CN103270012A - 支链仲醇烷氧基化物表面活性剂及制备它们的方法 - Google Patents
支链仲醇烷氧基化物表面活性剂及制备它们的方法 Download PDFInfo
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Abstract
Description
相关申请的交叉引用
本申请要求2010年11月23日提交的临时申请序号61/416,462的优先权,所述申请以其全部内容通过引用并入本文。
发明领域
本发明涉及烷氧基化物组合物及制备和使用它们的方法。所述烷氧基化物表现出有利的性质例如窄的分子量分布或低含量的残余醇。
发明背景
醇乙氧基化物是工业上重要的材料类别,其发现用于各种各样的应用中,例如作为表面活性剂和洗涤剂。仲醇烷氧基化物通常通过仲醇的碱催化乙氧基化来制备。制造方法的简便性或其提供优质产品(例如窄的分子量分布和/或低的残余醇含量)的能力已经产生了各种各样的这些待制备材料的类型。
与伯醇相反,高支化仲醇的活性相当低,并因此通过碱催化方法进行乙氧基化要困难得多。因此,已经开发了用于制造高支化仲醇烷氧基化物的替代程序。
常用的替代程序基于两步法。在第一步中,醇或醇混合物用环氧乙烷(EO)在路易斯酸催化剂(通常使用BF3)存在下反应,以添加少量的EO至所述醇中。低EO加合物通过彻底的洗涤以除去催化剂和副产物来进行纯化,然后进行蒸馏以将期望的产物与未反应的醇和低级加合物分离。纯化的低EO产物(平均2-4摩尔EO)进行其中碱催化常规烷氧基化物的第二步,以生产最终表面活性剂产物。
两步法具有许多缺点。例如,来自第一步的产物一般含有相当量的需要去除的副产物1,4-二噁烷。此外,乙氧基化物产物通常表现出不利的宽分子量分布和大量的未反应的醇起始材料。因此,如果要制备可接受品质的最终材料,需要进行中间体得分离和纯化。然而,这样的分离和纯化,以及额外的第二烷氧基化方法显著增加了该方法的成本并导致产生大量废物。
新的高支化仲醇烷氧基化物,其表现出窄分子量分布和低含量的残余醇、以及制备它们的低成本和产生低废物的方法,将是本领域的显著进步。
发明简述
在一方面,本发明提供了表现出窄分子量分布的烷氧基化物组合物。在一些实施方式中,所述烷氧基化物组合物还可以包含低含量的未反应残余醇。所述组合物包含一种或多种式I的烷氧基化物:
其中,EO、n、R、R1和R2如下面所定义。
在另一方面,本发明提供了制备式I的烷氧基化物的方法。所述方法包括:在烷氧基化条件下,将具有7-16个碳原子且支化度为3或更高的仲醇与环氧乙烷进行反应。所述烷氧基化在双金属氰化物催化剂存在下进行。
附图描述
图1显示了与使用双金属氰化物(DMC)催化剂相比较,使用KOH用2.0摩尔的环氧乙烷(EO)对2,6,8-三甲基壬-4-醇(TMN)进行乙氧基化的GPC色谱图。
图2显示了与使用双金属氰化物(DMC)催化剂相比较,使用KOH用6.6摩尔的环氧乙烷(EO)对2,6,8-三甲基壬-4-醇(TMN)进行乙氧基化的GPC色谱图。
图3显示了与使用双金属氰化物(DMC)催化剂相比较,使用KOH用9.5摩尔的环氧乙烷(EO)对2,6,8-三甲基壬-4-醇(TMN)进行乙氧基化的GPC色谱图。
发明详述
如上所述,在第一方面,本发明提供了包含一种或多种式I的烷氧基化物的组合物:
其中,EO是亚乙氧基;n为1-40;R和R1独立地是C1-C14烷基;和R2是H或C1-C13烷基,其中由R、R1、R2和它们连接的碳形成的基团含有7-16个碳原子,并具有至少3的支化度。
已经令人惊讶的发现根据本文描述的方法制备的式I的烷氧基化物表现出窄分子量分布,其由材料的多分散指数(由凝胶渗透色谱测定的重均分子量/数均分子量(Mw/Mn))表示。窄分子量分布通常产生更好的表面活性剂性质。在一些实施方式中,烷氧基化物的多分散指数(PDI)是2.0或更低、可选地1.75或更低、可选地1.5或更低、可选地1.2或更低、或可选地1.15或更低。
除了表现出低PDI,在一些实施方式中,式I的烷氧基化物还可以如本文所描述进行制备,以包含令人惊讶的低水平的未反应残余醇。相比之下,由传统的氢氧化钾催化反应制备的包含相同或类似数量环氧烷重复单元的烷氧基化物包含高得多的量的残余醇(参见实施例)。具有低含量醇的优点包括增强的表面活性、低气味、和提高的水性制剂的澄清度。在一些实施方式中,本发明的组合物包含10重量%或更少、可选地5重量%或更少、可选地3重量%或更少、可选地2重量%或更少、可选地1重量%或更少、或可选地0.5重量%或更少的残余醇。
式I包括变量“n”,其描述了在制备所述化合物中使用的所加载的环氧乙烷的摩尔量。在一些实施方式中,n是至少约2、可选地至少约3、可选地至少约4、可选地至少约5、可选地至少约6、可选地至少约7、或可选地至少约8。在一些实施方式中,n是约30或更少、可选地n是约20或更少、可选地n是约15或更少、或可选地n是约12或更少。在一些实施方式中,n落入约2至约15、可选地约4至约15、或可选地约8至约15的范围内。在一些实施方式中,n是约8。在一些实施方式中,n是约11。
在式I的烷氧基化物中,R、R1、R2和它们连接的碳形成一个基团,其是用于制备烷氧基化物的高支化仲醇的有机残基。一般而言,所述基团含有7-16个碳原子。在一些实施方式中,所述基团含有9-12个碳原子。所述基团还具有3或更大的支化度。在本发明的一些实施方式中,所述支化度为4或更大。本文中使用的术语“支化度”指甲基(-CH3)的总数减去1。例如,如果有4个甲基,那么支化度为3。
在本发明的一些实施方式中,R是C3-C12烷基、可选地为C3-C8烷基或可选地为C4-C6烷基。在一些实施方式中,R含有至少2个甲基。
在本发明的一些实施方式中,R1是C3-C12烷基、可选地为C4-C10烷基或可选地为C6-C8烷基。在一些实施方式中,R1含有至少2个甲基。
在本发明的一些实施方式中,R2是C1-C3烷基。在一些实施方式中,R2是H。
在本发明的一些实施方式中,所述烷氧基化物为式II:
其中,R3是H或异丙基且n如上所定义。
在本发明的一些实施方式中,所述烷氧基化物为下式:
其中,n如上所定义。
在一些实施方式中,所述烷氧基化物为下式:
其中,n如上所定义。
在另一方面,本发明提供了制备式I的烷氧基化物的方法。根据所述方法,高支化仲醇在催化剂存在下在烷氧基化条件下与环氧乙烷反应。用于烷氧基化的催化剂是双金属氰化物。
高支化仲醇是含有7-16个碳原子、支化度为3或更大以及一个羟基的化合物。在一些实施方式中,所述化合物包含9-12个碳原子。在一些实施方式中,所述支化度为4或更大。合适的仲醇的例子包括2,6,8-三甲基-4-壬醇、和2,6-二甲基庚-4-醇。
在烷氧基化反应之前,干燥起始醇以降低其水含量可能是有利的。可以使用各种技术,包括例如应用减压、升温、氮吹扫、或这些的组合。水含量可以降低至例如300ppm或更低、可选地200ppm或更低、或可选地100ppm或更低、或可选地50ppm或更低、或可选地25ppm或更低。
环氧乙烷与醇在烷氧基化条件下反应。在说明合适的烷氧基化条件的非限制性实施方式中,该反应可以在约80℃至约180℃的一个升高的温度或多个升高的温度下进行。在其它非限制性实施方式中,温度范围为约100℃至约160℃。在某些非限制性实施方式中,约14psia至约60psia的压力是特别有效的,但其它压力也可以有效地使用。本领域技术人员将能够至多使用常规实验来确定合适的条件。
烷氧基化反应在有效量的作为催化剂的双金属氰化物化合物存在下进行。在一些实施方式中,所述催化剂的量基于醇和氧化物的总载量可以为以重量计约1ppm至约1000ppm。在一些实施方式中,所述量可以为约10ppm至约300ppm。合适的双金属氰化物催化剂包括在U.S.专利6,429,342中描述的那些,所述专利通过引用并入本文。通过举例的方式,可以使用Zn3[Co(CN)6]2作为催化剂。
在说明本发明的典型方法中,所述催化剂可以溶解或分散在干燥的醇中或,可选地这两种物质可以先混合然后例如使用上述技术干燥醇,以降低残余水含量。然后可以连续地添加环氧乙烷,且反应持续进行直至发生期望水平的烷氧基化。在一些实施方式中,环氧乙烷可以以分批方式,例如在整个反应过程中通过二、三、或四批进行添加。所述反应在环氧乙烷添加之间和/或在最后的环氧乙烷添加之后经历消化期间(例如在约100℃至160℃下约1-10小时)。
烷氧基化反应之后,产物可以从反应器中排出直接进行包装,而不用除去催化剂。如果需要,所述产物可以在包装或使用之前过滤,或通过各种方式处理以除去或回收所述催化剂,例如在US4,355,188、4,721,818、4,877,906、5,010,047、5,099,075、5,416,241中所教导的,每篇文献通过引用并入本文。
所述产物还可以经历其它的纯化步骤。例如,在一些实施方式中,可以通过在升高的温度,例如120℃或更高、可选地150℃或更高下加热所述粗乙氧基化产物来进一步降低残余醇的水平。此外,在一些实施方式中,可以使用真空,例如250托或更低、或200托或更低、或150托或更低,使得超过任何残余醇的沸点。惰性气体例如氮气可以流经(顶空喷射)或流过(液面下喷射)所述产物以进一步促进醇的去除。可以使用前述技术的组合。
本发明最终的式I的烷氧基化物可以以任何期望量用于制剂和组合物中。通过举例的方式,当用作表面活性剂时,在许多常规应用中的通常量基于总制剂为约0.05重量%至约90重量%、更经常为约0.1重量%至约30重量%,以及在一些用途中为约0.5重量%至约20重量%。本领域技术人员将能够通过结合应用领域的普通知识以及常规实验(需要的话)来确定用量。
本发明的烷氧基化物的应用可以包括各种各样的制剂和产品。这些包括但不限于在清洁剂、洗涤剂、硬表面清洁制剂、聚氨酯、环氧制剂、乳液聚合、热塑性塑料、金属产品、农业产品包括除草剂和杀虫剂、油田产品和工艺、纸浆和纸产品、织物、水处理产品、地板产品、油墨、着色剂、药用产品、清洁产品、个人护理产品、和润滑剂中作为表面活性剂、或润湿、乳化、增溶、分散、破乳、清洁、泡沫控制剂、或助剂、或这些功能的组合。作为分散应用的一个实例,本发明的烷氧基化物可以用作氟树脂的分散剂。
下面的实施例是说明本发明但不旨在限制其范围。除非另有指示,本文中使用的比率、百分比、份数等以重量计。
实施例
原料
2,6,8-三甲基壬-4-醇(TMN)和2,6-二甲基庚-4-醇(二异丁基甲醇或DIBC)由The Dow Chemical Company提供。
双金属氰化物(DMC)催化剂由Bayer提供。
环氧乙烷(EO)由The Dow Chemical Company提供。
生产装置
DMC催化的烷氧基化物样品在9升的有搅拌、挡板和夹套反应器中使用半分批方法制备。
性质测试方法
常规GPC用于一般分子量分析。报告的结果是相对于线性聚乙二醇标准品。聚合物Laboratories PEG-10聚乙二醇用于三阶拟合。使用在40℃下运行的配备有Polymer Labs Mixed E柱偶联示差折光检测器的Agilent 1100系统测量分子量。色谱流动相为四氢呋喃(THF)。每个样品(100μl,25mg/mL)溶解在THF中,两次注入,并以1.0mL/min洗脱。
对烷氧基样品的%OH和羟基当量分子量(HEMW)通过根据ASTM D4274(测试法B)的滴定来确定。HEMW使用方程式1来计算:
其中,N是样品的官能度(1,在仲醇乙氧基化物情况下,本研究使用单醇)。
烷氧基化物样品中未反应的醇的量通过气相色谱使用内标1-壬醇的响应来确定。称量(最接近0.1mg)大约0.05g的乙氧基化物样品和0.03-0.1g的内标储液(己烷中的正壬醇,9.9%(w/w))装入自动进样小瓶中。样品在60℃下使用1mL的Regisil(99%的BSTFA和1%的TMCS)衍生化15分钟以增加高分子量组分的挥发性。样品根据需要进一步稀释在己烷和四氢呋喃中。衍生化的样品使用配备有HP-7673自动进样器、柱上入口、和火焰离子化检测器的Agilent6890仪器进行评价。报告的醇浓度数据来自单次注入。
实施例1
TMN醇的乙氧基化
通过在DMC催化剂的存在下,EO与TMN之间的反应来制备TMN醇的乙氧基化物。DMC催化剂(0.15g)在1,193g的干燥(90℃,氮气吹洗,直至水少于200ppm(23ppm))的起始醇(TMN)中制浆、活化(200g的EO,130℃,在20psia的氮气下)、然后在搅拌下连续地(5g/min)加入626g的EO(总共826g),在81min的消化期间(130℃)之后产生烷氧基化产物。除去中间体样品(表1中的1-A,120g)。反应产物测量为5.37%OH的羟基含量和317的羟基当量分子量(HEMW),对应于2.9EO/TMN摩尔比的烷氧基化物。随后,使用第二环氧乙烷(1,268g EO,总计2,094g EO)进料(5g/min)和消化期间(67min,130℃)。除去中间体样品(1-B,123g)。反应产物测量为3.33%OH的羟基含量和511的HEMW,对应于7.3EO/TMN摩尔比的烷氧基化物。随后,使用第三环氧乙烷(879g EO,总计2,976g EO)进料(5g/min)和消化期间(7小时,130℃)。反应产物(1-C)测量为2.56%OH的羟基含量和663的HEMW,对应于10.8EO/TMN摩尔比的烷氧基化物。如表1中所列,TMN/2.9EO样品包含18.6%的未反应TMN醇残余并具有1.24的PDI。TMN/7.3EO样品包含2.8%的未反应TMN醇残余并具有1.13的PDI。TMN/10.8EO样品包含2.3%的未反应TMN醇残余并具有1.24的PDI。
根据相同的程序制备其它TMN/EO产物,并列在表1中(实施例2-8)
表1.DMC催化的TMN醇烷氧基化物的性质结果
a醇引发剂中的水含量
实施例9
DMC催化的DIBC醇的直接乙氧基化
通过在DMC催化剂的存在下,EO与DIBC之间的反应来制备DIBC醇的乙氧基化物。DMC催化剂(0.16g)在1,535g的干燥(90℃,氮气吹洗,直至水少于200ppm(23ppm))的起始醇(DIBC)中制浆、活化(215g的EO,130℃,在20psia氮气下)、然后在搅拌下连续地(5g/min)加入1,320g的EO(总共1,535g),在75min的消化期间(130℃)之后产生烷氧基化产物。反应产物(表2中的9)被除去并测量为2.90%OH的羟基含量和587的HEMW,对应于10.0EO/DIBC摩尔比的烷氧基化物。如表2中所列,DIBC/10.0EO样品包含0.2wt%的未反应DIBC醇残余并具有1.04的PDI。
根据相同的程序制备其它DIBC/EO产物,并列在表2中(实施例9-11)
表2.DMC催化的DIBC烷氧基化物的性质结果
a醇引发剂中的水含量
比较例12
用KOH制备的TMN/EO烷氧基化物
通过在KOH催化剂的存在下,EO与TMN之间的反应来制备烷氧基化物产物。KOH催化剂(5.80g,45%的水溶液,包含2.55gKOH)溶解在999g的TMN醇中、汽提(90℃,真空下,用氮气吹扫,直至水少于300ppm(215ppm))、活化(200g的EO,130℃,在20psia的氮气下)、然后在搅拌下连续地(5g/min)加入1,425g的EO(总共1,625g),在120min的消化期间(130℃)之后产生烷氧基化产物。除去中间体样品(12-A,122g)。反应产物测量为3.5%OH的羟基含量和486的HEMW,对应于6.7EO/TMN摩尔比的烷氧基化物。随后,使用第二环氧乙烷(552g EO,总计2,177g EO)进料(5g/min)和消化期间(122min,130℃)。除去中间体样品(12-B,153g)。反应产物测量为2.8%OH的羟基含量和601的HEMW,对应于9.4EO/TMN摩尔比的烷氧基化物。随后,使用第三环氧乙烷(607g EO,总计2,784g EO)进料(5g/min)和消化期间(112min,130℃)。反应产物(12-C)测量为2.2%OH的羟基含量和762的HEMW,对应于13.0EO/TMN摩尔比的烷氧基化物。如表3中所列举,TMN/6.7EO样品包含16.7%的未反应TMN醇残余并具有2.59的PDI。TMN/9.4EO样品包含16.5%的未反应TMN醇残余并具有2.43的PDI。TMN/13.0EO样品包含10.7%的未反应TMN醇残余并具有2.09的PDI。
根据相同的程序制备其它TMN/EO产物,并列在表3中(实施例13)
表3.KOH催化的TMN乙氧基化物和烷氧基化物的性质结果
a醇引发剂中的水含量
在同样的EO/TMN载荷比率下,相比于KOH催化剂,DMC催化剂转化了更多的起始醇,并具有更少的杂质(聚乙二醇,PEG)。图1-3比较了用DMC催化剂制备的烷氧基化物和用KOH催化剂制备的烷氧基化物的GPC色谱图。图1显示了2.0摩尔EO的烷氧基化,图2显示了6.6摩尔EO的烷氧基化,和图3显示了9.5摩尔EO的烷氧基化。PEG在小于29分钟处被洗脱,TMN烷氧基化物产物在29-33.6分钟之间洗脱,和TMN醇在33.6-35.0分钟之间洗脱。
实施例14:后乙氧基化方法
即使本发明的DMC催化的乙氧基化方法产生了具有期望的低多分散性的产物,在某些情况下,其还希望进一步降低产物中残余醇的浓度,例如为了提高浊点和/或降低气味。一般来说,后乙氧基化处理包括在真空下用顶空氮气喷射和搅拌下加热烷氧基化产物。通过后乙氧基化处理可以获得包含残余醇含量<1wt%的样品。示例性数据显示在表4中。该表显示了用于后处理的大约的温度、压力、和时间。还显示了最终产物的残余醇含量、浊点和PDI。
表4.各种乙氧基化物样品的后处理
虽然已经根据本发明的优选实施方式对本发明进行了如上描述,但其可以在该公开的精神和范围内修改。因此本申请旨在使用本文中公开的一般原理来覆盖本发明的任何变体、用途、或改编。而且,本发明旨在覆盖在本发明所属领域的已知或常规实践内并落入下面的权利要求的限制内的对本公开的这些背离。
Claims (14)
1.包含一种或多种式I的烷氧基化物的组合物:
其中,EO是亚乙氧基;n为1-40;R和R1独立地是C1-C14烷基;和R2是H或C1-C13烷基,其中由R、R1、R2和它们连接的碳形成的基团含有7-16个碳原子,并具有至少3的支化度,其中所述烷氧基化物的多分散指数是2.0或更低。
2.根据权利要求1的组合物,其中由R、R1、R2和它们连接的碳形成的基团含有9-12个碳原子。
6.根据权利要求1-5任一项的组合物,其中n为约8至约15。
7.根据权利要求1-6任一项的组合物,其中所述多分散指数是1.15或更低。
8.根据权利要求1-7任一项的组合物,其包含不超过10重量%的残余醇。
9.用于制备权利要求1-8任一项的烷氧基化物组合物的方法,其包括:在烷氧基化条件下,将具有7-16个碳原子和支化度为3或更高的仲醇与环氧乙烷进行反应,其中所述烷氧基化在双金属氰化物催化剂存在下进行。
10.根据权利要求9的方法,其中所述仲醇具有9-12个碳原子和3或更高的支化度。
11.根据权利要求9-10任一项的方法,其中所述仲醇为2,6,8-三甲基-4-壬醇或2,6-二甲基庚-4-醇。
12.根据权利要求9-11任一项的方法,其中所述仲醇在所述烷氧基化步骤之前干燥,以将残余水含量降低至200ppm或更低。
13.根据权利要求9-12任一项的方法,其中在所述烷氧基化反应之后,所述烷氧基化物组合物在升高的温度下、在减压下、或用惰性气体喷射、或这三者的任何组合下进行加热,以除去含于所述组合物中的至少部分残余醇。
14.一种制剂,其选自洗涤剂、硬表面清洁剂、聚氨酯制剂、环氧制剂、乳液聚合制剂、热塑性制剂、金属产品、农业产品包括除草剂和杀虫剂、油田产品、纸浆和纸产品、织物制剂、水处理产品、地板产品、油墨制剂、着色制剂、药用产品、清洁产品、个人护理产品、氟树脂分散体、和润滑剂,其中所述制剂包含根据权利要求1-8任一项的组合物。
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EP (1) | EP2643282A2 (zh) |
JP (1) | JP2014506238A (zh) |
CN (1) | CN103270012A (zh) |
WO (1) | WO2012071149A2 (zh) |
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CN107963959A (zh) * | 2017-11-29 | 2018-04-27 | 常州大学 | 一步法合成2,6,8-三甲基-4-壬醇的工艺方法 |
CN111423575A (zh) * | 2020-05-07 | 2020-07-17 | 江苏赛科化学有限公司 | 一种仲醇聚氧乙烯醚的制备方法 |
WO2021081732A1 (en) * | 2019-10-29 | 2021-05-06 | Dow Global Technologies Llc | Two-component polyurethane composition |
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WO2013164492A1 (en) * | 2012-07-13 | 2013-11-07 | Basf Se | Use of alkoxylated non-ionic surfactants as additive in aqueous membrane cleaning compositions |
MX2017003315A (es) * | 2014-09-18 | 2017-06-21 | Akzo Nobel Chemicals Int Bv | Uso de alcoholes ramificados y alcoxilatos de los mismos como colectores secundarios. |
SG11202002103VA (en) * | 2017-09-14 | 2020-04-29 | Dow Global Technologies Llc | Process of manufacturing polyols |
SG11202002126WA (en) | 2017-09-14 | 2020-04-29 | Univ Northwestern | Process of manufacturing polyols |
FR3073519A1 (fr) | 2017-11-10 | 2019-05-17 | Arkema France | Alcool secondaire alcoxyle |
FR3073517A1 (fr) | 2017-11-10 | 2019-05-17 | Arkema France | Sulfates d'alcools secondaires alcoxyles |
FR3073521A1 (fr) | 2017-11-10 | 2019-05-17 | Arkema France | Ester de phosphate d'alcool secondaire |
JP7251308B2 (ja) * | 2019-05-20 | 2023-04-04 | コニカミノルタ株式会社 | インクジェット記録液セット、画像形成方法および印刷物 |
JP2021021022A (ja) * | 2019-07-29 | 2021-02-18 | 株式会社リコー | インク、インクジェット記録方法、及びインクジェット記録装置 |
WO2021171209A1 (en) * | 2020-02-28 | 2021-09-02 | Oxiteno S.A. Indústria E Comércio | Low 1,4-dioxane production in sulfation of an ethoxylated mixture prepared by using dmc catalyst |
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WO2021081732A1 (en) * | 2019-10-29 | 2021-05-06 | Dow Global Technologies Llc | Two-component polyurethane composition |
CN111423575A (zh) * | 2020-05-07 | 2020-07-17 | 江苏赛科化学有限公司 | 一种仲醇聚氧乙烯醚的制备方法 |
Also Published As
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JP2014506238A (ja) | 2014-03-13 |
US20130231508A1 (en) | 2013-09-05 |
WO2012071149A2 (en) | 2012-05-31 |
WO2012071149A3 (en) | 2012-12-06 |
EP2643282A2 (en) | 2013-10-02 |
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