Amidoxime group-containing polymer, and preparation method and application thereof

文档序号：1458541 发布日期：2020-02-21 浏览：29次中文

阅读说明：本技术 一种含偕胺肟基的聚合物及其制备方法和应用 (Amidoxime group-containing polymer, and preparation method and application thereof ) 是由杨亮亮李舒琦刘大卫谢龙朱刘于 2019-11-29 设计创作，主要内容包括：本发明涉及一种含偕胺肟基的聚合物,所述聚合物的通式如下式所示：[RCHCH2CH2NHCH2CH2CH[CH2CHCNOHNH2]n]a[R[CH2CHCNOHNH2]m]b[RV]c,其中,n、m、b分别表示正整数,a、c分别表示0或正整数,c与a+b的比值为0～100；R选自氢、C1～C22烷基、交联或链状R1xTi(OR2)yOz、聚合物[CH2CHR1]f或聚合物[VCHCHR1]f；其中,x、y分别表示0～2的整数,z表示1～4的整数,f表示大于1000的整数；R1选自C1～C6烷基,R2选自C1～C12烷基,R1选自C1～C22烷基、C2～C22烯烃基、芳基或取代芳基；V选自C2～C12烯烃基、取代芳基、聚合物[CH2CHPh]r或聚合物[R2CHCHPh]r；其中r表示正整数,R2选自C2～C12烯烃基、芳基或取代芳基。本发明含偕胺肟基的聚合物可作为吸附材料,对稀散金属镓、锗具有极高的亲和力,能有效去除/捕捉工艺、污水中的有价元素,吸附后材料可通过洗脱液重复使用。(The invention relates to an amidoxime group-containing polymer, which has a general formula shown as the following formula: [ RCHCH ] 2 CH 2 NHCH 2 CH 2 CH[CH 2 CHCNOHNH 2 ] n ] a [R[CH 2 CHCNOHNH 2 ] m ] b [RV] c Wherein n, m and b respectively represent positive integers, a and c respectively represent 0 or a positive integer, and the ratio of c to a + b is 0-100; r is selected from hydrogen and C 1 ～C 22 Alkyl, cross-linked or chain R 1 x Ti(OR 2 ) y O z Polymer [ CH ] 2 CHR 1 ] f Or polymers [ VCHCHR ] 1 ] f (ii) a Wherein x and y represent an integer of 0-2, z represents an integer of 1-4, and f represents an integer greater than 1000; r 1 Is selected from C 1 ～C 6 Alkyl radical, R 2 Is selected from C 1 ～C 12 Alkyl radical, R 1 Is selected from C 1 ～C 22 Alkyl radical, C 2 ～C 22 Alkylene, aryl, or substituted aryl; v is selected from C 2 ～C 12 Alkylene, substituted aryl, polymer [ CH 2 CHPh] r Or polymers [ R 2 CHCHPh] r (ii) a Wherein R represents a positive integer, R 2 Is selected from C 2 ～C 12 Alkenyl, aryl or substituted aryl. The amidoxime group-containing polymer can be used as an adsorption material, has extremely high affinity to rare metal gallium and germanium, can effectively remove/capture valuable elements in the process and sewage, and can be reused through eluent after adsorption.)

1. An amidoxime group-containing polymer having the formula: [ RCHCH ]₂CH₂NHCH₂CH₂CH[CH₂CHCNOHNH₂]_n]_a[R[CH₂CHCNOHNH₂]_m]_b[RV]_c

Wherein n, m and b respectively represent positive integers, a and c respectively represent 0 or a positive integer, and the ratio of c to a + b is 0-100;

r is selected from hydrogen and C₁～C₂₂Alkyl, cross-linked or chain R¹ _xTi(OR²)_yO_zPolymer [ CH ]₂CHR₁]_fOr polymers [ VCHCHR ]₁]_f(ii) a Wherein x and y are each an integer of 0 to 2, and z is 1 to 4An integer, f represents an integer greater than 1000; r¹Is selected from C₁～C₆Alkyl radical, R²Is selected from C₁～C₁₂Alkyl radical, R₁Is selected from C₁～C₂₂Alkyl radical, C₂～C₂₂Alkylene, aryl, or substituted aryl;

v is selected from C₂～C₁₂Alkylene, substituted aryl, polymer [ CH₂CHPh]_rOr polymers [ R₂CHCHPh]_r(ii) a Wherein R represents a positive integer, R₂Is selected from C₂～C₁₂Alkenyl, aryl or substituted aryl.

2. The amidoxime group-containing polymer of claim 1, wherein the substituent of the substituted aryl group is selected from the group consisting of an amino group, a nitro group, an amide group, a vinyl group, a nitrile group, a hydroxyl group, a carboxylic acid group, a sulfone group, and a sulfoxide group.

3. The process for preparing an amidoxime group-containing polymer according to any one of claims 1 to 2, comprising the steps of:

(1) preparing a polymer precursor by chemical modification: dissolving the skeleton carrier in solvent, adding polymer [ CH ]₂CH₂CH₂NHCH₂CH₂CH[CH₂CHCN]_w]_kAnd/or acrylonitrile, stirring and mixing uniformly, then adding an initiator, starting reaction in a stage of sectional temperature rise control, and after the reaction is finished, filtering, washing and drying to obtain a polymer precursor;

wherein k and w respectively represent an integer of 2-1000, and the skeleton carrier is titanium dioxide and polymer [ CH ]₂CHR₁]_fPolymers [ VCHCHR ]₁]_fAt least one of [ CH ] or [ C ] or a salt thereof, the polymer₂CH₂CH₂NHCH₂CH₂CH[CH₂CHCN]_w]_kPrepared by mixing acrylonitrile and diallylamine according to the molar ratio of 1: 1;

(2) functionalized reaction for preparing amidoxime group-containing polymer: adding hydroxylamine hydrochloride or hydroxylamine sulfate into a solvent, stirring until the hydroxylamine hydrochloride or hydroxylamine sulfate is completely dissolved to obtain a mixed solution, and adjusting the pH value to 7; and (2) adding the polymer precursor obtained in the step (1) into the mixed solution, and stirring for reaction to obtain the amidoxime group-containing polymer.

4. The method for preparing amidoxime group-containing polymer according to claim 3, wherein in the step (1) and the step (2), the solvent is at least one of water, xylene, toluene, ethylene glycol, ethanol, and methanol; in the step (1), the initiator is at least one of azobisisobutyronitrile, tert-butyl hydroperoxide, tert-butyl peroxide and benzoyl peroxide.

5. The process for preparing amidoxime group-containing polymer according to claim 3, wherein in step (1), the polymer [ CH ]₂CH₂CH₂NHCH₂CH₂CH[CH₂CHCN]_w]_kAnd the mass ratio of the total mass of the acrylonitrile to the skeleton carrier is 1: (1.4-2.6), the dosage of the solvent is 2-10 times of the mass of the skeleton carrier, and each kg of the polymer [ CH ]₂CH₂CH₂NHCH₂CH₂CH[CH₂CHCN]_w]_kAnd 15-30 g of acrylonitrile is added into the mixture.

6. The method for preparing an amidoxime group-containing polymer according to claim 3, wherein in step (2), the solvent is used in an amount of 2.5 times the mass of the polymer precursor, and the hydroxylamine hydrochloride or hydroxylamine sulfate is used in an amount of 2 times the mass of the polymer precursor.

7. The method for preparing amidoxime group-containing polymer according to claim 3, wherein in step (1), the stirring speed is 150 to 200r/min, and the stirring time is 0.5 h; the step of controlling temperature rise in sections is that reaction is carried out for 3 hours at the temperature of 45-70 ℃, then the temperature rises to 70-80 ℃ for reaction for 2 hours, and finally the temperature rises to 80-90 ℃ for reaction for 3 hours; the washing was 5 times with pure water, and the drying temperature was 60 ℃.

8. The process for producing an amidoxime group-containing polymer according to claim 3, wherein in the step (2), the pH is adjusted with a sodium carbonate solution at a mass fraction of 20%, a sodium hydroxide solution at a mass fraction of 15%, or a potassium hydroxide solution at a mass fraction of 10%; the stirring speed is 300r/min, the stirring reaction is carried out for 3 hours at the temperature of 45-55 ℃, and then the temperature is increased to 70-80 ℃ for 5 hours.

9. Use of the amidoxime group-containing polymer according to any one of claims 1 to 2 as an adsorbent material.

10. Use according to claim 9, wherein the adsorbent material is used for purifying, separating organic, biological or inorganic molecules from gaseous, liquid or solid environments.

Technical Field

The invention relates to an amidoxime group-containing polymer, and a preparation method and application thereof, and belongs to the technical field of adsorption materials.

Background

Scattered metals (scattered metals) are abbreviated as SM, and are mainly comprehensively recovered and regenerated from byproducts, leftover materials and waste products generated in the production process of industries such as metallurgy, chemical industry, thermal power generation and the like. The rare metal has extremely important application and is an important component of the modern high-tech new material. A series of compound semiconductors, electron-optical materials, special alloys, novel functional materials, organic metal compounds and the like, which are composed of rare-earth metals and non-ferrous metals, all need to use rare-earth metals with unique properties, and although the dosage is not large, the dosage is very important and is not necessary. Therefore, the material is widely used in modern communication technology, electronic computers, space navigation development, medicine and health, photosensitive materials, photoelectric materials, energy materials, catalyst materials and the like. Among them, gallium and germanium are very important and widely used as small metals among rare metal elements in many fields.

However, the rare and dispersive characteristics of the rare and dispersive metals make resource integration difficult and loss serious. In Critical metals in strategic energy technologies (ISBN 978-92-79-20698-6), fourteen metals have been labeled as Critical metals, with small metals such as gallium and germanium presenting high risk, and this report provides part of the technical solutions for metal recovery technology. The production and recovery processes of the scattered metal gallium and germanium are multiple, the adsorption material can be used for purifying products, the specific metal cost in the process and the waste liquid, and the commercial purposes of product purification, circular economy and the like are finally achieved.

Conventional adsorbent materials use styrene and/or divinylbenzene as a backbone to which organic adsorbent structures are fused by copolymerization and oximation. However, such adsorbent materials have limitations such as poor chemical and thermal stability, low adsorption capacity, and poor mechanical strength. Therefore, the method cannot be applied to a harsh strong acid or strong base-containing metallurgical process for a long time, so that a large amount of consumable cost is increased, and the profit is influenced.

The emergence of new technologies is crucial in order to meet the existing challenges of business, technology, environment and society and the higher demands expected by the market. There is a need to develop a simple and environmentally friendly adsorption material which can be used for removing organic and inorganic compounds from products, processes and sewage, can be used as a metal removal and recovery material, or can be used for removing organic and inorganic compounds from products, processes and sewage, or can be used as a solid phase purification or extraction material, a biomolecule immobilization material and a solid phase synthesis material.

Disclosure of Invention

The invention aims to overcome the defects of the prior art and provides a amidoxime group-containing polymer, and a preparation method and application thereof.

In order to achieve the purpose, the invention adopts the technical scheme that: an amidoxime group-containing polymer having the formula:

[RCHCH₂CH₂NHCH₂CH₂CH[CH₂CHCNOHNH₂]_n]_a[R[CH₂CHCNOHNH₂]_m]_b[RV]_c

wherein n, m and b respectively represent positive integers, a and c respectively represent 0 or a positive integer, and the ratio of c to a + b is 0-100;

r is selected from hydrogen and C₁～C₂₂Alkyl, cross-linked or chain R¹ _xTi(OR²)_yO_zPolymer [ CH ]₂CHR₁]_fOr polymers [ VCHCHR ]₁]_f(ii) a Wherein x and y represent an integer of 0-2, z represents an integer of 1-4, and f represents an integer greater than 1000; r¹Is selected from C₁～C₆Alkyl radical, R²Is selected from C₁～C₁₂Alkyl radical, R₁Is selected from C₁～C₂₂Alkyl radical, C₂～C₂₂Alkylene, aryl, or substituted aryl;

As a preferred embodiment of the amidoxime group-containing polymer of the present invention, the substituent of the substituted aryl group is selected from an amino group, a nitro group, an amide group, a vinyl group, a nitrile group, a hydroxyl group, a carboxylic acid group, a sulfone group or a sulfoxide group.

In a second aspect, the present invention provides a method for preparing the amidoxime group-containing polymer, comprising the following steps:

The invention realizes the control of the ratio of local polymerization reaction (integers n and m) to functional groups a, b and c by controlling the reaction conditions and the relative molar concentration, thereby generating more complex spatial distribution, providing higher affinity to a target object and having higher adsorption capacity.

Skeleton carrier titanium dioxide, polymer [ CH₂CHR₁]_fPolymers [ VCHCHR ]₁]_fWith polymers [ CH₂CH₂CH₂NHCH₂CH₂CH[CH₂CHCN]_w]_kAnd/or acrylonitrile can generate different loading amounts, polymerization degrees (integers n and m) and space chemical structures (proportions of a, b and c) under different proportioning and reaction conditions, and finally, the corresponding properties and the high-quality removal of the target substances can be achieved through the control of the reaction conditions. The practical process shows that the higher n and m, the higher n: the higher m and the reasonable adjustment of the V structure can lead the adsorption material to present better hydrophilicity, thus being beneficial to removing the target in the water body.

The polymer [ CH ] can be controlled by the ratio of diallylamine to acrylonitrile and the reaction conditions, at which the desired degree of polymerization (integer n, m) and stereochemistry (ratio a, b, c) are determined₂CH₂CH₂NHCH₂CH₂CH[CH₂CHCN]_w]_kAnd acrylonitrile and a, b.

As a preferred embodiment of the method for preparing the amidoxime group-containing polymer according to the present invention, in the step (1) and the step (2), the solvent is at least one of water, xylene, toluene, ethylene glycol, ethanol, and methanol; in the step (1), the initiator is at least one of azobisisobutyronitrile, tert-butyl hydroperoxide, tert-butyl peroxide and benzoyl peroxide.

As a preferred embodiment of the process for preparing the amidoxime group-containing polymer of the present invention, in the step (1), the polymer [ CH₂CH₂CH₂NHCH₂CH₂CH[CH₂CHCN]_w]_kAnd/or the mass ratio of the total mass of acrylonitrile to the framework carrier is 1: (1.4-2.6), the dosage of the solvent is 2-10 times of the mass of the skeleton carrier, and each kg of the polymer [ CH ]₂CH₂CH₂NHCH₂CH₂CH[CH₂CHCN]_w]_kAnd/or 15-30 g of acrylonitrile is added into the initiator.

As a preferred embodiment of the method for preparing the amidoxime group-containing polymer of the present invention, in the step (2), the solvent is used in an amount of 2.5 times the mass of the polymer precursor, and the hydroxylamine hydrochloride or hydroxylamine sulfate is used in an amount of 2 times the mass of the polymer precursor.

As a preferable embodiment of the preparation method of the amidoxime group-containing polymer, in the step (1), the stirring speed is 150-200 r/min, and the stirring time is 0.5 h; the step of controlling temperature rise in sections is that reaction is carried out for 3 hours at the temperature of 45-70 ℃, then the temperature rises to 70-80 ℃ for reaction for 2 hours, and finally the temperature rises to 80-90 ℃ for reaction for 3 hours; the washing was 5 times with pure water, and the drying temperature was 60 ℃.

As a preferable embodiment of the method for preparing the amidoxime group-containing polymer of the present invention, in the step (2), the pH is adjusted with a sodium carbonate solution with a mass fraction of 20%, a sodium hydroxide solution with a mass fraction of 15%, or a potassium hydroxide solution with a mass fraction of 10%; the stirring speed is 300r/min, the stirring reaction is carried out for 3 hours at the temperature of 45-55 ℃, and then the temperature is increased to 70-80 ℃ for 5 hours.

In a third aspect, the invention provides the use of the amidoxime group-containing polymer as described above as an adsorbent material.

As a preferred embodiment of the application according to the invention, the adsorbent material is used for the purification, separation of organic, biological or inorganic molecules from gaseous, liquid or solid environments.

As a preferred embodiment of the application of the present invention, the adsorption material is used for recovering and removing small metal gallium or germanium from reaction mixtures, process fluids, products or wastewater.

In order to realize the selectivity of the adsorption material, different base materials can be added into the grafting and polymerization process, the process has great flexibility, the surrounding environment of polymer functional groups can be modified, the hydrophilicity is adjusted, the selective bonding capability is increased, and finally better performance is provided.

The amidoxime group-containing polymer can be filtered, washed and dried, and finally put into application. The application method of the amidoxime group-containing polymer as the adsorbing material comprises the following steps:

(1) adsorption and filtration: filling the amidoxime group-containing polymer into a stirring and filtering device, fully stirring and mixing the amidoxime group-containing polymer with fluid, and separating the adsorbed compound; or fixed bed or fluidized bed and other application equipment and processes can be used for adsorption and filtration, and the amidoxime group-containing polymer is adopted as an adsorption material for repeated adsorption, mixing and filtration until the adsorption rate is less than 20-40%;

(2) washing with water: when the adsorption rate is less than 20-40%, separating the adsorbed compound, and washing until the pH value is 6-8;

(3) and (3) elution and water washing: eluting the adsorbate by using an eluent, and washing the eluted compound until the pH value is 6-8;

(4) and (3) repeated use: repeating the steps until the adsorption capacity is less than 2 g/kg.

In the using method of the amidoxime group-containing polymer as the adsorbing material, in the adsorbing and filtering processes, fluid can be continuously injected, and a fixed bed process is preferred; batch sample introduction can also be adopted, and a stirring and filtering process is preferred; compared with the traditional oxime group adsorbing material, the amidoxime group-containing polymer provided by the invention has stronger mechanical strength, and a fluidized bed process can be selected; during the mixing process, the adsorbent material needs to be in sufficient contact with the fluid to better position and capture the target analyte.

After the fluid is fully contacted, the target object in the fluid can be captured by the affinity and spatial structure of the functional group of the adsorbing material, so as to achieve the purpose of product purification, such as removing metal impurities in biomolecules (such as peptide, protein and nucleic acid) or drug products.

In the using method of the amidoxime group-containing polymer as the adsorbing material, the stirring time is 2-240 min and the temperature is 10-60 ℃ in the adsorbing and filtering processes; in the elution and water washing processes, the eluent is at least one of sulfuric acid, nitric acid, phosphoric acid, hydrochloric acid and chloroacetic acid, and the pH value of the eluent is 0.2-1.

In the using method of the amidoxime group-containing polymer as the adsorbing material, the eluent is precipitated, purified, concentrated and/or electrolyzed to obtain valuable metals or compounds. The using temperature is 10-110 ℃, a solution prepared from at least one of sodium carbonate, sodium hydroxide and potassium hydroxide is used, and the concentration of the solution is more than 5%; the raw material used for purification is at least one of ferric hydroxide, manganese hydroxide, aluminum hydroxide, calcium oxide, sodium sulfide and hydrogen peroxide.

Compared with the prior art, the invention has the beneficial effects that:

(1) according to the invention, a novel and compound organic functional structure is connected to base materials such as titanium dioxide and polymers through simple and easily-obtained raw materials, and amidoxime groups are polymerized by chemical modification on a skeleton with stronger mechanical strength and chemical temperature, so that the adsorption material with high capacity and strong selectivity is finally prepared;

(2) the amidoxime group-containing polymer can be used as a metal removing and recycling material, can remove organic and inorganic compounds from products, processes or wastewater, and can be used as a solid phase purification or extraction material, a biomolecule immobilization material and a solid phase synthesis material;

(3) the preparation method of the amidoxime group-containing polymer is simple, environment-friendly, suitable for large-scale production, and has commercial values in productivity, cost and purity compared with the prior art;

(4) the amidoxime group-containing polymer has extremely high affinity to rare metal gallium and germanium, can effectively remove/capture valuable elements in the process and sewage, and the adsorbed material can be reused through eluent; valuable elements in the eluent can be prepared into corresponding products by carrying out precipitation, purification, concentration and/or electrolysis on the eluent.

Drawings

FIG. 1 is a Fourier transform infrared spectrum of the polypropylene of example 2.

FIG. 2 is a Fourier transform infrared spectrum of the polymer precursor of example 2.

FIG. 3 is a Fourier transform infrared spectrum of polystyrene of example 3.

FIG. 4 is a Fourier transform infrared spectrum of the polymer precursor of example 3.

Detailed Description

To better illustrate the objects, aspects and advantages of the present invention, the present invention will be further described with reference to the accompanying drawings and specific embodiments.

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