|Publication number||US3630902 A|
|Publication date||Dec 28, 1971|
|Filing date||Jul 23, 1969|
|Priority date||Jul 23, 1969|
|Publication number||US 3630902 A, US 3630902A, US-A-3630902, US3630902 A, US3630902A|
|Inventors||Keith Coupland, John Crawford|
|Original Assignee||Chevron Res|
|Export Citation||BiBTeX, EndNote, RefMan|
|Referenced by (41), Classifications (27)|
|External Links: USPTO, USPTO Assignment, Espacenet|
United States Patent Int. Cl. ClOm 1/20, 1/32 I US. Cl. 25251.5 A Claims ABSTRACT OF THE DISCLOSURE A process is described for the preparation of lubricant additives having detergency and viscosity index-improving properties wherein a succinimide detergent having a free primary amino group isreacted with a'polymerizable acid or acid derivative and the reaction product polymerized. A further polymerization witha copolymerizable monomer is also described.
BACKGROUND on THE INVENTION Field of the invention 3,630,902 Patented Dec. 28, 1971 erizable acid or acid derivative and polymerizing the product to obtain the lubricant additive.
One of the two principalreactants is a succinimide detergent having a free amino group. As used herein, succinimide detergent refers to compounds having the for- I mula: 1
wherein R isa 'long-chainpol'yolefin radical having a number average molecular weight of about 300 to 3,000,
. R is an alkylene radical containing 2 to 8 carbon atoms,
The present invention relates to a process for producing novel lubricantadditives and the, additives produced. More particularly, it relates, to additives derived from succinimide detergents."
Description of the priorart It is known to prepare lubricant additives by reaction of a substituted succinic acid or anhydride with an amine". See, for example, US. Pat-3,361,673. The substituent in the succinic acid or anhydride is asubstantially-Saturated aliphatic group having about 30 to 200 carbon atoms. The
acid or anhydride reacts with the amine to give a product or mixture of products which includes a succinimide structure. These compounds are used as detergents in lubricant compositions. Compounds which may be 0btained in this manner and have detergency properties are a hereafter referred to as succinimide detergents.
In many cases the amine used in the preparation of the succinimide detergent contains more than one amino nitrogen atom, and the product of reaction of the substituted succinic acid or anhydride with the amine may, therefore,
contain a free primary amino group.
SUMMARY The present invention is a process for producing a lubricant additive having detergency and viscosity indeximproving properties by reacting a succinimide detergent having a free primary amino group with a polymerizable acid or acid additive and polymerizing the product to obtain the lubricant additive.
DETAILED DESCRIPTION OF THE INVENTION In its broadest form, this invention is a process for producing a lubricant additive having detergency and viscosity index-improving properties by reacting a succinimide detergent having a free amino group with a polymand y is an integer from O" to 10. These compounds are described in more detail in numerous references in the art-See, for instance,.the aforesaid US. Pat. 3,219,666 'as well as US. Pats. 3,018,250, 3,087,936, 3,172,892, and
3,202,678. Usually they are prepared by reacting polyolefin, succinic' anhydride, and ammonia, alkylene monoamines,-or.alkylene polyamines.- Such reactions are also described in the art. See, for instance, the patents cited immediately above.
The preferred succinimide detergents are polyisobuten- ,yl succinimides prepared ,byreacti0n of a substituted succinic acid or anhydride derived from a polybutene of (number average) molecular weight about 950 to 2,800 and tetraethylene pentamine. Polyolefins having number average molecular weights of 950 or greater are preferred as solubility problems may be encountered with "the lower molecular weight materials, particularly where the succinimideis derived from a high polyamine. Other typical succinimides are those derived from polybutenes of 350 and 3,000 molecular weight, respectively. Particularly preferred are succinimides derived from polybutenes having 950, 1,400, or 2,700 molecular weight and which are commercially available from Chevron Chemical Company under the trade names of, respectively, Polybutene 24, Polybutene 32, and Polybutene 128. The succinic acid or anhydride and the amine are preferably reacted in approximately equimolar ratio to obtain the succinimide dispersant.
Typical polyolefins which can be used to prepare the succinimide detergents include polyethylene, polypropylene, and polyisobutylene. Typical monoamine reactants may be methylamine, ethylamine, propylamine, and higher alkyl monoamines. Typical polyamine reactants include ethylene diamine, propylene diamine, pentylene diamine, octylene diamine, diethylene triamine, triethylene tetramine, tetraethylene pentamine, tetrapropylene pentamine, tetrabutylene pentamine, and nonaethylene decamine.
Suitable polymerizable acids are those which have unsaturation in the molecule, as, for example, acrylic methacrylic, or crotonic acids. Acrylic and methacrylic acids are preferred. While this explanation is in no way to be considered limiting, it is believed that the acid or derivative reacts with a free amino group to form an amide. Accordingly, the acid derivative which may be used is any which will form an amide on reaction with an amino group, as, for example, an anhydride, acid chloride, or ester. The reaction between the succinimide detergent and polymerizable acid is usually carried out in an inert solvent, such as toluene, and if solubility problems are encountered, the product of reaction may be dissolved in lubricating oil by solvent extraction with the oil from the inert solvent. It is preferred to react the succinimide detergent and polymerizable acid in equimolar proportions.
The product may be polymerized with or without a catalyst, although use of a catalyst is preferred. If a catalyst is used, it is preferred that it be a free radical catalyst such as azo-bis(isobutyronitrile) or a peroxide such as benzoyl peroxide, t-butylhydroperoxide or di-t-butylhydroperoxide. Although it is not known with certainty, it is believed that with acrylic acid the final product of reaction in the presence of a free radical catalyst has the structure A it when x is an integer and A is the residue of the succinimide detergent having a free amino group. The catalyst may also be a base, in which case the product may contain the structure Suitable basic catalysts include alkali metal alkoxides, Grignard reagents, zinc alkyls, lithium alkyls and the like.
Reactions to give both structures may occur simultaneously.
The product of reaction of the succinimide detergent and the polymerizable acid may be further copolymerized with a copolymerizable monomer in the presence of a free radical polymerization catalyst. The copolymerizable monomer may be a further quantity of the polymerizable acid, although this is not preferred as the product will be acidic, which is undesirable in a lubricant additive. It is, therefore, preferred that the copolymerizable monomer be a neutral compound having an olefinic double bond which is activated by another group in the molecule to make it polymerize under mild conditions, for example, alkyl ester of acrylic or methacrylic acid such as methyl, n-butyl, 2-ethylhexyl or laurylacrylate, or methacrylate, acrylamide, vinyl esters such as vinyl acetate or vinyl propionate, styrene, a-methyl styrene, allyl acetate and acrylonitrile.
When producing a copolymer, it is preferred to react 2 to 3 moles of the copolymerizable monomer with 1 mole of the product of reaction between the succinimide detergent and polymerizable acid.
The amount of polymerization in the final product can vary greatly depending on the ease of polymerization of the constituent monomer, and the value of the integer x may range from 2 to 200. A typical lubricant which can be improved by the additives described herein comprises a mixture of a lubricating oil and the additive produced by the process of this invention. The additives are generally present as 0.1 to weight percent of the whole lubricant composition. The preferred concentration is about 2 weight percent. It is also possible to use these additives in concentrates, in which the concentration of additive in the mixture of oil and additive is 10 to 80 weight percent. Preferably the concentration is about weight percent.
The invention is further illustrated in the examples.
Example 1 An oil solution of a polyisobutenyl succinimide (1,000 g.), containing 36% active succinimide and prepared from Cit tetraethylene pentamine and a substituted succinic anhydride derived from polybutene of 1,000 M.W. at a molar ratio of 09:10, was charged to a glass reactor. The succinimide was further diluted with toluene and the mixture stirred. The temperature of the contents was raised to 40 C. and acrylic acid (29 g.) added dropwise. When addition of acrylic acid was complete, the temperature of the reactants was raised until the mixture boiled. Water of reaction was then removed continuously as a toluenetwater azeotrope with the aid of a Dean and Stark receiver. When the water of reaction had ceased to be evolved, the reaction mixture was cooled to 30 C. and 4 g. of azo-bis(isobutyronitrile) was added. The temperature was raised and the mixture stirred at 70 C. for 5 hours. The temperature was further raised to C. and stirring continued for a further hour. The toluene was then removed by distillation under reduced pressure. The final product was a viscous dark amber liquid having a characteristic odor. Infrared examination of the product revealed the presence of both imide and amide groups. The nitrogen content was found to be 2 weight percent.
The product was evaluated for viscosity index-improving tendencies by blending at various concentrations into a base oil having a viscosity index of 68. The results of these tests are tabulated below in Table I. The viscosity index was calculated according to ASTM method D-S 67.
TABLE I Material of example (wt. percent) Viscosity index 0 (base oil) 68 1 70.1 2 77.4 5 83.2 10 90.2
The product of the example was evaluated for detergency in the Petter AV-l l20-hour Engine Test operated to Ministry of Defense Specification DEF 2101D. It was evaluated in a formulation containing an overbased calcium sulfurized alkyl phenate as a basic additive and a zine dialkyldithiophosphate in which the alkyl groups were derived from C and C primary alcohols as an antioxidant. It is compared with a similar nitrogen-containing succinimide commercially available at the equivalent concentration (based on nitrogen content). The results from the test are listed below in Table II. In the test, results are reported on a scale of 0 to 10, with 10 representing a clean engine.
TABLE II Grooves and lands, average Lubricant A (Material of Example 1) 8.2 Lubricant B (Commercial succinimide) 5.2
As may be seen from the tests, the material of this invention has both viscosity index-improving properties and shows excellent detergency when tested in a diesel engine.
Examples A1 through I1 In each of the examples tabulated in Table III, below, a succinimide detergent with an alkenyl side chain and derived from tetraethylenepentamine was reacted on a mole-to-mole basis with a polymerizable acid. The reactants plus toluene and, in some cases, a catalyst, were heated to toluene reflux temperature and the water of reaction removed via a Dean and Stark receiver, leaving an intermediate product. The polymerization catalyst was then added and the intermediate product polymerized under the conditions noted. Heating was continued until no more water was evolved. In some examples, the polymeric material was then further polymerized with the same acid or another monomer. The data in Table III illustrate the wide variety of conditions under which the viscosity indeximproving polymers of this invention may be produced.
TABLE III Viscosity index of noted wt. Number of percent polycarbon atoms in Polymerization conditions Reactants and mole ratio (MR) meric product alkenyl portion in oil of polyiso- Reaction Tempera- Catalyst, Poliso- Acid Other solution butenyl time, ure, wt. bntonyl succinimide hrs. 0. percent l succinimide MR Compound MR Compound 70 48 50 0. 13 1 1 Acrylic. 108 118 70 6 80 0. 13 1 1 d 108 114 70 110 0. 26 1 108 112 70 2 100 0. 13 1 109 113 70 2 100 0.66 1 107 110 70 2 100 1. 3 1 104 106 70 24 60 0. 13 1 108 106 70 24 60 0. 13 1 109 118 70 24 60 0. 13 1 111 118 70 24 60 0.13 1 d 107 111 70 24 60 0. 13 1 Methyl acrylate- 115 115 70 24 60 0. 13 1 n-butyl methacryla 112 116 70 24 60 0. 13 1 Acrylamide 108 114 70 24 60 0. 1 1 Methyl acrylate. 108 115 70 24 75 2 0.2 1 1.0 do 99 103 70 24 75 0.2 1 1.0 do 110 110 70 24 75 0.2 1 1 0 do 98 105 24 60 0.1 1 2 0 do 106 118 70 24 60 0.1 1 1 do 100 110 70 24 60 0. 1 1 Methyl acrylate- 107 1 14 70 24 60 01 1 (1 Acrylic (excess) "i6; "iii l The catalyst was azo-bis(isobutyronitrile) unless otherwise noted. 2 The catalyst was benzoyl peroxide.
3 The catalyst was t-butylhydroperoxide.
4 The catalyst was di-t-butylhydroperoxide.
It is apparent from the data that a wide variety of reaction conditions and reactants may be used to produce the polymeric viscosity index improvers of this invention. .Runs A1 through A3 illustrate the effect of varying polymerization reaction time and temperature. It is seen that high viscosity index products are obtained under all conditions. Runs B1 through B3 llustrate the eflect of increasing the amount of catalyst present. Runs C1 through C7 illustrate the eifectof further polymerization following removal of the water with additional acid or other monomers. Run D1 illustrates the effectiveness of polymerizable acids other than acrylic. RunsEl through E3 illustrate the effects of polymerization catalysts other than azo-bis(isobutyronitrile). Run F1 illustrates a lower molecular weight polyisobutenyl succinimide as a reactant.
In Runs G1 and G2, the polymerizationreactants were heated at the listed temperature to form a salt. The salt was then contacted with the polymerization catalyst to form an intermediate polymer. The intermediate polymer was then heated to the reflux temperature of the solvent to form the final polymeric product/Water of reaction was removed via a Dean and Stark receiver. Run I1 was conducted under substantially the same conditions as Runs G1 and G2, with the exception that excess acrylic acid was used and the succinimide detergent was diluted 50% with oil.
It will be seen from these data that a wide variety of polymeric materials may be made by the process of this invention, and that these polymers find: considerable utility as viscosity index improvers for lubricating oils.
1. A process for the production of a lubricant additive having detergency and viscosity index-improving properties which comprises polymerizing substantially equimolar proportions of a polymerizable compound and a succinimide detergent by heating the reaction mixture of said compound and succinimide at its boiling point until essentially all water of reaction has been evolved and then contacting the dehydrated mixture with a free radical or basic polymerization catalyst; wherein said succinimide has a free amino group and is the reaction product of the reaction of substantially equimolar amounts of an aliphatic substituted succinic acid or anhydride, the aliphatic substituent being substantially saturated and having a molecular weight of about 300 to 3000, and an alkylene polyamine having 2-12 amino groups and 1-11 alkylene groups each containing 2-8 carbon atoms; and wherein said polymerizable compound is selected from the group consisting of acrylic, methacrylic, and crotonic acids and their anhydrides.
.2. The process described in claim 1, wherein polymerizatiou of the product of reaction between the succinimide and the polymerizable compound is carried out in the presence of a free radical polymerization catalyst.
3. The process described in claim 2, wherein said free radical polymerization catalyst is azo-bis(isobntyronitrile), benzoyl peroxide, t-butylhydroperoxide, or di-tbutylhydroperoxide.
4. The process described in claim 1, wherein polymerization of the product of reaction between the succinimide and the polymerizable compound is carried out in the presence of a basic catalyst.
5. The process described in claim 4, wherein said basic catalyst is an alkali metal alkoxide, Grignard Reagent, zinc alkyl, or lithium alkyl.
6. The process described in claim 1, wherein the aliphatic substituent of said succinimide is derived from a polyolefin having a number average molecular weight of at least 950.
7. The process described in claim 6, wherein said polyolefin is polybutene.
8. The process described in claim 1, wherein following the polymerization of said succinimide and polymerizable compound to form a polymerized reaction product, said reaction product is further catalytically polymerized with a copolymerizable monomer selected from the group consisting of alkyl esters of acrylic or methacrylic acid, vinyl acetate, vinyl propionate, styrene, u-methyl styrene, allyl acetate, acrylamide, and acrylonitrile, the mole ratio of said copolymerizable monomer to said reaction product being in the range 2-3 1.
9. The process described in claim 8, wherein said copolymerizable monomer is methyl-, n-butyl-, 2-ethylhexyl-, or lauryl-acrylate or methacrylate, vinyl acetate or vinyl propionate.
7 8 10. A lubricant composition comprising a mixture of 3,298,955 1/1967 Strang 25251.5 A lubricating oil and 0.1 to 10 Weight percent of the 3,374,174 3/1968 Le Suer 252-515 A additive produced by the process described in claim 1.
DANIEL E. WYMAN, Prlmary Examiner References Cited 5 W. J. SHINE, Assistant Examiner UNITED STATES PATENTS 3,048,544 8/1962 Stewart 61: a1. 252 51.5 A 3,185,704 5/1965 Kahn et a1. 252 51.5 A 260--78.5 R, 326.5 F, 326.5 FM 3,216,936 11/1965 Le Suer 252-515 A
|Citing Patent||Filing date||Publication date||Applicant||Title|
|US3897454 *||Jun 11, 1973||Jul 29, 1975||Atlantic Richfield Co||Polyalkylene glycol polyalkylene polyamine dispersants for lubricant fluids|
|US4140643 *||Jun 3, 1977||Feb 20, 1979||The Lubrizol Corporation||Nitrogen- and sulfur-containing lubricant additive compositions of improved compatibility|
|US4194985 *||Jan 14, 1974||Mar 25, 1980||The Lubrizol Corporation||Polymeric compositions, method for their preparation, and lubricants containing them|
|US4230843 *||Feb 2, 1979||Oct 28, 1980||The Lubrizol Corporation||Polymeric compositions, method for their preparation, and lubricants containing them|
|US4248719 *||Aug 24, 1979||Feb 3, 1981||Texaco Inc.||Quaternary ammonium salts and lubricating oil containing said salts as dispersants|
|US4374034 *||Apr 16, 1980||Feb 15, 1983||The Lubrizol Corporation||Polymeric compositions, method for their preparation, and lubricants containing them|
|US4536312 *||Mar 20, 1984||Aug 20, 1985||Mobil Oil Corporation||Sulfurized amine condensation products and lubricant compositions containing same|
|US4614603 *||Apr 12, 1985||Sep 30, 1986||Chevron Research Company||Modified succinimides (III)|
|US4617138 *||Apr 12, 1985||Oct 14, 1986||Chevron Research Company||Modified succinimides (II)|
|US4618450 *||Nov 7, 1984||Oct 21, 1986||The Lubrizol Corporation||Aqueous systems containing amino sulfonic acid derivatives of carboxylic acids|
|US4666460 *||Apr 18, 1986||May 19, 1987||Chevron Research Company||Modified succinimides (III)|
|US4668246 *||Apr 25, 1986||May 26, 1987||Chevron Research Company||Modified succinimides (IV)|
|US4686054 *||Jun 24, 1986||Aug 11, 1987||Exxon Research & Engineering Co.||Succinimide lubricating oil dispersant|
|US4783275 *||May 26, 1987||Nov 8, 1988||Chevron Research Company||Modified succinimides (IV)|
|US4857217 *||Nov 30, 1987||Aug 15, 1989||Exxon Chemical Patents Inc.||Dispersant additives derived from amido-amines|
|US5034018 *||May 30, 1989||Jul 23, 1991||Exxon Chemical Patents Inc.||Fuel additives derived from amido-amines (PT-731)|
|US5043084 *||May 30, 1989||Aug 27, 1991||Exxon Chemical Patents, Inc.||Novel polymer substituted amino phenol mannich base amido-amine dispersant additives (PT-742)|
|US5186853 *||Mar 25, 1991||Feb 16, 1993||Bp Chemicals (Additives) Limited||Polyacrylate-modified bis-succinimide lubricant additives|
|US5221491 *||Aug 9, 1991||Jun 22, 1993||Exxon Chemical Patents Inc.||Two-cycle oil additive|
|US5229020 *||Aug 5, 1992||Jul 20, 1993||Exxon Chemical Patents Inc.||Branched amido-amine dispersant additives|
|US5230834 *||May 30, 1989||Jul 27, 1993||Exxon Chemical Patents Inc.||Viscosity stable multifunctional viscosity index modifier additives derived from amido amines|
|US5238466 *||Jul 15, 1991||Aug 24, 1993||Exxon Chemical Patents Inc.||Fuel additives derived from amido-amines|
|US5308364 *||Jul 14, 1993||May 3, 1994||Exxon Chemical Patents Inc.||Fuel compositions containing improved branched amido-amine dispersant additives|
|US5385684 *||Jul 15, 1993||Jan 31, 1995||Exxon Chemical Patents, Inc.||Branched amido-amine dispersant additives|
|US5395539 *||Mar 15, 1993||Mar 7, 1995||Exxon Chemical Patents Inc.||Amide containing friction modifier for use in power transmission fluids|
|US5397489 *||Oct 26, 1992||Mar 14, 1995||Bp Chemicals (Additives) Limited||Lubricating oil additives, their preparation and use|
|US5484543 *||Nov 18, 1994||Jan 16, 1996||Exxon Chemical Patents Inc.||Amide containing friction modifier for use in power transmission fluids|
|US6020061 *||Apr 15, 1997||Feb 1, 2000||S. C. Johnson Commercial Markets, Inc.||Emulsion polymerization using polymeric surfactants|
|US6083287 *||Sep 17, 1997||Jul 4, 2000||Elf Antar France||Detergent and anti-corrosive additive for fuels and fuel composition|
|US6617287||Oct 22, 2001||Sep 9, 2003||The Lubrizol Corporation||Manual transmission lubricants with improved synchromesh performance|
|US9481841||Dec 8, 2005||Nov 1, 2016||The Lubrizol Corporation||Process of preparation of an additive and its use|
|EP0319229A2 *||Nov 28, 1988||Jun 7, 1989||Exxon Chemical Patents Inc.||Improved dispersant additives derived from amido-amines|
|EP0319229A3 *||Nov 28, 1988||Sep 6, 1989||Exxon Chemical Patents Inc.||Improved dispersant additives derived from amido-amines|
|EP0336664A2 *||Mar 31, 1989||Oct 11, 1989||Exxon Chemical Patents Inc.||Improved dispersant additives derived from amido-amine adducts|
|EP0336664A3 *||Mar 31, 1989||Nov 29, 1989||Exxon Chemical Patents Inc.||Improved dispersant additives derived from amido-amine adducts|
|EP0368548A1 *||Nov 1, 1989||May 16, 1990||Exxon Chemical Patents Inc.||Improved amide dispersant additives derived from amido-amines|
|EP0400865A1 *||May 22, 1990||Dec 5, 1990||Exxon Chemical Patents Inc.||Improved viscosity stable multifunctional viscosity index modifier additives derived from amido amines|
|EP0400874A1 *||May 22, 1990||Dec 5, 1990||Exxon Chemical Patents Inc.||Improved multifunctional viscosity index modifier additives derived from amido amines|
|WO1990004625A2 *||Oct 24, 1989||May 3, 1990||Exxon Chemical Company||Amide containing friction modifier for use in power transmission fluids|
|WO1990004625A3 *||Oct 24, 1989||Jul 26, 1990||Exxon Chemical Co||Amide containing friction modifier for use in power transmission fluids|
|WO1998012283A1 *||Sep 17, 1997||Mar 26, 1998||Elf Antar France||Detergent and anti-corrosive additive for fuels and fuel composition|
|U.S. Classification||508/221, 525/386, 525/264, 508/242, 508/291, 525/382, 525/322, 525/301, 525/319, 525/381|
|International Classification||C08F20/52, C10M149/10|
|Cooperative Classification||C10M2217/024, C10M2215/28, C10M2217/06, C10M2209/02, C10M2217/028, C10M2217/02, C08F20/52, C10M2215/04, C10M2215/26, C10M2205/00, C10M2205/02, C10M2217/046, C10M149/10|
|European Classification||C08F20/52, C10M149/10|