CN104502474A - Liquid chromatographic detection method for diphenyl ketone ultraviolet-proof finishing agents in textile - Google Patents
Liquid chromatographic detection method for diphenyl ketone ultraviolet-proof finishing agents in textile Download PDFInfo
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Abstract
The invention discloses a liquid chromatographic detection method for diphenyl ketone ultraviolet-proof finishing agents in a textile. The liquid chromatographic detection method for the diphenyl ketone ultraviolet-proof finishing agents in the textile comprises the following steps: 1) preparing a to-be-tested sample solution; 2) preparing a standard solution, and thus mixed standard working solution of eight diphenyl ketone ultraviolet-proof finishing agents concentration of which are 0.01-100Mug/mL respectively is prepared and is taken as gradient standard solution; 3) injecting the gradient standard solution into a liquid chromatograph, measuring by adopting a photodiode array detector, determining the peak positions of the eight diphenyl ketone ultraviolet-proof finishing agents, recording corresponding peak area, thereby obtaining a standard curve equation by taking concentration as a horizontal ordinate and the peak area as a vertical coordinate; and 4) determining the eight diphenyl ketone ultraviolet-proof finishing agents in supernate obtained in the step 1) according to a method described in the step 3) and peak areas of the eight diphenyl ketone ultraviolet-proof finishing agents, and calculating according to the standard curve equation obtained in the step 3), and thus contents of the diphenyl ketone ultraviolet-proof finishing agents in the to-be-tested sample are obtained.
Description
Technical field
The present invention relates to a kind of liquid phase chromatography detection method being applicable to benzophenone anti-ultraviolet finishing agent in textile.
Background technology
In recent years due to Ozone hole, ultraviolet strengthens, and ultraviolet radiation preventing is more and more subject to people's attention, and anti-ultraviolet function textile is also subject to the favor of people.Ultraviolet is a kind of High energy electromagnetic ripple, and expose under ultraviolet light for a long time, skin pathology can occur, and organic molecule light degradation can occur.The anti-ultraviolet function of pupil's haberdashery has even been listed in legal provision, the importance of textile antiultraviolet as can be seen here by the states such as Japan, the U.S..Textile anti-uv finishing generally has two kinds of methods, and one utilizes inorganic pigment to be mechanically coated on textile surface, as zinc paste, titania etc., with light reflection ultraviolet; Another kind utilizes organism, can absorb the ultraviolet light of ultraviolet light particularly 290nm ~ 400nm, and carry out energy conversion, with form of thermal energy or harmless low-energy radiation by fault offset or consumption.Benzophenone anti-ultraviolet finishing agent is a most widely used class in anti-ultraviolet finishing agent, feature is the derivant all containing O-hydroxyl-diphenyl ketone, there is monohydroxy, two hydroxyl, trihydroxy, the derivants such as tetrahydroxy, principal item has: 2, 4-dihydroxy benaophenonel, ESCALOL 567, 2-hydroxyl-4-octyloxybenzophenone, 2-hydroxyl-4-dodecyloxy benzophenones, 2, 2 '-dihydroxy-4-methoxy benzophenone, 2, 2 '-dihydroxy-4, 4 '-dimethoxy-benzophenone, 2, 2 '-4, 4 '-tetrahydroxybenzophenone, 5-chlorine-2-hydroxyl benzophenone etc.
Anti-ultraviolet finishing agent as functional textile should have following characteristics: safety non-toxic, to no skin irritation and allergic reaction; Absorption ultraviolet range is wide, and absorption efficiency is high; Heat, light and chemicals are stablized, without photocatalysis; Colourless change, does not affect whiteness, colour fastness, feel and brute force; Washability is good.But also lack desirable detection method at present, for the safety evaluation also rarely seen report of anti-ultraviolet finishing agent.Conventional organic anti-ultraviolet finishing agent has potential harmfulness to ecologic environment, can affect water body COD value and biodegradability.
In China, benzophenone anti-ultraviolet finishing agent due to combination property better, price is low, applied widely, in anti-ultraviolet finishing agent, occupy critical role.Abroad, benzophenone anti-ultraviolet finishing agent has the history of more than 50 year, is widely used, and manufacturer is numerous, and output is comparatively large, great variety of goods, once commercially absolute advantage.In recent years, although other kind anti-ultraviolet finishing agent constantly occurs, but the output of benzophenone anti-ultraviolet finishing agent is also in continuous expansion, according to reports, on foreign market, benzophenone anti-ultraviolet finishing agent still rises with the speed of 5%, and the output as the U.S. accounts for 40% of light stabilizer, and the output of Japan accounts for 50% of light stabilizer.But benzophenone compound has pungency and anesthetic action, Long Term Contact there will be headache, Nausea and vomiting, dizzy, drowsiness, insensitive, and mood irritability waits reaction.Especially nearest research shows: benzophenone compound is a kind of environment incretion interferent, it can cause the dysendocrinism comprising the various biologies such as the mankind, poultry and wild animal, and the decline of human reproductive systems's function and Animals Male feminisation are also relevant with the discharge of the incretion interferents such as benzophenone.Therefore, the impact of benzophenone compound on the mankind and ecologic environment can not be despised.
At present, the domestic research report that there is no the liquid chromatography detecting method of benzophenone anti-ultraviolet finishing agent in relevant textile.The ecology of textile product is produced, ecological consumption and ecology process are inexorable trends, developing ecology textile is related to the foreign exchange earning level of China's textile product, be related to industry value chain strategy, also will play considerable effect to China's textile industry of running business big and strong.In order to safeguard national basic security, ensureing human health, preserve the ecological environment; break through the TBT (Technical Barriers to Trade) of developed country; also in order to carry out cleaner production and enterprise self-technique development level, research fabric in benzophenone anti-ultraviolet finishing agent detection method have important practical significance.
Summary of the invention
The technical problem to be solved in the present invention is to provide a kind of qualitative, quantitative, and what clever length was high is applicable to the liquid phase chromatography that in textile, benzophenone anti-ultraviolet finishing agent detects.
In order to solve the problems of the technologies described above, the invention provides the liquid phase chromatography detection method of benzophenone anti-ultraviolet finishing agent in a kind of textile, comprising the following steps:
1), testing sample solution is prepared:
(1) testing sample is shredded rear mixing, obtain sample;
(2) 0.1 ~ 5.0g (being preferably 1.0g) sample is taken, be accurate to 0.01g, be placed in the extraction apparatus (glass extraction apparatus) of band screw top, add methylene chloride (as extraction agent), thus make all samples be immersed in methylene chloride;
The solid-liquid ratio of described sample and methylene chloride is: 1g/10 ~ 50mL (being preferably 1g/30mL);
(3) after extraction apparatus being sealed, ultrasonic extraction 10 ~ 60min (being preferably 30min) in ultrasonic generator; After being cooled to room temperature, by closely dry for extract reduced pressure concentration in 30 ~ 50 DEG C of (being preferably 40 DEG C) water-baths, then use N
2dry up;
(4) 1 ~ 10mL (being preferably 2mL) organic solvent (methyl alcohol or acetonitrile) vortex dissolving step (3) gains (referred to as residue) are added, with 0.20 ~ 0.45 μm of filtering head, sample liquid is filtered, obtain supernatant; Object carries out qualitative and quantitative analysis for Ultra Performance Liquid Chromatography instrument;
2), preparation standard solution:
(1) with organic solvent (methyl alcohol or acetonitrile) 8 kinds of benzophenone anti-ultraviolet finishing agents (being standard substance, as shown in table 1) dissolvings respectively, 8 kinds of Standard Stock solutions that concentration is 100 ~ 1000 μ g/mL are mixed with;
(2) with organic solvent (methyl alcohol or acetonitrile), above-mentioned 8 kinds of Standard Stock solutions are dissolved, thus the concentration being mixed with 8 kinds of benzophenone anti-ultraviolet finishing agents is the hybrid standard working solution of 0.01 ~ 100 μ g/mL as gradient standard solution;
Remarks illustrate: in often kind of hybrid standard working solution (that is, each gradient standard solution), the concentration of 8 kinds of benzophenone anti-ultraviolet finishing agents is consistent;
3), by gradient standard solution injection liquid chromatography, photodiode array detector (PDA) measures, that determines 8 kinds of benzophenone anti-ultraviolet finishing agents goes out peak position, the peak area that record is corresponding, take concentration as horizontal ordinate, peak area is ordinate, production standard curvilinear equation;
4), step 1 is got) supernatant of gained is by step 3) method measures each benzophenone anti-ultraviolet finishing agent and peak area thereof in supernatant, according to step 3) the typical curve equation of gained calculates, and obtains the content of each benzophenone anti-ultraviolet finishing agent in testing sample.
Improvement as the liquid phase chromatography detection method of benzophenone anti-ultraviolet finishing agent in textile of the present invention: described 8 kinds of benzophenone anti-ultraviolet finishing agents: 2,4-dihydroxy benzophenone, (2-hydroxy-4-methoxyphenyl) phenyl ketone, Octabenzone, 2,2'-hydroxyl-4-methoxy benzophenone, 2,2'-dihydroxy-4,4'-dimethoxy-benzophenone, 2,2', 4,4'-tetrahydroxybenzophenone, 2-hydroxyl-5-chlorobenzophenone and 2-hydroxyl-4-dodecyloxy benzophenones;
Further improvement as the liquid phase chromatography detection method of benzophenone anti-ultraviolet finishing agent in textile of the present invention:
Described liquid phase chromatogram condition (that is, Ultra Performance Liquid Chromatography (UPLC) detect liquid phase chromatogram condition) is: determined wavelength: 190 ~ 400nm; Flow velocity: 0.2 ~ 0.8mL/min (being preferably 0.3mL/min); Column temperature: 20 ~ 45 DEG C (being preferably 40 DEG C); Sampling volume: 1 ~ 10 μ L (being preferably 5 μ L);
Mobile phase is made up of mobile phase A and Mobile phase B; Mobile phase A is acetonitrile; Mobile phase B is volumetric concentration is 0.05 ~ 1% (volume %) aqueous formic acid;
Gradient elution program is: 0 ~ 0.5min, 10%A ~ 75%A; 0.5 ~ 3.5min, 75%A; 3.5 ~ 4min, 75%A ~ 100%A; 4 ~ 8.5min, 100%A; 8.5 ~ 8.6min, 100%A ~ 10%A; 8.6 ~ 10min, 10%A.
Further improvement as the liquid phase chromatography detection method of benzophenone anti-ultraviolet finishing agent in textile of the present invention: described liquid-phase chromatographic column is: Acquity
bEH C
18, 100mm × 2.1mm, 1.7 μm of chromatographic columns or quite person.
Further improvement as the liquid phase chromatography detection method of benzophenone anti-ultraviolet finishing agent in textile of the present invention: described organic solvent is methyl alcohol, acetonitrile.
Further improvement as the liquid phase chromatography detection method of benzophenone anti-ultraviolet finishing agent in textile of the present invention: described step 1) in, testing sample is shredded into the small pieces of 5mm × 5mm, as sample.
Table 1.8 kind of benzophenone anti-ultraviolet finishing agent chemical information table
The present invention compared with prior art has following remarkable result:
(1) this method utilizes the photodiode array detector of Ultra Performance Liquid Chromatography (PDA) can gather full three-dimensional spectroscopic data, full spectral range can be gathered in whole chromatogram, the inventive method adopts the full three-dimensional spectroscopic data of the disposable collection of PDA detecting device 8 kinds of benzophenone anti-ultraviolet finishing agents, point wavelength acquisition method relatively, save detection time, improve detection sensitivity.
(2) this method utilizes the peculiar UHV (ultra-high voltage) advantage of Ultra Performance Liquid Chromatography system and BEH post to possess short grained all potential and advantage and hydrophilic feature, its complete compatible pure water phase mobile phase, there is extremely low Bonded Phase run off, especially while raising degree of separation, analysis speed is faster obtained to target compound, because chromatographic peak becomes narrower, peak height is also just higher, thus obtain higher sensitivity, simultaneously, due to UHV (ultra-high voltage) effect, substantially reduce the chromatographic resolution time.
(3) assay method disclosed by the invention is better in 0.01 ~ 10.0 μ g/mL linear relationship, and linearly dependent coefficient is more than 0.99, and method minimum detectability is 0.048mg/kg.
Ultra-performance liquid chromatography of the present invention just can carry out separation determination to 8 kinds of benzophenone anti-ultraviolet finishing agents quickly and accurately in 7 minutes, and method is highly sensitive, easy and simple to handle, accurately and reliably.
Accompanying drawing explanation
Below in conjunction with accompanying drawing, the specific embodiment of the present invention is described in further detail.
Fig. 1 is 8 kinds of benzophenone anti-ultraviolet finishing agent liquid chromatograms.In figure, 1 ~ 8 represents this 8 kinds of benzophenone anti-ultraviolet finishing agent liquid respectively.
Fig. 2 is 8 kinds of benzophenone anti-ultraviolet finishing agent ultraviolet spectrograms.In Fig. 2, be followed successively by 2 from top to bottom, 2', 4,4'-tetrahydroxybenzophenone, 2,4-dihydroxy benzophenone, 2,2'-hydroxyl-4-methoxy benzophenones, (2-hydroxy-4-methoxyphenyl) phenyl ketone, 2, the ultraviolet spectrogram of 2'-dihydroxy-4,4'-dimethoxy-benzophenone, 2-hydroxyl-5-chlorobenzophenone, Octabenzone, 2-hydroxyl-4-dodecyloxy benzophenones.
Embodiment
Below in conjunction with embodiment and comparative example, the present invention is set forth, but protection scope of the present invention is not only confined to following examples.Person of an ordinary skill in the technical field, according to content disclosed by the invention, all can realize result of the present invention.
1 reagent and material
Except as otherwise noted, in analysis, agents useful for same is HPLC level, and useful water is one-level water.
1.1 methyl alcohol.
1.2 acetonitrile.
1.3 methylene chloride.
1.4 benzophenone anti-ultraviolet finishing agent standard substances: 2, 4-dihydroxy benaophenonel (namely, 2, 4-dihydroxy benzophenone), ESCALOL 567 (namely, (2-hydroxy-4-methoxyphenyl) phenyl ketone), 2-hydroxyl-4-octyloxybenzophenone (namely, Octabenzone), 2-hydroxyl-4-dodecyloxy benzophenones, 2, 2 '-dihydroxy-4-methoxy benzophenone, 2, 2 '-dihydroxy-4, 4 '-dimethoxy-benzophenone, 2, 2 '-4, 4 '-tetrahydroxybenzophenone, 5-chlorine-2-hydroxyl benzophenone (namely, 2-hydroxyl-5-chlorobenzophenone) etc., purity all >=97.5%.
1.5 standard reserving solutions: above-mentioned 8 kinds of benzophenone anti-ultraviolet finishing agent standard substances are handled as follows respectively: respectively 8 kinds of benzophenone anti-ultraviolet finishing agent standard substances are mixed with the Standard Stock solutions that concentration is about 1000 μ g/mL with methyl alcohol or other suitable solvents (such as acetonitrile); Respectively get appropriate above-mentioned Standard Stock solutions methyl alcohol again and be mixed with the hybrid standard stock solution that concentration is about 100 μ g/mL.
1.6 standard working solution: hybrid standard storing solution methyl alcohol is mixed with the hybrid standard working solution that concentration is respectively 1 μ g/mL, 3 μ g/mL, 5 μ g/mL, 7 μ g/mL and 10 μ g/mL.
Note: standard stock solution keeps in Dark Place at 4 DEG C, the term of validity is 12 months.Standard working solution keeps in Dark Place at 4 DEG C, and can be mixed with more suitably concentration as required, is valid for three months.
2 instrument and equipments
2.1 Ultra Performance Liquid Chromatography instrument (UPLC): band photodiode array detector (PDA).
2.2 ultrasonic generators: frequency of operation is 40kHz.
2.3 analytical balances: sensibility reciprocal is 0.0001g and 0.01g.
2.4 extraction apparatuss: the glass tube of band screw top, 50mL.
2.5 rotary vacuum evaporator.
2.6 organic phase filtering membranes: 0.45 μm.
Embodiment 1, a kind of liquid phase chromatography detection method being applicable to 8 kinds of benzophenone anti-ultraviolet finishing agents in textile, carry out following steps successively:
1), testing sample solution is prepared:
(1) get representational sample, shredded into about 5mm × 5mm small pieces, mixing;
(2) take that 1.0g is above-mentioned shreds sample, be accurate to 0.01g, be placed in the glass extraction apparatus of band screw top, add 30mL methylene chloride, making all samples be immersed in liquid, after being sealed by extraction apparatus, is ultrasonic extraction 30min in 40kHz ultrasonic generator in frequency;
That is, the solid-liquid ratio of described testing sample and extraction agent is: 1g/30mL;
(3), after being cooled to room temperature, reduced pressure in 40 DEG C of water-baths by extract (pressure is 90mbar) is concentrated near dry, then uses N
2dry up, add 2mL methyl alcohol vortex dissolved residue;
(4) after being filtered by sample liquid with 0.45 μm of filtering head, the filtration sample liquid of gained is placed in sample injection bottle and seals, and object carries out qualitative and quantitative analysis for Ultra Performance Liquid Chromatography instrument;
Remarks illustrate: the volume filtering sample liquid is 2ml, namely ignores to the very little change of the volume that " dissolved residue ", " filtration " cause.
2), preparation standard solution
(1) respectively 8 kinds of benzophenone anti-ultraviolet finishing agent standard substances are mixed with the Standard Stock solutions that concentration is 1000 μ g/mL with methyl alcohol;
(2) respectively get appropriate above-mentioned Standard Stock solutions methyl alcohol and be mixed with the hybrid standard stock solution that concentration is 100 μ g/mL; Remarks illustrate: in hybrid standard stock solution, it is 100 μ g/mL that the concentration of 8 kinds of benzophenone anti-ultraviolet finishing agent standard substances is concentration;
(3) hybrid standard storing solution methyl alcohol is mixed with the gradient standard working solution that concentration is respectively 1 μ g/mL, 3 μ g/mL, 5 μ g/mL, 7 μ g/mL and 10 μ g/mL;
3), gradient standard solution is injected super effect liquid phase chromatogram instrument, measure with band photodiode array detector (PDA), that determines various benzophenone anti-ultraviolet finishing agent goes out peak position, the peak area that record is corresponding, take concentration as horizontal ordinate, peak area is ordinate, production standard curvilinear equation.Specific as follows:
A) chromatographic column: Acquity
bEH C
18, 100mm × 2.1mm, 1.7 μm of chromatographic columns or quite person;
B) flow velocity: 0.3mL/min;
C) detecting device: photodiode array detector (PDA);
D) determined wavelength: 190 ~ 400nm;
E) column temperature: 40 DEG C;
F) sampling volume: 5 μ L;
G) mobile phase A: acetonitrile; Mobile phase B: concentration is 0.05% (volume %) aqueous formic acid;
H) gradient elution program is in table 2.
Table 2. Ultra Performance Liquid Chromatography gradient elution program table
| Time (min) | Flow velocity (mL/min) | Acetonitrile (%) | Water (%) | Curve type |
| 0 | 0.3 | 10 | 90 | Initial |
| 0.5 | 0.3 | 75 | 25 | 6 |
| 3.5 | 0.3 | 75 | 25 | 6 |
| 4 | 0.3 | 100 | 0 | 6 |
| 8.5 | 0.3 | 100 | 0 | 6 |
| 8.6 | 0.3 | 10 | 90 | 6 |
| 10 | 0.3 | 10 | 90 | 1 |
Ultra-performance liquid chromatography disclosed by the invention is 1,3 in concentration range, 5,7, and during 10 μ g/mL, 8 kinds of benzophenone anti-ultraviolet finishing agent linear relationships are all better, in table 3.
Table 3. ultra-performance liquid chromatography measures linear equation and the linearly dependent coefficient of 8 kinds of benzophenone anti-ultraviolet finishing agents
4), step 1 is got) the filtration sample liquid (supernatant) of gained is by step 3) 8 kinds of benzophenone anti-ultraviolet finishing agents measuring in testing sample solution of method (namely substitute the gradient standard solution of 5 μ L with the filtration sample liquid of 5 μ L, all the other are equal to), utilize the typical curve (linear equation) set up, obtain 8 kinds of benzophenone anti-ultraviolet finishing agent content in sample liquid; Extension rate (conversion relation namely between sample 1g and supernatant) per sample again; Obtain 8 kinds of benzophenone anti-ultraviolet finishing agent content in testing sample.
5), qualitative analysis
Corresponding step 4), under same test conditions, in sample, determinand has identical retention time with the standard substance detected simultaneously, and the ultraviolet spectrogram of the ultraviolet spectrogram of sample and standard solution compares, if ultraviolet spectrogram is also consistent, then can judge in sample, to there is corresponding determinand.
6), quantitative test
Corresponding step 4), this method adopts quantified by external standard method, according to measured matter content situation in sample liquid, the standard working solution of selected concentration comparable, standard working solution and sample liquid equal-volume are joined and injects sample and measure, standard working solution and treat that the response of 8 kinds of benzophenone anti-ultraviolet finishing agents in sample measuring liquid all should in the range of linearity of instrument.
Note 1: if the detection response of sample liquid exceeds the range of linearity that instrument detects, can suitably dilute rear mensuration.
Note 2: under above-mentioned chromatographic condition, the Ultra Performance Liquid Chromatography figure of 8 kinds of benzophenone anti-ultraviolet finishing agents and corresponding ultraviolet spectrogram are see Fig. 1 and Fig. 2.
7), detect and track
Concentration limit (LOD) is determined with 3 times of signal to noise ratio (S/N ratio)s (S/N=3), determine minimum quantitative concentrations (LOQ) with 10 times of signal to noise ratio (S/N ratio)s (S/N=10), this method is to being applicable to the mensuration lower bound of liquid phase chromatography detection method of 8 kinds of benzophenone anti-ultraviolet finishing agents in textile in table 3.
Remarks illustrate: LOD calculates with 3 times of signal to noise ratio (S/N ratio)s (S/N=3), and LOQ calculates with 10 times of signal to noise ratio (S/N ratio)s (S/N=10), generally determines detect and track with LOD.
Experiment 1, the experiment of sample TIANZHU XINGNAO Capsul and Precision Experiment
The standard mixed solution of 8 kinds of benzophenone anti-ultraviolet finishing agents is added respectively in blank terylene sample, add concentration and be respectively 1mg/kg, 5mg/kg and 10mg/kg, each concentration arranges 6 repetitions, by above-mentioned pre-treatment and analytical approach, measure the TIANZHU XINGNAO Capsul of 8 kinds of benzophenone anti-ultraviolet finishing agents in terylene sample, in table 4.
The anti-ultraviolet finishing agent recovery and the relative standard deviation (n=6) of variable concentrations is added in table 4. terylene sample
Experiment 2, actual sample detect
Several parts of ultra violet resistant clothes samples randomly drawed in laboratory are (known in advance: sample 1# is containing 2,2', 4,4'-tetrahydroxybenzophenone 250mg/kg, sample 2 contains 2 containing 2,4-dihydroxy benzophenone 250mg/kg, sample 3#, 2', 4,4'-tetrahydroxybenzophenone 350mg/kg, sample 4# detects 2,2'-hydroxyl-4-methoxy benzophenone 450mg/kg), by aforesaid operations step, carry out extracting, concentrate, constant volume, each sample parallel 6 times, measure with ultra-performance liquid chromatography, the sample determination obtained the results are shown in Table 5.
Table 5. actual sample measurement result
ND: represent and do not detect.
According to table 5, we learn: sample 1# detects 2,2', 4,4'-tetrahydroxybenzophenone 245.1mg/kg, sample 2 detects 2,4-dihydroxy benzophenone 254.3mg/kg, sample 3# detects 2,2', 4,4'-tetrahydroxybenzophenone 347.9mg/kg, sample 4# detect 2,2'-hydroxyl-4-methoxy benzophenone 456.8mg/kg.
Finally, it is also to be noted that what enumerate above is only several specific embodiments of the present invention.Obviously, the invention is not restricted to above embodiment, many distortion can also be had.All distortion that those of ordinary skill in the art can directly derive from content disclosed by the invention or associate, all should think protection scope of the present invention.
Claims (6)
1. the liquid phase chromatography detection method of benzophenone anti-ultraviolet finishing agent in textile, is characterized in that comprising the following steps:
1), testing sample solution is prepared:
(1) testing sample is shredded rear mixing, obtain sample;
(2) take 0.1 ~ 5.0g sample, be accurate to 0.01g, be placed in the extraction apparatus of band screw top, add methylene chloride, thus make all samples be immersed in methylene chloride;
The solid-liquid ratio of described sample and methylene chloride is: 1g/10 ~ 50mL;
(3) after extraction apparatus being sealed, ultrasonic extraction 10 ~ 60min in ultrasonic generator; After being cooled to room temperature, by closely dry for extract reduced pressure concentration in 30 ~ 50 DEG C of water-baths, then use N
2dry up;
(4) add 1 ~ 10mL organic solvent vortex dissolving step (3) gains, with 0.20 ~ 0.45 μm of filtering head, sample liquid is filtered, obtain supernatant;
2), preparation standard solution:
(1) with organic solvent 8 kinds of benzophenone anti-ultraviolet finishing agents dissolvings respectively, 8 kinds of Standard Stock solutions that concentration is 100 ~ 1000 μ g/mL are mixed with;
(2) with organic solvent, above-mentioned 8 kinds of Standard Stock solutions are dissolved, thus the concentration being mixed with 8 kinds of benzophenone anti-ultraviolet finishing agents is the hybrid standard working solution of 0.01 ~ 100 μ g/mL as gradient standard solution;
3), by gradient standard solution injection liquid chromatography, photodiode array detector measures, and that determines 8 kinds of benzophenone anti-ultraviolet finishing agents goes out peak position, the peak area that record is corresponding, take concentration as horizontal ordinate, peak area is ordinate, production standard curvilinear equation;
4), step 1 is got) supernatant of gained is by step 3) method measures each benzophenone anti-ultraviolet finishing agent and peak area thereof in supernatant, according to step 3) the typical curve equation of gained calculates, and obtains the content of each benzophenone anti-ultraviolet finishing agent in testing sample.
2. the liquid phase chromatography detection method of benzophenone anti-ultraviolet finishing agent in textile according to claim 1, it is characterized in that: described 8 kinds of benzophenone anti-ultraviolet finishing agents: 2,4-dihydroxy benzophenone, (2-hydroxy-4-methoxyphenyl) phenyl ketone, Octabenzone, 2,2'-hydroxyl-4-methoxy benzophenone, 2,2'-dihydroxy-4,4'-dimethoxy-benzophenone, 2,2', 4,4'-tetrahydroxybenzophenone, 2-hydroxyl-5-chlorobenzophenone and 2-hydroxyl-4-dodecyloxy benzophenones.
3. the liquid phase chromatography detection method of benzophenone anti-ultraviolet finishing agent in textile according to claim 2, is characterized in that:
Described liquid phase chromatogram condition is: determined wavelength: 190 ~ 400nm; Flow velocity: 0.2 ~ 0.8mL/min; Column temperature: 20 ~ 45 DEG C; Sampling volume: 1 ~ 10 μ L;
Mobile phase is made up of mobile phase A and Mobile phase B; Mobile phase A is acetonitrile; Mobile phase B is volumetric concentration is 0.05 ~ 1% aqueous formic acid;
Gradient elution program is: 0 ~ 0.5min, 10%A ~ 75%A; 0.5 ~ 3.5min, 75%A; 3.5 ~ 4min, 75%A ~ 100%A; 4 ~ 8.5min, 100%A; 8.5 ~ 8.6min, 100%A ~ 10%A; 8.6 ~ 10min, 10%A.
4. the liquid phase chromatography detection method of benzophenone anti-ultraviolet finishing agent in textile according to claim 3, is characterized in that: described liquid-phase chromatographic column is:
100mm × 2.1mm, 1.7 μm of chromatographic columns or quite person.
5. the liquid phase chromatography detection method of benzophenone anti-ultraviolet finishing agent in textile according to claim 4, is characterized in that: described organic solvent is methyl alcohol, acetonitrile.
6. the liquid phase chromatography detection method of benzophenone anti-ultraviolet finishing agent in textile according to claim 5, is characterized in that: described step 1) in, testing sample is shredded into the small pieces of 5mm × 5mm, as sample.
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| CN105021725A (en) * | 2015-07-03 | 2015-11-04 | 中华人民共和国台州出入境检验检疫局 | Liquid chromatography-tandem mass spectrometry method for detection of specific total migration of nine ultraviolet absorbers |
| CN105021753A (en) * | 2015-07-03 | 2015-11-04 | 中华人民共和国台州出入境检验检疫局 | Liquid chromatography UV method for detection of specific migration of 9 specific UV absorbers |
| CN105021753B (en) * | 2015-07-03 | 2016-07-13 | 中华人民共和国台州出入境检验检疫局 | Liquid chromatograph ultraviolet method measures 9 kinds of ultraviolet absorber specific transfer metering methods |
| CN109212105A (en) * | 2018-11-15 | 2019-01-15 | 吴刚 | The LC-MS detection method of textile salicylic acid esters anti-ultraviolet finishing agent |
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