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

摘要/Abstract

摘要：

以6-（双（4-羟基-3-甲氧基苯基）甲基）二苯并[c，e]氧磷酸6-氧化物（BDB）、环氧氯丙烷（ECH）为原料，四丁基溴化铵（TBAB）为催化剂，制备生物基环氧树脂（DGEBDB），再与含有β-氨基醇结构的固化剂双酚A（DHABA）固化得到同时具有阻燃以及抗菌功能的生物基环氧树脂（EB/DHABA），通过调节DGEBDB与商用环氧树脂E51的比例探究EB/DHABA的结构与性能的关系。利用核磁共振氢谱（¹H NMR）对DGEBDB的结构进行了表征，通过红外光谱（FT-IR）、热重分析（TG）仪、漆膜冲击器、菌落计数器、垂直燃烧测试仪等对环氧树脂的固化行为、热学、力学、抗菌、阻燃等性能进行测试分析。结果表明：EB/DHABA成功制备，且具有优异的综合性能，玻璃化转变温度最高可以达到130.62℃。当DGEBDB为10%时制备的E₉B₁/DHABA，体系的交联密度最高，为3 519 mol/m³，失重率为10%的温度约为350℃；漆膜的铅笔硬度最高可达5H，同时均具有良好的抗冲击强度和耐溶剂性；对大肠杆菌和金黄色葡萄球菌具有良好的杀灭作用，杀菌率≥99.4%。当DGEBDB为30%时制备的E₇B₃/DHABA，其阻燃效果最好，UL-94等级可以达到V-0级别。

关键词: 阻燃, 本征抗菌, β-氨基醇, 环氧树脂, 生物基

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

中图分类号:

TQ35

陈明暄, 代金月, 曹培占, 陈夏伟, 刘小青. 生物基阻燃抗菌环氧树脂的制备及其性能研究[J]. 生物质化学工程, 2024, 58(2): 13-21.

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.

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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

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