Polymers origins

Calculate Mn and Mvv the ratio M /Mn for the original polymer. Also evaluate the ratio Mw/Mn for the individual fractions. Comment on the significance of Mvv/Mn for both the fractionated and unfractionated polymer. 

These new synthetic mbbers were accessible from potentially low cost raw materials and generated considerable woddwide interest. For a time, it was hoped that the polysulftde mbbers could substitute for natural mbber in automobile tires. Unfortunately, these original polymers were difficult to process, evolved irritating fumes during compounding, and properties such as compression set, extension, and abrasion characteristics were not suitable for this apphcation. 

The chlorination of polypropylene has been the subject of several fundamental studies and a variety of products is obtainable according to the tacticity of the original polymer and to the extent of chlorination. 

By reduction in the degree of polymerisation. To produce processable rubbers the original polymers are masticated with substances such as benzothiazole disulphide and tetramethylthiuram disulphide. The more severe degradation techniques to produce liquid polysulphides are mentioned below. 

Figure 12.5. (a) Lattice model showing a polymer chain of 200 beads , originally in a random configuration, after 10,000 Monte Carlo steps. The full model has 90% of lattice sites occupied by chains and 10% vacant, (b) Half of a lattice model eontaining two similar chain populations placed in contact. The left-hand side population is shown after 50,0000 Monte Carlo steps the short lines show the loeation of the original polymer interface (courtesy K. Anderson). 

Fortunately, the optical activity of the polymer freed from the optically active substituent was of the opposite direction than that of the original polymer. Hence, the observed effect cannot be due to a trace of alcohol which was not removed in the hydrolysis. 

Typically, large-scale gas filling makes the main characteristics of foam plastics — coefficients of heat and temperature conductivity, dielectric permeability, and the tangent of the dielectric loss angle — totally independent of the chemical structure of the original polymer [1],... 

This study involved the preparation and characterization of poly(N-phenyl 3,4-dimethylenepyrrolidine) and the subsequent oxidation and reduction of this polymer. The parent polymer was not very soluble, so it was difficult to characterize. However, after oxidizing in the presence of palladium on carbon in nitrobenzene, the resultant poly(N-phenyl 3,4-dimethylenepyrrole) was soluble in several organic solvents. Attempts to reduce the original polymer to the pyrrolidone were unsuccessful. 

Solubility - The oxidized polymer (VIII) has a greater solubility than the original polymer (VII). It was found to be soluble in acetone, chloroform, benzene, DMF and DMSO. Unlike the polymer (VII), (VIII) was not soluble in formic acid or trifluoroacetic acid that was expected since the pyrrole moiety is less basic than pyrrolidine. In the oxidized polymer, the pair of unshared electrons on the nitrogen atom are contributing to the pyrrole ring aromaticity, therefore, unavailable for protonation as in the case of polymer (VII). A comparison of the solubilities is given in Table I. 

The DSC and TGA plots of the oxidized polymer (VIII) showed that the Tm is 130°C and the weight loss of 20% and 80% was observed at 455°C and 600°C, respectively, compared to 400° and 482°C for the original polymer VII indicating the oxidized polymer was more stable to heat. This observation was consistent with the chemical structure of the oxidized polymer, which consisted of a repeating aromatic pyrrole structure and, therefore, should be more thermodynamically stable. The thermal data of the polymers are tabulated in Table II. 

Poly(N-phenyl-3,4-dimethylenepyrroline) had a higher melting point than poly(N-phenyl-3,4-dimethylenepyrrole) (171° vs 130°C). However, the oxidized polymer showed a better heat stability in the thermogravimetric analysis. This may be attributed to the aromatic pyrrole ring structures present in the oxidized polymer, because the oxidized polymer was thermodynamically more stable than the original polymer. Poly(N-phenyl-3,4-dimethylenepyrroline) behaved as a polyelectrolyte in formic acid and had an intrinsic viscosity of 0.157 (dL/g) whereas, poly(N-pheny1-3,4-dimethylenepyrrole) behaved as a polyelectrolyte in DMF and had an intrinsic viscosity of 0.099 (dL/g). No common solvent for these two polymers could be found, therefore, a comparison of the viscosities before and after the oxidation was not possible. 

Unfortunately, the number of systems in which it can be established whether Keller s model is realistic for a particular case is severely limited since the original polymer is usually not soluble in the same medium as the ultimate reaction product. In cases where the entire course of the reaction can be followed, as in the basic hydrolysis of polyacrylamide, investigators have analyzed their results by a computer search for the k, k, k values which fit best their kinetic data (9). This, or course, does not answer the question whether the model using these three rate constants provides a full description of a particular case. 

Figure 19 Chemiluminescence from oxidation of polypropylene containing 0.5 % wt. of Irganox 1010 at 150°C in oxygen. Line 1 represents the original polymer film line 2 is the same sample after 7,890 s of annealing at 130°C.

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