carrying agent, stirred at 165℃ under reflux for 2 h, after the reaction was completed, the cyclohexane was removed by distillation under reduced pressure, washed and dried to obtain a modified imidazole;

[0061] (7) 74 parts by weight of polymethyl methacrylate, 1 part by weight of modified carbon nanotubes, 1.2 parts by weight of modified imidazole, 0.6 parts by weight of zinc stearate, and 0.2 parts by weight of antioxidant 1010 were placed in a high-speed mixer, melt blended for 22 min at a melt blending temperature of 178℃, and then extruded and pelletized in a twin-screw extruder to obtain a composite material containing polymethyl methacrylate.

[0062] Example 5

[0063] (1) 7.11 g of cardanol, 4.07 g of triethylamine, and 1.87 g of melamine were added into 19 mL of chloroform solvent, stirred and refluxed, reacted at 3℃ for 5 h, then warmed to 88℃ and continued to react for 4 h, after the reaction was completed, naturally cooled to room temperature, filtered, rotary evaporated to remove the solvent, washed with deionized water, and dried to obtain tri-(3-pentadecenylphenoxy) triazine;

[0064] (2) 3.71 g of tri-(3-pentadecenylphenoxy) triazine and 3.49 g of 3-chloroperbenzoic acid were added into 12 mL of tetrahydrofuran solvent, reacted under ice water bath for 6 h, after the reaction was completed, filtered, the filtrate was washed with 10% by mass sodium carbonate solution, rotary evaporated to remove the solvent, and dried to obtain epoxidized tri-(3-pentadecenylphenoxy) triazine;

[0065] (3) 0.18 g of hydroxyl carbon nanotubes was first loaded into a digestion tube, 27 mL of N,N-dimethylformamide was added, ultrasonically treated for 50 min to disperse, to obtain a suspension, then 8.05 g of hexamethylene diisocyanate and 19 mL of N,N-dimethylformamide were added into the reactor, stirred uniformly, heated to 58℃, then the suspension was slowly added dropwise into the reactor, 0.16 g of dibutyltin dilaurate catalyst was added, and the stirring reaction was maintained at 58℃ for 10 h, after the reaction was completed, centrifuged, washed, and vacuum dried at 52℃ for 6 h to obtain isocyanate-functionalized carbon nanotubes;

[0066] (4) Under the protection of nitrogen gas, 1.4 mmol of isocyanate functionalized carbon nanotubes was added into 58 mL of N,N-dimethylformamide solvent, and ultrasonic treatment was performed for 38 min, then 0.8 mmol of epoxidized tris-(3-pentadecenylphenoxy) triazine, 0.02 mmol of tetramethylammonium chloride catalyst was added, the mixture was stirred, and reaction was performed at 148°C for 11 h. After the reaction was completed, centrifugation, washing and drying were performed to obtain modified carbon nanotubes;

[0067] (5) 39 mL of acetone, 42 mmol of 4-hydroxyethyl imidazole and 17 mmol of 2,2-bis(bromomethyl)-1,3-propanediol were added into a reactor, the mixture was stirred, then 4 mL of 5 mol / L sodium hydroxide aqueous solution was added dropwise, reaction was performed at 65°C for 7 h, after the reaction was completed, neutralization was performed by dropwise addition of 5% dilute hydrochloric acid, acetone was removed by concentration, the remaining aqueous solution was suction filtered, the precipitate was washed with water, and drying was performed to obtain intermediate 1;

[0068] (6) 12 mmol of intermediate 1, 6 mmol of fumaric acid and 0.02 g of p-toluenesulfonic acid were added into a reactor, the mixture was uniformly mixed, then 14 mL of cyclohexane was added as a water-carrying agent, reaction was performed at 175°C for 4 h under stirring reflux, after the reaction was completed, cyclohexane was removed by distillation under reduced pressure, and washing and drying were performed to obtain modified imidazole;

[0069] (7) 82 parts by weight of polymethyl methacrylate, 1.5 parts by weight of modified carbon nanotubes, 2 parts by weight of modified imidazole, 0.7 parts by weight of zinc stearate and 0.3 parts by weight of antioxidant 1010 were placed into a high-speed mixer, melt blending was performed for 28 min, the melt blending temperature was 182°C, then extrusion granulation was performed in a twin-screw extruder to obtain a composite material containing polymethyl methacrylate.

[0070] Comparative Example 1

[0071] This comparative example is different from Example 5 in that tris-(3-pentadecenylphenoxy) triazine is used instead of modified carbon nanotubes.

[0072] Comparative Example 2

[0073] This comparative example is different from Example 5 in that 4-hydroxyethyl imidazole is used instead of modified imidazole.

[0074] Performance test:

[0075] The composite materials prepared in Examples 1-5 and Comparative Examples 1-2 were subjected to performance tests.

[0076] (1) Mechanical property test: The Izod notched impact test was carried out according to GB / T 1843-2008 "Determination of Izod Impact Strength of Plastics", and the condition was type A notch; the flexural modulus test was carried out according to GB / T 9341-2000 "Standard Test Methods for Flexural Properties of Plastics". The test results are shown in Table 1.

[0077] Table 1: Mechanical property test

[0078]

[0079] As can be seen from Table 1, the composite materials prepared in Examples 1-5 have good mechanical properties.

[0080] (2) Flame retardant property test: The flame retardant property test was carried out according to the UL94 burning test method, and the oxygen index tester was used to test the oxygen index of the composite material. The test results are shown in Table 2.

[0081] Table 2: Flame retardant property test

[0082]

[0083] As can be seen from Table 2, the composite materials prepared in Examples 1-5 have good flame retardant properties.

[0084] (3) Antibacterial property test: The antibacterial property test was carried out according to GB / T 31402-2015 "Plastics - Test methods for antibacterial property of plastics surface", and the test bacteria were Escherichia coli AS1.90 and Staphylococcus aureus ACTT6538P. The test results are shown in Table 3.

[0085] Table 3: Antibacterial property test

[0086]

[0087] As can be seen from Table 3, the composite materials prepared in Examples 1-5 have good antibacterial properties.

[0088] It should be noted that in this article, the terms "include", "contain" or any other variant thereof are intended to cover non-exclusive inclusion, so that the process, method, article or equipment including a series of elements not only includes those elements, but also includes other elements not explicitly listed, or includes elements inherent to such process, method, article or equipment. Without more limitation, the element defined by the statement "including a" does not exclude the presence of another identical element in the process, method, article or equipment including the element.

[0089] The above examples are only used to illustrate the technical solutions of the present application, but not limit the present application; although the present application has been described in detail with reference to the foregoing examples, those skilled in the art should understand that the technical solutions recorded in the foregoing examples can be modified, or some technical features can be replaced equivalently; and these modifications or replacements do not make the essence of the corresponding technical solutions deviate from the spirit and scope of the technical solutions of the embodiments of the present application.

[0090] Those skilled in the art should understand that the above only describes several specific embodiments of the present application, but not all embodiments. It should be noted that many modifications and improvements can be made by those skilled in the art, and all modifications and improvements that do not exceed the scope of the claims should be considered as the protection scope of the present application.

Claims

1. A composite material containing polymethyl methacrylate, characterized in that, It includes the following components by weight: 70-85 parts by weight of polymethyl methacrylate, 1-1.5 parts by weight of modified carbon nanotubes, 1-2 parts by weight of modified imidazole, 0.5-0.8 parts by weight of zinc stearate, and 0.2-0.3 parts by weight of antioxidant 1010. The method for preparing the modified carbon nanotubes is as follows: Step 1: Add cashew phenol, triethylamine, and melamine to chloroform solvent, stir and reflux, and react at 0-5℃ for 3-5 hours. Then raise the temperature to 80-90℃ and continue the reaction for 2-4 hours. After the reaction is completed, cool naturally to room temperature, filter, remove the solvent by rotary evaporation, wash with deionized water, and dry to obtain tris-(3-pentadenephenoxy)triazine. Step 2: Add tri-(3-pentadenephenoxy)triazine and 3-chloroperoxybenzoic acid to tetrahydrofuran solvent, and react in an ice-water bath for 4-6 hours. After the reaction is complete, filter, wash the filtrate with a 10% sodium carbonate solution, remove the solvent by rotary evaporation, and dry to obtain epoxidized tri-(3-pentadenephenoxy)triazine. Step 3: First, load 0.1-0.2g of hydroxyl carbon nanotubes into a digestion tube, add 25-28mL of N,N-dimethylformamide, and sonicate for 30-60min to disperse them and obtain a suspension. Then, add 8.02-8.06g of hexamethylene diisocyanate and 15-20mL of N,N-dimethylformamide to the reactor, stir evenly, and heat to 50-60℃. Next, slowly add the suspension dropwise to the reactor, add 0.13-0.17g of dibutyltin dilaurate catalyst, and maintain the temperature at 50-60℃ for 8-10h with stirring. After the reaction is completed, centrifuge, wash, and vacuum dry at 45-55℃ for 4-6h to obtain isocyanate-functionalized carbon nanotubes. Step 4: Under nitrogen protection, add isocyanate-functionalized carbon nanotubes to N,N-dimethylformamide solvent, sonicate for 30-40 min, then add epoxidized tri-(3-pentadenephenoxy)triazine and tetramethylammonium chloride catalyst, stir and mix, and react at 140-150℃ for 8-12 h. After the reaction is completed, centrifuge, wash and dry to obtain modified carbon nanotubes. The modified imidazole is prepared by: S1: Add acetone, 4-hydroxyethylimidazolium and 2,2-di(bromomethyl)-1,3-propanediol to the reactor, stir and mix, then add sodium hydroxide aqueous solution with a molar concentration of 2-6 mol / L dropwise, stir and react at 50-70℃ for 5-8 h, after the reaction is completed, add 5% dilute hydrochloric acid dropwise to neutralize, concentrate to remove acetone, filter the remaining aqueous solution, wash the precipitate with water, dry it, and obtain intermediate 1; S2: Add intermediate 1, fumaric acid, and p-toluenesulfonic acid to the reactor and mix well. Then add cyclohexane as a dehydrating agent and stir and reflux at 160-180℃ for 2-4 hours. After the reaction is completed, remove cyclohexane by vacuum distillation, wash and dry to obtain modified imidazole.

2. The composite material containing polymethyl methacrylate according to claim 1, characterized in that, In step one, the ratio of chloroform, cashew nut shell extract, triethylamine, and melamine is 15-20 mL: 7.08-7.12 g: 4.04-4.08 g: 1.84-1.88 g.

3. The polymethyl methacrylate-containing composite material according to claim 1, characterized in that, In step two, the ratio of tetrahydrofuran, tris-(3-pentadenephenoxy)triazine, and 3-chloroperoxybenzoic acid is 10-12 mL: 3.68-3.72 g: 3.45-3.5 g.

4. The polymethyl methacrylate-containing composite material according to claim 1, characterized in that, In step four, the ratio of N,N-dimethylformamide, isocyanate-functionalized carbon nanotubes, epoxidized tri-(3-pentadenephenoxy)triazine, and tetramethylammonium chloride is 50-60 mL: 1.2-1.5 mmol: 0.6-0.8 mmol: 0.01-0.02 mmol.

5. The polymethyl methacrylate-containing composite material according to claim 1, characterized in that, The ratio of acetone, 4-hydroxyethylimidazol, and 2,2-di(bromomethyl)-1,3-propanediol in S1 is 35-40 mL: 35-45 mmol: 15-18 mmol.

6. The polymethyl methacrylate-containing composite material according to claim 1, characterized in that, The ratio of intermediate 1, fumaric acid, p-toluenesulfonic acid, and cyclohexane in S2 is 10-12 mmol: 4-6 mmol: 0.01-0.02 g: 12-15 mL.

7. A method for preparing a polymethyl methacrylate-containing composite material as described in any one of claims 1-6, characterized in that, The preparation method of the polymethyl methacrylate-containing composite material is as follows: polymethyl methacrylate, modified carbon nanotubes, modified imidazole, zinc stearate, and antioxidant 1010 are placed in a high-speed mixer and melt-blended for 20-30 minutes at a melt-blending temperature of 175-185℃. Then, the mixture is extruded and granulated in a twin-screw extruder to obtain the polymethyl methacrylate-containing composite material.

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