CN1032221C - 馏分燃料添加剂及含该添加剂的馏分燃料 - Google Patents
馏分燃料添加剂及含该添加剂的馏分燃料 Download PDFInfo
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Abstract
本发明发现含以下重复单元的数均分子量1000-20000聚合物可用作馏分燃料的低温流动改进剂,尤其是与基它添加剂并用。
Description
本发明涉及可用作燃料油流动改进剂的新聚合物以及加流动改进剂的油和燃料油组合物。
油和燃料油处于低环境温度下,会分离出蜡,若不加低温流动改进剂,就会影响流动性。蜡的性质取决于燃料的种类,本发明特别涉及可用来处理可沉积正链烷蜡而在不加添加剂时会形成堵塞燃料管道和过滤器的大块蜡的馏分燃料的添加剂。
本发明涉及含蜡馏分燃料,可用添加剂处理,该添加剂尺寸和结构特征特别适宜于馏分燃料冷却时形成的蜡晶体结晶,使添加剂在结晶过程中与这些蜡相互作用而形成细晶沉积蜡。
含石蜡矿物油温降低时,其流动性会降低。这种流动性丧失的原因是蜡结晶成块状晶,最终会形成海绵状物质,在其中捕集油。蜡晶体开始形成温度称为浊点,蜡阻止油倒出的温度称为倾点。但在这两个温度点之间,蜡晶体会堵塞过滤器和管道,致使柴油机和家用加热等***停止工作。添加剂改进低温操作性能的有效性可用CFPP和PCT等试验评价,其抑制浊点和起蜡点的能力也可确定。
长期以来,已知有各种添加剂可与蜡质矿物油混合而作为蜡晶体改性剂。这些组合物可改善蜡晶体的尺寸和形状并降低晶体间和蜡与油之间的结合力,从而使油保持低温流动性,有时还可改进浊点和倾点间的可滤性。
各种倾点抑制剂已见于文献,某些已投入工业应用。如US3048479建议用乙烯与1-5碳乙烯酯,如乙酸乙烯酯的共聚物作为燃料,尤其是加热油,柴油和喷气燃料倾点抑制剂。还已知以乙烯和高碳α—烯烃,如丙烯为基础的烃聚合倾点抑制剂。
US3961916建议用共聚物混合物控制蜡晶体尺寸,UK1263152建议用低度侧链共聚物控制蜡晶体尺寸。这两种体系可改善燃料经过过滤器能力,可用低温过滤堵塞点(CFPP)试验测定,因为与无添加剂时形成的块状晶不同,形成的针晶不会堵塞过滤器的孔,而是在过滤器上形成多孔滤饼,可使剩余流体流通。
还提出其它添加剂,如UK1469016建议用富马酸二正烷基酯和乙酸乙烯酯的共聚物,过去用作润滑油倾点抑制剂,现在建议用作共添加剂而与乙烯/乙酸乙烯酯共聚物一起用来处理高终沸点馏分燃料,以改进其低温流动性。。US3252771涉及16—18碳α—烯烃聚合物的应用,其中用三氯化铝/烷基卤催化剂使主要为正16—18碳α—烯烃混合物聚合而得该聚合物,可作为60年代早期美国所用宽沸点范围馏分燃料的倾点抑制剂。
还提出以烯烃/马来酸酐共聚物为基础的添加剂。如US2542542建议用烯烃,如十八碳烯与醇,如月桂醇酯化的马来酸酐的共聚物作为倾点抑制剂,UK1468588建议用22—28碳烯烃与二十二碳醇酯化的马来酸酐的共聚物作为馏分燃料的共添加剂。
同样,JP56—54037建议用烯烃/马来酸酐共聚物与胺反应后作为倾点抑制剂,JP56—54038又建议烯烃/马来酸酐共聚物的衍生物与常用中馏分流动改进剂,如乙烯/乙酸乙烯共聚物一起使用。
JP55—40640建议用烯烃/马来酸酐共聚物(未酯化),并指出所用烯烃应含20碳以上,以得到CFPP活性。
UK2129012建议用酯化烯烃/马来酸酐共聚物和低分子聚乙烯的混合物,酯化共聚物单独用作添加剂时没有效果。该专利指出,烯烃应含10—30碳,醇应含6—28碳,醇中最长链含22—40碳。
US3444082,4211534,4375973和4402708建议用某些含氮化合物。
还已知双官能化合物的长正烷基链衍生物可用作馏分燃料蜡晶体改性剂,衍生物可特别举出烯基琥珀酸的胺衍生物(US3444082),马来酸(US4211534)和苯二甲酸(GB2923645,US4375973和US4402708)。某些烷基化芳族磺酸胺盐已见于UK1209676,可用作汽轮机油和液压油的防锈剂。
加这些专利所述添加剂可改进CFPP活性,其中改善形成蜡晶体的尺寸和形状,生成针状晶,粒径一般10000nm或以上,通常30000—100000nm。在柴油机和加热***低温操作时,这些晶体一般不能经过过滤器,而是在过滤器上形成渗透滤饼,可让液体燃料通过,随后在发动机和燃料加热过程中,蜡晶体会溶解,可用循环燃料加热大部分燃料。但蜡晶体可能堵塞过滤器,致使燃料加热***起动困难和冷天开始时出现问题或失效。
EP0225688中我们建议用衣康酸酯和柠康酸酯聚合物和共聚物作为流动改进剂,可有效地改进油(原油或润滑油)和燃料油,如渣油燃料的中馏分燃料和喷气燃料的低温流动性或作为润滑油的脱蜡助剂并可特制而适宜于有关特殊油品或燃料油。据说这些聚合物和共聚物数均分子量经凝胶渗透色谱测得为1000—500000,实例中所举具体材料分子量20000或更高。
更具体地讲,EP0225688提出含少量(重量)聚合物的原油,润滑油或燃料油,聚合物中含以下单元: 其中x为整数,y为0或整数,x+y至少为2,单元(II)与单元(I)之比0—2,单元( I)与单元(III)之比0—2,R1和R2相同或不同,为10—30碳烷基,R3为H,—OOCR6,1—30碳烷基,—COOR6,—OR6,芳基或烷芳基或卤素,R4为H或甲基,R5为H,1—30碳烷基或—COOR6,R6为1—22碳烷基,R1,R2,R3,R4,R5和R6中每一个必要时均可进行惰性取代。
我们现已发现,用数均分子量1000—20000的上式聚合物和共聚物作为馏分燃料添加剂可在燃料中形成特别细小蜡晶体,小于用高分子同系物时得到的晶体。我们还发现,将低分子量聚合物和共聚物与其它添加剂并用时,这一效果特别明显。
因此,本发明提出用数均分子量1000—20000的聚合物作为馏分燃料油的流动改进剂,该聚合物中含以下重复单元:其中x为整数,y为0或整数,x+y至少为2,单元(II)与单元(I)之比0—2,单元(II)与单元(III)之比0—2,R1和R2相同或不同,为10—30碳烷基,R3为H,—OOCR6,1—30碳烷基,—COOR6,芳基或烷芳基或卤素,R4为H或甲基,R5为H,1—30碳烷基或—COOR6,R6为1—22碳烷基,R1,R2,R3,R4,R5和R6中每一个均可进行惰性取代。
本发明还提出含上述聚合物的馏分燃料,以及添加剂浓缩物,包括适宜于加入馏分燃料的上述聚合物溶液。
优选聚合物为衣康酸或柠康酸二烷基酯的均聚物或衣康酸或柠康酸二烷基酯与脂族烯烃,乙烯基醚,链烷酸乙烯基酯,不饱和酸的烷基酯,芳族烯烃,乙烯基卤或富马酸或马来酸二烷基酯的共聚物。
R1和R2相同或不同,为10—30碳烷基,优选直链,当然也可支化。若支化,优选支链为单一甲基,处在1或2位。R1和R2例子为癸基,十二碳烷基,十六碳烷基和二十碳烷基。R1和R2中每一个均可为单一10—30碳烷基或为烷基混合基。已发现,聚合物用作中间馏分燃料油流动改进剂时,12—20碳烷基混合基特别合适。同样,聚合物用于重质燃料油和原油时,适宜链长16—22碳,用于润滑油时,10—18碳。这些优选链长既适宜于均聚物,又适宜于共聚物。
本发明定义的至少两种聚合物可有利地用于本发明特定实施方案。因此,如后续实例所述,第一聚合物可选择来抑制低温下蜡从馏分燃料中沉降的趋势,而第二聚合物不同于第一聚合物,可选择来防止第一聚合物抑制燃料CFPP性能的趋势。例如,这种第一和第二聚合物可为衣康酸二烷基酯均聚物,其中第一聚合物的烷基相互相同,第二聚合物的烷基相互相同,第一聚合物的烷基碳原子数少于第二聚合物的烷基,可至少少两个(优选少两个)。这样的第一聚合物例子中烷基(即上述通式中R1和R2)为14,16或18碳。在具体例子中,第二聚合物烷基为18碳时,第一聚合物烷基为16碳,而第二聚合物烷基为20碳时,第一聚合物烷基为18碳。
在上述特殊实施方案中,第一聚合物与第二聚合物之比如10∶1—1∶10。在应用一种或多种其它流动改进剂(如后述)时,这些流动改进剂与第一和第二聚合物之和之比如10∶1—1∶10。作为例子,第一聚合物与第二聚合物之比1∶1,其和与任何其它流动改进剂之比也为1∶1。上述所有比例均为重量∶重量(ai)。
在共聚单体为脂族烯烃时,R3和R5为氢或等同或非等同的1—30碳烷基,优选正烷基。因此,在R3,R4和R5均为氢时,烯烃为乙烯,在R3为甲基,R4和R5为氢时,烯烃为正丙烯。在R3为烷基时,优选R4和R5为氢。其它适宜烯烃的例子为1—丁烯,2—丁烯,异丁烯,1—戊烯,1—己烯,1—十四碳烯,1—十六碳烯和1—十八碳烯及其混合物。
其它适宜的共聚单体为乙烯基酯或2—31碳链烷酸烷基取代乙烯基酯,即对于乙烯基酯,R3为R6COO—,R4为H和R5为H时,而对于烷基取代乙烯基酯,R3为R6COO—,R4为甲基和/或R5为1—30碳烷基时。优选非取代乙烯基酯,适宜例子为乙酸乙烯酯,丙酸乙烯酯,丁酸乙烯酯,癸酸乙烯酯,十六碳烷酸乙烯酯和硬脂酸乙烯酯。
另一类共聚单体为不饱和酸烷基酯,即在R3为R6COO—时,R5为H或1—30碳烷基。R4和R5为氢时,这些共聚单体为丙烯酸烷基酯。R4为甲基时,共聚单体为甲基丙烯酸或1—30碳烷基取代甲基丙烯酸酯。适宜的丙烯酸烷基酯例子为丙烯酸甲酯,丙烯酸正己酯,丙烯酸正癸酯,丙烯酸正十六碳烷酯,丙烯酸正十八碳烷酯和丙烯酸2—甲基十六碳烷酯,而适宜的甲基丙烯酸烷基酯例子为甲基丙烯酸丙酯,甲基丙烯酸正丁酯,甲基丙烯酸正辛酯,甲基丙烯酸正十四碳烷酯,甲基丙烯酸正十六碳烷酯和甲基丙烯酸正十八碳烷酯。其它例子为R为烷基,如甲基,乙基,正己基,正癸基,正十四碳烷基和正十六碳烷基的相应酯。
另一类适宜的共聚单体为R3和R5均为R6OOC—时,即均为富马酸或马来酸1—22碳二烷基酯,烷基可为正烷基或支化烷基,如正辛基,正癸基,正十四碳烷基,正十六碳烷基。
其它共聚单体例子为R3为芳基时。R4和R5为氢,R3为苯基时,共聚单体为苯乙烯,而R4和R5之一为甲基时,共聚单体为甲基苯乙烯,如甲基苯乙烯。R3为芳基时的另一例子为乙烯基萘。R3为烷芳基的其它适宜例子为如取代苯乙烯,如乙烯基甲苯或4—甲基苯乙烯。
另一适宜的共聚单体为R3为卤素,如氯时,如乙烯基氯(R4和R5为氢)。
所有情况之下,应注意到,R1,R2,R3,R4,R5和R6中某些或全部可进行惰性取代,如用一个或多个卤原子,如氯或氟取代。因此,共聚单体可为三氯乙酸乙烯酯。另一方面,取代基又可为烷基,如甲基。
单元(II)与单元(I)之比为0(聚合物为衣康酸酯或柠康酸酯均聚物)至2(聚合物为共聚物),但对于共聚物,该比值实际上通常为0.5—1.5。一般来说,共聚物仅由单元(I)和(II)或单元(II)和(III)组成,但并不排除其它单元。然而,实际上可要求共聚物中单元(I)和(II)或单元(II)和(III)之重量百分比为至少60%,优选至少70%。
对均聚物和共聚物二者而言,聚合物分子量1000—20000,优选1000—10000,更优选2200—5000。我们已发现,应用该范围分子量的均聚物或共聚物时,馏分燃料中可得到特别小的蜡晶体。分子量是用凝胶渗透色谱(GPC)并以聚苯乙烯为基准测得的。
均聚物和均聚物的制法一般是让单体净聚合或在溶液中进行,其中用烃溶剂,如庚烷,苯,环己烷或烃油,温度范围一般20—150℃,通常用过氧化物或偶氮类催化剂,如苯甲酰过氧化物或偶氮二异丁晴助催化,在惰性气,如氮气或二氧化碳气封而排除氧气的情况下操作。聚合物在蒸压釜中加压或回流制得。
制取共聚物时,聚合反应混合物应优选高达2mol的共聚物单体(如乙酸乙烯酯)/mol衣康酸二烷酯或柠康酸二烷酯。
共聚物宜作燃料油的低温流动改进剂。这些燃料油可为中间馏分燃料油,如柴油燃料,航空燃料,煤油,燃料油,喷气燃料,取暖用油等。一般来说,适宜的馏分燃料沸程120—500℃(ASTM D—86),优选150—400℃,如终沸点(FBP)相当高,360℃以上。代表性取暖用油规定要求10%馏出点不高于约226℃,50%馏出点不高于约272℃,而90%馏出点至少282℃,不高于约338℃至343℃,当然有些规定要求90%馏出点高至357℃。取暖用油优选由直馏分,如粗柴油,石脑油等和裂化馏分,如催化循环油料制成。柴油燃料代表性规定包括最低闪点38℃和90%馏出点282—338℃(见ASTMD esignations D—396和D—975)。
本发明聚合物添加剂与其它已知的一般性用来提高馏分燃料低温流动性的添加剂并用时,通常可取得最好的效果。但本发明聚合物添加剂又可单独使用。
本发明添加剂与下式梳型聚合物并用时特别有效:其中D=R,C(O),OR,OC(O).R,R1C(O),
OR或OR
E=H或CH3或D或R1
G=H或D
m=1.0(均聚物)至0.4(mol比)
J=H,R1,芳基或杂环基,R1CO,OR
K=H,C(O),OR1,OC(O),R1,OR1,
C(O)OH
L=H,R1,C(O),OR1,OC(O).R1,芳基,
C(O)OH
n=0.0至0.6(mol比)
R为烃基,含10碳以上,优选10—30碳
R1为1—30碳烃基。
梳型聚合物可含第三共聚单体。
适宜硫型聚合物例子为富马酸酯/乙酸乙烯酯,尤其已见于我们的EP0153176,0153177和酯化烯烃/马来酸酐共聚物和α—烯烃聚合物和共聚物和酯化的苯乙烯和马来酸酐共聚物。
可包括在本发明组合物中的其它添加剂例子为聚氧化烯酯,醚,酯/醚酰胺/酯及其混合物,特别是含至少一个,优选至少两个100—5000,优选200—5000分子量聚烷二醇基的10—30碳线性饱和烷基,所说聚烷二醇中烷基含1—4碳。EP0061895A2说明了某些这类添加剂。
优选酯,醚或酯/醚结构式如下:
R—O—(A)—O—R1其中R和R相同或不同,可为
i)正烷基烷基为线性饱和的,含10—30碳,A代表二醇的聚烷二醇链段,其中亚烷基含1—4碳,如聚氧亚甲基,聚氧亚乙基或聚氧三亚甲基,基本上为直链,可允许用低碳烷基侧链(如在聚氧化丙烯二醇中)进行一定程度支化,但优选二醇应当为基本上线性的。
适宜二醇一般为基本上直链聚乙二醇(PEG)和聚丙二醇(PPG),分子量约100—5000,优选约200—2000。酯为优选且10—30碳脂肪酸可用来与二醇反应而形成酯添加剂,优选用18—24碳脂肪酸,尤其是二十二碳烷酸。也可将聚乙氧化脂肪酸或聚乙氧化醇酯化而得酯。A也可含氮,此时乙氧化胺酯化可得要求材料。
其它可包括在本发明燃料组合物中的适宜添加剂为乙烯/不饱和酯共聚物流动改进剂。可与乙烯共聚的不饱和单体可包括下式不饱和单酯和二酯:其中R8为氢或甲基,R7为—OOCR,其中R10为氢或1—28碳,通常1—17碳,优选1—8碳直链或支化链烷基或R7为—COOR10,其中R10如前述,但不为氢,R9为氢或前述—COOR10。R7和R9为氢,R8为—OOCR10的单体包括1—29碳,通常1—18碳,优选2—29碳,更优选1—18碳单羧酸,特别优选2—5碳单羧酸乙烯基醇酯。可与乙烯共聚的乙烯酯例子包括乙酸乙烯酯,丙酸乙烯酯和丁酸乙烯酯或异丁酸乙烯酯,优选乙酸乙烯酯。优选聚合物含10—40wt%乙烯基酯,更优选25—35wt%。也可用两种共聚物的混合物,如已见于US3961916。优选的是,这些共聚物数均分子量1000—6000,更优选1000—4000,用气相渗透压测定法测定。
可加入本发明燃料组合物的其它适宜添加剂为极性化合物,可为离子型或非离子型,在燃料中具备蜡晶体生长抑制剂能力。这些极性化合物一般为胺盐和/或酰胺,由至少1mol烃取代胺与1mol 1—4羧酸根的烃基酸或其酸酐反应而形成,也可用含30—300,优选50—150总碳数的酯/酰胺。这些含氮化合物已见于例如US4211534。适宜胺通常为长链12—40碳伯,仲,叔或季胺或其混合物,但短链胺也可用,只要形成的含氮化合物为油溶性并因而通常含约30—300总碳数就行。含氮化合物优选含至少一个8—40碳,优选14—24碳直链烷基链段。
适宜胺包括伯,仲,叔或季胺盐,但优选为仲胺。叔和季胺仅形成胺盐。胺例子包括十四碳烷胺,可可胺和氢化脂胺等。叔胺例子包括二—十八碳烷胺和甲基—二十二碳烷胺等。胺混合物也合适,天然原料衍生物的许多胺为混合物。优选胺为式NHR1R2的仲氢化脂胺,其中R1和R2为由大致4%14碳,31%16碳,59%18碳构成的氢化脂肪衍生的烷基。
用来制取这些含氮化合物(和其酸酐)的适宜羧酸或其酸酐例子包括环己烷—1,2—二羧酸,环己烷二羧酸,环戊烷—1,2—二羧酸和萘二羧酸等。一般来说,这些酸的环中含约5—13碳。优选酸为苯二羧酸,如邻苯二羧酸,对苯二羧酸和间苯二羧酸。特别优选邻苯二羧酸或其酸酐。也可用烷基取代琥珀酸或酸酐。特别优选化合物为酰胺—胺盐,由1mol邻苯二酸酐与2mol二氢脂胺反应形成的。另一优选化合物为二酰胺,由该酰胺一胺盐脱水而形成。
其它适宜共添加剂例子包括EP0261957所述化合物,如下式:其中A和B可相同或不同,可为烷基,烯基和芳基,L选自>CH—CH<和>C=C<并且A,B和L可一起构成环结构的一部分,可为芳环,脂环或芳/脂混合物,条件是A,B和L不构成环结构的一部分时,A和B之一可为氢并且L为非环烯结构时,所说X—X1和Y—Y1为顺式构型,X选自SO3(-);—C(O)—,—C(O)O(-),—R4—C(O)O—,—NR3C(O)—,—R4O—,R4OC(O)—,—R4—和—NC(O)—,X1选自N(+)R3 3R2,HN(+)R3R2 2,H2N(+)R3R2,H3N(+)R2,N(+)R3 3R1,N(+)HR2 3R1,H2N(+)R3R1,H3N(+)R1,NR3R2,—R2,—NR3R1和R1,Y为—SO3—或—SO2—,在Y为SO3 (-)时,Y1选自N(+)R3 3R2,HN(+)R3 3R2,H2N(+)R3R2,H3N(+)R2,在Y为—SO2—时,Y1—OR2,—NR3R2或—R2,R1和R2可分别选自烷基,一般10—40碳,优选10—30碳,更优选14—24碳烷基,烷氧烷基或聚烷氧烷基,其主链中含至少10,一般10—40碳,R3为烃基,优选烷基,更优选1—30,特别优选10—30碳直链烷基且每一R3可相同或不同,R4为—(CH2)n,n为0—5。
优选X1和Y1一起含至少3个烷基,烷氧烷基或聚烷氧烷基。
在这些化合物中,A和B一起或分别形成一个或多个主体基,L为连接基,也可为主体基的一部分,X和/或Y为构型基并且X1和/或Y1构成吸收基。
L与A和B一起构成环结构时,该环结构可为芳环,脂环或芳/脂混合环。更具体地讲,环结构可为单环或多环芳环,多核芳环,杂芳环和杂脂环。环结构可饱和或不饱和,可有一个或多个不饱和键,至少一个环含4个或以上的原子,可为多环,桥连并可取代。环结构为杂环时,可包括一个或多个N,S或O原子。
适宜单环结构例子为苯,环己烷,环己烯,环戊烷,吡啶和呋喃。环结构可含其它取代基。
有两个或多个环结构的适宜多环化合物可取各种形式。可为(a)稠合芳环结构,(b)稠合部分氢化芳环结构,其中至少一个,但并不是所有环为芳环,(c)脂环,包括稠合脂环,桥连脂环,螺脂环化合物,(d)相同或不同芳环,脂环或混合环的烃环组合,(e)含至少一个杂原子的(a)—(d)之一。
由A,B和L一起定义的化合物衍生出来的稠合芳环结构包括如萘,蒽,菲,芴,芘和茚。完全没有或不是所有为苯环的适宜化合物包括如奥,氢化萘,氢化茚,氢化芴,联二亚苯。适宜桥连脂环结构包括双环庚烷和双环庚烯。适宜环组合包括联苯和环己苯。
适宜杂多环结构包括奎宁环和吲哚。
由L,A和B一起定义的可衍生出本发明化合物的适宜杂环化合物包括喹啉,吲哚,2,3—二氢吲哚,苯并呋喃,香豆素和异香豆素,苯并噻吩,咔唑和吩噻嗪。
由L,A和B一起定义的适宜非芳环或部分饱和环体系包括萘烷(+氢化萘),蒎烯,荜澄茄烯,冰片烯。适宜桥连化合物包括降冰片烯,双环庚烷(降冰片烷),双环辛烷和双环辛烯。
L,A和B形成环结构的一部分时,X和Y优选连接到完全位于单一环内的邻近环原子上,单环或多环均如此。例如,若用萘,则这些取代基不能连于1,8—或4,5—位上,而必须连于1,2—,2,3—,3,4—,5,6—,6,7—或7,8—位上。
L为烯结构且又不属于与A和B成环结构的一部分时,A和B中含氢和含碳基优选为烷基,通常为1—24碳烷基或烯基,芳基,一般6—14碳芳基。这些基团也可卤代,优选仅含少量卤原子(如氯),如少于20wt%。A和B基优选为脂肪基,如亚烷基。优选呈直链。不饱和烃基,如烯基也可用,但并不优选。
在这些化合物用作馏分燃料添加剂时,优选R1,R2和R3存在时含10—24碳,如14—22,优选18—22碳,还优选直链或1或2位支化。适宜烷基包括癸基,十二碳烷基,十四碳烷基,二十碳烷基和二十二碳烷基(山萮基)。另一方面,这些基团又可为聚环氧乙烷或聚环氧丙烷,这些基团主链为最长线性链段。
特别优选化合物为酰胺或仲胺盐。虽然上述环衍生物必须有两个取代基,但应该认识到,这些环化合物可含一个或多个其它取代基,连于环化合物的环原子上。
将Y2-H基和X2-H基与胺,醇,季胺盐等或其混合物反应可制得这些化合物,最终化合物为酰胺或胺盐时,优选为仲胺,其中有含氢和碳的基,含至少10碳,优选为含10—30,更优选16—24碳直链烷基。将酸或酸酐与仲胺或另一种办法与胺衍生物反应可制得这些酰胺或盐。去除水并加热一般是必须的,以便用酸制得酰胺。另一方面,Y2-H和X2-H基可与含至少10碳醇或醇和胺的混合物反应或顺序与胺和醇反应或相反。
因此,最终添加剂化合物因X-X1和Y-Y1等同而可包括酯,酰胺,醚,伯,仲或叔胺盐,氨基酰胺,氨基醚等。
U=H,T或芳基
v=1.0—0.0(mol比)
w=0.0—1.0(mol比)其中R1为烷基。
这些聚合物可直接用烯属不饱和单体制备或间接将异戊二烯和丁二烯等单体制成的聚合物加氢而制成。
特别优选烃聚合物为乙烯和丙烯共聚物,其中乙烯含量优选20—60%(w/w),一般是用均相催化法制成的。
在本发明组合物中可应用一种或多种其添加剂。
应用添加剂混合物时,则混合物中所用添加剂相对比例为,每1份其它添加剂优选用0.05—20重量份,优选0.1—5重量份衣康酸酯或柠康酸酯聚合物或共聚物。
加入燃料油的添加剂总量优选0.0001—5.0wt%,如0.001—0.5wt%(活性物质),以燃料油重量计。
添加剂可方便地溶于适当溶剂中而形成溶剂中含20—90,如30—80wt%聚合物的浓缩物。适宜溶剂包括煤油,芳族石脑油,矿物润滑油等。这些浓缩物也属于本发明。
下述实例详述本发明,共中用以下添加剂。
添加剂A
苯磺酸2—二烷基酰氨酯的N,N—二烷基铵盐,其中烷基为nC16-18H33-37
将1mol邻磺基苯甲酸环酸酐与2mol二(氢化)牛脂胺在二甲苯溶剂中以50%(w/w)浓度反应而制得,反应混合物100℃至回流温度搅拌。溶剂和化学品应尽可能保持干燥,以使酸酐不至于水解。
产品用500MHz NMR谱分析,结构如下:
添加剂B
数均分子量3500的乙烯/乙酸乙烯酯共聚物,含13.5wt%乙酸乙烯酯和8个甲基/100亚甲基
添加剂C
在环己烷溶剂中用自由基催化剂使单体聚合而得的各种衣康酸酯聚合物。
制成数均分子量4000的齐聚物料和分子量80000的聚合物料作比较,每一种在衣康酸酯中含12—18碳线性烷基,下表中称之为C10PI,C12PI和C14PI等。
添加剂D
1mol苯二酸酐与2mol二氢牛脂胺反应产品,形成半酰胺/半胺盐。
添加剂E
数均分子量3000的乙烯/乙酸乙烯酯共聚物,含29%乙酸乙烯酯和4个甲基/100个亚甲基。
添加剂F
添加剂D与10%作为稳定剂的苯甲酸混合物
添加剂G
添加剂D的3硝基衍生物
各种添加剂并用时,每种在馏分燃料中的处理量为250ppm,馏分燃料特性如下:
浊点—2℃
未处理CFPP—4℃
ASTM D—86蒸馏℃
初沸点178
5%227 50%291
10%243 10%301
20%261 70%311
30%272 80%324
40%282 90%341
终沸点368
进行如下试验:
试验
添加剂体系在馏分燃料中作可滤性改进剂的效率用下法测定。。一种方法中,油对添加剂的反应用低温过滤堵塞点试验(CFPP)测定,按“Journel of the Institute ofPetroleum”,V52,Number 510.June 1966,pp.173-285中详述的方法进行。该试验考虑机车发动机用中间馏分低温流动性。
简而言之,40ml待试样品在保持约-34℃的浴中冷却,以约1℃/min的非线性冷却。隔一定时间(从浊点开始每隔1℃),用冷却样品油测试其在规定时间内经过细筛的流动能力,试验仪器为吸移管,其下端设有逆转漏斗,位于待试油面以下。漏斗口上布置350目筛,以12mm直径定义其面积。每次在吸移管上端抽真空而开始定期试验,借此将油吸过筛而进入吸移管,达到指定20ml油的标定位置。每次顺利通过后,油立即回到CFPP管。温度每下降1℃,重复1次试验,直到油在60秒种内仍不能进入吸移管为止。这一温度被称之为CFPP点。无添加剂燃料和含添加剂燃料之CFPP区别称为添加剂CFPP抑制(dCFPP)。在同一添加剂浓度下,更有效流动改进剂达到更大的CFPP抑制。
另一流动改进剂效率测定方法在流动改进剂按程序冷却试验(PCT)条件下进行,此为一种慢冷试验,旨在指明燃料中蜡是否经过过滤器,如在取暖用油分布体系中。
在该试验中,上述含添加剂燃料低温流动性测定法如下。300ml燃料按1℃/h线性冷至试验温度,然后该温度保持恒定。-12℃2h后,大约20ml表面层作为不合格大块蜡晶体去除,这是在冷却过程中于油/空气界面上形成的。瓶中沉积蜡搅拌分散。然后送入CFPP过滤器装置。开盖而加以500mmHg的真空并在200ml燃料通过过滤器而进入刻度接收器时关闭。若60秒钟内经过给定筛目量达到200ml,则记为PASS,若流速太慢表明过滤器已堵塞,则记为FAIL。
应用滤筛目数20,30,40,60,80,100,120,150,200,250,350, VW,LTFT和500,然后用25,20,15,和10微米的OFPP过滤装置测定燃料可通过的最细过滤器。含蜡燃料经过的目数越大,则蜡晶体越小,添加剂作为流动改进剂的效率就越好。应注意到,两份燃料在同一流动改进剂的同一处理量条件下不大可能达到恰好相同的试验结果。在下面所列表中,还给出了相对顺序,数值越大,表示能通过的过滤器越细。
PCT过滤之前,还对蜡沉积进行了研究。沉积层(WAS)量可肉眼确定,其中将处理燃料留在测量瓶中,观察总燃料体积的%。这种大量蜡沉积可能给出低值,而未沉积流体燃料值为100%。必须加以注意,因为带有大蜡晶体的胶凝劣质燃料样品也总是能达到高值,因此应将这些结果记为“gel”。
本发明添加剂降低馏分燃料浊点的效率可用标准浊点试验(IP-219或ASTM-D 2500)测定,出现结晶的其它测定法为起蜡点(WAP)试验(ASTM D3117-72)和起蜡温度(WAT),用差式扫描量热法测定,应用Mittler TA2000B差式扫描量热仪。在该试验中,25ml燃料样品按2℃/min冷却,从预计燃料浊点以上至少30℃的温度开始冷却。评估观察到的结晶点,无需对热传导尽缓(大致2℃)进行校正,实际上为差式扫描量热仪指出的起蜡温度。这为优选法,因为其精度高,可重复,因此是本发明首选方法。
燃料起蜡温度(WAT)用差式扫描量热计(DSC)测定,在该试验中,少量燃料样品(25μl)按2℃/min冷却,同时冷却类仪热容量参考样品,但该样品在有关温度范围内不会沉淀蜡(如煤油)。样品中开始结晶时可观察到放热现象。例如,燃料WAT可用Mettler TA2000B用外推技术测定。dWAT为基本燃料中加添加剂而达到的起蜡温度抑制情况。
将基准线和放热线直下到规定温度所包括的面积积分即可用DSC轨迹得到蜡含量。已先用已知量的结晶蜡进行了校正。
蜡晶体平均粒径通过分析燃料样品的光学显微照片并测定晶体最长轴而得。
晶体形状由燃料中蜡晶体照片放大而确定。
试验结果列于下表1。
表 1
添 加 剂 | 聚衣康酸酯组合物%聚合物 | %齐聚物 | %WAS | 晶体尺寸(nm) | 晶体形状 | PCT | 相对值PCT | CFPP | dCFPP | dWAT |
A BA B C10 P1A B C10 P1A B C12 P1A B C12 P1A B C12 P1A B C12 P1A B C14 P1A B C14 P1A B C14 P1A B C14 P1 | 10020100200010045300 | 08008010010005570100 | 100100100100100100100梯级絮凝7050100 | 30-8030-5010-205-2010-5010-80>200>200>20010-30 | 片""双棱锥"片"条带&枝晶枝晶"球结节 | 120120150VM25μm120120606060100 | 7781215774446 | -16-17-18-19-19-17-20-8-10-11-18 | 1213141515131646514 | 0.51.20.60.60.60.80.81.81.51.41.7 |
表 1(续1)
A B C16 P1A B C16 P1A B C16 P1A B C16 P1A B C18 P1A B C18 P1 | 1002510000 | 07590100100100 | 100100100100100100 | 10-5010-20~10<1010->20010->200 | 片小""片" | 15020015μm20μm4040 | 89171633 | -14-14-14-15-17-15 | 101010111311 | 1.01.61.92.10.50.6 |
表 1(续2)
添 加 剂 | 聚衣康酸酯组合物%聚合物 | %齐聚物 | %WAS | 晶体尺寸(nm) | 晶体形状 | PCT | 相对值PCT | CFPP | dCFPP | dWAT |
D BD B C10 P1D B C10 P1D B C12 P1D B C12 P1D B C12 P1D B C12 P1D B C14 P1D B C14 P1D B C14 P1D B C14 P1 | 10020100200010045300 | 08008010010005570100 | 100100100100100100100梯级絮凝""30 | 10-3010-3010-2010-20<=10<=10<=20>300>300>300>200 | 小""针小""线""很大未决定 | 120120120500500VW25μm60404040 | 777141412154333 | -12-1413-19-15-13-14-6-7-7-8 | 91110161210113445 | 0.90.80.81.90.70.80.91.61.41.41.5 |
表 1 (续3)
D B C16 P1D B C16 P1D B C16 P1D B C16 P1D B C18 P1D B C18 P1 | 1002510000 | 07590100100100 | 5080100100严重絮凝" | 10-70<10-250<10<1030-75030-550 | 小&片"小"针&片" | 608015μm25μm6060 | 45171544 | -12-9-7-6-10-11 | 964378 | 1.01.61.92.00.60.7 |
表 1(续4)
添 加 剂 | %聚合物 | %齐聚物 | %WAS | PCT | 相对值PCT | CFPP | dCFPP | dWAT |
EFE FEE GB FB AB GE F C16 P1E F C16 P1E F C16 P1B F C16 P1B F C16 P1B F C16 P1 | 010100010100 | 100900100900 | 6020808095250100100100100FLoc10010060 | 60401205001006012012015μm15μmVW25μm500120 | 43714647717171215147 | -16-10-14-19-16-17-16-12-10-14-18-8-8-13 | 1261015121312961014449 | 0.80.80.10.50.91.90.81.91.70.8 |
表 1(续5)
E A C16 P1E A C16 P1E A C16 P1B A C16 P1B A C16 P1B A C16 P1E D C16 P1E D C16 P1E D C16 P1B D C16 P1B D C16 P1B D C16 P1 | 010100010100010100010100 | 100900100900100900100900 | 1001001001001001001001008010010050 | 15μm20μm50020μm15μm15020μm20μm8025μm15μm60 | 171614161781616515174 | -14-13-18-15-14-14-7-7-15-6-7-12 | 109141110103311349 | 2.22.11.22.11.91.02.12.01.12.01.91.0 |
表 1(续6)
添 加 剂 | %聚合物 | %齐聚物 | %WAS | PCT | 相对值PCT | CFPP | dCFPP |
C10 P1C12 P1C14 P1C16 P1C18 P1E C10 P1C12 P1C14 P1C16 P1C18 P1F C10 P1C12 P1C14 P1C16 P1C18 P1E F C10 P1C12 P1C14 P1C16 P1C18 P1 | 202030100202030100202030100202030100 | 80807090100808070901008080709010080807090100 | GelGelGelFlocGel606075Floc803020802050758580100100 | 3030302040608060200804060406010012015010015μm120 | 222134549534347786177 | -3-3-3-4-8-13-16-9-7-12-6-4-5-1-13-17-19-17-14-19 | -1-1-104912538201-391315131015 |
在另一系列试验中,应用了下述另一些添加剂。
添加剂H
两种乙烯/乙酸乙烯酯共聚物之混合,一种Mn2580,含36.5wt%乙酸乙烯酯,另一种Mn5000,含13.5wt%乙酸乙烯酯,两种共聚物之比3∶1(w/w)。
添加剂I
同于添加剂H,只是两种共聚物之比13∶1(w/w)。
添加剂J
乙烯/乙酸乙烯酯共聚物,数均分子量2000,含28.0wt%乙烯基
添加剂试验所用燃料性能列于表2。
表 2
燃料 No浊点 ℃ | 1-2 | 2-7 | 33 | 4-4 | 5-5 | 6-6 | 7-7 | 8+1 | 9-5 | 10-6 | 11-5 |
ASTM D-8ibp5%10%20%30%40%50%60%70%80%90%95%fbp基本 CFPP | 178227243261272282291301311324341355368-4 | 141187197210222235249264282300324341357-9 | 1792242382572702822933053183333503633730 | 145225260329350367 | 168215229248261271279287297309327341358-8 | 135182192213239261277290303315332344361-9 | 136177187200214230248265283304329342364-7 | 208232238250260270281293306321342361372-4 | 155195207228247264277289302216333346359-6 | 166209231250265276287298310325348-8 | 170200219238270296334371-7 |
在这些试验中,处理量250ppm每种添加剂有效成分。抗蜡沉积效果测定法如下:
(a)如前述实例用肉眼观测容器,数值给出蜡沉积量并进而标为字母代号。
C=%层上清晰,即燃料在试验温度以上完全脱蜡,所有蜡沉底,
F=絮凝,表明存在不合格大晶体,
CL=底层浑浊,抗蜡沉积效果良好,
所示结果中,H意指不清晰,M意指呈乳状,C指清晰,F指絮凝;
(b)取5mls顶部和底部样品,如上述用DSC测定其WATS,对其进行检测。在未沉积样品中,两个数值相同。数值之差越大,蜡沉积量越大。因此T-B范围=WAT底-WAT顶(℃)。
结果列于表3。
表 3
燃料2 | WAS(-18℃) | PCT | 相对值PCT | CFPP | ||||
HHHHHHHHHHHHH燃料3HHHHHHHH | FFFFFFFFFFFFFFFFFFF | C10 FVAC10-12 FVAC12 FVAC12-14 FVAC14 FVAC10 SFECC10-12 SFECC12 SFECC12-14SFECC14 SFECC16 PI(olig)C12 FVAC12-14 FVAC14 FVAC14-16 FVAC16 FVAC12 SFEC | 30H80CL80C80C25/75CL25CL10H75H80H90H25/75HGrad hazy100F(-9℃)5/15C50C50C80H40H100 gel100 gol60H | 100500500500500VW100LTFT50025μm500VW10μm406080100150606060 | 61414141413613141514121834568444 | -19-23-26-21-29-20-16-20-23-22-23-19-19-11-14-15-17-12-3-1-17 |
表3(续)
燃料3 | WAS | PCT | 相对值PCT | CFPP | ||
HHHHHH燃料4HHHHHHHHHHHH | FFFFFFFFFFFFFFFFF | C12-14 SFECC14 SFECC14-16 SFECC16 SFECC16 PI(olig)C18 PI(olig)C12 FVACC12-14 FVACC14 FVACC14-16 FVACC12 SFECC12-14 SFECC14 SFECC14-16 SFECC16 Pl(olig)C18 Pl(olig) | -50C60C30C100 gol30CL90CL10H10H5HHHH10H10HHHmilky20H | 80100606060150100LTFTLTFT25μmVW100LTFTLTFTLTFTVW10μm20μm | 5644486131315126331313121816 | -15-15-11-2-4-16-22-26-20-18-18-16-24-22-25-17-11-24 |
表3(续)
燃料5 | 晶体尺寸 | 晶体形状 | PCT | 相对值PCT | CFPP | dWAT | T-B范围 | WAS | |
II FI FI FI F燃料6I FI FI FI F燃料7II FI FI FI F燃料8I | C16 PI(olig)C12-14 FVACC16 FVACC16 PI(olig)C12-14 FVACC16 FVACC16 PI(olig)C12-14 FVACC16 FVAC | 2020-50<<10<10-402020-50<1030-5010-50<10-20<<<10<1010-3010-60 | 针针粒组合细针针粒粗粒针针很小球结节球结节&块混合物 | 6025015μmVW200<35020μm<350VW<35015μm500<35080 | 41017129<1116<1112<111714<115 | -16-18-18-15-15-23-17-19-20-29-15-19-13-17 | -0.5-0.41.11.70.7-0.41.20.61.10.33.11.23.1-0.5 | 18.88.38.514.611.212016.5222312.51924.5 | 26C47C40CL<10CL48H70F10026F100F24096CL35CL31F27C |
表3(续)
晶体尺寸 | 晶体形状 | PCT | 相对值PCT | CFPP | dWAT | T-B范围 | WAS | ||
I FI FI FI F燃料9II FI FI FI F燃料10EE FE FE FE FE F | C16 PI(olig)C12-14 FVACC16 FVACC16 PI(olig)C12-14 FVACC16 FVACC12-14 FVACC16 FVACC16 PI(olig)C18 PI(olig) | 10-50<<1010-2050-10020-30<1010-4020-50100-20080-10070-170100-45020-4050-150 | 针粒双棱锥&针球结节&片针粒针针混合物针针针针 | 200VWVW1006025025μm25025μm406015060VW120 | 9121264101510153484127 | -19-9-17-5-11-16-11-14-12-12-19-18-10-13-17 | -0.32.30.13.1-10.21.60.71.4-0.9-0.6-0.20.80.7-0.6 | 20.311.62.920.122.525.712.52.216.520.11708.811.7 | 40C10CL5CL26C20C98CL100CL80H100CL17C30C42C100M100M65H |
表3(续)
燃料11 | 晶体尺寸 | 晶体形状 | PCT | 相对值PCT | CFPP | dWAT | T-B范围 | WAS | |
EE FE FE FE FE F燃料1EEJIB FE FJ FI FB FE FJ FI FB FE FJ FI F | C12-14 FVAC16 FVAC16 PI(olig)C18 PI(olig)C16 PI(olig)C16 PI(olig)C16 PI(olig)C16 PI(olig)C12-14 FVACC12-14 FVACC12-14 FVACC12-14 FVAC | 10-15010-401030-50<=10<10500100-300100-20070204020-4050<10<10<10<30150305030-50 | 针&片球结节&针球结节&块针很小片针&片针&双棱锥针&片针细针细针针微针双棱锥针针针&双棱锥 | 80250VM12020μm15μm40808060801201008015μm15μm15μm500100LTFT250120 | 41012716153554576517171712613107 | -19-20-20-12-12-11-8-16-15-13-18-20-19-18-8-11-4-6-16-17-17 | -22-1.72.72-1.2-4.6-2.13.50-0.30-0.41.31.62.11.80.20.20.30.05 | 21.115.717.615.50.50.525.423.423.413.46.417.712.72.30.35.68.220.59.715.58.9 | 45C30H30H30C100M1004Gol43C25C25C40H95H77H77C10010010010038H87CL49CL58H |
还进行另一系列试验。所用添加剂如下标为A1,B1,D1,E1和F1-M1,所用燃料特性如下:
A1:燃料I和II进行的试验中,A为两种乙烯/乙酸乙烯酯共聚物的混合物,含36.5wt%乙酸乙烯酯和3-4个甲基/100个亚甲基的Mn 2580共聚物和含13.5wt%乙酸乙烯酯和6个甲基/100个亚甲基的Mn 5000共聚物,两种聚合物之比93∶7(w/w),对于其它燃料的试验,A为含29.0wt%乙酸乙烯酯和4个甲基/100个亚甲基的Mn3000乙烯/乙酸乙烯共聚物。
B1:1mo苯二酸酐与2mol二氢化牛脂胺的反应产物,形成半酰胺/半胺盐。
D1:衣康酸酯的均聚物,酯中线性烷基含16碳,用自由基催化剂使单体聚合,Mw 4000。
E1:D1和第二种聚衣康酸酯的混合物,聚合物制法同于添加剂D1,但酯中烷基含18碳,Mw 4000。
F1:如含于E1中的第二种聚衣康酸酯。
应注意到,某些添加剂对应于前述试验中所用添加剂。不过,不论是否带有上标1,同一字母代表的添加剂之间不必具有任何联系。
添加剂(包括后续结果中由字母并列所代表的添加剂成分的混合物)可加入柴油中,A1浓度200ppm(ai),B1浓度200ppm(ai);D1,E1或F1为200ppm(ai),所说添加剂如上述。用这种处理的燃料进行以下试验:CFPP,WAS和晶体尺寸,方法均如上述。所用燃料为燃料I-VIII,其特性列在下面的图表1中,所有温度为℃。
图表1
燃料
燃料性能 | I | II | III | IV | V | VI | VII | VIII |
浊点基本CFPPD-86 ibp20%50%90%Fbp试验温度: | -6-8166231276325348-17 | -5-8168248279327358-15 | -6-9135213277332361-17 | -7-7136200248329364-17 | -4-4200252284335364-15 | -4145225260329367-15 | -2-4178261291341368-15 | +30179257293350373-9 |
添加剂A1,B1和D1-F1或其混合物和上述用燃料I-VIII中每一种进行试验。CFPP,WAS和晶体尺寸结果分别列于下示三表4,5和6中,各表说明如下:
表4(CFPP):所有结果为负值
表5(WAS):所有结果为分散百分数100为全分散,试验温度下2-3小时后进行观察。
表6(晶体尺寸):所有值标为1-10,其中
10为<10 μm
9为10 ″
8为10-20 ″
7为20-50 ″
6为50-100 ″
5为100-200 ″
4为200-300 ″
3为300-500 ″
2为500-700 ″
1为>700 ″
从表4-6所列结果可总结出如下结论:
添加剂A1和A1B1(比较例)可达到良好的CFPP性能,但WAS和晶体尺寸性能即不大好。
添加剂A1B1D1和A1B1F1的WAS和晶体尺寸性能良好,而CFPP抑制性能下降。
至少燃料I-V用添加剂A1B1E1可弥补上述的下降(fbp<365℃)。
表4(CFPP)
燃料
添加剂 | I | II | III | IV | V | VI | VII | VIII |
A1A1B1A1B1D1A1B1E1A1B1F1 | 111381615 | 1419181818 | 1420152122 | 2514161518 | 81471416 | 1924121213 | 131871718 | 10133815 |
表5 (WAS)
燃料
添加剂 | I | II | III | IV | V | VI | VII | VIII |
A1A1B1A1B1D1A1B1E1A1B1F1 | 20701009595 | 20801009595 | 401080100100 | 2015100100100 | 30100100100100 | 15100100100100 | 408075 | 2040100100100 |
表6(晶体尺寸)
燃料
添加剂 | I | II | III | IV | V | VI | VII | VIII |
A1A1B1A1B1D1A1B1E1A1B1F1 | 56665 | 5*9999 | 79101010 | 89101010 | 56765 | 6*9101010 | 56975 | 36886 |
*还含小晶体
最后,上述某些燃料单独用并含上述某些添加剂时的浊点按上述方法进行测定。所得结果如下(℃)
表 7(浊点)
燃料 添加剂
II IV VI VII
A1 -7 -6 -5 -1
A1B1 -8 -8 -8 -2
A1B1D1 -8 -10 -10 -4
A1B1E1 -8 -9 -9 -2
A1B1F1 -8 -9 -9 -2
无 -7 -8 -5 -1这些结果表明,本发明添加剂组合物可抑制(降低)浊点。
Claims (22)
2.权利要求1的馏分燃料,其中聚合物为衣康酸或柠康酸二烷基酯的均聚物或衣康酸或柠康酸二烷基酯与脂族烯烃、乙烯基醚、链烷酸乙烯基酯、不饱和酸的烷基酯、芳族烯烃、乙烯基卤或富马酸或马来酸二烷基酯的共聚物。
3.权利要求2的馏分燃料,其中聚合物为衣康酸二烷基酯与脂族烃、2—31碳链烷酸乙烯基酯或烷基取代乙烯基酯的共聚物,或R3为一芳基时的共聚物。
4.权利要求1的馏分燃料,其中低温流动改进剂包括至少两种权利要求1定义的聚合物,第一种选来抑制低温下蜡从馏分燃料中沉降的趋势,而第二种聚合物不同于第一种聚合物,选来防止第一种聚合物抑制燃料CFPP性能的趋势。
5.权利要求4的馏分燃料,其中第一和第二聚合物为衣康酸二烷基酯均聚物,第一聚合物的烷基相互相同,第二聚合物的烷基相互相同,第一聚合物烷基碳原子数比第二聚合物的烷基少至少两个。
6.权利要求5的馏分燃料,其中第一聚合物的每一烷基在第二聚合物的第一烷基含18碳时含16碳或在第二聚合物的每一烷基含20碳时含18碳。
7.权利要求1—6中任一项的馏分燃料,其中进一步含有其它的馏分燃料低温流动改进剂。
9.权利要求7的馏分燃料,其中其它低温流动改进剂为乙烯/不饱和酯共聚物。
10.权利要求7的馏分燃料,其中其它低温流动改进剂为胺盐和/或酰胺,该酰胺由取代胺与具有1—4个羧酸根或相应酸酐基的烃基酸反应而成。
11.添加剂浓缩物,该浓缩物包括含20—80wt%数均分子量2200—10000的聚合物的溶液,该聚合物中含以下重复单元:其中x为整数,y为0或整数,x+y至少为2,单元(II)与单元(I)之比为0—2,单元(II)与单元(III)之比为0—2,R1和R2相同或不同,为10—30碳烷基,R3为H,—OOCR6,1—30碳烷基,—COOR6,—OR6,芳基或烷芳基或卤素,R4为H或甲基,R5为H、1—30碳烷基或—COOR6,R6为1—22碳烷基,R1、R2、R3、R4、R5和R6中每一个均可进行惰性取代。
12.权利要求11的添加剂浓缩物,其中聚合物为衣康酸或柠康酸二烷基酯的均聚物或衣康酸或柠康酸二烷基酯与脂族烯烃、乙烯基醚、链烷酸乙烯基酯、不饱和酸的烷基酯、芳族烯烃、乙烯基卤或富马酸或马来酸二烷基酯的共聚物。
13.权利要求11或12的添加剂浓缩物,其中的共聚物是衣康酸二烷基酯或柠康酸二基酯与脂族烯烃、2—31碳链烷酸乙烯基酯或烷基取代乙烯基酯的共聚物,或R3为芳基时的共聚物。
14.权利要求11的添加剂浓缩物,其中聚合物分子量为1,000—10,000。
15.权利要求11的添加剂浓缩物,其中低温流动改进剂包括至少两种权利要求1定义的聚合物,第一种选来抑制低温下蜡从馏分燃料中沉降的趋势,而第二种聚合物不同于第一种聚合物,选来防止第一种聚合物抑制燃料CFPP性能的趋势。
16.权利要求15的添加剂浓缩物,其中第一和第二聚合物为衣康酸二烷基酯均聚物,第一聚合物的烷基相互相同,第二聚合物的烷基相互相同,第一聚合物烷基碳原子数比第二聚合物的烷基至少少两个。
17.权利要求16的添加剂浓缩物,其中第一聚合物的每一烷基在第二聚合物的每一烷基含18碳时含16碳或在第二聚合物的第一烷基含20碳时含18碳。
18.权利要求11的添加剂浓缩物,其中进一步含有其它的馏分燃料低温流动改进剂。
20.权利要求18的添加剂浓缩物,其中其它低温流动改进剂为乙烯/不饱和酯共聚物。
21.权利要求18的添加剂浓缩物,其中其它低温流动改进剂为胺盐和/或酰胺,由取代胺与具有1—4个羧酸根或相应酸酐基的烃基酸反应而成。
22.权利要求20的添加剂浓缩物,其中其它低温流动改进剂为胺盐和/或酰胺,由取代胺与具有1—4个羧酸根或相应酸酐基的烃基酸反应而成。
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GB909025499A GB9025499D0 (en) | 1990-11-23 | 1990-11-23 | Fuel oil compositions |
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CN91102537A Expired - Fee Related CN1032221C (zh) | 1990-04-19 | 1991-04-19 | 馏分燃料添加剂及含该添加剂的馏分燃料 |
Country Status (8)
Country | Link |
---|---|
US (1) | US5478368A (zh) |
EP (1) | EP0525040B1 (zh) |
JP (1) | JP2902481B2 (zh) |
CN (1) | CN1032221C (zh) |
AT (1) | ATE139558T1 (zh) |
CA (1) | CA2080468A1 (zh) |
DE (1) | DE69120406T2 (zh) |
WO (1) | WO1991016407A1 (zh) |
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GB9122351D0 (en) * | 1991-10-22 | 1991-12-04 | Exxon Chemical Patents Inc | Oil and fuel oil compositions |
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GB9301752D0 (en) * | 1993-01-29 | 1993-03-17 | Exxon Chemical Patents Inc | Oil and fuel oil compositions |
GB9411614D0 (en) * | 1994-06-09 | 1994-08-03 | Exxon Chemical Patents Inc | Fuel oil compositions |
GB9610363D0 (en) | 1996-05-17 | 1996-07-24 | Ethyl Petroleum Additives Ltd | Fuel additives and compositions |
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GB9707367D0 (en) * | 1997-04-11 | 1997-05-28 | Exxon Chemical Patents Inc | Improved oil compositions |
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GB9725581D0 (en) | 1997-12-03 | 1998-02-04 | Exxon Chemical Patents Inc | Additives and oil compositions |
GB9725578D0 (en) | 1997-12-03 | 1998-02-04 | Exxon Chemical Patents Inc | Oil additives and compositions |
GB9725582D0 (en) * | 1997-12-03 | 1998-02-04 | Exxon Chemical Patents Inc | Fuel oil additives and compositions |
GB9725579D0 (en) | 1997-12-03 | 1998-02-04 | Exxon Chemical Patents Inc | Additives and oil compositions |
EP1302526A1 (en) * | 2001-10-15 | 2003-04-16 | Infineum International Limited | Additive compositions |
EP1357168A1 (en) * | 2002-04-16 | 2003-10-29 | Infineum International Limited | Jet fuel compositions |
DE10254640A1 (de) * | 2002-11-22 | 2004-06-03 | Basf Ag | Verwendung von Homopolymeren ethylenisch ungesättigter Ester zur Vebesserung der Wirkung von Kaltfließverbesserern |
DE10324102A1 (de) * | 2003-05-27 | 2004-12-16 | Basf Ag | Brennstoffzusammensetzungen mit verbesserten Kaltfließeingenschaften |
CA2562255C (en) | 2004-04-06 | 2013-01-29 | Rodney Lee Cravey | Pour point depressant additives for oil compositions |
EP1640438B1 (en) | 2004-09-17 | 2017-08-30 | Infineum International Limited | Improvements in Fuel Oils |
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EP2336206B1 (en) | 2009-12-21 | 2012-01-25 | Infineum International Limited | Polymers and fuel oil compositions containing them |
ES2782549T3 (es) | 2014-08-07 | 2020-09-15 | Clariant Int Ltd | Aditivos para diésel marino con bajo contenido de azufre |
GB2621686A (en) * | 2022-06-24 | 2024-02-21 | Innospec Ltd | Compositions, and methods and uses relating thereto |
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-
1991
- 1991-04-19 CN CN91102537A patent/CN1032221C/zh not_active Expired - Fee Related
- 1991-04-19 US US07/937,907 patent/US5478368A/en not_active Expired - Fee Related
- 1991-04-19 WO PCT/GB1991/000622 patent/WO1991016407A1/en active IP Right Grant
- 1991-04-19 EP EP91908027A patent/EP0525040B1/en not_active Expired - Lifetime
- 1991-04-19 DE DE69120406T patent/DE69120406T2/de not_active Expired - Fee Related
- 1991-04-19 CA CA002080468A patent/CA2080468A1/en not_active Abandoned
- 1991-04-19 JP JP3507808A patent/JP2902481B2/ja not_active Expired - Lifetime
- 1991-04-19 AT AT91908027T patent/ATE139558T1/de not_active IP Right Cessation
Also Published As
Publication number | Publication date |
---|---|
CA2080468A1 (en) | 1991-10-20 |
DE69120406T2 (de) | 1996-11-07 |
WO1991016407A1 (en) | 1991-10-31 |
JP2902481B2 (ja) | 1999-06-07 |
ATE139558T1 (de) | 1996-07-15 |
EP0525040B1 (en) | 1996-06-19 |
DE69120406D1 (de) | 1996-07-25 |
US5478368A (en) | 1995-12-26 |
CN1056118A (zh) | 1991-11-13 |
JPH05506265A (ja) | 1993-09-16 |
EP0525040A1 (en) | 1993-02-03 |
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