CN1095073A - 取代的酰化剂 - Google Patents
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Abstract
本发明涉及通过烯酰基化合物与烯化合物经热
路线的反应制备取代的酰化剂的方法，其中a)烯酰
基化合物与烯化合物的摩尔比至少为3∶1，b)至少
在向反应中加入烯酰基化合物完毕后，反应压力在
20psig以上，并且基本保持该压力不变，直至至少
80％的烯化合物与烯酰基化合物反应生成相应的取
代的酰化剂。这样制得的试剂基本上不含氯，并且可
进一步与胺或羟基化合物反应生成可用作润滑油或
燃料添加剂的衍生物。
Description
本发明涉及新的和改进的取代的酰化剂，尤其涉及聚丙烯基或聚丁烯基取代的酰化剂及其制备方法。
人们都知道通过烯化合物例如聚丙烯或聚丁烯与烯酰基化合物（enophile）例如马来酸酐的反应来生产取代的酰化剂。作为这种路线之一的所谓“氯化路线”包括用氯与烯化合物形成相应的氯化衍生物，使烯化合物的双键活化，这种生成的氯化衍生物随后与象马来酸酐之类的烯酰基化合物反应生成取代的酰化剂而官能化。这种路线是有效的并导致取代的酰化剂的高转化率。但是，一个严重的缺陷是取代的酰化剂中含有氯已越来越不能令人接受，当该试剂用于润滑油或燃料添加剂的生产过程中时尤其如此。
另一路线是所谓的“热路线”其中烯化合物（例如：聚丙烯或聚丁烯）与烯酰基化合物（例如：马来酸酐）简单地加热，还可加入催化剂或其它添加剂，以形成取代的酰化剂。该路线避免了氯化路线中混入氯的问题。公开的EP-A-457599描述了一种上述方法，它提出烯酰基化合物马来酸酐与烯化合物如聚丁烯的摩尔比小于3∶1，优选小于1.9∶1（第3页，第46-47页）。在该说明书中，反应开始后（对所有实施例而言）相当一段时间（至少在开始后的前三个小时）采用低于20 psig的优选的反应压力，并且反应在诸如三氯化铝之类的催化剂存在下进行。但是，该热路线通常转化率低而且在制得的取代的酰化剂中残留高浓度的未反应聚丙烯，这是人们所不希望的。根据EP-A-457599的实施例9，将未反应马来酸酐再循环后，残留量为24-27%上下。高浓度的未反应聚丁烯是不合需要的，因为它们对用酰化剂制得的润滑油或燃料添加剂的性能产生不利影响。
现已发现，先有技术方法的这些问题可通过严格控制反应物浓度和反应条件而得以减轻。
因此，本发明是通过烯酰基化合物与烯化合物经热路线的反应制备取代的酰化剂的方法，其特征在于：
a） 烯酰基化合物与烯化合物的摩尔比大于3∶1，
b） 至少在向反应中加入烯酰基化合物完毕后，反应压力在20 psig以上，并且基本保持该压力不变，直至至少80%的烯化合物与烯酰基化合物反应生成相应的取代的酰化剂。
本发明方法所用的烯酰基化合物以不饱和二羟酸酐为宜，优选马来酸酐。
本发明方法所用的烯化合物可以是聚丙烯或聚丁烯，优选聚丁烯。
本说明书中“聚丁烯”一词是指聚丁烯、聚异丁烯或其混合物，它所包含的双键的50%以上是终端亚乙烯基基用，即＝CH2基团。这样的聚丁烯是可从BP Chemical Ltd.购得的商标为“ULTRAVIS
”的各级聚丁烯。该聚丁烯是所谓“高活性聚丁烯”。该聚丁烯可通过例如残液混合物（例如：所谓“残液Ⅰ”）的阳离子聚合制备。残液Ⅰ是丁二烯残液，它是在炼油厂热裂解或催化裂解操作时形成的副产物（不论是否液体），主要包括C4烃类，尤其是丁烯-1、丁烯-2和异丁烯与某些饱和烃的混合物。更具体地说，残液Ⅰ至少包含10%w/w的异丁烯、20-40%w/w的丁烯-1和丁烯-2和10-20%w/w的丁烷类。制备这样的聚丁烯的这种方法之一在公开的EP-A-145235中被描述并要求保护。本发明方法可用的高活性聚丁烯的一个典型例子是ULTRAVIS
30。
反应中烯酰基化合物与烯化合物的摩尔比至少为3∶1，大于3∶1较合适，优选大于3.5∶1，例如约4-4.5∶1。烯化合物和烯酰基化合物之间的反应以通过迅速和完全地将烯酰基化合物充入反应器的方式进行为宜。这与常规工业实践相反，在常规工业实践中，烯酰基化合物一般在整个反应过程中逐渐加到烯化合物中。应将烯酰基化合物加到装有烯化合物的容器中，使得在反应时间过去50%、优选25%之前便完成烯酰基化合物的添加。
反应进行的温度以大于220℃为宜，优选230℃以上，例如约231-232℃，并且优选反应前将烯化合物例如聚丁烯在高温下短时加热，并且反应器填装高度以高为宜。
反应压力升至高于大气压力的20 psig以上，优选大于25 psig，例如35 psig。一般在向反应体系中加入全部烯酰基化合物反应物后立即升压，该反应压力在整个反应过程中基本保持一恒定值不变。所谓“整个反应过程”本文是指从反应开始直到至少80%的烯化合物反应物已与烯酰基化合物反应转化成相应的酰化剂为止。
热路线的一个特点是烯化合物与烯酰基化合物的反应优选在无任何催化剂或任何添加的氯的情况下进行。
本发明取代的酰化剂的一个具体例子是聚丁烯基琥珀酸酐。它是通过至少3mol、优选至少3mol的烯酰基化合物（即马来酸酐）与1mol的烯化合物（即聚丁烯）反应制备的。
本发明方法的一个特点是它制得的酰化剂在取代的酰化剂中有少于20%，通常不超过15%的未反应聚丁烯。这不仅可通过控制诸如活性聚丁烯的使用、高的烯酰基化合物与烯化合物摩尔比和加完烯酰基化合物后较高的反应压力等方面来达到，而且也可通过保持烯酰基化合物（例如马来酸酐）向反应器中的高进料速率而易于达到。因而，根据另一实施方案，本发明是由高活性聚丁烯与马来酸酐经热路线生成的取代的酰化剂，其特征在于所述酰化剂的未反应聚丁烯含量低于20%。
本发明方法制得的取代的酰化剂基本上不含氯，因为在制备烯化合物或在其与烯酰基化合物反应的任何一个步骤中都未使用氯。
本发明制得的取代的酰化剂可进一步官能化，例如可通过分别与胺或羟基化合物反应官能化为相应的胺化衍生物或羟基化衍生物。这样的衍生物，例如用胺官能化产生的酰亚胺，能够改善润滑油或燃料的粘度指数、分散性或洗涤性。
我们参照下列实施例进一步说明本发明。
实施例1
将高活性聚丁烯ULTRAVIS
30（亚乙烯基含量68%，Mn＝1375）投入反应器，加热反至231℃并于该温度下保温3.5小时。在加热升温过程中用1小时的时间向反应器中加入4.3∶1摩尔过量的马来酸酐，在整个反应期间压力保持在35 psig。将反应产物洗涤以除去未反应的马来酸酐，随后过滤。过滤后，所得取代的酰化剂中未反应聚丁烯含量测定为15%w/w。反应器未变污，可不经过任何进一步清洗的步骤再次使用。
实施例2
将高活性聚丁烯ULTRAVIS
30（亚乙烯基含量68%，Mn＝1375，264 kg）投入马来化反应器中，反应器装有位于循环回路中的马来酸酐贮罐。聚丁烯在真空和175℃下脱气。然后用氮气将反应器压力升至15 psig。用2.5小时的时间将5.7∶1摩尔过量的马来酸酐（116kg）加入反应器。在加入马来酸酐的期间用1小时55分钟将反应器加热到231-232℃，并在该温度下保温3.5小时。在加入马来酸酐期间，反应器压力保持在15 psig。加入马来酸酐完毕后，即达到反应温度35分钟后，用氮气将反应器压力升至40psig，保持该压力直到231-232℃下3.5小时的反应结束。随后降低反应压力，用四小时的时间真空洗涤过量的未反应马来酸酐。迅速从反应器中取出反应产物，然后过滤。过滤后，所得取代的酰化剂中未反应聚丁烯含量测定为10%w/w。反应器未变污，可不经过任何进一步清洗的步骤再次使用。
实施例3
将高活性聚丁烯ULTRAVIS
10（亚乙烯基含量66%，Mn＝950，261 kg）投入马来化反应器中，反应器装有位于循环回路中的马来酸酐贮罐。聚丁烯在真空和165℃下脱气。然后用氮气将反应器压力升至15 psig。并将反应温度升至175℃。用2小时将3.05∶1摩尔过量的马来酸酐（82.1kg）送入反应器，在加入马来酸酐期间反应器压力保持在15psig。在加完马来酸酐的前半小时，将反应器升温至231-232℃。反应器在此温度下保温3.5小时。加入马来酸酐完毕后，即达到反应温度30分钟后，用氮气将反应器压力升至37psig以进行反应，231-232℃下3.5小时的反应结束后，降低反应压力，用四小时的时间真空洗涤过量的未反应马来酸酐。从反应器中极易取出反应产物，然后过滤。过滤后，所得取代的酰化剂中未反应聚丁烯含量测定为15w/w。反应器未变污，可不经过任何进一步清洗的步骤再次使用。
对比试验1 （不按本发明方法进行）
将一种常规聚丁烯Parapol
（亚乙烯基＜10%，266kg）加到马来化反应器中并于160℃脱气。向反应器充氮气至15 psig，从开始加入4.3摩尔过量的马来酸酐（86kg）起，将温度升至184℃，所述加热过程进行2.5小时。在最后一等份马来酸酐加入前半小时，在加入马来酸酐期间将反应器温度升至231-232℃并保持该温度3.5小时。加完马来酸酐后，用氮气将反应器压力升至40 psig。反应于231-232℃下结束时（3.5小时），降低反应器压力，用4小时的时间真空洗涤过量的未反应产物，然后过滤。经过滤的反应产物含有28%w/w的未反应聚丁烯，发现反应器被马来酸酐树脂弄污。反应器必须经过充分的清洗步骤才能再次使用。
对比试验2 （不按本发明方法进行）、
将高活性聚丁烯Ultravis
10（亚乙烯基66% Mn＝950，214kg）投入装有浆式搅拌机的热马来化反应器中。将聚丁烯真空脱气2小时，然后向反应器充氮气至15 psig并升温至175℃。向反应器里加入11kg马来酸酐，20分钟加完。在加入酸酐期间，将反应器升温至220℃，并在此较高温度下再开始加55.2kg马来酸酐。在加马来酸酐期间将反应器用继续加热约1.25小时，直至温度达到232℃。在15 psig的反应器总压下，以恒速再继续加入马来酸酐3.5小时，使得在4.75小时中共加入55.2kg马来酸酐。加完马来酸酐后，即在231-232℃的反应温度下3.5小时后，解除反应器压力，用4个小时从反应器中真空除去未反应的马来酸酐。随后，通大气，从反应器中取出反应产物，经硅藻土床过滤。过滤后的反应产物含26%w/w的未反应聚丁烯。
对比试验3 （不按本发明方法进行）
将一种称为Hyvis
10的常规聚丁烯（亚乙烯基＜10%，Mn＝950，200g）与马来酸酐（100g，马来酸酐4.85mol）一起投入高压釜中。将高压釜真空脱气2小时，然后向反应器中充氮气至0psig。然后在搅拌下将高压釜加热至232℃并保持该温度。让高压釜的压力升至40psig，在3.5小时的反应期间，在不断搅拌的情况下将反应力保持在40±2psig。然后，停止搅拌，让高压釜冷却至100℃，解除压力。然后取出高压釜的内容物，用庚烷稀释并过滤。发现高压釜完全被焦油状副产物弄污。将全部焦油状副产物称重，为51.8g。由此计算产物中未转化聚丁烯的含量，相应地为约29%w/w。
Claims (12)
1、通过烯酰基化合物与烯化合物经热路线的反应制备取代的酰化剂的方法，其特征在于：
a)烯酰基化合物与烯化合物的摩尔比大于3∶1，
b)至少在向反应中加入烯酰基化合物完毕后，反应压力在20psig以上，并且基本保持该压力不变，直至至少80%的烯化合物与烯酰基化合物反应生成相应的取代的酰化剂。
2、权利要求1的方法，其中烯酰基化合物是不饱和二羧酸酐。
3、权利要求1或2的方法，其中烯酰基化合物是马来酸酐。
4、上述任一权利要求的方法，其中烯化合物是聚丙烯或聚丁烯。
5、上述任一权利要求的方法，其中烯酰基化合物与烯化合物反应中摩尔比大于3.5∶1。
6、上述任一权利要求的方法，其中烯化合物与烯酰基化合物之间的反应是这样进行的：应迅速、完全地将烯酰基化合物投入反应器，使得在反应时间过去50%以前完成烯酰基化合物的加入。
7、上述任一权利要求的方法，其中反应在220℃以上的温度下进行。
8、上述任一权利要求的方法，其中反应在无任何催化剂的条件下进行。
9、上述任一权利要求的方法，其中超过3mol的马来酸酐与1mol聚丁烯反应，使得在所得的取代的酰化剂中未反应聚丁烯含量低于所述酰化剂的20%w/w。
10、用热路线将聚丁烯与马来酸酐反应生成的取代的酰化剂，其特征在于所述酰化剂的未反应聚丁烯含量小于20%，并且酰化剂基本上不含氯。
11、取代的酰化剂的胺化或羟基化衍生物，所述衍生物是通过权利要求10的取代的酰化剂分别与胺或羟基化合物反应制备的。
12、一种润滑油或燃料的添加剂，所述添加剂包含权利要求11所述的取代的酰化剂的胺化或羟基化衍生物。
Applications Claiming Priority (2)
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|---|---|---|---|
| GB9309121.3 | 1993-05-04 | ||
| GB939309121A GB9309121D0 (en) | 1993-05-04 | 1993-05-04 | Substituted acylating agents |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN1095073A true CN1095073A (zh) | 1994-11-16 |
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| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN94104780.6A Pending CN1095073A (zh) | 1993-05-04 | 1994-05-04 | 取代的酰化剂 |
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| Country | Link |
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| US (1) | US5454964A (zh) |
| EP (1) | EP0623631B1 (zh) |
| JP (1) | JPH0711275A (zh) |
| CN (1) | CN1095073A (zh) |
| BR (1) | BR9401863A (zh) |
| CA (1) | CA2122791A1 (zh) |
| DE (2) | DE69408359T2 (zh) |
| GB (1) | GB9309121D0 (zh) |
| HU (1) | HU213729B (zh) |
| MY (1) | MY131672A (zh) |
| SG (1) | SG46152A1 (zh) |
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| US5891953A (en) * | 1996-02-09 | 1999-04-06 | Exxon Chemical Patents Inc | Process for preparing polyalkenyl substituted mono- and dicarboxylic acid producing materials (PT-1302) |
| US5696060A (en) * | 1996-04-15 | 1997-12-09 | The Lubrizol Corporation | Acylated nitrogen compounds useful as additives for lubricating oil and fuel compositions |
| WO1997047666A1 (en) * | 1996-06-10 | 1997-12-18 | Bp Chemicals Limited | Substituted carboxylated derivatives |
| US5779742A (en) * | 1996-08-08 | 1998-07-14 | The Lubrizol Corporation | Acylated nitrogen compounds useful as additives for lubricating oil and fuel compositions |
| DE69703324T2 (de) * | 1996-08-08 | 2001-03-01 | The Lubrizol Corp., Wickliffe | Acylierte stickstoffenthaltende Verbindungen verwendbar als Zusätze für Schmieröl- und Brennstoffzusammensetzungen und Zwischenprodukte verwendbar zu ihrer Herstellung |
| US5840920A (en) | 1996-08-08 | 1998-11-24 | The Lubrizol Corporation | Process for preparing compositions useful as intermediates for preparing lubricating oil and fuel additives |
| GB9726831D0 (en) | 1997-12-20 | 1998-02-18 | Bp Chem Int Ltd | Additives for hydrocarbon fuels |
| US6648929B1 (en) * | 1998-09-14 | 2003-11-18 | The Lubrizol Corporation | Emulsified water-blended fuel compositions |
| US20060048443A1 (en) * | 1998-09-14 | 2006-03-09 | Filippini Brian B | Emulsified water-blended fuel compositions |
| US6368367B1 (en) | 1999-07-07 | 2002-04-09 | The Lubrizol Corporation | Process and apparatus for making aqueous hydrocarbon fuel compositions, and aqueous hydrocarbon fuel composition |
| US6383237B1 (en) | 1999-07-07 | 2002-05-07 | Deborah A. Langer | Process and apparatus for making aqueous hydrocarbon fuel compositions, and aqueous hydrocarbon fuel compositions |
| US6368366B1 (en) | 1999-07-07 | 2002-04-09 | The Lubrizol Corporation | Process and apparatus for making aqueous hydrocarbon fuel compositions, and aqueous hydrocarbon fuel composition |
| US6530964B2 (en) | 1999-07-07 | 2003-03-11 | The Lubrizol Corporation | Continuous process for making an aqueous hydrocarbon fuel |
| US6419714B2 (en) | 1999-07-07 | 2002-07-16 | The Lubrizol Corporation | Emulsifier for an acqueous hydrocarbon fuel |
| US6913630B2 (en) | 1999-07-07 | 2005-07-05 | The Lubrizol Corporation | Amino alkylphenol emulsifiers for an aqueous hydrocarbon fuel |
| US20040111956A1 (en) * | 1999-07-07 | 2004-06-17 | Westfall David L. | Continuous process for making an aqueous hydrocarbon fuel emulsion |
| US6652607B2 (en) | 1999-07-07 | 2003-11-25 | The Lubrizol Corporation | Concentrated emulsion for making an aqueous hydrocarbon fuel |
| US6827749B2 (en) | 1999-07-07 | 2004-12-07 | The Lubrizol Corporation | Continuous process for making an aqueous hydrocarbon fuel emulsions |
| US6606856B1 (en) | 2000-03-03 | 2003-08-19 | The Lubrizol Corporation | Process for reducing pollutants from the exhaust of a diesel engine |
| US20030084658A1 (en) | 2000-06-20 | 2003-05-08 | Brown Kevin F | Process for reducing pollutants from the exhaust of a diesel engine using a water diesel fuel in combination with exhaust after-treatments |
| WO2005012468A1 (en) * | 2003-08-01 | 2005-02-10 | The Lubrizol Corporation | Mixed dispersants for lubricants |
| US20050101496A1 (en) * | 2003-11-06 | 2005-05-12 | Loper John T. | Hydrocarbyl dispersants and compositions containing the dispersants |
| US7645728B2 (en) | 2004-02-17 | 2010-01-12 | Afton Chemical Corporation | Lubricant and fuel additives derived from treated amines |
| US7361629B2 (en) * | 2004-03-10 | 2008-04-22 | Afton Chemical Corporation | Additives for lubricants and fuels |
| US20060122073A1 (en) | 2004-12-08 | 2006-06-08 | Chip Hewette | Oxidation stable gear oil compositions |
| US7485734B2 (en) * | 2005-01-28 | 2009-02-03 | Afton Chemical Corporation | Seal swell agent and process therefor |
| US7422161B2 (en) | 2006-03-30 | 2008-09-09 | Afton Chemical Corporation | Treated port fuel injectors |
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| WO2011085000A2 (en) * | 2010-01-06 | 2011-07-14 | The University Of North Carolina At Chapel Hill | Fatty acid derivatives and analogs of drugs |
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-
1993
- 1993-05-04 GB GB939309121A patent/GB9309121D0/en active Pending
-
1994
- 1994-04-28 US US08/234,045 patent/US5454964A/en not_active Expired - Fee Related
- 1994-04-29 SG SG1995001780A patent/SG46152A1/en unknown
- 1994-04-29 DE DE69408359T patent/DE69408359T2/de not_active Revoked
- 1994-04-29 DE DE0623631T patent/DE623631T1/de active Pending
- 1994-04-29 EP EP94303143A patent/EP0623631B1/en not_active Revoked
- 1994-05-03 HU HU9401294A patent/HU213729B/hu not_active IP Right Cessation
- 1994-05-03 CA CA002122791A patent/CA2122791A1/en not_active Abandoned
- 1994-05-04 MY MYPI94001111A patent/MY131672A/en unknown
- 1994-05-04 BR BR9401863A patent/BR9401863A/pt not_active Application Discontinuation
- 1994-05-04 CN CN94104780.6A patent/CN1095073A/zh active Pending
- 1994-05-06 JP JP6094412A patent/JPH0711275A/ja active Pending
Also Published As
| Publication number | Publication date |
|---|---|
| DE69408359D1 (de) | 1998-03-12 |
| HU9401294D0 (en) | 1994-08-29 |
| DE69408359T2 (de) | 1998-05-20 |
| EP0623631A2 (en) | 1994-11-09 |
| GB9309121D0 (en) | 1993-06-16 |
| HUT66999A (en) | 1995-01-30 |
| HU213729B (en) | 1997-09-29 |
| CA2122791A1 (en) | 1994-11-05 |
| SG46152A1 (en) | 1998-02-20 |
| EP0623631A3 (en) | 1995-06-07 |
| DE623631T1 (de) | 1996-01-18 |
| JPH0711275A (ja) | 1995-01-13 |
| BR9401863A (pt) | 1995-03-07 |
| US5454964A (en) | 1995-10-03 |
| EP0623631B1 (en) | 1998-02-04 |
| MY131672A (en) | 2007-08-30 |
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