Polyacrylonitrile-1-methyl piperazine chromogenic fiber and synthetic method and application thereof
阅读说明：本技术 聚丙烯腈基-1-甲基哌嗪显色纤维及其合成方法和应用 (Polyacrylonitrile-1-methyl piperazine chromogenic fiber and synthetic method and application thereof ) 是由 熊春华 王小青 娄燕 张维权 方城旭 范晨阳 厉炯慧 陆海霞 沈忱 于 2020-06-19 设计创作，主要内容包括：本发明公开了一种聚丙烯腈基-1-甲基哌嗪显色纤维,以聚丙烯腈纤维PAN为母体,以1-甲基哌嗪MP作为配体,在乙二醇中加入PAN、MP、碳酸钠,加热至110～145℃反应10～40min,得到PAN-MP；PAN-MP、乙二醇、甲醛、PAR混合后加热合成显色纤维,合成温度110～140℃、时间10～30min,得到聚丙烯腈基-1-甲基哌嗪显色纤维PAN-MP-PAR。PAN-MP-PAR选择性吸附Cu(Ⅱ),能用于快速检测Cu(Ⅱ)。(The invention discloses polyacrylonitrile-1-methyl piperazine chromogenic fiber, which is prepared by taking Polyacrylonitrile (PAN) as a matrix and 1-Methyl Piperazine (MP) as a ligand, adding PAN, MP and sodium carbonate into ethylene glycol, heating to 110-145 ℃, and reacting for 10-40 min to obtain PAN-MP; and mixing the PAN-MP, the glycol, the formaldehyde and the PAR, heating to synthesize the color-developing fiber, and synthesizing at the temperature of 110-140 ℃ for 10-30 min to obtain the PAN-MP-PAR of the polyacrylonitrile-1-methylpiperazine color-developing fiber. PAN-MP-PAR selectively adsorbs Cu (II), and can be used for rapidly detecting Cu (II).)
1. The polyacrylonitrile-1-methyl piperazine chromogenic fiber is characterized in that the structural formula is as follows:
2. the method for synthesizing polyacrylonitrile-1-methylpiperazine color-developing fiber according to claim 1, characterized by comprising the following steps:
1) PAN is used as a matrix, and MP is used as a ligand; adding PAN, MP and sodium carbonate into ethylene glycol, heating to 110-145 ℃, and reacting for 10-40 min to obtain PAN-MP;
functional group-C ≡ N of PAN: MP ═ 1: 2-5 molar ratio; PAN: sodium carbonate 1: 2-5 mass ratio;
PAN: polyacrylonitrile fiber, MP: 1-methylpiperazine; PAN-MP: polyacrylonitrile-1-methylpiperazine chelate fibers;
2) adding PAN-MP, ethylene glycol, formaldehyde and PAR into a container, heating to synthesize the color-developing fiber, and synthesizing at the temperature of 110-140 ℃ for 10-30 min to obtain the polyacrylonitrile-1-methylpiperazine color-developing fiber;
PAN-MP: PAR 1-3: 1 in mass ratio;
PAR: 4- (2-pyridylazo) resorcinol.
3. The method for synthesizing polyacrylonitrile-1-methylpiperazine color-developing fiber according to claim 2, characterized in that:
in the step 1), the material-liquid ratio of PAN to glycol is 50.0mg (30 +/-5) ml;
in the step 2), the feed-liquid ratio of PAN-MP to glycol to formaldehyde is 30.0mg: (25. + -. 5) ml: (5 +/-1) ml;
the step 1) and the step 2) both adopt a microwave-assisted heating mode.
4. The method for synthesizing polyacrylonitrile-1-methylpiperazine color fibers according to claim 2 or 3, characterized in that:
in the step 1), the material-liquid ratio of PAN to glycol is 50.0mg to 30 ml; functional group-C ≡ N of PAN: MP ═ 1: 2 in a molar ratio; PAN: sodium carbonate 1: 3 in mass ratio; the heating temperature is 130 ℃, and the reaction time is 15 min;
in the step 2), the feed-liquid ratio of PAN-MP to glycol to formaldehyde is 30.0mg:25 ml: 5ml of the solution; PAN-MP: PAR 3: 1 in mass ratio; the reaction temperature is 120 ℃ and the reaction time is 15 min.
5. The use of polyacrylonitrile-1-methylpiperazine colored fibers as claimed in claim 1, characterized in that: selectively adsorbing Cu (II).
6. The use of polyacrylonitrile-1-methylpiperazine color fibers according to claim 5, characterized in that: and rapidly detecting Cu (II).
7. The use of polyacrylonitrile-1-methylpiperazine color fibers according to claim 6, characterized in that:
adding a metal salt to be tested and PAN-MP-PAR into a HAc-NaAc buffer solution with the pH value of 6 and the concentration of 0.2mol/L, wherein the color of the fiber is darkened, and the metal salt is Cu (II) salt.
8. The use of polyacrylonitrile-based-1-methylpiperazine color-developing fiber according to any one of claims 5 to 7, characterized in that: the structural formula after PAN-MP-PAR binds copper ions is:
Technical Field
The invention belongs to the technical field of chemistry, and particularly relates to a polyacrylonitrile-based-1-methylpiperazine color-developing fiber, a synthetic method and application thereof.
Background
Because the heavy metal has serious damage effect on human bodies and is difficult to metabolize, the detection of the content of the heavy metal in food is an important barrier for limiting the excessive intake of heavy metal ions by human bodies. In the existing detection method, the detection precision of a large-scale instrument and equipment is high, the result accuracy is high, but the equipment is expensive, complex to maintain and maintain, complex to operate, high in requirement on operators, long in detection period and suitable for detection scenes of laboratories and the like. The rapid detection method can save cost to a certain extent, quickens detection efficiency, improves detection capability and is more flexible and flexible to apply. The simple safety detection of large-scale food by means of large-scale instrument detection equipment cannot meet the detection requirement, and the simple, convenient, cheap, rapid, accurate and digital rapid detection equipment is the trend of food safety detection.
The polyacrylonitrile chelate fiber is developed on the basis of ion exchange fiber research, the working principle of adsorption is that a chelate with stable structure is formed between lone pair electrons contained in N, O, P, S and other elements in functional groups in an adsorption material and target ions, and a color developing agent is grafted on the basis, so that the rapid detection of the selected adsorbed heavy metal ions is significant according to the color change of the fiber.
2018102997183 patent of invention provides a modified polyacrylamide and its preparation method and application, taking polyacrylonitrile microsphere as parent, carrying out synthetic reaction with ligand (2-amino-4, 6-dimethyl pyrimidine) (ADMP), able to obtain chelate resin with high nitrogen content, which has good adsorption property to Cd (II).
201510447588X invention, namely 'a modified polyacrylonitrile', discloses a modified polyacrylonitrile, which consists of polyacrylonitrile, a filler, a curing agent, an accelerator, a coupling agent, a toughening agent and a vulcanizing agent, wherein the filler is glass fiber, the curing agent is N-aminoethyl piperazine, the accelerator is zinc dimethyldithiocarbamate, the coupling agent is methacryloxypropyl trimethoxysilane, the toughening agent is an acrylonitrile-butadiene-styrene copolymer, and the vulcanizing agent is benzoyl peroxide. The modified polyacrylonitrile has the characteristics of high strength, high wear resistance, good tear resistance and good fatigue resistance by adding the filler, the curing agent, the accelerator, the coupling agent, the toughening agent and the vulcanizing agent into the polyacrylonitrile.
Disclosure of Invention
The invention aims to provide a polyacrylonitrile-based chromogenic fiber PAN-MP-PAR which integrates the functions of enrichment, separation, chromogenic reaction and detection and is applied to the rapid detection of copper ions.
In order to solve the technical problems, the invention provides polyacrylonitrile-1-methyl piperazine chromogenic fiber (PAN-MP-PAR), which has a structural formula as follows:
the invention also provides a synthetic method of the PAN-MP-PAR, which comprises the following steps:
1) polyacrylonitrile (PAN) is used as a matrix, and 1-Methylpiperazine (MP) is used as a ligand; adding polyacrylonitrile fiber, 1-methylpiperazine and sodium carbonate into ethylene glycol (serving as a solvent), heating (microwave-assisted heating) to 110-145 ℃, and reacting for 10-40 min to obtain polyacrylonitrile-1-methylpiperazine chelate fiber (PAN-MP);
functional group-C ≡ N of PAN: MP ═ 1: 2-5 molar ratio; PAN: sodium carbonate 1: 2-5 mass ratio;
PAN: polyacrylonitrile fiber, MP: 1-methylpiperazine; PAN-MP: polyacrylonitrile-1-methylpiperazine chelate fibers;
the reaction process is as follows:
2) adding PAN-MP, ethylene glycol, formaldehyde and 4- (2-pyridylazo) resorcinol (PAR) into a container, heating (microwave-assisted heating) to synthesize a color-developing fiber, wherein the synthesis temperature is 110-140 ℃, and the synthesis time is 10-30 min, so as to obtain polyacrylonitrile-1-methylpiperazine color-developing fiber (PAN-MP-PAR);
PAN-MP: PAR 1-3: 1 in mass ratio;
PAR: 4- (2-pyridylazo) resorcinol;
the reaction process is as follows:
the post-treatment modes after the reaction of the step 1) and the step 2) are as follows: and filtering the reaction product, washing a filter cake with water, and drying.
The improvement of the synthesis method of the polyacrylonitrile-1-methyl piperazine chromogenic fiber (PAN-MP-PAR) of the invention comprises the following steps:
in the step 1), the material-liquid ratio of PAN to glycol is 50.0mg (30 +/-5) ml;
in the step 2), the feed-liquid ratio of PAN-MP to glycol to formaldehyde is 30.0mg: (25. + -. 5) ml: (5 +/-1) ml;
the step 1) and the step 2) both adopt a microwave-assisted heating mode.
Step 1), the microwave power is 800W; in the step 2), the microwave power is 400W. This parameter can be used when every 50mg of polyacrylonitrile fiber is used as the raw material.
As a further improvement of the synthesis method of the polyacrylonitrile-1-methylpiperazine colored fiber (PAN-MP-PAR) of the invention:
in the step 1), the material-liquid ratio of PAN to glycol is 50.0mg to 30 ml; functional group-C ≡ N of PAN: MP ═ 1: 2 in a molar ratio; PAN: sodium carbonate 1: 3 in mass ratio; the heating (microwave-assisted heating) temperature is 130 ℃, and the reaction time is 15 min;
in the step 2), the feed-liquid ratio of PAN-MP to glycol to formaldehyde is 30.0mg:25 ml: 5ml of the solution; PAN-MP: PAR 3: 1 in mass ratio; the reaction temperature is 120 ℃ and the reaction time is 15 min.
The invention also provides the application of the polyacrylonitrile-1-methyl piperazine chromogenic fiber (PAN-MP-PAR): selectively adsorbing Cu (II).
As an improvement of the use of the present invention: and (3) rapidly detecting the Cu (II), namely establishing a qualitative detection method for macroscopic variation of the Cu (II).
As a further improvement of the use of the invention: in HAc-NaAc buffer solution with
As a further improvement of the use of the invention: the HAc-NaAc buffer solution with the pH value of 6 and the concentration of 0.2mol/L is added with metal salt to be tested (or food suspected to contain Cu (II) pollution) and PAN-MP-PAR, the fiber color is darkened (the fiber color is changed from orange red to tan), and the metal salt is Cu (II) salt. The time required for the color reaction is at least 5 min.
In a HAc-NaAc buffer solution at a concentration of 0.2mol/L at
As a further improvement of the use of the invention: the structural formula after PAN-MP-PAR binds copper ions is:
the synthetic formula of the invention is as follows:
the invention adopts the microwave-assisted method to prepare PAN-MP-PAR, so that the PAN-MP-PAR can effectively and selectively adsorb Cu (II), has good adsorption effect, and can be applied to the rapid detection of Cu (II) in food.
In the invention, the response surface method is used for further optimizing the synthesis parameters, and considering that the PAN-MP-PAR fiber obtained by the invention detects the target heavy metal ions based on the color change, the selection of the synthesis conditions also needs to refer to the color depth of the fiber. Wherein the response surface method model is subjected to three-factor three-level experimental design on the reaction temperature, the reaction time and the molar ratio of the raw materials in the step 1), and takes the adsorption capacity as a measurement standard, and the specific model is as follows:
the table of variance analysis of the quadratic polynomial of the synthetic model in the three-factor three-level response surface optimization experiment process is shown in table 1.
TABLE 1 ANOVASTIC TABLE OF SECONDARY POLYMER OF RESPONSE SURFACE METHOD OPTIMIZED SYNTHETIC MODEL FOR PAN-MP SYNTHESIS
The concrete model obtained finally is as follows:
the influence of the interaction of the three factors on the adsorption amount and the screening of the optimization conditions are shown in FIG. 1. In combination with the color change of the developed fiber (fig. 2), the optimal level of the three factors finally determined is: 130 ℃, 15min, -CN: the MP molar ratio is 1: 2.
The invention has the following technical advantages:
(1) the compound synthesized by the invention is a new compound;
(2) the invention adopts the microwave-assisted method for preparation, and has simple synthetic method, high speed and less byproducts;
(3) the polyacrylonitrile-1-methylpiperazine color-developing fiber synthesized by the invention has the advantages of good adsorption selectivity to Cu (II), high adsorption speed, large adsorption quantity, good color development and the like.
(4) The polyacrylonitrile-1-methylpiperazine color fiber synthesized by the invention has good detection and removal effects on Cu (II) in food polluted by Cu (II).
Drawings
The following describes embodiments of the present invention in further detail with reference to the accompanying drawings.
FIG. 1 shows the influence of the interaction of three factors on the adsorption amount during the PAN-MP synthesis process and the screening of optimization conditions;
FIG. 2 is a photograph comparison of fibers for PAN, PAN-MP-PAR;
FIG. 3 is an infrared spectrum;
(a) is an infrared spectrum of PAN-MP fiber or the like
(b) Is a synthetic infrared spectrogram of PAN-MP-PAR fiber;
FIG. 4 is a thermogravimetric plot of PAN, PAN-MP-PAR;
FIG. 5 is an XRD pattern for PAN, PAN-MP, and PAN-MP-PAR;
FIG. 6 shows the selective adsorption effect of PAN-MP-PAR fibers;
FIG. 7 is a representation of the presence of copper ions in solution;
FIG. 8 shows the adsorption effect of PAN-MP-PAR fibers at different contact times;
FIG. 9 is the effect of initial concentration on the adsorption capacity of PAN-MP-PAR fibers;
FIG. 10 is a graph of the effect of buffer solution pH on the matrix color produced by PAN-MP-PAR fibers;
FIG. 11 shows the effect of heavy metal ion species on the color rendering effect of PAN-MP-PAR;
FIG. 12 is a graph showing the effect of contact time on PAN-MP-PAR color rendering.
Detailed Description
The invention will be further described with reference to specific examples, but the scope of the invention is not limited thereto:
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