CN113376144A - Analysis method for low bromine content in fluororubber - Google Patents
Analysis method for low bromine content in fluororubber Download PDFInfo
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- GDTBXPJZTBHREO-UHFFFAOYSA-N bromine Substances BrBr GDTBXPJZTBHREO-UHFFFAOYSA-N 0.000 title claims abstract description 61
- 229910052794 bromium Inorganic materials 0.000 title claims abstract description 61
- WKBOTKDWSSQWDR-UHFFFAOYSA-N Bromine atom Chemical compound [Br] WKBOTKDWSSQWDR-UHFFFAOYSA-N 0.000 title claims abstract description 58
- 229920001973 fluoroelastomer Polymers 0.000 title claims abstract description 35
- 238000004458 analytical method Methods 0.000 title claims abstract description 16
- 239000000523 sample Substances 0.000 claims abstract description 68
- 238000002485 combustion reaction Methods 0.000 claims abstract description 32
- 238000000034 method Methods 0.000 claims abstract description 31
- 238000002354 inductively-coupled plasma atomic emission spectroscopy Methods 0.000 claims abstract description 17
- 229920001971 elastomer Polymers 0.000 claims abstract description 15
- 239000012488 sample solution Substances 0.000 claims abstract description 14
- 239000012086 standard solution Substances 0.000 claims abstract description 8
- 239000012490 blank solution Substances 0.000 claims abstract description 6
- 238000011088 calibration curve Methods 0.000 claims abstract description 5
- 239000007788 liquid Substances 0.000 claims abstract description 5
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims description 15
- 229910052760 oxygen Inorganic materials 0.000 claims description 15
- 239000001301 oxygen Substances 0.000 claims description 15
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 claims description 12
- 239000007789 gas Substances 0.000 claims description 11
- 239000000243 solution Substances 0.000 claims description 11
- 238000005259 measurement Methods 0.000 claims description 10
- CPELXLSAUQHCOX-UHFFFAOYSA-M Bromide Chemical compound [Br-] CPELXLSAUQHCOX-UHFFFAOYSA-M 0.000 claims description 8
- 229940006460 bromide ion Drugs 0.000 claims description 7
- 230000003595 spectral effect Effects 0.000 claims description 7
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 7
- 229910052786 argon Inorganic materials 0.000 claims description 6
- 238000002347 injection Methods 0.000 claims description 6
- 239000007924 injection Substances 0.000 claims description 6
- 238000000197 pyrolysis Methods 0.000 claims description 5
- 238000010521 absorption reaction Methods 0.000 claims description 4
- 238000007664 blowing Methods 0.000 claims description 3
- 238000004364 calculation method Methods 0.000 claims description 3
- 238000001816 cooling Methods 0.000 claims description 3
- 239000000112 cooling gas Substances 0.000 claims description 3
- 230000001590 oxidative effect Effects 0.000 claims description 3
- -1 polytetrafluoroethylene Polymers 0.000 claims description 3
- 229920001343 polytetrafluoroethylene Polymers 0.000 claims description 3
- 239000004810 polytetrafluoroethylene Substances 0.000 claims description 3
- 230000006641 stabilisation Effects 0.000 claims description 3
- 238000011105 stabilization Methods 0.000 claims description 3
- 238000005406 washing Methods 0.000 claims description 3
- 238000005303 weighing Methods 0.000 claims description 3
- 239000012224 working solution Substances 0.000 claims description 3
- 238000007865 diluting Methods 0.000 claims description 2
- 239000000126 substance Substances 0.000 description 5
- 238000012360 testing method Methods 0.000 description 5
- 229920001774 Perfluoroether Polymers 0.000 description 4
- 238000001514 detection method Methods 0.000 description 4
- 238000011084 recovery Methods 0.000 description 4
- 238000011160 research Methods 0.000 description 4
- 238000012795 verification Methods 0.000 description 4
- 239000000178 monomer Substances 0.000 description 3
- 238000004073 vulcanization Methods 0.000 description 3
- YCKRFDGAMUMZLT-UHFFFAOYSA-N Fluorine atom Chemical compound [F] YCKRFDGAMUMZLT-UHFFFAOYSA-N 0.000 description 2
- 239000003153 chemical reaction reagent Substances 0.000 description 2
- 238000009841 combustion method Methods 0.000 description 2
- 229910052731 fluorine Inorganic materials 0.000 description 2
- 239000011737 fluorine Substances 0.000 description 2
- 238000009616 inductively coupled plasma Methods 0.000 description 2
- 238000004255 ion exchange chromatography Methods 0.000 description 2
- 150000002500 ions Chemical class 0.000 description 2
- 238000002360 preparation method Methods 0.000 description 2
- 239000012498 ultrapure water Substances 0.000 description 2
- KOMNUTZXSVSERR-UHFFFAOYSA-N 1,3,5-tris(prop-2-enyl)-1,3,5-triazinane-2,4,6-trione Chemical compound C=CCN1C(=O)N(CC=C)C(=O)N(CC=C)C1=O KOMNUTZXSVSERR-UHFFFAOYSA-N 0.000 description 1
- FSPQCTGGIANIJZ-UHFFFAOYSA-N 2-[[(3,4-dimethoxyphenyl)-oxomethyl]amino]-4,5,6,7-tetrahydro-1-benzothiophene-3-carboxamide Chemical compound C1=C(OC)C(OC)=CC=C1C(=O)NC1=C(C(N)=O)C(CCCC2)=C2S1 FSPQCTGGIANIJZ-UHFFFAOYSA-N 0.000 description 1
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 description 1
- 102100023593 Fibroblast growth factor receptor 1 Human genes 0.000 description 1
- 101000827746 Homo sapiens Fibroblast growth factor receptor 1 Proteins 0.000 description 1
- 206010021143 Hypoxia Diseases 0.000 description 1
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 description 1
- 102100020718 Receptor-type tyrosine-protein kinase FLT3 Human genes 0.000 description 1
- 101710151245 Receptor-type tyrosine-protein kinase FLT3 Proteins 0.000 description 1
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 1
- 108010053096 Vascular Endothelial Growth Factor Receptor-1 Proteins 0.000 description 1
- 108010053100 Vascular Endothelial Growth Factor Receptor-3 Proteins 0.000 description 1
- 102100033178 Vascular endothelial growth factor receptor 1 Human genes 0.000 description 1
- 102100033179 Vascular endothelial growth factor receptor 3 Human genes 0.000 description 1
- 230000006978 adaptation Effects 0.000 description 1
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- 238000009614 chemical analysis method Methods 0.000 description 1
- 229910052801 chlorine Inorganic materials 0.000 description 1
- 239000000460 chlorine Substances 0.000 description 1
- 238000009838 combustion analysis Methods 0.000 description 1
- 239000000567 combustion gas Substances 0.000 description 1
- 238000010276 construction Methods 0.000 description 1
- 238000005336 cracking Methods 0.000 description 1
- 230000007123 defense Effects 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 230000018109 developmental process Effects 0.000 description 1
- 239000003814 drug Substances 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 238000003912 environmental pollution Methods 0.000 description 1
- 229910052736 halogen Inorganic materials 0.000 description 1
- 150000002367 halogens Chemical class 0.000 description 1
- 238000012417 linear regression Methods 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 238000006864 oxidative decomposition reaction Methods 0.000 description 1
- 238000010060 peroxide vulcanization Methods 0.000 description 1
- 150000002978 peroxides Chemical class 0.000 description 1
- 229910052698 phosphorus Inorganic materials 0.000 description 1
- 239000011574 phosphorus Substances 0.000 description 1
- 238000002203 pretreatment Methods 0.000 description 1
- 238000003908 quality control method Methods 0.000 description 1
- 150000003254 radicals Chemical class 0.000 description 1
- 238000013040 rubber vulcanization Methods 0.000 description 1
- 238000005556 structure-activity relationship Methods 0.000 description 1
- 229910052717 sulfur Inorganic materials 0.000 description 1
- 239000011593 sulfur Substances 0.000 description 1
- 229910021642 ultra pure water Inorganic materials 0.000 description 1
- 239000004636 vulcanized rubber Substances 0.000 description 1
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- 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
- G01N21/62—Systems in which the material investigated is excited whereby it emits light or causes a change in wavelength of the incident light
- G01N21/71—Systems in which the material investigated is excited whereby it emits light or causes a change in wavelength of the incident light thermally excited
- G01N21/73—Systems in which the material investigated is excited whereby it emits light or causes a change in wavelength of the incident light thermally excited using plasma burners or torches
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Abstract
The invention relates to the technical field of rubber analysis, in particular to a method for analyzing low bromine content in fluororubber. The method comprises the following steps: (1) pretreating a rubber sample by adopting an automatic rapid combustion furnace to obtain a sample to-be-detected liquid; (2) preparing a blank solution and a bromine element standard solution series; (3) measuring the standard solution by utilizing ICP-OES to obtain a calibration curve of signal intensity and bromine concentration; (4) and (3) measuring the sample solution to be measured by utilizing ICP-OES, combining a calibration curve to obtain the bromine content in the sample solution to be measured, and further converting the bromine content in the rubber. The method is convenient and rapid, can continuously process samples, and has high accuracy.
Description
Technical Field
The invention relates to the technical field of rubber analysis, in particular to a method for analyzing low bromine content in fluororubber.
Background
Fluororubbers have excellent characteristics of heat resistance, oil resistance, aging resistance and the like, and are widely applied to various fields of transportation, construction, machinery, electronics, medicine, military and the like. With the continuous improvement of the requirements of the application field on the performance of the fluororubber, the development of a new vulcanization system and the research on new vulcanization monomers to obtain vulcanized rubber with better weak mechanical properties are the current research hotspots. In the middle and later period of the 70 s, triallyl isocyanurate is used as a free radical trapping group for peroxide vulcanization of fluororubber, so that vulcanization of the fluororubber is broken through. In order to improve the problem that fluororubbers are not readily vulcanized by peroxides, researchers have added monomers that provide a cure site, typically bromine-containing fluoroolefin monomers. The method for accurately measuring the bromine content in the fluororubber has important significance for evaluating the rubber structure-activity relationship and improving the rubber vulcanization quality.
At present, for the analysis of bromine in fluororubber, China has no corresponding national standard, and at present, analytical methods such as a chemical method, an ion selective electrode method, an ion chromatography method and the like are mostly adopted in scientific research work. The chemical method has complex steps, time and labor consumption and poor reproducibility; the ion selective electrode method has lower accuracy and lacks related standard substances; the ion chromatography for measuring bromide ions is easily interfered by other components. In addition, the fluorine content in the fluororubber is as high as more than 60%, and the fluororubber has certain flame retardance, and conventional sample treatment methods such as oxygen bottle combustion and oxygen bomb combustion are easy to cause incomplete combustion of samples due to the introduction of quantitative oxygen, so that large errors are caused. In view of the above technical problems, studies on low bromine content in fluororubbers are rarely reported at present.
Therefore, whether an analysis method for low bromine content in fluororubber can be provided to fill up the relevant technical blank in China becomes one of the problems to be solved urgently by technical personnel in the field.
Disclosure of Invention
The invention provides a method for analyzing the low bromine content in fluororubber, aiming at the blank in the prior art. In view of the disadvantages of the prior art, the object of the invention is: provides an analysis method for measuring the low bromine content in the fluororubber, which is convenient and rapid, can continuously process samples, and has high accuracy and good precision.
The invention provides a method for analyzing low bromine content in fluororubber, which is used for analyzing the bromine content and comprises the following steps:
(1) setting a combustion program, and adopting an automatic rapid combustion furnace to carry out pretreatment on a rubber sample to obtain a sample to-be-detected liquid;
(2) preparing a blank solution and a bromine element standard solution series;
(3) measuring the standard solution prepared in the step (2) by utilizing ICP-OES to obtain a standard curve of signal intensity and bromine concentration;
(4) measuring the sample solution to be measured obtained in the step (1) by utilizing ICP-OES, combining a calibration curve to obtain the bromine content in the sample solution to be measured, and further converting the bromine content in the rubber, wherein the calculation formula of the bromine is as follows:
in the formula: x-bromine content,%;
c, calculating the concentration of bromine element in the sample solution to be detected, mg/L, according to the standard curve;
v is the total volume of the solution to be measured (volume after constant volume of the sample), L;
m is sample mass, mg.
The specific step (1) is as follows:
accurately weighing 10-20 mg of sample, placing the sample in a sample boat, carrying the sample into a combustion furnace by argon, introducing oxygen, argon and a small amount of water into the combustion furnace, and carrying out pyrolysis combustion reaction at 800-1000 ℃. And oxidizing the sample by oxygen, absorbing the sample by a double-stage absorption tower, and fixing the volume to 100mL to obtain the solution to be detected of the sample.
The existing method is mainly an oxygen bottle combustion method, and due to the fact that the content of fluorine in the fluoroether rubber is more than 60%, the fluoroether rubber has certain flame retardance, and due to the adoption of the oxygen bottle combustion method, incomplete combustion is easily caused due to insufficient oxygen introduction, and a large error is caused. The automatic and rapid combustion furnace adopted by the invention can continuously introduce oxygen, ensure the sufficient combustion of the sample, and automatically carry out sample introduction, combustion and absorption on line, so that the operation is more convenient and rapid.
Further, in the step (1), the automatic combustion furnace conditions are as follows: gas flow rate: ar of the inner tube is 180mL/min, and O of the inner tube2210mL/min, outer tube O2Is 330 mL/min; the flow rate of the pyrolysis water is 0.30 mL/min; the air flow is 100 mL/min; the inlet temperature of the combustion tube was 900 ℃ and the outlet temperature was 1000 ℃. The combustion analysis program is that the position 1 is 150mm, and the time is kept for 100 s; position 2 is 100mm, hold 150 s; position 3 is 30mm, hold 150 s; position 4 is 20mm, hold 150 s; position 5, 180mm, hold for 200 s; the end time was 150 s; the cooling time is 100 s; the sample feeding speed of the sample feeding boat is 5.0 mm/s.
In order to ensure the complete combustion of the rubber sample, the sample is firstly kept in a low-temperature area for a period of time, is subjected to oxidative decomposition, and then enters a high-temperature area for sufficient combustion. The temperature range lift sequence designed by the invention can avoid the phenomenon of insufficient combustion of the sample at the inner side position due to instantaneous oxygen deficiency. The recovery rate of the sample obtained by the procedure is 99-101%, and the effect is good.
The specific step (2) is as follows:
empty burning the sample boat to obtain a blank solution; diluting the standard bromide ion solution by 1000mg/L step by step to obtain standard bromide ion working solutions with the concentrations of 0.1, 0.5, 1.0, 2.0 and 5.0mg/L respectively;
ICP-OES working conditions in the steps (3) and (4): the RF power is 1400W; the auxiliary gas flow is 1.0L/min; the flow rate of the atomizer is 0.8L/min; the flow rate of the cooling gas is 13.00L/min; the reverse blowing gas flow is 1.0L/min; the pre-washing time is 60 s; the stabilization time is 30 s; the sample injection system is a polytetrafluoroethylene sample injection system; in the ICP-OES measurement, analysis spectral lines are selected as follows: 154.065 nm.
When the emission power is changed within the range of 1000-1600W, the spectral line intensity of bromine is enhanced along with the improvement of the power, but 1400W is finally selected in the invention in consideration of the influence of the power increase on the signal-to-back ratio and the service life of the rectangular tube; the flow of the atomizer is in the flow range of 0.5-0.8L/min, the spectral line intensity of bromine is enhanced along with the increase of the flow, but when the flow exceeds 0.8L/min, the spectral line intensity begins to be reduced, and the flow of the atomizer is selected to be 0.8L/min in the invention; the sensitive line of bromine is mainly concentrated in a far ultraviolet region, a rubber sample generally contains elements such as chlorine, sulfur, phosphorus and the like, and the optimal analysis spectral line is selected to be 154.065nm by comparing the interference conditions of the spectral line of the elements with the wavelength range of 130-160 nm, the signal-to-back ratio and the halogen coexisting elements. Under the condition, the relative deviation of the obtained bromine content measurement result is 0.90 percent, which indicates that the method has good precision.
The invention provides a method for analyzing low bromine content in fluororubber, which utilizes an inductively coupled plasma emission spectrometer to determine the bromine content in the fluororubber; the method is mainly characterized in that a sample pretreatment method is optimized, the traditional oxygen bottle and oxygen bomb combustion treatment method is abandoned, an automatic rapid combustion furnace is adopted, a combustion program is optimized, the full combustion of the fluororubber is ensured, and the combustion gas is fully absorbed. The ICP-OES is adopted to determine the bromine element in the sample, so that the detection limit is reduced, the correlation coefficient of a linear regression equation of a calibration curve is not lower than 0.999, and the accuracy is improved.
Drawings
FIG. 1 is a bromine standard curve obtained in example 1;
Detailed Description
The present invention is further illustrated below with reference to examples, which will enable those skilled in the art to more fully understand the present invention, but which are not intended to limit the invention in any way; the embodiments of the present invention described below do not limit the scope of the present invention.
Other embodiments of the invention will be apparent to those skilled in the art from consideration of the specification and practice of the disclosure. This invention is intended to cover any variations, uses, or adaptations of the invention following, in general, the principles of the invention and including such departures from the present disclosure as come within known or customary practice within the art to which the invention pertains. The following examples are to be considered exemplary only, with the true scope and spirit of the invention being indicated by the following claims.
Example 1:
1. conditions of analysis
The main apparatus is as follows: iCAP 6300 model, inductively coupled plasma emission spectrometer (Thermo Fisher Scientific, USA); an SH-CIC3000 automatic rapid combustion furnace (the Qingdao is in the vast majority); electronic analytical balance (METTLER TOLEDO, switzerland), MAX 120g, d 0.01 mg; an ultrapure water preparation instrument: millipore, a high purity water system with a resistivity of 18M Ω. cm.
Reagent: standard substance of bromide ion solution in water, GBW (E)080521, concentration 1000mg/L, national defense science and technology industry applied chemical first-class metering station.
ICP-OES working conditions: the RF power is 1400W; the auxiliary gas flow is 1.0L/min; the flow rate of the atomizer is 0.8L/min; the flow rate of the cooling gas is 13.00L/min; the reverse blowing gas flow is 1.0L/min; the pre-washing time is 60 s; the stabilization time is 30 s; the sample injection system is a polytetrafluoroethylene sample injection system.
Selection of analytical lines: 154.065 nm.
(1) Sample pretreatment: 10mg of a fluororubber sample is accurately weighed and placed in a sample boat, the fluororubber sample is carried by argon gas and enters a combustion furnace, oxygen, argon gas and a small amount of water are introduced into the combustion furnace, and cracking combustion reaction is carried out at 800-1000 ℃. And oxidizing the sample by oxygen, absorbing the sample into a bottle by bubbling, and fixing the volume to 100mL after the absorption is finished to obtain the solution to be detected of the sample.
Wherein, the automatic combustion furnace conditions are as follows: gas flow rate: ar of the inner tube is 180mL/min, and O of the inner tube2210mL/min, outer tube O2Is 330 mL/min; the flow rate of the pyrolysis water is 0.30 mL/min; the air flow is 100 mL/min; the inlet temperature of the combustion tube was 900 ℃ and the outlet temperature was 1000 ℃.
The combustion analysis procedure was: position 1 is 150mm, and is kept for 100 s; position 2 is 100mm, hold 150 s; position 3 is 30mm, hold 150 s; position 4 is 20mm, hold 150 s; position 5, 180mm, hold for 200 s; the end time was 150 s; the cooling time was 100 s. The sample feeding speed of the sample feeding boat is 5.0 mm/s.
(2) Preparation of standard solution series:
empty burning the sample boat to obtain a blank solution;
the standard bromide ion solution of 1000mg/L is diluted step by step to obtain standard bromide ion working solutions of 0.1, 0.5, 1.0, 2.0 and 5.0mg/L concentration respectively, which are used for establishing a standard curve during ICP-OES measurement, as shown in FIG. 1.
(3) Measurement:
and (3) starting the machine for 2 hours, measuring the intensity value of bromine in the sample to-be-measured liquid obtained in the step (1) under the ICP-OES working condition, and obtaining the content of bromine in the sample to-be-measured liquid according to the standard curve obtained in the step (2).
The formula for bromine is:
in the formula: x-bromine content,%;
c, calculating the concentration of bromine element in the sample solution to be detected, mg/L, according to the standard curve;
v is the total volume of the solution to be measured (volume after constant volume of the sample), L;
m is sample mass, mg.
10 batches of samples were tested as different batches of crude fluoroether rubber according to the above method, and the test results are shown in Table 1. The bromine content of the fluoroether rubber is low, about 0.3%. The experimental test result is basically consistent with the theoretical predicted value. The result shows that the ICP-OES method for determining the low bromine content in the fluororubber has high precision and good accuracy, provides a new way for analyzing the low bromine content in the fluororubber, has strong practicability, can be applied to element analysis and quality control of the fluororubber, and meets the requirements of production and scientific research.
TABLE 1 results of sample measurement
| Sample (I) | Bromine/%) | Sample (I) | Bromine/%) |
| FLT-1 | 0.26 | FLT-6 | 0.31 |
| FLT-2 | 0.24 | FLT-7 | 0.34 |
| FLT-3 | 0.28 | FLT-8 | 0.32 |
| FLT-4 | 0.33 | FLT-9 | 0.29 |
| FLT-5 | 0.31 | FLT-10 | 0.30 |
Precision verification
By using the procedure described in example 1, 1 part of the fluororubber sample was selected and continuously analyzed 8 times according to the analytical method, the results are shown in table 2, and the relative deviation of the measurement results of the bromine element concentration in the solution was calculated to be 0.90%, indicating that the method is good in precision.
TABLE 2 bromine determination results (mg/L)
Verification of detection limits
Under the optimal working condition of the instrument, 12 parts of a fluororubber sample are weighed, the measurement is respectively carried out according to a determined method, the concentration value and the standard deviation of the sample solution are obtained, and the detection limit of bromine is calculated to be 0.05mg/L according to the formula (1).
The formula is as follows:
in the formula: kiTaking 3 as a confidence factor;
Sistandard deviation of the sample solution measurements;
c is the concentration of the sample solution;
TABLE 3 detection limit verification test data (unit: mg/L)
Accuracy verification
Accuracy tests were performed as spiked recoveries. Weighing 3 parts of a fluororubber sample with known bromine content under the optimal working conditions of the instrument, obtaining a sample solution to be detected through the step (1), respectively adding a bromine standard solution, obtaining a bromine element measurement value through ICP-OES, and calculating the recovery rate according to a formula (2), wherein the data are shown in a table 4.
The recovery rate calculation formula is as follows:
TABLE 4 accuracy test results
The result shows that the analysis method for determining the low bromine content in the fluororubber by the ICP-OES has high accuracy and good precision. In addition, the pretreatment of the sample is convenient and quick, the sample can be continuously treated, the analysis period is greatly shortened, the use of organic reagents in a chemical analysis method is avoided, and the environmental pollution is reduced.
Claims (5)
1. A method for analyzing the low bromine content in fluororubber is characterized by comprising the following steps:
(1) setting a combustion program, and adopting an automatic rapid combustion furnace to carry out pretreatment on a rubber sample to obtain a sample to-be-detected liquid;
(2) preparing a blank solution and a bromine element standard solution series;
(3) measuring the standard solution prepared in the step (2) by utilizing ICP-OES to obtain a standard curve of signal intensity and bromine concentration;
(4) measuring the sample solution to be measured obtained in the step (1) by utilizing ICP-OES, combining a calibration curve to obtain the bromine content in the sample solution to be measured, and further converting the bromine content in the rubber, wherein the calculation formula of the bromine is as follows:
in the formula:
x-bromine content,%;
c, calculating the concentration of bromine element in the sample solution to be detected, mg/L, according to the standard curve;
v is the total volume of the solution to be measured (volume after constant volume of the sample), L;
m is sample mass, mg.
2. The method for analyzing the low bromine content in the fluororubber according to claim 1, wherein the specific step (1) is:
accurately weighing 10-20 mg of a sample, placing the sample in a sample boat, carrying the sample into a combustion furnace by argon, introducing oxygen, argon and a small amount of water into the combustion furnace, and carrying out pyrolysis combustion reaction at 800-1000 ℃; and oxidizing the sample by oxygen, absorbing the sample by a double-stage absorption tower, and fixing the volume to 100mL to obtain the solution to be detected of the sample.
3. The method for analyzing low bromine content in fluororubber according to claim 1, wherein the automatic combustion furnace conditions in step (1) are: gas flow rate: ar of the inner tube is 180mL/min, and O of the inner tube2210mL/min, outer tube O2Is 330 mL/min; the flow rate of the pyrolysis water is 0.30 mL/min; the air flow is 100 mL/min; the inlet temperature of the combustion pipe is 900 ℃, and the outlet temperature is 1000 ℃; the combustion analysis program is that the position 1 is 150mm, and the time is kept for 100 s; position 2 is 100mm, hold 150 s; position 3 is 30mm, hold 150 s; position 4 is 20mm, hold 150 s; position 5, 180mm, hold for 200 s; the end time was 150 s; the cooling time is 100 s; the sample feeding speed of the sample feeding boat is 5.0 mm/s.
4. The method for analyzing the low bromine content in the fluororubber according to claim 1, wherein the specific step (2) is:
empty burning the sample boat to obtain a blank solution; and diluting the standard bromide ion solution by 1000mg/L step by step to obtain standard bromide ion working solutions with the concentrations of 0.1, 0.5, 1.0, 2.0 and 5.0mg/L respectively.
5. The method for analyzing low bromine content in fluororubber according to claim 1, wherein the ICP-OES working conditions in steps (3) and (4) are as follows: the RF power is 1400W; the auxiliary gas flow is 1.0L/min; the flow rate of the atomizer is 0.8L/min; the flow rate of the cooling gas is 13.00L/min; the reverse blowing gas flow is 1.0L/min; the pre-washing time is 60 s; the stabilization time is 30 s; the sample injection system is a polytetrafluoroethylene sample injection system; in the ICP-OES measurement, analysis spectral lines are selected as follows: 154.065 nm.
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