CN115785027B - Synthesis method of low-chlorine long-chain alkyl glycidyl ether - Google Patents
Synthesis method of low-chlorine long-chain alkyl glycidyl ether Download PDFInfo
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- chain alkyl
- glycidyl ether
- perchlorate
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- -1 alkyl glycidyl ether Chemical compound 0.000 title claims abstract description 44
- 239000000460 chlorine Substances 0.000 title claims abstract description 18
- 229910052801 chlorine Inorganic materials 0.000 title claims abstract description 18
- 238000001308 synthesis method Methods 0.000 title claims abstract description 7
- 239000003054 catalyst Substances 0.000 claims abstract description 29
- 238000000034 method Methods 0.000 claims abstract description 22
- 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
- 150000007517 lewis acids Chemical class 0.000 claims abstract description 14
- 239000002131 composite material Substances 0.000 claims abstract description 13
- 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
- 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
- LRWZZZWJMFNZIK-UHFFFAOYSA-N 2-chloro-3-methyloxirane Chemical compound CC1OC1Cl LRWZZZWJMFNZIK-UHFFFAOYSA-N 0.000 claims abstract description 3
- 238000006243 chemical reaction Methods 0.000 claims description 38
- 238000010438 heat treatment Methods 0.000 claims description 17
- 239000003513 alkali Substances 0.000 claims description 14
- KZMGYPLQYOPHEL-UHFFFAOYSA-N Boron trifluoride etherate Chemical compound FB(F)F.CCOCC KZMGYPLQYOPHEL-UHFFFAOYSA-N 0.000 claims description 13
- 230000002194 synthesizing effect Effects 0.000 claims description 10
- BRLQWZUYTZBJKN-UHFFFAOYSA-N Epichlorohydrin Chemical compound ClCC1CO1 BRLQWZUYTZBJKN-UHFFFAOYSA-N 0.000 claims description 9
- 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
- 239000002585 base Substances 0.000 claims description 6
- JIAARYAFYJHUJI-UHFFFAOYSA-L zinc dichloride Chemical compound [Cl-].[Cl-].[Zn+2] JIAARYAFYJHUJI-UHFFFAOYSA-L 0.000 claims description 6
- 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 4
- 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
- 239000011592 zinc chloride Substances 0.000 claims description 3
- 235000005074 zinc chloride Nutrition 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
- 239000004593 Epoxy Substances 0.000 abstract description 10
- 230000008901 benefit Effects 0.000 abstract description 7
- 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 1
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 45
- 239000000047 product Substances 0.000 description 20
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 11
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 8
- 239000003822 epoxy resin Substances 0.000 description 8
- 239000000203 mixture Substances 0.000 description 8
- 229920000647 polyepoxide Polymers 0.000 description 8
- 230000007935 neutral effect Effects 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
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 description 5
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 4
- 230000015572 biosynthetic process Effects 0.000 description 4
- 238000003786 synthesis reaction Methods 0.000 description 4
- DPVYDTACPLLHCF-UHFFFAOYSA-N 2-phenylethyl pivalate Chemical compound CC(C)(C)C(=O)OCCC1=CC=CC=C1 DPVYDTACPLLHCF-UHFFFAOYSA-N 0.000 description 3
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-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
- 229910052799 carbon Inorganic materials 0.000 description 3
- 230000003197 catalytic effect Effects 0.000 description 3
- 230000000052 comparative effect Effects 0.000 description 3
- 230000009286 beneficial effect Effects 0.000 description 2
- 230000018044 dehydration Effects 0.000 description 2
- 238000006297 dehydration reaction Methods 0.000 description 2
- 238000001514 detection method Methods 0.000 description 2
- 231100000053 low toxicity Toxicity 0.000 description 2
- 238000002360 preparation method 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
- FQYUMYWMJTYZTK-UHFFFAOYSA-N Phenyl glycidyl ether Chemical compound C1OC1COC1=CC=CC=C1 FQYUMYWMJTYZTK-UHFFFAOYSA-N 0.000 description 1
- DGQNHSVGKNZFSM-UHFFFAOYSA-N [C].CCCCCCCCCCCCCCO Chemical compound [C].CCCCCCCCCCCCCCO DGQNHSVGKNZFSM-UHFFFAOYSA-N 0.000 description 1
- LNXUQKDKOXLHDD-UHFFFAOYSA-N [C].CCCCCCCCCCCCO Chemical compound [C].CCCCCCCCCCCCO LNXUQKDKOXLHDD-UHFFFAOYSA-N 0.000 description 1
- 230000001070 adhesive effect Effects 0.000 description 1
- 125000000217 alkyl group Chemical group 0.000 description 1
- 125000004432 carbon atom Chemical group C* 0.000 description 1
- 238000004891 communication Methods 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
- 230000000694 effects Effects 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 150000002118 epoxides Chemical class 0.000 description 1
- 125000003700 epoxy group Chemical group 0.000 description 1
- LNEPOXFFQSENCJ-UHFFFAOYSA-N haloperidol Chemical compound C1CC(O)(C=2C=CC(Cl)=CC=2)CCN1CCCC(=O)C1=CC=C(F)C=C1 LNEPOXFFQSENCJ-UHFFFAOYSA-N 0.000 description 1
- 231100000086 high toxicity Toxicity 0.000 description 1
- 238000009776 industrial production Methods 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- 230000035699 permeability Effects 0.000 description 1
- 238000003918 potentiometric titration 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
- 238000007086 side reaction Methods 0.000 description 1
- 150000003384 small molecules Chemical class 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
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; the chlorohydrin ether intermediate product and a base catalyst undergo intramolecular cyclization reaction to obtain long-chain alkyl glycidyl ether; the method has the advantages of short flow, simple operation, high yield, no need of using organic solvents, 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 method for synthesizing glycidyl ether, in particular to a method for synthesizing low-chlorine long-chain alkyl glycidyl ether, and belongs to the technical field of epoxy resin reactive diluent synthesis.
Background
The epoxy resin has excellent mechanical property, chemical medium resistance, adhesive property, insulating property and other advantages, and is widely applied to the fields of high and new technologies of machinery, electronics, communication and aerospace. However, in practical application, the epoxy resin has high viscosity and poor fluidity and permeability, and a proper diluent is needed to be added to reduce the viscosity, increase the fluidity, improve the wetting force and improve the process operability.
Reactive diluents generally refer to low molecular weight compounds having one or more epoxy groups, which can directly participate in the curing reaction of the epoxy resin and become a part of the crosslinked network structure of the cured epoxy resin, and have little effect on the properties of the cured epoxy resin. Reactive diluents therefore occupy an important place in epoxy resin applications. Reactive diluents commonly used, such as phenyl glycidyl ether, butyl glycidyl ether and the like, cannot meet the increasingly higher environmental protection requirements due to low boiling point, high volatility and high toxicity. There is a need to develop new reactive diluents for epoxy resins that have low toxicity and low volatility. The carbon dodecyl/tetradecyl glycidyl ether synthesized by the alcohol has high boiling point, low volatility, low toxicity and better flexibility due to the longer carbon chain and higher boiling point. At present, few reports are made on the preparation method of the carbon dodecyl/tetradecyl glycidyl ether in China, and only the preparation method of the carbon dodecyl/tetradecyl glycidyl ether is disclosed in Chinese patent CN101440074A, but the synthesis method is complex and is not beneficial to industrial production.
Disclosure of Invention
Aiming at the defects existing in the prior art, the invention aims to provide a synthesis method of low-chlorine long-chain alkyl glycidyl ether, which has the advantages of short flow, simple operation, high yield, no need of using organic solvents, environmental protection and energy saving, and the obtained long-chain alkyl glycidyl ether has the advantages of low epoxy equivalent, low halogen content and the like.
In order to achieve the technical aim, the invention provides a synthesis method of low-chlorine long-chain alkyl glycidyl ether, which comprises the steps of 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 (3) carrying out intramolecular cyclization reaction on the chlorohydrin ether intermediate product and a base catalyst to obtain the long-chain alkyl glycidyl ether.
The key of the invention is that a special perchlorate/Lewis acid composite catalyst is adopted in the process of ring opening etherification, and the composite catalyst has strong catalytic activity, high selectivity for the ring opening etherification reaction, high yield of the obtained product and low epoxy equivalent.
As a preferred embodiment, the long-chain alkyl fatty alcohol is a C 12～C14 alkyl fatty alcohol. Typically, the commercially available alkyl fatty alcohol of C 12～C14 is a mixture of carbon dodecanol and carbon tetradecanol in a specific mass ratio of about 7:3.
As a preferable scheme, the mol ratio of the long-chain alkyl fatty alcohol to the epichlorohydrin is 1:0.8-1.5.
As a preferable scheme, the perchlorate/lewis acid composite catalyst comprises perchlorate and lewis acid catalyst according to the weight ratio of 1: (0.1-5). The perchlorate/Lewis acid composite catalyst is further preferably prepared from perchlorate and Lewis acid catalyst in a weight ratio of 1: (1-2).
As a preferred embodiment, the perchlorate includes at least one of magnesium perchlorate, zinc perchlorate, and aluminum perchlorate.
As a preferred embodiment, the Lewis acid comprises at least one of aluminum trichloride, tin tetrachloride, zinc dichloride, boron trifluoride etherate.
As a most preferred embodiment, the perchlorate/Lewis acid complex catalyst consists of magnesium perchlorate in combination with 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 0.1-6:100; more preferably 0.15 to 0.3:100.
As a preferred embodiment, the ring-opening etherification reaction conditions are: 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 preferable scheme, the intramolecular cyclization reaction adopts a gradient heating reaction mode: first stage reaction: reacting for 0.5 to 1.5 hours at the temperature of between 50 and 65 ℃; second stage reaction: reacting for 1.5 to 2.5 hours at the temperature of 65 to 75 ℃; third stage reaction: reacting for 1.5-2.5 hours at 75-90 ℃. The preferential gradient heating reaction mode can lead the intramolecular cyclization reaction to be more thoroughly carried out, 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 heating 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 alkali catalyst to the long-chain alkyl fatty alcohol is 1-5:1. The method can ensure that the intramolecular cyclization reaction can be carried out at a constant speed by controlling the adding mode of the base catalyst. The molar ratio of the total amount of the base catalyst to the long-chain alkyl fatty alcohol is further preferably 1 to 1.5:1.
The long-chain alkyl glycidyl ether crude product prepared by the method is subjected to water washing and vacuum dehydration treatment to obtain a long-chain alkyl glycidyl ether pure product, deionized water is adopted in the water washing process, the water temperature is 40-60 ℃, the temperature is 110-140 ℃ in the vacuum dehydration process, and the vacuum degree is-0.02 to-0.1 MPa.
The specific molecular structural formula of the long-chain alkyl glycidyl ether is as follows:
wherein R represents a C 12～C14 alkyl chain.
Compared with the prior art, the technical scheme of the invention has the beneficial effects that:
1) The invention adopts a 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 reduce the epoxy equivalent of the product.
2) The invention carries out intramolecular cyclization reaction in the synthesis process of long-chain alkyl glycidyl ether through a sectional temperature control mode, can improve the cyclization reaction efficiency, reduce the residual chlorine content, improve the product yield and have low halogen content.
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 solvents and good environmental protection benefit.
Detailed Description
The following examples are intended to further illustrate the present invention and are not intended to limit the scope of the claims.
The detection methods involved in the following embodiments are common detection methods in the industry:
epoxy equivalent: the measurement is carried out by a hydrochloric acid-acetone method.
Organic chlorine content: measured by potentiometric titration.
Yield: actual yield and theoretical yield percentage.
Example 1
Introducing N 2 into a four-necked round bottom flask 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, heating to 50 ℃, dropwise adding 102g of epichlorohydrin within 3 hours, maintaining the reaction for 2 hours, and then carrying out cyclization reaction in a sectional temperature control mode: heating to 55 ℃ in the first stage, and dropwise adding 98g of 30% sodium hydroxide solution within 2 hours; the second stage is heated to 65 ℃, 48g of 30% sodium hydroxide solution is added dropwise within 1 hour, the alkali addition is completed, the third stage is heated to 75 ℃, and the reaction is maintained for 2 hours. After the reaction was completed, the mixture was washed with water until the pH was neutral, dehydrated under reduced pressure until the product was transparent, at a pressure of-0.08 MPa, and at a temperature of 130 ℃. The yield of the obtained product is 98%, the epoxy equivalent is 285g/mol, and the organic chloride is 0.05%.
Example 2
Introducing N2 into a four-neck round bottom flask with a thermometer, a stirrer, a dropping funnel and a condenser, adding 200g of C12-14 alcohol, starting stirring, adding 0.1g of aluminum perchlorate, 0.2g of aluminum trichloride, heating to 50 ℃, dropwise adding 102g of epichlorohydrin within 3 hours, maintaining the reaction for 2 hours, and performing cyclization reaction in a sectional temperature control mode: heating to 55 ℃ in the first stage, and dropwise adding 98g of 30% sodium hydroxide solution within 2 hours; the second stage is heated to 65 ℃, 48g of 30% sodium hydroxide solution is added dropwise within 1 hour, the alkali addition is completed, the third stage is heated to 75 ℃, and the reaction is maintained for 2 hours. After the reaction was completed, the mixture was washed with water until the pH was neutral, dehydrated under reduced pressure until the product was transparent, at a pressure of-0.08 MPa, and at a temperature of 130 ℃. The yield of the obtained product is 90%, the epoxide equivalent is 289g/mol, and the organochlorine is 0.06%.
Example 3
Introducing N 2 into a four-neck round bottom flask with a thermometer, a stirrer, a dropping funnel and a condenser, adding 200g of C12-14 alcohol, starting stirring, adding 0.4g of zinc perchlorate and 0.8g of zinc dichloride, heating to 50 ℃, dropwise adding 138g of epichlorohydrin within 3 hours, maintaining the reaction for 2 hours, and performing cyclization reaction in a sectional temperature control mode: heating to 58 ℃ in the first stage, and dropwise adding 98g of 30% sodium hydroxide solution within 2 hours; the second stage is heated to 70 ℃, 48g of 30% sodium hydroxide solution is added dropwise within 1 hour, the alkali addition is completed, the third stage is heated to 80 ℃, and the reaction is maintained for 2 hours. After the reaction was completed, the mixture was washed with water until the pH was neutral, dehydrated under reduced pressure until the product was transparent, at a pressure of-0.08 MPa, and at a temperature of 130 ℃. The yield of the obtained product is 95%, the epoxy equivalent is 298g/mol, and the organic chloride is 0.06%.
Example 4
Introducing N 2 into a four-necked round bottom flask with a thermometer, a stirrer, a dropping funnel and a condenser, adding 200g of C12-14 alcohol, starting stirring, adding 0.3g of zinc perchlorate and 0.5g of boron trifluoride diethyl etherate, heating to 50 ℃, dropwise adding 120g of epichlorohydrin within 3 hours, maintaining the reaction for 2 hours, and then carrying out cyclization reaction in a sectional temperature control mode: heating to 55 ℃ in the first stage, and dropwise adding 98g of 30% sodium hydroxide solution within 2 hours; the second stage is heated to 65 ℃, 48g of 30% sodium hydroxide solution is added dropwise within 1 hour, the alkali addition is completed, the third stage is heated to 75 ℃, and the reaction is maintained for 2 hours. After the reaction was completed, the mixture was washed with water until the pH was neutral, dehydrated under reduced pressure until the product was transparent, at a pressure of-0.08 MPa, and at a temperature of 130 ℃. The yield of the obtained product is 97%, the epoxy equivalent is 293g/mol, and the organic chloride is 0.04%.
Comparative example 1
Introducing N2 into a four-neck round-bottom flask with a thermometer, a stirrer, a dropping funnel and a condenser, adding 200g of C12-14 alcohol, starting stirring, adding 0.3g of magnesium perchlorate, heating to 50 ℃, dropwise adding 102g of epichlorohydrin within 3 hours, maintaining the reaction for 2 hours, and performing cyclization reaction in a sectional temperature control mode: heating to 55 ℃ in the first stage, and dropwise adding 98g of 30% sodium hydroxide solution within 2 hours; the second stage is heated to 65 ℃, 48g of 30% sodium hydroxide solution is added dropwise within 1 hour, the alkali addition is completed, the third stage is heated to 75 ℃, and the reaction is maintained for 2 hours. After the reaction was completed, the mixture was washed with water until the pH was neutral, dehydrated under reduced pressure until the product was transparent, at a pressure of-0.08 MPa, and at a temperature of 130 ℃. The yield of the obtained product is 76%, the epoxy equivalent is 310g/mol, and the organic chloride is 0.1%.
Comparative example 2
Into a four-necked round bottom flask equipped with a thermometer, a stirrer, a dropping funnel and a condenser, 200g of C12-14 alcohol is added, stirring is started, 0.1g of magnesium perchlorate, 0.2g of boron trifluoride diethyl ether complex is added, the temperature is raised to 50 ℃, 102g of epichlorohydrin is dropwise added within 3 hours for reaction for 2 hours, then the temperature is raised to 75 ℃, 146g of 30% sodium hydroxide solution is dropwise added within 3 hours for reaction for 2 hours. After the reaction was completed, the mixture was washed with water until the pH was neutral, dehydrated under reduced pressure until the product was transparent, at a pressure of-0.08 MPa, and at a temperature of 130 ℃. The yield of the obtained product is 75%, the epoxy equivalent is 327g/mol, and the organic chloride is 0.15%.
Comparative example 3
Introducing N2 into a four-neck round bottom flask with a thermometer, a stirrer, a dropping funnel and a condenser, adding 200g of alcohol with 12-14 carbon atoms, starting stirring, heating to 50 ℃, dropwise adding 102g of epichlorohydrin within 3 hours, maintaining the reaction for 2 hours, and performing cyclization reaction in a sectional temperature control mode: heating to 55 ℃ in the first stage, and dropwise adding 98g of 30% sodium hydroxide solution within 2 hours; the second stage is heated to 65 ℃, 48g of 30% sodium hydroxide solution is added dropwise within 1 hour, the alkali addition is completed, the third stage is heated to 75 ℃, and the reaction is maintained for 2 hours. After the reaction was completed, the mixture was washed with water until the pH was neutral, dehydrated under reduced pressure until the product was transparent, at a pressure of-0.08 MPa, and at a temperature of 130 ℃. The yield of the obtained product was 0.
While the invention has been described in terms of preferred embodiments, the scope of the invention is not limited thereto, but rather, variations or alternatives will be apparent to those skilled in the art in light of the foregoing description, and are intended to be included within the scope of the invention. The invention is to be considered as protected by the scope of the appended claims.
Claims (9)
1. A synthesis 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; the chlorohydrin ether intermediate product and a base catalyst undergo intramolecular cyclization reaction to obtain long-chain alkyl glycidyl ether;
the perchlorate/Lewis acid composite catalyst comprises perchlorate and Lewis acid catalyst according to the weight ratio of 1: (0.1-5);
The perchlorate comprises at least one of magnesium perchlorate, zinc perchlorate and aluminum perchlorate;
The Lewis acid comprises at least one of aluminum trichloride, tin tetrachloride, zinc dichloride and boron trifluoride diethyl etherate;
The intramolecular cyclization reaction adopts a gradient heating reaction mode: first stage reaction: reacting for 0.5-1.5 hours at 50-65 ℃; second stage reaction: reacting for 1.5-2.5 hours at 65-75 ℃; third stage reaction: and reacting for 1.5-2.5 hours at the temperature of 75-90 ℃.
2. The method for synthesizing the 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~C14 alkyl fatty alcohol.
3. The method for synthesizing the low-chlorine long-chain alkyl glycidyl ether according to claim 1 or 2, which is characterized in that: the molar ratio of the long-chain alkyl fatty alcohol to the epichlorohydrin is 1:0.8-1.5.
4. The method for synthesizing the low-chlorine long-chain alkyl glycidyl ether according to claim 1, which is characterized in that: the perchlorate/Lewis acid composite catalyst consists of magnesium perchlorate and boron trifluoride diethyl etherate.
5. The method for synthesizing the low-chlorine long-chain alkyl glycidyl ether according to claim 1, which is characterized in that: the mass ratio of the perchlorate/Lewis acid composite catalyst to the long-chain alkyl fatty alcohol is 0.1-6:100.
6. The method for synthesizing the low-chlorine long-chain alkyl glycidyl ether according to claim 5, which is characterized in that: the mass ratio of the perchlorate/Lewis acid composite catalyst to the long-chain alkyl fatty alcohol is 0.15-0.3:100.
7. The method for synthesizing the 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.
8. The method for synthesizing the 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.
9. The method for synthesizing the low-chlorine long-chain alkyl glycidyl ether according to claim 1, which is characterized in that: the gradient heating reaction process adopts the steps of adding an alkali catalyst in a sectional manner, wherein 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 base catalyst to the long-chain alkyl fatty alcohol is 1-5:1.
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| CN109020925A (en) * | 2018-09-19 | 2018-12-18 | 江苏三木化工股份有限公司 | The preparation method of Polyethylene Glycol Bisglycidyl Ether |
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