Influences of Electrolytes on the Soap-free Emulsion Copolymerization of St-MMA-AA

Monodisperse functional polymer microspheres with different particle size and with clean surface were prepared by batch soap-free emulsion polymerization of styrene, methyl methacrylate and acrylic acid in the presence of salts, and the influences of type and amount of electrolytes on polymerization process and particle morphology were investigated. Results showed that there was a critical concentration for different electrolyte to make polymerization process and the resultant emulsion stable, and the particle size increased with the increase of electrolyte concentration. The effect of metal ions was Ca^2＋〉〉K^＋〉Na^＋〉Li^＋, and the effect of haloids was Br〉Cl〉F. Keywords： Electrolyte, soap-free emulsion polymerization, polystyrene, latex particle morphology.

Synthesis and Characterization of Poly (Methyl Methacrylate)/Polyethylenimine Grafting Core-Shell Nanoparticles for CO2 Adsorption Using Soap-Free Emulsion Copolymerization

Unlike previous emulsion polymerization, we used grafting reactions in soap-free emulsion systems. In this study, we synthesized grafted PMMA/PEI core-shell nanoparticles by varying the MMA/PEI content and molecular weight of PEI (Mn = 600, 8000, and 10,000). The size and morphology of the core-shell nanoparticles were characterized by a particle size analyzer and scanning electron microscopy. The nanoparticles were 178 - 408 nm in diameter and swelled in water or methanol by 30 - 75 nm. The size of the nanoparticles increased with MMA contents, whereas the size distribution progressively became homogeneous with increasing molecular weight of PEI. Lastly, we measured CO2 adsorption capacity of the grafted PMMA/PEI core-shell nanoparticles, and we found the capacity to be limited at a level of 0.69 mg, which occurred for nanoparticles prepared from emulsions at a pH value of 11.

CATALYTIC COPOLYMERIZATION OF STYRENE AND ETHYLENE BY NEUTRAL NICKEL(Ⅱ) COMPLEXES IN EMULSION

Emulsion copolymerization of styrene and ethylene catalyzed by a series of neutral nickel(Ⅱ) complexes was carried out in an aqueous system to give high-molecular-weight copolymers.The copolymers and emulsions were characterized by an array of techniques including NMR,GPC,TEM,WAXD and DSC.The results indicate that the copolymers obtained are mostly block copolymers of polyethylene with random insertion of styrene units,and their M_W is in the range of 10~5-10~6.By enhancing the electron withdrawing of the s...

PREPARATION AND CHARACTERIZATION OF AFFINITY POLYMER BASIC MICROSPHERES BY SOAP-FREE EMULSION POLYMERIZATION

Poly(styrene-co-glycidyl methacrylate) latex microspheres with uniform size and high-density epoxy groups on the surface were prepared by soap-free emulsion polymerization with batch wise operation mode in the presence of 2.2′- azobis(2-methylpropionamidine) dihydrochloride as an initiator.The kinetics of soap-free emulsion polymerization and the effects of polymerization factors were examined.In addition,the optimum polymerization conditions of poly(styrene-co- glycidyl methacrylate) latex microspheres for...

Preparation of Self-crosslinked Fluorocarbon Polymer Emulsion with Core-shell Structure by the Method of Soap-free Emulsion Polymerization

Using methyl methacrylate （MMA）, butyl acrylate（BA） and hexafluorobutyl acrylate（HFBA） as main raw materials, we prepared self-crosslinked fluorocarbon polymer emulsion with core-shell structure via soap-free emulsion polymerization when the conception of particle design and polymer morphology was adopted. Moreover, the influence of mole ratio of BA to MAA, pH value on the oligomer was studied. And the effects of the added amount of oligomer, self-crosslinked monomer and HFBA, mass ratio of BA to MMA, reaction temperature and the initiator on the polymerization technology and the performance of the product, were investigated and optimized. The structure and performance of the fluorocarbon polymer emulsion were characterized and tested with FTIR, TEM, MFT and contact angle and water absorption of the latex film. The experimental results show that the optimal conditions for preparing fluorocarbon polymer emulsion are as follows： for preparing the oligomer, tool ratio of BA to MAA is equal to 1.0 ： 1.60, and pH value is controlled within the range of 8.0 and 9.0; for preparing fluorocarbon polymer emulsion, the added amount of oligmer[P（BA/MANa）] is 6%; mass ratio of BA to MMA is 40 ＂ 60; the added amount of self-crosslinked monomer is 2%, the added amount of HFBA is 15 %; reaction temperature is 80 ℃; the mixture of potassium persulfate and sodium bisulfite is used as the initiator. The film-forming stability of the fluorocarbon polymer emul- sion and the performance of the latex film, which is prepared with the soap-free emulsion polymerization, are better than that prepared with the conventional emulsion polymerization.

INFLUENCES OF ACID POST-TREATMENT ON THE MORPHOLOGY OF SOAP-FREE P(MMA-EA-MAA)PARTICLES PREPARED BY SEEDED EMULSION POLYMERIZATION

Soap-free poly（methyl methacrylate-ethyl acrylate-methacrylic acid） latex particles with narrow size distribution were synthesized by seeded emulsion polymerization, and the porous particles were created by a stepwise alkali/acid treatment method. Effects of acid treatment conditions on the particle morphology were investigated. Results show that one to three pores were formed inside most of particles after post-treatment. At pH 7.0, when the treatment temperature was lower than 70℃, the size of particles and the volume of pores remained almost unchanged, and these two values increased significantly when the temperature was higher than 70℃. Both the particle size and the pore volume decreased with the increase of initial pH value and treatment time in the acid treatment. As the pH was below 4.0 and the treatment time was longer than 180 min, the particles shrunk in size.

SOAPLESS EMULSION COPOLYMERIZATION IN THE PRESENCE OF BARIUM SULFATE POWDER

To investigate soapless emulsion copolymerization in the presence of a solid phase, copolymerization experiments were carried out for the styrene-butyl acrylate-K_2S_2O_8-water system by using barium sulfate powder,which is assumed to be chemically inert.Reaction conditions were varied with respect to barium sulfate powder quantity,initiator concen- tration and temperature.These factors were investigated with respect to the effect on reaction rate and conversion,polymer particle number and diameter,and latex stability.

Semibatch Emulsifier-free Emulsion Copolymerization of Methyl Methacrylate and n-Butyl Acrylate in the Presence of 2-Hydroxyethyl Methacrylate

The semibatch emulsifier-free emulsion copolymerization of methyl methacrylate (MMA) and n-butyl acrylate (BA) in the presence of 2-hydroxyethyl methacrylate (HEMA) initiated by K2S2O8 (PSP) was studied. The average particle diameter increases with an increase of total solids content, HEMA content, PSP content, ionic strength of the system and monomer feed rate, and decreases with the monomer feed ratio from 3/1 (MMA/BA mole.) to 1/3. The stability of this reaction system is improved by adding HEMA as nonionic comonomer. The high solids content (50%) latex with monodisperse particle can be obtained using this process.

EFFECT OF 2-HYDROXYETHYL METHACRYLATEON SEMIBATCH EMULSIFIER-FREE EMULSION COPOLYMERIZATION OF METHYLMETHACRYLATE AND BUTYL ACRYLATE

The semibatch emulsifier-free emulsion copolymerization of methyl methacrylate(MMA and butyl acrylate (BA) in the presence of 2-hydroxyethyl methacrylate (HEMA)initiated by K2S2O8 (PSP) was studied. The latex particles can maintain an appreciablestability during the emulsifier-free emulsion copolymerization of MMA and BA in thepresence of HEMA The average particle diameter increase with an increase of totalsolids content, HEMA content, PSP content, ioniC strength of the system and monomerfeed rate, and decrease with the monomer feed ratio From 3/1(MMA/BA;molar ratio.)to1/3. The stability of this reaction system is improved by adding HEMA as nonioniccomonomer High solids content (50%) latex with monodisperse particle can beobtained using this process.

EFFECTS OF ω-ACRYLOYL POLY (ETHYLENE OXIDE) MACROMONOMER ON EMULSIFIER-FREE EMULSI0N COPOLYMERIZATION OF METHYL METHACRYLATE AND n-BUTYL ACRYLATE

Well-defined nonionic hydrophilic ω-acryloyl poly(ethylene oxide) macro-monomer (PEO-A) has been prepared by living anionic polymerization of ethylene oxidewith diphenyl methyl potassium as the initiator and acryloyl chloride as the reaction termi-nating agent. The polymer was characterized by FTIR and SEC. The emulsifier-free emul-sion polymerization of methyl methacrylate (MMA) and n-butyl acrylate (BA) containingvarious concentrations of PEO-A was studied. In all cases stable emulsion coplymerizationsof MMA and BA were obtained. The stabilizing effect was found to be dependent on themolecular weight and the feed amount of the macromonomer.

Self-assembly of Gradient Copolymer Synthesized by Spontaneous Batch RAFT Emulsion Polymerization and Its Application on Encapsulating Ag Nanoparticles

The gradient copolymers of acrylic acid and trifluoroethyl methacrylate（coded as P（TFEMAgrad-AA）） were synthesized via reversible addition-fragmentation transfer（RAFT） emulsifier-free emulsion polymerization. The spontaneous batch feeding approach was used to control the gradient chain sequence. Transmission electron microscopy（TEM） analysis revealed that the P（TFEMA-grad-AA） can self-assemble to form spherical micelles, rodlike micelles or vesicles in selective solvents. Morphological transition of the P（TFEMA-grad-AA） micelles was sensitive to the water content of the dioxane/water mixed solvent. More interestingly, Ag nanoparticles（NPs） were encapsulated by the P（TFEMA-grad-AA） micelles during the selfassembly process. The gradient chain sequence made the Ag NPs easily enter the core of the micelles, even when P（TFEMA-grad-AA） had less hydrophobic fluoro-units and more hydrophilic units. TEM images with energy dispersive spectrometer indicated that the nanocomposite micelles consisted of a Ag NPs core and a gradient copolymer shell.

Study on N-Phenylmaleimide/Styrene /Acrylonitrile Copolymer Prepared by Emulsion Polymerization

The emulsion polymerization of N-phenylmaleimide, Styrene and acrylonitrile was studied. The thermal property of this copolymer was measures by dynamic thermomechanical analysis(DMA). The mechanical properties, such as tensile strength, hardness and fie-cural Strength were StUdied experimentally. The results indicated that not only the monomer component but also the polymerization technologies have effect on the properties of the copolymer. The optimum monomer content and suitable polymerization method were obtained.

Ether-/Ester-/Fluorine-Rich Binding Emulsion Formula for Lithium-Ion Batteries

Practical application of a Si anode in a high-energy-density battery cannot be achieved due to the huge volume expansion of these anodes.Researchers have focused on binders of the anode to restrict volume expansion in order to address this issue,as the hydrogen bonds and mechanical properties of binders can be used to enhance adhesion and accommodate the volume changes of a Si anode.Herein,we comprehensively consider binders’hydrogen bonds,mechanical properties,stability,and compatibility with the electrolyte solution,and design an ether-/ester-/fluorine-rich composite polymer,named P(TFEMAco-IBVE).The proposed binder formula possesses outstanding stability,adhesion,and mechanical strength;moreover,it can accommodate the dramatic volume changes of a Si electrode and exhibits excellent electrochemical performance,achieving a high areal capacity of about 5.4 mA·h·cm^(-2).This novel polymer design may be applied to other electrode materials in the next generation of lithium-ion batteries.

A New Kind of Void Soap-free P(MMA-EA-MAA) Latex Particles

Soap-free P(MMA-EA-MAA) particles with narrow size distribution were synthesized by seeded emulsion polymerization of methyl methacrylate (MMA), ethyl acrylate (EA) and methacrylic acid (MAA), and large voids inside the particles were generated by alkali posttreatment in the presence of 2-butanone. Results indicated that the size of void and the particle volume were related with the amount of 2-butanone. The generation mechanism of voids was proposed.

Preparation of Chitosan-g-PAM PS in H_2O/scCO_2 Inverse Emulsion

Chitosan （CS） was successfully modified in supercritical carbon dioxide （ scCOz ） by grafting method to enhance its water solubility. In this work, a three.arm star-like fluorinated polymer was synthesized by atom transfer radical polymerization （ ATRP ） method and applied as a surfactant in supereriticul carbon dioxide （scCO2 ）. Then 2-acrylamido-2-methyl propane sulfonie acid （AMPS） was grafted onto CS （CS-g-PAMPS） in H2O/scCO2 inverse emulsion. The effects of mass ratio of water and surfactants （Rw/s ） and pressure of scCO2 on the grafting reaction were investigated. The grafting rate, partide size, and dispersity in water of CS-g-PAMPS varied greatly as Rw/s and pressure of scCO2 changed. It could be found that the value of Rw/s at 12 and the pressure of scCO2 at 30 MPa were the optimum conditions for the grafting reaction. CS-g-PAMPS prepared in this reaction system has higher grafting rate, smaller particle sizes, and better dispersity in water than those prepared via conventional methods.

Synthesis of submicron-sized peanut-shaped poly(methyl methacrylate)/polystyrene particles by seeded soap-free emulsion polymerization

Submicron-sized peanut-shaped poly（methyl methacrylate）/polystyrene （PMMA/PS） particles were successfully synthesized by seeded soap-free emulsion polymerization of styrene on the spherical crosslinked PMMA seed particles. The obtained peanut- shaped particles showed a novel internal morphology： PS phase formed one domain which linked to the other domain having PMMA core encased by PS shell.

PREPARATION OF MICRON-SIZED NONSPHERICAL POLYSTYRENE/POLY(STYRENE-co-ETHYLENEGLYCOL DIMETHACRYLATE) PARTICLES BY SEEDED SOAP-FREE EMULSION POLYMERIZATION

Micron-sized nonspherical polymer particles having different morphologies were synthesized by seeded soap-free emulsion polymerization of styrene （St） and ethyleneglycol dimethacrylate （EGDMA, used as a crosslinker） on spherical, linear polystyrene （PS） seed particles. The morphology of the resulting PS/poly（St-co-EGDMA） particles was dependent on the crosslinker concentration and polymerization temperature.

One-step synthesis of self-healable hydrogels by the spontaneous phase separation of linear multi-block copolymers during the emulsion copolymerization

Self-healable polyacrylamide-based hydrogels were prepared at room temperature via a one-step emulsion copolymerization of acrylamide（AM）,dodecyl 2-methacryIate（DM）,and 5-acetylaminopentyl acrylate（AAPA） using sodium dodecyl sulfonate（SDS） as the emulsifier and ammonium persulfate（APS）as the initiator.The produced linear multi-block copolymer chains are composed of randomly-linked hydrophilic polyacrylamide segments（PAM） and hydrophobic segments constituted by DM and AAPA units（P（DM-co-AAPA））.The P（DM-co-AAPA） segments will self-aggregate into hydrophobic microdomains during the polymerization process driven by the hydrophobic interactions,and finally separate from water phase,acting as the crosslinks and leading to the formation of strong hydrogels with a storage modulus as high as 400 Pa.These hydrophobic microdomains will be dissolved in water when the temperature increases to 70℃,resulting in a temperature-responsive reversible sol-gel transition of the prepared hydrogels.Furthermore,the prepared hydrogels have excellent self-healing ability.The broken hydrogels can be automatically healed into a body with a same strength within 2-min＇s contact.This work provides a new simple way to prepare reversible physical crosslinked hydrogel with high strength and self-healing efficiency.

Synthesis of submicron-sized composite particles with unique morphology by emulsifier-free seeded emulsion copolymerization

Polystyrene （PSt） microspheres with diameter of 375 nm to be used as the seeds for seeded emulsion polymerization were prepared via emulsion polymerization using potassium persulfate （KPS） as initiator in ethanol-water mixed solvents. Emulsifier-free seeded emulsion copolymerization of styrene （St） with acrylonitrile （AN） was carried out in the presence of poly（ethylene glycol） monomethoxymonomethacrylate （PEGm） macromonomer as reactive stabilizer and 2,2＇-azobisisobutyronitrile （AIBN） as initiator to obtain submicron-sized PEGm graft poly（styrene-coacrylonitrile） （PEGm-g-PSAN） composite particles with unique morphology. Scanning electron microscopy （SEM） indicated that St and AN together contributed to forming the unusual morphology. The concentration of St and AN, total monomer concentration, initiator type and the monomer adding method remarkably affected the morphology of the composite polymer particles.

Effect of stirring on preparation of hollow copolymer particles by alkali/cooling method

Hollow particles were prepared by the treatment of styrene-metbacrylic acid copolymer particles with alkali/cooling method. The influences of stirring position （in aqueous phase or at the interface of O/W） and stirring speed （90, 110 and 240 r/min） on the formation of hollow particles were investigated. It is found that the soft stirring in aqueous phase at 90 r/min leads to the formation of monohollow particles, while the violent stirring at the interface of O/W and 240 r/min gives non-hollow products. In contrast, the weak stirring in aqueous phase at 110 r/min results in sterically heterogeneous dispersion of methacrylic acid-rich regions within the original particles, and hence the formation of multihollow particles. Further investigation indicates that the change of stirring efficiency provides a way to tune the diffusion behavior of monomer styrene, and therefore influences the distribution of methacrylic acid units in the original particles as well as the morphology of the treated particles.