CN1036782C - 包含仲烷基硫酸脂/沸石的表面活性剂组合物 - Google Patents
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Abstract
制备含有仲烷基(C8-C22)硫酸酯的表面活性剂组合物的方法，包括a)用硫酸酯化试剂对(C8-C22)烯烃和/或(C8-C22)仲醇进行硫酸酯化，b)把含有烷基硫酸和仲烷基硫酸酯的硫酸酯化产物用碱中和，c)加热步骤b)的产物以皂化二烷基硫酸酯并从混合物中除去基本上所有的水，d)在非离子有机液体稀释剂存在下把步骤c)的产物冷却到室温，这时有结晶状固体组合物析出，e)回收并干燥结晶状固体组合物，本方法的特征为沸石是在步骤c)和/或步骤d)中加入并从而制得表面活性剂组合物。
Description
本发明有关于一种制备含有仲烷基硫酸酯的表面活性剂组合物的方法，以及这样制得的表面活性剂组合物，更具体地说，本发明是有关于一种含有仲烷基硫酸酯/沸石的组合物以及制备这种组合物的方法。
在国际专利申请No.PCT/EP93/01339(WO-A-9324452)中，指出了一种固体仲烷基硫酸酯组合物以及它们的制备方法。这种组合物可与通常的表面活性剂组合物配伍，后者基本上不含水和未反应的有机物质(UOM)。这样的组合物因而具有最大的处置方面的灵活性。
但是，为把表面活性剂组合物制备成无水的可自由流动的粉末形式，专利中公开的方法要求把中间体组合物彻底地干燥(加热至106℃)。此外，它还提议往已经回收的含有固体仲烷基硫酸酯的表面活性剂组合物中加入碳酸钠。
本发明人准备提供一种简化的制备无水的可自由流动的粉状表面活性剂组合物的方法，其中避免了过度加热一步，而且本发明的方法无需后来的混合槽即可产生可自由流动的粉末。
已经发现一种制备表面活性剂组合物的方法，其中由烯烃和/或醇类衍生的仲烷基硫酸酯可以这样的方式来产生，即含有仲烷基硫酸酯/沸石的产物是一种固体。这种表面活性剂组合物可被用作表面活性剂和/或洗涤剂组合物，特别适于家庭应用(自由流动的粉状物)。
本发明进一步提供含有仲烷基硫酸酯和一种沸石的固体表面活性剂组合物，它基本上不含未反应的有机物质和水。这些表面活性剂组合物是按下面叙述的方法制备的。
具体地，本发明方法包括以下步骤：
a)用一种硫酸酯化试剂对(C8-C22)烯烃和/或(C8-C22)仲醇，任选地含有伯醇，进行硫酸酯化，
b)把步骤a)中产生的含有烷基硫酸和二烷基硫酸酯的硫酸酯化产物用一种在水溶液中的碱中和，
c)加热步骤b)的产物以皂化二烷基硫酸酯并从混合物中除去基本上所有的水，
d)在非离子有机液体稀释剂存在下把步骤c)的产物冷却到室温，这时有结晶状固体组合物析出，
e)回收并干燥步骤d)的结晶状固体组合物，
其中非离子有机液体稀释剂是在先于步骤d)的某步加入的；本方法的特征为沸石是在步骤c)和/或步骤d)中加入的。
令人惊奇的是，如所附的实施例所阐明的那样，沸石可以在步骤c)和或步骤d)引入组合物中，从而避免了国际专利申请中要求进行的那种彻底的干燥操作(加热至106℃)。
在上述方法中，非离子有机液体稀释剂可在硫酸酯化一步的过程中加入，也可在硫酸酯化这一步骤之后加入，或在中和或皂化一步的过程中加入，只要稀释剂在它具体加入的那一步操作中基本上是惰性的就行。同时只要稀释剂在结晶一步以前加入，则非离子有机液体稀释剂是在什么时间加入并不是很关键性的。
术语“基本上不含未反应的有机物质和水”是指组合物中含有少于10(重量)，最好是少于5％(重量)的未反应的有机物质，以及少于5％(重量)，最好是少于2％(重量)数的水。
在本方法的步骤a)中，烯烃，醇类或它们的混合物可被硫酸酯化。在一个经优选的具体实施例中，步骤a)中的烷基硫酸是通过硫酸酯化烯烃或者硫酸酯化烯烃和醇类的混合物而制得的。
合适的烯烃，醇类和硫酸化试剂对于熟练的专业人员是已知的，也可参照例如上述国际专利申请NO.PCT/EP93/01339(WO-A-9324452)。具体的烯烃是C12-C18范围内的烯烃，用浓硫酸作硫酸化试剂被认为是合适的。同样，合适的非离子有机液体稀释剂诸如庚烷、甲苯、异辛烷、壬烷和它们的混合物在本专利申请中是已知的。此外，在这一文献中还有进行步骤a)直至步骤e)并包括步骤e)的合适的方法。
适用于本发明的沸石典型地是那些适合于在洗涤剂组合物中用作助洗涤的沸石。术语“沸石”是用来指那些具有笼状网络结构，孔径为几个埃的结晶状铝硅酸盐矿物。一些普通的材料诸如沸石Y(八面沸石)或沸石A具有三维结构，其小孔的横断面(“超笼”)稍大于小孔的大小。其它沸石诸如沸石L和丝光沸石则具有通道。对于每种类型的沸石都可用理论的晶体结构或“框架结构”来表征，它是由相互连接的硅原子、铝原子和氧原子以有规则的方式组成。在框架结构中找到的铝被称为“框架铝”。典型的沸石框架结构包含角共用的SiO4和AlO4四面体。在Si-O-Al框架中的过量负电荷被存在的合适的正离子诸如氢、铵、碱金属、碱土金属、稀土金属等的正电荷所平衡。每种具体的沸石都有其特定硅铝比例或特定的硅铝比例范围，它应该相应于该种沸石类型的理论晶体结构。
适用于本发明的沸石是沸石A、沸石X、沸石Y以及它们的混合物，其中沸石A是特别优选的。沸石A可从市场上买到，诸如PQ公司以商品名称VALFOR100出售的产品和Ethyl公司的产品等。用于本发明中的沸石用量典型地是在最终的仲烷基硫酸酯/沸石组合物中含有至少25％(重量)，最好是由50至75％(重量)(基于组合物的总重量计)。
沸石可以在皂化一步(步骤c)的过程中加入，或在结晶一步(步骤d)的过程中加入。相信沸石是在回收含仲烷基硫酸酯/沸石的产物时作为助滤剂用的。在许多步骤中的任何一步加入沸石也是在本发明的范围之内，诸如，例如，沸石可以在结晶一步之前，在结晶一步的过程中以及在结晶一步之后，但在回收产物之前被加入。
在皂化和除去基本上所有的水之后，再把得到的产物在非离子有机液体稀释剂存在的条件下冷却到20℃至85℃的范围内，以使固体的仲烷基硫酸酯由步骤c)的皂化产物中结晶出来。冷却一步一般需要0.25小时至18小时，最好是0.5小时至16小时，虽然更短和更长的时间也是可以接受的。在冷却一步的过程中，仲烷基硫酸酯的溶解度被进一步降低，从而有更多的仲烷基硫酸酯形成。
然后结晶的仲烷基硫酸酯/沸石产物即以含有仲烷基硫酸酯/沸石的组合物的形式被回收和干燥。仲烷基硫酸酯/沸石结晶可通过过滤或离心操作回收。含有结晶的仲烷基硫酸酯/沸石的产物典型地是在40℃至80℃的温度范围内，用真空氮气吹扫或别的通常使用的干燥方法来进行干燥。在干燥之前，可以用具体使用的那种非离子性有机液体稀释剂或用任何别的通常用的洗涤剂洗涤结晶，以增加含有仲烷基硫酸酯/沸石产物的纯度。
步骤d)的产物的其余部份中包含未反应的原料、仲醇和非离子性有机液体稀释剂以及一些未结晶析出的仲烷基硫酸酯，可以重新循环使用。另外，如果需要，可在重新循环之前由步骤d)的产物中除去未结晶析出的仲烷基硫酸酯。此外，如果需要，也可由未反应的原料中通过本专业熟练人员知道的方法，诸如，例如蒸馏来分离仲醇。
本发明的方法可以间歇方式或连续操作方式来进行操作。
用本发明方法所制备的含有固体仲烷基硫酸酯/沸石的表面活性剂组合物，典型地含有至少80％(重量)(基于组合物的总重量)的仲烷基硫酸酯和沸石的组合，更好是含有至少90％(重量)的仲烷基硫酸酯和沸石的组合。所产生的固体的仲烷基硫酸酯/沸石产物中包含至少25至75％(重量)，最好是25至50％(重量)的仲烷基硫酸酯，以及至少25至75％(重量)，最好是50至75％(重量)的沸石。产物中一般还包含一些残余量的硫酸钠。产物中典型地包含少于12％(重量)，最好是少于9％(重量)的硫酸钠(基于组合物的总重量计)。
在目前的说明书和权利要求中提供的范围和限制，是那些相信能具体地指出并清楚地提出本发明权利要求的范围和限制。但是，应该理解，以基本上相同的方法，完成基本上相同的功能，得到相同或基本上相同结果的其它范围和限制，也应被包括在被目前的说明书和权利要求所定义的目前这发明的范围之内。
本发明将通过以下的实施例进行描述，提供这些实施例是为了解释的目的，而不应理解为对本发明的限制。
解释性的具体实施例
实施例1
往装有桨式搅拌器、温度计和顶端有氮气层保护的滴加瓶的2立升带夹套的三颈玻璃容器中加入400克97％(重量)的C16线型α-烯烃。通过夹套层用冷到0℃的乙二醇循环。在良好的搅拌条件下加入115克95％(重量)的硫酸，加入的速度应使反应温度不超过20℃。加完硫酸后把混合物搅拌大约1小时，然后往混合物中加入200克庚烷。把500克这样的混合物加到另外一个含有212.5克20％(重量)NaOH的2立升三口玻璃容器中，后者装有桨式搅拌器，温度计，带有氮气保护层的迪安-斯达克分水器和滴加瓶。在酸中和过程中，反应瓶中的温度由大约24℃升至70℃。加完酸后，往这混合物中加入150克庚烷。
用带氮气保护层的迪安-斯达克分水器替换滴加瓶，并把反应容器加热到可由反应混合物中恒沸蒸出水的温度。在除去172克水，反应温度达到100℃后，往反应混合物中加入50克的VALFOR100沸石(VALFOR是PQ公司的商标，该公司出售这种沸石)。另外50克庚烷也被加入这反应混合物中。在恒沸蒸出另外16克水以后，即总共蒸出188克水以后，停止加热，并把迪安-斯达克分水器中的庚烷倒回反应容器中。
冷却过夜到室温，用10厘米直径的瓷漏斗过滤反应容器的内容物，滤器上分出的固体用1200克庚烷洗涤。然后把固体产物转移到一个已称重的皿中，在60℃以及22英寸汞柱真空的氮气吹扫条件下干燥至恒重。经干燥后的固体产物重193.8克。分析表明这回收的产物含75.0％(重量)的阴离子表面活性剂和0.18％(重量)的硫酸钠。没有对沸石含量进行分析，但所有加入的沸石都保留在滤器上，因而都应包含在固体产物中，它应是产物中其余的25％(重量)。阴离子表面活性剂的产率为35％(基于起始用的烯烃按摩尔/摩尔计)。结果被列于表I中。
实施例2
实施例2是按类似于实施例1的方法进行的，只是用150克VALFOR100(VALFOR是一种商品名)来代替原来的50克。回收得到288克固体产物，它含有53.8％(重量)的阴离子表面活性剂，0.25％(重量)的硫酸钠，和大约50％(重量)的沸石。阴离子表面活性剂的收率为36％(摩尔/摩尔)。结果被列于表I中。
实施例3
实施例3是按类似于实施例1和2的方法进行的，只是沸石的加入是在把反应混合物或浆状物冷却到室温后进行的。这样加入沸石使得固体产物主要包含阴离子表面活性剂，而只有较小量的硫酸钠和氢氧化钠。在实施例3中，中和后是加入150克庚烷，而不是实施例1中加入的200克。回收得到640克浆状物。把214克浆状物在不加沸石的条件下过滤并用404克庚烷洗涤，可制得50.4克含有97.0％(重量)阴离子表面活性剂和0.34％(重量)硫酸钠的固体产物。220克上述浆状物与100克沸石掺和并把形成的混合物过滤，用409克庚烷洗涤。这样可回收150克固体产物，它包含34.4％(重量)的阴离子表面活性剂和大约66％(重量)的沸石。在两种情形下基于原来的烯烃计算的阴离子表面活性剂的收率均为36％(摩尔/摩尔)。还有，虽然带有沸石的滤饼的重量大约要大三倍，滤饼的稠度大两倍，但它和不带沸石的浆液过滤的速度却没有什么不同。实验结果列于表I中。
实施例4
实施例4是按类似于实施例3的方法进行的。一部份浆状物与沸石掺和后给出一种固体产物，它包含35.5％(重量)的阴离子表面活性剂，其余主要是沸石。浆状物也可不加沸石过滤，得到的固体产物中包含99.1％(重量)的阴离子表面活性剂和1.3％(重量)的硫酸钠。两种情形下基于烯烃计算的阴离子表面活性剂的收率都是38％(摩尔/摩尔)。但是，在实施例4中，含有沸石的浆液的过滤速度要快三倍。结果被列于表I中。
表I
| 实施例号(重量％) | 烯和/或醇 | 酸/烯和/或醇的比例(摩尔/摩尔) | 稀释剂 | 沸石 | 作为固体回收的仲烷基硫酸酯(％) | 仲烷基硫酸酯的纯度 | 产物中的沸石(重量％) |
| 1234 | C16C16C16C16 | 0.620.620.620.62 | 庚烷″″″ | VALFOR.100VALFOR.100VALFOR.100VALFOR.100 | 35363638 | 75.053.834.435.5 | 25506666 |
Claims (4)
1.一种制备含有仲烷基(C8-C22)硫酸酯的表面活性组合物的方法，它包括：
a)用一种硫酸酯化试剂对(C8-C22)烯烃和/或(C8-C22)仲醇，任选地含有伯醇，进行硫酸酯化，
b)把步骤a)中产生的含有烷基硫酸和二烷基硫酸酯的硫酸酯化产物用一种在水溶液中的碱中和，
c)加热步骤b)的产物以皂化二烷基硫酸酯并从混合物中除去基本上所有的水，
d)在非离子有机液体稀释剂存在的条件下把步骤c)的产物冷却到室温，这时有结晶状固体组合物析出，
e)回收并干燥步骤d)的结晶状固体组合物，
其中非离子有机液体稀释剂是在先于步骤d)的某步加入的；本方法的特征为沸石是在步骤c)和/或步骤d)中加入的，并且在步骤e)中回收的含有固体仲烷基硫酸酯的表面活性剂组合物中含有25至75％(重量)的仲烷基硫酸酯以及75至25％(重量)的沸石。
2.权利要求1所述的方法，其中的沸石是选自沸石A，沸石X，沸石Y以及它们的混合物。
3.权利要求2所述的方法，其中的沸石是沸石A。
4.一种在室温是固体的表面活性剂组合物，它是由权利要求1的方法制得的，其中含有25至75％(重量)的仲烷基(C8-C22)硫酸酯和75-25％(重量)的沸石，并且仲烷基(C8-C22)硫酸酯和沸石的总和为80至99％(重量)；低于20％(重量)的硫酸钠；低于10％(重量)的相应的(C8-C22)烯烃和/或(C8-C22)醇，以及低于5％(重量)的水。
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| US990920 | 1992-12-15 |
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| EP (1) | EP0674617B1 (zh) |
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| DE (1) | DE69314504T2 (zh) |
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| GB9417356D0 (en) * | 1994-08-26 | 1994-10-19 | Unilever Plc | Detergent particles and process for their production |
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| USH1665H (en) * | 1994-12-09 | 1997-07-01 | Brumbaugh; Ernest H. | Liquid dishwashing detergent |
| GB9604000D0 (en) * | 1996-02-26 | 1996-04-24 | Unilever Plc | Production of anionic detergent particles |
| GB9604022D0 (en) * | 1996-02-26 | 1996-04-24 | Unilever Plc | Anionic detergent particles |
| CN1085245C (zh) * | 1996-03-08 | 2002-05-22 | 普罗格特-甘布尔公司 | 具有改进溶解性的仲烷基硫酸盐颗粒的制备 |
| US5955418A (en) * | 1997-02-26 | 1999-09-21 | The Procter & Gamble Company | Secondary alkyl sulfate surfactant with improved solubility by kneading/extruding process |
| US6423678B1 (en) | 1998-05-05 | 2002-07-23 | Amway Corporation | Alcohol ethoxylate-peg ether of glycerin |
| CN1112233C (zh) * | 1999-12-16 | 2003-06-25 | 山东新华制药股份有限公司 | 一种阳离子表面活性剂的制备工艺及该工艺的制备装置 |
| KR100642838B1 (ko) * | 2000-06-13 | 2006-11-13 | 김인규 | 계면활성제 활성성분의 제조방법, 계면활성제 및계면활성제를 사용하는 방법 |
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| Publication number | Publication date |
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| CA2151746A1 (en) | 1994-06-23 |
| AU5811694A (en) | 1994-07-04 |
| ES2109665T3 (es) | 1998-01-16 |
| EP0674617B1 (en) | 1997-10-08 |
| DE69314504T2 (de) | 1998-02-12 |
| CN1090218A (zh) | 1994-08-03 |
| WO1994013632A1 (en) | 1994-06-23 |
| NZ259340A (en) | 1996-05-28 |
| DE69314504D1 (de) | 1997-11-13 |
| KR950704241A (ko) | 1995-11-17 |
| AU674920B2 (en) | 1997-01-16 |
| JPH08504423A (ja) | 1996-05-14 |
| EP0674617A1 (en) | 1995-10-04 |
| US5427717A (en) | 1995-06-27 |
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