Polyisobutylene-block-poly

N. Martinez-Castro, M.G. Lanzendorfer, A.H.E. Muller, J.C. Cho, M.H. Acar, and R. Faust, Polyisobutylene stars and polyisobutylene-block-poly(tert-butyl methacrylate) block copolymers by site transformation of thiophene end-capped polyisobutylene chain ends, Macromolecules, 36(19) 6985-6994, September 2003. 

Pergushov, D.V., Remizova, E.V., Gradzielski, M., Lindner, P., Feldthusen, J., Zezin, A.B., Muller, A.H.E. and Kabanov, V.A. (2004) Micelles of polyisobutylene-block-poly(methacrylic acid) diblock copolymers and their water-soluble interpolyelectrolyte complexes formed with quaternized poly(4 vinylpyridine). Polymer, 45, 367-378. 

Schuch H, Klingler J, Rossmanith P, Frechen T, Gerst M, Feldthusen J, Muller AHE (2000) Characterization of micelles of polyisobutylene-block-poly(methacrylic acid) in aqueous medium. Macromolecules 33(5) 1734-1740... 

Pergushov DV et al. Micelles of polyisobutylene-block-poly(methacrylic acid) diblock copolymers and their water-soluble interpolyelectrolyte complexes formed with quat-emized poly(4-vinylpyridine). Polymer 2004 45(2) 367-378. 

Polyisobutylene-b-poly(methacrylic acid) (PIB-b-PMAA) was prepared by hydrolysis of the ester group under acidic conditions, using HCl(aq) in dioxane. After hydrolysis a new amphiphilic diblock copolymer is formed as shown in Scheme 3. The resulting amphiphilic block copolymers form a stable polymeric emulsions in dioxane. 

The direct coupling of preformed living blocks (usually cation and anion or group transfer) also enables the formation of block copolymers, such as polytetrahydrofuran-b-polystyrene-b-polytetrahydrofuran [13], polystyrene-b-polytetrahydrofuran [14], polystyrene-b-poly(ethyl vinyl ether) [15], poly(methyl methacrylate)-b-polytetrahydrofuran [16], poly[0-(jS-D- glucopyranosyl)-L-serine]-b-poly(2-methyl-2-oxazoline) [8], poly(methyl methacrylate)-b-poly(butyl vinyl ether) [17], polyisobutylene-b-poly(vinyl ferrocene), and poly(vinyl ferrocene)-polyisobutylene-b-poly(vinyl ferrocene) [18]. A typical example of such a coupling process between oppositely charged macroions is presented in Scheme 11.1, for the preparation of polystyrene-b-poly(ethyl vinyl ether) [15]. 

Keszler, B., Fenyvesi, G., and Kennedy, J. P. (2000). Novel star-block pol5mers three polyisobutylene-b-poly(methyl methacrylate) arms radiating from an aromatic core. J. Polym. 

Binder, W.H. and Machl, D. (2005) Poly(ether ketone)-polyisobutylene block copolymers Synthesis and phase behavior. Journal of Polymer Science Part A-Polymer Chemistry, 43,188-202. 

Cao X. and Faust R., Polyisobutylene based thermoplastic elastomer 5. Poly(styrene-b-isobutylene-b-styrene) tri-block copolymers by coupling of living poly(styrene-b-isobutylene) di-block copolymers. Macromolecules, 32, 5487, 1999. 

Walch E. and Caymans R.J., Synthesis and properties of poly(butylenes terephthalate)-b-polyisobutylene segmented block copolymers, Polymer, 35, 636, 1994. 

Among the many unusual properties that the arborescent architecture leads to, most notable is the discovery that block copolymers with a high MW dendritic (arborescent) polyisobutylene core and poly(para-methylstyrene) end blocks can manifest themselves either as a rubber, or as a plastic, depending on their environment (Figures 7.16 and 7.17). The behavior is thermally irreversible. 

Puskas, J.E., Pattern, W.E., Wetmore, P.M., and Krukonis, A. Multiarm-star polyisobutylene-polystyrene thermoplastic elastomers from a novel multifunctional initiator, Polym. Mater. Set Eng., 82,42 3, 1999. Brister, L.B., Puskas, J.E., and Tzaras, E. Star-branched PIB/poly(p-t-bu-Styrene) block copolymers from a novel epoxide initiator, Polym. Prepr., 40, 141-142, 1999. 

Polyisobutylene-based block anionomers and cationomers, ( ), were prepared by Kennedy et al. (3) and used in drug release devices. Poly(2-dimethylami-no)ethyl methacrylate was quaternized after the block copolymer was synthesized to form a cationic block copolymer. 

D. Feng, T. Higashihara, and R. Faust, Facile synthesis of diphenyl-ethylene end-functional polyisobutylene and its applications for the synthesis of block copolymers containing poly(methacrylate)s, Polymer, 49(2) 386-393, January 2008. 

Z. Fodor and R. Faust, Polyisobutylene-based thermoplastic elastomers. IV. Synthesis of poly (styrene-block-isobutylene-block-styr-ene) triblock copolymers using n-butyl chloride as solvent, J. Macromol. Sci.-Chem., 33(3) 305-324, March 1996. 

HMX HMX HMX HMX HMX HMX HMX HMX HMX HMX HMX HMX HNS NTO NTO/HMX NTO/HMX NTO/HMX PETN PETN PETN PETN PETN PETN PETN PETN PETN PETN RDX RDX RDX RDX RDX RDX RDX RDX RDX RDX RDX RDX RDX TATB/HMX Cariflex (thermoplastic elastomer) Hydroxy-terminated polybutadiene (polyurethane) Hydroxy-terminated polyester Kraton (block copolymer of styrene and ethylene-butylene) Nylon (polyamide) Polyester resin-styrene Polyethylene Polyurethane Poly(vinyl) alcohol Poly(vinyl) butyral resin Teflon (polytetrafluoroethylene) Viton (fluoroelastomer) Teflon (polytetrafluoroethylene) Cariflex (block copolymer of butadiene-styrene) Cariflex (block copolymer of butadiene-styrene) Estane (polyester polyurethane copolymer) Hytemp (thermoplastic elastomer) Butyl rubber with acetyl tributylcitrate Epoxy resin-diethylenetriamine Kraton (block copolymer of styrene and ethylene-butylene) Latex with bis-(2-ethylhexyl adipate) Nylon (polyamide) Polyester and styrene copolymer Poly(ethyl acrylate) with dibutyl phthalate Silicone rubber Viton (fluoroelastomer) Teflon (polytetrafluoroethylene) Epoxy ether Exon (polychlorotrifluoroethylene/vinylidine chloride) Hydroxy-terminated polybutadiene (polyurethane) Kel-F (polychlorotrifluoroethylene) Nylon (polyamide) Nylon and aluminium Nitro-fluoroalkyl epoxides Polyacrylate and paraffin Polyamide resin Polyisobutylene/Teflon (polytetrafluoroethylene) Polyester Polystyrene Teflon (polytetrafluoroethylene) Kraton (block copolymer of styrene and ethylene-butylene)... 

Poly (iso butylene) glycol is a suitable rubbery segment in thermoplastic elastomers. An oligomer such as 56 with a tertiary chloro group at both ends could be employed also as the initiator of cationic polymerization of a-methylstyrene (a-MeSt) in the synthesis of a three-block copolymer of poly(a MeSt)-polyisobutylene-poly(a-MeSt)52). 

Other multifunctional initiators include star polymers prepared from initiators via living radical or other living polymerizations. In particular, all of the star polymers via metal-catalyzed living polymerization, by definition, carry a halogen initiating site at the end of each arm, and thus they are potentially all initiators. Thus, star-block copolymers with three polyisobutylene-Mock-PMMA arms and four poly-(THF) -A/oc/F polystyrene or poly(THF)-Woc/c-polysty-rene-Wock-PMMA were synthesized via combination of living cationic and copper-catalyzed living radical polymerizations.381,388 Anionically synthesized star polymers of e-caprolactone and ethylene oxide have... 

QU2 Quintana, J.R., Salazar, R.A, and Katime, I., Micelle formation and polyisobutylene solubilization by polystyrene-Z>/oc -poly(ethylene-co-butylene)-Z>/ocA -polystyrene block copolymers, Macrowo/. Chem. Phys., 196, 1625, 1995. 

A new technique was developed recently, by introducing cationic to anionic transformation. A living carbocationic polymerization of isobutylene is carried out first. After it is complete, the ends of the chains are transformed quantitatively to polymerization-active anions. The additional blocks are then built by an anionic polymerization. A triblock polymer of poly(methyl methacrylate)-polyisobutylene-poly(methyl methacrylate) can thus be formed. The transformation involves several steps. In the first, a compound like toluene is Friedel-Craft alkylated by a,6t>"di-rerr-chloro-polyisobutylene. The ditolylpolyisobutylene which forms is lithiated in step two to form a,cu-dibenzyllithium polyisobutylene. It is then reacted with 1,1-diphenylethylene to give the corresponding dianion. After cooling to -78 °C and dilution, methyl methacrylate monomer is introduced for the second polymerization in step three. 

In a more recent study [88], the chlorine end groups of PIB were quantitatively converted to bromoester groups to facilitate ATRP from end-positioned activated ester groups (Scheme 11.21). In this way, the capping with short blocks of PSt observed in the earlier method could be avoided. The concept was further extended to the preparation of PIB-h-PMMA diblock [89], poly(t-butyl acrylate)-b-polyisobutylene-b-polystyrene triblock [90], and amphiphilic pentablock copolymers based on PIB [91]. 

Orientations in elongated mbbers are sometimes regular to the extent that there is local crystallization of individual chain segments (e.g., in natural rubber). X-ray diffraction patterns of such samples are very similar to those obtained from stretched fibers. The following synthetic polymers are of technical relevance as mbbers poly(acrylic ester)s, polybutadienes, polyisoprenes, polychloroprenes, butadiene/styrene copolymers, styrene/butadiene/styrene tri-block-copolymers (also hydrogenated), butadiene/acrylonitrile copolymers (also hydrogenated), ethylene/propylene co- and terpolymers (with non-conjugated dienes (e.g., ethylidene norbomene)), ethylene/vinyl acetate copolymers, ethyl-ene/methacrylic acid copolymers (ionomers), polyisobutylene (and copolymers with isoprene), chlorinated polyethylenes, chlorosulfonated polyethylenes, polyurethanes, silicones, poly(fluoro alkylene)s, poly(alkylene sulfide)s. 

Common SS include polyethers, polyesters and polyalkyl glycols with glass transition temperatures in the range of -70°to -30°C. Commonly used macrodiols in the PUs synthesis are polyalkyl-diols, such as polyisobutylene diol [70], polybutadiene (PBU) [20, 71], or oligo-butadiene diols [72] as well as hydrogenated polybutadiene diol [20] polyether diols polytetrahydrofuran (PTHF or PTMO) [50-52], polyethylene glycol (PEG) or (PEO) [73], polypropyleneoxide (PPO) [73] or mixed blocks of them PEO-PPO-PEO [74] and PPO-THF [54] polyester diols poly(ethylene adipate) (PEA) [4,20], poly(butylene adipate) (PBA) [20, 73], and latterly polycaprolactone diol (PCL or PCD) [75], polyalkylcarbonate polyol [20] or mixed blocks of them, for example poly(carbonate-co-ester)diol [76], poly(hexamethylene-carbonate)diol [77], as well as poly(hexamethylene-carbonate-co-caprolactone)diol [78] and a mixed block copolymer of polyether and polyester blocks PCL-b-PTHF-b-PCL [79]. Examples schemes of macrodiols are shown in Eig. 1.9. 

The partial molar quantities of mixing were determined for normal and branched alkanes (O5 — Cio), cyclohexane, benzene and tetrachloromethane in polyisobutylene [57]. Partial molar enthalpies of mixing were measured for normal alkenes in low and high density polyethylene, polypropylene, polybutene-1, polystyrene, poly(methyl acrylate), poly(vinyl chloride), polyCN-isopropyl-acrylamide), ethylene-vinyl acetate copolymer, ethylene-carbon oxide copolymer [88] normal, branched and cyclic alkanes, benzene, n-butylbenzene, ois- and ra s-decalin, tetraline and naphthalene in polystyrene at 183, 193 and 203°C [60] these solutes in poly (methyl acrylate) [57] n-nonane, n-dodecane and benzene in polystyrene in the range 104.8 — 165.1 C [71] O7—C, C12 normal alkanes and aromatic hydrocarbons in polystyrene at an average temperature of 204.9°C [72], C7—Cg normal alkanes in poly(ethylene oxide) at an average temperature of 66.5 "C [72] normal alkanes in ethylene oxide—propylene oxide block copolymers (Pluronics L 72, L 64 and F 68) at the same average temperature [72]. 

There are three major classes of polymers used in PSAs today block copolymer, natural rubber, and acryhc. A munber of other polymers used in smaller, specialty applications include sihcones, polyisobutylenes, polyolefins, styrene-butadiene, poly(vinyl alkyl ether)s, and polsmrethanes. 

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