Preparation of main‐chain imidazolium‐functionalized amphiphilic block copolymers through combination of condensation polymerization and nitroxide‐mediated free radical polymerization and their micelle study

Main‐chain imidazolium‐functionalized amphiphilic block copolymers (PIL‐b‐PS) consisting of polyionic liquid (PIL) and polystyrene (PS) blocks have been first synthesized by condensation polymerization combined with nitroxide‐mediated free radical polymerization (NMP). The di‐functional imidazolium‐based ionic liquid (IL) having both hydroxyl and ester end groups was synthesized through Michael addition between imidazole and methylacrylate (MA) and further quaternization by 2‐chloroethanol. The HTEMPO (4‐hydroxy‐2,2,6,6‐tetramethyl‐1‐piperidinyloxy) terminated polyionic liquid (HTEMPO‐PIL) as the hydrophilic block was prepared by condensation polymerization of di‐functional imidazolium IL and HTEMPO at a certain ratio. The hydrophobic PS block was synthesized by controlled radical polymerization of styrene using HTEMPO‐PIL through NMP, resulting PIL‐b‐PS block copolymers. The structure of block copolymers obtained has been characterized and verified by FTIR, ¹H NMR, and size exclusion chromatography analyses. In addition, the morphology and size of the micelles formed by PIL‐b‐PS block copolymers in water were investigated by transmission electron microscopy and dynamic light scattering. © 2012 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem, 2012     

Phase Behavior of Nonaqueous Microemulsions of n‐Methyl‐2‐Pyrrolidinone/Diisooctylsodium Sulfosuccinate (AOT)/Alkanes

The phase behavior of n‐methyl‐2‐pyrrolidinone (NMP) microemulsions formed by the combination of NMP and oils (hexane, heptane, octane, and isooctane) in the presence of diisooctylsodium sulfosuccinate (AOT) were studied. The ternary plots were constructed and found to be similar in nature and consisted of a gel, a clear, or microemulsion, and a two phase region. Effects of varying amounts of water added to NMP and varying the chain length of n‐alkane (as oil) on the microemulsion region were investigated. Fluorescence probes such as Auramine‐O and the sodium salt of aniline‐1‐ napthalenesulfonic acid were employed to investigate the nature of the microemulsion region. Volume and temperature induced percolation studies have indicated the absence of percolation process in these microemulsion systems.     

A Comprehensive Study and Characterization of Colloidal Emeraldine-Base

Soluble emeraldine-base (PANI-EB) was prepared and its structure was characterized using ¹H, ¹³C and 2D (COSY, HMQC and HMBC) NMR. The solubility of the polymer in two solvents (N-methylpyrrolidone (NMP) and dimethyl sulfoxide (DMSO), the structure of the solution (aggregation) and the behavior of polyaniline were studied by viscometry and by dynamic light scattering (DLS) in dilute solution. Viscometric behavior in NMP and Huggins constant determination confirm supramolecular interactions also evidenced by DLS; at end, the molecular weight of the soluble fraction of PANI-EB is determined.     

Efficient Synthesis of Spiro[diindenopyridine-indoline]triones Catalyzed by PEG-OSO3H-H2O and [NMP]H2PO4

One-pot, three-component synthesis of spiro[diindenopyridine-indoline]triones has been reported via the reaction of 1,3-indandione, aromatic amines, and isatins with (PEG-OSO₃H) as an efficient, polymeric acid surfactant–based catalyst in water and also in presence of acidic ionic liquid [NMP]H₂PO₄, which acts both as a medium and catalyst under conventional heating and ultrasonic irradiation. The reactions were complete in short reaction times with excellent yield of products. Surfactant-based PEG-OSO₃H could be recycled and reused several times without any significant loss of activity. The compounds exhibit fluorescence in methanol with large Stokes shift.     

Covalent attachment of polystyrene on multi-walled carbon nanotubes via nitroxide mediated polymerization

A new method to attach polymers on carbon nanotubes has been studied. We used nitroxide mediated polymerization (NMP) to graft polystyrene from multi-walled carbon nanotubes (MWNTs). Carboxyl groups on MWNTs were activated with thionyl chloride (SOCl₂) to give acyl chloride derivative (MWNT-COCl). NMP initiator was introduced to MWNT by esterification of 1-hydroxy-2-phenyl-2-(2′,2′, 6′, 6′-tetramethyl-1′-piperidinyloxy)ethane (HO-PE-TEMPO) with acyl chloride groups of MWNTs. The obtained MWNT-PE-TEMPO was used for initiation of bulk polymerization of styrene, yielding polystyrene-grafted MWNTs (MWNT-g-pSt). The resulting composites of MWNT-g-pSt were analyzed by TEM, SEM, FT-IR and TGA.     

Importance of the Position of the Chromophore Group on the Dissociation Process of Light Sensitive Alkoxyamines

New photosensitive alkoxyamines have been designed using molecular orbital calculations to improve the selective C O versus N O cleavage. The targeted light‐sensitive alkoxyamine is synthesized in one step and its reactivity under UV has been investigated using both ESR and LFP. The ability of this alkoxyamine to control the photopolymerization of n‐butyl acrylate is evidenced through a process called nitroxide‐mediated photopolymerization NMP². The selected alkoxyamine is finally used to prepare covalently bonded multilayered micropatterns. This original application highlights the high potential of this technique for some specific applications that require spatial control.

     

Re‐formation Reaction of Cyclic Nitroxide‐Based Alkoxyamines: Steric and Polar/Stabilization Effects

In nitroxide‐mediated radical polymerization, the polymerization times decrease with the increasing re‐formation rate constant of the C? ON bond (→ alkoxyamine) between the growing polymer chain and the nitroxide radical. The factors influencing the re‐formation rate constant are of considerable interest, but up to now, the polar/stabilization effects have not been addressed thoroughly. The combination of new data with previously reported data now showed that the re‐formation rate constant k_c increases with the increasing polar character of the substituents attached to the nitroxide moiety. The polar/stabilization effects are weaker for the re‐formation than for the homolysis of the C? ON bond, and may be mainly attributed to the relocation of the odd electron onto the O‐atom of the N? O moiety, i.e., the stabilization of the nitroxide moiety. Hence, it is possible to predict the values of k_c by combining both the polar/stabilization (σ_I) and steric effects (E ), i.e., log(k_c/M ^?1 s^?1) = 9.86 + 0.57 ? σ_I + 0.40 ? E_s.     

2,5‐Dihydro‐1H‐imidazole‐Based Nitroxides as Prospective Mediators in Living Radical Polymerization

A number of spectroscopic methods were applied to obtain kinetic parameters of reactions modelling the 2,5‐dihydro‐1H‐imidazole 1‐oxide mediated living polymerization of acrylates. The homolysis rate constants of alkoxyamines based on five nitroxides were measured by EPR spectroscopy at different temperatures. The recombination rate constants k_c between the corresponding alkyl radicals and the nitroxides were measured by means of laser flash photolysis. The time‐resolved chemically induced dynamic nuclear polarization (TR‐CIDNP) experiments revealed the negligible contribution of disproportionation in the recombination reaction. In addition, the thermodecomposition of alkoxyamines in the NMR probe showed the absence of intramolecular elimination of hydroxylamines from the corresponding alkoxyamines. Analysis of the kinetic parameters showed that the 2,5‐dihydro‐1H‐imidazole 1‐oxide type radicals are promising mediators for the living polymerization of acrylates and methacrylates.     

Synthesis of polymer grafted carbon nanotubes by nitroxide mediated radical polymerization in the presence of spin-labeled carbon nanotubes

Multiwalled carbon nanotubes (MWCNT) were grafted with polystyrene by in situ nitroxide mediated radical polymerization in the presence of TEMPO (2,2,6,6-tetramethylpiperidinyl-1-oxyl) functionalized MWCNT, which was synthesized by the reaction between 4-hydroxyl-TEMPO (HO-TEMPO) and carbonyl chloride groups on the MWCNT. Although the controllability of the polymerization was not high, highly soluble grafted MWCNTs were indeed obtained, indicating that the graft polymerization was efficient. The resulting polystyrene grafted MWCNTs were easily defunctionalized at room temperature using 3-chloroperoxybenzioc acid. TEM, SEM, and TGA were employed to determine the structure, morphology, and the grafting quantities of the resulting products.     

SYNTHESIS AND CHARACTERIZATION OF WELL-DEFINED BLOCK COPOLYMERS CONTAINING PENDANT, SELF-COMPLEMENTARY QUADRUPLE HYDROGEN BONDING SITES

The title block copolymer (defined as PSUEA) containing pendant,self-complementary quadruple hydrogen bonding sites has been prepared successfully by three steps.First,poly(styrene-b-2-hydroxyethyl acrylate) (defined as PSHEA) was prepared by living radical polymerizing 2-hydroxyethyl acrylate (HEA) initiated by polystyrene (PSt) macro- initiator,which was prepared via nitroxide-mediated polymerization (NMP) technique.After treated by excessive 3-isocyanatomethyl-3,5,5-trimethylcyclohexyl isocyanate (IPD...