某些高分子受阻胺对聚丙烯稳定化作用的研究

众所周知,受阻胺光稳定剂对聚烯烃有良好的光稳定效率,已引起世界的注意。然而,小分子量的受阻胺易于挥发,从而影响它的效率发挥^[1,2],为了克服这个缺点,使小分子受阻胺的高分子化是近年来受阻胺光稳定剂发展的方向,本文主要是研究三种商品化高分子受阻胺光稳定剂对聚丙烯的稳定化作用及其效率和机理。     

聚合物光老化、光稳定机理与光稳定剂(下)

大多数聚合物材料,包括塑料、橡胶、纤维、涂料等,在户外使用时会发生光老化而使使用寿命缩短。为有效防止聚合物材料的光劣化,人们已对聚合物的光老化和光稳定机理进行了广泛的研究并先后研发出了几个类型的光稳定剂。但由于户外应用范围不断扩大和环境不断恶化正使聚合物的光老化变得越来越复杂而光防护难度也日益加大,因此国内外有关聚合物光老化、光稳定机理的研究和光稳定剂的研发一直十分活跃。本文下篇阐述光稳定剂的作用机理并综述光稳定剂的研发进展。     

聚合物涂层光稳定化研究进展

用于改造各种材料的表面性质并防止其光老化的聚合物涂层的光稳定化技术近年来已经成为高分子材料科学和光化学领域的又一研究热点。本文以紫外光固化聚合物涂层为重点综述了该研究领域的发展过程、理论研究特点和应用技术的生长点,并对聚合物涂层光稳定化技术的最新进展进行了评述,讨论了聚合物涂层光稳定化技术中新型光固化树脂,多功能单体、光引发剂和光稳定剂（包括紫外吸收剂和受阻胺类稳定剂）的特点及作用机理。     

丙烯-马来酸哌啶酯共聚物的合成与表征

<正> 以2,2,6,6-四甲基哌啶为母体的衍生物作为受阻胺光稳定剂,其效率约为镍-螯合物光稳定剂的2—6倍,已引起人们的注意,但是小分子受阻胺易于挥发,从而使其光稳定作用较差。为了克服上述缺点,使受阻胺稳定剂高分子化是近年来展的趋势,本文合成了含有“丙烯”单元的高分子受阻胺光稳定剂——丙烯-马来酸哌啶酯共聚物,力求改进它与丙烯的相容性,提高光稳定效率,本文还对共聚物进行表征。     

受阻胺光稳定剂

本文介绍第4代光稳定剂——受阻胺光稳定剂的结构、合成、效率和其光稳定化作用机理,并介绍受阻胺光稳定剂的未来发展.本文可供从事高分子工业的科研、生产、助剂合成及高分子材料的老化与防老化的研究工作者参考.     

聚合物光老化、光稳定机理与光稳定剂(上)

大多数聚合物材料,包括塑料、橡胶、纤维、涂料等,在户外使用时会发生光老化而使使用寿命缩短。为有效防止聚合物材料的光劣化,人们已对聚合物的光老化和光稳定机理进行了广泛的研究并先后研发出了几个类型的光稳定剂。但由于户外应用范围不断扩大和环境不断恶化正使聚合物的光老化变得越来越复杂而光防护难度也日益加大,因此国内外有关聚合物光老化、光稳定机理的研究和光稳定剂的研发一直十分活跃。本文上篇主要阐述聚合物的光老化机理。     

高分子三重态敏化剂的研究IV: 高分子苯乙酮及其衍生物的光谱, 磷光量子产率及光敏化光稳定问题的研究

本工作合成和研究了高分子苯乙酮及其衍生物的光谱、磷光量子产率、磷光寿命以及光敏化、光稳定等问题。结量表明高分子光敏化剂和光稳定剂保持着它们原来相应小分子的光化学和光物理行为。高分子敏化剂由于T-T湮灭, 分子链中的光敏基团的存在一最佳值, 此时磷光量子产率最高, 敏化效率最好。但高分子光稳定剂则光稳定基团含量愈高光稳定能力愈强。     

高分子三重态敏化剂的研究IV: 高分子苯乙酮及其衍生物的光谱, 磷光量子产率及光敏化光稳定问题的研究

本工作合成和研究了高分子苯乙酮及其衍生物的光谱、磷光量子产率、磷光寿命以及光敏化、光稳定等问题。结量表明高分子光敏化剂和光稳定剂保持着它们原来相应小分子的光化学和光物理行为。高分子敏化剂由于T-T湮灭, 分子链中的光敏基团的存在一最佳值, 此时磷光量子产率最高, 敏化效率最好。但高分子光稳定剂则光稳定基团含量愈高光稳定能力愈强。     

高分子受阻胺对顺1,4-聚丁二烯溶液光敏降解过程的稳定作用

 本文研究了高分子受阻胺光稳定剂苯乙烯4-(甲基丙烯酸)-2,2,6,6-四甲基哌啶醇酯共聚物在用罗丹明6G光敏氧化降解顺1,4-聚丁二烯过程中的稳定作用。它具有淬灭单线态氧、分解过氧化氢以及捕获大分子自由基的能力,对其光稳定机理也进行了初步的讨论。     

苯乙烯和4-(甲基丙烯酸)2,2,6,6-四甲基哌啶醇酯共聚物PDS在聚丙烯中的分散状况及其对光稳定作用的影响

<正> 苯乙烯和4-(甲基丙烯酸)2,2,6,6-四甲基哌啶醇酯共聚物(PDS)是一种新的高分子受阻胺光稳定剂。对于高分子稳定剂来说,研究它和被稳定的高分子之间的相容性以及它在其所稳定的高分子中的分散性是十分重要的。樊宇祥等曾用显微镜观察过含5％PDS的共混体系的形态,指出PDS是以颗粒的形式分散于PP连续相中。作为光稳定剂,     

Reactions of stabilizer compounds. IV. ESR studies of the formation of stable nitroxyl radicals in the photooxidation of polypropylene containing hindered amine light stabilizers

ESR studies of the formation of stable nitroxyl radicals in the photooxidation of polypropylene containing 2,2,6,6-tetramethyl-4-hydroxypiperidine (II) and the commercial light stabilizer bis(2,2,6,6-tetramethyl-4-piperidinyl)sebacate (III) are described. Spectra of the stable nitroxyl radicals in solid polymer and in solution after extraction from the polymer were obtained. The extract from photooxidized polypropylene containing the bifunctional stabilizer (III) showed only the mononitroxyl radical. The possible formation of polymer-bonded nitroxyl radicals from (III) is discussed.     

Dispersion polymerization of acrylamide. III. Partial isopropyl ester of poly(vinyl methyl ether-alt-maleic anhydride) as a stabilizer

Dispersion polymerization of acrylamide at 40 degrees C in t-butyl alcohol-water media of varying composition (50 to 90 vol% alcohol) using a partial isopropyl ester of poly(vinyl methyl ether-alt-maleic anhydride) as the stabilizer has been studied. The isopropyl ester derivative proves to be a better stabilizer than its precursor polymer. However, the particles were polydisperse in size. The number average diameter of the particles increases linearly with the solubility parameter of the dispersion medium. Dispersions of nanoparticles of polyacrylamide are produced when the t-butyl alcohol content of the dispersion medium is 90% by volume. Comparison of the particle diameter measured by transmission electron microscopy with that measured by dynamic light scattering in acetone reveals a thickness of the hairy stabilizer layer on the dispersion particles of 31 nm.     

聚丙烯膜表面光接枝聚合

对聚合物表面进行接枝聚合是一种有效的材料改性方法。近年来,S.Tazuke,Y.Ogiwara,高志民等人做了一些用紫外光引发接枝方面的工作,获得了较满意的结果。为提高聚丙烯(简称为PP)膜的光稳定性,我们研究了将一种受阻胺类光稳定剂,甲基丙烯酸2,2,6,6-四甲基哌啶醇酯(简称为MTMP)光接枝到PP膜表面的聚合过程。     

Photostabilization of recycled pigmented polypropylene crate material

The photostabilizing efficiencies of various light stabilizer systems in recycled pigmented polypropylene crate materials, previously in use for 6–7 years, have been examined using the standard carbonyl index and time to embrittlement methods. Thirty-two polymer film samples with and without additional stabilizer have been prepared and exposed in both a Xenotest-150 and Microscal apparatus. The performance of the various light stabilizer systems in both exposure units are compared and discussed.     

一种受阻胺封端的聚芴蓝光材料的合成及其稳定性研究

以五甲基哌啶醇、对溴苯酰氯为原料合成了一种受阻胺抗氧稳定剂,通过Suzuki反应将其封端到聚(9,9-二辛基)芴上.通过核磁共振谱、凝胶渗透色谱对合成材料的分子结构进行了表征;并利用荧光发射光谱和退火方法,对其光谱热稳定性进行了细致研究.实验结果表明,当在聚芴分子链上引入受阻胺五甲基哌啶醇后,其荧光发射光谱的稳定性显著提高,绿光区发射现象明显减弱.     

Highly sensitive determination of a polymeric hindered amine light stabilizer in polypropylene by reactive thermal desorption-gas chromatography using nitrogen-specific detection

Highly sensitive and specific determination of trace amounts of a polymeric hindered amine light stabilizer (HALS) in polypropylene (PP) materials could be established by improving reactive thermal desorption-gas chromatography (RTD-GC) in the presence of an organic alkali, tetramethylammonium hydroxide. By using nitrogen-phosphorus detection, highly selective detection of the HALS-related components was attained. In addition, the use of a polar poly(ethylene glycol) separation column alleviated the adsorption of minor specific pyrolysis products. This modified RTD-GC method allowed the determination of the polymeric HALS (Mr 1900) in PP even for trace concentrations between 100 and 500 ppm, through observing selectively the characteristic products containing a tetramethylpiperidine moiety, which had been impossible to detect under the previous RTD-GC conditions using a non-polar separation column and conventional flame ionization detection.     

高分子受阻胺光稳定剂存在下聚丁二烯的单线态氧氧化

用粘度法、ESR、IR、GPC等方法研究了三种商品高分子受阻胺存在下聚丁二烯的单线态氧氧化,结果表明,高分子受阻胺抑止聚丁二烯的单线态氧氧化,其效率是944>PDS>770>622。用Monroe方法测定了受阻胺对单线态氧的猝灭速率常数,K_q~(-O_2),它们是944(3.2×10~6M~(-1)s~(-1)),PDS(8.2×10~5M~(-1)s~(-1)),622,770为2×10~5M~(-1)s~(-1),ESR研究表明,在本实验条件下,944和PDS能够产生稳定的氮氧自由基No,而622则不产生。用GPC研究还发现,在本实验条件下,PDS具有对聚丁二烯的接枝——交联效应,提出了这种接枝交联效应的机理。     

Loss of light stabilizers from polypropylene

Loss of light stabilizers. related to 2-hydroxybenzophenone and 2-(2-hydroxyphenyl) benzotriazole. from isotactic polypropylene was measured over the range 60–120° and during storage at 25'. The light stabilizer content in polypropylene corresponded to that used in practice. The rate constants and the activation energy were calculated from the rate of loss. The influence of the structure of stabilizer on the rate of loss from polymer is discussed. The losses of stabilizers from polymer were compared with the vapour pressure of stabilizers and with the losses of stabilizers alone at 280. The rate of diffusion of stabilizers to the surface of polypropylene and the rate of even evaporation may cause a rapid diminution of stabilizer or undesirable accumulation on the polymer surface.     

Photochemical processes involving TiO2 pigments and TiO2–light stabilizer combinations in commercial polyolefins

The photoactivity of titania pigments at different loadings in both polyethylene and polypropylene is examined by phosphorescence and carbonyl formation and a correlation between the two observed. A nickel (II) chelate stabilizer proved more effective than a hydroxybenzophenone stabilizer in the presence of anatase. This difference in stabilizing efficiency appears to be due to more efficient quenching of the excited state of the anatase by the nickel chelate than by the hydroxybenzophenone.