CN116371376B

CN116371376B - Bifunctional phloroglucinol adsorption material and preparation method and application thereof

Info

Publication number: CN116371376B
Application number: CN202310281890.7A
Authority: CN
Inventors: 咸漠; 徐超; 姜龙; 陈西敏
Original assignee: Qingdao Institute of Bioenergy and Bioprocess Technology of CAS
Current assignee: Qingdao Institute of Bioenergy and Bioprocess Technology of CAS
Priority date: 2023-03-22
Filing date: 2023-03-22
Publication date: 2024-05-24
Anticipated expiration: 2043-03-22
Also published as: CN116371376A

Abstract

A bifunctional phloroglucinol adsorption material and its preparation method and application are provided. The invention belongs to the technical field of adsorption separation materials. The invention aims to solve the technical problem that the phloroglucinol lacks high-affinity and high-selectivity separation materials due to good water solubility and poor stability. The method comprises the following steps: specifically, a matrix material, a functional monomer and a catalyst are mixed for reaction to prepare a quaternized material, and a C=C structure of the introduced monomer is utilized to carry out free radical polymerization reaction with the pre-assembled phloroglucinol and the functional monomer to construct a molecular imprinting cavity. The method firstly generates the quaternized material, utilizes the interaction of hydrogen bond and static electricity to be specifically combined with the phenolic hydroxyl group of the phloroglucinol, and on the basis, utilizes the unique size matching and hydrogen bond action of the surface molecularly imprinted polymer to efficiently identify the phloroglucinol, thereby finally realizing the difunctional adsorption separation of the phloroglucinol.

Description

Bifunctional phloroglucinol adsorption material and preparation method and application thereof

Technical Field

The invention belongs to the technical field of adsorption separation materials, and particularly relates to a difunctional phloroglucinol adsorption material and a preparation method and application thereof.

Background

The phloroglucinol is an important medical intermediate and an organic synthesis intermediate, has good pharmacological activities of resisting virus, resisting tumor, resisting bacteria, diminishing inflammation, stopping bleeding and the like, and has extremely broad market prospect. The demand of the chemical synthesis method is increased year by year at home and abroad, the traditional chemical synthesis method production technology is lagged, the environmental pollution is serious, and the product quality is difficult to meet the development of medicine production. In 2005, the total biosynthesis of phloroglucinol was first reported (Achkar J, xian M, zhao H, et al j.ame. Chem. Soc.,2005, 127:5332), and the yield of phloroglucinol in the engineered strain was 780mg/L by expressing the polyketide synthase gene ph1D from pseudomonas fluorescens directly in escherichia coli. In recent years, the yield of phloroglucinol has been increased to 5.3g/L (Zhang R, cao Y, liu W, et al Microb.cell act,2017, 16:227) by rational design of the phloroglucinol synthesis pathway and increased host tolerance to phloroglucinol. The biological method has the advantages of green and safe raw materials, good process safety, low three wastes and good prospect in the aspect of replacing petrochemical phloroglucinol. However, in complex biological fermentation systems, thalli, proteins, salts, acids and the like generally coexist, and the phloroglucinol has high water solubility (11.17 g/L, room temperature), so how to design specific acting force to realize efficient and selective separation of the phloroglucinol and effectively improve the adsorption performance of the material on the phloroglucinol is a problem to be solved urgently.

Disclosure of Invention

The invention aims to solve the technical problem of lack of high affinity and high selectivity separation materials caused by good water solubility and poor stability of phloroglucinol, and the invention takes chloromethyl polystyrene-divinylbenzene as a matrix, firstly utilizes quaternization reaction to introduce nitrogenous olefin compounds into chloromethyl sites, and realizes the introduction of basic functional groups; the surface molecular imprinting cavity is further constructed on the basis of the introduced olefin structure, so that the difunctional phloroglucinol adsorbing material is synthesized.

The aim of the invention is achieved by the following technical scheme:

the invention aims at providing a preparation method of a difunctional phloroglucinol adsorbing material, which comprises the following steps:

Step 1: adding a matrix material, a functional monomer and a catalyst into a solvent A, reacting for a certain time at a certain temperature, alternately washing with an alcohol solvent and water after the reaction is finished, and drying in vacuum to obtain a quaternized material;

step 2: mixing quaternized material, template molecules and functional monomers, adding a solvent B and a solvent C, and pre-assembling under certain conditions;

Step 3: and (3) adding an initiator and a cross-linking agent into the pre-assembled product, reacting for a certain time at a certain temperature in a nitrogen atmosphere, washing the obtained product with a solvent D, and drying in vacuum to obtain the difunctional phloroglucinol adsorbing material.

In one embodiment of the present invention, the matrix material in step 1 is chloromethyl polystyrene divinylbenzene, wherein the amount of chlorine species is 4 to 5mmol/g.

In one embodiment of the invention, the functional monomer in step 1-2 is N-Vinylimidazole (VIM), N-dimethylaminoethyl ester (DHAM) or 4-vinylpyridine (4-VP).

In one embodiment of the invention, the catalyst in step 1 is KI or NaI.

In one embodiment of the present invention, the molar ratio of the functional monomer, the catalyst and the chlorine in chloromethyl polystyrene divinylbenzene in step 1 is (1 to 5): (0.01-0.1): 1.

In one embodiment of the present invention, the solvent a in step 1 is one or a mixture of several of ethanol, acetonitrile, N-dimethylformamide, tetrahydrofuran, dimethyl sulfoxide and water according to any ratio.

In one embodiment of the present invention, the ratio of the volume of the solvent a to the mass of chloromethyl polystyrene divinylbenzene in step 1 is (5 to 10) mL:1g.

In one embodiment of the present invention, the temperature in step 1 is 25 to 80 ℃ for 1 to 48 hours.

In one embodiment of the present invention, the template molecule in step 2 is phloroglucinol.

In one embodiment of the present invention, the mass ratio of the functional monomer, the template molecule and the quaternized material in the step 2 is (3 to 6): 1: (0.33-1).

In one embodiment of the present invention, the solvent B in step 2 is one of toluene, methanol, and ethanol.

In one embodiment of the present invention, the solvent C in step 2 is acetonitrile or water.

In one embodiment of the present invention, the volume ratio of the solvent B to the solvent C in the step 2 is (1 to 3): 1.

In one embodiment of the present invention, the pre-assembly condition in step 2 is stirring at room temperature for 2-6 hours.

In one embodiment of the present invention, the initiator in the step 3 is one or a mixture of several of Azobisisobutyronitrile (AIBN), azobisiso Ding Gengjing, azobisisobutyronimidine hydrochloride, azobisiso Ding Mi, benzoyl peroxide in any ratio.

In one embodiment of the present invention, the mass ratio of the initiator in step 3 to the functional monomer in step 2 is (0.005 to 0.03): 1.

In one embodiment of the present invention, the crosslinking agent in step 3 is ethylene glycol dimethacrylate.

In one embodiment of the invention, the molar ratio of the crosslinker in step3 to the template molecule in step2 is (1-3): 1.

In one embodiment of the present invention, the temperature in step 3 is 40 to 80 ℃ for 2 to 24 hours.

In one embodiment of the present invention, the solvent D in step 3 is one or a mixture of several of methanol, acetic acid, ethanol, acetonitrile and water according to any ratio.

The second object of the present invention is to provide a bifunctional phloroglucinol adsorbent material obtained in accordance with the above method.

The invention also provides an application of the bifunctional phloroglucinol adsorbing material obtained by the method in phloroglucinol adsorption.

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

Aiming at the problems that phloroglucinol has high water solubility and poor stability, so that separation is difficult to realize through selective adsorption, the invention designs a type of double-functional group phloroglucinol adsorption material, which has the following advantages:

(1) The selected 4-vinyl pyridine, N-vinyl imidazole and N, N-dimethyl amino ethyl ester monomer can be subjected to efficient nucleophilic substitution reaction with matrix chloromethyl polystyrene divinylbenzene (namely chlorine ball) under the catalysis of KI to generate quaternized materials, and the materials can be specifically combined with phenolic hydroxyl groups of phloroglucinol by utilizing hydrogen bonds and electrostatic interaction to realize the first adsorption effect of the phloroglucinol;

(2) The invention uses phloroglucinol and 4-vinyl pyridine, N-vinyl imidazole and N, N-dimethyl amino ethyl ester monomer to pre-assemble, constructs a ligand structure matched with phloroglucinol, carries out free radical polymerization reaction with C=C double bond structure loaded by quaternized material, introduces surface molecularly imprinted polymer, and realizes the second adsorption effect of phloroglucinol;

(3) According to the invention, under weak interaction forces such as hydrogen bond, electrostatic interaction and the like and recognition of a molecular imprinting cavity, the adsorption capacity of the material to phloroglucinol can reach more than 120 mg/g.

Drawings

FIG. 1 shows the infrared results of CMPS, CMPS-VIM-1, and CMPS-PG-5 described in example 5.

Detailed Description

The present invention will be described in further detail with reference to the following examples in order to make the objects, technical solutions and advantages of the present invention more apparent. It should be understood that the specific embodiments described herein are for purposes of illustration only and are not intended to limit the scope of the invention.

The experimental methods used in the following examples are conventional methods unless otherwise specified. The materials, reagents, methods and apparatus used, without any particular description, are those conventional in the art and are commercially available to those skilled in the art.

The terms "comprising," "including," "having," "containing," or any other variation thereof, as used in the following embodiments, are intended to cover a non-exclusive inclusion. For example, a composition, step, method, article, or apparatus that comprises a list of elements is not necessarily limited to only those elements but may include other elements not expressly listed or inherent to such composition, step, method, article, or apparatus.

When an equivalent, concentration, or other value or parameter is expressed as a range, preferred range, or a range bounded by a list of upper preferable values and lower preferable values, this is to be understood as specifically disclosing all ranges formed from any pair of any upper range limit or preferred value and any lower range limit or preferred value, regardless of whether ranges are separately disclosed. For example, when ranges of "1 to 5" are disclosed, the described ranges should be construed to include ranges of "1 to 4", "1 to 3", "1 to 2 and 4 to 5", "1 to 3 and 5", and the like. When a numerical range is described herein, unless otherwise indicated, the range is intended to include its endpoints and all integers and fractions within the range. In the description and claims of the application, the range limitations may be combined and/or interchanged, if not otherwise specified, including all the sub-ranges subsumed therein.

The indefinite articles "a" and "an" preceding an element or component of the invention are not limited to the requirement (i.e. the number of occurrences) of the element or component. Thus, the use of "a" or "an" should be interpreted as including one or at least one, and the singular reference of an element or component includes the plural reference unless the amount clearly dictates otherwise.

Example 1:

the preparation method of the bifunctional phloroglucinol adsorbing material comprises the following steps:

Step 1: 6g of chlorine spheres (chlorine content 4.88 mmol/g), N-dimethylaminoethyl ester (DHAM) (24.67 mL, chlorine content: DHAM/mol: mol=1:5), KI (0.486 g) were added to 40mL of ethanol and reacted at 60℃for 36 hours. After the reaction, methanol and water are used for washing alternately, and finally the quaternized material is obtained after vacuum drying at 60 ℃, and is marked as CMPS-DHAM-1.

Step 2: quaternized material CMPS-DHAM-1 (0.15 g), phloroglucinol (0.2522 g,2 mmol), 4-VP (0.945 mL,8 mmol) was added to a mixed solvent of 10mL toluene and 5mL acetonitrile and stirred at room temperature for 2h for preassembly.

Step 3: AIBN (4.1 mg) and ethylene glycol dimethacrylate (0.75 mL,4 mmol) were dissolved in the above-mentioned pre-assembled product, and polymerized and crosslinked under a nitrogen atmosphere at 65℃for 12 hours, and the obtained product was washed with a mixed solution of methanol and acetic acid, and dried in a vacuum oven at 60℃to obtain a bifunctional phloroglucinol adsorbent material designated as CMPS-PG-1.

Example 2:

Step 1: 6g of chlorine spheres (chlorine content 4.88 mmol/g), VIM (13.273 mL, chlorine content: VIM/mol: mol=1:5), KI (0.486 g) were added to 40mL of ethanol and reacted at 60℃for 36 hours. After the reaction, methanol and water are used for washing alternately, and finally the quaternized material is obtained after vacuum drying at 60 ℃, which is marked as CMPS-VIM-1.

Step 2: quaternized material CMPS-VIM-1 (0.15 g), phloroglucinol (0.2522 g,2 mmol) and 4-VP (0.945 mL,8 mmol) were added to a mixed solvent of 10mL toluene and 5mL acetonitrile, and the mixture was stirred at room temperature for 2h for preassembly.

Step 3: AIBN (4.1 mg) and ethylene glycol dimethacrylate (0.75 mL,4 mmol) were dissolved in the above pre-assembled product, polymerized and crosslinked for 12 hours at 65℃under a nitrogen atmosphere, and the obtained product was washed with a mixed solution of methanol and acetic acid, and dried at 60℃in a vacuum oven to give a bifunctional phloroglucinol adsorbent material designated as CMPS-PG-2.

Example 3:

Step 1: 6g of chlorine spheres (chlorine content 4.88 mmol/g), 4-VP (15.563 mL, chlorine content: 4-VP/mol: mol=1:5) and KI (0.486 g) were added to 40mL of ethanol and reacted at 60℃for 36h. After the reaction, methanol and water are used for washing alternately, and finally the quaternized material is obtained after vacuum drying at 60 ℃, which is marked as CMPS-4-VP-1.

Step 2: quaternized material CMPS-4-VP-1 (0.15 g), phloroglucinol (0.2522 g,2 mmol) and 4-VP (0.945 mL,8 mmol) were added to a mixed solvent of 10mL toluene and 5mL acetonitrile, and the mixture was stirred at room temperature for 2h for pre-assembly.

Step 3: AIBN (4.1 mg) and ethylene glycol dimethacrylate (0.75 mL,4 mmol) were dissolved in the above pre-assembled product, polymerized and crosslinked for 12 hours at 65℃under a nitrogen atmosphere, and the obtained product was washed with a mixed solution of methanol and acetic acid, and dried at 60℃in a vacuum oven to give a bifunctional phloroglucinol adsorbent material designated as CMPS-PG-3.

Example 4:

Step 2: quaternized material CMPS-VIM-1 (0.15 g), phloroglucinol (0.2522 g,2 mmol), DHAM (1.348 mL,8 mmol) was added to a mixed solvent of 10mL toluene and 5mL acetonitrile and stirred at room temperature for 2h for preassembly.

Step 3: AIBN (4.1 mg) and ethylene glycol dimethacrylate (0.75 mL,4 mmol) were dissolved in the above pre-assembled product, polymerized and crosslinked for 12 hours at 65℃under a nitrogen atmosphere, and the obtained product was washed with a mixed solution of methanol and acetic acid, and dried at 60℃in a vacuum oven to give a bifunctional phloroglucinol adsorbent material designated as CMPS-PG-4.

Example 5:

Step 2: quaternized material CMPS-VIM-1 (0.15 g), phloroglucinol (0.2522 g,2 mmol), DHAM (1.01 mL,6 mmol) were added to a mixed solvent of 10mL toluene and 5mL acetonitrile and stirred at room temperature for 2h for preassembly.

Step 3: AIBN (4.1 mg) and ethylene glycol dimethacrylate (0.75 mL,4 mmol) were dissolved in the above pre-assembled product, polymerized and crosslinked for 12 hours at 65℃under a nitrogen atmosphere, and the obtained product was washed with a mixed solution of methanol and acetic acid, and dried at 60℃in a vacuum oven to give a bifunctional phloroglucinol adsorbent material designated as CMPS-PG-5.

Example 6:

Step 1: 6g of chlorine spheres (chlorine content 4.88 mmol/g), VIM (7.964 mL, chlorine content: VIM/mol: mol=1:3), KI (0.486 g) were added to 40mLN, N-dimethylformamide and reacted at 60℃for 36h. After the reaction, methanol and water are used for washing alternately, and finally the quaternized material is obtained after vacuum drying at 60 ℃, and is marked as CMPS-VIM-2.

Step 2: quaternized material CMPS-VIM-2 (0.15 g), phloroglucinol (0.2522 g,2 mmol), DHAM (1.348 mL,8 mmol) was added to a mixed solvent of 10mL toluene and 5mL acetonitrile and stirred at room temperature for 2h for preassembly.

Step 2: AIBN (4.1 mg) and ethylene glycol dimethacrylate (0.75 mL,4 mmol) were dissolved in the above pre-assembled product, polymerized and crosslinked for 12 hours at 65℃under a nitrogen atmosphere, and the obtained product was washed with a mixed solution of methanol and acetic acid, and dried at 60℃in a vacuum oven to give a bifunctional phloroglucinol adsorbent material designated as CMPS-PG-6.

Example 7:

Step 3: azobisisoheptonitrile (6.3 mg) and ethylene glycol dimethacrylate (0.75 ml,4 mmol) were dissolved in the above-mentioned pre-assembled product, polymerized and crosslinked under nitrogen atmosphere at 65℃for 12 hours, and the obtained product was washed with a mixed solution of methanol and acetic acid, and dried in a vacuum oven at 60℃to obtain a bifunctional phloroglucinol adsorbent material designated CMPS-PG-7.

Example 8:

Step 1: 6g of chlorine spheres (chlorine content 4.88 mmol/g), 4-VP (9.338 mL, chlorine content: 4-VP/mol: mol=1:3), KI (0.486 g) were added to 40mLN, N-dimethylformamide and reacted at 60℃for 36h. After the reaction, methanol and water are used for washing alternately, and finally the quaternized material is obtained after vacuum drying at 60 ℃, which is marked as CMPS-4-VP-2.

Step 2: quaternized material CMPS-4-VP-2 (0.15 g), phloroglucinol (0.2522 g,2 mmol), DHAM (1.348 mL,8 mmol) was added to a mixed solvent of 10mL toluene and 5mL acetonitrile and stirred at room temperature for 2h for pre-assembly.

Step 3: azobisisoheptonitrile (6.3 mg) and ethylene glycol dimethacrylate (0.75 ml,4 mmol) were dissolved in the above-mentioned pre-assembled product, polymerized and crosslinked under nitrogen atmosphere at 65℃for 12 hours, and the obtained product was washed with a mixed solution of methanol and acetic acid, and dried in a vacuum oven at 60℃to obtain a bifunctional phloroglucinol adsorbent material designated CMPS-PG-8.

Example 9:

Step 1: 6g of chlorine spheres (chlorine content 4.88 mmol/g), 4-VP (15.563 mL, chlorine content: 4-VP/mol: mol=1:5) and KI (0.486 g) were added to 40mLN, N-dimethylformamide and reacted at 60℃for 36h. After the reaction, methanol and water are used for washing alternately, and finally the quaternized material is obtained after vacuum drying at 60 ℃, which is marked as CMPS-4-VP-3.

Step 2: quaternized material CMPS-VP-3 (0.15 g), phloroglucinol (0.2522 g,2 mmol), DHAM (1.01 mL,6 mmol) was added to a mixed solvent of 10mL toluene and 5mL acetonitrile and stirred at room temperature for 4h for preassembly.

Step 3: azobisisoheptonitrile (6.3 mg) and ethylene glycol dimethacrylate (0.75 ml,4 mmol) were dissolved in the above-mentioned pre-assembled product, polymerized and crosslinked under nitrogen atmosphere at 65℃for 12 hours, and the obtained product was washed with a mixed solution of methanol and acetic acid, and dried in a vacuum oven at 60℃to obtain a bifunctional phloroglucinol adsorbent material designated as CMPS-PG-9.

Application example

The bifunctional phloroglucinol adsorption materials prepared in examples 1-9 were used for adsorbing phloroglucinol, and the specific test procedure was as follows:

10mg of the above-mentioned adsorbent was added to 20mL of an aqueous solution containing phloroglucinol (1000 ppm), and the adsorbent was subjected to shaking adsorption at 180rpm at 25℃for 12 hours, and the adsorption capacity was measured, and the results are shown in Table 1.

TABLE 1 adsorption Capacity measurement results for phloroglucinol for the adsorption Material of examples 1-9

Material name	Adsorption capacity (mg/g)
		CMPS	0
CMPS-DHAM-1	33.5
		CMPS-VIM-1	55.9
CMPS-PG-1	87.6
		CMPS-PG-2	93.4
CMPS-PG-3	80.8
		CMPS-PG-4	100.4
CMPS-PG-5	124.5
		CMPS-PG-6	85.4
CMPS-PG-7	110.2
		CMPS-PG-8	106.4
CMPS-PG-9	108.7

In the foregoing, the present invention is merely preferred embodiments, which are based on different implementations of the overall concept of the invention, and the protection scope of the invention is not limited thereto, and any changes or substitutions easily come within the technical scope of the present invention as those skilled in the art should not fall within the protection scope of the present invention. Therefore, the protection scope of the present invention should be subject to the protection scope of the claims.

Claims

1. The preparation method of the bifunctional phloroglucinol adsorbing material is characterized by comprising the following steps of:

Step 1: adding a matrix material, a functional monomer and a catalyst into a solvent A, reacting for 1-48 hours at 25-80 ℃, alternately washing with an alcohol solvent and water after the reaction is finished, and drying in vacuum to obtain a quaternized material; the matrix material is chloromethyl polystyrene divinylbenzene, wherein the amount of chlorine substances is 4-5 mmol/g, the functional monomer is VIM, DHAM or 4-VP, and the molar ratio of the functional monomer, the catalyst and the chlorine in the chloromethyl polystyrene divinylbenzene is (1-5): (0.01-0.1): 1, a step of;

Step 2: mixing quaternized material, template molecules and functional monomers, adding a solvent B and a solvent C, and pre-assembling; the functional monomer is VIM, DHAM or 4-VP, the template molecule is phloroglucinol, and the mass ratio of the functional monomer, the template molecule and the quaternized material is (3-6): 1: (0.33-1);

step 3: and (3) adding an initiator and a cross-linking agent into the pre-assembled product, reacting for 2-24 hours at 40-80 ℃ in a nitrogen atmosphere, washing the obtained product with a solvent D, and drying in vacuum to obtain the bifunctional phloroglucinol adsorbing material.

2. The method according to claim 1, wherein the catalyst in the step 1 is KI or NaI, and the solvent a is one or a mixture of several of ethanol, acetonitrile, N-dimethylformamide, tetrahydrofuran, dimethyl sulfoxide, and water; the ratio of the volume of the solvent A to the mass of chloromethyl polystyrene divinylbenzene is (5-10) mL:1g.

3. The method according to claim 1, wherein in step 2, solvent B is one of toluene, methanol, and ethanol, and solvent C is acetonitrile or water; the volume ratio of the solvent B to the solvent C is (1-3): 1.

4. The method according to claim 1, wherein the pre-assembly condition in step2 is stirring at room temperature for 2-6 hours.

5. The method according to claim 1, wherein the initiator in the step 3 is one or a mixture of more of AIBN, azobisiso Ding Gengjing, azobisisobutyrimidine hydrochloride, azobisiso Ding Mi hydrochloride and benzoyl peroxide, the cross-linking agent is ethylene glycol dimethacrylate, and the mass ratio of the initiator in the step 3 to the functional monomer in the step 2 is (0.005-0.03): 1, the molar ratio of the cross-linking agent in the step 3 to the template molecules in the step 2 is (1-3): 1.

6. The method according to claim 1, wherein the solvent D in the step3 is one or a mixture of several of methanol, acetic acid, ethanol, acetonitrile and water.

7. A bifunctional phloroglucinol adsorbent material obtainable by the process of any of claims 1-6.

8. Use of the bifunctional phloroglucinol adsorbent material obtainable by the process of any of claims 1-6 for adsorbing phloroglucinol.