Design of polylactide-grafted copolymeric stabilizer for dispersion polymerization of D,L-lactide

Poly(D,L-lactide) (PDLLA) microspheres with narrow diameter distribution were prepared by dispersion polymerization of D,L-lactide in xylene/heptane (1:2, v/v) using poly(dodecyl methacrylate)-g-poly(D,L-lactide) (PDMA-g-PDLLA) as a dispersion stabilizer. The particle diameters of PDLLA microspheres were controlled from 200 nm to 5 μm by altering the concentration and the graft chain number of PDMA-g-PDLLA. The effect of the copolymer composition on the particle diameter was investigated to clarify an important factor of the copolymer structure for the control of the particle diameter. As a result, it was necessary for anchor block in diblock copolymer as a dispersion stabilizer to have low solubility in the solution rather than the compatibility with particles. Moreover, we confirmed by dynamic light scattering measurement that PDMA-g-PDLLA formed micelles in the solution. In conclusion, it was clarified that PDLLA microspheres with a wide range of particle diameter were prepared due to the different kinetic stability of micelles.     

Role of dispersion stabilizer with hydroxy groups in preparation of monodisperse polylactide microspheres

Monodisperse poly(D ,L ‐lactide) (PDLLA) microspheres were prepared by dispersion polymerization of D ,L ‐lactide in xylene/heptane (1/2, v/v) with poly[(dodecyl methacrylate)‐co‐(2‐hydroxyethyl methacrylate)] (P(DMA‐co‐HEMA)) as a dispersion stabilizer. P(DMA‐co‐HEMA) contains hydroxy groups, which act as an initiation group for pseudoanionic dispersion polymerization. The best coefficient of variation (CV) values concerning particle diameter distribution and the particle diameter of obtained PDLLA microspheres were 3.7% and 5.3 μm, respectively. The particle diameter decreased with increasing concentration of P(DMA‐co‐HEMA) and HEMA maintained low CV (<10%) values. As a result, monodisperse PDLLA microspheres ranging from 1.3 to 5.3 μm were obtained. In addition, it was found that monodisperse PDLLA microspheres were obtained by sufficient capture of growing polymers and monomers in the particle growth stage. Therefore, the HEMA concentration in P(DMA‐co‐HEMA) strongly affecting the capturing capability is the most important factor. © 2009 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 47: 5230–5240, 2009     

Nonaqueous dispersion polymerization of styrene in methanol with the ionomer block copolymer poly[(4‐methylstyrene)‐co‐(4‐vinyltriethylbenzyl ammonium bromide)]‐b‐polyisobutene as a stabilizer

The nonaqueous dispersion polymerization of styrene in methanol with poly[(4‐methylstyrene)‐co‐(4‐vinyltriethylbenzyl ammonium bromide)]‐b‐polyisobutene as a stabilizer was investigated. There was no observable inducing period or autoacceleration in the polymerization process. The conversion increased almost linearly with the polymerization time as high as 80%. The average sizes of the obtained polystyrene particles increased, and the size distributions of the polystyrene particles tended to become narrower, with increasing conversion. The mechanism of the dispersion polymerization in the presence of polyisobutene‐b‐poly[(4‐methylstyrene)‐co‐(4‐vinyltriethylbenzyl ammonium bromide)] was nucleation/growth. When the stabilizer/monomer ratio (w/w) was greater than 2.0%, the polystyrene dispersion was stable, and there was no observable polymer particle coagulation taking place during the whole polymerization process. The average diameter of the polymer particles can be mediated through changes in the polymerization conversion, monomer, and stabilizer. Nearly monodispersed polystyrene particles with average diameters of approximately 0.45–2.21 μm were obtained under optimal conditions. © 2004 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 42: 2678–2685, 2004     

Mechanism of dispersion polymerization of L-lactide initiated with 2,2-dibutyl-2-stanna-1,3-dioxepane

 Biodegradable polyester microspheres were synthesized directly by ring-opening polymerization of l-lactide initiated with 2,2-dibutyl-2-stanna-1,3-dioxepane. The polymerizations were carried out at 95 °C in a mixture of organic solvents (heptane/1,4–dioxane 4:1 v:v), in the presence of poly(dodecyl acrylate)-g-poly(ɛ-caprolactone) used as a surface-active agent. Under these conditions the poly(L-lactide) synthesized was shaped into microspheres. The absence of new particles in the polymerizations with multistep monomer addition indicated that after the formation of particle seeds the propagation proceeds exclusively inside the microspheres. The mean volume of these microspheres was proportional to the monomer conversion. It was found that regardless of the initiator concentration the average number of poly(L-lactide) macromolecules in one microsphere was 1.84 × 10⁸. Matrix-assisted laser desorption ionization time of flight spectroscopy of poly(L-lactide) in the microspheres indicated that the propagation in the particles was accompanied by intra- and intermolecular transesterification side reactions, resulting in reshuffling of the polymer segments and the formation of cyclic oligomers. Received: 20 December 2000 Accepted: 7 June 2001     

Synthesis of polystyrene/SiO2 composite microparticles by dispersion polymerization in supercritical fluid

A novel synthetic route to prepare polystyrene/SiO₂ composite microparticles in supercritical carbon dioxide (scCO₂) is presented. Silica particles with the size of 130 nm which were surface-modified with 3-(trimethoxysilyl) propyl methacrylate were used as seeds in the dispersion polymerization of styrene in the presence of a polymeric stabilizer, poly(1,1-dihydroheptafluorobutyl methacrylate-co-diisopropylaminoethyl methacrylate) to produce dry composite particles. The transmission electron microscopy analysis revealed that the composite microspheres contained several silica particles.     

Thermal properties of amphiphilic biodegradable triblock copolymer of <Emphasis Type="SmallCaps">l</Emphasis>,<Emphasis Type="SmallCaps">l</Emphasis>-lactide and ethylene glycol

Samples of poly(l,l-lactide)-block-poly(ethylene glycol)-block-poly(l,l-lactide) (PLLA-PEG-PLLA) were synthesized from l,l-lactide polymerization using stannous 2-ethylhexanoate, Sn(Oct)₂ as initiator and di-hydroxy-terminated poly(ethylene glycol) (PEG) (M _n  = 4000 g mol⁻¹) as co-initiator. The chemical linkage between the PEG segment and the PLA segments was characterized by Fourier transform infrared spectroscopy (FTIR). Thermogravimetry analysis (TG) revealed the copolymers composition and was capable to show the deleterious effect of an excess of Sn(Oct)₂ in the polymer thermal stability, while Differential Scanning Calorimetry (DSC) allowed the observation of the miscibility between the PLLA and PEG segments in the different copolymers.     

Effects of dispersion stabilizer and reaction solvent on forming monodisperse polystyrene microspheres by dispersion polymerization

We used poly(aspartic acid) (PAsp) synthesized by ion exchange with sodium polyaspartate (PAspNa) as a dispersion stabilizer. PAsp improved the dispersion stability and the solubility in the medium for dispersion polymerization. The effects of the stabilizer hydrophobicity on particle formation, conversion, particle diameter, and its distribution of polystyrene microspheres were investigated by using both biodegradable polymers as a dispersion stabilizer. According to these results, we concluded that the polymerization rate of the styrene with PAsp was higher than that of styrene with PAspNa. That is why, smaller and more monodisperse microspheres were prepared with PAsp, compared to those with PAspNa.     

Synthesis of polyaspartate macromonomer having a vinyl end group and application to dispersion copolymerization of styrene

Sodium polyaspartate (PAspNa) macromonomer with an acryloyl end group was synthesized for dispersion polymerization. At first, a poly(succinimide) (PSI) derivative with a hydroxyphthalimide end group was synthesized by polycondensation of l-aspartic acid and 4-hydroxyphthalic acid. Then, the PSI derivative was end-capped with an acryloyl group by a reaction with acrlyloyl chloride. Finally, a PAspNa derivative with a vinyl end group was synthesized by a hydrolysis of succinimide units by sodium hydroxide. The synthesized macromonomer was applied as a polymerizable stabilizer in dispersion copolymerization of styrene in a mixture of ethanol and water. The PAspNa macromonomer acted as an effective stabilizer and gave sub-micron-sized polymeric particles in dispersion polymerization in polar medium.     

Living Polymerization of Lactide Using Titanium Alkoxide Catalysts

Several titanium isopropoxides have facilitated the ring opening polymerization of l-lactide (LA) and rac-lactide in toluene solution at various polymerization temperatures via a coordination insertion mechanism. Depending on catalysts, the controlled/living poly(l-lactide), or the heterotactic-biased poly(rac-lactide) were obtained. The stereochemical microstructure of polylactide (PLA) was determined from homonuclear decoupled ¹H NMR spectral studies. Such spectra of PLA derived from rac-LA featured the characteristic five-methine resonance pattern, whereas corresponding spectra derived from l-LA exhibited only one methine peak.     

Preparation of Monodisperse Polylactide Microspheres by Dispersion Polymerization Using a Polymeric Stabilizer with Hydroxy Groups

Monodisperse poly(D ,L ‐lactide) (PDLLA) microspheres have been prepared by dispersion polymerization of D ,L ‐lactide with a synthetic polymeric stabilizer. The polymerization is carried out in xylene/heptane (1:2, v/v) at 368 K for 3 h with poly[(dodecyl methacrylate)‐co‐(2‐hydroxyethyl methacrylate)] (P(DMA‐co‐HEMA)). P(DMA‐co‐HEMA) has hydroxy groups as an initiation group for pseudoanionic dispersion polymerization. The particle diameter and the coefficient of variation concerning the diameter distribution of the obtained PDLLA microspheres are 3.9 µm and 4.3%, respectively. In addition, from the results of dynamic light scattering measurements, it is found that P(DMA‐co‐HEMA) and the PDLLA‐grafted copolymer form a micellar structure in solution.

     

Synthesis of monodisperse polystyrene microspheres by dispersion polymerization using sodium polyaspartate

We prepared monodisperse polystyrene microspheres by dispersion polymerization using sodium polyaspartate (PAspNa) as a dispersion stabilizer in an ethanol/water medium. The influence of reaction parameters, i.e., the volume fraction of ethanol in the medium, stabilizer concentration, and the monomer concentration, on the average diameter of the prepared polystyrene microspheres and its distribution were investigated. Polystyrene microspheres were successfully prepared, and the average diameter of the prepared monodisperse polystyrene microspheres was controlled by adjusting the reaction parameters. The zeta potential of the microspheres and the time course of conversion, the particle diameter and its distribution, and particle numbers were also examined. It was found that PAspNa as a dispersion stabilizer provides an environmentally benign process for the preparation of monodisperse polymer microspheres by dispersion polymerization.     

Anionic dispersion polymerization. I. control of particle size

Studies on the mechanism for the formation of the stable dispersion polystyrene prepared by anionic dispersion polymerization of styrene in n-hexane using poly(t-butylstyrene) as the stabilizing moiety in steric stabilizer have been performed by a combination of size exclusion chromatographic (SEC) and transmission electron microscopic (TEM) analyses. When the molecular weight of poly(t-butylstyrene) as the stabilizing moiety exceeded 1.76 X 10⁴ g/mol, the formed polymer particles successfully retained a steric stability. Block copolymerization of t-butylstyrene and styrene in n-hexane has also provided the dispersion polymer particles with a relatively narrow size distribution. The stable dispersion polystyrenes have been produced in n-hexane by polymerization of styrene using the mixture of sec-butyllithium and poly(t-butylstyryl)lithium. The polymerization is called living dispersion polymerization (LDP), in which poly(t-butylstyrene-b-styrene) as the steric stabilizer and polystyrene can be formed simultaneously. The particle size was readily controlled by a combination of the concentration of monomer and the molar ratio of poly(t-butylstyryl)lithium to sec-butyllithium, for instance, [stabilizing moiety]/[RLi]. © 1996 John Wiley & Sons, Inc.     

Photoinitiated dispersion polymerization of methyl methacrylate: A quick approach to prepare polymer microspheres with narrow size distribution

Photoinitiated dispersion polymerization of methyl methacrylate was carried out in a mixture of ethanol and water as dispersion medium in the presence of poly(N‐vinylpyrrolidone) (PVP) as the steric stabilizer and Darocur 1173 as photoinitiator. 93.7% of conversion was achieved within 30 min of UV irradiation at room temperature, and microspheres with 0.94 μm number–average diameter and 1.04 polydispersity index (PDI) were obtained. X‐ray photoelectron spectroscope (XPS) analysis revealed that only parts of surface of the microspheres were covered by PVP. The particle size decreased from 2.34 to 0.98 μm as the concentration of PVP stabilizer increased from 2 to 15%. Extra stabilizer (higher than 15%) has no effect on the particle size and distribution. Increasing medium polarity or decreasing monomer and photoinitiator concentration resulted in a decrease in the particle size. Solvency of reaction medium toward stabilizer, which affects the adsorption of stabilizer on the particle surface, was shown to be crucial for controlling particle size and uniformity because of the high reaction rate in photoinitiated dispersion polymerization. © 2008 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 46: 1329–1338, 2008     

Preparation of polymer microspheres from solutions

Polymer microspheres are obtained by the dropwise addition of a precipitant, containing a polymeric stabilizer, into a polymer solution, containing a polymeric stabilizer. The polymer and stabilizer concentrations, the stirring speed, and the precipitation temperature determine the size and size uniformity of the microspheres. Seven polymer microspheres of polyimide, poly(ether imide), poly(ether ketone), poly(phenylene oxide), polysulfone, poly(vinylidene fluoride), and cellulose diacetate have been prepared with dimethylacetamide as the solvent, with water as the precipitant, and with poly(vinyl alcohol) as the stabilizer. The size and size uniformity of the obtained microspheres are d = 2.3–25.7 μm and ? = 0.15–0.50, respectively (? = σ/d, where ? is the dispersion coefficient, d is the average diameter, and σ is the standard deviation of the diameter). © 2002 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys 41: 159–165, 2003     

Magnetic poly(glycidyl methacrylate) microspheres prepared by dispersion polymerization in the presence of electrostatically stabilized ferrofluids

Fine magnetite nanoparticles, both electrostatically stabilized and nonstabilized, were synthesized in situ by precipitation of Fe(II) and Fe(III) salts in alkaline medium. Magnetic poly(glycidyl methacrylate) (PGMA) microspheres with core‐shell structure, where Fe₃O₄ is the magnetic core and PGMA is the shell, were obtained by dispersion polymerization initiated with 2,2′‐azobisisobutyronitrile (AIBN), 4,4′‐azobis(4‐cyanovaleric acid) (ACVA), or ammonium persulfate (APS) in ethanol containing poly(vinylpyrrolidone) or ethylcellulose stabilizer in the presence of iron oxide ferrofluid. The average microsphere size ranged from 100 nm to 2 μm. The effects of the nature of ferrofluid, polymerization temperature, monomer, initiator, and stabilizer concentration on the PGMA particle size and polydispersity were studied. The particles contained 2–24 wt % of iron. AIBN produced larger microspheres than APS or ACVA. Polymers encapsulating electrostatically stabilized iron oxide particles contained lower amounts of oxirane groups compared with those obtained with untreated ferrofluid. © 2004 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 42: 5827–5837, 2004     

Synthesis of polymeric microspheres from a Merrifield resin by surface‐initiated nitroxide‐mediated radical polymerization

Polymeric microspheres were prepared from a Merrifield resin via nitroxide‐mediated radical polymerization. Polystyrene, poly(acetoxystyrene), and poly[styrene‐b‐(methyl methacrylate‐co‐styrene)], poly(acetoxystyrene‐b‐styrene), and poly(styrene‐co‐2‐hydroxyethyl methacrylate) copolymers were demonstrated to graft onto 2,2,6,6‐tetramethyl‐1‐piperidinyloxy nitroxide bound Merrifield resins. The polymerization control was enhanced both on the surface and in solution by the addition of sacrificial nitroxide. The significant increase in the particle diameter (more than a fivefold volume increase for polystyrene brushes) showed that polymer growth was not only on the surface but also within the particles, and this diameter increase could be adjusted through changes in the molecular weight of the polymers. The microspheres were characterized by elemental analysis, IR spectroscopy, particle size analysis, and optical microscopy. © 2005 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 43: 2145–2154, 2005     

Preparation of polyvinylpyrrodione microspheres by dispersion polymerization

The preparation of polyvinylpyrrolidone (PVP) microspheres in ethyl acetate by dispersion polymerization with N-vinylpyrrolidone (NVP) as initial monomer, poly(N-vinylpyrrolidone-co-vinyl acetate) (P (NVP-co-VAc)) as dispersant, and 2, 2′-azobisisobutyronitrile(AIBN) as initiator is reported. The influences of monomer concentration, dispersant concentration and initiator concentration on the size of PVP microspheres as well as the monomer conversion were studied. The structure and properties of PVP microspheres were analyzed. The results show that the prepared PVP microspheres have a mean diameter of 3-4 μm. With an increase in NVP concentration, the size and the molecular weight of the PVP microspheres as well as the monomer conversion all increase. With increasing P(NVP-co-VAc) concentrations, the PVP molecular weight and monomer conversion both increase while the size of the microspheres becomes smaller. As the concentration of AIBN increases, the microsphere size and monomer conversion increase whereas the PVP molecular weight decreases. The PVP prepared by dispersion polymerization has a crystal structure, and its molecular weight is lower compared to that prepared by solution polymerization. __________ Translated from Acta Polymerica Sinica, 2007, 11 (in Chinese)     

Effect of reaction parameters on the dispersion polymerization of 1‐vinyl‐2‐pyrrolidone

Nonporous hydrogel microspheres 0.1–1.3 μm in diameter were prepared by the dispersion copolymerization of 1‐vinyl‐2‐pyrrolidone and ethylene dimethacrylate as a crosslinking agent. The crosslinking was evidenced by solid state ¹³C NMR and elemental analysis. The effect of various parameters including selection of solvent (cyclohexane, butyl acetate), initiator (4,4′‐azobis(4‐cyanopentanoic acid), 2,2′‐azobisisobutyronitrile, dibenzoyl peroxide) and stabilizer on the properties of resulting microspheres has been studied. Dynamic light scattering and photographic examination were used for determination of the diameter and polydispersity of microspheres. Increasing concentration of steric stabilizer in the initial polymerization mixture decreased the particle size. The particle size depended on the molecular weight of polystyrene‐block‐hydrogenated polyisoprene stabilizer, but not on the number of PS and polybutadiene blocks in the styrene–butadiene block copolymer stabilizers. Dibenzoyl peroxide used as an initiator resulted in agglomeration of particles. © 2000 John Wiley & Sons, Inc. J Polym Sci A: Polym Chem 38: 653–663, 2000     

Poly(N,N‐diethylacrylamide) microspheres by dispersion polymerization

Poly(N,N‐diethylacrylamide)‐based microspheres were prepared by ammonium persulfate (APS)‐initiated and poly(vinylpyrrolidone) (PVP)‐stabilized dispersion polymerization. The effects of various polymerization parameters, including concentration of N,N′‐methylenebisacrylamide (MBAAm) crosslinker, monomer, initiator, stabilizer and polymerization temperature on their properties were elucidated. The hydrogel microspheres were described in terms of their size and size distribution and morphological and temperature‐induced swelling properties. While scanning electron microscopy was used to characterize the morphology of the microspheres, the temperature sensitivity of the microspheres was demonstrated by dynamic light scattering. The hydrodynamic particle diameter decreased sharply as the temperature reached a critical temperature ～ 30 °C. A decrease in the particle size was observed with increasing concentration of both the APS initiator and the PVP stabilizer. The microspheres crosslinked with 2–15 wt % of MBAAm had a fairly narrow size distribution. It was found that the higher the content of the crosslinking agent, the lower the swelling ratio. High concentration of the crosslinker gave unstable dispersions. © 2008 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 46: 6263–6271, 2008     

Reactive poly(glycidyl methacrylate) microspheres prepared by dispersion polymerization

Poly(glycidyl methacrylate) [poly(GMA)] microspheres of narrow size distribution were prepared in a simple one‐step procedure by dispersion radical polymerization. Depending on the solvent used, poly(GMA) particle size could be controlled in the range of 0.5–4 μm by changing the solubility parameter of the reaction mixture. In N,N′‐dimethylformamide (DMF)/methanol mixture, the particle size increased and the size distribution broadened with decreasing initial solubility parameter. While in the DMF/methanol solvent system, hydroxypropyl cellulose (HPC) or cellulose acetate butyrate (CAB) were taken as steric stabilizers of the dispersion polymerization, poly(vinylpyrrolidone) (PVP) was used in alcoholic media. Contrary to the DMF/methanol system, narrow particle size distributions were obtained with PVP‐stabilized polymerizations in ethanolic, methanolic, propan‐1‐olic or butan‐1‐olic medium. Both the particle size and polydispersity were reduced with increasing stabilizer concentration. If lower molecular‐weight PVP was used, larger microspheres were obtained. Poly(GMA) samples prepared in a neat alcoholic medium virtually quantitatively retained oxirane group content after the polymerization. Reactivity of the poly(GMA) microspheres was confirmed by their hydrolysis and aminolysis. © 2000 John Wiley & Sons, Inc. J Polym Sci A: Polym Chem 38: 3855–3863, 2000