CN110964189A - 用于酯化反应的催化剂及催化酯化反应的方法 - Google Patents
用于酯化反应的催化剂及催化酯化反应的方法 Download PDFInfo
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- CN110964189A CN110964189A CN201911165256.7A CN201911165256A CN110964189A CN 110964189 A CN110964189 A CN 110964189A CN 201911165256 A CN201911165256 A CN 201911165256A CN 110964189 A CN110964189 A CN 110964189A
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Abstract
一种用于酯化反应的催化剂,其是由包括至少一第一化合物和至少一第二化合物的混合物反应而成,其中至少一第一化合物是具有钛、铝、锆、铪、锌或铋的金属烷氧化物、无机金属盐、金属羧酸盐、无机金属化合物或其组合;至少一第二化合物是α羟基酸、由α羟基酸及醇类形成的烷基酯、由α羟基酸及胺类形成的烷基酰胺、氨基酸、由氨基酸及醇类形成的烷基酯、由氨基酸及胺类形成的烷基酰胺、或其组合。用于聚酯化反应的催化剂具备良好催化性能,同时解决连续式生产因催化剂水解必须关闭系统并清洁系统的困扰,提高生产效益。
Description
技术领域
本发明是有关于一种用于酯化反应(esterification)的催化剂及其催化方法。
背景技术
酯类化合物在当今生活中被广泛使用,常见用于进行酯化反应的催化剂包括锡基催化剂(例如,二月桂酸二丁基锡(dibutyltin dilaurate,DBTDL)、辛酸锡或乙酰丙酮锡)、钛基催化剂(例如,钛醇盐、乳酸钛或柠檬酸钛)或锑基催化剂(例如,三氧化二锑或乙二醇锑)。锡基催化剂的反应速率快,且较不会影响产物颜色,然而有机锡化合物毒性较高,欧盟已立法限制其应用。相同情形亦发生在锑基催化剂上,举例来说,日本在热充填瓶聚对苯二甲酸乙二酯(polyethylene terephthalate,PET)中限制使用锑基催化剂。对于传统钛基催化剂而言,虽然钛是无毒金属且拥有良好反应性,但是催化剂容易变色并发生水解,因而造成使用上的困扰。
一般而言,使用连续式生产制造聚酯时,如聚对苯二甲酸丁二酯(polybutyleneterephthalate,PBT),催化剂水解将造成每隔数月即需停车清洁设备,不仅消耗大量人力且减少产能。此外,近年来环保意识抬头,对环境友好的催化剂需求更是不容小觑。有鉴于此,目前急需发展出更好的催化剂以改善上述问题。
发明内容
本发明的目的之一在于提供能够克服上述现有技术的催化剂存在的种种问题的更好的催化剂。
本发明的一态样是提供一种用于酯化反应的催化剂,此催化剂是由包括至少一第一化合物和至少一第二化合物的混合物反应而成。至少一第一化合物是具有钛、铝、锆、铪、锌或铋的金属烷氧化物、无机金属盐、金属羧酸盐、无机金属化合物或其组合。至少一第二化合物是α羟基酸、由α羟基酸及醇类形成的烷基酯、由α羟基酸及胺类形成的烷基酰胺、氨基酸、由氨基酸及醇类形成的烷基酯、由氨基酸及胺类形成的烷基酰胺、或其组合。
在一些实施方式中,具有钛、铝、锆、铪、铋或锌的金属烷氧化物的化学式为M(OR1)(OR2)(OR3)x(OR4)y,R1、R2、R3及R4独立地为C2~C8烷基。当M为钛、锆或铪时,x=1且y=1。当M为铋或铝时,x=1且y=0。当M为锌时,x=0且y=0。
在一些实施方式中,具有钛、铝、锆、铪、铋或锌的无机金属盐包括氯盐、硝酸盐、硫酸盐或其组合。具有钛、铝、锆、铪、铋或锌的金属羧酸盐包括醋酸盐、丙酸盐或其组合。具有钛、铝、锆、铪、铋或锌的无机金属化合物包括金属氧化物、金属氢氧化物或其组合。
在一些实施方式中,α羟基酸包括乙醇酸、乳酸、柠檬酸、苹果酸、酒石酸或其组合。
在一些实施方式中,由α羟基酸及醇类形成的烷基酯具有C2~C18烷基。由α羟基酸及胺类形成的烷基酰胺具有C2~C18烷基。由氨基酸及醇类形成的烷基酯具有C2~C18烷基。由氨基酸及胺类形成的烷基酰胺烷基具有C2~C18烷基。
在一些实施方式中,以催化剂的重量为基准,催化剂中的钛、铝、锆、铪、铋和锌的总重量百分浓度为0.01wt%~50wt%。
在一些实施方式中,至少一第一化合物与至少一第二化合物的摩尔比为1:0.1~1:6。
本发明的另一态样是提供一种催化酯化反应的方法,此方法包括以下操作:(i)提供一混合物,混合物包括至少一醇类及至少一酸类,于混合物加入先前任一实施方式中所述的催化剂,以形成酯类。
在一些实施方式中,至少一醇类包括乙二醇、丙二醇、丁二醇、戊二醇、己二醇、丙三醇(甘油)、异山梨醇、环己烷二甲醇、季戊四醇、新戊二醇、三甲醇丙烷、乳酸、柠檬酸、或其组合。
在一些实施方式中,至少一酸类包括对苯二甲酸、间苯二甲酸、偏苯三甲酸、偏苯三甲酸酐、2,6-萘二甲酸、己二酸、琥珀酸、丙二酸、辛二酸、癸二酸、顺丁烯二酸、反丁烯二酸、乳酸、柠檬酸、柠康酸、中康酸、衣康酸或其组合。
与现有技术相比,本发明的优点在于:本发明的催化剂在酯化反应上不仅拥有优异催化速度,且为无毒性催化剂,因此是对环境友善的环保催化剂,符合永续经营的概念;本发明的用于聚酯化反应的催化剂具备良好催化性能,同时解决连续式生产因催化剂水解必须关闭系统并清洁系统的困扰,提高生产效益。
具体实施方式
为了使本揭示内容的叙述更加详尽与完备,下文针对了本发明的实施态样与具体实施例提出了说明性的描述;但这并非实施或运用本发明具体实施例的唯一形式。以下所揭露的各实施例,在有益的情形下可相互组合或取代,也可在一些实施例中附加其他的实施例,而无须进一步的记载或说明。
于本文中,除非内文中对于冠词有所特别限定,否则『一』与『该』可泛指单一个或多个。将进一步理解的是,本文中所使用的『包含』、『包括』、『具有』及相似词汇,指明其所记载的特征、区域、整数、步骤、操作、元件与/或组件,但不排除其所述或额外的其一个或多个其它特征、区域、整数、步骤、操作、元件、组件,与/或其中的群组。
本发明的一态样是提供一种用于酯化反应的催化剂。此催化剂是由包括至少一第一化合物和至少一第二化合物的一混合物反应而成。
具体而言,至少一第一化合物是具有钛、铝、锆、铪、锌或铋的金属烷氧化物、无机金属盐、金属羧酸盐、无机金属化合物或其组合。在一些实施方式中,具有钛、铝、锆、铪、铋或锌的金属烷氧化物的化学式为M(OR1)(OR2)(OR3)x(OR4)y,其中R1、R2、R3及R4独立地为C2~C8烷基。当M为钛、锆或铪时,x=1且y=1。当M为铝或铋时,x=1且y=0。当M为锌时,x=0且y=0。在某些实施方式中,R1、R2、R3及R-4是独立为直链烷基或支链烷基。举例来说,R1、R2、R3及R-4包括但不限于甲基、乙基、正丙基、异丙基、正丁基、仲丁基、异丁基、叔丁基、正戊基、叔戊基、新戊基、异戊基、仲戊基、3-戊基、己基、庚基、辛基、壬基或癸基。
在一些实施例中,具有钛、铝、锆、铪、铋或锌的无机金属盐包括氯盐、硝酸盐、硫酸盐、或其组合,具有钛、铝、锆、铪、铋或锌的金属羧酸盐包括醋酸盐、丙酸盐、或其组合,具有钛、铝、锆、铪、铋或锌的无机金属化合物包括金属氧化物、金属氢氧化物或其组合。
具体而言,至少一第二化合物是α羟基酸、由α羟基酸及醇类形成的烷基酯、由α羟基酸及胺类形成的烷基酰胺、氨基酸、由氨基酸及醇类形成的烷基酯、由氨基酸及胺类形成的烷基酰胺、或其组合。在各种实施方式中,α羟基酸包括乙醇酸、乳酸、柠檬酸、苹果酸、酒石酸或其组合。氨基酸包括天冬氨酸、甘氨酸、精氨酸、组氨酸、离氨酸、麸氨酸、丙氨酸、丝氨酸、苏氨酸、天门冬酰胺、麸酰氨酸、半胱氨酸、脯氨酸、缬氨酸、异白氨酸、白氨酸、甲硫氨酸、苯丙氨酸、酪氨酸、色氨酸、或其组合。
在一些实施例中,由α羟基酸及醇类形成的烷基酯具有C2~C18烷基,由α羟基酸及胺类形成的烷基酰胺具有C2~C18烷基,由氨基酸及醇类形成的烷基酯具有C2~C18烷基,由氨基酸及胺类形成的烷基酰胺烷基具有C2~C18烷基。前述C2~C18烷基可以是直链烷基或支链烷基,但不限于此。
在一些实施例中,以催化剂的重量为基准,催化剂中的钛、铝、锆、铪、铋和锌的总重量百分浓度为0.01wt%~50wt%。举例来说,0.01wt%、1wt%、5wt%、10wt%、20wt%、30wt%、40wt%或50wt%。在一些实施例中,至少一第一化合物与至少一第二化合物的摩尔比为1:0.1~1:6。例如,1:0.1、1:1、1:2、1:3、1:4、1:5、或1:6。总重量百分浓度和摩尔比介于本揭示的区间可增进催化剂反应性能,加速酯化反应速率且不会发生催化剂水解。
本发明的另一态样是提供一种催化酯化反应的方法。此方法包括提供混合物,混合物包括至少一醇类及至少一酸类,于混合物加入前文所述任一实施例中的催化剂,以形成酯类。
在一些实施方式中,至少一醇类包括二元醇、多元醇或其组合。举例来说,二元醇包括乙二醇、丙二醇、丁二醇、戊二醇、己二醇、丙三醇、异山梨醇、环己烷二甲醇、新戊二醇、或其组合。多元醇包括季戊四醇、三甲醇丙烷、乳酸、柠檬酸或其组合。
在另外一些实施方式中,至少一酸类包括一元酸、二元酸、多元酸或其组合。举例来说,一元酸包括偏苯三甲酸酐。二元酸包括对苯二甲酸、间苯二甲酸、2,6-萘二甲酸、己二酸、琥珀酸、丙二酸、辛二酸、癸二酸、顺丁烯二酸、反丁烯二酸、柠康酸、中康酸、衣康酸、或其组合。多元酸包括偏苯三甲酸、乳酸、柠檬酸、或其组合。
以下的实施例是用以详述本发明的特定态样,并使本发明所属技术领域中具有通常知识者得以实施本发明。然而,以下的实施例不应该用来限制本发明。
实验例一:合成催化剂
实施例1的实验步骤简述如下。首先,在装有搅拌器和冷凝管的圆底烧瓶中加入3.50克(12mmol)的异丙醇钛(titanium tetra-isopropoxide,TIPT,由Borica公司提供,商标为Tytan)以及6.00克(24mmol)的混合物1(柠檬酸、柠檬酸单丁酯、双丁酯及三丁酯的混和物,混合物1酸值=200mg KOH/g),以形成反应混合物,其中混合物1的总摩尔数与异丙醇钛的摩尔数的比为2:1。接着,将上述反应混合物搅拌30分钟后,即得到实施例1的催化剂。
实施例2~9的催化剂亦可利用上述步骤制备。实施例2~9使用相同或不同于实施例1的第一化合物、第二化合物以及摩尔比制备催化剂,详细的实验条件汇整在以下表一中。表一列出反应混合物的摩尔比和金属含量(wt%),其中摩尔比表示为第一化合物中具有Ti的化合物的摩尔数:第一化合物中不具有Ti的化合物的摩尔数:第二化合物的摩尔数;金属含量为第一化合物内的不同金属的重量百分比。第一化合物可以是正丙醇锆(zirconium tetra-n-propoxide,TNPZ)、氯化锌、仲丁醇铝(aluminum tri-s-butoxide)、正丁醇锆(zirconiumn-butoxide,TNBZ)、或是钛酸乙酯(titanium tetra-ethoxide,ET)。第二化合物可以是混合物1、混合物2(柠檬酸、柠檬酸单乙酯、双乙酯及三乙酯的混和物,混合物2酸值=200mg KOH/g)或乳酸乙酯(ethyl lactate)。正丙醇锆、钛酸乙酯和正丁醇锆由Borica公司提供,商标为Tytan。
表一
实验例二:催化剂性能测试
利用上述实施例1~9的催化剂及二月桂酸二丁基锡(DBTDL)、正丁醇钛(titaniumtetrabutoxide,TNBT),以对苯二甲酸双(羟乙)酯(bis(2-hydroxyethyl)terephthalate,BHET,试药级,纯度85%)模拟PET聚合反应,进行实施例1~9反应活性快速量测。实验步骤如下。首先,在温度107~110℃的条件下融化BHET,并添加10ppm(以金属原子计)的催化剂(DBTDL的Sn用量为285ppm),以形成反应混合物。持续搅拌此反应混合物使其均匀混合。接着,冷却反应混合物,并将冷却后的反应混合物研磨成粉末,取10毫克研磨的粉末放至配置有盖子的40uL标准铝坩埚中,使用热重分析仪/示差热扫描分析仪(购自Mettler Toledo公司,TGA/DSC 3+STAR)量测样品热重损失,实验参数如下所示:
第一阶段:从50℃加热至280℃,加热速率为10K/min,氮气流量为50mL/min。
第二阶段:280℃持温50分钟,氮气流量为50mL/min。
表二列出在添加催化剂(实施例1~9)下,BHET进行缩和反应的实验后所得的反曲点温度(℃),其中反曲点是藉由BHET的重量损失对温度作图而得。
表二
反曲点温度越低表示BHET进行缩合反应的速率越快,催化剂的效果越好。由表二可知,实施例1~6和8~9的反曲点温度跟比较例1~2相比都在良好范围内,此结果证实催化剂具备绝佳的催化效果。
实验例三:催化剂水解测试
利用实验例一制备的催化剂(实施例1~5和9)进行水解测试,探讨催化剂在水中的稳定性,实验方法简述如下。首先,将实施例1的催化剂和水以重量比9:1进行混合后,即可得到样品。接着,将此样品在200℃下加热1小时,进行耐水解的测试。加热前和加热后样品的外观汇整于下表三。
实施例2~5和9的样品亦可利用上述步骤来制备。表三的比较例3的样品为正丁醇钛(TNBT)和水,重量比=9:1。
表三
样品 | 加热前 | 加热后 | |
比较例3 | 正丁醇钛+水 | 混浊 | 混浊 |
实施例1 | 催化剂1+水 | 清澈 | 清澈 |
实施例2 | 催化剂2+水 | 清澈 | 清澈 |
实施例3 | 催化剂3+水 | 清澈 | 清澈 |
实施例4 | 催化剂4+水 | 清澈 | 清澈 |
实施例5 | 催化剂5+水 | 清澈 | 清澈 |
实施例9 | 催化剂9+水 | 清澈 | 清澈 |
加热前,实施例1~5和9的样品目测时呈现清澈,表示催化剂没有水解现象。经过200℃下加热1小时之后,目测样品时依旧保持清澈,由此证实本文实验例一制备的催化剂在水中不会水解,因此在催化酯化反应时可维持良好催化性能。反观比较例3的样品,当催化剂与水混合时,尚未加热前即呈现混浊状,表示比较例3的催化剂完全不具抗水解性质,导致较差催化性能。
综上所述,本揭示内容提供一种用于酯化反应的催化剂以及催化酯化反应的方法。催化剂在加热后不会发生水解反应,因此有利于进行酯化反应且保持良好催化性能,同时解决连续式生产因催化剂水解必须定期停车清洁设备的困扰,提高生产效益。值得注意的是,本文使用的催化剂在酯化反应上不仅拥有优异催化速度,且为无毒性催化剂,因此是对环境友善的环保催化剂,符合永续经营的概念。
虽然本发明已以实施方式揭露如上,然其并非用以限定本发明,任何熟习此技艺者,在不脱离本发明的精神和范围内,当可作各种的更动与润饰,因此本发明的保护范围当视后附的申请专利范围所界定者为准。
Claims (10)
1.一种用于酯化反应的催化剂,其特征在于,该催化剂是由包括至少一第一化合物和至少一第二化合物的混合物反应而成,其中该至少一第一化合物是具有钛、铝、锆、铪、锌或铋的金属烷氧化物、无机金属盐、金属羧酸盐、无机金属化合物或其组合;该至少一第二化合物是α羟基酸、由α羟基酸及醇类形成的烷基酯、由α羟基酸及胺类形成的烷基酰胺、氨基酸、由氨基酸及醇类形成的烷基酯、由氨基酸及胺类形成的烷基酰胺、或其组合。
2.如权利要求1所述的催化剂,其中所述具有钛、铝、锆、铪、铋或锌的金属烷氧化物的化学式为M(OR1)(OR2)(OR3)x(OR4)y,R1、R2、R3及R4独立地为C2~C8烷基,其中当M为钛、锆或铪时,x=1且y=1,当M为铝或铋时,x=1且y=0,当M为锌时,x=0且y=0。
3.如权利要求1所述的催化剂,其中所述具有钛、铝、锆、铪、铋或锌的无机金属盐包括氯盐、硝酸盐、硫酸盐、或其组合,所述具有钛、铝、锆、铪、铋或锌的金属羧酸盐包括醋酸盐、丙酸盐、或其组合,所述具有钛、铝、锆、铪、铋或锌的无机金属化合物包括金属氧化物、金属氢氧化物或其组合。
4.如权利要求1所述的催化剂,其中所述α羟基酸包括乙醇酸、乳酸、柠檬酸、苹果酸、酒石酸或其组合。
5.如权利要求1所述的催化剂,其中所述由α羟基酸及醇类形成的烷基酯具有C2~C18烷基,所述由α羟基酸及胺类形成的烷基酰胺具有C2~C18烷基,所述由氨基酸及醇类形成的烷基酯具有C2~C18烷基,所述由氨基酸及胺类形成的烷基酰胺烷基具有C2~C18烷基。
6.如权利要求1所述的催化剂,其中以所述催化剂的重量为基准,所述催化剂中的钛、铝、锆、铪、铋和锌的总重量百分浓度为0.01wt%~50wt%。
7.如权利要求1所述的催化剂,其中所述至少一第一化合物与所述至少一第二化合物的摩尔比为1:0.1~1:6。
8.一种催化酯化反应的方法,其特征在于,包括:
提供一混合物,该混合物包括至少一醇类及至少一酸类,于该混合物加入如权利要求1至7任一项所述的催化剂,以形成酯类。
9.如权利要求8所述的方法,其中所述至少一醇类包括乙二醇、丙二醇、丁二醇、戊二醇、己二醇、丙三醇(甘油)、异山梨醇、环己烷二甲醇、季戊四醇、新戊二醇、三甲醇丙烷、乳酸、柠檬酸或其组合。
10.如权利要求8所述的方法,其中所述至少一酸类包括对苯二甲酸、间苯二甲酸、偏苯三甲酸、偏苯三甲酸酐、2,6-萘二甲酸、己二酸、琥珀酸、丙二酸、辛二酸、癸二酸、顺丁烯二酸、反丁烯二酸、乳酸、柠檬酸、柠康酸、中康酸、衣康酸或其组合。
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