Ester compound and preparation method and application thereof
阅读说明：本技术 一种酯类化合物及其制备方法、用途 (Ester compound and preparation method and application thereof ) 是由 张耀 段庆华 鱼鲲 李勇 于 2019-10-24 设计创作，主要内容包括：本发明提供了一种酯类化合物及其制备方法、用途。本发明的酯类化合物,其结构如式(I)所示：其中各基团的定义见说明书。本发明的酯类化合物具有非常优异的抗磨减摩性能,能够用作抗磨剂、减摩剂,特别用作石油产品的抗磨剂、减摩剂。(The invention provides an ester compound and a preparation method and application thereof. The structure of the ester compound is shown as the formula (I):)
1. An ester compound has a structure shown in formula (I):
in the formula (I), I is an integer of 1 to 10 (preferably an integer of 1 to 8, more preferably an integer of 1 to 5); j is an integer of 1 to 10 (preferably an integer of 1 to 8, more preferably an integer of 1 to 5);
the L group being selected from (i + j) -valent C1-30A hydrocarbon group, a single bond (preferably selected from (i + j) -valent C1-20Straight or branched alkyl, more preferably C selected from (i + j valent)1-10Straight or branched chain alkyl); when one of i and j is greater than 1, the L group is selected from (i + j) -valent C1-30Hydrocarbyl (preferably selected from (i + j) -valent C1-20Straight or branched alkyl, more preferably C selected from (i + j valent)1-10Straight or branched chain alkyl); when i ═ j ═ 1, the L group is selected from C1-30Alkylene, single bond(preferably selected from C)1-20Straight or branched alkylene, single bond, more preferably selected from C1-10Linear or branched alkylene, single bond);
each R group, which may be the same or different from each other, is independently selected from C1-10Straight or branched chain alkyl, — L' - (OH)nH (preferably selected from C)1-6Straight or branched chain alkyl, — L' - (OH)nH, more preferably C1-3Straight or branched chain alkyl, — L' - (OH)nH), wherein n is an integer of 1 to 10 (preferably an integer of 1 to 6, more preferably 1, 2 or 3), and the L' group is C having a valence of (n +1)1-17Hydrocarbyl (preferably selected from (n +1) -valent C1-15Straight or branched alkyl, more preferably C selected from (n +1 valent)1-11Straight or branched chain alkyl);
each R' group is the same or different from each other and is independently selected from single bond, C1-20Alkylene (preferably C)1-12Straight or branched alkylene, more preferably C1-8Linear or branched alkylene);
m is an integer of 1 to 12 (preferably an integer of 1 to 8, more preferably an integer of 1 to 5);
each R' group, equal to or different from each other, is independently selected from a single bond, C1-10Alkylene (preferably C)1-6Straight or branched alkylene, more preferably C1-3Linear or branched alkylene);
each R is0The radicals, equal to or different from each other, are each independently selected from H, C1-10Hydrocarbyl (preferably C)1-6Straight or branched alkyl, more preferably C1-3Straight or branched chain alkyl);
each A group, which may be the same or different from each other, is independently selected from the group consisting of a group represented by the formula (II), a group represented by the formula (III) - (CH) -,ethylene, propylene, and at least one A group is selected from a group represented by formula (II), or a group represented by formula (III), or at least two A groups are selected from a group represented by formula (IV);
in formulae (II) and (III), each G1Each independently selected from-O-,(wherein the carbonyl carbon is bonded to R1Group attachment); n is an integer of 1 to 10 (preferably an integer of 1 to 6, more preferably 1, 2 or 3); r1Selected from (n +1) -valent C1-17Hydrocarbyl (preferably selected from (n +1) -valent C1-15Straight or branched alkyl, more preferably C selected from (n +1 valent)1-11Straight or branched chain alkyl);
each G2Each independently selected from-OR2、Wherein each R is2Each independently selected from H, C1-10Straight or branched chain alkyl (preferably selected from H, C)1-6Straight or branched chain alkyl, more preferably selected from H, C1-3Straight or branched alkyl), each R3Each independently selected from H, C1-10Straight or branched chain alkyl (preferably selected from H, C)1-6Straight or branched chain alkyl, more preferably selected from H, C1-3Straight or branched chain alkyl);
in the formula (IV), G3The radicals being selected from(wherein the carbonyl carbon is bonded to R1Group attachment); g4Each independently selected fromWherein each R is3Each independently selected from H, C1-10Straight or branched chain alkyl (preferably selected from H, C)1-6Straight or branched chain alkyl, more preferably selected from H, C1-3Straight or branched chain alkyl).
2. Esters according to claim 1, characterized in that in the formulae (II) and (III), each G is1Each independently selected from-O-; each G2Each independently selected from-OR2Wherein each R is2Each independently selected from H, C1-10Straight or branched chain alkyl.
3. Esters according to claim 1, characterized in that in the formulae (II) and (III), each G is1Each independently selected from(wherein the carbonyl carbon is bonded to R1Group attachment); each G2Each independently selected fromWherein each R is3Each independently selected from H, C1-10Straight or branched chain alkyl (preferably selected from H, C)1-6Straight or branched chain alkyl, more preferably selected from H, C1-3Straight or branched chain alkyl).
4. An ester compound according to claim 1, wherein i ═ j ═ 1, and the ester compound has a structure represented by formula (V):
in formula (V), the L group is selected from C1-30Alkylene, single bond (preferably selected from C)1-20Straight or branched alkylene, single bond, more preferably selected from C1-10Linear or branched alkylene, single bond).
5. An ester compound as claimed in claim 1, wherein the ester compound comprises one or more of the following compounds:
6. a process for producing an ester compound, comprising the steps of epoxidizing at least one ethylenic bond in a compound represented by the formula (alpha) and reacting the resultant product with a compound represented by the formula (beta),
in the formula (alpha), i is an integer of 1 to 10 (preferably an integer of 1 to 8, more preferably an integer of 1 to 5); j is an integer of 1 to 10 (preferably an integer of 1 to 8, more preferably an integer of 1 to 5);
the L group being selected from (i + j) -valent C1-30A hydrocarbon group, a single bond (preferably selected from (i + j) -valent C1-20Straight or branched alkyl, more preferably C selected from (i + j valent)1-10Straight or branched chain alkyl); when one of i and j is greater than 1, the L group is selected from (i + j) -valent C1-30Hydrocarbyl (preferably selected from (i + j) -valent C1-20Straight or branched alkyl, more preferably C selected from (i + j valent)1-10Straight or branched chain alkyl); when i ═ j ═ 1, the L group is selected from C1-30Alkylene, single bond (preferably selected from C)1-20Straight or branched alkylene, single bond, more preferably selected from C1-10Linear or branched alkylene, single bond);
the individual R radicals being identical to one another or differentAnd each is independently selected from C1-10Straight or branched chain alkyl, — L' - (OH)nH (preferably selected from C)1-6Straight or branched chain alkyl, — L' - (OH)nH, more preferably C1-3Straight or branched chain alkyl, — L' - (OH)nH), wherein n is an integer of 1 to 10 (preferably an integer of 1 to 6, more preferably 1, 2 or 3), and the L' group is C having a valence of (n +1)1-17Hydrocarbyl (preferably selected from (n +1) -valent C1-15Straight or branched alkyl, more preferably C selected from (n +1 valent)1-11Straight or branched chain alkyl);
each R' group is the same or different from each other and is independently selected from single bond, C1-20Alkylene (preferably C)1-12Straight or branched alkylene, more preferably C1-8Linear or branched alkylene);
m is an integer of 1 to 12 (preferably an integer of 1 to 8, more preferably an integer of 1 to 5);
each R' group, equal to or different from each other, is independently selected from a single bond, C1-10Alkylene (preferably C)1-6Straight or branched alkylene, more preferably C1-3Linear or branched alkylene);
each R is0The radicals, equal to or different from each other, are each independently selected from H, C1-10Hydrocarbyl (preferably C)1-6Straight or branched alkyl, more preferably C1-3Straight or branched chain alkyl);
each A' group, which may be the same or different from each other, is independently selected from the group consisting of,Ethylene, propylene, and at least one a' group is selected from-CH ═ CH —;
in the formula (. beta.), G1A group selected from-O-,(wherein the carbonyl carbon is bonded to R1Group attachment);
n is an integer of 1 to 10 (preferably an integer of 1 to 6, more preferably 1, 2 or 3);
the X group is selected from H;
R1selected from (n +1) -valent C1-17Hydrocarbyl (preferably selected from (n +1) -valent C1-15Straight or branched alkyl, more preferably C selected from (n +1 valent)1-11Straight or branched chain alkyl);
each G2Each of the radicals is independently selected from-OR2、Wherein each R is2Each independently selected from H, C1-10Straight or branched chain alkyl (preferably selected from H, C)1-6Straight or branched chain alkyl, more preferably selected from H, C1-3Straight or branched alkyl), each R3Each independently selected from H, C1-10Straight or branched chain alkyl (preferably selected from H, C)1-6Straight or branched chain alkyl, more preferably selected from H, C1-3Straight or branched chain alkyl).
7. The process according to claim 6, wherein in the formula (β), G1A group selected from-O-; each G2Each of the radicals is independently selected from-OR2Wherein each R is2Each independently selected from H, C1-10Straight or branched chain alkyl.
8. The process according to claim 6, wherein in the formula (β), G1A group selected from(wherein the carbonyl carbon is bonded to R1Group attachment); each G2Each of the radicals is independently selected fromWherein each R is3Each independently selected from H, C1-10Straight or branched chain alkyl (preferably selected from H, C)1-6Straight or branched chain alkyl, more preferably selected from H, C1-3Straight or branched chain alkyl).
9. The process according to claim 6, wherein i ═ j ═ 1, and the compound represented by formula (α) has a structure represented by formula (γ):
in formula (. gamma.), the L group is selected from C1-30Alkylene, single bond (preferably selected from C)1-20Straight or branched alkylene, single bond, more preferably selected from C1-10Linear or branched alkylene, single bond).
10. The process according to claim 6, wherein the compound of formula (α) is selected from one or more of the following compounds, or a condensation product of these compounds with each other or with each other: eicosenoic acid, oleic acid, linoleic acid, linolenic acid, hexadecenoic acid, tetradecenoic acid, dodecenoic acid, undecenoic acid, decenoic acid, octenoic acid;
or the compounds of the formula (. beta.) are selected from one or more of the following compounds, or the condensation products of these compounds with themselves or with one another: ethylene glycol, propylene glycol, butylene glycol, pentanediol, hexanediol, nonanediol, decanediol, undecanediol, dodecanediol, tridecanediol, tetradecanediol, pentadecanediol, phenol, cresol, benzenediol, tert-butyldiphenol, benzenetriol, naphthalenediol, glycerol, trimethylolpropane, pentaerythritol, oxalic acid, malonic acid, succinic acid, glutaric acid, adipic acid, azelaic acid, sebacic acid, undecanedioic acid, dodecanedioic acid, tridecanedioic acid, tetradecanedioic acid, pentadecanedioic acid, phthalic acid, terephthalic acid.
11. The process according to claim 6, wherein the compound of formula (α) is epoxidated with an oxidizing agent (preferably comprising an organic peroxide and/or an inorganic peroxide).
12. A process according to claim 6, characterized in that the epoxidation product of the compound of formula (α) (based on the amount of epoxide groups) is reacted with a compound of formula (β) (based on the amount of epoxide groups-XO-andamount of) is 1: 0.5 to 100 (preferably 1: 1 to 10); the reaction temperature is 20-200 ℃ (preferably 40-150 ℃).
13. The process according to claim 6, wherein a catalyst (which may be one or more of an inorganic acid, an organic acid, a solid acid, a heteropolyacid, an acidic ionic liquid, an acidic resin, an acidic molecular sieve, a metal chloride and a metal oxide, for example, sulfuric acid, perchloric acid, AlCl, etc.) is added to the reaction of the epoxidation product of the compound represented by the formula (α) with the compound represented by the formula (β)3One or more of tin chloride, n-butyl tin oxide, dibutyl tin oxide, p-toluenesulfonic acid, acidic resins, phosphotungstic heteropoly acids, acidic ionic liquids, and acidic molecular sieves).
14. The ester compound of any one of claims 1 to 5 or the ester compound produced by the method of any one of claims 6 to 13 for use as an antiwear agent and/or a friction reducing agent (preferably for use as an antiwear agent and/or a friction reducing agent for petroleum products).
15. A lubricating oil composition comprising the ester compound according to any one of claims 1 to 5 or the ester compound obtained by the method according to any one of claims 6 to 13, and a lubricating oil base oil.
Technical Field
The invention relates to the field of petroleum products, in particular to an ester compound.
Background
Reducing frictional wear is an important means for improving fuel economy and prolonging the service life of equipment. Research shows that low molecular alkane with relatively low polarity and alkane structure can only be physically adsorbed on metal surface and has relatively low adsorption energy and thus no good lubricating effect. The sulfur, nitrogen and oxygen compounds and aromatic hydrocarbon substances with higher polarity can be stably adsorbed on the metal surface, and play a good role in lubrication. However, with increasingly strict environmental requirements, the removal of sulfur, nitrogen and aromatic substances by deep processing refining processes such as hydrofining, hydrocracking and the like has become a necessary trend in the development of oil refining, the lubricating performance of oil products is synchronously reduced, and the abrasion of engine parts is aggravated.
Therefore, the introduction of a proper amount of a lubricating property improver to improve the lubricating property of the oil becomes an effective means for solving the above-mentioned contradiction. Many additives of ester structure have been developed in the prior art.
CN 1524935A reports an application method of modified grease as a low-sulfur diesel antiwear agent, which comprises the following steps: adding 10-2000 ppm of modified oil into low-sulfur diesel, wherein the modified oil is prepared by mixing natural oil and alcohol or amine according to the weight ratio of 1: 0.1-5, and reacting at 50-200 ℃ for 1-20 hours. The natural oil can be vegetable oil or animal oil. The alcohol is one or more selected from C1-C10 fatty alcohol, C2-C18 polyalcohol and alcohol amine. The amine is selected from one or more of C1-C10 fatty amine, polyene polyamine with the nitrogen atom number of 2-7, C5-C6 cyclylamine and heterocyclic amine. The modified grease is added into diesel oil with the sulfur content of less than 500ppm in an amount of 10-2000 ppm, so that the lubricity of low-sulfur diesel oil can be improved.
US 5282990 reports an improvement in the fuel economy of lubricating oils for internal combustion engines comprising adding to the oil an amine/amide and ester/alcohol blended friction modifier, for example, by reacting a carboxylic acid such as oleic acid or the isomeric stearic acids with an amine such as diethylenetriamine or tetraethylenepentamine, and glycerol monooleate or glycerol monoricinoleate.
Although the existing ester structure additive can improve the lubricating performance of oil products, the improvement space is large. In view of this, there is still a need in the art for friction performance modifiers with even better performance.
Disclosure of Invention
The invention provides an ester compound and a preparation method and application thereof.
The structure of the ester compound is shown as the formula (I):
in the formula (I), I is an integer of 1 to 10 (preferably an integer of 1 to 8, more preferably an integer of 1 to 5); j is an integer of 1 to 10 (preferably an integer of 1 to 8, more preferably an integer of 1 to 5);
the L group being selected from (i + j) -valent C1-30A hydrocarbon group, a single bond (preferably selected from (i + j) -valent C1-20Straight or branched alkyl, more preferably C selected from (i + j valent)1-10Straight or branched chain alkyl); when one of i and j is greater than 1, the L group is selected from (i + j) -valent C1-30Hydrocarbyl (preferably selected from (i + j) -valent C1-20Straight or branched alkyl, more preferably C selected from (i + j valent)1-10Straight or branched chain alkyl); when i ═ j ═ 1, the L group is selected from C1-30Alkylene, single bond (preferably selected from C)1-20Straight or branched alkylene, single bond, more preferably selected from C1-10Linear or branched alkylene, single bond);
each R group, which may be the same or different from each other, is independently selected from C1-10A straight or branched alkyl group,H (preferably selected from C)1-6A straight or branched alkyl group,H, more preferably selected from C1-3A straight or branched alkyl group,H) Wherein n is an integer of 1 to 10 (preferably an integer of 1 to 6, more preferably 1, 2 or 3), and the L' group is C having a valence of (n +1)1-17Hydrocarbyl (preferably selected from (n +1) -valent C1-15Straight or branched alkyl, more preferably C selected from (n +1 valent)1-11Straight or branched chain alkyl);
each R' group is the same or different from each other and is independently selected from single bond, C1-20Alkylene (preferably C)1-12Straight or branched alkylene, more preferably C1-8Linear or branched alkylene);
m is an integer of 1 to 12 (preferably an integer of 1 to 8, more preferably an integer of 1 to 5);
each R' group is the same or different from each other and is independently selected from the group consisting of a single bond, C1-10Alkylene (preferably C)1-6Straight or branched alkylene, more preferably C1-3Linear or branched alkylene);
each R is0The radicals, equal to or different from each other, are each independently selected from H, C1-10Hydrocarbyl (preferably C)1-6Straight or branched alkyl, more preferably C1-3Straight or branched chain alkyl);
each A group, which may be the same or different from each other, is independently selected from the group consisting of a group represented by the formula (II), a group represented by the formula (III) - (CH) -,ethylene, propylene, and at least one A group is selected from a group represented by formula (II), or a group represented by formula (III), or at least two A groups are selected from a group represented by formula (IV);
in formulae (II) and (III), each G1Each independently selected from-O-,(wherein the carbonyl carbon is bonded to R1Group attachment); n is an integer of 1 to 10 (preferably an integer of 1 to 6, more preferably 1, 2 or 3); r1Selected from (n +1) -valent C1-17Hydrocarbyl (preferably selected from (n +1) -valent C1-15Straight or branched alkyl, more preferably C selected from (n +1 valent)1-11Straight or branched chain alkyl);
each G2Each independently selected from-OR2、Wherein each R is2Each independently selected from H, C1-10Straight or branched chain alkyl (preferably selected from H, C)1-6Straight or branched chain alkyl, more preferably selected from H, C1-3Straight or branched alkyl), each R3Each independently selected from H, C1-10Straight or branched chain alkyl (preferably selected from H, C)1-6Straight or branched chain alkyl, more preferably selected from H, C1-3Straight or branched chain alkyl);
in the formula (IV), G3The radicals being selected from(wherein the carbonyl carbon is bonded to R1Group attachment); g4Each independently selected fromWherein each R is3Each independently selected from H, C1-10Straight or branched chain alkyl (preferably selected from H, C)1-6Straight or branched chain alkyl, more preferably selected from H, C1-3Straight or branched chain alkyl).
According to the invention, optionally in formulae (II) and (III), eachG1Each independently selected from-O-; each G2Each independently selected from-OR2Wherein each R is2Each independently selected from H, C1-10Straight or branched chain alkyl. Further, n is 1 or 2.
According to the invention, optionally, in formulae (II) and (III), each G1Each independently selected from(wherein the carbonyl carbon is bonded to R1Group attachment); each G2Each independently selected fromWherein each R is3Each independently selected from H, C1-10Straight or branched chain alkyl (preferably selected from H, C)1-6Straight or branched chain alkyl, more preferably selected from H, C1-3Straight or branched chain alkyl). Further, n is 1 or 2.
According to the present invention, when i ═ j ═ 1, the structure of the ester compound is represented by formula (V):
in formula (V), the L group is selected from C1-30Alkylene, single bond (preferably selected from C)1-20Straight or branched alkylene, single bond, more preferably selected from C1-10Linear or branched alkylene, single bond).
The ester compound with a specific structure comprises one or more of the following compounds:
the invention also provides a preparation method of the ester compound, which comprises the steps of carrying out epoxidation reaction on at least one olefinic bond in the compound shown in the formula (alpha) and then carrying out reaction with the compound shown in the formula (beta),
in the formula (alpha), i is an integer of 1 to 10 (preferably an integer of 1 to 8, more preferably an integer of 1 to 5); j is an integer of 1 to 10 (preferably an integer of 1 to 8, more preferably an integer of 1 to 5);
the L group being selected from (i + j) -valent C1-30A hydrocarbon group, a single bond (preferably selected from (i + j) -valent C1-20Straight or branched alkyl, more preferably C selected from (i + j valent)1-10Straight or branched chain alkyl); when one of i and j is greater than 1, the L group is selected from (i + j) -valent C1-30Hydrocarbyl (preferably selected from (i + j) -valent C1-20Straight or branched alkyl, more preferably C selected from (i + j valent)1-10Straight or branched chain alkyl); when i ═ j ═ 1, the L group is selected from C1-30Alkylene, single bond (preferably selected from C)1-20Straight or branched alkylene, single bond, more preferably selected from C1-10Linear or branched alkylene, single bond);
each R group, which may be the same or different from each other, is independently selected from C1-10A straight or branched alkyl group,H (preferably selected from C)1-6A straight or branched alkyl group,H, more preferably selected from C1-3A straight or branched alkyl group,H) Wherein n is an integer of 1 to 10 (preferably an integer of 1 to 6, more preferably 1, 2 or 3), and the L' group is C having a valence of (n +1)1-17Hydrocarbyl (preferably selected from (n +1) -valent C1-15Straight or branched alkyl, more preferably C selected from (n +1 valent)1-11Straight or branched chain alkyl);
each R' group is the same or different from each other and is independently selected from single bond, C1-20Alkylene (preferably C)1-12Straight or branched alkylene, more preferably C1-8Linear or branched alkylene);
m is an integer of 1 to 12 (preferably an integer of 1 to 8, more preferably an integer of 1 to 5);
each R' group is the same or different from each other and is independently selected from the group consisting of a single bond, C1-10Alkylene (preferably C)1-6Straight or branched alkylene, more preferably C1-3Linear or branched alkylene);
each R is0The radicals, equal to or different from each other, are each independently selected from H, C1-10Hydrocarbyl (preferably C)1-6Straight or branched alkyl, more preferably C1-3Straight or branched chain alkyl);
each A' group, which may be the same or different from each other, is independently selected from the group consisting of,Ethylene, propylene, and at least one a' group is selected from-CH ═ CH —;
in the formula (. beta.), G1A group selected from-O-,(wherein the carbonyl carbon is bonded to R1Group attachment);
n is an integer of 1 to 10 (preferably an integer of 1 to 6, more preferably 1, 2 or 3);
the X group is selected from H;
R1selected from (n +1) -valent C1-17Hydrocarbyl (preferably selected from (n +1) -valent C1-15Straight or branched chainAlkanyl, more preferably C selected from (n +1 valent)1-11Straight or branched chain alkyl);
each G2Each of the radicals is independently selected from-OR2、Wherein each R is2Each independently selected from H, C1-10Straight or branched chain alkyl (preferably selected from H, C)1-6Straight or branched chain alkyl, more preferably selected from H, C1-3Straight or branched alkyl), each R3Each independently selected from H, C1-10Straight or branched chain alkyl (preferably selected from H, C)1-6Straight or branched chain alkyl, more preferably selected from H, C1-3Straight or branched chain alkyl).
According to the preparation process of the invention, optionally in the formula (. beta.), G1A group selected from-O-; each G2Each of the radicals is independently selected from-OR2Wherein each R is2Each independently selected from H, C1-10Straight or branched chain alkyl. Further, n is 1, 2, 3 or 4.
According to the preparation process of the invention, optionally in the formula (. beta.), G1A group selected from(wherein the carbonyl carbon is bonded to R1Group attachment); each G2Each of the radicals is independently selected fromWherein each R is3Each independently selected from H, C1-10Straight or branched chain alkyl (preferably selected from H, C)1-6Straight or branched chain alkyl, more preferably selected from H, C1-3Straight or branched chain alkyl). Further, n is 1, 2, 3 or 4.
According to the preparation method of the present invention, when i ═ j ═ 1, the structure of the compound represented by formula (α) is represented by formula (γ):
in formula (. gamma.), the L group is selected from C1-30Alkylene, single bond (preferably selected from C)1-20Straight or branched alkylene, single bond, more preferably selected from C1-10Linear or branched alkylene, single bond).
According to the preparation method of the invention, the compound represented by the formula (alpha) can be selected from one or more of the following specific compounds, or condensation products of the compounds with themselves or each other: eicosenoic acid, oleic acid, linoleic acid, linolenic acid, hexadecenoic acid, tetradecenoic acid, dodecenoic acid, undecenoic acid, decenoic acid, octenoic acid.
According to the preparation method of the present invention, the compound represented by the formula (β) may be optionally selected from one or more of the following specific compounds, or condensation products of these compounds with themselves or with each other: ethylene glycol, propylene glycol, butylene glycol, pentanediol, hexanediol, nonanediol, decanediol, undecanediol, dodecanediol, tridecanediol, tetradecanediol, pentadecanediol, phenol, cresol, benzenediol, tert-butyldiphenol, benzenetriol, naphthalenediol, glycerol, trimethylolpropane, pentaerythritol, oxalic acid, malonic acid, succinic acid, glutaric acid, adipic acid, azelaic acid, sebacic acid, undecanedioic acid, dodecanedioic acid, tridecanedioic acid, tetradecanedioic acid, pentadecanedioic acid, phthalic acid, terephthalic acid.
According to the preparation method of the present invention, the compound represented by the formula (α) may be optionally subjected to an epoxidation reaction with an oxidizing agent. The oxidant is capable of epoxidizing at least one olefinic bond in the compound of formula (α) (conversion of an alkenyl group to an epoxy group). The oxidant comprises organic peroxide and/or inorganic peroxide, and specifically can be one or more of the following compounds: hydrogen peroxide, tert-butyl hydroperoxide, ethylbenzene hydroperoxide, cumene hydroperoxide. The reaction equivalent ratio between the compound represented by the formula (α) (in terms of-C ═ C-) and the oxidizing agent is preferably 1: 1 to 5, more preferably 1: 1-3; the reaction temperature is preferably 0 to 200 ℃, more preferably 30 to 100 ℃. The time of the epoxidation reaction is preferably as long as the epoxidation reaction proceeds smoothly, and generally, the longer the reaction time is, the more preferably 0.5 to 24 hours, and the more preferably 1 to 10 hours. The epoxidation reaction of the compound represented by the formula (α) may be carried out by a conventional phase transfer reaction, for example, by reacting hydrogen peroxide with formic acid in situ to generate peroxy acid, and then completing an oxygen atom transfer reaction with an olefinic bond, or by adding a catalyst to the epoxidation reaction of the compound represented by the formula (α). The catalyst can be a catalyst and/or an acid catalyst containing one or more metals of titanium, tungsten, molybdenum, rhenium and aluminum, and specifically can be one or more of a titanium-silicon material, a tungsten heteropoly acid salt, a molybdenum-containing complex, methyl rhenium trioxide, aluminum sulfate, sulfuric acid, hydrochloric acid, nitric acid or phosphoric acid. The amount of the catalyst is preferably 0.01 to 10% by mass of the compound represented by the formula (α).
According to the preparation method of the invention, at least one olefinic bond in the compound shown in the formula (alpha) is subjected to epoxidation reaction to generate an epoxidation product of the compound shown in the formula (alpha). The epoxidation product of the compound represented by the formula (α) may be subjected to the next reaction after purification, or may be subjected to the next reaction without purification. And (c) reacting the epoxidation product of the compound shown in the formula (alpha) with the compound shown in the formula (beta) to obtain the ester compound. The ester compound can be a compound with a single structure, and can also be a mixture containing compounds with different structures. For a mixture of compounds of different structures, it is sometimes possible to separate it into compounds of a single structure, and it is sometimes also possible to use the mixture of compounds of different structures as it is without separating it into compounds of a single structure.
According to the preparation process of the present invention, preferably, an epoxidation product of a compound represented by the formula (. alpha.) in terms of epoxy groups is reacted with a compound represented by the formula (. beta.) in terms of-XO-andamount of (d) is preferably 1: 0.5 to 100, more preferably 1: 1-10; the reaction temperature is preferably 20 to 200 ℃, and more preferably 40 to 150 ℃. The above-mentionedThe reaction time is preferably such that the reaction proceeds smoothly, and generally, the longer the reaction time is, the better the reaction time is, preferably 1 to 24 hours, and more preferably 2 to 10 hours.
According to the present invention, a catalyst may or may not be added, preferably a catalyst is added, to the reaction of the epoxidation product of the compound represented by the formula (α) with the compound represented by the formula (β). The catalyst can be one or more of inorganic acid, organic acid, solid acid, heteropoly acid, acidic ionic liquid, acidic resin, acidic molecular sieve, metal chloride and metal oxide, for example, sulfuric acid, perchloric acid, AlCl can be selected3One or more of tin chloride, n-butyl tin oxide, dibutyl tin oxide, p-toluenesulfonic acid, acidic resins, phosphotungstic heteropoly acids, acidic ionic liquids and acidic molecular sieves, preferably one or more of sulfuric acid, tin chloride, n-butyl tin oxide, p-toluenesulfonic acid, acidic resins and phosphotungstic heteropoly acids. The amount of the catalyst added is preferably 0.1 to 10% of the amount of the compound represented by the formula (α).
According to the preparation method of the present invention, a solvent may or may not be added, preferably a solvent is added, in the epoxidation reaction of the compound represented by the formula (α) and/or the reaction of the epoxidation product of the compound represented by the formula (α) with the compound represented by the formula (β). The solvent is preferably a hydrocarbon solvent, preferably one or more of alkane, aromatic hydrocarbon and ether, more preferably an alkane solvent, and for example, one or more of hexane, heptane, octane, nonane, decane, cyclohexane, cycloheptane, cyclooctane, cyclononane, cyclodecane, benzene, toluene, xylene, ethylbenzene, propylbenzene, diethyl ether, propyl ether, isopropyl ether and dibutyl ether may be used. The amount of the solvent to be added is not particularly limited, as long as the reaction is promoted to proceed smoothly. The solvent may be removed by a known method, for example, distillation, rectification, etc., and is not particularly limited.
According to the production method of the present invention, in the epoxidation reaction of the compound represented by the formula (α) and/or the reaction of the epoxidation product of the compound represented by the formula (α) with the compound represented by the formula (β), the reaction product is preferably washed and purified with a solvent, and the solvent which can be washed is preferably a hydrocarbon solvent. The solvent may be removed by conventional techniques such as drying, evaporation, distillation, and the like.
According to the preparation method of the present invention, the epoxidation reaction of the compound represented by the formula (α) and/or the reaction of the epoxidation product of the compound represented by the formula (α) with the compound represented by the formula (β) may be carried out in a continuous or batch reaction apparatus such as a reaction vessel, a fixed bed, a fluidized bed, a microchannel reactor, or the like.
The ester compound has excellent wear resistance and friction reduction performance, can be used as a wear resistance agent and a friction reducing agent, and is particularly used as the wear resistance agent and the friction reducing agent of petroleum products (especially lubricating oil/grease).
The invention also provides a lubricating oil composition which comprises the ester compound or the ester compound prepared by the method and lubricating oil base oil. Wherein the ester compound accounts for 0.1-100% of the total mass of the lubricating oil composition, preferably 0.1-90%, more preferably 1-50%, further optionally 2-30%, and 3-25%. The lubricating oil composition has excellent wear resistance and friction reduction performance.
According to the present invention, the lubricating oil composition may further comprise other components. Examples of the other components include various additives which are allowed to be added to the lubricating oil composition in the art, and specific examples thereof include phenol type, amine type or sulfur phosphorus type antioxidants, carboxylate, sulfonate or alkylphenate detergents, succinimide type ashless dispersants, polyester, polyolefin or alkylnaphthalene type pour point depressants, methacrylate ester copolymers, ethylene-propylene copolymers, polyisobutylene, hydrogenated styrene/butadiene copolymer type viscosity index improvers, sulfur/phosphorus type friction modifiers, sulfur/phosphorus and boric acid type extreme pressure agents, and silicon type or non-silicon type antifoaming agents. The kind and amount of these additives are well known to those skilled in the art and will not be described herein. These additives may be used singly or in combination in any ratio.
Detailed Description
In the context of the present specification, the definition of a groupThe term "single bond" is sometimes used herein. By "single bond", it is meant that the group is absent. For example, assume the formula-CH2-A-CH3Wherein the group a is defined as being selected from the group consisting of a single bond and a methyl group. In this respect, if A is a single bond, this means that the group A is absent, in which case the formula is correspondingly simplified to-CH2-CH3。
In the context of the present specification, the expression "number + valence + group" or the like refers to a group obtained by removing the number of hydrogen atoms represented by the number from the basic structure (such as a chain, a ring, a combination thereof, or the like) to which the group corresponds, and preferably refers to a group obtained by removing the number of hydrogen atoms represented by the number from a carbon atom (preferably a saturated carbon atom and/or a non-identical carbon atom) contained in the structure. For example, "3-valent straight or branched alkyl" refers to a group obtained by removing 3 hydrogen atoms from a straight or branched alkane (i.e., the base chain to which the straight or branched alkyl corresponds), and "2-valent straight or branched heteroalkyl" refers to a group obtained by removing 2 hydrogen atoms from a straight or branched heteroalkane (preferably from a carbon atom contained in the heteroalkane, or further, from a non-identical carbon atom). For example, the 2-valent propyl group may be-CH2-CH2-CH2-*、The 3-valent propyl group may beThe 4-valent propyl group may beWherein represents a binding end in the group that may be bonded to other groups.
Example 1: preparation of epoxy methyl oleate A
The reaction was carried out in a reaction vessel equipped with a vent, stirrer and thermocouple. Adding 2000g of methyl oleate, 158g of formic acid and 15g of sulfuric acid into a reaction kettle, heating to 60 ℃, pumping 1150g of hydrogen peroxide with the concentration of 30% into the reaction kettle for 6h, removing the residual formic acid and water in a distillation mode after the reaction is finished, cooling to room temperature, and washing with deionized water for three times to obtain epoxy methyl oleate.
Example 2: preparation of ester Compound A-1
62g of ethylene glycol and 1.5g of p-toluenesulfonic acid catalyst are added into a 500mL three-neck glass flask, the mixture is heated to 100 ℃, 156g of epoxy methyl oleate A is gradually dripped into the three-neck flask within 3h, the reaction is continued for 2h while maintaining the temperature at 100 ℃ after the dripping is finished, and the excessive ethylene glycol is removed by distillation. And washing the crude product with water to remove the catalyst and to be neutral to obtain the ester compound A-1, wherein the structure of the ester compound A-1 is shown as follows.
Example 3: preparation of ester Compound A-2
Adding 146g of adipic acid and 1.5g of p-toluenesulfonic acid catalyst into a 500mL three-neck glass flask, heating to 150 ℃, gradually dropwise adding 156g of epoxy methyl oleate A into the three-neck flask within 3H, and collecting H generated in the reaction process by using a water separator2And O, after the dropwise addition is finished, maintaining the temperature at 100 ℃ for further reaction for 2 hours. And washing the crude product with water to remove the catalyst and to be neutral to obtain the ester compound A-2, wherein the structure of the ester compound A-2 is shown as follows.
Comparative example 1: preparation of ester Compound D-1
The preparation method of D-1 is the same as that of A-1 except that the ethylene glycol is replaced by the ethanol with the same mole, and the ester compound D-1 is obtained.
Comparative example 2: preparation of ester Compound D-2
The preparation method of D-2 is the same as that of A-2 except that adipic acid is replaced by equal moles of caproic acid, and the ester compound D-2 is obtained.
Example 4: preparation of epoxy oleic acid B
The reaction was carried out in a reaction vessel equipped with a vent, stirrer and thermocouple. Adding 1900g of oleic acid, 158g of formic acid and 15g of sulfuric acid into a reaction kettle, heating to 60 ℃, pumping 1150g of hydrogen peroxide with the concentration of 30% into the reaction kettle for 6 hours, removing the rest formic acid and water in a distillation mode after the reaction is finished, cooling to room temperature, and washing with deionized water for three times to obtain epoxy oleic acid B.
Example 5: preparation of ester Compound B-1
Adding 76g of 1, 3-propanediol and 1.5g of p-toluenesulfonic acid catalyst into a 500mL three-neck glass flask, heating to 120 ℃, gradually dropwise adding 150g of epoxy oleic acid B into the three-neck flask within 3H, and collecting H generated in the reaction process by using a water separator2And O, after the dropwise addition is finished, maintaining the temperature at 120 ℃ for continuously reacting for 5h, and distilling to remove the excessive propylene glycol. And washing the crude product with water to remove the catalyst and to be neutral to obtain the ester compound B-1, wherein the structure of the ester compound B-1 is shown as follows.
Example 6: preparation of ester Compound B-2
Adding 146g of adipic acid and 1.5g of p-toluenesulfonic acid catalyst into a 500mL three-neck glass flask, heating to 150 ℃, gradually dropwise adding 150g of epoxy oleic acid B into the three-neck flask within 3H, and collecting H generated in the reaction process by using a water separator2And O, after the dropwise addition is finished, maintaining the temperature at 150 ℃ for continuously reacting for 2 hours. And washing the crude product with water to remove the catalyst and to be neutral to obtain an ester compound B-2, wherein the structure of the ester compound B-2 is shown as follows.
Comparative example 3: preparation of ester Compound D-3
The preparation method of D-3 was the same as that of B-2 except that the adipic acid was replaced with methanol in an equimolar amount and the reaction temperature was controlled at 50 ℃ to obtain an ester compound D-3.
Example 7: preparation of epoxy linoleic acid C
The reaction was carried out in a reaction vessel equipped with a vent, stirrer and thermocouple. Adding 1900g of linoleic acid, 300g of formic acid and 15g of sulfuric acid into a reaction kettle, heating to 60 ℃, pumping 2300g of hydrogen peroxide with the concentration of 30% into the reaction kettle for 6h, removing the rest formic acid and water in a distillation mode after the reaction is finished, cooling to room temperature, and washing with deionized water for three times to obtain the epoxy linoleic acid C.
Example 8: preparation of ester Compound C-1
180g of butanediol and 1.5g of p-toluenesulfonic acid catalyst are added into a 500mL three-neck glass flask, the flask is heated to 120 ℃, 156g of epoxy linoleic acid C is gradually dripped into the three-neck flask within 3h, the reaction is continued for 5h while maintaining at 120 ℃ after the dripping is finished, and excessive butanediol is removed by distillation. And washing the crude product with water to remove the catalyst and to be neutral to obtain the ester compound C-1.
Comparative example 4: preparation of ester Compound D-4
The preparation method of D-4 is the same as that of C-1 except that butanediol is replaced by butanol of the same mole, and the ester compound D-4 is obtained.
The ester compounds of examples and comparative examples were examined for their frictional wear properties, respectively, and the evaluation of the lubricating properties in diesel oil was carried out according to ISO12156-1 method using a High Frequency Reciprocating Rig (HFRR) and the evaluation of the sliding properties in lubricating oil was carried out according to SH/T0762 method of measuring the coefficient of friction of lubricating oil (four-ball method). The results are shown in Table 1.
TABLE 1
Sample (I)
Steel ball grinding spot diameter/mum
Average coefficient of friction
A-1
301
0.065
A-2
254
0.062
D-1
531
0.089
D-2
483
0.087
B-1
267
0.064
B-2
229
0.059
D-3
610
0.095
C-1
289
0.061
D-4
459
0.079
The above embodiments are only used to illustrate the technical solutions of the embodiments of the present disclosure, and not to limit them; although the present invention has been described in detail with reference to the foregoing embodiments, it will be understood by those of ordinary skill in the art that: the technical solutions described in the foregoing embodiments may still be modified, or some technical features may be equivalently replaced; and such modifications or substitutions do not depart from the spirit and scope of the corresponding technical solutions of the embodiments of the present disclosure.
- 上一篇：一种医用注射器针头装配设备
- 下一篇：酯类化合物及其制备方法、用途