CN105771925A - Skeleton polymer for extracting chondroitin sulfate and preparation method of skeleton polymer - Google Patents
Skeleton polymer for extracting chondroitin sulfate and preparation method of skeleton polymer Download PDFInfo
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Abstract
The invention relates to a three-dimensional skeleton polymer and a preparation method thereof. The specific three-dimensional skeleton structure of a melamine sponge is used, and a chitosan coating is cladded on a skeleton; then through a reaction of ethylene glycol diglycidyl ether and the chitosan coating, the ethylene glycol diglycidyl ether and the chitosan coating are in cross-linking, and a large number of epoxy groups are carried on surfaces; then through a reaction of the epoxy groups and diethanolamine, tertiary amine groups are generated; then through an oxidation-reduction reaction of the tertiary amine groups and potassium persulfate at a room temperature, free radicals are generated on the surface of the skeleton, the graft polymerization reaction of the dimethyldiallyl ammonium chloride is further initiated, a large number of cations are introduced on the surface of the skeleton, and the material through cationization is liable to generate electrostatic interaction with chondroitin sulfate macromolecules with negative charges. The material can be used as a whole adsorbing column, and has a pivotal role in the rapid and efficient extraction of the chondroitin sulfate. The material has the advantages that the absorbing capacity is high, the operation is simplified, the material can be repeatedly recycled, the cost is reduced, and the production efficiency is improved.
Description
Technical field
The present invention relates to the technical field of polymer materials extracted for bioactive substance, especially a kind of chemical modification method based on melamine sponge skeleton polymer, obtained adsorbing material can be used for the rapidly and efficiently extraction of chondroitin sulfate.
Background technology
Chondroitin sulfate (chondroitinsulfate, CS) it is the sulfated glycosaminoglycans (acid mucopolysaccharide) obtained from animal cartilaginous tissue, CS is a kind of polyanionic compound, relative molecular mass is about 10000～35000, white powder, odorless, tasteless, there is hygroscopicity, soluble in water form thick liquid, insoluble in most of organic solvents.CS is mainly used in treatment migraine, neuralgia, arthritis as medicine, prevent and treat the auxiliary treatment of the dysacousis because streptomycin causes and hepatitis, because it has blood fat reducing, anticoagulant active, it is also used for the preventing and treating of the cardiovascular disease such as hyperlipidemia, coronary heart disease, atherosclerosis.Discovered in recent years; CS also has antiinflammatory, anticancer, AntiHIV1 RT activity isoreactivity, and neurocyte, mucomembranous cell, nephrocyte etc. are had protective effect, and CS is with its good toleration and safety; having wide application and development prospect, CS has become one of maximum biochemical drug of China's export amount.
In the industrial production, the common method that CS extracts is diluted alkaline hydrolysis binding resin exchange process, and its advantage is that hydrolysis combines with resins exchange technology, it is ensured that chondroitin sulfate molecule is not degraded, and finished product purity is high, method is easy, yield is high.Ion exchange is based on CS molecule and contains the fundamental characteristics of electronegative sulfate group, and by forming complex with cation electrostatic interaction, then eluting under electrolyte effect again, thus reaching the purpose of extraction and purification.Ion exchange should use a kind of positively charged cellular solid, conventionally used polymeric anion exchanger resin, such as AmberliteIRA-933 type resin, this resin aperture less (being typically less than the micropore of 20nm), generally all it is used for exchanging low-molecular-weight anion, CS is as a kind of macromole anion, its diffusion rate in the liquid phase is far below common low-molecular-weight, anionic, it is not easily accessible in micropore, mostly acting only on the surface of exchanger resin, in viscous liquid, its exchange rate and efficiency are all a problem.The present invention provides the macromolecular material of a kind of three dimensional skeletal structure, its aperture reaches 100 μm, it is very beneficial for mass transfer, and material surface is with abundant positive charge, so being highly suitable for the CS molecule of exchange macromolecule, the method adopting globality pillar significantly improves efficiency and the speed of ion exchange, is conducive to improving the industrial production efficiency of CS.
Summary of the invention
To be solved by this invention primarily technical problem is that provides a kind of three-dimensional framework polymer for there is the less problem in ion exchange resin aperture in CS extraction process, it has the through duct of three-dimensional net structure and 100 μm, its skeleton surface is through special chemical modification, thus with abundant positive charge, it is prone to the CS molecule that absorption is electronegative, keeps away
Exempt to affect because of diffusion rate problem adsorption efficiency and speed, and can be easy to adsorbent eluting, it is achieved the repeatedly recycling of material, improve the production efficiency of CS.
Another technical problem to be solved by this invention is to provide syntheti c route and the method for above-mentioned three-dimensional framework polymer, and it is practical, easy and simple to handle, it is easy to prepare in a large number.
Another technical problem to be solved by this invention is to provide the concrete application in CS extracts of a kind of above-mentioned three-dimensional framework polymer.
1, this invention address that the technical scheme that primary technical problem adopts is: a kind of three-dimensional framework polymer, it is characterized in that it is to be obtained by the chemical modification to melamine sponge (having structure as shown in Figure 1), chemical modification only changes the surface nature of skeleton, and do not change the three-dimensional net structure of material, still retaining the duct interconnected of about 100 μm, this duct is conducive to liquid communication.
It is beneficial that above-mentioned three-dimensional framework polymer surfaces is with a large amount of cation groups, existing very strong hydrophilic, there is electrostatic interaction in the CS easily with a large amount of barium white ionic groups again, strengthens absorbability.
2, this invention address that the technical scheme that another technical problem adopts is: the ioning method of a kind of above-mentioned high-molecular bone frame material, chemical reaction route is as in figure 2 it is shown, its characterization step is:
1) it is dissolved in dilute acetic acid aqueous solution by the viscosity chitosan more than 400mpa.s being made into the concentration of 1～2wt.%, add a small amount of cationic surfactant (such as Dodecyl trimethyl ammonium chloride, concentration in solution is 0.1～0.2wt.%), by commercially available melamine sponge, (tripolycyanamide and formaldehyde crosslinking react the foamed materials made, now commercialization) soak in the solution, unnecessary solution is sopped up by vacuum after taking-up, ensure that it does not have solution to flow out under standing, then dry 2～3 hours at 60 DEG C in an oven, soak 20～30 minutes in the sodium carbonate liquor of pH=9～10 again, form insoluble thin film after chitosan deprotonation and cover skeleton surface；2) material clear water is soaked in after washing in the alcoholic solution of the Ethylene glycol diglycidyl ether of 10～12wt.% again and reacts 1～2 hour under room temperature, then by 95% washing with alcohol 1～2 time, it is soaked in the alcoholic solution of diethanolamine of 12～15wt.% again, react 2～3 hours at normal temperatures, the epoxide group hung changes into tertiary amine group, then by 95% washing with alcohol 1～2 time；3) sample is soaked in the aqueous solution of the dimethyl diallyl ammonium chloride containing 3～4wt.% and 1～2wt. ‰ potassium peroxydisulfate, there is graft reaction 3～4 hours at normal temperatures, wash 2～3 times with clear water, remove, with centrifugal method, the moisture that material internal is unnecessary.
It is beneficial that above-mentioned Ethylene glycol diglycidyl ether can play two effects: one is that amino with chitosan surface reacts, and draws the epoxide group hung；Two is react with the amino within chitosan, makes chitosan generation cross-linking reaction, is conducive to the stabilisation of this clad；
Very usefully, above-mentioned graft reaction utilizes tertiary amine and potassium peroxydisulfate that redox reaction occurs at normal temperatures, tertiary amine group produces free radical, further Inducing Graft Polymerization, by suitably controlling the concentration of grafted monomers, both made cation chain segments on skeleton surface grafting, made again chitosan coat firm attachment, will not come off easily.
3, this invention address that the technical scheme that another technical problem adopts is: above-mentioned skeleton polymer application process in CS extracts, it is characterized in that being superimposed some block of material, it is placed in a glass columns, constituting globality absorption pillar, infiltrated by material solution and flow through this material, extract is adsorbed on the skeleton of polymer, washing through clear water and buffer solution, remove other impurity, then pass through eluting and extract is collected, to reach the purpose of Separation & Purification.
Very usefully, above-mentioned processing method is filled pillar than general resin and is wanted efficient quick, on skeleton, substantial amounts of cation is all likely to have an effect with the sulfate anion group on CS, the problem being absent from diffusion hindered, find through overtesting, each gram of material can adsorb the CS of 79～90mg, and its absorbability is higher than existing anion exchange resin.
It is an advantage of the current invention that: 1) new adsorbing material aperture is big, is conducive to solid tumor, mass transfer；2) its three-dimensional net structure is conducive to the circulation of liquid, reduces flow resistance；3) polycation segment has bigger free property than relatively-stationary cation group, it is easier to CS, electrostatic attraction effect occurs.
Detailed description of the invention
Below in conjunction with embodiment, the present invention is described in further detail.
Prepared by material:
1, it is dissolved in dilute acetic acid aqueous solution by the viscosity chitosan more than 400mpa.s being made into the concentration of 1～2wt.%, add a small amount of cationic surfactant (Dodecyl trimethyl ammonium chloride, concentration in solution is 0.1～0.2wt.%), by cylindric melamine sponge (diameter 10cm, thickness is 20cm) soak in the solution, unnecessary solution is sopped up by vacuum after taking-up, ensure that it does not have solution to flow out under standing, then again in baking oven at 60 DEG C dry 2～3 hours, soak 20～30 minutes in the sodium carbonate liquor of pH=9～10 again, form insoluble thin film after chitosan deprotonation and cover skeleton surface；
2, material clear water is soaked in after washing in the alcoholic solution of the Ethylene glycol diglycidyl ether of 10～12wt.% again and reacts 1～2 hour under room temperature, then by 95% washing with alcohol 1～2 time, it is soaked in the alcoholic solution of diethanolamine of 12～15wt.% again, react 2～3 hours at normal temperatures, the epoxide group hung changes into tertiary amine group, then by 95% washing with alcohol 1～2 time；
3, then sample is soaked in the aqueous solution of the dimethyl diallyl ammonium chloride containing 3～4wt.% and 1～2wt. ‰ potassium peroxydisulfate, there is graft reaction 3～4 hours at normal temperatures, finally wash 2～3 times with clear water, get rid of, with centrifugal method, the liquid that material internal is unnecessary.
The extraction of CS is undertaken by following operating procedure:
A. extract, fresh clean cartilage pulverizer is pulverized, the cartilage of rubbing is placed in stainless steel reaction tank, add 1mol/L sodium hydroxide solution to soak, be under agitation heated to 40 DEG C, insulation hydrolysis 2～3 hours, then add hydrochloric acid again and be neutralized to neutrality, filter and collect filtrate；
B. purification, above filtrate is adjusted sodium chloride concentration and reaches 0.5mol/L, by solution integral post (10cm × 100cm by being made up of three-dimensional framework polymer, it is formed by stacking by 5 pieces of cylindric samples), the volume of filtrate should be 1: 2～1: 2.5 with the volume of pillar ratio with it, flow speed control is at 50～80mL/min, then with the 0.5mol/L aqueous NaCl wash of pillar volume 1 times amount, with the 1.8mol/L sodium chloride eluting pillar of pillar volume 1 times amount, flow speed control, at 70～90mL/min, collects eluent；
C. desalination, by eluent through ultrafilter desalination, collects ultrafiltrate；
D. precipitating, be poured in Enamel jar by above-mentioned ultrafiltrate, be subsequently adding 95% ethanol, make the volume fraction of ethanol reach 50～60%, deposit to clearly, siphon removes the supernatant, collects precipitation；
E. dry, precipitation is filtered dry or hangs with calico dry, with 95% ethanol dehydration 2～3 times, vacuum drying at 70 DEG C, obtain chondroitin sulfate finished product.
Quality testing:
1) aminohexose assay, aminohexose is produced with HCl/water solution chondroitin sulfate, react with acetylacetone,2,4-pentanedione in the basic conditions, again with paradime thylaminobenzaldehyde condensation, generate red compound, with glucosamine hydrochloride for standard reference material, with spectrophotometry, obtaining the average content of aminohexose in sample is 31.3%；
2) sulfur determination, with HCl and H2O2Process, make chondroitin sulfate hydrolysis discharge sulfate radical, then add barium salt and make it generate BaSO4Precipitation, then presses BaSO4Molecular forms, with its average sulfur content of gravimetric detemination for 7.2%；
Material absorbability is assessed: the dry state density of anion frame material is generally 0.04～0.05g/mL, the volume of integral post is 7.85L, its quality is 314～393g, meansigma methods is 353g, integral post is after fully absorption, through eluting, the CS amount every time obtained after purification is 28～32g, therefore every gram of material can adsorb the amount of CS in 79～90mg scope, and the absorbability of general ion exchange resin only has 16～25mg/g, so, material provided by the invention has a clear superiority on absorbability, this is mainly attributed to its large aperture and the feature of high porosity (low-density).
Accompanying drawing explanation
The SEM image of Fig. 1 melamine sponge
The reaction scheme figure that Fig. 2 three-dimensional framework materials chemistry is modified.
Claims (5)
1. a three-dimensional framework polymer, it is characterised in that it is based on the chemical modification of melamine sponge, has both remained the duct interconnected of three-dimensional continuous print network structure and 100 μm, has made again Skeleton Table mask have special absorption property.
2. three-dimensional framework polymer according to claim 1, it is characterised in that described polymer surfaces passes through graft polymerization reaction, PDDA segment in suspension.
3. three-dimensional framework polymer according to claim 1 and 2, it is characterized in that described three-dimensional framework polymer can adsorb electronegative chondroitin sulfate macromole by ion exchange principle in the way of globality pillar so that it is absorbability and speed significantly improve.
4. the preparation method of the three-dimensional framework polymer described in a claim 1, it is characterised in that step is followed successively by:
(1) viscosity chitosan more than 400mpa.s is taken, melamine sponge is immersed in 1～2wt.% chitosan solution, unnecessary solution is sopped up by vacuum after taking-up, ensure that it does not have solution to flow out under standing, then dry 2～3 hours at 60 DEG C in an oven, soak 20～30 minutes in the sodium carbonate liquor of pH=9～10 again, form insoluble thin film after chitosan deprotonation and cover skeleton surface；
(2) be soaked in again after the washing of above-mentioned material clear water 10～12wt.% diethylene glycol diglycidyl ether alcoholic solution in reaction 1～2 hour under room temperature, then by 95% washing with alcohol 1～2 time；
(3) being soaked in the alcoholic solution of diethanolamine of 12～15wt.% again, react 2～3 hours at normal temperatures, the epoxide group of suspension changes into tertiary amine group, then by 95% washing with alcohol 1～2 time；
(4) again sample is soaked in the aqueous solution containing dimethyl diallyl ammonium chloride and potassium peroxydisulfate, graft reaction occurs 3～4 hours at normal temperatures, finally wash 2～3 times with clear water, get rid of, with centrifugal method, the liquid that material internal is unnecessary.
5. the graft polymerization reaction in preparation method according to claim 4, it is characterised in that the concentration of dimethyl diallyl ammonium chloride and potassium peroxydisulfate respectively 3～4wt.% and 1～2wt. ‰.
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Cited By (4)
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| CN107459778A (en) * | 2017-08-30 | 2017-12-12 | 复旦大学 | A kind of epoxy matrix composite with high heat conductance and preparation method thereof |
| WO2020052679A1 (en) * | 2018-09-14 | 2020-03-19 | Versitech Limited | Gravity-driven chitosan-enhanced melamine sponge for stable ultrafast filtration |
| CN112756016A (en) * | 2020-12-11 | 2021-05-07 | 安徽皖仪科技股份有限公司 | Grafting type anion exchange resin chromatographic packing and preparation method thereof |
| US20210268447A1 (en) * | 2016-03-03 | 2021-09-02 | Versitech Limited | Gravity-driven chitosan-enhanced melamine sponge for stable ultrafast filtration |
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Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
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| US20210268447A1 (en) * | 2016-03-03 | 2021-09-02 | Versitech Limited | Gravity-driven chitosan-enhanced melamine sponge for stable ultrafast filtration |
| CN107459778A (en) * | 2017-08-30 | 2017-12-12 | 复旦大学 | A kind of epoxy matrix composite with high heat conductance and preparation method thereof |
| CN107459778B (en) * | 2017-08-30 | 2019-10-15 | 复旦大学 | A kind of epoxy matrix composite and preparation method thereof with high heat conductance |
| WO2020052679A1 (en) * | 2018-09-14 | 2020-03-19 | Versitech Limited | Gravity-driven chitosan-enhanced melamine sponge for stable ultrafast filtration |
| CN112756016A (en) * | 2020-12-11 | 2021-05-07 | 安徽皖仪科技股份有限公司 | Grafting type anion exchange resin chromatographic packing and preparation method thereof |
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Effective date of registration: 20210528 Address after: 210000 Lishui Economic Development Zone, Nanjing, Jiangsu Province Patentee after: NANJING FENCHEM BIOLOGICAL TECHNOLOGY Co.,Ltd. Address before: No. 412, 4th floor, building 4, No. 588 Shuhui Road, Qingyang District, Chengdu, Sichuan 610000 Patentee before: Chengdu Feiyou Trading Co.,Ltd. Effective date of registration: 20210528 Address after: No. 412, 4th floor, building 4, No. 588 Shuhui Road, Qingyang District, Chengdu, Sichuan 610000 Patentee after: Chengdu Feiyou Trading Co.,Ltd. Address before: 315211 School of Material Chemistry, Ningbo University, 818 Fenghua Road, Jiangbei District, Ningbo City, Zhejiang Province Patentee before: Ningbo University |