CN1060106A - 烃油组合物 - Google Patents

烃油组合物 Download PDF

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CN1060106A
CN1060106A CN91109170A CN91109170A CN1060106A CN 1060106 A CN1060106 A CN 1060106A CN 91109170 A CN91109170 A CN 91109170A CN 91109170 A CN91109170 A CN 91109170A CN 1060106 A CN1060106 A CN 1060106A
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polymkeric substance
composition
ester
carbon
olefin
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CN1032371C (zh
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M·J·雷恩休特
H·P·M·托马森
D·博特
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Shell Internationale Research Maatschappij BV
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Abstract

烃油组合物,其特征是其中含有含石油烃油和如 下添加剂:
a)一氧化碳与一种或多种烯烃的线性聚合物,烯 烃至少部分由C10+α-烯烃组成,该聚合物中基本上 交替出现一氧化碳单元和烯烃单元,以及选自以下聚 合物的一种或多种聚合物:
b)至少部分由C8+烷基酯的烯属不饱和化合物 的聚合物和
c)乙烯与一种或多种饱和脂族单羧酸乙烯基酯 的聚合物。

Description

本发明涉及含烃油和聚合添加剂的新烃油组合物。
瓦斯油,柴油,润滑油和原油等烃油可能含大量石蜡。这些油低温下贮存,运输和应用时,石蜡结晶而引起问题。为避免这些问题,常向含石蜡烃油中加些聚合物。为此所用的第一类聚合物是一氧化碳与一种或多种烯烃的线性聚合物,烯烃至少部分由每分子含至少10碳的α-烯烃(下称C10+α-烯烃)组成,该聚合物中基本上交替出现一氧化碳单元和烯烃单元。适用的第二类聚合物是由一种或多种烯属不饱和化合物聚合物构成,该化合物至少部分由丙烯酸烷基酯或甲基丙烯酸烷基酯(下称C8+烷基酯)组成,而烷基中含至少8碳。第三类适用聚合物由乙烯与一种或多种饱和脂族单羧酸乙烯基酯的聚合物构成。
申请人对用聚合物在含石蜡烃油中作添加剂以改善这些油的低温性能的深入研究已表明,第一类聚合物与第二和/或第三类聚合物的混合物显示出协同活性,这些聚合物中每一类本身均具有降低倾点(PP),浊点(CP)和/或低温过滤堵塞点(CFPP)的活性。这意味着,混合物以给定浓度应用时比每一类聚合物单独以相同浓度应用时达到更大幅度的PP,CP和/或CFPP降低,或混合物可在更低浓度下达到相同PP,CP和/或CFPP降低幅度。
因此本专利申请涉及新烃油组合物,其特征是其中含有含石油烃油和如下添加剂:
a)一氧化碳与一种或多种烯烃的浅性化合物,烯烃至少部分由C10+α-烯烃组成,该聚合物中基本上交替出现一氧化碳是C10和烯烃单元,以及选自以下聚合物的一种或多种聚合物;
b)至少部分由C8+烷基酯的烯属不饱和化合物的聚合物和
c)乙烯与一种或多种饱和脂族单羧酸乙烯基酯的聚合物。
可按本发明提高低温性能的含石蜡烃油可举出瓦斯油,柴油,润滑油和原油。本发明聚合物混合物用含石蜡瓦斯油和原油可达到极佳结果。宜于按本发明用于烃油组合物的聚合物分子量范围很宽,优选重均分子量( Mw)为103-106,特别是104-106
a)中聚合物制备时的C10+α-烯烃单体和b)中聚合物制备时的C8+烷基酯中的烷基优选为直链。C10+α-烯烃和C8+烷基酯中的烷基优选含少于40,特别是少于30个碳原子。聚合物优选给定分子量以及聚合物制备时作单体的C10+α-烯烃和C8+烷基酯中烷基的优选给定碳原子数很大程度上由烃油中石蜡性质决定的。
a)中聚合物制备时,除C10+α-烯烃而外,可用少于10碳的烯烃,如乙烯,丙烯,1-丁烯和环戊烯,但a)中聚合物制备时,优选仅用C10+α-烯烃。a)中聚合物制备时的单体混合物中,除一氧化碳外,还可含一种或多种C10+α-烯烃。按本发明可得到极佳效果的共聚物例子可举出一氧化碳/1-十八碳烯共聚物。本发明可用的三元共聚物可举出一氧化碳/1-十四碳烯/1-十八碳烯三元共聚物。已发现一氧化碳与每分子含20-24碳直链α-烯烃的混合物的聚合物也很宜于用在本发明聚合物混合物之中。
如上述,a)中聚合物优选为一氧化碳与一种或多种C10+α-烯烃的聚合物, Mw为104以上。申请人最近对这些聚合物的研究揭示出吸引人的制备方法,其中基本上是高温高压并在90%v以上由非质子液组成的稀释剂存在下将单体与含Ⅷ族金属和式(R1R2P)2R磷二齿配位体的催化剂组合物接触,其中R1和R2相同或不同,为必要时极性取代脂肪烃基,R为二价有机桥基,连接两个磷原子的桥中含至少两个碳原子。优选用催化剂组合物含0.75~1.5mol磷二齿配位体/克原子Ⅷ族金属,其中R1和R2为不多于6碳的相同烷基且每克原子Ⅷ族金属可含2-50mol pKa低于2的酸根阴离子和必要时的10-1000mol有机氧化剂。特别优选催化剂组合物基于乙酸钯,1,3-双(二正丁基膦)丙烷,1,4-萘醌和三氟乙酸或高氯酸镍。制备聚合物时优选温度30-130℃,压力5-100巴,烯烃:一氧化碳mol比为5∶1至1∶5,而催化剂组合物用量应达到每mol得聚合烯烃含10-6-10-3克原子Ⅷ族金属。聚合优选在含少量质子液的稀释剂中进行,极适宜稀释剂为四氢呋喃和甲醇混合物。
b)中聚合物制备时,除C8+烷基酯外,也可用其它烯属不饱和化合物,如丙烯酸烷基酯和甲基丙烯酸烷基酯,烷基中含少于8个碳原子,烯属不饱和芳族化合物,如苯乙烯和烯属不饱和杂环化合物,如乙烯基吡啶。b)中聚合物制备时的单体混合物可含一种和多种C8+烷基酯。可按本发明达到极佳结果的三元共聚物例子可举出甲基丙烯酸1-十二碳烷基酯/甲基丙烯酸1-十八碳烷基酯/2-乙烯基吡啶三元共聚物以及丙烯酸1-十八碳烷基酯/丙烯酸1-二十碳烷基酯/丙烯酸1-二十二碳烷基酯三元共聚物。可按本发明同样达到极佳效果的聚合物可举出4-乙烯基吡啶与烷基含18-22碳的丙烯酸正烷基酯混合物的聚合物,烷基含12-15碳的丙烯酸正烷基酯混合物的聚合物以及丙烯酸甲酯与烷基含12-15碳的丙烯酸正烷基酯混合物的聚合物。
可获得优异结果的c)中聚合物例子为乙烯与丙酸或乙酸乙烯酯的共聚物,特别是后者可达到优良结果,其分子量及其分布各异,可特别而即时加入烃油中。
在本发明烃油组合物中,可含一种或多种a)中聚合物和一种或多种b)和c)中聚合物。优选烃油组合物中仅含两种添加剂:仅有一种a)中聚合物和仅有一种b)和c)中聚合物。除现有聚合物混合物而外,烃油组合物还可含其它添加剂,如抗氧化剂,防腐剂和金属钝化剂。
可加入本发明含石蜡烃油的聚合物混合物量和混合物中各聚合物相对比例变化范围很大,优选0.1-10000,特别是1-1000mg聚合物混合物/kg烃油。优选用聚合物混合物含1-90%w,特别是10-75%wa)中聚合物,以及优选10-99,特别是25-90%wb)和c)中聚合物。
以下实例详述本发明。
例1
制取一氧化碳/1-十八碳烯共聚物,在250ml搅拌釜中充氮气,加100ml四氢呋喃和40g  1-十八碳烯,并引入催化剂,其中含:
0.5ml甲醇,
0.1mmol乙酸钯,
0.5mmol高氯酸镍,
0.12mmol1,3-双(二正丁基膦)丙烷和6mmol1,4-萘醌。
注入一氧化碳至40巴压力,将釜中物料加热至50℃,30h后混合物冷至室温并卸压而终止聚合。反应混合物中加丙酮后,滤出聚合物,丙酮洗后干燥。共聚物收率40g, Mw为20300。
例2
制取一氧化碳/1-十四碳烯/1-十八碳烯三元共聚物,方法基本上同例1,但有以下不同:
a)釜中含30g1-十八碳烯,而不是40g,还含30g1-十四碳烯,
b)反应温度35℃,而不是50℃和
c)反应时间20h,而不是30h。
三元共聚物41g, Mw为78000。
例3
制取一氧化碳与每分子20-24碳线性α-烯烃混合物的聚合物,方法基本上同例1,但有以下不同:
a)釜中含40g每分子20-24碳线性α-烯烃混合物代替1-十八碳烯,
b)釜中注入一氧化碳至70巴压力,而不是40巴和
c)反应时间15h,而不是30h。
聚合物收率38g, Mw为22700。
例4
制取一氧化碳/1-十六碳烯共聚物,方法基本同例1,但有以下不同点:
a)釜中含38g1-十六碳烯,而不是40g1-十八碳烯,
b)釜中注入一氧化碳至压力70巴,而不是40巴和
c)反应时间15h,而不是30h。
共聚物收率40g, Mw为35000。
例5
制取一氧化碳/1-十四碳烯/1-十六碳烯/1-十八碳烯四元共聚物,方法基本同例1,但有以下不同点:
a)釜中含38gmol比1∶2∶1的n-C14/n-C16/n-C18α-烯烃混合物,代替40g1-十八碳烯,
b)釜中注入一氧化碳至压力70巴,而不是40巴和
c)反应时间15h,而不是30h。
四元共聚物42g, Mw为22000。
例6
以下聚合物作为添加剂用于两种原油(A和B)以及两种瓦斯油(C和D)以降低其PP。
添加剂1:例1共聚物。
添加剂2:例2三元共聚物。
添加剂3:例3聚合物。
添加剂4: Mw为66000的甲基丙烯酸1-十二烷酯/甲基丙烯酸,1-十八烷酯/2-乙烯基吡啶三元共聚物。
添加剂5: Mw为220000的丙烯酸1-十八烷酯/丙烯酸1-二十烷酯/丙烯酸1-二十二烷酯三元共聚物。
添加剂6: Mw为135000的4-乙烯基吡啶与丙烯酸18-22碳正烷基酯混合物的聚合物。
添加剂7: Mw为160000的丙烯酸12-15碳烷基酯混合物的聚合物。
添加剂8: Mw为224000的丙烯酸甲酯与丙烯酸12-15碳烷基酯混合物的聚合物。
聚合物以50%固体甲苯液态引入油中。试验结果列于表1,其中PP为预热至规定温度(50或90℃)并且必要时50℃加规定量聚合物液后得到,示为mg聚合物液/kg含石蜡油。所有添加剂混合物重量比1∶1,试验5混合物除外,其重量比1∶2。PPs按ASTM  D97标准法测定。
表1-倾点
试验号    油    添加剂  溶液    预热℃   ppNos.      mg/kg                            ℃
*1            A          -         -         50       302            A          1+6       2000        50       213            A          1+6       4000        50       154            A          1+6       6000        50       12"5            A          1+6       6000        50       12*6            A           -         -          90       307            A          3+6        400        90       218            A          3+6        600        90       189            A          3+6       1000        90       1210            A          3+6       2000        90       1211            B           -          -         90       2712            B          3+5        400        90        313            B          3+5        600        90        014            B          3+5        800        90        0*15           C           -          -         50       -1216            C          2+7        200        50       -21*17           C           1         100        50       -15*18           C           1        2000        50       -18*19           C           1        4000        50       -18*20           C           4         100        50       -15*21           C           4        2000        50       -21*22           C           4        4000        50       -2123            C          1+4        100        50       -2124            C          1+4       2000        50       -3325            C          1+4       4000        50       -36*26           D           -          -         50       -18*27           D           1         200        50       -21*28           D           8         200        50       -2429            D          1+8        200        50       -27
*=不是本发明,作为对比
″=添加剂1∶添加剂6重量比=1∶2
上述并作PP试验的16种含聚合物混合物烃油组合物为本发明组合物。用a)中聚合物与b)中聚合物的混合物时的协同作用可从添加剂1(试验17-19)或添加剂4(试验20-22)的试验结果与添加剂1和4(试验23-25)的1∶1混合物的试验结果比较中清楚地看出。将瓦斯油D的试验26-29的结果进行比较也可清楚地看出该协同作用。
例7
以下聚合物作为添加剂用于瓦斯油(E)以降低其CFPP。
添加剂9:例4共聚物。
添加剂10:例5共聚物。
添加剂11:市售商标PARAMIN  ECA  5920的乙烯/乙酸乙烯酯共聚物液。
添加剂12:市售商标PARAMIN  PARAFLOW的乙烯/乙酸乙烯酯共聚物液。
添加剂13:市售商标PARAMIN  ECA  8182的乙烯/乙酸乙烯酯共聚物液。
添加剂9和10以50%w固体的甲苯液态加入油中。添加剂11-13以其市售态加入油中。试验结果列于表Ⅱ,其中CFPP为预热到50℃并且50℃加入规定量聚合物液后得到,示为mg溶液/kg瓦斯油。所有添加剂混合物重量比1∶1。CFPPs按IP309标准法测得。
表2-CFPP
试验        添加剂    溶液号                               CFPP                    Nos.             mg/kg               ℃*30                   -                 -                -6*31                   9                40                -9*32                   12               40                -1233                  9+12              40                -19*34                   9               75                -12*35                   12               75                -14*36                   12               300               -1937                  9+12              75                -20*38                   11               40                -12*39                   11               75                -16*40                   11               300               -2141                  9+11              75                -24*42                   13               40                -1543                  9+13              40                -2044                 10+12              75                -19*45                   10               75                -13*46                   13               75                -1647                 10+13              75                -19
*=不是本发明,作为对比
上述并作CFPP试验的6种含聚合物混合物烃油组合物为本发明组合物。用a)中聚合物与c)中聚合物的混合物时出现的协同作用从试验31-33,试验34,35和37,试验34,39和41,试验31,42和43,试验35,44和45或试验45-47的结果之相互比较中很清楚地看出来。
说明用作例6和7添加剂的聚合物制法的例1-5在本发明范围之外。13C-NMR分析可知这些聚合物由线性链构成,其中交替出现一氧化碳单元和α-烯烃单元。在含两种或多种C10+α-烯烃的单体混合物制成的聚合物中,各种C10+α-烯烃单元相互以任意顺序出现。

Claims (10)

1、烃油组合物,其特征是其中含有含石油烃油和如下添加剂:
a)一氧化碳与一种或多种烯烃的线性聚合物,烯烃至少部分由C10+α-烯烃组成,该聚合物中基本上交替出现一氧化碳单元和烯烃单元,以及选自以下聚合物的一种或多种聚合物:
b)至少部分由C8+烷基酯的烯属不饱和化合物的聚合物和
c)乙烯与一种或多种饱和脂族单羧酸乙烯基酯的聚合物。
2、权利要求1的组合物,其特征是聚合物重均分子量( MW)103-106
3、权利要求1或2的组合物,其特征是C10+α-烯烃和C8+烷基酯中的烷基含碳少于40。
4、权利要求1-3中任一项的组合物,其特征是在制备a)中聚合物时仅用C10+α-烯烃作烯烃。
5、权利要求1-4中任一项的组合物,其特征是其中含a)中聚合物,为一氧化碳与一种或多种C10+α-烯烃聚合而得, MW为104以上,可由单体在高温高压并有90%v以上由非质子液组成的稀释剂存在下与催化剂组合物接触而得,催化剂中含Ⅷ族金属和磷二齿配位体(R1R2P)2R,其中R1和R2相同或不同,为必要时极性取代脂肪烃基,R为二价有机桥基,连接两个磷原子的桥中含至少2个碳原子。
6、权利要求1-5中任一项的组合物,其特征是其中含b)中聚合物,选自甲基丙烯酸正十二烷基酯/甲基丙烯酸正十八烷基酯/2-乙烯基吡啶三元共聚物,丙烯酸正十八烷基酯/丙烯酸正二十烷基酯/丙烯酸正二十二烷基酯三元共聚物,4-乙烯基吡啶与丙烯酸正18-22碳烷基酯混合物的聚合物,丙烯酸正12-15碳烷基酯混合物的聚合物以及丙烯酸甲酯与丙烯酸正12-15碳烷基酯混合物的聚合物。
7、权利要求1-6中任一项的组合物,其特征是其中含c)中聚合物,选自乙烯与丙酸或乙酸乙烯酯的共聚物。
8、权利要求1-7中任一项的组合物,其特征是其中仅含一种a)中聚合物并仅含一种b)和c)中聚合物。
9、权利要求1-8中任一项的组合物,其特征是其中含0.1-10000mg聚合物混合物/kg烃油。
10、权利要求1-9中任一项的组合物,其特征是聚合物混合物含1-90%wa)中聚合物。
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RU2027741C1 (ru) 1995-01-27
TW215106B (zh) 1993-10-21

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