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.

Synthesis and Characterization of Fluorine-containing Polyacrylate Emulsion with Core-Shell Structure

A fluorine-containing polyacrylate copolymer emulsion was synthesized by a seed emulsion polymerization method, in which methyl methacrylate （MMA） and butyl acrylate （BA） were used as main monomers and hexafluorobutyl methacrylate （HFMA） as fluorine-containing monomer. The structure and properties were characterized by Fourier transform infrared spectrum （FT-IR）, transmission electron microscopy （TEM）, particle size analysis, X-ray photoelectron spectroscopy （XPS）, contact angle （CA）, differential scanning calorimetry （DSC） and thermogravimetry （TG） analysis. The FTIR and TEM results showed that HFMA was effectively involved in the emulsion copolymerization, and the formed emulsion particles had a core-shell structure and a narrow particle size distribution. XPS and CA analysis revealed that a gradient concentration of fluorine existed in the depth profile of fluorine-containing emulsion film which was richer in fluorine and more hydrophobic in one side. DSC and TG analysis also showed that a clear core-shell structure existed in the fluorine-containing emulsion particles, and their film showed higher thermal stability than that of fluorine-free emulsion.

INTERACTION OF ANTIGEN AND ANTIBODY ON CORE-SHELL POLYMERIC MICROSPHERES

Monodispersed microspheres with polystyrene as the core and poly（acrylamide-co-N-acryloxysuccinirnide） as the shell were synthesized by a two-step surfactant-free emulsion copolymerization.The core-shell morphology of the microspheres was shown by scanning electron microscopy and transmission electron microscopy.Rabbit immunoglobulin G （as antigen） was covalently coupled onto the microspheres by the reaction between succinimide-activated ester groups on the shell of the microspheres and amino groups of the antigen molecules.The size of particles was characterized by dynamic light scattering technique and was found to vary upon bioconjugation and interaction with proteins.The binding process was shown to be specific to goat anti-rabbit immunoglobulin G（as antibody） and reversible upon the addition of free antigen into the system.

Preparation of Styrene-acrylate Latex Used in Ultralow VOC Building Internal Wall Coating

Styrene-acrylate latex with high glass transition temperature （T）, low minimum film forming temperature（MFT） and good stability was prepared via core-shell emulsion polymerization. With semicontinuous process, high conversion rate of monomer and low gel rate were achieved. The weight ratio of core monomer to shell monomer was approximately 1.35. It is found that many factors such as emulsifiers, initiators, reaction temperature, pH value and polymerization technology have influences on the permormance of styrene-acrylate latex. The prepared latex was characterized by TEM and FTIR. The obtained latex with T of 20.57 ℃, MFT or5.0 ℃, and good stability, had good stability of film forming.

DESIGN AND CONTROL OF SOAP-FREE HYDROPHILIC-HYDROPHOBIC CORE-SHELL LATEX PARTICLES WITH HIGH CARBOXYL CONTENT IN THE CORE OF THE PARTICLES

Soap-flee hydrophilic-hydrophobic core-shell latex particles with high carboxyl content in the core of the particles were synthesized via the seeded emulsion polymerization using methyl methacrylate （MMA）, butyl acrylate （BA）, methacrylic acid （MAA）, styrene （St） and ethylene glycol dimethacrylate （EGDMA） as monomers, and the influences of MMA content used in the core preparation on polymerization, particle size and morphology were investigated by transmission electron microscopy, dynamic light scattering and conductometric titration. The results showed that the seeded emulsion polymerization could be carried out smoothly using ＂starved monomer feeding process＂ when MAA content in the core preparation was equal to or less than 24 wt%, and the encapsulating efficiency of the hydrophilic P（MMA-BA-MAA- EGDMA） core with the hydrophobic PSt shell decreased with the increase in MAA content. When an interlayer of P（MMA- MAA-St） with moderate polarity was inserted between the P（MMA-BA-MAA-EGDMA） core and the PSt shell, well designed soap-free hydrophilic-hydrophobic core-shell latex particles with 24 wt% MAA content in the core preparation were obtained.

Fabrication and Characterization of Sulfonate-containing Polystyrene/CaCO_(3) 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)/CaCO_(3) core-shell nanoparticles were fabricated by sequentially introducing Ca(OH)_(2) aqueous solution and CO_(2) 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 CaCO_(3) 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 CaCO_(3)(ACC)and prevented ACC from sequent transformation into crystalline states.The amount of the anchored CaCO_(3) increased with the growth of PNaSS hair length,and reached 51 wt%(by thermalgravimetric analysis)under the optimal encapsulating temperature of 45℃.Moreover,the forming mechanism of P(St-NaSS)/CaCO_(3) coreshell nanoparticles was proposed.

Preparation of Core-Shell Structured Polyacrylic Modifiers and Effects of the Core-Shell Weight Ratio on Toughening of Poly(butylene terephthalate)

Core-shell structured polyacrylic（named CSSP） impact modifiers consisting of a rubbery poly（n-butyl acrylate） core and a rigid poly（methyl methacrylate） shell with a size of about 353 nm were prepared by seed emulsion polymerization. The CSSP modifiers with different core-shell weight ratios（90/10, 85/15, 80/20, 75/25, 70/30, 65/35 and 60/40） were used to modify the toughness of poly（butylene terephthalate）（PBT） by melt blending. It was found that the polymerization had a very high instantaneous conversion（ 95.7%） and overall conversion（99.7%）. The morphology of the core-shell structure was confirmed by means of transmission electron microscopy. Scanning electron microscopy was used to observe the morphology of the fractured surfaces. Differential scanning calorimeter was used to study the crystallization behaviors of PBT/CSSP blends. The dynamic mechanical analyses of PBT/CSSP blends showed two merged transition peaks of PBT matrix, with the presence of CSSP core-shell structured modifier, that were responsible for the improvement of PBT toughness. The results indicated that the notch impact strength of PBT/CSSP blends with a core-shell weight ratio of 75/25 was almost 8.64 times greater than that of pure PBT, and the mechanical properties agreed well with the SEM observation.

Effect of cationic monomer on properties of fluorinated acrylate latex

Cationic fluorinated acrylate latex was prepared via semi-continuous emulsion copolymerization of cationic monomer and other monomers. The resultant latex and its film were characterized with dynamic light scattering detector and contact angle meter. Influences of amount of DMDAAC on the properties of resultant latex and its film were investigated in detail. Results show that the particle size of the latex has the minimum value knd the zeta potential of the latex is increased when the amount of DMDAAC is increased. In addition, the particle size of the latex is unimodal distribution when the amount of DMDAAC is not more than 2.5%. However, the particle size of the latex is bimodal distribution when the amount of DMDAAC is more than 2.5%. The contact angle is varied slightly with the increase of amount of DMDAAC when it is not more than 2.5%. Nevertheless, the contact angle is decreased with the increase of the amount of DMDAAC when it is more than 2.5%.