CN1214078A - 用作粘度指数改进剂或胶凝剂的基本线性乙烯/α－烯烃聚合物 - Google Patents

用作粘度指数改进剂或胶凝剂的基本线性乙烯/α－烯烃聚合物 Download PDF

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Publication number
CN1214078A
CN1214078A CN96180200A CN96180200A CN1214078A CN 1214078 A CN1214078 A CN 1214078A CN 96180200 A CN96180200 A CN 96180200A CN 96180200 A CN96180200 A CN 96180200A CN 1214078 A CN1214078 A CN 1214078A
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China
Prior art keywords
composition
oil
polymkeric substance
linear ethylene
polymer
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CN96180200A
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CN1098344C (zh
Inventor
M·M·胡赫斯
M·K·劳纳
R·H·麦吉尔克
W·C·施克拉姆
R·G·米勒
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Dupont Characteristic Elastomers Inc
Wen Ben
Dow Chemical Co
Dow Global Technologies LLC
EIDP Inc
Original Assignee
Tang Chemical Materials Co
EI Du Pont de Nemours and Co
DuPont Dow Elastomers LLC
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    • A61K8/81—Cosmetics or similar toiletry preparations characterised by the composition containing organic macromolecular compounds obtained by reactions involving only carbon-to-carbon unsaturated bonds
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Abstract

当把基本线性乙烯聚合物,比如乙烯/辛烯共聚物和乙烯/丙烯/二烯改性聚合物以粘度改性量加入到含油材料中去时使材料的粘度指数超过其材料本身。用几何受限催化剂制备的基本线型乙烯聚合物可用一种或多种如的马来酸酐之类含不饱和烯键不饱和有机化合物来接枝。接枝了的聚合物可通过与一诸如醇或胺化合物的反应而进一步官能化。当基本线型乙烯聚合物在加入到含油材料之前或之后承受一剪切作用时,则含油材料的剪切稳定性就得到了改进。无论是接技,接技后是否进一步反应,该基本线型乙烯聚合物均可用作比如在润滑脂、电缆填充混合料和化妆品之类中使用的组合物的增稠剂。此外,基本线型乙烯聚合物与传统含油材料组合物的其他组分共混的结果也有效。

Description

用作粘度指数改进剂或胶凝剂的基本 线性乙烯/α-烯烃聚合物
本申请要求1996.8.30提交的美国临时申请号60/024,913
和1996.3.8．提交的美国临时申请号60/013,052的权益。
本发明一般而言涉及含至少一种作为粘度指数(以下简称为VI)改进剂或胶凝剂的乙烯/α-烯烃共聚体的含油组合物。本发明更具体涉及这样的组合物，其中共聚物基本上为线型，尤其是具有均匀支化分布和窄分子量分布(MWD)。该共聚体可通过一步或多步的进一步反应来改性以提供另外的功能。一个令人特别感兴趣的这种反应包括，将如马来酸酐这样的烯烃类不饱和有机化合物接枝到该共聚体上，所得到的接枝聚合物再进一步与一种或多种如胺之类另外的化合物进行反应。
当把VI改进剂加入到含油组合物中去之后，组合物在高温下的粘度更为可人或有所改进。高温粘度的改善和提高而没有其他变化被称之为VI改进。
VI是一个用来度量润滑剂粘度和温度稳定性的经验数。高VI表示在升温或高温下抗变稀，而低VI则表示在这样的温度下有变稀的倾向。
VI改进剂的性能指标包括增稠能力、剪切稳定性以及化学与热氧化稳定性，所有这些是与聚合物结构相关的。一个提供所期高温测粘行为的给定VI改进剂的能力取决于诸如聚合物分子量、浓度和与含油组合物的化学结构相关的化学结构之类的因素。剪切稳定性在很大程度上取决于聚合物分子量和MWD。
已有各种不同的油溶性聚合物被用来作为润滑油的VI改进剂。例证聚合物包括氢化苯乙烯/二烯聚合物、氢化聚异戊二烯、聚甲基丙烯酸烷基酯，以及如乙烯/丙烯共聚物和乙烯/丙烯/二烯三元共聚物之类乙烯/α-烯烃共聚物以及这些二元共聚物与三元共聚物的不同衍生物。这些聚合物可用来制备那些同时满足SAE(汽车工程师协会)高温和低温测粘要求的多级通用润滑油(如10W-30)。
至少某些油溶性聚合物对于作为其他的如矿物油、石蜡油和环烷油的含油材料的增稠剂或胶凝剂以制备适合作为润滑脂或化妆材料使用的组合物来说也是有用的。
基于在茂金属催化剂存在下制备的乙烯烯烃共聚物之VI改进剂也已有文献公开，如USP 5,151,204和USP5,446,221。
发明概述
本发明的一个方面是一种含含油材料和粘度改进有效量的基本线型乙烯聚合物(以下简称SLEP)的含油组合物，该SLEP的特征在于：(ⅰ)熔体流动比，I10/I2≥5.63；(ⅱ)MWD,Mw/Mn，由方程Mw/Mn≤(I10/I2)-4.63所定义；和(ⅲ)开始出现表面熔体破裂(以下简称OSMF)的临界剪切速率至少要比有类似I2和Mw/Mn的线型烯烃聚合物在OSMF的临界剪切速率大50％。
第一个相关方面是，聚合物的数量是使得组合物适合用于制备润滑脂或化妆材料的有效增稠或胶凝用量。
第二个相关方面是，含油组合物还含一种倾点下降剂(以下简称PPD)，其用量足以使其低温性质比不合PPD的相似组合物的低温性质得到改进。
第三个相关方面是，至少部分SLEP为剪切改性的SLEP所替代，借此，含油组合物的剪切稳定性得以提高。该剪切改性聚合物的适当制法为：对SLEP施加足以提高其熔体指数(I2)的剪切作用。
第四个相关方面是，该含油组合物除包含SLEP之外还包含至少一种聚合物，选自氢化聚异戊二烯、苯乙烯/丁二烯嵌段聚合物、苯乙烯/异戊二烯嵌段聚合物、氢化苯乙烯/丁二烯嵌段聚合物、氢化苯乙烯/异戊二烯嵌段聚合物、接枝苯乙烯/丁二烯嵌段聚合物、接枝苯乙烯/异戊二烯嵌段聚合物、聚甲基丙烯酸烷基酯、聚丙烯酸烷基酯、乙烯聚合物和丙烯酸酯/甲基丙烯酸酯聚合物。
上述方面与相关方面的每一方面又包括3个进一步相关方面(a)至(c)。方面(a),SLEP中的乙烯含量在聚合物重量的20至80重量百分数范围内。方面(b),SLEP被接枝上至少为接枝后SLEP重量的0.01重量百分数的含可接枝部分的不饱和有机化合物。方面(c)，含活性部分的接枝SLEP与含羟基或胺基官能团的化合物进一步反应。例证化合物包括醇，尤其是脂族饱和一元醇、酸和胺特别是伯胺。
“嵌段共聚物”包括二嵌段聚合物、三嵌段聚合物、辐射状嵌段或星形嵌段聚合物和锥形共聚体。
“乙烯聚合物”意指乙烯/α-烯烃共聚物或二烯改性乙烯/α-烯烃共聚物。例证聚合物包括乙烯/丙烯(以下简称EP)共聚物、乙烯/辛烯(以下简称EO)共聚物和乙烯/丙烯/二烯改性(以下简称EPDM)共聚体。
“基本线型”意指聚合物的主链中每1000个主链碳原子被0.01至3个长支链所取代。
“长支链”或“LCB”意指链长至少6个碳原子。在此长度以上，碳-13核磁共振谱(C-13 NMR)不再能区分和确定链中的碳原子数。在某些情况下，链长可与它所连接的聚合物主链一样长。
“共聚体”是指至少由二种单体聚合的聚合物。它包括，例如共聚物、三元共聚物和四元共聚物。它尤其包括由乙烯与至少一个共聚单体，典型的为3至20个碳原子(C3～C20)的α-烯烃的共聚单体聚合制得的聚合物。例证α-烯烃包括丙烯、丁烯-1、己烯-1、4-甲基戊烯-1、庚烯-1、辛烯-1和苯乙烯。C3～C10的α-烯烃是所希望的。优选的共聚物包括EP和乙烯-辛烯共聚物。例证三元共聚物包括乙烯/丙烯/辛烯三元共聚物以及乙烯、C3～C20的α-烯烃与诸如二环戊二烯、己二烯-1,4、戊二烯-1,3、5-亚乙基降冰片烯-2、之类的二烯的三元共聚物。
基本线型乙烯α-烯烃共聚体(“SLEP”或“基本线型乙烯聚合物”)可按如美国专利USP5,272,236和5,278,272所述来制备，这两篇专利的相关部分被列作为本发明的参考文献。USP5,272,236(从5栏67行至6栏28行)叙述了经过用至少一个反应器，但允多个反应器，在足够产生有所期性质的SLEP的温度和压力下连续控制聚合生产SLEP的过程。聚合方法优选采用在20至250℃下用几何受限催化剂技术的溶液聚合。
合适的几何受限催化剂在USP5,272,236的6栏29行至13栏50行列出。可以这样来描述这类催化剂：即它包含一种金属配合物，该配合物包含元素周期表中第3～10族或镧系的金属，以及由一个约束诱导部分所取代的离域π键部分。配合物具有围绕金属原子的受限几何构型，致使取代的离域π键部分的中心与至少一个其余取代基中心之间以该金属为顶点的角度要比含缺少这种约束诱导取代基的类似π键部分的类似配合物的相应角度小。如果这样的配合物包含多于一个取代的离域π键部分，则配合物的每个金属原子仅有一个这样的部分是取代的环状、离域π键部分。催化剂还进一步含一个如三(五氟苯基)甲硼烷之起活化作用的助催化剂。USP5,272,236的6栏57行至8栏58行和USP5,278,272的7栏48行至9栏37行讨论了特定的催化剂配合物。有关这些催化剂一般技术和这些特定催化剂的具体技术被收作本发明的参考文献。
SLEP的特征在于其窄MWD以及若是共聚体的话为窄共聚单体分布。SLEP的特征还在于其于低残余量，具体地说指催化剂残余物、未反应共聚单体和聚合过程中产生的低分子量齐聚物的残余含量而言。SLEP的进一步特征是通过控制分子构造而提供好的加工性，即便其MWD比普通烯烃聚合物窄。
优选的SLEP有一系列鲜明的特征，一是共聚单体含量中有20至80重量百分数更优选30至70重量百分数的乙烯，而其余则为一种或多种共聚单体。SLEP共聚单体含量可用红外光谱(IR)按照美国材料试验学会(以下简称ASTM)D-2238的方法B或ASTM D-3900来测量。共聚单体含量也可由C-13 NMR谱来确定。
SLEP的另一个鲜明特征包括I2和熔体流动比(MFR或I10/I2)。按照ASTM D-1238，在190℃/2.16Kg条件(原来的条件E)下所希望的共聚体的I2为0.01～500g/10min，而以0.05～50g/10min为更好。按照D-1238,SLEP的MFR≥5.63，而以6.5～15为宜，7～10更好。对SLEP来说，I10/I2比值是LCB程度的表征，故而I10/I2比值越大就等于说聚合物的LCB程度越高。
SLEP的又一个鲜明特征在于其由凝胶渗透色谱(GPC)测定的MWD(Mw/Mn或“多分散指数”)。Mw/Mn由下面的方程来定义：
Mw/Mn≤(I10/I2)-4.63
希望MWD＞0且＜5，特别是在1.5至3.5之间，优选为1.7至3。
令人惊奇的是，均匀支化SLEP的MFR是基本上与其MWD无关的。这是与普通的线型均匀支化和线型杂支化乙烯共聚物形成了明显的反差，后者，必须增大MWD以提高MFR。
SLEP的进一步特征在于它的OSMF的临界剪切速率比具有类似I2和Mw/Mn的线型烯烃聚合物的OSMF临界剪切速度大50％。
满足上述标准的SLEP包括，例如牌号为ENGAGETM的聚烯烃弹性体和其他的由杜邦道弹性体股份有限公司用几何受限催化剂生产的聚合物。
SLEP可以在经诸如接枝的改性或未改性的情况下加入到含油组合物中。若用接枝改性，所得接枝SLEP也可在经或未经一步或多步附加的反应后再加入到含油组合物中去。也可以在SLEP已经加入到含油组合物中之后再接枝。
任何一种含有至少一个烯键不饱和结构(至少一个双键)的且能接枝到SLEP上的不饱和有机化合物均可用来使SLEP改性。例证不饱和化合物包括乙烯基醚、乙烯基取代的杂环化合物、乙烯基
Figure A9618020000091
唑啉、乙烯基胺、乙烯基环氧化物、不饱和环氧化物、不饱和羧酸和这些酸的酐、醚、胺、或酯。代表性的化合物包括马来酸、富马酸、丙烯酸、甲基丙烯酸、衣康酸、巴豆酸、α-甲基巴豆酸和肉桂酸以及它们的酐、酯或醚衍生物、乙烯基取代的烷基酚和甲基丙烯酸缩水甘油酯。合适的不饱和胺包括那些含至少一个双键和至少一个胺基(至少一个一级、二级或三级胺)的脂族和杂环有机氮化合物。代表性的例子包括乙烯基吡啶和乙烯基吡咯烷酮。马来酐是优选的不饱和有机化合物。
接枝SLEP中的不饱和有机化舍物的含量为≥聚合物与有机化合物重量之和的0.0l重量百分数，优选≥0.05重量百分数。不饱和有机化合物的最大含量可能有所变化，不过典型的为≤10重量百分数，优选为≤5重量百分数，而≤2重量百分数更好。
可以用任何已知技术，比如那些在USP3,236,917和USP5,194,509中所描述的技术来把不饱和有机化合物接枝到SLEP上，这些相关技术被收入本发明作为本发明参考文献的一部分。在USP3,236,917中，把EP共聚物之类的聚合物加入到双辊式混合机中并在600℃温度下混合。然后把马来酐之类不饱和有机化合物与过氧化苯甲酰之类自由基引发剂一起加入，并在30℃把组分混合直至接枝完成。
USP5,194,509公开了一种类似于USP3,236,9l7的方法的专利，不过它的反应温度更高(210至300℃，优选210至280℃)以及不用或限制自由基引发剂的用量。USP5,194,509特别提出不饱和羧酸、酐及其衍生物的无过氧化物接枝可在普通的如Werner & Pfleiderer的ZDSK53双螺杆挤出机或其他一些如Brabender反应器之类普通装置中进行。乙烯聚合物以及必要时待接枝单体，在140℃或更高温度下彻底混合，然后在高温(从210至300℃，优选210至280℃,210至260℃更好)下反应。在乙烯聚合物熔融之前还是之后把待接枝上去的单体引入反应器这点并不重要。所用的待接枝单体的浓度为乙烯聚合物重量的0.01～0.5重量百分数，而以0.05～0.25重量百分数为优选。
USP4,950,541中公开了一种替代且为优选的接枝方法，它的相关技术作本发明的参考文献。该替代方法使用的是双螺杆排气式挤塑机作为混合装置。SLEP和不饱和有机化合物在挤塑机中于反应物的熔融温度和自由基引发剂存在下混合和反应。优选的是把不饱和有机化合物注入到挤塑机的保持压力的区中。
第二种优选的替代的接枝方法是USP4,810,754所涉及的溶液接枝法，其相关技术也作为本发明的参考文献。该方法包括，在矿物油之类溶剂中把引发剂、待接枝的单体和如EP聚合物之类聚合物混合，然后在足够引发接枝反应的温度下反应。一种这样的温度是190℃。
接枝改性的SLEP可与改性材料发生进一步的反应以引入一种或多种官能团，进而改进含有接枝并进一步反应的SLEP的含油组合物中氧化剂或燃烧副产物的分散性、低温粘度以及氧化/热稳定性。例证的改性材料包括醇，长链(典型的最高36个碳原子的)脂肪酸和胺。醇的例子包括有≥2个碳原子的脂族和芳族醇，大于12个碳原子的醇为优选，小于36个碳原子的醇更好。代表性的醇和长链脂肪酸包括癸基、月桂基和十八烷基醇和酸。胺的例子包括那些含≥一个一级和/或≥一个二级且任选地≥一个三级胺的脂族和杂环氮化合物。某些胺，比如三亚乙基四胺、四亚乙基五胺和多亚乙基多胺(比如市售的道化学公司的Ethyleneamine E-100)既含有脂族也含有杂环部分。市售多亚乙基多胺典型的是线性、支化和杂环亚乙基胺的共混物或混合物。代表性的例子包括多亚乙基(如二亚乙基三胺)、3-氨基乙基咪唑-1、氨基乙基哌嗪、4-(3-氨基丙基)吗啉和多氧亚烷基多胺(如由Huntsman化学公司生产的JeffaminesTM)。USP5,401,427申请了附加的醇和胺的专利，特别是在其中的45栏40行至49栏29行，相关技术已被引入本专利作为参考文献。
USP5,401,427公开了其他合适的亚烷基多胺，包括亚甲基胺、亚乙基胺、亚丁基胺、亚丙基胺、亚戊基胺、亚己基胺、亚庚基胺、亚辛基胺、其他的多亚甲基胺、这些胺的环状物和更高级的同系物如哌嗪、氨烷基取代哌嗪等。这些胺包括，例如乙二胺、二亚乙基三胺、三亚乙基四胺、丙二胺、二(七亚甲基)三胺、三亚丙基四胺、四亚乙基五胺、三亚甲基二胺、五亚乙基六胺、二(三亚甲基)三胺、2-庚基-3-(2-氨基丙基)咪唑啉、4-甲基咪唑啉、1,3-二(2-氨基丙基)咪唑啉、嘧啶、1-(2-氨基丙基)哌嗪、1,4-二(2-氨基乙基)哌嗪、N,N’-二甲氨基丙胺、N,N’-二辛基乙胺、N-辛基-N’-甲基亚乙基二胺和2-甲基-1-(2-氨基丁基)哌嗪。术语多胺涵盖羟烷基多胺，特别是氮原子上有一个或多个羟烷取代基的羟基烷基亚烷基多胺。这类羟烷基取代的多胺的例子包括N-(2-羟基乙基)亚乙基二胺、N,N-二(2-羟基乙基)亚乙基二胺、1-(2-羟基乙基)哌嗪、单羟基丙基取代二亚乙基三胺、二羟丙基取代四亚乙基五胺和N-(3-羟丁基)四亚甲基二胺。
USP5,401,427中公开的醇和多元醇包括含≤100碳原子和2至10个羟基的脂肪多元醇。按照需要，这些醇可是取代或未取代的、受阻或未受阻的、或支链或直链的。典型的醇是如乙二醇、丙二醇、1,3-丙二醇、丁二醇之类亚烷基二醇，以及如二甘醇、三甘醇、四甘醇、二丙二醇、三丙二醇、二丁二醇、三丁二醇之类的多二元醇和其他含2至8个碳原子的亚烷基二醇和多亚烷基二醇。优选的含≤20个碳原子的脂肪醇包括甘油、赤藓醇、季戊四醇、二季戊四醇、三季戊四醇、葡糖酸、甘油醛、葡萄糖、***糖、1,7-庚二醇、2,4-庚二醇、1,2,3-己三醇、1,2,4-己三醇、1,2.5-己三醇、2,3,4-己三醇、1,2,3-丁三醇、1,2,4-丁三醇、2,2,6,6-四(羟甲基)环己醇和1,10-癸烷二醇。
当把SLEP、接枝改性的SLEP和/或进一步反应的接枝改性SLEP加入到不同的基油或含油材料中后，与不含这种SLEP或这种接枝改性的SLEP或这种进一步反应的接枝改性的SLEP的含油材料相比，此种含油材料的VI、分散性、稳定性和胶凝或增稠等指标中至少一种指标改善了。
适合用于润滑油配方中的含油材料或基油可包含用来自于天然和合成来源制成的未精制、精制和再精制(再生)油。例证含油材料包括任何的形成本发明组合物的不同烃油、基于烯化氧聚合物及其衍生物的润滑油、二元酸酯油、或硅基油。这些油可是天然的或合成的，包括润滑油和燃油。合适的油的例子包括煤油、石蜡润滑油、环烷润滑油和石蜡-环烷的混合型润滑油、煤或页岩提炼的油、聚(α-烯烃)油、植物油、动物油、由一种或多种环氧乙烷、环氧丙烷或环氧丁烷、四氢呋喃制备的聚氧化烯聚合物或共聚物、聚烷基、聚芳基、聚烷氧基或聚芳氧基硅氧烷油和硅酸酯油。也可使用这些油的共混物。USP5,446,221的8栏47行至10栏34行揭示了不同含油材料的附加信息，这也作为本发明的参考文献。
当无论是未接枝的、接枝或接枝并进一步反应的SLEP用作为含油组合物中的VI改性剂时，组合物也可含有几种不同类型的增加对含这种组合物的材料所要求特性的添加剂。这些添加剂可包括传统的VI改进剂，一般包括分散剂、洗涤剂、抗氧化剂、耐磨添加剂和耐压剂、摩擦改性剂、PPD、腐蚀抑制剂、无灰分散剂(如聚异丁烯基琥珀酰亚胺和其含硼衍生物)和抗沫剂。这些添加剂一般存在的量为相对于油重量的0.001至20重量百分数。传统VI改进剂包括高分子量碳氢聚合物、聚甲基丙烯酸烷基酯和含不饱和C3至C8一元与二元羧酸的共聚单元之聚酯。添加剂可以浓缩物或在油中的分散液或未稀释的形式加入。
在制备调配润滑油配制物中，通常引入的添加剂为油中含活性组分浓度5至80重量百分数的形式。采用浓缩物使不同材料处理起来困难较少而且促添加剂在配制物中的溶解或分散。
PPD可降低润滑油流动或可倾倒的温度。这样的PPD是大家熟悉的。典型的可用于改善润滑油低温流动性的那些添加剂是富马酸二烷基酯醋酸乙烯酯共聚物、聚甲基丙烯酸酯(USP2,091,627和2,100,993)与萘蜡(USP2,174,246)。
当在制备润滑脂、应用于电线和电缆头用材料或触变胶凝剂中把无论是未接枝的、接枝的或接技并进一步反应了的SLEP加入到含油组合物中作为增稠剂或胶凝剂时，它可与那些规定在采用浓缩物用作润滑油含油组合物中使用的，任何或所有的添加剂结合使用。例证的电线和电缆头用途包括普通使用的比如铸封料、防水材料和绝缘材料。这些应用对光缆是特别重要的。
当把这样的聚合物加入到含油组合物中作为增稠剂或胶凝剂以用作化妆品、药膏或外用药时，它们可与其他的如香料、着色剂、染料、稳定剂、表面活性剂、软化剂和油(比如椰子油)结合使用。
具有改进的低温性质的含油组合物包含含油材料、PPD和改进粘度有效量的SLEP。当SLEP为基本上无定形(它可含≤6％的结晶度，以3％为宜，更优选≤1％、但≥0更好)时，只要含油材料中所含的蜡的开始结晶温度(Tc)不在SLEP中所含蜡的Tc范围内，可以使用任何普通的PPD。当SLEP为半结晶(结晶度6至25％，以6至20％为优选，6至16％更好)时，加入某种优选的PPD，即富马酸二正烷基酯和醋酸乙烯酯的共聚物，就可得到满意的低温性质。用作PPD的共聚物宜于按USP4,839,074所述来制备，有关内容也加入到本发明作为参考文献。
USP4,839,074中的一部分内容提道，先把诸如富马酸之类二元酸酯化，然后再与如乙烯酯之类可聚合单体化合物反应或共聚，采用传统的自由基聚合技术来得到无规聚合物。合适的聚合是在惰性烃类溶剂(如己烷或庚烷)、无氧环境(如氮气氛)及65-150℃温度下进行的。虽然优选将二酸单体的所有羧基完全酯化，但部分酯化(≥70摩尔百分数的可酯化羧基已酯化)也已足够了。典型的酯化是用混合醇来进行的，所用的醇可是少许支化的，但以直链C1至C20的脂肪醇为优选，C6至C20脂肪醇更好。
据信，半结晶SLEP可与富马酸二正烷基酯/醋酸乙烯酯共聚物配合使用效果很好，它的(用差示扫描量热(DSC)测定的)峰值结晶温度不同于含油材料中所含蜡的此温度，因而SLEP和含油材料中所含的蜡将如期望的那样不发生共结晶。由于含油材料的峰值结晶温度因诸如蜡含量等因素而明显改变，含油材料、半结晶SLEP和富马酸二正烷基酯/醋酸乙烯酯共聚物的每种组合必须接受对其低温性质的评价。
本发明的组合物是把改性(如接枝、接枝后进一步反应或未进一步反应)或未改性的SLEP用普通的共混技术加入到油或含油组合物中形成的。聚合物可以单独或以油浓缩物形式加入。一般，加入的聚合物量的范围为被改性油的重量之0.1至20重量百分数(干聚合物)，0.2至5重量百分数的干聚合物对粘度改性是优选的，而作增稠或胶凝应用时则5-15重量百分数的干聚合物为优选。
在制备润滑油的配料中，添加剂通常是以活性组分在烃油(如矿物润滑油)或一些其他合适溶剂中的浓缩物形式加入的。典型浓缩物的活性组分含量为浓缩物总重量的5至80重量百分数。在调配精制润滑剂如曲轴箱马达油的过程中，浓缩物通常是每重量份添加剂以3至100重量份，有时以5至40重量份的润滑油来稀释的。所用浓缩物使不同添加剂的操作变得较为容易，从而使添加剂在最终润滑剂中容易形成溶液或分散体系。作为一个例子，典型的VI改进剂是以在润滑油5至20重量百分数的浓缩物来应用的。
本发明部分涉及到VI有改进的含油或油组合物，特别涉及包含润滑油和作为VI改进剂的SLEP的油组合物。与不含这样的VI改进剂之油组合物相比，含有这样的VI改进剂之油组合物的高温粘度改进了。由VI改进剂出发也可衍生出其他的性质或功能，如对燃油和润滑油组合物的分散性。衍生的聚合物包括比如(按如上和USP5,346,963的3栏67行至4栏24行所述来制备的)马来酐接枝的SLEP之类接枝SLEP，它可与醇或胺进一步反应，比如USP3,702,300(4栏56行至5栏60行涉及用混合醇使比如含马来酐共聚体之类含羧基共聚体的酯化，然后用多胺来中和残留的羧基)；USP4,089,794(3栏37行至4栏59行涉及烯类不饱和羧酸材料，如马来酐按溶液接枝于乙烯/α-烯烃聚合物如EP共聚物上然后用多胺与接枝了的聚合物反应)；USP4,160,739(6栏35-52行涉及由非聚合性多胺与马来酸或酐接枝物的反应所提供的羧基的后反应)；或USP4,137,185(7栏4-17行涉及在溶液中接枝了的羧酸材料的反应，如马来酐接枝了的乙烯/α-烯烃聚合物与多(一级胺)的反应)；或如USP4,068,056所示的接枝了氮化合物的SLEP(4栏47行至5栏23行涉及齐格勒-纳塔催化的碳氢聚合物在含氧气体存在下与胺化合物于130℃至300℃在混合条件下的反应)；USP4,146,489(2栏49行至3栏15行，涉及C-乙烯基哟啶或W-乙烯基吡咯烷酮按自由基接枝聚合到EP橡胶或EPDM橡胶上；以及USP4,149,984涉及可聚合杂环化合物如乙烯吡啶或乙烯吡咯烷酮接枝于一种在聚烯烃聚合物溶液中甲基丙烯酸C8～C18醇酯聚合形成的聚合物上)。这些专利的有关技术作为本发明的参考文献。
下面的实施例用以说明本发明，但本发明不受它们的无论是明确还是含蓄的限制。除非另外提到，所有的份数和百分数都是指相对于总重量而言的。
实施例
用于实施例的11种基本聚合物中的8种代表本发明，聚合物B、E和I不代表本发明。所用聚合物为：
A：市售的杜邦道弹性体股份有限公司生产的乙烯/辛烯共聚物(乙烯含量61.7重量百分数)，商品名EG8200；
B：市售的Exxon化学公司生产的乙烯/丁烯共聚物，商品名EXACTTM4024；
C：市售的杜邦道弹性体股份有限公司生产的乙烯/辛烯共聚物(乙烯含量68.2重量百分数)，商品名EG8100；
D：杜邦道弹性体股份有限公司研制的乙烯/丙烯/亚乙基降冰片烯三元共聚物(乙烯含量57重量百分数)；
E：市售的Mitsui石化公司生产的EP共聚物TAFMERTM P-0480；
F：市售的杜邦道弹性体股份有限公司生产的乙烯/辛烯共聚物(乙烯含量64.7重量百分数)EG8150；
G：市售的杜邦道弹性体股份有限公司生产的乙烯/辛烯共聚物(乙烯含量61.0重量百分数)EG8180；
H：杜邦道弹性体股份有限公司研制生产的EP共聚物(乙烯含量53.1重量百分数)；
I：市售的Mitsui石化公司生产的EP共聚物TAFMERTM P-0480；
J：杜邦道弹性体股份有限公司研制的EP共聚物(乙烯含量34.7重量百分数)；
K：道化学公司研制的乙烯/苯乙烯共聚物(乙烯含量60重量百分数)。
表IA和IB列出了基本聚合物A～K的物理性质数据。
表IA
聚合物/性质   A   B     C    D   E   F
I2(g/10min)密度(g/cm3)I10/I2比Mw/MnOSMF的临界剪切速率(秒-1)  5.00.8707.381.925423  3.30.8785.81.95250  1.00.8707.991.96366  1.720.8608.132.361670  1.10.8706.061.90105  0.500.8687.372.03385
表IB-聚合物描述
聚合物/性质   G    H    I       J   K
I2(g/10min)密度(g/cm3)I10/I2比例Mw/MnOSMF的临界剪切速率(秒-1)  0.500.8637.302.00101  0.470.8608.851.91134   0.30.8706.101.9558     0.640.85510.52.6290  2.00.9749.53.1-*
*没得到实施例1～8
试验了7种SLEP作为基油A(Exxon化学公司的FN1365 100N)的VI改进剂。每种SLEP的浓缩物(聚合物浓度6重量百分数)是由把聚合物溶于热(110～120℃)的基油中而制得的。然后把浓缩物加入到基油中并进行测试。测定了基油A和基油A与0.9重量百分数的SLEP的每种组合以厘瘄(centistokes，简称cSt)为单位的运动粘度(KV)。KV值是在40℃和100℃下按照ASTM D-445测定的，表Ⅱ列出了这些KV值及聚合物对100℃下的KV的贡献。
表Ⅱ
实施例编号  聚合物 40℃下的KV(cSt)    100℃下的KV(cSt) 聚合物对100℃下KV的贡献(cSt)
    1*   无     19.87     4.009     -
    2     A     **     7.361     3.352
    3     C     58.08     8.855     4.846
    4     D     45.07     8.160     4.151
    5     F     56.97     9.656     5.647
    6     G     54.59     9.684     5.675
    7     H     56.31     9.927     5.918
    8     K     32.05     6.179     2.170
*非本发明的实施例；**没测量
表Ⅱ所示的KV值表明SLEP可起到一种油的添加剂功能，当把它加入到含油组合物中后使在如100℃的高温下的粘度得到改进。这些KV值也表明聚合物添加剂的增稠能力，且可进一步的用来计算加入到如5W-30马达油之类全配方润滑油中的量。实施例9～13
进行5种SLEP作为5W-30调配润滑油的VI改进剂的试验。SLEP浓缩物(6重量百分数)是按实施例2-8一样制备的。表Ⅲ示出了配制物的组成。使用二种不同的基油，即基油A和基油B(Exxon化学公司的FN1243 150N油)来制备这些配制物。分散抑制剂(DI)添加剂(DI-1)用的是乙基公司的8482-A1。PPD添加剂(PPD-1)用的是Rohm &Hass开发的定名为XPD-194的聚甲基丙烯酸烷基酯聚合物。
用含SLEP VI改进剂的配制物进行三项试验：如实施例1-7所测定的100℃之KV值；按照SAE J300附录在-25℃下的曲轴低温模拟器中的测定(CCX)；以及按照ASTM D-4741和D-4683测定150℃下的高温热剪切(HTHS)。表Ⅲ也示出了这些试验的结果。
表Ⅲ
实施例编号   9   10    11    12    13
组分    重量百分数    重量百分数   重量百分数   重量百分数   重量百分数
基油A     68.97     67.94     68.93     71.29     78.25
基油B     2.49     8.22     8.92     6.23     0.00
DI-1     11.31     11.31     11.31     11.31     11.31
PPD-1     0.30     0.30     0.30     0.30     0.30
聚合物A浓缩物     16.94     -     -     -     -
聚合物C浓缩物     -     12.23     -     -     -
聚合物F浓缩物     -     -     10.54     -     -
聚合物G浓缩物     -     -     -     10.88     -
聚合物H浓缩物     -     -     -     -     10.15
试验结果     -     -     -     -     -
KV(cSt)     10.69     11.78     10.56     10.66     10.31
 CCS(cP)     3,190     3,250     3,180     3,100     3,220
 HTHS(cP)     3.11     3.18     2.91     3.04     3.00
表Ⅲ的数据表明，实施例9～13的含按照本发明SLEP的配制物满足5W-30调配润滑油的SAE SH分类标准。该标准是，KV为9.1至12.5cSt,CCS＜3500 cP(厘泊，下同)和HTHS＞2.9cP。实施例14～21
对用聚合物G(乙烯/辛烯共聚物)和D(乙烯/丙烯/亚乙基降冰片烯三元共聚物)掺入溶剂中性油(SN)和加氢裂化油(HC)等基油制备的配制物5W-30(实施例14,15,18和19)与10W-30(实施例16,17,20和21)的性能进行评估。SN基油是基油A和B。HC基油是ChevronUSA产品公司的100R RLOP油(基油C)与240R RLOP油(基油D)。DI(DI-2)是ParaminsTMPDN2977,PPD是PPD-1。聚合物G和D是以如实施例2～8中的6重量百分数浓缩物加入的。表Ⅳ示出了组分量和如实施例9～13同样试验的试验结果。10W-30调配润滑油的SAE SH分类标准除了CCS是在-20℃测定外，其余均与5W-30配制物标准一样。
表Ⅳ
实施例编号  14    15   16  17     18     19   20   21
配制物种类 5W-30SN  5W-30HC  10W-30SN 10W-30HC  5W-30SN  5W-30HC  10W-30SN  10W-30HC
组分 重量百分数 重量百分数  重量百分数 重量百分数   重量百分数 重量百分数  重量百分数  重量百分数
基油A 74.87  -  0.07   -  78.71   -  7.03    -
基油B 3.65  -  82.10   -    -   -  72.15    -
基油C -  74.40    -  48.23    -  77.59    -  53.03
基油D -  4.44    -  33.51    -  0.17    -  25.42
DI-2 9.91  9.91  9.91  9.91  9.91  9.91  9.91  9.91
PPD-1 0.20  0.20  0.20  0.20  0.20  0.20  0.20  0.20
聚合物G浓缩物 11.40  11.04  7.72  8.15    -    -    -    -
聚合物D浓缩物  -   -    -    -  11.17  12.14  10.71  11.44
试验结果
KV(cSt) 10.65  10.52  10.65  10.48  9.24  9.55  10.78  10.49
-25℃的CCS(cP) 3,210  3,365    -    -  3,600  3,600    -    -
-20℃的CCS(cP) -  -  3,145  2,760    -    -  3,245  2,770
HTHS(cP) 2.91  2.81  2.94  2.92  2.83  2.76  3.20  3.01
表Ⅳ的数据表明，按照10W-30润滑油组合物的SAE SH分类准标，所有的聚合物与基油A、B、C和D调配效果很好。在基油A中聚合物G满足5W-30润滑油组合物的所有SAE SH分类标准，而在基油B中，聚合物G满足除了HTHS之外的所有标准。在基油A和B中，聚合物D仅满足5W-30的KV标准。作者相信，一个熟练的工作者能方便地对实施例15、18和19进行配方优化以满足5W-30配制物的所有SAE SH标准。实施例22～25
重复实施例14～21只是其中信采用基油C和D,DI改变为(实施例22和24中的)从乙基公司得到的HitecTM1117(DI-3)或是只是其中仅采用(实施例23和25中的)从Oronite公司得到的OLOA9250RXA1736(DI-4),PPD改用市售的Exxon化学公司的牌号为ParaminsParaflowTM392的富马酸二烷基酯。表Ⅴ示出了组分用量和试验结果。
表Ⅴ
实施例编号 22 23 24 25
    配制物种类  5W-30    5W-30  10W-30  10W-30
    组分 重量百分数   重量百分数 重量百分数 重量百分数
    基油C  72.40     72.69  43.13  34.41
    基油D  5.17     6.02  37.81  48.28
    DI-3  10.84       -  10.85    -
    DI-4    -     8.76     -  8.75
    PPD-3  0.20     0.20  0.20  0.20
    聚合物G浓缩物  11.39     12.34  8.01  8.75
    试验结果
    KV(cSt)  10.67     10.53  10.56  10.43
    -25℃的CCS(cP)  3,130     2,960     -    -
    -20℃的CCS(cP)    -       -  2,700  2,760
    HTHS(cP)  3.11     3.08  3.16  3.14
表Ⅴ所示数据表明，本发明的基本线型乙烯聚合物都可满足5W-30和10W-30二者的SAE SH分类标准，而且都有作为润滑油的VI改进剂的功能。实施例26～28
重复实施例1～7的制备程序，只是改用聚合物G与三种其他聚合物之一的混合物，其量示于表Ⅶ中。三种其他聚合物是聚合物D(实施例26)、市售的Exxon化学公司的牌号为ParatoneTM8452的EP共聚物(实施例27)和市售的壳化学公司的牌号为ShellVisTM250的苯乙烯嵌段共聚物(实施例28)。完全照实施例1～7一样测定40℃和100℃的KV值及聚合物对100℃下的KV的贡献，试验结果连同实施例1的结果一起示于表Ⅵ中。
表Ⅵ
  实施例编号     组分 重量百分数 40℃的KV(cSt) 100℃的KV(cSt)    聚合物对100℃下的KV的贡献(cSt)
    1*     基油A  100  19.87  4.009     -
    26     基油A聚合物G聚合物D  99.10.360.54  48.78  8.802     4.973
    27     基油A聚合物GParatoneTM8452  99.10.360.54  65.23  11.24     7.231
    28     基油A聚合物GShellVisTM250  99.10.360.54  47.45  8.687     4.678
*非本发明的实施例
表Ⅵ示出的数据证明，SLEP特别是EPDM SLEP可与其他聚合物共混，而且仍具有作为改进高温粘度的有效油添加剂的功能。实施例29～32
重复实施例22～25，只是用聚合物G和一附加聚合物的共混物来替代聚合物G。该附加聚合物是市售的Rohm & Hass的牌号为AcryloidTM954的聚甲基丙烯酸之聚合物(实施例29)、市售的杜邦道弹性体股份有限公司的牌号为Nordel4523的乙烯/丙烯/己二烯三元共聚物(实施例30和32)和市售的杜邦道弹性体股份有限公司的牌号为Nordel4549的乙烯/丙烯/己二烯三元共聚物(实施例31)。AcryloidTM954是制成热油中的40％浓缩物形式加入的，Nordel4523和Nordel4549则是如聚合物G那样，制成热油中的6％浓缩物加入形式。表ⅦA和ⅦB分别列出了组分量与试验结果。
表ⅦA
    实施例编号     29     30      31      32
    配方     5W-30     5W-30     5W-30     10W-30
 组分/重量百分数
    基油C     76.13     74.04     76.56     35.21
    基油D     1.89     0.80     0.05     45.80
    DI-3     10.84     10.84     10.85      -
    DI-4      -     -       -     8.75
    PPD-3     0.20     0.20     0.20     0.20
    聚合物G浓缩物     9.85     5.67     4.93     6.02
    AcryloidTM954     1.09     -       -      -
    Nordel4523      -     8.45       -     4.03
    Nordel4549      -     -     7.42      -
表ⅦB
实施例编号     29     30   31   32
试验结果
KV(cSt)     10.76     10.58  10.46 10.57
-25℃的CCS(cP)     3,170     3,330  3,230    -
-20℃的CCS(cP)        -       -   -  2,825
HTHS(cP)     3.08     3.06  3.06  3.11
表Ⅶ(A和B)中的数据证明，含SLEP的聚合物共混物可起到满足5W-30和10W-30 SAE SH分类标准的组合物润滑油的VI改进剂的功能。实施例33～36
重复实施例22～25，只是改用DI-3、或PPD-3(实施例34和36)或PPD-1(实施例33和35)以及或聚合物G的浓缩物(实施例33和34)或聚合物J的浓缩物(实施例35和36)。此外，物理性质测试包括按照ASTMD-5133在30,000 cP下测定扫描Brookfield(SB)温度。5W-30配制物的SAE SH标准包括SB温度为-30℃。表ⅧA和ⅧB列出了组分量和试验结果。
表ⅧA
    实施例编号     33     34     35     36
    调配     5W-30     5W-30     5W-30     5W-30
 组分/重量百分数
    基油C     72.44     72.40     75.71     75.72
    基油D     5.14     5.17     0.56     0.56
    DI-3     10.85     10.84     10.86     10.86
    PPD-1     0.20       -     0.20       -
    PPD-3       -     0.20       -     0.20
表ⅧB
实施例编号     33    34    35   36
聚合物G浓缩物     11.38  11.39    -    -
聚合物J浓缩物       -     -  12.67  12.66
试验结果
KV,cSt     10.76  10.58  10.43  10.43
CCS,cP     3,170  3,330  3,570  3,570
HTHS,cP     3.08  3.06  3.01  3.01
SB,℃     -26.1  -30.1 -35.3  -35.5
表Ⅷ示出的数据表明，用加入了富马酸二烷基酯的PPD改进了低温粘度(实施例34和36)，虽然用乙烯辛烯共聚物的效应(实施例34)要比用EP共聚物(实施例36)的更显著，对这两种情况PPD都产生满意的结果。由于实施例33的配制物满足了5W-30的所有其他SAESH标准，一个本领域技术人员应能修改实施例33的配方以满足该SB标准。实施例37和38
重复实施例1～7的过程，采用剪切的(实施例38)和未剪切的(实施例37)聚合物H和基油A。聚合物H剪切前的I2为1.72g/10min，剪切后为4.20g/10min。聚合物在双转子的高速混合器(Haake)中以每分钟200转，于250℃剪切20min。也可用其他已知的机械装置如挤出机来代替高速混合器。测定每个例子的剪切稳定指数(SSI)。SSI是按照公式SSI=100×(V0-Vs)(V0-Vb)来确定的，式中的V0是在100℃下试验前溶液的KV值，Vs是在100℃下试验后溶液的KV值，Vb是基油的KV值。低SSI值表示聚合物-油溶液剪切稳定性比高SSI值的聚合物-油溶液更稳定。试验前基油的KV为4.009(实施例1)。实施例37的V0为6.55cSt,Vs为5.81cSt,SSI为29.1。实施例38的V0为5.94cSt,Vs为5.64cSt,SSI为15.5。
实施例37和38的数据证明，在加入到油中并进行所得聚合物-油溶液的剪切稳定性试验以前对SLEP先进行剪切将增强溶液的剪切稳定性(降低溶液的SSI)。
当在形成聚合物-油溶液之后把聚合物象其他SLEP和含油材料一样进行剪切，可期得到与实施例1～38类似的结果。所有这一切都在上面揭示了。实施例39
把聚合物G按USP5,346,963所述过程用马来酐接枝。具体地说，把聚合物G以每小时750磅聚合物的速度送入到Werner-PfleidererZSK70顺旋转双螺杆挤出机中。挤出机在挤压螺杆速度260rpm和机筒温度：区1=水冷、区2=370°F(188℃)、区3=380°F(193℃)、区4=430°F(221℃)、区5=410°F(210℃)、区6=410°F(210℃)、区7=410°F(210℃)、区8=430°F(221℃)、区9=410°F(210℃)、区10=345°F(174℃)、区11=345°F(174℃)和口模=360°F(182℃)的条件下进行操作，提供温度为446°F(230℃)的聚合物熔体。马来酐(MAH)是通过挤出机的区1末端的一个注入喷嘴以计量泵每小时14.5磅的计量速度加入的。Atochem制造和销售的牌号为LUPERSOLTM130的过氧化物2,5-二(叔丁基过氧)己炔-3是通过挤出机的区4末端的一个注入喷嘴以计量泵每小时1.5磅的计量速率加入的。挤出机保持在≥26英寸汞柱压力的真空水平以促进溶剂、未反应的MAH和其他杂质的脱除。加入到聚合物G中的MAH百分数为1.2％。由挤出机输出的料经水下造粒法在60°F(16℃)下造粒。
然后把MAH接枝的SLEP与一种试制的单官能胺封端的聚环氧丁烷化合物进行共混并反应，所述聚环氧丁烷的重均分子量Mw为1500，是道化学公式制备的。共混以及反应是在Werner-PfleidererZSK-30顺旋转双螺杆挤出机中进行的，挤出机的螺杆速度为150rpm，物料通过量为每小时20磅，挤压温度为190℃。胺化合物是以胺化合物对聚合物的比例0.15比1加入到接枝的聚合物中去的。
把所得的接枝和反应了的聚合物按实施例1～8所用的同样的基油和程序来进行VI改进剂的试验。KV值为40℃下60.45cSt、100℃下9.706cSt。聚合物对100℃下KV的贡献为5.611cSt。
实施例39表明，当用如马来酐之类不饱和有机化合物进行接枝，然后再与如胺基封端的化合物之类官能化合物进一步反应的SLEP，用作含油组合物的VI改进剂时，可提供满意的结果。
实施例2～39都表明加入SLEP改进了含油组合物的VI。含油组合物的其他性质可通过调整配方来优化。用其他的SLEP、不饱和有机化合物和官能化合物预期也可得到类似的结果。所有这些在上面都已揭示。

Claims (24)

1．一种包含含油材料和粘度改性有效量的基本上是线型的乙烯聚合物的含油组合物，其特征在于：a)熔体流动比I10/I2≥5.63；b)分子量分布Mw/Mn由方程Mw/Mn≤(I10/I2)-4.63所定义；以及c)开始出现表面熔体破裂的临界剪切速率至少要比具有类似I2和Mw/Mn的线型烯烃聚合物开始出现表面熔体破裂的临界剪切速率大50％。
2．权利要求1的组合物，其中基本上是线型的乙烯聚合物是接枝聚合物的原料，该接枝聚合物是用于替代基本上线型的乙烯聚合物的，所述接枝聚合物接枝了至少为接枝乙烯聚合物重量的0.01重量百分数的含至少一个不饱和烯键的不饱和有机化合物。
3．权利要求1或2的组合物，其中所述接枝聚合物的乙烯含量在聚合物重量的20至80重量百分数范围内。
4．权利要求1或2的组合物，其中所述基本上是线型的乙烯聚合物的又一特征在于它是乙烯与C3～C20的α-烯烃的共聚物。
5．权利要求1或2的组合物，其中所述基本上是线型的乙烯聚合物是包含乙烯、C3～C20的α-烯烃和至少一种二烯单体的共聚单元的共聚体。
6．权利要求5的组合物，其中所述二烯单体选自二环戊二烯、己二烯-1,4、戊二烯-1,3和5-亚乙基降冰片烯-2、辛二烯-1,7和乙烯基降冰片烯。
7．权利要求1或2的组合物，其中分子量分布小于5。
8．权利要求1或2的组合物，其中熔体流动比为6.5至15。
9．权利要求2的组合物，其中所述不饱和有机化合物选自羧酸、羧酸酐、羧酸酯、羧酸醚、羧酸胺、羧酸酰胺和琥珀酰亚胺类、不饱和环氧化合物、乙烯基取代的杂环化合物、乙烯基胺、乙烯基噁唑啉类和乙烯基环氧化物。
10．权利要求9的组合物，其中所述不饱和有机化合物是选自马来酸、富马酸、丙烯酸、甲基丙烯酸、衣康酸、巴豆酸、α-甲基巴豆酸和肉桂酸之羧酸。
11．权利要求9的组合物，其中所述不饱和有机化合物是马来酸酐。
12．权利要求9～11的组合物，其中所述不饱和有机化合物还与酸、胺或醇反应物进一步反应。
13．权利要求12的组合物，其中所述反应物是能与接枝后的基本上是线型的乙烯聚合物起反应的、选自含至少一个一级和/或至少一w个二级，及任选地至少一个三级胺基团的脂族和杂环有机氮化合物的胺。
14．权利要求13的组合物，其中所述胺选自多亚乙基多胺、亚烷基多胺、亚烷基多胺的环状或高级同系物、胺基封端的聚氧化烯化合物和羟烷基多胺。
15．权利要求12的组合物，其中所述醇是含有最多100个碳原子的，有2至10个羟基的脂族多元醇。
16．权利要求15的组合物，其中所述醇是亚烷基二醇、聚二醇或含有最多20个碳的脂族醇。
17．权利要求9的组合物，其中所述不饱和有机化合物是乙烯基吡啶或N-乙烯基吡咯烷酮-2。
18．权利要求1或2的组合物，其中所述含油材料选自于烃油、以烯化氧聚合物及其衍生物为基础的润滑油、二元羧酸酯油和硅基油。
19．权利要求18的组合物，其中所述含油材料选自煤油、石蜡润滑油、环烷润滑油和石蜡-环烷混合型润滑油、由煤或页岩提炼的油、聚(α-烯烃)油、植物油、动物油、由环氧乙烷、环氧丙烷、环氧丁烷、四氢呋喃制备的聚烯化氧聚合物、聚烷基、聚芳基、聚烷氧基或聚芳氧基硅氧烷油和硅酸酯油。
20．权利要求1或2的组合物，其中所述基本上是线型的乙烯聚合物的用量是使组合物适合用于制备润滑脂、电缆填充复合料或化妆品材料的发生胶凝或增稠的量。
21．权利要求1或2的组合物，其中组合物还包含足够数量之倾点下降剂，以使它的低温性质比不合倾点下降剂的类似组合物得到改进。
22．权利要求1或2的含油组合物，其中它还包含至少一种选自于氢化聚异戊二烯、苯乙烯/丁二烯嵌段聚合物、苯乙烯/异戊二烯嵌段聚合物、氢化苯乙烯/丁二烯嵌段聚合物、氢化苯乙烯/异戊二烯嵌段聚合物、接枝苯乙烯/丁二烯嵌段聚合物、接枝苯乙烯/异戊二烯嵌段聚合物、聚甲基丙烯酸烷基酯、聚丙烯酸烷基酯、乙烯聚合物和丙烯酸酯/甲基丙烯酸酯共聚物之聚合物。
23．权利要求1的含油组合物，其中至少一部分基本上是线型的乙烯聚合物被剪切改性的基本线型乙烯聚合物所替代从而增加含油组合物的剪切稳定性。
24．一种油添加剂浓缩组合物，它包含矿物油稀释剂和5至60重量百分数的权利要求1或2的基本上是线型的乙烯聚合物。
CN96180200A 1996-03-08 1996-11-01 用作粘度指数改进剂或胶凝剂的基本线性乙烯/α-烯烃聚合物 Expired - Fee Related CN1098344C (zh)

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CN103936908A (zh) * 2009-04-28 2014-07-23 埃克森美孚化学专利公司 基于乙烯的共聚物，含有该共聚物的润滑油组合物和它们的制备方法
CN104812366A (zh) * 2012-09-24 2015-07-29 罗门哈斯公司 个人护理感官试剂
CN106061460A (zh) * 2014-03-10 2016-10-26 陶氏环球技术有限责任公司 头发护理感觉剂
CN106318351A (zh) * 2015-06-16 2017-01-11 中石化石油工程技术服务有限公司 一种无土相油包水钻井液及其制备方法
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KR100490071B1 (ko) 2005-08-12
CA2248368C (en) 2004-12-28
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