Molecular Weight Defined in Sol-Gel Analysis and Its Application to Evaluate Branching

1995 ◽  
Vol 68 (2) ◽  
pp. 287-296 ◽  
Author(s):  
Asahiro Ahagon

Abstract It is considered that many “linear” polymers are actually branched; however, it is difficult to show this with ordinary methods for an arbitrarily chosen polymer. Branching can be regarded as premature crosslinking below the gel point. Attention is then paid to the well-established Charlesby-Pinner Equation used for sol-gel analysis in crosslinking studies. It contains the number average degree of polymerization before crosslinking as a parameter. The molecular parameter is considered here to be that of the virtual linear polymer which would be obtained by unlinking any branch points contained in the polymer. Evidence is shown to support this. It is then possible to estimate the total number of linear components on an average molecule of a branched polymer by taking the ratio of the number average molecular weight measured by two methods, i.e., sol-gel analysis and an ordinary method like GPC. Further information about the branching structure can be obtained by additional measurements of effective crosslink density for a series of polymers obtained from similar polymerization processes.

2021 ◽  
Vol 10 (12) ◽  
pp. e493101218433
Author(s):  
Anny Carolinny Tigre Almeida Chaves ◽  
Raphael Ferreira Queiroz ◽  
Sandra Aparecida de Assis

Fungi are source of polysaccharides that can show biological activity. The objective of this research was obtained polysaccharides from Periconia byssoides and evaluate antibacterial and hypoglycemic activity in vitro. The number-average molecular weight and degree of polymerization were determined. The results show that the polysaccharide of P. byssoides has potential as hypoglycemic. Therefore, it would be interesting to conduct in vivo research with this polysaccharide, to know about its hypoglycemic activity.


1963 ◽  
Vol 41 (9) ◽  
pp. 2346-2350 ◽  
Author(s):  
S. K. Sen

The chlorite holocellulose of mesta fiber (Hibiscus cannabinus) was extracted with alkaline solutions of successively increasing concentration and finally with alkaline borate solution. Hemicellulose fractions (I–IV) were thus obtained. Analytical data are recorded for each fraction.Partial acid hydrolysis of the mesta hemicellulose gave 2-O-(4-O-methyl-α-D-glucopyranosyl uronic acid)-D-xylopyranose. Methanolysis and hydrolysis of the fully methylated hemicellulose (fraction II) gave a mixture of 3-O-methyl-D-xylose, 2,3-di-O-methyl-D-xylose, 2,3,4-tri-O-methyl-D-xylose, and 2-O-(2,3,4-tri-O-methyl-α-D-glucopyranosyl uronic acid)-3-O-methyl-D-xylopyranose in the approximate molar ratio of 1.6:34:1:6.4. The number-average molecular weight of the methylated polysaccharide was 18,400 ± 500 (degree of polymerization, 110 ± 3). The number-average molecular weight of the original hemicellulose (fraction II) was found to be 23,000 ± 500 (degree of polymerization, 164 ± 3). On the basis of this and other evidences it is suggested that the polysaccharide is composed of chains of 144 (1 → 4)-linked β-D-xylopyranose residues having approximately every seventh residue carrying a terminal 4-O-methyl-α-D-glucuronic acid residue linked through position 2. A small degree of branching in the backbone of D-xylose is indicated.


2000 ◽  
Vol 12 (1) ◽  
pp. 213-223 ◽  
Author(s):  
J G Smith ◽  
J W Connell

As an extension of work on pendent phenylethynyl-containing imide oligomers, three new diamines containing pendent phenylethynyl groups were prepared and characterized. These diamines were used to prepare pendent and pendent and terminal phenylethynyl imide oligomers via the amide acid route in N-methyl-2-pyrrolidinone at a calculated number average molecular weight of 5000 g mol−1. The pendent phenylethynyl groups were randomly distributed along the oligomer backbone and provided a means of controlling the distance between reactive sites. The imide oligomers were characterized and thermally cured, and the cured polymers evaluated as thin films and compared with materials of similar composition prepared from 3,5-diamino-4′-phenylethynylbenzophenone. This work was performed as part of a continuing research effort to develop structural resins for potential aeronautical applications.


e-Polymers ◽  
2003 ◽  
Vol 3 (1) ◽  
Author(s):  
Thomas Fey ◽  
Helmut Keul ◽  
Hartwig Höcker

Abstract Alternating poly(ester amide)s 6a - e were prepared by polycondensation of α-carboxyl-ω-hydroxyamides 3a - e which were obtained by aminolysis of glutaric anhydride (1) and α,ω-aminoalcohols, H2N-(CH2)x-OH (x = 2 - 6) 2a - e. The polycondensation was performed in dimethylformamide solution using a carbodiimide as activating agent, or in bulk with Bu2Sn(OMe)2, Ti(OBu)4 and Sn(octoate)2 as a catalyst. For the polycondensation in bulk, the influence of catalyst and of temperature on the number-average molecular weight was studied. 1H NMR analyses of the poly(ester amide)s clearly show the alternating microstructure. The poly(ester amide)s from glutaric anhydride and the homologous series of α,ω-aminoalcohols are semicrystalline materials; their melting points show the odd/even effect observed for other poly(ester amide)s.


1974 ◽  
Vol 47 (2) ◽  
pp. 342-356 ◽  
Author(s):  
V. A. Grechanovskii ◽  
I. Ya Poddubnyi ◽  
L. S. Ivanova

Abstract By changing the sol-gel ratio and the structure of the gel fraction it is possible to obtain various grades of synthetic cis-poly(isoprene) which show promise for different applications in the tire and mechanical rubber goods industries. The processability of commercial SKI-3 rubber (at a given average molecular weight of sol) depends mainly on the structure of the gel fraction. Thus, for example, inferior processing properties of rubber compounds is associated primarily with the presence of tight gel. The content and structure of the gel fraction also significantly affect plasto-elastic properties of raw rubbers, e.g. a low plasticity of raw rubbers owes to the increased content of gel fraction. The reduced green strength of compounds based on SKI—3 rubber is accounted for by its chemical structure. Conventional methods used to change the properties of rubbers (including the variation in molecular weight, molecular weight distribution, branching degree, and variation in the content and structure of gel fraction) cannot be considered to be adequate to tackle the problem of the green strength of SKI—3 black stocks. The way to solve the problem appears to be the introduction of functional groups into the polymer chain at the stage of synthesis or processing. These functional groups should be active as to the formation of labile rubber—carbon black—rubber and/or rubber—rubber bonds. High purity of microstructure is necessary but not sufficient for obtaining the required level of green strength of compounded SKI—3. The gel fractions of SKI—3 rubber yield vulcanizates with a more dense network than the corresponding sol vulcanizates. The temperature dependence of the tensile strength is controlled by the network density of vulcanizates from high cis-1,4 poly(isoprene).


1976 ◽  
Vol 49 (5) ◽  
pp. 1290-1304
Author(s):  
M. Kurata ◽  
H. Okamoto ◽  
M. Iwama ◽  
M. Abe ◽  
T. Homma

Abstract An iterative computer method was proposed for estimating the degree of branching and molecular weight distribution simultaneously from a pair of measurements on intrinsic viscosity and gel-permeation chromatography. The validity of the method as applied to randomly branched polymers was tested by using both fractionated and unfractionated samples of branched polystyrenes. It was experimentally concluded that the average number of branch points per unit molecular weight, λ, can be determined by this method with an accuracy of about 15%, and the weight-average molecular weight with accuracy of about 10%.


2011 ◽  
Vol 418-420 ◽  
pp. 13-17
Author(s):  
Su Ran Liao ◽  
Yuan Wei ◽  
Yu Qi Zhang ◽  
Meng Zhang ◽  
Gao Fei Feng

The study of polyurethanes are of continuing interest due to their excellent physical properties. In this study, the reaction kinetics and polymerization conditions in two-step process of toluene diisocyante (TDI) and polypropylene glycol (PPG) with organo-tin mixed catalyst were investigated by di-n-butylamine back-titration. It was showed that the reaction obeyed the second-order equation of step-growth polymerization, the rate constants of TDI and PPG reaction at 50, 60 and 70°C were 0.0922, 0.3373 and 0.5828 kg•mol-1•min-1,respectively. The activation energy obtained from the result was 71.63 kJ•mol-1. The number average molecular weight (Mn) and molecular-weight distribution (Mw/Mn) of the polyurethane were 45175 and 1.53, respectively, and the content of hydrogen bonding in the N-H group from Fourier transform infrared spectrum (FTIR) was 80.75%, which manifested that the large amount of N-H were present in hydrogen bonding.


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