ABSTRACT
For the first time, double stimuli-responsive properties of poly(N-isopropylacrylamide) (PNIPA) and poly(1-vinylimidazole) (PVIM) block copolymers in aqueous solutions were studied. The synthesis of PNIPA60-b-PVIM90 and PNIPA28-b-PVIM62-b-PNIPA29 was performed using reversible addition-fragmentation chain transfer (RAFT) polymerization. The polymers were characterized by size exclusion chromatography and 1H NMR spectroscopy. The conformational behavior of the polymers was studied using dynamic light scattering (DLS) and fluorescence spectroscopy (FS). It was found that PNIPA and block copolymers conformation and ability for self-assembly in aqueous medium below and above cloud point temperature depend on the locus of hydrophobic groups derived from the RAFT agent within the chain. Additionally, the length of PVIM block, its locus in the chain and charge perform an important role in the stabilization of macromolecular micelles and aggregates below and above cloud point temperature. At 25 °C the average hydrodynamic radius (Rh) of the block copolymer particles at pH 3 is lower than at pH 9 implying the self-assembling of macromolecules in the latter case. Cloud points of PNIPA60-b-PVIM90 are ~43 °C and ~37 °C at a pH of 3 and 9 and of PNIPA28-b-PVIM62-b-PNIPA29 they are ~35 °C and 31 °C at a pH of 3 and 9. Around cloud point independently of pH, the Rh value for triblock copolymer rises sharply, achieves the maximum value, then falls and reaches the constant value, while for diblock copolymer, it steadily grows after reaching cloud point. The information about polarity of microenvironment around polymer obtained by FS accords with DLS data.
Subject(s)
Acrylic Resins , Polymers , Polymers/chemistry , Acrylic Resins/chemistry , ImidazolesABSTRACT
The review summarizes recent advances in the production of carbon fiber precursors based on melt-spun acrylonitrile copolymers. Approaches to decrease the melting point of polyacrylonitrile and acrylonitrile copolymers are analyzed, including copolymerization with inert comonomers, plasticization by various solvents and additives, among them the eco-friendly ways to use the carbon dioxide and ionic liquids. The methods for preliminary modification of precursors that provides the thermal oxidative stabilization of the fibers without their melting and the reduction in the stabilization duration without the loss of the mechanical characteristics of the fibers are discussed. Special attention is paid to different ways of crosslinking by irradiation with different sources. Examples of the carbon fibers preparation from melt-processable acrylonitrile copolymers are considered in detail. A patent search was carried out and the information on the methods for producing carbon fibers from precursors based on melt-spun acrylonitrile copolymers are summarized.
ABSTRACT
Reversible addition-fragmentation chain transfer polymerization was successfully applied to the synthesis of the gradient copolymer of acrylic acid and vinyl acetate in the selective solvent. The gradient degree of the copolymer was varied by the monomer feed. The monomer conversion was found to affect the ability of the copolymer to self-assemble in aqueous solutions in narrowly dispersed micelles with an average hydrodynamic radius of about 250 nm. Furthermore, the synthesized copolymers also tended to self-assemble throughout copolymerization in the selective solvent.
