Styrene propylene sulfide

A survey of chemistries used for spontaneously anchoring polymer thin films is shown in Fig. 3. Early work by Stouffer and McCarthy [27] in this area showed that styrene polymers bearing only one terminal thiol group or styrene-propylene sulfide block copolymers could both form stable films via attachment to gold surfaces. Since those initial studies, several different polymer chemistries and architectures have been characterized as chemisorbed monolayers on gold, extending this concept. 

The range of monomers that can be incorporated into block copolymers by the living anionic route includes not only the carbon-carbon double-bond monomers susceptible to anionic polymerization but also certain cyclic monomers, such as ethylene oxide, propylene sulfide, lactams, lactones, and cyclic siloxanes (Chap. 7). Thus one can synthesize block copolymers involving each of the two types of monomers. Some of these combinations require an appropriate adjustment of the propagating center prior to the addition of the cyclic monomer. For example, carbanions from monomers such as styrene or methyl methacrylate are not sufficiently nucleophilic to polymerize lactones. The block copolymer with a lactone can be synthesized if one adds a small amount of ethylene oxide to the living polystyryl system to convert propagating centers to alkoxide ions prior to adding the lactone monomer. 

Among the variations in chemical structure of these triblock copolymers developed in our laboratories were the use of poly(a-methyl styrene)(43, 44) as end blocks, and poly(alkylene sulfides) (42, 45 ) 311 d polydimethylsiloxanes (43, 46) as center blocks. The reactions of cyclic sulfides with organolithium is illustrated in Figure 10. Both the propylene sulfide and the methyl thietane can be used for the center block with styrene or a-methylstyrene end blocks, but the chemistry shown in Figure 10... 

This method has been applied for the synthesis of ethylene sulfide,4 u- 2-47 propylene sulfide, a eia- and gran 2-butene sulfides,74 7 isobutylene sulfide,1 7 cyclohexene Hulfide,1 107 3-lMsethoxypropytoir. sulfide,122 and styrene sulfide.40 A modification of thie reaction ha, been used for the synthesis of carbohydrates possessing episulfidc structures.4 ... 

In a practical sense the hydrocarbon monomers that work best in anionic systems are styrene, a-methylstyrene, p-(tert-butyl)styrene, butadiene, isoprene, 2,3-dimethyIbutadiene, piperylene, stilbene, and 1,1-diphenylethylene. The latter two monomers give rise to alternating copolymers with other dienes but do not homopolymerize. Among the polar monomers (C) that can be polymerized are such monomers as 2-vinyIpyridine, pivalolactone, methacrylonitrile, methyl-methacrylate, ethylene oxide (not with Li-counterion), ethylene sulfide, and propylene sulfide. However, polymerization of many of these polar monomers suffers from side reactions and complicating termination or transfer reactions not present in the... 

MAJOR APPLICATIONS Poly(propylene sulfide) is an elastic material that compares with styrene-butadiene rubbers. However, this polymer has not yet achieved commercial production, although the PPS elastomer offers a combination of good solvent and weather resistance. Low molecular weight functional PPS is suitable... 

Although the reactivity increase caused by crown ethers and cryptands in anionic polymerizations has already found a wide range of application, more details have been reported and a number of questions concerning the type and the behavior of the different species present, both in the initiation and in the propagation steps, have been clarified by, for example, kinetic studies [235], Special polymerization reactions that were effected in the presence of crown compounds are those starting with butadiene, propene, styrene, 2-vinyl pyridine, ethylene oxide, propylene sulfide, isobutylene sulfide, methyl methacrylate, p-propyllactone, or e-caprolactone as monomers and alkali metals as initiators [238-246],... 

Boileau, Kaempf, Schue and coworkers have studied the cryptate mediated anionic addition polymerization of several systems including ethylene oxide [38], propylene sulfide [39-40], isobutylene sulfide [40], isoprene [38], methyl methacrylate [38], hexamethyl trisiloxane [40], e-caprolactone [41], styrene [38, 40, 41], ct-methylstyrene [41], 1,1-diphenylethylene [41] and /3-propiolactone [42]. The polymerization of the latter compound induced by dibenzo-18-crown-6 complexed sodium acetate has also been reported [43]. In general, it was found that the polymer-... 

As a continuation of this work, various analogs of these triblock copolymers were synthesized, such as a-methylstyrene-b-isoprene-b-a-methylstyrene, a-methylstyrene-b-(propylene sulfide)-b-a-methylstyrene and a-methylstyrene-b-dimethylsiloxane-b-a-methylstyrene. All of these showed similar morphology and structure-property relations as the styrene-diene triblocks, as might have been expected. It was noteworthy, however, that when the polystyrene end blocks were replaced by poly-a-methylstyrene, there was a noticeable increase in modulus and tensile strength, at any given temperature. This was presumably due to the enhanced ability of the poly-a-methylstyrene domains to withstand greater stresses and higher temperatures,... 

The two noteworthy, and unexpected, phenomena are, of course, the B-elimination reaction involved in the initiation step of propylene sulfide, and the carhanionic nature of the ring-K)pening reaction of the thiacyclohutane ring. Hence it is possible, for example, to initiate the polymerization of styrene with a block of polythiabutyllithium, since the latter has a carbanionic chain end, rather than a thiolate, as in the case of poly( opylene sulfide). 

Ethyl tert-butvl ether. Ethylene dibromide, Ethyl ether, Ethvl sulfide. 2-Heptanone, Methanol, 2-Methyl-1,3-butadiene, 2-Methvl-2-butene. Methyl chloride, Methylene chloride, Methyl iodide. Methyl mercaptan, 2-Methylphenol, Methyl sulfide. Monuron. Nitromethane, 2-Nitropropane, A-Nitrosodimethylamine, 1-Octene, 2-Pentanone, Propylene oxide, Styrene, Thiram, Toluene, Vinyl chloride, o-Xylene, tn-Xylene Formaldehyde cyanohydrin, see Acetontrile,... 

It is claimed that styrene/butadiene diblock polymers bring about an improvement in the hardness, strength, and processability of polybutadiene elastomers (27), as well as an improvement in the ozone resistance of neoprene rubber (28). Styrene diblock polymers have also been made with isoprene, a-methyIstyrene, methyl methacrylate, vinylpyridine, and a-olefins. Block copolymers of ethylene, propylene, and other a-olefins with each other have been made as well. Heteroatom block copolymers based on styrene or other hydrocarbons and alkylene oxides, phenylene oxides, lactones, amides, imides, sulfides, or slloxanes have been prepared. 

Blends of PET/HDPE have been treated previously in the literature [157, 158]. These are immiscible, but the addition of compatibilizers improves the mechanical properties of the blend, such as styrene-ethylene/butylene-styrene (SEBS) and ethylene propylene diene monomer (EPDM) [157], MAH [158], Poly(ethylene-stat-glycidyl metha-crylate)-graft-poly(acrilonitrile-stat-styrene) (EGMA), poly (ethylene acrylic acid), and maleated copolymers of SEBS, HDPE, ethylene-propylene copolymer (EP). The addition of compatibilizers modifies the rheological properties of blends of PET with HDPE, in such a way that increases in viscosity are observed as the component interactions augment. Changes in crystallization of PET were evaluated in blends with Polyphenylene sulfide (PPS), PMMA, HDPE aromatic polyamides, and copolyesters [159]. 

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. 

Figure 5. Correlation of rate of hydration of terminal alkenes with

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