Effects of surface charge density on emulsion kinetics and secondary particle formation in emulsifier-free seeded emulsion polymerization of methyl methacrylate

 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     

Charged polystyrene nanoparticles: role of ionic comonomers structures

Emulsion copolymerizations of styrene were carried out with four structurally different ionic comonomers namely acrylic acid (AAc), methacrylic acid (MAA), 2-hydroxyethyl methacrylate (HEMA), and sodium styrene sulfonate (NaSS) to study the effect of monomer structure on the copolymerization kinetics and size, morphology, charge density, and the self-assembly of the particles. The copolymerization kinetics was found to be highly dependent upon the ionic comonomer structure, and the nature of this dependence altered from homogeneous to micellar nucleation regime. The decrease in particle size (D) with increasing surfactant concentration (S) was observed in all the cases; however, the exponents of D vs. S were not similar for all the cases. In the homogeneous nucleation regime, exponents followed the order as AAc (0.446) > MAA (0.396) > NaSS (0.252) > HEMA (0.241), whereas the order was almost reversed in the micellar nucleation regime as NaSS (0.406) > HEMA (0.228) > AAc (0.206) > MAA (0.172). The hydrophobic/hydrophilic character and the steric factors were found to be the driving force for the variation in D vs. S exponents with ionic comonomer structure. The presence of charges on the particle surface contributed by the ionic comonomers triggered the self-assembly of the particles upon sedimentation and diffracted visible light obeying Bragg's law.     

Emulsifier-free emulsion copolymerization of styrene and butyl acrylate. II. Kinetic studies in the presence of ionogenic comonomers

Batch emulsifier-free copolymerizations of styrene (S) and butyl acrylate (BuA) have been performed for a S/BuA weight ratio = 50/50 in the presence of two types of functional comonomers [methacrylic acid (MAA) at different pHs] or potassium sulfopropylmethacrylate (SPM) and two initiators [potassium persulfate or 4–4′azobiscyanopentanoic acid (AZO)]. The use of AZO/MAA system results in the formation of polymer particles with only surface carboxylic end groups. The particle size of the final latexes can be adjusted with the MAA concentration, provided the polymerization is carried out at pH > 6.5. However, the higher the MAA concentration, the sooner the polymerization levels off in conversion. With the K₂S₂O₈/SPM system, particles bearing only sulfate and sulfonate groups are produced and the polymerization is complete. In that case, the particle size of the final latexes is smaller than with the previous system and 30% of the SPM is fixed on the particle surface, instead of 10% with MAA. Using SPM, a too high functional monomer concentration results in the latex destabilization caused by the formation of a large amount of polyelectrolytes. Kinetic studies indicate that most of the functional monomer is incorporated onto the particle surface during the last 30% conversion of the polymerization. A tentative explanation of such a behavior is discussed, based on the existence of two polymerization loci in the latex system.     

Fabrication and Characterization of Sulfonate‐containing Polystyrene/CaCO3 Core‐shell Nanoparticles

Polystyrene (PSt) seed latex was first prepared via soap‐free emulsion polymerization in the presence of a small amount of methacrylic acid using ammonium persulfate as initiator, and then seeded emulsion polymerization of sodium 4‐styrenesulfonate (NaSS) and St was carried out to synthesize P(St‐NaSS) core latex using 2,2′‐azobisisobutyronitrile as initiator. After that, P(St‐NaSS)/CaCO₃ core‐shell nanoparticles were fabricated by sequentially introducing Ca(OH)₂ aqueous solution and CO₂ gas into the core latex. The morphology of the core and core‐shell nanoparticles was characterized by dynamic light scattering (DLS) and transmission electron microscopy (TEM), and the state of CaCO₃ shell was confirmed with high‐resolution scanning transmission electron microscope (HR‐STEM) and selected area electron diffraction (SAED). Results showed that PNaSS chains were successfully grafted onto the PSt seed surface, and length of the PNaSS "hairs" could be modulated by adjusting NaSS amount. Sulfonic groups of the PNaSS hairs served as additives in the formation and stabilization of amorphous CaCO₃(ACC) and prevented ACC from sequent transformation into crystalline states. The amount of the anchored CaCO₃ increased with the growth of PNaSS hair length, and reached 51 wt% (by thermalgravimetric analysis) under the optimal encapsulating temperature of 45°C. Moreover, the forming mechanism of P(St‐NaSS)/CaCO₃ core‐shell nanoparticles was proposed.     

Water-soluble Polyelectrolytes Contaning Sulfonic Acid Groups with Metal Ion Binding Ability by Using the Liquid Phase Polymer Based Retention Technique

Water-soluble polyelectrolytes from 2-acrylamido-2-methyl-1-propane sulfonic acid (APSA) were obtained by radical polymerization with different comonomers which contain weak acid and neutral groups. These copolymers were investigated as polyelectrolytes and polychelatogens, in view of their metal ion binding properties using the liquid-phase polymer-based retention (LPR) technique under different experimental conditions. The metal ions investigated were: Ag(I), Co(II), Cu(II), Zn(II), Cd(II), and Pb(II). APSA allowed increase metal ion interaction of weak acid, meanwhile did not improve the metal ion interaction of neutral monomers at these experimental conditions. Results indicated that retention capability depended strongly on the structure of the polyelectrolyte, arrangement of comonomers at main chain, pH, and the filtration factor, Z.     

Preparation of CO2‐switchable latexes using N‐[3‐(dimethylamino)propyl]‐methacrylamide (DMAPMAm)

CO₂‐switchable polystyrene (PS), poly(methyl methacrylate) (PMMA), and poly(butyl methacrylate) (PBMA) latexes were prepared via surfactant‐free emulsion polymerization (SFEP) under a CO₂ atmosphere, employing N‐[3‐(dimethylamino)propyl]methacrylamide (DMAPMAm) as a CO₂‐switchable, water‐soluble, and hydrolytically stable comonomer. The conversion of the SFEP of styrene reaches >95% in less than 5 h. The resulting latexes have near monodisperse particles (PDI ≤ 0.05), as confirmed by DLS and TEM. The latexes could be destabilized by bubbling nitrogen (N₂) and heating at 65 °C for 30 min, and easily redispersed by only bubbling CO₂ for a short time without using sonication. © 2017 Wiley Periodicals, Inc. J. Polym. Sci., Part A: Polym. Chem. 2017 , 55, 1059–1066     

Preparation of sulphonate-containing core/shell latex particles via seeded emulsion copolymerization

<正>In this study,P(St-MAA) seed latex particles were first prepared via soap-free emulsion polymerization of styrene(St) and methacrylic acid(MAA),then the seed particles were allowed to swell with St at room temperature,and the P(St-MAA)/P(StNaSS) core/shell latex particles were then synthesized via seeded emulsion copolymerization of St and sodium styrene sulphonate (NaSS) using AIBN as initiator in the presence of N,N'-methylenebisacrylamide(BAA,water-soluble crosslinker).Results showed that the polymerization could be carried out smoothly when the ratio of BAA to total monomers was less than 3 mol%,the narrow dispersed P(St-MAA) seed particles with the diameter of 150 nm and the P(St-MAA)/P(St-NaSS) core/shell latexes with the particle size of about 200 nm were synthesized.When the 25/75 mole ratio of NaSS/(St + MAA) and 2 mol%of BAA were used in the seeded emulsion polymerization,the resulted P(St-MAA)/P(St-NaSS) latex product showed a low weight loss after water extraction,and the NaSS unit content in the whole particle and in the shell reached 11.7 mol%and 34.6 mol%,respectively.     

Preparation of micrometer-sized poly(methyl methacrylate) particles with amphoteric initiator in aqueous media

A previously proposed method based on soap-free emulsion polymerization with an amphoteric initiator for producing micrometer-sized polystyrene particles was extended to application with methyl methacrylate (MMA). The aggregation and dispersion stability of polymer particles, which have ionizable groups arising from initiator radicals, can be controlled by adjusting the pH of the reaction system accompanied with the addition of ionic monomer. Polymerizations were carried out with 2,2'-azobis[N-(2-carboxyethyl)-2-methylpropionamidine] tetrahydrate amphoteric initiator, NH(3)/NH(4)Cl pH buffer, and sodium p-styrenesulfonate anionic monomer (NaSS) in ranges of MMA concentration (0.58-2.32 kmol/m(3) H(2)O) and NH(3) concentration (2.5-20 mol/m(3) H(2)O) at fixed concentrations of 5 mol/m(3) H(2)O initiator, 10 mol/m(3) H(2)O NH(4)Cl, and 1 mol/m(3) H(2)O NaSS at 65 degrees C. The addition of NaSS during the polymerization could improve stability in dispersion of particles, which coagulated in the absence of NaSS after the disappearance of monomer drops. An increase in the monomer concentration in the present method could enlarge the particle size without lowering the monodispersity of the particle size distribution. On the other hand, an increase in NH(3) concentration decreased the particle size. The highest monodispersity of particle sizes was obtained at a NH(3) concentration of 5 mol/m(3) H(2)O, which gave an average size of 1.5 microm and a coefficient of variation of particle size distribution of 2.2% that was much smaller than the standard criterion for monodispersity, 10%.     

Structural effects of dopants and polymerization methodologies on the solid‐state ordering and morphology of polyaniline

The solid‐state three‐dimensional ordering of polyaniline–dopant complexes was investigated with four structurally different sulfonic acid dopants. The doped materials were produced in three different ways: polyaniline emeraldine base doped with sulfonic acid (aqueous route), in situ polymerization at the organic–water solvent interface (interfacial route), and in situ polymerization in organic and aqueous solvent mixtures (bilayer route). p‐Toluenesulfonic acid (PTSA), 5‐sulfosalicilic acid (SSA), camphorsulfonic acid (CSA), and dodecylbenzene sulfonic acid (DBSA) were employed as dopants. The conductivity of the aqueous‐route samples showed 10 and 100 times higher conductivity than the interfacial and bilayer routes, respectively. WXRD studies suggested that the crystallinity of the doped samples was dependent on both the structure of the dopants and the polymerization techniques. DBSA increases the polyaniline interplanar distance and produced highly crystalline materials via the aqueous and bilayer routes but failed with the interfacial route because of poor solubility in water. CSA, PTSA, and SSA produced highly crystalline samples by the interfacial route but failed with the aqueous (except for CSA) and bilayer routes. SEM analysis revealed that the doped materials of the interfacial route had excellent continuous morphology and uniform submicrometer‐size particle distributions in comparison with those of the aqueous and bilayer routes. © 2005 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys 43: 1321–1331, 2005     

Copolymeric nano/microgels of N-isopropylacrylamide and carboxyalkyl methacrylamides: Effect of methylene chains and the ionization state of the weak acids on size and sensitivity to pH and temperature

ABSTRACT

We prepared nano/microgels by precipitation copolymerization of N-isopropylacrylamide (NIPAAm), and one of three different carboxyalkyl methacrylamides [methacryloylamido hexanoic acid (M₅), 8-methacryloylamido octanoic acid (M₇), and 11-methacryloylamido undecanoic acid (M₁₀)], either in the acid forms or as carboxylates (potassium salts). The hydrodynamic diameter (Dh) of the nano/microgels prepared with the carboxylates was smaller (≈100 nm for M₁₀ copolymers), compared to the size of homopolymeric NIPAAm microgels prepared by dispersion polymerization (around 600 nm), indicating that the carboxylates act as surfactants reducing the size of the seeds during the polymerization process. These materials presented a swollen-shrunken transition temperature (T _tr) similar to the T _tr of the homopolymeric NIPAAm microgels, without pH sensitivity. On the other hand, the copolymeric microgels prepared from the acid form of the comonomers have a similar or bigger size than NIPAAm microgels. For these copolymers, the T _tr can be tuned by the type and proportion of acid comonomer used and present pH sensitivity. This is important for biomedical applications such as positive temperature control release. Polyelectrolyte titration demonstrates that the nano/microgels prepared with the carboxylates behave as hard spheres, while the microgels prepared with the weak acid behave as porous materials.     

不同碳源合成Na2MnPO4F/C及其作为锂离子电池正极材料的性能

采用湿法球磨和原位热解碳包覆相结合的方法, 分别以硬脂酸、柠檬酸、聚乙二醇-6000 (PEG-6000)、β-环糊精为碳源, 制备了不同结构的Na₂MnPO₄F/C 复合材料, 并研究了它们作为锂离子电池正极材料的电化学行为. 通过X射线衍射(XRD)、扫描电镜(SEM)、BET比表面积测试、恒流充放电等表征手段, 比较和分析了产物的结构、形貌及电化学性能. 研究结果表明, 由不同碳源制备的材料在形貌和颗粒尺寸上有明显差异, 进而对它们的电化学性能造成很大影响. 影响电化学性能的关键因素在于材料一次颗粒的大小. 其中, 以柠檬酸为碳源制备的样品呈现出典型的微纳结构和最小的一次颗粒(10-40 nm). 并给出最佳的电化学性能: 在1.5-4.8 V电压范围内, 以5 mA·g^-1充放电电流获得的首次放电比容量约为80 mAh·g^-1, 且循环稳定性良好.     

Magnetically loaded poly(methyl methacrylate-co-acrylic acid) nano particles

Magnetically loaded polymeric nano-particles carrying functional groups on their surface were prepared by a two-stage process. In the first stage, super-paramagnetic magnetite (Fe₃O₄) nano-particles were produced by a co-precipitation method from the aqueous solutions of FeCl₂·4H₂O and FeCl₃·6H₂O using a NaOH solution. The smallest size obtained was 40.9 nm with poly-dispersity index of 0.194 obtained by using a Zeta Sizer. The effects of Fe²⁺/Fe³⁺ molar ratio, stirring rate, temperature, base concentration, and pH on the particle size/size distribution and stability of the dispersions were examined. Increasing the relative concentration of Fe²⁺ ion and decreasing the stirring rate and pH increased the particle size, while the concentration of NaOH and temperature did not change the particle size significantly. Polymer coating was achieved by emulsion polymerization at high surfactant to monomer ratio of methyl methacrylate (MMA) and acrylic acid which were used as comonomers (comonomer ratio: 90/10 weight) with high surfactant to monomer ratio. The surfactant and initiator were SDS and KPS, respectively. Nano-particles in the range of 115 and 300 nm in diameter were produced depending on recipe. Increasing the Fe₃O₄/monomer and surfactant/monomer ratios, the KPS concentration caused a decrease in the average diameter. Magnetic properties of the nano-particles were obtained by electron spin resonance and vibrating-sample magnetometer. Most of the polymer-coated nano-particles exhibited super paramagnetic behavior.An erratum to this article can be found at     

Effect of temperature and water as additive on the MW and thermal properties of copoly(p-phenylene/biphenylene sulfide)s

Copoly(p-phenylene/biphenylene sulfide)s, PPBS were prepared from sodium sulfide trihydate(Na₂S·3H₂O), p-dichlorobenzene (DCB), and 4,4′-dibromobiphenyl (DBB) comonomers in N-methyl-2-pyrrolidinone (NMP) solvent using an autoclave. The molecular weights of PPBS copolymers were determined by high temperature (210°C) GPC in 1-chloronaphthalene solvent. The reaction temperature had little effect on the molecular weights of PPBS copolymers with water as additive at the level of 3 mol H₂O per 1 mol Na₂S. PPBS copolymer, however, showed maximum molecular weight of M_w = 24.1 × 10³ with the total water content of 9 mol H₂O per 1 mol Na₂S at an optimum polymerization temperature of 270°C. The resulting PPBS copolymer sample showed higher T_g (by 30°C) and lower T_m (by 10°C) than PPS homopolymer prepared under similar conditions. © 1996 John Wiley & Sons, Inc.     

Fluorinated copolymers and terpolymers based on vinylidene fluoride and bearing sulfonic acid side‐group

The radical co‐ and terpolymerization of perfluoro(4‐methyl‐3,6‐dioxaoct‐7‐ene) sulfonyl fluoride (PFSVE) with 1,1‐difluoroethylene (or vinylidene fluoride, VDF or VF₂), hexafluoropropene (HFP), chlorotrifluoroethylene (CTFE), and bromotrifluoroethylene (BrTFE) is presented. Although PFSVE could not homopolymerize under radical initiation, it could be copolymerized in solution under a radical initiator with VDF, while its copolymerizations with HFP or CTFE led to oligomers in low yields. The terpolymerizations of PFSVE with VDF and HFP, with VDF and CTFE, or with VDF and BrTFE also led to original fluorinated terpolymers bearing sulfonyl fluoride side‐groups. The conditions of co‐ and terpolymerization were optimized in terms of the nature and the amount of the radical initiators, of the nature of solvents (fluorinated or nonhalogenated), and of the initial amounts of fluorinated comonomers. The different mol % contents of comonomers in the co‐ and terpolymers were assessed by ¹⁹F NMR spectroscopy. A wide range of co‐ and terpolymers containing mol % of PFSVE functional monomer ranging from 10 to 70% was produced. The kinetics of copolymerization of VDF with PFSVE enabled to assess the reactivity ratios of both comonomers: r_VDF = 0.57 ± 0.15 and r_PFSVE = 0.07 ± 0.04 at 120 °C. The thermal and physicochemical properties were also studied. Moreover, the glass transition temperatures (T_gs) of poly(VDF‐co‐PFSVE) copolymers containing different amounts of VDF and PFSVE were determined and the theoretical T_g of poly(PFSVE) homopolymer was deduced. Then, the hydrolysis of the ? SO₂F into ? SO₃H function was investigated and enabled the synthesis of fluorinated copolymers bearing sulfonic acid functions. © 2007 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 45: 1814–1834, 2007     

Emulsifier-free emulsion polymerization with ionic comonomer

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.     

Study on soap‐free P(MMA‐EA‐AA or MAA) latex particles with narrow size distribution

Soap‐free poly(methyl methacrylate‐ethyl acrylate‐acrylic acid or methacrylic acid) [P(MMA‐EA‐AA or MAA)] particles with narrow size distribution were synthesized by seeded emulsion polymerization of methyl methacrylate (MMA), ethyl acrylate (EA) and acrylic acid (AA) or methacrylic acid (MAA), and the influences of the mass ratio of core/shell monomers used in the two stages of polymerization ([C/S]_w) and initiator amount on polymerization, particle size and its distribution were investigated by using different monomer addition modes. Results showed that when the batch swelling method was used, the monomer conversion was more than 96.0% and particle size distribution was narrow, and the particle size increased first and then remained almost unchanged at around 600 nm with the [C/S]_w decreased. When the drop‐wise addition method was used, the monomer conversion decreased slightly with [C/S]_w decreased, and large particles more than 750 nm in diameter can be obtained; with the initiator amount increased, the particle size decreased and the monomer conversion had a trend to increase; the particle size distribution was broader and the number of new particles was more in the AA system than in the MAA system; but the AA system was more stable than the MAA system at both low and high initiator amount. Copyright © 2006 John Wiley & Sons, Ltd.     

Acrylic emulsifier-free emulsion polymerization containing hydrophilic hydroxyl monomer in the presence or absence of nano-SiO2

The acrylic emulsifier-free emulsion polymerization containing hydrophilic hydroxyl monomer (23 wt.%) in the presence or absence of nano-SiO₂ particles was studied. The effects of reaction temperature, level of nano-SiO₂, variation of core monomer composite on the coagulum, particle size and monomer conversion were investigated. Transmission electron microscopy (TEM) was used to observe the particle morphology in the presence of nano-SiO₂ particles. It showed that the systems produced larger size of particles than that with emulsifier, and the addition of nano-SiO₂ particles increased the particle size but decreased the coagulum. When polymerization temperature rose from 65 °C to 80 °C, the coagulum produced decreased greatly irrelative of the existence of nano-SiO₂, and the particle size decreased with nano-SiO₂ but increased without nano-SiO₂. The increase of level of acrylic acid (AA) and 2-hydroxyethyl methacrylate (HEMA) in core monomer composite all decreased particle sizes; furthermore, the level of AA had more efficiency than the level of HEMA irrespective of the existence of nano-SiO₂ particle.     

Synthesis and characterization of sulphonated core-shell latices in the size range between 30 and 80 nm

The objective of the current work was the synthesis of sulphonated core-shell nanolatices and to investigate to which extend it is possible to control the final surface charge of such latices. For this purpose differently sized polystyrene seed latices with average diameters in the size range between 30 and 80 nm were synthesized by emulsion polymerization. To obtain the final latices, a sulphonated comonomer was incorporated in the outer surface shell of the particles by further reaction of the seed latices with styrene and sodium styrene sulphonate (NaSS). In a first test series the seed latex surface was modified with four different amounts of NaSS. In a second test series four different seed latices were reacted with the same amount of NaSS. In the last set of reactions the seed latices were reacted with different amounts of NaSS and in these reactions the ratio of added NaSS to the specific surface area of the seed latex was kept constant to obtain differently sized latices of the same surface charge density. The yield of sulphonic acid groups in the particle shell was found between 57 and 74% after an intensive cleaning step by ion exchange. The results show possibilities for a reproducible synthesis of small sulphonated latex particles with a desired surface charge density.     

硅酸及其盐的研究——ⅩⅤⅢ.硅溶胶胶粒的生长速度

为弄清各种影响因素对硅溶胶胶粒生长的作用,实验测定了胶粒自发生长速度与温度、pH和胶粒粒径等之间的关系,得到了复杂的胶粒生长过程的一些信息。并根据本实验室提出的硅酸聚合理论推导了胶粒生长速度公式,用该式推出的结果与实验所得结果基本符合,说明该式能较正确地反映胶粒生长规律,因而在哇溶胶实际生产中有一定的参考价值。     

Synthesis of nanostructured polyaniline via chemical oxidative polymerization: Investigation of morphology and conductivity of the prepared polymers

In this study, nanostructure polyaniline was prepared from aniline monomer via chemical oxidative polymerization in the presence of ammonium persulfate as an oxidizing agent. Interfacial, emulsion, rapid mixing and ultrasonic techniques are used for polymer synthesis. In the interfacial method, chloroform, n-hexane, hexanole and toluene were used as organic solvents and sulfuric acid, methane sulfonic acid and acetic acid were employed as electrolyte solutions. In the emulsion polymerization, dodecyl benzene sulfonic acid and aqueous solution of hydrochloric acid were used as emulsion agent and electrolyte solution respectively. In rapid mixing reaction and ultrasonic method, hydrochloric acid and salicylic acid were used as dopants. The structure, conductivity, morphology and particle size distribution of prepared polymers were investigated after purification and drying by FTIR spectroscopy, scanning electron microscopy and electrical conductivity measurements.