Application mechanism of micromixer in the synthesis of methyl thioglycolate Application mechanism of micromixer in the synthesis of methyl thioglycolate and process value-added research and process value-added research
Application of Micromixer in Methyl Mercaptoacetate Synthesis Application of Micromixer in Methyl Mercaptoacetate Synthesis
Introduction Introduction
Methyl mercaptoacetate, as the core intermediate of sulfur-containing fine chemical industry, has irreplaceable application value in the fields of pesticide creation, pharmaceutical synthesis, fragrance refining, polymer additives, optical curing materials, etc. Its downstream-derived thiophensulfuron herbicide, high-end tobacco fragrance, epoxy resin low-temperature curing system, PVC environmental protection organotin heat stabilizer and other products have strict requirements on the purity, impurity content and color index of intermediates, and are the key raw materials to support the high-end development of fine chemical industry. Methyl mercaptoacetate, as the core intermediate of sulfur-containing fine chemical industry, has irreplaceable application value in the fields of pesticide creation, pharmaceutical synthesis, fragrance refining, polymer additives, and optical curing materials, etc. Its downstream-derived thiophensulfuron herbicide, high-end tobacco flavor, epoxy resin low-temperature curing system, PVC environmental protection organotin heat stabilizer and other products have strict requirements on intermediate purity, impurity content and chromaticity index, and are the key raw materials to support the high-end development of fine chemicals.
Compared with the mature synthesis technology systems in Europe, America and Japan, the research on thioglycolic acid and derivatives in our country started in the 1970s. The industrial technology accumulation is weak, and industrialization has long relied on extensive batch production processes. The traditional sulfuric acid catalytic tank esterification process has structural shortcomings such as low yield, long reaction cycle, strong corrosion of equipment, large emissions of three wastes, and poor batch stability. Domestic high-purity and low-impurity high-end thioglycolate methyl ester products have long relied on imports, and the high-end supply gap is significant. Industrial technology upgrading and process innovation are imminent. In this context, microfluidic process strengthening technology with micromixers as the core has become the core technology path to crack the bottleneck of traditional processes and achieve high-quality and efficient green production. Compared with the mature synthesis technology systems in Europe, America and Japan, the research on thioglycolic acid and derivatives in our country started in the 1970s, and the industrial technology accumulation was weak. Industrialization has long relied on extensive batch production processes. The traditional sulfuric acid catalytic tank esterification process has structural shortcomings such as low yield, long reaction cycle, strong corrosion of equipment, large emissions of three wastes, and poor batch stability. Domestic high-purity and low-impurity high-end thioglycolate methyl ester products have long been dependent on imports, and the high-end supply gap is significant. Industrial technology upgrading and process innovation are imminent. In this context, microfluidic process strengthening technology with micromixers as the core has become the core technology path to crack the bottleneck of traditional processes and achieve high-quality and efficient green production.
Domestic Research and Industrial Process Status of Methyl 1 Mercaptoacetate Domestic Research and Industrial Process Status of Methyl 1 Mercaptoacetate
The domestic industry-university-research field has gradually completed the landing and downstream application verification of the basic synthesis technology of thiophenylacetate methyl ester. Anhui Fengle Agrochemical took the lead in realizing industrial synthesis and successfully applied it to the large-scale production of thiophenylsulfuron herbicide, opening up the supporting industrial chain of pesticide intermediates; Guizhou Institute of Chemical Technology and Yisheng Fine Chemical have completed the synthesis of high-end fragrance monomers such as 3-carbonyl-2-methylhydrothiophenylcarboxylate methyl ester and 4-carbonyl-2-tetrahydrothiophenylcarboxylate methyl ester relying on this intermediate, verifying its application potential in the field of fine fragrances and providing raw material support for domestic fragrance localization. The domestic industry-university-research field has gradually completed the landing and downstream application verification of the basic synthesis technology of thiophenylacetate methyl ester. Anhui Fengle Agrochemical took the lead in realizing industrialized synthesis, and successfully applied it to the large-scale production of thiophenesulfuron herbicide, opening up the supporting industrial chain of pesticide intermediates; Guizhou Institute of Chemical Industry and Yisheng Fine Chemicals relied on this intermediate to complete the synthesis of high-end fragrance monomers such as 3-carbonyl-2-methylhydrothiophenecarboxylate methyl ester and 4-carbonyl-2-tetrahydrothiophenecarboxylate methyl ester, verifying its application potential in the field of fine fragrances and providing raw material support for domestic fragrance localization.
However, from the perspective of the mainstream process of industrialization, the current domestic production system is highly single, relying entirely on the mainstream process of industrialization. However, from the perspective of the mainstream process of industrialization, the current domestic production system is highly single, relying entirely on the thioglycolic acid-methanol homogeneous sulfuric acid catalytic batch esterification process. Although the process has low equipment investment and low operating threshold, there are unavoidable underlying defects: first, the strong acid catalytic system corrodes the reaction kettle and supporting equipment, which has high operation and maintenance costs and fast equipment depreciation; second, the batch kettle type mixing efficiency is limited, and the uneven mixing of materials leads to poor reaction selectivity and frequent side reactions; third, the reversible reaction balance of esterification is obviously limited, the product cannot be separated in time, and the raw material conversion rate and product yield are difficult to break through the upper limit; fourth, the high temperature of the sulfur-containing system for a long time can easily lead to thiol oxidation and polymerization side reactions, and the accumulation of impurities is serious, making it difficult to produce high-end products. Overall, the traditional process has been unable to adapt to the current development requirements of green, high-end and fine chemical industry, and new process strengthening technologies are urgently needed to complete the process iteration... Although the process has low equipment investment and low operating threshold, there are unavoidable underlying defects: first, the strong acid catalytic system corrodes the reaction kettle and supporting equipment, which has high operation and maintenance costs and fast equipment depreciation; second, the batch kettle type mixing efficiency is limited, and the uneven mixing of materials leads to poor reaction selectivity and frequent side reactions; third, the reversible reaction balance of esterification is obviously limited, the product cannot be separated in time, and the raw material conversion rate and product yield are difficult to break through the upper limit; fourth, the high temperature of the sulfur-containing system for a long time can easily lead to thiol oxidation and polymerization side reactions, and the accumulation of impurities is serious, making it difficult to produce high-end products. Overall, the traditional process has been unable to adapt to the current green, high-end and fine chemical development requirements, and new process strengthening technologies are urgently needed to complete the process iteration.2 Micromixer core characteristics and esterification reaction adaptation advantages 2 Micromixer core characteristics and esterification reaction adaptation advantages
Micromixer is the core functional unit of microfluidic chemical industry. It relies on precision micromachining technology to build a three-dimensional micro-scale flow channel structure, which specifically solves the industry common problem of low efficiency of laminar flow mixing in micro-reaction systems. It is an independent strengthening core equipment that is different from ordinary microchannel reactors. According to the operation mechanism, it can be divided into active and passive types. Among them, micromixer is the core functional unit of microfluidic chemical industry. It relies on precision micromachining technology to build a three-dimensional micro-scale flow channel structure, which specifically solves the industry common problem of low efficiency of laminar flow mixing in micro-reaction systems. It is an independent strengthening core equipment that is different from ordinary microchannel reactors. According to the operating mechanism, it can be divided into active and passive types, among which the passive micro-mixer passive micro-mixer has become the mainstream selection of fine esterification reaction by virtue of the advantages of no moving parts, no external power, stable operation, and adaptation to industrial continuous production. It relies on the geometric structure of the flow channel to reconstruct the fluid motion state to achieve efficient mixing at the microscale. With the advantages of no moving parts, no external power, stable operation, and adaptation to industrial continuous production, it has become the mainstream selection of fine esterification reaction, and relies on the geometric structure of the flow channel to reconstruct the fluid motion state to achieve efficient mixing at the microscale.
In the conventional cognition, the advantages of microchannel reactors focus on heat transfer enhancement and plank flow without backmixing, while in the conventional cognition, the advantages of microchannel reactors focus on heat transfer enhancement and plank flow without backmixing, while the core value of the micromixer focuses on mass transfer limit enhancement. The core value of the micromixer focuses on mass transfer limit enhancement , and the two form a complementary strengthening system. In the conventional microchannel reaction system, the Reynolds number of the fluid in the microchannel is extremely low, it is always in a stable laminar flow state, the fluid has no turbulent disturbance, and only relies on slow molecular diffusion to achieve mixing. It is prone to problems such as uneven radial concentration layer, imbalance of local raw material ratio, and uneven distribution of catalytic activity, which restrict the improvement of esterification reaction rate and yield. The micromixer forces the fluid to stratify, tear, fold, and accelerate through special bending, shunting, converging, and shearing channel structures, which greatly increases the specific surface area of fluid contact, breaks the limit of laminar diffusion, and significantly improves the microscopic mixing efficiency. It improves the quality and efficiency of the esterification reaction from the mass transfer level., the two form a complementary strengthening system. In the conventional microchannel reaction system, the Reynolds number of the fluid in the microscale flow channel is extremely low, and it is always in a stable laminar flow state. The fluid has no turbulent disturbance, and only relies on slow molecular diffusion to achieve mixing. It is prone to problems such as uneven radial concentration layer, imbalance of local raw material ratio, and uneven distribution of catalytic activity, which restricts the improvement of the esterification reaction rate and yield. The micromixer uses a special bending, shunting, converging, and shearing channel structure to force the fluid to stratify, tear, fold, and accelerate, which greatly increases the specific surface area of the fluid contact, breaks the laminar diffusion limit, and significantly improves the micromixing efficiency.
At present, the micro-mixing strengthening technology has been widely verified in various esterification reactions, and has universal process advantages. The quartz capillary microsystem can realize the rapid and high yield synthesis of short URL esters, and the ester yield can reach more than 97.2%; the glass chip microstructure reactor can increase the esterification reaction rate by more than 50 times; the borosilicate glass micro-mixing system can achieve nearly 100% conversion of aromatic esters, and the reaction time is greatly compressed. A large number of studies have confirmed that the micro-mixing strengthening technology can specifically solve the pain points of mass transfer lag, uneven mixing, and multiple side reactions in esterification reactions, providing precise technical support for sulfur-containing esterification systems such as mercaptoacetate methyl esters that are sensitive to mixing accuracy. At present, the micro-mixing strengthening technology has been widely verified in various esterification reactions, and has universal technological advantages. The quartz capillary microsystem can realize the rapid and high yield synthesis of short URL esters, and the ester yield can reach more than 97.2%; the glass chip microstructure reactor can increase the esterification reaction rate by more than 50 times; the borosilicate glass micro-mixing system can achieve nearly 100% conversion of aromatic esters, and the reaction time is greatly compressed. A large number of studies have confirmed that the micro-mixing strengthening technology can specifically solve the pain points of mass transfer lag, uneven mixing, and multiple side reactions in the esterification reaction, providing precise technical support for sulfur-containing esterification systems such as mercaptoacetate methyl esters that are sensitive to mixing accuracy.
Iterative Application and Mechanism Innovation of 3 Micromixer in Synthesis of Methyl Mercaptoacetate
Domestic research on the synthesis of thioglycolate methyl ester enhanced by micromixer has completed two rounds of technology iterations, upgrading from a single microchannel reaction to a coupled system of "micro-mixing pre-strengthening + microchannel reaction", which completely solves the shortcoming of pure microchannel system mixing lag. Jia Shaoming's team took the lead in using a single-pump feed capillary microchannel synthesis process, verifying that the microscale reaction can greatly compress the reaction time, confirming the synergy of microfluidic technology for the esterification reaction, but the single-pump premixing mode still has the problems of uneven macro mixing and insufficient feed ratio accuracy, and the mixing strengthening effect is limited. Domestic research on the synthesis of thioglycolate methyl ester enhanced by micromixer has completed two rounds of technology iterations, upgrading from a single microchannel reaction to a coupled system of "micro-mixing pre-strengthening + microchannel reaction", which completely solves the shortcoming of pure microchannel system mixing lag. Jia Shaoming's team took the lead in using a single-pump feed capillary microchannel synthesis process, verifying that the microscale reaction can greatly compress the reaction time, confirming the synergy of microfluidic technology for the esterification reaction, but the single-pump premixed mode still has the problems of uneven macro mixing and insufficient feed ratio accuracy, and the mixing strengthening effect is limited. The Niu Berlin team completed the key process upgrade on this basis, and constructed the Niu Berlin team to complete the key process upgrade on this basis. The continuous system of double-pump precision feeding - micro-mixer pre-strengthening - capillary reaction double-pump precision feeding - micro-mixer pre-strengthening - capillary reaction has realized the precision of material ratio, the extreme of micro-mixing, and the stabilization of the reaction process. The core innovation of this device is to decouple the mixing process from the reaction process, and use the micro-mixer to complete the homogeneous mixing of thioglycolic acid, methanol, and catalyst in advance, and then feed it into the micro-channel for constant temperature esterification, completely avoiding the mixing defects of traditional processes and pure micro-channel processes. The core innovation of this device is to decouple the mixing process from the reaction process, using a micromixer to complete the homogeneous mixing of thioglycolic acid, methanol and catalyst in advance, and then feed it into the microchannel for constant temperature esterification reaction, completely avoiding the mixing defects of traditional and pure microchannel processes. The controlled experiment data directly confirms the core value-added role of the micromixer: under the same working conditions of 0.6mm inner diameter capillary and 60 ° C, the product yield is only 86.2% when the micromixer is strengthened, and the yield is increased to 91.0% after the installation of the micromixer. The yield of a single working condition is increased by 4.8 percentage points, and the synergistic effect is significant. Multiple controlled experiments show that the micromixer can stably improve the reaction yield and reaction uniformity under different pipe diameters and different temperature conditions, and the microchannel system with small pipe diameter has better adaptability and stronger process amplification stability. The controlled experiment data directly confirms the core value-added role of the micro-mixer: under the same working conditions of 0.6mm inner diameter capillary and 60 ° C, the product yield is only 86.2% when the micro-mixer is strengthened, and the yield is increased to 91.0% after the installation of the micro-mixer. The yield of a single working condition is increased by 4.8 percentage points, and the synergistic effect is significant. Several sets of controlled experiments show that the micro-mixer can stably improve the reaction yield and reaction uniformity under different pipe diameters and different temperature conditions, and the micro-channel system with small pipe diameter has better adaptability and stronger process amplification stability. Disassembled from the depth of fluid mechanics and reaction mechanism, the synergistic core logic of the micromixer is different from the conventional reaction enhancement methods, and has unique technical barriers. Macro-scale reactors rely on turbulent disturbance to achieve mixing, while the micro-scale system has an extremely low Reynolds number, which naturally cannot form turbulence. The traditional stirring and mixing logic is completely invalid. It only relies on molecular diffusion to mix, resulting in slow mass transfer rate and large local concentration difference. The micromixer reconstructs the flow state of the microscale fluid by changing the flow channel structure and the friction coefficient of the fluid, triggers the laminar transition effect in advance, and realizes the rapid homogeneous mixing of multiple fluids in milliseconds, eliminating the problems of local alkyd ratio imbalance, local catalyst enrichment or lack. Disassembled from the depth of fluid mechanics and reaction mechanism, the synergistic core logic of the micromixer is different from the conventional reaction enhancement methods, and has unique technical barriers. Macro-scale reactors rely on turbulent disturbance to achieve mixing, while the micro-scale system has an extremely low Reynolds number, which naturally cannot form turbulence. The traditional stirring and mixing logic is completely ineffective, and only relies on molecular diffusion mixing. The mass transfer rate is slow and the local concentration difference is large. The micromixer reconstructs the flow state of the microscale fluid by changing the flow channel structure and the friction coefficient of the fluid, triggers the laminar transition effect in advance, and realizes the rapid homogeneous mixing of multiple fluids in milliseconds, eliminating the problems of local alcohol-acid ratio imbalance, local catalyst enrichment or lack. Aiming at the particularity of the esterification reaction of thioglycolate methyl ester, the precise mixing of the micro-mixer can effectively avoid the reaction lag caused by the low concentration of local methanol, the thiolactone esterification and oxidation side reactions caused by the high concentration of local acid. While increasing the main reaction rate, it significantly reduces the amount of impurities generated. Simultaneously realizes the particularity of the esterification reaction of thioglycolate methyl ester. The precise mixing of the micro-mixer can effectively avoid the reaction lag caused by the low concentration of local methanol, and the thiolactone esterification and oxidation side reactions caused by the high concentration of local acid. While increasing the main reaction rate, it significantly reduces the amount of impurities generated. Simultaneously realizes the triple effect of yield improvement + purity optimization + side reaction inhibition yield improvement + purity optimization + side reaction inhibition . This It is a technical advantage that cannot be achieved by traditional kettle process and pure micro-channel process. Triple effect, which is a technical advantage that cannot be achieved by traditional kettle process and pure micro-channel process. 4 Industrial Adaptation Value and Differentiation Advantage of Microhybrid Enhancement Process 4 Industrial Adaptation Value and Differentiation Advantage of Microhybrid Enhancement Process Compared with the traditional batch process and the ordinary micro-channel process, the pre-mixed enhanced coupling system has a strong industrial landing value, accurately matching the upgrading needs of the current methyl thioglycolate industry. First, to solve the inherent shortcomings of the microfluidic process, ordinary microchannels rely on the self-diffusion and mixing of materials, feed fluctuations and ratio deviations can easily lead to a decrease in reaction stability, and the pre-strengthening of the micromixer can achieve feed homogenization, which greatly improves the operating stability of the device and the consistency of the product batch. Second, it is suitable for the sensitive reaction characteristics of the sulfur-containing system. The precise and mild mixing reaction environment can protect the sulfhydryl active groups, reduce the generation of by-products, and help the localization of high-end and high-purity products. Third, it can reduce industrial energy consumption and costs, shorten the reaction induction period with efficient mixing, improve the utilization rate of raw materials, reduce the excessive input of methanol and the energy consumption of subsequent rectification. At the same time, the low liquid holding capacity characteristics greatly improve the intrinsic safety of production and avoid the Compared with the traditional batch process and the ordinary micro-channel process, the pre-mixed enhanced coupling system has a strong industrial landing value, accurately matching the upgrading needs of the current thioglycolate methyl ester industry. First, to solve the inherent shortcomings of the microfluidic process, ordinary microchannels rely on the self-diffusion and mixing of materials, feed fluctuations and ratio deviations can easily lead to a decrease in reaction stability, and the pre-strengthening of the micromixer can achieve feed homogenization, which greatly improves the operation stability of the device and the consistency of the product batch. Second, it is suitable for the sensitive reaction characteristics of the sulfur-containing system. The precise and mild mixing reaction environment can protect the sulfhydryl active groups, reduce the generation of by-products, and help the localization of high-end and high-purity products. Third, it can reduce industrial energy consumption and costs, shorten the reaction induction period with efficient mixing, improve the utilization rate of raw materials, reduce the excessive input of methanol and the energy consumption of subsequent rectification. At the same time, the low liquid holding capacity characteristics greatly improve the intrinsic safety of production and avoid the risk of high temperature
From an industrial perspective, this technological breakthrough has broken the "low-efficiency, high-pollution, and low-quality" curing pattern of the domestic methylthioglycolate industry. Traditional processes are subject to uneven mixing and unbalanced reactions, unable to break through the bottleneck of yield and purity, and high-end products are imported for a long time. Micro-mixing strengthening technology has the advantages of low cost, easy adaptation, and continuity, and can achieve process quality improvement and efficiency without high equipment transformation investment, providing a new path for the transformation of domestic excess basic fine chemical production capacity into high-end intermediate production. From an industrial perspective, this technological breakthrough has broken the "low-efficiency, high-pollution, and low-quality" curing pattern of the domestic methylthioglycolate industry. The traditional process is subject to uneven mixing and unbalanced reaction, unable to break through the bottleneck of yield and purity, and high-end products are imported for a long time. Micro-hybrid strengthening technology has the advantages of low cost, easy adaptation and continuity, and does not require high equipment transformation investment. It can achieve process quality improvement and efficiency, providing a new path for the transformation of domestic excess basic fine chemical production capacity into high-end intermediate production. Conclusion As the core mass transfer enhancement equipment of the microfluidic system, the micromixer specifically solves the core pain points of low-efficiency microscale laminar mixing, uneven material, frequent side reactions, and limited yield in the esterification reaction of thioglycolate methyl acetate. Through the coupling process of pre-micromixing enhancement and microchannel reaction, the homogeneous mixing of materials at millisecond level can be achieved, the reaction is precise and controllable, and the side reaction is effectively suppressed. The product yield and product purity can be significantly improved under mild working conditions, making up for the technical shortcomings of traditional batch process and pure microchannel process. The process is green, efficient, safe and stable, and has strong industrial adaptability. It can effectively promote the production of methyl thioglycolate from extensive intermittent to precise continuous iteration, and solve the dilemma of import dependence of domestic high-end products. It has important theoretical research value and engineering application value for the green, high-end and domestic development of sulfur-containing fine ester intermediates. As the core mass transfer strengthening equipment of the microfluidic system, the micromixer specifically solves the core pain points of low efficiency of microscale laminar mixing, uneven material, multiple side reactions and limited yield in the esterification reaction of methyl thioglycolate. Through the coupling process of pre-micromixing strengthening and microchannel reaction, millisecond-level homogeneous mixing of materials can be achieved, the reaction is precise and controllable, and the side reactions are effectively suppressed. The product yield and product purity can be significantly improved under mild working conditions, making up for the technical shortcomings of traditional batch process and pure microchannel process. The process is green, efficient, safe and stable, and has strong industrial adaptability. It can effectively promote the production of thioglycolate methyl ester from extensive batch to precision continuous iteration, and solve the domestic high-end product import dependence dilemma. It has important theoretical research value and engineering application value for the green, high-end and domestic development of sulfur-containing fine ester intermediates. References References [1] Yu Yijun, Shi De. Pesticide Application Daquan [M]. Agricultural Press, 2008. [1] Yu Yijun, Shi De. Pesticide Application Daquan [M]. Agricultural Press, 2008. [2] Shepherd. Robin Gerald. Intermediates for Drugs and Sweet-eners. EurPat. 344.983 GBAppl88/12,718. [2] Shepherd. Robin Gerald. Intermediates for Drugs and Sweet-eners. EurPat. 344.983 GBAppl88/12,718.
[4] Lin Changzhi. Synthesis of methyl thioglycolate [J]. Anhui Chemical Industry, 2004, 30 (3): 26-27. [4] Lin Changzhi. Synthesis of methyl thioglycolate [J]. Anhui Chemical Industry, 2004, 30 (3): 26-27.
[5] Ye Xingxing, Mansur EHA, Wang Yundong, et al. Research progress of micro-mixing technology [J]. Chemical Industry Progress, 2007, 26 (6): 755-761. [5] Ye Xingxing, Mansur EHA, Wang Yundong, et al. Research progress of micro-mixing technology [J]. Chemical Industry Progress, 2007, 26 (6): 755-761.
Du Dongxing. Effects of compressibility and roughness on flow and heat transfer characteristics in microtubes [D]. Beijing: Tsinghua University, 2000. [6] Du Dongxing. Effects of compressibility and roughness on flow and heat transfer characteristics in microtubes [D]. Beijing: Tsinghua University, 2000.[7] Yao X, Yao J, Zhang L, et al. Fast Esterification of Acetic Acids with Short Chain Alcohols in Microchannel Reactors [J]. Catalysis Letters, 2009, 132 (1-2): 147-152. [7] Yao X, Yao J, Zhang L, et al. Fast Esterification of Acetic Acids with Short Chain Alcohols in Microchannel Reactors [J]. Catalysis Letters, 2009, 132 (1-2): 147-152.
[8] Brivio M, Oosterbroek R E, Verboom W, et al. Surface effects in the esterification of 9-pyrenebutyric acid within a glass micro reactor. [J]. Chemical Communications, 2003, 2003 (15): 1924-5. [8] Brivio M, Oosterbroek R E, Verboom W, et al. Surface effects in the esterification of 9-pyrenebutyric acid within a glass micro reactor. [J]. Chemical Communications, 2003, 2003 (15): 1924-5.
[9] Benitolopez F, Tiggelaar R M, Salbut K, et al. Substantial rate enhancements of the esterification reaction of phthalic anhydride with methanol at high pressure and using supercritical CO2 as a co-solvent in a glass microreactor. [J]. Lab on A Chip, 2007, 7 (10): 1345-51. [9] Benitolopez F, Tiggelaar R M, Salbut K, et al. Substantial rate enhancements of the esterification reaction of phthalic anhydride with methanol at high pressure and using supercritical CO2 as a co-solvent in a glass microreactor. [J]. Lab on A Chip, 2007, 7 (10): 1345-51.
[10] Wiles C, Watts P, Haswell S J, et al. Solution phase synthesis of esters within a micro reactor [J]. Tetrahedron, 2003, 59 (51): 10173-10179. [10] Wiles C, Watts P, Haswell S J, et al. Solution phase synthesis of esters within a micro reactor [J]. Tetrahedron, 2003, 59 (51): 10173-10179.
Jia Shaoming, Li Yafang, Zhao Jianhong, et al. Application of microstructure reactor in synthesis of methyl thioglycolate [J]. Advances in Chemical Engineering, 2011 (S1): 56-58. [11] Jia Shaoming, Li Yafang, Zhao Jianhong, et al. Application of microstructure reactor in synthesis of methyl thioglycolate [J]. Advances in Chemical Engineering, 2011 (S1): 56-58. Jia Shaoming. Application of microstructure reactor in synthesis of methyl thioglycolate [D]. Zhengzhou University, 2012. [12] Jia Shaoming. Application of microstructure reactor in synthesis of methyl thioglycolate [D]. Zhengzhou University, 2012.[13] Niu Berlin, Jia Shaoming, Li Yafang, et al. Rapid synthesis of methyl thioglycolate in a microchannel reactor [J]. Journal of Nanjing University of Technology: Natural Science Edition, 2013, 35 (2): 36-40. [13] Niu Berlin, Jia Shaoming, Li Yafang, et al. Rapid synthesis of methyl thioglycolate in a microchannel reactor [J]. Journal of Nanjing University of Technology: Natural Science Edition, 2013, 35 (2): 36-40.
| (Note: Parts of the document may be AI-generated) | (Note: Parts of the document may be AI-generated)
