CN1095073A - 取代的酰化剂 - Google Patents
取代的酰化剂 Download PDFInfo
- Publication number
- CN1095073A CN1095073A CN94104780.6A CN94104780A CN1095073A CN 1095073 A CN1095073 A CN 1095073A CN 94104780 A CN94104780 A CN 94104780A CN 1095073 A CN1095073 A CN 1095073A
- Authority
- CN
- China
- Prior art keywords
- compound
- reaction
- acylating agent
- enoyl
- polybutene
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Pending
Links
- 238000006243 chemical reaction Methods 0.000 claims abstract description 47
- -1 enoyl compound Chemical class 0.000 claims abstract description 44
- 239000003795 chemical substances by application Substances 0.000 claims abstract description 35
- 150000001875 compounds Chemical class 0.000 claims abstract description 29
- 238000000034 method Methods 0.000 claims abstract description 23
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 claims abstract description 8
- 239000000460 chlorine Substances 0.000 claims abstract description 8
- 229910052801 chlorine Inorganic materials 0.000 claims abstract description 8
- 239000000446 fuel Substances 0.000 claims abstract description 5
- 239000010687 lubricating oil Substances 0.000 claims abstract description 5
- 150000001412 amines Chemical class 0.000 claims abstract description 3
- 229920001083 polybutene Polymers 0.000 claims description 41
- FPYJFEHAWHCUMM-UHFFFAOYSA-N maleic anhydride Chemical compound O=C1OC(=O)C=C1 FPYJFEHAWHCUMM-UHFFFAOYSA-N 0.000 claims description 40
- 239000004743 Polypropylene Substances 0.000 claims description 5
- 229920001155 polypropylene Polymers 0.000 claims description 5
- 238000005576 amination reaction Methods 0.000 claims description 3
- 230000033444 hydroxylation Effects 0.000 claims description 3
- 238000005805 hydroxylation reaction Methods 0.000 claims description 3
- 239000000654 additive Substances 0.000 claims description 2
- 230000000996 additive effect Effects 0.000 claims description 2
- 230000035484 reaction time Effects 0.000 claims description 2
- 239000003153 chemical reaction reagent Substances 0.000 abstract description 2
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 16
- 229910052757 nitrogen Inorganic materials 0.000 description 8
- 125000002573 ethenylidene group Chemical group [*]=C=C([H])[H] 0.000 description 7
- 230000009257 reactivity Effects 0.000 description 7
- 239000007795 chemical reaction product Substances 0.000 description 6
- 238000001914 filtration Methods 0.000 description 6
- VXNZUUAINFGPBY-UHFFFAOYSA-N 1-Butene Chemical compound CCC=C VXNZUUAINFGPBY-UHFFFAOYSA-N 0.000 description 4
- 238000004140 cleaning Methods 0.000 description 4
- 238000003556 assay Methods 0.000 description 3
- 239000006227 byproduct Substances 0.000 description 3
- 238000007872 degassing Methods 0.000 description 3
- 238000010438 heat treatment Methods 0.000 description 3
- 239000000203 mixture Substances 0.000 description 3
- 238000002360 preparation method Methods 0.000 description 3
- 239000000376 reactant Substances 0.000 description 3
- 238000010407 vacuum cleaning Methods 0.000 description 3
- 238000010792 warming Methods 0.000 description 3
- KAKZBPTYRLMSJV-UHFFFAOYSA-N Butadiene Chemical group C=CC=C KAKZBPTYRLMSJV-UHFFFAOYSA-N 0.000 description 2
- VQTUBCCKSQIDNK-UHFFFAOYSA-N Isobutene Chemical group CC(C)=C VQTUBCCKSQIDNK-UHFFFAOYSA-N 0.000 description 2
- IMNFDUFMRHMDMM-UHFFFAOYSA-N N-Heptane Chemical compound CCCCCCC IMNFDUFMRHMDMM-UHFFFAOYSA-N 0.000 description 2
- 150000008065 acid anhydrides Chemical class 0.000 description 2
- VSCWAEJMTAWNJL-UHFFFAOYSA-K aluminium trichloride Chemical compound Cl[Al](Cl)Cl VSCWAEJMTAWNJL-UHFFFAOYSA-K 0.000 description 2
- 239000002585 base Substances 0.000 description 2
- IAQRGUVFOMOMEM-UHFFFAOYSA-N butene Natural products CC=CC IAQRGUVFOMOMEM-UHFFFAOYSA-N 0.000 description 2
- 238000005660 chlorination reaction Methods 0.000 description 2
- 229930195733 hydrocarbon Natural products 0.000 description 2
- 150000002430 hydrocarbons Chemical class 0.000 description 2
- 229920001748 polybutylene Polymers 0.000 description 2
- 239000000047 product Substances 0.000 description 2
- 238000003756 stirring Methods 0.000 description 2
- IAQRGUVFOMOMEM-ONEGZZNKSA-N trans-but-2-ene Chemical compound C\C=C\C IAQRGUVFOMOMEM-ONEGZZNKSA-N 0.000 description 2
- 239000004215 Carbon black (E152) Substances 0.000 description 1
- 239000005909 Kieselgur Substances 0.000 description 1
- 229920002367 Polyisobutene Polymers 0.000 description 1
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 1
- 230000004913 activation Effects 0.000 description 1
- 238000001994 activation Methods 0.000 description 1
- 238000013019 agitation Methods 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 235000013844 butane Nutrition 0.000 description 1
- 238000007233 catalytic pyrolysis Methods 0.000 description 1
- 238000005336 cracking Methods 0.000 description 1
- 230000002950 deficient Effects 0.000 description 1
- 238000010790 dilution Methods 0.000 description 1
- 239000012895 dilution Substances 0.000 description 1
- 125000004050 enoyl group Chemical group 0.000 description 1
- 125000000524 functional group Chemical group 0.000 description 1
- 150000003949 imides Chemical class 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 238000012423 maintenance Methods 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- IJDNQMDRQITEOD-UHFFFAOYSA-N n-butane Chemical class CCCC IJDNQMDRQITEOD-UHFFFAOYSA-N 0.000 description 1
- 239000011347 resin Substances 0.000 description 1
- 229920005989 resin Polymers 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- RINCXYDBBGOEEQ-UHFFFAOYSA-N succinic anhydride Chemical compound O=C1CCC(=O)O1 RINCXYDBBGOEEQ-UHFFFAOYSA-N 0.000 description 1
- 230000009466 transformation Effects 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
- C10M133/00—Lubricating compositions characterised by the additive being an organic non-macromolecular compound containing nitrogen
- C10M133/52—Lubricating compositions characterised by the additive being an organic non-macromolecular compound containing nitrogen having a carbon chain of 30 or more atoms
- C10M133/56—Amides; Imides
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F8/00—Chemical modification by after-treatment
- C08F8/30—Introducing nitrogen atoms or nitrogen-containing groups
- C08F8/32—Introducing nitrogen atoms or nitrogen-containing groups by reaction with amines
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F8/00—Chemical modification by after-treatment
- C08F8/46—Reaction with unsaturated dicarboxylic acids or anhydrides thereof, e.g. maleinisation
-
- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
- C10M2215/00—Organic non-macromolecular compounds containing nitrogen as ingredients in lubricant compositions
- C10M2215/02—Amines, e.g. polyalkylene polyamines; Quaternary amines
- C10M2215/04—Amines, e.g. polyalkylene polyamines; Quaternary amines having amino groups bound to acyclic or cycloaliphatic carbon atoms
-
- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
- C10M2215/00—Organic non-macromolecular compounds containing nitrogen as ingredients in lubricant compositions
- C10M2215/086—Imides
-
- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
- C10M2215/00—Organic non-macromolecular compounds containing nitrogen as ingredients in lubricant compositions
- C10M2215/26—Amines
-
- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
- C10M2215/00—Organic non-macromolecular compounds containing nitrogen as ingredients in lubricant compositions
- C10M2215/28—Amides; Imides
-
- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
- C10M2217/00—Organic macromolecular compounds containing nitrogen as ingredients in lubricant compositions
- C10M2217/04—Macromolecular compounds from nitrogen-containing monomers obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds
- C10M2217/046—Polyamines, i.e. macromoleculars obtained by condensation of more than eleven amine monomers
-
- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
- C10M2217/00—Organic macromolecular compounds containing nitrogen as ingredients in lubricant compositions
- C10M2217/06—Macromolecular compounds obtained by functionalisation op polymers with a nitrogen containing compound
Landscapes
- Chemical & Material Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- General Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Health & Medical Sciences (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Oil, Petroleum & Natural Gas (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
- Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)
- Lubricants (AREA)
- Liquid Carbonaceous Fuels (AREA)
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)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| 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 |
Family
ID=10734871
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN94104780.6A Pending CN1095073A (zh) | 1993-05-04 | 1994-05-04 | 取代的酰化剂 |
Country Status (11)
| Country | Link |
|---|---|
| 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) |
Families Citing this family (33)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| GB9503380D0 (en) * | 1995-02-21 | 1995-04-12 | Bp Chem Int Ltd | Substituted azo-dicarbonylo deriratives |
| GB9507305D0 (en) * | 1995-04-07 | 1995-05-31 | Bp Chem Int Ltd | Substituted acylating agents |
| US5777025A (en) * | 1996-02-09 | 1998-07-07 | Exxon Chemical Patents Inc. | Process for preparing polyalkenyl substituted C4 to C10 dicarboxylic acid producing materials |
| 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 |
| 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 |
| EP0823471B1 (en) * | 1996-08-08 | 2000-10-18 | The Lubrizol Corporation | Acylated nitrogen compounds useful as additives for lubricating oil and fuel compositions and intermediates useful for preparing same |
| 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 |
| 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 |
| 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 |
| US6827749B2 (en) | 1999-07-07 | 2004-12-07 | The Lubrizol Corporation | Continuous process for making an aqueous hydrocarbon fuel emulsions |
| 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 |
| US6530964B2 (en) | 1999-07-07 | 2003-03-11 | The Lubrizol Corporation | Continuous process for making an aqueous hydrocarbon fuel |
| US6652607B2 (en) | 1999-07-07 | 2003-11-25 | The Lubrizol Corporation | Concentrated emulsion for making an aqueous hydrocarbon fuel |
| US6419714B2 (en) | 1999-07-07 | 2002-07-16 | The Lubrizol Corporation | Emulsifier for an acqueous hydrocarbon fuel |
| 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 |
| JP5046644B2 (ja) * | 2003-08-01 | 2012-10-10 | ザ ルブリゾル コーポレイション | 潤滑剤用の混合分散剤 |
| 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 |
| US20090156445A1 (en) * | 2007-12-13 | 2009-06-18 | Lam William Y | Lubricant composition suitable for engines fueled by alternate fuels |
| EP2072544A1 (en) * | 2007-12-19 | 2009-06-24 | Akzo Nobel Coatings International B.V. | Triglyceride macromonomers |
| CA2785834A1 (en) * | 2010-01-06 | 2011-07-14 | The University Of North Carolina At Chapel Hill | Fatty acid derivatives and analogs of drugs |
Family Cites Families (17)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US3030387A (en) * | 1956-08-01 | 1962-04-17 | California Research Corp | Preparation of hydrocarbon substituted succinic acid anhydrides |
| US3231587A (en) * | 1960-06-07 | 1966-01-25 | Lubrizol Corp | Process for the preparation of substituted succinic acid compounds |
| US3288714A (en) * | 1961-12-06 | 1966-11-29 | Monsanto Co | Lubricating oil compositions containing alkenyl succinic anhydrides |
| US3474110A (en) * | 1964-10-09 | 1969-10-21 | Gaf Corp | Process of alkylating cyclic anhydrides |
| US4086251A (en) * | 1975-02-10 | 1978-04-25 | Standard Oil Company (Indiana) | Process for manufacturing polyalkenyl succinic anhydrides |
| DE2965642D1 (en) * | 1978-12-07 | 1983-07-14 | Exxon Research Engineering Co | Process for producing oil soluble derivatives of unsaturated c4-c10 dicarboxylic acid materials |
| US4472588A (en) * | 1981-11-25 | 1984-09-18 | Bp Chemicals Limited | Production of polyalkenyl succinic anhydrides |
| US4434071A (en) * | 1982-01-15 | 1984-02-28 | Texaco Inc. | 1,3-Dibromo dialkylhydantoin and olefin oligomer reaction product as a catalyst for preparing alkenyl dicarboxylic acid anhydride |
| US4431825A (en) * | 1982-04-12 | 1984-02-14 | Texaco Inc. | Preparation of alkenyl succinic anhydrides |
| JPS58214598A (ja) * | 1982-06-07 | 1983-12-13 | 三菱石油株式会社 | 製紙用サイズ剤 |
| DE3411531A1 (de) * | 1984-03-29 | 1985-10-10 | Basf Ag, 6700 Ludwigshafen | Verfahren zur umsetzung von olefinen mit maleinsaeureanhydrid und verwendung der erhaltenen bernsteinsaeureanhydride zur herstellung von korrosionsschutzmitteln und mineraloelhilfsmitteln |
| US4581464A (en) * | 1984-12-24 | 1986-04-08 | Monsanto Company | Preparation of alkenyl succinic anhydrides |
| JP2584802B2 (ja) * | 1987-12-14 | 1997-02-26 | 三菱化学株式会社 | アルケニルコハク酸無水物の製造法 |
| GB8818711D0 (en) * | 1988-08-05 | 1988-09-07 | Shell Int Research | Lubricating oil dispersants |
| GB9006577D0 (en) * | 1990-03-23 | 1990-05-23 | Shell Int Research | Thermosetting polyol resins and coating compositions based upon such resins |
| US5071919A (en) * | 1990-05-17 | 1991-12-10 | Ethyl Petroleum Additives, Inc. | Substituted acylating agents and their production |
| US5137980A (en) * | 1990-05-17 | 1992-08-11 | Ethyl Petroleum Additives, Inc. | Ashless dispersants formed from substituted acylating agents and their production and use |
-
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 EP EP94303143A patent/EP0623631B1/en not_active Revoked
- 1994-04-29 DE DE69408359T patent/DE69408359T2/de not_active Revoked
- 1994-04-29 DE DE0623631T patent/DE623631T1/de active Pending
- 1994-04-29 SG SG1995001780A patent/SG46152A1/en unknown
- 1994-05-03 CA CA002122791A patent/CA2122791A1/en not_active Abandoned
- 1994-05-03 HU HU9401294A patent/HU213729B/hu not_active IP Right Cessation
- 1994-05-04 BR BR9401863A patent/BR9401863A/pt not_active Application Discontinuation
- 1994-05-04 CN CN94104780.6A patent/CN1095073A/zh active Pending
- 1994-05-04 MY MYPI94001111A patent/MY131672A/en unknown
- 1994-05-06 JP JP6094412A patent/JPH0711275A/ja active Pending
Also Published As
| Publication number | Publication date |
|---|---|
| CA2122791A1 (en) | 1994-11-05 |
| HUT66999A (en) | 1995-01-30 |
| US5454964A (en) | 1995-10-03 |
| EP0623631A3 (en) | 1995-06-07 |
| EP0623631B1 (en) | 1998-02-04 |
| DE623631T1 (de) | 1996-01-18 |
| JPH0711275A (ja) | 1995-01-13 |
| DE69408359T2 (de) | 1998-05-20 |
| GB9309121D0 (en) | 1993-06-16 |
| EP0623631A2 (en) | 1994-11-09 |
| MY131672A (en) | 2007-08-30 |
| DE69408359D1 (de) | 1998-03-12 |
| HU9401294D0 (en) | 1994-08-29 |
| HU213729B (en) | 1997-09-29 |
| SG46152A1 (en) | 1998-02-20 |
| BR9401863A (pt) | 1995-03-07 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN1095073A (zh) | 取代的酰化剂 | |
| US5137978A (en) | Substituted acylating agents and their production | |
| US5071919A (en) | Substituted acylating agents and their production | |
| US7411104B2 (en) | Method for producing polybutene | |
| US5286799A (en) | Two-step free radical catalyzed process for the preparation of alkenyl succinic anhydride | |
| EP0145235B1 (en) | Cationic polymerisation of 1-olefins | |
| US5420207A (en) | Preparation of polyisobutylsuccinic anhydrides | |
| US4810754A (en) | High temperature peroxide induced telomerization processes for grafting vinyl nitrogen containing monomers onto olefin polymers | |
| JP3119452B2 (ja) | イソブチレン重合のためのｂｆ▲下３▼・第三エーテレート錯体 | |
| EP0377240B1 (en) | Preparation of modified star polymers and the use of such polymers as luboil additives | |
| CA2369500C (en) | Method for making monoamines | |
| AU745384B2 (en) | Intermediates useful for preparing dispersant-viscosity improvers for lubricating oils | |
| US6025308A (en) | Amine-functionalized polymers | |
| US3884988A (en) | Production of synthetic lubricants from alpha-olefins through a ternary catalytic system | |
| EP0260140A2 (en) | Hydrocarbyl anhydrides, hydraulic fluid compositions and epoxy curing agents threfrom | |
| EP0677572A2 (en) | Detergent-dipersant additive for lubricating oils of internal combustion engines and its preparation process | |
| CN111978439B (zh) | 形成高活性烯烃官能聚合物的改进方法 | |
| JP4632547B2 (ja) | フリーラジカル重合したコポリマーを製造するための改良された方法 | |
| WO1991011469A1 (en) | Fuel oil compositions and additives | |
| KR100827273B1 (ko) | 삼불화붕소 착물 촉매의 제조방법 및 이를 이용한 고반응성폴리부텐의 제조방법 | |
| JP2000080127A (ja) | ブテンポリマーの製造法 | |
| JP2000063436A (ja) | ブテンポリマーの製造方法 | |
| JP2003252927A (ja) | 変性ポリオレフィンとその製造方法およびポリオレフィン置換ジカルボン酸誘導体の製造方法 | |
| EP0700932A1 (en) | Process for modifying a polyolefin | |
| EP0645402A1 (en) | Polybutenes |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| C01 | Deemed withdrawal of patent application (patent law 1993) | ||
| WD01 | Invention patent application deemed withdrawn after publication |