Highly monodisperse polymethylmethacrylate (PMMA) microparticles crosslinked with carboxylic group-containing urethane acrylates
(CUA) were produced by simple dispersion polymerization in methanol solution. In contrast to conventional crosslinkers, the
CUA employed as a crosslinker was excellent for maintaining the monodispersity of PMMA microparticles even at moderate crosslinker
concentrations (to about 5 wt%). It was believed that the CUA helped form the monomer-swellable surface of primary particles,
because of the structurally long tetramethylene oxide groups in the molecule. Carboxylic groups in the molecular backbone
resulted in larger primary particles by increasing the solubility of the monomer mixture in the medium. Owing to these larger
primary particles, the crosslinked PMMA particles showed lower polymerization rates than the linear ones during particle growth.
However, at high CUA concentrations (about 10 wt%), bimodal distributions were observed. This was attributed to the high crosslinking
density of the primary particle surfaces. Therefore, monomer diffusion toward the polymer phase was restricted, resulting
in more favorable secondary nucleation in the medium.
Received: 12 May 1998 Accepted: 19 August 1998 相似文献
Porous polymethyl methacrylate scaffolds were produced by phase separation during polymerisation in solution, using ethanol
as solvent, with monomer/ethanol weight ratios from 80/20 up to 20/80 and different ethylenglycol dimethacrylate contents
(1, 5 and 10 wt%) as crosslinker agent. For ethanol weight ratios equal to or lower than 50 wt%, the material presents a homogeneous
distribution of dispersed pores. For higher ethanol contents, a highly interconnected porous structure is obtained. The transition
from one type of morphology to the other can be also controlled with the amount of crosslinker added in the reactive mixture.
Bulk polymethyl methacrylate samples (non-porous) with the same crosslinking densities were also synthesised as reference.
The effect of crosslinker is studied by porosity measurements, scanning electron microscopy, dynamic-mechanical spectroscopy
and differential scanning calorimetry. 相似文献
In this communication, we report the first simple and fast one-step method for synthesizing highly monodisperse micron-size PMMA particles in organic media through dispersion polymerization in the presence of PHSA (a polyhydroxyl-stearic-acid graft PMMA copolymer) as a stabilizer. There are two significant advantages of our method over earlier methods. First, by optimizing the composition of a solvent mixture of hexane and dodecane, we were able to increase the concentration of monomer up to 50-56% and obtain unusually large (up to 10 mum in diameter) PMMA particles. Second, by strictly controlling the nucleation time, we were able to make PMMA particles with a low polydispersity of around 1%, much lower than has ever before been achieved for such large particles. We also report an unusual apparent metastable state in the nucleation stage. 相似文献
Atom transfer radical polymerization (ATRP) of MMA was conducted successfully at ambient temperature (25 °C) using 2-bromomethyl-4,5-diphenyloxazole as initiator, CuBr/2,2′-bipyridine (BPY) as catalyst, and 1,4-Dioxane as solvent. Factors such as the reaction temperature, mole ratio of monomer and catalyst to initiator, solvent and so on, which can affect the ATRP system, were discussed in the paper. Chain extension was conducted using polymer as the macro-initiator which was characterized via 1H NMR. The optical property of initiator was well preserved in the obtained PMMA, and the end-functionalized PMMA exhibited obvious fluorescent emission at 367 nm. 相似文献
Abstract Seed dispersion polymerization of methyl methacrylate (MMA) in the presence of monodisperse PMMA particles was carried out in an aqueous methanol using poly(methacrylic acid) stabilizer. The polymerization using 2. 5 μ. m-sized seed particles gave monodisperse PMMA particles in the diameter up to 4. 9 μm. The solvent composition and monomer concentration greatly affected the polymerization behavior. Under appropriate conditions, monodisperse PMMA particles in the diameter up to 8. 9 μ, m was prepared from 4. 6 μm-sized seed particles. The seed dispersion polymerization of styrene in the presence of the seed particles produced monodisperse PMMA-polystyrene particles in the micron range. The particles were supposed to have a structure consisting of PMMA-core and polystyrene-shell from ESCA analysis. 相似文献
The use of a new class of graft polymer surfactants, based on inulin, in emulsion polymerization of poly(methyl methacrylate) (PMMA) and polystyrene (PS) particles is described. PS and PMMA were synthesized by emulsion polymerization, and stable particles with a high monomer content (50 wt %) were obtained with a very small amount of polymeric surfactant ([surfactant]/[monomer] = 0.0033). The latex dispersions were characterized by dynamic light scattering and by transmission electron microscopy to obtain the average particle size and the polydispersity index, and the stability was determined by turbidimetry measurements and expressed in terms of critical coagulation concentration. The last section gives a comparison of PMMA particles prepared by emulsion polymerization using classical surfactants from different types as emulsifiers with that obtained using the copolymer surfactant. It shows the superiority of INUTEC SP1 as it is the only one that allows stable particles at 20 wt % monomer content, with a smaller ratio [surfactant]/[monomer] = 0.002. 相似文献
Summary: Radiation‐induced polymerization of methyl methacrylate (MMA) in ethanol (EtOH) and N,N‐dimethylformamide (DMF) in the presence of ionic liquid [Me3NC2H4OH]+[ZnCl3]− is reported. A substantial increase in monomer conversion and molecular weight is observed at room‐temperature ionic liquid (RTIL) >60 vol.‐%, and the resulting PMMA has a broad multimodal MWD. A clear difference in the MWD pattern is noted between EtOH/RTIL and DMF/RTIL systems, probably due to the complicated interactions between the solvent and ionic liquid.
Gel permeation chromatography traces of poly(methyl methacrylate) obtained by radiation polymerization in EtOH/RTIL and DMF/RTIL mixed solvent. Organic/RTIL (v/v): 1) 100:0; 2) 80:20; 3) 60:40; 4); 40:60; 5) 0:100. 相似文献
The effect of the weight ratio of seed polymer/monomer on the morphology of the poly(methyl methacrylate) (PMMA)/polystyrene
(PS) monodispersed composite particles produced by batch seeded dispersion polymerization of styrene with 1.64-μm-sized monodispersed
PMMA seed particles in a methanol/water medium (4/1 w/w) was examined. In the PMMA/PS weight ratios of 3/1 and 2/1, the composite
particles had a clear morphology consisting of a PMMA core and a PS shell. In the ratio of 1/1, a lot of small PS domains
were observed in the PMMA core though the PS shell was still formed. By stepwise addition of styrene monomer, the formation
of the small PS domain was depressed and complete core/shell morphology was formed. Absorption/release treatments of toluene
into/from the PMMA/PS (1/1 w/w) composite particles resulted in a drastic morphological change from the core/shell structure
to a multi- layered one.
Received: 2 February 1999 Accepted in revised form: 7 April 相似文献
The free-radical polymerization of 2,2,2-trifluoroethyl methacrylate (TEMA) was carried out in fluoroalcohols to achieve stereoregulation. The polymerization reactivity at low temperature and syndiotactic specificity were enhanced by the use of fluoroalcohol as a solvent. The polymer having triad syndiotacticity (rr) of 70% was obtained in perfluoro-t-butyl alcohol. It was noted that the stereochemistry was nearly independent of reaction temperature. The stereoeffect of fluoroalcohols seemed to be due to the hydrogen-bonding interaction between the alcohol and the monomer or growing species. The hydrogen-bonding formation was determined by FTIR. The copolymerization of TEMA with methyl methacrylate (MMA) in hexafluoroisopropanol afforded a copolymer with syndiotactic specificity. By this method, a cladding material for an optical fiber based on poly(methyl methacrylate) (PMMA) with high mechanical strength and low refractive index could be obtained. 相似文献
Poly(methylmetacrylate)/montmorillonite (PMMA)/(MMT) nanocomposites were prepared by one-step in situ intercalative solution polymerization involving simultaneous modification of MMT with quaternary ammonium salts (QAS), polymerization and polymer intercalation. Polymerization proceeded at 70 °C in a mixture of ethanol and water, whereas the nanocomposite was precipitated with only water. Four QAS’s with different alkyl chain lengths, as well as a QAS with an additional acrylic group, were used to study the influence of the type of quaternary ammonium salt on intercalation. The largest extent of intercalation was achieved in nanocomposites with the QAS having one long alkyl (C16) chain. The obtained PMMA/MMT intercalated nanocomposites exhibited a higher glass transition temperature, better thermal stability, and improved solvent resistance than the pure PMMA. 相似文献