菜籽油的改性及其在皮革加脂剂中的应用

【作者】 任斌；

【导师】 汤克勇；

【作者基本信息】 郑州大学 ， 皮革化学与工程， 2007， 硕士

【摘要】 中国已成为世界公认的皮革加工和贸易中心，皮革加工离不开皮革化工材料。加脂剂是皮革加工中用量最大的化工材料之一，是左右皮革身骨、手感、风格且制约皮革工业发展的重要因素。目前，在质量和性能方面，国产加脂剂尚难以满足迅速发展和日益高档化的皮革加工的需要，开发高性能的皮革加脂剂新品势在必行。本文根据皮革加脂工艺对加脂剂的要求，首先对加脂剂进行分子设计，在醇(甲醇)油摩尔比为2.5：1、催化剂(KOH)用量为1.2％(以菜籽油的质量为基准，下同)、反应温度65℃、反应时间3.0h的条件下，对菜籽油进行醇解改性，以引入羟基和降低油脂的分子量；然后以醋酸作为活性氧载体，在强酸性阳离子交换树脂用量为5.0％、反应温度55℃、双氧水用量为40.0％的条件下，对醇解油脂进行环氧化改性，以引入活性环氧基团；再对环氧化产物进行亚硫酸化改性、胶原蛋白接枝改性和羟化乙氧基化双重改性，分别引入亲水性的磺酸基、多肽链和醚链，使其具有自乳化性，制得加脂剂中的改性油脂成分。为改进加脂皮革的手感，本文还引入了新的材料——氨基硅油和蜂蜡。在保持氨基硅油原有优异性能的前提下，选用乙酸酐作为酰胺化改性剂，在改性反应条件为：以氨基硅油的质量为基准，改性剂用量为6.0％、溶剂用量55-65％、反应温度50-55℃、反应时间1.5h的情况下，对氨基硅油进行有效的改性，减弱其阳离子性，经红外光谱测试验证了改性后有酰胺基团的存在。并以复合乳化剂2作为乳化剂，在其用量为蜂蜡质量的20.0％、乳化时间60min、乳化温度85℃的条件下，对蜂蜡进行有效乳化，得到了细小、稳定的蜂蜡乳液。按照胶原蛋白改性油脂10份、亚硫酸化改性油脂15份、羟化乙氧基化双重改性油脂25份、复合乳化剂15份、改性氨基硅油2.5份、凡士林2.5份、蜂蜡液30份、水40份的比例，将上述改性产物进行复配，即得本文研制的加脂剂，并进行了大量的加脂应用试验。结果表明，本试验所得加脂剂的最佳应用条件为：中和至pH=6.5，加脂温度为60℃。加脂革丰满、柔软、弹性好，而且有滑爽、丝光、油润的“硅感”效果。不仅体现了植物油的特性，同时也显现了有机硅的优点，为一种新型、高效、多功能的制革用加脂材料。更多还原

【Abstract】 China has become an important center of leather-making and trading. In the leather-making process, leather chemicals are needed, in which fat-liquoring agent is one of the most important chemical materials. The feeling and style of leathers are always determined by fatliquoring agents to some extent. It may even be said that fat-liquoring agent is one of the most important factors restricting the development of leather industry. At present, both in the qualities and performances, the domestic fatliquoring agents can not meet the demands of leather industry. The preparation of fat-liquoring agent with high qualities and performances is imperative.The principle of molecule design was applied in this paper. First, in order to introduce the hydroxyl groups and reduce the molecular weight of vegetable oil, the rapeseed oil was modified by transesterification. The modifying conditions were described as follows: the ratio of the rapeseed oil and carbinol was l:2.5(mol:mol), the catalyst dosage was 1.2% of rapeseed oil in weight, reaction temperature was 65°C, and reaction time was 3hr. Acetic acid was chosen as the active oxygen carrier, and a strong-acid ion exchange resin was chosen as the catalyst, the transesterification product was modified by epoxidation. The modifying conditions were described as follows: the catalyst dosage was 5.0%, the oxydol dosage was 40.0% and the reaction temperature was 55°C. Then the epoxidation product was modified by sulphitation, collagen and polyethylene glycol, respectively. The hydrophilic groups such as sulfonic groups, collagen chains and ether chains were introduced. The self-emulsifiable oil was prepared.For the improvement of the handfeeling of the fatliquored leathers, both amino silicone oil and beeswax were introduced, too. In order to weaken the cationic and keep the excellent properties of the flexibility, smoothness and the elasticity, the amino silicone oil was modified by acetic anhydride. And the modifying conditions were described as follows: modifying agent was 6.0% of amino silicone oil in weight, solvent was 55-65% of the amino silicone oil, reaction temperature was 50-55℃, and reaction time was 1.5h. The FTIR spectra were successfully applied to characterize the structure of the modified amino silicone oil. The beeswax was emulsified when the conditions were as follows: the composite emulsification agent dosage was 20.0% of beeswax in weight, emulsification temperature was 85℃and emulsification time was 60min. Then the above-mentioned products were compounded according to the following proportions: the rapeseed oil modified by collagen was 10.0 in weight, the sulphited rapeseed oil was 15.0 in weight, the hydroxide and ethoxyl rapeseed oil was 25.0 in weight, the composite emulsification agent was 15.0 in weight, the modified amino silicone oil was 2.5 in weight, the beeswax emulsion was 30.0 in weight, the vaseline was 2.5 in weight and the water was 40.0 in weight. Then a compound fatliquoring agent with high qualities was prepared. The fatliquoring experiments were conducted. The results indicated that the optimal fatliquoring conditions were as described as follows: the fatliquoring temperature was 60℃, the pH of neutralization was 6.5. The leathers fatliquored with it showed good fullness, softness, elasticity, greasy and silky feeling.更多还原