Dispersion polymerization of anionic polyacrylamide in an aqueous salt medium

Anionic polyacrylamide dispersions were prepared by dispersion polymerization in an aqueous salt medium, using acrylamide（AM） and acrylic acid（AA） as monomers and anionic polyelectrolytes as stabilizer. Effects of salt concentration, and molecular weight and concentration of stabilizers on the stability of the dispersions were investigated using a HAAKE rheometer and optical microscopy. The results showed that stable anionic polyacrylamide dispersions, consisting of smooth, spherical, polydisperse particles, could be obtained under the conditions of salt concentration ranging from 26 wt% to 30 wt%, concentration of stabilizers from 1.2 wt% to 1.8 wt%, and intrinsic viscosity of stabilizers from 2.98 dL·g^-1 to 3.74 dL·g^-1. The apparent viscosity of the stable dispersions changed very little with the shear rate, showing Newton fluid behavior.

MONODISPERSE MICRON-SIZED POLYACRYLAMIDE PARTICLES SYNTHESIZED BY DISPERSION POLYMERIZATION

Monodisperse micron-sized polyacrylamide （PAM） particles with a regular shape have been successfully prepared through dispersion polymerization of the monomer using a rotary reactor. FTIR and NMR spectroscopic results demonstrated the formation of PAM. POM and TEM observations revealed that PAM particles had a regular shape and good dispersity. A thick layer of surfactant （PVP） still existed on PAM particles after multiple centrifugation and ultrasonic re-dispersion in ethanol, which indicates a strong interaction between PVP and PAM. The effects of various polymerization factors on the average size of PAM particles have also been studied.

Preparation and Characterization of Non-porous Superparamagnetic Microspheres with Epoxy Groups by Dispersion Polymerization

Non-porous superparamagnetic polymer microspheres with epoxy groups were prepared by dispersion polymerization of glycidyl methacrylate (GMA) in the presence of magnetic iron oxide (Fe3O4) nanoparticles coated with oleic acid. The polymerization was carried out in the ethanol/water medium using polyvinylpyrrolidone (PVP) and 2,2’-azobisisobutyronitrile (AIBN) as stabilizer and initiator, respectively. The magnetic microspheres obtained were characterized with scanning electron microscopy (SEM), vibrating sample magnetometry (VSM) and Fourier transform infrared spectroscopy (FTIR). The results showed that the magnetic microspheres had an average size of-1μm with superparamagnetic characteristics. The saturation magnetization was found to be 4.5emu.g-1. There was abundance of epoxy groups with density of 0.028 mmol·g^-1 in microspheres. The magnetic PGMA microspheres have extensive potential uses in magnetic bioseparation and biotechnology.

The Surface Properties of PAVAc Prepared by Dispersion Polymerization in ScCO_2

Dispersion copolymerization of acryionitrile-vinyi acetate （AN-VAc） has been successfully performed in supercriticai carbon dioxide （ScCO2） with a series of iipophilic/CO2-philic diblock copolymers, such as poly（ styrener-acrylonitrile）-b- poly （ 1, 1, 2, 2-tetrahydroperfluorooctyl methacrylate） （PSAN-b-PFOMA）, as steric stabilizers. The structure and the particle morphology of the product were characterised by FT-IR and SEM. In addition, the effects of the stabilizer on the surface properties of the products were investigated in detail. Results indicate that the surface free energy of the poly （AN-r-VAc） （PAVAc） film decreases dramatically because of the existence of the stabilizer. And, when the initial concentration of the monomer was 10% （the mass （g） of monomer to the volume （mL） of ScCO2 ） the optimal concentration of the stabilizer is about 5% （w/w% to monomers）.

Preparation of Fe_3O_4/PS Magnetic Particles by Dispersion Polymerization

Fe_3O_4/PS magnetic particles with core/shell structure has been prepared in the presence of Fe3O4 magnetic fluid in ethanol/water mixture.Magnetic particles with diameter size range from 5. 54 t0 187. 32 μm were obtained by different reaction conditions.Some parameters such as ethanol, PEG and monomer which affect particle size diameter and size distribution are discussed briefly in this paper.

ATRP-Template Dispersion Polymerization of Methacrylic Acid/PVP

ATRP-template dispersion polymerization of methacrylic acid （MAA） on the template of polyvinyl pyrrolidone （PVP K-30） was carried out in the aqueous solution by using methyl 2-bromopropionate （MBP）/CuC1/2,2＇-bipyridine （bpy） as the initiation system. The scanning electron microscopy （SEM）, dynamic light scattering （DLS） and gel permeation chromatography （GPC） were employed for evaluating the results of polymerization. As a result, the minimonomer droplets formed due to the H-bond interaction of PVP-MAA. The stability of droplets was dependent on pH and the concentrations of both PVP and MAA. When pH 〈 2, the coagulum of PVP-MAA formed, whereas when pH 〉 4.5, the droplets were not observable by DLS. In order to prepare the stable latex, the concentration of PVP should be lower than 9 wt%, whilst the concentration of MAA should be lower than 5.5 wt%. The optimum condition was pH 2.4, PVP 4.76 wt% and MAA 5 wt%, by which the stable latex of ca. 50 nm nanoparticles of PMAA/PVP was prepared by ATRP polymerization and simultaneously the molar mass of PVP was duplicated by PMAA according to GPC diagrams. In contrast, by using AIBN, KPS and KPS-Na2SO3 redox initiation system, the coagulum accompanying with the larger molar mass of PMAA was obtained, irrespective of pH and concentrations of PVP and MAA.

In Situ Synthesis of Branched Block Copolymer Assemblies via RAFT Dispersion Polymerization Using Branched Macro-RAFT Agents

Here,we demonstrate the use of branched macromolecular reversible addition-fragmentation chain transfer (macro-RAFT) agents in RAFT dispersion polymerization,to access branched block copolymers as well as well-defined branched block copolymer assemblies.Two types of branched macro-RAFT agents were first synthesized by using either a monofunctional chain transfer monomer or a difunctional chain transfer monomer in RAFT polymerization,and subsequently utilized in RAFT dispersion polymerization.It was found that only branched macro-RAFT agents synthesized from the difunctional chain transfer monomer could lead to colloidally stable assemblies with well-defined morphologies.Reaction conditions including monomer concentration,degree of polymerization (DP) of the core-forming block,and DP of the solvophilic segment on morphologies of branched block copolymer assemblies were investigated in detail.Size exclusion chromatography (SEC) analysis further confirmed the successful formation of branched block copolymers by using branched macro-RAFT agents.This work on the synthesis of branched block copolymer assemblies by RAFT dispersion polymerization offers new opportunities for the rational design of polymer assemblies with well-defined structures.

Preparation of microsized crosslinked microspheres by dispersion copolymerization of polystyrene/polyethylene glycol 200-dimethacrylae

Dispersion copolymerization of styrene with polyethylene glycol 200-dimethacrylae as the cross-linking agent was completed by using poly（N-vinyl pyrrolidone） and 2,2-azo-bisisobutyronitrile as the steric stabilizer and initiator, respectively. Crosslinked copolymeric microspheres were prepared directly by the one-step method of dispersion copolymerization. The effects of the content of polyethylene glycol 200-dimethacrylae on the particle morphology and the copolymerization rate were investigated. It shows that the crosslinking agent plays an important role in the particle morphology and the system stability. When the content of crosslinking reached 2.5wt%, the floriated particles were obtained.

HIGH IMMOBILIZATION OF ANTIBACTERIAL MOIETIES ONTO MONODISPERSE MICROSPHERES BY DISPERSION POLYMERIZATION USING BICATIONIC VIOLOGEN SURFMER

In order to achieve monodisperse particles with high content of antibacterial groups covalently bonded on surface, a bicationie viologen, N-hexyl-N-（4-vinylbenzyl）-4,4＇-bipyridinium bromide chloride （HVV） was devised as a surfrner in dispersion polymerization of styrene （St） using a mixture of methanol （or ethylene glycol） and water as media. Effects of content of HVV, its addition profile and composition of reaction media on particles size and incorporation of HVV moieties were mainly investigated. The attachment of silver and gold nanoparticles on particle surface under UV irradiation ascertained the surface-bonded HVV segments. SEM, TEM observations and XPS, zata potential measurements indicated that increase of initial HVV contents and addition of HVV （when polymerization had been performed for 3 h） led to grown particles and enhanced immobilization of HVV moieties. Using a mixture of ethylene glycol and water as reaction media, small particles （520-142 nm） with highly attached HVV moieties were prepared. Furthermore, antibacterial efficacy of the resultant particles against S. aureus was assayed, and particles with more HVV moieties anchored on surface demonstrated greater efficiency of antibacterial activity.

CONTROLLED/"LIVING" RADICAL POLYMERIZATION OF STYRENE IN AN AQUEOUS DISPERSION SYSTEM

Atom transfer radical polymerization (ATRP) of styrene catalyzed by cuprous (CuX)/1,10-phenanthroline (Phen) and CuX/CuX2/Phen was conducted in an aqueous dispersed system. A stable latex was obtained by using ionic surfactant sodium lauryl sulfonate (SLS) or composite surfactants, such as SLS/polyoxyethylene nonyl phenyl ether (OP-10), SLS/hexadecanol and SLS/OP-10/hexadecanol, Among which SLS and SLS/OP-10/hexadecanol systems established better dispersed effect during the polymerization, It was found that Phen was a more suitable ligand than N,N,N',N',N'-pentamethyldiethylenetriamine (PMDETA) to maintain an appropriate equilibrium of the activator Cu(I) and the deactivator Cu(II) between the organic phase and the water phase, The effect of several initiators (such as EBiB, CCl4 and 1-PEBr) and the temperature on such a kind of ATRP system was also observed. The number-average molar mass (M-n) of polystyrene (PS) increased with the conversion and the molar mass distribution (M-w/M-n) remained narrow. These experimental data show that the polymerization could be controlled except for the quick increase of monomer conversion and the number-average molar mass of PS in the initial stage of polymerization. Furthermore, the initiator efficiency was found to be low (similar to57%) in CuX/Phen catalyzed system. To overcome this problem, Cu(II)X-2 (20 mol%-50 mol% based on CuX) was introduced into the polymerization system. In this case, higher initiator efficiency (60%-90%), low M-w/M-n of PS (as low as 1.08) were achieved and the molar masses of the PS fit with the theoretical ones.

Synthesis of crosslinked polystyrene particles by seeded batch polymerization with monomer absorption

A highly crosslinked, monodispersed polystyrene（PS） particle was prepared by a seeded batch dispersion polymerization with a monomer absorption method. Prior to polymerization, 1,9 lam monodispersed PS seed particles were treated under an optimum condition of monomer absorption. The effects of divinylbenzebe（DVB） concentration and polymerization temperature were examined for styrene（in PS seed）/styrene（in the second stage） mass ratio of 1：1 in the medium range of EtOH/water mass ratio of 100/0-80/20 and 2.3 μm uniform crosslinked PS particles containing 15%-20% （mass fraction） DVB were prepared at 60-70 ℃. The results show that monomer absorption before the second stage of polymerization is more effective to prepare highly crosslinked monodispersed PS particles.

Influence of polymer dispersants on dispersion stability of nano-TiO_2 aqueous suspension and its application in inner wall latex paint

The effects of SN5040 and polyethylene glycol（PEG） individually and in combination on the dispersion stability of nano-TiO2 aqueous suspension were investigated by ultraviolet-visible absorption spectroscopy. The adsorption mechanism of these dispersants was detected by zeta potential, isothermal absorption and FTIR analysis. It is found that SN5040 is superior for stabilizing nano-TiO2 in aqueous suspension to PEG in basic region, and the optimum mass fraction of SN5040 addition is 3%. In the case of NaCl addition, the optimum value increases with .the increase of NaCl concentration in the solution. When the mixture of SN5040 and PEG is employed, the antagonism appears preponderant. When SN5040 and PEG are added sequentially, the synergistic reaction takes place. The synergistic reaction can be attributed to the mechanism that PEG adsorption decreases the electronic repulsion between SN5040 molecules, which results in the increase of SN5040 adsorption density. PEG is adsorbed by the interaction with the pre-adsorbed SN5040 layer. Furthermore, the modified inner wall latex paint with well dispersed nano-YiO2 suspension is endowed with excellent ultraviolet absorption and antibacterial properties.

Preparation and Properties of Aqueous SCNTs Dispersion based on A UV-curable Polymeric Dispersant

A novel photosensitive copolymer P（SS-co-AA-g-GMA）（PSAG） was synthesized and utilized to noncovalently functionalize pristine single-walled carbon nanotubes（SCNTs）. PSAG was highly effective for the solubilization of SCNTs in water and validated by UV-vis absorption spectra experiments, resulting in homogeneous and stable PSAG-SCNT aqueous dispersion. The microstructure of SCNTs was observed through Raman spectroscopy and transmission electron microscopy. In addition, compared with the two common polymeric dispersants of Triton X-100 and PSS, PSAG demonstrated more effective performances for dispersing SCNTs under identical conditions. Furthermore, the photosensitive PSAG-SCNTs can be crosslinked after UV irradiation, leading to significant improvement in the water resistance of SCNT films. UV-cured films can be transferred to plastic wrap to form a flexible film with high electrical conductivity.

PREPARATION OF POLYMER DISPERSED LIQUID CRYSTALS USING PHOTOPOLYMERIZATION

2-Hydroxyethyl methacrylate (HEMA) and styrene copolymers are prepared by photopolymerization. The electrooptical behavior and microstructure of the polymer dispersed liquid crystal films are investigated by using He-Ne laser and scanning electron microscopy, respectively. With increasing E7 content in the copolymer, droplet size increased, threshold voltage decreased.

Phase Transition of Poly（acrylic acid-co-N-isopropylacrylamide） Core-shell Nanogels

A series of poly（acrylic acid） macromolecular chain transfer agents with different molecular weights were synthesized by reversible addition-fragmentation chain transfer （RAFT） poly- merization and characterized by 1^H NMR and gel permeation chromatography. Multiresponsive core-shell nanogels were prepared by dispersion polymerization of N-isopropylacrylamide in water using these poly（potassium acrylate） macro-RAFT agents as the electrostcric stabilizer. The size of the nanogels decreases with the amount of the macro-RAFT agent, indicating that the surface area occupied by per polyelectrolyte group is a critical parameter for stabilizing the nanogels. The volume phase transition and the zeta potentials of the nanogels in aqueous solutions were studied by dynamic light scattering and zetasizer analyzer, respectively.

Preparation of cationic polyacrylamide microsphere emulsion and its performance for permeability reduction

In this paper, cationic polyacrylamide microspheres （CPAM） were synthesized using acrylamide （AM） and methacryloyloxyethyl trimethyl ammonium chloride （TMAEMC） as monomers, ammonium sulfate as dispersant, poly（acryloyloxyethyl trimethyl ammonium chloride） （PAETAC） as dispersion stabilizer, and ammonium persulfate as initiator. The synthetic method was dispersion polymerization. The effects of monomer ratio （AM/TMAEMC）, dispersant concentration, and dispersion stabilizer dosage on dispersion polymerization were systematically studied to determine the optimal preparation conditions. The structure and viscosity of the synthesized polymer were characterized by FTIR and capillary viscometry, respectively, and the particle sizes and distribution of the polymer microspheres were characterized by microscopy and dynamic light scattering, respectively. Finally, flow tests were conducted to measure the permeability reduction performance of the microspheres at various concentrations in sand packs with different permeability. Results show that CPAM emulsion of a solids content of 1 wt% has excellent performance in low-to-medium permeability formations （〈 1,000 mD）, and the efficiency may reach above 90%.

Understanding Broad Polydispersity in Step-growth Polymerization via Catalyst Competition Mechanism

Conjugated polymers are mainly synthesized by cross-coupling polymerizations catalyzed with transition metal(Pd,Ni)catalysts through step-growth polymerization(SGP)mechanism.According to the classical theory of SGP,the polymer dispersion index(D)of the synthesized polymers will never be higher than 2.However,the cases where conjugated polymers synthesized with D value far exceeding 2 are very common in reality,which severely limits their processing property,performance and applications.To investigate the reason behind the D value deviation from the theoretical value of SGP,direct arylation polycondensation(DArP)of 2-bromo-3-hexylthiophene(3HT)was chosen as the model reaction,and the reaction process was tracked using gel permeation chromatography analysis.When Pd(OAc)_(2) was used as the catalyst,the D value linearly increased with the increase of the weight-average molecular weight(M_(w))of polymer(P3HT)after a short period and reached up to 7.2 at prolonged reaction time.Scanning transmission electron microscopic images of the reaction mixture showed the fibril-like aggregation of P3HT and assembling of Pd species in P3HT aggregates.A catalyst competition mechanism was thus proposed,together with numerical calculation,giving a good fitting to the experimental results,which is believed to have far-reaching significance for guiding the design,synthesis and processing of conjugated polymers.

Preparation of Core-shell Structured Particles and Their Nucleation in Polyester:I. Preparation of Monodisperse SiO_2/PS Core-shell Composite Particles

To enhance the nucleation and crystallization properties of polyester (e.g., polyethylene terephthalate, PET), core-shell structured particles are used to improve these properties by controlling the inorganic dispersion properties in the polymers. In the paper, monodisperse particles of silica/polystyrene (PS) are prepared with both dispersion and emulsion polymerization techniques. The monodisperse silicon dioxide particles are first prepared with the seed growth method and modified by the coupling agents. Silica is properly modified with KH-570, and its size deviation is 3.0% or so. The modified silica then reacts with the mixture of ethanol, water medium, and monomer of styrene under dispersion polymerization. Results show that the dispersion polymerization technique is more suitable for monodisperse core-shell SiO2/PS particles than that of the emulsion. The morphology and molecular structure of the core-shell particles are investigated with the transmission electron microscope (TEM), and fourier transform infra-red spectroscopy (FTIR). The results show that the modified silica particles are successfully encapsulated with polystyrene. The average number of silica particles encapsulated into each polystyrene sphere decreases when the size of silica particles increases from 50 nm to 600 nm, and will approach one when the silica is greater than 380nm in size. The mass ratio for silica/PS particles in emulsion polymerization is 4.7/1, lower than that of 6.8/1 for dispersion polymerization, which is the first reported optimized data for preparing the similar monodisperse composite particles. Thus, the PS shell in the former is thinner than that in the latter.

PREPARATION OF POLYMER PARTICLES WITH HIGH CONTENT OF MAGNETIC MATERIAL

A method for preparing polymer microspheres with high magnetic content is introduced.First of all,the ferrofluid prepared by co precipitation was treated with ethanol.Then,in the presence of the treated Fe 3O 4 particles,the dispersion polymerization of acrylamide was performed using poly (ethylene glycol) (PEG) as dispersant,AIBN as initiator,and ethanol as dispersing medium.The effects of the dispersing medium,the agitation intensity,the amount and properties of magnetic particles on the polymerization and magnetic content in the polymer microspheres are discussed.Finally,polyacrylamide particles having as high as 32.2% (by weight) magnetic Fe 3O 4 particles were prepared.

Electrically tunable holographic polymer templated blue phase liquid crystal grating

In this paper, we demonstrate an alternative approach to fabricating an electrically tunable holographic polymer tem- plated blue phase liquid crystal grating. This grating is obtained by preforming a polymer template comprised of periodic fringes, and then refilling it with a blue phase liquid crystal. Compared with conventional holographic polymer dispersed liquid crystal gratings, our grating can remarkably reduce its switching voltage from 200 V to 43 V while maintaining a sub-millisecond response time. The holographic polymer templated blue phase liquid crystal （HPTBPLC） grating is free from electrode patterning, thus leading to a lower cost and more flexible applications.