CN114324727A - Method for detecting upper limit of total migration volume of glycolic acid and oligomers thereof in PGA food packaging material - Google Patents

Method for detecting upper limit of total migration volume of glycolic acid and oligomers thereof in PGA food packaging material Download PDF

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CN114324727A
CN114324727A CN202111411191.7A CN202111411191A CN114324727A CN 114324727 A CN114324727 A CN 114324727A CN 202111411191 A CN202111411191 A CN 202111411191A CN 114324727 A CN114324727 A CN 114324727A
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glycolic acid
solution
detected
upper limit
sample
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陈春云
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Pujing Chemical Industry Co Ltd
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Pujing Chemical Industry Co Ltd
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Abstract

The invention relates to a method for detecting the upper limit of the total migration volume of glycolic acid and oligomers thereof in a PGA food packaging material, which comprises the steps of mixing a sample to be detected with a simulation solution, sealing, standing for a preset time at a constant temperature, taking out the sample to be detected, and cooling to room temperature to obtain a solution to be detected; mixing the obtained solution to be detected with an alkaline aqueous solution, and carrying out thermal reaction to obtain a pretreatment solution; the content of glycolate in the pretreatment solution was detected by ion chromatography, and the upper limit of the total transport amount of glycolic acid and its oligomers was determined based on the content of glycolate. The detection method provided by the invention can convert glycolic acid and the glycolic acid oligomer transferred into the simulation solution into glycolate after undergoing a thermal reaction, and then detects the content of glycolate in the solution by ion chromatography, so that the upper limit of the total transfer amount of glycolic acid and glycolic acid oligomer with the molecular weight less than 1000 is determined, and the detection method is simple in detection steps, easy to operate and accurate in test.

Description

Method for detecting upper limit of total migration volume of glycolic acid and oligomers thereof in PGA food packaging material
Technical Field
The invention relates to the field of detection, in particular to a method for detecting the upper limit of the total migration volume of glycolic acid and oligomers thereof in a PGA food packaging material.
Background
Nowadays, with the increasing concern of people on food safety, the safety of food packaging materials is also generally concerned. Materials used in food packaging can affect the odor, taste, and color of the food during contact with the food, and can also release certain amounts of toxic chemicals, such as heavy metals, toxic processing aids, and the like, that can migrate into the food and be ingested by the human body, which can pose a serious health hazard over time. For this reason, the country has already produced a series of relevant laws and test standards to regulate the safety quality requirements and test guidelines of food packaging materials. Depending on national standards, the amount of expected and unexpected additives that a material migrates to a simulated fluid when the edible contact material is contacted with a particular simulated fluid at a specified temperature for a specified time needs to be determined.
The polyglycolic acid which is the most promising biodegradable resin for replacing the traditional plastic can also be made into food packaging materials. It has been found through experiments that polyglycolic acid (PGA) -based materials undergo a slight amount of degradation when contacted with alcohol simulants (e.g., 10% ethanol in water), and the degradation products are glycolic acid and glycolic acid oligomers having a molecular weight of less than 1000, and these degradation products migrate into the alcohol simulants, risking ingestion by the human body, and therefore, the migration amount of glycolic acid and glycolic acid oligomers having a molecular weight of less than 1000 in polyglycolic acid food packaging materials needs to be strictly controlled.
At present, in the process of the migration amount test, the concentration of glycolic acid can be generally determined by liquid chromatography, while the concentration of glycolic acid oligomer having a molecular weight of less than 1000 is difficult to determine by liquid chromatography or gel permeation chromatography. However, it is to be noted that since the limit of quantitation by liquid chromatography is high, usually about 50mg/L, this means that the result measured by liquid chromatography has high accuracy only in the case where the actual concentration of glycolic acid detected is greater than 50mg/L, whereas in the case where the actual concentration of glycolic acid is less than 50mg/L, it is difficult to achieve accurate measurement by liquid chromatography. As can be seen from this, even when the actual total migration amount of glycolic acid and glycolic acid oligomer having a molecular weight of less than 1000 in food packaging materials based on polyglycolic acid is less than 50mg/L, the migration amount cannot be accurately measured by liquid chromatography or gel permeation chromatography, which is a technical problem in detecting the migration amount of current food packaging materials based on polyglycolic acid. However, since there is only a few description about effective and accurate detection of the total migration amount of glycolic acid and its oligomers in food packaging materials based on polyglycolic acid, there is a need for research on a method for detecting the total migration amount of glycolic acid and its oligomers in food packaging materials based on polyglycolic acid.
Disclosure of Invention
The present invention has been made to solve the above problems, and an object of the present invention is to provide a method for measuring the upper limit of the total migration amount of glycolic acid and oligomers thereof in a PGA food packaging material.
The purpose of the invention is realized by the following technical scheme:
the detection method for the upper limit of the total migration volume of the glycolic acid and the oligomers thereof in the PGA food packaging material comprises the following steps:
step 1: mixing a sample to be detected with a simulation solution, sealing, standing at a constant temperature of 30-100 ℃ for a preset time, taking out the sample to be detected, and cooling the simulation solution to room temperature to obtain a solution to be detected;
step 2: mixing the solution to be detected obtained in the step 1 with an alkaline aqueous solution, and carrying out a thermal reaction to obtain a pretreatment solution;
and step 3: the content of the glycolate in the pretreatment solution obtained in step 2 is detected by ion chromatography, and the upper limit of the total migration amount of glycolic acid, glycolic acid oligomer having a molecular weight of less than 1000, can be determined based on the content of the glycolate.
As a preferred embodiment, the sample to be detected is pretreated before being mixed with the simulation solution, including cutting the sample to be detected to a proper size. For example, in order to better mix the sample to be detected with the simulation liquid, in the actual operation process, the sample to be detected can be cut to a specified size and then mixed with the simulation liquid, and the sample to be detected can be generally cut to a surface area of about 30-200cm2Preferably 80-120cm2
In a preferred embodiment, the simulated liquid is an ethanol solution with the volume percentage of 10-95%.
As a preferred embodiment, the relationship between the amount of the sample to be detected and the amount of the simulant is as follows: per surface area of 1cm2The sample to be tested is mixed with 1-5mL of a simulant.
In a preferred embodiment, the alkaline aqueous solution is Na2CO3Or NaHCO3Aqueous solution of Na in2CO3Or NaHCO3The mass percentage of the components is 0.01-0.5%. According to the invention, glycolic acid in the liquid to be detected is converted into glycolate by adopting an alkaline aqueous solution, the alkaline aqueous solution is beneficial to hydrolysis of glycolic acid oligomer with the molecular weight of less than 1000 and is converted into glycolate, and thus, the content of the glycolate can be accurately detected by ion chromatography.
As a preferred embodiment, the volume ratio of the solution to be detected to the alkaline aqueous solution is 1: 1-5.
As a preferred embodiment, the conditions of the thermal reaction are: reacting at 50-90 deg.c for 0.5-3 hr. Under the above-mentioned heat, hydrolysis of glycolic acid oligomer having a molecular weight of less than 1000 and formation of glycolate can be accelerated.
In a preferred embodiment, the ion chromatography is performed by using an anion exchange chromatography column, wherein the sample injection volume is controlled to be 10-100 μ L, the temperature of the chromatography column is controlled to be 20-40 ℃, and the flow rate of the leacheate is controlled to be 0.3-0.7 mL/min.
Further, the leacheate is Na with the molar concentration of 1-4mmol/L2CO3Or NaHCO3An aqueous solution.
Further, the sample to be detected is mixed with the simulation liquid and then is placed in a container with pressure resistance or telescopic deformation capacity for sealing. In actual operation, because the simulation liquid is usually a volatile liquid (e.g., ethanol) with a low boiling point, after the sample to be detected is mixed with the simulation liquid, a container is used for sealing, but because the temperature in the container is high (possibly higher than the boiling point of the simulation liquid) when the container is kept at a constant temperature, a material with certain elasticity or ductility can be used for sealing to prevent the container from bursting due to excessive internal pressure, for example, a preservative film or an elastic plastic sheet can be used for sealing.
The predetermined time can be flexibly selected according to the actual application of the sample material to be detected, for example, the predetermined time can be selected to be 20-60 minutes, the predetermined time can be selected to be 1-10 hours, the predetermined time can be selected to be 1-7 days, and the like.
Compared with the prior art, the invention has the following beneficial effects:
the detection method comprises the steps of mixing a solution to be detected with an alkaline aqueous solution, then carrying out thermal reaction, converting glycolic acid transferred into a simulation solution and glycolic acid oligomer with the molecular weight less than 1000 into glycolate, detecting the content of glycolate in the solution by ion chromatography, determining the upper limit of the total transfer amount of glycolic acid and glycolic acid oligomer with the molecular weight less than 1000 according to the content of glycolate, and effectively overcoming the problem of inaccurate detection result caused by incomplete separation of glycolic acid oligomer and glycolic acid. In addition, the detection method can reduce the detection limit of glycolic acid and the oligomer thereof to below 1mg/L, can realize accurate detection, adopts easily obtained equipment, has good economic practicability, is convenient for large-scale popularization, and has good application prospect.
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FIG. 1 is an ion chromatogram of the glycolate in example 1;
FIG. 2 is an ion chromatogram of the glycolate in example 2;
FIG. 3 is an ion chromatogram of the glycolate in example 4.
Detailed Description
The invention is described in detail below with reference to the figures and specific embodiments.
Example 1
In this example, the sample to be examined was a polyglycolic acid film (film thickness about 400 μm) for food packaging, which was cut to a surface area of 60cm2Immersing the film sample in 100mL of ethanol solution with the volume percentage content of 10% which is kept at the constant temperature of 30 ℃, sealing, transferring the film sample to a constant-temperature constant-humidity incubator with the temperature of 30 ℃, standing for 1 hour, taking out the film sample, and naturally cooling the simulation liquid to the room temperature to obtain the solution to be detected; then 300mL of NaHCO with a mass percentage of 0.2% was added to the solution to be tested (about 100mL)3Heating the aqueous solution to 60 deg.C, reacting for 1 hr, and cooling to room temperatureObtaining a pretreatment solution; then, a Switzerland IC Eco ion chromatograph (a Switzerland SUPP A5 anion exchange chromatographic column) is adopted to detect the concentration of the glycolate in the pretreatment solution, and the specific detection conditions are as follows: controlling the injection volume to be 20 mu L, the temperature of a chromatographic column to be 30 ℃, and adopting NaHCO with the molar concentration of 1.5mmol/L3An aqueous solution was used as an eluent, and the flow rate of the eluent was controlled to 0.5 mL/min.
The ion chromatogram of the glycolate in this example is shown in FIG. 1 below. Based on the above detection experiment procedure, the concentration of glycolate in the solution to be detected in this example was about 0.6mg/L, and accordingly it was determined that the upper limit of the total migration amount of glycolic acid, glycolic acid oligomer having a molecular weight of less than 1000, was about 0.6 mg/L.
Example 2
In this example, the sample to be examined was a polyglycolic acid film (film thickness about 400 μm) for food packaging, which was cut to a surface area of 80cm2Immersing the film sample in 300mL of ethanol solution with the volume percentage content of 95% and the constant temperature of 30 ℃, sealing, transferring to a constant temperature and humidity incubator with the temperature of 50 ℃, standing for 8 hours, taking out the film sample, and naturally cooling the simulation solution to room temperature to obtain a solution to be detected; then 300mL of NaHCO with the mass percentage of 0.5% was added to the solution to be tested (about 300mL)3Heating the aqueous solution to about 72 ℃, reacting for 2 hours, and cooling to room temperature to obtain a pretreatment solution; then, a Switzerland IC Eco ion chromatograph (a Switzerland SUPP A5 anion exchange chromatographic column) is adopted to detect the concentration of the glycolate in the pretreatment solution, and the specific detection conditions are as follows: controlling the injection volume to be 50 mu L, the temperature of a chromatographic column to be 35 ℃, and adopting NaHCO with the molar concentration of 2mmol/L3An aqueous solution was used as an eluent, and the flow rate of the eluent was controlled to 0.4 mL/min.
Based on the above detection experiment procedure, the concentration of glycolate in the solution to be detected in this example was about 2.8mg/L, and accordingly it was determined that the upper limit of the total migration amount of glycolic acid, glycolic acid oligomer having a molecular weight of less than 1000, was about 2.8 mg/L.
Example 3
In this example, the sample to be examined was a polyglycolic acid film (film thickness about 400 μm) for food packaging, which was cut to a surface area of 30cm2Immersing the film sample into 150mL of ethanol solution with the volume percentage content of 30% and the constant temperature of 60 ℃, sealing, transferring to a constant-temperature constant-humidity incubator with the temperature of 60 ℃, standing for 1 day, taking out the film sample, and naturally cooling the simulation solution to room temperature to obtain a solution to be detected; 750mL of Na with the mass percent of 0.08 percent is added into the solution to be detected (about 150mL)2CO3Heating the aqueous solution to 50 ℃, reacting for 3 hours, and cooling to room temperature to obtain a pretreatment solution; then, a Switzerland IC Eco ion chromatograph (a Switzerland SUPP A5 anion exchange chromatographic column) is adopted to detect the concentration of the glycolate in the pretreatment solution, and the specific detection conditions are as follows: controlling the injection volume to be 10 mu L, the temperature of a chromatographic column to be 20 ℃, and adopting Na with the molar concentration of 4mmol/L2CO3An aqueous solution was used as an eluent, and the flow rate of the eluent was controlled to 0.3 mL/min.
The ion chromatogram of the glycolate in this example is shown in FIG. 2 below. Based on the above test procedure, the concentration of glycolate in the solution to be tested in this example was about 5.0mg/L, and accordingly it was determined that the upper limit of the total migration amount of glycolic acid, glycolic acid oligomer having a molecular weight of less than 1000, was about 5.0 mg/L.
Example 4
In this example, the sample to be examined was a polyglycolic acid film (film thickness about 400 μm) for food packaging, which was cut to a surface area of 200cm2Immersing the film sample in 200mL of ethanol solution with the volume percentage content of 50% and the constant temperature of 40 ℃, sealing, transferring to a constant temperature and humidity incubator with the temperature of 40 ℃, standing for 5 days, taking out the film sample, and naturally cooling the simulation liquid to room temperature to obtain a solution to be detected; 700mL of Na with a mass percent of 0.01% was then added to the solution to be tested (about 200mL)2CO3Heating the aqueous solution to about 90 deg.C, reacting for 0.5 hr, and cooling to room temperature to obtain the desired productConditioning the solution; then, a Switzerland IC Eco ion chromatograph (a Switzerland SUPP A5 anion exchange chromatographic column) is adopted to detect the concentration of the glycolate in the pretreatment solution, and the specific detection conditions are as follows: controlling the injection volume to be 100 mu L, the temperature of a chromatographic column to be 40 ℃, and adopting Na with the molar concentration of 1mmol/L2CO3An aqueous solution was used as an eluent, and the flow rate of the eluent was controlled to 0.7 mL/min.
The ion chromatogram of the glycolate in this example is shown in FIG. 3 below. Based on the above test procedure, the concentration of glycolate in the solution to be tested in this example was about 9.7mg/L, and accordingly it was determined that the upper limit of the total migration amount of glycolic acid, glycolic acid oligomer having a molecular weight of less than 1000, was about 9.7 mg/L.
The embodiments described above are described to facilitate an understanding and use of the invention by those skilled in the art. It will be readily apparent to those skilled in the art that various modifications to these embodiments may be made, and the generic principles described herein may be applied to other embodiments without the use of the inventive faculty. Therefore, the present invention is not limited to the above embodiments, and those skilled in the art should make improvements and modifications within the scope of the present invention based on the disclosure of the present invention.

Claims (10)

  1. The method for detecting the upper limit of the total migration amount of the glycolic acid and the oligomers thereof in the PGA food packaging material is characterized by comprising the following steps:
    step 1: mixing a sample to be detected with a simulation solution, sealing, standing for a preset time at a constant temperature, taking out the sample to be detected, and cooling the simulation solution to room temperature to obtain a solution to be detected;
    step 2: mixing the solution to be detected obtained in the step 1 with an alkaline aqueous solution, and carrying out a thermal reaction to obtain a pretreatment solution;
    and step 3: the content of the glycolate in the pretreatment solution obtained in step 2 is detected by ion chromatography, and the upper limit of the total migration amount of glycolic acid, glycolic acid oligomer having a molecular weight of less than 1000, can be determined based on the content of the glycolate.
  2. 2. The method for detecting the upper limit of the total migration amount of glycolic acid and the oligomers thereof in the PGA food packaging material as claimed in claim 1, wherein the sample to be detected is pre-treated before being mixed with the simulant, including cutting the sample to be detected to a suitable size.
  3. 3. The method for detecting the upper limit of the total migration amount of glycolic acid and oligomers thereof in PGA food packaging material as claimed in claim 1, wherein the simulated liquid is ethanol solution with a volume percentage of 10-95%.
  4. 4. The method for detecting the upper limit of the total migration amount of glycolic acid and the oligomers thereof in the PGA food packaging material as claimed in claim 1, wherein the usage relationship between the sample to be detected and the simulation liquid is as follows: per surface area of 1cm2The sample to be tested is mixed with 1-5mL of a simulant.
  5. 5. The method of claim 1, wherein the aqueous alkaline solution is Na2CO3Or NaHCO3Aqueous solution of Na in2CO3Or NaHCO3The mass percentage of the components is 0.01-0.5%.
  6. 6. The method for detecting the upper limit of the total migration amount of glycolic acid and oligomers thereof in PGA food packaging material according to claim 1, wherein the volume ratio of the solution to be detected to the alkaline aqueous solution is 1: 1-5.
  7. 7. The method of claim 1, wherein the conditions of the thermal reaction include: reacting at 50-90 deg.c for 0.5-3 hr.
  8. 8. The method for detecting the upper limit of the total migration amount of glycolic acid and the oligomers thereof in the PGA food packaging material as claimed in claim 1, wherein the ion chromatography employs an anion exchange chromatography column, the sample injection volume is controlled to be 10-100 μ L, the temperature of the chromatography column is controlled to be 20-40 ℃, and the flow rate of the leacheate is 0.3-0.7 mL/min.
  9. 9. The method of claim 8, wherein the leacheate is Na having a molar concentration of 1 to 4mmol/L2CO3Or NaHCO3An aqueous solution.
  10. 10. The method for detecting the upper limit of the total migration amount of glycolic acid and the oligomers thereof in the PGA food packaging material as claimed in claim 1, wherein the sample to be detected is mixed with a simulant and then placed in a container having a pressure resistance or a stretching deformation capability for sealing.
CN202111411191.7A 2021-11-25 2021-11-25 Method for detecting upper limit of total migration volume of glycolic acid and oligomers thereof in PGA food packaging material Pending CN114324727A (en)

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Citations (8)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN1441248A (en) * 2003-04-10 2003-09-10 厦门大学 Detection method of glyoxalic acid, glycolic acid, glyoxal and oxalic acid
CN1501923A (en) * 2001-04-12 2004-06-02 ��Ԩ��ѧ��ҵ��ʽ���� Glycolide production process, and glycolic acid oligomer for glycolide production
CN102608228A (en) * 2012-02-29 2012-07-25 广州市质量监督检测研究院 Method for detecting restricted substances in food contact material
CN105044235A (en) * 2015-07-03 2015-11-11 中华人民共和国台州出入境检验检疫局 Method for detecting specific migration amounts of nine anti-oxidants in plastic products by liquid chromatography method
CN106442804A (en) * 2016-11-23 2017-02-22 福建出入境检验检疫局检验检疫技术中心 Detection method for migration quantity of alcamine substances in food plastic package bag
CN110927324A (en) * 2019-12-26 2020-03-27 广州医科大学附属第一医院 Method for simultaneously detecting concentration of glycolic acid and hippuric acid in human urine
CN111757873A (en) * 2018-03-20 2020-10-09 株式会社吴羽 Method for producing glycolide
CN112098582A (en) * 2020-09-03 2020-12-18 深圳天祥质量技术服务有限公司 Method for measuring special migration amount of tetrafluoroethylene in food contact material

Patent Citations (8)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN1501923A (en) * 2001-04-12 2004-06-02 ��Ԩ��ѧ��ҵ��ʽ���� Glycolide production process, and glycolic acid oligomer for glycolide production
CN1441248A (en) * 2003-04-10 2003-09-10 厦门大学 Detection method of glyoxalic acid, glycolic acid, glyoxal and oxalic acid
CN102608228A (en) * 2012-02-29 2012-07-25 广州市质量监督检测研究院 Method for detecting restricted substances in food contact material
CN105044235A (en) * 2015-07-03 2015-11-11 中华人民共和国台州出入境检验检疫局 Method for detecting specific migration amounts of nine anti-oxidants in plastic products by liquid chromatography method
CN106442804A (en) * 2016-11-23 2017-02-22 福建出入境检验检疫局检验检疫技术中心 Detection method for migration quantity of alcamine substances in food plastic package bag
CN111757873A (en) * 2018-03-20 2020-10-09 株式会社吴羽 Method for producing glycolide
CN110927324A (en) * 2019-12-26 2020-03-27 广州医科大学附属第一医院 Method for simultaneously detecting concentration of glycolic acid and hippuric acid in human urine
CN112098582A (en) * 2020-09-03 2020-12-18 深圳天祥质量技术服务有限公司 Method for measuring special migration amount of tetrafluoroethylene in food contact material

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