Polyisobutylene-b-poly

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. 

Synthesis of poly(methyl methacrylate)"b-polyisobutylene-b-poly(methyl methacrylate) (PMMA-b-PIB-b-PMMA) triblock copolymers was also performed (see Table I). First, a series of DPE-capped telechelic PIBs were prepared by using a difiinctional initiator (tBuDiCumCl) for LCCP of IB. 

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. 

Figure 5.1. Molecular structures of the chemical repeat units for common polymers. Shown are (a) polyethylene (PE), (b) poly(vinyl chloride) (PVC), (c) polytetrafluoroethylene (PTFE), (d) polypropylene (PP), (e) polyisobutylene (PIB), (f) polybutadiene (PBD), (g) c/5-polyisoprene (natural rubber), (h) traw5-polychloroprene (Neoprene rubber), (i) polystyrene (PS), (j) poly(vinyl acetate) (PVAc), (k) poly(methyl methacrylate) (PMMA), ( ) polycaprolactam (polyamide - nylon 6), (m) nylon 6,6, (n) poly(ethylene teraphthalate), (o) poly(dimethyl siloxane) (PDMS).

PCP = polychloroprene, PDMS = polydimethylsiloxane, PE = polyethylene, B-PE = branched polyethylene, L-PE = linear polyethylene, PEO = poly(ethylene oxide), PE VAc = poly(ethylene-co-vinyl acetate), PIB = polyisobutylene, PMMA = poly(methyl methacrylate), PnBMA = poly(n-butyl methacrylate), PiBMA = poly(isobutyl methacrylate), PtBMA = poly(t-butyl methacrylate), PP = polypropylene, PS = polystyrene, PTMO = poly(tetramethylene oxide) or polytetrahydrofuran, PVAc = poly(vinyl acetate). 

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]. 

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. 

In principle, A can be any polymer normally regarded as a hard thermoplastic, eg, polystyrene, poly(methyl methacrylate), or polypropylene, and B can be any polymer normally regarded as elastomeric, eg, polyisoprene, polybutadiene, polyisobutylene, or polydimethylsiloxane (Table 2). 

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. 

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. 

FIGURE 20.10 (a,b) Phase images of cryo-ultramicrotomed surfaces of triblock copolymer styrene and ethylene-butylene (SEES) samples of neat material and loaded with oil (40 wt%), respectively. (c,d) Phase images of film of triblock copolymer poly(methyl methacrylate-polyisobutylene-poly(methyl methacrylate) (PMMA-PIB-PMMA) immediately after spin-casting and after 3 h annealing at 100°C, respectively. Inserts in the top left and right comers of the images show power spectra with the value stmctural parameter of microphase separation. 

Analytical procedures The molecular weights of the polyisobutylenes (Systematic name poly(l,l-dimethylethylene) and of the polynorbornadienes (Systematic name poly(3,5-tricyclo[2.2.1.02, b]heptylene) were determined by membrane osmometry in toluene solution and those of the polystyrenes were determined by vapour-pressure osmometry in chloroform. 

Noordermeer JaWM, Ferry JD, Nemoto N (1975) Viscoelastic properties of polymer solutions in high-viscosity solvents and limiting high-frequency behaviour. Ill Poly (2-substituted methyl acrylates). Macromolecules 8(5) 672-677 Okamoto H, Inoue T, Osaki K (1995) Viscoelasticity and birefringence of polyisobutylene. J Polym Sci B Polym Phys 33 1409-1416... 

Suvegh, K., Domjan, A., Vanko, G., Ivan, B., Vertes, A. (1998) Free volume and swelling dynamics of the poly[(2-dimethylamino)ethyl methacry-late]-l-polyisobutylene amphiphilic network by positron annihilation investigations . Macromolecules, 31,7770. 

FIGURE 7-50 H NMR spectra of (A) poly(vinylidine chloride) homopolymer (B) polyisobutylene... 

Figure 7.9 Shear-stress dependence of the relative viscosity for dispersions in white spirit of acrylic copolymer particles of radius a = 157 nm at a volume fraction of p =0.40 for differing concentrations of nonadsorbing polyisobutylene polymer of molecular weight 411,000. The particles had been stabilized by addition of a comb-graft copolymer of PMMA backbone (which adsorbed to the particles) with non-adsorbing poly(12-hydroxystearic acid) teeth. The con-centrations (in weight per unit volume) of polyisobutylene are 1.0% ( ), 0.85%(B), 0.6%(D), 0.5%(V), 0.4%( ), and 0.1 %(0)- (From Bus-call et al. 1993, with permission from the Journal of Rheology.)...

Preparation, In the laboratory prepn of Composition C-4, dry RDX is added to a petroleum ether soln of di(2-ethylhexyl)sebacate, poly-isobutylene SAE 10 engine oil. The solvent is evaporated and the residue worked by hand into a homogenous dough-like mass. Since the use of a Volatile flammable solv Is undesirable in plant production, a solventless process was developed. In the plant process two different granulations of RDX are used 61 parts of Class (or Class B) 30 parts of Class 3 (See description of RDX classes under Cyclo-trimethylenetrinitramine in this vol of Encyclopedia). The water-wet mixture of both is placed in a stainless steel mixing kettle and 9 parts of "polyisobutylene binder are added. 

B. Techniques. The synthesis and purification of a, u)-di (tejrt.-chloro ) poly isobutylene C1-PIB-C1 (formula I in Scheme I) and the preparation of ct, io-di ( isobut-enyl)polyisobutylene (formula II in Scheme I) by quantitative regioselective dehydrochlorination of Cl-PIB-C1 have been described [1,3]. Details of the synthesis of a, u-di (hydroxy)polyisobutylenes HO-CH2-PIB-CH2-OH (formula IV in Scheme I) by hydroborations of ct,w-di-( isobutenyl)polyisobutylene with 9-BBN or BH3 THF, have been given elsewhere [4]. 

FIGURE 13.16 AFM phase images of poly(styrene-b-isobutylene-b-styrene) (SIBS) triblock copolymers. The images are for (a) polyisobutylene homopolymer (b) branched SIBS with 16% styrene content and (c) linear SIBS with 30% styrene. The darker regions have greater hardness and thus represent the polystyrene domains. (From Puskas et al. (2000) reprinted with permission from John Wiley Sons, Ltd., copyright 2003.)... 

Notes The values of A, B, and C and thus of y are based on a reference volume Vre/ = 0.1 nm Polymer notation A d- label preceding the polymer acronym indicates a per-deuterated polymer partially deuterated polymers are labeled as dy, df, etc., for selective deuteration of 3, 4, etc., hydrogens. Numbers in subscripted parentheses after the polymer name indicate the primary comonomer fraction, e.g., SPB(6s) is a saturated polybutadiene with 66 mol% butadiene Polymer acronyms P2VP poly(2-vinyl pyridine), P4MS poly(4-methylstyrene), PBMA poly(n-butyl methacrylate), PCHA poly(cyclohexyl acrylate), PEB poly(ethyl butylene), PIB polyisobutylene, PI polyisoprene, PMMA poly(methyl methacrylate), PPMA poly(n-pentyl methacrylate), PP polypropylene, HHPP head-to-head polypropylene, PS polystyrene, PVME poly(vinyl methyl ether), PXE poly(2,6-dimethyl-l,4-phenylene oxide), SPB saturated polybutadiene, SPI saturated polyisoprene... 

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. 

Fonagy, T., Ivan, B., and Szesztay, M. (1998). Polyisobutylene-graft-polystyrene by quasiliving atom-transfer radical polymerization of styrene from poly(isobutylene-co-p-methyl-styrene-co-p-bromomethylstyrene). Macromol. Rapid Common., 19(9) 479-483. 

Fig. 18 Activation energy of p-relaxation in (a) low-molecular weight glasses and (b) linear polymers vs the cohesion energy or cohesion energy of Kuhn statistical segment, respectively [86, 88,103]. (a) (1) Pentanol (2) isopropylbenzene (3) 5-methyl-3-heptanol (4) decalin (5) 1,1-diphenylpropane (6) diethyl phthalate (7) glycerol (8) 6>-terphenyl (9) hexamethyl disolox-ane (10) tetra-a-methylstyrene (11) pentastyrene. (b) (1) Polyethylene (2) polyisoprene (3) poly(dimethylsiloxane) (4) poly(diethylsiloxane) (5) poly(phenylene oxide) (6) poly(ethylene terephthalate) (7) polytetrafluoroethylene (8) polycarbonate (9) polyamide (10) polypropylene (11) polymethacrylate (12) poly(vinyl fluoride) (13) poly(vinyl acetate) (14) poly(vinyl chloride) (15) poly(vinyl alcohol) (16) poly(methyl methacrylate) (17) poly(diphenyl oxypheny-lene) (18) poly(butyl methacrylate) (19) polystyrene (20) polyacrylonitrile (21) poly(a-methylstyrene) (22) poly(cyclohexyl methacrylate) (23) polyimide I (24) polyimide II (25) poly(metaphenylene isophthalamide) (26) polyisobutylene...

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