CN111499775A - Polyamino modified cyclodextrin and application thereof - Google Patents
Polyamino modified cyclodextrin and application thereof Download PDFInfo
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Abstract
The invention relates to a polyamino modified cyclodextrin method, which comprises the following preparation steps of polyamino modified cyclodextrin in parts by weight: (1) dispersing cyclodextrin into water, and slowly adding 10-15% of strong alkali aqueous solution into the water until the system is transparent to obtain a solution I; (2) adding p-toluenesulfonyl chloride and acetonitrile into a reactor, dropwise adding the solution I into the reactor, continuously reacting for 3-5 h at room temperature after dropwise adding is finished for 0.5-1 h, finishing the reaction and carrying out suction filtration, putting the filtrate into a refrigerator overnight, separating out a large amount of white precipitates, carrying out suction filtration to obtain white solids, dissolving the white solids with water, carrying out suction filtration, refrigerating the filtrate to separate out a large amount of white precipitates, filtering, and carrying out vacuum drying to obtain poly-6-p-toluenesulfonyl cyclodextrin; (3) dissolving poly-6-p-toluenesulfonyl cyclodextrin and polyamine in a dipolar solvent, reacting for 4-6 h at 50-80 ℃, adding glycidyl methacrylate, continuing to react for 2-4 h, cooling to room temperature, adding methanol, adding acetone for precipitation, performing suction filtration to obtain a white solid, and repeating the dissolution of methanol and the precipitation of acetone to obtain the polyamino modified cyclodextrin containing double bonds.
Description
The invention relates to a divisional application of a cyclodextrin-based photocatalyst composite hydrogel and a preparation method thereof in a Chinese patent, wherein the application date is 11 and 27 in 2017, and the application number is 201711208765.4.
Technical Field
The invention relates to cyclodextrin, in particular to polyamino modified cyclodextrin and application thereof, and belongs to the technical field of chemical industry.
Technical Field
China is a country with water resource shortage, the per capita water resource amount is only 1/4 in the world, the water resource distribution is seriously uneven, and the problem of how to relieve the problems of water resource shortage, pollution and the like becomes a problem which is not slow at all. Heavy metal ion pollution causes harm to water environment and the whole ecological system through modes of water body accumulation and the like, and can endanger human health through direct contact or through a food chain. How to rapidly and efficiently remove heavy metal ions in water becomes a major topic in the research field of water pollution control.
Chinese patent CN201410123913.2 relates to a hydrogel for sewage treatment and a preparation method thereof, wherein the hydrogel comprises 5-90 parts of polyvinyl alcohol, 5-90 parts of chitosan, 0-20 parts of sodium carboxymethylcellulose, 0.05-0.3 part of graphene oxide and 3-5 parts of sodium alginate. The hydrogel disclosed by the invention can efficiently adsorb heavy metal ions in water, and has the characteristics of high adsorption capacity, high selectivity, cyclic recycling, biodegradability and the like. However, the hydrogel prepared by the method has poor comprehensive performance in water treatment, is easy to be polluted by microorganisms and the like to cause structural damage, and reduces the adsorption quantity.
Disclosure of Invention
In order to overcome the defect of small metal ion adsorption capacity in the prior art, the invention aims to provide a photocatalyst composite hydrogel based on cyclodextrin and a preparation method thereof.
The photocatalyst composite hydrogel based on cyclodextrin is a composite hydrogel with a three-dimensional network structure, contains a large number of amino groups and carboxylate groups for chelating heavy metal ions and nanometer titanium dioxide with a photocatalyst effect, and the preparation method comprises the following steps:
a. preparation of polyamino-modified cyclodextrins containing double bonds: dispersing 5-10 parts of cyclodextrin into 10-15 parts of water, and slowly adding 5-10 parts of 10% -15% strong base aqueous solution until the system is transparent to obtain a solution I; adding 5-15 parts of p-toluenesulfonyl chloride and 15-20 parts of acetonitrile into a reactor, dropwise adding the solution I into the reactor, continuously reacting for 3-5 hours at room temperature after 0.5-1 hour of dropwise addition is finished, finishing the reaction and carrying out suction filtration, putting the filtrate into a refrigerator overnight, separating out a large amount of white precipitate, carrying out suction filtration to obtain a white solid, dissolving the white solid with water, carrying out suction filtration, refrigerating the filtrate to separate out a large amount of white precipitate, filtering, and carrying out vacuum drying to obtain poly-6-p-toluenesulfonyl cyclodextrin; dissolving 3-5 parts of poly-6-p-toluenesulfonyl cyclodextrin and 15-20 parts of polyamine in 20-30 parts of dipolar solvent, reacting for 4-6 hours at 50-80 ℃, adding 1-3 parts of glycidyl methacrylate, continuing to react for 2-4 hours, cooling to room temperature, adding 20-30 parts of methanol, adding 20-30 parts of acetone for precipitation, performing suction filtration to obtain a white solid, and repeating the methanol dissolution and the acetone precipitation to obtain the polyamino modified cyclodextrin containing double bonds.
b. Preparation of composite hydrogel: weighing 15-20 parts of acrylamide, 15-25 parts of anionic monomer, 5-10 parts of crosslinking monomer, 10-15 parts of double-bond-containing polyamino modified cyclodextrin, 60-100 parts of water, 0.1-0.5 part of initiator and 0.5-1 part of reducing agent, adding into a reactor, stirring for dissolving, heating to 40-60 ℃, continuing to react for 3-5 h, then adding 5-8 parts of 10-30% nano titanium dioxide sol, stirring for 0.5-1 h, and cooling to room temperature to obtain a composite liquid; and (3) dripping the prepared composite solution into 3% calcium chloride-boric acid saturated solution by using an injector for chemical crosslinking, preparing spherical particle hydrogel with the particle size of 0.5-5 mm, soaking for 24h, finally washing with deionized water for 3-6 times, and naturally drying to obtain the cyclodextrin-based photocatalyst composite hydrogel.
The cyclodextrin is at least one of α -cyclodextrin, β -cyclodextrin and gamma-cyclodextrin.
The strong base is at least one of sodium hydroxide, potassium hydroxide and barium hydroxide.
The dipolar solvent is at least one of dimethyl sulfoxide (DMSO), N-Dimethylformamide (DMF), dimethylacetamide and hexamethylphosphoramide.
The polyamine is at least one of ethylenediamine, 1, 6-hexanediamine, diethylenetriamine, triethylene tetramine, tetraethylene pentamine, 1, 3-propane diamine and 1, 4-butane diamine.
The anion monomer is at least one of sodium acrylate, sodium methacrylate, itaconic acid disodium and fumaric acid disodium.
The crosslinking monomer is preferably at least one of N, N' -methylene bisacrylamide, N-dimethyl diallyl ammonium chloride, poly (hexamethylene dimethacrylate) and polyethylene glycol dimethacrylate.
The initiator is at least one of hydrogen peroxide, tert-butyl hydroperoxide, ammonium persulfate and potassium persulfate.
The reducing agent is at least one of ferrous chloride, sodium bisulfite, sodium hypophosphite, sodium formaldehyde sulfoxylate, ferrous pyrophosphate and ferrous sulfate.
An application method of a photocatalyst composite hydrogel based on cyclodextrin can be used in the fields of ion adsorption and industrial sewage treatment to remove heavy metals in water.
Compared with the prior art, the invention has the following advantages or beneficial results:
(1) the polyamino modified cyclodextrin containing double bonds is prepared for the first time, and the three-dimensional structure of the composite hydrogel after copolymerization contains a large amount of polyamino modified cyclodextrin, so that the chelating capacity of the composite hydrogel is stronger, and the composite hydrogel is more sensitive to capture of metal ions; (2) the composite hydrogel is modified by adopting nano titanium dioxide, absorbs and converts visible light and ultraviolet light, and then has the sterilization effect.
Detailed Description
The present application will be described in further detail with reference to examples. It is to be understood that the specific embodiments described herein are merely illustrative of the relevant invention and not restrictive of the invention.
It should be noted that the embodiments and features of the embodiments in the present application may be combined with each other without conflict.
Example 1
A cyclodextrin-based photocatalyst composite hydrogel is a composite hydrogel with a three-dimensional network structure, contains a large number of amino groups and carboxylate groups for chelating heavy metal ions and nanometer titanium dioxide with a photocatalyst effect, and is prepared by the following steps:
a. the preparation method of the polyamino modified cyclodextrin containing double bonds comprises the steps of dispersing 6 parts of α -cyclodextrin into 12 parts of water, slowly adding 8 parts of 13% potassium hydroxide aqueous solution into the water until a system is transparent to obtain a solution I, adding 10 parts of paratoluensulfonyl chloride and 15 parts of acetonitrile into a reactor, dropwise adding the solution I into the reactor, continuously reacting for 4 hours at room temperature after 0.5 hour of dropwise adding is finished, finishing reaction and suction filtering, placing the filtrate into a refrigerator overnight to separate out a large amount of white precipitate, suction filtering to obtain a white solid, dissolving the white solid in water, suction filtering, refrigerating the filtrate to separate out a large amount of white precipitate, filtering, and drying in vacuum to obtain poly-6-paratoluenesulfonyl cyclodextrin, dissolving 4 parts of poly-6-paratoluenesulfonyl cyclodextrin and 20 parts of ethylenediamine into 21 parts of DMSO, reacting for 5 hours at 60 ℃, adding 2 parts of glycidyl methacrylate, continuously reacting for 2 hours, cooling to room temperature, adding 30 parts of methanol, adding 20 parts of acetone into the mixture for precipitation to obtain a white solid, and repeatedly dissolving and precipitating the acetone to obtain the polyamino modified cyclodextrin containing double bonds.
b. Preparation of composite hydrogel: weighing 16 parts of acrylamide, 20 parts of sodium acrylate, 8 parts of N, N' -methylene bisacrylamide, 12 parts of polyamino modified cyclodextrin containing double bonds, 85 parts of water, 0.3 part of hydrogen peroxide and 0.6 part of sodium formaldehyde sulfoxylate, adding into a reactor, stirring and dissolving, heating to 50 ℃, continuing to react for 5 hours, then adding 6 parts of 15% nano titanium dioxide sol, stirring for 1 hour, and cooling to room temperature to obtain a composite solution; and (3) dripping the prepared composite solution into 3% calcium chloride-boric acid saturated solution by using an injector to carry out chemical crosslinking, preparing spherical particle hydrogel with the particle size of 2.2-3 mm, soaking for 24h, finally washing with deionized water for 4 times, and naturally drying to obtain the cyclodextrin-based photocatalyst composite hydrogel.
Example 2
A cyclodextrin-based photocatalyst composite hydrogel is a composite hydrogel with a three-dimensional network structure, contains a large number of amino groups and carboxylate groups for chelating heavy metal ions and nanometer titanium dioxide with a photocatalyst effect, and is prepared by the following steps:
a. preparation of polyamino-modified cyclodextrins containing double bonds: dispersing 5 parts of gamma-cyclodextrin into 12 parts of water, and then slowly adding 8 parts of 10% sodium hydroxide aqueous solution into the water until the system is transparent to obtain a solution I; adding 15 parts of p-toluenesulfonyl chloride and 18 parts of acetonitrile into a reactor, dropwise adding the solution I into the reactor, continuously reacting for 5 hours at room temperature after 1 hour of dropwise adding is finished, finishing the reaction and carrying out suction filtration, putting the filtrate into a refrigerator overnight, separating out a large amount of white precipitates, carrying out suction filtration to obtain white solids, dissolving the white solids with water, carrying out suction filtration, refrigerating the filtrate to separate out a large amount of white precipitates, filtering, and carrying out vacuum drying to obtain poly-6-p-toluenesulfonyl cyclodextrin; dissolving 5 parts of poly-6-p-toluenesulfonyl cyclodextrin and 19 parts of triethylene tetramine in 30 parts of DMSO, reacting for 4 hours at 80 ℃, adding 1.8 parts of glycidyl methacrylate, continuing to react for 4 hours, cooling to room temperature, adding 30 parts of methanol, adding 22 parts of acetone for precipitation, performing suction filtration to obtain a white solid, and repeating the methanol dissolution and the acetone precipitation to obtain the polyamino modified cyclodextrin containing double bonds.
b. Preparation of composite hydrogel: weighing 20 parts of acrylamide, 25 parts of disodium itaconate, 6 parts of N, N-dimethyl diallyl ammonium chloride, 12 parts of polyamino modified cyclodextrin containing double bonds, 90 parts of water, 0.1 part of ammonium persulfate and 0.5 part of ferrous chloride, adding into a reactor, stirring for dissolving, heating to 40 ℃, continuing to react for 5 hours, then adding 8 parts of 15% nano titanium dioxide sol, stirring for 0.6 hour, and cooling to room temperature to obtain a composite solution; and (3) dripping the prepared composite solution into 3% calcium chloride-boric acid saturated solution by using an injector for chemical crosslinking, preparing spherical particle hydrogel with the particle size of 4.5-5 mm, soaking for 24h, finally washing with deionized water for 5 times, and naturally drying to obtain the cyclodextrin-based photocatalyst composite hydrogel.
Example 3
A cyclodextrin-based photocatalyst composite hydrogel is a composite hydrogel with a three-dimensional network structure, contains a large number of amino groups and carboxylate groups for chelating heavy metal ions and nanometer titanium dioxide with a photocatalyst effect, and is prepared by the following steps:
a. the preparation method of the polyamino modified cyclodextrin containing double bonds comprises the steps of dispersing 7 parts of β -cyclodextrin into 13 parts of water, slowly adding 7 parts of 14% sodium hydroxide aqueous solution into the water until a system is transparent to obtain a solution I, adding 9 parts of paratoluensulfonyl chloride and 20 parts of acetonitrile into a reactor, dropwise adding the solution I into the reactor, continuously reacting for 4.5 hours at room temperature after 0.6 hour of dropwise adding is finished, finishing reaction and suction filtration, placing the filtrate into a refrigerator overnight to separate out a large amount of white precipitate, obtaining the white solid through suction filtration, dissolving the white solid in water, then performing suction filtration, refrigerating the filtrate to separate out a large amount of white precipitate, filtering, and performing vacuum drying to obtain the poly-6-paratoluenesulfonyl cyclodextrin, dissolving 3.6 parts of the poly-6-paratoluenesulfonyl cyclodextrin and 18 parts of diethylenetriamine into 23 parts of DMF, reacting for 5.5 hours at 65 ℃, adding 2 parts of glycidyl methacrylate, continuously reacting for 3 hours, cooling to room temperature, adding 28 parts of methanol, then adding 22 parts of acetone to precipitate, obtaining the white solid, and repeatedly dissolving the methanol and acetone precipitate to obtain the polyamino modified cyclodextrin containing double bonds.
b. Preparation of composite hydrogel: weighing 17 parts of acrylamide, 25 parts of disodium fumarate, 10 parts of polyhexamethylene dimethacrylate, 14 parts of polyamino modified cyclodextrin containing double bonds, 75 parts of water, 0.4 part of tert-butyl hydroperoxide and 0.8 part of sodium bisulfite, adding the mixture into a reactor, stirring and dissolving the mixture, heating the mixture to 55 ℃, continuing to react for 4 hours, then adding 6 parts of 25% nano titanium dioxide sol, stirring the mixture for 1 hour, and cooling the mixture to room temperature to obtain a composite solution; and (3) dripping the prepared composite solution into 3% calcium chloride-boric acid saturated solution by using an injector for chemical crosslinking, preparing spherical particle hydrogel with the particle size of 2.5-3.5 mm, soaking for 24h, finally washing with deionized water for 6 times, and naturally drying to obtain the cyclodextrin-based photocatalyst composite hydrogel.
The hydrogel in the examples and the commercially available anionic carboxymethyl chitosan hydrogel were selected for Cu with different concentrations2+、Pb2+、Cd2+、Cr3+、Ni2+And (5) carrying out an adsorption performance test under the same condition. The specific test method comprises the steps of weighing a certain mass of hydrogel, adding the hydrogel into a heavy metal ion solution with a certain initial concentration, testing the concentration change after adsorption, and calculating the maximum adsorption capacity. The specific data are as follows:
Claims (10)
1. the preparation method of the polyamino modified cyclodextrin is characterized in that the preparation method comprises the following steps of:
(1) dispersing cyclodextrin into water, and slowly adding 10-15% of strong alkali aqueous solution into the water until the system is transparent to obtain a solution I;
(2) adding p-toluenesulfonyl chloride and acetonitrile into a reactor, dropwise adding the solution I into the reactor, continuously reacting for 3-5 h at room temperature after dropwise adding is finished for 0.5-1 h, finishing the reaction and carrying out suction filtration, putting the filtrate into a refrigerator overnight, separating out a large amount of white precipitates, carrying out suction filtration to obtain white solids, dissolving the white solids with water, carrying out suction filtration, refrigerating the filtrate to separate out a large amount of white precipitates, filtering, and carrying out vacuum drying to obtain poly-6-p-toluenesulfonyl cyclodextrin;
(3) dissolving poly-6-p-toluenesulfonyl cyclodextrin and polyamine in a dipolar solvent, reacting for 4-6 h at 50-80 ℃, adding glycidyl methacrylate, continuing to react for 2-4 h, cooling to room temperature, adding methanol, adding acetone for precipitation, performing suction filtration to obtain a white solid, and repeating the dissolution of methanol and the precipitation of acetone to obtain the polyamino modified cyclodextrin containing double bonds.
2. The method of claim 1, wherein the polyamino-modified cyclodextrin is prepared by the following steps in parts by mass:
(1) dispersing 5-10 parts of cyclodextrin into 10-15 parts of water, and slowly adding 5-10 parts of 10% -15% strong base aqueous solution until the system is transparent to obtain a solution I;
(2) adding 5-15 parts of paratoluensulfonyl chloride and 15-20 parts of acetonitrile into a reactor, dropwise adding the solution I into the reactor, continuously reacting for 3-5 hours at room temperature after 0.5-1 hour of dropwise addition is finished, finishing the reaction and carrying out suction filtration, putting the filtrate into a refrigerator overnight, separating out a large amount of white precipitates, carrying out suction filtration to obtain white solids, dissolving the white solids with water, carrying out suction filtration, refrigerating the filtrate to separate out a large amount of white precipitates, filtering, and carrying out vacuum drying to obtain poly-6-paratoluenesulfonyl cyclodextrin;
(3) dissolving 3-5 parts of poly-6-p-toluenesulfonyl cyclodextrin and 15-20 parts of polyamine in 20-30 parts of dipolar solvent, reacting for 4-6 hours at 50-80 ℃, adding 1-3 parts of glycidyl methacrylate, continuing to react for 2-4 hours, cooling to room temperature, adding 20-30 parts of methanol, adding 20-30 parts of acetone for precipitation, performing suction filtration to obtain a white solid, and repeating the methanol dissolution and the acetone precipitation to obtain the polyamino modified cyclodextrin containing double bonds.
3. A polyamino modified cyclodextrin process of claim 1 or 2, wherein said cyclodextrin is at least one of α -cyclodextrin, β -cyclodextrin, γ -cyclodextrin.
4. The method of claim 1 or 2, wherein the strong base is at least one of sodium hydroxide, potassium hydroxide, and barium hydroxide.
5. A polyamino modified cyclodextrin according to claim 1 or 2, wherein: the dipolar solvent is at least one of dimethyl sulfoxide (DMSO), N-Dimethylformamide (DMF), dimethylacetamide and hexamethylphosphoramide.
6. A polyamino modified cyclodextrin according to claim 1 or 2, wherein: the polyamine is at least one of ethylenediamine, 1, 6-hexanediamine, diethylenetriamine, triethylene tetramine, tetraethylene pentamine, 1, 3-propane diamine and 1, 4-butane diamine.
7. The method for applying the polyamino-modified cyclodextrin as claimed in claim 1 or 2, wherein the polyamino-modified cyclodextrin is applied to the cyclodextrin-based photocatalyst composite hydrogel, and is widely applied to the fields of ion adsorption and industrial sewage treatment.
8. The method for applying the polyamino-modified cyclodextrin of claim 7, wherein the cyclodextrin-based photocatalyst composite hydrogel is prepared by the following steps:
(1) weighing 15-20 parts of acrylamide, 15-25 parts of anionic monomer, 5-10 parts of crosslinking monomer, 10-15 parts of double-bond-containing polyamino modified cyclodextrin, 60-100 parts of water, 0.1-0.5 part of initiator and 0.5-1 part of reducing agent, adding into a reactor, stirring for dissolving, heating to 40-60 ℃, continuing to react for 3-5 h, then adding 5-8 parts of 10-30% nano titanium dioxide sol, stirring for 0.5-1 h, and cooling to room temperature to obtain a composite liquid;
(2) and (3) dripping the prepared composite solution into 3% calcium chloride-boric acid saturated solution by using an injector for chemical crosslinking, preparing spherical particle hydrogel with the particle size of 0.5-5 mm, soaking for 24h, finally washing with deionized water for 3-6 times, and naturally drying to obtain the cyclodextrin-based photocatalyst composite hydrogel.
9. The method of claim 8, wherein the anionic monomer is at least one of sodium acrylate, sodium methacrylate, disodium itaconate, and disodium fumarate; the crosslinking monomer is preferably at least one of N, N' -methylene bisacrylamide, N-dimethyl diallyl ammonium chloride, poly (hexamethylene dimethacrylate) and polyethylene glycol dimethacrylate.
10. The method of claim 8, wherein the initiator is at least one of hydrogen peroxide, tert-butyl hydroperoxide, ammonium persulfate, and potassium persulfate; the reducing agent is at least one of ferrous chloride, sodium bisulfite, sodium hypophosphite, sodium formaldehyde sulfoxylate, ferrous pyrophosphate and ferrous sulfate.
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| CN201711208765.4A Pending CN107903409A (en) | 2017-11-27 | 2017-11-27 | A kind of photocatalyst composite hydrogel based on cyclodextrin and preparation method thereof |
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2017
- 2017-11-27 CN CN202010358507.XA patent/CN111499775A/en not_active Withdrawn
- 2017-11-27 CN CN201711208765.4A patent/CN107903409A/en active Pending
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| CN115536138B (en) * | 2022-08-26 | 2024-05-14 | 龙海市雷尔生物科技有限公司 | Cyclodextrin cross-linked chitosan embedded nitrifying bacteria wastewater treatment agent and preparation method thereof |
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| CN107903409A (en) | 2018-04-13 |
| CN111499887A (en) | 2020-08-07 |
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