N‐vinylcaprolactam‐based microgels: Synthesis and characterization

Poly(N‐vinylcaprolactam) (PVCL) is well known for its thermoresponsive behavior in aqueous solutions. PVCL combines useful and important properties; it is biocompatible polymer with the phase transition in the region of physiological temperature (32–38 °C). This combination of properties allows consideration of PVCL as a material for design biomedical devices and use in drug delivery systems. In this work, PVCL based temperature‐sensitive crosslinked particles (microgels) were synthesized in a batch reactor to analyze the effect of the crosslinker, initiator, surfactant, temperature, and VCL concentration on polymerization process and final microgels characteristics. The mean particle diameters at different temperatures and the volume phase‐transition temperature of the final product were analyzed. To obtain information about the inner structure of microgel particles, semicontinuous polymerizations were carried out and the evolution of the hydrodynamic average particle diameters at different temperatures of the microgel synthesized was investigated. In the case of microgel particles obtained in a batch reactor the size and the swelling‐de‐swelling behavior as a function of the temperature of the medium can be tuned by modulating the reaction variables. When the microgel particles were synthesized in a semibatch reactor different swelling‐de‐swelling behaviors were observed depending on particles inner structure. © 2008 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 46: 2510–2524, 2008     

Resilient collapse of thermal sensitive polymer on the surface of the optical fiber taper

In this work, collapse of poly(N‐isopropyl‐acrylamide) (pNIPAM) grafted on the surface of the optical fiber taper is probed by measuring fluorescence of rhodamine B solution at various temperatures. It is observed that the fluorescence intensity through the taper shows a nonlinear response to temperature. According to the optical model for the special designed taper, it is realized that the nonlinear response results from changing in effective refractive index of interfacial layer between taper and solution. Analysis on relationship between signal change and collapse process reveals a springback process during the collapse of pNIPAM chains. Such a novel phenomenon is further investigated on method for fluorescence measurement and molecular weight of the polymer. These results have not only revealed details of the collapse, but also establish a novel technique for study the collapse of thermal sensitive polymers on the surface. © 2018 Wiley Periodicals, Inc. J. Polym. Sci., Part B: Polym. Phys. 2018 , 56, 778–785     

风险敏感性控制在CEV模型的应用研究

假设股票的价格遵循CEV过程,经济因子满足两个相互独立的布朗运动,运用风险敏感性随机最优控制理论得到新的结论,最后对于简化的模型,得到最优长期增长率的解析解.     

一种双扰动数量特征随机化问答策略

本文给出一种双扰动随机化回答模型.理论上扰动变量的引入会降低随机化调查的效率,本文使用两个设计参数设计了一种合理的双扰动变量随机化问答技术,在不降低装置对个体保护度的情况下,得出的结论表明,使用两个扰动变量可以提高调查装置的效率.通过数值模拟验证了本文模型的效率优于Bar-Lev,Bobovitch和Boukai 2004年单扰动回答模型的效率.     

Using filament stretching rheometry to predict strand formation and “processability” in adhesives and other non-Newtonian fluids

The spinning of polymeric fibers, the processing of numerous foodstuffs and the peel and tack characteristics of adhesives are all associated with the formation, stability and, ultimately, the longevity of thin fluid `strands'. This tendency to form strands is usually described in terms of the tackiness of the fluid or by heuristic concepts such as `stringiness' (Lakrout et al. J Adhesion 1999). The dynamics of such processes are complicated due to spatially and temporally non-homogeneous growth of extensional stresses, the action of capillary forces and the evaporation of volatile solvents. We describe the development and application of a simple instrument referred to as a microfilament rheometer (MFR) that can be used to readily differentiate between the dynamical response of different pressure-sensitive adhesive fluid formulations. The device relies on a quantitative observation of the rate of extensional thinning or `necking' of a thin viscous or viscoelastic fluid filament in which the solvent is free to evaporate across the free surface. This high-resolution measurement of the radial profile provides a direct indication of the ultimate time to break up of the fluid filament. This critical time is a sensitive function of the rheological properties of the fluid and the mass transfer characteristics of the solvent, and can be conveniently reported in terms of a new dimensionless quantity we refer to as a processability parameter P. We demonstrate the usefulness of this technique by presenting our results in the form of a case study in which we measure the visco-elasto-capillary thinning of slender liquid filaments for a number of different commercial polymer/solvent formulations and relate this to the reported processing performance of the materials. We also compare the MFR observations with the prediction of a simple 1D theory derived from the governing equations that model the capillary thinning of an adhesive filament. Received: 22 December 1999/Accepted: 4 January 2000     

Synthesis and characterization of pH sensitive poly(glycidol)‐b‐poly(4‐vinylpyridine) block copolymers

Block copolymers of poly(glycidol)‐b‐poly(4‐vinylpyridine) were obtained by ATRP of 4‐vinylpyridine initiated by ω‐(2‐chloropropionyl) poly(glycidol) macroinitiators. By changing the monomer/macroinitiator ratio in the synthesis polymers with varied P4VP/PGl molar ratio were obtained. The obtained block copolymers showed pH sensitive solubility. It was found that the linkage of a hydrophilic poly(glycidol) block to a P4VP influenced the pK_a value of P4VP. DLS measurements showed the formation of fully collapsed aggregates exceeding pH 4.7. Above this pH values the collapsed P4VP core of the aggregates was stabilized by a surrounding hydrophilic poly(glycidol) corona. The size of the aggregates depended significantly upon the composition of the block copolymers. © 2009 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 47: 1782–1794, 2009     

The effect of structure on the thermoresponsive nature of well‐defined poly(oligo(ethylene oxide) methacrylates) synthesized by ATRP

Statistical copolymers of di(ethylene glycol) methyl ether methacrylate (MEO₂MA) and tri(ethylene glycol) methyl ether methacrylate (MEO₃MA) were synthesized by atom transfer radical polymerization (ATRP) providing copolymers with controlled composition and molecular weights ranging from M_n = 8,300–56,500 with polydispersity indexes (M_w/M_n) between 1.19 and 1.28. The lower critical solution temperature (LCST) of the copolymers increased with the mole fraction of MEO₃MA in the copolymer over the range from 26 to 52 °C. The average hydrodynamic diameter, measured by dynamic light scattering, varied with temperature above the LCST. These two monomers were also block copolymerized by ATRP to form polymers with molecular weight of M_n = 30,000 and M_w/M_n from 1.12 to 1.21. The LCST of the block copolymers shifted toward the LCST of the major segment, as compared to the value measured for the statistical copolymers at the same composition. As temperature increased, micelles, consisting of aggregated PMEO₂MA cores and PMEO₃MA shell, were formed. The micelles aggregated upon further heating to precipitate as larger particles. © 2007 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 46: 194–202, 2008     

The synthesis and self‐assembly of ABA amphiphilic block copolymers containing styrene and oligo(ethylene glycol) methyl ether methacrylate in dilute aqueous solutions: Elevated cloud point temperatures for thermoresponsive micelles

A series of ABA amphiphilic triblock copolymers possessing polystyrene (PS) central hydrophobic blocks, one group with “short” PS blocks (DP = 54–86) and one with “long” PS blocks (DP = 183–204) were synthesized by atom transfer radical polymerization. The outer hydrophilic blocks were various lengths of poly(oligoethylene glycol methyl ether) methacrylate, a comb‐like polymer. The critical aggregation concentrations were recorded for certain block copolymer samples and were found to be in the range circa 10⁻⁹ mol L⁻¹ for short PS blocks and circa 10⁻¹² mol L⁻¹ for long PS blocks. Dilute aqueous solutions were analyzed by transmission electron microscopy (TEM) and demonstrated that the short PS block copolymers formed spherical micelles and the long PS block copolymers formed predominantly spherical micelles with smaller proportions of cylindrical and Y‐branched cylindrical micelles. Dynamic light scattering analysis results agreed with the TEM observations demonstrating variations in micelle size with PS and POEGMA chain length: the hydrodynamic diameters (D_H) of the shorter PS block copolymer micelles increased with increasing POEGMA block lengths while maintaining similar PS micellar core diameters (D_C); in contrast the values of D_H and D_C for the longer PS block copolymer micelles decreased. Surface‐pressure isotherms were recorded for two of the samples and these indicated close packing of a short PS block copolymer at the air–water interface. The aggregate solutions were demonstrated to be stable over a 38‐day period with no change in aggregate size or noticeable precipitation. The cloud point temperatures of certain block copolymer aggregate solutions were measured and found to be in the range 76–93 °C; significantly these were ∼11 °C higher in temperature than those of POEGMA homopolymer samples with similar chain lengths. © 2008 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 46: 7739–7756, 2008     

Well‐defined poly[(dimethylamimo)ethyl methacrylate]‐b‐poly(fluoroalkyl methacrylate) diblock copolymers: Effects of different fluoroalkyl groups on the solution properties

A series of well‐defined, fluorinated diblock copolymers, poly[2‐(dimethylamino)ethyl methacrylate]‐b‐poly(2,2,2‐trifluoroethyl methacrylate) (PDMA‐b‐PTFMA), poly[2‐(dimethylamino)ethyl methacrylate]‐b‐poly(2,2,3,4,4,4‐hexafluorobutyl methacrylate) (PDMA‐b‐PHFMA), and poly[2‐(dimethylamino)ethyl methacrylate]‐b‐poly(2,2,3,3,4,4,5,5‐octafluoropentyl methacrylate) (PDMA‐b‐POFMA), have been synthesized successfully via oxyanion‐initiated polymerization. Potassium benzyl alcoholate (BzO^?K⁺) was used to initiate DMA monomer to yield the first block PDMA. If not quenched, the first living chain could be subsequently used to initiate a feed F‐monomer (such as TFMA, HFMA, or OFMA) to produce diblock copolymers containing different poly(fluoroalkyl methacrylate) moieties. The composition and chemical structure of these fluorinated copolymers were confirmed by ¹H NMR, ¹⁹F NMR spectroscopy, and gel permeation chromatography (GPC) techniques. The solution behaviors of these copolymers containing (tri‐, hexa‐, or octa‐ F‐atom)FMA were investigated by the measurements of surface tension, dynamic light scattering (DLS), and UV spectrophotometer. The results indicate that these fluorinated copolymers possess relatively high surface activity, especially at neutral media. Moreover, the DLS and UV measurements showed that these fluorinated diblock copolymers possess distinct pH/temperature‐responsive properties, depending not only on the PDMA segment but also on the fluoroalkyl structure of the FMA units. © 2009 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 47: 2702–2712, 2009