The effect of reaction conditions on the chain end structure and functionality during dehydrochlorination oftert-chlorine-telechelic polyisobutylene by potassium tert-butoxide

Dehydrochlorination of tert-chlorine-telechelic polyisobutylene with potassium tert-butoxide in refluxing tetrahydrofuran is quantitative after 22 h, but results in ca. 3% endo olefin chain ends which are not reactive in some subsequent functionalization reactions. The formation of these undesired structures is most likely due to simultaneous thermally induced HCl loss. Lower temperatures and longer reaction times led to exclusive formation of external double bonds in some cases but to incomplete dehydrochlorination.

Endfunctional Polymers by Functionalization of Living Cationic Chain Ends with 1,1-Diphenylethylene

Abstract A new functionalization method has been developed for the synthesis of 2,2-diphenylvinyl(DPV)-telechelic polyisobutylene (PIB). First, living carbocationic polymerization (LCCP) of isobutylene (IB) is quantitatively end-quenched with a nonpolymerizable olefin, 1,1-diphenylethylene (DPE). This process yields a mixture of diphenyl substituted vinyl and tertiary chlorine endgroups. Treatment of the resulting polymer with potassium-tert-butoxide (tBuOK) leads to the quantitative formation of DPV-telechelic PIB which is a potential macroinitiator precursor for living anionic polymerizations.

Characterization of Micelles of Polyisobutylene-block-poly(methacrylic acid) in Aqueous Medium

Four amphiphilic block copolymers polyisobutylene-block-poly(methacrylic acid) (IBm-MAAn; m = 70−134, n = 52−228) were synthesized and transferred into aqueous medium at pH 10−12. Their structure in solution was characterized by fluorescence correlation spectroscopy (FCS), static and dynamic light scattering (SLS, DLS), analytical ultracentrifuge (AUC), and by transmission electron microscopy (TEM) with freeze-fracturing and staining techniques. DLS data, AUC sedimentation traces, and TEM images indicate at least two different kinds of particles. TEM shows spherical micelles; however, especially for polymers with larger hydrophobic blocks, additional particles are observed. FCS shows extrem…

Synthesis of Linear and Star-Shaped Block Copolymers of Isobutylene and Methacrylates by Combination of Living Cationic and Anionic Polymerizations

A new synthetic route for the preparation of polyisobutylene (PIB)-based linear and star-shaped block copolymers was developed by combining living carbocationic and anionic polymerizations. Living PIB chains were quantitatively endcapped with 1,1-diphenylethylene, leading to 1,1-diphenyl-1-methoxy (DPOMe) or 2,2-diphenylvinyl (DPV) termini, or both. Both the DPOMe- and DPV-terminated PIBs, and the mixtures of both endgroups were quantitatively metalated with K/Na alloy, Cs metal, or Li dispersion in THF at room temperature. The resulting stable macrocarbanion obtained by metalation with K/Na alloy was used to initiate living anionic polymerization of tert-butyl methacrylate (tBMA) yielding …

Synthetic approaches towards new polymer systems by the combination of living carbocationic and anionic polymerizations

This study summarizes recent efforts to obtain by combination of living carbocationic and anionic polymerizations block copolymers which are potential precursors for building new well-defined polymeric architectures with microphase separated morphology. Living carbocationic polymerization (LCCP) yields telechelic polyisobutylene (PIB) chains with a variety of useful endgroups, such as tert-chlorine, isopropenyl, primary hydroxyl, tolyl etc. When tolyl-ended PIB was used as precursor for macroinitiator of living anionic polymerization of 2-(tert-butyldimethylsilyloxy)ethyl methacrylate (tBuMe2SiOEMA), mixtures of homopolymers and block copolymers were formed due to incomplete lithiation of t…

Synthesis strategies and properties of smart amphiphilic networks

This paper briefly surveys recent developments in the field of amphiphilic networks (APN) which are a new class of crosslinked polymer systems consisting of covalently bonded hydrophobic and hydrophilic chain segments. The covalent bonds between immiscible hydrophobic and hydrophilic polymer chains prevent demixing and yield polymer networks with unique structure and properties. Telechelic macromonomers provide the basis for the first generation of APNs obtained by copolymerization of the macromonomer with selected low molecular weight monomers. Synthesis of a variety of APNs using methacrylate-telechelic polyisobutylene (PIB) macromonomers prepared by living carbocationic polymerization (L…

Synthesis of linear and three-arm star tert-chlorine-telechelic polyisobutylenes by a two-step conventional laboratory process

A two-step conventional laboratory process was developed for the synthesis of mono- and difunctional linear and three-arm star tert-chlorine-telechelic polyisobutylenes (PIB) with desired molecular weights (MW) and narrow molecular weight distribution (MWD) by living carbocationic polymerization (LCCP). This polymerization method applies easy to handle operations and chemicals. LCCP of isobutylene (IB), was carried out in CH2Cl2 as solvent and with BCl3 as coinitiator in the first step to obtain soluble low MW PIB prepolymer with narrow MWD. This was followed by addition of hexane, TiCl4 and additional monomer in the second step to prepare PIBs with desired MW and narrow MWD in practically …

Stable Carbanions by Quantitative Metalation of Cationically Obtained Diphenylvinyl and Diphenylmethoxy Compounds:  New Initiators for Living Anionic Polymerizations

Micelles of polyisobutylene-block-poly(methacrylic acid) diblock copolymers and their water-soluble interpolyelectrolyte complexes formed with quaternized poly(4-vinylpyridine)

The micellization of ionic amphiphilic diblock copolymers, polyisobutylene-block-poly(methacrylic acid) (PIB-b-PMAA), with a constant degree of polymerization of the non-ionic block ðDPn ¼ 20Þ and various degrees of polymerization of the polyelectrolyte block ðDPn ¼ 100 – 425Þ was examined in aqueous media by means of fluorescence spectroscopy using pyrene as a polarity probe. The molar values of the critical micellization concentration (cmc) were found to be around 2 £ 10 26 mol/l, being nearly independent of the length of the polyelectrolyte block as well as pH (in the range 6 – 9) and ionic strength (# 0.5 M NaCl) while the specific cmc values varied from 20 to 100 mg/l. Small-angle neut…