CN101918131B - 用于环氧化大豆脂肪酸/脂肪酸酯的酯化的催化剂及其使用方法 - Google Patents
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Abstract
本发明揭示了一种催化剂的组合，用来促进环氧化大豆脂肪酸/脂肪酸酯与多元醇的酯交换反应，在环氧官能团得到保留的情况下得到高百分产率的环氧化大豆脂肪酸二酯。主催化剂是金属氢氧化物，次催化剂是钛酸酯。制得可以用于热塑性材料和热固性材料的生物来源的增塑剂。
Description
优先权要求
本申请要求于2008年1月24日提交的美国临时专利申请序列第60/61/023,182号(代理机构案卷号12008007)的优先权，该专利申请通过参考结合于此。
发明领域
本发明涉及使用两种不同的催化剂促进环氧化大豆脂肪酸/脂肪酸酯(soyate)与二醇的酯交换反应，形成环氧化大豆脂肪酸二酯。
发明背景
自从二十世纪中叶以来，在氯乙烯聚合反应并且需要使聚氯乙烯具有挠性以后，来自石油原料和其它合成来源的增塑剂在工业中一直占优势。邻苯二甲酸酯增塑剂是最普遍使用的。
近年来，由于对石油原料的可用性、成本以及维护健康的担心，人们已探寻来自生物的可再生来源的增塑剂。
美国专利第6,797,753号(Benecke等)揭示了由脂肪酸制备大量环氧化二酯，包括环氧化二大豆脂肪酸丙二醇酯。Benecke等所采用的方法是开始进行酯化反应，然后进行环氧化。这是一条复杂的反应路径，因为在环氧化过程中使用强氧化剂，而且在环氧化以后产生要求维护环境的废物流。
发明概述
本领域需要一种以保留所得二酯中的高活性环氧部分的方式由天然可再生原料制备环氧化大豆脂肪酸二酯的方法。
Benecke等的制备方法包括在酯化反应之后进行环氧化，人们尚未发现该方法适用于小规模定制合成增塑剂，该方法需要避免建立准备处理强氧化剂作为反应物以及对环境麻烦的废物流的大规模反应装置。
本发明通过以下方式解决了本领域的问题：从环氧化大豆脂肪酸/脂肪酸酯开始，通过使用催化剂的组合促进酯交换反应，使得制得的环氧化大豆脂肪酸二酯上的完好的环氧基团得到很好保留。
从市售的环氧化大豆脂肪酸/脂肪酸酯(在用来处理上述氧化剂和废物流的大装置制得)开始，然后人们可以在复杂程度低得多的装置继续进行酯交换反应，也许甚至可以在与所得环氧化大豆油脂肪酸二酯一起制得的化合物相关的装置进行操作。
本发明的一个方面涉及一种催化剂体系，该催化剂体系用来促进环氧化大豆脂肪酸/脂肪酸酯与多元醇反应以制备环氧化大豆脂肪酸二酯，所述催化剂体系包含：(a)包含金属氢氧化物的主催化剂，以及(b)包含钛酸酯的次催化剂。
任选但是优选地，如果所述主催化剂中的金属氢氧化物是固态形式，则所述主催化剂还包含一元醇作为所述金属氢氧化物的溶剂。
本发明的另一个方面涉及一种使用上述催化剂体系的方法，所述方法包括以下步骤：(a)将环氧化大豆脂肪酸/脂肪酸酯与多元醇和主催化剂混合，以及(b)将所述次催化剂加入所述步骤(a)的混合物中，以制备环氧化大豆脂肪酸二酯。
令人吃惊的是，所述反应的效率可以高达96％，所需二酯的产率可以高达80％。
同样出人意料的是，仅使用金属氢氧化物仅能制得产率为42％的所需的二酯，而仅使用钛酸酯则制得产率很少(4％)的二酯。
本发明的一个优点在于，通过将作为主催化剂的金属氢氧化物与作为次催化剂的钛酸酯的催化剂组合，结果出人意料地在增塑剂分子的环氧基团保持完好的情况下以高产率制得了环氧化大豆脂肪酸二酯。这些环氧基团在酯交换反应中保持完好，与需要在酯化反应之后进行环氧化的Benecke等所述的方法相比，这是出人意料的。
下面将对本发明的其它特征和优点进行说明。
发明实施方式
反应物
环氧化大豆脂肪酸/脂肪酸酯(epoxidized Soyate)
任何生物来源的环氧化大豆脂肪酸/脂肪酸酯均是适合用于本发明的候选物。应当理解，术语″大豆脂肪酸/脂肪酸酯″是一种羧酸/羧酸酯部分，其表示任意天然存在的或后来精制的脂肪酸及其酯的混合物，其中所述脂肪酸包括硬脂酸，油酸，亚油酸，亚麻酸等。这些脂肪酸酯(例如大豆脂肪酸甲酯)的环氧化通常会形成环氧基团，也称为缩水甘油基或环氧乙烷环，代替脂肪酸主链中的双键。
通常用来制备生物来源的环氧化大豆脂肪酸/脂肪酸酯的生物来源原料是环氧化大豆油(ESO)，是一种已知可从生物来源获得的商品。其一些可能的单酯也是可在市场上购得的。环氧化大豆脂肪酸/脂肪酸酯的非限制性例子包括环氧化大豆脂肪酸甲酯，环氧化大豆脂肪酸乙酯，环氧化大豆脂肪酸丁酯，环氧化大豆脂肪酸辛酯，以及它们的组合。其中优选的是环氧化大豆脂肪酸甲酯(CAS编号68082-35-9)，这是因为大豆脂肪酸甲酯与多元醇的酯交换反应要比更长烃链的酯类分子与多元醇的酯交换反应有利。
所述环氧化大豆脂肪酸/脂肪酸酯可以在市场上购得，或者通过以下反应制备得到：使用圆底烧瓶反应容器，在金属氢氧化物催化剂的存在下，在温度为23-45℃、压力为一个大气压(常压)、相对湿度50％的条件下，使得环氧化大豆油与醇(例如甲醇)反应约36小时。关于合成环氧化大豆脂肪酸甲酯的另一描述可以参见以下文献：Miyagowa等的″含环氧的环氧化亚麻子油的热-物理性质和冲击性能，1酸酐固化的环氧(Thermo-Physicaland Impact Properties of Epoxy Containing Epoxidized Linseed Oil)，1Anhydride-Cured Epoxy)″Macrom0l.Mater.Eng.2004，289，629-635。
环氧化大豆脂肪酸/脂肪酸酯的一个商业来源是购自美国宾夕法尼亚州费城的阿科玛公司(Arkema ofPhiladelphia，PA)的
7010牌环氧化大豆脂肪酸甲酯。
可以用于本发明的环氧化大豆脂肪酸/脂肪酸酯每个分子中应包含约0.5-4％，优选约1-2％的环氧基团。该含量是所得环氧化大豆脂肪酸二酯中环氧基含量的起点和理想完成点。因此，无论是购自商业来源还是由前体制备，对于在催化剂的存在下成功完成反应来说，环氧基都是很重要的。
多元醇
任何生物来源的多元醇均是适合用于本发明的候选物。多元醇的非限制性例子是丙二醇、丁二醇、己二醇、以及它们的组合。二醇是优选的，因为它们用于聚卤乙烯的性能、增塑能力优于其它多元醇，而用于聚卤乙烯的挥发性少于其它的多元醇。在优选的二元醇中，丙二醇也被称为丙烷二醇，是最优选的，因为其价格性能比最平衡。
制得的环氧化大豆脂肪酸二酯的每个分子中环氧基团的密度也是选择多元醇的一个因素。多元醇与两种相同或不同的环氧化大豆脂肪酸/脂肪酸酯反应形成了A-B-A/C结构，其中A/C表示多元醇B与另一种A大豆脂肪酸/脂肪酸酯或不同的C大豆脂肪酸/脂肪酸酯反应。当所有其它因素不变的情况下，多元醇碳链的长度会影响每个分子中环氧基团的密度。
为了说明本发明方法的效果，使用1，3-丙二醇(CAS No.504-63-2)。
1，3-丙二醇的一个商业来源是购自奥尔德瑞奇化学品公司(AldrichChemicals)的Fluka牌丙二醇。
催化剂
主催化剂
任何金属氢氧化物均是适合用于本发明的主催化剂的候选物。金属氢氧化物的非限制性例子包括碱金属氢氧化物和碱土金属氢氧化物。其中最常见的是钠、钾、钙和镁的氢氧化物，更优选使用氢氧化钾作为该反应的主催化剂，因为其溶解度和催化活性高于其它的金属氢氧化物。
氢氧化钾是可以从很多来源，包括西格玛-奥尔德瑞奇公司(Sigma-Aldrich)购得的化学商品。如果以薄片的形式获得，可以使用甲醇溶解这些薄片，然后将其加入反应容器中。在所有的金属氢氧化物中，氢氧化钾在甲醇中的溶解度是最高的。
在甲醇中稀释KOH薄片，可以制得KOH在甲醇中的浓度约1-30％、优选约10-15％的溶液。
次催化剂
任意钛催化剂均是可用作本发明的次催化剂的候选物。基于钛的催化剂的非限制性例子包括例如钛酸-2-乙基己酯、钛酸四异丙酯，钛酸四丁酯，钛酸四(2-乙基己)酯，以及它们的组合。其中优选的是钛酸四(2-乙基己)酯(CAS No.1070-10-6)，这是因为其催化活性与抗水解影响的耐久性平衡，所述水解会在大气中的水分的存在下发生，导致失活。
迄今为止的实验表明，尽管结构更简单的钛酸酯(例如钛酸四异丙酯)能够催化所述反应，产生较小的二酯产率，但是随着我们进行更多的研究以使反应优化，发现结构更复杂的钛酸酯，例如钛酸四(2-乙基己)酯已经能够达到工业上实用的产率。因此，本领域普通技术人员无需过多的实验便可以选择各种钛酸酯或其组合，用作本发明的次催化剂。
表1显示了可以接受的、所需的、优选的反应物和催化剂以及任选的溶剂的范围，以摩尔表示。
操作
通过以下步骤制备环氧化大豆脂肪酸二酯：在催化剂的存在下，在加热至约60-80℃、优选约65-75℃的温度的磁力搅拌的反应容器中反应进行约18-22小时，同时用磁力搅拌器进行剧烈混合。由于使用了钛酸酯催化剂，还需要进行氮气保护。
加入组分的顺序如下：首先加入两种反应物和主催化剂，在氮气气氛下搅拌约30分钟，然后加入次催化剂，然后在氮气气氛下再搅拌数小时。
反应产物是粘度极大的液体，因为环氧化大豆脂肪酸二酯可以用作增塑剂，因此人们希望其具有这样的粘度。所述液体静置过夜之后可以固化。
所述反应容器可以是常规的实验室玻璃器皿(例如具有磁力搅拌器的烧杯放置在混合加热板上)，到专业的设置在加热罩上的装有机械搅拌器的三颈圆底烧瓶，或者其工业规模的等价装置。从实验室规模反应到工业生产的放大是本领域普通技术人员所熟悉的过程，无需过多的实验。通过放大可以将间歇操作改为连续操作。
本发明的实用性
催化剂组合使用的效用是很显著的，因为该催化剂组合能够制得包含完好的环氧基团的环氧化大豆油脂肪酸二酯，而且二酯的产率高达80％，残留环氧化大豆脂肪酸/脂肪酸酯的含量小于5％。这一成果完全是意外的，这是因为(a)在通常为了获得高转化率而使用强碱的强制性条件下，环氧基团不大可能在酯化反应中保持完好，所述强制性条件会使环氧基团破坏，(b)由大豆脂肪酸单酯酯交换为大豆脂肪酸二酯不大可能得到超过50％的大豆脂肪酸二酯的产率，这是因为酯交换反应是反应物、大豆脂肪酸单酯和大豆脂肪酸二酯之间的平衡反应，特别是在上表1所示的摩尔比条件下。
如下面的实施例所示，单独使用任一种催化剂都无法获得该些结果。
包含完好的环氧基团的环氧化大豆脂肪酸二酯的实用性是，首先(最重要地)用作任何需要具有更高挠性的热塑性或热固性基质的生物来源的增塑剂。目前使用任何邻苯二甲酸酯增塑剂的任何常规用途均是使用本发明方法、依靠本发明的催化剂的组合制得的环氧化大豆脂肪酸二酯的候选物。
增塑剂最经常用于聚氯乙烯之类的硬质热塑性材料，制得固体但是挠性的聚氯乙烯配混物，或者用来制得聚氯乙烯分散的树脂的粘性液体增塑溶胶。
目前优选作为生物来源增塑剂的是根据本发明环氧化大豆脂肪酸甲酯和丙二醇的反应制得的环氧化二大豆脂肪酸丙二醇酯。
实施例
比较例A和B以及实施例1-3
表2显示了组分及其来源。表3显示了配方、制备及其所得的性质。
利用尺寸排阻色谱法(SEC)测定残留的环氧化大豆脂肪酸甲酯的量，单酯的产率，以及二酯的产率。使用碳核磁共振谱(13C-NMR)测定反应后环氧基团的完好程度。
通过比较二酯产率显示本发明具有相当高的价值。只有同时使用KOH和钛酸酯的组合催化剂体系才能得到可接受的二酯百分比的产率。实施例1的二酯与单酯产率之比极佳，实施例2则是意想不到的好。实施例2中残留的环氧化大豆脂肪酸/脂肪酸酯含量极少，同时二酯产率为80％，这是完全出乎意料的。在75℃进行的反应有助于得到该结果。
本发明不限于上述实施方式。以下是所附权利要求书。
Claims (6)
1.一种制备环氧化大豆脂肪酸二酯的方法,所述方法包括以下步骤:
(a)将环氧化大豆脂肪酸/脂肪酸酯与多元醇和金属氢氧化物主催化剂混合，以及
(b)将钛酸酯次催化剂加入所述步骤（a）的混合物，制备环氧化大豆脂肪酸二酯。
2.如权利要求1所述的方法，其特征在于，所述金属化氢氧化物是碱金属氢氧化物或碱土金属氢氧化物，所述环氧化大豆脂肪酸/脂肪酸酯选自：环氧化大豆脂肪酸甲酯,环氧化大豆脂肪酸乙酯,环氧化大豆脂肪酸丁酯,环氧化大豆脂肪酸辛酯，及其组合。
3.如权利要求2所述的方法，其特征在于，所述环氧化大豆脂肪酸/脂肪酸酯每个分子包含0.5-4个环氧基团，所述金属氢氧化物是氢氧化钾。
4.如权利要求3所述的方法，其特征在于，所述多元醇选自丙二醇、丁二醇、己二醇、及其组合。
5.如权利要求4所述的方法，其特征在于，所述环氧化大豆脂肪酸/脂肪酸酯是环氧化大豆脂肪酸甲酯，所述多元醇是丙二醇，制得的反应产物是环氧化二大豆脂肪酸丙二醇酯。
6.如权利要求2所述的方法，其特征在于，所述多元醇、金属氢氧化物、钛酸酯、以及醇溶剂相对于环氧化大豆脂肪酸/脂肪酸酯的摩尔比如下表所示:
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| AU2010220406C1 (en) * | 2009-03-05 | 2016-07-21 | Akzo Nobel Coatings International B.V. | Hydroxyl functional oil polyols and coating compositions prepared from hydroxyl functional oil polyols |
| CN102762707B (zh) | 2009-12-17 | 2014-09-24 | Npc化工有限公司 | 使植物油改性的方法和用于乙烯基聚合物的主增塑剂 |
| DE102010040939A1 (de) * | 2010-09-17 | 2012-03-22 | Evonik Degussa Gmbh | Katalysatorsysteme für die Biodieselherstellung |
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| CA3149052A1 (en) * | 2019-09-18 | 2021-03-25 | Eric W. Cochran | Biosolvents useful for improved asphalt products utilizing recycled asphalt pavement or other brittle asphalt binders such as vacuum tower bottom |
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| WO2009094310A2 (en) | 2009-07-30 |
| US20100292492A1 (en) | 2010-11-18 |
| EP2574397A1 (en) | 2013-04-03 |
| US8481767B2 (en) | 2013-07-09 |
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| ES2437599T3 (es) | 2014-01-13 |
| CN103788027A (zh) | 2014-05-14 |
| EP2234716A4 (en) | 2011-12-07 |
| EP2234716A2 (en) | 2010-10-06 |
| EP2234716B1 (en) | 2013-11-20 |
| EP2574397B1 (en) | 2016-04-13 |
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