Styrene-siloxane copolymers

The initiation of the cyclic siloxane monomers with a living polymeric lithium species such as polystyryl lithium leads to block copolymers, as outlined in Scheme 2, were also of interest. These styrenic-siloxane block copolymers were prepared with siloxane contents from 10 to 50 weight percent. 

Table VI. ESCA Study of Styrenic-Siloxane Block and Graft Copolymers (Copolymer Composition 10 wt.% PSX)...

Styrenic-siloxane block and graft copolymers, Tg dependence on architecture and molecular weight, 95,95/ Styrenic-siloxane block copolymers, 86 Substrate catalyst ratio, chloromethylation, 18 Sulfonation, instability of sulfonated PPO, improvement, 6 Surface grafting... 

Samples of styrene-dimethylsiloxane and poly (2,6-diphenyl )phenylene ether-dimethylsiloxane block copolymers were also examined as spread films. The styrene-siloxane copolymers included AB, ABA, and repeating block copolymer types. In these cases, as with the polycarbonate, the organic homopolymers do not form monolayers when we try to spread volatile solvent solutions on water. The characteristics of the copolymer spread films, however, were similar to those of the BPAC—DMS copolymers. In all cases, sigmoidal 7r-A curves were obtained, and surface pressures above 10 dynes/cm were unstable. (All of the samples examined had organic blocks of 15 or more monomer units.) A typical curve, for a styrene-dimethylsiloxane repeating block copolymer (19), is shown in Figure 4. 

M. Bertolucci, G. Galli, E. Chiellini, K.J. Wynne, Wetting behavior of films of new fluorinated styrene-siloxane block copolymers. Macromolecules 37 (10) (2004) 3666-3672. 

The TG profiles of vinyl triethoxy silane-methyl methacrylate (VTES-MMA) copolymers in N2 have been reported to be similar to that of PMMA [a.l85]. However, the initial decomposition temperature (IDT) of the copolymers decreased with increasing VTES content in the copolymer. This behaviour was attributed to the decrease in the molecular weight of these copolymers during degradation. A similar tendency for TG was also reported for styrene-siloxane block copolymers synthesised with a living anionic initiator [a.l86]. 

The synthesis of a siloxane-styrene copolymer by ring-opening polymerization of a cyclic siloxane in the presence of a styrene radical that is generated by nitroxide and bromine was recently reported. With the advancement of controlled free-radical polymerization (CFRP), block copolymers of varying architecture can be prepared. Pollack et al." have synthesized a styrene-siloxane diblock copolymer (Scheme 5) using the hydrolyzed (R=OH) form 9 of Hawkers initiator 8 which was bthiated... 

Figure 9.17 Plot of log [i ]M versus retention volume for various polymers, showing how different systems are represented by a single calibration curve when data are represented in this manner. The polymers used include linear and branched polystyrene, poly(methyl methacrylate), poly(vinyl chloride), poly(phenyl siloxane), polybutadiene, and branched, block, and graft copolymers of styrene and methyl methacrylate. [From Z. Grubisec, P. Rempp, and H. Benoit, Polym. Lett. 5 753 (1967), used with permission of Wiley.]...

Interestingly, the first example of a macromonomer, long before the names Macro-mer or macromonomer have been coined 94), is a styrene terminated polydimethyl-siloxane synthesized by the reaction of a Grignard derivative of p-ch loro styrene and an co-chlorodimethylsiloxane oligomer 90) as shown in Reaction Scheme IX. Later, these macromonomers have been reacted with different vinyl monomers such as styrene and acrylates, and relatively well defined graft copolymers have been synthesized. 

Somewhat limited work has been reported over the last decade. There are several reports on the synthesis and physical and structural characterization of styrene-dimethylsiloxane 141 144) and methylmethacrylate-dimethylsiloxane145> diblock, triblock and multiblock copolymers. Several reports are also available on the thermal223), solution 224,2251 and surface196 2261 characterization of various styrene-dimethyl-siloxane block copolymers synthesized by anionic techniques. 

Styrene-maleic anhydride-siloxane copolymer Improved impact resistance... 

In our own research, the functional termination of the living siloxanolate with a chlorosilane functional methacrylate leading to siloxane macromonomers with number average molecular weights from 1000 to 20,000 g/mole has been emphasized. Methacrylic and styrenic monomers were then copolymerized with these macromonomers to produce graft copolymers where the styrenic or acrylic monomers comprise the backbone, and the siloxane chains are pendant as grafts as depicted in Scheme 1. Copolymers were prepared with siloxane contents from 5 to 50 weight percent. 

SMITH ETAL. Styrenic- and Acrylic-Siloxane Copolymers... 

Table II. NMR Analysis of Poly(Dimethyl Siloxane) Content in Styrenic Graft and Block Copolymers...

THERMAL CHARACTERIZATION OF POLY (DIMETHYL SILOXANE) COPOLYMERS WITH POLY (HYDROXY STYRENE) AND 2-METHYL... 

The additional complexity present in block copolymer synthesis is the order of monomer polymerization and/or the requirement in some cases to modify the reactivity of the propagating center during the transition from one block to the next block. This is due to the requirement that the nucleophilicity of the initiating block be equal or greater than the resulting propagating chain end of the second block. Therefore the synthesis of block copolymers by sequential polymerization generally follows the order dienes/styrenics before vinylpyridines before meth(acrylates) before oxiranes/siloxanes. As a consequence, styrene-MMA block copolymers should be prepared by initial polymerization of styrene followed by MMA, while PEO-MMA block copolymers should be prepared by... 

Block copolymers of styrene(A)/dimethyl siloxane (B) are even more unusual in the respect that in many solvents t>A and nB are roughly of similar magnitude, but the former is positive and the latter negative156. Hence, depending on the composition WA [cf. Eq. (97)], the value of v for the copolymer can be positive, negative... 

Based on this approach Schouten et al. [254] attached a silane-functionalized styrene derivative (4-trichlorosilylstyrene) on colloidal silica as well as on flat glass substrates and silicon wafers and added a five-fold excess BuLi to create the active surface sites for LASIP in toluene as the solvent. With THF as the reaction medium, the BuLi was found to react not only with the vinyl groups of the styrene derivative but also with the siloxane groups of the substrate. It was found that even under optimized reaction conditions, LASIP from silica and especially from flat surfaces could not be performed in a reproducible manner. Free silanol groups at the surface as well as the ever-present impurities adsorbed on silica, impaired the anionic polymerization. However, living anionic polymerization behavior was found and the polymer load increased linearly with the polymerization time. Polystyrene homopolymer brushes as well as block copolymers of poly(styrene-f)lock-MMA) and poly(styrene-block-isoprene) could be prepared. 

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. 

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