Hydrocarbon block copolymers

Finally, we have designed and synthesized a series of block copolymer surfactants for C02 applications. It was anticipated that these materials would self-assemble in a C02 continuous phase to form micelles with a C02-phobic core and a C02-philic corona. For example, fluorocarbon-hydrocarbon block copolymers of PFOA and PS were synthesized utilizing controlled free radical methods [104]. Small angle neutron scattering studies have demonstrated that block copolymers of this type do indeed self-assemble in solution to form multimolecular micelles [117]. Figure 5 depicts a schematic representation of the micelles formed by these amphiphilic diblock copolymers in C02. Another block copolymer which has proven useful in the stabilization of colloidal particles is the siloxane based stabilizer PS-fr-PDMS [118,119]. Chemical... 

Properties and Morphology of Amorphous Hydrocarbon Block Copolymers... 

Antonietti et al. described the preparation of mesoporous silica in systems containing mixtures of nonionic fluorinated surfactants and nonionic hydrocarbon block copolymer surfactants [60], The fluorinated surfactant was CF3(CF2)6-i6 C2H4(E0)4 5 and the hydrocarbon-based copolymer was poly(ethylene-co-bulylene)-block-poly(ethylene oxide). 

Leube, W. Monkenbusch, M. Schneiders, D. Richter, D. Adamson, D. Fetters, L. Dounis, P. (2000). Wax-Crystal Modification for Fuel Oils by Self-Aggregating Partially Crystallizable Hydrocarbon Block-Copolymers. Energy Fuels, Vol.l4. No.2, pp.419-430, ISSN 0887-0624... 

G-5—G-9 Aromatic Modified Aliphatic Petroleum Resins. Compatibihty with base polymers is an essential aspect of hydrocarbon resins in whatever appHcation they are used. As an example, piperylene—2-methyl-2-butene based resins are substantially inadequate in enhancing the tack of 1,3-butadiene—styrene based random and block copolymers in pressure sensitive adhesive appHcations. The copolymerization of a-methylstyrene with piperylenes effectively enhances the tack properties of styrene—butadiene copolymers and styrene—isoprene copolymers in adhesive appHcations (40,41). Introduction of aromaticity into hydrocarbon resins serves to increase the solubiHty parameter of resins, resulting in improved compatibiHty with base polymers. However, the nature of the aromatic monomer also serves as a handle for molecular weight and softening point control. 

Other Uses. Large quantities of hydrocarbon resins are used in mastics, caulks, and sealants (qv). Polymers for these adhesive products include neoprene, butyl mbber, polyisoprene, NR, SBR, polyisobutylene, acryHcs, polyesters, polyamides, amorphous polypropylene, and block copolymers. These adhesives may be solvent or water-borne and usually contain inorganic fillers. 

GopolymeriZation Initiators. The copolymerization of styrene and dienes in hydrocarbon solution with alkyUithium initiators produces a tapered block copolymer stmcture because of the large differences in monomer reactivity ratios for styrene (r < 0.1) and dienes (r > 10) (1,33,34). In order to obtain random copolymers of styrene and dienes, it is necessary to either add small amounts of a Lewis base such as tetrahydrofuran or an alkaU metal alkoxide (MtOR, where Mt = Na, K, Rb, or Cs). In contrast to Lewis bases which promote formation of undesirable vinyl microstmcture in diene polymerizations (57), the addition of small amounts of an alkaU metal alkoxide such as potassium amyloxide ([ROK]/[Li] = 0.08) is sufficient to promote random copolymerization of styrene and diene without producing significant increases in the amount of vinyl microstmcture (58,59). 

All these elastomers, especially poly(ethylene- (9-butylene) and poly(ethylene- (9-propylene), are nonpolar. The corresponding block copolymers can thus be compounded with hydrocarbon-based extending oils, but do not have much oil resistance. Conversely, block copolymers with polar polyester or polyether elastomer segments have Htde affinity for such hydrocarbon oils and so have better oil resistance. 

Thermoplastic block copolymers were used for pressure-sensitive and hot-melt rubber adhesives as from the middle sixties. These adhesives found application in packaging, disposable diapers, labels and tapes, among other industrial markets. The formulation of these adhesives generally includes an elastomer (generally containing styrene endblocks and either isoprene, butadiene or ethylene-butylene midblocks) and a tackifier (mainly a rosin derivative or hydrocarbon resin). 

New copolymers based on a copolymerization of isobutylene and p-methyl-styrene with improved heat resistance have been reported [64]. Once copolymerization was accomplished, the polymer was selectively brominated in the p-methyl position to yield a terpolymer called EXXPO. In contrast to butyl and halobutyl, the new terpolymer has no unsaturation in the backbone and therefore shows enhanced thermal stability and resistance to oxidation. Useful solvent-based adhesives can be formulated using the new terpolymer in combination with block copolymers [65]. The hydrocarbon nature of the new terpolymer results in excellent compatibility with hydrocarbon resins and oils. 

For gas absorption, the water or other solvent must be treated to remove the captured pollutant from the solution. The effluent from the column may be recycled into the system and used again. This is usually the case if the solvent is costly (e.g., hydrocarbon oils, caustic solutions, amphiphilic block copolymer). Initially, the recycle stream may go to a treatment system to remove the pollutants or the reaction product. Make-up solvent may then be added before the liquid stream reenters the column. 

S-B-S Triblocks are block copolymers consisting of a block of butadiene units flanked by blocks of styrene. Below the T, of polystyrene blocks from different chains congregate into domains which act both as cross-links and reinforcing fillers. The jDolymers will dissolve in hydrocarbon solvents. Hydrogenated S-B-S materials have better resistance to ageing. 

Thermoplastic polyester rubbers are also block copolymers of polyethers and polyesters. The polyester groups are capable of crystallisation and the crystal structures act like cross-links. These materials have good hydrocarbon resistance. Similar thermoplastic polyamide rubbers are also now available. 

Polymer Synthesis and Characterization. This topic has been extensively discussed in preceeding papers.(2,23,24) However, we will briefly outline the preparative route. The block copolymers were synthesized via the sequential addition method. "Living" anionic polymerization of butadiene, followed by isoprene and more butadiene, was conducted using sec-butyl lithium as the initiator in hydrocarbon solvents under high vacuum. Under these conditions, the mode of addition of butadiene is predominantly 1,4, with between 5-8 mole percent of 1,2 structure.(18) Exhaustive hydrogenation of polymers were carried out in the presence of p-toluenesulfonylhydrazide (19,25) in refluxing xylene. The relative block composition of the polymers were determined via NMR. 

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