Radical copolymerization of acrylonitrile with 2,2,2‐trifluoroethyl acrylate for dielectric materials: Structure and characterization

Abstract

Radical copolymerization based on acrylonitrile (AN) and 2,2,2‐Trifluoroethyl acrylate (ATRIF) initited by AIBN was investigated in acetonitrile solution. The resulting poly(AN‐co‐ATRIF) copolymers were characterized by 1H, 13C, and 19F NMR and IR spectroscopy, and size exclusion chromatography (SEC). Their compositions were assessed by 1H NMR. The kinetics of radical copolymerization of AN with ATRIF was investigated from sereval experiments achieved at 70 °C from initial [AN]0/[ATRIF]0 molar ratios ranging between 20/80 and 80/20 and was enabled to determine the reactivity ratios of both comonomers. From the monomer—polymer copolymerization curve, the Fineman–Ross and Kelen–Tüdos laws enabled to assess the reactivity ratios (rAN= r1 = 1.25 ± 0.04 and rATRIF = r2 = 0.93 ± 0.05 at 70 °C) while the revised patterns scheme led to r12 = rAN = 1.03, and r21 = rATRIF = 0.78 at 70 °C. In all cases, rAN x rATRIF product was close to unity, which indicates that poly(AN‐co‐ATRIF) copolymers exhibit a random structure. This was also confirmed by the Igarashi's and Pyun's laws which revealed the presence of AN‐ATRIF, AN‐AN, and ATRIF‐ATRIF dyads. The Q and e values for ATRIF were also assessed (Q2 = 0.62 and e2 = 0.93). The glass transition temperature values, Tg, of these copolymers increased from 17 to 61 °C as the molar percentage of ATRIF decreased from 77 to 16% in the copolymer. Thermogravimetry analysis of poly(AN‐co‐ATRIF) copolymers showed a good thermal stability compared to that of poly(ATRIF) homopolymer due to incorporation of AN comonomer. © 2013 Wiley Periodicals, Inc. J. Polym. Sci., Part A: Polym. Chem. 2013, 51, 3856–3866

Poly(fluoroacrylate)s with tunable surface hydrophobicity via radical copolymerization of 2,2,2-trifluoroethyl α-fluoroacrylate and 2-(trifluoromethyl)acrylic acid

“…In addition, our team achieved the synthesis of novel copolymers composed of cyano co-monomer such as acrylonitrile, methacrylonitrile, methylvinylidene cyanide, and TFEM. [38][39][40] Chen and Wu 41 Among α-fluoroacrylates, 42 homopolymers of 2,2,2-trifluoroethyl α-fluoroacrylate (PFATRIFE), prepared by conventional radical homopolymerization, 10,43 possess a low refractive index (n = 1.385) due to the low content of hydrogen atoms in the polymer and a high glass transition temperature (T g = 117-123 °C ). FATRIFE was also used in copolymerization with numerous comonomers, including tert-butyl trifluoromethacrylate, 44 MMA, 45 methyl αfluoroacrylate, 46 1,1,3,3-tetrafluoropropyl α-fluoroacrylate, 47 methyl α-fluoroacrylate and ethyl methacrylate, [48][49][50] acrylates 51 and α-fluoroacrylates bearing a nonlinear optical chromophore.…”

Photoinduced Copolymerization of APMP-MMA: The Role of Reactive Hindered Amine APMP

“…The cumulative copolymer composition versus total monomer conversion for the photoinduced APMP-MMA copolymerization was shown in Figure 6, where the plots were obtained from the experimental results of the copolymerization and the lines obtained from the reactivity ratios ( 1 = 0.353, 2 = 0.168) by (4) and (5). The constant composition of the APMP in the copolymers would be 0.57 when the azeotropic copolymerization would occur with the initial feed ratio of APMP of 0.57.…”

“…The acrylate monomer with functional groups can provide plenty of excellent characteristics. For example, the acrylates containing fluorine provide the polymers with unique surface properties in high thermal stability, good chemical inertness and oxidative stability, superior weatherability, oil and water repellency, low flammability, and good biocompatibility as well as low refractive index [3,4]. The acrylates containing silicon enhanced the adhesion to the surface and extraction resistance in coating [5].…”

Fabrication of asymmetrically superhydrophobic cotton fabrics via mist copolymerization of 2,2,2‐trifluoroethyl methacrylate

“…We designed a novel functional copolymer as shown in Scheme . By comparing with other highly fluorinated monomers often used for fabricating superhydrophobic surfaces, monomer of 2,2,2‐trifluoroethyl methacrylate (TFMA) is inexpensive and environmentally friendly . Meanwhile, 2‐isocyanatoethyl methacrylate (IEM) could covalently link the copolymer chains onto the cotton surface through the reaction between the isocyanate group and the hydroxyl groups in cellulose.…”