CN109046451A - The high glycan class new construction derivative and preparation method, application in vinegar grain source - Google Patents
The high glycan class new construction derivative and preparation method, application in vinegar grain source Download PDFInfo
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- CN109046451A CN109046451A CN201811092872.XA CN201811092872A CN109046451A CN 109046451 A CN109046451 A CN 109046451A CN 201811092872 A CN201811092872 A CN 201811092872A CN 109046451 A CN109046451 A CN 109046451A
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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
- B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
- B01J31/02—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides
- B01J31/06—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides containing polymers
- B01J31/08—Ion-exchange resins
- B01J31/10—Ion-exchange resins sulfonated
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D233/00—Heterocyclic compounds containing 1,3-diazole or hydrogenated 1,3-diazole rings, not condensed with other rings
- C07D233/54—Heterocyclic compounds containing 1,3-diazole or hydrogenated 1,3-diazole rings, not condensed with other rings having two double bonds between ring members or between ring members and non-ring members
- C07D233/66—Heterocyclic compounds containing 1,3-diazole or hydrogenated 1,3-diazole rings, not condensed with other rings having two double bonds between ring members or between ring members and non-ring members with hetero atoms or with carbon atoms having three bonds to hetero atoms with at the most one bond to halogen, e.g. ester or nitrile radicals, directly attached to ring carbon atoms
- C07D233/72—Two oxygen atoms, e.g. hydantoin
- C07D233/74—Two oxygen atoms, e.g. hydantoin with only hydrogen atoms or radicals containing only hydrogen and carbon atoms, attached to other ring members
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
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- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P20/00—Technologies relating to chemical industry
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Abstract
The invention discloses the high glycan class new construction derivatives and preparation method, application in vinegar grain source, the new fresh vinegar grain, sodium metaperiodate, benzene sulfonic acid or the p-methyl benzenesulfonic acid that generate are as phenols in starting material, high glycan or the oxidant and sulfonating agent raw material of D- pyran ring structure unit specific site after first being brewed using mature vinegar, oxidation sulfonating reaction is carried out using stepwise reaction method or " chemical cascade coupling " method technique, reaction obtains the high glycan class new construction derivative in vinegar grain source under the baking of low-grade fever wet process；Then it using the high glycan class new construction derivative in vinegar grain source as catalyst, is catalyzed benzilic acid and is reacted with urea condensation, prepare phenytoinum naticum.The high glycan class new construction derivative in vinegar grain source of the present invention, preparation is simple, reaction is efficient, sulfonation degree (being calculated with sulfonic acid group in vinegar grain) is 101.1-156.6 milligrams per grams, catalyst reaches 2607.76-3096.89 micromoles per gram hour than living, catalyst life is 96 hours (remaining vigor >=70%), and catalyst can be reproduced and reuse.
Description
Technical field
The invention belongs to chemical industry and pharmaceutical technology field, are related to the high glycan class new construction derivative in vinegar grain source, especially
It is to be related to the high glycan class component oxidation-sulfonation new construction derivative and preparation method, application in vinegar grain source.
Background technique
Mature vinegar ranks first of Chinese four big vinegar, is china national geography famous special product.Mature vinegar is brewed skill and is won
First batch of national level non-material cultural heritage, it uses the second order fermentation technique of all solid state, lactic acid bacteria and acetic acid bacteria, with sorghum, bran
Skin, cavings and water are high-quality saccharifying ferment with barley, the made red heart yeast of pea as primary raw material, be saccharified after starch,
Vinegar is made in the processes such as alcoholic fermentation, acetic fermentation, smoked unstrained spirits, ageing.In recent years, the amount that mature vinegar is produced in Shanxi per year is more than 300,000
Ton, can form about 200,000 tons of vinegar grains.However, the availability of vinegar grain is generally lower, a small part is used as the circulation of all solid state vinegar processed
Material, ruminant/plant-eating animal feed for nursing, culture medium of edible fungus and plant culture fertilizer, biogas anaerobic fermentation raw material etc..
In addition to this, still there are a large amount of unused vinegar grains in Shanxi, it is long-term stack serious waste land resource and caused by environmental pressure it is big.
Since the Regional Distribution where Zhi Cu enterprise is relatively intensive, for synthetical collection, transport and exploitation vinegar grain, there have to be objective, convenient
Condition.
As a kind of natural organic substance, vinegar grain contains high percentage up to 66.4% carbon aqueous polymer, wherein wrapping
A large amount of cellulose, hemicellulose class, lignin component materials are included, diversity is formd by the orderly accumulation of hydrogen bond structure
Supermolecule skeleton.Component materials have the characteristics that surface hydrophilic and hydrophobic is moderate, bio-compatibility is big and chiral selectivity is high, in quotient
There is very high Development volue in the application fields such as industry fiber, advanced function material and sensor.In the research of early period, invention
Testimony of a witness reality vinegar grain source fiber element class, hemicellulose class, lignin component materials crystallinity index be up to 28.18%, compare table
Area is 14.55 ± 1.28 meters squared per grams, and intensity is high and has cell morphology, and aperture is about 0.31 ± 0.04 micron.Therefore,
It is novel industrial catalyst product that vinegar grain, which is suitable for exploitation, is applied especially to few with residual when pharmaceutical intermediate preparation, poison
Property it is small, Catalytic processes are simple, green advantage.
Red heart yeast grow nonparasitically upon another plant multienzyme system, multi items aspergillus hyphae, under the amylase and carbohydrase forceful action of aspergillus,
The starch material of vinegar raw material processed is through saccharification at D glucose.At the same time, sorghum, wheat bran, the cellulose family of cavings, half fiber
Tie up plain class, 1,4 glycosidic bond of β of lignin component partially hydrolyzes to form lactic acid, succinic acid, malic acid, lemon under aspergillus effect
The precursor substance of the precursor substance of a variety of organic acids such as lemon acid, and formation alcohols, aldehydes, esters etc..Precursor substance
Through leading to the fibre in vinegar grain source in chemical bond joining to cellulose family, hemicellulose class, the skeleton structure of lignin component
It ties up plain class, hemicellulose class, lignin skeleton structure and generates a large amount of solid acid, alcohols, aldehydes and ester groups are into one
The high glycan class component structure in step optimization vinegar grain source prepares new construction derivative and has established and reacts basis.Inventors have found that through
After crossing red heart great Qu saccharification, hydrolysis starch, the solid acid value of remaining vinegar grain reaches 0.082 mM/gram, it is a kind of side chain band
There are acidic-group, cation exchange and natural high molecular material, is suitable for catalysis diphenyl α glycolic and urine
5,5 xenyl hydantoins (phenytoinum naticum) are made in the condensation reaction of element.Therefore, for preparing important drug in pharmaceutical field
Intermediate, cellulose family, hemicellulose class, the lignin new construction derivative in vinegar grain source are a kind of novel, source letters
High-quality catalyst that is single and having potential application foreground.
Phenytoinum naticum is one for the treatment of big disease of human central nervous system three, the i.e. pharmaceutical intermediate of epileptics, in maincenter
In nervous system patient, the epilepsy total incidence in China is about 7%, and there are about 10,000,000 people to need to obtain rational therapy every year.Power
The data that prestige medical market research center provides show that domestic epileptics treatment gap is up to 63%.From discovery anti-epileptic in 1938
Drug effect since, using phenytoinum naticum as intermediate be used for antiepileptic drug preparation, patent medicine kind include phenobarbital,
Dilantin, dilantin and Sodium Phenytoin are that the still widely applied first-line treatment drug in clinic, the domestic approval of ranking list at present
Antiepileptic first of.The patent medicine of these kinds is the regulator of a Na-like ions and calcium channel, has stabilizing cell membrane
Potential polarization, the activity for quickly inhibiting sodium ion, flow of calcium ions, increase the maximum rate and action potential width of " 0 phase " depolarization
Degree accelerates conduction, is suitable for the breaking-out for the treatment of generalized tonic-clonic, complex partial seizures (psychomotor attack, temporal lobe
Epilepsy), simple partial seizure (localized episode) and status epilepticus, it can also be used to treat trigeminal neuralgia and adjusting
Rhythm abnormality caused by reentrant impulse.
The preparation process of phenytoinum naticum relies primarily on chemically synthesized method.Bucherer-Berg response path is initially to use
The method used to prepare phenytoinum naticum, reaction are that 60 70 DEG C are heated in 50% ethanol medium, 1,2 diphenylthanedione
Phenytoinum naticum is prepared with direct react of potassium cyanide, ammonium carbonate.This method is easy to operate, and raw material is easy to get, however has used severe toxicity
Cyanide, purifying products complex process, liquid waste processing are extremely difficult, and environmental protection pressure is larger, this response path has been forbidden for benzene
The preparation process of appropriate English and other drugs intermediate.Allantoin method is to prepare the common chemical method of phenytoinum naticum now, by 1,2
Benzilic acid and urea Cross-condensation reaction are made, and the catalyst of use has strong acid, such as sulfuric acid, nitric acid and hydrochloric acid, dosage
Up to 30% or more.The reaction mechanism mechanism of reaction of acid catalysis method be urea occur first proton dissociation reaction, generate hydantoins just from
Son, then with 1, electrophilic substitution reaction occurs for 2 benzilic acids, generates phenytoinum naticum.The shortcomings that allantoin reaction method is using strong
Acidic catalyst easily causes serious corrosion effect to consersion unit, and produces in the concentration of the phenytoinum naticum in later period and crystallization processes
Raw a large amount of waste water, catalyst recycle difficult.In addition, the sodium hydroxide aqueous alkali that concentration is about 30% can also catalyzing urea
With 1, the reaction of 2 diphenylthanediones prepares phenytoinum naticum, which needs the dosage of urea more than 1 times of theoretical value or more, generation
Side components it is more, product separating technology is complicated, and needs to be acidified, desalting steps.It is estimated that strong base catalyst technique about increases
The preparation cost about 30% or more for adding phenytoinum naticum easily remains in the product of phenytoinum naticum, in stimulation due to using ethanol system
Pivot nervous system.
The environmental protection of comprehensive phenytoinum naticum preparation process, economy, raw material and byproduct residue characteristic and patent medicine safety etc.
Factor, it can be seen that design, the synthesis of catalyst are the important process that phenytoinum naticum efficiently synthesized, reduced preparation cost always.Together
When, catalyst type is the key factor for restricting phenytoinum naticum synthetic reaction rate and manufacturing cycle.Therefore, exploitation has catalysis effect
Can it is high, surface property is stable, intensity is big, poison high and low to raw material affinity and without equipment corrosion, easily separated and recycling
New catalyst is the key that this important antiepileptic pharmaceutical intermediate skill urgently to be resolved of large scale preparation phenytoinum naticum always
Art hot spot.
201610077187.4 sulfonation vinegar grain, and the preparation method and application thereof in, disclose and changed using sulphur esterification techniques
Property vinegar grain, reaction conversion ratio be 14.7 36.9 milligrams of sulfonic acid groups/gram vinegar grain, sulphur esterification vinegar grain catalyst apply include benzene
In hydantoins structural derivative preparation reaction including appropriate English, there is preferable catalytic activity.
Summary of the invention
In order to solve the problems, such as existing phenytoinum naticum technology of preparing, it is poly- that the invention discloses a kind of height in vinegar grain source
Carbohydrate new construction derivative and application, using stepwise reaction method or the height in " chemical cascade coupling " method new process preparation vinegar grain source
Glycans new construction derivative catalyst, compared to 201610077187.4, the sulfonation conversion ratio of reaction improves 2.44 2.94
Again, the application performance of catalyst is more superior, has and accelerates phenytoinum naticum preparation reaction rate, and wastewater emission amount less waits spies
Point, the regeneration of catalyst, recovery process are simple, are easy to reuse for a long time.
The present invention is achieved through the following technical solutions:
It on the one hand, is with vinegar grain the invention discloses a kind of preparation method of the high glycan class new construction derivative in vinegar grain source
Powder is raw material, using sodium metaperiodate as oxidant, using benzene sulfonic acid or p-methyl benzenesulfonic acid as sulfonating agent, using stepwise reaction method or
" chemical cascade coupling " method carries out oxidation sulfonating reaction, and reaction obtains the height in vinegar grain source under the wet process baking conditions of low-grade fever
Glycans new construction derivative；The high glycan class new construction derivative in the vinegar grain source is side chain with acidic-group, positive
Ion-exchange type high molecular material can be used as a kind of natural infant industry catalyst；The vinegar grain powder is chemical work
It is bold and vigorous, brew the fresh feed that Particular craft generates by mature vinegar, granularity is 160-180 mesh, 0.082 mM of solid acid value/
Gram, carbon-nitrogen ratio 26.32 ± 2.03, vinegar grain particle is large pore material, crystalline form index 28.18%, BET specific surface area 14.55 ± 1.28
Meters squared per gram, aperture is at 0.31 ± 0.04 micron.
When specifically, using the high glycan class new construction derivative in stepwise reaction method preparation vinegar grain source, specific steps
Are as follows:
(1) vinegar grain powder and oxidant are mixed, spray watering is packed into volatilization porcelain crucible after mixing evenly, uses red soil after sealing
Crucible is wrapped up, is baked under the conditions of 50 ± 3 DEG C 5-8 hours, then stops heating, takes out reaction mass, it is 30 minutes cooling, repeatedly
It with deionized water elution reaction mass, filters, until the detection of anaerobic agent, merging filtrate, solid product drying is to get vinegar
The high glycan class component oxide (referred to as the high glycan type oxide or vinegar grain oxide in vinegar grain source) in poor source；The filter
Contain sodium iodate and the remaining sodium metaperiodate of reaction in liquid；
(2) vinegar grain oxide and sulfonating agent are mixed, spray watering is packed into porcelain crucible, with red soil packet after sealing after mixing evenly
Crucible is wrapped up in, is baked under the conditions of 50 ± 3 DEG C 12-24 hours, then stops heating, takes out reaction mass, it is 30 minutes cooling, it spends
Ionized water elution filters, until in filtrate without sulfonating agent, the dry high glycan class group to get vinegar grain source of solid product
Divide oxidation-sulfonation new construction derivative (the referred to as high glycan class new construction derivative in vinegar grain source).
When using the high glycan class new construction derivative in " chemical cascade coupling " method preparation vinegar grain source, specific steps
Are as follows: vinegar grain powder, oxidant, sulfonating agent are mixed, spray watering is packed into volatilization porcelain crucible, with red after sealing after mixing evenly
Mud drum wraps up in crucible, bakes 12 ± 0.5 hours under the conditions of 50 ± 3 DEG C, then stops heating, cooled down, takes out reaction mass,
It cooling 30 minutes, with deionized water elution, filters, until, without sulfonating agent and until oxidant, solid product is dry, i.e., in filtrate
Obtain the high glycan class new construction derivative in vinegar grain source；Contain sodium iodate, the remaining sodium metaperiodate of reaction and sulfonation in the filtrate
Agent.
When as a preferred implementation manner, prepared by stepwise reaction method: the mass ratio of the oxidant and vinegar grain powder is
(1-2): 1, the mass ratio of the high glycan class component oxide in the sulfonating agent and vinegar grain source is (1.3-1.41): 1；The sulphur
Agent is benzene sulfonic acid or p-methyl benzenesulfonic acid, and the mass ratio of benzene sulfonic acid sulfonating agent and vinegar grain oxide is 1.30:1, described to toluene
The mass ratio of sulfonated acid agent and vinegar grain oxide is 1.41:1；Preferably, the mass ratio of the oxidant and vinegar grain powder is
1.5:1.
When as a preferred implementation manner, prepared by " chemical cascade coupling " method: the vinegar grain powder, oxidant, sulfonation
The mass ratio of agent is 1:(1-2): (1.3-1.41)；Preferably, the mass ratio of the oxidant and vinegar grain powder is 1.5:1, institute
Sulfonating agent is stated as benzene sulfonic acid or p-methyl benzenesulfonic acid, the mass ratio of the benzene sulfonic acid and vinegar grain powder is 1.3:1, described to toluene sulphur
The mass ratio of acid and vinegar grain powder is 1.41:1.
As a preferred implementation manner, by the way that vinegar grain is smashed it through 160-180 mesh, then the vinegar grain powder is
It is rinsed with water, obtains after drying.
When further, using the high glycan class new construction derivative in stepwise reaction method preparation vinegar grain source, to step (1)
It is resulting containing sodium iodate and to react sodium hypochlorite is added in the filtrate of remaining sodium metaperiodate and is sufficiently stirred, be protected from light, depressurize,
It is reacted under heating condition, through filtering, crystallization, drying, obtains regenerated oxidant, for substituting fresh oxidant；Described time
The molar ratio of sodium chlorate and sodium iodate is (0.38-1.52): 1；The dosage of the regenerating oxidant is fresh oxidizer
1.2 times, it is preferable that the molar ratio of the sodium hypochlorite and sodium iodate is (0.95-1.52): 1.
On the other hand, the invention also discloses the high glycan class new construction derivatives in the vinegar grain source of above-mentioned preparation to be catalyzed
Application in phenytoinum naticum preparation.
Further, application of the high glycan class new construction derivative in the vinegar grain source in catalysis phenytoinum naticum preparation,
It the steps include:
(1) the high glycan class new construction derivative catalyst of reaction mass and vinegar grain source is placed in be protected from light, the temperature control of vacuum dress
In setting, reacted 24 ± 0.5 hours in 70 ± 3 DEG C of aqueous systems；
(2) solid catalyst and filtrate are separated while hot by reaction product rapid filtration under suction after reaction, filtrate is first analysed through cooling
Crude product is precipitated out, is washed after filtering with cold water, it is dry, obtain phenytoinum naticum；
(3) the high glycan class new construction derivative catalyst in vinegar grain source is reused, and is used to prepare phenytoinum naticum.
The reaction mass is the molar ratio by benzilic acid and urea by 1:1 as a preferred implementation manner,
Mixing composition, the mass ratio of reaction raw materials and water is 1:(9-11), and effectively sulfonic acid group quality accounts for reaction in the catalyst
The 4 5% of total mass of raw material.
The cellulose new construction derivative in vinegar grain source of the invention, using the cascade coupling of oxidation sulfonating reaction
Technique, oxidant meaning is can be with phenols in high glycan or D- pyran ring structure unit specific site (C2And C3) quantitative reaction
Sodium metaperiodate, the present invention also creatively use sodium hypochlorite oxidization regenerating oxidant, reuse oxidant it is new
Technology, sulfonating agent of the present invention be found for the first time in the technology scheme, can be with the dialdehyde of high glycan class component
The benzene sulfonic acid or p-methyl benzenesulfonic acid of base oxide reaction, matched using 8.0 software design reaction mass of Umetrics MODDE,
The group scheme of reaction temperature and time, the parameter of screening oxidation sulfonating reaction cascade coupling technique, the height in optimization vinegar grain source are poly-
Carbohydrate new construction derivative technology of preparing.
The high glycan class new construction derivative preparation method in vinegar grain source, technical characteristic first is that being baked using wet process anti-
The technology for answering material, with phenols or D- pyran ring structure unit C in the high glycan in oxidant cracking vinegar grain source2‒C3Key, system
Standby vinegar grain oxide, in this, as cascade reaction material, the high glycan class new construction for preparing vinegar grain source by sulfonation method is derivative
Object (see attached drawing 1).It is preparing after reaction, remaining oxidant or sulfonating agent collect filtrate skill using water elution, suction filtration
Art, according to N, the color change of N diethyl p-phenylenediamine dyestuff and oxidant reaction is surveyed at 552 nm with spectrophotometry
Determine absorbance, difference assay calculates the degree of reaction and conversion ratio of vinegar grain oxide；Further dripped with normal concentration sodium hydroxide solution
Fixed acidic sulfonated dose of remainder, is computed and acquires sulfonation degree, elutes through water to clean solid product, dry, obtains vinegar
The high glycan class new construction derivative in poor source uses infrared FTS and nuclear magnetic resonance chemical analyser measurement property
Energy.
The feature of technical solution of the present invention second is that invention oxidant regeneration, recycling new technology, the vinegar grain of preparation
Contain sodium iodate and the remaining sodium metaperiodate of reaction, foundation in the filtrate that oxide is eluted through water, filters, collectedn(sodium hypochlorite)
:nThe graded doses ratio of (sodium iodate)=0.38 1.52, accurately weighs the sodium hypochlorite solid of brand-new, is slowly dissolved in filtrate, aluminium
Film encapsulation reaction container, is protected from light, and vacuumizes (pressure is less than 0.01MPa), is slowly heated to boil, maintains 2.5-4 hours, obtain
Sodium metaperiodate regeneration product filters, and crystallizes, dry, reuses, is used to prepare vinegar grain oxide.
The high glycan class new construction derivative preparation method in vinegar grain source, technical characteristic are suitable for " grade third is that inventing
The implementation technology of connection reaction coupling ", vinegar grain are sufficiently mixed according to the proportion of optimization material with oxidant, sulfonating agent, are drenched with water,
It is reacted in closing, light resistant container, cools down, in transfer reaction material to Buchner funnel, filled with pure water after reaction
Divide elution material, filters, the dry high glycan class new construction derivative to get vinegar grain source, weighing, calculated yield.
The present invention prepares the technology of phenytoinum naticum using heterogeneous catalysis method, is the high glycan class new construction using vinegar grain source
Derivative is reacted in this, as the heterogeneous catalysis of phenytoinum naticum preparation reaction with sulfonic acid group effective quantity accounting in catalyst
Subject to the gross mass 4-5% of material, catalyst amount is calculated, using 1,2 benzilic acid and urea Cross-condensation reaction way
Diameter prepares phenytoinum naticum (see attached drawing 2).It feeds intake by 1:1 molar ratio, using the water of 9-11 times of quality as reaction system medium, 70 ±
It is reacted 24 ± 0.5 hours at 3 DEG C, stops reaction, sampled, dilution detects reaction conversion ratio.Testing conditions are as follows: high-efficient liquid phase color
Spectral technology (C18Splitter, measurement 210 nm of wavelength), measurement mobile phase be water/acetonitrile/phosphoric acid=90/10/0.01 volume
Than calculating the conversion ratio of reaction with calibration curve method.After reaction, while hot by reaction product rapid filtration under suction, separating catalyst,
Filtrate is precipitated precipitating crude product, is washed after filtering with cold water through cooling, dry, obtains phenytoinum naticum sterling, weighs, calculated yield.It urges
After agent separation, wash, it is dry, it reuses.
The present invention utilizes sodium periodate oxidation agent or its regenerated oxidant, prepares vinegar grain oxide, and anti-using sulfonation
The high glycan class new construction derivative in technology preparation vinegar grain source is answered, product is used as catalyst after detection is qualified.Sodium metaperiodate
Oxidant regeneration techniques, the high glycan class new construction derivative reuse in vinegar grain source and catalyst regeneration techniques, embody
Efficient, friendly process feature of the invention.
Compared with prior art, the invention has the following beneficial effects:
(1) the high glycan class new construction derivative in vinegar grain source is cheap and easy to get using vinegar grain as raw material, can pass through " chemistry cascade coupling
Close " method come realize vinegar grain source high glycan class component aoxidize sulfonating reaction new process, in conjunction with low-grade fever wet process bake technology,
Keep reaction time consumption shorter, more efficient；
(2) when preparing the high glycan class new construction derivative in vinegar grain source by stepwise reaction method, the adjoint production of vinegar grain oxide
Object (i.e. sodium iodate) is by regeneration, achievable recycling；
(3) the high glycan class new construction derivative in vinegar grain source is as a kind of for being catalyzed important pharmaceutical intermediate-phenytoinum naticum
The raw catelyst of preparation, compared to the catalytic effect of existing phenytoinum naticum catalyst, reaction conversion ratio raising, catalyst performance are more
Add superior, is in particular in phenytoinum naticum preparation reaction rate faster, wastewater emission amount is less, the regeneration of catalyst, recycling work
Skill is simple, is easy to reuse for a long time.
Detailed description of the invention
Attached drawing 1 is the schematic diagram of the high glycan class new construction derivative in vinegar grain source.
Attached drawing 2 is the chemical reaction schematic diagram that phenytoinum naticum is prepared using benzilic acid, urea as catalytic material method.
Attached drawing 3 is the infrared conversion spectrum figure of Fourier of the high glycan class new construction derivative in vinegar grain source.
Attached drawing 4 is the high glycan class new construction derivative in vinegar grain source13C NMR spectrum figure.
Attached drawing 5 is the high performance liquid chromatography separation figure of phenytoinum naticum.
Attached drawing 6 is the infrared conversion spectrum figure of Fourier of phenytoinum naticum.
Attached drawing 7 is phenytoinum naticum1H NMR spectrum figure.
Specific embodiment
It is described below for disclosing the content of present invention, so that those skilled in the art can be realized the present invention.It is described below
In preferred embodiment be only used as illustrating, it may occur to persons skilled in the art that other obvious modifications.
Embodiment 1 prepares the high glycan class new construction derivative in vinegar grain source using stepwise reaction method
The preparation method of the high glycan class new construction derivative in vinegar grain source, the specific steps are that:
(1) 50 grams of vinegar grain powders and 50 grams of sodium metaperiodates are mixed, with 40 ml deionized waters, mixture is drenched using spray-on process
Material, is packed into volatilization porcelain crucible after mixing evenly, wraps up crucible with red soil after sealing, and it is small that 8 ± 0.5 are baked under the conditions of 50 ± 3 DEG C
When, then stop heating, takes out reaction mass, it is 30 minutes cooling, it is transferred in 250 milliliters of Buchner funnels, uses deionization repeatedly
Water elution filters, and until anaerobic agent in filtrate, collects filtrate, contains reaction product acid iodide in the collection filtrate
Remaining sodium metaperiodate takes filtrate sample in this, as the regenerated sample solution of oxidant after sodium and reaction, measures residual oxidizing agent
Amount, and calculate vinegar grain oxidizability；Solid product drying, constant weight, weighing, obtain vinegar grain oxide, calculated yield, and use Fourier
Infrared transform spectrometer and13The measurement of C nuclear magnetic resonance chemical analyser；
(2) vinegar grain oxide is mixed with benzene sulfonic acid or p-methyl benzenesulfonic acid by the mass ratio of 1:1.30 or 1:1.41, with 32 or 34
Ml deionized water drenches mixed material using spray-on process, is packed into porcelain crucible after mixing evenly, wraps up earthenware with red soil after sealing
Crucible bakes 12 ± 0.5 hours under the conditions of 50 ± 3 DEG C, then stops heating, cooled down, and takes out reaction mass, 30 points cooling
Clock with deionized water elution, filters, and until in filtrate without sulfonating agent, the dry height to get vinegar grain source of solid product is poly-
Carbohydrate new construction derivative.Solid product weigh, calculated yield, and with the infrared transform spectrometer of Fourier with13C nuclear magnetic resonance wave
Spectrometer measurement.
Through detecting, the oxidizability of vinegar grain is 38.23%, and vinegar grain oxide yield is 100%；The sulfonation degree of vinegar grain oxide
(in terms of sulfonic acid group) is that 14.69 or 10.11%(using benzene sulfonic acid or p-methyl benzenesulfonic acid is used as sulfonating agent), the height in vinegar grain source gathers
The yield of carbohydrate new construction derivative is 80.02 or 76.28%(using benzene sulfonic acid or p-methyl benzenesulfonic acid as sulfonating agent).
Embodiment 2 prepares the high glycan class new construction derivative in vinegar grain source using stepwise reaction method
The preparation method of the high glycan class new construction derivative in vinegar grain source, the specific steps are that:
(1) 50 grams of vinegar grain powders and 100 grams of sodium metaperiodates are mixed, with 60 ml deionized waters, mixing is drenched using spray-on process
Material is packed into volatilization porcelain crucible after mixing evenly, wraps up crucible with red soil after sealing, 8 ± 0.5 are baked under the conditions of 50 ± 3 DEG C
Hour, then stop heating, take out reaction mass, cooling 30 minutes, be transferred in 250 milliliters of Buchner funnels, spend repeatedly from
Sub- water elution filters, and until anaerobic agent in filtrate, collects filtrate, contains reaction product iodine in the collection filtrate
Remaining sodium metaperiodate takes filtrate sample in this, as the regenerated sample solution of oxidant after sour sodium and reaction, measures residual oxidizing agent
Amount, and calculate the oxidizability of vinegar grain；Solid product drying, constant weight, weighing, obtain vinegar grain oxide, calculated yield；
(2) vinegar grain oxide is mixed with benzene sulfonic acid or p-methyl benzenesulfonic acid by the mass ratio of 1:1.30 or 1:1.41, with 32 or 34
Ml deionized water drenches mixed material using spray-on process, is packed into porcelain crucible after mixing evenly, wraps up earthenware with red soil after sealing
Crucible bakes 18 ± 0.5 hours under the conditions of 50 ± 3 DEG C, then stops heating, cooled down, and takes out reaction mass, 30 points cooling
Clock with deionized water elution, filters, and until in filtrate without sulfonating agent, the dry height to get vinegar grain source of solid product is poly-
Carbohydrate new construction derivative weighs, calculated yield.
Through detecting, the oxidizability of vinegar grain is 80.02%, and vinegar grain oxide yield is 93.03%；The sulfonation degree of vinegar grain oxide
(in terms of sulfonic acid group) is that 15.48 or 13.05%(using benzene sulfonic acid or p-methyl benzenesulfonic acid is used as sulfonating agent), the height in vinegar grain source gathers
Carbohydrate new construction derivative yield is 81.23 or 77.32%(using benzene sulfonic acid or p-methyl benzenesulfonic acid as sulfonating agent).
Embodiment 3 prepares the high glycan class new construction derivative in vinegar grain source using stepwise reaction method
The preparation method of the high glycan class new construction derivative in vinegar grain source, the specific steps are that:
(1) 50 grams of vinegar grain powders and 75 grams of sodium metaperiodates are mixed, with 50 ml deionized waters, mixture is drenched using spray-on process
Material, is packed into volatilization porcelain crucible after mixing evenly, wraps up crucible with red soil after sealing, and it is small that 5 ± 0.5 are baked under the conditions of 50 ± 3 DEG C
When, then stop heating, takes out reaction mass, it is 30 minutes cooling, it is transferred in 250 milliliters of Buchner funnels, uses deionization repeatedly
Water elution filters, and until anaerobic agent in filtrate, collects filtrate, contains reaction product acid iodide in the collection filtrate
Remaining sodium metaperiodate takes filtrate sample in this, as the regenerated sample solution of oxidant after sodium and reaction, measures residual oxidizing agent
Amount, and calculate the oxidizability of vinegar grain；Solid product drying, constant weight, weighing, obtain vinegar grain oxide, calculated yield；
(2) vinegar grain oxide is mixed with benzene sulfonic acid or p-methyl benzenesulfonic acid by the mass ratio of 1:1.3 or 1:1.41, with 32 or 34 millis
Deionized water is risen, mixed material is drenched using spray-on process, is packed into porcelain crucible after mixing evenly, wraps up crucible with red soil after sealing,
It is baked under the conditions of 50 ± 3 DEG C 24 ± 0.5 hours, then stops heating, cooled down, take out reaction mass, it is 30 minutes cooling,
With deionized water elution, filter, until in filtrate without sulfonating agent, the dry high glycan to get vinegar grain source of solid product
Class new construction derivative weighs, calculated yield.
Through detecting, the oxidizability of vinegar grain is 52.44%, and the yield of vinegar grain oxide is 94.32%；The sulfonation of vinegar grain oxide
Spending (in terms of sulfonic acid group) is 15.66 or 13.63%(using benzene sulfonic acid or p-methyl benzenesulfonic acid as sulfonating agent), the height in vinegar grain source
Glycans new construction derivative yield is 82.08 or 78.23%(using benzene sulfonic acid or p-methyl benzenesulfonic acid as sulfonating agent).
Embodiment 4 prepares the high glycan class new construction derivative in vinegar grain source using " chemical cascade coupling " method
" chemical cascade coupling " method prepares the high glycan class new construction derivative in vinegar grain source, specific steps are as follows: by 50 grams of vinegar grains
Powder, 75 grams of sodium metaperiodates and 65 grams of benzene sulfonic acid mixing, drench mixed material using spray-on process with 76 ml deionized waters,
It is packed into 250 milliliters of volatilization porcelain crucibles after mixing evenly, crucible is wrapped up with red soil after aluminium film covering sealing, under the conditions of 50 ± 3 DEG C
It bakes 12 ± 0.5 hours, then stops heating, take out reaction mass, it is 30 minutes cooling, it is transferred in Buchner funnel, uses repeatedly
Deionized water elution filters, until, without sulfonating agent and until oxidant, collecting filtrate in filtrate, taking filtrate sample, measure vinegar respectively
The oxidizability of grain and the sulfonation degree of vinegar grain oxide；Solid product is dry, constant weight to get vinegar grain source high glycan class new construction
Derivative, weighing, calculated yield.
Through detecting, the oxidizability of vinegar grain is 36.32%, the sulfonation degree of vinegar grain oxide is 14.66%, the height in vinegar grain source is poly-
Carbohydrate new construction derivative yield is 70.28%.
Embodiment 5 prepares the high glycan class new construction derivative in vinegar grain source using " chemical cascade coupling " method
" chemical cascade coupling " method prepares the high glycan class new construction derivative in vinegar grain source, specific steps are as follows: by 50 grams of vinegar grains
Powder, 75 grams of sodium metaperiodates and 70.5 grams of p-methyl benzenesulfonic acid mixing, drench mixing using spray-on process with 78 ml deionized waters
Material is packed into 250 milliliters of volatilization porcelain crucibles after mixing evenly, crucible is wrapped up with red soil after aluminium film covering sealing, in 50 ± 3 DEG C of items
It is baked under part 12 ± 0.5 hours, then stops heating, cooled down, take out reaction mass, it is 30 minutes cooling, it is transferred to Bu Shi
In funnel, repeatedly with deionized water elution, filter, until, without sulfonating agent and until oxidant, collecting filtrate in filtrate, taking filtrate
Sample measures the oxidizability of vinegar grain and the sulfonation degree of vinegar grain oxide respectively；Solid product drying, constant weight are to get vinegar grain source
High glycan class new construction derivative, weighing, calculated yield.
Through detecting, the oxidizability of vinegar grain is 33.28%, the sulfonation degree of vinegar grain oxide is 10.83%, the height in vinegar grain source is poly-
Carbohydrate new construction derivative yield is 66.64 %.
The high glycan class new construction derivative in vinegar grain source is yellowish or brown fine grained in above-described embodiment, sulfonic acid group
Content is 101.1-156.6 milligrams (being calculated with every gram of vinegar grain), and product is not soluble in water.Infrared absorption spectra is (see attached drawing 3, bromination
Potassium tabletting): the high glycan class new construction derivative absorption spectra in vinegar grain source is in 3241.5 3243.0 cm-1Place occurs wide and strong
It absorbs, is the stretching vibration peak of hydroxyl, 2910.6 2924.8 cm-1For-CH2Stretching vibration absworption peak, 1760cm-1For C=
O OH stretching vibration 1082.6-1087.8 cm-1For sulfonic group S (=O)2Stretching absorbance peak, 624-627 cm-1Nearby occur
Sulfonic group swings absorption peak, 990 cm-1For C S stretching vibration absworption peak, 1100 cm-1For C=S stretching vibration absworption peak, this
Outside, 1616.07 cm-1、1583.28 cm-1、1500.00 cm-1、1463.72 cm-1The four groups of peaks occurred are phenyl ring or toluene
Characteristic absorption.Solid-state nuclear magnetic resonance carbon spectrum (13C NMR, is shown in attached drawing 4): 60 ppm correspond to J (6 CH) chemical shift, 63.4 ppm
For J (C S) chemical shift, 60 80 ppm are J (4 CH) chemical shift, and 70 80 ppm are J (2,3,5 CH) chemical potential
It moves, 100 110 ppm are the displacement of J (1 CH), and 170 180 ppm are J (C=S) chemical shift.
The regeneration and preparation of 6 oxidant of embodiment
Sodium metaperiodate is reacted with vinegar grain, generates vinegar grain oxide and the acid iodide with product sodium iodate, according to bootstrap filtrate
Sodium actual concentrations, the amount of substance for calculation, according to sodium hypochlorite: mole 0.38:1 weighing sodium hypochlorite of sodium iodate is added to again
In the filtrate of raw sample, aluminium film encapsulation reaction container is protected from light, and is vacuumized (pressure is less than 0.01MPa), is slowly heated to boil,
It maintains 4 ± 0.5 hours, stops reaction, be cooled to room temperature, precipitating filtered on buchner funnel, cold water elution, dry, constant weight obtains
Regenerated oxidant.
After measured, regenerated oxidant yield is 7.0%.
The regeneration and preparation of 7 oxidant of embodiment
According to sodium hypochlorite: the molar ratio 0.95:1 of sodium iodate calculates hypochlorous acid dosage, and precise is added to bootstrap
Filtrate in, aluminium film encapsulation reaction container is protected from light, and is vacuumized (pressure be less than 0.01MPa), is slowly heated to boil, and maintains 2.5
± 0.5 hour, stop reaction, be cooled to room temperature, precipitating filtered on buchner funnel, cold water elution, dry, constant weight is regenerated
Oxidant is repeatedly applied in the preparation reaction of vinegar grain oxide.
After measured, regenerating oxidant yield is 76.02 %.
The regeneration and preparation of 8 oxidant of embodiment
According to sodium hypochlorite: the molar ratio 1.52:1 of sodium iodate calculates hypochlorous acid dosage, and precise is added to bootstrap
Solution in, aluminium film encapsulation reaction container is protected from light, and is vacuumized (pressure be less than 0.01MPa), is slowly heated to boil, and maintains 2.5
± 0.5 hour, stop reaction, be cooled to room temperature, precipitating filtered on buchner funnel, cold water elution, dry, constant weight is regenerated
Oxidant is repeatedly applied in the preparation reaction of vinegar grain oxide.
After measured, regenerating oxidant yield is 81.33%.
9 vinegar grain source high glycan class new construction derivatives catalysis application of embodiment
Sodium periodate oxidation-benzene sulfonic acid sulfonation vinegar grain source high glycan class new construction derivative is in catalysis phenytoinum naticum preparation
Using the steps include:
(1) benzilic acid and urea are added in three-necked flask by the molar ratio of 1:1, add the preparation of embodiment 4
Vinegar grain source high glycan class new construction derivative catalyst is placed in and is protected from light, in vacuum temp control device of the pressure not higher than 0.01MPa
In, it is reacted 24 ± 0.5 hours in 70 ± 3 DEG C of aqueous systems；The mass ratio of reaction raw materials and water is 1:(9-11), the catalysis
Effective sulfonic acid group quality accounts for the 4-5% of reaction mass gross mass in agent.
(2) 30 microlitres of reaction solutions are taken after reaction, are centrifuged, supernatant is removed, are diluted with water to 1.0 milliliters, are carried out high
Effect liquid phase chromatogram instrument measures content, and conversion ratio, the catalyst vigor of reaction are calculated with calibration curve method (see attached drawing 5).Detection
Condition are as follows: C18Splitter, measurement 210 nm of wavelength, the mobile phase of measurement are water/acetonitrile/phosphoric acid=90/10/0.01 volume ratio；
Take after reaction solution while hot by reaction product rapid filtration under suction, solid catalyst and filtrate separated, filtrate first through it is cooling be precipitated it is heavy
Shallow lake crude product, is washed after filtering with cold water, dry, obtains phenytoinum naticum sterling, and weighing calculates the yield that phenytoinum naticum preparation is reacted, and
With the infrared transform spectrometer of Fourier and1The measurement of H nuclear magnetic resonance chemical analyser；
After measured, the catalysis of sodium periodate oxidation-benzene sulfonic acid sulfonation vinegar grain source high glycan class new construction derivative is than work
2607.76 mM/gram hours (were calculated) with the sulfonic acid group in vinegar grain, and the conversion ratio of phenytoinum naticum preparation reaction is 71.69
%, phenytoinum naticum yield are 64.23 %.
The high glycan class new construction derivative in 10 sodium periodate oxidations of embodiment-p-methyl benzenesulfonic acid sulfonation vinegar grain source is urged
Change application
Sodium periodate oxidation-p-methyl benzenesulfonic acid sulfonation vinegar grain source high glycan class new construction derivative is in catalysis phenytoinum naticum preparation
In application, the steps include:
(1) benzilic acid and urea are added in three-necked flask by the molar ratio of 1:1, add the preparation of embodiment 5
Vinegar grain source high glycan class new construction derivative catalyst is placed in and is protected from light, in vacuum temp control device of the pressure not higher than 0.01MPa
In, it is reacted 24 ± 0.5 hours in 70 ± 3 DEG C of aqueous systems；The mass ratio of reaction raw materials and water is 1:(9-11), it is described to urge
Effective sulfonic acid group quality accounts for the 4-5% of reaction mass gross mass in agent.
(2) 30 microlitres of reaction solutions are taken after reaction, are centrifuged, supernatant is removed, are diluted with water to 1.0 milliliters, are carried out high
Effect liquid phase chromatogram instrument measures content, and calculates the conversion ratio of reaction with calibration curve method and calculate catalyst vigor.Testing conditions
Are as follows: C18Splitter, measurement 210 nm of wavelength, the mobile phase of measurement are water/acetonitrile/phosphoric acid=90/10/0.01 volume ratio；It takes
Reaction product rapid filtration under suction is separated solid catalyst and filtrate while hot after reaction solution, first precipitating is precipitated slightly through cooling in filtrate
Product are washed after filtering with cold water, dry, obtain phenytoinum naticum sterling, weighing, the yield for calculating phenytoinum naticum preparation reaction；
(3) the high glycan class new construction derivative catalyst in vinegar grain source made from embodiment 5 is repeated 3 times use, is used to prepare
Phenytoinum naticum.
The catalysis of sodium periodate oxidation-benzene sulfonic acid sulfonation vinegar grain source high glycan class new construction derivative is than work
3096.89 mM/gram hours (were calculated) with the sulfonic acid group in vinegar grain, and the conversion ratio of phenytoinum naticum preparation reaction is 85.14
%, phenytoinum naticum yield are 70.72 %；It reuses 3 catalyst and is followed successively by 3096.89,2823.34,2642.32 millis than living
Moles per gram hour, the service life of catalyst are 96 hours (70 % that remaining vigor is not less than initial value).
The regeneration of the high glycan class new construction derivative catalyst in 11 vinegar grain source of embodiment
(1) (1) middle high glycan class new construction using " chemical cascade coupling " method preparation vinegar grain source prepared by embodiment 9 is spread out
Biocatalyst, specific steps are as follows: the regenerating oxidant and benzene sulfonic acid for preparing catalyst, embodiment 8 are by 1:1.80:
1.30 mass ratio mixing drenches mixed material using spray-on process with deionized water, is packed into volatilization porcelain crucible, aluminium after mixing evenly
Crucible is wrapped up with red soil after film covering sealing, is baked under the conditions of 50 ± 3 DEG C 12 ± 0.5 hours, then stops heating, is taken out anti-
Answer material, it is 30 minutes cooling, be transferred in Buchner funnel, repeatedly with deionized water elution, filter, until in filtrate without sulfonating agent
Until oxidant, filtrate is collected, filtrate sample is taken, measures oxidizability and sulfonation degree respectively；Solid product is dry, constant weight to get
Regenerated vinegar grain source high glycan class new construction derivative catalyst.
(2) it is operated according to (3) the step of embodiment 10.
3 catalysis of regenerated vinegar grain source high glycan class new construction derivative catalyst are followed successively by than work after measured
2552.30,2336.13,2005.26 mM/gram hour.
The regeneration of the high glycan class new construction derivative catalyst in 12 vinegar grain source of embodiment
(1) (1) prepared by embodiment 10 is spread out using the high glycan class new construction in " chemical cascade coupling " method preparation vinegar grain source
Biocatalyst, specific steps are as follows: the regenerating oxidant and p-methyl benzenesulfonic acid for preparing catalyst, embodiment 8 are by 1:
The mass ratio of 1.80:1.41 mixes, and drenches mixed material using spray-on process with deionized water, is packed into volatilization porcelain earthenware after mixing evenly
Crucible wraps up crucible with red soil after aluminium film covering sealing, bakes 12 ± 0.5 hours under the conditions of 50 ± 3 DEG C, take out reaction mass,
Cooling 30 minutes, be transferred in Buchner funnel, repeatedly with deionized water elution, filter, until in filtrate without sulfonating agent and oxidation
Until agent, filtrate is collected, filtrate sample is taken, measures oxidizability and sulfonation degree respectively；Solid product is dry, constant weight is fine to get regeneration
Tie up plain class new construction derivative catalyst.
(2) it is operated according to (3) the step of embodiment 10.
3 catalysis of regenerated vinegar grain source high glycan class new construction derivative catalyst are followed successively by than work after measured
2742.68,2216.44,1923.32 mM/gram hour.
Phenytoinum naticum made from catalyst is colourless or light yellow solid in embodiment 9-12,296 297 DEG C of fusing point, is not dissolved in
Cold water is soluble in 70 DEG C or so of hot water.Infrared spectrum measurement result (pressing potassium bromide troche): 748.41,700.18 cm-1For benzene
The plane vibration of the monosubstituted C H of ring absorbs, 1398.44 cm-1For C N stretching vibration absorption, 1741.78,1774.57 cm-1
For C=O stretching vibration absorption, 3074.63 cm-1For phenyl ring C H stretching vibration absorption, 3265.59,3201.94 cm-1For N H
Stretching vibration absorbs.1H NMR spectrum measurement result: 10.88 ppm are (1H),sChemical shift, 9.03 ppm are
(1H),sChemical shift, 7.04-7.12 ppm are (10H),mChemical shift, as shown in attached drawing 6-7.
The basic principles, main features and advantages of the present invention have been shown and described above.The technology of the industry
Personnel are it should be appreciated that the present invention is not limited to the above embodiments, and what is described in the above embodiment and the description is only the present invention
Principle, various changes and improvements may be made to the invention without departing from the spirit and scope of the present invention, these variation and
Improvement is both fallen in the range of claimed invention.The present invention claims protection scope by appended claims and its
Equivalent defines.
Claims (10)
1. the preparation method of the high glycan class new construction derivative in vinegar grain source, it is characterised in that: be using vinegar grain powder as raw material,
Using sodium metaperiodate as oxidant, using benzene sulfonic acid or p-methyl benzenesulfonic acid as sulfonating agent, using stepwise reaction method or " chemistry cascade coupling
Conjunction " method carries out oxidation sulfonating reaction, and reaction obtains the high glycan class new construction in vinegar grain source under the wet process baking conditions of low-grade fever
Derivative；The granularity of the vinegar grain powder be 160 180 mesh, 0.082 mM/gram of solid acid value, carbon-nitrogen ratio 26.32 ±
2.03, vinegar grain powder is large pore material, and crystalline form index 28.18%, 14.55 ± 1.28 meters squared per gram of BET specific surface area, aperture exists
0.31 ± 0.04 micron.
2. the preparation method of the high glycan class new construction derivative in vinegar grain source as described in claim 1, which is characterized in that use
Stepwise reaction method, specific steps are as follows:
(1) vinegar grain powder and oxidant are mixed, spray watering is packed into volatilization porcelain crucible after mixing evenly, uses red soil after sealing
Crucible is wrapped up, is baked under the conditions of 50 ± 3 DEG C 5-8 hours, then stops heating, takes out reaction mass, it is 30 minutes cooling, repeatedly
It with deionized water elution, filters, until the detection of anaerobic agent, merging filtrate, solid product drying is to get vinegar grain source
High glycan class component oxide；Contain sodium iodate and the remaining sodium metaperiodate of reaction in the filtrate；
(2) the high glycan class component oxide and sulfonating agent in vinegar grain source are mixed, spray watering is packed into porcelain earthenware after mixing evenly
Crucible wraps up crucible with red soil after sealing, bakes 12-24 hours under the conditions of 50 ± 3 DEG C, then stops heating, takes out reactant
Material, it is 30 minutes cooling, it with deionized water elution, filters, until in filtrate without sulfonating agent, solid product is dry to get vinegar
The high glycan class component oxidation-sulfonation new construction derivative in poor source.
3. the preparation method of the high glycan class new construction derivative in vinegar grain source as described in claim 1, which is characterized in that use
" chemical cascade coupling " method, specific steps are as follows: mix vinegar grain powder, oxidant, sulfonating agent, spray watering, after mixing evenly
It is packed into volatilization porcelain crucible, wraps up crucible with red soil after sealing, is baked under the conditions of 50 ± 3 DEG C 12 ± 0.5 hours, then stops adding
Heat is cooled down, and reaction mass is taken out, 30 minutes cooling, is eluted, is filtered with deionized water repeatedly, until no sulfonating agent and oxygen
Until agent detects, merging filtrate, the dry high glycan class new construction derivative to get vinegar grain source of solid product；The filter
Contain sodium iodate, the remaining sodium metaperiodate of reaction and sulfonating agent in liquid.
4. the preparation method of the high glycan class new construction derivative in vinegar grain source as claimed in claim 2, it is characterised in that: described
The mass ratio of oxidant and vinegar grain powder is (1-2): 1, the high glycan class component oxide in the sulfonating agent and vinegar grain source
Mass ratio is (1.3-1.41): 1；The sulfonating agent is benzene sulfonic acid or p-methyl benzenesulfonic acid.
5. the preparation method of the high glycan class new construction derivative in vinegar grain source as claimed in claim 3, it is characterised in that: described
Vinegar grain powder, oxidant, sulfonating agent mass ratio be 1:1.5:(1.30-1.41)；The sulfonating agent is for benzene sulfonic acid or to toluene
Sulfonic acid.
6. the preparation method of the high glycan class new construction derivative in vinegar grain source as described in claim 1, it is characterised in that: described
Vinegar grain powder is then rinsed with water, obtains after drying by the way that vinegar grain is smashed it through 160-180 mesh.
7. the preparation method of the high glycan class new construction derivative in vinegar grain source as claimed in claim 2, it is characterised in that: Xiang Bu
Suddenly sodium hypochlorite is added in the filtrate containing sodium iodate and the remaining sodium metaperiodate of reaction stated obtained by (1) and is sufficiently stirred, is keeping away
Reaction is heated under light, reduced pressure, is generated sodium metaperiodate converted product and is obtained fresh for substituting through filtering, crystallization, drying
The regenerating oxidant of oxidant；The preferable molar ratio of the sodium hypochlorite and sodium iodate is (0.38-1.52): 1；The oxygen regeneration
Agent dosage is 1.2 times of fresh products dosage.
8. the high glycan class new construction derivative in the vinegar grain source of any preparation prepares benzene in catalysis method in claim 1-7
Appropriate English-Chinese application.
9. the high glycan class new construction derivative in vinegar grain source as claimed in claim 8 prepares answering in phenytoinum naticum in catalysis method
With, which is characterized in that step are as follows:
(1) high glycan class component oxidation-sulfonation new construction derivative catalyst of reaction mass and vinegar grain source is placed in be protected from light,
In the temperature regulating device of vacuum, reacted 24 ± 0.5 hours in 70 ± 3 DEG C of aqueous systems；
(2) solid catalyst and filtrate are separated while hot by reaction product rapid filtration under suction after reaction, filtrate is first analysed through cooling
Crude product is precipitated out, is washed after filtering with cold water, it is dry, obtain phenytoinum naticum；
(3) the high glycan class new construction derivative catalyst in vinegar grain source is reused, and is used to prepare phenytoinum naticum.
10. the high glycan class new construction derivative in vinegar grain source as claimed in claim 9 prepares answering in phenytoinum naticum in catalysis method
It is mixed and is formed by the molar ratio of 1:1 with urea by benzilic acid with, it is characterised in that: the reaction mass, reaction
The mass ratio of raw material and water is 1:(9-11), and effectively sulfonic acid group quality accounts for the 4 of reaction mass gross mass in the catalyst
5%。
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Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1126260A (en) * | 1994-05-27 | 1996-07-10 | 金伯特-克拉克公司 | Sulfonated cellulose and method of preparation |
| WO2012119229A1 (en) * | 2011-03-08 | 2012-09-13 | The Royal Institution For The Advancement Of Learning/Mcgill University | Highly charge group-modified cellulose fibers which can be made into cellulose nanostructures or super-absorbing cellulosic materials and method of making them |
| CN105562082A (en) * | 2016-02-04 | 2016-05-11 | 吕梁学院 | Sulfonated vinegar residues and preparation method and application thereof |
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Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1126260A (en) * | 1994-05-27 | 1996-07-10 | 金伯特-克拉克公司 | Sulfonated cellulose and method of preparation |
| WO2012119229A1 (en) * | 2011-03-08 | 2012-09-13 | The Royal Institution For The Advancement Of Learning/Mcgill University | Highly charge group-modified cellulose fibers which can be made into cellulose nanostructures or super-absorbing cellulosic materials and method of making them |
| CN105562082A (en) * | 2016-02-04 | 2016-05-11 | 吕梁学院 | Sulfonated vinegar residues and preparation method and application thereof |
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