阅读说明：本技术 一种硼化磺酸钙的制备方法 (Preparation method of calcium borosulfonate ) 是由 李学文 卜卫元 王龙龙 范金凤 张超 于 2021-09-07 设计创作，主要内容包括：本发明公开了一种硼化磺酸钙的制备方法,包括：将有机溶剂、长链烷基苯磺酸、重烷基苯磺酸、基础油、低碳醇、助剂和氧化钙混合以进行中和反应；加入聚异丁烯丁二酸酐或者十二烷基琥珀酸酐中的一种、一种硫化烷基酚钙及一种低碳醇搅拌均匀,加入氧化钙、水、通入二氧化碳进行两次碳酸化反应,使游离碱度达到预设值；加入硼化物进行硼化反应,脱醇水并离心除渣,蒸馏溶剂得到硼化磺酸钙产品。通过本发明的技术方案,减少了繁杂的操作步骤,避免了碳酸钙胶核的破坏,产品的过滤性好,有效提高了硼酸的转化率,产品渣含量低,收率高,有效降低了游离酚含量,使产品具有极好的清净性、抗氧化性和抗磨性能,产品粘度低,胶体稳定性好。(The invention discloses a preparation method of calcium borosulfonate, which comprises the following steps: mixing an organic solvent, long-chain alkyl benzene sulfonic acid, heavy alkyl benzene sulfonic acid, base oil, low-carbon alcohol, an auxiliary agent and calcium oxide to perform a neutralization reaction; adding one of polyisobutylene succinic anhydride or dodecyl succinic anhydride, one of sulfurized calcium alkyl phenolate and one of low carbon alcohol, stirring uniformly, adding calcium oxide, water and introducing carbon dioxide to perform carbonation reaction twice, so that the free alkalinity reaches a preset value; adding boride to carry out a boronization reaction, dealcoholizing water, centrifuging to remove slag, and distilling a solvent to obtain a calcium boronate product. By adopting the technical scheme of the invention, the complex operation steps are reduced, the damage of calcium carbonate gel cores is avoided, the filterability of the product is good, the conversion rate of boric acid is effectively improved, the content of product slag is low, the yield is high, the content of free phenol is effectively reduced, and the product has excellent detergency, oxidation resistance and wear resistance, low product viscosity and good colloid stability.)

1. A preparation method of calcium borosulfonate is characterized by comprising the following steps:

the method comprises the following steps: adding an organic solvent, long-chain alkyl benzene sulfonic acid, heavy alkyl benzene sulfonic acid, base oil, low-carbon alcohol, an auxiliary agent and calcium oxide into a reaction container, and mixing to perform neutralization reaction, wherein the auxiliary agent adopts ammonium carbonate, ammonium bicarbonate, urea or calcium chloride, and comprises the following components, by weight, 40% -50% of the organic solvent, 10% -15% of the total amount of the long-chain alkyl benzene sulfonic acid and the heavy alkyl benzene sulfonic acid, 13% -16% of the base oil, 2% -6% of the low-carbon alcohol, 0.5% -1% of the auxiliary agent and 1% -3% of the calcium oxide;

step two: adding one of polyisobutylene succinic anhydride or dodecyl succinic anhydride, one of sulfurized calcium alkyl phenolate and one of low-carbon alcohol into the reaction vessel, uniformly stirring, adding calcium oxide, water and carbon dioxide into the reaction vessel, and performing carbonation reaction twice to enable the free alkalinity to reach a preset value; wherein, the weight percentage of the polyisobutylene succinic anhydride or the dodecyl succinic anhydride accounts for 1 to 3 percent, the sulfurized calcium alkyl phenolate accounts for 1 to 5 percent, the low carbon alcohol accounts for 1 to 5 percent, the calcium oxide accounts for 3 to 4 percent respectively and the water accounts for 0.5 to 1 percent respectively in the two times of carbonation reaction;

step three: adding a preset amount of boride into the reaction container to perform a boronization reaction, wherein the boride accounts for 3-14 wt%;

step four: and after the boronization reaction is finished, removing alcohol water, centrifugally removing slag, and distilling the solvent to obtain a calcium boronate product.

2. The method for preparing calcium boronate sulfonate according to claim 1, wherein in the first step, the organic solvent is toluene or xylene, the base oil is 150N or 150SN, and the lower alcohol is C₁～C₆The alcohol of (1).

3. The method for preparing calcium borosulfonate according to claim 1, wherein the reaction temperature of the neutralization reaction in the first step is 40-60 ℃ and the reaction time is 1.5 hours.

4. The method for preparing calcium borosulfonate according to claim 1, wherein the active substance in the long-chain alkylbenzene sulfonic acid is 85-95%, the active substance in the heavy alkylbenzene sulfonic acid is 65-75%, and the long-chain alkylbenzene sulfonic acid is toluene and C₁₀-C₃₀The product obtained by alkylating the olefin a is obtained by sulfonation reaction of sulfur trioxide and the heavy alkylbenzene sulfonic acid is obtained by sulfonation reaction of heavy alkylbenzene and sulfur trioxide.

5. The method for producing calcium borosulfonate according to claim 1 or 4, wherein the mass ratio of the long-chain alkylbenzene sulfonic acid to the heavy alkylbenzene sulfonic acid is 1:1 to 3: 1.

6. The method for preparing calcium boronate sulfonate according to claim 1, wherein in the two carbonation reactions of the second step, calcium monoxide and water are added first, and carbon dioxide is introduced for carbonation reaction until the free alkalinity reaches 30-60 mgKOH/g;

then adding secondary calcium oxide and secondary water, and introducing secondary carbon dioxide to carry out carbonation reaction until the free alkalinity reaches 70-200 mgKOH/g.

7. The method for preparing calcium borosulfonate according to claim 1 or 6, wherein in the second step, the lower alcohol is C₁～C₆The sulfurized calcium alkyl phenate adopts one of different base numbers.

8. The method for preparing calcium borosulfonate according to claim 1 or 6, wherein the reaction temperature of the carbonation reaction is maintained at 40-60 ℃.

9. The method for preparing calcium borosulfonate according to claim 1, wherein boric acid, boron oxide or borax is used as the boride, and the boride is uniformly added in a fractional manner;

according to the increase of the boron content of the calcium boronate to be prepared, the total adding amount of the boride is increased, and the adding times of the boride are increased.

10. The method for preparing calcium borosulfonate according to claim 1, wherein in the third step, the reaction temperature of the boronization reaction is 60-70 ℃, and the constant-temperature reaction time after the boride is added into the reaction vessel is 2.0-4.0 hours.

Technical Field

The invention relates to the technical field of calcium sulfonate preparation, in particular to a preparation method of calcium boronate sulfonate.

Background

Calcium sulfonate belongs to one of the metal detergents which is used earlier, is most widely used and is used in the largest amount, and is an essential additive in internal combustion engine oil. The sulfonate is used in engine oil, can neutralize acid oxide formed during the use of engine oil and fuel oil, and can inhibit the deterioration of lubricating oil or reduce the formation of high temperature deposit on the surface of piston ring area to maintain the inside of engine clean. At the same time, the non-oil-soluble colloid or oxide simple substance generated by the oxidation of the lubricating oil and the incomplete combustion of the fuel can be dissolved in the oil. Due to this solubilization, various reactive groups in the gum are rendered inactive, or the gum is allowed to continue to react while maintaining the solubilization conditions, thereby inhibiting their formation of deposits such as varnish, carbon deposit, sludge, and the like.

The calcium sulfonate has the advantages of easily obtained preparation raw materials and low cost, can simultaneously utilize byproducts in chemical production, and is not high in price even if the specially prepared raw materials are low, so that the production method is researched more at home and abroad, the synthesis process is mature, and the synthesis process of the high-alkalinity calcium sulfonate is characterized in that alkylbenzene sulfonic acid, diluent oil, a solvent, a metal oxide or hydroxide, water and an accelerant are added into a reactor, carbon dioxide is introduced for high alkalization, the solvent, water and the like are removed by flash evaporation, and the product is obtained by centrifugation or filtration refining.

While studying the cleaning effect of calcium sulfonate, people are also continuously studying the influence of calcium sulfonate on the service performance such as the wear resistance, the oxygen resistance and the like of oil products. Workers skilled in the art have also sought to synthesize overbased sulfonates, such as calcium boronate sulfonate, which have multifunctional and versatile properties.

US 4965004 discloses a method for preparing a boron-containing calcium sulfonate: adding a boronizing reagent into the overbased calcium sulfonate under the coexistence of a polar solvent and a hydrocarbon solvent, and reacting for 0.25 to 5 hours at the temperature of between 15 and 100 ℃; then distilling the solvent, filtering the residue, and finally distilling under reduced pressure to remove the solvent to obtain the product. The method has simple process and few operation steps, but the filterability is difficult because the slag contains fine substances. US5470495 discloses a process for the preparation of a calcium sulphonate containing detergent: dissolving high-alkaline calcium sulfonate in a solvent, fully stirring and heating to 130 ℃, adding alkyl benzene sulfonic acid, adding a certain amount of methanol after dehydration, and adding boric acid until the calcium sulfonate is completely dissolved to participate in reaction. Finally, the methanol, the water and the solvent are distilled off to obtain the product. US5470495 discloses a process for preparing boron-containing calcium sulfonate grease, which comprises dissolving an overbased calcium sulfonate in a base oil, adding diluted alkylbenzenesulfonic acid, heating to 130 ℃, then adding methanol and boric acid, finally distilling off the methanol, removing water, filtering and desolventizing to obtain the boron-containing calcium sulfonate grease product.

At present, the general method for preparing the boron-containing overbased sulfonate is to add a boron compound on the basis of the overbased sulfonate and then carry out a boronation reaction at a certain temperature. In the method, the sulfonate part colloid is destroyed by boric acid to form fine calcium carbonate, so that the base number of the product is reduced, and the filtration is influenced. The two-step method has complicated operation process, needs twice dealcoholization and twice filtration or centrifugation, and causes overhigh operation cost and low production efficiency. In addition, the boronizing process is a simple neutralization reaction, but the conversion rate of boric acid is very low, and the direct appearance is that after the boronizing process, partial boric acid particles are not completely dissolved and participate in the reaction, so that the conversion rate of boric acid is low and the product yield is low.

The proportion of the high-alkalinity sulfonate in the complexing agent reaches 30% -50%, the phenol content is required to be below 0.3% along with the increasing standards of Europe and America on the phenol content of the complexing agent, and the sulfonate with low free phenol has attracted the attention of researchers because the proportion of the sulfonate in the complexing agent is high.

Disclosure of Invention

Aiming at the problems, the invention provides a preparation method of calcium boronate sulfonate, which utilizes a one-step method for producing calcium sulfonate, reduces complicated operation steps, avoids the damage of boric acid to a formed calcium carbonate colloid core in the boronizing process, has good filterability, and can be used for preparing calcium boronate sulfonate through carbonation reaction and boronizing reaction, the conversion rate of boric acid is effectively improved through effective auxiliary agent combination, the adding amount of boride is calculated through accurate detection of free alkali, the full reaction of boride and residual calcium oxide can be fully ensured, so that the content of the product slag is very low, the yield is high, the calcium alkyl phenate is selected to replace the conventional dodecylphenol, the colloid wrapping effect in the carbonization reaction process is not influenced, and the free phenol content of the product is effectively reduced, so that the product has excellent detergency, oxidation resistance and wear resistance, low viscosity and good colloid stability.

In order to achieve the above object, the present invention provides a method for preparing calcium boronate sulfonate, comprising:

the method comprises the following steps: adding an organic solvent, long-chain alkyl benzene sulfonic acid, heavy alkyl benzene sulfonic acid, base oil, low-carbon alcohol, an auxiliary agent and calcium oxide into a reaction container, and mixing to perform neutralization reaction, wherein the auxiliary agent adopts ammonium carbonate, ammonium bicarbonate, urea or calcium chloride, and comprises the following components, by weight, 40% -50% of the organic solvent, 10% -15% of the total amount of the long-chain alkyl benzene sulfonic acid and the heavy alkyl benzene sulfonic acid, 13% -16% of the base oil, 2% -6% of the low-carbon alcohol, 0.5% -1% of the auxiliary agent and 1% -3% of the calcium oxide;

step two: adding one of polyisobutylene succinic anhydride or dodecyl succinic anhydride, one of sulfurized calcium alkyl phenolate and one of low-carbon alcohol into the reaction vessel, uniformly stirring, adding calcium oxide, water and carbon dioxide into the reaction vessel, and performing carbonation reaction twice to enable the free alkalinity to reach a preset value; wherein, the weight percentage of the polyisobutylene succinic anhydride or the dodecyl succinic anhydride accounts for 1 to 3 percent, the sulfurized calcium alkyl phenolate accounts for 1 to 5 percent, the low carbon alcohol accounts for 1 to 5 percent, the calcium oxide accounts for 3 to 4 percent respectively and the water accounts for 0.5 to 1 percent respectively in the two times of carbonation reaction;

step three: adding a preset amount of boride into the reaction container to perform a boronization reaction, wherein the boride accounts for 3-14 wt%;

step four: and after the boronization reaction is finished, removing alcohol water, centrifugally removing slag, and distilling the solvent to obtain a calcium boronate product.

In the above technical solution, preferably, in the first step, the organic solvent is toluene or xylene, the base oil is 150N or 150SN, and the lower alcohol is C₁～C₆The alcohol of (1).

In the above technical scheme, preferably, the reaction temperature of the neutralization reaction in the step one is 40 to 60 ℃, and the reaction time is 1.5 hours.

In the above technical solution, preferably, the long-chain alkylbenzene sulfonic acid contains 85% to 95% of active matter, and the heavy alkylbenzene sulfonic acid contains 65% to 75% of active matter, and the long-chain alkylbenzene sulfonic acid is toluene and C₁₀-C₃₀The product obtained by alkylating the olefin a is obtained by sulfonation reaction of sulfur trioxide and the heavy alkylbenzene sulfonic acid is obtained by sulfonation reaction of heavy alkylbenzene and sulfur trioxide.

In the above technical solution, preferably, the mass ratio of the long-chain alkylbenzene sulfonic acid to the heavy alkylbenzene sulfonic acid is 1:1 to 3: 1.

In the above technical solution, preferably, in the two carbonation reactions in the second step, first calcium oxide and first water are added, and first carbon dioxide is introduced to perform the carbonation reaction until the free alkalinity reaches 30-60 mgKOH/g;

then adding secondary calcium oxide and secondary water, and introducing secondary carbon dioxide to carry out carbonation reaction until the free alkalinity reaches 70-200 mgKOH/g.

In the above technical solution, preferably, in the second step, the lower alcohol is C₁～C₆The sulfurized calcium alkyl phenate adopts one of different base numbers.

In the technical scheme, preferably, the reaction temperature of the carbonation reaction is kept at 40-60 ℃.

In the above technical solution, preferably, in the third step, the boride is boric acid, boron oxide or borax, and the boride is uniformly added in several times;

according to the increase of the boron content of the calcium boronate to be prepared, the total adding amount of the boride is increased, and the adding times of the boride are increased.

In the above technical scheme, preferably, in the third step, the reaction temperature of the boronation reaction is 60-70 ℃, and the constant-temperature reaction time of the boride after being added into the reaction vessel is 2.0-4.0 hours.

Compared with the prior art, the invention has the beneficial effects that: the method has the advantages that by utilizing the one-step method for producing the calcium sulfonate, the complex operation steps are reduced, the damage of boric acid to a formed calcium carbonate colloid core in the boronizing process is avoided, the filterability of the product is very good, the conversion rate of the boric acid is effectively improved through the carbonation reaction and the boronizing reaction through the effective auxiliary agent combination, the adding amount of boride is calculated through the accurate detection of free alkali, the full reaction of the boride and residual calcium oxide can be fully ensured, the content of product slag is very low, the yield is high, calcium alkyl phenate is selected to replace conventional dodecylphenol, the colloid wrapping effect in the carbonization reaction process is not influenced, the content of free phenol in the product is effectively reduced, the product has very good detergency, oxidation resistance and wear resistance, the viscosity of the product is low, and the colloid stability is good.

Drawings

Fig. 1 is a schematic flow chart of a method for preparing calcium boronate sulfonate, which is disclosed in an embodiment of the present invention.

Detailed Description

In order to make the objects, technical solutions and advantages of the embodiments of the present invention clearer, the technical solutions in the embodiments of the present invention will be clearly and completely described below with reference to the drawings in the embodiments of the present invention, and it is obvious that the described embodiments are some, but not all, embodiments of the present invention. All other embodiments, which can be obtained by a person skilled in the art without any inventive step based on the embodiments of the present invention, are within the scope of the present invention.

The invention is described in further detail below with reference to the attached drawing figures:

as shown in fig. 1, the preparation method of calcium boronate sulfonate provided by the invention comprises the following steps:

the method comprises the following steps: adding an organic solvent, long-chain alkyl benzene sulfonic acid, heavy alkyl benzene sulfonic acid, base oil, low-carbon alcohol, an auxiliary agent and calcium oxide into a reaction container, and mixing to perform neutralization reaction, wherein the auxiliary agent adopts ammonium carbonate, ammonium bicarbonate, urea or calcium chloride, and comprises the following components, by weight, 40% -50% of the organic solvent, 10% -15% of the total amount of the long-chain alkyl benzene sulfonic acid and the heavy alkyl benzene sulfonic acid, 13% -16% of the base oil, 2% -6% of the low-carbon alcohol, 0.5% -1% of the auxiliary agent and 1% -3% of the calcium oxide;

step two: adding one of polyisobutylene succinic anhydride or dodecyl succinic anhydride, one of sulfurized calcium alkyl phenolate and one of low-carbon alcohol into a reaction vessel, uniformly stirring, adding calcium oxide, water and introducing carbon dioxide into the reaction vessel to perform carbonation reaction twice, and enabling the free alkalinity to reach a preset value; wherein, the weight percentage of the polyisobutylene succinic anhydride or the dodecyl succinic anhydride accounts for 1 to 3 percent, the sulfurized calcium alkyl phenolate accounts for 1 to 5 percent, the low carbon alcohol accounts for 1 to 5 percent, the calcium oxide accounts for 3 to 4 percent respectively and the water accounts for 0.5 to 1 percent respectively in the two times of carbonation reaction;

step three: adding a preset amount of boride into a reaction container for carrying out a boronization reaction, wherein the boride accounts for 3-14% by weight;

step four: and after the boronization reaction is finished, removing alcohol water, centrifugally removing slag, and distilling the solvent to obtain a calcium boronate product.

In the embodiment, by utilizing the one-step method for producing the calcium sulfonate, the complex operation steps are reduced, the damage of boric acid to a formed calcium carbonate colloid core in the boronizing process is avoided, the filterability of the product is very good, the conversion rate of the boric acid is effectively improved through the carbonation reaction and the boronizing reaction through effective auxiliary agent combination, the addition amount of boride is calculated through the accurate detection of free alkali, the full reaction of the boride and residual calcium oxide can be fully ensured, the content of product slag is very low, the yield is high, calcium alkylphenol is selected to replace conventional dodecylphenol, the colloid wrapping effect in the carbonization reaction process is not influenced, the free phenol content of the product is effectively reduced, the product has very good detergency, oxidation resistance and wear resistance, the product viscosity is low, and the colloid stability is good.

Specifically, firstly, adding an organic solvent, long-chain alkyl benzene sulfonic acid, heavy alkyl benzene sulfonic acid, base oil, low-carbon alcohol, an auxiliary agent and calcium oxide into a four-neck flask provided with a stirrer, a reflux condenser tube and a thermocouple thermometer, heating and stirring to realize a neutralization synthesis reaction.

Secondly, adding one of polyisobutylene succinic anhydride or dodecyl succinic anhydride, one of sulfurized calcium alkyl phenolate and one of low-carbon alcohol into the four-neck flask, stirring for 30-60min, and then carrying out carbonation reaction twice.

Then weighing a certain amount of boride, putting the boride into the four-neck flask, carrying out boride reaction at constant temperature to generate a micelle with calcium carbonate particles and calcium borate particles as cores, and wrapping the micelle by neutral calcium sulfonate, wherein the micelle is uniformly dispersed in an oil phase to form a stable colloidal system.

And finally, after the boration reaction is finished, carrying out dealcoholization water and centrifugal deslagging on the mixture in the four-neck flask, distilling the solvent to obtain the product, wherein the TBN of the product is 300-330 mgKOH-g < -1 >, the boron content is 1.0-4.0 percent, the free phenol content is lower than 0.2 percent, and the product has good colloidal stability and oil solubility after three months of observation.

Wherein, in the preparation process, the higher the content of the lower alcohol in the carbonation process, the higher the conversion rate of the boride, so that more lower alcohol needs to be added in the carbonation process to prepare a product with higher boron content.

In the preparation process, the higher the content of the added auxiliary agent is, the easier the product with high boron content can be prepared.

In the preparation process, under the condition of certain content of calcium oxide, products with the same TBN300 base number are prepared, a series of products with different boron contents, such as products with low boron contents, are prepared by controlling the starting point of the boronizing process, sufficient air is introduced in the carbonation process, more base numbers are provided by the coated calcium carbonate, and partial base numbers are provided by a small amount of calcium borate. Conversely, for products with high boron content, less aeration is required during carbonation, less reduction is provided by calcium carbonate, more boric acid is added, and more base number is provided by calcium borate.

In the above embodiment, preferably, in the step one, toluene or xylene is used as the organic solvent, the addition amount is preferably 40%, 150N or 150SN type is used as the base oil, the addition amount is preferably 15%, and C is used as the lower alcohol₁～C₆The alcohol (2) and the auxiliary are preferably ammonium carbonate, and the addition amount thereof is preferably 0.4%.

In the above embodiment, preferably, in the step one, the reaction temperature of the neutralization reaction is 40 to 60 ℃, and the reaction time is 1.5 hours.

In the above embodiment, it is preferable that the active substance in the long-chain alkylbenzene sulfonic acid is 85% to 95%, the active substance in the heavy alkylbenzene sulfonic acid is 65% to 75%, and the total amount of the long-chain alkylbenzene sulfonic acid and the heavy alkylbenzene sulfonic acid added is 12%. Preferably, the mass ratio of the long-chain alkyl benzene sulfonic acid to the heavy alkyl benzene sulfonic acid is 1: 1-3: 1. Wherein the long-chain alkylbenzene sulfonic acid is toluene and C₁₀-C₃₀The product obtained by alkylating the alpha olefin is obtained by sulfonation reaction of sulfur trioxide and the heavy alkylbenzene sulfonic acid is obtained by sulfonation reaction of heavy alkylbenzene and sulfur trioxide. Among them, alpha-olefin is preferably C₂₀-C₂₄。

In the above embodiment, preferably, in the two carbonation reactions in the second step, first, the primary calcium oxide and the primary water are added, and the primary carbon dioxide is introduced to perform the carbonation reaction until the free alkalinity reaches 30-60 mgKOH/g;

then adding secondary calcium oxide and secondary water, and introducing secondary carbon dioxide to carry out carbonation reaction until the free alkalinity reaches 70-200 mgKOH/g.

In the two carbonation reactions, the amount of calcium oxide added is preferably 3.6% of the total mass, respectively, and the corresponding amount of water is 0.8% of the total mass, respectively.

In the above embodiment, preferably, in the second step, one of the isobaric acid substances of polyisobutylene succinic anhydride or dodecyl succinic anhydride is adoptedPolyisobutylene succinic anhydride is preferably used, and the addition amount of the polyisobutylene succinic anhydride is preferably 1.6%; the lower alcohol is C₁～C₆The alcohol (2) is preferably n-butanol or isobutanol, the addition amount is preferably 3%, and calcium alkyl phenate salts with different base numbers are adopted as the calcium alkyl phenate sulfide, and the addition amount is preferably 2.5%. Wherein, the reaction temperature of the carbonation reaction is preferably kept between 40 and 60 ℃.

In the above embodiment, preferably, in the third step, boric acid, boric oxide or borax is used as the boride, preferably boric acid is used, and the boride is uniformly added in a fractional manner;

according to the increase of the boron content of the calcium boronate to be prepared, the total addition amount of boride is increased, and the addition times of boride are increased.

Specifically, a product having a boron content of 1.0% is prepared, the amount of boric acid is preferably 3.3%, a product having a boron content of 2.0% is prepared, the amount of boric acid is preferably 6.6%, a product having a boron content of 3.0% is prepared, the amount of boric acid is preferably 10%, a product having a boron content of 4.0% is prepared, and the amount of boric acid is preferably 13.8%.

In addition, the feeding mode of the boride is that a product with the boron content of 1.0% is prepared, the boride is added averagely for 2 times, a product with the boron content of 2.0% is prepared, the boride is added averagely for 3 times, a product with the boron content of 3.0% is prepared, the boride is added averagely for 4 times, a product with the boron content of 4.0% is prepared, and the boride is added averagely for 5 times. Wherein the reaction temperature of the boronization reaction is 60-70 ℃, and the constant-temperature reaction time of the boride after being added into the reaction container is 2.0-4.0 hours.

According to the preparation methods of calcium boronate sulfonates provided in the above examples, the preparation methods of calcium boronate sulfonates with different boron contents are specifically described below by using specific examples.

Example 1: preparation of calcium sulfonate with boron content of 1.0%

Adding 150g of xylene # solvent, 23g of long-chain alkylbenzene sulfonic acid, 23g of heavy alkylbenzene sulfonic acid, 65g of 150SN, 10g of methanol, 1.0g of ammonium carbonate and 7.5g of calcium oxide into a 500ml four-neck flask, heating to 40-60 ℃, carrying out neutralization reaction for 60min, and after the neutralization reaction is finished, adding 15g of n-butyl alcohol, 5.0g of polyisobutylene succinic anhydride and 9.0g of vulcanized sodium sulfateStirring calcium alkyl phenolate for 30min, and controlling the temperature to be 40-60 ℃. Then 13.0g of calcium oxide and 4.0g of water are added, carbon dioxide is introduced at the gas speed of 75ml/min at the temperature of 40-60 ℃, the gas is introduced to 4L, the first free alkali reaches 40-60mgKOH/g, the temperature is kept unchanged, 13.0g of calcium oxide and 4.0g of water are added again, the gas is introduced to 8.0L, the second free alkali reaches 30-40mgKOH/g, and the gas introduction is stopped. 16.0g of boric acid is added in two times, the reaction temperature is 55-60 ℃, and the constant temperature is kept for 120 min. And after the constant temperature is finished, dealcoholizing water to 110 ℃, then centrifuging to remove slag, wherein the slag amount is 0.8g/100g of the product, and finally removing the solvent from the centrifugate by reduced evaporation. The base number of the obtained product is 330mgKOH/g, and the kinematic viscosity at 100 ℃ is 30mm²A bright reddish brown product. The boron content by ICP detection is 1.1%. The content of free phenol is 0.12 percent by liquid phase detection.

Example 2: preparation of calcium sulfonate with boron content of 2.0%

150g of xylene # solvent, 23g of long-chain alkylbenzene sulfonic acid, 23g of heavy alkylbenzene sulfonic acid, 65g of 150SN, 10g of methanol, 1.2g of ammonium carbonate and 7.5g of calcium oxide are added into a 500ml four-neck flask, the temperature is raised to 40-60 ℃ for neutralization reaction for 60min, after the neutralization reaction is finished, 17g of n-butyl alcohol, 5.0g of polyisobutylene succinic anhydride and 8.0g of sulfurized calcium alkyl phenate are added, the mixture is stirred for 30min, and the temperature is controlled to be kept at 40-60 ℃. Then 13.0g of calcium oxide and 4.0g of water are added, carbon dioxide is introduced at the gas speed of 75ml/min at the temperature of 40-60 ℃, the gas is introduced to 4L, the first free alkali reaches 40-60mgKOH/g, the temperature is kept unchanged, 13.0g of calcium oxide and 4.0g of water are added again, the gas is introduced to 6.5L, the second free alkali reaches 60-80mgKOH/g, and the gas introduction is stopped. 24.0g of boric acid is added for three times, the reaction temperature is 55-60 ℃, and the constant temperature is 150 min. And after the constant temperature is finished, dealcoholizing water to 110 ℃, then centrifuging to remove slag, wherein the slag amount is 1.0g/100g of the product, and finally removing the solvent from the centrifugate by reduced evaporation. The base number of the obtained product is 328mgKOH/g, and the kinematic viscosity at 100 ℃ is 50mm²A bright reddish brown product. The boron content by ICP detection is 2.1%. The content of free phenol is 0.10 percent by liquid phase detection.

Example 3: preparation of calcium sulfonate with boron content of 3.0%

Into a 500ml four-necked flask, 200g of xylene # solvent, 23g of long-chain alkylbenzene sulfonic acid, 23g of heavy alkylbenzene sulfonic acid, 65g of 150SN, and 10g of methyl ether were chargedHeating alcohol, 1.4g of ammonium carbonate and 7.5g of calcium oxide to 40-60 ℃, carrying out neutralization reaction for 60min, adding 20g of n-butyl alcohol, 5.0g of polyisobutylene succinic anhydride and 7.0g of sulfurized calcium alkyl phenate after the neutralization reaction is finished, stirring for 30min, and controlling the temperature to be kept at 40-60 ℃. Then 13.0g of calcium oxide and 4.0g of water are added, carbon dioxide is introduced at the gas speed of 75ml/min at the temperature of 40-60 ℃, the gas is introduced to 4L, the primary free alkali reaches 40-60mgKOH/g, the temperature is kept unchanged, 13.0g of calcium oxide and 4.0g of water are added again, the gas is introduced to 5.0L, the secondary free alkali reaches 100-120mgKOH/g, and the gas introduction is stopped. 32.0g of boric acid is added in four times, the reaction temperature is 55-60 ℃, and the constant temperature is kept for 180 min. And after the constant temperature is finished, dealcoholizing water to 110 ℃, then centrifuging to remove slag, wherein the slag amount is 1.5g/100g of product, and finally removing the solvent from the centrifugate by reduced evaporation. The base number is 327mgKOH/g, the kinematic viscosity at 100 ℃ is 68mm²A bright reddish brown product. The boron content by ICP assay was 3.1%. The content of free phenol in the liquid phase detection is 0.09%.

Example 4: preparation of calcium sulfonate with boron content of 4.0%

200g of xylene # solvent, 23g of long-chain alkylbenzene sulfonic acid, 23g of heavy alkylbenzene sulfonic acid, 65g of 150SN, 10g of methanol, 1.5g of ammonium carbonate and 7.5g of calcium oxide are added into a 500ml four-neck flask, the temperature is raised to 40-60 ℃ for neutralization reaction for 60min, after the neutralization reaction is finished, 25g of n-butyl alcohol, 5.0g of polyisobutylene succinic anhydride and 5.0g of sulfurized calcium alkyl phenate are added, the mixture is stirred for 30min, and the temperature is controlled to be kept at 40-60 ℃. Then 26.0g of calcium oxide and 8.0g of water are added, carbon dioxide is introduced at 40-60 ℃ at a gas speed of 75ml/min, the gas is introduced to 3.5L, the primary free alkali reaches 150-. 40.0g of boric acid is added for five times, the reaction temperature is 55-60 ℃, and the constant temperature is 240 min. And after the constant temperature is finished, dealcoholizing water to 110 ℃, then centrifuging to remove slag, wherein the slag amount is 2.0g/100g of the product, and finally removing the solvent from the centrifugate by reduced evaporation. The base number of which is 325mgKOH/g and the kinematic viscosity of which is 76mm at 100 ℃ are obtained²A bright reddish brown product. The boron content by ICP assay was 4.1%. The content of free phenol is 0.07% by liquid phase detection.

The performance data of the products obtained in examples 1 to 4 above were compared with those of the TBN300 calcium sulphonate samples to obtain the following table.

Note: the addition amount of the antioxidant is 2 percent and the base oil is 150N in the measurement of the oxidation induction period and the abrasion spot diameter.

According to the table, the oxidation induction period of the TBN300 calcium sulfonate without boron element is 23min, while the oxidation induction period of the samples is longer to 104min in the examples 1-4 along with the gradual increase of the boron content from 1.1% to 4.1%, which shows that the oxidation resistance of the calcium boronate of the invention is better.

From the above table, it can be seen that the wear-leveling diameter of TBN300 calcium sulfonate containing no boron element is 0.79, and the wear-leveling diameter of example 4 containing 4.1% of boron element is 0.32, which indicates that the anti-extrusion performance of the calcium boronate of the present invention is better.

According to the table, the calcium sulfonate product with the boron content of 1.0-4.0% has the boric acid conversion rate of 94.3-99.5%, the product with the boron content of 1.0% is close to 100%, and the higher the boron content is, the boric acid conversion rate is correspondingly reduced, but the boric acid conversion rate of the whole series of products is higher.

According to the table, the alkylphenol calcium salt is selected in the carbonization process, the free phenol content of the series products prepared in the embodiments 1 to 4 is low, and the data distribution is 0.07 to 0.12 percent.

The above is only a preferred embodiment of the present invention, and is not intended to limit the present invention, and various modifications and changes will occur to those skilled in the art. Any modification, equivalent replacement, or improvement made within the spirit and principle of the present invention should be included in the protection scope of the present invention.