CA2057196A1 - Process for the preparation of calcium sulfonate/calcium carbonate complexes - Google Patents
Process for the preparation of calcium sulfonate/calcium carbonate complexesInfo
- Publication number
- CA2057196A1 CA2057196A1 CA 2057196 CA2057196A CA2057196A1 CA 2057196 A1 CA2057196 A1 CA 2057196A1 CA 2057196 CA2057196 CA 2057196 CA 2057196 A CA2057196 A CA 2057196A CA 2057196 A1 CA2057196 A1 CA 2057196A1
- Authority
- CA
- Canada
- Prior art keywords
- carboxylic acids
- acids
- water
- calcium
- mixture
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Abandoned
Links
- 238000000034 method Methods 0.000 title claims abstract description 23
- 239000011575 calcium Substances 0.000 title claims abstract description 14
- VTYYLEPIZMXCLO-UHFFFAOYSA-L Calcium carbonate Chemical class [Ca+2].[O-]C([O-])=O VTYYLEPIZMXCLO-UHFFFAOYSA-L 0.000 title claims abstract description 12
- 229910052791 calcium Inorganic materials 0.000 title claims abstract description 11
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 title claims abstract description 8
- 238000002360 preparation method Methods 0.000 title claims abstract description 8
- BDHFUVZGWQCTTF-UHFFFAOYSA-M sulfonate Chemical compound [O-]S(=O)=O BDHFUVZGWQCTTF-UHFFFAOYSA-M 0.000 title claims abstract description 6
- 150000001735 carboxylic acids Chemical class 0.000 claims abstract description 23
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 claims abstract description 16
- 239000002253 acid Substances 0.000 claims abstract description 16
- 239000000203 mixture Substances 0.000 claims abstract description 14
- 150000007513 acids Chemical class 0.000 claims abstract description 11
- 229910002092 carbon dioxide Inorganic materials 0.000 claims abstract description 9
- 238000006243 chemical reaction Methods 0.000 claims abstract description 8
- 239000002904 solvent Substances 0.000 claims abstract description 8
- 239000007788 liquid Substances 0.000 claims abstract description 7
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 7
- AXCZMVOFGPJBDE-UHFFFAOYSA-L calcium dihydroxide Chemical compound [OH-].[OH-].[Ca+2] AXCZMVOFGPJBDE-UHFFFAOYSA-L 0.000 claims abstract description 6
- 239000000920 calcium hydroxide Substances 0.000 claims abstract description 6
- 229910001861 calcium hydroxide Inorganic materials 0.000 claims abstract description 6
- 239000001569 carbon dioxide Substances 0.000 claims abstract description 6
- 239000003795 chemical substances by application Substances 0.000 claims abstract description 6
- 239000012429 reaction media Substances 0.000 claims abstract description 6
- 239000000292 calcium oxide Substances 0.000 claims abstract description 4
- ODINCKMPIJJUCX-UHFFFAOYSA-N calcium oxide Inorganic materials [Ca]=O ODINCKMPIJJUCX-UHFFFAOYSA-N 0.000 claims abstract description 4
- -1 unsaturated aliphatic fatty acids Chemical class 0.000 claims description 8
- 229910000019 calcium carbonate Inorganic materials 0.000 claims description 4
- 235000014113 dietary fatty acids Nutrition 0.000 claims description 3
- 239000000194 fatty acid Substances 0.000 claims description 3
- 229930195729 fatty acid Natural products 0.000 claims description 3
- LNETULKMXZVUST-UHFFFAOYSA-N 1-naphthoic acid Chemical class C1=CC=C2C(C(=O)O)=CC=CC2=C1 LNETULKMXZVUST-UHFFFAOYSA-N 0.000 claims description 2
- 150000001413 amino acids Chemical class 0.000 claims description 2
- 125000003118 aryl group Chemical group 0.000 claims description 2
- 125000004432 carbon atom Chemical group C* 0.000 claims description 2
- 150000004665 fatty acids Chemical class 0.000 claims description 2
- 229920006395 saturated elastomer Polymers 0.000 claims 1
- 239000000047 product Substances 0.000 description 11
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 8
- 229940043430 calcium compound Drugs 0.000 description 7
- 150000001674 calcium compounds Chemical class 0.000 description 7
- 238000006386 neutralization reaction Methods 0.000 description 6
- 229930195733 hydrocarbon Natural products 0.000 description 5
- 150000002430 hydrocarbons Chemical class 0.000 description 5
- 239000011541 reaction mixture Substances 0.000 description 5
- 150000003460 sulfonic acids Chemical class 0.000 description 5
- XNWFRZJHXBZDAG-UHFFFAOYSA-N 2-METHOXYETHANOL Chemical compound COCCO XNWFRZJHXBZDAG-UHFFFAOYSA-N 0.000 description 4
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 3
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 3
- 239000004215 Carbon black (E152) Substances 0.000 description 3
- 239000004264 Petrolatum Substances 0.000 description 3
- 150000001875 compounds Chemical class 0.000 description 3
- 229940066842 petrolatum Drugs 0.000 description 3
- 235000019271 petrolatum Nutrition 0.000 description 3
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 2
- UFWIBTONFRDIAS-UHFFFAOYSA-N Naphthalene Chemical compound C1=CC=CC2=CC=CC=C21 UFWIBTONFRDIAS-UHFFFAOYSA-N 0.000 description 2
- 125000001931 aliphatic group Chemical group 0.000 description 2
- 229910052784 alkaline earth metal Inorganic materials 0.000 description 2
- 150000001342 alkaline earth metals Chemical class 0.000 description 2
- WPYMKLBDIGXBTP-UHFFFAOYSA-N benzoic acid Chemical compound OC(=O)C1=CC=CC=C1 WPYMKLBDIGXBTP-UHFFFAOYSA-N 0.000 description 2
- 238000009835 boiling Methods 0.000 description 2
- BRPQOXSCLDDYGP-UHFFFAOYSA-N calcium oxide Chemical compound [O-2].[Ca+2] BRPQOXSCLDDYGP-UHFFFAOYSA-N 0.000 description 2
- 150000001732 carboxylic acid derivatives Chemical class 0.000 description 2
- 238000004821 distillation Methods 0.000 description 2
- 239000003921 oil Substances 0.000 description 2
- YNPNZTXNASCQKK-UHFFFAOYSA-N phenanthrene Chemical compound C1=CC=C2C3=CC=CC=C3C=CC2=C1 YNPNZTXNASCQKK-UHFFFAOYSA-N 0.000 description 2
- 238000004321 preservation Methods 0.000 description 2
- 239000007787 solid Substances 0.000 description 2
- 238000003756 stirring Methods 0.000 description 2
- WRIDQFICGBMAFQ-UHFFFAOYSA-N (E)-8-Octadecenoic acid Natural products CCCCCCCCCC=CCCCCCCC(O)=O WRIDQFICGBMAFQ-UHFFFAOYSA-N 0.000 description 1
- UZCGWDVAAVGXFV-KTKRTIGZSA-N 2-[[(z)-octadec-9-enyl]amino]acetic acid Chemical compound CCCCCCCC\C=C/CCCCCCCCNCC(O)=O UZCGWDVAAVGXFV-KTKRTIGZSA-N 0.000 description 1
- ZNQVEEAIQZEUHB-UHFFFAOYSA-N 2-ethoxyethanol Chemical compound CCOCCO ZNQVEEAIQZEUHB-UHFFFAOYSA-N 0.000 description 1
- LQJBNNIYVWPHFW-UHFFFAOYSA-N 20:1omega9c fatty acid Natural products CCCCCCCCCCC=CCCCCCCCC(O)=O LQJBNNIYVWPHFW-UHFFFAOYSA-N 0.000 description 1
- QSBYPNXLFMSGKH-UHFFFAOYSA-N 9-Heptadecensaeure Natural products CCCCCCCC=CCCCCCCCC(O)=O QSBYPNXLFMSGKH-UHFFFAOYSA-N 0.000 description 1
- 239000005711 Benzoic acid Substances 0.000 description 1
- BVKZGUZCCUSVTD-UHFFFAOYSA-L Carbonate Chemical compound [O-]C([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-L 0.000 description 1
- 235000006696 Catha edulis Nutrition 0.000 description 1
- 240000007681 Catha edulis Species 0.000 description 1
- 235000008733 Citrus aurantifolia Nutrition 0.000 description 1
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 1
- LCGLNKUTAGEVQW-UHFFFAOYSA-N Dimethyl ether Chemical compound COC LCGLNKUTAGEVQW-UHFFFAOYSA-N 0.000 description 1
- 239000005642 Oleic acid Substances 0.000 description 1
- ZQPPMHVWECSIRJ-UHFFFAOYSA-N Oleic acid Natural products CCCCCCCCC=CCCCCCCCC(O)=O ZQPPMHVWECSIRJ-UHFFFAOYSA-N 0.000 description 1
- 241000324401 Superba Species 0.000 description 1
- 239000004784 Superba Substances 0.000 description 1
- 235000011941 Tilia x europaea Nutrition 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 150000007933 aliphatic carboxylic acids Chemical class 0.000 description 1
- 125000000217 alkyl group Chemical group 0.000 description 1
- 125000003710 aryl alkyl group Chemical group 0.000 description 1
- 235000010233 benzoic acid Nutrition 0.000 description 1
- 159000000007 calcium salts Chemical class 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 150000007942 carboxylates Chemical class 0.000 description 1
- 230000003197 catalytic effect Effects 0.000 description 1
- 239000000470 constituent Substances 0.000 description 1
- 238000005260 corrosion Methods 0.000 description 1
- 230000007797 corrosion Effects 0.000 description 1
- 239000010779 crude oil Substances 0.000 description 1
- 150000002170 ethers Chemical class 0.000 description 1
- 239000000706 filtrate Substances 0.000 description 1
- 238000001914 filtration Methods 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-M hydroxide Chemical compound [OH-] XLYOFNOQVPJJNP-UHFFFAOYSA-M 0.000 description 1
- WGCNASOHLSPBMP-UHFFFAOYSA-N hydroxyacetaldehyde Natural products OCC=O WGCNASOHLSPBMP-UHFFFAOYSA-N 0.000 description 1
- 239000012535 impurity Substances 0.000 description 1
- 239000003112 inhibitor Substances 0.000 description 1
- QXJSBBXBKPUZAA-UHFFFAOYSA-N isooleic acid Natural products CCCCCCCC=CCCCCCCCCC(O)=O QXJSBBXBKPUZAA-UHFFFAOYSA-N 0.000 description 1
- 239000004571 lime Substances 0.000 description 1
- 239000010687 lubricating oil Substances 0.000 description 1
- 238000002844 melting Methods 0.000 description 1
- 230000008018 melting Effects 0.000 description 1
- MYWUZJCMWCOHBA-VIFPVBQESA-N methamphetamine Chemical compound CN[C@@H](C)CC1=CC=CC=C1 MYWUZJCMWCOHBA-VIFPVBQESA-N 0.000 description 1
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 1
- 239000002480 mineral oil Substances 0.000 description 1
- 235000010446 mineral oil Nutrition 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 239000012454 non-polar solvent Substances 0.000 description 1
- ZQPPMHVWECSIRJ-KTKRTIGZSA-N oleic acid Chemical compound CCCCCCCC\C=C/CCCCCCCC(O)=O ZQPPMHVWECSIRJ-KTKRTIGZSA-N 0.000 description 1
- 239000003791 organic solvent mixture Substances 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- 239000003348 petrochemical agent Substances 0.000 description 1
- 239000003208 petroleum Substances 0.000 description 1
- 239000002798 polar solvent Substances 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 238000007789 sealing Methods 0.000 description 1
- 230000003381 solubilizing effect Effects 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 125000001273 sulfonato group Chemical class [O-]S(*)(=O)=O 0.000 description 1
- 150000004670 unsaturated fatty acids Chemical class 0.000 description 1
- 235000021122 unsaturated fatty acids Nutrition 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D5/00—Coating compositions, e.g. paints, varnishes or lacquers, characterised by their physical nature or the effects produced; Filling pastes
- C09D5/08—Anti-corrosive paints
-
- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
- C10M159/00—Lubricating compositions characterised by the additive being of unknown or incompletely defined constitution
- C10M159/12—Reaction products
- C10M159/20—Reaction mixtures having an excess of neutralising base, e.g. so-called overbasic or highly basic products
- C10M159/24—Reaction mixtures having an excess of neutralising base, e.g. so-called overbasic or highly basic products containing sulfonic radicals
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Oil, Petroleum & Natural Gas (AREA)
- General Chemical & Material Sciences (AREA)
- Life Sciences & Earth Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Materials Engineering (AREA)
- Wood Science & Technology (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
- Lubricants (AREA)
- Preventing Corrosion Or Incrustation Of Metals (AREA)
- Compounds Of Alkaline-Earth Elements, Aluminum Or Rare-Earth Metals (AREA)
Abstract
ABSTRACT OF THE DISCLOSURE:
Process for the preparation of calcium sulfonate/calcium carbonate complexes In the process for the preparation of superbasic calcium sulfonate/calcium carbonate complexes, a mixture of - oil-soluble aralkylsulfonic acids, - calcium oxide and/or calcium hydroxide and - carboxylic acids, is reacted in the presence of a liquid non-polar reaction medium, water-soluble polar solubilizing agents and water.
The reaction with carbon dioxide is then carried out.
Water-immiscible or water-insoluble carboxylic acids are employed as the carboxylic acids. The process products are used as anticorrosive agents.
Process for the preparation of calcium sulfonate/calcium carbonate complexes In the process for the preparation of superbasic calcium sulfonate/calcium carbonate complexes, a mixture of - oil-soluble aralkylsulfonic acids, - calcium oxide and/or calcium hydroxide and - carboxylic acids, is reacted in the presence of a liquid non-polar reaction medium, water-soluble polar solubilizing agents and water.
The reaction with carbon dioxide is then carried out.
Water-immiscible or water-insoluble carboxylic acids are employed as the carboxylic acids. The process products are used as anticorrosive agents.
Description
7 ~ ~ ~
HOECHST AKTIE21GESELLSCH~FT HOE 90/F 366 Dr. GT/PP
Description Process for the preparation o calcium sulfonate/calcium carbonate complexes The invention relates to a process of the type mentioned in the precharacterizing clause of claim 1. Such a process has been disclosed in GB-B-2,146,348. The result-ing products are oil-soluble superba ic calcium sulfon-ate calcium carbona~e complexes. The invention also relates to the use of these products.
In the process of the Bri~ish paten~ specification, oil-soluble aralkylsulfonic acids are neutralized with a stoichiometric excess of basic calcium compounds in a liquid non-polar reaction medium. Aliphatic carbo~ylic acids having 1 to 4 carbon atoms or benzoic acid, but preferably acetic acid, and lower aliphatic alcohols and/or alkoxyalkanols, in particular the monomethyl ether of ethylene glycol, are urthermore also present in the reaction medium during this reaction. The excess basic calcium compounds still present aiEter the neutralization are converted into calcium carbonate by passing in carbon dioxide. The desired superbasic sulfonate/carbonate complex is form~d in this proced~re. Unreacted basic calcium compounds are removed by filtration and the volatile fractions of the reaction mixture are removed by distillation. Precisely this last step of puriication of the product to remove undesired concomitant substances often presents major problems and i8 technically very complex. The filtered product~ often show non-reproducible, varying properties, so tha~ they are unusable ~or commercial further processing.
The process product is used as a starting component for the preparation of lubricating oil additives and as a raw material for the preparation of anticorrosive agents for the sector of preservation of hollow spaces and under-sealing on, for example, road vehicles. In this connec-tion, these sulfonate~carbonate complexes are often mixed -- 2 ~
with alkaline ear~h me~al derivatives of aliphatic carbo~ylic acid~, which are themselves anticorrosive agents, in order to intensify their action. The - preparation of these mixtures which can be used as anticorrosive agents means an additional st~p during processing of the calcium ~ulfonate/calcium carbonate comple~es / and furthermore the alkaline earth metal derivative of the alipha~ic carboxylic acids mu~t be prepared separately beforehand.
The object of the invention i6 thus to improve the known pxocess to ~he extent ~hat the process product s~an be ~eparated o~f from the concomitant subs~ance~ wi~hout problems. The resulting process product should furth~r-more have an improved action when used as an anti-corrosi~e agent, so khat subsequent mixing with alkaline earth metal derivatives of aliphatic carboxylic acid~ can be dispensed with.
According to the invention, this object i~ achiaved by replacing the water-soluble or wat;er-miscible carboxylic acids present in the reaction mixture in the known process by higher, water-immis~ible and practically water-insoluble carboxylic acids.
The invention thus relates to the proceEs having the features mentioned in claim 1, the dependen~ claims describing ad~antageous embodiments of the process. The particular content of the individual components, with the exception of the water-insoluble or water-immiscible carboxylic acids which are essential to the inventiont corresponds to the amounts described in th~ prior art, - 30 although the pxoportions stated below are particularly advantageous for the present invention.
The carboxylic acids employed according to th~ invention are naturally occurring or synth~tic fatty acids and have at least B, preferably 8 to 24, carbon atomsn They are in general in the form of a mixture. Water-insolublel ~ 3 water-immiscible aromatic carboxylic acids, such as, for example, naphthalenecarboxylic acids, are also suitable.
Paraffincarboxylic acids, which are prepared by catalytic oxidation of petrochemicals or polyethyl2ne wax, the former being known by the name oxidized petrolatum, are preferably employed. Suitable carboxylic acids are, for example, also unsaturated fatty acids, such a~ oleic acid, and amino acids, æuch as oleylaminoacetic acid. The content of water-insoluble or wa~er-immiscible carboxylic acids i~ in general more than 2, in particular 2.5 ~o 15 % by weight, based on the aral~ylsulfonic acids, but can also be up to 50 % by weight.
In the process of the in~ention, the constituents of the reaction mixture are ~irst mixed with one another, the acid~ being neutralized at room temperature by an excess of basic calcium compounds, and the mixture is then charged with carbon dioxide at elevated temperature. The entire couxse of the process can thus take place in a single reaction container, i.e. a~ a one-stage process.
The neutralization of the sulfonic acids and carboxylic acids takes place in a liquid non-polar reaction medium, for example in the form of liquid hydrocarbons, oils, for example mineral oil, or in mixtures of these compounds, a polar solubilizing agent being added to accelerate the neutralization re~ction.
The oil-soluble aralkylsulfonic acids consist of an aromatic nucleus, for example naphthalene or phenan-threne, but in particular a benzene nucleu6, having ak lea3t one S03H group and one or two straight-chain or branched alkyl radicals, such as axe describedr for example, in U.S. Patents 3,342,079; 3,372,115; 3,492,831;
3,746,643 and 3,816,310. These compounds axe also known by thP term oil-soluble crude oil sulfonic acids or petroleumsulfonic acids. The aralkyl~ulfonic acids are added to the liquid non-polar reaction medium, while stirring, the calcium oxide andior calcium hydroxide (~white lime h~drate~ required for neu~ralization of the aralkylsulfonic acids and the carboxylic acids being added in excess simultaneously, beforehand and/or there-after. The amount of basic calcium compound is more than S twice the amount required for neutralization o~ the sulfonic and carboxylic acids.
After an after-stirring time of 15 to 30 minutes, water and the polar solubilizing agent in the form of water-soluble or water-miscible aliphatic alcohols, prefer bly Cl-C4-alkanols, or w~ter-soluble or water-miscible alkoxy-alkanols, in particular water-soluble monoal~yl ethers of a water-soluble glycol, such as, for example, the mono-methyl or monoethyl ether of ethylene glycol (methyl-glycol or ethylglycol), are added. The amount of polar solubilizing a~ent is in general 3 to 15 ~ by weight, based on the liquid non-polar reaction medlum. In con-trast, the amount of water is in general lower than the amount of polar solubilizing agent and is usually 1 to 15 % by weight, based on the polar solubilizing agent.
The water-immiscible or water-insoluble carboxylic acids which are essential to the invention arQ then also added to the reaction mixkure. This component can al80 be added before, at the same tim~ as or after the aralkylsulfonic acids. Since the carboxylic acid~ are solid at room temperature, they are usually first liquefied by melting and added to the reaction mixture in this form. The carboxylic acids, like the aral~ylsulfonic acids, are neutralized by the calcium oxide or calcium hydroxide and converted into the corresponding calcium salts.
The neutralization reactions are advantageously carried out at room temperature, i.e. at 15 to 30C.
Af~er the neutralization of the sulfonic and carboxylic acids, the carbonation is carried ou~ to neutralize and solubilize excess basic calcium compounds. For this, C02 is usually passed in gaseous form into the reaction - 5 ~
mixture, which has been heated to 30 to 95, in particulax 40 to 70C. It is in general sufficient to add not more than 1 mol of CO2 p~r mol of calcium, the minimum amount of CO2 being 0.7 mol per mol of Ca.
The process product is a complex of superbasic calcium aralkylsulfona~es, calcium carbonate and calcium car-boxylate and is pre~ent in an organic polar/non polar solvent mixture. ~he Ca content measured i6 greater than that determined stoichiometrically. The solid particles of unreacted basic calcium compounds and othex impurities can be remo~ed without problems ~hrough a suitable clarifying filter, mesh width, for example, 200 to 400 ~m. The process product dis~olved or finely dispersed in the organic solvent mixture i~ obtained in concentra~-ed`form by removal of some or substantially all the sol-vents by distillation.
The product ha~ the advantage that it is obtained in a concentrated form without problems and can be employed a~
a corrosion inhibitor without further addition of Ca carboxylate. It is particularly suitable for preservation of hollow spaces and as an underseal for road vehicles.
The invention is illustrated in more detail by the following example~.
Exam~le 1 The following components are reacted in a stirred container:
HOECHST AKTIE21GESELLSCH~FT HOE 90/F 366 Dr. GT/PP
Description Process for the preparation o calcium sulfonate/calcium carbonate complexes The invention relates to a process of the type mentioned in the precharacterizing clause of claim 1. Such a process has been disclosed in GB-B-2,146,348. The result-ing products are oil-soluble superba ic calcium sulfon-ate calcium carbona~e complexes. The invention also relates to the use of these products.
In the process of the Bri~ish paten~ specification, oil-soluble aralkylsulfonic acids are neutralized with a stoichiometric excess of basic calcium compounds in a liquid non-polar reaction medium. Aliphatic carbo~ylic acids having 1 to 4 carbon atoms or benzoic acid, but preferably acetic acid, and lower aliphatic alcohols and/or alkoxyalkanols, in particular the monomethyl ether of ethylene glycol, are urthermore also present in the reaction medium during this reaction. The excess basic calcium compounds still present aiEter the neutralization are converted into calcium carbonate by passing in carbon dioxide. The desired superbasic sulfonate/carbonate complex is form~d in this proced~re. Unreacted basic calcium compounds are removed by filtration and the volatile fractions of the reaction mixture are removed by distillation. Precisely this last step of puriication of the product to remove undesired concomitant substances often presents major problems and i8 technically very complex. The filtered product~ often show non-reproducible, varying properties, so tha~ they are unusable ~or commercial further processing.
The process product is used as a starting component for the preparation of lubricating oil additives and as a raw material for the preparation of anticorrosive agents for the sector of preservation of hollow spaces and under-sealing on, for example, road vehicles. In this connec-tion, these sulfonate~carbonate complexes are often mixed -- 2 ~
with alkaline ear~h me~al derivatives of aliphatic carbo~ylic acid~, which are themselves anticorrosive agents, in order to intensify their action. The - preparation of these mixtures which can be used as anticorrosive agents means an additional st~p during processing of the calcium ~ulfonate/calcium carbonate comple~es / and furthermore the alkaline earth metal derivative of the alipha~ic carboxylic acids mu~t be prepared separately beforehand.
The object of the invention i6 thus to improve the known pxocess to ~he extent ~hat the process product s~an be ~eparated o~f from the concomitant subs~ance~ wi~hout problems. The resulting process product should furth~r-more have an improved action when used as an anti-corrosi~e agent, so khat subsequent mixing with alkaline earth metal derivatives of aliphatic carboxylic acid~ can be dispensed with.
According to the invention, this object i~ achiaved by replacing the water-soluble or wat;er-miscible carboxylic acids present in the reaction mixture in the known process by higher, water-immis~ible and practically water-insoluble carboxylic acids.
The invention thus relates to the proceEs having the features mentioned in claim 1, the dependen~ claims describing ad~antageous embodiments of the process. The particular content of the individual components, with the exception of the water-insoluble or water-immiscible carboxylic acids which are essential to the inventiont corresponds to the amounts described in th~ prior art, - 30 although the pxoportions stated below are particularly advantageous for the present invention.
The carboxylic acids employed according to th~ invention are naturally occurring or synth~tic fatty acids and have at least B, preferably 8 to 24, carbon atomsn They are in general in the form of a mixture. Water-insolublel ~ 3 water-immiscible aromatic carboxylic acids, such as, for example, naphthalenecarboxylic acids, are also suitable.
Paraffincarboxylic acids, which are prepared by catalytic oxidation of petrochemicals or polyethyl2ne wax, the former being known by the name oxidized petrolatum, are preferably employed. Suitable carboxylic acids are, for example, also unsaturated fatty acids, such a~ oleic acid, and amino acids, æuch as oleylaminoacetic acid. The content of water-insoluble or wa~er-immiscible carboxylic acids i~ in general more than 2, in particular 2.5 ~o 15 % by weight, based on the aral~ylsulfonic acids, but can also be up to 50 % by weight.
In the process of the in~ention, the constituents of the reaction mixture are ~irst mixed with one another, the acid~ being neutralized at room temperature by an excess of basic calcium compounds, and the mixture is then charged with carbon dioxide at elevated temperature. The entire couxse of the process can thus take place in a single reaction container, i.e. a~ a one-stage process.
The neutralization of the sulfonic acids and carboxylic acids takes place in a liquid non-polar reaction medium, for example in the form of liquid hydrocarbons, oils, for example mineral oil, or in mixtures of these compounds, a polar solubilizing agent being added to accelerate the neutralization re~ction.
The oil-soluble aralkylsulfonic acids consist of an aromatic nucleus, for example naphthalene or phenan-threne, but in particular a benzene nucleu6, having ak lea3t one S03H group and one or two straight-chain or branched alkyl radicals, such as axe describedr for example, in U.S. Patents 3,342,079; 3,372,115; 3,492,831;
3,746,643 and 3,816,310. These compounds axe also known by thP term oil-soluble crude oil sulfonic acids or petroleumsulfonic acids. The aralkyl~ulfonic acids are added to the liquid non-polar reaction medium, while stirring, the calcium oxide andior calcium hydroxide (~white lime h~drate~ required for neu~ralization of the aralkylsulfonic acids and the carboxylic acids being added in excess simultaneously, beforehand and/or there-after. The amount of basic calcium compound is more than S twice the amount required for neutralization o~ the sulfonic and carboxylic acids.
After an after-stirring time of 15 to 30 minutes, water and the polar solubilizing agent in the form of water-soluble or water-miscible aliphatic alcohols, prefer bly Cl-C4-alkanols, or w~ter-soluble or water-miscible alkoxy-alkanols, in particular water-soluble monoal~yl ethers of a water-soluble glycol, such as, for example, the mono-methyl or monoethyl ether of ethylene glycol (methyl-glycol or ethylglycol), are added. The amount of polar solubilizing a~ent is in general 3 to 15 ~ by weight, based on the liquid non-polar reaction medlum. In con-trast, the amount of water is in general lower than the amount of polar solubilizing agent and is usually 1 to 15 % by weight, based on the polar solubilizing agent.
The water-immiscible or water-insoluble carboxylic acids which are essential to the invention arQ then also added to the reaction mixkure. This component can al80 be added before, at the same tim~ as or after the aralkylsulfonic acids. Since the carboxylic acid~ are solid at room temperature, they are usually first liquefied by melting and added to the reaction mixture in this form. The carboxylic acids, like the aral~ylsulfonic acids, are neutralized by the calcium oxide or calcium hydroxide and converted into the corresponding calcium salts.
The neutralization reactions are advantageously carried out at room temperature, i.e. at 15 to 30C.
Af~er the neutralization of the sulfonic and carboxylic acids, the carbonation is carried ou~ to neutralize and solubilize excess basic calcium compounds. For this, C02 is usually passed in gaseous form into the reaction - 5 ~
mixture, which has been heated to 30 to 95, in particulax 40 to 70C. It is in general sufficient to add not more than 1 mol of CO2 p~r mol of calcium, the minimum amount of CO2 being 0.7 mol per mol of Ca.
The process product is a complex of superbasic calcium aralkylsulfona~es, calcium carbonate and calcium car-boxylate and is pre~ent in an organic polar/non polar solvent mixture. ~he Ca content measured i6 greater than that determined stoichiometrically. The solid particles of unreacted basic calcium compounds and othex impurities can be remo~ed without problems ~hrough a suitable clarifying filter, mesh width, for example, 200 to 400 ~m. The process product dis~olved or finely dispersed in the organic solvent mixture i~ obtained in concentra~-ed`form by removal of some or substantially all the sol-vents by distillation.
The product ha~ the advantage that it is obtained in a concentrated form without problems and can be employed a~
a corrosion inhibitor without further addition of Ca carboxylate. It is particularly suitable for preservation of hollow spaces and as an underseal for road vehicles.
The invention is illustrated in more detail by the following example~.
Exam~le 1 The following components are reacted in a stirred container:
2 500 kg of hydrocarbon mixture (boiling point 150-200C) 1 720 kg of pPtroleumsulfonic acid (oil-soluble ~rude oil sulfonic acids) 999 kg of calcium hydroxide 287 kg of methylglycol 2b7 kg of water ~ 3 172 kg of oxidized petrolatum (water-in601uble carboxylic acid~) 470 kg of carbon dioxide gas The hydrocarbon mixtllre is first initially introduced into the contaîner at room temperature and the ~ated amount~ of petroleum~ulfoni~ acid and calcium hydroxide are introduced.
After an after-~tirring time of 20 minutes, the methyl-glycol and the water are added at ambient temperature.
The molten oxidized petrolatum is also added, and the stated amoun~ of C2 i8 then passed into ~he reaction mixture at 50 - 60C in the course of 2 to 3 hour~.
When the introduction of the gas has ended, the mixtuxe i5 filtered over a 300 ~m sieve .into a second reactor.
Tha resulting filtrate is finally freed from the volatile solvents ~hydrocarbons, meth~lglycol) by di~tillation under a slight vacuum.
The result is 5 250 kg of a product which contains about 20 ~ by weight of active compound and has a TB~ ~total basic number) of at lea~t 230 mg of ~OH/g (AST~D 2 896).
Example 2 The following amounts are employed in a manner analogous to that described in Example 1:
2 400 kg of hydrocarbon mixture (boiling point 150-200~) 1 660 kg of petroleumsulfonic acid 1 030 kg of calci~m hydroxide 558 kg of methylglycol 257 kg of water 147 kg of oxidi2ed petrolat~um 440 kg of carbon dioxide gas.
' ~
~ ~2 a~
The result is 5 800 kg of a mixture h2ving an active content of 20 ~ by weight, a TBN of 217, a dry content o 93 % by weight and a flashpoint of 73~C.
.
After an after-~tirring time of 20 minutes, the methyl-glycol and the water are added at ambient temperature.
The molten oxidized petrolatum is also added, and the stated amoun~ of C2 i8 then passed into ~he reaction mixture at 50 - 60C in the course of 2 to 3 hour~.
When the introduction of the gas has ended, the mixtuxe i5 filtered over a 300 ~m sieve .into a second reactor.
Tha resulting filtrate is finally freed from the volatile solvents ~hydrocarbons, meth~lglycol) by di~tillation under a slight vacuum.
The result is 5 250 kg of a product which contains about 20 ~ by weight of active compound and has a TB~ ~total basic number) of at lea~t 230 mg of ~OH/g (AST~D 2 896).
Example 2 The following amounts are employed in a manner analogous to that described in Example 1:
2 400 kg of hydrocarbon mixture (boiling point 150-200~) 1 660 kg of petroleumsulfonic acid 1 030 kg of calci~m hydroxide 558 kg of methylglycol 257 kg of water 147 kg of oxidi2ed petrolat~um 440 kg of carbon dioxide gas.
' ~
~ ~2 a~
The result is 5 800 kg of a mixture h2ving an active content of 20 ~ by weight, a TBN of 217, a dry content o 93 % by weight and a flashpoint of 73~C.
.
Claims (5)
1. A process for the preparation of a superbasic calcium sulfonate/calcium carbonate complex by reaction of a mixture of - oil-soluble aralkylsulfonic acids, - calcium oxide and/or calcium hydroxide and - carboxylic acids, in the presence of a liquid non-polar reaction medium, water-soluble polar solubilizing agents and water, and subsequent reaction with carbon dioxide, which comprises employing water-immiscible or water-insoluble carboxylic acids as the carboxylic acids.
2. The process as claimed in claim 1, wherein the car-boxylic acids consist of naturally occurring or syn-thetic, branched or unbranched, saturated or unsaturated aliphatic fatty acids or a fatty acid mixture having at least 8, in particular 8 to 24, carbon atoms.
3. The process as claimed in claim 1 or 2, wherein the carboxylic acids consist of aromatic carboxylic acids, in particular naphthalenecarboxylic acids, if appropriate as a mixture with the carboxylic acids of claim 2.
4. The process as claimed in one of claims 1 to 3, wherein the carboxylic acids include amino acids, if appropriate as a mixture with the carboxylic acids as claimed in claim 2 and/or 3.
5. The use of a process product as claimed in claim 1 as an anticorrosive agent.
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| DEP4039033.0 | 1990-12-07 | ||
| DE4039033 | 1990-12-07 |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CA2057196A1 true CA2057196A1 (en) | 1992-06-08 |
Family
ID=6419779
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CA 2057196 Abandoned CA2057196A1 (en) | 1990-12-07 | 1991-12-06 | Process for the preparation of calcium sulfonate/calcium carbonate complexes |
Country Status (5)
| Country | Link |
|---|---|
| EP (1) | EP0490255A1 (en) |
| JP (1) | JPH04266866A (en) |
| BR (1) | BR9105278A (en) |
| CA (1) | CA2057196A1 (en) |
| MX (1) | MX9102416A (en) |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US6875731B1 (en) | 2003-03-04 | 2005-04-05 | Patrick Joseph Bence | Thixotropic compounds and methods of manufacture |
| US20130280543A1 (en) * | 2010-12-16 | 2013-10-24 | 3M Innovative Properties Company | Anti-corrosive compositions |
Families Citing this family (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP4684806B2 (en) * | 2005-08-26 | 2011-05-18 | 富士フイルム株式会社 | Dampening solution composition for lithographic printing |
Family Cites Families (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| GB1028063A (en) * | 1962-04-06 | 1966-05-04 | Lubrizol Corp | Grease composition |
| US3282835A (en) * | 1963-02-12 | 1966-11-01 | Lubrizol Corp | Carbonated bright stock sulfonates and lubricants containing them |
| GB1134608A (en) * | 1966-05-23 | 1968-11-27 | Chevron Res | Alkaline earth metal carbonate dispersions containing organic sulfonate dispersants |
| FR2588270B1 (en) * | 1985-10-03 | 1988-02-05 | Elf France | PROCESS FOR THE PREPARATION OF AN ADDITIVE FOR LUBRICATING OILS, THE ADDITIVE THUS OBTAINED AND A LUBRICATING COMPOSITION CONTAINING SAID ADDITIVE |
| US5013463A (en) * | 1986-11-19 | 1991-05-07 | Amoco Corporation | Process for overbased petroleum oxidate |
| GB8814010D0 (en) * | 1988-06-14 | 1988-07-20 | Bp Chemicals Addivites Ltd | Lubricating oil additives |
-
1991
- 1991-12-04 EP EP91120842A patent/EP0490255A1/en not_active Ceased
- 1991-12-05 JP JP32213691A patent/JPH04266866A/en not_active Withdrawn
- 1991-12-06 BR BR919105278A patent/BR9105278A/en unknown
- 1991-12-06 CA CA 2057196 patent/CA2057196A1/en not_active Abandoned
- 1991-12-06 MX MX9102416A patent/MX9102416A/en unknown
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US6875731B1 (en) | 2003-03-04 | 2005-04-05 | Patrick Joseph Bence | Thixotropic compounds and methods of manufacture |
| US20130280543A1 (en) * | 2010-12-16 | 2013-10-24 | 3M Innovative Properties Company | Anti-corrosive compositions |
| US8911542B2 (en) * | 2010-12-16 | 2014-12-16 | 3M Innovative Properties Company | Anti-corrosive compositions |
Also Published As
| Publication number | Publication date |
|---|---|
| EP0490255A1 (en) | 1992-06-17 |
| JPH04266866A (en) | 1992-09-22 |
| MX9102416A (en) | 1994-01-31 |
| BR9105278A (en) | 1992-08-18 |
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