CN106146431A - 一种环氧低热油脂增塑剂及其制备方法 - Google Patents

一种环氧低热油脂增塑剂及其制备方法 Download PDF

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CN106146431A
CN106146431A CN201610510195.3A CN201610510195A CN106146431A CN 106146431 A CN106146431 A CN 106146431A CN 201610510195 A CN201610510195 A CN 201610510195A CN 106146431 A CN106146431 A CN 106146431A
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李科
蒋剑春
聂小安
陈洁
李小英
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Abstract

本发明涉及一种环氧低热油脂增塑剂及其制备方法。采用一切可制备环氧油脂及环氧脂肪酸甲酯增塑剂的油料为原料油,可通过与甘油醇解再与甲酸、乙酸等低级酸的酯化反应或其直接与甲酸、乙酸、乙酸酐等低级酸的酸解反应,亦可通过与三甲酸甘油酯、三乙酸甘油酯等低级酸甘油酯酯交换技术制备低热油脂;最后再通过环氧化反应将所得低热油脂环氧化制备出环氧低热油脂环保型增塑剂产品。本发明无需改变现有反应设备,且所得新型环保增塑剂产品的分子量介于对应环氧油脂与环氧脂肪酸甲酯之间,其分子结构具有亲油结构少于环氧大豆油,平均分子环氧化率高于环氧脂肪酸甲酯等特点,具有挥发性低,不易迁移,且耐久性好,闪点高等诸多优良特性。

Description

一种环氧低热油脂增塑剂及其制备方法
技术领域
本发明涉及一种环氧低热油脂增塑剂及其制备方法,属油脂利用与增塑剂领域。
背景技术
塑化剂(增塑剂)是高分子材料(橡胶、塑料、涂料等)成型加工时为增加原料流动性、可塑性并使成所得品具有一定柔韧性而加入的低分子化合物,是PVC(聚氯乙烯)等塑料加工中必不可少的添加助剂之一,且用量最大,我国已是世界第一大增塑剂生产国及消费国,产能已超过每年2 800kt,并在逐年持续快速增长。但现阶段,邻苯二甲酸酯类(如DOP)使用量最大,占主导地位,目前研究表明邻苯二甲酸类增塑剂具有潜在的毒性和致癌性,欧、美、日等发达国家已经禁用。新型环保型增塑剂的开发越来越活跃,其中油脂基增塑剂的研究也较为突出,这其中主要包括环氧油脂类(环氧大豆油等)、环氧脂肪酸酯类、C22-三酸酯类等,但环氧油脂与PVC相容性差、环氧脂肪酸甲酯的闪点低、耐抽出性差等缺陷,市场急需改良或替代产品。
发明内容
本发明公开了一种环氧低热油脂增塑剂及其制备方法,具有挥发性低,不易迁移,且耐久性好,闪点高、环保、可再生等特点。
本发明的技术方案为:一类环氧低热油脂增塑剂,其主要成分结构式如下:
其中:R1为C1到C4的低级酸;R、R’为饱和或不饱和脂肪酸碳链;a,b处单环氧或双环氧。
低热油脂环氧化得到;所述的低热油脂为只具有1-2个长链脂肪酸的油脂。
环氧化试剂一般包括过氧甲酸、过氧乙酸、间氯过氧苯甲酸、过氧化叔丁醇、双氧水、二甲基过氧化酮中的任意一种。
所述的低热油脂是油脂先与甘油醇解再与低级脂肪酸或酸酐酯化得到。
所述低热油脂是油脂与低级脂肪酸或酸酐直接酸解得到。
所述的低级脂肪酸或酸酐为碳分子数≤4的低级脂肪酸或酸酐。
所述低热油脂是油脂与低级酸甘油酯进行酯交换反应得到。
所述的低级酸甘油酯包括三甲酸甘油酯、三乙酸甘油酯。
所述的油脂为C原子数在14到22之间的可制备环氧油脂及环氧脂肪酸甲酯增塑剂的油脂、甲酯或脂肪酸。
所述的油脂包括大豆油、菜籽油、棉籽油、乌桕籽油、桐油、光皮树油、茶油、麻风树油、黄连木油、文冠果油、玉米油、葵花籽油、蓖麻油、微藻油等植物油脂及液态地沟油中的任意一种。
有益效果:
本发明不仅为塑料加工行业提供了一种新型的环保型环氧油脂基增塑剂产品,还为油脂 利用开辟了新的途径,且所发明增塑剂产品具有挥发性低,不易迁移,且耐久性好,闪点高,保,可再生等特点。
附图说明
图1为环氧低热乙酸甘油酯的红外谱图;
图2为合成路线图。
具体实施方式
一种环氧低热油脂增塑剂及其制备方法。可采用一切可制备环氧油脂及环氧脂肪酸甲酯增塑剂的油料为原料油,通过其与甘油醇解再与甲酸、乙酸等低级酸的酯化反应或其直接与甲酸、乙酸、乙酸酐等低级酸的酸解反应,亦可通过与三甲酸甘油酯、三乙酸甘油酯等低级酸甘油酯酯交换技术制备低热油脂;最后再通过环氧化反应将所得低热油脂环氧化制备出环氧低热油脂环保型增塑剂产品。本发明得到的环氧低热油脂为多结构混合产品,其两种主要成分结构为
其中:R1为C1到C4的低级酸;R、R’为饱和或不饱和脂肪酸碳链;a,b处单环氧或双
环氧。
本发明无需改变现有反应设备,且所得新型环保增塑剂产品的分子量介于对应环氧油脂与环氧脂肪酸甲酯之间,其分子结构具有亲油结构少于环氧大豆油,平均分子环氧化率高于环氧脂肪酸甲酯等特点。
所述的原料油为一切可制备环氧油脂及环氧脂肪酸甲酯增塑剂的油料;合成低热油的试剂包括甘油、甲酸、乙酸、丙酸、丁酸、乙酸酐、三甲酸甘油酯、三乙酸甘油酯等;环氧化试剂包括过氧甲酸、过氧乙酸、间氯过氧苯甲酸、过氧化叔丁醇、双氧水、二甲基过氧化酮等。
实施例1:
原料:大豆油,甲醇,氢氧化钾,三乙酸甘油酯,甲醇钠,双氧水,硫酸;
将大豆油与甲醇通过氢氧化钾催化酯交换合成脂肪酸甲酯,产物提纯后再与10倍摩尔比的三乙酸甘油酯混合,并在甲醇钠催化下与85℃减压脱除低沸物的情况下制备乙酸型低热甘油三酯(低热油),再经水洗蒸馏等纯化处理后既得中间原料低热油;再向反应器中投入适量(此物质的量为单位一(及1份),下同)低热油,0.5份甲酸,0.005份硫酸,加热至50℃滴加1.4份双氧水,在1小时内滴完,再升温至65℃反应3小时。降温后分液除水再经碱洗水洗蒸馏等常规后处理既得产品,产物为浅黄色透明液体。
实施例2:
原料:大豆油,三乙酸甘油酯,甲醇钠,双氧水,对甲苯磺酸;
将大豆油与三乙酸甘油酯按物质的量之比为1:3的量投入反应釜,在甲醇钠的催化下 120℃反应2小时制备低热油;向反应器中投入适量纯化后低热油,0.5份甲酸,0.01份对甲苯磺酸,加热至55℃滴加1.2份双氧水,在40分钟内滴完,再升温至65℃反应4小时。降温后分液除水再经碱洗水洗蒸馏等常规后处理既得产品,产物为浅黄色透明液体。
实施例3:
原料:棉籽油,甘油,甲酸,浓硫酸,间氯过氧苯甲酸;
将棉籽油与甘油制备相应的甘油单酯或二酯,再与物质的量之比为1:1到2:1的甲酸通过酯化反应合成甲酸型低热甘油三酯(低热油);向反应器中投入适量纯化后低热油,保持温度在0-30℃滴加1.2份间氯过氧苯甲酸溶液,在1小时内滴完,再反应5小时。最后经过过滤、碱洗、水洗、脱水等一定的常规后处理既得产品,产物为浅黄色透明液体。
实施例4:
原料:菜籽油,甘油,乙酸酐,甲醇钠,过氧化叔丁醇,离子液体;
将菜籽油与甘油制备相应的甘油单酯或二酯,再将甘油酯与乙酸酐按物质的量之比为1:1.2的量投入反应釜,回流反应1.5小时,除乙酸后记得乙酸型低热油;再向反应器中投入适量纯化后低热油,0.05-0.2份离子液体,加热至55℃滴加0.7份过氧化叔丁醇,在1小时内滴完,再什温至70℃反应2小时。降温后经过一定的常规后处理既得产品,产物为浅黄色透明液体。
实施例只在于表述实施方法,改变其中比例或时间但采用此方法的依旧落入本专利的保护范围。

Claims (10)

1.一类环氧低热油脂增塑剂,其特征在于:主要成分结构式如下:
其中:R1为C1到C4的低级酸;R、R’为饱和或不饱和脂肪酸碳链;a,b处单环氧或双环氧。
2.权利要求1所述的环氧低热油脂增塑剂的制备方法,其特征在于,低热油脂环氧化得到;所述的低热油脂为只具有1-2个长链脂肪酸的油脂。
3.如权利要求2所述的环氧低热油脂增塑剂的制备方法,其特征在于,环氧化试剂一般包括过氧甲酸、过氧乙酸、间氯过氧苯甲酸、过氧化叔丁醇、双氧水、二甲基过氧化酮中的任意一种。
4.如权利要求2所述的环氧低热油脂增塑剂的制备方法,其特征在于,所述的低热油脂是油脂先与甘油醇解再与低级脂肪酸或酸酐酯化得到。
5.如权利要求2所述的环氧低热油脂增塑剂的制备方法,其特征在于,所述低热油脂是油脂与低级脂肪酸或酸酐直接酸解得到。
6.如权利要求4或5所述的环氧低热油脂增塑剂的制备方法,其特征在于,所述的低级脂肪酸或酸酐为碳分子数≤4的低级脂肪酸或酸酐。
7.如权利要求2所述的环氧低热油脂增塑剂的制备方法,其特征在于,所述低热油脂是油脂与低级酸甘油酯进行酯交换反应得到。
8.如权利要求7所述的环氧低热油脂增塑剂的制备方法,其特征在于,所述的低级酸甘油酯包括三甲酸甘油酯、三乙酸甘油酯。
9.如权利要求4、5、7任一所述的环氧低热油脂增塑剂的制备方法,其特征在于,所述的油脂为C原子数在14到22之间的可制备环氧油脂及环氧脂肪酸甲酯增塑剂的油脂、甲酯或脂肪酸。
10.如权利要求4、5、7任一所述的环氧低热油脂增塑剂的制备方法,其特征在于,所述的油脂包括大豆油、菜籽油、棉籽油、乌桕籽油、桐油、光皮树油、茶油、麻风树油、黄连木油、文冠果油、玉米油、葵花籽油、蓖麻油、微藻油等植物油脂及液态地沟油中的任意一种。
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CN106967015A (zh) * 2017-03-30 2017-07-21 中国林业科学研究院林产化学工业研究所 一种环氧二缩脂肪酸酯及其制备方法和应用
CN107383417A (zh) * 2017-07-21 2017-11-24 中国林业科学研究院林产化学工业研究所 一种二元酸改性环氧梓油甲酯增塑剂及其制备方法
CN108219225A (zh) * 2016-12-15 2018-06-29 东洋橡胶工业株式会社 橡胶组合物

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CN108219225A (zh) * 2016-12-15 2018-06-29 东洋橡胶工业株式会社 橡胶组合物
CN108219225B (zh) * 2016-12-15 2021-02-19 东洋橡胶工业株式会社 橡胶组合物
CN106967015A (zh) * 2017-03-30 2017-07-21 中国林业科学研究院林产化学工业研究所 一种环氧二缩脂肪酸酯及其制备方法和应用
CN107383417A (zh) * 2017-07-21 2017-11-24 中国林业科学研究院林产化学工业研究所 一种二元酸改性环氧梓油甲酯增塑剂及其制备方法
CN107383417B (zh) * 2017-07-21 2019-05-21 中国林业科学研究院林产化学工业研究所 一种二元酸改性环氧梓油甲酯增塑剂及其制备方法

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