CN101747192B - Method for synthesizing polyethylene glycol (PEG) oleate - Google Patents
Method for synthesizing polyethylene glycol (PEG) oleate Download PDFInfo
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Abstract
The invention discloses a method for synthesizing polyethylene glycol (PEG) oleate, comprising the following steps: making PEG and oleate which are used as raw materials carry out esterification reaction at 100-150 DEG C for 2-6h under the action of organic acid catalyst by controlling the vacuum degree at -0.098 Mpa or higher; after the PEG and the oleate finishing reaction, neutralizing the product of reaction with triethanolamine until the pH value of the product of reaction being 5-7; and filtering the product of reaction to obtain solution which is PEG oleate. The organic acid catalyst is dodecyl benzene sulfonic acid, and the addition amount of the organic acid catalyst is 0.3-1.0 percent of the total mass of the PEG and the oleate. The invention has the advantages that the source of the organic acid catalyst is wide, the price of the organic acid catalyst is low, the reaction condition is mild, the method for synthesizing the PEG oleate omits the washing process and the dewatering process, hardly pollutes the environment, is simple, is convenient to operate, ensures high conversion rate and overcomes the defects that the byproducts of reaction are more and have deep color and the PEG oleate has stable quality and outstanding emulsifying, wetting and solubilizing properties.
Description
Technical field
The present invention relates to a kind of synthetic method of polyethylene glycol (PEG) oleate, belong to the synthesis technical field of ester compound in the organic chemistry.
Background technology
Polyethylene glycol (PEG) oleate is a kind of multi-functional nonionogenic tenside that has than high emulsibility, wettability and lyotropy, comprises monoesters and dibasic acid esters.Because it possesses wide HLB value, high reactivity, high waterproof, hypotoxicity, low whipability, to functional performances such as mineral strong detergencies, its use range is particularly extensive.Can be used as static inhibitor, softening agent, levelling agent and smooth agent in textile industry uses; Can be used as the elimination detergent of metallic substance, fabric, fiber, electron device, precision mechanical part etc. in the washing industry; Can be used as solubilizing agent, emulsifying agent, whipping agent and wetting Agent for Printing Inks at cosmetic industry uses; Can be used as heavy oil combustion supporting agent, sanitas, rust remover and lubricating oil additive in petrochemical processing industry uses.In a word, its prospects for commercial application is wide, has great product development value.
The synthetic vitriol oil or the tosic acid of adopting of traditional ester class is as catalyzer.As catalyzer, although reactive behavior is high, its corrodibility and oxidisability are excessively strong with the vitriol oil, byproduct of reaction is many, and product colour is dark, has affected the use value of product, and products made thereby need pass through the operations such as washing, dehydration, has increased production cost and environmental pollution.Although it is relatively gentle to make the catalyzer reaction conditions with tosic acid, needs equally the operations such as washing, dehydration, and partially catalyzed agent meeting remains in the product and affects use properties and the stability of product.At present, academia has developed the method for utilizing solid super-strong acid to come the synthesizing polyethylene glycol oleic acid ester as catalyzer.Such as work " SO such as Luo Xiaomin
4 2-/ ZrO
2Catalyze and synthesize oleic acid polyoxyethylene glycol monoesters "; (" daily chemical industry " 2008); the method drops into reaction flask with polyoxyethylene glycol, oleic acid and catalyzer; rotary heating; decompression minute water reacts to acid number and no longer descends, behind the cold filtration product, this technique environmental protection, simple to operate; but solid acid catalyst preparation technology is loaded down with trivial details, temperature of reaction is higher.
The work such as bandit's show sweet smell " influence factor of lipase synthesis poly(oxyethylene glycol) 400 oleic acid monoester and dibasic acid esters " (" biotechnology journal " 1999) and for example, bibliographical information utilize lipase to come the method for synthesizing polyethylene glycol oleic acid ester as catalyzer.Utilize lipase as catalyzer, in Erlenmeyer flask, drop into oleic acid, PEG400 and immobilized lipase, get product behind 40 ℃ of lower oscillatory reaction certain hours, this technique environmental protection, reaction temperature and, but condition control is strict, and the reaction times is long, and productive rate is on the low side, and lipase-catalyzed dose expensive, and commercial application also need be done more deep research.
Summary of the invention
For above-mentioned situation, the problem that quasi-solution of the present invention is determined provides a kind of synthetic method of high-quality polyethylene glycol (PEG) oleate, and it has, and technique is simple, environmental protection, the advantage such as easy to operate.
For achieving the above object, the present invention is by the following technical solutions: a kind of synthetic method of polyethylene glycol (PEG) oleate, it is take polyoxyethylene glycol (PEG) and oleic acid as raw material, under the effect of organic acid catalyst, carry out esterification, react complete after, being neutralized to pH with trolamine is 5-7 (be generally PEG and oleic acid raw materials quality and 0.2～0.25%), the solution that gets after the filtration is product polyethylene glycol (PEG) oleate of the present invention, described organic acid catalyst is Witco 1298 Soft Acid, and described Witco 1298 Soft Acid add-on is 0.3～1.0% of polyoxyethylene glycol and oleic acid total mass; The temperature of reaction of described esterification is 100～150 ℃, and the reaction times is 2～6 hours, vacuum tightness is 〉=-0.098MPa.
The synthetic method of above-mentioned polyethylene glycol (PEG) oleate, described synthetic polyethylene glycol (PEG) oleate can be the polyoxyethylene glycol oleic acid monoester, the mol ratio of polyoxyethylene glycol and oleic acid is in the described esterification: 1: 0.95～1.1.Described synthetic polyethylene glycol (PEG) oleate also can be the polyoxyethylene glycol Glycol Oleic Acid Ester, and the mol ratio of polyoxyethylene glycol and oleic acid is in the described esterification: 1: 1.9～2.0.
The molecular weight of described polyoxyethylene glycol is 400～1000.
Because Witco 1298 Soft Acid (DBSA) is a kind of wide material sources, have more highly acid bronsted acid catalyst, directly catalytic esterification.In addition, it or the comparatively superior tensio-active agent of a kind of performance can make esterification System forming reverse micro emulsion system, increase the touch opportunity between reactant, thereby improve esterification efficient and productive rate.Therefore the present invention compared with prior art has following outstanding advantages and positively effect:
The one, catalyst system therefor Witco 1298 Soft Acid wide material sources, cheap react complete rear only the need with an amount of trolamine neutralization, and the salt of generation can be removed after filtration, has saved washing and dehydration procedure, favourable and environment protection.The 2nd, utilize Witco 1298 Soft Acid to make catalyst to synthesize ethylene glycol oleic acid ester, reaction conditions is gentle, technique is simple, easy to operate, pollute less, transformation efficiency is high, has avoided making the defective that the product by product is many, color and luster is dark with strong oxidizing property materials such as the vitriol oils as catalyzer.The 3rd, by the polyethylene glycol (PEG) oleate steady quality that the present invention synthesizes, emulsification, wetting and characteristic of solubilizing are outstanding, can be widely used in weaving, makeup, refining of petroleum and washing industry.In sum, the synthetic method of polyethylene glycol (PEG) oleate of the present invention have that technique is simple, environmental protection, the advantage such as easy to operate.And the polyethylene glycol (PEG) oleate by product that makes is few, quality is high.
Embodiment
The synthetic method of polyethylene glycol (PEG) oleate of the present invention, it is take polyoxyethylene glycol and oleic acid as raw material, under the effect of organic acid catalyst Witco 1298 Soft Acid, carry out esterification, react complete after, being neutralized to pH with trolamine is 5-7 (be generally PEG and oleic acid raw materials quality and 0.2～0.25%), the solution that gets after the filtration is product polyethylene glycol (PEG) oleate of the present invention, and the mol ratio of described polyoxyethylene glycol and oleic acid is: monoesters 1: 0.95～1.1, dibasic acid esters 1: 1.9～2.0; Described Witco 1298 Soft Acid add-on is 0.3～1.0% of polyoxyethylene glycol and oleic acid total mass; The temperature of reaction of described esterification is 100～150 ℃, and the reaction times is 2～6 hours, vacuum tightness is 〉=-0.098MPa.The molecular weight of described polyoxyethylene glycol is 400～1000.
Described esterification equation is:
Monoesters:
Dibasic acid esters:
Annotate: n is that 9～22, RCOOH is oleic acid in the formula.
Embodiment 1
In the reactor of 1000ml, add successively 400gPEG400,310.2g oleic acid, 2.2gDBSA vacuumizes, slowly be warming up to 100～115 ℃ after opening stirring, vacuum tightness 〉=-0.098MPa, and under this temperature and vacuum condition, react, distillate the water that reaction generates, anhydrous distillating behind the reaction 2.0h, with an amount of trolamine neutralization, get after filtering product P E6400 oleic acid monoester after being cooled to 60 ℃, the esterification yield of oleic acid reaches 99.1%.
Embodiment 2
In the reactor of 1000ml, add successively 300gPEG400,423g oleic acid, 2.9gDBSA vacuumizes, slowly be warming up to 110～125 ℃ after opening stirring, vacuum tightness 〉=-0.098MPa, and under this temperature and vacuum condition, react, distillate the water that reaction generates, anhydrous distillating behind the reaction 3.0h, with an amount of trolamine neutralization, get after filtering product P EG400 Glycol Oleic Acid Ester after being cooled to 60 ℃, the esterification yield of oleic acid reaches 98.5%.
Embodiment 3
In the reactor of 1000ml, add successively 450gPEG600,211.5g oleic acid, 3.3gDBSA vacuumizes, slowly be warming up to 110～120 ℃ after opening stirring, vacuum tightness 〉=-0.098MPa, and under this temperature and vacuum condition, react, distillate the water that reaction generates, anhydrous distillating behind the reaction 3.5h, with an amount of trolamine neutralization, get after filtering product P EG600 oleic acid monoester after being cooled to 60 ℃, the esterification yield of oleic acid reaches 98.6%.
Embodiment 4
In the reactor of 1000ml, add successively 350gPEG600,320.8g oleic acid, 4.0gDBSA vacuumizes, slowly be warming up to 115～130 ℃ after opening stirring, vacuum tightness 〉=-0.098MPa, and under this temperature and vacuum condition, react, distillate the water that reaction generates, anhydrous distillating behind the reaction 4.0h, with an amount of trolamine neutralization, get after filtering product P EG600 Glycol Oleic Acid Ester after being cooled to 60 ℃, the esterification yield of oleic acid reaches 98.0%.
Embodiment 5
In the reactor of 1000ml, add successively 500gPEG800,167.4g oleic acid, 4.6gDBSA vacuumizes, slowly be warming up to 125～140 ℃ after opening stirring, vacuum tightness 〉=-0.098MPa, and under this temperature and vacuum condition, react, distillate the water that reaction generates, anhydrous distillating behind the reaction 4.5h, with an amount of trolamine neutralization, get after filtering product P EG800 oleic acid monoester after being cooled to 60 ℃, the esterification yield of oleic acid reaches 98.2%.
Embodiment 6
In the reactor of 1000ml, add successively 400gPEG800,267.9g oleic acid, 5.3gDBSA vacuumizes, slowly be warming up to 125～140 ℃ after opening stirring, vacuum tightness 〉=-0.098MPa, and under this temperature and vacuum condition, react, distillate the water that reaction generates, anhydrous distillating behind the reaction 5.0h, with an amount of trolamine neutralization, get after filtering product P EG800 Glycol Oleic Acid Ester after being cooled to 60 ℃, the esterification yield of oleic acid reaches 97.5%.
Embodiment 7
In the reactor of 1000ml, add successively 500gPEG1000,140g oleic acid, 5.8gDBSA vacuumizes, slowly be warming up to 130～145 ℃ after opening stirring, vacuum tightness 〉=-0.098MPa, and under this temperature and vacuum condition, react, distillate the water that reaction generates, anhydrous distillating behind the reaction 5.5h, with an amount of trolamine neutralization, get after filtering product P EG1000 oleic acid monoester after being cooled to 60 ℃, the esterification yield of oleic acid reaches 97.3%.
Embodiment 8
In the reactor of 1000ml, add successively 500gPEG1000,268g oleic acid, 7.7gDBSA vacuumizes, slowly be warming up to 140～150 ℃ after opening stirring, vacuum tightness 〉=-0.098MPa, and under this temperature and vacuum condition, react, distillate the water that reaction generates, anhydrous distillating behind the reaction 6.0h, with an amount of trolamine neutralization, get after filtering product P EG1000 Glycol Oleic Acid Ester after being cooled to 60 ℃, the esterification yield of oleic acid reaches 97.0%.
Following table is the various embodiments described above reaction conditions summary sheet
| Embodiment | PEG quality (g) | Oleic acid quality (g) | PEG: oleic acid (mole) | Single (two) ester | DBSA quality (g) | The DBSA mass ratio | Temperature (℃) | Time (hr) |
| 1 | 400 | 310.2 | 1∶1.1 | Monoesters | 2.2 | 0.31％ | 100～115 | 2.0 |
| 2 | 300 | 423.0 | 1∶2.0 | Dibasic acid esters | 2.9 | 0.40％ | 110～125 | 3.0 |
| 3 | 450 | 211.5 | 1∶1.0 | Monoesters | 3.3 | 0.50％ | 110～120 | 3.5 |
| 4 | 350 | 320.0 | 1∶1.95 | Dibasic acid esters | 4.0 | 0.60％ | 115～130 | 4.0 |
| 5 | 500 | 167.4 | 1∶0.95 | Monoesters | 4.6 | 0.69％ | 125～140 | 4.5 |
| 6 | 400 | 267.9 | 1∶1.9 | Dibasic acid esters | 5.3 | 0.79％ | 125～140 | 5.0 |
| 7 | 500 | 140.0 | 1∶1.0 | Monoesters | 5.8 | 0.91％ | 130～145 | 5.5 |
| 8 | 500 | 268.0 | 1∶1.9 | Dibasic acid esters | 7.7 | 1.00％ | 140～150 | 6.0 |
Claims (4)
1. the synthetic method of a polyethylene glycol (PEG) oleate, it is take polyoxyethylene glycol and oleic acid as raw material, under the effect of organic acid catalyst, carry out esterification, react complete after, being neutralized to pH with trolamine is 5-7, the solution that gets after the filtration is the product polyethylene glycol (PEG) oleate, it is characterized in that described organic acid catalyst is Witco 1298 Soft Acid, and described Witco 1298 Soft Acid add-on is 0.3～1.0% of polyoxyethylene glycol and oleic acid total mass; The temperature of reaction of described esterification is 100～150 ℃, and the reaction times is 2～6 hours, vacuum tightness is 〉=-0.098MPa.
2. the synthetic method of polyethylene glycol (PEG) oleate according to claim 1 is characterized in that described synthetic polyethylene glycol (PEG) oleate is the polyoxyethylene glycol oleic acid monoester, and the mol ratio of described polyoxyethylene glycol and oleic acid is: 1: 0.95～1.1.
3. the synthetic method of polyethylene glycol (PEG) oleate according to claim 1 is characterized in that described synthetic polyethylene glycol (PEG) oleate is the polyoxyethylene glycol Glycol Oleic Acid Ester, and the mol ratio of described polyoxyethylene glycol and oleic acid is: 1: 1.9～2.0.
4. according to claim 1 and 2 or the synthetic method of 3 described polyethylene glycol (PEG) oleates, the molecular weight that it is characterized in that described polyoxyethylene glycol is 400～1000.
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| CN102516073A (en) * | 2011-12-09 | 2012-06-27 | 江南大学 | Method for preparing fatty acid ester antistatic agent from industrial waste polyethylene glycol |
| CN102628230B (en) * | 2012-04-01 | 2013-02-06 | 晋江市南星印染材料有限公司 | Multifunctional high-temperature oil removing levelling agent |
| CN104479126B (en) * | 2013-12-02 | 2016-10-05 | 天津键凯科技有限公司 | Multi-arm polyethylene glycol stearic acic derivative and oleic acid derivatives |
| CN104974340B (en) * | 2015-06-25 | 2017-03-29 | 淄博德信联邦化学工业有限公司 | The preparation method of the polyether polyol with high activity containing ester bond in main chain |
| CN106496078A (en) * | 2016-10-13 | 2017-03-15 | 天津市富特斯科技发展有限公司 | A kind of palmitoleic acid hexahydrobenzoid acid polyethylene glycol sulfonated ester manufacture method |
| CN106634356B (en) * | 2017-01-03 | 2018-12-18 | 阮潇禾 | A kind of lower shrinkage antifouling ceramic tile joint trimming agent |
| CN111171307A (en) * | 2019-12-30 | 2020-05-19 | 华南农业大学 | Vegetable oil-based reactive nonionic surfactant and preparation method and application thereof |
| CN111172793B (en) * | 2020-01-19 | 2020-10-16 | 珠海华大浩宏化工有限公司 | Environment-friendly high-temperature repairing agent and application thereof |
| CN115417985A (en) * | 2022-09-16 | 2022-12-02 | 唐山东沅化工有限公司 | Preparation method of polyethylene glycol oleate |
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| CN1069964A (en) * | 1991-07-02 | 1993-03-17 | 联合碳化化学品及塑料技术公司 | Esterification process |
| CN101177396A (en) * | 2007-12-10 | 2008-05-14 | 东北师范大学 | Method for synthesizing ester in dodecyl benzene sulfonic acid reverse micro emulsion |
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