CN1137533A - 取代的偶氮-二羰基衍生物 - Google Patents
取代的偶氮-二羰基衍生物 Download PDFInfo
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- CN1137533A CN1137533A CN96105751A CN96105751A CN1137533A CN 1137533 A CN1137533 A CN 1137533A CN 96105751 A CN96105751 A CN 96105751A CN 96105751 A CN96105751 A CN 96105751A CN 1137533 A CN1137533 A CN 1137533A
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- C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
- C10M171/00—Lubricating compositions characterised by purely physical criteria, e.g. containing as base-material, thickener or additive, ingredients which are characterised exclusively by their numerically specified physical properties, i.e. containing ingredients which are physically well-defined but for which the chemical nature is either unspecified or only very vaguely indicated
- C10M171/007—Coloured or dyes-containing lubricant compositions
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- 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
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- C10L—FUELS NOT OTHERWISE PROVIDED FOR; NATURAL GAS; SYNTHETIC NATURAL GAS OBTAINED BY PROCESSES NOT COVERED BY SUBCLASSES C10G, C10K; LIQUEFIED PETROLEUM GAS; ADDING MATERIALS TO FUELS OR FIRES TO REDUCE SMOKE OR UNDESIRABLE DEPOSITS OR TO FACILITATE SOOT REMOVAL; FIRELIGHTERS
- C10L1/00—Liquid carbonaceous fuels
- C10L1/10—Liquid carbonaceous fuels containing additives
- C10L1/14—Organic compounds
- C10L1/22—Organic compounds containing nitrogen
- C10L1/234—Macromolecular compounds
- C10L1/238—Macromolecular compounds obtained otherwise than by reactions involving only carbon-to-carbon unsaturated bonds
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- C10L10/00—Use of additives to fuels or fires for particular purposes
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- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10L—FUELS NOT OTHERWISE PROVIDED FOR; NATURAL GAS; SYNTHETIC NATURAL GAS OBTAINED BY PROCESSES NOT COVERED BY SUBCLASSES C10G, C10K; LIQUEFIED PETROLEUM GAS; ADDING MATERIALS TO FUELS OR FIRES TO REDUCE SMOKE OR UNDESIRABLE DEPOSITS OR TO FACILITATE SOOT REMOVAL; FIRELIGHTERS
- C10L10/00—Use of additives to fuels or fires for particular purposes
- C10L10/04—Use of additives to fuels or fires for particular purposes for minimising corrosion or incrustation
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- 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
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- 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
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- 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
- C10M2215/042—Amines, e.g. polyalkylene polyamines; Quaternary amines having amino groups bound to acyclic or cycloaliphatic carbon atoms containing hydroxy groups; Alkoxylated derivatives thereof
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- C10M2215/00—Organic non-macromolecular compounds containing nitrogen as ingredients in lubricant compositions
- C10M2215/18—Containing nitrogen-to-nitrogen bonds, e.g. hydrazine
- C10M2215/182—Azo compounds
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- C10M2215/00—Organic non-macromolecular compounds containing nitrogen as ingredients in lubricant compositions
- C10M2215/26—Amines
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- 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
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- 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
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- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10N—INDEXING SCHEME ASSOCIATED WITH SUBCLASS C10M RELATING TO LUBRICATING COMPOSITIONS
- C10N2040/00—Specified use or application for which the lubricating composition is intended
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- C—CHEMISTRY; METALLURGY
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Abstract
本发明涉及新的由式
表示的C3~C4烯烃的偶氮-二羰基衍生物。
这类化合物可通过烯属化合物例如聚丙烯或聚丁烯、特别是具有亚乙烯基的烯属化合物与ENOPHILE例如X-CO-N=N-CO-Y反应来制备。所得到的产物本身或在用例如多胺进一步官能化后可用作燃料和润滑剂的添加剂。
Description
本发明涉及新的偶氮-二羰基衍生物及其本身或在经进一步反应后的产物作为润滑剂和燃料添加剂的用途。
由取代的聚(异)丁烯和聚丙烯生产燃料和润滑剂的添加剂在本技术领域是熟知的。许多这样的添加剂是由例如聚(异)丁烯基琥珀酐(在下文中称“PIBSA”类)制成的,而聚(异)丁烯基琥珀酐是通过所谓的“ENE”例如聚(异)丁烯(在下文中称为“PIB”)与所谓的“ENOPHILE”、通常为马来酐(在下文中称为“MA”)之间的反应而获得的。ENE与聚合物反应不是很通常的,商业上也仅仅只有进行马来化反应。PIB与MA之间的这种反应既可以在不使用任何氯或其他的氯化的中间体的情况下用热的方法进行,也可以在使用氯促进的反应的条件下进行。生产PIBSA的PIB与MA的反应是在相当严格的条件下例如温度高于200℃、持续时间为2~20小时的条件下进行的,并且经常导致大量的MA作为不希望有的树脂杂质而损失掉,作为树脂杂质必须在产物可被使用前通过纯化步骤而除掉,而且,在这样的反应中PIB的转化率通常很低例如在50%与90%之间并且还产生许多不想要的副产品。所需的纯化步骤难而费钱并且可能造成树脂的处理问题。氯,作为环境上不希望有的产物,通常存在于这样生产的PIBSA类中。在无氯的热方法中,相对于PIB来说MA转化率通常在58%与76%之间,其剩余量高于未反应的PIB。现还由聚丙烯生产类似的相应的衍生物,但这样的产物遇到与PIBSA相类似的问题,并且纯化产物被用于类似用途。
总的说来,对ENE类与ENOPHILE类如马来酐的反应已进行了充分的研究。现还证实,某些工业上非惯用的ENOPHILE类能以高的反应速率与低分子量的烯烃反应。然而,现未进行使用高分子量合成聚合物作为ENE类的常用ENOPHILE类的这样的反应。
现已发现一种生产其本身或被转化为相关的衍生物适用作润滑剂和燃料添加剂的中间体的方法,在该方法中上述问题基本上被减轻,并且高分子量ENE类转化成这些中间体的转化率得到很大的提高。现还发现,通过仔细选择用于此反应的专门的ENOPHILE类以及在合适的反应条件下ENOPHILE类与ENE类的反应速率能被大大地提高。
式中X和Y的每一个代表相同或不相同的烷氧基烷氨基、烷氧烷氨基、氨烷氨基、氨烷氧基,或者,X与Y一起代表-O-、=N-烷基、=N-芳基、=N-烷基(氨烷基)胺,或者,当X或Y是=N-烷基(氨烷基)氨烷基-N=基时,它是这样的以致当此基通过其=N-官能之一既可取代式(I)中的X也可取代Y时,得到具有分别取代式(I)化合物相邻的Y或X的游离=N-官能的产物;和其中
当
R是H时,R1和R2中的每一个也代表氢原子;当
R是结构为(R3)(R4)C=的二价亚烷基时,当与R2一起考虑时,二价亚烷基的一价取代R2并与碳原子形成环状结构,R2被附着在环上,二价亚烷基的另一价与最接近的氮原子相结合,以及取代基R1、R3和R4代表H或烷基;和
当R为H时,合成聚合物基[包括C(R1)(R2基1是由与结构式(I)相符合的C3~C4烯烃的低聚物或聚合物或所说的低聚物或聚合物的取代衍生物得到的。
表示。
根据另一实施方案,本发明涉及一种生产上述式(1)化合物的方法,该方法包括在10~200℃更合适为35~200℃的温度下使ENE化合物a与ENOPHILE化合物b相反应。ENE化合物a是一种C3~C4烯烃的低聚物或聚合物;而ENOPHILE化合物b的通式为X-CO-N=N-CO-Y(III),
在式(III)中,X和Y与式(I)中的意义相同。
ENE最好是数均分子量Mn低于5000、优选为250~3000的丙烯、丁烯或异丁烯的低聚物或聚合物。在ENE类中在其结构中具有亚乙烯基的聚丙烯和聚(异)丁烯最为优选。
ENOPHILE类的具体例子是4-苯基-1,2,4一三唑啉-3,5-二酮(在下文中称为“PTAD”)、偶氮二羧酸二乙酯(在下文中称为“DADC”)和偶氮二羧酸二异丙酯(在下文中称为“DIADC”)。
此反应可通过氢转移进行,以得到ENE仍是不饱和的产物,即,反应产物具有结构式(II)。然而,此反应产物尤其可以是包含化合物(II)的混合物。
我们现发现,ENOPHILE例如PTAD与ENE例如高分子量(例如Mn=650~2300,按GPC或VPO法测定)的PIB的反应可在从例如10°~70℃的很低温下进行并在约30分钟后基本上完成。既没有形成氯也没有形成副产品树脂或焦油,而PIB的转化率基本上高于90%。此反应适于在较低的压力例如大气压下进行。
我们还发现,ENE例如PIB与ENOPHILE例如DADC或DIADC之间的反应大大地快于正常的工业方法中ENE,即PIB,与MA之间所观察到的反应,并且反应进行时不存在氯而且基本上没有副产品树脂;此反应所用的温度非常低例如为100~170℃,并且基本上消耗所有的ENOPHILE。
我们的发明之另一优点在于多于一分子的ENOPHILE能与一分子的ENE例如聚(异)丁烯反应而形成每一被结合的合成聚合物链含有多于一个偶氮二羰基官能基的加合物;这样的加合物在通过低聚或交联制备高分子量聚合物时是有用的。
本发明的另一个最重要的好处在于当不含氯的PIB类[例如由BP化学品公司提供的高活性ULTRAVIS(R)聚(异)丁烯或BASF提供的GLISSOPAL(R),两者的各自的结构中均含有高浓度的亚乙烯基]被用作ENE时,如此形成的中间体和化学改性的中间体不含氯并因此此由氯促进反应制得的PIBSA类更符合环境保护要求。ENOPHILE与这样的活性聚(异)丁烯反应还以远高于与惯用的聚丁烯类反应的速率进行。被用于与ENOPHILE反应的聚(异)丁烯类最好具有数均分子量Mn为低于5000、优选为250~2500。
ENE与ENOPHILE之间的反应最好,但并非必须,在反应温度时能溶解ENOPHILE与ENE两者的溶剂中进行。当使用溶剂时,其常压下的沸点最好为40℃~200℃。优选的溶剂是三氯或四氯乙烷、二噁烷、二烃基二醇、二烃基二甘醇、环状聚烷氧基化合物、以及烃类例如苯、甲苯或二甲苯。溶剂可在反应期间逐步除掉或在反应结束时基本上完全除掉。由于反应使用的压力相当低(在反应温度时各反应剂的混合蒸汽压)使玻璃或钢反应器可以被使用。此反应可在空气中进行,但最好在氮气氛中进行由此而提高反应的安全性。具有由C3~C4烯烃产生的不饱和度的任何商品液态合成聚烯烃可被用作ENE,在添加ENOPHILE和完成反应后,除了去掉溶剂外基本上无需纯化步骤。
反应温度取决于所用的ENOPHILE类,例如,当PTAD作为ENOPHILE时,优选的温度范围为40~70℃;当DADC作为ENOPHILE时,最好,反应温度范围为100~200℃,而优选为120~170℃。
反应剂ENE∶ENOPHILE的摩尔比为1∶0.5至1∶2、优选为1∶0.7至1∶1.6。反应持续时间为15分钟至40小时、优选为15分钟至6小时。ENE与ENOPHILE的加成产物,如先前提到的可以是包括(II)的混合物[为方便起见在下文中称它为“A”]。
当需要时,产物A可在同一容器中与另外的化学改性剂按以下所述进行反应:
例如,在DADC与PIB反应情况时,产物A是双官能的聚丁烯基-偶氮-二羧酸酯(在下文中称为“PIBAD”),或者是聚丁烯基偶氮-烷基羧酰胺(在下文中称为“PAACA”)。这些PIAD类和PAACA类可通过与胺或多胺、醇、水、二醇、羟胺、P2S5、P2O5、烷氧官能化的硅酮、硫醇等反应而被化学改性,得到可用于润滑剂和燃料的添加剂。PIBAD类还能与金属氢氧化物或类似的金属-氧化合物反应而产生其中金属被聚丁烯基-偶氮-二羧基螯合的材料。
特别有意义的是胺类与PIBAD类反应,尤其是当用多胺进行胺化反应时,产生相应的聚丁烯基-偶氮-二胺类(在下文中称为“PIBADA”)。PIBADA类是燃料、润滑剂、洗涤剂和/或分散剂的有用的添加剂。当在某些条件下多胺与PIBAD类反应时,通过二氨基-多胺或其衍生物二个或更多个的PIBAD类分子能连在一起。这类交联分子,例如琥珀酰亚胺,显示出有用的分散性并具有高的粘度指数。尽管我们仅确定了一些有关ENOPHILE类和由其形成的中间体以及及其化学改性成燃料和润滑剂中有用的添加剂的特定的例子,但是本发明并未被限于这些特定的例子与改性方法。
化学改性反应既可以在无任何溶剂下进行也可以通过使用与生产A用的相同溶剂中进行。该反应可在大气压下方便地进行。每摩尔产物A至少使用0.5摩尔的化学改性剂。反应的温度与时间取决于产物A的性质和与其反应的化学改性剂的性质。[通过化学改性剂与A反应而形成的产物在下文中称为“B”]
本发明的新化合物可被用作分散剂、洗涤剂、火花助剂(SparK aider)、耐磨剂、摩擦改进剂、生物杀伤剂等。含有这类化合物的配方还可含钾、氮或磷化合物、氟碳醇、硫化合物等等,这取决配方想望的性质。
参考以下例子将对本发明作进一步的说明
所用的原料及它们的特性
所用的原料及它们的特性
所用的ENE化合物 | 粘度(mm2/s)在100℃时 | 通过NMR测定的=CH2Gps(%) |
Ultravis(U3),Mn=645 | 58 | 65 |
Glissopal10(G10),Mn=930 | 201 | 74 |
Ultravis70(U70),Mn=1960 | 1409 | 65 |
Hyvis10(H10),Mn=935 | 235 | 2 |
所用的ENOPHILE | 颜色 | 其他特征 |
4-苯基-1,2,4-三唑啉-3,5-二酮(PTAD),Mn=175 | 深红色 | 通过IR测定没有>NH基 |
偶氮二羧酸二乙酯(DADC),Mn=174 | 深橙色 | 无>NH基(通过IR测定)密度=1.106 |
偶氮二羧酸二异丙酯(DIADC),Mn=202 | 深橙色 | 存在>NH基(通过IR测定)密度=1.03 |
实施例1-制造A的反应
向装有回流冷凝器与搅拌器的双颈100毫升园底烧瓶添加19.7g的Glissopal10(Mn=930,一种在其结构中具有亚乙烯基不饱和度的活性聚丁烯,购自BASF)和27.9g的1,1,1-三氯乙烷;通过在氮气中的搅拌对所得的混合物进行脱气。添加2.36g的4-苯基-1,2,4-三唑啉-3,5-二酮(PTAD)而形成红色的混合物。
在氮气氛中加热搅拌全部的红色混合物直至所有的PTAD被溶解;在65℃下经20~30分钟后所有的红色混合物变成透明的稻草色溶液。
在旋转蒸发器中在真空和最终温度为140℃下对混合物进行30分钟的汽提溶剂的操作。
对产物-一种稻草色的非常粘稠的液体进行分析。将16.2g的产物回收在两个管形瓶中。产物的1H核磁共振谱显示以下特征:NH质子(8.2ppm);苯基(多重峰,7.5ppm);二个被连接到聚合物链上的亚甲基与氮原子(4.2,4.4ppm);一个新的=C=CH2基(5.08,5.23ppm);一个新的-CH=C=基(5.6ppm);和(TMS=0.0ppm)。这些特征与预期的一对一的ene加合物的两对异物体的谱图相符合。
实施例2-制造A的反应
在装有搅拌器与回流冷凝器的100毫升园底烧瓶中放置9.8g的Ultravis3(一种在其结构中具有高亚乙烯基浓度的高活性聚(异)丁烯,购自BP化学品公司,Mn=645)和34.5g的1,1,1-三氯乙烷。对烧瓶进行氮气清洗。添加2.7g的4-苯基-1,2,4-三唑啉-3,5-二酮形成红色混合物。将烧瓶及其内含物一起在氮气氛与强烈的搅拌下加热13分钟使温度从室温提高到70℃,此时烧瓶的内含物已达到70℃,红色溶液变成淡的稻草色。将烧瓶的内含物转移到旋转蒸发器,在真空下汽提掉1,1,1-三氯乙烷和其他的挥发物,最终温度为140℃、时间30分钟。
对剩余的稻草色液体进行分析。得到11.1g的物料。
实施例3-制造A的反应
向与迪安-斯达克装置和冷凝器相连接的250毫升园底烧瓶添加34g的Ultravis70(一种在其结构中具有高浓度亚乙烯基的高活性聚(异)丁烯,购自BP化学品公司,Mn=1960)、30ml的1,4-二噁烷和20ml的二氯甲烷;在氮气氛下搅拌所有的物料直至烧瓶的内含物均匀一致为止。添加3.01g的4-苯基-1,2,4-三唑啉-3,5-二酮(PTAD)并在氮气氛下搅拌和加热烧瓶的内含物而形成红色混合物。在39~40℃之间蒸出二氯甲烷,烧瓶中的红色溶液在30分种内变为浅的稻草色。最后蒸出大部分的溶剂二噁烷并将烧瓶中的产物转移到旋转蒸发器。在真空下在最终温度为150℃对产物进行1小时的汽提。产物的1H核磁共振谱显示以下特征:苯基(多重峰,7.5ppm);二个亚甲基被连到聚合物链与氮原子(4.2,4.4ppm);一个新的=C=CH2基(5.08,5.23ppm);一个新的-CH=C=基(5.6ppm);和(TMS=0.0ppm)。NH基信号被苯基吸附所掩蔽。
留下8g试样供分析用,而余量(24g)被用于下面的实施例9。
实施例4-制造A的反应
称取71.74g的Ultravis3(一种购自BP化学品公司的高活性聚(异)丁烯,Mn=645)放入到园底烧瓶,添加50ml作为溶剂的1,4-二噁烷。通过搅拌使所有的物料匀化。将烧瓶连接到回流冷凝器并通过该装置缓慢地吹入氮气。用量筒添加17.2ml的偶氮-二羧酸二乙酯(DADC)到呈橙色的搅拌溶液中。将烧瓶的全部内含物加热到101℃回流24小时。溶液的颜色消失。在135℃的旋转蒸发器上通过真空汽提除去溶剂、时间为1小时。回收的物料重量为70g。
实施例5-制造A的反应
在250毫升的园底烧瓶中将67.1g的Glissopal(Mn=930,购自GPC)试样溶于50ml的1,1,1-三氯乙烷并由量筒添加11.4ml的DADC到搅拌溶液中。通过在其上吹入氮气而对烧瓶的内含物进行脱气。
将烧瓶连接到回流冷凝器并将内含物在氮气氛下(回流)加热到约70℃、时间八小时。通过蒸镏除掉溶剂并将剩余料在氮气氛下加热到120℃时间16小时。此时橙色消失。最后将烧瓶的内含物在温度140℃的旋转蒸发器上进行1小时的汽提以除去残余的挥发物。留下透明无色的粘稠的液体。该液体的重量为65g。此产物的13C核磁共振谱显示以下特征:二组双峰羰基[156.0(D),156.8(D)ppm];非相等的-CH2-O-基(61.5,62.3ppm);两个甲基(14.2ppm);在聚合物链中的一个新的ene基(116.0,141.5ppm,与之相比,原料聚合物在114.5和143.3ppm处)和(TMS=0ppm)。
实施例6-制造A的反应
在与回流冷凝器相连的250毫升园底烧瓶中,将72.45g的Ultravis(R)70(Mn=1960由VPO提供)与100ml的1,4-二噁烷相混合。通过该装置缓慢地吹入氮气,然后由量筒添加6.0ml的DADC而形成橙色溶液。在101℃和N2下对烧瓶及其内含物进行搅拌、加热,时间为40小时。橙色完全消失。
将生成的溶液冷却并从烧瓶中取出100ml的冷却溶液并放置在旋转蒸发器中。在真空下和150℃经三小时除去溶剂和其他的挥发份。从旋转蒸发器回收35g含有芳香酯的非常粘稠的物料。园底烧瓶中的剩余产物被用于下面的实施例8。
实施例7-制造A的反应
向装有回流冷凝器的园底烧瓶添加69g的Hyvis10(由BP化学品公司提供的聚丁烯,由VPO测定的Mn=936)和60ml的1,4-二噁烷。由量筒添加12ml的DADC并且在氮气氛下加热搅拌混合物而形成橙色溶液。在氮气氛下将烧瓶的内含物回流(约101℃)120小时。在此之后溶液的橙色未完全消失。将烧瓶的内含物放置在旋转蒸发器中并在真空下、最终温度为160℃、时间2小时进行汽提。回收含芳香酯的制成料,其重量为74g。
实施例8-制造“B”型产物的反应
将来自实施例6中的反应产物和溶剂的剩余物(在其被去掉100ml后)以以下的方式反应。将实施例6中所用的回流冷凝器复原以致使烧瓶及其内含物形成正常的蒸镏并蒸掉约90%的二噁烷溶剂。向烧瓶添加2.7ml的三乙四胺并继续蒸镏直到不再有二噁烷被蒸出。烧瓶及其内含物被加热到180℃时间为1小时并收集镏出液。此镏出液含二噁烷和乙醇。在加热期间烧瓶中的物料已成为稻草色,从烧瓶中得到32.0g的非常粘稠的稻草色液体,对其分析后显示含3.2%重量的氮。
实施例9-制造“B”型产物的反应
向来自实施例3的汽提产物添加4ml的三乙四胺并将其放置在氮气氛下的100ml烧瓶中加热并搅拌。当反应温度为220℃时保温30分钟同时通过烧瓶以10ml/min的速率混入氮。然后将温度提高到235~240℃时间为1小时并继续鼓入氮气泡。然后将烧瓶冷却并添加庚烷。通过作为不溶混的甲醇相的甲醇洗涤去掉游离的三乙四胺。烧瓶所含的庚烷部分(含有B型产物)是稻草色溶液并含有少量的白色半结晶状油。通过倾析从油中分离庚烷溶液并通过真空蒸发除去庚烷溶剂。收集到黄色的、非常粘稠液体的B型产物,其重为18.2g。
实施例10-制造A的反应
在100毫升的三颈园底烧瓶中将6.4g的Ultravis3(通过VPO测定Mn=645)与15ml的二氯甲烷和10ml的1,4-二噁烷混合并添加2.4g的PTAD。将深红色的全部混合物搅拌并在氮气氛下加热到约39℃。在39~40℃下蒸出二氯甲烷,在此期间深红色变化而剩下淡稻草色液体。在除掉二氯甲烷后,在140℃和氮气氛下经1小时汽提掉二噁烷。剩余的淡稻草色粘稠液体重量为8.1g。这是产物A,它含有平均不多于一分子的被结合到聚丁烯基链的PTAD。在此例中,胺化率为1.37。胺化率的定义如下:
被结合的偶氮二羧酸酯的摩尔数
---------------------------------
聚合物的摩尔数
实施例No | ENE摩尔数 | ENOPHILE摩尔数 | A.R* | C,H,N%重量 | 粘度.mm2/S100℃ | 红外线分析 | 颜色 |
1 | G100.0212 | PTAD0.0135 | 0.636 | 82,13,2.3 | - | >NH,>CO,苯基 | 稻草色 |
2 | U30.0152 | PTAD0.0154 | 1.015 | 75.8,11.3,4.6 | - | - | 稻草色 |
3 | U700.0173 | PTAD0.0172 | 0.994 | 83.4,13.4,1.7 | - | - | 稻草色 |
4 | U30.111 | DADC0.1093 | 0.985 | 76.6,12.5,3.1 | 147 | >NH>CO | 无色 |
5 | G100.0722 | DADC0.0725 | 1.004 | 79,12.9,2.3 | 388 | 无色 | |
6 | U700.0370 | DADC0.0381 | 1.03 | 82.5,13.7,1.1 | 1473 | - | 无色 |
7 | H100.0738 | DADC0.0763 | 1.03 | -,-,- | >250 | - | 浅黄色 |
10 | U30.010 | PTAD0.0137 | 1.37 | 77.3,11.1,6.5 | - | - | 稻草色 |
实施例11:
在装有机械搅拌器、回流冷凝器和热电偶温度控制仪的三颈烧瓶中将Glissopal聚丁烯(Mn=1000,491.6g)和偶氮一二羧酸二异丙酯与1,4-二噁烷(450ml)相混合。在氮气掩蔽下将搅拌溶液加热到110℃为时72小时。然后在部份真空和120℃下除去溶剂。将温度增高到180℃并在高的真空度下经90分钟对产物进行汽提。
通过分光镜法的产物分析显示,原料聚丁烯中的90%以上的亚乙烯基已消失并且产物的谱图完全符合聚丁烯和偶氮-二羧酸二异丙酯的一对一的加合物。例如,产物的13C NMR谱显示以下的特征;二个不相当的羰基碳峰(155.7,155.4ppm);二个不相当的叔碳原子>CH-O-(69.5,70.2ppm);四个甲基碳原子(22ppm);一个连到聚合物链和氮原子的亚甲基碳原子(49ppm);一个在聚合物链中的新的ene基(116,141.5ppm,与之相比,原料聚合物为在144.5,143.3ppm处);和(TMS=0ppm)。产物的粘度为435mm2/S(100℃)。产物的元素分析的结果为:
C=79.8%,H=13.2%,N=2.2%,和O=5.0%。
一对一加合物元素分析的计算值为:
C=79.8%,H=13.1%,N=2.2%,和O=5.1%,由此确定了给定产物的结构。
此产物被称为“材料D”。
实施例12:
将包含各约为1/3重量的来自实施例11的材料D、载体和溶剂的商品汽油添加剂配方用作分散剂。此添加剂被添加到标准燃料[根据CO-ordinating EuropeanCouncil for Refernce Fuels(在下文中称为“CEC RF”)83-A-91]中并进行Mercedes-Benz M102E Deposit Fu-el试验(CEC F-05-T-92)。添加剂在燃料中的含量为800ppmV/V。在试验后平均的阀面和阀口的沉积重量(average valve face and tulip deposit weight)为132mg和ITV制质量等级(专属于使用CEC RF试验的Mercedes-Benz发动机的标准级别)为8.3。无添加剂的基本燃料在试验后的平均的阀面和阀口的沉积重量为高于248mg其质量等级仅为7.6。
实施例13:
在装有机械搅拌器、热电偶温度控制器、分馏柱、蒸馏头和冷凝器的三颈烧瓶中将来自实施例11的材料D(158.9g)与二甲氨基丙胺(200ml)相混合并搅拌。将搅拌混合物回流16小时并在此期间通过冷凝器抽出二等分的少量头馏分(每种30ml)。发现此两馏分含二甲氨基丙胺稀释的异丙醇和二异丙醚。在完成反应后,通过在Buchi蒸发器中的真空汽提从反应混合物中除掉过量的二甲氨基丙胺与其他的挥发物。
然后冷却残留物并将蒸发器中取出的冷却产物进行光谱分析并显示出二甲氨丙基和异丙氧基的存在。此产物的元素分析结果如下:
C=79%,H=13.5%,N=4.3%和O=3.5%,
偶氮异丙基羧基二甲基氨丙基-酰胺的加合物的计算值为:
C=78.9%,H=13.1%,N=4.3%和O=3.7%
由此确定了给定产物的结构。此产物是上述定义的“B”型产物。
可以看出,本发明与用于生产作为燃料添剂的中间体及其化学改性产物的常规方法相比具有许多优点,特别是在生产这些产物时:
·不使用氯;
·反应在大气压下和适中的温度下进行;
·不需要过量的ENOPHILE并且未形成副产物而浪费掉;
·在某些情况下反应比ENE类与马来酐反应快得多;
·可在与ENE反应器相同的反应器中进行化学改性;
·除要除去溶剂外,产物(A)或(B)无需提纯步骤;
·就生产B而言,如果需要的话,化学改性剂可被用作溶剂;
·可以生产双官能化的ENE类;
·此ENE反应是普通的并可被用于许多聚烯烃;
·一步法生产出最终应用中有价值的胺化产物。
Claims (19)
式中X和Y的每一个代表相同或不相同的烷氧基、烷氨基、烷氧基烷基氨基、氨烷氨基、氨烷氧基,或者,X与Y一起代表-O-、=N-烷基、=N-芳基、=N-烷基(氨烷基)胺,或者,当X或Y是=N-烷基(氨烷基)氨烷基-N=基时,它是这样的以致当此基通过其=N-官能之一既可取代式(I)中的X也可取代Y时,得到具有分别取代式(I)化合物相邻的Y或X的游离=N-官能的产物;和其中
当
R是H时,R1和R2中的每一个还代表氢原子;
当
R是结构为(R3)(R4)C=的二价亚烷基时,当与R2一起考虑时,二价亚烷基的一价取代R2并与碳原子形成环状结构,R2被附着在环上,二价亚烷基的另一价与最接近的氮原子相结合,以及取代基R1、R3和R4代表H或烷基;和
当R为H时合成聚合物基[包括C(R1)(R2)基]是由与结构式(I)相符合的C3~C4烯烃的低聚物或聚合物或所说的低聚物或聚合物的取代衍生物得到的。
3.一种根据权利要求1或2的化合物,其中合成聚合物基是丙烯或异丁烯的低聚物或聚合物衍生的,所述化合物不含氯。
4.根据前述的权利要求1~3的任何一项权利要求的化合物,其中丙烯或异丁烯的低聚物或聚合物在其结构中具有高浓度的亚乙烯基。
5.根据任何一项的前述的权利要求的化合物,其中所说的化合物是双官能的聚丁烯基-偶氮-二羧酸酯(在下面称为“PIBAD”)。
6.一种生产通式(I)化合物的方法,
式中X和Y的每一个代表相同或不相同的烷氧基、烷氨基、烷氧烷氨基、氨烷氨基、氨烷氧基、或者,X与Y一起代表-O-、=N-烷基、=N-芳基、=N-烷基(氨烷基)胺,或者,当X或Y是=N-烷基(氨烷基)氨烷基-N=基时,它是这样的以致当此基通过其=N-官能之一既可取代式(I)中的X也可取代Y时,得到具有分别取代式(I)化合物相邻的Y或X的游离=N-官能的产物;和其中当
R是H时,R1和R2中的每一个还代表氢原子;当
R是结构为(R3)(R4)C=的二价亚烷基时,当与R2一起考虑时,二价亚烷基的一价取代R2并与碳原子形成环状结构,R2被附着在环上,二价亚烷基的另一价与最接近的氮原子相结合,以及取代基R1、R3和R4代表H或烷基;和
当R为H时,合成聚合物基[包括C(R1)(R2)基]是由与结构式(I)相符合的C3~C4烯烃的低聚物或聚合物或所说的低聚物或聚合物的取代衍生物得到的,所说的方法包括:使
a,一种为C3-C4烯烃的低聚物或聚合物的ENE化合物与
b,一种通式(III)
X-CO-N=N-CO-Y(III)
式中X和Y与上述通式(I)中的X和Y相同的ENOPHILE在10~200℃的温度下反应。
7.根据权利要求6的方法,其中ENE是丙烯、丁烯或异丁烯的低聚物或聚合物。
8.根据前述的权利要求6或7的任何一项权利要求的方法,其中丙烯或异丁烯的低聚物或聚合物在其结构中具有高浓度的亚乙烯基。
9.根据权利要求6~8的方法,其中ENOPHILE是4-苯基-1,2,4-三唑啉-3,5-二酮(以下称为“PTAD”)、偶氮-二羧酸二乙酯(以下称“DADC”)或偶氮-二羧酸二异丙酯(以下称“DIADC”)。
10.根据前述权利要求6~9的任一项权利要求的方法,其中ENE是高分子量的PIB(例如,根据GPC或VPO测定,Mn=650~2300),ENOPHILE是PTAD,并且其中两者之间的反应是在温度为10°~70℃下进行的。
11.根据前述权利要求6~10的任一项权利要求的方法,其中ENE是PIB和ENOPHILE是DADC或DIADC,并且两者之间的反应是在100~170℃下进行的。
12.根据前述权利要求6~11的任一项权利要求的方法,其中反应剂ENE:ENOPHILE的摩尔比为1∶0.5至1∶2。
13.根据前述权利要求6~12的任一项权利要求的方法,其中ENE与ENOPHILE之间的反应是在大气压下沸点为40℃至200℃范围的溶剂中进行的,在反应温度下溶剂溶解ENOPHILE和ENE以致形成基本上无焦油和树脂的产物。
14.根据权利要求13的方法,其中溶剂选自三氯一或四氯乙烷、二噁烷、二烃基二醇、二烃基二甘醇、环状聚烷氧基化合物、苯、甲苯和二甲苯。
15.根据前述权利要求6~14的任一项权利要求的方法,其中ENE与ENOPHILE的反应产物是包含式(II)化合物的化合物的混合物。
16.一种改性权利要求5的PIBAD的方法,其中所说的PIBAD与一种选自胺或多胺、醇、水、二醇、羟胺、五氧化二磷、五硫化二磷、烷氧基官能化硅氧烷、硫醇、金属氢氧化物、金属氧化物的化合物反应。
17.一种包含通过根据权利要求16方法生产的改性PIBAD的燃料或润滑剂的添加剂。
18.一种改性权利要求5的PIBAD的方法,其中所说的PIBAD与多胺反应而产生相应的聚丁烯基一偶氮-二胺(以下称为“PIBADA”),或聚丁烯基-偶氮-烷羧基酰胺(以下称为“PAACA”)。
19.一种包含通过权利要求18方法生产的PIBADA或PAACA。
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