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1.
A novel method to prepare organic/inorganic composite particles, i.e. poly(methyl methacrylate)/CaCO3/SiO2 three-component composite particles, using emulsion polymerization of methyl methacrylate with sodium lauryl sulfate as a surfactant in an aqueous medium was reported. CaCO3/SiO2 two-component inorganic composite particles were obtained firstly by the reaction between Na2CO3 and CaCl2 in porous silica (submicrometer size) aqueous sol and the specific surface area of the particles was measured by the Brunauer–Emmett–Teller (BET) method. The results show that the BET specific surface area of the CaCO3/SiO2 composite particle is much smaller than that of the silica particle, indicating that CaCO3 particles were adsorbed by porous silica and that two-component inorganic composite particles were formed. Before copolymerization with methyl methacrylate, the inorganic composite particles were coated with a modifying agent through covalent attachment. The chemical structures of the poly(methyl methacrylate)/CaCO3/SiO2 composite particles obtained were characterized by Fourier transform IR spectroscopy and thermogravimetric analysis. The results show that the surface of the modified inorganic particles is grafted by the methyl methacrylate molecules and that the grafting percentage is about 15.2%.  相似文献   

2.
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   

3.
The attempt to prepare structurally well-defined polymer/inorganic composite particles, i.e., poly(methyl methacrylate) (PMMA)/CaCO3/SiO2 three-component composite particles, via reverse atom transfer radical polymerization (ATRP), using 2-2′-azo-bis-isobutyronitrile as initiator and Cu(II) bromide as catalyst was reported. CaCO3/SiO2 two-component composite particles were first obtained through sol–gel method, and their morphology and surface element information were determined by transmission electron microscopy and X-ray photoelectron spectroscopy, respectively. The results indicate that the CaCO3 was encapsulated by the obtained SiO2. After being modified by silane coupling agent, the CaCO3/SiO2 composite particles copolymerized with methyl methacrylate (MMA) under standard reverse ATRP conditions to produce PMMA/CaCO3/SiO2 three-component composite particles. In the case concerned, first-order kinetic plots and linear increase of molecular weight (Mn) vs conversion and narrow molecular weight distribution for the graft polymer samples were observed. Furthermore, the gel permeation chromatography results illustrated that both the free PMMA chains from the solvent and the graft PMMA chains from the surface of CaCO3/SiO2 two-component composite particles were growing at the same rate. Characterizations of the PMMA-grafted CaCO3/SiO2 composite particles were done by Fourier transform infrared and thermogravimetric analysis. The results showed that the surface of the modified inorganic particles was grafted by the MMA and that the grafting percentage was about 8.7%.  相似文献   

4.
 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   

5.
In order to develop the seeded dispersion polymerization technique for the production of micron-sized monodispersed core/shell composite polymer particles the effect of polymerization temperature on the core/shell morphology was examined. Micron-sized monodispersed composite particles were produced by seeded dispersion polymerizations of styrene with about 1.4-μm-sized monodispersed poly(n-butyl methacrylate) (Pn-BMA) and poly(i-butyl methacrylate) (Pi-BMA) particles in a methanol/water (4/1, w/w) medium in the temperature range from 20 to 90 °C. The composite particles, PBMA/polystyrene (PS) (2/1, w/w), consisting of a PBMA core and a PS shell were produced with 2,2′-azobis(4-methoxy-2,4-dimethyl valeronitrile) initiator at 30 °C for Pn-BMA seed and with 2,2′-azobis(isobutyronitrile) initiator at 60 °C for Pi-BMA seed. The polymerization temperatures were a little above the glass-transition temperatures (T g) of both Pn-BMA (20 °C) and Pi-BMA (40 °C). On the other hand, when the seeded dispersion polymerizations were carried out at much higher temperatures than the T g of the seed polymers, composite particles having a polymeric oil-in-oil structure were produced. Received: 14 October 1998 Accepted in revised form: 2 June 1999  相似文献   

6.
Magnetic poly(methyl methacrylate) (PMMA)/poly(methyl methacrylate‐co‐methacrylic acid) [P(MMA–MAA)] composite polymer latices were synthesized by two‐stage soapless emulsion polymerization in the presence of magnetite (Fe3O4) ferrofluids. Different types and concentrations of fatty acids were reacted with the Fe3O4 particles, which were prepared by the coprecipitation of Fe(II) and Fe(III) salts to obtain stable Fe3O4 ferrofluids. The Fe3O4/polymer particles were monodisperse, and the composite polymer particle size was approximately 100 nm. The morphology of the magnetic composite polymer latex particles was a core–shell structure. The core was PMMA encapsulating Fe3O4 particles, and the shell was the P(MMA–MAA) copolymer. The carboxylic acid functional groups (COOH) of methacrylic acid (MAA) were mostly distributed on the surface of the composite polymer latex particles. Antibodies (anti‐human immunoglobulin G) were then chemically bound with COOH groups onto the surface of the magnetic core–shell composite latices through the medium of carbodiimide to form the antibody‐coated magnetic latices (magnetic immunolatices). The MAA shell composition of the composite latex could be adjusted to control the number of COOH groups and thus the number of antibody molecules on the magnetic composite latex particles. With a magnetic sorting device, the magnetic immunolatices derived from the magnetic PMMA/P(MMA–MAA) core–shell composite polymer latex performed well in cell‐separation experiments based on the antigen–antibody reaction. © 2005 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 43: 1342–1356, 2005  相似文献   

7.
In this paper, poly(MMA-M12-BPMA)/TiO2 composite particles were prepared by the copolymerization of a reactive surfactant sodium sulfopropyl-laurylmaleate (M12) and a reactive UV-stabilizer 2-hydroxy-4-(3-methacryloxy-2-hydroxylpropoxy) benzophenone (BPMA) with methyl methacrylate (MMA) in the presence of TiO2. The structure and performance of composite particles were characterized by Fourier transform infrared spectroscopy, thermogravimetric analysis, X-ray photoelectron spectroscopy, gel permeation chromatography, ultraviolet–visible absorption spectroscopy, differential scanning calorimeter, and scanning electron microscope.The measurement results indicate that the percentage of grafting and the grafting efficiency can reach 336.87% and 36.38%, respectively, and the glass transition temperature of poly(MMA-M12-BPMA)/TiO2 composite particles is higher than that of poly(MMA-M12-BPMA); the size of the composite particles is about 130–200 nm. The poly(MMA-M12-BPMA) grafted from the surface of TiO2 keeps the excellent characteristic of BPMA that possesses high absorbance of ultraviolet light, which is very important for improving UV-resistant performance of the polymethyl methacrylate. These research results are very useful for preparing polymethyl methacrylate with resistance to UV light.  相似文献   

8.
 Monodispersed polystyrene (PS)/poly(n-butyl methacrylate) (PBMA) composite particles having 9.4 μm in diameter were produced by seeded polymerization for the dispersion of highly n-butyl methacrylate (BMA)-swollen PS particles, and their morphologies were examined. The highly BMA-swollen PS particles (about 150 times the weight of the PS seed particles) were prepared by mixing monodispersed 1.8 μm-sized PS seed particles and 0.7 μm sized BMA droplets prepared with an ultrasonic homogenizer in ethanol/water (1/2, w/w) medium at room temperature. After NaNO2 aqueous solution as inhibitor was added in the dispersion, the seeded polymerization was carried out at 70 °C. In an optical microscopic observation, one or two spherical high contrast regions which consisted mainly of PS were observed inside PS/PBMA composite particles. In the PS domain, there were many fine spherical PBMA domains. Such morphologies were based on the phase separation of PS and PBMA within the homogeneous swollen particles during the seeded polymerization. Received: 04 June 1997 Accepted: 27 August 1997  相似文献   

9.
Fe3O4/SiO2/poly (N-isopropylacrylamide-co-N,N-dimethylaminoethyl methacrylate) [P(NIPAM-co-DMA)] multiresponsive composite microspheres with core–shell structure were synthesized by template precipitation polymerization. First, the magnetite nanoparticles were coated with silica and then modified with 3-(trimethoxysilyl)-propyl methacrylate (MPS). Subsequently, the Fe3O4/SiO2 particles grafted with MPS were used to seed the precipitation copolymerization of NIPAM and DMA. The composite microspheres with core–shell structure were superparamagnetic, pH-sensitive, and thermoresponsive. The swelling ratio (D25 °C, pH = 3/D50 °C, pH = 9)3 coupling of pH and temperature increased up to 21.2, which was much higher than that without comonomer DMA.  相似文献   

10.
Encapsulation of nickel oxide (NiO) particles is of great interest to the researchers as such modification produces remarkable improvement in properties and versatility in application potential. In this investigation, nanosized NiO particles were first prepared by calcination of nickel hydroxide precursor obtained using a simple liquid‐phase process. The produced NiO particles were stabilized with oleic acid and then treated with tetraethylorthosilicate to produce NiO/SiO2 composite seed particles. Finally tri‐layered inorganic/organic composite particles were prepared by seeded copolymerization of styrene and 2‐hydroxyethyl methacrylate (HEMA) in the presence of NiO/SiO2 composite seed particles. The produced composite particles named as NiO/SiO2/P(S‐HEMA) were colloidally stable, and the obtained particles were characterized by Fourier transform infrared spectroscopy, scanning electron microscopy, X‐ray diffraction, X‐ray photoelectron spectroscopy and thermogravimetric analyses. Copyright © 2015 John Wiley & Sons, Ltd.  相似文献   

11.
Summary: We previously discovered that structurally well-defined polymer/inorganic composite particles, i.e., poly(methyl methacrylate) (PMMA)/CaCO3/SiO2 three-component composite particles, can be achieved via reverse atom transfer radical polymerization (ATRP), using 2,2′-azo-bis-isobutyronitrile as initiator and CuII bromide as catalyst. In the present study, the influence of the mass ratio of CaCO3/SiO2 two-component composite particles to methyl methacrylate (MMA) on the rate and behavior of the polymerization was studied in detail. The results illustrate that increasing the mass ratio of CaCO3/SiO2 two-component composite particles will decrease the overall rate of polymerization of MMA under standard reverse ATRP conditions. Thermal properties of the obtained well-defined particles were characterized and determined by thermogravimetric analysis (TGA). The results indicate that well-defined PMMA chains grafted on the surface of CaCO3/SiO2 particles were only degraded by random chain scission of C C linkages within the PMMA chain, which is different from the degradation of PMMA chains prepared via traditional radical polymerization. This difference is reasonably ascribed to the difference between the end groups of PMMA prepared via reverse ATRP and that via traditional radical polymerization, which has been confirmed by end group analysis measured by 1H–NMR spectroscopy.  相似文献   

12.
We report a novel strategy for incorporation of titanium dioxide (TiO2) particles, which were crystallized from peroxotitanic acid in the presence of hydrophilic polymer by hydrothermal treatment in aqueous solution, into poly(methyl methacrylate) (PMMA) via dispersion into chloroform. Dispersion of TiO2 particles into chloroform was achieved by solvent change from water to chloroform in aid of amphiphilic polymer dispersant, poly(N-vinyl pyrrolidone) (PVP), poly(N-vinyl pyrrolidone-co-methyl methacrylate) (PVP-co-PMMA), poly(N-vinyl pyrrolidone-block-methyl methacrylate) (PVP-b-PMMA) through azeotropical removal of water. Incorporation of TiO2 particles into PMMA was carried out by a casting process of a mixture of TiO2 particles dispersed with PVP154-b-PMMA156 in chloroform and PMMA on a glass substrate. Resultant hybrid film containing TiO2 less than 10 wt.% showed high transparency in visible region attributable to homogeneous dispersion into PMMA matrix. The refractive index of the hybrid films increased with TiO2 content and agreed with the calculated values.  相似文献   

13.
Micrometer-sized, monodisperse, “hamburger-like” polystyrene (PS)/poly(2-ethylhexyl methacrylate)/decane composite particles were obtained by seeded dispersion polymerization of 2-ethylhexyl methacrylate with PS seed particles in the presence of decane. The morphological stability of the hamburger-like particles was investigated based on thermodynamic and kinetic aspects. The hamburger-like morphology was maintained at 60 °C (above glass transition temperature (T g)) for at least 1 week in spite of less thermodynamic stability than hemispherical morphology. T g of the particles gradually increased throughout the polymerization due to monomer consumption. Geometric calculation result indicates that the degree of reduction of the interfacial free energy at the early stage of the morphological development is significantly low. From these results, it is concluded the morphological stability of the hamburger-like particles is considerably high because the development from hamburger-like to hemispherical morphologies is retarded by the gradual increase in viscosity inside the particles and the significantly lower interfacial free energy reduction.  相似文献   

14.
Al(OH)3/PMMA nanocomposites were prepared by the emulsion polymerization of methyl methacrylate (MMA) in the presence of surface‐functionalized Al(OH)3 particles. Nanosized Al(OH)3 particles were previously functionalized with a silane coupling agent, 3‐(trimethoxysilyl) propyl methacrylate (γ‐MPS), which was confirmed by FT‐IR and XRF analysis. The average size of seed particles was around 70 nm, and the density of the coupling agent on the particles was calculated to be 8.9 µmol m?2. The emulsion polymerization was attempted at relatively high solid content of 40–46 wt%. The ratio of the seed particles to MMA had a strong influence on the stability of latex as well as the morphology of composites. Nanocomposites where several PMMA nodules were attached on the surface of Al(OH)3 core were produced with stable latex emulsion when the weight percents of Al(OH)3 to MMA were below 20. In the case of higher ratio of 30%, however, the latexes became unstable with an aggregation, and the product morphology was in the shape of large composite. Thermogravimetric analysis showed an improved thermal stability of PMMA composites with the incorporation of Al(OH)3 nanoparticles. Copyright © 2008 John Wiley & Sons, Ltd.  相似文献   

15.
In this study, the poly(NIPAAm–MAA)/Fe3O4 hollow latex particles were synthesized by three steps. The first step was to synthesize the poly(methyl methacrylate‐co‐methylacrylate acid) (poly(MMA‐MAA)) copolymer latex particles by the method of soapless emulsion polymerization. Following the first step, the second step was to polymerize N‐isopropylacrylamide (NIPAAm), MAA, and crosslinking agent (N,N'‐methylene‐bisacrylamide (MBA)) in the presence of poly(MMA‐MAA) latex particles to form the linear poly(MMA‐MAA)/crosslinking poly (NIPAAm‐MAA) core‐shell latex particles. After the previous processes, the core‐shell latex particles were heated in the presence of NH4OH to dissolve the linear poly(MMA‐MAA) core in order to form the poly(NIPAAm‐MAA) hollow latex particles. In the third step, Fe2+ and Fe3+ ions were introduced to bond with the ? COOH groups of MAA segments in the poly(NIPAAm‐MAA) hollow polymer latex particles. Further by a reaction with NH4OH and then Fe3O4 nanoparticles were generated in situ and the poly(NIPAAm‐MAA)/Fe3O4 magnetic composite hollow latex particles were formed. The concentrations of MAA, crosslinking agent (N,N'‐methylene bisacrylamide), and Fe3O4 nanoparticles were important factors to influence the morphology of hollow latex particles and lower critical solution temperature of poly(NIPAAm–MAA)/Fe3O4 magnetic composite hollow latex particles. © 2012 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem, 2012  相似文献   

16.
In this study, the poly(N‐isopropylacrylamide‐methylacrylate acid)/Fe3O4/poly(N‐isopropylacrylamide‐methylacrylate acid) (poly(NIPAAm‐MAA)/Fe3O4/poly(NIPAAm‐MAA)) two‐shell magnetic composite hollow latex particles were synthesized by four steps. The poly(methyl methacrylate‐co‐methylacrylate acid) (poly(MMA‐MAA)) copolymer latex particles were synthesized first. Then, the second step was to polymerize NIPAAm, MAA, and crosslinking agent in the presence of poly(MMA‐MAA) latex particles to form the linear poly(MMA‐MAA)/crosslinking poly(NIPAAm‐MAA) core–shell latex particles. Then, the core–shell latex particles were heated in the presence of NH4OH to dissolve the linear poly(MMA‐MAA) core to form the poly(NIPAAm‐MAA) hollow latex particles. In the third step, the Fe3O4 nanoparticles were generated in the presence of poly(NIPAAm‐MAA) hollow polymer latex particles and formed the poly(NIPAAm‐MAA)/Fe3O4 magnetic composite hollow latex particles. The fourth step was to synthesize poly(NIPAAm‐MAA) in the presence of poly(NIPAAm‐MAA)/Fe3O4 latex particles to form the poly(NIPAAm‐MAA)/Fe3O4/poly(NIPAAm‐MAA) two‐shell magnetic composite hollow latex particles. The effect of various variables such as reactant concentration, monomer ratio, and pH value on the morphology and volume‐phase transition temperature of two‐shell magnetic composite hollow latex particles was studied. Moreover, the latex particles were used as carriers to load with caffeine, and the caffeine‐loading characteristics and caffeine release rate of latex particles were also studied. © 2013 Wiley Periodicals, Inc. J. Polym. Sci., Part A: Polym. Chem. 2013, 51, 2880–2891  相似文献   

17.
Before polymerization, the introduction of double bonds onto the surface of the TiO2 particles was achieved by the treatment of the TiO2 particles with the silane-coupling agent. Via in-situ emulsion polymerization, the poly(methyl methacrylate) (PMMA)/titanium oxide (TiO2) composite particles were prepared by graft polymerization of MMA from the surface of the modified TiO2 particles. The structure of the obtained PMMA/TiO2 composite particles was characterized using fourier transform infrared spectra (FT-IR), thermo-gravimetric analysis (TGA), differential scanning calorimetry (DSC) and size excluding chromatography (SEC). The morphology of the obtained PMMA/TiO2 composite particles was observed by transmission electron microscope (TEM). The results of FT-IR and TGA measurements show that PMMA is successfully grafted from the surface of the TiO2 particles and that the percentage of grafting and the grafting efficiency can reach 208.3% and 96.6%, respectively. At the same time, the TGA and DSC measurements indicate an enhancement of thermal stability. TEM images demonstrate a better dispersion of the TiO2 particles in the composite latex. In addition, UV-visible absorption measurements show that the PMMA/TiO2 composite particles can absorb over 95% UV light at 210–400 nm wavelength.  相似文献   

18.
Near-monodisperse, siloxane-functionalised silica particles are used as a colloidal substrate for the surface-initiated polymerisation of various hydrophilic methacrylates: oligo(ethylene glycol) methacrylate (OEGMA), 2-(N-morpholino)ethyl methacrylate (MEMA), and ammonium 2-sulfatoethyl methacrylate (SEM) by atom transfer radical polymerisation in aqueous media at room temperature. The bulk and surface compositions of the resulting composite particles were assessed using various techniques. Thermogravimetric analysis of the resulting silica-polymer composites indicated polymer loadings of 5.4-8.6%, depending on the nature, structure and target degree of polymerisation (Dp). Dynamic light scattering studies indicate increases in hydrodynamic diameter of 14-87 nm compared to the reference silica particles. FT-IR spectroscopy confirmed additional features characteristic of the carbonyl group and pendant end-chain functionalities of the methacrylic polymer chains. The elemental and chemical surface compositions of the initial silica particles and final polymer-grafted composite particles were extensively investigated by X-ray photoelectron spectroscopy (XPS). The composite particles had appreciably higher C/Si atomic ratios, compared to the original initiator-functionalised silica particles, and these ratios increased with increasing target Dp. In addition, close inspection revealed that the relative intensities of the various components of the peak-fitted C1s envelopes varied significantly, depending on the target degree of polymerisation and the chemical structure of the methacrylic monomer. Moreover, in the case of the MEMA and SEM polymerisations, new nitrogen (MEMA) and sulfur (SEM) XPS signals were detected. This XPS study confirmed the presence of a thin outer layer of grafted polymer chains surrounding the silica particles.  相似文献   

19.
We describe the synthesis and characterization of latex particles labeled with a brightly fluorescent yellow dye (HY) based on the benzothioxanthene ring structure. Three dye derivatives were synthesized with different spacers connecting the HY nucleus to a methacrylate group. For one of the dyes (HY2CMA, rA), we show that the reactivity ratios with styrene (rA = 0.71, rB = 0.25) and butyl methacrylate (rA = 0.87, rB = 0.14) should lead to random dye incorporation if the amount of dye in the feed is small. Seeded emulsion polymerization fails to lead to significant dye incorporation unless large amounts of nonionic surfactant are present. In contrast, miniemulsion polymerization worked well to yield latex particles of polystyrene, poly(butyl methacrylate), and poly(methyl methacrylate) with high monomer conversion and essentially quantitative dye incorporation. © 2003 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 41: 766–778, 2003  相似文献   

20.
 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   

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