Photo-Induced Copolymerization of Chlorotrifluoroethylene and Methyl Isopropenyl Ether★

doi:10.6023/A23080387

Abstract

Fluoropolymers exhibit unique properties, such as outstanding thermal stability and chemical inertness, ultralow surface energy, and have found broad applications in lots of areas. Many fluoropolymers show high crystallinity and low solubility, restricting their practical usage through melting and solution processing. To address such issues, copolymerization of fluoroalkenes and comonomers have been developed to prepare fluorinated copolymers that retain fluoroalkyl characteristics and good processibility, bringing many important commercial products, for example, copolymers of chlorotrifluoroethylene (CTFE) and vinyl ethers. However, such copolymers could possess low glass transition temperature (T_g), which is a key property to influence the applicable scope. In this work, we report copolymerization of CTFE and methyl isopropenyl ether (MIE) for the first time, which have enabled the synthesis of novel fluorinated copolymers under LED (light emitting diode) light irradiation conditions by merging an organic thermally activated delayed fluorescence catalyst and a redox active organic amine via a redox-relay catalysis. In comparison to conventional free radical (co)polymerization of fluoroalkenes, this method not only provides main-chain fluoropolymers of readily tunable molecular weights as evidenced by gel permeation chromatography (GPC) and multi-angle light scattering detection coupled with GPC (GPC-MALS), but also allows smooth transformation of fluoroalkene feedstock at ambient pressure using common Schlenk glassware without needing high-pressure metallic vessels. Although the obtained CTFE-MIE copolymers exhibited less controlled molecular weight distributions (MWDs) and limited chain-end fidelity as confirmed by chain-extension polymerization and GPC analysis, the chain-growth process presents first-order kinetics as validated by monitoring the monomer consumption, and follows alternating copolymerization as supported by the variation of degrees of polymerization (DPs) of both vinyl compounds along the light irradiation time, presenting improved chain-growth control as compared to conventional free radical transformation. Notably, as analyzed by differential scanning calorimetry (DSC), in contrast to copolymers of CTFE and ethyl vinyl ether (EVE), the CTFE-MIE copolymers with similar molecular weights exhibit clearly improved T_g of about 50 ℃ via simply introducing methyl substituents on the polymer backbone. Given the broad interests in fluoropolymers and established applications of fluoroalkene-vinyl ether copolymers, we believe that this work should be informative to the rational design of novel fluoropolymers and attractive for material engineering with improved thermal stability.

Key words: fluoropolymer, copolymer, photopolymerization, reversible deactivation radical polymerization, chlorotrifluoroethylene

Cite this article

Jinglin Yi, Mao Chen. Photo-Induced Copolymerization of Chlorotrifluoroethylene and Methyl Isopropenyl Ether^★[J]. Acta Chimica Sinica, 2024, 82(2): 126-131.

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Fig. & Tab. 7

Figure 1. (A) Chemical structures of PMA and PMMA and their glass transition temperatures; (B) design in this study

Figure 2. (A) Photopolymerization of CTFE and MIE; (B) chemical structure of PC; (C) chemical structure of CTAs

Entry	CTA	Light source	Conv. (MIE)^b/%	M_n,GPC^c/kDa	Ð^c
1	1a	blue	85	10.7	2.11
2	1b	blue	80	9.9	1.96
3	1c	blue	20	4.4	2.13
4	2a	blue	90	8.3	1.96
5	2b	blue	85	5.6	1.64
6	2c	blue	76	5.9	1.57
7	3c	blue	<5	—	—
8	4c	blue	83	8.6	2.02
9	5c	blue	<5	—	—
10	2c	—	0	—	—
11	2c	purple	79	5.3	1.64
12	2c	white	52	3.4	1.53
13^d	2c	white	<5	—	—

Table 1. Optimization of reaction conditions for the copolymerization of CTFE and MIE under light irradiationa

Entry	[CTFE]/[MIE]/[CTA]	Conv. (MIE)^b/%	M_n,GPC^c/kDa	M_n,MALS^d/kDa	Ð^c
1	400/200/1	>99	19.1		1.77
2	400/300/1	83	16.2		1.75
3	800/400/1	>99	24.8	87.5	1.85
4	1000/500/1	>99	34.8	212.8	1.90

Table 2. Synthesis of CTFE-MIE copolymers with different molecular weightsa

Figure 3. (A) DPs of CTFE (empty symbols) and MIE (filled symbols) vs. exposure time; (B) ln([M]0/[M]t) vs. exposure time. [M]0 and [M]t are the concentrations of MIE at time points 0 and t, respectively; (C) Mn (filled symbols) and ? (empty symbols) vs. MIE conversion (%)

Figure 4. GPC results of fluorinated block copolymers synthesized via chain extensions. P1=P(CTFE-alt-MIE), P1a=P(CTFE-alt-MIE)- b-PMMA, P1b=P(CTFE-alt-MIE)-b-PVAc

Figure 5. DSC profiles of CTFE-EVE copolymers (P2 and P3) and CTFE-MIE copolymers (P4 and P5)

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三氟氯乙烯与甲基异丙烯基醚的光诱导共聚反应^★