【作者】 李治国；

【导师】 范宏； 李伯耿；

【作者基本信息】 浙江大学 ， 化学工程， 2003， 硕士

【摘要】 松香改性酚醛树脂是平版油墨用连接料树脂的主要代表，也是印刷油墨中用量最大的一类树脂。为满足国际、国内对工业品高质化的需求，只有浅色的松香改性酚醛树脂才具有更好的应用前景与国际市场竞争力。 本文选用多种催化剂、浅色剂及抗氧剂合成松香改性酚醛树脂，研究相关反应的机理和树脂性能的变化规律，降低树脂色泽，探索生产浅色松香改性酚醛树脂的较佳工艺路线。 本文通过紫外分光光度计测定合成的松香改性酚醛树脂中游离酚的含量，研究了游离酚含量与树脂色泽的关系，表明：游离酚含量过高，树脂色泽会随之加深。通过对树脂产品的红外谱图分析发现，松香改性酚醛树脂产品中存在醌式结构，且醌式结构越多，树脂色泽越深，以上研究的综合分析表明，游离酚及树脂本身氧化成醌式结构是松香改性酚醛树脂色泽加深的主要原因。 本文还考察了多种不同的催化剂、浅色剂、抗氧剂及其复合体系作用下的松香改性酚醛树脂保温酯化反应进程，研究表明单一催化剂体系中磷酸酯类A效果最优，但仍不能满足快速酯化的要求，选用复合催化体系时，磷酸酯类A与AT215或受阻酚酯类物质四[β-(3，5-二叔丁基-4-羟基苯基)丙酸]季戊四醇酯的配合均较显著的加快了保温酯化进程，而由磷酸酯类A、硫代受阻酚B及有机酸按一定比例配合组成的复合催化剂体系对松香改性酚醛树脂酯化催化效率最高，且三者之间的配比催在一个最佳值使得其对松香改性酚醛树脂的协同酯化催化作用最大。 本研究还考察了不同的催化剂、浅色剂、抗氧剂及其复合体系作用下树脂综合性能的变化规律，研究表明，不同的催化剂、浅色剂及抗氧剂对松香改性酚醛树脂酯化反应过程中物料的色泽及最终产品色泽均有明显影响：单一催化剂体系中，丁基锡酸所得树脂色泽较浅、透明性较好，但酯化效率偏低；磷酸酯类A在催化酯化同时，还具有改善树脂色泽作用；次亚磷酸具有明显浅色效果，当其加入量占松香的1％可使树脂色泽降低2个色号。复合催化体系SKW与次亚磷酸的匹配具有最佳浅色效果。不同催化剂、浅色剂及抗氧剂体系作用下所得松香 浙江大学硕士学位论文 ＊改性酚醛树脂的软化点、粘度，正庚烷值明显不同。但它们一般均随保温酯化时间而提高。 本研究通过对松香改性酚醛树脂催化体系的选择、酯化阶段原料配比和操作工艺的调整，确定：SKW复合催化体系用量占松香重量的1．0％，次亚磷酸用量占松香重量的1刀％，醇羟基与松香梭基摩尔比为1刀500；复合催化剂中的硫代受阻酚组分B在保温酯化2小时后加入，次亚磷酸在保温酯化3小时后加入，酯化升温时间减为3小时，是生产浅色松香改性酚醛树脂的一条较佳工艺路线。更多还原

【Abstract】 The rosin modified phenolic resin, a mainly important one among all resins used as bands for offset inks, has the call for printing ink. With the development of industry which is demainding the high-qulity for product more and more, light colored rosin modified phenolic resin will become the only one which would have the better application prospect and competition in the international market than other.The esterification reaction in the presence of several catalysts , lightening agents, antioxidants for the synthesis of rosin modified phenolic resin was carried out in the research. The correlative reaction mechanism and the principle of the change of the resins properties were studied. The preferred synthetic process of light colored rosin modified phenolic resin was developed.In this thesis the content of free phenol in the rosin modified phenolic resins were determined by UV spectrophotometry. Meanwhile, the relationship between the content of free phenol and the color of the obtained resin was studied. It was shown that when the content of free phenol in the final resin was higher, the color of the obtained resin was deeper. The structure similar to quinone was discovered in the rosin modified phenolic resin, moreover, when the content of this structure was higher, the color of the obtained resin was deeper. The overall analysis of the above was shown that the presence of the structure similar to quinone which was resulted from the oxidation of free phenol in the obtained resin was the main cause for the deeper color of the rosin modified phenolic resin.In the presence of different kinds of catalysts , lightening agents, antioxidants, the esterification reaction course of rosin modified phenolic resin was also researched. It was shown that the substances belonging to phosphonate behaved the highest esterification catalytic efficiency among all the single catalysts system, but its catalytic efficiency was not good enough for the demand of shortening esterification time. Among the mutiply catalysts system, the phosphonate and AT215 or pentaerythrityl tetrakis [p-(3,5-di-tert-butyl-4-hydroxyphen)propionate] using together accelerate the esterification reaction obviously. The complex catalysts system SKW which was composed of salt of phosphonate, the phenol sulfide compound, a organic acid, showed the highest esterification catalytic efficiency among all. Moreover, the ratio of the three chemicals existed a optimum value which resulted in the highest cooperating esterification catalytic efficiency.Changes in the properties of the resin obtained by using different catalysts , lightening agents, antioxidants were also studied in the thesis. Results showed that the color of the resin in esterification reaction and the final products varied obviously with different catalysts, lightening agents, antioxidants. The resin with butyl stannonic acid as catalysts which showed lower esterification catalytic efficiency had relatively lighter color and better transparence than other single catalysts system, by comparison, substance A belonging to phosphonate used as catalysts could also improve the color of the obtained resin. The color of the obtained resin was decreased over 2 grades in the presence of phosphinic acid used as lightening agents in an amount of1.0 wt% based on the wight of rosin. The resin obtained by using the complex catalysts system SKW and phosphinic acid together had the lightest color among all. It was also found that the properties of the resin including n-heptane tolerance degree, softening point, viscosity varied obviously with different catalysts , lightening agents, antioxidants but they were all increased generally with time of temperature holding stage.In the research, by selecting new kind of catalysts system and adjusting ratio of raw materials in the temperature holding stage of esterification and changing operation process of synthesis of rosin modified phenolic resin, the color of the obtained resin is 3 grades lighter than that required by China enterprise’s standard.更多还原