• 专利附录
  • 专利说明
  • 权利要求
  • 类似技术
  • 同族专利
  • 引用文献
  • 法律状态
  • 优先权
    • 专利摘要:
    A process for producing over-based sulfurized alkaline earth metal phenates useful as lubricating oil or fuel oil additives comprising reacting a phenol, sulfur, a dihydric alcohol and an alkaline earth metal oxide or hydroxide with about 0.99 to about 0.001 gram equivalents per phenolic hydroxyl group, and reacting the reaction product with carbon dioxide at a temperature of about 50 DEG to about 230 DEG C.
    公开号:SU888816A3
    申请号:SU772562901
    申请日:1977-12-28
    公开日:1981-12-07
    发明作者:Хори Такаси；Хаясида Суетоу
    申请人:Марузен Ойл Ко (Инофирма)；
    IPC主号:
    专利说明:

    (5) A METHOD FOR OBTAINING SUPER-BASIC SULFURATED
    I
    This invention relates to an improved process for the preparation of superbasic sulfonated alkaline earth metal phenols, which are used as additives to 5 lubricating oils and liquid fuels.
    A known method of half-milling superbase sulfurized phenols and alkaline earth metals involves the interaction of phenol, sulfur 10 and an alkaline earth metal salt in the presence of a dihydric alcohol, followed by distilling off water and further treating the reaction product with an alkaline earth metal salt and 15 dihydric alcohol til.
    The closest to the described method is the production of superbasic sulfurized phenols of alkaline earth metals, consisting in 20 interactions of phenol, sulfur and an excess of an oxide or hydroxide of alkaline earth metals in the presence of a dihydric alcohol, followed by distillation of water and alcohol from the reaction mixture, added 25 alkaline earth minerals
    mineral oil and carbon dioxide treatment at 90-290 ° С 2.
    The disadvantage of this method is to obtain the desired products with an alkaline earth metal content not exceeding 170 from the theoretical value even when using a twofold excess of an oxide or hydroxide of an alkaline earth metal. To increase the alkaline earth metal content in the target product in order to increase its effectiveness as an additive, it is necessary to re-treat the reaction mixture with an alkaline earth metal oxide or hydroxide or use polyhydric alcohols, which greatly complicates the process. The presence of a large amount of unreacted alkaline earth metal hydroxide in the reaction mixture leads to low speed filter eanip.
    权利要求:
    Claims (2)
    [1]
    The purpose of the invention is to improve the quality of the target product and simplify the process. The goal is achieved when implementing the described method of producing superbasic sulfurized alkaline earth metal phenols, which consists in the interaction of phenol, sulfur and alkaline earth oxide or hydroxide of alkaline earth metal, taken in an amount of 0.001-0.99 per phenyl hydroxyl group, followed by distilling water and alcohol from the reaction mixture and treating it with carbon dioxide, at 50, 230 ° C. The content of alkaline earth metal in the target product reaches 10 About the value of Sulfur is used preferably in an amount of 0.001 mol and dihydric alcohol in an amount of 0.1-0.65 mol per I mol of alkaline earth metal oxide or hydroxide, and the interaction of phenol, sulfur and alkaline earth metal oxide or hydroxide is preferably carried out at 60-200 ° C, and the treatment of the reaction product with carbon dioxide at 80-200 ° C. Example 1. A 2-liter, four-necked flask equipped with a coil stirrer, a nitrogen gas tube and a thermometer was charged with 1233.7 g (5.6 mol) of nonylphenol 10.8 g of sulfur and 32 g {0.5 b mol) calcium oxide having a purity of 98.3. Under stirring under a nitrogen atmosphere, 118.2 g of ethylene glycol was added to the resulting suspension. The mixture was stirred at 135 ° C for 5 hours. Then the water and most of the unreacted ethylene glycol under vacuum were distilled to a vapor temperature of 87 ° C / 3 mm, thus forming 1276, + g of a dark yellowish-green liquid residue. Then the residue is placed in an autoclave and treated with carbon dioxide at an elevated pressure of not more than II kg / cm at 123 ° C and left at 155 ° C for 2 hours at elevated pressure (not more than 8 kg / cm), thus forming 1289.5 g of dark yellowish-green reaction product solution. A 2-liter pear-shaped two-neck flask is charged with 1278.3 g of reaction product, 133.7 g of neutral oil 150 (paraffin lubricating oil. Viscosity 5.386 cSt at 99 ° C) A small amount of ethylene glycol, most of the unreacted but nilphenol and a small amount of fracz dab of the oil is distilled from the mixture under reduced pressure to a vapor temperature of 1 ° C / 3 mm, 262.1 g of residue are obtained. After removing a small amount of insoluble substances in the residue after distillation, for example, by filtration or centrifuge separation, 261, k g of dark a yellow, transparent viscous product, which contains 281 (in terms of the theoretical amount) of calcium per equivalent of the hydroxyl group of the phenol. Viscosity at 99 ° C 318.7 cS Total base number (O.SH.CHO) KON 232 mg / g; calcium 8.40 weight .; sulfur 2.31 wtL, Example 2, To a mixture of 771.1 g (3.5 mol) of nonylphenol, 22.5 sulfur and 78.5 g (1.4 mol) of calcium oxide with a purity of 99.9 under nitrogen at 130 ° C at atmospheric pressure, 313 g of ethylene glycol are added, the mixture is stirred at 135 ° C for 5 hours, water and 99.3 g of ethylene glycol are distilled under vacuum to a vapor temperature of 105 ° C / 15 mm, yielding 1053.7 g of a dark yellow-green liquid residue. 6 g of residue is placed in an autoclave and treated; with carbon dioxide at an elevated pressure (not more than 11 kg / cm and a temperature of 127 ° C), left at 155 ° C and an increased pressure (not more than 8.7 kg / cm for 2 h, 7 g of a dark red solution of the reaction product are obtained A 2 liter two-neck flask was charged with 1008.9 g of the reaction product solution, 226.7 g of neutral oil 150 and unreacted ethylene glycol, most of the unreacted nonylphenol and a small amount of oil fraction to a vapor temperature of 179 ° were distilled off under reduced pressure. C / 3 mm. Receive 536.5 g of residue If removed from 532.7 g of a dark yellow transparent viscous liquid product are obtained from the residue of the distillation process by filtration or separation on a centrifuge. The final product has the following characteristics: viscosity (at 9 ° C) 879.4 cSt; mg / g, calcium content (in terms of theoretical amount) P1%, calcium 10.1% by weight, sulfur 3.67% E. 5 Example 3. In suspension obtained by mixing 1079.5 g (4.9 mol) nonylphenol, 2.25 g of sulfur and g (1.4 mol) of calcium oxide with a purity of 98.51 are added in an atmosphere, nitrogen at and at Under atmospheric pressure, ethylene glycol (, 8 g), the mixture is stirred for 5 hours. In vacuum, the water that forms during the reaction is distilled off, most of the unreacted ethylene glycol and a small amount of nonylphenol are formed to a vapor temperature of 99 ° C / 13 mm, forming 1277 g dark yellowish green product. 12b5.5 g of the residue is treated with carbon dioxide at a temperature of 123 to 129 ° C at a pressure not exceeding 11 kg / cm, then left at a pressure not exceeding 8.7 kg / cm and a temperature of 155 ° C for 2 hours. 1332.6 g of a reaction product solution about 1319 are formed, g is mixed with 332.8 g of neutral oil 150 and a small amount of ethylene glycol, a large part of unreacted nonylphenol and a small amount of lubricant fraction to vapor temperature 181 is distilled under reduced pressure under nitrogen. ° C / 3.5 mm, whereby a g of liquid residue is formed. After 1.6 g of insoluble materials are removed from the final product, it has the following characteristics: viscosity (at 99 ° C), 7 cSt; SCR, KOH 240 mg / g; calcium content (in terms of theoretical amount) calcium 8.82 wt.%; sulfur 0.31 wt.%. An example. In the suspension obtained by mixing 1079, 5 g (A, 9 mol) of nonylphenol, 27 g of sulfur and 78.4 g (1, mol) of calcium oxide, having a purity of 99.9, are added to the atmosphere of nitrogen at .130 ° C and atmospheric pressure ethylene glycol (, 8 g). The mixture was stirred at 135 ° C for 5 hours. The water that forms during the reaction is distilled off, most of the unreacted ethylene glycol and a small amount of nonylphenol are obtained at a vapor temperature of 100 ° C / 6 1261, 6 g of a yellowish-green residue are obtained. 1192.4 g of the residue is treated with carbon dioxide at a pressure not exceeding 11 kg / cm, temperature from 153 to 15b ° C, then left at a pressure of from 3.5 to 7 kg / cm2. At l85 ° C for 2 h, the result is 1,239.7 reaction product solutions. Then, 1228.7 g of it is mixed with 335 g of neutral oil 150. After distilling a small amount of ethylene glycol from the mixture under a nitrogen atmosphere and under reduced pressure, most of the unreacted nonylphenol and a small amount of lubricant fraction to a vapor temperature of 1bC ° C / 5mm forms a liquid residue 6.67 g. After removing the product of insoluble substances, it has the following characteristics: viscosity (at 99 ° C) 116.8 cSt; SCR, KOH 228 mg / g. The calcium content (in terms of the theoretical amount) of calcium is 8.1 b weight; sulfur 3,02 weight. Example 5. In suspension 1035.4 g (4.7 mol) of nonylphenol, 25.9 g of sulfur and 7b, 6 g (1.34 mol) of calcium oxide having a purity of 98.3% in a nitrogen atmosphere at 1b5 ° C and ethylene glycol (141.8 g) is added under atmospheric pressure, stirred at 167 ° C for 5 hours, and then the temperature of the reaction mixture is reduced to 140 ° C. In vacuum, the water formed during the reaction is distilled off, most of the unreacted ethylene glycol and a small amount of nonylphenol are heated to 94C / 7 mm vapors, as a result of chego 1137.1 g of liquid residue is formed. 1132.1 g of the residue is treated with carbon dioxide at a pressure not exceeding 11 kg / cm and a temperature of 136 to, then left at ij (j) by pressure (10.8 kg / cm) for 2 hours, as a result 1186.2 g of a dark yellow solution of the reaction product.The solution of the reaction product is mixed with 322.9 g of neutral oil 150. After distilling a small amount of ethylene glycol from the mixture in a nitrogen atmosphere under reduced pressure, most unreacted nonylphenol and a small amount of lubricant oil are obtained 789.2 g of liquid viscous residue After removing 1.5 g of insoluble substances, the product has the following characteristics: viscosity (at 99 ° C) 218.1 cSt; SCEP, KOH 186 mg / g; calcium content (calculated on a theoretical amount) 220, calcium 6.63 weightD; sulfur 2.24% weight. Example 6 A suspension consisting of 848.2 g (3.85 mol) of nonyl phenol, 105.9 sulfur and 62.7 g (1.1 mol) of calcium oxide having a purity of 98.5, under an atmosphere of nitrogen at 130 ° C, ethylene glycol (239.1 g) is added, stirred for 6 hours, the water formed during the reaction is distilled to a vapor temperature of 117 ° C / 51 mm, resulting in 1216 , 8 g dark red 1201.3 g of the residue is treated with carbon monoxide at a pressure not exceeding 11.5 kg / cm, temperatures 125 ° С, left at elevated pressure (7.8 kg / cm) and temperature for 1 hour. This produces 1230.6 g of a dark red solution of the reaction product. A solution of the reaction product (119.5 is mixed with 255, and g neutral 150 После. After distilling most of the unreacted ethylene glycol and unreacted nonylphenol and also a small amount of lubricant oil into the vapor temperature of 178 ° C / 3 mm from the mixture under nitrogen at a reduced pressure , 823.7 g of a dark red viscous liquid residue are obtained. After removing 1 g of insoluble substances from the product, it has the following characteristics / viscosity: viscosity (at 99 ° C) 89.2 cSt; SCREAM, KOH 1 h4 mg / g Content calcium (in terms of theoretical amount o) calcium sulfur 5.61 wt%, Example 7. A suspension prepared from 1336.6 g (4.55 mol per lane, counting for nonylphenol) of regenerated nonylphenol containing 6.5 ethylene glycol and 17.5 fractions of lubricant oils, 25 g of sulfur and 74.4 g (1.3 mol) of calcium oxide with a purity of 98.5% under nitrogen atmosphere, ethylene glycol (37.6 g) is added, stirred at 135 ° C for 4 hours. The water formed during the reaction, most of the unreacted ethylene glycol and a small amount of nonylphenol to a vapor temperature of 82 ° C / 6 mm, get 1343.7 g of a liquid residue, about 1334.6 g of a residue about It is activated with carbon dioxide at a pressure not exceeding 11 kg / cm, 6B temperature of from 122 to then allowed to stand at elevated pressure (13 kg / cm) and a temperature of 155 ° C for 2 hours. The obtained 1386.8 g of a reaction product solution. The solution of the reaction product (1370.4 g): mixed with 75.7 g of neutral maiel 150, distilling away a small amount of ethylene glycol, most of the unreacted nonylphenol and a small amount of lubricating oil to a vapor temperature of 183 ° C / 5 mm, resulting in 631.6 g of liquid residue. After removing 1.8 g of insoluble substances from the product, it has the following characteristics: viscosity (at 99 ° C) 225.6 cSt; OCHCH, KOI 218mg / g; the calcium content (in terms of theoretical amount) is 220, calcium is 8.0 wt.%, sulfur is 3.13 weight. Example 8. In this example, an alkylphenol prepared by alkylation of phenol with a mixture of ct-olefins containing from 6 to 28 carbon atoms is used as the starting material. A suspension of 1410 g (4.49 mol) of a mixture of alkylphenol isomers (42 ortho-isomers, 42 para-isomers, and 16 meta-isomers), having an average molecular weight of 314, and obtained by alkylation of the phenol with mixture Y.- olefins (ethylene telomeres containing from 6 to 28 carbon atoms and more than 88.6 straight chain alkenes), 24.7 g of sulfur and 73 g (1.28 mol) of calcium oxide, having a purity of 98.3, are mixed under a nitrogen atmosphere at 130 ° C with ethylene glycol (135.1 g), then the mixture is stirred at 135 ° C for 5 hours. The water formed during the reaction is distilled off, most of the time is ethylene glycol and a small amount of alkylphenols to a vapor temperature of 7 ° C / 2 mm, resulting in 1520.3 g of a liquid residue. Next, 1518.2 g of the residue is treated with carbon dioxide at a pressure not exceeding 11 kg / cm, a temperature of 124 ° C, then left at an elevated pressure (7 kg / cm) and a temperature of 155 ° C for 2 hours, yielding 1576, 2 g dark red solution of the reaction product. A solution of the reaction product (1539.9 g) is mixed with 235, г of neutral oil 150 о. A small amount of ethylene glycol, a part of alkylphenol and a small amount of lubricant oil to a vapor temperature of 220 ° C / 1.5 are distilled from the mixture under a nitrogen atmosphere under reduced pressure. mm, 9b8 g of liquid residue is obtained. After removing from the product 2.2 g of insoluble substances, it has the following characteristics: viscosity (at 99 ° C) 40.7 cSt; .SCHON, KOH U mg / g; calcium content (in terms of theoretical amount) 300, calcium 5.16 weight ,; sulfur 1, B2 weight,%. Example3-. In a suspension of 1233.3 (k, 7 mol) of dodecylphenol, 25.9 g of sulfur and 7b, 6 g (1.3 mol) of calcium oxide with a purity of 98.5% in an atmosphere of nitrogen at 129 ° C, ethylene glycol (, 8 g), stirred at 135 ° C for k hours. The water formed during the reaction is distilled off, most of the unreacted ethylene glycol and a small amount of dodecylphenol are obtained, 2 liquid residues are obtained at a temperature of 112 ° C / 5, 1338.6 g of residue is treated carbon monoxide at a pressure not exceeding 10 kg / cm and a temperature of 125-127 ° C, is left at an elevated pressure (6.0 kg / cm) and a temperature of 150 ° C by 1.5 g, 1396.5 g of the reaction product solution are obtained. A solution of the reaction product (1372.2 g is mixed with 289.5 g of neutral oil 150, a small amount of ethylene glycol is distilled off under a mixture of nitrogen under reduced pressure, a large part of unreacted dodecylphenol and a small amount lube oil fractions; get b77.2 g of viscous residue. After removing 1.6 g of insoluble substances from the product, it has the following characteristics: viscosity (at) 173.7 cSt; SCEP, KOH 211 mg / g, calcium content (in terms of theoretical value) 2% OO; Calcium 7.5 wtD, sulfur 2.9 wtD. Example 10 To a suspension of 1321.8 g (6 mol) of nonylphenol, 2.9 g (0.09 mol) of sulfur and 8.6 g (0.15 mol) of calcium oxide with a purity of 98.3% in a stream of nitrogen at atmospheric pressure 6 g (2 mol) of ethylene glycol in a stream of nitrogen at 130 ° C are added, and the mixture is stirred at 135 ° C for 5 hours. The water formed during the reaction, most of the unreacted ethylene glycol and a small amount of nonylphenol are distilled to a vapor temperature of 99 ° C / 18 mm, thus, 7 g of a dark yellow-green liquid residue is obtained. Then 1338.5 g of the residue are placed in an autoclave, carbon dioxide is treated at a pressure of not more than 7 kgf / cm and a temperature of 113-115 ° C, left at 155 ° C for 2 hours at a pressure of not more than 7 kgf / cm, and 7 g dark yellow-green solution of the reaction product. In a two-necked flask with a capacity of 2 liters, 1336.8 g of the reaction product solution and +8.5 g of neutral oil 150 are loaded and unreacted ethylene glycol in a stream of nitrogen under reduced pressure, most of the unreacted: its nonylphenol and the oil fraction are distilled off, to obtain 78.8 g viscous residue. After separation from the residue, 0.13 g of substances insoluble in n-hexane, a product is obtained with the following properties: viscosity (at 210 ° C) 128.6, OSHCH, KOH mg / g, calcium content (in terms of theoretical amount), calcium 7 , wt.%, sulfur 0.31 wt.%. Claims 1. A method for producing alkaline earth metal sulphurized phenols of superbasic phenol, comprising reacting phenol, sulfur and an alkaline earth metal oxide or hydroxide in the presence of a dihydric alcohol, followed by distilling water and alcohol from the reaction mixture and treating it with carbon dioxide with heating, electrolyzing what with in order to simplify the process and improve the quality of the target product, the process is carried out with the use of 0.001-0.99 gEq of oxide or alkaline earth metal hydroxide calculated on the hydroxyl group of phenol, and carbon dioxide treatment at 0-230 ° C.
    [2]
    2. Method pop, 1, differs from the fact that sulfur is used in an amount of 0.001 mol, and dihydric alcohol in an amount of 0.1-0.65 mol and 1 mol of an oxide or hydroxide of a silk-earth metal. 3, The method according to claim 1, wherein the interaction of the enol, sulfur and oxide or hydroxide
    88881612
    alkaline earth metal is carried out 1. Patent of Great Britain N900059, at 60-200 C, and the processing of the product CLI1 F, published. 1962. reaction with carbon dioxide at 80-200 ° C. 2. US patent No. 3036971,
    Sources of information, cl. 252-i 2.7, publication, 19b2 (proto, taken into account in the examination of the type).
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    同族专利:
    公开号 | 公开日
    GB1599310A|1981-09-30|
    US4123371A|1978-10-31|
    FR2376159B1|1981-07-10|
    JPS6028878B2|1985-07-06|
    JPS5441829A|1979-04-03|
    FR2376159A1|1978-07-28|
    引用文献:
    公开号 | 申请日 | 公开日 | 申请人 | 专利标题
    DE1055006B|1953-04-30|1959-04-16|Exxon Research Engineering Co|Process for the production of lubricating oil additives|
    US3464970A|1967-03-13|1969-09-02|Maruzen Oil Co Ltd|Process for preparing over-based sulfurized calcium phenates|
    GB1280749A|1970-06-18|1972-07-05|Maruzen Oil Company Ltd|Process for preparation of over-based sulphurized phenates|US4261692A|1979-11-01|1981-04-14|Davy Mckee Corporation|Roll press for forming briquettes|
    US4710308A|1982-04-08|1987-12-01|Amoco Corporation|Process for preparing overbased sulfurized phenates|
    JPH0425996B2|1983-12-12|1992-05-06|Cosmo Oil Co Ltd|
    US4744800A|1985-01-18|1988-05-17|Nippon Oil Co., Ltd.|Gasoline compositions for automotive vehicles|
    JPH0374716B2|1985-01-29|1991-11-27|
    US4664824A|1986-01-14|1987-05-12|Amoco Corporation|Phenate product and process|
    US4971710A|1986-10-21|1990-11-20|Chevron Research Company|Methods for preparing, Group II metal overbased sulfurized alkylphenols|
    US4744921A|1986-10-21|1988-05-17|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|
    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|
    US7435709B2|2005-09-01|2008-10-14|Chevron Oronite Company Llc|Linear alkylphenol derived detergent substantially free of endocrine disruptive chemicals|
    ES2655116T3|2006-09-19|2018-02-16|Infineum International Limited|A lubricating oil composition|
    EP1903093B1|2006-09-19|2017-12-20|Infineum International Limited|A lubricating oil composition|
    法律状态:
    优先权:
    申请号 | 申请日 | 专利标题
    JP51160376A|JPS6028878B2|1976-12-29|1976-12-29|
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