CN108707074A - A method of preparing low acid value tricarboxymethyl propane oleate - Google Patents
A method of preparing low acid value tricarboxymethyl propane oleate Download PDFInfo
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- CN108707074A CN108707074A CN201810734595.1A CN201810734595A CN108707074A CN 108707074 A CN108707074 A CN 108707074A CN 201810734595 A CN201810734595 A CN 201810734595A CN 108707074 A CN108707074 A CN 108707074A
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- Prior art keywords
- trimethylolpropane
- acid
- small
- oleic acid
- reaction
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C67/00—Preparation of carboxylic acid esters
- C07C67/08—Preparation of carboxylic acid esters by reacting carboxylic acids or symmetrical anhydrides with the hydroxy or O-metal group of organic compounds
Abstract
The invention discloses a kind of methods preparing low acid value tricarboxymethyl propane oleate, it is characterised in that includes the following steps：The first step is less than 3 with trimethylolpropane molar ratio by oleic acid and oleic acid and trimethylolpropane is added, and is reacted under conditions of catalyst, water entrainer is added；Second step adds small-molecular-weight acid anhydrides, the complete hydroxyl of unreacted is all closed, obtain trimethylolpropane tris oleate and trimethylolpropane dioleate small carboxylic acid molecules' ester admixture, third step the reaction was complete postcooling is to room temperature, washing, organic layer in vacuo sloughs water entrainer, obtains pale yellowish oil transparency liquid tricarboxymethyl propane oleate.Esterification is divided into two steps by the present invention, and final step esterification uses small-molecular-weight carboxylic acid, can directly wash removing, and products obtained therefrom contains only a small amount of two oleic acid small molecule acid esters of trimethylolpropane, and acid value is less than 0.1mgKOH/g, and quality is far above same veriety in the market.
Description
Technical field
The present invention relates to fine organic chemical industry field, it is specifically related to a kind of preparing low acid value tricarboxymethyl propane oleate
Method.
Background technology
Tricarboxymethyl propane oleate biological degradation rate is high, is a kind of green ester lubricant, and excellent lubricating properties glue
Degree index is high, flash-point is high, hydrolytic stability is good, volatilization is low, low temperature flow is good.The trimethylolpropane oil of low acid value high-quality
Acid esters can be used for allocating synthesis ester type fire resistant hydraulic oil, environment-friendly type hydraulic oil and water ride engine oil.
There are two types of methods for the synthesis of trimethylolpropane tris oleate, the first is methyl oleate and trimethylolpropane
TMP transesterification (Xing Fenglan etc., finely and specialty chemicals, 2007,15 (18)：16-18 pages), be for second by TMP with
Oleic acid is obtained through esterification.Common second method, reaction are as follows：
In order to ensure TMP, the reaction was complete as far as possible, all uses oleic acid excessive in actual production.But excessive oleic acid removing is compared
Difficulty, cannot direct alkali cleaning because oleic acid can generate enuatrol when alkali cleaning, and enuatrol is strong emulsifier, may cause oil-water
It is not stratified, it is difficult to obtain qualified products.Sour in order to which excess oil is removed, someone did good try, such as Chinese invention patent
Apply for CN104387271A after obtaining tricarboxymethyl propane oleate crude product, the adsorption tower by being filled with adsorbent adsorbs de-
Except impurity such as organic acids.But have no the acid value data of final products.In Chinese patent ZL02111552.4, using soild oxide
It is catalyzed the esterification of oleic acid and trimethylolpropane, then high temperature, condition of high vacuum degree (20-100Pa) slough residual oleic acid, yield
92%, product acid value is not reported.Chinese patent CN104672085 B are using oleic acid and trimethylolpropane 3:1 molar ratio carries out
Reaction, final products acid value are higher than 0.8mgKOH/g, do not carry out depickling processing.The high trimethylolpropane tris oleate of acid value is only
It can be used for metal working fluid, cannot act as hydraulic oil, engine oil.
Tricarboxymethyl propane oleate product acid value currently on the market is typically greater than 1mgKOH/g, and some is even as high as
5~10 mgKOH/g.When doing lubricant product using the tricarboxymethyl propane oleate of high acid value, oil flash point reduces, and pour point carries
Height, quality decline naturally.The acid value of base oil is high, the performance of finished lube is directly affected, such as corrosivity, rust-preventing characteristic, oxidation
Stability and service life.Due to corroding metal, causes machinery lubrication system loss to accelerate, shorten mechanical service life.
The prior art indicate that trimethylolpropane tris oleic acid Lipase absobed and acid stripping method are it has been reported that but by anti-
The method that acid value should be obtained less than 0.1mgKOH/g products has no document report.
Invention content
The purpose of the present invention is to provide it is a kind of prepare low acid value, high-quality tricarboxymethyl propane oleate product side
Method.
The technical solution adopted by the present invention is：A method of preparing low acid value tricarboxymethyl propane oleate, feature
It is to include the following steps：The first step is less than 3 with trimethylolpropane molar ratio by oleic acid and oleic acid and trimethylolpropane is added,
It is reacted under conditions of catalyst, water entrainer is added；Second step adds small-molecular-weight acid anhydrides, by the complete hydroxyl of unreacted
Base is all closed, and trimethylolpropane tris oleate and trimethylolpropane dioleate small carboxylic acid molecules' ester admixture are obtained,
The wherein molal quantity of oleic acid and small molecule acid anhydrides and the molal quantity more than or equal to trimethylolpropane；Third step is after the reaction was complete
It is cooled to room temperature, washes, organic layer in vacuo sloughs water entrainer, obtains pale yellowish oil transparency liquid trimethylolpropane oleic acid
Ester.
Small-molecular-weight acid anhydrides of the present invention are the mixture of any one or more in acetic anhydride, propionic andydride, butyric anhydride.
The molar ratio of oleic acid and trimethylolpropane is 2.90 ~ 2.95 in the present invention：1, small molecule acid anhydrides and trihydroxy methyl
The molar ratio of propane is 0.1 ~ 0.05.
The reaction condition of the first step of the present invention is：Catalyst is p-methyl benzenesulfonic acid, and water entrainer is petroleum ether, and heating temperature is
110-140 DEG C, preferably 130-135 DEG C, reaction time are 2.0-6.0 hours, preferably 3.0h；The reaction condition of second step
It is：Reaction temperature is 30 ~ 70 DEG C, and preferably 55-60 DEG C, the reaction time is 0.5-2.0 hours, preferably 1.0h.
Esterification in the present invention is that following two step is divided to carry out：
The first step：Since the molar ratio of oleic acid and trimethylolpropane is less than 3, oleic acid and trimethylolpropane is added, it is main raw
At trimethylolpropane tris oleate, trimethylolpropane dioleate, since hydroxyl is excessive, oleic acid energy in this step
React relatively more complete, chemical equation is as follows：
。
Second step：Small molecule acid anhydrides is added, remaining hydroxyl in trimethylolpropane dioleate molecule is closed, it is raw
At two oleic acid small molecule acid esters of trimethylolpropane, and small molecule acid anhydrides is strong acylating agent, can be with quantitative reaction, and chemistry is anti-
Answer formula as follows：
。
After the above two-step reaction, oleic acid fundamental reaction is complete, and hydroxyl is also closed, and by-product is a small amount of small molecule
Quantity carboxylic acid, and since small-molecular-weight carboxylic acid is water-soluble, can directly be removed by washing, can very easily obtain low acid
The tricarboxymethyl propane oleate product of value.When such as using acetic anhydride, two oleic acid acetate content of trimethylolpropane is about
3.85%-7.79%, remaining is trimethylolpropane tris oleate.
The biological degradability of the tricarboxymethyl propane oleate product obtained using the method for the present invention is unaffected, and is glued
Though degree is declined slightly, viscosity index (VI) is basically unchanged, and greasy property is constant, may also used to allotment synthesis ester type fire-resistant hydraulic pressure
The lube products such as oil, aviation engine lubricating oil and water ride engine oil.
Esterification is divided into two steps by the present invention, and final step esterification generates small molecular by product quantity carboxylic acid, can directly wash and remove
It goes, products obtained therefrom contains only a small amount of two oleic acid acetic acid esters of trimethylolpropane, and acid value is less than 0.1mgKOH/g, and quality is far above city
Same veriety on field, while material performance of the present invention is stable, cheap and easy to get, it is easy to operate, it is industrial easy to implement.
Specific implementation mode
Below according to specific implementation mode, the invention will be further described：
Embodiment 1：
67.1g (0.5mol) trimethylolpropane, the oleic acid of 409.6g (1.45mol) are successively added in the reactor, addition is urged
Agent p-methyl benzenesulfonic acid, water entrainer petroleum ether, 130-135 DEG C of control oil bath heating temperature under nitrogen protection, are stirred at reflux, point
Water 3.0 ~ 4.0 hours, it is cooling, then add 5.1g acetic anhydrides (0.05mol), oil bath is warming up to 55 ~ 60 DEG C, is stirred to react 1 hour.Instead
It answers complete postcooling to room temperature, washes, organic layer in vacuo sloughs water entrainer, obtains pale yellowish oil transparency liquid, acid value
0.06mgKOH/g, yield 99%.
Embodiment 2：
67.1g (0.5mol) trimethylolpropane, the oleic acid of 409.6g (1.45mol) are successively added in the reactor, addition is urged
Agent p-methyl benzenesulfonic acid, water entrainer petroleum ether, 130-135 DEG C of control oil bath heating temperature under nitrogen protection, are stirred at reflux, point
Water 3.0 ~ 4.0 hours, it is cooling, then add 6.5g propionic andydrides (0.05mol), oil bath is warming up to 55 ~ 60 DEG C, is stirred to react 1 hour.Instead
It answers complete postcooling to room temperature, washes, organic layer in vacuo sloughs water entrainer, obtains pale yellowish oil transparency liquid, acid value
0.07mgKOH/g, yield 99%.
Embodiment 3：
67.1g (0.5mol) trimethylolpropane is successively added in the reactor, the oleic acid of 416.6g (1.475mol) is added
Catalyst p-methyl benzenesulfonic acid, water entrainer petroleum ether, 130-135 DEG C of control oil bath heating temperature under nitrogen protection, are stirred at reflux,
Divide water 3.0 ~ 4.0 hours, it is cooling, then add 4.0g acetic anhydrides (0.025mol), oil bath is warming up to 55 ~ 60 DEG C, it is small to be stirred to react 1
When.Postcooling that the reaction was complete to room temperature, washing, organic layer in vacuo sloughs water entrainer, obtains pale yellowish oil transparency liquid, acid value
0.08mgKOH/g, yield 99%.
Embodiment of the present invention is not only the description carried out to the preferred embodiment of the present invention, not to this hair
Bright conception and scope is defined, and under the premise of not departing from design philosophy of the present invention, engineers and technicians are to this in this field
The all variations and modifications that the technical solution of invention is made, should all fall into protection scope of the present invention, and the present invention is claimed
Technology contents have all been recorded in detail in the claims.
Claims (5)
1. a kind of method preparing low acid value tricarboxymethyl propane oleate, it is characterised in that include the following steps：The first step is pressed
Oleic acid is less than 3 with trimethylolpropane molar ratio and oleic acid and trimethylolpropane is added, in the condition that catalyst, water entrainer is added
Under reacted；Second step adds small-molecular-weight acid anhydrides, and the complete hydroxyl of unreacted is all closed, trihydroxy methyl third is obtained
Alkane trioleate and trimethylolpropane dioleate small carboxylic acid molecules' ester admixture, wherein mole of oleic acid and small molecule acid anhydrides
Molal quantity several and more than or equal to trimethylolpropane；Third step the reaction was complete postcooling is to room temperature, washing, organic layer in vacuo
Water entrainer is sloughed, pale yellowish oil transparency liquid tricarboxymethyl propane oleate is obtained.
2. according to the method described in claim 1, it is characterized in that：The small-molecular-weight acid anhydrides are acetic anhydride, propionic andydride, butyric acid
The mixture of any one or more in acid anhydride, isobutyric anhydride.
3. according to the method described in claim 1, it is characterized in that：The molar ratio of oleic acid and trimethylolpropane be 2.90 ~
2.95：1, the molar ratio of small molecule acid anhydrides and trimethylolpropane is 0.1 ~ 0.05.
4. according to the method described in claim 1, it is characterized in that：The reaction condition of the first step is：Catalyst is to toluene sulphur
Acid, water entrainer are petroleum ether, and heating temperature is 110-140 DEG C, and the reaction time is 2.0-6.0 hours；Second step reaction temperature is
30 ~ 70 DEG C, the reaction time is 0.5-2.0 hours.
5. according to the method described in claim 4, it is characterized in that：First step heating temperature is 130-135 DEG C, and the reaction time is
3.0h；Second step reaction temperature is 55-60 DEG C, reaction time 1.0h.
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| Application Number | Priority Date | Filing Date | Title |
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| CN201810734595.1A CN108707074A (en) | 2018-07-06 | 2018-07-06 | A method of preparing low acid value tricarboxymethyl propane oleate |
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| CN201810734595.1A CN108707074A (en) | 2018-07-06 | 2018-07-06 | A method of preparing low acid value tricarboxymethyl propane oleate |
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2023189293A1 (en) * | 2022-03-31 | 2023-10-05 | Ｅｎｅｏｓ株式会社 | Base oil for lubricating oil, lubricating oil and working fluid |
Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US20090305922A1 (en) * | 2008-06-09 | 2009-12-10 | Hyundai Motor Company | Lubricating oil composition for automobile transmission and lubricating method using same |
| CN103159625A (en) * | 2011-12-08 | 2013-06-19 | 沈阳工业大学 | Method of producing trimethylolpropane oleate with single kettle |
| CN104945247A (en) * | 2015-06-30 | 2015-09-30 | 百川化工(如皋)有限公司 | Preparation process of neopentyl polyol oleate |
| CN105189441A (en) * | 2013-02-28 | 2015-12-23 | 马来西亚国家石油公司 | The preparation of biopolyol esters for lubricant application |
-
2018
- 2018-07-06 CN CN201810734595.1A patent/CN108707074A/en active Pending
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US20090305922A1 (en) * | 2008-06-09 | 2009-12-10 | Hyundai Motor Company | Lubricating oil composition for automobile transmission and lubricating method using same |
| CN103159625A (en) * | 2011-12-08 | 2013-06-19 | 沈阳工业大学 | Method of producing trimethylolpropane oleate with single kettle |
| CN105189441A (en) * | 2013-02-28 | 2015-12-23 | 马来西亚国家石油公司 | The preparation of biopolyol esters for lubricant application |
| CN104945247A (en) * | 2015-06-30 | 2015-09-30 | 百川化工(如皋)有限公司 | Preparation process of neopentyl polyol oleate |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2023189293A1 (en) * | 2022-03-31 | 2023-10-05 | Ｅｎｅｏｓ株式会社 | Base oil for lubricating oil, lubricating oil and working fluid |
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