Porous Organic Polymers

Postgraduate course
Advanced Porous Materials
Fundamental & Applications

Dr. Lê Vũ Hà
Dr. Nguyễn Đăng Khoa

Ho Chi Minh city, 09/2021

State-Of-The-Art

10.1002/anie.201000167
2
Classification

According to their structural characteristics, porous organic polymers (POPs)

can be divided into four types:
1. Polymers of intrinsic microporosity (PIMs)
2. Hypercrosslinked polymers (HCPs)
3. Covalent organic frameworks (COFs)
4. Conjugated microporous polymers (CMPs)

There are two classes of POPs:

1. Disordered, amorphous POPs (PIMs, HCPs, and CMPs)
2. Ordered, crystalline POPs (COFs)

3
Classification

10.1021/acs.chemrev.9b00399
4
Basic structure

10.1016/B978-0-12-817561-3.00001-9 5
Synthesis via Condensation Reactions
(A) BO2C2 ring formation

(B) Boroxine ring formation

(C) Dioxane ring formation

10.1016/j.progpolymsci.2011.09.002
6
Synthesis via Condensation Reaction
(D) Imine reaction

(E) Amide reaction

(F) Imide reaction

10.1016/j.progpolymsci.2011.09.002
7
Synthesis via Metal-Catalyzed Reactions
(G) Cyclotrimerisation

(H) Friedel–Crafts alkylation

10.1016/j.progpolymsci.2011.09.002
8
Synthesis via Metal-Catalyzed Reactions
(I) Sonogashira coupling

(K) Yamamoto coupling

(L) oxidative homocoupling

(M) Suzuki coupling

10.1016/j.progpolymsci.2011.09.002
9
Hypercrosslinked Polymers

Monographs in Supramolecular Chemistry No. 17, Porous Polymers: Design, Synthesis and Applications, By Shilun Qiu and Teng Ben The Royal Society of
Chemistry 2016
10
Hypercrosslinked Polymers (HCPs)

Chem. Soc. Rev., 2017, 46, 3322--3356

11
Hypercrosslinked Polymers (HCPs)

Chem. Soc. Rev., 2017, 46, 3322--3356

12
Hypercrosslinked Polymers (HCPs)

10.1016/j.progpolymsci.2011.09.002
13
Hypercrosslinked Polymers (HCPs)

Monographs in Supramolecular Chemistry No. 17, Porous Polymers: Design, Synthesis and Applications, By Shilun Qiu and Teng Ben The Royal Society of
Chemistry 2016
14
Porous Aromatic Frameworks (PAFs)

10.1021/acscentsci.9b00047
15
Porous Aromatic Frameworks (PAFs)

Monographs in Supramolecular Chemistry No. 17, Porous Polymers: Design, Synthesis and Applications, By Shilun Qiu and Teng Ben The Royal Society of
Chemistry 2016
16
Porous Aromatic Frameworks (PAFs)
In 2009, Profs. Qiu and Zhu synthesized the porous aromatic framework PAF-1
viaa one-step Ullmann polycondensation of tetrakis(4-bromophenyl)methane

10.1002/anie.200904637, 10.1021/acscentsci.9b00047
17
Porous Aromatic Frameworks (PAFs)

10.1039/c4mh00163j
18
Conjugated Microporous Polymers

The first CMPs were reported in 2007

and used Sonogashira palladium
coupling to link aromatic halides to
aromatic alkynes, thus forming
poly(aryleneethynylene) networks

Angew. Chem. Int. Ed. 2007, 46, 8574 –8578

19
Conjugated Microporous Polymers
The first CMPs were reported in 2007 and used Sonogashira palladium coupling to link
aromatic halides to aromatic alkynes, thus forming poly(aryleneethynylene) networks

Monographs in Supramolecular Chemistry No. 17, Porous Polymers: Design, Synthesis and Applications, By Shilun Qiu and Teng Ben The Royal Society of
Chemistry 2016
20
Conjugated Microporous Polymers (CMPs)

10.1021/ja8010176
21
Conjugated Microporous Polymers (CMPs)

10.1016/j.progpolymsci.2011.09.002
22
Covalent Triazine Frameworks (CTFs)
In 2008, Thomas et al. reported the dynamic trimerization reaction of simple,
cheap, and abundant aromatic nitriles in ionothermal conditions in molten ZnCl2
to produce first triazine-based materials with high porosities and surface areas

10.1002/anie.200705710
23
Covalent Triazine Frameworks (CTFs)

10.1002/anie.200705710
24
Covalent Triazine Frameworks (CTFs)

10.1002/anie.200705710
25
Covalent Organic Frameworks (COFs)

10.1021/acscentsci.0c00463, 10.1038/natrevmats.2016.68
26
Covalent Organic Frameworks (COFs)

10.1021/acscentsci.0c00463
27
Covalent Organic Frameworks (COFs)

10.1002/adsc.202001086 28
Covalent Organic Frameworks (COFs)

10.1039/c7cs00695k 29
Covalent Organic Frameworks (COFs)

10.1126/science.1120411 30
Covalent Organic Frameworks (COFs)

10.1126/science.1120411 31
Covalent Organic Frameworks (COFs)

10.1126/science.1120411 32
Covalent Organic Frameworks (COFs)

10.1126/science.1120411 33
Covalent Organic Frameworks (COFs)

10.1126/science.1120411 34
Covalent Organic Frameworks (COFs)

10.1021/ja9015765 35
Covalent Organic Frameworks (COFs)

10.1038/NCHEM.2771 36
Applications

10.1016/B978-0-12-817561-3.00001-9 37
Applications

10.1021/acscentsci.9b00047 38
Applications

Monographs in Supramolecular Chemistry No. 17, Porous Polymers: Design, Synthesis and Applications, By Shilun Qiu and Teng Ben The Royal Society of
Chemistry 2016
39
Applications

10.1016/B978-0-12-817561-3.00001-9 40
Applications

10.1016/j.progpolymsci.2011.09.002 41
Applications

10.1016/j.progpolymsci.2011.09.002 42
Applications

Monographs in Supramolecular Chemistry No. 17, Porous Polymers: Design, Synthesis and Applications, By Shilun Qiu and Teng Ben The Royal Society of
Chemistry 2016
43
Applications

44
Applications

10.1002/adsc.202001086 45
Covalent Organic Frameworks (COFs)

10.1002/anie.200902009 46
Applications

10.1002/anie.200902009 47
Covalent Organic Frameworks (COFs)

Synthesis and Applications of Copolymers, First Edition. Edited by Anbanandam Parthiban.

© 2014 John Wiley & Sons, Inc 48
Conclusions

10.1021/cr200440z 49
Conclusions

50