US 3045042 A
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v 3,045,042 Patented July 17, 1 962 3,045,042 ACID POLYESTER SUCCINATES- Donald D. Staker, Nitro, W. Va., assignor to Monsanto Chemical Company, St. Louis, M0., a corporation of Delaware No Drawing. Filed Aug. 16, 1957, Ser. No. 678,525
13 Claims; (Cl'. 260-485) e The present invention relates to use of chemical compounds which are oil soluble, particularly in petroleum oil fractions andwhich exhibit rust preventive properties towards metals, especially steel and ferrous iron surfaces.
The simplest and most convenient method of developing a rust protecting film on the metal surface is to dissolve one of the preferred rust preventive compounds disclosed herein in a suitable petroleum base carrier such as motor gasoline, aviation gasoline, jetfuel, turbine oils and the like. Inasmuch as the lead salts of compounds of the preferred class of compounds do not form, or if formed are completely soluble. in the petroleum fraction employed, the compounds hereinafter described may be used in leadedfuels. Thus the fuels mentioned and containing the preferred rust preventive compound may be employed as a fuel in. internal combustionengines, jet engines and the like and the various pants and fittings of the engines are not damaged by deposition of insolubles and are protected from rusting. In particular fuel injection systems are not clogged or damaged by fuels containing the new adjuvants. Moreover, no insoluble alkaline earth salts are formed by reaction of sea water with the preferred class of compounds, thereby permitting the use of storage tanks previously containing a sea water ballast to be loaded with an oil fraction or a fuel treated with one of the preferred rust preventive compounds, as well as enabling storage of the treated fuel over sea water without serious loss of inhibitor taking place.
The preferred class of chemical compounds hereinafter described and set forth as rust preventive compounds are the partial esters of an alkyl or alkenylsuccinio anhydride and preferably are the products obtained by the reaction of one molar equivalent of a polyhydric alcohol with two molar equivalents of the anhydride. Structurally the preferred class of rust preventive compounds are most conveniently represented by the formula:
wherein of the radicals R and R, one is hydrogen and the other is selected from a group comprising alkyl and alkenyl radicals preferably containing from 8 to carbon atoms and R" is the residue of thetpolyhydric alcohol which generically may contain oxygen, sulfur or nitrogen in the chain as well as ester substituents, and preferably contains from 3 to 6 carbon atoms. The integer n represents a number from- 1 to'4 to indicate that within the purview of the invention are included the derivatives of diols, triols and other polyhydroxy compounds;
A typical procedure for the preparation of the chemical rust preventive compound employed in the: present invention is the following which is illustrative only as a non-limiting procedure.
Thedesire'd substituted succi'nic:
anhydride and alcohol charges are weighed into a suitable jacketed acid-resisting vessel equipped with agitation temperature recording means and a reflux condenser: The charge is heated to, about 95100 C. while agitating and held thereat and the progress of the reaction observed from time to time by withdrawing a sample anddetermining the neutralization number thereof. Heating is continued until the desired neutralization number is obtained or until it remains substantially constant. The reaction occurring is represented as follows: a
. 2O zH2 CH-(\ 0+ HO-ROH Hz-C H.
o 7 o ll ll C 2Hg -CHGO RO ?H2 H2 l-IC-CnHza (Ol'OH C(O)OH.
The following are illustrative of products obtained by heating one molecular proportion of a dihydric alcohol with twomolecularproportions of anankenylsuccinic anhydride. In each case the alkenylsuccinic anhydride used was dodecenylsuccinic anhydride prepared from propylene tetramer and maleic anhydride and the product was prepared from the intermediate by heating at about -100 C. for the indicated times, generally without a solvent or diluent although in a few cases the reaction was carried out by heating in kerosene.
Neutralization Time of Number E xarnple Alcohol Heating,
hours Found Gale.
1 Ethylene glycol 15.0 199 188. 5 2- Propylene glycoL 23. 0 210 184 3 1,4-Butane diol 4.0 181 4. 1 3-Butane diol 9. 0 178 180 5. 2,3-Butane (1101. 16. 5 104 180 6..- 2Butene-1,4-dio1 l4. 0 190 181 7. Diethylene glycol. 4. O 183. 4 175 8- 2,2'-Thi0 diethanoL 11.0 187 171 9; 1,5-Pentane diol... 10.0 184 176 10 1,4-Pentane diol 8.0 189 176 11 Neopentyl glyco 15. 0 176 12 1,6-Hexane diol 4. 0 176 172 13 2-Methyl-2,4pentane diol- 18.0 250 172 14 -1 Methyl-1,3-pentane dioL- 25.0 187 172 15 Dipropylene g1ycol 9.0 175 i 168 16--- Triethylene glycol 4. 5 183 163 17-.- 2,2,4Trimethyl-1,3penta l5. 0 165 165 18. 2-Ethylhexane diol.-1,3 13.0 181 165 19 2-,2-Diethylpropane (1101-1, 9. 0 159 169 20 2,5-Dimethylhexaue-2,5-d1ol 24. 5 271 165 21- Phenyl-Likethane diol 13. 5 188 167 22 1 2-Ethyl-2-butylpropane diol-1,3 10.0 161 162 23 3,6-Dimcthyloctane 3,6-diol. 18. 5 263 158 24--- Polyethylene glycol 200 4.0 153 25 Polyethylene glycol 400-- 4.0 126 121 26. Polypropylene glycol 150 19. 0 179 164 27 Polypropylene glycol 425- 15.0 129 118 28 3-Methyl 1,5-pentane diol 10.0 174 172 29 Trimethylene glycol 11.0 210 184 All of the foregoing products were soluble in petroleum The. numbersfollowing the glycol polymers indicate the molecular weight.
3 4 Using the same dodecenylsuccinic anhydride as emof the products identified in the foregoing tables and will ployed in the above exam le further ill t ti x serve to identify the particular material tested. ples are set forth below in which the ratio of the reactants varied. All these products were prepared by heating at 91 Strip Rust approximately 95-105 C. for the times indicated. TPSA Example Hydroxy Reactant means tetrapropenyl (dodecenyl) succinic anhydride. 10 5 p.p.m. p.p.m. p.p.m.
Ratio of Neutralization T]? SA to Time of Number Example Hydroxy Reactant Hydroxy Heating,
Reacta'nt Hours Found Gale.
l2A-Butnane triol g 1g;
astor 0' Trlethanolamine 3/1 6.5 170 177 kfi Glycerol 2/1 15.0 196 180 1 8%? Y 8? Pentaerythritol. 2/1 23.0 168 dn 4/1 19.0 187 e y pentane d1ol Methyl-1,3-pentane d1o1.
Dipropylene glycol 'lrlethylene glycol- 2,2 4-Tn'methyl-l,3-pentane d i0l Z-Ilthylhexane diol-1,3 2,2-Diethylpropane diol-1,3 2,5-Dimethylhexane-2,5-diol. Phenyl-LQ-ethane diol 2-Ethyl-2-butylpropane diol-1,3- 3,6-Dimethyloctane-3fi-diol The various chemical products of the class described were tested to determine their solubility in petroleum oil by adding 1% by weight of the chemical product to 100 parts of petroleum ether and stirring. If any residue is Polyethylene glycol 200". observed, the product 1s 1nd1cated as insoluble. 0f Polyethylene glycol the products in the foregomg table were soluble 1n pegolyplr opylene glycol s 0 yp opy ene g yco troleurn ether and gasoline. iil- Metlggl-llj-peptarie diol--. m time y ene g yco In order to obtain products which do not tend to for 172 443mm mob permanent emulsions nor to precipitate alkaline earth and lead salts, the alkenyl or alkyl group is desirably within the range of 8-15 carbon atoms. However, ex-
Oastor oil cellent rust inhibiting properties are obtained from refifitlgrz en diol actants containing alkyl and alkenyl groups outside this range. The following are illustrative of products in ::do:: Do: which the alkenylsuccinic anhydride varied. These prod- :33: none g3:
ucts were prepared by heating one molecular proportion of a dihydric alcohol with two molecular proportions of the alkenylsuccinic anhydride at 95-125 C.
Various other tests employed in the art were also utilized in the further testing of chemical products of the Neutralization present invention. A description of these tests and the Time of Number results obtained follow. EXample Anhydnde fi z f Water tolerance test.'l his test is used to evaluate the Found Cale. emulsion characteristics of the rust inhibited petroleum fraction, such as a petroleum fuel, as set forth in as 2-Meth 1-24- NOSA 28 0 267 208 A.S.T.M. D 1094-53. The apparatus consists of a 100 cc. 37 3? 28.0 224 173 glass stoppered graduated cylinder, which after thorough HDSA 32. cleaning is rinsed throughly with distilled water and 225 220 stored completely full of distilled water until used in a $8 iii 12% test. The water is removed and 80 cc. of iso-octane con- 13:0 118 142 taining 20 parts per million of the inhibitor under test is placed in the graduate and 20 cc. of distilled water Noslknmtenylsuccmic anhydride added thereto and the m xture 1s shaken vigorously at gllglsDgAil-dogecenylsuecinic ang grige. room temperature for 2 minutes. The mlxture is then al- -n- 9X8. eceny SIICOLHIOEH y I! e. v r oDsA nmtadecenylsuccmic anhydride. lowed to stand on a v1brat1on free surface for 5 rnmutes whereupon the volume of the aqueous layer and the All of the products in the foregoing table were soluble amount of emulsion, if any, are recorded. In order to in petroleum ether except the reaction product of 1,4- pass the test, the fuel shall separate sharply from the water butane diol and NOSA which was partially soluble, and there shall be no evidence of an emulsion, precipitate h rust preventive propel-ties f the chemical d- 50 or suspended matter within or upon either layer. Neither ucts were observed by carefully cleaning and polishing layer Shall have f g more ha 1 cc. in volume.
in the well recognized manner for performing this test f water MVP-T1115 l 1S s gn d t detest Strips f Steel 1 X 5/ X 1 having an ten nine the solub1l1ty of the alkahne earth salts of rust inhibitors. Synthetic sea water was prepared according h grade deslgnatm and gomusly shakmg to the method set forth in Procedure B, A.S.T.M. D665- specimen in 75 cc. of petroleum ether containing the desired concentration 01' concentrations (from 5 to 20 method conslsts m addmg 250 of n'heptane conta1mng about 200 ppm. of the material to be tested mllhon of Solvent) of the After and 25 cc. of synthetic sea water to a 500 cc. 3-neck standing for one-half hour, 2 cc. of dlstilled water are flask equipped with stirrer and reflux condenser and added and the sample is reshaken. The strip is allowed stirring for 30 minutes at 1.00m temperature Agitation to Stand the Wet Petroleum ether at room temperature was stopped and when motion had ceased the interface f r about three hours, is then removed and Visually was examined for scum and the walls of the flask ex- Spected for f 0f the tests 1 ar P amined for precipitate of which there shall be none. ucts of the present 1nvent1on are set forth in the fol- Lead salt tam-This test is designed to indicate the poslowing table. The example numbers correspond to those sibility of precipitate from the use of rust inhibitor in a the invention.
leaded gasoline. In this test, an ionizable lead salt is added to assure a concentration of lead ion. The test solution is prepared by dissolving 25 parts of. lead naphthenate in 2500 parts of a regular gasoline and the solution is filtered through a double thickness of filter paper and then through a layer of fullers earth. Thereupon 100 cc. of the test solution is added to a 500 cc. 3-neck flask equipped with a stirrer and air condenser. Agitation is started and the rust inhibitor under test is added dropwise until about 0.5 gram has been added whereupon agitation is continued for an hour at room temperature and the mixture is examined for haziness or insolubles with the aid of a flashlight. To pass the test there shall be no more haze than is exhibited by use of a blank test with no inhibitor present. The results obtained from the above-describedtests are set forth in Table I wherein various reaction products of an alkenylsuccinic anhydride with the diol indicated in the table are shown.
T able' I Sea Lead Water Water Salt Example Diol Test Tolerance Test (insol- Test (insolubles) ubles) 3 L t-Butane diol none palss bordernone.
me. 4. 1,3-Butane diol Do. 5. 2,3-Butane diol Do. 11... Neopeutyl glyco Do. 12 1,6-Hexane diol Do. i 13 -2-l\ ic1ithyl-2,4-pentane none i .do Do.
Trirnethyleue glycol-.- trace do Do. 1,2,4-Butane trioL. .none fail Do. Castor o' trace palssborder- Do.
me. 4 Trie h'mnl min nonedo Do. 33 lycerol trace pass trace 36 2-(I1l\ r1ethy1-2,4-pentane fail"; do il.
10 4O 1,4-Butane diol do do none.
The rust preventing characteristics of steam turbine oil in the presence of water was determined by following A.S.T.M. Test D665-53T, Procedure B thereof. The oil employed was a base stock in commercial use for the formulation of steam turbine finished lubricants and of course contained no inhibitor of any kind. In this test, the reaction product comprising the partial ester from tetrapropenylsuccinic anhydride with the indicated diol yielded the results shown in Table H.
lustrating the formation of the preferred rust preventive compounds, no water is evolved in the reaction of the 'diol and succinic anhydride derivative. The products, while containing carboxyl group-s, are Weak acids and do not liberate hydrogen on contact with ferrous metal or other metallic fittings used in a motor or engine. It is apparent that a wide range of products are included in Other alkenylsuccinic anhydrides have been reacted with diols as described. Thus, octenylsuccinic anhydride, dodecenylsuccinic anhydride, hexadecenylsuccinic anhydride and octadecenylsuccinic anhydride were reacted with 1,4-butane diol.
It is intended to cover all changes and modifications of the examples of the invention herein chosen for purposes of disclosure which do not constitute departures from the spirit and scope. of the invention.
What is claimed is: e 1. A composition of matter soluble in petroleum oil fractions having the general formula i-on ii-on. R-cH H R R -dH nb n' ll ll wherein of R and R one is hydrogen, and the other an alkenyl radical which contains 8 to 18 carbon atoms, R" is a residue of a polyhydric alcohol remaining from removal of "1+1 hydroxy groups from an alcohol containing two to four hydroxy groups attached to aliphatic carbon and n is an. integer at least one but less than four.
wherein of R and R one is hydrogen and the other an alkenyl radical containing 8 to. 15' carbon atoms, R" is a residue of a polyhydric alcohol remaining from removal of n +1 hydroxy groups from an aliphatic alcohol containing three to six carbon atoms and n is an integer at at least one but less than four.
3. A composition of matter soluble in petroleum oil fractions having the general formula wherein of R and R one represents hydrogen and the other an alkenyl group of 8-15 carbon atoms and R" is an alkylene group of 3-6 carbon atoms.
4. A composition of matter soluble in petroleum oil wherein of R and R one represents hydrogen and the other a branched chain dodecenyl group.
5. A composition of matter soluble in petroleum oil fractions having the general formula 0 0-0H (I) R(|1H H? '-(]]H CH3 (llHz HCfi-R' COCCHz-COO II I H H 0 CH3 0 ,wherein of R and R one represents hydrogen and the other a branched chain dodecenyl group.
6. The process which comprises heating one mole proportion of an organic polyhydroxy compound containing from 2 to 4 hydroxy radicals linked to aliphatic carbon with alkenylsuccinic anhydride the number of carbon atoms in the side chain being 818, the mole proportion of said anhydride being at least two, and continuing heating without formation of water until the neutralization number is essentially constant and a reaction product soluble in petroleum ether forms.
7. The process which comprises heating one mole proportion of a polyhydric alcohol containing 2-4 hydroxy radicals and two mole proportions of any alkenylsuccinic anhydride containing 8-15 carbon atoms in the alkenyl chain and continuing heating without formation of water until the neutralization number is essentially constant and a reaction product soluble in petroleum ether forms.
8. The process which comprises heating one mole pro portion of a polyhydric alcohol containing 2-3 hydroxy radicals and 3-6 carbon atoms with 2-3 mole proportions of dodecenyl-succinic anhydride, heating being continued without formation of water until the neutralization number is essentially constant and a reaction product soluble in petroleum ether forms.
9. The process which comprises heating at 95125 C., without forming water, until the neutralization number essentially constant two mole proportions of dodecenyl-succinic anhydride and one mole proportion of 1,4-butane diol and a reaction product soluble in petroleum ether forms.
10. The process which comprises heating at 95-125 C., without forming water, until the neutralization number is essentially constant two mole proportions of dodecenyl-succinic anhydride and one mole proportion of 2methyl-2,4-pentane diol and a reaction product soluble in petroleum ether forms.
11. The process which comprises heating at 95-125 wherein of R and R one represents hydrogen and the other a branched chain dodecenyl group where N represents nitrogen.
References Cited in the file of this patent UNITED STATES PATENTS 2,294,259 Van Peski et al Aug. 25, 1942 2,435,619 Young et al. Feb. 10, 1948 2,442,672 Von Fuchs et al. June 1, 1948 2,497,433 Blake Feb. 14, 1950 2,723,286 Young et al. Nov. 8, 1955 2,890,210 Phillips et al. June 9, 1959