生物基阻燃抗菌环氧树脂的制备及其性能研究

doi:10.3969/j.issn.1673-5854.2024.02.002

Abstract

Abstract:

Biobased epoxy resin(DGEBDB) was created using 6-(bis(4-hydroxy-3-methoxyphenyl) methyl) dibenzo [c, e] oxyphosphate 6-oxide(BDB) and epichlorohydrin(ECH) as raw materials and tetrabutylammonium bromide(TBAB) as catalyst. Then, it was solidified with bisphenol A(DHABA), a curing agent containing β-amino alcohol structure, to obtain a bio-based flame retardant and antibacterial epoxy resin(EB/DHABA) with both intrinsic antibacterial and intrinsic flame retardant properties. The relationship between structure and performance was investigated by varying the ratio of DGEBDB to commercial epoxy resin E51. The structure of DGEBDB was characterized by nuclear magnetic resonance spectroscopy(¹H NMR). The curing behavior, thermal, mechanical, antibacterial and flame retardant properties of epoxy resin were tested and analyzed by FT-IR, TG, paint film impactor, colony counter and vertical combustion tester. The results showed that EB/DHABA had been successfully prepared, the resin had excellent comprehensive properties, and the glass transition temperature could reach 130.62℃. When the content of DGEBDB in the system was 10%, the crosslinking density of the system was highest, which was 3 519 mol/m³. T_10% was about 350℃, and it decreased with the increase of DGEBDB addition. The pencil hardness of the paint film could reach up to 5H and it had good impact strength and solvent resistance. It also had good killing effect on E. coli and S. aureus, with a sterilization rate of 99.4%. The results of vertical combustion test revealed that when the content of DGEBDB in the system reached 30%, the flame retardant effect was the best, and UL-94 grade could reach V-0 grade.

Key words: flame retardant, intrinsic antibacterial, β-aminoalcohol, epoxy resin, bio-based

CLC Number:

TQ35

Mingxuan CHEN, Jinyue DAI, Peizhan CAO, Xiawei CHEN, Xiaoqing LIU. Preparation and Properties of Bio-based Flame Retardant and Antibacterial Epoxy Resin[J]. Biomass Chemical Engineering, 2024, 58(2): 13-21.

Figures/Tables 12

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References 31

1	郑炳云, 陈彰旭, 傅明连, 等. SiO₂/C₆₀/环氧树脂阻燃涂层的制备及性能表征[J]. 涂料工业, 2023, 53 (8): 14- 19.
2	WANG S , MA S Q , XU C X , et al. Vanillin-derived high-performance flame retardant epoxy resins: Facile synthesis and properties[J]. Macromolecules, 2017, 50 (5): 1892- 1901. doi: 10.1021/acs.macromol.7b00097
3	TENG N , DAI J Y , WANG S P , et al. Hyperbranched flame retardant for epoxy resin modification: Simultaneously improved flame retardancy, toughness and strength as well as glass transition temperature[J]. Chemical Engineering Journal, 2022, 428, 1385- 8947.
4	MALBURET S , BERTRAND H , RICHARD C , et al. Biobased epoxy reactive diluents prepared from monophenol derivatives: Effect on viscosity and glass transition temperature of epoxy resins[J]. RSC Advances, 2023, 13 (22): 15099- 15106. doi: 10.1039/D3RA01039B
5	BERTANI R, BARTOLOZZI A, PONTEFISSO A, et al. Improving the antimicrobial and mechanical properties of epoxy resins via nanomodification: An overview[J/OL]. Molecules, 2021, 26(17): 5426[2023-06-10]. https://doi.org/10.3390/molecules26175426.
6	张晓璇, 韩雨珊, 余源元, 等. 银纳米颗粒-季铵化木质素-纤维素水凝胶的制备及抗菌性能[J]. 生物质化学工程, 2023, 57 (2): 55- 61.
7	DEMIR C , SÜER N C , YAPAÖZ M A , et al. Biocidal activity of ROMP-polymer coatings containing quaternary phosphonium groups-ScienceDirect[J]. Progress in Organic Coatings, 2019, 135, 299- 305. doi: 10.1016/j.porgcoat.2019.06.008
8	杨嵘晟, 朱俊芳, 冯树波. 纤维素/超细氧化锌复合气凝胶的制备及抗菌性能研究[J]. 生物质化学工程, 2019, 53 (5): 39- 43.
9	吴秀琳, 台立民. 淀粉/PE共混体系水解释放杀菌剂的研究[J]. 塑料, 2009, 38 (2): 27- 29.
10	董耀华, 郭娜, 刘涛, 等. 载银自抛光/低表面能环保涂层的制备及其耐微生物附着性能研究[J]. 表面技术, 2015, 44 (3): 100- 106.
11	胡定军, 刘朝军, 章浩荣. 聚丙烯单原子铜抗菌纤维的制备及其性能[J]. 工程塑料应用, 2023, 51 (5): 51- 55.
12	LI R , YANG G X , WANG Y D , et al. Synthesis of antibacterial polyether biguanide curing agent and its cured antibacterial epoxy resin[J]. Designed Monomers & Polymers, 2021, 24 (1): 63- 72.
13	冯浩洋, 胡婧媛, 金丹丹, 等. 具有可控降解与抗菌功能的生物基环氧树脂合成[J]. 高分子学报, 2022, 53 (9): 1083- 1094.
14	UYSALMAN T , SAGLAM M , ERASLAN K , et al. Investigation of the fire performance of polyamide 6-based composites with halogen-free flame retardants and synergistic materials[J]. ACS Omega, 2022, 7 (33): 28885- 28895. doi: 10.1021/acsomega.2c02018
15	YI L, YANG Q, YAN L, et al. Facile fabrication of multifunctional transparent fire-retardant coatings with excellent fire resistance, antibacterial and anti-aging properties[J/OL]. Progress in Organic Coatings, 2022, 169: 106925[2023-06-10]. https://doi.org/10.1016/j.porgcoat.2022.106925.
16	CHAI W H, SU X Y, XIA Y R, et al. Construction of a novel halogen-free and phosphorus-free and synergistic flame retardant system with low addition in simultaneously improving the flame retardancy, water resistance and mechanical properties for silicone rubber[J/OL]. Applied Clay Science, 2023, 238: 106926[2023-06-10]. https://doi.org/10.1016/j.clay.2023.106926.
17	郑峤, 夏溦, 付荣, 等. DOPO衍生物阻燃环氧树脂研究新进展[J]. 辽宁化工, 2023, 52 (3): 401- 404.
18	WANG P , CHEN L , XIAO H . Flame retardant effect and mechanism of a novel DOPO based tetrazole derivative on epoxy resin[J]. Journal of Analytical and Applied Pyrolysis, 2019, 139 (5): 104- 113.
19	NIU H X, WU G L, WANG X, et al. Synthesis of a vanillin-derived bisDOPO co-curing agent rendering epoxy thermosets simultaneously improved flame retardancy, mechanical strength and transparency[J/OL]. Polymer Degradation and Stability, 2023, 211: 110333[2023-06-10]. https://doi.org/10.1016/j.polymdegradstab.2023.110333.
20	CHI Z Y, GUO Z W, XU Z C, et al. A DOPO-based phosphorus-nitrogen flame retardant bio-based epoxy resin from diphenolic acid: Synthesis, flame-retardant behavior and mechanism[J/OL]. Polymer Degradation and Stability, 2020, 176: 109151[2023-06-10]. https://doi.org/10.1016/j.polymdegradstab.2020.109151.
21	LIU J K, DAI J Y, WANG S P, et al. Facile synthesis of bio-based reactive flame retardant from vanillin and guaiacol for epoxy resin[J/OL]. Composites Part B: Engineering, 2020, 190: 107926[2023-06-10]. https://doi.org/10.1016/j.compositesb.2020.107926.
22	MORA A S , TAYOUO R , BOUTEVIN B , et al. Vanillin-derived amines for bio-based thermosets[J]. Green Chemistry, 2018, 20 (17): 4075- 4084. doi: 10.1039/C8GC02006J
23	ROTHENHAUSLER F, RUCKDAESCHEL H. Amino acids as bio-based curing agents for epoxy resin: Correlation of network structure and mechanical properties[J/OL]. Polymers(Basel), 2023, 15(2): 385[2023-06-10]. https://doi.org/10.3390/polym15020385.
24	ZHANG X , HAO X X , QIU S H , et al. Efficient capture and release of carboxylated benzisothiazolinone from UiO-66-NH₂ for antibacterial and antifouling applications[J]. Journal of Colloid and Interface Science, 2022, 623, 710- 722. doi: 10.1016/j.jcis.2022.05.065
25	XIAO L H , HUANG J R , WANG Y G , et al. Tung oil-based modifier toughening epoxy resin by sacrificial bonds[J]. ACS Sustainable Chemistry & Engineering, 2019, 7 (20): 17344- 17353.
26	YU X Y, HONG H Y, LI X, et al. The effect of polysulfone(PSU) grafting copolymers on improving the processability of its composites[J/OL]. Journal of Polymer Research, 2023, 30(2): 87[2023-06-10]. https://doi.org/10.1007/s10965-023-03459-2.
27	BODEN J , BOWEN C R , BUCHARD A , et al. Understanding the effects of cross-linking density on the self-healing performance of epoxidized natural rubber and natural rubber[J]. ACS Omega, 2022, 7 (17): 15098- 15105. doi: 10.1021/acsomega.2c00971
28	QIU S L, ZHOU Y F, ZHOU X, et al. Air-stable polyphosphazene-functionalized few-layer black phosphorene for flame retardancy of epoxy resins[J/OL]. Small, 2019, 15(10): e1805175[2023-06-10]. https://doi.org/10.1002/smll.201805175.
29	赵婉, 操倩文, 武海棠, 等. 紫外光固化漆酚铈聚合物涂层的制备与性能研究[J]. 林产化学与工业, 2019, 39 (4): 113- 119.
30	ZHAO Z Q , MA X L , CHEN R , et al. Universal antibacterial surfaces fabricated from quaternary ammonium salt-based PNIPAM microgels[J]. ACS Applied Materials & Interfaces, 2020, 12 (17): 19268- 19276.
31	VAIDERGORN M M , CARNEIRO Z A , LOPES C D , et al. beta-Amino alcohols and their respective 2-phenyl-N-alkyl aziridines as potential DNA minor groove binders[J]. European Journal of Medicinal Chemistry: Chimie Therapeutique, 2018, 157, 657- 664. doi: 10.1016/j.ejmech.2018.07.055

样品sample	T_g/℃	T_10%/℃		残炭率(750 ℃)/% residual carbon ratio		室温下储能模量/MPa energy storage modulus	交联密度/(mol·m^-3) crosslinking density
样品sample	T_g/℃	空气air	N₂	空气air	N₂	室温下储能模量/MPa energy storage modulus	交联密度/(mol·m^-3) crosslinking density
EP	86.1	356	359	0.5	9.1	3 055.3	1 372
E₉B₁/DHABA	120.3	343	347	2.2	14.2	4 085.7	3 519
E₈B₂/DHABA	124.7	330	333	3.2	14.8	3 045.4	2 190
E₇B₃/DHABA	130.6	314	319	8.2	15.5	2 893.4	2 120

样品sample	抗冲击强度/(kg·cm) impact strength	铅笔硬度pencil hardness	耐溶剂性/次solvent resistance
样品sample	抗冲击强度/(kg·cm) impact strength	铅笔硬度pencil hardness	丙酮acetone	乙醇ethyl alcohol
EP	45	3H	>250	>400
E₉B₁/DHABA	70	5H	>400	>400
E₈B₂/DHABA	50	5H	>400	>400
E₇B₃/DHABA	40	5H	>400	>400

样品sample	含磷量/% phosphorus content	有无燃烧物滴落drip condition of burnt matter	极限氧指数/% limiting oxygen index	UL-94
样品sample	含磷量/% phosphorus content	有无燃烧物滴落drip condition of burnt matter	极限氧指数/% limiting oxygen index	t₁/s	t₂/s	等级rank
EP	0	有yes	21.6	>60	>60	无no
E₉B₁/DHABA	0.5	无no	24.7	7.3	6.2	V-1
E₈B₂/DHABA	1.0	无no	28.1	6.7	4.6	V-1
E₇B₃/DHABA	1.5	无no	31.8	3.1	2.7	V-0

[1]	Shanyuan TONG, Yun HU, Jinni YU, Puyou JIA, Qin HUANG, Yonghong ZHOU. Research Progress on Bio-based Vitrimer Materials [J]. Biomass Chemical Engineering, 2023, 57(6): 37-46.
[2]	Yu BEI, Shuxian WENG, Puyou JIA, Caiying BO, Lihong HU, Yonghong ZHOU. Research Progress on Lignin-based Flame Retardants [J]. Biomass Chemical Engineering, 2023, 57(2): 71-78.
[3]	Lili JIANG, Baowei ZHU, Changli LI, Wei YANG, Fengyi LIU. Research Progress in Microbial Conversion Crude Glycerol to High Value-added Products [J]. Biomass Chemical Engineering, 2021, 55(5): 60-66.
[4]	Ze YU, Xu LI, Jianan WANG, Zhiming LIU. Preparation and Flame Retardant Properties of Dimethyl Methylphosphonate/Sodium Lignosulfonate Polyurethane Foam [J]. Biomass Chemical Engineering, 2021, 55(2): 50-54.
[5]	Hongkun ZHANG, Zan LI, Xianyun GONG, Yang WANG. Properties of Co-cured Flame Retardant Epoxy Resin Materials Obtained by Lignin and Phosphorus-containing Flame Retardant [J]. Biomass Chemical Engineering, 2020, 54(6): 59-64.
[6]	Mengmeng WANG,Lequn LIU,Zhentao LIU,Ying ZHAO. Flame Retardant Modification of Bamboo Liquefied Wall Foam Materials [J]. Biomass Chemical Engineering, 2020, 54(5): 25-32.
[7]	GUO Jiawen, CHEN Lijing, WANG Jun, XU Xu. Synthesis and Application Progress of Terpene-based Polymer Materials [J]. bce, 2018, 52(3): 59-64.
[8]	DENG Kun-ming, WANG Peng-fei, MA Yan, WANG Hong-xiao, SHEN Juan-zhang, TAN Wei-hong. Research Progress of Determination Method of Bio-based Content in Bio-based Solid Material [J]. bce, 2016, 50(5): 53-59.
[9]	CHANG Xia;NIE Xiao-an;WANG Yi-gang;CHEN Jie;LI Ke. Preparation and Properties of Random Carboxylated Butadiene Nitrile Rubber Modified Epoxy Resins [J]. , 2013, 47(6): 1-5.
[10]	ZHANG Ye;CHEN Ming-qiang;WANG hua;YANG Zhong-lian;LIU Shao-min;WANG Jun. Research Progress of Lignin-based Materials [J]. , 2012, 46(5): 45-52.
[11]	HU Su-qin;CAI Fei-peng;WANG Jian-mei;LIU Qiang;JIN Fu-qiang;YANG Gai;WANG Bo. The Planting and Utilization of Jerusalem Artichoke [J]. , 2012, 46(1): 51-54.
[12]	MI Zhen;NIE Xiao-an;. Research Status and Development Trend on Preparation of Flame-resistant Plasticizer [J]. , 2011, 45(5): 46-50.
[13]	ZHU Li-jing;CHEN Fan-geng. The State of the Art on Lignocellusic-based Polyurethane Materials [J]. , 2011, 45(4): 56-60.
[14]	LIN Gui-fu;NIE Xiao-an. Curing Reaction of Epoxy Resin/Maleopimaric Polyamides and the Cured Product Properties [J]. , 2011, 45(3): 21-26.
[15]	CHEN Jian;KONG Zhen-wu;WU Guo-min;CHU Fu-xiang;. Research Progress on Natural Vegetable Fibres Reinforced Epoxy Resin Composites [J]. , 2010, 44(5): 53-59.

Preparation and Properties of Bio-based Flame Retardant and Antibacterial Epoxy Resin

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