CN114199803A - Method for detecting sulfonated and non-sulfonated primary aromatic amine in toner - Google Patents
Method for detecting sulfonated and non-sulfonated primary aromatic amine in toner Download PDFInfo
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- 239000011259 mixed solution Substances 0.000 claims abstract description 21
- 238000005070 sampling Methods 0.000 claims abstract description 15
- 238000001914 filtration Methods 0.000 claims abstract description 12
- LNOPIUAQISRISI-UHFFFAOYSA-N n'-hydroxy-2-propan-2-ylsulfonylethanimidamide Chemical compound CC(C)S(=O)(=O)CC(N)=NO LNOPIUAQISRISI-UHFFFAOYSA-N 0.000 claims abstract description 12
- 229910000029 sodium carbonate Inorganic materials 0.000 claims abstract description 12
- 235000010288 sodium nitrite Nutrition 0.000 claims abstract description 12
- 238000012360 testing method Methods 0.000 claims description 65
- NLKNQRATVPKPDG-UHFFFAOYSA-M potassium iodide Chemical compound [K+].[I-] NLKNQRATVPKPDG-UHFFFAOYSA-M 0.000 claims description 27
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 24
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- 238000000605 extraction Methods 0.000 claims description 16
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- VNEBWJSWMVTSHK-UHFFFAOYSA-L disodium;3-hydroxynaphthalene-2,7-disulfonate Chemical compound [Na+].[Na+].C1=C(S([O-])(=O)=O)C=C2C=C(S([O-])(=O)=O)C(O)=CC2=C1 VNEBWJSWMVTSHK-UHFFFAOYSA-L 0.000 description 2
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- G—PHYSICS
- G01—MEASURING; TESTING
- G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
- G01N21/00—Investigating or analysing materials by the use of optical means, i.e. using sub-millimetre waves, infrared, visible or ultraviolet light
- G01N21/17—Systems in which incident light is modified in accordance with the properties of the material investigated
- G01N21/25—Colour; Spectral properties, i.e. comparison of effect of material on the light at two or more different wavelengths or wavelength bands
- G01N21/31—Investigating relative effect of material at wavelengths characteristic of specific elements or molecules, e.g. atomic absorption spectrometry
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- G—PHYSICS
- G01—MEASURING; TESTING
- G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
- G01N1/00—Sampling; Preparing specimens for investigation
- G01N1/28—Preparing specimens for investigation including physical details of (bio-)chemical methods covered elsewhere, e.g. G01N33/50, C12Q
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Abstract
The application provides a method for detecting sulfonated and non-sulfonated primary aromatic amines in toner, comprising the steps of: sampling; pretreating and detecting the content of sulfonated and non-sulfonated primary aromatic amine in the pretreated toner, wherein the pretreatment step comprises the following steps: oscillating, filtering and extracting the solution to be detected to obtain primary aromatic amine extract; adding concentrated hydrochloric acid to adjust the pH value, and then fixing the volume to obtain sulfonated aromatic amine detection sample liquid; purifying the primary aromatic amine extract and then fixing the volume to obtain non-sulfonated aromatic amine detection sample liquid; sequentially adding sodium nitrite and sulfamic acid solution into the sulfonated and non-sulfonated aromatic amine detection sample solution to obtain sulfonated and non-sulfonated aromatic amine mixed solution; and respectively adding sodium carbonate and 2-naphthol-3, 6-disodium disulfonate into the mixed solution, and reacting to obtain sulfonated and non-sulfonated aromatic amine solutions to be detected. The method can realize the separation and independent determination of sulfonated and non-sulfonated aromatic amine, and has the advantages of simple operation, stability and reliability, strong anti-interference capability, high repeatability, economy and practicality.
Description
Technical Field
The application relates to the technical field of detection, in particular to a method for detecting sulfonated and non-sulfonated primary aromatic amine in toner.
Background
The primary aromatic amine is also called primary aromatic amine, and is a general name of a large class of organic compounds, and the structure of the primary aromatic amine comprises one or more amino (-NH2) groups which are directly connected with an aromatic ring. Wherein, the structure is divided into two categories according to whether the structure contains sulfonic acid groups: sulfonated primary aromatic amines and non-sulfonated primary aromatic amines. The substances are important chemical raw materials, one important application is to synthesize azo pigments, and the azo pigments are widely used as the most common dyeing components for products such as plastics, textiles and the like. However, during the synthesis, some of the primary aromatic amine may remain in the finished toner and may be indirectly added to the finished consumer product.
Most of the primary aromatic amines have certain toxicity and carcinogenicity, and four primary aromatic amines are classified as carcinogenic substances by the international agency for research on cancer (IARC). In view of the hazardous nature of these materials, the European Union AP (89) No. 1 directive sets out that toners for plastics require a total amount of residual free non-sulfonated primary aromatic amine and sulfonated primary aromatic amine of less than 500 mg/kg.
Currently, for non-sulfonated primary aromatic amines, the test Method is given in the standard (ETAD Method No.212(7)), whereas for sulfonated primary aromatic amines, there is currently no standard test Method available. However, the standard test method also has the problems of complicated operation, poor interference resistance and the like. While other testing methods using instruments such as GC-MS, LC-MS-MS and the like can only measure single primary aromatic amine, cannot measure the total amount and cannot meet the requirements of regulations.
Disclosure of Invention
In view of the problems, the present application is proposed in order to provide a method for detecting sulfonated and non-sulfonated primary aromatic amines in toner that overcomes or at least partially solves the problems.
In order to solve the above problems, embodiments of the present application disclose a method for detecting sulfonated and non-sulfonated primary aromatic amines in toner, comprising the steps of: sampling; pretreating and detecting the content of sulfonated and non-sulfonated primary aromatic amine in the pretreated toner;
wherein the pre-processing step comprises:
oscillating the sample solution to be detected at a specified rotating speed for a first time period, filtering, adding a sodium hydroxide solution until the pH value of the solution is 14, and adding chloroform for extraction to obtain a primary aromatic amine extract;
adding a concentrated hydrochloric acid solution into the primary aromatic amine extract until the primary aromatic amine extract reaches a specified pH value, and performing constant volume by using hydrochloric acid with specified concentration to obtain a sulfonated aromatic amine detection sample solution;
purifying the primary aromatic amine extract, and then fixing the volume with hydrochloric acid with specified concentration to obtain non-sulfonated aromatic amine detection sample liquid;
cooling the sulfonated aromatic amine detection sample liquid and the non-sulfonated aromatic amine detection sample liquid through ice bath for a second time, respectively adding a sodium nitrite solution for a third time, respectively adding a sulfamic acid solution, standing until the solution is dropwise added on a starch potassium iodide test paper and the test paper does not turn blue, so as to obtain a sulfonated aromatic amine mixed liquid and a non-sulfonated aromatic amine mixed liquid;
and taking two other test tubes, respectively adding sodium carbonate and 2-naphthol-3, 6-disodium disulfonate into the first test tube and the second test tube, uniformly mixing, cooling in an ice bath, dropwise adding the sulfonated aromatic amine mixed solution into the first test tube under the ice bath condition, dropwise adding the non-sulfonated aromatic amine mixed solution into the second test tube under the ice bath condition, and taking out after the fourth time-length reaction is completed to obtain the sulfonated aromatic amine solution to be detected and the non-sulfonated aromatic amine solution to be detected.
Further, the specified rotating speed is 90r/min, the specified concentration is 1mol/L, and the specified pH value is 5.5-6.5.
Further, the first time period is 30 min; the second time period is 10min, the third time period is 15min, and the fourth time period is 10 min.
Further, the sampling step includes: weighing a sample with a specified weight, adding ethanol into the sample, and adding hydrochloric acid after the sample is completely soaked to obtain the sample solution to be detected.
Further, the specified weight is 0.49-0.51g, the ratio of the sample to the ethanol is 0.49-0.51 g: 3mL, and the ratio of the ethanol to the hydrochloric acid is 3: 22.
Further, the step of purifying the primary aromatic amine extract and then fixing the volume with hydrochloric acid with specified concentration to obtain a non-sulfonated aromatic amine detection sample solution comprises the following steps:
adding water into the primary aromatic amine extract to wash the primary aromatic amine extract to remove a water phase; adding hydrochloric acid to extract for 2 times to remove an organic phase to obtain hydrochloric acid extract; and filtering the hydrochloric acid extract, and then fixing the volume by using hydrochloric acid with specified concentration to obtain non-sulfonated aromatic amine detection sample liquid.
Further, when the sulfonated aromatic amine detection sample liquid and the non-sulfonated aromatic amine detection sample liquid are colored, adding a proper amount of polycaprolactam powder respectively for oscillation until the sulfonated aromatic amine detection sample liquid and the non-sulfonated aromatic amine detection sample liquid are colorless.
Further, the step of detecting the content of sulfonated and non-sulfonated primary aromatic amines in the pretreated toner comprises:
and analyzing the sulfonated aromatic amine solution to be detected and the non-sulfonated aromatic amine solution to be detected respectively through a spectrophotometer to obtain the content of sulfonated primary aromatic amine and non-sulfonated primary aromatic amine in the toner.
Further, the wavelength of the spectrophotometer is 500 nm.
Further, the sulfonated primary aromatic amine is quantified by taking 2-aminobenzenesulfonic acid as a standard substance; the non-sulfonated primary aromatic amine was quantified using aniline as a standard.
The application has the following advantages:
the application provides a method for detecting sulfonated and non-sulfonated primary aromatic amine in toner, which comprises the following steps: sampling; pretreating and detecting the content of sulfonated and non-sulfonated primary aromatic amine in the pretreated toner; wherein the pre-processing step comprises: oscillating the sample solution to be detected at a specified rotating speed for a first time period, filtering, adding a sodium hydroxide solution until the pH value of the solution is 14, and adding chloroform for extraction to obtain a primary aromatic amine extract; adding a concentrated hydrochloric acid solution into the primary aromatic amine extract until the primary aromatic amine extract reaches a specified pH value, and performing constant volume by using hydrochloric acid with specified concentration to obtain a sulfonated aromatic amine detection sample solution; purifying the primary aromatic amine extract, and then fixing the volume with hydrochloric acid with specified concentration to obtain non-sulfonated aromatic amine detection sample liquid; cooling the sulfonated aromatic amine detection sample liquid and the non-sulfonated aromatic amine detection sample liquid through ice bath for a second time, respectively adding a sodium nitrite solution for a third time, respectively adding a sulfamic acid solution, standing until the solution is dropwise added on a starch potassium iodide test paper and the test paper does not turn blue, so as to obtain a sulfonated aromatic amine mixed liquid and a non-sulfonated aromatic amine mixed liquid; and taking two other test tubes, respectively adding sodium carbonate and 2-naphthol-3, 6-disodium disulfonate into the first test tube and the second test tube, uniformly mixing, cooling in an ice bath, dropwise adding the sulfonated aromatic amine mixed solution into the first test tube under the ice bath condition, dropwise adding the non-sulfonated aromatic amine mixed solution into the second test tube under the ice bath condition, and taking out after the fourth time-length reaction is completed to obtain the sulfonated aromatic amine solution to be detected and the non-sulfonated aromatic amine solution to be detected. The method can realize the separation and independent determination of the sulfonated aromatic amine and the non-sulfonated aromatic amine, fills the blank of the national standard method, has low detection limit, simple operation, stable and reliable method and strong anti-interference capability, can simultaneously detect the contents of the sulfonated primary aromatic amine and the non-sulfonated primary aromatic amine, can also be used for extracting colored samples, and has easy acquisition of used equipment and great popularization.
Drawings
In order to more clearly illustrate the technical solutions of the present application, the drawings needed to be used in the description of the present application will be briefly introduced below, and it is apparent that the drawings in the following description are only some embodiments of the present application, and it is obvious for those skilled in the art that other drawings can be obtained according to the drawings without inventive labor.
FIG. 1 is a flow chart illustrating the steps of a method for detecting sulfonated and non-sulfonated primary aromatic amines in toner according to one embodiment of the present disclosure;
FIG. 2 is a flow chart illustrating the steps of a method for detecting sulfonated and non-sulfonated primary aromatic amines in toner according to one embodiment of the present disclosure.
Detailed Description
In order to make the aforementioned objects, features and advantages of the present application more comprehensible, the present application is described in further detail with reference to the accompanying drawings and the detailed description. It is to be understood that the embodiments described are only a few embodiments of the present application and not all embodiments. All other embodiments, which can be derived by a person skilled in the art from the embodiments given herein without making any creative effort, shall fall within the protection scope of the present application.
One of the core ideas of the application is that sulfonated primary aromatic amine and non-sulfonated primary aromatic amine in toner are separated by specific extraction and purification pretreatment steps on a toner sample, and sodium nitrite and sulfamic acid solution are sequentially added at a specified temperature for color development to obtain sulfonated aromatic amine mixed liquor and non-sulfonated aromatic amine mixed liquor; respectively adding sodium carbonate and 2-naphthol-3, 6-disodium disulfonate mixed liquor, obtaining sulfonated and non-sulfonated aromatic amine solutions to be detected after complete reaction, and detecting by a spectrophotometer, wherein the sulfonated primary aromatic amine takes 2-aminobenzenesulfonic acid as a standard substance for quantification, and the non-sulfonated primary aromatic amine takes aniline as a standard substance for quantification, so that the contents of the sulfonated primary aromatic amine and the non-sulfonated primary aromatic amine are determined, the detection limit is low, the method is simple to operate and the popularization is strong.
Referring to fig. 1-2, a flow chart illustrating steps of a method for detecting sulfonated and non-sulfonated primary aromatic amines in toner according to an embodiment of the present application is provided, which may specifically include the following steps; s1, sampling; s2, preprocessing and S3, detecting the content of sulfonated and non-sulfonated primary aromatic amine in the toner after preprocessing,
wherein the pre-processing step comprises:
s21, oscillating the sample solution to be tested at a specified rotation speed for a first time period, filtering, adding a sodium hydroxide solution until the pH value of the solution is 14, and adding chloroform for extraction to obtain a primary aromatic amine extract;
s22, adding a concentrated hydrochloric acid solution into the primary aromatic amine extraction liquid until the primary aromatic amine extraction liquid reaches a specified pH value, and performing constant volume by using hydrochloric acid with specified concentration to obtain a sulfonated aromatic amine detection sample liquid;
s23, purifying the primary aromatic amine extract, and then fixing the volume with hydrochloric acid with specified concentration to obtain non-sulfonated aromatic amine detection sample liquid;
s24, cooling the sulfonated aromatic amine detection sample liquid and the non-sulfonated aromatic amine detection sample liquid through ice bath for a second time, respectively adding sodium nitrite solution for a third time, respectively adding sulfamic acid solution, standing until the solution is dropwise added on starch potassium iodide test paper and the test paper does not turn blue, so as to obtain sulfonated aromatic amine mixed liquid and non-sulfonated aromatic amine mixed liquid;
and S25, adding sodium carbonate and 2-naphthol-3, 6-disodium disulfonate into a first test tube and a second test tube respectively, uniformly mixing, cooling in an ice bath, adding the sulfonated aromatic amine mixed solution into the first test tube dropwise under the ice bath condition, adding the non-sulfonated aromatic amine mixed solution into the second test tube dropwise under the ice bath condition, and taking out after the fourth time period reaction is completed to obtain the sulfonated aromatic amine solution to be detected and the non-sulfonated aromatic amine solution to be detected.
The sampling step comprises the following steps:
s11, weighing a sample with a specified weight;
and S12, adding ethanol into the sample, and adding hydrochloric acid after the sample is completely soaked to obtain the sample solution to be detected.
In an embodiment of the present application, the method includes the steps of: s1, sampling; s2, preprocessing and S3, detecting the content of sulfonated and non-sulfonated primary aromatic amine in the preprocessed toner; wherein the pre-processing step comprises: s21, oscillating the sample solution to be tested at a specified rotation speed for a first time period, filtering, adding a sodium hydroxide solution until the pH value of the solution is 14, and adding chloroform for extraction to obtain a primary aromatic amine extract; s22, adding a concentrated hydrochloric acid solution into the primary aromatic amine extraction liquid until the primary aromatic amine extraction liquid reaches a specified pH value, and performing constant volume by using hydrochloric acid with specified concentration to obtain a sulfonated aromatic amine detection sample liquid; s23, purifying the primary aromatic amine extract, and then fixing the volume with hydrochloric acid with specified concentration to obtain non-sulfonated aromatic amine detection sample liquid; s24, cooling the sulfonated aromatic amine detection sample liquid and the non-sulfonated aromatic amine detection sample liquid through ice bath for a second time, respectively adding sodium nitrite solution for a third time, respectively adding sulfamic acid solution, standing until the solution is dropwise added on starch potassium iodide test paper and the test paper does not turn blue, so as to obtain sulfonated aromatic amine mixed liquid and non-sulfonated aromatic amine mixed liquid; and S25, adding sodium carbonate and 2-naphthol-3, 6-disodium disulfonate into a first test tube and a second test tube respectively, uniformly mixing, cooling in an ice bath, adding the sulfonated aromatic amine mixed solution into the first test tube dropwise under the ice bath condition, adding the non-sulfonated aromatic amine mixed solution into the second test tube dropwise under the ice bath condition, and taking out after the fourth time period reaction is completed to obtain the sulfonated aromatic amine solution to be detected and the non-sulfonated aromatic amine solution to be detected. The method can realize the separation and independent determination of the sulfonated aromatic amine and the non-sulfonated aromatic amine, fills the blank of the national standard method, has low detection limit, simple operation, stable and reliable method and strong anti-interference capability, can simultaneously detect the contents of the sulfonated primary aromatic amine and the non-sulfonated primary aromatic amine, can also be used for extracting colored samples, and has easy acquisition of used equipment and great popularization.
Next, the method for detecting sulfonated and non-sulfonated primary aromatic amines in toner in the present exemplary embodiment will be further described.
As mentioned in step S1, the sampling step includes: s11, weighing a sample with a specified weight; and S12, adding ethanol into the sample, and adding hydrochloric acid after the sample is completely soaked to obtain the sample solution to be detected.
In an embodiment of the present application, the sampling of step S1 "can be further explained with reference to the following description, and the steps include: s11, weighing a sample with a specified weight; s12, adding ethanol into the sample, and adding hydrochloric acid after the sample is completely soaked to obtain the sample solution to be detected.
Weighing a sample to be detected with a specified weight, placing the sample in a container, adding 3mL of ethanol into the sample, adding 22mL of hydrochloric acid after the sample is completely soaked, and uniformly mixing the solution to obtain the sample solution to be detected.
In the present embodiment, the sample may be a colored sample, and in other embodiments, the sample may also be a colorless sample; the sample has a specified weight of 0.49-0.51g, preferably 0.49g, 0.50g or 0.51 g; the ratio of the sample to the ethanol is 0.49-0.51 g: 3mL, the ratio of the ethanol to the hydrochloric acid is 3:22, and the preferred concentration of the hydrochloric acid is 1 mol/L.
It should be noted that sampling is generally one of the important steps of extracting a small amount of target substances from a target object for detection, and has one of the effective ways of obtaining various data by testing the target object without affecting the main properties of the target object, the extraction amount of the measured object needs to be enough for 3-5 times of testing, the process of selecting a sampling area of the measured object during sampling is required to have randomness, subjective selection cannot be doped in the selection process, and the sample is uniformly mixed to ensure the randomness of sampling.
As the above step S2, preprocessing, the preprocessing step includes:
s21, oscillating the sample solution to be tested at a specified rotation speed for a first time period, filtering, adding a sodium hydroxide solution until the pH value of the solution is 14, and adding chloroform for extraction to obtain a primary aromatic amine extract;
s22, adding a concentrated hydrochloric acid solution into the primary aromatic amine extraction liquid until the primary aromatic amine extraction liquid reaches a specified pH value, and performing constant volume by using hydrochloric acid with specified concentration to obtain a sulfonated aromatic amine detection sample liquid;
s23, purifying the primary aromatic amine extract, and then fixing the volume with hydrochloric acid with specified concentration to obtain non-sulfonated aromatic amine detection sample liquid;
s24, cooling the sulfonated aromatic amine detection sample liquid and the non-sulfonated aromatic amine detection sample liquid through ice bath for a second time, respectively adding sodium nitrite solution for a third time, respectively adding sulfamic acid solution, standing until the solution is dropwise added on starch potassium iodide test paper and the test paper does not turn blue, so as to obtain sulfonated aromatic amine mixed liquid and non-sulfonated aromatic amine mixed liquid;
and S25, adding sodium carbonate and 2-naphthol-3, 6-disodium disulfonate into a first test tube and a second test tube respectively, uniformly mixing, cooling in an ice bath, adding the sulfonated aromatic amine mixed solution into the first test tube dropwise under the ice bath condition, adding the non-sulfonated aromatic amine mixed solution into the second test tube dropwise under the ice bath condition, and taking out after the fourth time period reaction is completed to obtain the sulfonated aromatic amine solution to be detected and the non-sulfonated aromatic amine solution to be detected.
In an embodiment of the present application, a specific process of step S2 can be further explained in conjunction with the following description.
The pretreatment is generally a step for the purpose of impurity removal and purification of the target object before effective procedures, and in some special experiments, the pretreatment step also comprises the purpose of changing the material property, and in the embodiment of the application, the pretreatment step is preferably steps S21-S25, mainly comprising three steps of extraction, separation and color development.
And as stated in step S21, oscillating the sample solution to be tested at the specified rotation speed for a first time period, filtering, adding a sodium hydroxide solution until the pH of the solution is 14, and adding chloroform for extraction to obtain a primary aromatic amine extract.
In the embodiment of the application, the speed of an oscillator is set to be 90r/min, the sample solution to be tested is placed on the oscillator to be oscillated for 30min, the filtration is carried out after the oscillation, the filtrate is collected, 12.5mL of the filtrate is taken to be placed in a container, then a sodium hydroxide solution with the concentration of 5mol/L is added to adjust the pH value of the solution, and a pH meter is used for measuring until the solution is strong alkaline (the pH value is 14); extracting with chloroform for 2 times, mixing chloroform solutions, adding into another container, retaining water phase, and collecting to obtain primary aromatic amine extract; the amount of chloroform to be used is 5 to 10mL, preferably 7.5 mL.
And as stated in step S22, adding a concentrated hydrochloric acid solution to the primary aromatic amine extract until the primary aromatic amine extract reaches a specified pH, and diluting to a constant volume with a hydrochloric acid solution of a specified concentration to obtain a sulfonated aromatic amine detection sample solution.
In the examples of the present application, a concentrated hydrochloric acid solution with a concentration of 37% was added dropwise to the primary aromatic amine extract obtained above to adjust the pH of the solution to weak acidity (5.5-6.5), and a volume of 25mL was made using 1mol/L hydrochloric acid to obtain a sulfonated aromatic amine assay sample.
And as in the step S23, purifying the primary aromatic amine extract, and then making a constant volume with hydrochloric acid of a specified concentration to obtain a non-sulfonated aromatic amine detection sample solution.
In the examples of the present application, the primary aromatic amine extract obtained above is washed with water to discard the aqueous phase, extracted twice with hydrochloric acid to discard the organic phase, and then diluted to 25mL with 1mol/L hydrochloric acid to obtain a non-sulfonated aromatic amine detection sample solution, wherein the amount of water is 5-15mL, preferably 10mL, and the amount of hydrochloric acid is 3-7mL, preferably 5 mL.
In one specific implementation, when the sulfonated aromatic amine test sample solution and the non-sulfonated aromatic amine test sample solution are colored, about 0.5g of polycaprolactam powder can be added, the solution is oscillated for about 30s, most of the pigment can be adsorbed on the polycaprolactam powder, the solution is colorless and transparent, and if the solution is colored, the oscillation of increasing the amount of the polycaprolactam powder can be continued until the solution is colorless.
And step S24, cooling the sulfonated aromatic amine detection sample liquid and the non-sulfonated aromatic amine detection sample liquid through an ice bath for a second time, respectively adding a sodium nitrite solution for a third time, respectively adding a sulfamic acid solution, and standing until the solution is dropwise added on a starch potassium iodide test paper and the test paper does not turn blue, so as to obtain a sulfonated aromatic amine mixed liquid and a non-sulfonated aromatic amine mixed liquid.
In the embodiment of the application, 5mL of the obtained sulfonated aromatic amine detection sample liquid and non-sulfonated aromatic amine detection sample liquid are respectively measured and placed in a container for ice bath cooling for 10min, sodium nitrite solution is respectively added for mixing and ice bath for 15min, sulfamic acid solution is respectively added for standing until the solution is dropwise added on a starch potassium iodide test paper and the test paper does not turn blue, so that sulfonated aromatic amine mixed liquid and non-sulfonated aromatic amine mixed liquid are obtained, wherein the concentration of the sodium nitrite solution is 0.5mol/L, and the dosage of the sodium nitrite solution is 40-60 muL, preferably 50 muL; the concentration of the sulfamic acid solution is 2.5 percent, and the dosage of the sulfamic acid solution is 120-180 mu L, preferably 150 mu L; the solution is dropped onto a starch potassium iodide paper preferably for a waiting time of 5 min.
And step S25, adding sodium carbonate and 2-naphthol-3, 6-disodium disulfonate into a first test tube and a second test tube respectively, uniformly mixing, cooling in an ice bath, adding the sulfonated aromatic amine mixed solution into the first test tube dropwise under the ice bath condition, adding the non-sulfonated aromatic amine mixed solution into the second test tube dropwise under the ice bath condition, and taking out after the fourth long-term reaction is completed to obtain the sulfonated aromatic amine solution to be detected and the non-sulfonated aromatic amine solution to be detected.
In the embodiment of the application, another two test tubes are taken, sodium carbonate and 2-naphthol-3, 6-disodium disulfonate are respectively added into a first test tube and a second test tube, the mixture is uniformly mixed and cooled in an ice bath, the sulfonated aromatic amine mixed solution is added into the first test tube dropwise while shaking up under the condition of the ice bath, the non-sulfonated aromatic amine mixed solution is added into the second test tube dropwise, and after the sulfonated aromatic amine mixed solution and the non-sulfonated aromatic amine mixed solution are added dropwise, the mixture is taken out after the reaction is completed, so that the sulfonated aromatic amine solution to be detected and the non-sulfonated aromatic amine solution to be detected are obtained; wherein the concentration of the sodium carbonate is 1mol/L, and the dosage of the sodium carbonate is 3 mL; the concentration of the disodium 2-naphthol-3, 6-disulfonate is 0.05mol/L, and the dosage of the disodium 2-naphthol-3, 6-disulfonate is 0.5 mL; after the mixed solution is added dropwise, the waiting time is preferably 10 min.
In the embodiment of the application, the sulfonated aromatic amine solution to be measured and the non-sulfonated aromatic amine solution to be measured are obtained and subjected to ultrasonic wave for 30 seconds at normal temperature to expel supersaturated carbon dioxide bubbles so as to avoid the bubbles from interfering with subsequent measurement, wherein the ultrasonic frequency provided by the ultrasonic wave extractor is generally between 20kHz and 80kHz, the preferred ultrasonic frequency is between 20kHz and 50kHz, the ultrasonic power is generally between 100W and 800W, and the preferred ultrasonic power is between 100W and 500W.
The pretreated toner was tested for sulfonated and non-sulfonated primary aromatic amine content as described in step S3.
In the embodiment of the application, the obtained sulfonated aromatic amine solution to be detected and the non-sulfonated aromatic amine solution to be detected are respectively filtered by 0.45um filter membranes again, then the wavelength of a spectrophotometer is adjusted to be 500nm, the absorbance of the sample solution to be detected is read, and the sulfonated primary aromatic amine takes 2-aminobenzenesulfonic acid as a standard substance for quantification; and quantifying the non-sulfonated primary aromatic amine by taking aniline as a standard substance, and calculating according to the content and absorbance of the standard substance and the absorbance of a sample solution to be detected to obtain the content of sulfonated and non-sulfonated primary aromatic amine in the toner.
In the embodiment of the application, the typical sample is subjected to simulated migration, a quantitative target substance to be detected is added into the migration liquid, and the corresponding equipment is adopted to perform verification experiment detection analysis.
And (3) a labeling process: weighing 0.50g of toner sample, adding 25 mu L (the theoretical solution concentration is 1mg/L) of standard substance (aniline and 2-aminobenzenesulfonic acid) stock solution of 1000mg/L, processing according to the sample pretreatment step, filtering the solution to be detected again by using a 0.45um filter membrane, adjusting the wavelength of a spectrophotometer to be 500nm, reading the absorbance of the sample solution to be detected, and calculating to obtain the contents of sulfonated primary aromatic amine and non-sulfonated primary aromatic amine in the toner.
The recovery rates are shown in Table 1:
| material of | Sulfonated primary aromatic amines | Non-sulfonated primary aromatic amines |
| Red toner | 69 | 76 |
TABLE 1
Linear range (mg/L): 0.5, 1, 2, 5; coefficient of correlation R2Comprises the following steps: 0.996, and a minimum detection limit of 50 ppm.
From the above results, it can be seen that the minimum detection limit of the method of the present application is about 50ppm, the recovery rate is high, and it can be seen that the contents of sulfonated and non-sulfonated primary aromatic amine in the toner product can be accurately measured.
The embodiments in the present specification are described in a progressive manner, each embodiment focuses on differences from other embodiments, and the same and similar parts among the embodiments are referred to each other.
While preferred embodiments of the present application have been described, additional variations and modifications of these embodiments may occur to those skilled in the art once they learn of the basic inventive concepts. Therefore, it is intended that the appended claims be interpreted as including the preferred embodiment and all such alterations and modifications as fall within the true scope of the embodiments of the application.
Finally, it should also be noted that, herein, relational terms such as first and second, and the like may be used solely to distinguish one entity or action from another entity or action without necessarily requiring or implying any actual such relationship or order between such entities or actions. Also, the terms "comprises," "comprising," or any other variation thereof, are intended to cover a non-exclusive inclusion, such that a process, method, article, or terminal that comprises a list of elements does not include only those elements but may include other elements not expressly listed or inherent to such process, method, article, or terminal. Without further limitation, an element defined by the phrase "comprising an … …" does not exclude the presence of other like elements in a process, method, article, or terminal that comprises the element.
The method for detecting sulfonated and non-sulfonated primary aromatic amines in toner provided by the present application is described above in detail, and the principle and the implementation manner of the present application are explained in the present application by using specific examples, and the description of the above examples is only used to help understand the method and the core concept of the present application; meanwhile, for a person skilled in the art, according to the idea of the present application, there may be variations in the specific embodiments and the application scope, and in summary, the content of the present specification should not be construed as a limitation to the present application.
Claims (10)
1. A method for detecting sulfonated and non-sulfonated primary aromatic amines in toner comprising the steps of: sampling; pretreating and detecting the content of sulfonated and non-sulfonated primary aromatic amine in the pretreated toner;
wherein the pre-processing step comprises:
oscillating the sample solution to be detected at a specified rotating speed for a first time period, filtering, adding a sodium hydroxide solution until the pH value of the solution is 14, and adding chloroform for extraction to obtain a primary aromatic amine extract;
adding a concentrated hydrochloric acid solution into the primary aromatic amine extract until the primary aromatic amine extract reaches a specified pH value, and performing constant volume by using hydrochloric acid with specified concentration to obtain a sulfonated aromatic amine detection sample solution;
purifying the primary aromatic amine extract, and then fixing the volume with hydrochloric acid with specified concentration to obtain non-sulfonated aromatic amine detection sample liquid;
cooling the sulfonated aromatic amine detection sample liquid and the non-sulfonated aromatic amine detection sample liquid through ice bath for a second time, respectively adding a sodium nitrite solution for a third time, respectively adding a sulfamic acid solution, standing until the solution is dropwise added on a starch potassium iodide test paper and the test paper does not turn blue, so as to obtain a sulfonated aromatic amine mixed liquid and a non-sulfonated aromatic amine mixed liquid;
and taking two other test tubes, respectively adding sodium carbonate and 2-naphthol-3, 6-disodium disulfonate into the first test tube and the second test tube, uniformly mixing, cooling in an ice bath, dropwise adding the sulfonated aromatic amine mixed solution into the first test tube under the ice bath condition, dropwise adding the non-sulfonated aromatic amine mixed solution into the second test tube under the ice bath condition, and taking out after the fourth time-length reaction is completed to obtain the sulfonated aromatic amine solution to be detected and the non-sulfonated aromatic amine solution to be detected.
2. The method according to claim 1, wherein the specified rotation speed is 90r/min, the specified concentration is 1mol/L, and the specified pH value is 5.5-6.5.
3. The method of claim 1, wherein the first time period is 30 min; the second time period is 10min, the third time period is 15min, and the fourth time period is 10 min.
4. The method of claim 1, wherein the sampling step comprises: weighing a sample with a specified weight, adding ethanol into the sample, and adding hydrochloric acid after the sample is completely soaked to obtain the sample solution to be detected.
5. The method of claim 4, wherein the specified weight is 0.49-0.51g, and the ratio of the sample to the ethanol is 0.49-0.51 g: 3mL, and the ratio of the ethanol to the hydrochloric acid is 3: 22.
6. The method as claimed in claim 1, wherein the step of purifying the primary aromatic amine extract and then diluting the purified primary aromatic amine extract with hydrochloric acid with a specified concentration to obtain a non-sulfonated aromatic amine detection sample solution comprises:
adding water into the primary aromatic amine extract to wash the primary aromatic amine extract to remove a water phase; adding hydrochloric acid to extract for 2 times to remove an organic phase to obtain hydrochloric acid extract; and filtering the hydrochloric acid extract, and then fixing the volume by using hydrochloric acid with specified concentration to obtain non-sulfonated aromatic amine detection sample liquid.
7. The method as claimed in claim 1, wherein when the sulfonated aromatic amine test sample and the non-sulfonated aromatic amine test sample are colored, a proper amount of polycaprolactam powder is added to the colored sulfonated aromatic amine test sample and the non-sulfonated aromatic amine test sample, respectively, and the colored sulfonated aromatic amine test sample and the non-sulfonated aromatic amine test sample are shaken until the sulfonated aromatic amine test sample and the non-sulfonated aromatic amine test sample are colorless.
8. The method of claim 1, wherein the step of detecting the amount of sulfonated and non-sulfonated primary aromatic amine in the pretreated toner comprises:
and analyzing the sulfonated aromatic amine solution to be detected and the non-sulfonated aromatic amine solution to be detected respectively through a spectrophotometer to obtain the content of sulfonated primary aromatic amine and non-sulfonated primary aromatic amine in the toner.
9. The method of claim 8, wherein the spectrophotometer has a wavelength of 500 nm.
10. The method according to claim 1, wherein the sulfonated primary aromatic amine is quantified with 2-aminobenzenesulfonic acid as a standard; the non-sulfonated primary aromatic amine was quantified using aniline as a standard.
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