Synthesis and characterization of temperature‐responsive copolymers based on N‐vinylcaprolactam and their grafting on fibres

Abstract

BACKGROUND: Responsive materials are able to respond reversibly to an environmental stimulus. When the stimulus is temperature in the physiological range, the responsive material is particularly interesting for textile applications. We describe here the synthesis and characterization of reactive temperature‐responsive copolymers and their subsequent grafting on cotton fabrics. RESULTS: Copolymers of N‐vinylcaprolactam and various reactive monomers were synthesized via free radical polymerization in solution. The copolymers were characterized in terms of chemical structure, molecular weight and temperature‐responsive properties. The copolymer of N‐vinylcaprolactam and methacrylic acid (11 or 22 wt%) and the hydrolysed copolymer of N‐vinylcaprolactam and acryloyl chloride were found to be temperature responsive. They were subsequently grafted on cotton fabrics. The grafting was studied using X‐ray photoelectron spectroscopy and scanning electron microscopy measurements and was found to be effective. Finally, the modified cotton fabrics were found to exhibit temperature‐responsive water regain and water vapour transmission rates. CONCLUSION: Temperature‐responsive copolymers were synthesized, characterized and successfully grafted on cotton fabrics, yielding responsive fabrics. Such fabrics can hence be used to modulate the skin microclimate under textiles. Copyright © 2009 Society of Chemical Industry

Temperature responsive copolymers of N‐vinylcaprolactam and di(ethylene glycol) methyl ether methacrylate and their interactions with drugs

“…For both types of polymerizations, the fraction of VCL units in the copolymers was always smaller than the VCL fraction in the comonomer mixtures (Supporting Information Table S1) although an oil‐soluble initiator was employed for the miniemulsions. This is explained by the lower reactivity of N ‐vinylcaprolactam, which was already observed for other copolymerizations . A similar behavior was observed for the copolymerization of N ‐isopropylacrylamide and di(ethylene glycol) methyl ether methacrylate …”

“…This is explained by the lower reactivity of N-vinylcaprolactam, which was already observed for other copolymerizations. 10 A similar behavior was observed for the copolymerization of N-isopropylacrylamide and di(ethylene glycol) methyl ether methacrylate. 31 A striking difference between both types of polymerization is their respective yield (see Table S1, Supporting Information).…”

“…4,5 Poly(N-vinylcaprolactam) (PVCL) has a LCST in water in the range of 32-38 C, depending on the solution concentration 6 and, to some extent, on the molecular weight. [7][8][9][10] This range of temperature is included in the physiological range and the temperature dependent collapse does not show a significant hysteresis. PVCL is also particularly interesting for biomedical applications as it has a much lower cytotoxicity than poly(N-isopropylacrylamide) and hence the application of PVCL nanoparticles as drug delivery vehicles has been recently reported.…”

Poly(N-vinylcaprolactam), a comprehensive review on a thermoresponsive polymer becoming popular

“…To further modulate the features of PNVCL aqueous solutions, PNVCL has been modified via copolymerization with a variety of monomers: 1-vinylimidazole (VIm) [51][52][53][54], 1-vinyl-2-methylimidazole (VMI) [55], N-vinylpyrrolidone (NVP) [14,20,29,[56][57][58], methacrylic acid (MAA) [19,59,60], Acrylic acid (AA) [50], 2-methacryloiloxybenzoic acid (2MBA) [19], sodium acrylate (SA) [61], N-acryloylsuccinimide (NASI) [62], nbutylacrylate (BA) [14,62], N,N-dimethylaminoethyl methacrylate (DMAEMA) [63,64], N,N-diethylaminoethyl methacrylate (DEAEMA) [19], methyl methacrylate (MMA) [47,65], vinyl acetate (VAc) [66], N-vinyl pivalate (NVPi) [66], 5-vinyltetrazole (VT) [67,68], 2-methyl-5-vinyltetrazole (MVT) [67], N-t-Boc-tryptophanamido-N'-methacryl thioureas (TrpAMT) [14], glycidyl methacrylate (GMA) [69], N-vinyl-N-acetate (VAc) [70], N-methyl-N-vinylacetamide (NVMA) [66,70], n-hexyl acrylate (HA) [19], acryloyl chloride (AC) [71], maleic acid (MA) [72], N-(t-butoxycarbonylaminopropyl)methacrylamide (t-BOCAPMA) [73], and alkyl acrylate derivations labeled with pyrene or naphthalene, as well as via grafting with PEO as an effective stabilizing agent …”

A straightforward synthesis of fluorescent and temperature‐responsive nanogels

“…Poly( N ‐vinylcaprolactam) PVCL is a temperature‐responsive polymer of great interest for biomedical applications, as it possesses a lower critical solution concentration in water in the physiological range,1–3 very similar to the well‐known poly( N ‐isopropylacrylamide) PNIPAM (32 °C) 4. Other groups already proposed interesting alternatives to PNIPAM such as copolymers of oligo(ethylene glycol) methacrylate and 2‐(2‐methoxyethoxy)ethyl methacrylate 5…”