In this work, we synthesized surfactant-free latex dispersions of nanoparticles (NPs) based upon emulsification of a preformed proprietary BASF polymer (M_n^GPC = 5000 g/mol, Р= 3, denoted as Pol), in which the —COOH groups were partially neutralized by ammonia. To obtain useful coatings with polymers of such low molecular weight (MW), we approached this problem through the reaction of carboxylated polymer dispersions with neopentyl glycol diglycidyl ether (NGDE, 20 to 60 mol% based on carboxyl groups) to increase the MW and to introduce gel content. We employed AFM to monitor the influence of cross-link density on the surface roughness and found the presence of cross-links increases the resistance of particles to deformation. Fluorescence resonance energy transfer (FRET) measurements were carried out to determine the extent of polymer mixing upon film formation. Our most important finding is that the gel content substantially limited the extent of molecular mixing at long annealing times or in corresponding solvent-cast films. In parallel, we carried out a series of similar reactions on the secondary dispersion particles with a monoepoxide, consisting of a mixture of dodecyl and tetradecyl glycidyl ether. This reaction maintained the size and size distribution of the latex particles. These polymers had no gel content, but the reaction with the epoxide lowered the T_g of the polymer. FRET studies showed a pronounced influence of T_g on the rates of polymer diffusion in these films.

在这项工作中，我们基于预成型的专有 BASF 聚合物（M _n ^GPC  = 5000 g/mol，D = 3，表示为 Pol），其中 -COOH 基团被氨部分中和。为了获得具有如此低分子量 (MW) 的聚合物的有用涂层，我们通过羧化聚合物分散体与新戊二醇二缩水甘油醚 (NGDE，基于羧基的 20 至 60 mol%) 的反应来解决这个问题，以增加 MW 和介绍凝胶含量。我们采用 AFM 来监测交联密度对表面粗糙度的影响，发现交联的存在增加了颗粒对变形的抵抗力。进行荧光共振能量转移 (FRET) 测量以确定膜形成时聚合物混合的程度。我们最重要的发现是凝胶含量大大限制了长时间退火或相应的溶剂流延薄膜中分子混合的程度。同时，我们用单环氧化物对二级分散颗粒进行了一系列类似的反应，单环氧化物由十二烷基和十四烷基缩水甘油醚的混合物组成。该反应保持了胶乳颗粒的尺寸和尺寸分布。这些聚合物没有凝胶含量，但与环氧化物的反应降低了Ť_克聚合物。FRET 研究表明T _g对这些薄膜中聚合物的扩散速率有显着影响。