CN100343289C - 形成聚烯烃基酰化剂的方法 - Google Patents
形成聚烯烃基酰化剂的方法 Download PDFInfo
- Publication number
- CN100343289C CN100343289C CNB2004100487856A CN200410048785A CN100343289C CN 100343289 C CN100343289 C CN 100343289C CN B2004100487856 A CNB2004100487856 A CN B2004100487856A CN 200410048785 A CN200410048785 A CN 200410048785A CN 100343289 C CN100343289 C CN 100343289C
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- China
- Prior art keywords
- reaction
- polyolefine
- compound
- dicarboxylic acid
- acid
- Prior art date
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- Expired - Lifetime
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- 238000000034 method Methods 0.000 title claims abstract description 59
- 230000008569 process Effects 0.000 title claims abstract description 14
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- 238000006243 chemical reaction Methods 0.000 claims abstract description 68
- 239000011541 reaction mixture Substances 0.000 claims abstract description 25
- OFOBLEOULBTSOW-UHFFFAOYSA-N Malonic acid Chemical compound OC(=O)CC(O)=O OFOBLEOULBTSOW-UHFFFAOYSA-N 0.000 claims abstract description 24
- 239000003795 chemical substances by application Substances 0.000 claims abstract description 19
- 150000001875 compounds Chemical class 0.000 claims description 65
- 239000000203 mixture Substances 0.000 claims description 40
- FPYJFEHAWHCUMM-UHFFFAOYSA-N maleic anhydride Chemical compound O=C1OC(=O)C=C1 FPYJFEHAWHCUMM-UHFFFAOYSA-N 0.000 claims description 20
- 150000008065 acid anhydrides Chemical class 0.000 claims description 18
- LSNNMFCWUKXFEE-UHFFFAOYSA-M Bisulfite Chemical compound OS([O-])=O LSNNMFCWUKXFEE-UHFFFAOYSA-M 0.000 claims description 17
- 239000000376 reactant Substances 0.000 claims description 16
- 150000003254 radicals Chemical class 0.000 claims description 15
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- 150000001412 amines Chemical group 0.000 claims description 14
- 239000003112 inhibitor Substances 0.000 claims description 14
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- 239000004215 Carbon black (E152) Substances 0.000 claims description 9
- 229930195733 hydrocarbon Natural products 0.000 claims description 9
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- 239000007795 chemical reaction product Substances 0.000 claims description 7
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical group [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 claims description 5
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- 239000013543 active substance Substances 0.000 description 10
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- KZNICNPSHKQLFF-UHFFFAOYSA-N succinimide Chemical compound O=C1CCC(=O)N1 KZNICNPSHKQLFF-UHFFFAOYSA-N 0.000 description 10
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- UPYPTOCXMIWHSG-UHFFFAOYSA-N 1-dodecylsulfanyldodecane Chemical compound CCCCCCCCCCCCSCCCCCCCCCCCC UPYPTOCXMIWHSG-UHFFFAOYSA-N 0.000 description 2
- HECLRDQVFMWTQS-RGOKHQFPSA-N 1755-01-7 Chemical compound C1[C@H]2[C@@H]3CC=C[C@@H]3[C@@H]1C=C2 HECLRDQVFMWTQS-RGOKHQFPSA-N 0.000 description 2
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- 125000004433 nitrogen atom Chemical group N* 0.000 description 1
- 229910017464 nitrogen compound Inorganic materials 0.000 description 1
- 125000001400 nonyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- LIXVMPBOGDCSRM-UHFFFAOYSA-N nonylbenzene Chemical compound CCCCCCCCCC1=CC=CC=C1 LIXVMPBOGDCSRM-UHFFFAOYSA-N 0.000 description 1
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- 125000002347 octyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
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- 239000011368 organic material Substances 0.000 description 1
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- WXZMFSXDPGVJKK-UHFFFAOYSA-N pentaerythritol Chemical compound OCC(CO)(CO)CO WXZMFSXDPGVJKK-UHFFFAOYSA-N 0.000 description 1
- 239000003348 petrochemical agent Substances 0.000 description 1
- 150000002989 phenols Chemical class 0.000 description 1
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- 229910052698 phosphorus Inorganic materials 0.000 description 1
- 239000011574 phosphorus Substances 0.000 description 1
- 229920000333 poly(propyleneimine) Polymers 0.000 description 1
- 229920001748 polybutylene Polymers 0.000 description 1
- 229920000573 polyethylene Polymers 0.000 description 1
- 229920001155 polypropylene Polymers 0.000 description 1
- 238000001556 precipitation Methods 0.000 description 1
- 150000003141 primary amines Chemical group 0.000 description 1
- TVDSBUOJIPERQY-UHFFFAOYSA-N prop-2-yn-1-ol Chemical compound OCC#C TVDSBUOJIPERQY-UHFFFAOYSA-N 0.000 description 1
- 235000019260 propionic acid Nutrition 0.000 description 1
- IUVKMZGDUIUOCP-BTNSXGMBSA-N quinbolone Chemical compound O([C@H]1CC[C@H]2[C@H]3[C@@H]([C@]4(C=CC(=O)C=C4CC3)C)CC[C@@]21C)C1=CCCC1 IUVKMZGDUIUOCP-BTNSXGMBSA-N 0.000 description 1
- 229920013730 reactive polymer Polymers 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- 239000011347 resin Substances 0.000 description 1
- 229920005989 resin Polymers 0.000 description 1
- 238000004904 shortening Methods 0.000 description 1
- 229910001220 stainless steel Inorganic materials 0.000 description 1
- 239000010935 stainless steel Substances 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- 125000001424 substituent group Chemical group 0.000 description 1
- 125000002730 succinyl group Chemical group C(CCC(=O)*)(=O)* 0.000 description 1
- 150000005846 sugar alcohols Polymers 0.000 description 1
- FAGUFWYHJQFNRV-UHFFFAOYSA-N tetraethylenepentamine Chemical compound NCCNCCNCCNCCN FAGUFWYHJQFNRV-UHFFFAOYSA-N 0.000 description 1
- 150000003568 thioethers Chemical class 0.000 description 1
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- 229960001124 trientine Drugs 0.000 description 1
- QQBLOZGVRHAYGT-UHFFFAOYSA-N tris-decyl phosphite Chemical compound CCCCCCCCCCOP(OCCCCCCCCCC)OCCCCCCCCCC QQBLOZGVRHAYGT-UHFFFAOYSA-N 0.000 description 1
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 description 1
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- 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
- C10L1/2383—Polyamines or polyimines, or derivatives thereof (poly)amines and imines; derivatives thereof (substituted by a macromolecular group containing 30C)
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- C08F8/00—Chemical modification by after-treatment
- C08F8/46—Reaction with unsaturated dicarboxylic acids or anhydrides thereof, e.g. maleinisation
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- C10L1/00—Liquid carbonaceous fuels
- C10L1/10—Liquid carbonaceous fuels containing additives
- C10L1/14—Organic compounds
- C10L1/18—Organic compounds containing oxygen
- C10L1/192—Macromolecular compounds
- C10L1/198—Macromolecular compounds obtained otherwise than by reactions involving only carbon-to-carbon unsaturated bonds homo- or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon to carbon double bond, and at least one being terminated by an acyloxy radical of a saturated carboxylic acid, of carbonic acid
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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
- C10M129/00—Lubricating compositions characterised by the additive being an organic non-macromolecular compound containing oxygen
- C10M129/86—Lubricating compositions characterised by the additive being an organic non-macromolecular compound containing oxygen having a carbon chain of 30 or more atoms
- C10M129/92—Carboxylic acids
- C10M129/93—Carboxylic acids having carboxyl groups bound to acyclic or cycloaliphatic carbon atoms
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- C10M129/00—Lubricating compositions characterised by the additive being an organic non-macromolecular compound containing oxygen
- C10M129/86—Lubricating compositions characterised by the additive being an organic non-macromolecular compound containing oxygen having a carbon chain of 30 or more atoms
- C10M129/95—Esters
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- 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
- C10M133/54—Amines
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- 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
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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
- C10M159/00—Lubricating compositions characterised by the additive being of unknown or incompletely defined constitution
- C10M159/12—Reaction products
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- C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
- C10M177/00—Special methods of preparation of lubricating compositions; Chemical modification by after-treatment of components or of the whole of a lubricating composition, not covered by other classes
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- C10M2207/00—Organic non-macromolecular hydrocarbon compounds containing hydrogen, carbon and oxygen as ingredients in lubricant compositions
- C10M2207/10—Carboxylix acids; Neutral salts thereof
- C10M2207/12—Carboxylix acids; Neutral salts thereof having carboxyl groups bound to acyclic or cycloaliphatic carbon atoms
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- C10M2207/00—Organic non-macromolecular hydrocarbon compounds containing hydrogen, carbon and oxygen as ingredients in lubricant compositions
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- C10M2207/34—Esters having a hydrocarbon substituent of thirty or more carbon atoms, e.g. substituted succinic acid derivatives
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Abstract
一种用于制备聚烯烃基酰化剂的方法,其中,一旦聚烯烃与不饱和单-或二羧酸或酸酐化合物的热反应完成,就使反应混合物冷却到低于反应温度,将额外量的不饱和单-或二羧酸或酸酐化合物加入冷却的反应混合物中,然后在任选的搅拌下使反应混合物在反应器中保留一定时间。在引入额外的不饱和单-或二羧酸或酸酐化合物之前降低反应混合物的温度使额外的不饱和单-或二羧酸或酸酐化合物与任意残留未反应聚烯烃之间的进一步反应以及不饱和单-或二羧酸或酸酐化合物的自聚合最小化。反应器中以沉淀物的形式悬浮在反应混合物中或者作为焦油沉积在反应器容器内壁上的聚合的不饱和单-或二羧酸或酸酐化合物被额外的不饱和单-或二羧酸或酸酐化合物化合物溶解并在反应器排空时从反应器中除去。
Description
发明背景
本发明涉及一种通过聚烯烃与产生单-或二羧酸或酸酐的烯属物质的反应来制备油溶性聚烯烃基酰化剂的热方法,该方法具有减低了的反应器积垢水平。更具体而言,本发明涉及一种间歇式反应方法,其中产生单-或二羧酸或酸酐的化合物(如马来酸酐等)与聚烯烃热反应。该方法中,在反应基本完成时,使反应混合物冷却,将额外量的产生单-或二羧酸或酸酐的烯属化合物加入冷却的反应混合物中,并使混合物在反应器中保持一定的时间。这样形成的聚烯烃基酰化剂本身可用作润滑油、功能流体和燃料中的添加剂,也可作为制备其它可用作润滑油、功能流体和燃料中的添加剂的产品(如琥珀酰亚胺)的中间体。
发明背景
聚烯烃基取代的产生单-和二羧酸或酸酐的烯属物质(最引人注目的是聚异丁烯基琥珀酸和酸酐)是已知的用于制备用作润滑剂、燃料和功能流体中的添加剂的产品的中间体。特别地,聚烯烃基琥珀酸酐已用作乳化剂和增容剂,并且通过单胺或多胺与聚烯烃基琥珀酸酐的反应所制得的琥珀酰胺和琥珀酰亚胺已用作润滑油中和燃料中的无灰分散剂和去垢添加剂。
利用一步卤素辅助反应方法已经能制备聚烯烃基取代的产生单-或二羧酸或酸酐的烯属物质,上述方法中聚烯烃与产生单-或二羧酸或酸酐的不饱和烯属化合物(为方便起见以下称作“CAP化合物”)在氯的存在下在升高的温度下反应。利用两步卤素辅助的方法也已经制备了这样的聚烯烃基二羧酸物质,上述方法中在第一步中聚烯烃被氯化,所得的氯化聚烯烃然后与CAP在升高了的温度下反应。一步和两步氯方法都可以以相对较高的产率制备聚烯烃基取代的二羧酸物质。然而,这些产品一般含有残留的氯,而与含氯物质有关的对环境的担忧使得人们不希望使用氯方法。
通过聚烯烃与CAP化合物的直接热反应(本领域中通常称作热(或“烯”)方法),也可制备聚烯烃基取代的羧酸物质。然而,尽管热方法具有避免使用氯的优点,在低于约150℃的反应温度下,反应趋于仅缓慢地进行并产率低。在较高的反应温度(如高于180℃的温度)下,热方法的产率会得到改善。
利用具有相当高比例终端双键的聚烯烃反应物,已经得到了增加了的热方法产率。与内部的双键相比,认为聚烯烃中的终端双键、特别是终端亚乙烯基键在热方法中通常是更有活性的。例如,USPN 4,152,499指出实际上仅在马来酸酐和终端双键之间形成马来酸酐与聚异丁烯的加成物。USPN 4,152,499进一步指出β位的双键也能够反应到一定的程度,而实际上在离链尾更远的双键处不发生反应。USPN 4,086,251指出终端亚乙烯基被认为是聚丁烯末端双键中最有活性的。利用氯化铝催化剂(如AlCl3)通过阳离子聚合而形成的常规聚异丁烯一般具有相对低含量的终端双键。具有高含量终端双键的聚异丁烯(即所谓的“反应性”聚异丁烯)已通过异丁烯的BF3催化聚合而得到。文献中也已经公开了具有在茂金属催化体系存在下通过对应单体的聚合而制备的、高含量终端双键(如乙烯-α-烯烃共聚物和α-烯烃均聚物和共聚物)的其它聚烯烃。
上述卤素辅助反应和热反应都趋于产生显著数量的、在将最终产品用作添加剂或中间体之前必须从其中滤掉沉淀副产物。热方法还趋于产生覆盖反应器壁的焦油,从而使频繁的、耗时且昂贵的反应器清理成为必须。沉淀物被认为至少部分归因于CAP化合物的分解和/或自聚合。焦油的形成被认为是由于CAP化合物(一般为马来酸酐)的自聚合。
与热反应的实施相联系,已知反应性聚烯烃的使用与“常规”聚烯烃相比将提高产率并降低焦油形成。而且,某些处理步骤的使用和某些添加剂的加入已知会进一步减少焦油和沉淀物的形成。例如,USPN 4,235,786指出通过在油溶性强有机酸的存在下进行反应可减少这样的热反应中焦油和沉淀物的形成。USPN 5,777,025描述了一种方法,其中在可抑制沉淀物的量的油溶性烃基取代磺酸的存在下在升高的温度和压力下进行热反应。USPN 4,472,588描述了聚烯烃与马来酸酐之间的热反应,其中逐步添加马来酸酐使得反应器中维持单一的均匀相。该专利指出这一方法导致了减低了的量的树脂(焦油)的形成。
由CAP化合物自聚合引起的反应器结垢降低了反应器加热介质与反应器内容物之间的热传递速率。这加长了循环时间并因此降低了工厂的生产能力。另外CAP化合物自聚合的过程是自催化的。因此,将焦油的存在量最小化降低了额外的焦油的形成速率。反应器结垢导致大量沉淀物形成的极端例子中,可产生对混合设备的机械损坏和/或堵塞排料阀。尽管已发现在热反应中反应性聚合物的使用可降低焦油和沉淀物的形成,且某些处理步骤和添加剂已知可以进一步改善焦油和沉淀物的形成,找到进一步降低了沉淀物和/或焦油(特别是焦油)的数量或者完全消除之、从而使反复清扫反应器成为不必要的改善的热方法是有利的。更具体而言,虽然已知的方法可降低所焦油的形成的量,但随着时间的推移即使最少量的焦油仍可堆积在反应器壁上、使反应器结垢。因此,仍然需要一种使聚烯烃与CAP化合物热反应的方法,该方法能够减少任意一个的反应批次中所形成焦油的量,并且从反应器壁上除去在过去的反应中沉积在反应器壁上的残留焦油。
发明概述
根据本发明的第一个方面,提供了制备聚烯烃基酰化剂的方法,其中在聚烯烃与CAP化合物的热反应完成时,使反应混合物冷却到反应温度以下,并将额外量的CAP化合物添加到冷却的反应混合物中,然后将其在搅拌下在反应器中保持一段时间。在引入额外的CAP化合物之前降低反应混合物的温度以进一步最小化CAP化合物与残留未反应聚烯烃之间的反应和CAP化合物的自聚合。反应器中聚合的CAP化合物(其以沉淀物的形式悬浮在反应混合物中或者作为焦油沉积在反应器容器内壁上)被额外的CAP化合物溶解并且在反应容器排空时从反应器中除去。
根据本发明的第二方面,提供了一种方法,正如在第一方面中的,其中聚烯烃为Mn为900至2500的聚丁烯,CAP化合物为马来酸酐。
根据本发明的第三方面,提供了一种方法,正如在第一和第二方面中的,其中聚烯烃是终端亚乙烯基含量为至少约30%的反应性聚烯烃。
根据本发明的第四方面,提供了一种方法,正如在第一、第二或第三方面中的,其中反应物CAP化合物被逐步地加入反应混合物中。
根据本发明的第五方面,提供了一种方法,正如在第一、第二、第三或第四方面中的,其中在对减少焦油有效的量的油溶性磺酸的存在下进行该反应。
根据本发明的第六方面,提供了一种方法,正如在第一、第二、第三、第四或第五方面中的,其中聚烯烃是终端亚乙烯基含量为至少约30%的反应性聚烯烃,且在一定量自由基抑制剂(如吩噻嗪化合物)的存在下进行反应以减少沉淀物。
通过参考以下对优选实施方案的详细描述会更好地理解本发明的这些和其它目的、优点和特征。
本发明的详细描述
优选的聚烯烃是α-烯烃均聚物、α-烯烃共聚物和乙烯-α-烯烃共聚物。α-烯烃共聚和均聚物分别是一种和至少两种具有式CH2=CHR’的C3至C12α-烯烃的聚合物,其中R’为具有1至10个碳原子的直链或支化烷基自由基。不饱和乙烯-α-烯烃共聚物是乙烯和上式的至少一种α-烯烃的聚合物。前述均聚物和共聚物中所用的α-烯烃更优选选自上式的C3至C12α-烯烃,R’为具有1至4个碳原子的直链或支化烷基。因此,有用的α-烯烃单体和共聚单体包括例如丙烯、丁烯-1、己烯-1、辛烯-1、4-甲基戊烯-1、癸烯-1、十二烯-1及其混合物(如丙烯与丁烯-1的混合物)。这种聚合物的例子是丙烯均聚物、丁烯-1均聚物、乙烯-丙烯共聚物等。优选的聚合物类型是从乙烯和上式的C3至C4α-烯烃衍生的聚合物;即聚乙烯、聚丙烯、聚丁烯-1以及乙烯与丙烯、乙烯与丁烯-1、丁烯-1与丙烯、乙烯与丙烯与丁烯-1的共聚物。
本发明的方法中所用的不饱和乙烯共聚物的摩尔乙烯含量优选在约20至80%的范围内,更优选约30至70%。当丙烯和/或丁烯-1用作与乙烯的共聚单体时,这种共聚物的乙烯含量最优选在约45和65%之间,尽管可以存在更高或更低的乙烯含量。其它适用的共聚物包括其中少量共聚物(如1至20摩尔%)从C4至C18非共轭烯烃(如EPDM)衍生得到的共聚物。EPDM共聚物包括乙烯和丙烯与二环戊二烯、与亚乙基降冰片烯和与1,4-己二烯的共聚物。
尽管聚烯烃一般为烃聚烯烃,适当的聚烯烃可含有非烃部分(如低级烷氧基(将具有最高7个碳原子的基团定义为低级)、低级烷基巯基、羟基、巯基和羰基)),其条件是非烃部分基本不干扰本发明的方法;即,它们不干扰聚烯烃与亲烯体(enophile)之间的热反应。制备聚烯烃时通过使用含有非烃取代基的可聚合烯烃单体可将非烃部分引入聚烯烃中。
聚烯烃的数均分子量在约300到5000(如700到4000)的范围内,优选约450到3000(如700到2500),更优选约900到2500(如1000到2300)。数均分子量可利用几种已知的技术来测定,如凝胶渗透色谱法(“GPC”),气相渗透压法,质子NMR和碳-13 NMR。GPC还提供了通过重均分子量(Mw)与Mn的比率来测定的分子量分布(“MWD”)信息(本领域中也称作多分散性)。MWD不是本发明的方法中起始烃聚合物的关键方面。然而,聚烯烃通常具有低于约6的MWD。特别优选的聚烯烃是具有约450至约3000、更优选约900至2500的数均分子量(Mn)的聚异丁烯和聚丁烯。
反应性聚烯烃与常规聚烯烃的的不同在于终端亚乙烯基含量。具有终端亚乙烯基的聚烯烃链可表示为POLY-C(R)=CH2,其中R为烷基基团,其种类取决于衍生聚烯烃的单体单元(如对于聚异丁烯R为甲基),POLY为聚烯烃链的其它部分。具有终端亚乙烯基的聚合物链的百分比和其它类型的烯烃不饱和基团的百分比可通过质子、或碳-13NMR确定。具有至少约30%(如40至100%)终端亚乙烯基链的聚烯烃被称为反应性聚烯烃,因为当被用于热方法中时,相对于终端亚乙烯基含量低于30%的类似的“常规”聚烯烃,这种聚烯烃趋于具有较高的反应性。优选至少50%、更优选至少60%、最优选至少75%(如75至98%)的这种聚合物链表现出具有终端亚乙烯基不饱和基团。
可以通过在包含至少一种茂金属(如茂过渡金属化合物)和铝氧烷化合物的催化剂体系的存在下聚合α-烯烃单体或者α-烯烃单体的混合物或者含有乙烯和至少一种α-烯烃单体的混合物制备反应性α-烯烃均聚物、α-烯烃共聚物和乙烯-α-烯烃共聚物。制备这些聚合物的适当的方法在例如USPN 5,266,223和5,225,092中公开。反应性乙烯-α-烯烃共聚物可用式POLY-C(R’)=CH2表示,其中R’如以上所定义的,并且其中POLY表示聚合物链。R’烷基基团的链长将根据选择用于聚合的共聚单体而变化。少量聚合物链可含有终端乙烯基不饱和基团,即POLY-CH=CH2,且聚合物的一部分可含有内部单不饱和基团,如POLY-CH=CH(R’)。
优选的反应性聚烯烃包括反应性聚异丁烯(即异丁烯的均聚物)和反应性聚丁烯。反应性聚异丁烯和聚丁烯含有优选至少约50%(如50至95%)、更优选至少约60%(如60至99%)的终端亚乙烯基链。这些反应性聚异丁烯和聚丁烯可利用三氟化硼通过阳离子聚合来形成,且优选使用如水或醇的极性助催化剂和缩短的聚合时间。例如USPN 4,152,499、4,605,808、5,674,955和WO 01/19873 A1中详细描述了可以制备反应性聚异丁烯和聚丁烯的方法。HR-PIB可以商标名GlissopalTM(来自BASF)、UltravisTM(来自BP-Amoco)和TPCxxxx而购得(其中xxxx表示指示分子量的各种数字)(来自Texas Petrochemicals L.P.)。
CAP化合物含有烯属单-和二羧酸或酐物质,即酸、酐、或者酸酯物质,包括(i)单不饱和的C4至C10二羧酸,其中(a)羧基基团是vicinyl(即位于相邻的碳原子上)并且(b)至少一个、优选两个所述的相邻碳原子为所述的单不饱和基团的组成部分;(ii)(i)的衍生物(如酐或者(i)的C1至C5醇衍生的单-或二酯;(iii)单不饱和的C3至C10单羧酸,其中碳-碳双键与羧基基团共轭,即,具有-C=C-CO-的结构;(iv)(iii)的衍生物如(iii)的C1至C5醇衍生的单-或二酯。也可使用CAP化合物(i)至(iv)的混合物。一旦与骨架反应,反应物CAP化合物的单不饱和基团就变得饱和。这样,例如,马来酸酐变成了骨架取代的琥珀酸酐,丙烯酸变成了骨架取代的丙酸。这种单不饱和羧酸反应物的例子是富马酸、衣康酸、马来酸、马来酸酐、氯代马来酸、氯代马来酸酐、丙烯酸、甲基丙烯酸、巴豆酸、肉桂酸和以上的低级烷基(如C1至C4烷基)酸酯,如马来酸甲酯、富马酸乙酯和富马酸甲酯。特别优选的CAP化合物为马来酸酐。与聚烯烃反应的CAP化合物可以与随后加入根据本发明的方法的反应中的CAP化合物相同或不同。
在使用反应性聚烯烃时任选加入反应混合物中以减少沉淀物形成的自由基抑制剂包括酚化合物,如2,6-二叔丁基苯酚、2,4,6-三叔丁基苯酚、2,6-二叔丁基-4-甲基苯酚、2,6-二叔丁基-4-乙基苯酚、o-叔丁基苯酚、2-甲基-6-叔丁基苯酚、2,4,6-三叔辛基苯酚、2,4-二甲基-6-叔丁基苯酚、2-叔丁基-6-(α-甲基苄基)苯酚、2,6-二(α-甲基苄基)苯酚、2,4-二(α,α-二甲基苄基)苯酚、2,4-二叔辛基苯酚、2,4,6-三(α-甲基苄基)苯酚、2,6-二叔丁基-4-羟基苯甲醚、2,6-二叔丁基-4-甲氧基苯酚、2-甲基-6-环己基苯酚、2,6-二叔-α-二甲基氨基-p-甲酚、2,6-二叔辛基-4-癸氧基苯酚、2-叔丁基-4-氯代苯酚、2-叔丁基-4(N,N’-二甲基氨基甲基苯酚)、2,2’-亚甲基-双(4-甲基-6-叔丁基苯酚)、2,2’-亚甲基-双(4-乙基-6-叔丁基苯酚)、2,2’-亚甲基-双(4-甲基-6-壬基苯酚)、2,2’-亚异丁基双(4,6-二甲基苯酚)、2,2’-亚甲基-双(4-甲基-6-环己基苯酚)、4,4’-亚甲基-双(2,6-二叔丁基苯酚)、4,4’-双(2-甲基-6-叔丁基苯酚)、4,4’-亚丁基双(3-甲基-6-叔丁基苯酚)、4,4’-亚异丙基双(2,6-二叔丁基苯酚)、2,2’-硫代双(4-甲基-6-叔丁基苯酚)、4,4’-硫双(2-甲基-6-叔丁基苯酚)、4,4’硫双(3-甲基-6-叔丁基苯酚)、正十八烷基-β-(4’-羟基-3’-5’-二叔丁基苯酚);丙酸酯、双(3-甲基-4-羟基-5-叔丁基苄基)硫醚、双(3,5-二叔丁基-4-羟基苄基)硫化物等;磷化合物,如磷酸三(壬基苯基)酯、亚磷酸三癸酯、二亚磷酸二硬脂基季戊四醇基酯等;萘酚类化合物,如1,2-二羟基萘、1-氨基-2-萘酚、1-硝基-2-萘酚等;胺类化合物,如三甲基胺、苯基-β-萘基胺、p-亚苯基二胺(p-phenylene diamine)、巯基乙基胺、N-亚硝基二甲基胺、苯并三唑、吩噻嗪、卤代二氢-2,2,4-三甲基苯醌等;或者硫化合物,如二丙酸二月桂基硫醇酯、二月桂基硫醚(dilauryl sulfide)、2-巯基苯并咪唑、2-巯基苯并噻唑、二硫化二苯并噻基物、2-巯基苯并噻唑的金属盐、二亚硫酸二乙基黄原酸酯等;喹啉化合物,如氢醌、脲化合物等。以上清单并非旨在穷举所有物质;许多类抑制有机材料中自由基形成的化合物是公知的,且可用于本发明的实施中。自由基抑制剂可以为单一的化合物,或者为这些化合物的组合的混合物。自由基抑制剂优选胺类化合物,更优选吩噻嗪和取代吩噻嗪,最优选吩噻嗪。
任选用于进一步抑制焦油形成的磺酸是油溶性烃基取代磺酸。此处术语“油溶性”是指在20℃的矿物油中至少50%可溶烃基取代磺酸。烃基磺酸可以为天然或合成磺酸,如石油磺酸或石油烷基磺酸、烷基磺酸或者烷芳基磺酸,其中烃基取代基(即,石油烷基、直链和/或支化烷基、烷芳基等)带来了油溶性。油溶石油磺酸可以通过用浓或发烟硫酸处理润滑油基油而得到。
磺酸的烃基取代基可含有非烃基团如硝基、氨基、卤素(如氯或溴)、低级烷氧基、低级烷基巯基、氧(=O)、硫(=S)、亚氨基(-NH-)、醚(-O-)和硫醚(-S-),只要保留了用作本发明的目的的取代基固有烃性能。当存在这种非烃基团时,它们一般占据不超过烃基取代基的总原子重量的约10重量%。
优选的烃基取代基为烷芳基,由此优选的磺酸为烷芳基磺酸。烷芳基磺酸可通过烷基取代芳香烃(例如通过蒸馏和/或提取从石油中分馏得到的那些)的磺化得到,或者通过芳香烃(例如通过苯、甲苯、二甲苯、萘和联苯的烷基化得到的那些)的烷基化得到的。优选的烷芳基磺酸包括通过烃的磺化而得到的那些,所述烃是通过用由丙烯聚合所得的三-、四-或五-丙烯馏分烷基化苯或甲苯而制备的。
烷芳基磺酸一般含有15至76个、优选24至40个、更优选28至36个的总碳原子。芳基部分可从任何芳香烃(如苯、萘、蒽、联苯等)衍生得到,但优选从苯或萘衍生得到,最优选从苯衍生得到。优选的烷基苯磺酸在芳基部分中的一个或多个烷基取代基中含有一般9至70个、优选18至34个、更优选22至30的总碳原子。特别优选数均分子量(Mn)为475至600、平均具有2个烷基基团(其中每个烷基基团平均含有11至15碳原子)的烷基化苯磺酸,
用于制备磺酸的烷基化苯是通过已知的烷基化方法(例如在三氟化硼的存在下苯可以与适当的烯烃或其低聚物或者聚合物反应)得到的。在C9至C70烷基化苯中优选用于制备磺酸的是壬基苯、十二烷基苯、蜡状烷基化苯、以及用由丙烯、丁烯、戊烯或其混合物等得到的具有最多70碳原子的适当的支化的聚合物烷基化的苯。优选使用壬基或十二烷基或烷基混合物中的它们的等价物中的任一种用来制备磺酸。
聚烯烃与CAP化合物之间的反应在间歇反应器中进行,温度为约180至300℃、优选约210至250℃、最优选约220至245℃(如225至235℃),压力为约0至1000kPag。优选在约0至700kPag、更优选在0至400kPag的压力下进行反应。当适用时,部分压力可通过用惰性气体对反应器充气提供。惰性气体可以是在所选择反应时间和条件下不干扰热烯反应的任何气体。该气体一般选自惰性气体(即,氦、氖、氩等)、氮、二氧化碳和一氧化碳。优选的惰性气体是氮和二氧化碳,并最优选氮。因为反应物的气体副产物和/或气体分解产物通常(虽然不是总是)在反应过程中形成(如从马来酸酐分解中形成的CO2),总体系压力一般高于惰性气体分压。
反应时间可以大范围地变化,这取决于如聚烯烃反应性、所需转化率、所选择反应温度等的因素。不论如何,反应时间一般在约1至30小时的范围内,更典型地为约2至10小时(如4至8小时)。
CAP化合物和聚烯烃以约0.9∶1至3∶1(如1∶1至2.5∶1)、优选约1.3∶1至2.5∶1(如1.4∶1至2.2∶1)的CAP化合物与聚烯烃的摩尔比反应。
在增压和加热到反应温度之前,反应物混合物可以任何常规的方式引入到反应器中。例如,反应物可按照任何顺序同时或顺序各自加入反应器中;或者可在另外的混合容器中将反应物混合在一起,然后将混合物加入反应器中。聚烯烃和CAP化合物通常为液体形式(如,将室温下通常为固体的聚烯烃和CAP化合物作为在高温下的熔融物加入)。
另一优选实施方案中,将CAP化合物分阶段地加入反应器中,从而使在反应开始时或者反应开始之前CAP化合物的初始装料与聚烯烃接触,在反应开始之后将一个或多个额外的CAP化合物装料引入所得反应混合物中。
在另一优选实施方案中,当聚烯烃为反应性聚烯烃时,在约10至约3000ppm、优选约10至约2000ppm、更优选约20至约500ppm(基于反应性聚烯烃装料的重量)的自由基抑制剂的存在下进行聚烯烃与CAP化合物之间的反应。
另一优选的实施方案中,进一步在约10至约3000ppm、优选约10至约2000ppm、更优选约20至约500ppm重量(基于聚烯烃装料的重量)的油溶性磺酸的存在下进行聚烯烃与CAP化合物之间的反应。
自由基抑制剂和油溶性磺酸都可以与聚烯烃、CAP化合物的混合物一起引入反应器中。或者,自由基抑制剂和油溶性磺酸可单独地装入反应器中,在另外的混合容器中与聚烯烃混合在一起,然后将混合物装入反应器中;或者可以在装入CAP化合物同时或者随后以任何顺序分别地装入反应器中。自由基抑制剂和磺酸一般都以固体、液体使用,或者优选作为在溶解在一种反应物中的惰性溶剂(如矿物油)中的溶液以促进自由基抑制剂和/或油溶性磺酸与聚烯烃的混合。在特别优选的方法中,优选在聚烯烃与CAP化合物之间反应完成至少约50%后将至少一部分、优选至少50重量%的磺酸装入反应器中。自由基抑制剂也可以分阶段地加入反应混合物中,其中在反应引发之前或者在引发时加入初始数量的自由基抑制剂,在反应过程中,在一个或多个额外装料中,进一步引入自由基抑制剂装料。
在反应基本完成(如理论进程的至少约25、优选至少约50、更优选至少约75、如约80至100%,或者当达到所需的皂化(SAP)值)时,使反应混合物冷却到一定温度,所述温度下聚烯烃与CAP化合物之间的反应速率小于或等于峰值反应速率的约40%,优选小于或等于峰值反应速率的约25%。对于聚烯烃和CAP化合物之间的反应,峰值反应速率基本上与反应器内达到的最高温度时的反应速率一致,且在从约210至250℃的温度下每冷却10℃会使反应速度减少约50%。一旦反应冷却后,加入额外量(如约1至10重量%、优选约1至6重量%,基于装入反应器的聚烯烃的重量)的CAP化合物(优选在搅拌下加入),且使向其中加入额外量的CAP化合物的冷却反应混合物在反应器中保留足以使得焦油和沉淀物溶解在额外量的CAP化合物中或者被额外量的CAP化合物溶解的时间。使向其中加入额外量的CAP化合物的冷却反应混合物在反应器中保留至少约0.2小时、如约0.3至约6小时、优选约0.4至约3小时、更优选约0.5至约1小时。优选地,在引入额外量的CAP化合物之前将反应混合物冷却到低于210℃(如约120至约200℃的温度)。在210℃以下,CAP化合物自聚合的趋势被最小化。另外,从安全的角度优选在低于其沸点的温度下引入额外量的CAP。
在使已向其中加入额外量的CAP化合物的冷却反应混合物在反应器内静置所述的时间后,可以通过例如氮气提或者通过有或没有真空的蒸馏除去过量的CAP化合物、挥发性副产物和分解产物,可加入烃容剂以降低粘度并沉淀焦油和/或沉淀物,并且优选过滤所得混合物。所得产品混合物一般含有所需的聚烯烃衍生物(即,聚烯烃基取代的CAP化合物)和至少一些非官能化的聚烯烃。通常不从产物混合物中去除非官能化的聚烯烃,因为这种去除在工业规模上是昂贵的并且是困难的。
可用其官能度、即与每摩尔加入反应中的聚烯烃(不管其是否进行了官能化)发生反应的CAP化合物的摩尔数的平均值来表征产品混合物。官能度是基于产品混合物的皂化值(“SAP”)和加入的聚烯烃的Mn的。SAP是完全中和1克所得产品混合物所消耗的KOH的毫克数,且可用ASTM D94测定。
利用下式来测定马来酸酐与聚烯烃反应时所得每摩尔产品混合物的琥珀酸基团的平均数:
F=(SAP×Mn)/((112,200×A.I.)-(SAP×98))
其中SAP为皂化值;Mn为初始烯烃聚合物的数均分子量;AI为含有琥珀的反应产物的活性成分百分比(剩余物是未反应的烯烃聚合物、马来酸酐和稀释剂)。由本发明的方法所得的聚烯烃基衍生物的官能度一般为至少约0.5、优选至少约0.7(如至少约0.9)。官能度一般在约0.7至2(如0.9至2)的范围内。一个优选的实施方案中,官能度在约1至2的范围内,优选约1.3至约1.7(如1.3至1.6),更优选约1.3至约1.5。
产品混合物也可依其活性成分(“AI”)来表征,如上所述,活性成分是基于反应的和未反应的聚烯烃的总重量的反应的聚烯烃的重量分数。所得产品混合物的AI一般为至少约0.65(如0.65至0.80),优选至少约0.75(如0.75至0.90),更优选至少约0.80(如0.85至0.99)。通过使用柱色谱法分离官能化的和未官能化的聚合物组分、然后测定所分离组分的重量分数可测出AI。
本发明的方法的产品本身可用作润滑油、燃料和功能流体中的添加剂,但更典型地用作用于制备添加剂的中间体。例如,聚烯烃基衍生物可与亲核反应物(如胺、氨基醇、醇、金属化合物或其混合物)衍生以形成相应的衍生物。用于衍生官能化聚合物的有用的胺化合物包括至少一种胺、并且可以包括一种或多种另外的胺或其它反应性或极性基团。这些胺可以是烃基胺或者可以主要是烃基胺,其中烃基基团包括其它基团(如羟基基团、烷氧基团、酰胺基团、腈、咪唑啉基团等)。特别有用的胺化合物包括单胺和多胺,例如,总碳原子数约2至60、如2至40(如3至20)、每摩尔具有约1至12、如3至12、优选3至9、最优选约6至约7氮原子的的聚烯烃和聚氧化烯聚胺。可有利地使用胺化合物的混合物,如那些通过亚烷基二卤化物与氨的反应而制得的。优选的胺为脂族饱和胺,包括例如1,2-二氨基乙烷、1,3-二氨基丙烷、1,4-二氨基丁烷、1,6-二氨基己烷;聚乙烯胺,如二乙烯三胺、三乙烯四胺、四乙烯五胺;以及聚丙烯胺,如1,2-丙烯二胺和二(1,2-丙烯)三胺。这些被称作PAM的聚胺混合物是可购得的。特别优选的聚胺混合物为通过从PAM产品中蒸馏轻馏分烃所得的混合物。所得的被称作“重”PAM或HPAM的混合物也是可购得的。PAM和/或HPAM的性能和特性描述于例如美国专利4,938,881、4,927,551、5,230,714、5,241,003、5,565,128、5,756,431、5,792,730和5,854,186中。
其它有用的胺化合物包括脂环族二胺(如1,4-二(氨基甲基)环己烷)和杂环氮化合物(如咪唑啉)。另一种有用的胺是如美国专利4,857,217、4,956,107、4,963,275和5,229,022中所公开的多酰胺基和相关的酰胺基胺。也可使用的是如美国专利4,102,798、4,113,639、4,116,876和UK 989,409中所描述的三(羟基甲基)氨基甲烷(TAM)。也可使用dendrimer,星形的胺和梳状结构的胺。类似地,可以使用如美国专利5,053,152中所述的缩合胺。利用如美国专利4,234,435和5,229,022及EP-A-208,560中描述的常规技术来使官能化的聚合物与胺化合物反应。
优选的分散剂组合物包括至少一种聚烯烃基琥珀酰亚胺,所述聚烯烃基琥珀酰亚胺为聚烯烃基取代的琥珀酸酐(如PIBSA)与聚胺的反应产物,其具有约0.65至约1.25、优选约0.8至约1.1、最优选约0.9至约1的偶合比。在该说明书中,“偶合比”可以定义为PIBSA中琥珀酰基团的数目与聚胺反应物中伯胺基团的数目的比值。
以低的偶合比得到低混浊和低自由胺的聚胺衍生的聚烯烃基取代的琥珀酸酐是非常困难的。已发现通过调整胺化反应的速度和顺序可有效解决与混浊和低自由胺含量相关的问题。具体而言,已发现低于约1小时、优选15分钟或更少的较快的胺化(聚胺反应物加入聚烯烃基取代的琥珀酸酐溶液的速度较快)消除了分散剂中的混浊问题,其中所述分散剂是通过聚胺与聚烯烃基取代的琥珀酸酐在小于约1.0(如小于约0.9)、优选小于约0.8的聚烯烃基取代的琥珀酸酐与聚胺的摩尔偶合比下反应得到的。已发现将聚胺衍生的聚烯烃基取代的琥珀酸酐溶液冷却到低于140℃、优选低于约120℃、更优选约60℃至110℃并维持该温度至少约5小时、优选约5至约720小时可有效地将自由胺含量降低到低水平。
官能化的油溶聚合物烃骨架也可以用羟基化合物(如一元和多元醇)或与芳香族化合物(如苯酚和萘酚)衍生。优选的多元醇包括亚烷基二醇,其中亚烷基基团含有2至8个碳原子。其它有用的多元醇包括甘油、甘油的单油酸酯、甘油的单硬脂酸酯、甘油的单甲基醚、季戊四醇及其混合物。酯分散剂也可从不饱和醇(如烯丙醇、肉桂醇、炔丙醇、1-环己烯-3-醇和油醇中衍生得到。能够产生无灰分散剂的其它种醇包括醚-醇(包括氧-亚烷基和氧-亚芳基)。这种醚醇的例子为具有最多150个氧-亚烷基基团的醚醇,其中亚烷基基团含有1至8个碳原子。酯分散剂可以是琥珀酸的二酯或者酸酯(即部分酯化的琥珀酸)以及部分酯化的多元醇或苯酚(即具有自由醇或酚羟基基团的酯)。酯分散剂可以通过几种已知方法(如美国专利3,381,022中所述)中的任一种来制备。
当形成分散剂产物时,官能化的油溶性聚合物骨架通常在稀释油中衍生。由于润滑油组合物越来越要求低硫含量,并且稀释油与分散剂产物保持联系在一起,因此优选利用低硫稀释油或者更优选基本不含(如低于2重量%,如低于1.5重量%)或完全不含硫的稀释油。
所得分散剂优选为非聚合的(如单-或双-琥珀酰亚胺)并且被任选地硼酸化。这种分散剂可通过常规的方式进行硼酸化处理,如美国专利3,087,936、3,254,025和5,430,105中所述。分散剂的硼酸化可通过用其量应足以为每摩尔酰化氮组合物提供约0.1至约20原子比例硼的硼化合物(如氧化硼、卤化硼、硼酸和硼酸酯)处理酰基含氮分散剂容易地完成。
实施例
利用不锈钢壁间歇反应器进行四次连续的间歇反应,其中1000g(0.44摩尔)的聚异丁烯和81g(0.82摩尔)的马来酸酐在0至250kPa的压力和230℃的峰值反应温度下、在持续8小时的搅拌下反应,从而得到琥珀酰亚胺反应产物。一旦反应完成,对反应混合物进行真空气提以除去过量的马来酸酐并过滤所得的反应产物。对每一批次而言,测定过滤的沉淀物并目视测定反应器的清澈程度。结果如表1中所示。
表1
批次 | 对比1 | 对比2 | 对比3 | 对比4 |
沉淀物(体积%) | 0.10 | 0.20 | 0.60 | 0.65 |
可见的反应器污垢(%) | 12 | 32 | 47 | 63 |
SAP(mgKOH/g) | 56.9 | 57.2 | 57.2 | 56.1 |
活性物质(AI)(质量%) | 86.3 | 86.0 | 85.2 | 84.7 |
然后如上进行五次连续的间歇反应,所不同的是一旦反应完成后将反应混合物冷却到195℃并将21g(0.21摩尔,聚异丁烯装料的2.1重量%)的额外的马来酸酐引入反应混合物中。在引入额外的马来酸酐之后,在连续搅拌下使反应混合物在反应器中停留0.5小时。然后对混合物进行真空气提,并过滤所得产物。对每一批次而言,易于以上相同的方式测定过滤的沉淀物并目视测定反应器的清澈程度。结果如表2中所示。
表2
批次 | 发明1 | 发明2 | 发明3 | 发明4 | 发明5 |
沉淀物(体积%) | 0.15 | 0.30 | 0.40 | 0.45 | 0.45 |
可见的反应器污垢(%) | 16 | 28 | 32 | 35 | 35 |
SAP(mgKOH/g) | 58.0 | 58.7 | 58.5 | 57.3 | 57.4 |
活性物质(AI)(质量%) | 86.8 | 87.1 | 86.4 | 86.6 | 86.5 |
从表1的数据中,可以看出,在不引入额外的马来酸酐时,从反应器排出的产物中的沉淀物的数量以及反应器结垢的程度随着每一连续批次而增加,作为反应器结垢的结果,给定SAP的活性物质的量降低。相反,对完成了额外的马来酸酐的引入的批次而言(表2),沉淀物的量和反应器结垢的程度最初都增加,但随后达到稳定并保持基本恒定(AI也是如此)。
再此通过引用将所有此处描述的专利、文章及其他材料完整地引入本文。对组合物的包括、基本由......组成、或者由多种经限定的组分组成的描述应解释为进一步包括由所述经限定的组分的混合物构成的组合物。本发明的原则、优选实施方案和操作模式已经描述于以上说明书中。申请人所递交的是其发明,但不应被理解为仅限于所公开的特定实施方案,因为所公开的实施方案应被理解为是说明性的而不是限制性的。本领域技术人员可以进行改变而不偏离本发明的精神。
Claims (24)
1、一种用于制备聚烯烃基酰化剂的间歇反应方法,其中包括将至少一种聚烯烃与至少一种产生单-或二羧酸或酸酐的化合物在180℃至300℃的反应温度下进行反应,其中在所述反应至少基本完成时,使反应混合物冷却到聚烯烃与产生单-或二羧酸或酸酐的化合物之间的反应速率不高于所述反应过程中峰值反应速率的40%的温度,将额外量的产生单-或二羧酸或酸酐的烯属化合物加入冷却的反应混合物中,并将所得混合物维持在反应器中一段时间以引起反应器焦油的溶解。
2、根据权利要求1的方法,其中所述反应温度为210℃至250℃。
3、根据权利要求1的方法,其中所述反应在0至1000kPag的压力下进行。
4、根据权利要求3的方法,其中所述压力为0至400kPag。
5、根据权利要求1的方法,其中聚烯烃与产生单-或二羧酸或酸酐的化合物以0.9∶1至3∶1的摩尔比进行反应。
6、根据权利要求5的方法,其中所述摩尔比为1.3∶1至2.5∶1。
7、根据权利要求1的方法,其中所述聚烯烃具有300至5000的数均分子量。
8、根据权利要求1的方法,其中所述聚烯烃具有900至2500的数均分子量。
9、根据权利要求7的方法,其中所述聚烯烃为聚异丁烯。
10、根据权利要求7的方法,其中所述聚烯烃具有至少30%的终端亚乙烯基含量。
11、根据权利要求7的方法,其中所述聚烯烃基酰化剂具有1至2的官能度。
12、根据权利要求11的方法,其中所述官能度为1.3至1.7。
13、权利要求1的方法,其中所述产生单-或二羧酸或酸酐的化合物为马来酸酐。
14、根据权利要求1的方法,其中分多阶段将产生单-或二羧酸或酸酐的化合物反应物引入到反应器中。
15、根据权利要求1的方法,其中反应在一定量的油溶性磺酸的存在下进行。
16、根据权利要求15的方法,其中在至少50%的聚烯烃与产生单-或二羧酸或酸酐的化合物反应之后将所述磺酸引入所述反应器中。
17、根据权利要求10的方法,其中反应在一定量的自由基抑制剂的存在下进行。
18、根据权利要求17的方法,其中所述自由基抑制剂为取代或未取代的吩噻嗪。
19、根据权利要求1的方法,其中所述额外量的产生单-或二羧酸或酸酐的化合物为基于聚烯烃反应物的重量1重量%至10重量%。
20、根据权利要求1的方法,其中在反应器中保留所得混合物0.5至1小时的时间。
21、根据权利要求1的方法,其中包括至少一个进一步的步骤,即气提过量的产生单-或二羧酸或酸酐的化合物、加入烃溶剂和过滤反应产物。
22、根据权利要求21的方法,其中包括将反应产物与亲核反应物反应。
23、根据权利要求22的方法,其中所述亲核反应物选自胺、醇、氨基醇、金属化合物及其混合物。
24、根据权利要求23的方法,其中在低硫稀释油或者基本不含或完全不含硫的稀释油中将反应产物与亲核反应物反应。
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- 2003-06-20 US US10/600,677 patent/US6933351B2/en not_active Expired - Lifetime
-
2004
- 2004-05-21 AT AT04076498T patent/ATE462733T1/de not_active IP Right Cessation
- 2004-05-21 DE DE602004026246T patent/DE602004026246D1/de not_active Expired - Lifetime
- 2004-05-21 EP EP04076498A patent/EP1489107B1/en not_active Expired - Lifetime
- 2004-06-17 CA CA002471422A patent/CA2471422C/en not_active Expired - Fee Related
- 2004-06-18 CN CNB2004100487856A patent/CN100343289C/zh not_active Expired - Lifetime
- 2004-06-18 JP JP2004181330A patent/JP2005008638A/ja not_active Abandoned
- 2004-06-18 SG SG200403849A patent/SG117501A1/en unknown
Patent Citations (2)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
EP0899276A1 (en) * | 1997-08-26 | 1999-03-03 | The Lubrizol Corporation | Low chlorine content compositions for use in lubricants and fuels |
EP0987278A1 (en) * | 1998-09-16 | 2000-03-22 | Chevron Chemical Company LLC | Process for making a polyalkenyl derivative of an unsaturated acidic reagent |
Also Published As
Publication number | Publication date |
---|---|
EP1489107B1 (en) | 2010-03-31 |
US20040260027A1 (en) | 2004-12-23 |
US6933351B2 (en) | 2005-08-23 |
CN1572803A (zh) | 2005-02-02 |
EP1489107A3 (en) | 2006-06-21 |
EP1489107A2 (en) | 2004-12-22 |
CA2471422A1 (en) | 2004-12-20 |
DE602004026246D1 (de) | 2010-05-12 |
CA2471422C (en) | 2009-05-12 |
ATE462733T1 (de) | 2010-04-15 |
JP2005008638A (ja) | 2005-01-13 |
SG117501A1 (en) | 2005-12-29 |
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