Molecular weight distributions systems

Howardt describes a model system used to test the molecular weight distribution of a condensation polymer The polymer sample was an acetic acid-stabilized equilibrium nylon-6,6. Analysis showed it to have the following end group composition (in equivalents per 10 g) acetyl = 28.9,... 

AlCl efficiency (based on g resin/g catalyst) can be markedly improved by polymerizing dry feeds (<10 ppm H2O) with an AlCl /anhydrous HCl system. Proceeding from 250 ppm H2O down to 10 ppm H2O, catalyst efficiency improves from 30.6 to 83.0 (26). Low levels of tertiary hydrocarbyl chlorides have been shown to gready enhance the activity of AlCl, while yielding resins with narrow molecular weight distributions relative to systems employing water or HCl (27). 

Chromium Oxide-Based Catalysts. Chromium oxide-based catalysts were originally developed by Phillips Petroleum Company for the manufacture of HDPE resins subsequendy, they have been modified for ethylene—a-olefin copolymerisation reactions (10). These catalysts use a mixed sihca—titania support containing from 2 to 20 wt % of Ti. After the deposition of chromium species onto the support, the catalyst is first oxidised by an oxygen—air mixture and then reduced at increased temperatures with carbon monoxide. The catalyst systems used for ethylene copolymerisation consist of sohd catalysts and co-catalysts, ie, triaLkylboron or trialkyl aluminum compounds. Ethylene—a-olefin copolymers produced with these catalysts have very broad molecular weight distributions, characterised by M.Jin the 12—35 and MER in the 80—200 range. 

Membrane stmcture is a function of the materials used (polymer composition, molecular weight distribution, solvent system, etc) and the mode of preparation (solution viscosity, evaporation time, humidity, etc). Commonly used polymers include cellulose acetates, polyamides, polysulfones, dynels (vinyl chloride-acrylonitrile copolymers) and poly(vinyhdene fluoride). 

Cocatalysts, such as diethylzinc and triethylboron, can be used to alter the molecular-weight distribution of the polymer (89). The same effect can also be had by varying the transition metal in the catalyst chromium-based catalyst systems produce polyethylenes with intermediate or broad molecular-weight distributions, but titanium catalysts tend to give rather narrow molecular-weight distributions. 

The main problem of determination of molecular weight distribution (MWD) of dextrans (polysachaiides which ai e used as active substances for infusion medicines) is low robustness of the existing method. It means that obtained results are strongly dependent on controlled and uncontrolled pai ameters of chromatographic system standai d substances for calibration loading on columns etc. It has been shoved on practical examples. 

A mass of polymer will contain a large number of individual molecules which will vary in their molecular size. This will occur in the case, for example, of free-radically polymerised polymers because of the somewhat random occurrence of ehain termination reactions and in the case of condensation polymers because of the random nature of the chain growth. There will thus be a distribution of molecular weights the system is said to be poly disperse. 

Polystyrene produced by free-radical polymerisation techniques is part syndio-tactic and part atactic in structure and therefore amorphous. In 1955 Natta and his co-workers reported the preparation of substantially isotactic polystyrene using aluminium alkyl-titanium halide catalyst complexes. Similar systems were also patented by Ziegler at about the same time. The use of n-butyl-lithium as a catalyst has been described. Whereas at room temperature atactic polymers are produced, polymerisation at -30°C leads to isotactic polymer, with a narrow molecular weight distribution. 

The high-molecular weight was assigned to the PMMA grafted to the copolymer chains and the low-molecular weight to the PMMA initiated by the MMA radical (II). However, only one molecular weight distribution peak was observed for the PMMA initiated by the latter system, i.e., in combination with BP, which implies that only aminomethyl radicals are capable of initiating the polymerization. 

The block copolymer produced by Bamford s metal carbonyl/halide-terminated polymers photoinitiating systems are, therefore, more versatile than those based on anionic polymerization, since a wide range of monomers may be incorporated into the block. Although the mean block length is controllable through the parameters that normally determine the mean kinetic chain length in a free radical polymerization, the molecular weight distributions are, of course, much broader than with ionic polymerization and the polymers are, therefore, less well defined,... 

This relation was verified experimentally7 49 and it was shown that the degree of polymerization in a system containing "living polymers is independent of concentrations of initiator or monomer and of temperature. Furthermore, if all the growing centers were formed in a time much shorter than the time of polymerization, a Poisson molecular weight distribution would be obtained. Indeed, by using this technique samples of polystyrene were obtained for which MjMn = 1.04. 

The equilibrium between monomer and living polymer is dynamic and therefore the molecular weight distribution of the polymer will change with time until the equilibrium distribution is reached. This is a peculiar process in which the amount of polymer present in the system, as well as its number average molecular weight is constant. This means also that, the number of polymeric... 

Zucchini, U. and Cecchin,G. Control of Molecular-Weight Distribution in Polyolefins Synthesized with Ziegler-Natta Catalytic Systems. Vol. 51, pp. 101 — 154. 

The processes described in this section should be contrasted with RAFT polymerization (Section 9.5.3), which can involve the use of similar thioearbonylthio compounds. A. A -dialkyl dithiocarbamates have very low transfer constants in polymerizations of S and (mctb)acrylatcs and arc not effective in RAFT polymerization of these monomers. However, /V,A -dialkyl dithiocarbamates have been successfully used in RAFT polymerization of VAc. Certain O-alkyl xanthates have been successfully used to control RAFT polymerizations of VAc, acrylates and S. The failure of the earlier experiments using these reagents and monomers to provide narrow molecular weight distributions by a RAFT mechanism can he attributed to the use of non-ideal reaction conditions and reagent choice. A two part photo-initiator system comprising a mixture of a benzyl dithiocarhamate and a dithiuram disulfide has also been described and provides better control (narrower molecular weight distributions).43... 

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