Weather-resistant flame-retardant degradable resin and preparation method thereof
By introducing curing agents and flame retardants with specific structures into epoxy resins, the shortcomings of traditional epoxy resins in terms of weather resistance and flame retardancy have been solved, and high-performance weather-resistant, flame-retardant, and biodegradable resins have been prepared.
Patent Information
- Authority / Receiving Office
- CN · China
- Patent Type
- Patents(China)
- Current Assignee / Owner
- XIAMEN JINSHANG RESIN CO LTD
- Filing Date
- 2026-03-12
- Publication Date
- 2026-06-09
AI Technical Summary
Traditional epoxy resins are prone to aging under ultraviolet light and oxidizing environments, resulting in mechanical property degradation, yellowing and embrittlement, and are also flammable, making it difficult to meet the application requirements for weather resistance and flame retardancy.
A weather-resistant, flame-retardant, and biodegradable resin was prepared by using a four-arm primary amine curing agent containing a rigid naphthalene ring, a dynamic Diels-Alder structure, and a flexible long alkyl chain, and by adding a flame retardant and anti-aging agent, through the synergistic effect of phosphoramide, benzotriazole, and siloxane structures.
It improves the mechanical properties, aging resistance, and flame retardancy of the resin, while also achieving biodegradability and enhancing the resin's stability and safety.
Smart Images
Figure CN121801057B_ABST
Abstract
Description
Technical Field
[0001] This invention relates to the field of polymer materials technology, specifically to a weather-resistant, flame-retardant, and biodegradable resin and its preparation method. Background Technology
[0002] Epoxy resins are widely used in electronic packaging, building materials, and composite materials due to their excellent mechanical properties, bonding properties, electrical insulation properties, and chemical corrosion resistance. However, traditional epoxy resins still have certain limitations in practical applications: on the one hand, their highly cross-linked molecular structure and stable chemical bonds make them difficult to degrade after curing, which is not conducive to the sustainable use of materials; on the other hand, epoxy resins are prone to aging under ultraviolet light and oxidizing environments, exhibiting mechanical property degradation, yellowing, and embrittlement, and are inherently flammable, making it difficult to meet the increasingly demanding application requirements for flame retardancy and weather resistance. Therefore, developing an epoxy resin material that combines weather resistance, flame retardancy, and biodegradability is of great significance.
[0003] Chinese invention patent application CN119798922A discloses a biodegradable epoxy resin composition, a winding resin, its application, and a preparation method. The biodegradable epoxy resin composition of this invention, by weight, comprises 40-100 parts epoxy resin, 0-20 parts modified epoxy resin, and 0-60 parts biodegradable epoxy resin, with the weight percentage not being zero. The biodegradable winding resin composite material prepared from this invention's biodegradable epoxy resin composition can degrade under mild conditions, peel off reinforcing fibers, and achieve recycling, reducing environmental pressure. This invention utilizes the biodegradable epoxy resin composition in conjunction with an anhydride curing agent and a defoamer to enable the application of epoxy resin in the winding process. The prepared composite material exhibits excellent water resistance and high-temperature resistance. This invention's biodegradable winding resin composite material also has flame-retardant properties and good tensile and shear strength, but its anti-aging properties are still insufficient. Summary of the Invention
[0004] To address the shortcomings of existing technologies, the purpose of this invention is to provide a weather-resistant, flame-retardant, and biodegradable resin and its preparation method.
[0005] To achieve the above objectives, the present invention provides the following technical solution:
[0006] A weather-resistant, flame-retardant, and biodegradable resin comprises the following raw materials in parts by weight:
[0007] 60-80 parts epoxy resin, 1-2 parts silane coupling agent, 5-7 parts flame retardant and anti-aging agent, 12-15 parts filler, 15-25 parts curing agent, and 0.5-1 part curing accelerator;
[0008] The curing agent is a four-arm primary amine curing agent containing a rigid naphthalene ring, a dynamic Diels-Alder structure, and a flexible long alkyl chain, and is prepared by the following method:
[0009] S1: 2,6-Naphthyldimethylamine reacts with maleic anhydride to produce intermediate 1; the reaction equation is shown below:
[0010]
[0011] S2: Intermediate 1 reacts with 2,5-furandimethyl to form intermediate 2; the reaction equation is shown below:
[0012]
[0013] S3: Intermediate 2 reacts with 10-aminodecanoic acid to generate a curing agent. The reaction equation is shown below:
[0014]
[0015] In step S1, the molar ratio of 2,6-naphthyldimethylamine to maleic anhydride is 1:(2.05-2.1).
[0016] In step S2, the molar ratio of intermediate 1 to 2,5-furandiethanol is 1:(2.03-2.05).
[0017] In step S3, the molar ratio of intermediate 2 to 10-aminodecanoic acid is 1:(4.05-4.1).
[0018] The flame retardant and antioxidant is prepared by the following method:
[0019] N1: 3,9-Dichloro-2,4,8,10-tetraoxa-3,9-diphosphaspiro[5.5]undecane 3,9-dioxide reacts with p-aminobenzoic acid to generate intermediate A; the reaction equation is shown below:
[0020]
[0021] N2: Benzotriazol-1-ylmethylamine reacts with 3-(2,3-epoxypropoxy)propyltrimethoxysilane to generate intermediate B; the reaction equation is shown below.
[0022]
[0023] N3: Intermediate A reacts with intermediate B to produce a flame retardant and antioxidant. The reaction equation is shown below:
[0024]
[0025] In step N1, the molar ratio of 3,9-dichloro-2,4,8,10-tetraoxa-3,9-diphosphaspiro[5.5]undecane 3,9-dioxide to p-aminobenzoic acid is 1:2.1; in step N2, the molar ratio of benzotriazol-1-ylmethylamine to 3-(2,3-epoxypropoxy)propyltrimethoxysilane is 1:1.05; in step N3, the molar ratio of intermediate A to intermediate B is 1:2.05.
[0026] The silane coupling agent is silane coupling agent KH-550; the filler is silica; and the curing accelerator is 2-ethyl-4-methylimidazolium.
[0027] A method for preparing a weather-resistant, flame-retardant, and biodegradable resin includes the following steps:
[0028] (1) Weigh out the following by weight: 60-80 parts epoxy resin, 1-2 parts silane coupling agent, 5-7 parts flame retardant and anti-aging agent, 12-15 parts filler, 15-25 parts curing agent, and 0.5-1 parts curing accelerator.
[0029] (2) Heat and stir the epoxy resin, silane coupling agent, flame retardant and anti-aging agent and filler until they are evenly mixed, then cool down, add curing agent and curing accelerator, stir and mix until evenly mixed, place in a mold for curing, cool and demold to obtain weather-resistant flame retardant and biodegradable resin.
[0030] Due to the adoption of the above technical solutions, the beneficial effects of the present invention include:
[0031] The weather-resistant, flame-retardant, and biodegradable resin prepared by this invention has excellent mechanical properties, aging resistance, flame retardancy, and degradation properties. The added curing agent improves the mechanical properties and degradation properties of the resin through the synergistic effect of naphthalene rings, dynamic Diels-Alder structures, long-chain alkyl groups, and amino groups. The added flame retardant and antioxidant improves the flame retardancy and aging resistance of the resin through the synergistic effect of phosphoramide, benzotriazole, and siloxane structures. Attached Figure Description
[0032] Figure 1 The image shows the proton NMR spectrum of the curing agent prepared in Example 1.
[0033] Figure 2 The nuclear magnetic resonance hydrogen spectrum of the flame retardant and anti-aging agent prepared in Example 4. Detailed Implementation
[0034] The following description, in conjunction with specific embodiments, provides further details, but the present invention is not limited to these embodiments.
[0035] Example 1: Preparation of curing agent:
[0036] S1: 100 ml of dichloromethane and 0.205 mol of maleic anhydride were stirred and mixed. Under ice bath conditions, 120 ml of a dichloromethane solution containing 0.1 mol of 2,6-naphthyldimethylamine was slowly added dropwise over 2 hours. The mixture was then heated to 25°C and reacted for 20 hours. After distillation under reduced pressure at 30°C for 1 hour, 200 ml of acetone, 0.4 mmol of acetic anhydride, 2 mmol of nickel acetate, and 0.04 mol of triethylamine were added and stirred until mixed. The mixture was then refluxed for 48 hours. After cooling to room temperature, the mixture was distilled under reduced pressure at 35°C for 1 hour. 180 ml of ice water was slowly added and stirred to precipitate the product. The product was filtered, and the filter cake was washed with deionized water (3 × 30 ml). The product was then dried under vacuum at 60°C for 12 hours to obtain intermediate 1. Its 1H NMR data are as follows: 1 H NMR (400 MHz, DMSO- d 6 ) δ 7.83 (d, J = 7.4 Hz, 4H), 7.34 (s, 2H), 6.91 (s, 4H), 4.94 (s, 4H); HRMS(m / z):347.0946[M+H] + ;
[0037] S2: Under nitrogen protection, 300 ml of anhydrous ethanol, 0.1 mol of intermediate 1, and 0.203 mol of 2,5-furandimethylethanol were stirred and mixed. The mixture was heated to 70 °C and reacted for 24 h. After cooling to room temperature, the mixture was distilled under reduced pressure at 50 °C for 1 h. The crude product was purified by silica gel column chromatography (V... 二氯甲烷 :V 甲醇 The ratio of distillation solution to intermediate 2 was 50:1. The intermediate was distilled under reduced pressure at 30°C for 1 hour to obtain intermediate 2. Its 1H NMR data are as follows: 1 H NMR (400MHz, DMSO- d 6 ) δ 7.84 (s, 2H), 7.76 (s, 2H), 7.35 (s, 2H), 6.19 (s, 4H), 4.64(d, J = 12.4 Hz, 4H), 4.61-4.53 (m, 4H), 4.02-3.75 (m, 8H), 2.89 (s, 4H); HRMS(m / z):603.1911[M+H] + ;
[0038] S3: Under nitrogen protection, 70 ml of DMF (N,N-dimethylformamide), 0.0405 mol of 10-aminodecanoic acid, and 0.06 mol of triethylamine were stirred and mixed. Under ice bath conditions, 60 ml of a DMF solution containing 0.042 mol of fluorenyl chloroformate was slowly added dropwise over 30 min. After the addition was complete, the mixture was stirred at 25 °C for 12 h. Then, 0.042 mol of dicyclohexylcarbodiimide and 0.008 mol of 4-dimethylaminopyridine were added and stirred for 15 min. 0.01 mol of intermediate 2 was added, and the mixture was reacted at 25 °C for 18 h. After filtration, the reaction solution was poured into 300 ml of an ice-water mixture (containing 25 ml of 1 M HCl) and stirred for 30 min. Extraction was performed using ethyl acetate (3 × 250 ml). The combined organic phases were washed with 150 ml of saturated brine, dried over 60 g of anhydrous magnesium sulfate, filtered, and concentrated under reduced pressure at 50 °C for 1 h to obtain a concentrated solution. The concentrated solution was added to 200 ml of… In a mixed solution of DMF and piperidine (V DMF :V 哌啶 =4:1), stir at 25℃ for 35 min to deprotect, then pour into 300 ml of 0.5 M HCl solution at 0℃, stir to precipitate, filter, wash successively with 50 ml of cold water and 50 ml of 5 wt% sodium bicarbonate solution, and vacuum dry at 60℃ for 12 h to obtain the curing agent; its 1H NMR spectrum is shown below. Figure 1 As shown, the proton NMR data are as follows: 1 H NMR (400 MHz, DMSO-) d 6 ) δ 7.84 (s, 2H), 7.76 (s, 2H), 7.35 (s, 2H), 6.32 (s, 4H), 4.74-4.53 (m, 12H), 3.02 (s, 4H), 2.76-2.63 (m, 8H), 2.29 (s, 8H), 1.93 (dt,J = 11.7, 2.6 Hz, 8H), 1.55 (d, J = 12.9 Hz, 16H), 1.33-1.26 (m, 40H); HRMS(m / z):1279.7761[M+H] + .
[0039] Example 2: Preparation of curing agent:
[0040] S1: Mix 100 ml of dichloromethane and 0.208 mol of maleic anhydride. Under ice bath conditions, slowly add 120 ml of dichloromethane solution containing 0.1 mol of 2,6-naphthyldimethylamine dropwise over 2 hours. After the addition is complete, heat to 25°C and react for 20 hours. Distill under reduced pressure at 30°C for 1 hour. Add 200 ml of acetone, 0.4 mmol of acetic anhydride, 2 mmol of nickel acetate, and 0.04 mol of triethylamine. Stir and mix well. Reflux for 48 hours. Cool to room temperature and distill under reduced pressure at 35°C for 1 hour. Slowly add 180 ml of ice water and stir to precipitate the precipitate. Filter and wash the filter cake with deionized water (3 × 30 ml). Dry under vacuum at 60°C for 12 hours to obtain intermediate 1.
[0041] S2: Under nitrogen protection, 300 ml of anhydrous ethanol, 0.1 mol of intermediate 1, and 0.204 mol of 2,5-furandimethylethanol were stirred and mixed. The mixture was heated to 70 °C and reacted for 24 h. After cooling to room temperature, the mixture was distilled under reduced pressure at 50 °C for 1 h. The crude product was purified by silica gel column chromatography (V... 二氯甲烷 :V 甲醇 =50:1), distilled under reduced pressure at 30℃ for 1 h to obtain intermediate 2;
[0042] S3: Under nitrogen protection, 70 ml of DMF (N,N-dimethylformamide), 0.0408 mol of 10-aminodecanoic acid, and 0.06 mol of triethylamine were stirred and mixed. Under ice bath conditions, 60 ml of a DMF solution containing 0.042 mol of fluorenyl chloroformate was slowly added dropwise over 30 min. After the addition was complete, the mixture was stirred at 25 °C for 12 h. Then, 0.042 mol of dicyclohexylcarbodiimide and 0.008 mol of 4-dimethylaminopyridine were added and stirred for 15 min. 0.01 mol of intermediate 2 was added, and the mixture was reacted at 25 °C for 18 h. After filtration, the reaction solution was poured into 300 ml of an ice-water mixture (containing 25 ml of 1 M HCl) and stirred for 30 min. Extraction was performed using ethyl acetate (3 × 250 ml). The combined organic phases were washed with 150 ml of saturated brine, dried over 60 g of anhydrous magnesium sulfate, filtered, and concentrated under reduced pressure at 50 °C for 1 h to obtain a concentrated solution. The concentrated solution was added to 200 ml of… In a mixed solution of DMF and piperidine (V DMF :V 哌啶 =4:1), stir at 25℃ for 35 min to remove protection, then pour into 300 ml of 0.5 M HCl solution at 0℃, stir to precipitate, filter, wash successively with 50 ml of cold water and 50 ml of 5 wt% sodium bicarbonate solution, and vacuum dry at 60℃ for 12 h to obtain curing agent.
[0043] Example 3: Preparation of curing agent:
[0044] S1: Mix 100 ml of dichloromethane and 0.21 mol of maleic anhydride. Under ice bath conditions, slowly add 120 ml of dichloromethane solution containing 0.1 mol of 2,6-naphthyldimethylamine dropwise over 2 hours. After the addition is complete, heat to 30°C and react for 19 hours. Distill under reduced pressure at 30°C for 1 hour. Add 200 ml of acetone, 0.4 mmol of acetic anhydride, 2 mmol of nickel acetate, and 0.04 mol of triethylamine. Stir and mix well. Reflux for 48 hours. Cool to room temperature and distill under reduced pressure at 35°C for 1 hour. Slowly add 180 ml of ice water and stir to precipitate the precipitate. Filter the precipitate and wash it with deionized water (3 × 30 ml). Dry under vacuum at 60°C for 12 hours to obtain intermediate 1.
[0045] S2: Under nitrogen protection, 300 ml of anhydrous ethanol, 0.1 mol of intermediate 1, and 0.205 mol of 2,5-furandiethanol were stirred and mixed. The mixture was heated to 75 °C and reacted for 23 h. After cooling to room temperature, the mixture was distilled under reduced pressure at 50 °C for 1 h. The crude product was purified by silica gel column chromatography (V... 二氯甲烷 :V 甲醇 =50:1), distilled under reduced pressure at 30℃ for 1 h to obtain intermediate 2;
[0046] S3: Under nitrogen protection, 70 ml of DMF (N,N-dimethylformamide), 0.041 mol of 10-aminodecanoic acid, and 0.06 mol of triethylamine were stirred and mixed. Under ice bath conditions, 60 ml of a DMF solution containing 0.042 mol of fluorenyl chloroformate was slowly added dropwise over 30 min. After the addition was complete, the mixture was stirred at 25 °C for 12 h. Then, 0.042 mol of dicyclohexylcarbodiimide and 0.008 mol of 4-dimethylaminopyridine were added and stirred for 15 min. 0.01 mol of intermediate 2 was added, and the mixture was reacted at 30 °C for 17 h. After filtration, the reaction solution was poured into 300 ml of an ice-water mixture (containing 25 ml of 1 M HCl) and stirred for 30 min. Extraction was performed using ethyl acetate (3 × 250 ml). The combined organic phases were washed with 150 ml of saturated brine, dried over 60 g of anhydrous magnesium sulfate, filtered, and concentrated under reduced pressure at 50 °C for 1 h to obtain a concentrated solution. The concentrated solution was added to 200 ml of… In a mixed solution of DMF and piperidine (V DMF :V 哌啶 =4:1), stir at 25℃ for 35 min to remove protection, then pour into 300 ml of 0.5 M HCl solution at 0℃, stir to precipitate, filter, wash successively with 50 ml of cold water and 50 ml of 5 wt% sodium bicarbonate solution, and vacuum dry at 60℃ for 12 h to obtain curing agent.
[0047] Example 4: Preparation of flame retardant and antioxidant:
[0048] N1: 400 ml of tetrahydrofuran, 0.1 mol of 3,9-dichloro-2,4,8,10-tetraoxa-3,9-diphosphaspiro[5.5]undecane 3,9-dioxide, and 0.21 mol of p-aminobenzoic acid were stirred and mixed. 0.21 mol of triethylamine was added, and the mixture was reacted at 50 °C for 8 h. After cooling to room temperature, the mixture was filtered and distilled under reduced pressure at 40 °C for 1 h. The crude product was purified by silica gel column chromatography (V... 石油醚 :V 乙酸乙酯 The mixture was distilled at 50°C under reduced pressure for 1 hour (r=1:1) to obtain intermediate A; its 1H NMR data are as follows: 1 H NMR (400 MHz, DMSO- d 6 ) δ 12.17 (s,2H), 8.26 (s, 2H), 7.94-7.86 (m, 4H), 7.35-7.27 (m, 4H), 4.06 (d, J = 14.6Hz, 8H); HRMS (m / z):499.0587[M+H] + ;
[0049] Under nitrogen protection, 200 ml of anhydrous acetonitrile and 0.1 mol of benzotriazol-1-ylmethylamine were stirred and mixed. 0.105 mol of 3-(2,3-epoxypropoxy)propyltrimethoxysilane was slowly added dropwise over 60 min. The mixture was then heated to 65 °C and reacted for 8 h. After cooling to room temperature, the mixture was distilled under reduced pressure at 50 °C for 1 h. 150 ml of cold anhydrous n-hexane was added and stirred to precipitate the precipitate. The precipitate was filtered, washed with cold anhydrous n-hexane (3 × 30 ml), and dried under vacuum at 50 °C for 8 h to obtain intermediate B. Its 1H NMR data are as follows: 1 H NMR (400 MHz, DMSO- d 6 ) δ 7.93 (d, J = 1.5 Hz, 1H), 7.67 (d, J = 1.6 Hz, 1H), 7.46 (d, J =12.9 Hz, 2H), 5.21-5.10 (m, 2H), 4.66 (d, J = 5.0 Hz, 1H), 3.89 (d, J = 5.0Hz, 1H), 3.80 (t, J = 1.5 Hz, 1H), 3.52 (s, 9H), 3.49-3.29 (m, 4H), 2.92-2.80(m, 2H), 1.77-1.59 (m, 2H), 1.12-0.98 (m, 2H); HRMS (m / z): 385.1821 [M+H] + ;
[0050] Under nitrogen protection, 850 ml of anhydrous tetrahydrofuran, 0.1 mol of intermediate A, 0.21 mol of dicyclohexylcarbodiimide, and 0.04 mol of 4-dimethylaminopyridine were mixed and stirred for 15 min. Then, 0.205 mol of intermediate B was added, and the mixture was reacted at 25 °C for 18 h. After filtration, the mixture was concentrated under reduced pressure at 40 °C for 2 h. The crude product was purified by silica gel column chromatography (V... 二氯甲烷 :V 甲醇 The ratio of the sample to the solvent (10:1) was 40℃ under reduced pressure for 1 hour to obtain a flame retardant and antioxidant; its proton NMR spectrum is shown below. Figure 2 As shown, the proton NMR data are as follows: 1 H NMR (400 MHz, DMSO- d 6 ) δ8.26 (s, 2H), 7.95-7.87 (m, 6H), 7.66 (d, J = 1.5 Hz, 2H), 7.46 (d, J = 13.9Hz, 4H), 7.41-7.34 (m, 4H), 5.23 (dd, J = 1.9, 1.5 Hz, 4H), 4.86 (s, 2H), 4.17 (s, 4H), 3.96 (s, 4H), 3.72 (d, J = 3.2 Hz, 4H), 3.55-3.53 (m, 2H), 3.52(s, 18H), 3.47 (d, J = 12.4 Hz, 4H), 3.06-2.94 (m, 4H), 1.76-1.60 (m, 4H),1.12-0.97 (m, 4H); HRMS (m / z):1231.4037[M+H] + .
[0051] Example 5: Preparation of weather-resistant, flame-retardant, and biodegradable resin:
[0052] (1) Weigh the following by weight: 60g epoxy resin, 1g silane coupling agent (silane coupling agent KH-550), 5g flame retardant and antioxidant (prepared in Example 4), 12g filler (silica), 15g curing agent (prepared in Example 1), and 0.5g curing accelerator (2-ethyl-4-methylimidazolium);
[0053] (2) Mix epoxy resin, silane coupling agent, flame retardant and anti-aging agent and filler, heat to 80℃, stir at 800rpm for 30min, cool to 50℃, add curing agent and curing accelerator, stir at 500rpm for 20min, place in polytetrafluoroethylene mold (90mm×20mm×10mm), cure at 80℃ for 2h, cure at 110℃ for 3h, cool naturally to room temperature, demold to obtain weather-resistant flame retardant and biodegradable resin.
[0054] Example 6 Preparation of weather-resistant, flame-retardant, and biodegradable resin:
[0055] (1) Weigh the following by weight: 70g epoxy resin, 1.5g silane coupling agent (silane coupling agent KH-550), 6g flame retardant and antioxidant (prepared in Example 4), 13g filler (silica), 20g curing agent (prepared in Example 2), and 0.8g curing accelerator (2-ethyl-4-methylimidazolium);
[0056] (2) Mix epoxy resin, silane coupling agent, flame retardant and anti-aging agent and filler, heat to 80℃, stir at 800rpm for 30min, cool to 50℃, add curing agent and curing accelerator, stir at 500rpm for 20min, place in polytetrafluoroethylene mold (90mm×20mm×10mm), cure at 80℃ for 2h, cure at 110℃ for 3h, cool naturally to room temperature, demold to obtain weather-resistant flame retardant and biodegradable resin.
[0057] Example 7 Preparation of weather-resistant, flame-retardant, and biodegradable resin:
[0058] (1) Weigh the following by weight: 80g epoxy resin, 2g silane coupling agent (silane coupling agent KH-550), 7g flame retardant and anti-aging agent (prepared in Example 4), 15g filler (silica), 25g curing agent (prepared in Example 3), and 1g curing accelerator (2-ethyl-4-methylimidazolium).
[0059] (2) Mix epoxy resin, silane coupling agent, flame retardant and anti-aging agent and filler, heat to 80℃, stir at 800rpm for 30min, cool to 50℃, add curing agent and curing accelerator, stir at 500rpm for 20min, place in polytetrafluoroethylene mold (90mm×20mm×10mm), cure at 80℃ for 2h, cure at 110℃ for 3h, cool naturally to room temperature, demold to obtain weather-resistant flame retardant and biodegradable resin.
[0060] Comparative Example 1
[0061] The raw material composition and preparation method of the weather-resistant flame-retardant biodegradable resin are basically the same as those in Example 6, except that the curing agent is replaced with an equal weight of curing agent prepared by the following method:
[0062] The preparation method of the curing agent is basically the same as that in Example 2, except that 2,6-naphthyldimethylamine in step S1 is replaced with an equimolar amount of 1,4-phenylenediamine.
[0063] Comparative Example 2
[0064] The raw material composition and preparation method of the weather-resistant flame-retardant biodegradable resin are basically the same as those in Example 6, except that the curing agent is replaced with an equal weight of curing agent prepared by the following method:
[0065] The preparation method of the curing agent is basically the same as that in Example 2, except that 2,5-furandiethanol in step S2 is replaced with an equimolar amount of 2-furanmethanol; and the amount of 10-aminodecanoic acid in step S3 is replaced with 0.0208 mol.
[0066] Comparative Example 3
[0067] The raw material composition and preparation method of the weather-resistant flame-retardant biodegradable resin are basically the same as those in Example 6, except that the curing agent is replaced with an equal weight of curing agent prepared by the following method:
[0068] The preparation method of the curing agent is basically the same as that in Example 2, except that 10-aminodecanoic acid in step S3 is replaced with an equimolar amount of β-alanine.
[0069] Comparative Example 4
[0070] The raw material composition and preparation method of the weather-resistant flame-retardant biodegradable resin are basically the same as those in Example 6, except that the curing agent is replaced with an equal weight of 4,4'-diaminodiphenylmethane.
[0071] Comparative Example 5
[0072] The raw material composition and preparation method of the weather-resistant flame-retardant biodegradable resin are basically the same as those in Example 6, except that the flame retardant and antioxidant are replaced with an equal weight of the flame retardant and antioxidant prepared by the following method:
[0073] The preparation method of the flame retardant and antioxidant is basically the same as that in Example 4. The difference is that the 3,9-dichloro-2,4,8,10-tetraoxa-3,9-diphosphaspiro[5.5]undecane 3,9-dioxide in step N1 is replaced with 0.2 mol of 5,5-dimethyl-2-chloro-1,3,2-dioxaphosphacaprolactone phosphate; and the amount of intermediate B in step N3 is replaced with 0.105 mol.
[0074] Comparative Example 6
[0075] The raw material composition and preparation method of the weather-resistant flame-retardant biodegradable resin are basically the same as those in Example 6, except that the flame retardant and antioxidant are replaced with an equal weight of the flame retardant and antioxidant prepared by the following method:
[0076] The preparation method of the flame retardant and antioxidant is basically the same as that in Example 4, except that the benzotriazol-1-ylmethylamine in step N2 is replaced with an equimolar amount of 1-(1H-indol-1-yl)methylamine (CAS No.: 214204-10-1).
[0077] Comparative Example 7
[0078] The raw material composition and preparation method of the weather-resistant flame-retardant biodegradable resin are basically the same as those in Example 6. The difference is that the flame retardant and anti-aging agent is replaced with a mixture of 5.5g intermediate A (prepared in step N1 of Example 4) and 3.5g intermediate B (prepared in step N2 of Example 4).
[0079] The epoxy resin used in the embodiments and comparative examples of this application is bisphenol A type epoxy resin E-44, produced by Shandong Deyuan Epoxy Technology Co., Ltd.; the particle size of the silica is uniformly distributed in the range of 30-60nm.
[0080] The weather-resistant, flame-retardant, and biodegradable resins prepared in Examples 5-7 and Comparative Examples 1-7 were tested, and the test results are shown in Table 1.
[0081] Tensile property test: The weather-resistant flame-retardant biodegradable resins prepared in Examples 5-7 and Comparative Examples 1-7 were subjected to tensile property test according to GB / T 1040.2-2022 standard. The resins were cut into 5A dumbbell-shaped specimens and the tensile speed was 50 mm / min.
[0082] Anti-aging performance test: The samples were placed in a QUV accelerated aging test chamber for aging tests, with an ultraviolet wavelength of 340nm and an irradiance of 0.76W / m. 2 The tensile properties of the aged samples were tested again after the temperature was 60℃ and the aging time was 1000h.
[0083] Flame retardant performance test: The weather-resistant flame retardant biodegradable resins prepared in Examples 5-7 and Comparative Examples 1-7 were cut into samples with a size of 80mm×10mm×4mm. The flame retardant performance of the samples was tested according to Method B—Diffusion Ignition Method in GB / T 2406.2-2009.
[0084] Degradation performance test: The weather-resistant flame-retardant biodegradable resin prepared in Examples 5-7 was cut into 20mm×20mm×2mm samples, and the initial weight m0 was measured. The samples were immersed in a glass bottle containing 100ml of 0.15mol / L hydrochloric acid solution, sealed, and subjected to accelerated degradation treatment at 180℃ for 12h. After treatment, the samples were filtered, and the filter cake was vacuum dried at 80℃ for 24h. The weight m1 after drying was measured. According to the formula: The degradation rate was calculated. The resin prepared in Comparative Example 4 was used as a control.
[0085] Table 1 Performance Test Data
[0086]
[0087] As can be seen from Table 1, the weather-resistant, flame-retardant, and biodegradable resins prepared in Examples 5-7 of this application have excellent mechanical properties, aging resistance, flame retardancy, and degradation properties.
[0088] The curing agent added to the resin components prepared in Examples 5-7 of this application is a four-arm primary amine curing agent containing a rigid naphthalene ring, a dynamic Diels-Alder structure, and a flexible long alkyl chain. Its molecular structure regulates the network structure and properties of the resin through multi-scale synergistic effects during curing. During curing, the primary amine groups in the curing agent molecule undergo ring-opening addition reactions with the epoxy groups of the epoxy resin, constructing a dense three-dimensional cross-linked network structure in the system, providing a stable structural basis for the subsequent functional units. In the cross-linked network, the naphthalene ring structure, as a rigid aromatic skeleton, is embedded in the main chain and branches of the network. Its large conjugated plane can form significant π-π stacking interactions in the cured system, effectively restricting the disordered movement of molecular chain segments, improving the rigidity and structural stability of the cross-linked network, thereby significantly enhancing the mechanical strength of the resin. Simultaneously, the long-chain flexible alkyl segments introduced into the curing agent molecule in the rigid cross-linked network... The curing agent acts as a "molecular buffer layer," dispersing stress concentration through chain segment movement under external forces, mitigating brittle fracture tendencies, and enhancing the system's energy dissipation capacity, thereby improving the resin's tensile properties. Furthermore, the dynamic Diels-Alder structure introduced into the curing agent molecule, as a reversible covalent bond unit, exists stably at room temperature and participates in the construction of the cross-linking network. Under heating at 180℃, it can undergo a reversible cycloaddition reaction, leading to the dynamic dissociation of some cross-linking points, causing network rearrangement or relaxation. This dynamic dissociation-reorganization process significantly reduces network structural stability, providing the material with thermally triggered degradation properties. The synergistic effect of the various structures in the four-arm primary amine curing agent within the three-dimensional cross-linking network achieves a balance between high mechanical properties and thermally triggered degradability in the resin system. In Comparative Example 3, the curing agent used has a shorter alkyl chain, resulting in a weakened stress-relieving ability and a decrease in the tensile strength of the prepared resin.
[0089] The flame retardants and antioxidants added to the resin components prepared in Examples 5-7 of this application simultaneously introduce phosphoramide, benzotriazole, and siloxane structures. These functional structures work synergistically under combustion and aging conditions to improve the flame retardancy and aging resistance of the resin. During combustion, the phosphoramide structure in the flame retardant and antioxidant preferentially undergoes thermal decomposition, generating phosphorus-containing active species (such as PO· radicals). These effectively capture highly active free radicals in the flame, thereby inhibiting the combustion chain reaction and achieving gas-phase flame retardancy. Simultaneously, the thermal decomposition of phosphoramide promotes the dehydration and carbonization reaction of the epoxy resin matrix, accelerating char layer formation and improving char layer stability, demonstrating a significant condensed-phase flame retardant effect. Furthermore, the NH3 inert gas released during the decomposition of the phosphoramide structure can dilute the oxygen in the combustion zone, jointly constructing a phosphorus-nitrogen synergistic gas-phase flame retardant mechanism with the phosphorus-containing free radicals. Meanwhile, the siloxane structure in the flame retardant and antioxidant molecule hydrolyzes to generate Si-OH under high temperature or moisture conditions. This Si-OH can further condense with the hydroxyl groups on the surface of the epoxy resin matrix and inorganic fillers, forming a stable Si-O-Si cross-linked network. This significantly improves the density and structural integrity of the char layer during combustion, achieving a synergistic enhancement of condensed-phase flame retardancy through silicon and phosphorus. Regarding anti-aging, the benzotriazole structure in the flame retardant and antioxidant molecule efficiently removes ultraviolet energy through ultraviolet light absorption and intramolecular proton transfer effects, slowing down the photo-oxidative degradation of the resin under ultraviolet irradiation. The synergistic effect of the various functional structures in the flame retardant and antioxidant molecule significantly improves the flame retardant and aging resistance of the resin. The flame retardant and antioxidant used in Comparative Example 7 was a mixture of intermediates A and B, which failed to exert the synergistic silicon-phosphorus condensed-phase flame retardant effect, resulting in a decrease in the flame retardant performance of the prepared resin.
[0090] The above description is merely a preferred embodiment of the present invention and is not intended to limit the present invention. However, any modifications, alterations, and variations made by those skilled in the art without departing from the scope of the present invention based on the disclosed technical content are equivalent embodiments of the present invention. Furthermore, any modifications, alterations, and variations made to the above embodiments based on the essential technology of the present invention are still within the protection scope of the present invention.
Claims
1. A weather-resistant, flame-retardant, and biodegradable resin, characterized in that, The ingredients include the following parts by weight: 60-80 parts epoxy resin, 1-2 parts silane coupling agent, 5-7 parts flame retardant and anti-aging agent, 12-15 parts filler, 15-25 parts curing agent, and 0.5-1 part curing accelerator; The curing agent is a four-arm primary amine curing agent containing a rigid naphthalene ring, a dynamic Diels-Alder structure, and a flexible long alkyl chain, and is prepared by the following method: S1: 2,6-Naphthyldimethylamine reacts with maleic anhydride to form intermediate 1. S2: Intermediate 1 reacts with 2,5-furandimethyl to form intermediate 2. S3: Intermediate 2 reacts with 10-aminodecanoic acid to generate a curing agent.
2. The weather-resistant, flame-retardant, and biodegradable resin according to claim 1, characterized in that, In step S1, the molar ratio of 2,6-naphthyldimethylamine to maleic anhydride is 1:(2.05-2.1).
3. The weather-resistant, flame-retardant, and biodegradable resin according to claim 1, characterized in that, In step S2, the molar ratio of intermediate 1 to 2,5-furandiethanol is 1:(2.03-2.05).
4. The weather-resistant, flame-retardant, and biodegradable resin according to claim 1, characterized in that, In step S3, the molar ratio of intermediate 2 to 10-aminodecanoic acid is 1:(4.05-4.1).
5. The weather-resistant, flame-retardant, and biodegradable resin according to claim 1, characterized in that, The flame retardant and antioxidant is prepared by the following method: N1: 3,9-Dichloro-2,4,8,10-tetraoxa-3,9-diphosphaspiro[5.5]undecane 3,9-dioxide reacts with p-aminobenzoic acid to generate intermediate A. N2: Benzotriazole-1-ylmethylamine reacts with 3-(2,3-epoxypropoxy)propyltrimethoxysilane to generate intermediate B. N3: Intermediate A reacts with intermediate B to generate a flame retardant and antioxidant.
6. The weather-resistant, flame-retardant, and biodegradable resin according to claim 5, characterized in that, In step N1, the molar ratio of 3,9-dichloro-2,4,8,10-tetraoxa-3,9-diphosphaspiro[5.5]undecane 3,9-dioxide to p-aminobenzoic acid is 1:2.1; in step N2, the molar ratio of benzotriazol-1-ylmethylamine to 3-(2,3-epoxypropoxy)propyltrimethoxysilane is 1:1.05; in step N3, the molar ratio of intermediate A to intermediate B is 1:2.
05.
7. The weather-resistant, flame-retardant, and biodegradable resin according to claim 1, characterized in that, The silane coupling agent is silane coupling agent KH-550.
8. The weather-resistant, flame-retardant, and biodegradable resin according to claim 1, characterized in that, The filler is silicon dioxide.
9. The weather-resistant, flame-retardant, and biodegradable resin according to claim 1, characterized in that, The curing accelerator is 2-ethyl-4-methylimidazole.
10. A method for preparing the weather-resistant, flame-retardant, and biodegradable resin according to any one of claims 1-9, characterized in that, Includes the following steps: (1) Weigh out the following by weight: 60-80 parts epoxy resin, 1-2 parts silane coupling agent, 5-7 parts flame retardant and anti-aging agent, 12-15 parts filler, 15-25 parts curing agent, and 0.5-1 parts curing accelerator. (2) Heat and stir the epoxy resin, silane coupling agent, flame retardant and anti-aging agent and filler until they are evenly mixed, then cool down, add curing agent and curing accelerator, stir and mix until evenly mixed, place in a mold for curing, cool and demold to obtain weather-resistant flame retardant and biodegradable resin.