Ashless dispersants formed from substituted acylating agents and their production and use

• US 5,241,003 A
• Filed: 06/08/1992
• Issued: 08/31/1993
• Est. Priority Date: 05/17/1990
• Status: Expired due to Term

• Current Assignee: Afton Chemical Corporation
• Original Assignee: Ethyl Petroleum Additives Incorporated (Newmarket Corporation)
• Inventors: Degonia, David J., Griffin, Paul G.
• Primary Examiner(s): Lipman, Bernard
• Application Number:
  US07/895,001
• Time in Patent Office: 449 Days
• Field of Search: 525/123, 525/327.6, 525/327.7, 525/329.5, 525/329.6
• US Class Current: 525/123
• CPC Class Codes: C07C 51/567 by reactions not involving carboxylic acid anhydride groups
• CPC Class Codes: C07C 57/13 Dicarboxylic acids
• CPC Class Codes: C08F 10/00 Homopolymers and copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond
• CPC Class Codes: C08F 222/06 Maleic anhydride
• CPC Class Codes: C08F 255/10 on to butene polymers
• CPC Class Codes: C08F 8/14 Esterification
• CPC Class Codes: C08F 8/32 by reaction with amines
• CPC Class Codes: C08F 8/46 Reaction with unsaturated dicarboxylic acids or anhydrides thereof, e.g. maleinisation
• CPC Class Codes: C08F 8/48 Isomerisation; Cyclisation
• CPC Class Codes: C10L 1/221 compounds of uncertain formula; reaction products where mixtures of compounds are obtained
• CPC Class Codes: C10L 1/238 obtained otherwise than by reactions involving only carbon-to-carbon unsaturated bonds C10L1/221 takes precedence
• CPC Class Codes: C10M 133/52 having a carbon chain of 30 or more atoms
• CPC Class Codes: C10M 141/08 at least one of them being an organic sulfur-, selenium- or tellurium-containing compound
• CPC Class Codes: C10M 141/10 at least one of them being an organic phosphorus-containing compound
• CPC Class Codes: C10M 163/00 Lubricating compositions characterised by the additive being a mixture of a compound of unknown or incompletely defined constitution and a non-macromolecular compound, each of these compounds being essential
• CPC Class Codes: C10M 2207/028 Overbased salts thereof
• CPC Class Codes: C10M 2207/26 Overbased carboxylic acid salts
• CPC Class Codes: C10M 2207/262 derived from hydroxy substituted aromatic acids, e.g. salicylates
• CPC Class Codes: C10M 2215/04 having amino groups bound to acyclic or cycloaliphatic carbon atoms
• CPC Class Codes: C10M 2215/042 containing hydroxy groups; Alkoxylated derivatives thereof
• CPC Class Codes: C10M 2215/08 : Amides
• CPC Class Codes: C10M 2215/082 : containing hydroxyl groups; Alkoxylated derivatives
• CPC Class Codes: C10M 2215/12 : Partial amides of polycarboxylic acids
• CPC Class Codes: C10M 2215/22 : Heterocyclic nitrogen compounds
• CPC Class Codes: C10M 2215/221 : Six-membered rings containing nitrogen and carbon only
• CPC Class Codes: C10M 2215/225 : the rings containing both nitrogen and oxygen
• CPC Class Codes: C10M 2215/226 : Morpholines
• CPC Class Codes: C10M 2215/24 : having hydrocarbon substituents containing thirty or more carbon atoms , e.g. nitrogen derivatives of substituted succinic acid
• CPC Class Codes: C10M 2215/26 : Amines
• CPC Class Codes: C10M 2215/28 : Amides; Imides
• CPC Class Codes: C10M 2215/30 : Heterocyclic compounds
• CPC Class Codes: C10M 2217/046 : Polyamines, i.e. macromoleculars obtained by condensation of more than eleven amine monomers
• CPC Class Codes: C10M 2217/06 : Macromolecular compounds obtained by functionalisation op polymers with a nitrogen containing compound
• CPC Class Codes: C10M 2219/02 : Sulfur-containing compounds obtained by sulfurisation with sulfur or sulfur-containing compounds
• CPC Class Codes: C10M 2219/022 : of hydrocarbons, e.g. olefines polyolefins C10M2221/041
• CPC Class Codes: C10M 2219/024 : of esters, e.g. fats
• CPC Class Codes: C10M 2219/046 : Overbasedsulfonic acid salts
• CPC Class Codes: C10M 2219/08 : Thiols; Sulfides; Polysulfides; Mercaptals
• CPC Class Codes: C10M 2219/082 : containing sulfur atoms bound to acyclic or cycloaliphatic carbon atoms
• CPC Class Codes: C10M 2219/083 : Dibenzyl sulfide
• CPC Class Codes: C10M 2219/086 : containing sulfur atoms bound to carbon atoms of six-membered aromatic rings
• CPC Class Codes: C10M 2219/087 : containing hydroxy groups; Derivatives thereof, e.g. sulfurised phenols
• CPC Class Codes: C10M 2219/089 : Overbased salts
• CPC Class Codes: C10M 2223/04 : Phosphate esters
• CPC Class Codes: C10M 2223/041 : Triaryl phosphates
• CPC Class Codes: C10M 2223/042 : Metal salts thereof
• CPC Class Codes: C10M 2223/043 : Ammonium or amine salts thereof
• CPC Class Codes: C10M 2223/045 : Metal containing thio derivatives
• CPC Class Codes: C10M 2223/047 : Thioderivatives not containing metallic elements
• CPC Class Codes: C10M 2223/06 : having phosphorus-to-carbon bonds
• CPC Class Codes: C10M 2223/061 : Metal salts
• CPC Class Codes: C10M 2223/063 : Ammonium or amine salts
• CPC Class Codes: C10M 2223/065 : containing sulfur
• CPC Class Codes: C10M 2227/061 : Esters derived from boron
• CPC Class Codes: C10N 2010/04 : Groups 2 or 12
• CPC Class Codes: C10N 2040/00 : Specified use or application for which the lubricating composition is intended
• CPC Class Codes: C10N 2040/02 : Bearings
• CPC Class Codes: C10N 2040/04 : Oil-bath; Gear-boxes; Automatic transmissions; Traction drives
• CPC Class Codes: C10N 2040/042 : for automatic transmissions
• CPC Class Codes: C10N 2040/044 : for manual transmissions
• CPC Class Codes: C10N 2040/046 : for traction drives
• CPC Class Codes: C10N 2040/06 : Instruments or other precision apparatus, e.g. damping fluids
• CPC Class Codes: C10N 2040/08 : Hydraulic fluids, e.g. brake-fluids
• CPC Class Codes: C10N 2040/16 : Dielectric; Insulating oil or insulators
• CPC Class Codes: C10N 2040/17 : for electric contacts
• CPC Class Codes: C10N 2040/20 : Metal working
• CPC Class Codes: C10N 2040/22 : with essential removal of material , e.g. cutting, grinding or drilling
• CPC Class Codes: C10N 2040/24 : without essential removal of material , e.g. forming, gorging, drawing, pressing, stamping, rolling or extruding; Punching metal
• CPC Class Codes: C10N 2040/241 : Manufacturing joint-less pipes
• CPC Class Codes: C10N 2040/242 : Hot working
• CPC Class Codes: C10N 2040/243 : Cold working
• CPC Class Codes: C10N 2040/244 : of specific metals
• CPC Class Codes: C10N 2040/245 : Soft metals, e.g. aluminum
• CPC Class Codes: C10N 2040/246 : Iron or steel
• CPC Class Codes: C10N 2040/247 : Stainless steel
• CPC Class Codes: C10N 2040/25 : Internal-combustion engines
• CPC Class Codes: C10N 2040/251 : Alcohol fueled engines
• CPC Class Codes: C10N 2040/252 : Diesel engines
• CPC Class Codes: C10N 2040/253 : Small diesel engines
• CPC Class Codes: C10N 2040/255 : Gasoline engines
• CPC Class Codes: C10N 2040/28 : Rotary engines
• CPC Class Codes: C10N 2040/30 : Refrigerators lubricants or compressors lubricants
• CPC Class Codes: C10N 2040/32 : Wires, ropes or cables lubricants
• CPC Class Codes: C10N 2040/34 : Lubricating-sealants
• CPC Class Codes: C10N 2040/36 : Release agents or mold release agents
• CPC Class Codes: C10N 2040/38 : Conveyors or chain belts
• CPC Class Codes: C10N 2040/40 : Generators or electric motors in oil or gas winning field
• CPC Class Codes: C10N 2040/42 : Flashing oils or marking oils
• CPC Class Codes: C10N 2040/44 : Super vacuum or supercritical use
• CPC Class Codes: C10N 2040/50 : Medical uses
• CPC Class Codes: C10N 2070/02 : Concentrating of additives

Abstract

Succinimides, succinic esters, and succinic ester-amides are formed by (A) reacting (i) at least one substantially aliphatic polymer of at least one lower olefin, and (ii) an acidic reactant or a mixture of two or more acidic reactants represented by the general formula

R--CO--CH═CH--CO--R'"'"'

wherein R and R'"'"' are independently --OH, --O-lower alkyl, a halogen atom, or taken together are a single oxygen atom; the process being characterized in that:

a) the substantially aliphatic polymer is comprised predominantly or entirely of polyisobutene, at least 50% of the polyisobutene content of such polymer having an end group represented by the formula ##STR1## b) the mole ratio of said acidic reactant(s):said polymer(s) is at least 1:1;

c) the reaction mixture is maintained under superatmospheric pressure during at least a substantial portion of the reaction period; and

d) said acylating agent is characterized by having an average total tar rating as determined by the method described in the specification hereof that is at least 25% lower than the average total tar rating of a corresponding product made in the same way under the same reaction conditions using a polyisobutene containing up to 10% of the above-depicted end group; and

(B) reacting such acylating agent with at least one alcohol (preferably a polyhydric alcohol) or amine (preferably a polyamine having at least one primary amino group).

Claims

1. A post-treated carboxylic derivative composition produced by:

(A) forming a succinic derivative composition by reacting at least one substituted succinic acylating agent with a reactant selected from the group consisting of (1) at least one amine having at least one primary or secondary amino group, (2) at least one alcohol, and (3) a combination of at least one amine having at least one primary or secondary amino group and at least one alcohol, the components of (3) being reacted with said at least one substituted succinic acylating agent concurrently or sequentially in any order, said at least one succinic acylating agent being prepared by reacting (i) at least one substantially aliphatic polymer of at least one lower olefin, and (ii) an acidic reactant or a mixture of two or more acidic reactants represented by the general formula

space="preserve" listing-type="equation">R--CO--CH═

CH--CO--R'"'"'

wherein R and R'"'"' are independently --OH, --O-lower alkyl, a halogen atom, or taken together are a single oxygen atoms;

the process of preparing said at least one succinic acylating agent being characterized in that;

a) the substantially aliphatic polymer is comprised predominantly or entirely of polyisobutene, at least 50% of the polyisobutene content of such polymer having an end group represented by the formula ##STR17## b) the mole ratio of said acidic reactant(s);

said polymer(s) is at least 1;

1; and

c) the reaction mixture is maintained under superatmospheric pressure during at least a substantial portion of the reaction period; and

d) said acylating agent is characterized by having an average total tar rating as determined by the method described in the specification herein that is at least 25% lower than the average total tar rating of a corresponding product made in the same way under the same reaction conditions using a polyisobutene containing up to 10% of the above-depicted end group; and

(B) reacting said succinic derivative composition with at least one post-treating agent selected from the group consisting of inorganic phosphorus acid or anhydride;

organic phosphorus compound;

phosphorus pentasulfide;

boron compound;

mono- or polycarboxylic acid, anhydride or acid halide;

mono- or polyepoxide or thioepoxide;

aldehyde or ketone;

carbon disulfide;

glycidol;

urea, thiourea or guanidine;

organic sulfonic acid;

alkenyl cyanide;

diketene;

a diisocyanate;

alkane sultone;

1,3-dicarbonyl compound;

sulfate of alkoxylated alcohol or phenol;

cyclic lactone;

cyclic carbonate or thiocarbonate, linear monocarbonate or polycarbonate, or chlorophormate;

nitrogen-containing carboxylic acid;

hydroxy-protected chlorodicarbonyloxy compound;

lactam, thiolactam, thiolactone or dithiolactone;

cyclic carbamate, cyclic thiocarbamate or cyclic dithiocarbamate;

hydroxyaliphatic carboxylic acid;

oxidizing agent;

combination of phosphorus pentasulfide and a polyalkylene polyamine;

combination of carboxylic acid or an aldehyde or ketone and sulfur or sulfur chloride;

combination of a hydrazine and carbon disulfide;

combination of an aldehyde and a phenol;

combination of an aldehyde and an O,O-diester of dithiophosphoric acid;

combination of a hydroxyaliphatic carboxylic acid and a boric acid;

combination of a hydroxyaliphatic carboxylic acid, then formaldehyde and a phenol;

combination of a hydroxyaliphatic carboxylic acid, and then an aliphatic dicarboxylic acid;

combination of formaldehyde and a phenol, and then glycolic acid;

combination of a hydroxyaliphatic carboxylic acid or oxalic acid and then a diisocyanate;

combination of inorganic acid or anhydride or phosphorus or a partial or total sulfur analog thereof and a boron compound;

combination of an organic diacid, then an unsaturated fatty acid, and then a nitrosoaromatic amine, optionally followed by a boron compound and then a glycolating agent;

Combination of an aldehyde and a triazole;

combination of an aldehyde and a triazole, then a boron compound; and

combination of cyclic lactone and a boron compound.

2. A composition of claim 1 wherein said carboxylic derivative composition is produced by reaction between said succinic acylating agent and at least one polyamine.

3. A composition of claim 1 wherein said carboxylic derivative composition is produced by reaction between said succinic acylating agent and at least one alkylene polyamine.

4. A composition of claim 1 wherein said carboxylic derivative composition is produced by reaction between said succinic acylating agent and a mixture of straight chain, branched chain, and cyclic polyethylene polyamines having an overall approximate composition falling in the range of triethylene tetramine to pentaethylene hexamine.

5. A composition of claim 1 wherein said carboxylic derivative composition is produced by reaction between said succinic acylating agent and at least one polyhydric alcohol.

6. A composition of claim 1 wherein said carboxylic derivative composition is produced by reaction between said succinic acylating agent and at least one polyol.

7. A composition of claim 1 wherein said carboxylic derivative composition is produced by reaction between said succinic acylating agent and at least one polyamine and at least one polyhedric alcohol.

8. A composition as claimed in claim 1 wherein the succinic acylating agent used in producing said carboxylic derivative composition is further characterized by having, after removal of residual acidic reactant or reactants, an acid number of at least 0.7.

9. A composition as claimed in claim 8 wherein said acid number is at least 0.9.

10. A carboxylic derivative composition of claim 1 in admixture with at least one oil of lubricating viscosity or at least one hydrocarbonaceous liquid fuel in weight proportions falling in the range of about 0.1:

99.9 to about 99.9;

0.1.

11. A composition of any one of claims 1 through 7 wherein the succinic acylating agent used in producing said carboxylic derivative compositions is further characterized by having a succination ratio of less than 1.3.

12. A composition of claim 1 wherein the polymer consists essentially of polyisobutene at least 75% of which has said end group.

13. A composition of claim 1 wherein the mole ratio of said acidic reactant(s):

said polymer(s) in the reaction of (A) is in the range of 1.1;

1 to about 1.9;

1.

14. A composition of claim 1 wherein the acidic reactant in the reaction of (A) consists essentially of maleic anhydride, and wherein the mole ratio of maleic anhydride:

said polymer(s) in the reaction of (A) is in the range of 1.1;

1 to about 1.9;

1.

15. A composition of claim 1 wherein the acidic reactant in the reaction of (A) consists essentially of maleic anhydride and wherein the polymer consists essentially of polyisobutene.

16. A composition of claim 1 wherein the mole ratio of said acidic reactant(s):

said polymer(s) in the reaction of (A) is such that the product contains in chemically combined form an average of less than 1.3 moles of said acid groups per mole of polymer chains chemically combined therewith.

17. A composition of claim 1 wherein said reactant in the reaction of (A) is at least one alkylene polyamine selected from ethylene or propylene diamines, diethylene triamine, triethylene tetramine, tetraethylene pentamine, and pentaethylene hexamine.

18. A composition of claim 1 wherein said reactant in the reaction of (A) is a mixture of straight chain, branched chain, and cyclic polyethylene polyamines having an overall approximate composition falling in the range of triethylene tetramine to pentaethylene hexamine.

19. A composition of any one of claims 1, 3, 5, 7 and 10 wherein said post-treating agent comprises at least one boron compound.