Polymerization behavior and polymer properties of eosin-mediated surface modification reactions

Surface modification by surface-mediated polymerization necessitates control of the grafted polymer film thicknesses to achieve the desired property changes. Here, a microarray format is used to assess a range of reaction conditions and formulations rapidly in regards to the film thicknesses achieved and the polymerization behavior. Monomer formulations initiated by eosin conjugates with varying concentrations of poly(ethylene glycol) diacrylate (PEGDA), N-methyldiethanolamine (MDEA), and 1-vinyl-2-pyrrolidone (VP) were evaluated. Acrylamide with MDEA or ascorbic acid as a coinitiator was also investigated. The best formulation was found to be 40 wt% acrylamide with MDEA which yielded four to eightfold thicker films (maximum polymer thickness increased from 180 nm to 1420 nm) and generated visible films from fivefold lower eosin surface densities (2.8 versus 14 eosins/μm²) compared to a corresponding PEGDA formulation. Using a microarray format to assess multiple initiator surface densities enabled facile identification of a monomer formulation that yields the desired polymer properties and polymerization behavior across the requisite range of initiator surface densities.     

Synthesis and properties of PDMS modified waterborne polyurethane–acrylic hybrid emulsion by solvent-free method

A new type of polysiloxane modified polyurethane–acrylic hybrid emulsion was synthesized by solvent-free method and the polysiloxane was introduced into the soft segment of polyurethane chains using dihydroxybutyl-terminated polydimethylsiloxane (PDMS). The formed film from the hybrid emulsion could provide obviously higher water-resistance property. The preparation technologies such as the content of carboxy group and acrylic monomer, the rate and the time of emulsification were discussed systematically. The chain structure and the particle size were confirmed by the analysis of Fourier transform infrared spectroscopy and transmission electron microscopy, respectively. The effect of PDMS content on the water resistance and the mechanical property were investigated by absorbed water ratio, water contact angle and dynamic mechanical measurement.     

Influence of Two Salicylate Components on the Particle Size of an Oil-in-Water Emulsion with Nonionic Surfactants

This paper reports a study undertaken using techniques of static and dynamic light scattering to investigate the influence of sodium salicylate and methyl salicylate on droplet size of oil-in-water emulsions. The rates of changes were measured by determining the size and distribution of the oil droplet in the material. All emulsions showed a bimodal size distribution; the mean diameters and polydispersity were calculated from intensity. These data were analyzed with nonlinear regressions and bootstrap methodology. An amount of methyl salicylate component induced a decrease of mean diameter and standard deviation. On the contrary, sodium salicylate entailed the growth of all droplet populations and coalescence for the highest concentration.     

γ 射线引发 VAc 乳液聚合以制备白乳胶的动力学及工艺条件研究

研究了ＶＡｃ的辐射乳液聚合动力学，并对其聚合工艺条件作了初步探索。得出ＶＡｃ乳液在进行辐射聚合时，成核期结束较早（转化率在１０％以下），有相当长的恒速期存在。乳胶粒子直径在０．５～３μｍ之间，比一般的乳液聚合乳胶粒子要大。同时从动力学数据还可以看出几种成核机理（胶束成核，水相成核和液滴成核）同时存在，由此对试验条件提出了相应的要求。     

FTIR investigation of ethylene coordination and polymerization on reduced Cr/SiO2 catalyst

FTIR spectroscopy was applied to study the initial steps of ethylene polymerization on reduced chromia-silica (0.5 wt% Cr/SiO₂). To decrease the speed of the reaction small doses of gas were introduced to the catalyst in each run and C₂D₄ was used to confirm band assignments. At the initial steps of the reaction only ethylene molecules coordinated to probably Cr _A ²⁺ cations were observed. The concentration of such complexes was estimated to be about 50% of the total amount of Cr atoms in the sample. The FTIR spectrum of the polymer formed at the initial doses of C₂H₄ (when [C₂H₄] [Cr]) was found to be slightly different from that formed after excess ethylene was introduced onto the catalyst ([C₂H₄] > [Cr]).     

Properties of poly(n‐butyl methacrylate) prepared by reverse atom transfer radical polymerization in an aqueous dispersed system

Reverse atom transfer radical polymerization (ATRP) of n‐butyl methacrylate (BMA) in waterborne media using Cu(II) complexes with azo initiators (i.e., reverse ATRP) was conducted. The influence of several factors, such as surfactant, catalyst, and reaction time, on the stability of the emulsion, the particle size, the morphology of the emulsion particles, and the control of the polymerization was investigated. The results showed great differences between ATRP and conventional emulsion polymerization, especially the nucleation mechanism and the kinetics. © 2003 Wiley Periodicals, Inc. J Appl Polym Sci 89: 1542–1547, 2003     

改性丙烯酸-环氧树脂纳米乳液的制备及应用

介绍了水性丙烯酸-环氧树脂纳米乳液的制备及其在油罐防腐工程中的应用。讨论了亲水侧链聚乙二醇相对分子质量大小对涂膜性能的影响以及乳化剂各组分的用量对乳液粒径的影响。     

High solids content emulsions. III. Synthesis of concentrated latices by classic emulsion polymerization

Two different methods of producing bi‐ and trimodal latices of a mixture of methyl methacrylate, butyl acrylate, and small amounts of acrylic acid were tested. It is shown that a combination of concentrating blends of seed particles by semibatch reaction, followed by a nucleation of small particles plus a second semibatch phase allowed us to obtain stable latices with solids contents over 65% and viscosities of below 2500 mPa s^?1 with little coagulum formation. The key parameter in determining latex stability, coagulum formation, and viscosity appears to be the the particle size distribution, and especially its modification attributed to secondary nucleation. Because it is not possible to eliminate water‐soluble monomers from the polymerization recipe, secondary (homogeneous) nucleation must be minimized by careful addition of the free‐radical initiator and choice of monomer feed flow rates. The nucleation of the third population in the trimodal latices is best accomplished with a mixed surfactant system because renucleation by anionic surfactant alone leads to detrimental changes in the particle size distribution (PSD) resulting from excessive flocculation of particles. In addition, it was found that the viscosity of the final products was not sensitive to small changes in the ionic strength of the latex, although neutralization to a pH of 6 effectively doubles the final latex viscosity. © 2002 Wiley Periodicals, Inc. J Appl Polym Sci 84: 1916–1934, 2002; DOI 10.1002/app.10513     

Poly(butylene terephthalate)/organoclay nanocomposites prepared by in situ interlayer polymerization and its fiber (II)

Intercalated nanocomposites with poly(butylene terephthalate) (PBT) incorporated between the montmorillonite layers were synthesized from dimethyl terephthalate and 1,4-butane diol by using an in situ interlayer polymerization. The PBT nanocomposites were melt-spun at different organoclay contents to produce monofilaments. The samples were characterized by using wide angle X-ray diffraction, electron microscopy, thermal analysis, and tensile testing. The extent of the clay layer in the PBT was confirmed by using X-ray diffraction and electron microscopy, and the clay layer was found to be highly dispersed on a nanometer scale. The addition of only a small amount of organoclay was enough to improve the thermo-mechanical properties of the PBT hybrid fibers. The hybrids were extruded with various draw ratios (DRs) to examine the tensile mechanical property of the fibers. At DR=1, the ultimate tensile strength of the hybrid fibers increased with the addition of clay up to a critical content and then decreased. However, the initial modulus monotonically increased with increasing amount of organoclay in the PBT matrix. When the DR was increased from 1 to 6, for example, the strength and the initial modulus values of the hybrids containing 3 wt% organoclay decreased linearly.     

悬浮法合成聚丙烯腈高吸水性树脂

以偶氮二异丁腈为引发剂，用悬浮聚合法合成了交联聚丙烯腈，然后对其进行水解，得到了高吸水性聚丙烯腈。交联剂用量和水解条件对树脂吸水倍数的影响很大。树脂吸去离子水倍数为420倍，平均粒径为250μm。