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，主要研究方向为光控聚合。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: 220
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- PDF下载量: 16
- 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

PET-RAFT Polymerization Based on Recyclable Fluorinated 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，开关光源还可以控制反应进程，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，单体转化率未显著降低。
- 含氟卟啉 /
- 非均相催化 /
- PET-RAFT /
- 光聚合 /
- 可回收
Abstract: A heterogeneous photocatalyst TPPF₂₀-TPA based on 5, 10, 15, 20-tetrakis (pentafluorophenyl) porphyrin (TPPF₂₀) was synthesized, which could 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 could be obtained through the PET-RAFT polymerization process. The monomer conversion rate and the polymer molecular weight were detected by ¹H-NMR and GPC. Through these experiments, the reaction process of the catalyst was compared under different light sources,different monomer relative concentrations or different monomer conditions. The results showed that TPPF₂₀-TPA could catalyze the polymerization of common monomers(MMA,GMA,B_ZMA), making the reaction process controllable, and its insolubility in common solvents (e.g. ethanol, dichloromethane, dimethyl sulfoxide) could be used for 3 independent PET-RAFT polymerizations reactions without significant reduction in polymerization efficiency.
- fluorinated porphyrin /
- heterogeneous catalysis /
- PET-RAFT /
- photopolymerization /
- recyclable

HTML全文

图 1 TPPF₂₀-TPA的合成路线

Figure 1. Synthesis route of TPPF₂₀-TPA

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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); FT-IR spectra of TPA, TPPF₂₀ and TPPF₂₀-TPA (c); UV-Vis spectra of TPPF₂₀-TPA, TPPF₂₀ and CDB(d)

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图 3 不同浓度TPPF₂₀-TPA的MMA的RAFT聚合动力学曲线

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

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图 4 聚合物在不同时间的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

Figure 4. GPC curves of polymer at different time and the corresponding M_n，th，M_n，GPC and PDI vs monomer conversion rate

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图 5 开/关光源控制的聚合动力学(n_MMA∶n_CDB∶$n{_{\rm{TPPF_{20}}{}{\text{-} } {\rm{TPA}}}}$=200∶1∶0.010)

Figure 5. Polymerization kinetics controlled by on/off light source(n_MMA∶n_CDB∶$n{_{\rm{TPPF_{20}}{}{\text{-} } {\rm{TPA}}}}$=200∶1∶0.010)

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图 6 PMMA-b-B_ZMA的¹H-NMR谱图(a)和GPC曲线(c)；PMMA-b-GMA的¹H-NMR谱图(b)和GPC曲线(d)

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

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图 7 聚合物（n_MMA∶n_CDB∶$n{_{\rm{TPPF}{_{20}}{\text{-}} {\rm{TPA}}}}$=200:1:0.010）3次循环测试的GPC曲线(a)、转化率和M_n，GPC(b)

Figure 7. GPC curves (a), conversion rate and M_n，GPC (b) of polymer (n_MMA∶n_CDB∶$n{_{\rm{TPPF}{_{20}}\text{-} {\rm{TPA}}}}$=200:1:0.010) with three-cycle tests

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表 1 在蓝光LED下，不同浓度TPPF₂₀-TPA、不同单体对PET-RAFT聚合的影响

Table 1. Effects of different concentrations of TPPF₂₀-TPA and different monomers on PET-RAFT polymerization under blue LED

Entry	n_M∶n_CDB∶$n{_{\rm{TPPF}{_{20}}\text{-} {\rm{TPA}}}}$	Monomer	α²⁾/%	M_n,th	M_n,GPC	PDI³⁾
1	200∶1∶0	MMA	−	−	−	−
2	200∶0∶0.010	MMA	21.5	4572	175000	2.21
3	200∶1∶0.010	MMA	65.3	13332	19960	1.11
4	200∶1∶0.020	MMA	71.3	14532	18210	1.18
5	200∶1∶0.005	MMA	59.3	12132	12838	1.21
6	200∶1∶0.010	GMA	55.3	15977	16005	1.27
7	200∶1∶0.010	B_ZMA	53.1	18963	18462	1.21
1) M stands for monomer; 2) α is calculated from ¹H-NMR; 3) PDI = M_w/M_n, determined by GPC

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