Epoxy resin coating containing organic silicon flame retardant and preparation method thereof

Abstract

The invention relates to the technical field of coatings, and discloses an epoxy resin coating containing an organosilicon flame retardant and a preparation method. According to the invention, bisphenol A epoxy resin, modified graphene oxide, silicon-containing epoxy resin, hexamethylenetetramine, talcum powder, calcium carbonate and water are added into a stirrer and stirred at room temperature to obtain the epoxy resin coating containing the organosilicon flame retardant; the graphene oxide in the modified graphene oxide has a good flame retardant effect; the sulfur element contained therein has a flame retardant effect; the sulfur element in the sodium sulfonate contained therein releases sulfate or sulfur dioxide at high temperature, and these substances can dilute oxygen in the air to a certain extent and also have a flame retardant effect; and the modified graphene oxide also contains a diquaternary ammonium salt structure, which has a good antibacterial effect; the modified graphene oxide and the silicon-containing epoxy resin contain stable Si-O-Si bonds, which have high bond energy and are not easily destroyed, and have a synergistic flame retardant effect.

Description

Technical Field

[0001] The invention relates to the technical field of coatings, in particular to an epoxy resin coating containing an organosilicon flame retardant and a preparation method thereof. Background Art

[0002] The occurrence of fire has brought great damage to human society. The burning of furniture and building materials surfaces poses a huge hidden danger to ecological and property safety. Therefore, how to avoid this phenomenon is the key to solving the problem. Silicon-based flame retardants have good flame retardancy and good processing performance, showing good application prospects. For example, patent CN10448214B discloses a method for preparing a phosphorus-containing silicon-containing polyurethane epoxy resin for flame-retardant packaging materials. The phosphorus-containing silicon-containing polyurethane epoxy resin prepared by the present invention has a simple synthesis process, easy control of conditions, and stable production. It is a green and environmentally friendly material and has broad application prospects in the field of electronic packaging. It has excellent flame retardant properties, but the antibacterial effect has not been improved. Summary of the invention

[0003] 1. Technical issues to be solved

[0004] In view of the deficiencies of the prior art, the present invention provides an epoxy resin coating containing an organosilicon flame retardant and a preparation method thereof, which has good flame retardant and antibacterial effects.

[0005] (II) Technical solution

[0006] To achieve the above-mentioned purpose, the present invention provides the following technical scheme: an epoxy resin coating containing an organosilicon flame retardant, comprising the following components by weight: 85-100 parts by weight of bisphenol A epoxy resin, 10-20 parts by weight of modified graphene oxide, 15-25 parts by weight of silicon-containing epoxy resin, 2-4 parts by weight of hexamethylenetetramine, 1-3 parts by weight of talc, 3-5 parts by weight of calcium carbonate, and 35-40 parts by weight of water.

[0007] Preferably, the preparation method of the modified graphene oxide is:

[0008] (1) ultrasonically dispersing graphene oxide in thionyl chloride, and after being evenly dispersed, reacting at 75-85° C. for 20-30 hours, and after the reaction, filtering, washing and drying to obtain chlorinated graphene;

[0009] (2) adding di(dimethylamino)methylvinylsilane to N,N-dimethylamide solvent, stirring and dispersing, and then adding benzoin dimethyl ether photoinitiator and aminoethanethiol thereto, irradiating with 365 nm ultraviolet light at 25-40° C. for 2-3 h, centrifuging, washing with deionized water, and drying to obtain intermediate 1;

[0010] (3) adding intermediate 1 and chlorinated graphene to toluene solvent, stirring to dissolve, adding pyridine catalyst thereto, reacting at 65-80° C. for 6-12 h, and then removing the solvent by distillation under reduced pressure, filtering and drying to obtain intermediate 2;

[0011] (4) Add 6-12 parts by weight of intermediate 2 and 8-15 parts by weight of sodium 3-chloro-2-hydroxypropanesulfonate to a mixed solution of 25-40 parts by weight of ethanol and 10-15 parts by weight of water, stir magnetically, and react at 95-110° C. for 7-10 hours. After reaction, wash with petroleum ether, and rotary evaporate to obtain modified graphene oxide.

[0012] Preferably, the mass ratio of graphene oxide to thionyl chloride in (1) is 1:10-16.

[0013] Preferably, the mass ratio of di(dimethylamino)methylvinylsilane, benzoin dimethyl ether photoinitiator and aminoethanethiol in (2) is 1.2-1.5:0.01-0.03:1.

[0014] Preferably, the mass ratio of the intermediate 1, the chlorinated graphene, and the pyridine catalyst in (3) is 1:1.1-1.3:0.02-0.03.

[0015] Preferably, the preparation method of the silicon-containing epoxy resin is:

[0016] S1. Add pentaerythritol methyl silicate to N,N-dimethylformamide solvent, stir and disperse, then add vinyl trichlorosilane, react at 95-110° C. for 10-17 hours, filter after completion, distill the filtrate under reduced pressure, wash with deionized water, and dry to obtain olefinated silane;

[0017] S2.4-10 parts by weight of alkenyl silane, 12-15 parts by weight of allyl alcohol glycidyl ether, 10-20 parts by weight of glycidyl acrylate and 1-3 parts by weight of chloroplatinic acid are added to a reactor, reacted at 60-85°C for 8-12h, washed with water until neutral, to obtain a silicon-containing epoxy resin.

[0018] Preferably, the mass ratio of pentaerythritol methyl silicate to vinyl trichlorosilane in S1 is 2.3-4:1.

[0019] Preferably, the preparation method of the epoxy resin coating containing silicone flame retardant is: add bisphenol A epoxy resin, modified graphene oxide, silicon-containing epoxy resin, hexamethylenetetramine, talcum powder, calcium carbonate, and water into a stirrer, and stir at room temperature for 10-16 minutes to obtain the epoxy resin coating containing silicone flame retardant.

[0020] (III) Beneficial technical effects

[0021] The present invention prepares the epoxy resin coating containing the organosilicon flame retardant by adding bisphenol A epoxy resin, modified graphene oxide, silicon-containing epoxy resin, hexamethylenetetramine, talcum powder, calcium carbonate and water into a stirrer and stirring at room temperature.

[0022] The graphene oxide in the modified graphene oxide can rapidly promote the formation of a stable carbon layer on the polymer surface under high temperature. This carbon layer can effectively block the propagation of oxygen and heat, thereby slowing down the combustion rate of the coating and achieving a good flame retardant effect. The sulfur element contained therein can promote the formation of a carbon layer on the polymer surface at high temperature. This carbon layer can serve as a barrier layer for heat and oxygen, thereby slowing down the combustion rate and achieving a flame retardant effect. The sulfur element in the sodium sulfonate contained therein will release sulfate or sulfur dioxide at high temperature. These substances can dilute the oxygen in the air to a certain extent and also have a flame retardant effect. The modified graphene oxide also contains a diquaternary ammonium salt structure, which has a good antibacterial effect. The modified graphene oxide and the silicon-containing epoxy resin contain stable Si-O-Si bonds, which have high bond energy and are not easily destroyed, and have a synergistic flame retardant effect. DETAILED DESCRIPTION

[0023] Example 1

[0024] (1) ultrasonically dispersing graphene oxide in thionyl chloride, wherein the mass ratio of graphene oxide to thionyl chloride is 1:10, and after being evenly dispersed, reacting at 75° C. for 20 h, and after the reaction, filtering, washing and drying to obtain chlorinated graphene;

[0025] (2) adding di(dimethylamino)methylvinylsilane to N,N-dimethylamide solvent, stirring and dispersing, and then continuing to add benzoin dimethyl ether photoinitiator and aminoethanethiol, wherein the mass ratio of di(dimethylamino)methylvinylsilane, benzoin dimethyl ether photoinitiator and aminoethanethiol is 1.2:0.01:1, irradiating with 365nm ultraviolet light at 25°C for 2h, centrifuging, washing with deionized water, and drying to obtain intermediate 1;

[0026] (3) adding intermediate 1 and chlorinated graphene to toluene solvent, stirring to dissolve, and continuing to add pyridine catalyst, wherein the mass ratio of intermediate 1, chlorinated graphene, and pyridine catalyst is 1:1.1:0.02, reacting at 65° C. for 6 h, and after the reaction, removing the solvent by reduced pressure distillation, filtering and drying to obtain intermediate 2;

[0027] (4) adding 6 parts by weight of intermediate 2 and 8 parts by weight of sodium 3-chloro-2-hydroxypropanesulfonate to a mixed solution of 25 parts by weight of ethanol and 10 parts by weight of water, stirring magnetically, reacting at 95° C. for 7 h, washing with petroleum ether after the reaction, and rotary evaporation to obtain modified graphene oxide;

[0028] (5) adding pentaerythritol methyl silicate to N,N-dimethylformamide solvent, stirring and dispersing, and then adding vinyl trichlorosilane thereto, wherein the mass ratio of pentaerythritol methyl silicate to vinyl trichlorosilane is 2.3:1, reacting at 95° C. for 10 h, filtering after completion, distilling the filtrate under reduced pressure, washing with deionized water, and drying to obtain olefinated silane;

[0029] (6) 4 parts by weight of alkenyl silane, 12 parts by weight of allyl alcohol glycidyl ether, 10 parts by weight of glycidyl acrylate and 1 part by weight of chloroplatinic acid were added to a reactor, reacted at 60° C. for 8 hours, and washed with water until neutral to obtain a silicon-containing epoxy resin;

[0030] (7) 85 parts by weight of bisphenol A epoxy resin, 10 parts by weight of modified graphene oxide, 15 parts by weight of silicon-containing epoxy resin, 2 parts by weight of hexamethylenetetramine, 1 part by weight of talc, 3 parts by weight of calcium carbonate, and 35 parts by weight of water were added into a stirrer and stirred at room temperature for 10 minutes to obtain an epoxy resin coating containing an organosilicon flame retardant.

[0031] Example 2

[0032] (1) ultrasonically dispersing graphene oxide in thionyl chloride, wherein the mass ratio of graphene oxide to thionyl chloride is 1:16, and after being uniformly dispersed, reacting at 85° C. for 30 h, and after the reaction, filtering, washing and drying to obtain chlorinated graphene;

[0033] (2) adding di(dimethylamino)methylvinylsilane to N,N-dimethylamide solvent, stirring and dispersing, and then continuing to add benzoin dimethyl ether photoinitiator and aminoethanethiol, wherein the mass ratio of di(dimethylamino)methylvinylsilane, benzoin dimethyl ether photoinitiator and aminoethanethiol is 1.5:0.03:1, irradiating with 365nm ultraviolet light at 40°C for 3h, centrifuging, washing with deionized water, and drying to obtain intermediate 1;

[0034] (3) adding intermediate 1 and chlorinated graphene to toluene solvent, stirring to dissolve, and continuing to add pyridine catalyst, wherein the mass ratio of intermediate 1, chlorinated graphene, and pyridine catalyst is 1:1.3:0.03, reacting at 80° C. for 12 h, and after the reaction, removing the solvent by reduced pressure distillation, filtering and drying to obtain intermediate 2;

[0035] (4) adding 12 parts by weight of intermediate 2 and 15 parts by weight of sodium 3-chloro-2-hydroxypropanesulfonate to a mixed solution of 40 parts by weight of ethanol and 15 parts by weight of water, stirring with a magnetic stirrer, reacting at 110° C. for 10 h, washing with petroleum ether after the reaction, and rotary evaporation to obtain modified graphene oxide;

[0036] (5) adding pentaerythritol methyl silicate to N,N-dimethylformamide solvent, stirring and dispersing, and then adding vinyl trichlorosilane thereto, wherein the mass ratio of pentaerythritol methyl silicate to vinyl trichlorosilane is 4:1, reacting at 110° C. for 17 h, filtering after the reaction, distilling the filtrate under reduced pressure, washing with deionized water, and drying to obtain olefinated silane;

[0037] (6) 10 parts by weight of alkenyl silane, 15 parts by weight of allyl alcohol glycidyl ether, 20 parts by weight of glycidyl acrylate and 3 parts by weight of chloroplatinic acid are added to a reactor, reacted at 85° C. for 12 hours, and washed with water until neutral to obtain a silicon-containing epoxy resin;

[0038] (7) 100 parts by weight of bisphenol A epoxy resin, 20 parts by weight of modified graphene oxide, 25 parts by weight of silicon-containing epoxy resin, 4 parts by weight of hexamethylenetetramine, 3 parts by weight of talc, 5 parts by weight of calcium carbonate, and 40 parts by weight of water are added into a stirrer and stirred at room temperature for 16 minutes to obtain an epoxy resin coating containing an organosilicon flame retardant.

[0039] Example 3

[0040] (1) ultrasonically dispersing graphene oxide in thionyl chloride, wherein the mass ratio of graphene oxide to thionyl chloride is 1:13, after being evenly dispersed, reacting at 80° C. for 25 h, filtering after the reaction, washing and drying to obtain chlorinated graphene;

[0041] (2) adding di(dimethylamino)methylvinylsilane to N,N-dimethylamide solvent, stirring and dispersing, and then continuing to add benzoin dimethyl ether photoinitiator and aminoethanethiol, wherein the mass ratio of di(dimethylamino)methylvinylsilane, benzoin dimethyl ether photoinitiator and aminoethanethiol is 1.35:0.02:1, irradiating with 365 nm ultraviolet light at 32.5° C. for 2.5 h, centrifuging, washing with deionized water, and drying to obtain intermediate 1;

[0042] (3) adding intermediate 1 and chlorinated graphene to toluene solvent, stirring to dissolve, and continuing to add pyridine catalyst, wherein the mass ratio of intermediate 1, chlorinated graphene, and pyridine catalyst is 1:1.2:0.025, reacting at 72.5° C. for 9 h, and then removing the solvent by reduced pressure distillation after the reaction, filtering and drying to obtain intermediate 2;

[0043] (4) adding 9 parts by weight of intermediate 2 and 11.5 parts by weight of sodium 3-chloro-2-hydroxypropanesulfonate to a mixed solution of 32.5 parts by weight of ethanol and 12.5 parts by weight of water, stirring with a magnetic stirrer, reacting at 102.5° C. for 8.5 h, washing with petroleum ether after the reaction, and rotary evaporation to obtain modified graphene oxide;

[0044] (5) adding pentaerythritol methyl silicate to N,N-dimethylformamide solvent, stirring and dispersing, and then adding vinyl trichlorosilane thereto, wherein the mass ratio of pentaerythritol methyl silicate to vinyl trichlorosilane is 3.15:1, reacting at 102.5° C. for 13.5 hours, filtering after the reaction, distilling the filtrate under reduced pressure, washing with deionized water, and drying to obtain olefinated silane;

[0045] (6) 7 parts by weight of alkenyl silane, 13.5 parts by weight of allyl alcohol glycidyl ether, 15 parts by weight of glycidyl acrylate and 2 parts by weight of chloroplatinic acid were added to a reactor, reacted at 72.5° C. for 10 hours, and washed with water until neutral to obtain a silicon-containing epoxy resin;

[0046] (7) 92.5 parts by weight of bisphenol A epoxy resin, 15 parts by weight of modified graphene oxide, 20 parts by weight of silicon-containing epoxy resin, 3 parts by weight of hexamethylenetetramine, 2 parts by weight of talc, 4 parts by weight of calcium carbonate, and 37.5 parts by weight of water were added into a stirrer and stirred at room temperature for 13 minutes to obtain an epoxy resin coating containing an organosilicon flame retardant.

[0047] Comparative Example 1

[0048] (1) 92.5 parts by weight of bisphenol A epoxy resin, 15 parts by weight of modified graphene oxide, 3 parts by weight of hexamethylenetetramine, 2 parts by weight of talc, 4 parts by weight of calcium carbonate, and 37.5 parts by weight of water were added to a stirrer and stirred at room temperature for 13 minutes to obtain an epoxy resin coating containing an organosilicon flame retardant.

[0049] Comparative Example 2

[0050] (1) 92.5 parts by weight of bisphenol A epoxy resin, 20 parts by weight of silicon-containing epoxy resin, 3 parts by weight of hexamethylenetetramine, 2 parts by weight of talc, 4 parts by weight of calcium carbonate, and 37.5 parts by weight of water were added into a stirrer and stirred at room temperature for 13 minutes to obtain an epoxy resin coating containing an organosilicon flame retardant.

[0051] The limiting oxygen index of water-based paint was tested using an oxygen index meter; the combustion level of water-based paint was tested using a horizontal and vertical combustion instrument. The test results are shown in Table 1.

[0052] Table 1: Flame retardancy tests.

[0053] project Limiting oxygen index (%) Combustion level Example 1 29 V-0 Example 2 32 V-0 Example 3 31 V-0 Comparative Example 1 22 V-1 Comparative Example 2 21 V-1

[0054] It can be seen from Table 1 that the epoxy resin coating containing silicone flame retardant prepared in Examples 1-3 of the present invention has better flame retardant effect than that in Comparative Examples 1-2.

[0055] Staphylococcus aureus was inoculated into beef extract peptone for culture activation, and then the activated Staphylococcus aureus suspension was added to a sterile culture dish, and culture medium and phosphate buffer solution were added, and cultured at a constant temperature of 37°C for 24 hours. The sand-like exterior wall coating with the protective coating prepared in Example 1-5 and Comparative Example 1-2 was added, and the antibacterial rate was calculated after culture. The test results are shown in Table 2.

[0056] Table 2: Antimicrobial testing.

[0057] project Antibacterial rate (%) Example 1 99.5 Example 2 99.8 Example 3 99.7 Comparative Example 1 98.1 Comparative Example 2 73.5

[0058] As can be seen from Table 2, the epoxy resin coating containing silicone flame retardant prepared by the present invention, Comparative Example 2 has no antibacterial quaternary ammonium salt group, so the antibacterial effect of Comparative Example 2 is lower than that of Examples 1-3 and Comparative Example 1.

[0059] The preferred embodiments of the present invention disclosed above are only used to help illustrate the present invention. The preferred embodiments do not describe all the details in detail, nor do they limit the invention to the specific implementation methods described. Obviously, many modifications and changes can be made according to the content of this specification. This specification selects and specifically describes these embodiments in order to better explain the principles and practical applications of the present invention, so that those skilled in the art can understand and use the present invention well. The present invention is limited only by the claims and their full scope and equivalents.

Claims

1. An epoxy resin coating containing a silicone flame retardant, characterized in that: The invention comprises the following components by weight: 85-100 parts by weight of bisphenol A epoxy resin, 10-20 parts by weight of modified graphene oxide, 15-25 parts by weight of silicon-containing epoxy resin, 2-4 parts by weight of hexamethylenetetramine, 1-3 parts by weight of talc, 3-5 parts by weight of calcium carbonate, and 35-40 parts by weight of water; The preparation method of the modified graphene oxide is: (1) ultrasonically dispersing graphene oxide in thionyl chloride, and after being evenly dispersed, reacting at 75-85° C. for 20-30 hours, and after the reaction, filtering, washing and drying to obtain chlorinated graphene; (2) Add di(dimethylamino)methylvinylsilane to N,N-dimethylamide solvent, stir and disperse, then continue to add benzoin dimethyl ether photoinitiator and aminoethanethiol, irradiate with 365nm ultraviolet light at 25-40°C for 2-3h, centrifuge, wash with deionized water, and dry to obtain intermediate 1; (3) Add intermediate 1 and chlorinated graphene to toluene solvent, stir to dissolve, continue to add pyridine catalyst, react at 65-80°C for 6-12h, remove the solvent by vacuum distillation, filter and dry to obtain intermediate 2; (4) adding 6-12 parts by weight of intermediate 2 and 8-15 parts by weight of sodium 3-chloro-2-hydroxypropanesulfonate to a mixed solution of 25-40 parts by weight of ethanol and 10-15 parts by weight of water, stirring with a magnetic stirrer, reacting at 95-110° C. for 7-10 hours, washing with petroleum ether after reaction, and rotary evaporation to obtain modified graphene oxide; The mass ratio of graphene oxide to thionyl chloride in (1) is 1:10-16; The mass ratio of di(dimethylamino)methylvinylsilane, benzoin dimethyl ether photoinitiator and aminoethanethiol in (2) is 1.2-1.5:0.01-0.03:1; The mass ratio of the intermediate 1, the chlorinated graphene, and the pyridine catalyst in (3) is 1:1.1-1.3:0.02-0.03; The preparation method of the silicon-containing epoxy resin is: S1. Add pentaerythritol methyl silicate to N,N-dimethylformamide solvent, stir and disperse, then add vinyl trichlorosilane, react at 95-110° C. for 10-17 hours, filter after completion, distill the filtrate under reduced pressure, wash with deionized water, and dry to obtain olefinated silane; S2.4-10 parts by weight of alkenyl silane, 12-15 parts by weight of allyl alcohol glycidyl ether, 10-20 parts by weight of glycidyl acrylate and 1-3 parts by weight of chloroplatinic acid are added to a reactor, reacted at 60-85°C for 8-12h, washed with water until neutral, to obtain a silicon-containing epoxy resin; The mass ratio of pentaerythritol methyl silicate to vinyl trichlorosilane in S1 is 2.3-4:

1.

2. A method for preparing an epoxy resin coating containing an organosilicon flame retardant as claimed in claim 1, characterized in that: The preparation method of the epoxy resin coating containing the organosilicon flame retardant is as follows: bisphenol A epoxy resin, modified graphene oxide, silicon-containing epoxy resin, hexamethylenetetramine, talcum powder, calcium carbonate and water are added into a stirrer, and stirred at room temperature for 10-16 minutes to obtain the epoxy resin coating containing the organosilicon flame retardant.