CN106397368B - A kind of fatty alcohol polyoxyethylene ether glycidol ether and preparation method thereof - Google Patents
A kind of fatty alcohol polyoxyethylene ether glycidol ether and preparation method thereof Download PDFInfo
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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
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D301/00—Preparation of oxiranes
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- 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
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- 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
Abstract
The present invention relates to a kind of fatty alcohol polyoxyethylene ether glycidol ethers and preparation method thereof, belong to technical field of fine.Using fatty alcohol polyoxyethylene ether and epoxychloropropane as raw material, fatty alcohol polyoxyethylene ether, phase transfer catalyst, alkali and polymerization inhibitor are uniformly mixed in a kettle, again plus ECH, reaction a period of time at a certain temperature, it is filtered to remove solid, liquid pressure-reducing is distilled to recover the ECH for reaction, after reduce the temperature to room temperature, adsorbent, sodium hydroxymethanesulfinate, water is added, at a temperature of adsorption bleaching for a period of time, then 1 h of heat preservation dehydration at 110 DEG C, -0.098 Mpa, is then obtained by filtration finished product at 80 DEG C.The application is applied to the preparation of fatty alcohol polyoxyethylene ether glycidol ether, has many advantages, such as that product color is low, epoxide number is secure.
Description
Technical field
The present invention relates to a kind of fatty alcohol polyoxyethylene ether glycidol ethers and preparation method thereof, belong to fine chemical technology
Field.
Background technology
Fatty alcohol polyoxyethylene ether glycidol ether, using fatty alcohol as initiator, epoxy addition obtains fatty alcohol polyoxy second
Alkene ether, then obtains fatty alcohol polyoxyethylene ether glycidol ether product by epoxy radicals end-blocking, and molecular structure feature is：Point
It is polyoxyethylene ether chain in the middle part of subchain, is alkyl carbon chain with good flexible and hydrophily, one end, there is lipophile, separately
One end is epoxy group, has the good active group of reactivity, structural formula as follows：
Non-ionic oxyethylene chain is introduced into surfactant, the solubility property of surfactant can be improved, it can be with
Increase resistance to ion stability, can make the performance of surfactant more preferably by adjusting ethylene oxide unit number in molecule.Fatty alcohol
It first passes through epoxy addition and obtains fatty alcohol polyoxyethylene ether, then fatty alcohol polyoxyethylene ether glycidol is obtained with epoxy radicals end-blocking
Ether, the product reactivity worth and hydrophily are all improved.Fatty alcohol polyoxyethylene ether glycidol ether by with dimethylamine, chlorine
The reactions such as sodium acetate can obtain beet alkali ampholytic surface active agent；Fatty alcohol polyoxyethylene ether glycidol ether and sodium sulfite
Fatty alcohol-ether sodium sulfate anion surfactant can be obtained by carrying out sulfonating reaction, it is because there is good salt tolerance, excellent
Good antidecomposition ability and dispersibility and be widely used；It is formed by addition, hydrolysis for painting and coatings industry
Various reagents；It can also be used as additive, solvent, catalyst in epoxy resin, chemical fibre, plastics and rubber production simultaneously
And chain-transferring agent；In addition, it still synthesizes many industrial products, such as antistatic agent, emulsifier, plastic additive, cosmetics
Important intermediate.
Currently, production alkyl capped polyether method mainly divides one-step method and two-step method, ring-opening reaction and closed loop anti-both at home and abroad
It should be carried out at the same time referred to as one-step method, generally make polyethers and ECH in the presence of a phase transfer catalyst using alkali, by single step reaction
Product is obtained, alkali is both ring opening catalyst and closed loop removes hcl reaction reagent；Ring-opening reaction and ring-closure reaction substep into
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 with alkali carry out removing hydrogen chloride closed loop arrive final product.One step
Method is few relative to two-step process, total yield of products is high, simple for process；The multiple ECH of the easy addition of two-step method ring-opening reaction are formed neat
Polymers, intermediate product are converted in ring-closure reaction and are not thorough, and cause 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 element.
Under normal pressure aerobic conditions, polyethers (ROH), which is exposed in strong alkali environment, is easy to happen a variety of side reactions, generates some aldehyde
Ketone and there are color substance, ECH autohemagglutinations also to will produce colour substance, this will influence 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, the preferable product of purity can be obtained by vacuum distillation, such as specially
The process for purification that sharp CN100999507 is announced.
When 78,423-429 (April 2001) synthesizing epoxy bases of document JAOCS block octanol, need to use per 132g alcohol
250ml n-hexanes washing extraction organic phase carrys out purified product, and solvent also needs to remove by being evaporated under reduced pressure.
It can be seen that above-mentioned process for purification not only needs to use a large amount of organic solvents, and product epoxy group may be deposited also
It is centainly destroying, and the usual molecular weight of polyethers product is big, boiling point is high, the high color of purity cannot be obtained simply by vacuum distillation
The good sealing end product in pool.Patent CN104387576A is disclosed can be high by the low ending ratio of one-step method acquisition color and luster using NaH
The method of epoxy radicals end-blocking allyl alcohol polyether, but will produce H using NaH2There are explosion dangers, are not suitable for industrial production.
General polyethers is post-processed, when using adsorbent adsorption bleaching, is required to pH value of the addition acid to polyethers
It is adjusted, it is made to carry out refinement treatment under mildly acidic conditions, but it is more difficult to control to the accurate addition of acid, it can give practical
Bring the inconvenience of operation in production, and the polyethers pair with epoxy radicals end-blocking, acid can also make active epoxy bond that open loop occur,
To influence the ending ratio quality of product.
Therefore it needs to develop to obtain low color, there is epoxy bond the post-processing process for refining centainly protected to obtain Gao Pin
Matter product meets the market demand with this.
Develop in order to overcome the disadvantages of the above prior art a kind of fatty alcohol polyoxyethylene ether glycidol ether prepare and
Its post-processing approach, is compared compared with technique, and fatty alcohol polyoxyethylene ether glycidol is prepared using one-step method in the present invention
Ether crude product, by adding polymerization inhibitor in end capping reaction, on the one hand can reduce leads to product color by epoxychloropropane autohemagglutination
On the other hand too deep problem can also reduce polymerizeing between autohemagglutination and product and epoxychloropropane between product epoxy group
Caused yield reduces and the high problem of product viscosity.By crude product after being filtered to remove solid, using modified magnesium silicate and hydroxyl
Methyl sulfinic acid sodium mixture is adsorbent and decolorising agent, does not need outer acid adding to polyethers crude product pH value adjustment, makes technological operation
Simply, it and can also play a protective role to epoxy bond, color and luster is obtained less than 60 (platinum-cobalt methods), production by post-processing of decolourizing
Product ending ratio is more than 90% fatty alcohol polyoxyethylene ether glycidol ether.
Based on this, the application is made.
Invention content
In the presence of overcoming existing fatty alcohol polyoxyethylene ether glycidol ether to prepare and its post-processing subtractive process
Drawbacks described above, the present invention provides a kind of preparation method of fatty alcohol polyoxyethylene ether glycidol ether, and this method is conducive to drop
Low product color plays certain protective role to product epoxide number, prepares and its aftertreatment technology is simple.
To achieve the above object, the technical solution adopted by the present invention is as follows：
A kind of preparation method of fatty alcohol polyoxyethylene ether glycidol ether, with fatty alcohol polyoxyethylene ether and epoxy chloropropionate
Alkane (ECH) is raw material, and fatty alcohol polyoxyethylene ether, phase transfer catalyst, alkali and polymerization inhibitor are uniformly mixed in a kettle, then
Slowly plus ECH, at a certain temperature reaction for a period of time, are filtered to remove solid, liquid pressure-reducing are distilled to recover unreacted
ECH, after reduce the temperature to room temperature, adsorbent, sodium hydroxymethanesulfinate, water is added, at a temperature of one section of adsorption bleaching when
Between, then the heat preservation dehydration 1h at 110 DEG C, -0.098Mpa, is then obtained by filtration finished product at 80 DEG C.
Mainly comprise the following steps that：
(1) addition polymerization ether, phase transfer catalyst, alkali, polymerization inhibitor into reaction kettle, stir evenly, are then slowly added into ECH,
Reaction a period of time, obtain end capped polyether crude product；
(2) by after crude product filtering desalination in step (1), vacuum distillation recycling epoxychloropropane is cooled to room temperature, adds
Adsorbent, sodium hydroxymethanesulfinate, water are refining to obtain qualified finished product.
Further, as preferred：
In step (1), the molar ratio into polyethers and ECH in reaction kettle is 1:The molar ratio of 1-10, polyethers and alkali is
1:1-4, reaction time 1-10h, 30-60 DEG C of reaction temperature.It is furthermore preferred that the alkali selects sodium hydroxide, potassium hydroxide, first
The mixture of one or more of sodium alkoxide, sodium carbonate, potassium carbonate or sodium hydride etc. substance or a kind of this substance or several substances
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 the polymerization inhibitor selects para hydroxybenzene first
The mixture of one or more of ether, 2- tert-butyl hydroquinone, methylnaphthohydroquinone, 1,4-benzoquinone, nitrobenzene etc. substance, preferably
It is p-hydroxyanisole.
In step (1), select quaternary ammonium salt catalyst as the catalyst of reaction, the dosage of quaternary ammonium salt catalyst is to close
The 0.3-3% of the reactant quality of ring reaction.It is furthermore preferred that the quaternary ammonium salt catalyst selection tetra-n-butyl ammonium bromide,
Etamon chloride, benzyltriethylammoinium chloride, tetrabutylammonium bromide, tetrabutylammonium chloride, 4-butyl ammonium hydrogen sulfate or three are pungent
The mixture of one or more of methyl ammonium substance, most preferably tetrabutylammonium bromide.
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 are the 1-10% of the thick quality product of polyethers；
In step (2), purification condition is 65-90 DEG C of thermostatic absorption 30-120min, is kept the temperature at 110 DEG C, -0.098Mpa
It is dehydrated 1h, finished product then is obtained by filtration at 80 DEG C.
In step (2), the adsorbent is modified magnesium silicate adsorbent.
The magnesium silicate adsorbent modified is made by the following method：
By AlCl3Powder, magnesium silicate, acid and suitable quantity of water are uniformly mixed modulation and squeeze into the plastic pug of tool, 80-90
Then hot submersion 12-24h in DEG C oil bath is squeezed into item, 90-110 DEG C of drying, 300-600 DEG C of air atmosphere by extruder
Lower roasting 1-3h is sieved and 100-200 mesh adsorbents is made.
The AlCl3Powder quality is the 1.0-5.0% of magnesium silicate, and acid is sulfuric acid, hydrochloric acid, nitric acid, phosphoric acid oxalic acid or vinegar
The mixed acid of one or more of acid substance in any proportion, most preferably hydrochloric acid, sour addition are magnesium silicate quality
1-10%.
The present invention is using fatty polyoxyethylene esters and epoxychloropropane as raw material, and using one-step synthesis method, synthesis technology is simple,
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 is played a protective role to product epoxy bond.The present invention is shunk using fatty alcohol polyoxyethylene ether
The preparation and its post-processing of glycerine, synthesis technology is practical simple, and convenient post-treatment, adsorbent magnesium silicate may be reused, energy
While obtaining higher ending ratio (> 90%) simultaneously, assign product high reaction activity compared with low color (< 60), also ensure into
The condition index of product.
The working principle and beneficial effect of the present invention is as follows：
1) present invention obtains fatty alcohol polyoxyethylene ether glycidol ether using one-step method, and reaction condition is mild, controllability
It is high, side reaction is few, under aerobic conditions, peroxidating can occur under conditions of alkali with oxygen and from oxygen for fatty alcohol polyoxyethylene ether
The side reactions such as change generate some aldoketones and have color substance, this is answered product sole mass, color and luster and downstream product is influenced
Use performance.In the present invention, deoxygenation or other specially treateds need not be done to raw material and reaction process, will greatly simplify preparation work
Skill.
2) it can get as post-processing treating adsorbent and decolorising agent using modified magnesium silicate and sodium hydroxymethanesulfinate
Color and luster is less than the high-quality product of 60 (platinum-cobalt colorimetric methods), ending ratio more than 90%, and product quality foreign enterprise's product can refer to shoulder to shoulder
Mark.
3) it not only can effectively be dropped together to polyethers crude product refining using processed magnesium silicate and sodium hydroxymethanesulfinate
Low product color, but also certain protective role is played to the epoxy group of product.
4) reaction condition of the present invention is mild, controllable, and sorbent preparation method is simple, do not need outer acid adding to polyethers crude product into
Row neutralizes, and avoids the complexity and uncertainty of operation.
5) magnesium silicate can be reused by recycling, regenerating, not only increase economic benefits, and reduce solid
The generation of waste, plays Environmental Role.
6) excessive epoxychloropropane can be recycled by being evaporated under reduced pressure in reacting, and can be continuing with by processing.
7) reaction need not add water or other organic solvents, meet green chemical industry requirement, decrease solvent recovery
Energy consumption.
8) reaction is closed-loop operation, avoids volatile epoxychloropropane from damaging worker, reduces production process
Environmental pollution, greatly improve production operation environment.
Specific implementation mode
A kind of preparation method of fatty alcohol polyoxyethylene ether glycidol ether of the present embodiment, with fatty alcohol polyoxyethylene ether and
Epoxychloropropane is raw material, and end capped polyether crude product is prepared by one-step method, using modified magnesium silicate and methylol sulfinic acid
The sodium adsorbent and decolorising agent refined as post-processing, synthesis basic line are as follows：
Mainly comprise the following steps that：
(1) it prepares：Add fatty alcohol polyoxyethylene ether, phase transfer catalyst, alkali, polymerization inhibitor into reaction kettle, stir evenly,
It is then slowly added into ECH, reaction a period of time, obtains end capped polyether crude product；
(2) it refines：After crude product filtering desalination in step (1), vacuum distillation recycling epoxychloropropane is cooled to room temperature,
Adsorbent, sodium hydroxymethanesulfinate, water are added, qualified finished product is refining to obtain.
Wherein, fatty alcohol polyoxyethylene ether has following general formula：
Fatty alcohol polyoxyethylene ether glycidol ether has following general formula：
The method that this field routine may be used in the raw material used in the present invention is made, and can also use commercial product.
The reaction principle of the present invention is as follows：
Wherein：R is aliphatic alcohol polyethenoxy base；
M is alkali metal element；
PTC is phase transfer catalyst.
The present invention measures product color using GB1664-1981 (platinum-cobalt colorimetric method) the method, using GBT1677-
1981 the methods measure product epoxide number, in embodiment ending ratio and yield be defined as follows：
Wherein, VO1：Product epoxide number after fatty alcohol polyoxyethylene ether sealing end；VO0：100% envelope of fatty alcohol polyoxyethylene ether
Theoretical epoxy value when end；Epoxide number is the quality of the oxygen in 100g sample epoxide epoxy group groups.
Below by way of specific embodiment, the invention will be further described, but following embodiment should not be construed as to this hair
The limitation that bright scope of the claims are made.Wherein embodiment 1-1,1-2,1-3 is to produce modified magnesium silicate, embodiment
2-1,2-2,2-3,2-4 be prepared epoxy radicals end-blocking fatty alcohol polyoxyethylene ether crude product, and using embodiment 1-1,1-2,
Magnesium silicate system is produced in 1-3, and to carry out post-processing to polyethers crude product refined.
Embodiment 1-1,1-2 and 1-3 are the preparation of modified magnesium silicate.
Embodiment 1-1
By 1.0gAlCl3, 100g magnesium silicate powders, add 5.6g concentrated hydrochloric acids and suitable water to squeeze mixing and be bonded to semi-moist shape
It is most suitable that item, which can be smoothly squeezed into, and hot submersion for 24 hours, is then squeezed in single screw extrusion machine in 80-90 DEG C of oil bath pan
Then strip is dried at 110 DEG C, 2h is roasted in 450 DEG C of air atmospheres, and screening obtains the processed silicic acid of 100-200 mesh
Magnesium adsorbent.
Embodiment 1-2
By 3.0gAlCl3, 100g magnesium silicate powders, add 16g concentrated hydrochloric acids and suitable water to squeeze mixing and be bonded to semi-moist shape
It is most suitable that item, which can be smoothly squeezed into, and hot submersion for 24 hours, is then squeezed in single screw extrusion machine in 80-90 DEG C of oil bath pan
Then strip is dried at 110 DEG C, 2h is roasted in 450 DEG C of air atmospheres, and screening obtains the processed silicic acid of 100-200 mesh
Magnesium adsorbent.
Embodiment 1-3
By 5.0gAlCl3, 100g magnesium silicate powders, add 27.8g concentrated hydrochloric acids and suitable water squeeze mixing be bonded to it is semi-moist
It is most suitable that shape, which can smoothly be squeezed into item, and hot submersion for 24 hours, is then squeezed in single screw extrusion machine in 80-90 DEG C of oil bath pan
It is pressed into strip, is then dried at 110 DEG C, 2h is roasted in 450 DEG C of air atmospheres, screening obtains the processed silicon of 100-200 mesh
Sour magnesium adsorbent.
Embodiment 2-1,2-2,2-3,2-4 are the preparation of fatty alcohol polyoxyethylene ether and are post-processed using modified magnesium silicate
It is refined.
Embodiment 2-1
By 2mol 1028g butanol polyoxyethylene ether (n=3, m=10), 3mol NaOH, 10g tetrabutylammonium bromide, 1g resistances
3mol ECH are slowly added in 2.5L reaction kettles by poly- agent, and control temperature is no more than 40 DEG C, then are warming up to 40 DEG C of stirrings instead
5h is answered, solid is filtered to remove, vacuum distillation recycles excessive ECH, is cooled to room temperature.
In the modification magnesium silicate, 2g sodium hydroxymethanesulfinates, 50g water to above-mentioned polyethers that add 10g embodiments 2, stir evenly,
75 DEG C of absorption 90min are warming up to, then in 110 DEG C of dehydration and drying 1h of -0.098MPa vacuum conditions, 80 DEG C is cooled to and is filtered to remove
Solid obtains light yellow transparency liquid, color and luster 38, ending ratio 96%.Embodiment 2-2
By 2mol 954g laruyl alcohol alcohol polyoxyethylene ether (n=12, m=7), 3mol NaOH, 10g tetrabutylammonium bromide,
3mol ECH are slowly added in 2.5L reaction kettles by 1g polymerization inhibitors, and control temperature is no more than 40 DEG C, then is warming up to 40 DEG C and stirs
Reaction 5h is mixed, solid is filtered to remove, vacuum distillation recycles excessive ECH, is cooled to room temperature.
In the modification magnesium silicate, 2g sodium hydroxymethanesulfinates, 50g water to above-mentioned polyethers that add 10g embodiments 1-2, stirring is equal
It is even, 75 DEG C of absorption 90min are warming up to, then in 110 DEG C of dehydration and drying 1h of -0.098MPa vacuum conditions, are cooled to 80 DEG C of filterings
Solid is removed, light yellow transparency liquid, color and luster 36, ending ratio 93% are obtained.
Embodiment 2-3
Difference lies in the modification magnesium silicate for using embodiment 1-1 to prepare, products obtained therefrom envelopes fully according to embodiment 2-2 for method
End rate 96%, color and luster 46.
Embodiment 2-4
Method is fully according to embodiment 2-2, and difference lies in the modification magnesium silicate for using embodiment 1-3 to prepare, products obtained therefroms
Ending ratio 94%, color and luster 35.
Pass through embodiment 2-2,2-3,2-4, it can be seen that different quality AlCl3Magnesium silicate with hydrochloric Acid Modification is to product matter
Amount has certain influence, but can reach ending ratio > 90%, color and luster < 60.
Embodiment 3-1 is magnesium silicate recovery and reusing and recycling.
Embodiment 3-1
Add water to stir embodiment 2-2 post-processing filter residues, magnesium silicate is then obtained by filtration, is then dried at 110 DEG C, in
2h is roasted in 450 DEG C of air atmospheres, is recycled regeneration magnesium silicate.
Method is fully according to embodiment 2-2, difference lies in using reclaiming magnesium silicate, products obtained therefrom ending ratio 94%,
Color and luster 42.
Above-mentioned magnesium silicate is subjected to regeneration treatment again, and during application and post-processing are refined, a regeneration time can be obtained
The tables of data of number and its performance.
The final product quality table of comparisons under 1 different technology conditions of table
| Regeneration times | Ending ratio/% | Color and luster (platinum-cobalt colorimetric method) |
| 1 | 94 | 42 |
| 2 | 94 | 45 |
| 3 | 94 | 53 |
As can be seen from the data in the table, modified magnesium silicate is after repeated reproducibility 3 times, product color still 60 <, ending ratio
> 90%.
Comparative example 1
By 2mol 954g laruyl alcohol alcohol polyoxyethylene ether (n=12, m=7), 3mol NaOH, 10g tetrabutylammonium bromide,
Slowly 3mol ECH are added in 2.5L reaction kettles, control temperature is no more than 40 DEG C, then is warming up to 40 DEG C and is stirred to react 5h,
It is filtered to remove solid, vacuum distillation recycles excessive ECH, is cooled to room temperature.
It phosphorates in acid to above-mentioned polyethers, adjusts pH value to faintly acid, then add the commercially available magnesium silicates of 10g, 2g activated carbons, 50g water,
It stirs evenly, is warming up to 75 DEG C of absorption 90min, then in 110 DEG C of dehydration and drying 1h of -0.098MPa vacuum conditions, be cooled to 80
DEG C it is filtered to remove solid, obtains brown yellow transparent liquid, color and luster 500, ending ratio 87%.
Pass through embodiment 2-2 and comparative example 1, it can be seen that prepared according to document mode, and using after conventional polyether
Process for refining is handled, product color is very deep, and ending ratio also wants small, illustrates that the present invention can not only 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 control table can be obtained, as shown in table 2.
The final product quality table of comparisons under 2 different technology conditions of table
| 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 |
By the present invention using fatty alcohol polyoxyethylene ether glycidol it can be seen from the various embodiments described above and the table of comparisons
It prepares and its post-processes, synthesis technology is practical simple, and convenient post-treatment, adsorbent magnesium silicate may be reused, and can obtain simultaneously
While obtaining higher ending ratio (> 93%), assign product high reaction activity compared with low color (< 46), the product of finished product are also ensured
Phase index.
The above content is the preferred embodiments of combination the invention to further detailed made by provided technical solution
Describe in detail bright, and it cannot be said that the invention specific implementation is confined to these above-mentioned explanations, for the affiliated technology of the invention
For the those of ordinary skill in field, without departing from the concept of the premise of the invention, several simple deductions can also be made
Or replace, it all shall be regarded as belonging to the protection domain of the invention.
Claims (8)
1. a kind of preparation method of fatty alcohol polyoxyethylene ether glycidol ether, it is characterised in that：Add fatty alcohol into reaction kettle
Polyoxyethylene ether, catalyst, alkali, polymerization inhibitor, stir evenly, and epoxychloropropane is added, and reaction finishes, and it is thick to obtain end capped polyether
Product；After end capped polyether crude product is filtered desalination, vacuum distillation recycling epoxychloropropane is cooled to room temperature, adds adsorbent, hydroxyl
Methyl sulfinic acid sodium, water, are refining to obtain finished product；
The adsorbent is modified magnesium silicate adsorbent, and preparation method is, by AlCl 3Powder, magnesium silicate, acid and water are mixed
It closes homogeneous modulation and squeezes into the plastic pug of tool, in 80-90 DEG C of oil bath after 24 h of hot submersion, in 110 DEG C of bakings
It is dry, then 2 h are roasted under 450 DEG C of air atmospheres, it sieves and 100-200 mesh adsorbents is made.
2. a kind of preparation method of fatty alcohol polyoxyethylene ether glycidol ether as described in claim 1, it is characterised in that：
Fatty alcohol polyoxyethylene ether and the molar ratio of epoxychloropropane are 1:The molar ratio of 1-10, fatty alcohol polyoxyethylene ether and alkali is
1:1-4, reaction time 1-10 h, 30-60 DEG C of reaction temperature.
3. a kind of preparation method of fatty alcohol polyoxyethylene ether glycidol ether as described in claim 1, it is characterised in that：
The alkali selects the mixing of one or more of sodium hydroxide, potassium hydroxide, sodium methoxide, sodium carbonate, potassium carbonate, sodium hydride
Object, the alkali are solid mixture, aqueous solution or the alcoholic solution of one or more.
4. a kind of preparation method of fatty alcohol polyoxyethylene ether glycidol ether as described in claim 1, it is characterised in that：
The polymerization inhibitor addition is the 0.1-0.5% of fatty alcohol polyoxyethylene ether quality, and polymerization inhibitor selects p-hydroxyanisole, 2-
The mixture of one or more of tert-butyl hydroquinone, methylnaphthohydroquinone, 1,4-benzoquinone, nitrobenzene substance.
5. a kind of preparation method of fatty alcohol polyoxyethylene ether glycidol ether as described in claim 1, it is characterised in that：
It is the 0.3-3% of the reactant quality of ring-closure reaction that the catalyst, which selects quaternary ammonium salt catalyst, dosage,.
6. a kind of preparation method of fatty alcohol polyoxyethylene ether glycidol ether as described in claim 5, it is characterised in that：
The quaternary ammonium salt catalyst selects etamon chloride, benzyltriethylammoinium chloride, tetrabutylammonium bromide, tetrabutyl chlorination
The mixture of one or more of ammonium, 4-butyl ammonium hydrogen sulfate or tri-n-octyl methyl ammonium chloride substance.
7. a kind of preparation method of fatty alcohol polyoxyethylene ether glycidol ether as described in claim 1, it is characterised in that：
The addition of the adsorbent is the 0.5-5% of end capped polyether crude product quality, and sodium hydroxymethanesulfinate is end capped polyether crude product
The 0.08-0.5% of quality, water are the 1-10% of end capped polyether crude product quality.
8. a kind of preparation method of fatty alcohol polyoxyethylene ether glycidol ether as described in claim 1, it is characterised in that：
The purification condition is 65-90 DEG C of thermostatic absorption 30-120 min, the heat preservation dehydration 1 at 110 DEG C, -0.098 Mpa
Then finished product is obtained by filtration at 80 DEG C in h.
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| 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 |
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