Evaluation of the Parameters of Poly(Butylene succinate) Enzymatic Polymerization

2021 ◽  
Vol 7 (1) ◽  
pp. 11
Author(s):  
Christina I. Gkountela ◽  
Dimitrios N. Markoulakis ◽  
Dimitrios M. Korres ◽  
Stamatina N. Vouyiouka

Poly(butylene succinate) (PBS) is a bio-based and biodegradable polyester that can be used in numerous applications, ranging from clothing to food packaging and from the car industry to the biomedical sector (e.g., drug release systems). The conventional polymerization method of PBS requires the presence of metal-based transesterification catalysts (e.g., titanium-based catalysts) and high reaction temperatures (T > 150 °C). However, under these conditions side reactions may occur along with undesirable yellowing. Green polymerization routes such as biocatalysis are being developed. However, there is a very limited literature on the enzymatic synthesis of PBS. Additionally, in most of the works where high-molecular-weight PBS is produced from the typical monomers (BDO and DES), several drawbacks, e.g., the use of various solvents for polymer isolation and the requirement of high vacuum for by-products removal may impede the process being scaled up. On that basis, an eco-friendly, solvent-free, enzyme-based process for the production of PBS was applied. It was conducted in two steps with the use of Novozym 435: the first at 40 °C, under atmospheric pressure for 24 h, and the second at 90 °C, 20 mbar for 2 h. This work focused on the optimization of the second step’s conditions, by varying reaction temperature (80–95 °C), pressure (20 mbar, 200 mbar) and reaction time (2 h, 6 h). Based on the optimization results, the process was scaled up (ca. 10 g of product). A PBS grade free of thermal degradation and metal catalyst residues, of weight-average molecular weight 4700 g/mol and melting point 103 °C, was obtained.

2015 ◽  
Vol 2015 ◽  
pp. 1-9 ◽  
Author(s):  
N. Ugur Kaya ◽  
Y. Avcibasi Guvenilir

Poly(ε-caprolactone) (PCL) macromonomers comprising acrylate end-functionality were synthesized via enzymatic ring-opening polymerization (eROP) by utilizing commercially availableCandida antarcticaLipase B (CALB), Novozyme-435. 2-Hydroxyethyl methacrylate (HEMA) was purposed to be the nucleophilic initiator in eROP. The side reactions generated due to the cleavage of ester bonds in HEMA and the growing polymer chains were investigated through altering polymerization period, initiator concentration, temperature, and enzyme concentration.1H NMR evaluations showed that minimum quantities of side reactions were in lower temperatures, initiator concentration, enzyme concentration, and lower monomer conversions. Gel permeation chromatography (GPC) results revealed that lower polydispersity along with number-average molecular weight of end-functionalized PCL macromonomers was obtained depending on higher initiator/monomer ratios, lower temperature (60°C), enzyme concentration (100 mg), and/or polymerization time (2 h). Furthermore, 0.1 HEMA/ε-caprolactone (CL) ratio had higher molecular weight than 0.5 HEMA/CL ratio, while keeping a close value of methacrylate transfer, total methacrylate end-groups, and lower polyester transfer.


2003 ◽  
Vol 15 (3) ◽  
pp. 361-370 ◽  
Author(s):  
S. Tamai ◽  
C. Tanaka ◽  
T. Abe ◽  
T. Kuroki ◽  
J. Ishikawa

Several types of poly[(arylenedioxy)(diphenylsilylene)]s and poly[(alkylenedioxy)(diphenylsilylene)] were synthesized from various diols and dichlorodiphenylsilane by the step polymerization method. The thermal properties, solubility in organic solvents and optical properties of the obtained polymers were investigated by focusing on the chemical structures of their repeating structural units. The weight-average molecular weight ( Mw) of the obtained polymers based on polystyrene ranged from 43000 to 194000. High molecular weight, ductile materials with a high degree of optical clarity were obtained. These polymers display glass transition temperatures ( Tg) between 96 and 130°C. The obtained poly[(arylenedioxy) (diphenylsilylene)]s and poly[(alkylenedioxy)(diphenylsilylene)] were soluble in chloroform and toluene. The refractive index ( nd) was 1.64 for a biphenol-based poly[(arylenedioxy)(diphenylsilylene)] and 1.61 for a bisphenol-A based poly[(arylenedioxy)(diphenylsilylene)]. The poly[(arylenedioxy)(diphenylsilylene)]s and poly[(alkylenedioxy)(diphenylsilylene)] display very low birefringence (Δ n) between 0.0005 and 0.0022. The 70 μm thick film transmission of bicyclohexanol-based poly[(alkylenedioxy)(diphenylsilylene)] was 91% at a 350 nm wavelength.


2013 ◽  
Vol 821-822 ◽  
pp. 937-940 ◽  
Author(s):  
Shi Jie Zhang ◽  
Yi Wen Tang ◽  
Li Hua Cheng

Poly (butylene succinate) (PBS) was mixed with Poly (lactic acid) (PLA) in the melt state. The PLA/PBS blends with different constitution were produced. The samples were buried in laterite. Samples were dug out of soil after the burial for 10, 20, 30, 40, 50 and 60 days, respectively. The weight loss and molecular weight of the sample were tested. The analysis showed that the nearly exponential decrease in average molecular weight as a function of degradation time. The PLA and PBS have the similar degradation behavior in the soil.


1943 ◽  
Vol 16 (1) ◽  
pp. 45-57
Author(s):  
Ernest Harold Farmer ◽  
Donald A. Sutton

Abstract One of the most astonishing phenomena connected with the chemistry of rubber is the ease with which it absorbs progressively very small percentages of oxygen, and suffers as a result drastic and progressive reduction of its molecular weight. The natural conclusion to be drawn is that the polyisoprene chains of the rubber are undergoing oxidative scission at one after another of their unsaturated centers, so that the original long hydrocarbon chains become divided into smaller and smaller fragments possessing oxygenated ends. Recent estimates of the molecular weight of rubber by viscosity and osmotic methods range from 240,000 to 360,000 for fractions of decreasing solubility in hydrocarbon solvents. If we accept these figures and assume for the moment that two atoms of oxygen are sufficient to sever the hydrocarbon chains at a double bond, then an absorption of only 0.009–0.013 per cent of oxygen (applied, of course, exclusively to scission reactions) should suffice to reduce the average molecular weight to one-half. If the observed reductions of molecular weight are to be ascribed solely to oxidative scission of the chains, then, provided oxygen-consuming side reactions are few, a fairly exact inverse proportionality may be expected to hold between the uptake of oxygen and the average molecular weight of the degraded rubber. The most striking reductions in the molecular weight per unit of oxygen absorbed must, of course, occur at the very early stages of oxidative fission, while the hydrocarbon chains are still very long, and to be able to follow effectively the quantitative relationship between these important reductions and the oxygen uptake, it is necessary to make experimental provision for the absorption, even distribution, and measurement of very minute quantities of oxygen. Minute though the overall proportion of oxygen necessary to produce a substantial reduction in molecular weight appears in practice to be, however, there is no evidence to indicate that the scission reaction ever follows the course most economical in oxygen, i.e.,


2013 ◽  
Vol 821-822 ◽  
pp. 1023-1026 ◽  
Author(s):  
Kai Shen ◽  
Sheng Lin Yang

Relatively high molecular weight poly(glycolic acid)(PGA) was prepared by improved melting polycondensation of glycolic acid. Firstly, two kinds of catalyst, zinc acetate dihydrate and tin dichloride dehydrate, were utilized respectively, and a selection was made according to the molecular weight of final product. It has been found that the tin catalyst was the better one. Then the catalyst usage, the heating program, the polymerization time, as well as the vacuum condition were optimized. It was found that the high vacuum at 220~230°C contributed much to the molecular weight to the polymer, however, the polymerization time should be less than 1.5hr to avoid the discolor of the product. Finally, the PGA with a weight average molecular weight of 45,000g/mol were obtained directly without solid phase polycondensation, which was rather higher than some reported previously. The structure and properties of PGA were also characterized by means of intrinsic viscosity, FTIR, NMR and DSC testing.


1959 ◽  
Vol 32 (3) ◽  
pp. 706-717
Author(s):  
L. H. Howland ◽  
A. Nisonoff ◽  
L. E. Dannals ◽  
V. S. Chambers

Abstract 1. A method has been developed for the measurement of crosslink density of diene polymers. This method, which involves the use of radioactive chain transfer agents, is applicable to ungelled polymer prepared under a wide variety of conditions so that any polymerization variable can be studied independently. 2. The crosslink density in polybutadiene decreases with decreasing polymerization temperature. At low molecular weight of polymers, the amount of crosslinking varies linearly with the polymerization temperature. 3. The crosslink density of polybutadiene increases with increasing number-average polymer molecular weight. The rate of increase is less for polymer prepared at −18° C than for that polymerized at 5° to 50° C. This means that, in a polymerization, as the average molecular weight increases with conversion the crosslink density increases. However, when the molecular weight is kept constant, by changes in the modifier loading, the crosslink density of polybutadiene appears to be independent of the degree of conversion attained within the range of 0.12–0.48. 4. The crosslink density of a high molecular weight fraction of polybutadiene was not significantly different from that of the whole polymer (from which about 3% of low molecular weight material had been removed). 5. The kind of initiator system does not affect the crosslink density of polybutadiene, providing the initiator loading is not too high. However, if large amounts of initiator are used in the polymerization, 10% or more of the polymer molecules may not contain mercaptan modifier. 6. Tertiary alkyl mercaptans are necessary for the crosslinking studies because they do not appear to give side reactions. Primary dodecylmercaptan and diisopropyl xanthogen disulfide are unsatisfactory for determinations because they appear to add to the double bonds of the polymer molecule in addition to the usual chain transfer reactions. 7. Incomplete emulsification of monomers in some 5° C recipes apparently increased the crosslink density of polybutadiene by retarding the diffusion of monomer into the monomer-polymer particles.


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.


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