CN1150807A - 制备管能化烯烃的连续方法 - Google Patents
制备管能化烯烃的连续方法 Download PDFInfo
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- CN1150807A CN1150807A CN95193644A CN95193644A CN1150807A CN 1150807 A CN1150807 A CN 1150807A CN 95193644 A CN95193644 A CN 95193644A CN 95193644 A CN95193644 A CN 95193644A CN 1150807 A CN1150807 A CN 1150807A
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Abstract
在CSTR或管式反应器中官能化烯烃,尤其聚合物烯烃的连续方法,优选由烯烃与一氧化碳和亲核捕集剂的连续反应生产酯类。充满液体的管式反应器按活塞流方式与静态混合机一起操作和CSTR在基本上没有空气的情况下在恒定的液面下进行操作。
Description
发明背景
本发明涉及官能化烯烃的连续制备方法,更具体地说,通过让聚合烯烃与一氧化碳和官能化剂在酸催化剂存在下连续反应来生产羧化烯烃如聚酯。
本发明涉及由Koch(科赫)反应官能化的改进聚合物,具体的说,通过让至少一个碳-碳双键与一氧化碳在酸性催化剂和亲核捕集剂存在下进行反应而形成羰基或硫代羰基官能基团,和它们的衍生物。
这里使用的术语“聚合物”是指由小而简单的化学单元的重复所组合的大分子物质。在烃类聚合物中,那些单元主要由氢和碳组成。聚合物由平均性质定义,和在本发明的上下文中具有数均分子量(Mn)至少为500。这里使用的术语“烃”是指具有均匀性质如分子量的、包含氢和碳的非聚合化合物。然而,术语“烃”并不想排除此类化合物的混合物,这些化合物的各自的特征在于此类均匀的性质。
烃类化合物以及聚合化合物经反应后形成含羧基化合物和它们的衍生物。羧基具有通式-CO-OR,其中R是H,烃基,或取代烃基。在金属羧酸盐存在下从烯属烃化合物、一氧化碳和水合成含羧基化合物的方法已公开在文献中,如N.Bahrmann,第5章,Koch反应,“New Synthesis withCarbon Monoxide”J. Falbe;Springer-Verlag,New York,1980。具有烯属双键的烃类经两个步骤反应后形成含羧酸化合物。在第一步中,烯烃化合物与酸催化剂和一氧化碳在没有水存在的情况下进行反应。随后进行第二步,其中在第一步中形成的中间体经过水解或醇解后形成羧酸或酯。Koch反应的优点是它可在-20℃-+80℃的中等温度下和至多100巴的压力下进行。
当两个碳都被单取代或一个被单取代和一个没有被取代时,也可发生科赫反应,形成“异”酸(即-R′HC-COOR)。Bahrmann等人公开了异丁烯经过科赫型反应转变成异丁酸。US-A-2831877公开了用一氧化碳使烯烃羧化的一种多相的酸催化两步方法。曾经研究过用无机酸在水中与BF3形成的配合物来使烯烃羧化。 US-A-3349107公开了一种方法,它使用低于化学计量用量的酸作为催化剂。此类配合物的实例是H2O·BF3·H2O,H3PO4·BF3·H2O和HF·BF3·H2O。
EP-A-0148592涉及由具有碳-碳双键的聚合物,一氧化碳和水或醇,任意性地可有可无地在氧存在下,进行催化反应来制备羧酸酯和/或羧酸的方法。催化剂是金属类如钯,铑,钌,铱和钴与铜化合物的混合物,在质子酸如盐酸存在下。优选的聚合物是聚异丁烯,它的碳-碳双键中至少有80%是端部双键形式。描述了液体聚异丁烯,它的数均分子量为200-2,500,优选至多1,000。
US-A-4927892涉及由共轭二烯的聚合物或共聚物(其中至少一部分是由1,2-聚合反应形成的)与一氧化碳和水和/或醇在催化剂存在下进行反应的方法,该催化剂是由钯化合物、某些配位体和/或除pKa低于2的氢卤酸以外的酸混合制备的。有用的路易斯酸包括BF3。
US-A-5235067公开了链烯基取代的单-和双-琥珀酰亚胺和它们的Mannich偶合中间体的连续酰化方法,但没有给出烯烃的官能化方法。
虽然在现有技术中有关于烯属烃类经过科赫型化学反应在碳-碳双键上官能化形成羧酸或其衍生物的公开物,但没有公开含有碳-碳双键,包括端部烯属双键,或者仲类或者叔类烯属双键,的聚合物能够按照科赫反应机理成功地反应。另外,已经发现,本发明的方法特别适用于制造新酸和新酯官能化的聚合物。用来使低分子量烯属烃类按科赫反应机理羧化的已知催化剂已发现不适合与聚合物一起使用。已经发现特定的催化剂,它们能够在聚合物的碳-碳双键上形成羧酸或酯。科赫化学反应,通过使用高酸性的催化剂和/或小心控制浓度,能够实现使用中等温度和压力的优点。
发明概述
本发明是生产官能化聚合物的方法,包括让聚合烯烃和气态官能化剂连续反应和回收官能化的聚合物。本发明也是连续官能化方法,它包括让烯烃与一氧化碳和亲核捕集剂在酸催化剂存在下反应。本发明也是生产羧化聚合烯烃的连续方法,它包括让该烯烃与一氧化碳和亲核捕集剂在酸催化剂存在下在基本上充满液体的管式反应器(优选以层流方式操作)中进行反应,然后回收羧化聚合物。
本发明涉及官能化的烃聚合物,其中聚合物骨架具有Mn≥500,被下式的基团官能化:
-CO-Y-R3其中Y是O或S,和R3是H,烃基和至少50摩尔%的官能基连接于聚合物骨架的叔碳原子上,或者R3是芳基,取代芳基或取代烃基。
因此,官能化聚合物可由下式表示:
POLY-(CR1R2-CO-Y-R3)n (I)其中POLY是数均分子量为至少500的烃聚合物骨架,n是大于0的数,R1、R2和R3可以相同或不同并且是H,烃基,其前提是R1和R2经选择后应使至少50摩尔%的-CR1R2基团中,R1和R2不是H,或R3是芳基,取代的芳基或取代的烃基。
本发明也是按雷诺数低于10的层流方式进行操作的气-液管式反应器方法,包括让反应物料流过静态混合机,以将气体分散入液体中进行反应。
这里使用的术语“烃基”在本发明的上下文中表示有碳原子直接连接于分子的剩余部分和主要具有烃类属性的基团,并包括聚合烃基。此类基团包括以下这些:
(1)烃基;即脂族(例如烷基或链烯基),脂环族(例如,环烷基或环链烯基),芳族,脂族和脂环族取代的芳族,芳族取代的脂族和脂环族基团,和类似基团,以及环状基团,其中环完全通过分子的另一部分(即,两个指定的取代基一起形成环状基团)。此类基团对本技术领域中的那些熟练人员是已知的;实例包括甲基,乙基,丁基,己基,辛基,癸基,十二烷基,十四烷基,十八烷基,二十烷基,环己基,苯基和萘基(所有的异构化基团也包括在内)。
(2)取代的烃基;即含有非烃取代基的基团,在本发明的上下文中该取代基不会显著改变基团的烃类属性。本技术领域中的那些熟练人员将会知道合适的取代基(例如卤素,羟基,烷氧基,烷酯基,硝基,烷基磺酰氧基)。
(3)杂基团;即这样一种基团:在本发明的上下文中,它主要具有烃的属性,含有除存在于另外由碳原子构成的链或环中的碳原子以外的原子。合适的杂原子对于本技术领域中的熟练人员来说是显然的,并包括,例如氮(尤其非碱性氮,它不使科赫催化剂失活),氧和硫。
一般来说,在基于烃的基团中每10个碳原子将会存在不多于三个取代基或杂原子,和优选不多于一个。聚合烃基是从烃类聚合物衍生而来的那些基团,它们可以是取代的和/或含有杂原子,只要它们主要保留烃的属性。官能化的聚合物可从包含非芳族碳-碳双键(也称作烯属不饱和键),或烯属双键的烃类聚合物衍生而来。该聚合物经科赫反应在双键上官能化,形成羧酸、羧酸酯或硫代酸或硫代酯。
迄今科赫反应还没有用于数均分子量大于500的聚合物。烃类聚合物优选具有Mn大于1,000。在科赫反应方法中,有至少一个烯属双键的聚合物与酸催化剂和一氧化碳在亲核捕集剂如水或醇存在下接触。催化剂优选是经典的布朗斯台德酸或路易斯酸催化剂。这些催化剂优越于现有技术中所述类型的过渡金属催化剂。科赫反应,若用于本发明的方法中,可导致良好产率的官能化聚合物,甚至90摩尔%或更高。
通式I中的POLY代表Mn至少为500的烃类聚合物骨架。Mn可由合适的技术如凝胶渗透色谱法(GPC)来测定。POLY是从不饱和的聚合物衍生而来的。
附图的简述
图1是装有反应试剂进给、产物回收和气体循环装置的带夹套管式反应器的示意图。
优选实施方案的叙述
烯烃类可用于本发明的方法中。可以按照下面关于聚合物所描述的那样将烯属不饱和键官能化。可作为油添加剂应用的烯烃类包括如下所述的低级烯烃物质,中间烯烃类如C18烯烃和聚合烯烃。所有的烯烃都可用于本发明,只要它们能够在本发明的改进的连续方法中操作而将烯属不饱和键官能化。
可用于本发明的聚合物是含有至少一个碳-碳双键(烯属)不饱和键的聚合物。因此,每一聚合物链的官能基最高数目受到每一链的双键数目的限制。已发现,通过使用本发明的催化剂和亲核捕集剂,此类聚合物易接受科赫反应机理,形成羧酸或其衍生物。
在本发明中有用的聚合物包括聚链烯烃类,包括均聚物,共聚物(与共聚体可交换地使用)和混合物。均聚物和共聚体包括从具有2-约16个碳原子,通常2-约6个碳原子的可聚合烯烃单体衍生而来的那些。
尤其要提到的是通过使用有机金属配位化合物制得的α-烯烃聚合物。特别优选的一类聚合物是乙烯-α-烯烃共聚物,如在US-A-5017299中描述的那些。聚合物不饱和键可以是端部的,内部的或两者均可。优选的聚合物具有端部不饱和键,优选高度的端部不饱和键。端部不饱和键是由位于聚合物中的最后一个单体单元提供的不饱和键。该不饱和键能够位于这一端部单体单元的任何地方。端部烯属基团包括:亚乙烯基不饱和键,RaRbC=CH2;三取代的烯烃不饱和键,RaRbC=CRcH;乙烯基不饱和键,RaHC=CH2;1,2-二取代的端部不饱和键,RaHC=CHRb;和四取代的端部不饱和键,RaRbC=CRcR。Ra和Rb中至少一个是本发明的聚合基团,和剩下的Rb,Rc和Rd是与以上R,R1,R2和R3的定义相同的烃基。
低分子量聚合物,这里也称作分散剂分子量范围内的聚合物,是Mn低于20,000,优选500-20,000(例如1,000-20,000),更优选1,500-10,000(例如2,000-8,000)和最优选1,500-5,000的聚合物。由气相渗透法测定数均分子量。低分子量的聚合物可用来制备用于润滑添加剂的分散剂。Mn在20,000-200,000,优选25,000-100,000;和更优选25,000-80,000范围内的中等分子量聚合物可用作润滑油组合物,粘合剂涂料,增粘剂和密封剂的粘度指数改进剂。由膜渗透法测定中等Mn。
高分子量物质所具有的Mn大于约200,000并可高达15,000,000,具体的是300,000-10,000,000和更具体的是500,000-2,000,000。这些聚合物可用于聚合物组合物和共混物,包括弹性体组合物。Mn为20,000-15,000,000的高分子量物质能够用常规的校准物由凝胶渗透色谱法测定或由光散射法测定。比例Mw/Mn的值,称作分子量分布(MWD),不是重要的。然而,大约1.1-2.0的常见最低Mw/Mn值是优选的,一般为约1.1至约4。
烯烃单体优选是可聚合的端部烯烃,即特征在于它们的结构中存在基团-R-C=CH2的烯烃,其中R是H或烃基。然而,特征在于它们的结构中存在以下基团的可聚合的内部烯烃单体(在专利文献中有时称作中间烯烃):也能够用来制备聚链烯烃。当使用内部烯烃单体时,它们通常与端部烯烃一起用来制备聚链烯烃,它们是共聚体。对于本发明,能够被同时分类为端部烯烃和内部烯烃的具体的聚合的烯烃单体必定是端部烯烃。所以,戊二烯-1,3(即戊间二烯)注定是端部烯烃。
尽管聚链烯烃一般是烃类聚链烯烃,但它们可含有取代的烃基,如低级烷氧基,低级烷硫基,羟基,巯基,和羰基,只要非烃部分基本上不干扰本发明的官能化或衍生反应。当存在时,这类取代的烃基一般不超过聚链烯烃总重量的约10wt%。由于聚链烯烃可含有此类非烃取代基,很明显,烯烃单体(从它制得聚链烯烃)也可含有这类取代基。在这里使用时,与化学基团一起使用的术语“低级”如“低级烷基”或“低级烷氧基”,是想要表述至多有7个碳原子的基团。
聚链烯烃可包括芳族基团和环脂族基团,如能够从可聚合的环状烯烃或环脂族基团取代的可聚合的丙烯酸系烯烃获得的基团。通常优选的是,聚链烯烃不含芳族和环脂族基团(早已指出的例外的二烯烃-苯乙烯共聚物除外)。进一步优选的是从具有2-16个碳原子的端部烃类烯烃的均聚物和共聚体得到的聚链烯烃。该进一步优选是由以下条件确定的:尽管端部烯烃的共聚物通常是优选的,任意性可有可无地含有至多约40%的从至多有大约16个碳原子的内部烯烃得到的聚合物单元的共聚物也包括在优选组内。更优选的一类聚链烯烃是从具有2-6个碳原子,更优选2-4个碳原子的端部烯烃的均聚物和共聚物中选择的那些。然而,另一类优选的聚链烯烃是后者,更优选聚链烯烃任意性可有可无地含有至多大约25%的从具有至多大约6个碳原子的内部烯烃得到的聚合物单元。
可在本方法中使用的和根据普通的、众所周知的聚合技术用来制备聚链烯烃的端部和内部烯烃单体的特定实例包括乙烯,丙烯,丁烯-1,丁烯-2,异丁烯,戊烯-1,等;丙烯四聚体,二聚异丁烯(diisobutylene),异丁烯三聚体,丁二烯-1,2,丁二烯-1,3,戊二烯-1,2,戊二烯-1,3,等;C6-C12烯烃,C13-C24,和C24-C29中间烯烃。
有用的聚合物包括α-烯烃均聚物和共聚物,和乙烯-α-烯烃共聚物和三元共聚物。聚链烯烃的特定实例包括聚丙烯,聚丁烯,乙烯-丙烯共聚物,乙烯-丁烯共聚物,丙烯-丁烯共聚物,苯乙烯-异丁烯共聚物,异丁烯-丁二烯-1,3共聚物等,和异丁烯、苯乙烯和戊间二烯的三元共聚物和含有80%的乙烯和20%的丙烯的共聚物。聚链烯烃的一个有用的来源是由丁烯含量为大约35wt%-大约75wt%和异丁烯含量为大约30wt%-大约60wt%的C4炼油厂气流在路易斯酸催化剂如三氯化铝或三氟化硼存在下进行聚合反应获得的聚(异丁烯)。也有用的是USSN 992871(1992年12月17日申请)的高分子量聚正丁烯。用来制造聚正丁烯的优选单体来源是石油原料流,如残油II。这些原料描述在现有技术中,如US-A-4952739。
优选的聚合物是乙烯和至少一种具有通式H2C=CHR4的α-烯烃的聚合物,其中R4是有1-18个碳原子的直链或支链烷基和其中聚合物含有高度的端部亚乙烯基不饱和键。在以上通式中的R4优选是具有1-8个碳原子的烷基和更优选具有1-2个碳原子的烷基。所以,在本发明中与乙烯共聚的有用共聚单体包括丙烯,1-丁烯,己烯-1,辛烯-1等,和它们的混合物(例如丙烯和1-丁烯的混合物,和类似混合物)。优选的聚合物是乙烯和丙烯以及乙烯和丁烯-1的共聚物。
所使用的聚合物的乙烯摩尔含量优选在约20%和约80%之间,和更优选在约30%和约70%之间。当丁烯-1用作与乙烯共聚的共聚单体时,这一共聚物的乙烯含量最优选在约20%和约45%之间,虽然可以存在更高或更低含量的乙烯。最优选的乙烯-丁烯-1共聚物公开于USSN 992192(1992年12月17日申请)。制造低分子量乙烯/α-烯烃共聚物的优选方法描述在USSN 992690(1992年12月17日申请)中。
用作分散剂的前体的聚合物的优选数均分子量范围是500-10,000,优选1,000-8,000,最优选2,500-6,000。进行这一测定的方便方法是尺寸排阻色谱法(也已知为凝胶渗透色谱法(GPC)),它另外还提供分子量分布信息。此类聚合物一般具有特性粘度(在1,2,3,4-四氢萘中于135℃下测定)在0.025和0.6dl/g之间,优选在0.05和0.5dl/g之间,最优选在0.075和0.4dl/g之间。这些聚合物优选显示一定的结晶度,以使得,当被接枝时,它们基本上是无定形的。
优选的乙烯-α-烯烃聚合物再一特征在于,高达约95%和更多的聚合物链具有端部亚乙烯基类型的不饱和键。因此,这类聚合物的一端具有通式POLY-C(R11)=CH2,其中R11是C1-C18烷基,优选C1-C8烷基,和更优选甲基或乙基,和其中POLY表示聚合物链。少量聚合物链可含有端部乙烯基不饱和键,即POLY-CH=CH2,和一部分的聚合物可含有内部单不饱和键,例如POLY-CH=CH(R11),其中R11如上所定义。
优选的乙烯-α-烯烃聚合物包含聚合物链,其中至少约30%具有端部亚乙烯基不饱和键。优选至少约50%,更优选至少约60%,和最优选至少约75%(例如75-98%)的这类聚合物链存在端部亚乙烯基不饱和键。存在端部亚乙烯基不饱和键的聚合物链的百分数可由FTIR光谱分析方法,滴定,H NMR或13C NMR来测定。
由包含乙烯和其它单体如α-烯烃(优选具有3-4个碳原子)的单体混合物在包含至少一种金属茂(例如环戊二烯基-过渡金属化合物)和活化剂(例如铝氧烷化合物)的金属茂催化剂体系存在下进行聚合反应来制备聚合物。共聚单体的含量能够通过选择金属茂催化剂组分和通过控制各单体的分压来控制。
用于本发明的聚合物可包括从包含至少一种共轭二烯烃与至少一种单乙烯基芳族单体(优选苯乙烯)的单体得到的嵌段和组成递变共聚物。此类聚合物不应该被完全氢化,这样聚合物组成含有烯属双键,优选每分子有至少一个双键。本发明还包括在诸如US-A-5070131,US-A-4108945,US-A-3711406和US-A-5049294的专利中公开的星形聚合物。
通式(I)中的字母n是大于0,并表示官能度(F)或每一聚合物链的平均官能基的数目。因此,官能度能够表达为每“摩尔的聚合物”的官能基的平均摩尔数。应该理解术语“摩尔的聚合物”包括官能化的和未官能化的聚合物,这样F对应于通式(I)中的n。官能化聚合物包括没有官能基的分子。n的特定的优选实例包括1≥n>0,2≥n>1和n>2。n能够由13CNMR测定。为理想性能所需要的最佳官能基数目一般随聚合物的数均分子量的增大而增大。n的最大值将由未官能化聚合物中每一聚合物链的双键数来决定。
在特定和优选的实例中,“离去基团”(-YR3)的pKa值低于或等于12,优选低于10和更优选低于8。pKa是从相应的酸性物质HY-R3在水中于室温下测定的。当离去基团是简单的酸或烷基酯时,官能化的聚合物是非常稳定的,尤其随着%新(neo)取代的增加。本发明尤其可用来制造“新”官能化的聚合物,它一般比“异”结构更加稳定和不稳定。在一优选的实例中,聚合物能够被新官能化至少60摩尔%,更优选至少80摩尔%。在一个优选组成中,由通式(I)定义的聚合物中,Y是O(氧),R1和R2可以相同或不同,并选自H,烃基和聚合基团。
在另一优选实例中,Y是O或S,R1和R2可以相同或不同,并选自H,烃基,取代烃基和聚合基团,和R3选自取代的烃基,芳族基团和取代的芳族基团。这一实例一般对用胺和醇化合物进行衍生反应有更高的活性,尤其当R3取代基含有吸电子结构时。已经发现,在这一实例中,优选的离去基团,HYR3,具有pKa值低于12,优选低于10和更优选8或8以下。pKa值一般能够在5-12,优选6-10,和更优选6-8的范围内。离去基团的pKa值决定了该体系如何容易地与衍生化合物反应,形成衍生的产物。
在一个特别优选的组成中,R3由下式表示:其中X,可以相同或不同,是吸电子取代基,T,可以相同或不同,表示非吸电子取代基(例如给电子取代基),以及m和p是0-5,m和p之和是0-5。更优选地,m是1-5和更好是1-3。在一个特别优选的实例中,X是选自卤素,优选F或Cl,CF3,氰基和硝基,以及p=0。优选的R3是从2,4-二氯苯酚衍生而来的。
本发明的组合物包括衍生而来的聚合物,它是科赫官能化聚合物和衍生化合物的反应产物。优选的衍生化合物包括亲核反应物化合物,包括胺类、醇类、氨基醇类、金属反应物化合物和它们的混合物。衍生而来的聚合物一般含有至少一个以下基团:酰胺,酰亚胺,恶唑啉,和酯,以及金属盐。对于具体的最终用途的适合性可通过适当地选择聚合物Mn和在下文中所讨论的衍生聚合物中使用的官能度来改进。
科赫反应允许不饱和聚合物的受控官能化。当碳-碳双键的碳被氢取代时,将产生“异”官能基团,即通式(I)的一个R1或R2是H,或当双键的碳全部被烃基取代时,将会得到“新”官能基,即通式I的R1或R2是非氢基团。根据本发明的方法,由生产端部不饱和聚合物链的方法所得到的聚合物能够被官能化到较高的产率。已经发现“新”酸官能化的聚合物能够被衍生到较高的产率。科赫反应也可利用相对便宜的物质,即一氧化碳,在较低温度和压力下进行。也可在用胺类或醇类将科赫官能化的聚合物衍生时除去和回收离去基团-YR3。
本发明的官能化或衍生的聚合物可用作润滑添加剂,如分散剂,粘度改进剂和多功能粘度改进剂。
本发明包括含油组合物,该组合物包括上述官能化的,和/或衍生的聚合物。此类组合物包括润滑油组合物和浓缩物。
本发明还提供一种方法,它包括让以下物质的混合物进行催化反应的步骤:
(a)至少一种烃(聚合物),它的数均分子量为至少大约500,和每一聚合物链有平均至少一个烯属双键;
(b)一氧化碳,
(c)至少一种酸催化剂,和
(d)选自水,含羟基的化合物和含硫醇的化合物的亲核捕集剂,该反应按以下进行:a)在没有依靠作为催化剂的过渡金属的情况下;或b)用至少一种哈梅特酸度低于-7的酸催化剂;或c)其中在至少40摩尔%的烯属双键上形成官能基;或d)其中亲核捕集剂的pKa低于12。
本发明的方法涉及有至少一个烯属双键经过科赫机理反应形成了含羰基或含硫代羰基的化合物的烯烃/聚合物,它随后被衍生。该聚合物与一氧化碳在酸催化剂或优选与亲核捕集剂配合的催化剂存在下反应。优选的催化剂是BF3和优选的催化剂配合物包括BF3·H2O和与2,4-二氯苯酚配合的BF3。起始聚合物与一氧化碳在不饱和点反应形成异-或新-酰基,再与亲核捕集剂,例如与水、醇(优选取代的酚类)或硫醇反应,分别形成羧酸,羧酸酯基或硫代酯。
在优选的方法中,至少一种有至少一个碳-碳双键的聚合物与哈梅特标度酸值低于-7,优选-8.0--11.5和最优选-10--11.5的酸催化剂或催化剂配合物接触。不想受任何特殊理论的束缚,据信在一个碳-碳双键的部位可形成碳正离子。碳正离子然后与一氧化碳反应形成酰基阳离子。酰基阳离子与至少一种如上所定义的亲核捕集剂反应。
本发明的连续方法用粘性聚合物烯烃尤其理想。管式反应器不依赖湍流来提供混合作用,而是按照层流方式操作。在一个优选的实例中,乙烯/丁烯共聚物烯烃与气态官能化剂,优选一氧化碳和醇如2,4-二氯苯酚或其它合适的含羟基捕集剂在催化剂,优选BF3存在下进行反应,从减少的(与间歇操作相比)反应器体积以高产率生产酯产物。对于等量生产量的有害物质的低投料量,用气相反应物的循环进行自动操作,和更紧密密封的条件都减少了意外释放的机会。本发明的连续方法大大地减少了烷基化副反应;在高CO分压下,反应条件和停留时间能够加以控制,最大程度地减少苯酚的烷基化和其它副反应。对于本发明的一些实例,例如CSTR,稍高份额的一些组分降低粘度,进而促进CO气体更快速地溶解于混合物中,从而减少烷基化作用。因此,较高的亲核捕集剂/聚合物比例最大程度地减少烷基化作用。
至少40摩尔%,优选至少50摩尔%,更优选至少80摩尔%和最优选90摩尔%的烯烃/聚合物双键经过反应形成酰基,其中酰基的非羧基部分由亲核捕集剂的类别来确定,即水形成酸,醇形成酸酯和硫醇形成硫代酯。由所列举的本发明方法官能化的聚合物能够用氟化物盐来加以分离。氟化物盐能够选自氟化铵,和氟化钠。
优选的亲核捕集剂选自水,单羟基醇类,多羟基醇类,含羟基的芳族化合物和杂原子取代的酚类化合物。催化剂和亲核捕集剂能够单独地添加或经过混合形成催化剂配合物。下面是端部不饱和的聚合物经科赫机理反应形成酸或酯的实施例。聚合物与一氧化碳或合适的一氧化碳源如甲酸在酸性催化剂存在下接触。催化剂为碳-碳双键提供质子,形成碳正离子。随后添加CO形成酰基正离子,它再与亲核捕集剂反应。POLY,Y,R1,R2和R3如上所定义。(碳正离子)(酰基正离子)
科赫反应尤其可用来将通过使用金属茂型催化剂制得的聚(α-烯烃)和乙烯-α-烯烃共聚物官能化。这些聚合物含有端部亚乙烯基。这一端部基团趋向于占主导地位并得到新-类(叔)碳正离子。为了形成碳正离子,酸催化剂优选是较强的。然而,优选的是酸催化剂的强度需要平衡,以防止有害副反应的发生,该反应在酸太强时发生。科赫催化剂是通过用所建议的亲核捕集剂预先制备催化剂配合物或通过将催化剂和捕集剂单独加入到反应混合物中来使用的。该后一实例已发现特别有利,因为它消除了制造催化剂配合物的步骤。下面是合适的酸性催化剂和催化剂配合物物质的例子,及它们各自的哈梅特标度酸值:60%H2SO4,-4.32;BF3·3H2O,-4.5;BF3·2H2O,-7.0;WO3/A12O3,低于-8.2;SiO2/A12O3,低于-8.2;HF,-10.2;BF3·H2O,-11.4;-11.94;ZrO2,低于-12.7;SiO2/Al2O3,-12.7--13.6;AlCl3,-13.16--13.75;AlCl3/CuSO4,-13.75--14.52。
已经发现,BF3·2H2O在通过科赫机理离子将聚合物官能化时对聚合物类无效。相反,BF3·H2O对于同样的反应得到高产率的羧酸。H2SO4作为催化剂的使用包括酸浓度的控制,来达到所需要的哈梅特标度值范围。优选的催化剂是H2SO4和BF3催化剂体系。用于本发明中的合适的BF3催化剂配合物可由下式表示:
BF3·xHOR其中R代表氢,烃基(与下面对于R′的定义一样),-CO-R′,-SO2-R′,-PO-(OH)2,和它们的混合物,其中R′是烃基,典型地烷基,例如C1-C20烷基,和例如C6-C14芳基,芳烷基和烷芳基,和x是小于2。
与CO反应后,反应混合物进一步与水或另一种亲核捕集剂如醇或酚类,或硫醇化合物反应。水的使用使催化剂释放出来形成酸。羟基捕集剂的使用是催化剂释放出来,形成酯,硫醇的使用释放催化剂形成硫代酯。
科赫产物,下面也称作官能化聚合物,典型地按照下文所述加以衍生。酯官能化的聚合物的衍生反应一般将从聚合物中置换出醇衍生的部分。因此,科赫官能化聚合物的醇衍生部分有时称作离去基团。在衍生反应过程中离去基团被置换的容易程度将取决于它的酸性,即酸性越高置换越容易。按醇计算的酸性以它的pKa表示。
优选的亲核捕集剂包括水和含羟基的化合物。有用的羟基捕集剂包括脂族化合物类,如单羟基和多羟基醇类或芳族化合物类,如酚类和萘酚类。芳族羟基化合物(从它可衍生出本发明的酯)可由下面的特定的实例来说明:苯酚,萘酚,甲苯酚,间苯二酚,儿茶酚,2-氯苯酚。特别优选的是2,4-二氯苯酚。
醇类优选含有至多大约40个脂族碳原子。它们可以是单羟基醇类,如甲醇,乙醇,苄基醇,2-甲基环己醇,β-氯乙醇,乙二醇的单甲基醚,等等。多羟基醇类优选含有2-约5个羟基;例如乙二醇,二甘醇。其它有用的多羟基醇类包括甘油,甘油单甲基醚,和季戊四醇。有用的不饱和醇类包括烯丙基醇和炔丙基醇。
特别优选的醇类包括具有通式R* 2CHOH的那些醇类,其中R*独立地是氢,烷基,芳基,羟烷基,或环烷基。特定的醇类包括链烷醇类,如甲醇和乙醇等。也优选的有用醇类包括芳族醇类,酚类化合物和多羟基醇类以及单羟基醇类如1,4-丁二醇。已经发现新-酸酯官能化的聚合物是极其稳定的,据信这归因于空间位阻。因此,从它获得的衍生聚合物的产率将根据衍生化合物置换官能化聚合物的离去基团的容易程度来变化。
最优选的醇捕集剂可通过用至少一个吸电子取代基取代苯酚来获得,以使取代的苯酚所具有的pKa在以上描述的优选pKa范围内。还有,苯酚也可以被至少一个非吸电子取代基(例如给电子取代基)取代,优选在吸电子取代基的间位,以便在科赫反应过程中阻断不需要的聚合物对苯酚的烷基化反应。这进一步改进了所需酯官能化聚合物产率。所以,和鉴于上述原因,最优选的捕集剂是酚类和由下式表示的取代酚类化合物:其中X,可以相同或不同,是吸电子取代基,和T,可以相同或不同,是非吸电子取代基;m和p是0-5,m和p之和是0-5,m优选是1-5,和更优选m是1或2。X优选是选自卤素,氰基和硝基的基团,优选位于2-和/或4-位,和T是选自烃基和羟基的基团,和p是1或2,T优选位于4-和/或6-位。更优选地,X是选自Cl,F,Br,氰基或硝基,和m优选是1-5,更优选1-3,再进一步优选1-2,和最优选2,位于相对于-OH的2-和4-位。
反应物和催化剂的相对用量,和各条件按照足以使最初存在于未官能化聚合物中的碳-碳双键的至少约40%,优选至少约80%,更优选至少约90%和最优选至少约95摩尔%官能化的这样一种方式来控制。
水,醇或硫醇的用量优选是与酰基正离子反应所需要的至少化学计量的量。优选使用比化学计量过量的醇。该醇具有作为反应的反应物和稀释剂的双重作用。然而,醇或水的用量应该足以提供所需要的产率,而同时不致于将酸催化剂稀释到不利地影响哈梅特标度值酸度的程度。
聚合物能够以液相形式加入到反应体系中。任意性地,聚合物能够溶于惰性溶剂中。在反应完成之后通过分离含有酰基的聚合物分子(它是极性的,因而容易与来反应的非极性化合物分离)来确定产率。通过使用现有技术中已知的吸附技术来进行分离操作。能够由13C NMR技术测定初始碳-碳双键和反应后保留的碳-碳双键的量。
根据该方法,聚合物被加热到所需要的温度范围,一般是在-20℃至200℃之间,优选0℃至80℃和更优选40℃至65℃之间。通过安装在反应器中的加热和冷却装置来控制温度。由于反应是放热反应,通常需要冷却装置。在整个反应过程中进行混合,确保反应介质均匀。对于本发明的连续方法,合适的操作温度范围是0-100℃,较好地40-80℃和优选55-100℃。对于更加粘稠的反应混合物,至少约80℃的温度是有效的。
催化剂(和亲核捕集剂)能够预先反应制成催化剂配合物,或在所需温度和压力下,优选在氮气气氛下以一步单独加入到反应器中就地形成催化剂配合物。在一个优选的体系中,亲核捕集剂是与BF3混合使用的取代苯酚。反应器内容物连续进行混合,然后通过使用高压一氧化碳源快速调节到所需操作压力。有用的压力是高达138,000kPa(20,000磅/英寸2),和典型地是至少2,070kPa(300磅/英寸2),优选至少5,520kPa(800磅/英寸2),和最优选至少6,900kPa(1,000磅/英寸2),典型地是在3,450-34,500kPa(500-5,000磅/英寸2),优选4,485-20,700kPa(650-3,000磅/英寸2)和最优选4,485-13,800kPa(650-2000磅/英寸2)。通过添加催化剂如铜化合物能够降低一氧化碳的压力。催化剂与聚合物的体积比可以在0.25-4,优选0.5-2和最优选0.75-1.3范围内。对于本发明的连续方法,这一比例可以是0.05-4.0,较好0.10-2,尤其0.20-1.5。
优选地,聚合物,催化剂,亲核捕集剂和CO在单一的步骤中加入到反应器中。反应器内容物然后在一氧化碳压力下保持所需时间。反应时间至多为5小时,典型地为0.5-4小时和更典型地为1-2小时。反应器内容物然后被排出和所得产物是分离出来的科赫官能化聚合物,它包括羧酸或羧酸酯或硫醇酯官能基。排料时任何来反应的CO可排空。氮气可用来冲洗反应器和接收聚合物的容器。
在本发明的优选的连续方法中,反应物通过泵或压缩机供给该方法,并刚好在进入反应器、CSTR或管之前或之后一起混合。随着反应的进行,气相反应物如BF3和一氧化碳溶入液体中。在反应器出口进行闪蒸,使大部分BF3催化剂和来消耗的CO从液相中释放出来并加以循环。第二步分离可用来除去和循环多余的亲核捕集剂/含羟基捕集剂如醇类,例如2,4-二氯苯酚。
在CSTR型反应器构造中,液相和气相反应物被加入到单级反应器中,该反应器装有机械搅拌器以促进液体/气体接触和在整个反应器中提供均匀的浓度。本发明的CSTR构造可以使用一个以上的串联的反应器/级,尽管单级简单一些和便宜一些。多级可用来减少总体积和停留时间。在管式反应器中,串联的各混合机以一定的间隔设置,以促进液体/气体在没有机械密封的情况下在最低总体积构造中进行接触。串联混合机可以是静态或机械类型的(包括有外部驱动的叶轮的那些)。这些混合机能够有效地以在混合机之间0.25-5分钟,较好0.25-3分钟,尤其0.5-1.5分钟范围内的停留时间间隔设置。混合机之间的内部是从反应器的入口到出口增加。每一个混合机使液体均匀地混合并将气泡分散成尺寸为0.01-3mm,较好0.1-2mm,尤其0.1-1mm。混合机强度朝反应器出口方向被削弱,因为主要在反应器前部要求高速的气体/液体接触(尽管在出口处需要均匀地掺混)。所以,在管式反应器的前面优选气体分散混合机和在反应器的后端优选掺混型混合机。Sulzer SMV静态混合机是气体/液体接触的合适混合机。可以设计出混合机,它使反应器中气泡尺寸和分布最佳化。较大的设备需要较大的混合机。每一个混合机具有一系列的元件,如劈开/再混合装置,典型地有4个,它将料流劈开和再混合几次。本发明的优选的连续方法包括层流方法,其中雷诺数是非常低的,优选低于10,并使用静态混合机将气体分散入液体和促进反应。混合机之后接着开路管道(open pipe),它为反应提供停留时间。
管式反应器方法也是有利的,因为它不需要液面控制,具有简单的控制和操作,具有短的反应时间,获得高的产率,最大程度地提高固有安全性;和允许使用大范围的聚合物粘度。与间歇方法相比而言,本发明的连续方法还提供了非常洁净的、白色的产物,尤其避免暴露于空气和氧气。
取决于所用的具体的反应物,含有官能化聚合物的反应混合物可以是单相的,可分离聚合物和酸相的混合物,或者聚合物相或酸相是连续相的乳液。反应完成之后,聚合物通过合适的装置回收。在一些情况下,有必要在回收产物之后快速分离或中和催化剂组分,以避免所需要的酯产物转变到起始原料或其它副产物(例如快速降低压力和提高温度促进BF3释放;或用过量的离去基团或中和剂终止。当混合物是乳液时,合适的方法可用来分离聚合物。优选的方法是使用氟化物盐,如氟化钠或铵与醇如丁醇或甲醇的混合物来中和催化剂和使反应混合物发生相分离。氟离子有助于捕集配合到官能化聚合物上的BF3和有助于破裂所产生的乳液(当粗产物用水洗涤时)。醇类如甲醇和丁醇和商品破乳剂也有助于破乳,尤其与氟离子结合。优选地,亲核捕集剂与氟化物盐和醇类(当用来分离聚合物时)混合。亲核捕集剂作为溶剂的存在最大程度地减少了官能化聚合物的酯基转移作用。
当亲核捕集剂所具有的pKa低于12时,通过减压和蒸馏,官能化聚合物能够与亲核捕集剂和催化剂分离。已经发现,当亲核捕集剂具有低的pKa值时,催化剂,即BF3,从反应混合物中释放更容易。
正如以上所指出的,经历了科赫反应的聚合物也称作官能化聚合物。因此,官能化聚合物包括已经由至少一个官能基化学改性的分子,这样,官能化聚合物(a)能够进行其它化学反应(例如衍生反应)或(b)具有所需要的性能,它不为没有此种化学改性的单独聚合物所具有。
从通式I的讨论可以看出,官能基的特征是它可由括号内的表达式表示:该表达式含有酰基
,应该明白,尽管部分在从单独的反应物衍生而来的意义上没有加到聚合物上,但仍然是指官能基的一部分,以便讨论和描述。严格地讲,正是酰基构成官能基,因为正是这一基团在化学改性中加上去了。而且,R1和R2表示最初存在于桥接官能化前的双键的两个碳原子上的基团或其构成部分。然而,R1和R2被包括在括号内,这样,在取决于R1和R2类别的通式中,新酰基能够区别于异酰基。
典型地,聚合物的最终用途是用于制造分散剂,例如作衍生的聚合物时,该聚合物将具有下面所要定义的分散剂范围的分子量(Mn),和官能度典型地显著低于用来制造衍生的多官能度V.I.改进剂的聚合物,其中该聚合物具有下面所要定义的粘度改进剂范围的分子量(Mn)。
因此,尽管能够使想要用于随后的衍生反应的官能化聚合物具有有效的官能度,还是希望对于分散剂最终应用的这一官能度,表达为F,一般不高于约3,优选不高于约2,并且典型地在约0.5-约3范围内,优选0.8-约2.0(例如0.8-1)。类似地,对于衍生的聚合物的粘度改进剂最终应用的有效官能度F希望典型地高于约3,优选高于约5,和典型地在5-约10范围内。极高分子量的聚合物的最终应用需要这样的官能度:它典型地高于约20,优选高于约30,和最优选高于约40,和典型地在20-60,优选25-55和最优选30-50范围内。
适合于说明的带夹套的管式反应器和相关的装置说明如下。聚合物和亲核捕集剂如2,4-二氯苯酚在进料罐2中进行混合并由泵4连续导入反应器6中。CO和催化剂,合适的是BP3气体,作为补充料流提供,通过物料流控制器8和10,供到循环气体管道12,压缩机14,和物料流控制器16,到达主进料管道18。反应器6具有一系列的有绝热夹套22的管道20。第一批8根管道具有两个按图上所示设置的静态混合机24和第二批8根管道中每根管道仅仅有一个静态混合机24(如图中所示)。反应器6可以从图中所示位置颠倒过来提供不同的混合型式(profile),但仍然按照有夹带气体的层流方式操作。
反应物料流过闪蒸鼓26和28,为管道12提供循环气体,而亲核捕集剂,较好2,4-二氯苯酚,通过使用真空和加热在30处收集。由泵32推动产物,优选通过刮擦式薄膜蒸发器34在36处分离轻馏分和在鼓38中收集产物,优选酯。这一描述并不适合于所有的操作。亲核捕集剂,如2,4-二氯苯酚,和聚合物/烯烃可以单独加入并在导入气体之后掺混。调节夹套来保持所需要的温度分布(profile)。温度也可由以下方法控制:预冷原料和让反应热使温度升高;预热原料,例如100℃,和使用冷却夹套。优选地,温度在整个反应器中保持在优选的范围内,在前半部分,优选反应器长度的第一个四分之一,达到所需要的温度。可以使用增强的热转移装置,如含有静态混合机元件的带夹套的管来提高热转移系数(反应物料进行混合)或带有内部冷却膜(veil)的管来提供更大的表面积和热转移系数(例如Sulzer SMR混合机/换热器)。
USSN 261,507,代理登记号(Attorney Docket Number)PT-1143,酯官能化聚合物的酰胺化;USSN 261,557,代理登记号PT-1144,用来改进科赫反应分散添加剂的预汽提聚合物;USSN 261,559,代理登记号PT-1145,间歇式科赫羰基化方法;USSN 261,534,代理登记号PT-1146,聚胺与一种伯胺和仲或叔胺类的衍生物;USSN 261,554,代理登记号PT-1150,从重质聚胺衍生而来的润滑油分散剂;和USSN 261,558,代理登记号PT-1151,可用于二冲程发动机的官能化添加剂,全部在1994年6月17日申请,全部含有由它们的标题指定的相关主题物质,因而它们全部被引入本文供参考。
衍生的聚合物
如果官能基含有所需极性基团,则官能化聚合物能够用作分散剂/多官能度粘度改进剂。该官能基还能够使聚合物参与各种化学反应。通过官能基的反应能够形成官能化的聚合物的衍生物。这些衍生的聚合物对于各种用途如用作分散剂和粘度改进剂来说具有所需性能。衍生的聚合物是经过化学改性而以相对于未官能化聚合物和/或官能化聚合物来说显著改进的方式发挥一种或多种作用的聚合物。这类作用的代表是在润滑油组合物中的分散性和/或粘度改进作用。
衍生化合物一般含有至少一个反应活性的衍生基团,该基团被选择来与由各种反应加以官能化的聚合物的官能基团进行反应。这类反应的代表是亲核取代反应,酯基转移反应,成盐反应,和类似反应。衍生化合物优选也含有至少一个适合于赋予衍生的聚合物以所需性能的附加基团,例如极性基团。因此,这一衍生化合物典型地含有一个或多个基团,包括胺,羟基,酯,酰胺,酰亚胺,硫代,硫代酰胺基,噁唑啉,或羧酸酯基或者在衍生反应完成之后形成此类基团。
衍生的聚合物包括以上列举的官能化聚合物与亲核反应物(包括胺类,醇类,氨基醇类和它们的混合物)的反应产物,形成油溶性盐类,酰胺类,噁唑啉和酯类。此外,官能化聚合物能够与碱性金属盐反应形成聚合物的金属盐。优选的金属是Ca,Mg,Cu,Zn,Mo和类似金属。赋予衍生的聚合物的合适性能包括分散性,多官能度粘度改进作用,抗氧化性,摩擦改进作用,抗磨性,防锈作用,密封膨胀性(seal swell)等中的一种或多种。赋予衍生的聚合物的优选性能包括分散性(单-和多-官能度)和主要具有附加的次要分散性能的粘度改进作用。多官能度分散剂典型地主要用作具有附加的次要的粘度改进作用的分散剂。
尽管用来制备多官能度粘度改进剂(也称作多官能度粘度指数改进剂或MFVI)的科赫官能化和衍生技术与无灰分散剂的相同,但用于衍生反应和最后用作MFVI的官能化聚合物的官能度将被控制高于最终用作分散剂的官能化聚合物。这归因于MFVI聚合物骨架的Mn与分散剂聚合物骨架的Mn的区别。因此,希望MFVI从官能化聚合物衍生而来,该聚合物对于骨架聚合物中每20,000,优选每10,000,最优选每5,000Mn分子量片段来说一般具有至多约一个和至少约0.5个官能基团(即通式I中的“n”)。
分散剂将从油的使用得到的油不溶物保持在流体的悬浮液中,从而防止淤渣絮凝和沉淀。合适的分散剂包括,例如,产生灰分的分散剂(也已知为洗涤剂)和无灰分型分散剂,后者是优选的。本发明的衍生的聚合物组合物能够用作润滑油和燃料组合物中的无灰分散剂和多官能度粘度指数改进剂。
至少一种官能化聚合物与胺,醇(包括多元醇),氨基醇等当中的至少一种混合,形成分散添加剂。一类特别优选的分散剂是从本发明的官能化聚合物与(i)羟基化合物,例如多羟基醇或多羟基取代的脂族伯胺如季戊四醇或三羟甲基氨基甲烷,(ii)聚氧化亚烷基多胺,例如聚氧丙烯二胺,和/或(iii)聚亚烷基多胺,例如聚亚乙基多胺如四亚乙基五胺(这里称作TEPA)的反应衍生而来的那些。
用于将官能化聚合物衍生的有用的胺类化合物包括至少一种胺和包括一种或多种附加的胺或其它的反应活性的或极性的基团。当官能基是羧酸,羧酸酯或硫代酯时,它与胺反应形成酰胺。优选的胺类是脂族饱和胺类。合适的胺类化合物的非限制性实例包括: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,聚亚乙基胺类如二亚乙基三胺,三亚乙基四胺,四亚乙基五胺,等。
其它有用的胺类化合物包括:脂环族二胺类,如1,4-二(氨基甲基)环己烷,和杂环氮化合物,如咪唑啉。使用胺类化合物的混合物是有利的。有用的胺类也包括聚氧化亚烷基多胺。特别有用的一类胺类是聚酰胺基化合物和相关的胺类。
本发明的官能化聚合物能够与醇反应形成酯。该醇类可以是脂族化合物,如单羟基和多羟基醇类或芳族化合物如酚类和萘酚类。芳族羟基化合物(从它可衍生出酯)可由下面的特定实例来说明:苯酚,β-萘酚,α-萘酚,甲苯酚,间苯二酚,儿茶酚,等。苯酚和具有至多三个烷基取代基的烷基化苯酚是优选的。醇类(从它可衍生出酯)优选含有至多40个脂族碳原子。它们可以是单羟基醇类如甲醇,乙醇,异辛醇等。有用的一类多羟基醇类是具有至少三个羟基的那些,其中一些已用具有约8-约30个碳原子的单羧酸,如辛酸、油酸、硬脂酸、亚油酸、十二烷酸或浮油酸加以酯化。
该酯类也可以从不饱和的醇类如烯丙基醇,肉桂醇,炔丙基醇衍生而来。能够得到本发明的酯类的另-类醇类包括醚-醇类和氨基-醇类,例如包括氧化亚烷基-,氧化亚芳基-,氨基-亚烷基-,和氨基-亚芳基-取代的、具有一个或多个氧化亚烷基,氨基-亚烷基,氨基-亚芳基或氧化亚烷基基团的醇类。它们可由溶纤剂,卡必醇,苯氧基乙醇,等等来例举。
根据普通的酯化或酯基转移技术,本发明的官能化聚合物与醇类反应。这通常包括让官能化聚合物与醇一起加热,任意性地在通常为液体的、基本上惰性的有机液体溶剂/稀释剂存在下和/或在酯基转移催化剂存在下。
有用的反应活性金属或反应活性金属化合物是与官能化聚合物形成官能化聚合物的金属盐或含金属配合物的那些化合物。金属配合物典型地是通过官能化聚合物与以上所讨论的胺类和/或醇类和也与配合物形成(complex-forming)反应物在胺化过程中或在胺化之后进行反应而获得的。配合物形成金属反应物包括硝酸盐,亚硝酸盐,卤化物,羧酸盐,等等。
本发明的合适的官能化聚合物能够与任何各衍生化合物如胺,醇,反应活性金属,反应活性金属化合物或任何这些化合物中两种或多种的任何混合物,即,例如,一种或多种胺类,一种或多种醇类,一种或多种反应活性金属或一种或多种反应活性金属化合物,或任何这些化合物的混合物,进行反应。基本上惰性的有机液体稀释剂可用来改善混合效果,温度控制和反应混合物的后处理。
由本发明的官能化聚合物与衍生化合物如醇类、含氮反应物、金属反应物和类似化合物的反应所生产的反应产物实际上是各种反应产物的混合物。官能化聚合物本身是各物质的混合物。尽管官能化聚合物本身具有一些分散特性并能够用作润滑油和燃料中的分散添加剂,但当至少约30,优选至少约50,最优选100%的官能基被衍生时获得最佳结果。
官能化和/或衍生的聚合物可以进行后处理。将衍生的聚合物进行后处理的方法类似于对于普通分散剂和现有技术中的MFVI所使用的后处理方法。所以,能够使用同样的反应条件,反应物比例等。所以,衍生的聚合物能够用诸如脲,硫脲,二硫化碳,醛类, 酮类,羧酸类,烃基取代的琥珀酸酐,腈类,环氧化物类,硼化合物类,磷化合物或类似化合物的反应试剂进行后处理。
如上所述的本发明的胺衍生的聚合物能够通过让所述聚合物与一种或多种后处理试剂,如硼化合物、氮化合物、磷化合物,氧化合物,琥珀酸和酸酐类(例如琥珀酸酐,十二烷基琥珀酸酐,和C1-C30烃基取代的琥珀酸酐),其它酸类和酸酐类如马来酸和富马酸和酸酐类,和以上所述酸的酯类如马来酸甲酯,接触进行后处理,尤其用作分散剂和粘度指数改进剂时。胺衍生的聚合物优选用氧化硼,卤化硼,硼酸酯类或硼酯(boron ester)进行处理,其用量足以为每摩尔的氮组分提供0.1-20.0原子比例(atomicproportions)的硼。可用作分散剂的硼化(borated)的衍生的聚合物能够含有0.05-2.0wt%,例如0.05-0.7wt%的硼,以该硼化的含氮分散剂化合物的总重为基础计。通过将所述硼化合物,优选硼酸,通常以淤浆的形式,加入到该氮化合物中和然后在约135℃-190℃,例如140℃-170℃下加热搅拌1-5小时,能够容易地进行处理。本发明的衍生的聚合物也能够用可聚合的内酯(如ε-己内酯)处理形成分散加合物。
科赫官能化聚合物,除了用作制造分散剂和MFVI的中间体以外,还能够用作脱模剂,模塑剂,金属加工润滑剂,点增稠剂(point thickener)和类似物。本发明产物,从官能化聚合物一直到后处理过的衍生的聚合物,的主要用途是作为含油组合物的添加剂。
本发明的添加剂通过引入含油物质如燃料和润滑油中来利用。燃料包括通常为液体的石油燃料,如沸点为65℃-430℃的中间馏分,包括煤油、柴油燃料、家用加热燃料油,喷气式发动机燃料,等等。添加剂在燃料中的浓度通常是在0.001-0.5wt%,优选0.005-0.15wt%范围内,以组合物的总重为基础计。
本发明的添加剂可用于润滑油组合物中,它使用基油,添加剂溶于或分散于其中。这类基油可以是天然的或合成的。适合用来制备本发明的润滑油组合物的基油包括常常用作火花点火和压缩点火式内燃发动机,如汽车和卡车发动机,船舶和铁路柴油发动机等的曲轴箱润滑油的那些。通过在常常用于和/或用作动力传递液、通用拖拉机液体和液压用液体、重载液压用液体、动力转向液体和类似液体的基油中使用本发明的添加剂混合物也获得有利的结果。齿轮润滑油,工业用油,泵油和其它润滑油组合物也能够从引入本发明的添加剂受益。
天然油包括动物油和植物油(例如蓖麻油,猪油),液体石油以及链烷烃、环烷烃和混合链烷烃-环烷烃类型的加氢精制的,溶剂处理过的或酸处理过的矿物润滑油。从煤或页岩衍生而来的润滑粘度油也是有用的基油。
合成润滑油包括烃油类和卤素取代的烃油类,如聚合的和共聚合的烯烃(例如聚丁烯类,聚丙烯类,丙烯-异丁烯共聚物,氯化聚丁烯等)。端羟基通过酯化、醚化等改性的烯化氧聚合物和共聚物及其衍生物是另一类已知的合成润滑油。另一类合适的合成润滑油包括二羧酸的酯类。可用作合成油的酯类也包括从C5-C12单羧酸和多元醇以及多元醇醚如新戊二醇等得到的那些酯类。基于硅的油如多烷基-,多芳基-,多烷氧基-或多芳氧基硅氧烷油类和硅酸酯油类属于另一类有用的合成润滑油。未提炼的,提炼的和再提炼的油类能够用于本发明的润滑剂中。
本发明的添加剂,尤其用作分散剂或粘度改进剂的那些,能够以任何方便的方式引入润滑油中。因此,它们能够通过分散在油中或溶于油中而直接加入到油中。掺入到另外的润滑油中的操作能够在室温下或升高的温度下进行。此外,添加剂可以首先制成浓缩物,然后掺混入油中。这类分散剂浓缩物典型地含有在基油中作为活性成分(A.I.)的10-80wt%,典型地20-60wt%和优选40-50wt%的添加剂(以浓缩物重量为基础计)MFVI浓缩物通常含有5-50wt%AI。
本发明的添加剂可以与选择来发挥至少一种所需作用的其它添加剂混合。典型的这类附加的添加剂是洗涤剂,粘度改进剂,抗磨损添加剂,氧化抑制剂,腐蚀抑制剂,改善摩擦添加剂,泡沫抑制剂,防锈剂,破乳剂,抗氧化剂,润滑油流动改性剂,和密封膨胀控制剂。
组合物,当含有这些添加剂时,典型地以能够有效提供它们的正常作用的量掺混入基油中。此类添加剂的代表性有效量说明如下:
(宽的范围) (优选的范围)组分 wt% wt%V.I.改进剂 1-12 1-4腐蚀抑制剂 0.01-3 0.01-1.5氧化抑制剂 0.01-5 0.01-1.5分散剂 0.1-10 0.1-5润滑油流动改进剂 0.01-2 0.01-1.5洗涤剂和防锈剂 0.01-6 0.01-3倾点下降剂 0.01-1.5 0.01-1.5消泡剂 0.001-0.1 0.001-0.01抗磨损剂 0.001-5 0.001-1.5密封膨胀剂 0.1-8 0.1-4摩擦改性剂 0.01-3 0.01-1.5润滑基油 平衡量 平衡量
当使用其它添加剂时,需要(尽管不是必须的)制备添加剂的浓缩物或包装物,它们包含本发明的主题添加剂与一种或多种所述其它添加剂的浓缩溶液或分散液。由溶剂和通过混合及附带温和的加热(但不是必要的)有利于添加剂浓缩物溶于润滑油。最终的配制剂典型地使用2-20wt%,例如约10wt%的添加剂包装物,剩余物是基油。所有在本文中表达的重量百分数(除非另有说明)是以各添加剂的活性成分(A.I.)含量,和添加剂包装物或配制剂的总重量(包括全部油或稀释剂的重量)为基础。
实施例
组合物的份数和百分数是按重量计算的,除非另有说明。所有的分子量Mn是数均分子量。
连续方法实施例A
在73℃和12,420kPa(1800磅/英寸2)的稳定状态下进行CSTR方法。将Mn为3850和25wt%乙烯含量的乙烯/丁烯(EB)共聚物以35kg/hr的速度加入到反应器中,同时2,4-二氯苯酚单独地以11.8摩尔/摩尔EB共聚物添加。混合CO和BF3气体通过循环压缩机和补充供料管(若需要)进料以在反应器的气相空间中保持8722kPa(1264磅/英寸2)CO分压和3698kPa(536磅/英寸2)BF3分压。这一方法在41%全液面高度(full liquidlevel)以及16.3分钟的停留时间下进行操作,获得91%活性成分产率(由红外技术(IR)测得)。改变压力,反应物,温度和流速得到类似的结果,转化率高达91%活性成分。
连续方法实施例B
在具有串联的16根4.27米(14英尺)长、2.032cm(0.8英寸)内径的带夹套管的管式反应器中进行该连续方法。第一批8根管具有0.5英寸(1.27cm)Sulzer SMV-DY静态混合机,在入口处和每一管长度的一半处有1/16英寸(1.5mm)的板隔开。每一个混合机具有四个混合元件。第二批8根管在每一管的“入口”端具有单个静态混合机。反应器可以反向进行操作,如果需要,以让反应物首先通过有单个混合机的8根管。
在原料罐中实施例A的聚合物与2,4-二氯苯酚按1∶6摩尔比混合并在反应器温度75℃下以37.5kg/hr的速度加入到管式反应器中。循环一氧化碳和BF3(0.26摩尔BF3/摩尔CO)在12,420kPa(1800磅/英寸2)总压的入口压力下加入到反应器中,提供初始的气体/液体体积(60%体积的液体)。稳定状态的操作获得88.8%的转化率,由IR估测,得到非常洁净的、白色的产物酯。
实施例1-13
羧酸基团的产率(实施例1-5)
实施例1(对比)
溶于36.2份正庚烷(nC7)的34.5份聚正丁烯聚合物(PNB)(Mn=550)被投入到压力釜中,混合和加热到50℃。然后加入662份BF3二水合物(BF3·2H2O),随后立即通CO,它使总的压力釜压力升高到1500磅/英寸2。混合物然后在该温度和压力下搅拌3小时。释放压力,和反应产物用大量的水和丁醇洗涤,使聚合物相从酸相游离出来。聚合物在烘箱中干燥。所生产的聚合物的分析结果显示出转化成羧酸基团的转化率低于5%。
实施例2
重复实施例1中所述的方法,只是37.1份PNB(Mn=550)溶于40.2份nC7,和690份BF3.2H2O代替BF3.2H2O并通过将BF3鼓泡通入BF3·2H2O,一直到足够的BF3被吸附得到所需组合物为止来制备。用CO调节压力至2000磅/英寸2。最终产物的分析显示出聚合物转变成新-羧酸的转化率为85%。
实施例3
按照实施例1中所述操作程序,只是203.6份乙烯-丙烯(EP)共聚物(Mn=1800,和约50wt%乙烯)和159.9份nC7,和34份BF3·1.1H2O代替反应物投料。用CO将压力升高至2000磅/英寸2。转变成新-羧酸的转化率是56%。
实施例4
按照实施例1的操作程序,只是使用803份乙烯-丁烯(EB)共聚物(Mn=3700,约45wt%乙烯),568份异辛烷,和670份BF3·1.1H2O。用CO将压力升高至2000磅/英寸2。将反应产物加入到含有600份氟化钠(NaF),756份水,302份己烷,和50份丁醇的水溶液中。容易地从水相分离出来的聚合物产物被回收并干燥。分析显示出转变成新-羧酸的转化率为85.1%。
实施例5
按照实施例4中所述操作程序,只是使用543份丙烯-丁烯(PB)共聚物(Mn=2800,和约30wt%丙烯),454份异辛烷,和659份BF3·1.1H2O。将反应产物加入到600份氟化钠(NaF),945份水和302份己烷中。最终产物的分析显示出转变成新-羧酸的转化率为75.4%。实施例1-5的结果总结在下表1中:
表1实施例 聚合物 Mn 催化剂配合物 产率(%)对比1 PNB 550 BF3·2H2O 5
2 PNB 550 BF3·1.2H2O 85
3 EP 1800 BF3·1.1H2O 56
4 EB 3700 BF3·1.1H2O 85.1
5 PB 2800 BF3·1.1H2O 75.4
烷基酯(实施例6-12)
实施例6(对比)
按照实施例1中所述操作程序,只是使用1119.2份PNB(Mn=550)(没有溶剂),和350份BF3·二丁醇(将BF3气体鼓泡通入正丁醇中制得)。用CO将压力升高至2000磅/英寸2。最终产物的分析显示出转变成新-烷基酯的转化率低于5%。
实施例7
按照实施例1中所述操作程序,只是在本配方中使用153.3份EP聚合物(Mn=900,约50wt%乙烯)和137.9份nC7,和88份BF3·单丁醇。聚合物被干燥,转变成新-烷基酯的转化率是86%。
实施例8
按照实施例4中所述操作程序,只是使用143份PNB(Mn=550)(没有溶剂),和37份BF3·单甲醇(将BF3气体鼓泡通入甲醇中制得)(BF3·CH3OH)。将反应产物加入到230份氟化铵和765份甲醇中。转变成新-甲基酯的转化率是91.3%。
芳基酯
实施例9
按照实施例1中所述操作程序,只是使用440份PNB(Mn=550)(没有溶剂),和244份BF3·四(4-氯苯酚)。通过将BF3气体鼓泡通入熔化的4-氯苯酚中制得BF3配合物。用CO将压力釜升压至1485磅/英寸2,反应在55℃下保持2小时。分析显示出以下结果:
转变至4-氯苯基新-酯/酸的产率=60%聚合物
至烷基苯基酯 =1.1.7%聚合物
至烷基苯酚 =10.1%聚合物
总产率 =81.8%聚合物被转化
实施例10
(催化剂配合物)
通过向熔化的4-氯苯酚鼓泡通入BF3制得BF3与4-氯苯酚的配合物。为了增强BF3气体的吸收来产生BF3·二(4-氯苯酚),冷却溶液。几分钟后,溶液固化。将配合物熔化,快速释放出BF3。
(羰基化)
在30℃下将391磅/英寸2的BF3气体加入到压力釜中,随后另外用118磅/英寸2的CO升压至约500磅/英寸2的总压力。在搅拌压力釜的同时,440份PNB(Mn=550)和108份3-氟苯酚的混合物加入到反应器中,压力用CO升高至1500磅/英寸2,和温度升高至50℃。在这些条件下将反应保持2小时,然后压力釜解压。反应产物被汽提除去BF3气体和多余的取代苯酚。最终产物的分析显示出91.5%的产率。
实施例11
按照实施例10中所述操作程序,只是在50℃下压力釜用BF3升压至199磅/英寸2,随后用301磅/英寸2的CO,将总压力升高至500磅/英寸2,然后将406份EB共聚物(Mn=4600,20wt%乙烯)和100.6份2,4-二氯苯酚(pKa=7.85)在50℃下加入到压力釜中,并用CO升压至1430磅/英寸2。产率是84.5%。
实施例12
按照实施例10中所述操作程序,只是在50℃下压力釜用BF3升压至254磅/英寸2,随后用254磅/英寸2的CO,将总压力升高至508磅/英寸2,然后将110份EB聚合物(Mn=2200,约50wt%乙烯)和31份二氯苯酚(pKa=7.85)在50℃下加入到压力釜中,并用CO升压至2000磅/英寸2。转化率是85.4%。实施例6-9和10-12的结果总结在下表2中:
表2实施例 聚合物 Mn 催化剂配合物 产率(%)对比6 PNB 550 BF3·二丁醇 5
7 EB 900 BF3·单丁醇 86
8 PNB 550 BF3·单甲醇 91.3
9 PNB 550 BF3·四(4-氯苯酚) 81.8
10 PNB 550 *BF3+3-氟苯酚 91.5
11 EB 4600 *BF3+2,4-二氯苯酚 84.5
12 EB 2200 *BF3+二氯苯酚 85.4
*催化剂和酚类化合物以一步单独添加。
实施例13-17
PNB-新羧酸与PAM的胺化反应
实施例13
在搅拌下,将200份由类似于实施例2的方法制得的PNB新羧酸和31.2份的每分子平均有5-8个氮的聚(亚乙基胺)(PAM)加入到反应器中。反应器内容物用氮气吹扫。密封反应器和用氮气将压力升高至60磅/英寸2。反应器被加热至240℃并保持5小时。内容物用氮气经浸管和顶部排气管道鼓泡吹扫,然后冷却到30℃。羧酸酰胺的产率由13C NMR测得是45.4%。
实施例14
将溶于700份庚烷中的374份实施例4的新酸官能化的EB共聚物加入到反应器中。溶液在混合下加热至90℃。然后,缓慢地将70份亚硫酰氯加入到溶液中,再添加300份庚烷。在反应成酰氯的反应结束之后,在常压下和用N2吹扫的情况下将溶液加热升温至100℃,随后经过高真空闪蒸除去反应副产物和庚烷。冷却酰氯产物。然后,将新鲜的、干燥的庚烷加到酰氯产物中。然后将酰氯产物加热到90℃。然后,将10份聚胺(PAM)和17.8份三乙基胺缓慢地加入到酰氯中。过滤反应混合物,多余的三乙基胺被汽提,生产出由红外分析所显示的胺化产物。
实施例15
将17.8份的实施例11的EB共聚物的2,4-二氯苯基酯加到反应器中。反应器内容物在混合下加热至80℃。然后,将0.442份聚胺(PAM)加入反应器中。反应器内容物然后经8小时的时间从150℃缓慢升温至220℃,同时让释放出来的二氯苯酚(pKa=7.85)回流。在完全转变成酰胺之后,用N2吹扫除去苯酚。将反应器内容物冷却至室温。13C NMR分析显示出酯到酰胺的定量的转化率。
实施例16
按照实施例15中所述的操作程序,只是20.2份实施例12的2,4-二氯苯基酯与0.954份PAM一起使用。13C NMR分析显示出酯到酰胺的定量的转化率。
实施例17
在混合下在反应器中,19.4份在实施例16中所述的胺化聚合物与10.0份基油混合并加热升温至140℃。然后,1.407份在基油中磨细的30%硼酸淤浆被缓慢地加入到反应器内容物中。在该温度下用N2吹扫反应器2小时,然后将另外的6.26份基油加到反应器中。反应器内容物被冷却至120℃,然后过滤。产物的分析显示出45%的活性成分水平(0.73%N,0.26%B)。
Claims (23)
1.一种生产官能化聚合物的方法,它包括让聚合烯烃和气体官能化剂连续反应和回收官能化的聚合物。
2.权利要求1的方法,在酸催化剂压力下进行反应。
3.权利要求1的方法,其中所述官能化剂包括一氧化碳。
4.权利要求1的方法,其中所述官能化剂进一步包括亲核捕集剂,由此该聚合烯烃被-CO-YR3官能化,其中Y是O或S,和R3是H或烃基。
5.权利要求4的方法,其中-YR3具有pKa<12。
6.权利要求4的方法,其中R3是烃基和回收的官能化聚合物是酯。
7.权利要求1的方法,它包括所述聚合烯烃在连续的搅拌釜式反应器中反应。
8.权利要求1的方法,它包括所述聚合烯烃在管式反应器中反应。
9.权利要求8的方法,其中所述管式反应器包括静态混合机。
10.权利要求8的方法,是以层流方式操作的。
11.一种连续官能化方法,包括让烯烃与一氧化碳和亲核捕集剂在酸催化剂存在下反应。
12.权利要求11的连续方法,其中所述烯烃是聚合烯烃。
13.权利要求11的方法,其中所述烯烃已被式-CO-YR3基团官能化,其中Y是O或S,和R3是H或烃基。
14.权利要求13的方法,其中R3是烃基和所述烯烃被官能化成酯。
15.权利要求11的方法,它是在连续的搅拌釜式反应器中进行。
16.权利要求15的方法,它是在基本上没有空气的情况下按稳态方式进行的,其中液面保持恒定。
17.权利要求11的方法,它是在管式反应器中进行的。
18.权利要求17的方法,它是在基本上充满液体的管道中按层流方式进行的。
19.权利要求18的方法,其中所述管式反应器包括静态混合机以增大气液界面。
20.生产羧化聚合烯烃的连续方法,包括让所述烯烃与一氧化碳和亲核捕集剂在酸催化剂存在下和在按层流方式操作的、基本上充满液体的管式反应器中进行反应,和回收羧化聚合物。
21.权利要求20的方法,其中所述管式反应器包括静态混合机以增大气液界面。
22.权利要求20的方法,其中所述酸催化剂是BF3和所述羧化聚合物被式-CO-YR3基团官能化,其中Y是O或S,和R3是烃基,因而所述羧化聚合物是酯。
23.气-液管式反应器方法,它按照层流方式操作,雷诺数低于10并包括让反应物料通过静态混合机,将气体分散入反应用的液体中。
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-
1994
- 1994-06-17 US US08/261,560 patent/US5650536A/en not_active Expired - Fee Related
-
1995
- 1995-06-14 ES ES95925254T patent/ES2123268T3/es not_active Expired - Lifetime
- 1995-06-14 DE DE69504668T patent/DE69504668T2/de not_active Expired - Fee Related
- 1995-06-14 JP JP8502449A patent/JPH10502106A/ja active Pending
- 1995-06-14 EP EP95925254A patent/EP0765348B1/en not_active Expired - Lifetime
- 1995-06-14 CA CA002190654A patent/CA2190654A1/en not_active Abandoned
- 1995-06-14 CN CN951936441A patent/CN1064973C/zh not_active Expired - Fee Related
- 1995-06-14 WO PCT/US1995/007557 patent/WO1995035325A1/en active IP Right Grant
- 1995-06-14 AU AU29443/95A patent/AU684206B2/en not_active Ceased
- 1995-06-14 BR BR9508039A patent/BR9508039A/pt not_active Application Discontinuation
- 1995-06-14 EP EP97202753A patent/EP0815935A3/en not_active Ceased
-
1999
- 1999-10-11 CN CN99121308A patent/CN1258664A/zh active Pending
Cited By (4)
Publication number | Priority date | Publication date | Assignee | Title |
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CN1900139B (zh) * | 2000-12-07 | 2012-11-14 | 奇派特石化有限公司 | 制造缩聚物的方法 |
CN103201250A (zh) * | 2010-11-12 | 2013-07-10 | 三菱瓦斯化学株式会社 | 新型羧酸酯化合物及其制造方法以及其香料组合物 |
US8829228B2 (en) | 2010-11-12 | 2014-09-09 | Mitsubishi Gas Chemical Company, Inc. | Carboxylate compound and method of producing the same and perfume composition thereof |
CN103201250B (zh) * | 2010-11-12 | 2015-08-05 | 三菱瓦斯化学株式会社 | 新型羧酸酯化合物及其制造方法以及其香料组合物 |
Also Published As
Publication number | Publication date |
---|---|
AU684206B2 (en) | 1997-12-04 |
DE69504668D1 (de) | 1998-10-15 |
EP0765348A1 (en) | 1997-04-02 |
BR9508039A (pt) | 1997-11-18 |
US5650536A (en) | 1997-07-22 |
EP0815935A3 (en) | 1999-06-16 |
DE69504668T2 (de) | 1999-01-28 |
EP0765348B1 (en) | 1998-09-09 |
JPH10502106A (ja) | 1998-02-24 |
WO1995035325A1 (en) | 1995-12-28 |
AU2944395A (en) | 1996-01-15 |
EP0815935A2 (en) | 1998-01-07 |
CA2190654A1 (en) | 1995-12-28 |
CN1064973C (zh) | 2001-04-25 |
CN1258664A (zh) | 2000-07-05 |
ES2123268T3 (es) | 1999-01-01 |
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