10-(pyren-1-yl)-10h-phenothiazine and pyrene as organic catalysts for photoinitiated ATRP of 4-vinylpyridine

The UV light-mediated metal-free polymerizations of 4-vinylpyridine (4VP) have been successfully performed by using 10-(pyren-1-yl)-10H-phenothiazine (PPTh) and pyrene as photocatalysts. The preparation of narrow polydispersity poly (4-vinyl pyridine) (P4VP) with high conversions was enabled in both protic as well as unprotic reaction media at ambient temperature. Additionally, copolymerizations of 4VP with acrylate and methacrylate monomers were also demonstrated, affording metal-free copolymer products.

Keywords:
organic photocatalyst; metal-free atom transfer radical polymerization; 4-vinylpyridine; pyrene

Graphical Abstract

Authorship

Loc Tan Nguyen

National Key Laboratory of Polymer and Composite Materials, Ho Chi Minh City University of Technology – HCMUT, Vietnam National University–Ho Chi Minh City – VNU–HCM, Ho Chi Minh City, VietnamVietnam National UniversityVietnamHo Chi Minh City, VietnamNational Key Laboratory of Polymer and Composite Materials, Ho Chi Minh City University of Technology – HCMUT, Vietnam National University–Ho Chi Minh City – VNU–HCM, Ho Chi Minh City, Vietnam

Hung Quang Pham

Duc Anh Song Nguyen

Luan Thanh Nguyen

Ky Phuong Ha Huynh

Faculty of Chemical Engineering, Ho Chi Minh City University of Technology – HCMUT, Vietnam National University - Ho Chi Minh City - VNU–HCM, 268 Ly Thuong Kiet, District 10, Ho Chi Minh City, VietnamVietnam National UniversityVietnamHo Chi Minh City, VietnamFaculty of Chemical Engineering, Ho Chi Minh City University of Technology – HCMUT, Vietnam National University - Ho Chi Minh City - VNU–HCM, 268 Ly Thuong Kiet, District 10, Ho Chi Minh City, Vietnam

Hai Le Tran

Phong Thanh Mai

Ha Tran Nguyen ^**nguyentranha@hcmut.edu.vn; **trtthuy@hcmut.edu.vn

Faculty of Materials Technology, Ho Chi Minh City University of Technology - HCMUT, Vietnam National University – Ho Chi Minh City - VNU–HCM, Ho Chi Minh City, VietnamVietnam National UniversityVietnamHo Chi Minh City, VietnamFaculty of Materials Technology, Ho Chi Minh City University of Technology - HCMUT, Vietnam National University – Ho Chi Minh City - VNU–HCM, Ho Chi Minh City, Vietnam

https://orcid.org/0000-0001-5201-201X

Le-Thu Thi Nguyen

Thuy Thu Truong

*nguyentranha@hcmut.edu.vn; **trtthuy@hcmut.edu.vn

SCIMAGO INSTITUTIONS RANKINGS

Figures | Tables

Figures (9)
Tables (1)

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Figure 1
A proposed general photoinitiated ATRP mechanism (P_n = polymer chain)

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Scheme 1
Synthetic pathways of P4VP (a), P(4VP-r-SA) (b), P(4VP-r-SMA) using o-PCs.

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Figure 2
Conversion of polymerizations of 4VP during time catalyzed by Pyrene and PPTh

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Figure 3
(a)) GPC traces vs conversions of P4VP synthesized using PPTh as photocatalyst in ethanol (b) Dependence of molecular weight (M_n, GPC) and polydispersity (M_w/M_n) on monomer conversion.

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Figure 4
Monomer conversion vs. time in ON-OFF experiments demonstrating photo-controlled polymerization propagation using PPTh (blue triangle line) and pyrene (red dot line)

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Figure 5
¹H-NMR spectra of (a) P(4VP-r-SA) and (b) P(4VP-r-SMA).

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Figure 6
FTIR spectrum of P(4-vinylpyridine) (blue line), Poly (stearyl methacrylate) (orange line), Poly (4-Vinylpyridine-r-Steary acrylate) (black line) and Poly (4-Vinylpyridine-r-Stearylmethacrylate) (green line).

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Figure 7
Differential scanning calorimetry (DSC) curve of P4VP product.

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Figure 2
Conversion of polymerizations of 4VP during time catalyzed by Pyrene and PPTh

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Figure 4
Monomer conversion vs. time in ON-OFF experiments demonstrating photo-controlled polymerization propagation using PPTh (blue triangle line) and pyrene (red dot line)

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Figure 5
¹H-NMR spectra of (a) P(4VP-r-SA) and (b) P(4VP-r-SMA).

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Figure 7
Differential scanning calorimetry (DSC) curve of P4VP product.

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Table 1
Results of photo-induced metal-free ATRP of 4VP*.

Figure 1 A proposed general photoinitiated ATRP mechanism (P_n = polymer chain)

Scheme 1 Synthetic pathways of P4VP (a), P(4VP-r-SA) (b), P(4VP-r-SMA) using o-PCs.

Figure 2 Conversion of polymerizations of 4VP during time catalyzed by Pyrene and PPTh

Figure 3 (a)) GPC traces vs conversions of P4VP synthesized using PPTh as photocatalyst in ethanol (b) Dependence of molecular weight (M_n, GPC) and polydispersity (M_w/M_n) on monomer conversion.

Figure 4 Monomer conversion vs. time in ON-OFF experiments demonstrating photo-controlled polymerization propagation using PPTh (blue triangle line) and pyrene (red dot line)

Figure 5 ¹H-NMR spectra of (a) P(4VP-r-SA) and (b) P(4VP-r-SMA).

Figure 6 FTIR spectrum of P(4-vinylpyridine) (blue line), Poly (stearyl methacrylate) (orange line), Poly (4-Vinylpyridine-r-Steary acrylate) (black line) and Poly (4-Vinylpyridine-r-Stearylmethacrylate) (green line).

Figure 7 Differential scanning calorimetry (DSC) curve of P4VP product.

Figure 2 Conversion of polymerizations of 4VP during time catalyzed by Pyrene and PPTh

Figure 3 (a)) GPC traces vs conversions of P4VP synthesized using PPTh as photocatalyst in ethanol (b) Dependence of molecular weight (M_n, GPC) and polydispersity (M_w/M_n) on monomer conversion.

Figure 4 Monomer conversion vs. time in ON-OFF experiments demonstrating photo-controlled polymerization propagation using PPTh (blue triangle line) and pyrene (red dot line)

Figure 5 ¹H-NMR spectra of (a) P(4VP-r-SA) and (b) P(4VP-r-SMA).

Figure 6 FTIR spectrum of P(4-vinylpyridine) (blue line), Poly (stearyl methacrylate) (orange line), Poly (4-Vinylpyridine-r-Steary acrylate) (black line) and Poly (4-Vinylpyridine-r-Stearylmethacrylate) (green line).

Figure 7 Differential scanning calorimetry (DSC) curve of P4VP product.

Table 1 Results of photo-induced metal-free ATRP of 4VP*.

Entry	Monomer	[4VP]₀:[I]₀:[C]₀	Solvent	Catalyst	Time (h)	M_n^b (g/mol)	PDI^b	Conv^a (%)
1	4VP	150:1:0.1	Ethanol	PPTh	24	14,186	1.12	91
2	4VP	150:1:0.1	Methanol	PPTh	24	14,260	1.09	90
3	4VP	150:1:0.1	THF: Ethanol (1/1 v/v)	PPTh	24	14,450	1.12	90
4	4VP	150:1:0.1	THF: Ethanol (7/2 v/v)	PPTh	24	12,323	1.19	75
5	4VP	150:1:0.1	THF	PPTh	24	10,750	1.18	65
6	4VP	150:1:0.1	THF	PPTh	48	14,225	1.11	92
7	4VP	150:1:1	Ethanol	Pyrene	24	9,257	1.15	60
8	4VP	150:1:0.1	Methanol	Pyrene	24	9,442	1.16	58
9	4VP	150:1:0.1	THF	Pyrene	24	7,201	1.12	45
10	4VP, SA (2:1)	100:1:0.1	THF	PPTh	48	6,804	1.77	71
11	4VP, SMA (2:1)	100:1:0.1	THF	PPTh	48	11,670	1.59	78

^*
Polymerizations was carried out under a 365 nm UV irradiation;
^a
Conversion was determined gravimetrically: conversion = (m - m_I - m_PC)/m_M where m denotes the weight of product, and m_I, m_PC, m_M are the weights of the initiator, photocatalyst and monomers, respectively.
^b
PDI, M_n were determined by GPC.

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10-(pyren-1-yl)-10h-phenothiazine and pyrene as organic catalysts for photoinitiated ATRP of 4-vinylpyridine

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[1] *nguyentranha@hcmut.edu.vn; **trtthuy@hcmut.edu.vn