CN104974355A - pH-responsive amino sodium lignosulphonate as well as preparation method and application thereof - Google Patents
pH-responsive amino sodium lignosulphonate as well as preparation method and application thereof Download PDFInfo
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Abstract
The invention discloses a preparation method and application of pH-responsive amino sodium lignosulphonate. The preparation method comprises the following steps: dissolving sodium lignosulphonate in water to prepare a sodium lignosulphonate water solution, regulating the pH of the solution to be 10-13, and activating at 50-70 DEG C for 0.5-1.0 hour; adding an amination modifier, dropwise adding an aldehyde reagent, and reacting at 70-90 DEG C for 2-4 hours after the dropwise adding, so as to obtain an amino sodium lignosulphonate water solution; extracting the obtained amino sodium lignosulphonate water solution by virtue of an alcohol reagent, washing residual solids by virtue of petroleum ether after the extraction, and carrying out freeze drying on washed remnants. The amino sodium lignosulphonate prepared by virtue of the preparation method has remarkable pH response characteristic; by regulating the pH of the water solution of the product, the molecular configuration and the aggregation extent of the product can be changed, and a regular nanoparticle structure can be spontaneously formed; the amino sodium lignosulphonate can be used as a wall material to be applied field of pesticide microcapsules and is hopefully applied to the field of lignin-based nanometer materials.
Description
Technical field
The present invention relates to a kind of preparation method of pH response type amido sodium lignosulfonate and prepare pesticide micro capsule as wall material.Specifically with wood pulp or bamboo pulp sulfite pulping by product sodium lignosulfonate for raw material, in alkaline aqueous solution, carry out Mannich reaction with polyamine and aldehydes and prepare a kind of pH response type amido sodium lignosulfonate.
Background technology
Xylogen is the second largest natural reproducible resource of nature, is the valuable source of human future.Industrial xylogen raw material major part derives from paper industry.Up to now, the domestic xylogen more than 95%, is all directly enter rivers with " black liquor " form or burn after concentrating, is seldom utilized effectively.Xylogen enriches and reproducible Biological resources as one, especially when the nonrenewable resourceses such as current oil are day by day in short supply, causes the extensive concern of people gradually.Along with the raising of lignin product performance and continually developing of domestic market, its demand will constantly increase, and have good market application foreground.
Containing the abundant several functions group such as phenolic hydroxyl group, alcoholic extract hydroxyl group, carbonyl, carboxyl, methoxyl group, conjugated double bond in lignin molecule, all can there is many modified-reactions such as sulfomethylation, oxidation, methylolation, carboxymethylation, Mannich in its side chain and aromatic proton.These reactions can change space structure, molecular weight, content of phenolic hydroxyl groups, the carboxyl-content of xylogen or introduce other functional groups etc., thus improve the application performance of xylogen.
Research both at home and abroad about xylogen amination modifying is a lot, introduces and has the water-soluble and amine groups of positively charged, strengthen xylogen surfactivity, all have good effect in multiple field because of it.[the Peter Dilling such as Peter Dilling, Gamini S Samaranayake, StaciL Waldrop.Amine modified sulfonated alkali lignin for dispersedye.US:5972047, 1999 ?10 ?26.] use xylogen, formaldehyde and morpholine, tetramethyleneimine, the secondary amine reactions such as sarkosine, containing tertiary amine group in the modified lignin resin amine of synthesis, dye dispersant is it can be used as to find, the electronegativity of dispersion agent can not be affected when grinding in the basic conditions, but with positive charge under the acidic conditions of dyeing, in and the negative charge of sulfonate ion, add the coverage of dispersion agent on dyestuff surface, effectively protect dye granule.[the DurgaParajuli such as Durga Parajuli, Hidetaka Kawakita, et al.Recovery of Gold (III), Palladium (II), and Platinum (IV) AminatedLignin Derivatives.Ind.Eng.Chem.Res, 2006,45,6405 ?6412.] propose a kind of synthetic method of aminated lignin derivative, xylogen first obtains lignin phenol with phenol reactant, react with quadrol in the basic conditions after the lignin phenol obtained mixes with DMSO solution, be obtained by reacting amination lignin phenol product.Product being used for the noble metals such as gold recovering, palladium and platinum has good effect, and wherein the rate of recovery of gold element is the highest.
The patent No. be 96106784.5 Chinese invention patent disclose a kind of lignin modification synthesis quaternary cation flocculant technique.This modified technique have employed mannich condensation reaction and rabbet ammonium salt groups on xylogen skeleton, and then quaternary cation flocculant is prepared in alkylation, and last underpressure distillation is separated solvent and product.Products obtained therefrom of the present invention can be used for the multiple reluctant waste water such as dye wastewater treatment, dyeing waste water, has good percent of decolourization and COD clearance.The method is by after xylogen organic solvent dissolution, under strongly acidic conditions Mannich reaction occurs with aldehydes and ammonium component, then reacts with alkylating reagent and finally obtain lignin quaternary cation flocculant.This patent relates to amination modifying agent and aldehydes reagent, but xylogen raw material, reaction principle, purposes are all different from the present invention.
Patent CN103408767A discloses a kind of preparation method of the aminated lignin containing reactive amino, xylogen and epichlorohydrin reaction are first generated the epoxy xylogen containing multiple epoxide group by this invention, then this epoxy xylogen and polyamine compounds are reacted the aminated lignin prepared containing multiple primary amine groups and secondary amine isoreactivity group.Because it has good resistance toheat and reactive behavior, can become and prepare the good substrate material of macromolecule polymer material.
The amination reaction overwhelming majority at present about xylogen take all alkali lignin as raw material, seldom has the report about sulfonated lignin amination reaction, and does not all relate to its pH responsiveness.Sulfonated lignin are main components of liquid waste of pulping by sulfite process, are a kind of anion surfactants, have hydrophobe surfactivity, adsorb the good characteristics such as dispersed, sequestering, be industrially widely used.
Summary of the invention
One is the object of the present invention is to provide to have pH responsiveness, can the amido sodium lignosulfonate and preparation method thereof of the regular three-dimensional aggregate state Nano microsphere of spontaneous formation.
Another object of the present invention is to provide the application of amido sodium lignosulfonate in pesticide micro capsule.
Containing functional groups such as sulfonic group, phenolic hydroxyl group, alcoholic extract hydroxyl group, carboxylic acid group, carbonyl, methoxyl groups in sodium lignosulfonate, the present invention adopts Mannich graft reaction to access polyamines base in lignosulfonic acid sodium molecule, and preparation contains the amido sodium lignosulfonate of anion sulfoacid base and positively charged ion amido simultaneously.The amido sodium lignosulfonate of preparation has following physicochemical characteristic: by the pH of amido lignosulfonic acid sodium water solution, the charge distribution in its molecule, degree of ionization and water-soluble can be changed, and cause the change of aqueous solution Middle molecule configuration and aggregation extent, therefore this product molecule has significant pH responsiveness.The present invention also attempts the preparation pH response type amido sodium lignosulfonate of preparation being used for avermectin microcapsule.
The present invention is directed to sodium lignosulfonate and there is the sulfonic feature of strong acid cation ion group, amido cation group is grafted on lignosulfonic acid sodium molecule, make the amido sodium lignosulfonate of preparation simultaneously containing zwitterion group; And the degree of ionization by regulating the pH of product water solution to regulate and control amido sodium lignosulfonate cationic groups in one molecule, reach the charge distribution changing amido lignosulfonic acid sodium molecule, thus realize regulating and controlling its molecular configuration and aggregation extent, realize its pH responsiveness.Because the amido sodium lignosulfonate of preparation has pH responsiveness, the aggregate with regular three-dimensional net structure can be formed within the scope of certain pH, this characteristic therefore can be utilized to be applied to the preparation of nano material and microcapsule.
The object of the invention is to be achieved through the following technical solutions:
A preparation method for pH response type amido sodium lignosulfonate, comprises the following steps:
(1) lignosulfonic acid sodium water solution is mixed with by soluble in water for sodium lignosulfonate, pH to 10.0 ~ 13.0 of regulator solution, at 50 ~ 70 DEG C of activation 0.5 ~ 1.0h; Add amination modifying agent, then drip aldehydes reagent, after dropwising, at 70 ~ 90 DEG C of reaction 2 ~ 4h, obtain amido lignosulfonic acid sodium solution;
(2) in mass fraction, the amido lignosulfonic acid sodium solution alcohol reagent obtained is carried out extracting, residual solid thing after extracting uses petroleum ether again, and debris carries out lyophilize again, can obtain the powdery amido sodium lignosulfonate product of purifying;
Described amination reagent is diethylamine, propylene diamine, triethylamine, diethylenetriamine or triethylene tetramine;
Described aldehydes reagent is formaldehyde, acetaldehyde, propionic aldehyde, oxalic dialdehyde or glutaraldehyde;
Described alcohol reagent is one or more in methyl alcohol, ethanol, propyl alcohol, Virahol and butanols.
For realizing the object of the invention further, preferably, in mass fraction, described lignosulfonic acid sodium water solution is dissolved in 150 ~ 400 parts of water by 100 parts of sodium lignosulfonates being mixed with.
Preferably, in mass fraction, the add-on of described amination modifying agent is 20 ~ 200 parts.
Preferably, in mass fraction, the add-on of described part aldehydes reagent is 20 ~ 200 parts.
Preferably, in mass fraction, described dropping is in 0.5 ~ 1.0h, add 20 ~ 200 parts of aldehydes reagent.
Preferably, in mass fraction, described the amido lignosulfonic acid sodium solution alcohol reagent obtained to be carried out extracting be that the amido lignosulfonic acid sodium solution be obtained by reacting 100 parts carries out extracting with 100 ~ 300 parts of alcohol reagents.
Preferably, in mass fraction, described washing be by extracting after residual solid thing use 100 ~ 300 parts of petroleum ether again.
A kind of pH response type amido sodium lignosulfonate, is obtained by above-mentioned preparation method.
The application in pesticide micro capsule prepared by described amido sodium lignosulfonate.The amido sodium lignosulfonate prepared by aforesaid method can be used for preparing the Nano microsphere of particle diameter at about 100nm, and can be used as the wall material of pesticide micro capsule; When preparing avermectin microcapsule powder using it as wall material, the drug loading of the microcapsule of preparation can reach 41.33%, and it is 94% that bag rate of carrying reaches 86.97%, 72h cumulative release amount, and slow release effect is remarkable.
The present invention except sodium lignosulfonate all by pure content meter.
The present invention compared with prior art tool has the following advantages and effect:
1, the amido sodium lignosulfonate that prepared by the present invention has significant pH responsiveness, and raw material wood element sodium sulfonate does not then have pH responsiveness substantially; Product of the present invention gives the new chemical structure of sodium lignosulfonate and physicochemical characteristic, can widen Application Areas and the added value of product of sodium lignosulfonate.
2, the amido sodium lignosulfonate prepared of the present invention can spontaneous formation is regular within the scope of certain pH value of solution three-dimensional aggregate state Nano microsphere, this character can be utilized to prepare lignin-base nano material, widen the application of xylogen in field of nanometer material technology.
3, the amido sodium lignosulfonate that prepared by the present invention may be used for the preparation of pesticide micro capsule, its pH response characteristic contributes to its molecule to the embedding of pesticide molecule and release, and the reactive behavior of its amido can realize carrying out to wall material the microcapsule that crosslinking reaction prepares high-crosslinking-degree.
Accompanying drawing explanation
Fig. 1 is the nuclear magnetic spectrogram of embodiment 1 gained amido sodium lignosulfonate and sodium lignosulfonate.
Fig. 2 is the infrared spectrum of embodiment 1 gained amido sodium lignosulfonate and sodium lignosulfonate.
Fig. 3 is the reaction equation of sodium lignosulfonate grafting amination reagent.
Fig. 4 is embodiment 1 gained amido sodium lignosulfonate and the Zeta potential figure of sodium lignosulfonate under different pH.
Fig. 5 is embodiment 1 gained amido sodium lignosulfonate and the aggregate particle size figure of sodium lignosulfonate under different pH.
Fig. 6 is the transmission electron microscope picture of embodiment 1 gained amido sodium lignosulfonate in the DMSO aqueous solution of pH=6.0.
Fig. 7 is the microscope figure of avermectin microcapsule prepared by embodiment 1 gained amido sodium lignosulfonate, 96 × 72 μm.
Embodiment
Below in conjunction with drawings and Examples, the present invention is further illustrated, but embodiment does not form the restriction to the scope of protection of present invention.
Embodiment 1
(1) 100g sodium lignosulfonate is dissolved in 400g water, regulates pH to 12, in 50 DEG C of water-baths, activate 0.5h, add 50g diethylenetriamine, slowly drip 50g formaldehyde, dropwise in 0.5h, be warming up to 70 DEG C, continue reaction 4h, obtain amido lignosulfonic acid sodium solution;
(2) with 100mL ethanolic extraction amido lignosulfonic acid sodium solution, then filter by 300mL petroleum ether, lyophilize obtains powdery amido sodium lignosulfonate.
Fig. 1 is the nucleus magnetic hydrogen spectrum figure of sodium lignosulfonate and amido sodium lignosulfonate.Can obviously find out from figure, compared with sodium lignosulfonate, amido sodium lignosulfonate weakens to some extent at the aromatic protons peak of chemical shift 6.50 ~ 7.50ppm, significantly strengthens in the alkyl proton peak be connected with N element of 2.50 ~ 3.00ppm.Can illustrate thus, amination reagent is successfully grafted on sodium lignosulfonate.
Fig. 2 is the infrared spectrum of sodium lignosulfonate and amido sodium lignosulfonate, contrast raw material wood element sodium sulfonate and amido sodium lignosulfonate known, the 2850cm of amido sodium lignosulfonate
?1chu ?CH
2?stretching vibration absorption peak and 1419cm
?1?CH
2?singly-bound vibration absorption peak strengthening all to some extent than sodium lignosulfonate.Meanwhile, at 1512cm
?1and 1036cm
?1?NH
2absorption peak also strengthens to some extent compared with raw material.According to this infrared spectrogram, can illustrate that amination reagent is successfully grafted on sodium lignosulfonate.
According to the characterization result of Fig. 1 and Fig. 2, infer the reaction equation of sodium lignosulfonate and amination reagent as shown in Figure 3.As seen from Figure 3, containing anionic sulfonic group and cationic amido hydrophilic group in the amido lignosulfonic acid sodium molecule that modification obtains, noticeable change is there is in the ionization character of these two kinds of hydrophilic groups along with the change of pH value of solution, thus cause the physico-chemical properties such as this amido sodium lignosulfonate particle diameter in aqueous, Zeta potential, aggregate state also to change, as shown in Figure 4, Figure 5 and Figure 6.
Fig. 4 is the Zeta potential curve that in the aqueous solution, sodium lignosulfonate and amido sodium lignosulfonate change with pH.Sodium lignosulfonate Zeta potential within the scope of tested pH change little ?about 30mV fluctuate, the Zeta potential absolute value of amido sodium lignosulfonate then first reduces rear increase with pH change, this is because along with the reduction of pH, amine radical ion ionizes gradually, shielding effect is risen to part sulfonate radical, thus system negative charge amount constantly reduces.
Fig. 5 is the grain size curve that in the aqueous solution, sodium lignosulfonate and amido sodium lignosulfonate change with pH.In test specification, the particle diameter of sodium lignosulfonate does not have considerable change equally, and the particle diameter of amido sodium lignosulfonate is then along with first the diminishing by a small margin of reduction of pH sharply increases again.When pH reduces, amine root ionizes gradually, and intramolecular zwitterion combines, molecular structure shrinks, and therefore particle diameter first declines by a small margin, and reduces further along with pH, amine radical ion increases rapidly, and form rapidly large aggregate because strengthening with intermolecular electrostatic effect in molecule, particle diameter increases fast.As can be seen from Figure, particle diameter first drops to the 50nm of pH=8 from the 200nm of pH=9, then increases to rapidly the 3500nm of pH=7.
Fig. 6 is the accumulation shape of amido sodium lignosulfonate in the pure water (a) and dimethyl sulphoxide aqueous solution (b) of pH=7.0.Amido sodium lignosulfonate embodiment 1 obtained is dissolved in pure water and dimethyl sulfoxide (DMSO) respectively, then slowly rare HCl aqueous solution is dripped while stirring, regulator solution pH=7.0, amido sodium lignosulfonate generation molecular configuration change in solution, in pure water, form netted aggregate, then can assemble in dimethyl sulfoxide (DMSO) and form particle diameter at about 100nm Nano microsphere.This is because amido sodium lignosulfonate intermolecular zwitterion combines formation aggregate when pH reduces, and this aggregate is water insoluble and can be dissolved in dimethyl sulfoxide (DMSO), so there is different accumulation shapes at different solvent systems, in pure water, become three-dimensional netted aggregate, in dimethyl sulphoxide aqueous solution, then can form comparatively regular microballoon.
Fig. 4,5, the result of 6 shows, by regulating the mode of pH to regulate and control cationic degree of ionization, can realize the pH responsiveness of amido sodium lignosulfonate.
Fig. 7 is the microscope figure of the avermectin microcapsule adopting amido sodium lignosulfonate to prepare.Amido sodium lignosulfonate embodiment 1 obtained is as wall material, mix in water with the Avrmectin as core, regulate aqueous solution pH to 6, amido sodium lignosulfonate generation aggregation forms tridimensional network by Avrmectin particle encapsulation interior, form micron-scale microcapsule, as shown in Figure 7, the microcapsule size of preparation is homogeneous, particle diameter at about 3 μm, and is evenly distributed.Gained avermectin microcapsule drug loading 41.33%, bag carries rate 86.97%; Compared with former medicine, slow release effect is obvious, and under same test condition, namely release is complete in 10min for former medicine, and microcapsule product 72h cumulative release amount is 94%.
Wherein the testing method of drug loading and bag year rate is as follows:
(1) precise certain mass microcapsule sample (being accurate to 0.0001g), join in the about 50mL 50%DMF aqueous solution, then use the broken 10min of cell crushing instrument, then the suspension obtained is transferred in 500mL volumetric flask, use ethanol constant volume, then leave standstill 24h.
(2) get a certain amount of volumetric flask clear liquid at the middle and upper levels, after filtering with 0.45 μm of aqueous phase filtering head, adopt the former medicine content in high effective liquid chromatography for measuring filtrate.Drug loading and bag year rate according to following formulae discovery microcapsule:
Drug loading=(microcapsule Central Plains medicine quality)/(microcapsule total mass) × 100%
Bag carries rate=(microcapsule total mass) × (drug loading)/(microcapsule Central Plains medicine theoretical value) × 100%.
Embodiment 2
(1) 100g sodium lignosulfonate is dissolved in 150g water, regulates pH to 10, in 60 DEG C of water-baths, activate 1.0h, add 20g triethylamine, slowly drip 20g acetaldehyde, dropwise in 1h, be warming up to 80 DEG C, continue reaction 2h, obtain amido lignosulfonic acid sodium solution;
(2) with 200mL methyl alcohol extracting amido lignosulfonic acid sodium solution, then filter by 200mL petroleum ether, lyophilize obtains powdery amido sodium lignosulfonate.
Embodiment 3
(1) 100g sodium lignosulfonate is dissolved in 200g water, regulates pH to 11, in 70 DEG C of water-baths, activate 1.0h, add 200g diethylamine, slowly drip 200g propionic aldehyde, dropwise in 1h, be warming up to 90 DEG C, continue reaction 3h, obtain amido lignosulfonic acid sodium solution;
(2) with 300mL propyl alcohol extracting amido lignosulfonic acid sodium solution, then filter by 200mL petroleum ether, lyophilize obtains powdery amido sodium lignosulfonate.
Embodiment 4
(1) 100g sodium lignosulfonate is dissolved in 300g water, regulates pH to 13, in 50 DEG C of water-baths, activate 0.5h, add 100g triethylene tetramine, slowly drip 100g glutaraldehyde, dropwise in 0.5h, be warming up to 70 DEG C, continue reaction 2h, obtain amido lignosulfonic acid sodium solution;
(2) with 200mL Virahol extracting amido lignosulfonic acid sodium solution, then filter by 100mL petroleum ether, lyophilize obtains powdery amido sodium lignosulfonate.
Embodiment 5
(1) 100g sodium lignosulfonate is dissolved in 300g water, regulates pH to 12, in 60 DEG C of water-baths, activate 0.5h, add 150g propylene diamine, slowly drip 150g oxalic dialdehyde, dropwise in 1h, be warming up to 80 DEG C, continue reaction 4h, obtain amido lignosulfonic acid sodium solution;
(2) with 300mL butanols extracting amido lignosulfonic acid sodium solution, then filter by 100mL petroleum ether, lyophilize obtains powdery amido sodium lignosulfonate.
Compared with embodiment 1, amination reagent used, aldehydes reagent and consumption thereof in embodiment 2 ~ 5, temperature of reaction, reaction times are different, and this can have an impact to its graft effect, but principle is identical, the product property obtained is also close, is therefore no longer elaborated here.
Claims (9)
1. a preparation method for pH response type amido sodium lignosulfonate, is characterized in that comprising the following steps:
(1) lignosulfonic acid sodium water solution is mixed with by soluble in water for sodium lignosulfonate, pH to 10.0 ~ 13.0 of regulator solution, at 50 ~ 70 DEG C of activation 0.5 ~ 1.0h; Add amination modifying agent, then drip aldehydes reagent, after dropwising, at 70 ~ 90 DEG C of reaction 2 ~ 4h, obtain amido lignosulfonic acid sodium solution;
(2) the amido lignosulfonic acid sodium solution alcohol reagent obtained is carried out extracting, the residual solid thing after extracting uses petroleum ether again, and debris carries out lyophilize again, can obtain the powdery amido sodium lignosulfonate product of purifying;
Described amination reagent is diethylamine, propylene diamine, triethylamine, diethylenetriamine or triethylene tetramine;
Described aldehydes reagent is formaldehyde, acetaldehyde, propionic aldehyde, oxalic dialdehyde or glutaraldehyde;
Described alcohol reagent is one or more in methyl alcohol, ethanol, propyl alcohol, Virahol and butanols.
2. the preparation method of pH response type amido sodium lignosulfonate according to claim 1, is characterized in that, in mass fraction, described lignosulfonic acid sodium water solution is dissolved in 150 ~ 400 parts of water by 100 parts of sodium lignosulfonates being mixed with.
3. the preparation method of pH response type amido sodium lignosulfonate according to claim 1, is characterized in that, in mass fraction, the add-on of described amination modifying agent is 20 ~ 200 parts.
4. the preparation method of pH response type amido sodium lignosulfonate according to claim 1, is characterized in that, in mass fraction, the add-on of described part aldehydes reagent is 20 ~ 200 parts.
5. the preparation method of pH response type amido sodium lignosulfonate according to claim 1, is characterized in that, in mass fraction, described dropping is in 0.5 ~ 1.0h, add 20 ~ 200 parts of aldehydes reagent.
6. the preparation method of pH response type amido sodium lignosulfonate according to claim 1, it is characterized in that, in mass fraction, described the amido lignosulfonic acid sodium solution alcohol reagent obtained to be carried out extracting be that the amido lignosulfonic acid sodium solution be obtained by reacting 100 parts carries out extracting with 100 ~ 300 parts of alcohol reagents.
7. the preparation method of pH response type amido sodium lignosulfonate according to claim 1, is characterized in that, in mass fraction, described washing be by extracting after residual solid thing use 100 ~ 300 parts of petroleum ether again.
8. a pH response type amido sodium lignosulfonate, is characterized in that: it is obtained by the preparation method described in any one of claim 1 ?7.
9. the application in pesticide micro capsule prepared by amido sodium lignosulfonate according to claim 8.
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