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CN106397368A - Fatty alcohol-polyoxyethylene ether glycidyl ether and preparation method thereof - Google Patents

Fatty alcohol-polyoxyethylene ether glycidyl ether and preparation method thereof Download PDF

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CN106397368A
CN106397368A CN201610790474.XA CN201610790474A CN106397368A CN 106397368 A CN106397368 A CN 106397368A CN 201610790474 A CN201610790474 A CN 201610790474A CN 106397368 A CN106397368 A CN 106397368A
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preparation
aeo
glycidol ether
product
fatty alcohol
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CN106397368B (en
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张美军
金丰
金一丰
王俊
陈荧杰
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Zhejiang Huangma Technology Co Ltd
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Zhejiang Huangma Technology Co Ltd
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    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D303/00—Compounds containing three-membered rings having one oxygen atom as the only ring hetero atom
    • C07D303/02—Compounds containing oxirane rings
    • C07D303/12—Compounds containing oxirane rings with hydrocarbon radicals, substituted by singly or doubly bound oxygen atoms
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D301/00—Preparation of oxiranes
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G65/00—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule
    • C08G65/02—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule from cyclic ethers by opening of the heterocyclic ring
    • C08G65/30—Post-polymerisation treatment, e.g. recovery, purification, drying
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G65/00—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule
    • C08G65/02—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule from cyclic ethers by opening of the heterocyclic ring
    • C08G65/32—Polymers modified by chemical after-treatment
    • C08G65/329—Polymers modified by chemical after-treatment with organic compounds
    • C08G65/337—Polymers modified by chemical after-treatment with organic compounds containing other elements

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  • Organic Chemistry (AREA)
  • Health & Medical Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • General Chemical & Material Sciences (AREA)
  • Epoxy Compounds (AREA)
  • Solid-Sorbent Or Filter-Aiding Compositions (AREA)

Abstract

The invention relates to fatty alcohol-polyoxyethylene ether glycidyl ether and a preparation method thereof and belongs to the technical field of fine chemical engineering. With fatty alcohol-polyoxyethylene ether and epoxy chloropropane being raw materials, the fatty alcohol-polyoxyethylene ether, a phase-transfer catalyst, alkali and a polymerization inhibitor are evenly mixed in a reaction kettle, then ECH is added, reaction is carried out for some time at certain temperature, solids are removed through filtering, liquid is subjected to reduced pressure distillation and recovery to be reactive ECH, the temperature is decreased to room temperature after completion, an absorbing agent, hydroxymethyl sodium sulfinate and water are added, adsorption and decoloring are carried out for some time at the temperature, heat-preserved dehydration is carried out for 1 h under the conditions of 110 DEG C and 0.098 Mpa, and then the finished product is obtained through filtering at the temperature of 80 DEG C. The preparation method is applied to preparation of the fatty alcohol-polyoxyethylene ether glycidyl ether, and has the advantages that the color of the product is light, and an epoxy value is guaranteed.

Description

A kind of AEO glycidol ether and preparation method thereof
Technical field
The present invention relates to a kind of AEO glycidol ether and preparation method thereof, belong to fine chemical technology Field.
Background technology
AEO glycidol ether, with fatty alcohol as initiator, epoxy addition obtains fatty alcohol polyoxy second Alkene ether, then obtains AEO glycidol ether product by epoxy radicals end-blocking, and its molecular structure feature is：Point It is APEO chain in the middle part of subchain, it has good flexibility and hydrophily, one end is alkyl carbon chain, has lipophile, separately One end is epoxy radicals, has the good active group of reactivity, and structural formula is as follows：
Non-ionic oxyethylene chain is introduced surfactant, the solubility property of surfactant can be improved, acceptable Increase resistance to ion stability, the performance that can make surfactant by oxygen ethylene unit number in Molecular regulator is more preferably.Fatty alcohol First pass through epoxy addition and obtain AEO, then obtain AEO glycidol with epoxy radicals end-blocking Ether, this product reactivity worth and hydrophily are all improved.AEO glycidol ether by with dimethylamine, chlorine The reaction such as sodium acetate can obtain beet alkali ampholytic surface active agent；AEO glycidol ether and sodium sulfite Carry out sulfonating reaction and can obtain fatty alcohol-ether sodium sulfate anion surfactant, it has good salt tolerance, excellent because having Good antidecomposition ability and dispersiveness and be widely used；Formed for paint and coatings industry by addition, hydrolysis Various reagents；It also can be used as additive, solvent, catalyst in epoxy resin, chemical fibre, plastics and rubber production simultaneously And chain-transferring agent；Additionally, it still synthesizes a lot of industrial products, such as antistatic additive, emulsifying agent, plastic additive, cosmetics etc. Important intermediate.
At present, producing alkyl capped polyether method both at home and abroad mainly divides one-step method and two-step method, ring-opening reaction and closed loop anti- Referred to as one-step method should be carried out simultaneously, typically make polyethers and ECH in the presence of a phase transfer catalyst using alkali, through single step reaction Obtain product, alkali is ring opening catalyst and closed loop removing hcl reaction reagent；Ring-opening reaction and ring-closure reaction substep enter Row is referred to as two-step method, in acidic catalyst (H2SO4、HCl、HClO4、BF3·O(CH2CH3)2、SnC14Deng) catalysis under, polyethers First be etherified open loop with ECH and obtain chloropharin ether intermediate product, then carried out with alkali remove hydrogen chloride closed loop to final product.One step Method is few with respect to two-step process, total yield of products is high, process is simple；The multiple ECH of the easy addition of two-step method ring-opening reaction, forms neat Polymers, intermediate product converts thoroughly in ring-closure reaction, causes final products epoxide number relatively low, water or solvent in ring-closure reaction Participation will increase post-processing difficulty.
One-step method principle is as follows：
Two-step method principle is as follows：
Wherein：R is aliphatic alcohol polyethenoxy base；
M is alkali metal.
Under normal pressure aerobic conditions, polyethers (ROH) is exposed in strong alkali environment and is susceptible to multiple side reactions, generates some aldehyde Ketone and have color class material, ECH autohemagglutination also can produce colour substance, and this will affect quality, the color of itself and downstream product Pool and application performance.
The epoxy radicals end-blocking product boiling point of small molecule is relatively low, can obtain the preferable product of purity by vacuum distillation, such as specially The process for purification that sharp CN100999507 announces.
During document JAOCS 78,423 429 (April 2001) synthesizing epoxy base end-blocking octanol, every 132g alcohol needs to use 250ml n-hexane washing extraction organic phase carrys out purified product, and solvent also needs to remove by vacuum distillation.
It can be seen that above-mentioned process for purification not only needs using a large amount of organic solvents, and product epoxy radicals may also be deposited Destroy certain, and the usual molecular weight of polyethers product is big, boiling point high it is impossible to obtain the high color of purity simply by vacuum distillation The good end-blocking product in pool.Patent CN104387576A discloses can be high by the one-step method acquisition low ending ratio of color and luster using NaH The method of epoxy radicals end-blocking allyl alcohol polyether, but H can be produced using NaH2There is explosion danger, be not suitable for industrial production.
For general polyethers post processing, when using adsorbent adsorption bleaching, it is required to add the pH value to polyethers for the acid It is adjusted so as to carry out refinement treatment under mildly acidic conditions, but to the sour more difficult control of accurate addition, can be to reality Bring the inconvenience of operation in production, and to the polyethers with epoxy radicals end-blocking, acid also can make active epoxy bond that open loop occurs, Thus affecting the ending ratio quality of product.
It is thus desirable to exploitation can obtain low color, epoxy bond be had the post processing process for refining of certain protection to obtain Gao Pin Matter product, to meet the market demand with this.
Shortcoming in order to overcome above-mentioned prior art develop a kind of preparation of AEO glycidol ether and Its post-processing approach, compares compared with technique, and the present invention prepares AEO glycidol using one-step method Ether crude product, by adding polymerization inhibitor in end capping reaction, on the one hand can reduce and lead to product color by epoxychloropropane autohemagglutination Too deep problem, on the other hand it is also possible to reduce being polymerized between autohemagglutination and product and the epoxychloropropane between product epoxy radicals The yield being led to reduces and the high problem of product viscosity.By crude product after solids removed by filtration, using modified magnesium silicate and hydroxyl Methyl sulfinic acid sodium mixture makes technological operation for adsorbent and decolorising agent it is not necessary to outer acid adding is adjusted to polyethers crude product pH value Simply, and epoxy bond can also be played a protective role, by decolour post processing obtain color and luster be less than 60 (platinum-cobalt method), produce The AEO glycidol ether that product ending ratio is more than 90%.
Based on this, make the application.
Content of the invention
In the presence of overcoming existing AEO glycidol ether preparation and its post processing subtractive process Drawbacks described above, the present invention provide a kind of preparation method of AEO glycidol ether, the method be conducive to drop Low product color, plays certain protective role to product epoxide number, and preparation and its aftertreatment technology are simple.
For achieving the above object, the technical scheme that the present invention takes is as follows：
A kind of preparation method of AEO glycidol ether, with AEO and epoxy chloropropionate Alkane (ECH) is raw material, and AEO, phase transfer catalyst, alkali and polymerization inhibitor are mixed in a kettle., then Slowly add ECH, at a certain temperature reaction a period of time, solids removed by filtration, will be unreacted for liquid pressure-reducing Distillation recovery ECH, reduces the temperature to room temperature after terminating, add adsorbent, sodium hydroxymethanesulfinate, water, at a temperature of one section of adsorption bleaching when Between, then insulation dehydration 1h under 110 DEG C, -0.098Mpa, is then filtrated to get finished product at 80 DEG C.
Mainly comprise the following steps that：
(1) to addition polymerization ether, phase transfer catalyst, alkali, polymerization inhibitor in reactor, stir, be then slowly added into ECH, Reaction a period of time, obtain end capped polyether crude product；
(2) crude product in step (1) is filtered after desalination, vacuum distillation reclaims epoxychloropropane, after being down to room temperature, adds Adsorbent, sodium hydroxymethanesulfinate, water, are refining to obtain qualified finished product.
Further, as preferred：
In step (1), entering the polyethers in reactor and the mol ratio of ECH is 1:The mol ratio of 1-10, polyethers and alkali is 1:1-4, reaction time 1-10h, reaction temperature 30-60 DEG C.It is furthermore preferred that described alkali selects NaOH, potassium hydroxide, first The mixture of one or more of sodium alkoxide, sodium carbonate, potassium carbonate or sodium hydride etc. material, or a kind of this material or several material Mixture aqueous solution or alcoholic solution, most preferred alkali selects solid sodium hydroxide.
In step (1), polymerization inhibitor addition is the 0.1-0.5% of polyether quality, and para hydroxybenzene first selected by described polymerization inhibitor The mixture of one or more of ether, 2- TBHQ, methylnaphthohydroquinone, 1,4-benzoquinone, nitrobenzene etc. material, preferably It is MEHQ.
In step (1), from quaternary ammonium salt catalyst as the catalyst reacting, the consumption of quaternary ammonium salt catalyst is to close The 0.3-3% of the reactant quality of ring reaction.It is furthermore preferred that described quaternary ammonium salt catalyst select tetra-n-butyl ammonium bromide, Etamon chloride, benzyltriethylammoinium chloride, TBAB, tetrabutylammonium chloride, 4-butyl ammonium hydrogen sulfate or three are pungent The mixture of one or more of methyl ammonium material, most preferably TBAB.
In step (2), the addition of adsorbent is the 0.5-5% of polyethers crude product quality, and sodium hydroxymethanesulfinate is polyethers The 0.08-0.5% of crude product quality, water is the 1-10% of polyethers thick quality product；
In step (2), purification condition is 65-90 DEG C of thermostatic absorption 30-120min, is incubated under 110 DEG C, -0.098Mpa Dehydration 1h, is then filtrated to get finished product at 80 DEG C.
In step (2), described adsorbent is modified magnesium silicate adsorbent.
Described is obtained by the following method through modified magnesium silicate adsorbent：
By AlCl3Powder, magnesium silicate, acid and suitable quantity of water mix modulation and squeeze into has plastic pug, 80-90 Hot submersion 12-24h in DEG C oil bath, is then squeezed into bar, 90-110 DEG C of drying, 300-600 DEG C of air atmosphere by extruder Lower roasting 1-3h, screening is obtained 100-200 mesh adsorbent.
Described Al2O3Powder quality is the 1.0-5.0% of magnesium silicate, and acid is sulfuric acid, hydrochloric acid, nitric acid, phosphoric acid oxalic acid or acetic acid One or more of material mixed acid in any proportion, most preferably hydrochloric acid, the addition of acid is magnesium silicate quality 1-10%.
, with fatty polyoxyethylene esters and epoxychloropropane as raw material, using one-step synthesis method, synthesis technique is simple for the present invention, Side reaction is few, by using modified magnesium silicate and sodium hydroxymethanesulfinate collectively as post processing treating adsorbent, not only makes Product color is decreased obviously, and product epoxy bond is played a protective role.Present invention application AEO is shunk The preparation of glycerine and its post processing, synthesis technique is practical simple, convenient post-treatment, and adsorbent magnesium silicate can be reused, energy While obtaining higher ending ratio (＞ 90%) simultaneously, give product high reaction activity compared with low color (＜ 60), also ensure that into The condition index of product.
The operation principle of the present invention and having the beneficial effect that：
1) present invention adopts one-step method to obtain AEO glycidol ether, and reaction condition is gentle, controllability High, side reaction is few, and under aerobic conditions, AEO can occur peroxidating and from oxygen with oxygen under conditions of alkali The side reactions such as change, generate some aldoketoneses and have color class material, and this will affect product sole mass, color and luster and downstream product should Use performance.It is not necessary to deoxygenation or other specially treateds are done to raw material and course of reaction in the present invention, preparation work will be greatly simplified Skill.
2) using modified magnesium silicate and sodium hydroxymethanesulfinate as post processing treating adsorbent and decolorising agent, can obtain The high-quality product that color and luster is less than 60 (platinum-cobalt colorimetric methods), ending ratio is more than 90%, product quality can foreign enterprise's product refer to shoulder to shoulder Mark.
3) use the magnesium silicate processing to polyethers crude product refining together with sodium hydroxymethanesulfinate, not only can effectively drop Low product color, but also certain protective role is played to the epoxy radicals of product.
4) reaction condition of the present invention is gentle, controlled, and sorbent preparation method is simply it is not necessary to outer acid adding is entered to polyethers crude product Row neutralization, it is to avoid the complexity of operation and uncertainty.
5) magnesium silicate by reclaiming, can regenerate, and reuse, not only increased economic benefits, and decrease solid The generation of waste, serves Environmental Role.
6) in reacting, excessive epoxychloropropane can be reclaimed by vacuum distillation, can be continuing with by processing.
7) reaction does not need to add water or other organic solvent, meets green chemical industry requirement, decreases solvent recovery Energy consumption.
8) react for closed-loop operation, it is to avoid volatile epoxychloropropane damages to workman, reduces production process Environmental pollution, greatly improve production operation environment.
Specific embodiment
A kind of preparation method of the present embodiment AEO glycidol ether, with AEO and Epoxychloropropane is raw material, prepares end capped polyether crude product through one-step method, using modified magnesium silicate and methylol sulfinic acid , as the refined adsorbent of post processing and decolorising agent, its synthesis basic line is as follows for sodium：
Mainly comprise the following steps that：
(1) prepare：Add AEO, phase transfer catalyst, alkali, polymerization inhibitor in reactor, stir, It is then slowly added into ECH, reaction a period of time, obtain end capped polyether crude product；
(2) refine：Crude product in step (1) is filtered after desalination, vacuum distillation reclaims epoxychloropropane, after being down to room temperature, Add adsorbent, sodium hydroxymethanesulfinate, water, be refining to obtain qualified finished product.
Wherein, AEO has below general formula：
AEO glycidol ether has below general formula：
Used in the present invention, raw material all can be obtained using the conventional method in this area, it would however also be possible to employ commercially available prod.
The reaction principle of the present invention is as follows：
Wherein：R is aliphatic alcohol polyethenoxy base；
M is alkali metal；
PTC is phase transfer catalyst.
The present invention adopts GB1664-1981 (platinum-cobalt colorimetric method) methods described to measure product color, using GBT1677- 1981 methods describeds measure product epoxide number, and the ending ratio in embodiment and yield are defined as follows：
Wherein, VO1：Product epoxide number after AEO end-blocking；VO0：AEO 100% envelope Theoretical epoxy value during end；Epoxide number is the quality of the oxygen in 100g sample epoxide epoxy group group.
Below by way of specific embodiment, the invention will be further described, but following examples should not be construed as to this The restriction that bright scope of the claims is made.Wherein embodiment 1-1,1-2,1-3 are to produce modified magnesium silicate, embodiment 2-1,2-2,2-3,2-4 be prepare epoxy radicals end-blocking AEO crude product, and using embodiment 1-1,1-2, It is refined that magnesium silicate system of producing in 1-3 carries out post processing to polyethers crude product.
Embodiment 1-1,1-2 and the preparation that 1-3 is modified magnesium silicate.
Embodiment 1-1
By 1.0gAlCl3, 100g magnesium silicate powders, plus 5.6g concentrated hydrochloric acid and appropriate water squeezes mixing and is bonded to semi-moist shape It is most suitable, hot submersion 24h in 80-90 DEG C of oil bath pan that bar can be smoothly squeezed into, and then extrudes in single screw extrusion machine Strip, then dries at 110 DEG C, roasting 2h in 450 DEG C of air atmospheres, and screening obtains the silicic acid that 100-200 mesh was processed Magnesium adsorbent.
Embodiment 1-2
By 3.0gAlCl3, 100g magnesium silicate powders, plus 16g concentrated hydrochloric acid and appropriate water squeezes mixing and is bonded to semi-moist shape It is most suitable, hot submersion 24h in 80-90 DEG C of oil bath pan that bar can be smoothly squeezed into, and then extrudes in single screw extrusion machine Strip, then dries at 110 DEG C, roasting 2h in 450 DEG C of air atmospheres, and screening obtains the silicic acid that 100-200 mesh was processed Magnesium adsorbent.
Embodiment 1-3
By 5.0gAlCl3, 100g magnesium silicate powders, plus 27.8g concentrated hydrochloric acid and appropriate water squeeze mixing be bonded to semi-moist It is most suitable, hot submersion 24h in 80-90 DEG C of oil bath pan that shape can smoothly be squeezed into bar, then squeezes in single screw extrusion machine It is pressed into strip, then dries at 110 DEG C, roasting 2h in 450 DEG C of air atmospheres, screening obtains the silicon that 100-200 mesh was processed Sour magnesium adsorbent.
Embodiment 2-1,2-2,2-3,2-4 are the preparation of AEO and are post-processed using modified magnesium silicate Refined.
Embodiment 2-1
By 2mol 1028g butanol APEO (n=3, m=10), 3mol NaOH, 10g TBAB, 1g resistance Poly- agent, slowly 3mol ECH is added in 2.5L reactor, controls temperature to be less than 40 DEG C, then it is anti-to be warmed up to 40 DEG C of stirrings Answer 5h, solids removed by filtration, vacuum distillation reclaims excessive ECH, is cooled to room temperature.
Plus the modified magnesium silicate of 10g embodiment 2,2g sodium hydroxymethanesulfinate, 50g water, in above-mentioned polyethers, stir, Be warmed up to 75 DEG C absorption 90min, then in -0.098MPa vacuum condition 110 DEG C dehydrate 1h, be cooled to 80 DEG C and be filtered to remove Solid, obtains light Huang transparency liquid, color and luster 38, ending ratio 96%.
Embodiment 2-2
By 2mol 954g laruyl alcohol alcohol APEO (n=12, m=7), 3mol NaOH, 10g TBAB, 1g polymerization inhibitor, slowly 3mol ECH is added in 2.5L reactor, controls temperature to be less than 40 DEG C, then is warmed up to 40 DEG C and stirs Mix reaction 5h, solids removed by filtration, vacuum distillation reclaims excessive ECH, is cooled to room temperature.
Plus the modified magnesium silicate of 10g embodiment 1-2,2g sodium hydroxymethanesulfinate, 50g water are in above-mentioned polyethers, stirring is all Even, be warmed up to 75 DEG C absorption 90min, then in -0.098MPa vacuum condition 110 DEG C dehydrate 1h, be cooled to 80 DEG C of filtrations Remove solid, obtain light Huang transparency liquid, color and luster 36, ending ratio 93%.
Embodiment 2-3
Method is the modified magnesium silicate using the preparation of embodiment 1-1 fully according to the difference of embodiment 2-2, and products obtained therefrom seals End rate 96%, color and luster 46.
Embodiment 2-4
Method is the modified magnesium silicate using the preparation of embodiment 1-3, products obtained therefrom fully according to embodiment 2-2, difference Ending ratio 94%, color and luster 35.
By embodiment 2-2,2-3,2-4 it can be seen that different quality AlCl3With the magnesium silicate of hydrochloric Acid Modification to product matter Amount has certain impact, but all can reach ending ratio ＞ 90%, color and luster ＜ 60.
Embodiment 3-1 is magnesium silicate recovery and reusing and recycling.
Embodiment 3-1
Embodiment 2-2 post processing filter residue is added water stirring, is then filtrated to get magnesium silicate, then in 110 DEG C of drying, in Roasting 2h in 450 DEG C of air atmospheres, is recycled regeneration magnesium silicate.
Fully according to embodiment 2-2, difference is using reclaiming magnesium silicate method, products obtained therefrom ending ratio 94%, Color and luster 42.
Above-mentioned magnesium silicate is carried out regeneration process again, and apply and post-process refined in, a regeneration time can be obtained Number and the tables of data of its performance.
The end product quality table of comparisons under table 1 different technology conditions
Regeneration times Ending ratio/% Color and luster (platinum-cobalt colorimetric method)
1 94 42
2 94 45
3 94 53
Modified magnesium silicate be can be seen that after repeating to regenerate 3 times by data in table, product color still ＜ 60, ending ratio ＞ 90%.
Comparative example 1
By 2mol 954g laruyl alcohol alcohol APEO (n=12, m=7), 3mol NaOH, 10g TBAB, Slowly 3mol ECH is added in 2.5L reactor, controls temperature to be less than 40 DEG C, then be warmed up to 40 DEG C of stirring reactions 5h, Solids removed by filtration, vacuum distillation reclaims excessive ECH, is cooled to room temperature.
Phosphorate acid in above-mentioned polyethers, adjust pH value to faintly acid, then plus the commercially available magnesium silicate of 10g, 2g activated carbon, 50g water, Stir, be warmed up to 75 DEG C absorption 90min, then in -0.098MPa vacuum condition 110 DEG C dehydrate 1h, be cooled to 80 DEG C solids removed by filtration, obtains brown yellow transparent liquid, color and luster 500, ending ratio 87%.
By embodiment 2-2 and comparative example 1 it can be seen that preparing according to document mode, and using after conventional polyether Process process for refining, product color is very deep, and ending ratio is also little, illustrates that the present invention not only can effectively reduce product color Pool moreover it is possible to play a protective role to epoxy bond, improve product quality.
According to above example and comparative example, a comparison form can be obtained, as shown in table 2.
The end product quality table of comparisons under table 2 different technology conditions
Ending ratio/% Color and luster (platinum-cobalt colorimetric method)
Embodiment 2-1 96 38
Embodiment 2-2 93 36
Embodiment 2-3 96 46
Embodiment 2-4 94 35
Comparative example 1 87 500
Be can be seen that present invention application AEO glycidol by the various embodiments described above and the table of comparisons Preparation and its post processing, synthesis technique is practical simple, convenient post-treatment, and adsorbent magnesium silicate can be reused, and can obtain simultaneously While obtaining higher ending ratio (＞ 93%), give product high reaction activity compared with low color (＜ 46), also ensure that the product of finished product Phase index.
Above content be preferred embodiment with reference to the invention provided technical scheme is made detailed further Describe in detail bright it is impossible to assert that the invention is embodied as being confined to these explanations above-mentioned, the affiliated technology for the invention For the those of ordinary skill in field, without departing from the concept of the premise of the invention, some simple deductions can also be made Or replace, all should be considered as belonging to the protection domain of the invention.

Claims (10)

1. a kind of preparation method of AEO glycidol ether it is characterised in that：Fatty alcohol is added in reactor APEO, catalyst, alkali, polymerization inhibitor, stir, and add epoxychloropropane, reaction finishes, and obtains end capped polyether thick Product；End capped polyether crude product is filtered after desalination, vacuum distillation reclaims epoxychloropropane, after being down to room temperature, adds adsorbent, hydroxyl Methyl sulfinic acid sodium, water, are refining to obtain finished product.
2. as claimed in claim 1 a kind of preparation method of AEO glycidol ether it is characterised in that：Fat The mol ratio of fat alcohol APEO and epoxychloropropane is 1:The mol ratio of 1-10, AEO and alkali is 1:1- 4, reaction time 1-10h, reaction temperature 30-60 DEG C.
3. as claimed in claim 1 a kind of preparation method of AEO glycidol ether it is characterised in that：Institute The alkali stated selects the mixing of one or more of NaOH, potassium hydroxide, sodium methoxide, sodium carbonate, potassium carbonate, sodium hydride Thing, this alkali is solid mixture, the aqueous solution or the alcoholic solution of one or more.
4. as claimed in claim 1 a kind of preparation method of AEO glycidol ether it is characterised in that：Institute The polymerization inhibitor addition stated is the 0.1-0.5% of AEO quality, and polymerization inhibitor selects MEHQ, uncle 2- The mixture of one or more of butylhydroquinone, methylnaphthohydroquinone, 1,4-benzoquinone, nitrobenzene material.
5. as claimed in claim 1 a kind of preparation method of AEO glycidol ether it is characterised in that：Institute Quaternary ammonium salt catalyst selected by the catalyst stated, and consumption is the 0.3-3% of the reactant quality of ring-closure reaction.
6. as claimed in claim 5 a kind of preparation method of AEO glycidol ether it is characterised in that：Institute The quaternary ammonium salt catalyst stated selects tetra-n-butyl ammonium bromide, etamon chloride, benzyltriethylammoinium chloride, tetrabutyl phosphonium bromide The mixture of one or more of ammonium, tetrabutylammonium chloride, 4-butyl ammonium hydrogen sulfate or tri-n-octyl methyl ammonium chloride material.
7. as claimed in claim 1 a kind of preparation method of AEO glycidol ether it is characterised in that：Institute The addition of the adsorbent stated is the 0.5-5% of end capped polyether crude product quality, and sodium hydroxymethanesulfinate is end capped polyether crude product matter The 0.08-0.5% of amount, water is the 1-10% of end capped polyether crude product quality.
8. as claimed in claim 1 a kind of preparation method of AEO glycidol ether it is characterised in that：Institute The purification condition stated is 65-90 DEG C of thermostatic absorption 30-120min, and insulation dehydration 1h under 110 DEG C, -0.098Mpa, then 80 DEG C it is filtrated to get finished product.
9. the preparation method of a kind of AEO glycidol ether as described in claim 1 or 7, its feature exists In described adsorbent is modified magnesium silicate adsorbent, and its preparation method is：By AlCl3Powder, magnesium silicate, acid and water mixing Homogeneous modulation squeezes into has plastic pug, after hot submersion 12-24h in 80-90 DEG C of oil bath, dries in 90-110 DEG C, Roasting 1-3h under 300-600 DEG C of air atmosphere again, screening is obtained 100-200 mesh adsorbent.
10. method as claimed in claim 1 preparation AEO glycidol ether it is characterised in that：Fatty alcohol APEO glycidol ether has below general formula：
Wherein, 3 ＜ n ＜ 22,1<m<20.
CN201610790474.XA 2016-08-31 2016-08-31 A kind of fatty alcohol polyoxyethylene ether glycidol ether and preparation method thereof Active CN106397368B (en)

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CN110358073A (en) * 2018-03-26 2019-10-22 中国石油化工股份有限公司 A kind of poly- two glycerin ether of aliphatic alcohol polyethenoxy and preparation method thereof
CN113637154A (en) * 2021-10-18 2021-11-12 常熟耐素生物材料科技有限公司 Nonionic polyether type high-molecular surfactant and preparation method and application thereof
CN113956462A (en) * 2021-10-21 2022-01-21 万华化学集团股份有限公司 A kind of preparation method of low aldehyde content polyether polyol
CN114149578A (en) * 2021-12-29 2022-03-08 滨化集团股份有限公司 Method for removing potassium and sodium ions in polyether polyol
CN114702371A (en) * 2022-03-29 2022-07-05 浙江皇马科技股份有限公司 Preparation method of etherate of C8-10-alkyl alcohol and oxyethylpropoxy monophenyl ether
CN114934392A (en) * 2022-03-23 2022-08-23 宜兴市事成织物后整理有限公司 Compound finishing agent for water and oil repellent treatment of pure cotton knitted fabric and preparation method thereof
CN115850683A (en) * 2023-02-24 2023-03-28 山东尚正新材料科技股份有限公司 Preparation process of refined polyether suitable for textile auxiliary
CN116082627A (en) * 2022-12-30 2023-05-09 江苏奥克化学有限公司 A kind of epoxy-terminated fatty alcohol polyether, the capping method of fatty alcohol polyether
CN118812821A (en) * 2024-09-18 2024-10-22 化学与精细化工广东省实验室 A kind of terminal allyl epoxy polyether and preparation method thereof

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CN107793378A (en) * 2017-11-27 2018-03-13 湖北绿色家园材料技术股份有限公司 A kind of novel method for synthesizing of glycerin triglycidyl ether
CN108299638A (en) * 2017-12-29 2018-07-20 浙江皇马科技股份有限公司 A kind of synthetic method of allyl alcohol polyethenoxy ether carboxylic acid ethylene oxidic ester
CN108299638B (en) * 2017-12-29 2020-04-28 浙江皇马科技股份有限公司 Synthesis method of allyl alcohol polyoxyethylene ether carboxylic glycidyl ester
CN110358073A (en) * 2018-03-26 2019-10-22 中国石油化工股份有限公司 A kind of poly- two glycerin ether of aliphatic alcohol polyethenoxy and preparation method thereof
CN113637154A (en) * 2021-10-18 2021-11-12 常熟耐素生物材料科技有限公司 Nonionic polyether type high-molecular surfactant and preparation method and application thereof
CN113956462B (en) * 2021-10-21 2023-07-14 万华化学集团股份有限公司 Preparation method of polyether polyol with low aldehyde content
CN113956462A (en) * 2021-10-21 2022-01-21 万华化学集团股份有限公司 A kind of preparation method of low aldehyde content polyether polyol
CN114149578A (en) * 2021-12-29 2022-03-08 滨化集团股份有限公司 Method for removing potassium and sodium ions in polyether polyol
CN114934392A (en) * 2022-03-23 2022-08-23 宜兴市事成织物后整理有限公司 Compound finishing agent for water and oil repellent treatment of pure cotton knitted fabric and preparation method thereof
CN114702371A (en) * 2022-03-29 2022-07-05 浙江皇马科技股份有限公司 Preparation method of etherate of C8-10-alkyl alcohol and oxyethylpropoxy monophenyl ether
CN114702371B (en) * 2022-03-29 2023-08-08 浙江皇马科技股份有限公司 Preparation method of etherate of C8-10-alkyl alcohol and oxyethyl propoxy monophenyl ether
CN116082627A (en) * 2022-12-30 2023-05-09 江苏奥克化学有限公司 A kind of epoxy-terminated fatty alcohol polyether, the capping method of fatty alcohol polyether
CN115850683A (en) * 2023-02-24 2023-03-28 山东尚正新材料科技股份有限公司 Preparation process of refined polyether suitable for textile auxiliary
CN118812821A (en) * 2024-09-18 2024-10-22 化学与精细化工广东省实验室 A kind of terminal allyl epoxy polyether and preparation method thereof

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