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UNITED STATES PATENT OFFICE

2,616,904

ORGANIC ALKALINE EARTH METAL COMPLEX AND METHOD OF MAKING SAME

Peter A. Asseff, Thomas W. Mastin, and Alan Rhodes, Cleveland, Ohio, assignors to The Lubrizol Corporation, Wickliffe, Ohio, a corporation of Ohio
No Drawing. Original application March 16, 1951, Serial No. 216,103. Divided and this application December 28, 1951, Serial No. 263;963
7 Claims. (C1. 260-399)

1

This application is a division of our copending application Serial No. 216,103, filed March 16, 1951, and is related to copending applications: Ser. No. 216,101 , filed March 16, 1951; Ser. No. 216,102, filed March 16,1951 ; Ser. No. 224,458, filed May 3, 1951 ; Ser. No. 263,961 ; filed December 28, 1951; Ser. No. 263,962, filed December 28, 1951; Ser. No. 276,462, filed March 13, 1952; and Ser. No. 279,258, filed March 28, 1952.
This invention relates to organic metal complexes and novel methods for the production of such complexes.
It is now well known that when preparing a salt or soap of an organic acid, the mere use of an excess of neutralizing agent, which in the prior art has been in the form of the oxide, hydroxide, carbonate, etc. of the desired metal, may result in a product which contains an amount of metal in excess of that theoretically required to replace the acidic hydrogens of the organic acid used as the starting material.
现在众所周知，在制备有机酸的盐或肥皂时，仅使用过量的中和剂（在现有技术中以所需金属的氧化物、氢氧化物、碳酸盐等的形式存在）可能会导致产品中含有超过理论上所需的金属量，以替代用作起始剂的有机酸的酸性氢材料。
Work with this type of product has shown that for many uses, particularly where extreme care must be exercised to prevent the composition from being corrosive, as for example in lubricants, desirable results are secured by the use of these so-called basic salts or soaps.
使用此类产品的工作表明，对于许多用途，特别是必须格外小心以防止组合物具有腐蚀性的地方，例如在润滑剂中，使用这些所谓的碱性盐或肥皂可以确保理想的结果。
Among the earlier workers in the art who recognized this factor and indicated that the use of basic soaps was desirable was Bergstrom who, in his Patents Nos. 2,270,577 and
在认识到这一因素并指出使用基本肥皂是可取的本领域早期工作者中，Bergstrom 在他的专利号 2,270,577 和 2 , 279 , 086 2 , 279 , 086 2,279,0862,279,086, made reference to the desirability of using the basic soap without, however, giving any specific method for the preparation of such soaps. A similar disclosure is found in Van Ess Patent No. 2,372,411.
，提到了使用基本肥皂的可取性，但是，没有给出任何制备此类肥皂的具体方法。类似的披露见 Van Ess 专利号 2,372,411。
With the demonstrated superiority of such basic soaps over the normal or slightly acidic soaps, the prior art workers then attempted to find ways of increasing the basicity of the soaps, or stated in another way; increasing the amount of metal, for example, held in stable form in what was termed as a metal complex. One of the earliest patents referring to these basic salts as complexes or coordination compounds is McNab No. 2,418,894, who gives no indication in his patent as to the molecular structure of the product. As might be expected, one of the first steps employed to produce a metal salt having an intended large excess of metal in combination was to use an unusually large excess of neutralizing agent, such as lime. A representative patent disclosing this procedure is Griesinger et al. No. 2,402,325 who suggested the use of neutralizing agent up to
随着这种碱性肥皂优于普通或微酸性肥皂，现有技术工作者随后试图找到增加肥皂碱性的方法，或以另一种方式陈述;增加金属的数量，例如，以所谓的金属络合物形式保持稳定。最早将这些碱性盐称为复合物或配位化合物的专利之一是 McNab No. 2,418,894，他在他的专利中没有说明产品的分子结构。正如预期的那样，生产具有大量过量金属组合的金属盐的第一步是使用异常大量的中和剂，例如石灰。公开该程序的代表性专利是 Griesinger 等人，第 2,402,325 号，他们建议使用高达 220 % 220 % 220%220 \% of the theoretical amount. This large excess of neutralizing agent was employed in a process more or less conventional for producing salts or soaps excepting that the process was carried
的理论量。这种大量过量的中和剂被用于或多或少常规的生产盐或肥皂的工艺中，除非该工艺是进行的
out in the presence of steam in order to facilitate the formation of the product.
在蒸汽存在下取出，以促进产物的形成。
The work of Griesinger was followed by the work of Campbell and Dellinger as given in Patent No.
Griesinger 的工作之后是 Campbell 和 Dellinger 的工作，如专利号所示。 2 , 485 , 861 2 , 485 , 861 2,485,8612,485,861. These patentees base their disclosure on the hypothesis that minor amounts of an alkaline earth metal hydroxide or carbonate can be peptized, or held in a state of colloidal suspension in oil by means of an oil-soluble mahogany sulphonate. Another worker in the art who sought to combine in such complexes an excess amount of metal was Mertes whose Patent No. 2,501,731 was granted March 28, 1950. Mertes first prepared the normal soap and stated that such soap or soap concentrate “may have additional base combined therewith by a more or less simple mixing and heating operation followed by filtering.” The disclosure in Mertes appears to indicate that his product is similar to that of Campbell and Dellinger, in that the excess neutralizing agent was held in the product in the form of a colloidal suspension.
.这些专利权人的披露基于这样一个假设，即少量的碱土金属氢氧化物或碳酸盐可以通过油溶性桃花心木磺酸盐被消化，或保持在油中的胶体悬浮状态。另一位试图在此类复合物中结合过量金属的本领域工人是 Mertes，其专利号 2,501,731 于 1950 年 3 月 28 日获得。Mertes 首先制备了普通肥皂，并指出这种肥皂或肥皂浓缩物“可能具有额外的碱，通过或多或少简单的混合和加热操作，然后进行过滤。Mertes 案中的披露似乎表明，他的产品与 Campbell 和 Dellinger 的产品相似，因为过量的中和剂以胶体悬浮液的形式保留在产品中。
All of the previously enumerated processes have been tried, not only duplicating certain of the examples given in the above-identified patents, but also using different acids and different neutralizing agents. As a result of these experiments, it has been found that there is a definite upper limit to the amount of alkaline earth metal which can be held in combination or in colloidal suspension by means of these prior art processes. The greatest total amount of alkaline earth metal which can possibly be thus incorporated in the product by means of any of these prior art processes has been obtained when using barium and in that case it is equal to about 2.3 times the theoretical amount present in the normal salt. For the purpose of the present invention the ratio of the total metal in the complex to the amount of metal which is in the form of the normal salt of the oil soluble organic acid will hereinafter be referred to as the “metal ratio.”
已经尝试了所有先前列举的工艺，不仅复制了上述专利中给出的某些示例，而且还使用了不同的酸和不同的中和剂。作为这些实验的结果，已经发现通过这些现有技术方法可以组合或胶体悬浮的碱土金属的量有一个明确的上限。使用钡时，已经获得了可能通过任何这些现有技术方法掺入产品中的碱土金属的最大总量，在这种情况下，它等于正常盐中理论量的约 2.3 倍。为本发明的目的，络合物中的总金属与以油溶性有机酸的正常盐形式存在的金属量的比率在下文中称为“金属比率”。
By means of the present invention, it is now possible to obtain alkaline earth metal organic complexes which contain more metal or higher metal ratios than is possible by prior art processes. With regard to lubricants, these high metal containing complexes are for example particulariy suited as detergents, and by reason of the metal concentration can be used in amounts appreciably less than other additives known in the prior art in order to attain a desired level of performance. It will also be observed that by virtue of the more effective nature of the present complexes in lubricants, usually it will cost less to obtain a desired result, because appreciably less additive is required. The alkaline earth metal
通过本发明，现在可以获得碱土金属有机络合物，其含有比现有技术工艺可能更多的金属或更高的金属比例。就润滑剂而言，这些高金属含量的络合物例如特别适合用作洗涤剂，并且由于金属浓度的原因，可以使用比现有技术中已知的其他添加剂少得多的量，以达到所需的性能水平。还将观察到，由于目前润滑剂中络合物的更有效性质，通常获得所需结果的成本会更低，因为需要的添加剂明显较少。碱土金属
organic complexes are produced in accordance with the present invention as a fluid, which is readily adapted for application where high concentrations of alkaline earth metal are desired, e. g. in lubricants. For example, if the complex alone is desired, it can be produced in mineral oil solutions of at least about
有机络合物根据本发明以流体形式生产，其很容易适应于需要高浓度碱土金属的应用，例如在润滑剂中。例如，如果需要单独的复合物，它可以在至少约 20 % 20 % 20%20 \% concentrations; whereas if the complex is wanted in combination with other additives, it can be available in concentrations of at least about
浓度;而如果需要将复合物与其他添加剂结合使用，则其浓度至少约为 10 % 10 % 10%10 \% in mineral oils.  在矿物油中。
It is a principal object of our invention to provide an alkaline earth metal organic complex which contains in stable form an amount of metal substantially greater than that contained in any of the so-called alkaline earth metal complexes previously produced. It has been found that a metal ratio substantially greater than that possible with the prior art processes give results which are strikingly superior, especially in the field of lubricants in which these products have particular utility.
我们发明的主要目标是提供一种碱土金属有机配合物，其稳定形式的金属含量大大大于先前生产的任何所谓的碱土金属配合物中的金属量。已经发现，大大大于现有技术工艺可能产生的金属比率会产生明显优越的结果，尤其是在这些产品具有特殊用途的润滑剂领域。
It is a further object of this invention to produce by our improved process, complexes which; while containing the same amount of alkaline earth metal as in complexes produced by the prior art process above described, are nevertheless different from and superior to such prior art complexes.
本发明的另一个目标是通过我们改进的工艺生产复合物，其中;虽然含有与上述现有技术方法产生的络合物相同量的碱土金属，但仍然不同于并优于此类现有技术络合物。
Still another object of this invention is to provide novel methods of producing organic alkaline earth metal complexes.
本发明的另一个目标是提供生产有机碱土金属络合物的新方法。
Further objects of our invention will appear as the description proceeds.
随着描述的进行，我们发明的更多对象将出现。
To the accomplishment of the foregoing and related ends, said invention then comprises the features hereinafter fully described and particularly pointed out in the claims, the following description setting forth in detail certain iliustrative embodiments of the invention, these being indicative, however, of but a few of the various ways in which the principle of the invention may be employed.
为了实现上述和相关目的，所述发明包括下面在权利要求中充分描述和特别指出的特征，以下描述详细阐述了本发明的某些具体实施例，然而，这些只是指示可以采用本发明原理的各种方式中的几种。
Griesinger 的工作之后是 Campbell 和 Dellinger 的工作，如专利号所示。 2 , 485 , 861 2 , 485 , 861 2,485,8612,485,861 。这些专利权人的披露基于这样一个假设，即少量的碱土金属氢氧化物或碳酸盐可以通过油溶性桃花心木磺酸盐被消化，或保持在油中的胶体悬浮状态。另一位试图在此类复合物中结合过量金属的本领域工人是 Mertes，其专利号 2,501,731 于 1950 年 3 月 28 日获得。Mertes 首先制备了普通肥皂，并指出这种肥皂或肥皂浓缩物“可能具有额外的碱，通过或多或少简单的混合和加热操作，然后进行过滤。Mertes 案中的披露似乎表明，他的产品与 Campbell 和 Dellinger 的产品相似，因为过量的中和剂以胶体悬浮液的形式保留在产品中。
有机络合物根据本发明以流体形式生产，其很容易适应于需要高浓度碱土金属的应用，例如在润滑剂中。例如，如果需要单独的复合物，它可以在至少大约 20 % 20 % 20%20 \% 浓度的矿物油溶液中生产;而如果需要将复合物与其他添加剂结合使用，则其浓度至少可以在矿物油 10 % 10 % 10%10 \% 中得到。
In its broadest aspects, the process of the present invivention comprises combining a salt-forming material with an organic acid compound (to be understood hereinafter as the acid itself and/or an alkaline earth metal salt thereof) in the presence of a material which is referred to hereinafter as the “promoter.” The precise function of the promoter material is not specifically understood since it has not been possible to specifically identify the molecular structure of the product produced. At present; it appears that none of the complexes, i. e., either those prepared by prior art techniques or those obtained under the present invention are susceptible of precise identification. This is clearly shown with respect to the prior art complexes by reason of the apparent disagreement among workers as to the nature of compounds which contribute metal in excess of the normal salt. In one instance, it is held that this pheromenon is a result of partial replacement of the hydroxyl groups in the inorganic metal compound, whereas among another group of prior art workers it is held that the high métal containing complexes are actually colloidal suspensions or dispersions in which the salt of the organic acid is the peptizing agent. In the present invention, the immediate product is produced by the use of a promoter, and at least one stage contains the promoter in chemical combination. It is possibie, however, to recover the promoter from the product by suitable treatment as hereinafter explained, and the final product which then has a constitution different from the
initial end product is, similar to the initial product, of utility as a lubricant additive.
Stated more particularly, the present invention comprises the improvement in the process of producing an alkaline earth metal complex of oilsoluble organic acids, wherein an organic acid compound (to be understood hereinafter as the acid itself and/or an alkaline earth metal salt thereof) is caused to combine with a salt-forming metal compound under conditions which would produce a normal salt, which comprises increasing the amount of metal which will be thus combined by having present in the process mass.
(a) An amount of such metal compound substantially in excess of the stoichiometric amount required to form the normal metal salt;
(b) An organic compound selected from the class consisting of those organic compounds which are water-soluble at a temperature of 50 ∘ C 50 ∘ C 50^(@)C50^{\circ} \mathrm{C}. to the extent of at least 0.0005 % 0.0005 % 0.0005%0.0005 \% and which in the presence of water have an ionization constant greater than about 1 × 10 − 10 1 × 10 − 10 1xx10^(-10)1 \times 10^{-10} at about 25 ∘ 25 ∘ 25^(@)25^{\circ} C.; and the salts of such organic compounds; and
© Water, including free and combined water in the other components;
and maintaining the mass at a temperature and for a period of time sufficient to drive off substantially all free water and water of hydration which may be present.
以及将质量保持在足以驱除可能存在的几乎所有游离水和水合水的温度和时间。
A more specific aspect of the process comprising this invention may be defined as the process of producing an alkaline earth metal organic complex which comprises:
构成本发明的过程的更具体方面可以定义为产生碱土金属有机络合物的过程，其包括：
I. Preparing and mixing a mass in which; at 50 ∘ C 50 ∘ C 50^(@)C50^{\circ} \mathrm{C}.; at least 50 % 50 % 50%50 \% of the components are in the liquid state and which mass the active components consist of:
I. 制备和混合一个质量，其中;在 50 ∘ C 50 ∘ C 50^(@)C50^{\circ} \mathrm{C} .; 至少 50 % 50 % 50%50 \% 成分处于液态，并且活性成分由以下质量组成：
A. An oil soluble organic acid compound;
一个。一种油溶性有机酸化合物;
B. An organic compound containing an element of group VI of the periodic chart which has an atomic number less than 17, which compound is selected from the class consisting of:
B.一种有机化合物，包含元素周期图中 VI 族元素，其原子序数小于 17，该化合物从以下类别中选择：
(1) An organic compound AH in which H H HH is hydrogen and A A AA is an organic anionic radical, having:
（1） 一种有机化合物 AH，其中 H H HH 为氢， A A AA 为有机阴离子自由基，具有：
(a) An ionization constant in water of at least about 1 × 10 − 10 1 × 10 − 10 1xx10^(-10)1 \times 10^{-10} at about 25 ∘ C 25 ∘ C 25^(@)C25^{\circ} \mathrm{C}.;
（a） 水中电离常数至少 1 × 10 − 10 1 × 10 − 10 1xx10^(-10)1 \times 10^{-10} 25 ∘ C 25 ∘ C 25^(@)C25^{\circ} \mathrm{C} 约为 .;
(b) A water solubility at 50 ∘ 50 ∘ 50^(@)50^{\circ} C. of at least about 0.0005 % 0.0005 % 0.0005%0.0005 \%; and
（b） 在 C. 处 50 ∘ 50 ∘ 50^(@)50^{\circ} 的水溶性至少约为 0.0005 % 0.0005 % 0.0005%0.0005 \% ;以及
© In saturated aqueous solutions at about 25 ∘ C 25 ∘ C 25^(@)C25^{\circ} \mathrm{C}. a pH of not greater than about 7;
© 在饱和水溶液中， 25 ∘ C 25 ∘ C 25^(@)C25^{\circ} \mathrm{C} pH 值不大于约 7;
(2) The alkaline earth metal salts of such organic compounds;
（2） 此类有机化合物的碱土金属盐;
the relative amounts of A A AA and B B BB used being in the range of from about one equivalent of A to about 10 equivalents of B B BB to about 10 equivalents of A A AA to about one equivalent of B B BB;
的相对数量 和 B B BB 使用的相对数量 A A AA 在大约 1 当量 A 到大约 10 当量 B B BB 到大约 10 A A AA 当量到大约 1 当量 B B BB 的范围内;
C. An inorganic alkaline earth metal compound
C. 无机碱土金属化合物
(1) Which is water-soluble at a temperature of 50 ∘ C 50 ∘ C 50^(@)C50^{\circ} \mathrm{C}. of at least 0.0003 % 0.0003 % 0.0003%0.0003 \%
（1） 在至少 0.0003 % 0.0003 % 0.0003%0.0003 \% 的温度下 50 ∘ C 50 ∘ C 50^(@)C50^{\circ} \mathrm{C} 是水溶性的 。
(2) In an amount such that there are present in the mass substantially more than 1 equivalent of alkaline earth metal, including the alkaline earth metal present in the remaining components; per equivalent of A A AA plus B B BB; and
（2） 以使质量中存在的碱土金属量大大超过 1 当量的碱土金属，包括存在于其余成分中的碱土金属;每当量 A A AA 为加 B B BB ;以及
D. Water, in an amount equal to at least about one mole per mole of C ,
D. 水，量至少等于每摩尔 C 约 1 摩尔，
II: And then maintaining the mass at a temperature and for a period of time sufficient to drive off substantially all free water and water of hydration which may be present.
II：然后将质量保持在足以驱除可能存在的几乎所有游离水和水合水的温度和一段时间。
In the above-outine processes, following Step II, the mass or product can be optionally treated in accordance with Steps III and IV given below.
在上述过程中，在步骤 II 之后，可以选择性地按照下面给出的步骤 III 和 IV 处理质量或产物。
III. Then treating the mass or product with a material which in the presence of the mass or product will form a material having a higher ionization constant than the promoter, and optionally;
III. 然后用一种材料处理质量或产品，该材料在质量或产品存在下会形成具有比促进剂更高的电离常数的材料，并且是可选的;
IV. Removing from the mass or product so much of the liberated or released promoter as may have been formed by Step III.
IV. 从质量或产物中去除步骤 III 可能形成的大量释放或释放的启动子。
The following examples give the preparation of a plurality of products which range in metal content from about that of the normal salt up to many times that amount.
以下示例给出了多种产品的制备，这些产品的金属含量范围从普通盐的金属含量到该量的许多倍。
We have found that sulphate ash and/or metal content values, and the metal ratio values calculated therefrom, are one means for characterizing certain of the salt complexes. As the description of the invention proceeds, it will become apparent that the neutralization number of a salt complex is in certain instances an unreliable index of the amount of excess metal in such complex, since it is greatly affected by the type of inorganic alkaline earth compound employed and can be varied within wide limits without significantly changing the metal content of the product by treatment of the mass with air, CO 2 CO 2 CO_(2)\mathrm{CO}_{2}, and the like.
我们发现硫酸盐灰分和/或金属含量值，以及由此计算的金属比例值，是表征某些盐络合物的一种方法。随着本发明描述的进行，很明显，盐络合物的中和值在某些情况下是这种络合物中过量金属量的不可靠指标，因为它受所采用的无机碱土化合物类型的影响很大，并且可以在很宽的范围内变化，而不会通过用空气处理质量来显着改变产品的金属含量， CO 2 CO 2 CO_(2)\mathrm{CO}_{2} 等。
The above is not to be construed as a statement that the neutralization number is not an important property of a salt complex. For some uses, for example in lubricants, it is advantageous in certain instances to employ a salt complex of a substantially neutral character, whereas in other instances a salt complex of high alkalinity has been found to produce the desired results.
以上内容不应被解释为中和值不是盐络合物的重要特性的陈述。对于某些用途，例如在润滑剂中，在某些情况下使用基本中性特性的盐络合物是有利的，而在其他情况下，已发现高碱度的盐络合物可以产生所需的结果。

EXAMPLE 1  示例 1

1980 grams of the barium salt of petrolatum sulphonic acid (which contains 9.2 % 9.2 % 9.2%9.2 \% sulphate ash, and is derived from Pa. amber petrolatum) and 132 grams of para-tertiary-butyl phenol were placed into a 5 -liter, 3 -neck flask and heated to 95 ∘ 95 ∘ 95^(@)95^{\circ} C. To this mixture was added a barium oxide slurry ( 417 grams of barium oxide and 1100 grams of water) and the mixture was heated for about one hour at reflux temperature. Then the temperature was slowly raised to about 150 − 160 ∘ 150 − 160 ∘ 150-160^(@)150-160^{\circ} C. and maintained there for one hour to remove substantially all of the water. The product was then filtered. The salt complex is a viscous liquid, light brown in color and having a very slight odor. The salt complex had the following properties:
将 1980 克凡士林磺酸钡盐（含有 9.2 % 9.2 % 9.2%9.2 \% 硫酸盐灰分，来源于 Pa. amber petrolatum）和 132 克对叔丁基苯酚放入 5 升 3 颈烧瓶中并加热至 95 ∘ 95 ∘ 95^(@)95^{\circ} C。向该混合物中加入氧化钡浆液（417 克氧化钡和 1100 克水），并将混合物在回流温度下加热约一小时。然后慢慢将温度升高到摄氏度左右 150 − 160 ∘ 150 − 160 ∘ 150-160^(@)150-160^{\circ} 并保持在那里 1 小时以去除几乎所有的水。然后对产品进行过滤。盐络合物是一种粘稠液体，呈浅棕色，具有非常轻微的气味。盐复合物具有以下特性：
Sa  萨
Solvent  溶剂

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month  月
Sa Solvent "Percent of" "Initial Product added" "Appear- ance" "Appear- anter ance after week" month | Sa | | | | | | :---: | :---: | :---: | :---: | :---: | | Solvent | Percent <br> of | Initial <br> Product <br> added | Appear- <br> ance | Appear- <br> anter <br> ance <br> after <br> week | | month | | | | |
The above preparation, which is an example of the present invention, is compared with a basic sulphonate prepared in accordance with a conventional technique and which is described below.
将上述制剂（作为本发明的一个例子）与根据常规技术制备的碱性磺酸盐进行比较，如下所述。

EXAMPLE 2  示例 2

500 grams of the barium salt of the petrolatum sulphonic acid given in Example 1 were mixed with a slurry of barium oxide (containing 38 grams of barium oxide and 50 grams of water) and placed in a 2 -liter, 3 -neck flask; heated at about 160 ∘ C 160 ∘ C 160^(@)C160^{\circ} \mathrm{C}. for one hour until substantially all of the water was removed, and then the product was filtered. The resultant basic sulphonate has the following properties:
将实施例1中给出的凡士林磺酸的500克钡盐与氧化钡浆液（含有38克氧化钡和50克水）混合，并置于2升、3颈烧瓶中;在约 160 ∘ C 160 ∘ C 160^(@)C160^{\circ} \mathrm{C} .加热1小时，直到基本上除去所有的水， 然后对产品进行过滤。所得的碱性磺酸盐具有以下特性：
Basic No 5.27  基本 No 5.27
Per cent sulphate ash 9.85
硫酸盐灰分 9.85
Metal ratio 1.08  金属比 1.08

HXAMPLE 3  HXAMPLE 3 系列

1000 grams of the barium salt of unsaturated paraffin wax sulphonic acid containing 13.1 % 13.1 % 13.1%13.1 \% sulphate ash were mixed with 455 grams of a mineral oil having a viscosity of 160 SSU at 100 ∘ 100 ∘ 100^(@)100^{\circ} F. and 109.5 grams of para-tertiary-butyl phenol (ratio of equivalents is 1.54 ), placed in a suitable vessel and heated to about 95 ∘ C 95 ∘ C 95^(@)C95^{\circ} \mathrm{C}. with stirring. To this mixture was added a slurry of barium oxide (containing 269 grams of barium oxide and 920 grams of water) and the total mixture was heated at about 100 ∘ C 100 ∘ C 100^(@)C100^{\circ} \mathrm{C}. for one hour. The temperature was slowly raised to about 150 ∘ C 150 ∘ C 150^(@)C150^{\circ} \mathrm{C}. and held there for about one hour until substantially all of the water was removed. Then about 3 % 3 % 3%3 \% Hyflo (a filter-aid) was added to the product to facilitate filtering. The salt complex was then separated by filtration. The salt complex thus prepared had the following properties:
将 1000 克含硫酸盐灰分的不饱和石蜡磺酸钡 盐与 455 克 F 时粘度为 160 SSU 的矿物油和 109.5 克对叔丁基苯酚（当量比为 1.54）混合，置于合适的容器中并加热至约 95 ∘ C 95 ∘ C 95^(@)C95^{\circ} \mathrm{C} 100 ∘ 100 ∘ 100^(@)100^{\circ} 13.1 % 13.1 % 13.1%13.1 \% .搅拌。向该混合物中加入氧化钡浆液（含有 269 克氧化钡和 920 克水），并将总混合物加热约 100 ∘ C 100 ∘ C 100^(@)C100^{\circ} \mathrm{C} .一小时。温度缓慢升高到大约 150 ∘ C 150 ∘ C 150^(@)C150^{\circ} \mathrm{C} 。并保持约 1 小时，直到几乎所有的水都被去除。然后将 Hyflo 3 % 3 % 3%3 \% （一种助滤剂）添加到产品中以方便过滤。然后通过过滤分离盐络合物。这样制备的盐络合物具有以下特性：

Per cent sulphate ash__-_ 26.5
硫酸盐百分比 ash__-_ 26.5

Solubility  溶解度
Solvent  溶剂 Percent of Product added  Percent   of   Product   added  {:[" Percent "],[" of "],[" Product "],[" added "]:}\begin{aligned} & \text { Percent } \\ & \text { of } \\ & \text { Product } \\ & \text { added } \end{aligned} Initial Appear- ance  初次出现 Appearance after 1 week  1 周后出现 Appearance after 1 month  1 个月后出现
Pa. 150 Neutral Oil. 50 Clear  清楚 Clear  清楚 Clear.  清楚。
Do.  做。 -do  -做 -do.-  -做。- Do.  做。
-..do.....  -..做。。。。。 -.do.  -。做。 Do.  做。
Solvent " Percent of Product added " Initial Appear- ance Appearance after 1 week Appearance after 1 month Pa. 150 Neutral Oil. 50 Clear Clear Clear. Do. -do -do.- Do. -..do..... -.do. Do.| Solvent | $\begin{aligned} & \text { Percent } \\ & \text { of } \\ & \text { Product } \\ & \text { added } \end{aligned}$ | Initial Appear- ance | Appearance after 1 week | Appearance after 1 month | | :---: | :---: | :---: | :---: | :---: | | Pa. 150 Neutral Oil. | 50 | Clear | Clear | Clear. | | Do. | | -do | -do.- | Do. | | | | -..do..... | -.do. | Do. |
The salt complex product was fluid, brown in color, and did not contain any odor.
盐复合物产物是液体，呈棕色，不含任何气味。
The preparation given in Example 3 is a typical illustration of the present invention. In Example 4 given below, a basic sulphonate was prepared in accordance with a conventional technique for comparison with the product given in Example 3.
实施例 3 中给出的制备是本发明的典型说明。在下面给出的实施例 4 中，根据常规技术制备碱性磺酸盐，以便与实施例 3 中给出的产品进行比较。

EXAMPLE 4  示例 4

511 grams of the barium salt of unsaturated paraffin wax sulphonic acid given in Example 3 were mixed with 75 grams of water and heated to about 60 ∘ C 60 ∘ C 60^(@)C60^{\circ} \mathrm{C}. with stirring. 58 grams of barium oxide were added to the mixture, which was then heated to about 150 ∘ C 150 ∘ C 150^(@)C150^{\circ} \mathrm{C}. and held there for one hour until substantially all of the water was removed. The product was filtered with the aid of Hyflo in order to separate the complex salt. The salt complex had the following properties:
将实施例3中给出的不饱和石蜡磺酸的511克钡盐与75克水混合，并在搅拌下加热至约 60 ∘ C 60 ∘ C 60^(@)C60^{\circ} \mathrm{C} 。将58克氧化钡加入混合物中，然后将其加热至约 150 ∘ C 150 ∘ C 150^(@)C150^{\circ} \mathrm{C} 。 并在那里保持一小时，直到基本上除去所有的水。该产品在 Hyflo 的帮助下过滤，以分离复合盐。盐复合物具有以下特性：
Basic No.  基本编号

Metal ratio  金属比例