Main chains

Viscosity additives are aliphatic polymers of high molecular weight whose main chain is flexible. It is known that in a poor solvent, interactions between the elements making up the polymer chain are stronger than interactions between the solvent and the chain (Quivoron, 1978), to the point that the polymer chain adopts a ball of yarn configuration. The macromolecules in this configuration occupy a small volume. The viscosity of a solution being related to the volume occupied by the solute, the effect of polymers on the viscosity in a poor solvent will be small. 

Di stefano D L and Wand A J 1987 Two-dimensional NMR study of human ubiquitin a main chain directed assignment and structure analysis Biochemistry 26 7272-81... 

Schneider D M, Deliwo M J and Wand A J 1992 Fast internal main-chain dynamics of human ubiquitin Biochemistry 31 3645-52... 

Figure C2.1.2. Polymers witli linear and nonlinear chain architectures. The nonlinear polymers can have branched chains. Short chains of oligomers can be grafted to tire main chain. The chains may fonn a. stor-like stmcture. The chains can be cross-linked and fonn a network.

Another approach to the fabrication of LB films from prefonned polymers is to fonn a hydrophobic main chain by reacting monomers tenninated by a vinyl group [102, 103, 104, 105 and 106]. The side groups studied also included perfluorinated hydrocarbon chains, which tilt with respect to the nonnal to the plane of the film, whereas the analogous ordinary hydrocarbon chains do not [105]. 

The polymers described so far have relatively flexible main chains which can result in complex confonnations. In some cases, tliey can double back and cross over tliemselves. There are also investigations on polymers which are constrained to remain in a confonnation corresponding, at least approximately, to a straight line, but which have amphiphilic properties tliat ensure tliat tliis line is parallel to tire water surface. Chiral molecules are one example and many polypeptides fall into tliis class [107]. Another example is cofacial phtlialocyanine polymers (figure C2.4.9). 

Biddle M B, Lando J B, Ringsdorf H, Schmidt G and Schneider J 1988 Polymeric amphiphiles with hydrophilic main chain spacers—studies in monolayers and Langmuir-Blodgett multilayers Oollold Polymer Scl. 266 806-13... 

Incorporation of cyclic aliphatic (aUcycHc) side groups markedly improves the plasma etch resistance of acryhc polymers, without reduciag optical transparency at 193 nm (91). Figure 32 presents stmctures of some acryhc polymers currendy under study for use ia 193-nm CA resists (92—94). Recendy, polymers with main-chain aUcycHc stmctures have been described that offer similar properties (95,96). 

The term "acetal resins" commonly denotes the family of homopolymers and copolymers whose main chains are completely or essentially composed of repeating oxymethylene units (—CH2—O—). The polymers are derived chiefly from formaldehyde or methanal [50-00-00] either directly or through its cychc trimer, trioxane or 1,3,5-trioxacyclohexane [110-88-3]. 

Both side-chain and main-chain scission products are observed when polyacrylates are irradiated with gamma radiation (60). The nature of the alkyl side group affects the observed ratio of these two processes (61,62). 

Peifluoioalkoxy (PFA) fluoiocaibon lesins aie designed to meet industry s needs in chemical, electrical, and mechanical appHcations. These melt processible copolymers contain a fluorocarbon backbone in the main chain and randomly distributed perfluorinated ether side chains ... 

In 1975, the synthesis of the first main-chain thermotropic polymers, three polyesters of 4,4 -dihydroxy-a,a -dimethylbenzalazine with 6, 8, and 10 methylene groups in the aHphatic chain, was reported (2). Shortly thereafter, at the Tennessee Eastman Co. thermotropic polyesters were synthesized by the acidolysis of poly(ethylene terephthalate) by/ -acetoxybenzoic acid (3). Copolymer compositions that contained 40—70 mol % of the oxybenzoyl unit formed anisotropic, turbid melts which were easily oriented. 

Ethylene oxide is a coproduct, probably formed by the reaction of ethylene and HOO (124—126). Chain branching also occurs through further oxidation of ethylene hydroxyl radicals are the main chain centers of propagation (127). 

The newly formed short-chain radical A then quickly reacts with a monomer molecule to create a primary radical. If subsequent initiation is not fast, AX is considered an inhibitor. Many have studied the influence of chain-transfer reactions on emulsion polymerisation because of the interesting complexities arising from enhanced radical desorption rates from the growing polymer particles (64,65). Chain-transfer reactions are not limited to chain-transfer agents. Chain-transfer to monomer is ia many cases the main chain termination event ia emulsion polymerisation. Chain transfer to polymer leads to branching which can greatiy impact final product properties (66). 

Fig. 14. Main-chain polymer Hquid crystal phases (a) nematic, (b) smectic.

The polyamides are soluble in high strength sulfuric acid or in mixtures of hexamethylphosphoramide, /V, /V- dim ethyl acetam i de and LiCl. In the latter, compHcated relationships exist between solvent composition and the temperature at which the Hquid crystal phase forms. The polyamide solutions show an abmpt decrease in viscosity which is characteristic of mesophase formation when a critical volume fraction of polymer ( ) is exceeded. The viscosity may decrease, however, in the Hquid crystal phase if the molecular ordering allows the rod-shaped entities to gHde past one another more easily despite the higher concentration. The Hquid crystal phase is optically anisotropic and the texture is nematic. The nematic texture can be transformed to a chiral nematic texture by adding chiral species as a dopant or incorporating a chiral unit in the main chain as a copolymer (30). 

Mechanical Properties Related to Polymer Structure. Methacrylates are harder polymers of higher tensile strength and lower elongation than thek acrylate counterparts because substitution of the methyl group for the a-hydrogen on the main chain restricts the freedom of rotation and motion of the polymer backbone. This is demonstrated in Table 3. 

L. mesenteroides strain NRRL B-512F produces a water-soluble dextran with 95% a(l 6) main-chain linkages and 5% a(l 3) branch linkages (78). This strain was subcultured from NRRL strain B-512, isolated in 1943. Strain NRRL B-512F is the strain used for commercial dextran production in the United States and most other countries. Nearly all of the studies done on the industrial production and utilisation of dextran have used this strain. 

Structure of xanthan has been determined by chemical degradation and methylation analysis (335,336) it is composed of repeating units consisting of a main chain of D-glucopyranosyl residues with trisaccharide side chains made up of D-mannopyranosyl and D-glucopyranosyluronic acid residues. 

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