Polyester Particles Research Articles

Study of multivesiculated polyester particles synthesis by double emulsion process

This work studies the synthesis of multivesiculated particles (MVPs) from a w/o/w double emulsion comprising water and unsaturated polyester dissolved in styrene. These particles can be used as opacifying agents in paint formulations, due to light refraction within the air-containing voids, after water evaporation. The effect of some key variables was analyzed: time of dispersion and concentrations of added amine, polyester and protective colloids. The final products were characterized in terms of particle size distribution, vesicle morphology and dry film opacity. All the studied variables were shown to play a role in the quality of vesiculation. The underlying mechanisms were proposed, allowing for a better understanding of this sparsely studied process.

Effect of added amines on the morphology of multivesiculated polyester particles

Multivesiculated polyester particles (MVPs) are obtained by reticulation of a double emulsion system formed by a polyester/styrene solution dispersed in an aqueous colloidal solution. During its synthesis, the acid/base reaction between polyester carboxylic end groups and an added amine plays an important role in stabilizing the two emulsion systems (water‐in‐oil and oil‐in‐water). This work studies the influence of diethylenetriamine, aminoethylethanolamine, diethanolamine, and triethanolamine on MVPs' average particle size, vesiculation morphology, dry film opacity, and yellowing. The particular aspects observed for each amine are discussed, allowing identification of the relevant mechanisms taking place in the formation of MVPs. POLYM. ENG. SCI., 53:2261–2269, 2013. © 2012 Society of Plastics Engineers

Mechanical anisotropy in unidirectional glass fabric reinforced oligomeric siloxane modified polyester composites

In this study, the effect of incorporation of oligomeric siloxane into unsaturated polyester on mechanical behavior of unidirectional glass fiber/polyester composites has been investigated by means of tensile, flexural and short beam shear tests. The amount of oligomeric siloxane added into unsaturated polyester was in the range 1–3 % by weight of the glass fabrics. Mechanical tests were conducted at different angles (0 °, 45 °, and 90 °) with respect to fiber direction. The higher siloxane content exhibited a tendency to have greater tensile, flexural and interlaminar shear strength values in machine direction, bias direction and cross direction. From Scanning electron microscopy images, the presence of polyester particles on the unidirectional glass fiber surface confirmed better adhesion.

Protein-loaded PLGA–PEO blend nanoparticles: encapsulation, release and degradation characteristics

The aim of this work was to study the variables that affect the encapsulation and release of proteins from nanoparticles based on poly(lactic-co-glycolic acid; PLGA)–poloxamer and PLGA–poloxamine blend matrices, using bovine serum albumin (BSA) and immuno-γ-globulin (IgG) as model proteins. The nanoparticles were prepared by a solvent diffusion technique, and the studied variables were (1) PLGA molecular weight, (2) type of PEO-block copolymers, (3) protein loading, (4) pH and, (5) volume of the protein solution. Our results showed that the proteins can be efficiently incorporated into and released from the blend matrices. The type of the PEO derivative and the pH of the internal aqueous phase were the most important factors influencing protein encapsulation and release kinetics. Moreover, comparative degradation study of PLGA, PLGA–poloxamer and PLGA–poloxamine nanoparticles confirmed that the degradation and release characteristics of polyester particles can be improved by the incorporation of polyoxyethylene derivatives with different hydrophilia–lipophilia balance.

Approach to Formation of Multifunctional Polyester Particles in Controlled Nanoscopic Dimensions

We present the synthesis of discrete functionalized polyester nanoparticles in selected nanoscale size dimensions via a controlled intermolecular chain cross-linking process. The novel technique involves the controlled coupling of epoxide functionalized polyesters with 2,2'-(ethylenedioxy)bis(ethylamine) to give well-defined nanoparticles with narrow size distribution and selected nanoscopic size dimensions. Diverse functionalized polyesters, synthesized with pendant functionalities via ring-opening copolymerization of delta-valerolactone with alpha-allyl-delta-valerolactone, alpha-propargyl-delta-valerolactone and 2-oxepane-1,5-dione, were prepared as linear precursors which facilitated 3-D nanoparticles with functionalities such as amines, keto groups, and alkynes for post modification reactions. We found that the nanoparticle formation and the control over the nanoscopic dimension is primarily influenced by the degree of the epoxide entity implemented in the precursor polymers and the amount of 2,2'-(ethylenedioxy)bis(ethylamine) as cross-linking reagent. The other functionalities in the linear polyester do not participate in the nanoparticle formation and particles with defined functionalities can be prepared from batches of identical linear polymers containing various functionalities or by mixing different polyester materials to achieve controlled amounts of specific functional groups. The utilization of integrated functionalities was demonstrated in one post-modification reaction with N-Boc-ethylenediamine via reductive amination. This work describes the development of a novel methodology to prepare functionalized well-defined 3-D nanoparticle polyester materials in targeted nanoscopic ranges with amorphous morphologies or tailored crystallinities that offer a multitude of utilizations as a result of their unique properties and control in preparation.

Engineering Biodegradable Polyester Particles With Specific Drug Targeting and Drug Release Properties

Poly(lactic acid) (PLA) and poly(lactic-co-glycolic acid) (PLGA) microspheres and nanoparticles remain the focus of intensive research effort directed to the controlled release and in vivo localization of drugs. In recent years engineering approaches have been devised to create novel micro- and nano-particles which provide greater control over the drug release profile and present opportunities for drug targeting at the tissue and cellular levels. This has been possible with better understanding and manipulation of the fabrication and degradation processes, particularly emulsion-solvent extraction, and conjugation of polyesters with ligands or other polymers before or after particle formation. As a result, particle surface and internal porosity have been designed to meet criteria-facilitating passive targeting (e.g., for pulmonary delivery), modification of the drug release profile (e.g., attenuation of the burst release) and active targeting via ligand binding to specific cell receptors. It is now possible to envisage adventurous applications for polyester microparticles beyond their inherent role as biodegradable, controlled drug delivery vehicles. These may include drug delivery vehicles for the treatment of cerebral disease and tumor targeting, and co-delivery of drugs in a pulsatile and/or time-delayed fashion.

The Time Dependence of the Detachment Force of Ground Micrometer-Size Particles from a Planar Substrate: Effect of Particle Rotation

The time dependence of the detachment force applied to 7 µm ground polyester particles coated with silica nanoparticles was determined by ultracentrifugation. It was found that the force required to separate the particles from the substrate increased during the first 24 hours and changed very little thereafter. Scanning electron microscopy (SEM) results suggest that the increase in adhesion is due to the particles rotating from their initial positions obtained during deposition. The role of the silica nanoparticles in determining the time dependence of the detachment force is discussed in terms of the JKR and Fuller–Tabor models.

Biogenesis of Microbial Polyhydroxyalkanoate Granules: a Platform Technology for the Production of Tailor-made Bioparticles

Biopolyester (PHAs = polyhydroxyalkanoates) composed of hydroxy fatty acids represent a rather complex class of storage polymers synthesized by various eubacteria and archaea and are deposited as water-insoluble cytoplasmic nano-sized inclusions. These spherical shell-core particles are composed of a polyester core surrounded by phospholipids and proteins. The key enzymes of polyester biosynthesis and polyester particle formation are the polyester synthases, which catalyze the enantio-selective polymerization of (R)-hydroxyacyl-CoA thioesters to polyesters. Various metabolic routes have been identified and established in bacteria to provide substrate for polyester synthases. The role of the polyester synthases in morphogenesis and presumably self-assembly of these natural polyester particles will be described. Although not essential for particle formation, non-covalently attached proteins, the so-called phasins, can be found at the particle surface and are considered as structural proteins. A multiple alignment of 88 polyester synthases indicated an identity varying from 8% to 96% with eight strictly conserved amino acid residues. Protein engineering of polyester synthases and phasins was used to functionalize the polyester particle surface. The current knowledge enables the microbial and biocatalytic production of particles with controlled size, polyester core composition and surface functionality, which suggested numerous potential applications of these biocompatible and biodegradable nanostructures particularly in the medical field.

Time-Dependence of the Adhesion of Micrometer-Size Particles to Substrates: Correlation with Postdeposition Particle Rotation

The time dependence of the detachment force of 7-µm ground polyester particles coated with silica nanoparticles from a ceramer-coated substrate was determined by ultracentrifugation. The detachment force of the particles from the substrate was found to increase with the time since the particle deposition. Scanning electron microscopy (SEM) results show that, following deposition, the particles rotate at approximately the same scale as the observed increase in the detachment force. This suggests that the increase in adhesion may be due to particle rotation from their initial positions obtained upon deposition to a more stable position that results from torques generated by either electrostatic or van der Waals forces acting on the particles.

Effect of Young's Modulus on the Detachment Force of 7 μm Particles

The detachment force of ground, 7-microm-diameter polyester particles overcoated with clusters of silica having a cluster radius of approximately 100 nm from ceramer substrates with varying Young's moduli has been measured. It was found that the detachment force varied inversely with the Young's modulus of the ceramer. The results are attributed to the role of the silica, acting as asperities on the particles, and the degree of embedment of the particles into the substrate.

Encapsulation and Controlled Release of a Hydrophobic Drug Using a Novel Nanoparticle‐Forming Hyperbranched Polyester

An amphiphilic, hyperbranched polymer suitable for use in controlled drug delivery is reported. This polymer was obtained by modification of the hyperbranched aliphatic polyester Boltorn H20 (H20) with succinic anhydride and then glycidyl methacrylate, and formed nanoparticles in aqueous solution. The critical association concentration was 7.4 x 10(-3) g . L(-1), as determined by fluorescence spectroscopy using pyrene as a molecular probe. A static/dynamic laser light scattering (LLS) study revealed that the average particle size was 39.4 nm with a low particle size distribution (PDI=0.04), and that each particle was composed of about 350 amphiphilic molecules. Daidzein, a hydrophobic traditional Chinese medicine, was encapsulated during particle formation and the release properties were determined. The optimal feeding concentration of daidzein to hyperbranched polyester was 4.9 x 10(-5) g . mL(-1) to 5.0 x 10(-3) g . mL(-1) with a loading efficiency of 76.1%. In the presence of the enzyme Lipase PS, the drug loaded nanoparticles degraded in a random one-by-one manner and released the drug over a few days. This system is therefore a novel controlled drug release system based on nanoparticles formed of hyperbranched polyester. Encapsulation of daidzein by hyperbranched polyester particles.

Experimental study of particle trajectory in electrostatics powder coating process

Experimental studies of particle trajectory were conducted in an isolated Plexiglass coating booth. Polyester particles were injected with a Norsdon® electrostatics spray gun with a fixed distance from the gun to a grounded plate. Using a Dantec® Particle Dynamic Analyzer, the particle velocity and size distribution were measured simultaneously. The experimental results showed that the effect of electrostatics charging on the particle trajectory is strong in the close vicinity of the target, but can be neglected at locations away from the target. The influence on particle size and velocity profile due to the electric field between the charged particles and grounded target was weakened as more particles deposited on the target. When no charge is introduced on the coating powder, particle segregation is observed for particles larger than 100 μm. Particle gravitational settlement is noticed even near the gun tip. However, particle charging largely eliminates the segregation at a gun-to-target distance of 25 cm and helps break agglomerates formed in the spray system. The gun-to-target velocities of larger particles exhibited noticeable deviation from those of the flow field as the grounded target was approached. The study revealed that the onset of electrostatic coating is an important period that can affect the transfer efficiency and film thickness.

Enzymatic Polymerization towards Biodegradable Polyester Nanoparticles

AbstractThe direct enzymatic polymerization of miniemulsions consisting of lactone nanodroplets represents a new and convenient pathway for the synthesis of biodegradable polymer nanoparticles, where the chemical composition and molecular weight can be varied in a certain range. Oligoesters completely end‐capped with an alkene or diene group can also be prepared by this technique. These building blocks extend polyester application as they allow to impart improved biodegradability to both siloxane and resin chemistry.TEM image of the polyester particles obtained by enzymatic polymerization in miniemulsion.magnified imageTEM image of the polyester particles obtained by enzymatic polymerization in miniemulsion.

The Adhesion of Irregularly-shaped 8 μm Diameter Particles to Substrates: The Contributions of Electrostatic and van der Waals Interactions

The forces needed to remove irregularly-shaped, 8 μm diameter, polyester particles from a polyester substrate were measured using an ultracentrifuge. Measurements were also made on a second set of similar particles where nanometer-size silica clusters had been placed on their surfaces. These silica clusters acted as spacers, reducing direct contact between the particle and the substrate. It was found that the separation forces for the bare particles were consistent with predictions of the JKR theory of adhesion, but were much larger than could be accounted for from simple electrostatic interactions associated with either uniformly-charged particles or particles with localized charged patches. It was found, however, that the forces needed to effect separation decreased with increasing silica concentration. For particles with 2% by weight silica clusters on their surfaces, the separation force was only about 5% of the separation forces of the bare particles. At this concentration of silica, the estimates of the separation forces obtained from JKR theory, from the uniformly-charged model, and from the localized-charged-patch model are all about equal. The numerical estimates are consistent with the experimentally-obtained values.

Optimal performance of pneumatic transport systems

In order to improve the operation of pneumatic transport systems, we developed two techniques that can be employed on existing systems to increase their efficiency. These techniques can be applied on-line to a system striving toward optimal performance. As an application of the technique, a 0.10-m diameter conveying line transporting 1 mm polyester particles over a 30-m distance was employed. The first approach to optimal performance uses either constant inlet pressure conditions or constant solids throughput. The iso-pressure drop method is performed by operating this system at two state parameters at a constant pressure while the constant solids throughput employs a similar procedure. The two state parameters are pressure drop and either the gas mass flow rate or solids rate. By individual changes in these parameters, one can explore small variations around an operating point and develop an approximation to the derivative of the parameter. Extrapolation of the information to the optimal condition can be carried out pursuing the point where the derivative goes to zero. Expanding the data set refines the operation and produces a more exact optimal condition. The second approach to optimal performance utilizes a neural network description of the conveying phase diagram. Once the description is defined, optimization procedures can be applied to hone in on the optimal operating point. This procedure involves training the neural network, which sometimes requires a large database for accuracy. The present application shows the speed with which the network can be trained.

Epoxy and hydroxy functional polyolefin macromonomers

Methods for preparing saturated polyolefin oligomers with Si(SINGLE BOND)H, epoxy groups, and with dihydroxy groups have been developed. Anionic polymerization of butadiene, then termination of the chains with chlorodimethylsilane leads to controlled molecular weight oligomers with silane functionality, and wherein the microstructure can be tailored. Hydrogenation of these materials proceeds smoothly using colloidal nickel catalysts to yield the corresponding saturated materials, which are stable to conditions used for melt polyesterifications. Hydrosilation of allyl glycidyl ether with the Si(SINGLE BOND)H end groups produces epoxy functional oligomers, and subsequent hydrolysis of the epoxy rings yields oligomers with a dihydroxy group at one end. Melt copolymerization of the olefin macromers with 1,4-butanediol and 1,4-dimethylcyclohexanedicarboxylate in the presence of titanium isopropoxide affords poly(ester-g-olefin) graft copolymers. These copolymers are under study as model interfacial agents for polyester/polyolefin blends and as suspension agents for polyester particles in nonpolar media. © 1996 John Wiley & Sons, Inc.

Epoxy and hydroxy functional polyolefin macromonomers

Methods for preparing saturated polyolefin oligomers with Si(SINGLE BOND)H, epoxy groups, and with dihydroxy groups have been developed. Anionic polymerization of butadiene, then termination of the chains with chlorodimethylsilane leads to controlled molecular weight oligomers with silane functionality, and wherein the microstructure can be tailored. Hydrogenation of these materials proceeds smoothly using colloidal nickel catalysts to yield the corresponding saturated materials, which are stable to conditions used for melt polyesterifications. Hydrosilation of allyl glycidyl ether with the Si(SINGLE BOND)H end groups produces epoxy functional oligomers, and subsequent hydrolysis of the epoxy rings yields oligomers with a dihydroxy group at one end. Melt copolymerization of the olefin macromers with 1,4-butanediol and 1,4-dimethylcyclohexanedicarboxylate in the presence of titanium isopropoxide affords poly(ester-g-olefin) graft copolymers. These copolymers are under study as model interfacial agents for polyester/polyolefin blends and as suspension agents for polyester particles in nonpolar media. © 1996 John Wiley & Sons, Inc.

Synthesis of Bioerodible Poly(ε-caprolactone) Latexes and Poly(D, L-lactide) Microspheres by Ring-Opening Polymerization

Poly(ε-caprolactone) [poly(CL)] latexes and poly(D,L-lactide) [poly(D,L-Lc)] microspheres were prepared directly by ring-opening precipita tion polymerization carried out in heptane-dioxane (4:1 v/v) mixed solvent in the presence of poly(dodecyl acrylate)-g-poly(ε-caprolactone) used as the surface active agent. This designed synthetic method yielded latexes and microspheres with narrow size distribution; poly(CL) latex Dv/Dn = 1.038 and for poly(D,L- Lc) microspheres Dv/Dn = 1.15. (Dv and Dn denote the volume and number average diameters of particles.) The poly(CL) latex, synthesized by using CH3CH2OAl(CH2CH3) 2 as initiator, had a narrow polymer polydispersity of 1.11. Poly(D,L-Lc) microspheres, besides polymer with Mw/M n = 1.05 contained some unreacted lactide. Adsorption of human serum albumin and human gamma globulins on both kinds of polyester particles was studied for their potential use as polypeptide and protein delivery systems.

Determination of thermal parameters of non‐spherical particles in a packed bed from svstem response analysis in the time domain

AbstractThe thermal conductivity and the particle‐to‐fluid heat‐transfer coefficient for peanut‐shaped polyester particles in a packed bed were determined simultaneously using the pseudo‐random binary noise sequence (PRBNS) response technique. The modified Dispersion‐Concentric (D‐C) model was applied to beds packed with the non‐spherical particles. A time domain method, using the convolution integral, was developed for removing the effects of the bed ends and the transducer time lag on the experimental responses. Parameter estimation was performed in the time domain, using a simplex method to fit the thermal response calculated from the parametric D‐C model to the experimental response curve. The particle‐to‐fluid heat transfer coefficient in the bed was determined to be 106 W/m2. K at an interstitial fluid velocity of 2.0 m/s. The thermal conductivity of polyester was 0.22 W/m. K at 313 K.

Early results of the leeds–keio anterior cruciate ligament replacement

We report the two- to four-year results following the insertion of the Leeds-Keio prosthetic ligament for chronic anterior cruciate deficiency. Virtually all the 20 patients were less disabled by instability, but objective results were good or excellent in only two-thirds and under anaesthesia the pivot shift sign was still positive in half. Arthroscopic and histological assessment in 16 patients failed to show the development of a functional neoligament, and the common appearance of a synovitic reaction to polyester particles gave concern.