CN105259290A - Detecting method for cyclic methyl siloxane in surface water - Google Patents
Detecting method for cyclic methyl siloxane in surface water Download PDFInfo
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Abstract
The invention provides a detecting method for cyclic methyl siloxane in surface water and relates to a detecting method for cyclic methyl siloxane. The invention aims to solve the problems of long detecting time and incapability of accurate, qualitative and quantitative detecting under the existence of impurities of the present method for detecting the methyl siloxane. The detecting method comprises the following steps: 1) utilizing a liquid-liquid extraction method to preprocess a to-be-detected sample; 2) setting GC-MS-MS instrument parameters; 3) detecting a standard liquid; 4) detecting the to-be-detected sample. The detecting method for cyclic methyl siloxane in surface water, provided by the invention, has the characteristics of short detecting time, simplicity in operation, good preprocessing effect and capability of effectively eliminating interference and accurately, qualitatively and quantitatively detecting the cyclic methyl siloxane.
Description
Technical field
The present invention relates to a kind of detection method of cyclic methyl siloxane.
Background technology
Methylsiloxane is divided into chain and ring-type on molecular structure, and chain is mainly L3-L15, and ring-type is mainly D3-D7, is all alternately arranged as skeleton using silicone atom, silicon atom is directly connected with methyl group, forms compound.All siloxane are Prof. Du Yucang, the silicone oil, silica gel etc. of different polymerization degree is aggregated into by the methylsiloxane of Primary Speciation, be present in the most cosmetics such as emulsion, face cream, mildy wash, shampoo, hair conditioner, toilet paper, lipstick, nail polish, shower cream, perfume, sunscreen product, antiperspirant and commodity, small part is also applied to the fields such as building, automobile, food as defomaing agent, lubricant, brilliant polish etc. more.
Due to methylsiloxane hydrophobic oleophobic, there is high volatile volatile, the amount of the methylsiloxane in the environment such as cosmetics and personal care articles nearly 90% can evaporate in air, and remaining 10% can enter in sanitary sewage, Environment Canada in 2008, healthy portion, and European Union in 2009 carries out risk assessment to part silicone, unanimously think that volatile methyl siloxane is the priority pollutant in environment, list " essence elimination " list in.
In recent years, China's methylsiloxane output has accounted for the whole world 1/4, and wherein the ring-type gross output value is that the whole world is the first.Methylsiloxane has genotoxicity, can grow distance drift in an atmosphere.Therefore, methylsiloxane is very serious to the potential hazard of China.
At present, FID, GC, GC-FID, GC-MS are mainly contained to the detection method of methylsiloxane.Above-mentioned cannot be accurately qualitative when there being impurity to exist.
Summary of the invention
The detection time that the method that the object of the invention is to solve existing detection methylsiloxane exists is longer and cannot the problem of accurate qualitative, quantitative when having impurity to exist, and provides the detection method of cyclic methyl siloxane in a kind of surface water.
In a kind of surface water of the present invention, the detection method of cyclic methyl siloxane is carried out according to the following steps:
One, liquid-liquid extraction method is utilized to carry out pre-service to testing sample: 1. to carry out first time extraction with extract methylene chloride to testing sample, shake during extraction, static layering, obtain the first organic phase and the more than first phase; Step 1. described in extract and the volume ratio of testing sample be 1:10; 2. with extract methylene chloride to step 1. obtain more than first carry out mutually second time extraction, shake during extraction, static layering, obtain Second Organic Phase and the more than second phase; Step 1. described in extract and step 2. described in the volume ratio of extract be 2:1; 3. with extract methylene chloride to step 2. obtain more than second carry out mutually third time extraction, shake during extraction, static layering, obtain the 3rd organic phase and the more than the 3rd phase; Step 1. described in extract and step 3. described in the volume ratio of extract be 2:1; 4. the first organic phase, Second Organic Phase and the 3rd organic phase are merged, then in the organic phase merged, isooctane is added, obtain the organic phase adding isooctane, then Rotary Evaporators is first used to concentrate the organic phase adding isooctane, be concentrated into 2mL, obtain concentrated rear sample, re-use Nitrogen evaporator and concentrated rear sample is concentrated, be concentrated into 1mL, obtain processing rear testing sample; Described isooctane and step 1. described in the volume ratio of extract be 1:20;
Two, GC-MS-MS instrument parameter setting: 1. 180 DEG C ~ 220 DEG C are set as to gas chromatographic sample introduction mouth temperature, sample size is set as 2 μ L, pressure setting is 13Psi ~ 14Psi, pattern is set as that pulse is not shunted, sample introduction pulse is 38Psi ~ 42Psi, time is 7min ~ 9min, shunting outlet purge flow rate is set as 48mL/min ~ 52mL/min, purge time is 1.2ms, gas chromatograph is opened carrier gas and is saved after enabling 3min ~ 4min, carrier gas flux is set as 15mL/min ~ 25mL/min; 2. be set as 1mL/min ~ 1.4mL/min to chromatographic column helium gas flow, average linear velocity is 28cm/sec ~ 29cm/sec, and the hold-up time is 1.5min ~ 2.0min, constant rate, rear operating flux is set as 1.5mL/min, and post case open temp is 35 ~ 45 DEG C, and equilibration time is 0.1min; 3. heating up to chromatographic column Program is set as from temperature is 35 ~ 45 DEG C, 2min ~ 3min is kept at temperature is 35 ~ 45 DEG C, then being 35 ~ 45 DEG C with the heating rate of 20 DEG C/min by temperature, to be warming up to temperature be 200 ~ 240 DEG C, being 200 ~ 240 DEG C with the heating rate of 60 DEG C/min by temperature again, to be warming up to temperature be 250 ~ 300 DEG C, rear running temperature is set as 300 DEG C, and rear working time is 15min; 4. be set as 200 ~ 300 DEG C to the mass ions source temperature of mass detector, the solvent delay time is 3.5min ~ 4min, and broad peak is set as wide, and residence time is set as 100ms; 5. many reaction patterns are set as to the reaction pattern of mass detector, hexamethyl cyclotrisiloxane quota ion to for: 207 → 191, qualitative ion pair is: 207 → 189, collision voltage be: 20eV; Octamethylcy-clotetrasiloxane quota ion to for: 281 → 265, qualitative ion pair is: 281 → 249, collision voltage be: 20eV; Decamethylcyclopentaandoxane quota ion to for: 355 → 267, qualitative ion pair is: 355 → 251, collision voltage be: 20eV; Ten diformazan basic ring six siloxane quota ions to for: 429 → 341, qualitative ion pair is: 429 → 147, collision voltage be: 20eV;
Three, examination criteria liquid: 1. prepare titer a; In described titer a, the mass concentration of hexamethyl cyclotrisiloxane is 5ng/mL, the mass concentration of octamethylcy-clotetrasiloxane is 5ng/mL, the mass concentration of decamethylcyclopentaandoxane is 5ng/mL, the mass concentration of ten diformazan basic ring six siloxane is 5ng/mL; 2. titer b is prepared; In described titer b, the mass concentration of hexamethyl cyclotrisiloxane is 10ng/mL, the mass concentration of octamethylcy-clotetrasiloxane is 10ng/mL, the mass concentration of decamethylcyclopentaandoxane is 10ng/mL, the mass concentration of ten diformazan basic ring six siloxane is 10ng/mL; 3. titer c is prepared; In described titer c, the mass concentration of hexamethyl cyclotrisiloxane is 20ng/mL, the mass concentration of octamethylcy-clotetrasiloxane is 20ng/mL, the mass concentration of decamethylcyclopentaandoxane is 20ng/mL, the mass concentration of ten diformazan basic ring six siloxane is 20ng/mL; 4. titer d is prepared; In described titer d, the mass concentration of hexamethyl cyclotrisiloxane is 50ng/mL, the mass concentration of octamethylcy-clotetrasiloxane is 50ng/mL, the mass concentration of decamethylcyclopentaandoxane is 50ng/mL, the mass concentration of ten diformazan basic ring six siloxane is 50ng/mL; 5. titer e is prepared; In described titer e, the mass concentration of hexamethyl cyclotrisiloxane is 100ng/mL, the mass concentration of octamethylcy-clotetrasiloxane is 100ng/mL, the mass concentration of decamethylcyclopentaandoxane is 100ng/mL, the mass concentration of ten diformazan basic ring six siloxane is 100ng/mL; 6. successively titer a, titer b, titer c, titer d and titer e are detected by concentration gradient with the GC-MS-MS instrument that step 2 sets, obtain the total ion current amount chromatogram of typical curve and titer;
Four, testing sample is detected: when the coefficients R of the regression equation corresponding to the typical curve that step 3 obtains
2when being greater than 0.95, the testing sample after the process obtained step one in GC-MS-MS technology is utilized to carry out the detection of cyclic methyl siloxane type and content, testing sample after the process that step one is obtained is by the injection port of GC-MS-MS instrument, enter in chromatographic column, each component of testing sample decomposition product is separated, enter Mass Spectrometer Method part by the interface of GC-MS-MS instrument after separation and carry out Mass Spectrometer Method, for detecting the time of hexamethyl cyclotrisiloxane after Mass Spectrometer Method starts 3.8min, residence time 100ms, for detecting the time of octamethylcy-clotetrasiloxane after Mass Spectrometer Method starts 4.5min, residence time 100ms, for detecting the time of decamethylcyclopentaandoxane after Mass Spectrometer Method starts 6.0min, residence time 100ms, Mass Spectrometer Method is the time of detection ten diformazan basic ring six siloxane after starting 7.3min, residence time 100ms, obtain the total ion current amount chromatogram of testing sample, the type that can draw cyclic methyl siloxane in testing sample is contrasted by the mass spectrum total ion current spirogram of the titer obtained with step 3, the typical curve obtained by step 3 can obtain the concentration of cyclic methyl siloxane in testing sample.
Beneficial effect of the present invention
The invention provides a kind of method detecting cyclic methyl siloxane in water body, it is short that the method has detection time, simple to operate, and pretreating effect is good, effectively can eliminate interference, accurately to the feature of cyclic methyl siloxane qualitative, quantitative.
Accompanying drawing explanation
Fig. 1 is the canonical plotting of hexamethyl cyclotrisiloxane (D3) in the titer that obtains of test one step 3;
Fig. 2 is the canonical plotting of octamethylcy-clotetrasiloxane (D4) in the titer that obtains of test one step 3;
Fig. 3 is the canonical plotting of decamethylcyclopentaandoxane (D5) in the titer that obtains of test one step 3;
Fig. 4 is the canonical plotting of ten diformazan basic ring six siloxane (D6) in the titer that obtains of test one step 3;
Fig. 5 is the total ion current amount chromatogram of the titer that test one step 3 obtains;
Fig. 6 is the total ion current amount chromatogram of the testing sample that test one step 4 obtains.
Embodiment
Embodiment one: in a kind of surface water of present embodiment, the detection method of cyclic methyl siloxane is carried out according to the following steps:
One, liquid-liquid extraction method is utilized to carry out pre-service to testing sample: 1. to carry out first time extraction with extract methylene chloride to testing sample, shake during extraction, static layering, obtain the first organic phase and the more than first phase; Step 1. described in extract and the volume ratio of testing sample be 1:10; 2. with extract methylene chloride to step 1. obtain more than first carry out mutually second time extraction, shake during extraction, static layering, obtain Second Organic Phase and the more than second phase; Step 1. described in extract and step 2. described in the volume ratio of extract be 2:1; 3. with extract methylene chloride to step 2. obtain more than second carry out mutually third time extraction, shake during extraction, static layering, obtain the 3rd organic phase and the more than the 3rd phase; Step 1. described in extract and step 3. described in the volume ratio of extract be 2:1; 4. the first organic phase, Second Organic Phase and the 3rd organic phase are merged, then in the organic phase merged, isooctane is added, obtain the organic phase adding isooctane, then Rotary Evaporators is first used to concentrate the organic phase adding isooctane, be concentrated into 2mL, obtain concentrated rear sample, re-use Nitrogen evaporator and concentrated rear sample is concentrated, be concentrated into 1mL, obtain processing rear testing sample; Described isooctane and step 1. described in the volume ratio of extract be 1:20;
Two, GC-MS-MS instrument parameter setting: 1. 180 DEG C ~ 220 DEG C are set as to gas chromatographic sample introduction mouth temperature, sample size is set as 2 μ L, pressure setting is 13Psi ~ 14Psi, pattern is set as that pulse is not shunted, sample introduction pulse is 38Psi ~ 42Psi, time is 7min ~ 9min, shunting outlet purge flow rate is set as 48mL/min ~ 52mL/min, purge time is 1.2ms, gas chromatograph is opened carrier gas and is saved after enabling 3min ~ 4min, carrier gas flux is set as 15mL/min ~ 25mL/min; 2. be set as 1mL/min ~ 1.4mL/min to chromatographic column helium gas flow, average linear velocity is 28cm/sec ~ 29cm/sec, and the hold-up time is 1.5min ~ 2.0min, constant rate, rear operating flux is set as 1.5mL/min, and post case open temp is 35 ~ 45 DEG C, and equilibration time is 0.1min; 3. heating up to chromatographic column Program is set as from temperature is 35 ~ 45 DEG C, 2min ~ 3min is kept at temperature is 35 ~ 45 DEG C, then being 35 ~ 45 DEG C with the heating rate of 20 DEG C/min by temperature, to be warming up to temperature be 200 ~ 240 DEG C, being 200 ~ 240 DEG C with the heating rate of 60 DEG C/min by temperature again, to be warming up to temperature be 250 ~ 300 DEG C, rear running temperature is set as 300 DEG C, and rear working time is 15min; 4. be set as 200 ~ 300 DEG C to the mass ions source temperature of mass detector, the solvent delay time is 3.5min ~ 4min, and broad peak is set as wide, and residence time is set as 100ms; 5. many reaction patterns are set as to the reaction pattern of mass detector, hexamethyl cyclotrisiloxane quota ion to for: 207 → 191, qualitative ion pair is: 207 → 189, collision voltage be: 20eV; Octamethylcy-clotetrasiloxane quota ion to for: 281 → 265, qualitative ion pair is: 281 → 249, collision voltage be: 20eV; Decamethylcyclopentaandoxane quota ion to for: 355 → 267, qualitative ion pair is: 355 → 251, collision voltage be: 20eV; Ten diformazan basic ring six siloxane quota ions to for: 429 → 341, qualitative ion pair is: 429 → 147, collision voltage be: 20eV;
Three, examination criteria liquid: 1. prepare titer a; In described titer a, the mass concentration of hexamethyl cyclotrisiloxane (D3) is 5ng/mL, the mass concentration of octamethylcy-clotetrasiloxane (D4) is 5ng/mL, the mass concentration of decamethylcyclopentaandoxane (D5) is 5ng/mL, the mass concentration of ten diformazan basic ring six siloxane (D6) is 5ng/mL; 2. titer b is prepared; In described titer b, the mass concentration of hexamethyl cyclotrisiloxane (D3) is 10ng/mL, the mass concentration of octamethylcy-clotetrasiloxane (D4) is 10ng/mL, the mass concentration of decamethylcyclopentaandoxane (D5) is 10ng/mL, the mass concentration of ten diformazan basic ring six siloxane (D6) is 10ng/mL; 3. titer c is prepared; In described titer c, the mass concentration of hexamethyl cyclotrisiloxane (D3) is 20ng/mL, the mass concentration of octamethylcy-clotetrasiloxane (D4) is 20ng/mL, the mass concentration of decamethylcyclopentaandoxane (D5) is 20ng/mL, the mass concentration of ten diformazan basic ring six siloxane (D6) is 20ng/mL; 4. titer d is prepared; In described titer d, the mass concentration of hexamethyl cyclotrisiloxane (D3) is 50ng/mL, the mass concentration of octamethylcy-clotetrasiloxane (D4) is 50ng/mL, the mass concentration of decamethylcyclopentaandoxane (D5) is 50ng/mL, the mass concentration of ten diformazan basic ring six siloxane (D6) is 50ng/mL; 5. titer e is prepared; In described titer e, the mass concentration of hexamethyl cyclotrisiloxane (D3) is 100ng/mL, the mass concentration of octamethylcy-clotetrasiloxane (D4) is 100ng/mL, the mass concentration of decamethylcyclopentaandoxane (D5) is 100ng/mL, the mass concentration of ten diformazan basic ring six siloxane (D6) is 100ng/mL; 6. successively titer a, titer b, titer c, titer d and titer e are detected by concentration gradient with the GC-MS-MS instrument that step 2 sets, obtain the total ion current amount chromatogram of typical curve and titer;
Four, testing sample is detected: when the coefficients R of the regression equation corresponding to the typical curve that step 3 obtains
2when being greater than 0.95, the testing sample after the process obtained step one in GC-MS-MS technology is utilized to carry out the detection of cyclic methyl siloxane type and content, testing sample after the process that step one is obtained is by the injection port of GC-MS-MS instrument, enter in chromatographic column, each component of testing sample decomposition product is separated, enter Mass Spectrometer Method part by the interface of GC-MS-MS instrument after separation and carry out Mass Spectrometer Method, for detecting the time of hexamethyl cyclotrisiloxane after Mass Spectrometer Method starts 3.8min, residence time 100ms, for detecting the time of octamethylcy-clotetrasiloxane after Mass Spectrometer Method starts 4.5min, residence time 100ms, for detecting the time of decamethylcyclopentaandoxane after Mass Spectrometer Method starts 6.0min, residence time 100ms, Mass Spectrometer Method is the time of detection ten diformazan basic ring six siloxane after starting 7.3min, residence time 100ms, obtain the total ion current amount chromatogram of testing sample, the type that can draw cyclic methyl siloxane in testing sample is contrasted by the mass spectrum total ion current spirogram of the titer obtained with step 3, the typical curve obtained by step 3 can obtain the concentration of cyclic methyl siloxane in testing sample.
Embodiment two: present embodiment and embodiment one unlike: when using Rotary Evaporators to carry out concentrated to the organic phase adding isooctane in step one, water-bath temperature is set as 28 DEG C.Other steps and parameter identical with embodiment one.
Embodiment three: present embodiment and embodiment one or two are unlike the nitrogen that adopts purity 99.99% when using Nitrogen evaporator to carry out concentrated to sample after concentrated in step one.Other steps and parameter identical with embodiment one or two.
Embodiment four: one of present embodiment and embodiment one to three unlike: 1. step 2 is set as 200 DEG C to gas chromatographic sample introduction mouth temperature, sample size is set as 2 μ L, pressure setting is 13.312Psi, pattern is set as that pulse is not shunted, and sample introduction pulse is 40Psi, and the time is 8min, shunting outlet purge flow rate is set as 50mL/min, purge time is 1.2ms, and gas chromatograph is opened carrier gas and saved after enabling 3min, carrier gas flux is set as 20mL/min.Other steps and parameter identical with one of embodiment one to three.
Embodiment five: one of present embodiment and embodiment one to four unlike: step 2 2. described in chromatographic column model be AgilentHP-5, dimensions is 30m × 250 μm × 0.25 μm.Other steps and parameter identical with one of embodiment one to four.
Embodiment six: one of present embodiment and embodiment one to five unlike: 2. step 2 is set as 1.2mL/min to chromatographic column helium gas flow, average linear velocity is 28.644cm/sec, hold-up time is 1.7456min, constant rate, rear operating flux is set as 1.5mL/min, post case open temp is 40 DEG C, and equilibration time is 0.1min.Other steps and parameter identical with one of embodiment one to five.
Embodiment seven: 3. one of present embodiment and embodiment one to six heat up to chromatographic column Program unlike: step 2 and be set as from temperature is 40 DEG C, 2min is kept at temperature is 40 DEG C, then being 40 DEG C with the heating rate of 20 DEG C/min by temperature, to be warming up to temperature be 220 DEG C, being 220 DEG C with the heating rate of 60 DEG C/min by temperature again, to be warming up to temperature be 280 DEG C, rear running temperature is set as 300 DEG C, and rear working time is 15min.Other steps and parameter identical with one of embodiment one to six.
Embodiment eight: one of present embodiment and embodiment one to seven unlike: 4. step 2 is set as 250 DEG C to the mass ions source temperature of mass detector, the solvent delay time is 3.8min, broad peak is set as wide, and residence time is set as 100ms.Other steps and parameter identical with one of embodiment one to seven.
Following test is adopted to verify beneficial effect of the present invention
Water sample takes from Song Hua River river, with methylene chloride washing test glassware used before test, then 3h is soaked with red fuming nitric acid (RFNA), use respectively again clear water and distilled water flushing clean, put into drying box dry for standby under temperature is 100 DEG C of conditions, with again using acetone and each washing test of normal hexane glassware used 3 times before using, then by the glassware after cleaning as having in the muffle furnace of anhydrous sodium sulfate, at temperature is 600 DEG C, toasts 12h, takes out glassware and test.
In a kind of surface water of test one, this test, the detection method of cyclic methyl siloxane is carried out according to the following steps:
One, liquid-liquid extraction method is utilized to carry out pre-service to testing sample: 1. to carry out first time extraction with extract methylene chloride to 1L testing sample, carry out concussion 3min during extraction, static 20min layering, obtain the first organic phase and the more than first phase; Step 1. described in extract and the volume ratio of testing sample be 1:10; 2. with extract methylene chloride to step 1. obtain more than first carry out mutually second time extraction, shake during extraction, static layering, obtain Second Organic Phase and the more than second phase; Step 1. described in extract and step 2. described in the volume ratio of extract be 2:1; 3. with extract methylene chloride to step 2. obtain more than second carry out mutually third time extraction, shake during extraction, static layering, obtain the 3rd organic phase and the more than the 3rd phase; Step 1. described in extract and step 3. described in the volume ratio of extract be 2:1; 4. the first organic phase, Second Organic Phase and the 3rd organic phase are merged, then in the organic phase merged, isooctane is added, obtain the organic phase adding isooctane, then Rotary Evaporators is first used to concentrate the organic phase adding isooctane, be concentrated into 2mL, obtain concentrated rear sample, re-use Nitrogen evaporator and concentrated rear sample is concentrated, be concentrated into 1mL, obtain processing rear testing sample; Described isooctane and step 1. described in the volume ratio of extract be 1:20;
Two, GC-MS-MS instrument parameter setting: 1. 200 DEG C are set as to gas chromatographic sample introduction mouth temperature, sample size is set as 2 μ L, pressure setting is 13.312Psi, pattern is set as that pulse is not shunted, and sample introduction pulse is 40Psi, and the time is 8min, shunting outlet purge flow rate is set as 50mL/min, purge time is 1.2ms, and gas chromatograph is opened carrier gas and saved after enabling 3min, carrier gas flux is set as 20mL/min; 2. be set as 1.2mL/min to chromatographic column helium gas flow, average linear velocity is 28.644cm/sec, and the hold-up time is 1.7456min, constant rate, and rear operating flux is set as 1.5mL/min, and post case open temp is 40 DEG C, and equilibration time is 0.1min; 3. heating up to chromatographic column Program is set as from temperature is 40 DEG C, 2min is kept at temperature is 40 DEG C, then being 40 DEG C with the heating rate of 20 DEG C/min by temperature, to be warming up to temperature be 220 DEG C, being 220 DEG C with the heating rate of 60 DEG C/min by temperature again, to be warming up to temperature be 280 DEG C, rear running temperature is set as 300 DEG C, and rear working time is 15min; 4. be set as 250 DEG C to the mass ions source temperature of mass detector, the solvent delay time is 3.8min, and broad peak is set as wide, and residence time is set as 100ms; 5. many reaction patterns are set as to the reaction pattern of mass detector, hexamethyl cyclotrisiloxane quota ion to for: 207 → 191, qualitative ion pair is: 207 → 189, collision voltage be: 20eV; Octamethylcy-clotetrasiloxane quota ion to for: 281 → 265, qualitative ion pair is: 281 → 249, collision voltage be: 20eV; Decamethylcyclopentaandoxane quota ion to for: 355 → 267, qualitative ion pair is: 355 → 251, collision voltage be: 20eV; Ten diformazan basic ring six siloxane quota ions to for: 429 → 341, qualitative ion pair is: 429 → 147, collision voltage be: 20eV;
Three, examination criteria liquid: 1. prepare titer a; In described titer a, the mass concentration of hexamethyl cyclotrisiloxane (D3) is 5ng/mL, the mass concentration of octamethylcy-clotetrasiloxane (D4) is 5ng/mL, the mass concentration of decamethylcyclopentaandoxane (D5) is 5ng/mL, the mass concentration of ten diformazan basic ring six siloxane (D6) is 5ng/mL; 2. titer b is prepared; In described titer b, the mass concentration of hexamethyl cyclotrisiloxane (D3) is 10ng/mL, the mass concentration of octamethylcy-clotetrasiloxane (D4) is 10ng/mL, the mass concentration of decamethylcyclopentaandoxane (D5) is 10ng/mL, the mass concentration of ten diformazan basic ring six siloxane (D6) is 10ng/mL; 3. titer c is prepared; In described titer c, the mass concentration of hexamethyl cyclotrisiloxane (D3) is 20ng/mL, the mass concentration of octamethylcy-clotetrasiloxane (D4) is 20ng/mL, the mass concentration of decamethylcyclopentaandoxane (D5) is 20ng/mL, the mass concentration of ten diformazan basic ring six siloxane (D6) is 20ng/mL; 4. titer d is prepared; In described titer d, the mass concentration of hexamethyl cyclotrisiloxane (D3) is 50ng/mL, the mass concentration of octamethylcy-clotetrasiloxane (D4) is 50ng/mL, the mass concentration of decamethylcyclopentaandoxane (D5) is 50ng/mL, the mass concentration of ten diformazan basic ring six siloxane (D6) is 50ng/mL; 5. titer e is prepared; In described titer e, the mass concentration of hexamethyl cyclotrisiloxane (D3) is 100ng/mL, the mass concentration of octamethylcy-clotetrasiloxane (D4) is 100ng/mL, the mass concentration of decamethylcyclopentaandoxane (D5) is 100ng/mL, the mass concentration of ten diformazan basic ring six siloxane (D6) is 100ng/mL; 6. successively titer a, titer b, titer c, titer d and titer e are detected by concentration gradient with the GC-MS-MS instrument that step 2 sets, obtain the total ion current amount chromatogram (see Fig. 5) of the typical curve (see Fig. 1) of D3, the typical curve (see Fig. 2) of D4, the typical curve (see Fig. 3) of D5, the typical curve (see Fig. 4) of D6 and titer;
The regression equation that in step 3, the typical curve of D3 is corresponding is Y=469.025916*X, R
2=0.99329650;
The regression equation that in step 3, the typical curve of D4 is corresponding is Y=161.569911*X, R
2=0.99264404;
The regression equation that in step 3, the typical curve of D5 is corresponding is Y=234.517991*X, R
2=0.99976244;
The regression equation that in step 3, the typical curve of D6 is corresponding is Y=220.786486*X, R
2=0.99463584;
Four, testing sample is detected: when the coefficients R of the regression equation corresponding to the typical curve that step 3 obtains
2when being greater than 0.95, the testing sample after the process obtained step one in GC-MS-MS technology is utilized to carry out the detection of cyclic methyl siloxane type and content, testing sample after the process that step one is obtained is by the injection port of GC-MS-MS instrument, enter in chromatographic column, each component of testing sample decomposition product is separated, enter Mass Spectrometer Method part by the interface of GC-MS-MS instrument after separation and carry out Mass Spectrometer Method, for detecting the time of hexamethyl cyclotrisiloxane after Mass Spectrometer Method starts 3.8min, residence time 100ms, for detecting the time of octamethylcy-clotetrasiloxane after Mass Spectrometer Method starts 4.5min, residence time 100ms, for detecting the time of decamethylcyclopentaandoxane after Mass Spectrometer Method starts 6.0min, residence time 100ms, Mass Spectrometer Method is the time of detection ten diformazan basic ring six siloxane after starting 7.3min, residence time 100ms, obtain the total ion current amount chromatogram (see Fig. 6) of testing sample, by the mass spectrum total ion current spirogram of the titer obtained with step 3 contrast can draw cyclic methyl siloxane in testing sample type respectively: D3, D4, D5, D6, the concentration that the typical curve obtained by step 3 can obtain cyclic methyl siloxane in testing sample is 10.0ng/mL.
When wherein using Rotary Evaporators to carry out concentrated to the organic phase adding isooctane in step one, water-bath temperature is set as 28 DEG C.
The nitrogen of purity 99.99% is adopted when wherein using Nitrogen evaporator to carry out concentrated to concentrated rear sample in step one.
Wherein step 2 2. described in chromatographic column model be AgilentHP-5, dimensions is 30m × 250 μm × 0.25 μm.
Claims (8)
1. the detection method of cyclic methyl siloxane in surface water, is characterized in that the method is carried out according to the following steps:
One, liquid-liquid extraction method is utilized to carry out pre-service to testing sample: 1. to carry out first time extraction with extract methylene chloride to testing sample, shake during extraction, static layering, obtain the first organic phase and the more than first phase; Step 1. described in extract and the volume ratio of testing sample be 1:10; 2. with extract methylene chloride to step 1. obtain more than first carry out mutually second time extraction, shake during extraction, static layering, obtain Second Organic Phase and the more than second phase; Step 1. described in extract and step 2. described in the volume ratio of extract be 2:1; 3. with extract methylene chloride to step 2. obtain more than second carry out mutually third time extraction, shake during extraction, static layering, obtain the 3rd organic phase and the more than the 3rd phase; Step 1. described in extract and step 3. described in the volume ratio of extract be 2:1; 4. the first organic phase, Second Organic Phase and the 3rd organic phase are merged, then in the organic phase merged, isooctane is added, obtain the organic phase adding isooctane, then Rotary Evaporators is first used to concentrate the organic phase adding isooctane, be concentrated into 2mL, obtain concentrated rear sample, re-use Nitrogen evaporator and concentrated rear sample is concentrated, be concentrated into 1mL, obtain processing rear testing sample; Described isooctane and step 1. described in the volume ratio of extract be 1:20;
Two, GC-MS-MS instrument parameter setting: 1. 180 DEG C ~ 220 DEG C are set as to gas chromatographic sample introduction mouth temperature, sample size is set as 2 μ L, pressure setting is 13Psi ~ 14Psi, pattern is set as that pulse is not shunted, sample introduction pulse is 38Psi ~ 42Psi, time is 7min ~ 9min, shunting outlet purge flow rate is set as 48mL/min ~ 52mL/min, purge time is 1.2ms, gas chromatograph is opened carrier gas and is saved after enabling 3min ~ 4min, carrier gas flux is set as 15mL/min ~ 25mL/min; 2. be set as 1mL/min ~ 1.4mL/min to chromatographic column helium gas flow, average linear velocity is 28cm/sec ~ 29cm/sec, and the hold-up time is 1.5min ~ 2.0min, constant rate, rear operating flux is set as 1.5mL/min, and post case open temp is 35 ~ 45 DEG C, and equilibration time is 0.1min; 3. heating up to chromatographic column Program is set as from temperature is 35 ~ 45 DEG C, 2min ~ 3min is kept at temperature is 35 ~ 45 DEG C, then being 35 ~ 45 DEG C with the heating rate of 20 DEG C/min by temperature, to be warming up to temperature be 200 ~ 240 DEG C, being 200 ~ 240 DEG C with the heating rate of 60 DEG C/min by temperature again, to be warming up to temperature be 250 ~ 300 DEG C, rear running temperature is set as 300 DEG C, and rear working time is 15min; 4. be set as 200 ~ 300 DEG C to the mass ions source temperature of mass detector, the solvent delay time is 3.5min ~ 4min, and broad peak is set as wide, and residence time is set as 100ms; 5. many reaction patterns are set as to the reaction pattern of mass detector, hexamethyl cyclotrisiloxane quota ion to for: 207 → 191, qualitative ion pair is: 207 → 189, collision voltage be: 20eV; Octamethylcy-clotetrasiloxane quota ion to for: 281 → 265, qualitative ion pair is: 281 → 249, collision voltage be: 20eV; Decamethylcyclopentaandoxane quota ion to for: 355 → 267, qualitative ion pair is: 355 → 251, collision voltage be: 20eV; Ten diformazan basic ring six siloxane quota ions to for: 429 → 341, qualitative ion pair is: 429 → 147, collision voltage be: 20eV;
Three, examination criteria liquid: 1. prepare titer a; In described titer a, the mass concentration of hexamethyl cyclotrisiloxane is 5ng/mL, the mass concentration of octamethylcy-clotetrasiloxane is 5ng/mL, the mass concentration of decamethylcyclopentaandoxane is 5ng/mL, the mass concentration of ten diformazan basic ring six siloxane is 5ng/mL; 2. titer b is prepared; In described titer b, the mass concentration of hexamethyl cyclotrisiloxane is 10ng/mL, the mass concentration of octamethylcy-clotetrasiloxane is 10ng/mL, the mass concentration of decamethylcyclopentaandoxane is 10ng/mL, the mass concentration of ten diformazan basic ring six siloxane is 10ng/mL; 3. titer c is prepared; In described titer c, the mass concentration of hexamethyl cyclotrisiloxane is 20ng/mL, the mass concentration of octamethylcy-clotetrasiloxane is 20ng/mL, the mass concentration of decamethylcyclopentaandoxane is 20ng/mL, the mass concentration of ten diformazan basic ring six siloxane is 20ng/mL; 4. titer d is prepared; In described titer d, the mass concentration of hexamethyl cyclotrisiloxane is 50ng/mL, the mass concentration of octamethylcy-clotetrasiloxane is 50ng/mL, the mass concentration of decamethylcyclopentaandoxane is 50ng/mL, the mass concentration of ten diformazan basic ring six siloxane is 50ng/mL; 5. titer e is prepared; In described titer e, the mass concentration of hexamethyl cyclotrisiloxane is 100ng/mL, the mass concentration of octamethylcy-clotetrasiloxane is 100ng/mL, the mass concentration of decamethylcyclopentaandoxane is 100ng/mL, the mass concentration of ten diformazan basic ring six siloxane is 100ng/mL; 6. successively titer a, titer b, titer c, titer d and titer e are detected by concentration gradient with the GC-MS-MS instrument that step 2 sets, obtain the total ion current amount chromatogram of typical curve and titer;
Four, testing sample is detected: when the coefficients R of the regression equation corresponding to the typical curve that step 3 obtains
2when being greater than 0.95, the testing sample after the process obtained step one in GC-MS-MS technology is utilized to carry out the detection of cyclic methyl siloxane type and content, testing sample after the process that step one is obtained is by the injection port of GC-MS-MS instrument, enter in chromatographic column, each component of testing sample decomposition product is separated, enter Mass Spectrometer Method part by the interface of GC-MS-MS instrument after separation and carry out Mass Spectrometer Method, for detecting the time of hexamethyl cyclotrisiloxane after Mass Spectrometer Method starts 3.8min, residence time 100ms, for detecting the time of octamethylcy-clotetrasiloxane after Mass Spectrometer Method starts 4.5min, residence time 100ms, for detecting the time of decamethylcyclopentaandoxane after Mass Spectrometer Method starts 6.0min, residence time 100ms, Mass Spectrometer Method is the time of detection ten diformazan basic ring six siloxane after starting 7.3min, residence time 100ms, obtain the total ion current amount chromatogram of testing sample, the type that can draw cyclic methyl siloxane in testing sample is contrasted by the mass spectrum total ion current spirogram of the titer obtained with step 3, the typical curve obtained by step 3 can obtain the concentration of cyclic methyl siloxane in testing sample.
2. the detection method of cyclic methyl siloxane in a kind of surface water according to claim 1, when it is characterized in that using Rotary Evaporators to carry out concentrated to the organic phase adding isooctane in step one, water-bath temperature is set as 28 DEG C.
3. the detection method of cyclic methyl siloxane in a kind of surface water according to claim 1, adopts the nitrogen of purity 99.99% when it is characterized in that using in step one Nitrogen evaporator to carry out concentrated to sample after concentrated.
4. the detection method of cyclic methyl siloxane in a kind of surface water according to claim 1, it is characterized in that 1. step 2 is set as 200 DEG C to gas chromatographic sample introduction mouth temperature, sample size is set as 2 μ L, pressure setting is 13.312Psi, pattern is set as that pulse is not shunted, sample introduction pulse is 40Psi, time is 8min, shunting outlet purge flow rate is set as 50mL/min, purge time is 1.2ms, gas chromatograph is opened carrier gas and is saved after enabling 3min, carrier gas flux is set as 20mL/min.
5. the detection method of cyclic methyl siloxane in a kind of surface water according to claim 1, is characterized in that the chromatographic column model described in step 2 is 2. AgilentHP-5, and dimensions is 30m × 250 μm × 0.25 μm.
6. the detection method of cyclic methyl siloxane in a kind of surface water according to claim 1, it is characterized in that 2. step 2 is set as 1.2mL/min to chromatographic column helium gas flow, average linear velocity is 28.644cm/sec, hold-up time is 1.7456min, constant rate, rear operating flux is set as 1.5mL/min, and post case open temp is 40 DEG C, and equilibration time is 0.1min.
7. the detection method of cyclic methyl siloxane in a kind of surface water according to claim 1, it is characterized in that 3. step 2 heats up to chromatographic column Program is set as from temperature is 40 DEG C, 2min is kept at temperature is 40 DEG C, then being 40 DEG C with the heating rate of 20 DEG C/min by temperature, to be warming up to temperature be 220 DEG C, being 220 DEG C with the heating rate of 60 DEG C/min by temperature again, to be warming up to temperature be 280 DEG C, rear running temperature is set as 300 DEG C, and rear working time is 15min.
8. the detection method of cyclic methyl siloxane in a kind of surface water according to claim 1, it is characterized in that 4. step 2 is set as 250 DEG C to the mass ions source temperature of mass detector, the solvent delay time is 3.8min, and broad peak is set as wide, and residence time is set as 100ms.
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