Polymerization Of PLA Research Articles

Improvement of Thermo-Stability and Solvent Tolerant Property of Streptomyces sp. A3301 Lipase by Immobilization Techniques with Application in Poly (lactic acid) Polymerization by Using Biological Process

The thermo-solvent-tolerant lipase-producing actinomycete, Streptomyces sp. A3301, was utilized as a biocatalyst for poly (lactic acid) or PLA polymerization. The study aimed to optimize lipase immobilization conditions, characterize the immobilized lipase and apply it for PLA polymerization. The results showed using a sponge as the immobilizing matrix was the most effective method, achieving a maximum activity of 277 U/g of sponge. The optimal sponge size was determined to be 0.125 cm³ and pre-soaking the sponge in 0.1 M phosphate buffer at pH 7.0 for 24 h before use proved advantageous. Immobilization significantly enhanced the thermo-stability of the enzyme, with a relative activity ranging from 140 to 190 % within the temperature range of 30 to 60 °C. In contrast, the crude lipase exhibited thermo-stability only within the 30 - 50 °C range. The immobilized lipase demonstrated stability under PLA polymerization conditions, which involved a reaction mixture containing toluene and lactic acid and performed at 60 °C for 8 h. The immobilized lipase maintained its activity under this condition for 5 h, retaining a relative activity of 230 %, which was 1.2 times higher than the activity of the crude lipase. When the immobilized lipase was used in PLA polymerization, the resulting PLA product exhibited a molecular weight of 5,333 ± 0.02 Da, and the degree of polymerization was approximately 72. These findings underscore the potential of the immobilization technique to enhance lipase activity for PLA polymerization. HIGHLIGHTS PLA polymerization via a biological process is demonstrated. PLA can be polymerized by enzyme lipase produced by Streptomyces sp. A3301. Improving PLA polymerization with enzyme immobilization techniques. Sponge is the best immobilizer for PLA polymerization. PLA can be synthesized under mild conditions. GRAPHICAL ABSTRACT

Quinolyl/pyridyl-amino Li complexes as dual catalysts for the ring-opening polymerization of cyclic esters and degradation toward a circular economy approach

Bi- and tetra-lithium quinolyl/pyridyl-amino complexes 1–4 were synthesized and characterized. These lithium complexes were capable of initiating the polymerization of rac-lactice (rac-LA) and ε-caprolactone (ε-CL) with high catalytic activity, respectively, whether in the presence or absence of BnOH. Both number of metal centers and ligand structures are identified as the crucial factors that determine the reactivity of a catalyst in the ROP. Their kinetic analyses indicated that tetrametallic complex 3 showed a more cooperativity comparable to that achieved with bimetallic analogues in the ring-opening polymerization (ROP) of ε-CL, however, number of metal centers has no obvious effect on catalytic activity for the ROP of rac-LA. Polymer end-group analysis by 1H NMR and MALDI-TOF MS support the reaction initiated by Li complexes without or with BnOH switching mechanism from a coordination-insertion to an active monomer in the ROP processes reasonably. The diblock copolymer PCL-b-PLA can be effectively prepared by polymerizing ε-CL firstly followed by addition of rac-LA. However, the formation of PLA-b-PCL or PLA-random-PCL is limited, and the resulting copolymers only contain a short sequence of PCL moieties which produced by the transesterification between PLA and ε-CL, whether the two monomers are added sequentially or simultaneously. Interestingly, these Li complexes not only exhibit a high activity for the polymerization of PLA, but also can fully degrade the resultant PLA into methyl lactate (Me-La) in the presence of MeOH, which is a rare example of making or breaking polymer for chemical recycling.

Synthesis, properties, and applications of polylactic acid‐based polymers

AbstractPolylactic acid (PLA) is known as one of the greatest promising bioabsorbable and compostable polyesters with the capability of high molecular weight synthesis. Lactic acid condensation, azeotropic dehydration, and condensation ring‐open polymerize of lactide are three methods for PLA polymerization. Comprehension of material properties is critical for choosing the right processing method and adjusting PLA characteristics. A variety of mechanical properties of this material, from soft and elastic to stiff and high strength makes PLA suitable for a wide range of applications. Besides, PLA can be blended or copolymerized with other polymeric or non‐polymeric substances. Thus, this polymer can achieve suitable chemical, mechanical, and rheological properties. Understanding the role of these properties and selecting a suitable processing technique is necessary for its intended consumer and various applications. This study elaborated a general summary of the polymerization, processing, and characteristics of PLA (i.e., structural diversities, rheological performances, mechanical properties, and permeability). Besides, this work presented some information regarding essential factors that can be used for modifying PLA properties to address the requirements for various applications such as biomedical, food packing, biocomposite, and additive manufacturing.

Enzymatic Polymerization as a Green Approach to Synthesizing Bio-Based Polyesters

Given the fossil fuel crisis and the steady consumption of finite resources, the use of green polymers is becoming necessary. However, the term “green” describes materials that present green properties (such as biological origin and/or biodegradability) and are produced via sustainable processes conducted under mild conditions and not requiring the use of chemical catalysts, toxic solvents or reagents. Truly green materials must combine these characteristics; consequently, enzymatically synthesized bio-based and/or biodegradable polymers can be characterized as truly green. The present review focuses on the most promising, commercially available aliphatic and alipharomatic polyesters that can be synthesized enzymatically. In particular, the recent developments in the enzymatic polymerization of PLA and PBS and alipharomatic furan-based polyesters (e.g., PBF) are herein analyzed. Based on this analysis, it can be concluded that important steps have been taken toward synthesizing sustainably green polymers. Still, it is necessary to evaluate the applied methods regarding their capability to be used on an industrial scale.

Poly(lactic acid) fibers, yarns and fabrics: Manufacturing, properties and applications

Poly(lactic acid) (PLA) fiber was developed more than a decade ago. It has been regarded as the most promising sustainable and biodegradable fiber to replace conventional polyethylene terephthalate (PET) polyester fiber in textile products. This paper reviews recent developments in PLA polymerization, PLA filament and fiber spinning, staple yarn spinning, fabric production, dyeing and finishing and aftercare procedures. The properties of PLA fiber are broadly similar to those of PET fiber; however, the properties of PLA fiber that differ, including thermal degradation and low hydrolytic resistance to strong alkaline, significantly affect the method selection and parameter setting of production and processing of PLA fibers and fabrics. PLA filaments are mainly produced by two-step melt spinning to get fibers with stable quality, but degradation at high temperature is still a problem. PLA staple yarns are normally spun using ring spinning. Currently existing knitting or weaving techniques can be used to produce PLA fabrics. PLA fabrics can be dyed with disperse dyes at 110°C, but their color fastness and shades are different from PET fabrics when using the same dyes. The scouring and dyeing of PLA/cotton blended fabrics and the reductive clearing after dyeing remain to be improved. As a new fiber, the entry of PLA fiber into the textile market faces difficult challenges as well as great opportunities in the future.

New insight into thermo-solvent tolerant lipase produced by Streptomyces sp. A3301 for re-polymerization of poly (dl-lactic acid)

Poly (lactic acid) (PLA) is a biodegradable plastic that has received considerable attention since it plays an important role in replacing commercial plastics and resolving the global warming problem. Recently, biological degradation and polymerization studies of PLA have been an active topic. Microbial solvent-tolerant and thermostable lipases are interesting since they have the potential to induce PLA polymerization. The aims of this study are to isolate solvent-tolerant and thermostable lipase-producing actinomycetes and to apply the crude enzyme produced by an isolated strain for PLA polymerization. According to the results, the best solvent-tolerant and thermostable lipase-producing actinomycete was strain A3301, with a lipase activity of 108 U/ml in the production medium. The crude enzyme produced by strain A3301 demonstrated the optimum temperature and thermostability at 60 °C and 45–55 °C, respectively. Moreover, the enzyme showed the ability to tolerate 10–20% (v/v) hexane and toluene. Strain A3301 was identified as Streptomyces sp. by using the 16S rDNA sequence. A thermo-solvent-tolerant lipase from this strain was used in PLA polymerization experiments. The optimal conditions for PLA synthesis were 60 °C for 8 h, using dried lipase at a concentration of 10% (w/v) and a fixed lactic acid concentration of 450 g/L under a nitrogen atmosphere. The highest molecular weight of the PLA product was 525 Da, and the degree of polymerization was approximately 7. Subsequently, the repolymerization process of PLA using this enzyme was investigated. The maximum molecular weight of the PLA product was 577 Da, and the degree of polymerization was approximately 8.

Synthesis of Heterobifunctional Thiol‐poly(lactic acid)‐b‐poly(ethylene glycol)‐hydroxyl for Nanoparticle Drug Delivery Applications

AbstractBiocompatible, amphiphilic block copolymers, such as poly(lactic acid)‐b‐poly(ethylene glycol) (PLA‐b‐PEG), that can be conjugated to targeting ligands, therapeutics, and imaging agents are required for the development of polymeric nanoparticle drug delivery systems. Synthesis of targetable, heterobifunctional X‐PLA‐b‐PEG‐Y has required the use of heterobifunctional PEG, which involves specialty equipment to synthesize and is expensive to purchase. Herein, a new method for the synthesis of bifunctional HS‐PLA‐b‐PEG‐OH is described. The approach takes advantage of polymer solution properties to improve a critical purification step, and uses inexpensive and readily available PEG‐diol as a starting material. In the method demonstrated here, the ring‐opening polymerization of PLA is initiated by both ends of a cleavable bifunctional initiator. PEG is conjugated to each PLA end, resulting in a high molecular weight intermediate which is simple to purify from the excess PEG, with recoveries that are nearly three times higher than when a monofunctional initiator is used. Following purification, the triblock copolymer is cleaved to produce the final HS‐PLA‐b‐PEG‐OH product, in which both polymer ends are reactive. Moreover, the polymers successfully stabilize nanoparticles produced by Flash NanoPrecipitation. Importantly, the synthesis method can be adopted by non‐polymer experts.

Synthesis and Characterization of Poly(Lactic Acid)-Grafted Natural Rubber by Reactive Melt-Blending Technique

This study investigated the synthesis and characterization of poly(lactic acid)-grafted natural rubber (PLA-g-NR) in molten state. The grafting was carried out in an internal mixer without and with the presence of tin octoate catalyst (TO). The grafting of lactide onto NR was carried out by using maleic anhydride (MA) as a linker. The FTIR and 1H-NMR spectra revealed new peaks for the MA-grafted NR (NR-g-MA) and PLA indicating that MA was grafted onto NR and that LA was successfully polymerized into PLA. It was also found that MA grafted onto NR could assist as a linker for connecting PLA with NR via esterification reaction between hydroxyl group (OH) at the end chain of PLA and carboxylic group (COOH) from ring opening reaction of MA. Moreover, the decrease of residual LA peak in FTIR spectra suggested that the presence of TO catalyst in the reactive blend promoted higher degree of polymerization of PLA from ring opening reaction of LA.

Evaluating The Extent of Bio-Polyester Polymerization in Solid Wood by Thermogravimetric Analysis

In this study, the thermogravimetric analysis (TGA) technique has been applied to determine the extent of in situ polymerization achievable in solid wood on treating with bio-polyester oligomers. Low-molecular-weight oligomers of poly(lactic acid) (PLA), poly(glycolic acid) (PGA), poly(butylene succinate) (PBS), and poly(butylene adipate) (PBA) were impregnated and then thermally polymerized within solid wood to enhance the physical properties of wood. TGA revealed a similar degree of oligomer polymerization was achieved either with pure oligomers or within the wood structure. The influence of relatively acidic treatments, such as low-molecular-weight PGA oligomers, was observed to lead to degradation of the hemicellulose wood component. Polymerization of PLA and PGA oligomer treatments which penetrate the wood cell wall gave relatively lower wood thermal stability. Treatment and polymerization of lumen filling PBS and PBA oligomers contributed to increased wood thermal stability.

Poly(l-histidine) based triblock copolymers: pH induced reassembly of copolymer micelles and mechanism underlying endolysosomal escape for intracellular delivery.

Various poly(l-histidine) based amphiphilic copolymers have been developed for intracellular drug delivery due to the pH responsive properties and the escape from endolysosomal pathway. However, the pH induced reassembly of copolymer micelles and the assumed endolysosome membrane rupture during the copolymer facilitated endolysosomal escape have never been elucidated. To address these issues, a series of poly(ethylene glycol)-poly(d,l-lactide)-poly(l-histidine) (mPEG-PLA-PHis) with different degrees of polymerization of PLA and PHis block were synthesized. The self-assembly and reassembly behaviors of the copolymers were characterized using transmission electron microscopy (TEM), (1)H NMR, fluorescence probe technique, and dynamic light scattering (DLS). The copolymers self-assembled into micelles with PLA and unprotonated PHis blocks as hydrophobic core and PEG as hydrophilic shell at neutral pH. The changes in TEM images, (1)H NMR spectrum of PHis peak, pyrene fluorescene spectrum, and particle size as well as size distribution over the pH range from pH 8.5 to 4.5 suggest that the copolymer micelles reassembled into micelles with PLA as hydrophobic core and protonated PHis and PEG as hydrophilic shell under acidic environment. The pH induced reassembly triggered the incoporated doxorubicin (DOX) release, as indicated by the in vitro accelerated drug release and enhanced cytotoxicity. The integrity of endolysosome membrane during the copolymer facilitated DOX endolysosomal escape was observed by confocal laser scan microscopy (CLSM) and further evaluated by hemolysis test and calculation of the critical size of endolysosomal membrane. The results indicate that the endolysosomal membrane remained intact during the copolymer facilitated endolysosomal escape of DOX. It is more reasonable to ascribe the PHis based copolymer facilitation endolysosomal escape to the "proton sponge" hypothesis without rupturing the endolysosomal membrane.

Construction of late transition metal complex on amine-functionalized SiO2 and SBA-15 for L-lactide polymerization.

We report the in-situ synthesis of a late transition metal catalyst on amine-functionalized SBA-15 and amorphous silica and their ring opening polymerizations of L-lactide. Funtionalizations of SBA-15 and amorphous silica with N-[3-(trimethoxysilyl)propyl]-ethylenediamine (2NS) were carried out to in-situ synthesize late transition metal catalysts on the surface of nanoporous materials. FT-IR spectra indicates that the 1,2-dimethoxyethane ligand did not participate in the reaction when (DME)NiBr2 was immobilized on the amine-functionalized silica. In addition, the XPS spectrum confirmed the presence of Ni compound on the 2NS-functionalized SiO2. SBA-15/2NS/Ni and SBA-15/ 2NS/Pd catalysts showed higher conversion of PLA polymerization in comparison to SiO2/2NS/Ni and SiO2/2NS/Pd, respectively. The molecular weights of PLA produced by SBA-15/2NS/Ni or Pd were larger than those of SiO2/2NS/Ni or Pd, respectively. The effects of polymerization conditions such as the polymerization temperature, time, the catalyst amount in the feed, and the polymerization medium in L-lactide polymerization were also investigated.

Kinetic parameters estimation of ring-opening poly(lactic acid) polymerization by modeling and simulation

Abstract The modeling of ring-opening polymerization of lactide to poly(lactic acid) (PLA) has been carried out. Carothers first synthesized PLA in 1932. Since then, hundreds of research papers and patents have appeared in the literature. However, there is a lack of data concerning the rate constants for initiation, propagation and termination steps of PLA polymerization, except some data about the apparent rate constant. This work investigates, theoretically, the individual rate constants using a simple numerical technique. The progress of lactide polymerization can be modeled by assuming a ring opening reaction mechanism comprising chain initiation, chain propagation, and chain termination. The simulator developed, based on the solutionof differential equations corresponding to the above-mentioned kinetic scheme, Generates a detailed molecular weight distribution that can be used to estimate average molecular weights (or average degree of polymerization) vs. polymerization time curves. These simulated curves, on matching with the reported experimental data (for different catalysts), yield the absolute values of rate constants. The values have been determined for zinc lactate. Rate constants could be determined by using the molecular weight and the polydispersity vs. polymerization data. This methodology offers greater opportunity for capturing high, non-equilibrium polymer yield through appropriately timed termination of the polymerization reaction.

Synthesis and characterization of poly( l-lactic acid) reinforced by biomesogenic units

To increase the thermal and mechanical properties of poly( l-lactic acid) (PLA), a nontoxic biomesogen PFBH derived from ferulic acid (FA), 4-hydroxybenzoic acid (HBA) and 1,6-hexanediol (HD) was introduced into the PLA backbones by solution polymerization of PLA, PFBH and chain linker hexamethylene diisocyanate (HDI). The content of PFBH was varied from 0 to 30 mol% so that the effects of the biomesogen content on the thermal and physical properties, morphological textures and enzymatic degradation were examined, respectively. The synthesized materials were characterized by means of differential scanning calorimetry (DSC), thermogravimetric analysis (TGA), wide angle X-ray diffraction (WAXD), polarizing light microscopy (PLM) and mechanical property measurements. It was found that introducing biomesogenic units could increase the thermal stability and reinforce the elastic properties, while reduced the melting temperature, the degree of crystallinity and the enzymatic degradation rate. The nontoxicity and biocompatibility of degradation would make the products promising candidates for medical applications in the area of tissue engineering.

Two-Step Process for Continuous Polymerization of Polylactic Acid

We examined a two-step process concept for PLA polymerization with a small amount of catalyst addition to achieve both a high conversion ratio and a small degree of yellowing. First, we developed a calculation program for the chemical reactions. Next, we carried out beaker-scale PLA polymerization experiments to measure the degrees of yellowing. The measured values were compared to amounts of thermal degradation estimated from the calculations simulating the experiments. Then, bench-scale equipment experiments were carried out on the basis of the obtained conditions. The conversion ratios and the degrees of yellowing of the PLA samples obtained from the bench-scale equipment were compared to the numerical simulation results to verify the process concept and conditions. 170°C was good for a first polymerization temperature to avoid a runaway reaction due to heat generation in the ring-opening polymerization. To minimize the degree of yellowing at conversion ratio of 0.9, we chose 5 h as both the first polymerization time at 170°C and the second polymerization time at 190°C. From bench-scale continuous polymerization experiments, we got PLA that had a conversion ratio of 0.92, a weight average molecular weight of 1.96 × 105, and a b-value of 2.42 to verify the concept of the two-step process.

Mathematical Modeling of the Poly(lactic acid) Ring–Opening Polymerization Kinetics

The modeling of ring-opening polymerization of (D,L)-lactide to poly(lactic acid) (PLA) has been performed. Except some reported data on the apparent rate constant, there is lack of data in the literature on the rate constants for initiation, propagation and termination steps of PLA polymerization. Using a simple numerical technique, the individual rate constants are evaluated theoretically and the results are compared with the available experimental data for ring-opening polymerization of PLA. The proposed method works well without requiring a polymer chain length independent rate constant. It is also shown that presence of even small amount of impurity (e.g., water) in the reaction kettle can greatly limit the polymer molecular weight.

Synthesis of Poly(Lactic Acid): A Review

Poly(lactic acid), a bio‐degradable polymer, has been studied extensively during the past 15 years. This paper presents a review on poly(lactic acid) (PLA) with focus on its stereochemistry, synthesis via ring‐opening polymerization, reaction kinetics and thermodynamics, synthesis of low molecular weight polymer, a continuous process for production of PLA from lactic acid, and blends. The different polymerization mechanisms, which have been proposed in the literature, are also summarized. Various catalyst systems, solvents, and reaction temperature and time give products of an entire range of molecular weights, ranging from a few thousand to over a million. Modeling and simulation of the ring‐opening polymerization of PLA is also discussed.