氧化锆负载硒催化苯胺氧化聚合反应

doi:10.6023/cjoc202404022

摘要/Abstract

聚苯胺(PANIs)是通过苯胺的氧化聚合合成的材料, 已被广泛使用. 目前的合成方法需要使用化学氧化剂, 并使用HCl/NaOH作为酸碱调节剂, 会带来大量废盐, 也会导致材料中的杂离子残留而影响其性能, 这些缺点不利于其工业应用. 报道了一种制备聚苯胺的新方法, 即氧化锆负载硒催化苯胺在无酸碱调节剂的条件下以氧气为氧化剂的氧化聚合. 该方法的相对安全和绿色的特点使其更适合大规模应用. 研究表明, 该方法制备的聚苯胺可用作载体负载钯催化剂, 其性能与传统方法合成的材料无异.

关键词: 硒, 氧化锆, 催化氧化, 苯胺, 聚苯胺

Polyanilines (PANIs) are widely employed materials that are synthesized via the oxidative polymerization of anilines. However, the present synthetic methods always require the use of chemical oxidants and employ HCl/NaOH as the acid-base regulator, resulting in a large amount of waste salt and residual impurities in the material that affect its performance. These drawbacks are unfavorable for industrial applications. A novel method for the preparation of PANIs, i.e. the Se/ZrO₂- catalyzed oxidative polymerization of aniline with O₂ free of the acid-base regulator is developed. The relatively safe and green features of the method make it more practical for large-scale applications. Researches showed that PANIs prepared by this method could be used as the support to anchor palladium catalyst, and its activity was as good as that of the materials synthesized via traditional methods.

Key words: selenium, zirconia, catalyzed oxidation, aniline, polyaniline

引用此文

雍达明, 左婷婷, 吴启超, 张旭. 氧化锆负载硒催化苯胺氧化聚合反应[J]. 有机化学, 2024, 44(11): 3392-3398.

Daming Yong, Tingting Zuo, Qichao Wu, Xu Zhang. Se/ZrO₂-Catalyzed Oxidative Polymerization of Aniline[J]. Chinese Journal of Organic Chemistry, 2024, 44(11): 3392-3398.

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图/表 6

图式1. 聚苯胺合成方法.

Scheme 1. Methods for the synthesis of PANI

图1. (a)分别反应3、5、8或10 h后的样品照片(从左到右)、(b)样品在不同反应时间的紫外-可见光谱及(c)制备的聚苯胺的FT-IR光谱

Figure 1. (a) Photographs of the samples after 3, 5, 8 or 10 h reaction respectively (from left to right), (b) UV-Vis spectra of the samples at different reaction times, and (c) FT-IR spectrum of the prepared PANI

图2. 催化剂回收和再利用(反应10 h)

Figure 2. Catalyst recycling and reusing (reaction for 10 h)

Entry	Method^b	X	R	Product	Yield^c/%	TON^d
1	V	I	H	A	99	8.8×10³
2	I	I	H	A	82	6.2×10³
3	II	I	H	A	86	5.7×10³
4	III	I	H	A	99	0.2×10³
5	IV	I	H	A	94	8.0×10³
6	V	Br	H	A	72	6.4×10³
7	I	Br	H	A	55	4.2 ×10³
8	II	Br	H	A	55	3.6×10³
9	III	Br	H	A	68	0.1×10³
10	IV	Br	H	A	66	5.6×10³
11	V	Br	NO₂	B	75	6.7×10³
12	V	Cl	H	A	8	0.7×10³
13	V	Cl	NO₂	B	17	1.5×10³

表1. 不同方法制备Pd@PANI反应活性的评估a

Table 1. Catalytic activity evaluation of the Pd@PANI prepared via different methods

图式2. 催化循环机理

Scheme 2. Mechanism of the catalysis circle

图式3. 聚合物链增长机理

Scheme 3. Mechanism for the polymer chain growing

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