scholarly journals Flexible and rigid core molecules in the synthesis of poly(lactic acid) star polymers

2011 ◽  
Vol 89 (4) ◽  
pp. 499-505 ◽  
Author(s):  
Mitchell R. Perry ◽  
Michael P. Shaver
Keyword(s):  
Molecular Weight ◽  
Star Polymers ◽  
Gel Permeation Chromatography ◽  
Star Polymer ◽  
Poly Lactic Acid ◽  
Melt Crystallization ◽  
Scanning Calorimetry ◽  
The Core ◽  
Total Molecular Weight ◽  
The Individual

This study presents the synthesis and physical characterization of a series of structurally well-defined star-shaped poly(lactic acids). Polymer stars are prepared from a series of multifunctional alcohol cores including flexible polyols pentaerythritol and dipentaerythritol (four-armed and six-armed cores, respectively) and rigid substituted arenes tri(hydroxymethyl)benzene and hexa(hydroxymethyl)benzene. Utilizing a tin(II) octanoate catalyst, arms of 10 monomer units long are built from rac-lactide and l-lactide to form atactic and isotactic star polymers. Polymers were subsequently characterized by means of NMR spectroscopy, gel permeation chromatography, differential scanning calorimetry, and thermogravimetric analysis. Our results support previous work that suggests that the length of the individual arms, not the total molecular weight, correlates to physical characteristics including glass, melt, crystallization, and decomposition temperatures. In addition, differences between core molecules suggest that the chemical nature of the core can significantly alter the physical properties of the star polymer. Trends in crystallization and glass transition temperatures relative to the core used merit further study and correlate closest to the molecular weight and the number of arms emanating from the star core. It is also clear that the rigidity provided by aromatic cores has a significant effect on the melting temperatures of these macromolecules.

scholarly journals Poly(lactic acid) polymer stars built from early generation dendritic polyols

2013 ◽  
Vol 91 (6) ◽  
pp. 392-397 ◽  
Author(s):  
Genny E. Keefe ◽  
Jean-d'Amour K. Twibanire ◽  
T. Bruce Grindley ◽  
Michael P. Shaver
Keyword(s):  
Molecular Weight ◽  
Ring Opening ◽  
Gel Permeation Chromatography ◽  
Poly Lactic Acid ◽  
Reactive Site ◽  
Scanning Calorimetry ◽  
Early Generation ◽  
Sequential Reaction ◽  
Cyclic Esters ◽  
Total Molecular Weight

A family of polymer stars has been prepared from early generation dendritic cores with four, six, and eight arms. Four dendritic cores were prepared from the sequential reaction of a multifunctional alcohol with a protected anhydride, followed by deprotection to afford two or three new alcohol functionalities per reactive site. These cores were used as initiators for the tin-catalyzed ring-opening polymerization of l-lactide and rac-lactide to afford isotactic and atactic degradable stars, respectively. Two series of stars were prepared for each monomer, either maintaining total molecular weight or number of monomer units per arm. The polymers were characterized by NMR spectroscopy, light-scattering gel-permeation chromatography, differential scanning calorimetry, and thermogravimetric analysis. Our results support previous work that suggests that the length of the arms dictates thermal properties rather than the total molecular weight of the star. Little effect was noted between aromatic and aliphatic cores, presumably due to the flexibility of the rest of the core molecule. We have shown that early generation dendrimers can serve as excellent core structures for building core-first polymer stars via the ring-opening of cyclic esters.

scholarly journals Analysis of the Degradation During Melt Processing of PLA/Biosilicate® Composites

2019 ◽  
Vol 3 (2) ◽  
pp. 52 ◽  
Author(s):  
Eduardo H. Backes ◽  
Laís de N. Pires ◽  
Lidiane C. Costa ◽  
Fabio R. Passador ◽  
Luiz A. Pessan
Keyword(s):  
Molecular Weight ◽  
Gel Permeation Chromatography ◽  
Melt Processing ◽  
Poly Lactic Acid ◽  
Processing Route ◽  
Mechanical Resistance ◽  
Scanning Calorimetry ◽  
Oxidative Reactions ◽  
Bioactive Composites ◽  
Internal Mixer

Poly (lactic acid) (PLA)/bioactive composites are emerging as new biomaterials since it is possible to combine stiffness, mechanical resistance, and bioactive character of the bioglasses with conformability and bioabsorption of the PLA. In this study, PLA/Biosilicate® composites were prepared using a melt-processing route. The processability and properties were evaluated aiming to produce composites with bioactive properties. Two different PLA (PLA 2003D and PLA 4043D) were tested with the addition of 1 wt. % of Biosilicate®. Both materials presented a huge reduction in melt viscosity after internal mixer processing. The degradation effects of the addition of Biosilicate® in the PLAs matrices were evaluated using zeta potential tests that showed a very high liberation of ions, which catalyzes PLA thermo-oxidative reactions. To understand the extension of degradation effects during the processing, the composites were characterized using thermogravimetric analysis (TGA), differential scanning calorimetry (DSC), gel permeation chromatography (GPC), and rheological tests. GPC results showed that PLA with the lowest residual acid content (RAC), PLA 2003D, presented higher thermal stability, higher molecular weight, and viscosity baseline compared to PLA 4043D. The composites showed a significant decrease in molecular weight for both PLA with the addition of Biosilicate®. TGA results showed that Biosilicate® might have reduced the activation energy to initiate thermodegradation reactions in PLAs and it occasioned a reduction in the Tonset by almost 40 °C. The DSC results showed that severe matrix degradation and the presence of bioglass did not significantly affect glass transition temperature (Tg), melting temperature (Tm) and crystallinity of PLAs, but it influenced cold crystallization peak (Tcc). In this way, the type of PLA used influences the processability of this material, which can make the production of filaments of this material for 3D printing unfeasible.

The Influence of Amount of Succinic Anhydride in Chain Extension Reaction on Increasing Molecular Weight of Poly(lactic acid)

2013 ◽  
Vol 747 ◽  
pp. 148-152
Author(s):  
Chaichana Piyamawadee ◽  
Duangdao Aht-Ong
Keyword(s):  
Molecular Weight ◽  
Lactic Acid ◽  
Succinic Anhydride ◽  
Gel Permeation Chromatography ◽  
Chain Extension ◽  
Proton Nuclear Magnetic Resonance ◽  
Poly Lactic Acid ◽  
Condensation Polymerization ◽  
Scanning Calorimetry ◽  
Molar Ratios

High molecular weight PLA was successfully synthesized by chain extension reaction of hydroxylated prepolymer using succinic anhydride as a chain extender. Hydroxylated prepolymer was prepared by direct condensation polymerization of L-lactic acid in the presence of 1,4-butanediol. Various molar ratios between hydroxylated prepolymer and succinic anhydride (i.e, 1:1, 1:2, 1:3) were investigated. The results showed that succinic anhydride can help increasing molecular weight of hydroxylated prepolymer approximately up to 47% as characterized by gel permeation chromatography (GPC) technique. Proton nuclear magnetic resonance (1H-NMR) was used to investigate structure of chain-extended PLA. Differential scanning calorimetry (DSC) and thermogravimetric analysis (TGA) were used to examine thermal properties while the crystallinity was investigated by X-ray diffraction (XRD).

Synthesis of Poly(2-methyl-2-oxazoline) Star Polymers with a β-Cyclodextrin Core

2012 ◽  
Vol 65 (8) ◽  
pp. 1145 ◽  
Author(s):  
Guillaume Pereira ◽  
Cécile Huin ◽  
Simona Morariu ◽  
Véronique Bennevault-Celton ◽  
Philippe Guégan
Keyword(s):  
Molecular Weight ◽  
Ring Opening ◽  
Allyl Bromide ◽  
Star Polymers ◽  
Star Polymer ◽  
Kinetic Measurements ◽  
Hydrodynamic Volume ◽  
The Core ◽  
Initiation And Propagation ◽  
Propagation Kinetic

Synthesis of star polymers with a β-cyclodextrin (CD) core was undertaken using the arm-first, then the core-first strategy. Cationic ring opening polymerisation (CROP) of 2-methyl-2-oxazoline (MeOx) was first initiated by allyl bromide, and then quenched with heptakis(6-deoxy-6-amino)β-CD in order to get a 7-arm star polymer. Then heptakis(6-deoxy-6-iodo-2,3-di-O-acetyl)β-CD was synthesised in order to get an initiator for the CROP of MeOx. Initiation and propagation kinetic measurements were undertaken and the ratio kp/ki was found to be too high to provide a controlled polymerisation. Using iodine as co-initiator allowed a decrease of the kp/ki ratio that gave better control of the polymerisation. DOSY NMR and viscosity characterisations were undertaken, and both techniques lead to the demonstration of a lower hydrodynamic volume of the star polymers versus the linear counterparts, for compounds of the same molecular weight.

Processing and characterization of poly(lactic acid) blended with polycarbonate and chain extender

2014 ◽  
Vol 34 (7) ◽  
pp. 665-672 ◽  
Author(s):  
Yottha Srithep ◽  
Wuttipong Rungseesantivanon ◽  
Bongkot Hararak ◽  
Krisda Suchiva
Keyword(s):  
Molecular Weight ◽  
Lactic Acid ◽  
Gel Permeation Chromatography ◽  
Chain Extender ◽  
Chain Extension ◽  
Morphological Properties ◽  
Poly Lactic Acid ◽  
Scanning Calorimetry ◽  
Commercial Applications ◽  
A Chain

Abstract Currently, use of poly(lactic acid) (PLA) is limited for commercial applications because it has a low heat resistance. In this research, an increase of over 40°C heat distortion temperature (HDT) of PLA alloy was obtained by blending PLA with polycarbonate (PC) and a chain extender (CE). Molecular weight, thermal, mechanical and morphological properties of PLA and PC blend with different CE contents were investigated. Gel permeation chromatography (GPC) results showed that some PLA-PC copolymers were produced and the compatibility of the PLA phase and in the PC phase was improved via the chain extension reaction. In addition, the reaction induced by CE also affected the crystallization behaviors of PLA, as observed from differential scanning calorimetry (DSC) results and the enthalpy of melting of PLA decreased with increasing CE content. The combined effects of the CE increasing molecular weight, improving compatibility and limiting the crystallization behavior of PLA/PC alloy greatly improved the HDT.

scholarly journals Effects of Inorganic Fillers on the Thermal and Mechanical Properties of Poly(lactic acid)

2014 ◽  
Vol 2014 ◽  
pp. 1-8 ◽  
Author(s):  
Xingxun Liu ◽  
Tongxin Wang ◽  
Laurence C. Chow ◽  
Mingshu Yang ◽  
James W. Mitchell
Keyword(s):  
Mechanical Properties ◽  
Molecular Weight ◽  
Gel Permeation Chromatography ◽  
Mechanical Analysis ◽  
Poly Lactic Acid ◽  
Inorganic Filler ◽  
Homogeneous Distribution ◽  
Thermal And Mechanical Properties ◽  
Scanning Calorimetry ◽  
Tensile Tester

Addition of filler to polylactic acid (PLA) may affect its crystallization behavior and mechanical properties. The effects of talc and hydroxyapatite (HA) on the thermal and mechanical properties of two types of PLA (one amorphous and one semicrystalline) have been investigated. The composites were prepared by melt blending followed by injection molding. The molecular weight, morphology, mechanical properties, and thermal properties have been characterized by gel permeation chromatography (GPC), scanning electron microscope (SEM), instron tensile tester, thermogravimetric analysis (TGA), differential scanning calorimetry (DSC), and dynamic mechanical analysis (DMA). It was found that the melting blending led to homogeneous distribution of the inorganic filler within the PLA matrix but decreased the molecular weight of PLA. Regarding the filler, addition of talc increased the crystallinity of PLA, but HA decreased the crystallinity of PLA. The tensile strength of the composites depended on the crystallinity of PLA and the interfacial properties between PLA and the filler, but both talc and HA filler increased the toughness of PLA.

scholarly journals Methylene-Bridged Tridentate Salicylaldiminato Binuclear Titanium Complexes as Copolymerization Catalysts for the Preparation of LLDPE through [Fe]/[Ti] Tandem Catalysis

Polymers ◽  
2019 ◽  
Vol 11 (7) ◽  
pp. 1114 ◽  
Author(s):  
Yani Luo ◽  
Jian Li ◽  
Derong Luo ◽  
Qingliang You ◽  
Zifeng Yang ◽  
...  
Keyword(s):  
Molecular Weight ◽  
High Temperature ◽  
Gel Permeation Chromatography ◽  
13C Nmr Spectroscopy ◽  
Molar Ratio ◽  
Tandem Catalysis ◽  
Titanium Complexes ◽  
Scanning Calorimetry ◽  
Molecular Weights ◽  
Branching Degree

A novel tandem catalysis system consisted of salicylaldiminato binuclear/mononuclear titanium and 2,6-bis(imino)pyridyl iron complexes was developed to catalyze ethylene in-situ copolymerization. Linear low-density polyethylene (LLDPE) with varying molecular weight and branching degree was successfully prepared with ethylene as the sole monomer feed. The polymerization conditions, including the reaction temperature, the Fi/Ti molar ratio, and the structures of bi- or mononuclear Ti complexes were found to greatly influence the catalytic performances and the properties of obtained polymers. The polymers were characterized by differential scanning calorimetry (DSC), high temperature gel permeation chromatography (GPC) and high temperature 13C NMR spectroscopy, and found to contain ethyl, butyl, as well as some longer branches. The binuclear titanium complexes demonstrated excellent catalytic activity (up to 8.95 × 106 g/molTi·h·atm) and showed a strong positive comonomer effect when combined with the bisiminopyridyl Fe complex. The branching degree can be tuned from 2.53 to 22.89/1000C by changing the reaction conditions or using different copolymerization pre-catalysts. The melting points, crystallinity and molecular weights of the products can also be modified accordingly. The binuclear complex Ti2L1 with methylthio sidearm showed higher capability for comonomer incorporation and produced polymers with higher branching degree and much higher molecular weight compared with the mononuclear analogue.

scholarly journals Feasibility of Reprocessing Natural Fiber Filled Poly(lactic acid) Composites: An In-Depth Investigation

2017 ◽  
Vol 2017 ◽  
pp. 1-10 ◽  
Author(s):  
Sujal Bhattacharjee ◽  
Dilpreet S. Bajwa
Keyword(s):  
Lactic Acid ◽  
Natural Fiber ◽  
Environmental Concern ◽  
Wood Flour ◽  
Gel Permeation Chromatography ◽  
Thermomechanical Properties ◽  
Poly Lactic Acid ◽  
Filler Concentration ◽  
Scanning Calorimetry ◽  
Abrupt Decrease

Poly(lactic acid) (PLA) based composites are biodegradable; their disposal after single use may be needless and uneconomical. Prodigal disposal of these composites could also create an environmental concern and additional demand for biobased feedstock. Under these circumstances, recycling could be an effective solution, since it will widen the composite service life and prevent the excessive use of natural resources. This research investigates an in-depth impact of recycling on the mechanical and thermomechanical properties of oak wood flour based PLA composites. Two composite formulations (30 and 50 wt% filler), each with 3 wt% coupling agent (PLA-g-MA), were produced and reprocessed six times by extrusion followed by injection molding. Measurements of fiber length and molecular weight of polymer were, respectively, carried out by gel permeation chromatography (GPC). Scanning electron microscopy (SEM), differential scanning calorimetry (DSC), thermogravimetric analysis (TGA), and Fourier transform infrared spectroscopy (FTIR) tools were used to study morphological and molecular alterations. With consecutive recycling, PLA composites showed a gradual decrease in strength and stiffness properties and an increase in strain properties. The 50% and 30% filler concentration of fibers in the composite showed an abrupt decrease in strength properties after six and two reprocessing cycles, respectively.

Crystallization and Thermal Degradation of Green Nanocomposites Based on Lignin Coated Cellulose Nanocrystals and Poly(Lactic Acid)

2017 ◽  
Vol 737 ◽  
pp. 256-261 ◽  
Author(s):  
Martin Boruvka ◽  
Luboš Bĕhálek
Keyword(s):  
Lactic Acid ◽  
Cellulose Nanocrystals ◽  
Raw Material ◽  
Degree Of Crystallinity ◽  
Poly Lactic Acid ◽  
Crystalline Cellulose ◽  
Melt Crystallization ◽  
Scanning Calorimetry ◽  
Wide Range ◽  
Twin Screw

Cellulose is almost inexhaustible source of raw material comprising at least one-third of all biomass matter. Through deconstruction of cellulose hierarchical structure can be extracted highly crystalline cellulose nanocrystals (CNC) with impressive properties. However, the main barrier in the processing of the nanocomposites based on CNC is their inhomogeneous dispersion and distribution in the non-polar polymer matrix. In this paper is this problem addressed by use of novel hydrophobic lignin coated CNC as a biobased nucleation agents in poly (lactic acid) (PLA) nanocomposites. These green nanocomposites based on natural plant derived substances have enormous potential to replace materials originated from non-renewable resources and show promise of providing degradation back into the environment when they are no longer needed. Resulted composites prepared by twin screw extrusion and injection moulding were characterized by means of scanning electron microscopy (SEM), differential scanning calorimetry (DSC) and thermogravimetric analysis (TGA). The addition of L-CNC (1, 2 and 3 wt. %) into PLA increased melt crystallization enthalpy and decreases the cold crystallization enthalpy. The degree of crystallinity (cc) increased from 5.6 % (virgin PLA) to 8.5 % (PLA/1-L-CNC), 10.3 % (PLA/2-L-CNC) and 10.7 % (PLA/3-L-CNC). The wide range of degradation temperatures of lignin coating has been observed starting at 100 °C.

scholarly journals A Greener Enzymatic Oligoesterification of Biobased Renewable Synthons

2021 ◽  
Author(s):  
Juan Villavicencio ◽  
Ferley Orozco ◽  
Ricardo Benitez ◽  
Jaime Martin ◽  
Giovanni Rojas
Keyword(s):  
Molecular Weight ◽  
Molar Mass ◽  
Gel Permeation Chromatography ◽  
Scanning Calorimetry ◽  
Reaction Conditions ◽  
Step Process ◽  
Gel Permeation ◽  
One Step ◽  
First Time ◽  
Temperature Time

Polyesters of xylitol and succinic acid were prepared yielding from 70 to 75% by enzymecatalyzed esterification using a molar mass from 1:1 to 2:5 at 120 and 140 °C employing from 1 to 10% m/m of enzyme. Control over branching degree was achieved by tuning the reaction conditions (temperature, time, comonomer ratio, enzyme content). This one-step process from renewable starting materials avoids protection-deprotection techniques, as well as the use of toxic solvents by introducing limonene as solvent for polyesterification for the first time. All materials were structurally characterized by infrared (IR) and nuclear magnetic resonance (NMR)spectroscopy, their thermal properties were studied by differential scanning calorimetry (DSC)and thermogravimetric analysis (TGA), and the molecular weight of samples were obtained by gel-permeation chromatography (GPC).

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