CN103191761A - Catalyst, preparation method thereof and method for preparing aliphatic glycidyl ether by using catalyst - Google Patents
Catalyst, preparation method thereof and method for preparing aliphatic glycidyl ether by using catalyst Download PDFInfo
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Abstract
The invention discloses a catalyst which comprises an activated carbon body, wherein boron trifluoride is fixedly loaded on the outer surface of the activated carbon body. The solid-phase catalyst formed by fixedly loading boron trifluoride on the activated carbon is good in selectivity on the main reaction in the ring-opening reaction process that aliphatic glycidyl ether is prepared, and a final product is high in epoxy value, low in organic chloride content and good in quality; and in addition, the solid-phase catalyst is low in equipment corrosion, easy to be separated from a reaction product after the ring-opening reaction is accomplished, and can be recycled and reused after being separated.
Description
Technical field
The present invention relates to the synthetic field of aliphatic glycidyl ether, be specifically related to a kind of Catalysts and its preparation method and the method for utilizing this Preparation of Catalyst aliphatic glycidyl ether.
Background technology
Aliphatic glycidyl ether is a kind of aliphatic epoxy base diluent of line style, comprises ehter bond and epoxy radicals in the molecule, has 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 using always, can be widely used in the dilution of 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 fatty amine, imidazoles.
Synthetic one-step method, two-step method and the oxidizing process of mainly containing of aliphatic glycidyl ether, synthctic fat family glycidol ether mainly adopts two-step process both at home and abroad at present.The two-step method synthesis technique is under the acidic catalyst effect, carries out ring-opening reaction by fatty alcohol and epoxychloropropane, and then carries out ring-closure reaction with NaOH and generate corresponding glycidol ether; Be that feedstock fat alcohol, acidic catalyst and epoxychloropropane carry out ring-opening reaction, generate chloropharin ether intermediate, carry out the ring-closure reaction reaction with NaOH again and make glycidol ether, wherein ring-opening reaction is the synthetic key of two-step method, and the acidic catalyst that uses in the ring-opening reaction is mainly strong-acid type catalyst such as the concentrated sulfuric acid, perchloric acid and lewis acid BF at present
3O (C
2H
5)
2, butter of tin, alchlor, titanium tetrachloride or ferric trichloride etc.Use such acidic catalyst not only to exist shortcomings such as consersion unit seriously corroded, use inconvenience, the recovery uses that can not circulate; And selectively relatively poor in ring-opening reaction, cause the accessory substance in the intermediate product many, make the epoxide number of end product low, chloride content is high.
Summary of the invention
First purpose of the present invention provides a kind of catalyst, the main reaction that improves ring-opening reaction in the aliphatic glycidyl ether preparation process is selective, increase the epoxide number of end product and reduce chlorinity, simultaneously this catalyst can be recycled, low to the corrosivity of equipment.
Its scheme of taking is, a kind of catalyst comprises the active carbon body, and immobilized on the outer surface of active carbon body have a boron trifluoride.
By with the immobilized solid-phase catalyst that constitutes at active carbon of boron trifluoride, selectively good to main reaction in for the preparation of the ring-opening reaction process of aliphatic glycidyl ether, epoxide number height and the content of organic chloride of end product are low, the quality better of product; In addition, this solid-phase catalyst is low to equipment corrosion, ring-opening reaction is separated with product after finishing easily, and can be recycled after separating.
Those skilled in the art can produce the immobilized boron trifluoride catalyst of the active carbon that obtains different supported quantities by different preparation method and application's demands, but easy the to be capable property that the inventor produces through long term test, in conjunction with this catalyst and to the optimality of the ring-opening reaction influence of preparation aliphatic glycidyl ether, the supported quantity of preferably choosing boron trifluoride is 5～20%, to obtain best preparation and result of use.
Second purpose of the present invention provides a kind of this Preparation of catalysts method, comprises following operating procedure:
S1: active carbon is carried out modification handle, and with active carbon washing, drying after the modification processing;
S2: dried active carbon be impregnated in the organic solution that contains boron trifluoride, dipping fully back suction filtration, drying get final product this catalyst.
Organic solution described in the step S2 comprises toluene, phenmethylol, anhydrous butanols.
Modification described in the above-mentioned steps S1 is handled the surface group that comprises active carbon and is carried out modification and/or the duct of active carbon is expanded; In addition, can effectively load on the active carbon for making boron trifluoride, catalytic selectivity the best of main reaction is preferably implemented according to following operation in the divided ring reaction, that is:
S1: it is 10～30% HNO that absorbent charcoal carrier at first is immersed in mass fraction
3In the solution, the solid-liquid mass ratio of control dipping is 1:5～1:15, and dipping temperature is 20～100 ℃, and dip time is 1～4h, takes out active carbon then and is washed to neutrality, filter, get final product after the drying the active carbon of modification;
S2: the active carbon of modification be impregnated in to contain the boron trifluoride mass fraction be in 0.5～5% the toluene solution, the solid-liquid mass ratio of control dipping is that 1:10～1:15, dipping temperature are 30～70 ℃, dip time is 1～4h, filter, get final product after the drying this catalyst.
The 3rd purpose of the present invention provides a kind of purposes of this catalyst, that is for the preparation of aliphatic glycidyl ether, concrete is: be that fatty alcohol and epoxychloropropane are carried out ring-opening reaction under the catalytic action of the immobilized boron trifluoride catalyst of active carbon, generate chloropharin ether intermediate; And then chloropharin ether intermediate and NaOH are carried out ring-closure reaction make aliphatic glycidyl ether.Described fatty alcohol comprises that described fatty alcohol comprises phenmethylol, octanol, C
12-14Alcohol, ethylene glycol, propane diols, glycerine, polyoxy alkane enediol.Certainly the fatty alcohol here also can be chosen alkylol, alkenyl alcohol or the polyalcohol etc. of other carbochain numbers.
For the productive rate that improves aliphatic glycidyl ether with shorten the consuming time of entire reaction, the present invention preferably implements by following detail operations:
The material ratio of fatty alcohol and epoxychloropropane is 1～2:1, the consumption of the immobilized boron trifluoride catalyst of active carbon be ring-opening reaction the reactant quality 0.5～2%; The material ratio of epoxychloropropane and NaOH is 1:1～1.2; The reaction temperature of ring-opening reaction is 80～100 ℃; The reaction temperature of ring-closure reaction is 35～45 ℃.In addition, ring-closure reaction can select for use the quaternary ammonium salt catalyst as catalyst for reaction, the quaternary ammonium salt catalyst consumption be ring-closure reaction the reactant gross mass 0.05～0.1%.
The above-mentioned raw materials ratio choose and catalyst amount limits, can effectively suppress the generation of side reaction in ring-opening reaction and the ring-closure reaction, the epoxide number height of the end product that makes, organochlorine are low.Use the reaction of quaternary ammonium salt catalyst in addition in ring-closure reaction, more be conducive to the carrying out of ring-closure reaction, the hydrolyzable chlorine of product is low, the epoxide number height.
The specific 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 active carbon, embodiment 4～12 is for to utilize the immobilized boron trifluoride catalyst of the active carbon of producing among the embodiment 1～3 to produce aliphatic glycidyl ether, and the raw material that each embodiment is used: epoxychloropropane, fatty alcohol, 32% NaOH are technical grade; Benzyltriethylammoinium chloride, benzyl triethyl ammonium bromide, hexadecyltrimethylammonium chloride, softex kw, tetrabutylammonium chloride, TBAB, 4 bromide are chemical pure, are produced by Shanghai chemical reagents corporation of Chinese Medicine group.
The supported quantity operating weight method of the immobilized boron trifluoride of active carbon that makes is measured.
The epoxide number of aliphatic glycidyl ether detects with hydrochloric acid-acetone method and detects.
Embodiment 1
Getting carried by active carbon 5g, at first to be immersed in mass fraction be 10～30% 75g HNO
3In the solution, dipping temperature is 20～40 ℃, and dip time is 3～4h, takes out active carbon then and is washed to neutrality, filter, get final product after the drying the active carbon of modification; Impregnated at the active carbon with modification that to contain the boron trifluoride mass fraction be that dipping temperature is 30～45 ℃ in 0.5% the 75g toluene solution, dip time is 3～4h, filter, get final product after the drying this catalyst.The supported quantity that records the immobilized boron trifluoride catalyst of this active carbon is 5%.
Embodiment 2
Getting carried by active carbon 5g, at first to be immersed in mass fraction be 10～30% 50g HNO
3In the solution, dipping temperature is 40～70 ℃, and dip time is 2～3h, takes out active carbon then and is washed to neutrality, filter, get final product after the drying the active carbon of modification; Impregnated at the active carbon with modification that to contain the boron trifluoride mass fraction be that dipping temperature is 45～60 ℃ in 2% the 50g toluene solution, dip time is 2.5～3h, filter, get final product after the drying this catalyst.The supported quantity that records the immobilized boron trifluoride catalyst of this active carbon is 16%.
Embodiment 3
Getting carried by active carbon 5g, at first to be immersed in mass fraction be 10～30% 25g HNO
3In the solution, dipping temperature is 70～100 ℃, and dip time is 1～2h, takes out active carbon then and is washed to neutrality, filter, get final product after the drying the active carbon of modification; Impregnated at the active carbon with modification that to contain the boron trifluoride mass fraction be that dipping temperature is 60～70 ℃ in 5% the 50g toluene solution, dip time is 1～2.5h, filter, get final product after the drying this catalyst.The supported quantity that records the immobilized boron trifluoride catalyst of this active carbon is 20%.
Embodiment 4
In the 1000ml four-hole boiling flask of mechanical agitator, reflux condenser and thermometer that band mechanical seal is housed, add phenmethylol 216g respectively, the immobilized boron trifluoride catalyst 5g of active carbon, turn on agitator, be warming up to 80 ℃, drip epoxychloropropane 189g, 80～90 ℃ of control reaction temperatures, 2h finishes, insulation reaction 4h; Be cooled to 35 ℃, filter out catalyst, add benzyltriethylammoinium chloride 0.2g, drip 32%NaOH263g again, 35～45 ℃ of control reaction temperatures, stirring reaction 6h, reaction finishes, and filters out accessory substance NaCl, isolates lower floor's salt solution, refinement treatment gets benzyl glycidyl ether product 265g, and the epoxide number that records product is 0.433eq/100g.Embodiment 5
In the 1000ml four-hole boiling flask of mechanical agitator, reflux condenser and thermometer that band mechanical seal is housed, add phenmethylol 216g respectively, the immobilized boron trifluoride catalyst of active carbon that example 4 reclaims, turn on agitator, be warming up to 90 ℃, drip epoxychloropropane 189g, 90～100 ℃ of control reaction temperatures, 2h finishes, insulation reaction 4h; Be cooled to 35 ℃, filter out catalyst, add benzyltriethylammoinium chloride 0.2g, drip 32%NaOH263g again, 35～45 ℃ of control reaction temperatures, stirring reaction 6h, reaction finishes, and filters out accessory substance NaCl, isolates lower floor's salt solution, refinement treatment gets benzyl glycidyl ether product 259g, and the epoxide number that records product is 0.424eq/100g.
Embodiment 6
In the 1000ml four-hole boiling flask of mechanical agitator, reflux condenser and thermometer that band mechanical seal is housed, add the immobilized boron trifluoride catalyst of active carbon that phenmethylol 216g and example 5 reclaim, turn on agitator, be warming up to 50 ℃, drip epoxychloropropane 189g, 50～60 ℃ of control reaction temperatures, 2h finishes, insulation reaction 4h; Be cooled to 35 ℃, filter out catalyst, add benzyltriethylammoinium chloride 0.2g, drip 32%NaOH263g again, 35～45 ℃ of control reaction temperatures, stirring reaction 6h, reaction finishes, and filters out accessory substance NaCl, isolates lower floor's salt solution, refinement treatment gets benzyl glycidyl ether product 202g, and the epoxide number that records product is 0.288eq/100g.
Embodiment 7
In the 1000ml four-hole boiling flask of mechanical agitator, reflux condenser and thermometer that band mechanical seal is housed, add 2-Ethylhexyl Alcohol 260g respectively, the immobilized boron trifluoride catalyst 4g of active carbon, turn on agitator, be warming up to 50 ℃, drip epoxychloropropane 189g, 50～60 ℃ of control reaction temperatures, 2h finishes, insulation reaction 4h; Be cooled to 35 ℃, filter out catalyst, add softex kw 0.2g, drip 32%NaOH263g again, 35～45 ℃ of control reaction temperatures, stirring reaction 6h, reaction finishes, and filters out accessory substance NaCl, isolates lower floor's salt solution, refinement treatment gets 2-ethylhexyl glycidol ether product 341g, and the epoxide number that records product is 0.376eq/100g.
Embodiment 8
In the 1000ml four-hole boiling flask of mechanical agitator, reflux condenser and thermometer that band mechanical seal is housed, add 2-Ethylhexyl Alcohol 650g respectively, the immobilized boron trifluoride catalyst 6g of active carbon, turn on agitator, be warming up to 50 ℃, drip epoxychloropropane 189g, 50～60 ℃ of control reaction temperatures, 2h finishes, insulation reaction 4h; Filter out catalyst, unreacted 2-Ethylhexyl Alcohol 370g is reclaimed in rectification under vacuum, is cooled to 35 ℃, adds tetramethyl ammonium chloride 0.2g, drip 32%NaOH263g again, 35～45 ℃ of control reaction temperatures, stirring reaction 6h, reaction finishes, filter out accessory substance NaCl, isolate lower floor's salt solution, refinement treatment gets 2-ethylhexyl glycidol ether product 333g, and the epoxide number that records product is 0.432eq/100g.
Embodiment 9
In the 1000ml four-hole boiling flask of mechanical agitator, reflux condenser and thermometer that band mechanical seal is housed, add C10 fatty alcohol 316g respectively, the immobilized boron trifluoride catalyst 6g of active carbon, turn on agitator, be warming up to 50 ℃, drip epoxychloropropane 189g, 50～60 ℃ of control reaction temperatures, 6h finishes; Be cooled to 35 ℃, filter out catalyst, add TBAB 0.2g, drip 32%NaOH263g again, 35～45 ℃ of control reaction temperatures, stirring reaction 6h, reaction finishes, and filters out accessory substance NaCl, isolates lower floor's salt solution, refinement treatment gets C10 fatty alcohol glycidol ether product 363g, and the epoxide number that records product is 0.354eq/100g.
Embodiment 10
In the 1000ml four-hole boiling flask of mechanical agitator, reflux condenser and thermometer that band mechanical seal is housed, add C respectively
12-14Fatty alcohol 400g, the immobilized boron trifluoride catalyst 7g of active carbon, turn on agitator is warming up to 50 ℃, drips epoxychloropropane 189g, 60～70 ℃ of control reaction temperatures, 6h finishes; Be cooled to 35 ℃, filter out catalyst, add hexadecyltrimethylammonium chloride 0.4g, drip 32%NaOH263g again, 35～45 ℃ of control reaction temperatures, stirring reaction 6h, reaction finishes, and filters out accessory substance NaCl, isolates lower floor's salt solution, and refinement treatment gets C
10-12Fatty alcohol glycidol ether product 480g, the epoxide number that records product is 0.291eq/100g.
Embodiment 11
In the 1000ml four-hole boiling flask of mechanical agitator, reflux condenser and thermometer that band mechanical seal is housed, add glycerine 92g respectively, toluene 300g, the immobilized boron trifluoride catalyst 7g of active carbon, turn on agitator is warming up to 50 ℃, drips epoxychloropropane 305g, 55～65 ℃ of control reaction temperatures, 6h finishes; Be cooled to 35 ℃, filter out catalyst, add benzyltriethylammoinium chloride 0.4g, drip 32%NaOH375g again, 35～45 ℃ of control reaction temperatures, stirring reaction 6h, reaction finishes, and filters out accessory substance NaCl, isolate lower floor's salt solution, with 30g water washing secondary, get glycerine three-glycidyl ether product 195g behind the recovery toluene respectively, the epoxide number that records product is 0.676eq/100g.
Embodiment 12
In the 500ml four-hole boiling flask of mechanical agitator, reflux condenser and thermometer that band mechanical seal is housed, add polypropylene glycol (200) 100g respectively, toluene 150g, the immobilized boron trifluoride catalyst 7g of active carbon, turn on agitator is warming up to 50 ℃, drips epoxychloropropane 105g, 60～70 ℃ of control reaction temperatures, 6h finishes; Be cooled to 35 ℃, filter out catalyst, add 4 bromide 0.4g, add solid NaOH42g, 35～45 ℃ of control reaction temperatures, stirring reaction 6h, reaction finishes, and filters out accessory substance NaCl, isolates lower floor's salt solution, get polypropylene glycol (200) 2-glycidyl ether product 216g behind the washing of 30g water, the recovery toluene, the epoxide number that records product is 0.483eq/100g.
Claims (9)
1. a catalyst comprises the active carbon body, and immobilized on the outer surface of active carbon body have a boron trifluoride.
2. catalyst as claimed in claim 1, it is characterized in that: the supported quantity of boron trifluoride is 5～20%.
3. method for preparing the described catalyst of claim 1 comprises following operating procedure:
S1: active carbon is carried out modification handle, and with active carbon washing, drying after the modification processing;
S2: dried active carbon be impregnated in the organic solution that contains boron trifluoride, dipping fully back suction filtration, drying get final product this catalyst.
4. the method for preparing catalyst as claimed in claim 3, it is characterized in that: the organic solution described in the step S2 comprises toluene, phenmethylol, anhydrous butanols.
5. the method for preparing catalyst as claimed in claim 4 is characterized in that:
S1: it is 10～30% HNO that absorbent charcoal carrier at first is immersed in mass fraction
3In the solution, the solid-liquid mass ratio of control dipping is 1:5～1:15, and dipping temperature is 20～100 ℃, and dip time is 1～4h, takes out active carbon then and is washed to neutrality, filter, get final product after the drying the active carbon of modification;
S2: the active carbon of modification be impregnated in to contain the boron trifluoride mass fraction be in 0.5～5% the toluene solution, the solid-liquid mass ratio of control dipping is that 1:10～1:15, dipping temperature are 30～70 ℃, dip time is 1～4h, filter, get final product after the drying this catalyst.
6. method of utilizing the described Preparation of Catalyst aliphatic glycidyl ether of claim 1, it is characterized in that: be that fatty alcohol and epoxychloropropane are carried out ring-opening reaction under the catalytic action of the immobilized boron trifluoride catalyst of active carbon, generate chloropharin ether intermediate; And then chloropharin ether intermediate and NaOH are carried out ring-closure reaction make aliphatic glycidyl ether.
7. the method for utilizing the Preparation of Catalyst aliphatic glycidyl ether as claimed in claim 6, it is characterized in that: described fatty alcohol comprises phenmethylol, octanol, C
12-14Alcohol, ethylene glycol, propane diols, glycerine, polyoxy alkane enediol.
8. as claim 6 or the 7 described methods of utilizing the Preparation of Catalyst aliphatic glycidyl ether, it is characterized in that: the material ratio of fatty alcohol and epoxychloropropane is 1～3:1, the consumption of the immobilized boron trifluoride catalyst of active carbon be ring-opening reaction the reactant gross mass 0.5～2%; The material ratio of epoxychloropropane and NaOH is 1:1～1.2; The reaction temperature of ring-opening reaction is 50～120 ℃; The reaction temperature of ring-closure reaction is 30～60 ℃.
9. the method for utilizing the Preparation of Catalyst aliphatic glycidyl ether as claimed in claim 6, it is characterized in that: ring-closure reaction selects for use the quaternary ammonium salt catalyst as catalyst for reaction, the quaternary ammonium salt catalyst consumption be ring-closure reaction the reactant gross mass 0.05～0.1%.
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| CN113372301A (en) * | 2021-05-18 | 2021-09-10 | 张家港衡业特种树脂有限公司 | Preparation process of alkyl glycidyl ether serving as active epoxy resin diluent |
| CN114262309A (en) * | 2021-12-14 | 2022-04-01 | 江苏三木化工股份有限公司 | Environment-friendly preparation method of polypropylene glycol diglycidyl ether |
| CN114289039A (en) * | 2021-11-12 | 2022-04-08 | 南京林业大学 | Bentonite-loaded stannic chloride solid acid catalyst, and preparation method and application thereof |
| CN115960057A (en) * | 2022-12-29 | 2023-04-14 | 苏州元素集化学工业有限公司 | Method for preparing alkyl glycidyl ether by novel catalyst |
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Cited By (8)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN106749106A (en) * | 2016-12-23 | 2017-05-31 | 湖北绿色家园材料技术股份有限公司 | The synthetic method of ethylene glycol diglycidylether |
| CN106749106B (en) * | 2016-12-23 | 2019-05-14 | 湖北绿色家园材料技术股份有限公司 | The synthetic method of ethylene glycol diglycidylether |
| CN107793378A (en) * | 2017-11-27 | 2018-03-13 | 湖北绿色家园材料技术股份有限公司 | A kind of novel method for synthesizing of glycerin triglycidyl ether |
| CN113372301A (en) * | 2021-05-18 | 2021-09-10 | 张家港衡业特种树脂有限公司 | Preparation process of alkyl glycidyl ether serving as active epoxy resin diluent |
| CN114289039A (en) * | 2021-11-12 | 2022-04-08 | 南京林业大学 | Bentonite-loaded stannic chloride solid acid catalyst, and preparation method and application thereof |
| CN114289039B (en) * | 2021-11-12 | 2024-01-26 | 南京林业大学 | Bentonite-loaded stannic chloride solid acid catalyst, and preparation method and application thereof |
| CN114262309A (en) * | 2021-12-14 | 2022-04-01 | 江苏三木化工股份有限公司 | Environment-friendly preparation method of polypropylene glycol diglycidyl ether |
| CN115960057A (en) * | 2022-12-29 | 2023-04-14 | 苏州元素集化学工业有限公司 | Method for preparing alkyl glycidyl ether by novel catalyst |
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| TA01 | Transfer of patent application right |
Effective date of registration: 20130813 Address after: Nanjing City, Jiangsu province 210037 Longpan Road No. 159 Applicant after: Nanjing Forestry University Applicant after: New far Chemical Industry Co., Ltd. of Anhui Applicant after: Anhui Hengyuan Chemical Co., Ltd. Address before: Nanjing City, Jiangsu province 210037 Longpan Road No. 159 Applicant before: Nanjing Forestry University Applicant before: New far Chemical Industry Co., Ltd. of Anhui |
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| CB02 | Change of applicant information |
Address after: Nanjing City, Jiangsu province 210037 Longpan Road No. 159 Applicant after: Nanjing Forestry University Applicant after: Anhui Xinyuan Chemical Co., Ltd. Applicant after: Anhui Hengyuan New Material Co. Ltd. Address before: Nanjing City, Jiangsu province 210037 Longpan Road No. 159 Applicant before: Nanjing Forestry University Applicant before: New far Chemical Industry Co., Ltd. of Anhui Applicant before: Anhui Hengyuan Chemical Co., Ltd. |
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| COR | Change of bibliographic data | ||
| C12 | Rejection of a patent application after its publication | ||
| RJ01 | Rejection of invention patent application after publication |
Application publication date: 20130710 |