CN115785027A - Synthetic method of low-chlorine long-chain alkyl glycidyl ether - Google Patents
Synthetic method of low-chlorine long-chain alkyl glycidyl ether Download PDFInfo
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- CN115785027A CN115785027A CN202111058888.0A CN202111058888A CN115785027A CN 115785027 A CN115785027 A CN 115785027A CN 202111058888 A CN202111058888 A CN 202111058888A CN 115785027 A CN115785027 A CN 115785027A
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- long
- chain alkyl
- glycidyl ether
- chlorine
- perchlorate
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- -1 alkyl glycidyl ether Chemical compound 0.000 title claims abstract description 47
- 239000000460 chlorine Substances 0.000 title claims abstract description 27
- 229910052801 chlorine Inorganic materials 0.000 title claims abstract description 27
- 238000010189 synthetic method Methods 0.000 title claims description 3
- 239000003054 catalyst Substances 0.000 claims abstract description 29
- 238000000034 method Methods 0.000 claims abstract description 27
- 239000003513 alkali Substances 0.000 claims abstract description 20
- VLTRZXGMWDSKGL-UHFFFAOYSA-M perchlorate Inorganic materials [O-]Cl(=O)(=O)=O VLTRZXGMWDSKGL-UHFFFAOYSA-M 0.000 claims abstract description 17
- VLTRZXGMWDSKGL-UHFFFAOYSA-N perchloric acid Chemical compound OCl(=O)(=O)=O VLTRZXGMWDSKGL-UHFFFAOYSA-N 0.000 claims abstract description 17
- 239000002841 Lewis acid Substances 0.000 claims abstract description 14
- 239000002131 composite material Substances 0.000 claims abstract description 14
- 150000007517 lewis acids Chemical class 0.000 claims abstract description 14
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 claims abstract description 12
- 238000006266 etherification reaction Methods 0.000 claims abstract description 10
- 238000007142 ring opening reaction Methods 0.000 claims abstract description 9
- 238000003402 intramolecular cyclocondensation reaction Methods 0.000 claims abstract description 8
- LRWZZZWJMFNZIK-UHFFFAOYSA-N 2-chloro-3-methyloxirane Chemical compound CC1OC1Cl LRWZZZWJMFNZIK-UHFFFAOYSA-N 0.000 claims abstract description 7
- XENVCRGQTABGKY-ZHACJKMWSA-N chlorohydrin Chemical compound CC#CC#CC#CC#C\C=C\C(Cl)CO XENVCRGQTABGKY-ZHACJKMWSA-N 0.000 claims abstract description 6
- 239000013067 intermediate product Substances 0.000 claims abstract description 6
- 230000009471 action Effects 0.000 claims abstract description 3
- 238000006243 chemical reaction Methods 0.000 claims description 38
- KZMGYPLQYOPHEL-UHFFFAOYSA-N Boron trifluoride etherate Chemical compound FB(F)F.CCOCC KZMGYPLQYOPHEL-UHFFFAOYSA-N 0.000 claims description 14
- 238000010438 heat treatment Methods 0.000 claims description 9
- 230000008569 process Effects 0.000 claims description 8
- MPCRDALPQLDDFX-UHFFFAOYSA-L Magnesium perchlorate Chemical compound [Mg+2].[O-]Cl(=O)(=O)=O.[O-]Cl(=O)(=O)=O MPCRDALPQLDDFX-UHFFFAOYSA-L 0.000 claims description 7
- JIAARYAFYJHUJI-UHFFFAOYSA-L zinc dichloride Chemical compound [Cl-].[Cl-].[Zn+2] JIAARYAFYJHUJI-UHFFFAOYSA-L 0.000 claims description 6
- BRLQWZUYTZBJKN-UHFFFAOYSA-N Epichlorohydrin Chemical compound ClCC1CO1 BRLQWZUYTZBJKN-UHFFFAOYSA-N 0.000 claims description 5
- VSCWAEJMTAWNJL-UHFFFAOYSA-K aluminium trichloride Chemical compound Cl[Al](Cl)Cl VSCWAEJMTAWNJL-UHFFFAOYSA-K 0.000 claims description 3
- ZRGUXTGDSGGHLR-UHFFFAOYSA-K aluminum;triperchlorate Chemical compound [Al+3].[O-]Cl(=O)(=O)=O.[O-]Cl(=O)(=O)=O.[O-]Cl(=O)(=O)=O ZRGUXTGDSGGHLR-UHFFFAOYSA-K 0.000 claims description 3
- 239000011968 lewis acid catalyst Substances 0.000 claims description 3
- 238000002156 mixing Methods 0.000 claims description 3
- 239000011592 zinc chloride Substances 0.000 claims description 3
- 235000005074 zinc chloride Nutrition 0.000 claims description 3
- RXBXBWBHKPGHIB-UHFFFAOYSA-L zinc;diperchlorate Chemical compound [Zn+2].[O-]Cl(=O)(=O)=O.[O-]Cl(=O)(=O)=O RXBXBWBHKPGHIB-UHFFFAOYSA-L 0.000 claims description 3
- 229910021627 Tin(IV) chloride Inorganic materials 0.000 claims description 2
- 229910052783 alkali metal Inorganic materials 0.000 claims description 2
- 150000008044 alkali metal hydroxides Chemical group 0.000 claims description 2
- HPGGPRDJHPYFRM-UHFFFAOYSA-J tin(iv) chloride Chemical compound Cl[Sn](Cl)(Cl)Cl HPGGPRDJHPYFRM-UHFFFAOYSA-J 0.000 claims description 2
- 230000002194 synthesizing effect Effects 0.000 claims 11
- 239000004593 Epoxy Substances 0.000 abstract description 11
- 230000008901 benefit Effects 0.000 abstract description 7
- 238000001308 synthesis method Methods 0.000 abstract description 6
- 230000007613 environmental effect Effects 0.000 abstract description 4
- 229910052736 halogen Inorganic materials 0.000 abstract description 3
- 150000002367 halogens Chemical class 0.000 abstract description 3
- 239000003960 organic solvent Substances 0.000 abstract description 3
- 238000004134 energy conservation Methods 0.000 abstract description 2
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 45
- 239000000047 product Substances 0.000 description 20
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 description 9
- 239000000203 mixture Substances 0.000 description 8
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 8
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 7
- 230000018044 dehydration Effects 0.000 description 7
- 238000006297 dehydration reaction Methods 0.000 description 7
- 239000003822 epoxy resin Substances 0.000 description 7
- 230000007935 neutral effect Effects 0.000 description 7
- 229920000647 polyepoxide Polymers 0.000 description 7
- 238000007363 ring formation reaction Methods 0.000 description 7
- 238000003756 stirring Methods 0.000 description 7
- 239000003085 diluting agent Substances 0.000 description 6
- 230000015572 biosynthetic process Effects 0.000 description 4
- LQZZUXJYWNFBMV-UHFFFAOYSA-N dodecan-1-ol Chemical compound CCCCCCCCCCCCO LQZZUXJYWNFBMV-UHFFFAOYSA-N 0.000 description 4
- 238000003786 synthesis reaction Methods 0.000 description 4
- IFPMZBBHBZQTOV-UHFFFAOYSA-N 1,3,5-trinitro-2-(2,4,6-trinitrophenyl)-4-[2,4,6-trinitro-3-(2,4,6-trinitrophenyl)phenyl]benzene Chemical compound [O-][N+](=O)C1=CC([N+](=O)[O-])=CC([N+]([O-])=O)=C1C1=C([N+]([O-])=O)C=C([N+]([O-])=O)C(C=2C(=C(C=3C(=CC(=CC=3[N+]([O-])=O)[N+]([O-])=O)[N+]([O-])=O)C(=CC=2[N+]([O-])=O)[N+]([O-])=O)[N+]([O-])=O)=C1[N+]([O-])=O IFPMZBBHBZQTOV-UHFFFAOYSA-N 0.000 description 3
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical group [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 3
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 description 3
- 238000009835 boiling Methods 0.000 description 3
- 125000004432 carbon atom Chemical group C* 0.000 description 3
- 230000003197 catalytic effect Effects 0.000 description 3
- 230000000052 comparative effect Effects 0.000 description 3
- DGQNHSVGKNZFSM-UHFFFAOYSA-N [C].CCCCCCCCCCCCCCO Chemical compound [C].CCCCCCCCCCCCCCO DGQNHSVGKNZFSM-UHFFFAOYSA-N 0.000 description 2
- 230000009286 beneficial effect Effects 0.000 description 2
- 229910052799 carbon Inorganic materials 0.000 description 2
- 238000001514 detection method Methods 0.000 description 2
- 231100000053 low toxicity Toxicity 0.000 description 2
- 125000001421 myristyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 2
- 238000002360 preparation method Methods 0.000 description 2
- 238000007086 side reaction Methods 0.000 description 2
- 238000005406 washing Methods 0.000 description 2
- YSUQLAYJZDEMOT-UHFFFAOYSA-N 2-(butoxymethyl)oxirane Chemical compound CCCCOCC1CO1 YSUQLAYJZDEMOT-UHFFFAOYSA-N 0.000 description 1
- NVKSMKFBUGBIGE-UHFFFAOYSA-N 2-(tetradecoxymethyl)oxirane Chemical compound CCCCCCCCCCCCCCOCC1CO1 NVKSMKFBUGBIGE-UHFFFAOYSA-N 0.000 description 1
- FQYUMYWMJTYZTK-UHFFFAOYSA-N Phenyl glycidyl ether Chemical compound C1OC1COC1=CC=CC=C1 FQYUMYWMJTYZTK-UHFFFAOYSA-N 0.000 description 1
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 description 1
- 125000000217 alkyl group Chemical group 0.000 description 1
- 239000002585 base Substances 0.000 description 1
- 238000004891 communication Methods 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 239000012043 crude product Substances 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 239000008367 deionised water Substances 0.000 description 1
- 229910021641 deionized water Inorganic materials 0.000 description 1
- GYZLOYUZLJXAJU-UHFFFAOYSA-N diglycidyl ether Chemical compound C1OC1COCC1CO1 GYZLOYUZLJXAJU-UHFFFAOYSA-N 0.000 description 1
- 125000003700 epoxy group Chemical group 0.000 description 1
- 231100000086 high toxicity Toxicity 0.000 description 1
- 238000009776 industrial production Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000035699 permeability Effects 0.000 description 1
- 238000003918 potentiometric titration Methods 0.000 description 1
- 238000011112 process operation Methods 0.000 description 1
- HPOKESDSMZRZLC-UHFFFAOYSA-N propan-2-one;hydrochloride Chemical compound Cl.CC(C)=O HPOKESDSMZRZLC-UHFFFAOYSA-N 0.000 description 1
- QDRKDTQENPPHOJ-UHFFFAOYSA-N sodium ethoxide Chemical compound [Na+].CC[O-] QDRKDTQENPPHOJ-UHFFFAOYSA-N 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 238000009736 wetting Methods 0.000 description 1
- 229910052725 zinc Inorganic materials 0.000 description 1
- 239000011701 zinc Substances 0.000 description 1
Classifications
-
- 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
- Y02P20/10—Process efficiency
-
- 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
- Low-Molecular Organic Synthesis Reactions Using Catalysts (AREA)
Abstract
The invention discloses a synthesis method of low-chlorine long-chain alkyl glycidyl ether. Dripping epoxy chloropropane into long-chain alkyl fatty alcohol, and carrying out ring-opening etherification reaction under the action of a perchlorate/Lewis acid composite catalyst to obtain a chlorohydrin ether intermediate product; performing intramolecular cyclization reaction on the chlorohydrin ether intermediate product and an alkali catalyst to obtain long-chain alkyl glycidyl ether; the method has the advantages of short flow, simple operation, high yield, no need of organic solvent, environmental protection and energy conservation, and the obtained long-chain alkyl glycidyl ether has the advantages of low epoxy equivalent, low halogen content and the like.
Description
Technical Field
The invention relates to a synthesis method of glycidyl ether, in particular to a synthesis method of low-chlorine long-chain alkyl glycidyl ether, belonging to the technical field of synthesis of epoxy resin reactive diluents.
Background
The epoxy resin has excellent mechanical property, has the advantages of chemical medium resistance, bonding property, insulating property and the like, and is widely applied to the high and new technical fields of machinery, electronics, communication and aerospace. However, in practical application, due to large viscosity and poor fluidity and permeability, proper diluent is required to be added to reduce the viscosity, increase the fluidity, improve the wetting power and improve the process operation performance.
The reactive diluent generally refers to a low-molecular compound with one or more than two epoxy groups, can directly participate in the curing reaction of the epoxy resin, becomes a part of a cross-linked network structure of a cured epoxy resin, and has almost no influence on the performance of the cured epoxy resin. Reactive diluents therefore occupy an important position in epoxy resin applications. Commonly used reactive diluents such as phenyl glycidyl ether, butyl glycidyl ether and the like cannot meet the increasing environmental requirements due to low boiling point, high volatility and high toxicity. There is a need to develop new epoxy resin reactive diluents with low toxicity and low volatility. The dodeca/tetradecyl mixed alcohol has longer carbon chain, higher boiling point, high boiling point of the dodeca/tetradecyl glycidyl ether synthesized by the dodeca/tetradecyl mixed alcohol, small volatility and low toxicity, and also has better flexibility. At present, few reports on the preparation method of the C-dodecyl/tetradecyl glycidyl ether are reported in China, and only Chinese patent CN101440074A discloses a preparation method of the C-dodecyl/tetradecyl glycidyl ether, but the synthesis method is relatively complex and is not beneficial to industrial production.
Disclosure of Invention
Aiming at the defects in the prior art, the invention aims to provide the synthesis method of the low-chlorine long-chain alkyl glycidyl ether, the method has the advantages of short flow, simple operation, high yield, no need of using an organic solvent, environmental protection and energy conservation, and the obtained long-chain alkyl glycidyl ether has the advantages of low epoxy equivalent, low halogen content and the like.
In order to realize the technical purpose, the invention provides a synthesis method of low-chlorine long-chain alkyl glycidyl ether, which comprises the steps of dropwise adding epoxy chloropropane into long-chain alkyl fatty alcohol, and carrying out ring-opening etherification reaction under the action of a perchlorate/Lewis acid composite catalyst to obtain a chlorohydrin ether intermediate product; and carrying out intramolecular cyclization reaction on the chlorohydrin ether intermediate product and an alkali catalyst to obtain the long-chain alkyl glycidyl ether.
The key point of the invention is that a special perchlorate/Lewis acid composite catalyst is adopted in the ring-opening etherification reaction process, the composite catalyst not only has strong catalytic activity, but also has high selectivity for the ring-opening etherification reaction, can effectively reduce the occurrence of side reaction, and has high yield of the obtained product and low epoxy equivalent.
As a preferred embodiment, the long-chain alkyl fatty alcohol is C 12 ～C 14 Alkyl fatty alcohols of (2). C is generally purchased conventionally on the market 12 ～C 14 The alkyl fatty alcohol is mixed alcohol of carbon dodecyl alcohol and carbon tetradecanol, and the specific mass ratio is that the mass ratio of the carbon dodecyl alcohol to the carbon tetradecanol is about 7:3.
In a preferred embodiment, the molar ratio of the long-chain alkyl fatty alcohol to the epichlorohydrin is 1.
As a preferable scheme, the perchlorate/lewis acid composite catalyst is prepared by mixing perchlorate and lewis acid catalyst according to a weight ratio of 1: (0.1-5). The perchlorate/Lewis acid composite catalyst is further preferably prepared by mixing perchlorate and Lewis acid catalyst according to the weight ratio of 1: (1-2).
In a preferred embodiment, the perchlorate comprises at least one of magnesium perchlorate, zinc perchlorate and aluminum perchlorate.
As a preferred scheme, the Lewis acid comprises at least one of aluminum trichloride, stannic chloride, zinc dichloride and boron trifluoride diethyl etherate.
As a most preferred embodiment, the perchlorate/lewis acid composite catalyst consists of magnesium perchlorate and boron trifluoride etherate.
As a preferable scheme, the mass ratio of the perchlorate/lewis acid composite catalyst to the long-chain alkyl fatty alcohol is 0.1 to 6; more preferably 0.15 to 0.3.
As a preferred embodiment, the ring-opening etherification reaction conditions are as follows: the temperature is 50-85 ℃ and the time is 2-7 hours. The temperature of the ring-opening etherification reaction is preferably 55 to 75 ℃.
As a preferred embodiment, the base catalyst is an alkali metal hydroxide and/or an alkali metal alkoxide, such as sodium hydroxide, potassium hydroxide, sodium ethoxide, and the like, preferably sodium hydroxide.
As a preferred scheme, the intramolecular cyclization reaction process adopts a gradient temperature-rising reaction mode: the first stage reaction: reacting for 0.5-1.5 hours at 50-65 ℃; and (3) second-stage reaction: reacting for 1.5-2.5 hours at 65-75 ℃; and (3) third stage reaction: reacting for 1.5-2.5 hours at 75-90 ℃. The preferable gradient heating reaction mode can ensure that the intramolecular cyclization reaction is carried out more completely, reduce the content of residual chlorine in the product and improve the product yield.
As a preferable scheme, the alkali catalyst is added in a sectional manner in the gradient temperature-rising reaction process, 50-80% of the total mass of the alkali catalyst is added in the first stage reaction process, and the rest alkali catalyst is added in the second stage reaction process, wherein the molar ratio of the total amount of the alkali catalyst to the long-chain alkyl fatty alcohol is 1-5:1. The uniform speed of the intramolecular cyclization reaction can be ensured by controlling the addition mode of the alkali catalyst. The molar ratio of the total amount of the alkali catalyst to the long-chain alkyl fatty alcohol is more preferably 1 to 1.5.
The crude product of the long-chain alkyl glycidyl ether prepared by the method is washed and vacuum-dehydrated to obtain a pure product of the long-chain alkyl glycidyl ether, deionized water is adopted in the washing process, the water temperature is 40-60 ℃, the vacuum dehydration process is carried out, the temperature is 110-140 ℃, and the vacuum degree is-0.02-0.1 MPa.
The long-chain alkyl glycidyl ether has the following specific molecular structural formula:
wherein R representsC 12 ～C 14 An alkyl chain.
Compared with the prior art, the technical scheme of the invention has the following beneficial effects:
1) The invention adopts special composite catalyst to catalyze the ring-opening etherification reaction in the synthesis process of the long-chain alkyl glycidyl ether, has high catalytic selectivity and good catalytic effect, can reduce the occurrence of etherification side reaction, and reduces the epoxy equivalent of the product.
2) According to the invention, the intramolecular cyclization reaction is carried out in the synthesis process of the long-chain alkyl glycidyl ether in a sectional temperature control mode, so that the cyclization reaction efficiency can be improved, the content of residual chlorine can be reduced, the product yield can be improved, and the halogen content is low.
3) In the synthesis process of the long-chain alkyl glycidyl ether, the method has the advantages of short process flow, simple operation, mild reaction conditions, no use of organic solvent and good environmental protection benefit.
Detailed Description
The following examples are intended to further illustrate the present disclosure, but not to limit the scope of the claims.
The detection methods referred to in the following examples are detection methods common in the industry:
epoxy equivalent: measured by a hydrochloric acid-acetone method.
Organic chlorine content: measured by potentiometric titration.
Yield: percent actual to theoretical yield.
Example 1
Introducing N into a four-neck round-bottom flask provided with a thermometer, a stirrer, a dropping funnel and a condensing tube 2 Adding 200g of C12-C14 alcohol, starting stirring, adding 0.1g of magnesium perchlorate and 0.2g of boron trifluoride diethyl etherate complex, heating to 50 ℃, dropwise adding 102g of epichlorohydrin within 3 hours, maintaining the reaction for 2 hours, and then performing cyclization reaction in a segmented temperature control mode: in the first stage, the temperature is raised to 55 ℃, and 98g of 30 percent sodium hydroxide solution is dropwise added within 2 hours; the second section is heated to 65 ℃, 48g of 30 percent sodium hydroxide solution is dripped in 1 hour, after the alkali is added, the third section is heated to 75 ℃, and the reaction is maintained for 2 hours. After the reaction is completed, washing with waterThe mixture is dehydrated under reduced pressure until the product is transparent when the pH value of the mixture is neutral, the pressure is-0.08 MPa, and the temperature is 130 ℃. The yield of the obtained product is 98 percent, the epoxy equivalent is 285g/mol, and the organic chlorine is 0.05 percent.
Example 2
Introducing N2 into a four-neck round-bottom flask provided with a thermometer, a stirrer, a dropping funnel and a condenser, adding 200g of alcohol with 12-14 carbon atoms, starting stirring, adding 0.1g of aluminum perchlorate and 0.2g of aluminum trichloride, heating to 50 ℃, dropwise adding 102g of epoxy chloropropane within 3 hours, maintaining the reaction for 2 hours, and then carrying out cyclization reaction by a segmented temperature control mode: in the first stage, the temperature is raised to 55 ℃, and 98g of 30% sodium hydroxide solution is dropwise added within 2 hours; the second section is heated to 65 ℃, 48g of 30 percent sodium hydroxide solution is dripped in 1 hour, after the alkali is added, the third section is heated to 75 ℃, and the reaction is maintained for 2 hours. After the reaction is finished, the mixture is washed by water until the pH value is neutral, and dehydration is carried out under reduced pressure until the product is transparent, wherein the pressure is-0.08 MPa, and the temperature is 130 ℃. The yield of the obtained product is 90 percent, the epoxy equivalent is 289g/mol, and the organic chlorine is 0.06 percent.
Example 3
Introducing N into a four-neck round-bottom flask provided with a thermometer, a stirrer, a dropping funnel and a condenser 2 Adding 200g of C12-C14 alcohol, starting stirring, adding 0.4g of zinc perchlorate and 0.8g of zinc dichloride, heating to 50 ℃, dropwise adding 138g of epoxy chloropropane within 3 hours, maintaining the reaction for 2 hours, and then carrying out cyclization reaction by a segmented temperature control mode: in the first stage, the temperature is raised to 58 ℃, and 98g of 30% sodium hydroxide solution is dropwise added within 2 hours; the temperature of the second section is raised to 70 ℃, 48g of 30 percent sodium hydroxide solution is dripped in 1 hour, after the alkali is added, the temperature of the third section is raised to 80 ℃, and the reaction is maintained for 2 hours. After the reaction is finished, the mixture is washed by water until the pH value is neutral, and dehydration is carried out under reduced pressure until the product is transparent, wherein the pressure is-0.08 MPa, and the temperature is 130 ℃. The yield of the obtained product is 95 percent, the epoxy equivalent is 298g/mol, and the organic chlorine is 0.06 percent.
Example 4
Introducing N into a four-neck round-bottom flask provided with a thermometer, a stirrer, a dropping funnel and a condensing tube 2 Adding 200g of C12-C14 alcohol, starting stirring, and adding 0.3g of zinc perchlorateHeating boron trifluoride diethyl etherate 0.5g to 50 ℃, dropwise adding 120g of epichlorohydrin within 3 hours, maintaining the reaction for 2 hours, and then carrying out cyclization reaction by a segmented temperature control mode: in the first stage, the temperature is raised to 55 ℃, and 98g of 30% sodium hydroxide solution is dropwise added within 2 hours; the second section is heated to 65 ℃, 48g of 30 percent sodium hydroxide solution is dripped in 1 hour, after the alkali is added, the third section is heated to 75 ℃, and the reaction is maintained for 2 hours. After the reaction is finished, the mixture is washed by water until the pH value is neutral, and dehydration is carried out under reduced pressure until the product is transparent, wherein the pressure is-0.08 MPa, and the temperature is 130 ℃. The yield of the product obtained is 97%, the epoxy equivalent is 293g/mol and the organic chlorine is 0.04%.
Comparative example 1
Introducing N2 into a four-neck round-bottom flask provided with a thermometer, a stirrer, a dropping funnel and a condenser, adding 200g of alcohol with 12-14 carbon atoms, starting stirring, adding 0.3g of magnesium perchlorate, heating to 50 ℃, dropwise adding 102g of epoxy chloropropane within 3 hours, maintaining the reaction for 2 hours, and then carrying out cyclization reaction by a segmented temperature control mode: in the first stage, the temperature is raised to 55 ℃, and 98g of 30% sodium hydroxide solution is dropwise added within 2 hours; the second section is heated to 65 ℃, 48g of 30 percent sodium hydroxide solution is dripped in 1 hour, after the alkali is added, the third section is heated to 75 ℃, and the reaction is maintained for 2 hours. After the reaction is finished, the mixture is washed by water until the pH value is neutral, and dehydration is carried out under reduced pressure until the product is transparent, wherein the pressure is-0.08 MPa, and the temperature is 130 ℃. The yield of the product obtained was 76%, the epoxy equivalent weight was 310g/mol and the organic chlorine was 0.1%.
Comparative example 2
Introducing N2 into a four-neck round-bottom flask provided with a thermometer, a stirrer, a dropping funnel and a condenser, adding 200g of C12-14 alcohol, starting stirring, adding 0.1g of magnesium perchlorate and 0.2g of boron trifluoride diethyl etherate complex, heating to 50 ℃, dropwise adding 102g of epichlorohydrin within 3 hours, maintaining the reaction for 2 hours, heating to 75 ℃, dropwise adding 146g of 30% sodium hydroxide solution within 3 hours, and maintaining the reaction for 2 hours. After the reaction is finished, the mixture is washed by water until the pH value is neutral, and dehydration is carried out under reduced pressure until the product is transparent, wherein the pressure is-0.08 MPa, and the temperature is 130 ℃. The product yield was 75%, the epoxy equivalent was 327g/mol, and the organic chlorine was 0.15%.
Comparative example 3
Introducing N2 into a four-neck round-bottom flask provided with a thermometer, a stirrer, a dropping funnel and a condensing tube, adding 200g of alcohol with 12-14 carbon atoms, starting stirring, heating to 50 ℃, dropwise adding 102g of epoxy chloropropane within 3 hours, maintaining the reaction for 2 hours, and then carrying out cyclization reaction by a segmented temperature control mode: in the first stage, the temperature is raised to 55 ℃, and 98g of 30 percent sodium hydroxide solution is dropwise added within 2 hours; the second section is heated to 65 ℃, 48g of 30 percent sodium hydroxide solution is dripped in 1 hour, after the alkali is added, the third section is heated to 75 ℃, and the reaction is maintained for 2 hours. After the reaction is finished, the mixture is washed by water until the pH value is neutral, and dehydration is carried out under reduced pressure until the product is transparent, wherein the pressure is-0.08 MPa, and the temperature is 130 ℃. The product yield was 0.
While the invention has been described with reference to specific preferred embodiments, it will be understood by those skilled in the art that various changes and modifications may be made without departing from the spirit and scope of the invention as defined in the following claims. The invention is to be considered in all respects as illustrative and not restrictive.
Claims (12)
1. A synthetic method of low-chlorine long-chain alkyl glycidyl ether is characterized by comprising the following steps: dripping epoxy chloropropane into long-chain alkyl fatty alcohol, and carrying out ring-opening etherification reaction under the action of a perchlorate/Lewis acid composite catalyst to obtain a chlorohydrin ether intermediate product; and carrying out intramolecular cyclization reaction on the chlorohydrin ether intermediate product and an alkali catalyst to obtain the long-chain alkyl glycidyl ether.
2. The method for synthesizing low-chlorine long-chain alkyl glycidyl ether according to claim 1, which is characterized in that: the long-chain alkyl fatty alcohol is C 12 ～C 14 The alkyl fatty alcohol of (2).
3. The method for synthesizing low-chlorine long-chain alkyl glycidyl ether according to claim 1 or 2, which is characterized in that: the mol ratio of the long-chain alkyl fatty alcohol to the epichlorohydrin is 1.8-1.5.
4. The method for synthesizing low-chlorine long-chain alkyl glycidyl ether according to claim 1, which is characterized in that: the perchlorate/Lewis acid composite catalyst is prepared by mixing perchlorate and Lewis acid catalyst according to the weight ratio of 1: (0.1-5).
5. The method for synthesizing low-chlorine long-chain alkyl glycidyl ether according to claim 4, which is characterized in that:
the perchlorate comprises at least one of magnesium perchlorate, zinc perchlorate and aluminum perchlorate;
the Lewis acid comprises at least one of aluminum trichloride, stannic chloride, zinc dichloride and boron trifluoride diethyl etherate complex.
6. The method for synthesizing low-chlorine long-chain alkyl glycidyl ether according to claim 4 or 5, wherein the method comprises the following steps: the perchlorate/Lewis acid composite catalyst consists of magnesium perchlorate and boron trifluoride diethyl etherate complex.
7. The method for synthesizing low-chlorine long-chain alkyl glycidyl ether according to claim 1, 4 or 5, wherein the method comprises the following steps: the mass ratio of the perchlorate/Lewis acid composite catalyst to the long-chain alkyl fatty alcohol is 0.1-6.
8. The method for synthesizing low-chlorine long-chain alkyl glycidyl ether according to claim 7, which is characterized in that: the mass ratio of the perchlorate/Lewis acid composite catalyst to the long-chain alkyl fatty alcohol is 0.15-0.3.
9. The method for synthesizing low-chlorine long-chain alkyl glycidyl ether according to claim 1, which is characterized in that: the ring-opening etherification reaction conditions are as follows: the temperature is 50-85 ℃ and the time is 2-7 hours.
10. The method for synthesizing low-chlorine long-chain alkyl glycidyl ether according to claim 1, which is characterized in that: the alkali catalyst is alkali metal hydroxide and/or alkali metal alkoxide.
11. The method for synthesizing low-chlorine long-chain alkyl glycidyl ether according to claim 1, which is characterized in that: the intramolecular cyclization reaction process adopts a gradient heating reaction mode: the first stage reaction: reacting for 0.5-1.5 hours at 50-65 ℃; and (3) second-stage reaction: reacting for 1.5-2.5 hours at 65-75 ℃; and (3) third stage reaction: reacting for 1.5-2.5 hours at 75-90 ℃.
12. The method for synthesizing low-chlorine long-chain alkyl glycidyl ether according to claim 11, wherein the method comprises the following steps: the gradient temperature-rising reaction process adopts sectional addition of an alkali catalyst, 50-80% of the total mass of the alkali catalyst is added in the first stage of reaction process, and the rest of the alkali catalyst is added in the second stage of reaction process; wherein the molar ratio of the total amount of the alkali catalyst to the long-chain alkyl fatty alcohol is 1-5:1.
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