Methyl-terminated poly

FERRY A, Ionic interactions and transport properties in methyl terminated poly(propylene glycol)(4000) complexed with LiCFjSOj ./P/jys ChemB, 1997, 101,150-157... 

J.P. Cohen-Addad, P. Huchot, P. Jost, A. Pouchelon. Hydroxyl or methyl terminated poly(dimethylsiloxane) chains kinetics of adsorption on silica in mechanical mixtures. Polymer, 30,143-146,1989. 

Thus, the ring-opening polymerization of 2-methyl-2-oxazoline followed by the treatment of the resulting oxazolinium propagating end group with 3-aminopropyltriethoxysilane produced successfully triethoxysilyl-terminated poly-oxazoline as shown in Scheme 3 [29]. 

Table 11. Characteristics of ethylpiperzine-terminated poly(dimethyl-tri-fluoropropyl,methyl)siloxane oligomers 69>...

Poly(methyl 3-(l-oxypyridinyl)siloxane) was synthesized and shown to have catalytic activity in transacylation reactions of carboxylic and phosphoric acid derivatives. 3-(Methyldichlorosilyl)pyridine (1) was made by metallation of 3-bromopyridine with n-BuLi followed by reaction with excess MeSiCl3. 1 was hydrolyzed in aqueous ammonia to give hydroxyl terminated poly(methyl 3-pyridinylsiloxane) (2) which was end-blocked to polymer 3 with (Me3Si)2NH and Me3SiCl. Polymer 3 was N-oxidized with m-ClC6H4C03H to give 4. Species 1-4 were characterized by IR and H NMR spectra. MS of 1 and thermal analysis (DSC and TGA) of 2-4 are discussed. 3-(Trimethylsilyl)-pyridine 1-oxide (6), l,3-dimethyl-l,3-bis-3-(l-oxypyridinyl) disiloxane (7) and 4 were effective catalysts for conversion of benzoyl chloride to benzoic anhydride in CH2Cl2/aqueous NaHCC>3 suspensions and for hydrolysis of diphenyl phosphorochloridate in aqueous NaHCC>3. The latter had a ti/2 of less than 10 min at 23°C. 

Another approach is to use an initiator for ATRP that produces a polymer with a functional group capable of initiating a non-ATRP polymerization. ATRP polymerization of methyl methacrylate with 2,2,2-tribromoethanol produces an HO-terminated poly(methyl methacrylate). The hydroxyl group acts as an initiator in the presence of triethyl aluminum for the ring-opening polymerization of caprolactone. 

There are a number of inert binders such as polyester, epoxy, polysulfide, polyurethane which have been reported as binders for composite propellants and plastic bonded explosives (PBXs). At present, hydroxy-terminated polybutadiene (HTPB) is regarded as the state-of-the-art workhorse binder for such applications. However, the recent trend is to use energetic binders such as poly [3,3-bis(azidomethyl oxetane)] [poly(BAMO)], poly (3-azidomethyl-3-methyl oxetane) [poly(AMMO)], PNP, GAP diol and triol, nitrated HTPB(NHTPB), poly(NiMMO), poly(GlyN) and nitrated cyclodextrin polymers poly(CDN) for PBXs and composite propellants in order to get better performance. 

Pentadienyl-terminated poly(methyl methacrylate) (PMMA) as well as PSt, 12, have been prepared by radical polymerization via addition-fragmentation chain transfer mechanism, and radically copolymerized with St and MMA, respectively, to give PSt-g-PMMA and PMMA-g-PSt [17, 18]. Metal-free anionic polymerization of tert-butyl acrylate (TBA) initiated with a carbanion from diethyl 2-vinyloxyethylmalonate produced vinyl ether-functionalized PTBA macromonomer, 13 [19]. 

Polypropylene imine) dendrimers (see Scheme 1 for structure) have been constructed step by step onto an amine functionalized polystyrene [38, 130, 131]. The challenge in this synthesis is finding conditions for the polypropylene imine) synthesis under which the low MW polystyrene (MW=3200) is soluble [38]. Similar poly(imine) dendrimers with carboxylic acid end groups have also been prepared [130]. The polypropylene imine) dendrimer has also been synthesized on an amino-terminated poly(2-methyl-2-oxazoline) [132]. 

Abbreviations y x AFM AIBN BuMA Ca DCP DMA DMS DSC EGDMA EMA EPDM FT-IR HDPE HTV IPN LDPE LLDPE MA MAA MDI MMA PA PAC PB PBT PBuMA PDMS PDMS-NH2 interfacial tension viscosity ratio atomic force microscopy 2,2 -azobis(isobutyronitrile) butyl methacrylate capillary number dicumyl peroxide dynamic mechanical analysis dynamic mechanical spectroscopy differential scanning calorimetry ethylene glycol dimethacrylate ethyl methacrylate ethylene-propylene-diene rubber Fourier transform-infra-red high density polyethylene high temperature vulcanization interpenetrating polymer network low density polyethylene linear low density polyethylene maleic anhydride methacrylic acid 4,4 -diphenylmethanediisocyanate methyl methacrylate poly( amide) poly( acrylate) poly(butadiene) poly(butylene terephtalate) poly(butyl methacrylate) poly(dimethylsiloxane) amino-terminated poly(dimethylsiloxane)... 

Scheme 2 Hydrogen bonding between DBSA and tertiary amino-terminated poly(methyl methacrylate) [76]...

Living anionic polymerization of 4-vinylphenol was performed after transformation of the phenolic hydroxy group into trialkybilyl ether group and removal of the protection group after polymerization [125]. n-Butyl lithium was used for the synthesis of poly[2-hydroxy-4-methacryloyloxybenzophenone] [61] (102) or HALS terminated poly(methyl methacrylate) [126]. 2-Hydroxy-4-methacryloyl-... 

Coextrusion of L-lactide (a cyclic dimer lactone of lactic acid) with hydroxy-terminated poly(caprolactone) in the presence of stannous octoate gave a block copolymer.74 Block copolymers can also be used as compatibilizers for the homopolymers, in addition to having interesting properties in their own right.75 Copolymers of ethylene and vinyl acetate can be treated with methanol and a little sodium methoxide to remove some of the acetate groups from the copolymer.76 The by-product methyl acetate comes out the vent of the extruder. n-Butyl alcohol can be used in the same way.77 The product copolymer is useful as a gas barrier coating on films for packaging food. 

The depolymerization mechanism from the polymer end has been recently revisited in the design of positive electron beam resists. 2-Phenylallyl-termi-nated poly(a-methylstyrene) was prepared by living anionic polymerization, which exhibited a significantly lower depolymerization temperature on TGA than the H-terminated counterpart [340]. The 2-phenylallyl-terminated polymer depolymerized completely when treated with n-BuLi in THF at room temperature. A single-component resist (without PAG) formulated with the 2-phenylallyl-terminated poly(a-methylstyrene) demonstrated a higher e-beam sensitivity (500 pC/cm2 at 20 keV) than the one based on the H-terminated polymer when developed with methanol/methyl isobutyl ketone (2/3 vol/vol) [340]. However, the sensitivity of the non-catalyzed single-component system... 

The reactions of composite 1 with secondary polymer of amino-terminated poly(methyl acrylate), poly(methyl methacrylate) or polystyrene were carried out in acetone or tetrahydrofuran under refluxing for 24 h. The amount of the binding polymer decreased with increasing of the molecular weight, as shown in Table 17.1. 

In ATRP, the nature of the halogen end group can play an important role. The initiation of MMA polymerization by a Cl-terminated poly(methyl acrylate) macroinitiator is poor, but is much faster if a Br-terminated poly(methyl acrylate) is used. In general, efficient block copolymer formation occurs when the rate of... 

In addition to the work previously described, the studies of Bielawski and coworkers in which hemi-telechelic pyridine-end-terminated poly(methyl acrylate) was utilized to initiate ionic polymerization upon mechanically activated scission of the boron-nitrogen coordination bond should be mentioned [97]. Although the design of these systems is in principle very interesting, an expression of concern was published and editorial review is currently underway to investigate the reliability of the data reported in the article. Nevertheless, at this stage, no definitive conclusion has been drawn. 

Fig. 20 Multilayer deposition on a hydrophilically/hydrophobically patterned gold substrate. Upper AFM images height (left) and friction force (right) images of patterned methyl- and hydroxyl- alkanethiol self-assembled monolayers. Adsorption of poly(ferrocenylsilane) polyions (5/7, 12 bUayers) occms selectively on the broad methyl-terminated stripes (lower AFM images). Reprinted with permission from [94]. Copyright 2002, American Chemical Society...

Fra Francis, B., Thomas, S., Jose, J., Ramaswamy, R., Rao, V. L. Hydroxyl terminated poly (ether ether ketone) with pendent methyl group toughened epoxy resin miscibility, morphology and mechanical properties. Polymer 46 (2005) 12372-12385. 

FrOlich et al. [ 140] investigated a system in which DGEBA was mixed with hydroxy-terminated poly(propylene oxide-block-ethylene oxide) as the rubber, with the nanoclay being a synthetic fluorohectorite treated with bis (2-hydroxyethyl) methyl tallow alkylammonium ions. The clay was first blended with rubber, before being dispersed into the reactive epoxy mixture. Modification of the rubber allowed variation in miscibility and differing morphologies and properties. If the rubber was miscible, the intercalated clay led to improved toughness. If the rubber is sufficiently modified, such as with... 

Poly (p-toluenesulfonamide-co-formaldehyde). See Tosylamide/formaldehyde resin Polytrap 6603, Polytrap Q5-6603. See Acrylates copolymer Polytrifluorochloroethylene Poly (trifluoroethylene chloride) Poly (trifluoromonochloroethylene). See Chlorotrifluoroethylene polymer Poly (trifluoropropyl (methyl) siloxane Poly (3,3,3-trifluoropropylmethylsiloxane). See Polymethyl-3,3,3-trifluoropropylsiloxane Polytrifluoropropylmethylsiloxane, silanol-terminated. See Polymethyl-3,3,3-trifluoropropylsiloxane, silanol-terminated Poly(trifluorovinyl chloride). See Chlorotrifluoroethylene polymer Polytrimethylene terephthalate Synonyms PIT... 

Similar block copolymers have also been prepared by coupling methyl methacrylate macroanions and suitably terminated poly(ethylene oxide)( )and by the initiation of methyl and ethyl methacrylate by alkali metal alkoxides of poly(ethylene oxide)( 3). styrene containing block copolymers have also been produced( ). In the former plus latter techniques the ester containing block segments were subsequently hydrolyzed to methacrylic acid thus making them water soluble. 

Hergenrother and Ambrose have prepared butadiene-imide and butadiene-caprolactam(73,74)block copolymers using polybutadiene capped on each terminus by isocyanate groups. Poly(ethylene-propylene adipate-b-methyl methacrylate) was prepared by heating hydroxy terminated poly(methyl methacrylate) with the isocyanate terminated reaction products of hydroxy terminated poly(ethylene-propylene... 

Other workers have reported the preparation of methyl methacrylate-styrene and methyl methacrylate-vinyl chloride block copolymers by a two stage free radical polymerization. First they prepared telomers of styrene (or vinyl chloride) and poly(methyl methacrylate) terminated by carbon tetrachloride. Then they heated the telomers of the desired monomers in the presence of bis-(ephedrine) copper to prepare sequential ABAB block copolymers(87). Poly(methyl methacrylate-b-acrylonitrile) was prepared by heating (CO)5Mn(CF2)2 terminated poly(methyl methacrylate) and acrylonitrile at 100 C(88) ... 

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