多乙烯多胺桥联受阻酚类抗氧剂的合成及其清除DPPH·性能

doi:10.16085/j.issn.1000-6613.2019-1210

摘要/Abstract

摘要：

以二乙烯三胺和三乙烯四胺为桥联基，β-(3,5-二叔丁基-4-羟基苯基)丙酰氯为抗氧化功能基团，通过酰胺化缩合反应合成了两类具有不同对位桥联基团的受阻酚类抗氧剂。采用傅里叶红外光谱和核磁共振氢谱证实了合成的多乙烯多胺桥联受阻酚类抗氧剂的化学结构。DPPH法研究了多乙烯多胺桥联受阻酚类抗氧剂清除自由基的性能，并探索了酚羟基个数和对位桥联基结构对受阻酚类抗氧剂清除自由基性能的影响。结果表明，多乙烯多胺桥联受阻酚类抗氧剂具有良好的清除DPPH·能力，且随着抗氧剂分子中酚羟基个数的增加，清除DPPH·的活性增加，分子中含有4个酚羟基的三乙烯四胺受阻酚类抗氧剂的抗氧化效率（AE）达到2.65×10^-2 L/(mol·s)。对位桥联基结构对受阻酚类抗氧剂清除DPPH·能力有较大影响，季戊四醇为桥联基的受阻酚类抗氧剂1010清除DPPH·能力最强，其抗氧化效率（AE）为3.08×10^-2L/(mol·s)；乙二胺为核的1.0代树枝状受阻酚类抗氧剂清除DPPH·能力最弱，其抗氧化效率（AE）为2.60×10^-2L/(mol·s)。

关键词: 多乙烯多胺, 受阻酚类抗氧剂, 构效关系

Abstract:

Two types of polyethylene polyamine bridged hindered phenolic antioxidants with different number of para-bridged group were synthesized by amidation condensation reaction using β-(3,5-di-tert-butyl-4-hydroxyphenyl) propionyl chloride as antioxidant groups and diethylenetriamine and triethylenetetramine as bridged groups, respectively. The structures of polyethylene polyamine bridged hindered phenolic antioxidants had been characterized by FTIR and ¹H NMR. The antioxidant properties of polyethylene polyamine bridged hindered phenolic antioxidants were evaluated by the DPPH method, and the relationships between the free radical scavenging properties and the number of phenolic hydroxyl groups or the structure of the para-bridged groups were studied. The results showed that polyethylene polyamine bridged hindered phenolic antioxidants had a good scavenging ability on DPPH radical. As the number of the phenolic hydroxyl groups in hindered phenolic antioxidant increased, the activity of scavenging DPPH· increased. The AE value of triethylenetetramine bridged hindered phenolic antioxidant containing four phenolic hydroxyl groups was 2.65×10^-2L·mol^-1·s^-1. The para-bridged group played an important role in the scavenging DPPH· activity for hindered phenolic antioxidants. The hindered phenolic antioxidant 1010 with pentaerythritol as the bridging group had the strongest ability in scavenging DPPH·, and the AE value was 3.08×10^-2L·mol^-1·s^-1. The 1.0G dendritic antioxidants using ethylenediamine as the nuclear have the weakest DPPH· scavenging ability, and the AE value was 2.60×10^-2L·mol^-1·s^-1.

Key words: polyethylene polyamine, hindered phenol, structure-activity relationship

中图分类号:

O623.738

李翠勤,李杨,郭苏月,高宇新,李锋. 多乙烯多胺桥联受阻酚类抗氧剂的合成及其清除DPPH·性能[J]. 化工进展, 2020, 39(4): 1469-1477.

Cuiqin LI,Yang LI,Suyue GUO,Yuxin GAO,Feng LI. Synthesis and antioxidant activity of polyethylene polyamine bridged hindered phenolic antioxidants[J]. Chemical Industry and Engineering Progress, 2020, 39(4): 1469-1477.

图/表 14

图1 多乙烯多胺桥联受阻酚类抗氧剂的合成路线

表1 多乙烯多胺桥联受阻酚类抗氧剂的合成结果分析

抗氧剂名称	熔程/℃	收率/％	元素分析实测值（理论值）/%
抗氧剂名称	熔程/℃	收率/％	C	H	N
二乙烯三胺1098	104.0～104.6	76.49	74.46（74.52）	9.55（9.62）	4.96（4.84）
三乙烯四胺1098	133.3～134.8	68.67	74.76（74.87）	9.69（9.61）	4.77（4.72）

图2 多乙烯多胺桥联受阻酚类抗氧剂的FTIR谱图

图3 多乙烯多胺桥联受阻酚类抗氧剂的1H NMR谱图

图4 多乙烯多胺桥联受阻酚类抗氧剂的TG曲线图

图5 多乙烯多胺桥联受阻酚类抗氧剂酚羟基浓度对其清除DPPH·活性的影响

图6 受阻酚类抗氧剂清除DPPH·的作用原理

表2 多乙烯多胺桥联受阻酚类抗氧剂清除DPPH·的EC50

抗氧剂	半数有效浓度EC₅₀
抗氧剂	30min	400min
二乙烯三胺1098	1.62	0.32
三乙烯四胺1098	1.14	0.31

图7 清除反应时间对多乙烯多胺桥联受阻酚类抗氧剂清除DPPH·活性的影响

表3 多乙烯多胺桥联受阻酚类抗氧剂清除DPPH·的TC50

抗氧剂	半数有效时间TC₅₀/min
抗氧剂	30min	400min
二乙烯三胺1098	32.71	319.55
三乙烯四胺1098	33.23	339.95

图8 乙二胺1098抗氧剂的化学结构

图9 酚羟基个数对3种受阻酚类抗氧剂清除DPPH·活性的影响

图10 桥联基结构对3种受阻酚类抗氧剂清除DPPH·活性的影响

图11 1.0G抗氧剂和抗氧剂1010的化学结构

参考文献 27

1	徐保明, 裴智山, 韩洋洋, 等. 聚合型受阻酚抗氧剂的研究进展[J]. 化学世界, 2014, 55(9): 561-563.
	XU Baoming，PEI Zhishan，HAN Yangyang，et al. Research progress of polymeric hindered phenolic antioxidants[J]. Chemical World, 2014, 55(9): 561-563.
2	徐志华, 王忠冬, 吴文剑, 等. 受阻酚抗氧剂KY-616和JY-1520在顺丁橡胶中的应用研究[J]. 合成材料老化与应用, 2015, 44(2): 1-4.
	XU Zhihua，WANG Zhongdong，WU Wenjian，et al. Application of hindered phenol antioxidant KY-616 and JY-1520 in butadiene rubber[J]. Synthetic Materials Aging and Application, 2015, 44(2): 1-4.
3	SUN C Z, WU W J, MA Y R, et al. Physicochemical, functional properties, and antioxidant activities of protein fractions obtained from mulberry (morus atropurpurea roxb.) leaf[J]. International Journal of Food Properties, 2017, 20(3): 3311-3325.
4	白琪俊, 刘先龙, 李阳, 等. 受阻酚类抗氧剂在高分子领域的研究进展[J]. 合成树脂及塑料, 2015, 32(5): 72-76.
	BAI Qijun，LIU Xianlong，LI Yang，et al. Research progress of hindered phenolic antioxidants in polymer area[J]. China Synthetic Resin and Plastics, 2015, 32(5): 72-76.
5	NAZARBAHJAT N, NORDIN N, ABDULLAH Z, et al. New thiosemicarbazides and 1,2,4-triazo lethiones derivedfrom 2-(ethylsulfanyl) benzohydrazide as potent antioxidants[J]. Molecules, 2014, 19(8): 11520-11537.
6	AMORATI R, PEDULLI G F, VALGIMIGLI L, et al. Organochalcogen substituents in phenolic antioxidants[J]. Organic Letters, 2010, 12(10): 2326-2329.
7	李翠勤, 翟雪, 孙鹏, 等. 树状桥联半受阻酚类抗氧剂的合成与抗氧化性能[J]. 高等学校化学学报, 2019, 40(7): 1535-1543.
	LI Cuiqin, ZHAI Xue, SUN Peng, et al. Synthesis and antioxidant activity of dendrimer bridged primary antioxidant with four semi-hindered phenolic antioxidant groups[J]. Chemical Journal of Chinese Universities, 2019, 40(7): 1535-1543.
8	马建民, 吴爱芹. 抗氧剂的特征及作用[J]. 高分子材料科学与工程, 2004, 20(4): 46-49.
	MA Jianmin, WU Aiqin. Characteristic and effect of antioxidant[J]. Polymer Materials Science and Engineering, 2004, 20(4): 46-49.
9	王华. 受阻酚类抗氧剂结构与其抗氧化性能的影响关系[J]. 工业催化, 2017, 25(4): 74-77.
	WANG Hua. The relationship between structures and properties of hindered phenolic antioxidants[J]. Industrial Catalysis, 2017, 25(4): 74-77.
10	LI C Q, SUN P, GUO S Y, et al. Relationship between bridged groups and antioxidant activity for aliphatic diamine bridged hindered phenol in polyolefins[J]. Journal of Applied Polymer Science, 2017, 134(30): 45095.
11	LIM M Y, OH J, KIM H J, et al. Effect of antioxidant grafted graphene oxides on the mechanical and thermal properties of polyketone composites[J]. European Polymer Journal, 2015, 69: 156-167.
12	SHI X M, WANG J D, JIANG B B, et al. Hindered phenol grafted carbon nanotubes for enhanced thermal oxidative stability of polyethylene[J]. Polymer, 2013, 54(3): 1167-1176.
13	SALEHI M H, KARIMI A R. Novel octa-substituted metal (Ⅱ) phthalocyanines bearing 2, 6-di-tert-buthylphenol groups: synthesis, characterization, electronic properties, aggregation behavior and their antioxidant activities as stabilizer for polypropylene and high density polyethylene[J]. Polymer Degradation and Stability, 2018, 151: 105-113.
14	王俊, 张会平, 李翠勤, 等. β-(3,5-二叔丁基-4-羟基苯基)丙酰氯的合成研究[J]. 精细化工中间体, 2007, 37(5): 61-63.
	WANG Jun, ZHANG Huiping, LI Cuiqin, et al. Synthesis of β-(3,5-diterbutyl-4-hydroxyphenyl)propionyl chloride[J]. Fine Chemical Intermediates, 2007, 37(5): 61-63.
15	李翠勤, 康伟伟, 张志秋, 等. 脂肪二胺桥联受阻酚的合成及抗氧化活性研究[J]. 分子科学学报, 2015, 31(6): 502-508.
	LI Cuiqin, KANG Weiwei, ZHANG Zhiqiu, et al. Synthesis and antioxidant activity of aliphatic diamine bridged hindered phenol[J]. Journal of Molecular Science, 2015, 31(6): 502-508.
16	李翠勤, 郭苏月, 王鹏祥, 等. 树状聚酰胺-胺桥联受阻酚类抗氧化剂的合成及清除DPPH·活性研究[J]. 高分子通报, 2016(10): 68-77.
	LI Cuiqin, GUO Suyue, WANG Pengxiang, et al. Synthesis and activities of scavenging DPPH· of dendritic PAMAM bridged hindered phenol antioxidants[J]. Polymer Bulletin, 2016(10): 68-77.
17	WAGEEH A Y, NOORSAADAH A R, AZHAR A, et al. Understanding the chemistry behind the antioxidant activities of butylated hydroxy toluene (BHT): a review[J]. European Journal of Medicinal Chemistry, 2015, 46(41): 295-312.
18	王俊, 史春霞, 李翠勤, 等. DPPH法研究聚烯烃抗氧剂的抗氧化能力及反应动力学[J]. 石油学报（石油加工）, 2012, 28(6): 973-977.
	WANG Jun, SHI Chunxia, LI Cuiqin, et al. Study on the antioxidant capacity and kinetics of polyolefin antioxidant by using DPPH method[J]. Acta Petrolei Sinica (Petroleum Processing Section), 2012, 28(6): 973-977.
19	吕九琢, 李燕芸, 刘霞,等. 合成N,N’-双[3-(3,5-二叔丁基-4-羟基苯基)丙酰]六甲撑二胺的新工艺[J]. 精细化工, 1999, 16(3): 29-32.
	LV Jiuzhuo, LI Yanyun, LIU Xia, et al. Synthesis of N, N’-bis-[3-(3,5-di-tert-buty-4-hydroxyphenyl)propionyl]-hyxamethylene-diamine by a new method[J]. Fine Chemicals, 1999, 16(3): 29-32.
20	李翠勤, 王俊, 栾书春, 等. 一类新型受阻酚抗氧剂的合成与表征[J]. 分子科学学报, 2011, 27(3): 180-184.
	LI Cuiqin, WANG Jun, LUAN Shuchun, et al. Synthesis and charaterization of a novel hindered phenolic antioxidant[J]. Journal of Molecular Science, 2011, 27(3): 180-184.
21	LI C Q, SUN P, YU H Y, et al. Scavenging ability of dendritic PAMAM bridged hindered phenolic antioxidants towards DPPH· and ROO· free radicals[J]. RSC Advances, 2017, 7(4): 1869-1876.
22	LI C Q, ZHAI X, GUO S Y, et al. Antiradical ability of dendrimer-bridged hindered phenol and its antioxidant property in polyolefin[J]. Chemistry Select, 2017, 2(24): 7202-7209.
23	SHARMA O P, BHAT T K. DPPH antioxidant assay revisited[J]. Food Chemistry, 2009, 113(4): 1202-1205.
24	JIA Z S, ZHOU B, YANG L, et al. Antioxidant synergism of tea polyphenols and α-tocopherol against free radical induced peroxidation of linoleic acid in solution[J]. Journal of the Chemical Society, Perkin Transactions2, 1998(4): 911-916.
25	王华, 王丹, 杨勇. 受阻酚类抗氧剂在PE100管材专用树脂中的性能研究[J]. 塑料科技, 2017, 45(5): 108-113.
	WANG Hua，WANG Dan，YANG Yong. Study on the properties of the hindered phenolic antioxidants in PE100 resins[J]. Plastics Science and Technology, 2017, 45(5): 108-113.
26	LI C Q, WEI Y J, SHI W G, et al. Antioxidant capacity and kinetics of dendritic hindered phenols using DPPH assay[J]. Progress in Reaction Kinetics and Mechanism, 2015, 40(3): 279-290.
27	王长春,费逸伟,马军,等.酚类抗氧剂的影响因素及发展趋势[J]. 化工时刊, 2019, 33(1): 33-37.
	WANG Changchun, FEI Yiwei, MA Jun, et al. Influence factors and development trend of phenolic antioxidant[J]. Chemical Industry Times, 2019, 33(1): 33-37.

[1]	许春树, 姚庆达, 梁永贤, 周华龙. 氧化石墨烯/碳纳米管对几种典型高分子材料的性能影响[J]. 化工进展, 2023, 42(6): 3012-3028.
[2]	李云鹏, 彭东岳, 管翠诗. 芳烃与烯烃烷基化反应的催化机理进展[J]. 化工进展, 2020, 39(S2): 204-211.
[3]	朱丹琛,肖伽励,杨丽丽,傅明连. 水热合成MnO₂及其染料吸附性能的构效关系[J]. 化工进展, 2019, 38(08): 3774-3781.
[4]	邱松山, 姜翠翠, 周如金, 刘杰凤. 反丁烯二酸酯类物质结构与抑菌性能关系[J]. 化工进展, 2016, 35(03): 879-883.
[5]	王哲，王普，黄金. 分子模拟技术在脂肪酶性质及催化机理研究中的应用进展[J]. 化工进展, 2013, 32(10): 2475-2479.
[6]	左华江1，2，温婉华2，吴丁财2，符若文2 . 季铵盐类抗菌聚合物的研究现状[J]. 化工进展, 2013, 32(10): 2416-2422.
[7]	左华江1，2，温婉华2，吴丁财2，符若文2 . 高分子抗菌剂的研究现状[J]. 化工进展, 2013, 32(03): 604-609.
[8]	陈学勇，韦朝海. 点源有机毒物污（废）水排放的生态风险管理技术分析 [J]. 化工进展, 2010, 29(2): 342-.
[9]	卢圣茂；吴祖望；董振堂；王志伟；陈光顺. 甲型活性染料及其构效关系的研究进展 [J]. 化工进展, 2007, 26(11): 1529-.