微反应器内颜料红57连续化合成工艺

doi:10.11949/0438-1157.20240304

摘要/Abstract

摘要：

偶氮色淀颜料属于重要的有机颜料品种之一，广泛应用于各类工业领域。利用微反应器技术实现颜料红57的连续化合成，对于偶氮色淀颜料生产技术的革新有重要意义。首先，搭建微反应器系统，并在系统内对重氮化反应、偶合反应、色淀化反应过程进行反应条件优化。在最优的反应条件下，重氮盐的收率大于99%，颜料红收率大于99%，颜料红色淀后的固体回收率接近100%。然后，采用不同碱金属盐或者碱土金属溶液进行色淀化反应，实现对颜料色光的调控。其中，Sr²⁺、Ba²⁺色淀后色光偏亮，同时偏红偏黄；Zn²⁺、Mg²⁺、Mn²⁺色淀后色光偏暗，同时偏绿偏蓝。

关键词: 微反应器, 微尺度, 重氮化反应, 偶合反应, 色淀化反应, 偶氮色淀颜料

Abstract:

Azo lake pigments are one of the important organic pigment varieties and are widely used in various industrial fields. The continuous-flow synthesis of Pigment Red 57 using the microreactor technology is of great significance for the innovation of azo lake pigments production technology. First, a microreactor system was built, and the reaction conditions of diazotization, coupling and laking process were optimized in the system. Under the optimal reaction conditions, the yield of diazonium salt was greater than 99%, the yield of pigment red was greater than 99%, and the solid recovery after laking was close to 100%. Finally, different alkali metal salts or alkaline earth metal solutions were used for laking process to achieve the regulation of chromatic light. Among them, the chromatic light after Sr²⁺ and Ba²⁺ laking was brighter, and the red and yellow hues were intense. The chromatic light after Zn²⁺, Mg²⁺, Mn²⁺ laking was dark, and the green and blue hues were intense.

Key words: microreactor, microscale, diazotization, coupling, laking, azo lake pigment

中图分类号:

TQ 052.5

王法军, 陈安, 徐建鸿. 微反应器内颜料红57连续化合成工艺[J]. 化工学报, 2024, 75(10): 3600-3609.

Fajun WANG, An CHEN, Jianhong XU. Continuous-flow synthesis of Pigment Red 57 in a microreactor system[J]. CIESC Journal, 2024, 75(10): 3600-3609.

图/表 16

图1 颜料红57微反应连续化合成装置示意图

Fig.1 Experimental setup for continuous-flow synthesis of Pigment Red 57

图2 颜料红57的合成反应（以Ca2+色淀为例）

Fig.2 Reactions for Pigment Red 57 (Ca2+ laking) synthesis

表1 洗脱梯度

Table 1 Elution gradient

时间/min	乙酸铵缓冲液比例/%	乙腈比例/%
0	85	15
12.0	45	55
19.0	15	85
19.1	85	15
25.0	85	15

图3 溶液的液相色谱出峰位置

Fig.3 Peak positions in liquid chromatography of the solution

图4 不同化合物标准工作曲线

Fig.4 Standard operating curves for different compounds

表2 标准工作曲线方程

Table 2 Standard working curve equation

化合物	标准工作曲线方程	R²
4-氨基甲苯-3-磺酸	C=0.1275A	0.9996
2-羟基-3-萘甲酸	C=0.0297A	0.9999
颜料红57	C=0.0695A	1.0000

图5 反应温度对重氮盐收率的影响

Fig.5 Effect of reaction temperature on the yield of diazonium salt

图6 反应时间对重氮盐收率的影响

Fig.6 Effect of reaction time on the yield of diazonium salt

图7 N(NaNO2)/N(Ar-NH2)对重氮盐收率的影响

Fig.7 Effect of N(NaNO2)/N(Ar-NH2) on the yield of diazonium salt

图8 反应pH对重氮盐剩余率（X）及颜料红收率（Y）的影响

Fig.8 Effect of pH on the residual rate of diazonium salt (X) and the yield of Pigment Red 57 (Y)

图9 反应时间对重氮盐剩余率（X）及颜料红收率（Y）的影响

Fig.9 Effect of reaction time on the residual rate of diazonium salt (X) and the yield of Pigment Red 57 (Y)

图10 反应温度对重氮盐剩余率（X）及颜料红收率（Y）的影响

Fig.10 Effect of reaction temperature on the residual rate of diazonium salt (X) and the yield of Pigment Red 57 (Y)

图11 反应温度对颜料红剩余率的影响

Fig.11 Effect of reaction temperature on the residual rate of Pigment Red 57

图12 反应时间对颜料红剩余率的影响

Fig.12 Effect of reaction time on the residual rate of Pigment Red 57

图13 不同离子色淀后的颜料色光示意图

Fig.13 Chromatic light diagram of pigment after different ion color laking

图14 不同离子色淀颜料色光对比

Fig.14 Contrast of chromatic light of different ionic lake pigments

参考文献 31

1	李政. 新型偶氮缩合颜料的合成及性能研究[D]. 天津: 天津大学, 2016.
	Li Z. The synthesis and properties of new disazocondenation pigments[D]. Tianjin: Tianjin University, 2016.
2	张振坤. 颜料红146的合成工艺研究[D]. 北京: 北京化工大学, 2021.
	Zhang Z K. Study on the synthesis of Pigment Red 146[D]. Beijing: Beijing University of Chemical Technology, 2021.
3	黄钧. 偶氮颜料及其环保性[J]. 网印工业, 2011(2): 36-38.
	Huang J. Azo pigments and their environmental properties[J]. Screen Printing Industry, 2011(2): 36-38.
4	严钫. 偶氮类颜料中间体DCB与红色基B的合成及工业化设计[D]. 济南: 济南大学, 2023.
	Yan F. Synthesis and industrial design of azo pigment intermediates DCB and Fast Red B[D]. Jinan: University of Jinan, 2023.
5	Lomax S Q, Learner T. A review of the classes, structures, and methods of analysis of synthetic organic pigments[J]. Journal of the American Institute for Conservation, 2006, 45(2): 107-125.
6	Lomax S Q, Lomax J F. The synthesis characterization of historical novel azo pigments: implications for conservation science[J]. Heritage Science, 2019, 7(1): 101.
7	张瑾. 偶氮色淀颜料在水介质中分散性及相关机理研究[D]. 上海: 上海应用技术大学, 2023.
	Zhang J. Study on dispersion and related mechanism of azo lake pigments in aqueous medium[D]. Shanghai: Shanghai Institute of Technology, 2023.
8	Schmidt M U, Brüning J, Wirth D, et al. Two azo pigments based on β-naphthol[J]. Acta Crystallographica Section C: Crystal Structure Communications, 2008, 64(9): o474-o477.
9	Christie R M, Mackay J L. Metal salt azo pigments[J]. Coloration Technology, 2008, 124(3): 133-144.
10	费学宁, 于艳, 周春隆. 红色色酚类色淀颜料的结构与性能[J]. 天津化工, 1996, 10(3): 5-8.
	Fei X N, Yu Y, Zhou C L. Structure and properties of red phenolic lake pigment[J]. Tianjin Chemical Industry, 1996, 10(3): 5-8.
11	俞鸿安. 我国C.I.颜料红57∶1的生产现状和发展前景[J]. 染料工业, 1992, 29(6): 53-55.
	Yu H A. Production status and development prospect of C.I. Pigment Red 57∶1 in China[J]. Dyestuffs and Coloration, 1992, 29(6): 53-55.
12	金炳生, 何珉, 董国兴. C.I.颜料红57∶1的新制备方法[J]. 染料与染色, 2008, 45(5): 10-11.
	Jin B S, He M, Dong G X. The new preparation method of C. I. Pigment Red 57∶1[J]. Dyestuffs and Coloration, 2008, 45(5): 10-11.
13	Seo H S, Lee H K, Yoo E S. Particle size, morphology and color characteristics of C.I. Pigment Red 57∶1∶2. Effect of salt milling process[J]. Textile Coloration and Finishing, 2015, 27(4): 245-260.
14	梁玉华, 吕东军. C.I颜料红57∶1合成条件和改性的研究[J]. 应用化工, 2002, 31(1): 35-38.
	Liang Y H, Lv D J. Research on synthetic condition and modification of C.I. Pigment Red 57∶1[J]. Applied Chemical Industry, 2002, 31(1): 35-38.
15	Zhang X N, Stefanick S, Villani F J. Application of microreactor technology in process development[J]. Organic Process Research & Development, 2004, 8(3): 455-460.
16	Gutmann B, Cantillo D, Kappe C O. Continuous-flow technology— a tool for the safe manufacturing of active pharmaceutical ingredients[J]. Angewandte Chemie International Edition, 2015, 54(23): 6688-6728.
17	Zhang M X, Roth P. Flow photochemistry—from microreactors to large-scale processing[J]. Current Opinion in Chemical Engineering, 2023, 39: 100897.
18	王法军, 黄晋培, 徐建鸿. 微反应器内红色基KD重氮化反应动力学研究[J]. 化工学报, 2021, 72(2): 984-992.
	Wang F J, Huang J P, Xu J H. Kinetics of Red Base KD diazotization in microreactor system[J]. CIESC Journal, 2021, 72(2): 984-992.
19	Wang F J, Huang J P, Xu J H. Continuous-flow synthesis of azo dyes in a microreactor system[J]. Chemical Engineering and Processing - Process Intensification, 2018, 127: 43-49.
20	石至平. 偶氮颜料的连续化合成工艺研究[D]. 天津: 天津大学, 2020.
	Shi Z P. Study on the continuous synthetic process of azo pigments[D]. Tianjin: Tianjin University, 2020.
21	王旭东. 颜料红146与颜料黄12的连续化合成工艺研究[D]. 天津: 天津大学, 2021.
	Wang X D. Study on continuous synthesis process of Pigment Red 146 and Pigment Yellow 12[D]. Tianjin: Tianjin University, 2021.
22	McCormack A T, Stephens J C. The continuous flow synthesis of azos[J]. Journal of Flow Chemistry, 2024, 14(2): 377-396.
23	Dietz E, Weber J, Schnaitmann D, et al. Process for fine division of organic pigments by precipitation: US6537364[P]. 2003-03-25.
24	Pennemann H, Forster S, Kinkel J, et al. Improvement of dye properties of the Azo Pigment Yellow 12 using a micromixer-based process[J]. Organic Process Research & Development, 2005, 9(2): 188-192.
25	杨林涛, 刘东, 王永华. 微通道反应器在重氮化偶合反应中的应用研究[J]. 染料与染色, 2017, 54(2): 57-62.
	Yang L T, Liu D, Wang Y H. Application of microchannel reactors in diazotization and coupling[J]. Dyestuffs and Coloration, 2017, 54(2): 57-62.
26	Wang F J, Huang J P, Xu J H. Continuous-flow synthesis of the Azo Pigment Yellow 14 using a three-stream micromixing process[J]. Organic Process Research & Development, 2019, 23(12): 2637-2646.
27	Mao Y X, Zhou C L, Wang C Y, et al. Continuous-flow synthesis and crystal modification of Pigment Red 53[J]. Chinese Chemical Letters, 2023, 34(8): 108061.
28	丁云成, 王法军, 艾宁, 等. 微反应器内连续重氮化/偶合反应进展[J]. 化工学报, 2018, 69(11): 4542-4552.
	Ding Y C, Wang F J, Ai N, et al. Research progress on continuous diazotization/azo-coupling reaction in microreactors[J]. CIESC Journal, 2018, 69(11): 4542-4552.
29	Abdelmaksoud W M A, Aboaly M M M, Taleb S M. Synthesis and characterization of novel pigments derived from Red Lake C[J]. Pigment & Resin Technology, 2019, 48(5): 383-388.
30	Fei X N, Li S, Wu B, et al. Properties of a composite pigment of C.I. Pigment Red 177 prepared via a solid-state ball milling method[J]. Dyes and Pigments, 2022, 203: 110331.
31	Ren F X, Fei X N, Cui L F, et al. Preparation and properties of hydrophilic P.R. 57∶1 with inorganic core/solid solution shell[J]. Dyes and Pigments, 2020, 183: 108699.

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