Method of producing basic sulfur-containing phenolates of alkaline-earth metals

专利摘要:
A process for the production of a basic alkaline earth metal phenate is disclosed. The process comprises reacting a phenol, a dihydric alcohol, and an alkaline earth metal agent selected from alkaline earth metal oxides and hydroxides to achieve the addition of the alkaline earth metal to the phenol, wherein water is added to the reaction system in an amount of from 0.01 to 10 mols per mol of the alkaline earth metal agent. This basic alkaline earth metal phenate is useful as an additive for lubricating oils and fuel oils.
公开号:SU1450732A3
申请号:SU833635271
申请日:1983-08-15
公开日:1989-01-07
发明作者:Хори Такаси；Уеда Санае；Коима Есихиро
申请人:Космо Ойл Ко.,Лтд (Фирма)；
IPC主号:

专利说明:


cm
This invention relates to an improved process for the preparation of basic sulfur-containing alkaline-earth phenols. metals used as stable additives to hydrocarbon oils or fuel oils.
The purpose of the invention is to simplify the process.
This goal is achieved by preparing a mixture of alkylphenol containing 6-32 carbon atoms in the side chain, oxide or hydroxide of an alkaline earth metal selected from calcium or barium, taken in an amount of 0.1-10 mol per 1 mole of sulfur alkylphenol, taken in an amount of 0 , 1-3.0 mol per 1 mol of an alkaline earth metal oxide or hydroxide, and dihydric alcohol in an amount of 0.15-2.5 mol per 1 mol of an alkaline earth metal oxide or hydroxide, by the interaction of this mixture, ensuring the addition of alkaline earth metal to alkylphenol at 60- and a pressure of 1-8 kg / cm in the presence of water, added in an amount of 0.05-10 mol per 1 mol of alkaline earth metal oxide or hydroxide, by distilling water by distilling water, treating the residue with carbon dioxide at 80-205 0 and pressure 1-30 kg / cm by distillation of unreacted alkylphenol.
Water is preferably added in an amount of 0.1-2.0 mol per 1 mol of alkaline earth metal oxide or hydroxide.
Preferably, the reaction is carried out in the presence of a diluent - a fraction of lubricating oils or higher C | C2 5-alcohol; insoluble materials are removed from the reaction product after its treatment; oxide or hydro
45,558.2 g of neutral oil 150 (alkaline earth metal oxide is used in an amount of 0.1-6 mol per raffin lubricating oil having 1 mol of alkylphenol; ethylene glycol is used as two-P "temperature of 100 ° C; Propylene glycol in the amount of 5, 38 cSt) is placed in a two-liter two-neck pear-shaped flask
50 and distilled, during which para-methylphenol is removed from the solution, using lauryl alcohol and a small amount of ethylene glycol as a solvent.
0.3–1.5 mol per 1 mol of alkaline earth metal oxide or hydroxide; after completion of the reaction by distillation, 60% or more of the added and
50 and subjected to distillation, during which paraokylphenol, using lauryl alcohol and a small amount of ethylene glycol as the solvent, is removed from the solution.
formed during the 55 "reaction, resulting in a distillation residue in an amount of 835.0 g. The temperature at the end of the distillation process is (1.0 mm Hg)
water.
Example 1. In a four-necked flask equipped with a stirrer, a pipe
5 0 5 p
five
0
206 g (1.0 mol) of paraoctylphenol, 48.1 g (1.5 mol) of sulfur, 57.1 g (1.0 mol) of calcium oxide having a purity of 98 are placed in a cooler, an inlet for nitrogen gas and a thermometer. , 3 microns% and 999 g of lauric alcohol, after which the reagents are mixed. In a stream of nitrogen at atmospheric pressure, a mixture consisting of 62 g (1.0 mol) of ethylene glycol and 10.8 g (0.6 mol) of water is introduced into the reactor for 30 minutes. The resulting mixture for carrying out the metal addition reaction at 135 ° C is stirred in the reactor for 4.5 hours. Then, while the pressure in the reactor gradually decreases, the water, water formed during the reaction, and a small amount of ethylene glycide are removed from it by distillation. As a result, a distillation residue in the form of a dark yellowish-green liquid in the amount of 1348 g is formed in the reactor. The final distillate temperature is 104 ° C (19 mm Hg). water
The distillate residue obtained is placed in an autoclave, where it is treated with carbon dioxide at a BbmieHHOM pressure (no more than 12 kg / cm2) at a temperature of 123-126 ° C, which lasts for 30 minutes. Then, the reaction system for 2 hours is maintained at a temperature of 155 s at a higher pressure (no more than .9 kg / cm), as a result of which a solution of a dark yellowish-green color is obtained in an amount of 1,384 g.
After the described treatment of the reaction product solution with carbon dioxide, the resulting solution in, mixed with
5,558.2 g of neutral oil 150 (paraffin lubricating oil having a P "temperature of 100 ° C; viscosity
raffin lubricating oil having a P "temperature of 100 ° C; viscosity
5.38 cSt) is placed in a two-liter two-neck pear-shaped flask
raffin lubricating oil having a P "temperature of 100 ° C; viscosity
and distilled, during which para-methylphenol, using lauryl alcohol and a small amount of ethylene glycol, is removed from the solution.
"Resulting in a distillate residue in an amount of 835.0 g. The temperature at the end of the distillation process is (1.0 mm Hg).
2.9 g of insoluble material is removed by filtration from the distillation residue obtained. The final product thus obtained is a dark yellow transparent liquid, the amount of which is 332.0 g.
For the final product containing the basic alkaline earth metal as the active element, the conversion of each source reagent (conversion of each source reagent to the basic alkaline earth metal phenol), the composition, main characteristics and equivalent ratio of the attached metal (ratio in gram to -equivalent alkaline earth metal oxide or hydroxide i-alkylphenol, indicating the amount of reacted reactants in the formation of the main phenol and alkaline earth metal). The data obtained are given in table. one. ,
The conversion of each of the starting materials and the equivalent ratio of the attached metal are calculated based on the material balance of the starting materials. The viscosity of the final product, the basicity index (in accordance with JISK 2500), the calcium content and the sulfur content are determined on the basis of actual measurements.
In carrying out the experiment described in Example 1, higher alcohol was used as a solvent in the reaction step of adding a metal to an alkylphenol and water was added to the reaction system from the outside. This can be seen from the data presented in Table 1, the conversion of each starting material, in particular calcium oxide, is very high (as a result, the content of insoluble material in the distillate residue is very low) and basic alkaline earth metal phenols can be obtained with a high equivalent metal addition ratios.
Example 1 (comparative). The basic alkaline earth metal phenol is obtained in the same manner as in Example 1, except that water is not added to the reaction system and the amount of mineral oil added to the reaction system after carbon dioxide.
d 5 5
0 5
0 5 0
five
la is reduced to 500 g. 11.3 g of insoluble material is filtered off from the obtained product solution. The yield of the final product is 635.7 g. The conversion of each of the starting materials and the characteristics of the final product are shown in Table 1.
From the table. 1 of the results of example 1 and comparative example 1, it can be seen that upon receipt of the main phenol and alkaline earth metal in the usual way, i.e. without adding water to the reaction system during the addition of the metal to the alkylphenol, the conversion of calcium oxide is much lower than in example 1, which indicates its unproductive use. In addition, the amount of insoluble material in the distillate residue is much more than example 1.
Example 2. For the experiment, the four-necked flask described in Example 1 was used, in which 4.0 moles of nonylphenol, 1.0 moles of calcium oxide and 0.6 moles of sulfur were placed, followed by stirring the reagents to obtain a suspension. Then, for 30 minutes, a mixture consisting of 0.8 mol of ethylene glycol and 0.9 mol of water is introduced into the prepared suspension under stirring in a stream of nitrogen at normal pressure and temperature. The mixture thus obtained is stirred at 130 ° C for 5 hours in order to carry out the metal addition reaction. Then, with a gradual decrease in pressure in the reactor, the reaction system is distilled, resulting in the removal of water and a very small amount of ethylene glycol. thus, a liquid distillate residue is obtained in the reactor. The temperature at the end of the distillation process is 25 ° C (32 mm Hg).
The liquid distillate residue thus obtained is a solution of a basic phenol of an alkaline earth metal, having a viscosity of 200 cSt (with a calcium content of 4.08% by weight, a sulfur content of 1.46% by weight and having an equivalent metal addition ratio of 2.50 .In order to increase the stability of the product obtained, it is subjected to carbon dioxide treatment.
To absorb carbon dioxide, the liquid distillate residue is placed in an autoclave, where it is held for 30 minutes at a higher pressure (no more than 12 kg / cm) and at. After that, the product solution is kept in an autoclave for 2 hours at elevated pressure (no more than 6 kg / cm) and at 175 ° C. To the resulting product solution, 242.3 g of neutral oil 150 is added as a solvent, after which 2.1 g of insoluble material is removed from the solution by filtration. The obtained filtrate is placed in a two-liter, two-neck flask of opal form and is distilled under reduced pressure, as a result of which the majority of the unreacted ethylene glycol and nonylphenol is removed from it and a distillate residue is obtained in an amount of 520.1 g, which represents a final product. For the final product, which is the solution of the main phenol of the slit metal, the conversion of each source material and the main characteristics and composition are determined (the content of carbon dioxide in the product is calculated from the material balance of the source materials).
The data obtained are given in table. 2
Part of the final product, the characteristics of which are given in Table. 2, subjected to chromatographic analysis using silica gel as an absorbent and normal hexane as an eluent to isolate the active component. The resulting active component, in the form of a pale yellow powder, is hydrolyzed using an excess of 1N. sulfuric acid solution (.), resulting in an oil film. Liquid chromatographic analysis of the oil film showed that 15.3 mol% nonylphenol, the active component, is nonylsalicylic acid.
In this example, the solvent (lauryl alcohol) was not used at the stage of the addition of metal to phenol, and phenol was used in large quantities. The conversion of each starting material, in particular calcium oxide, turned out to be quite
high (Table 2), and the resulting basic ferolate of an alkaline earth metal has a high equivalent bearing capacity of the metal.
Example 2 (comparative). The basic alkaline earth metal phenol t is prepared in the same manner as in Example 2, except that water is not added to the mixture of raw materials. The content of the insoluble material in the distillate residue is quite significant and as a result of filtration is 24.6 g. The duration of the filtration operation of the distillate residue for the purpose of separating insoluble material considerably exceeds the duration of the analogous operation described in Example 2. The yield of the final product is em 458.1 g. Conversion of each source material and the characteristics of the final product are given in table. 2
The conversion of calcium oxide (Table 2) is much lower compared to the conversion of calcium oxide in Example 2, since no water is added to the reaction mixture when performing the described metal addition operation.
Example 3 (comparative). The basic alkaline earth metal phenol t is prepared in the same manner as in Example 2, except that water is not added to the mixture of raw materials, and the amount of ethylene glycol used is increased to 1.7 mol. Due to the use of a large amount of ethylene glycol, a distillation operation was necessary in order to remove excess unreacted ethylene glycol from the addition product of the addition product before carbon dioxide treatment of the solution. The duration of the distillation operation in this case is three times longer than the duration of such an operation in Example 2. The temperature of the final distillate is 79 ° C (3.0 mm Hg). The content of insoluble material in the distillate residue is 1.9 g and the yield of the final product is 529.2 g.
Since in comparative example 3, water into the reaction system during the implementation of the metal addition reaction, in contrast to example 2, from the outside
was not added (Table 2), but a large amount of ethylene glycol was used, the conversion of calcium oxide was high, and the amount of insoluble material in the solution of the final product decreased.
However, due to the use of a large amount of ethylene glycol, a longer period of time was required to remove excess unreacted ethylene glycol from the solution of the metal addition reaction product by distilling the solution. Thus, the time and cost of energy, starting with the preparation of a mixture of raw materials and ending with the completion of the operation of treating a solution of the product with carbon dioxide, are 1.35 times the time and energy required to perform the same operations in Example 2.
Example 3. For the experiment, a four-necked flask, identical to that described in Example 1, was used. The flask was placed 4.0 moles of nonylphenol, 1.0 moles of calcium oxide, having a purity of 100.%, and 0.6 moles of sulfur.
Then, a mixture consisting of 0.6 mol of ethylene glycol and 2.5 mol of water is introduced into the prepared suspension for 30 minutes at normal pressure. The mixture thus obtained, in order to carry out the metal addition reaction, is stirred for 5 hours while heating at 130 ° C. Then, with a gradual decrease in pressure in the reactor, the reaction mixture is distilled, resulting in the removal of water from the reactor and a very small amount of ethylene glycol so that a distillate residue is formed in the reactor, the amount of which is 967 4 g. The final temperature of the distillate residue in the reactor is 23 ° C (19 mm Hg). The distillation process is completed within a short time.
To absorb carbon dioxide, the distillate residue (036.1 g) is placed in an autoclave, where it is held under elevated pressure (no more than 3.5 kg / cm) and for 30 minutes. After that, the reaction product solution is incubated for 2 hours at an increased pressure (6.0 kg / cm) and at 178 ° C. The amount of product solution thus obtained is 967.5 Go. Then, to 956.1 g of the reaction product solution, 231.7 g of neutral oil 150 is added as a solvent and the resulting mixture is distilled under reduced pressure to remove unreacted nonylphenol and ethylene glycol. The temperature of the residue at the end of the distillation is 134 ° C (3 mm Hg). By filtration of the distillation residue, 2.4 g of insoluble material is removed from it and 546.6 g of filtrate are obtained, which represents the final product. Characteristics of the final product, i.e. solution of the main phenol and alkaline earth metal, and the conversion of each source material are given in table. 3
Example 4. For the experiment, the four-necked flask described in Example 1 was used, in which 651.8 g of recovered nonylphenol (a mixture containing 2.50 mol of nonylphenol, 0.07 mol of ethylene glycol and 96.4 g of mineral oil) were placed. 1.0 mol of calcium oxide, which had a purity of 98.1 wt.%, 0.8 mol of sulfur and 145.9 g of neutral oil 150. In the suspension thus obtained, for 30 minutes at atmospheric pressure and at 125 ° C is introduced a mixture consisting of 0.73 mol of ethylene glycol and 0.20 mol of water. The resulting mixture in order to carry out the reaction, the metal compounds are stirred for 4 hours with heating at 130 ° C. As a result of subsequent distillation, water and a small amount of ethylene glycol are removed from the reaction product solution. The distillation operation is carried out under reduced pressure. Upon completion of the distillation of the reaction product solution, 894.5 g of a liquid distillation residue is obtained. The temperature of the distillation residue, at the end of the solution distillation operation, is (1.0 mm Hg). The distillation process is carried out in a short period of time.
To absorb carbon dioxide, the distillate residue (881.9 g) is placed in an autoclave, where it is under elevated pressure (not more than 2.4 kg / cm) at 120 ° C for 30 minutes. After that, the reaction product solution is incubated for
2 hours at elevated pressure (6.0 kg (6.0 kg / cm) and at 178 ° C, resulting in 917.4 g of solution being obtained. Then 867.4 g of the reaction product solution is distilled under reduced pressure in order to removing unreacted nonylphenol and ethylene glycol from it. The temperature of the distillate residue at the end of the distillation of the solution is 158 C (1.0 mm Hg). The resulting distillate containing nonylphenol and ethylene glycol is reused in metal addition reactions as recovered nonylphenol. The resulting residue removes 2.5 g of insoluble material from the filter, resulting in filtration of 398.6 g of final product A. The characteristics of the final product, i.e. the solution of the basic alkaline earth metal phenol, and the conversion of each source material are given in table.3.
In carrying out the experiment described in Example 3, a large amount of water with respect to alkaline earth oxide and hydroxide is added to the reactor, and in the experiment described in Example 4, a small amount of water relative to oxide or hydroxide of alkaline earth metal is added. In both cases, the addition of iodine provides a simplified distillation operation, carried out after the addition reaction of the metal, and a very high conversion of the alkaline earth metal-containing reagent.
Example 5. For the experiment, the four-necked flask described in example 1 was used, in which 3. 0 mol of nonylphenol, 0.914 mol of calcium hydroxide, having a purity of 91.4 wt.%, 0.6 mol of sulfur, and as a solvent, 242.3 g of neutral oil is 150. To the suspension prepared in such a way, under a mixture of 0.8 mol of ethylene glycol and 0.9 mol of water, under a condition of atmospheric pressure and at 125 ° C, for 30 minutes. The resulting mixture in order to carry out the metal addition reaction is stirred for 4 hours with heating at 115 ° C.
As a result of subsequent distillation under reduced pressure from oa
0
five
five
0
five
0
five
Water and a very small amount of ethylene glycol are removed from the reaction product and a liquid distillation residue is obtained. The finite temperature of the distillate is 87 ° C (12 mm Hg). The distillation process is carried out for a short period of time. To absorb carbon dioxide, the liquid distillation residue is placed in an autoclave, where it is held for 30 minutes under conditions of increased pressure (not more than 12 kg / cm) at 120 ° C. Then, in order to produce the thief of the reaction product, the liquid distillate residue is kept in the reactor at an elevated pressure (6 kg / cm) and for 2 hours. The solution of the reaction product thus obtained is distilled off at a reduced pressure in order to remove unreacted nonylphenol and etxtenglycolide, resulting in a distillation residue of 493.1 g. The temperature of the final distillate is 118 ° C (0.5 mm Hg). By filtration of this distillation residue, 14.9 g of insoluble material is removed from it.
0 and get the final product. The characteristics of the final product, i.e. The main phenol is an alkaline earth metal in solution, and the conversion of each source material is given in Table. four.
In this experiment, calcium hydroxide was used as the alkaline earth metal hydroxide. The distillation operation after completion of the metal addition reaction was carried out without any difficulties and a relatively high degree of conversion of calcium hydroxide was achieved.
Example 4 (comparative). For a comparative experiment, a four-necked one was used, the flask described in Example 1, into which 4.0 moles of nonylphenol, 1.0 moles of calcium hydroxide, having a purity of 95.0 wt.% And 0.6 moles of sulfur, are placed. 0.6 mol of ethylene glycol (water is not added) is added to the suspension thus prepared at atmospheric pressure and at 125 ° C for 30 minutes. In order to carry out the metal addition reaction, the resulting mixture is stirred for 5 hours by heating at the thus obtained solution of the reaction product is distilled under reduced pressure in order to remove water and a very small amount of ethylene glycol, resulting in a liquid and distillation residue in 981.2 g. The temperature of the final distillate is (21 mm Hg). The distillation process is completed within a short period of time.
For carbon dioxide absorption, the liquid distillation residue is in
in the same way as described in example 2, except that in this experiment the amounts of nonylphenol and added water are changed from 4.0 to 0.8, mol and from 0.9 to 1.1 mol, respectively, and the addition in the reaction system, 242.3 g of neutral oil 150 is produced after the treatment of the intermediate with carbon dioxide, and at the beginning of the metal addition reaction. The amount separated from the solution of the reaction product by centrifuging
In the amount of 961.1 g is placed in an autoclave, g van n-hexane, representing so20
where it is held for 30 minutes under pressure (not more than 3.65 kg / cm) at 120 ° C. Then, to obtain 987.1 g of the reaction product solution, the liquid distillation residue is held in the reactor at elevated pressure (6.0 kg / cm) and at 178 s for 2 hours. Thereafter, 974.7 g of the reaction product solution is diluted with 234, 4 g of neutral oil is 150. The mixture thus obtained is distilled under reduced pressure in order to remove unreacted nonylphenol and ethylene glycol from it, resulting in a distillation residue in an amount of 411.5 g. The temperature of the final distillate is 145.5 C (4 mm Hg). By filtration of this distillation residue, 32.5 g of insoluble material is removed from it and the final pro- is obtained. duct The characteristics of the final product, which is a solution of the basic phenol of the alkaline earth metal, and the conversion of each of the starting materials are given in Table. four.
thirty
Beat Insoluble material, is 14.8 g, and the yield of the final product is 428.6 g. Conversion of each of the raw materials and the characteristics of the final product are given in table. five.
Example 7. The basic alkaline earth metal phenol is obtained in the same manner as in Example 2, except that in this experiment the amount of sulfur is changed from 0.6 to 3.0 mol, and the temperature and duration of the metal addition reaction are changed from 130 to 123 C and from 5 to 4 h, respectively. In this experiment, the amount of insoluble matter is 1.2 g, and the yield of the final product is 780.4 g. The conversion of each of the starting materials and the characteristics of the final product are listed in Table 5.
Example -8. A mixture of 2383.5 g of recovered nonylphenol (a mixture containing 9.0 mol of nonylphenol, 0.69 mol of ethylene glycol and 357.9 g of mineral oil), 3.0 mol of fresh nonylphenol, 3.0 mol of calcium oxide, purity 95, 7 May.% And 2.1 mol of sulfur are placed in a four-necked flask equipped with a stirrer, a tubular condenser, a nozzle for the introduction of nitrogen gas and a thermometer, where a suspension is prepared from this mixture. To this suspension, a mixture consisting of 0.96 mol of ethylene glycol and 3.0 mol of water is added at 30 ° C under elevated pressure (2 kg / cm) and at 145 ° C. Received
40
When carrying out this experiment, as in the experiment described in example 5, the quality of alkaline earth metal hydroxide was calcium hydroxide, however, unlike example 5, water was not added to the reaction system during the metal addition reaction and therefore compared to example 5 in this case, the conversion of calcium hydroxide was very low. The content of insoluble material was very high.
Example 6. The main phenol t alkaline earth metal polupigot
five
0
Beat Insoluble material, is 14.8 g, and the yield of the final product is 428.6 g. Conversion of each of the raw materials and the characteristics of the final product are given in table. five.
Example 7. The basic alkaline earth metal phenol is obtained in the same manner as in Example 2, except that in this experiment the amount of sulfur is changed from 0.6 to 3.0 mol, and the temperature and duration of the metal addition reaction are changed from 130 to 123 C and from 5 to 4 h, respectively. In this experiment, the amount of insoluble matter is 1.2 g, and the yield of the final product is 780.4 g. The conversion of each of the starting materials and the characteristics of the final product are listed in Table 5.
Example -8. A mixture of 2383.5 g of recovered nonylphenol (a mixture containing 9.0 mol of nonylphenol, 0.69 mol of ethylene glycol and 357.9 g of mineral oil), 3.0 mol of fresh nonylphenol, 3.0 mol of calcium oxide, purity 95, 7 May.% And 2.1 mol of sulfur are placed in a four-necked flask equipped with a stirrer, a tubular condenser, a nozzle for the introduction of nitrogen gas and a thermometer, where a suspension is prepared from this mixture. To this suspension, a mixture consisting of 0.96 mol of ethylene glycol and 3.0 mol of water is added at 30 ° C under elevated pressure (2 kg / cm) and at 145 ° C. Received
the mixture is thus stirred for 4 hours at a pressure of 2 kg / cm and at 160 ° C in order to carry out the metal addition reaction. Obtained from the metal addition reaction
five
five
ten
25
The reaction product is subjected to distillation under reduced pressure in the removal of water and a very small amount of ethylene glycol, with the result that a liquid distillation residue is obtained in an amount of 3,268.6 g. The final distillate temperature is 41.5 ° C (7, 5 mm Hg). The distillation process is completed in a short period of time.
For the adsorption of carbon dioxide, the distillation residue is placed in an autoclave, where it is held for 30 minutes under a high pressure (not more than 2.4 kg / cm) and, further, the liquid distillation residue is kept in the reaction . torus at elevated pressure (6 kg / cm) and at a temperature of 178 ° C for 20–2 h, resulting in a solution of 3350.6 g of the reaction product to be obtained. Thereafter, 3202.5 g of the reaction product solution is diluted with neutral oil 150j 695.5 g. The mixture thus obtained is distilled under reduced pressure in order to remove unreacted nonylphenol and ethylene glycol from it, resulting in a distillation residue in an amount of 1555.0 g. The temperature of the final distillate is em 157 C (1 mm Hg). The distillate obtained by this distillation and containing nonylphenol and ethylene glycol is reused as the recovered nonylphenol in the described metal addition reaction. By filtering the distillation residue, insoluble material in the amount of 5.5 g is removed from it and the final product is obtained in the amount of 1549.5 g. The characteristics of the final product, which is a solution of the basic alkaline earth metal phenol, and the conversion of each of them Nyh raw materials are given in table. five.
Example 6 describes an experiment in which a large amount of alkaline earth metal was used with respect to alkylphenol. Example 7 describes an experiment in which a large amount of sulfur was used with respect to alkaline earth metal hydroxide, and example 8 described an experiment in which the reaction with 15
thirty
35
40
45
50
0
five
0
The metal compound is carried out at an elevated temperature. In each of the above experiments, distillation was carried out upon completion. Reactivity of the metal, takes a short period of time, and this means that a corresponding reduction in the production cycle time and energy costs for the production of the main phenol and alkaline earth metal,
In tab. Figure 6 shows the process indicators of Examples 1-8 and Comparative 5 Examples Examples 1-4, as well as data on the amount of water in ethylene glycol distilled off at the distillation stage after completion of the reaction mixture coupling to the alkaline earth metal to alkylphenol; the degree of water distilled off with respect to the amount of water and water formed in the reaction mixture added to the reaction mixture; degrees of ethylene glycol distant relative to added ethylene glycol; the time required for the distillation of water; the time required to complete the distillation; and the temperature and pressure during the final distillation.
Examples 9-20 and example 5 (comparative).
Products containing basic additives such as alkaline earth metal phenols are prepared in the same way as in Example 3. Starting materials: alkylphenol, alkaline earth metal oxide or hydroxide, dihydric alcohol, sulfur and water are placed in a reactor to carry out a reaction with metal. The reaction product is distilled (first distillation step), and the resulting distillation residue is subjected to a carbonization process. The reaction product is mixed with mineral oil and the resulting mixture is distilled (second distillation step). The distillation residue is filtered to remove the insoluble portion to obtain the desired product.
In the process described, alkylphenols (AP) are used as the starting phenolic materials, and dodecylphenol (DP) is used in Example 9, in Example 10 an alkylphenol isomeric mixture is used (containing
0
five
0
five
0
 5U
42%, ortoforms, 42% of the steam form and 16% of the metaform; average molecular weight: 314 (MAP), which is formed by alkylation of phenol with an alpha olefin mixture containing from 6 to 32 carbon atoms, and nonylphenol (NP) is used in other examples. As substances containing alkaline earth metals, oxides (MO) of alkaline earth metal (M) j are used, with barium oxide being used in Example 20, and calcium oxide being used in other examples.
Propylene glycol (PG) is used as the dihydric alcohol in Example 14, and ethylene glycol (PG) is used in other examples. In Example 12, an alcohol containing 24 carbon atoms is used as a reaction diluent, but in other examples an alcohol diluent is not used. As a mineral oil, added after the end of the processing stage, two


thirty
35
carbon monoxide, in example 10 used alcohol.
The neutral oil is 500. Further, the process conditions in examples 21-23 and comparative examples 6 and 7 are given in table. ten; The amounts of raw materials used, the amount of intermediate products and the amount of the target products are given in Table. 11, and the properties of the target products and the conversion of the starting materials to the target product are given in table. 12,
Examples 21 and 22 illustrate the use of small amounts of sulfur and water to an alkaline earth metal. In Example 23, large amounts of dihydric alcohol to an alkaline earth metal are used. As a result of Examples 21-23, it can be seen that the added amount of water should be at least 0.05 mol per 1 mol of alkaline earth metal, and the added amount of sulfur should be at least 0.1 mol per 1 mol of alkaline earth metal, but a good quality designated 500 H (viscosity at 100 ° C: 11.3 cps); in other examples, neutral oil 150 is used, hereinafter referred to as 150N.
Comparative Example 5 is for comparison with Example 1.
The conditions of the process in examples 9-20, as well as in comparative example 5 are given in table. 7, the amounts of the starting materials used, the amounts of the intermediate products and the quantity of the final products are given in table. 8, and the properties, composition and conversion of the initial Q products to the target products are given in table. 9.
In the examples in which the amount of undissolved material was small, for example in Example 9 (since the products have the same properties as the products from which insoluble materials were removed), the products are obtained without removing the insoluble material.
Products containing additives from basic alkaline earth metal phenols are prepared in the same manner as in Example 3. Raw materials containing alkylphenols, alkaline earth metal oxides and hydroxides, sulfur, dihydric alcohol, and water are placed in a reactor 3, to react with metals Pro45
50
55
in the product, it can be obtained at a higher conversion rate, and the added amount of the dihydric alcohol should be as high as 2.5 mol per 1 mol of alkaline earth metal, but a good amount of the product can be obtained with a higher conversion rate.
In examples 21 and 22 and examples 6 and 7 (comparative), the relative amount (degree) of otistilliro
32
sixteen
The product reaction is distilled (first distillation step), and the resulting residue is subjected to a carbonation process. The reaction product is further subjected to additional distillation (the second stage of distillation). The residue after distillation is filtered to remove the insoluble portion to obtain the desired product.
In Examples 1 and 2 and Examples 6 and 7 (comparative), neutral oil 150 is used as a diluent (solvent) when the metal is added, and in example 23 neutral oil 150 is used as a diluent after the carbonization process.
In the described process, (NP) is used as an AP, CaO is used as the MO of an MO of a substance M containing an alkaline earth metal, and EG is used as a diatomic 30

35

Q
45
in the product, it can be obtained at a higher conversion rate, and the added amount of the dihydric alcohol should be as high as 2.5 mol per 1 mol of alkaline earth metal, but a good amount of the product can be obtained with a higher conversion rate.
In examples 21 and 22 and examples 6 and 7 (comparative), the relative amount (degree) of distilled water (relative to the total amount of added and formed water) in the first stage of distillation after the stage of interaction with the metal is excellent: 100, 60, 30 and 18%,. but the other process conditions are identical in all cases. For examples 21 and 22 and comparative examples 6 and 7, the degree of distilled water, the conversion of the calcium product and the properties of the product (solubility and stability to moisture absorption of the product) at the first distillation stage are given in Table. 13. As can be seen from the table. 13, in the first distillation stage, the degree of distilled water is 60% or higher, the conversion of the calcium product is high, and the solubility of the product and its stability to moisture absorption are good. Moreover, when the degree of distilled water reaches 30%, the solubility of the product becomes slightly lower, and when the degree of distilled water reaches 18%, the conversion of the calcium product deteriorates significantly, which slows down the production reaction (the content of insoluble increases greatly).
For examples 1-23 in table. The 14 values of the degrees of distilled water are given for the first distillation stage after the metal reaction stage.
For lubricating oils to which the resulting product is added (examples 1 and 2, 4 and 5, 7 and 8, 11-21), engine tests have been carried out. The following conditions were used to test engine performance and the following results were obtained.
Test engine: Kubota's 4-cylinder water-cooled diesel engine:
Inner diameter
X stroke, mm85x111
Total working volume
cm 567
Compression ratio 20
Durable rated power, PS Combustion Maximum pressure, kg / cm Test conditions: Shaft, rpm
1. A method for producing basic sulfur-6 alkaline earth-containing phenols of metal Pre-metals, which includes a preparative 55 reaction mixture of alkylphenol containing 6-32 carbon atoms in 65 side chain, oxide or hydroxide, alkaline-earth metal, taken in 80P amount of 0.1-10 mol per 1 mol al
Output power, PS Not less than 6 Cooling water temperature, ° С85t2 Fuel consumption, g / h 1295 ± 15 Operating time, h 120 Fuel for testing: Industrial standard of Japan to 2204 (gAsoil) No. 1, vol. % 97 Bright stock 150, vol.% 3 Sulfur content, wt.% 1.0 + 0.05 Oil for testing. For the tests, the SAE 30 paraffin base oil was used as the main 5
Test Oil
Amount of additive
0 phenol and regulated that. So that the main number. was 11.0
Composition
Additive type phenol ta
Antioxidant, detergent,% 0.37 The test results of the main sulfur-containing phenols as additives to oils are given in Table. 15.
The industrial-supplied phenols A and B have the following properties, represented in -Tab. sixteen.
The results of testing the performance of the Kubota engine of the ME by the company show that the products obtained by the proposed method have properties equivalent to or more corresponding to the additives supplied by the industry.
The proposed method allows increasing the conversion of an alkaline earth metal oxide or hydroxide while simplifying the distillation step of a dihydric alcohol, reducing time and energy costs for distilling the target product, and simplifying removal of insoluble materials from the product.

权利要求:
Claims (8)
[1]
Invention Formula
kilphenol, sulfur, taken in an amount of 1.0-3.0 mol per 1 mol of alkaline earth metal oxide or hydroxide A, and a dihydric alcohol, its interaction ensuring the addition of alkaline earth metal to alkylphenol, at a temperature of 60-200 ° С and pressure 1-8 kg / cm, distilling off water, treating the residue obtained with carbon dioxide at a temperature of 80-205 ° C and a pressure of 1-CQg / cm, distilling off unreacted alkylphenol, characterized by.
which, in order to simplify the process, is water interaction.
hydroxide or alkaline earth metal oxide selected from calcium or barium is used; a C -C} -hydric alcohol in an amount of 0.15-2.5 mol per t mole of alkaline earth metal hydroxide or alkali metal is taken as the dihydric alcohol, and the reaction is carried out in the presence of water, 0.05–10 mol per 1 mol of alkaline earth metal oxide or hydroxide.
[2]
2. Method POP.1, characterized in that water is added 0.1-2.0 mol per 1 mol of alkaline earth metal oxide or hydroxide,
[3]
3. Method POP1, characterized in that the reaction is carried out in the presence of a diluent.
[4]
4. The method according to claim 3, differing from that with the fact that lubricant fractions or higher C-C j-alcohol are used as the diluent.
[5]
5. Method POP1, characterized in that insoluble materials are removed from the reaction product after it is treated with carbon dioxide.
[6]
6. Method POP.1, distinguished by the fact that the oxide or hydroxide of alkaline earth metal is
use in the amount of 0.1-6 mol per 1 mol of alkylphenol,
[7]
7. The method according to claim 1, about tl and h and y - y and with the fact that ethylene glycol or propylene glycol in the amount of 0.3-1.5 mol per 1 mole of alkaline earth metal oxide or hydroxide is taken as the dihydric alcohol.
[8]
8. The method according to claim 1, characterized by the fact that, after completion of the reaction, distillation removes 60% and more added and formed during
Table 1
Conversion of source material,%: CaO
Paraoctylphenol S
Ethylene glycol CO
The characteristics of the final product:
Viscosity at 100 ° C, cSt
The basicity index, KOH mg / g
Content Sa, May. %
S content, wt. %
Equivalent metal addition ratio
19.73 53.71
132
152
4.70 3.52
5.45 4.35
2.79 2.03
23
OptionsExample
„„ I G
S content, May.% 3,61
The content of reacted CO2, wt.%
Equivalent metal addition ratio
Conversion of source material,%:
Ca (OH)
Nonylphenol
S
Ethylene glycol
SOG
The characteristics of the final product:
Viscosity at 100 ° C
cSt
The basicity index, KOH mg / g
Ca content, wt.% S content, wt.%
The content of reacted CO2, wt.%
Equivalent metal addition ratio
1A5073224
Continuation of table 3
3.046.12
2,052.53
Table 4
62,89
178 6.36 3.10
2.64 2.00
Coatus of similar p «a- gmtov en, mol / mole
. AR / I
Two-current emtpT / H 0.8
S / M.
Ispolyeuem crawling klter- apy: MO
AR
 Dual Atom Stft
rmboan tel
Eagruis "with the scorched materials
fCxXP / CM X
X h: AR
YU
S
Diatomic
alcohol
Stage interaction with me0,6 0.9
Cao DP
EU
3.5
0.8 0.6 0.9
Cao Car
EU
10.0
1.5 0.6 0.9
Cao
Yar
EU
o, t
1.0
0.35
0.9
.0
0.25 0.6 10.0
CaO, CaO BP YR
EU S, -s1
EU
J.3
0,8, 0.
Cao P
pc
J.5
0.8 0.6 0.9
KR
in
Hon atna temperature
KotaaTxa tcmparatura
 125x1x0.5 130x1x0.5 130x1x0.5 135x1x1.0 125x1x0.5 130x1x0.560x6.0x0.5
 hg / sn x, 130x1x5.0135x1x5.0 135x1x5.0 135x1x5.0 130x1x5.0 135x1.5.0 80x6.0x6.0
Stage 1 distillation:
Ending
DISTILLATION 3 .6
3.9
5.03,7
8.9
2.0
n less
120xO, 5 g 120x0.5 h
Kovech
pressure..
when serving; COj, hg / ck A 3.3
Stabilization, ° С X
hkg / sn AxX h150x0.6x2,0155x7.0x2. 155x0.8x2.0 145x7.0x2.0 175x6.0x2.0 155x9.0x2.0 155x1.0x2.0
Stage 2 dns:
The temperature of the end
t hashtah, Shmmmmtst 183x1213x1,5 165x2215x1.0 166x2,5185x2,5175x2.
Tab color 7
o, t
1.0
0.35
0.9
.0
0.25 0.6 10.0
J.3
0,8, 0.
J.5
0.8 0.6 0.9
CaO, CaO BP YR
EU S, -s1
EU
Cao P
pc
KR
in
KotaaTxa tcmparatura
3.9
5.03,7
8.9
2.0
to
38x35 0.6 0.6
50hza
0.8 0.8
95x13 3x50
0,80,7
0,60,7
43x35 0.8 0.8
81xS, 0
M. 2.0
SSr e t65x8, OxO, 5 ЗОж1хО 5, 5 t25xtJtO, 5 115x1x0.5 130x1x0.5
Stage vzaiyuyu-
action with
 hch 200x8.0x3.0 115 "1x5.0 135x1x5.0 130x1x5.0 130x1x5.0 135x1x5.0
STAGE -. /,
d st ll chi:.
Oka cha av
dvstzhshig-, .., ..
vdu, with 4
Zhzhft.st.
DISTCLE time
Hjo h
06giee. and dist l l CC, h
Stage of the ball. "CO flow}, -.:.
° С9 П / ЯВХ
hch120x75x0,5 185x75x0,5, 5 120x75x0.5 120x0.75x0.5125x50x0.5
Kovvchn about
pressure
when serving.
CO „kg / C1“ A2,82,13,13,22,9,7
Stabipisec, C X, .-.
X kg / s AhJ
hch178x0.6x2.0205x8.0x5.0 30x6.0x5.0 178x30x1.5 155x6.0x2,0155x0.8x2.0
Herds 2nd.
distillation:
Temperature-
co-op -.
all the way will give the game,. ..
Schmnrtst160x1182x5. 173x4 173x1172x1 .167x2
CO 1 pre-arntelko “agruzhavt before the reaction; The process is terminated by a continuous flow of CO2 reactor.
Continued table. 7
 . "-.
.P.
3x50
0.7
0.7
43x35 0.8 0.8
81xS, 0,
M. 2.0
AR
MO
D17SHTOK1SHY
SUFT
Raebipggal
About "av kvhh- iat & -
CTJUQU (“Schmodsyst” with nonall 1HI complex, g
Number of BjOs
. Kolshestm otdnshishrovshogo. dkhtatomvogo stripping
. Amount of two G1S5 OTHNSTILLED materials
Remainder disputes
Stadm karOovshaPk, G1
Stake of ka-
.
Product
Filing M1 “bounce, rt
Katchestvo nasda
Polchach a mixture
Stage - 2-A d stklDP "ARV NAGS
918.10, QtlOt. S22.0v 1.2771.1
98,5198,5198,5t98,5 lOOI98,5Z
CaOC “OCaOCaOCaO. C "0
57,057,028,557,056,157,0
ecECECEGEC C
49,749,74в, 662, t9,360,9
19,319,39, -I1, J19,319,3
16,216,2B, l16,2180,016,2
905,8HPHPYAR
771,1881,2771,1
tOOZlOOZ1001
CaOC 0CaO
56,156,15 ", 1
EGEC EC
9.734, 7
19,322,519, J
16, 016.2
irPHPHPYAR
771.1 771.1 771.1 1101, i
CaO 56.1
CaO BaO CaO 56.1 153.3 28.5
ECECEGEG
49, 549,746,6
19,322,519.39,6
16,214,416,20
t060.6 1141.2 1194.3 1074.3 1145.9 924.5 912.4 1012.0 912.4 912.4 907.6 1009.6 1166.2
34.3- 34.0 17.1 28.7 95.0 31.6 33.8 35.8 34.2 34.3 32.3 34.0 6.5
0 0 0 0 0.9 0
5. 5.3 4.5 7.1 7.3 6.2 1021.2 1201.9 1172.7 1038.5 942.7 886.5
42.9 45.6 20.9 53.3 29.7 20.5 1064.1 1247.5 1193.8 1091.8 872.4 907.1
t50H) (JOOH) (150I) (150H) (150I) (I50N) 221.5 241.7 121.3 171.0 242.3 242.3
02,32,5
5,07,85,2
673.6 966.1 670, S
43.3 29.0 35.9 916.9 595.1 906.4
(150I) (15011) (150I) 245.8 242.3. 243.7
3,73,15,123,3
4,95,05.1,3
869.5 867.2 965.4, 1152.1
40.5 41.3 32.3 17.8 910.0 908.5 997.7 1165.9
(1501) (I50H) (150I) (150I) 245.8 242.3 242.3 121.3
1285.6 1489.2 1374.9 1262.8 1214.7 1249.4 1162.7 1237.4 1150.1 1155.8 1150.8 1240.0 1291.2


717.1 712.9 1079.1 922.0 699.7 617.7 568.5: 776.3 235.8 340.8 515.0 531.7
2,01,81,0. 30.0 13.5 9.5
566.5 7M, 5,234.8 310.8 50.5 522.2
t in l to
HPNR
881,2771,1
lOOZ1001
C 0CaO
56.15 ", 1
EC EC
34, 7
22,519, J
18,016,2
irPHPHPYAR
771.1 771.1 771.1 1101, i
CaO 56.1
CaO BaO CaO 56.1 153.3 28.5
ECECEGEG
49, 549,746,6
19,322,519.39,6
16,214,416,20
2,32,5
7.85.2
966.1 670, S
3,73,15,123,3
4,95,05.1,3
869.5 867.2 965.4, 1152.1
43.3 29.0 35.9 916.9 595.1 906.4
40.5 41.3 32.3 17.8 910.0 908.5 997.7 1165.9
(150I) (15011) (150I) 245.8 242.3. 243.7
(1501) (I50H) (150I) (150I) 245.8 242.3 242.3 121.3
615.4 "98.5 643.6 547.3 538.9 506.5
579.0 649.4 638.2 1074.0 576.8 501.4 601.9 217.2
2,01,50,8
545.3 537.4 505.7
2,61,29,630,
574.2 500.2 592.3 187.1
35
The ratio of the starting materials in the mixture, col / mol:
AR / M
Diatomic alcohol / M
S / M,
N (0 / N
Used raw materials:
MO AR Dioatomic alcohol
Download raw materials, ° C x kg / cm G X h:
AR MO S
Duplicate alcohol
Stage of interaction with metal, С x kg / m А х ч
Stage 1 distillation:
Distillation termination. qing, Schmmrt.st.
Distillation time, min
Total distillation time, min
Stage Carrrh of the Back: COi Feed, C x h
Final pressure at the supply of CO, kg / cm A
Stabilization, С X kg / cm А X h
Stage 2 distillation:
The temperature of course is distillate, ° Cmmmm Hg.
Room temperature
25 ScheO, 5 125x0.5 125x0.5125x0.5 125x0.5
130x1x3.0 130x1x3.0 130x1x3,0130x1x3.0 130x1x3.0
72x10 99x40 99x80100x80 36x24
32 30 2015 28
32 30 2015 58
120x0.5 120x0.5 120x0.5120x0.5 120x0.5
. 2.4 178x6.0x2.0
2.1
2, and
1.3
2.9
178x6: 0x2.0 178x6.0x2.0 178x6.0x2.0 178x6, O
x2.0
158x1
163x1
162x1
178x2
1450732
36 Table
ten
Room temperature
2.1
2, and
1.3
2.9
178x6: 0x2.0 178x6.0x2.0 178x6.0x2.0 178x6, Ox
x2.0
163x1
162x1
178x2
MO 98.1Z CaO (57.2 98.1X CeO (S7.2) 98.1Z CaO (S7.2) 98.1Z CaO (57.2) 98.1Z CaO (57.2)
Diatom-
. NEW alcohol EC (49,7) EG (49,7) EG (49,) EG (49,7) EG (155.3)
S3,23,2 3,23,2t9,3
, 90.9 0.90.90, e ...
Raebavi. .
 tedi mi eral ora Mineralnoe mineral oil
oil (242.3) (242.3) (242.3) (242.3) Total co-. . . .
the number. , .
cutter-.
Lov 904.1 904.1 904.1 904.1 893.6. Stage veai
iodine action
with metal and stage 1
DISTILLATIONS ..
Amount .
at the end
tishshro-.
.. “NOY-d. ,, 35,73,4.18,9
Degree - - ...
otdistil-. -
lnrova-,.,.
1, 00603018100
Number from-. distribution company
dvuatok-.
leg ". Ooo.31.1.
cruft
Amount ...
at the end of ...
tshyshro-- ..
bathroom ma ... 525,03,0I.O
materials, g3,3e, / j.
The remainder.
, 9887,6893.4. 897,7832,6
Stage carvon-.
gati, g:
The number of aras.
rrS; 38,138.8 36,952.7355
PRODUCT- 918.0 926.4 930.3 "0.4 868.1 Filing
la g:
Property of iodava ...
to be .Oo
butter
417, 8

431.0
Viscosity at, spp
The amount of basicity, mg KOH / g
Sa, May. % S, wt.% WITH, may. % Free AR, May. % The composition of the product; AR / Sa, mol / mol EG / Ca, mol / mol CO-j / Ca, mol / mol S / Ca, mol / mol
Equivalent quantities
added metal
The degree of transformation of the original product,%:
408.6
383.9
523.0
T65,1
6,503 108,5
3.84
0.52
2.13
41
 The degree of distilled water is the percentage of the theoretical amount of water (formed water + added water) i
The transformation of the calcium product is the solubility after stirring for 5 minutes at 60 ° C, and the numbers 5 and 3 are the SAE 50 and SAE 30, respectively;
 The moisture absorption stability of the product is the time it takes to form films on the entire surface of the solution at 28 ° C, 98% relative humidity.
Table 14
30.8 35.5 62.7 21.6 47.6
 35.5 33.3
107.5 34.3 34.0 17.1 28.7
195.0
1450732
42 Table 13
43
four
five
7
eight
eleven
12
13
14
15
1b
17
18
nineteen
20
108
100
98
90
112
109
86
103
110
87
103
89
89
VNIIPI Order 6981/58
Random polygons pr-tie, Uzhgorod, st. Project, 4
. e
1450732
44 Continuation of table 14
The product is obtained under the same conditions as in Example 1, other additives are obtained under the same conditions as the conditions given in the respective examples.
Table 16
Circulation 370
Subscription

类似技术:

---

公开号 | 公开日 | 专利标题

---

SU1450732A3|1989-01-07|Method of producing basic sulfur-containing phenolates of alkaline-earth metals

---

US3801507A|1974-04-02|Sulfurized metal phenates

---

US5808145A|1998-09-15|Detergent-dispersant additives for lubricating oils of the sulfurized and superalkalized alkaline earth alkylsalicylate-alkylphenate type

---

CN1093374A|1994-10-12|The succimide of no resin

---

JP2004346327A|2004-12-09|Unsulfurized, carboxylate-containing additive for lubricating oil

---

CN1021740C|1993-08-04|Improved phenate product and process for preparing same

---

US4251379A|1981-02-17|Detergent-dispersants of high alkalinity for lubricating oils and process for their preparation

---

US5178781A|1993-01-12|Process for producing over-based sulfurized alkaline earth metal phenate type detergent

---

US4293431A|1981-10-06|Process of preparing metallic detergent-dispersant additives of high alkalinity in particular for lubricating oils, and product obtained thereby

---

US6001785A|1999-12-14|Detergent-dispersant additives for lubricating oils of the sulphurised and superalkalised, alkaline earth alkylsalicylate-alkaylphenate type

---

US4902436A|1990-02-20|Process for producing a mixture of sulfides of alkaline earth metal salts of alkylhydroxybenzoic acid and alkylphenol

---

US3135729A|1964-06-02|Process for preparing salts of hydrocarbon-phosphorus sulfide reaction products

---

US3194761A|1965-07-13|Preparation of overbased sulphurized calcium alkylphenate lubricant additives

---

EP0558021B1|1996-05-08|Process for producing over-based alkaline earth metal phenate

---

US5538650A|1996-07-23|Process for producing mixture of sulfurized alkaline earth metal salts of salicylic acid compound and phenol

---

US3014868A|1961-12-26|Lubricating oil compositions containing complex metal salts of alkylphenolaldehyde condensation products

---

RU2215022C1|2003-10-27|Lubrication oil additive preparation method

---

JP2737096B2|1998-04-08|Method for producing overbased sulfurized alkaline earth metal phenates

---

US2169545A|1939-08-15|Lubricating oil

---

JP2819491B2|1998-10-30|Preparation of alkaline earth metal sulfide mixtures of salicylic acids and phenols

---

RU2611431C2|2017-02-22|Method of producing low-ash alkylsalicylate detergent-dispersing oil additive

---

JP2696784B2|1998-01-14|Process for producing overbased sulfurized alkaline earth metal phenates

---

US3152069A|1964-10-06|Refining hydrocarbon fractions

---

Gulaliyev et al.2020|Synthetic sulfonate additives for motor oils

---

RU2086608C1|1997-08-10|Method of preparing multifunctional additive to lubricating materials

同族专利:

---

公开号 | 公开日

---

JPH0310611B2|1991-02-14|

---

GB2126602B|1986-03-19|

---

US4518807A|1985-05-21|

---

JPS5931724A|1984-02-20|

---

GB8321709D0|1983-09-14|

---

GB2126602A|1984-03-28|

引用文献:

---

公开号 | 申请日 | 公开日 | 申请人 | 专利标题

---

---

GB684155A|1948-07-03|1952-12-10|California Research Corp|Manufacture of metal salts of organic acids|

---

GB785468A|1954-01-04|1957-10-30|Lubrizol Corp|Preparation of fluid polyvalent metal phenates|

---

US2870134A|1956-12-12|1959-01-20|Texas Co|Preparation of calcium phenolates and sulfurized derivatives thereof|

---

US3333020A|1963-03-14|1967-07-25|American Cyanamid Co|Metal salts of phenols as inhibitors for unsaturated polyester resin|

---

GB1105217A|1965-10-05|1968-03-06|Lubrizol Corp|Process for preparing basic metal phenates|

---

US3755170A|1971-05-17|1973-08-28|Continental Oil Co|Preparation of highly basic alkylphenates and sulfurized alkyphenates|

---

FR2429831B2|1978-06-26|1982-06-11|Orogil|US4664824A|1986-01-14|1987-05-12|Amoco Corporation|Phenate product and process|

---

US4744921A|1986-10-21|1988-05-17|Chevron Research Company|Methods for preparing, group II metal overbased sulfurized alkylphenols|

---

US4971710A|1986-10-21|1990-11-20|Chevron Research Company|Methods for preparing, Group II metal overbased sulfurized alkylphenols|

---

US5024773A|1986-10-21|1991-06-18|Chevron Research Company|Methods for preparing, group II metal overbased sulfurized alkylphenols|

---

JPH0676589B2|1987-07-24|1994-09-28|コスモ石油株式会社|Process for the preparation of alkaline earth metal sulphurised mixtures of hydroxyalkylbenzoic acids and alkylphenols|

---

GB8730220D0|1987-12-29|1988-02-03|Exxon Chemical Patents Inc|Detergents|

---

US4885406A|1988-07-05|1989-12-05|Texas Alkyls, Inc.|Hydrocarbon-soluble complexes of magnesium alkoxides with magnesium aryl oxides|

---

JPH0739586B2|1989-06-23|1995-05-01|コスモ石油株式会社|Preparation of overbased alkaline earth metal phenate type detergent|

---

JPH04183792A|1990-11-19|1992-06-30|Idemitsu Kosan Co Ltd|Perbasic sulfurized alkaline earth metal phenate and use thereof|

---

US5292968A|1992-02-26|1994-03-08|Cosmo Research Institute|Process for producing over-based alkaline earth metal phenate|

---

JPH05238976A|1992-02-26|1993-09-17|Cosmo Sogo Kenkyusho:Kk|Production of over-basic alkaline earth metal phenate or over-basic alkaline earth metal sulfide phenate|

---

JPH0665192A|1992-08-15|1994-03-08|Cosmo Sogo Kenkyusho:Kk|Production of perbasic alkaline earth metal sulfide phenate|

---

TW277057B|1993-08-25|1996-06-01|Cosmo Sogo Kenkyusho Kk|

---

EP2682451B1|2012-07-06|2015-11-18|Infineum International Limited|Detergent modification|

法律状态:

优先权:

---

申请号 | 申请日 | 专利标题

---

JP57142393A|JPH0310611B2|1982-08-16|1982-08-16|

---