Structural Characteristics of Alkyllithium Catalyzed Polymers Derived from Butadiene and Styrene

1967 ◽  
Vol 40 (2) ◽  
pp. 590-601 ◽  
Author(s):  
F. C. Weissert ◽  
B. L. Johnson

Abstract More than a million miles of tire testing is generally required to prove the utility of a new elastomer. For example, such a program has recently demonstrated that an alkyllithium solution polymerized butadiene styrene copolymer (Duradene rubber) has improved abrasion resistance over that of emulsion SBR1. It is, thus, extremely important to find meaningful relationships between the structure of an elastomer and its commercial importance to further guide the polymer chemist toward the development of new general purpose or specific application elastomers from laboratory sample through to final tire evaluation. Butadiene homopolymers and butadiene styrene copolymers prepared by alkyllithium catalysis in hydrocarbon solution offer unique opportunities to relate basic polymer structure parameters to tire compound performance. Their mixed micro-structure (cis-1, 4, trans-1, 4, and vinyl) preclude crystalline transitions which would otherwise complicate the interpretation of structural behavior. Furthermore, this polymerization system permits the production of controlled and specific variations in molecular weight distribution and degree of branching. n-Butyllithium catalyzed 1, 4-polybutadiene with its mixed microstructure and high cis-1, 4-polybutadiene have both shown outstanding abrasion resistance, especially under conditions of severe tire service. There is as yet no generally clear molecular interpretation for the outstanding abrasion resistance of the 1, 4-polybutadienes. For reasons of both improved processing and increased wet traction, these 1, 4-polybutadienes are seldom used alone but are blended with either natural rubber or SBR plus large amounts of extending oils. As a start, using as few fundamental concepts as possible, attempts were made to relate the industrial processing, heat build up, traction, and abrasion resistance characteristics of amorphous elastomers to two features measurable in terms of molecular parameters. The macrostructure (molecular weight distribution and branching) of the polymer is especially related to processing behavior. The glass temperature, Tg, of a polymer characterizes both the temperature and rate of deformation conditions in which the polymer exhibits rubbery behavior. Hence, the polymer Tg is directly related to both heat build-up and failure characteristics of an elastomer. Thus we shall be mostly discussing polymer structure in just two terms (i) macrostructure and (ii) Tg.

1970 ◽  
Vol 43 (6) ◽  
pp. 1424-1438
Author(s):  
C. A. Uraneck ◽  
J. E. Burleigh

Abstract Polystyrene and butadiene—styrene copolymers (SBR) were parepared in emulsion systems with a homologous series of commercial mercaptan modifiers. The molecular weight distribution (MWD) of the sets of polymers changed in a consistant manner when the regulating index of the mercaptan was relatively low. However the shape of the MWD curves appeared distorted in comparison to theoretical curves when the modifier depleted rapidly and when divinyl-benzene was present in the system. The divergence from the theoretical curve is attributed to a higher degree of branching in the high molecular weight fractions. Differences in MWD of SBR made with n- and tert-dodecyl mercaptans was marked. Notable differences were also found for SBR 1500 samples from the industry at random, but only slight differences were seen in a set of SBR 1503 samples. This study shows how the MWD of polymers prepared in emulsions can be varied simply by use of modifiers with different regulating indexes.


2013 ◽  
Vol 10 (2) ◽  
pp. 29
Author(s):  
Normah Ismail ◽  
Nur' Ain Mohamad Kharoe

Unripe and ripe bilimbi (Averrhoa bilimbi L.) were ground and the extracted juices were partially purified by ammonium sulfate precipitation at the concentrations of 40 and 60% (w/v). The collected proteases were analysed for pH, temperature stability, storage stability, molecular weight distribution, protein concentration and protein content. Protein content of bilimbi fruit was 0.89 g. Protease activity of both the unripe and ripe fruit were optimum at pH 4 and 40°C when the juice were purified at 40 and 60% ammonium sulfate precipitation. A decreased in protease activity was observed during the seven days of storage at 4°C. Molecular weight distribution indicated that the proteases protein bands fall between IO to 220 kDa. Protein bands were observed at 25, 50 and 160 kDa in both the unripe and ripe bilimbi proteases purified with 40% ammonium sulfate, however, the bands were more intense in those from unripe bilimbi. No protein bands were seen in proteases purified with 60% ammonium sulfate. Protein concentration was higher for proteases extracted with 40% ammonium sulfate at both ripening stages. Thus, purification using 40% ammonium sulfate precipitation could be a successful method to partially purify proteases from bilimbi especially from the unripe stage. 


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