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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 Roka  1 , Olga Kokkorogianni  1 , Philippos Kontoes-Georgoudakis  1 , Ioannis Choinopoulos  1 , Marinos Pitsikalis  1
Affiliations
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). .

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.

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Conflict of interest statement

The authors declare no conflict of interest.

Figures

Scheme 1
Scheme 1
Simplified mechanism of RAFT polymerization.
Scheme 2
Scheme 2
Structures of CTAs.
Scheme 3
Scheme 3
Detailed mechanism of RAFT polymerization.
Figure 1
Figure 1
CTAs used in the literature for the RAFT polymerization of NVP [28].
Scheme 4
Scheme 4
Possible reaction resulting in PNVP homopolymers with various end groups.
Scheme 5
Scheme 5
Chain transfer between growing polymer chains and the solvent (dioxane).
Scheme 6
Scheme 6
Synthesis of block copolymers PNVP-b-PVAc with various end groups.
Scheme 7
Scheme 7
Possible formation of PVAc homopolymer by initiation via butyronitrile radicals and/or dioxane radicals and chain transfer with dioxane.
Scheme 8
Scheme 8
Synthesis of PNVP-b-PVAc block copolymers.
Scheme 9
Scheme 9
Synthesis of PNVP-b-PVAc by sequential addition of monomers.
Scheme 10
Scheme 10
Synthesis of PVA-b-PNVP double hydrophilic copolymers from the PVAc-b-PNVP precursors.
Scheme 11
Scheme 11
Synthesis of the RAFT agent benzyl piperidine dithiocarbamate.
Scheme 12
Scheme 12
Synthesis of PNVP-b-PNVK block copolymers.
Scheme 13
Scheme 13
Synthesis of PNVP-b-PNVCL block copolymers.
Scheme 14
Scheme 14
Synthesis of PNVP-b-PENVP block copolymers starting the polymerization from either the NVP or the ENVP.
Scheme 15
Scheme 15
Thermolysis of the xanthate end-group of ENVP forming unsaturated chain ends.
Scheme 16
Scheme 16
Synthesis of PHEVE-b-PNVP block copolymers.
Scheme 17
Scheme 17
RAFT polymerization of 1,2,4-triazolium salts using different CTAs.
Scheme 18
Scheme 18
Synthesis of PNVP-b-PNVETri-Br block copolymers.
Scheme 19
Scheme 19
Synthesis of PVDF-b-PNVP block copolymers.
Scheme 20
Scheme 20
Universal RAFT agents for block MAMs and LAMs.
Scheme 21
Scheme 21
Switchable RAFT agent.
Scheme 22
Scheme 22
Acid/base switchable dithiocarbamate RAFT agents.
Scheme 23
Scheme 23
Synthesis of poly(MAMs)-b-poly(LAMs) block copolymers using switchable RAFT agents.
Scheme 24
Scheme 24
Synthesis of PNVP-b-P2VP block copolymers.
Scheme 25
Scheme 25
Synthesis of PNVP-b-poly(styrene-maleic anhydride) PNVP-b-PSMA (A) and PNVP-b-PDMAEMA (B) block copolymers.
Scheme 26
Scheme 26
Structure of CTA for the synthesis of PDEAM-b-PNVP block copolymers.
Scheme 27
Scheme 27
Synthesis of PNVP-b-PDMAEMA block copolymers.
Scheme 28
Scheme 28
Synthesis of PMMA-b-PNVP block copolymers.
Scheme 29
Scheme 29
Synthesis of PNVP-b-PAMPS block copolymers.
Scheme 30
Scheme 30
Synthesis of PNVP-b-PMAA block copolymers.
Scheme 31
Scheme 31
Synthesis of double hydrophilic block copolymers.
Scheme 32
Scheme 32
Synthesis of PNVP-b-PI block copolymers.
Scheme 33
Scheme 33
Synthesis of PnBuA-b-PNVP block copolymers.
Scheme 34
Scheme 34
CTAs employed for the synthesis of alternating copolymers of VAc and MAF-TBE.
Scheme 35
Scheme 35
Synthesis of P(Vac-alt-MAF-TBE)-b-PNVP block copolymers.
Scheme 36
Scheme 36
Synthesis of O-phenyl-S-[1-(phenylethyl)] dithiocarbonate.
Scheme 37
Scheme 37
Switchable CTAs for RAFT copolymerization (A). Application for the synthesis of PMMA-b-PVAc block copolymers (B).
Scheme 38
Scheme 38
Synthesis of PDMAm-b-PNVP block copolymers.
Scheme 39
Scheme 39
Synthesis of PtBuMA-b-PNVP and PMAA-b-PNVP block copolymers.
Scheme 40
Scheme 40
Synthesis of PS-b-PNVP and PPFS-b-PNVP block copolymers.
Scheme 41
Scheme 41
Acid-base switchable RAFT agents.
Scheme 42
Scheme 42
Synthesis of PNIPAM-b-PNVP block copolymer.
Scheme 43
Scheme 43
Synthesis of the CPX (a) and CiBX (b) RAFT agents.
Scheme 44
Scheme 44
Structure of the chloroxanthate RAFT agent.
Scheme 45
Scheme 45
Synthesis of PNVP-b-PTEGMA block copolymers.
Scheme 46
Scheme 46
Synthesis of PCL-b-(PVCL-stat-PNVP) block terpolymers.
Scheme 47
Scheme 47
Synthesis of PNVP-b-PCL block copolymers.
Scheme 48
Scheme 48
Synthesis of PNVP-b-PLLA block copolymers.
Scheme 49
Scheme 49
Transformation of PEG-OH to macro-CTA.
Scheme 50
Scheme 50
Synthesis of PCL-b-PNVP block copolymers.
Scheme 51
Scheme 51
Synthesis of PCL-b-PNVP block copolymers.
Scheme 52
Scheme 52
Synthesis of PNVP-b-DLLA block copolymers.
Scheme 53
Scheme 53
Synthesis of P(C2NVP-co-NVP)-b-PCL block terpolymers.
Scheme 54
Scheme 54
Synthesis of the CTAs X3, X4, X’3, X’4.
Scheme 55
Scheme 55
Synthesis of P(D,L-Lactide-co-glycolide)-b-PNVP block terpolymers.
Scheme 56
Scheme 56
Reaction of 4,2-aminothiol with an aldehyde to form thiazolidine.
Scheme 57
Scheme 57
Synthesis of PNVP-b-PBLG block copolymers through the formation of a thiazolidine ring.
Scheme 58
Scheme 58
Modification of NVP xanthate chain-ends into hydroxyl and aldehyde end-groups.
Scheme 59
Scheme 59
Deprotection of PBLG chains.
Scheme 60
Scheme 60
Various methodologies for the synthesis of symmetric and asymmetric triblock copolymers and terpolymers.
Scheme 61
Scheme 61
Synthesis of P(S-co-AA)-b-PNVP-b-P(S-co-AA) triblock terpolymers.
Scheme 62
Scheme 62
Synthesis of PNVP-b-PMMA-b-PNVP triblock copolymers.
Scheme 63
Scheme 63
Synthesis of PNIPAAm-b-PNVP-b-PNIPAAm triblock copolymers.
Scheme 64
Scheme 64
Synthesis of PNVP-b-PVK-b-PNVP triblock copolymers.
Scheme 65
Scheme 65
Synthesis of PNVP-b-PDMS-b-PNVP triblock copolymers.
Scheme 66
Scheme 66
Synthesis of PMA-b-P(AC-co-HEMA)-b-PNVP triblock quaterpolymers.
Scheme 67
Scheme 67
Various types of star polymers.
Scheme 67
Scheme 67
Various types of star polymers.
Scheme 68
Scheme 68
General methods for the synthesis of star polymers.
Scheme 69
Scheme 69
Synthesis of star polymers through RAFT via the Z-group (left) and R-group (right) approach.
Scheme 70
Scheme 70
Mechanistic considerations regarding the synthesis of star polymers via the R-group approach.
Scheme 71
Scheme 71
Mechanistic considerations regarding the synthesis of star polymers via the Z-group approach.
Scheme 72
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
Scheme 73
Synthesis of the tetrafunctional CTA.
Scheme 74
Scheme 74
Synthesis of four-arm PNVP stars.
Scheme 75
Scheme 75
Synthesis of the tetrafunctional CTA agent.
Scheme 76
Scheme 76
Synthesis of 4-arm star block PNVP-co-PVAc copolymers.
Scheme 77
Scheme 77
Synthesis of 4-arm block-star copolymer PNVP-b-PVAc.
Scheme 78
Scheme 78
Synthesis of PNVP 4-arm stars and (PNVP-co-PMA) copolymers.
Scheme 79
Scheme 79
Synthesis of six arm star copolymers.
Scheme 80
Scheme 80
Synthesis of (PCL-b-PNVP)4 star block copolymers.
Scheme 81
Scheme 81
Synthesis of (PDLLA-b-PNVP)4 star block copolymers.
Scheme 82
Scheme 82
Synthesis of (PCL-b-PNVP)3 star block copolymers.
Scheme 83
Scheme 83
Synthesis of (PNVP)7 seven-arm star.
Scheme 84
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
Scheme 85
Three general methods of synthesis of randomly branched graft copolymers.
Scheme 86
Scheme 86
Synthesis of graft copolymers bearing PNVP side chains through click chemistry.
Scheme 87
Scheme 87
Grafting from (R-group and Z-group approach) for the synthesis of graft copolymers.
Scheme 88
Scheme 88
Grafting from procedure using a multi-initiator polymer chain.
Scheme 89
Scheme 89
Synthesis of PVAc-g-PNVP copolymers.
Scheme 90
Scheme 90
Synthesis of PCL-g-(PNVP-co-NVCL) graft terpolymers.
Scheme 91
Scheme 91
Synthesis of PNVP-g-PDMAEMA graft copolymers.
Scheme 92
Scheme 92
Synthesis of PVBPA-g-PNVP graft copolymers.
Scheme 93
Scheme 93
Synthesis of polymer brushes via RAFT polymerization.
Scheme 94
Scheme 94
Synthesis of PVDF-g-(PNVP-b-PDMAEMA) graft terpolymers.
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