共查询到20条相似文献,搜索用时 15 毫秒
1.
Show-An Chen Herng-Show Chang 《Journal of polymer science. Part A, Polymer chemistry》1990,28(9):2547-2561
The emulsifier-free emulsion polymerizations of styrene in the presence of about 0.33–2.7% (relative to styrene) of the water soluble comonomer, 2-hydroxyethyl methacrylate (HEMA), and of the initiator, potassium persulfate (KPS), were carried out. It was found that KPS plays a predominant role in the particle nucleation process, since the number density of polymer particles (Np) was dependent on the 0.97-power of [KPS]. The nucleation ability of HEMA was weak, since Np was dependent only on the 0.17-power of [HEMA]. The particle nucleation stage ceased quite early before 1% conversion, leading to nearly monodispersed polymer particles. The nucleation is suggested to be via the homogeneous nucleation mechanism. The particles grow via the core-shell structure mechanism (shell region polymerization), since the particle size is rather large—from 1500 to 6000 Å. The amount of HEMA can affect the shell thickness and physical properties of the shell, such as the monomer swelling capacity and monomer diffusion rate. 相似文献
2.
Herng-Show Chang Show-An Chen 《Journal of polymer science. Part A, Polymer chemistry》1988,26(4):1207-1229
The emulsifier-free emulsion polymerizations of styrene in the presence of about 1 wt% (related to styrene) of the water soluble comonomer, sodium methallyl sulfonate (NaMS), which has short hydrophobic group and strong hydrophilic ionic group, and of the initiator, potassium persulfate, are carried out. Under constant ionic strength, the number density of polymer particles (Np) is found to depend on 0.5-power of the initiator concentration and shows a minimum in the comonomer concentration plot. Under constant concentration of monomer, comonomer and initiator, Np is found to depend on ?1.1-power of the ionic strength. In the earlier period, the presence of styrene oligomer having MW about 1000 and water soluble poly(NaMS) or copolymer with high NaMS content suggests a micellar nucleation mechanism, by which the styrene oligomer behaves as emulsifier and the poly(NaMS) can either stabilize or destabilize the existing particles, depending on its concentration in the aqueous phase. The particle size is rather uniform having an uniformity very close to 1 (ca. 1.001) throughout the entire process. It is much larger than that of the conventional emulsion polymerization or emulsifier-free emulsion polymerization with the other comonomers by about 3 to 4 times in diameter or 27 to 64 times in volume, leading to that the average radical number in the particle could be much greater than 0.5. The (conversion)2/3 versus time plot is found to be linear from 6 to 50% conversion. During this period, for the conversion from 10 to 40% the polymerization rate increases twice but the particle volume increases four-fold. In addition, MWD shows bimodal (excluding the styrene oligomer peak in the earlier period) during the growth period. But the lower MW peak shifts to higher MW and become larger, while the higher MW peak decreases, and finally the MWD becomes single mode after 58.6% conversion. These results suggest a “gradient polymerization” or “transition stage to core-shell structure” in the earlier stage of particle growth and a “shell part polymerization” in the later stage. 相似文献
3.
Mike Shi-Der Juang Irvin M. Krieger 《Journal of polymer science. Part A, Polymer chemistry》1976,14(9):2089-2107
Emulsion polymerization of styrene in the absence of emulsifier with K2S2O8 as initiator produced uniform latices. Incorporation of ca. 0.5% ionic comonomer (sodium styrenesulfonate) reduced the particle size from the range 0.5–1.0 μm achieved in prior emulsifier free formulations to a range of 0.15–0.40 μm. Some advantages achieved by incorporation of ionic comonomer were higher polymer content and independently controllable surface charge density. Particle diameter varied as the 0.64 power of the ratio of ionic strength to comonomer, as the ?0.20 power of initiator concentration, and as the 0.46 power of monomer content. Kinetic data suggest that copolymerization takes place in the aqueous phase, and that nuclei for particle growth are formed by precipitation of the initially water-soluble copolymer. The latex is stabilized by sulfonic acid groups of the comonomer, as well as by sulfate end groups from the initiator. 相似文献
4.
Show-An Chen Herng-Show Chang 《Journal of polymer science. Part A, Polymer chemistry》1992,30(10):2077-2083
For seeded emulsifier-free emulsion polymerizations of styrene/potassium persulfate (KPS)/water system using the three sizes of seeds: 1020, 1620, and 1923 Å, analysis on the data of conversion and MWD suggests a shell region polymerization mechanism for the particle growth period as the particle diameter is larger than about 1500–2000 Å. The shell region has thickness of about 100 Å. The occurrence of shell region polymerization is attributed to the higher average number of radicals per particle (n ? 2?7) for the large particle, causing the polymer radicals (with the sulfate ends anchoring on the particle surface) to be terminated by combination at lower MW. Thus, the radical ends have no chance to arrive at the core of the particles. As the smallest seed is used, the rate of polymerization is of zero order, the same as in the conventional emulsion polymerization. MW of the polymer produced in the cases, in which the shell region polymerization occurs, increases with conversion in the entire process, different from the conventional case in which the MW increases first up to about 60% conversion and then decreases. © 1992 John Wiley & Sons, Inc. 相似文献
5.
Cui'e Yan Shiyuan Cheng Linxian Feng 《Journal of polymer science. Part A, Polymer chemistry》1999,37(14):2649-2656
The emulsifier-free emulsion copolymerization of styrene (St) and methyl methacrylate (MMA) in the presence of functional monomer acrylic acid (AA) was carried out in batch process. The kinetics was investigated in detail using model function, Integrated Gamma Function. The morphology and size of particles were monitored continuously by TEM all along the polymerization. It was found that the nucleation, polymerization rate increase with increasing concentration of the functional monomer AA, initiator ammonium persulfate (APS), and polymerization temperature T, and APS plays a predominant role in the particle nucleation process. The particle nucleation stage ceased at about 10% conversion and the steady stage can be extended to about 70% conversion. The particle nucleation is likely to yield primary particle via the mechanism of homogeneous coagulative nucleation and coagulation of the primary particle to yield uniform particles. The particle growth in the postnucleation stage is via a shell growth mechanism. © 1999 John Wiley & Sons, Inc. J Polym Sci A: Polym Chem 37: 2649–2656, 1999 相似文献
6.
For the emulsifier-free emulsion copolymerization of styrene with the water-soluble comonomer 4-vinylpyrindine (4VP), and
using ammonium persulfate as an initiator, the kinetics, the content of 4VP, the molecular weight and the molecular weight
distributions of the polymer at various conversions, and particle morphologies have been investigated. Based on the results
obtained, the particle nucleation mechanism was discussed.
Received: 9 September 1998 Accepted in revised form: 23 February 1999 相似文献
7.
The emulsifier-free emulsion copolymerization of styrene and tetrahydrofurfuryl methacrylate (TMA) in aqueous phase is described.
Monodisperse latex particles with diameters from about 280 to 620 nm are obtained consisting of a hydro-phobic polystyrene
core and a hydrophilic poly-TMA shell. The influence of a variation of TMA, styrene and initiator (potassium persulfate) concentration
in the original emulsion on particle size, molecular weight and composition of the copolymer is described. The concentration
of TMA and initiator affects the number of primary particles but not the size of the final particles, whereas the styrene
concentration strongly influences the particle diameter, a large size being favored by a high styrene concentration. The molecular
weights of the polymers are between 6.2×104 and 7.0×105 g/mole. Size exclusion chromatography of polymer solutions in tetra-hydrofuran shows that high molecular weights are especially
found in large particles, which are preferentially formed in emulsions with a high concentration of styrene. 1H-NMR spectroscopy of the polymer shows that only about 50% of the initial TMA concentration are polymerized in the particles.
Thus the copolymers prepared at increasing styrene concentration and constant initiator concentration of the emulsion show
an increasing polystyrene content and are formed in particles of increasing size.
Received: 4 June 1997 Accepted: 19 August 1997 相似文献
8.
9.
Gottfried Lichti Brian S. Hawkett Robert G. Gilbert Donald H. Napper David F. Sangster 《Journal of polymer science. Part A, Polymer chemistry》1981,19(4):925-938
Data are presented on the time evolution of particle-size distributions (PSDs) in seeded and ab initio styrene emulsion polymerization systems. Initiation was by chemical reagent (potassium persulfate) or γ-radiation. The unswollen PSDs at various times during interval II of the polymerization were obtained by direct measurement of calibrated electron micrographs. Experimental results were fitted with the equations that describe the time evolution of an initial PSD. Analytic solutions to these equations that allow for entry, exit, and propagation of free radicals were obtained. The values of the rate coefficients for these processes used to fit the experimental data were in excellent agreement with those obtained from dilatometric kinetics experiments. 相似文献
10.
David F. Wood Barry C. Y. Whang Donald H. Napper Robert G. Gilbert Gottfried Lichti 《Journal of polymer science. Part A, Polymer chemistry》1983,21(4):985-997
The results are reported of studies on the kinetics and the time evolution of the particle size distribution in seeded styrene emulsion polymerization systems wherein the seed latex particles were highly swollen with monomer as a result of prior swelling by dodecane. Conditions were such that no new latex particles were formed nor was a significant number of monomer droplets present (“Interval III”). The data were fitted to obtain values for the rate coefficients for entry and exit (desorption) of free radicals. It was found that, during the early part of the polymerization (when the polymer:monomer ratio in the latex particles is considerably less then in an equivalent emulsion polymerization system without dodecane), the entry rate coefficient was much smaller than that measured in systems without dodecane. This effect is consistent with an entry mechanism wherein entering free radicals must displace surfactant molecules from the latex particles. 相似文献
11.
The hydrophobic monomer dodecafluoroheptyl methacrylate has been copolymerized with hydrophilic monomer methacrylic acid in aqueous solution without any additional emulsifier used via a two-step polymerization process of RAFT. The FTIR and GPC results indicated that amphiphilic copolymers with a narrow molecular weight distribution and well-defined blocks have been synthesized successfully. And the copolymers are likely to form steady micelles in the emulsion. Indicated by TEM, it is clear that micelles with a diameter of 70-120 nm have been formed. Despite a content of 22 wt% of hydrophilic carboxyl, films formed by casting the emulsion onto the baseplate can be hydrophobic after heating treatment. 相似文献
12.
Polytetrafluoroethylene (PTFE)/polyacrylate core-shell nanoparticles were produced via the emulsifier-free seeded emulsion
polymerization of acrylate monomers with PTFE latex as seed. The monomer conversions under different synthesis parameters
were monitored by a gravimetric method. The polymerization conditions for preparing PTFE/polyacrylate core-shell nanoparticles
were surveyed and optimized. The chemical component of the PTFE/polyacrylate particles was confirmed by comparing the Fourier-transform
infrared spectra of PTFE and PTFE/polyacrylate particles. The core-shell structure of the resulting PTFE/polyacrylate nanocomposite
particles was investigated by transmission electron microscopy. The water contact angles of the films prepared from PTFE/polyacrylate
nanocomposite particles showed that the films were hydrophilic, which confirmed that polyacrylate covered the surface of the
PTFE particles. This kind of PTFE/polyacrylate core-shell nanoparticles might advance the compatibility of PTFE with other
materials due to the covering of the polyacrylate shell on the surface of PTFE, which would make them promising in various
fields. 相似文献
13.
J. Ugelstad P. C. Mrk J. O. Aasen 《Journal of polymer science. Part A, Polymer chemistry》1967,5(9):2281-2288
The quantitative theory of the free-radical mechanism in emulsion polymerization is reexamined. A mechanism involving desorption and reabsorption of radicals is discussed. The average number of radicals per particle has been calculated as a function of three parameters. A simplified, approximate solution for the average number of radicals per particle is given for cases where this number is low. 相似文献
14.
Experiments were carried out to investigate the effects of surface charge density on emulsion kinetics and secondary particle
formation in emulsifier-free seeded emulsion polymerization. Three monodisperse seed latices with different surface charge
densities were prepared from styrene/NaSS comonomers using the two-stage shot-growth process. After purification of the seed
latices, they were used in seeded emulsion polymerization of methyl methacrylate. The initial rate of poly-merization and
the average number of radicals per particle for the high-charged seed latex system were lower than that of the low-charged
case. The low rate of polymerization resulted from the low rate of radical adsorption in the beginning of the reaction due
to the electrical repulsion between seeds and oligomeric radicals. In this case, because of the secondary particles, particle
size distribution became bimodal. The low rate of radical adsorption and the formation of secondary particles reduced the
average number of radicals per particle. The rate of polymerization (R
p) increased, but the rate of polymerization per particle (R
p/N
p) decreased.
Received: 9 December 1996 Accepted: 7 March 1997 相似文献
15.
16.
Preparation of polystyrene latex particles by γ-rays-induced emulsifier-free emulsion polymerization
《Radiation Physics and Chemistry》2006,75(9):1001-1005
Monodisperse polystyrene latex particles were prepared by 60Co-γ-ray radiation-induced emulsifier-free emulsion polymerization with the use of surfactant monomer at room temperature. The surfactant monomer 10(9)-hydroxyl-9(10)-allyl ether octadecanoic acid (HAEOA) was synthesized and characterized by FT-IR and 1H-NMR spectra. TEM was used to characterize the polystyrene latex particles. HAEOA acted as not only a comonomer but also a stabilizer to copolymerize with styrene and stabilize the polystyrene latex particles. Kinetics analysis shows that there is no constant rate stage which seems to indicate a droplet nucleation mechanism. 相似文献
17.
18.
Particle formation in polymerization of styrene induced within two stratified layers of a monomer and water containing an initiator was studied in the absence of emulsifiers and stirring. A polymerization-induced decrease of interfacial surface tension was observed. The particle size distribution was characterized by dynamic light scattering during polymerization. The results confirm particle nucleation through spontaneous emulsification process. 相似文献
19.
Peter Harriott 《Journal of polymer science. Part A, Polymer chemistry》1971,9(4):1153-1163
The emulsion polymerization of vinyl acetate has generally been considered a special type of reaction that is not covered by the Smith-Ewart theory. Although the number of particles depends on coalescence rates and can not be predicted by this theory, the polymerization rate data are consistent with the general concepts of Smith and Ewart, including reaction primarily inside swollen polymer particles, escape of radicals from particles, and termination of chains inside the particles. Allowing for rapid exchange of radicals following chain transfer leads to a simple equation which fits much of the published data for cases of both very low and very high values of n , the average number of radicals per particle. 相似文献
20.
The polymerization of styrene with novel catalytic systems of anilido-imino nickel complexes (Ar1N = CHC6H4NAr2) NiBr (Ar1 = Ar2 = 2,6-dimethylphenyl, 1; Ar1 = 2,6-dimethylphenyl, Ar2 = 2,6-diisopropylphenyl, 2; Ar1 = Ar2 = 2,6-diisopropylphenyl, 3; Ar1 = 2,6-diisopropylphenyl, Ar2 = 2,6-dimethylphenyl, 4) activated by methylaluminoxane was investigated. The influence of reaction parameters (temperature, Al/Ni mole ratio, and polymerization time) on styrene polymerization was evaluated. The influence of the bulkiness of the substituents on polymerization activity and polymer characteristics was also ascertained. The obtained polystyrene was an iso-rich atactic polymer and its weight-average molecular weight reached 70 500. NMR analysis of the end groups further confirmed that styrene polymerization catalyzed by anilido-imino nickel complexes/MAO systems proceeded through a coordination mechanism, and the chain was initiated through styrene secondary insertion into the NiH and terminated mainly through β-H elimination of styrene producing the chain-end group (CHCHPh). 相似文献