CN117929615A - Qualitative and quantitative analysis method for impurities in cyanoacrylate adhesive - Google Patents
Qualitative and quantitative analysis method for impurities in cyanoacrylate adhesive Download PDFInfo
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- CN117929615A CN117929615A CN202410331435.8A CN202410331435A CN117929615A CN 117929615 A CN117929615 A CN 117929615A CN 202410331435 A CN202410331435 A CN 202410331435A CN 117929615 A CN117929615 A CN 117929615A
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- 239000012535 impurity Substances 0.000 title claims abstract description 106
- 239000004830 Super Glue Substances 0.000 title claims abstract description 86
- FGBJXOREULPLGL-UHFFFAOYSA-N ethyl cyanoacrylate Chemical compound CCOC(=O)C(=C)C#N FGBJXOREULPLGL-UHFFFAOYSA-N 0.000 title claims abstract description 48
- 238000004445 quantitative analysis Methods 0.000 title claims abstract description 32
- 238000000034 method Methods 0.000 title claims abstract description 30
- 238000004451 qualitative analysis Methods 0.000 title claims abstract description 30
- 239000000243 solution Substances 0.000 claims abstract description 85
- 239000012086 standard solution Substances 0.000 claims abstract description 56
- 239000007788 liquid Substances 0.000 claims abstract description 18
- 239000007789 gas Substances 0.000 claims description 66
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 claims description 58
- 239000000126 substance Substances 0.000 claims description 26
- 238000004364 calculation method Methods 0.000 claims description 16
- 239000003960 organic solvent Substances 0.000 claims description 16
- JYTXVMYBYRTJTI-UHFFFAOYSA-N 2-methoxyethyl 2-cyanoprop-2-enoate Chemical compound COCCOC(=O)C(=C)C#N JYTXVMYBYRTJTI-UHFFFAOYSA-N 0.000 claims description 14
- NIQCNGHVCWTJSM-UHFFFAOYSA-N Dimethyl phthalate Chemical group COC(=O)C1=CC=CC=C1C(=O)OC NIQCNGHVCWTJSM-UHFFFAOYSA-N 0.000 claims description 10
- 238000007865 diluting Methods 0.000 claims description 9
- 238000002347 injection Methods 0.000 claims description 8
- 239000007924 injection Substances 0.000 claims description 8
- 230000014759 maintenance of location Effects 0.000 claims description 7
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 claims description 6
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 6
- HEDRZPFGACZZDS-UHFFFAOYSA-N Chloroform Chemical compound ClC(Cl)Cl HEDRZPFGACZZDS-UHFFFAOYSA-N 0.000 claims description 6
- 238000002360 preparation method Methods 0.000 claims description 6
- FBSAITBEAPNWJG-UHFFFAOYSA-N dimethyl phthalate Natural products CC(=O)OC1=CC=CC=C1OC(C)=O FBSAITBEAPNWJG-UHFFFAOYSA-N 0.000 claims description 5
- 229960001826 dimethylphthalate Drugs 0.000 claims description 5
- 238000002156 mixing Methods 0.000 claims description 5
- 239000012159 carrier gas Substances 0.000 claims description 4
- 238000004587 chromatography analysis Methods 0.000 claims description 4
- 239000004205 dimethyl polysiloxane Substances 0.000 claims description 4
- 235000013870 dimethyl polysiloxane Nutrition 0.000 claims description 4
- 229920000435 poly(dimethylsiloxane) Polymers 0.000 claims description 4
- 229910001873 dinitrogen Inorganic materials 0.000 claims description 2
- 238000002474 experimental method Methods 0.000 claims description 2
- 238000004817 gas chromatography Methods 0.000 claims description 2
- 238000005259 measurement Methods 0.000 claims description 2
- 239000000203 mixture Substances 0.000 claims description 2
- 239000000853 adhesive Substances 0.000 abstract description 3
- 230000001070 adhesive effect Effects 0.000 abstract description 3
- 238000003908 quality control method Methods 0.000 abstract description 2
- 239000000523 sample Substances 0.000 description 40
- SGLKIEOMYXTGBH-UHFFFAOYSA-N 2-methoxyethyl 2-cyanoacetate Chemical compound COCCOC(=O)CC#N SGLKIEOMYXTGBH-UHFFFAOYSA-N 0.000 description 21
- LTMRRSWNXVJMBA-UHFFFAOYSA-L 2,2-diethylpropanedioate Chemical compound CCC(CC)(C([O-])=O)C([O-])=O LTMRRSWNXVJMBA-UHFFFAOYSA-L 0.000 description 20
- XNWFRZJHXBZDAG-UHFFFAOYSA-N 2-METHOXYETHANOL Chemical compound COCCO XNWFRZJHXBZDAG-UHFFFAOYSA-N 0.000 description 20
- DKMROQRQHGEIOW-UHFFFAOYSA-N Diethyl succinate Chemical compound CCOC(=O)CCC(=O)OCC DKMROQRQHGEIOW-UHFFFAOYSA-N 0.000 description 20
- 238000004519 manufacturing process Methods 0.000 description 5
- 239000003153 chemical reaction reagent Substances 0.000 description 4
- WSFSSNUMVMOOMR-UHFFFAOYSA-N Formaldehyde Chemical compound O=C WSFSSNUMVMOOMR-UHFFFAOYSA-N 0.000 description 3
- 238000005516 engineering process Methods 0.000 description 3
- 238000000556 factor analysis Methods 0.000 description 3
- 238000010813 internal standard method Methods 0.000 description 3
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- 230000009286 beneficial effect Effects 0.000 description 2
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- 238000001514 detection method Methods 0.000 description 2
- 229910052757 nitrogen Inorganic materials 0.000 description 2
- 239000002994 raw material Substances 0.000 description 2
- 239000012488 sample solution Substances 0.000 description 2
- MLIREBYILWEBDM-UHFFFAOYSA-M 2-cyanoacetate Chemical compound [O-]C(=O)CC#N MLIREBYILWEBDM-UHFFFAOYSA-M 0.000 description 1
- 229920001651 Cyanoacrylate Polymers 0.000 description 1
- IYXGSMUGOJNHAZ-UHFFFAOYSA-N Ethyl malonate Chemical compound CCOC(=O)CC(=O)OCC IYXGSMUGOJNHAZ-UHFFFAOYSA-N 0.000 description 1
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 1
- 229930040373 Paraformaldehyde Natural products 0.000 description 1
- 239000000919 ceramic Substances 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000004821 distillation Methods 0.000 description 1
- 238000001914 filtration Methods 0.000 description 1
- 239000011521 glass Substances 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- -1 methoxyethyl Chemical group 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
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- 239000004033 plastic Substances 0.000 description 1
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- 239000002904 solvent Substances 0.000 description 1
- 239000012085 test solution Substances 0.000 description 1
- 238000005303 weighing Methods 0.000 description 1
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Abstract
The invention provides a qualitative and quantitative analysis method for impurities in cyanoacrylate adhesives, and belongs to the technical field of adhesives. The invention solves the technical problems that the qualitative and quantitative analysis method of impurities in the existing cyanoacrylate adhesive is not disclosed and the quality control requirement of the product is difficult to meet; the method comprises quantitative analysis and qualitative analysis of impurities in cyanoacrylate adhesives, wherein the quantitative analysis of the impurities in the cyanoacrylate adhesives comprises the following steps: preparing an internal standard solution; preparing corresponding impurity standard liquid; preparing a cyanoacrylate adhesive response factor solution to be tested; preparing corresponding impurity response factor solution; and respectively injecting the prepared response factor solution of the sample to be detected and the prepared corresponding impurity response factor solution into a gas chromatograph, and determining and calculating to obtain the percentage content of the component to be detected in the sample.
Description
Technical Field
The application relates to the technical field of adhesives, in particular to a qualitative and quantitative analysis method for impurities in cyanoacrylate adhesives.
Background
At present, cyanoacrylate adhesives are single-component, liquid and solvent-free adhesives, have the advantages of simplicity, easiness in use, rapid solidification at room temperature, high bonding strength and the like, can generate stronger bonding to polar materials such as rubber, metal, plastic, ceramic, glass, organism tissues and the like, and therefore have wide application prospects in many fields of China.
The production process of cyanoacrylate adhesive generally adopts liquid formaldehyde or paraformaldehyde and cyanoacetate as raw materials, and mainly adopts three stages of polymerization, depolymerization and distillation purification to finally prepare the corresponding cyanoacrylate adhesive. The prepared cyanoacrylate adhesive product is inevitably free of residual impurities, and takes a cyanoacrylate methoxyethyl product as an example, and mainly comprises the impurities such as cyanoacetic methoxyethyl, ethylene glycol monomethyl ether, diethyl malonate, diethyl succinate and the like. When the impurity content in the cyanoacrylate adhesive product exceeds 1%, stability and curing speed of the product during use will be affected. Therefore, in order to ensure the quality control of the product, qualitative and quantitative analysis of impurities in the product is necessary. However, no qualitative and quantitative analysis method for impurities in cyanoacrylate adhesives is found at present.
Disclosure of Invention
The invention aims to solve the defects of the technology, and provides a qualitative and quantitative analysis method for impurities in cyanoacrylate adhesives, which is used for carrying out qualitative and quantitative analysis on the impurities in products and meeting the requirement of controllable product quality.
The invention provides a qualitative and quantitative analysis method for impurities in cyanoacrylate adhesives, which comprises quantitative analysis and qualitative analysis for the impurities in the cyanoacrylate adhesives, wherein the quantitative analysis for the impurities in the cyanoacrylate adhesives comprises the following steps:
preparing an internal standard solution in the step a): dissolving and diluting an internal standard substance with an organic solvent to obtain an internal standard solution for later use;
Step b) preparing corresponding impurity standard solution: analyzing various impurities in cyanoacrylate adhesives to be detected as components to be detected, respectively taking standard substances of the corresponding impurities, dissolving and diluting the standard substances with an organic solvent to respectively obtain corresponding impurity standard solutions for later use;
Step c), preparing a cyanoacrylate adhesive response factor solution to be tested: taking the cyanoacrylate adhesive to be tested as a sample to be tested, mixing the cyanoacrylate adhesive with the internal standard solution obtained in the step a), and diluting the mixture with an organic solvent to obtain a cyanoacrylate adhesive response factor solution to be tested, namely a sample response factor solution to be tested;
Step d) preparation of corresponding impurity response factor solution: mixing the corresponding impurity standard solution obtained in the step b) with the internal standard solution obtained in the step a), and diluting with an organic solvent to obtain a corresponding impurity response factor solution;
Step e), the response factor solution of the sample to be detected prepared in the step c) and the corresponding impurity response factor solution prepared in the step d) are respectively injected into a gas chromatograph, and the percentage content of the component to be detected in the sample can be obtained through measurement and calculation; the calculation formula is as follows:
wherein,
S Component to be tested is the peak area of the component to be detected in the gas chromatogram of the response factor solution of the sample to be detected;
m Sample to be measured is the mass of the sample to be measured in the response factor solution of the sample to be measured;
m Internal standard A is the total mass of the internal standard solution in the response factor solution of the sample to be detected;
S Internal standard A is the peak area of an internal standard substance in a gas chromatogram of the sample response factor solution to be detected;
m Internal standard is the mass of an internal standard in the prepared internal standard solution;
m Internal standard is the total mass of the prepared internal standard solution;
RF is the response factor of the component to be measured;
S Standard of is the peak area of a standard substance of the corresponding impurity in the gas chromatogram of the corresponding impurity response factor solution;
m Standard solution is the mass of the standard solution of the corresponding impurity in the corresponding impurity response factor solution;
m Standard substance is the quality of the standard substance of the corresponding impurity in the prepared standard liquid of the corresponding impurity;
m Standard solution is the total mass of the prepared corresponding impurity standard solution;
m Internal standard liquid is the mass of the internal standard solution in the corresponding impurity response factor solution;
S Internal standard is the peak area of the internal standard in the gas chromatogram of the corresponding impurity response factor solution.
In the quantitative analysis process of the impurities in the cyanoacrylate adhesive, according to the obtained gas chromatogram of the corresponding impurity response factor solution, the gas chromatogram is respectively compared with the gas chromatogram of the response factor solution of the sample to be detected, and when the RF value and the percentage content of the component to be detected in the sample are calculated, the qualitative analysis of the impurities is completed.
Preferably, the internal standard is dimethyl phthalate.
Preferably, the corresponding impurity response factor solutions prepared in the step e) are respectively injected into a gas chromatograph, are subjected to parallel experiments for multiple times, and are arithmetically averaged to calculate RF.
Preferably, the further qualitative analysis of impurities in cyanoacrylate adhesives comprises the following steps:
a) Analyzing various impurities in the cyanoacrylate adhesive, and fixing the volume of the various impurities by using an organic solvent to prepare gas-phase qualitative solutions of the various impurities respectively for later use;
b) The cyanoacrylate adhesive to be measured is subjected to constant volume by using an organic solvent, and a gas-phase qualitative solution of the cyanoacrylate adhesive to be measured is prepared for standby;
c) And c), respectively injecting the gas-phase qualitative solution of various impurities prepared in the step a) and the gas-phase qualitative solution of the cyanoacrylate adhesive to be tested prepared in the step b) into a gas chromatograph for chromatographic analysis, respectively comparing the gas-phase chromatograms of the gas-phase qualitative solution of various impurities with the gas-phase chromatograms of the gas-phase qualitative solution of the cyanoacrylate adhesive to be tested, and combining the gas-phase chromatograms of the gas-phase qualitative solution of the cyanoacrylate adhesive to be tested with the retention time of various impurities to complete qualitative analysis of the impurities in the cyanoacrylate adhesive to be tested.
Preferably, the gas chromatography conditions include:
Chromatographic column: a dimethylpolysiloxane column, 30m×0.53mm;
Carrier gas: nitrogen gas;
Sample inlet temperature: 260-300 ℃;
Column temperature: the initial column temperature is 160-190 ℃, and the temperature is increased to 240-260 ℃ at 20 ℃/min;
Sample injection amount: 0.2-0.6 mu L;
The total flow of the chromatographic column is 0.4-2mL/min, and the split ratio is (20-26): 1;
Detector temperature: 280-300 ℃.
Preferably, the organic solvent is one of dichloromethane, acetone and chloroform.
Preferably, the cyanoacrylate adhesive is a methoxyethyl cyanoacrylate adhesive.
The beneficial effects of the invention are as follows: the qualitative and quantitative analysis method for the impurities in the cyanoacrylate adhesive is convenient to operate and accurate in detection, and can accurately reflect the content of the impurities such as methoxy ethyl cyanoacetate in the product, so that reliable data support is provided for production, the quality of the product is effectively improved, and the stability of the production is ensured.
(1) Qualitative analysis: under the same chromatographic conditions, respectively carrying out chromatographic analysis on known impurities (namely standard samples) and cyanoacrylate adhesive samples to be detected to obtain gas chromatograms of the known impurities (namely standard samples) and the cyanoacrylate adhesive samples to be detected, and then comparing the retention values of the known impurities (namely standard samples) and the cyanoacrylate adhesive samples to be detected, wherein when parameters of the known impurities (namely standard samples) and the cyanoacrylate adhesive samples to be detected are the same, the samples can be considered to contain the same compound as the impurities. And comparing the retention time with the impurity peak in the cyanoacrylate adhesive to be detected through the standard sample, thereby determining the impurity type in the cyanoacrylate adhesive to be detected.
(2) Quantitative analysis: when the internal standard method is used as the technology in the quantitative analysis of the gas chromatograph, a certain amount of standard substance is added into the sample, the standard substance can be separated by the chromatograph column and is not interfered by peaks of other components in the sample, and the percentage content of the component to be measured in the sample can be obtained by only measuring and calculating the peak areas and response factors of the internal standard liquid and the component to be measured.
Drawings
In order to more clearly illustrate the technical solutions of the embodiments of the present application, the following description will briefly introduce the drawings that are needed in the embodiments or the description of the prior art, and it is obvious that the drawings in the following description are only some embodiments of the present application.
FIG. 1 is a gas chromatogram of a gas phase qualitative solution of methoxyethyl cyanoacetate in example 1;
FIG. 2 is a gas chromatogram of a qualitative gas phase solution of ethylene glycol monomethyl ether in example 1;
FIG. 3 is a gas chromatogram of a diethyl malonate gas phase qualitative solution in example 1;
FIG. 4 is a gas chromatogram of a diethyl succinate gas phase qualitative solution in example 1;
FIG. 5 is a gas chromatogram of a test solution of methoxyethyl cyanoacrylate adhesive in example 1;
FIG. 6 is a gas chromatogram of methoxyethyl cyanoacetate response factor solution in example 2;
FIG. 7 is a gas chromatogram of the ethylene glycol monomethyl ether response factor solution of example 2;
FIG. 8 is a gas chromatogram of diethyl malonate response factor solution in example 2;
FIG. 9 is a gas chromatogram of the diethyl succinate response factor solution in example 2;
fig. 10 is a gas chromatogram of the sample response factor solution to be tested in example 2.
Detailed Description
In order to make the technical problems, technical schemes and beneficial effects to be solved more clear, the application is further described in detail below with reference to the accompanying drawings and embodiments. It should be understood that the specific embodiments described herein are for purposes of illustration only and are not intended to limit the scope of the application. The method used in the application is a conventional method unless specified otherwise; the raw materials and devices used, unless otherwise specified, are all conventional commercial products.
Example 1
Example 1 is a qualitative analysis method of impurities in cyanoacrylate adhesives to be tested, taking methoxy ethyl cyanoacrylate adhesives to be tested as an example.
1. Reagent(s)
Methoxyethyl cyanoacetate: the content is more than 99.5 percent;
Ethylene glycol monomethyl ether: the content is more than 99.5 percent;
diethyl malonate: the content is more than 99.5 percent;
diethyl succinate: the content is more than 99.5 percent;
Dichloromethane: 99.5% or more.
2. Apparatus and device
Volumetric flask: 10mL;
Reagent bottle: 100g;
Microsyringe: 10. Mu.L;
Gas chromatograph: matching with an FID detector and programming temperature;
chromatographic column: agilent DB-1 type contains 100% dimethylpolysiloxane column (30 m×0.53mm×5 μm);
carrier gas: nitrogen, total flow 0.4-2mL/min, split ratio: (20-26): 1;
Sample inlet temperature: 260-300 ℃;
column temperature: the initial column temperature is 160-190 ℃, the temperature is kept for 1min, the temperature is increased to 240-260 ℃ at 20 ℃/min, and the temperature is kept for 15-20min;
Sample injection amount: 0.2-0.6 mu L;
Detector temperature: 280-300 ℃.
3. Preparing a gas-phase qualitative solution:
(1) Preparing a methoxy ethyl cyanoacetate gas-phase qualitative solution:
1g of methoxyethyl cyanoacetate was weighed and taken up in methylene chloride to a volume of 10mL, which was a gas phase qualitative solution of methoxyethyl cyanoacetate.
(2) Preparing a gas-phase qualitative solution of ethylene glycol monomethyl ether:
1g of ethylene glycol monomethyl ether was weighed and fixed to a volume of 10mL with methylene chloride, which was a gas phase qualitative solution of ethylene glycol monomethyl ether.
(3) Preparing diethyl malonate gas-phase qualitative solution:
1g diethyl malonate was taken and fixed to a volume of 10mL with methylene chloride, which was a gas phase qualitative solution of diethyl malonate.
(4) Preparing a diethyl succinate gas-phase qualitative solution:
1g of diethyl succinate is taken and fixed to a volume of 10mL by using methylene dichloride, and the volume is a gas-phase qualitative solution of diethyl succinate.
4. Preparing a methoxy ethyl cyanoacrylate adhesive to be tested:
1g of methoxyethyl cyanoacrylate adhesive to be measured is weighed, and the volume is fixed to 10mL by using methylene dichloride, so that the methoxyethyl cyanoacrylate adhesive to be measured is liquid to be measured.
5. Feeding 0.2uL of methoxyethyl cyanoacetate gas-phase qualitative solution with a10 uL sample injection needle, and performing gas-phase chromatogram as shown in figure 1;
Feeding 0.2uL of ethylene glycol monomethyl ether gas-phase qualitative solution with a 10uL sample injection needle, and performing gas-phase chromatogram as shown in FIG. 2;
Feeding 0.2uL diethyl malonate gas-phase qualitative solution with 10uL sample injection needle, and gas-phase chromatogram as shown in figure 3;
Feeding 0.2uL diethyl succinate gas-phase qualitative solution with a 10uL sample injection needle, and performing gas-phase chromatogram as shown in FIG. 4;
Feeding the methoxy ethyl cyanoacrylate adhesive to be measured with the same method, and obtaining a gas chromatogram, as shown in FIG. 5;
According to the comparison of the figures 1-4 with the figure 5, the methoxy ethyl cyanoacrylate adhesive is determined to contain methoxy ethyl cyanoacetate, ethylene glycol monomethyl ether, diethyl malonate and diethyl succinate.
Example 2
Example 2 is a quantitative analysis method of impurities in cyanoacrylate adhesives to be tested, taking methoxy ethyl cyanoacrylate adhesives to be tested as an example.
1. Reagent(s)
Dimethyl phthalate: the content is more than 99.5 percent;
Methoxyethyl cyanoacetate: the content is more than 99.5 percent;
Ethylene glycol monomethyl ether: the content is more than 99.5 percent;
diethyl malonate: the content is more than 99.5 percent;
diethyl succinate: the content is more than 99.5 percent;
Dichloromethane: 99.5% or more.
2. Apparatus and device
Volumetric flask: 10mL;
Reagent bottle: 100g;
Microsyringe: 10. Mu.L;
Gas chromatograph: matching with an FID detector and programming temperature;
chromatographic column: agilent DB-1 type contains 100% dimethylpolysiloxane column (30 m×0.53mm×5 μm);
carrier gas: nitrogen, total flow 0.4-2mL/min, split ratio: (20-26): 1;
Sample inlet temperature: 260-300 ℃;
column temperature: the initial column temperature is 160-190 ℃, the temperature is kept for 1min, the temperature is increased to 240-260 ℃ at 20 ℃/min, and the temperature is kept for 15-20min;
Sample injection amount: 0.2-0.6 mu L;
Detector temperature: 280-300 ℃.
3. Preparing a methoxy ethyl cyanoacetate gas phase standard solution:
Methoxy ethyl cyanoacetate is selected as a gas phase standard substance, 0.5g (0.0001 g is accurately weighed and recorded as M Standard substance 1 g), dichloromethane is used for fixing the volume to 50g (0.0001 g is accurately weighed and recorded as M Standard solution 1), and gas phase standard liquid 1 is obtained.
4. Preparing a gas phase standard liquid of ethylene glycol monomethyl ether:
Ethylene glycol monomethyl ether is selected as a gas-phase standard substance, 0.5g (0.0001 g is accurately weighed and recorded as M Standard substance 2 g), and dichloromethane is used for fixing the volume to 50g (0.0001 g is accurately recorded as M Standard solution 2) to obtain a gas-phase standard liquid 2.
5. Preparing diethyl malonate gas phase standard solution:
Diethyl malonate is selected as a gas phase standard, 0.5g (to the nearest 0.0001g, denoted as M Standard substance 3) is accurately weighed, and dichloromethane is used for fixing the volume to 50g (to the nearest 0.0001g, denoted as M Standard solution 3) to obtain a gas phase standard solution 3.
6. Preparing diethyl succinate gas phase standard liquid:
Diethyl succinate is selected as a gas phase standard, 0.5g (0.0001 g is accurately weighed and marked as M Standard substance 4), and dichloromethane is used for fixing the volume to 50g (0.0001 g is accurately weighed and marked as M Standard solution 4), so that a gas phase standard solution 4 is obtained.
7. Preparing a gas-phase internal standard solution:
1g of dimethyl phthalate (accurate to 0.0001g, denoted as M Internal standard ) was weighed out accurately, and the volume was fixed to 100g (accurate to 0.0001g, denoted as M Internal standard ) with methylene chloride to obtain a gas-phase internal standard solution.
8. Preparing a response factor solution:
a. Preparation of methoxyethyl cyanoacetate response factor solution ①:
1g of gas phase standard solution 1 (accurate to 0.0001g, denoted as m Standard solution 1) and 1g of gas phase internal standard solution (accurate to 0.0001g, denoted as m Internal standard liquid 1) were accurately weighed into a 10mL volumetric flask, diluted to 10mL with dichloromethane and shaken well.
B. preparation of ethylene glycol monomethyl ether response factor solution ②:
1g of gas phase standard solution 2 (accurate to 0.0001g, denoted as m Standard solution 2) and 1g of gas phase internal standard solution (accurate to 0.0001g, denoted as m Internal standard liquid 2) were accurately weighed into a 10mL volumetric flask, diluted to 10mL with dichloromethane and shaken well.
C. Preparation of diethyl malonate response factor solution ③:
1g of gas phase standard solution 3 (accurate to 0.0001g, denoted as m Standard solution 3) and 1g of gas phase internal standard solution (accurate to 0.0001g, denoted as m Internal standard liquid 3) were accurately weighed into a 10mL volumetric flask, diluted to 10mL with dichloromethane and shaken well.
D. Preparation of diethyl succinate response factor solution ④:
1g of gas phase standard solution 4 (accurate to 0.0001g, marked m Standard solution 4) and 1g of gas phase internal standard solution accurate to 0.0001g, marked m Internal standard liquid 4) were accurately weighed into a 10mL volumetric flask, diluted to 10mL with dichloromethane and shaken well.
9. Preparing a sample solution of the methoxy ethyl cyanoacrylate adhesive to be tested:
1g of methoxyethyl cyanoacrylate adhesive sample to be measured (accurate to 0.0001g, marked as m Sample to be measured ) is accurately weighed, 1g of gas phase internal standard solution (accurate to 0.0001g, marked as m Internal standard A) is accurately weighed into a 10mL volumetric flask, 3mL of dichloromethane is added, and shaking is carried out uniformly.
10. Response factor solution and sample analysis:
a. Analysis of methoxyethyl cyanoacetate response factor: the same procedure was run in parallel with 10uL of methoxyethyl cyanoacetate response factor solution ① and the relative standard deviation of the 3 results required to be no greater than 3% taking the arithmetic mean as the final response factor ①. See figure 6 for a gas chromatogram.
B. ethylene glycol monomethyl ether response factor analysis: the same procedure was run in parallel with 10uL of the ethylene glycol monomethyl ether response factor solution ②, with the relative standard deviation of the 3 results required to be no greater than 3%, taking the arithmetic mean as the final response factor ②. See figure 7 for a gas chromatograph.
C. Diethyl malonate response factor analysis: the same procedure was run in parallel with 10uL of diethyl malonate response factor solution ③ and the relative standard deviation of the 3 results required no more than 3% taking the arithmetic mean as the final response factor ③. See figure 8 for a gas chromatograph.
D. Diethyl succinate response factor analysis: the same procedure was run in parallel with 10uL of the diethyl succinate response factor solution ④ and the relative standard deviation of the 3 results required to be no more than 3% taking the arithmetic mean as the final response factor ④. The gas chromatogram is shown in fig. 9.
11. The sample solution of methoxyethyl cyanoacrylate adhesive to be measured was subjected to 0.2uL in the same manner, and the peak areas of the respective impurities and the peak areas of the internal standard solution were recorded. The gas chromatogram is shown in fig. 10.
12. Results and calculations:
a. calculating the content of methoxyethyl cyanoacetate:
① The response factor of methoxyethyl cyanoacetate is represented by RF 1 and is calculated as follows:
Table 1: methoxyethyl cyanoacetate response factor ① calculation record table
② The content (%) of methoxyethyl cyanoacetate (component 1 to be measured) in the sample is calculated as follows:
Table 2: methoxyethyl cyanoacetate content calculation recording table
B. calculating the content of ethylene glycol monomethyl ether:
① Response factor calculation
The response factor of ethylene glycol monomethyl ether is represented by RF 2, which is expressed as follows:
table 3: ethylene glycol monomethyl ether response factor ② calculation record table
② The content (%) of ethylene glycol monomethyl ether (component 2 to be measured) in the sample is calculated as follows:
table 4: ethylene glycol monomethyl ether content calculation record table
C. Calculating the content of diethyl malonate:
① Diethyl malonate response factor calculation
The response factor of diethyl malonate is represented by RF 3, and the calculation formula is as follows:
table 5: diethyl malonate response factor ③ calculation record table
② The content (%) of diethyl malonate (component 3 to be measured) in the sample was calculated as follows:
table 6: malonic acid diethyl ester content calculation record table
D. calculating the content of diethyl succinate:
① Response factor calculation
The response factor of diethyl succinate is represented by RF 4, and the calculation formula is as follows:
table 7: calculating and recording table of diethyl succinate response factor ④
② The content (%) of diethyl succinate (component 4 to be measured) in the sample is calculated as follows:
Table 8: calculating and recording table for diethyl succinate content
The invention provides a qualitative and quantitative analysis method for impurities in cyanoacrylate adhesives, which comprises the steps of weighing a sample, placing the sample in a quantitative solvent bottle, adding an internal standard solution, diluting to a specified scale with an organic solvent, vibrating and uniformly mixing, filtering, separating by a gas chromatographic column, detecting by a hydrogen flame ionization detector, and quantifying by a retention time qualitative and peak area internal standard method. The method is convenient to operate and accurate in detection, and can accurately reflect the content of the impurities such as methoxy ethyl cyanoacetate in the product, so that reliable data support is provided for production, the product quality is effectively improved, and the production stability is ensured.
(1) Qualitative analysis: under the same chromatographic conditions, respectively carrying out chromatographic analysis on known impurities (namely standard samples) and cyanoacrylate adhesive samples to be detected to obtain gas chromatograms of the known impurities (namely standard samples) and the cyanoacrylate adhesive samples to be detected, and then comparing the retention values of the known impurities (namely standard samples) and the cyanoacrylate adhesive samples to be detected, wherein when parameters of the known impurities (namely standard samples) and the cyanoacrylate adhesive samples to be detected are the same, the samples can be considered to contain the same compound as the impurities. And comparing the retention time with the impurity peak in the cyanoacrylate adhesive to be detected through the standard sample, thereby determining the impurity type in the cyanoacrylate adhesive to be detected.
(2) Quantitative analysis: when the internal standard method is used as the technology in the quantitative analysis of the gas chromatograph, a certain amount of standard substance is added into the sample, the standard substance can be separated by the chromatograph column and is not interfered by peaks of other components in the sample, and the percentage content of the component to be measured in the sample can be obtained by only measuring the peak areas and response factors of the internal standard liquid and the component to be measured.
It should be noted that:
1. The internal standard substance can be dimethyl phthalate, and can also be replaced by other internal standard substances with the same function and no mutual interference;
2. the organic solvent can be dichloromethane, or acetone or chloroform;
3. in the embodiment of the invention, a quantitative analysis method of the methoxy ethyl cyanoacrylate adhesive to be detected is taken as an example, and other cyanoacrylate adhesives can be also suitable for the method.
The foregoing description of the preferred embodiments of the application is not intended to be limiting, but rather is intended to cover all modifications, equivalents, and alternatives falling within the spirit and principles of the application.
Claims (7)
1. The qualitative and quantitative analysis method of the impurities in the cyanoacrylate adhesive is characterized by comprising quantitative analysis and qualitative analysis of the impurities in the cyanoacrylate adhesive, wherein the quantitative analysis of the impurities in the cyanoacrylate adhesive comprises the following steps:
preparing an internal standard solution in the step a): dissolving and diluting an internal standard substance with an organic solvent to obtain an internal standard solution for later use;
Step b) preparing corresponding impurity standard solution: analyzing various impurities in cyanoacrylate adhesives to be detected as components to be detected, respectively taking standard substances of the corresponding impurities, dissolving and diluting the standard substances with an organic solvent to respectively obtain corresponding impurity standard solutions for later use;
Step c), preparing a cyanoacrylate adhesive response factor solution to be tested: taking the cyanoacrylate adhesive to be measured as a sample to be measured, mixing the cyanoacrylate adhesive with the internal standard solution obtained in the step a), and diluting the mixture with an organic solvent to obtain a cyanoacrylate adhesive response factor solution to be measured, namely a sample response factor solution to be measured;
step d) preparation of corresponding impurity response factor solution: mixing the corresponding impurity standard solution obtained in the step b) with the internal standard solution obtained in the step a), and diluting with an organic solvent to obtain a corresponding impurity response factor solution;
Step e), the response factor solution of the sample to be detected prepared in the step c) and the corresponding impurity response factor solution prepared in the step d) are respectively injected into a gas chromatograph, and the percentage content of the component to be detected in the sample can be obtained through measurement and calculation;
the calculation formula is as follows:
wherein,
S Component to be tested is the peak area of the component to be detected in the gas chromatogram of the response factor solution of the sample to be detected;
m Sample to be measured is the mass of the sample to be measured in the response factor solution of the sample to be measured;
m Internal standard A is the total mass of the internal standard solution in the response factor solution of the sample to be detected;
S Internal standard A is the peak area of an internal standard substance in a gas chromatogram of the sample response factor solution to be detected;
m Internal standard is the mass of an internal standard in the prepared internal standard solution;
m Internal standard is the total mass of the prepared internal standard solution;
RF is the response factor of the component to be measured;
S Standard of is the peak area of a standard substance of the corresponding impurity in the gas chromatogram of the corresponding impurity response factor solution;
m Standard solution is the mass of the standard solution of the corresponding impurity in the corresponding impurity response factor solution;
m Standard substance is the quality of the standard substance of the corresponding impurity in the prepared standard liquid of the corresponding impurity;
m Standard solution is the total mass of the prepared corresponding impurity standard solution;
m Internal standard liquid is the mass of the internal standard solution in the corresponding impurity response factor solution;
S Internal standard is the peak area of the internal standard in the gas chromatogram of the corresponding impurity response factor solution.
2. The method for qualitative and quantitative analysis of impurities in cyanoacrylate adhesives according to claim 1, wherein the internal standard is dimethyl phthalate.
3. The method for qualitative and quantitative analysis of impurities in cyanoacrylate adhesives according to claim 1, wherein the corresponding impurity response factor solutions prepared in step e) are respectively injected into a gas chromatograph, and are subjected to parallel experiments for a plurality of times, and the arithmetic average value is taken to calculate RF.
4. The method for qualitative and quantitative analysis of impurities in cyanoacrylate adhesives according to claim 1, wherein the qualitative analysis of impurities in cyanoacrylate adhesives comprises the steps of:
a) Analyzing various impurities in the cyanoacrylate adhesive, and fixing the volume of the various impurities by using an organic solvent to prepare gas-phase qualitative solutions of the various impurities respectively for later use;
b) The cyanoacrylate adhesive to be measured is subjected to constant volume by using an organic solvent, and a gas-phase qualitative solution of the cyanoacrylate adhesive to be measured is prepared for standby;
c) And c), respectively injecting the gas-phase qualitative solution of each impurity prepared in the step a) and the gas-phase qualitative solution of the cyanoacrylate adhesive to be tested prepared in the step b) into a gas chromatograph for chromatographic analysis, respectively comparing the gas-phase chromatographic patterns of the gas-phase qualitative solution of each impurity with the gas-phase chromatographic patterns of the gas-phase qualitative solution of the cyanoacrylate adhesive to be tested according to the gas-phase chromatographic patterns of the gas-phase qualitative solution of each impurity, and combining the gas-phase chromatographic patterns with the retention time of each impurity to complete the qualitative analysis of the impurities in the cyanoacrylate adhesive to be tested.
5. The method for qualitative and quantitative analysis of impurities in cyanoacrylate adhesives according to any one of claims 1 to 4, wherein the gas chromatography conditions include:
Chromatographic column: a dimethylpolysiloxane column, 30m×0.53mm;
Carrier gas: nitrogen gas;
Sample inlet temperature: 260-300 ℃;
Column temperature: the initial column temperature is 160-190 ℃, and the temperature is increased to 240-260 ℃ at 20 ℃/min;
Sample injection amount: 0.2-0.6 mu L;
The total flow of the chromatographic column is 0.4-2mL/min, and the split ratio is (20-26): 1;
Detector temperature: 280-300 ℃.
6. The method for qualitative and quantitative analysis of impurities in cyanoacrylate adhesives according to any one of claims 1 to 4, wherein the organic solvent is one of dichloromethane, acetone and chloroform.
7. The method for qualitative and quantitative analysis of impurities in cyanoacrylate adhesives according to any one of claims 1 to 4, wherein the cyanoacrylate adhesive is a methoxyethyl cyanoacrylate adhesive.
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