CN100338019C - Lauryl alcohol polyethylene glycol oxide ester benzoic ether and its synthesis - Google Patents
Lauryl alcohol polyethylene glycol oxide ester benzoic ether and its synthesis Download PDFInfo
- Publication number
- CN100338019C CN100338019C CNB2006100866796A CN200610086679A CN100338019C CN 100338019 C CN100338019 C CN 100338019C CN B2006100866796 A CNB2006100866796 A CN B2006100866796A CN 200610086679 A CN200610086679 A CN 200610086679A CN 100338019 C CN100338019 C CN 100338019C
- Authority
- CN
- China
- Prior art keywords
- polyethylene glycol
- glycol oxide
- benzoic ether
- lauryl alcohol
- benzoyl chloride
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Expired - Fee Related
Links
Images
Landscapes
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
A lauryl-polyethenoxy ether benzoate and its synthesis are disclosed. The process is carried out by esterification reacting lauryl-polyethylene glycol with benzoyl chloride in proportion of 1:1.05-1.20 at 85-90 degree for 3-4hrs, washing reactant by 5% sodium carbonate solution for twice, drying and inspection analyzing to obtain final product. It has excellent detersive power, wetting ability and surface reactive compatibility. It can be used for industrial organic raw mterial and alcohol non-ionic surface activator.
Description
Technical field
The present invention relates to a kind of alcohol is nonionogenic tenside, relates to a kind of lauryl alcohol polyethylene glycol oxide ester benzoic ether tensio-active agent in particular, belongs to organic chemistry auxiliary agent technical field.
Background technology
Along with the arrival of 21 century, the problem of the Sustainable development of society and related ecology thereof, environment, resource, economic dispatch aspect more and more becomes the focus that international community pays close attention to, the height of referred development strategy.More severe is requirement on environmental protection, impel chemical circles that attention is focused on from origin and stop or reduce generation of waste, i.e. and the prevention of original pollution, and be not the improvement that produces after polluting.Current many Chemicals and production process thereof, how the technology with eighties of last century fifties is that base growth is got up, they have produced many detrimentally affects to physical environment again when being made contributions in aspects such as the mankind's clothing, food, lodging and transportion--basic necessities of life and health care.This must propose new requirement to science and technology, to chemistry, especially synthetic chemistry has been proposed challenge especially, also provides simultaneously the chance of discipline development.In recent years, Green Chemistry, the gentle chemistry of environment, clean technology, environmentally friendly process etc. have become hot issue, and environment, economy are just becoming the main impellent of technological innovation.
Tensio-active agent industry is the chemical engineering industry that eighties of last century grows up the thirties, and along with the development of petrochemical industry, the output of tensio-active agent increases rapidly, has now become one of basic industry of national economy.At present, external existing tensio-active agent kind reaches more than 5000, and trade names also reach more than hundred kinds, and ultimate production is above ten million ton.Wherein the rate of increase of nonionogenic tenside be 1%/, reach more than 5% and alcohol is the rate of increase of nonionogenic tenside.
China's tensio-active agent industry is in developmental stage at present, and scientific research, production, application, exploitation all are subjected to the attention of relevant department.Along with the development of China's economy and petroleum industry, the Application Areas of state's internal surfactants is widened gradually, and the status of tensio-active agent in national economy also day by day promotes, and alcohol is that the Application and Development of nonionogenic tenside is even more important.Domestic Koryo newly waits the people once to report, with CCl
4Be the synthetic a kind of tensio-active agent of solvent---ethoxylated dodecyl alcohol phosphoric acid ester (being published in 2000 the 5th phases the 30th volume daily chemical industry magazine 63-66 page or leaf).This reaction is at organic solvent CCl
4In carry out, not only can bring harm in the reaction process to environment, also wasted the resource and the energy etc. simultaneously.The 50-100 that is generally the raw material consumption because of the organic reaction solvent load of routine doubly, and do not have any solvent because of having avoided the use of a large amount of toxics and volatile organic compounds, not only reduced pollution, operation and last handling process have been simplified, shortened the reaction times, reduced production cost, and be to have the yield height, advantages such as selectivity is strong are so the class organic reaction has become an important channel of realization " Green Chemistry ".
Purpose of the present invention is exactly in order to overcome above-mentioned the deficiencies in the prior art, and proposition is synthetic a kind of nontoxic substantially under condition of no solvent, and free of contamination alcohol is the solvent-free new synthesis technology of nonionogenic tenside-lauryl alcohol polyethylene glycol oxide ester benzoic ether product innovation.This kind tensio-active agent not only has the potential bright prospects in industrial application, and also innovation to some extent on synthetic method.
Summary of the invention
The objective of the invention is to be achieved through the following technical solutions.
Lauryl alcohol polyethylene glycol oxide ester benzoic ether is that a kind of nontoxic, free of contamination alcohol is nonionogenic tenside,
Its molecular structure is
Or write and become
General nonionogenic tenside molecule has asymmetric amphiphilic structure, i.e. molecule oleophylic, and one is hydrophilic.And lauryl alcohol polyethylene glycol oxide ester benzoic ether, two oleophylic, middle hydrophilic, and the hydrophilic radical in the molecule is the Soxylat A 25-7 chain, i.e. (OCH
2CH
2)
nOH.Sauerstoffatom in the chain and hydroxyl all have the ability that generates hydrogen bond with water molecules, make compound have some special nature, are that a kind of special alcohol is nonionogenic tenside.
This product acid number mgKOH/g≤10,, ester content (%) 〉=95, refractive index (20 ℃) 1.471-1.477.
The step of lauryl alcohol polyethylene glycol oxide ester benzoic ether synthetic method is as follows:
At first a certain amount of ethoxylated dodecyl alcohol is put in the heating container, heat temperature raising stops heating during to 55-60 ℃; A certain amount of Benzoyl chloride slowly is added drop-wise in the heating container that has filled ethoxylated dodecyl alcohol by proportioning raw materials then, the limit edged stirs, and after dropwising, continues heat temperature raising to 85-90 ℃, esterification 3-4 hour; Stopped reaction, cool to room temperature leaves standstill; The sodium carbonate solution of adding 5% carries out the washing first time in the container that fills reaction product, leaves standstill; Add 5% sodium carbonate solution again and carry out the washing second time, leave standstill; Place moisture eliminator dry reaction product, analysis characterizes product at last after testing.
The present invention is to be raw material with the ethoxylated dodecyl alcohol, carries out substitution reaction with Benzoyl chloride under condition of no solvent.Reaction itself is an esterification, and is a reversible reaction.For reaction is carried through to the end, improve reaction yield, proportioning raw materials is most important, if adopt Benzoyl chloride excessive, so that reaction carries out towards positive dirction, but problem is the Benzoyl chloride decomposition that easily distils
The phenylformic acid that generates is owing to be slightly soluble in water.If Benzoyl chloride is excessive many, the aftertreatment of product is brought a lot of difficulties.Through repetition test, be 1: 1.05～1.20 to be advisable with the mol ratio of ethoxylated dodecyl alcohol and Benzoyl chloride.Generate a spot of phenylformic acid in reaction system when temperature is increased to 100 ℃, can be sublimate on the vacuum tube wall crystallization and separate out and remove, the HCL that reaction generates is absorbed by the salt absorber acid, so reaction process does not produce pollutent.
Ethoxylated dodecyl alcohol and Benzoyl chloride can react at normal temperatures, and product is almost colourless.But need to react more than 24 hours under the normal temperature, and transformation efficiency is only below 80%.In order to improve speed of response, shorten the reaction times, we adopt the method for heating under the normal pressure in the hope of the shortening reaction times, and can reach higher transformation efficiency.Evidence is adopted under the normal pressure and was reacted 3～4 hours under 85～90 ℃, and yield can reach 95%.
Heating container of the present invention can be four-hole boiling flask or the round bottom band mouth flask that agitator, thermometer, prolong are housed, and type of heating can be oil bath or electrically heated or other type of heating.
The present invention compared with prior art has following advantage and performance:
(1) have remarkable molten oiliness, can be miscible with crude oil, diesel oil, kerosene, machine oil, lubricating oil, plant wet goods arbitrary proportion;
(2) can with multiple immiscible organic solvent;
(3) still, have concurrently and press down bubble, antifoam performance;
(4) can mix, match with negatively charged ion, positively charged ion, nonionic, zwitterionics, and the energy synergy;
(5) have dispersion, wetting, infiltration, solubilising, antistatic property, stable in acid-basicity solution;
(6) gentle, safe, non-stimulated, skin, clothing, machine and various metallic surface are had provide protection.
Description of drawings
Fig. 1 is a technological process block-diagram of the present invention.
Embodiment
Below in conjunction with the drawings and specific embodiments the present invention is further described.
As shown in Figure 1, at first a certain amount of ethoxylated dodecyl alcohol is put in the round-bottomed flask, again round-bottomed flask is placed oil bath heater, heat temperature raising makes when temperature rises to 55～60 ℃ in the flask, stop heating, by proportioning a certain amount of Benzoyl chloride slowly is added drop-wise in the round-bottomed flask then, the limit edged stirs, after dropwising, temperature rises 2～3 ℃ in the flask, continues heating subsequently and temperature in the flask is risen to 85～90 ℃, esterification 3-4 hour, stopped reaction, be cooled to room temperature, leave standstill, add 5% sodium carbonate solution washed twice, after leaving standstill reaction product placed moisture eliminator dry, analyze after testing the finished product.
Embodiment 1:
1mmol ethoxylated dodecyl alcohol (n=9) after the metering is put in the 50ml round-bottomed flask, place oil bath heater to heat in flask again, the 1.00mmol Benzoyl chloride that measures joins in the constant pressure funnel, after temperature in the flask rises to 55～60 ℃, stop heating, turn on agitator slowly drips Benzoyl chloride simultaneously; After dropwising, Heating temperature is risen to 85～90 ℃, reacted 3-4 hour, stop to stir, leave standstill.
Embodiment 2:
1mmol ethoxylated dodecyl alcohol (n=9) after the metering is put in the 50ml round-bottomed flask, place oil bath heater to heat in flask again, the 1.05mmol Benzoyl chloride that measures joins in the constant pressure funnel, after temperature in the flask rises to 55～60 ℃, stop heating, turn on agitator slowly drips Benzoyl chloride simultaneously; After dropwising, Heating temperature is risen to 85～90 ℃, reacted 3-4 hour, stop to stir, leave standstill.
Embodiment 3:
1mmol ethoxylated dodecyl alcohol (n=9) after the metering is put in the 50ml round-bottomed flask, place oil bath heater to heat in flask again, the 1.20mmol Benzoyl chloride that measures joins in the constant pressure funnel, after temperature in the flask rises to 55～60 ℃, stop heating, turn on agitator slowly drips Benzoyl chloride simultaneously; After dropwising, Heating temperature is risen to 85～90 ℃, reacted 3-4 hour, stop to stir, leave standstill.
Embodiment 4:
1mmol ethoxylated dodecyl alcohol (n=9) after the metering is put in the 50ml round-bottomed flask, place oil bath heater to heat in flask again, the 1.30mmal Benzoyl chloride that measures joins in the constant pressure funnel, after temperature in the flask rises to 55～60 ℃, stop heating, turn on agitator slowly drips phenylformic acid chlorine simultaneously; After dropwising, Heating temperature is risen to 85～90 ℃, reacted 3-4 hour, stop to stir, leave standstill.
After the foregoing description 1-4 reaction finishes, use the refractive index of refractometer assaying reaction product, judge according to refractive index whether the esterification degree is good; Test find when the prescription of raw material ratio in 1: 1.05～1: 1.20 scope, refractive index is about 1.4730, after meeting the requirements, reaction product need be with 5% sodium carbonate solution washed twice, leave standstill, acid number dry, that record product is about 1.043mgKOH/g, acid number is below 10mgKOH/g, and then the transformation efficiency that should react has reached re-set target more than 95%.
The performance assessment criteria of products obtained therefrom is as follows:
Outward appearance: light yellow transparent liquid
Color and luster≤180
Acid number (mgKOH/g)≤10
Ester content (%) 〉=95
Refractive index (20 ℃) 1.471～1.477
The nuclear magnetic data of products obtained therefrom is as follows:
1H NMR (400MHz, CDCl
3), δ=8.07-7.42 (m, 5H, Ph-H), 4.91-4.47 (m, 2H), 3.85-3.43 (m, 36H), 1.76 (s, 2H), 1.59-1.55 (m, 2H), 1.25 (s, 16H), 0.90-0.86 (m, 3H). infrared analysis is as follows: IR (ν/cm
-1): 2924,2855,1720,1453,1275,1111,950,714. from nuclear magnetic resonance data as can be seen: chemical shift has two hydrogen at 4.91-4.47ppm, is PhCOOCH
2-, methylene radical on hydrogen, illustrate that ethoxylated dodecyl alcohol and Benzoyl chloride react.From infrared data, also this point can be described in addition, at 1275cm
-1Very strong absorption peak is arranged, the existence of ester group is described, also this point can be described from other absorption peaks.
Claims (3)
1. lauryl alcohol polyethylene glycol oxide ester benzoic ether, it is characterized in that: molecular structure is
Or write and become
Acid number is about 1.043mgKOH/g, and refractive index is about 1.4730, ester content 〉=95%.
2. the synthetic method of a lauryl alcohol polyethylene glycol oxide ester benzoic ether as claimed in claim 1 is characterized in that: when at first by proportioning raw materials ethoxylated dodecyl alcohol being put in the heating container heat temperature raising to 55～60 ℃, stop heating; By proportioning raw materials Benzoyl chloride slowly is added drop-wise in the heating container then, the limit edged stirs, and after dropwising, continues heat temperature raising to 85～90 ℃, esterification 3-4 hour; Stopped reaction, be cooled to room temperature, leave standstill; The sodium carbonate solution of adding 5% carries out the washing first time in the heating container that fills reaction product, leaves standstill; Add 5% sodium carbonate solution again and carry out the washing second time, leave standstill, place moisture eliminator dry reaction product, analyze after testing and at last product is characterized, the proportioning raw materials of described ethoxylated dodecyl alcohol and Benzoyl chloride is: 1: 1.05～1.20.
3. the synthetic method of a kind of lauryl alcohol polyethylene glycol oxide ester benzoic ether according to claim 2, it is characterized in that: described heating container can be four-hole boiling flask or the round bottom band mouth flask that agitator, thermometer, prolong are housed, and type of heating can be oil bath or electrically heated.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CNB2006100866796A CN100338019C (en) | 2006-06-28 | 2006-06-28 | Lauryl alcohol polyethylene glycol oxide ester benzoic ether and its synthesis |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CNB2006100866796A CN100338019C (en) | 2006-06-28 | 2006-06-28 | Lauryl alcohol polyethylene glycol oxide ester benzoic ether and its synthesis |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN1896046A CN1896046A (en) | 2007-01-17 |
| CN100338019C true CN100338019C (en) | 2007-09-19 |
Family
ID=37608723
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CNB2006100866796A Expired - Fee Related CN100338019C (en) | 2006-06-28 | 2006-06-28 | Lauryl alcohol polyethylene glycol oxide ester benzoic ether and its synthesis |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN100338019C (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2012146889A1 (en) * | 2011-04-26 | 2012-11-01 | Syngenta Limited | Formulation component |
Families Citing this family (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101029281B (en) * | 2007-03-11 | 2010-12-15 | 李泽潜 | Cleaner |
| CN101709032B (en) * | 2009-11-26 | 2012-09-26 | 聊城大学 | Lauryl alcohol polyoxyethylene ether acetate and cleaning agent taking lauryl alcohol polyoxyethylene ether acetate as main component |
| CN105862454B (en) * | 2016-04-13 | 2018-09-11 | 杭州美高华颐化工有限公司 | The synthetic method of disperse dyes in low-temperature dyeing accelerating agent for dacron |
| CN106631924A (en) * | 2016-12-19 | 2017-05-10 | 聊城大学 | Laurinol polyoxyethylene ether benzene sulfonate, preparation method and application |
| CN108586234B (en) * | 2017-12-29 | 2021-01-26 | 浙江皇马科技股份有限公司 | Preparation method of isooctanol polyoxypropylene ether fatty acid ester |
| CN117682945A (en) * | 2024-02-01 | 2024-03-12 | 苏州博研医药科技有限公司 | Preparation method of polidocanol and intermediate thereof |
Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1135487A (en) * | 1994-11-08 | 1996-11-13 | 莱雅公司 | Anti-tanning agent, and light-protection cosmetic composition containing said agent and application thereof |
-
2006
- 2006-06-28 CN CNB2006100866796A patent/CN100338019C/en not_active Expired - Fee Related
Patent Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1135487A (en) * | 1994-11-08 | 1996-11-13 | 莱雅公司 | Anti-tanning agent, and light-protection cosmetic composition containing said agent and application thereof |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2012146889A1 (en) * | 2011-04-26 | 2012-11-01 | Syngenta Limited | Formulation component |
Also Published As
| Publication number | Publication date |
|---|---|
| CN1896046A (en) | 2007-01-17 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN100338019C (en) | Lauryl alcohol polyethylene glycol oxide ester benzoic ether and its synthesis | |
| CN102230278B (en) | Concentrated fabric softener and preparation method thereof | |
| CN102021082A (en) | Method for preparing fatty acid methyl ester and glycerol from kitchen waste oil by utilizing acid-base two-step method | |
| CN101862649B (en) | Preparation method and application of single-phase bismuth titanate nano-material | |
| CN109225271B (en) | A kind of SrTiO3/SnCoS4The preparation method and applications of high efficiency photocatalyst | |
| CN101318640A (en) | Process for synthesizing CePO4 nano-material with monocline structure | |
| CN102824928B (en) | Solid acid catalyst for preparing biodiesel and preparation method as well as application of solid acid catalyst | |
| CN111548445B (en) | Optical activity AIE fluorescent material and preparation method of aqueous polymer thereof | |
| CN102838487A (en) | Synthesis method of 2-ethylhexyl salicylate | |
| CN110627970B (en) | Process method for preparing polyester antistatic agent by using pentaerythritol tetraacrylate wastewater | |
| CN1810931A (en) | Microwave process to prepare biological diesel oil | |
| CN101020632A (en) | Ethoxylated dodecyl alcohol acetate or propionate and its prepn process | |
| CN101406842B (en) | Al-pillared paligorskite modified solid acid catalyst and preparation and application thereof | |
| CN104014342A (en) | Dual-function magnetic nano solid-base catalyst and preparation method and application thereof | |
| CN111151262A (en) | Mn-Cu2O-modified photocatalyst and preparation method thereof | |
| CN103586031B (en) | For preparing bimetal solid base catalyst and the using method thereof of biodiesel | |
| CN101711959A (en) | Polymerizable ester-group Gemini cation gemini surfactant and preparation method thereof | |
| CN1974001A (en) | Polyoxometallate catalyst for preparing biological diesel oil | |
| CN110055138A (en) | A method of utilizing kitchen garbage preparing biological diesel oil and glycerol | |
| CN109796337A (en) | A kind of technique of ester-interchange method Glycerin oleate | |
| CN111269116B (en) | Method for realizing preparation and in-situ separation of ricinoleic acid oligomer | |
| CN101148599A (en) | Method for preparing biological diesel oil from waste animals and plants grease with high acid value | |
| CN104164304A (en) | Novel method for preparing biodiesel under catalysis of modified resin | |
| CN110644056B (en) | Formula of composite texturing solution additive for preparing fine and dense pyramid monocrystalline silicon textured surface | |
| CN101709032B (en) | Lauryl alcohol polyoxyethylene ether acetate and cleaning agent taking lauryl alcohol polyoxyethylene ether acetate as main component |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| C14 | Grant of patent or utility model | ||
| GR01 | Patent grant | ||
| C17 | Cessation of patent right | ||
| CF01 | Termination of patent right due to non-payment of annual fee |
Granted publication date: 20070919 Termination date: 20100628 |