FR2551765A1 - ONE OPERATION PROCESS FOR THE PREPARATION OF FAT AND THICK COMPOSITIONS BASED ON BASIC EXCESS CALCIUM SULFONATE - Google Patents

Abstract

ONE-OPERATION PROCESS FOR THE PREPARATION OF FATS OR THICK COMPOSITIONS BASED ON THIXOTROPIC COMPLEX OF BASIC EXCESS CALCIUM SULPHONATE CONTAINING CALCIUM SULPHONATE AS A DISPERSION AGENT AS WELL AS CALCIUM CARBONATE IN THE CALCITE FORM EXTREMELY THIN DIVIDED OR COLLOIDALLY DISPERSED IN SUCH FATS OR THICK COMPOSITIONS.

Description

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  The present invention relates to an improved process in a single operation for the preparation of greases and thick compositions based on calcium sulfonate with basic excess. The greases and thick compositions conforming to the present invention are currently known as of thixotropic type and advantageously comprise a support or liquid solvent of volatile and / or non-volatile type such as, for example, Varsol or mineral spirits, or else a mineral oil or an oily medium of equivalent type, as well as calcium sulfonates soluble in l oil and derivatives of sulphonic acids soluble in oil and of high molecular weight, these fats and thick compositions also containing calcium carbonate such as calcite in colloidal form or in a finely divided form In accordance with the present invention, whereas such types of greases and thick compositions have so far been prepared by the con naked in the art as a one-step process, such one-step processes currently practiced have had many disadvantages

  which the present invention seeks to remedy.

  Thixotropic greases or thick compositions based on basic excess calcium sulfonate and exhibiting corrosion-inhibiting properties as well as being useful for numerous uses such as, for example, as undercoat for coating automobile bodies and trucks, as well as many other uses, are known in the art and have already been described in numerous publications and patents, including US Patents Nos. 3,242,079; 3,372,115;

  3,376,222; 3,377,283; 3,523,898; 3,661,622; 3,671,012;

  3,746,643; 3,730,895; 3,816,310 and 3,492,231 as well as

Canadian Patent No. 949,055.

  Such greases or thick compositions are widely used either as such or mixed with other products, to produce compositions which can be used in many environments and, in such a way.

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  general, they are characterized for good PE, as well as their anti-wear properties, high dropping points, good resistance to mechanical rupture, their resistance to salt spray and to corrosion by water, their high temperature thermal stabilities and other desirable properties, as described in the above patents Such greases or thick compositions currently known are usually prepared by what is known as a two-step process, as is is more particularly shown in

  US patents above Nos 3,242,079, 3,372,115 and 3,492,231.

  These greases or thick compositions have also been prepared by what is known under the name of process in one operation, as indicated above and as shown, for example 15 ple, in the US patents mentioned above Nos. 3,671,012, 3,746,643 and 3 816,310 as well as in Canadian patent N 9,149,055, these documents also describing processes

  in two operations currently known.

  In the two-step process illustrated in particular in US Pat. Nos. 3,242,079, 3,372,115 and 3,492,231, mentioned above, a Newtonian solution is first prepared by example by mixing a oil, normally liquid, usually a mineral oil or a mixture of a mineral oil and a volatile organic solvent based on non-mineral oil, generally a hydrocarbon solvent such as hexane with a normally liquid sulfonic acid comprising or containing a straight or branched aliphatic chain having at least 12 carbon atoms but, preferably a molecular weight of the order of about 370 to about 700, to which or to which is added calcium oxide and / or calcium hydroxide as well as a so-called promoter which is used to produce a basic excess calcium sulfonate which can commonly have a metallic ratio of at least 4.5, generally significantly above this value , and the mixture resulting is heated with stirring and then carbonated. A Newtonian solution is thus obtained containing the basic excess calcium sulfonate dissolved or dispersed colloidally in mineral oil or the like, this solution then being filtered to form a clear solution The clear Newtonian solution resulting produced in such a first operation is then subjected, in a second operation, to a treatment which involves the fact of vigorously mixing as well as, in general, heating said solution produced during the first operation with a so-called converter agent which can, for example, be water or water-soluble alcohols or alternatively glycol ethers such as methylcellosolve (mono methyl ether of ethylene glycol), or mixtures of water and such alcohols; it is also possible to use water-soluble acids such as acetic acid or propionic acid, this second operation having the result of converting the Newtonian solution into a non-Newtonian dispersion system under

  the form of a fat or thick composition.

  The one-step process for forming fats or thick compositions differs from the two-step process in that in the one-step process, in general almost all products are mixed together and then carbonated, and there is no There are no, separately formed or formed separately and recovered, Newtonian solutior of a basic excess sulfonate dissolved or colloidally dispersed in mineral oil or other suitable liquid carrier or carrier From a Economically, the one-step process has a definite advantage over the two-step process, but the one-step process has not achieved the same commercial use as the two-step process because the one-step process , as it is currently known and commercially put into practice or sought to be put into practice, has been characterized by

  a number of significant drawbacks.

  US Patent 3,746,643 describes a one-step process

  operation for the preparation of thixotropic greases based on basic excess calcium sulfonate as well as

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  rust inhibiting conditions in which small amounts of water and an alcohol are incorporated into a mixture of a non-volatile diluent oil, a calcium carbonate complex, and a dispersing agent soluble in l oil based on calcium sulfonate complex In such a mixture, the dispersing agent based on calcium sulfonate is indicated to be able to vary from approximately 2 to approximately 65% by weight, the non-volatile oil forming diluent is indicated be able to vary between about 5 and 80% by weight; the calcium carbonate complex is said to be able to vary between about 1 and about 25% by weight; finally the water and the alcohol are indicated to be able to vary between approximately 1 and approximately 6% by weight and, respectively, between approximately 1 and approximately 40% by weight In addition, the mixture 15 of these ingredients is indicated to comprise, possibly,

  up to 60% by weight of a volatile treatment solvent.

  The resulting mixture of ingredients is then indicated to be heated under controlled conditions to transform the mixture into a grease or rust inhibiting composition (when fluxed with a light hydrocarbon solvent). The patent states that to obtain the desired products, the mixture must be heated to a temperature exceeding 50 'C (122 F) and that it is necessary, when crossing the temperature zone from about 50' C (1220 F) to about 100 'C (212 * F) that the rate of temperature increase does not exceed a certain maximum limit value for which the amount of water present

  in the mixture is less than 2.5 moles of water per mole of calcium metal present in the form of a carbonate-based complex.

  US Patent No. 3,671,012 describes a one-step process for the preparation of basic excess calcium sulfonate thixotropic fats as well as fat-like compositions. This is more particularly described from line 40 of column 6 up to line 25 of column 9 passing through columns-7 and 8 The process described in US Pat. No. 3,671,012 is generally similar to that illustrated in

  US Patent No. 3,746,643 except that the description given in US Patent 3,671,012 is much more detailed

  than that given in US Patent No. 3,746,643.

  US Patent No. 3,816,310 is generally similar,

  in the description he gives of known methods in a

  operation, to the one-step process described in the above patents Nos. 3,746,643 and 3,671,012 Taking, by way of example, the one-step process described in U.S. Patent No. 3,816,310 in the form of typical embodiment taken as an example, a mixture comprising essentially a water-soluble sulfonic acid and a water-soluble calcium sulfonate is formed as a dispersing agent, for example linear or chained "NAB" residues Branched or a C 15 to C 18 linear alkyl benzene sulfonic acid; a support or a liquid carrier material, for example a mineral oil; a C 1 -C 3 alkanol, for example methyl alcohol; calcium oxide and / or calcium hydroxide and water; then carbonation of the resulting mixture is carried out with carbon dioxide while keeping the temperature below about 75 C (165 F) until at least 1.5 moles of carbon dioxide per mole of calcium are present in the mixture as calcium carbonate and the carbonate mixture is then heated to a temperature above 100 C (212 'F), this heating operation being characterized in that the time necessary to heat up to 100 C (212 F) is between about 0.5 and about 8 hours, the process being further characterized in that, alternatively, the water used initially can be added after the carbonation operation or just before heating operation after carrying out the carbonation operation Numerous liquid or non-volatile media or support materials are described in this document, the use of mineral oils being generally preferred when it is desired to obtain greases US Patent No. 3,816,310 also indicates that a light or relatively light hydrocarbon solvent

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  volatile such as, for example, n-decane, benzene, toluene, Stoddard solvent or n-hexane, although not a critical product, can be incorporated into the composition comprising the ingredients mentioned above and, when such a product is incorporated, it is preferable that it be used in proportions, by weight, of between approximately 20 and 80% of the total of the calcium sulfonate and of the non-volatile carrier present in the composition to be treated In cases where the final composition produced by the process is to be used as fat, a high percentage of the mixture of non-volatile carrier and volatile hydrocarbon solvent should be volatile hydrocarbon solvent; whereas, if the final product produced by the process is to be used as an anti-rust or anti-corrosion protective coating or film, the non-volatile support can be used alone as a support or mixed with relatively small amounts of volatile support The patent also indicates in a particular way that, when the final product obtained by the process according to this patent is to be used as fat, the consistency or the thickness of the fat is controlled by using, as support, a relatively non-volatile mineral oil having for example the general properties of a Bright Stock cut (lubricating oil of

  high viscosity base) produced during petroleum refining.

  One of the main problems with such known in-use processes in one operation is that of the unpredictability of whether or not the fat or thick product obtained will have a reasonably satisfactory character for commercial uses. Greases and thick compositions having reasonably satisfactory characteristics and which can be used commercially were obtained in less than 50% of cases when the methods in a single operation were then carried out, then known for obtaining the desired fats or thick compositions Attempts to find out why certain batches grease or thick compositions were suitable

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  while others were unusable did not give

  result despite numerous studies and considerable experimental work.

  The present invention has had the result of effectively remedying the previous shortcomings of the known processes by producing greases based on basic calcium sulfonate with a basic excess using a new process in a single operation. It has been discovered that by implementing the process in a single operation of the improved type in accordance with the present invention, since provision is made for a mixture containing the volatile carriers mentioned above such as, for example, Varsol, mineral spirits or n-hexane or alternatively a mixture of these with variable amounts of a non-volatile carrier, in particular a mineral oil of the same type as that described hitherto and used in the preparation of greases or thick compositions of the kind of those concerned the present invention; or an oil, in particular a mineral oil without any mixture of a volatile carrier; an oil-soluble sulfonic acid or a mixture of oil-soluble sulfonic acids, as a dispersing agent, as is already known and used; calcium oxide and / or calcium hydroxide, all of these products being already known and used; but comprising, in the mixture of ingredients, small proportions of water-soluble aliphatic acids such as acetic acid and an aliphatic alcohol or acoxyalkanol such as methyl alcohol or methylcellosolve, before performing the carbonation operation; and the fact that the carbonation operation is carried out under conditions which do not require rigid controls, specified for example in said US Pat. No. 3,816,310 and the other methods in one operation described in said other patents, obtained improvements making the process in one operation much more practical and much more compatible, to produce batches which can be used commercially in a satisfactory manner of greases and thick compositions based on calcium sulfonate with basic excess of general type obtained by the process in one operation as was the case with previously known methods of operation

and put into practice.

  More particularly in the practice of the present invention, the mixture of ingredients which must be subjected to the carbonation operation uses (a) an aliphatic carboxylic acid soluble in water or miscible in water and containing up to 4 atoms carbon, or an aromatic carboxylic acid, such as acetic acid, propionic acid, butyric acid or benzoic acid, more particularly acetic acid; (b) a water-soluble or water-miscible alcohol preferably containing from 1 to 4 carbon atoms or an alkoxyalkanol, for example a water-soluble monoalkyl ether of a glycol soluble in water, such as methylcellosolve or ethylcellosolve (mono methyl or mono ethyl ether of ethylene glycol), particularly methylcellosolve; and (c) water This combination of ingredients can be mixed beforehand and added as such to the other ingredients or alternatively the ingredients (a), (b) and (c) can be added separately or in a any mixture of two of them with the other ingredients Proceed in this way, when, as indicated above, the entire mixture of the ingredients comprises the ingredients (a), (b) and (c) before carrying out the carbonation operation, the desired formation of colloidal calcium carbonate in the form of calcite crystals and the desired viscosity change to obtain a fat or a thick composition

  occur at the end of the carbonation operation or cycle The volatile solvent may or may not be completely removed by distillation or it may be partially removed.

  The result of practicing such a method in one operation is to produce a non-Newtonian colloidal dispersion system, in the form of a fat or thick composition, containing calcium sulfonate and also containing calcium carbonate which is colloidally dispersed or extremely finely divided in the form of calcite crystals, sometimes mixed with small proportions of calcium carbonate in the form of vaterite. The ratios of ingredients (a), (b) and (c) of which particular and advantageous examples are given by acetic acid, methyl alcohol or methylcellosolve, and water can vary within reasonable limits but, in general, the quantity 6 of acetic acid measured in the form of glacial acetic acid will be appreciably less than that of methyl alcohol or methylcellosolve; similarly the amount of water will be about the same as that of alcohol or methylcellosolve, or somewhat lower

  or somewhat higher than that of alcohol or Methylcellosolve.

  With respect to the question regarding the proportions of the above ingredients as carriers, whether volatile or non-volatile, or mixtures thereof; with regard to calcium oxide and / or calcium hydroxide; sulfonic acids, alcohols or ethers glycols or even alkoxyalkanols as well as water, no novelty is claimed in such proportions because these proportions can vary and are generally described and taught by the methods in a known operation of the PRIOR ART As regards the use of hydrosoluble acids, such as in particular acetic acid, no document known in the prior art shows the use of such acids nor in particular that of acetic acid in a process an operation for producing greases or thick compositions based on a basic excess calcium sulfonate complex; and the same is true with regard to the use of acids, such as acetic acid, and alcohols such as methanol or glycol esthers, such as M 6thylcellosolve or other alkoxyalkanol, at the same time in a process in one operation of the type identified by the present invention, which involves the best and most important embodiments of the process in one operation according to the present invention

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  such as acetic acid and the amount of alcohols such as methanol or Methylcellosolve are minor points in the proportions by weight of the mixture of ingredients which is prepared for reaction and carbonation, as is well visible from the manufacturing examples set out below in this specification The acid, such as acetic acid, will be present in proportions somewhat less than 0.5% by weight of the total mixture of ingredients (before the operation of carbonation) and can generally be between about 0.2 and about 2%

  by weight of said mixture of ingredients The alcohol or the methylcellosolve or other alkoxyalkanol used is in variable proportion but will generally be employed in optimal proportions of approximately 4 to approximately 6% by weight, more or less, based on said mixture ingredients.

  In accordance with the one-step process described in the previously mentioned US Pat. No. 3,816,310, at least 1.5 moles of carbon dioxide per mole of calcium should be present in the mixture of ingredients. This is stated in the patent, for example in column 2, operation B. In the one-operation process according to the present invention, the effective carbonation is, for the invention, sufficiently complete using only about 0.78

  0.9 moles per mole of carbonate dioxide per mole of cal25 cium.

  In US Patent No. 3,816,310 above, the C 1 to C 3 alcohols are used in proportions of between 10 and 40% by weight, 20 to 30% being preferred and a proportion of 30% being recommended. the present invention, said alcohols, when used, but in conjunction or in admixture with a carboxylic acid such as acetic acid, can be used in proportions as low as about 4 to about 8% by weight

with said acetic acid.

  While US Patent No. 3,816,310 insists that the temperature at which carbonation is carried out should not exceed 50 C (122 'F) in the present invention, the carbonation operation can be performed at temperatures included between around 38 C (1000 F) at

about 93 * C (200 F).

  Furthermore, while said US Pat. No. 3,816,310 requires a limited time / temperature distillation profile, after the carbonation operation, in order to obtain a correct structure based on crystalline calcite as well as an appropriate viscosity, the present The invention does not necessarily have such a limited time / temperature profile 6 in a "controlled" manner 10 but in fact has a greater latitude, which again clearly shows another of the many differences between the process according to the prior patent and the process according to the present invention in that, in the latter,

  it is not necessary to use any distillation time table.

  In the Scope of the Description of US Patent No

  3,816,310 regarding starting charges, the patent states that a thixotropic character is obtained as long as sulphonic acids as sulphonate of residue "NAB" 20 are combined with at least 60% of branched chain alkylbenzane Again the process according to the present invention has greater flexibility in that it is a process

  which differs in many respects from the process to an operation described in US Patent No. 3,816,310.

  In the practice of the new process in one operation according to the present invention, the usual ingredients which are initially mixed to form a single composition, together with or without additional ingredients which are not essential to the invention, are the 30 following: 1 '/ a liquid support which may be a light or volatile hydrocarbon having a boiling point below 220 C (430 F) for example hexane, heptane, or mineral spirits, or alternatively a volatile oil, in particular a mineral oil, or finally a mixture of such volatile and non-volatile liquid supports 2 ′ / a sulfonic acid which can be of the same type as that described here and which is commonly used in the production of fats or compositions thick thixotropics based on basic excess calcium sulfonate; 3 '/ calcium oxide or calcium hydroxide; 4 '/ water-soluble aliphatic carboxylic acids, in particular acetic acid; / for optimum results, in conjunction with the carboxylic acid, an alkoxyalkanol which may be one or more of the many substituted or unsubstituted or unavailable alcohols containing from 1 to 8 carbon atoms, the preferred alcohol being methanol and the preferred alkoxyalkanol being

methylcellosolve.

  Water is generally produced during the reaction, but it is preferred to add water In cases where the basic excess calcium sulfonate is not formed in situ by a reaction which includes the reaction of the volatile solvent solution of sulfonic acid with calcium oxide and / or calcium hydroxide, Calcium sulfonate can be formed beforehand and incorporated as

as in the other ingredients.

  The mixture of ingredients prepared under stirring conditions is preferably first heated to temperatures between about 35 'C (95 F) to about 25 93 C (200' F), temperatures at which or heating during of which carbonation is carried out by introducing carbon dioxide directly into the mixture over a period of time making it possible to convert substantially from% to 100% of calcium oxide and / or calcium hydroxide to calcium carbonate In the product finally obtained, the calcium carbonate is present in the form of crystalline calcite divided in an extremely fine manner or dispersed colloidally in the support Under certain conditions, and only in certain cases, during the implementation of the process an operation according to the present invention, and as noted above, the solid calcium carbonate which forms is not only calcite but contains some vaterite at temperatures high such as, for example, at 88 C (190 F) vaterite tends to form This does not appear to adversely affect the production of fats or thick compositions or their usefulness when vaterite is present in relatively small proportions However, when calcium carbonate is wholly or largely in the form of vaterite, the desired properties of fats or thick compositions are affected in a way

  harmful and it is desirable to avoid such vaterite formation.

  Thick greases or complexes produced in accordance with the one-step process of the present invention must have a metal ratio of at least 5, more preferably at least 6, and for many uses, they have a metal ratio of 10 or 12 or, in fact, as high as 25 or even somewhat higher This is controlled, among other considerations, by the amount and choice of particular promoters These questions, regardless of the basis of the present invention, are known by themselves 20 same in the art and few patentable novelties can be envisaged in the processes for the production of greases or thick compositions based on calcium sulfonate with basic excess having metal ratios

  such as those mentioned above.

  While reference has been made to the oil-soluble sulfonate acids which are useful in the practice of the present process in one operation, or to their calcium salts which contain in their molecules an aliphatic radical having at least 12 atoms of carbon, said sulfonic acid can be represented by the formula E Rx) A so 3 ly M in which R is in a linear or branched chain aliphatic radical, in general an alkyl radical containing at least 12 carbon atoms; A is a 6, preferably a cyclic, hydrocarbon ring such as benzene, naphthalene, phenanthrene or the like; x is 1 or 2 and M is calcium or hydrogen When M is hydrogen y = 1; and when M is the calcium y = 2 As seen above, the basic excess calcium sulfonates can be formed beforehand and dissolved in the medium or the liquid support and can be formed therein by incorporating, in the mixture of ingredients, sulfonic acid, preferably in solution in a volatile organic solvent such as Varsol or mineral spirits or in an oil, in particular, mineral oil and calcium oxide and / or l calcium hydroxide, preferably calcium hydroxide, calcium sulfonate is formed in situ when promoters are used in amounts and under conditions to produce calcium excess basic sulfonates at the desired metal ratio. is preferred to use, as sulfonic acid, a Varsol solution of a mixture of sulfonic acids of linear monoalkylbenzenes, branched chain alkylbenzenes and dialkoylbenzenes, said sulfonic acids having a molecular weight between about 450 and about 550, but there is nothing really critical in the use of such sulfonic acids In general, the preferred sulfonic acids will be those with a molecular weight between about 300 and about 650 or 700 These are, in general, commercially available compounds sold by a number of chemical companies under various trade names. Many more sulfonic acids useful in practicing the present process in a single operation are described in many of the patents referred to above, such as US Pat. Nos. 3,442,079, 3,372,115, 3,492,831 and 3,746,643 30 and 3,816,310 The statements of such sulfonic acids are considered to be part of the present memory by being there

incorporated for reference.

  As seen above, the carbonation temperature should preferably be in the range of between about 35 C (95 F) and 93 C (200 F) After the carbonation operation has been finished, which, as seen above, can be from about 80% to 100% of the theoretical value, the fat or thick carbonate composition otherwise obtained can be heated to higher temperatures, by example At about 138 C (280 F) or somewhat higher to remove volatiles, to the extent desired. The examples given below are given by way of illustration of the production of greases or thick compositions produced according to the improved process in an operation in accordance with the present invention. It should be understood that the present invention does not is not limited to the specific conditions and to the details of construction illustrated in the said examples, since various modifications can be made without departing from the scope and

  of the principles taught above All the indi15 quêeg parts are given by weight.

  Exe Mple 1 Apparatus of 1 Distillation container of 300 Cl

  laboratory used 6: folded and three-necked.

  2 Explosion-proof variable speed mixer with 75 mm propeller

diameter and 300 mm shaft.

  3 Thermometer 0-300 C 4 Friedricks condenser Heating sleeve 25 6 Universal two-stage CO 2 flow meter 7 Gas sprayer Loaded ingredients: Grams 870 Active Varsol solution containing 28% sulfonic acid 173 Ca (o H ) 2 54 Methylcellosolve Water 4.6 Glacial acetic acid 350 cm 3 / min Carbon dioxide (For example 2 hours for conversion)

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  Process The Varsol solution of sulfonic acid is added to the three-necked distillation vessel, the Friedricks condenser is hooked up and the mixing operation begins. Ca (OH 2) is added to the vessel followed by the addition of Methylcellosolve then water The container is heated to 52 C (1250 F) then glacial acetic acid is added and the ingredients are mixed for about minutes The gaseous CO 2 is then introduced via the sprayer via the flow meter The carbonate peak is set to 882 886 by IR When all the calcium carbonate is in this form (rather than 860), the reaction

  is complete The introduction of C 02 is stopped.

Example 2

  In a suitable installation comprising a reactor of adequate capacity and the general equipment modified for an installation operation, 3,236 kg of a 28% solution in varsol of sulphonic acid is loaded into the reactor followed by the addition of l '' order of 636 kg of Ca (OH 2) 201 kg of methylcellosolve, 167 kg of water; the reaction mixture is heated to about 52 C (125 F) and 16.7 kg of glacial acetic acid are added, the resulting mixture being carbonated at a rate of about 2.8 kg per minus, until that carbonation gives a carbonate peak controlled 25 to 882-886 by I R. Final product Non-volatile 52% typical viscosity 80,000 Pin N 6 viscosity A 40% 20,000 Brookfield A NV 10 rpm Example 3 In a suitable installation, one loading into the reactor under stirring conditions 16,466.5 liters of a 28% Varsol solution of a sulfonic acid comprising a mixture of sulfonic acids of mono-alkylbenzenes, of sulfonic acids of mono-alkylbenzenes branched chalne and linear dialkoylbenzenes of sulfonic acid, said mixtures of sulfonic acids having

  a molecular weight of about 465; 2894 kg of hydrated lime

  Mississippi tée, 814 liters of methylcellosolve, 647 liters of water and 61.7 liters of glacial acetic acid The resulting mixture, heated to a temperature of 60 ° C (140 F), is then carbonated with 1197.5 kg of carbon dioxide pumped into the reaction mixture at a rate of 10 kg per minute The temperature profile of carbonate dioxide

is 52-58 C (125-137 'F).

Example 4

  A suitable reactor having heat exchange elements and an agitator is charged with 140 parts of a 28% solution in Varsol of a commercial oil-soluble sulfonic acid comprising a mixture of mono-alkyl acids and di-alkyl sulfonates having a molecular weight of approximately 465 To this solution are added: 15 hydrated lime 32 parts water 8 parts Methylcellosolve 10 parts Acetic acid 0.8 parts C 02 is introduced into the mixture with stirring for a period of 100 minutes until the hydroxide

  of calcium is almost neutralized.

  The temperature is maintained at about 54.5 'C (130' F) during the reaction When the reaction is complete, the water and the M 6 ethylcellosolve are removed by distillation. The contents of the reactor are filtered through a sieve. a 70 micron (200 mesh) mesh opening to remove any coarse solid residue The purified composition is

  the thick complex desired in mineral spirits.

Example 5

  A suitable reaction of the above type is charged with 130 parts of a 32% solution of calcium sulfonate

  in a mineral oil based on pale oil.

  To this solution are added: Hydrated lime 60 parts Naphta 150 parts Methanol 6 parts Acetic acid 6 parts C 02 is introduced into the mixture with stirring for a period of 120 minutes until the calcium hydroxide is approximately completely neutralized The temperature is maintained at around 850 C (185 F) during the reaction When the reaction is complete, water, methanol and naphtha are removed by distillation The contents of the reactor are filtered through a sieve of a 70 micron mesh opening to remove any coarse solid residue The purified composition obtained is the desired thick complex 10 based on basic excess calcium sulfonate in

mineral oil.

  Examples 6 to 14 The effect of carbonation time searches is

  shown below. The process of Example 1 is followed and the level of carbon dioxide is varied.

  Examples Time reaction for product carbonation (minute) 6 30 not thick 7 40 not thick 8 50 not thick 9 60 thick 80 thick 11 100 thick 12 120 thick 13 160 thick Examples 15 to 21

  The effect of methylcellosolve on the product is shown below. The process of example 1 is followed, but the amount of methylcellosolve is varied.

  Examples Amount of Methylcellosolve Product (parts)

35 16

  17 18 8 10 not thick not thick thick thick Examples Quantity of Methyl Cellosolve Product (parts) 19 12 thick 20 15 thick 21 20 thick Examples 22 to 27

  The effect of the carbonation temperature is shown below. The process is the same as in Example 1, but the reaction temperature is varied.

  Examples Reaction Product Temperature C (CF) 22 50 (122) thick 23 60 (140) thick 24 70 (158) thick 80 (176) thick 26 90 (194) thick 27 100 (212) thick Examples 28 to 30 L ' effect of acetic acid on the product is shown below The process is the same as in Example 2 but we

  varies the acetic acid content.

  Examples Acetic acid Product (part) 28 O not thick 29 3 thick 9 thick Examples 31 to 35 The effect of the amount of water on the product is shown below 30 The process is the same as in Example 1 but

  the water concentration is varied.

  Examples Addition of water Product (parts) 31 O thick 32 3 thick 33 6 thick 34 15 thick 24 thick The products of the improved process in an operation according to the present invention provide excellent protection against rust when mixed as described in US Patent 3,746,643, as illustrated by Example 5 ple A.

Example A

  The product of Example 1 (30 parts) is mixed with wax (30 parts), oxidized petrolatum (10 parts) and mineral spirits (40 parts) Steel panels covered with such a composition have been tested in a

  salt spray enclosure in accordance with ASTM B 117.

  Result: 0.0125 mm dry coating after 300 hours, none

rust has not been observed.

  The previous examples show the flexibility of the process.

  Various additional ingredients can and are commonly incorporated in fats or thick compositions made in accordance with the one-step process of the present invention, in small proportions, but they are in no way essential to the present invention and little novelty patentable relates to their use in cases where they are incorporated in the preparation of fats or thick compositions Examples of some additional ingredients which can be used are given by oxidation inhibitors such as phenyl alpha naphthylamine (PAN) ; viscosity improvers which may include certain polymers (Acryloid 155-C); as well as other products to obtain particular properties and generally known in greases or thick compositions. Such ingredients are preferably added after the preparation of the grease.

  or thick composition has been completed.

  The fats or complex thick compositions based on basic excess calcium sulfonate produced in accordance with the process in one operation of the present invention can easily be mixed with oleaginous materials such as oils and fatty substances as well as waxes. paraffins, microcrystalline waxes, asphalts, oxidized petrolatum and other materials according to known practices, as well as other uses

  in practice used alternatively to produce compositions having utility as greases, rust inhibiting coatings and for various other uses.

Claims (10)

  1 One-step process for the preparation of a thixotropic complex based on basic excess calcium sulfonate in the form of a fat or a thick composition, characterized in that a liquid mixture containing a material is formed liquid carrier in the form of a volatile liquid hydrocarbon or a non-volatile oil or a mixture of the latter; a sulfonic acid having or including an aliphatic chain containing at least 12 carbon atoms and having a molecular weight between about 300 and about 700; calcium oxide and / or calcium hydroxide; a product chosen from C 1 to C 4 water-soluble aliphatic alcohols and water-soluble alkoxyalkanols; a water-soluble carboxylic acid; and water; said mixture is stirred and heated to a temperature of between approximately 35 ° C (95 'F) and approximately 93 C (200 F), then carbonation of said mixture is carried out for a period allowing between approximately 80 and 100% of carbonation to produce a fat or thick composition in which the reaction mixture is transformed into a fat or thick composition containing colloidally dispersed particles of calcium carbonate obtained under the form of calcite crystals.   2 Method according to claim 1, characterized in that the molecular weight of the sulfonic acid is included   between about 400 C (500 'F) and about 550' C (550 'F).   3 Method according to claim 1, characterized in   what the alkoxyalkanol is methylcellosolve.   4 Method according to claim 1, characterized in that   that the carboxylic acid is acetic acid.   One-step process for the preparation of greases or thick compositions based on thixotropic complexes of basic calcium sulfonate, characterized in that a liquid and volatile hydrocarbon solution of one or more is introduced into a reactor more than one sulfonic acid having or including an aliphatic chain of at least 12 carbon atoms, said sulfonic acid or said acids having a molecular weight between about 450 and about 550; calcium oxide and / or calcium hydroxide so as to obtain a dispersing agent based on calcium sulfonate; a product chosen from water-soluble aliphatic alcohols having from 1 to 4 carbon atoms and an alkoxyalkanol; a water-soluble carboxylic acid and water; said mixture is heated under stirring conditions to temperatures between about 35 C (95 F) and about 93 C (2000 F); then carbonation of said mixture is carried out at a temperature of between approximately 35 C (95 F) and approximately 93 C (200 F) until the reaction mixture is transformed into a fat or a thick composition containing dispersed particles of colloidal way of carbonate of   calcium which is obtained in the form of calcite crystals.   6 Method according to claim 5, characterized in that the alkoxyalkanol is methylcellosolveo   7 Method according to claim 5, characterized in that the carboxyl oxide that is acetic acid.   8 One-step process for preparing a thixotropic complex based on basic excess calcium sulfonate in the form of a fat or a thick composition, characterized in that a liquid mixture containing a material is formed liquid carrier in the form of a volatile liquid hydrocarbon or a non-volatile oil or a mixture of the latter; a sulfonic acid having or including an aliphatic chain containing at least 12 carbon atoms and having a molecular weight between about 300 and about 700; calcium oxide and / or calcium hydroxide; a product chosen from C 1 to C 4 water-soluble aliphatic alccols and water-soluble alkoxyalkanols; a water-soluble carboxylic acid; and water; said mixture is stirred and heated to a temperature between about 35 C (95 F) and about 930 C (2000 F) and then a carbonation of said mixture is carried out for a period allowing between about 80% and 100% of carbonation to produce a fat or thick composition 3-se in which the reaction mixture is transformed into a fat or thick composition containing colloidally dispersed particles of calcium carbonate obtained under the form of calcite crystals.   9 process in one operation for the preparation of a thixotropic complex based on basic excess calcium sulfonate in the form of a fat or a thick composition, characterized in that a liquid mixture containing a material is formed liquid carrier in the form of a volatile liquid hydrocarbon, a sulfonic acid having or including an aliphatic chain containing at least 12 carbon atoms and having a molecular weight between about 450 and about 550; calcium hydroxide; methylcellosolve; acetic acid; and water; methylcellosolve constituting about 4 to about 6% by weight and acetic acid (calculated as glacial acetic acid) constituting from about 0.2% to about 2% of said mixture of ingredients; said mixture is stirred and heated to a temperature between approximately 35 'C (95' F) and approximately 930 C (2000 F) then carbonation of said mixture is carried out for a period allowing to obtain between approximately 80% and 100% of carbonation so as to produce a fat or a thick composition in which the reaction mixture is transformed into a fat or a thick composition containing colloidally dispersed particles of calcium carbonate obtained under the form of calcite crystals.   10 One-step process for the preparation of greases or thick compositions based on a basic excess calcium sulfonate thixotropic complex, characterized in that a volatile liquid hydrocarbon solution of a dispersing agent is introduced into a reactor based on calcium sulfonate, calcium oxide and / or calcium hydroxide; a product chosen from water-soluble aliphatic alcohols having from 1 to 4 carbon atoms and a water-soluble alkoxyalkanol; and water; said mixture is heated under stirring conditions to a temperature between approximately 35 C (95 F) and approximately 93 C (200 F) then carbonation of said mixture is carried out at a temperature between approximately 350 C (95 'F) and about 93 C (200 * F) until the reaction mixture is transformed into a fat or a thick composition containing colloidally dispersed particles of calcium carbonate obtained in the form of calcite crystals.   11 Method according to claim 10, characterized in 10 that the alkoxyalkanol is methylcellosolve.