JP2008517908A - Alkylated methylnaphthalene as a synthetic lubricant base - Google Patents

Abstract

The present invention relates to alkylated methylnaphthalene and its use in lubricating oil bases. More particularly, the alkylated methylnaphthalene of the present invention unexpectedly has excellent thermal and oxidation properties and may be used to improve the performance characteristics of other lubricating base oils.
[Selection figure] None

Description

  The present invention relates to alkylated methylnaphthalene and its use in synthetic lubricating oil bases.

  Alkyl aromatic fluids have been proposed for use as a type of functional fluid that requires good thermal and oxidation properties. For example, Patent Document 1 (Yoshida) describes excellent heat and oxidation stability, low vapor pressure and flash point, good fluidity and high heat transfer capacity, and suitable for using them as heat transfer oil. Monoalkylated naphthalenes having other properties are described. The use of a mixture of monoalkylated and polyalkylated naphthalene as a substrate for a synthetic functional fluid is described in US Pat. Patent Documents 3 and 4 describe the use of alkyl aromatics as transformer oils.

  The alkylated naphthalene is usually obtained by converting naphthalene or substituted naphthalene into an acidic alkylation catalyst such as Friedel-Crafts catalyst (for example, acidic clay described in Patent Document 1 or Patent Document 2, or Patent Document 3 and Patent Document 4). Prepared by alkylation in the presence of a Lewis acid such as aluminum trichloride as described. The use of a catalyst described as a decayed silica-alumina zeolite for aromatic alkylation such as naphthalene is described in US Pat. The use of various zeolites, including intermediate pore size zeolites such as ZSM-5, and large pore size zeolites such as zeolite L and ZSM-4, for the alkylation of various monocyclic aromatics such as benzene is patented. Document 6 (Young).

  In the formulation of alkyl naphthalene-based functional fluids, the preferred alkyl naphthalene is said to be mono-substituted naphthalene. Because they show the best combination for the properties of the finished product. Mono-substituted naphthalenes have less benzylic hydrogen than the corresponding di- or poly-substituted species. This was said to have better oxidative stability and thus form better functional fluids and additives. In addition, mono-substituted naphthalenes have a kinematic viscosity (100 ° C.) in the desired range of about 5-8 cSt when using alkyl substituents with chain lengths of about 14-18 carbon atoms. Numerous studies have been made to improve the selectivity to the desired monoalkylated naphthalene.

  U.S. Patent No. 6,057,034 (Ashjian et al.) (Incorporated by reference) teaches the use of zeolites containing bulky cations. For example, the use of USY with cations having a radius of at least about 2.5 angstroms increases the selectivity for the desired monoalkylated product. Suitable zeolites include those containing hydrated cations of Group IA metals, divalent cations (particularly Group IIA), and rare earth cations.

  U.S. Patent No. 6,057,049 (Le et al.) (Incorporated by reference) discusses desirable properties of alkylated naphthalenes with higher alpha: beta ratios, including improved thermal and oxidative stability. . Le et al. (Inventor) generally describe alkylation of naphthalene and substituted naphthalenes that may include one or more short chain alkyl groups (such as methyl or ethyl) containing less than about 8 carbons; Several parameters that affect the alpha: beta ratio of the alkylated naphthalene product include zeolite steaming (ie use of steamed USY or steamed zeolite beta), reduced alkylation temperature, or acid treated clay. Found to include the use of. Lowering the alkylation temperature increases the alpha: beta ratio and leads to an improvement in the quality of the alkylated naphthalene product (including RBOT oxidation time).

U.S. Patent No. 6,099,017 (Dwyer et al.) (Incorporated by reference) discloses the effect of co-feed water on the alkylation reaction when using large pore zeolite catalysts (such as zeolite Y). Patent Document 10 and Patent Document 11 (which is incorporated by reference), respectively, similar alkylation process using MCM-41 and mixtures H / NH ₄ catalyst is disclosed.

  As noted above, most of the prior art generally teaches that mono-substituted naphthalenes are the most desirable components of synthetic lubricating oil bases and have optimal thermal and oxidative stability and viscosity characteristics. The Thus, the prior art teaches processes for improving selectivity and achieving the desired monoalkylated product. Dialkylnaphthalenes are taught to have poor lubricating oil properties. This is because dialkylation prevents the naphthalene ring from neutralizing oxygen, peroxides, or free radicals. Alkylated naphthalenes having a di- or trialkyl component are taught to have insufficient thermal and oxidative stability.

  U.S. Patent No. 6,057,096, however, teaches that alkylated methylnaphthalene is also a good substrate candidate. Methylnaphthalene, preferably 2-methylnaphthalene substituted with a long chain alkyl group (at least 35% of the substituted long chain alkyl group is bonded to naphthalene at the 2-position of the long chain alkyl group) is RBOT oxidation It was found to have over 800 minutes of time. Even with alkylated methylnaphthalene (only 30% of the substituted long chain alkyl group is attached to naphthalene at position 2 of the long chain alkyl group, but is synthesized using activated kaolin) RBOT oxidation time 420 minutes It was reported as having.

U.S. Pat. No. 4,714,794 U.S. Pat. No. 4,604,491 U.S. Pat. No. 4,211,665 U.S. Pat. No. 4,238,343 US Pat. No. 4,570,027 U.S. Pat. No. 4,301,316 US Pat. No. 5,034,563 US Pat. No. 5,177,284 US Pat. No. 5,191,135 US Pat. No. 5,191,134 US Pat. No. 5,457,254 JP-A-8-302371 US Pat. No. 3,402,966 US Pat. No. 3,923,192 US Pat. No. 3,449,070 US Pat. No. 3,354,078 US Pat. No. 4,663,492 US Pat. No. 4,594,146 US Pat. No. 4,522,929 US Pat. No. 4,429,176 “Catalytic Cracking, Catalysts, Chemistry and Kinetics” by Wojciechowski (Chemical Industries, Vol. 25, Mercer Dek (Merke Dek) ), 1986) (ISBN0-8247-7503-8) J. et al. Catalysis (4, 527, 1965) J. et al. Catalysis (6, 278, 1966) J. et al. Catalysis (61, 395, 1980)

  Here, in 1-methyl and / or 2-methylnaphthalene in which long-chain alkyl is substituted, 30% or less of the long-chain alkyl group to be substituted is bonded to naphthalene at the 2-position of the long-chain alkyl group, and RBOT It has been found in the oxidation test to have excellent thermal and oxidation properties over 500 minutes. This is often much better than mono-substituted naphthalene.

  Thus, the present invention broadens the range of raw materials that can be used to produce synthetic substrates, and 1-methyl and / or 2-methylnaphthalene (30% long chain alkyl groups) in which the long chain alkyl is substituted. Or less, preferably less than 30%, more preferably about 29% or less are attached to naphthalene at the 2-position of the long chain alkyl group), but better oxidative stability than that of known alkyl naphthalene fluids, or Based on the teachings, it is established that these long chain alkyl group substituted methylnaphthalene fluids have the oxidative stability expected.

式中、Ｒ^１およびＲ^２は、Ｈ、メチルであり、
Ｒ^３およびＲ^４は、炭素原子約６〜約２４個を有するアルキル基であり、
ｘは、０〜約２であり、
ｙは、０〜約４である。
但し、Ｒ^１およびＲ^２の少なくとも一種は、Ｈ以外であり、ｘおよびｙの少なくとも一種は、０以外であり、しかもＲ^３およびＲ^４基の３０％以下、好ましくは３０％未満、より好ましくは２９％以下は、長鎖アルキル基の２位でナフタレンに結合される。その際、前記長鎖アルキル置換メチルナフタレンは、アルキル化剤を、１−メチルナフタレン、２−メチルナフタレン、または１−メチルおよび２−メチルナフタレンの混合物と、ナフタレン／アルキル化剤のモル比少なくとも約２：１で、触媒としてＵＳＹゼオライトを用いて、約１５０℃〜約２５０℃、好ましくは約１５０℃〜約２２５℃、より好ましくは約１７５℃〜約２００℃の範囲の温度で反応させる工程、好ましくは、１−メチルナフタレン、または１−メチルおよび２−メチルナフタレンの混合物を、アルキル化剤と、ナフタレン／アルキル化剤比約２：１で、ＵＳＹゼオライト触媒により、温度約１７５℃〜約２００℃で反応させる工程、またはアルキル化剤を、２−メチルナフタレンと、ナフタレン／アルキル化剤のモル比少なくとも約２：１で、触媒としてＵＳＹゼオライトを用いて、約１５０℃〜約２２５℃の範囲の温度で反応させる工程を含む方法によって調製される。 The present invention includes dialkylnaphthalene. It has utility as an additive for synthetic lubricant bases, blends, or other base fluids or liquid fuels. The present invention includes alkylated naphthalenes selected from the group consisting of blends of compounds of formula (I) or mixtures of the compounds.

In which R ¹ and R ² are H, methyl;
R ³ and R ⁴ are alkyl groups having from about 6 to about 24 carbon atoms;
x is from 0 to about 2,
y is from 0 to about 4.
However, at least ^one of R ¹ and R ² is other than H, and at least one of x and y is other than 0, and 30% or less, preferably less than 30%, more preferably less than R ³ and R ⁴ groups. 29% or less is bonded to naphthalene at the 2-position of the long-chain alkyl group. In this case, the long-chain alkyl-substituted methylnaphthalene has an alkylating agent of 1-methylnaphthalene, 2-methylnaphthalene, or a mixture of 1-methyl and 2-methylnaphthalene and a molar ratio of naphthalene / alkylating agent of at least about Reacting at a temperature in the range of about 150 ° C. to about 250 ° C., preferably about 150 ° C. to about 225 ° C., more preferably about 175 ° C. to about 200 ° C. at 2: 1 using USY zeolite as a catalyst; Preferably, 1-methylnaphthalene, or a mixture of 1-methyl and 2-methylnaphthalene, with an alkylating agent and a naphthalene / alkylating agent ratio of about 2: 1 and a USY zeolite catalyst at a temperature of about 175 ° C. to about 200 The step of reacting at 0 ° C., or the alkylating agent, the moles of 2-methylnaphthalene and naphthalene / alkylating agent At least about 2: 1, with the USY zeolite as catalyst, it is prepared by a method comprising the step of reacting at a temperature ranging from about 0.99 ° C. ~ about 225 ° C..

Preferably, R ³ and R ⁴ include alkyl groups having from about 8 to about 18 carbon atoms. Exemplary R ³ and R ⁴ groups include hexyl, heptyl, octyl, nonyl, isooctyl, 2-ethylhexyl, decyl, undecyl, dodecyl, tetradecyl, pentadecyl, hexadecyl, heptadecyl, and octadecyl, each Optionally having linear or branched alkyl groups.

The sum of x and y is preferably from about 1 to about 3. More preferably, the synthetic oil comprises a dialkylnaphthalene, where the sum of x and y is 1, R ¹ is H and R ² is methyl.

  The compounds of formula (I) unexpectedly have excellent thermal and oxidative stability, especially when compared to mono-substituted naphthalenes, which are based on the teachings of the literature, these alkylmethyl naphthalenes Would be expected. Alkylated 1-methyl or 2-methylnaphthalene compounds made as cited herein have an RBOT oxidation time of about 500 minutes or more, preferably about 600 minutes or more, more preferably about 700 minutes or more, most preferably Indicates about 700 to 1300 minutes.

  Another aspect of the present invention relates to a method for improving the oxidative stability of a lubricating oil composition. The method includes adding a compound of formula (I) to a base oil.

  As used herein, “alkylated methylnaphthalene” means at least one additional alkyl group having a methyl group at the 1- or 2-position of the naphthalene ring and containing from about 6 to about 24 carbon atoms. Refers to a naphthalene compound bonded to another position of the ring. In addition, all values stated herein include all combinations and subcombinations of the ranges and specific values set forth therein.

  Naphthalene starting materials for preparing compounds of formula (I) include 1-methylnaphthalene, 2-methylnaphthalene, or (in any proportion) two substantially pure mixtures. For example, 1- and 2-methylnaphthalene can be used in coke liquids or heavy fractions of aromatic reformate streams (greater than 10 carbon atoms), heavy bottom streams from toluene disproportionation processes, or catalytic cracking. Present in heavy fractions from the process (such as light cycle oils from the FCC process). A feed stream having a higher 2-methylnaphthalene content (such as from a highly selective toluene disproportionation process) is preferred. Because alkylated 2-methylnaphthalene products generally have better oxidative stability, the alkylation process is more effective when compared to feed streams containing higher amounts of 1-methylnaphthalene. This is because there is a tendency to be appropriate. In addition, the starting material may comprise a mixture of methylnaphthalene and naphthalene. However, using 1-methyl alone, or 2-methyl alone, or a substantially pure mixture of 1-methyl and 2-methylnaphthalene, under the alkylation conditions listed herein, may result in RBOT oxidative stability. The production of alkylated methylnaphthalene products having about 500 minutes or more, preferably about 600 minutes or more, most preferably about 200 minutes or more, and most preferably about 700 to 1300 minutes is ensured.

  Alkylating agents that may be used to alkylate 1-methyl and / or 2-methyl substituted naphthalenes have one or more available alkylated aliphatic groups that can alkylate substituted naphthalenes. Any aliphatic or aromatic organic compound is included. The alkylatable group itself should have at least about 6, preferably at least about 8, and even more preferably at least about 12 carbon atoms. For the production of functional fluids and additives, the alkyl group of naphthalene preferably has from about 12 to about 24 carbon atoms, particularly preferably from about 14 to 18 carbon atoms. A preferred class of alkylating agents are olefins having the requisite number of carbon atoms. For example, dodecene, tetradecene, pentadecene, hexadecene, heptadecene, octadecene, nonadecene, and branched analogs thereof.

  In preferred embodiments, the alkylating agent is an internal olefin (such as 2- or 3-tetradecene), an alpha (or 1-) olefin, a vinylidene olefin (2-methyl-1-tetradecene, or 2,3,3-trimethyl). -1-butene, 2,4,4-trimethyl-1-pentene, or 2,4,4-trimethyl-2-pentene). Alpha olefins and linear internal olefins are most readily available. Although the alkylating agent used is zeolite USY (in itself, the long chain alkyl group bonded to naphthalene at the 2-position of the long chain alkyl group is 30% or less, preferably less than 30%, more preferably 29 %), The probability of producing more than 30% of the long chain alkyl group attached to naphthalene at the 2-position of the long chain alkyl group should be the lowest.

Mixtures of olefins, e.g., _C 12 _{-C 20} or _C 14 _{-C 18} mixture of olefins may also be used in the present invention. Branched alkylating agents, particularly oligomerized olefins (such as trimers, tetramers, or pentamers of light olefins such as ethylene, propylene, and butylene) are also useful. Other useful alkylating agents that may be used include alcohols. Hexadecanol, heptadecanol, octadecanol, nonadecanol, dodecanol, doundecanol, and the like. Alkyl halides such as hexadecyl chloride, octadecyl chloride, dodecanyl chloride, and higher homologues may also be used in the present invention.

  The alkylation reaction between the substituted naphthalene and the alkylating agent is performed in the presence of an ultrastable Y (USY) zeolite alkylation catalyst.

  When USY contains a hydrated cation, it catalyzes the alkylation in good yield with good selectivity. Zeolite USY is a commercial material available in large quantities as a catalyst for petroleum cracking. It is produced by stabilization of zeolite Y by repeated ammonium exchange and controlled steaming procedures. A method for producing zeolite USY is described in US Pat. Nos. 6,099,028 (McDaniel), US Pat. See also Non-Patent Document 1. This refers to zeolite USY, a description of its preparation and properties. Zeolite USY, prepared in accordance with the teachings of US Pat. Nos. 5,099,086 and 5,037,797, both of which are incorporated herein by reference, is a preferred form of zeolite USY and provides the desired results.

  The zeolite USY of Patent Document 7 and Patent Document 8 is a porous crystalline zeolite containing cations having a radius of at least 2.50Å, preferably at least about 3.0Å. It may also be characterized as having a minimum pore size of at least 7.4 mm and an alpha value of about 0.1 alpha to about 1000 alpha, preferably an alpha value of less than about 300 alpha. More preferably, it ranges from about 5 alpha to about 250 alpha.

  The zeolite USY catalyst may be complexed with a matrix material or binder that is resistant to the temperatures and other conditions used in the alkylation process. These materials include active and inert materials, and synthetic or natural zeolites, as well as inorganic materials such as clay, silica, or silica-alumina. The latter may be either naturally occurring or in the form of a gelatinous precipitate or gel (including a mixture of silica and metal oxide). By using the active substance in combination with the zeolite, the conversion and / or selectivity of the catalyst may be changed. The inert material suitably acts as a diluent and the conversion is controlled so that the alkylation product can be obtained economically without using other means to control the reaction rate. . Binders that may be combined to improve the crush strength and other physical properties of the catalyst under commercial alkylation operating conditions include, but are not limited to, natural clays (eg, bentonite and kaolin), As well as silica, alumina, zirconia, and mixtures thereof.

The alpha value of the zeolite is an approximate measure of the catalytic cracking activity of the catalyst compared to the standard catalyst. The alpha test shows the relative rate constant of the test catalyst (normal hexane conversion rate / catalyst volume / unit time) compared to a standard catalyst (rate constant = 0.016 sec ⁻¹ ) where alpha is expressed as 1. . The alpha test is described in US Pat. This refers to the test description.

  Zeolite USY has a high initial alpha value of about 1000 or less.

  The stability of the alkylation catalyst may be increased by steaming. Patent Literature 17, Patent Literature 18, Patent Literature 19, and Patent Literature 20 are incorporated herein by reference. This describes the conditions for steam stabilization of a zeolite catalyst that can be used to steam-stabilize the catalyst.

  The alkylation process of the present invention allows an organic reactant (eg, an alkylatable methylnaphthalene compound and an alkylating agent) to be catalyzed in a suitable reaction zone (eg, a flow reactor containing a fixed bed catalyst composition). And in contact under effective alkylation conditions.

  30% or less of the long chain alkyl group, preferably less than 30%, more preferably 29% or less is bonded to methyl naphthalene at the 2-position of the long chain alkyl group, and the RBOT oxidation line is about 500 minutes or more, preferably about 600 The alkylation reaction conditions used in the present invention to produce long chain alkylated methylnaphthalene that exhibits greater than or equal to minutes, more preferably greater than or equal to about 700 minutes, and most preferably greater than or equal to about 700 to 1300 minutes include alkylating agents, and 1 A methylnaphthalene, 2-methylnaphthalene, or a substantially pure mixture of 1-methyl and 2-methylnaphthalene, with a naphthalene / alkylating agent molar ratio of at least about 2: 1, preferably about 2: 1 to 10: 1, more preferably about 2: 1 to 4: 1, most preferably about 2: 1 and a temperature of about 150 ° C. to about 250 ° C., preferably about 150 Reaction at 225 ° C, more preferably about 175 ° C to 200 ° C, in the presence of a USY zeolite catalyst, preferably 1-methylnaphthalene or a substantially pure mixture of 1-methyl and 2-methylnaphthalene An alkylating agent and a naphthalene / alkylating agent ratio of at least about 2: 1, preferably about 2: 1 to 10: 1, more preferably about 2: 1 to 4: 1, most preferably about 2: 1. Reacting in the presence of a USY zeolite catalyst at a temperature of about 175 ° C. to about 200 ° C., or the alkylating agent at a molar ratio of 2-methylnaphthalene to naphthalene / alkylating agent of at least about 2: 1, preferably About 2: 1 to about 10: 1, more preferably about 2: 1 to 4: 1, most preferably about 2: 1, and a temperature of about 150 ° C. to about 225 ° C., preferably about 150 ° C. to about 2 0 ° C., more preferably at about 175 ° C. ~ about 200 ° C., comprising the step of reacting in the presence of a USY zeolite catalyst.

  Typical reaction pressures include pressures of about 0.1 to about 100 atmospheres, preferably about 1 to about 30 atmospheres. The required pressure may be maintained by inert gas pressurization. Preferably, nitrogen is used.

  Typical reaction times are about 0.5 to about 100 hours, preferably about 2 to about 72 hours, more preferably about 4 to 24 hours. The reaction time depends on the temperature used in the process and the amount of catalyst. In general, higher reaction temperatures and higher catalyst loading facilitate faster reaction rates.

  Generally, the amount of catalyst charged is from about 0.1% to about 10% by weight in the slurry reactor. Low catalyst loading may result in longer reaction times. High catalyst loading may be uneconomic to operate. This causes filter clogging in the catalyst removal step. Preferably, the catalyst loading is from about 0.5% to about 5% by weight. The reaction may be performed in a fixed bed continuous operation. The catalyst is then packed in a tubular reactor that is in the form of pellets or in extruded form and is heated to the desired temperature. The feedstock is introduced at a specific weight hourly space velocity (WHSV) ranging from about 0.1 to about 20, preferably from about 0.5 to about 5, more preferably from about 0.2 to about 4, and high conversion Is achieved.

  The reactants can be either in the gas phase or in the liquid phase, and can be simple (ie, without intentional mixing or dilution with other materials). Alternatively, they can be contacted with the catalyst composition with the aid of a carrier gas or diluent (such as hydrogen or nitrogen). Alkylation is carried out as a batch type reaction (typically using a closed pressure stirred reactor with an inert gas seal system) or in semi-continuous or continuous operation using a fixed bed or moving bed catalyst system. Can be

  In preparing the compound of formula (I), the amount of dimer of alkylated olefin will be co-produced. The alkylated methylnaphthalene herein, including formula (I), will typically contain dimer <1% by weight, whether used as a substrate or as a co-substrate.

  They may be separated from the reaction mixture by stripping off the unreacted alkylating agent and recovering the compound of formula (I) in a conventional manner. Also, the stability of the alkylated product is improved by removing the impurities (particularly acidic by-products formed by oxidation during the reaction process) by filtration with activated carbon and alkali treatment. It was found to be good. The alkali treatment is preferably performed by filtration with a solid alkaline substance, preferably calcium carbonate (lime).

  In general, a raw material having a high 2-methylnaphthalene is more preferable. Because they may be more reactive than 1-methylnaphthalene, 2-methylnaphthalene alkylation products have better oxidative stability than 1-methylnaphthalene alkylation products. . As mentioned above, the heavy bottom stream from the highly shape selective toluene disproportionation process is typically high in 2-methylnaphthalene and is particularly suitable for use in the present invention.

  The compounds of formula (I) may be used to improve the oxidative stability of lubricating oils. For example, the oxidative stability (measured by Rotating Bomb Oxidation Test (RBOT) (ASTM D2272)) of compounds of formula (I) is generally greater than about 500 minutes, preferably greater than about 600 minutes, more preferably about 700 More than a minute. In a preferred embodiment, the RBOT value is about 700-1300 minutes. All values stated herein include all combinations and subcombinations of the ranges and specific values indicated therein.

  In addition, the compound of formula (I) has a kinematic viscosity (100 ° C.) of about 2 to about 30 cS, more preferably about 3 to about 20 cS, and a viscosity index (VI) value of about 50 to about 180, preferably Is greater than 60. The pour point of the compound of formula (I) is about 0 to about −60 ° C., more preferably −10 to about −55 ° C. All values stated in this specification include all combinations and subcombinations of the ranges and specific values indicated therein.

  The long chain alkylated naphthalene base oil comprising the compound of formula (I) may itself be used as a base material for synthetic lubricating oil formulations. They can also be used with other synthetic substrates (such as polyalphaolefins (PAO), polyalkylene glycols (PAG), polybutenes (PIB), alkylbenzenes (AB)), or conventional mineral oils (from catalytic or conventional dewaxing processes). 100-800 SUS SN oil, etc.). Base oils containing compounds of formula (I) will also be used with hydrocracking or hydroisomerization substrates. UCBO from Chevron, BP hydrocracked oil, slack wax isomerized substrate, or Fischer-Tropsch wax isomerized substrate, etc. (collectively these fluids are referred to as Group II and Group III substrates) It is. Such substrates typically have RBOT ≦ about 150.

  Generally, when used as a co-substrate, the alkylated methylnaphthalene constitutes from about 2 to about 90% by weight of the total lubricant base, and preferably greater than about 5% by weight of the total lubricant base. The use of alkylated methylnaphthalene substantially reduces the heat, oxidation, and hydrolysis stability of the finished lubricant, as well as the solubility, sludge dispersibility, and wear resistance or extreme pressure metal surface protection of the lubricant additive. improves.

  As described above and shown in the following examples, compounds of formula (I) have excellent oxidative stability and viscosity characteristics when compared to monoalkylated naphthalene. Accordingly, the synthetic base oil of the present invention may be substantially free of monoalkylated naphthalene. This still shows excellent lubricating oil properties.

  The alkylated methylnaphthalene may incorporate a conventionally used additive for lubricating oil. Antioxidant, detergent dispersant, viscosity index improver, pour point depressant, oiliness improver, antiwear agent, extreme pressure agent, friction modifier, corrosion inhibitor, metal deactivator, rust inhibitor, seal affinity Property improvers, antifoaming agents, demulsifiers, bactericides, or coloring agents.

  The alkylated methylnaphthalene may be used to lubricate the surfaces of various structures and elements that require lubrication. As used herein, “surface” refers to the outer portion of a structure or particle. The compounds of formula (I) may be used in various functional fluids. Crankcase lubricating oil, 2-cycle engine oil, operating lubricating oil, drilling lubricating oil, grease, gear oil, transmission oil, and papermaking oil.

  The following examples are illustrative and not meant to be limiting.

The general procedure described herein was used to collect the following data. This is described in particular for Example 2 in Table 1. In this experiment, 142 g of 1-methylnaphthalene (1-M) (1 mole) and 12.5 g of USY catalyst (prepared as described in US Pat. Premixed in and the complete reaction was purged with N ₂ to remove air. The reaction flask was heated to 200 ° C. under a nitrogen atmosphere. 112 g (0.5 mol) of 1-hexadecene was slowly added into the mixture over 2 hours. The reaction mixture was reacted for more than 3 hours and then cooled to room temperature. Analysis of the reaction mixture by gas chromatography was used to determine the amount of unreacted reactants, indicating that most of the C ₁₆ olefins were converted to product. The product, i.e., the lubricating oil product, is isolated by filtering off the solid catalyst, which is distilled at 120 ° C / vacuum less than 1 millitorr for more than 1 hour to yield any unreacted olefin and methylnaphthalene (MN). Was also removed.

  The resulting product was analyzed. The product characteristics are summarized below. Oxidative stability was analyzed in a rotary bomb oxidation test (RBOT) and a B-10 oxidation test. The procedure for the RBOT test is described in ASTM D2272.

  The B-10 oxidation test is used to evaluate mineral oils and synthetic lubricating oils with or without additives. The evaluation is based on the oxidation resistance of the lubricating oil by air under specific conditions. This is measured by sludge formation, lead specimen corrosion, and changes in neutralization number and viscosity. In this method, a sample is placed in a glass oxidation cell with an iron, copper, and aluminum catalyst and a weighed lead corrosion specimen. The cell and its contents are placed in a bath maintained at a specific temperature, and a measured amount of dry air is bubbled through the sample throughout the test. The cell is removed from the bath and the catalyst set is removed from the cell. The oil is tested for the presence of sludge, total acid number (TAN) (ASTM 664), and kinematic viscosity (Kv) increase (100 ° C.) (ASTM D445). The lead specimen is cleaned and weighed to determine weight loss.

  Other properties to be measured include bromine number (ASTM D1159), VI, and pour point (ASTM D97).

  The following examples show the excellent thermal and oxidative stability of the compounds of formula (I) and the effect of several variables on the yield and properties of the compounds, i.e. lubricating oil products.

  The data in Table 1 shows the effect of the molar ratio of MN / olefin to lubricating oil product (for the purposes of the examples herein, methylnaphthalene acts as the starting material and the olefin is the alkylating agent. Act as). Examples 1-3 show that increasing the 1-MN / olefin molar ratio from 1/1 to 4/1 improves the oxidative stability of the lubricating oil product. This is measured by RBOT (RBOT time increases from 145 minutes to 805 minutes). A similar trend is observed for the 2-MN / olefin molar ratio (Examples 4 and 5). Variations in the MN / olefin ratio did not appear to change the product viscosity, VI, and pour point, and olefin conversion was very high (> 90%) for all MN / olefin ratios. A MN / olefin molar ratio of at least about 2: 1 is required to produce an alkylation product exhibiting RBOT of 500 minutes or more.

  The data in Table 2 shows the effect of reaction temperature on the yield and properties of lubricating oil from 1-MN or 2-MN at a MN / olefin ratio of 2/1. Examples 6 and 8 show that increasing the reaction temperature from 175 ° C. to 225 ° C. increases the 1-hexadecene conversion from 74% to 100%, but this has an effect on viscosity, VI, and pour point. Indicates that it does not have at all. At lower reaction temperatures (such as 175 ° C. and 200 ° C.) (Examples 6 and 7), the lubricating oil product has a longer RBOT time than the product produced at 225 ° C. (Example 8, 168 minutes). Similar trends were observed for products from 2-MN (Examples 9-12). For example, by performing the reaction at lower reaction temperatures (such as 150 and 175 ° C.) (Examples 9 and 10), a lubricating oil product with an RBOT time> 1000 minutes was obtained. For 1-MN alkylation, a maximum temperature of about 200 ° C. is required when the product has an RBOT of 500 min or more, whereas for 2-MN alkylation, the temperature is 150-225 ° C. It can be seen that the product has an RBOT of 500 minutes or more.

  The data in Table 3 shows the effect of different olefins, different MN materials, and different catalysts on lubricant yield and properties.

  Examples 13-15 show that 1-tetradecene, 1-hexadecene, and 1-octadecene may be used as alkylating agents. By changing the olefin raw material, a product of 4.6-6.1 cS was obtained. All products had very long RBOT times (744 min-1000 min).

  Examples 16-18 show the results obtained when using different materials of methylnaphthalene or a mixture of naphthalene and methylnaphthalene. Suresol-187 [Suresol-187] used in Examples 16 and 17 is a commercial product available from Koch Chemical Co. and contains 2-MN52% and 1-MN45%. In Example 18, raw materials containing equal weights of naphthalene, 1-MN, and 2-MN were used. The products of Examples 16-18 were produced in high yields, but had RBOT times significantly inferior to those of products produced by individual alkylation of 1-methylnaphthalene or 2-methylnaphthalene.

  Examples 19 and 20 show that the use of MCM-22 catalyst instead of USY catalyst produced a lubricating oil product having a RBOT time lower than that of the product produced using zeolite USY catalyst. Indicates.

  In Table 4, the properties of lubricants made from 1-MN or 2-MN are disclosed in commercial mono-alkylated naphthalene lubricants available from Mobile Chemical Co. Manufactured according to the method of The data shows that the MN based lubricant product has better oxidative stability as measured by RBOT.

  Example 21 is an analysis of a representative sample of alkylated methylnaphthalene for the degree of long chain alkyl group substitution through the secondary carbon atom of the 1-methyl long chain alkyl group.

  The long-chain alkyl-substituted methylnaphthalene used in the present invention is different from that of Patent Document 12. The long-chain alkyl-substituted methylnaphthalene used in the present invention contains about 30% or less of the long-chain alkyl group bonded to naphthalene at the 2-position of the long-chain alkyl group, while the alkylmethylnaphthalene of Patent Document 12 is a long-chain alkyl group. At least 35% of the long chain alkyl group bonded to naphthalene at the 2-position of the group.

  In a typical operation, USY catalyst is used at 200 ° C. with a MN / alkylating agent ratio of 2: 1 and the product is 29% long chain alkyl group attached to naphthalene at position 2 of the long chain alkyl group. And a high amount (about 55%) of long chain alkyl groups attached to naphthalene at 4 or more positions of the long chain alkyl group. The low amount of long chain alkyl group attached to naphthalene at the 2-position of the long chain alkyl group is important for consistently good product properties.

  In the present invention, all alkylated methylnaphthalene products were made from either 1-methylnaphthalene or 2-methylnaphthalene. This has a pour point of −26 ° C. or less, and the majority (19 of 20 samples) have a pour point of less than −40 ° C. In a comparative run using a catalyst other than USY and reaction conditions to produce a product with a high long chain alkyl group attached to naphthalene at the 2-position of the long chain alkyl group, the product has a higher pour point ( −23 ° C.). The data is summarized below.

  Although the present invention has been described in detail and with reference to specific embodiments thereof, it will be apparent to those skilled in the art that various modifications and changes can be made without departing from the scope and spirit of the invention. It will be obvious.

Claims (13)

An alkylated methylnaphthalene having an RBOT of at least 500 minutes,
An alkylating agent having at least 6 carbon atoms is selected from 1-methylnaphthalene, 2-methylnaphthalene, or a substantially pure mixture of 1-methylnaphthalene and 2-methylnaphthalene, and a methylnaphthalene / alkylating agent ratio of at least 2 : 1 by a method comprising a step of reacting with USY zeolite at a temperature of 150 ° C to 250 ° C and a pressure of 0.1 to 100 atm for 0.5 to 100 hours,
An alkylated methylnaphthalene, wherein 30% or less of a long-chain alkyl group is bonded to naphthalene at the 2-position of the long-chain alkyl group. An alkylated methylnaphthalene having an RBOT of at least 500 minutes,
An alkylating agent having at least 6 carbon atoms is 1-methylnaphthalene and a methylnaphthalene / alkylating agent ratio of at least 2: 1 with USY zeolite at a temperature of 175 ° C. to 200 ° C. and a pressure of 0.1 to 100 atmospheres. Produced by a method comprising a step of reacting for 0.5 to 100 hours,
The alkylated methylnaphthalene according to claim 1, wherein 30% or less of the long-chain alkyl group is bonded to naphthalene at the 2-position of the long-chain alkyl group. An alkylated methylnaphthalene having an RBOT of at least 500 minutes,
An alkylating agent having at least 6 carbon atoms is 2-methylnaphthalene and a methylnaphthalene / alkylating agent ratio of at least 2: 1 with a USY zeolite catalyst at a temperature of 150 ° C. to 225 ° C. and a pressure of 0.1 to 100 atm. And a process comprising a step of reacting for 0.5 to 100 hours,
The alkylated methylnaphthalene according to claim 1, wherein 30% or less of the long-chain alkyl group is bonded to naphthalene at the 2-position of the long-chain alkyl group. An alkylated methylnaphthalene having an RBOT of at least 500 minutes,
The alkylating agent having at least 6 carbon atoms is converted to a substantially pure mixture of 1-methylnaphthalene and 2-methylnaphthalene and a methylnaphthalene / alkylating agent ratio of at least 2: 1 with a USY zeolite catalyst at a temperature of 175 Produced by a method comprising a step of reacting at a pressure of 0.1 to 100 atm for 0.5 to 100 hours,
The alkylated methylnaphthalene according to claim 1, wherein 30% or less of the long-chain alkyl group is bonded to naphthalene at the 2-position of the long-chain alkyl group.   The alkylated naphthalene according to claim 1, 2, 3 or 4, characterized in that it has an RBOT of 600 minutes or more.   The alkylated naphthalene according to claim 1, 2, 3 or 4, characterized in that it has an RBOT of 700 minutes or more.   The alkylated naphthalene according to claim 1, 2, 3 or 4, characterized in that it has an RBOT of 700 to 1300 minutes or more.   The alkylated naphthalene according to claim 1, 2, 3 or 4, wherein the methylnaphthalene / alkylating agent ratio is 2: 1 to 10: 1.   The alkylated naphthalene according to claim 1, 2, 3 or 4, wherein the methylnaphthalene / alkylating agent ratio is 2: 1 to 4: 1.   The alkylated naphthalene according to claim 3, wherein the reaction temperature is from 150C to 200C.   The alkylated naphthalene according to claim 3, wherein the reaction temperature is 175C to 200C.   The alkylated naphthalene according to claim 1, 2, 3 or 4, wherein less than 30% of the long-chain alkyl group is bonded to naphthalene at the 2-position of the long-chain alkyl group.   The alkylated methylnaphthalene according to claim 1, 2, 3 or 4, wherein 29% or less of the long-chain alkyl group is bonded to naphthalene at the 2-position of the long-chain alkyl group.