CN114965537A - Method for measuring total chlorine and inorganic chlorine content in polycarbonate resin - Google Patents
Method for measuring total chlorine and inorganic chlorine content in polycarbonate resin Download PDFInfo
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Abstract
The invention relates to a method for measuring the content of total chlorine and inorganic chlorine in polycarbonate resin. In the total chlorine content measurement, the polycarbonate resin to be measured is fully hydrolyzed by adopting a mixed solution of metal hydroxide and carbonate with certain concentration under certain temperature and pressure, and chlorine in various forms is converted into sodium chloride for total chlorine detection. In the measurement of the content of the inorganic chlorine, the invention sufficiently dissolves the inorganic chlorine in the polycarbonate by a method of combining water phase reverse phase extraction and organic phase liquid-liquid extraction. The detection method can easily realize the detection of the content of the chloride ions in the aqueous solution by converting the object to be detected by the method of spectrum or ion chromatography, has the advantages of simple operation, good repeatability, high accuracy and the like, and can be used for detecting the content of the chloride in the polycarbonate product produced by the interfacial polycondensation method and the production process control.
Description
Technical Field
The invention belongs to the technical field of determination of chlorine content in polycarbonate, and particularly relates to a determination method of total chlorine content in polycarbonate resin and a determination method of inorganic chlorine content.
Background
The information in this background section is only for enhancement of understanding of the general background of the invention and is not necessarily to be construed as an admission or any form of suggestion that this information forms the prior art that is already known to a person of ordinary skill in the art.
During the interfacial reaction of polycarbonate, a carbonyl source such as phosgene often undergoes a phosgenation reaction with bisphenol A (BPA) sodium salt to produce polycarbonate with sodium chloride (NaC1) as a by-product. In this case, sodium chloride is dissolved as a reaction by-product in the light phase of the aqueous solution and can be removed by washing. Hydrolysis to form hydrogen chloride or residual methylene chloride may occur during the removal of the solvent from the polymerization mother liquor. If these impurities remain in the polycarbonate, they cause yellowing of the polycarbonate resin during the later processing, which limits the application of the polycarbonate. In order to produce low chlorine polycarbonates and to improve the quality of the product appearance, the residual chlorine levels in the production process and in the end product should be monitored and controlled.
No report is found in the prior art about a method for measuring total chlorine in polycarbonate resin. Inorganic chlorine has been reported, but has many disadvantages. For example, PCT/IB2016/054177 discloses a method for measuring the chloride ion content of polycarbonate by dissolving polycarbonate in a non-chlorinated solvent, adding to boiling water to precipitate polycarbonate, volatilizing the non-chlorinated solvent, and measuring chloride ion by ion chromatography. The disadvantages are that the non-chlorinated solvent can not be completely removed in boiling water, and simultaneously, a large amount of water carries partial chlorine to evaporate, so that the deviation of the detection result is large.
Disclosure of Invention
Based on the above technical background, the present invention is directed to a method for measuring the total chlorine and inorganic chlorine contents in polycarbonate; through determination, the two determination methods provided by the invention are simple to operate and high in accuracy.
In a first aspect of the present invention, there is provided a method for measuring the total chlorine content in a polycarbonate resin, the method comprising adding a sample of a polycarbonate resin to be measured to a mixed solution of a hydroxide and a carbonate, hydrolyzing the mixture at a predetermined temperature and pressure, and measuring the chlorine content in the hydrolyzed solution.
In the above detection method, at a certain temperature and pressure, the polycarbonate resin is completely hydrolyzed and converted into soluble salts such as sodium bisphenol a and sodium carbonate through hydrolysis of hydroxide and carbonate, and methylene chloride, terminal chloroformate and the like in the resin are converted into sodium chloride, i.e. in the first aspect of the invention, the polycarbonate resin polymer is first converted into soluble salt micromolecule substances through hydrolysis, and organic chlorine components in a sample are converted into inorganic sodium chloride for determination, and the advantages of the determination mode at least include the following aspects:
(1) in the detection method, the polycarbonate resin is subjected to hydrolysis reaction completely under the conditions specified by the invention, the resin material is completely degraded and converted into a water-soluble substance, and the chlorine-containing substance in the resin can be fully converted into sodium chloride in an aqueous solution, so that the accuracy and the stability of the detection method can be effectively ensured;
(2) in the detection method, the polycarbonate resin is used for pretreating the sample before the chlorine content is measured in a hydrolysis mode, so that the defects of inaccurate chlorine content measurement result and low result in a traditional method by high-temperature digestion or a direct extraction method are overcome;
(3) the detection method converts organic chlorine into sodium chloride as a determination object, the sodium chloride is easy to obtain and has economic cost, which means that quantitative standard products of the detection method are very easy to obtain, and the reagent cost of an enterprise in a product detection link can be effectively reduced; in addition, the sodium chloride has good solubility and stability in water, the sodium chloride generated after hydrolysis is completely dissolved in a reaction system, other purification or extraction and separation steps are not needed, and the possibility of system errors is reduced;
(4) the reagents involved in the hydrolysis reaction are easy to obtain, have high safety, and have mild hydrolysis reaction conditions and low harm to operators.
The detection method needs to measure the content of chlorine in the hydrolyzed solution, and the measurement can be carried out through a spectrum or an ion spectrum.
The second aspect of the invention provides a method for measuring the content of inorganic chlorine in polycarbonate resin, which is characterized in that a polycarbonate resin sample to be measured is added into a first non-chlorine solvent to be shaken and dissolved, then water is added into the first non-chlorine solvent to fully dissolve inorganic chlorine, and a mixed solution of the non-chlorine solvent and the water is obtained through separation; and adding a second non-chlorine solvent into the mixed solution for extraction to obtain a lower-layer water phase, and measuring the content of inorganic chlorine in the water phase.
In the above measurement method, the first non-chlorine solvent is soluble in water and the second non-chlorine solvent, and has a better solubility in the second non-chlorine solvent; the second non-chlorine solvent is immiscible with water. In the second aspect of the present invention, by adopting the above design, the polycarbonate resin is dissolved in the first non-chlorine solvent, the polycarbonate resin is precipitated from the solvent by using the difference between the solubilities of the polycarbonate resin and the inorganic chlorine in water, the inorganic chlorine is dissolved in the mixed solution of water and the first non-chlorine solvent, the first non-chlorine solvent miscible with water is extracted by using another second non-chlorine solvent immiscible with water, and the inorganic chlorine is dissolved in water and can be detected by a spectroscopic or ionic spectroscopic method.
The beneficial effects of one or more technical schemes are as follows:
1. the invention adopts alkali catalysis, heating and pressurizing methods to convert insoluble polycarbonate resin into soluble substances, simultaneously converts various forms of chlorine into sodium chloride, and adopts single-wavelength X-ray fluorescence spectrometry to detect total chlorine, and the methods are not reported at home and abroad at present.
2. The method adopts a method of combining aqueous phase back extraction and organic phase liquid-liquid extraction to dissolve inorganic chlorine in the polycarbonate, is accurate and reliable, and has not been reported at home and abroad.
3. The method disclosed by the invention has the advantages of strong operability, simplicity in operation, good repeatability, high accuracy and the like, and is suitable for measuring the chlorine content in the similar substances.
Drawings
The accompanying drawings, which are incorporated in and constitute a part of this specification, are included to provide a further understanding of the invention, and are included to illustrate an exemplary embodiment of the invention and not to limit the invention.
FIG. 1 is a standard graph of total chlorine content measured by single-wavelength X-ray fluorescence spectroscopy as described in example 1.
FIG. 2 is a chromatogram of inorganic chlorine measured by ion chromatography in example 8.
FIG. 3 is a standard graph of the content of inorganic chlorine measured by ion chromatography in example 8.
FIG. 4 is a standard graph of inorganic chlorine content by single wavelength X-ray fluorescence spectroscopy in example 8.
Detailed Description
It is to be understood that the following detailed description is exemplary and is intended to provide further explanation of the invention as claimed. Unless defined otherwise, all technical and scientific terms used herein have the same meaning as commonly understood by one of ordinary skill in the art to which this invention belongs.
It is noted that the terminology used herein is for the purpose of describing particular embodiments only and is not intended to be limiting of exemplary embodiments according to the invention. As used herein, the singular forms "a", "an", and "the" are intended to include the plural forms as well, and it should be understood that when the terms "comprises" and/or "comprising" are used in this specification, they specify the presence of stated features, steps, operations, devices, components, and/or combinations thereof, unless the context clearly indicates otherwise.
In a first aspect of the present invention, there is provided a method for measuring the total chlorine content in a polycarbonate resin, the method comprising adding a sample of a polycarbonate resin to be measured to a mixed solution of hydroxide and carbonate, hydrolyzing the mixture at a temperature and a pressure, and measuring the chlorine content in the hydrolyzed solution.
In the above scheme, the polycarbonate resin sample to be tested is powder, flakes or resin particles dried by desolventizing, and is added into the mixed solution after being processed into a powder form, wherein the particle size of the powder is 1um to 1000um, and more preferably 1um to 500 um. The flakes or resin particles may be processed into powder by shearing or pressing, including but not limited to, crushing using an ultra-low temperature crusher or a grinder, or shearing and crushing after cooling by liquid nitrogen.
Preferably, the hydroxide is one or two of sodium hydroxide, potassium hydroxide, barium hydroxide and lithium hydroxide, and further preferably sodium hydroxide or potassium hydroxide.
Preferably, the carbonate is one of sodium carbonate, sodium bicarbonate, potassium carbonate and potassium bicarbonate.
Preferably, in the mixed solution, the mass percentage concentration of the hydroxide solution is 20-40%, and the mass percentage concentration of the carbonate solution is 2-8%.
Preferably, the amount of the hydroxide added is 6 to 16 times, and more preferably 7 to 13 times, the mass of the polycarbonate resin.
Preferably, the temperature of the hydrolysis reaction is 80-230 ℃, and more preferably 95-200 ℃; the hydrolysis reaction is carried out under a pressure of 0.1 to 4MPa, preferably 0.1 to 3MPa, and if necessary, under a closed condition.
Preferably, the method for measuring the content of the chlorine element is detection by spectrum or ion chromatography; further, the detection mode is spectrum detection, and in a specific example, single-wavelength X-ray fluorescence spectrum is used for detection.
In an embodiment of the above preferred technical solution, the detection method specifically includes the following steps:
(1) preparing a series of sodium chloride standard substance solutions with concentration gradients, measuring the counting rate of the sodium chloride standard solution by adopting a single-wavelength X-ray fluorescence spectrometer, and acquiring a regression curve of the counting rate relative to the sodium chloride concentration by taking the standard solution concentration as an abscissa and the counting rate as an ordinate;
(2) taking the mixed solution of hydroxide and carbonate as a blank solution, measuring the counting rate of chlorine element in the blank solution by using single-wavelength X-ray fluorescence spectrometry or ion chromatography, and obtaining the concentration value C of chlorine element in the blank solution according to a standard curve 0-a (ii) a Measuring the counting rate of the chlorine element in the hydrolyzed solution by adopting a single-wavelength X-ray fluorescence spectrometry, and obtaining the concentration value C of the chlorine element in the sample solution according to a standard curve i According to the formula ω ═ C i-a -C 0-a ) And multiplied by V/m, and the content of the total chlorine in the polycarbonate is calculated.
Wherein omega represents the content of total chlorine in the polycarbonate sample to be detected; c i-a Representing the concentration of chlorine element in the sample solution to be detected; c 0-a Indicating the concentration of chlorine element in the blank solution; v represents the volume of the sample solution to be measured; m represents the mass of the polycarbonate sample to be tested.
The second aspect of the invention provides a method for measuring the content of inorganic chlorine in polycarbonate resin, which is characterized in that a polycarbonate resin sample to be measured is added into a first non-chlorine solvent to be shaken and dissolved, then water is added into the first non-chlorine solvent to fully dissolve inorganic chlorine, and a mixed solution of the non-chlorine solvent and the water is obtained through separation; and adding a second non-chlorine solvent into the mixed solution for extraction to obtain a lower-layer water phase, and measuring the content of inorganic chlorine in the water phase.
It should be noted that the polycarbonate resin sample described in the second aspect is the same as that of the first aspect, but differs therefrom in that when the polycarbonate resin is in the form of powder, the material should be subjected to extrusion preforming or extrusion granulation.
Preferably, the first non-chlorine solvent is tetrahydrofuran, NN-dimethylformamide or a combination thereof, and more preferably, the first non-chlorine solvent is tetrahydrofuran, NN-dimethylformamide.
Preferably, the second non-chlorine solvent is one of cyclohexane, petroleum ether, ethyl acetate, benzene, toluene, n-butane, pentane, n-hexane, benzyl alcohol and cyclohexanone.
Preferably, the amount of the added water is 0.1 to 2 times, and more preferably 0.3 to 1.8 times, the volume of the first non-chlorine solvent.
Preferably, the adding amount of the second non-chlorine solvent is 0.5-5 times of the volume of the first non-chlorine solvent; more preferably, the amount is 1 to 3 times.
Preferably, the inorganic chlorine content is measured by spectrum detection or ion chromatography, in a specific embodiment, the inorganic chlorine content is measured by single-wavelength X-ray fluorescence spectrum detection or ion chromatography, in which the detection steps are as follows:
(1) obtaining a sample solution: adding a polycarbonate resin sample to be detected into a first non-chlorine solvent for shaking and dissolving, then adding water into the first non-chlorine solvent to fully dissolve out inorganic chlorine, and separating to obtain a mixed solution of a non-chlorinated solvent and water; adding a second non-chlorine solvent into the mixed solution for extraction to obtain a lower-layer water phase, namely a sample solution;
(2) obtaining a blank liquid: adding a first non-chlorine solvent into water, adding a second non-chlorine solvent for extraction, wherein the dosage of the first non-chlorine solvent, the dosage of the water and the dosage of the second non-chlorine solvent are the same as that in the step (1), and separating to obtain a water phase as a blank liquid;
(3) obtaining a regression curve: preparing a series of sodium chloride standard substance solutions with concentration gradients, measuring the counting rate of the sodium chloride standard solution by adopting a single-wavelength X-ray fluorescence spectrometer, and acquiring a regression curve of the counting rate relative to the sodium chloride concentration by taking the standard solution concentration as an abscissa and the counting rate as an ordinate; determining the area or peak height of the chloride ion absorption peak in the sodium chloride standard solution by adopting ion chromatography, and drawing a curve by taking the concentration of the standard solution as a horizontal coordinate and the area or peak height of the chloride ion absorption peak as a vertical coordinate;
(4) determination of inorganic chlorine content: measuring the counting rate of chlorine element or the area or peak height of the chlorine ion absorption peak in the blank solution by adopting single-wavelength X-ray fluorescence spectrometry or ion chromatography, and obtaining the concentration value C of chlorine element in the blank solution according to a standard curve 0-b ；
Measuring the counting rate of chlorine element in the sample liquid by single-wavelength X-ray fluorescence spectrometry or ion chromatographyThe area or the peak height of the chloride ion absorption peak is respectively obtained according to a standard curve to obtain the concentration value C of the chlorine element in the sample solution i-b According to the formula ω ═ C i-b -C 0-b ) And x V/m, and calculating to obtain the content of the inorganic chlorine in the polycarbonate resin.
Wherein omega represents the content of inorganic chlorine in the polycarbonate resin sample to be detected; c i Representing the concentration of chlorine element in the sample solution to be detected; c 0 Indicating the concentration of chlorine element in the blank solution; v represents the volume of the sample solution to be measured; m represents the mass of the polycarbonate resin sample to be tested.
In order to make the technical solutions of the present invention more clearly understood by those skilled in the art, the technical solutions of the present invention will be described in detail below with reference to specific embodiments.
Example 1
In the present embodiment, there is provided a method for measuring a total chlorine content in a polycarbonate resin, the method comprising the steps of:
(1) sample pretreatment: about 50g of polycarbonate resin particles were weighed and pulverized by a liquid nitrogen ultra-low temperature pulverizer, and the average particle diameter of the powder was 82 um. 6.5024g, 6.2216g and 6.7186g of polycarbonate powder are accurately weighed in sequence and placed in a 150mL reaction tank, 53g, 50g and 54g of potassium hydroxide (20 wt%) and sodium carbonate (5 wt%) mixed solution are respectively added, and the mixture is heated to 180 ℃ under the pressure of 1.5MPa under stirring and undergoes hydrolysis reaction for 8 hours.
(2) Preparing a sample solution: and cooling to room temperature, transferring the reaction solution into a 100mL volumetric flask, and diluting to a constant volume to obtain 3 parallel samples of the solution to be detected.
(3) Preparing a blank solution: the same amount of potassium hydroxide (20 wt%) and sodium carbonate (5 wt%) mixed solution was weighed according to step (1) and placed in 3 100mL volumetric flasks, diluted to the mark, as a blank solution of 3 parallel samples.
(4) Preparation of sodium chloride standard solution: the sodium chloride standard solution with the concentration of 100ug/mL is diluted by deionized water to prepare the sodium chloride standard solution with the concentration of 2ug/mL, 4ug/mL, 6ug/mL, 8ug/mL, 10ug/mL and 13 ug/mL.
(5) Drawing a standard curve: the counting rates of chlorine elements of 6 standard solutions are measured by a single-wavelength X-ray fluorescence spectrometer, the instrument automatically processes data to obtain a standard curve, the obtained linear fitting equation is that Y is 0.2541X +0.189, and the correlation coefficient r is 0.9998.
(6) And (3) determination of a sample: and measuring the chlorine element counting rates of the blank solution and the sample solution of the 3 parallel samples by using a single-wavelength X-ray fluorescence spectrometer, and respectively calculating the sodium chloride concentration in the 3 parallel sample solutions according to a linear fitting equation. According to the formula ω ═ C i-a -C 0-a ) The total chlorine content was calculated for 3 parallel samples of polycarbonate resin x V/m.
TABLE 1
Example 2
In this embodiment, there is provided a method for measuring the total chlorine content in a polycarbonate resin, the method comprising the steps of:
6.4812g, 6.4089g and 6.5126g of the polycarbonate powder in example 1 were weighed out in sequence, placed in a 150mL reaction tank, and mixed solutions of 45g, 44g and 46g of potassium hydroxide (30 wt%) and sodium carbonate (4 wt%) were added thereto, and heated to 170 ℃ under 2.1MPa with stirring, followed by hydrolysis reaction for 5 hours.
After completion of the reaction, the reaction mixture was cooled to room temperature, and the total chlorine content of 3 parallel samples of the polycarbonate resin was measured in accordance with the procedures (2), (3), (4), (5) and (6) of example 1.
TABLE 2
Example 3
In this embodiment, there is provided a method for measuring the total chlorine content in a polycarbonate resin, the method comprising the steps of:
5.8612g, 6.0365g and 5.9862g of the polycarbonate powder in example 1 were weighed out in sequence, placed in a 150mL reaction tank, and mixed solutions of 41g, 42g and 42g of sodium hydroxide (30 wt%) and potassium carbonate (5 wt%) were added, heated to 170 ℃ under stirring and at a pressure of 1.8MPa, and subjected to hydrolysis reaction for 6 hours.
After completion of the reaction, the reaction mixture was cooled to room temperature, and the total chlorine content of 3 parallel samples of the polycarbonate resin was measured in accordance with the procedures (2), (3), (4), (5) and (6) of example 1.
TABLE 3
Example 4
In this embodiment, there is provided a method for measuring the total chlorine content in a polycarbonate resin, the method comprising the steps of:
sample pretreatment: 5.5024g, 5.3325g and 5.4156g of polycarbonate resin granules are accurately weighed in sequence and placed in a 150mL reaction tank, and mixed solution of 45g, 44g and 46g of potassium hydroxide (30 wt%) and sodium carbonate (5 wt%) is added respectively, and the mixture is heated to 100 ℃ under stirring and subjected to hydrolysis reaction for 16h under normal pressure.
After completion of the reaction, the reaction mixture was cooled to room temperature, and the total chlorine content of 3 parallel samples of the polycarbonate resin was measured in accordance with the procedures (2), (3), (4), (5) and (6) of example 1.
TABLE 4
Example 5
In the present example, there is provided a method for measuring the total chlorine content in a polycarbonate resin, the pretreatment method in the measuring method being as follows:
sample pretreatment: 4.3452g, 5.0845g and 4.8352g of polycarbonate resin granules are accurately weighed in sequence and placed in a 150mL reaction tank, 48g, 56g and 53g of potassium hydroxide (10 wt%) and sodium carbonate (5 wt%) mixed solution are respectively added, and the mixture is heated to 180 ℃ under the pressure of 2MPa under the stirring, the hydrolysis reaction lasts for 16h, and the polycarbonate hydrolysis rate is 52%.
Example 6
In the present example, there is provided a method for measuring the total chlorine content in a polycarbonate resin, the pretreatment method in the measuring method being as follows:
sample pretreatment: 6.5024g, 6.3325g and 6.4156g of polycarbonate resin granules are accurately weighed in sequence and placed in a 150mL reaction tank, 45g, 44g and 46g of potassium hydroxide (35 wt%) and sodium carbonate (5 wt%) mixed solution are respectively added, the mixture is heated to 80 ℃ under stirring, the mixture is hydrolyzed under normal pressure for 16h, and the hydrolysis rate of the polycarbonate is 86%.
Example 7
In this example, there is provided a method for measuring the total chlorine content in a polycarbonate resin by a blank spiking recovery measurement, the method comprising the steps of:
(1) preparation of a sample: analytically pure sodium chloride was ground to a fine powder using a grinder. Putting 2000g of non-phosgene polycarbonate resin into a high-speed mixer, adding 0.2g of standard substance sodium chloride powder, fully mixing, extruding, granulating and drying after mixing.
(2) Pretreatment of the sample: 50g of the extruded particles are taken and crushed by a liquid nitrogen low-temperature crusher, and the average particle size of the powder is 95 um. 5.0889g, 5.0138g, 5.1013g and 5.0315g of polycarbonate resin powder were weighed out and subjected to hydrolysis reaction in the same manner as in example 1.
The total chlorine content in 4 parallel samples of the polycarbonate resin was measured according to the steps (2), (3), (4), (5) and (6) of example 1, and the recovery rate of chlorine was calculated.
TABLE 5
In examples 1 to 6, the same batch of polycarbonate resin samples was subjected to hydrolysis with an alkali solution and a carbonate and then repeatedly measured, and it can be seen from the results in tables 1 to 4 that the measurement deviation of the total chlorine content in the polycarbonate resin was 0.1 or less, indicating that the above-mentioned measurement method has good reproducibility. In example 7, the chlorine recovery rate of the sample treatment method was measured by a sample loading and recovery method, and the results in table 5 show that the recovery rates of 4 parallel samples in the same batch are not very different and can reach 100.03% on average, and the data also confirm that the detection method provided by the invention can fully extract and recover chlorine element in the samples, and the method is stable and has high accuracy.
Example 8
In this embodiment, a method for measuring the content of inorganic chlorine in a polycarbonate resin is provided, which includes the steps of:
(1) pretreatment of samples
3.5121g, 3.5093g and 3.5109g of polycarbonate resin pellets were accurately weighed and placed in 100mL stoppered bottles, and 50mL of tetrahydrofuran was added thereto and dissolved completely in a shaker. Accurately measuring 15mL of deionized water, slowly dropwise adding the deionized water into the tetrahydrofuran solution under stirring, and stirring for 30min after dropwise adding. Transferring the mixed solution of tetrahydrofuran and water into a separating funnel, measuring 100mL of cyclohexane by using a measuring cylinder, adding the cyclohexane into the mixed solution, fully shaking, standing, layering and taking a lower-layer water phase.
(2) Preparation of sample solution
The aqueous solution separated from the two phases was directly used as a sample solution for measurement.
(3) Preparation of blank solution
Measuring 50mL of tetrahydrofuran by using a measuring cylinder, adding the tetrahydrofuran into a 200mL separating funnel, accurately measuring 15mL of deionized water, adding the deionized water into the tetrahydrofuran, uniformly mixing, then adding 100mL of cyclohexane, fully shaking, standing, layering, and then taking a lower-layer water phase, wherein the lower-layer water phase is a blank solution of a sample to be detected.
(4) Preparation of sodium chloride standard solution
The sodium chloride standard solution with the concentration of 100ug/mL is diluted by water to prepare the sodium chloride standard solution with the concentration of 1ug/mL, 2ug/mL, 4ug/mL, 6ug/mL, 8ug/mL and 10 ug/mL.
(5) Drawing a standard curve:
the counting rates of chlorine elements of 6 standard solutions are measured by a single-wavelength X-ray fluorescence spectrometer, the counting rates are used as vertical coordinates, the concentration is used as horizontal coordinates, the instrument automatically processes data to obtain a standard curve, the obtained linear fitting equation is that Y is 0.2622X +0.163, and the correlation coefficient r is 0.9995.
Measuring the area of the chloride ion absorption peak of 6 concentration gradient standard solutions by adopting ion chromatography, taking the area of the chloride ion absorption peak as a vertical coordinate and the concentration (ug/mL) of the chloride ion as a horizontal coordinate, automatically processing data by using an instrument to obtain a standard curve of the area and the concentration of the chloride ion absorption peak, wherein the obtained linear fitting equation is that Y is 1123800X-34859, and the correlation coefficient r is 0.9998.
(6) And (3) determination of a sample:
measuring the counting rates of chlorine elements of a blank solution and 3 parallel sample solutions by using a single-wavelength X-ray fluorescence spectrometer, and respectively calculating the concentration of chlorine ions in the 3 parallel sample solutions according to a linear fitting equation. According to the formula ω ═ C i-b -C 0-b ) The inorganic chlorine content of 3 parallel samples was calculated x V/m.
Secondly, measuring the areas of the chlorine absorption peaks of the blank solution and the 3 parallel sample solutions by adopting ion chromatography, and obtaining the concentration of the chlorine ions of the sample to be measured according to a standard curve linear fitting equation. According to the formula ω ═ C i-b -C 0-b ) The inorganic chlorine content of 3 parallel samples of polycarbonate resin was calculated at x V/m.
TABLE 6
TABLE 7
As can be seen from the results in tables 6 and 7, the results of the X-ray fluorescence spectrum detection are substantially consistent with the results of the ion chromatography detection, indicating that both of the above two detection methods can be applied to the method for detecting inorganic chlorine.
Example 9
In this embodiment, a method for measuring the content of inorganic chlorine in a polycarbonate resin is provided, which includes the steps of:
(1) sample pretreatment
3.1078g, 3.1231g and 3.1099g of polycarbonate resin pellets were accurately weighed and placed in 100mL stoppered bottles, and 40mL of tetrahydrofuran was added thereto and dissolved completely in a shaker. Accurately measuring 20mL of deionized water, slowly dropwise adding the deionized water into the tetrahydrofuran solution under stirring, and stirring for 30min after dropwise adding. Transferring the mixed solution of tetrahydrofuran and water into a separating funnel, measuring 90mL of methylbenzene by using a measuring cylinder, adding the methylbenzene into the mixed solution, fully shaking, standing, layering and taking a lower-layer aqueous phase.
The inorganic chlorine content of 3 parallel samples of the polycarbonate resin was measured by ion chromatography in accordance with the procedures (2) (3) (4), (5) and (6) of example 8.
TABLE 8
Example 10
In this embodiment, a method for measuring the content of inorganic chlorine in a polycarbonate resin is provided, which includes the steps of:
the test sample is polycarbonate resin powder produced in the production process, is extruded into a strip at 300 ℃ by a melt index tester, and is cut into particles. 3.5209g, 3.5176g and 3.5213g of resin particles are accurately weighed respectively and placed in a 100mL bottle with a stopper, 50mL of tetrahydrofuran is added respectively and placed in a shaker to be completely dissolved. 30mL of deionized water is accurately measured and slowly dripped into the tetrahydrofuran solution under stirring, and the mixture is stirred for 30min after the dripping is finished. Transferring the mixed solution of tetrahydrofuran and water into a separating funnel, measuring 70mL of methylbenzene by using a measuring cylinder, adding the methylbenzene into the mixed solution, fully shaking, standing, layering and taking a lower-layer water phase.
The content of inorganic chlorine in 3 parallel samples of polycarbonate resin was measured by X-ray fluorescence spectroscopy according to the procedures (2), (3), (4), (5) and (6) of example 8.
TABLE 9
Example 11
In this embodiment, a method for measuring the content of inorganic chlorine in a polycarbonate resin is provided, which includes the steps of:
5.0011g, 5.0087g and 5.0056g of polycarbonate resin granules are accurately weighed respectively and placed in 200mL bottles with stoppers, 50mL of tetrahydrofuran is added respectively and placed in a shaker to be completely dissolved. Accurately measuring 100mL of deionized water, slowly dropwise adding the deionized water into the tetrahydrofuran solution under stirring, and stirring for 30min after dropwise adding. Transferring the mixed solution of tetrahydrofuran and water into a separating funnel, measuring 100mL of methylbenzene by using a measuring cylinder, adding the methylbenzene into the mixed solution, fully shaking, standing, layering and taking a lower-layer water phase.
The inorganic chlorine content of 3 parallel samples of polycarbonate resin was measured according to the procedures (2), (3), (4), (5) and (6) of example 9. Because the volume of added water is large, the chlorine content in the extracted water is low, the signal response is weak, the result is low, and the stability, the repeatability and the accuracy are poor.
Example 12
In this embodiment, a method for measuring the content of inorganic chlorine in a polycarbonate resin is provided, which includes the steps of:
a sample of the polycarbonate extruded pellets of example 7 was taken and subjected to a blank spiked recovery assay. 2.0135g, 2.0189g, 2.0156g and 2.0110g of polycarbonate resin granules are accurately weighed respectively and placed in a 100mL bottle with a plug, and 25mL of tetrahydrofuran is added respectively and placed in a shaker to be completely dissolved. 40mL of deionized water is accurately measured and slowly dripped into the tetrahydrofuran solution under stirring, and the mixture is stirred for 30min after the dripping is finished. Transferring the mixed solution of tetrahydrofuran and water into a separating funnel, measuring 50mL of methylbenzene by using a measuring cylinder, adding the methylbenzene into the mixed solution, fully shaking, standing, layering and taking a lower-layer water phase.
The inorganic chlorine content of 4 parallel samples of polycarbonate resin was measured by using a single-wavelength X-ray fluorescence spectrometer according to the procedures (2), (3), (4) and (5) of example 8. The blank spiked recovery was calculated as the ratio of the measured value of the sample to the theoretical value of 100 ug/g.
TABLE 11
Similarly, in example 12, the chlorine recovery rate of the sample treatment method was measured by a sample-loading recovery method, and the results in table 11 show that the recovery rates of parallel samples of 4 polycarbonate resins of the same batch are substantially the same and can reach 99.87% on average, which confirms that the inorganic chlorine detection method provided by the present invention has good stability and accuracy.
The above description is only a preferred embodiment of the present invention and is not intended to limit the present invention, and various modifications and changes may be made by those skilled in the art. Any modification, equivalent replacement, or improvement made within the spirit and principle of the present invention should be included in the protection scope of the present invention.
Claims (10)
1. A method for measuring the total chlorine content in a polycarbonate resin is characterized in that a polycarbonate resin sample to be measured is added into a mixed solution of hydroxide and carbonate to be hydrolyzed under certain temperature and pressure, and the chlorine content in the hydrolyzed solution is measured.
2. The method for determining the total chlorine content in the polycarbonate resin according to claim 1, wherein the polycarbonate resin sample to be determined is a powder, a flake or a resin particle, preferably a polycarbonate resin powder, and the particle size of the powder is 1um to 1000um, more preferably 1um to 500 um.
3. The method for measuring the total chlorine content in a polycarbonate resin according to claim 1, wherein the hydroxide is one or two of sodium hydroxide, potassium hydroxide, barium hydroxide and lithium hydroxide, and is preferably sodium hydroxide or potassium hydroxide;
or the carbonate is one of sodium carbonate, sodium bicarbonate, potassium carbonate and potassium bicarbonate.
4. The method for measuring the total chlorine content in a polycarbonate resin according to claim 1, wherein the mixed solution has a concentration of 20 to 40% by mass of the hydroxide solution and a concentration of 2 to 8% by mass of the carbonate solution;
or, the adding amount of the hydroxide is 6-16 times of the mass of the polycarbonate, and the further optimization is 7-13 times;
or the temperature of the hydrolysis reaction is 80-230 ℃, and more preferably 95-200 ℃; the hydrolysis reaction is carried out under a pressure of 0.1MPa to 4MPa, more preferably 0.1MPa to 3MPa, and if necessary, under a closed condition.
5. The method for measuring the total chlorine content in a polycarbonate resin according to claim 1, wherein the method for measuring the chlorine content is a spectroscopic or ion chromatographic method; further, the detection mode is spectral detection, and in a specific example, single-wavelength X-ray fluorescence spectrum is used for detection.
6. The method for measuring the total chlorine content in a polycarbonate resin according to claim 5, wherein the detection method comprises the following specific steps:
(1) preparing a series of sodium chloride standard substance solutions with concentration gradients, measuring the counting rate of the sodium chloride standard solution by adopting a single-wavelength X-ray fluorescence spectrometer, and acquiring a regression curve of the counting rate relative to the sodium chloride concentration by taking the standard solution concentration as an abscissa and the counting rate as an ordinate;
(2) taking the mixed solution of hydroxide and carbonate as a blank solution, measuring the counting rate of chlorine element in the blank solution by using single-wavelength X-ray fluorescence spectrometry or ion chromatography, and obtaining the concentration value C of chlorine element in the blank solution according to a standard curve 0-a (ii) a And (3) measuring the counting rate of the chlorine element in the hydrolyzed solution by adopting a single-wavelength X-ray fluorescence spectrometry, and obtaining a concentration value C of the chlorine element in the sample solution according to a standard curve.
7. The method for measuring the content of inorganic chlorine in the polycarbonate resin is characterized by comprising the steps of adding a polycarbonate resin sample to be measured into a first non-chlorine solvent to be shaken and dissolved, adding water into the first non-chlorine solvent to fully dissolve inorganic chlorine, and separating to obtain a mixed solution of the non-chlorine solvent and the water; and adding a second non-chlorine solvent into the mixed solution for extraction to obtain a lower-layer water phase, and measuring the content of inorganic chlorine in the water phase.
8. The method of claim 7, wherein the first non-chlorine solvent is tetrahydrofuran, NN-dimethylformamide or a combination thereof, and more preferably, the first non-chlorine solvent is a combination of tetrahydrofuran and NN-dimethylformamide;
or, the second non-chlorine solvent is one of cyclohexane, petroleum ether, ethyl acetate, benzene, toluene, n-butane, pentane, n-hexane, benzyl alcohol and cyclohexanone.
9. The method for measuring the inorganic chlorine content in a polycarbonate resin according to claim 7, wherein the amount of the water added is 0.1 to 2 times, more preferably 0.3 to 1.8 times, the volume of the first non-chlorine solvent;
or the addition amount of the second non-chlorine solvent is 0.5-5 times of the volume of the first non-chlorine solvent; more preferably, the amount is 1 to 3 times.
10. The method for measuring the content of inorganic chlorine in a polycarbonate resin according to claim 7, wherein the inorganic chlorine content is measured by spectroscopic measurement or ion chromatography, and specifically, the inorganic chlorine content is measured by single-wavelength X-ray fluorescence spectroscopic measurement or ion chromatography, and in this embodiment, the measurement steps are as follows:
(1) obtaining a sample solution: adding a polycarbonate resin sample to be detected into a first non-chlorine solvent for shaking and dissolving, then adding water into the first non-chlorine solvent to fully dissolve out inorganic chlorine, and separating to obtain a mixed solution of a non-chlorinated solvent and water; adding a second non-chlorine solvent into the mixed solution for extraction to obtain a lower-layer water phase, namely a sample solution;
(2) obtaining a blank liquid: adding a first non-chlorine solvent into water, adding a second non-chlorine solvent for extraction, wherein the dosage of the first non-chlorine solvent, the dosage of the water and the dosage of the second non-chlorine solvent are the same as that in the step (1), and separating to obtain a water phase as a blank liquid;
(3) obtaining a regression curve: preparing a series of sodium chloride standard substance solutions with concentration gradients, measuring the counting rate of the sodium chloride standard solution by adopting a single-wavelength X-ray fluorescence spectrometer, and acquiring a regression curve of the counting rate relative to the sodium chloride concentration by taking the standard solution concentration as an abscissa and the counting rate as an ordinate; determining the area or peak height of the chloride ion absorption peak in the sodium chloride standard solution by adopting ion chromatography, and drawing a curve by taking the concentration of the standard solution as a horizontal coordinate and the area or peak height of the chloride ion absorption peak as a vertical coordinate;
(4) determination of inorganic chlorine content: measuring the counting rate of chlorine element or the area or peak height of the chlorine ion absorption peak in the blank solution by adopting single-wavelength X-ray fluorescence spectrometry or ion chromatography, and obtaining the concentration value C of chlorine element in the blank solution according to a standard curve 0-b ；
Measuring the counting rate of chlorine element or the area or peak height of the chlorine ion absorption peak in the sample solution by using single-wavelength X-ray fluorescence spectrometry or ion chromatography, and respectively obtaining the concentration value C of chlorine element in the sample solution according to a standard curve i-b And calculating to obtain the content of the inorganic chlorine in the polycarbonate.
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