scholarly journals Enzymatic Polycondensation of 1,6-Hexanediol and Diethyl Adipate: A Statistical Approach Predicting the Key-Parameters in Solution and in Bulk

Polymers ◽  
2020 ◽  
Vol 12 (9) ◽  
pp. 1907
Author(s):  
Kifah Nasr ◽  
Julie Meimoun ◽  
Audrey Favrelle-Huret ◽  
Julien De Winter ◽  
Jean-Marie Raquez ◽  
...  

Among the various catalysts that can be used for polycondensation reactions, enzymes have been gaining interest for three decades, offering a green and eco-friendly platform towards the sustainable design of renewable polyesters. However, limitations imposed by their delicate nature, render them less addressed. As a case study, we compare herein bulk and solution polycondensation of 1,6-hexanediol and diethyl adipate catalyzed by an immobilized lipase from Candida antarctica. The influence of various parameters including time, temperature, enzyme loading, and vacuum was assessed in the frame of a two-step polymerization with the help of response surface methodology, a statistical technique that investigates relations between input and output variables. Results in solution (diphenyl ether) and bulk conditions showed that a two-hour reaction time was enough to allow adequate oligomer growth for the first step conducted under atmospheric pressure at 100 °C. The number-average molecular weight (Mn) achieved varied between 5000 and 12,000 g·mol−1 after a 24 h reaction and up to 18,500 g∙mol−1 after 48 h. The statistical analysis showed that vacuum was the most influential factor affecting the Mn in diphenyl ether. In sharp contrast, enzyme loading was found to be the most influential parameter in bulk conditions. Recyclability in bulk conditions showed a constant Mn of the polyester over three cycles, while a 17% decrease was noticed in solution. The following work finally introduced a statistical approach that can adequately predict the Mn of poly(hexylene adipate) based on the choice of parameter levels, providing a handy tool in the synthesis of polyesters where the control of molecular weight is of importance.

Polymers ◽  
2019 ◽  
Vol 11 (10) ◽  
pp. 1690
Author(s):  
Lee ◽  
Kang ◽  
Kim ◽  
Seo ◽  
Pyo ◽  
...  

1,9-Nonanedioic acid is one of the valuable building blocks for producing polyesters and polyamides. Thereby, whole-cell biosynthesis of 1,9-nonanedioic acid from oleic acid has been investigated. A recombinant Corynebacterium glutamicum, expressing the alcohol/aldehyde dehydrogenases (ChnDE) of Acinetobacter sp. NCIMB 9871, was constructed and used for the production of 1,9-nonanedioic acid from 9-hydroxynonanoic acid, which had been produced from oleic acid. When 9-hydroxynonanoic acid was added to a concentration of 20 mM in the reaction medium, 1,9-nonanedioic acid was produced to 16 mM within 8 h by the recombinant C. glutamicum. The dicarboxylic acid was isolated via crystallization and then used for the production of biopolyester by a lipase. For instance, the polyesterification of 1,9-nonanedioic acid and 1,8-octanediol in diphenyl ether by the immobilized lipase B from Candida antarctica led to formation of the polymer product with the number-average molecular weight (Mn) of approximately 21,000. Thereby, this study will contribute to biological synthesis of long chain dicarboxylic acids and their application for the enzymatic production of long chain biopolyesters.


Author(s):  
C. E. Cluthe ◽  
G. G. Cocks

Aqueous solutions of a 1 weight-per cent poly (ethylene oxide) (PEO) were degassed under vacuum, transferred to a parallel plate viscometer under a nitrogen gas blanket, and exposed to Co60 gamma radiation. The Co60 source was rated at 4000 curies, and the dose ratewas 3.8x105 rads/hr. The poly (ethylene oxide) employed in the irradiations had an initial viscosity average molecular weight of 2.1 x 106.The solutions were gelled by a free radical reaction with dosages ranging from 5x104 rads to 4.8x106 rads.


1998 ◽  
Vol 38 (6) ◽  
pp. 209-217 ◽  
Author(s):  
Jianhua Lei ◽  
Sveinung Sægrov

This paper demonstrates the statistical approach for describing failures and lifetimes of water mains. The statistical approach is based on pipe inventory data and the maintenance data registered in the data base. The approach consists of data pre-processing and statistical analysis. Two classes of statistical models are applied, namely counting process models and lifetime models. With lifetime models, one can estimate the probability which a pipe will fail within a time horizon. With counting process models one can see the deteriorating (or improving) trend in time of a group of “identical” pipes and their rates of occurrence of failure (ROCOF). The case study with the data base from Trondheim municipality (Norway) demonstrates the applicability of the statistical approach and leads to the following results: 1). In the past 20 years, Trondheim municipality has experienced approximately 250 to 300 failures per year. However, the number of failures per year will significantly increase in the near future unless better maintenance practice is implemented now. 2). Unprotected ductile iron pipes have a higher probability of failures than other materials. The average lifetime of unprotected ductile iron pipes is approximately 30 to 40 years shorter than the lifetime of a cast iron pipe. 3). Pipes installed 1963 and 1975 are most likely to fail in the future; 4) The age of a pipe does not play a significant role for the remaining lifetime of the pipe; 5). After 2 to 3 failures, a pipe enters a fast-failure stage (i.e., frequent multiple between failures).


1988 ◽  
Vol 53 (1) ◽  
pp. 145-156 ◽  
Author(s):  
Jana Pírková ◽  
Svetlana Churkina ◽  
Vladimír Gut ◽  
Ivo Frič ◽  
Karel Bláha

The sequential polypeptides (Lys-Ala)n, (Lys-Ala-Ala)n, (Lys-Ala-Ala-Ala)n, (Lys-Leu-Ala)n, (Lys-Leu-Ala-Ala)n, (Lys-Leu-Ala-Ala-Ala)n, (Lys-Ala-Leu)n, (Lys-Ala-Leu-Ala)n, (Orn-Leu-Ala)n,(Arg-Ala-Ala)n, (Arg-Leu-Ala)n, (Arg-Leu-Ala-Ala)n, (Arg-Ala-Leu)n, and (Arg-Ala-Leu-Ala)n were synthesized by polymerization of active esters (1-succinimidyl or pentafluorophenyl) of the corresponding Nα-deblocked monomers. The monomers were prepared using the usual methods of peptide synthesis in solution. Upon dialysis, the average molecular weight of the polymer was 6 000-9 000 as determined by sedimentation in ultracentrifuge. Polypeptides, containing leucine in addition to the basic amino acid, showed a marked tendency to aggregation. CD spectra of the products were measured for characterization.


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