CN1539005A - 减少烟雾生成的二冲程发动机润滑油 - Google Patents

减少烟雾生成的二冲程发动机润滑油 Download PDF

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CN1539005A
CN1539005A CNA018203965A CN01820396A CN1539005A CN 1539005 A CN1539005 A CN 1539005A CN A018203965 A CNA018203965 A CN A018203965A CN 01820396 A CN01820396 A CN 01820396A CN 1539005 A CN1539005 A CN 1539005A
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lubricating oil
weight
oil
cst
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CN1261551C (zh
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G・C・勒赫
G·C·勒赫
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Infineum International Ltd
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    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10N—INDEXING SCHEME ASSOCIATED WITH SUBCLASS C10M RELATING TO LUBRICATING COMPOSITIONS
    • C10N2030/00—Specified physical or chemical properties which is improved by the additive characterising the lubricating composition, e.g. multifunctional additives
    • C10N2030/50—Emission or smoke controlling properties
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10N—INDEXING SCHEME ASSOCIATED WITH SUBCLASS C10M RELATING TO LUBRICATING COMPOSITIONS
    • C10N2040/00—Specified use or application for which the lubricating composition is intended
    • C10N2040/25—Internal-combustion engines
    • C10N2040/255—Gasoline engines
    • C10N2040/26—Two-strokes or two-cycle engines

Abstract

公开了一种含有溶剂和5％～20％(重量)聚异丁烯的低烟雾二冲程发动机润滑油。所述的润滑油在100℃下的动力粘度KV为至少6.5mm2/s(cSt)且JASO M342烟雾指数为至少85。

Description

减少烟雾生成的二冲程发动机润滑油
本发明涉及用作二冲程发动机润滑油的润滑油组合物。更具体地说，本发明涉及这样的二冲程发动机润滑油，其特征在于，它含有相对少量的聚异丁烯，但提供能符合陆地设备、汽油二冲程发动机例如机动自行车发动机、轻便摩托车发动机、雪地摩托车发动机、割草机发动机等的某些烟雾生成试验标准和粘度要求的油品。二冲程汽油发动机现有从小于50cc的发动机到超过500cc的更高性能发动机。这样的高性能发动机的开发需要新的二冲程发动机润滑油标准和试验方法。
二冲程发动机通过以下方法来润滑：燃料和润滑油混合，然后使混合的组合物通过发动机。在本领域中已描述了与燃料相容的各种类型二冲程发动机润滑油。通常，这样的润滑油含有各种添加剂组分，以便使润滑油通过二冲程发动机的工业标准试验。
本发明基于以下发现，聚异丁烯聚合物、溶剂和润滑油基础油的适当均衡可提供具有超过JASO(日本汽车标准协会)M342烟雾指数试验的适合粘度性能的二冲程发动机润滑油。
因此，已发现一种含有以下混合物的二冲程发动机润滑油组合物，其100℃下的动力粘度为至少6.5mm2/s(cSt)和JASO M342烟雾指数为至少85：
(a)5％～20％(重量)数均分子量为约400～2200的聚丁烯聚合物，为聚丁烯、聚异丁烯或聚丁烯和聚异丁烯混合物；
(b)30％～45％(重量)40℃下的粘度为2～12mm2/s(cSt)的正常液体烃或矿物油溶剂；
(c)0％～10％(重量)二冲程发动机润滑油添加剂的添加剂配方，其用量满足二冲程发动机润滑油组合物的JASO M345清净性标准；以及
(d)其余为40℃下的粘度为20～180mm2/s(cSt)的润滑油。
除非另加说明，所有的百分数都以整个配方润滑油组合物重量中活性成分的重量计。
优选用于本发明润滑油组合物的聚丁烯混合物为通常由C4烯烃聚合制得的聚正丁烯和聚异丁烯的混合物，通常数均分子量为约400～2200，而数均分子量为约400～1300的聚异丁烯和聚正丁烯是特别优选的，最优选的是数均分子量为约950的聚正丁烯和聚异丁烯的混合物。数均分子量(Mn)用凝胶渗透色谱测量。由100％聚异丁烯或100％聚正丁烯组成的聚合物也在本发明的范围内和在术语聚丁烯聚合物”的含义范围内。优选的聚丁烯聚合物用量为10％～20％(重量)、最优选12％～15％(重量)。
优选的聚丁烯聚合物为C4烯烃炼制物流制得的聚丁烯和聚异丁烯的混合物，所述的C4烯烃炼制物流含有约6％～50％(重量)异丁烯，其余为丁烯(顺式和反式)异丁烯和小于1％(重量)丁二烯的混合物。具体来说，优选由含6％～45％(重量)异丁烯、25％～35％(重量)饱和丁烯和15％～50％(重量)1-丁烯和2-丁烯的C4物流制得的聚合物。聚合物制备时采用路易斯酸催化剂。
适用于本发明的溶剂通常可为40℃下的粘度为2～12mm2/s(cSt)、优选3～5mm2/s(cSt)的正常液体天然烃或合成烃或矿物油溶剂。这样的溶剂还必需有约60℃～120℃的闪点，以使本发明的二冲程发动机润滑油的闪点大于70℃。典型的例子包括烷族的、异构烷族的和环烷族的脂肪烃或矿物油溶剂。这样的溶剂可含有除碳和氢以外的官能团，只要这样的基团对二冲程发动机润滑油的性能没有坏的影响。优选由Sun Oil Company以“Sun HPO 40”销售的40℃下的粘度为3.5～4.0mm2/s(cSt)烷族矿物油溶剂。优选的是，使用35％～40％(重量)例如38％或39％(重量)这样的溶剂或其混合物。
溶剂和聚丁烯聚合物的适当均衡是本发明的基本方面。传统上，在二冲程发动机润滑领域，各种配方需要22％～30％聚丁烯聚合物和较低粘度溶剂例如煤油，以便满足至少85的JASO M342烟雾指数数值。但是，相对低粘度溶剂例如煤油的使用虽然有助于烟雾性能，但对动力粘度(KV)有坏影响，在100℃下的动力粘度必需为6.5mm2/s(cSt)或更高，以便满足商用产品的JASO要求。本发明的配方不含煤油，不含40℃粘度小于2.0mm2/s(cSt)、优选40℃小于3.0mm2/s(cSt)的溶剂，通过减少聚丁烯聚合物(一种昂贵的成分)的用量来降低成本，同时又满足KV和JASO烟雾指数要求。
本发明还含有0％～10％、优选1％～7％(重量)含有一种或多种传统二冲程发动机润滑油添加剂的添加剂配方作为第三组分，它们可为任何一种通常包含在这样的润滑油中的用于特定目的的添加剂。
可在本发明组合物中用于添加剂配方组分的传统添加剂包括优选的腐蚀抑制剂、氧化抑制剂、摩擦改进剂、分散剂、消泡剂、抗磨剂、降凝剂、金属清净剂、防锈剂、润滑剂等。所有的百分数都以活性成分(a.i.)的重量计。
优选的添加剂配方含有(i)聚异丁烯基(Mn400～2500、优选Mn950)琥珀酰亚胺或其他油溶性的丙烯酸酯化的含氮润滑油分散剂，其用量为在润滑油中提供0.2％～5％、优选1％～3％(重量)的分散剂，以及(ii)金属酚盐、磺酸盐或水杨酸盐油溶性清净添加剂，它为中性或高碱性金属清净剂，以致总碱值为200或更小，其用量为在润滑油中提供0.1％～2％、优选0.2％～1％(重量)的金属清净添加剂。金属优选为钙、钡或镁。中性水杨酸钙是优选的，在润滑油中的用量为约0.5％～1.5％(重量)。
腐蚀抑制剂在润滑油中的用量为0.01％～3％、优选0.01％～1.5％(重量)，它们用硫磷化烃类和硫磷化烃类与碱土金属氧化物或氢氧化物反应得到的产物说明。苯并三唑(在丙二醇中35％(重量)活性成分)优选用于本发明。
氧化抑制剂在润滑油中的用量为0.01％～5％、优选0.01％～1.5％(重量)，它们的例子为优选有C5～C12烷基侧链的烷基酚硫代酯的碱土金属盐抗氧化剂，例如壬基酚钙硫化物、叔辛基酚钡硫化物、二辛基苯基胺以及硫化的或硫磷化的烃类。还包括油溶性的抗氧化剂铜化合物，例如C10～C18油溶性脂肪酸的铜盐。
摩擦改进剂在润滑油中的用量为0.01％～3％、优选0.01％～1.5％(重量)，包括脂肪酸酯和酰胺、二聚脂肪酸的甘油酯和琥珀酸酯或其金属盐。
降凝剂也称为润滑油流动改进剂，在润滑油中的用量为0.01％～2％、优选0.01％～1.5％(重量)，它们可降低流体流动的温度，这些添加剂中具有代表性的是C8～C18或C14二烷基富马酸酯乙烯基乙酸酯共聚物(优选的)、聚甲基丙烯酸酯和蜡萘。
还可通过聚硅氧烷型抗泡剂例如硅油和聚二甲基硅氧烷来提供泡沫控制；丙烯酸酯聚合物也是适用的。它们在润滑油中的用量为0.01％～5％、优选0.01％～1.5％(重量)。
抗磨剂使金属部件的磨损减少，代表性的抗磨剂为二烷基二硫代磷酸锌、二芳基二磷酸锌和硫化的异丁烯。它们在润滑油中的用量为0.01％～5％(重量)。
用于本发明的润滑剂可选自各种油溶性的材料。通常，它们在润滑油中的用量为1％～20％、优选1％～7％(重量)。润滑剂包括多元醇醚和多元醇酯，例如C5～C15一元羧酸的多元醇酯，特别是这样的酸的季戊四醇、三羟甲基丙烷和新戊二醇合成润滑酯，其中酯的粘度为至少9mm2/s(cSt)(100℃)，以及包括天然油例如优选的光亮油，它为由石油制备润滑油馏分生成的蒸馏残渣得到的高粘度的矿物油馏分。
本发明的润滑油组合物的第四组分为具有润滑粘度的油，即40℃粘度为约20～180mm2/s(cSt)、优选55～180mm2/s(cSt)，使成品二冲程发动机润滑油的KV为6.5～14mm2/s(cSt)(100℃)。
这些用于本发明具有润滑粘度的油可为天然油或合成油。这些油的混合物也经常使用。各种油的调合油也可使用，只要最后的粘度为20～180mm2/s(cSt)(40℃)。
天然油优选包括矿物润滑油，例如液体石油油品和经溶剂处理或酸处理的烷族、环烷族或烷族-环烷族混合矿物润滑油。由煤或页岩制得的具有润滑粘度的油也为适用的基础油。
合成润滑油包括烃油，例如聚合的和共聚合的烯烃烷基化的二苯基醚和烷基化的二苯基硫醚及其衍生物，类似物和同系物。
小于5个碳原子的烯烃聚合得到的油品及其混合物为典型的合成聚合物油。制备这样的聚合物油的方法是本领域的技术人员熟知的，如US 2278445；US2301052；US2318719；US2329714；US2345574和US2422443公开的。
环氧烷聚合物(即均聚物、共聚物及其衍生物，其中末端羟基经酯化、醚化等改性)构成优选用于本发明的一类已知的合成润滑油，特别是与链烷醇燃料组合使用。它们的例子是环氧乙烷或环氧丙烷聚合制得的油品、这些聚氧亚烷基聚合物的烷基醚和芳基醚(例如平均分子量为1000的甲基聚丙二醇醚、分子量为500～1000的聚丙二醇的二苯基醚、分子量为1000～1500的聚丙二醇的二乙基醚等)，或它们的一元羧酸酯和多元羧酸酯，例如乙酸酯、混合的C3～C8脂肪酸酯或四乙二醇的C13羰基酸二酯。
另一类适合的合成润滑油包括二元羧酸(例如邻苯二甲酸、琥珀酸、烷基琥珀酸、链烯基琥珀酸、马来酸、壬二酸、辛二酸、癸二酸、富马酸、己二酸、油酸二聚物、丙二酸、烷基丙二酸、链烯基丙二酸等)与各种醇(例如丁醇、己醇、辛醇、癸醇、十三烷醇、2-乙基己醇、乙二醇、二乙二醇单醚、丙二醇等)的酯。这些酯的具体例子包括己二酸二辛酯、癸二酸二(2-乙基己基)酯、富马酸二正己酯、癸二酸二辛酯、壬二酸二异辛酯、壬二酸二异癸酯、邻苯二甲酸二辛酯、邻苯二甲酸二癸酯、癸二酸二(二十烷基)酯、油酸二聚物的2-乙基己二酯、1mol癸二酸与2mol四乙二醇和2mol 2-乙基己酸反应生成的复合
Figure A0182039600071
(complex ester)等。
适用作合成油的酯还包括那些由C5～C18一元羧酸与多元醇和多元醇醚例如新戊二醇、三羟甲基丙烷、季戊四醇、二季戊四醇、三季戊四醇等制得的酯。
未精制的、精制的和再精制的油，无论是天然的还是合成的，(以及其中任两种或两种以上的混合物)都可用于本发明的润滑油组合物。未精制的油是那些直接由天然来源或合成来源未经进一步纯化处理得到的油。例如，未进一步处理，直接由干馏操作得到的页岩油、直接由常压蒸馏得到的石油或直接由酯化法得到的酯油为未精制的油。精制的油类似未精制的油，不同的是它们在一个或多个纯化步骤中进一步处理，以便改进一种或多种性能。对于熟悉本领域的技术人员来说，许多纯化技术是已知的，例如溶剂萃取、二次蒸馏、酸或碱萃取、过滤、渗滤等。用类似已用于制备精制油的那些方法来制得所述的再精制油。这样的精制油也称为再生油或再加工油，常常用旨在除去废添加剂和油分解产物的技术再处理。
本发明的润滑油组合物能与用于二冲程发动机的燃料自由混合。这样的润滑油与燃料的混合物为本发明的另一实施方案。对于熟悉本领域的技术人员来说，适用于二冲程发动机的燃料是大家熟悉的，通常含有大量正常的液体燃料，例如含烃质的石油馏分油燃料，例如ASTM技术规格D-439-73规定的发动机汽油。这样的燃料也可含有非烃质材料，例如醇类、醚类、有机硝基化合物等，例如甲醇、乙醇、二乙基醚、甲乙醚、硝基甲烷，并且这样的燃料都在本发明的范围内，例如由植物和矿物来源如谷物、α页岩和煤得到的液体燃料。这样的燃料混合物的例子是汽油和乙醇、柴油燃料和醚、汽油和硝基甲烷的组合物等。汽油是优选的，即10％馏分点为60℃和90％馏分点为约205℃ASTM沸点的烃类混合物。无铅汽油是特别优选的。
本发明的润滑油用于与燃料的混合物中，其用量为每份(重)润滑油混合约20～250份(重)燃料、优选每份(重)润滑油混合约30～100份(重)燃料。
用以下实施例来进一步说明本发明，这些实施例不作为对本发明范围的限制。“活性成分”或“a.i.”指在矿物油或这里所指的其他载体中的添加剂溶液。百分数为重量百分数。
实施例1
按JASO M345试验方法JASO M340、M341、M342、M343评价本发明的润滑油。它们是由日本汽车工程师协会(JSAE)为二冲程汽油发动机润滑油建立的发动机试验方法。根据1994年7月1日的资料，根据日本汽车标准协会(JASO)公布的JASO M345标准，将用于二冲程发动机的润滑油分类。JASO 1994年4月公布了JASO M345标准。“E GD Detergency”为通常的JASO M341清净性试验(1小时)方法另一改型的参考方法，其中试验进行3小时。它是预计会被ISO(国际标准组织)接受的更加严格的标准，正如技术委员会28在1995年1月5日的委员会草案公布的。“FC”为JASO M345标准的最高性能标准。结果列入下表。
                          表
组分                            质量％
(a)Dispersant Adpack            4.1
(b)Mn950的PIB                   14.0
(c)“Sun HPO-40”溶剂           38.0
(d)抗氧化剂                     0.2
(e)防锈剂                       0.2
(f)基础油                       38.5
(g)光亮油                       5.0
                                100.0
                                                 EGD/FC
分析测试                方法           结果      范围
KV@100℃，mm2/s(cSt)   ASTM D445      6.86      ≥6.5
PM闪点，℃              ASTM D93       1.22      ≥70
硫化灰分，％(重量)      ASTM D874      0.17      ≤0.18
                                      EGD/FC
                                      范围
ISO-EGD 3小时清净性指数      132      ≥125
ISO-EGD 3小时活塞漆膜指数    102      ≥95
JASO 1小时清净性指数         104      ≥95
JASO 1小时活塞漆膜指数       102      ≥90
JASO润滑性指数               97       ≥95
JASO初始扭矩指数             100      ≥98
JASO废气烟雾指数             92       ≥85
JASO废气胶粘指数             95       ≥85
表注：
(a)Dispersant Adpack含有49％(50.5％(重量)活性成分)的Mn950聚异丁烯基琥珀酰亚胺分散剂和48.8％(40％活性成分)的TBN58的中性水杨酸钙清净剂，其余为稀释剂矿物油。
(b)“PIB”为聚异丁烯。
(c)溶剂为烷族矿物油，40℃粘度(KV)为3.5～4.0mm2/s(cSt)。
(d)抗氧化剂为30％a.i.的4，4-亚甲基-双-2，6-二叔丁基酚溶液。
(e)防锈剂为62％a.i.的四丙基琥珀酸酐、丙二醇和水的反应产物的矿物油溶液。
(f)基础油为“Sun CN 725”，40℃粘度为127mm2/s(cSt)。
(g)光亮油为Sun Brightstock，一种润滑剂。
实施例2-对比例
制备有实施例1相同组成的另一润滑油，不同的是用煤油代替SunHPO-40。这种润滑油作为商业产品不能令人满意，因为它的粘度为4.38mm2/s(cSt)(100℃)，它低于6.5mm2/s(cSt)(100℃)的KV最低值。
实施例3-对比例
制备有实施例1相同组成的另一润滑油，不同的是它含有45％的40℃下KV为13mm2/s(cSt)的烷族矿物油溶剂、7.0％光亮油和29.9％“Exxon 600N”基础油，该基础油40℃下的粘度为129mm2/s(cSt)。这种润滑油是不能令人满意的，因为经试验发现JASO烟雾指数为60。100℃下的KV为9.07mm2/s(cSt)。

Claims (8)

1.一种100℃下的动力粘度为至少6.5mm2/s(cSt)和JASO M342烟雾指数为至少85的二冲程发动机润滑油，所述的润滑油含有以下混合物：
(a)5％～20％(重量)数均分子量为约400～2200的聚丁烯聚合物，为聚正丁烯、聚异丁烯或聚正丁烯和聚异丁烯的混合物；
(b)30％～45％(重量)40℃下粘度为2～12mm2/s(cSt)的正常液体烃或矿物油溶剂；
(c)0％～10％(重量)用于二冲程发动机润滑油添加剂的添加剂配方，其用量满足二冲程发动机润滑油组合物的JASO M345标准；以及
(d)其余为40℃下的粘度为20～180mm2/s(cSt)的润滑油。
2.根据权利要求1的组合物，其中(a)成分的Mn为约950。
3.根据权利要求1的组合物，其中(b)成分为40℃下的粘度为3～5mm2/s(cSt)的烷烃矿物油溶剂。
4.根据权利要求1的组合物，其中(c)成分含聚异丁烯基琥珀酰亚胺分散剂。
5.根据权利要求1的组合物，其中(c)成分含总碱值为200或更小的金属酚盐、磺酸盐或水杨酸盐清净剂。
6.根据权利要求1的组合物，其中有约12％～15％(重量)(a)成分。
7.根据权利要求1的组合物，其中有35％～40％(重量)(b)成分。
8.根据权利要求1的组合物，其中有1％～7％(重量)(c)成分。
CNB018203965A 2000-12-11 2001-12-03 减少烟雾生成的二冲程发动机润滑油 Expired - Fee Related CN1261551C (zh)

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