New intramolecular effect observed for polyesters: An anomeric effect

A series of polyesters was prepared to evaluate hydrolytic stability as a function of cyclohexyl dibasic acid content. The three cyclohexyl dibasic acids: 1,2; 1,3; and 1,4 were formulated into polyesters with two glycols. The proportion of cis and trans isomers was evaluated via ¹H NMR. The hydrolytic stability of short chain polyesters was evaluated in an acetone/water mixture which solubilized the polyesters to mimic oligoester behavior within a thermosetting polyester coating environment. The rate of hydrolysis was monitored by acid titration and corroborated by GPC. Surprisingly, 1,2-cylohexyl diacid-based polyesters were robust, and 1,3-cyclohexyl diacid-based polyesters were the most susceptible to hydrolysis. Evidently, a 1,2-anchimeric effect for cyclohexyl dibasic acid polyesters was not an important consideration, while the 1,3-cyclohexyl ester interaction was. Consequently, an anomeric effect was proposed. Presented at the 81st Annual Meeting of the Federation of Societies for Coatings Technology, November 12–14, 2003, in Philadelphia, PA.     

Microstructure and morphology of amine-cured epoxy coatings before and after outdoor exposures—An AFM study

Atomic force microscopy (AFM) has been used to study the morphology and microstructure of an amine-cured epoxy before and after outdoor exposure. Measurements were made from samples prepared in an essentially CO₂-free, H₂O-free glove box and from samples prepared in ambient conditions. For those prepared in a CO₂-free glove box, AFM imaging was conducted on (1) an unexposed air/coating surface, (2) an unexposed coating bulk, (3) an unexposed coating/substrate interface, and (4) a field exposed air/coating surface. For samples prepared in ambient conditions, only the unexposed air/coating surface was investigated. The same regions of the exposed samples were scanned periodically by the AFM to monitor changes in the surface morphology of the coating as UV exposure progressed. Small angle neutron scattering and Fourier transform infrared spectroscopy (FTIR) studies were performed to verify the microstructure and to follow chemical changes during outdoor exposure, respectively. The results have shown that amine blushing, which occurs only under ambient conditions, had a significant effect on the surface morphology and microstructure of the epoxy. The surface morphology of the samples prepared under CO₂-free, dry conditions was generally smooth and homogeneous. However, the interface and the bulk samples clearly revealed a two-phase structure consisting of bright nodular domains and dark interstitial regions, indicating an inhomogeneous microstructure. Such heterogeneous structure of the bulk was in good agreement with results obtained by small angle neutron scattering of unexposed samples and by AFM phase imaging of the degraded sample surface. The relationship between submicrometer physical changes and molecular chemical degradation is discussed. Presented at the 82nd Annual Meeting of the Federation of Societies for Coatings Technology, October 27–29, 2004, in Chicago, IL.     

Use of laser scanning confocal microscopy for characterizing changes in film thickness and local surface morphology of UV-exposed polymer coatings

Laser scanning confocal microscopy (LSCM) has been used to characterize the changes in film thickness and local surface morphology of polymer coatings during the UV degradation process. With the noninvasive feature of LSCM, one can obtain thickness information directly and nondestructively at various exposure times without destroying the specimens or deriving the thickness values from IR measurement by assuming uniform film ablation. Two acrylic polymer coatings were chosen for the study, and the physical and chemical changes of the two systems at various exposure times were measured and analyzed. Those measurable physical changes caused by UV exposure include film ablation, formation of pits and other surface defects, and increases in surface roughness. It was found in both coatings that changes in measured film thickness by LSCM were not correlated linearly to the predicted thickness loss using the changes in the CH band obtained by the Fourier Transform Infrared (FTIR) spectroscopy measurements in the later degradation stages. This result suggested it was not a uniform film ablation process during the UV degradation. At later stages, where surface deformation became severe, surface roughness and profile information using LSCM were also proven to be useful for analyzing the surface degradation process Presented at the 81st Annual Meeting of the Federation of Societies for Coatings Technology, November 13–14, 2004 in Philadelphia, PA.     

Long-term weathering behavior of UV-curable clearcoats: Depth profiling of photooxidation,UVA, and HALS distributions

The long-term weathering performance of two UV-curable clearcoat systems was studied using in-plane microtomy in combination with infrared spectroscopy, UV spectroscopy, and ESR spectroscopy. Oxygen transport characteristics were also studied using the half-time method. The photooxidation versus depth profile was highly dependant on the presence of hindered amine light stabilizers (HALS) for both coating systems. Ultraviolet light absorbers (UVA) had little effect on the photooxidation profile. A photooxidation gradient was formed in both clearcoats due to a reduction in oxygen solubility when compared to standard thermoset clearcoats. This gradient was only seen in formulations not containing HALS. Presented at the 82nd Annual Meeting of the Federation of Societies for Coatings Technology, on October 27–29, 2004, in Chicago, IL.     

氟丙防腐涂料的耐候性研究

运用冷拼法制备氟丙树脂并配制了氟丙防腐涂料,比较研究了其与氟碳树脂涂料、含羟基丙烯酸树脂涂料性能及耐老化性能。结果表明:氟丙涂料比氟碳涂料具有更高的光泽度,比丙烯酸涂料有更好的耐候性,树脂含氟量与涂料的光泽度和失光率之间存在线性对应关系,含氟量增加,光泽度和失光率均线性降低。     

含纳米ATO聚氨酯弹性抗静电涂料

以脂肪族聚氨酯弹性树脂为基体，透明纳米ATO导电粉为导电介质，添加超分散剂，采用物理与化学相结合的分散方法对纳米ATO进行预处理。主要解决纳米粒子的分散与团聚的难题，制备出可常温固化、颜色可调的含纳米ATO聚氨酯弹性抗静电涂料。讨论了基体树脂、纳米ATO含量、超分散剂种类与加量、研磨时间以及助剂等因素对抗静电涂料的表面电阻、耐候性、弹性、强度以及稳定性等性能的影响。同时对涂料的性能进行了测试与表征。     

Weathering modification of acrylic emulsion by introducing UV absorbing groups

A new kind of UV-absorbing silicon-fluorinated acrylic emulsion was prepared by emulsion polymerization with 4-allyloxy-2-hydroxybenzophenone, 3-methacryloxypropyltrimethoxysilane (MPS) and hexafluorobutyl methacrylate (HFMA) as functional monomers. The emulsion and its coating were characterized by transmission electron microscope, Fourier transform infrared spectrum (FTIR), X-ray photoelectron spectroscopy, ultraviolet absorption spectrum,thermo-gravimetric analysis, water contact angle (CA), and artificial accelerated aging test. The results indicated that the emulsion with core-shell structure was synthesized and showed prominent absorption peaks at 320 and 350 nm. The water CA of the coating was increased from 70.2° to 86.7° because of the incorporated HFMAs and MPSs. Both of the initial and final decomposition temperatures of the coating were increased by more than 20°C compared with those of the unmodified coating. After 10 days of accelerated aging, the color difference (ΔE) and rate of loss of gloss (ΔG) were only 2.78% and 5.22%, while those of the unmodified coating were as high as 22.94% and 78.57%, respectively. Because of the UV absorbers were incorporated by chemical reaction, the new coating had a more durable and effective anti-ultraviolet performance compared with the coatings the UV absorbers were introduced by physical blending.     

LDPE农用耐候棚膜专用料的配方研究及工业化生产

研究了LDPE农用聚乙烯耐候棚膜专用料的配方及老化问题,介绍了选用母粒掺混法制备专用料的工艺路线。经人工加速老化和扣棚自然老化试验证明,用该专用料吹制的棚膜,其使用寿命可达1.5～2年,比普通膜寿命长3～4倍。     

配方组成对UPVC异型材耐候性的影响

从配方角度研究不同UPVC异型材的耐候性，探讨了不同原料和助剂（PVC、稳定剂、钛白粉、冲击改性剂、CaCO3等）对异型材老化和长期耐候性的影响，并提出优化配方的要点。     

多层复合PVC胶粘膜的性能改进

针对普通PVC胶粘膜在使用过程中存在的问题,开发了无残胶、不脱漆、耐候性能和阻燃性能优良的多层复合PVC胶粘膜.