CN103554510B - A kind of Amino End Group modified-cellulose and its preparation method and application - Google Patents
A kind of Amino End Group modified-cellulose and its preparation method and application Download PDFInfo
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Abstract
The invention discloses a kind of Amino End Group modified-cellulose and its preparation method and application, first in concentrated base, soak 10 hours more than by through cleaning-drying to the bagasse raw material of constant weight, after washing, suction filtration, oven dry, obtain alkali baggasse fiber; Then under lucifuge condition, be there is oxidizing reaction in alkali baggasse fiber and strong oxidizer and obtain dialdehyde bagasse cellulose; Then with methyl methacrylate and quadrol for raw material, stir polymerization reaction take place under lucifuge, oxygen barrier condition in organic solvent and obtain Hyperbranched Polymer with Terminal Amido; Carry out back flow reaction after finally dialdehyde bagasse cellulose and Hyperbranched Polymer with Terminal Amido being dissolved in organic solvent and can obtain amine-terminated hyperbranced thing grafting dialdehyde cellulose.Not only there is good absorption property to the heavy metal ion in waste water solution through modified Mierocrystalline cellulose, and be easy to after absorption be separated, thus there is method purifying water effect simple, with low cost.
Description
Technical field
The invention belongs to field of organic polymer compound, be specifically related to a kind of Amino End Group modified-cellulose and its preparation method and application.
Background technology
Heavy metal is the persistent pollutant with potential hazard, due to heavy metal ion difficult degradation, and can accumulate enrichment in fish and farm crop tissue, by food chain effect, can produce harm to people.In heavy metal containing wastewater treatment, carry out environmentally safe medicament or at short notice environment can get along alone reason the development & application of medicament, the development & application of nontoxic new type water reagent treatment etc. research significant.
At present in the process of heavy metal wastewater thereby, main sorbent material or the sorbing material of still leaning on is by removal settlement separate after the heavy metal adsorption of ionic state.In recent years, prepare high-absorption material with cellulose and its derivates and obtain increasing attention in PRODUCTION TRAITS at home and abroad, wherein the cellulosic report of nitrogen containing plasma chelating type is also very many.The nineties in 20th century, Chen Guanzhan regenerated cellulose is matrix, is acted on, obtained a kind of spherical regenerated cellulose amidoxim resin by vinyl cyanide addition in the methanol solution of azanol, and have studied its absorption property to part heavy metal.Zeng Qingru take rice husk cellulose as skeleton, and grafting quadrol after alkalization, epoxidation, prepares nitrogen-containing fiber element, and discusses the absorption property of this nitrogen-containing fiber element to Cr6+ and Cu2+.Absorbent cotton after epoxidation, reacts with two seed amino acids by Meng Lingzhi respectively, obtained two kinds of porous cellulose spheres amino acid derivative, they are to transition metal and heavy metal ion, especially have good adsorption effect to poisonous Hg2+, and along with the increase of pH value, loading capacity increases.Wang Gehui cotton fibre, as raw material, through alkalization, reacts with diethylenetriamine, triethylene tetramine, tetraethylene pentamine respectively after epoxidation process, has obtained three polyamine species class ion chelating agents, and have studied its adsorption and desorption behavior to Cu2+.Ji Chunnuan is with carboxymethyl cellulose and quadrol-glycerol epoxy resin for raw material, and synthesized a kind of novel weak acid and weak base type gabion type resin, this resin is to Cu
2+, Ni
2+, Pb
2+, Zn
2+loading capacity can reach 1.72 respectively, and 0.43,0.37 and 0.13mmol/g.Abroad, Moritam take wood chip as raw material, and react with itself and amidoxim and prepare amidoxime type wood chip sorbent material, this sorbing material can extract the uranium metal in seawater.
Amino compound, as primary amine groups, secondary amino group, pyridine compounds and their etc., has the characteristic of harmful anion in planar water.Meanwhile, the lone-pair electron in primary amine groups can metallic cation in planar water.Therefore, modify upper this kind of group on cellulose, can heavy metal cation effectively in planar water, reach the object purified water.
Amine-terminated hyperbranced compound is a kind of highly branched, containing the water-soluble mono dispersed polymeres enriching amino and imino-, is grafted on cellulosic molecule and makes it have water-fast character.Recycle its coordination ability that is amino and imino-, form inner complex to reach the object of heavy-metal ion removal with the heavy metal ion in waste water.
Application Number (patent) CN200710191878.8 discloses a kind of amine-terminated hyperbranced compound quaternary ammonium salt and preparation method thereof, belongs to technical field of polymer materials.The method adopts amine-terminated hyperbranced compound to be parent, by the polyquaternium that quaternized for the amino on its surface or grafting quaternary ammonium salt side chain obtain.Preparation method is: be dissolved in deionized water by amine-terminated hyperbranced compound, then adds a certain amount of quaternizing agent, can both be had over-expense compound characteristic after stirring, and has again the polyquaternium of polycation feature simultaneously.Its building-up process is simple, synthesis cost is lower, product can be used for cellulosic fibre, protein fibre cation-modified, realize the salt-free dyeing of reactive dyestuffs, substantive dyestuff, matching stain, chrome dye etc., improve anti-microbial property and the uvioresistant performance of fabric, be applicable to sewage-treating agent, antiseptic-germicide, tensio-active agent, functional materials precursor, medical carrier etc. simultaneously.
Application Number (patent): CN201310039208.X discloses silicon oil modified amine-terminated hyperbrancedization polyamide resin of Amino End Group and preparation method thereof and application, the method is made up of following steps: diprotic acid and trimeric cyanamide are mixed post-heating to 70 ~ 90 DEG C, adds Amino End Group silicone oil and dimethylbenzene; Heat 1 ~ 3h at 180 ~ 210 DEG C after, be warming up to 220 ~ 240 DEG C, after heating 1 ~ 3h; Be cooled to 90 DEG C, organic solvent, silicone oligomer and crosslinking catalyst; Be heated to 110 ~ 120 DEG C, heating 2 ~ 3h; Be cooled to 90 DEG C, finally adding organic solvent adjustment solid content is 60 ~ 70%.The method will add Amino End Group silicone oil when synthesizing amine-terminated hyperbrancedization polymeric amide, improve resistance toheat and the snappiness of polymeric amide; Silicone oligomer and polymeric amide are carried out crosslinking reaction, improves the resistance toheat of polymeric amide.Resin prepared by the method for the invention may be used for preparing high temperature resistant low surface energy coatings.
Application Number (patent): CN02111578.8 discloses end-amino water-soluble ultrabranching polyamide and preparation method thereof.The preparation method of end-amino water-soluble ultrabranching polyamide is as follows: step (a): by the monomer A B containing double bond (the present invention claims A group) and carboxyl or ester group (the present invention claims B group) with containing two or more amino monomers, (the present invention claims polyamino monomer; referred to as Cn type monomer; wherein n >=2) direct reaction; solvent for use is aprotic solvent; temperature of reaction is-50 DEG C ~ 100 DEG C, and the reaction times is 1 minute to 15 days; Step (b): step (a) gained mixture is warming up to 50 DEG C ~ 280 DEG C, decompression is lower continues reaction 5 minutes to 10 days, obtained ultrabranching polyamide.Resulting polymers contains a large amount of Amino End Group, water soluble and organic solvent, degradable, suitable matrix, antioxidant, sterilant, tensio-active agent, the stream doing efficient coating, linking agent, biological medicine carrier, immobilized enzyme and protein becomes processing additives, functional materials precursor etc., has a wide range of applications.
Above in disclosed document, existing sorbent material (comprising amine-terminated hyperbranced compound) has following some shortcomings part:
1. adsorption effect affects comparatively large by environment pH, and peracid or excessively alkali all can cause the reduction of the removal capacity of sorbent material (comprising amine-terminated hyperbranced compound) heavy metal ion.And in actual applications, the pH of solution is a more random factor, not easily regulate, thus affect the removal effect of sorbent material (comprising amine-terminated hyperbranced compound) heavy metal.
2. " desorption " effect after absorption is not ideal enough.Namely sorbent material recycling rate is lower.
3. adsorpting type is single.In actual production, the heavy metal cation often both containing positively charged in waste water, again containing aobvious electronegative harmful organic waste; And existing sorbent material (comprising amine-terminated hyperbranced compound) only can process a kind of electrical toxic substance mostly, as only can the cationic anion adsorbent of Adsorption of Heavy Metals, and only can adsorb harmful organic cation adsorbent.
Summary of the invention
The object of the invention is to for the deficiencies in the prior art, provide that a kind of production cost is low, advantages of good adsorption effect, high adsorption capacity desorption are easy to Amino End Group modified-cellulose and its preparation method and application.The present invention studies the modification technology of bagasse cellulose, has synthesized amine-terminated hyperbranced Mierocrystalline cellulose, and is applied to absorption mixture-metal waste water solution with the modified product of synthesis.
To achieve these goals, present invention employs following technical scheme:
A kind of Amino End Group modified-cellulose, this Mierocrystalline cellulose is: amine-terminated hyperbranced thing grafting dialdehyde cellulose; Its skeleton symbol is:
The structural unit of the CELL described in formula is:
Described HBPN is Hyperbranched Polymer with Terminal Amido, and its skeleton symbol is:
The amine-terminated hyperbranced thing grafting dialdehyde cellulose structural formula obtained after being replaced by CELL and HBPN structural formula is:
Prepare a method for described Amino End Group modified-cellulose, its processing step is:
(1) raw materials pretreatment: soak more than 10 hours by through cleaning-drying to the bagasse raw material of constant weight in concentrated base, obtain alkali baggasse fiber after washing, suction filtration, oven dry;
(2) dialdehyde bagasse cellulose preparation: oxidizing reaction is occurred under lucifuge condition for alkali baggasse fiber and strong oxidizer and obtains dialdehyde bagasse cellulose;
(3) synthesis of Hyperbranched Polymer with Terminal Amido: with methyl methacrylate and quadrol for raw material, stir polymerization reaction take place under lucifuge, oxygen barrier condition in organic solvent and obtain Hyperbranched Polymer with Terminal Amido;
(4) amine-terminated hyperbranced thing grafting dialdehyde cellulose synthesis: carry out back flow reaction after dialdehyde bagasse cellulose and Hyperbranched Polymer with Terminal Amido being dissolved in organic solvent and can obtain amine-terminated hyperbranced thing grafting dialdehyde cellulose.
The present invention prepares the reaction mechanism of the method for described Amino End Group modified-cellulose:
Raw materials pretreatment mechanism: in bagasse except the Mierocrystalline cellulose needed for experiment, the impurity also containing a large amount of xylogen and five-carbon sugar, ash content.The existence of these impurity can have influence on chemical reagent to cellulosic effective modification, and with reagent, the side reaction of various complexity may occur.Simultaneously, a large amount of crystalline structures is there is in natural cellulose supramolecular structure, these " crystallizing fields " be by the hydroxyl (-OH) of three in the repeating unit of each cellulosic molecule mutually by Robert Van de Walle hereby power form hydrogen bond and be formed by connecting, the energy of cellulosic molecule entirety can be reduced like this, Mierocrystalline cellulose can be existed in occurring in nature long-term stability.
But utilize these hydroxyls to carry out the chemist of graft modification for wanting, these regions are " regions that chemical reagent cannot arrive ", and namely inside, crystallizing field is almost without chemically reactive, be the unfavorable factor of impact to cellulose chemistry modification.For cellulosic chemical modification reaction, the speed of reaction of whole reaction depend mainly on reaction reagent penetrate into non-crystalline region and surface, crystalline region can and hydroxyl on speed, or reaction product is diffused into the speed in solubility bulk solution, to reaction reagent and product penetration, diffusion play a decisive role be in cellulose molecular chain diameter 5.0 × 10
-9the micropore number of m and Crystalline size.
Therefore, we will carry out suitable pre-treatment to the baggasse fiber raw material obtained, the crystalline region abolished in Mierocrystalline cellulose supramolecule as much as possible, the present invention uses concentrated base to carry out immersion treatment to Bagasse Material, while destruction crystal region, also eliminate the impurity such as a large amount of xylogen, and then obtain alkali baggasse fiber (being called for short MB).
Dialdehyde bagasse cellulose (being called for short DABC) preparation principle: the o-dihydroxy in alkali baggasse fiber structure and strong oxidizer are (as HIO
4) there is high-selectivity oxidation reaction, its product dialdehyde Mierocrystalline cellulose prepares not containing the raw material of glucose ring skeleton novel cellulose derivative, utilize the reactive behavior of aldehyde radical, the functional high molecule materials such as there is fluorescence, energy storage, sequestrant and bio-medical can be obtained.Its reaction equation and relevant reaction mechanism as follows:
Described
be DABC, the structure after its simplification is:
The composition principle of Hyperbranched Polymer with Terminal Amido: with AB3 and the AB2 type monomer of methyl methacrylate and the quadrol yellow transparent that has been Material synthesis, then pass through further polyreaction, synthesized Hyperbranched Polymer with Terminal Amido (HBPN).This material is photosensitive material, therefore, should note lucifuge, low temperature place short-term preservation, should not place for a long time during preservation.(see: Zhang Feng, Chen Yuyue, etc. the fabrication & properties of Hyperbranched Polymer with Terminal Amido and quaternary ammonium salt thereof. polymer material science and engineering, 2009,25 (8)), the equation of reaction is as follows:
Amine-terminated hyperbranced thing grafting dialdehyde cellulose composition principle: because bagasse cellulose supramolecule itself has " crystalline region " of more passivation, although even if add through the content of pretreated alkali bagasse cellulose free hydroxyl group, but the repeating unit of cellulose macromolecule is pyrans ring texture, still have larger sterically hindered, for to grafting polymer compound H BPN on its ring, can infer, its difficulty is larger.
The present invention selects DABC as carrier, and compared with Bagasse Material (RB) or MB, the oxidized part of DABC is linear structure, and the carbon-carbon bond fracture between C2 and C3, six-membered cyclic is destructurized, changes linear molecule into.Greatly reduce the sterically hindered of carrier molecule (bagasse cellulose), make graft reaction become possibility.By the reactional equation on HBPN grafting and DABC be:
Described
be amine-terminated hyperbranced thing grafting dialdehyde cellulose, referred to as HBPN-g-DABC.
In order to prove the success of Amino End Group modification further, analyzing the infrared spectra of three kinds of materials MB, DABC and HBPN-g-DABC, the results are shown in Figure 1.Contrasted from wave number, have relative to the absorption wavenumber of MB, HBPN-g-DABC and changed, known-NH
2at wave number 3300 ~ 3400cm
-1place is a very sharp-pointed peak.By relatively finding out, at 3400cm
-1the peak at place becomes sharp-pointed, and the success of polyamino modification bagasse is described from another side.
Invention product is carried out infrared spectra to carry out analysis and can obtain: at 3336.15cm
-1place, occur the absorption peak of N-H medium tenacity, this peak is the stretching vibration peak of N-H; At 1652.64cm
-1absorption peak be-NH
2vibration absorption peak; At 1456.60cm
-1what occur be structure is-N-CH
2-vibration absorption peak.
Total nitrogen content and infrared absorpting light spectra in comprehensive analysis polyamino modification bagasse, can determine to adopt the method in this research to carry out polyamino modification success to bagasse sorbent material.
Through carrying out Infrared spectroscopy, ultimate analysis to product, confirm that the structure of the product that the present invention obtains is:
Above-described concentrated base is 5 ~ 80%(Wt%) more than the alkaline solution of first family metallic element; The bath raio of described concentrated base and bagasse raw material is 8 ~ 100 (V/W).
Above-described strong oxidizer is KIO
4, H
5iO
6, NaIO
4, Pb (OAc)
4in any.According to the general knowledge that those of ordinary skill in the art grasp, the amount that strong oxidizer adds is generally as a little, 0.5 ~ 5% (wt%) of about alkali baggasse fiber weight.
Above-described oxygen barrier condition is for pass into N in the reaction
2or rare gas element.
Above-described organic solvent is C
4any one following alcoholic solution or their combination.
The back flow reaction of above-described amine-terminated hyperbranced thing grafting dialdehyde cellulose synthesis is the organic solution slowly dripping Hyperbranched Polymer with Terminal Amido in the organic solution of dialdehyde bagasse cellulose.
The application of described Amino End Group modified-cellulose, this Mierocrystalline cellulose is applied to the heavy metal adsorption to ionic state.
HBPN itself is water-soluble, if be therefore directly used as metal biosorption in water surrounding, the more difficult separation of adsorbed product.Now the hyperbranched compound of synthesis is grafted in non-water-soluble bagasse cellulose, take bagasse as carrier, not only make use of " capturing ability " that Amino End Group is excellent to metal ion, and adsorbed product is solid particulate, just itself and the aqueous solution can be separated by simple filter operation.
The application of above-described Amino End Group modified-cellulose, described heavy metal comprises the combination of any or they in copper, lead, zinc, tin, nickel, cobalt, antimony, mercury, cadmium and bismuth.
The application of above-described Amino End Group modified-cellulose, described heavy metal comprises the combination of any or they in copper, lead, mercury, cadmium.
Advantage of the present invention:
1. select bagasse to be raw material, not only reduce production cost, also substantially increase the added value of bagasse processing.Sugarcane is a kind of Featured crops of generally planting in Guangxi, and its juice can be used for refining sugar, and the bagasse remained by sugaring is used for papermaking, and its added value of product is not high, and pollutes large.Bagasse primarily of Mierocrystalline cellulose, hemicellulose and xylogen three part composition, wherein, Mierocrystalline cellulose is in molecule and under intermolecular hydrogen bonding effect, form microcrystalline cellulose silk, its essentially consist is that α-D-Glucopyranose is with β – D-Glucopyranose, glucose connects into chain molecule by glycosidic link, and water-soluble rear cooling is intermolecular with hydrogen bonded.The present invention it can be used as the raw material of Amino End Group modified-cellulose, and compared with general method, Mierocrystalline cellulose is pollution-free, readily biodegradable, and wide material sources are cheap.
2. Amino End Group modified-cellulose of the present invention, introduce acidity, alkalescence or sequestering ionic group on cellulose, the original character of Mierocrystalline cellulose can be changed, make it have the feature of ion exchange resin, the advantages such as cellulosic porous, specific surface area are large can be ensured again.
3. Amino End Group modified-cellulose of the present invention is used for the absorption of heavy metal ion, has advantages of good adsorption effect, affect less by environment pH, the removal effect of heavy metal is good; Adsorption efficiency is high, and general only needs can reach adsorption equilibrium in 10 minutes; Adsorption of Heavy Metal Ions kind is many, and can realize adsorbing contents of many kinds of heavy metal ion simultaneously, can also adsorb harmful organic positively charged ion simultaneously; Desorption is easy to after absorption, during desorption only need by filter the absorption that obtain after a small amount of 3%HCl of baggasse fiber of metal ion soaks 30min, filter, then use suction filtration after a small amount of 5%NaOH solution soaking 30min, then with distilled water, filter residue is washed till neutrality, at 60 DEG C, is dried to constant mass.
4., through testing discovery further, the better heat stability of product, more easily preserves.Without the need to special storage equipment, can place for a long time and undergo no deterioration or affect its adsorption effect in atmosphere.
Accompanying drawing explanation
Accompanying drawing 1 is the infrared spectra of MB, DABC and HBPN-g-DABC.
1,2,3 infrared spectras being followed successively by MB, DABC and HBPN-g-DABC in figure.
Embodiment
Below in conjunction with embodiment, the present invention further illustrates, but protection scope of the present invention is not limited to these embodiments.
Embodiment 1:
Prepare the method for described Amino End Group modified-cellulose, its processing step is:
(1) raw materials pretreatment: by through cleaning-drying to the bagasse raw material of constant weight at 3%(Wt%) lithium hydroxide concentrated alkali solution; The bath raio of described concentrated base and bagasse raw material is 5 (V/W)) in soak more than 10 hours, obtain alkali baggasse fiber after washing, suction filtration, oven dry;
(2) dialdehyde bagasse cellulose preparation: by alkali baggasse fiber and the strong oxidizer (KIO accounting for alkali baggasse fiber weight 0.3%
4) oxidizing reaction occurs under lucifuge condition obtain dialdehyde bagasse cellulose;
(3) synthesis of Hyperbranched Polymer with Terminal Amido: with methyl methacrylate and quadrol for raw material, (pass into N in the reaction under lucifuge, oxygen barrier condition in methyl alcohol
2) stir polymerization reaction take place obtain Hyperbranched Polymer with Terminal Amido;
(4) amine-terminated hyperbranced thing grafting dialdehyde cellulose synthesis: carry out back flow reaction (for slowly dripping the organic solution of Hyperbranched Polymer with Terminal Amido in the organic solution of dialdehyde bagasse cellulose) after dialdehyde bagasse cellulose and Hyperbranched Polymer with Terminal Amido being dissolved in organic solvent and can obtain amine-terminated hyperbranced thing grafting dialdehyde cellulose.
By analyzing the infrared spectra of three kinds of materials MB, DABC and HBPN-g-DABC, the results are shown in Figure 1.Contrasted from wave number, have relative to the absorption wavenumber of MB, HBPN-g-DABC and changed, known-NH
2at wave number 3300 ~ 3400cm
-1place is a very sharp-pointed peak.By relatively finding out, at 3400cm
-1the peak at place becomes sharp-pointed, and the success of polyamino modification bagasse is described from another side.
Invention product is carried out infrared spectra to carry out analysis and can obtain: at 3336.15cm
-1place, occur the absorption peak of N-H medium tenacity, this peak is the stretching vibration peak of N-H; At the vibration absorption peak that the absorption peak of 1652.64cm-1 is-NH2; At 1456.60cm
-1what occur be structure is-N-CH
2-vibration absorption peak.
Total nitrogen content and infrared absorpting light spectra in comprehensive analysis polyamino modification bagasse, can determine to adopt the method in this research to carry out polyamino modification success to bagasse sorbent material.
Through carrying out Infrared spectroscopy, ultimate analysis to reactant and product, confirm that the structure of the product that the present invention obtains is:
The amine-terminated hyperbranced thing grafting dialdehyde cellulose prepared is carried out the adsorption applications of heavy metal ion:
The application of described Amino End Group modified-cellulose, this Mierocrystalline cellulose is applied to the heavy metal adsorption to ionic state: Amino End Group modified-cellulose of the present invention is placed in cadmium-ion solution, adsorption equilibrium is reached through detecting after 10 minutes, analyze the concentration of heavy metal in the solution before and after absorption, adsorption rate reaches as high as 87.5%.
Embodiment 2:
Prepare the method for described Amino End Group modified-cellulose, its processing step is:
(1) raw materials pretreatment: by through cleaning-drying to the bagasse raw material of constant weight at 5%(Wt%) sodium hydroxide concentrated alkali solution; The bath raio of described concentrated base and bagasse raw material is 8 (V/W)) in soak more than 15 hours, obtain alkali baggasse fiber after washing, suction filtration, oven dry;
(2) dialdehyde bagasse cellulose preparation: by alkali baggasse fiber and the strong oxidizer H accounting for alkali baggasse fiber weight 0.5%
5iO
6under lucifuge condition, there is oxidizing reaction obtain dialdehyde bagasse cellulose;
(3) synthesis of Hyperbranched Polymer with Terminal Amido: with methyl methacrylate and quadrol for raw material, under lucifuge, oxygen barrier condition, (passing into helium in the reaction) is stirred polymerization reaction take place and obtained Hyperbranched Polymer with Terminal Amido in ethanol;
(4) amine-terminated hyperbranced thing grafting dialdehyde cellulose synthesis: carry out back flow reaction (for slowly dripping the organic solution of Hyperbranched Polymer with Terminal Amido in the organic solution of dialdehyde bagasse cellulose) after dialdehyde bagasse cellulose and Hyperbranched Polymer with Terminal Amido being dissolved in organic solvent and can obtain amine-terminated hyperbranced thing grafting dialdehyde cellulose.
Through carrying out Infrared spectroscopy, ultimate analysis to reactant and product, obtaining the same conclusion, amino modified success can be proved, and obtain the product the same with embodiment 1 structure.
The amine-terminated hyperbranced thing grafting dialdehyde cellulose prepared is carried out the adsorption applications of heavy metal ion:
The application of described Amino End Group modified-cellulose, this Mierocrystalline cellulose is applied to the heavy metal adsorption to ionic state: Amino End Group modified-cellulose of the present invention is placed in copper ion solution, adsorption equilibrium is reached through detecting after 10 minutes, analyze the concentration of heavy metal in the solution before and after absorption, adsorption rate reaches as high as 90.5%.
Embodiment 3:
Prepare the method for described Amino End Group modified-cellulose, its processing step is:
(1) raw materials pretreatment: by through cleaning-drying to the bagasse raw material of constant weight at 10%(Wt%) potassium hydroxide concentrated alkali solution; The bath raio of described concentrated base and bagasse raw material is 10 (V/W)) in soak more than 20 hours, obtain alkali baggasse fiber after washing, suction filtration, oven dry;
(2) dialdehyde bagasse cellulose preparation: by alkali baggasse fiber and the strong oxidizer (NaIO accounting for alkali baggasse fiber weight 0.8%
4) oxidizing reaction occurs under lucifuge condition obtain dialdehyde bagasse cellulose;
(3) synthesis of Hyperbranched Polymer with Terminal Amido: with methyl methacrylate and quadrol for raw material, under lucifuge, oxygen barrier condition, (passing into neon in the reaction) is stirred polymerization reaction take place and obtained Hyperbranched Polymer with Terminal Amido in propyl alcohol;
(4) amine-terminated hyperbranced thing grafting dialdehyde cellulose synthesis: carry out back flow reaction (for slowly dripping the organic solution of Hyperbranched Polymer with Terminal Amido in the organic solution of dialdehyde bagasse cellulose) after dialdehyde bagasse cellulose and Hyperbranched Polymer with Terminal Amido being dissolved in organic solvent and can obtain amine-terminated hyperbranced thing grafting dialdehyde cellulose.
Through carrying out Infrared spectroscopy, ultimate analysis to reactant and product, obtaining the same conclusion, amino modified success can be proved, and obtain the product the same with embodiment 1 structure.
The amine-terminated hyperbranced thing grafting dialdehyde cellulose prepared is carried out the adsorption applications of heavy metal ion:
The application of described Amino End Group modified-cellulose, this Mierocrystalline cellulose is applied to the heavy metal adsorption to ionic state: Amino End Group modified-cellulose of the present invention is placed in plumbous and zine ion solution, adsorption equilibrium is reached through detecting after 10 minutes, analyze the concentration of heavy metal in the solution before and after absorption, adsorption rate reaches as high as 94.3%.
Embodiment 4:
Prepare the method for described Amino End Group modified-cellulose, its processing step is:
(1) raw materials pretreatment: by through cleaning-drying to the bagasse raw material of constant weight at 20%(Wt%) rubidium hydroxide concentrated alkali solution; The bath raio of described concentrated base and bagasse raw material is 20 (V/W)) in soak more than 24 hours, obtain alkali baggasse fiber after washing, suction filtration, oven dry;
(2) dialdehyde bagasse cellulose preparation: by alkali baggasse fiber and the strong oxidizer (Pb (OAc) accounting for alkali baggasse fiber weight 1%
4) oxidizing reaction occurs under lucifuge condition obtain dialdehyde bagasse cellulose;
(3) synthesis of Hyperbranched Polymer with Terminal Amido: with methyl methacrylate and quadrol for raw material, under lucifuge, oxygen barrier condition, (passing into argon gas in the reaction) is stirred polymerization reaction take place and obtained Hyperbranched Polymer with Terminal Amido in butanols;
(4) amine-terminated hyperbranced thing grafting dialdehyde cellulose synthesis: carry out back flow reaction (for slowly dripping the organic solution of Hyperbranched Polymer with Terminal Amido in the organic solution of dialdehyde bagasse cellulose) after dialdehyde bagasse cellulose and Hyperbranched Polymer with Terminal Amido being dissolved in organic solvent and can obtain amine-terminated hyperbranced thing grafting dialdehyde cellulose.
Through carrying out Infrared spectroscopy, ultimate analysis to reactant and product, obtaining the same conclusion, amino modified success can be proved, and obtain the product the same with embodiment 1 structure.
The amine-terminated hyperbranced thing grafting dialdehyde cellulose prepared is carried out the adsorption applications of heavy metal ion:
The application of described Amino End Group modified-cellulose, this Mierocrystalline cellulose is applied to the heavy metal adsorption to ionic state: Amino End Group modified-cellulose of the present invention is placed in tin, nickel and cadmium ion mixing solutions, adsorption equilibrium is reached through detecting after 10 minutes, analyze the concentration of heavy metal in the solution before and after absorption, adsorption rate reaches as high as 95.0%.
Embodiment 5:
Prepare the method for described Amino End Group modified-cellulose, its processing step is:
(1) raw materials pretreatment: by through cleaning-drying to the bagasse raw material of constant weight at 30%(Wt%) hydroxide francium concentrated alkali solution; The bath raio of described concentrated base and bagasse raw material is 40 (V/W)) in soak more than 30 hours, obtain alkali baggasse fiber after washing, suction filtration, oven dry;
(2) dialdehyde bagasse cellulose preparation: by alkali baggasse fiber and the strong oxidizer (KIO accounting for alkali baggasse fiber weight 2%
4) oxidizing reaction occurs under lucifuge condition obtain dialdehyde bagasse cellulose;
(3) synthesis of Hyperbranched Polymer with Terminal Amido: with methyl methacrylate and quadrol for raw material, under lucifuge, oxygen barrier condition, (passing into Krypton in the reaction) is stirred polymerization reaction take place and obtained Hyperbranched Polymer with Terminal Amido in methyl alcohol and alcohol mixed solution;
(4) amine-terminated hyperbranced thing grafting dialdehyde cellulose synthesis: carry out back flow reaction (for slowly dripping the organic solution of Hyperbranched Polymer with Terminal Amido in the organic solution of dialdehyde bagasse cellulose) after dialdehyde bagasse cellulose and Hyperbranched Polymer with Terminal Amido being dissolved in organic solvent and can obtain amine-terminated hyperbranced thing grafting dialdehyde cellulose.
Through carrying out Infrared spectroscopy, ultimate analysis to reactant and product, obtaining the same conclusion, amino modified success can be proved, and obtain the product the same with embodiment 1 structure.
The amine-terminated hyperbranced thing grafting dialdehyde cellulose prepared is carried out the adsorption applications of heavy metal ion:
The application of described Amino End Group modified-cellulose, this Mierocrystalline cellulose is applied to the heavy metal adsorption to ionic state: Amino End Group modified-cellulose of the present invention is placed in cobalt and antimony ion solution, adsorption equilibrium is reached through detecting after 10 minutes, analyze the concentration of heavy metal in the solution before and after absorption, adsorption rate reaches as high as 92,8%.
Embodiment 6:
Prepare the method for described Amino End Group modified-cellulose, its processing step is:
(1) raw materials pretreatment: by through cleaning-drying to the bagasse raw material of constant weight at 50%(Wt%) sodium hydroxide concentrated alkali solution; The bath raio of described concentrated base and bagasse raw material is 60 (V/W)) in soak more than 36 hours, obtain alkali baggasse fiber after washing, suction filtration, oven dry;
(2) dialdehyde bagasse cellulose preparation: by alkali baggasse fiber and the strong oxidizer H accounting for alkali baggasse fiber weight 3%
5iO
6under lucifuge condition, there is oxidizing reaction obtain dialdehyde bagasse cellulose;
(3) synthesis of Hyperbranched Polymer with Terminal Amido: with methyl methacrylate and quadrol for raw material, in the mixing solutions of propyl alcohol and butanols, under lucifuge, oxygen barrier condition, (passing into radon gas in the reaction) is stirred polymerization reaction take place and is obtained Hyperbranched Polymer with Terminal Amido;
(4) amine-terminated hyperbranced thing grafting dialdehyde cellulose synthesis: carry out back flow reaction (for slowly dripping the organic solution of Hyperbranched Polymer with Terminal Amido in the organic solution of dialdehyde bagasse cellulose) after dialdehyde bagasse cellulose and Hyperbranched Polymer with Terminal Amido being dissolved in organic solvent and can obtain amine-terminated hyperbranced thing grafting dialdehyde cellulose.
Through carrying out Infrared spectroscopy, ultimate analysis to reactant and product, obtaining the same conclusion, amino modified success can be proved, and obtain the product the same with embodiment 1 structure.
The amine-terminated hyperbranced thing grafting dialdehyde cellulose prepared is carried out the adsorption applications of heavy metal ion:
The application of described Amino End Group modified-cellulose, this Mierocrystalline cellulose is applied to the heavy metal adsorption to ionic state: Amino End Group modified-cellulose of the present invention is placed in bismuth ion solution, adsorption equilibrium is reached through detecting after 10 minutes, analyze the concentration of heavy metal in the solution before and after absorption, adsorption rate reaches as high as 93.5%.
Embodiment 7:
Prepare the method for described Amino End Group modified-cellulose, its processing step is:
(1) raw materials pretreatment: by through cleaning-drying to the bagasse raw material of constant weight at 60%(Wt%) potassium hydroxide concentrated alkali solution; The bath raio of described concentrated base and bagasse raw material is 70 (V/W)) in soak more than 20 hours, obtain alkali baggasse fiber after washing, suction filtration, oven dry;
(2) dialdehyde bagasse cellulose preparation: by alkali baggasse fiber and the strong oxidizer (NaIO accounting for alkali baggasse fiber weight 4%
4) oxidizing reaction occurs under lucifuge condition obtain dialdehyde bagasse cellulose;
(3) synthesis of Hyperbranched Polymer with Terminal Amido: with methyl methacrylate and quadrol for raw material, (pass into N in the reaction under lucifuge, oxygen barrier condition in propyl alcohol
2) stir polymerization reaction take place obtain Hyperbranched Polymer with Terminal Amido;
(4) amine-terminated hyperbranced thing grafting dialdehyde cellulose synthesis: carry out back flow reaction (for slowly dripping the organic solution of Hyperbranched Polymer with Terminal Amido in the organic solution of dialdehyde bagasse cellulose) after dialdehyde bagasse cellulose and Hyperbranched Polymer with Terminal Amido being dissolved in organic solvent and can obtain amine-terminated hyperbranced thing grafting dialdehyde cellulose.
Through carrying out Infrared spectroscopy, ultimate analysis to reactant and product, obtaining the same conclusion, amino modified success can be proved, and obtain the product the same with embodiment 1 structure.
The amine-terminated hyperbranced thing grafting dialdehyde cellulose prepared is carried out the adsorption applications of heavy metal ion:
The application of described Amino End Group modified-cellulose, this Mierocrystalline cellulose is applied to the heavy metal adsorption to ionic state: Amino End Group modified-cellulose of the present invention is placed in copper, lead, zinc, tin, nickel ion solution, adsorption equilibrium is reached through detecting after 10 minutes, analyze the concentration of heavy metal in the solution before and after absorption, adsorption rate reaches as high as 94.6%.
Embodiment 8:
Prepare the method for described Amino End Group modified-cellulose, its processing step is:
(1) raw materials pretreatment: by through cleaning-drying to the bagasse raw material of constant weight at 70%(Wt%) rubidium hydroxide concentrated alkali solution; The bath raio of described concentrated base and bagasse raw material is 80 (V/W)) in soak more than 48 hours, obtain alkali baggasse fiber after washing, suction filtration, oven dry;
(2) dialdehyde bagasse cellulose preparation: by alkali baggasse fiber and the strong oxidizer (Pb (OAc) accounting for alkali baggasse fiber weight 5%
4) oxidizing reaction occurs under lucifuge condition obtain dialdehyde bagasse cellulose;
(3) synthesis of Hyperbranched Polymer with Terminal Amido: with methyl methacrylate and quadrol for raw material, (pass into Ar in the reaction under lucifuge, oxygen barrier condition in methyl alcohol, ethanol, propyl alcohol, butanols
2) stir polymerization reaction take place obtain Hyperbranched Polymer with Terminal Amido;
(4) amine-terminated hyperbranced thing grafting dialdehyde cellulose synthesis: carry out back flow reaction (for slowly dripping the organic solution of Hyperbranched Polymer with Terminal Amido in the organic solution of dialdehyde bagasse cellulose) after dialdehyde bagasse cellulose and Hyperbranched Polymer with Terminal Amido being dissolved in organic solvent and can obtain amine-terminated hyperbranced thing grafting dialdehyde cellulose.
Through carrying out Infrared spectroscopy, ultimate analysis to reactant and product, obtaining the same conclusion, amino modified success can be proved, and obtain the product the same with embodiment 1 structure.
The amine-terminated hyperbranced thing grafting dialdehyde cellulose prepared is carried out the adsorption applications of heavy metal ion:
The application of described Amino End Group modified-cellulose, this Mierocrystalline cellulose is applied to the heavy metal adsorption to ionic state: Amino End Group modified-cellulose of the present invention is placed in lead ion mixing solutions, adsorption equilibrium is reached through detecting after 10 minutes, analyze the concentration of heavy metal in the solution before and after absorption, adsorption rate reaches as high as 96.0%.
Embodiment 9:
Prepare the method for described Amino End Group modified-cellulose, its processing step is:
(1) raw materials pretreatment: by through cleaning-drying to the bagasse raw material of constant weight at 80%(Wt%) hydroxide francium concentrated alkali solution; The bath raio of described concentrated base and bagasse raw material is 90 (V/W)) in soak more than 30 hours, obtain alkali baggasse fiber after washing, suction filtration, oven dry;
(2) dialdehyde bagasse cellulose preparation: by alkali baggasse fiber and the strong oxidizer (KIO accounting for alkali baggasse fiber weight 2%
4) oxidizing reaction occurs under lucifuge condition obtain dialdehyde bagasse cellulose;
(3) synthesis of Hyperbranched Polymer with Terminal Amido: with methyl methacrylate and quadrol for raw material, (pass into N in the reaction under lucifuge, oxygen barrier condition in methyl alcohol and alcohol mixed solution
2) stir polymerization reaction take place obtain Hyperbranched Polymer with Terminal Amido;
(4) amine-terminated hyperbranced thing grafting dialdehyde cellulose synthesis: carry out back flow reaction (for slowly dripping the organic solution of Hyperbranched Polymer with Terminal Amido in the organic solution of dialdehyde bagasse cellulose) after dialdehyde bagasse cellulose and Hyperbranched Polymer with Terminal Amido being dissolved in organic solvent and can obtain amine-terminated hyperbranced thing grafting dialdehyde cellulose.
Through carrying out Infrared spectroscopy, ultimate analysis to reactant and product, obtaining the same conclusion, amino modified success can be proved, and obtain the product the same with embodiment 1 structure.
The amine-terminated hyperbranced thing grafting dialdehyde cellulose prepared is carried out the adsorption applications of heavy metal ion:
The application of described Amino End Group modified-cellulose, this Mierocrystalline cellulose is applied to the heavy metal adsorption to ionic state: Amino End Group modified-cellulose of the present invention is placed in mercury ion solution, adsorption equilibrium is reached through detecting after 10 minutes, analyze the concentration of heavy metal in the solution before and after absorption, adsorption rate reaches as high as 92,8%.
Embodiment 10:
Prepare the method for described Amino End Group modified-cellulose, its processing step is:
(1) raw materials pretreatment: by through cleaning-drying to the bagasse raw material of constant weight at 85%(Wt%) hydroxide francium concentrated alkali solution; The bath raio of described concentrated base and bagasse raw material is 100 (V/W)) in soak more than 30 hours, obtain alkali baggasse fiber after washing, suction filtration, oven dry;
(2) dialdehyde bagasse cellulose preparation: by alkali baggasse fiber and the strong oxidizer (KIO accounting for alkali baggasse fiber weight 6%
4) oxidizing reaction occurs under lucifuge condition obtain dialdehyde bagasse cellulose;
(3) synthesis of Hyperbranched Polymer with Terminal Amido: with methyl methacrylate and quadrol for raw material, (pass into N in the reaction under lucifuge, oxygen barrier condition in methyl alcohol and alcohol mixed solution
2) stir polymerization reaction take place obtain Hyperbranched Polymer with Terminal Amido;
(4) amine-terminated hyperbranced thing grafting dialdehyde cellulose synthesis: carry out back flow reaction (for slowly dripping the organic solution of Hyperbranched Polymer with Terminal Amido in the organic solution of dialdehyde bagasse cellulose) after dialdehyde bagasse cellulose and Hyperbranched Polymer with Terminal Amido being dissolved in organic solvent and can obtain amine-terminated hyperbranced thing grafting dialdehyde cellulose.
Through carrying out Infrared spectroscopy, ultimate analysis to reactant and product, obtaining the same conclusion, amino modified success can be proved, and obtain the product the same with embodiment 1 structure.
The amine-terminated hyperbranced thing grafting dialdehyde cellulose prepared is carried out the adsorption applications of heavy metal ion:
The application of described Amino End Group modified-cellulose, this Mierocrystalline cellulose is applied to the heavy metal adsorption to ionic state: Amino End Group modified-cellulose of the present invention is placed in copper, lead, mercury, cadmium-ion solution, adsorption equilibrium is reached through detecting after 10 minutes, analyze the concentration of heavy metal in the solution before and after absorption, adsorption rate reaches as high as 92.3%.
Claims (10)
1. an Amino End Group modified-cellulose, is characterized in that: this Mierocrystalline cellulose is: amine-terminated hyperbranced thing grafting dialdehyde cellulose; Its skeleton symbol is:
；
The structural unit of the CELL described in formula is:
；
Described HBPN is Hyperbranched Polymer with Terminal Amido, and its skeleton symbol is:
；
The amine-terminated hyperbranced thing grafting dialdehyde cellulose structural formula obtained after being replaced by CELL and HBPN structural formula is:
。
2. prepare a method for Amino End Group modified-cellulose described in claim 1, it is characterized in that: its processing step is:
Raw materials pretreatment: soak more than 10 hours by through cleaning-drying to the bagasse raw material of constant weight in concentrated base, obtain alkali baggasse fiber after washing, suction filtration, oven dry;
Prepared by dialdehyde bagasse cellulose: oxidizing reaction is occurred under lucifuge condition for alkali baggasse fiber and strong oxidizer and obtains dialdehyde bagasse cellulose;
The synthesis of Hyperbranched Polymer with Terminal Amido: with methyl methacrylate and quadrol for raw material, stir polymerization reaction take place under lucifuge, oxygen barrier condition in organic solvent and obtain Hyperbranched Polymer with Terminal Amido;
Amine-terminated hyperbranced thing grafting dialdehyde cellulose synthesis: carry out back flow reaction after dialdehyde bagasse cellulose and Hyperbranched Polymer with Terminal Amido being dissolved in organic solvent and can obtain amine-terminated hyperbranced thing grafting dialdehyde cellulose.
3. preparation method according to claim 2, is characterized in that: described concentrated base is 5 ~ 80%(Wt%) more than the alkaline solution of the Ith race's metallic element; The bath raio of described concentrated base and bagasse raw material is 8 ~ 100 (V/W).
4. preparation method according to claim 2, is characterized in that: described strong oxidizer is KIO
4, H
5iO
6, NaIO
4, Pb (OAc)
4in any.
5. preparation method according to claim 3 or 4, is characterized in that: described oxygen barrier condition is for pass into N in the reaction
2or rare gas element.
6. preparation method according to claim 5, is characterized in that: described organic solvent is C
4any one following alcoholic solution or their combination.
7. according to claim 2-4,6 arbitrary described preparation methods, it is characterized in that: the back flow reaction of described amine-terminated hyperbranced thing grafting dialdehyde cellulose synthesis is the organic solution slowly dripping Hyperbranched Polymer with Terminal Amido in the organic solution of dialdehyde bagasse cellulose.
8. an application for Amino End Group modified-cellulose as claimed in claim 1, is characterized in that: this Mierocrystalline cellulose is applied to heavy metal adsorption to ionic state and desorption.
9. the application of Amino End Group modified-cellulose according to claim 8, is characterized in that: described heavy metal comprises the combination of any or they in copper, lead, zinc, tin, nickel, cobalt, antimony, mercury, cadmium and bismuth.
10. the application of Amino End Group modified-cellulose according to claim 9, is characterized in that: described heavy metal comprises the combination of any or they in copper, lead, mercury, cadmium.
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