CN1259151A - 具有低水亲合力的聚氧化烯单醚 - Google Patents

具有低水亲合力的聚氧化烯单醚 Download PDF

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CN1259151A
CN1259151A CN98805703A CN98805703A CN1259151A CN 1259151 A CN1259151 A CN 1259151A CN 98805703 A CN98805703 A CN 98805703A CN 98805703 A CN98805703 A CN 98805703A CN 1259151 A CN1259151 A CN 1259151A
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G·科姆布斯
K·G·麦丹尼尔
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Abstract

公开了具有减小水亲合力性能的亲油性聚氧化烯单醚。该单醚含有烃基残基,聚氧化烯部分和羟基端基。这种单醚含有少于大约6%(摩尔)的烷氧基化不饱和物,并且优选地含少于5%(摩尔)的聚氧化烯二醇。这种单醚能使燃料组合物具有很大的优点,特别是减小水亲合力。通过用基于这种单醚的沉积控制添加剂,配方设计者能为清洁发动机提供更好的燃料。

Description

具有低水亲合力的聚氧化烯单醚
                       发明领域
本发明涉及聚氧化烯单醚。具体地说，本发明涉及具有低水亲合力的聚氧化烯单醚，他们可用作燃料添加剂净化体系的组分。
                       发明背景
聚氧化烯单醚和他们的衍生物是人们所熟知的，并且被广泛地用作燃料添加剂净化体系的组分，以保持内燃机进气系统的清洁。许多传统的净化体系含有两种组分：(1)聚氧化烯组分，它作为载体；和(2)去垢剂。已知有各种各样的去垢剂，包括氨基甲酸酯，琥珀酸酯，氨基聚醚和聚异丁烯胺(PIB胺)。这种双组分体系的例子就是在美国专利5,298,039和4,877,416中所公开的。新近，把聚氧化烯部分和净化功能基结合到单一高分子主链上的单组分净化体系也已经出现(例如，参见美国专利5,427,591和5,600,025)。
作为燃料添加剂的聚氧化烯单醚必须是亲油的，以便能与汽油和用以阻止或消除沉积物形成的亲脂性去垢剂混溶。为了达到在燃料中有良好的溶解性并与燃料有良好的混溶性，聚氧化烯组分一般以C4-C60(更优选C9-C30)烃基(烷基、芳基，或芳烷基)封端，例如，在美国专利5,298,039、4,877,416和4,422,865中所描述的那些。既使带有这样烃基，这种聚氧化烯组分仍可能是亲水的，以致在与燃料中的水接触时能足以形成乳浊液，或者导致从其他烃类组分中相分离。
为了增强聚氧化烯单醚的油溶解性，配方设计者采取增加起始物醇的亲油性(例如见美国专利5,298,093和5,600,025)，或者接入比较疏水性的氧亚烷基单元，如从C4环氧化物得到的(例如见美国专利5,044,478)或者从枝化的C11-C14环氧化物得到的(例如见美国专利4,274,837)。不幸的是，相对于可取的方法这些改性常常是太昂贵了一些。
聚氧化烯单醚通常含有比较少量的聚氧化烯二醇杂质。这些二醇杂质是由于氧化烯，如环氧丙烷，在水存在的情况下碱催化聚合而产生的，这里水是作为聚合的起始剂。这些二醇缺乏上述单醚的烃基部位。直到现在，这些少量的二醇杂质还没有被认为对燃料中的聚氧化烯单醚的性能会有有害的影响。
用C3和更高的氧化烯生成的聚氧化烯单醚含有第二种类型的杂质；烷氧基化的不饱和物。一种副反应使许多氧化烯的碱催化聚合复杂化：即在反应条件下某些氧化烯会异构化，成为烯丙基醇和其他不饱和物。例如，环氧丙烷在碱性条件下会异构成烯丙醇。这些烯丙基醇与氧化烯反应会产生烷氧基化的不饱和物。虽然这些杂质是“单醚”，但他们缺少比较疏水性的端基。直到现在，这些烷氧基化的不饱和物，通常为丙氧基化的烯丙醇，还没有被认为对燃料中的聚氧化烯单醚会有有害的影响。
                       发明概述
本发明是一种亲油的聚氧化烯单醚。这种单醚的结构为：
                   Z-(A)n-OH其中A是氧亚烷基，Z是选自C4-C60烷基，芳基和芳烷基的一种烃基残基，n是氧亚烷基的平均数，其数值为约2-500。该单醚含有少于大约6％(摩尔)的烷氧基化的不饱和物，且优选含少于大约5％(摩尔)的聚氧化烯二醇。
我们惊奇地发现，含少于大约6％(摩尔)的烷氧基化不饱和物的聚氧化烯单醚，使燃料具有显著的优点。特别是，这种单醚对水的亲合力小，并且显著减小了与亲脂体系中存在的水形成乳浊液的趋势。单醚的这些优点意味着其在燃料中有较好的可溶性。我们也惊奇地发现，在该单醚中，聚氧化烯二醇杂质的含量减少到少于约5％(摩尔)时，显现出类似的优点。通过用以本发明的聚氧化烯单醚为基础的沉积控制添加剂，燃料的配方设计者能提供用于清洁发动机的更好的溶液。
                       发明详述
本发明的亲油性聚氧化烯单醚的大致结构是Z-(A)n-OH，其中A是一种氧亚烷基，Z是烃基残基，n是氧亚烷基的平均数。
适合的氧亚烷基(A)来自于一种或多种环氧化物的开环聚合，包括诸如环氧丙烷，环氧丁烷，环氧戊烷等。优选地，这种单醚的聚氧化烯部分包含由至少50％(摩尔)的环氧丙烷，至多约49％(摩尔)的环氧丁烷，以及不大于约10％(摩尔)的环氧乙烷得到的重复单元。所有氧亚烷基单元均为氧亚丙基的聚氧化烯单醚是特别优选的。聚氧化烯部分可能包含氧亚烷基单元的一种随机构型，或者它可能是一种嵌段共聚物。
在结构式中用“n”表示的单醚中氧亚烷基的平均数为约2-约500。对于优选的单醚，n为约5-约100。更优选的是约10-约30。最优选的是约10-约25。
该单醚包含烃基残基(Z)。这种烃基残基是C4-C60，更优选的是C9-C30的烷基，芳基，或芳烷基。这种烃基残基一般从单羟基化合物(如一种醇或酚)衍生，它是环氧化物聚合形成这种聚氧化烯单醚的起始剂。从带有C4-C15烷基取代基的酚，如壬基酚，得到的单醚，以及从C10-C20，更优选地C12-C15的脂族醇得到的单醚是特别优选的。对于聚氧化烯单醚，一般适合的结构的例子在美国专利4,234,321、4,288,612，和5,600,025中已有叙述，其内容引入本文作为参考。适合的烃基残基包括“针轮”型烷氧基化的烷基酚，如在美国专利No.5,600,025中所描述的那些。
聚氧化烯单醚通常通过碱催化制得，因此他们包含相当浓度的烷氧基化的不饱和物，典型地为丙氧基化C3不饱和物。直到现在，这些杂质还没有被认为会对燃料中的聚氧化烯单醚的性能起有害的影响。然而，我们惊奇地发现，烷氧基化不饱和物的浓度是重要的，并发现含少于大约6％(摩尔)烷氧基化不饱和物的聚氧化烯单醚，能使燃料具有显著的优点，包括对水的亲合力小和与亲脂体系中的水产生乳化的趋势小。更优选的聚氧化烯单醚含少于大约3％(摩尔)的烷氧基化不饱和物；最优选的是含少于大约1.5％(摩尔)烷氧基化不饱和物的单醚。
虽然本技术中已知有若干种制备含非常低浓度烷氧基化不饱和物(即少于大约6％(摩尔))的聚醚组合物的方法，但用双金属氰化物(DMC)催化剂制备聚氧化烯组分仍是一种特别有价值的方法。适合的DMC催化剂，他们的制备方法，以及用他们来催化环氧化物聚合的步骤在美国专利3,278,457、3,941,849、4,472,560、5,158,922、5,470,813、5,482,908中已有描述，其内容引入本文作为参考。用基本上非晶形的各种各样双金属氰化物催化剂制备的聚氧化烯单醚是特别推荐的方法，因为这些催化剂倾向于得到含有最低水平的烷氧基化不饱和物的聚合物，典型地含少于大约3％(摩尔)，常常少于大约1.5％(摩尔)。
优选的聚氧化烯单醚也含有少于大约5％(摩尔)的聚氧化烯二醇。由于用来制备聚氧化烯单醚的醇和酚起始剂，通常含有相当大浓度的水，这种起始剂的碱催化烷氧基化将产生所希望的单醚，但是也产生相当大比例的聚氧化烯二醇，这来自于以水作为起始剂的环氧化物的聚合。直到现在，这些二醇杂质还没有被认为会对燃料中的聚氧化烯单醚的性能起有害的影响。然而，我们惊奇地发现，聚氧化烯二醇的浓度是重要的，并且发现含少于大约5％(摩尔)二醇的聚氧化烯单醚，使燃料具有如同前面描述的使用含低含量烷氧基化不饱和物的单醚的燃料同样的优点：对水的亲合力小和与亲脂体系中的水产生乳化的趋势小。更优选的聚氧化烯单醚含少于大约2％(摩尔)的聚氧化烯二醇。
为了制备含少于大约5％(摩尔)聚氧化烯二醇的聚氧化烯单醚，通常需要对起始剂分子(由烃基部分，Z，衍生出来的醇或酚)进行真空汽提以减少起始剂的含水量。这种汽提通常在提高温度下进行，优选地在约60℃-约200℃，更优选在约90℃-约150℃进行。用惰性气体，如氮气，清洗这种装置常常有利于除去水。共沸溶剂(例如甲苯，己烷)也可用于帮助抽提掉水。在任何环氧化合物加到起始剂和催化剂中之前，起始剂中的水含量应优选地少于大约5％(摩尔)。
正如表1中的结果所表明的，当聚氧化烯单醚含有足够低的二醇和烷氧基化不饱和物杂质的含量时，就导致较小的水亲合力。当二醇和烷氧基化不饱和物的含量均低时，与水形成乳浊液的趋势是比较低的。参见例子1，2，5和7，在这些例子中，二醇含量低于5％(摩尔)，烷氧基化不饱和物含量低于6％(摩尔)。界面厚度是单醚形成乳浊液趋势的一种度量，在每一种情况下它都少于5mm。相反，当二醇和/或烷氧基化不饱和物杂质的含量高时(比较例3，4和6)，这种单醚与水产生乳化的趋势较大(界面厚度大于10mm)。本发明包括基于聚氧化烯单醚的沉积控制添加剂。本发明的两组分沉积控制添加剂包含一种去垢剂和上述单醚。适合的去垢剂在本技术中是众所周知的，例如在美国专利5,298,039和4,877,416中已有描述，其内容引入本文作为参考。例如，适合的去垢剂包括氨基甲酸酯，琥珀酸酯，氨基聚醚，聚异丁烯胺等及其混合物。本发明的单组分沉积控制添加剂，把聚氧化烯部分和净化功能基结合到单一高分子的主链上。这种单组分沉积控制添加剂的例子在美国专利5,427,591和5,600,025中已有描述，其内容引入本文作为参考。
本发明也包括用亲油性聚氧化烯单醚制备的燃料组合物。该组合物包含一种燃料和一种添加剂，这种添加剂如上面所描述的为本发明的或者单组分或者两组分的沉积控制添加剂。这种燃料组合物还可以包括本技术中人所共知的其他添加剂，例如附加去垢添加剂，抗爆剂，十六烷值增强剂，辛烷值增强剂等。
下面的例子仅仅举例说明本发明。本领域的技术人员将认识到，在本发明的精神和权利要求的范围内可以有许多变化。
                       实例A
从壬基酚制备聚氧化烯单醚
将壬基酚(1006g)加入到不锈钢反应器中。再加入六氰合钴酸锌-叔丁醇配合物(0.143g，用美国专利5,482,908中描述的方法制备)，然后在真空和搅拌条件下将该混合物在130℃加热一小时，以除去壬基酚起始剂中痕量水。用6小时的时间将环氧丙烷(4694g)加入到反应器中。在环氧化合物加入完毕后，将该混合物在加热130℃，直到压力不再降低为止。经真空抽提的产品从反应器中排出。
                       实例B
从C12-C15丙氧基化物制备聚氧化烯单醚
一般，除了用一种C12-C15的脂肪醇来引发聚合反应外，一般按实例A的步骤进行。调整环氧丙烷的用量，以制备含有所希望的氧亚丙基(PO)单元数目的单醚产品(见表1)。
                       实例C
二醇和丙氧基化C3不饱和物的％(摩尔)浓度的测定
表1中所列出的聚氧化烯二醇和丙氧基化C3不饱和物的％(摩尔)浓度按如下方法测定。使聚氧化烯单醚样品中的羟基与过量的邻苯二甲酸酐反应而将其转化成衍生物。除了聚氧化烯“二醇”外，这种样品还包含两种“单醇”(所希望的聚氧化烯单醚和丙氧基化C3不饱和物)。样品中的羟基被转换成邻苯二甲酸半酯，它有自由的-COOH基。然后通过离子色谱对二醇和单醇的相对量进行定量分析。由于这种色谱方法并不能区分存在的两种类型的单醇，因此丙氧基化C3不饱和物％(摩尔)浓度的测定需要有第二种测定方法。用通常的乙酸汞滴定法测定的多羟基化合物的不饱和度，将给出来自丙氧基化C3不饱和物的单醇的％(摩尔)浓度。从用色谱方法得到的单醇总％(摩尔)浓度减去上面的值就得出聚氧化烯单醚的％(摩尔)浓度。
                       实例1-7
聚氧化烯单醚水亲合力的乳化试验
通常按改进的ASTM方法D-1094-96进行试验。将聚氧化丙烯单醚样品(0.02g)在带螺旋盖的管形瓶中与己烷(3.6g)合并。轻轻旋转盖好的瓶子使聚醚完全溶解。移去盖子，然后把水(1.0g)加入到己烷溶液中。盖上瓶子并以活塞式运动方式将其振荡2分钟，这种振动幅度大约为12英寸的一个弧度。这个瓶子以每秒钟敲打2-3次进行振荡2分钟，随后令其静置5分钟。5分钟后用尺子测定界面区(浮化的部分)的高度，以毫米表示，30分钟后再测一次。
                               表1.乳化实验结果：聚氧化丙烯单醚
  实验编号 单醚     #PO单元数     二醇(摩尔％)    C3烯烃(摩尔％)   纯度(％)    5分钟后界面厚度(mm)  30分钟后界面厚度(mm)
    1     A     24     ＜0.5      0.4   ＞99      5.6     4.0
    2     B     18     ＜0.5      0.5   ＞99      4.8     4.0
    C3     C     24       1.4     12.4     86       13     9.5
    C4     D     17     ＜0.5      6.8     93       16      13
    5     E     18       2.4      5.5     92    ＜3.2     2.4
    C6     F     19       9.0       11     80       16      15
    7     G     18       3.0      0.6     96      4.0     3.2
A，B＝C12-C15醇起始的；用于丙氧基化的六氰合钴酸锌-叔丁醇催化剂。C，D＝C12-C15醇起始的；丙氧基化KOH催化剂。E，F＝壬基酚起始的；丙氧基化KOH催化剂。G＝壬基酚起始的；丙氧基化用的六氰合钴酸锌-叔丁醇催化剂。
前面的例子仅意味着举例说明；下面的权利要求书将确定本发明的范围。

Claims (31)

1.有下式结构的亲油性聚氧化烯单醚：
                   Z-(A)n-OH其中A是氧亚烷基，Z是选自C4-C60烷基，芳基和芳烷基的一种烃基残基，n是氧亚烷基的平均数，其数值为约2-500；
其中该单醚含有少于大约5％(摩尔)的聚氧化烯二醇和少于大约6％(摩尔)烷氧基化不饱和物。
2.权利要求1的单醚，其中A是氧亚丙基。
3.权利要求1的单醚，其中Z从壬基酚形成。
4.权利要求1的单醚，其中Z从C12-C15脂族醇形成。
5.权利要求1的单醚，其中Z选自C4-C30烷基，芳基，芳烷基。
6.权利要求1的单醚，其中n的值为约10-约30。
7.权利要求1的单醚，含有少于大约2％(摩尔)的聚氧化烯二醇和少于大约3％(摩尔)的烷氧基化不饱和物。
8.有下式结构的亲油性聚氧化烯单醚：
                   Z-(A)n-OH其中A是氧亚烷基，Z是选自C4-C60烷基，芳基和芳烷基的一种烃基残基，n是氧亚烷基的平均数，其数值为约2-500；
其中该单醚含有少于大约5％(摩尔)的聚氧化烯二醇。
9.权利要求8的单醚，其中A是氧亚丙基。
10.权利要求8的单醚，其中Z选自C4-C30烷基，芳基，芳烷基。
11.权利要求8的单醚，其中n的值为约10-约30。
12.权利要求8的单醚，含有少于大约2％(摩尔)的聚氧化烯二醇。
13.有下式结构的亲油性聚氧化烯单醚：
                   Z-(A)n-OH其中A是氧亚烷基，Z是选自C4-C60烷基，芳基和芳烷基的一种烃基残基，n是氧亚烷基的平均数，其数值为约2-500；
其中该单醚含有少于大约6％(摩尔)的烷氧基化不饱和物。
14.权利要求13的单醚，其中A是氧亚丙基。
15.权利要求13的单醚，其中Z选自C4-C30烷基，芳基，芳烷基。
16.权利要求13的单醚，其中n的值为约10-约30。
17.权利要求13的单醚，含有少于大约3％(摩尔)的烷氧基化不饱和物。
18.有下式结构的亲油性聚氧化丙烯单醚：
                   Z-(A)n-OH
其中A是氧亚丙基，Z是选自C4-C60烷基，芳基，芳烷基的一种烃基残基，n是氧亚丙基的平均数，其数值为约10-约30；
其中该单醚含有少于大约5％(摩尔)的聚氧化丙烯二醇和少于大约6％(摩尔)的丙氧基化C3不饱和物。
19.权利要求18的单醚，含有少于大约2％(摩尔)的聚氧化丙烯二醇和少于大约3％(摩尔)的丙氧基化C3不饱和物。
20.一种单组分沉积控制添加剂，它从权利要求1的聚氧化烯单醚制得。
21.一种双组分沉积控制添加剂，它包含去垢剂和权利要求1的聚氧化烯单醚。
22.一种组合物，它包含燃料和权利要求20的单组分沉积控制添加剂。
23.一种组合物，它包含燃料和权利要求21的双组分沉积控制添加剂。
24.一种单组分沉积控制添加剂，它从权利要求13的聚氧化烯单醚制得。
25.一种双组分沉积控制添加剂，它包含去垢剂和权利要求13的聚氧化烯单醚。
26.一种组合物，它包含燃料和权利要求24的单组分沉积控制添加剂。
27.一种组合物，它包含燃料和权利要求25的双组分沉积控制添加剂。
28.权利要求1的单醚，它是用双金属氰化物作催化剂制备的。
29.权利要求13的单醚，它是用双金属氰化物作催化剂制备的。
30.减小燃料组合物的水亲合力的方法，该方法包括用权利要求1的聚氧化烯单醚作为燃料组分。
31.减小燃料组合物的水亲合力的方法，该方法包括用权利要求13的聚氧化烯单醚作为燃料组分。
CNB988057034A 1997-04-02 1998-03-20 具有低水亲合力的聚氧化烯单醚 Expired - Lifetime CN1222558C (zh)

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CN101289372B (zh) * 2007-04-16 2013-07-10 拜尔材料科学有限公司 烷基苯酚乙氧基化物的高产率生产方法

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ES2294812T3 (es) 2008-04-01
JP2001526709A (ja) 2001-12-18
CA2282365C (en) 2008-05-20
CA2282365A1 (en) 1998-10-08
US20030024154A1 (en) 2003-02-06
EP0971970A1 (en) 2000-01-19
US6821308B2 (en) 2004-11-23
EP0971970B1 (en) 2007-10-10
CN1222558C (zh) 2005-10-12
DE69838543T2 (de) 2008-07-24
WO1998044022A1 (en) 1998-10-08
BR9808401A (pt) 2000-05-16
AU7039298A (en) 1998-10-22
DE69838543D1 (de) 2007-11-22

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