Review

. 2022 Feb 11;14(4):701.

doi: 10.3390/polym14040701.

Recent Advances in the Synthesis of Complex Macromolecular Architectures Based on Poly(N-vinyl pyrrolidone) and the RAFT Polymerization Technique

Nikoletta Roka¹, Olga Kokkorogianni¹, Philippos Kontoes-Georgoudakis¹, Ioannis Choinopoulos¹, Marinos Pitsikalis¹

Affiliations

PMID: 35215614
PMCID: PMC8880212
DOI: 10.3390/polym14040701

Review

Recent Advances in the Synthesis of Complex Macromolecular Architectures Based on Poly(N-vinyl pyrrolidone) and the RAFT Polymerization Technique

Nikoletta Roka et al. Polymers (Basel). 2022.

. 2022 Feb 11;14(4):701.

doi: 10.3390/polym14040701.

Authors

Nikoletta Roka¹, Olga Kokkorogianni¹, Philippos Kontoes-Georgoudakis¹, Ioannis Choinopoulos¹, Marinos Pitsikalis¹

Affiliation

¹ Industrial Chemistry Laboratory, Department of Chemistry, National and Kapodistrian University of Athens, Panepistimiopolis Zografou, 15771 Athens, Greece.

PMID: 35215614
PMCID: PMC8880212
DOI: 10.3390/polym14040701

Abstract

Recent advances in the controlled RAFT polymerization of complex macromolecular architectures based on poly(N-vinyl pyrrolidone), PNVP, are summarized in this review article. Special interest is given to the synthesis of statistical copolymers, block copolymers, and star polymers and copolymers, along with graft copolymers and more complex architectures. In all cases, PNVP is produced via RAFT techniques, whereas other polymerization methods can be employed in combination with RAFT to provide the desired final products. The advantages and limitations of the synthetic methodologies are discussed in detail.

Keywords: RAFT polymerization; block copolymers; graft copolymers; macromolecular architecture; poly(N-vinyl pyrrolidone); star polymers; statistical copolymers.

PubMed Disclaimer

Conflict of interest statement

The authors declare no conflict of interest.

Figures

**Scheme 1**
Simplified mechanism of RAFT polymerization.

**Scheme 3**
Detailed mechanism of RAFT polymerization.

**Figure 1**
CTAs used in the literature for the RAFT polymerization of NVP [28].

**Scheme 4**
Possible reaction resulting in PNVP homopolymers with various end groups.

**Scheme 5**
Chain transfer between growing polymer chains and the solvent (dioxane).

**Scheme 6**
Synthesis of block copolymers PNVP-b-PVAc with various end groups.

**Scheme 7**
Possible formation of PVAc homopolymer by initiation via butyronitrile radicals and/or dioxane radicals and chain transfer with dioxane.

**Scheme 8**
Synthesis of PNVP-b-PVAc block copolymers.

**Scheme 9**
Synthesis of PNVP-b-PVAc by sequential addition of monomers.

**Scheme 10**
Synthesis of PVA-b-PNVP double hydrophilic copolymers from the PVAc-b-PNVP precursors.

**Scheme 11**
Synthesis of the RAFT agent benzyl piperidine dithiocarbamate.

**Scheme 12**
Synthesis of PNVP-b-PNVK block copolymers.

**Scheme 13**
Synthesis of PNVP-b-PNVCL block copolymers.

**Scheme 14**
Synthesis of PNVP-b-PENVP block copolymers starting the polymerization from either the NVP or the ENVP.

**Scheme 15**
Thermolysis of the xanthate end-group of ENVP forming unsaturated chain ends.

**Scheme 16**
Synthesis of PHEVE-b-PNVP block copolymers.

**Scheme 17**
RAFT polymerization of 1,2,4-triazolium salts using different CTAs.

**Scheme 18**
Synthesis of PNVP-b-PNVETri-Br block copolymers.

**Scheme 19**
Synthesis of PVDF-b-PNVP block copolymers.

**Scheme 20**
Universal RAFT agents for block MAMs and LAMs.

**Scheme 22**
Acid/base switchable dithiocarbamate RAFT agents.

**Scheme 23**
Synthesis of poly(MAMs)-b-poly(LAMs) block copolymers using switchable RAFT agents.

**Scheme 24**
Synthesis of PNVP-b-P2VP block copolymers.

**Scheme 25**
Synthesis of PNVP-b-poly(styrene-maleic anhydride) PNVP-b-PSMA (A) and PNVP-b-PDMAEMA (B) block copolymers.

**Scheme 26**
Structure of CTA for the synthesis of PDEAM-b-PNVP block copolymers.

**Scheme 27**
Synthesis of PNVP-b-PDMAEMA block copolymers.

**Scheme 28**
Synthesis of PMMA-b-PNVP block copolymers.

**Scheme 29**
Synthesis of PNVP-b-PAMPS block copolymers.

**Scheme 30**
Synthesis of PNVP-b-PMAA block copolymers.

**Scheme 31**
Synthesis of double hydrophilic block copolymers.

**Scheme 32**
Synthesis of PNVP-b-PI block copolymers.

**Scheme 33**
Synthesis of PnBuA-b-PNVP block copolymers.

**Scheme 34**
CTAs employed for the synthesis of alternating copolymers of VAc and MAF-TBE.

**Scheme 35**
Synthesis of P(Vac-alt-MAF-TBE)-b-PNVP block copolymers.

**Scheme 36**
Synthesis of O-phenyl-S-[1-(phenylethyl)] dithiocarbonate.

**Scheme 37**
Switchable CTAs for RAFT copolymerization (A). Application for the synthesis of PMMA-b-PVAc block copolymers (B).

**Scheme 38**
Synthesis of PDMAm-b-PNVP block copolymers.

**Scheme 39**
Synthesis of PtBuMA-b-PNVP and PMAA-b-PNVP block copolymers.

**Scheme 40**
Synthesis of PS-b-PNVP and PPFS-b-PNVP block copolymers.

**Scheme 41**
Acid-base switchable RAFT agents.

**Scheme 42**
Synthesis of PNIPAM-b-PNVP block copolymer.

**Scheme 43**
Synthesis of the CPX (a) and CiBX (b) RAFT agents.

**Scheme 44**
Structure of the chloroxanthate RAFT agent.

**Scheme 45**
Synthesis of PNVP-b-PTEGMA block copolymers.

**Scheme 46**
Synthesis of PCL-b-(PVCL-stat-PNVP) block terpolymers.

**Scheme 47**
Synthesis of PNVP-b-PCL block copolymers.

**Scheme 48**
Synthesis of PNVP-b-PLLA block copolymers.

**Scheme 49**
Transformation of PEG-OH to macro-CTA.

**Scheme 50**
Synthesis of PCL-b-PNVP block copolymers.

**Scheme 51**
Synthesis of PCL-b-PNVP block copolymers.

**Scheme 52**
Synthesis of PNVP-b-DLLA block copolymers.

**Scheme 53**
Synthesis of P(C₂NVP-co-NVP)-b-PCL block terpolymers.

**Scheme 54**
Synthesis of the CTAs X₃, X₄, X’₃, X’₄.

**Scheme 55**
Synthesis of P(D,L-Lactide-co-glycolide)-b-PNVP block terpolymers.

**Scheme 56**
Reaction of 4,2-aminothiol with an aldehyde to form thiazolidine.

**Scheme 57**
Synthesis of PNVP-b-PBLG block copolymers through the formation of a thiazolidine ring.

**Scheme 58**
Modification of NVP xanthate chain-ends into hydroxyl and aldehyde end-groups.

**Scheme 59**
Deprotection of PBLG chains.

**Scheme 60**
Various methodologies for the synthesis of symmetric and asymmetric triblock copolymers and terpolymers.

**Scheme 61**
Synthesis of P(S-co-AA)-b-PNVP-b-P(S-co-AA) triblock terpolymers.

**Scheme 62**
Synthesis of PNVP-b-PMMA-b-PNVP triblock copolymers.

**Scheme 63**
Synthesis of PNIPAAm-b-PNVP-b-PNIPAAm triblock copolymers.

**Scheme 64**
Synthesis of PNVP-b-PVK-b-PNVP triblock copolymers.

**Scheme 65**
Synthesis of PNVP-b-PDMS-b-PNVP triblock copolymers.

**Scheme 66**
Synthesis of PMA-b-P(AC-co-HEMA)-b-PNVP triblock quaterpolymers.

**Scheme 67**
Various types of star polymers.

**Scheme 68**
General methods for the synthesis of star polymers.

**Scheme 69**
Synthesis of star polymers through RAFT via the Z-group (**left**) and R-group (**right**) approach.

**Scheme 70**
Mechanistic considerations regarding the synthesis of star polymers via the R-group approach.

**Scheme 71**
Mechanistic considerations regarding the synthesis of star polymers via the Z-group approach.

**Scheme 72**
Hindered accessibility of the RAFT group during star synthesis via the Z-group approach caused by the shielding of the growing polymer arms.

**Scheme 73**
Synthesis of the tetrafunctional CTA.

**Scheme 74**
Synthesis of four-arm PNVP stars.

**Scheme 75**
Synthesis of the tetrafunctional CTA agent.

**Scheme 76**
Synthesis of 4-arm star block PNVP-co-PVAc copolymers.

**Scheme 77**
Synthesis of 4-arm block-star copolymer PNVP-b-PVAc.

**Scheme 78**
Synthesis of PNVP 4-arm stars and (PNVP-co-PMA) copolymers.

**Scheme 79**
Synthesis of six arm star copolymers.

**Scheme 80**
Synthesis of (PCL-b-PNVP)₄ star block copolymers.

**Scheme 81**
Synthesis of (PDLLA-b-PNVP)₄ star block copolymers.

**Scheme 82**
Synthesis of (PCL-b-PNVP)₃ star block copolymers.

**Scheme 83**
Synthesis of (PNVP)₇ seven-arm star.

**Scheme 84**
Graft copolymers (1) random graft copolymer (identical branches randomly distributed along the backbone); (2) regular graft copolymer (identical branches equally spaced along the backbone); (3) simple graft copolymer (3-miktoarm star copolymer); and (4) graft copolymer with two trifunctional branch points. Exact graft copolymers.

**Scheme 85**
Three general methods of synthesis of randomly branched graft copolymers.

**Scheme 86**
Synthesis of graft copolymers bearing PNVP side chains through click chemistry.

**Scheme 87**
Grafting from (R-group and Z-group approach) for the synthesis of graft copolymers.

**Scheme 88**
Grafting from procedure using a multi-initiator polymer chain.

**Scheme 89**
Synthesis of PVAc-g-PNVP copolymers.

**Scheme 90**
Synthesis of PCL-g-(PNVP-co-NVCL) graft terpolymers.

**Scheme 91**
Synthesis of PNVP-g-PDMAEMA graft copolymers.

**Scheme 92**
Synthesis of PVBPA-g-PNVP graft copolymers.

**Scheme 93**
Synthesis of polymer brushes via RAFT polymerization.

**Scheme 94**
Synthesis of PVDF-g-(PNVP-b-PDMAEMA) graft terpolymers.

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Recent Advances in the Synthesis of Complex Macromolecular Architectures Based on Poly(N-vinyl pyrrolidone) and the RAFT Polymerization Technique

Affiliation

Recent Advances in the Synthesis of Complex Macromolecular Architectures Based on Poly(N-vinyl pyrrolidone) and the RAFT Polymerization Technique

Authors

Affiliation

Abstract

Conflict of interest statement

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