JP2008533274A - Blends containing Group III and Group IV base stock - Google Patents

Abstract

The invention relates to compositions comprising a blend of Group III basestocks and low volatility, low viscosity PAO basestocks. The blend is particularly useful for preparing finished lubricants that meet or even exceed the criteria for SAE Grade 0 W multi-grade engine oils. The combination of these low volatility, low viscosity PAOs with Group III basestocks provide, in embodiments, the necessary performance criteria in automatic transmission fluids, automotive or industrial gear oils, hydraulic fluids, or any other high performance lubricant requiring a combination of excellent low fluidity and low volatility.

Description

  The present invention relates to a composition comprising a blend of a Group III base stock and a low volatility, low viscosity PAO base stock. This blend is particularly useful in preparing final lubricants that meet or exceed SAE grade OW multi-grade engine oil standards.

  For applications that require excellent low temperature properties as well as high temperature stability, for example, ACEA (European Automobile Manufacturers Association), ATIEL (European Lubricating Oil Industry Association), API (American Petroleum Institute), ILSAC (Lubricating Oil International) Achieve specific requirements set by organizations such as the Standardization and Accreditation Committee, ASTM (American Materials Testing Association), EOLCS (Engine Oil Certification System), SAE (Society of Automotive Engineers, Inc.) There is currently a need in the art for catalytically dewaxed Group III basestocks or polyalphaolefins based on wax isomers as the primary basestock. Specific examples are SAE grade 0W multi-grade engine oil and ILSAC GF-4 standard products. Currently, the supply of these relatively expensive base stocks is limited, and the development of alternatives is required to meet growing demand. There is a need for a technology that allows for the use of more dormitories of base stock derived from more petroleum in such formulations.

  US 5,693,598 describes a low-viscosity oil having a kinematic viscosity at 100 ° C. of about 4 cSt or less, and a composition having anti-wear properties, comprising the oil. .

  US 5,789,355 relates to higher grade multi-grade oils including SAE grade 5W and base stock and surfactant inhibitor packages. This base stock is selected from API Group I and II. The surfactant inhibitor package includes an ashless dispersant derived from ethylene α-olefin.

  US 6,303,548 relates to a base oil for SAE grade 0W40 lubricating oil compositions comprising PAO and synthetic ester lubricating oil.

US Pat. No. 6,824,671 discloses two consecutive runs using BF _{3 in} which a mixture of about 50-80% by weight of 1-decene and about 20-50% by weight of 1-dodecene contains an ethanol acetate: ethyl accelerator. It describes co-oligomerization in a stirred tank reactor. Monomers and dimers are removed from the top and the bottom product is hydrogenated to saturate the trimer / oligomer to produce 5cStPAO. This product is further distilled and the distillation fractions are mixed to produce 4cStPAO containing mainly trimers and tetramers and 6cStPAO containing trimers, tetramers and pentamers. The lubricating oil thus obtained has a characteristic of Noack Volatility of about 4% to 12% and a pour point of -40 ° C to -65 ° C. See also pending US patent application Ser. No. 10/959544.

US Patent Application No. 2004/0033908 discloses a complete formulation comprising PAO prepared by an oligomerization process comprising contacting an α-olefin feedstock with a BF ₃ catalyst and a promoter (cocatalyst) system comprising an alcohol and an ester. Describes the lubricating oil used.

  US patent applications 20004/0129603, 2004/0154957, and 2004/0154958 describe formulations using catalytically dewaxed Group III materials.

  The inventor has surprisingly found that in order to meet the increasingly demanding requirements for lubricating oils, blends containing new PAOs can also contain large amounts of conventional hydrocracked Group III basestocks.

  As mentioned above, currently, the supply of these relatively expensive base stocks is limited, and the development of alternatives is sought to meet growing demand. There is a need for a technique that allows the use of base stocks derived from more petroleum in such formulations.

  The present invention relates to a composition comprising a blend of (a) a Group III base stock and (b) a low volatility, low viscosity PAO base stock characterized by low kinematic viscosity, low Noack volatility and low pour point.

  The invention also relates to a process for producing a blend comprising (a) at least one Group III basestock, and (b) the PAO of the invention.

  In a preferred embodiment, the PAO of the present invention comprises a process comprising contacting one or more α-olefins with an oligomerization catalyst in the presence of a double promoter system comprising one or more alcohols and one or more esters. It has the characteristic that it is obtained by.

  In a preferred embodiment, the PAO of the present invention comprises a process comprising contacting one or more α-olefins with an oligomerization catalyst in the presence of a double promoter system comprising one or more alcohols and one or more esters. It is characterized by being produced by.

  In a preferred embodiment, the PAO of the present invention is characterized by having a pour point of less than -54 ° C and one or more of the following relationships. (I) Noack volatility relationship to CCS on or below curve A in FIG. 1; (ii) Noack volatility relationship to CCS on curve B or below curve B in FIG. (Iii) Noak volatility relationship to KV on curve A in FIG. 2 or below curve A, (iv) Noack volatility relationship to KV on curve B in FIG. 1 or below curve B, (v 3) Noak volatility relationship to KV on curve A in FIG. 3 or below curve A, and (vi) Noack volatility relationship to KV on curve B in FIG. 3 or below curve B. Preferably 2 or more, or 3 or more, or 4 or more, or 5 or more, or all 6 of these relationships.

In a preferred embodiment, the PAO of the present invention has a pour point of less than −54 ° C. and (ia) a range of 3.5 to 3.95 cSt at 100 ° C. and Noack Volatility = (900) (KV) ^−3.2 (Ib) in the range greater than 3.95-6 cSt at 100 ° C., Noack volatility = (175) (KV) ⁻² , characterized by the relationship of Noack volatility to KV at 100 ° C.

  In a preferred embodiment, the Group III base stock used in the composition or blend of the present invention is not a Group III base stock obtained by a wax isomerization process.

  In a preferred embodiment, PAO characterized by low kinematic viscosity, low Noack volatility, and low pour point is used without blending with other PAOs.

  An object of the present invention is to provide a simple method for upgrading a conventional petroleum-derived base stock, particularly a Group III base stock, to a premium lubricating oil product capable of meeting new requirements regarding low temperature performance and high temperature stability. It is.

  It is further provided to provide an improved lubricating oil basestock blend, i.e. an improvement comprising an improved pour point as well as at least one of the properties defined by (i) to (vi) above. It is an object of the invention.

  These and other objects, features, and advantages will become apparent from the following detailed description, preferred embodiments, examples, and the appended claims. These and other aspects, objects, features, and advantages will become apparent from the following drawings, detailed description, examples, and appended claims.

  In the following description, the upper curve in each figure is referred to as curve A, and the uppermost curve is referred to as curve B.

  In the present invention, one or more PAOs of the present invention that can be characterized by (a) one or more Group III basestocks, and (b) a PAO having low kinematic viscosity, low Noack volatility, and low pour point A blend comprising a base stock is provided.

Group III Base Stock The first component of the composition of the present invention is selected from one or more Group III base stocks.

  In the present invention, the term “Group III base stock” refers to the API Group III base stock. Group III base stocks are characterized by having a sulfur content of less than 300 ppm, a saturation of more than 90% by weight, and a viscosity index (VI) of 120 cSt or higher. Typically, such base stocks are liquid petroleum and solvent or acid treated paraffinic, naphthenic, or mixed paraffin / naphthenic that can be further refined and dewaxed by a hydrocracking or hydrofinishing process. Any natural oil derived from petroleum having characteristics as a Group III basestock including animal oils and vegetable oils (eg lard oil, castor oil) as well as mineral lubricating oils of the type. Group III base stocks are available from a wide variety of commercial sources.

  Exemplary and useful Group III basestocks in the blends of the present invention include those shown in US Pat. Nos. 6,503,872, 6,649,576, and 6,713,438.

  Group III basestocks useful in the present invention can also be characterized as mineral oils that are highly hydrotreated or hydrocracked and have the aforementioned characteristics specified by the API for Group III basestocks. In these processes, the mineral oil is exposed to very high hydrogen pressure at high temperatures in the presence of a hydrogenation catalyst. Typical process conditions include a hydrogen pressure of about 3000 pounds per square inch (psi) at a temperature of 300 ° C. to 450 ° C. over a hydrogenation type catalyst. This process removes sulfur and nitrogen from the lubricating oil and saturates all alkylene and aromatic structures in the feed. This results in a base oil having very good oxidation resistance and viscosity index. A side benefit of these processes is the ability to isomerize low molecular weight components of raw materials such as waxes from linear to branched structures, providing a finished base oil with significantly improved low temperature properties. It can be done. These hydrotreated base oils can then be further dewaxed catalytically or by conventional means to lower the pour point and improve low temperature fluidity.

  A particular advantage of the present invention is that no wax isomer Group III material is required in the composition of the present invention to achieve the specific property values mentioned in the Background section. Thus, in one embodiment, component (i) does not include a wax isomer material. However, such materials are nevertheless considered to be a Group III basestock embodiment useful in blends comprising the PAOs of the present invention. Similarly, the compositions of the present invention may or may not contain a catalytically dewaxed Group III material, and may or may not contain a solvent dewaxed Group III material.

  Representative examples of Group III basestocks are materials such as Visom, commercially available from ExxonMobil Lubricants & Specialties, or US Patent Publications 2004/0129603, 2004/0154957, and 2004. / 0154958 as described.

  Although not important to the broad invention considered, the Group III basestock is also characterized by its performance in the cold crank simulator test (CCS), as described more fully below. A fully formulated SAE grade 0W engine oil is required to have a CCS at −35 ° C. of 6200 or less. Traditionally, fully formulated 0W engine oils using large amounts of Group III base stock (eg, greater than 30% by volume) were required to have a CCS at -35 ° C of 2600 or less. This was not compatible with the prior art with materials based on wax isomers such as the Visom ™ basestock described in this invention. However, with the PAO of the present invention, a high concentration Group III basestock with CCS at -35 ° C. greater than 2600, greater than 2700, greater than 2800, or even greater than SAE Grade 0W engine oil. Can be blended to achieve. This is one of the great advantages of the present invention.

  Preferred Group III base stocks include S.I. K. Yubase 4 (having 99.5% saturation) and Yubase 6 (having 97.5% saturation) available from the Corporation are included.

  Also preferably, the Group III material is characterized by having a viscosity of 3 cSt or more, more preferably 3 cSt or more.

  Other preferred Group III basestocks are those available from Fortum, S-Oil, Petro-Canada, Chevron Texaco, and Motiva.

Low Volatility, Low Density PAO Base Stock The second component of the composition of the present invention is one or more PAO base stocks characterized by low kinematic viscosity, low Noack volatility, and low pour point.

  PAOs and methods of making PAO useful in the present invention have been described recently in US 6,824,671 and US patent application 2004/0033908, and in pending co-application xx / xxxxxxxx (attorney file 2005B031). Is also described.

  In one embodiment, the PAO useful in the present invention contacts a feed comprising one or more α-olefins with a polymerization catalyst and a double promoter (or cocatalyst) system comprising one alcohol and one ester. And polymerizing the one or more α-olefins to obtain a product substantially comprising a trimer of the one or more α-olefins.

Preferred PAOs of the present invention are one or more trimer-rich oligomers produced by controlling the degree of polymerization involving the use of a double accelerator system comprising an ester and an alcohol. This process is carried out under polymerization conditions in two or more continuously linked continuous stirred reactors in the presence of a promoter comprising alcohol and acid, or ester formed therefrom. Contacting the raw material containing olefin with the catalyst containing BF ₃ . The product lighter than the trimer is distilled off from the second reaction vessel after polymerization and the lower product is hydrogenated. The hydrogenated product is then distilled to obtain a trimer rich product. In one embodiment, the product is a narrow fraction (narrow molecular weight distribution), low viscosity, low Noack volatile PAO. In another embodiment, the resulting bottom product is used unblended with the second PAO.

  In one embodiment, the product is a low density, low Noack volatile PAO with a narrow fraction (narrow molecular weight distribution). As in the present invention, the term “narrow fraction” means a narrow molecular weight range. In the most preferred embodiment of the present invention, the narrow fraction low viscosity, low Noack volatile PAO is preferably 85 wt% or more, more preferably 90 wt% or more, even more preferably 95 wt% or more, even more preferably. Will comprise a very high percentage of one or more α-olefin trimers, greater than 99% by weight. The term “narrow molecular weight range” can be understood by those skilled in the art from the above viewpoint.

  The raw material includes one or more α-olefins. The terms “α-olefin” and “alpha olefin” are used interchangeably in the present invention. The alpha olefin may be selected from any one or more of C3 to C21 alpha olefins, preferably C6 to C16 alpha olefins, more preferably 1-octene, 1-decene, 1-dodecene. , And 1-tetradecene. The alpha olefin is preferably a linear alpha olefin (LAO). Mixtures of any of the aforementioned alpha olefins can be used.

  In a preferred embodiment, two or more selected from 1-octene, 1-decene, 1-dodecene, and 1-tetradecene are used as raw materials. In another preferred embodiment, the feedstock contains 40% or more 1-decene, or more than 40% 1-decene, or 50% or more 1-decene.

  In another preferred embodiment, the olefin feedstock is 40 wt% or more 1-decene, or more than 40 wt% 1-decene, or 50 wt% or more 1-decene, and 1-octene, 1-dodecene. And the remaining olefin raw material consisting essentially of one or more selected from 1-tetradecene.

  In another preferred embodiment, the olefin feed consists essentially of 1-decene, and in yet another preferred embodiment, the olefin feed consists essentially of 1-decene and 1-dodecene, and in yet another preferred embodiment. The olefin feed consists essentially of 1-decene and 1-tetradecene, and in yet another preferred embodiment, the olefin feed consists essentially of 1-dodecene.

  In another embodiment, the raw material comprises 1-decene. In a preferred embodiment, the feedstock consists essentially of 1-decene and the promoter of the present invention fed together to a reactor containing a polymerization catalyst, and the product of the process of the present invention is about 3.6 cSt at 100 ° C. Includes a distillation fraction having the characteristics of viscosity.

  In another embodiment, the feedstock consists essentially of 1-decene, 1-dodecene, and the promoter of the present invention fed to a reaction vessel containing an oligomerization catalyst, wherein the product of the process of the present invention is 100 It contains a distillation fraction characterized by having a viscosity of about 3.9 cSt at ° C.

  In one embodiment, the olefin used for the raw material is supplied together with the reaction vessel. In another embodiment, the olefin is fed separately to the reaction vessel.

In addition to conventional BF ₃ oligomerization catalysts, two or more different promoters (or promoters) are also included. In the present invention, the two different promoters are selected from (i) alcohols and (ii) esters as one or more alcohols and one or more esters present.

  Alcohols useful in the process of the present invention are selected from C1 to C10 alcohols, more preferably C1 to C6 alcohols. These can be linear or branched alcohols. Preferred alcohols are methanol, ethanol, n-propanol, n-butanol, n-pentanol, n-hexanol, and mixtures thereof.

  Esters useful in the process of the present invention are one or more reaction products of one alcohol and one acid. The alcohols useful for preparing the esters in the present invention are preferably selected from the same alcohols as described above. However, the alcohol used to produce the ester for the accelerator used in (ii) may be different from or the same as the alcohol used as the accelerator in (i). The acid is preferably acetic acid, but can be any low molecular weight monobasic carboxylic acid such as formic acid, propionic acid, and the like.

If the alcohol in (i) is different from the alcohol used in (ii), it may be difficult to tell exactly what kind of alcohol and ester the ester in (ii) may be somewhat dissociated Those skilled in the art understand that this is not the case. Furthermore, (i) and / or (ii) can be added separately or together and separately or together with one or more olefin feeds. BF ₃ and acid / ester are preferably added to the raw material together with one or more α-olefins.

  In this process, the ratio of group (i) cocatalyst to group (ii) cocatalyst (ie (i) :( ii)) is from about 0.2; 1 to 15; 1, preferably from 0.5: 1. A range of 7: 1 is preferred.

It is preferable to introduce bromine trifluoride into the reaction vessel at the same time as the cocatalyst and the olefin raw material. In the case of two or more connected continuous stirred reaction vessels, it is preferred to introduce BF ₃ , cocatalyst and olefin raw material only into the first reaction vessel, preferably simultaneously. More preferably, the one or more reaction zones comprise excess bromine trifluoride governed by the pressure or partial pressure of bromine trifluoride. In this regard, bromine trifluoride is preferably maintained in the reaction zone at a pressure of about 2 to about 500 psig, preferably about 2 to 50 psig (1 psi = 703 kg / m ² ). Alternatively, bromine trifluoride can be introduced into the reaction mixture by sparge, but can also be introduced according to other known methods of introducing bromine trifluoride into the reaction zone.

  Suitable temperatures for the reaction are also conventional and can vary from about -20 ° C to about 90 ° C, with a range of about 15 ° C to 70 ° C being preferred. Appropriate residence times in each reactor and other details of the process are within the ability of one skilled in the art to determine from this disclosure.

  In one embodiment, after reaching steady state in the final reactor, the product from the last reactor is sent to the first distillation column, in which unreacted monomer and promoter are distilled off. One of ordinary skill in the art can ascertain steady state conditions by knowing when the disclosure of the present invention, for example, the QI (described below) of the collected sample from the final reaction is no longer changing. The bottom product is then sent to a second distillation column where dimer is distilled off. In some embodiments, for example where the dimer is the desired product, the bottom product is preferably first hydrogenated prior to dimer distillation. A useful dimer product can be, for example, a PAO having an apparent viscosity of 2 cSt. Alternatively, it is first distilled off and then the lower product from the second distillation product is hydrogenated.

  The product withdrawn from this hydrogenated bottom product to the top in the third distillation column is preferably a narrow fraction, i.e. a high content trimer. In one embodiment, the product contains 85% by weight or more trimer. In another embodiment, the product contains 95% or more trimer. In yet another embodiment, the product contains about 99% by weight trimer and about 1% by weight tetramer. The actual molecular weight range depends on the raw material. Thus, using a feed consisting essentially of 1-decene, the preferred product is a narrow fraction with, for example, 85% by weight of C30 PAO. In the case of raw materials consisting essentially of 1-decene and 1-dodecene, the preferred product is a narrow fraction with, for example, 85% by weight of C30, C32, C34, C36 PAO. The percentage of each particular carbon number can be narrowed by those skilled in the art by the present disclosure.

  The lower product from this third distillation column also provides a useful PAO product such as PAO having an apparent viscosity of 6 cSt.

  In one embodiment, a particular advantage of the present invention is the surprising discovery that the viscosity can be controlled by the ratio of alcohol to ester, such that the higher the alcohol / ester ratio, the higher the viscosity is obtained. Also, the degree of polymerization can be narrowed more precisely by controlling the concentration of alcohol and ester. This is also within the knowledge of those skilled in the art from the disclosure of the present invention.

  In the examples below, the improvement in trimer yield selectivity is indicated by the factor QI, which is the weight ratio of trimer to the sum of trimer, tetramer, and higher oligomers. The results are shown in Tables 1 and 2. Properties of narrow fraction trimers and by-products produced in the same process are shown in Tables 3 and 4. These are compared with conventional PAOs with similar viscosities. These examples illustrate the present invention and it will be appreciated by those skilled in the art that many modifications and variations are possible by the disclosure of the present invention. Accordingly, it can be seen that, within the scope of the appended claims, the invention may be practiced unless otherwise indicated.

Comparative Example 1
Oligomerization of 1-decene in two continuous stirred tank reactors connected at 18 ° C. and 5 psig with feedstock consisting essentially of olefin, BF ₃ and BF ₃ butanol (complex of catalyst and alcohol) did. The free BF ₃ concentration was 0.1 wt% (1.8 mmole / 100 parts olefin feed), the weight ratio of BF ₃ with respect to BF ₃ · butanol complex in the raw material is 0.2: 1. The residence times in the first and second reactors were 1.4 hours and 1 hour, respectively. When the system reached steady state, a sample was taken from the second reactor and the composition of the crude polymer was determined by gas chromatography (GC). The% conversion and QI shown in Table 1 were calculated from the GC results. The QI obtained was 0.375, which means that only 37.5% of the oligomer mixture (trimer and higher) was a trimer.

Example 2
Accelerator system comprises a BF ₃ · butanol and BF ₃ · butyl acetate, except that the residence time in the first and second reaction tank is 0.5 hours and 1.3 hours, respectively, in the same manner as in Comparative Example 1 went. The molar ratio of butanol to butyl acetate was 7: 1 and the weight ratio of free BF ₃ to complex BF ₃ was 0.1: 1. Addition of BF ₃ · butyl acetate in the accelerator system reduces the conversion as compared to Comparative Example 1 as shown in Table 1 and produces many trimers as shown by the high QI of Example 2. It was done.

Example 3
Accelerator system is 4; raise the BF ₃ · butyl acetate complex concentration to have a first BF ₃ · butanol / BF ₃ · butyl acetate ratio, the weight ratio of free BF ₃ with respect to complex BF ₃ is 0.08: The same procedure as in Example 2 was performed except that 1. The conversion rate was similar to Example 2 due to more acetate and incorporation in the accelerator system, but the QI of the polymer increased to 0.651 as shown in Table 1.

Example 4
BF ₃ · acetate / BF ₃ · butanol ratio is 2.5: 1 and further raise the BF ₃ · butyl acetate concentration accelerator system so that the reaction temperature was 21 ° C., the residence of the first and second reaction tank Same as Example 2 except that the times were 1.7 hours and 0.7 hours, respectively. As shown in Table 1, not only was high conversion achieved, but there was also a further increase in QI with increasing temperature and acetate content.

Comparative Example 5
The raw material is a mixture containing 70% by weight of 1-decene and 30% by weight of 1-dodecene, the accelerator system is BF ₃ · ethanol, and the residence times in the first and second reaction vessels are 1.3 hours each. And Comparative Example 1 except that the time was 0.94 hours. Table 2 shows the conversion rate and QI of the polymer. By using a mixture of 1-decene and 1-dodecene, and an alcohol having a lower molecular weight than Comparative Example 1, the QI increased to 0.51.

Example 6
The same as Comparative Example 5, except that a double promoter system of BF ₃ · ethanol and BF ₃ · ethyl acetate was used in a ratio of 12: 1. Although the conversion rate was lower than that of Comparative Example 5 due to the addition of BF ₃ · ethyl acetate to the accelerator system, QI higher than that of Comparative Example 5 was obtained as shown in Table 2 below.

Example 7
Same as Comparative Example 5, except that the accelerator system used was 3.5: 1 BF ₃ .butanol and BF ₃ .butyl acetate. The QI was further increased using a high molecular weight alcohol / alkyl acetate system. However, the conversion rate decreased.

Example 8
Same as Example 7 except that the olefin feed mixture contained 60 wt% 1-decene and 40 wt% 1-dodecene. When the raw material mixture contained more 1-dodecene, the QI decreased even though the conversion rate was the same as in Example 7.

Comparative Example 9
A low viscosity mixture containing 7.2% by weight of PAO with an apparent viscosity of 2cSt and 92.8% by weight of PAO with an apparent viscosity of 4cSt was prepared from a commercial sample. This characteristic is shown in Table 3 below. Although the viscosity of the blend was low, Noack volatility was high due to the high dimer content.

  Table 3 also shows two reference examples, namely Reference Example A (SpectraSyn [trademark] 4PAO) and Reference Example B (Synfluid [registered trademark] 4PAO). These are both PAOs with an apparent viscosity of 4 cSt, commercially available from ExxonMobil Chemical Company and Chevron Philip. Both reference examples have a broad molecular weight distribution indicated by the oligomer distribution.

Example 10
In this example, the product obtained in Example 4 was used. In Example 4, a sample was taken from the second reaction tank that reached a steady state. This sample was distilled to remove monomer and dimer. The bottom stream was hydrogenated to saturate the trimer and higher oligomers. The hydrogenated product was distilled to obtain two PAO fractions. One (top) has an apparent viscosity of 4 cSt as shown in Table 3 below as Example 10A, and the other (bottom product) is further shown as Example 10B in Table 4 below. Has an apparent viscosity of 6 cSt.

  From Example 10A, the PAO with an apparent viscosity of 4 cSt produced in this process is mostly more than 95% trimmer. It had a narrow molecular weight distribution and a lower viscosity of 100 ° C. and −40 ° C. than the reference example. It also had good Noack volatility.

  The by-products shown in Table 4 are PAOs derived from 1-decene with an apparent viscosity of 6 cSt and a conventional commercially available 6 cSt viscosity (Reference Example C: Apparent viscosity of 6 cSt). And Noac Volatility and low temperature viscosity better than those available from ExxonMobil Chemical Company.

Example 11
As in Example 10, except that the product prepared in Example 8 was used instead of Example 4. A PAO produced with an apparent viscosity of 4 cSt as shown as Example 11A in Table 3 also has a narrow fraction and a PAO with an apparent viscosity of conventional 4 cSt (Reference Examples A and B) Had better low temperature viscosity and Noack volatility.

  Another fraction of the product, Example 11B, has an apparent viscosity of 6 cSt and is any of the commercially available C10 and mixed olefin derived (C8 / C10 / C12) reference examples C and D. Was better than. Reference Example D is also a PAO with an apparent viscosity of 6 cSt, commercially available from ExxonMobil Chemical Company.

Blends of the Invention Compositions in the present invention comprise (a) one or more Group III basestocks in the present invention, and (b) one or more PAOs.

  In one embodiment, component (a) of the composition comprises about 1-99% by volume and component (b) comprises about 1-99% by volume. In another embodiment, component (a) is included at about 30 to 90% by volume and component (b) is included at about 10 to about 70% by volume. In yet another embodiment, component (a) is included at 30 to about 80% by volume and component (b) is included at about 20 to less than about 70% by volume. Further contemplated embodiments include amounts from any given lower limit to any given upper limit, and thus, for example, component (a) may be included from about 1 to about 80% by volume, component (b) ) May be included from about 20 to about 99% by volume. The percentage is based on the total volume of the composition.

  The blend of one or more Group III materials and PAO in the present invention can be used alone as a functional liquid such as a carrier or diluent, or other base stock and / or surfactant, anti-wear One or more additives selected from additives, extreme pressure additives, viscosity index improvers, antioxidants, dispersants, pour point depressants, preservatives, seal compatibility agents, etc. Can be further blended with the additives described more fully below. Fully formulated lubricants are useful for lubrication engines, industrial or automotive gear sets, and the like.

  PAOs suitable for use in the present invention have been synthesized and the relationship between Noack Volatility at -35 ° C vs. CCS (Figure 1) and Noack Volatility vs. KV at 100 ° C (Figures 2 and 3) is relative to the actual commercial product Indicated. The curve shown is created using the Excel graph function and shows the approximate boundary function of PAO in the present invention.

  In FIG. 1, “C10 trimer” is taken as overhead from the third distillation column (ie, after the first distillation excluding unreacted monomer and promoter, hydrogenation step, and the second distillation excluding dimer). The low-volatility and low-viscosity PAO of the present invention. The “C10 / C12 trimer (1)” is collected in the same manner, but with 55 volume% C10 and the remaining C12, and has a KV100 of 3.9 cSt. The “C10 / C12 trimer (2)” is collected in the same manner, that is, from the top, but uses 60% by volume of C10 and the remaining C12 raw material, and has a KV100 of 4.1 cSt. The “C10 / C12 oligomer (3)” is a lower product using this raw material, and has a KV100 of 5.9 cSt. “C10 / C12 oligomer (3)” is designated as “C10 / C12 trimer (3)” in the figure.

  Also shown in FIGS. 1 and 2 are those identified as commercial products with apparent viscosities of 2 cSt and 4 cSt, respectively, and “2/4” of a conventional PAO made without using a double accelerator system. The mixture is shown. The upper curve (A) in each graph is drawn with data points representing the actual product, and the lower curve (B) is drawn with data points representing the product of the present invention. These curves are obtained directly by Excel's graphing / power hit function. Although certain actual commercial products appear to be under the “B” curve, such products do not have a pour point below 54 ° C.

FIG. 3 is similar to FIG. 2 and shows the mathematical relationship between the Noack volatility and the kinematic viscosity (KV100) at 100 ° C. for both the conventional low viscosity PAO and the low volatile low viscosity PAO of the present invention. Used. In both sets of PAO data (curves A and B), the curves are plotted based on a set of conditions between 3.5 and 3.95 cSt in one relationship, and then between 3.95 and 6 cSt. Plotted based on another set of conditions. A curve A drawn by data points of a conventional PAO is described by the following equation. (Ia) Noac volatility at 3.5-3.95 cSt at 100 ° C. = (50,000) (KV100) ⁻⁶ , and (ib) Noac volatility at greater than 3.95 at 100 ° C. and below 6 cSt Sex = (182) (KV100) ^−1.9 . The curve B drawn by the data points representing the PAO of the present invention can be described by the following equation: (Iii) Noac Volatility at 3.5-3.95 cSt at 100 ° C. = (900) (KV100) ^−3.2 and (iib) Noac Volatility => 3.95 at 100 ° C. and below 6 cSt = (175) (KV100) ^-2 . These equations accurately model the actual relationship at 100 ° C. between Noack volatility and kinematic viscosity for both classes of PAO. The distinct difference in Noac volatility and kinematic viscosity for PAO of the present invention at 100 ° C. with a pour point of less than 54 ° C. provides a significant advantage of blending many finished lubricants with conventional PAO.

In a preferred embodiment, the PAO of the present invention is characterized by having a pour point of less than -54 ° C and one or more of the following properties. (I) The relationship between Noack volatility (% by weight) at 35 ° C. vs. Cooling Crank Simulator Test (CCS), approximately equal to or better than Curve A in FIG. Preferably similar results are obtained in curve B. Here, these curves have the formula: Noack Volatility (wt%) = (6473.1) (cP, CCS at −35 ° C.) ^−0.834 and Noack Volatility (wt%) = (500) (cP, −35 CCS at 0 ° C.) ^-0.83 respectively. (Ii) The relationship between Noack volatility (% by weight) and kinematic viscosity (KV100) at 100 ° C., which is almost equal to or better than curve A in FIG. 2 (under the curve). Preferably similar results are obtained in curve B. Here, these curves are represented by the formula: Noack Volatility (wt%) = (354.75) (cP, CCS at −35 ° C.) ^−2.2629 and Noack Volatility (wt%) = (234.58) (cP, CCS at −35 ° C.) ^2.1632 , respectively. (Iii) The relationship between Noack volatility (% by weight) vs. kinematic viscosity as shown in curve A or preferably curve B in FIG.

In a preferred embodiment, the PAO of the present invention is characterized by having a pour point below -54 ° C and a Noack volatility (KV100) relationship to KV at 100 ° C as follows. That is, in one embodiment, (ia) from 3.5 to 3.95 cSt at 100 ° C., Noack volatility = (50,000) (KV100) ⁻⁶ , and (ib) from 3.95 at 100 ° C. Larger than 6 cSt, Noack volatility = (182) (KV100) ^-1.9 . In another embodiment, (iia) Noac Volatility = (900) (KV100) ^−3.2 at 3.5-3.95 cSt at 100 ° C. and (iib) greater than 3.95 at 100 ° C. and not more than 6 cSt Noack volatility = (175) (KV100) ⁻² .

Experimental Example-Blend The present invention is described below in the same manner as in the previous examples and comparative examples, and in comparison with other methods and the products obtained by that method. It will be understood that many modifications and variations are possible and may be practiced except where specifically noted herein within the scope of the appended claims.

  Figures 5a and 5b below show a formulation of a PAO of the present invention comprising a Group III basestock that meets the requirements of SAE grade 0W multi-grade engine oil.

  Tables 5a and 5b show the low temperature viscosity and high temperature stability requirements of a significant concentration blend of Yubase 4 and / or Yubase 6 with low volatility and low viscosity PAO in the present invention is SAE grade 0W multi-grade engine oil. It shows that it can be used to meet. One or more advantages of the present invention are that conventional Group III basestock availability is significantly greater than Group III basestocks derived from PAO and / or wax isomers. The “C10 trimmer”, “C10 / C12 (1)” and “C10 / C12 (3)” materials are the same as in FIGS. 1 and 2 above.

  Table 6 above outlines how more than 50% of the conventional Group III base stock blended with this new class of PAO provides the same low temperature viscosity and Noack volatility as 100% of the conventional PAO. Show. “Group IV +” indicates the same as the low volatility and low viscosity PAO base stock in the present invention.

  In one embodiment, the Group III and IV basestock mixture in the present invention is used with an amount of additional lubricating oil component effective to produce a lubricating oil composition. Additional components include, for example, other polar and / or non-polar lubricant base stocks (eg, API Group I, II, V, and mixtures thereof), and, for example, oxidation, depending on the use of the composition Inhibitors, metal and nonmetal dispersants, metal and nonmetal surfactants, corrosion and rust inhibitors, metal deactivators, antiwear agents (metal and nonmetal, phosphorus and nonphosphorous, sulfur and nonsulfur) Type), extreme pressure additive (metal and non-metal, phosphorus-containing and non-phosphorus, sulfur-containing and non-sulfur type), anti-trapping agent, pour point depressant, wax modifier, viscosity modifier, seal compatibility imparting agent , Friction modifiers, lubricants, antifouling agents, color formers, defoamers, demulsifiers, emulsifiers, diluting agents (sometimes also called Group VI improvers such as PIB, some PMAs, etc.), fuel Stabilization Additives of performance such as, but not limited to, agents, adhesives and the like.

  For example, the fuel stabilizer is added to a two-cycle engine in which fuel and lubricating oil are mixed. Demulsifiers are added to lubricating oil compositions that are expected to come into contact with water, while emulsifiers are primarily used for metal action.

  For a review of many commonly used additives, see “Lubricating Oils and Related Products” (Belle Lark Hemy, Deerfield Beach, Florida, ISBN 0-89573), which is well described for many of the lubricating oil additives described below. -177-0) by Klamann. M.M. W. See also Ranney's “Lubricant Additives” (Noyes Data, Park Ridge, NJ, 1973).

  In a preferred embodiment, the lubricating oil composition of the present invention will comprise a Group III / Group IV blend of the present invention and one or more components selected from:

Surfactants Suitable surfactants include alkali metal or alkaline earth metal salts of one or more sulfonic acids, phenols, carboxylic acids, phosphoric acids, and salicylic acids.

  Sulfates can be prepared from sulfonic acids typically obtained by sulfonation of alkyl-substituted aromatic hydrocarbons. Examples of hydrocarbons include those obtained with alkylated benzene, toluene, xylene, naphthalene, biphenyl, and their halogenated derivatives (eg, chlorobenzene, chlorotoluene, and chloronaphthalene). The alkylating agent typically has about 3 to 70 carbon atoms. The alkaryl sufonates typically contain from about 9 to 80 or more carbon atoms, more typically from about 16 to 60 carbon atoms.

  Raney in the aforementioned “lubricating oil additives” discloses a number of overbased metal salts of various sulfonic acids useful as surfactants and dispersants in lubricating oils. A book entitled “Lubricant Additives” (by CV Small Here and RK Smith, Regius Hyles, Cleveland, Ohio, 1967) also discloses many overbased sulfonates. These are useful as dispersants / surfactants.

Alkaline earth phenol salts are another useful class of surfactants. These surfactants are alkyl earths or sulfurized alkaline earth metal hydroxides or oxides (eg, CaO, Ca (OH) ₂ , BaO, Ba (OH) ₂ , MgO, Mg (OH) ₂ ). Made by reacting with alkylphenols. Useful alkyl groups include linear or branched C1-C30, preferably C4-C20 alkyl groups. Specific examples of suitable phenols include isobutylphenol, 2-ethylhexylphenol, nonylphenol, 1-ethyldecylphenol and the like. It should be noted that the starting alkylphenol can contain two or more alkyl substituents, each of which is independently linear or branched. If non-sulfurized alkylphenol is used, the sulfurized product can be obtained by methods well known in the art. These methods include heating a mixture of alkylphenol and sulfurizing agent (including elemental sulfur, sulfur halides such as sulfur dichloride, etc.), and then reacting the sulfurized phenol with an alkaline earth metal base. A process is included.

  Metal salts of carboxylic acids other than salicylic acid are also used as surfactants. These carboxylic acid surfactants are prepared by methods similar to those used for salicylates.

  The surfactant may be what is known simply as a surfactant or a hybrid or composite surfactant. The latter surfactant can provide the properties of two surfactants without the need to blend separate materials. See for example US Pat. No. 6,034,039. This document is incorporated herein by reference in its entirety. In a preferred embodiment, the total surfactant concentration is from about 0.01 to about 6.0 wt%, preferably from 0.1 to 0.4 wt%, based on the total weight of the composition.

Antiwear and Extreme Pressure Additives Internal combustion engine lubricants typically contain antiwear and / or extreme pressure additives to provide sufficient antiwear protection to the engine. Characteristics for engine oil performance are increasingly showing a trend for improved anti-wear characteristics of oil. Anti-wear and extreme pressure additives achieve this role by reducing the friction and wear of metal parts.

There are many different types of anti-wear additives, but for decades, the main additive in internal combustion engine crankcase oil is zinc or zinc dialkyldithiophosphate (ZDDP) as the main metal component It was an alkylthiophosphate metal, in particular a dialkyldithiophosphate metal. ZDDP compounds are generally represented by the formula Zn [SP (S) (OR ¹ ) (OR ² )] ₂ , where R ¹ and R ² are C ¹ -C 18 alkyl groups, preferably C ² -C 12 alkyl groups. These alkyl groups can be linear or branched and can be derived from alkylaryl groups such as primary and / or secondary alcohols and / or alkylphenols. The ZDDP is typically used in an amount of about 0.4-1.4% by weight of the total lubricating oil composition, although amounts greater or less than that range can often be used advantageously.

  However, it has been found that phosphorus from these additives also has an adverse effect on catalytic converter catalysts and automotive oxygen sensors. One way to minimize this effect is to replace some or all of the ZDDP with an anti-wear additive that does not contain phosphorus.

Various non-phosphorous additives have also been used as anti-wear additives. Sulfurized olefins are useful as antiwear and extreme pressure additives. Sulfur-containing olefins are prepared by sulfurization or various organic materials including aliphatic, arylaliphatic, or cycloaliphatic olefinic hydrocarbons containing about 3-30 carbon atoms, preferably about 3-20 carbon atoms. Can do. The olefinic compound contains one or more non-aromatic double bonds. Such compounds are of the formula
R ³ R ⁴ C = CR ⁵ R ⁶
In the formula, each R ³ , R ⁴ , R ⁵ , R ⁶ is independently hydrogen or a hydrocarbon radical. Preferred hydrocarbon radicals are alkyl or alkenyl groups. Any two of R ³ , R ⁴ , R ⁵ and R ⁶ can be linked to form a ring. Further information regarding sulfurized olefins and their preparation can be found in US Pat. No. 4,941,984, which is incorporated herein by reference in its entirety.

  The use of polysulfides and thiophosphates of thiophosphates as lubricating oil additives is disclosed in US Pat. Nos. 2,443,264, 2,471,115, 2,526,497, and 2,591,577. ing. Anti-wear, antioxidant, and addition of phosphorothionyl disulfide as an extreme pressure additive are disclosed in US Pat. No. 3,770,854. Alkylthiocarbamoyl compounds (eg, bis (dibutyl) thio) in combination with molybdenum compounds (eg, oxymolybdenum diisopropyl phosphorodithioate disulfide) and phosphorus esters (eg, dibutyl hydrogen phosphite) as antiwear additives in lubricating oils. The use of carbamoyl) is disclosed in US Pat. No. 4,501,678. U.S. Pat. No. 4,758,362 discloses the use of carbamate additives that provide improved anti-wear and extreme pressure properties. The use of thiocarbamate as an antiwear additive is disclosed in US Pat. No. 5,693,598. Also useful as antiwear agents are thiocarbamate / molybdenum complexes such as moly-sulfur alkyldithiocarbamate trimer complexes (R = C8-C18 alkyl).

  Glycerol esters can be used as antiwear agents. For example, mono-, di-, and tri-oleate, mono-palmitate, and mono-myristate can be used.

  ZDDP has been combined with other compositions that provide anti-wear properties. US Pat. No. 5,034,141 discloses that a combination of a thiodixanthogen compound (eg, octylthiodi-xanthogen) and a metal thiophosphate (eg, ZDDP) improves antiwear properties. US Pat. No. 5,034,142 shows the use of metal alkoxyalkylxanthates (eg, nickel ethoxy-ethylxanthate) and dixanthogens (eg, diethoxyethyldixanthogen) in combination with ZDDP to improve anti-wear properties Is disclosed.

  Preferred antiwear additives include phosphorus and sulfur compounds such as zinc dithiophosphate and / or sulfur, nitrogen, boron, molybdenum phosphorodithioate, molybdenum dithiocarbamate, and various heterocycles (dimercaptothiadiazole, mercapto). Organic molybdenum derivatives including benzothiazole, triazine and the like, and alicyclic compounds, amines, alcohols, esters, diols, fatty acid amides and the like are also used. In a preferred embodiment, such additives can be used in an amount of about 0.01 to 6% by weight, preferably about 0.01 to 4% by weight, based on the weight of the total composition.

Viscosity index improver Viscosity index improvers (also known as Group VI improvers, viscosity modifiers, and viscosity improvers) provide lubricating oils having high and low temperature operability. These additives provide shear stability at elevated temperatures and acceptable viscosity at low temperatures.

  Suitable viscosity index improvers include high molecular weight hydrocarbons, olefin polymers and copolymers, polyesters, and viscosity index improver dispersants that function as both viscosity index improvers and dispersants. Typical molecular weights of these polymers are about 10,000 to about 1,000,000, more typically about 20,000 to 500,000, and more typically about 50,000 and about 200,000. In the range of 000.

  Specific examples of suitable viscosity index improvers are methacrylates, butadiene, olefins, or alkylated styrene polymers and copolymers. Polyisobutylene (PIB) is a commonly used viscosity index improver. Another suitable viscosity index improver is PMA or polymethacrylate (eg, copolymers of alkyl methacrylates of various chain lengths), and some of these formulations also serve as pour point depressants. Other suitable viscosity index improvers include copolymers of ethylene and propylene, hydrogenated block copolymers of styrene and isoprene, and polyacrylates (eg, copolymers of acrylates of various chain lengths). Specific examples include polymers based on styrene-isoprene or styrene-butadiene having a molecular weight of about 50,000 to 200,000.

  In one embodiment of the invention, the viscosity index improver is used in an amount of about 0.01 to 6% by weight, preferably about 0.01 to 4% by weight, based on the weight of the total composition.

Antioxidants Antioxidants delay the oxidative degradation of the base stock during operation. Such decomposition can result in deposition on the metal surface, generation of deposits, or increased viscosity in the lubricating oil. A wide range of oxidation inhibitors useful in lubricating oil compositions are well known. See, for example, Klamann's portion in “Lubricating Oils and Related Products” above, and US Pat. Nos. 4,798,684 and 5,084,197. These disclosures are incorporated herein by reference in their entirety.

  Useful antioxidants include hindered phenols. These phenolic antioxidants can be ashless (metal-free) phenolic compounds or neutral or basic metal salts of certain phenolic compounds. Typical phenolic antioxidant compounds are hindered phenolic compounds containing sterically hindered hydroxyl groups, including derivatives of dihydroxyaryl compounds in which the hydroxyl groups are in the o- or p-position relative to each other. Exemplary phenolic antioxidants include hindered phenols substituted with C6 + alkyl groups and derivatives of these hindered phenols linked to alkylene. Specific examples of this type of phenolic material include 2-t-butyl-4-heptylphenol, 2-t-butyl-4-octylphenol, 2-t-butyl-4-dodecylphenol, 2,6-di- t-butyl-4-heptylphenol, 2,6-di-t-butyl-4-dodecylphenol, 2-methyl-6-t-butyl-4-heptylphenol, and 2-methyl-6-t-butyl- 4-dodecylphenol is included. Other useful hindered monophenolic antioxidants can include, for example, hindered 2,6-dialkylphenolic propionic acid derivatives. Bis-phenolic antioxidants can also be advantageously used in combination with the present invention. Specific examples of ortho-linked phenol include 2,2′-bis (6-tert-butyl-4-heptylphenol), 2,2′-bis (6-tert-butyl-4-octylphenol), and 2,2 '-Bis (6-tert-butyl-4-dodecylphenol) is included. Para-linked bisphenols include, for example, 4,4'-bis (2,6-di-t-butylphenol) and 4,4'-methylenebis (2,6-di-t-butylphenol).

Non-phenolic oxidation inhibitors that can be used include aromatic amine antioxidants, which can be used alone or in combination with phenolic ones. Specific examples of non-phenolic antioxidants include alkylated and non-alkylated aromatic amines such as aromatic monoamines represented by the formula That is, R ⁸ R ⁹ R ¹⁰ N (wherein R ⁸ is an aliphatic, aromatic or substituted aromatic group, R ⁹ is an aromatic or substituted aromatic group, R ¹⁰ is a hydrogen atom, alkyl An aryl group), or R ¹¹ S (O) XR ¹² (wherein R ¹¹ is an alkylene, alkenylene, or aralkylene group, R ¹² is a higher alkyl group, or an alkenyl, aryl, or alkaryl group; x is 0, 1, or 2). The aliphatic group R ⁸ can contain 1 to 20 carbon atoms, preferably 6 to 12 carbon atoms. This aliphatic group is a saturated aliphatic group. Preferably, R ⁸ and R ⁹ are both aromatic or substituted aromatic groups, and this aromatic group may be a condensed ring aromatic group such as naphthyl. Aromatic groups R ⁸ and R ⁹ can also be formed with other groups such as S.

  Typical aromatic amine antioxidants have alkyl substituents of about 6 or more carbon atoms. Specific examples of aliphatic groups include hexyl, heptyl, octyl, nonyl, and decyl groups. Generally, the aliphatic group will have more than about 14 carbon atoms. Common types of amine antioxidants useful in the present invention include diphenylamines, phenylnaphthylamines, phenothiazines, imidodibenzyls, and diphenylphenylenediamines. Mixtures of two or more aromatic amines are also useful. Polymeric amine antioxidants can also be used. Specific examples of aromatic amine antioxidants useful in the present invention include p, p'-dioctyldiphenylamine, t-octylphenyl-α-naphthylamine, phenyl-α-naphthylamine, and p-octylphenyl-α-naphthylamine. Is included.

  Sulfurized alkylphenols and their alkali metal or alkaline earth metal salts are also useful antioxidants. Low sulfur peroxide decomposers are useful as antioxidants.

  Another class of antioxidants used in lubricating oil compositions are oil-soluble copper compounds. Any oil-soluble copper compound can be blended into the lubricating oil. Specific examples of suitable copper antioxidants include copper dihydrocarbyl thiophosphate or copper salt of carboxylic acid (natural or synthetic) and copper dithiophosphate. Other suitable copper salts include copper dithiocarbamate, copper sulfonate, copper phenate, and copper acetylacetonate. It is known that Cu (I) and / or Cu (II) which are bases, neutral or acidic copper derived from alkenyl succinic acid or anhydride are particularly useful.

  Preferred antioxidants include hindered phenols, arylamines, low sulfur peroxide decomposers, and other related components. These antioxidants can be used by type or in combination with each other. In a preferred embodiment, such additives can be used in an amount of about 0.01 to 5% by weight, preferably about 0.01 to 1.5% by weight, based on the weight of the total composition.

Oil-insoluble oxidation by-products are formed during dispersant engine operation. The dispersant helps dissolve these by-products and reduces their deposition on the metal surface. The dispersant may actually be ashless or ash generating. Preferably, the dispersant is ashless. So-called ashless dispersants are organic substances that produce virtually no ash upon combustion. For example, a metal-free dispersant or a metal bromide-free dispersant is considered ashless. Conversely, the metal-containing surfactants described above produce ash upon combustion.

  Suitable dispersants typically contain polar groups attached to relatively high molecular weight hydrocarbon chains. The polar group typically includes at least one element of nitrogen, oxygen, or phosphorus. Typical hydrocarbon chains contain about 50 to 400 carbon atoms.

  Chemically, many dispersants are characterized as phenates, sulfonates, sulfurized phenates, salicylates, naphthenates, stearates, carbamates, thiocarbamates, and phosphorus derivatives. A particularly useful class of dispersants are alkenyl succinic acid derivatives typically prepared by reaction of long chain substituted alkenyl succinic acid compounds, usually substituted succinic anhydrides with polyhydroxy or polyamino compounds. The long chain groups that make up the lipophilic portion of the molecule that provide solubility in oil are usually polyisobutylene groups. Many specific examples of this dispersant are commercially available and well known in the literature. US Patents describing such dispersants are, for example, 3,172,892, 3,2145,707, 3,219,666, 3,316,177, 3,341,542, 3, 444,170, 3,454,607, 3,541,012, 3,630,904, 3,632,511, 3,787,374, and 4,234,435. Other types of dispersants are U.S. Pat. Nos. 3,036,003, 3,200,107, 3,254,025, 3,275,554, 3,438,757, 3,454,555. No. 3,565,804, 3,413,347, 3,697,574, 3,725,277, 3,725,480, 3,726,882, 4,454,059 3,329,658, 3,449,250, 3,519,565, 3,666,730, 3,687,849, 3,702,300, 4,100,082, And 5,705,458, which are fully incorporated herein by reference. Further descriptions of dispersants are found, for example, in European Patent Application No. 471071, which is incorporated herein by reference.

  Hydrocarbyl substituted succinic acid compounds are well known dispersants. In particular, succinic acid amides, succinic acid esters, or succinic acid esters prepared by reaction with one or more equivalents of an alkylene amine of a hydrocarbon-substituted succinic acid compound, preferably having 50 or more carbon atoms in the hydrocarbon substituent. Amides are particularly useful.

  Succinamide is produced by a condensation reaction between an alkenyl succinic anhydride and an amine. The molar ratio can vary depending on the polyamine. For example, the molar ratio of alkenyl succinic anhydride to TEPA can vary from about 1: 1 to about 5: 1. Typical examples are US Pat. Nos. 3,087,936, 3,172,892, 3,219,666, 3,272,746, 3,322,670, 3,652,616, 3 , 948,800, and Canadian Patent No. 1,094,044, which are incorporated herein by reference in their entirety.

  Succinic acid esters are produced by a condensation reaction between an alkenyl succinic anhydride and an alcohol or polyol. The molar ratio can vary depending on the alcohol or polyol used. For example, the condensation product of alkenyl succinic anhydride and pentaerythritol is a useful dispersant.

  Succinic ester amides are produced by a condensation reaction between alkenyl succinic anhydrides and alkanolamines. For example, suitable alkanolamines include polyalkenyl polyamines such as ethoxylated polyalkylpoamines, propoxylated polyalkylpolyamines and polyethylene polyamines. One specific example is propoxylated hexamethylenediamine. A representative example is shown in US Pat. No. 4,426,305, which is incorporated by reference into the present invention.

  The molecular weight of the alkenyl succinic anhydride used in the above paragraph is in the range of about 800 to 2,500 or more. The hydrocarbyl group can be, for example, a single group such as polyisobutylene having a molecular weight of about 500 to 5,000, or a combination of such groups. The product is followed by various reagents such as sulfur, oxygen, formaldehyde, carboxylic acids such as oleic acid, hydrocarbyl dibasic acids or anhydrides, and boron compounds such as borate esters or polyborated dispersants. Can be processed. In one embodiment of the invention, the dispersant is from about 0.1 to about 0.1 moles per mole of dispersant reaction product comprising monosuccinimide, bissuccinimide (also known as disuccinimide), and mixtures thereof. Brominated with 5 moles of bromine.

  Mannich base dispersants are prepared by reaction of alkylphenols, formaldehyde, and amines. See U.S. Pat. No. 4,767,551. This document is incorporated by reference into the present invention. Process acids and catalysts such as oleic acid and sulfuric acid can also be part of the reaction mixture. The molecular weight of the alkylphenol is in the range of 800 to 2,500. Representative examples are US Pat. Nos. 3,697,574, 3,703,536, 3,704,308, 3,751,365, 3,756,953, 3,798,165, And 3,803,039, which are incorporated herein by reference in their entirety.

Representative high molecular weight fatty acid modified Mannich condensation products useful in the present invention can be prepared from high molecular weight alkyl-substituted hydroxyaromatic compounds or HN (R) ₂ group-containing reactants.

  Specific examples of high molecular weight alkyl-substituted hydroxyaromatic compounds are polypropylphenol, polybutylphenol, and other polyalkylphenols. These polyalkylphenols are obtained by alkylation of high molecular weight polypropylene, polybutylene, and other polyalkylene compounds in the presence of an alkylation catalyst with alkyl substituents on the benzene ring of the phenol having an average value of about 600 to about 100,000 molecular weight. Can be obtained by putting

Specific examples of the HN (R) ₂ group-containing reactant are alkylene polyamines, mainly polyethylene polyamines. Other representative organic compounds containing one or more HN (R) ₂ groups suitable for use in the preparation of Mannich condensation products are well known, mono- or di-amino alkanes such as ethylamine and diethanolamine and the like Substituted aromatic analogs such as phenylenediamine, diaminonaphthalene, heterocyclic amines such as morpholine, pyrrole, pyrrolidine, imidazole, imidazolidine, and piperidone, melamine, and substituted analogs thereof.

Specific examples of the alkylene polyamide reactant include ethylenediamine, diethylenetriamine, triethylenetetraamine, tetraethylenepentamine, pentaethylenehexamine, hexaethyleneheptamine, heptaethyleneoctamine, octaethylenenonamine, nonaethylenedecamine, deca Ethyleneundecamine and mixtures of such amines having a nitrogen content corresponding to the alkylene polyamines represented by the formula H ₂ N— (Z—NH—) _n H are included. In the formula, Z is divalent ethylene, and n is 1 to 10. Corresponding propylene polyamines such as propylene diamine and di-, tri-, tetra-, penta-, propylene tri-, tetra-, penta-, and hexaamine are also suitable reactants. This alkylene polyamine is usually obtained by reaction of dihalogenated alkanes such as ammonia and dichloroalkanes. Thus, alkylene polyamines obtained by reaction of 2 to 11 moles of ammonia with 2 to 6 carbon atoms and 1 to 10 moles of dichloroalkane having different carbon strips of chlorine are preferred alkylene polyamine reactants.

  Aldehyde reactants useful for the preparation of polymeric products useful in the present invention include aliphatic aldehydes such as formaldehyde (paraformaldehyde and formalin), acetaldehyde and aldols (eg, b-hydroxybutyraldehyde). Formaldehyde or a formaldehyde-forming reactant is preferred.

  Ashless dispersant additives for hydrocarbyl substituted amines are well known to those skilled in the art. See, for example, U.S. Pat. Nos. 3,438,757, 3,565,804, 3,755,433, 3,822,209, and 5,084,197. These are incorporated herein by reference in their entirety.

  Preferred dispersants include brominated and non-brominated succinimides including derivatives from mono-succinimides, bis-succinimides, and / or mixtures of mono- and bis-succinimides. Here, the hydrocarbyl succinimide is derived from a hydrocarbylene group such as polyisobutylene having a number average molecular weight (Mn) of about 500 to about 5,000, and a mixture of such hydrocarbylene groups. Other preferred dispersants include succinic esters and amides, alkylphenol-linked Mannich adducts, their capped derivatives, and other related ingredients. In one embodiment, such additives are used in an amount of about 0.1-20% by weight, preferably about 0.1-8% by weight.

Pour Point Depressants
Conventional pour point depressants (also known as lubricating oil flow improvers) can be added to the compositions of the present invention if desired. This pour point depressant can be added to the lubricating composition of the present invention to lower the minimum temperature at which the liquid will flow or can be injected. Specific examples of suitable pour point depressants include polymethacrylates, polyacrylates, polyarylamides, condensation products of haloparaffin waxes with aromatic compounds, vinyl carboxylate polymers, and dialkyl fumarate, fatty acid vinyl esters. And terpolymers of allyl vinyl ethers. U.S. Pat.Nos. 1,815,022, 2,015,748, 2,191,498, 2,387,501, 2,655,479, 2,666,746, 2,721,877 Nos. 2,721,878, and 3,250,715, which are fully incorporated by reference into the present invention, describe useful pour point depressants and / or their preparation. In one embodiment of the invention, such additives are used in an amount of about 0.01 to 5% by weight, preferably about 0.01 to 1.5% by weight.

Corrosion inhibitors Corrosion inhibitors are used to reduce the degradation of metal parts in contact with the lubricating oil composition. Suitable corrosion inhibitors include thiadiazole and triazole. See, for example, U.S. Pat. Nos. 2,719,125, 2,719,126, and 3,087,932. These are incorporated herein by reference in their entirety. In one embodiment of the invention, such additives are used in an amount of about 0.01 to 5% by weight, preferably about 0.01 to 1.5% by weight.

Seal compatibility imparting agent Seal compatibility imparting agent assists in blistering of the elastomeric seal by causing a chemical reaction in the fluid or a physical change in the elastomer. Suitable lubricating oil seal compatibility agents include organophosphates, aromatic esters, aromatic hydrocarbons, esters (eg, butyl benzyl phthalate), and polybutenyl succinic anhydrides . This type of additive is commercially available. In one embodiment of the invention, such additives are used in an amount of about 0.01 to 3% by weight, preferably 0.01 to 2% by weight.

Antifoam agent An antifoam agent can advantageously be added to the lubricating oil composition. These reagents delay the formation of stable foam. Silicones and organic polymers are typical antifoam agents. For example, polysiloxanes such as silicone oil or polydimethylsiloxane provide antifoam properties. Antifoam agents are commercially available and can be used in conventional small amounts with other additives such as demulsifiers. Usually, the amount of these formulated additives is less than 1% and often less than 0.1%.

Inhibitors and anti-rust additives Anti-rust additives (or corrosion inhibitors) are additives that protect lubricating metal surfaces against chemical attack by water or other impurities. A wide variety of these reagents are commercially available. These are also mentioned in the Clamman part of the aforementioned “lubricating oils and related products”.

  One type of anti-rust additive is a polar compound that preferentially wets the metal surface and protects it with an oil film. Another type of anti-rust additive absorbs water by incorporating water into an emulsion of water in the oil so that only the oil contacts the metal surface. Yet another type of anti-rust additive chemically adsorbs to the metal to produce a non-reactive surface. Specific examples of suitable additives include zinc dithiophosphate, metal phenolates, basic metal sulfonates, fatty acids, and amines. In one embodiment of the invention, such additives are used in an amount of about 0.01 to 5% by weight, preferably about 0.01 to 1.5% by weight.

Typical additive amounts When the lubricating oil includes one or more of the above-described additives, the additive or additives are blended in an amount sufficient for the additive to perform its intended function. The amounts of such additives useful in the present invention are shown in Table 7 below.

  It should be noted that many additives are shipped from the manufacturer and are used with a certain amount of process oil solvent in the formulation. Thus, as with the other amounts described in this invention, the amounts in Table 7 relate to the amount of active ingredient (ie, non-solvent portion in the ingredient). The weight percentages below are based on the total weight of the lubricating oil composition.

  The important physical properties shown in the present invention were determined according to the following method.

  Kinematic viscosity (KV) was measured according to ASTM D445 at the indicated temperatures (eg, 100 ° C. or −40 ° C.).

  The viscosity index (VI) was determined according to ASTM D-2270.

  Noack volatility was determined according to the method of ASTM D5800, except that temperature adjustment was performed every two years instead of every year.

  The pour point was determined according to ASTM 5950.

  The cooling crank stimulation (CCS) test was determined according to ASTM D5293.

The (registered) trademarks used in the present invention are represented by the TM symbol or the ^R symbol, indicating that these names can be protected with certain trademark rights, for example, that they can be registered as trademarks in the legal system. Yes.

  All patents and patent applications cited in the present invention, test procedures (such as ASTM methods), and other documents are such that such incorporation is to the extent that such disclosure is consistent with the present invention. To the extent permitted by the legal system, it is fully incorporated into the present invention by reference.

    In the present invention, when a numerical lower limit and a numerical upper limit are shown, it means that any range from an arbitrary lower limit to an arbitrary upper limit is included. While specific embodiments of the present invention have been described, including specific, many different modifications will be apparent to and readily made by those skilled in the art without departing from the spirit and scope of the invention. Will. Accordingly, the claims appended hereto are not intended to be limited to the examples and descriptions herein, but rather the claims are treated as equivalents by those of ordinary skill in the relevant arts. All features of patentable novelty belonging to the present invention are to be construed as including all features.

  The present invention has been described above with reference to a number of aspects and specific examples. Many modifications will be apparent to those skilled in the art in light of the above detailed description. All such modifications are fully within the scope of the appended claims.

FIG. 4 is a diagram showing the relationship between Noack volatility and a low temperature crank simulator (CCS) test at −35 ° C. for the composition of the present invention compared to the composition of the first technique. It is a figure which shows the relationship between Noack volatility and kinematic viscosity in 100 degreeC about the composition of this invention compared with the composition of the first technique. FIG. 3 is a view similar to FIG. 2 except that the curve is idealized using a small set of data points.

Claims (32)

(A) one or more API Group III base stocks; (b) a pour point less than -54 ° C; and (i) a Noack for CCS on or below curve A in FIG. Volatile relationship,
(Ii) Noack volatility relationship to CCS on or under curve B in FIG.
(Iii) Noack volatility relationship to KV on curve A or below curve A in FIG.
(Iv) Noack volatility relationship to KV on or under curve B in FIG.
(V) Noack volatility relationship to KV on curve A in FIG. 3 or below curve A; and (vi) Noack volatility relationship to KV on curve B in FIG.
One or more PAO base stocks characterized by having one or more of the following relationships:
A composition comprising   The composition of claim 1, wherein (b) comprises one or more PAOs further having at least one of relationships (i) and (iii).   The composition according to claim 1 or 2, wherein (b) comprises one or more PAOs further having any of the relationships (i) and (iii).   The said (b) contains one or more PAO which further has the relationship of at least any one of relationship (ii) and (iv), The statement of any one of Claims 1-3 characterized by the above-mentioned. Composition.   The composition according to any one of claims 1 to 4, wherein (b) comprises one or more PAOs further having any of the relationships (ii) and (iv).   Said (b) is obtained by a process comprising oligomerizing one or more α-olefins in the presence of one oligomerization catalyst and a double promoter system comprising one alcohol and one ester. The composition according to any one of claims 1 to 5, further having the following characteristics.   Wherein (b) is produced by a process comprising oligomerizing one or more α-olefins in the presence of one oligomerization catalyst and a double promoter system comprising one alcohol and one ester. The composition according to any one of claims 1 to 6, further having a feature of: The (b) further comprises an oligomerized α-olefin subjected to hydrogenation,
Wherein the oligomerized α-olefin is prepared from an olefin feedstock comprising 50-80 wt% 1-decene and 50-20 wt% 1-dodecene, and the oligomerized α-olefin is BF ₃ , and 1 Oligomerized in the presence of a double accelerator system comprising one or more alcohols and one or more alkyl acetates;
The composition according to any one of claims 1 to 7, wherein   9. The (b) comprises 5cStPAO comprising about 40 to 80% by weight 1-decene and about 60 to about 20% by weight 1-dodecene, based on the weight of 5cStPAO. The composition of any one of these. (B)
(A) one or more α-olefins, one α-olefin for a time sufficient to produce one or more α-olefin trimers in one or more continuously stirred reactors under oligomerization conditions; Contacting an olefin oligomerization catalyst, an alcohol promoter, and an ester promoter;
(B) distilling off unreacted α-olefin and the α-olefin dimer to obtain a lower product containing the trimer;
(C) hydrogenating said lower product to obtain a hydrogenated lower product; and (d) next, said lower product to obtain one or more fractions comprising a trimer product. Fractionating the product,
The composition according to claim 1, further produced by a process comprising oligomerization of an α-olefin comprising   The step (a) comprises contacting one or more α-olefins selected from C8, C10, C12, C14, and C16 α-olefins and mixtures thereof. 11. The composition according to 10. Wherein (b) is one or more α-olefins, for a time sufficient to produce one or more α-olefin trimers in one or more continuously stirred reactors under oligomerization conditions; Further characterized in that it can be obtained or produced by an improved process comprising contacting one α-olefin oligomerization catalyst, one alcohol promoter, and one ester promoter,
The improvement includes distilling off unreacted monomers and promoters in a first distillation column; removing lower product from the first distillation column; distilling off dimers in a second distillation column; and the second distillation column. The lower product is taken out from the process, the lower product is hydrogenated to obtain a hydrogenated product, the hydrogenated product is transferred to a third distillation column, the upper or lower part of the third distillation column 12. A composition according to any one of the preceding claims, comprising the step of obtaining one or more products from any.   The (a) is selected from a solvent dewaxed API Group III basestock, a catalytic dewaxed API Group III basestock, and a wax isomer API Group III basestock. The composition of any one of 1-12.   13. A composition according to any one of the preceding claims, wherein (a) does not comprise a wax isomer API Group III base stock. (B)
(I) PAO containing 85 wt% or more of 1-decene trimer and having a viscosity of about 3.6 cSt at 100 ° C, and (ii) 85 wt% or more of 1-decene trimer, PAO with a viscosity of 3.9 cSt
The composition according to claim 1, wherein the composition is selected from at least one of the following. Oligomerization of one or more α-olefins in the presence of (a) one or more Group III basestocks, and (b) an oligomerization catalyst, and a double accelerator system comprising one alcohol and one ester. One or more PAOs that are more obtainable or manufactured by a process that includes
A composition comprising   The (a) is selected from a solvent dewaxed API Group III basestock, a catalytic dewaxed API Group III basestock, and a wax isomer API Group III basestock. 17. The composition according to 16.   17. The composition of claim 16, wherein (a) is free of wax isomer API Group III base stock. (A) one or more Group III base stocks, and (b) having a pour point of less than -54 ° C and the following: (ia) at 3.5-3.95 cSt at 100 ° C, Noack volatility = ( (50,000) (KV100) ⁻⁶ , and (ib) Noac volatility = (182) (KV100) ^−1.9 at 3.degree. C. and below 6 cSt at 100 ° C.
(Iia) Noac volatility at 3.5-3.95 cSt at 100 ° C = (900) (KV100) ^-3.2 , and (iib) Noac volatility at greater than 3.95 at 100 ° C and 6 cSt or less = (175) (KV100) ^-2 .
One or more PAOs having one or more characteristics of:
A composition comprising   The (a) is selected from a solvent dewaxed API Group III basestock, a catalytic dewaxed API Group III basestock, and a wax isomer API Group III basestock. 20. The composition according to 19.   20. The composition of claim 19, wherein (a) is free of wax isomer API Group III base stock. A composition comprising 3.6 cStPAO,
The 3.6 cStPAO comprises about 99 wt% C30 linear hydrocarbon, less than 0.5 wt% C20 linear hydrocarbon, and less than 0.5 wt% C40 linear hydrocarbon; Characteristic composition.   A fully formulated SAE grade 0W multi-grade lubricating oil composition comprising 30% or more by volume of one or more API Group III base stocks and about 1 to 70% by volume of one or more PAOs.   24. The composition of claim 23, wherein the one or more API Group III basestocks are free of wax isomer API Group III basestocks.   25. The composition of claim 23 or 24, wherein the one or more API Group III basestocks have a CCS at -35 [deg.] C greater than 2600.   26. The composition of any one of claims 23-25, wherein the one or more API Group III base stocks have a CCS at -35 [deg.] C greater than 2700. A product that satisfies at least one of the requirements of ILSAC GF-4 standard product and SAE grade 0W multi-grade lubricant,
One or more API Group III basestocks, and the following conditions:
(A) the oligomerization of one or more α-olefins in the presence of a double promoter system wherein the PAO comprises an oligomerization catalyst and one alcohol and one ester, and two or more distillation steps Can be obtained or produced by a process comprising recovering the PAO as an overhead and / or bottom product from a process comprising
(B) the PAO has a pour point of less than −54 ° C. and one or more of the following relationships: (i) Noac volatility relationship to CCS on or under curve A in FIG.
(Ii) Noack volatility relationship to CCS on or under curve B in FIG.
(Iii) Noack volatility relationship to KV on curve A or below curve A in FIG.
(Iv) Noack volatility relationship to KV on or under curve B in FIG.
(V) Noak volatility relationship to KV on curve A in FIG. 3 or below curve A, and (vi) Noack volatility relationship to KV on curve B in FIG. And (c) the PAO has a pour point of less than −54 ° C., and (i) a Noack volatility relationship to KV at 100 ° C.
(Ia) Noac volatility at 3.5-3.95 cSt at 100 ° C. = (900) (KV100) ^−3.2 and (ib) Noac volatility at greater than 3.95 at 100 ° C. and below 6 cSt = (175) (KV100) ^-2 .
Having at least one of the following relationships:
A product comprising PAO having the characteristics of at least one of the following.   28. The product of claim 27, wherein the one or more API Group III base stocks are free of wax isomer API Group III base stock.   The one or more API Group III base stocks may be 30 based on the volume of solvent dewaxed API Group III base stock, catalytic dewaxed base stock, or combinations thereof relative to the total product volume. 29. A product according to claim 27 or 28 comprising at least one volume percent of one or more solvent dewaxed or catalytic dewaxed API Group III base stock.   30. Product according to any one of claims 27 to 29, comprising 30% or more by volume of one or more solvent dewaxed API Group III base stock, based on the total product volume. (A) the composition according to any one of claims 1 to 26, and (b) antioxidants, metallic and nonmetallic dispersants, metallic and nonmetallic surfactants, corrosion and rust inhibition. Agent, metal deactivator, antiwear agent, extreme pressure additive, anti-trapping agent, pour point depressant, wax modifier, viscosity modifier, seal compatibility imparting agent, friction modifier, lubricant, stain prevention A product comprising one or more additives selected from agents, color formers, defoamers, demulsifiers, emulsifiers, diluting agents, fuel stabilizers, and adhesives.   27. An automatic transmission fluid, automobile or industrial gear oil or control oil comprising the composition of any one of claims 1-26.

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