CN117849213A - Method for measuring contents of p-tert-butylbenzoic acid and barium in PVC heat stabilizer - Google Patents
Method for measuring contents of p-tert-butylbenzoic acid and barium in PVC heat stabilizer Download PDFInfo
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- CN117849213A CN117849213A CN202311727854.5A CN202311727854A CN117849213A CN 117849213 A CN117849213 A CN 117849213A CN 202311727854 A CN202311727854 A CN 202311727854A CN 117849213 A CN117849213 A CN 117849213A
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- KDVYCTOWXSLNNI-UHFFFAOYSA-N 4-t-Butylbenzoic acid Chemical compound CC(C)(C)C1=CC=C(C(O)=O)C=C1 KDVYCTOWXSLNNI-UHFFFAOYSA-N 0.000 title claims abstract description 77
- 239000012760 heat stabilizer Substances 0.000 title claims abstract description 37
- DSAJWYNOEDNPEQ-UHFFFAOYSA-N barium atom Chemical compound [Ba] DSAJWYNOEDNPEQ-UHFFFAOYSA-N 0.000 title claims abstract description 34
- 229910052788 barium Inorganic materials 0.000 title claims abstract description 32
- 238000000034 method Methods 0.000 title claims abstract description 31
- 239000000047 product Substances 0.000 claims abstract description 58
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims abstract description 34
- 239000003381 stabilizer Substances 0.000 claims abstract description 31
- TZCXTZWJZNENPQ-UHFFFAOYSA-L barium sulfate Chemical compound [Ba+2].[O-]S([O-])(=O)=O TZCXTZWJZNENPQ-UHFFFAOYSA-L 0.000 claims abstract description 28
- 238000005303 weighing Methods 0.000 claims abstract description 21
- 239000002244 precipitate Substances 0.000 claims abstract description 17
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims abstract description 16
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 13
- 238000001914 filtration Methods 0.000 claims abstract description 12
- 238000005406 washing Methods 0.000 claims abstract description 11
- 238000001035 drying Methods 0.000 claims abstract description 9
- 238000001556 precipitation Methods 0.000 claims abstract description 7
- 238000002156 mixing Methods 0.000 claims abstract description 4
- 239000007789 gas Substances 0.000 claims description 25
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 claims description 21
- 239000008041 oiling agent Substances 0.000 claims description 18
- 239000003960 organic solvent Substances 0.000 claims description 18
- 239000003085 diluting agent Substances 0.000 claims description 10
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims description 9
- 238000012360 testing method Methods 0.000 claims description 9
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 6
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 claims description 6
- 238000004587 chromatography analysis Methods 0.000 claims description 5
- 239000012528 membrane Substances 0.000 claims description 5
- 239000012445 acidic reagent Substances 0.000 claims description 4
- 239000000126 substance Substances 0.000 claims description 4
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims description 3
- 239000012159 carrier gas Substances 0.000 claims description 3
- 239000001257 hydrogen Substances 0.000 claims description 3
- 229910052739 hydrogen Inorganic materials 0.000 claims description 3
- 229910052757 nitrogen Inorganic materials 0.000 claims description 3
- 239000003208 petroleum Substances 0.000 claims description 3
- 238000009834 vaporization Methods 0.000 claims description 3
- 230000008016 vaporization Effects 0.000 claims description 3
- 150000007524 organic acids Chemical class 0.000 abstract description 5
- 239000004800 polyvinyl chloride Substances 0.000 description 20
- 229920000915 polyvinyl chloride Polymers 0.000 description 19
- 229910052751 metal Inorganic materials 0.000 description 7
- 239000002184 metal Substances 0.000 description 7
- 238000012545 processing Methods 0.000 description 7
- 238000005259 measurement Methods 0.000 description 6
- 230000008569 process Effects 0.000 description 6
- 239000000344 soap Substances 0.000 description 6
- 239000002904 solvent Substances 0.000 description 6
- 238000006243 chemical reaction Methods 0.000 description 4
- 238000004364 calculation method Methods 0.000 description 3
- 239000007788 liquid Substances 0.000 description 3
- 208000033962 Fontaine progeroid syndrome Diseases 0.000 description 2
- 238000004458 analytical method Methods 0.000 description 2
- 229910052793 cadmium Inorganic materials 0.000 description 2
- BDOSMKKIYDKNTQ-UHFFFAOYSA-N cadmium atom Chemical compound [Cd] BDOSMKKIYDKNTQ-UHFFFAOYSA-N 0.000 description 2
- 238000001514 detection method Methods 0.000 description 2
- 238000002290 gas chromatography-mass spectrometry Methods 0.000 description 2
- 238000004128 high performance liquid chromatography Methods 0.000 description 2
- 238000002329 infrared spectrum Methods 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 238000002360 preparation method Methods 0.000 description 2
- 239000000376 reactant Substances 0.000 description 2
- 150000003839 salts Chemical class 0.000 description 2
- SMNNDVUKAKPGDD-UHFFFAOYSA-N 2-butylbenzoic acid Chemical group CCCCC1=CC=CC=C1C(O)=O SMNNDVUKAKPGDD-UHFFFAOYSA-N 0.000 description 1
- ZDFKSZDMHJHQHS-UHFFFAOYSA-N 2-tert-butylbenzoic acid Chemical compound CC(C)(C)C1=CC=CC=C1C(O)=O ZDFKSZDMHJHQHS-UHFFFAOYSA-N 0.000 description 1
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 description 1
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 1
- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical compound [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 description 1
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 229910052791 calcium Inorganic materials 0.000 description 1
- 239000011575 calcium Substances 0.000 description 1
- 230000015556 catabolic process Effects 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 238000002485 combustion reaction Methods 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 230000008094 contradictory effect Effects 0.000 description 1
- 238000005260 corrosion Methods 0.000 description 1
- 230000007797 corrosion Effects 0.000 description 1
- 238000000354 decomposition reaction Methods 0.000 description 1
- 238000006731 degradation reaction Methods 0.000 description 1
- 230000002708 enhancing effect Effects 0.000 description 1
- 238000004817 gas chromatography Methods 0.000 description 1
- IXCSERBJSXMMFS-UHFFFAOYSA-N hydrogen chloride Substances Cl.Cl IXCSERBJSXMMFS-UHFFFAOYSA-N 0.000 description 1
- 229910000041 hydrogen chloride Inorganic materials 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 230000002401 inhibitory effect Effects 0.000 description 1
- 239000000314 lubricant Substances 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 239000003550 marker Substances 0.000 description 1
- 238000000691 measurement method Methods 0.000 description 1
- 229910001510 metal chloride Inorganic materials 0.000 description 1
- 238000004806 packaging method and process Methods 0.000 description 1
- 229920003023 plastic Polymers 0.000 description 1
- 239000004033 plastic Substances 0.000 description 1
- 238000010998 test method Methods 0.000 description 1
- 238000003856 thermoforming Methods 0.000 description 1
- 229910052725 zinc Inorganic materials 0.000 description 1
- 239000011701 zinc Substances 0.000 description 1
Classifications
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- G—PHYSICS
- G01—MEASURING; TESTING
- G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
- G01N30/00—Investigating or analysing materials by separation into components using adsorption, absorption or similar phenomena or using ion-exchange, e.g. chromatography or field flow fractionation
- G01N30/02—Column chromatography
-
- G—PHYSICS
- G01—MEASURING; TESTING
- G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
- G01N30/00—Investigating or analysing materials by separation into components using adsorption, absorption or similar phenomena or using ion-exchange, e.g. chromatography or field flow fractionation
- G01N30/02—Column chromatography
- G01N30/04—Preparation or injection of sample to be analysed
- G01N30/06—Preparation
-
- G—PHYSICS
- G01—MEASURING; TESTING
- G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
- G01N30/00—Investigating or analysing materials by separation into components using adsorption, absorption or similar phenomena or using ion-exchange, e.g. chromatography or field flow fractionation
- G01N30/02—Column chromatography
- G01N30/04—Preparation or injection of sample to be analysed
- G01N30/06—Preparation
- G01N30/14—Preparation by elimination of some components
-
- G—PHYSICS
- G01—MEASURING; TESTING
- G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
- G01N30/00—Investigating or analysing materials by separation into components using adsorption, absorption or similar phenomena or using ion-exchange, e.g. chromatography or field flow fractionation
- G01N30/02—Column chromatography
- G01N30/62—Detectors specially adapted therefor
- G01N30/64—Electrical detectors
- G01N30/68—Flame ionisation detectors
-
- G—PHYSICS
- G01—MEASURING; TESTING
- G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
- G01N30/00—Investigating or analysing materials by separation into components using adsorption, absorption or similar phenomena or using ion-exchange, e.g. chromatography or field flow fractionation
- G01N30/02—Column chromatography
- G01N30/86—Signal analysis
- G01N30/8675—Evaluation, i.e. decoding of the signal into analytical information
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- G—PHYSICS
- G01—MEASURING; TESTING
- G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
- G01N5/00—Analysing materials by weighing, e.g. weighing small particles separated from a gas or liquid
- G01N5/04—Analysing materials by weighing, e.g. weighing small particles separated from a gas or liquid by removing a component, e.g. by evaporation, and weighing the remainder
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- G—PHYSICS
- G01—MEASURING; TESTING
- G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
- G01N30/00—Investigating or analysing materials by separation into components using adsorption, absorption or similar phenomena or using ion-exchange, e.g. chromatography or field flow fractionation
- G01N30/02—Column chromatography
- G01N30/04—Preparation or injection of sample to be analysed
- G01N2030/042—Standards
- G01N2030/047—Standards external
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- G—PHYSICS
- G01—MEASURING; TESTING
- G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
- G01N30/00—Investigating or analysing materials by separation into components using adsorption, absorption or similar phenomena or using ion-exchange, e.g. chromatography or field flow fractionation
- G01N30/02—Column chromatography
- G01N30/04—Preparation or injection of sample to be analysed
- G01N30/06—Preparation
- G01N30/14—Preparation by elimination of some components
- G01N2030/146—Preparation by elimination of some components using membranes
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- Life Sciences & Earth Sciences (AREA)
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- Biochemistry (AREA)
- General Health & Medical Sciences (AREA)
- General Physics & Mathematics (AREA)
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Abstract
The invention discloses a method for measuring the contents of p-tert-butylbenzoic acid and barium in a PVC heat stabilizer, which comprises the following steps: s1, mixing a stabilizer sample with dilute sulfuric acid, standing, and adding pure water to obtain a first product which is obviously layered; s2, filtering and drying the water layer and the precipitation part of the first product to obtain a second product, and weighing; s3, washing the second product with ethanol for multiple times to obtain a third product, weighing, wherein the mass of the third product is the mass of barium sulfate, calculating the content of barium element in the stabilizer sample, and the difference value between the mass of the second product and the mass of the third product is the content of p-tert-butylbenzoic acid in the precipitate; s4, measuring the content of free p-tert-butylbenzoic acid by a gas chromatograph-mass spectrometer, wherein the content of the p-tert-butylbenzoic acid is the sum of the content of the p-tert-butylbenzoic acid and the content of the free p-tert-butylbenzoic acid in the precipitate. The invention can effectively detect the content of part of organic acid in the heat stabilizer.
Description
Technical Field
The invention relates to the technical field of analytical chemistry, in particular to a method for measuring contents of p-tert-butylbenzoic acid and barium in a PVC heat stabilizer.
Background
Polyvinyl chloride (PVC) is one of the main general plastics, has the advantages of high strength, corrosion resistance, difficult combustion, good insulativity and transparency, and the like, and the product is widely applied to industries such as building, chemical industry, electrical appliances, packaging and the like. However, PVC has a disadvantage of poor thermal stability, and therefore an appropriate amount of a heat stabilizer must be added during processing to inhibit thermal degradation thereof. The existing heat stabilizer mainly comprises lead salts, organic tin and metal (barium, cadmium, calcium, zinc and the like) soaps, wherein the lead salts, the barium and the cadmium soaps have better performance, the soaps formed by combining the metal and the organic acid can be directly contacted with PVC in the use process, and the stabilizer reacts with hydrogen chloride released by partial explanation of the PVC after the PVC thermoforming processing, so that the stabilizer is easily converted into corresponding metal chloride, thereby achieving the aim of stopping or inhibiting the decomposition of the PVC, and further enhancing the thermal stability.
The metal soap has the advantages of simple production process, proper price, no peculiar smell, lubricant and other functions, is always a main heat stabilizer for processing soft PVC, and is also partially applied to processing hard PVC. The practical metal soap heat stabilizer is a metal soap compound with different characteristics, the performances are closely related to the contents of all components, wherein the contents of organic acid and metal in the stabilizer are critical to the performances of the heat stabilizer, the yield of the PVC heat stabilizer in China is continuously increased at present, the product quality is not standardized by unified national standards and industry standards, few methods for detecting the contents of components in the heat stabilizer are reported, the formula of each PVC profile and the formula of the heat stabilizer are not completely the same, and the error of a measurement result is larger. The existing HPLC, IC, GCMS and other single conventional testing means have the problems of complex sample preparation, large quantitative result difference and the like. Therefore, a simpler, faster and more convenient method is needed to effectively detect the content of part of the organic acid in the heat stabilizer.
Disclosure of Invention
The invention mainly aims to provide a method for measuring the contents of p-tert-butylbenzoic acid and barium in a PVC heat stabilizer, which aims to rapidly, simply and effectively detect the contents of p-tert-butylbenzoic acid and barium in the heat stabilizer.
In order to achieve the above purpose, the invention provides a method for measuring the contents of p-tert-butylbenzoic acid and barium in a PVC heat stabilizer, which comprises the following steps:
s1, mixing a stabilizer sample with dilute sulfuric acid, standing, and adding pure water to obtain a first product which is obviously layered;
s2, sucking out the upper-layer oiling agent of the first product by using a dropper, preserving for later testing, filtering and drying a water layer and a precipitation part of the first product to obtain a second product, weighing and recording the quality of the second product;
s3, washing the second product with ethanol for multiple times, washing off p-tert-butylbenzoic acid precipitated together with barium sulfate to obtain a third product, weighing and recording the mass of the third product, wherein the mass of the third product is the mass of barium sulfate, the content of barium element in a stabilizer sample is calculated according to a formula by the mass of barium sulfate, and the difference between the mass of the second product recorded in the step S2 and the mass of the third product recorded in the step S3 is the content of p-tert-butylbenzoic acid in a precipitate;
s4, filtering the upper-layer oiling agent sucked out by the dropper by using an organic filter membrane to obtain an oiling agent sample, and determining the content of free p-tert-butylbenzoic acid in the oiling agent sample by using a gas chromatograph-mass spectrometer, wherein the content of the p-tert-butylbenzoic acid in the PVC heat stabilizer is the sum of the content of the p-tert-butylbenzoic acid in the precipitate and the content of the free p-tert-butylbenzoic acid.
Optionally, the determination of the content of free p-tert-butylbenzoic acid by the gas chromatograph comprises the following steps:
s41, dissolving a standard substance p-tert-butylbenzoic acid reagent in an organic solvent to obtain a diluent;
s42, dispersing the diluent in organic solvents with different masses to obtain standard products 1, 2, 3, 4 and 5 with different concentrations;
s43, weighing and recording the oil solution sample, dispersing the oil solution sample in a certain amount of organic solvent, and recording the oil solution sample as a sample 6;
s44, measuring chromatographic peak areas of the standard and the sample by adopting a gas chromatograph-mass spectrometer, drawing a standard curve by taking the concentrations of the standard products 1-5 as the abscissa and the chromatographic peak areas measured by the gas chromatograph-mass spectrometer as the ordinate, and obtaining the content of free p-tert-butylbenzoic acid through the standard curve and the peak areas of the sample 6.
Optionally, in step S41, the organic solvent is at least one of dichloromethane, petroleum ether, and methanol.
Optionally, in step S43, the oil sample is taken to have a mass of 0.01 to 0.1g, and dispersed in 10 to 20g of an organic solvent.
Optionally, in step S1, the mass fraction of the dilute sulfuric acid is 10% -30%, and the mass ratio of the stabilizer sample to the sulfuric acid is 2-10: 1 to 5.
Optionally, in step S1, the mass ratio of the stabilizer sample to sulfuric acid is 2-10: 1 to 5.
Optionally, in step S1, the standing time is 20 to 60 minutes.
Optionally, in step S2, filtering is performed using slow filter paper, and the drying temperature is 40-80 ℃.
Optionally, in step S3, the number of times of washing is 1 to 5.
Optionally, in step S4, the test conditions of the marker and the sample measured by the gas chromatograph are:
chromatographic column: size 30m x 0.53mm x 1.0 μm using a (5% -phenyl) -methylpolysiloxane capillary chromatography column;
a detector: flame ionization detector;
detecting the temperature of the chamber: 300 ℃;
vaporization chamber temperature: 300 ℃;
heating program: after the initial column temperature is kept at 230 ℃ for 2min, the temperature is raised to 300 ℃ at a speed of 10 ℃/min;
carrier gas: the purity of the nitrogen is more than or equal to 99.999 percent, and the flow rate is 1.0mL/min;
gas: the purity of the hydrogen is more than or equal to 99.999 percent, and the flow rate is 30mL/min;
combustion-supporting gas: air, flow rate 400mL/min.
The invention has the following beneficial effects:
(1) According to the technical scheme provided by the invention, the use amount of the organic solvent is small, the resource is saved, the operation method is convenient and quick, and the batch treatment is easy to realize;
(2) The pretreatment process of the sample is simple, and reactants are simply mixed;
(3) The filtering process has short time and high efficiency, and the target in the oiling agent can be quickly transferred after the solvent is added, so that excessive manpower and material resources are not needed;
(4) The reaction process has low temperature and low risk.
Drawings
In order to more clearly illustrate the embodiments of the present invention or the technical solutions in the prior art, the drawings that are required in the embodiments or the description of the prior art will be briefly described, and it is obvious that the drawings in the following description are only some embodiments of the present invention, and other related drawings can be obtained according to the drawings without inventive effort for a person skilled in the art.
FIG. 1 is an infrared spectrum of the precipitate generated in example 1 of the present invention;
FIG. 2 is a gas chromatogram of p-tert-butylbenzoic acid in example 1 of the present invention.
The achievement of the objects, functional features and advantages of the present invention will be further described with reference to the accompanying drawings, in conjunction with the embodiments.
Detailed Description
In order to make the objects, technical solutions and advantages of the embodiments of the present invention more clear, the technical solutions of the embodiments of the present invention will be clearly and completely described below. The specific conditions are not noted in the examples and are carried out according to conventional conditions or conditions recommended by the manufacturer. The reagents or apparatus used were conventional products commercially available without the manufacturer's attention. In addition, the meaning of "and/or" as it appears throughout includes three parallel schemes, for example "A and/or B", including the A scheme, or the B scheme, or the scheme where A and B are satisfied simultaneously. In addition, the technical solutions of the embodiments may be combined with each other, but it is necessary to base that the technical solutions can be realized by those skilled in the art, and when the technical solutions are contradictory or cannot be realized, the combination of the technical solutions should be regarded as not exist and not within the protection scope of the present invention. All other embodiments, which can be made by those skilled in the art based on the embodiments of the invention without making any inventive effort, are intended to be within the scope of the invention.
In view of the problems that the existing heat stabilizer has fewer detection methods for the content of components, the conventional HPLC, IC, GCMS single test means have complex sample preparation, large quantitative result difference and the like, the invention provides a method for measuring the content of partial organic acid and metal in the PVC heat stabilizer so as to better adjust the formula, improve the performance of the stabilizer and provide a new analysis idea for the detection of other components in the heat stabilizer.
The invention provides a method for measuring the contents of p-tert-butylbenzoic acid and barium in a PVC heat stabilizer, which comprises the following steps:
s1, mixing a stabilizer sample with dilute sulfuric acid, standing, and adding pure water to obtain a first product which is obviously layered;
in the step, the mass fraction of the dilute sulfuric acid is 10% -30%, and the mass ratio of the stabilizer sample to the sulfuric acid is 2-10: 1 to 5; the standing time is 20-60 min, and the sulfuric acid with proper proportion is added to make the reaction complete, and the product can be obviously layered after standing.
S2, sucking out the upper-layer oiling agent of the first product by using a dropper, preserving for later testing, filtering and drying a water layer and a precipitation part of the first product to obtain a second product, weighing and recording the quality of the second product;
in this step, the aqueous layer and the precipitated fraction are filtered using a slow filter paper, and after the filtration is completed, the product is dried in an oven at a temperature of 40 to 80 ℃.
S3, washing the second product with ethanol for multiple times, washing off p-tert-butylbenzoic acid precipitated together with barium sulfate to obtain a third product, weighing and recording the mass of the third product, wherein the mass of the third product is the mass of barium sulfate, the content of barium element in a stabilizer sample is calculated according to a formula by the mass of barium sulfate, and the difference between the mass of the second product recorded in the step S2 and the mass of the third product recorded in the step S3 is the content of p-tert-butylbenzoic acid in a precipitate;
in this step, the number of times of washing is 1 to 5.
S4, filtering the upper-layer oiling agent sucked out by the dropper by using an organic filter membrane to obtain an oiling agent sample, and determining the content of free p-tert-butylbenzoic acid in the oiling agent sample by using a gas chromatograph-mass spectrometer, wherein the content of the p-tert-butylbenzoic acid in the PVC heat stabilizer is the sum of the content of the p-tert-butylbenzoic acid in the precipitate and the content of the free p-tert-butylbenzoic acid.
In this step, the test conditions for the markers and samples determined by the gas chromatograph are:
chromatographic column: size 30m x 0.53mm x 1.0 μm using a (5% -phenyl) -methylpolysiloxane capillary chromatography column; a detector: flame ionization detector; detecting the temperature of the chamber: 300 ℃; vaporization chamber temperature: 300 ℃; heating program: after the initial column temperature is kept at 230 ℃ for 2min, the temperature is raised to 300 ℃ at a speed of 10 ℃/min; carrier gas: the purity of the nitrogen is more than or equal to 99.999 percent, and the flow rate is 1.0mL/min; gas: the purity of the hydrogen is more than or equal to 99.999 percent, and the flow rate is 30mL/min; combustion-supporting gas: air, flow rate 400mL/min.
According to the technical scheme provided by the invention, the sample pretreatment process is simple, the reactants are simply mixed to obtain different layered products, the p-tert-butylbenzoic acid and the barium content can be obtained by weighing and further processing, the organic solvent usage amount in the determination process is small, the resources are saved, the operation method is convenient and rapid, and the batch treatment is easy to realize; the filtering process has short time and high efficiency, and the target in the oiling agent can be quickly transferred after the solvent is added, so that excessive manpower and material resources are not needed; and the reaction process has low temperature and low risk.
Specifically, the method for determining the content of the free p-tert-butylbenzoic acid by using the gas chromatograph/mass spectrometer comprises the following steps:
s41, dissolving a standard substance p-tert-butylbenzoic acid reagent in an organic solvent to obtain a diluent;
in this step, the organic solvent is at least one of dichloromethane, petroleum ether, and methanol.
S42, dispersing the diluent in organic solvents with different masses to obtain standard products 1, 2, 3, 4 and 5 with different concentrations;
s43, weighing and recording the oil solution sample, dispersing the oil solution sample in a certain amount of organic solvent, and recording the oil solution sample as a sample 6;
in this step, in order to facilitate calculation of the concentration of free p-tert-butylbenzoic acid, a certain amount of free p-tert-butylbenzoic acid is dissolved in a certain mass of organic solvent, preferably, the mass of the oil sample is taken to be 0.01 to 0.1g, and dispersed in 10 to 20g of organic solvent.
S44, measuring chromatographic peak areas of the standard and the sample by adopting a gas chromatograph-mass spectrometer, drawing a standard curve by taking the concentrations of the standard products 1-5 as the abscissa and the chromatographic peak areas measured by the gas chromatograph-mass spectrometer as the ordinate, and obtaining the content of free p-tert-butylbenzoic acid through the standard curve and the peak areas of the sample 6.
In this embodiment, the implementation steps of a specific measurement method are provided:
(1) Sample processing
Placing 5.17g of stabilizer sample and 3.57g of 20% dilute sulfuric acid in a beaker, standing for 30min, adding a small amount of pure water into the beaker to obviously delaminate the product, and sucking out and preserving the upper layer oiling agent by using a dropper; after the water layer and the precipitation part are filtered by slow filter paper, the product is put into a 60 ℃ oven to be dried for 2 hours, and the water layer and the precipitation part are weighed after the drying is finished and the first quality is recorded; washing the dried product with ethanol for 3 times, weighing the obtained precipitate again and recording the second quality; the upper layer oil is filtered by a 0.22 mu m organic filter membrane, and the content of free p-tert-butylbenzoic acid is measured by a gas chromatograph-mass spectrometer.
(2) Quantitative determination of external standard
The standard p-tert-butylbenzoic acid reagent was dispersed in methylene chloride solvent and recorded as a diluent. Preparing 5 standard use solutions with different concentrations from the diluent, wherein the standard use solutions are numbered 1, 2, 3, 4 and 5, the mass fractions are respectively 0.1%, 0.125%, 0.167%, 0.25% and 0.5%, the concentration is on the abscissa, the chromatographic peak area is on the ordinate, and a standard working curve y=ax+b is drawn.
Dispersing the separated oil sample in dichloromethane solvent, with number of 6 and content of C 0 . And substituting the peak area obtained after chromatographic analysis of the sample to be detected into a working curve, and calculating to obtain the concentration C of the p-tert-butylbenzoic acid in the liquid to be detected.
The content (%) of p-tert-butylbenzoic acid in the upper layer oil is calculated according to the following formula (1):
wherein:
c: the content of p-tert-butylbenzoic acid in the liquid to be detected,%;
C 0 : oil sample content,%;
W upper part : the content of p-tert-butyl benzoic acid in the upper layer oiling agent is percent.
The test method takes the average value of three parallel measurement as the final measurement result, and the relative standard deviation of the parallel measurement result is less than 10%.
(3) Calculating the contents of barium metal and p-tert-butyl benzoic acid in the sample
By utilizing the characteristic that the p-tert-butylbenzoic acid can be dissolved in ethanol, the sample is washed by ethanol for multiple times in the sample treatment example, the p-tert-butylbenzoic acid precipitated together with the barium sulfate is washed off, and the quality recorded in the second weighing is the quality of the barium sulfate.
The content (%) of the barium element in the stabilizer sample can be calculated by the mass of barium sulfate according to the formula (2):
wherein:
m 2 : the mass recorded during the second weighing, g;
m: mass of stabilizer sample, g;
W Ba : the content of barium metal in the sample,%.
The total content of p-tert-butylbenzoic acid in the stabilizer sample was the sum of the content in the precipitate and the content in the oil phase.
The difference between the first and second weighing is the content of p-tert-butylbenzoic acid in the precipitate.
The total content (%) of p-tert-butylbenzoic acid in the stabilizer sample was calculated according to formula (3):
wherein:
m 1 : mass, g, recorded during the first weighing;
m 2 : the mass recorded during the second weighing, g;
W upper part : the content of p-tert-butyl benzoic acid in the upper layer oiling agent is percent.
W Total (S) : the total content of p-tert-butylbenzoic acid in the stabilizer sample,%.
The following technical solutions of the present invention will be described in further detail with reference to specific examples and drawings, and it should be understood that the following examples are only for explaining the present invention and are not intended to limit the present invention.
Example 1 determination of the content of para-t-butylbenzoic acid and barium in PVC Heat stabilizer
(1) Sample processing
A sample of the stabilizer, 4.99g, and 3.4g of 20% dilute sulfuric acid were placed in a beaker, and after standing for 30min, a small amount of pure water was added thereto to cause the product to separate significantly. And (3) sucking the upper-layer oiling agent out by a dropper, measuring by a gas supply mass spectrometer, detecting the generated precipitate by using an infrared spectrum to obtain the figure 1, putting the product into a 60 ℃ oven for drying for 2 hours after the water layer and the precipitate are filtered by using slow filter paper, weighing after the drying is finished, and recording the first quality. The dried product was washed 2 times with ethanol, the resulting precipitate was weighed again and the second mass was recorded. The upper layer oil was filtered through a 0.22 μm organic filter membrane, and the free p-tert-butylbenzoic acid was quantitatively tested, and the results of each test are shown in Table 1 below.
Table 1 table of quality recordings of two precipitations produced by reaction of a stabilizer sample with sulfuric acid
| Sample of | Weight/g | 20% sulfuric acid/g | First weight/g | Second weighing/g | Difference/g |
| Stabilizing agent | 4.99 | 3.4 | 0.5 | 0.4 | 0.1 |
The mass recorded during the second weighing is the mass of barium sulfate, and the content of barium in the sample is calculated according to the formula (2) and compared with the actual content, and the result is shown in the following table 2.
Table 2 calculated barium content in stabilizer samples
(2) Quantitative determination of external standard
The standard p-tert-butylbenzoic acid was taken and dissolved in methylene chloride solvent and recorded as a diluent. Preparing 5 standard use solutions with different concentrations from the diluent, wherein the standard use solutions are numbered 1, 2, 3, 4 and 5, the mass fractions are respectively 0.105%, 0.129%, 0.163%, 0.246% and 0.491%, the concentration is taken as an abscissa, the chromatographic peak area is taken as an ordinate, and a standard working curve y=ax+b is drawn. Dispersing the separated oil sample in dichloromethane solvent, with number of 6 and content of C 0 And (3) carrying out gas chromatography analysis on the oil solution sample by adopting a gas chromatograph-mass spectrometer to obtain the figure 2. And substituting the peak area obtained after chromatographic analysis of the sample to be detected into a working curve, and calculating to obtain the concentration C of the p-tert-butylbenzoic acid in the liquid to be detected. The calculated p-tert-butylbenzoic acid content in the stabilizer sample top oil is shown below.
TABLE 3 calculation of the para-tertiary butyl benzoic acid content in the stabilizer sample upper layer finish
(3) Calculation of the content of p-tert-butylbenzoic acid in the sample
The total content of p-tert-butylbenzoic acid in the stabilizer sample was calculated according to formula (3) as the sum of the content in the precipitate and the content in the oil phase, and the content of each component was recorded as shown in table 4 below.
TABLE 4 Table 4 record of the content of p-tert-butylbenzoic acid in the precipitate and in the oil phase
From the measurement results, it was found that the difference between the measured values and the actual values of the contents of p-t-butylbenzoic acid and barium in the PVC heat stabilizer was small, and the measurement was carried out by this method.
In summary, the method for measuring the contents of the p-tert-butylbenzoic acid and the barium in the PVC heat stabilizer provided by the invention can be used for effectively detecting the contents of the barium element and the tert-butylbenzoic acid in the stabilizer sample, and is convenient and quick, and batch treatment is easy to realize.
The foregoing is merely a preferred embodiment of the present invention and is not intended to limit the scope of the present invention, but various modifications and variations will be apparent to those skilled in the art. Any modification, equivalent replacement, improvement, etc. made within the spirit and principle of the present invention should be included in the scope of the present invention.
Claims (10)
1. The method for measuring the contents of p-tert-butylbenzoic acid and barium in the PVC heat stabilizer is characterized by comprising the following steps of:
s1, mixing a stabilizer sample with dilute sulfuric acid, standing, and adding pure water to obtain a first product which is obviously layered;
s2, sucking out the upper-layer oiling agent of the first product by using a dropper, preserving for later testing, filtering and drying a water layer and a precipitation part of the first product to obtain a second product, weighing and recording the quality of the second product;
s3, washing the second product with ethanol for multiple times, washing off p-tert-butylbenzoic acid precipitated together with barium sulfate to obtain a third product, weighing and recording the mass of the third product, wherein the mass of the third product is the mass of barium sulfate, the content of barium element in a stabilizer sample is calculated according to a formula by the mass of barium sulfate, and the difference between the mass of the second product recorded in the step S2 and the mass of the third product recorded in the step S3 is the content of p-tert-butylbenzoic acid in a precipitate;
s4, filtering the upper-layer oiling agent sucked out by the dropper by using an organic filter membrane to obtain an oiling agent sample, and determining the content of free p-tert-butylbenzoic acid in the oiling agent sample by using a gas chromatograph-mass spectrometer, wherein the content of the p-tert-butylbenzoic acid in the PVC heat stabilizer is the sum of the content of the p-tert-butylbenzoic acid in the precipitate and the content of the free p-tert-butylbenzoic acid.
2. The method for determining the content of p-tert-butylbenzoic acid and barium in a PVC heat stabilizer according to claim 1, wherein the determination of the content of free p-tert-butylbenzoic acid by a gas chromatograph/mass spectrometer comprises the following steps:
s41, dissolving a standard substance p-tert-butylbenzoic acid reagent in an organic solvent to obtain a diluent;
s42, dispersing the diluent in organic solvents with different masses to obtain standard products 1, 2, 3, 4 and 5 with different concentrations;
s43, weighing and recording the oil solution sample, dispersing the oil solution sample in a certain amount of organic solvent, and recording the oil solution sample as a sample 6;
s44, measuring chromatographic peak areas of the standard and the sample by adopting a gas chromatograph-mass spectrometer, drawing a standard curve by taking the concentration of the standard 1-5 as an abscissa and the chromatographic peak area measured by the gas chromatograph-mass spectrometer as an ordinate, and obtaining the content of free p-tert-butylbenzoic acid through the standard curve and the peak area of the sample 6.
3. The method for measuring the contents of p-tert-butylbenzoic acid and barium in the PVC heat stabilizer according to claim 2, wherein in the step S41, the organic solvent is at least one of dichloromethane, petroleum ether and methanol.
4. The method for measuring the contents of p-tert-butylbenzoic acid and barium in a PVC heat stabilizer according to claim 1, wherein in step S43, the oil sample is taken to have a mass of 0.01-0.1 g, and dispersed in 10-20 g of an organic solvent.
5. The method for determining the content of p-tert-butylbenzoic acid and barium in a PVC heat stabilizer according to claim 1, wherein in the step S1, the mass fraction of the dilute sulfuric acid is 10% -30%, and the mass ratio of the stabilizer sample to sulfuric acid is 2-10: 1-5.
6. The method for determining the content of p-tert-butylbenzoic acid and barium in a PVC heat stabilizer according to claim 1, wherein in the step S1, the mass ratio of the stabilizer sample to sulfuric acid is 2-10: 1-5.
7. The method for measuring the contents of p-tert-butylbenzoic acid and barium in a PVC heat stabilizer according to claim 1, wherein in the step S1, the standing time is 20 to 60 minutes.
8. The method for determining the content of p-tert-butylbenzoic acid and barium in a PVC heat stabilizer according to claim 1, wherein in the step S2, filtering is performed by using a slow filter paper, and the drying temperature is 40-80 ℃.
9. The method for measuring the contents of p-tert-butylbenzoic acid and barium in a PVC heat stabilizer according to claim 1, wherein in the step S3, the number of times of washing is 1 to 5.
10. The method for determining the content of p-tert-butylbenzoic acid and barium in a PVC heat stabilizer according to claim 1, wherein in step S4, the test conditions for determining the standard and the sample by a gas chromatograph are:
chromatographic column: size 30m x 0.53mm x 1.0 μm using a (5% -phenyl) -methylpolysiloxane capillary chromatography column;
a detector: flame ionization detector;
detecting the temperature of the chamber: 300 ℃;
vaporization chamber temperature: 300 ℃;
heating program: after the initial column temperature is kept at 230 ℃ for 2min, the temperature is raised to 300 ℃ at a speed of 10 ℃/min;
carrier gas: the purity of the nitrogen is more than or equal to 99.999 percent, and the flow rate is 1.0mL/min;
gas: the purity of the hydrogen is more than or equal to 99.999 percent, and the flow rate is 30mL/min;
combustion-supporting gas: air flow rate was 400mL/min.
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