JPH03505342A - Synthetic lubricant containing polar groups - Google Patents

Abstract

(57) [Summary] This bulletin contains application data before electronic filing, so abstract data is not recorded.

Description

[Detailed description of the invention] Synthetic lubricant containing polar groups The present invention is directed to novel compositions useful as lubricants with polar functional groups. Especially the present invention is a novel lubricant composition and its lubricant range of olefins and enophiles. From the production method.

Lubricant formulations are generally formulated for specific applications, particularly internal combustion engine and mechanical applications. There are bulk additives that combine various chemicals to improve or protect lubricity. more normal Additives used include antioxidants, rust inhibitors, anti-wear agents, pour point depressants, and detergents. These include dispersants, viscosity index (Vl) improvers, antifoaming agents, and the like. About lubricant technology overview Kirkuk Odmer's “Encyclopedia of Chemical” Technology” 3rd edition, Volume 14, pages 477-526. Indicated by the number of additives and their amounts added to typical lubricant compositions Given the variety of chemical structures, lubricant manufacturing engineers have the ability to create lubricant products that are stable or liquid in stock and in use. There is a need to investigate the production of homogeneous formulations with Lubricant, especially according to the invention The types of lubricating oils of interest are typically hydrogenated olefins. the hydrocarbon Due to the structure of Extremely incompatible with additives. Therefore to make the lubricant compatible with polar additives There are no convenient commercial preparations that require the addition of large amounts of expensive polar organic esters to the formulation. In order to obtain a sufficiently homogeneous mixed lubricant of lubricant and additives, for example, bis-trideca Contains 20% or more of esters such as noradipate.

While improving the solvent properties of lubricants with solubilizers such as organic esters, Solving the manufacturing problem of stable mixtures is more than just an added cost to the product and other performance-related problems. cause or compel A weak substance that causes oxidative deterioration of the solubilizer and promotes tar and rubber formation. Points must be taken into account, seal expansivity can be changed. Seal expansion is a lubricant The seal is swollen and its ability to improve seal performance is measured. The solubilizer is Affects properties such as material viscosity and viscosity index.

The effectiveness of the lubricant may be impaired if large amounts of materials that adversely affect these properties are added. Probably. Considering these complex relationships, there is no need to compromise on the quality of the product or the additional cost of the product. There is a need for new methods for improving or manufacturing lubricants by adding additives to them. It's obvious.

One method of improving the compatibility of lubricants with additives is the addition of polar groups to the lubricant structure.

Lubricants, particularly synthetic lubricants, are known to have some olefinic unsaturation and are not suitable for the present invention. This unsaturation is useful for reactions with polar groups that add polar functionality to the lubricant molecule. It turned out that it can be used effectively. The polar groups added to the lubricant are adipate esters. Sufficient solubilizing properties to successfully dissolve bulk additives without the addition of solubilizers such as The functionality required in the present invention, that is, the functional group, has a lubricant olefin group. It has been found that it can be added to lubricants by reacting with chemically negative enofil.

Hydrocarbons in the unsaturated C2@10 lubricant range with allylic hydrogen are C21+ unsaturated lubricants. Structure in which the agent has one or more allylic hydrogens: RI-C'' C-C-RJ (However, R+, R2, R3, Ra and Rs may be hydrogen, alkyl or alkenyl. (well, the total carbon atoms are at least 17) By adding to alkenes with olefinic unsaturation in the alpha, beta position It was found to react thermally or catalytically.

All alpha, beta unsaturated alkenes useful in this invention have the structural formula: %formula%: (At least one of Rs, Ry, Ra and R9 in the above formula is an electrically negative group. is hydrogen, alkyl, alkenyl, alkynalkyl, aryl or aral These structural formulas are called enophiles.

In particular, a polar lubricant is produced, which contains the unsaturated lubricant and the unsaturated lubricant. The alkene adduct has the following structural formula: % formula % (At least one of R8 or R9 in the above formula is an electronegative group, and the remaining Rs, Rt, Ra and R9 are electronegative groups or hydrogen, alkyl, alkenyl, alkynalky R+, Rt, Rs, Ra and R5 are water, aryl or aralkyl. C+y+alkyl, at least one of which is C+y+alkyl The unsaturated C2@10 lubricant molecule has many allylic groups (or alkenyl groups). If more than 1 mole of enophile reacts with the lubricant, the electrically negative group of l or produces an adduct with multipolar sites. Hydrogenation of gives a polar lubricant with dispersant properties.

In the present invention, the adduct between the C2@+ olefin lubricant and F-fill is by high temperature heating or catalytic reaction with Lewis salts such as BFs or AICIs. It can be manufactured by

Olefinic lubricants useful in the present invention in adduct formation with enophiles include carbon Unsaturated groups having 20 to 5000 atoms and one or more of the unsaturated groups being allylic unsaturated There is a saturated lubricant. These include natural lubricants from mineral oils as well as 20 to 5 carbon atoms. For all synthetic lubricants useful in this invention to have a lubricant molecule having a Structural formula of: %formula% (R+ + R2@R3* in the above formula, Ra and Rs are hydrogen, alkyl, or alkyl represents kenyl and the total number of carbon atoms of R+, R2, Rs, Ra and R5 is small It is necessary to have one or more olefin groups having at least 17). Olef Even if the yn bond is in the alpha position, i.e. in the vinyl structure where R1 and R2 are hydrogen, Often, the bond is RI+R2-Rs, Ra and U (or) Rs are aliphatic hydrocarbons. Lubricants can be any internal olefin, usually with a wide range of molecular weights. The molecule consists of a mixture of alpha olefins and allylic structures. It has more than 1 olefinic bonds, including internal olefins. Therefore According to the present invention, the lubricant molecules that are After repulsion, a number of adducts with specific enophiles can also be produced.

Methods well known in the lubricant art are used to prepare the unsaturated lubricants required as feedstocks of the present invention. Used for construction. Mineral oil separation is achieved using CHI immersion lubrication with natural olefinic unsaturated groups. or other petroleum fractions are cracked or dehydrogenated to produce olefinically unsaturated Of particular interest as the feedstock of the present invention is the ability to produce a C2+ lubricant base material with There are synthetic lubricants, especially derivatives from C3+ olefins or polyalphaolefins. It's a fin.

Synthetic polyalphaolefins (PAOs) are gaining popularity in the lubricant field compared to mineral oil-based lubricants. It is known for its wide applicability and commercial utility due to its superiority. PAO is like BFs using typical Lewis acid catalysts, aluminum chloride or Ziegler-Natsuta catalysts. - produced by polymerization of c6Cam 1-alkenes such as decene. these The manufacturing method and properties of are described by J. Prennane, Ind. Eng. Chew, P. rod, Res.

Dev, 1981, pages 19.2-6. Improved with PAO addition The lubricant properties are also described in J. A. Prennnan, U.S. Pat. No. 3,382,291, 3,74. 2.082 and 3,789.363 and U4.041,098. It is. According to these documents, Cs-Cs olefin is similar to aluminosilicate. oligomerized in contact with an acidic medium-pore, shape-selective metallosilicate catalyst. Ru. The aluminosilicate catalyst surface is free from bulky amines or phosphines. Deactivated by activating agent. When oligomerized by the above method, PAO becomes enophyllized. It has olefinic unsaturation that is reactive with molecules.

PAO lubrication, herein referred to as IVI-PAO (with an incredibly high viscosity index) A new type of drug composition is produced. This new HVI-PAO lubricant is particularly effective against methyl Characterized by a low proportion of tyrene groups, i.e. a low branching ratio and a low pour point below -15°C. There is. This low branching ratio is detailed below. Generally 3 to 600 at 100℃ ■■ HVI-PA with a viscosity of 2/S and an extremely high VI of 130 or more The lubricant base material consists of an activated chromium catalyst in a reduced valence state supported on silica. made from alpha olefins, CsC2m1-alkenes alone or in mixtures. will be built. HV 1-PAO is further characterized by a branching ratio smaller than 0.19. There is. Both PAO and HVI/PAO are produced from an oligomerization process. It has olefinic unsaturation and can be used in the present invention.

The branching ratio is defined as the ratio of CHs groups to C)12 groups in the lubricating oil, and Red published in *i, Volume 25 No. 10.1466 (1953) Calculated from the methyl group weight percentage obtained by the external line method.

1-(Methyl group weight percentage) The method for producing HVI-PAO uses the present invention without hydrogenating the oligomerized product. The methods used are described in the Examples below.

! 1 hindrance 1 A commercially available Cr on silica catalyst containing 1% Cr on large pore volume silica gel was used. 7 catalysts 0 reactor using CO calcined at 00°C for 16 hours and reduced at 350'C for 1-2 hours. Add 1 part by weight of activated catalyst to 200 parts by weight of 1-decene in the mixture and heat to 185°C. Ta. L-decene was continuously fed to the reactor at a rate of 2-3.5 parts/min. For every 100 parts fed, 0.5 part catalyst was added. 1200 parts l-decene and 6 parts catalyst Charge soot slurry was stirred for 8 hours. The catalyst was separated by filtration and the pressure was 13 Pa (Hg0.1+w■ ), light products with boiling points below 150°C were removed. Pour the residue onto a diatomaceous earth catalyst. Hydrogenation was carried out at 200°C using i. The finished product is 18,5m at 100℃ It had a viscosity of *2/s, a Vl of 165 and a pour point of -55°C.

Fruit 11 Juice 21 Example 1 was repeated but the reaction temperature was 185°C. Finished product smells at 100℃ It has a viscosity of 145 mm2/s, a Vl of 214 and a pour point of -40°C. Ta.

fire turf doctor Example 1 was repeated, but the reaction temperature was 100°C. Finished products at 100℃ It also has a viscosity of 298 m+*2/s, a Vl of 246 and a pour point of -32°C. It was.

C3 in contact with an acidic, shape-selective metallosilicate catalyst such as ZSM-5 Allyl groups obtained from oligomerization of lower olefins such as s-olefins can also be used. Also useful in the present invention are unsaturated lubricants. These lubricants are generally heated at 100℃ U.S. Pat. No. 4,588,786 with a viscosity of 2 to 12 mm2/s in describes a low molecular weight lubricant olefin produced by oligomerization of propylene. , which is reacted according to the invention to form a novel adduct.

Other zeolite contact methods for producing olefin lubricants that are convenient for the present invention include C, Described in U.S. Pat. No. 4,520.221 and No. 4.658.786 to S. H. Chen has been done.

All alpha and beta saturated alkenes useful in the present invention have the structural formula: %formula% (At least one of Rs, Ry, R@ and R9 in the above formula is an electronegative group, and the remaining hydrogen, alkyl, alkenyl, aryl or aralkyl) There are things that have Those having these structural formulas are referred to as enophiles in this specification. , a convenient electrically negative group for enophiles with structural formula (II) (A in the above formula is O , NH, NR where R is alkyl), benzyl) and and -〇N-NO2, aryl, benzyl, -CH2CN, CH2X (however, X is halogen), -C-OQ (where Q is alkyl, aryl or benzyl) Particularly useful enophiles in the present invention include maleic anhydride. acid, maleimide, acrylonitrile, styrene, 4-carboethoxystyrene, Ethyl acrylate, acrylamide, acrolein, methyl vinyl ketone, fluoride phenyl vinyl ketone, cinnamyl chloride, 4-sulfamyl styrene, meta Acrylic acid, ethyl vinyl carbonate, 2-hydroxyethyl acrylate, etc. be.

The novel lubricant of the present invention combines an unsaturated lubricant and the above enophile through thermal or catalytic contact. a” produced by the known “Ene” reaction, which is reacted with Ene” reaction is “Account of Chemi” by B, B. Snyder. Cal　Re5earch”198ON　13.426-432 After completion of the reaction and production of the adduct, the adduct is hydrogenated to form the compound of the present invention. Produces polar lubricants. The adduct (III) and the polar saturated lubricant (IV) have the structure Formula:% formula% (In the above formula and formula (■), R1 to R5 are each hydrogen, alkyl or alkenyl and the total number of carbon atoms in the groups R1 to R is at least 17, and R@ At least one of R9 and R9 is an electronegative group, and the remaining groups from R6 to R9 are Electronegative group or hydrogen, alkyl, alkenyl, alkynalkyl, aryl or aralkyl) and R4R3R2R? R8 +1111 (IV)　　R5-C-C-C-C-C-Hllll1 HHR+RaR5 In this case, the unsaturated lubricant feedstock is a molecule with many allylic unsaturated sites. When the Ene reaction is particularly It will produce an adduct with a fill portion.

As mentioned above, the production of Ene reaction adducts of unsaturated lubricant molecules and enophile molecules is Vinification can be carried out as is or by heating to 100 to 400°C in a solvent. The method is continuous or It can be done in batch mode. If you use a catalyst, BF3, AICIs , (CH3) 2A I CI.

Catalysts such as 5nC14, C2H5Al, CI2 are preferred.

The scope of the present invention includes the polar functional groups of the hydrogenated adduct produced by the method of the present invention. Further reactions are included to generally improve the lubricating performance and make the product more useful. example For example, the nitrile functionality of adducts prepared from acrylonitrile is known in the art. It can be hydrolyzed to an acid or amide or esterified by the following method. unsaturated lubrication Hydrogenation of adducts produced with maleic anhydride and substituted succinic anhydride This is further reacted with alcohol by known methods to form the anhydride (Vl). Structural formula (V): +11111 RRRCHOR official C 0R1 RRHH (Vl)　R-C-C-C-C-C-Hllll　1 R.R.C.C. (V in the above formula and R in ■ are hydrogen, alkyl or alkenyl, and all carbon atoms in the R group the total number is at least 17, and the lubricant portion of the lubricant portion has at least IR groups; The elementary atom is preferably C+v C1g5s, preferably C3@Ce. , R1 of formula V is C+ Csa alkyl, such as methyl, ethyl, 2-hydroxy ethyl, probyl, octyl, lauryl, etc.) Ru.

The methods and products of the present invention are demonstrated in the following examples along with the characteristic properties of the novel lubricants. Describe it.

! Good doctor U.S. Pat. Nos. 3,382,291 and 3,742,082 to J. Brennan; a, 769. decene-1 by the method described in No. a6a and No. 4,041.098. Olefin mixture containing Cs@ and C4@olefin obtained by oligomerization 297g of solids and 44.5g of maleic anhydride in a gas inlet, stirrer, and sample outlet. After closing the 0 reactor charged in the 4501 Pal reactor and purging the mixture with nitrogen, A nitrogen pressure of 294 KPa (28 psi) was left for convenience in collecting samples. . When the mixture is heated to 175°C while stirring, the pressure is 793KPa (100 psig) and kept at this temperature for 14 days. Samples were routinely taken during the reaction. GC, FTIR and proton N for the entire boiling range and structural changes of the mixture. Analyzed by MR. The GC results show that the maleic anhydride and C3@ phases change over time. It showed a gradual decrease in the volume and a corresponding increase in the amount of high-boiling substances. FTIR and Proton N Both MR results are consistent with the progression of the corresponding succinic anhydride adduct of olefin and maleic anhydride. The 0 reaction, which showed a progressive production reaction, was carried out at 175°C for 14 days, but the analysis result was 9. It was shown that there was no noticeable change after 1 day.

The reaction mixture was cooled to room temperature, the reactor was opened, the reaction mixture was taken out and short-circuit distilled. All unreacted maleic anhydride was removed. Structured by IR and NMR spectra structure was confirmed. The product also had a significantly higher viscosity than the starting olefin mixture. However, as shown in Table I, the high viscosity index was still maintained.

Table-”- Shi　　゛　・　　　　　　　　　　　　104　　29 ．． 6 132212 5.43 Product 104 75.19 122212 10.3 5 Sotane mutual 227 g of the succinic anhydride adduct obtained in Example 4 was treated with a nickel catalyst ( Hirschau 5132-P) was hydrogenated at 140° C. until hydrogen was completely absorbed. Nike After filtering the catalyst, the hydrogenated succinic anhydride adduct was used as an esterification catalyst at HzSM-5. B catalyst was refluxed overnight in excess ethanol. Catalyst and excess ethanol removal The latter product was identified as diethyl succinic acid ester by TR and was subjected to various polar organic reactions. It was found to be soluble in the compound.

uratane shindan 305 g of Csa Cae mixture and 48 g of maleic anhydride as described in Example 4 The Ene reaction was carried out using a funnel. However, the 0 reaction in which the reaction temperature rose to 190°C was 5. Essentially completed in a day.

Branch doctor 100 g of the succinic anhydride adduct obtained in Example 6 was added to 100 g of ethanol on charcoal. % palladium at 50°C.

After filtering off the catalyst, the mixture was esterified on iZsM-5B (as described in Example 1). .

Sustainability Propylene is produced by the two-step zeolite contact process described in U.S. Pat. No. 4,568,786. 100 g of low molecular weight lubricating olefin obtained by oligomerization of and maleic anhydride 2 0 g was reacted as in Example 4 and was essentially complete at 30 hours. Raw from starting material The increase in boiling point range up to the composition is substantially shown in Table 1.

Table-”- centimeter Want 1Ω stop indigo <1515 (>C+s=) 99,8 98.2<1785 ( >Ca*=) 89.4 92.4<2160 (>Ca5=) 6.0 40.0 Although the preferred embodiments of the present invention have been described, As those experienced in this field will easily understand, as long as it does not deviate from the true meaning and scope of Ming. Modifications and variations of the method are also possible. This modification and modification method is patented. It is believed that the invention is within the scope of the claims.

Procedural amendment January 8, 1991 Commissioner of the Patent Office Toshi Ue Matsu 1.Display of the incident PCT/US8910284B 2. Name of the invention Synthetic lubricant containing polar groups 3. Person who makes corrections Relationship to the case Patent applicant Name: Mobil Oil Corporation 4, Agent Translated translation of the description and claims (no change in content) International search report ,,,,,,,,,,,,,,,,,,,,,,,,,,,, pc″:/υS E9102B4B international search report US 8902848 SA 29781

Claims (20)

[Claims] 1. produced from enophiles and olefinic hydrocarbons having at least 20 carbon atoms Structural formula made: ▲Contains mathematical formulas, chemical formulas, tables, etc.▼ [In the above formula, R1, R2, R3, R4 and R5 are hydrogen, alkyl or alkenyl. The total number of carbon atoms in the groups R1 to R5 is at least 17, or At least one of R8 and R9 has a mathematical formula, chemical formula, table, etc.▼ (However, A represents 0, N, or NR where R is alkyl); ▲Mathematical formula, chemical formula , tables, etc. ▼ (However, Z is H, OH, NH2, halogen, alkyl, aryl. -CH2CN; -CH2X (X is a halogen); ▲Mathematical formulas, chemical formulas, tables, etc.▼(Q is alkyl, ali is an electrically negative group selected from the group consisting of ; R6, R7, R8 and R9 are electrically negative groups or hydrogen, alkyl, alkenyl represents a substance selected from alkyl, alkynalkyl, aryl or aralkyl] A polar lubricating fluid characterized by comprising an additive having . 2. A polar lubricating fluid according to claim 1, wherein the adduct is hydrogenated. 3. Structural formula of enophile: ▲Contains mathematical formulas, chemical formulas, tables, etc.▼ (In the above formula, at least one of R6, R7, R9 and R9 is an electrically negative group and the remaining is hydrogen, alkyl, alkenyl, alkynalkyl, aryl or aralkyl 2. The lubricating fluid according to claim 1, wherein the lubricating fluid has: 4. Branching ratio of olefins less than 0.3 and a fraction of 280 to 20,000 2. The lubricating fluid of claim 1, comprising a C2+ alpha olefin having a molecular weight of C2. 5. A lubricating stream according to claim 4, wherein the olefin comprises a C38-C48 olefin. body. 6. Structural formula: ▲Contains mathematical formulas, chemical formulas, tables, etc.▼ Compounds with composition (R is hydrogen, alkyl or alkenyl, and the total number of carbon atoms in all R groups) is at least 17). 7. Structural formula: ▲Contains mathematical formulas, chemical formulas, tables, etc.▼ (In the above formula, R represents hydrogen, alkyl, or alkenyl, and the total carbon atoms of all R groups are the number is at least 17 and R1 is C1-C38 alkyl, methyl, ethyl, Represents 2-hydroxyethyl, propyl, octyl, lauryl or aryl ) The lubricating fluid according to claim 2. 8. The olefin is C6-C20 alpha olefin and Lewis acid or Ziegler. Oligomerization products with a VI of 80 or more obtained by contacting with a Natta-type catalyst The lubricating fluid according to claim 1, comprising: 9. Olefins are oxidized by contact with acidic mesopore shape-selective metallosilicate catalysts. The lubricating stream of claim 1 comprising a gomerized C3-C5 olefin product. body. 10. A lubricating stream according to claim 9, wherein the metallosilicate is an aluminosilicate. body. 11. Surface deactivator where the aluminosilicate consists of bulky amine or phosphine The lubricating fluid according to claim 10, wherein the surface of the lubricating fluid is deactivated by. 12. The hydrogenated adduct has a viscosity of 75 mm2/s at 104°C and a 3. The lubricating fluid of claim 2 having a VI of 22. 13. Claim 6 consisting of succinic acid having a C20+ hydrocarbon substituent in the alpha position. Lubricating fluids as described in. 14. The ratio of enophile moieties to olefinic hydrocarbon moieties in the adduct is greater than 1. The lubricating fluid according to claim 1. 15. Reaction after reacting enophile and olefin under heating in a closed reaction zone Enophile and C20, characterized in that the effluent is separated from the region to produce an adduct. + A method for producing polar lubricating fluids consisting of olefin adducts. 16. Claim 15, wherein the olefin and enophile are catalytically reacted with a Lewis acid catalyst. How to put it on. 17. Further, the adduct is mixed with a hydrogenation catalyst and hydrogen at a temperature of 20 to 300°C. A claim comprising the step of producing a hydrogenated polar lubricating fluid by contacting the polar lubricating fluid with hydrogen. 15. The method described in 15. 18. 16. The method according to claim 15, wherein the temperature is between 40 and 400<0>C. 19. The enophile is composed of maleic anhydride and the olefin is 1-decene. A process according to claim 15, comprising C30-C40 hydrocarbons obtained from gomerization. . 20. Enophile vs. C20+ olefin 16. The method according to claim 15, wherein the reaction is carried out in a molar ratio greater than 1.