|1.||A lubricant additive composition comprising the adduct of an olefinic oligomer and an enophile, the olefinic oligomer comprising the product of the oligomerization of C2 to C^ alphaolefin feedstock, or mixtures thereof, under oligomerization conditions in contact with a reduced valence state Group VIB metal catalyst on porous support, the adduct having the structure: Λ9 where R, through R£ are hydrogen, alkyl or alkenyl and the sum of carbon atoms of all R, through Rg groups totals at least 17, where at least one of Rg and Rg is an electronegative group taken from the group consisting essentially of " ■• C 0 ; where A is 0, S, N or NR where R is alkyl, aryl, alkenyl or polyal kenyl amine; " 0 ** CZ" where Z is H, OH, NH«, halogen, alkyl, aryl, benzyl and groups such as CN, N02, aryl, benzyl, CH2CN, CH2X where % . is , halogen; ° _COQ where Q is alkyl, aryl or benzyl and; with the remaining groups of Rg through Rg taken from the electronegative group or hydrogen, alkyl, alkenyl, alkynalkyl, aryl or aralkyl; and the enophile having the structure: where at least one of Rg, Ry, R« and Rg is the electronegative group and the remaining groups are hydrogen, alkyl , alkenyl , alkynalkyl, aryl or aralkyl .|
|2.||The composition of claim 1 wherein the catalyst is chromium oxide on silica support reduced with carbon monoxide.|
|3.||The composition of claim 1 wherein the oligomerization is carried out at a temperature between 90°C and 250°C.|
|4.||The composition of claim 1 wherein the oligomer has a branch ratio of less than 0.19, weight average molecular weight between 300 and 45,000, number average molecular weight between 300 and 18,000, molecular weight distribution between 1 and 5 and pour point below 15°C.|
|5.||The composition of claim 1 wherein the adduct comprises the olefin hydrogenation product of the adduct of the enophile and the olefinic oligomer.|
|6.||The composition of claim 1 having the structure: comprising maleic anhydride adduct of the oligomer and acidic or amido reaction products thereof with water, ammonia or amines, where R is hydrogen, alkyl or alkenyl and the total number of carbon atoms in all R groups is at least 17.|
|7.||The composition of claim 5 having the structure: | H |j . • RCCCCCH ή ή ft AA. 0 0 0 and acidic or amido reaction products thereof with water, ammonia or amines and where R is hydrogen, alkyl or alkenyl and the total number of carbon atoms in all R groups is at least 17.|
|8.||The composition of cl aim 6 having the structure comprising the alkenyl bissuccinimide reaction product of the maleic anhydride adduct and tetraethylene pentamine.|
|9.||A process for the production of lubricant additive compositions comprising the adduct of an olefinic oligomer and an enophile, the olefinic oligomer comprising the product of the oligomerization of C2 to C24 alphaolefin feedstock, or mixtures thereof, under oligomerization conditions in contact with a reduced valence state Group VIB metal catalyst on porous support, compr sing; reacting the olefinic oligomer and enophile in a reaction zone at a temperature between 40 and 400 C; separating effluent from the reaction zone whereby the adduct is produced.|
|10.||The process of claim 9 wherein the olefinic oligomer and the enophile are reacted in contact with a Lewis acid catalyst.|
|11.||The process of claim 9 comprising the further step of hydrogenating the adduct in contact with hydrogenating catalyst and hydrogen at temperature between 20 and 300°C whereby olefin hydrogenated adduct of the oligomer and enophile is produced.|
|12.||The process of claim 9 wherein the enophile comprises maleic anhydride and the olefin oligomer comprises oligomer from oligomerization of 1decene.|
|13.||A process for the production of alkenyl bissuccinimide from the adduct of an olefinic oligomer and maleic anhydride, the olefinic oligomer comprising the product of the oligomerization of C2 to C24 alphaolefin feedstock, or mixtures thereof, under oligomerization conditions in contact with a reduced valence state Group VIB metal catalyst on porous support, comprising: reacting the adduct in a reaction zone at a temperature of 204°C with a polyamine containing at least two primary amine groups; separating effluent from the reaction zone whereby the alkenyl bissuccinimide is produced.|
|14.||The process of claim 13 wherein the polyamine comprises tetraethylene pentamine and the alkenyl bissuccinimide has the structure RC=C where R is hydrogen, alkyl or alkenyl and the total number of carbon atoms in all R groups is at least 17.|
|15.||A process for the production of an alkenylsuccinic anhydride derivative of an adduct of maleic anhydride and an olefin oligomer comprising the oligomerization product of a C2 to C2 alphaolefin feed, produced under oligomerization conditions in contact with a catalyst comprising a reduced valence state Group IVB metal catalyst on a porous support, by reacting the adduct with an active hydrogencontaining compound.|
|16.||The process according to claim 15 wherein the active hydrogencontaining compound contains one or more amino groups.|
|17.||The process of claim 16 wherein the amino groups comprise amine or polyamine.|
|18.||The process of claim 16 wherein the active hydrogencontaining compound comprises hydroxyl or polyhydroxyl compounds.|
|19.||The process of claim 18 wherein the active hydrogencontaining compound comprises hindered polyols or a bifunctional active hydrogen compound.|
|20.||The process of claim 19 wherein the bifunctional compound comprises a compound having amine and hydroxyl functionality.|
|21.||The process of claim 20 comprising hydroxyl alkyl amines.|
This invention relates to novel coπpositions useful as lubricant additives having polar _!uι_ctional groups. In particular, the invention relates to novel lubricant additive compositions and methods for their preparation from unique synthetic hydrocarbon lubricants that exhibit a higji viscosity index.
The formulation of lubricants typically includes an additive package incorporating a variety of chemicals to iBprove or protect lubricant properties in application specific situations, particularly internal rartoustion engine and machinery applications. The more c rmonly used additives include oxidation inhibitors, rust inhibitors, antiwear agents, pour point depressants, detergent-dispersants, viscosity index (VI) improvers, foam inhibitors and the like, ϊhis aspect of the lubricant arts is specifically described in Kirk--Oϋ)mer "Encyclopedia of Chemical Technology", 3rd edition, Vol. 14, pp477-526. Considering the diversity of chemical strictures represented by the plethora of additives incorporated in a typical lubricant forπulation, and the quantity in which they are added, the artisan in the lubricant formulation arts faces a substantial challenge to provide a homogeneous formulation which will remain stable or in solution during inventory and during use. lubricants, particularly synthetic lubricants of the type of interest in the instant invention, are usually hydrogenated olefins. Due to their hydrocarbon structure they are largely incompatible with polar additives such as antioxidants, antirust and antiwear agents,etc. Acco__dingly, in order to render the lubricants ccπpatible with the polar additives large amounts of expensive polar organic esters must be added to the formulation. Useful coπinercial formulations may contain 20% percent or more of such esters as bis-tridecanol adipate for example, solely to provide a fully homogeneous lubricant blend of lubricant and additive.
ffadifying the solvent properties of lubricants with solubilizing agents such as organic esters, while solving the problem of how to prepare stable blends with lubricant additives, creates or accentuates other performance related problems beyond the added burden on cost of the product. The vulnerability of solubilizing agents to oxidative degradation prcπoting the formation of tars and gums must be taken into account. Seal swelling properties may be changed. Seal swell measures the ability of a lubricant to swell a seal, thus enhancing its sealing function. Solubilizing agents may effect viscαnetric properties such as -viscosity and viscosity index of the material. When materials deficient in these properties are added in large amounts, the lubricant's effectiveness will be iπpaired. In view of these ccrplications it is evident that novel approaches are called for in the modification or formulaticti of lubricants to incorporate additives without cuiipromising properties or adding significantly to the cost of the product.
One approach to iπprove lubricant cx-rcfatibility with additives is to add polar groups to the structure of the lubricant. lubricants, in particular synthetic lubricants, are kncwn to contain olefinic unsaturation and it has been determined in the present invention that such unsaturation can be effectively utilized to react with polar groups to add a polar ___un__tiGnality on to the lubricant molecule. The added polar group in the lubricant has sufficient solubilizing character to adequately dissolve additive packages without the addition of solubilizing agents such as adipate esters. It has been discovered in the instant invention that the necessary -.- • urtctionality i.e., functional group, can be added to the lubricant by .reacting the lubricant olefinic group with an electronegative enophile. Depending -upon the structure of the molecule added to the olefin unsaturation of the lubricant other property .utprovemeπts typical of additive packages may also be conferred upon the lubricant mixture.
Recently, lubricant σcupositions (referred to herein as HVT-PAO and the HVT-PAO process) coπprising polyalpha-olefins and methods for their preparation employing as catalyst reduced chromium on a silica support have been disclosed in U.S. Patents 4,827,064 and 4,827,073. The process cαrprises contacting C--C 20 1-alkene feedstock with reduced valence state chromium oxide catalyst on porous silica support under oligomerizing conditions in an oligcmerizatiαn zone whereby hiφ viscosity, high viscosity index (VI) liquid hyd__ocar_x_n lubricant is produced having branch ratios, i.e. OL/OL, less than 0.19 and pour point below -15°C. The process is distinctive in that little isomerization of the olefinic bond occurs compared to known oligomerization methods to produce polyalpha-olefins using Lewis acid catalyst. lubricants produced by the process cover the full range of lubricant viscosities and exhibit a ranarkably hiφ viscosity index (VI) and low pour point even at hiφ viscosity. The as-synthesized HVT-PAO oligomer has a preponderance of terminal olefinic unsaturation or exo-olefinic groups, e.g., viπylidene groups.
It has been found that unsaturated C_ n + HVT-PAO lubricant range hydrocarbons containing an allylic hydrogen will react thermally or catalytically by addition to an alkene which contains olefinic -unsaturation in the alpha,beta position to an electronegative group when the C 2Q + HVT-PAO unsaturated lubricant has the following structure αcπprising one or more allylic hydrogens:
where R_ , R_, R_, R. and R^ may be hydrogen, alkyl or alkeπyl and at least 17 carbon atoms in total. In a preferred embodiment R. and R_ are hydrogen and the unsaturated olef in is a vinlyidene group c πprising a terminal group of the HVT-PAO hydrocarbon molecule.
The alpha, beta unsaturated alkenes useful in the present .invention include all those having the st__ucture:
where at least one of R-, R_, R g and L is an electronegative group and the remainder hydrogen, alkyl, alkeπyl, alkynalkyl, aryl or aralkyl. These st__uctures are referred to herein,* as in the organic chemical arts, as enophiles. Maleic anhydride ia a preferred enophile.
More particularly, a polar lubricant ccnposition has been found which comprises the adduct of the above urisaturated lubricant and unsaturated alkene and having the structure:
where at least one of R_ or R_ is an electronegative group and
• t <. o y the -remainder R-, R_, R- and R. is an electronegative group or hydrogen., allcj^L, alkeπyl, alkynalkyl, aryl or aralkyl and R_, R,, R_, R. and _ is hydrogen, alkyl or alkeπyl at least one of which is G, 7 + alkyl or alkeπyl group. Where the xmsaturated C 2Q + HVT-PAD lubricant molecule contains multiple allylic groups more than one mole of enophile can react with the lubricant to form an adduct c_onta__πing more than one elect__ * or_egative group or multiple polar sites.
Typically, the product of the iπveπtica cx_πtaining olefinic unsaturation exhibits useful properties for additive applications and can be used as an additive without further change. However, hydrcge__at_Lc_n of the olefinic bonds of the adduct yields a polar product also with useful properties for additives applications, e.g., dispersant properties.
The HVT-PAO -unsaturated lubricant eπployed in the present invention cnprises a liquid lubricant hydrocarbon ccπposition
comprising the polymeric residue of 1-alkenes selected from linear C g - C 2Q 1-alkenes, said composition having a branch ratio of less than 0.19, weight average molecular weight between 300 and 45,000, number average molecular weight between 300 and 18,000, molecular weight distribution between 1 and 5 and pour point below -15°C.
The formation of the HVI-PAO adduct between C 2Q + olefinic lubricant and an enophile is accomplished in the present invention by heating the mixture at elevated temperature or by reaction catalyzed by a Lewis acid such as BF, or A1C1-.
The olefinic lubricants useful in the present invention in the formation of adducts with enophiles include all those unsaturated HVI-PAO lubricants having 20 to 5000 carbon atoms where one or more of the unsaturated groups is allylic unsaturation. To be useful in the present invention all such lubricant molecules must contain one or more olefinic group of the following structure:
where R,, R« ,R 3 , R, and R ς may be hydrogen, alkyl or alkenyl and at least 17 carbon atoms in total for the sum of carbon atoms in R., R„ ,R,, R. and R,-. The olefinic bond may be in the alpha position, i.e., a vinyl structure where R, and R« are hydrogen, or the bond may be an internal olefin where R, ,R 2 ,R 3 , R, and/or
R 5 is an aliphatic hydrocarbon. Preferably the olefinic group comprises a vinylidene group of the structure CH 2 =CR 2 where R is the HVI-PAO moiety. Since lubricants comprise a mixture of molecules usually having a wide range of molecular weights certain molecules may contain more than one olefinic bond, including alpha olefins and internal olefins of allylic structures. It is to be expected then that certain lubricant molecules may be produced according to this invention containing
multiple adducts with specific enophiles, fol lowing reaction at multiple olefinic sites in the unsaturated l ubricant molecule. As ol igomerized, HVI-PAO ol igomers are mixtures of dial kyl vinyl idenic and 1 ,2 dialkyl or tri alkyl mono-olefins. In general , the novel HVI-PAO ol igomers have the following regul ar head-to-tail structure where n can be 3 to 17:
with some head-to-head connections. It has been found that t_»he process described herein to produce the HVI-PAO oligomers. used in the present invention can be controlled to yield oligomers having weight average molecular weight between 300 and 45,000 and number average molecular weight between 300 and 18,000. Measured in carbon numbers, molecular weights range from C 30 to C, 300 and viscosity up to 750 mm /s (750cs) at 100°C, with a preferred range of C 3Q to , 000 and a viscosity of up to 500 mm s (500cs) at 100°C. Molecular weight distributions (MWD), defined as the ratio of weight average molecular to number average molecular weight, range from 1.00 to 5, with a preferred range of 1.01 to 3 and a more preferred MWD of about 1.05 to 2.5. Olefins suitable for use as starting material to prepare unsaturted HVI-PAO oligomers for this invention include those olefins containing from 2 to 24 carbon atoms such as ethylene, propylene, 1-butene, 1-pentene, 1-hexene, 1-octene, 1-decene, 1-dodecene and 1-tetradecene and branched chain iso ers such as 4-methyl-l-pentene. Also suitable for use are olefin-containing refiner feedstocks or effluents. However, the olefins used are preferably alphaolefinic as for example 1-heptene to 1-hexadecene and more preferably 1-octene to 1-tetradecene, or mixtures of such olefins. HVI-PAO oligomers of alpha-olefins have a low branch ratio of less than 0.19 and superior lubricating properties compared to the alpha-olefin oligomers with a high branch ratio, as produced in all known commercial methods.
HVI-PAO oligomers are prepared by oligomerization reactions in which a major proportion of the double bonds of the alphaolefins are not iso erized. 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 support material binds the metal oxide catalyst. Those porous substrates having a pore opening of at least 40 x 10 mm (40 angstroms) are preferred.
The support material usually has high surface area and large pore volumes with average pore size of 40 to 350 x 10 mm (40 to 350 angstroms). The high surface area is beneficial for support- ing large amounts of highly dispersive, active chromium metal centers and to give maximum efficiency of metal usage, resulting in very high activity catalyst. The support should have large average pore openings of at least 40 x 10 " mm (40 angstroms), with an average pore opening of >60 to 300 x 10 mm (>60 to 300 angstroms) being preferred. This large pore opening will not impose any diffusional restriction of the reactant and product to and away from the active catalytic metal centers, thus further optimizing the catalyst productivity. Also, for this catalyst to be used in fixed bed or slurry reactor and to be recycled and regenerated many times, a silica support with good physical strength is preferred to prevent catalyst particle attrition or disintegration during handling or reaction.
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 is then dried and calcined at 200 to 900°C by air or other oxygen-containing gas. Thereafter the catalyst is reduced by any of various, well known reducing agents such as,
for example, CO, H 2 , H 3 , H 2 S, CS 2 , CH 3 SCH 3 , CH 3 SSCH 3 ,metal alkyl containing compounds such as R-Al, R 3 B,R 2 Mg, RLi, R 2 ∑n, where R is aTtξ l, alkoxy, aryl and the like. Preferred are CO or H 2 or metal.alkyl containing compounds. Alternatively, the Group VIB meta] may be appl ed to the substrate in reduced form, such as CrII porapounds.The resultant catalyst is very active for oligomerizing olefins at a temperature range from below room temperature to 250°C at a pressure of 10 kPa to 34580 kPa (0.1 atmosphere to 5000 psi). Contact time of both the olefin and the catalyst can vary from one second to 24 hours. The catalyst can be used in. a batch type reactor or in a fixed bed, continuous-flow reactor.
In general the support material may be added to a solution of the metal compounds, e.g., acetates or nitrates, etc., and the mixture is tfien mixed and dried at room temperature. The dry solid gel is purged at successively higher temperatures to about 600 * C for a period of about 16 to 20 hours. Thereafter the catalyst is cooled under an inert atmosphere to a temperature of 250 to.45 * 0°C and a stream of pure reducing agent is contacted therewith for. a period when enough CO has passed through to reduce the catalyst as indicated by a distinct color change from bright orange to pale blue. Typically, the catalyst is treated with -an amount of CO equivalent to a two-fold stoichiometric excess to reduce the catalyst to a lower valence CrII state. Finally the catalyst is cooled down to room temperature and is ready for-use.
The product oligomers have a very wide range of viscosities with high viscosity indices suitable for high performance lubrication use. The product oligomers also have atactic molecular strαcture of mostly uniform head-to-tail connections with some head*-to-head type connections in the structure. These low branch ratio oligomers have high viscosity indices at least about 15 to 20 units and typically 30-40 units higher than equivalent viscosity prior art oligomers, which regularly have
higher branch ratios and correspondingly lower viscosity indices.
These low branch oligomers maintain better or comparable pour points.
The branch ratios defined as the ratios of CH, groups to CH 2 groups in the lube oil are calculated from the weight fractions of methyl groups obtained by infrared methods, published in
Analytical Chemistry. Vol. 25, No. 10, p. 1466 (1953).
Branch ratio = wt fraction of ethyl group l-(wt fraction of methyl group)
To produce the HVI-PAO low molecular weight products suitable for use in the present invention the reaction is carried out at a temperature of 90-250°C.
The following examples are presented for illustration of the preparation of HVI-PAO unsaturated oligomers used in the instant invention. Example 1 Catalyst Preparation and Activation Procedure
1.9 grams of chromium (II) acetate (Cr 2 (OCOCH 3 ) 4 2H 2 0) (5.58 mmole) (commercially obtained) is dissolved in 50 cc of hot acetic acid. Then 50 grams of a silica gel of 8-12 mesh size, a surface area of 300 m /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 temperature.
First, the dry solid (20 g) is purged with N 2 at 250°C in a tube furnace. The furnace temperature is then raised to 400°C for 2 hours. The temperature is then set at 600°C with dry air purging for 16 hours. At this time the catalyst is cooled down under N 2 to a temperature of 300°C. Then a stream of pure CO (99.99% from Matheson) is introduced for one hour. Finally, the catalyst is cooled to room temperature under N 2 and ready for use.
Example 2 The catalyst prepared in Example 1 (3.2 g) is packed in a 9.5 mm (3/8") stainless steel tubular reactor inside an 2 blanketed
dry box. The reactor under N. atmosphere is then heated to 150°C y a single-zone Lindberg 1-hexene is pumped into the reactor at 1070 kPa (140 psi) and 20 ml hr. The liquid effluent is collected and stripped of the unreacted starting material and the lew boiling material at 6.7 Pa (0.05 ran Hg) . The residual clear, colorless liquid has viscosities and VI's suitable as a lubricant base stock.
Samole Prerun 1 2 3
T.O.S.*, hr * 2 3 . 5 5.5 21. 5
Lube Yield, wt% 10 41 74 31
Viscosity, * mm /s, , at
40 C 208.5 123 . 3 104 . 4 166 . 2
100°C 26.1 17. 1 14. 5 20.4
VI 159 151 142 143 * Time on Stream
Example 3 Similar to Example 2, a fresh catalyst sample is charged into the r,eactor and 1-^aexene is puirped to the reactor at 101 kPa (1 atm) and 10 ml per hour. As shown below, a lube of hiφ viscosities and hiφ VI's is obtained. These runs show that at different reaction conditions, a lube product of hiφ viscosities can be obtained.
Sample A B
T.O.S., hrs. 20 44
Temp. , C 100 50
Lube Yield, % 8.2 8.0 Viscosities, mm /s at
4 ore 13170 19011
100 c 620 1048
VI 217 263
Example 4 A cαπrrercial __hrcroe/silica catalyst which contains 1% Cr on a large-pore volume synthetic silica gel is used. The catalyst is first calcined with air at 800°C for 16 hours and reduced with 00 at 300°C for 1.5 hcurs. Then 3.5 g of the catalyst is packed into a tubular reactor and heated to 100°C under the N_ atπosphere. 1-Hexene is pumped throυφ at 28 cc per hour at 1 atmosphere. The products are collected and analyzed as follows:
Sample C D E F
T. O. S . , hrs . 3 . 5 4 . 5 6. 5 22
Lube Yield, % 73 64 59 21 Viscosity, mm /s, at
40 β C 2548 2429 .3315 9031 lOO ' C 102 151 197 437
VI 108 164 174 199 These runs show that different Cr an a silica catalyst are also effective for oligαmerizing olefins to lube products.
As in Example 4, purified 1-decene is pumped thrσuφ the reactor at 1830 to 2310 kPa (250 to 320 psi). The product is collected periodically and stripped of liφt products boiling points below 243 β C (650°F). Hiφ quality lubes with hiφ VI are obt ined (see following table) .
Reaction WHSV lube Product Properties
Temo. 'C σ/σ/hr V at 40*C V at lOO'C VI
120 2.5 1555.4CS 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
The alpha,beta unsaturated alkenes useful in the present invention include all those having the sta cture:
(II) R 6 -C ?=AC-R 9
polar lubricants of the invention. The adduct (III) and the polar saturated lubricant (IV) have the structure:
(HI) R j K g l.,, where,in (III) and (IV), R, through R 5 may be hydrogen, alkyl or alkenyl and the sum of carbon atoms in all R, through R g groups totals at least 17, where at least one of R«, R g is an electronegative group with the remaining groups of R g through R g being an electronegative group or hydrogen, alkyl, alkenyl, al ynalkyl , aryl or aralkyl .
Where the unsaturated lubricant feedstock contains molecules having muliple sites of allylic unsaturation, the Ene reaction will produce an adduct containing multiple enophile moieties comprising lubricant molecules of particularly enhanced polarity.
As noted above, the Ene reaction adduct formation between unsaturated lubricant molecules and enophiles may be conducted thermally at temperatures between 100°C and 400°c either neat or in a solvent. The process may be conducted as a batch process or continuous. Where catalysts are used, Lewis acid catalysts are preferred such as BF 3 , A1C1 3 , (CH 3 ) 2 A1C1, SnCl 4 , C 2 H 5 A1C1 2 and the like.
The scope of the present invention includes the further reaction of the polar function of the hydrogenated or unsaturated adducts prepared by the process of the invention to provide further useful products, typically enhancing the properties of the lubricant. For example, the nitrile function of adducts prepared from acrylonitrile may be hydrolyzed to acid or amide or esterified by methods well known in the art. Hydrogenation of the adduct formed between an unsaturated
HVT-PAO lubricant and maleic anhydride produces the substituted succinic anhydride which may be further reacted with alcohol by known means to yield a diester of the st__ucture (V) from the anhydride (VI):
where R in (V) and (VI) is hydrogen, alkyl or alkenyl and the total lamber of carbon atoms in all R groups is at least 17 and, preferably, with at least one R group a lubricant moiety of between * _____ and C 100 _ carbon atoms, more preferably between C jQ -Cg-. R. of (V) is C.-C. alkyl such as methyl, ethyl, 2-h * yd * raxyethyl, propyl, σctyl, lauryl and the like.
The unsaturated HVI-PAO adduct with maleic anhydride, or the saturated adduct, can react with amines or polyamines such as tetraethyleneperitairine (TEPA), to form bis-succinimides (VH) :
where R is as noted in V and VI above.
In the following examples the process and products of the instant invention are described together with the distinguishing characteristics of the novel products.
EXAMPLE 6 2400 grams (2.20 moles) of HVT-PAO polydeoene prepared as described herein before having a braxiine number of 14.6 and a
calculated molecular weiφt of 1090 is reacted at 254°C with 235 grams (2.40 moles) of maleic anhydride for six hours. The batch after six hours is vacuum stripped at 175 C and 1330 Pa (10mm) to remove unreacted maleic anhydride. The yield after stripping is
• 5 2612 grams the acid number run under anhydride conditions is 44.8. Theoretical acid value for a molecular adduction of polydecene and maleic anhydride is 47.2. Therefore, conversion is 95% to anhydride adduct.
The adduct prepared from HVT-PAO polydecene was "char free" 0 with 13 evidence of tarry deposits on the reactor walls.
EXAMPLE 7 3000 grams (2.80 moles) of HVT-PAO polydecene with a bromine number of 14.87 and a calculated molecular weiφt of 1069 is reacted with 294 grams (3.0 moles) of maleic anhydride at 254°C 5 for eiφt hours. The batch is stripped at 175°C and 1330 Pa (10mm) pressure to remove any unreacted maleic anhydride. The yield en the stripped batch is 3275 grams and the acid number run under anhydrous conditions is 45.4. Theoretical acid number based on equi-molar is 48.0. Conversion, therefore is 94.5%. 0 Ihe reaction as in Example 6, was free from char or tarry deposits.
EXAMPLE 8 2000 grams (1.51 moles) of polydecene prepared using conventional Friedel-Crafts catalysis having a bromine number of 12.0 and a calculated molecular weiφt of 1325 is reacted with 175 grams of maleic anhydride (1.78 moles) for seven hours at 254°C. The batch is stripped free of excess maleic εirihydride at 175°C and 1330 Pa (10mm) pressure. Product yield is 2119 grams, and the acid number found is 21.0 as determined by ASTM 0 D-664 using an anhydrous solvent median. Theoretical acid number for equi-molar reaction is 39.4. Based on the 21.0 found and the low yield the conversion to anhydride is 54.3%. Considerable decomposition of maleic anhydride and polydecene occurred during adduction.
- 16 -
3035 grams (2 57 moles) of polydecene prepared using conventional catalysis with a bromine number of 13.5 and a calculated molecular weight of 11.77 is reacted at 254°C with 266 grams (2.71 moles) of maleic anhydride for 9 hours. The batch is
5 - stripped free of excess maleic anhydride at 175°C and 1330 Pa
(10mm) * Product yield is 3216 grams with an acid number of 24.5.
Theoretical acid number which would result from an equi-molar reaction of polydecene and maleic is 43.0. Accordingly, conversion is 56.0%. The reactor showed a considerable amount of
10 tar and char deposits.
1150 grams (1 mole) of HVI-PAO polybutene prepared as described herein before with a bromine number of 13.8 is reacted
;with 118 grams (1.20 moles) of maleic anhydride at 225°C for
15 weig t hours. The acid number of the unstripped material in the reactor after eight, hours is 51.9 versus a calculated value of f
53 f ,0 indicative of very little charring or decomposition of maleic anhydride. The batch is then stripped free of unreacted maleic anhydride. The yield in the reactor is 1235 grams, the
20 acid number is 41.0. Calculated acid number is 44.9.
Accordingly, conversion is 93.3%.
EXAMPLE 11 570 grams (0.427 moles) of HVI-PAO polybutene prepared as described herein before with a bromine number of 11.9 is reacted 2 with 5Q.4 grams of maleic anhydride (0.514 moles) for nine hours at 225°C. The batch is stripped free of excess maleic anhydride. The yield is 609 grams. The acid number is 36.5 versus a calculcited value of 39.2. The conversion therefore is 93.0%. .. EXAMPLE 12
30 15(fc grams (1,57- moles) of a commercially available polyisobutyleøe prepared via Friedel-Crafts catalysis with a molecular weight of 950 is reacted with 185 grams (1.89 moles) of
maleic anhydride for eiφt and one half hours. The acid number of the unstripped adduct is found to be 53 indicative of 15% maleic decomposition as evidenced by heavy char and tarry deposits. Upon stripping out the unreacted maleic anhydride, the acid number is found to be 40.2 versus a -theoretical acid number for equi-molar reaction of 53.2.
A__-_»-_τJingly, conversion is approximately 75%.
Approximately 1000 grams (0.786 moles) of alkenyl succinic anhydride (ASA) fom Example 6 with a calculated combining weiφt of 1272 (95% ASA; 5% polydecene) is reacted with 74 grams (0.39 moles) of tetraethylene pentamine at 204"C (400°F) to make the c_orre__pondir_g bis-suσc._n__mide. Upon analysis of the product the percent nitrogen was 2.5, with a total base number of 52.8 (ASTM D-2896) . The viscosity at 100% active at 99'C (210°F) is 106 cSt and the acid number is 0.67.
1000 grams (0.374 moles) of the alkenyl succinic anhydride
(ASA) from Example 8 with a calculated examining weiφt of 2671 (54.3% ASA; 45.7% polydecene) is reacted with 35 grams (0.185 moles) of tetraethylene pentamine at 204°C
(400 F) (204°C) to make the ∞÷rrespcnding bjώ-suσcini ide.
Approximately six and one half grams of water is removed. The final product on analysis has a total base number of 23.2%, with percent nitrogen of 1.2%. The viscosity at 99"C (210°F) is 84.6 2 mm /s. The acid number is 0.86.
From a cαrtparison of the preceding Exanples it is evident that the preparation of alkenyl succinic anhydrides using HVI-PAO oligomers to react with maleic anhydride proceeds with much hiφer conversion than comparable reactions using conventional oligomers prepared fcy oligomerization of alpha-olefins with Friedel-*Crafts catalyst. Surprisingly, the reaction of the present invention also preσeeds without the formation of substantial quantities of char and tarry deposits, as found in the art heretofore.
Examples 6 and 7 compare HVI-PAO polydecene oligomers of different molecular weight adducted with maleic anhydride versus polydecene prepared using conventional Friedel-Crafts catalyst as in Examples 9 and 10. Examples 11 and 12 compare HVI-PAO polybutene of different molecular weight versus a typical commercially available polyisobutylene prepared by Friedel-Crafts catalyst, as in Example 12.
In all cases the reactivity with the oligomers-polymers prepared by the HVI-PAO process is superior as shown by the amount of adducted maleic anhydride as measured by acid number and the resulting yield of anhydride in the stripped product.
The adducts prepared in these Examples can subsequently be reacted with a large variety of amines, alcohols, epoxides and combinations thereof for application in both fuel and lubes oil additives.
In Examples 13 and 14 a comparison is shown between two bis-succinimide ashless dispersants from alkenyl succinic anhydrides made from HVI-PAO oligomer, Example 13, and one from Friedel-Crafts catalysis, Example 14. The succinic adduct from the HVI-PAO decene contains 95% succinic adduct (Example 6) versus 53% for the one prepared from Friedel-Crafts catalysis (Example 9). Therefore, the resulting HVI-PAO alkyl bis-succinimide contains twice the nitrogen content. Since it is well known in the art that the percent nitrogen is related to dispersancy achievable in any one formulation containing a dispersant additive only one half as much bis-succinimide from Example 13 would be required compared to Example 14 which is the conventionally derived product.
The. foregoing process for the preparation of the adduct between an HVI-PAO olefinic oligomer and an enophile can be carried out at an elevated temperature between 40 and 400°C, but preferably about 250°C. The adduct containing olefinic unsaturated can be reacted to saturate the olefin group by
hydrogenating the adduct in contact with hydrogenating catalyst such as Pt or Pd and hydrogen at temperature between 20 and 300°C whereby the olefin hydrogenated adduct of said oligomer and enophile is produced. The surprising discovery has been made that the bis-succinimide ashless dispersants of the present invention prepared from the HVI-PAO and maleic anhydride adduct show significantly higher thermal stability than commercially available bis-succinimide prepared from polyisobutylene. A comparison of the two products is presented in Table 1 where Column A is the commercially available ashless dispersant (Amoco) and Column B is the product of the present invention. The alkenyl succinic anhydride of the present invention is prepared in substantially higher conversion (95% vs 75%) than the commercial product. Comparison of the thermal stability of the two products is made by thermogravametric analysis (TGA). That analysis shows a substantially lower weight loss for the product of the instant invention (79.83% vs 93.11%).
Alkenvl Succinic Anhydride
Type olefin polyisobutylene polydecer
4j00 88.14 56.9
450 93.11 79.83
" The ma|jeic anhydride adducts of the olefin oligomers may be used for the " preparation of a wide range of additives useful in lubricating oils, hydraulic fluids and other industrial fluids. The maleic anhydride adducts are especially useful for the prepaifiition of ashless detergents and dispersants formed by reaction of the anhydride group deriving from the maleic anhydride with one or more active hydrogen-containing compounds, especially nitrogen Containing compounds such as amines, organic hydroxy compounds such as phenols and alcohols, and compounds which contain more than one type of active hydrogen, for example, hydroxyamines, or which contain multiple functional groups of a similar type as in polyamines and polyols. Examples of such reaction products are disclosed in British Patent No. 1,306,529 as well as in a number of U.S. patents including those referred
to in U.S. Patent No. 4,344,854 (col. 10). Reference is made to those patents for a disclosure of exemplary reaction products of this type. The maleic anhydride adducts produced from the oligomers of the present invention can be produced in similar manner to those described in those patents except that the long chain alkenyl groups will be replaced by olefin oligomer groups produced by the present oligomerization technique. The olefin oligomers react readily with maleic anhydride using conventional techniques to form adducts which can then be reacted with other materials to form the additives.
A particularly useful class of reaction products are those produced by reaction of the maleic anhydride/olefin oligomer adduct with materials containing one or more amino groups. Those reaction products may generally be characterized as substituted succinimides (mono- and bis-succinimides ) which are useful as dispersants in lubricating oils. These succinimide type compounds may be made by reaction of the maleic anhydride adducts with various amino type compounds including amines e.g. alkylamines, polyamines, substituted amines such as hydroxyamines, haloalkylamines, Nsubstituted aminoalkylamines and other nitrogenous compounds such as the substituted and unsubstituted piperazines and piperidines.
The maleic anhydride adducts may also be reacted with hydroxylic type compounds such as alcohols including glycols and other polyols, polyalkylene glycols, aromatic hydroxyl compounds such as phenols and naphthols; alkylene oxide such as ethylene oxides and propylene oxide.
Examples of such dispersants are the derivatives of alkenyl succinimides disclosed in U.S. Patents Nos. 3,018,250 (N-dialkyl-aminoalkyl derivatives), 3,024,195 (N-alkylpiperzine derivatives), 3,219,666 (hydroxyalkyl piperazine derivatives), 3,216,936 (alkylene polyamine derivatives), 3,172,892 (ethylene polyamine derivatives), 3,515,669 and 3,779,922 (alkylene polyamine derivatives), 4,803,004 (anylamine derivatives).
- 22 -
Particularly preferred hydroxylic compounds are the hindered polyols such as pentaerythritol, dipentaerythritol and trimethylolpropane. Examples of such reaction products are disclosed in U.S. Patents Nos. 3,708,522 (pentaerythritol ester 5 derivatives post-treated with maleic anhydride), 3,632,510 and 3,522,179 (ester derivatives e.g. acid esters, di-esters, mixed esters, ester-metal salts derived from mono- and polyhydric alcohols, phenols, naphthols etc.); 3,579,450, 3,522,179 and 3,381,022 (ester derivatives of alcohols and alkylene oxides e.g.
-0 sorbitol and propylene oxide); 4,522,736 (tyrishydroxymethyl amino methane), and 4,803,004 (hindered alcohols).
The reaction products with bifunctional compounds containing two different types of functional group are also preferred, especially those containing both amino and hydroxyl
15 functionality. Reaction products of this type are described, for example, in U.S. Patents Nos. 4,016,092 and 4,097,389 (reaction with tris(hydroxy-methyl) aminomethane), 4,698,169 (alkanolamines) and 4,652,387 (aminoalcohols).
More than one type of compound may also be reacted with the
20 maleic anhydride adducts, for example, an amine and an alcohol or an amine and an alkanolamine. Reaction products of this kind are disclosed, for instance, in U.S. Patents Nos. 4,698,169 and 4,803,004 arylamines and alkanolamines or hindered alcohols), 4,522,736 (aromatic amines or phenols and alkarolamines or
25 aminomethanes), 4,652,387 (arylamines and aminoalcohols).
These reaction products of the maleic anhydride adducts with various active hydrogen containing compounds may themselves be subjected to further reaction with other compounds to create additional or different functional groups in the reaction
30 products. For example, esters formed by reaction of the maleic anhydride abducts with polyols such as pentaerythritol may be esterified further e.g. with carboxylic acids, anhydrides, acyl halides or anhydrides to introduce different ester groups, or with inorganic compounds e.g. acids such as boric acid,
phosphoric acid, sulfonic acid or substituted acids of these types, to produce borated, phosphorylated or sulfonated derivatives.
Examples of such esterified products are disclosed in U.S. Patents Nos. 4,016,092, 4,097,389, and 4,652,387. As described there, the initial reaction product between the maleic anhydride adduct and the active hydrogen compound may be reacted with an appropriate amount of the initial reaction product with alkyl borates, boric acid, a dialkyl phosphonate or a diary! phosphonate to produce the final borated or phosphonate derivatives. Alternative borating agents which may be used are disclosed in U.S. 4,652,387 and include metaboric acid, al ylmetaboraten, alkyl boroxines, boroxine boroxides.
The maleic anhydride adducts produced from the present olefin oligomers may be converted to similar materials to those described above, with the olefin oligomer group replacing the long chain alkenyl groups of the known derivatives. Reference is made to the patents identified above for details of such derivatives as well as of their manner of preparation. 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.
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