CA2123426A1 - Dehydrocyclization of polyalpha-olefin lubricants - Google Patents

Abstract

2123426 9310066 PCTABS00022 Aromatic structures can be introduced into the molecular structure of polyalpha-olefin (PAO) lubricant oligomers by subjecting the polyalpha-olefin to a dehydrocyclization reaction which converts a portion of the pendant or branching alkyl groups in the recurring polymeric unit of PAO to aromatic structures. When the starting material for dehydrocyclization is PAO prepared by oligomerization of C6-C20 alpha-olefins in contact with reduced chromium oxide catalyst on porous support the dehydrocyclization reaction produces a lubricant oligomer with increased aromaticity without significantly degrading the viscometric properties of the feedstock lubricant, particularly the high VI of the starting material.
The aromatic structures introduced lend increased thermal stability, wear resistance and solubilizing characteristics to the liquid lubricant oligomers so modified. The polyalpha-olefins produced by the dehydrocyclization process comprise novel compositions of matter containing up to five weight percent of aromatic structure attached as pendant groups to the backbone of the polyalpha-olefin structure.

Description

2 1 2 3 ~ 2 6 PCl/US91/08783 ~:
:

DEHYDROCYCLIZATION OF POLYALPHA-OLEFIN LUBRICANTS :~
'' ' This invention relates to novel compositions of , polyalpha-olefin (PAO) oligomers containing aromatic structures useful as lubricant basestock and lubricant additives and to their means of preparation. More particularly, the invention relates to novel lubricant compositions having high viscosity index (VI) and enhanced thermal stability prepared by dehydrocyclization of polyalpha-olefin oligomers that exhibit high VI and low pour point.
The synthesis of oligomeric hydrocarbon fluids, ~-which have improved performance over those of mineral oil based lubricants, has been the subject of important j;
research and development in the petroleum industry for many years and has led to the relatively recent market introduction of a number of superior polyalpha-olefin synthetic lubricants, primarily based on the oligomeri-zation of alpha-olefins or l-alkenes. The thrust of the industrial research effort on synthetic lubricants has been toward fluids exhibiting us~ful viscosities over a wide range of temperature, i.e., improved viscosity index, while also showing lubricity, thermal and oxidative stability and pour point equal to or better than mineral oil. These new synthetic lubricants lower friction and hence increase mechanical efficiency over a wider range of operating conditions than mineral oil lubricants.
Notwithstanding their generally superior properties, PAO lubricants are often formulated with additives, or an additive package, to enhance those properties for specific applications. The more commonly used additives include oxidation inhibitors, rust inhibitors, metal passivators, antiwear agents, extreme pressure additives, pour point depressants, detergent-dispersants, viscosity index (VI) improvers, foam 2123~26 inhibitors and the like. This aspect of the lubricant arts is specifically described in Kirk-Othmer "Encyclopedia of Chemical Technology", 3rd edition, Vol.
14, pp. 477-526.
Lube additive packages are complex and costly materials. Therefore, a significantly superior new lubricant is one in which the properties conferred on lube mixture by known additives are intrinsic to the structure of the new lubricant molecule, obviating or at least reducing the need for additives. Consequently, improvements in lubricant technology pursued by artisans in the field flow from both new additive development addressed to deficiencies in lubricant oligomers and new oligomer development for inherently better properties to displace additives. Increasing the aromaticity of lube mixtures is known to improve thermal stability and anti-wear properties. However, in view of the paraffinic nature of PAO lubricants aromatic additives to PAO are often confronted with problems of solubility that limit their usefulness or require the ~se of costly disper-sants.
Alkylated aromatics are known in the prior art as lubricant additives for their antiwear properties, thermal and oxidative stability as disclosed in U.S.
Patent Nos. 4,211,665, 4,238,343, 4,604,491 and 4,714,7944. Antiwear properties of alkylnaphthalene lubricating fluids are presented in Khimiya i Tekhnologiya Topliv i Masel, No. 8, pp. 28~29, August, 1986.
Recently, novel lubricant compositions ~referred to herein as HVI-PAO) comprising polyalpha-olefins and methods for their preparation employing as catalyst reduced chromium on a silica support have been disclosed :
in U.S. Patent Nos. 4,827,064 and 4,827,073. The process comprises contacting C6-C20 l-alkene feedstock with reduced valence state chromium oxide catalyst on porous :`
silîca support under oligomerizing conditions in an W093/l~u~ 2 1 2 3 4 2 6 PCT/US91~08783 oligomerization zone whereby high viscosity, high VI
liquid hydrocarbon lubricant is produced having branch ratios less than 0.19 and pour point below -15-C.
Lubricants produced by the process cover the full range s of lubricant viscosities and exhibit a remarkably high VI
and low pour point even at high viscosity. The molecular structure of HVI-PAO is novel and comprises the product of an essentially regular head to tail polymerization of alpha-olefin, thus providing an oligomer with large pendant alkyl groups on the recurring polymeric unit.
Dehydrocyclization is a well known reaction in the organic chemical arts for the conversion of linear and branched alkanes to aromatic compounds, as described in Royals "Advanced Organic Chemistry", Prentice-Hall, Inc., pp. 145-147. The reaction is carried out typically by catalysis with dehydrogenation catalysts and proceeds through ring closure and dehydrogenation to provide an aromatic structure. The dehydrocyclization reaction can be characterized as a type of aromatization reaction and the terms are used interchangeably herein.
It has been found that aromatic structures can be introduced into the molecular structure of polyalpha-olefin lubricant oligomers by subjecting the polyalpha-olefin to a dehydrocyclization reaction which converts a portion of the pendant or branching alkyl groups in the recurring polymeric unit of PAO to aromatic structures.
When the starting material for dehydrocyclization is HVI-PAO, it has been determined that carrying out the `
dehydrocyclization reaction produces a lubricant oligomer with increased aromaticity without significantly degrading the viscometric properties of the HVI-PAO, particularly the high VI of the starting material. As a result, PAO and HVI-PAO are produced containing aromatic structures that lend increased thermal stability, wear resistance and solubilizing characteristics to the liquid lubricant oligomers so modified. The improved solubilizing characteristics are particularly important 2 ~3 ~26 4 for improving the solubility of aromatic additives in the modified lubricant oligomer.
The polyalpha-olefins produced by the dehydro-cyclization process comprise novel compositions of matter containing up to five weight percent of aromatic structure attached as pendant groups to the backbone of the polyalpha-olefin structure.
For the more preferred HVI-PA0 oligomers, the compositions have the recurring polymeric structure:
~-CH2-CH-~n~CH2 CIH ~m (CH2)X R

where x is 5 to ll, n is less than 500 and the ratio of n to m is between 200 and 20; wherein R contains x+l carbon atoms comprising aryl, aralkyl or alkylaryl.
More particularly, the instant invention discloses a process for the dehydrocyclization of C6-C20 polyalpha-olefin which comprises contacting the polyalpha-olefin with dehydrocyclization catalyst in a dehydrocyclization reaction zone under dehydrocylclization conditions whereby modified polyalpha-olefin is produced containing aromatic structures.
The process is more specifically directed to the dehydrocyclization of HVI-PA0 wherein the polyalpha-olefin comprises the product of the oligomerization of alpha-olefins containing 6 to 20 carbon atoms, or mixtures of such olefins. The oligomerization comprises contacting the olefins under oligomerization conditions, at reaction temperature of 900 to 250C with a chromium catalyst on a porous support, which catalyst has been treated by oxidation at a temperature of 200 to 900C in the presence of an ~;
oxidizing gas and then by treatment with a reducing agent at a temperature and for a time sufficient to reduce the catalyst to a lower valence state. The oligomerization produces an oligomeric liquid lubricant composition comprising C30-Cl300 hydrocarbons having a branch ratio W093/10066 212 3 4 2 ~ PCT/US91/08783 of less than O.l9, weight average molecular weight between 420 and 45,000, number average molecular weight between 420 and 18,000, molecular weight distribution, i.e. (weight average molecular weight)/(number average molecular weight), between l and 5 and pour point below -l5C.
In the drawings, Figure l is a plot showing the relationship of hydrogen flow rate to aromaticity in the product of the present invention.
Figure 2 is a plot showing the relationship of hydrogen flow rate to bromine number in the product of the instant invention.
The polyalpha-olefin oligomers used as starting material in the dehydrocyclization step of the process of the instant invention are conventional commercially available PA0 or HVI-PA0 prepared as subsequently described. The conventional PA0 is typically prepared by Lewis acid or Ziegler catalyst initiated oligomerization of linear l-alkenes and can be obtained from commercial sources. The more commonly available commercial PA0 is prepared by oligomeri~ation of l-decene with aluminum chloride catalyst. The oligomer contains a preponderance of C short chain alkyl branches of less than 8 carbon atoms.
HVI-PA0 oligomers used as starting material in the present invention are prepared by the oligomerization of C6-C20 alpha-olefins in contact with reduced valence state chromium oxide catalyst on porous support. It has been found that the process described herein to produce the HVI-PA0 oligomers can be controlled to yield oligomers having weight average molecular weight between 420 and 60,000 and number average molecular weight between 420 and 24,000. Measured in carbon numbers, molecular weights range from C24 to C5000, with 3s number-averaged molecular weight of C30 to C2l00 and a preferred range of C30 to Cl400. Molecular weight WO93/lO0~ 2 1 2 3 4 2 6 PCT/US9l/08783 distributions, defined as the ratio of weight averaged molecular to number averaged molecular weight, range from 1.00 to 5, with a preferred range of 1.01 to 3.
l-hexene HVI-PAO oligomers of the present inven-tion have been shown to have a very uniform linear C4branch and contain regular head-to-tail connections indicative of the following structure as confirmed by NMR:
(-CH-CH-)n (CH2)3 The oligomerization of l-decene by reduced valence state, supported chromium also yields a HVI-PAO with a structure analogous to that of 1-hexene oligomer. The lubricant products after distillation to remove light fractions and hydrogenation have characteristic C-13 NMR
spectra confirming regular head-to-tail oligomerization of the alpha-olefin to produce a structure with mainly large alkyl group branches.
In general, the HVI-PAO oligomers have the following regular head-to-tail structure where n can be 3 to 17:
- ( CH2 -C~ ) x (CH2)n with some head-to-head connections. `~
Olefins suitable for use as starting material in the preparation of HVI-PA0 include those olefins containing from 2 to 20 carbon atoms such as ethylene, propylene, l-butene, l-pentene, l-hexene, l-octene, l-decene, l-dodecene and l-tetradecene and branched chain isomers such as 4-methyl-1-pentene. Also suitable for use are olefin-containing refinery feedstocks or effluents. However, the olefins used are preferably alpha-olefinic as for example l-heptene to l-hexadecene and more preferably l-octene to l-tetradecene, or mixtures of such olefins.

WOg3/l~K~ 212 3 ~ 2 G PCT/US91/08783 HVI-PAO oligomers of alpha-olefins have a low branch ratio of less than O.l9 and superior lubricating properties compared to the alpha-olefin oligomers with a high branch ratio, as produced in all known commercial methods. HVI-PA0 alpha-olefin oligomers are prepared by oligomerization reactions in which a major proportion of the double bonds of the alpha-olefins are not iæomerized.
These reactions include alpha-olefin oligomerization by supported metal oxide catalysts, such as Cr compounds on silica or other supported IUPAC Periodic Table Group VIB
compounds. The catalyst most preferred is a lower valence Group VIB metal oxide on an inert support.
Preferred supports include silica, alumina, titania, silica alumina, magnesia and the like. -~
The branch ratios used to characterize HVI-PAO are defined as the ratios of CH3 groups to CH2 groups in the lube oil calculated from the weight fractions of methyl groups obtained by infrared methods, as published in AnalYtical Chemistrv, Vol. 25, No. lO, p. 1466 (1953). ~-Branch ratio = wt fraction of methyl aroup l-(wt fraction of methyl group) The supported metal oxide catalysts are preferably prepared by impregnating metal salts in water or organic solvents onto the support. Any suitable organic solvent known to the art may be used, for example, ethanol, methanol, or acetic acid. The solid catalyst precursor 2s is then dried and calcined at 200 to ~OO^C by air or other oxygen-containing gas. Thereafter the catalyst is reduced by any of several various and well known reducing agents such as, for example, C0, H2, NH3, H2S, CS2, CH3SCH3, CH3SSCH3, metal alkyl containing compounds such as R3Al, R3B, R2Mg, RLi, R2Zn, where R is alkyl, alkoxy, aryl and the like. Preferred are C0 or H2 or metal alkyl containing compounds.

e 2123~126 8 Alternatively, the Group VIB metal may be applied to the substrate in reduced form, such as CrII compounds.
The res~ltant catalyst is very active for oligomerizing olefins at a temperature range from below room temperature to 500 C at a pressure of 10 to 34,580 kPa (0.1 atmosphere to 5000 psi). Preferably the oligomer-ization is carried out at a temperature between 90 and 250-C. Contact time of both the olefin and the catalyst can vary from one second to 24 hours. Very low catalyst concentrations based on feed, from 10 wt % to 0.01 wt %, are used to produce oligomers. The catalyst can be used in a batch type reactor or in a fixed bedl continuous flow reactor.
The following examples are presented to illustrate the preparation of the HVI-PAO catalyst and oligomeriza-tion process.

Example 1 Catalvst Preparation and Activation Procedure 1.9 grams of chromium (II) acetate (Cr2(OCOCH3)42H2O) (5.58 mmole) (COD ercially obtained) is dissolved in 50 ml of hot acetic acid. Then 50 grams of a silica gel of 8-12 mesh size, a surface area of 300 m2/g, and a pore volume of 1 ml/g, also is added. Most of the solution is absorbed by the silica gel. The final mixture is mixed for half an hour on a rotavap at room temperature and dried in an open-dish at room tempera-ture. First, the dry solid (20 g) is purged with N2 at 250C in a tube furnace. The furnace temperature is then raised to 400C for 2 hours. The temperature is then set at 600C with dry air purging for 16 hours. At this time the catalyst is cooled under N2 to a temperature of 300C. Then a stream of pure CO (99.99~ from Matheson) is introduced for one hour. Finally, the catalyst is cooled to room temperature under N2 and ready for use.

~123~2~
g Example 2 A commercial chrome/silica catalyst which contains 1% Cr on a large-pore volume synthetic silica gel is used. The catalyst is first calcined with air at 800C
for 16 hours and reduced with C0 at 300C for 1.5 hours.
Then 3.5 g of the catalyst is packed into a tubular reactor and heated to 100C under the N2 atmosphere.
Purified l-decene is pumped through the reactor at 1830 to 2310 kPa (250 to 320 psi). The product is collected periodically and stripped of light products having boiling points below 343 C (650-F). High quality HVI-PA0 lubes with high VI are obtained as presented in the following table.

Reaction WHSV Lube Product Properties Temp.-C q/a/hrV at 40 C V at lOO C VI
120 2.51555.4cs 157.6cs 217 135 0.6 389.4 53.0 202 150 1.2 266.8 36.2 185 166 0.6 67.7 12.3 181 197 0.5 21.6 5.1 172 In the process of the instant invention the HVI-PA0 oligomer is converted to oligomer containing aromaticity in the structure of the oligomer molecule by treating the HVI-PAo with dehydrocyclization. In the process a portion of the pendant alkyl groups of the oligomer are ring-closed and dehydrogenated to form aromatic ring structures. Depending upon the dehydrocycli~ation conditions employed it has been discovered that up to 5 wt % aromatic structures can be incorporated into the HVI-PAo molecular structure.

WO 93/10066 PCl/US91/08783 2123~26 Preferably, the dehydrocyclization reaction is performed on HVI-PAO oligomers produced from C8-C14 alpha-olefins, with l-decene a most preferred alpha-olefin material to produce poly-l-decene oligomer.
C-13 NMR analysis of the products of the dehydro-cyclization process of the present invention confirm that the products comprise liquid lubricant hydrocarbon having the recurring polymeric structure ~-CH2-CH-~n~~CH2~cH~]m where x is 5 to311, n is less than 500 and the -ra~io of n to m is between 200 and 20; wherein R contains x+l carbon atoms comprising aryl, aralky} or alkylaryl.
For the particular case of the dehydrocyclization of poly-l-decene produced by the HVI-PA0 process C-13 NMR
analysis supports the conclusion of the aforestated ;-structure where x is equal to 7. The poly-l-decene dehydrocyclization product has a viscosity of at least 2cS at lOO-C and a viscosity index of at least 130.
The catalysts used to affect the dehydrocyclization reaction of poly-alpha-olefin oligomers in the present invention includes those typically and conventionally employed to affect dehydrocyclization of alkanes, well known to those skilled in the organic chemical arts. These include Group VIII metals of the CAS version of the Periodic Table of the Elements, in particular platinum and palladium. Such catalysts are included on a solid support structure which may be taken from materials such as alumina, silica, clays, charcoal and zeolites. In the present invention zeolites and, more particularly, large pore zeolites have been found useful. Such zeolites include Beta, ZSM-12, Y, which possess a Constraint Index no greater than 2 with alpha values ranging between 1 and 100.
A convenient measure of the extent to which a zeolite provides controlled access to molecules of WO93/10066 2 1 2 3 ~ 2 ~ PCT~US91/08783 varying sizes to its internal structure is the aforementioned Constraint Index of the zeolite. The method by which Constraint Index is determined is described fully in U.S. Patent No. 4,016,218, to which reference is made for details of the method.
The zeolite(s) selected for use herein will -~
generally possess an alpha value of at least 1, `
preferably at least 10 and more preferably at least 50.
"Alpha value", or "alpha number", is a measure of zeolite acidic functionality and is more fully described together with details of its measurement in U.S. Patent No. ~
4,~16,218, J. CatalYsis, 6, pp. 278-287 (1966) and J. ;-Catalysis, 61, pp. 390-396 (1980). Zeolites of low acidity (alpha values of less than 200) can be achieved -`
by a variety of techniques including (a) synthesizing a zeolitè with a high silica/alumina ration, (b) steaming, (c) steaming followed by dealuminization and (d) substituting framework aluminum with other species. For example, in the case of steaming, the zeolite(s) can be exposed to steam at elevated temperatures ranging from 260 to 650-C (500- to 1200-F) and preferably from 399- to S38-C (750 to lOOO-F). This treatment can be accomplished in an atmosphere of 100% steam or an atmosphere consisting of steam and a gas which is substantially inert to the zeolite. A similar treatment can be accomplished at lower temperatures employing elevated pressure, e.g., at from 177 to 371C (350 to 700F) with from 1,010 to 20,200 kPa (10 to 200 atmospheres). Specific details of several steaming procedures may be gained from the disclosures of U.S.
Patent Nos. 4,325,994; 4,374,296: and 4,418,235.
It has been discovered that a particularly useful catalyst for the process comprises zeolite Beta bound with approximately 35 wt % alumina and containing 0.6%
platinum. This catalyst was steamed to yield an effective catalyst for dehydrocyclization having an alpha value of 50.

The process of the present invention can be run under aromatization conditions which include hydrogen feed or flow to the reactor. Hydrogen can be co-fed at a rate between 0 and 900 v/v (0 and 5000 SCF/BBL).
However, as illustrated in Figure l, the hydrogen flow rate effects the degree of aromatization achieved. The highest aromatic content is to be found when hydrogen flow rate is zero as shown in Figure 1. Hydrogen flow rate also affects the degree of residual unsaturation remaining in the product following dehydrocyclization.
The starting material HVI-PA0 typically contains at least `;~
one olefinic group per oligomer molecule. The degree to which this unsaturation is eliminated in the final product is influenced by hydrogen flow rate as shown in ~-Figure 2. At high hydrogen flow rates bromine numbers less than l are achieved whereas at no hydrogen flow the bromine number for the poly-l-decene HVI-PA0 - aromatization product is greater than 6.
- It has been determined that the process of this invention can be conducted at temperatures between 50-and 700-C, press~res between 940 and 7000 kPa (20 and 1000 psig) and liquid hourly space velocity (L~SV) between 0.1 and 10. Preferably, the dehydrocyclization conditions comprise a temperature between 100- and 300~C, a pressure between 2170 and 4240 kPa (300 and 600 psig), and LHSV between 0.4 and l.
The following Examples illustrate the dehydro-cyclization process of the present invention and the properties of the products produced therefrom. The Examples are presented strictly for illustration purposes and are not intended to limit the scope of the invention.
The feedstock used in Examples 3-6 is HVI-PA0 liquid lubricant and prepared in a fixed bed reactor according to the procedures previously described. The 3S oligomerization conditions and properties of the l-decene WO93/10~6 212 3 '~ 2 ~3 PCT/US91/08783 HVI-PA0 oligomer starting material produced in a fixed bed reactor are as follows: reaction temperature 165~C, pressure 380 kPa (40 psig), WHSV 2.5, lube yield 63.6~, viscosity at 40-C 130.4 cS, viscosity at lOO-C 19.7 cS, viscosity index 173.1.
In Examples 3-6 the dehydrocyclization process carried out on the feedstock was conducted in a fixed bed reactor containing an aromatization catalyst comprising ;~
zeolite Beta containing 35 wt % alumina and 0.6 wt ~ ;~
platinum. The catalyst is steamed to an alpha value of 50. All of the experiments are conducted at 0.5 LHSV and a unit pressure of 2860 kPa (400 psig). The hydrogen flow rate to the reactor is varied between 0 and 900 v/v (0 and 5000 SCF/B8L). Specific experimental conditions and properties of the product produced are described in Table 1.

Example Feed3 4 5 6 Reactor Temp. 124(256) 129(264)129(264) 146(295) C(-F) LHSV ~.48 0.51 0.50 O.S0 Pressure, kPa 2860(~00) 2860(400) 2860(400) 2860(400) (psig) H2 Flow,ml/min 21 0 80 75 Yieldj wt % 83.3 92.5 40.0 46.7 Bromine No. 10.5 3.9 6.6 0.5 1.0 Color Clear Brown BrownYellow Yellow KV, 40 C 30.4 186.1 191.4 151.1 277.2 KV, 100C 19.7 26.1 25.8 22.9 34.2 Visc. Index 173.1 175.2 168.7 181.1 169.5 Wt % Aromatic 0.0 2.2 3.2 1.3 0.5 From the above data it is evident that a significant degree of aromaticity can be incorporated in HVI-PAO by the described process. As shown in Table 1, and as previously noted, aromatic structure formation varies as a function of hydrogen flow rate with the highest aromatic content achieved under conditions of no hydrogen flow. Remarkably, the viscosity indices of the aromatized HVI-PA0 remains high with little or no decrease compared to the viscosity index of the starting material. Also, under conditions of high hydrogen flow WO93/10~6 PCT/US91/08783 2123~26 14 rate to the dehydrocyclization zone or reactor there is an appreciable reduction in bromine number signifying concurrent hydrotreatment as well as aromatization of the HVI-PA0 oligomer. Accordingly, those products with lowered bromine numbers can avoid subsequent ~;
hydrotreatment typically employed to stabilize the lubricant product.
These Examples serve to illustrate that between 0.4 and 5 wt % of aromatic structure, based on total product weight, can be incorporated into HVI-PA0 to provide new compositions as determined by C-13 NMR.
T~ese are new liquid lubricant compositions comprise C24-C5000 hydrocarbons, said composition having a branch ratio of less than O.l9, weight average molecular weight between 420 and 60,000, number average molecular weight between 420 and 24,000, molecular weight distribution between l and 5, pour point below -15-C and containing between 0.4 and 4 wt ~ of aromatic structure.
Although the present invention has been described with preferred embodiments, it is to be understood that modifications and variations may be resorted to, without departing from the spirit and scope of this invention, as ' those skilled in the art will readily understand. Such modifications and variations are considered to be within the purview and scope of the appended claims.

Claims (25)

CLAIMS:

1. A process for producing an polyalpha-olefin containing aromatic structures by the dehydrocyclization of polyalpha-olefin, comprising:
contacting a polyalpha-olefin produced by the oligomerization of a C6-C20 olefin with dehydrocycliza-tion catalyst in a dehydrocyclization reaction zone under dehydrocylclization conditions whereby modified polyalpha-olefin is produced which contains aromatic structure attached as pendant groups to the backbone of the polyalpha-olefin structure.

2. The process of Claim 1 wherein a polyalpha-olefin comprises the product of the oligomerization of alpha olefins containing 6 to 20 carbon atoms, or mixtures of such olefins; an oligomerization comprising: contacting olefins under oligomerization conditions, at reaction temperature of 90° to 250°C with a chromium catalyst on a porous support, which catalyst has been treated by oxidation at a temperature of 200° to 900°C in the presence of an oxidizing gas and then by treatment with a reducing agent at a temperature and for a time sufficient to reduce catalyst to a lower valence state; to obtain an oligomeric liquid lubricant composition comprising C30-C1300 hydrocarbons, said composition having a branch ratio of less than 0.19, weight average molecular weight between 420 and 45,000, number average molecular weight between 420 and 18,000, molecular weight distribution between 1 and 5 and pour point below -15°C.

3. The process of Claim 2 wherein the liquid lubricant composition has a viscosity index greater than 130.

4. The process of Claim 2 wherein the reducing agent comprises CO and the oligomerization temperature is 100° to 180°C.

5. The process of Claim 2 wherein the support comprises porous silica.

6. The process of Claim 2 wherein the olefin consists essentially of 1-octene, 1-decene, 1-dodecene, 1-tetradecene or mixtures thereof.

7. The process of Claim 1 wherein the dehydrocyclization catalyst is selected from supported Group VIII metals of the Periodic Table and zeolites ZSM-5, ZSM-12, Y, Beta containing the metals, wherein the support is selected from alumina, silica, clays and charcoal.

- 8. The process of Claim 1 wherein the dehydrocyclization catalyst comprises zeolite Beta on alumina support containing platinum, the catalyst having an alpha value of 50.

9. The process of Claim 1 wherein the dehydrocyclization conditions comprise temperature between 50° and 700 C, pressure between 240 and 7000 kPa, LHSV between 0.1 and 10.

10. The process of Claim 1 further comprising cofeeding hydrogen with the polyalpha-olefin to the dehydrocyclization zone.

11. The process of Claim 10 wherein the hydrogen is co-fed at a rate between 0 and 900 v/v.

12. The process of Claim 1 wherein the modified polyalpha-olefin comprises a liquid hydrocarbon lubricant having viscosity at 100°C greater than 2cS and VI greater than 130.

13. The process of Claim 1 wherein the modified polyalpha-olefin aromatic structure comprises between 0.4 and 4 weight percent.

14. A liquid lubricant composition comprising C20-C5000 hydrocarbons, the composition having a branch ratio of less than 0.19, weight average molecular weight between 420 and 60,000, number average molecular weight between 420 and 24,000, molecular weight distribution between 1 and 5, pour point below -15°C and containing between 0.4 and 4 wt % of aromatic structure.

15. The composition of Claim 14 having a VI
greater than 130.

16. The composition of Claim 14 wherein the hydrocarbons have the recurring polymeric structure where x is 5 to 11, n is less than 500 and the ratio of n to m is between 200 and 20; wherein R contains x+1 carbon atoms comprising aryl, aralkyl or alkylaryl.

17. The composition of Claim 16 wherein x is 7, the composition having a viscosity at 100°C of at least 2cS with VI greater than 130.

18. A process for introducing aromaticity into the structure of high VI liquid lubricant hydrocarbon, comprising:
contacting the product of the oligomerization of C6 to C20 alpha-olefin feedstock, or mixtures thereof, under oligomerization conditions in contact with a reduced valence state Group VIB metal catalyst on porous support, the product comprising lubricant having a branch ratio less than 0.19, viscosity index greater than 130 and a pour point less than -15°C, with an aromatization catalyst comprising Group VIII metal on solid support in an aromatization zone under aromatization conditions, whereby a liquid lubricant containing aromatic structure is produced.

19. The process of Claim 18 wherein the liquid lubricant product has a viscosity index greater than 130 and viscosity greater than 2cS at 100°C.

20. The process of Claim 18 wherein the aromatization catalyst is selected from supported metals platinum and palladium and zeolites ZSM-5, ZSM-12, Y, Beta containing the metals, wherein the support is selected from alumina, silica, clays and charcoal.

21. The process of Claim 18 wherein the aromatization catalyst comprises zeolite Beta on alumina support containing platinum, the catalyst having an alpha value of 50.

22. The process of Claim 18 wherein the aromatization conditions comprise temperature between 50 and 700°C, pressure between 138 and 7000 kPa, LHSV
between 0.1 and 10.

23. The process of Claim 18 further comprising co-feeding hydrogen with the polyalpha-olefin to the dehydrocyclization zone.

24. The process of Claim 23 wherein the hydrogen is co-fed at a rate between 0 and 900 v/v.

25. The process of Claim 18 wherein the liquid lubricant product aromatic structure comprises between 0.4 and 4 wt % of the product.