CN103145648A - Synthetic method of allyl glycidyl ether - Google Patents
Synthetic method of allyl glycidyl ether Download PDFInfo
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- CN103145648A CN103145648A CN2013100803176A CN201310080317A CN103145648A CN 103145648 A CN103145648 A CN 103145648A CN 2013100803176 A CN2013100803176 A CN 2013100803176A CN 201310080317 A CN201310080317 A CN 201310080317A CN 103145648 A CN103145648 A CN 103145648A
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- 238000010189 synthetic method Methods 0.000 title claims abstract description 10
- STMDPCBYJCIZOD-UHFFFAOYSA-N 2-(2,4-dinitroanilino)-4-methylpentanoic acid Chemical compound CC(C)CC(C(O)=O)NC1=CC=C([N+]([O-])=O)C=C1[N+]([O-])=O STMDPCBYJCIZOD-UHFFFAOYSA-N 0.000 title abstract description 5
- WTEOIRVLGSZEPR-UHFFFAOYSA-N boron trifluoride Chemical compound FB(F)F WTEOIRVLGSZEPR-UHFFFAOYSA-N 0.000 claims abstract description 70
- XXROGKLTLUQVRX-UHFFFAOYSA-N allyl alcohol Chemical compound OCC=C XXROGKLTLUQVRX-UHFFFAOYSA-N 0.000 claims abstract description 46
- 229910015900 BF3 Inorganic materials 0.000 claims abstract description 35
- 239000003054 catalyst Substances 0.000 claims abstract description 32
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims abstract description 30
- 238000007142 ring opening reaction Methods 0.000 claims abstract description 27
- LRWZZZWJMFNZIK-UHFFFAOYSA-N 2-chloro-3-methyloxirane Chemical compound CC1OC1Cl LRWZZZWJMFNZIK-UHFFFAOYSA-N 0.000 claims abstract description 20
- 238000007363 ring formation reaction Methods 0.000 claims abstract description 16
- -1 allyl chlorhydrin Chemical compound 0.000 claims abstract description 7
- LSWYGACWGAICNM-UHFFFAOYSA-N 2-(prop-2-enoxymethyl)oxirane Chemical compound C=CCOCC1CO1 LSWYGACWGAICNM-UHFFFAOYSA-N 0.000 claims description 27
- 239000012467 final product Substances 0.000 claims description 13
- 239000000463 material Substances 0.000 claims description 7
- 238000010992 reflux Methods 0.000 claims description 7
- DPDMMXDBJGCCQC-UHFFFAOYSA-N [Na].[Cl] Chemical compound [Na].[Cl] DPDMMXDBJGCCQC-UHFFFAOYSA-N 0.000 claims description 2
- 238000001816 cooling Methods 0.000 claims description 2
- 230000008030 elimination Effects 0.000 claims description 2
- 238000003379 elimination reaction Methods 0.000 claims description 2
- 239000000376 reactant Substances 0.000 claims description 2
- 238000003756 stirring Methods 0.000 claims description 2
- 238000006243 chemical reaction Methods 0.000 abstract description 34
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 abstract description 8
- 239000004593 Epoxy Substances 0.000 abstract description 5
- 238000007086 side reaction Methods 0.000 abstract description 4
- 239000007790 solid phase Substances 0.000 abstract description 3
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 abstract description 2
- 239000007795 chemical reaction product Substances 0.000 abstract description 2
- 239000000460 chlorine Substances 0.000 abstract description 2
- 229910052801 chlorine Inorganic materials 0.000 abstract description 2
- 238000003912 environmental pollution Methods 0.000 abstract description 2
- ZQXCQTAELHSNAT-UHFFFAOYSA-N 1-chloro-3-nitro-5-(trifluoromethyl)benzene Chemical compound [O-][N+](=O)C1=CC(Cl)=CC(C(F)(F)F)=C1 ZQXCQTAELHSNAT-UHFFFAOYSA-N 0.000 abstract 2
- 239000007787 solid Substances 0.000 abstract 1
- 238000007598 dipping method Methods 0.000 description 19
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 15
- 238000012986 modification Methods 0.000 description 13
- 230000004048 modification Effects 0.000 description 13
- IAYPIBMASNFSPL-UHFFFAOYSA-N Ethylene oxide Chemical compound C1CO1 IAYPIBMASNFSPL-UHFFFAOYSA-N 0.000 description 12
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 description 10
- 238000001035 drying Methods 0.000 description 10
- 239000000047 product Substances 0.000 description 10
- 239000000243 solution Substances 0.000 description 10
- 239000006227 byproduct Substances 0.000 description 6
- 238000009835 boiling Methods 0.000 description 5
- 238000009413 insulation Methods 0.000 description 5
- 238000000034 method Methods 0.000 description 5
- 239000012266 salt solution Substances 0.000 description 5
- 239000011780 sodium chloride Substances 0.000 description 5
- 238000010792 warming Methods 0.000 description 5
- 230000002378 acidificating effect Effects 0.000 description 4
- 229910052799 carbon Inorganic materials 0.000 description 4
- 230000015572 biosynthetic process Effects 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- 238000002360 preparation method Methods 0.000 description 3
- 238000003786 synthesis reaction Methods 0.000 description 3
- KZMGYPLQYOPHEL-UHFFFAOYSA-N Boron trifluoride etherate Chemical compound FB(F)F.CCOCC KZMGYPLQYOPHEL-UHFFFAOYSA-N 0.000 description 2
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 description 2
- 125000001931 aliphatic group Chemical group 0.000 description 2
- VSCWAEJMTAWNJL-UHFFFAOYSA-K aluminium trichloride Chemical compound Cl[Al](Cl)Cl VSCWAEJMTAWNJL-UHFFFAOYSA-K 0.000 description 2
- 238000006555 catalytic reaction Methods 0.000 description 2
- 238000010790 dilution Methods 0.000 description 2
- 239000012895 dilution Substances 0.000 description 2
- 125000003700 epoxy group Chemical group 0.000 description 2
- 239000007788 liquid Substances 0.000 description 2
- VLTRZXGMWDSKGL-UHFFFAOYSA-N perchloric acid Chemical compound OCl(=O)(=O)=O VLTRZXGMWDSKGL-UHFFFAOYSA-N 0.000 description 2
- 239000002994 raw material Substances 0.000 description 2
- WVDDGKGOMKODPV-UHFFFAOYSA-N Benzyl alcohol Chemical compound OCC1=CC=CC=C1 WVDDGKGOMKODPV-UHFFFAOYSA-N 0.000 description 1
- 239000002841 Lewis acid Substances 0.000 description 1
- LRHPLDYGYMQRHN-UHFFFAOYSA-N N-Butanol Chemical class CCCCO LRHPLDYGYMQRHN-UHFFFAOYSA-N 0.000 description 1
- 229910021627 Tin(IV) chloride Inorganic materials 0.000 description 1
- 239000002250 absorbent Substances 0.000 description 1
- 230000002745 absorbent Effects 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 150000008431 aliphatic amides Chemical class 0.000 description 1
- 150000001412 amines Chemical class 0.000 description 1
- 238000013459 approach Methods 0.000 description 1
- 229960004217 benzyl alcohol Drugs 0.000 description 1
- 235000019445 benzyl alcohol Nutrition 0.000 description 1
- 230000003197 catalytic effect Effects 0.000 description 1
- 239000003610 charcoal Substances 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 239000011248 coating agent Substances 0.000 description 1
- 238000000576 coating method Methods 0.000 description 1
- 238000005260 corrosion Methods 0.000 description 1
- 230000007797 corrosion Effects 0.000 description 1
- GYZLOYUZLJXAJU-UHFFFAOYSA-N diglycidyl ether Chemical compound C1OC1COCC1CO1 GYZLOYUZLJXAJU-UHFFFAOYSA-N 0.000 description 1
- 239000003085 diluting agent Substances 0.000 description 1
- 238000004821 distillation Methods 0.000 description 1
- 229940079593 drug Drugs 0.000 description 1
- 239000003814 drug Substances 0.000 description 1
- 238000005265 energy consumption Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 229920006332 epoxy adhesive Polymers 0.000 description 1
- 239000003822 epoxy resin Substances 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 238000001914 filtration Methods 0.000 description 1
- 238000009408 flooring Methods 0.000 description 1
- 150000002460 imidazoles Chemical class 0.000 description 1
- 239000013067 intermediate product Substances 0.000 description 1
- RBTARNINKXHZNM-UHFFFAOYSA-K iron trichloride Chemical compound Cl[Fe](Cl)Cl RBTARNINKXHZNM-UHFFFAOYSA-K 0.000 description 1
- 150000007517 lewis acids Chemical class 0.000 description 1
- 239000003921 oil Substances 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 239000003973 paint Substances 0.000 description 1
- 229920000647 polyepoxide Polymers 0.000 description 1
- HPOKESDSMZRZLC-UHFFFAOYSA-N propan-2-one;hydrochloride Chemical compound Cl.CC(C)=O HPOKESDSMZRZLC-UHFFFAOYSA-N 0.000 description 1
- 150000003242 quaternary ammonium salts Chemical class 0.000 description 1
- 238000011084 recovery Methods 0.000 description 1
- 230000000452 restraining effect Effects 0.000 description 1
- 238000007789 sealing Methods 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 238000000967 suction filtration Methods 0.000 description 1
- 238000012360 testing method Methods 0.000 description 1
- HPGGPRDJHPYFRM-UHFFFAOYSA-J tin(iv) chloride Chemical compound Cl[Sn](Cl)(Cl)Cl HPGGPRDJHPYFRM-UHFFFAOYSA-J 0.000 description 1
- XJDNKRIXUMDJCW-UHFFFAOYSA-J titanium tetrachloride Chemical compound Cl[Ti](Cl)(Cl)Cl XJDNKRIXUMDJCW-UHFFFAOYSA-J 0.000 description 1
- 238000005406 washing Methods 0.000 description 1
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- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
- Catalysts (AREA)
- Low-Molecular Organic Synthesis Reactions Using Catalysts (AREA)
Abstract
The invention discloses a synthetic method of allyl glycidyl ether. The synthetic method comprises the following steps that allyl alcohol and epoxy chloropropane have ring-opening reaction to prepare an allyl chlorhydrin intermediate, and the allyl chlorhydrin intermediate and sodium hydroxide have ring-closure reaction to prepare the allyl glycidyl ether, wherein a catalyst used in the ring-opening reaction is an activated carbon immobilized trifluoride catalyst, and the solid load of boron trifluoride is 5-20%. Sine the activated carbon immobilized trifluoride catalyst is used for catalyzing the ring-opening reaction between the allyl alcohol and the epoxy chloropropane, selectivity to the main reaction of the ring-opening reaction is high and side reactions are reduced, so that the prepared allyl glycidyl ether has high epoxy value, low organic chlorine content and good quality; and in addition, the solid-phase catalyst has low corrosivity on equipment, can be easily separated from reaction products after ring-opening reaction is ended and can be recycled after being separated, so that environmental pollution is avoided.
Description
Technical field
The present invention relates to the synthetic field of aliphatics monoglycidyl ether, be specifically related to a kind of synthetic method of glycidyl allyl ether.
Background technology
Glycidyl allyl ether is the single epoxy group(ing) thinner of a kind of aliphatics of line style, comprises ehter bond and epoxy group(ing) in molecule, has the advantages such as viscosity is low, dilution effect is good; Participate in curing reaction during curing, form the homogeneous system, it is the epoxide resin reactive diluent of commonly using, can be widely used in the dilution of the epoxy materials such as solvent-free insulated paint, epoxy sealing encapsulating material, no-solvent type epoxy flooring coating and epoxy adhesive, wherein the elaboration fraction of high epoxy value also can be used as the material modified of other amine curing agents such as aliphatic amide, imidazoles.
Synthetic single stage method, two-step approach and the oxidation style of mainly containing of glycidyl allyl ether, synthesis of allyl glycidyl ether mainly adopts two-step process both at home and abroad at present.Two step synthesis technique is under an acidic catalyst effect, carries out ring-opening reaction by vinyl carbinol and epoxy chloropropane, and then carries out the corresponding glycidyl allyl ether of ring-closure reaction generation with sodium hydroxide; Be that raw material vinyl carbinol, an acidic catalyst and epoxy chloropropane carry out ring-opening reaction, generate the chlorallylene alcohol intermediate, then carry out ring-closure reaction with sodium hydroxide and make glycidyl allyl ether, the reaction formula of open loop and ring-closure reaction is as follows:
(in formula: R=CH
2CH=CH
2);
Wherein ring-opening reaction is the key of two step synthesis, and an acidic catalyst that uses in ring-opening reaction at present is mainly strong acid type catalyzer such as the vitriol oil, perchloric acid and Lewis acid BF
3O (C
2H
5)
2, tin tetrachloride, aluminum chloride, titanium tetrachloride or iron trichloride etc.Use such an acidic catalyst not only to exist shortcomings such as conversion unit seriously corroded, use inconvenience, the recovery uses that can not circulate; And selectivity is relatively poor in ring-opening reaction, causes the by product in intermediate product many, makes the oxirane value of final product low, chloride content is high.
Summary of the invention
The object of the present invention is to provide a kind of synthetic method of glycidyl allyl ether, the oxirane value that obtains glycidyl allyl ether that it is produced is high.
A kind of synthetic method of glycidyl allyl ether, comprise that vinyl carbinol and epoxy chloropropane generation ring-opening reaction produce the chlorallylene alcohol intermediate, and chlorallylene alcohol intermediate and sodium hydroxide carry out ring-closure reaction and produce glycidyl allyl ether, ring-opening reaction catalyzer used is the immobilized boron trifluoride catalyst of gac, and the supported quantity of boron trifluoride is 5～20%.
Wherein the immobilized boron trifluoride catalyst of gac refers to the solid-phase catalyst that obtains after the immobilized boron trifluoride of the outside surface of gac.By using gac immobilized boron trifluoride catalyst catalysis vinyl carbinol and epoxy chloropropane generation ring-opening reaction, the selectivity of its divided ring reaction main reaction is high, reduce the generation of side reaction, make and produce that the oxirane value that obtains glycidyl allyl ether is high, content of organic chloride is low, quality better; In addition, this solid-phase catalyst is low to equipment corrosion, ring-opening reaction is easily separated with reaction product after finishing, and can be recycled after separating, and avoids causing environmental pollution.
Those skilled in the art can produce the immobilized boron trifluoride catalyst of the gac that obtains different supported quantities by different preparation method and application's demands, but easy the to be capable property that the contriver produces through test of long duration, in conjunction with this catalyzer and on the optimality of the ring-opening reaction impact of preparation glycidyl allyl ether, preferably selecting supported quantity is that 5～20% the immobilized boron trifluoride catalyst of gac carries out catalyzed reaction, to obtain best preparation and result of use.
The immobilized boron trifluoride catalyst of this gac can be by carrying out modification to gac, and with the washing active carbon after modification, drying; Then in dried gac being impregnated in the organic solution (comprising toluene, phenylcarbinol, anhydrous butanols) that contains boron trifluoride, dipping is produced after suction filtration, drying after fully and is obtained.Modification comprises that the surface group to gac carries out modification and/or the duct of gac is expanded; In addition, can be effectively immobilized on gac for making boron trifluoride, in the divided ring reaction, the catalytic selectivity of main reaction is best, preferably produces the immobilized boron trifluoride catalyst of gac according to following operation, that is:
Step (1): at first absorbent charcoal carrier is immersed in massfraction is 10～30% HNO
3In solution, the solid-liquid mass ratio of controlling dipping is 1:5～1:15, and dipping temperature is 20～100 ℃, and dipping time is 1～4h, then takes out gac and is washed to neutrality, filters, gets final product after drying and to get the gac of modification;
Step (2): the gac of modification be impregnated in to contain the boron trifluoride massfraction be in 0.5～5% toluene solution, the solid-liquid mass ratio of controlling dipping is that 1:10～1:15, dipping temperature are 30～70 ℃, dipping time is 1～4h, gets final product to get this catalyzer after filtration, drying.
For the productive rate that improves glycidyl allyl ether with shorten the consuming time of whole building-up reactions, the present invention preferably implements by following detailed operation:
The material ratio of vinyl carbinol and epoxy chloropropane is 2～3:1, and the material ratio of epoxy chloropropane and sodium hydroxide is 1:1～1.2; The consumption of the immobilized boron trifluoride catalyst of gac be ring-opening reaction the reactant total mass 0.5～2%.Epoxy chloropropane and the immobilized boron trifluoride catalyst of gac are added in vinyl carbinol, condensing reflux stirs and carries out ring-opening reaction, the temperature of controlling ring-opening reaction is 50～60 ℃, time 4h left and right, ring-opening reaction removes unreacted vinyl carbinol after finishing, the immobilized boron trifluoride catalyst of elimination gac after cooling; And then add sodium hydroxide to carry out ring-closure reaction, about 35～45 ℃ of the temperature control bits of ring-closure reaction, time 6h, ring-closure reaction is removed sodium-chlor after finishing, and gets final product to get glycidyl allyl ether after refinement treatment.
Can use the reaction of quaternary ammonium salt catalyst in ring-closure reaction, more be conducive to the carrying out of ring-closure reaction, the hydrolyzable chlorine that makes product is low, and oxirane value is high.Simultaneously, each reaction parameter of above-mentioned restriction is through contriver's lot of experiments, constantly modification and finally determine.For example, by considering vinyl carbinol when excessive, to the restraining effect of side reaction, improve the oxirane value of final product and the unit equipment that brings yields poorly, reclaims the negative impacts such as the energy consumption of vinyl carbinol is large, mole proportioning that limits vinyl carbinol and epoxy chloropropane is that 2～3:1 is to obtain optimized effect.In addition, the control of the consumption of the immobilized boron trifluoride catalyst of gac and ring-opening reaction, ring-closure reaction temperature and time, also to consider the raising speed of reaction to optimize final definite with the generation that suppresses side reaction, make each reaction carry out to the main reaction direction fast when carrying out ring-opening reaction and ring-closure reaction, make the oxirane value of the final product that makes high, organochlorine is low.
Embodiment
Below come by specific embodiment that the invention will be further described, but following examples should not be construed as the restriction that the protection domain of claim of the present invention is made.
Wherein embodiment 1～3 is for producing the immobilized boron trifluoride catalyst of gac, embodiment 4 is for utilizing prior art to produce glycidyl allyl ether, embodiment 5～8 is for utilizing technical scheme of the present invention to produce glycidyl allyl ether, and in embodiment 5～8, the immobilized boron trifluoride catalyst of gac used is to produce in embodiment 1～3 to obtain.Another each embodiment raw material epoxy chloropropane used is technical grade, is produced by Shandong petrochemical complex limited-liability company of petrochemical complex limited-liability company; Vinyl carbinol is chemical pure, is produced by Solution on Chemical Reagents in Shanghai company of Chinese Medicine group; 32% sodium hydroxide is technical grade, is produced by Wuhu Ronghui Chemical Co., Ltd..
The supported quantity operating weight method of the immobilized boron trifluoride of gac that makes is measured.
The oxirane value of glycidyl allyl ether detects with hydrochloric acid-acetone method and detects.
Embodiment 1
Getting carried by active carbon 5g, at first to be immersed in massfraction be 10～30% 75g HNO
3In solution, dipping temperature is 20～40 ℃, and dipping time is 3～4h, then takes out gac and is washed to neutrality, filters, gets final product after drying and to get the gac of modification; Impregnated at the gac with modification that to contain the boron trifluoride massfraction be that in 0.5% 75g toluene solution, dipping temperature is 30～45 ℃, dipping time is 3～4h, filters, gets final product to get this catalyzer after drying.The supported quantity that records the immobilized boron trifluoride catalyst of this gac is 5%.
Embodiment 2
Getting carried by active carbon 5g, at first to be immersed in massfraction be 10～30% 50g HNO
3In solution, dipping temperature is 40～70 ℃, and dipping time is 2～3h, then takes out gac and is washed to neutrality, filters, gets final product after drying and to get the gac of modification; Impregnated at the gac with modification that to contain the boron trifluoride massfraction be that in 2% 50g toluene solution, dipping temperature is 45～60 ℃, dipping time is 2.5～3h, filters, gets final product to get this catalyzer after drying.The supported quantity that records the immobilized boron trifluoride catalyst of this gac is 16%.
Embodiment 3
Getting carried by active carbon 5g, at first to be immersed in massfraction be 10～30% 25g HNO
3In solution, dipping temperature is 70～100 ℃, and dipping time is 1～2h, then takes out gac and is washed to neutrality, filters, gets final product after drying and to get the gac of modification; Impregnated at the gac with modification that to contain the boron trifluoride massfraction be that in 5% 50g toluene solution, dipping temperature is 60～70 ℃, dipping time is 1～2.5h, filters, gets final product to get this catalyzer after drying.The supported quantity that records the immobilized boron trifluoride catalyst of this gac is 20%.
Embodiment 4
In with the 500ml four-hole boiling flask with mechanical stirrer, reflux exchanger and the thermometer of mechanical seal, add respectively vinyl carbinol 116g, boron trifluoride diethyl etherate 0.6g, turn on agitator, be warming up to 40 ℃, drip epoxy chloropropane 189g, control 40～50 ℃ of temperature of reaction, 2h finishes, insulation reaction 4h; Be cooled to 35 ℃, then drip 32%NaOH263g, control 35～45 ℃ of temperature of reaction, reaction 6h finishes; Filter out by product NaCl, isolate lower floor's salt solution, refinement treatment gets glycidyl allyl ether product 186g, and the oxirane value that records product is 0.590eq/100g.
Embodiment 5
In with the 500ml four-hole boiling flask with mechanical stirrer, reflux exchanger and the thermometer of mechanical seal, add respectively vinyl carbinol 116g, the immobilized boron trifluoride 3g of gac, turn on agitator, be warming up to 40 ℃, drip epoxy chloropropane 189g, control 40～50 ℃ of temperature of reaction, 2h finishes, insulation reaction 4h; Be cooled to 35 ℃, filter out catalyzer, then drip 32%NaOH263g, control 35～45 ℃ of temperature of reaction, reaction 6h finishes; Filter out by product NaCl, isolate lower floor's salt solution, refinement treatment gets glycidyl allyl ether product 184g, oxirane value 0.598eq/100g.
Embodiment 6
In with the 500ml four-hole boiling flask with mechanical stirrer, reflux exchanger and the thermometer of mechanical seal, the immobilized boron trifluoride of gac that adds vinyl carbinol 116g and example 5 to reclaim, turn on agitator, be warming up to 40 ℃, drip epoxy chloropropane 189g, control 40～50 ℃ of temperature of reaction, 2h finishes, insulation reaction 4h; (stratographic analysis intermediate content 1.2% after open loop) is cooled to 35 ℃, filters out catalyzer, then drips 32%NaOH263g, controls 35～45 ℃ of temperature of reaction, reaction 6h; Filter out by product NaCl, isolate lower floor's salt solution, refinement treatment gets glycidyl allyl ether product 181g, and the oxirane value that records product is 0.592eq/100g.
Embodiment 7
In with the 500ml four-hole boiling flask with mechanical stirrer, reflux exchanger and the thermometer of mechanical seal, add respectively vinyl carbinol 116g, the immobilized boron trifluoride 3g of gac, turn on agitator, be warming up to 50 ℃, drip epoxy chloropropane 189g, control 60～70 ℃ of temperature of reaction, 2h finishes, insulation reaction 4h; Be cooled to 35 ℃, filter out catalyzer, then drip 32%NaOH263g, control 35～45 ℃ of temperature of reaction, reaction 6h; Filter out by product NaCl, isolate lower floor's salt solution, refinement treatment gets glycidyl allyl ether product 182g, and the oxirane value that records product is 0.640eq/100g.
Embodiment 8
In with the 1000ml four-hole boiling flask with mechanical stirrer, reflux exchanger and the thermometer of mechanical seal, add respectively vinyl carbinol 348g, the immobilized boron trifluoride catalyst 5g of gac, turn on agitator, be warming up to 90 ℃, drip epoxy chloropropane 189g, control 50～60 ℃ of temperature of reaction, 2h finishes, insulation reaction 4h, reaction is finished, and filters out catalyzer, air distillation removes unreacted vinyl carbinol 226g; Be cooled to 35 ℃, then drip 32%NaOH263g, control 35～45 ℃ of temperature of reaction, filter out by product NaCl, isolate lower floor's salt solution, refinement treatment gets glycidyl allyl ether product 198g, and the oxirane value that records product is 0.627eq/100g.
Claims (3)
1. the synthetic method of a glycidyl allyl ether, comprise that vinyl carbinol and epoxy chloropropane generation ring-opening reaction produce the chlorallylene alcohol intermediate, and chlorallylene alcohol intermediate and sodium hydroxide carry out ring-closure reaction and produce glycidyl allyl ether, ring-opening reaction catalyzer used is the immobilized boron trifluoride catalyst of gac, and the supported quantity of boron trifluoride is 5～20%.
2. the synthetic method of a kind of glycidyl allyl ether as claimed in claim 1, it is characterized in that: the material ratio of vinyl carbinol and epoxy chloropropane is 2～3:1, the material ratio of epoxy chloropropane and sodium hydroxide is 1:1～1.2; The consumption of the immobilized boron trifluoride catalyst of gac be ring-opening reaction the reactant total mass 0.5～2%.
3. the synthetic method of a kind of glycidyl allyl ether as claimed in claim 2, it is characterized in that: epoxy chloropropane and the immobilized boron trifluoride catalyst of gac are added in vinyl carbinol, condensing reflux stirs and carries out ring-opening reaction, the temperature of controlling ring-opening reaction is 50～60 ℃, time 4h left and right, ring-opening reaction removes unreacted vinyl carbinol after finishing, the immobilized boron trifluoride catalyst of elimination gac after cooling; And then add sodium hydroxide to carry out ring-closure reaction, about 35～45 ℃ of the temperature control bits of ring-closure reaction, time 6h, ring-closure reaction is removed sodium-chlor after finishing, and gets final product to get glycidyl allyl ether after refinement treatment.
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106279666A (en) * | 2016-08-27 | 2017-01-04 | 广东红墙新材料股份有限公司 | A kind of polyhydroxy PEG polymeric monomer and preparation method thereof |
| CN112279823A (en) * | 2020-10-22 | 2021-01-29 | 江苏扬农化工集团有限公司 | Method for preparing methyl glycidyl ether from epichlorohydrin by-product |
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| JPS5626886A (en) * | 1979-08-10 | 1981-03-16 | Asahi Glass Co Ltd | Preparation of glycidyl vinyl ether |
| JP2007297330A (en) * | 2006-04-28 | 2007-11-15 | Daiso Co Ltd | Method of manufacturing 2-methylglycidyl derivative |
| CN102432437A (en) * | 2011-11-28 | 2012-05-02 | 南京林业大学 | Synthesis method of glycol dialkyl ether |
| JP5626886B2 (en) * | 2010-11-22 | 2014-11-19 | Ｎｅｃプラットフォームズ株式会社 | Content purchase / playback apparatus and content providing method |
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| CN106279666B (en) * | 2016-08-27 | 2019-08-23 | 广东红墙新材料股份有限公司 | A kind of polyhydroxy PEG polymeric monomer and preparation method thereof |
| CN112279823A (en) * | 2020-10-22 | 2021-01-29 | 江苏扬农化工集团有限公司 | Method for preparing methyl glycidyl ether from epichlorohydrin by-product |
| CN112279823B (en) * | 2020-10-22 | 2023-09-12 | 江苏扬农化工集团有限公司 | Method for preparing methyl glycidyl ether from epoxy chloropropane by-product |
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