CN115754072A - Qualitative and quantitative method for sodium sulfopropane sulfonate brightener in acid copper electroplating solution - Google Patents
Qualitative and quantitative method for sodium sulfopropane sulfonate brightener in acid copper electroplating solution Download PDFInfo
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- -1 sodium sulfopropane sulfonate Chemical compound 0.000 title claims abstract description 49
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 title claims abstract description 21
- 229910052802 copper Inorganic materials 0.000 title claims abstract description 21
- 239000010949 copper Substances 0.000 title claims abstract description 21
- 238000009713 electroplating Methods 0.000 title claims abstract description 21
- 239000002253 acid Substances 0.000 title claims abstract description 19
- 238000004445 quantitative analysis Methods 0.000 title claims abstract description 9
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 claims abstract description 46
- 229910052708 sodium Inorganic materials 0.000 claims abstract description 46
- 239000011734 sodium Substances 0.000 claims abstract description 46
- BDHFUVZGWQCTTF-UHFFFAOYSA-M sulfonate Chemical compound [O-]S(=O)=O BDHFUVZGWQCTTF-UHFFFAOYSA-M 0.000 claims abstract description 41
- WEVYAHXRMPXWCK-UHFFFAOYSA-N Acetonitrile Chemical compound CC#N WEVYAHXRMPXWCK-UHFFFAOYSA-N 0.000 claims abstract description 36
- 239000000243 solution Substances 0.000 claims abstract description 33
- FRTIVUOKBXDGPD-UHFFFAOYSA-M sodium;3-sulfanylpropane-1-sulfonate Chemical compound [Na+].[O-]S(=O)(=O)CCCS FRTIVUOKBXDGPD-UHFFFAOYSA-M 0.000 claims abstract description 26
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims abstract description 22
- 239000012086 standard solution Substances 0.000 claims abstract description 22
- OBDVFOBWBHMJDG-UHFFFAOYSA-M 3-sulfanylpropane-1-sulfonate Chemical compound [O-]S(=O)(=O)CCCS OBDVFOBWBHMJDG-UHFFFAOYSA-M 0.000 claims abstract description 18
- USFZMSVCRYTOJT-UHFFFAOYSA-N Ammonium acetate Chemical compound N.CC(O)=O USFZMSVCRYTOJT-UHFFFAOYSA-N 0.000 claims abstract description 18
- 239000005695 Ammonium acetate Substances 0.000 claims abstract description 18
- 229940043376 ammonium acetate Drugs 0.000 claims abstract description 18
- 235000019257 ammonium acetate Nutrition 0.000 claims abstract description 18
- 238000012360 testing method Methods 0.000 claims abstract description 18
- 238000000034 method Methods 0.000 claims abstract description 15
- 239000007864 aqueous solution Substances 0.000 claims abstract description 9
- 238000000589 high-performance liquid chromatography-mass spectrometry Methods 0.000 claims abstract description 4
- 150000002500 ions Chemical class 0.000 claims description 18
- 238000004128 high performance liquid chromatography Methods 0.000 claims description 6
- 238000002347 injection Methods 0.000 claims description 5
- 239000007924 injection Substances 0.000 claims description 5
- 239000003643 water by type Substances 0.000 claims description 5
- 238000006243 chemical reaction Methods 0.000 claims description 4
- 238000010829 isocratic elution Methods 0.000 claims description 4
- 238000012544 monitoring process Methods 0.000 claims description 4
- 238000004366 reverse phase liquid chromatography Methods 0.000 claims description 4
- 239000001294 propane Substances 0.000 claims description 3
- 238000001819 mass spectrum Methods 0.000 claims description 2
- 238000001514 detection method Methods 0.000 abstract description 16
- 238000011084 recovery Methods 0.000 abstract description 11
- 238000000926 separation method Methods 0.000 abstract description 7
- 238000011002 quantification Methods 0.000 abstract description 6
- 229910000365 copper sulfate Inorganic materials 0.000 abstract description 3
- ARUVKPQLZAKDPS-UHFFFAOYSA-L copper(II) sulfate Chemical compound [Cu+2].[O-][S+2]([O-])([O-])[O-] ARUVKPQLZAKDPS-UHFFFAOYSA-L 0.000 abstract description 3
- 239000005416 organic matter Substances 0.000 abstract description 2
- 238000004458 analytical method Methods 0.000 description 11
- 239000000523 sample Substances 0.000 description 8
- 239000003795 chemical substances by application Substances 0.000 description 5
- 239000007788 liquid Substances 0.000 description 5
- 239000012528 membrane Substances 0.000 description 5
- 238000007747 plating Methods 0.000 description 5
- OYHHGYJKBOUMOB-UHFFFAOYSA-M sodium;oxido-oxo-propyl-sulfanylidene-$l^{6}-sulfane Chemical compound [Na+].CCCS([O-])(=O)=S OYHHGYJKBOUMOB-UHFFFAOYSA-M 0.000 description 5
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 5
- 239000007853 buffer solution Substances 0.000 description 4
- 239000008367 deionised water Substances 0.000 description 4
- 229910021641 deionized water Inorganic materials 0.000 description 4
- 239000012488 sample solution Substances 0.000 description 4
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 3
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical group OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 3
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 description 3
- 239000003638 chemical reducing agent Substances 0.000 description 3
- 238000001914 filtration Methods 0.000 description 3
- 239000000654 additive Substances 0.000 description 2
- 230000000996 additive effect Effects 0.000 description 2
- 238000005282 brightening Methods 0.000 description 2
- 239000003153 chemical reaction reagent Substances 0.000 description 2
- 239000011248 coating agent Substances 0.000 description 2
- 238000000576 coating method Methods 0.000 description 2
- 238000011161 development Methods 0.000 description 2
- 238000007865 diluting Methods 0.000 description 2
- ALVPFGSHPUPROW-UHFFFAOYSA-N dipropyl disulfide Chemical compound CCCSSCCC ALVPFGSHPUPROW-UHFFFAOYSA-N 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- KIUMMUBSPKGMOY-UHFFFAOYSA-N 3,3'-Dithiobis(6-nitrobenzoic acid) Chemical group C1=C([N+]([O-])=O)C(C(=O)O)=CC(SSC=2C=C(C(=CC=2)[N+]([O-])=O)C(O)=O)=C1 KIUMMUBSPKGMOY-UHFFFAOYSA-N 0.000 description 1
- OBDVFOBWBHMJDG-UHFFFAOYSA-N 3-mercapto-1-propanesulfonic acid Chemical compound OS(=O)(=O)CCCS OBDVFOBWBHMJDG-UHFFFAOYSA-N 0.000 description 1
- 238000012935 Averaging Methods 0.000 description 1
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000000052 comparative effect Effects 0.000 description 1
- 238000002425 crystallisation Methods 0.000 description 1
- 230000008025 crystallization Effects 0.000 description 1
- 238000002484 cyclic voltammetry Methods 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000000132 electrospray ionisation Methods 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000004451 qualitative analysis Methods 0.000 description 1
- 238000007670 refining Methods 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 239000000741 silica gel Substances 0.000 description 1
- 229910002027 silica gel Inorganic materials 0.000 description 1
- 238000012421 spiking Methods 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 238000010998 test method Methods 0.000 description 1
- 229910021642 ultra pure water Inorganic materials 0.000 description 1
- 239000012498 ultrapure water Substances 0.000 description 1
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P10/00—Technologies related to metal processing
- Y02P10/20—Recycling
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Abstract
The invention relates to the technical field of organic matter detection, in particular to a qualitative and quantitative method for a sodium sulfopropane sulfonate brightener in a copper sulfate electroplating solution. The method comprises the following steps: (1) Dissolving standard samples of sodium polydithio-dipropyl sulfonate and 3-mercapto-1-propane sulfonate by using sulfuric acid aqueous solution to prepare standard solutions with different concentrations, injecting the standard solutions into a high performance liquid chromatography-mass spectrometry instrument, and drawing a standard curve by using ammonium acetate aqueous solution/acetonitrile as a mobile phase; (2) And (3) testing the acid copper electroplating solution under the same test conditions as the step (1), and calculating the content of the sodium polydithio-dipropyl sulfonate and the content of the sodium 3-mercapto-1-propane sulfonate in the acid copper electroplating solution according to a standard curve. The method has the advantages of capability of realizing effective separation of the sodium polydithio-dipropyl sulfonate and the sodium 3-mercapto-1-propane sulfonate, high precision and recovery rate, low detection limit and quantification limit and high stability.
Description
Technical Field
The invention relates to the technical field of organic matter detection, in particular to a qualitative and quantitative method for a sodium sulfopropane sulfonate brightener in a copper sulfate electroplating solution.
Background
The sodium thiopropane sulfonate compound is mainly applied to electroplating acid copper plating, is used for preparing a copper plating brightener, is a main additive component in a copper plating additive, can perform the functions of refining the crystallization of a plating layer and effectively improving the current density, and is particularly suitable for electroplating of printed circuit boards. In the market of acid copper brightener, the product has large demand and excellent application effect. The addition of the sodium thiopropane sulfonate determines the light-emitting speed and stability of the formula, and the proper amount of the sodium thiopropane sulfonate can obviously adjust the growth and performance of a coating and improve the texture structure and performance of the coating, so that the content of the sodium thiopropane sulfonate is an important index for controlling the product quality, and the structure and the content of the sodium thiopropane sulfonate are very necessary to be accurately measured.
At present, the common sodium sulfopropane sulfonate brightening agents in the market are mainly sodium polydithio-dipropyl sulfonate (SPS) and sodium 3-mercapto-1-propane sulfonate (MPS), and the chemical structural formula of the brightening agent is shown as follows:
because the SPS and MPS are very similar in chemical structure, qualitative and quantitative determination of both has been difficult. Currently, research on sodium thiopropane sulfonate is mainly focused on quantitative analysis of SPS, including high performance liquid chromatography, derivative color development, cyclic voltammetry and the like.
For example, chinese patent application CN111157520A discloses a detection reagent and a detection method for detecting the content of sodium polydithio-dipropyl sulfonate in acid copper electroplating solution, the detection reagent used comprises a reducing agent, a buffer solution and a color-developing agent, wherein the reducing agent is a reducing agent for reducing disulfide bonds in sodium polydithio-dipropyl sulfonate to sulfydryl; the buffer solution has a pH value of 8-10; the color developing agent is 5,5' -dithiobis (2-nitrobenzoic acid). The invention provides a derivative color development method, which is characterized in that disulfide bonds in sodium polydithio-dipropyl sulfonate are reduced to sulfydryl, and then color developing agents are added, and the quantification is carried out by an ultraviolet spectrophotometer.
Chinese patent application CN105606738A discloses a high performance liquid chromatography analysis method of sodium polydithio-dipropyl sulfonate. The high performance liquid analysis method adopts a high performance liquid chromatograph equipped with an ultraviolet detector to carry out determination, octadecyl bonding silica gel is used as a filling column, the size of the chromatographic column is 250mm column length multiplied by 4.6mm inner diameter, and the grain diameter is 5 mu m; the mobile phase is methanol and buffer solution with the volume ratio of 0-50; the detection wavelength is 190-330 nm; the column temperature is 10-60 ℃; the speed of the mobile phase is 0.3-1.2 mL/min; the sample injection amount is 20 mu L; wherein the buffer solution is 0.17mol/L acetic acid, 0.142mol/L triethylamine and ultrapure water. The standard curve established by the standard solution can quickly and accurately measure the content of the sodium polydithio-dipropyl sulfonate in the sample to be measured, the measurement result has small error and strong repeatability, the precision is less than 2.8 percent, and the recovery rate is 96.7 to 99.3 percent. But the detection limit is high and it is difficult to distinguish SPS from MPS.
At present, more quantitative analysis of SPS has been reported, but there are few studies on how to distinguish SPS from MPS, and on qualitative and quantitative analysis of MPS.
Therefore, it is necessary to develop a method for qualitative and quantitative determination of sodium sulfopropane sulfonate brightener in copper sulfate electroplating solution, which can solve the above technical problems.
Disclosure of Invention
The invention aims to overcome the defects of the prior art and provide a method for qualitatively and quantitatively determining a sodium sulfopropane sulfonate brightener in an acid copper electroplating solution, which can realize effective separation of SPS and MPS, has high precision and recovery rate, low detection limit and quantitative limit and high stability.
The invention is realized by the following technical scheme:
a qualitative and quantitative method for a sodium sulfopropane sulfonate brightener in acid copper electroplating solution, wherein the sodium sulfopropane sulfonate brightener comprises sodium polydithio-dipropyl sulfonate and 3-mercapto-1-propane sulfonate, and comprises the following steps:
(1) Dissolving standard samples of sodium polydithio-dipropyl sulfonate and 3-mercapto-1-propane sulfonate by using aqueous solution of sulfuric acid, preparing standard solutions with different concentrations, injecting the standard solutions into a high performance liquid chromatography-mass spectrometry combination instrument, and drawing a standard curve by using ammonium acetate aqueous solution/acetonitrile as a mobile phase;
(2) And (3) testing the acid copper electroplating solution under the same test conditions as the step (1), and calculating the content of the sodium polydithio-dipropyl sulfonate and the content of the sodium 3-mercapto-1-propane sulfonate in the acid copper electroplating solution according to a standard curve.
Preferably, the concentration of the aqueous ammonium acetate solution in step (1) is 5mmol/L.
Preferably, the volume ratio of the aqueous ammonium acetate solution to the acetonitrile in step (1) is 95.
Preferably, a Waters CORTECS C18 reverse phase chromatography column is used in step (1).
More preferably, the Waters CORTECS C18 reverse phase chromatography column specification is 2.7 μm × 2.1mm × 100mm.
More preferably, the chromatographic conditions in step (1) are: the column temperature is 40 ℃, the flow rate is 0.2mL/min, isocratic elution is carried out, and the sample injection volume is 1 mu L.
Preferably, the mass spectrum conditions in step (1) are: the jet flow electrospray ion source has the advantages of 300 ℃ of dry gas, 300 ℃ of sheath gas, 5L/min of flow rate of the dry gas, 11L/min of flow rate of the sheath gas, 45psi of electrospray voltage, 4000V of capillary voltage, negative ion scanning and multi-reaction monitoring (MRM).
Preferably, the aqueous sulfuric acid solution in step (1) has a pH of 3.5; preparing standard solutions with different concentrations of 0.05-2 mg/L.
Preferably, the standard solution and/or the acid copper plating solution is filtered through an organic filter membrane before being injected into the triple quadrupole HPLC MS.
More preferably, the organic filter is 0.22 μm.
Preferably, the sodium polydithio-dipropyl sulfonate is a qualitative and quantitative ion pair of 309/154.8; the sodium 3-mercapto-1-propanesulfonate takes 155/80 as a qualitative and quantitative ion pair.
More preferably, the sodium polydithio-dipropyl sulfonate takes 309/81 as an auxiliary qualitative ion pair; the 3-mercapto-1-propane sodium sulfonate takes 155/121 as an auxiliary qualitative ion pair.
Preferably, the high performance liquid chromatography-mass spectrometer is a triple quadrupole high performance liquid chromatography-mass spectrometer.
Preferably, the purity of the sodium polydithio-dipropyl sulfonate standard sample is more than 97%, and the purity of the sodium 3-mercapto-1-propane sulfonate standard sample is more than 90%.
The invention has the beneficial effects that:
1. based on the difference of quantitative ions of SPS and MPS, the invention adopts a triple quadrupole high performance liquid chromatography-mass spectrometer to realize effective separation of SPS and MPS, thereby accurately quantifying the SPS and the MPS.
2. The invention is in the concentration range of 0.05-2 mg/L, the linear correlation coefficient of the standard curve is more than 0.9999, the precision is less than 2.0%, the recovery rate is 96.5-107.4%, the detection limits of MPS and SPS are respectively as low as 0.003mg/L and 0.004mg/L, and the quantification limit is as low as 0.01mg/L.
Drawings
FIG. 1 is a standard curve of sodium polydithio-dipropyl sulfonate and sodium 3-mercapto-1-propane sulfonate.
FIG. 2 is a chromatogram of sodium polydithiodipropanesulfonate and sodium 3-mercapto-1-propanesulfonate in aqueous ammonium acetate (5 mmol/L)/acetonitrile at a volume ratio of 90 and 95.
FIG. 3 is a chromatogram of sodium polydithio-dipropyl sulfonate and sodium 3-mercapto-1-propane sulfonate at ammonium acetate contents of 2.5, 5, 10mmol/L in aqueous ammonium acetate/acetonitrile (95, v/v).
Detailed Description
The invention is further described below in conjunction with specific embodiments, and the advantages and features of the invention will become more apparent as the description proceeds. These examples are illustrative only and do not limit the scope of the present invention in any way. It will be understood by those skilled in the art that various changes in form and details may be made therein without departing from the spirit and scope of the invention, and that such changes and substitutions are intended to be within the scope of the invention.
Example 1
1) And (3) testing conditions:
a triple quadrupole high performance liquid chromatography-mass spectrometry combination instrument with a jet electrospray ionization source is used as a testing instrument.
Waters CORTECS C18 reverse phase chromatography column (2.7 um. Times.2.1 mm. Times.100 mm), column temperature 40 ℃, flow rate 0.2mL/min, ammonium acetate aqueous solution (5 mmol/L)/acetonitrile as mobile phase (95, 5, v/v), isocratic elution, sample injection volume 1 u L.
The jet flow electrospray ion source has the advantages of 300 ℃ of dry gas, 300 ℃ of sheath gas, 5L/min of flow rate of dry gas, 11L/min of flow rate of sheath gas, 45psi of electrospray voltage, 4000V of capillary voltage, negative ion scanning and multi-reaction monitoring (MRM).
2) Standard curves for sodium polydithio-dipropyl sulfonate and sodium 3-mercapto-1-propane sulfonate:
0.01g of sodium polydithio-dipropyl sulfonate and 0.01g of sodium 3-mercapto-1-propane sulfonate are accurately weighed respectively, dissolved by a sulfuric acid solution (pH = 3.5) to a constant volume of 10mL to prepare a 1000mg/L mixed standard solution of sodium polydithio-dipropyl sulfonate and sodium 3-mercapto-1-propane sulfonate, and further diluted by the sulfuric acid solution (pH = 3.5) to prepare a mixed standard solution of 10mg/L and 1mg/L. Taking different volumes of solutions from mixed standard solutions of 10mg/L and 1mg/L, diluting the solutions with a sulfuric acid solution (pH = 3.5), preparing mixed standard solutions of 0.05mg/L, 0.1mg/L, 0.2mg/L, 0.5mg/L, 1mg/L and 2mg/L, filtering the solutions with a 0.22 mu m organic filter membrane, testing the solutions for 3 times according to 1) testing conditions, averaging results, respectively taking peak areas of the sodium polydithio-dipropyl sulfonate and the sodium 3-mercapto-1-propane sulfonate as vertical coordinates, mass concentrations of the sodium polydithio-dipropyl sulfonate and the sodium 3-mercapto-1-propane sulfonate as horizontal coordinates, and drawing a standard curve as follows: sodium polydithio-dipropanesulfonate y =344.1x-5.6; the sodium 3-mercapto-1-propane sulfonate y =258.7x-3.5, the linear ranges are 0.05 mg/L-2 mg/L, and the correlation coefficients are not less than 0.9999, as shown in figure 1.
3) Precision and recovery:
taking 3 parts of blank deionized water, adjusting the pH value to 3.5 by using sulfuric acid, sequentially adding 50 mu L and 200 mu L of 10mg/L mixed standard solution and 200 mu L of 100mg/L mixed standard solution, adding standard concentrations of 0.05mg/L, 0.2mg/L and 2mg/L respectively, and performing constant volume to 10mL to obtain a sample solution. The sample solution is filtered by an organic filter membrane of 0.22 mu m, and is subjected to machine analysis according to the test conditions of 1), each concentration point is independently tested for 3 times, the precision and the recovery rate of the sodium polydithio-dipropyl sulfonate are respectively 0.8-1.9 percent and 99.7-107.4 percent, the precision and the recovery rate of the sodium 3-mercapto-1-propane sulfonate are respectively 0.8-1.6 percent and 96.5-106.5 percent, and the results are shown in Table 1.
TABLE 1 precision and recovery calculations with spiking
4) Detection limit and quantification limit:
taking 10 parts of blank deionized water, adjusting the pH value to be =3.5 by using sulfuric acid, adding 50 mu L of 10mg/L mixed standard solution, adding standard concentrations of 0.05mg/L respectively, fixing the volume to 10mL, filtering the sample solution by using a 0.22 mu m organic filter membrane, performing machine analysis according to 1) test conditions, and independently performing 10 times of analysis, wherein the detection limit and the quantification limit of the sodium polydithio-dipropyl sulfonate are 0.003mg/L and 0.01mg/L respectively, the detection limit and the quantification limit of the sodium 3-mercapto-1-propanesulfonate are 0.0036mg/L and 0.012mg/L respectively, and the results are shown in Table 2.
TABLE 2 detection limit and quantitation limit calculations
Remarking: limit of detection =3 × standard deviation; limit of quantitation =10 × standard deviation.
5) The method has the following stability:
taking 6 parts of blank deionized water, adjusting the pH value to be =3.5 by using sulfuric acid, adding 50 mu L of 10mg/L mixed standard solution, wherein the adding standard concentration is 0.05mg/L respectively, the constant volume is 10mL, filtering the sample solution by using a 0.22 mu m organic filter membrane, performing machine analysis according to 1) test conditions, and independently performing 6 times of analysis, wherein the precision degrees of the poly (dipropyl disulfide) sodium sulfonate and the 3-mercapto-1-propane sodium sulfonate are 0% and 3.87% respectively, which shows that the test method is stable, and the result is shown in Table 3.
TABLE 3 calculation of precision
6) Detection and standard recovery rate of sodium polydithio-dipropyl sulfonate and 3-mercapto-1-propane sulfonic acid in industrial acid copper electroplating solution sample
Diluting 100 mu L of industrial-grade acid copper electroplating solution with deionized water, fixing the volume to 10mL, and performing computer analysis according to the test conditions in step 1), wherein according to the standard curve in the step 2), the content of the sodium polydithio-dipropyl sulfonate in the diluted industrial-grade acid copper electroplating solution is 0.1461mg/L, and no 3-mercapto-1-propane sulfonate is detected.
Taking 1mL of 3 parts of diluted industrial-grade acid copper electroplating solution, adding 0.05 mu g, 0.1 mu g and 2 mu g of sodium polydithio-dipropyl sulfonate and 3-mercapto-1-propane sulfonate standard solution into each part, and calculating the recovery rates of the sodium polydithio-dipropyl sulfonate to be 97.8%, 100.1% and 114.5% respectively, and the recovery rates of the sodium 3-mercapto-1-propane sulfonate to be 91.4%, 91.3% and 90.7% respectively.
Comparative example 1 examination of the influence of flow on the analysis of a mixed standard solution of sodium polydithio-dipropanesulfonate and sodium 3-mercapto-1-propanesulfonate
1) And (3) testing conditions are as follows:
a triple quadrupole high performance liquid chromatography mass spectrometer combined instrument with a jet electrospray ion source is used as a testing instrument.
Waters CORTECS C18 reversed phase chromatographic column (2.7 um × 2.1mm × 100 mm), column temperature 40 deg.C, flow rate 0.2mL/min, ammonium acetate water solution/acetonitrile as mobile phase, isocratic elution, sample injection volume 1 μ L.
The jet flow electrospray ion source has the advantages of 300 ℃ of dry gas, 300 ℃ of sheath gas, 5L/min of flow rate of dry gas, 11L/min of flow rate of sheath gas, 45psi of electrospray voltage, 4000V of capillary voltage, negative ion scanning and multi-reaction monitoring (MRM).
2) The separation of sodium polydithio-dipropanesulfonate and sodium 3-mercapto-1-propanesulfonate in aqueous ammonium acetate (5 mmol/L)/acetonitrile at volume ratios of 90 and 95, respectively, was investigated.
Preparing 1mg/L mixed standard solution, and performing machine analysis according to 1) test conditions to obtain: the sodium polydithio-dipropyl sulfonate and the sodium 3-mercapto-1-propane sulfonate were well separated at a volume ratio of 95 ammonium acetate aqueous solution (5 mmol/L) to acetonitrile of 95, whereas at a volume ratio of 90, the sodium polydithio-dipropyl sulfonate and the sodium 3-mercapto-1-propane sulfonate were not separated, as shown in FIG. 2.
3) The separation of sodium polydithiodipropanesulfonate and sodium 3-mercapto-1-propanesulfonate at different ammonium acetate contents was investigated. Preparing a 1mg/L mixed standard solution, and performing machine analysis according to 1) test conditions, wherein the volume ratio of the ammonium acetate aqueous solution to the acetonitrile is 95, and the separation of the sodium polydithio-dipropyl sulfonate and the 3-mercapto-1-propane sulfonate when the ammonium acetate content is respectively 2.5, 5 and 10mmol/L is inspected, so that the following results can be obtained: at an ammonium acetate content of 5mmol/L, the separation of sodium polydithio-dipropyl sulfonate and sodium 3-mercapto-1-propane sulfonate was best, and the results are shown in FIG. 3.
The above detailed description is directed to one of the possible embodiments of the present invention, which is not intended to limit the scope of the invention, but rather the scope of the invention is intended to include all equivalent implementations or modifications without departing from the scope of the invention.
Claims (10)
1. A qualitative and quantitative method for a sodium sulfopropane sulfonate brightener in acid copper electroplating solution, wherein the sodium sulfopropane sulfonate brightener comprises sodium polydithio-dipropyl sulfonate and 3-mercapto-1-propane sulfonate, and is characterized by comprising the following steps:
(1) Dissolving standard samples of sodium polydithio-dipropyl sulfonate and 3-mercapto-1-propane sulfonate by using sulfuric acid aqueous solution to prepare standard solutions with different concentrations, injecting the standard solutions into a high performance liquid chromatography-mass spectrometry instrument, and drawing a standard curve by using ammonium acetate aqueous solution/acetonitrile as a mobile phase;
(2) And (2) testing the acid copper electroplating solution under the same test conditions as the step (1), and calculating the content of the sodium polydithio-dipropyl sulfonate and the content of the sodium 3-mercapto-1-propane sulfonate in the acid copper electroplating solution according to a standard curve.
2. The method according to claim 1, wherein the concentration of the aqueous ammonium acetate solution in the step (1) is 5mmol/L.
3. The process according to claim 1, wherein the volume ratio of the aqueous ammonium acetate solution to the acetonitrile in the step (1) is 95.
4. The method of claim 1, wherein step (1) comprises using a Waters CORTECS C18 reverse phase chromatography column.
5. The method according to claim 4, wherein the chromatographic conditions in step (1) are: the column temperature is 40 ℃, the flow rate is 0.2mL/min, isocratic elution is carried out, and the sample injection volume is 1 mu L.
6. The method according to claim 1, wherein the mass spectrum conditions in step (1) are: the jet flow electrospray ion source has the advantages of 300 ℃ of dry gas, 300 ℃ of sheath gas, 5L/min of flow rate of the dry gas, 11L/min of flow rate of the sheath gas, 45psi of electrospray voltage, 4000V of capillary voltage, negative ion scanning and multi-reaction monitoring (MRM).
7. The method according to claim 1, wherein the aqueous sulfuric acid solution in step (1) has a pH of 3.5; preparing standard solutions with different concentrations of 0.05-2 mg/L.
8. The method of claim 1, wherein sodium polydithiodipropyl sulfonate is characterized as a qualitative and quantitative ion pair of 309/154.8; the sodium 3-mercapto-1-propanesulfonate takes 155/80 as a qualitative and quantitative ion pair.
9. The method of claim 8, wherein the sodium polydithio-dipropyl sulfonate is characterized by 309/81 as an auxiliary qualitative ion pair; the 3-mercapto-1-propane sodium sulfonate uses 155/121 as an auxiliary qualitative ion pair.
10. The method of claim 1, wherein the high performance liquid chromatography mass spectrometer is a triple quadrupole high performance liquid chromatography mass spectrometer.
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| CN117517487A (en) * | 2023-10-07 | 2024-02-06 | 湖北吉和昌化工科技有限公司 | Method for detecting content of N, N-dimethyl-dithio carbonyl propane sodium sulfonate |
Citations (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101363817A (en) * | 2008-05-23 | 2009-02-11 | 浙江大学宁波理工学院 | Method for detecting multi-brightener in liquid for brilliantly nickel plating |
| CN101492832A (en) * | 2008-01-25 | 2009-07-29 | 中芯国际集成电路制造(上海)有限公司 | Method for measuring organic additive by-product concentration in copper plating solution with SPE-HPLC |
| CN105606738A (en) * | 2016-02-05 | 2016-05-25 | 湖北吉和昌化工科技有限公司 | HPLC (High Performance Liquid Chromatography) analysis method for sodium 3,3'-dithiodipropane sulfonate |
| CN108760821A (en) * | 2018-06-04 | 2018-11-06 | 电子科技大学 | A kind of qualitative and quantitative analysis method of electroplating additive |
| CN112996933A (en) * | 2018-11-06 | 2021-06-18 | 德国艾托特克公司 | Electroless nickel plating solution |
| CN113341035A (en) * | 2021-07-29 | 2021-09-03 | 湖南沁森高科新材料有限公司 | Detection method of camphorsulfonic acid and sodium dodecyl sulfate |
| CN113686979A (en) * | 2021-05-31 | 2021-11-23 | 金川集团股份有限公司 | Method for detecting brightening agents saccharin sodium and sodium benzene sulfinate in nickel electrolyte |
-
2022
- 2022-11-24 CN CN202211485111.7A patent/CN115754072A/en active Pending
Patent Citations (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101492832A (en) * | 2008-01-25 | 2009-07-29 | 中芯国际集成电路制造(上海)有限公司 | Method for measuring organic additive by-product concentration in copper plating solution with SPE-HPLC |
| CN101363817A (en) * | 2008-05-23 | 2009-02-11 | 浙江大学宁波理工学院 | Method for detecting multi-brightener in liquid for brilliantly nickel plating |
| CN105606738A (en) * | 2016-02-05 | 2016-05-25 | 湖北吉和昌化工科技有限公司 | HPLC (High Performance Liquid Chromatography) analysis method for sodium 3,3'-dithiodipropane sulfonate |
| CN108760821A (en) * | 2018-06-04 | 2018-11-06 | 电子科技大学 | A kind of qualitative and quantitative analysis method of electroplating additive |
| CN112996933A (en) * | 2018-11-06 | 2021-06-18 | 德国艾托特克公司 | Electroless nickel plating solution |
| CN113686979A (en) * | 2021-05-31 | 2021-11-23 | 金川集团股份有限公司 | Method for detecting brightening agents saccharin sodium and sodium benzene sulfinate in nickel electrolyte |
| CN113341035A (en) * | 2021-07-29 | 2021-09-03 | 湖南沁森高科新材料有限公司 | Detection method of camphorsulfonic acid and sodium dodecyl sulfate |
Non-Patent Citations (2)
| Title |
|---|
| RYAN G. BRENNAN: "Characterization and Purification of Commercial SPS and MPS by Ion Chromatography and Mass Spectrometry", JOURNAL OF THE ELECTROCHEMICAL SOCIETY, 21 January 2011 (2011-01-21), pages 178 - 185 * |
| 周围;解迎双;王波;贾松涛;牛洪亮;: "固相萃取/高效液相色谱法同时测定水中4种直链烷基苯磺酸钠", 分析测试学报, no. 01, 25 January 2011 (2011-01-25), pages 95 - 98 * |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN117517487A (en) * | 2023-10-07 | 2024-02-06 | 湖北吉和昌化工科技有限公司 | Method for detecting content of N, N-dimethyl-dithio carbonyl propane sodium sulfonate |
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