Environmentally friendly flame-retardant photosensitive resin material and preparation method thereof

Abstract

The invention relates to the technical field of photosensitive resins, and in particular to an environmentally friendly flame-retardant photosensitive resin material and a preparation method thereof. In order to improve the environmental performance of the photosensitive resin, the invention uses eugenol as a raw material, mixes it with formaldehyde, and thus prepares a eugenol diene compound with a methylene group and two olefin groups. On this basis, the invention also prepares a benzophenone phosphosilicate intermediate with a large amount of phosphosilicate elements and benzophenone groups, grafts it to the eugenol diene compound under ultraviolet light irradiation, and performs epoxidation treatment on it, thereby preparing an environmentally friendly flame-retardant epoxy resin with a flame-retardant function. Adding the eugenol into the photosensitive resin can effectively reduce the use of petrochemical raw materials and improve the environmental performance of the raw materials.

Description

Technical Field

[0001] The invention relates to the technical field of photosensitive resins, and in particular to an environmentally friendly flame-retardant photosensitive resin material and a preparation method thereof. Background Art

[0002] 3D printing technology, also known as additive manufacturing technology, is flexible, efficient and has a high degree of freedom. It has gradually become an emerging product manufacturing technology. In the current 3D printing technology, photosensitive resin has become more and more popular due to its advantages of fast curing speed, low cost and easy molding. However, compared with metal printing, photosensitive resin has its own properties, high temperature resistance and flammability, which has brought great limitations to the popularization of 3D printing of photosensitive resin. In addition, photosensitive resins are mostly chemical products, and the preparation process is polluting and energy-consuming. In addition, the product cost caused by the scarcity of petroleum raw materials is also high. Therefore, it is necessary to conduct research on such defects. Summary of the invention

[0003] The object of the present invention is to provide an environmentally friendly flame-retardant photosensitive resin material and a preparation method thereof, so as to solve the problems raised in the above-mentioned background technology.

[0004] In order to solve the above technical problems, the present invention provides the following technical solutions: a method for preparing an environmentally friendly flame-retardant photosensitive resin material, comprising the following steps:

[0005] S1. Preparation of environmentally friendly flame-retardant epoxy resin;

[0006] S11. Mix eugenol with 85 wt % phosphoric acid for 15-30 min, heat the mixture to 50-55° C., keep the mixture warm for 30 min, then drop a formaldehyde solution therein for 1-2 h. After the addition is complete, heat the mixture to 88-95° C., keep the mixture warm for 5-8 h, remove excess solvent by rotary evaporation, wash the precipitate with deionized water for 2-5 times, disperse the remaining product in toluene for recrystallization, filter and dry to obtain a eugenol diene compound;

[0007] S12. Trimethyltrihydrogencyclotrisiloxane is mixed with DMF, and after ultrasonic oscillation dispersion for 10-15 minutes, Raney nickel is added, and the mixture is mixed for 1-3 minutes. After cooling to 5-10°C, bistrimethylsilyl vinyl phosphate is added dropwise for 1-2 hours. After the addition is completed, the mixture is heated to 75-85°C, and refluxed for 2-12 hours. The excess solvent is removed by rotary evaporation, and the precipitate is washed with a hydrochloric acid solution at a temperature of 2-4°C, and the precipitate is washed again with DMF for 2-3 times, and then vacuum dried to constant weight to obtain a phosphorus silicon intermediate;

[0008] S13. The phosphorus silicon intermediate prepared in step S12 is dispersed in DMF, mixed by ultrasonic oscillation for 30-45 min, cooled to 5-10 ° C, and set aside;

[0009] Disperse L-lysine diisocyanate in pure DMF, stir and mix for 15-30 minutes, cool to 5-15°C, add dropwise a DMF dispersion containing a phosphorus silicon intermediate for 1-2 hours, heat to 85-92°C after the addition is completed, stir and react for 2-4 hours, cool to 45-50°C, add 4-aminobenzophenone, continue to stir and react for 1-4 hours, and remove excess solvent by rotary evaporation to obtain a benzophenone phosphorus silicon intermediate;

[0010] S14. Disperse the eugenol diene compound in DMF, stir and disperse for 1-2 hours, add benzophenone phosphosilicon intermediate, continue mixing for 0.5-1 hour, perform UV irradiation cross-linking on the reaction system for 15-45 minutes, add m-chloroperbenzoic acid thereto, continue stirring and reacting for 24-48 hours, evaporate excess solvent, wash the precipitate with deionized water for 3-5 times, mix the precipitate with epichlorohydrin, stir and mix for 30-45 minutes, add tetrabutylammonium bromide, continue mixing for 1-2 hours, heat to 85-95°C, continue reacting for 4-8 hours, and evaporate in vacuo to constant weight to obtain an environmentally friendly flame-retardant epoxy resin;

[0011] S2. Heat the environmentally friendly flame-retardant epoxy resin to 80-90°C, add E51 epoxy resin, inhibitor and catalyst thereto, mix for 10-15 minutes, cool to 30-55°C, add acrylate thereto, continue mixing for 5-10 minutes, add diluent monomer and photoinitiator, continue mixing for 3-5 minutes, and then discharge the material to obtain an environmentally friendly flame-retardant photosensitive resin material.

[0012] Furthermore, in step S11, the molar ratio of eugenol to formaldehyde is 2:1.05 in terms of molar proportions.

[0013] Furthermore, in step S12, the mass ratio of trimethyltrihydrogencyclotrisiloxane, Raney nickel, and bistrimethylsilylated vinyl phosphate is 1:(0.001-0.003):(2.1-2.8).

[0014] Furthermore, in step S13, the mass ratio of the phosphorus silicon intermediate, L-lysine diisocyanate, and 4-aminobenzophenone is 1: (0.3-0.33): (0.25-0.29).

[0015] Furthermore, in step S14, the mass ratio of the eugenol diene compound, the benzophenone phosphosilicate intermediate, and the meta-chloroperbenzoic acid is 1:(1.5-3.1):(0.81-0.96).

[0016] Furthermore, in step S14, the mass ratio of the eugenol diene compound to epichlorohydrin is 1:(10-30).

[0017] Furthermore, in step S2, the environmentally friendly flame-retardant photosensitive resin material is composed of 20-30 parts of environmentally friendly flame-retardant epoxy resin, 15-25 parts of E51 epoxy resin, 15-25 parts of acrylate, 15-40 parts of diluent monomer, 0.3-0.8 parts of photoinitiator, 0.1-0.5 parts of inhibitor and 0.1-0.3 parts of catalyst in parts by weight.

[0018] Furthermore, in step S2, the acrylic acid ester is any one or more of hydroxyethyl acrylate, 4-hydroxybutyl acrylate, and hydroxyethyl methacrylate.

[0019] Furthermore, in step S2, the diluent monomer is resorcinol diglycidyl ether; the inhibitor is p-hydroxyanisole; the catalyst is triethylamine; and the photoinitiator is ethyl 2,4,6-trimethylbenzoylphenylphosphonate.

[0020] Compared with the prior art, the beneficial effects achieved by the present invention are:

[0021] In order to improve the environmental performance of the photosensitive resin, the present invention uses eugenol as a raw material and mixes it with formaldehyde to prepare a eugenol diene compound with a methylene group and two olefin groups;

[0022] Afterwards, the present invention mixes trimethyl trihydrogen cyclotrisiloxane with bistrimethyl silylated vinyl phosphate, utilizes the reaction between silicon-hydrogen bonds and olefin double bonds, and controls the reaction conditions to prepare a phosphorus-silicon intermediate containing a large amount of phosphorus and silicon. Both the phosphorus and silicon have strong flame retardant properties. In the combustion reaction, the phosphorus absorbs heat to generate phosphorus oxides, reducing heat accumulation, and the generated phosphorus oxides further generate gaseous substances, thereby reducing the oxygen concentration on the surface of the combustible and preventing the combustion reaction from proceeding. The silicon can form a silicon-carbon layer to hinder the combustion reaction, thereby improving the flame retardant properties.

[0023] On this basis, the present invention further reacts the phosphorus silicon intermediate with L-lysine diisocyanate and 4-aminobenzophenone in sequence, thereby generating a benzophenone phosphorus silicon intermediate with a benzophenone structure. Benzophenone is reactive under ultraviolet light irradiation and can react with the methylene group in the eugenol diene compound, thereby introducing phosphorus silicon elements into the eugenol diene compound to improve the flame retardant properties of the material. The present invention further uses meta-chloroperbenzoic acid to react with it, thereby epoxidizing the unsaturated carbon-carbon double bonds in the eugenol diene compound to generate epoxy groups. The present invention further uses epichlorohydrin to further treat the eugenol diene compound, and uses epichlorohydrin to react with the hydroxyl group in the eugenol diene compound, thereby further increasing the number of epoxy groups in the eugenol diene compound. Finally, an environmentally friendly flame-retardant epoxy resin is prepared. Adding the epoxy resin into a photosensitive resin can effectively improve the flame retardant properties of the photosensitive resin, reduce the use of petrochemical raw materials, and improve the environmental performance of the raw materials. DETAILED DESCRIPTION

[0024] The technical solutions in the embodiments of the present invention are described clearly and completely below. Obviously, the described embodiments are only part of the embodiments of the present invention, not all of them. 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.

[0025] Example 1. A method for preparing an environmentally friendly flame-retardant photosensitive resin material, comprising the following steps:

[0026] S1. Preparation of environmentally friendly flame-retardant epoxy resin;

[0027] S11. In terms of molar parts, 2 mol parts of eugenol were mixed with 85 wt % of phosphoric acid. After mixing for 15 min, the mixture was heated to 50 ° C. and kept warm for 30 min. Then, a formaldehyde solution containing 1.05 mol parts of formaldehyde was added dropwise thereto for 1 h. After the addition was completed, the temperature was raised to 90 ° C. After the reaction was kept warm for 6 h, the excess solvent was removed by rotary evaporation, and the precipitate was washed 4 times with deionized water. The remaining product was dispersed in toluene for recrystallization, filtered and dried to obtain a eugenol diene compound;

[0028] S12. According to the weight ratio, 1 part of trimethyltrihydrogencyclotrisiloxane was mixed with DMF, and after ultrasonic vibration dispersion for 10 minutes, 0.003 parts of Raney nickel was added, and the mixture was mixed for 2 minutes, and then cooled to 5°C, and 2.1 parts of bistrimethylsilyl vinyl phosphate were added dropwise thereto for 1 hour. After the addition was completed, the temperature was raised to 80°C, and after reflux reaction for 8 hours, the excess solvent was removed by rotary evaporation, and the precipitate was washed with a hydrochloric acid solution at a temperature of 4°C, and then the precipitate was washed twice with DMF, and then vacuum dried to constant weight to obtain a phosphorus silicon intermediate;

[0029] S13. In parts by weight, one portion of the phosphorus silicon intermediate prepared in step S12 was dispersed in DMF, ultrasonically mixed for 30 min, cooled to 5 ° C, and set aside;

[0030] Disperse 0.3 parts of L-lysine diisocyanate in pure DMF, stir and mix for 15 minutes, cool to 10°C, add dropwise DMF dispersion containing phosphosilicate intermediate for 1 hour, heat to 85°C after the addition, stir and react for 3 hours, cool to 45°C, add 0.25 parts of 4-aminobenzophenone, continue to stir and react for 1 hour, and remove excess solvent by rotary evaporation to obtain benzophenone phosphosilicate intermediate;

[0031] S14. Disperse 1 part of eugenol diene compound in DMF by weight, stir and disperse for 1 hour, add 1.5 parts of benzophenone phosphosilicone intermediate, continue mixing for 0.5 hour, crosslink the reaction system by ultraviolet irradiation for 30 minutes, add 0.81 parts of m-chloroperbenzoic acid, continue stirring and reacting for 24 hours, evaporate excess solvent, wash the precipitate with deionized water 3 times, mix the precipitate with 10 parts of epichlorohydrin, stir and mix for 30 minutes, add 0.05 parts of tetrabutylammonium bromide, continue mixing for 2 hours, heat to 95°C, continue reacting for 8 hours, and evaporate in vacuo to constant weight to obtain an environmentally friendly flame-retardant epoxy resin;

[0032] S2. By weight, 20 parts of environmentally friendly flame-retardant epoxy resin were heated to 80°C, 15 parts of E51 epoxy resin, 0.3 parts of p-hydroxyanisole inhibitor and 0.1 parts of triethylamine catalyst were added thereto, and mixed for 10 minutes. The temperature was then lowered to 35°C, 15 parts of hydroxyethyl methacrylate were added thereto, and the mixture was mixed for 5 minutes. Then, resorcinol diglycidyl ether and 0.5 parts of ethyl 2,4,6-trimethylbenzoylphenylphosphonate photoinitiator were added. The mixture was mixed for 4 minutes, and then the material was discharged to obtain an environmentally friendly flame-retardant photosensitive resin material.

[0033] Example 2. A method for preparing an environmentally friendly flame-retardant photosensitive resin material, comprising the following steps:

[0034] Compared with Example 1, this example increases the amount of bistrimethylsilylated vinyl phosphate added in step S12;

[0035] S1. Preparation of environmentally friendly flame-retardant epoxy resin;

[0036] S11. In terms of molar parts, 2 mol parts of eugenol were mixed with 85 wt % of phosphoric acid. After mixing for 15 min, the mixture was heated to 50 ° C. and kept warm for 30 min. Then, a formaldehyde solution containing 1.05 mol parts of formaldehyde was added dropwise thereto for 1 h. After the addition was completed, the temperature was raised to 90 ° C. After the reaction was kept warm for 6 h, the excess solvent was removed by rotary evaporation, and the precipitate was washed 4 times with deionized water. The remaining product was dispersed in toluene for recrystallization, filtered and dried to obtain a eugenol diene compound;

[0037] S12. According to the weight ratio, 1 part of trimethyltrihydrogencyclotrisiloxane was mixed with DMF, and after ultrasonic oscillation dispersion for 10 minutes, 0.003 parts of Raney nickel was added, and the mixture was mixed for 2 minutes, and then cooled to 5°C, and 2.8 parts of bistrimethylsilyl vinyl phosphate were added dropwise thereto for 1 hour. After the addition was completed, the temperature was raised to 80°C, and after reflux reaction for 8 hours, the excess solvent was removed by rotary evaporation, and the precipitate was washed with a hydrochloric acid solution at a temperature of 4°C, and then the precipitate was washed twice with DMF, and then vacuum dried to constant weight to obtain a phosphorus silicon intermediate;

[0038] S13. In parts by weight, one portion of the phosphorus silicon intermediate prepared in step S12 was dispersed in DMF, ultrasonically mixed for 30 min, cooled to 5 ° C, and set aside;

[0039] Disperse 0.3 parts of L-lysine diisocyanate in pure DMF, stir and mix for 15 minutes, cool to 10°C, add dropwise DMF dispersion containing phosphosilicate intermediate for 1 hour, heat to 85°C after the addition, stir and react for 3 hours, cool to 45°C, add 0.25 parts of 4-aminobenzophenone, continue to stir and react for 1 hour, and remove excess solvent by rotary evaporation to obtain benzophenone phosphosilicate intermediate;

[0040] S14. Disperse 1 part of eugenol diene compound in DMF by weight, stir and disperse for 1 hour, add 1.5 parts of benzophenone phosphosilicone intermediate, continue mixing for 0.5 hour, crosslink the reaction system by ultraviolet irradiation for 30 minutes, add 0.81 parts of m-chloroperbenzoic acid, continue stirring and reacting for 24 hours, evaporate excess solvent, wash the precipitate with deionized water 3 times, mix the precipitate with 10 parts of epichlorohydrin, stir and mix for 30 minutes, add 0.05 parts of tetrabutylammonium bromide, continue mixing for 2 hours, heat to 95°C, continue reacting for 8 hours, and evaporate in vacuo to constant weight to obtain an environmentally friendly flame-retardant epoxy resin;

[0041] S2. By weight, 20 parts of environmentally friendly flame-retardant epoxy resin were heated to 80°C, 15 parts of E51 epoxy resin, 0.3 parts of p-hydroxyanisole inhibitor and 0.1 parts of triethylamine catalyst were added thereto, and mixed for 10 minutes. The temperature was then lowered to 35°C, 15 parts of hydroxyethyl methacrylate were added thereto, and the mixture was mixed for 5 minutes. Then, resorcinol diglycidyl ether and 0.5 parts of ethyl 2,4,6-trimethylbenzoylphenylphosphonate photoinitiator were added. The mixture was mixed for 4 minutes, and then the material was discharged to obtain an environmentally friendly flame-retardant photosensitive resin material.

[0042] Example 3. A method for preparing an environmentally friendly flame-retardant photosensitive resin material, comprising the following steps:

[0043] Compared with Example 1, this example increases the amount of 4-aminobenzophenone added in step S13;

[0044] S1. Preparation of environmentally friendly flame-retardant epoxy resin;

[0045] S11. In terms of molar parts, 2 mol parts of eugenol were mixed with 85 wt % of phosphoric acid. After mixing for 15 min, the mixture was heated to 50 ° C. and kept warm for 30 min. Then, a formaldehyde solution containing 1.05 mol parts of formaldehyde was added dropwise thereto for 1 h. After the addition was completed, the temperature was raised to 90 ° C. After the reaction was kept warm for 6 h, the excess solvent was removed by rotary evaporation, and the precipitate was washed 4 times with deionized water. The remaining product was dispersed in toluene for recrystallization, filtered and dried to obtain a eugenol diene compound;

[0046] S12. According to the weight ratio, 1 part of trimethyltrihydrogencyclotrisiloxane was mixed with DMF, and after ultrasonic vibration dispersion for 10 minutes, 0.003 parts of Raney nickel was added, and the mixture was mixed for 2 minutes, and then cooled to 5°C, and 2.1 parts of bistrimethylsilyl vinyl phosphate were added dropwise thereto for 1 hour. After the addition was completed, the temperature was raised to 80°C, and after reflux reaction for 8 hours, the excess solvent was removed by rotary evaporation, and the precipitate was washed with a hydrochloric acid solution at a temperature of 4°C, and then the precipitate was washed twice with DMF, and then vacuum dried to constant weight to obtain a phosphorus silicon intermediate;

[0047] S13. In parts by weight, one portion of the phosphorus silicon intermediate prepared in step S12 was dispersed in DMF, ultrasonically mixed for 30 min, cooled to 5 ° C, and set aside;

[0048] Disperse 0.3 parts of L-lysine diisocyanate in pure DMF, stir and mix for 15 minutes, cool to 10°C, add dropwise the DMF dispersion containing the phosphorus silicon intermediate for 1 hour, raise the temperature to 85°C after the addition is completed, stir and react for 3 hours, cool to 45°C, add 0.29 parts of 4-aminobenzophenone, continue to stir and react for 1 hour, and remove the excess solvent by rotary evaporation to obtain benzophenone phosphorus silicon intermediate;

[0049] S14. Disperse 1 part of eugenol diene compound in DMF by weight, stir and disperse for 1 hour, add 1.5 parts of benzophenone phosphosilicone intermediate, continue mixing for 0.5 hour, crosslink the reaction system by ultraviolet irradiation for 30 minutes, add 0.81 parts of m-chloroperbenzoic acid, continue stirring and reacting for 24 hours, evaporate excess solvent, wash the precipitate with deionized water 3 times, mix the precipitate with 10 parts of epichlorohydrin, stir and mix for 30 minutes, add 0.05 parts of tetrabutylammonium bromide, continue mixing for 2 hours, heat to 95°C, continue reacting for 8 hours, and evaporate in vacuo to constant weight to obtain an environmentally friendly flame-retardant epoxy resin;

[0050] S2. By weight, 20 parts of environmentally friendly flame-retardant epoxy resin were heated to 80°C, 15 parts of E51 epoxy resin, 0.3 parts of p-hydroxyanisole inhibitor and 0.1 parts of triethylamine catalyst were added thereto, and mixed for 10 minutes. The temperature was then lowered to 35°C, 15 parts of hydroxyethyl methacrylate were added thereto, and the mixture was mixed for 5 minutes. Then, resorcinol diglycidyl ether and 0.5 parts of ethyl 2,4,6-trimethylbenzoylphenylphosphonate photoinitiator were added. The mixture was mixed for 4 minutes, and then the material was discharged to obtain an environmentally friendly flame-retardant photosensitive resin material.

[0051] Example 4. A method for preparing an environmentally friendly flame-retardant photosensitive resin material, comprising the following steps:

[0052] Compared with Example 1, this example increases the amount of benzophenone phosphosilicon intermediate added in step S14;

[0053] S1. Preparation of environmentally friendly flame-retardant epoxy resin;

[0054] S11. In terms of molar parts, 2 mol parts of eugenol were mixed with 85 wt % of phosphoric acid. After mixing for 15 min, the mixture was heated to 50 ° C. and kept warm for 30 min. Then, a formaldehyde solution containing 1.05 mol parts of formaldehyde was added dropwise thereto for 1 h. After the addition was completed, the temperature was raised to 90 ° C. After the reaction was kept warm for 6 h, the excess solvent was removed by rotary evaporation, and the precipitate was washed 4 times with deionized water. The remaining product was dispersed in toluene for recrystallization, filtered and dried to obtain a eugenol diene compound;

[0055] S12. According to the weight ratio, 1 part of trimethyltrihydrogencyclotrisiloxane was mixed with DMF, and after ultrasonic vibration dispersion for 10 minutes, 0.003 parts of Raney nickel was added, and the mixture was mixed for 2 minutes, and then cooled to 5°C, and 2.1 parts of bistrimethylsilyl vinyl phosphate were added dropwise thereto for 1 hour. After the addition was completed, the temperature was raised to 80°C, and after reflux reaction for 8 hours, the excess solvent was removed by rotary evaporation, and the precipitate was washed with a hydrochloric acid solution at a temperature of 4°C, and then the precipitate was washed twice with DMF, and then vacuum dried to constant weight to obtain a phosphorus silicon intermediate;

[0056] S13. In parts by weight, one portion of the phosphorus silicon intermediate prepared in step S12 was dispersed in DMF, ultrasonically mixed for 30 min, cooled to 5 ° C, and set aside;

[0057] Disperse 0.3 parts of L-lysine diisocyanate in pure DMF, stir and mix for 15 minutes, cool to 10°C, add dropwise DMF dispersion containing phosphosilicate intermediate for 1 hour, heat to 85°C after the addition, stir and react for 3 hours, cool to 45°C, add 0.25 parts of 4-aminobenzophenone, continue to stir and react for 1 hour, and remove excess solvent by rotary evaporation to obtain benzophenone phosphosilicate intermediate;

[0058] S14. Disperse 1 part of eugenol diene compound in DMF by weight, stir and disperse for 1 hour, add 3.1 parts of benzophenone phosphosilicon intermediate, continue mixing for 0.5 hour, crosslink the reaction system by ultraviolet irradiation for 30 minutes, add 0.81 parts of m-chloroperbenzoic acid, continue stirring and reacting for 24 hours, evaporate excess solvent, wash the precipitate with deionized water for 3 times, mix the precipitate with 10 parts of epichlorohydrin, stir and mix for 30 minutes, add 0.05 parts of tetrabutylammonium bromide, continue mixing for 2 hours, heat to 95°C, continue reacting for 8 hours, and evaporate in vacuo to constant weight to obtain an environmentally friendly flame-retardant epoxy resin;

[0059] S2. By weight, 20 parts of environmentally friendly flame-retardant epoxy resin were heated to 80°C, 15 parts of E51 epoxy resin, 0.3 parts of p-hydroxyanisole inhibitor and 0.1 parts of triethylamine catalyst were added thereto, and mixed for 10 minutes. The temperature was then lowered to 35°C, 15 parts of hydroxyethyl methacrylate were added thereto, and the mixture was mixed for 5 minutes. Then, resorcinol diglycidyl ether and 0.5 parts of ethyl 2,4,6-trimethylbenzoylphenylphosphonate photoinitiator were added. The mixture was mixed for 4 minutes, and then the material was discharged to obtain an environmentally friendly flame-retardant photosensitive resin material.

[0060] Example 5. A method for preparing an environmentally friendly flame-retardant photosensitive resin material, comprising the following steps:

[0061] Compared with Example 1, this embodiment increases the amount of environmentally friendly flame-retardant epoxy resin added in step S2;

[0062] S1. Preparation of environmentally friendly flame-retardant epoxy resin;

[0063] S11. In terms of molar parts, 2 mol parts of eugenol were mixed with 85 wt % of phosphoric acid. After mixing for 15 min, the mixture was heated to 50 ° C. and kept warm for 30 min. Then, a formaldehyde solution containing 1.05 mol parts of formaldehyde was added dropwise thereto for 1 h. After the addition was completed, the temperature was raised to 90 ° C. After the reaction was kept warm for 6 h, the excess solvent was removed by rotary evaporation, and the precipitate was washed 4 times with deionized water. The remaining product was dispersed in toluene for recrystallization, filtered and dried to obtain a eugenol diene compound;

[0064] S12. According to the weight ratio, 1 part of trimethyltrihydrogencyclotrisiloxane was mixed with DMF, and after ultrasonic vibration dispersion for 10 minutes, 0.003 parts of Raney nickel was added, and the mixture was mixed for 2 minutes, and then cooled to 5°C, and 2.1 parts of bistrimethylsilyl vinyl phosphate were added dropwise thereto for 1 hour. After the addition was completed, the temperature was raised to 80°C, and after reflux reaction for 8 hours, the excess solvent was removed by rotary evaporation, and the precipitate was washed with a hydrochloric acid solution at a temperature of 4°C, and then the precipitate was washed twice with DMF, and then vacuum dried to constant weight to obtain a phosphorus silicon intermediate;

[0065] S13. In parts by weight, one portion of the phosphorus silicon intermediate prepared in step S12 was dispersed in DMF, ultrasonically mixed for 30 min, cooled to 5 ° C, and set aside;

[0066] Disperse 0.3 parts of L-lysine diisocyanate in pure DMF, stir and mix for 15 minutes, cool to 10°C, add dropwise DMF dispersion containing phosphosilicate intermediate for 1 hour, heat to 85°C after the addition, stir and react for 3 hours, cool to 45°C, add 0.25 parts of 4-aminobenzophenone, continue to stir and react for 1 hour, and remove excess solvent by rotary evaporation to obtain benzophenone phosphosilicate intermediate;

[0067] S14. Disperse 1 part of eugenol diene compound in DMF by weight, stir and disperse for 1 hour, add 1.5 parts of benzophenone phosphosilicone intermediate, continue mixing for 0.5 hour, crosslink the reaction system by ultraviolet irradiation for 30 minutes, add 0.81 parts of m-chloroperbenzoic acid, continue stirring and reacting for 24 hours, evaporate excess solvent, wash the precipitate with deionized water 3 times, mix the precipitate with 10 parts of epichlorohydrin, stir and mix for 30 minutes, add 0.05 parts of tetrabutylammonium bromide, continue mixing for 2 hours, heat to 95°C, continue reacting for 8 hours, and evaporate in vacuo to constant weight to obtain an environmentally friendly flame-retardant epoxy resin;

[0068] S2. By weight, 30 parts of environmentally friendly flame-retardant epoxy resin were heated to 80°C, 15 parts of E51 epoxy resin, 0.3 parts of p-hydroxyanisole inhibitor and 0.1 parts of triethylamine catalyst were added thereto, and mixed for 10 minutes, then cooled to 35°C, 15 parts of hydroxyethyl methacrylate were added thereto, and mixed for 5 minutes, then resorcinol diglycidyl ether and 0.5 parts of 2,4,6-trimethylbenzoylphenylphosphonic acid ethyl ester photoinitiator were added, and mixed for 4 minutes, then the material was discharged to obtain an environmentally friendly flame-retardant photosensitive resin material.

[0069] Comparative Example 1. A method for preparing an environmentally friendly flame-retardant photosensitive resin material, comprising the following steps:

[0070] Compared with Example 1, this comparative example did not prepare an environmentally friendly flame-retardant epoxy resin, but only used E51 resin;

[0071] By weight, 35 parts of E51 epoxy resin were heated to 80°C, 0.3 parts of p-hydroxyanisole inhibitor and 0.1 parts of triethylamine catalyst were added thereto, mixed for 10 minutes, cooled to 35°C, 15 parts of hydroxyethyl methacrylate were added thereto, mixed for 5 minutes, resorcinol diglycidyl ether and 0.5 parts of 2,4,6-trimethylbenzoylphenylphosphonic acid ethyl ester photoinitiator were added, mixed for 4 minutes, and then discharged to obtain an environmentally friendly flame-retardant photosensitive resin material.

[0072] Comparative Example 2. A method for preparing an environmentally friendly flame-retardant photosensitive resin material, comprising the following steps:

[0073] Compared with Example 1, epichlorohydrin was not used for treatment in step S14 of this comparative example;

[0074] S1. Preparation of environmentally friendly flame-retardant epoxy resin;

[0075] S11. In terms of molar parts, 2 mol parts of eugenol were mixed with 85 wt % of phosphoric acid. After mixing for 15 min, the mixture was heated to 50 ° C. and kept warm for 30 min. Then, a formaldehyde solution containing 1.05 mol parts of formaldehyde was added dropwise thereto for 1 h. After the addition was completed, the temperature was raised to 90 ° C. After the reaction was kept warm for 6 h, the excess solvent was removed by rotary evaporation, and the precipitate was washed 4 times with deionized water. The remaining product was dispersed in toluene for recrystallization, filtered and dried to obtain a eugenol diene compound;

[0076] S12. According to the weight ratio, 1 part of trimethyltrihydrogencyclotrisiloxane was mixed with DMF, and after ultrasonic vibration dispersion for 10 minutes, 0.003 parts of Raney nickel was added, and the mixture was mixed for 2 minutes, and then cooled to 5°C, and 2.1 parts of bistrimethylsilyl vinyl phosphate were added dropwise thereto for 1 hour. After the addition was completed, the temperature was raised to 80°C, and after reflux reaction for 8 hours, the excess solvent was removed by rotary evaporation, and the precipitate was washed with a hydrochloric acid solution at a temperature of 4°C, and then the precipitate was washed twice with DMF, and then vacuum dried to constant weight to obtain a phosphorus silicon intermediate;

[0077] S13. In parts by weight, one portion of the phosphorus silicon intermediate prepared in step S12 was dispersed in DMF, ultrasonically mixed for 30 min, cooled to 5 ° C, and set aside;

[0078] Disperse 0.3 parts of L-lysine diisocyanate in pure DMF, stir and mix for 15 minutes, cool to 10°C, add dropwise DMF dispersion containing phosphosilicate intermediate for 1 hour, heat to 85°C after the addition, stir and react for 3 hours, cool to 45°C, add 0.25 parts of 4-aminobenzophenone, continue to stir and react for 1 hour, and remove excess solvent by rotary evaporation to obtain benzophenone phosphosilicate intermediate;

[0079] S14. By weight, 1 part of eugenol diene compound was dispersed in DMF, and after stirring and dispersing for 1 hour, 1.5 parts of benzophenone phosphorus silicon intermediate was added, and the mixture was mixed for 0.5 hours. After the reaction system was cross-linked by ultraviolet irradiation for 30 minutes, 0.81 parts of m-chloroperbenzoic acid was added thereto, and the reaction was stirred for 24 hours, and then vacuum evaporated to constant weight to obtain an environmentally friendly flame-retardant epoxy resin;

[0080] S2. By weight, 20 parts of environmentally friendly flame-retardant epoxy resin were heated to 80°C, 15 parts of E51 epoxy resin, 0.3 parts of p-hydroxyanisole inhibitor and 0.1 parts of triethylamine catalyst were added thereto, and mixed for 10 minutes. The temperature was then lowered to 35°C, 15 parts of hydroxyethyl methacrylate were added thereto, and the mixture was mixed for 5 minutes. Then, resorcinol diglycidyl ether and 0.5 parts of ethyl 2,4,6-trimethylbenzoylphenylphosphonate photoinitiator were added. The mixture was mixed for 4 minutes, and then the material was discharged to obtain an environmentally friendly flame-retardant photosensitive resin material.

[0081] Testing: After the products prepared in Examples 1-5 and Comparative Examples 1-2 were cured under 265 nm ultraviolet light for 25 min, product performance testing was performed on them;

[0082] The samples prepared in Examples 1-5 and Comparative Examples 1-2 were tested for Shore hardness according to ASTMD 2240-2005; the samples prepared in Examples 1-5 and Comparative Examples 1-2 were tested for tensile strength according to ASTMD638; the samples prepared in Examples 1-5 and Comparative Examples 1-2 were tested for limiting oxygen index according to GB / T2406.1-2008; the test results are shown in the following table;

[0083]

[0084] Finally, it should be noted that the above description is only a preferred embodiment of the present invention and is not intended to limit the present invention. Although the present invention has been described in detail with reference to the aforementioned embodiments, those skilled in the art can still modify the technical solutions described in the aforementioned embodiments or replace some of the technical features therein by equivalents. Any modification, equivalent replacement, improvement, etc. made within the spirit and principle of the present invention shall be included in the protection scope of the present invention.

Claims

1. A method for preparing an environmentally friendly flame-retardant photosensitive resin material, characterized in that: The following steps are involved: S1. Preparation of environmentally friendly flame-retardant epoxy resin; S11. Mix eugenol with 85 wt % phosphoric acid for 15-30 min, heat the mixture to 50-55° C., keep the mixture warm for 30 min, then drop a formaldehyde solution therein for 1-2 h. After the addition is complete, heat the mixture to 88-95° C., keep the mixture warm for 5-8 h, remove excess solvent by rotary evaporation, wash the precipitate with deionized water for 2-5 times, disperse the remaining product in toluene for recrystallization, filter and dry to obtain a eugenol diene compound; S12. Trimethyltrihydrogencyclotrisiloxane is mixed with DMF, and after ultrasonic oscillation dispersion for 10-15 minutes, Raney nickel is added, and the mixture is mixed for 1-3 minutes. After cooling to 5-10°C, bistrimethylsilyl vinyl phosphate is added dropwise for 1-2 hours. After the addition is completed, the mixture is heated to 75-85°C, and refluxed for 2-12 hours. The excess solvent is removed by rotary evaporation, and the precipitate is washed with a hydrochloric acid solution at a temperature of 2-4°C, and the precipitate is washed again with DMF for 2-3 times, and then vacuum dried to constant weight to obtain a phosphorus silicon intermediate; S13. The phosphorus silicon intermediate prepared in step S12 is dispersed in DMF, mixed by ultrasonic oscillation for 30-45 min, cooled to 5-10 ° C, and set aside; Disperse L-lysine diisocyanate in pure DMF, stir and mix for 15-30 minutes, cool to 5-15°C, add dropwise a DMF dispersion containing a phosphorus silicon intermediate for 1-2 hours, heat to 85-92°C after the addition is completed, stir and react for 2-4 hours, cool to 45-50°C, add 4-aminobenzophenone, continue to stir and react for 1-4 hours, and remove excess solvent by rotary evaporation to obtain a benzophenone phosphorus silicon intermediate; S14. Disperse the eugenol diene compound in DMF, stir and disperse for 1-2 hours, add benzophenone phosphosilicon intermediate, continue mixing for 0.5-1 hour, perform UV irradiation cross-linking on the reaction system for 15-45 minutes, add m-chloroperbenzoic acid thereto, continue stirring and reacting for 24-48 hours, evaporate excess solvent, wash the precipitate with deionized water for 3-5 times, mix the precipitate with epichlorohydrin, stir and mix for 30-45 minutes, add tetrabutylammonium bromide, continue mixing for 1-2 hours, heat to 85-95°C, continue reacting for 4-8 hours, and evaporate in vacuo to constant weight to obtain an environmentally friendly flame-retardant epoxy resin; S2. The environmentally friendly flame-retardant epoxy resin is heated to 80-90°C, E51 epoxy resin, polymerization inhibitor and catalyst are added thereto, mixed for 10-15 minutes, cooled to 30-55°C, acrylate is added thereto, mixed for 5-10 minutes, diluent monomer and photoinitiator are added thereto, mixed for 3-5 minutes, and then discharged to obtain an environmentally friendly flame-retardant photosensitive resin material; Wherein, the acrylic acid ester is any one or more of hydroxyethyl acrylate, 4-hydroxybutyl acrylate, and hydroxyethyl methacrylate.

2. The method for preparing an environmentally friendly flame-retardant photosensitive resin material according to claim 1, characterized in that: In terms of molar ratio, in step S11, the molar ratio of eugenol to formaldehyde is 2:1.

05.

3. The method for preparing an environmentally friendly flame-retardant photosensitive resin material according to claim 1, characterized in that: In step S12, the mass ratio of trimethyltrihydrogencyclotrisiloxane, Raney nickel, and bistrimethylsilylated vinyl phosphate is 1: (0.001-0.003): (2.1-2.8).

4. The method for preparing an environmentally friendly flame-retardant photosensitive resin material according to claim 1, characterized in that: In step S13, the mass ratio of the phosphorus silicon intermediate, L-lysine diisocyanate, and 4-aminobenzophenone is 1: (0.3-0.33): (0.25-0.29).

5. The method for preparing an environmentally friendly flame-retardant photosensitive resin material according to claim 1, characterized in that: In step S14, the mass ratio of the eugenol diene compound, the benzophenone phosphosilicone intermediate, and the meta-chloroperbenzoic acid is 1:(1.5-3.1):(0.81-0.96).

6. The method for preparing an environmentally friendly flame-retardant photosensitive resin material according to claim 1, characterized in that: In step S14, the mass ratio of the eugenol diene compound to epichlorohydrin is 1:(10-30).

7. The method for preparing an environmentally friendly flame-retardant photosensitive resin material according to claim 1, characterized in that: In step S2, the environmentally friendly flame-retardant photosensitive resin material is composed of 20-30 parts of environmentally friendly flame-retardant epoxy resin, 15-25 parts of E51 epoxy resin, 15-25 parts of acrylate, 15-40 parts of diluent monomer, 0.3-0.8 parts of photoinitiator, 0.1-0.5 parts of inhibitor and 0.1-0.3 parts of catalyst in parts by weight.

8. The method for preparing an environmentally friendly flame-retardant photosensitive resin material according to claim 1, characterized in that: In step S2, the diluent monomer is resorcinol diglycidyl ether; the inhibitor is p-hydroxyanisole; the catalyst is triethylamine; and the photoinitiator is ethyl 2,4,6-trimethylbenzoylphenylphosphonate.

9. An environmentally friendly flame-retardant photosensitive resin material prepared by the preparation method according to any one of claims 1 to 8.

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