Chemical constitutions and molecular weights

The parameter g is the ratio of the mean square radii of gyration of branched and linear polymers having the same chemical constitution and molecular weight. From this treatment, it follows that... 

Characterization of HTPBs chemical constitutions and molecular weights... 

There are two aspects in the characterization of polymers and their blends (1) chemical constitution, (2) molecular weight (MW) and its distribution (MWD). Identification of the chemical constitution is conducted by the manufacturer and rarely performed by the industrial or academic users. 

The constitutional formula and molecular weight of cellulose determined on the basis of chemical and physico-chemical experiments has been confirmed by X-ray analysis, which has also led to the discovery of the microcrystalline structure of cellulose. Today the structural model proposed by Meyer and Mark [21] and Mark and Misch [22] based on the X-ray measurements of Polanyi [23] and Sponsler and Dore [24] and taking into consideration Haworth s conclusions about the existence... 

The structure of polyamide fibers is defined by both chemical and physical parameters. The chemical parameters are related mainly to the constitution of the polyamide molecule and are concerned primarily with its monomeric units, end-groups, and molecular weight. The physical parameters are related essentially to chain conformation, orientation of both polymer molecule segments and aggregates, and to crystallinity. 

Poiymers consist of macromoiecuies that have a iarge number of either identical or different monomer units, which are connected by covalent bonds. The number of monomers usually varies between 10 and 10, yielding molecular weights of macromolecules (product of the number N and molecular weights of the monomers) ranging between lo and more than lo . The chemical structure, the arrangement of the monomers, and the shape of the macromolecular chains are described by three parameters, the three Cs constitution, configuration, and conformation. 

The previous sections of this chapter have been concerned with methods for determination of average molar masses, molar mass distributions and molecular dimensions. In many instances this information is all that is necessary to characterize a homopolymer when its method of preparation is known. However, for certain homopolymers (e.g. polypropylene, polyisoprene) knowledge of molecular microstructure is of crucial importance. Additionally, for a copolymer it is necessary to determine the chemical composition in terms of the mole or weight fractions of the different repeat units present. It is also desirable to determine the distribution of chemical composition amongst the different copolymer molecules which constitute the copolymer (Section 3.17.6), and to determine the sequence distribution of the different repeat units in these molecules. Furthermore, when characterizing a sample of an unknown polymer the first requirement is to identify the repeat unit(s) present. Thus methods for determination of chemical composition and molecular microstructure are of great intportance. 

Most properties of linear polymers are controlled by two different factors. The chemical constitution of tire monomers detennines tire interaction strengtli between tire chains, tire interactions of tire polymer witli host molecules or witli interfaces. The monomer stmcture also detennines tire possible local confonnations of tire polymer chain. This relationship between the molecular stmcture and any interaction witli surrounding molecules is similar to tliat found for low-molecular-weight compounds. The second important parameter tliat controls polymer properties is tire molecular weight. Contrary to tire situation for low-molecular-weight compounds, it plays a fimdamental role in polymer behaviour. It detennines tire slow-mode dynamics and tire viscosity of polymers in solutions and in tire melt. These properties are of utmost importance in polymer rheology and condition tlieir processability. The mechanical properties, solubility and miscibility of different polymers also depend on tlieir molecular weights. 

Some substances are odorous, others are not. Humans can smell at a distance if one smells the roses in a garden, it is not ordinarUy considered that part of the rose is in contact with the nose. Substances of different chemical constitution may have similar odors. Substances of similar constitution usuaUy have similar odors, eg, in a homologous series nevertheless, even stereoisomers may have different odors. Substances of high molecular weight are usuaUy inodorous and often nonvolatile and insoluble. The quaUty as weU as the strength of odor may change on dUution. 

Acid—mordant dyes have characteristics similar to those of acid dyes which have a relatively low molecular weight, anionic substituents, and an affinity to polyamide fibers and mordant dyes. In general, brilliant shades caimot be obtained by acid—mordant dyes because they are used as their chromium mordant by treatment with dichromate in the course of the dyeing procedure. However, because of their excellent fastness for light and wet treatment, they are predominandy used to dye wool in heavy shades (navy blue, brown, and black). In terms of chemical constitution, most of the acid—mordant dyes are azo dyes some are triphenyhnethane dyes and very few anthraquinone dyes are used in this area. Cl Mordant Black 13 [1324-21 -6] (183) (Cl 63615) is one of the few examples of currentiy produced anthraquinone acid—mordant dyes. It is prepared by condensation of purpurin with aniline in the presence of boric acid, followed by sulfonation and finally by conversion to the sodium salt (146,147). 

Resin viscosity is an important property to consider in handling the resins. It depends on the molecular weight, molecular weight distribution, chemical constitution of the resin and presence of any modifiers or diluents. Since even the diglycidyl ethers are highly viscous materials with viscosities of about 40-100 poise at room temperature it will be appreciated that the handling of such viscous resins can present serious problems. 

Plasticizers can be classified according to their chemical nature. The most important classes of plasticizers used in rubber adhesives are phthalates, polymeric plasticizers, and esters. The group phthalate plasticizers constitutes the biggest and most widely used plasticizers. The linear alkyl phthalates impart improved low-temperature performance and have reduced volatility. Most of the polymeric plasticizers are saturated polyesters obtained by reaction of a diol with a dicarboxylic acid. The most common diols are propanediol, 1,3- and 1,4-butanediol, and 1,6-hexanediol. Adipic, phthalic and sebacic acids are common carboxylic acids used in the manufacture of polymeric plasticizers. Some poly-hydroxybutyrates are used in rubber adhesive formulations. Both the molecular weight and the chemical nature determine the performance of the polymeric plasticizers. Increasing the molecular weight reduces the volatility of the plasticizer but reduces the plasticizing efficiency and low-temperature properties. Typical esters used as plasticizers are n-butyl acetate and cellulose acetobutyrate. 

The molecular refraction is a constant frequently quoted for individual chemical compounds, and is of considerable value as evidence of constitution, since it is generally true that the molecular refraction of a compound is composed additively of the refractive powers of the atoms contained in the-mmolecular refraction is the value obtained by multiplying the refractive power by the molecular weight. 

In 1868 two Scottish scientists, Crum Brown and Fraser [4] recognized that a relation exists between the physiological action of a substance and its chemical composition and constitution. That recognition was in effect the birth of the science that has come to be known as quantitative structure-activity relationship (QSAR) studies a QSAR is a mathematical equation that relates a biological or other property to structural and/or physicochemical properties of a series of (usually) related compounds. Shortly afterwards, Richardson [5] showed that the narcotic effect of primary aliphatic alcohols varied with their molecular weight, and in 1893 Richet [6] observed that the toxicities of a variety of simple polar chemicals such as alcohols, ethers, and ketones were inversely correlated with their aqueous solubilities. Probably the best known of the very early work in the field was that of Overton [7] and Meyer [8], who found that the narcotic effect of simple chemicals increased with their oil-water partition coefficient and postulated that this reflected the partitioning of a chemical between the aqueous exobiophase and a lipophilic receptor. This, as it turned out, was most prescient, for about 70% of published QSARs contain a term relating to partition coefficient [9]. 

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