Core–shell latex particles made of a poly(butyl methacrylate) (PBMA) core and a thin polypyrrole (PPy) shell were synthesized
by two-stage polymerization. In the first stage, PBMA latex particles were synthesized in a semicontinuous process by free-radical
polymerization. PBMA latex particles were labeled either with an energy donor or with an energy acceptor, in two different
syntheses. These particles were used in a second stage as seeds for the synthesis of the core–shell particles. The PPy shell
was polymerized around the PBMA core latex in an oxidative chemical in situ polymerization. Proofs for the success of the
core–shell synthesis were obtained using nonradiative energy transfer (NRET) and atomic force microscopy (AFM). NRET gives
access to the rate of polymer chain migration between adjacent particles in a film annealed at a temperature above the glass-transition
temperature Tg of the particles. Slower chain migration of the PBMA polymer chains was obtained with the PBMA–PPy core–shell particles compared
to rate of the PBMA polymer chain migration found with the pure, uncoated PBMA particles. This result is due to the coating
of PBMA by PPy, which hinders the migration of the PBMA polymer chains between adjacent particles in the film. This observation
has been confirmed by AFM measurements showing that the flattening of the latex film surface is much slower for the core–shell
particles than for the pure PBMA particles. This result can again be explained by the presence of a rigid PPy shell around
the PBMA core. Thus, these two complementary methods have given evidence that real core–shell particles were synthesized and
that the shell seriously hinders film formation of the particles in spite of the fact that it is very thin (thickness close
to 1 nm) compared to the size (750 and 780 nm in diameter) of the PBMA core. Transparency measurements confirm the results
obtained by NRET and AFM. When the films are placed at a temperature higher than the Tg of PBMA, the increase in transparency is faster for films made with the uncoated PBMA particles than for films made with
the coated PBMA particles. This result indicates again that the presence of the rigid PPy layer around the PBMA core reduces
considerably the speed at which the structure of the film is modified when heated above the Tg of PBMA.
Received: 02 September 1999 Accepted: 21 December 1999 相似文献
Three different styrene-butyl methacrylate copolymer latexes were prepared by a uniform procedure but introducing styrene
(S), butyl methacrylate (BMA), and minor amounts of acrylic acid (AA), in three different orders: i) simultaneous monomers
addition, which yielded {P(SBMA)}; ii) addition of S (and half of the AA) followed by BMA (and the remaining AA), yielding
{PS/PBMA} and iii) the inverse order, {PBMA/ PS}. Product characterization was done by centrifugation in density gradients
coupled to scattered light scanning photometry of the centrifugation tubes. IR and NMR spectra were obtained from bulk polymer
as well as from isopycnic centrifugation fractions. In agreement with findings of other authors, the particles produced by
simultaneous monomer addition {P(SBMA)} are made out of the statistical copolymer, whereas sequential monomer addition leads
to the formation of latex with homopolymer domains. IR and NMR spectra of {PS/PBMA} and {PBMA/PS} are identical but isopycnic
density band profiles of all three samples are distinct. Acrylic acid residues are not detected in the dialyzed latex, using
both IR and NMR. Spectra of latex isopycnic fractions do also show significant differences arising from their monomer chemical
compositions, but isopycnic centrifugation and spectral data do not reveal any correlation between particle density and monomer
composition. Isopycnic centrifugation can thus solve two problems on latex characterization: first, it is a high-resolution
preparative technique, unmatched by any other separation method. Second, it yields latex particle fingerprints, which are
dependent on particle chemical characteristics, rather than on particle diameters.
Received: 19 March 1996 Accepted: 29 August 1996 相似文献
Micron-sized mono-dispersed polystyrene (PS)/poly(n-butyl methacrylate) (PBMA) composite particles (PS/PBMA=2/1 by weight) having a heterogeneous structure in which many fine
PBMA domains dispersed in a PS matrix near the particle surface were produced by seeded polymerization of n-butyl methacrylate (BMA) of which almost all had been absorbed by 1.8 μm-sized monodispersed PS seed particles utilizing
the dynamic swelling method. The morphology was varied by changing the PS/BMA ratio and polymerization temperature. It was
concluded that the swelling state of 2 μm-sized BMA-swollen PS particles in the seeded polymerization process is one of the
important factors to control the morphology of the composite particles.
Received: 27 November 1996 Accepted: 21 March 1997 相似文献
Five poly(n-butyl methacrylate), PBMA, latex dispersions have been prepared, each incorporating a different fluorescent label, via a two-stage seeded emulsion polymerization. The resultant latices contain ca. 35% by weight total solids and are of 80 (+/-10) nm diameter as determined by photon correlation spectrometry. Luminescence spectroscopic techniques, namely fluorescence (and phosphorescence) excited state lifetime measurements in addition to time-resolved anisotropy experiments have provided useful information regarding the morphology, microviscosity and water permeability of the resultant particles. A picture of the PBMA colloid emerges of an interior which is highly viscous and water impermeable in nature. Indeed, the environment is protective enough to sustain room temperature stabilized phosphorescence from both an acenaphthylene and 9-phenanthrylmethyl methacrylate labeled dispersion through simple nitrogen purging of the solutions. However, the current spectroscopic measurements should be viewed with the knowledge that each luminescent label may fashion its own distinctive microenvironment within the latex during polymerization. 相似文献
Monodisperse homogeneous and core–shell latex particles of various sized between 200 and 600 nm were synthesized by emulsion copolymerization. Some of the core–shell particles were functionalized with epoxy groups at their peripheries upon introduction of glycidyl methacrylate (GMA) during the synthesis. The core consisted of crosslinked polybutylacrylate and the shell polymethylmethacrylate. Synthesis conditions at high and low temperatures were optimized to obtain coreshell particles with a well-defined morphology. The particles were characterized by quasi-elastic light scattering, scanning electron microscopy and transmission electron microscopy. The latex particles functionalized with GMA were then dispersed into a reactive matrix (styrene and maleic anhydride copolymer) using a batch mixer to obtain blends with well-defined and stabilized morphology. 4 Dimethylaminopyridine was used as a catalyst. The reaction between the epoxy groups at the particle surface and the maleic anhydride or diacid groups of the matrix was evaluated by torque and extraction techniques. A small amount of conversion generates sufficient amounts of grafted species at the matrix and particle interfaces to ensure a good interfacial adhesion. 相似文献
Fluorescence techniques (including time-resolved anisotropy measurements, TRAMS) have been used to probe differences in morphology between two stabilized aqueous latex dispersions (poly(n-butyl methacrylate), PBMA, and polyurethane, PU). Use of the emission characteristics of probes such as pyrene and phenanthrene dispersed within particles reveals that the PU latices are more heterogeneous in nature: evidence exists, particularly from quenching measurements and TRAMS, that voids and channels of water permeate the PU structure, resulting in a relatively soft, open particle, swollen by ingress of the bulk aqueous phase. Fluorescence measurements indicate that PBMA colloids, however, are composed of relatively hard, hydrophobic particles. In addition, TRAMS are considered to be a valuable tool both for probing the morphological characteristics of such dispersions and in estimating the average particle size. 相似文献
Micron-sized, monodispersed polystyrene (PS)/poly (n-butyl methacrylate) (PBMA) composite particles, in which the PS domain(s) were dispersed in a PBMA continuous phase, were
produced by seeded polymerization for dispersions of n-butyl methacrylate (BMA) swollen PS particles in a wide range of PS/BMA ratios in the presence of NaNO2 as a water-soluble inhibitor. Moreover, in order to change the diameter of the composite particles at same PS/BMA ratio,
PS/PBMA (1/150 w/w) composite particles were produced using five kinds of PS particles in a range of diameters from 0.64 to
3.27 μm as seeds. The percentages of the PS/PBMA composite particles having double and triple and over PS domains, which were
thermodynamically unstable morphologies, increased with the increase in the diameter of BMA swollen PS particles. There was
a clear influence of the size of the swollen particles on the morphology of the PS/PBMA composite particles produced.
Received: 30 September 1999/Accepted: 18 April 2000 相似文献
The preparation and characterization of polymer blends with structured natural rubber (NR)-based latex particles are presented. By a semicontinuous emulsion polymerization process, a natural rubber latex (prevulcanized or not) was coated with a shell of crosslinked polymethylmethacrylate (PMMA) or polystyrene (PS). Furthermore, core–shell latexes based on a natural rubber/crosslinked PS latex semi-interpenetrating network were synthesized in a batch process. These structured particles were incorporated as impact modifiers into a brittle polymer matrix using a Werner & Pfleiderer twin screw extruder. The mechanical properties of PS and PMMA blends with a series of the prepared latexes were investigated. In the case of PMMA blends, relatively simple core (NR)–shell (crosslinked PMMA) particles improved the mechanical properties of PMMA most effectively. An intermediate PS layer between the core and the shell or a natural rubber core with PS subinclusions allowed the E-modulus to be adjusted. The situation was different with the PS blends. Only core–shell particles based on NR-crosslinked PS latex semi-interpenetrating networks could effectively toughen PS. It appears that microdomains in the rubber phase allowed a modification of the crazing behavior. These inclusions were observed inside the NR particles by transmission electron microscopy. Transmission electron photomicrographs of PS and PMMA blends also revealed intact and well-dispersed particles. Scanning electron microscopy of fracture surfaces allowed us to distinguish PS blends reinforced with latex semi-interpenetrating network-based particles from blends with all other types of particles. 相似文献
The influence of solvent annealing on microscopic deformational behavior of a styrene/n-butyl acrylate copolymer latex film subjected to uniaxial tensile deformation was studied by small-angle X-ray scattering. It was demonstrated that the microscopic deformation mechanism of the latex films transformed from a nonaffine deformation behavior to an affine deformation behavior after solvent annealing. This was attributed to the interdiffusion of polymeric chains between adjacent swollen latex particles in the film. It turns out that solvent annealing is much more efficient than thermal annealing due to a much slow evaporation process after solvent annealing. 相似文献
Water dispersible latex particles with randomly mixed shells or chain segregated surface are synthesized from one‐pot reversible addition–fragmentation chain transfer heterogeneous polymerization of benzyl methacrylate (BzMA) using a mixture of poly(glycerol monomethacrylate) (PGMA) and poly(2,3‐bis(succinyloxy)propyl methacrylate) (PBSPMA) macromolecular chain transfer agents. In methanol, the two in situ synthesized PGMA‐b‐PBzMA and PBSPMA‐b‐PBzMA diblock copolymers coaggregate into spherical micelles, which contain PBzMA core and discrete PGMA and PBSPMA nanodomains on the shell. In contrast, in water–methanol mixture (V/V = 9/1), latex particles with homogeneous distribution of PGMA and PBSPMA polymer chains on the shell are obtained. The reasons leading to formation of latex particles with homogenous or chain‐segregated surface are discussed, and polymerization kinetics and physical state of PBSPMA in methanol and water–methanol mixtures are ascribed. These polymeric micelles with patterned functional group on the surface are potentially important for application in supracolloidal hierarchical assemblies and catalysis.
The effect of alkali-soluble resin (ASR), poly(ethylene-co-acrylic acid), EAA, postadded to emulsifier-free monodisperse
poly(butyl methacrylate) (PBMA) latexes on the kinetics of film formation was investigated using atomic force microscopy (AFM).
Corrugation height of latex particles in films was monitored at various annealing temperatures as a function of annealing
time. Enhanced polymer diffusion was found in a latex film containing ASR regardless of anneal-ing temperature. With increasing
annealing temperature, a much higher rate of polymer diffusion was found in latex films containing ASR. These results can
be interpreted that the low molecular weight and low Tg EAA resin adsorbed at the particle surface is more susceptible to
diffusion than that of the PBMA in the film formation stage, thus it enhances the mobility of PBMA polymer.
Received: 30 October 1997 Accepted: 20 March 1998 相似文献
Diblock copolymers containing polystyrene(PSt) and polybutyl methacrylate(PBMA) segments and random copolymer of styrene (St) and butyl methacrylate(BMA) have been prepared by atom transfer radical polymerization (ATRP).Diblock copolymers of BMA and St with predetermined molecular weight(1×10^4-6.5×10^4) and narrower molecular weight distribution(1.25-1.5) were obtained.The random copolymer compositions were determined by ^1HNMR spectroscopy and the reactivity ratios were evaluated by the extended Kelen-Tudos method to be YSt=0.91,YBMA=0.32. 相似文献
Micron-sized, monodisperse polystyrene (PS)/poly( n-butyl methacrylate) (PBMA) composite particles, in which PS domain(s) were dispersed in a PBMA continuous phase, were produced by seeded polymerization for the dispersion of highly n-butyl methacrylate (BMA)-swollen PS particles (PS/BMA=1/150, w/w) using various concentrations of benzoyl peroxide as initiator in the absence/presence of sodium nitrite (NaNO 2) as a water-soluble inhibitor. The percentages of the composite particles having double, triple and over PS domains, which were thermodynamically unstable morphologies, increased with a rapid increase of viscosity within the polymerizing particle. 相似文献