Polyethyleneimine polymer based on tetraphenyl ethylene carboxylic acid modification and preparation method, product and application thereof

Abstract

The invention provides a tetraphenyl ethylene carboxylic acid modified polyethyleneimine polymer as well as a preparation method, a product and application thereof, and belongs to the technical field of adsorption of VOCs (Volatile Organic Compounds) by polymer gel. The preparation method of the tetraphenyl ethylene carboxylic acid-based modified polyethyleneimine polymer comprises the following steps: sequentially dissolving polyethyleneimine and a terpyridyl compound with a carboxylic acid group in an organic solvent to obtain a mixture; and adding a styrene carboxylic acid compound into the mixture, adjusting the pH value to be alkaline, adding a condensing agent, and carrying out a stirring reaction to obtain a target product. After the target product is dissolved in different alcohol solvents to prepare the polymer gel, the adsorption rate of VOCs is high.

Description

Technical Field

[0001] The invention relates to the technical field of polymer gel adsorption of VOCs, and in particular to a polyethyleneimine polymer modified by tetraphenylethylene carboxylic acid, and a preparation method, product and application thereof. Background Art

[0002] Trace amounts of volatile organic compounds are produced in the body through metabolic processes or symbiotic bacteria, migrate through the blood circulation, and eventually cross the alveolar interface to appear in exhaled air. To date, there is no "universally reliable" single marker that can define any type of disease, but excessive amounts of specific volatile compounds are considered potential indicators of health status and disease screening. For example, asthma is associated with elevated concentrations of nitric oxide and ethane in the breath. There are also ketone bodies, especially acetone, which can reflect changes in metabolic processes caused by diabetes. Although fasting, ketogenic diets, and prolonged exercise can also produce ketone bodies, the concentration of acetone in the exhaled breath of diabetic patients is much higher than that of healthy individuals, increasing from an average of less than 0.9 ppm (parts per million) to more than 1.8 ppm, making acetone a prime candidate for therapeutic monitoring of metabolic disorders caused by diabetes. Traditional detection methods include distillation, evaporation, and gas chromatography-mass spectrometry. Although these technologies have certain efficiency, they have many disadvantages due to high operating and maintenance costs and the generation of byproducts (such as toxic sludge). Summary of the invention

[0003] In view of this, the object of the present invention is to provide a polyethyleneimine polymer modified by tetraphenylethylene carboxylic acid and a preparation method, product and application thereof.

[0004] In order to achieve the above object, the present invention provides the following technical solutions:

[0005] One of the technical solutions of the present invention is a method for preparing a polyethyleneimine polymer based on tetraphenylethylene carboxylic acid, comprising the following steps:

[0006] Dissolving polyethyleneimine and a terpyridine compound having a carboxylic acid group in an organic solvent in sequence to obtain a mixture;

[0007] Add a styrene carboxylic acid compound to the mixture, adjust the pH to be alkaline, then add a condensation agent to carry out stirring reaction to obtain the target product.

[0008] The second technical solution of the present invention is a tetraphenylethylene carboxylic acid-modified polyethyleneimine polymer prepared by the above-mentioned preparation method.

[0009] The third technical solution of the present invention is a polymer gel, which is prepared by dissolving the above-mentioned tetraphenylethylene carboxylic acid-modified polyethyleneimine polymer in an alcohol solvent and then subjecting it to ultrasonic treatment to form a gel.

[0010] A fourth technical solution of the present invention is an application of the above-mentioned polymer gel in the adsorption and detection of VOCs.

[0011] The present invention discloses the following technical effects:

[0012] The present invention grafts terpyridine substances and styrene carboxylic acid substances with carboxylic acid groups onto polyethyleneimine to obtain a polyethyleneimine polymer modified based on tetraphenylethylene carboxylic acid, which is then dissolved in different types of alcohol solvents to produce specific fluorescence, facilitating VOCs detection.

[0013] The preparation method provided by the invention requires mild conditions, has strong operability, good reproducibility, and the obtained product is stable, economical and low in cost.

[0014] The polymer gel provided by the present invention has a high adsorption rate for VOCs, and the fluorescence is quenched after the carbon tetrachloride is adsorbed, so carbon tetrachloride detection can be performed. In addition, the polymer gel can cyclically adsorb VOCs, proving that it can be reused. BRIEF DESCRIPTION OF THE DRAWINGS

[0015] In order to more clearly illustrate the embodiments of the present invention or the technical solutions in the prior art, the drawings required for use in the embodiments will be briefly introduced below. Obviously, the drawings described below are only some embodiments of the present invention. For ordinary technicians in this field, other drawings can be obtained based on these drawings without paying creative work.

[0016] Figure 1 The synthetic route of the target product of Example 1 is shown in FIG.

[0017] Figure 2 This is the NMR image of the target product of Example 1;

[0018] Figure 3 This is the adsorption diagram of different VOCs by the polymer gel obtained in Example 1;

[0019] Figure 4 This is a fluorescence image of carbon tetrachloride adsorbed by the polymer gel obtained in Example 1;

[0020] Figure 5 This is the adsorption diagram of the polymer gel obtained in Example 1 to ethyl acetate and acetone in different volume proportions;

[0021] Figure 6 This is the adsorption diagram of the polymer gel obtained in Example 1 to a mixed solution of acetone, ethyl acetate and carbon tetrachloride. DETAILED DESCRIPTION

[0022] Various exemplary embodiments of the present invention will now be described in detail. This detailed description should not be considered as limiting the present invention, but should be understood as a more detailed description of certain aspects, features, and embodiments of the present invention.

[0023] It should be understood that the terms described in the present invention are only for describing a particular embodiment and are not intended to limit the present invention. In addition, for the numerical range in the present invention, it should be understood that each intermediate value between the upper and lower limits of the scope is also specifically disclosed. The intermediate value in any stated value or stated range, and each smaller range between any other stated value or intermediate value in the described range is also included in the present invention. The upper and lower limits of these smaller ranges can be independently included or excluded in the scope.

[0024] Unless otherwise indicated, all technical and scientific terms used herein have the same meanings as those generally understood by those skilled in the art. Although the present invention describes only preferred methods and materials, any methods and materials similar or equivalent to those described herein may also be used in the implementation or testing of the present invention. All documents mentioned in this specification are incorporated by reference to disclose and describe the methods and / or materials associated with the documents. In the event of a conflict with any incorporated document, the content of this specification shall prevail.

[0025] It will be apparent to those skilled in the art that various modifications and variations may be made to the specific embodiments of the present invention description without departing from the scope or spirit of the present invention. Other embodiments derived from the present invention description will be apparent to the skilled artisan. The present invention description and examples are exemplary only.

[0026] The words “include,” “including,” “have,” “contain,” etc. used in this document are open-ended terms, meaning including but not limited to.

[0027] Compared with traditional detection methods (distillation, evaporation, gas chromatography-mass spectrometry), adsorption method has attracted wide attention due to its economy, environmental protection, flexible design and function, and high efficiency. Due to the presence of various functional groups (such as amides, amines and carboxylic acids) in the polymer network of the gel, the gel can bind heavy metal ions or organic compounds during the pollutant removal process, thus becoming an excellent adsorbent. Compared with other adsorption materials (including activated carbon, zeolites, silica gel, biomass and inorganic minerals), the gel has the advantages of simplicity, high adsorption and easy recovery. The present invention prepares a polymer gel based on tetraphenylethylene carboxylic acid modified polyethyleneimine polymer dissolved in different alcohol solvents, which has a high adsorption rate for VOCs.

[0028] Based on the above content, the present invention provides a preparation method of a tetraphenylethylene carboxylic acid-modified polyethyleneimine polymer, comprising the following steps:

[0029] Dissolving polyethyleneimine and a terpyridine compound having a carboxylic acid group in an organic solvent in sequence to obtain a mixture;

[0030] Add a styrene carboxylic acid compound to the mixture, adjust the pH to be alkaline, then add a condensation agent to carry out stirring reaction to obtain the target product.

[0031] In a preferred embodiment of the present invention, the polyethyleneimine is linear polyethyleneimine or branched polyethyleneimine; the terpyridine compound with a carboxylic acid group is bisterpyridine carboxylic acid, 4-[2,2':6',2"-terpyridine]-4'-benzoic acid, 5-[2,2':6',2"-terpyridine]-4'-isophthalic acid or [2,2':6',2"-terpyridine]-4'-carboxylic acid; the styrene carboxylic acid compound is distyrene carboxylic acid, tristyrene carboxylic acid or tetrastyrene carboxylic acid; the condensing agent is at least one of 1-hydroxybenzotriazole, N,N'-dicyclohexylcarbodiimide, diisopropylcarbodiimide and 1-(3-dimethylaminopropyl)-3-ethylcarbodiimide; the mass ratio of the polyethyleneimine, the terpyridine compound with a carboxylic acid group, the styrene carboxylic acid compound and the condensing agent is (12-16):2:1:2.5.

[0032] In a preferred embodiment of the present invention, the condensing agent is 1-hydroxybenzotriazole and N,N'-dicyclohexylcarbodiimide in a molar ratio of 1:1.

[0033] In a preferred embodiment of the present invention, the organic solvent is N,N-dimethylformamide. The present invention does not specifically limit the dissolution method of polyethyleneimine and terpyridine compounds with carboxylic acid groups in the organic solvent, and the commonly used technical means by those skilled in the art can be used, such as stirring dissolution.

[0034] In a preferred embodiment of the present invention, the pH is 7-8; and the reagent used to adjust the pH is triethylamine.

[0035] In a preferred embodiment of the present invention, the stirring reaction is carried out at a temperature of 10-30° C. and for a time of 48-72 h.

[0036] In a preferred embodiment of the present invention, after the stirring reaction is completed, the step of reducing the pressure on the reaction solution to distill off the organic solvent to obtain a yellow transparent viscous product is also included, and then water is added to the yellow transparent viscous product with stirring to precipitate a white solid, filtering and collecting the transparent solution, and freeze-drying the transparent solution is performed.

[0037] The present invention also provides a tetraphenylethylene carboxylic acid-modified polyethyleneimine polymer prepared by the preparation method described in the above technical solution.

[0038] The present invention also provides a polymer gel, which is prepared by dissolving the tetraphenylethylene carboxylic acid-modified polyethyleneimine polymer in an alcohol solvent and then subjecting it to ultrasonic treatment to form a gel; the power of the ultrasonic treatment is 500W and the time is 3-6 minutes.

[0039] In a preferred embodiment of the present invention, the alcohol solvent is methanol, ethanol, n-propanol, isopropanol, n-butanol, n-pentanol or cyclohexanol. The mass volume ratio of the tetraphenylethylene carboxylic acid-modified polyethyleneimine polymer to the alcohol solvent is 40-50 mg: 300-500 μL.

[0040] The present invention also provides an application of the polymer gel in adsorbing and detecting VOCs.

[0041] In a preferred embodiment of the present invention, the VOCs is at least one of acetone, ethyl acetate and carbon tetrachloride.

[0042] In order to better understand the present invention, the content of the present invention is further explained in conjunction with the following examples, but the content of the present invention is not limited to the following examples. Taking Example 1 as an example, the synthesis route of the tetraphenylethylene carboxylic acid-modified polyethyleneimine polymer in the present invention is as follows: Figure 1 shown.

[0043] Unless otherwise specified, the raw materials and reagents used in the examples can be obtained through commercial sources.

[0044] Example 1

[0045] Weigh 12g of branched polyethyleneimine, dissolve it in DMF, and stir at room temperature until it is clear and transparent to obtain a mixed solution. Then add 2g of bis(terpyridine)carboxylic acid and 1g of tetraphenylethylene carboxylic acid, add triethylamine dropwise to adjust the pH to 7-8, then add 1g of 1-hydroxybenzotriazole and 1.5g of N,N'-dicyclohexylcarbodiimide, and seal the reaction at room temperature for 48h. After the reaction is completed, the DMF solvent is distilled off under reduced pressure, and the product is yellow, transparent and viscous. Finally, add distilled water and stir, and a large amount of white solid will precipitate. Filter and remove the filter cake to obtain a transparent solution. Freeze dry in a freeze dryer to obtain a viscous, transparent target product (based on tetraphenylethylene carboxylic acid modified polyethyleneimine polymer). ( Figure 2 )

[0046] 60 mg of the target product was dissolved in 400 μL of cyclohexanol, ultrasonicated for 5 min, and allowed to stand to form a gel to obtain a polymer gel. The adsorption capacity of the polymer gel on acetone, ethyl acetate, and carbon tetrachloride was tested, and the adsorption results were as follows:

[0047] (1) When the polymer gel adsorbs acetone, ethyl acetate, and carbon tetrachloride, the adsorption of acetone is 12 g / g (40 days), the adsorption of ethyl acetate is 3.2 g / g (16 days), and the adsorption of carbon tetrachloride is 2.5 g / g (6 days). Figure 3 ) In addition, during the process of gel adsorption of carbon tetrachloride, the fluorescence of the gel will be quenched as time goes by. ( Figure 4 )

[0048] (2) Ethyl acetate and acetone with different volume ratios were adsorbed. When the ratio of ethyl acetate to acetone was 1:9, the total adsorption amount was 11 g / g. When the ratio of ethyl acetate to acetone was 1:1, the total adsorption amount was 5.6 g / g. Figure 5 )

[0049] (3) The adsorption capacity of the mixed solution of ethyl acetate, acetone and carbon tetrachloride (v / v / v=1:1:1) is 5g / g. Figure 6 )

[0050] Example 2

[0051] Weigh 15g of branched polyethyleneimine, dissolve it in DMF, and stir at room temperature until it is clear and transparent to obtain a mixed solution. Then add 2g of 4-[2,2':6',2"-terpyridine]-4'-benzoic acid and 1g of tetraphenylethylene carboxylic acid, add triethylamine dropwise to adjust the pH to 7-8, then add 1g of 1-hydroxybenzotriazole and 1.5g of N,N'-dicyclohexylcarbodiimide, and seal the reaction at room temperature for 48h. After the reaction is completed, distill the DMF solvent under reduced pressure, and the product is yellow, transparent and viscous. Finally, add distilled water and stir, and a large amount of white solid will precipitate. Filter and remove the filter cake to obtain a transparent solution. Freeze dry in a freeze dryer to obtain a viscous and transparent target product (based on tetraphenylethylene carboxylic acid modified polyethyleneimine polymer).

[0052] 60 mg of the target product was dissolved in 400 μL of cyclohexanol, ultrasonicated for 5 min, and allowed to stand to form a gel to obtain a polymer gel.

[0053] Example 3

[0054] Weigh 14g of branched polyethyleneimine, dissolve it in DMF, and stir at room temperature until it is clear and transparent to obtain a mixed solution. Then add 2g of [2,2':6',2"-terpyridine]-4'-carboxylic acid and 1g of tetraphenylethylene carboxylic acid, add triethylamine dropwise to adjust the pH to 7-8, then add 1g of 1-hydroxybenzotriazole and 1.5g of N,N'-dicyclohexylcarbodiimide, and seal the reaction at room temperature for 48h. After the reaction is completed, distill the DMF solvent under reduced pressure, and the product is yellow, transparent and viscous. Finally, add distilled water and stir, and a large amount of white solid will precipitate. Filter and remove the filter cake to obtain a transparent solution. Freeze-dry in a freeze dryer to obtain a viscous and transparent target product (based on tetraphenylethylene carboxylic acid modified polyethyleneimine polymer).

[0055] 60 mg of the target product was dissolved in 400 μL of cyclohexanol, ultrasonicated for 5 min, and allowed to stand to form a gel to obtain a polymer gel.

[0056] Example 4

[0057] Weigh 13g of branched polyethyleneimine, dissolve it in 100mL of DMF, and stir at room temperature until it is clear and transparent to obtain a mixed solution. Then add 2g of 5-[2,2':6',2"-terpyridine]-4'-isophthalic acid and 1g of tetraphenylethylene carboxylic acid, add triethylamine dropwise to adjust the pH to 7-8, then add 1g of 1-hydroxybenzotriazole and 1.5g of N,N'-dicyclohexylcarbodiimide, and seal the reaction at room temperature for 48h. After the reaction is completed, distill off the DMF solvent under reduced pressure, and the product is yellow, transparent and viscous. Finally, add distilled water and stir, and a large amount of white solid will precipitate. Filter and remove the filter cake to obtain a transparent solution. Freeze dry in a freeze dryer to obtain a viscous, transparent target product.

[0058] 60 mg of the target product was dissolved in 400 μL of cyclohexanol, ultrasonicated for 5 min, and allowed to stand to form a gel to obtain a polymer gel.

[0059] The present invention also tests the adsorption of acetone, ethyl acetate and carbon tetrachloride by the polymer gels prepared in Examples 2, 3 and 4 (the adsorption test is the same as that in Example 1). The results show that the adsorption effects of the polymer gels in Examples 2-4 on acetone, ethyl acetate and carbon tetrachloride are comparable to those in Example 1.

[0060] The above is only a preferred embodiment of the present invention. It should be pointed out that for ordinary technicians in this technical field, several improvements and modifications can be made without departing from the principle of the present invention. These improvements and modifications should also be regarded as the scope of protection of the present invention.

Claims

1. A method for preparing a tetraphenylethylene carboxylic acid-modified polyethyleneimine polymer, characterized in that: The following steps are involved: Dissolving polyethyleneimine and a terpyridine compound having a carboxylic acid group in an organic solvent in sequence to obtain a mixture; Add a styrene carboxylic acid compound to the mixture, adjust the pH to be alkaline, then add a condensation agent to carry out stirring reaction to obtain the tetraphenylethylene carboxylic acid-modified polyethyleneimine polymer.

2. The method for preparing a tetraphenylethylene carboxylic acid-modified polyethyleneimine polymer according to claim 1, characterized in that: The polyethyleneimine is linear polyethyleneimine or branched polyethyleneimine; the terpyridine compound with a carboxylic acid group is bisterpyridine carboxylic acid, 4-[2,2':6',2"-terpyridine]-4'-benzoic acid, 5-[2,2':6',2"-terpyridine]-4'-isophthalic acid or [2,2':6',2"-terpyridine]-4'-carboxylic acid; the styrene carboxylic acid compound is distyrene carboxylic acid, tristyrene carboxylic acid or tetrastyrene carboxylic acid; the condensing agent is at least one of 1-hydroxybenzotriazole, N,N'-dicyclohexylcarbodiimide, diisopropylcarbodiimide and 1-(3-dimethylaminopropyl)-3-ethylcarbodiimide; the mass ratio of the polyethyleneimine, the terpyridine compound with a carboxylic acid group, the styrene carboxylic acid compound and the condensing agent is (12-16):2:1:2.

5.

3. The method for preparing a tetraphenylethylene carboxylic acid-modified polyethyleneimine polymer according to claim 1, characterized in that: The organic solvent is N,N-dimethylformamide.

4. The method for preparing a tetraphenylethylene carboxylic acid-modified polyethyleneimine polymer according to claim 1, characterized in that: The stirring reaction is carried out at a temperature of 10-30°C and for a time of 48-72 hours.

5. The method for preparing a tetraphenylethylene carboxylic acid-modified polyethyleneimine polymer according to claim 1, characterized in that: After the stirring reaction is completed, the step also includes distilling the organic solvent from the reaction solution under reduced pressure to obtain a yellow transparent viscous product, then adding water to the yellow transparent viscous product and stirring to precipitate a white solid, filtering and collecting the transparent solution, and freeze-drying the transparent solution.

6. A tetraphenylethylene carboxylic acid-modified polyethyleneimine polymer prepared by the preparation method according to any one of claims 1 to 5.

7. A polymer gel, characterized in that The tetraphenylethylene carboxylic acid-modified polyethyleneimine polymer according to claim 6 is dissolved in an alcohol solvent, and then subjected to ultrasound to form a gel.

8. The polymer gel according to claim 7, characterized in that The alcohol solvent is methanol, ethanol, n-propanol, isopropanol, n-butanol, n-pentanol or cyclohexanol. The mass volume ratio of the tetraphenylethylene carboxylic acid-modified polyethyleneimine polymer to the alcohol solvent is 40-50 mg: 300-500 μL.

9. Use of the polymer gel according to claim 7 in the adsorption and detection of VOCs.

10. The use of the polymer gel according to claim 9 in adsorption and detection of VOCS, characterized in that: The VOCs are at least one of acetone, ethyl acetate and carbon tetrachloride.

Images