CN108863780A - A kind of solid-carrying heteropolyacid catalyst is in the application for preparing fluorenyl acrylate - Google Patents
A kind of solid-carrying heteropolyacid catalyst is in the application for preparing fluorenyl acrylate Download PDFInfo
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- CN108863780A CN108863780A CN201711323462.7A CN201711323462A CN108863780A CN 108863780 A CN108863780 A CN 108863780A CN 201711323462 A CN201711323462 A CN 201711323462A CN 108863780 A CN108863780 A CN 108863780A
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C67/00—Preparation of carboxylic acid esters
- C07C67/08—Preparation of carboxylic acid esters by reacting carboxylic acids or symmetrical anhydrides with the hydroxy or O-metal group of organic compounds
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J27/00—Catalysts comprising the elements or compounds of halogens, sulfur, selenium, tellurium, phosphorus or nitrogen; Catalysts comprising carbon compounds
- B01J27/14—Phosphorus; Compounds thereof
- B01J27/186—Phosphorus; Compounds thereof with arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
- B01J27/188—Phosphorus; Compounds thereof with arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium with chromium, molybdenum, tungsten or polonium
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C67/00—Preparation of carboxylic acid esters
- C07C67/24—Preparation of carboxylic acid esters by reacting carboxylic acids or derivatives thereof with a carbon-to-oxygen ether bond, e.g. acetal, tetrahydrofuran
- C07C67/26—Preparation of carboxylic acid esters by reacting carboxylic acids or derivatives thereof with a carbon-to-oxygen ether bond, e.g. acetal, tetrahydrofuran with an oxirane ring
Abstract
The present invention provides a kind of solid-carrying heteropolyacid catalyst in the application for preparing fluorenyl acrylate, the difference is that, the solid-carrying heteropolyacid catalyst includes solid heteropoly acid and load, and the solid heteropoly acid is one or both of heteropoly acids such as phosphotungstic acid, phosphomolybdic acid, silico-tungstic acid, silicomolybdic acid, germanotungstic acid or germanium molybdic acid；One or both of carriers such as the loaded article carclazyte, bentonite, diatomite, natural clay, silica, titanium dioxide, aluminium oxide, molecular sieve, kaolin or active carbon.Present invention uses solid-carrying heteropolyacid catalysts, instead of p-methyl benzenesulfonic acid used in original technique, it the advantage is that catalyst may be reused repeatedly, operation is easy, temperature-controllable is strong, yield is up to 90% or more, reduce production cost, production efficiency is improved, the pollution to environment is reduced, is suitable for green chemical industry production requirement.
Description
Technical field
The present invention relates to chemical fields, and in particular to a kind of solid-carrying heteropolyacid catalyst is preparing fluorenyl acrylic acid
The application of ester.
Background technique
It is poly- by optical resins such as the polyacrylic resin of skeleton, epoxy acrylic resins of fluorenes (Fluorene) architecture
Object material is closed, because (glass transition temperature reaches with superpower toughness and excellent insulating properties, chemical resistance, abrasion resistance, heat resistance for it
To 350 DEG C), high optical anisotropy and good shock resistance, splendid transparency and mouldability, service life
The advantages that long, light weight and simple production, it has also become a kind of new high-performance optical film functional material is widely used to
Including laser system, contemporary optics and the photoelectron technology such as high-performance optical communicates, light is shown, optical storage, photoswitch, optical waveguide
Field, for manufacturing various high-grade optical mirror slips, optical lens and lens, precision optical instrument, sophisticated electronic device, automobile
With necks such as engineering plastics and paint, top-grade furniture, film article etc.；Especially last decade photoelectron, optical instrument,
Various reflectance coatings, antireflective coating, polarizing coating, interference filter membrane material in liquid crystal display and organic light emitting display with
And the fields such as other non-linear optical film materials are rapidly developed, and 21st century high performance structures optical material is become,
Quickly, related new material, new product emerge one after another for technical research and industry development.As China's optical device, hand are mechanical, electrical
Depending on the increase in demand in, markets such as computer, glasses, fluorenyl acrylic resin monomer and its high refractive index acrylic resin product
Market application prospect is considerable.
New material such a for acrylate containing fluorene skeleton, with mixing acrylate product synthetic technology
Research and development also belong to a new issue at home, currently, the method for production fluorene skeleton acrylate is to use raw material both at home and abroad
With acrylic acid Catalyzed by p-Toluenesulfonic Acid effect under react (KR20150144103A, CN103864586A,
US2008043176A1, JP2012082387A).The catalyst that this method uses is p-methyl benzenesulfonic acid, p-methyl benzenesulfonic acid one
Kind organic acid soluble easily in water, can not recycle and reuse, reaction yield only has 75%~85% or so, and production cost is inclined
Height not only increases the solid waste amount and the useless amount of liquid of reaction, results in waste of resources, cause pollution to environment, do not meet sustainable
The requirement of environmentally protective development of chemical industry.
Heteropoly acid is by hetero atom (such as P, Si, Fe, Co) and polyatom (such as Mo, W, V, Nb, Ta) by certain knot
The oxygen-containing polyacid of one kind that structure is made up of oxygen atom ligand bridging.As a kind of novel catalysis material, heteropoly acid and its esters
Compound is with its unique acidity, " quasi- liquid phase " behavior, multi-functional (acid, oxidation, photoelectrocatalysis) etc. a little in catalytic field
In receive the extensive attention of researchers, have very big application prospect especially as homogeneous catalyst, and solid-carrying heteropolyacid is urged
It is strong to change performance, is easily recycled use, many reports existing for the application of solid acid catalysts；Such as：Zhang Jingchang, Cao
Tie up good, Lv Qing etc. report " acroleic acid esterification reaction in solid acid catalyst application " (Beijing University of Chemical Technology's journal, 1999,
26(1)：5-8), Meng Zhaoren report " esterification solid heteropoly acid (salt) Research advance in catalysts for production " (Xinjiang University's journal,
Vol.21, No.2：161-164)；Gu Tingting etc. reports " application of heteropoly acid (salt) catalyst in the esterification reaction " (Liaocheng
University's master thesis), but not yet see synthesis of the solid-carrying heteropolyacid as catalyst preparation acrylate containing fluorene skeleton
Method report.
Summary of the invention
The present invention has pollution for Catalyzed by p-Toluenesulfonic Acid agent environment in the prior art, and catalytic efficiency is relatively low, cannot repeat
It utilizes, the technological deficiencies such as result in waste of resources, and provides a kind of application of solid-carrying heteropolyacid catalyst.
A kind of solid-carrying heteropolyacid catalyst is preparing fluorenyl acrylate application, the difference is that, it is described immobilized miscellaneous
Polyacid catalyst includes solid heteropoly acid and load；
The solid heteropoly acid is in the heteropoly acids such as phosphotungstic acid, phosphomolybdic acid, silico-tungstic acid, silicomolybdic acid, germanotungstic acid or germanium molybdic acid
One or two；
The loaded article carclazyte, bentonite, diatomite, natural clay, silica, titanium dioxide, aluminium oxide, molecule
One or both of carriers such as sieve, kaolin or active carbon；
Shown in the structure of the acrylate containing fluorene skeleton such as formula (1)：
In formula (1), n1The integer of=0-10；R1=-H ,-R or-Ar；- R indicates alkyl or alkoxy；X=-H ,-F ,-
Cl、-Br、-NO2Or CN；A and B indicates substituted-phenyl, substituted biphenyl base or substituted naphthyl.
In above-mentioned technical proposal, mass percent of the solid heteropoly acid in the solid-carrying heteropolyacid catalyst is
15%~45%.
In above-mentioned technical proposal, the preparation that the solid-carrying heteropolyacid catalyst is applied to the acrylate containing fluorene skeleton includes
Following steps：
Reaction dissolvent, reaction main ingredient, solid-carrying heteropolyacid catalyst and polymerization inhibitor are added separately to reactor by step (1)
In, unlatching is uniformly mixed, heat up, flow back, dissolve after cool down, obtain the first liquid, wherein reaction main ingredient structure such as formula
(2) shown in：
In formula (2), n1The integer of=0-10, R1=-H ,-R or-Ar ,-R indicate alkyl or alkoxy, X=-H ,-Cl ,-
NO2Or CN, A and B indicate substituted-phenyl, substituted biphenyl base or substituted naphthyl；
Acrylic acid is added in step (1) described first liquid step (2), and back flow reaction carries out a point water during reaction
Processing, cools down after completion of the reaction, obtains second liquid.
In above-mentioned technical proposal, the solid heteropoly acid is applied to the preparation step (1) of the acrylate containing fluorene skeleton extremely
(2) in, the reaction dissolvent is one of toluene, hexahydrotoluene.
In above-mentioned technical proposal, the preparation that the solid-carrying heteropolyacid catalyst is applied to the acrylate containing fluorene skeleton is also wrapped
Include following steps：
Step (3) is filtered step (2) described second liquid to obtain third liquid, filters out solid-carrying heteropolyacid and urge
It is reused in the step of agent recycling, recycling can put into next secondary response after activating (1)；
Step (3) the third liquid is washed with deionized to neutrality, obtains the 4th liquid by step (4)；
Step (5) will be added after step (4) described 4th liquid is dried, filtering and solvent distillation after desiccant,
Obtain product；And it is reused step (1) is added as reaction dissolvent after solvent recovery.
In above-mentioned technical proposal, the mass ratio of the solid-carrying heteropolyacid catalyst and reaction solution is (0.01~0.05):
1；
In above-mentioned technical proposal, the solid-carrying heteropolyacid catalyst is applied to the preparation step of the acrylate containing fluorene skeleton
(3) in, the number of the solid-carrying heteropolyacid catalyst recycling is 1~10 time.
In above-mentioned technical proposal, the solid-carrying heteropolyacid catalyst is applied to the preparation step of the acrylate containing fluorene skeleton
(1) in, the mass ratio (2.0~6.0) of the reaction dissolvent and reaction main ingredient： 1.
In above-mentioned technical proposal, the solid-carrying heteropolyacid catalyst is applied to the preparation step of the acrylate containing fluorene skeleton
(2) in, the molar ratio of the acrylic acid and reaction main ingredient is (2.1~3.5)： 1.
Compared with prior art, present invention uses solid-carrying heteropolyacid catalysts, instead of right used in original technique
Toluenesulfonic acid the advantage is that catalyst may be reused repeatedly, and operation is easy, temperature-controllable is strong, yield is up to
90% or more, production cost is reduced, production efficiency is improved, reduces the pollution to environment, is suitable for green chemical industry and produces
It is required that.
Specific embodiment
In order to make the objectives, technical solutions, and advantages of the present invention clearer, combined with specific embodiments below to this
Invention is described in further detail.It should be appreciated that the specific embodiments described herein are merely illustrative of the present invention, not
For limiting the present invention.
Embodiment 1：
The preparation of Catalyzed By Immobilized Phosphotungstic agent：Using diatomite as carrier, phosphotungstic acid is loaded, matter shared by phosphotungstic acid
Measuring percentage is 20%；
By 100.0 grams of bis ether fluorenes, 25.0 grams of Catalyzed By Immobilized Phosphotungstic agent, 0.15 gram of p-hydroxyanisole and 0.15 gram time
Sodium phosphate is added to in churned mechanically 500 milliliters of four round flask, adds 300 milliliters of toluene solvants, unlatching is stirred
It mixes, heat and dissolves, after slowly dripping 41.0 grams of acrylic acid, be warming up to 110 DEG C of water that flow back and divide, react 4 hours.Cooling
It is filtered to 55 DEG C, collection immobilized phosphotungstic acid gives over to be used next time again.60 ml deionized waters are added and wash 5 times to neutrality.It is added
10 grams of anhydrous sodium sulfates, dry 2 hours caudacorias of stirring are filtered, are depressurized after adding 0.02 gram of p-hydroxyanisole in filtrate
Distillation, can be obtained 117.7 grams of colorless and transparent colloidal liquid products, APHA color 50Hazen or so, yield after steaming net toluene
It is 92.7%, solvent recovery is being used for next secondary response.
Embodiment 2：
The preparation of immobilized silicotungstic acid catalyst：Using carclazyte as carrier, silico-tungstic acid is loaded, quality shared by silico-tungstic acid
Percentage is 25%；
By 400 grams of bis ether fluorenes, 90 grams of immobilized silicotungstic acid catalysts, 0.5 gram of p-hydroxyanisole and 0.5 gram of sodium hypophosphite
It is added to in churned mechanically 2000 milliliters of three neck round bottom flask, adds 1100 milliliters of methyl cyclohexane alkane solvents, open
Agitating and heating is warming up to 80 DEG C and stirs 20 minutes, after 160 grams of acrylic acid have been slowly added dropwise, is brought rapidly up to flowing back and divide water,
Reaction 4.5 hours.60 DEG C or so are cooled to, is filtered, collects immobilized silico-tungstic acid so that next time is used again.It is added 500 milliliters
Deionized water wash 7 times to neutrality.25 grams of anhydrous sodium sulfates are added, stir 15 minutes, stand 5 hours, film filtering will
Filtered reaction solution is added 0.1 gram of p-hydroxyanisole and carries out vacuum rotary steam, and hexahydrotoluene distillation can completely be obtained
To 471.7 grams of colorless and transparent colloidal liquid products, yield 94.6%, 40 Hazen of APHA color or so recycles methyl cyclohexane
Alkane is being used for next secondary response.
Embodiment 3：
The preparation of solid silicomolybdic acid catalyst：Using carclazyte as carrier, silicomolybdic acid is loaded, quality shared by silicomolybdic acid
Percentage is 30%；
By 150 kilograms of bis ether fluorenes, 6 kilograms of immobilized silicomolybdic acid catalyst, 100 grams of p-hydroxyanisole and 150 grams of hypophosphorous acid
Sodium is added to in the 1000 liters of enamel stills stirred, adds 450 kilograms of toluene solvants, is opened stirring and heating, is slowly added
Enter 24.2 kilograms of acrylic acid, be brought rapidly up after adding to 110 DEG C and flowed back, divide water, reacts 6 hours.55 DEG C or so are cooled to,
It is filtered, collects immobilized silicomolybdic acid so that next time is used again.60 kilograms of deionized waters are added, stir 5 minutes, stand 25 minutes
After divide water, water washing operations 6 times are to neutral.15 kilograms of anhydrous sodium sulfates are added, stirs caudacoria filtering in 3 hours, is added in filtrate
40 grams of p-hydroxyanisole are evaporated under reduced pressure, and net toluene is steamed, and obtain 180.3 kilograms of colorless and transparent colloidal liquid products,
APHA color 50Hazen or so；Yield is 96.1%；It recycles toluene and is being used for next secondary response.
Embodiment 4：
Solid equipped with 100 grams of bis ether fluorenes, 35 grams of recycling carclazytes in churned mechanically 500 milliliters of four round flask, are added
The silicomolybdic acid catalyst of load (after recycling the 3rd time that embodiment 3 is reacted, reuses, silicomolybdic acid for 2 hours by 120 DEG C of activation
30%) accounting for mass ratio is.0.10 gram of p-hydroxyanisole and 0.15 gram of sodium hypophosphite, it is molten to add 350 milliliters of hexahydrotoluenes
Stirring and heating are opened in agent, after 41.0 grams of acrylic acid slowly are added dropwise, are brought rapidly up to 100 DEG C and are flowed back, react 6 hours.Cooling
To after 55 DEG C or so, filtering collects immobilized silicomolybdic acid catalyst so that next time is used again.60 ml deionized waters are added to wash 6 times
To neutrality.Suitable desiccant anhydrous sodium sulfate is added, stands 5 hours, filters, 0.02 gram of para hydroxybenzene first is added in filtrate
Vacuum rotary steam is carried out after ether, steams net toluene, obtains 120.0 grams of yellowish clear gum liquid products, APHA color 40Hazen
Left and right, yield 96.3%, recycling toluene are being used for next secondary response.
Embodiment 5：
Equipped in churned mechanically 2000 milliliters of three neck round bottom flask, 400 grams of bis ether fluorenes, 100 grams of recycling carclazytes are added
Immobilized silicomolybdic acid catalyst (recycling the 5th, mass ratio shared by silicomolybdic acid be 30%), 0.5 gram of p-hydroxyanisole and 0.5 gram
Sodium hypophosphite adds 1000 milliliters of toluene, opens stirring and heating, after slowly dripping 170.9 grams of acrylic acid, rises rapidly
Temperature is reacted 5 hours to 110 DEG C of water that flow back and divide.60 DEG C or so are cooled to, filtering collects immobilized silicomolybdic acid catalyst so as under
It is secondary to use again.200 grams of deionized waters are added and wash 6 times to neutrality.Suitable anhydrous sodium sulfate is added dry 6 hours overnight, film mistake
It filters, after 0.05 gram of p-hydroxyanisole is added in filtrate, vacuum rotary steam steams net toluene, obtains 470.2 grams of colorless and transparent glues
Liquid product, yield 94.3%；APHA color 50Hazen or so；Solvent recovery is used again.
Embodiment 6：
The preparation of Catalyzed By Immobilized Phosphotungstic agent：Using carclazyte as carrier, phosphotungstic acid is loaded, quality shared by phosphotungstic acid
Percentage is 35%.
100 grams of bis ether fluorenes, 26 grams of solid phosphotungstic acids, 0.1 gram of p-hydroxyanisole and 0.15 gram of sodium hypophosphite are added to
With 300 milliliters of toluene in churned mechanically 500 milliliters of four round flask, are added, stirring and heating are opened, is slowly dripped
It after adding 41.0 grams of acrylic acid, is brought rapidly up to 110 DEG C and flows back, react 3 hours.55 DEG C are cooled to, immobilized phosphorus is collected in filtering
Tungstic acid catalyst is to reuse.60 ml deionized waters are added and wash 6 times to neutrality；It is dry that appropriate anhydrous sodium sulfate is added
Dry 5 hours, net toluene was steamed in decompression after filtering, obtained 118.4 grams of colorless and transparent colloidal liquid products, yield 95.0%；APHA
Coloration 60Hazen or so；Solvent recovery is used again.
Embodiment 7：
Equipped in churned mechanically 500 milliliters of four round flask, it is added 100 grams of bis ether fluorenes, 24 grams of recycling carclazytes
Catalyzed By Immobilized Phosphotungstic agent (recycling the 12nd time, phosphotungstic acid account for mass ratio be 25%), 0.1 gram of p-hydroxyanisole, 0.2 gram time
Sodium phosphate, 300 milliliters of toluene open stirring and heating, after slowly dripping 41.0 grams of acrylic acid, are brought rapidly up to 110 DEG C and return
Stream reacts 4 hours；55 DEG C of filterings are cooled to, collect Catalyzed By Immobilized Phosphotungstic agent so that next time is used again.Be added 60 milliliters go from
Sub- water washes 6 times to neutrality.Suitable anhydrous sodium sulfate is added to be dried overnight, filters, 0.02 gram of para hydroxybenzene first is added in filtrate
After ether, vacuum rotary steam steams net toluene, obtains 117.5 grams of colorless and transparent colloidal liquid products, yield 95.4%；APHA color
50Hazen or so is spent, solvent recovery is used again.
Embodiment 8：
The preparation of immobilized phosphomolybdic acid catalyst：Using carclazyte as carrier, phosphomolybdic acid is loaded, quality shared by phosphomolybdic acid
Percentage is 30%；
By 100 grams of bisphenol fluorenes, 25 grams of immobilized phosphomolybdic acid catalyst, 0.75 gram of p-hydroxyanisole and 0.5 gram of sodium hypophosphite
It is added to in churned mechanically 500 milliliters of four round flask, adds 300 grams of toluene solvants, open stirring and add
Heat after 49.4 grams of acrylic acid have been slowly added dropwise, opens stirring, is brought rapidly up to 110 DEG C and flows back, reacts 3 hours, be cooled to 55
DEG C, it is filtered, collects immobilized phosphomolybdic acid catalyst to repeat to use again.60 ml deionized waters are added and wash 6 times into
Property.It is 5 hours dry that appropriate anhydrous sodium sulfate is added, net toluene is steamed in decompression after filtering, primary with ethyl alcohol and re-crystallizing in ethyl acetate
120.1 grams of white solid products can be obtained, yield 91.8%, solvent recovery is used again.
Embodiment 9：
The preparation of Catalyzed By Immobilized Phosphotungstic agent：Using silica as carrier, phosphotungstic acid is loaded, shared by phosphotungstic acid
Mass percent is 25%；
By 100 grams of epoxy bisphenol fluorenes, 25 grams of Catalyzed By Immobilized Phosphotungstic agent, 0.75 gram of p-hydroxyanisole and 0.5 gram phosphorus
Sour sodium is added to 300 grams of toluene solvants in churned mechanically 500 milliliters of four round flask, are added, open stirring and
Heating after 38.8 grams of acrylic acid are slowly added dropwise, opens stirring, is brought rapidly up to 110 DEG C and flows back, reacts 3 hours, liquid chromatogram
Without epoxy bisphenol fluorene, unilateral product assay can stop reacting less than 1% for analysis.55 DEG C are cooled to, is filtered, is collected solid
Phosphotungstic acid catalyst is carried to repeat to use again.60 ml deionized waters are added and wash 6 times to neutrality.Appropriate anhydrous slufuric acid is added
Sodium is 5 hours dry, and net toluene is steamed in decompression after filtering, and 112.7 grams of white gummy solid products, fusing point 43 DEG C~46 can be obtained
℃；Yield is 91.4%, and solvent recovery is used again.
Embodiment 10：
The preparation of immobilized phosphomolybdic acid catalyst：Using diatomite as carrier, phosphomolybdic acid is loaded, matter shared by phosphotungstic acid
Measuring percentage is 30%.
By 100 grams of adjacent methyl bisphenol fluorenes, 25 grams of immobilized phosphomolybdic acid catalyst, 0.75 gram of p-hydroxyanisole and 0.5 gram time
Sodium phosphate is added to 400 grams of toluene solvants in churned mechanically 500 milliliters of four round flask, are added, and opens stirring
And heating, after 47.4 grams of acrylic acid are slowly added dropwise, stirring is opened, is brought rapidly up to 110 DEG C and flows back, is reacted 3 hours, liquid phase color
Without adjacent methyl bisphenol fluorenes, unilateral product assay can stop reacting less than 1% spectrum analysis.55 DEG C are cooled to, is filtered, is received
Collect solid heteropoly acid phosphotungstic acid to reuse.60 ml deionized waters are added and wash 6 times to neutrality.It is added appropriate anhydrous
Sodium sulphate is 5 hours dry, and net toluene is steamed in decompression after filtering, once can be obtained 117.1 with ethyl alcohol and re-crystallizing in ethyl acetate
Gram white solid product product, yield 91.2%；Solvent recovery is used again.
Embodiment 11：
The preparation of immobilized phosphomolybdic acid catalyst：Using carclazyte as carrier, phosphomolybdic acid is loaded, quality shared by phosphotungstic acid
Percentage is 30%.
By 100 grams of phenyl bis ether fluorenes, 30 grams of immobilized phosphomolybdic acid catalyst, 0.70 gram of p-hydroxyanisole and 0.5 gram phosphorus
Sour sodium is added to 300 grams of toluene solvants in churned mechanically 500 milliliters of four round flask, are added, open stirring and
Heating after 30.5 grams of acrylic acid are slowly added dropwise, opens stirring, is brought rapidly up to 110 DEG C and flows back, reacts 4 hours, liquid chromatogram
Detection can stop reacting without phenyl bis ether fluorenes.55 DEG C are cooled to, is filtered, collects solid heteropoly acid phosphotungstic acid so as to weight
It is multiple to use.60 ml deionized waters are added and wash 6 times to neutrality.It is 5 hours dry that appropriate anhydrous sodium sulfate is added, subtracts after filtering
Pressure steams net toluene, can be obtained 109.4 grams of white solid products twice with ethyl alcohol and re-crystallizing in ethyl acetate, and fusing point 122~
124℃；Yield is 92.5%；Solvent recovery is used again.
Embodiment 12 (comparative example)：
100 grams of bis ether fluorenes, 5 grams of p-methyl benzenesulfonic acid, 0.1 gram of p-hydroxyanisole and 0.2 gram of sodium hypophosphite (are helped into polymerization inhibitor
Agent) it is added to 300 milliliters of toluene in churned mechanically 500 milliliters of four round flask, are added, it opens stirring and adds
Heat after 41.0 grams of acrylic acid have been slowly added dropwise, are brought rapidly up to 110 DEG C of water that flow back and divide, react 5 hours.80 DEG C are cooled to,
50 ml deionized waters are added and wash 6 times to neutrality.Appropriate anhydrous sodium sulfate is added to be dried overnight, after filtering, filtrate decompression is steamed
Toluene to the greatest extent, obtains 105.9 grams of yellowish clear gum liquid products, and yield is that 85.0% (p-methyl benzenesulfonic acid is washed with water, no
Conducive to environmental protection).
Embodiment 13 (comparative example)
By 100 grams of adjacent methyl bisphenol fluorenes, 5 grams to benzene methanesulfonic acid, 0.75 gram of p-hydroxyanisole and 0.5 gram of sodium hypophosphite
It is added to in churned mechanically 500 milliliters of four round flask, adds 300 grams of toluene solvants, open stirring and add
Heat after 47.4 grams of acrylic acid are slowly added dropwise, opens stirring, is brought rapidly up to 110 DEG C and flows back, reacts 5 hours, liquid chromatogram is anti-
It can should stop reacting completely.80 DEG C are cooled to, is filtered, collects solid heteropoly acid phosphotungstic acid to reuse.Add
Enter 60 ml deionized waters and washes 6 times to neutrality.It is 5 hours dry that appropriate anhydrous sodium sulfate is added, net first is steamed in decompression after filtering
115.5 grams of white solid product products once can be obtained with ethyl alcohol and re-crystallizing in ethyl acetate in benzene, and yield is 88.0% (to first
Benzene sulfonic acid can not be recycled and be reused, and be washed with water, and environmental protection is unfavorable for).
The foregoing is merely illustrative of the preferred embodiments of the present invention, is not intended to limit the invention, all in essence of the invention
Made any modifications, equivalent replacements, and improvements etc., should all be included in the protection scope of the present invention within mind and principle.
Claims (8)
1. a kind of solid-carrying heteropolyacid catalyst is in the application for preparing fluorenyl acrylate, which is characterized in that the solid-carrying heteropolyacid
Catalyst includes solid heteropoly acid and load；
The solid heteropoly acid is one in the heteropoly acids such as phosphotungstic acid, phosphomolybdic acid, silico-tungstic acid, silicomolybdic acid, germanotungstic acid or germanium molybdic acid
Kind or two kinds；
The loaded article carclazyte, bentonite, diatomite, natural clay, silica, titanium dioxide, aluminium oxide, molecular sieve, height
One or both of carriers such as ridge soil or active carbon；
Shown in the structure of the acrylate containing fluorene skeleton such as formula (1)：
In formula (1), n1The integer of=0-10；R1=-H ,-R or-Ar；- R indicates alkyl or alkoxy；X=-H ,-F ,-Cl ,-
Br、-NO2Or CN；A and B indicates substituted-phenyl, substituted biphenyl base or substituted naphthyl.
2. application according to claim 1, which is characterized in that the solid heteropoly acid is in the solid-carrying heteropolyacid catalyst
In mass percent be 15%~45%.
3. application according to claim 1, which is characterized in that the solid-carrying heteropolyacid catalyst is applied to contain fluorene skeleton third
The preparation of olefin(e) acid ester includes the following steps：
Step (1), reaction dissolvent, reaction main ingredient, solid-carrying heteropolyacid catalyst and polymerization inhibitor are added separately in reactor, opened
Open and be uniformly mixed, heat up, flow back, dissolve after cool down, the first liquid is obtained, wherein shown in reaction main ingredient structure such as formula (2)：
In formula (2), n1The integer of=0-10, R1=-H ,-R or-Ar ,-R indicate alkyl or alkoxy, X=-H ,-Cl ,-NO2Or
CN, A and B indicate substituted-phenyl, substituted biphenyl base or substituted naphthyl；
Step (2) acrylic acid is added in step (1) described first liquid, back flow reaction, and turnout reason is carried out during reaction,
Cool down after completion of the reaction, obtains second liquid.
4. application according to claim 3, which is characterized in that the solid heteropoly acid is applied to acrylate containing fluorene skeleton
Preparation step (1) into (2), the reaction dissolvent be one of toluene, hexahydrotoluene.
5. application according to claim 3 or 4, which is characterized in that the solid-carrying heteropolyacid catalyst is applied to bone containing fluorenes
The preparation of frame acrylate further includes following steps：
Step (3) is filtered step (2) described second liquid to obtain third liquid, filters out solid-carrying heteropolyacid catalyst
It is reused in the step of recycling, recycling can put into next secondary response after activating (1)；
Step (3) the third liquid is washed with deionized to neutrality, obtains the 4th liquid by step (4)；
Step (5) will be added after step (4) described 4th liquid is dried after desiccant, and filtering and solvent distillation are produced
Product；And it is reused step (1) is added as reaction dissolvent after solvent recovery.
6. application according to claim 5, which is characterized in that the solid-carrying heteropolyacid catalyst is applied to contain fluorene skeleton third
In the preparation step (3) of olefin(e) acid ester, the number of the solid-carrying heteropolyacid catalyst recycling is 1~10 time.
7. application according to claim 3 or 4, which is characterized in that the solid-carrying heteropolyacid catalyst is applied to bone containing fluorenes
In the preparation step (1) of frame acrylate, the mass ratio (2.0~6.0) of the reaction dissolvent and reaction main ingredient：1.
8. application according to claim 3 or 4, which is characterized in that the solid-carrying heteropolyacid catalyst is applied to bone containing fluorenes
In the preparation step (2) of frame acrylate, the molar ratio of the acrylic acid and reaction main ingredient is (2.1~3.5)：1.
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| CN110938207A (en) * | 2019-12-10 | 2020-03-31 | 烟台开发区金宏化工有限公司 | Preparation method of hydrogen-containing silicone oil |
| CN113024377A (en) * | 2021-03-15 | 2021-06-25 | 沧州临港丰亚化工有限公司 | Novel method for synthesizing multi-ethoxy acrylate with fluorenyl structure by using supported catalyst |
| CN113786863A (en) * | 2021-10-11 | 2021-12-14 | 江苏集萃光敏电子材料研究所有限公司 | Solid acid catalyst and preparation method and application thereof |
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