阅读说明：本技术 测定聚醚改性有机硅中醛酮含量的方法 (Method for determining aldehyde ketone content in polyether modified organic silicon ) 是由 范珺 刘振 祁争健 于 2020-12-29 设计创作，主要内容包括：本发明涉及有机硅聚合物检测技术领域,具体涉及测定聚醚改性有机硅中醛酮含量的方法。该方法包括：将待测的聚醚改性有机硅与DNPH进行衍生反应形成反应产物；以不含待测的聚醚改性有机硅为空白对照,并进行衍生反应,形成空白对照产物；而后利用高效液相分别对所述反应产物和空白对照产物进行检测分别得到不同醛酮的出峰面积,而后将不同醛酮所述出峰面积分别带入对应醛酮的标准曲线公式中进行计算,分别得到对应醛酮的检测含量；而后将对应醛酮的检测含量带入下述公式得到所述待测的聚醚改性有机硅对应醛酮的含量；W＝(Ai-A0)/m。该方法可以有效准确的定量检测聚醚改性有机硅中醛酮的含量,有利于提升聚醚改性有机硅的质量。(The invention relates to the technical field of organic silicon polymer detection, in particular to a method for determining aldehyde ketone content in polyether modified organic silicon. The method comprises the following steps: carrying out derivatization reaction on polyether modified organic silicon to be detected and DNPH to form a reaction product; taking polyether modified organic silicon without a to-be-detected polyether as a blank control, and carrying out a derivatization reaction to form a blank control product; respectively detecting the reaction product and the blank reference product by utilizing a high performance liquid phase to respectively obtain the peak areas of different aldehydes and ketones, and then respectively bringing the peak areas of different aldehydes and ketones into a standard curve formula corresponding to the aldehydes and ketones to calculate so as to respectively obtain the detection contents of the corresponding aldehydes and ketones; then substituting the detected content of corresponding aldehyde ketone into the following formula to obtain the content of corresponding aldehyde ketone in the polyether modified organic silicon to be detected; w is (Ai-A0)/m. The method can effectively and accurately quantitatively detect the content of aldehyde ketone in the polyether modified organic silicon, and is beneficial to improving the quality of the polyether modified organic silicon.)

1. A method for determining aldehyde ketone content in polyether modified organic silicon is characterized by comprising the following steps: carrying out derivatization reaction on polyether modified organic silicon to be detected and DNPH to form a reaction product;

taking polyether modified organic silicon without a to-be-detected polyether as a blank control, and carrying out a derivatization reaction to form a blank control product;

respectively detecting the reaction product and the blank reference product by utilizing a high performance liquid phase to respectively obtain the peak areas of different aldehydes and ketones, and then respectively bringing the peak areas of different aldehydes and ketones into a standard curve formula corresponding to the aldehydes and ketones to calculate so as to respectively obtain the detection contents of the corresponding aldehydes and ketones;

then substituting the detected content of corresponding aldehyde ketone into the following formula to obtain the content of corresponding aldehyde ketone in the polyether modified organic silicon to be detected;

w is (Ai-a0)/m, m is the mass (g) of the polyether modified organic silicon to be detected, Ai is the detected content (μ g) of the corresponding aldehyde ketone of the polyether modified organic silicon to be detected, a0 is the detected content (μ g) of the corresponding aldehyde ketone in the blank control, and W is the content (μ g/g) of the corresponding aldehyde ketone of the polyether modified organic silicon to be detected.

2. The method of claim 1, wherein the aldehyde ketone comprises a low molecular weight aldehyde ketone;

preferably, the low molecular weight aldehyde ketone comprises at least one of formaldehyde, acetaldehyde, acrolein, acetone, and propionaldehyde.

3. The method for determining the content of aldehyde ketone in polyether modified organosilicon according to claim 2, wherein the standard curve formula of formaldehyde is: Y1733.5X + 5.2585;

the standard curve formula of acetaldehyde is: Y11.977X + 6.2652;

the standard curve formula of acrolein is as follows: Y46.954X + 6.164;

the standard curve formula of the acetone is as follows: Y11.573X + 8.9671;

the standard curve formula of propionaldehyde is as follows: Y34.552X-48.126.

4. The method for determining the content of aldehyde ketone in polyether-modified silicone according to claim 2, wherein the detection limits of formaldehyde, acetaldehyde, acrolein, acetone, and propionaldehyde are 0.01 μ g, 0.10 μ g, and 0.10 μ g in this order.

5. The method for determining the aldehyde ketone content in polyether modified organosilicon according to claim 1, wherein the step of determining the formula of the standard curve corresponding to the aldehyde ketone comprises: preparing a series of standard substance solutions with different concentrations by using corresponding aldehyde ketone standard substances, and performing derivatization reaction on the standard substance solutions and DNPH respectively to form a series of derivatized standard substance solutions with different concentrations;

and then respectively detecting the derived standard substance solutions by using the high solutions, obtaining a standard curve according to the detection result, and obtaining a standard curve formula according to the standard curve.

6. The method of claim 1, wherein the standard curve equation is corrected before the peak area of the reaction product is substituted into the standard curve equation;

preferably, the correction method is: estimating the content of corresponding aldehyde ketone according to the peak area of the reaction product, if the estimated content is obviously higher than the highest content of the corresponding aldehyde ketone forming a standard curve, preparing a standard solution with the concentration higher than the estimated content by using a corresponding aldehyde ketone standard substance, then reacting and detecting the standard solution, and correcting a standard curve formula according to the detection result;

if the estimated content is obviously lower than the lowest content forming a standard curve, preparing a standard solution with the concentration lower than the estimated content by using a corresponding aldehyde ketone standard, then reacting and detecting the standard solution, and correcting a standard curve formula according to the detection result;

preferably, the above correction is performed if the difference between the estimated content and the minimum content or the maximum content is 20% or more.

7. The method for determining the content of aldehyde ketone in polyether modified organosilicon according to claim 1, wherein the detection conditions of the high performance liquid phase are as follows: mobile phase: acetonitrile: the volume ratio of water is 60: 40; flow rate (ml/min): 0.5; 20 sample volume (ul); column temperature (. degree. C.): 35; c18 liquid chromatography column; ultraviolet detection wavelength (nm): 360.

8. the method for determining the aldehyde ketone content in polyether modified organosilicon according to claim 1, wherein the derivatization reaction conditions are as follows: the reaction temperature is 40-60 ℃, and the reaction time is 1-2 h; the mass ratio of the polyether modified organic silicon to be detected to the DNPH is 0.1-1: 0.02.

9. The method of claim 1, wherein the step of performing the derivatization reaction comprises: mixing the polyether modified organic silicon to be detected, the DNPH and an acid solution, and then reacting;

preferably, the acid solution is a phosphoric acid solution;

preferably, the volume percentage of the phosphoric acid solution is 0.5-1.5%.

10. The method for determining the content of aldehyde ketone in polyether modified organosilicon according to claim 1, wherein the reaction product and the blank control product are separately filtered before the reaction product is detected by using the high performance liquid phase.

Technical Field

The invention relates to the technical field of organic silicon polymer detection, in particular to a method for determining aldehyde ketone content in polyether modified organic silicon.

Background

The organic silicon polymer contains silicon element in the molecular structure, and organic functional groups are connected to silicon atoms. According to their chemical structure and properties, they can be divided into three categories: (1) a silicone oil; (2) silicone rubber; (3) a silicone resin. Wherein, the polyether modified silicone oil is an organosilicon nonionic surfactant with unique performance which is prepared by graft copolymerization of polyether and dimethyl siloxane. The main uses of the polyether modified silicone oil are as follows: (1) the foam stabilizer for foaming polyurethane systems ensures that foam holes are fine, dense and uniform, and the obtained product is widely applied to household appliance heat-insulating materials, automobile seat sponge production, building heat-insulating layers and the like; (2) the additive in the cosmetics has the effects of lubricating skin, moisturizing and resisting wrinkles; (3) the wetting developing agent in the pesticide industry improves the pesticide effect and reduces the public nuisance; (4) the leveling agent of the paint or the polyurethane slurry reduces the internal friction of molecules and plays a role in leveling and defoaming.

Generally, the number of silicone oil chain links or the proportion of EO/PO in polyether is changed, and the number of the chain links and the end group are changed, so that various polyether modified silicone oils with different performances can be obtained to meet the needs of various industries. The by-product of the polyether modified silicone oil is mainly an aldehyde ketone substance generated by the breakage of polyether double bonds in the synthesis process of the polyether modified silicone oil. When the polyether modified silicone oil is applied to the industries of household appliances, automobiles, building materials, paints and the like, the content of aldehyde ketone substances in the product is concerned closely.

Aldehyde ketones generally refer to organic species that contain a carbonyl functionality in the molecule. At normal temperature, except that formaldehyde is gas, aliphatic aldehyde ketone with less than twelve carbon atoms is liquid, and common aldehyde ketone mainly comprises formaldehyde, acetaldehyde, propionaldehyde, acrolein and acetone. Of greatest concern in the environment are low molecular weight aldehyde ketone compounds, which on the one hand are highly toxic and on the other hand are the main constituents of photochemical smog. The aldoketone compounds can stimulate skin and mucosa and poison central nervous system, and can cause nasopharyngeal diseases, direct stimulation of eyes, headache, etc. Many studies have shown that aldonic compounds, especially formaldehyde, acetaldehyde and acrolein, are genotoxic. Formaldehyde is a carcinogenic and teratogenic substance determined by the world health organization, is a well-recognized source of allergy, and is also one of potential strong mutagens. Acetaldehyde toxicity mainly affects embryo development and has great harm to liver. Acrolein causes toxic reactions after entering human bodies, has carcinogenic effects on animals, and is classified as a priority control pollutant of the U.S. EPA. Ketones are less irritating to the skin and tracheal mucosa than aldehydes, but are more anesthetic and more potent on the central nerve. Acetone is mainly used for inhibiting and anesthetizing central nervous system, and damage to liver, kidney and pancreas can occur when high-concentration contact is carried out.

At present, the detection standard of the content of aldehyde ketone in the industries of buildings, automobiles, household appliances, paints and the like at home and abroad is mainly the detection of the content of aldehyde ketone substances in finished products such as plastic products, automotive interiors, electronic components, textile products and the like. There is no relevant standard or method for detecting low molecular aldehyde ketone substances in the raw material polyether modified organic silicon for a while.

In view of this, the invention is particularly proposed.

Disclosure of Invention

The invention aims to provide a method for determining the content of aldehyde ketone in polyether modified organic silicon. The method can effectively and accurately quantitatively detect the content of aldehyde ketone in the polyether modified organic silicon, and is beneficial to improving the quality of the polyether modified organic silicon.

The invention is realized by the following steps:

in a first aspect, the present invention provides a method for determining aldehyde ketone content in polyether modified organosilicon, comprising: carrying out derivatization reaction on polyether modified organic silicon to be detected and DNPH to form a reaction product;

taking polyether modified organic silicon without a to-be-detected polyether as a blank control, and carrying out a derivatization reaction to form a blank control product;

respectively detecting the reaction product and the blank reference product by utilizing a high performance liquid phase to respectively obtain the peak areas of different aldehydes and ketones, and then respectively bringing the peak areas of different aldehydes and ketones into a standard curve formula corresponding to the aldehydes and ketones to calculate so as to respectively obtain the detection contents of the corresponding aldehydes and ketones;

then substituting the detected content of corresponding aldehyde ketone into the following formula to obtain the content of corresponding aldehyde ketone in the polyether modified organic silicon to be detected;

w is (Ai-a0)/m, m is the mass (g) of the polyether modified organic silicon to be detected, Ai is the detected content (μ g) of the corresponding aldehyde ketone of the polyether modified organic silicon to be detected, a0 is the detected content (μ g) of the corresponding aldehyde ketone in the blank control, and W is the content (μ g/g) of the corresponding aldehyde ketone of the polyether modified organic silicon to be detected.

In alternative embodiments, the aldehyde ketone comprises a low molecular aldehyde ketone;

preferably, the low molecular weight aldehyde ketone comprises at least one of formaldehyde, acetaldehyde, acrolein, acetone, and propionaldehyde.

In an alternative embodiment, the standard curve formula for formaldehyde is: Y1733.5X + 5.2585;

the standard curve formula of acetaldehyde is: Y11.977X + 6.2652;

the standard curve formula of acrolein is as follows: Y46.954X + 6.164;

the standard curve formula of the acetone is as follows: Y11.573X + 8.9671;

the standard curve formula of propionaldehyde is as follows: Y34.552X-48.126.

In alternative embodiments, the detection limits of said formaldehyde, said acetaldehyde, said acrolein, said acetone, and said propionaldehyde are, in order, 0.01 μ g, 0.10 μ g, and 0.10 μ g.

In an alternative embodiment, the step of determining the standard curve formula for the aldehyde ketone comprises: preparing a series of standard substance solutions with different concentrations by using corresponding aldehyde ketone standard substances, and performing derivatization reaction on the standard substance solutions and DNPH respectively to form a series of derivatized standard substance solutions with different concentrations;

and then, respectively detecting the derived standard substance solutions by using high liquid, then obtaining a standard curve according to the detection result, and obtaining a standard curve formula according to the standard curve.

In an alternative embodiment, the standard curve equation is corrected before the peak area of the reaction product is brought into the standard curve equation;

preferably, the correction method is: estimating the content of corresponding aldehyde ketone according to the peak area of the reaction product, if the estimated content is obviously higher than the highest content forming a standard curve, preparing a standard solution with the concentration higher than the estimated content by using a corresponding aldehyde ketone standard substance, then reacting and detecting the standard solution, and correcting a standard curve formula according to the detection result;

if the estimated content is obviously lower than the lowest content forming a standard curve, preparing a standard solution with the concentration lower than the estimated content by using a corresponding aldehyde ketone standard, then reacting and detecting the standard solution, and correcting a standard curve formula according to the detection result;

preferably, the above correction is performed if the difference between the estimated content and the minimum content or the maximum content is 20% or more.

In an alternative embodiment, the detection conditions of the high performance liquid phase are: mobile phase: acetonitrile: the volume ratio of water is 60: 40; flow rate (ml/min): 0.5; 20 sample volume (ul); column temperature (. degree. C.): 35; c18 liquid chromatography column; ultraviolet detection wavelength (nm): 360.

in an alternative embodiment, the conditions of the derivatization reaction are: the reaction temperature is 40-60 ℃, and the reaction time is 1-2 h; the mass ratio of the polyether modified organic silicon to be detected to the DNPH is 0.1-1: 0.02.

In an alternative embodiment, the step of performing a derivatization reaction comprises: mixing the polyether modified organic silicon to be detected, the DNPH and an acid solution, and then reacting;

preferably, the acid solution is a phosphoric acid solution;

preferably, the volume percentage of the phosphoric acid solution is 0.5-1.5%.

In an alternative embodiment, the reaction product and blank product are separately filtered prior to detection of the reaction product using the high performance liquid phase.

The invention has the following beneficial effects: according to the method, through a derivatization reaction, aldehyde ketone in the polyether modified organic silicon to be detected forms aldehyde ketone-2, 4-dinitrophenylhydrazone, and then the content of the aldehyde ketone in the polyether modified organic silicon to be detected can be effectively detected according to a detection result of high liquid and an external standard method.

Drawings

In order to more clearly illustrate the technical solutions of the embodiments of the present invention, the drawings needed to be used in the embodiments will be briefly described below, it should be understood that the following drawings only illustrate some embodiments of the present invention and therefore should not be considered as limiting the scope, and for those skilled in the art, other related drawings can be obtained according to the drawings without inventive efforts.

FIG. 1 is a graph showing the results of detection of a standard substance provided in example 1 of the present invention;

FIG. 2 is a standard curve of formaldehyde provided in example 1 of the present invention;

FIG. 3 is a standard graph of acetaldehyde provided in example 1 of the present invention;

FIG. 4 is a standard graph of acrolein provided in example 1 of the present invention;

FIG. 5 is a standard curve of acetone provided in example 1 of the present invention;

figure 6 is a standard curve of propanal provided in example 1 of the present invention;

fig. 7 is a graph of the detection results provided in embodiment 1 of the present invention.

Detailed Description

In order to make the objects, technical solutions and advantages of the embodiments of the present invention clearer, the technical solutions in the embodiments of the present invention will be clearly and completely described below. The examples, in which specific conditions are not specified, were conducted under conventional conditions or conditions recommended by the manufacturer. The reagents or instruments used are not indicated by the manufacturer, and are all conventional products available commercially.

The embodiment of the invention provides a method for determining the content of aldehyde ketone in polyether modified organic silicon, which is used for detecting the content of aldehyde ketone in the polyether modified organic silicon, wherein the aldehyde ketone is low molecular weight aldehyde ketone, and can be at least one of formaldehyde, acetaldehyde, acrolein, acetone and propionaldehyde.

The present invention is illustrated by taking the simultaneous detection of formaldehyde, acetaldehyde, acrolein, acetone, and propionaldehyde as an example, but it is understood that some of the aldehyde ketone tests can be selectively performed.

The specific process is as follows:

s1, preparing liquid;

formaldehyde, acetaldehyde, acetone, acrolein and propionaldehyde are selected as standard substances, and acetonitrile is selected as a solvent. Acetonitrile is adopted to dissolve formaldehyde, acetaldehyde, acetone, acrolein and propionaldehyde respectively, and series of standard substance solutions with different concentrations are obtained, and at least 5 concentrations are selected from the standard substance solutions in each series, for example, the mixed preparation concentrations of formaldehyde and acetonitrile are as follows: 0.05. mu.g/ml, 0.1. mu.g/ml, 0.5. mu.g/ml, 1.0. mu.g/ml, 1.5. mu.g/ml, 3.0. mu.g/ml, 5.0. mu.g/ml and 10.0. mu.g/ml of the standard solution; the mixed preparation concentration of the acetone and the acetonitrile is as follows in sequence: 0.5. mu.g/ml, 1.0. mu.g/ml, 1.5. mu.g/ml, 3.0. mu.g/ml, 5.0. mu.g/ml and 10.0. mu.g/ml of the standard solution.

DNPH was mixed with acetonitrile to give a DNPH solution.

An acid (e.g., phosphoric acid) is mixed with acetonitrile to obtain an acid solution (e.g., phosphoric acid solution), and the volume percentage of the phosphoric acid solution is 0.5 to 1.5%, for example, 0.8%, 0.9%, 1.0%, 1.1%, and 1.2%, and may be preferably 1%.

S2, reacting;

respectively reacting the series of different aldehyde ketone standard substance solutions prepared in the step S1 with DNPH to form a series of derivative standard substance solutions with different concentrations, and specifically, respectively mixing the aldehyde ketone standard substance solutions with different concentrations with DNPH and an acid solution and then reacting; the reaction temperature is 40-60 ℃, and the reaction time is 1-2 h; and the DNPH added is excessive, so that complete reaction of aldehyde and ketone in the standard is ensured.

Carrying out derivatization reaction on polyether modified organic silicon to be detected and DNPH to form a reaction product; specifically, polyether modified organic silicon to be tested, the DNPH and an acid solution are mixed and then react; the reaction temperature is 40-60 ℃, and the reaction time is 1-2 h; the mass ratio of the polyether modified organic silicon to be detected to the DNPH is 0.1-1: 0.02. Namely, the DNPH is excessive in the derivatization reaction, so that the aldehyde-ketone substances such as formaldehyde, acetaldehyde, acetone, propionaldehyde and acrolein in the polyether modified organic silicon to be detected are fully and completely reacted, the accuracy of the detection result is ensured, the DNPH cannot cause the peak output area, the time and the like of the aldehyde-ketone substances such as formaldehyde, acetaldehyde, acetone, propionaldehyde and acrolein to be changed under the detection condition provided by the embodiment of the invention, the DNPH cannot influence the detection result under the detection condition provided by the embodiment of the invention, and the accuracy of the detection result is ensured.

Taking polyether modified organic silicon without a to-be-detected polyether as a blank control, and carrying out a derivatization reaction to form a blank control product; specifically, mixing DNPH and an acid solution and then reacting to form a blank control product; the reaction temperature is 40-60 ℃ and 1-2 h.

S3, detecting;

detecting aldehyde ketone derivative standard substance solutions with different concentrations formed in S2 by using high liquid, specifically, respectively detecting formaldehyde derivative standard substance solution, acetaldehyde derivative standard substance solution, acrolein derivative standard substance solution, acetone derivative standard substance solution and propionaldehyde derivative standard substance solution to obtain spectrograms. Wherein, 3 needles are injected for each concentration. And (3) processing the spectrogram after the detection is finished, determining the peak position of the standard aldehyde ketone-DNPH, then performing integration processing on the peak of the standard substance, and recording the peak time and the peak area. And summarizing the peak areas of the standard substances at different concentrations in an excel table to obtain a standard curve graph, and obtaining a standard curve formula and an R value according to the graph. The specific results are as follows:

components	Formula of standard curve	R2Value of	Detection limit
				Formaldehyde (I)	Y＝1733.5X+5.2585	0.9994	0.01μg
Acetaldehyde	Y＝11.977X+6.2652	0.9903	0.10μg
				Acrolein	Y＝46.954X+6.164	0.9912	0.10μg
Acetone (II)	Y＝11.573X+8.9671	0.9925	0.10μg
				Propionaldehyde	Y＝34.552X-48.126	0.9990	0.10μg

Further, the content of aldehyde ketone in the polyether modified silicone is generally low, so the calculation can be performed by directly using the above standard curve formula, but occasionally, the content of aldehyde ketone in the polyether modified silicone detected is too high or too low, and the above standard curve formula needs to be corrected. The method comprises the following specific steps: estimating the content of corresponding aldehyde ketone according to the peak area of the reaction product, comparing the content with the highest concentration and the lowest concentration which form a standard curve, if the estimated content is obviously higher than the highest content which forms the standard curve or is obviously lower than the lowest content which forms the standard curve, indicating that the standard curve formula is not applicable, and needing to be corrected, wherein the specific correction step is as follows:

if the estimated content is obviously higher than the highest content forming the standard curve, preparing a standard solution with the concentration higher than the estimated content by using a corresponding aldehyde ketone standard, then reacting and detecting the standard solution, and correcting a standard curve formula according to the detection result; and re-confirming the standard curve formula by taking the detection result as a parameter. If the estimated content is obviously lower than the lowest content forming the standard curve, preparing a standard solution with the concentration lower than the estimated content by using the corresponding aldehyde ketone standard, then reacting and detecting the standard solution, and correcting the standard curve formula according to the detection result. The correction is generally performed when the difference between the estimated content and the minimum content or the maximum content is 20% or more.

Further, the reaction product and the blank control product are respectively filtered, so that the detection result is not influenced by impurities in the subsequent detection process.

Then, detecting the filtered reaction product and the blank reference product by utilizing a high-performance liquid phase respectively to obtain peak areas of different aldehydes and ketones, and then respectively substituting the peak areas of the different aldehydes and ketones into a standard curve formula of corresponding aldehydes and ketones in the table above to calculate, so as to obtain the detection contents of the corresponding aldehydes and ketones respectively;

then substituting the detected content of corresponding aldehyde ketone into the following formula to obtain the content of corresponding aldehyde ketone in the polyether modified organic silicon to be detected;

w is (Ai-a0)/m, m is the mass (g) of the polyether modified organic silicon to be detected, Ai is the detected content (μ g) of the corresponding aldehyde ketone of the polyether modified organic silicon to be detected, a0 is the detected content (μ g) of the corresponding aldehyde ketone in the blank control, and W is the content (μ g/g) of the corresponding aldehyde ketone of the polyether modified organic silicon to be detected.

The content of aldehyde ketone corresponding to the polyether modified organic silicon to be detected can be effectively calculated according to the formula.

Further, the detection conditions of the high performance liquid phase in the embodiment of the invention are as follows: mobile phase: acetonitrile: the volume ratio of water is 60: 40; flow rate (ml/min): 0.5; 20 sample volume (ul); column temperature (. degree. C.): 35; c18 liquid chromatography column; ultraviolet detection wavelength (nm): 360. by adopting the detection conditions, formaldehyde-2, 4-dinitrophenylhydrazone, acetaldehyde-2, 4-dinitrophenylhydrazone, acrolein-2, 4-dinitrophenylhydrazone, acetone-2, 4-dinitrophenylhydrazone and propionaldehyde-2, 4-dinitrophenylhydrazone can be effectively detected, and then the content of aldehyde ketone in the polyether modified organic silicon to be detected can be effectively detected.

The features and properties of the present invention are described in further detail below with reference to examples.

Example 1

The instrument used in the experiment is a 1260 type high performance liquid chromatograph of Agilent company in America, which is provided with an ultraviolet detector, and the wavelength of the detector is set to be 360 nm. The analytical column was an Agilent C18 column, model 5um 4.6mm 250 mm.

The embodiment of the invention provides a method for determining aldehyde ketone content in polyether modified organic silicon, which comprises the following steps:

selecting formaldehyde, acetaldehyde, acetone, acrolein and propionaldehyde as standard substances to be detected, accurately weighing, and preparing standard solutions with the concentrations of 0.05 mu g/ml, 0.1 mu g/ml, 0.5 mu g/ml, 1.0 mu g/ml, 1.5 mu g/ml, 3.0 mu g/ml, 5.0 mu g/ml and 10.0 mu g/ml by using chromatographic grade acetonitrile respectively; preparing a 1 mass percent 2, 4-dinitrophenylhydrazine solution by using chromatographic grade acetonitrile, and preparing a 1 mass percent phosphoric acid solution by using chromatographic grade acetonitrile.

Accurately taking 1.0ml of each concentration standard solution by a pipette, adding the solution into a round-bottom flask, simultaneously adding 20ml of 1% 2, 4-dinitrophenylhydrazine solution and 2ml of 1% phosphoric acid solution, connecting a condensing tube above the round-bottom flask, and carrying out oil bath derivatization reaction at 60 ℃ for 1 h. Cooling to room temperature, washing the condenser tube with small amount of acetonitrile, filtering the derivative solution with 0.45 μm organic filter head, and detecting with high performance liquid chromatograph. Wherein, the detection conditions of the high performance liquid phase are as follows: mobile phase: acetonitrile: the volume ratio of water is 60: 40; flow rate (ml/min): 0.5; 20 sample volume (ul); column temperature (. degree. C.): 35; c18 liquid chromatography column; ultraviolet detection wavelength (nm): 360.

and (3) sampling 3 needles for each concentration, processing a spectrogram after detection, determining the peak emergence position of the standard substance, then performing integration processing on the peak emergence of the standard substance, and recording the peak emergence time and the peak emergence area. And summarizing the peak areas of the standard substances at different concentrations in an excel table to obtain a standard curve graph, and obtaining a standard curve formula and an R value according to the graph. Specific results are shown in FIGS. 1-6 and the following table:

components	Formula of standard curve	R2Value of
			Formaldehyde (I)	Y＝1733.5X+5.2585	0.9994
Acetaldehyde	Y＝11.977X+6.2652	0.9903
			Acrolein	Y＝46.954X+6.164	0.9912
Acetone (II)	Y＝11.573X+8.9671	0.9925
			Propionaldehyde	Y＝34.552X-48.126	0.9990

Accurately weighing 0.2g of polyether modified organic silicon sample (marked as sample 1, the molecular weight of the sample is about 1000), and recording the sample weighing amount when the data is accurate to four decimal places. 20ml of 1 percent 2, 4-dinitrophenylhydrazine solution and 2ml of 1 percent phosphoric acid solution are added, a condensing tube is connected above the round-bottom flask, and the derivatization reaction is carried out for 1h at 60 ℃ in an oil bath. After cooling to room temperature, the condenser tube was rinsed with a small amount of acetonitrile, and the derivative solution was filtered through a 0.45 μm organic filter.

Meanwhile, preparing an empty round-bottom flask as a blank control, adding 20ml of 1% 2, 4-dinitrophenylhydrazine solution and 2ml of 1% phosphoric acid solution, connecting a condensing tube above the round-bottom flask, and carrying out oil bath derivatization reaction at 60 ℃ for 1 h. After cooling to room temperature, the condenser tube was rinsed with a small amount of acetonitrile, and the derivative solution was filtered through a 0.45 μm organic filter.

And respectively injecting the derivative liquid of the sample and the derivative liquid of the blank control into a high performance liquid chromatograph for detection, wherein each sample is injected with 3 needles. And (3) processing the spectrogram after the experiment is finished, firstly, determining the peak appearance position of the aldehyde ketone substance by qualitatively comparing the peak appearance time of the standard substance with the peak appearance time of the sample, then, carrying out integral processing on the peak appearance of each component, and recording the peak appearance time and the peak appearance area. And substituting the peak area into the standard curve formula, and calculating to obtain the detection content Ai of each aldehyde ketone in the sample.

Calculating the content of aldehyde ketone component in the sample according to the formula W ═ (Ai-A0)/m;

w- - -the actual content of corresponding aldehyde ketone in the sample is mug/g;

ai- - -the detected content of corresponding aldehyde ketone in the sample is mu g;

a0- -corresponding to the content of aldehyde ketone in blank μ g;

m-sample mass g.

And (3) reporting a result: the results are expressed in μ g/g, with 2 significant digits retained.

The results of the measurements are shown in FIG. 7.

Example 2 to example 6

The test was conducted in accordance with the test method of example 1, except that the polyether modified silicone samples used were different, example 2 was designated as sample 2 and had a molecular weight of about 1300, example 3 was designated as sample 3 and had a molecular weight of about 2000, example 4 was designated as sample 4 and had a molecular weight of about 3200, example 5 was designated as sample 5 and had a molecular weight of about 5000, example 6 was designated as sample 6 and had a molecular weight of about 5700, and the test results were as follows:

the sample provided in the example of the present invention is a sample prepared by the inventors, and for example, sample 1 is a sample synthesized by the synthesis method of reference CN 109942823A.

And (3) verification:

1. repeatability test

The polyether modified silicone sample of example 5 above was selected and 10 parts, 0.2g per sample, with the data being accurate to four decimal places and the sample weights recorded. 20ml of 1 percent 2, 4-dinitrophenylhydrazine solution and 2ml of 1 percent phosphoric acid solution are respectively added, a condenser tube is connected above the round-bottom flask, and the derivatization reaction is carried out for 1h at 60 ℃ in an oil bath. After cooling to room temperature, the condenser tube was rinsed with a small amount of acetonitrile, and the derivative solution was filtered through a 0.45 μm organic filter. Meanwhile, preparing an empty round-bottom flask as a blank control, adding 20ml of 1% 2, 4-dinitrophenylhydrazine solution and 2ml of 1% phosphoric acid solution, connecting a condensing tube above the round-bottom flask, and carrying out oil bath derivatization reaction at 60 ℃ for 1 h. After cooling to room temperature, the condenser tube was rinsed with a small amount of acetonitrile, and the derivative solution was filtered through a 0.45 μm organic filter.

And respectively injecting the derivative liquid of the sample and the derivative liquid of the blank control into a high performance liquid chromatograph for detection, wherein each sample is injected with 3 needles. And (3) processing the spectrogram after the experiment is finished, firstly, determining the peak appearance position of the aldehyde ketone substance by qualitatively comparing the peak appearance time of the standard substance with the peak appearance time of the sample, then, carrying out integral processing on the peak appearance of each component, and recording the peak appearance time and the peak appearance area. And substituting the peak area into the standard curve formula, and calculating to obtain the detection content Ai of each aldehyde ketone in the sample.

Calculating the content of aldehyde ketone component in the sample according to the formula W ═ (Ai-A0)/m;

w- - -the actual content of corresponding aldehyde ketone in the sample is mug/g;

ai- - -the detected content of corresponding aldehyde ketone in the sample is mu g;

a0- -corresponding to the content of aldehyde ketone in blank μ g;

m-sample mass g.

And (3) reporting a result: the results are expressed in μ g/g, with 2 significant digits retained. The results of the tests are shown in the following table:

according to the results, the detection method provided by the embodiment of the invention has the advantages of high accuracy, high repeatability and small error among repeated experiments.

2. Standard recovery rate experiment

The experimental steps are as follows: selecting the polyether modified organic silicon sample of the embodiment 2 for removing the low part; specifically, the sample obtained by the low-temperature removal treatment is a polyether modified organic silicon sample obtained by processing through a reduced pressure distillation process at 110 ℃, the aldehyde ketone content is detected according to the steps of a repeatability experiment, the sample is parallelly detected for 5 times, and the content of each component of aldehyde ketone is averaged. To this sample, formaldehyde, acetaldehyde, propionaldehyde, acrolein, and acetone standards were added, the rotor was added, the cap was closed and stirred for 2 hours, while the mass of the added standards was recorded. Weighing 6 parts of each sample, wherein 0.2g of each sample is obtained, the data are accurate to four decimal places, and the sample weighing amount is recorded. The subsequent operation is the same as the operation steps of the repeated experiment, and the detection results are as follows:

from experimental data, the recovery rate of each component of aldehyde ketone is between 90% and 110%, and the recovery rate meets the requirement.

The above description is only a preferred embodiment of the present invention and is not intended to limit the present invention, and various modifications and changes may be made by those skilled in the art. Any modification, equivalent replacement, or improvement made within the spirit and principle of the present invention should be included in the protection scope of the present invention.