Viscosity, dilute solution molecular weight

On the basis of items 1 to 3 the linear relationship between viscosity and molecular weight in dilute solutions has proved accurate. 

Several researchers, e.g., Staudinger, Fikentscher, Houwink, Huggins, Hess, and Sakurada, developed a method to determine the influence of polymers with a certain molecular weight in diluted solutions by the use of the intrinsic viscosity [36-40]. And the intrinsic viscosity, which is a concentration limit where no interaction between the molecules in a solvent is given, is described by a power law function. It is only dependent mi the concentration of the polymer Cpoiy and the mean molecular weight M, see (20.24). 

Viscosity-molecular weight relationship Dilute solution properties Unperturbed dimensions of linear chain molecules... 

Linear increases of intrinsic viscosity, inherent viscosity, dilute solution viscosity (DSV), Mw, Mn or Mv on monomer conversion are reported in many studies. For example, Wilson emphasized the unique character of Nd-based catalysts in comparison to conventional transition-metal systems in the following terms the typically linear relationship between molecular weight and conversion of the Nd-based polymerization of BD indicates a quasi-living... 

Fig. 9. Rotational relaxation time as a function of molecular weight (viscosity average) for fluorescein conjugates of polyacrylamide in dilute aqueous solutions. Filled circle represents the value of for free dye (recalculated from Fig. 5 of ref. 11, using the directly measured lifetime t)...

The GPC-viscometry with universal calibration provides the unique opportunity to measure the intrinsic viscosity as a function of molecular weight (viscosity law, log [17] (it versus log M) across the polymer distribution (curves 3 and 4 in Fig. 1). This dependence is an important source of information about the macromolecule architecture and conformations in a dilute solution. Thus, the Mark-Houwink equation usually describes this law for linear polymers log[i7] = ogK+ a log M (see the entry Mark-Houwink Relationship). The value of the exponent a is affected by the macromolecule conformations Flexible coils have the values between 0.5 and 0.8, the higher values are typical for stiff anisotropic ( rod -like) molecules, and much lower (even negative) values are associated with dense spherical conformations. 

Anotlier simple way to obtain the molecular weight consists of measuring tire viscosity of a dilute polymer solution. The intrinsic viscosity [q] is defined as tire excess viscosity of tire solution compared to tliat of tire pure solvent at tire vanishing weight concentration of tire polymer [40] ... 

In addition, postreaction on high molecular weight polyacrylamides can be difficult because of the high viscosity of even fairly dilute aqueous polyacrylamide solutions. 

Solution Polymers. Acryflc solution polymers are usually characterized by their composition, solids content, viscosity, molecular weight, glass-transition temperature, and solvent. The compositions of acryflc polymers are most readily determined by physicochemical methods such as spectroscopy, pyrolytic gas—liquid chromatography, and refractive index measurements (97,158). The solids content of acryflc polymers is determined by dilution followed by solvent evaporation to constant weight. Viscosities are most conveniently determined with a Brookfield viscometer, molecular weight by intrinsic viscosity (158), and glass-transition temperature by calorimetry. 

Analytical and test methods for the characterization of polyethylene and PP are also used for PB, PMP, and polymers of other higher a-olefins. The C-nmr method as well as k and Raman spectroscopic methods are all used to study the chemical stmcture and stereoregularity of polyolefin resins. In industry, polyolefin stereoregularity is usually estimated by the solvent—extraction method similar to that used for isotactic PP. Intrinsic viscosity measurements of dilute solutions in decahn and tetraHn at elevated temperatures can provide the basis for the molecular weight estimation of PB and PMP with the Mark-Houwiok equation, [rj] = KM. The constants K and d for several polyolefins are given in Table 8. 

Among the techniques employed to estimate the average molecular weight distribution of polymers are end-group analysis, dilute solution viscosity, reduction in vapor pressure, ebuUiometry, cryoscopy, vapor pressure osmometry, fractionation, hplc, phase distribution chromatography, field flow fractionation, and gel-permeation chromatography (gpc). For routine analysis of SBR polymers, gpc is widely accepted. Table 1 lists a number of physical properties of SBR (random) compared to natural mbber, solution polybutadiene, and SB block copolymer. 

Molecular weights of PVDC can be determined directly by dilute solution measurements in good solvents (62). Viscosity studies indicate that polymers having degrees of polymerization from 100 to more than 10,000 are easily obtained. Dimers and polymers having DP < 100 can be prepared by special procedures (40). Copolymers can be more easily studied because of thek solubiUty in common solvents. Gel-permeation chromatography studies indicate that molecular weight distributions are typical of vinyl copolymers. 

The dilute solution properties of copolymers are similar to those of the homopolymer. The intrinsic viscosity—molecular weight relationship for a VDC—AN copolymer (9 wt % AN) is [77] = 1.06 x 10 (83). The characteristic ratio is 8.8 for this copolymer. 

Solutions of HEC are pseudoplastic. Newtonian rheology is approached by very dilute solutions as well as by lower molecular-weight products. Viscosities change Httie between pH 2 and 12, but are affected by acid hydrolysis or alkaline oxidation under pH and temperature extremes. Viscosities of HEC solutions change reversibly with temperature, increasing when cooled and decreasing when warmed. 

Hypalon CP 826. This is a chloriaated, maleic anhydride modified polypropylene having a chlorine content of about 25% and maleic anhydride content of about 0.8%, developed to promote adhesion of inks and coatiags to polypropyleae or bleads containing polypropyleae. It has a solutioa viscosity of 125 mPas(= cP) at 20% soHds ia xyleae and can be used ia dilute solutioas as a wash primer or a tie layer betweea materials that are difficult to adhere. CP 827 is a higher molecular-weight analogue with a solution viscosity of 280 mPas(= cP) at 20% soHds ia 80/20 xylene/methyl isobutyl ketoae. 

For commercial purposes the molecular weight is usually characterised from measurements of the viscosity of dilute solutions. It has been shown that, for dilute solutions, the relation between the viscosity and the molecular weight (in this case the viscosity average molecular weight) may be given by the relationship... 

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