CN115155529A - Boron adsorption resin and preparation method thereof - Google Patents

Boron adsorption resin and preparation method thereof Download PDF

Info

Publication number
CN115155529A
CN115155529A CN202110353290.8A CN202110353290A CN115155529A CN 115155529 A CN115155529 A CN 115155529A CN 202110353290 A CN202110353290 A CN 202110353290A CN 115155529 A CN115155529 A CN 115155529A
Authority
CN
China
Prior art keywords
resin
crosslinked
boron
resin containing
polymer resin
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Pending
Application number
CN202110353290.8A
Other languages
Chinese (zh)
Inventor
阎虎生
姚迁娜
毛进池
郭为磊
尹志义
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Kairui Environmental Protection Technology Co ltd
Nankai University
Original Assignee
Kairui Environmental Protection Technology Co ltd
Nankai University
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Kairui Environmental Protection Technology Co ltd, Nankai University filed Critical Kairui Environmental Protection Technology Co ltd
Priority to CN202110353290.8A priority Critical patent/CN115155529A/en
Publication of CN115155529A publication Critical patent/CN115155529A/en
Pending legal-status Critical Current

Links

Classifications

    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
    • B01J20/22—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising organic material
    • B01J20/26—Synthetic macromolecular compounds
    • B01J20/261—Synthetic macromolecular compounds obtained by reactions only involving carbon to carbon unsaturated bonds
    • C—CHEMISTRY; METALLURGY
    • C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F1/00—Treatment of water, waste water, or sewage
    • C02F1/28—Treatment of water, waste water, or sewage by sorption
    • C02F1/285—Treatment of water, waste water, or sewage by sorption using synthetic organic sorbents
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F212/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by an aromatic carbocyclic ring
    • C08F212/02—Monomers containing only one unsaturated aliphatic radical
    • C08F212/04—Monomers containing only one unsaturated aliphatic radical containing one ring
    • C08F212/06—Hydrocarbons
    • C08F212/08—Styrene
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F8/00—Chemical modification by after-treatment
    • C08F8/18—Introducing halogen atoms or halogen-containing groups
    • C08F8/24—Haloalkylation
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F8/00—Chemical modification by after-treatment
    • C08F8/30—Introducing nitrogen atoms or nitrogen-containing groups
    • C08F8/32—Introducing nitrogen atoms or nitrogen-containing groups by reaction with amines
    • C—CHEMISTRY; METALLURGY
    • C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F2101/00—Nature of the contaminant
    • C02F2101/10—Inorganic compounds
    • C—CHEMISTRY; METALLURGY
    • C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F2103/00—Nature of the water, waste water, sewage or sludge to be treated
    • C02F2103/007—Contaminated open waterways, rivers, lakes or ponds
    • C—CHEMISTRY; METALLURGY
    • C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F2103/00—Nature of the water, waste water, sewage or sludge to be treated
    • C02F2103/08—Seawater, e.g. for desalination

Landscapes

  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Health & Medical Sciences (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • General Chemical & Material Sciences (AREA)
  • Water Supply & Treatment (AREA)
  • Environmental & Geological Engineering (AREA)
  • Engineering & Computer Science (AREA)
  • Analytical Chemistry (AREA)
  • Hydrology & Water Resources (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)

Abstract

The invention discloses an adsorption resin for adsorbing boron and a preparation method thereof, wherein the skeleton of the resin is crosslinked polystyrene or crosslinked polyacrylamide or crosslinked polymethacrylamide, and the functional group for adsorbing boron is 2,3-dihydroxypropylamine. The synthesis process is to introduce polyamine group on the cross-linked polymer precursor and then 2,3-dihydroxypropyl group on the amine group. The boron adsorption resin has the advantages of high adsorption quantity, simple synthesis process and low cost.

Description

Boron adsorption resin and preparation method thereof
Technical Field
The invention relates to the field of boron adsorption resin, in particular to crosslinked polymer resin containing 2,3-dihydroxypropylamine as a boron adsorbent.
Background
Boron and boron compounds thereof are widely applied to modern industrial fields such as metallurgy, medicine, glass, ceramics, war industry, aerospace, atomic energy and the like, so that boron and boron compounds thereof not only serve as an important industrial raw material, but also serve as an important strategic substance to gain high attention of various countries. At present, the reserves of easily decomposed high-grade borate ores are reduced along with the large consumption of boron ore resources, and seawater and certain salt lake water often contain boron compounds with higher concentration, so that the development of a technology for extracting boron from the seawater and the salt lake water is emphasized in various countries in the world in recent years. On the other hand, with the application of boron and its compounds in numerous industrial processes, large amounts of boron-containing waste water are produced. Although boron is an essential element of plants, human beings and animals in many aspects, once the amount exceeds the requirement, the boron can cause great harm to animals, plants and human beings, for example, the immune system, the nervous system and the reproductive system of human bodies can be seriously damaged or even die due to excessive contact with the boron, and the boron is a very important industrial resource and is used in a plurality of industries for a long time. Due to the high volatility of boron, groundwater is polluted, which causes serious environmental problems, and the harm of boron in the environment has become a concern of environmental science. It is of great significance to effectively remove and recover boron from wastewater. It is also of practical interest to remove trace amounts of boron impurities from certain organic systems, such as from chlorosilanes.
The boron to be removed or extracted in the aqueous solution or organic system is mainly present in the form of boric acid or a salt thereof, and the methods for removing or extracting boron from the aqueous solution mainly include: (1) extraction method: the main technological principle of the extraction method is to use an organic reagent which contains ortho-dihydroxy and is not soluble in water as an extracting agent to be mixed with a solution containing boric acid or boric acid salt. Boric acid can react with polyhydroxy functional groups in an organic reagent to generate a complex which is extracted into an organic phase, thereby achieving the purpose of separating other ions in the water phase. However, the easy consumption of the extracting agent is the biggest disadvantage of the extraction method. (2) reverse osmosis: the membrane process is that the property of a reverse osmosis membrane that ionic substances are intercepted by selectively penetrating a solvent is utilized, and the static pressure difference at two sides of the membrane is taken as a driving force to overcome the osmotic pressure of the solvent, so that the solvent passes through the reverse osmosis membrane to realize the separation of a liquid mixture. However, the method has strong dependence on the pH of the solution, and the existing commercial reverse osmosis membrane has unsatisfactory effect on retaining boron. (3) adsorption method: boron is removed by utilizing the electron deficiency characteristic of boron and the characteristic of easy adsorption by an adsorbent. (4) ion exchange method: through ion exchange, borate anions are attached to anion exchange resin, so that the purposes of separation and concentration are achieved.
The resin containing amino and polyhydroxy functional groups is one of the most effective methods for adsorbing boron, borate anions and protonated amino form ionic bonds, and are coordinated with polyhydroxy groups adjacent to the amino to form stable five-membered ring or six-membered ring chelates, so that the resin has very high adsorption effect on boric acid. For example, N-methylglucamine is immobilized on a resin as a boron-adsorbing resin by nucleophilic substitution reaction of a chloromethylated crosslinked polystyrene resin with N-methylglucamine. A variety of such resins are commercially available, such as Amberlite-IRA 743 (Rohm and Haas Corporation), dowex XUS 43594 (Dow Chemicals), purolite S-108 (Purolite International), and Diaion CRB 02, diaion CRB 03, and Diaion CRB 05 (Mitsubishi Corporation). The disadvantage of this type of resin is that a maximum of 1 boron-adsorbing functional group N-methylglucamine can be attached to each polystyrene unit, and the formula weight of the polystyrene structural unit is large, and therefore the boron adsorption is low. Senkal et al (B.F. Senkal, N.Bicak, reactive & Functional Polymers 2003, 55, 27-33) reported that divinylbenzene, methyl methacrylate and glycidyl methacrylate were copolymerized to obtain a spherical resin, epoxy groups on the spherical resin were reacted with ethylenediamine, and then reacted with glycidyl to obtain a copolymer in which at most 2 amine groups can be attached to each glycidyl methacrylate structural unit, and 2 vicinal diol Functional groups are attached to each amine group, thereby having a large amount of boron adsorption. This boron adsorption resin has a disadvantage that glycidyl methacrylate, which is expensive, is used as a raw material in synthesizing the resin. Luo et al (Q.Luo, et al, reactive and Functional Polymers 2020, 150, 104543) also synthesized nanoscale microspheres using glycidyl methacrylate as a Functional monomer and introduced similar Functional groups for boron adsorption into the microspheres. The system not only uses the expensive glycidyl methacrylate as a raw material, but also the nano-scale microspheres cannot be applied to the conventional column adsorption or kettle adsorption application. There are also many reports of boron adsorption resins containing amine groups and ortho-dihydroxy groups, which either have low adsorption capacity, complicated synthesis process, or use expensive raw materials, and thus have limited practical applications in boron removal processes.
The invention content is as follows:
the invention overcomes the defects of boron adsorption resin reported in literature and provides the adsorption resin with simple synthesis process, low price and high boron adsorption capacity, and more amino and ortho-dihydroxy are introduced into each structural unit introduced by functional monomers of a polymer, or more functional groups are introduced by adopting the functional monomers with smaller formula weight, or the adsorption resin has the structural characteristics of the amino and ortho-dihydroxy. Specifically, the structural characteristics of the synthesized boron adsorption resin are represented by the following formula:
Figure BSA0000238104080000021
wherein:
Figure BSA0000238104080000022
the microsphere represents a crosslinked polymer skeleton with the conventional adsorption resin particle size, and the structural unit for connecting functional groups in the skeleton is as follows:
Figure BSA0000238104080000031
r = H or CH in the above formula 3 。
The crosslinked polymer backbone of the boron adsorbent resin of the present invention is divided into 2 series, which are described below.
The first series is a crosslinked polystyrene skeleton, the synthesis process comprises the steps of reacting chloromethylated crosslinked polystyrene resin with ethylenediamine, diethylenetriamine, triethylenetetramine, tetraethylenepentamine, pentaethylenehexamine, hexaethyleneheptamine or polyethylene polyamine, and then further reacting under the condition A to introduce a functional group for adsorbing boron, wherein the reaction formula is as follows:
Figure BSA0000238104080000032
in the above reaction formula where n =1, 2,3, 4, 5 or 6, reaction condition a includes 3: the reactants are epichlorohydrin and sodium hydroxide; (2) the reactant is glycidol; (3) The reactants were 3-chloro-1,2-propanediol and sodium hydroxide.
The second series is cross-linked polyacrylamide or cross-linked polymethacrylamide skeleton, which is synthesized by reacting cross-linked polymethyl acrylate, cross-linked polyacrylonitrile, cross-linked polymethyl methacrylate or cross-linked polymethacrylonitrile with ethylenediamine, diethylenetriamine, triethylenetetramine, tetraethylenepentamine, pentaethylenehexamine, hexaethyleneheptamine or polyethylene polyamine, or reacting with polyamine and a certain amount of water, and then further reacting under A condition to introduce a functional group for adsorbing boron, wherein the reaction formula is as follows:
Figure BSA0000238104080000033
Figure BSA0000238104080000041
n =1, 2,3, 4, 5 or 6 in the above 2 reaction formulae, r = h or CH 3 Reaction condition a is the same as 3 reaction conditions in the first series, namely: the reactants are epichlorohydrin and sodium hydroxide; (2) the reactant is glycidol; (3) The reactants were 3-chloro-1,2-propanediol and sodium hydroxide.
The chloromethylated crosslinked polystyrene resin used in the present invention can be synthesized by any conventional method, and the resin can be spherical or randomly granular, preferably spherical. The particle size of the resin is 0.001mm to 2mm, preferably 0.2mm to 1.2mm. The spherical chloromethylation crosslinked polystyrene resin can be subjected to suspension free radical copolymerization through styrene and divinylbenzene to obtain crosslinked polystyrene microspheres, and then the crosslinked polystyrene microspheres are subjected to chloromethylation to obtain chloromethyl crosslinked polystyrene microspheres. Chloromethylation can be carried out using a method of how chloromethylation is carried out, such as chloromethylation using a lewis acid such as anhydrous zinc chloride, anhydrous aluminum trichloride, etc. as a catalyst, and chloromethyl ether as a chloromethylating agent.
The crosslinked polymethyl acrylate, crosslinked polymethyl methacrylate, crosslinked polyacrylonitrile or crosslinked polymethacrylonitrile used in the present invention may be synthesized by any conventional method, and the resin may be spherical or randomly granular, preferably spherical. The particle size of the resin is 0.001mm to 2mm, preferably 0.2mm to 1.2mm. For example, methyl acrylate, methyl methacrylate, acrylonitrile or methacrylonitrile as functional monomer and cross-linking agent containing 2 or more than 2 double bonds are subjected to suspension free radical copolymerization to obtain cross-linked polymer microspheres containing ester groups or cyano groups, the cross-linking agent containing 2 or more than 2 double bonds includes but is not limited to divinylbenzene, ethylene glycol dimethacrylate, triallyl isocyanurate and triallyl cyanurate, and the cross-linking agent can be used alone or 2 or more than 2 kinds of cross-linking agents can be mixed for use.
Chloromethylated crosslinked polystyrene, crosslinked polymethyl acrylate, crosslinked polyacrylonitrile, crosslinked polymethyl methacrylate, or crosslinked polymethacrylonitrile, ethylenediamine, diethylenetriamine, triethylenetetramine, tetraethylenepentamine, pentaethylenehexamine, hexaethyleneheptamine or polyethylene polyamine react, or react with polyamine and a certain amount of water to introduce polyamine, the ratio of polyamine to water is less than or equal to 80/20, and the reaction temperature is from room temperature to 160 ℃ or reflux temperature. The reaction of introducing polyamine into resin and further introducing vicinal diol may be carried out by any of 3 methods, (1) reacting resin containing polyamine group with epichlorohydrin under alkaline condition, which may use any strong or weak base reagent, preferably sodium hydroxide, with water, methanol or ethanol as solvent, at room temperature to 100 ℃; (2) Reacting polyamine resin with glycidol, using water, methanol or ethanol as solvent, and reacting at room temperature to 100 ℃; (3) The polyamine group-containing resin is reacted with 3-chloro-1,2-propanediol under alkaline conditions, which may use any strong or weak base reagent, preferably sodium hydroxide, with water, methanol or ethanol as solvent, at room temperature to 100 ℃.
The resin containing amino and ortho-dihydroxy synthesized by the invention can be used for adsorbing boric acid and salts thereof from an aqueous solution, such as adsorbing boron from seawater or salt lake water, or adsorbing boron in boron-containing wastewater, or adsorbing boron impurities in an organic system.
Has the beneficial effects that:
the resin containing the o-dihydroxy functional group has the advantages of simple preparation process, low cost and large boron adsorption capacity.
Detailed Description
The invention is further illustrated by the following examples, which are intended only for a better understanding of the contents of the invention. It is to be understood that the scope of the invention is not to be limited by the embodiments, but is to be determined by the scope of the appended claims.
Example 1
A1000 mL three-neck flask is added with 400mL aqueous solution containing 1% gelatin and 10% sodium chloride, 58.4g styrene, 11.6g divinylbenzene (content: 50.2%), 35g n-heptane and 0.5g azobisisobutyronitrile are mixed uniformly, the organic phase is added into the flask, nitrogen is introduced, stirring is started to disperse the organic phase into oil globules with proper size, the mixture is heated to 60 ℃ for reaction for 4h, and then heated to 70 ℃ for reaction for 6h. Washing the formed resin with hot water for several times, extracting with acetone in a Soxhlet extractor for 6h, then air drying the resin, vacuum drying, sieving and collecting the resin with 30-60 meshes for later use.
150mL of chloromethyl ether and 50g of the resin obtained above were added to a 500mL three-necked flask, stirred for 2 hours, then 15g of anhydrous zinc chloride was added, heated to 40 ℃ under stirring to react for 12 hours, the resin obtained was sufficiently washed with methanol, air-dried, and vacuum-dried to obtain a chloromethylated polystyrene resin, and the chlorine content was measured to be 19.2%.
Adding 60mL of ethylenediamine and 10g of chloromethylated polystyrene resin into a 100mL three-neck flask, heating to 50 ℃ under stirring, reacting for 12h, fully washing the obtained resin with deionized water, airing, and drying in vacuum to obtain an amino-containing resin, wherein the weak base exchange capacity is 8.23mmol/g.
5g of the amino group-containing resin is suspended in 20mL of methanol, 10g of epichlorohydrin and 3.5g of sodium hydroxide are added, the mixture is heated to 50 ℃ under stirring to react for 12 hours, and the resin is washed by ethanol to obtain the resin containing amino group and ortho-dihydroxy. The hydroxyl group content of the obtained resin was measured to be 15.3mmol/g by a method of oxidizing periodic acid, reacting excess periodic acid with potassium iodide to form iodine, and then measuring the o-dihydroxy content by sodium thiosulfate reductive titration. 0.1000g of the resin was suspended in 25.00mL of a boric acid solution having a concentration of 1000ppm and shaken for 24 hours, and the concentration of boron in the mother liquor after adsorption was measured spectrophotometrically by the color reaction of azomethine-H acid with boric acid, and the adsorption amount of boron adsorbed by the resin was calculated to be 32.5mg/g.
Example 2
60mL of triethylene tetramine and 10g of chloromethylated polystyrene resin obtained in example 1 are added into a 100mL three-neck flask, the mixture is heated to 80 ℃ under stirring to react for 12 hours, the obtained resin is fully washed by deionized water, air-dried and vacuum-dried to obtain amino-containing resin, and the weak base exchange capacity is 10.1mmol/g.
5g of the amino group-containing resin is suspended in 20mL of water, 10g of glycidol is added, the mixture is heated to 50 ℃ under stirring to react for 12h, and the resin is washed with ethanol to obtain the amino group-containing resin and the ortho-dihydroxy resin. The hydroxyl group content of the resulting resin was measured to be 17.8mmol/g with reference to the method for measuring the hydroxyl group content in example 1. 0.1000g of the resin was suspended in 25.00mL of a boric acid solution having a concentration of 1000ppm and shaken for 24 hours, and the concentration of boron in the mother liquor after adsorption was measured with reference to the method for measuring the boron concentration in example 1, and the adsorption amount of boron adsorbed by the resin was calculated to be 46.7mg/g.
Example 3
A1000 mL three-necked flask was charged with 400mL of an aqueous solution containing 1% gelatin and 10% sodium chloride, 54.7g of methyl acrylate, 13.9g of divinylbenzene (content: 50.2%), 1.4g of triallyl isocyanurate, 12.5g of toluene, 12.5g of n-heptane and 0.5g of azobisisobutyronitrile were mixed uniformly, the organic phase was charged into a bottle, nitrogen was introduced, stirring was started to disperse the organic phase into oil droplets of appropriate size, the mixture was heated to 60 ℃ for 4 hours, and then heated to 70 ℃ for 6 hours. Washing the formed resin with hot water for several times, extracting with acetone in a Soxhlet extractor for 6h, then air drying the resin, vacuum drying, sieving and collecting the resin with 30-60 meshes for later use.
Adding 60mL of diethylenetriamine and 10g of the crosslinked polymethyl acrylate resin into a 100mL three-neck flask, heating to 140 ℃ under stirring, reacting for 12h, fully washing the obtained resin with deionized water, airing, and drying in vacuum to obtain the amino-containing resin, wherein the weak base exchange amount is 7.41mmol/g.
5g of the amino group-containing resin was suspended in 20mL of methanol, and then 10g of 3-chloro-1,2-propanediol and 4g of sodium hydroxide were added thereto, and the mixture was heated to 50 ℃ under stirring to react for 12 hours, and the resin was washed with ethanol to obtain an amino group-and o-dihydroxy group-containing resin. The hydroxyl group content of the obtained resin was measured to be 19.2mmol/g with reference to the method for measuring the hydroxyl group content in example 1. 0.1000g of the resin was suspended in 25.00mL of a boric acid solution having a concentration of 1000ppm and shaken for 24 hours, and the concentration of boron in the mother liquor after adsorption was measured with reference to the method for measuring the boron concentration in example 1, and the amount of boron adsorbed by the resin was calculated to be 47.1mg/g.
Example 4
60mL of hexaethyleneheptamine and 10g of the crosslinked polymethyl acrylate resin synthesized in the example were added into a 100mL three-necked flask, heated to 160 ℃ under stirring, reacted for 12 hours, and the obtained resin was sufficiently washed with deionized water, air-dried, and vacuum-dried to obtain an amine group-containing resin, and the weak base exchange amount was measured to be 8.82mmol/g.
5g of the amino group-containing resin was suspended in 20mL of water, and then 10g of 3-chloro-1,2-propanediol and 4g of sodium hydroxide were added thereto, and the mixture was heated to 50 ℃ under stirring to react for 12 hours, and the resin was washed with ethanol to obtain an amino group-and o-dihydroxy group-containing resin. The hydroxyl group content of the obtained resin was measured to be 18.9mmol/g with reference to the method for measuring the hydroxyl group content in example 1. 0.1000g of the resin was suspended in 25.00mL of a boric acid solution having a concentration of 1000ppm and shaken for 24 hours, and the concentration of boron in the mother liquor after adsorption was measured with reference to the method for measuring the boron concentration in example 1, and the adsorption amount of boron adsorbed by the resin was calculated to be 47.6mg/g.
Example 5
60mL of polyethylene polyamine and 10g of the crosslinked polymethyl acrylate resin synthesized in the example are added into a 100mL three-neck flask, the mixture is heated to 160 ℃ under stirring and reacts for 12 hours, the obtained resin is fully washed by deionized water, dried in the air and dried in vacuum, the amino group-containing resin is obtained, and the weak base exchange capacity is measured to be 9.56mmol/g.
5g of the amino group-containing resin is suspended in 20mL of water, 10g of glycidol is added, the mixture is heated to 80 ℃ under stirring to react for 12h, and the resin is washed with ethanol to obtain the amino group-containing resin and the ortho-dihydroxy resin. The hydroxyl group content of the obtained resin was found to be 22.3mmol/g with reference to the method for measuring the hydroxyl group content in example 1. 0.1000g of the resin was suspended in 25.00mL of a boric acid solution having a concentration of 1000ppm and shaken for 24 hours, and the concentration of boron in the mother liquor after adsorption was measured with reference to the method for measuring the boron concentration in example 1, and the adsorption amount of boron adsorbed by the resin was calculated to be 55.8mg/g.
Example 6
60mL of ethylenediamine and 10g of the crosslinked polymethyl acrylate resin synthesized in the example were added to a 100mL three-necked flask, and the mixture was heated to 80 ℃ with stirring to react for 12 hours, and the resulting resin was sufficiently washed with deionized water, air-dried, and vacuum-dried to obtain an amine group-containing resin, and the weak base exchange amount was measured to be 8.21mmol/g.
5g of the amino group-containing resin is suspended in 20mL of water, 10g of glycidol is added, the mixture is heated to 80 ℃ under stirring to react for 12 hours, and the resin is washed with ethanol to obtain the amino group-and ortho-dihydroxy group-containing resin. The hydroxyl group content of the resulting resin was measured to be 19.3mmol/g with reference to the method for measuring the hydroxyl group content in example 1. 0.1000g of the resin was suspended in 25.00mL of a boric acid solution having a concentration of 1000ppm and shaken for 24 hours, and the concentration of boron in the mother liquor after adsorption was measured with reference to the method for measuring the boron concentration in example 1, and the adsorption amount of boron adsorbed by the resin was calculated to be 39.8mg/g.
Example 7
A1000 mL three-necked flask was charged with 400mL of an aqueous solution containing 1% gelatin and 10% sodium chloride, 55.3g of acrylonitrile, 11.2g of divinylbenzene (content: 50.2%), 3.5g of triallyl isocyanurate, 35g of toluene, and 0.5g of azobisisobutyronitrile were mixed uniformly, the organic phase was charged into the flask, nitrogen was introduced, stirring was started to disperse the organic phase into oil droplets of appropriate size, heated to 60 ℃ for 4 hours, and then heated to 70 ℃ for 6 hours. Washing the formed resin with hot water for several times, extracting with acetone in a Soxhlet extractor for 6h, then air drying the resin, vacuum drying, sieving and collecting the resin with 30-60 meshes for later use.
Adding 60mL of triethylene tetramine, 10g of water and 10g of the crosslinked polyacrylonitrile resin into a 100mL three-neck flask, heating to 150 ℃ under stirring, reacting for 12h, fully washing the obtained resin with deionized water, airing, and drying in vacuum to obtain the amino-containing resin, wherein the weak base exchange capacity is 9.64mmol/g.
Suspending 5g of the amino-containing resin in 20mL of methanol, adding 10g of epoxy chloropropane and 4g of sodium hydroxide, heating to 60 ℃ under stirring, reacting for 12h, and washing the resin with ethanol to obtain the amino-containing and ortho-dihydroxy resin. The hydroxyl group content of the resulting resin was found to be 26.7mmol/g with reference to the method for measuring hydroxyl group content in example 1. 0.1000g of the resin was suspended in 25.00mL of a boric acid solution having a concentration of 1000ppm and shaken for 24 hours, and the concentration of boron in the mother liquor after adsorption was measured with reference to the method for measuring the boron concentration in example 1, and the adsorption amount of boron adsorbed by the resin was calculated to be 50.3mg/g.
Example 8
60mL of tetraethylenepentamine, 10g of water and 10g of the crosslinked polyacrylonitrile resin prepared in the example 6 are added into a 100mL three-neck flask, the mixture is heated to 150 ℃ under stirring to react for 12 hours, the obtained resin is fully washed by deionized water, dried and dried in vacuum, the amino-containing resin is obtained, and the weak base exchange capacity is measured to be 9.98mmol/g.
5g of the amino group-containing resin is suspended in 20mL of water, 10g of glycidol and 4g of sodium hydroxide are added, the mixture is heated to 60 ℃ under stirring to react for 12h, and the resin is washed with ethanol to obtain the amino group-and ortho-dihydroxy-containing resin. The hydroxyl group content of the obtained resin was measured to be 27.8mmol/g with reference to the method for measuring the hydroxyl group content in example 1. 0.1000g of the resin was suspended in 25.00mL of a boric acid solution having a concentration of 1000ppm and shaken for 24 hours, and the concentration of boron in the mother liquor after adsorption was measured with reference to the method for measuring the boron concentration in example 1, and the adsorption amount of boron adsorbed by the resin was calculated to be 54.9mg/g.
Description of the drawings: the above embodiments are only used to illustrate the present invention and do not limit the technical solutions described in the present invention; thus, while the present invention has been described in detail with reference to the foregoing embodiments, it will be understood by those skilled in the art that various changes may be made and equivalents may be substituted; all such modifications and variations are intended to be included herein within the scope of this disclosure and the present invention and protected by the following claims.

Claims (9)

1. A cross-linked polymer resin containing 2,3-dihydroxypropylamine groups, which is characterized by having the following characteristic structure:
Figure FSA0000238104070000011
in the above formula
Figure FSA0000238104070000012
Represents a resin having a crosslinked polymer skeleton in which structural units for connecting functional groups are:
Figure FSA0000238104070000013
r = H or CH in the above formula 3 。
2. The crosslinked polymer resin of claim 1 containing 2,3-dihydroxypropylamino groups, when in
Figure FSA0000238104070000014
Is composed of
Figure FSA0000238104070000015
N =1, 2,3, 4, 5 or 6; when in use
Figure FSA0000238104070000016
Is composed of
Figure FSA0000238104070000017
When n =0, 1,2, 3, 4 or 5.
3. The crosslinked polymer resin containing 2,3-dihydroxypropylamino groups according to claims 1 and 2, characterized in that the resin is of the gel type or macroporous type.
4. The crosslinked polymer resin containing 2,3-dihydroxypropylamino groups according to claims 1,2 and 3, characterized in that the particle size of the resin is 0.05 to 1.5mm, preferably 0.3 to 1.2mm.
5. The method of preparing a cross-linked polymer resin containing 2,3-dihydroxypropylamino group according to claims 1,2, 3 and 4, wherein the preparation reaction consists of 2 steps: the first step is that chloromethylated crosslinked polystyrene resin, crosslinked polymethyl acrylate, crosslinked polyacrylonitrile, crosslinked polymethyl methacrylate or crosslinked polymethyl acrylonitrile reacts with ethylenediamine, diethylenetriamine, triethylenetetramine, tetraethylenepentamine, pentaethylenehexamine, hexaethyleneheptamine or polyethylene polyamine, or reacts with polyamine and a certain amount of water; the second step is that the resin containing amido obtained from the first step reacts with epichlorohydrin, glycidol or 3-chloro-1,2-propylene glycol.
6. The method of claim 5, wherein the ratio of polyamine to water in the first step is 100/0 to 80/20, and the reaction temperature is between room temperature and 160 ℃ (or reflux temperature).
7. The process for preparing a crosslinked polymer resin containing 2,3-dihydroxypropylamino groups according to claim 5, characterized in that, when the reactant is epichlorohydrin or 3-chloro-1,2-propanediol in the second reaction step, the reaction requires the presence of an alkali, preferably sodium hydroxide.
8. The method for preparing a cross-linked polymer resin containing 2,3-dihydroxypropylamine groups according to claims 5 and 7, wherein the solvent used in the second reaction is water, methanol or ethanol; the reaction temperature is from room temperature to 100 ℃.
9. Use of the crosslinked polymer resin containing 2,3-dihydroxypropylamino groups as claimed in claims 1,2, 3 and 4 for adsorbing boron from an aqueous or organic solution.
CN202110353290.8A 2021-04-01 2021-04-01 Boron adsorption resin and preparation method thereof Pending CN115155529A (en)

Priority Applications (1)

Application Number Priority Date Filing Date Title
CN202110353290.8A CN115155529A (en) 2021-04-01 2021-04-01 Boron adsorption resin and preparation method thereof

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
CN202110353290.8A CN115155529A (en) 2021-04-01 2021-04-01 Boron adsorption resin and preparation method thereof

Publications (1)

Publication Number Publication Date
CN115155529A true CN115155529A (en) 2022-10-11

Family

ID=83475782

Family Applications (1)

Application Number Title Priority Date Filing Date
CN202110353290.8A Pending CN115155529A (en) 2021-04-01 2021-04-01 Boron adsorption resin and preparation method thereof

Country Status (1)

Country Link
CN (1) CN115155529A (en)

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN116078362A (en) * 2023-04-11 2023-05-09 四川大学 Boron isotope separation material of amino resin grafted plant polyphenol, preparation method and application

Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN101642700A (en) * 2009-09-03 2010-02-10 嘉应学院 Preparation method of boron adsorbent
JP2011212672A (en) * 2010-03-17 2011-10-27 Toshiba Corp Acrylic resin particle for adsorbent and column for water treatment
CN102336856A (en) * 2011-07-04 2012-02-01 常州大学 Special effect boron adsorption resin and synthetic method and application thereof
CN106422809A (en) * 2016-06-19 2017-02-22 贵州省材料产业技术研究院 Fast and efficient boron removal hollow fiber composite membrane and preparation method thereof
KR102189336B1 (en) * 2019-08-23 2020-12-09 (주)비피케미칼 Method of preparing chelate resin for adsorbing boron ions

Patent Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN101642700A (en) * 2009-09-03 2010-02-10 嘉应学院 Preparation method of boron adsorbent
JP2011212672A (en) * 2010-03-17 2011-10-27 Toshiba Corp Acrylic resin particle for adsorbent and column for water treatment
CN102336856A (en) * 2011-07-04 2012-02-01 常州大学 Special effect boron adsorption resin and synthetic method and application thereof
CN106422809A (en) * 2016-06-19 2017-02-22 贵州省材料产业技术研究院 Fast and efficient boron removal hollow fiber composite membrane and preparation method thereof
KR102189336B1 (en) * 2019-08-23 2020-12-09 (주)비피케미칼 Method of preparing chelate resin for adsorbing boron ions

Non-Patent Citations (2)

* Cited by examiner, † Cited by third party
Title
廖慧玲: ""多羟基胺基树脂的合成及对硼酸吸附性能的研究"", 《中国优秀硕士学位论文全文数据库工程科技Ⅰ辑》, no. 01, 15 January 2021 (2021-01-15), pages 014 - 1274 *
廖慧玲;朱美玲;付玉丽;胡海华;徐满才;钟世华;: "聚苯乙烯多羟基吸附树脂的合成及对硼酸的吸附性能", 广州化工, no. 09, 8 May 2020 (2020-05-08), pages 62 - 65 *

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN116078362A (en) * 2023-04-11 2023-05-09 四川大学 Boron isotope separation material of amino resin grafted plant polyphenol, preparation method and application

Similar Documents

Publication Publication Date Title
Dong et al. Recent progress in environmental applications of functional adsorbent prepared by radiation techniques: A review
Das et al. Exchanges of uranium (VI) species in amidoxime-functionalized sorbents
CN108525648B (en) Aminated magnetic polyphosphazene adsorbent and method for preparing, separating and enriching uranium
JP5590594B2 (en) Chelating polymer compound-containing metal adsorbent
Zhu et al. Highly efficient adsorption of Hg (II) and Pb (II) onto chitosan-based granular adsorbent containing thiourea groups
CN104262521A (en) Preparation method of styrene-divinylbenzene copolymer hydrophobic catalyst support
Huang et al. Efficient adsorption and recovery of Pb (II) from aqueous solution by a granular pH-sensitive chitosan-based semi-IPN hydrogel
Yuan et al. Successive grafting of poly (hydroxyethyl methacrylate) brushes and melamine onto chitosan microspheres for effective Cu (II) uptake
CN107552007A (en) Ion liquid modified magnalium laminar double-hydroxide adsorbent and its preparation and application
CN111410723A (en) Porous boron affinity imprinted polymer and preparation method and application thereof
Huang et al. One-step cross-linking of amino-rich chitosan aerogels for efficient and selective adsorption of uranium from radioactive nuclear wastewater
CN107999019B (en) Amphiphilic magnetic nanosphere and preparation method and adsorption application thereof
Meng et al. Preparation and characterization of surface imprinted polymer for selective sorption of uranium (VI)
Tripathi et al. Synthesis of a low-density biopolymeric chitosan–agarose cryomatrix and its surface functionalization with bio-transformed melanin for the enhanced recovery of uranium (vi) from aqueous subsurfaces
CN115155529A (en) Boron adsorption resin and preparation method thereof
Su et al. Surface ion-imprinted brewer’s spent grain with low template loading for selective uranyl ions adsorption from simulated wastewater
Tonghuan et al. Adsorptive features of polyacrylic acid hydrogel for UO 2 2+
Ali et al. Study on the synthesis of a macroporous ethylacrylate‐divinylbenzene copolymer, its conversion into a bi‐functional cation exchange resin and applications for extraction of toxic heavy metals from wastewater
CN102234344A (en) Preparation method of macroporous long alkyl side chain acrylic acid ester-styrene-ethylene dimethacrylate crosslinking copolymerization microballoon
US8835586B2 (en) Polycarbonate resin, poly (2-octadecyl-butanedioic acid) and the salts and esters thereof
Wang et al. Carboxyl and amino acid functionalized indole-based polymer for ultrafast uranium extraction in aqueous solution
Pivarčiová et al. Sorption of technetium on glutaraldehyde crosslinked chitosan
Ma et al. Crosslinking induced by irradiation raises selectivity of polymeric adsorbent
Yayayürük The use of acrylic-based polymers in environmental remediation studies
CN101245155B (en) Pyrrolyl modification complex function polymeric adsorbent and manufacture method thereof

Legal Events

Date Code Title Description
PB01 Publication
PB01 Publication
SE01 Entry into force of request for substantive examination
SE01 Entry into force of request for substantive examination