漆酚缩甲醛钕聚合物的特性与表征

由漆酚甲醛缩聚物(PUF)与三氯化钕制备漆酚缩甲醛钕聚合物(PUFN), 并采用元素分析、 IR、 DMTA和GPC对其进行表征. 结果表明, PUF与Nd3+发生配位反应, 其产物PUFN的弹性模量比PUF的大, 热稳定性提高, 并且具有优良的耐化学介质腐蚀性能, 对正丁醇和冰乙酸的酯化反应具有催化活性.     

漆酚钼螯合高聚物的合成及表征

采用漆酚与四氯氧化钼反应制得兼具螯合物特点和生漆固有性能的漆酚钼螯合高聚物 (PUM) .对不同反应条件下制备的高聚物的含钼量进行了测定 .并通过元素分析、红外光谱、电子顺磁共振谱、光电子能谱、质谱、高效液相色谱和热失重分析探讨高聚物的生成过程、结构特征和热性能 .结果表明 ,漆酚与四氯氧化钼首先发生氧化还原反应和配位反应生成螯合物 ,然后进一步聚合成为高聚物 ;该高聚物中存在漆酚钼螯合物结构单元且具有很好的热稳定性 ,其耐热性能比生漆和传统黑推光漆好得多 .     

漆酚缩甲醛钇聚合物的热性能及其表征

利用漆酚甲醛缩聚物(PUF)在非水热溶剂中与三异丙氧钇反应制得漆酚缩甲醛钇聚合物(PUFY),用IR、XPS和TG-DSC对其结构进行表征。结果表明,三异丙氧钇中Y(Ⅲ)与PUF中酚羟基上的氧形成了配位键;在Y(Ⅲ)的作用下PUF侧链进一步交联聚合,产物PUFY的耐热性和耐溶剂性较配体PUF的好。     

漆酚缩甲醛钕聚合物催化合成环己酮乙二醇缩酮

以环己酮和乙二醇为原料,漆酚缩甲醛钕聚合物为催化剂合成了环己酮乙二醇缩酮。实验结果表明：在环己酮100mmol,n(环己酮)：n(乙二醇)=1：1,漆酚缩甲醛钕聚合物3．0g,环己烷7．5mL,回流反应1．0h,目标化合物的收率达74％。     

漆酚醛缩聚物/丙烯酸树脂IPN涂料的制备及性能

漆酚醛缩聚物/丙烯酸树脂IPN涂料的制备及性能;漆酚甲醛缩聚物;丙烯酸树脂;互穿聚合物网络;涂料     

电化学聚合漆酚-铕配合物的合成及性质

稀土金属具有特殊的理化性质,若能把稀土引入聚合物基质中,可望获得有着广泛应用前景的稀土-聚合物材料[1].漆酚是侧基为不饱和直链的邻苯二酚.根据其特点,利用电化学技术,可使其在不饱和侧链上发生氧化聚合生成聚合漆酚EPU膜[2].本文提出利用三异丙氧基铕与EPU膜作用,合成漆酚铕稀土金属配合物EPU-Eu(),国内外尚未见报道.提出了漆酚铕稀土金属配合物合成方法,并对其结构和部分性质进行表征.结果表明,EPU-Eu()电阻比EPU大,配合物中Eu()含量高达9.6%.由于Eu()与EPU存在配位作用,并引起进一步交联,因而难溶于绝大多数有机溶剂,玻璃化…     

漆树液精油化学成分的研究

用GPC、GC-MS-DS法对中国漆树液中漆酚与虫漆酚精油化学成分进行了研究。其主要成分为3-C₁₅和C₁₇烃基取代的邻苯二酚化合物,其中三烯漆酚和单烯虫漆酚含量最高。其它成分为4-C₁₅,C₁₇烃基取代的邻苯二酚及3-C₁₅和C₁₇烃基取代的单酚化合物。气相色谱分离鉴定组分占精油含量的98%以上。原始漆树液中内含7%～9%漆酚聚合物。     

漆酚铝螯合聚合物的合成研究

本文报道漆酚与无水氯化铝反应合成漆酚铝螯合物的方法,并通过测定反应过程HCl析出量、产物含铝量,并用红外光谱、质谱,研究其结构特征。实验表明,部分螯合的漆酚铝螯合型高聚物涂料,具有优良的物理机械性能和优异的耐热性能。     

漆酚钛聚合物/蒙脱土纳米复合材料的制备、结构与性能

用溶液插层聚合方法制备漆酚钛聚合物/蒙脱土纳米复合材料(PUTi/OMMT),并用XRD、TEM和TG等对其结构、性能进行测试与表征.XRD结果表明,通过溶液插层,PUTi分子链进入了OMMT片层间,从而使片层间距增大.TEM观察表明OMMT片层在PUTi聚合物中基本达到纳米级分散.与PUTi相比,PUTi/OMMT纳米复合材料具有更好的耐热性能和抗紫外光性能.     

漆酚缩甲醛镧配合物的制备、结构及性能

利用漆酚缩甲醛(PUF)和三氯化镧在非水热溶剂中反应制得漆酚缩甲醛镧配合物(PUFLa)，IR、XPS和TG表征结果表明：三氯化镧中La^3 与漆酚缩甲醛中酚羟基上的氧形成了配位键；在La^3 的作用下，PUF上的侧链进一步交联聚合。PUFLa在亚硫酸钠水溶液中能引发催化甲基丙烯酸甲酯聚合。通过正交实验设计考察了PUFLa用量、反应温度、反应时间、单体甲基丙烯酸甲酯用量和亚硫酸钠浓度对单体转化率的影响。结果表明。反应温度和反应时间是影响单体转化率的主要因素。PUFLa还具有良好的耐热性和抗溶剂性。     

漆酚酯键合硅胶液相色谱固定相的制备与应用

以甲基丙烯酸漆酚酯为色谱配体,制备了一种新型色谱固定相。首先以漆酚和甲基丙烯酰氯为原料制备得到甲基丙烯酸漆酚酯,并通过物理吸附涂覆到由3-（甲基丙烯酰氧）丙基三甲氧基硅烷化学修饰的硅胶上,再通过自由基引发与硅烷化硅胶的双键聚合制得漆酚酯键合硅胶固定相（USP）。对固定相进行傅里叶红外光谱（FT-IR）、热重分析（TGA）、扫描电子显微镜（SEM）和元素分析（EA）表征,结果表明通过共聚反应成功地将漆酚酯固定在硅烷化硅胶上,且制备出的固定相具有良好的单分散性。采用匀浆法装柱,以乙腈-0.05%磷酸溶液（3：97,v/v）为流动相,流速为0.4 mL/min,检测波长为220 nm,考察固定相对天麻浸膏的分离性能。以乙腈-水（50：50,v/v）为流动相,流速为0.5 mL/min,检测波长为290 nm,考察固定相对吴茱萸浸膏的分离性能。结果表明该固定相对天麻浸膏和吴茱萸浸膏均具有良好的分离性能,从天麻浸膏中分离出5个色谱峰,从吴茱萸浸膏中分离出2个色谱峰。与商品化C₁₈ 柱相比,USP柱可以从天麻浸膏中分离出更多的有效组分并实现基线分离,分离吴茱萸浸膏的色谱条件更为环保和安全。采用低流速对天麻浸膏和吴茱萸浸膏进行分离,减少了流动相的使用量,分离结果令人满意。以天然产物漆酚制备色谱固定相,既为分离纯化天麻素和吴茱萸碱提供了一种新的方法,又为液相色谱固定相制备提供了新的思路,还拓展了生漆在色谱分离材料方面的应用。     

Studies of Japanese lacquer: Urushiol dimerization by the coupling reaction between urushiol quinone and a triolefinic component of urushiol

Previously, the formation of urushiol quinone from urushiol was demonstrated in the laccase-catalyzed oxidation process of the sap of the Japanese lacquer tree (Rhus vernicifera D.C.) or of lacquer formed from it. This paper presents the results of the investigation on the participation of urushiol quinone in the oxidative polymerization and crosslinking of the sap or the lacquer. The polymeric urushiol was obtained by the fractionation of the mildly oxidized sap (Japanese lacquer), and a specific dimeric urushiol was isolated from it by thin-layer chromatography (TLC). Structural analysis of the dimer illustrated that it has a conjugated triene structure and may be formed by a coupling reaction between urushiol quinone and a triolefinic component of urushiol. Further support for this was given by the spectroscopic study of the reaction between 4-tert-butyl-o-quinone and the triolefinic component of dimethylurushiol, and by the isolation and identification of the coupling product between them.     

Development and Characterization of Laccol Lacquer Blended with Urushiol Lacquer

A lacquer blending urushiol and laccol was investigated. The blended lacquer with 30wt.% urushiol and 100wt.% laccol has a good drying property and film hardness. 2-D-NMR and FD-MS measurements of the lacquer dimer showed that a transfer of radicals between urushiol and laccol occurred during the enzymatic polymerization, and 4-4′ biphenyl, 4-6′ (4′-6), and 6-6 (6-6′) dibenzofuran structures were obtained.     

漆酚钕高聚物的合成

研究采用漆酚与氯化钕合成制备漆酚钕螯合高聚物的方法和工艺条件；ＩＲ和ＭＳ测定表明该产物存在邻酚基上的Ｏ－Ｎｄ键．ＤＴＡ和ＴＧ分析结果表明它具有比生漆更高的热稳定性，热分解动力学属一级反应，平均表观活化能１．３５６×１０５Ｊ·ｍｏｌ－１，磁化率为８．６０×１０－６ｃ．ｇ．ｓ．有可能作为优良耐热性能的有机高分子磁性材料     

Structural study of oriental lacquer films during the hardening process

Oriental lacquer is the natural resin obtained by tapping lac trees. It hardens into a tough and insoluble film. The extreme hardness and insolubility are some of the most important functions, which are required for industrial coating materials. In this study, two kinds of oriental lacquer films, traditionally named Kiurushi (raw urushi) and Kuromeurushi produced by two different pretreatments, were analyzed during hardening with Fourier transform infrared spectroscopy (FT-IR), thermogravimetry/differential thermal analysis-mass spectrometry (TG/DTA-MS) and pyrolysis-gas chromatography/mass spectrometry (Py-GC/MS) to investigate their functional expression process. Typical functional groups of the lacquer films were detected by FT-IR. The TG/DTA-MS curves clarified that the thermal degradation of the lacquer films gradually began at around 200 °C, and reached the fastest rate at 400-500 °C. Apparently, FT-IR and TG/DTA-MS could not reveal any difference between the films. On the other hand, Py-GC/MS revealed differences between the films in the peak area ratios of 3-pentadecenylcatechol to 3-pentadecylcatechol and 3-pentadecadienylcatechol to 3-pentadecylcatechol. The ratios of Kiurushi lacquer film were higher than those of Kuromeurushi lacquer film. Both ratios, furthermore, decreased during hardening due to polymerization of the alkenylcatechols into an urushiol polymer skeleton comprising nucleus-side chain and side chain-side chain cross-linkages with 3-pentadecylcatechol at the terminal. The present results suggest that the reaction rate of these cross-linkages in Kuromeurushi lacquer film is faster than that in Kiurushi lacquer film. A good correlation was found between the peak area ratios obtained by Py-GC/MS and hardness obtained by pencil hardening testing. Oriental lacquer expresses the functions - an extreme hardness and insolubility - accelerating the nucleus-side chain and side chain-side chain cross-linkages. Furthermore, it has become clear that the traditional treatments called Nayashi and Kurome effectively accelerate the hardening rate by activating the cross-linkages.     

中国生漆饱和漆酚冠醚化合物的核磁共振研究

本实验用~1H-NMR法研究了中国生漆饱和漆酚冠醚化合物的结构与碱金属离子选择电极性能间的关系。研究结果表明,只有当饱和漆酚冠醚化合物实现全关环时才与碱金属离子有高的络合容量,且反式构型化合物的络合容量比顺式构型化合物大得多。     

Characterization of Chinese Lacquer in Historical Artwork by On-Line Methylation Pyrolysis-Gas Chromatography/Mass Spectrometry

An effective method for characterizing Chinese lacquer as binding medium in historical artwork has been developed by on-line methylation pyrolysis-gas chromatography–mass spectrometry (pyrolysis GC–MS). The characteristic pyrolytic components of Chinese lacquer were identified in artificially aged pure and pigmented lacquer. Methylation of urushiol (mainly composed of catechol derivatives) was performed by adding tetramethyl ammonium hydroxide to convert phenolic hydroxyl groups into methylated derivatives to improve the resolution of catechol derivatives and urushiol monomers. The mechanism of formation of small molecular components was proposed, and the influence of different mineral pigments (azurite, malachite, ochre, and cinnabar) on the determination of characteristic components was discussed. Aliphatic hydrocarbon components, benzene derivatives, catechol derivatives, and urushiol monomers were proposed as characteristic pyrolytic components. In addition to 3-pentadecene-catechol, 3-pentadecane-catechol, and 3-heptadecene-catechol, 3-pentadecene-phenol was also identified as an urushiol monomer in Chinese lacquer. Four pigments slightly reduced the detection of aliphatic hydrocarbon components, but were unconspicuous for the detection of benzene derivatives. Azurite, malachite, and cinnabar decreased the measurement of urushiol monomers, but ochre significantly increased their relative abundance. The established on-line methylation pyrolysis GC–MS procedure and summarized data were successfully applied to the identification of samples collected from Terra-Cotta Warriors and Horses of Qin Dynasty (221–207 BC), Han Yang Mausoleum of Han Dynasty (206 BC–24 AD), and Dazu Grotto of Tang Dynasty (618–907 AD).     

天然生漆/丙烯酸树脂IPN涂料的制备与性能

研究了直接由天然生漆(raw lacquer,RL)和多羟基丙烯酸树脂(multihydroxyl polyacrylate resin,MPAR)制备IPN(interpenetrating polymer network)涂料的方法,以及生漆的预聚合对涂料成膜的作用,并对共混物涂膜的物理机械性能、抗溶剂性能、抗紫外线性能等进行了测试表征。结果表明,天然生漆/丙烯酸树脂互穿网络共混能使RL与MPAR相互交联、缠结,其涂膜兼具有天然生漆和丙烯酸树脂的优良性能。