【作者】 廖金秀；

【导师】 苏涛；

【作者基本信息】 广西大学 ， 有机化学， 2007， 硕士

【摘要】 本文研究了从醋酸乙烯酯（VAc）工业废液中分离提纯丁烯酸乙烯酯（2-丁烯酸乙烯酯，VB）的方法，并将提纯得到的VB应用于白乳胶的改性；以及用VAc与C3～C4烷酸与烯酸反应制备相应的羧酸乙烯酯。从含VB10.71％的VAc工业废液中分离提纯VB，采用先常压精馏后减压精馏的方法，控制合适的回流比，常压精馏回流比控制在10左右，减压精馏回流比控制在15左右，经过一次常压精馏和两次减压精馏，提纯得含量为95％的VB；与水共沸法常压蒸馏提纯VB效果不明显。用乙烯基交换反应，常温常压下，用含量较低（86％）的VAc分别与丁烯酸、丙酸、正丁酸、异丁酸以及丙烯酸反应合成了VB、丙酸乙烯酯（VP）、正丁酸乙烯酯、异丁酸乙烯酯（VI）和丙烯酸乙烯酯（VA），用醋酸汞作催化剂活性最高，ZnAc₂和ZnO没有催化活性。用单因素法优化实验条件，得到合成VB、VP和正丁酸乙烯酯的最佳的反应条件为：相应的羧酸：VAc为1：2（mol比），醋酸汞用量是VAc的2％，反应温度25℃，合成VB反应时间10h，VB最高产率58.8％，合成VP反应时间3h，VP最高产率为67.6％，合成正丁酸乙烯酯反应时间3h，正丁酸乙烯酯最高产率为64.4％。在VA的蒸馏分离过程中，VA很容易与未反应的VAc和丙烯酸聚合，难以将VA从生成物中完全分离；合成的VI产率为54.2％。还对用过的汞盐催化剂进行了无害化处理制备低固含量（＜22％）的白乳胶（PVAc乳液）时，加入少量（白乳胶总质量的0.03％～0.56％）的VB与VAc共聚，可制得表观粘度为19～65Pa·s的白乳胶，而且其粘接强度和耐沸水性都比相同条件下制备的不加VB的白乳胶明显提高。用于已有的白乳胶改性时，加入0.6～12.9％（按白乳胶质量计）的VB进行加热反应，其粘接强度及耐沸水性均可明显增加。VB的加入对聚乙烯醇水溶液的表观粘度和粘接强度也有显著的增大作用。表明VB用于白乳胶的改性效果良好，工业废液中的VB具有提取应用的价值。更多还原

【Abstract】 The method to extract and purify vinyl 2-butenoate （VB） from the industrial waste liquid of vinyl acetate （VAc） production was studied in this paper. The obtained vinyl 2-butenoate from the purification was used to the modification of white glue; In addition, vinyl acetate was reacted with C3～C4 of alkanoic and alkenoic acids to produce the corresponding vinyl carboxylates.To extract and purify vinyl 2-butenoate from the industrial waste liquid of VAc which contents 10.71% of VB. Distillation in normal pressure was firstly used and then in reduced pressure, to control an appropriate reflux ratio, the reflux ratio in normal pressure distillation was controlled to be～10, and the reflux ratio in reduced pressure distillation to be～15. VB of 95% was obtained after one of normal pressure and twice of reduced pressure distillations; The effectiveness to purify VB by the azeotropic distillation with water in normal pressure was not obvious.Under normal temperature and normal pressure, Vinyl 2-butenoate, vinyl propionate （VP）, vinyl butyrate, vinyl isobutyrate （VI） and vinyl acrylate （VA） were synthesized by the transvinylation reaction of lower content （86%） of VAc with 2-butenoic acid, propanoic acid, butanoic acid, isobutanoic acid and acrylic acid, respectively. Mercury acetate as the catalyst had the highest activity. ZnAc₂ and ZnO had no activity. Using the method of single factor to optimize the experimental conditions, the following optimal reaction conditions were found. For synthesizing VB、VP and vinyl butyrate, the mol ratio of corresponding carboxylic acid to VAc was 1:2, the dosage of mercury acetate was 2% of vinyl acetate （mass）, reaction temperature was 25℃, reaction time of synthesizing VB was 10 h, the highest yield of VB was 58.8%. Reaction time of synthesizing VP was 3h, the highest yield of VP was 67.6%. Reaction time of synthesizing vinyl butyrate was 3h, the highest yield of vinyl butyrate was 64.4%. During the separation process of VA, VA was very easily polymerized with VAc and acrylic acid which hadn’t reacted yet. It was very difficult to separate VA from the products completely. The yield of synthesizing VI was 54.2%. And the used catalyst HgAc₂ was disposed in a harmless manner.When preparing polyvinyl acetate emulsion （white glue） of low solid content （<22%）, adding VB in small amounts （0.03%～0.56% of total mass of the white glue） to copolymerize with vinyl acetate can produce white glue whose apparent viscosity was 19～65 Pa·s, and its adhesive strength and tolerance to boiling water were obviously enhanced compared to the white glue without adding VB in the same preparing conditions. As to improve the existing white glue, adding VB （0.6～12.9% of the mass of white glue） and conducting a heating reaction, the glue’s adhesive strength and tolerance to boiling water could also be enhanced markedly. The apparent viscosity and cohesive strength of polyvinyl alcohol water solution were also enhanced markedly after adding VB. It was shown that the vinyl butenoate in the industrial waste liquid has the value to be recovered and utilized.更多还原