CN111855845A - Method for detecting plasticizer in leather product - Google Patents
Method for detecting plasticizer in leather product Download PDFInfo
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- CN111855845A CN111855845A CN202010645983.XA CN202010645983A CN111855845A CN 111855845 A CN111855845 A CN 111855845A CN 202010645983 A CN202010645983 A CN 202010645983A CN 111855845 A CN111855845 A CN 111855845A
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- G—PHYSICS
- G01—MEASURING; TESTING
- G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
- G01N30/00—Investigating or analysing materials by separation into components using adsorption, absorption or similar phenomena or using ion-exchange, e.g. chromatography or field flow fractionation
- G01N30/02—Column chromatography
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- G—PHYSICS
- G01—MEASURING; TESTING
- G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
- G01N30/00—Investigating or analysing materials by separation into components using adsorption, absorption or similar phenomena or using ion-exchange, e.g. chromatography or field flow fractionation
- G01N30/02—Column chromatography
- G01N30/04—Preparation or injection of sample to be analysed
- G01N30/06—Preparation
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- G—PHYSICS
- G01—MEASURING; TESTING
- G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
- G01N30/00—Investigating or analysing materials by separation into components using adsorption, absorption or similar phenomena or using ion-exchange, e.g. chromatography or field flow fractionation
- G01N30/02—Column chromatography
- G01N30/04—Preparation or injection of sample to be analysed
- G01N30/06—Preparation
- G01N2030/062—Preparation extracting sample from raw material
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Abstract
The invention discloses a method for detecting a plasticizer in a leather product, which comprises the following steps: step 1: quantitatively weighing a leather test sample; step 2: putting the leather test sample into tetrahydrofuran for fully dissolving; and step 3: adding n-hexane into the sample organic solution; and 4, step 4: adding the mixed standard solution into a chromatographic column; and 5: eluting the chromatographic column for multiple times; step 6: placing the flat-bottomed flask in a rotary evaporator to obtain a sample concentrated solution; and 7: extracting at normal temperature to obtain extract liquor; and 8: and (4) repeating the steps 4 to 6 on the extraction liquid to purify the extraction liquid, filtering the purified extraction liquid by using qualitative filter paper, and then supplying gas chromatography-mass spectrometry for plasticizer determination. The invention provides a method for detecting a plasticizer in a leather product, which can quickly and simply obtain a detection result of the content of a plasticizer compound, has high detection speed, does not need to depend on large equipment and has low detection cost.
Description
Technical Field
The invention relates to the technical field of leather detection, in particular to a method for detecting a plasticizer in a leather product.
Background
Phthalic Acid Esters (PAEs) are an important class of organic compounds. Generally, the liquid is colorless and transparent oily liquid, is insoluble in water and is soluble in methanol and ethanol. Dimethyl phthalate (DMP), diethyl phthalate (DEP), di-n-butyl phthalate (DBP), di-n-octyl phthalate (DOP), diisooctyl phthalate (DEHP), and Butyl Benzyl Phthalate (BBP) are common. PAEs are mainly used as plasticizers in plastic bags and plastic products to increase the plasticity and strength of the products, and also as a raw material for production of pesticide carriers, insect repellents, cosmetics, fragrances, lubricants and defoaming agents. In recent years, with the industrial production and the use of plastic products, phthalate ester is entering the environment, is commonly present in environmental samples such as soil, sediment, water, organisms, air dust-reducing substances and the like, and becomes an ubiquitous pollutant in the environment. The hazards of PAEs to humans are diverse, such as carcinogenicity, teratogenicity, and immunosuppression, with the most striking being the cause of abnormal human reproductive function. They play a role similar to estrogen in human bodies and animal bodies, interfere endocrine, reduce the amount of sperms and the number of sperms in men, reduce the motility of the sperms, abnormal sperm morphology and the like, and are classified as environmental estrogens. The pollution of PAEs to the atmosphere mainly comes from spraying paint, burning of plastic wastes and volatilization of plasticizers in agricultural films, wherein the pollution of plasticizers to the atmosphere is valued by people. PAEs enter a natural environment, migrate and convert in environmental media such as soil, water, atmosphere and the like through processes such as leaching, volatilization, sedimentation and the like, accumulate in soil and sediments, can enter organisms and accumulate in the organisms, and cause great harm.
With the rapid development of the textile industry, the synthetic fiber industry and the leather industry, plasticizers have become one of the most important processing aids, and various plasticizers are added during production in order to enable the processing of leather products and to improve the properties of products. However, the plasticizer added into the leather product is dissolved out, migrated and volatilized during the processing and using processes, which affects the using performance of the product on one hand, and may cause damage to human health and environment when released into the surrounding environment, especially to the human body on the other hand. Numerous studies have demonstrated that plasticizers can enter the human body and harm health through a variety of routes such as daily human inhalation, skin absorption, and environmental pollution. Therefore, the toxicity problem of the plasticizer causes a great concern, and the research on the method for measuring the migration of the plasticizer in leather products is increasingly emphasized.
Disclosure of Invention
The invention aims to provide a method for detecting a plasticizer in a leather product so as to solve the problems in the background technology.
In order to achieve the purpose, the invention provides the following technical scheme: a method for detecting a plasticizer in a leather product comprises the following steps:
step 1: quantitatively weighing a leather test sample, and removing glue and attachments on the leather test sample;
Step 2: putting a leather test sample into tetrahydrofuran for full dissolution to obtain a sample organic solution;
and step 3: adding normal hexane into the sample organic solution, and diluting the sample organic solution into a mixed standard solution;
and 4, step 4: adding the mixed standard solution into a chromatographic column, standing for 15min, and then leaching the chromatographic column with 30-40 ml of n-hexane for multiple times;
and 5: eluting the chromatographic column for multiple times by using 30-40 ml of mixed organic solvent of acetone and normal hexane, and collecting the eluted eluent into a 100ml flat-bottomed flask;
step 6: placing the flat-bottomed flask in a rotary evaporator, concentrating the eluent in the flat-bottomed flask to nearly 1ml in low vacuum, and blowing the eluent in a slow nitrogen flow to obtain a sample concentrated solution;
and 7: weighing 1g of sample concentrated solution, placing the sample concentrated solution in a triangular flask, adding 15-20 ml of trichloromethane, placing the triangular flask in an ultrasonic generator, and extracting at normal temperature for 15-20 min to obtain an extract liquor;
and 8: and (4) repeating the steps 4 to 6 on the extraction liquid to purify the extraction liquid, filtering the purified extraction liquid by using qualitative filter paper, and then supplying gas chromatography-mass spectrometry for plasticizer determination.
Preferably, in step 1, the leather test specimen is cut into strips, and the specific gravity of the moisture in the leather test specimen is less than 30% of the whole.
Preferably, in step 4, the column is an alumina column, which is rinsed with 5ml of n-hexane before use.
Preferably, in step 6, the low vacuum temperature of the rotary evaporator is kept between 55 and 60 ℃.
Preferably, in step 7, the frequency of the ultrasonic generator is 30 to 45 kHz.
Preferably, the plasticizer comprises at least one of the following: dibutyl phthalate, butyl benzyl phthalate, di (2-ethyl) hexyl phthalate, dioctyl phthalate, diisononyl phthalate, and diisodecyl phthalate.
Compared with the prior art, the invention has the beneficial effects that:
the invention provides a method for detecting a plasticizer in a leather product, which can quickly, simply and conveniently obtain a detection result of the content of a plasticizer compound, has high detection speed, does not need to depend on large equipment, and has low detection cost; meanwhile, chloroform, acetone or normal hexane is used as an extracting agent of the plasticizer, so that the plasticizer in the leather product can be extracted more thoroughly; meanwhile, ultrasonic waves with the frequency of 30-45 kHz are adopted, and the extraction method is simple and convenient and easy to operate.
Detailed Description
The technical solutions in the embodiments of the present invention will be clearly and completely described below with reference to the embodiments of the present invention, and it is obvious that the described embodiments are only a part of the embodiments of the present invention, and not all of the embodiments. All other embodiments, which can be derived by a person skilled in the art from the embodiments given herein without making any creative effort, shall fall within the protection scope of the present invention.
Example 1:
the invention provides a technical scheme that: a method of detecting a plasticizer in a leather product, the plasticizer comprising at least one of: dibutyl phthalate, butyl benzyl phthalate, di (2-ethyl) hexyl phthalate, dioctyl phthalate, diisononyl phthalate and diisodecyl phthalate, and the detection method comprises the following steps:
step 1: quantitatively weighing a leather test sample, removing glue and attachments on the leather test sample, cutting the leather test sample into strips, wherein the specific gravity of water in the leather test sample is less than 30% of the whole;
step 2: putting a leather test sample into tetrahydrofuran for full dissolution to obtain a sample organic solution;
and step 3: adding normal hexane into the sample organic solution, and diluting the sample organic solution into a mixed standard solution;
and 4, step 4: adding the mixed standard solution into a chromatographic column, standing for 15min, and then repeatedly leaching the chromatographic column with 30ml of n-hexane, wherein the chromatographic column is an alumina chromatographic column and is leached with 5ml of n-hexane before use;
and 5: eluting the chromatographic column for multiple times by using 30ml of mixed organic solvent of acetone and normal hexane, and collecting the eluted eluent into a 100ml flat-bottomed flask;
Step 6: placing the flat-bottomed flask in a rotary evaporator, concentrating the eluent in the flat-bottomed flask to nearly 1ml in low vacuum, blowing the eluent by slow nitrogen flow to obtain a sample concentrated solution, and keeping the low vacuum temperature of the rotary evaporator at 55 ℃;
and 7: weighing 1g of sample concentrated solution, placing the sample concentrated solution in a triangular flask, adding 15ml of trichloromethane, placing the triangular flask in an ultrasonic generator, and extracting for 15min at normal temperature to obtain an extract liquor, wherein the frequency of the ultrasonic generator is 30 kHz;
and 8: and (4) repeating the steps 4 to 6 on the extraction liquid to purify the extraction liquid, filtering the purified extraction liquid by using qualitative filter paper, and then supplying gas chromatography-mass spectrometry for plasticizer determination.
Example 2:
the invention provides a technical scheme that: a method of detecting a plasticizer in a leather product, the plasticizer comprising at least one of: dibutyl phthalate, butyl benzyl phthalate, di (2-ethyl) hexyl phthalate, dioctyl phthalate, diisononyl phthalate and diisodecyl phthalate, and the detection method comprises the following steps:
step 1: quantitatively weighing a leather test sample, removing glue and attachments on the leather test sample, cutting the leather test sample into strips, wherein the specific gravity of water in the leather test sample is less than 30% of the whole;
Step 2: putting a leather test sample into tetrahydrofuran for full dissolution to obtain a sample organic solution;
and step 3: adding normal hexane into the sample organic solution, and diluting the sample organic solution into a mixed standard solution;
and 4, step 4: adding the mixed standard solution into a chromatographic column, standing for 15min, and then repeatedly leaching the chromatographic column with 35ml of n-hexane, wherein the chromatographic column is an alumina chromatographic column and is leached with 5ml of n-hexane before use;
and 5: eluting the chromatographic column for multiple times by using 35ml of mixed organic solvent of acetone and normal hexane, and collecting the eluted eluent into a 100ml flat-bottomed flask;
step 6: placing the flat-bottomed flask in a rotary evaporator, concentrating the eluent in the flat-bottomed flask to nearly 1ml in low vacuum, blowing the eluent by slow nitrogen flow to obtain a sample concentrated solution, and keeping the low vacuum temperature of the rotary evaporator at 55 ℃;
and 7: weighing 1g of sample concentrated solution, placing the sample concentrated solution in a triangular flask, adding 15ml of trichloromethane, placing the triangular flask in an ultrasonic generator, and extracting at normal temperature for 20min to obtain an extract liquor, wherein the frequency of the ultrasonic generator is 40 kHz;
and 8: and (4) repeating the steps 4 to 6 on the extraction liquid to purify the extraction liquid, filtering the purified extraction liquid by using qualitative filter paper, and then supplying gas chromatography-mass spectrometry for plasticizer determination.
Example 3:
the invention provides a technical scheme that: a method of detecting a plasticizer in a leather product, the plasticizer comprising at least one of: dibutyl phthalate, butyl benzyl phthalate, di (2-ethyl) hexyl phthalate, dioctyl phthalate, diisononyl phthalate and diisodecyl phthalate, and the detection method comprises the following steps:
step 1: quantitatively weighing a leather test sample, removing glue and attachments on the leather test sample, cutting the leather test sample into strips, wherein the specific gravity of water in the leather test sample is less than 30% of the whole;
step 2: putting a leather test sample into tetrahydrofuran for full dissolution to obtain a sample organic solution;
and step 3: adding normal hexane into the sample organic solution, and diluting the sample organic solution into a mixed standard solution;
and 4, step 4: adding the mixed standard solution into a chromatographic column, standing for 15min, and then repeatedly leaching the chromatographic column with 40ml of n-hexane, wherein the chromatographic column is an alumina chromatographic column and is leached with 5ml of n-hexane before use;
and 5: eluting the chromatographic column for multiple times by using 40ml of mixed organic solvent of acetone and normal hexane, and collecting the eluted eluent into a 100ml flat-bottomed flask;
Step 6: placing a flat-bottom flask in a rotary evaporator, concentrating eluent in the flat-bottom flask to nearly 1ml in low vacuum, blowing the eluent in a slow nitrogen flow to obtain a sample concentrated solution, and keeping the low vacuum temperature of the rotary evaporator at 55-60 ℃;
and 7: weighing 1g of sample concentrated solution, placing the sample concentrated solution in a triangular flask, adding 20ml of chloroform, placing the triangular flask in an ultrasonic generator, and extracting at normal temperature for 20min to obtain an extract liquor, wherein the frequency of the ultrasonic generator is 45 kHz;
and 8: and (4) repeating the steps 4 to 6 on the extraction liquid to purify the extraction liquid, filtering the purified extraction liquid by using qualitative filter paper, and then supplying gas chromatography-mass spectrometry for plasticizer determination.
In summary, the three embodiments can quickly and simply obtain the detection result of the content of the plasticizer compound, the detection speed is high, large-scale equipment is not required, and the detection cost is low.
Application method
A method for detecting a plasticizer in a leather product comprises the following steps:
step 1: quantitatively weighing a leather test sample, removing glue and attachments on the leather test sample, cutting the leather test sample into strips, wherein the specific gravity of water in the leather test sample is less than 30% of the whole;
step 2: putting a leather test sample into tetrahydrofuran for full dissolution to obtain a sample organic solution;
And step 3: adding normal hexane into the sample organic solution, and diluting the sample organic solution into a mixed standard solution;
and 4, step 4: adding the mixed standard solution into a chromatographic column, standing for 15min, and then leaching the chromatographic column with 30-40 ml of n-hexane for multiple times, wherein the chromatographic column is an alumina chromatographic column and is leached with 5ml of n-hexane before use;
and 5: eluting the chromatographic column for multiple times by using 30-40 ml of mixed organic solvent of acetone and normal hexane, and collecting the eluted eluent into a 100ml flat-bottomed flask;
step 6: placing a flat-bottom flask in a rotary evaporator, concentrating eluent in the flat-bottom flask to nearly 1ml in low vacuum, blowing the eluent in a slow nitrogen flow to obtain a sample concentrated solution, and keeping the low vacuum temperature of the rotary evaporator at 55-60 ℃;
and 7: weighing 1g of sample concentrated solution, placing the sample concentrated solution in a triangular flask, adding 15-20 ml of trichloromethane, placing the triangular flask in an ultrasonic generator, and extracting for 15-20 min at normal temperature to obtain an extract liquor, wherein the frequency of the ultrasonic generator is 30-45 kHz;
and 8: and (4) repeating the steps 4 to 6 on the extraction liquid to purify the extraction liquid, filtering the purified extraction liquid by using qualitative filter paper, and then supplying gas chromatography-mass spectrometry for plasticizer determination.
Although embodiments of the present invention have been shown and described, it will be appreciated by those skilled in the art that changes, modifications, substitutions and alterations can be made in these embodiments without departing from the principles and spirit of the invention, the scope of which is defined in the appended claims and their equivalents.
Claims (6)
1. A method for detecting a plasticizer in a leather product is characterized by comprising the following steps:
step 1: quantitatively weighing a leather test sample, and removing glue and attachments on the leather test sample;
step 2: putting a leather test sample into tetrahydrofuran for full dissolution to obtain a sample organic solution;
and step 3: adding normal hexane into the sample organic solution, and diluting the sample organic solution into a mixed standard solution;
and 4, step 4: adding the mixed standard solution into a chromatographic column, standing for 15min, and then leaching the chromatographic column with 30-40 ml of n-hexane for multiple times;
and 5: eluting the chromatographic column for multiple times by using 30-40 ml of mixed organic solvent of acetone and normal hexane, and collecting the eluted eluent into a 100ml flat-bottomed flask;
step 6: placing the flat-bottomed flask in a rotary evaporator, concentrating the eluent in the flat-bottomed flask to nearly 1ml in low vacuum, and blowing the eluent in a slow nitrogen flow to obtain a sample concentrated solution;
and 7: weighing 1g of sample concentrated solution, placing the sample concentrated solution in a triangular flask, adding 15-20 ml of trichloromethane, placing the triangular flask in an ultrasonic generator, and extracting at normal temperature for 15-20 min to obtain an extract liquor;
and 8: and (4) repeating the steps 4 to 6 on the extraction liquid to purify the extraction liquid, filtering the purified extraction liquid by using qualitative filter paper, and then supplying gas chromatography-mass spectrometry for plasticizer determination.
2. The method for detecting the plasticizer in the leather product according to claim 1, wherein: in step 1, the leather test sample is cut into strips, and the specific gravity of the moisture in the leather test sample is less than 30% of the whole.
3. The method for detecting the plasticizer in the leather product according to claim 1, wherein: in step 4, the column was an alumina column, which was rinsed with 5ml of n-hexane before use.
4. The method for detecting the plasticizer in the leather product according to claim 1, wherein: in step 6, the low vacuum temperature of the rotary evaporator is kept at 55-60 ℃.
5. The method for detecting the plasticizer in the leather product according to claim 1, wherein: in step 7, the frequency of the ultrasonic generator is 30-45 kHz.
6. The method for detecting the plasticizer in the leather product according to claim 1, wherein: the plasticizer comprises at least one of the following: dibutyl phthalate, butyl benzyl phthalate, di (2-ethyl) hexyl phthalate, dioctyl phthalate, diisononyl phthalate, and diisodecyl phthalate.
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| Application Number | Priority Date | Filing Date | Title |
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| CN202010645983.XA CN111855845A (en) | 2020-07-07 | 2020-07-07 | Method for detecting plasticizer in leather product |
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| CN202010645983.XA CN111855845A (en) | 2020-07-07 | 2020-07-07 | Method for detecting plasticizer in leather product |
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Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN102279239A (en) * | 2011-07-21 | 2011-12-14 | 广东出入境检验检疫局检验检疫技术中心 | Method for detecting content of triocresyl phosphate fire retardant in rubber part of electrical or electronic product |
| CN107607648A (en) * | 2017-09-14 | 2018-01-19 | 浙江省海洋水产研究所 | The solid phase extraction GC MS detection method of phthalate compound in a kind of deposit |
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2020
- 2020-07-07 CN CN202010645983.XA patent/CN111855845A/en active Pending
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102279239A (en) * | 2011-07-21 | 2011-12-14 | 广东出入境检验检疫局检验检疫技术中心 | Method for detecting content of triocresyl phosphate fire retardant in rubber part of electrical or electronic product |
| CN107607648A (en) * | 2017-09-14 | 2018-01-19 | 浙江省海洋水产研究所 | The solid phase extraction GC MS detection method of phthalate compound in a kind of deposit |
Non-Patent Citations (4)
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| 中华人民共和国国家质量监督检验检疫总局 等: "《中华人民共和国国家标准 GB/T 22931-2008》", 30 December 2008 * |
| 王成云 等: "气相色谱/质谱-选择离子监测法同时测定皮革制品中21种邻苯二甲酸酯类化合物", 《皮革与化工》 * |
| 王成云 等: "超声萃取-超高效液相色谱/静电场轨道阱高分辨质谱法同时测定皮革及其制品中23种邻苯二甲酸酯类增塑剂的含量", 《皮革与化工》 * |
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