CN107141460B - 一种植物油基热塑性聚酯的合成方法 - Google Patents
一种植物油基热塑性聚酯的合成方法 Download PDFInfo
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- CN107141460B CN107141460B CN201710439379.XA CN201710439379A CN107141460B CN 107141460 B CN107141460 B CN 107141460B CN 201710439379 A CN201710439379 A CN 201710439379A CN 107141460 B CN107141460 B CN 107141460B
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Abstract
本发明公开了一种植物油基热塑性聚酯的合成方法，以植物油基二元醇单体为原料，与二元羧酸、酸酐或二元酸酯经缩合聚合反应得到植物油基热塑性聚酯；所述植物油基二元醇单体的结构式选自下式(Ⅰ‑1)‑(Ⅰ‑4)中的任意一种：式中，R独立地选自碳数为7～23的饱和直链烷基，和/或以下不饱和烃基团中的至少一种：该合成方法，以植物油基二元醇单体为原料，扩展了热塑性聚酯的原料来源。
Description
技术领域
本发明涉及热塑性聚酯合成的技术领域，具体涉及一种植物油基热塑性聚酯的合成方法。
背景技术
热塑性聚酯是一类由二元羧酸、酸酐或者二元酸酯和二元醇通过缩聚反应制得的线型聚合物的总称。热塑性聚酯按分子链的化学结构可分为脂肪族聚酯与芳香族聚酯。脂肪族聚酯是由脂肪族二元酸和脂肪族二元醇合成的聚酯，熔点低，柔性好，通常可作为聚酯弹性体、热溶胶以及可生物降解塑料等。另一类芳香族聚酯是由芳香族二元酸和各种二元醇合成的聚酯，具有熔点高、耐热性好、高强度、高模量等优点，某些种类还具有热致液晶的特性，因此广泛应用于各类工程塑料和液晶材料。这类聚酯包括聚对苯二甲酸乙二酯、聚对苯二甲酸丁二酯、聚萘二酸乙二酯、聚对苯二甲酸环己烯二亚甲酯、聚酯液晶聚合物、聚芳酯、聚酯弹性体等。
其中可生物降解性的热塑性聚酯作为一种“绿色材料”，对于解决“白色污染”和大量塑料废弃物焚烧引起的环境污染问题具有积极的意义。目前可生物降解性的热塑性聚酯主要以聚乳酸和聚丁二酸丁二酯及其同系物为代表，其价格低廉，力学性能优异，成为可广泛推广应用的通用型完全生物降解塑料研究的热点领域。自然界存在着大量可分解热塑性聚酯的微生物，可将这类聚酯分解为低聚物、单体，最后完全降解为水与二氧化碳。并且，热塑性聚酯在燃烧的情况下也不会像其它塑料一样释放有毒和腐蚀性气体。另一方面，热塑性聚酯的原料可来源于天然植物，通过生物发酵、植物光合作用等合成生产。因此，热塑性聚酯是一种可完全生态循环的环境友好型材料。
如公开号为CN 105001400 A的中国专利文献公开了一种非异氰酸酯法制备可生物降解脂肪族热塑性聚(酯氨酯)及其弹性体的方法。先以脂肪族二元酸和过量的二元醇熔融缩聚，合成端羟基的聚酯低聚物，再与二氨酯二醇自聚形成的预聚物进一步缩聚，获得可生物降解脂肪族热塑性聚(酯氨酯)及其弹性体。该方法操作简便、无污染、绿色环保，所得热塑性聚(酯氨酯)易结晶，便于结构调控，具有较高的熔点、良好的热性能和力学性能。
又如公开号为CN 104497318 A的中国专利文献公开了一种脂肪族可生物降解热塑性聚酯弹性体及其制备方法，涉及一种在高分子主链上形成羧酸酯键的反应制得的嵌段高分子聚合物，解决现有技术中热塑性聚酯弹性体生物降解能力差的问题，制备工艺简单，具有优异的可生物降解性能。
再如公开号为CN 1646596 A的中国专利文献公开了一种二元酸/二元醇类型的生物降解热塑性聚酯，包含脂肪族二元酸或其酯、脂肪族或者环脂族二元醇与第三种三官能度分子的共缩聚，可用于几种类型制品如膜、片材、网、膨胀模塑产品等的生产。
但上述专利均没有涉及采用生物质的植物油为原料，制备得到可生物降解的植物油基热塑性聚酯。
发明内容
本发明提供了一种植物油基热塑性聚酯的合成方法，以植物油基二元醇单体为原料，扩展了热塑性聚酯的原料来源。
具体技术方案如下：
一种植物油基热塑性聚酯的合成方法，以植物油基二元醇单体为原料，与二元羧酸、二酸酐或二元酸酯经缩合聚合反应，得到所述的植物油基热塑性聚酯；
所述植物油基二元醇单体的结构式选自下式(Ⅰ-1)-(Ⅰ-4)中的任意一种：
式中，R独立地选自碳数为7～23的饱和直链烷基，和/或以下不饱和烃基团中的至少一种：
作为优选，所述植物油基二元醇单体按照如下方法制备得到：
将植物油和二羟基仲胺混合，在碱性催化剂作用下，经缩合反应得到所述的植物油基二元醇单体；
所述植物油选自大豆油、蓖麻油、棕榈油、棕榈仁油、菜籽油、葵花籽油、花生油、棉籽油、亚麻油、椰子油、橄榄油、芝麻籽油、红花籽油、茶籽油中的至少一种；
以上列举的植物油均为由多种脂肪酸组成的甘油三酸酯，其中脂肪酸包含了碳数为7～23的饱和与不饱和脂肪酸。以大豆油为例，其脂肪酸组分主要包括亚油酸、油酸、亚麻酸、棕榈酸、硬脂酸、花生酸，含量最多的两个组分分别为亚油酸和油酸。因此，以大豆油为原料，与二羟基仲胺经缩合反应后得到的植物油基二元醇单体实际是由多种脂肪族二元醇单体组成的混合物。
除上述列举的植物油外，以下列举的单一脂肪酸所获得的二元醇单体也在本发明的保护范围内，如油酸、亚油酸、α-亚麻酸、蓖麻油酸、硬脂酸、棕榈酸、肉豆蔻酸、月桂酸、癸酸、辛酸、棕榈油酸、芥酸、11-二十烯酸、花生四烯酸、珠光脂酸、花生酸、山嵛酸、木焦油酸中的至少一种。
所述的二羟基仲胺选自二甲醇胺、二乙醇胺、二丁醇胺、二异丙醇胺或3-甲氨基-1,2-丙二醇；
所述的碱性催化剂选自甲醇钠、氢氧化钠、氨基钠或氢氧化钾/氧化铝负载型催化剂。
作为优选，所述缩合反应的温度为50～100℃，时间为10～24h；
以原料的总质量计，所述碱性催化剂的用量为0.05～2.0wt％。
作为优选，植物油基热塑性聚酯的合成过程中，所述的二元羧酸选自丁二酸、戊二酸、己二酸、庚二酸、辛二酸、壬二酸、癸二酸、对苯二甲酸、2,5-呋喃二甲酸中的至少一种；
所述的二酸酐选自丁二酸酐、戊二酸酐、己二酸酐、马来酸酐中的至少一种；
所述的二元酸酯选自丁二酸二甲酯、戊二酸二甲酯、己二酸二甲酯、对苯二甲酸二甲酯、2,5-呋喃二甲酸二甲酯中的至少一种。
作为优选，所述的缩合聚合反应在催化剂作用下进行，所述的催化剂选自甲醇钠、对甲苯磺酸、钛酸丁酯、氯化亚锡、二丁基氧化锡、乙二醇锑、三氧化二锑、三氟甲磺酸、三氟甲磺酸钪中的至少一种。
作为优选，以植物油基二元醇与二元酸、二酸酐或二元酸酯的总质量计，所述催化剂的用量为0.05～2.0wt％。
作为优选，所述植物油基二元醇单体与二元酸、二酸酐或二元酸酯的摩尔比为1:1。
作为优选，所述缩合聚合反应的温度为50～250℃，时间为2～24h。
与现有技术相比，本发明具有以下突出优势：
(1)本发明的合成方法为简单的缩聚法，不经过反应中间体的分离，直接获得植物油基的热塑性聚酯，制备工艺简单，生产效率高，生产过程产生的废物少，原料利用率高。
(2)本发明采用生物质来源的原料制备热塑性聚酯，原料无毒无害，清洁可再生，符合“绿色化学”的理念。
(3)本发明合成的植物油基热塑性聚酯，具备可生物降解、安全性强的特性，具有良好的市场应用空间和价值。
附图说明
图1为实施例1制备的大豆油基二元醇的1H NMR图；
图2为实施例1制备的大豆油基热塑性聚酯的1H NMR图。
具体实施方式
下面结合具体实施例并结合附图对本发明作进一步阐述，但本发明并不限于以下实施例。其目的仅在于更好地理解本发明而非限制本发明保护的范围。
实施例1
在250ml三口烧瓶中加入100g大豆油，在通氮气条件下加热至50℃，再逐滴加入60g二乙醇胺并搅拌30min，滴加2.7g市售30wt％甲醇钠的甲醇溶液，甲醇钠为碱性催化剂。搅拌反应10小时，用二氯甲烷溶解再以饱和食盐水洗涤除去催化剂，加入无水硫酸镁干燥，分液后旋蒸除去二氯甲烷，获得大豆油基二元醇。
称量20g大豆油基二元醇，加入6.38g丁二酸，同时加入0.26g对甲苯磺酸作催化剂，加入0.26g 1,3,5-三甲基-2,4,6-三(3,5-二叔丁基-4-羟苄)苯作阻聚剂，保持通氮气状态，反应温度75℃，反应时间15小时。反应的最后2小时通过油泵减压脱出体系中的水分以提高聚酯的分子量。反应完后加入二氯甲烷溶解，用无水甲醇沉淀提纯产物，离心分离后，再次用少量二氯甲烷溶解，加入无水硫酸镁干燥，抽滤，旋蒸除去溶剂，再置于真空干燥箱40℃下烘至恒重，得到大豆油基热塑性聚酯。
图1中给出了本实施例制备的大豆油基二元醇的1H NMR图，因大豆油为多种脂肪酸组成的甘油三酸酯，而亚油酸、油酸、亚麻酸为其最主要的成分，因此，图1的1H NMR图中仅标示出了大豆油基二元醇单体中主要的三种脂肪酸。图2中给出了以上述大豆油基二元醇为原料，与丁二酸反应后得到的植物油基热塑性聚酯的1H NMR图。
实施例2～4
同实施例1，区别仅在于将植物油基二元醇单体制备过程的反应温度依次替换为60℃、80℃和100℃。
实施例5～7
合成工艺同实施例1，区别仅在于将植物油基二元醇单体制备过程所用的植物油分别替换为蓖麻油、棕榈油和花生油。
实施例8～10
合成工艺同实施例1，区别仅在于将植物油基二元醇单体制备过程所用的二羟基仲胺分别替换为二甲醇胺、二异丙醇胺和3-甲氨基-1,2-丙二醇。
实施例11～13
合成工艺同实施例1，区别仅在于将植物油基二元醇单体制备过程所用的碱性催化剂的用量分别替换为原料总重量的0.05wt％、1wt％和2wt％。
实施例14～22
合成工艺同实施例1，区别仅在于植物基热塑性聚酯制备过程中，将丁二酸分别替换为戊二酸、己二酸、癸二酸、对苯二甲酸、2,5-呋喃二甲酸、丁二酸酐、戊二酸酐、己二酸酐和马来酸酐。
实施例23
在250ml三口烧瓶中加入100g大豆油，在通氮气条件下加热至60℃，再逐滴加入60g二乙醇胺并搅拌30min，滴加2.7g市售30wt％甲醇钠的甲醇溶液，甲醇钠为碱性催化剂。搅拌反应10小时，用二氯甲烷溶解再以饱和食盐水洗涤除去催化剂，加入无水硫酸镁干燥，分液后旋蒸除去二氯甲烷，获得大豆油基二元醇。
称量20g大豆油基二元醇，加入7.89g丁二酸二甲酯，同时加入0.28g对甲苯磺酸作催化剂，加入0.28g 1,3,5-三甲基-2,4,6-三(3,5-二叔丁基-4-羟苄)苯作阻聚剂，并保持通氮气状态，反应温度75℃，反应时间15小时。反应的最后2小时通过油泵减压脱出体系中的小分子，以提高聚酯的分子量。反应完后加入二氯甲烷溶解，用无水甲醇沉淀提纯产物，离心分离后，再次用少量二氯甲烷溶解，加入无水硫酸镁干燥，抽滤，旋蒸除去溶剂，再置于真空干燥箱40℃下烘至恒重，得到大豆油基热塑性聚酯。
实施例24～27
合成工艺同实施例23，区别仅在于植物基热塑性聚酯制备过程中，将丁二酸二甲酯分别替换为戊二酸二甲酯、己二酸二甲酯、对苯二甲酸二甲酯和2,5-呋喃二甲酸二甲酯。
实施例28
合成工艺同实施例23，区别仅在于植物基热塑性聚酯制备过程中，不添加额外的催化剂，使用第一步的甲醇钠进行催化。
实施例29～31
合成工艺同实施例23，区别仅在于植物基热塑性聚酯制备过程中，将催化剂分别替换为钛酸丁酯、二丁基氧化锡和三氟甲磺酸钪。
实施例32～34
合成工艺同实施例23，区别仅在于植物基热塑性聚酯制备过程中，反应温度依次替换为100℃、200℃和250℃。
实施例35～37
合成工艺同实施例23，区别仅在于植物基热塑性聚酯制备过程中，催化剂用量分别替换为植物油基二元醇单体质量的0.05wt％、0.1wt％和2wt％。
Claims (7)
1.一种植物油基热塑性聚酯的合成方法，其特征在于，以植物油基二元醇为单体，与二元羧酸、二酸酐或二元酸酯经缩合聚合反应，得到所述的植物油基热塑性聚酯；
所述植物油基二元醇的制备方法如下：
将植物油和二羟基仲胺混合，在碱性催化剂作用下，经缩合反应得到所述的植物油基二元醇单体；
所述植物油选自大豆油、蓖麻油、棕榈油、棕榈仁油、菜籽油、葵花籽油、花生油、棉籽油、亚麻油、椰子油、橄榄油、芝麻籽油、红花籽油、茶籽油中的至少一种；
所述的二羟基仲胺选自二甲醇胺、二乙醇胺、二丁醇胺、二异丙醇胺或3-甲氨基-1,2-丙二醇；
所述的碱性催化剂选自甲醇钠、氢氧化钠、氨基钠或氢氧化钾/氧化铝负载型催化剂。
2.根据权利要求1所述的植物油基热塑性聚酯的合成方法，其特征在于，所述缩合反应的温度为50~100 ℃，时间为10~24 h；
以原料的总质量计，所述碱性催化剂的用量为0.05~2.0 wt%。
3.根据权利要求1所述的植物油基热塑性聚酯的合成方法，其特征在于，所述的二元酸选自丁二酸、戊二酸、己二酸、庚二酸、辛二酸、壬二酸、癸二酸、对苯二甲酸、2,5-呋喃二甲酸中的至少一种；
所述的酸酐选自丁二酸酐、戊二酸酐、己二酸酐、马来酸酐中的至少一种；
所述的二元酸酯选自丁二酸二甲酯、戊二酸二甲酯、己二酸二甲酯、对苯二甲酸二甲酯、2,5-呋喃二甲酸二甲酯中的至少一种。
4.根据权利要求1所述的植物油基热塑性聚酯的合成方法，其特征在于，所述的缩合聚合反应在催化剂作用下进行，所述的催化剂选自甲醇钠、对甲苯磺酸、钛酸丁酯、氯化亚锡、二丁基氧化锡、乙二醇锑、三氧化二锑、三氟甲磺酸、三氟甲磺酸钪中的至少一种。
5.根据权利要求4所述的植物油基热塑性聚酯的合成方法，其特征在于，以植物油基二元醇与二元羧酸、二酸酐或二元酸酯的总质量计，所述催化剂的用量为0.05~2.0 wt%。
6.根据权利要求1所述的植物油基热塑性聚酯的合成方法，其特征在于，所述植物油基二元醇与二元羧酸、二酸酐或二元酸酯的摩尔比为1:1。
7.根据权利要求1所述的植物油基热塑性聚酯的合成方法，其特征在于，所述缩合聚合反应的温度为50~250 ℃，时间为2~24 h。
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| CN103804669A (zh) * | 2014-02-28 | 2014-05-21 | 江南大学 | 一种用作pvc增塑剂的蓖麻油基聚酯的制备方法 |
| CN105175697A (zh) * | 2014-10-16 | 2015-12-23 | 中国林业科学研究院林产化学工业研究所 | 一种植物油基聚酯增塑剂的制备方法 |
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| CN103804669A (zh) * | 2014-02-28 | 2014-05-21 | 江南大学 | 一种用作pvc增塑剂的蓖麻油基聚酯的制备方法 |
| CN105175697A (zh) * | 2014-10-16 | 2015-12-23 | 中国林业科学研究院林产化学工业研究所 | 一种植物油基聚酯增塑剂的制备方法 |
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