2-庚酮合成新工艺及苯酐聚酯多元醇的合成与改性.doc

山东大学硕士学位论文2-庚酮合成新工艺及苯酐聚醋多元醇的合成与改性姓名：乔洪申请学位级别：硕士专业：有机化学导教师：郝爱友20080510山东大学硕士学位论文摘要论文工作分为两部分：一.2-庚酮合成新工艺；二.苯軒聚酷多元醇的制备与 改性一、2-庚酮合成新工艺2-庚酮（ MAK)在美国、欧洲等国家被批准用于食品，微量用于日用香精, 广泛用于工业溶剂、纤维、医药、农药、香料、化工等领域，有较好的市场前景关于 2-庚酮的制备报道己经很多，不过多数路线生产工艺较为复杂，总产率 亦偏低，成本较髙，很难工业化生产本文发现了一个合成 2-庚酮的新方法：以常用的丙酮与正丁醒为原料，经过 径醒缩合脱水，一步得到中间体 3-庚炼-2-酮，再经催化加氢得到 2-庚酮此路 线原料成本低，操作步骤简单，通过控制温度，加入环己烧作溶剂、ZnCl2作助 剂，减少了酸性脱水这步反应，降低了处理过程中产品的损失，提高了收率本路线副产 2-乙基-2-己稀酸与 2-乙基己酸，同样具有较广阔的市场应用前 景，前者可以作为香精香料，后者氧化成异辛酸，是高档涂料和髙档油墨的绿色 环保溶剂本文的创新之处：1) 加入环己焼，既起到稀释正丁酸以抑制其自聚合的作用，又能起到相转 移提取剂的作用，提高了反应速率与原料的转化率；同时环己烧又可以作为催化 加氧的溶剂，有利于降低生产成本；2) 本路线可以副产 2-乙基-2-己稀醛与异辛醒，使正丁酸转化率达到 95.0% 以上，可以重复利用过量的丙酮与溶剂。

二、苯肝聚酯多元醇的制备与改性苯軒聚酯多元醇由于分子结构中引入苯环结构，增加了聚氨酷链中的苯环含 量，赋予了聚氧酷泡沫许多优良性能，如朝性、阻燃性、粘结性、耐化学性等 苯野聚酷多元醇的优良性能使其广泛应用于家电、汽车、石油化工、建筑材 料、家具行业，可用于冰箱保冷、消毒柜、冷库、冷藏车、管道保温保冷、建筑 板材、仿木家具、胶粘剂、鞋底原液、塑胶跑道及喷涂材料等领域本文以苯酐、二甘醇、两三醇等为基本原料，加入聚酸酐下脚料、聚酷瓶、山东大学硕士学位论文松香酷、工业级对苯二甲酸进行改性，一步法合成了具有不同酸值、轻值的芳香 族聚酷多元醇，并成功应用于工业化生产以低轻值的低聚多元醇与 MDI 合成 预聚体，作为胶粘剂的固化剂组分；以低酸值的高聚多元醇作为胶粘剂的轻基组 分，加入稀料与助剂，制备了建筑用彩钢夹芯板专用的双组分聚氨酯胶粘剂 本文的创新之处：1) 首次以聚酸酐下脚料代替部分苯酐作为酸组分，制备了性能优良的芳香 族聚酷多元醇，有效利用了工业下脚料；2) 结合工业化生产实际，为苯軒聚酷多元醇的制备与改性设计和完善了中 试方案，并直接应用于工业化生产关键词：2-庚酮；3-庚稀-2-酮；苯野聚酷多元醇；夹芯板；聚氨酷胶粘剂；合成AbstractThe thesis includes two parts: one is a new synthesis method of 2-heptanone, the other is the preparation and modification research of benzolic acid anhydride polyester polyols.1. A New Synthesis Method of 2-Heptanone2-Heptanone (MAK) has been authorized to use in food and daily flavor in US, Europe and other countries. It has also been widely used as industrial solvent, textile fiber, medicine, agricultural chemicals, spices etc.There are lots of works has been reported about 2-heptanone. But the most routes are more complex with somewhat lower yield.This work introduces a new synthesis method of 2-heptanone using acetone and butyraldehyde as the raw materials. 2-Heptanone could be obtained by the reaction of hydroxy aldehyde condensation, dehydration and catalytic hydrogenation. In the reaction, cyclohexane was used as the resolver and ZnCk as the assistant.The 2-ethyl-2-hexenoicaldehydes and 2-ethylhexyl aldehyde as by-product could also be need in the market, the former may take the essence spice, the latter could be oxidized to 2-ethyl hexanoic acid, which is the green environmental protection resolver of upscale coating and the upscale printing ink.Main innovations of this work:山东大学硕士学位论文1) The cyclohexane plays a very important role which contains the resolver dilution, extraction of the transfer agent, and raises reaction rate and raw material conversion rate.2) This route enables the conversion rate of butyraldehyde to 100% nearly with the reuse of the excessive acetone and cyclohexane.2. The Synthesis and Modified Research of Benzolic Acid Anhydride Polyester PolyolsThe benzene ring structure in the benzolic acid anhydride polyester polyols has entrusted polyurethane froth many fine performance, such as toughness, the flame retardance, cohesiveness, bear etc.The fine performances of benzolic acid anhydride polyester polyols causes it widely to apply in the electrical appliances, the automobile, the petroleum chemical industry, the building material, the furniture profession. It is used in the refrigerator guaranteeing cold, the disinfection cabinet, the cold storage, the refrigeration truck.the piping insulation to guarantee cold, the building board, imitate wooden domains, adhesive, shoe sole original fluid, plastic track, spray coating material, and so on.This work uses benzolic acid anhydride, 2,2'-oxydiethanol, glycerol as the base stock, and uses polyanhydride, the polyester bottles, the rosin ester, the dicarboxylic acid of technical grade to carry on the modification to prepare aromatic polyester polyols with different acid value and hydroxyl value in one-stage process.Main innovations of this work:1) It is the first time to prepare aromatic polyester polyols with fine performance by taking polyanhydride residue as the sour component.2) Combined with the practical production, a reasonable pilot programme of benzolic acid anhydride polyester polyols was designed and successfully applied into industrialized production.Keywords：2-heptanone; 3-hepten-2-one; benzolic acid anhydride polyester polyols;sandwich panel; polyurethane adhesive; synthesis山东大学硕士学位论文第一部分 2-庚酮合成新工艺第一章前言2-庚酮（ 2-Heptanone)，又名甲基正戊基酮 （Methyl n-Amyl Ketone)，简称 MAK, CAS： 110-43-0，无色透明液体，焰点-35.5 。

C,沸点 150.6-C， 闪点 47X： ’ 相对密度 0.8166 (20/4-C),折光率 1.4110 (20C); 具有强烈的类似香蕉水果香 气，微溶于水（0.4%),溶于乙醇、丙二醇、乙酸等有机溶剂0图 1-1 2-庚的结构1.1 2-庚酮的应用进展2-庚酮在美国、欧洲等国家被批准用于食品，微量用于康乃馨等日用香精中，主要用途是配制香蕉、相梧、桃子、椰子、草毒、奶酪等食用香精，广泛用于工 业溶剂、纤维、医药、农药、香料、化工等领域，有较好的市场前景 1.1.1 香精香料⑴在自然界中 2-庚酮存在于丁香精油、斯里兰卡肉桂油等芳香油中，还存在于 肉和乳酷中 2-庚酮有特别的香蕉香气，并伴有轻微的药香香韵，其香味是新鲜 而带乳脂样的辛香，稍微有些果香味因此，在香料工业中可用于调香2-庚酮既可用来调配康乃馨、药草香等化妆品香精，也可用于调配香蕉、椰 子、蜜桃、报橘、奶油、干酷等食品香精由 2-庚酮调配的香精可广泛用于软饮 料、冰激凌、糖果、烘烤食品和调味品的加香2-庚酮在水中香气阈值：140〜3000ppb,它在某些食品中的参考用量为：软 饮料 2.7ppm、冰激凌 6ppin、糖果 6.4ppm、烘烤食品 13ppm、调味晶10〜25ppm。

1.1.2 昆虫驱避剂2-庚酮是一种昆虫警戒信息素，它发现于成年。