CN103769061B - The synthetic method of a kind of collagen load hyper-branched polyester/metal ion fluoride adsorbent - Google Patents
The synthetic method of a kind of collagen load hyper-branched polyester/metal ion fluoride adsorbent Download PDFInfo
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Abstract
The invention discloses the synthetic method of a kind of collagen load hyper-branched polyester/metal ion fluoride adsorbent, superbrnaching end-hydroxy polyester is grafted on collagen under crosslinking agent effect, increase collagen surface active groups content, by the collagen after obtained load hyper-branched polyester and complexing of metal ion, the collagen load hyper-branched polyester/metal ion after complexing is used for the process of fluoride waste.Synthetic method of the present invention is simple, and easily realize suitability for industrialized production, the product of preparation is high to fluoride selective in the aqueous solution, absorption thoroughly, the discarded collagen that leather making process produces is used for after chemical modification the process of fluoride waste, reaches with useless pollution treatment, the target of maximization of economic benefit.
Description
Technical field
The invention belongs to fluoride wastewater treatment technical field, be specifically related to the synthetic method of a kind of collagen load hyper-branched polyester/metal ion fluoride adsorbent.
Background technology
Fluorine ion is extensively present in the water body of the earth, and in environment, the main source of fluoride pollution is iron and steel, aluminium processed, chemistry, phosphate fertilizer, glass, pottery, fluorine chemical, gives off fluorine-containing " three wastes " in the industry such as brick and tile and coal-fired process.Fluorine-containing " three wastes " that discharge in industrial process mainly use ice crystal (Na
3alF
6), fluorite (CaF
2), rock phosphate in powder (3Ca(PO
4)
2caF
2) and HF enterprise discharge.In recent years, underground water fluoride pollution becomes worldwide problem gradually and causes concern.In the drinking water of multiple countries and regions, the content of fluoride all exceedes World Health Organization's specified standard in the world, and the brain of fluorine ion to the tooth of people, bone, baby produces serious harm, and serious threat is to the health of animals and plants and the mankind.Some City is fluorine element content overproof in groundwater in large area comparatively, namely exceedes national hygiene standard for drinking water 0.5 ~ 1.0mg/L, and some region is even above standard 1.5 ~ 2.5 times of the upper limit, becomes high fluorine groundwater.Drink high-fluorine water for a long time, can cause endemic fluorosis, the lighter causes fluorine spot tooth disease, and severe one causes sclerotin deformation, and brings out other pathology, causes great harm to the healthy of city dweller.Therefore, find efficient fluoride processing method fast and seem particularly important.
Summary of the invention
The object of the present invention is to provide the synthetic method of a kind of collagen load hyper-branched polyester/metal ion fluoride adsorbent, the collagen load hyper-branched polyester that the method obtains/metal ion fluoride adsorbent can overcome that the adsorbent amount that prior art exists is large, absorption is thorough, and easily produces the problem of secondary pollution.
For achieving the above object, the technical solution used in the present invention comprises the following steps:
1) synthesis of load hyper-branched polyester collagen
1.1) be dissolved in hydrophilic organic solvent by superbrnaching end-hydroxy polyester, then add crosslinking agent wherein, wherein, the mol ratio of superbrnaching end-hydroxy polyester surface hydroxyl and crosslinking agent is (8 ~ 32): 1; Regulate pH to 4.5 ~ 10, then at 30 ~ 50 DEG C, react 1.5 ~ 3h;
1.2) react rear deionized water rinsing, until cross-linking agent-free detects in cleaning fluid, obtain the superbrnaching end-hydroxy polyester after crosslinking agent activation;
1.3) join in the aqueous solution of hydrophilic organic solvent by the collagen rinsed well with hydrophilic organic solvent, preparation collagen suspension liquid, wherein, the mol ratio of collagen surface amino groups and crosslinking agent is (0.8 ~ 1.2): 1; Again the superbrnaching end-hydroxy polyester after crosslinking agent activation is joined in collagen suspension liquid, 15 ~ 24h is reacted under the air-proof condition of 40 ~ 60 DEG C, the product with deionized water cleaning will obtained again, washes away free activation hyper-branched polyester, obtains load hyper-branched polyester collagen;
2) synthesis of collagen load hyper-branched polyester/metal ion
Load hyper-branched polyester collagen step 1) obtained joins in metal ion solution, and wherein, the mol ratio of load hyper-branched polyester collagen surface hydroxyl and metal ion is 1:(0.9 ~ 1.2); Again the pH of solution is adjusted to 3 ~ 6.5, and the 2 ~ 8h that vibrates at 25 ~ 40 DEG C, take out and filter, obtained collagen load hyper-branched polyester/metal ion fluoride adsorbent.
Described step 1.1) in, superbrnaching end-hydroxy polyester is Boltorn H20, Boltorn H30 or Boltorn H40.
Described step 1.1) in, crosslinking agent is epoxychloropropane, divinylsulfone or N, N '-methylene-bisacrylamide.
Described step 1.1) in, adjust ph is undertaken regulating by the NaOH solution of dropping 1mol/L or the HCl solution of dropping 0.5mol/L.
Described step 1.1) in, hydrophilic organic solvent is acetone, dioxane, dimethyl sulfoxide (DMSO) or DMF.
Described step 1.3) in, clean collagen is the hydrophilic organic solvent aqueous cleaning of 10%, 30% and 50% by mass concentration respectively, drains cleaning fluid after each cleaning by vacuum.
Described step 2) in, metal ion solution is aluminum sulfate solution, ferrum sulfuricum oxydatum solutum or solution of zinc sulfate.
Compared with prior art, the present invention has following beneficial effect:
First the present invention utilizes hyper-branched polyester to carry out modification to collagen under the effect of crosslinking agent, obtained load hyper-branched polyester collagen.Adopt and significantly can increase collagen surface hydroxyl active functional group content in this way; Complexation of metal ions modification is carried out to it in the basis of load hyper-branched polyester collagen, obtains collagen load hyper-branched polyester/metal ion.Adopt the electropositive that the collagen load hyper-branched polyester/metal ion prepared in this way can significantly improve this adsorbent, thus improve its absorption property to fluorine anion in water; Therefore, obtained collagen load hyper-branched polyester/metal ion adsorbent is high to fluoride adsorptive selectivity in water, and treatment effeciency is high, is easy to suitability for industrialized production, overcome the adsorbent amount that prior art exists large, adsorb halfway problem.
Collagen load hyper-branched polyester/metal ion adsorbent that the present invention obtains has stronger adaptability to fluoride waste change, stable performance, recyclability is good, be easy to reclaim, therefore, production and the use procedure of collagen load hyper-branched polyester/metal ion adsorbent of the present invention can not cause secondary pollution to environment, have a good application prospect, and the obtained absorption property of collagen load hyper-branched polyester/metal ion adsorbent to fluoride significantly improves.
Further, the solid waste that collagen can produce from leather production process extracts as raw material, and therefore, raw material sources of the present invention are extensive, and nontoxic, with low cost.
Accompanying drawing explanation
Fig. 1 is the molecular schematic diagram of collagen load hyper-branched polyester of the present invention/metal ion fluoride adsorbent.
Detailed description of the invention
Below in conjunction with specific embodiment, the present invention is further detailed explanation:
The synthetic method of collagen load hyper-branched polyester of the present invention/metal ion fluoride adsorbent, comprises the following steps:
1) synthesis of load hyper-branched polyester collagen
1.1) be dissolved in hydrophilic organic solvent by superbrnaching end-hydroxy polyester, then add crosslinking agent wherein, wherein, the mol ratio of superbrnaching end-hydroxy polyester surface hydroxyl and crosslinking agent is (8 ~ 32): 1; Regulate pH to 4.5 ~ 10, then at 30 ~ 50 DEG C, react 1.5 ~ 3h; Wherein, superbrnaching end-hydroxy polyester is BoltornH20, Boltorn H30 or Boltorn H40, Boltorn H20 is the hyper-branched polyester uniquely reaching pilot-scale production at present in the world, it is the second generation hyper-branched polyester adopting " divergent method " to synthesize as raw material using ethoxyquin pentaerythrite, dihydromethyl propionic acid, its Theoretical molecular terminal hydroxy group number is 16, relative molecular weight 1749.8; Boltorn H30 Theoretical molecular terminal hydroxy group number is 32, relative molecular weight 3607.6; Boltorn H40 Theoretical molecular terminal hydroxy group number is 64; Hydrophilic organic solvent is acetone, dioxane, dimethyl sulfoxide (DMSO) (DMSO) or DMF (DMF); Crosslinking agent is epoxychloropropane, divinylsulfone or N, N '-methylene-bisacrylamide;
1.2) react rear deionized water rinsing, until cross-linking agent-free detects in cleaning fluid, obtain the superbrnaching end-hydroxy polyester after crosslinking agent activation;
1.3) get some collagens, then clean with the hydrophilic organic solvent aqueous solution that mass concentration is 10%, 30% and 50% respectively, after each cleaning, drain cleaning fluid by vacuum.Join in the aqueous solution of hydrophilic organic solvent by the collagen rinsed well with hydrophilic organic solvent, preparation collagen suspension liquid, wherein, the mol ratio of collagen surface amino groups and crosslinking agent is (0.8 ~ 1.2): 1; Again the superbrnaching end-hydroxy polyester after crosslinking agent activation is joined in collagen suspension liquid, 15 ~ 24h is reacted under the air-proof condition of 40 ~ 60 DEG C, the product with deionized water cleaning will obtained again, washes away free activation hyper-branched polyester, obtains load hyper-branched polyester collagen;
2) synthesis of collagen load hyper-branched polyester/metal ion
Load hyper-branched polyester collagen step 1) obtained joins in metal ion solution, wherein, the mol ratio of load hyper-branched polyester collagen surface hydroxyl and metal ion is 1:(0.9 ~ 1.2), metal ion solution is aluminum sulfate solution, ferrum sulfuricum oxydatum solutum or solution of zinc sulfate; Again the pH of solution is adjusted to 3 ~ 6.5, and the 2 ~ 8h that vibrates at 25 ~ 40 DEG C, take out and filter, obtained collagen load hyper-branched polyester/metal ion fluoride adsorbent.
Principle of the present invention:
In the present invention, collagen is a kind of typical polyampholyte, and its surface is containing amino, carboxyl, hydroxyl isoreactivity functional group.Amino acid, carboxylic acid, carbohydrate, lower alcohol and aldehydes matter etc., can with metal fluoro complex compound cation (as FeF
2+, AlF
2+, CoF
2+, ZnF
+, H
2f
+, PbF
+, HgF
+deng) form complicated complex compound.And the active group quantity contained by collagen surface is limited, therefore, first the present invention utilizes hyper-branched polyester to carry out modification to collagen under the effect of crosslinking agent, obtained load hyper-branched polyester collagen.Adopt and significantly can increase collagen surface hydroxyl active functional group content in this way; Complexation of metal ions modification is carried out to it in the basis of load hyper-branched polyester collagen, obtains collagen load hyper-branched polyester/metal ion.Adopt the electropositive that the collagen load hyper-branched polyester/metal ion prepared in this way can significantly improve this adsorbent, thus improve its absorption property to fluorine anion in water; Therefore, obtained collagen load hyper-branched polyester/metal ion adsorbent is high to fluoride adsorptive selectivity in water, and treatment effeciency is high, is easy to suitability for industrialized production, overcome the adsorbent amount that prior art exists large, adsorb halfway problem.
Enumerate several specific embodiment of the present invention below:
Embodiment 1:
1) synthesis of load hyper-branched polyester collagen
1.1) Boltorn H20 is dissolved in the dimethyl sulfoxide (DMSO) (DMSO) of 10mL, add epoxychloropropane, the mol ratio of superbrnaching end-hydroxy polyester surface hydroxyl and epoxychloropropane is 8:1, by dripping the NaOH solution regulation system pH to 10 of 1mol/L, at 30 DEG C, reacts 2h;
1.2) rear deionized water rinsing has been reacted, until detect without epoxy radicals in cleaning fluid;
1.3) by collagen with 10%, the DMSO aqueous cleaning of 30%, 50%, drains cleaning fluid by vacuum after each cleaning.Be about 0.8:1 by the mol ratio of collagen surface amino groups and epoxychloropropane, then add DMSO in clean collagen, preparation collagen suspension liquid, joins the Boltorn H20 after Epichlorohydrin activation in collagen suspension liquid.Reaction system is warmed up to 50 DEG C, under air-proof condition, reacts 18h, the product with deionized water cleaning obtained, washes away free activated b oltorn H20;
2) synthesis of collagen load hyper-branched polyester/metal ion
The collagen taking 2g load hyper-branched polyester is placed in the Al configured by aluminum sulfate that 200ml contains 2g/L
3+in solution, regulated by pH value of solution and be about 3, vibrate 3h at 30 DEG C, takes out and filter.Filtrate is diluted to finite concentration, adopts ultraviolet scene photometer measuring method to measure the concentration of remaining metal ion in solution, calculate the complexing amount of metal ion, obtained collagen load hyper-branched polyester/metal ion fluoride adsorbent.
Embodiment 2:
1) synthesis of load hyper-branched polyester collagen
1.1) Boltorn H30 is dissolved in the N of 10mL, in dinethylformamide (DMF), add divinylsulfone, the mol ratio of superbrnaching end-hydroxy polyester surface hydroxyl and crosslinking agent is 16:1, by dripping the HCl solution regulation system pH to 4.5 of 0.5mol/L, at 40 DEG C, react 2h;
1.2) rear deionized water rinsing has been reacted, until detect without divinyl sulfoxide in cleaning fluid;
1.3) by collagen with 10%, the DMF aqueous cleaning of 30%, 50%, drains cleaning fluid by vacuum after each cleaning.Be about 1:1 by the mol ratio of collagen surface amino groups and divinyl sulfoxide, then add DMF in clean collagen, preparation collagen suspension liquid, the Boltorn H30 after being activated by divinyl sulfoxide joins in collagen suspension liquid.Reaction system is warmed up to 60 DEG C, under air-proof condition, reacts 15h, the product with deionized water cleaning obtained, washes away free activated b oltorn H30;
2) synthesis of collagen load hyper-branched polyester/metal ion
The collagen taking 2g load hyper-branched polyester is placed in the Fe configured by ferric sulfate that 200ml contains 2g/L
3+in solution, regulated by pH value of solution and be about 5, vibrate 3h at 30 DEG C, takes out and filter.Filtrate is diluted to finite concentration, adopts ultraviolet scene photometer measuring method to measure the concentration of remaining metal ion in solution, calculate the complexing amount of metal ion, obtained collagen load hyper-branched polyester/metal ion fluoride adsorbent.
Embodiment 3:
1) synthesis of load hyper-branched polyester collagen
1.1) Boltorn H40 is dissolved in the dimethyl sulfoxide (DMSO) (DMSO) of 10mL, add N, N '-methylene-bisacrylamide, the mol ratio of superbrnaching end-hydroxy polyester surface hydroxyl and crosslinking agent is 32:1, by dripping the HCl solution regulation system pH to 4.5 of 0.5mol/L, at 35 DEG C, react 2h;
1.2) rear deionized water rinsing has been reacted, until without N, N in cleaning fluid '-methylene-bisacrylamide detects;
1.3) by collagen with 10%, the DMSO aqueous cleaning of 30%, 50%, drains cleaning fluid by vacuum after each cleaning.By collagen surface amino groups and N, the mol ratio of N '-methylene-bisacrylamide is about 1:1, then adds DMSO in clean collagen, preparation collagen suspension liquid, by N, N '-methylene-bisacrylamide activation after Boltorn H40 join in collagen suspension liquid.Reaction system is warmed up to 65 DEG C, under air-proof condition, reacts 18h, the product with deionized water cleaning obtained, washes away free activated b oltorn H40;
2) synthesis of collagen load hyper-branched polyester/metal ion
The collagen taking 2g load hyper-branched polyester is placed in the Zn configured by zinc sulfate that 200ml contains 2g/L
2+in solution, regulated by pH value of solution and be about 6.5, vibrate 3h at 30 DEG C, takes out and filter.Filtrate is diluted to finite concentration, adopts ultraviolet scene photometer measuring method to measure the concentration of remaining metal ion in solution, calculate the complexing amount of metal ion, obtained collagen load hyper-branched polyester/metal ion fluoride adsorbent.
Embodiment 4:
1) synthesis of load hyper-branched polyester collagen
1.1) be dissolved in acetone by Boltorn H20, then add epoxychloropropane wherein, wherein, the mol ratio of superbrnaching end-hydroxy polyester surface hydroxyl and crosslinking agent is 10:1; By dripping the NaOH solution regulation system pH to 9 of 1mol/L, then at 30 DEG C, react 1.5h;
1.2) react rear deionized water rinsing, until detect without epoxy radicals in cleaning fluid, obtain the Boltorn H20 after Epichlorohydrin activation;
1.3) get some collagens, then clean with the aqueous acetone solution that mass concentration is 10%, 30% and 50% respectively, after each cleaning, drain cleaning fluid by vacuum.Join in the aqueous solution of acetone by the collagen clean with acetone rinsing, preparation collagen suspension liquid, wherein, the mol ratio of collagen surface amino groups and crosslinking agent is 0.9:1; Again the Boltorn H20 after Epichlorohydrin activation is joined in collagen suspension liquid, 16h is reacted under the air-proof condition of 40 DEG C, the product with deionized water cleaning will obtained again, washes away free activation hyper-branched polyester, obtains load hyper-branched polyester collagen;
2) synthesis of collagen load hyper-branched polyester/metal ion
Load hyper-branched polyester collagen step 1) obtained joins in aluminum sulfate solution, wherein, and load hyper-branched polyester collagen surface hydroxyl and Al
3+mol ratio be 1:0.9; Again the pH of solution is adjusted to 3.5, and the 2h that vibrates at 25 DEG C, take out and filter, obtained collagen load hyper-branched polyester/metal ion fluoride adsorbent.
Embodiment 5:
1) synthesis of load hyper-branched polyester collagen
1.1) be dissolved in dioxane by Boltorn H30, then add divinylsulfone wherein, wherein, the mol ratio of superbrnaching end-hydroxy polyester surface hydroxyl and crosslinking agent is 18:1; By dripping the HCl solution regulation system pH to 5 of 0.5mol/L, then at 35 DEG C, react 1.8h;
1.2) react rear deionized water rinsing, until detect without divinyl sulfoxide in cleaning fluid, obtain the Boltorn H30 after divinylsulfone activation;
1.3) get some collagens, then clean with the dioxane aqueous solution that mass concentration is 10%, 30% and 50% respectively, after each cleaning, drain cleaning fluid by vacuum.Join in the aqueous solution of dioxane by the collagen rinsed well with dioxane, preparation collagen suspension liquid, wherein, the mol ratio of collagen surface amino groups and crosslinking agent is 0.8:1; Again the Boltorn H30 after the activation of epoxy chlorine dioxane is joined in collagen suspension liquid, 18h is reacted under the air-proof condition of 45 DEG C, the product with deionized water cleaning will obtained again, washes away free activation hyper-branched polyester, obtains load hyper-branched polyester collagen;
2) synthesis of collagen load hyper-branched polyester/metal ion
Load hyper-branched polyester collagen step 1) obtained joins in ferrum sulfuricum oxydatum solutum, wherein, and load hyper-branched polyester collagen surface hydroxyl and Fe
3+mol ratio be 1:0.9; Again the pH of solution is adjusted to 4.5, and the 4h that vibrates at 28 DEG C, take out and filter, obtained collagen load hyper-branched polyester/metal ion fluoride adsorbent.
Embodiment 6:
1) synthesis of load hyper-branched polyester collagen
1.1) be dissolved in dimethyl sulfoxide (DMSO) (DMSO) by Boltorn H40, then add N wherein, N '-methylene-bisacrylamide, wherein, the mol ratio of superbrnaching end-hydroxy polyester surface hydroxyl and crosslinking agent is 22:1; By dripping the HCl solution regulation system pH to 5.5 of 0.5mol/L, then at 38 DEG C, react 2.2h;
1.2) the Boltorn H40 after '-methylene-bisacrylamide detect, obtain through N, N '-methylene-bisacrylamide activation of having reacted rear deionized water rinsing, until without N, N in cleaning fluid;
1.3) get some collagens, then clean with dimethyl sulfoxide (DMSO) (DMSO) aqueous solution that mass concentration is 10%, 30% and 50% respectively, after each cleaning, drain cleaning fluid by vacuum.Join in the aqueous solution of dimethyl sulfoxide (DMSO) (DMSO) by the collagen rinsed well with dimethyl sulfoxide (DMSO) (DMSO), preparation collagen suspension liquid, wherein, the mol ratio of collagen surface amino groups and crosslinking agent is 0.9:1; Again will through N, Boltorn H40 after N '-methylene-bisacrylamide activation joins in collagen suspension liquid, under the air-proof condition of 50 DEG C, react 20h, then the product with deionized water cleaning that will obtain, wash away free activation hyper-branched polyester, obtain load hyper-branched polyester collagen;
2) synthesis of collagen load hyper-branched polyester/metal ion
Load hyper-branched polyester collagen step 1) obtained joins in solution of zinc sulfate, wherein, and load hyper-branched polyester collagen surface hydroxyl and Zn
2+mol ratio be 1:1; Again the pH of solution is adjusted to 5.5, and the 5h that vibrates at 30 DEG C, take out and filter, obtained collagen load hyper-branched polyester/metal ion fluoride adsorbent.
Embodiment 7:
1) synthesis of load hyper-branched polyester collagen
1.1) be dissolved in DMF (DMF) by Boltorn H20, then add epoxychloropropane wherein, wherein, the mol ratio of superbrnaching end-hydroxy polyester surface hydroxyl and crosslinking agent is 26:1; By dripping the NaOH solution regulation system pH to 8.5 of 1mol/L, then at 40 DEG C, react 2.6h;
1.2) react rear deionized water rinsing, until detect without epoxy radicals in cleaning fluid, obtain the Boltorn H20 after Epichlorohydrin activation;
1.3) get some collagens, then clean with DMF (DMF) aqueous solution that mass concentration is 10%, 30% and 50% respectively, after each cleaning, drain cleaning fluid by vacuum.Join in the aqueous solution of DMF (DMF) by the collagen rinsed well with DMF (DMF), preparation collagen suspension liquid, wherein, the mol ratio of collagen surface amino groups and crosslinking agent is 1.1:1; Again the Boltorn H20 after Epichlorohydrin activation is joined in collagen suspension liquid, 20h is reacted under the air-proof condition of 55 DEG C, the product with deionized water cleaning will obtained again, washes away free activation hyper-branched polyester, obtains load hyper-branched polyester collagen;
2) synthesis of collagen load hyper-branched polyester/metal ion
Load hyper-branched polyester collagen step 1) obtained joins in aluminum sulfate solution, wherein, and load hyper-branched polyester collagen surface hydroxyl and Al
3+mol ratio be 1:1; Again the pH of solution is adjusted to 4, and the 6h that vibrates at 33 DEG C, take out and filter, obtained collagen load hyper-branched polyester/metal ion fluoride adsorbent.
Embodiment 8:
1) synthesis of load hyper-branched polyester collagen
1.1) be dissolved in acetone by Boltorn H30, then add divinylsulfone wherein, wherein, the mol ratio of superbrnaching end-hydroxy polyester surface hydroxyl and crosslinking agent is 28:1; By dripping the HCl solution regulation system pH to 5.5 of 0.5mol/L, then at 45 DEG C, react 2.8h;
1.2) react rear deionized water rinsing, until detect without divinyl sulfoxide in cleaning fluid, obtain the Boltorn H30 after divinylsulfone activation;
1.3) get some collagens, then clean with the aqueous acetone solution that mass concentration is 10%, 30% and 50% respectively, after each cleaning, drain cleaning fluid by vacuum.Join in the aqueous solution of acetone by the collagen clean with acetone rinsing, preparation collagen suspension liquid, wherein, the mol ratio of collagen surface amino groups and crosslinking agent is 1.2:1; Again the Boltorn H30 after divinylsulfone activation is joined in collagen suspension liquid, 22h is reacted under the air-proof condition of 58 DEG C, the product with deionized water cleaning will obtained again, washes away free activation hyper-branched polyester, obtains load hyper-branched polyester collagen;
2) synthesis of collagen load hyper-branched polyester/metal ion
Load hyper-branched polyester collagen step 1) obtained joins in ferrum sulfuricum oxydatum solutum, wherein, and load hyper-branched polyester collagen surface hydroxyl and Fe
3+mol ratio be 1:1.1; Again the pH of solution is adjusted to 5, and the 7h that vibrates at 35 DEG C, take out and filter, obtained collagen load hyper-branched polyester/metal ion fluoride adsorbent.
Embodiment 9:
1) synthesis of load hyper-branched polyester collagen
1.1) be dissolved in dioxane by Boltorn H40, then add N wherein, N '-methylene-bisacrylamide, wherein, the mol ratio of superbrnaching end-hydroxy polyester surface hydroxyl and crosslinking agent is 30:1; By dripping the HCl solution regulation system pH to 5 of 0.5mol/L, then at 50 DEG C, react 3h;
1.2) the Boltorn H40 after '-methylene-bisacrylamide detect, obtain through N, N '-methylene-bisacrylamide activation of having reacted rear deionized water rinsing, until without N, N in cleaning fluid;
1.3) get some collagens, then clean with the dioxane aqueous solution that mass concentration is 10%, 30% and 50% respectively, after each cleaning, drain cleaning fluid by vacuum.Join in the aqueous solution of dioxane by the collagen rinsed well with dioxane, preparation collagen suspension liquid, wherein, the mol ratio of collagen surface amino groups and crosslinking agent is 1.2:1; Again will through N, Boltorn H40 after N '-methylene-bisacrylamide activation joins in collagen suspension liquid, under the air-proof condition of 60 DEG C, react 24h, then the product with deionized water cleaning that will obtain, wash away free activation hyper-branched polyester, obtain load hyper-branched polyester collagen;
2) synthesis of collagen load hyper-branched polyester/metal ion
Load hyper-branched polyester collagen step 1) obtained joins in solution of zinc sulfate, wherein, and load hyper-branched polyester collagen surface hydroxyl and Zn
2+mol ratio be 1:1.2; Again the pH of solution is adjusted to 6, and the 8h that vibrates at 40 DEG C, take out and filter, obtained collagen load hyper-branched polyester/metal ion fluoride adsorbent.
Above content is only and technological thought of the present invention is described; protection scope of the present invention can not be limited with this; every technological thought proposed according to the present invention, any change that technical scheme basis is done, within the protection domain all falling into claims of the present invention.
Claims (6)
1. a synthetic method for collagen load hyper-branched polyester/metal ion fluoride adsorbent, is characterized in that, comprise the following steps:
1) synthesis of load hyper-branched polyester collagen
1.1) be dissolved in hydrophilic organic solvent by superbrnaching end-hydroxy polyester, then add crosslinking agent wherein, wherein, the mol ratio of superbrnaching end-hydroxy polyester surface hydroxyl and crosslinking agent is (8 ~ 32): 1; Regulate pH to 4.5 ~ 10, then at 30 ~ 50 DEG C, react 1.5 ~ 3h;
1.2) react rear deionized water rinsing, until cross-linking agent-free detects in cleaning fluid, obtain the superbrnaching end-hydroxy polyester after crosslinking agent activation;
1.3) join in the aqueous solution of hydrophilic organic solvent by the collagen rinsed well with hydrophilic organic solvent, preparation collagen suspension liquid, wherein, the mol ratio of collagen surface amino groups and crosslinking agent is (0.8 ~ 1.2): 1; Again the superbrnaching end-hydroxy polyester after crosslinking agent activation is joined in collagen suspension liquid, 15 ~ 24h is reacted under the air-proof condition of 40 ~ 60 DEG C, the product with deionized water cleaning will obtained again, washes away free activation hyper-branched polyester, obtains load hyper-branched polyester collagen;
2) synthesis of collagen load hyper-branched polyester/metal ion
By step 1) the load hyper-branched polyester collagen that obtains joins in metal ion solution, wherein, the mol ratio of load hyper-branched polyester collagen surface hydroxyl and metal ion is 1:(0.9 ~ 1.2); Again the pH of solution is adjusted to 3 ~ 6.5, and the 2 ~ 8h that vibrates at 25 ~ 40 DEG C, take out and filter, obtained collagen load hyper-branched polyester/metal ion fluoride adsorbent, metal ion solution is aluminum sulfate solution, ferrum sulfuricum oxydatum solutum or solution of zinc sulfate.
2. the synthetic method of collagen load hyper-branched polyester according to claim 1/metal ion fluoride adsorbent, it is characterized in that: described step 1.1) in, superbrnaching end-hydroxy polyester is BoltornH20, Boltorn H30 or Boltorn H40.
3. the synthetic method of collagen load hyper-branched polyester according to claim 1/metal ion fluoride adsorbent, it is characterized in that: described step 1.1) in, crosslinking agent is epoxychloropropane, divinylsulfone or N, N '-methylene-bisacrylamide.
4. the synthetic method of collagen load hyper-branched polyester according to claim 1/metal ion fluoride adsorbent, it is characterized in that: described step 1.1) in, adjust ph is undertaken regulating by the NaOH solution of dropping 1mol/L or the HCl solution of dropping 0.5mol/L.
5. the synthetic method of collagen load hyper-branched polyester according to claim 1/metal ion fluoride adsorbent, it is characterized in that: described step 1.1) in, hydrophilic organic solvent is acetone, dioxane, dimethyl sulfoxide (DMSO) or DMF.
6. the synthetic method of collagen load hyper-branched polyester/metal ion fluoride adsorbent according to claim 1 or 5, it is characterized in that: described step 1.3) in, clean collagen is the hydrophilic organic solvent aqueous cleaning of 10%, 30% and 50% by mass concentration respectively, drains cleaning fluid after each cleaning by vacuum.
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| CN105327690A (en) * | 2015-10-20 | 2016-02-17 | 西南科技大学 | Method for preparing fluorinion adsorption material by utilizing leather particle for basic hydrolysis and loading with zirconium |
| CN108314894A (en) * | 2018-01-30 | 2018-07-24 | 浙江理工大学 | A kind of composite material and preparation method and application |
| CN109763029A (en) * | 2019-03-13 | 2019-05-17 | 殷红平 | A kind of high stability zinc alloy material and its processing technology |
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| JPS5889982A (en) * | 1981-11-25 | 1983-05-28 | Ebara Yuujiraito Kk | Treating method for waste water of plating device |
| CN1150975C (en) * | 2002-03-14 | 2004-05-26 | 安徽工业大学华冶自动化工程公司 | Spherical porous light haydite for treating waste water and its production method |
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