CN113135843A - 一种双端胺基型亲水扩链剂的制备方法 - Google Patents
一种双端胺基型亲水扩链剂的制备方法 Download PDFInfo
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- FSSPGSAQUIYDCN-UHFFFAOYSA-N 1,3-Propane sultone Chemical compound O=S1(=O)CCCO1 FSSPGSAQUIYDCN-UHFFFAOYSA-N 0.000 claims abstract description 14
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- KCLIFOXATBWLMW-UHFFFAOYSA-M sodium;ethane-1,2-diamine;ethanesulfonate Chemical compound [Na+].NCCN.CCS([O-])(=O)=O KCLIFOXATBWLMW-UHFFFAOYSA-M 0.000 description 1
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- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
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Abstract
本发明公开了一种双端胺基型亲水扩链剂的制备方法,包括将乙二胺溶于溶剂中分散,控制体系温度,向体系中滴加1,3‑丙烷磺内酯,控制滴加速度并保持体系温度,滴加时间控制在2‑4h,后期老化时间控制在2‑5h;中控取样监控样品仲胺值及总胺值后,加入碱对其磺酸部分进行酸碱反应,调节pH至合适的范围,减压脱除体系中存在的溶剂,最后加水调节固含到合适的范围,即可得到双端胺基型亲水扩链剂水溶液。本发明提供一种与乙二胺基乙磺酸盐结构及性质类似的双端胺基型亲水扩链剂的制备方法,利用1,3‑丙烷磺内酯的开环反应及其选择性,在水溶液中选择性合成,合成工艺简单,无需使用大量有机溶剂,无需繁复的后处理工艺,绿色环保,可工业化程度高。
Description
技术领域
本发明属于有机化合物合成领域,具体涉及一种双端胺基型亲水扩链剂的制备方法。
技术背景
水性聚氨酯是指以水代替有机溶剂作为分散介质的新型聚氨酯体系,主要应用在涂料、皮革涂饰、胶黏剂及纺织印染等领域。传统的溶剂型聚氨酯体系,因其在环保性上的缺陷,目前已逐步被水性聚氨酯取代。合成水性聚氨酯的原料主要有多异氰酸酯、多元醇、催化剂、亲水扩链剂、水和溶剂等,其中亲水扩链剂是水性聚氨酯体系能在水中分散的关键基团。亲水扩链剂的亲水官能团主要为羧酸及其盐或者磺酸及其盐,根据其扩链基团的不同,亲水扩链剂可以分为两种:双端羟基型和双端胺基型。双端胺基型相比于双端羟基型具有更高的反应活性,通常以水溶液的形式存在。在合成水性聚氨酯时,双端胺基与异氰酸酯基团进行扩链反应时生成的特殊结构的基团,能赋予水性聚氨酯更高的性能。
目前,使用较为广泛的双端胺基型亲水扩链剂为乙二胺基乙磺酸盐(一般称为AAS盐或者A95),较为传统的合成工艺为采用乙二胺和2-氯乙磺酸钠进行合成,经过减压蒸馏、分层及干燥后得到成品乙二胺基乙磺酸钠,此方法原料利用率低、不易工业化生产及成品中存在氯离子使其应用范围受到局限等(康平平,宋文生.有机化学,2009,29(6):904~908)。
专利CN102702037以β-羟乙基乙二胺为原料,采用硫酸酯化后,再以亚硫酸盐对其进行磺化,经系列后处理得到乙二胺基乙基磺酸盐。该工艺耗时较长,对生产设备要求较高,后处理纯化步骤较为复杂。
专利CN106187829A以羟基乙腈、牛磺酸、碱金属氢氧化物为原料,经过脱水缩合反应制备得到氰乙基牛磺酸盐;然后在加氢催化剂作用下加氢制备得到乙二胺基乙磺酸盐加氢液;脱除溶剂后得到产品乙二胺基乙磺酸盐。该工艺路线中使用的羟基乙腈为管制品,催化加氢对设备要求高,不易工业化生产。
专利CN111100041A,以乙二胺、乙基磺酸内酯为原料合成乙二胺基乙磺酸,然后乙二胺基乙磺酸和碱性钠反应合成最终的产品乙二胺基乙磺酸钠。该工艺中使用的乙基磺酸内酯原料较为少有,难以大量使用,该合成路线不易工业化生产。
因此,鉴于乙二胺基乙磺酸盐合成路线存在着各方面的弊端,寻找一种结构及性质与其相似,且合成过程无大量三废产生,工艺过程简单,产品收率高的产品成为一种更优的选择。
发明内容
为解决上述问题,本发明提供了一种双端胺基型亲水扩链剂的制备方法,与乙二胺基乙磺酸盐结构及性质类似产品的合成方法,即乙二胺基丙磺酸盐,该产品的合成工艺简单,在合成过程中无需使用大量溶剂,无需繁复的后处理工艺,具有绿色环保,可工业化程度高等特点。
为实现上述目的,本发明通过以下技术方案予以实施:一种双端胺基型亲水扩链剂的制备方法,其步骤如下:
(1)将乙二胺溶于溶剂中分散,控制体系温度,向体系中滴加1,3-丙烷磺内酯,控制滴加速度并保持体系温度,滴加时间控制在2-4h,后期老化时间控制在2-5h。中控取样监控样品仲胺值及总胺值。
(2)加入碱对其磺酸部分进行酸碱反应,调节pH至合适的范围,保持温度在30-50℃,减压脱除体系中存在的溶剂,最后加水调节固含到合适的范围,即可得到乙二胺基丙磺酸盐水溶液。
本发明制备双端胺基型亲水扩链剂,即乙二胺基丙磺酸盐的反应方程式如下:
其中M为Na或者K。
作为优选,步骤(1)中所述的溶剂为水或水与甲醇、乙醇、异丙醇、丙酮、丁酮中的一种混合得到,其中,水与甲醇或乙醇或异丙醇或丙酮或丁酮的混合质量比为1-10:1.
作为优选,步骤(1)中所述乙二胺与溶剂的质量比为0.5-3:1。
作为优选,步骤(1)中反应体系的反应温度为0-10℃。
作为优选,步骤(1)中所述乙二胺与1,3-丙烷磺内酯的摩尔比为1-1.2:1。
作为优选,步骤(2)中所述碱为氢氧化钾、氢氧化钠中的一种。
作为优选,步骤(2)中所述碱与1,3-丙烷磺内酯的摩尔比为0.8-1:1。
作为优选,步骤(2)中所述pH范围为8-10,此范围内可消除体系中微量的1,3-丙烷磺内酯。
作为优选,步骤(2)中样品固含可在50-70%范围内任意调节。
与现有技术相比,本发明具有如下优点:
(1)本发明的产品与对应的产品结构及性质相似,但工艺路线中采用的原料均为常规产品,原料易得,且合成工艺过程简单,反应条件温和,反应原料转化率高,可达到98%以上。
(2)本发明采用水作为溶剂主体,辅以其他溶剂,合成过程绿色环保,对生产设备要求低,易于工业化生产。
(3)本发明合成过程中未引入氯离子,产品应用范围更广。相比于目前市面上存在的乙二胺基乙磺酸钠多为50%溶液,本发明所合成的产品固含上限可达70%,在运输及产品应用上更具备优势。
具体实施方式
为使本发明的上述特征及优点能够更明显易懂,下面结合说明书实施例对本发明的具体实施方式做详细的说明,但不以任何方式限制本发明。
实施例1。
一种双端胺基型亲水扩链剂的制备方法,其步骤如下:
(1)将97.6g乙二胺加入到500ml带有温度计、冷凝回流管及机械搅拌的四口烧瓶中,加入60g水搅拌溶解分散,控制体系温度在0-10℃。
(2)在上述温度范围条件下,滴加198g 1,3-丙烷磺内酯,维持体系温度范围在0-10℃。滴加时间为2-4h,老化时间2-5h。老化过程中,连续两次取样,中控样品仲胺值无明显变化。
(3)向反应体系中加入120g 50%氢氧化钠水溶液,调节体系pH至8-10,此过程保持温度在30-50℃。取样分析样品仲胺值与总胺值比例,由此判断原料的转化率为93.54%。加水调节固含至50%,即可得到乙二胺基丙磺酸钠水溶液。
实施例2。
一种双端胺基型亲水扩链剂的制备方法,其步骤如下:
(1)将94.7g乙二胺加入到500ml带有温度计、冷凝回流管及机械搅拌的四口烧瓶中,加入60g水与甲醇的混合溶液,其中水与甲醇的质量比为2:1,搅拌溶解分散,控制体系温度在0-10℃。
(2)在上述温度范围条件下,滴加190.5g 1,3-丙烷磺内酯,维持体系温度范围在0-10℃。滴加时间为2-4h,老化时间2-5h。老化过程中,连续两次取样,中控样品仲胺值无明显变化。
(3)向反应体系中加入115g 50%氢氧化钠水溶液,调节体系pH至8-10,此过程保持温度在30-50℃。取样分析样品仲胺值与总胺值比例,由此判断原料的转化率为97.61%。
减压脱除体系中甲醇,加水调节固含至50%,即可得到乙二胺基丙磺酸钠水溶液。
实施例3。
一种双端胺基型亲水扩链剂的制备方法,其步骤如下:
(1)将92.9g乙二胺加入到500ml带有温度计、冷凝回流管及机械搅拌的四口烧瓶中,加入60g水与乙醇的混合溶液,其中水与乙醇的质量比为2:1,搅拌溶解分散,控制体系温度在0-10℃。
(2)在上述温度范围条件下,滴加189.2g 1,3-丙烷磺内酯,维持体系温度范围在0~10℃。滴加时间为2-4h,老化时间2-5h。老化过程中,连续两次取样,中控样品仲胺值无明显变化。
(3)向反应体系中加入140g 50%氢氧化钾水溶液,调节体系pH至8-10,此过程保持温度在30-50℃。取样分析样品仲胺值与总胺值比例,由此判断原料的转化率为98.13%。
减压脱除体系中乙醇,加水调节固含至50%,即可得到乙二胺基丙磺酸钾水溶液。
实施例4。
一种双端胺基型亲水扩链剂的制备方法,其步骤如下:
(1)将95.2g乙二胺加入到500ml带有温度计、冷凝回流管及机械搅拌的四口烧瓶中,加入60g水与丙酮的混合溶液,其中水与丙酮的质量比为2:1,搅拌溶解分散,控制体系温度在0-10℃。
(2)在上述温度范围条件下,滴加193.1g 1,3-丙烷磺内酯,维持体系温度范围在0-10℃。滴加时间为2-4h,老化时间2-5h。老化过程中,连续两次取样,中控样品仲胺值无明显变化。
(3)向反应体系中加入142g 50%氢氧化钾水溶液,调节体系pH至8-10,此过程保持温度在30-50℃。取样分析样品仲胺值与总胺值比例,由此判断原料的转化率为98.24%。加水调节固含至50%,即可得到乙二胺基丙磺酸钾水溶液。
丙酮在水性聚氨酯的合成中,常用作降粘剂使用,因此在此实施例并未将丙酮脱除,乙二胺基丙磺酸盐水溶液中含有丙酮对后端应用基本无影响。
实施例5。
(1)带有机械搅拌和温度计的四口烧瓶中加入聚丙二醇(PPG-2000),120℃条件下真空脱水2h。
(2)降温至70℃,加入异佛尔酮二异氰酸酯(IPDI),与PPG-2000摩尔比1.6-2.2:1,滴加2-5滴二月桂酸二丁基锡,反应至NCO达到理论值,得到水性聚氨酯预聚体。
(3)加入1,4-丁二醇与50%含量的乙二胺基丙磺酸钠(EPS-Na)水溶液到用丙酮降粘的水性聚氨酯预聚体中,控制反应温度在30-40℃,其中1,4-丁二醇与EPS-Na的之和摩尔量与IPDI的摩尔量之比为0.1-0.5:1,EPS-Na质量占体系总质量的1-3%。
(4)向上述体系中在高速搅拌下加入去离子水乳化,减压脱除丙酮,乳液外观呈乳白色,离心后仍具有较好的稳定性,置于-5℃24h仍具有较好的稳定性。
聚丙二醇(PPG-2000)120℃条件下真空脱水2h后,降温至70℃,按与PPG-2000摩尔比1.6-2.2:1加入IPDI,在催化剂二月桂酸二丁基锡催化作用下,NCO反应至预定值,丙酮降粘后,采用1,4-丁二醇和EPS-Na扩链,反应3-5h后,在高速搅拌下向体系中加入去离子水乳化,减压脱除丙酮,乳液外观呈乳白色,离心后仍具有较好的稳定性,置于-5℃24h仍具有较好的稳定性。其中1,4-丁二醇与EPS-Na的之和摩尔量与IPDI的摩尔量之比为0.1-0.5:1。
以上所述是本发明的优选实施方式而已,当然不能以此来限定本发明之权利范围,应当指出,对于本技术领域的普通技术人员来说,在不脱离本发明原理的前提下,还可以做出若干改进和变动,这些改进和变动也视为本发明的保护范围。
Claims (9)
2.根据权利要求1中所述的双端胺基型亲水扩链剂的制备方法,其特征在于,步骤(1)中所述的溶剂为水或水与甲醇、乙醇、异丙醇、丙酮、丁酮中的一种混合得到,其中,水与甲醇或乙醇或异丙醇或丙酮或丁酮混合的质量比为1-10:1。
3.根据权利要求1中所述的双端胺基型亲水扩链剂的制备方法,其特征在于,步骤(1)中所述乙二胺与溶剂的质量比为0.5-3:1。
4.根据权利要求1中所述的双端胺基型亲水扩链剂的制备方法,其特征在于,步骤(1)中所述体系的反应温度为0-10℃。
5.根据权利要求1中所述的双端胺基型亲水扩链剂的制备方法,其特征在于,步骤(1)中所述乙二胺与1,3-丙烷磺内酯的摩尔比为1-1.2:1。
6.根据权利要求1中所述的双端胺基型亲水扩链剂的制备方法,其特征在于,步骤(2)中所述碱为氢氧化钾、氢氧化钠中的一种。
7.根据权利要求1中所述的双端胺基型亲水扩链剂的制备方法,其特征在于,步骤(2)中所述碱与1,3-丙烷磺内酯的摩尔比为0.8-1:1。
8.根据权利要求1中所述的双端胺基型亲水扩链剂的制备方法,其特征在于,步骤(2)中所述pH范围为8-10,此范围内可消除体系中微量的1,3-丙烷磺内酯。
9.根据权利要求1中所述的双端胺基型亲水扩链剂的制备方法,其特征在于,步骤(2)中样品固含在50-70%范围内任意调节。
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