Molecular weights of polymers

Most thermodynamic properties of polymers are best related to M . 

Viscosity-average molecular weight (Af ) This is obtained from viscosity measurement and is given by the expression  

Molecular weight is related to [r/] by the Mark-Houwink-Sakurada equation given as 

Both K and a are empirical (Mark-Houwink) constants that are specific for a given polymer, s(dvent, and temperature. 

For a polymer that is heterogeneous with respect to molecular weight, is always greater than,and is always greater than which in turn is greater than Af . When the exponent in the Mark-Houwink equation is equal to 1, then M is equal to Af ,. However, typical values of a are 0.5 to 0.8, and therefore, is usually greater than M (Fig. 14.2.  

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Chain transfer to solvent is an important factor in controlling the molecular weight of polymers prepared by this method. The chain-transfer constants for poly(methyl methacrylate) in various common solvents (C) and for various chain-transfer agents are Hsted in Table 10. 

Molecular weights of polymers are determined by the weight—average molecular weight, and the number—average molecular weight, M. The... 

Some slurry processes use continuous stirred tank reactors and relatively heavy solvents (57) these ate employed by such companies as Hoechst, Montedison, Mitsubishi, Dow, and Nissan. In the Hoechst process (Eig. 4), hexane is used as the diluent. Reactors usually operate at 80—90°C and a total pressure of 1—3 MPa (10—30 psi). The solvent, ethylene, catalyst components, and hydrogen are all continuously fed into the reactor. The residence time of catalyst particles in the reactor is two to three hours. The polymer slurry may be transferred into a smaller reactor for post-polymerization. In most cases, molecular weight of polymer is controlled by the addition of hydrogen to both reactors. After the slurry exits the second reactor, the total charge is separated by a centrifuge into a Hquid stream and soHd polymer. The solvent is then steam-stripped from wet polymer, purified, and returned to the main reactor the wet polymer is dried and pelletized. Variations of this process are widely used throughout the world. 

Molecular weights of polymers that function as bridging agents between particles are ca 10 —10. Ionic copolymers of acrylamide are the most significant commercially (see Acrylamide POLYMERS). Cationic comonomers include (2-methacryloyloxyethyl)trimethylammonium salts, diethyl aminoethyl methacrylate [105-16-8], and dimethyldiallylammonium chloride [7398-69-8], anionic comonomers include acryUc acid [79-10-7] and its salts. Both types of polyacrylamides, but especially the anionic, can be more effective in the presence of alum (10,11). Polyetbylenimine and vinylpyridine polymers, eg, po1y(1,2-dimethy1-5-viny1pyridiniiim methyl sulfa te) [27056-62-8] are effective but are used less frequentiy. 

Polymers. The molecular weights of polymers used in high energy electron radiation-curable coating systems are ca 1,000—25,000 and the polymers usually contain acryUc, methacrylic, or fumaric vinyl unsaturation along or attached to the polymer backbone (4,48). Aromatic or aUphatic diisocyanates react with glycols or alcohol-terrninated polyether or polyester to form either isocyanate or hydroxyl functional polyurethane intermediates. The isocyanate functional polyurethane intermediates react with hydroxyl functional polyurethane and with acryUc or methacrylic acids to form reactive p olyurethanes. 

Controlled stress viscometers are useful for determining the presence and the value of a yield stress. The stmcture can be estabUshed from creep measurements, and the elasticity from the amount of recovery after creep. The viscosity can be determined at very low shear rates, often ia a Newtonian region. This 2ero-shear viscosity, T q, is related directly to the molecular weight of polymer melts and concentrated polymer solutions. 

FIGURE 6.8 Guidelines for Shodex column selection depending on the molecular weight of polymer. Column Shodex GPC KF-800 series, 8 mm i.d. x 300 mm. Eluent THE. Flow rate 1.0 mUmin. Detector Shodex Rl. Column temp. 40°C. Sample EPIKOTE 828... 

Recently, interesting composite materials incorporating polymeric materials into the sol-gel glasses have been reported by Wilkes and his co-workers [9]. These materials are named ceramers . The properties of ceramers strongly depend on the reaction conditions, i.e., acidity, water content, reaction temperature, the amount of organic polymer, the molecular weight of polymer, solvent, and so on. 

Optimized molecular weight-conversion relationship is related to the system heat transfer coefficient. The degree of conversion improvement from improved heat transfer depends on the average molecular weights of polymer being produced for a given initiator system. 

After cooling, the microspheres were washed by decantation with petroleum ether to give a free-flowing powder. They were then sieved, dried, and stored in a freezer. Size distribution can be controlled by the stirring rate the yield is 70-90%. The process was quite reproducible with respect to yield, size, and loading distribution, if the same molecular weight of polymer was used. Less than 5% error was observed (5). 

In the view of molecular weight and molecular weight distribution we found that, the molecular weight of polymer obtained fix>m MMAO system p.ve the larger munber of molecular weight than the MAO system. This phenomenon was attributed to the present of TMA and TIBA in MAO and MMAO respectively. The molecular wei t distribution was independent with any almninoxane type. However, it essentially depended on typ i of cocatalyst (aluminoxane and borate)... 

It was shown that the logarithm of the product of intrinsic viscosity and molecular weight of polymers of different chemical and stereochemical composition, configuration, or molecular weight is linearly related to the elution volume.81 A plot of log (r) M) vs. elution volume provides a single calibration curve, useful for samples of similar composition, and is termed a universal... 

Occasionally there is the need for simultaneous determination of MW, MWD of polymers and identifica-tion/quantilication of additives [38]. This was the case for polymer and additive analysis of SBR/(softeners, flavour agents, stabilisers) (chewing gum) [41]. The many constituents of the SBR portion of the sample were not resolved, since adjacent components were similar in size. It should be stressed, however, that the need for simultaneous determination of the molecular weight of polymers and the identification/quantification of additives is exceptional rather than the rule. The determination of molecular weight distributions by SEC has indicated that oligomer fractions analysed by dissolution and (Soxhlet) extraction methods may differ essentially [42],... 

Vapor Pressure Osmometry - The number average molecular weights of polymers with Mn < 20,000 were determined using "Model 232A Molecular Weight Apparatus, Wescan Instruments, Inc., 3018 Scott Blvd., Santa Clara, CA 95050". Toluene was used as solvent and the instrument was calibrated using polystyrene of Mn 9,000 and 20,400. 

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