Abstract
Reversible addition-fragmentation chain transfer radical polymerization of styrene and maleic anhydride was successfully performed in continuous-flow microreactor. Results of the structural characterization showed that the obtained styrene-maleic anhydride (SMA) copolymers possessed controlled molecular weight, low dispersity and alternating structures. Subsequently, effects of the polymerization conditions, including reaction pressure, temperature, feed flowrate and tube length, on the polymerization kinetics and molecular structure of the SMA copolymers were investigated in detail. It was found that the reaction rate was increased as the reaction temperature increased within certain limits, as well as the feed flowrate due to the increased mass and heat transfer efficiency. Besides, first-order kinetics of the polymerization was observed when the reaction times were adjusted by only changing the tube length. Good stability was exhibited when the reaction conducted continuously for 10 h. This approach can reduce the reaction time significantly from several hours to about half an hour.
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References
Park ES, Kim MN, Lee IM et al (2000) Living radical copolymerization of styrene/maleic anhydride. Journal of Polymer Science Part a-Polymer Chemistry 38:2239–2244
Zhang P, Xiang S, Wang H et al (2019) Understanding the multiple functions of styrene-co-maleic anhydride in fabricating polyvinylidene fluoride hollow fiber membrane via coupled phase inversion process and its effect on surface infiltration behavior and membrane permeability. J Membr Sci 590:117269
Le CMQ, Cao XT, Kim DW et al (2017) Preparation of poly(styrene-alt-maleic anhydride) grafted multi-walled carbon nanotubes for pH-responsive release of doxorubicin. Mol Cryst Liq Cryst 654:181–189
Sirohi S, Jassal M, Agrawal AK (2018) Surfactant-free nanoencapsulation using reactive oligomers obtained by reversible addition fragmentation chain transfer polymerization of styrene and maleic anhydride. Appl Nanosci 8:1701–1710
Li L, Huang M, Zheng S (2016) Mesoporous carbons from nanostructured phenolic thermosets containing poly(styrene-alt-maleic anhydride)-block-polystyrene diblock copolymer. Ind Eng Chem Res 55:11502–11511
Luo S, Qiao X, Wang Q-Y et al (2019) Excellent self-healing and antifogging coatings based on polyvinyl alcohol/hydrolyzed poly(styrene-co-maleic anhydride). J Mater Sci 54:5961–5970
Moriceau G, Lester D, Pappas GS et al (2019) Well-defined alkyl functional poly(styrene-co-maleic anhydride) architectures as pour point and viscosity modifiers for lubricating oil. Energy Fuel 33:7257–7264
Sutekin SD, Atici AB, Guven O et al (2018) Controlling of free radical copolymerization of styrene and maleic anhydride via RAFT process for the preparation of acetaminophen drug conjugates chock. Radiat Phys Chem 148:5–12
Baranello MP, Bauer L, Benoit DSW (2014) Poly(styrene-alt-maleic anhydride)-based diblock copolymer micelles exhibit versatile hydrophobic drug loading, drug-dependent release, and internalization by multidrug resistant ovarian cancer cells. Biomacromolecules. 15:2629–2641
Hrib J, Chylikova Krumbholcova E, Duskova-Smrckova M et al (2019) Hydrogel tissue expanders for stomatology. Part II. poly(styrene-maleic anhydride) hydrogels. Polymers (Basel) 11:1087–1102
Lessard B, Maric M (2010) One-step poly(styrene-alt-maleic anhydride)-block-poly(styrene) copolymers with highly alternating styrene/maleic anhydride sequences are possible by nitroxide-mediated polymerization. Macromolecules. 43:879–885
Moriceau G, Tanaka J, Lester D et al (2019) Influence of grafting density and distribution on material properties using well-defined alkyl functional poly(styrene-co-maleic anhydride) architectures synthesized by RAFT. Macromolecules. 52:1469–1478
Goto A, Sato K, Tsujii Y et al (2001) Mechanism and kinetics of RAFT-based living radical polymerizations of styrene and methyl methacrylate. Macromolecules. 34:402–408
Davies MC, Dawkins JV, Hourston DJ (2005) Radical copolymerization of maleic anhydride and substituted styrenes by reversible addition-fragmentation chain transfer (RAFT) polymerization. Polymer. 46:1739–1753
Moriceau G, Gody G, Hartlieb M et al (2017) Functional multisite copolymer by one-pot sequential RAFT copolymerization of styrene and maleic anhydride. Polym Chem 8:4152–4161
Jose Benvenuta-Tapia J, Vivaldo-Lima E, Alfredo Tenorio-Lopez J et al (2018) Kinetic analysis of the RAFT copolymerization of styrene and maleic anhydride by differential scanning calorimetry. Thermochim Acta 667:93–101
Chernikova E, Terpugova P, Bui C et al (2003) Effect of comonomer composition on the controlled free-radical copolymerization of styrene and maleic anhydride by reversible addition-fragmentation chain transfer (RAFT). Polymer. 44:4101–4107
Yao Z, Zhang J-S, Chen M-L et al (2011) Preparation of well-defined block copolymer having one polystyrene segment and another poly(styrene-alt-maleic anhydride) segment with RAFT polymerization. J Appl Polym Sci 121:1740–1746
Junkers T (2017) Precise macromolecular engineering via continuous-flow synthesis techniques. Journal of Flow Chemistry 7:106–110
Lee C-Y, Fu L-M (2018) Recent advances and applications of micromixers. Sensors Actuators B Chem 259:677–702
Kuroki A, Martinez-Botella I, Hornung CH et al (2017) Looped flow RAFT polymerization for multiblock copolymer synthesis. Polym Chem 8(21):3249–3254
Liu X, Lu Y, Luo G (2017) Continuous flow synthesis of polystyrene nanoparticles via emulsion polymerization stabilized by a mixed nonionic and anionic emulsifier. Ind Eng Chem Res 56:9489–9495
Xiang L, Wang W-J, Li B-G et al (2017) Tailoring polymer molecular weight distribution and multimodality in RAFT polymerization using tube reactor with recycle. Macromol React Eng 11:1700023
Buss BL, Miyake GM (2018) Photoinduced controlled radical polymerizations performed in flow: methods, products, and opportunities. Chem Mater 30:3931–3942
Lu Y, Zhu S, Wang K et al (2016) Generation of poly(isobutene-co-isoprene) in a microflow device. Ind Eng Chem Res 55:1215–1220
Lauterbach F, Rubens M, Abetz V et al (2018) Ultrafast photoRAFT block copolymerization of isoprene and styrene facilitated through continuous-flow operation. Angew Chem Int Ed Engl 57:14260–14264
Lai JT, Filla D, Shea R (2002) Functional polymers from novel carboxyl-terminated trithiocarbonates as highly efficient RAFT agents. Macromolecules. 35:6754–6756
You YZ, Hong CY, Pan CY (2002) Controlled alternating copolymerization of St with MAh in the presence of DBTTC. Eur Polym J 38:1289–1295
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We are grateful for financial support from the National Natural Science Foundation of China (No. Y8A3401501).
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Liu, W., Li, Q., Zhang, Y. et al. Continuous-flow RAFT copolymerization of styrene and maleic anhydride: acceleration of reaction and effect of polymerization conditions on reaction kinetics. J Flow Chem 11, 867–875 (2021). https://doi.org/10.1007/s41981-021-00167-0
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DOI: https://doi.org/10.1007/s41981-021-00167-0