基于可回收含氟卟啉催化剂的PET-RAFT聚合研究

殷盼; 王武龙; 夏蕾; 杲云; 曹红亮

doi:10.14135/j.cnki.1006-3080.20210410005

基于可回收含氟卟啉催化剂的PET-RAFT聚合研究

doi: 10.14135/j.cnki.1006-3080.20210410005

华东理工大学材料科学与工程学院上海 200237

基金项目: 上海市自然科学基金(18ZR1408300)

详细信息

作者简介:
殷盼：殷　盼(1995-)，男，江苏人，硕士生，主要研究方向：光控聚合。E-mail：785944896@QQ.com

通讯作者:
曹红亮，E-mail：caohl@ecust.edu.cn

中图分类号: O69
计量
- 文章访问数: 53
- HTML全文浏览量: 45
- PDF下载量: 2
- 被引次数: 0
出版历程
- 收稿日期: 2021-04-10
- 网络出版日期: 2021-07-09

Study on PET-RAFT Polymerization Based on Recyclable Fluorin-containing Porphyrin Catalyst

School of Materials Science and Engineering, East China University of Science and Technology, Shanghai 200237, China

摘要

摘要: 基于5,10,15,20-四(五氟苯基)卟啉(TPPF₂₀)合成了一种非均相光催化剂TPPF₂₀-TPA，该催化剂可在蓝光下对单体进行光致电子/能量转移-可逆加成-断裂链转移(PET-RAFT)聚合。该聚合体系可以调节单体的转化率和聚合物分子量，而且开关光源可以控制反应进程，具有较好的单体适用性，并且生成的聚合物链末端具有较好的端基保留程度。TPPF₂₀-TPA可以循环用于3个独立的聚合反应，聚合效率未显著降低，显示出该催化剂在绿色化学中的潜力。
- 含氟卟啉 /
- 非均相催化 /
- PET-RAFT /
- 光聚合 /
- 可回收
Abstract: In this study, a heterogeneous photocatalyst TPPF₂₀-TPA based on 5, 10, 15, 20-tetrakis (pentafluorophenyl) porphyrin (TPPF₂₀) was synthesized, which can be used in photo-induced electron/energy transfer-reversible addition-fragmentation chain transfer (PET-RAFT) polymerization under the radiation of blue light (λ_max = 425 nm). A series of polymers with defined molecular weights and low dispersion can be obtained through the PET-RAFT polymerization process. It was confirmed by ¹H-NMR and GPC that the conversion rate of monomer methyl methacrylate (MMA) and molecular weight of the polymer can be controlled by changing the polymerization time, and the reaction process can also be controlled by switching the light source. In addition, the experimental results showed that different monomers can be handled by the PET-RAFT polymerization. Chain extension experiments show that the polymer chain ends have high fidelity. Based on the insolubility of TPPF₂₀-TPA in different organic solvents (e.g ethanol, dichloromethane, dimethyl sulfoxide), it can be easily purified and reused. The results show that it is recycled for 3 independent PET-RAFT polymerization reactions. The polymerization efficiency is not significantly reduced, showing the great potential of the catalyst in the RAFT polymerization system.
- Fluorinated porphyrin /
- heterogeneous catalysis /
- PET-RAFT /
- photopolymerization /
- recyclable

HTML全文

图 1 TPPF₂₀-TPA的合成路线

Figure 1. Synthesis method of TPPF₂₀-TPA

下载: 全尺寸图片幻灯片

图 2 TPPF₂₀(a)和中间产物(b)的¹H-NMR；TPA, TPPF₂₀和TPPF₂₀-TPA的红外光谱(c)；TPPF₂₀-TPA、TPPF₂₀和CDB的紫外吸收光谱(d)

Figure 2. ¹H-NMR of TPPF₂₀ (a) and intermediate product (b); the FT-IR spectrum of CDB, TPPF₂₀ and TPPF₂₀-TPA (c); the UV-vis spectra of TPPF₂₀-TPA and CDB(d)

下载: 全尺寸图片幻灯片

图 4 [MMA]∶[CDB]∶[TPPF₂₀-TPA]=200∶1∶0.005(a)，200∶1∶0.01(b)，200∶1∶0.02(c)的不同时间的GPC曲线以及对应的M_n，th，M_n，GPC和PDI与单体转化率的关系(d)(e)(f)

Figure 4. [MMA]∶[CDB]∶[TPPF₂₀-TPA]=200∶1∶0.005(a), 200:1:0.01(b), 200∶1∶0.02(c) GPC curves at different times and the corresponding M_n，th，M_n，GPC and PDI vs monomer conversion rate(d)(e)(f)

下载: 全尺寸图片幻灯片

图 3 不同浓度的TPPF₂₀-TPA的MMA的RAFT聚合动力学　　　

Figure 3. RAFT polymerization kinetics of MMA with different concentrations of TPPF₂₀-TPA

下载: 全尺寸图片幻灯片

图 5 开/关光源控制的聚合动力学([MMA]∶[CDB]∶[TPPF₂₀-TPA]=200∶1∶0.01)

Figure 5. Polymerization kinetics controlled by on/off light source([MMA]∶[CDB]∶[TPPF₂₀-TPA]=200∶1∶0.01)

下载: 全尺寸图片幻灯片

图 6 通过PMMA macro-CTA扩链得到的PMMA-b-B_ZMA的¹H NMR(a)、GPC曲线(c)和PMMA-b-GMA的¹H NMR(b)、GPC曲线(d)

Figure 6. ¹H-NMR spectrum (a) and GPC curve (c) of PMMA-b-B_ZMA and the ¹H NMR spectrum (b) and GPC curve (d) of PMMA-b-GMA

下载: 全尺寸图片幻灯片

图 7 [MMA]:[CDB]:[TPPF₂₀-TPA]=200:1:0.01的三次循环测试的GPC曲线(a)，转化率和M_n，GPC(b)([MMA]:[CDB]:[TPPF₂₀-TPA]=200:1:0.01)

Figure 7. GPC curve (a), conversion rate and M_n，GPC (b) of the three-cycle test([MMA]:[CDB]:[TPPF₂₀-TPA]=200:1:0.01)

下载: 全尺寸图片幻灯片

表 1 在蓝光LED(λ_max=425 nm)下，不同浓度TPPF₂₀-TPA、不同单体对PET-RAFT聚合的影响

Table 1. Under blue LED, the effect of different concentrations of TPPF₂₀-TPA and different monomers on PET-RAFT polymerization

Entry	[M]/[RAFT]/[Catalyst]	Monomer	RAFT agent	Conv.¹(α%)	M_n,th²	M_n,GPC³	PDI⁴
1	200∶1∶0	MMA	CDB	−	−	−	−
2	200∶0∶0.01	MMA	−	21.5	4572	175000	2.21
3	200∶1∶0.01	MMA	CDB	65.3	13332	19960	1.11
4	200∶1∶0.02	MMA	CDB	71.3	14532	18210	1.18
5	200∶1∶0.005	MMA	CDB	59.3	12132	12838	1.21
6	200∶1∶0.01	GMA	CDB	55.3	15977	16005	1.27
7	200∶1∶0.01	B_ZMA	CDB	53.1	18963	18462	1.21
[1] Yield (α%) is calculated from ¹H NMR; [2] M_n,th is calculated by [M]₀/[RAFT] × M_monomer × α%; [3] M_n,GPC is determined by Gel Permeation Chromatography (GPC); [4] Polydispersities PDI = M_w/M_n is determined by GPC; [5] The catalyst used in the PET-RAFT system was TPPF₂₀-TPA, and all polymerization were irradiated under blue light for 10 h.

下载: 导出CSV

参考文献(25)

[1]	CHEN M, ZHONG M, JOHNSON J A. Light-controlled radical polymerization: mechanisms, methods, and applications[J]. Chemical Reviews, 2016: 10167-10173.
[2]	WALSH D J, HYATT M G, MILLER S A, et al. Recent trends in catalytic polymerizations[J]. ACS Catalysis, 2019, 9(12): 11153-11188. doi: 10.1021/acscatal.9b03226
[3]	PAN X C, FANTIN M, YUAN F, et al. Externally controlled atom transfer radical polymerization[J]. Chemical Society Reviews, 2018, 47(14): 5457-5490. doi: 10.1039/C8CS00259B
[4]	MCKENZIE T G, FU Q, UCHIYAMA M, et al. Beyond Traditional RAFT: Alternative Activation of Thiocarbonylthio Compounds for Controlled Polymerization[J]. Advanced Science, 2016, 3(9): 1-9.
[5]	THERIOT J C, LIM C H, YANG H, et al. Organocatalyzed atom transfer radical polymerization driven by visible light[J]. Science, 2016, 352(6289): 1082-1086. doi: 10.1126/science.aaf3935
[6]	BRAUNECKER W A, MATYJASZEWSKI K. Controlled/living radical polymerization: features, developments, and perspectives[J]. Progress in Polymer Science, 2007, 32(1): 93-146. doi: 10.1016/j.progpolymsci.2006.11.002
[7]	JING J J, GANG Y. Localized surface plasmon resonance meets controlled/living radical polymerization: an adaptable strategy for broadband light‐regulated macromolecular synthesis[J]. Angewandte Chemie International Edition, 2019, 58(35): 12096-12101. doi: 10.1002/anie.201906194
[8]	HAKOBYAN K, GEGENHUBER T, MCERLEAN C, et al. Visible‐light‐driven madix polymerisation via a reusable, low‐cost, and non‐toxic bismuth oxide photocatalyst[J]. Angewandte Chemie International Edition, 2019, 58(6): 1828-1832. doi: 10.1002/anie.201811721
[9]	ZHU Y, LIU Y, MILLER K A, et al. Lead halide perovskite nanocrystals as photocatalysts for PET-RAFT polymerization under visible and near-infrared irradiation[J]. ACS Macro Letters, 2020, 9(5): 725-730. doi: 10.1021/acsmacrolett.0c00232
[10]	JIANG J, GANG Y, ZHE W, et al. Heteroatom-doped carbon dots (CDs) as a new class of metal-free photocatalysts for PET-RAFT polymerization under visible light and sunlight[J]. Angewandte Chemie International Edition, 2018, 130(37): 12212-12218.
[11]	Mcclelland K P, Clemons T D, Stupp S I, et al. Semiconductor quantum dots are efficient and recyclable photocatalysts for aqueous PET-RAFT polymerization[J]. ACS Macro Letters, 2019, 9(1): 7-13.
[12]	BOYER C A J M, ZHANG L, SHI X, et al. Porphyrinic zirconium MOFs as heterogeneous photocatalysts for PET‐RAFT polymerization and stereolithography[J]. Angewandte Chemie International Edition, 2020, 60(10): 5489-5496.
[13]	LI X, ZHANG Y C, ZHAO Y, et al. Xanthene dye-functionalized conjugated porous polymers as robust and reusable photocatalysts for controlled radical polymerization[J]. Macromolecules, 2020, 53(5): 1550-1556. doi: 10.1021/acs.macromol.0c00106
[14]	CAO H, WANG G, XUE Y, et al. Far-red light-induced reversible addition–fragmentation chain transfer polymerization using a man-made bacteriochlorin[J]. ACS Macro Letters, 2019, 8(15): 616-622.
[15]	WANG W, ZHONG S, WANG G, et al. Photo-controlled RAFT polymerization mediated by organic/inorganic hybrid photoredox catalysts: enhanced catalytic efficiency[J]. Polymer Chemistry, 2020, 11(18): 3188-3194. doi: 10.1039/D0PY00171F
[16]	陈帅, 庞瑞淇, 刘思奕, 等. 卟啉半遥爪聚合物的制备及其在光动力疗法中的应用探讨[J]. 华东理工大学学报(自然科学版), 2020, 46(3): 349-359.
[17]	肖潮, 田佳, 刘峰, 等. 基于pH响应两亲性卟啉嵌段共聚物的光动力与化学联合治疗[J]. 华东理工大学学报(自然科学版), 2020, 46(2): 208-218.
[18]	SHEN L, LU Q, ZHU A, et al. Photocontrolled RAFT polymerization mediated by a supramolecular catalyst[J]. ACS Macro Letters, 2017, 6(6): 625-631. doi: 10.1021/acsmacrolett.7b00343
[19]	HUANG Y, LI X, LI J L, et al. An environmentally benign and pH-sensitive photocatalyst with surface-bound metalloporphyrin for heterogeneous catalysis of controlled radical polymerization[J]. Macromolecules, 2018, 51(20): 7974-7982. doi: 10.1021/acs.macromol.8b01735
[20]	OBATA M, TANAKA S, MIZUKOSHI H, et al. RAFT synthesis of an amphiphilic block copolymer bearing chlorin rings in the hydrophobic segment and its application in photodynamic therapy[J]. Journal of Polymer Science Part A: Polymer Chemistry, 2017, 55(20): 3395-3403. doi: 10.1002/pola.28716
[21]	PENG C H, FRYD M, WAYLAND B B. Organocobalt mediated radical polymerization of acrylic acid in water[J]. Macromolecules, 2007, 40(19): 6814-6819. doi: 10.1021/ma070836n
[22]	BHUPATHIRAJU N, RIZVI W, BATTEAS J D, et al. Fluorinated porphyrinoids as efficient platforms for new photonic materials, sensors, and therapeutics[J]. Organic & Biomolecular Chemistry, 2015, 14(2): 389-408.
[23]	BHUPATHIRAJU N, RIZVI W, BATTEAS J D, et al. ChemInform Abstract: Fluorinated porphyrinoids as efficient platforms for new photonic materials, sensors, and therapeutics[J]. ChemInform, 2016, 47(9): 389-395.
[24]	SINGH S, AGGARWAL A, BHUPATHIRAJU N, et al. Glycosylated porphyrins, phthalocyanines, and other porphyrinoids for diagnostics and therapeutics[J]. Chemical Reviews, 2015, 115(18): 10261-10306. doi: 10.1021/acs.chemrev.5b00244
[25]	WU M S, ZHIYONGLIU, WEIANZ. An ultra-stable bio-inspired bacteriochlorin analogue for hypoxia-tolerant photodynamic therapy[J]. Chemical Science, 2021, 12(4): 1295-1301. doi: 10.1039/D0SC05525E