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Effect of Polymer Composition on Polymer Diffusion in Poly(butyl acrylate-co-methyl methacrylate)Latex Films

机译:聚合物组成对聚(丙烯酸丁酯-共甲基丙烯酸甲酯)乳胶薄膜中聚合物扩散的影响

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We describe polymer diffusion measurements in poly(butyl acrylate-co-methyl methacrylate)[P(BA-MMA)] copolymer latex films by fluorescence resonance energy transfer(FRET).Four sets of copolymers were prepared from various weight ratios of butyl acry late and methyl methacrylate by semicontinuous emulsion polymerization.Their glass transition temperatures range from 4 to 28 °C.Latex particles were labeled with phenanthrene(Phe)as the donor dye and with 4-(N,N-dimethylamino)benzophenone(NBen)as the acceptor dye.Latex films were cast from a 1:1 mixture of Phe-and NBen-labeled latex samples.Polymer diffusion was monitored as a function of annealing temperature,and apparent diffusion coefficients(D_(app))were calculated from the energy transfer data using a simple diffusion model.These values increased with annealing temperature and decreased with T_g.Rheology measurements recorded the response of the dynamic moduli(G',G")with respect to oscillatory shear frequency(omega)over a range of temperature close to that of the diffusion experiments.The temperature dependence of polymer dynamics extracted by the rheology experiments is in good agreement with the temperature dependence of D_(app).Increasing the BA copolymer content leads to an apparent increase in long-chain branching,which is reflected in both the time dependence of D_(app)and in the dynamic moduli measurements.A greater degree of branching leads to a broader distribution of polymer diffusion coefficients and a stronger time dependence of D_(app).
机译:我们通过荧光共振能量转移(FRET)描述了聚(丙烯酸丁酯-共-甲基丙烯酸甲酯)[P(BA-MMA)]共聚物胶乳薄膜中的聚合物扩散测量。由不同重量比的丙烯酸丁酯制备了四组共聚物它们的玻璃化转变温度在4至28°C之间。乳胶颗粒用菲(Phe)作为供体染料标记,4-(N,N-二甲基氨基)二苯甲酮(NBen)标记。用Phe和NBen标记的乳胶样品的1:1混合物浇铸乳胶薄膜,监测聚合物扩散与退火温度的关系,并根据能量转移计算表观扩散系数(D_(app))这些值随退火温度增加而随T_g减小。流变学测量记录了在一定温度范围内动态模量(G',G“)对振荡剪切频率ω的响应流变学实验得出的聚合物动力学的温度依赖性与D_(app)的温度依赖性非常吻合。BA共聚物含量的增加导致长链支化的明显增加, D_(app)的时间依赖性和动态模量测量均反映了这一点。支化度越高,聚合物扩散系数的分布越宽,D_(app)的时间依赖性越强。

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