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Abbreviation (ISO4): Prog Chem      Editor in chief: Jincai ZHAO

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Progress in Chemistry >

2026 , Vol. 38 >Issue 2: 274 - 282

DOI: https://doi.org/10.7536/PC20250312

Review

Continuous Flow Enzymatic/Chemo-Enzymatic Ring-Opening Polymerizations

  • Aiai Su 1 ,
  • Yihuan Liu 1 ,
  • Jin Huang , 1, * ,
  • Hengquan Yang , 2, * ,
  • Kai Guo 1 ,
  • Ning Zhu , 1, *
Expand
  • 1 State Key Laboratory of Materials-Oriented Chemical Engineering， College of Biotechnology and Pharmaceutical Engineering，Nanjing Tech University， Nanjing 211800， China
  • 2 Shanxi Key Laboratory of the Green Catalytic Synthesis of Coal-Based High Value Chemicals， School of Chemistry and Chemical Engineering，Shanxi University， Taiyuan 030006， China
*（Jin Huang）；
（Hengquan Yang）；
（Ning Zhu）

Received date: 2025-03-20

  Revised date: 2025-09-10

  Online published: 2026-01-31

Supported by

National Natural Science Foundation of China(22278223)

National Natural Science Foundation of China(22478188)

National Natural Science Foundation of China(U24A20492)

Sinopec R&D Program(223272)

Fold

Abstract

Ring-opening polymerizations （ROP） of cyclic monomers for the synthesis of biodegradable polymers have attracted growing research interest from polymer chemistry. As a green synthetic strategy，enzymatic ROP still suffers from bottlenecks，such as low efficiency and broad molecular weight distribution. In contrast to the traditional batch reactor，a microreactor featuring a huge surface-to-volume ratio and continuous flow characteristics enables process intensification and allows for applications in organic and polymeric synthesis. Recently，remarkable advantages have been demonstrated by the combination of microreactor-based flow chemistry and enzymatic ROP，such as accelerated apparent polymerization rate constant，lower polydispersity （Đ），and higher end-group fidelity. Moreover，continuous flow chemo-enzymatic platforms have been developed to efficiently prepare biodegradable block and bottlebrush copolymers. This review focuses on the advances in microreactor-based continuous flow enzymatic and chemo-enzymatic ring-opening polymerizations for the synthesis of biodegradable polymers. The challenges and opportunities are also discussed with the target for the development of biocatalysis and biodegradable polymers.

Contents

1 Introduction

2 Synthesis of biodegradable polymers by continuous flow enzymatic ROP

2.1 Water as initiator

2.2 Alcohol as initiator

2.3 Optimization of polymerizations

3 Synthesis of functional biodegradable polymers by continuous flow chemo-enzymatic routes

3.1 Block copolymers

3.2 Bottlebrush polymers

3.3 Polymer stabilized nanoparticles

4 Conclusion and outlook

Key words： continuous flow; enzymatic; chemo-enzymatic; ring-opening polymerizations; biodegradable polymers

Cite this article

Aiai Su , Yihuan Liu , Jin Huang , Hengquan Yang , Kai Guo , Ning Zhu . Continuous Flow Enzymatic/Chemo-Enzymatic Ring-Opening Polymerizations[J]. Progress in Chemistry, 2026 , 38(2) : 274 -282 . DOI: 10.7536/PC20250312

1 Introduction

Developing biodegradable materials is one of the important pathways to achieve sustainable development and a research hotspot in the field of polymer chemistry[1-6]. Aliphatic polyesters and polycarbonates possess ester and carbonate bonds in their repeating units, exhibiting excellent biodegradability and biocompatibility[7-11], in tissue engineering[12], drug delivery[13], packaging materials[14], electronic materials[15-16]and other fields have application value. Ring-opening polymerization (ROP) of cyclic monomers such as lactones, lactides, and carbonates is one of the main methods for preparing biodegradable materials with controllable structures[17], catalytic systems mainly include metal complexes[18-20], small organic molecules[21-24]and enzymes[25-26].
Enzymatic biocatalysis is a class of green synthesis methods[27-28], offering advantages such as mild conditions, safety, and environmental friendliness[29-31]. Scholars domestically and internationally have conducted systematic research on the lipase-catalyzed ring-opening polymerization of various cyclic monomers, achieving significant results. Lipases include Candida antarctica lipase B (CALB), archaeal thermophilic esterase (AFEST), Pseudomonas fluorescens lipase (PFL), and porcine pancreatic lipase (PPL), among others[32]. Among these, CALB and its immobilized form Novozyme 435 (N435) exhibit excellent substrate compatibility and high catalytic activity, making them the most widely applied[33]. However, enzymatic ring-opening polymerization still faces bottlenecks such as low synthesis efficiency and broad molecular weight distribution, urging the development of new improvement strategies[34-35].
Compared with traditional batch stirred-tank reactors, microreactors have characteristic dimensions at the hundred-micrometer scale, possessing extremely large specific surface areas and continuous flow characteristics, which can intensify mixing, mass transfer, and heat transfer rates, improve selectivity, and suppress side reactions.[36], and have been successfully applied in fields such as organic chemistry and polymer synthesis.[37-43]. For enzymatic reactions, microreactors can better maintain enzyme activity, significantly shorten reaction times, and reduce the formation of by-products.[44-45]. Furthermore, the excellent spatiotemporal controllability of microreactors facilitates the coupling of bio-chemical catalysis.[46-50], avoiding mutual interference between different catalysts and enabling the efficient preparation of functionalized copolymer materials.[51-52].
This article focuses on continuous-flow enzymatic and chemo-enzymatic ring-opening polymerization reactions in microreactors. It summarizes research progress on the preparation of biodegradable materials, such as homopolymers and copolymers, from cyclic monomers including lactones, lactides, and carbonates via ring-opening polymerization and polymerization-polymerization coupling. Furthermore, it discusses the associated challenges and opportunities, aiming to provide insights for research in related fields.

2 Continuous flow enzymatic ring-opening polymerization for the preparation of biodegradable polymers

Enzymatic ring-opening polymerization follows the "activated monomer" mechanism, where effective contact between residues and substrates is key to the polymerization reaction[53-54]. The confined space and continuous flow characteristics of microreactors provide opportunities for shortening enzymatic reaction time, reducing the molecular weight distribution index, and improving end-group fidelity[55].

2.1 Water as an initiator

Water present in the polymerization system can initiate ring-opening polymerization, yielding polymers end-capped with carboxyl and hydroxyl groups; however, enzymatic reactions suffer from issues such as slow rates and low molecular weights. In 2011, Gross et al.[56]established a continuous-flow enzymatic ring-opening polymerization method, which effectively increased the apparent polymerization rate constant and molecular weight compared to batch kettle reactors. An aluminum microreactor covered with a Kapton film was packed with immobilized CALB (N435) (Figure 1); under conditions of fixed retention volume, different residence times were conveniently regulated by changing the flow rate. The apparent rate constant for the enzymatic polymerization of ε-caprolactone (CL) in the batch kettle reactor was 0.0004~0.0008 s-1, and the molecular weight of the product, poly(ε-caprolactone) (PCL), was below 10,000 g/mol. Under the same conditions, the microreactor increased the apparent rate constant to 0.007~0.012 s-1, with the molecular weight reaching 15,000~20,000 g/mol. This is because the huge specific surface area of the microreactor enhanced the effective contact between the enzyme's active sites and the substrate, accelerating the reaction rate. Meanwhile, the higher diffusion efficiency within the microreactor facilitated the diffusion of polymer chain ends to the enzyme's active sites, thereby producing polymer products with higher molecular weights.[56].
图1 填充CALB微反应器中酶促ε-己内酯开环聚合[56]

Fig.1 CALB packed microreactor system for continuous flow enzymatic ROP of ε-caprolactone[56]. Copyright © 2011 American Chemical Society

2.2 alcohol as an initiator

The introduction of specific end groups is crucial for enhancing polymer performance and expanding application ranges[57]. Using alcohols as initiators for ring-opening polymerization can yield biodegradable materials with different end-group structures. However, when alcohols, water, thiols, amines, etc., coexist, competitive initiation reactions typically occur, resulting in mixtures with different end groups[58]. Continuous-flow enzymatic ring-opening polymerization offers advantages in improving chemoselectivity.
In 2012, Gross et al.[59]used benzyl alcohol as a model initiator to comparatively study the effects of different conditions in microreactors and stirred tank reactors on the benzyl alcohol-water initiation reaction and the end-group fidelity of poly(ε-caprolactone) (Figure 2a). Due to the dynamic flow characteristics in the microreactor, part of the water in the system was transferred to the enzyme, part flowed out with the solvent, and only a small portion participated in initiating the ring-opening polymerization. Therefore, when using toluene saturated with water as the solvent, the microreactor, while enhancing the apparent rate constant (kapp = 0.027 s-1vs. kapp = 0.001 s-1), achieved an end-group fidelity exceeding 75%, whereas under the same conditions, the stirred tank reactor achieved only 20%–30% end-group fidelity (Figure 2b).
图2 （a） 苯甲醇作为引发剂连续流酶促ɛ-己内酯开环聚合；（b） 微反应器和釜式反应器中苯甲醇引发占比-时间关系[59]

Fig.2 （a） Benzyl alcohol as initiator for continuous flow enzymatic ring-opening polymerization of ε-caprolactone in microreactors；（b） fraction of chains initiated by benzyl alcohol in microreactor and batch mode as a function of reaction time[59]. Copyright © 2012 American Chemical Society

In 2021, Rolando et al.[60]investigated the immobilized CALB-catalyzed initiation by 3-phenyl-1-propanol in a poly(ethylene-co-tetrafluoroethylene) tubular reactorε-caprolactone (CL) andδ-valerolactone (VL) ring-opening polymerization. Compared with stirred tank reactors, the tubular microreactor improved the controllability of the ring-opening polymerization and shortened the reaction time. At a residence time of 214 s, ε-caprolactone was completely converted, and the molecular weight distribution index (Đ) was approximately 1.30;δ-valerolactone (VL) conversion was 93%, with a molecular weight distribution index of approximately 1.27. By alternating the feeding of lactone monomers, block copolymers were successfully prepared. The immobilized enzyme could be reused more than 10 times while maintaining high catalytic activity.
As an initiator, mercaptoalcohol involves hydroxyl-mercapto competitive initiation in ring-opening polymerization, leading to the long-standing need for protecting the mercapto group during the synthesis of mercapto-terminated polyesters, followed by deprotection after polymerization, resulting in cumbersome steps and low efficiency.[58]. In 2005, Martinelle et al.[61]utilized the chemical selectivity of CALB, using 2-mercapto-1-ethanol as an initiator to directly synthesize mercapto-functionalized polyε-caprolactone without mercapto protection. However, due to competitive side reactions of the mercapto group and the aforementioned water-initiated reaction, the mercapto fidelity in the batch reactor was only about 70%, failing to meet the requirements for applications of mercapto-terminated polymers. AnotherCandida sp. 99-125 lipase achieved over 90% mercapto fidelity, but the reaction time was as long as 7 days, monomer conversion was below 80%, and the molecular weight distribution index exceeded 2.0.[62].
In response to the aforementioned issues, in 2018, Guo Kai et al.[63]proposed a method for preparing thiol-functionalized polyesters via microscale continuous-flow enzymatic selective ring-opening polymerization. In a constructed tubular microreactor packed with N435, using 6-mercapto-1-hexanol (MH) as an initiator, thiol-end-capped polylactones with well-defined structures and narrow molecular weight distributions were efficiently prepared (Figure 3). Compared to batch reactors, benefiting from dynamic flow characteristics and a significant reduction in residence time, the immobilized enzyme microreactor increased end-group fidelity from 77% to over 90%, resulting in more controllable polymer molecular weights and narrower molecular weight distributions. By varying the monomer-to-initiator feed ratio and adjusting the flow rate, thiol-end-capped polymers were synthesized with thiol fidelity of 90%–98%, molecular weights of 1150–9570 g/mol, and dispersity indices of 1.13–1.26. Furthermore, by constructing a series-connected immobilized enzyme microreactor system, block copolymers PVL-b-PCL and PCL-b-PVL with different structures, molecular weights, and high thiol incorporation rates were successfully prepared.
图3 连续流酶促合成巯基封端聚（δ-戊内酯）与聚（δ-戊内酯）-聚（ε-己内酯）嵌段共聚物[63]

Fig.3 Continuous flow enzymatic synthesis of thiol-terminated PVL and PCL-b-PVL[63]

2.3 Reaction system optimization

The reaction medium has a significant impact on enzymatic reactions[64]. Pickering emulsions refer to emulsions obtained using ultrafine solid particles as emulsifiers. They offer advantages such as good stability, strong designability, and environmental friendliness, and are widely applied in enzyme catalysis, bio-chemical coupled catalysis, and other fields[65-66]. In 2022, Sherazi et al.[67]developed a continuous flow catalytic system based on Pickering emulsions (Figure 4) for the ring-opening polymerization of ε-caprolactone catalyzed by free enzyme CALB. Stable water/toluene (W/O) Pickering emulsions were constructed using silica nanoparticles (SiNPs) modified with octyltrimethoxysilane (OTMS) and aminopropyltrimethoxysilane (APTMS) as emulsifiers, wherein the enzyme was encapsulated in the aqueous droplet dispersed phase. When the OTMS-to-APTMS ratio was 2:1, the emulsifier dosage was 5% (by mass), the enzyme dosage was 3% (by mass), and the flow rate was 3 mL/h, the monomer conversion rate reached a maximum of 88%. Compared with batch reactions, the continuous flow system demonstrated higher catalytic efficiency and product molecular weight, and the enzyme retained nearly 100% activity after 8 cycles of use.
图4 连续流Pickering乳液酶促开环聚合[67]

Fig. 4 Continuous flow enzymatic ROP by using Pickering emulsions [67].

Supercritical fluids are special fluids existing above critical temperature and critical pressure, with properties between those of liquids and gases, such as supercritical carbon dioxide (scCO2), etc. They exhibit strong permeability and solubility for materials and are applied in fields such as reactions and extraction.[68]. In 2004, Gross et al.[69]used CALB to catalyze the ring-opening polymerization of ε-caprolactone in scCO₂. After reacting for 6–72 h, the yield was approximately 95%–98%, producing poly(ε-caprolactone) with a molecular weight of 12,000–37,000 g/mol and a polydispersity index of 1.4–1.6. In 2018, de Oliveira et al.[70]investigated the CALB enzyme-catalyzed ring-opening polymerization of ε-caprolactone in scCO2 using compressed liquefied petroleum gas and carbon dioxide as solvents, based on a packed-bed reactor (-caprolactone ring-opening polymerization (Figure 5)[71]. Dichloromethane (DCM) was used as a co-solvent. Under conditions of 65 °C and 120 bar (1 bar = 100 kPa), a monomer conversion of 93% (by mass) was achieved within 15 min. The molecular weight of the poly(ε-caprolactone) reached 31,200 g/mol (Ð = 1.4–1.6). The addition of DCM significantly improved mass transfer in the system and reduced the pressure drop across the reactor (25 vs. 35.04 bar). The enzyme retained high activity after 6 cycles, but the product molecular weight decreased from 23,100 g/mol to 17,200 g/mol, possibly due to side reactions involving water catalyzed by the enzyme.
图5 超临界二氧化碳为溶剂连续流酶促开环聚合[71]

Fig.5 Schematic diagram of continuous flow enzymatic ROP by using ScCO2 as solvent[71]

Ultrasound assistance can enhance the mass transfer efficiency of the reaction system. In 2013, Annuar et al.[72]investigated ultrasound-assisted CALB-catalyzedε-caprolactone ring-opening polymerization. Ultrasonic irradiation increased the chain propagation rate constant (kp) by 34%–46% at high monomer concentrations of 18.0–22.5 mol/L; polymerization was sustained even when the viscosity of the reaction mixture increased to 2000 times its initial value, achieving a monomer conversion of 73.2%, a molecular weight of approximately 20,600 g/mol, and an increased crystallinity of 61%. Simulation results indicated that replacing a continuous stirred-tank reactor (CSTR) with a plug flow reactor (PFR) could reduce the reactor volume to at least one-tenth of the original.

3 Continuous flow bio-chemical coupling preparation of functionalized polymers

Bio-chemical catalytic coupling integrates the respective advantages of different catalysis methods, providing convenience for the design and synthesis of functionalized materials such as block copolymers, bottlebrush copolymers, and polymer-modified nanoparticles.[73-77]. The excellent spatiotemporal controllability of microreactors makes them an ideal platform technology for bio-chemical catalytic coupling.[78].

3.1 Block copolymer

Block copolymers are functional polymer materials formed by covalently linking two or more different structural homopolymer segments, widely used in biomaterials[79]and materials science[80-81]and many other fields. In 2018, Guo Kai et al.[82]designed a microscale continuous flow chemical-enzymatic reaction platform. Based on the enzymatic ring-opening polymerization to prepare thiol-end-capped poly(ε-caprolactone), coupled with free radical polymerization initiated by azobisisobutyronitrile (AIBN), they efficiently synthesized poly(ε-caprolactone)-block-poly(N-vinylpyrrolidone) (PCL-b-PVP) amphiphilic block copolymers (Figure 6). In an N435-packed microreactor, enzymatic selective ring-opening polymerization initiated by 6-mercapto-1-hexanol yielded narrowly distributed PCL with an end-group incorporation rate exceeding 90% (Mn=1230~10320 g/mol,Ð = 1.1~1.3). Further coupling with continuous flow free radical polymerization, using thiol end groups as chain transfer agents, by changing the molar ratio of vinylpyrrolidone to thiol and controlling reaction time via flow rate adjustment, amphiphilic block copolymers PVP30-b-PCL30and PVP60-b-PCL30.
图6 连续流化学-酶法开环聚合-自由基聚合耦合平台制备聚己内酯-聚乙烯基吡咯烷酮嵌段共聚物[82]

Fig.6 Continuous flow chemo-enzymatic ROP-radical polymerization platform for synthesis of PCL-b-PVL copolymer[82]

As monomers commonly used in ring-opening polymerization, ε-caprolactone (CL), trimethylene carbonate (TMC), and lactide (LA) exhibit similar yet distinct properties, making the synthesis of block copolymers using a single catalyst challenging.[83]. For instance, CALB can efficiently catalyze the polymerization of ε-caprolactone and trimethylene carbonate but exhibits low activity toward lactide; a typical representative of organic catalysts, 1,5,7-triazabicyclo[4.4.0]dec-5-ene (TBD), can rapidly catalyze the polymerization of lactide and trimethylene carbonate but catalyzes ε-caprolactone polymerization relatively slowly.[84]. In 2019, Ning Zhu, Kai Guo, et al.[84]developed a continuous-flow enzyme-organic catalysis coupling strategy based on a tandem microreactor system, suitable for the ring-opening copolymerization of various cyclic monomers, yielding a series of triblock copolymers (Figure 7). For ε-caprolactone, δ-valerolactone, and trimethylene carbonate, N435-packed microreactor units were constructed; for lactide, organocatalytic microreactor units were built. Through the tandem connection of different microreactor units and condition control, triblock copolymers with different molecular weights and narrow distributions were efficiently obtained (Đ<1.3), such as PCL-b-PTMC-b-PVL, PCL-b-PTMC-b-PLLA, PTMC-b-PCL-b-PLLA, etc. Compared with batch reactors, continuous-flow chemo-enzymatic ring-opening polymerization significantly shortens the overall reaction time (<40 min), avoids the separation and purification of enzymes and reaction intermediates, and offers better controllability in terms of molecular weight and dispersity index.
图7 连续流化学-酶法开环聚合-开环聚合耦合平台制备聚己内酯-聚碳酸酯-聚丙交酯三嵌段共聚物[84]

Fig.7 Continuous flow chemo-enzymatic ROP-ROP platform for synthesis of PCL-b-PTMC-b-PLLA copolymer[84]

3.2 Bottlebrush copolymer

Bottlebrush copolymers are comb-shaped polymers composed of side chains and a backbone[85], adopting cylindrical or worm-like conformations, and are widely used in photonic crystals[86], nanomedicine[87], antifouling coatings[88], and nanopatterning[89]and other fields. Significant progress has been made in the synthesis of bottlebrush copolymers, but challenges such as low synthesis efficiency, tedious purification steps, and unclear structures remain[90-91]. In 2022, Zhu Ning, Guo Kai, et al.[92]developed a microreactor-based chemo-enzymatic cascade platform for the synthesis of bottlebrush copolymers (Figure 8). First, enzymatic ring-opening polymerization of ε-caprolactone initiated by norbornene alcohol (NB-OH) was conducted in an N435-packed microreactor. Compared with a tank reactor, the reaction time was reduced to 1/10 of the original, and the resulting polyε-caprolactone macromonomers exhibited higher end-group incorporation rates (up to 97%), with more controllable molecular weight and dispersity (Mn=5070~11270 g/mol, Ð= 1.2~1.4). Second, ring-opening metathesis polymerization (ROMP) of the separated and purified polyε-caprolactone macromonomers catalyzed by the third-generation Grubbs catalyst (G3) was investigated in a tubular microreactor, achieving nearly complete conversion of the macromonomers (95%~99%). Finally, a tandem system consisting of an enzymatic ring-opening polymerization microreactor unit and a metal-catalyzed ring-opening metathesis polymerization unit (ROP-ROMP) was constructed. This eliminated the need for separation and purification of the enzyme and macromonomers, improving efficiency. By adjusting microreactor parameters and reaction conditions, polyε-caprolactone bottlebrush copolymers with various backbone and side chain lengths were efficiently obtained (Mn=36000~98100 g/mol, Ð = 1.09~1.29), providing key generic technologies for the efficient synthesis of bottlebrush copolymers.
图8 连续流化学-酶法开环聚合-开环易位聚合耦合平台制备聚己内酯瓶刷共聚物[92]

Fig.8 Continuous flow chemo-enzymatic ROP-ROMP platform for synthesis of PCL bottlebrush copolymer[92]

3.3 Polymer-modified nanoparticles

Precious metal nanoparticles possess unique electronic, optical, and catalytic properties; modification with small molecules or polymers can impart better dispersibility and functionality to the nanoparticles.[93-95]. As commonly used stabilizers, thiol-containing polymers modify precious metal nanoparticles by forming sulfur-metal bonds. In 2018, Guo Kai et al.[82]based on a microscale continuous flow chemical-enzymatic reaction platform, efficiently prepared poly(ε-caprolactone)-modified silver nanoparticles via a two-phase method (Figure 9). In the two-phase method, control of conditions such as the thiol/metal molar ratio and mass transfer efficiency are key factors influencing nanoparticle formation.[96]. Thiol-terminated poly(ε-caprolactone) obtained via continuous flow enzymatic ring-opening polymerization was mixed with tetraoctylammonium bromide. By regulating the flow rates of the toluene solution of thiol-terminated poly(ε-caprolactone)/tetraoctylammonium bromide, the aqueous silver nitrate (AgNO3) solution, and the aqueous sodium borohydride (NaBH4) solution, the molar ratio of metal to thiol was altered. Leveraging the process intensification effect of the microreactor to accelerate mixing and mass transfer efficiency, well-dispersed, size-controllable polymer-modified silver nanoparticles were successfully prepared.
图9 连续流化学-酶法合成聚ε-己内酯修饰的银纳米粒子[82]

Fig.9 Continuous flow chemo-enzymatic synthesis of PCL stabilized silver nanoparticles[82]

4 Conclusion and Outlook

As a green synthesis method, enzymatic ring-opening polymerization for preparing biodegradable materials has attracted research interest in fields such as polymer synthesis chemistry. Continuous flow microreactor technology, featuring process intensification effects, significantly enhances the enzymatic ring-opening polymerization process. Compared with traditional batch kettle reactions, it increases the apparent polymerization rate constant, reduces the molecular weight distribution index, and improves end-group fidelity. Based on microreactor technology, continuous flow bio-chemical catalytic coupling has been preliminarily achieved, efficiently preparing functionalized biodegradable materials such as block copolymers, bottlebrush copolymers, and polymer-modified nanoparticles. Looking ahead, research on continuous flow enzymatic/chemical-enzymatic ring-opening polymerization is suggested to focus on the following directions: (1) Deepen the understanding of enzymatic reaction mechanisms in confined spaces; based on emerging technologies such as artificial intelligence, elucidate the laws of enzymatic ring-opening polymerization in microreactors and create new enzymes with low cost and high activity; (2) Ingeniously design bio-chemical catalytic coupling systems; leveraging the unique advantages of technologies such as Pickering emulsions, develop chemical-enzymatic strategies oriented toward the synthesis of advanced functional materials and expand application fields; (3) Vigorously promote scale-up research on microreactors; utilizing powerful tools such as advanced imaging and fluid simulation, develop macro-micro reactors that combine microscale effects with large-scale preparation[97-98], laying a solid foundation for engineering translation.

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