CN116253702A - Synthesis method of alkyl glycidyl ether - Google Patents
Synthesis method of alkyl glycidyl ether Download PDFInfo
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- CN116253702A CN116253702A CN202211715278.8A CN202211715278A CN116253702A CN 116253702 A CN116253702 A CN 116253702A CN 202211715278 A CN202211715278 A CN 202211715278A CN 116253702 A CN116253702 A CN 116253702A
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- glycidyl ether
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- alkyl glycidyl
- alkyl
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- -1 alkyl glycidyl ether Chemical compound 0.000 title claims abstract description 37
- 238000001308 synthesis method Methods 0.000 title claims abstract description 14
- 239000003054 catalyst Substances 0.000 claims abstract description 34
- 238000006243 chemical reaction Methods 0.000 claims abstract description 31
- 238000000034 method Methods 0.000 claims abstract description 28
- 230000001105 regulatory effect Effects 0.000 claims abstract description 16
- 238000007363 ring formation reaction Methods 0.000 claims abstract description 12
- 125000005233 alkylalcohol group Chemical group 0.000 claims abstract description 11
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 11
- BRLQWZUYTZBJKN-UHFFFAOYSA-N Epichlorohydrin Chemical compound ClCC1CO1 BRLQWZUYTZBJKN-UHFFFAOYSA-N 0.000 claims abstract description 10
- 238000001816 cooling Methods 0.000 claims abstract description 10
- 239000012043 crude product Substances 0.000 claims abstract description 10
- 238000001914 filtration Methods 0.000 claims abstract description 10
- 238000010438 heat treatment Methods 0.000 claims abstract description 9
- 239000000126 substance Substances 0.000 claims abstract description 9
- 239000013049 sediment Substances 0.000 claims abstract description 8
- 238000003756 stirring Methods 0.000 claims abstract description 7
- 239000003513 alkali Substances 0.000 claims abstract description 6
- 239000000706 filtrate Substances 0.000 claims abstract description 6
- 238000005406 washing Methods 0.000 claims abstract description 6
- 230000007935 neutral effect Effects 0.000 claims abstract description 5
- YIWUKEYIRIRTPP-UHFFFAOYSA-N 2-ethylhexan-1-ol Chemical compound CCCCC(CC)CO YIWUKEYIRIRTPP-UHFFFAOYSA-N 0.000 claims description 26
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical group [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 claims description 14
- RBTARNINKXHZNM-UHFFFAOYSA-K iron trichloride Chemical compound Cl[Fe](Cl)Cl RBTARNINKXHZNM-UHFFFAOYSA-K 0.000 claims description 11
- LRWZZZWJMFNZIK-UHFFFAOYSA-N 2-chloro-3-methyloxirane Chemical compound CC1OC1Cl LRWZZZWJMFNZIK-UHFFFAOYSA-N 0.000 claims description 9
- 230000002194 synthesizing effect Effects 0.000 claims description 8
- 229910000029 sodium carbonate Inorganic materials 0.000 claims description 7
- 238000004817 gas chromatography Methods 0.000 claims description 6
- 239000008367 deionised water Substances 0.000 claims description 4
- 229910021641 deionized water Inorganic materials 0.000 claims description 4
- 150000002191 fatty alcohols Chemical class 0.000 claims description 4
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical group [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 3
- 150000001335 aliphatic alkanes Chemical group 0.000 claims description 3
- 239000011968 lewis acid catalyst Substances 0.000 claims description 3
- 239000000203 mixture Substances 0.000 claims description 3
- FBAFATDZDUQKNH-UHFFFAOYSA-M iron chloride Chemical group [Cl-].[Fe] FBAFATDZDUQKNH-UHFFFAOYSA-M 0.000 claims description 2
- 238000004321 preservation Methods 0.000 claims description 2
- 230000008569 process Effects 0.000 abstract description 13
- 238000007142 ring opening reaction Methods 0.000 abstract description 10
- 238000004519 manufacturing process Methods 0.000 abstract description 6
- 238000002360 preparation method Methods 0.000 abstract description 3
- NCZPCONIKBICGS-UHFFFAOYSA-N 3-(2-ethylhexoxy)propane-1,2-diol Chemical compound CCCCC(CC)COCC(O)CO NCZPCONIKBICGS-UHFFFAOYSA-N 0.000 description 8
- 229910021578 Iron(III) chloride Inorganic materials 0.000 description 8
- 229940100524 ethylhexylglycerin Drugs 0.000 description 8
- 239000000047 product Substances 0.000 description 8
- 239000003755 preservative agent Substances 0.000 description 7
- YCUKMYFJDGKQFC-UHFFFAOYSA-N 2-(octan-3-yloxymethyl)oxirane Chemical compound CCCCCC(CC)OCC1CO1 YCUKMYFJDGKQFC-UHFFFAOYSA-N 0.000 description 6
- ANZUDYZHSVGBRF-UHFFFAOYSA-N 3-ethylnonane-1,2,3-triol Chemical compound CCCCCCC(O)(CC)C(O)CO ANZUDYZHSVGBRF-UHFFFAOYSA-N 0.000 description 6
- 239000003377 acid catalyst Substances 0.000 description 5
- 239000002537 cosmetic Substances 0.000 description 5
- GYZLOYUZLJXAJU-UHFFFAOYSA-N diglycidyl ether Chemical compound C1OC1COCC1CO1 GYZLOYUZLJXAJU-UHFFFAOYSA-N 0.000 description 4
- 239000012535 impurity Substances 0.000 description 4
- 230000002335 preservative effect Effects 0.000 description 4
- 239000002699 waste material Substances 0.000 description 4
- WSFSSNUMVMOOMR-UHFFFAOYSA-N Formaldehyde Chemical compound O=C WSFSSNUMVMOOMR-UHFFFAOYSA-N 0.000 description 3
- 239000000654 additive Substances 0.000 description 3
- 230000002421 anti-septic effect Effects 0.000 description 3
- NMRPBPVERJPACX-UHFFFAOYSA-N (3S)-octan-3-ol Natural products CCCCCC(O)CC NMRPBPVERJPACX-UHFFFAOYSA-N 0.000 description 2
- PEDCQBHIVMGVHV-UHFFFAOYSA-N Glycerol Natural products OCC(O)CO PEDCQBHIVMGVHV-UHFFFAOYSA-N 0.000 description 2
- 238000005481 NMR spectroscopy Methods 0.000 description 2
- HEDRZPFGACZZDS-MICDWDOJSA-N Trichloro(2H)methane Chemical group [2H]C(Cl)(Cl)Cl HEDRZPFGACZZDS-MICDWDOJSA-N 0.000 description 2
- 229910052799 carbon Inorganic materials 0.000 description 2
- 150000001875 compounds Chemical class 0.000 description 2
- 230000001276 controlling effect Effects 0.000 description 2
- 230000001877 deodorizing effect Effects 0.000 description 2
- 238000006266 etherification reaction Methods 0.000 description 2
- 235000011187 glycerol Nutrition 0.000 description 2
- 230000036541 health Effects 0.000 description 2
- 239000007788 liquid Substances 0.000 description 2
- 230000003020 moisturizing effect Effects 0.000 description 2
- 238000006798 ring closing metathesis reaction Methods 0.000 description 2
- 230000001988 toxicity Effects 0.000 description 2
- 231100000419 toxicity Toxicity 0.000 description 2
- BBBUAWSVILPJLL-UHFFFAOYSA-N 2-(2-ethylhexoxymethyl)oxirane Chemical compound CCCCC(CC)COCC1CO1 BBBUAWSVILPJLL-UHFFFAOYSA-N 0.000 description 1
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 1
- XEFQLINVKFYRCS-UHFFFAOYSA-N Triclosan Chemical compound OC1=CC(Cl)=CC=C1OC1=CC=C(Cl)C=C1Cl XEFQLINVKFYRCS-UHFFFAOYSA-N 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 150000008065 acid anhydrides Chemical class 0.000 description 1
- 238000007171 acid catalysis Methods 0.000 description 1
- 238000007259 addition reaction Methods 0.000 description 1
- 230000000996 additive effect Effects 0.000 description 1
- 238000005904 alkaline hydrolysis reaction Methods 0.000 description 1
- 238000005815 base catalysis Methods 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 238000009835 boiling Methods 0.000 description 1
- 239000006227 byproduct Substances 0.000 description 1
- 125000002915 carbonyl group Chemical group [*:2]C([*:1])=O 0.000 description 1
- 238000006555 catalytic reaction Methods 0.000 description 1
- 230000007797 corrosion Effects 0.000 description 1
- 238000005260 corrosion Methods 0.000 description 1
- 239000000490 cosmetic additive Substances 0.000 description 1
- 238000002845 discoloration Methods 0.000 description 1
- 125000003700 epoxy group Chemical group 0.000 description 1
- 229960004887 ferric hydroxide Drugs 0.000 description 1
- 230000007062 hydrolysis Effects 0.000 description 1
- 238000006460 hydrolysis reaction Methods 0.000 description 1
- IEECXTSVVFWGSE-UHFFFAOYSA-M iron(3+);oxygen(2-);hydroxide Chemical compound [OH-].[O-2].[Fe+3] IEECXTSVVFWGSE-UHFFFAOYSA-M 0.000 description 1
- 239000002932 luster Substances 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 238000006116 polymerization reaction Methods 0.000 description 1
- 238000000746 purification Methods 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 230000035484 reaction time Effects 0.000 description 1
- 238000005070 sampling Methods 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 230000002195 synergetic effect Effects 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- 230000002110 toxicologic effect Effects 0.000 description 1
- 231100000027 toxicology Toxicity 0.000 description 1
- 229960003500 triclosan Drugs 0.000 description 1
- 238000012795 verification Methods 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D301/00—Preparation of oxiranes
- C07D301/27—Condensation of epihalohydrins or halohydrins with compounds containing active hydrogen atoms
- C07D301/28—Condensation of epihalohydrins or halohydrins with compounds containing active hydrogen atoms by reaction with hydroxyl radicals
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J27/00—Catalysts comprising the elements or compounds of halogens, sulfur, selenium, tellurium, phosphorus or nitrogen; Catalysts comprising carbon compounds
- B01J27/06—Halogens; Compounds thereof
- B01J27/128—Halogens; Compounds thereof with iron group metals or platinum group metals
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C41/00—Preparation of ethers; Preparation of compounds having groups, groups or groups
- C07C41/01—Preparation of ethers
- C07C41/18—Preparation of ethers by reactions not forming ether-oxygen bonds
- C07C41/26—Preparation of ethers by reactions not forming ether-oxygen bonds by introduction of hydroxy or O-metal groups
-
- 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
- C07D303/18—Compounds containing oxirane rings with hydrocarbon radicals, substituted by singly or doubly bound oxygen atoms by etherified hydroxyl radicals
- C07D303/20—Ethers with hydroxy compounds containing no oxirane rings
- C07D303/22—Ethers with hydroxy compounds containing no oxirane rings with monohydroxy compounds
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P20/00—Technologies relating to chemical industry
- Y02P20/50—Improvements relating to the production of bulk chemicals
- Y02P20/584—Recycling of catalysts
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Epoxy Compounds (AREA)
- Low-Molecular Organic Synthesis Reactions Using Catalysts (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
The invention discloses a synthesis method of alkyl glycidyl ether, which specifically comprises the following steps: adding alkyl alcohol and a catalyst into a reaction bottle, stirring and heating to start dripping epichlorohydrin, cooling after reacting to a certain degree, adding a terminator after cooling, adjusting the PH to a certain value by using an alkaline substance, filtering out sediment in the reaction bottle, adjusting the PH of the filtered filtrate to 11-12 by using alkali liquor, heating and preserving heat after adjustment, and performing ring closure reaction to generate a crude product; and (3) washing the prepared crude product to be nearly neutral, and separating an oil layer to obtain the alkyl glycidyl ether. The catalyst used in the invention simplifies the process, and after the ring opening is finished and the water addition is finished, the PH is regulated to be more than 5, the catalyst is precipitated and separated out, and then the catalyst is filtered and separated, so that the subsequent reaction is not influenced. The catalyst consumption is small, only 0.5% is needed, the ring-opening reaction can be finished only for about 2 hours, the production cost is low, and the preparation efficiency is high.
Description
Technical Field
The invention relates to preparation of a preservative ethylhexyl glycerol intermediate, in particular to a novel alkyl glycidyl ether synthesis method for preparing ethylhexyl glycerol through the alkyl glycidyl ether intermediate.
Background
The traditional preservative for daily chemical products has certain toxicity and is easy to cause harm to the environment and human health. The european union, month 1 of 2014, announced that triclosan was prohibited from use in cosmetics, with some of the unusual parabens accompanying the ban; the message that the infant bathroom products produced by the international famous daily chemical enterprises contain formaldehyde is reported by media, so that the increased risk of using the traditional preservative is warned, and the worldwide panic is caused. The safety of preservative is highly important in China's new implementation of technical Specification for safety of 2015 cosmetics (instead of the Specification for health of 2007 cosmetics). The ethylhexyl glycerin is a novel multifunctional cosmetic additive with antiseptic efficacy and moisturizing and deodorizing effects, brings hopes to people, particularly, the ethylhexyl glycerin and the synergistic effect of other traditional preservatives are utilized for daily chemical product systems, the adding amount of the traditional preservatives can be greatly reduced, the skin is not stimulated, the toxicity of the antiseptic system is remarkably reduced, the moisturizing and deodorizing effects are achieved, the capability of the traditional preservatives can be enhanced, and the ethylhexyl glycerin plays an important role in a future green antiseptic system.
The boiling point of the ethylhexyl glycerol is about 300 ℃, separation and purification are difficult in process production, oxidation and discoloration are easy in the process, impurities are easy to polymerize during synthesis, the ethylhexyl glycerol with high impurity content can influence the color and luster, has peculiar smell, and some impurities can influence the toxicological safety, so that the ethylhexyl glycerol cannot be used as a daily chemical additive. The route for producing ethylhexyl glycerin is mature, the process of generating glycidyl ether intermediate by etherification technology, then producing ethylhexyl glycerin is common, one is self-polymerization byproducts of acid anhydride and glycidyl ether which are produced by alkaline hydrolysis after addition reaction, the other is that alcohol and glycidyl ether are used for preparing ethylhexyl glycerin under acid or base catalysis, the reaction time is long, the impurity is more, and the third is that carbonyl addition is carried out by opening epoxy groups of ethylhexyl glycidyl ether by catalysis, and then hydrolysis. Although the process route for preparing the ethylhexyl glycerol is mature, in order to adapt to market competition, the production cost is continuously compressed, innovation is continuously carried out, and products with high efficiency and higher specification are expected to be a focus direction, so that the search of the catalyst of the etherification process is emphasized to improve the efficiency and simplify the process, and the purposes of low cost, high specification and high return green production are achieved.
The main synthesis method at present is to react the ethylhexanol with the epichlorohydrin under the acid catalyst, then carry out the ring-closure step to obtain the ethylhexanol, then carry out the ring-closure reaction with the epichlorohydrin under the acid catalyst, then carry out the ring-closure reaction under the alkaline condition to obtain the glycidyl ether, the acid catalyst needs additional steps to be removed, otherwise, the following steps of reaction can be influenced, thus the acid catalyst treatment is time-consuming and labor-consuming, and if the removal is incomplete, the quality and the performance of the product can be influenced, so the acid catalyst can be rapidly and effectively removed, and the problem of the industry concern is solved.
Disclosure of Invention
In view of the above problems, after the ring-opening reaction is finished, the catalyst is removed by a simple process, and the next ring-opening reaction is directly carried out.
According to the method for preparing the alkyl glycidyl ether, disclosed by the invention, the synthesis method of the alkyl glycidyl ether is improved through the use of the ferric chloride catalyst, the catalyst can be used for efficiently catalyzing the ring-opening reaction, after the ring-opening reaction is finished, water is added and stirred, the pH value of a reaction solution is regulated to be greater than 5, so that the catalyst is completely precipitated, and the ring-closing reaction of the second step can be directly carried out after the catalyst is removed by filtering. The method ensures that the post-treatment of the process is very simple and convenient, the ferric chloride catalyst can be removed rapidly and effectively, the PH is adjusted, and then the waste residue is removed by direct filtration, thereby reducing the generation of waste residue. The alkyl glyceryl ether prepared by the method can be directly used for preparing alkyl glycerin, in particular ethylhexyl glycerin after filtration and layering, and is suitable for multifunctional additives of cosmetics and household care products.
The invention uses ferric chloride catalyst to prepare alkyl glycidyl ether, especially ethylhexyl glycidyl ether, and the specific scheme is as follows:
the invention provides a synthesis method of alkyl glycidyl ether, which comprises the following steps:
s1: adding alkyl alcohol and a catalyst into a reaction bottle, stirring and heating to a temperature ranging from 100 ℃ to 120 ℃, and then beginning to dropwise add epoxy chloropropane, wherein the molar mass ratio of the alkyl alcohol to the epoxy chloropropane is 1:0.8-1.2;
s2: s1, cooling after reacting to a certain extent, adding a terminator after cooling, regulating the PH value to a certain value by using an alkaline substance, filtering out sediment in a reaction bottle, regulating the PH value of filtered filtrate to 11-12 by using alkali liquor, heating to 70-90 ℃ after regulating the PH value, preserving heat, and performing ring closure reaction to generate a crude product;
s3: washing the crude product obtained in the step S2 to be nearly neutral, and separating an oil layer to obtain the alkyl glycidyl ether with the structure conforming to the general formula (I);
wherein, the structural general formula of the prepared alkyl glycidyl ether is as follows:
r=c5 to C18 carbon chain
As a preferable scheme of the synthesis method of the alkyl glycidyl ether, the catalyst is ferric chloride Lewis acid catalyst.
As a preferable scheme of the synthesis method of the alkyl glycidyl ether, in the step S1, after stirring and heating to a temperature of 110 ℃, the epoxy chloropropane is started to be added dropwise;
in the step S2, the temperature is reduced to 60 ℃ after the reaction in the step S1 reaches a certain degree; the alkaline substance is sodium carbonate;
in the step S3, the pH value is adjusted, then the mixture is heated to 80 ℃ for heat preservation, and the cyclization reaction is carried out for 18 hours to generate a crude product.
As a preferable scheme of the synthesis method of the alkyl glycidyl ether, in the step S2, the temperature is reduced to 60 ℃ when the content of the alkyl alcohol is controlled to be lower than 5% by adopting gas chromatography.
In step S1, the alkyl alcohol is 2-ethylhexanol, and the molar mass ratio of the epichlorohydrin to the 2-ethylhexanol is preferably 1.1:1.
As a preferred embodiment of the method for synthesizing alkyl glycidyl ether described in the present patent, the catalyst accounts for 0.5% of the total mass of alkyl alcohol and epichlorohydrin.
As a preferable scheme of the synthesis method of alkyl glycidyl ether, in the step S2, the terminator is deionized water;
in the step S2, the PH value in the reaction bottle is regulated to be more than 5 by sodium carbonate, and sediment in the reaction bottle is filtered, so that the ferric trichloride catalyst can be separated and removed.
As a preferable scheme of the synthesizing method of the alkyl glycidyl ether, R is a straight carbon chain fatty alcohol or an alkane group of a branched carbon chain fatty alcohol with 5-18.
Compared with the prior art, the invention has at least one or more of the following beneficial effects:
after the ring-opening reaction is finished, the catalyst is removed through a simple process, and the next ring-closing reaction is directly carried out.
According to the method for preparing the alkyl glycidyl ether, disclosed by the invention, the synthesis method of the alkyl glycidyl ether is improved through the use of the ferric chloride catalyst, the catalyst can be used for efficiently catalyzing the ring-opening reaction, water is added and stirred after the ring-opening reaction is finished, the pH value of a reaction solution is regulated to be more than 5, the catalyst is completely precipitated, the catalyst can be separated out in the form of ferric hydroxide, and the ring-closing reaction of the second step can be directly carried out after the catalyst is filtered and removed, so that the subsequent reaction is not influenced. The method ensures that the post-treatment of the process is very simple and convenient, the ferric chloride catalyst can be removed rapidly and effectively, the PH is adjusted, and then the waste residue is removed by direct filtration, thereby reducing the generation of waste residue. The alkyl glyceryl ether prepared by the method can be directly used for preparing alkyl glycerin, in particular ethylhexyl glycerin after filtration and layering, and is suitable for multifunctional additives of cosmetics and household care products. Greatly simplifying the process steps.
The catalyst has the advantages of small dosage, low production cost and high preparation efficiency, and can catalyze the reaction only by 0.5 percent of the total mass of the reaction raw materials, and the ring-opening reaction can be finished only by about 2 hours.
The corrosion degree of the ferric chloride catalyst to equipment is relatively reduced, and the process production is facilitated.
Additional aspects and advantages of the invention will be set forth in part in the description which follows, and in part will be obvious from the description, or may be learned by practice of the invention.
Detailed Description
Embodiments of the present invention will be described in detail below, and technical solutions in the embodiments of the present invention will be clearly and completely described, and it is apparent that the described embodiments are only some embodiments of the present invention, not all embodiments. All other embodiments, which can be made by those skilled in the art based on the embodiments of the invention without making any inventive effort, are intended to be within the scope of the invention.
The synthesis method of the alkyl glycidyl ether provided by the embodiment specifically comprises the following steps:
s1: 2-ethylhexanol and a catalyst are put into a reaction bottle, after stirring and heating to 110 ℃, epoxy chloropropane is added dropwise, wherein the catalyst accounts for 0.5 percent of the total mass of the 2-ethylhexanol and the epoxy chloropropane, and the molar mass ratio of the 2-ethylhexanol to the epoxy chloropropane is 1:0.8-1.2; preferably, the molar mass ratio of 2-ethylhexanol to epichlorohydrin is preferably 1:1.1; preferably, the catalyst is preferably an iron chloride lewis acid catalyst;
s2: step S1, cooling to 60 ℃ after reacting to a certain degree, adding a terminator after cooling, adjusting the PH value with sodium carbonate, filtering out sediment in a reaction bottle, adjusting the PH value of the filtered filtrate to 11-12 with alkali liquor, heating to 80 ℃ after adjusting, preserving heat, and performing ring closure reaction for 18 hours to generate a crude product;
s3: washing the crude product obtained in the step S2 to be nearly neutral, and separating an oil layer to obtain the 2-ethylhexyl glycidyl ether with the structure conforming to the general formula (I);
wherein, the structural general formula (I) of the prepared alkyl glycidyl ether is as follows:
r=c5 to C18 carbon chain
Preferably, R is an alkane group of a straight chain fatty alcohol or a branched chain fatty alcohol of 5 to 18.
Preferably, in step S2, the temperature is reduced to 60 ℃ when the content of 2-ethylhexanol is controlled to be lower than 5% by gas chromatography.
Preferably, in step S2, the terminator is deionized water; and regulating the PH value in the reaction bottle to be more than 5 by sodium carbonate, and filtering out sediment in the reaction bottle to separate and remove the ferric trichloride catalyst.
Example 1
1. Adding 19.5g of 2-ethylhexanol and 0.086g of ferric chloride into a 150ml four-port reaction bottle provided with a mechanical stirrer, a thermometer and a dropping funnel, placing the four-port reaction bottle into an oil bath, controlling the temperature to 110 ℃ under the stirring of the mechanical stirrer, and dripping 15g of epichlorohydrin, and controlling the dripping speed to be about 1 hour;
2. after the epoxy chloropropane is dripped, the temperature is maintained and stirred for 2 hours, sampling gas chromatography is started until the content of 2-ethylhexanol is lower than 5%, cooling is carried out to 60 ℃ when the content of 2-ethylhexanol is lower than 5%, 40g deionized water is added into a four-port reaction bottle after cooling to terminate the reaction, sodium carbonate is used for regulating the PH value in the four-port reaction bottle to be larger than 5 after termination, stirring is carried out for 30 minutes after regulating the PH value, sediment in the four-port reaction bottle is filtered, the collected filtrate is regulated to be about 11 by 30% liquid alkali, the temperature is raised to 80 ℃ after regulating the PH value, the temperature is maintained and closed-loop reaction is carried out for 18 hours, the PH value is continuously detected in the process of the temperature maintaining and the PH value is maintained at about 11 by adding liquid alkali if the PH value is reduced; the gas chromatography monitors the ring closure condition until the content of the ethylhexyl glycidyl ether exceeds 90%, the ring closure reaction is stopped, water washing is started, the water washing is carried out twice until the water is nearly neutral, a water-washed oil phase is collected, 33.2g of a crude ethylhexyl glycidyl ether product is obtained after a small amount of water is removed from the oil phase, the content of the ethylhexyl glycidyl ether (GC content for short) in the oil phase is measured to be 92% by gas chromatography, and the calculated yield is 91.5%.
And (3) experimental verification: the prepared target compound is tested by nuclear magnetic resonance (H NMR), the test condition is that the instrument frequency is 400MHz, the solvent is CDCl3, and the test result is that: delta = 0.87-0.89 (6 h, m), 1.24-1.43 (8 h, m), 1.48-1.52 (1 h, m), 2.56 (1 h, m), 2.78 (1 h, q), 3.10-3.15 (1 h, m), 3.29-3.42 (3 h, m), 3.64-3.70 (1 h, m), confirming that the resulting target compound is ethylhexyl glycidyl ether.
While embodiments of the invention have been illustrated and described above, it should be understood that the above embodiments are illustrative and not to be construed as limiting the invention, and that any modifications, equivalent substitutions, improvements, etc. that fall within the spirit and principles of the invention are intended to be included within the scope of the invention.
Claims (7)
1. The synthesis method of the alkyl glycidyl ether is characterized by comprising the following steps of:
s1: adding alkyl alcohol and a catalyst into a reaction bottle, stirring and heating to a temperature ranging from 100 ℃ to 120 ℃, and then beginning to dropwise add epoxy chloropropane, wherein the molar mass ratio of the alkyl alcohol to the epoxy chloropropane is 1:0.8-1.2;
s2: cooling the reaction in the step S1 to a certain extent, adding a terminator after cooling, regulating the PH value to a certain value by using an alkaline substance, filtering out sediment in a reaction bottle, regulating the PH value of the filtered filtrate to 11-12 by using alkali liquor, heating the filtrate to 70-90 ℃ after regulating the PH value, preserving heat, and performing ring closure reaction to generate a crude product;
s3: washing the crude product obtained in the step S2 to be nearly neutral, and separating an oil layer to obtain the alkyl glycidyl ether with the structure conforming to the general formula (I);
wherein, the structural general formula (I) of the prepared alkyl glycidyl ether is as follows:
r=c5 to C18 carbon chain.
2. The method for synthesizing an alkyl glycidyl ether according to claim 1, wherein the catalyst is an iron chloride lewis acid catalyst.
3. The method for synthesizing an alkyl glycidyl ether according to claim 1 or 2, wherein in the step S1, the epichlorohydrin is started to be added dropwise after the mixture is stirred and heated to a temperature ranging from 110 ℃;
in the step S2, the temperature is reduced to 60 ℃ after the reaction in the step S1 reaches a certain degree; the alkaline substance is sodium carbonate;
in the step S3, the pH value is adjusted, then the mixture is heated to 80 ℃ for heat preservation, and the cyclization reaction is carried out for 18 hours to generate a crude product.
4. The method for synthesizing the alkyl glycidyl ether according to claim 3, wherein in the step S2, the temperature is reduced to 60 ℃ when the content of the alkyl alcohol is controlled to be lower than 5% by adopting gas chromatography;
in step S1, the alkyl alcohol is 2-ethylhexanol, and the molar mass ratio of the epichlorohydrin to the 2-ethylhexanol is preferably 1.1:1.
5. The method for synthesizing an alkyl glycidyl ether according to claim 1 or 2, wherein the catalyst accounts for 0.5% of the total mass of the alkyl alcohol and the epichlorohydrin.
6. The method for synthesizing alkyl glycidyl ether according to claim 3, wherein in the step S2, the terminator is deionized water;
in the step S2, the PH value in the reaction bottle is regulated to be more than 5 by sodium carbonate, and sediment in the reaction bottle is filtered, so that the ferric trichloride catalyst can be separated and removed.
7. The method for synthesizing an alkyl glycidyl ether according to claim 1, wherein R is an alkane group of a straight chain fatty alcohol or a branched chain fatty alcohol of 5 to 18.
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