CN101775089B - Boron-absorbing resin containing bifunctional groups - Google Patents
Boron-absorbing resin containing bifunctional groups Download PDFInfo
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- CN101775089B CN101775089B CN2010100179653A CN201010017965A CN101775089B CN 101775089 B CN101775089 B CN 101775089B CN 2010100179653 A CN2010100179653 A CN 2010100179653A CN 201010017965 A CN201010017965 A CN 201010017965A CN 101775089 B CN101775089 B CN 101775089B
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Abstract
本发明公开了一种含双官能团的吸硼树脂及其制备方法。其特征在于：该含双官能团的吸硼树脂由卤代酰基化树脂与氨基糖进行反应制得。本方法制得的吸硼树脂的双官能团的担载量为0.1-2.8mmol/g，树脂制备过程安全、简单。树脂中的α-胺乙酰基和邻羟基双官能团发生协同作用，增强了树脂对硼的吸附、鳌合作用，可代替传统的硼特效树脂。The invention discloses a boron-absorbing resin containing two functional groups and a preparation method thereof. It is characterized in that: the boron-absorbing resin containing bifunctional groups is prepared by reacting halogenated acylation resin and amino sugar. The bifunctional group loading capacity of the boron-absorbing resin prepared by the method is 0.1-2.8 mmol/g, and the resin preparation process is safe and simple. The synergistic effect of the α-aminoacetyl group and the o-hydroxyl difunctional group in the resin enhances the adsorption and chelation of boron by the resin, and can replace the traditional boron special-effect resin.
Description
Technical field
The invention belongs to filed of functional.Be specifically related to a kind of suction boron resin that contains bifunctional.
Background technology
Boron is as a kind of important industrial raw material, the general a plurality of fields such as metallurgy, nuclear technique, military project, space flight, the energy, agricultural, medicine and automobile that are applied to of factory.The discharging of large amount of sewage has not only caused a large amount of boron resource losses in the boron compound production process, also environment is caused serious pollution.Run off, the below standard discharging of waste water containing boron of contaminate environment, make boron too high levels in the people drinking water source, thereby cause numerous disease.(World Health Organization WHO) requires the boron concentration in the tap water to be lower than 0.3mg/L, and therefore, studying the boron waste water treatment and utilizing becomes the important topic that the mankind face in the World Health Organization.
At present, existing many to the bibliographical information that the boron in the waste water is removed, method commonly used has the precipitator method, extraction process, reverse osmosis method, electrocoagulation, resin adsorption method (Simonnot, M.-O, Castel, C., NicolaI M., et al.Boron removalfrom drinking water with a boron selective resin:Is the treatment really selective? WaterResearch, 2000,34 (1): 109-116.Senkal, B.F., Bicak, N.Polymer supported iminodipropylene glycolfunctions for removal of boron.Reactive ﹠amp; Functional Polymers, 2003,55:27-33.Liu, H., Ye, X., Li, Q., et al.Boron adsorption using a new boron-selective hybrid gel and the commercial resinD564.Colloids and Surfaces A:Physicochemical and Engineering Aspects, 2009,341:118-126.) etc.It is controlled thorough that wherein resin adsorption method has the boron of removal, and the boron resource can be recycled through desorption, and polymeric adsorbent then can repeat advantages such as recycling utilization, is one of enrichment or removal boron the best way.
Nineteen fifty-seven, Lyman and Preuss (Lyman, W.R., Abington, Preuss, A.F.Boron-adsorbing resin andprocess for removing boron compounds from fluids, USA 1957:Vol.2813838.) at first makes a kind of effects of boron resin with chloromethylated polystyrene and the reaction of N-methyl glucoside amine.This resin has higher selectivity to boron in the solution, but this resin is subjected to the influence of multiple ambient conditions in application, afterwards through constantly development, people have synthesized many novel polymeric adsorbents, but there is certain problem in these resins, as adsorption rate and less stable, the resin building-up process is more loaded down with trivial details.Comparatively speaking, the suction boron resin that contains α-amine ethanoyl and adjacent hydroxyl bifunctional simultaneously is not only safer in preparation process, has reduced the harm to environment, and the α on the resin-amine ethanoyl and adjacent hydroxyl synergy has increased the adsorptive capacity of resin.The resin absorption amount can reach 28mg/g-and do agent.But therefore waste water qualified discharge after the plastic resin treatment can replace traditional effects of boron resin.
Summary of the invention
The present invention relates to a kind of suction boron resin that contains bifunctional and preparation method thereof.
The suction boron resin of bifunctional of the present invention has following structure:
R and R '=H or CH in the formula
3R ": be the residue of aminosugar such as N-methyl glucoside amine or GalN or glucosamine or chitosan.
The preparation of the wetting ability polymeric adsorbent of bifunctional of the present invention can be synthesized by the following method: with the PS-Acyl-X resin after solvent-swollen 0-24 hour; with a certain proportion of aminosugar under 25-100 ℃; reacted 3-24 hour, and obtained containing the wetting ability suction boron resin of α-amine ethanoyl and adjacent hydroxyl bifunctional.
The described PS-Acyl-X resin of present method can be linear or crosslinked, macropore or gel; Particle diameter is 5-1300 μ m; In the reaction in aminosugar and the PS-Acyl-X resin-mol ratio of X is 1-5; Wherein solvent can be water, N, dinethylformamide, tetrahydrofuran (THF), methyl alcohol, ethanol or water and N, dinethylformamide or tetrahydrofuran (THF) or methyl alcohol or alcoholic acid mixture.
Advantage of the present invention: the suction boron resin that contains bifunctional of the present invention is reacted by halo acylations resin and aminosugar and makes.The poly-hydroxy of the suction boron resin that present method makes has very strong huge legendary turtle cooperation usefulness to boron, and the α on the resin-amine ethanoyl and adjacent hydroxyl synergy have increased the adsorptive capacity of resin.
Specific embodiments
Embodiment 1
0% (V/V) DVB), 1.790 GalNs, 20ml N (degree of crosslinking:, dinethylformamide adds to be furnished with in the reactor of stirring, 90 ℃ of reactions 7 hours to take by weighing 1g PS-Acyl-Br.Promptly obtaining loading is 2.12mmol/g.
Embodiment 2
Take by weighing 1g PS-Acyl-Br resin (degree of crosslinking: 7% (V/V) DVB; Particle diameter 5 μ m), 3.580g N-methyl glucoside amine, 20ml water adds and is furnished with in the reactor of stirring, 80 ℃ of reactions 5 hours.Promptly obtaining loading is 2.51mmol/g.
Embodiment 3
Take by weighing 1g PS-Acyl-Cl resin (degree of crosslinking: 7% (V/V) DVB; Particle diameter 200 μ m), 0.3804g N-methyl glucoside amine, 25ml tetrahydrofuran (THF) adds and is furnished with in the reactor of stirring, 60 ℃ of reactions 3.5 hours.Promptly obtaining loading is 0.50mmol/g.
Embodiment 4
Take by weighing 1g PS-Acyl-Cl resin (degree of crosslinking: 1% (V/V) DVB; Particle diameter 1300 μ m), 5ml ethanol adds and to be furnished with in the reactor of stirring, normal temperature swelling 12 hours adds 5ml water, 70 ℃ of reactions of 1.5659g N-methyl glucoside amine 4 hours again.Promptly obtaining loading is 1.65mmol/g.
Embodiment 5
Take by weighing 1g PS-Acyl-Br resin (degree of crosslinking: 1% (V/V) DVB; Particle diameter 500 μ m), 1.3425g glucosamine, 10ml water, 5ml methyl alcohol add and be furnished with in the reactor of stirring, 40 ℃ of reactions 10 hours.Promptly obtaining loading is 0.69mmol/g.
Embodiment 6
Take by weighing 1g PS-Acyl-Cl resin (degree of crosslinking: 30% (V/V) DVB; Particle diameter 800 μ m), 0.8482g N-methyl glucoside amine, 25ml methyl alcohol adds and is furnished with in the reactor of stirring, 50 ℃ of reactions 6 hours.Promptly obtaining loading is 1.01mmol/g.
Embodiment 7
Take by weighing 1g PS-Acyl-Cl resin (degree of crosslinking: 7% (V/V) DVB; Particle diameter 50 μ m), 0.5007g chitosan, 10ml dilute hydrochloric acid add and be furnished with in the reactor of stirring, 60 ℃ of reactions 24 hours.Promptly obtaining loading is 1.02mmol/g.
Embodiment 8
Take by weighing 1g PS-Acyl-Br (degree of crosslinking: 1% (V/V) DVB; Particle diameter 500 μ m), 4.4750g; Glucosamine, 30ml ethanol add to be furnished with in the reactor of stirring, and 70 ℃ were reacted 16 hours.Promptly obtaining loading is 1.38mmol/g.
Embodiment 9
Take by weighing 1g PS-Acyl-Cl resin (degree of crosslinking: 7% (V/V) DVB; Particle diameter 1000 μ m), 1.3425g GalN, 10ml water, 5ml tetrahydrofuran (THF) add and be furnished with in the reactor of stirring, 40 ℃ of reactions 10 hours.Promptly obtaining loading is 1.69mmol/g.
Embodiment 10
Take by weighing 1g PS-Acyl-Br resin (degree of crosslinking: 80% (V/V) DVB; Particle diameter 1000 μ m), 0.8201g chitosan, the rare nitric acid of 10ml, 5ml N, dinethylformamide adds to be furnished with in the reactor of stirring, 70 ℃ of reactions 20 hours.Promptly obtaining loading is 1.53mmol/g.
Claims (7)
1. suction boron resin that contains bifunctional is characterized in that the suction boron resin of described bifunctional contains following structure:
R and R '=H or CH in the formula
3R ": be the aminosugar residue.
2. a kind of suction boron resin that contains bifunctional according to claim 1 is characterized in that described aminosugar residue is: N-methyl glucoside amine residue or GalN residue or glucosamine residue or chitosan residue.
3. a kind of suction boron resin that contains bifunctional according to claim 1, it is characterized in that this resin can prepare by following synthetic method: with macromole halo acylations polystyrene resin, this resin abbreviates PS-Acyl-X as, aminosugar and solvent add to be furnished with in the reactor of stirring, reaction is 3-24 hour in 25-100 ℃ of oil bath, obtains above-mentioned hydrophilic, the suction boron resin that contains α-amine ethanoyl and adjacent hydroxyl bifunctional; Wherein, in described aminosugar and the PS-Acyl-X resin-mol ratio of X is the ratio of 1-5.
4. a kind of suction boron resin that contains bifunctional according to claim 1, the content that it is characterized in that α-amine ethanoyl in the described bifunctional resin and adjacent hydroxyl bifunctional are that 0.1-2.8mmol/g-does agent.
5. a kind of suction boron resin that contains bifunctional according to claim 3 is characterized in that described PS-Acyl-X resin for linear or crosslinked, macropore or gel, particle diameter is 5-1300 μ m.
6. a kind of suction boron resin that contains bifunctional according to claim 3, it is characterized in that in the described PS-Acyl-X resin-X is Cl or Br.
7. a kind of suction boron resin that contains bifunctional according to claim 3, it is characterized in that described solvent can be water or N, dinethylformamide or tetrahydrofuran (THF) or methyl alcohol or ethanol or water and N, the mixture of dinethylformamide, or the mixture of water and tetrahydrofuran (THF), or water and methanol mixture, or water and alcoholic acid mixture.
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| Application Number | Priority Date | Filing Date | Title |
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| CN2010100179653A CN101775089B (en) | 2010-01-19 | 2010-01-19 | Boron-absorbing resin containing bifunctional groups |
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| CN2010100179653A CN101775089B (en) | 2010-01-19 | 2010-01-19 | Boron-absorbing resin containing bifunctional groups |
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| CN101775089B true CN101775089B (en) | 2011-12-28 |
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| CN103421132A (en) * | 2013-06-04 | 2013-12-04 | 南京工业大学 | Method for recycling recovered liquid in synthesis of acyl ethyl meglumine resin |
| CN115023407B (en) * | 2020-11-05 | 2024-05-24 | 瓦克化学股份公司 | Method for removing impurities from chlorosilane mixtures |
| CN115945179B (en) * | 2023-02-20 | 2023-08-29 | 江苏苏青水处理工程集团有限公司 | Low-solution-loss high-adsorption capacity salt lake lithium-extracting boron-extracting adsorption material and preparation method thereof |
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