CN103698442B - Quantitative method of malonic acid in metal surface treatment agent - Google Patents
Quantitative method of malonic acid in metal surface treatment agent Download PDFInfo
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- CN103698442B CN103698442B CN201310742355.3A CN201310742355A CN103698442B CN 103698442 B CN103698442 B CN 103698442B CN 201310742355 A CN201310742355 A CN 201310742355A CN 103698442 B CN103698442 B CN 103698442B
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- malonic acid
- metal conditioner
- complexing agent
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Abstract
The invention discloses a quantitative method of malonic acid in a metal surface treatment agent. The quantitative method aims at replacing a complexing agent, namely malonic acid in the metal surface treatment agent with malonic acid in a complexing system formed by metal ions by utilizing a strong complexing agent, so that malonic acid in the metal surface treatment agent is quantified accurately and qualitatively by multiple detection means such as LC (liquid chromatography) and LC-MS (liquid chromatography-mass spectrometry).
Description
Technical field
The present invention relates to a kind of quantivative approach of metal conditioner complexing agent, specifically, is the quantivative approach of malonic acid in a kind of metal conditioner.
Background technology
Metal conditioner is primarily of component compositions such as slaine, complexing agent, buffering agent, stabilizing agent, pH value correctivess; be mainly used in Treatment of Metal Surface; after metal surface and metal conditioner soak and contact; metal surface produces microfabricated chemical reactor; metal surface active for original chemical property is changed into the metal surface of chemical inertness; reach and be difficult to produce chemical reaction again with external substance, thus reach the effect of digital preservation.
Malonic acid is Small molecular organic dibasic acid, itself has certain Complex effect, and be generally used as complexing agent and add in metal conditioner, addition is usually about 0.5% to 1.2%; Little owing to adding comparision contents, conventional infrared, nuclear-magnetism, MS qualitative, quantitative means all have some limitations, be difficult to accurate qualitative and quantitative analysis, this patent is quoted liquid phase chromatography and is carried out qualitative and quantitative analysis to the malonic acid in metal conditioner, and optimize chromatographic condition, explore pre-treatment analytical technology, develop a kind of analytical approach being best suited for malonic acid in metal conditioner sample system.
In metal conditioner system, malonic acid is added in system as complexing agent, its easy and reacting metal salt, generate slaine-malonic acid complex system, this complex system Stability Analysis of Structures, and it is all inconsistent with the relevant nature of malonic acid episome, and present stage technology be difficult to carry out qualitative and quantitative analysis to the malonic acid in slaine-malonic acid system, very large puzzlement is caused to the malonic acid analysis in metal conditioner, cause huge predicament also to the formulation analysis of metal conditioner, this patent passes through pre-treating method, add the stronger complexing agent of another complex performance and slaine carries out complexing, slaine-malonic acid complex system is decomposed, discharge malonic acid free molecule, re-use liquid phase chromatography and qualitative and quantitative analysis is carried out to malonic acid.
Summary of the invention
The present invention cements out in metal conditioner as the malonic acid in slaine-malonic acid complex system that the malonic acid of complexing agent and slaine generate by adding a kind of strong complexing agent, form more stable slaine-strong complexing agent system, thus realize with the malonic acid in the accurate qualitative, quantitative metal conditioner of the multiple detection means such as LC, LC-MS.
For achieving the above object, the quantivative approach of malonic acid in a kind of metal conditioner, comprises the following steps:
A) in metal conditioner, drip strong complexing agent, fully mix, obtain mixed liquor;
B) mixed liquor is put in 80 DEG C of water baths, heating and thermal insulation process, after 1-2 hour, adds ultrapure water and mend heavy, obtain solution to be measured.
According to the quantivative approach of malonic acid in a kind of metal conditioner of the present invention, pH adjusting agent is utilized to make metal conditioner system maintain pH=7-9, the complexing speed of strong complexing agent can be improved, pH adjusting agent has the ability with complex simultaneously, improves the Complexation Efficiency of strong complexing agent further.
Utilize pH adjusting agent to maintain the quantivative approach of malonic acid in a kind of metal conditioner of metal conditioner pH value, comprise the following steps:
A) in metal conditioner, drip pH adjusting agent, adjust ph, to 7-9, obtains alkaline solution;
B) add strong complexing agent in an acidic solution, fully mix, obtain mixed liquor;
C) be put in by mixed liquor in 80 DEG C of water baths, heating and thermal insulation process, after 1-2 hour, adds ultrapure water and mends heavy, obtain solution to be measured.
Strong complexing agent of the present invention include but not limited in Phen, oxine one or both.
Acidity regulator of the present invention includes but not limited to one or more in NaOH, sodium bicarbonate, sodium carbonate, sal tartari.
The preferred NaOH of acid of described adjust ph.
The invention is not restricted to the quantitative of the malonic acid in metal conditioner, the present invention all can be utilized to carry out quantitatively for the complexing agent in metal conditioner.
Specific embodiment
NaOH involved in following examples, for analyzing pure rank, is produced by Chemical Reagent Co., Ltd., Sinopharm Group.
Strong complexing agent Phen involved in following examples, for analyzing pure rank, is produced by Chemical Reagent Co., Ltd., Sinopharm Group.
Strong complexing agent oxine involved in following examples, for analyzing pure rank, is produced by lark prestige Science and Technology Ltd..
LC involved in following examples is the liquid chromatograph of the LC-20A type that Shimadzu Corporation produces.
LC-MS involved in following examples is the LC-MS-2020 type liquid chromatograph-mass spectrometer that Shimadzu Corporation produces.
Embodiment 1
Pre-service is to eliminate the impact of metallic ion on malonic acid:
Measure 100ml metal conditioner, drip the strong complexing agent oxine of 0.5g, fully mix, be put in by mixed liquor in 80 DEG C of water baths, heating and thermal insulation process, after 2 hours, adds ultrapure water and mends heavy, obtain testing sample 1;
Sample 1 is detected with LC:
Eliminating the sample 1 after metal ion disturbance directly uses LC as detection means, carries out analysis measure the levels of wherein contained malonic acid.LC determination step carries out in a conventional manner, and wherein, Details as Follows for each parameter:
Chromatographic condition: chromatographic column selects C18(250mm × 4.6mm × 5um) chromatographic column; Sample size 10 microlitre; Post case constant temperature is at 35 DEG C; Potassium dihydrogen phosphate aqueous solution=the 5:95 of mobile phase: methyl alcohol: 15mmol; Flow velocity: 0.8mL/min; Determined wavelength: 204nm.
The testing result of sample 1: malonic acid=0.83%.
Embodiment 2
Pre-service is to eliminate the impact of metallic ion on malonic acid:
Measure 100ml metal conditioner, drip the strong complexing agent Phen of 1g, fully mix, be put in by mixed liquor in 80 DEG C of water baths, heating and thermal insulation process, after 2 hours, adds ultrapure water and mends heavy, obtain testing sample 2;
Sample 2 is detected with LC:
Eliminating the sample 2 after metal ion disturbance directly uses LC as detection means, carries out analysis measure the levels of wherein contained malonic acid.LC determination step carries out in a conventional manner, and wherein, Details as Follows for each parameter:
Chromatographic condition: chromatographic column selects C18(250mm × 4.6mm × 5um) chromatographic column; Sample size 10 microlitre; Post case constant temperature is at 35 DEG C; Potassium dihydrogen phosphate aqueous solution=the 5:95 of mobile phase: methyl alcohol: 15mmol; Flow velocity: 0.8mL/min; Determined wavelength: 204nm.
The testing result of sample 2: malonic acid=0.88%.
Embodiment 3
Adjust ph:
Measure 100ml metal conditioner, drop to after 10g sodium hydrate solid is dissolved in 50ml water in the surface conditioning agent after measuring, adjust ph to 7, obtains alkaline solution;
Pre-service is to eliminate the impact of metallic ion on malonic acid:
Drip the strong complexing agent oxine of 0.5g in oxytropism solution, fully mix, be put in by mixed liquor in 80 DEG C of water baths, heating and thermal insulation process, after 2 hours, adds ultrapure water and mends heavy, obtain testing sample 3;
Sample 3 is detected with LC:
Eliminating the sample 3 after metal ion disturbance directly uses LC as detection means, carries out analysis measure the levels of wherein contained malonic acid.LC determination step carries out in a conventional manner, and wherein, Details as Follows for each parameter:
Chromatographic condition: chromatographic column selects C18(250mm × 4.6mm × 5um) chromatographic column; Sample size 10 microlitre; Post case constant temperature is at 35 DEG C; Potassium dihydrogen phosphate aqueous solution=the 5:95 of mobile phase: methyl alcohol: 15mmol; Flow velocity: 0.8mL/min; Determined wavelength: 204nm.
The testing result of sample 3: malonic acid=0.91%.
Embodiment 4
Adjust ph:
Measure 100ml metal conditioner, drop to after 10g sodium hydrate solid is dissolved in 50ml water in the surface conditioning agent after measuring, adjust ph to 8, obtains alkaline solution;
Pre-service is to eliminate the impact of metallic ion on malonic acid:
Drip the strong complexing agent oxine of 0.5g in oxytropism solution, fully mix, be put in by mixed liquor in 80 DEG C of water baths, heating and thermal insulation process, after 1 hour, adds ultrapure water and mends heavy, obtain testing sample 4;
Sample 4 is detected with LC-MS:
Eliminating the sample 4 after metal ion disturbance directly uses LC-MS as detection means, carries out analysis measure the levels of wherein contained malonic acid.LC-MS determination step carries out in a conventional manner, and wherein, Details as Follows for each parameter:
Chromatographic condition: chromatographic column selects C18 (150mm × 2.1mm × 5um) chromatographic column; Sample size 10 microlitre; Post case constant temperature is at 35 DEG C; Mobile phase: methyl alcohol: the aqueous formic acid=5:95 of 0.1; Flow velocity: 0.2mL/min;
Mass Spectrometry Conditions: ionization source: electron spray (ESI); Ionization mode: negative ion mode; Interface parameters: atomizer: 40 psi; Dry gas: 10Lmin
-l; Dry gas temperature: 350 DEG C; Capillary voltage: 3500 V; Detector voltage: 1.50kV; Ionization mode: ESI Positive nitrogen flow: 1.5L/min.
The testing result of sample 4: malonic acid=0.87%.
Embodiment 5
Carry out quantitatively to metal conditioner complexing agent monoethanolamine:
Adjust ph:
Measure 100ml metal conditioner, drop to after 10g sodium hydrate solid is dissolved in 50ml water in the surface conditioning agent after measuring, adjust ph to 7, obtains alkaline solution;
Pre-service is to eliminate the impact of metallic ion on monoethanolamine:
Drip the strong complexing agent oxine of 0.5g in oxytropism solution, fully mix, be put in by mixed liquor in 80 DEG C of water baths, heating and thermal insulation process, after 5 hours, adds ultrapure water and mends heavy, obtain testing sample 5;
Sample 5 is detected with LC-MS:
Eliminating the sample 5 after metal ion disturbance directly uses LC-MS as detection means, carries out analysis measure the levels of wherein contained monoethanolamine.LC-MS determination step carries out in a conventional manner, and wherein, Details as Follows for each parameter:
Chromatographic condition: chromatographic column selects C18 (150mm × 2.1mm × 5um) chromatographic column; Sample size 10 microlitre; Post case constant temperature is at 35 DEG C; Mobile phase: methyl alcohol: the aqueous formic acid=5:95 of 0.1; Flow velocity: 0.2mL/min;
Mass Spectrometry Conditions: ionization source: electron spray (ESI); Ionization mode: negative ion mode; Interface parameters: atomizer: 40 psi; Dry gas: 10Lmin
-l; Dry gas temperature: 350 DEG C; Capillary voltage: 3500 V; Detector voltage: 1.50kV; Ionization mode: ESI Positive nitrogen flow: 1.5L/min.
The testing result of sample 5: monoethanolamine=0.89%.
Monoethanolamine is extremely unstable in acid condition, and make slaine-monoethanolamine complex system be destroyed under the condition of 4 at pH, the slaine in complex system is free out, promotes the Complexation Efficiency of strong complexing agent.
Embodiment 6
Relative standard deviation (RSD) is tested
To sample 1 and 3 respectively according to embodiment 1, embodiment 3 repeat 6 times independently pre-service to prepare solution to be detected, and carry out analysis mensuration respectively, statistical treatment is carried out to 6 measurement results and assesses precision of the present invention according to relative standard deviation (RSD), the results are shown in following table:
As seen from the above table, RSD < 2%, it shows that precision of the present invention is good, and operation is succinct easily to be grasped, and repeatedly the sample solution measurement result prepared of independent operation is consistent, and repeatability, repeatability are good.
Embodiment 7
Add the test of slaine impact
First carry out pre-service to sample 1 and 4 according to embodiment 1, embodiment 4 prepare solution to be detected and carry out analysis mensuration, then in its primary sample, artificially add the metallic impurity of the iron of 50mg/L, copper, nickel respectively, again carry out pre-service according to embodiment 1, embodiment 4 again prepare solution to be detected and carry out analysis mensuration, relatively add the measurement result of both sides before and after metallic impurity, in order to verify that this method eliminates the actual effect of slaine impact, result sees table:
Unit: %
As seen from the above table, it is basically identical that metallic impurity add front and back sample tests result, indicates that the present invention effectively can eliminate the impact of slaine, have good reliability.
The present invention utilizes acid that metal conditioner is adjusted to pH=7-9, this not only makes the strong complexing agent complexes effect in the present invention strong, and pH adjusting agent also has the ability of complexation heavy metal ion, complexation of metal ions common with strong complexing agent, promotes the Complexation Efficiency of strong complexing agent.
Although illustrate and describe the present invention in conjunction with the embodiments, the present invention is not limited thereto.When not departing from spirit of the present invention and instruction, amendment and distortion can be made to embodiment.Scope of the present invention is by claim and equivalents thereof.
Claims (4)
1. the quantivative approach of malonic acid in metal conditioner, is characterized in that, comprise the following steps:
A) in metal conditioner, drip strong complexing agent, fully mix, obtain mixed liquor;
B) be put in by mixed liquor in 80 DEG C of water baths, heating and thermal insulation process, after 1-2 hour, adds ultrapure water and mends heavy, obtain solution to be measured;
Wherein, metal conditioner is primarily of slaine, complexing agent, buffering agent, stabilizing agent, pH value regulator composition; Quantivative approach is:
HPLC detects, chromatographic condition: 250mm × 4.6mm × 5um C
18chromatographic column; Sample size 10 microlitre; Post case constant temperature is at 35 DEG C; Mobile phase is, the potassium dihydrogen phosphate aqueous solution=5:95 of methyl alcohol: 15mmol; Flow velocity: 0.8mL/min; Determined wavelength: 204nm or MS detects.
2. the quantivative approach of malonic acid in metal conditioner, is characterized in that, comprise the following steps:
A) in metal conditioner, drip pH adjusting agent, adjust ph, to 7-9, obtains alkaline solution;
B) in alkaline solution, add strong complexing agent, fully mix, obtain mixed liquor;
C) be put in by mixed liquor in 80 DEG C of water baths, heating and thermal insulation process, after 1-2 hour, adds ultrapure water and mends heavy, obtain solution to be measured;
Wherein, metal conditioner is primarily of slaine, complexing agent, buffering agent, stabilizing agent, pH value regulator composition; Quantivative approach is:
HPLC detects, chromatographic condition: 250mm × 4.6mm × 5um C
18chromatographic column; Sample size 10 microlitre; Post case constant temperature is at 35 DEG C; Mobile phase is, the potassium dihydrogen phosphate aqueous solution=5:95 of methyl alcohol: 15mmol; Flow velocity: 0.8mL/min; Determined wavelength: 204nm or MS detects.
3., according to the quantivative approach of malonic acid in the metal conditioner in claim 1 or 2 described in any one claim, it is characterized in that, described strong complexing agent be selected from phytic acid, Phen, oxine one or more.
4. the quantivative approach of malonic acid in metal conditioner according to claim 2, is characterized in that, described acidity regulator be selected from NaOH, sodium bicarbonate, sodium carbonate, sal tartari one or more.
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