CN1064271C - 一种乳化液膜用表面活性剂及其制备方法 - Google Patents
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Abstract
一种乳化液膜用表面活性剂,其结构通式为:
它以分子量40~70万的丁基胶为原料,依次经过以下工艺步骤:(1)温度为280℃~300℃,恒温时间为40~90分钟的热降解;(2)加入非极溶剂溶解;(3)在200~240℃下与马来酸酐恒温反应8~12小时的热加合;(4)加入乙烯胺类化合物胺化反应等。本发明的制备方法工艺简单且节能,该方法制备的乳化液膜用表面活性剂,适用范围大,液膜稳定性好、溶胀小。它不仅是一种性能优良的乳化剂,而且还是有效的膜增强剂。
Description
本发明涉及液膜分离技术,具体地说是提供一种用于液膜分离工业化应用的表面活性剂及其制备方法。
国际上,液膜分离技术在七十年代逐渐兴起。在液膜分离技术中最关键的问题之一是采用一种理想的表面活性剂,而目前国内外市售的用于液膜分离技术的表面活性剂均存在溶胀率过大,破损率高,液膜稳定性差的缺点,因此,不能满足工业规模连续运行的要求。
国外正处中试和向工业应用过渡阶段的取得成效的液膜用表面活性剂有美国专利US4,259,189公开的ENJ-3029和英国专利Brit、UK2,038,201公开的ECA-4360。根据这两项专利文献记载的内容,这两种表面活性剂均为聚胺类衍生物,平均分子量均为2000左右,其结构式分别如下:式中m约为40,平均分子量约为2000式中n约为40,平均分子量约为2000
虽然上述两种液膜用表面活性剂在较高温度下液膜稳定性较span-80等有较大提高,但是它们属低分子范围,仍存在着溶胀过大、运行过程液膜稳定性欠佳的缺点。
上述与本发明最接近的两篇对比文献中均未公开其制备方法。
本发明的目的在于克服背景技术的缺点,创造一种能满足工业规模连续运行要求的液膜用表面活性剂及其制备方法。从原料的选择、工艺路线的设定入手,以改变亲油基、亲水基的组成和分子量、分子量分布,使本发明的表面活性剂不仅在多种条件下能极大地降低液膜的溶胀,而且破损率低、液膜稳定性好。本发明的制备方法工艺简单、易操作、设备投资少且节能,原料来源充裕,且价格低廉,产品成本低。
本发明的目的可通过以下措施来达到:
一种乳化液膜用表面活性剂,其特征在于它的有效成份主要为长链烃基单丁二酰亚胺的聚胺类衍生物,它的结构通式为:式中,R为异丁烯与异戊二烯的共聚物,其中异丁烯组份含量的重量百分比为97.5~98%,异戊二烯组份含量的重量百分比为2~2.5%;n为2~10的整数,其平均分子量为2000~10000,分子量分布指数大于3。
一种聚胺类乳化液膜用表面活性剂的制备方法,其特征在于它依次包括如下步骤:
步骤一:分子量为2000~10000的裂解丁基胶的制备
a)分子量为40~70万的丁基胶为原料,
b)采用远红外加热炉,N2保护下进行热降解,其热降解温度为280℃~300℃,恒温时间为40~90分钟,制得平均分子量在2000~10000范围内不等的裂解丁基胶:
步骤二:30%~60%重量百分比的裂解丁基胶胶液的配制
紧接步骤一,趁热加入非极性溶剂磺化煤油或精制柴油或白矿油或液体石蜡,配制成按丁基胶重量百分比计的30%~60%的裂解丁基胶胶液,且趁热过滤,除去残留的小胶块;
步骤三:热加合
将经溶解、过滤后的丁基胶胶液放入密封且带搅拌的反应器中,加热至120℃~150℃时,按马来酸酐/裂解丁基胶的摩尔比为1.0~1.2/1的量加入马来酸酐,然后缓慢升温至200℃~240℃,并在该温度下恒温、搅拌反应8~12小时,制得长链烃基丁二酸酐溶液;
步骤四:胺化
将长链烃基丁二酸酐溶液冷却至60℃~室温后用苯或甲苯按1∶1~3重量份混合稀释,过滤后放入带搅拌的回流的反应器中,按乙烯胺类化合物/长链烃基丁二酸酐的摩尔比为1.0~1.2/1.0加入乙烯胺类化合物,进行胺化反应,加热回流二小时;再将其产物升温至130℃~150℃后,经减压蒸馏至除尽混合反应物中的水及溶剂苯或甲苯,制得乳化液膜用表面活性剂。
本发明与背景技术相比具有如下优点:
(1)本发明的表面活性剂以来源充裕、价格低廉的丁基胶为原料,并通过控制制备的工艺条件,制得数均分子量在2000~10000范围内,分散指数大于3的中间原料裂解丁基胶,分别加入不同的非极性溶剂和乙烯胺类化合物胺化制备出不同组成、不同结构的能满足不同条件需要的系列产品,因而扩大了适用范围。
(2)本产品不溶于水、丙酮和乙醇,而溶于汽油、煤油、柴油、矿物油、石蜡油、正己烷等有机溶剂,因此,特别适用制备油包水型乳液。在乳化液膜中,本表面活性剂不仅是一种性能优良的乳化剂,而且还是有效的膜增强剂。在它的作用下,液膜稳定性好、破损率低、溶胀率小。且与各类载体配伍性能极佳,能广泛适用于酸、中、碱性液膜体系。表面活性剂分子量大小,组成与液膜稳定性和溶胀的关系,见附表1。
(3)本发明的制备方法,工艺简单、易操作,设备投资少且节能。
附表1
图1为一种乳化液膜用表面活性剂制备工艺流程示意图。
下面将通过实施例及附图对本发明作进一步详述:
步骤一:裂解丁基胶的制备
以市售日本268丁基胶为原料,将其切成胶片,其厚度以不大于0.5cm为宜,称取1000克均匀地平铺于不锈钢托盘中,然后把托盘置于密闭的远红外加热炉中,N2保护下,升温至200℃,这时丁基胶开始膨化--熔化--分解,开启排风机及时将产生的气体排出。继续升温至280℃~300℃,升温过程时间约为30分钟,丁基胶开始裂解,在280℃~300℃的温度范围内,恒温40~90分钟,中间可打开炉门进行搅拌,当胶液的流动性明显增加时,控制恒温时间,随裂解温度的升高和恒温时间的延长可制得不同分子量的裂解丁基胶,其裂解温度、恒温时间与分子量及分子量分布的关系由表2列表提供。
步骤二:
按表2中的用量趁热加入磺化煤油或精制柴油或白矿油或液体石蜡等非极性溶剂分别配制重量百分比为30%~60%的裂解丁基胶胶液,然后再趁热过滤、除去残留小胶块。
步骤三:热加合
称取经溶解、过滤后的丁基胶胶液放入密封且带搅拌的反应器中,加热至120℃~150℃时按表2中所列工艺条件加入马来酸酐,然后分别升温至各实施例的热加合温度,并在该温度下恒温、搅拌按各实施例所需反应时间反应数小时,制得长链烃基丁二酸酐溶液。
步骤四:胺化
将长链烃基丁二酸酐溶液冷却至60℃至室温后,按表2中用量加入苯或甲苯稀释,过滤后放入带搅拌的四口回流反应器中,再按表2中用量和名称加入乙烯胺类化合物,经加热、回流使其胺化反应,各实施例的胺化温度和时间由表2给出。最后用分水器除去反应生成的水和溶剂苯或甲苯。当绝大部分溶剂和水被除去后,升温至130℃~150℃,减压蒸馏,除尽反应物中水和溶剂,所得产物即为主要有效成份为长链烃基单丁二酰亚胺的乳化液膜用表面活性剂。
附表2
Claims (5)
2、根据权利要求1所述的乳化液膜用表面活性剂,其最佳平均分子量为5000~10000。
3、一种聚胺类乳化液膜用表面活性剂的制备方法,其特征在于它依次包括如下步骤:
步骤一:分子量为2000~10000的裂解丁基胶的制备
a)分子量为40~70万的丁基胶为原料,
b)采用远红外加热炉,N2保护下进行热降解,其热降解温度为280℃~300℃,恒温时间为40~90分钟,制得平均分子量在2000~10000范围内不等的裂解丁基胶;
步骤二:30%~60%重量百分比的裂解丁基胶胶液的配制
紧接步骤一,趁热加入非极性溶剂配制按丁基胶重量百分比计的30%~60%的裂解丁基胶胶液,且趁热过滤,除去残留的小胶块;
步骤三:热加合
将经溶解、过滤后的丁基胶胶液放入密封且带搅拌的反应器中,加热至120℃~150℃时,按马来酸酐/裂解丁基胶的摩尔比为1.0~1.2/1的量加入马来酸酐,然后缓慢升温至200℃~240℃,并在该温度下恒温、搅拌反应8~12小时,制得长链烃基丁二酸酐溶液;
步骤四:胺化
将长链烃基丁二酸酐溶液冷却至60℃~室温后用苯或甲苯按1∶1~3重量份混合稀释、过滤后放入带搅拌的回流的反应器中,按乙烯胺类化合物/长链烃基丁二酸酐摩尔比为1.0~1.2/~1.0加入乙烯胺类化合物,进行胺化反应,回流反应2小时;再将其产物升温至130℃~150℃后,经减压蒸馏至除尽混合反应物中的水及溶剂苯或甲苯,制得乳化液膜用表面活性剂。
4、根据权利要求3所述的乳化液膜用表面活性剂的制备方法,其特征在于步骤二所采用的非极性溶剂为磺化煤油或精制柴油或白矿油或液体石蜡。
5、根据权利要求3、4所述的乳化液膜用表面活性剂的制备方法,其特征在于步骤四所采用的乙烯胺类化合物为二乙烯三胺或三乙烯四胺或四乙烯五胺或多乙烯多胺。
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US3172892A (en) * | 1959-03-30 | 1965-03-09 | Reaction product of high molecular weight succinic acids and succinic anhydrides with an ethylene poly- amine | |
US3202678A (en) * | 1959-08-24 | 1965-08-24 | California Research Corp | Alkenyl succinimides of tetraethylene pentamine |
US3272746A (en) * | 1965-11-22 | 1966-09-13 | Lubrizol Corp | Lubricating composition containing an acylated nitrogen compound |
US4259189A (en) * | 1978-01-19 | 1981-03-31 | Exxon Research And Engineering Co. | Novel liquid membrane formulations |
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