Lateral combined polymers

Dichromated Resists. The first compositions widely used as photoresists combine a photosensitive dichromate salt (usually ammonium dichromate) with a water-soluble polymer of biologic origin such as gelatin, egg albumin (proteins), or gum arabic (a starch). Later, synthetic polymers such as poly(vinyl alcohol) also were used (11,12). Irradiation with uv light (X in the range of 360—380 nm using, for example, a carbon arc lamp) leads to photoinitiated oxidation of the polymer and reduction of dichromate to Ct(III). The photoinduced chemistry renders exposed areas insoluble in aqueous developing solutions. The photochemical mechanism of dichromate sensitization of PVA (summarized in Fig. 3) has been studied in detail (13). 

Polymer science was bom in the great industrial laboratories of the world of the need to make and understand new kinds of plastics, rubber, adhesives, libers, and coatings. Only much later did polymer science come to academic life. Perhaps because of its origins, polymer science tends to be more interdisciplinary than most sciences, combining chemistry, chemical engineering, materials, and other fields as well. 

The first commercially available acetal resin was marketed by Du Pont in 1959 under the trade name Delrin after the equivalent of ten million pounds had been spent in research or polymers of formaldehyde. The Du Pont monopoly was unusually short lived as Celcon, as acetal copolymer produced by the Celanese Corporation, became available in small quantities in 1960. This material became commercially available in 1962 and later in the same year Farbwerke Hoechst combined with Celanese to produce similar products in Germany (Hostaform). In 1963 Celanese also combined with the Dainippon Celluloid Company of Osaka, Japan and Imperial Chemical Industries to produce acetal copolymers in Japan and Britain respectively under the trade names Duracon and Alkon (later changed to Kematal). In the early 1970s Ultraform GmbH (a joint venture of BASF and Degussa) introduced a copolymer under the name Ultraform and the Japanese company Asahi Chemical a homopolymer under the name Tenal. 

The SFA, originally developed by Tabor and Winterton [56], and later modified by Israelachvili and coworkers [57,58], is ideally suited for measuring molecular level adhesion and deformations. The SFA, shown schematically in Fig. 8i,ii, has been used extensively to measure forces between a variety of surfaces. The SFA combines a Hookian mechanism for measuring force with an interferometer to measure the distance between surfaces. The experimental surfaces are in the form of thin transparent films, and are mounted on cylindrical glass lenses in the SFA using an appropriate adhesive. SFA has been traditionally employed to measure forces between modified mica surfaces. (For a summary of these measurements, see refs. [59,60].) In recent years, several researchers have developed techniques to measure forces between glassy and semicrystalline polymer films, [61-63] silica [64], and silver surfaees [65,66]. The details on the SFA experimental procedure, and the summary of the SFA measurements may be obtained elsewhere (see refs. [57,58], for example.). 

Polymerizations catalyzed with coordination compounds are becoming more important for obtaining polymers with special properties (linear and stereospecific). The first linear polyethylene polymer was prepared from a mixture of triethylaluminum and titanium tetrachloride (Ziegler catalyst) in the early 1950s. Later, Natta synthesized a stereoregular polypropylene with a Ziegler-type catalyst. These catalyst combinations are now called Zieglar-Natta catalysts. 

The steric frustrations have also been detected in LC polymers [66-68]. For example, the smectic A phase with a local two-dimensional lattice was found by Endres et al. [67] for combined main chain/side chain polymers containing no terminal dipoles, but with repeating units of laterally branched mesogens. A frustrated bilayer smectic phase was observed by Watanabe et al. [68] in main-chain polymers with two odd numbered spacers sufficiently differing in their length (Fig. 7). 

The process proceeds through the reaction of pairs of functional groups which combine to yield the urethane interunit linkage. From the standpoint of both the mechanism and the structure type produced, inclusion of this example with the condensation class clearly is desirable. Later in this chapter other examples will be cited of polymers formed by processes which must be regarded as addition polymerizations, but which possess within the polymer chain recurrent functional groups susceptible to hydrolysis. This situation arises most frequently where a cyclic compound consisting of one or more structural units may be converted to a polymer which is nominally identical with one obtained by intermolecular condensation of a bifunctional monomer e.g., lactide may be converted to a linear polymer... 

The combined results of kinetic studies on condensation polymerization reactions and on the degradation of various polymers by reactions which bring about chain scission demonstrate quite clearly that the chemical reactivity of a functional group does not ordinarily depend on the size of the molecule to which it is attached. Exceptions occur only when the chain is so short as to allow the specific effect of one end group on the reactivity of the other to be appreciable. Evidence from a third type of polymer reaction, namely, that in which the lateral substituents of the polymer chain undergo reaction without alteration in the degree of polymerization, also support this conclusion. The velocity of saponification of polyvinyl acetate, for example, is very nearly the same as that for ethyl acetate under the same conditions. ... 

X represents the combined number of both types of units in the polymer chain. Eq. (3) applies also to polymers stabilized (see Chap. Ill) with small amounts of monofunctional units, although here it becomes necessary to replace the extent of reaction p with another quantity, namely, the probability that a given functional group has reacted with a bifunctional monomer. Type ii polymers stabilized with an excess of one or the other ingredient will be discussed later. 

Among the properties measured here, the settling rate is mainly a measure of the size of the floes and in later stages the compressibility of floes and floe networks, and the supernatant clarity is a measure of the size distribution of floes and size dependent capture of the particles and floes by the polymer. The sediment volume and the pulp viscosity on the other hand, are direct measures, not only of floe size and structure but also of adsorbed polymer layers. It is to be noted in this regard that it is this latter aspect which makes it possible to estimate the thickness of adsorbed polymer layers by measuring the viscosity of the medium and the suspension in the presence of polymers (20,21). This combination of effects is another reason one cannot always expect correlation between various flocculation responses. 

One dimensional conjugated carbon polymers can occur in many configurations as depicted in Figure 2 where also we included some chains with nitrogen and sulfur for later reference. Also included there are inorganic one dimensional semiconductors, like SbSI and SbSBr for later comparison. Besides the depicted one-dimensional system others like TCNQ- and KCP-salts could be included here as well but rough measurements of their nonlinear coefficients gave deceptively small values which combined with their ill-characterisation make them poor candidates for nonlinear optical devices. 

As stated above, we postulated that fast, reversible chain transfer between two different catalysts would be an excellent way to make block copolymers catalytically. While CCTP is well established, the use of main-group metals to exchange polymer chains between two different catalysts has much less precedent. Chien and coworkers reported propylene polymerizations with a dual catalyst system comprising either of two isospecific metallocenes 5 and 6 with an aspecific metallocene 7 [20], They reported that the combinations gave polypropylene (PP) alloys composed of isotactic polypropylene (iPP), atactic polypropylene (aPP), and a small fraction (7-10%) claimed by 13C NMR to have a stereoblock structure. Chien later reported a product made from mixtures of isospecific and syndiospecific polypropylene precatalysts 5 and 8 [21] (detailed analysis using WAXS, NMR, SEC/FT-IR, and AFM were said to be done and details to be published in Makromolecular Chemistry... 

Later Rytter et al. reported possible polymer chain exchange with polypropylene produced with a combination of 8 and 11 with TMA [32], The number of stereoerrors increased in the binary system at higher TMA levels. As discussed in the case of Przybyla and Fink (vida supra), pentad analysis is less compelling evidence for reversible chain transfer. In addition, the gel permeation chromatography (GPC) data showed bimodal peaks, indicating very limited reversible transfer. 

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