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Continuous flow photoinduced phenothiazine derivatives catalyzed atom transfer radical polymerization
European Polymer Journal 126 (2020) 109565
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European Polymer Journal journal homepage: www.elsevier.com/locate/europolj
Continuous flow photoinduced phenothiazine derivatives catalyzed atom transfer radical polymerization ⁎
T
⁎
Weijun Huanga,c, Jinglin Zhaia,c, Xin Hub,c, , Jindian Duana,c, Zheng Fanga,c, Ning Zhua,c, , Kai Guoa,c a
College of Biotechnology and Pharmaceutical Engineering, Nanjing Tech University, Nanjing, Jiangsu 211800, China College of Materials Science and Engineering, Nanjing Tech University, Nanjing, Jiangsu 211800, China c State Key Laboratory of Materials-Oriented Chemical Engineering, Nanjing Tech University, Nanjing, Jiangsu 211800, China b
A R T I C LE I N FO
A B S T R A C T
Keywords: Flow Photoinduced Organocatalysis ATRP Phenothiazine derivatives
Continuous flow photoinduced organocatalyzed atom transfer radical polymerizations (O-ATRP) are investigated by using phenothiazine derivatives as organic photoredox catalysts. A series of phenothiazine derivatives with different substituents are designed and synthesized. The structure-reactivity relationship is examined in both batch and tubular reactor by employing methyl methacrylate (MMA) and ethyl αbromophenylacetate (EBP) as the monomer and initiator. By transferring the polymerization from the batch reactor to the tubular reactor, the accelerated apparent polymerization constants, better control of molecular weights and narrower molecular weight distributions are achieved. The effect of the inner diameter of the tubular reactor on O-ATRP is explored and it suggests that 1.5 mm and 2.0 mm are the optimized inner diameter based on the consideration of polymerization controllability. By applying this continuous flow photoinduced OATRP protocol, poly(methyl methacrylate) (PMMA) and block copolymers are synthesized with varied molecular weights.
1. Introduction Atom transfer radical polymerization (ATRP) has been one of the most powerful reversible deactivation radical polymerization (RDRP) protocols for precision polymer synthesis [1–5]. Controlled-molecular weights, narrow molecular weight distributions, good end group fidelities, advanced chain architectures and topologies could be achieved by applying ATRP. The efficient activation of alkyl halide initiator and deactivation to the dormant state by metal catalyst enable the control of ATRP process. Although improved ATRP strategies were developed to decrease the metal loading into parts per million (ppm) level, the challenge of metal contamination still remains, especially for biomedical or microelectronic applications [6–20]. Photoinduced metal-free organocatalyzed atom transfer radical polymerizations (O-ATRP) have been established to address the challenge of metal contamination since 2014 [21–22]. From ultraviolet (UV) to visible light, various organic photoredox catalysts were presented, including but not limited to phenothiazines [21,23–27], polynuclear aromatic hydrocarbons [22,28], dihydrophenazines [29–30], N-arylphenoxazines [31], p-anisaldehyde [32], fluorescein [33], dicyanobenzenes [34], thienothiophenes [35], 2,4,5,6-Tetrakis ⁎
(diphenylamino)-1,3-benzenedicarbonitrile and 5,5′-(sulfonyldi-4,1phenylene)bis[5,10-dihydro-10-phenyl-phenazine] [36], etc. The emerging O-ATRP proves to be a versatile and robust approach to yield tailor-made polymers [37–39]. The scope of the photoredox catalyst and the structure–activity relationship should be explored in further [40–42]. In the other hand, due to the inherent light gradient effect by the Beer-Lambert law, the process and scalability of O-ATRP are limited in the batch reactor [43–44]. In contrast to the traditional batch reactors, tubular reactors with huge surface-to-volume ratio provide improved mixing and heat/mass transfer efficiency, flow characteristic and high-level control of reaction conditions [45–48]. Continuous flow polymerizations [49], such as ionic polymerizations [50–52], radical polymerizations [53–56] and ring-opening polymerizations [57–61], have achieved remarkable advances compared with the batch reactor. The combination of photopolymerization and microflow technology would allow for the benefits of uniform light penetration intensity, spatial and temporal control and easy to scale up, etc [62–63]. Recently, progress in continuous flow photoinduced controlled radical polymerizations were achieved. Oxygen tolerent RAFT photopolymerization [64–65] and photoinduced copper-RDRP [66] were presented by using microreactors. Cross-linked
Corresponding authors at: College of Biotechnology and Pharmaceutical Engineering, Nanjing Tech University, Nanjing, Jiangsu 211800, China. E-mail addresses: [email protected] (X. Hu), [email protected] (N. Zhu).
https://doi.org/10.1016/j.eurpolymj.2020.109565 Received 29 January 2020; Accepted 10 February 2020 Available online 11 February 2020 0014-3057/ © 2020 Elsevier Ltd. All rights reserved.
European Polymer Journal 126 (2020) 109565
W. Huang, et al.
star polymers were synthesized via flow photoinduced copper mediated polymerization [67]. Ultrafast photoRAFT block copolymerizations of isoprene and styrene in flow were performed to prepare polystyreneblock-polyisoprene-block-polystyrene (PS-b-PI-b-PS) triblock copolymers [68]. Moreover, continuous flow photopolymerization induced self-assembly (PISA) was explored to obtain nano-objects with varied morphologies [69–70]. The potential has not fully been explored so that more efforts should be made on the continuous flow O-ATRP [71–72]. In this contribution, the scope of the phenothiazine derivatives was expanded and the structure–activity relationship of the catalysts was evaluated in both batch and tubular reactor. The interesting finding of the enhanced catalytic activities in flow encouraged us to investigate the effect of the inner diameter of the tubular reactor on the O-ATRP. By applying this continuous flow photoinduced O-ATRP approach, poly (methyl methacrylate) (PMMA) and block copolymers were synthesized with varied molecular weights.
in Fig. 2. Ph-PTZ, CNPh-PTZ, CF3Ph-PTZ and Py-PTZ exhibited relative high Kapp over 0.05 h−1. The molecular weights and distributions versus conversions were ploted in Fig. S3. The molecular weight distributions (Ð) were kept between 1.20 and 1.80. However, the molecular weights were not linearly increased with the conversions. It might be attributed to the fast activation but inefficient deactivation [24]. Next, we transferred the structure-reactivity relationship study from the batch reactor to the tubular reactor (Fig. 3). A simple quartz tubular reactor with UV light in the middle while cooling with an air fan was assembled according to the literature (Fig. S2) [71,72]. All catalysts achieved higher monomer conversions, better control of molecular weight distributions and narrower molecular distributions (Table 2). The apparent rate constants were much higher than those in batchwise reactions (Fig. 2). In flow mode, except for the CF3Ph-PTZ (Kapp = 0.0948 h−1) and Py-PTZ (Kapp = 0.2681 h−1), other phenothiazine derivatives showed almost the same Kapp (0.15–0.17 h−1), 3–5 times larger than those in the batch reactors. The linear indipendence between molecular weights and conversions was improved (Fig. S3). It was attributed to higher concentrations of excited state photoredox catalyst for the subsequent faster activation of the EBP initiator in the microreactor in the benefit of an improved irradiation efficiency due to the large surface-to-volume ratio of the microreactor, together with the flow characteristic. [65] The interesting finding of the enhanced catalytic activities of phenothiazine derivatives encouraged us to investigate the effect of inner diameter of the tubular reactor on the flow O-ATRP. To the best of our knowledge, there was no related research about scale effect study on OATRP. Quarts tubular reactors with varied scales (inner diameter (ID) = 1.0 mm, 1.5 mm, 2.0 mm, 2.5 mm, 3.0 mm) were assembled. The residence volume was fixed by matching the length of the reactor. The residence time was constant by using the same flow rate. The polymerizations in N, N-dimethylacetamide (DMAc) (3.75 mol/L) with a target degree of polymerization (DP) of 100 were performed with PhPTZ as the organocatalyst. The semilogarithmic kinetic plots were shown in Fig. 4. The apparent rate constants increased from 0.057 to 0.143 with the reduction of ID from 3.0 mm to 2.0 mm and then changed slightly by further decreasing the ID. The polymerization results were summarized in Table 2. For the ID of 2.0 mm and 1.5 mm, relatively good initiator efficiency (Table2, run 2 and 3) was obtained which indicated that the experimental molecular weights were agreed with the theoretical values. The molecular weight distributions were narrower than those in other IDs. For the ID = 1.0 mm, the apparent rate constant was close to those in 1.5 mm and 2.0 mm reactor. However, the molecular weight distribution became broader. It was noteworthy that scale effect study did not tell us the smaller must enable the better. In order to demonstrate the versatility of flow O-ATRP method, monomer/initiator feed ratio ([MMA]/[EBP]) was adjusted to obtain
2. Results and discussion For the photoinduced O-ATRP system, the structure of photoredox organocatalyst has significant impact on the catalytic performance [39–41]. Based on the previous work [21,24], we designed and synthesized a series of phenothiazine derivatives with different substituents (MeOPh-PTZ, Ph-PTZ, ClPh-PTZ, CNPh-PTZ, CF3Ph-PTZ, PyPTZ, 1-Nap-PTZ, 2-Nap-PTZ) (Fig. 1). The UV-Vis spectra of the synthesized catalysts were shown in Fig. S1. The structure-reactivity relationship was evaluated by employing methyl methacrylate (MMA) and ethyl α-bromophenylacetate (EBP) as the model monomer and initiator. All the batchwise reactions were carried out at room temperature under UV irradiation while cooling with an air fan. Two commercial UV lamps (λmax ~ 365 nm, 8Wx2) were utilized with irradiation intensity of about 2.86 mW/cm2. The control experiments were conducted. Removal of the light, no polymers were collected after 30 h (Table S1, run 1). In the absence of photo catalyst, the molecular weight lost control and it reached 43250 g/mol with a wide molecular weight distribution (ÐM = 2.43) (Table S1, run 2). In contrast, phenothiazine derivatives catalzyed O-ATRP of MMA exhibited the control manner (Table 1). The monomer conversions could be achieved over 85% by extending the reaction time. Generally, the residence time for the microreactor was regulated as a short-time process. Therefore, to ensure the same reaction conditions, all reaction time in both batch (BR) and microreactor (MR) was set up to 3–4 h, with relative low monomer conversions. All semilogarithmic plots of monomer conversions as a function of times showed linear correlations by all phenothiazine derivatives, which indicated the polymerization rate to be first order in monomer concentration (Fig. S3). The slopes of plots represented the apparent polymerization rate constants (Kapp), which were summarized
Fig. 1. (a) O-ATRP of MMA catalyzed by phenothiazine derivatives as the organic photoredox catalyst. (b) Structure of the phenothiazine derivatives. 2
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Table 1 Photoinduced O-ATRP of MMA in the batch (BR) and tubular reactor (MR). Runa
Catalyst
Reactor
τ h
Conv.b %
Mn,theoc g mol−1
Mn,NMRb g mol−1
Mn,GPCd g mol−1
Ð Md
I*e
1 2 3 4 5 6 7 8 9 10 11 12 13 14 15 16
MeOPh-PTZ MeOPh-PTZ Ph-PTZ Ph-PTZ ClPh-PTZ ClPh-PTZ CNPh-PTZ CNPh-PTZ CF3Ph-PTZ CF3Ph-PTZ Py-PTZ Py-PTZ 1-Nap-PTZ 1-Nap-PTZ 2-Nap-PTZ 2-Nap-PTZ
BR MR BR MR BR MR BR MR BR MR BR MR BR MR BR MR
4 4 3 3 4 4 3 3 3 3 3 3 4 4 3 3
15 48 15 34 14 50 9 42 20 29 22 54 17 46 17 42
1740 5050 1740 3650 1640 5250 1140 4450 2250 3150 2450 5650 1940 4850 1940 4450
4950 10,050 4048 3750 4050 5750 6650 4850 4048 4950 6150 4250 2980 5950 3350 10,160
5530 11,350 4890 4700 4980 6710 7430 5720 4860 5630 6790 5120 3770 6720 4010 11,070
1.52 1.32 1.50 1.13 1.29 1.87 1.58 1.22 1.20 1.09 1.42 1.36 1.31 1.21 1.36 1.20
0.35 0.50 0.43 0.97 0.40 0.91 0.17 0.92 0.55 0.63 0.40 1.33 0.65 0.81 0.58 0.44
a Polymerizations were conducted at room temperature in N, N-dimethylacetamide (DMAc) (3.75 mol L−1) with [MMA]/[EBP]/[Catalyst] feed ratio of 100:1:0.05, for the microreactor, diameter=2.0 mmm, first tubing, volume=1.18 mL, length=0.37 m, second tubing, volume=1.28 mL, length=0.41 m, total volume=2.46 mL. b Calculated by 1H NMR. c Determined by conversion and the monomer feed ratio. d Calculated by GPC, dn/dc=0.083. e Determined by Mn,theo/Mn,NMR.
Table 2 The effect of the inner diameter of the tubular reactor on flow O-ATRP. Runa
ID mm
τ h
Flow rate ul/min
Conv.b %
Mn,theoc g mol−1
Mn,NMRb g mol−1
Mn,GPCd g mol−1
ÐMd
I*e
1 2 3 4 5
1.0 1.5 2.0 2.5 3.0
3 3 3 3 3
14.33 15.39 13.67 14.39 14.67
33 36 34 37 21
3550 3850 3650 3950 2350
3800 3920 3750 2650 2640
4720 4980 4530 3560 3710
1.33 1.25 1.13 1.22 1.27
0.93 0.98 0.97 1.49 0.89
a Polymerizations were conducted at room temperature in DMAc (3.75 mol L−1) with [MMA]/[EBP]/[Catalyst] feed ratio of 100:1:0.05, irradiation by 2.86 mW/cm2, 365 nm; The size of the five sets of flow reactor: (1) diameter=1.0 mm, first tubing, volume=1.15 mL, length=1.46 m, second tubing, volume=1.43 mL, length=1.82 m, total volume=2.58 mL; (2) diameter=1.5 mm, first tubing, volume=1.41 mL, length=0.80 m, second tubing, volume=1.36 mL, length=0.77 m, total volume=2.77 mL; (3) diameter=2.0 mmm, first tubing, volume=1.18 mL, length=0.37 m, second tubing, volume=1.28 mL, length=0.41 m, total volume=2.46 mL; (4) diameter=2.5 mm, first tubing, volume=1.32 mL, length=0.27 m, second tubing, volume=1.27 mL, length =0.26 m, total volume=2.59 mL; (5) diameter=3.0 mm, first tubing, volume=1.10 mL, length=0.15 m, second tubing, volume=1.54 mL, length=0.22 m, total volume=2.64 mL. b Calculated by 1H NMR. c Determined by conversion and the monomer feed ratio. d Calculated by GPC, dn/dc=0.083. e Determined by Mn,theo /Mn,NMR.
Fig. 2. Apparent polymerization rate constants (Kapp) of O-ATRP catalyzed by phenothiazine derivatives in the batch (BR) and tubular reactor (MR).
polymers with different molecular weights. Based on the results mentioned above, we chose Ph-PTZ and 2.0 mm ID tubing as the organic photoredox catalyst and the tubular reactor. The monomodal SEC traces (Fig. 5) shifted to high molecular weight regions by raising the MMA/ EBP feed ratios. The molecular weights of PMMA could be modulated
Fig. 3. The schematic tubular reactor for continuous flow photoinduced O-ATRP. 3
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from 2150 g/mol to 15880 g/mol with narrow distributions (ÐM < 1.30) and good initiation efficiency (Table 3, run 1–4). Further increasing the feed ratio to 700, 51290 g/mol PMMA was obtained but the control of polymerization became poor (ÐM = 1.48) (Table 3, run 5). To demonstrate the presence of the bromide as the polymer end group, chain extension experiments were conducted in the microreactor by using the isolated purified PMMA as the macroinitiator. Solution (comonomer (monomer 2 or 3)/PMMA/Ph-PTZ/DMAc) was prepared in glove box and then introduced into the microreactor to fabricate block copolymers. By modulating the monomer feed ratios and monomer types, poly(methyl methacrylate)-b-poly(methacrylic acid) (PMMA-b-PMAA) and poly(methyl methacrylate)-b-polystyrene (PMMA-b-PS) were efficiently synthesized (PMMA34-b-PMAA20, PMMA34-b-PMAA35, and PMMA34-b-PS21, PMMA34-b-PS40, and) (Table 3, Run 6–9). The predictable molecular weights and narrow distributions were confirmed according to SEC. The monomodal GPC trace of PMMA shifted to short elution time section after the re-initiated O-ATRP while still keeping the narrow molecular weight distribution (Fig. 6). It was indicated the presence of bromide end group and the successful copolymerization.
Fig. 4. Semilogarithmic kinetic plots for O-ATRP of MMA in the tubular reactor with different inner diameters.
3. Conclusions In summary, we reported continuous flow photoinduced phenothiazine derivatives catalyzed atom transfer radical polymerizations. The scope of the catalyst was expanded and the structure-reactivity relationship was studied in both batch and tubular reactor. By transferring the polymerization from the batch reactor to the tubular reactor (ID = 1.0–3.0 mm), accelerated apparent polymerization constants , better control of the molecular weights and narrower molecular weight distributions were achieved. Further study suggested that 1.5 mm and 2.0 mm inner diameters were the optimized reactor scale based on the consideration of apparent rate constant and polymerization controllability. By employing the optimized catalyst and tubular reactor, narrowly distributed PMMA and block copolymers were prepared with varied molecular weights. Acknowledgements This study was supported by National Natural Science Foundation of China (21604037) and National Key R&D Program of China (2019YFA0905000).
Fig. 5. SEC traces of PMMA (DPtarget = 50, 100, 300, 500, 700) (Table 3, Runs 1–5).
Data availability The data presented in this article and the Supporting Information Table 3 Flow synthesis of PMMA, PMMA-b-PMAA and PMMA-b-PS. Runa
[M1]/[M2]/[M3] /[EBP]/[Ph-PTZ]
τ h
Conv.b %
Mn,theoc g mol−1
Mn,NMRb g mol−1
Mn,GPCb g mol−1
Ð Md
I*e
1 2 3 4 5 6 7 8 9
50:0:0:1:0.025 100:0:0:1:0.05 300:0:0:1:0.15 500:0:0:1:0.25 700:0:0:1:0.35 100:100:0:1:0.05 100:50:0:1:0.05 100:0:100:1:0.05 100:0:50:1:0.05
2 3 4 6 8 3 2 3 2
39 34 38 34 41 36 35 36 39
2190 3650 11,660 17,260 28,980 6850 5260 7500 5780
2150 3750 9440 15,880 51,290 6760 5470 7920 5940
3090 4930 10,580 16,430 52,030 7560 6320 8790 7010
1.10 1.13 1.19 1.25 1.48 1.16 1.14 1.15 1.14
1.02 0.97 1.23 1.09 0.56 1.01 0.96 0.95 0.97
a b c d e
Polymerizations were conducted at room temperature in DMAc (3.75 mol L−1); [M1]=MMA; [M2]=MAA; [M3]=Styrene. Calculated by 1H NMR. Determined by conversion and the monomer feed ratio. Calculated by GPC, dn/dc=0.083. Determined by Mn,theo/Mn,NMR. 4
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Fig. 6. SEC traces of block copolymers (Table 3, Runs 6–9).
fully enable the reproduction of the scientific findings presented in the manuscript.
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Continuous flow photoinduced phenothiazine derivatives catalyzed atom transfer radical polymerization ⁎
T
⁎
Weijun Huanga,c, Jinglin Zhaia,c, Xin Hub,c, , Jindian Duana,c, Zheng Fanga,c, Ning Zhua,c, , Kai Guoa,c a
College of Biotechnology and Pharmaceutical Engineering, Nanjing Tech University, Nanjing, Jiangsu 211800, China College of Materials Science and Engineering, Nanjing Tech University, Nanjing, Jiangsu 211800, China c State Key Laboratory of Materials-Oriented Chemical Engineering, Nanjing Tech University, Nanjing, Jiangsu 211800, China b
A R T I C LE I N FO
A B S T R A C T
Keywords: Flow Photoinduced Organocatalysis ATRP Phenothiazine derivatives
Continuous flow photoinduced organocatalyzed atom transfer radical polymerizations (O-ATRP) are investigated by using phenothiazine derivatives as organic photoredox catalysts. A series of phenothiazine derivatives with different substituents are designed and synthesized. The structure-reactivity relationship is examined in both batch and tubular reactor by employing methyl methacrylate (MMA) and ethyl αbromophenylacetate (EBP) as the monomer and initiator. By transferring the polymerization from the batch reactor to the tubular reactor, the accelerated apparent polymerization constants, better control of molecular weights and narrower molecular weight distributions are achieved. The effect of the inner diameter of the tubular reactor on O-ATRP is explored and it suggests that 1.5 mm and 2.0 mm are the optimized inner diameter based on the consideration of polymerization controllability. By applying this continuous flow photoinduced OATRP protocol, poly(methyl methacrylate) (PMMA) and block copolymers are synthesized with varied molecular weights.
1. Introduction Atom transfer radical polymerization (ATRP) has been one of the most powerful reversible deactivation radical polymerization (RDRP) protocols for precision polymer synthesis [1–5]. Controlled-molecular weights, narrow molecular weight distributions, good end group fidelities, advanced chain architectures and topologies could be achieved by applying ATRP. The efficient activation of alkyl halide initiator and deactivation to the dormant state by metal catalyst enable the control of ATRP process. Although improved ATRP strategies were developed to decrease the metal loading into parts per million (ppm) level, the challenge of metal contamination still remains, especially for biomedical or microelectronic applications [6–20]. Photoinduced metal-free organocatalyzed atom transfer radical polymerizations (O-ATRP) have been established to address the challenge of metal contamination since 2014 [21–22]. From ultraviolet (UV) to visible light, various organic photoredox catalysts were presented, including but not limited to phenothiazines [21,23–27], polynuclear aromatic hydrocarbons [22,28], dihydrophenazines [29–30], N-arylphenoxazines [31], p-anisaldehyde [32], fluorescein [33], dicyanobenzenes [34], thienothiophenes [35], 2,4,5,6-Tetrakis ⁎
(diphenylamino)-1,3-benzenedicarbonitrile and 5,5′-(sulfonyldi-4,1phenylene)bis[5,10-dihydro-10-phenyl-phenazine] [36], etc. The emerging O-ATRP proves to be a versatile and robust approach to yield tailor-made polymers [37–39]. The scope of the photoredox catalyst and the structure–activity relationship should be explored in further [40–42]. In the other hand, due to the inherent light gradient effect by the Beer-Lambert law, the process and scalability of O-ATRP are limited in the batch reactor [43–44]. In contrast to the traditional batch reactors, tubular reactors with huge surface-to-volume ratio provide improved mixing and heat/mass transfer efficiency, flow characteristic and high-level control of reaction conditions [45–48]. Continuous flow polymerizations [49], such as ionic polymerizations [50–52], radical polymerizations [53–56] and ring-opening polymerizations [57–61], have achieved remarkable advances compared with the batch reactor. The combination of photopolymerization and microflow technology would allow for the benefits of uniform light penetration intensity, spatial and temporal control and easy to scale up, etc [62–63]. Recently, progress in continuous flow photoinduced controlled radical polymerizations were achieved. Oxygen tolerent RAFT photopolymerization [64–65] and photoinduced copper-RDRP [66] were presented by using microreactors. Cross-linked
Corresponding authors at: College of Biotechnology and Pharmaceutical Engineering, Nanjing Tech University, Nanjing, Jiangsu 211800, China. E-mail addresses: [email protected] (X. Hu), [email protected] (N. Zhu).
https://doi.org/10.1016/j.eurpolymj.2020.109565 Received 29 January 2020; Accepted 10 February 2020 Available online 11 February 2020 0014-3057/ © 2020 Elsevier Ltd. All rights reserved.
European Polymer Journal 126 (2020) 109565
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star polymers were synthesized via flow photoinduced copper mediated polymerization [67]. Ultrafast photoRAFT block copolymerizations of isoprene and styrene in flow were performed to prepare polystyreneblock-polyisoprene-block-polystyrene (PS-b-PI-b-PS) triblock copolymers [68]. Moreover, continuous flow photopolymerization induced self-assembly (PISA) was explored to obtain nano-objects with varied morphologies [69–70]. The potential has not fully been explored so that more efforts should be made on the continuous flow O-ATRP [71–72]. In this contribution, the scope of the phenothiazine derivatives was expanded and the structure–activity relationship of the catalysts was evaluated in both batch and tubular reactor. The interesting finding of the enhanced catalytic activities in flow encouraged us to investigate the effect of the inner diameter of the tubular reactor on the O-ATRP. By applying this continuous flow photoinduced O-ATRP approach, poly (methyl methacrylate) (PMMA) and block copolymers were synthesized with varied molecular weights.
in Fig. 2. Ph-PTZ, CNPh-PTZ, CF3Ph-PTZ and Py-PTZ exhibited relative high Kapp over 0.05 h−1. The molecular weights and distributions versus conversions were ploted in Fig. S3. The molecular weight distributions (Ð) were kept between 1.20 and 1.80. However, the molecular weights were not linearly increased with the conversions. It might be attributed to the fast activation but inefficient deactivation [24]. Next, we transferred the structure-reactivity relationship study from the batch reactor to the tubular reactor (Fig. 3). A simple quartz tubular reactor with UV light in the middle while cooling with an air fan was assembled according to the literature (Fig. S2) [71,72]. All catalysts achieved higher monomer conversions, better control of molecular weight distributions and narrower molecular distributions (Table 2). The apparent rate constants were much higher than those in batchwise reactions (Fig. 2). In flow mode, except for the CF3Ph-PTZ (Kapp = 0.0948 h−1) and Py-PTZ (Kapp = 0.2681 h−1), other phenothiazine derivatives showed almost the same Kapp (0.15–0.17 h−1), 3–5 times larger than those in the batch reactors. The linear indipendence between molecular weights and conversions was improved (Fig. S3). It was attributed to higher concentrations of excited state photoredox catalyst for the subsequent faster activation of the EBP initiator in the microreactor in the benefit of an improved irradiation efficiency due to the large surface-to-volume ratio of the microreactor, together with the flow characteristic. [65] The interesting finding of the enhanced catalytic activities of phenothiazine derivatives encouraged us to investigate the effect of inner diameter of the tubular reactor on the flow O-ATRP. To the best of our knowledge, there was no related research about scale effect study on OATRP. Quarts tubular reactors with varied scales (inner diameter (ID) = 1.0 mm, 1.5 mm, 2.0 mm, 2.5 mm, 3.0 mm) were assembled. The residence volume was fixed by matching the length of the reactor. The residence time was constant by using the same flow rate. The polymerizations in N, N-dimethylacetamide (DMAc) (3.75 mol/L) with a target degree of polymerization (DP) of 100 were performed with PhPTZ as the organocatalyst. The semilogarithmic kinetic plots were shown in Fig. 4. The apparent rate constants increased from 0.057 to 0.143 with the reduction of ID from 3.0 mm to 2.0 mm and then changed slightly by further decreasing the ID. The polymerization results were summarized in Table 2. For the ID of 2.0 mm and 1.5 mm, relatively good initiator efficiency (Table2, run 2 and 3) was obtained which indicated that the experimental molecular weights were agreed with the theoretical values. The molecular weight distributions were narrower than those in other IDs. For the ID = 1.0 mm, the apparent rate constant was close to those in 1.5 mm and 2.0 mm reactor. However, the molecular weight distribution became broader. It was noteworthy that scale effect study did not tell us the smaller must enable the better. In order to demonstrate the versatility of flow O-ATRP method, monomer/initiator feed ratio ([MMA]/[EBP]) was adjusted to obtain
2. Results and discussion For the photoinduced O-ATRP system, the structure of photoredox organocatalyst has significant impact on the catalytic performance [39–41]. Based on the previous work [21,24], we designed and synthesized a series of phenothiazine derivatives with different substituents (MeOPh-PTZ, Ph-PTZ, ClPh-PTZ, CNPh-PTZ, CF3Ph-PTZ, PyPTZ, 1-Nap-PTZ, 2-Nap-PTZ) (Fig. 1). The UV-Vis spectra of the synthesized catalysts were shown in Fig. S1. The structure-reactivity relationship was evaluated by employing methyl methacrylate (MMA) and ethyl α-bromophenylacetate (EBP) as the model monomer and initiator. All the batchwise reactions were carried out at room temperature under UV irradiation while cooling with an air fan. Two commercial UV lamps (λmax ~ 365 nm, 8Wx2) were utilized with irradiation intensity of about 2.86 mW/cm2. The control experiments were conducted. Removal of the light, no polymers were collected after 30 h (Table S1, run 1). In the absence of photo catalyst, the molecular weight lost control and it reached 43250 g/mol with a wide molecular weight distribution (ÐM = 2.43) (Table S1, run 2). In contrast, phenothiazine derivatives catalzyed O-ATRP of MMA exhibited the control manner (Table 1). The monomer conversions could be achieved over 85% by extending the reaction time. Generally, the residence time for the microreactor was regulated as a short-time process. Therefore, to ensure the same reaction conditions, all reaction time in both batch (BR) and microreactor (MR) was set up to 3–4 h, with relative low monomer conversions. All semilogarithmic plots of monomer conversions as a function of times showed linear correlations by all phenothiazine derivatives, which indicated the polymerization rate to be first order in monomer concentration (Fig. S3). The slopes of plots represented the apparent polymerization rate constants (Kapp), which were summarized
Fig. 1. (a) O-ATRP of MMA catalyzed by phenothiazine derivatives as the organic photoredox catalyst. (b) Structure of the phenothiazine derivatives. 2
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Table 1 Photoinduced O-ATRP of MMA in the batch (BR) and tubular reactor (MR). Runa
Catalyst
Reactor
τ h
Conv.b %
Mn,theoc g mol−1
Mn,NMRb g mol−1
Mn,GPCd g mol−1
Ð Md
I*e
1 2 3 4 5 6 7 8 9 10 11 12 13 14 15 16
MeOPh-PTZ MeOPh-PTZ Ph-PTZ Ph-PTZ ClPh-PTZ ClPh-PTZ CNPh-PTZ CNPh-PTZ CF3Ph-PTZ CF3Ph-PTZ Py-PTZ Py-PTZ 1-Nap-PTZ 1-Nap-PTZ 2-Nap-PTZ 2-Nap-PTZ
BR MR BR MR BR MR BR MR BR MR BR MR BR MR BR MR
4 4 3 3 4 4 3 3 3 3 3 3 4 4 3 3
15 48 15 34 14 50 9 42 20 29 22 54 17 46 17 42
1740 5050 1740 3650 1640 5250 1140 4450 2250 3150 2450 5650 1940 4850 1940 4450
4950 10,050 4048 3750 4050 5750 6650 4850 4048 4950 6150 4250 2980 5950 3350 10,160
5530 11,350 4890 4700 4980 6710 7430 5720 4860 5630 6790 5120 3770 6720 4010 11,070
1.52 1.32 1.50 1.13 1.29 1.87 1.58 1.22 1.20 1.09 1.42 1.36 1.31 1.21 1.36 1.20
0.35 0.50 0.43 0.97 0.40 0.91 0.17 0.92 0.55 0.63 0.40 1.33 0.65 0.81 0.58 0.44
a Polymerizations were conducted at room temperature in N, N-dimethylacetamide (DMAc) (3.75 mol L−1) with [MMA]/[EBP]/[Catalyst] feed ratio of 100:1:0.05, for the microreactor, diameter=2.0 mmm, first tubing, volume=1.18 mL, length=0.37 m, second tubing, volume=1.28 mL, length=0.41 m, total volume=2.46 mL. b Calculated by 1H NMR. c Determined by conversion and the monomer feed ratio. d Calculated by GPC, dn/dc=0.083. e Determined by Mn,theo/Mn,NMR.
Table 2 The effect of the inner diameter of the tubular reactor on flow O-ATRP. Runa
ID mm
τ h
Flow rate ul/min
Conv.b %
Mn,theoc g mol−1
Mn,NMRb g mol−1
Mn,GPCd g mol−1
ÐMd
I*e
1 2 3 4 5
1.0 1.5 2.0 2.5 3.0
3 3 3 3 3
14.33 15.39 13.67 14.39 14.67
33 36 34 37 21
3550 3850 3650 3950 2350
3800 3920 3750 2650 2640
4720 4980 4530 3560 3710
1.33 1.25 1.13 1.22 1.27
0.93 0.98 0.97 1.49 0.89
a Polymerizations were conducted at room temperature in DMAc (3.75 mol L−1) with [MMA]/[EBP]/[Catalyst] feed ratio of 100:1:0.05, irradiation by 2.86 mW/cm2, 365 nm; The size of the five sets of flow reactor: (1) diameter=1.0 mm, first tubing, volume=1.15 mL, length=1.46 m, second tubing, volume=1.43 mL, length=1.82 m, total volume=2.58 mL; (2) diameter=1.5 mm, first tubing, volume=1.41 mL, length=0.80 m, second tubing, volume=1.36 mL, length=0.77 m, total volume=2.77 mL; (3) diameter=2.0 mmm, first tubing, volume=1.18 mL, length=0.37 m, second tubing, volume=1.28 mL, length=0.41 m, total volume=2.46 mL; (4) diameter=2.5 mm, first tubing, volume=1.32 mL, length=0.27 m, second tubing, volume=1.27 mL, length =0.26 m, total volume=2.59 mL; (5) diameter=3.0 mm, first tubing, volume=1.10 mL, length=0.15 m, second tubing, volume=1.54 mL, length=0.22 m, total volume=2.64 mL. b Calculated by 1H NMR. c Determined by conversion and the monomer feed ratio. d Calculated by GPC, dn/dc=0.083. e Determined by Mn,theo /Mn,NMR.
Fig. 2. Apparent polymerization rate constants (Kapp) of O-ATRP catalyzed by phenothiazine derivatives in the batch (BR) and tubular reactor (MR).
polymers with different molecular weights. Based on the results mentioned above, we chose Ph-PTZ and 2.0 mm ID tubing as the organic photoredox catalyst and the tubular reactor. The monomodal SEC traces (Fig. 5) shifted to high molecular weight regions by raising the MMA/ EBP feed ratios. The molecular weights of PMMA could be modulated
Fig. 3. The schematic tubular reactor for continuous flow photoinduced O-ATRP. 3
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from 2150 g/mol to 15880 g/mol with narrow distributions (ÐM < 1.30) and good initiation efficiency (Table 3, run 1–4). Further increasing the feed ratio to 700, 51290 g/mol PMMA was obtained but the control of polymerization became poor (ÐM = 1.48) (Table 3, run 5). To demonstrate the presence of the bromide as the polymer end group, chain extension experiments were conducted in the microreactor by using the isolated purified PMMA as the macroinitiator. Solution (comonomer (monomer 2 or 3)/PMMA/Ph-PTZ/DMAc) was prepared in glove box and then introduced into the microreactor to fabricate block copolymers. By modulating the monomer feed ratios and monomer types, poly(methyl methacrylate)-b-poly(methacrylic acid) (PMMA-b-PMAA) and poly(methyl methacrylate)-b-polystyrene (PMMA-b-PS) were efficiently synthesized (PMMA34-b-PMAA20, PMMA34-b-PMAA35, and PMMA34-b-PS21, PMMA34-b-PS40, and) (Table 3, Run 6–9). The predictable molecular weights and narrow distributions were confirmed according to SEC. The monomodal GPC trace of PMMA shifted to short elution time section after the re-initiated O-ATRP while still keeping the narrow molecular weight distribution (Fig. 6). It was indicated the presence of bromide end group and the successful copolymerization.
Fig. 4. Semilogarithmic kinetic plots for O-ATRP of MMA in the tubular reactor with different inner diameters.
3. Conclusions In summary, we reported continuous flow photoinduced phenothiazine derivatives catalyzed atom transfer radical polymerizations. The scope of the catalyst was expanded and the structure-reactivity relationship was studied in both batch and tubular reactor. By transferring the polymerization from the batch reactor to the tubular reactor (ID = 1.0–3.0 mm), accelerated apparent polymerization constants , better control of the molecular weights and narrower molecular weight distributions were achieved. Further study suggested that 1.5 mm and 2.0 mm inner diameters were the optimized reactor scale based on the consideration of apparent rate constant and polymerization controllability. By employing the optimized catalyst and tubular reactor, narrowly distributed PMMA and block copolymers were prepared with varied molecular weights. Acknowledgements This study was supported by National Natural Science Foundation of China (21604037) and National Key R&D Program of China (2019YFA0905000).
Fig. 5. SEC traces of PMMA (DPtarget = 50, 100, 300, 500, 700) (Table 3, Runs 1–5).
Data availability The data presented in this article and the Supporting Information Table 3 Flow synthesis of PMMA, PMMA-b-PMAA and PMMA-b-PS. Runa
[M1]/[M2]/[M3] /[EBP]/[Ph-PTZ]
τ h
Conv.b %
Mn,theoc g mol−1
Mn,NMRb g mol−1
Mn,GPCb g mol−1
Ð Md
I*e
1 2 3 4 5 6 7 8 9
50:0:0:1:0.025 100:0:0:1:0.05 300:0:0:1:0.15 500:0:0:1:0.25 700:0:0:1:0.35 100:100:0:1:0.05 100:50:0:1:0.05 100:0:100:1:0.05 100:0:50:1:0.05
2 3 4 6 8 3 2 3 2
39 34 38 34 41 36 35 36 39
2190 3650 11,660 17,260 28,980 6850 5260 7500 5780
2150 3750 9440 15,880 51,290 6760 5470 7920 5940
3090 4930 10,580 16,430 52,030 7560 6320 8790 7010
1.10 1.13 1.19 1.25 1.48 1.16 1.14 1.15 1.14
1.02 0.97 1.23 1.09 0.56 1.01 0.96 0.95 0.97
a b c d e
Polymerizations were conducted at room temperature in DMAc (3.75 mol L−1); [M1]=MMA; [M2]=MAA; [M3]=Styrene. Calculated by 1H NMR. Determined by conversion and the monomer feed ratio. Calculated by GPC, dn/dc=0.083. Determined by Mn,theo/Mn,NMR. 4
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Fig. 6. SEC traces of block copolymers (Table 3, Runs 6–9).
fully enable the reproduction of the scientific findings presented in the manuscript.
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