JPH03504141A - New synthetic lubricant composition and its manufacturing method - 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] New synthetic lubricant composition and its manufacturing method The present invention describes new compositions and compositions made from synthetic lubricants by reaction with olefins. and its manufacturing method. In particular, the present invention provides high viscosity index synthetic lubricant oligomers. - Regarding the modification of fraxin, low molecular weight by-product oligomer wallac is used as a reactant. Use one scene. Modified synthetic lubricants are useful in their own right, among other improvements. Useful as a thermally stable lubricant.

Improving the performance of natural mineral oil-based lubricants by synthesis of oligomeric hydrocarbon fluids has been an important research and development challenge in the petroleum industry for at least 50 years, and in recent years Based mainly on the oligomerization of α-olefins or 1-alkenes, many Excellent poly-alpha-olefin synthetic lubricants have been supplied to the market. Modification of lubricant properties Industrial research into synthetic lubricants has shown that their lubricity is equal to or better than that of mineral oil. useful over a wide temperature range while exhibiting thermal and oxidative stability and pour point The present invention has been directed toward fluids with improved viscosity, ie, improved viscosity index. These new Synthetic lubricants reduce friction and therefore reduce the mechanical load from the worm gear to the traction device. increases efficiency across the entire load range and over a wider range of operating conditions than mineral oil lubricants. Similarly, efficiency is increased in the surrounding area as well.

found to correlate very well with improved lubrication properties of industrially synthesized lubricants. One feature of the molecular structure of the 1-alkene oligomer that has been It is the ratio of methyl groups to methylene groups. This ratio is called the branching ratio. Endo＼Idrocarbons of High Molecular Weight (S) Standard Hydrocarbons of High Mo1ec ular Weight) J (Analytical Chemistry (Ana) Lytical Chemistry), Volume 25, No. 10, Page 1466 (1953)) from infrared data. viscosity finger It is known that the number increases as the branching ratio decreases. As described herein Until recently, oligomeric liquid lubricants with very small branching ratios were It was not synthesized from Ken. For example, in cationic polymerization or Ziegler catalysts. Oligomers produced from l-decene by polymerization have a branching ratio of 0°20 or more. do. Shubkin is an industrial and engineering company. Ginning Chemistry, Product Research and Development (Ind, Eng, Chem, Prod.

Branched out in Res, Dev, Volume 19, pp. 15-19 (1980) The value of the branching ratio is based on the cationic polymerization reaction mechanism involving the rearrangements that produce The explanation is that the appearance is limited. Another explanation is that when a branch occurs, It has been proposed that isomerization of the olefinic group occurs at the position to form an internal olefin. Ru. Whether by rearrangement, isomerization, or a mechanism that will soon become clear, this is not the case. 1-Alkenes to produce synthetic lubricants as practiced industrially In the technology of oligomerization, excessive branching occurs and this can be achieved in lubricants. It is clear that the properties are limited, especially with respect to the viscosity index. The increase in branching is , it is clear that increasing the number of isomers in the oligomer mixture is consistent with the theoretical outline above. This will lead the composition to move away from the structure that would be preferred from careful consideration.

U.S. Pat. No. 4,282.392 to Cupple et al. , a tetramer with an improved viscosity-volatility relationship and by a hydrogenation method that undergoes skeletal rearrangement. and lubricants containing large proportions of pentamers and isomerized components are described.

The claimed composition is a tetramer of a trimer not greater than 1:1. It is a percentage of The branching ratio is not explained.

Coordination catalysts for producing high polymers from 1-alkenes, especially those supported on silica supports. A method using ROM catalyst was developed by Weiss et al. Jour, Catalysis Volume 88, Nos. 424-430 (1984) and in West German Patent Publication No. 3.427,319. has been done. This method produces high polymers at low temperatures, but it also produces polymers with unique structures. Lubricants are not disclosed.

In recent years, a new lubricant composition (hereinafter referred to as HVI-PA) containing a poly-α-olefin has been developed. O) and its use using reduced chromium supported on a silica support as a catalyst. The manufacturing method is described in U.S. Patent Nos. 4,827.064 and 4,827,0. It is described in No. 73. HVl-PA○ lubricant in the oligomerization region Reduced valence state chromium oxide supported on a porous silica support under oligomerization conditions Catalyst and C@-C,. The 1-alkene feedstock is brought into contact, thereby reducing the High viscosity, high Vl (viscosity index) liquid carbonization with branching ratio and pour point below -15℃ A hydrogen lubricant is produced by a method comprising producing a hydrogen lubricant. This method Comparison with known oligomerization methods for producing polyα-olefin 7 using isic acid They differ in that only a small amount of isomerization of olefinic bonds occurs. this method The lubricants manufactured by cover the entire range of lubricant viscosities and have very high viscosity index (VI) and also has a low pour point even at high viscosity.

When synthesized, HVI-PAO oligomers are It's advantageous. Generally, HVI-PAO oligomers are hydrogenated for lubricant applications. Improved stability. HVI-PAO oligomer provides improved thermal stability These modifications to are particularly preferred.

When producing new HV I-PAO lubricants, α-olefinic unsaturation The olefin 2 positioner may be separated from the oligomerization reaction.

The composition of the dimer mixture shows almost no double bond isomerization and a low branching ratio. Compatible with the unique peculiarities of oligomerization reactions. Non-lubricating materials with molecular weight range Separation of representative dimers is necessary to control product volatility and viscosity. It is essential. However, lower viscosity with lower average molecular weight is important in the market. When changing the oligomerization conditions to produce a product with a degree of The yield of non-lubricating dimer fluxin by-products increases as the average molecular weight of the product decreases. increase. Increased yield of dimer by-products improves the overall process of producing useful low viscosity lubricants. This means a substantial economic burden.

Therefore, to avoid the economic burden associated with producing low viscosity lubricants, non-lubricating It is desirable to incorporate side range flux into the product.

Olefins in the non-lubricating range produced in the oligomerization process are converted into lubricating range olefins. It has been found that they can be effectively converted into lubricant range products by reaction with substances.

Also, other olefins can be used in the same process, and the reaction products are Regardless of their properties, they have unexpectedly better thermal stability than the original lubricant range materials. It was found that This method also improves the yield of lubricant material.

Therefore, in the present invention, the oligomerization of 1-alkenes (α-olefins) Provided is a method for improving the thermal stability of synthetic lubricants comprising olefins and The method comprises reacting oligomers. Mainly like cracking It is thought to proceed by alkylation, isomerization and polymerization with side reactions of the species. The reaction is carried out in the presence of an alkylation catalyst under conditions suitable for alkylation. The preferred olefin for reaction with the lubricant oligomer is the olefin of the α-olefin starting material. It is a lower molecular weight non-lubricating olefin produced during the oligomerization process. this Using these lower molecular weight substances, the final lubricant formulation This not only improves the thermal stability of the product, but also increases product yield and olefin utilization. Accordingly, the economic burden associated with manufacturing lubricants in the low viscosity range is avoided. follow Therefore, in a preferred embodiment of the present invention, the compound produced in the process of oligomerization of 1-alkene lubricant range using lower molecular weight non-lubricating range hydrocarbons. Modify oligomers.

The reaction is carried out using an acid type catalyst. Effective acid-type catalysts include alkylation catalysts, Preferably open pores such as those derived from fluorinated alumina ) preferably comprises a catalyst.

The compositions of the invention contain at least one higher alkyl per oligomer molecule. (C,, -C,.) Linear C, -C, with branching. 30-13 per molecule 00 carbon atoms. In a preferred embodiment, the novel composition has a It has a branching ratio of methyl to methylene and a pour point below -15°C.

Converting alpha-olefins into high viscosity index lubricant products with desired thermal stability A preferred method is under oligomerization conditions of C,-C,.

Reduced valence state of α-olefin raw material or its mixture supported on a porous carrier Hydrocarbons and olefinic lubricants from the olefinic lubricant range are Oligos containing oligomers comprising hydrocarbon by-products in the refinic non-lubricating range obtaining a merization product, separating lubricant hydrocarbons and non-lubricant hydrocarbons, The process of hydrogenating hydrocarbons in the lubricant range, alkylating conditions, alkylate acid-type catalysts and hydrogenated hydrocarbons and as alkylating agents. Contacting olefinic by-product hydrocarbons and thereby alkylated lubrication the step of obtaining a range of hydrocarbons.

Figure 1 of the drawings shows the relationship between alkylation degree and viscosity loss of modified HVr-PAO. show.

Figure 2 shows HV I-PAOt:rmer tj and modified HVI-PAO oligomer. - shows the relationship between viscosity and viscosity index.

In a preferred embodiment of the invention, the synthetic hydrocarbon lubricant is manufactured by the origin producing the synthetic lubricant. Aluminum containing a unique olefin dimer produced as a by-product in the gomerization reaction It is denatured by a reaction using Ken.

Can be used to react with HV r-PAO oligomers as described herein. Alkenes that can be converted include C, -C,. Includes linear or branched alkenes, especially 1- Alkenes and )(Olefinic dimer by-products of the Vl-PAO oligomerization reaction) It is. Preferred 1-alkenes for reaction with HVI-PAO oligomers include 1- Hexene, 1-octene, 1-decene, 1-dodecene and 1-tetradecene. and branched-chain isomers, such as 4-methyl-1-pentene, containing 6 or more carbon atoms. Fourteen olefins are included. Particularly preferred 1-alkenes are C, -C,. α ~Olefins such as 1-octene, ■-decene and the first lubricant range materials It is an olefin dimer produced in the oligomerization process.

The oligomerization reaction is carried out using a reducing metal catalyst supported on a silica support, preferably a 1-alkene. Preferably, it is carried out by contacting with reduced chromium oxide. Alkylation in the present invention The characteristics of the new oligomerization reaction, which produces by-product dimers used as agents, are and dialkylvinylidene, 1,2 dialkyl as determined by NMR analysis. or trial bovine monoolefin oligomer or HV I-PAO oligo The result is that a mixture of mer is produced. However, in general, HVl-PAO The oligomer has some head-to-head bonds, but preferably n is O, such that It has a regular head-to-tail structure that is ~17 and terminates in olefinic unsaturation: CH.

In the HVI-PAO process, BF or AlC1, which is used industrially, is Surprisingly, compared to dimers produced by oligomerization of 1-alkenes, A simple and useful dimer is produced.

Typically, the present invention includes a significant proportion of non-hydrogenated dimerized 1-alkenes or alpha-ols. It was found that the lefin has the following vinylisonyl structure: CH,=CR,Rf In the formula, R3 and R2 are alkyl groups, and from the head-to-tail addition of the 1-alkene molecule Residues of are shown. For example, H The by-product diopter from the oligomerization of 1-decene by the VI-PAO process is When measured by chromatography (GC), it was found to contain three main components. It was done. Based on IsC-NMR analysis, the non-hydrogenated components are 8-eicosene, 9 -eicosene, 2-octyldodecene and 9-methyl-8 or 9-methyl- It turned out to be 9-nonadecene.

Olefinic HVI-PAO oligomers and those used as starting materials in the present invention Olefins suitable for use as starting materials in the production of by-product dimers for use in Includes 1-hexene, 1-octene, 1-decene, 1-dodecene and 1-tetho. carbon such as rhadecene and branched chain isomers, e.g. 4-methyl-1-pentene Olefins having 6 to 14 atoms are included. Preferred 1-alkene is l-decene It is. It is also suitable to use raw materials for refining processes containing olefins or is the effluent. However, the olefin used in the present invention is an α-olefin , for example, preferably l-octene to 1-dodecene, more preferably 1-decene or a mixture of such olefins.

The α-olefin HVI-PAO oligomer in the lubricant range used in the present invention is 0. It has a small branching ratio of less than 19 and is manufactured by all known industrial methods. Excellent lubrication compared to α-olefin oligomers with a large branching ratio have characteristics.

This type of unsaturated HVI-PAO α-olefin oligomer is an α-olefin The majority of double bonds are generated by oligomerization reactions without isomerization. This anti Optionally, supported metal oxide catalysts, such as Cr on silica or other supported Group VIB compounds of the periodic table are related. The most preferred catalysts are A supported lower valence Group VIB metal oxide. Preferred carriers include , silica, alumina, titanium oxide, silica alumina, magnesia, etc. Ru. The support material binds the metal oxide catalyst. Has at least 40 pore openings These porous substrates are preferred.

The carrier material usually has a large surface area and average pore size of 40 x 10-'m11 to 35 It has a large pore volume of 0x10-'+*m. Large surface area, highly dispersed In order to maximize the efficiency of metal use by supporting a large amount of sexually active chromium metal centers, It is effective for many purposes, and a very highly active catalyst can be obtained. The carrier is small (40X1 Must have a large average pore opening of 0-'m+a, 60X 10-'am~ An average pore opening of 300X 10-'+ue is preferred. This large pore opening is Diffusion as substances and products approach and away from the active catalytic metal center Therefore, the productivity of the catalyst is optimized. Also available on fixed floors or slabs. Such catalysts are used in Lee reactors and are recycled and regenerated many times. , silica supports with good physical strength and wear during handling or reactions are preferred. or collapse is prevented.

Supported metal oxide catalysts are produced by impregnating the support with metal salts in water or organic solvents. Preferably, it is prepared by: For example, ethanol, methanol or acetic acid Any suitable organic solvent known in the art can be used, such as. Next, solid catalyst destination The precursor is dried and calcined at 200-900°C with air or other oxygen-containing gas. . Then, Co, H,, NH3, H, S, C5,, CH, SCH,, CH, 5S CH,, R, AI, R, B, R, Mg, RLi, R*Zn (R is alkyl, alkyl Well-known compounds such as metal alkyl-containing compounds such as alkyl, aryl, etc. The catalyst is reduced using various reducing agents. Preferably C01H1 or metal aluminum It is a kill-containing compound.

Alternatively, the Group VIB metal is applied to the substrate in reduced form, such as a CrII compound. good. The resulting catalyst has a temperature of below room temperature to 250°C and a pressure of 10.1 kPa ( Olefin at a pressure of 0.1 atm) to 34580 kPa (5000 psi) Very active in oligomerization. However, the feedstock to catalyst weight ratio When 10=1 to 30:1, the oligomerization temperature is preferably 90 to 250°C. Ru. The contact time between olefin and catalyst may vary from 1 second to 24 hours.

The catalyst can be used in a batch reactor or a fixed bed continuous flow reactor.

Generally, a carrier material is added to a solution of a metal compound, such as an acetate or a nitrate; The mixture is then mixed and dried at room temperature. Then dry the solid gel at a higher temperature. and purge to 600° C. for 16 to 20 hours. 250 ml of catalyst under an inert atmosphere Cool to ~450°C and contact the pure reductant stream with the catalyst to generate sufficient C O flows and reduces the catalyst as indicated by an obvious color change from bright orange to blue-white. do. Generally, in excess of the amount that reduces the catalyst to the lower valence CrII state. The catalyst is treated with an amount of CO corresponding to twice the chemical equivalent.

The product oligomers are very broad with high viscosity index suitable for high performance lubricant applications. Has a wide range of viscosities. In addition, the product oligomer has a nearly uniform head-to-tail structure. It has an atactic molecular structure with a few head-to-head bonds. These small Low branching ratio oligomers typically have higher branching ratios and correspondingly lower viscosities. of the prior art with a viscosity index of at least 15 ~20 units, typically 30-40 units higher. these Low branching ratio oligomers maintain better or similar pour points.

The proportion defined as the proportion of reaction products and by-products to CH, groups to CH, groups. The branching ratio is calculated from the weight fraction of methyl groups obtained by infrared method, and this method is Analytical Che+m1stry ) Vol. 25, No. 10, p. 1466 (1953).

Weight fraction of methyl groups Branching ratio = □ 1-(weight fraction of methyl groups) The unique olefinic dimer used as the alkylating agent of the present invention is HVI -Produced as a by-product of the PAO oligomerization reaction.

Generally, in the production of HVI-PAO oligomer lubricant bases, oligomerization The reaction mixture is separated from the catalyst to remove unreacted α-olefin and oligomerization reaction mixture. reduced pressure to remove by-products in the lower boiling range, e.g. α-olefin dimer Separate by distillation. This allows lubricants with suitably high volatility and viscosity A base is obtained. alpha-oleclease using other methods known to those skilled in the art such as solvent extraction. Although the fin dimer by-product can be separated, distillation is preferred.

The following examples illustrate the oligomerization reaction and the resulting lubricant grade oligomerization reaction. Explain ligoma. By reaction, the alkylating agent or reactant of the present invention An olefinic dimer is obtained as a by-product, which is used as a by-product. dimer is oligo It is separated from the merization reaction mixture by distillation.

, 1.9 g of chromium(II) acetate (Crt(OCOCR-)-2HtO), commercially available (5.58 mmol) is dissolved in 50 ml of hot acetic acid. Next, mesh size 8 -12, 50 g of silica gel with a surface area of 300/g and a pore volume of 1 ml/g are also added.

Most of the solution is absorbed into the silica gel. Rotate the final mixture at room temperature. Mix on a rotavap for half an hour and dry in an open dish at room temperature. At first, Purge the dry solid (20 g) with N in a tube oven at 250°C.

Next, the furnace temperature is raised to 400° C. and heated for 2 hours. After that, the temperature was set to 600℃. Purge dry air for 16 hours. At this point, cool the catalyst under N to 300℃. . 1 pure Co (Matheson, 99.99%) stream Supply time. Finally, the catalyst under Ng is cooled to room temperature and ready for use. .

Example 2 The catalyst prepared in Example 1 (3.2 g) was heated to 9.5 liters of N in an outer drying box. Fill a 3/8 inch (3/8 inch) Steffles Steel tubular reactor. next, N, in a single-zone Lindberg furnace under atmosphere. Heat the reactor to 150°C. Pre-purified 1-hexene at 1069kPa (140psi) and 20ml/Hr. liquid spill Unreacted starting material and low boiling point Remove range materials. The remaining colorless transparent liquid has an appropriate viscosity and viscosity as a lubricant base. and viscosity index (Vl).

Recruitment course Pre-run 1 2 3 Distribution time (hours) 2 3.5 5.5 21.5 Lubricant yield (wt%) 1 0 41 74 31 Viscosity, 1Iiys”/s (c 5) 40℃ 20g, 5 123.3 104.4 166.21 00℃ 26.1 17.1 14.5 20.4 Viscosity Index (Vl) 159, 151 142 143 Examples 3 Commercial chromium/silica catalyst with 1% Cr on large pore volume synthetic silica gel use. First, the catalyst was calcined in air at 800°C for 16 hours, and then at 300°C for 16 hours. ．． Reduce with CO for 5 hours. Next, 3.5 g of catalyst was filled into the front reactor, and N, Heat to 100°C under atmosphere. 1-hexene at 101 kPa (1 atm), 28 Charge by pump at m1/Hr. When the products are collected and analyzed, the following results are obtained. : Test firing CDEF Distribution time (hours) 3.5 4.5 6.5 22.5 yen Lubricant yield (wt%) 73 64 59 21 Viscosity, m” /5(cS) 40℃ 2548 2429 3315 9031100℃ 102 151 +97 437 Viscosity index (Vl) 108 164 174 199 Lubrication produced by the above method Because they contain olefinic unsaturation, they are typically stabilized by hydrogenation for use in lubricants. let However, very large molecular weight oligomers contain olefins. Since the number of bonds is relatively small, hydrogenation may not be necessary. low viscosity lubrication Oligomers with smaller molecular weights are of particular interest in the present invention for producing agents. - is hydrogenated by methods well known to those skilled in the lubricant art.

In the present invention, the thermal stability of the oligomers in the hydrogenated lubricant range is or reaction with the non-lubricant range produced as a by-product of the oligomerization reaction. This will be improved by responding. Although not bound by theoretical considerations, HVI-P The reaction used here to modify the AO oligomer is an alkylation reaction. and the reactant alkene is an alkylating agent. Alkylation is , which is an important reaction that occurs in the present invention and is carried out under alkylating conditions. , other reactions such as thalassoking, isomerization and polymerization occur as well. Therefore, As used herein, the term alkylation refers to HV Includes all such reactions that result in useful modification of I-PAO oligomers.

The catalyst used in the alkylation reaction of the present invention preferably has large pore openings. It is a porous solid acid type catalyst. Preferred catalysts are prepared as described below. fluorinated alumina. Other useful solid catalysts include acid zeolites. It will be done. Zeolites useful as catalysts in the present invention can be any naturally occurring or synthetic acid type. Large pore size zeolites, typically 6.4 x 10-'am to 7.5 x 10 - All natural or synthetic acidic large pore size zeolites with pore size of Included. In addition to fluorinated alumina, particularly useful catalysts include ZSM-4, ZS M-12, ZSM-20, houge with hole size 7.4X10-'+n (7° 4 people) X and Y1 canculinite, gmelinite, mazzite e) includes acid forms of mordenite and offretite. The present invention Other alkylation catalysts that are also useful in the process include HF SA Ic Is, B F, and BF, complex, 5bC1s, 5IIC14, TiCL, Ptos%Hy SO-1ZnClt as well as conventional alkylene oxides known to those skilled in the art such as acidic clays. Rating catalysts are included.

Alkylation with large alkyl branches by the alkylation reaction of the present invention Synthetic lubricants are produced. The alkyl branch is the olefin used in the alkylation reaction. pins, such as C, -C,. Depending on the α-olefin, preferably 12 to 40 Contains carbon atoms or mixtures thereof. Monomer olefins, e.g. ethylene 2-40 when using decene, propylene, 1-decene as alkylating agent Branching introduced by olefins can be used to form dimeric olefins in alkylate reactions. It can be controlled by the molar ratio of alkenes such as lubricants to synthetic lubricants. one Generally, the molar ratio of olefin to lubricant range material is 40:1-1:1. preferred The molar ratio is 5:I-1:I. As a result, the product properties are Alkylated synthetic lubricants from synthetic lubricants containing at least one large alkyl group The reaction products may range from mixtures of lubricants and synthetic lubricants. Surprising surprise In particular, when the synthetic lubricant is an HVI-PAO oligomer, the application according to the invention High Vl and unalkylated H due to alkylation with Lukene 2j1 An alkylate product with a low pour point of the VI-PA○ oligomer is formed and Shows improved stability.

The following examples illustrate the preparation of preferred alkylation catalysts of the present invention and further illustrate the preparation of preferred alkylation catalysts of the present invention. A standard alkylation reaction will be explained.

Example 4 Preparation of alkylate catalyst Alumina (Harshaw Catapal) in 30 ml of water l) -3,0,8+a++ (1/32 inch)) 25g of aluminum nitrate Contact with 15.8 g of nonahydrate for 1 hour. After contact, excess water was removed under reduced pressure at 80°C. Remove. Aluminum nitrate impregnated alumina with ammonium fluoride in 50ml of water Aluminum fluoride is formed in alumina by contacting with 8.17 g. under reduced pressure , dry the aluminum fluoride/alumina catalyst at 115°C for 18 hours, then dry the aluminum fluoride/alumina catalyst at 538°C. Bake at ℃ for 12 hours.

Example 5 Synthetic lubricant/dimer production HVI-P in which 1-decene is reacted with chromium-supported silica as explained earlier. Synthetic lubricants are manufactured by the AO method. Unsaturated decene dimer is produced as a by-product by distillation. to remove unreacted decene and hydrogenated lubricant products. raw lubricant The viscosity of the product was 9.2 ms”/s (9.2 cS) when measured at 100°C. .

Cold - Keiichi Gar 1 Alkylation of HVI-PAO lubricantsFull chelation reaction was carried out in a fixed bed reactor. give The apparatus was maintained at 2861 kPa (400 psig) and the liquid hourly space velocity (L H3V) is 0.5. i charge 1t, 1-decene HV I-PAO7'a lubricant 3 15 g and 140 g (30.8% by weight) of 1-decene dimer. a In Examples 7-1.7-2 and 7-3, each reaction temperature was 1. 67. Run at 204 and 250'C. The results of these alkylation reactions are shown in Table 1.

Table 1 Examples Raw materials 7-1 7-2 7-3 Reaction temperature, 'C 167204250 LH3V, 0.5 0.5 pressure, kPa (PISG) -2861 (400) 2861 (400) 2861 (400) Preparation BVI-PAO, g -40,150!　　　 46.2 recovered HVI-PAO, g -46,757,350, 1% by weight Increase 15.9 13. il 8.4KV, 4 Q℃ 50.0 74.0 79.5 70.5KV, 1 00℃ 9.2 11.7 12.1 11.3 Viscosity index ( Vl) 167 153 148 154 Molecular weight 710 786 795 825 HV I- present in raw materials Calculate the amount of HVI-PAO delivered based on the initial percentage of PAO Table 1 shows each example. After alkylation, weight increase is expected. and shown in the table. The weight gain varies from 8.4 to 15.9% and is a function of reaction temperature. Conceivable.

Using this method, the overall yield of the final product is lower than the synthesis of dimeric byproduct HVI-PA. ○Increases due to alkylation into lubricants. The alkylated product is the starting H These oligomers have an increased viscosity when compared to VI-PAO lubricants. Maintains high Vl characteristics.

The following examples further illustrate the method of the invention. Surprisingly, explained below As such, the thermal stability of the lubricant obtained by the alkylation process is substantially It was found that there was an increase in Exposure for 24 hours at 300'C in an inert atmosphere results in non-alcoholic The chelated HV I-PAO has a 35% reduction in viscosity at 100°C. same When Hv■-PAO is alkylated to 30% using a by-product dimer, the viscosity Losses are reduced to 10%.

Example 7 Preparation of catalyst A solution comprising 5.3 g of alumina nitrate (9 hydrate) in 30 ml of water and aluminum 25g of Na was left in contact for 1 hour. Excess water is removed by vacuum. dry aluminum Nitrate-impregnated alumina containing 2.7g of ammonium fluoride in 50ml of water Contact with one solution. After 5 minutes, excess water is separated from the resulting fluorinated alkali. The mina is dried under vacuum at 95°C for 3 days. This catalyst contains 5% aluminum fluoride. Alkylation reaction of Ni 7.0 g of the above fluorinated alumina catalyst was placed in a fixed bed reactor and heated at 538°C for 18 hours. Bake for a while. HVI- of 18.9 am”/s (cs) at GoOO°C 300 g (61.2% by weight) of PA0 and 190 g (38 , 8% by weight) for Example 9-1.9-2 and 9-3. Passed over a fluorinated alumina catalyst under the conditions indicated in the table. Example weight percentage increase Measure the degree of alkylation. The degree of alkylation ranges from 7.5 to 30.6%. It is changing around.

Table 3 shows the results of studies on the thermal stability of the alkylated products. non-alky Rated HV I-PAO has a temperature of 10 when exposed to an inert atmosphere at 300°C for 24 hours. The viscosity at 0°C is reduced by 35.4%.

As the degree of alkylation increases, the stability of alkylated HVI-PAO increases. Ru. In the case of 30.6% alkylation, the viscosity loss decreases to 10.1 ( 100'C).

In the drawing, the relationship between the degree of alkylation and viscosity loss is shown. This is according to the present invention. Figure 2 shows increased thermal stability of alkylated H1-PAO.

Table 2 Examples Raw materials 9-1 9-2 9-3 Reaction temperature, 'C 138139139 LH3V O, 50, 50, 5 pressure, kPa (PIS G) -2861 (400) 2413 (350) 2413 (350 ) Preparation HVI-PAO, g -22,223,853,0 Recovery HVI-PA O, g 29.0 26.7 57.0% increase by weight 30.6 12.2 7.5KV, 40℃ 18.9 15.4 17.0 16.5KV, 100 'CI30.9 103.6 115.2 108.5 Viscosity index (V l) 164.1 15? , 5 161.3 165.3 Molecular weight 1054 871 99 978 Table 3 Thermal stability (300℃, 24 hours) TIVI-PAO130, 91g, 9 164 75.9 12.3 15 9 35.4*9-1 103°6 15.4 158 91! 13 ．． 9 155 10.1*9-2 115.2 17.0 161 84. 7 13.5 163 20.4*9-3 108.5 16.5 1B 5 74.8 12J 163 25.7**100°C viscosity loss standard In the following examples, instead of the HV I-PA021L form, 1;1-de The same fuel and hydrogenated alumina catalyst were used, except that only Sen was mixed with HVI-PAO. and alkylate the HV I-PAO as previously described.

Example 9 18.9mm″/5(C3)HV 1- alkylated with 1-decene P conditions: Reaction temperature, “C169 Pressure, kPa (psig) 2861 (400) LH3V 　O, 4 Preparation RVI-PAO, g 30.7 Result: Recovery 111VI-PAO, g 36.6% increase by weight 19, 2 KV, 40℃ 13.1 KV, 100℃ 84.7 Viscosity index (Vl) 155.6 Table 4 shows the results of thermal stability testing of the product of Example 9.

Table 4 KV, 40'CKV, 100℃ Vl Loss % before heat treatment 84.7 13.1 156 --- After heat treatment 75.5 12.0 154 8.4 Figure 2 shows the viscosity of unreacted HV 1-PAO and reacted HVI-PA○. In the case of the reaction product of the present invention, Vl remains unchanged. It turns out that there is something.

Having described the invention in terms of preferred embodiments, the inventive concept lies within the scope of the following claims. It is not limited except for.

Viscosity 1 history (%, too’c) Sticky 1,000 rules revised international search report international search report

Claims (20)

[Claims] 1. At least one higher alkali having 12 to 40 carbon atoms per oligomer molecule. Liquid lubricant oligomers comprising C30-C1300 hydrocarbons with kill branches - composition. 2.Has a methyl to methylene branching ratio of 0.19 or less and a pour point of -15°C or less The composition according to claim 1. 3. Viscosity index of 130 or higher and viscosity of 3 to 750 mm2/s at 100°C The composition according to claim 1, comprising: 4. A composition according to claim 1, wherein the alkyl branch contains 20 carbon atoms. 5. Claim 1 comprising an essentially linear liquid lubricant oligomer. Composition. 6. Hydrogenated polymer residue of 1-alkene from linear C6-C20 1-alkene A composition according to claim 1, comprising: 7.1-Alkene contains 1-decene, and the number of carbon atoms in the higher alkyl branch is 20. The composition according to claim 1, wherein the composition has a molecular weight of 20. 8. Viscosity index of 130 or higher and viscosity of 3 to 750 mm2/s at 100°C The composition according to claim 6, which has the following. 9. Increase yield of α-olefins to lubricant range hydrocarbons with high viscosity index A method for converting i. Under oligomerization conditions, the reduced Group VIB metal catalyst in original valence state and C■-C20α-olefin raw material or its A mixture of olefinic lubricants ranges from hydrocarbons to olefinic non-lubricants. obtaining an oligomerization product mixture comprising a lubricant range hydrocarbon by-product; ii. Lubricating hydrocarbons and non-lubricating hydrocarbons are separated to form lubricating range hydrocarbons. hydrogenating; and iii. Under alkylating conditions, the alkylating region an alkyl containing hydrogenated hydrocarbons and olefinic by-product hydrocarbons in the A lating agent is contacted with a solid acid catalyst to produce an alkylated lubricant range hydrocarbon. process of forming A method comprising: 10. The alkylating agent is the olefinic C12-C40 of the oligomerization product. 10. A method according to claim 9, comprising a dimer fraction. 11. Solid acid type catalysts are a group consisting of large pore size zeolites and fluorinated aluminas. 10. The method of claim 9, wherein the method is selected from: 12. Hydrocarbons in the alkylated lubricant range have a viscosity index of 130 or higher, -15 Claim 9, which has a pour point of not more than °C and a viscosity of 3 to 750 mm2/s. How to put it on. 13. The metal catalyst is chromium oxide supported on silica, which is reduced by carbon monoxide. 10. The method of claim 9, comprising: 14. Claim 9 wherein the alkylating agent comprises a C2-C40 alkene. Method described. 15. Acid type catalysts include HF, ALCL3, BF3 and BF3 complexes, SbCl5, SnCl4, TiCl4, P2O5, H2SO4, ZnCl2 and acidic The method according to claim 9, wherein the method is selected from A. 16. The method of claim 9, wherein the acid type catalyst comprises a large pore size zeolite. . 17. 10. The method of claim 9, wherein the acid type catalyst comprises fluorinated alumina. 18. The Group VIB metal catalyst in a reduced valence state supported on a porous carrier is supported on silica. 10. A method according to claim 9, comprising chromium oxide to be reduced. 19. 19. The method of claim 18, wherein the metal catalyst is reduced by carbon monoxide. . 20. The alkylating agent is the olefinic C12-C40 of the oligomerization product. 11. The method of claim 10, comprising a non-lubricating range of hydrocarbons.