CN105294432A - Method for synthesizing ethylene glycol distearate in absence of solvent at ordinary pressure - Google Patents
Method for synthesizing ethylene glycol distearate in absence of solvent at ordinary pressure Download PDFInfo
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- CN105294432A CN105294432A CN201510593608.4A CN201510593608A CN105294432A CN 105294432 A CN105294432 A CN 105294432A CN 201510593608 A CN201510593608 A CN 201510593608A CN 105294432 A CN105294432 A CN 105294432A
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- ethylene glycol
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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
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Abstract
The invention discloses a method for synthesizing ethylene glycol distearate in the absence of a solvent at ordinary pressure. In the presence of a solid acidic catalyst, the ethylene glycol distearate is prepared under certain technological conditions with ethylene glycol and stearic acid as raw materials. According to the method disclosed by the invention, the ethylene glycol distearate product can be synthesized at high efficiency in the absence of the solvent at ordinary pressure, wherein the acid value of the product can be less than 5 at least, and the acid conversion rate of the product can reach over 97%. The method disclosed by the invention is simple and highly-efficient, convenient and feasible to operate, safe and environment-friendly, and free of toxicity pollution and recovery problem of the solvent and has better generalization and application value.
Description
Technical field
The present invention relates to a kind of method of solvent-free normal pressure synthesis ethylene glycol stearate.
Background technology
Ethylene glycol stearate is a kind of nonionogenic tenside, the up-and-coming youngster of progressively commercial tensio-active agent kind, it not only has the features such as surfactivity is high, nontoxic, non-stimulated, use safety, again due to its low foaming and high emulsibility, commonly use and do emulsifying agent, dispersion agent, solubilizing agent, lubricant, softening agent, defoamer, static inhibitor, pearling agent etc.Be used widely in daily-use chemical industry, metal, fiber process and various emulsion class makeup, washing composition, drug manufacture.
Current production technique both domestic and external is that raw material sulphuric acid catalysis esterification process produces ethylene glycol stearate mainly with stearic acid or lipid acid and ethylene glycol greatly.The method product color is easily partially dark, and equipment corrosion is serious, and aftertreatment is complicated, produces a large amount of waste liquor contamination environment simultaneously, thus seeks new synthetic technology and day by day receive publicity and attention.In recent years, along with to ethylene glycol stearate progress of research, many new synthesis techniques and new catalyst have been there is, such as, have and adopt tosic acid to be the catalyzer of this reaction, adopt higher vacuum, reaction times is 6 hours, and the stearic acid transformation efficiency of the product obtained is up to 98%; Have and adopt silicotungstic acid as esterifying catalyst, dewatering agent made by toluene. during reaction times 6h, the light base transformation efficiency of alcohol of obtained product is all greater than 98%; Have and adopt metal oxide to be catalyzer, reaction times is 4 hours, under these processing condition, stearic transformation efficiency reaches 99.98% etc., these methods respectively have himself feature, their exploitation, make ethylene glycol stearate synthetic technology obtain significant progress, allow this technology more trend towards simply, efficient, environmental protection.But above-mentioned synthetic technology is Shortcomings part also, and the reaction times is oversize, there is impact in various degree to the colourity of product; Adopt the organic solvents such as toluene to do water entrainer, have disadvantageous effect to environment, there is certain environmental pollution and cost recovery problem; Adopt silicotungstic acid to make catalyzer, cost is higher, brings larger pressure to applying of product; Employing high vacuum is synthesized, and production energy consumption is increased, and product cost improves, and also will affect applying of product.
Summary of the invention
Technical advance of the present invention is to provide a kind of without water entrainer, the method preparing ethylene glycol stearate without the need to vacuum or pressurization, efficient building-up reactions, and to avoid the weak point of above-mentioned technology, more environmental protection is safer more efficient to make its building-up process.
The present invention's taked technical scheme that solves the problem is: without water entrainer high-efficiency synthesis of ethylene glycol stearate, its method is:
1. a method for solvent-free normal pressure synthesis ethylene glycol stearate, is characterized in that:
A takes quantitative stearic acid in proportion, ethylene glycol is placed in reactor, and then adds catalyzer;
B heats this reactor, makes reaction mass insulation reaction 2 to 4 hours at 230 ~ 260 DEG C of temperature;
The acid number of c sampling and measuring sample, according to its acid number of GB/T9104-2008 standard test (mgKOH/g); Get Product samples analysis: scales/electronic balance weighing, according to its acid number of GB/T9104-2008 standard test (mgKOH/g), being calculated as follows its transformation efficiency (Q) is:
；
D, when the acid number of sample is at below 6mgKOH/g, gets final product stopped reaction, filters and obtains product ethylene glycol stearate.
Heating means of the present invention are: the reacting by heating that is rapidly heated material, make its actual temperature 230 DEG C and more than;
Heating temperature of the present invention is: reacting by heating material actual temperature, at 230 ~ 260 DEG C, is advisable to be no more than 260 DEG C, otherwise is easily caused material coloured product to deepen;
Reaction times of the present invention is: the reaction times should not be too short, should control in 2 to 4 hours window, otherwise the reaction times is inadequate, and product acid number is higher, and remaining acid is more, affects quality product; Reaction times is long, easily produces oxidation side reaction, causes product color to be deepened;
The optional technical grade stearic acid of starting material stearic acid of the present invention or AG stearic acid;
The optional technical grade ethylene glycol of starting material ethylene glycol of the present invention or AG ethylene glycol;
Catalyzer of the present invention is solid acid catalyst;
Catalyst levels of the present invention is: 1% ~ 5%(is with stearic acid weighing scale);
Proportion of raw material of the present invention is: the mol ratio of stearic acid and ethylene glycol is 1:0.5 ~ 0.9;
The acid number of the product that this synthetic method of employing of the present invention obtains is close to below 5 or 5, and its sour transformation efficiency can reach more than 97%.
The present invention compared with prior art, has the following advantages and effect:
Without the need to adding water entrainer, avoiding the problem such as toxicity, environmental pollution, cost recovery that organic solvent brings, simplifying technological process, make building-up reactions more convenient operation feasible;
Adopt silica gel load high-performance solid acid catalyst, make esterification comparatively complete, the sour transformation efficiency of product is high, can synthesize and obtain high-quality ethylene glycol stearate;
Without the need to vacuumizing or the reaction of logical nitrogen pressurization, not increasing the peroxide value of product, there is no sulphur and heavy metal contamination, running cost is low, without refining consumption, safety environment protecting energy saving.
Synthesis technique of the present invention is simple, and starting material are the common stable chemical industry material on market, without starting material problem in short supply;
Technology provided by the present invention is not only applicable to ethylene glycol stearate, also be applicable to the serial glycol fatty acid dibasic acid esters such as ethylene glycol lauric acid dibasic acid esters, ethylene glycol palmitinic acid dibasic acid esters, ethylene glycol eicosanoic acid dibasic acid esters, ethylene glycol behenic acid dibasic acid esters, have broad application prospects.
Embodiment
Be described in further details solvent-free non-pressure process synthesizing glycol stearate technology by following examples, following examples are explanation of the invention and the present invention is not limited to following examples.
Embodiment 1:
Stearic acid 142g
Ethylene glycol 23.3g
Solid acid catalyst 2.13g
Temperature of reaction 230 ~ 260 DEG C
Reaction times 3hr
Product acid number 4.33mgKOH/g
Product acid transformation efficiency 99.38%.
Embodiment 2:
Stearic acid 298g
Ethylene glycol 48.8g
Solid acid catalyst 2.4g
Temperature of reaction 260 ~ 268 DEG C
Reaction times 2.5hr
Product acid number 5.31mgKOH/g
Product acid transformation efficiency 97.42%.
Embodiment 3:
Stearic acid 284g
Ethylene glycol 46.5g
Solid acid catalyst 4.3g
Temperature of reaction 230 ~ 260 DEG C
Reaction times 2.5hr
Product acid number 5.72mgKOH/g
Product acid transformation efficiency 97.22%.
Above-described embodiment operating process is as follows:
Take quantitative stearic acid in proportion, ethylene glycol, solid acid catalyst equals in 1000ml four-hole boiling flask reactor, and this flask is placed in heating jacket;
The outlet of four, this flask connects reflux condensing tube, glass-stem thermometer sleeve pipe, water trap, straight-adjustable siphunculus etc. respectively;
Heat this reactor, setting initial heating temperature is 230 DEG C, and visual response situation regulates temperature of reaction;
Insulation reaction 4 hours at 230 ~ 260 DEG C of temperature;
The acid number of sampling and measuring sample, according to its acid number of GB/T9104-2008 standard test (mgKOH/g);
For ethylene glycol stearate, when the acid number of sample is at below 5mgKOH/g, get final product stopped reaction, filter and obtain product;
Get Product samples analysis: scales/electronic balance weighing, according to its acid number of GB/T9104-2008 standard test (mgKOH/g), be calculated as follows its turn
Rate (Q) is:
。
Claims (7)
1. a method for solvent-free normal pressure synthesis ethylene glycol stearate, is characterized in that:
A takes quantitative stearic acid in proportion, ethylene glycol is placed in reactor, and then adds catalyzer;
B heats this reactor, makes reaction mass insulation reaction 2 to 4 hours at 230 ~ 260 DEG C of temperature;
The acid number of c sampling and measuring sample, according to its acid number of GB/T9104-2008 standard test (mgKOH/g); Get Product samples analysis: scales/electronic balance weighing, according to its acid number of GB/T9104-2008 standard test (mgKOH/g), being calculated as follows its transformation efficiency (Q) is:
；
D, when the acid number of sample is at below 6mgKOH/g, gets final product stopped reaction, filters and obtains product ethylene glycol stearate.
2. method according to claim 1, is characterized in that: in described step a, the mol ratio of stearic acid and ethylene glycol is 1:0.5 ~ 1:0.9.
3. method according to claim 1, is characterized in that: described stearic acid comprises technical grade stearic acid and AG stearic acid.
4. method according to claim 1, is characterized in that: described ethylene glycol comprises technical grade ethylene glycol and AG ethylene glycol.
5. method according to claim 1, is characterized in that: in described step a, catalyst levels is with stearic acid weighing scale, is 1% ~ 5%.
6. method according to claim 1 or 5, is characterized in that: described catalyzer is solid acid catalyst.
7. method according to claim 1, is characterized in that: the acid number of the product adopting this synthetic method to obtain is close to below 5 or 5, and its sour transformation efficiency can reach more than 97%.
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| Application Number | Priority Date | Filing Date | Title |
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| CN201510593608.4A CN105294432A (en) | 2015-09-18 | 2015-09-18 | Method for synthesizing ethylene glycol distearate in absence of solvent at ordinary pressure |
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| Application Number | Priority Date | Filing Date | Title |
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| CN201510593608.4A CN105294432A (en) | 2015-09-18 | 2015-09-18 | Method for synthesizing ethylene glycol distearate in absence of solvent at ordinary pressure |
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Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| RO109731B1 (en) * | 1994-05-19 | 1995-05-30 | Scinstitutul De Cercetari Pent | Ethylenglycole distearate preparation process |
| JP2001329291A (en) * | 2000-05-23 | 2001-11-27 | Maruha Corp | Process for preparing polyalcohol fatty acid ester |
| CN102311338A (en) * | 2011-08-25 | 2012-01-11 | 四川泸天化股份有限公司 | Method for high-efficiency synthesis of ethylene glycol mono stearate |
| CN103880658A (en) * | 2014-03-13 | 2014-06-25 | 四川泸天化股份有限公司 | Direct esterification synthesis method of pentaerythritol oleate |
| CN104045554A (en) * | 2014-07-09 | 2014-09-17 | 江苏天音化工有限公司 | Method for preparing ethylene glycol diacetate |
-
2015
- 2015-09-18 CN CN201510593608.4A patent/CN105294432A/en active Pending
Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| RO109731B1 (en) * | 1994-05-19 | 1995-05-30 | Scinstitutul De Cercetari Pent | Ethylenglycole distearate preparation process |
| JP2001329291A (en) * | 2000-05-23 | 2001-11-27 | Maruha Corp | Process for preparing polyalcohol fatty acid ester |
| CN102311338A (en) * | 2011-08-25 | 2012-01-11 | 四川泸天化股份有限公司 | Method for high-efficiency synthesis of ethylene glycol mono stearate |
| CN103880658A (en) * | 2014-03-13 | 2014-06-25 | 四川泸天化股份有限公司 | Direct esterification synthesis method of pentaerythritol oleate |
| CN104045554A (en) * | 2014-07-09 | 2014-09-17 | 江苏天音化工有限公司 | Method for preparing ethylene glycol diacetate |
Non-Patent Citations (4)
| Title |
|---|
| 傅挺进: "乙二醇硬脂酸酯的合成探讨", 《四川化工》 * |
| 傅挺进: "乙二醇硬脂酸酯的合成研究", 《泸天化科技》 * |
| 汪碧容 等: "乙二醇硬脂酸酯合成技术进展", 《泸天化科技》 * |
| 解田 等: "乙二醇硬脂酸酯的合成新工艺研究", 《广西工业》 * |
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