CN1300092C - 多元醇脂肪酸酯的生产方法 - Google Patents
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Abstract
本发明是一种多元醇与脂肪酸用金属氧化物催化酯化合成多元醇脂肪酸酯的方法这种其中多元醇采用乙二醇或聚乙二醇脂肪酸采用月桂酸、棕榈酸、硬脂酸、油酸等,采用金属氧化物作酯化催化剂,该生产方法工序简单、可靠、稳定,首先是金属氧化物与脂肪酸生成脂肪酸皂,脂肪酸皂再催化多元醇与脂肪酸的酯化反应,由于反应完全在均相条件下进行,反应完毕后,脂肪酸皂作为橡塑加工过程中常用的加工助剂,不须与产物分离,反应条件温和,简化了工序,反应产物比例能较准确控制,即可能稳定、可靠地生产优质产品,产品可用于橡胶混炼作分散剂,能提高橡胶制品的内在品质和外观质量。
Description
技术领域
本发明专利涉及多元醇脂肪酸酯的合成方法,特别是涉及用乙二醇或聚乙二醇等与多元醇脂肪酸用金属氧化物催化经过酯化合成得到多元醇脂肪酸酯的方法。
背景技术
多元醇脂肪酸酯品种较多,有的可以作润滑剂、复合润滑剂、橡胶脱模剂等,还有合成脂肪酸酯可用于橡胶混炼分散剂,能有效降低胶料的熔融粘度,加速熔融,改善胶料流动性能,改善胶料与炭黑、抗老化剂等配合料的分散性能,使各组分在混料胶中分散均匀,最终提高制品的内在品质和外观质量。多元醇脂肪酸酯的合成,传统合成方法是采用硫酸作催化剂酯化合成。优点是催化活性高,价廉易得,但由于H2SO4催化易发生副反应,导致产物中混有少量的醚、硫酸酯、碳化物等,给产品精制带来一定困难;而且浓硫酸严重腐蚀设备,致使设备要定期更新,使成本提高;反应物的后处理要经过碱中和,水洗以除去作为催化剂的硫酸,致使工艺复杂,产品流失,产生三废,污染环境。
在现有技术中的涉及用多元醇与脂肪用金属盐等催化酯化合成多元醇脂肪酸酯的方法有一些,如发明[多元醇脂肪酸酯的制备方法](88105350.3)涉及一种以多元醇与油脂经酯交换而制得的聚氯乙烯塑料加工工业用润滑剂。多元醇脂肪酸酯合成的原料为:多元醇采用甘油或聚甘油,油脂采用动物油脂或植物油脂,在氮气保护下,经催化剂催化酯化合成而得多元醇脂肪酸酯。椐申请人介绍:产品质量好,性能指标达国外同类产品水平,填补了我国塑料加工工业用这类型号内润滑剂的空白。
根据过去的一些多元醇脂肪酸酯资料和专利发明主要用在塑料方面作润滑剂,而这些产品使用于橡塑加工方面效果不理想,本发明的的目的是生产一种橡塑加工中专门使用的润滑剂,要求原料易得,产品性能良好,反应条件温和,工艺简单,能满足橡塑加工生产的需要方法的产品及其生产方法,通过发明人几年的辛勤劳动,反复试验达到了这一目的。
发明内容
1.一种由多元醇与脂肪酸用金属氧化物催化酯化合成多元醇脂肪酸酯的方法,本发明的特征是:
1.1多元醇采用乙二醇或聚乙二醇;
1.2脂肪酸采用饱和或不饱和脂肪酸,包括月桂酸、棕榈酸、硬脂酸、油酸等;
1.3采用金属氧化物作酯化催化剂,包括氧化亚锡、氧化锌、氧化镁等;
1.4原料配比为(摩尔比):多元醇∶脂肪酸=1~2∶1;
1.5反应温度为150~250℃;
1.6反应时间为2~10h;
1.7反应在氮气气氛下进行。
2、按照上述的方法,其特征是所述酯化合成反应中酯化催化剂的用量为总投料量的0.1~1.0%,最佳用量为0.2~0.5%;
3、按照上述的方法,其特征是酯化合成反应的最佳反应时间为3.5~6h;
4、按照上述的方法,其特征是酯化合成反应的最佳反应温度为175~190℃;
5、按照上述的方法,其特征是酯化合成反应的最佳原料配比(摩尔比)为多元醇∶脂肪酸=1.2~1.42∶1。
本发明的生产方法工序简单、可靠、稳定,首先是金属氧化物与脂肪酸生成脂肪酸皂,脂肪酸皂再催化多元醇与脂肪酸的酯化反应,由于反应完全在均相条件下进行,反应完毕后,脂肪酸皂作为橡塑加工过程中常用的加工助剂,不须与产物分离,反应条件温和,简化了工序,反应产物比例能较准确控制,即可能稳定、可靠地生产优质产品。
本发明的合成方法得到的多元醇脂肪酸酯,可用于橡胶混炼分散剂,能有效降低胶料的熔融粘度,加速熔融,改善胶料流动性能,改善胶料与炭黑、抗老化剂等配合料的分散性能,使各组分在混料胶中分散均匀,最终提高制品的内在品质和外观质量。
具体实施方式
实施例1
使用2000mL四颈瓶作反应釜,装有电动恒速搅拌器、N2导入管、温度计、蒸馏头、冷凝器,依次加入硬脂酸(酸值200mgKOH/g)500g(1.76mol)、乙二醇86.8g(1.4mol)、二甘醇90.1g(0.85mol)、氧化锌2.5g,搅拌下升温至85℃,反应瓶中物料完全溶解,通N2气,继续升温至185℃,并在此温度下反应,馏出反应生成的水及过量的乙二醇、二甘醇,反应3.5h后,已无液体馏出,出料,浇盘、冷却后得乳白色蜡状物574.7g,酸值1.5mgKOH/g。
实施例2
使用2000mL四颈瓶作为反应釜,装有电动恒速搅拌器、N2导入管、温度计、蒸馏头、冷凝器,依次加入硬脂酸(酸值200mgKOH/g)99.6g(0.35mol),油酸(酸值195mgKOH/g)42.4g(0.15mol)、聚乙二醇(平均分子量M=1000)500g(0.5mol)、氧化亚锡2.1g,通N2气,搅拌下升温至185℃,并在此温度下反应,馏出反应生成的水,反应4.5h后,已无液体馏出,出料,浇盘、冷却后得到微黄色蜡状物625.3g,酸值2.5mgKOH/g。
Claims (5)
1、一种由多元醇与脂肪酸用金属氧化物催化酯化合成多元醇脂肪酸酯的方法,其特征是:
(1)多元醇采用乙二醇或聚乙二醇;
(2)脂肪酸采用月桂酸、棕榈酸、硬脂酸或油酸;
(3)酯化催化剂采用的金属氧化物为氧化亚锡、氧化锌或氧化镁;
(4)原料摩尔比为:多元醇∶脂肪酸=1~2∶1;
(5)反应温度为150~250℃;
(6)反应时间为2~10h;
(7)反应在氮气氛下进行。
2、根据权利要求1所述的方法,其特征是酯化合成反应中所采用的金属氧化物酯化催化剂用量为总投料量质量的0.1%~1.0%。
3.根据权利要求1所述的方法,其特征是酯化合成反应的反应时间为3.5~6h。
4、根据权利要求1所述的方法,其特征是酯化合成反应的反应温度为175~190℃。
5、根据权利要求1所述的方法,其特征是酯化合成反应的原料摩尔比为:多元醇∶脂肪酸=1.2~1.42∶1,所采用的金属氧化物酯化催化剂用量为总投料量质量的0.2%~0.5%。
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN100443460C (zh) * | 2005-12-27 | 2008-12-17 | 中国石油化工股份有限公司 | 一种羧酸酯的制备方法 |
| CN101831357B (zh) * | 2010-05-05 | 2012-07-04 | 付斌 | 一种利用非酸法生产生物柴油的工艺 |
| CN102311338A (zh) * | 2011-08-25 | 2012-01-11 | 四川泸天化股份有限公司 | 一种高效合成乙二醇硬脂酸单酯的方法 |
| CN105132192A (zh) * | 2014-05-29 | 2015-12-09 | 中国石油化工股份有限公司 | 一种制备生物柴油的方法 |
| CN114394899A (zh) * | 2021-12-29 | 2022-04-26 | 广东科力新材料有限公司 | 一种双季戊四醇酯及其制备方法和应用 |
Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS6256452A (ja) * | 1985-09-04 | 1987-03-12 | Nippon Oil & Fats Co Ltd | エステルの製造法 |
| US5087730A (en) * | 1989-06-27 | 1992-02-11 | Mitsubishi Kasei Vinyl Company | Method for producing a purified ester |
| CN1118158A (zh) * | 1993-01-19 | 1996-03-06 | 埃克森化学专利公司 | 生产增塑剂和多醇酯的方法 |
| CN1199043A (zh) * | 1997-05-10 | 1998-11-18 | 许绍东 | 多元醇烷基醚乙酸酯类及多元醇乙酸酯类产品的制备方法 |
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Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS6256452A (ja) * | 1985-09-04 | 1987-03-12 | Nippon Oil & Fats Co Ltd | エステルの製造法 |
| US5087730A (en) * | 1989-06-27 | 1992-02-11 | Mitsubishi Kasei Vinyl Company | Method for producing a purified ester |
| CN1118158A (zh) * | 1993-01-19 | 1996-03-06 | 埃克森化学专利公司 | 生产增塑剂和多醇酯的方法 |
| CN1199043A (zh) * | 1997-05-10 | 1998-11-18 | 许绍东 | 多元醇烷基醚乙酸酯类及多元醇乙酸酯类产品的制备方法 |
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