CN106518815B - A kind of continuous esterification prepares the method for tetrahydrofuran acrylate and its preparation method of catalyst - Google Patents
A kind of continuous esterification prepares the method for tetrahydrofuran acrylate and its preparation method of catalyst Download PDFInfo
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- CN106518815B CN106518815B CN201510575768.6A CN201510575768A CN106518815B CN 106518815 B CN106518815 B CN 106518815B CN 201510575768 A CN201510575768 A CN 201510575768A CN 106518815 B CN106518815 B CN 106518815B
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- C07D307/02—Heterocyclic compounds containing five-membered rings having one oxygen atom as the only ring hetero atom not condensed with other rings
- C07D307/04—Heterocyclic compounds containing five-membered rings having one oxygen atom as the only ring hetero atom not condensed with other rings having no double bonds between ring members or between ring members and non-ring members
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- B01J2231/40—Substitution reactions at carbon centres, e.g. C-C or C-X, i.e. carbon-hetero atom, cross-coupling, C-H activation or ring-opening reactions
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Abstract
The method that a kind of continuous esterification of disclosure of the invention prepares tetrahydrofuran acrylate, using acrylic acid and tetrahydrofurfuryl alcohol as raw material, using the composite catalyst of metal ion-modified solid acid catalyst and graphite, silicon carbide in submicro level whisker, nanoscale tungsten, nanoscale zirconia, metal ion etc. are added in the catalyst to be modified ion exchange resin, realize two-part continuous esterification.The present invention passes through control temperature, reaction pressure etc.; realize the continuous production of tetrahydrofuran acrylate; conversion ratio can reach 100%; monoesters selectively reaches 97%, and total yield of products reaches 97%, and the method for the present invention is easy to operate; it is remarkably improved production efficiency; production cost is reduced, and greatly reduces the discharge amount of waste water, there is good large-scale industrial application value.
Description
Technical field
The present invention relates to the preparation methods of tetrahydrofuran acrylate, and in particular to a kind of to be prepared using continuous esterification
The method of tetrahydrofuran acrylate belongs to photo-curing material field.
Background technique
Tetrahydrofuran acrylate (hereinafter referred to as TFA) is a kind of important Specialty Acrylates, and structural formula is
The special construction of TFA assigns its subsequent product special property, firstly, the cyclic ether group in TFA molecule compares straight chain
Ether is more imbued with activity, and the hydrogen on the alpha-position carbon of ehter bond also has certain activity, therefore, using TFA as the third of copolymer composition
Olefin(e) acid resin and amino resins and used time, it can solidify under lower temperature (about 100 DEG C).Secondly, TFA molecule valence link have it is certain
Flexibility, with other resins and with the effect that can play plasticising.In addition, TFA, which is also used as monomer diluent, is applied to purple
Outer light (UV) cured article, special cyclic ether structure have it more compared with other monofunctional monomers to most of grounds
Good adhesive force, while having low-shrinkage, strong weatherability, strong wearability and strong water resistance, therefore, it is solid to be widely used in light
The fields such as adhesive, coating, the ink of change.
Chinese publication CN102146037A discloses a kind of by esterification, neutralization, washing, solvent removal step preparation third
The method of olefin(e) acid ester；EP Published Patent EP0609127 and DE Published Patent DE19851983 describes a kind of mixed from reaction
It closes azeotropic distillation in object to go out to react the water generated, the method for then preparing (methyl) acrylate by extraction.It reacted above
Catalyst used in journey generallys use strong acid, such as phosphoric acid, sulfuric acid, chlorosulfonic acid, p-methyl benzenesulfonic acid, sulfamic acid, reacts and is
Homogeneous reaction, the route technical maturity used in technology disclosed above, but there are many disadvantages: 1, the removal of homogeneous catalyst want
By the multiple alkali cleaning and washing after reaction, System Catalyst is by irreversible change in this process, so that they cannot
It is reused, while this process generates a large amount of waste water, causes very big environmental protection pressure；2, washing repeatedly causes under yield
Drop, remaining moisture also affect product quality；3, intermittently operated production efficiency is low, complicated for operation, is unfavorable for scale
Production, and unstable quality between batch.In addition intermittently operated side reaction is obvious, and oligomer is excessive in system, product face
Colour cast is deep.
In Chinese publication CN1355161A, DE Published Patent DE3423443 and US publication US6194530
It discloses and the method that transesterification prepares target product is carried out by acrylate and small molecular alcohol in the presence of a catalyst.It should
The not reproducible use of method catalyst, target product yield are low, and generate a large amount of waste water.
It is increasingly developed with material science, it is contemplated that TFA, which has, to be more and more widely used.In view of the above problems,
It is badly in need of the new process that R and D are used to prepare TFA.
Summary of the invention
The purpose of the present invention is intended to provide a kind of method that continuous esterification prepares tetrahydrofuran acrylate (TFA),
Using acrylic acid and tetrahydrofurfuryl alcohol as raw material, using solid acid catalyst, while metal ion is added in the catalyst to catalyst
It is modified, realizes two-part continuous esterification.The method overcome products present in existing batch production technique to need
Through alkali cleaning, neutralization and washing process, a large amount of waste water and complex process are generated, the disadvantages of production efficiency is low, and side reaction is more.
The present invention is able to achieve the continuous production of TFA, and reduces the discharge of waste water in process of production, can greatly improve the life of TFA
Efficiency is produced, its production cost is reduced.
Another object of the present invention is to provide the catalyst that tetrahydrofuran acrylate is prepared for continuous esterification
Preparation method.
In order to realize that the above goal of the invention, the technical solution adopted in the present invention are as follows:
A kind of technique that continuous esterification prepares tetrahydrofuran acrylate (TFA), comprising the following steps:
1) using acrylic acid and tetrahydrofurfuryl alcohol as raw material, under the action of catalyst A, continuous ester is carried out in first segment reactor
Change reaction；
2) it using first segment reactor outlet reaction solution as raw material, under the action of catalyst B, is carried out in second segment reactor
Complete esterification.
Reaction solution after being esterified completely obtained in step 2) of the present invention obtains tetrahydrofuran third by vacuum distillation
Alkene acid ester product.
The catalyst A and catalyst B is metal ion-modified netted composite enhanced styryl amberlite
The composite catalyst of rouge and graphite；Metal ion-modified netted composite enhanced benzene second in the catalyst A and catalyst B
Alkenyl ion exchange resin is identical, and in the catalyst A, content of graphite is 40~80wt% of the gross mass of catalyst A, preferably
50~70wt%；In the catalyst B, content of graphite is the 5~40wt%, preferably 10~35wt% of the gross mass of catalyst B.
In the present invention, metal ion-modified netted composite enhanced styryl described in catalyst A and catalyst B from
Metal ion described in sub-exchange resin is Li+、Cs+、Rb+、Cu+、Pd2+、Sr2+、Co2+、Ni2+、La3+、Ce3+、Rh3+And Ru3+
One or both of or a variety of, preferably Li+、Rb+、Cu+、Pd2+、Co2+、Rh3+And Ru3+One or both of or it is a variety of,
More preferably Li+、Cu+、Pd2+、Co2+And Ru3+One or both of or it is a variety of；In the catalyst A and catalyst B, it is based on
The gross mass of the metal ion-modified netted composite enhanced styryl ion exchange resin, the metal ion contain
Amount is 0.005~0.1wt%, preferably 0.01~0.07wt%, more preferable 0.03~0.05wt%.
In the present invention, metal ion-modified netted composite enhanced styrene described in the catalyst A and catalyst B
Group ion exchange resin is made by ortho-chlorostyrene and divinylbenzene, wherein ortho-chlorostyrene and divinylbenzene rub
You are than being 1:1~7:1, preferably 3:1~5:1.
In the present invention, the gross mass based on the ortho-chlorostyrene and divinylbenzene, the catalyst A and catalyst B
In also the monomer silicon carbide in submicro level whisker containing 1~5wt%, the nanoscale tungsten of 0.1~0.5wt% and 0.1~
The nanoscale zirconia of 1wt%.
In the present invention, the molar ratio of the raw material propylene acid and tetrahydrofurfuryl alcohol is 1:1~1.6:1, preferably 1.1:1~
1.4:1。
In the present invention, the esterification of step 1) and step 2) is to be respectively provided with the two of catalyst A and catalyst B at two
It is carried out continuously in a reactor.
In the present invention, the first segment reactor of step 1) and the second segment reactor of step 2) are separately added into atent solvent,
First segment reactor it is identical or different with solvent used in second segment reactor, it is preferable to use solvent it is identical；It is described molten
Agent is one or both of benzene, toluene, n-hexane, normal heptane, normal octane and hexamethylene or a variety of, preferably benzene, toluene, just
One or both of hexane and hexamethylene are a variety of, more preferably toluene and/or hexamethylene；First segment reactor and second segment
The used solvent usage of reactor is identical, the dosage of the solvent be based on acrylic acid and tetrahydrofurfuryl alcohol gross mass 20~
80wt%, preferably 40~60wt%.
In the present invention, it is separately added into polymerization inhibitor in the first segment reactor of step 1) and the second segment reactor of step 2),
The polymerization inhibitor being added in first segment reactor and second segment reactor is identical or different, and the polymerization inhibitor being preferably added to is identical；It is described
Polymerization inhibitor is one or both of hydroquinone, p-hydroxyanisole and tert-butyl hydroquinone or three kinds；First segment reaction
Device is identical with the dosage of polymerization inhibitor in second segment reactor, and the dosage of the polymerization inhibitor is based on acrylic acid and the total matter of tetrahydrofurfuryl alcohol
0.005~the 0.06wt%, preferably 0.01~0.04wt% of amount.
In the present invention, the first segment reactor includes but is not limited to tubular reactor, and reaction temperature is 50~100 DEG C,
It is preferred that 70~90 DEG C；React 70~103KPa of absolute pressure, preferably 80~95KPa；Mass space velocity is 1h-1~2.5h-1, excellent
Select 1.2h-1~2h-1。
In the present invention, after first segment reactor, the conversion ratio of raw material tetrahydrofurfuryl alcohol is 75~85%.
In the catalyst A and catalyst B that the present invention uses, with adjacent chlorine in the enhanced styryl ion exchange resin
Styrene replace traditional technology in styrene, can effectively reduce aromatic ring cloud density, improve acidic-group sulfonic group with
The bonding force of aromatic ring alleviates catalyst using sulfonic loss during especially applied at elevated temperature, to improve catalysis effect
Rate, the service life for extending catalyst.It can secondly, silicon carbide in submicro level whisker is added in catalyst A of the present invention and catalyst B
To effectively improve the mechanical strength of catalyst substrates, while filling of the catalyst in fixed bed can be improved, make the catalysis
Agent can be with large-scale application in high-intensitive operating condition.In addition, a small amount of nanoscale tungsten is added in catalyst A and catalyst B
And nanoscale zirconia, the nano particle of both oxides can cooperate with the duct intensity for promoting catalyst, stablize duct
Structure avoids tunnel collapse, while both oxides also substantially increase the heat-resisting ability of catalyst substrates.Finally, this
Ion exchange resin is modified with metal ion by using ion-exchange in invention, avoids acrylicacidandesters class
The incidental polymerization reaction on ordinary resin, hence it is evident that reduce the content of oligomer in product, reduce product coloration, improve and produce
Quality, while avoiding occurring situations such as carbon deposit, coking on catalyst.
In the present invention, second segment reactor can be identical as first segment reactor, can also be different, preferably anti-with first segment
Answer device identical.Second segment reactor is preferably tubular reactor, and reaction temperature is 90~150 DEG C, preferably 100~130 DEG C；Reaction
Pressure (absolute pressure) 50~90KPa, preferably 60~85KPa；Second segment reactor mass space velocity is 1h-1~3.5h-1, preferably 1.5h-1
~2.5h-1。
Catalyst B of the present invention is identical as the ontology of catalyst A described in step 1), but content of graphite can be identical
It can be different.Graphite has stable chemical structure, excellent electron transport ability and high specific surface area, the present invention
In, a certain amount of graphite is added in the catalyst A and catalyst B, the esterification process reaction time can be shortened, improves esterification effect
Rate.But a large amount of graphite use meeting so that product colour increase, therefore, under the premise of guaranteeing esterifying efficiency, and does not deepen to produce
The color of object controls the content of graphite in catalyst A and catalyst B in the present invention, anti-come the esterification of realizing of the invention
Answer effect.
In the present invention, the reaction solution after being esterified completely obtained in step 2) of the present invention is concentrated by vacuum distillation,
Removing solvent and excessive propene acid obtain tetrahydrofuran acrylate product.The operation temperature of vacuum distillation is 25~60 DEG C, excellent
Select 35~45 DEG C；Operating pressure (absolute pressure) is 50~300Pa, preferably 100~200Pa.
In order to reinforce conducting heat and avoid side reaction caused by strongly acidic catalyst, institute in heretofore described two reactor
Metal ion-modified netted composite enhanced styryl ion exchange resin is stated to be uniformly mixed to obtain with graphite crystal particle
The laggard luggage of composite catalyst is filled out.Since esterification is the reversible reaction controlled by thermodynamical equilibrium, for be conducive to reaction to
It is esterified direction to carry out, all leaves reaction system with the water formation azeotropic mixture generated is reacted using solvent in two reactor,
After reactor head condensation, split-phase, solvent Returning reactor, hydromining goes out to handle.In order to make fully reacting and control side reaction journey
Degree, two reactor individually control temperature and pressure.
The tetrahydrofuran acrylate product that the present invention is prepared is transparency liquid, and purity is 95~100wt%, acid value
For 0.3~0.5mg KOH/g, 25 DEG C of 6~10cps of viscosity@, coloration (Pt-Co) is 35~50；By first and second section of reactor
Afterwards, tetrahydrofurfuryl alcohol conversion ratio is 95~100%, yield 90~97%, monoesters selectivity 95~97%.
The present invention, the preparation method of used catalyst A and B, comprising the following steps:
1), ortho-chlorostyrene and divinylbenzene, silicon carbide in submicro level whisker, nanoscale tungsten and nanoscale
Zirconium mixing, heating stirring reaction；
2), the reaction solution that step 1 obtains through cooling, be filtered, washed, dry and extract after obtain netted composite enhanced benzene
Ethylene group ion exchange resin；
3) it, takes step 2 gained ion exchange resin to be placed in metal salt solution, is filtered, washed, dries after sufficiently impregnating,
Obtain metal ion-modified resin；
4), that the metal ion-modified resin of gained and graphite in step 3 is uniform through mechanical mixture, respectively obtain catalyst A
With catalyst B.
In catalyst preparation process of the present invention, need the addition sodium chloride into reactor full before heating stirring reaction in step 1)
And aqueous solution, gelatin and polyvinyl alcohol dispersing agent are added, is dispersed with stirring；Based on the ortho-chlorostyrene and divinylbenzene
Gross mass, the dosage of the saturated aqueous sodium chloride are 100~150wt%, and the dosage of the gelatin is 20~30wt%, are gathered
Vinyl alcohol dispersant dosage is 1~1.5wt%.
In the step 1) of catalyst preparation of the present invention, also need to be added based on ortho-chlorostyrene and divinylbenzene quality
1~3wt% pore-foaming agent paraffin wax and 0.2~0.5wt% initiator benzoyl peroxide.
In the step 1) of catalyst preparation of the present invention, the molar ratio of ortho-chlorostyrene and divinylbenzene be 1:1~
7:1, preferably 3:1~5:1；Gross mass based on the ortho-chlorostyrene and divinylbenzene, the silicon carbide in submicro level
The dosage of whisker is 1~5wt%, and nanoscale tungsten dosage is 0.1~0.5wt%, and the dosage of nanoscale zirconia is 0.1
~1wt%.
In the step 1) of catalyst preparation of the present invention, the reaction temperature of heating stirring is 45~60 DEG C, the reaction time
For 2~6h.
In the step 2) of catalyst preparation of the present invention, after going out pore-foaming agent with petroleum ether extraction at room temperature, obtain straight
Diameter is the resin matrix of 0.4~0.6mm, and gained resin matrix is swollen through excessive dichloroethanes, is then added and is based on resin quality
The concentrated sulfuric acid of 2~5wt% of score is warming up to reflux 1h at 75~80 DEG C；Dichloroethanes is steamed, is added based on resin quality point
The oleum of 0.5~2wt% of number, temperature reaction cool down after resins exchange amount reaches 90~95%, and reaction was completed；With 50
~70 DEG C of distilled water washing resins are filtered dry to washing lotion neutrality；Above-mentioned resin is added to the Lanthanum trichloride hexahydrate of mass fraction 2-8%
In deionized water solution, ion-exchanged is carried out at 45~65 DEG C；It is washed with deionized water to chloride ion after the completion of modification
It disappears；It is put in after being filtered dry in vacuum drying oven in 45~60 DEG C of netted composite enhanced strong acidic ion exchange trees obtained by drying
Rouge.
In the step 3) of catalyst preparation of the present invention, the metal salt solution is that anion is Cl-、Br-Or SO4 2-,
Cation is Li+、Cs+、Rb+、Cu+、Pd2+、Sr2+、Co2+、Ni2+、La3+、Ce3+、Rh3+Or Ru3+Compound aqueous solution in
One or two or more, the mass concentration of the metal salt solution are 2~10wt%；Soaking temperature is 40~60 DEG C, impregnates 3
It is filtered after~6h, solid is washed with distilled water, and obtained metal ion-modified resin is placed in 55~75 DEG C of baking ovens and dries.It is based on
The gross mass of the metal ion-modified netted composite enhanced styryl ion exchange resin, the metal ion contain
Amount is 0.005~0.1wt%, preferably 0.01~0.07wt%, more preferable 0.03~0.05wt%.
In the step 4) of catalyst preparation of the present invention, based on graphite and metal ion-modified netted composite enhanced
The gross mass of strong-acid ion exchange resin, graphite levels are 40~80wt%, and the present invention is prepared in preferably 50~70wt%
The catalyst A；Graphite levels are 5~40wt%, preferably 10~35wt%, and catalyst B of the present invention is prepared.
The beneficial effects of the present invention are:
(1) for the first time by the compound of metal ion-modified netted composite enhanced styryl ion exchange resin and graphite
Catalyst is used to be catalyzed the continuous esterification of acrylic acid and tetrahydrofurfuryl alcohol, and the addition of graphite can be reinforced conducting heat and highly acid is avoided to urge
Side reaction caused by agent reduces product coloration, improves product quality, while avoiding occurring the feelings such as carbon deposit, coking on catalyst
Condition；
(2) ion exchange resin is modified using metal ion, avoids acrylicacidandesters class in ordinary resin
Upper incidental polymerization reaction, hence it is evident that reduce the content of oligomer in product；Introduce submicron order carbon in the catalyst simultaneously
SiClx whisker, nanoscale tungsten and nanoscale zirconia, can effectively improve the mechanical strength of catalyst substrates；Increase duct
Intensity improves catalyst heat-resisting ability；
(3) conventional styrene is replaced in netted composite enhanced styryl ion exchange resin with ortho-chlorostyrene,
Sulfonic loss in catalyst use process is alleviated, thus the service life for improving catalytic efficiency, extending catalyst；
(4) by the way of two sections of esterifications, two reactor can be controlled separately reaction temperature and pressure, and pass through control two
Content of graphite in section reactor used catalyst, can be improved conversion ratio and selectivity, and tetrahydrofurfuryl alcohol conversion ratio may be up to 100%,
Monoesters selectively up to 97%, reduces the generation of side reaction, guarantees product quality.Pass through continuous esterification new process, energy
Enough efficient industrialized productions for realizing TFA.Compared with Batch Process mode, continuous esterification of the invention prepares TFA
Method, mode of operation is simple, high production efficiency, and largely avoids the generation of various side reactions.Place after simultaneously
Reason is simple, is neutralized without a large amount of lye, avoids the generation of a large amount of waste water, and scale continuous production is suitable for, and product is raw
It produces cost to substantially reduce, there is good economic benefit and social benefit.
Detailed description of the invention
Fig. 1 is the main part flow diagram that continuous esterification prepares TFA technique
Specific embodiment
The present invention will be described in detail combined with specific embodiments below.The scope of the present invention is not with specific embodiment
It is limited, but is limited by the scope of the claims.
Analysis instrument:
Shimadzu GC-2010, testing conditions: carrier gas: high pure nitrogen, 6ml/min；Temperature program:, keeping 2~5min by 70 DEG C,
10 DEG C/min of heating rate, keeps 10~15min by 280 DEG C of final temperature；350 DEG C of fid detector temperature；Injector temperature 250~
300℃；Split ratio 2.
ICP: Agilent plasma emission spectrometer 720ICP-OES, testing conditions: power 1.2kw；Plasma gas flow rate:
15L/min；Secondary air amount: 1.5L/min；Atomization gas flow: 0.8L/min；Detection wavelength Li+: 670.783nm, Cu+:
327.395nm、Pd2+: 340.458nm, Co2+: 238.892nm, Ru3+: 267.876nm.
Acrylic acid: 99.99wt%, Wanhua Chemical Group Co., Ltd.；
Tetrahydrofurfuryl alcohol: 99.20wt%, western Gansu Province chemical industry；
Toluene: 99.90wt%, western Gansu Province chemical industry；
P-hydroxyanisole: 99.90wt%, western Gansu Province chemical industry；
Hydroquinone: 99.90wt%, western Gansu Province chemical industry；
Graphite: 0.4~0.6mm of partial size, western Gansu Province chemical industry；
As shown in Figure 1,1 is first segment reactor, 2 be the first condenser, and 3 be the first water segregator, and 4 be second segment reaction
Device, 5 be the second condenser, and 6 be the second water segregator, and 7 be first segment reactor feed pipeline, 8 be first segment reactor solvent and
Water azeotropic mixture is into condenser pipe, and 9 be first segment reactor solvent Returning reactor pipeline, and 10 be first segment reactor reaction water
Mutually extraction pipeline, 11 be the discharging of first segment reactor and second stage reactor feeding pipe, and 12 be second segment reactor solvent and water
Azeotropic mixture is into condenser pipe, and 13 be second segment reactor solvent Returning reactor pipeline, and 14 be second segment reactor reaction water
Mutually extraction pipeline, 15 be crude product discharging pipeline.
After acrylic acid, tetrahydrofurfuryl alcohol, polymerization inhibitor, solvent are uniformly mixed and preheat, is entered by 7 and be equipped with the first of catalyst A
In section reactor 1, acrylic acid and tetrahydrofurfuryl alcohol occur continuous esterification and generate TFA and water under the action of catalyst A, water with
Solvent forms azeotropic mixture and constantly enters condenser 2 by 8, enters 3 after cooling, and after split-phase, solvent returns to first segments reaction by 9
In device 1, water phase is through 10 extraction.
Reaction mass in first segment reactor 1 is directly entered second segment reactor 4 by 11, in the effect of catalyst B
Under continue complete esterification.Water and solvent form azeotropic mixture and constantly enter condenser 5 by 12, enter 6 after cooling, point
Xiang Hou, solvent pass through 13 Returning reactors, and water phase is through 14 extraction.Crude product carries out concentration after collection through 15 extraction, will be molten
Agent and excessive propene acid obtain TFA product, solvent and acrylic acid reuse after steaming.
Embodiment 1
1, saturated aqueous sodium chloride 267g and gelatin are added in the reactor equipped with high speed agitator, thermometer
35g and polyvinyl alcohol dispersing agent 1.8g；2, stirring is opened, after dispersing agent is dispersed in system, weighs the adjacent chlorine of 150g
Styrene and 28g divinylbenzene, based on the silicon carbide in submicro level of ortho-chlorostyrene and divinylbenzene quality 1wt% crystalline substance
Palpus, the nanoscale tungsten of 0.1wt%, the nanoscale zirconia of 1wt%, 1wt% white oil pore-foaming agent and 0.5wt% peroxide
Change benzoyl initiator to be added in reactor, is warming up to 60 DEG C of stirring 2h；3, cold filtration after reaction, with 50 DEG C of hot water wash
It washs, dry；4, with excessive petroleum ether extraction pore-foaming agent, the resin matrix of 0.4~0.6mm of diameter is screened out；5, gained resin bone
Frame is swollen with excessive dichloroethanes；6, it is added after the completion of swelling based on 2% concentrated sulfuric acid of resin quality, is warming up to while stirring
75 DEG C of reflux 1h；7, dichloroethanes is steamed, the oleum based on resin quality 1% is added, resins exchange is worked as in temperature reaction
Amount cools down after reaching 95%, and reaction was completed；8, it is filtered dry with distilled water washing resin to washing lotion neutrality；9, above-mentioned resin is added
In the Lanthanum trichloride hexahydrate deionized water solution of extra mass score 2%, ion-exchanged is carried out at 55 DEG C；10, modified
It is washed after the completion with deionized water to chloride ions disappeared；11, it is put in after being filtered dry in vacuum drying oven and is dried in 45~60 DEG C；12, institute
It obtains resin to be placed in the LiCl aqueous solution that extra mass score is 2%, be filtered after 60 DEG C of immersion 6h, solid is washed with distilled water
3 times, obtained metal ion-modified resin is placed in 60 DEG C of baking ovens and dries, and obtains metal ion-modified netted composite enhanced
Styryl ion exchange resin 1, Li+Content is 0.005wt%.
Foregoing ion exchanger resin 1 is uniformly mixed with same particle size graphite particle, and graphite quality accounts for gross mass 40%, graphite
Quality accounts for gross mass 35%, respectively obtains catalyst A-1 and catalyst B-1.
Embodiment 2
1, saturated aqueous sodium chloride 225g and gelatin are added in the reactor equipped with high speed agitator, thermometer
51g and polyvinyl alcohol dispersing agent 2.6g；2, stirring is opened, after dispersing agent is dispersed in system, weighs 130g neighbour's chlorobenzene
Ethylene and 41g divinylbenzene, the silicon carbide in submicro level whisker based on ortho-chlorostyrene and divinylbenzene quality 3%,
0.5% nanoscale tungsten, 0.5% nanoscale zirconia, 2% white oil pore-foaming agent and 0.2% benzoyl peroxide
Initiator is added in reactor, is warming up to 45 DEG C of stirring 6h；3, cold filtration after reaction, with 70 DEG C of hot water washings, drying；
4, with excessive petroleum ether extraction pore-foaming agent, the resin matrix of 0.4~0.6mm of diameter is screened out；5, gained resin matrix is with excess
Dichloroethanes swelling；6, it is added while stirring after the completion of swelling based on 2% concentrated sulfuric acid of resin quality, is warming up to 80 DEG C of reflux
1h；7, dichloroethanes is steamed, the oleum based on resin quality 2%, temperature reaction, when resins exchange amount reaches are added
Cool down after 91.5%, reaction was completed；8, it is filtered dry with distilled water washing resin to washing lotion neutrality；9, above-mentioned resin is added excessive
In the Lanthanum trichloride hexahydrate deionized water solution of mass fraction 4%, ion-exchanged is carried out at 45 DEG C；10, modified to complete
It is washed afterwards with deionized water to chloride ions disappeared；11, it is put in after being filtered dry in vacuum drying oven and is dried in 45~60 DEG C；12, gained tree
Rouge is placed in the CuCl aqueous solution that extra mass score is 5%, is filtered after 40 DEG C of immersion 3h, and solid is washed with distilled water 3 times,
Obtained metal ion-modified resin is placed in 55 DEG C of baking ovens and dries, and obtains metal ion-modified netted composite enhanced benzene second
Alkenyl ion exchange resin 2, Cu+Content is 0.010wt%.
Foregoing ion exchanger resin 2 is uniformly mixed with same particle size graphite particle, and graphite quality accounts for gross mass 80%, graphite
Quality accounts for gross mass 5%, respectively obtains catalyst A-2 and catalyst B-2.
Embodiment 3
1, saturated aqueous sodium chloride 175g and gelatin are added in the reactor equipped with high speed agitator, thermometer
45g and polyvinyl alcohol dispersing agent 2.2g；2, stirring is opened, after dispersing agent is dispersed in system, weighs 140g neighbour's chlorobenzene
Ethylene and 33g divinylbenzene, the silicon carbide in submicro level whisker based on ortho-chlorostyrene and divinylbenzene quality 5%,
0.2% nanoscale tungsten, 0.1% nanoscale zirconia, 3% white oil pore-foaming agent and 0.3% benzoyl peroxide
Initiator is added in reactor, is warming up to 50 DEG C of stirring 4h；3, cold filtration after reaction, with 60 DEG C of hot water washings, drying；
4, with excessive petroleum ether extraction pore-foaming agent, the resin matrix of 0.4~0.6mm of diameter is screened out；5, gained resin matrix is with excess
Dichloroethanes swelling；6, it is added while stirring after the completion of swelling based on 3% concentrated sulfuric acid of resin quality, is warming up to 78 DEG C of reflux
1h；7, dichloroethanes is steamed, the oleum based on resin quality 1%, temperature reaction, when resins exchange amount reaches are added
Cool down after 93%, reaction was completed；8, it is filtered dry with distilled water washing resin to washing lotion neutrality；9, excessive matter is added in above-mentioned resin
In the Lanthanum trichloride hexahydrate deionized water solution for measuring score 6%, ion-exchanged is carried out at 55 DEG C；10, after the completion of modified
It is washed with deionized water to chloride ions disappeared；11, it is put in after being filtered dry in vacuum drying oven and is dried in 45~60 DEG C；12, gained resin
It is placed in the CoCl that extra mass score is 8%2In aqueous solution, being filtered after 50 DEG C of immersion 5h, solid is washed with distilled water 3 times,
Obtained metal ion-modified resin is placed in 75 DEG C of baking ovens and dries, and obtains metal ion-modified netted composite enhanced benzene second
Alkenyl ion exchange resin 3, Co2+Content is 0.070wt%.
Foregoing ion exchanger resin 3 is uniformly mixed with same particle size graphite particle, and graphite quality accounts for gross mass 50%, graphite
Quality accounts for gross mass 10%, respectively obtains catalyst A-3 and catalyst B-3.
Embodiment 4
1, saturated aqueous sodium chloride 250g and gelatin are added in the reactor equipped with high speed agitator, thermometer
40g and polyvinyl alcohol dispersing agent 2.1g；2, stirring is opened, after dispersing agent is dispersed in system, weighs 138g neighbour's chlorobenzene
Ethylene and 37g divinylbenzene, the silicon carbide in submicro level whisker based on ortho-chlorostyrene and divinylbenzene quality 4%,
0.3% nanoscale tungsten, 0.8% nanoscale zirconia, 1.5% white oil pore-foaming agent and 0.3% benzoyl peroxide first
Acyl initiator is added in reactor, is warming up to 50 DEG C of stirring 5h；3, cold filtration after reaction with 55 DEG C of hot water washings, dries
It is dry；4, with excessive petroleum ether extraction pore-foaming agent, the resin matrix of 0.4~0.6mm of diameter is screened out；5, gained resin matrix is with mistake
Measure dichloroethanes swelling；6, it is added while stirring after the completion of swelling based on 4% concentrated sulfuric acid of resin quality, is warming up to 75 DEG C and returns
Flow 1h；7, dichloroethanes is steamed, the oleum based on resin quality 0.5%, temperature reaction, when resins exchange amount reaches are added
Cool down after to 95%, reaction was completed；8, it is filtered dry with distilled water washing resin to washing lotion neutrality；9, above-mentioned resin is added excessive
In the Lanthanum trichloride hexahydrate deionized water solution of mass fraction 8%, ion-exchanged is carried out at 65 DEG C；10, modified to complete
It is washed afterwards with deionized water to chloride ions disappeared；11, it is put in after being filtered dry in vacuum drying oven and is dried in 45~60 DEG C；12, gained tree
Rouge is placed in the RuCl that extra mass score is 5%3In aqueous solution, filtered after 50 DEG C of immersion 6h, solid is washed with distilled water 3
Time, obtained metal ion-modified resin is placed in 60 DEG C of baking ovens and dries, and obtains metal ion-modified netted composite enhanced
Styryl ion exchange resin 4, Ru3+Content is 0.050wt%.
Foregoing ion exchanger resin 4 is uniformly mixed with same particle size graphite particle, graphite quality account for ion exchange resin with
The 60% of the gross mass of graphite, graphite quality account for gross mass 20%, respectively obtain catalyst A-4 and catalyst B-4.
Embodiment 5
1, saturated aqueous sodium chloride 325g and gelatin are added in the reactor equipped with high speed agitator, thermometer
64g and polyvinyl alcohol dispersing agent 3.4g；2, stirring is opened, after dispersing agent is dispersed in system, weighs 207g neighbour's chlorobenzene
Ethylene and 43g divinylbenzene, the silicon carbide in submicro level whisker based on ortho-chlorostyrene and divinylbenzene quality 3.5%,
0.4% nanoscale tungsten, 0.3% nanoscale zirconia, 2.5% white oil pore-foaming agent and 0.4% benzoyl peroxide first
Acyl initiator is added in reactor, is warming up to 50 DEG C of stirring 5h；3, cold filtration after reaction with 65 DEG C of hot water washings, dries
It is dry；4, with excessive petroleum ether extraction pore-foaming agent, the resin matrix of 0.4~0.6mm of diameter is screened out；5, gained resin matrix is with mistake
Measure dichloroethanes swelling；6, it is added while stirring after the completion of swelling based on 5% concentrated sulfuric acid of resin quality, is warming up to 75 DEG C and returns
Flow 1h；7, dichloroethanes is steamed, the oleum based on resin quality 0.5%, temperature reaction, when resins exchange amount reaches are added
Cool down after to 90%, reaction was completed；8, it is filtered dry with distilled water washing resin to washing lotion neutrality；9, above-mentioned resin is added excessive
In the Lanthanum trichloride hexahydrate deionized water solution of mass fraction 6%, ion-exchanged is carried out at 50 DEG C；10, modified to complete
It is washed afterwards with deionized water to chloride ions disappeared；11, it is put in after being filtered dry in vacuum drying oven and is dried in 45~60 DEG C；12, gained tree
Rouge is placed in the PdCl that extra mass score is 10%2In aqueous solution, filtered after 40 DEG C of immersion 6h, solid is washed with distilled water 3
Time, obtained metal ion-modified resin is placed in 70 DEG C of baking ovens and dries, and obtains metal ion-modified netted composite enhanced
Styryl ion exchange resin 5, Pd2+Content is 0.100wt%.
Foregoing ion exchanger resin 5 is uniformly mixed with same particle size graphite particle, and graphite quality accounts for gross mass 70%, graphite
Quality accounts for gross mass 40%, respectively obtains catalyst A-5 and catalyst B-5.
Embodiment 6
Process flow as shown in Figure 1, with acrylic acid 72g, tetrahydrofurfuryl alcohol 102g prepare reaction raw materials, be added solvent toluene and
Polymerization inhibitor p-hydroxyanisole, the gross mass based on acrylic acid and tetrahydrofurfuryl alcohol, wherein toluene quality accounts for 80%, para hydroxybenzene first
Ether accounts for 0.06%.100g catalyst A-1 is taken to be packed into first segment reactor；80g catalyst B-1 is separately taken to be packed into second segment reaction
Device.By raw material preheating to 85 DEG C, first segment reactor is inputted continuously with the speed of 120g/h, 90 DEG C of first segment temperature of reactor,
Pressure 95KPa.150 DEG C of second segment temperature of reactor, pressure 90KPa.After reaction system is stablized, from pipeline 11 and pipeline 15
Sampling carries out component analysis with gas chromatograph-mass spectrometer.Raw material is after first segment reactor, tetrahydrofurfuryl alcohol conversion ratio 82%, monoesters
Selectivity 98%, after second segment reactor, tetrahydrofurfuryl alcohol conversion ratio 100%, monoesters selectivity 95%.It 15 collects by the road
Crude product with laboratory conventional method carry out concentration, obtain finished product TFA after solvent and excessive propene acid are steamed.Gained
TFA is transparency liquid, purity 96wt%, acid value < 0.3mg KOH/g, 25 DEG C of viscosity 8cps@, coloration (Pt-Co) 50, TFA yield
95% (in terms of tetrahydrofurfuryl alcohol).
Embodiment 7
Process flow is as shown in Figure 1, prepare reaction raw materials, addition solvent hexamethylene with acrylic acid 230g, tetrahydrofurfuryl alcohol 204g
Alkane and hydroquinone of polymerization retarder, the gross mass based on acrylic acid and tetrahydrofurfuryl alcohol, hexamethylene quality account for 20%, and hydroquinone accounts for
0.005%.It takes 100g catalyst A-2 to be packed into first segment reactor, 80g catalyst B-2 is taken to be packed into second segment reactor.It will
Raw material preheating continuously inputs first segment reactor to 85 DEG C, with the speed of 200g/h, and 50 DEG C of first segment temperature of reactor, pressure
85KPa.90 DEG C of second segment temperature of reactor, pressure 60KPa.After reaction system is stablized, sampled from pipeline 11 and pipeline 15,
Component analysis is carried out with gas chromatograph-mass spectrometer.Raw material is after first segment reactor, tetrahydrofurfuryl alcohol conversion ratio 80%, monoesters selectivity
95%, after second segment reactor, tetrahydrofurfuryl alcohol conversion ratio 100%, monoesters selectivity 97%.The 15 thick production collected by the road
Product carry out concentration with laboratory conventional method, obtain finished product TFA after solvent and excessive propene acid are steamed.Gained TFA is
Transparency liquid, purity 96wt%, acid value < 0.5mg KOH/g, 25 DEG C of viscosity 10cps@, coloration (Pt-Co) 35, TFA yield 90%
(in terms of tetrahydrofurfuryl alcohol).
Embodiment 8
Process flow as shown in Figure 1, with acrylic acid 187g, tetrahydrofurfuryl alcohol 204g prepare reaction raw materials, be added solvent benzol and
Polymerization inhibitor p-hydroxyanisole, the gross mass based on acrylic acid and tetrahydrofurfuryl alcohol, benzene quality account for 40%, and p-hydroxyanisole accounts for
0.01%.100g catalyst A-3 is taken to be packed into first segment reactor.Separately 80g catalyst B-3 is taken to be packed into second segment reactor.
By raw material preheating to 80 DEG C, first segment reactor is inputted continuously with the speed of 150g/h, 80 DEG C of first segment temperature of reactor, pressure
90KPa.120 DEG C of second segment temperature of reactor, pressure 50KPa.After reaction system is stablized, taken from pipeline 11 and pipeline 15
Sample carries out component analysis with gas chromatograph-mass spectrometer.Raw material is after first segment reactor, tetrahydrofurfuryl alcohol conversion ratio 87%, monoesters choosing
Selecting property 93%, after second segment reactor, tetrahydrofurfuryl alcohol conversion ratio 100%, monoesters selectivity 94%.15 collections by the road
Crude product carries out concentration with laboratory conventional method, obtains finished product TFA after solvent and excessive propene acid are steamed.Gained
TFA is transparency liquid, purity 97wt%, acid value < 0.4mg KOH/g, 25 DEG C of viscosity 6cps@, coloration (Pt-Co) 30, TFA yield
97% (in terms of tetrahydrofurfuryl alcohol).
Embodiment 9
Process flow is as shown in Figure 1, prepare reaction raw materials, addition solvent toluene with acrylic acid 108g, tetrahydrofurfuryl alcohol 102g
With polymerization inhibitor tert-butyl hydroquinone, the gross mass based on acrylic acid and tetrahydrofurfuryl alcohol, toluene quality accounts for 60%, and tert-butyl is to benzene
Diphenol accounts for 0.01%.100g catalyst A-4 is taken to be packed into first segment reactor.Separately 52g catalyst B-4 is taken to be packed into second segment anti-
Answer device.By raw material preheating to 80 DEG C, first segment reactor, first segment temperature of reactor 70 are inputted continuously with the speed of 180g/h
DEG C, pressure 80KPa.130 DEG C of second segment temperature of reactor, pressure 85KPa.After reaction system is stablized, from pipeline 11 and pipeline
It is sampled at 15, component analysis is carried out with gas chromatograph-mass spectrometer.Raw material is after first segment reactor, tetrahydrofurfuryl alcohol conversion ratio 87%,
Monoesters selectivity 93%, after second segment reactor, tetrahydrofurfuryl alcohol conversion ratio 100%, monoesters selectivity 95%.By the road 15
The crude product of collection carries out concentration with laboratory conventional method, obtains finished product TFA after solvent and excessive propene acid are steamed.
Gained TFA is transparency liquid, purity 96wt%, acid value < 0.4mg KOH/g, 25 DEG C of viscosity 9cps@, coloration (Pt-Co) 45, TFA
Yield 94% (in terms of tetrahydrofurfuryl alcohol).
Embodiment 10
Process flow as shown in Figure 1, with acrylic acid 156g, tetrahydrofurfuryl alcohol 158g prepare reaction raw materials, be added solvent just oneself
Alkane and hydroquinone of polymerization retarder, the gross mass based on acrylic acid and tetrahydrofurfuryl alcohol, n-hexane quality account for 50%, and hydroquinone accounts for
0.02%.100g catalyst A-5 is taken to be packed into first segment reactor.Separately 130g catalyst B-5 is taken to be packed into second segment reactor.
By raw material preheating to 80 DEG C, first segment reactor is inputted continuously with the speed of 130g/h, 100 DEG C of first segment temperature of reactor, is pressed
Power 83KPa.100 DEG C of second segment temperature of reactor, pressure 75KPa.After reaction system is stablized, taken from pipeline 11 and pipeline 15
Sample carries out component analysis with gas chromatograph-mass spectrometer.Raw material is after first segment reactor, tetrahydrofurfuryl alcohol conversion ratio 88%, monoesters choosing
Selecting property 92%, after second segment reactor, tetrahydrofurfuryl alcohol conversion ratio 100%, monoesters selectivity 97%.15 collections by the road
Crude product carries out concentration with laboratory conventional method, obtains finished product TFA after solvent and excessive propene acid are steamed.Gained
TFA is transparency liquid, purity 97wt%, acid value < 0.5mg KOH/g, 25 DEG C of viscosity 7cps@, coloration (Pt-Co) 35, TFA yield
96% (in terms of tetrahydrofurfuryl alcohol).
Reference examples
Reaction raw materials are prepared with acrylic acid 187g, tetrahydrofurfuryl alcohol 204g, toluene, p-hydroxyanisole, are esterified with one-step method
Technique prepares TFA, the gross mass based on acrylic acid and tetrahydrofurfuryl alcohol, and toluene quality accounts for the 40% of gross mass, p-hydroxyanisole
The 0.01% of gross mass is accounted for, using p-methyl benzenesulfonic acid as catalyst, catalyst accounts for the 1% of gross mass.After there-necked flask is added in material
Start to warm up reaction, temperature opens negative pressure equipment, so that system is kept tiny structure, enable the azeotropic mixture of toluene and water to after 100 DEG C
Smoothly steam.Azeotropic mixture condenses after steaming in condenser, into water segregator split-phase, toluene Returning reacting system after split-phase, and water phase
Extraction on demand.Reaction process is detected with gas chromatograph-mass spectrometer, until tetrahydrofurfuryl alcohol fully reacting, monoesters is selectively 92% at this time.
Reaction solution washs removal catalyst with 10% sodium hydroxide solution, then with water washing to neutrality, oil mutually adds 100ppm to hydroxyl
Concentration is carried out with laboratory conventional method after methyl phenyl ethers anisole, finished product TFA is obtained after solvent is steamed, yield 90% is (with tetrahydro
Furfuryl alcohol meter), platinum cobalt color number 60.
Claims (28)
1. a kind of method that continuous esterification prepares tetrahydrofuran acrylate, comprising the following steps:
1) using acrylic acid and tetrahydrofurfuryl alcohol as raw material, under the action of catalyst A, continuous esterification is carried out in first segment reactor
Reaction；
2) it using first segment reactor outlet reaction solution as raw material, under the action of catalyst B, has been carried out in second segment reactor
Full esterification；
The catalyst A and catalyst B be metal ion-modified netted composite enhanced styryl ion exchange resin with
The composite catalyst of graphite.
2. the method according to claim 1, wherein metal ion-modified in the catalyst A and catalyst B
Netted composite enhanced styryl ion exchange resin it is identical, in the catalyst A, content of graphite be catalyst A it is total
40~80wt% of quality；In the catalyst B, content of graphite is 5~40wt% of the gross mass of catalyst B.
3. the method according to claim 1, wherein the metal ion-modified netted composite enhanced benzene second
Metal ion described in alkenyl ion exchange resin is Li+、Cs+、Rb+、Cu+、Pd2+、Sr2+、Co2+、Ni2+、La3+、Ce3+、Rh3 +And Ru3+One or both of or it is a variety of；It is handed over based on the metal ion-modified netted composite enhanced styryl ion
The gross mass of resin is changed, the content of the metal ion is 0.005~0.1wt%.
4. the method according to claim 1, wherein the netted composite enhanced styryl amberlite
Rouge is made by ortho-chlorostyrene and divinylbenzene, and wherein the molar ratio of ortho-chlorostyrene and divinylbenzene is 1:1~7:1；
Also containing 1~5wt%'s in gross mass based on the ortho-chlorostyrene and divinylbenzene, the catalyst A and catalyst B
Monomer silicon carbide in submicro level whisker, the nanoscale tungsten of 0.1~0.5wt% and the nanoscale zirconia of 0.1~1wt%.
5. according to the method described in claim 1, the conversion ratio of tetrahydrofurfuryl alcohol is 75~85% after first segment reactor.
6. the method according to claim 1, wherein first segment reactor mass space velocity is 1h-1~2.5h-1, instead
Answering temperature is 50~100 DEG C, and absolute pressure is 70~103KPa；Second segment reactor mass space velocity is 1h-1~3.5h-1, reaction
Temperature is 90~150 DEG C, and reaction absolute pressure is 50~90KPa.
7. according to the method described in claim 6, it is characterized in that, first segment reactor mass space velocity is 1.2h-1~2h-1。
8. according to the method described in claim 6, it is characterized in that, first segment reactor reaction temperature is 70~90 DEG C.
9. according to the method described in claim 6, it is characterized in that, first segment reactor absolute pressure is 80~95KPa.
10. according to the method described in claim 6, it is characterized in that, second segment reactor mass space velocity is 1.5h-1~2.5h-1。
11. according to the method described in claim 6, it is characterized in that, second segment reactor reaction temperature is 100~130 DEG C.
12. according to the method described in claim 6, it is characterized in that, second segment reactor reaction absolute pressure be 60~
85KPa。
13. the method according to claim 1, wherein adding respectively in first segment reactor and second segment reactor
Enter polymerization inhibitor, the polymerization inhibitor being added in first segment reactor and second segment reactor is identical or different；The polymerization inhibitor is to benzene
One or both of diphenol, p-hydroxyanisole and tert-butyl hydroquinone or three kinds；First segment reactor and second segment are anti-
Answer polymerization inhibitor dosage in device identical, the dosage of the polymerization inhibitor be based on acrylic acid and tetrahydrofurfuryl alcohol gross mass 0.005~
0.06wt%.
14. according to the method for claim 13, which is characterized in that be added in first segment reactor and second segment reactor
Polymerization inhibitor is identical.
15. according to the method for claim 13, which is characterized in that the dosage of the polymerization inhibitor is based on acrylic acid and tetrahydro
0.01~0.04wt% of furfuryl alcohol gross mass.
16. the method according to claim 1, wherein adding respectively in first segment reactor and second segment reactor
Enter atent solvent, first segment reactor and atent solvent described in second segment reactor are identical or different；The atent solvent is
One or both of benzene, toluene, n-hexane, normal heptane, normal octane and hexamethylene are a variety of；First segment reactor and second segment
The solvent usage of reactor is identical, the dosage of the atent solvent be based on acrylic acid and tetrahydrofurfuryl alcohol gross mass 20~
80wt%.
17. according to the method for claim 16, which is characterized in that first segment reactor with it is lazy described in second segment reactor
Property solvent is identical.
18. according to the method for claim 16, which is characterized in that the atent solvent is benzene, toluene, n-hexane and hexamethylene
One or both of alkane is a variety of.
19. according to the method for claim 18, which is characterized in that the atent solvent is toluene and/or hexamethylene.
20. according to the method for claim 16, which is characterized in that the dosage of the atent solvent is based on acrylic acid and four
40~60wt% of hydrogen furfuryl alcohol gross mass.
21. the method according to claim 1, wherein the molar ratio of acrylic acid and tetrahydrofurfuryl alcohol is 1:1~1.6:
1。
22. the preparation method of catalyst A and catalyst B used in a kind of described in any item methods of claim 1-21,
Characterized by comprising the following steps:
1), ortho-chlorostyrene and divinylbenzene, silicon carbide in submicro level whisker, nanoscale tungsten and nanoscale zirconia are mixed
It closes, heating stirring reaction；
2), the reaction solution that step 1 obtains through cooling, be filtered, washed, dry and extract after obtain netted composite enhanced styrene
Group ion exchange resin；
3) it, takes step 2 gained ion exchange resin to be placed in metal salt solution, is filtered, washed, dries after sufficiently impregnating, obtain
Metal ion-modified netted composite enhanced styryl ion exchange resin；
4), the metal ion-modified netted composite enhanced styryl ion exchange resin of gained in step 3 and graphite are passed through
Mechanical mixture is uniform, respectively obtains catalyst A and catalyst B.
23. preparation method according to claim 22, which is characterized in that metal salt solution described in step 3) is anion
For Cl-、Br-Or SO4 2-, cation is Li+、Cs+、Rb+、Cu2+、Pd2+、Sr2+、Co2+、Ni2+、La3+、Ce3+、Rh3+Or Ru3+'s
One or both of aqueous solution of compound is a variety of, and the mass concentration of the metal salt solution is 2-10wt%, impregnates temperature
Degree is 40-60 DEG C, and soaking time is 3~6h.
24. preparation method according to claim 22, which is characterized in that ortho-chlorostyrene and divinylbenzene in step 1)
Molar ratio be 1:1~7:1；Silicon carbide in submicro level described in gross mass based on the ortho-chlorostyrene and divinylbenzene is brilliant
Must dosage be 1~5wt%, nanoscale tungsten dosage is 0.1~0.5wt%, the dosage of nanoscale zirconia is 0.1~
1wt%.
25. preparation method according to claim 24, which is characterized in that ortho-chlorostyrene and divinylbenzene in step 1)
Molar ratio be 3:1~5:1.
26. preparation method according to claim 22, which is characterized in that based on graphite and metal ion-modified netted multiple
The gross mass of enhanced strong-acid ion exchange resin is closed, graphite levels are 40~80wt%, and the catalyst A is prepared；
Graphite levels are 5~40wt%, and the catalyst B is prepared.
27. preparation method according to claim 26, which is characterized in that based on graphite and metal ion-modified netted multiple
The gross mass of enhanced strong-acid ion exchange resin is closed, graphite levels are 50~70wt%, and the catalyst A is prepared.
28. preparation method according to claim 26, which is characterized in that based on graphite and metal ion-modified netted multiple
The gross mass of enhanced strong-acid ion exchange resin is closed, graphite levels are 10~35wt%, and the catalyst B is prepared.
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| US2229997A (en) * | 1940-05-07 | 1941-01-28 | Houston V Claborn | Process for the manufacture of tetrahydrofurfuryl acrylate and its polymers |
| US5510514A (en) * | 1993-01-27 | 1996-04-23 | Elf Atochem S.A. | Process for the production of alkyl (meth)acrylates by direct esterification |
| CN1326431A (en) * | 1998-11-11 | 2001-12-12 | 巴斯福股份公司 | Method for continuous production of (METH) acrylic acid alkyl esters |
| CN101723830A (en) * | 2009-12-04 | 2010-06-09 | 广东工业大学 | Method for synthesizing (methyl) acrylate |
| WO2014208686A1 (en) * | 2013-06-27 | 2014-12-31 | 大阪有機化学工業株式会社 | (meth)acrylate production system |
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| US5510514A (en) * | 1993-01-27 | 1996-04-23 | Elf Atochem S.A. | Process for the production of alkyl (meth)acrylates by direct esterification |
| CN1326431A (en) * | 1998-11-11 | 2001-12-12 | 巴斯福股份公司 | Method for continuous production of (METH) acrylic acid alkyl esters |
| CN101723830A (en) * | 2009-12-04 | 2010-06-09 | 广东工业大学 | Method for synthesizing (methyl) acrylate |
| WO2014208686A1 (en) * | 2013-06-27 | 2014-12-31 | 大阪有機化学工業株式会社 | (meth)acrylate production system |
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