CN111855727B - Method for detecting purity and impurity content of foaming agent product - Google Patents

Method for detecting purity and impurity content of foaming agent product Download PDF

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CN111855727B
CN111855727B CN202010715759.3A CN202010715759A CN111855727B CN 111855727 B CN111855727 B CN 111855727B CN 202010715759 A CN202010715759 A CN 202010715759A CN 111855727 B CN111855727 B CN 111855727B
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detection method
internal standard
deuterated
mass
foaming agent
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CN111855727A (en
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刘理华
盛江峰
潘卫东
孟令国
刘书群
瞿小新
许宗伟
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Anhui Run Yue Technology Co ltd
Huaibei Normal University
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Anhui Runyue Science And Technology Co ltd
Huaibei Normal University
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    • G—PHYSICS
    • G01—MEASURING; TESTING
    • G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
    • G01N24/00—Investigating or analyzing materials by the use of nuclear magnetic resonance, electron paramagnetic resonance or other spin effects
    • G01N24/08—Investigating or analyzing materials by the use of nuclear magnetic resonance, electron paramagnetic resonance or other spin effects by using nuclear magnetic resonance
    • G—PHYSICS
    • G01—MEASURING; TESTING
    • G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
    • G01N1/00—Sampling; Preparing specimens for investigation
    • G01N1/28—Preparing specimens for investigation including physical details of (bio-)chemical methods covered elsewhere, e.g. G01N33/50, C12Q
    • G—PHYSICS
    • G01—MEASURING; TESTING
    • G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
    • G01N1/00—Sampling; Preparing specimens for investigation
    • G01N1/28—Preparing specimens for investigation including physical details of (bio-)chemical methods covered elsewhere, e.g. G01N33/50, C12Q
    • G01N1/44—Sample treatment involving radiation, e.g. heat
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
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Abstract

The invention relates to the technical field of content analysis of organic foaming agents, and provides a method for detecting the purity and impurity content of a foaming agent product, which comprises the following specific steps: (1) Respectively measuring moisture and ash content of the sample by adopting a constant-temperature drying and high-temperature roasting method; (2) By using 1 According to the HNMR method, a proper amount of foaming agent and an internal standard substance are dissolved in DMSO (deuterated reagent), and the contents of N, N-dinitroso pentamethylene tetramine and tri-nitroso trimethylene triamine in the foaming agent can be measured simultaneously. The invention provides a method for detecting the purity and impurity content of a foaming agent product, which has the advantages of low cost, easy acquisition, simplicity, accuracy, good repeatability and the like of an internal standard.

Description

Method for detecting purity and impurity content of foaming agent product
Technical Field
The invention relates to the technical field of purity analysis of organic foaming agents, in particular to a method for detecting the purity and impurity content of a foaming agent product.
Background
The foaming agent H is an organic chemical foaming agent, the main component is N, N-dinitroso pentamethylene tetramine, nitrogen is generated by heating (> 205 ℃) decomposition, the foaming agent H has the characteristics of large gas generation amount, high bubbling efficiency and the like, can be used as the foaming agent of polyvinyl chloride and copolymers thereof, polyolefin, polystyrene, polyamide, polyester, phenolic resin, polyvinylidene chloride, polysiloxane, polychloroprene, ethylene and propylene copolymers, polyethylene oxide and elastomers thereof, and is an aid widely used for producing rubber and plastic series products with light weight, heat insulation and good mechanical damping characteristics.
The nuclear magnetic resonance hydrogen spectrum technology is mainly used for the structural determination of the organic compound, and is also an important means for quantitative analysis of the organic compound, the basic principle is that the formant area in the 1H-NMR is in direct proportion to the number of hydrogen atoms contained in the formant, and the method has the advantages of no need of introducing any correction factor, high speed, simplicity and accuracy, and the quantitative nuclear magnetic analysis method is already recorded in pharmacopoeias of many countries and regions at present. At present, no technology for determining and detecting the content of N, N-dinitroso pentamethylene tetramine in the foaming agent H through nuclear magnetic resonance hydrogen spectrum is known.
Disclosure of Invention
At present, the foaming agent H is synthesized by taking hexamethylene tetramine and sodium nitrite as raw materials through reaction under low temperature and acidic conditions, and main byproducts in the production process are inorganic salt and Trinitroso Trimethylene Triamine (TTT), wherein the inorganic salt can be removed through water washing, and the trinitroso trimethylene triamine and N, N-dinitroso pentamethylene tetramine have similar physical and chemical properties due to the same functional groups, so that the two are difficult to thoroughly separate, and the TTT can be inhibited only by optimizing process conditions and parameters. However, the purity of the foaming agent H product mainly depends on an empirical method for detecting the nitrogen content in a sample, and the method is not only unscientific, but also difficult to determine the content of the by-product trisnitrosotrimethylene triamine.
Aiming at the situation, the invention provides a method for detecting the purity of a foaming agent H product, which aims at solving the defect that N, N-dinitroso pentamethylene tetramine and trinitroso trimethylene triamine cannot be accurately distinguished in the traditional method for detecting the foaming agent H. In the prior art, no detection method for distinguishing and detecting the contents of components such as N, N-dinitroso pentamethylene tetramine, trinitroso trimethylene triamine and the like by adopting nuclear magnetic resonance hydrogen spectrum exists.
Specifically, the invention provides the following technical scheme:
the invention provides a method for detecting the purity and impurity content of a foaming agent product, which is characterized by comprising the following steps:
(1) Weighing a sample, drying, and calculating the water content W% in the sample;
(3) Roasting the sample, and calculating ash S in the sample;
(3) Weighing a foaming agent and an internal standard, placing the foaming agent and the internal standard in a sample bottle, adding a deuterated solvent for dissolution, and then performing nuclear magnetic resonance hydrogen spectrum test;
(4) Determining characteristic peaks of the N, N-dinitroso pentamethylene tetramine and an internal standard substance in the nuclear magnetic resonance hydrogen spectrum in the step (3), setting nuclear magnetic resonance hydrogen spectrum measurement conditions, and measuring relative integral areas of the characteristic peaks to be A respectively H And A S Substituting the data into the following formula to obtain the mass fraction of the N, N-dinitroso pentamethylene tetramine:
wherein P is H The mass fraction of N, N-dinitroso pentamethylene tetramine; p (P) S Is the purity of the internal standard substance; a is that H Peak area for N, N-dinitroso pentamethylene tetramine; a is that S Peak area for internal standard; n (N) H 1 mole of the number of resonance cores on the functional group of the characteristic signal of N, N-dinitroso pentamethylene tetramine; n (N) S The number of resonating nuclei on the functional group that is characteristic signal of 1 mole of internal standard; m is M H Is the molar mass of N, N-dinitroso pentamethylene tetramine; m is M S Is the molar mass of the internal standard; m is m H The mass of N, N-dinitroso pentamethylene tetramine; m is m S The mass of the internal standard;
(5) The mass fraction of the compound trinitroso trimethylene triamine in the blowing agent was determined and calculated using the same procedure as in step (4).
Preferably, the internal standard in the step (3) is selected from paradichlorobenzene or paradinitrobenzene, and preferably, the internal standard is a high-purity product or standard product.
Preferably, the mass of the sample used in the step (1) or the step (2) is 3-4 g;
preferably, the mass of the sample used in step (3) is 30 to 60mg.
Preferably, wherein the blowing agent product has a moisture content of 0.20 to 0.29wt% and an ash content of 0.060 to 0.083wt%;
preferably, the content of trisnitrosotrimethylene triamine is 0.8 to 2.0wt%.
Preferably, the deuterated solvent is used in the amount of 2.0-8.0mL in the step (3); preferably, the mass of the internal standard in step (4) is 10-25mg.
Preferably, the hydrogen nuclear magnetic resonance spectrum test conditions in the step (4) include: the resonance frequency of the nuclear magnetic spectrometer is 400-600 MHz;
preferably, the temperature is 20-35 ℃; preferably, the pulse angle is 90 °;
preferably, the delay time is 20 to 40 seconds; preferably, the number of samplings is 32 to 128.
Preferably, the drying in step (1) is carried out at a temperature of 70 to 100 ℃, preferably for a drying time of 2 to 4 hours.
Preferably, the temperature at which the calcination in step (2) is carried out is 500 to 800 ℃, and the calcination time is preferably 2 to 4 hours.
Preferably, the deuterated solvent is one or more than two of heavy hydrogen dimethyl sulfoxide (DMSO-d 6), deuterated chloroform and deuterated acetonitrile; preferably heavy hydrogen dimethyl sulfoxide (DMSO-d 6).
The invention also provides application of the method in the technical field of purity analysis of the organic foaming agent.
The beneficial effects of the invention include:
the invention uses 1H-NMR technique to select cheap and stable internal standard substance, which can rapidly and accurately analyze the content of N, N-dinitroso pentamethylene tetramine and trinitroso trimethylene triamine in the foaming agent H sample, and can replace the traditional experience analysis method.
Drawings
FIG. 1 is a nuclear magnetic resonance hydrogen spectrum of example 1-1, wherein the number 1 is a characteristic chemical shift peak of N, N-dinitroso pentamethylene tetramine, the number 2 is a characteristic chemical shift peak of trinitroso trimethylene triamine, and the number 3 is a characteristic chemical shift peak of an internal standard substance.
Detailed Description
Aiming at the defects of the traditional detection method for the purity of the foaming agent product, the invention provides a nuclear magnetic resonance hydrogen spectrum measurement method capable of rapidly and accurately detecting the contents of N, N-dinitroso pentamethylene tetramine and trinitroso trimethylene triamine.
The invention provides a method for detecting the purity and impurity content of a foaming agent product, which is characterized by comprising the following steps:
(1) Weighing a sample, drying, and calculating the water content W% in the sample;
(4) Roasting the sample, and calculating ash S in the sample;
(3) Weighing a foaming agent and an internal standard, placing the foaming agent and the internal standard in a sample bottle, adding a deuterated solvent for dissolution, and then performing nuclear magnetic resonance hydrogen spectrum test;
(4) Determining characteristic peaks of the N, N-dinitroso pentamethylene tetramine and an internal standard substance in the nuclear magnetic resonance hydrogen spectrum in the step (3), setting nuclear magnetic resonance hydrogen spectrum measurement conditions, and measuring relative integral areas of the characteristic peaks to be A respectively H And A S Substituting the data into the following formula to obtain the mass fraction of the N, N-dinitroso pentamethylene tetramine:
wherein P is H The mass fraction of N, N-dinitroso pentamethylene tetramine; p (P) S Is the purity of the internal standard substance; a is that H Peak area for N, N-dinitroso pentamethylene tetramine; a is that S Peak area for internal standard; n (N) H 1 mole of the number of resonance cores on the functional group of the characteristic signal of N, N-dinitroso pentamethylene tetramine; n (N) S The number of resonating nuclei on the functional group that is characteristic signal of 1 mole of internal standard; m is M H Is the molar mass of N, N-dinitroso pentamethylene tetramine; m is M S Is the mole of the internal standard substanceA molar mass; m is m H The mass of N, N-dinitroso pentamethylene tetramine; m is m S The mass of the internal standard;
(5) The mass fraction of the compound trinitroso trimethylene triamine in the blowing agent was determined and calculated using the same procedure as in step (4).
Preferably, the internal standard in the step (3) is selected from paradichlorobenzene or paradinitrobenzene, and preferably, the internal standard is a high-purity product or standard product.
Preferably, the mass of the sample used in the step (1) or the step (2) is 3-4 g;
preferably, the mass of the sample used in step (3) is 30 to 60mg.
Preferably, wherein the blowing agent product has a moisture content of 0.20 to 0.29wt% and an ash content of 0.060 to 0.083wt%;
preferably, the content of trisnitrosotrimethylene triamine is 0.8 to 2.0wt%.
Preferably, the deuterated solvent is used in the amount of 2.0-8.0mL in the step (3); preferably, the mass of the internal standard in step (4) is 10-25mg.
Preferably, the hydrogen nuclear magnetic resonance spectrum test conditions in the step (4) include: the resonance frequency of the nuclear magnetic spectrometer is 400-600 MHz;
preferably, the temperature is 20-35 ℃; preferably, the pulse angle is 90 °;
preferably, the delay time is 20 to 40 seconds; preferably, the number of samplings is 32 to 128.
Preferably, the drying in step (1) is carried out at a temperature of 70 to 100 ℃, preferably for a drying time of 2 to 4 hours.
Preferably, the temperature at which the calcination in step (2) is carried out is 500 to 800 ℃, and the calcination time is preferably 2 to 4 hours.
Preferably, the deuterated solvent is one or more than two of heavy hydrogen dimethyl sulfoxide (DMSO-d 6), deuterated chloroform and deuterated acetonitrile; preferably heavy hydrogen dimethyl sulfoxide (DMSO-d 6).
The invention also provides application of the method in the technical field of purity analysis of the organic foaming agent.
The foaming agent is an amine-containing foaming agent. The foaming agent H is a foaming agent mainly containing N, N-dinitroso pentamethylene tetramine.
Wherein the molar mass of the N, N-dinitroso pentamethylene tetramine and the trinitroso trimethylene triamine is 186.17 and 174.12g/mol, and the chemical formula is C 5 H 10 N 6 O 2 And C 3 H 6 N 6 O 3 The chemical structural formula is as follows:
the characteristic peaks of the nuclear magnetic resonance hydrogen spectrum of the N, N-dinitroso pentamethylene tetramine are as follows: synδ:5.23 (d, j=13 hz, 2H), 5.45 (d, j=13 hz, 2H), 4.22 (d, j=14 hz, 2H), 5.46 (d, j=14 hz, 2H), 4.46 (s, 1H), 5.35 (d, 1H). Anti delta: 5.35 (d, j=13 hz, 2H), 5.77 (d, j=13 hz, 2H), 4.29 (d, j=14 hz, 2H), 5.76 (d, j=14 hz, 2H), 4.46 (s, 2H).
The characteristic peaks of the nuclear magnetic resonance hydrogen spectrum of the trisnitrosotrimethylene triamine are Anti 5.62 (s, 2H), 6.26 (s, 2H), 6.90 (s, 2H), syn 6.22 (s, 2H),
in a preferred embodiment of the invention, a method for detecting the purity of a foaming agent H product is provided, which comprises the following specific steps:
(1) 3-4 g of sample (accurate to 0.0001 g) is weighed in a constant-weight weighing bottle, placed in a constant-temperature drying oven for drying, naturally cooled, and the water content W% in the sample is calculated.
(2) 3-4 g of sample (accurate to 0.0001 g) is weighed in a crucible with constant weight, placed in a muffle furnace for roasting, naturally cooled, and the S% of ash in the sample is calculated.
(3) 30-60 mg of N, N-dinitroso pentamethylene tetramine and 10-25mg of internal standard substance are weighed and placed in a sample bottle, 2.0-8.0mL of deuterated solvent is added for dissolution, and nuclear magnetic resonance hydrogen spectrum test is carried out.
(4) Determining characteristic peaks of N, N-dinitroso pentamethylene tetramine and internal standard substance in the nuclear magnetic resonance hydrogen spectrum of the step (3), and determining relative integral areas of the characteristic peaks to be A respectively H And A S Will beSubstituting the data into the following formula to obtain the mass fraction of the N, N-dinitroso pentamethylene tetramine:
wherein P is H The mass fraction of N, N-dinitroso pentamethylene tetramine; p (P) S Is the purity of the internal standard substance; a is that H Peak area for N, N-dinitroso pentamethylene tetramine; a is that S Peak area for internal standard; n (N) H 1 mole of the number of resonance cores on the functional group of the characteristic signal of N, N-dinitroso pentamethylene tetramine; n (N) S The number of resonating nuclei on the functional group that is characteristic signal of 1 mole of internal standard; m is M H Is the molar mass of N, N-dinitroso pentamethylene tetramine; m is M S Is the molar mass of the internal standard; m is m H The mass of N, N-dinitroso pentamethylene tetramine; m is m S The mass of the internal standard. The content of trisnitrosotrimethylene triamine (blowing agent H by-product) was determined in the same manner.
In a preferred embodiment of the present invention, the internal standard is p-dichlorobenzene, p-dinitrobenzene, which is a high purity product or standard. The corresponding degree of the two internal standards in nuclear magnetic resonance is better, and when nuclear magnetic resonance test is carried out by adopting the internal standard commonly used in the field, such as paradiphenol as the internal standard, the chemical shift of hydrogen on benzene ring is located in the middle of the characteristic peak of trisnitrosotrimethylene triamine, so that the nuclear magnetic resonance test is more messy.
In a preferred embodiment of the invention, the nmr hydrogen spectrum test conditions: the resonance frequency of the nuclear magnetic spectrometer is 400-600 MHz, the temperature is 20-35 ℃, the pulse angle is 90 degrees, the delay time is 20-40 s, and the sampling times are 32-128 times.
In a preferred embodiment of the present invention, the sample foaming agent H used is tested for the content of by-product trisnitrosotrimethylene triamine (TTT) of 0.8 to 2.0wt% and the moisture of 0.20 to 0.29wt%; ash content is 0.060-0.083wt%.
In a preferred embodiment of the invention, the accuracy of the method for testing the purity of N, N-dinitroso pentamethylene tetramine by nuclear magnetic resonance hydrogen spectrum is as high as 99 percent.
In order to verify the optimal detection conditions for nuclear magnetic resonance hydrogen spectrometry for detecting the purity of N, N-dinitroso pentamethylene tetramine, the specific experimental procedures of the following examples were performed. The present invention is described in further detail below.
The reagents and instrument sources used in the examples below are shown in Table 1 below:
table 1 reagents and apparatus used in the examples
Reagents/apparatus Purity/model Manufacturer' s
Foaming agent H 95.0-99.1％ ANHUI RUNYUE SCIENCE AND TECHNOLOGY Co.,Ltd.
Para-dichlorobenzene 99.5％ SHANGHAI ALADDIN BIOCHEMICAL TECHNOLOGY Co.,Ltd.
Para-dinitrobenzene 99.9％ SHANGHAI ALADDIN BIOCHEMICAL TECHNOLOGY Co.,Ltd.
Deuterated dimethyl sulfoxide DMSO-d6 Sinopharm Group Chemical Reagent Co., Ltd.
Constant temperature drying cabinet DHG-9070 Shanghai essence macro experimental facility is limited
Nuclear magnetic spectrometer Avance III 400 or Avance NEO600 Bruce Germany
Examples
Example 1
Example 1-1
3.1473g of foaming agent H (sample 1) is weighed in a constant-weight weighing bottle, placed in a constant-temperature drying oven at 80 ℃, dried for 4 hours, naturally cooled, dried and subjected to dry foaming agent H, 3.1381g in net weight, and the water content of the sample is calculated to be 0.29%.
3.6728g of foaming agent H (sample 1) was weighed in a crucible with constant weight, placed in a muffle furnace with a temperature of 800 ℃ and baked for 2 hours, naturally cooled, and ash content of 0.071% in the sample was calculated.
40.5mg of blowing agent H (sample 1) and 13.9mg of p-dichlorobenzene (purity: 99.5%) were weighed into a sample bottle, dissolved in 2.00mL of DMSO, and subjected to a nuclear magnetic resonance hydrogen spectrum test, the nuclear magnetic resonance hydrogen spectrum of which is shown in FIG. 1, wherein peaks numbered 1, 2 and 3 in the figures are peaks of N, N-dinitroso pentamethylene tetramine, trinitroso trimethylene triamine and an internal standard substance, respectively. The characteristic peaks of N, N-dinitroso pentamethylene tetramine and p-dichlorobenzene (internal standard) in the nuclear magnetic resonance hydrogen spectrum are integrated, the relative integrated areas are AH1 and AS1 respectively, and the content of the N, N-dinitroso pentamethylene tetramine is 97.76% through calculation according to the following mathematical formula (1); wherein, the resonance frequency of the nuclear magnetic spectrometer is 400MHz, the temperature is 20 ℃, the pulse angle is 90 degrees, the delay time is 20s, and the sampling times are 32 times.
The content of trisnitrosotrimethylene triamine in the sample was then calculated to be 1.85% based on the peak area of trisnitrosotrimethylene triamine in fig. 1-1 of the nuclear magnetic resonance hydrogen spectrum by the same method, and the results of example 1 are summarized in table 2 below.
Examples 1 to 2
The experimental procedure was the same as in example 1-1, except that the mass of p-dichlorobenzene (purity 99.5%) as an internal standard was modified to 18.9mg.
Examples 1 to 3
The experimental procedure was the same as in example 1-1, except that the mass of p-dichlorobenzene (purity 99.5%) as an internal standard was changed to 24.8mg.
Examples 1 to 4
The experimental procedure was the same as in example 1-1, except that the nuclear magnetic spectrometer was set to have a resonance frequency of 600MHz, a temperature of 35℃and a pulse angle of 90℃with a delay time of 40s and a sampling number of 128 times.
Examples 1 to 5
The experimental procedure was the same as in example 1-1, except that the nuclear magnetic spectrometer was set to 400MHz for a resonance frequency of 28℃at a pulse angle of 90℃for a delay time of 30s and the number of samples was 80.
TABLE 2 example 1 results of purity test of blowing agent H product
Example 2
Example 2-1
3.4432g of foaming agent H (sample 2) is weighed in a constant-weight weighing bottle, placed in a constant-temperature drying oven at 90 ℃, dried for 3 hours, naturally cooled, dried and subjected to dry foaming agent H with a net weight of 3.4363g, and the water content of the sample is calculated to be 0.20%.
3.1013g of foaming agent H (sample 2) was weighed in a constant weight crucible, placed in a 660 ℃ muffle furnace, baked for 3 hours, naturally cooled, and the ash content in the foaming agent H was calculated to be 0.083%.
41.8mg of blowing agent H (sample 2) and 12.7mg of p-dinitrobenzene (purity: 99.5%) were weighed into a sample bottle, and dissolved in 2.00mL of DMSO to perform a nuclear magnetic resonance hydrogen spectrum test. The characteristic peaks of N, N-dinitroso pentamethylene tetramine and p-dinitrobenzene in the nuclear magnetic resonance hydrogen spectrum are integrated, the relative integration areas are AH2 and AS2 respectively, the content of the N, N-dinitroso pentamethylene tetramine is 98.07% through calculation, wherein the resonance frequency of a nuclear magnetic spectrometer is 400MHz, the temperature is 30 ℃, the pulse angle is 90 degrees, the delay time is 30s, and the sampling times are 64 times.
Then, by the same method, the content of trisnitrosotrimethylene triamine in the sample was calculated from the peak area of trisnitrosotrimethylene triamine on the chart of the nuclear magnetic resonance hydrogen spectrum to be 1.49%, and the results of example 2 are summarized in the following table 3.
Example 2-2
The experimental procedure is the same as in example 2-1, except that the mass of the internal standard p-dinitrobenzene (purity 99.5%) is modified to 16.2mg.
Examples 2 to 3
The experimental procedure is the same as in example 2-1, except that the mass of the internal standard p-dinitrobenzene (purity 99.5%) is modified to 23.7mg.
Examples 2 to 4
The experimental procedure was the same as in example 2-1, except that the nuclear magnetic spectrometer was set to have a resonance frequency of 600MHz, a temperature of 35℃and a pulse angle of 90℃with a delay time of 40s and a sampling number of 128 times.
Examples 2 to 5
The experimental procedure was the same as in example 2-1, except that the nuclear magnetic spectrometer was set to 400MHz for a resonance frequency of 28℃at a pulse angle of 90℃for a delay time of 30s and the number of samples was 80.
TABLE 3 example 2 results of blowing agent H product purity test
Example 3 accuracy detection
Preparing a sample in advance: the pure compounds N, N-dinitroso pentamethylene tetramine and tri-nitroso trimethylene triamine are mixed according to the mass ratio of 99:1, then detecting according to the detection method of the embodiment 1-1, and comparing the detected result with the original mixed content to obtain the accuracy of the detection method. 682.26mg of N, N-dinitroso pentamethylene tetramine (99.5%), 13.91mg of tri-nitroso trimethylene triamine (purity 99.5%) and 218.93mg of p-dichlorobenzene (purity 99.5%) were weighed into a sample bottle by a ten-thousandth balance, and dissolved by adding 10.00mL of DMSO, and subjected to a nuclear magnetic resonance hydrogen spectrum test. The nuclear magnetic spectrometer has a resonance frequency of 600MHz, a temperature of 20 ℃, a pulse angle of 90 degrees, a delay time of 20s and sampling times of 32 times.
Integrating characteristic peaks of N, N-dinitroso pentamethylene tetramine and paradichlorobenzene in a magnetic resonance hydrogen spectrum, wherein relative integration areas are AH3, AT3 and AS3 respectively, and the contents of N, N-dinitroso pentamethylene tetramine and trinitroso trimethylene triamine are 97.90% and 1.97% respectively through calculation; the theoretical contents of N, N-dinitroso pentamethylene tetramine and trinitroso trimethylene triamine in the sample are 98.00% and 2.00%, respectively, and the accuracy of the experimental results is 99.89% and 98.59% respectively.
It will be evident to those skilled in the art that the invention is not limited to the details of the foregoing illustrative embodiments, and that the present invention may be embodied in other specific forms without departing from the spirit or essential characteristics thereof. The present embodiments are, therefore, to be considered in all respects as illustrative and not restrictive, the scope of the invention being indicated by the appended claims rather than by the foregoing description, and all changes which come within the meaning and range of equivalency of the claims are therefore intended to be embraced therein. Any reference sign in a claim should not be construed as limiting the claim concerned.

Claims (30)

1. The method for detecting the purity and impurity content of the foaming agent H is characterized by comprising the following steps of:
(1) Weighing a sample, drying, and calculating the water content W% in the sample;
(2) Roasting the sample, and calculating ash S in the sample;
(3) Weighing a foaming agent and an internal standard substance, placing the foaming agent and the internal standard substance in a sample bottle, adding a deuterated solvent for dissolution, and then performing nuclear magnetic resonance hydrogen spectrum test, wherein the internal standard substance is p-dichlorobenzene;
(4) Determining characteristic peaks of the N, N-dinitroso pentamethylene tetramine and an internal standard substance in the nuclear magnetic resonance hydrogen spectrum in the step (3), setting nuclear magnetic resonance hydrogen spectrum measurement conditions, and measuring relative integral areas of the characteristic peaks to be A respectively H And A S Substituting the data into the following formula to obtain the mass fraction of the N, N-dinitroso pentamethylene tetramine:
wherein P is H The mass fraction of N, N-dinitroso pentamethylene tetramine; p (P) S Is the purity of the internal standard substance; a is that H Peak area for N, N-dinitroso pentamethylene tetramine; a is that S Peak area for internal standard; n (N) H 1 mole of the number of resonance cores on the functional group of the characteristic signal of N, N-dinitroso pentamethylene tetramine; n (N) S The number of resonating nuclei on the functional group that is characteristic signal of 1 mole of internal standard; m is M H Is the molar mass of N, N-dinitroso pentamethylene tetramine; m is M S Is the molar mass of the internal standard; m is m H The mass of N, N-dinitroso pentamethylene tetramine; m is m S The mass of the internal standard;
the nuclear magnetic resonance hydrogen spectrum test conditions are as follows: the resonance frequency of the nuclear magnetic spectrometer is 400-600 MHz; the temperature is 20-35 ℃; the pulse angle is 90 degrees; the delay time is 20-40 s; the sampling times are 32 to 128 times;
(5) The mass fraction of the compound trinitroso trimethylene triamine in the blowing agent was determined and calculated using the same procedure as in step (4).
2. The method of claim 1, wherein the internal standard in step (3) is a high purity or standard.
3. The detection method according to claim 1, wherein the mass of the sample used in the step (1) or the step (2) is 3 to 4g.
4. The detection method according to claim 1, wherein the mass of the sample used in the step (3) is 30 to 60mg.
5. The process according to any one of claims 1 to 4, wherein the blowing agent H has a moisture content of 0.20 to 0.29wt% and an ash content of 0.060 to 0.083wt%; the content of trisnitrosotrimethylene triamine is 0.8-2.0wt%.
6. The method of any of claims 1-4, wherein the deuterated solvent is present in step (3) in an amount of 2.0-8.0mL.
7. The method of claim 5, wherein the deuterated solvent is present in step (3) in an amount of 2.0-8.0mL.
8. The method according to any one of claims 1 to 4, wherein the mass of the internal standard in step (4) is 10 to 25mg.
9. The method according to claim 5, wherein the mass of the internal standard in step (4) is 10-25mg.
10. The method according to claim 6, wherein the mass of the internal standard in step (4) is 10-25mg.
11. The method of claim 7, wherein the mass of the internal standard in step (4) is 10-25mg.
12. The detection method according to any one of claims 1 to 4, wherein the drying in the step (1) is performed at a temperature of 70 to 100 ℃.
13. The detection method according to claim 12, wherein the drying time is 2 to 4 hours.
14. The detection method according to claim 5, wherein the drying in the step (1) is performed at a temperature of 70 to 100 ℃.
15. The detection method according to claim 6, wherein the drying in the step (1) is performed at a temperature of 70 to 100 ℃.
16. The detection method according to claim 8, wherein the drying in the step (1) is performed at a temperature of 70 to 100 ℃.
17. The detection method according to any one of claims 1 to 4, wherein the temperature at which the calcination in step (2) is performed is 500 to 800 ℃.
18. The detection method according to claim 17, wherein the baking time in the step (2) is 2 to 4 hours.
19. The detection method according to claim 5, wherein the baking temperature in the step (2) is 500 to 800 ℃.
20. The detection method according to claim 6, wherein the baking temperature in the step (2) is 500 to 800 ℃.
21. The detection method according to claim 8, wherein the baking temperature in the step (2) is 500 to 800 ℃.
22. The detection method according to claim 12, wherein the baking temperature in the step (2) is 500 to 800 ℃.
23. The detection method of any of claims 1-4, wherein the deuterated solvent is one or more of heavy hydrogen dimethyl sulfoxide (DMSO-d 6), deuterated chloroform, and deuterated acetonitrile.
24. The detection method according to claim 5, wherein the deuterated solvent is one or more of heavy hydrogen dimethyl sulfoxide (DMSO-d 6), deuterated chloroform, and deuterated acetonitrile.
25. The detection method according to claim 6, wherein the deuterated solvent is one or more of heavy hydrogen dimethyl sulfoxide (DMSO-d 6), deuterated chloroform, and deuterated acetonitrile.
26. The detection method according to claim 8, wherein the deuterated solvent is one or more of heavy hydrogen dimethyl sulfoxide (DMSO-d 6), deuterated chloroform, and deuterated acetonitrile.
27. The detection method of claim 12, wherein the deuterated solvent is one or more of heavy hydrogen dimethyl sulfoxide (DMSO-d 6), deuterated chloroform, and deuterated acetonitrile.
28. The detection method of claim 17, wherein the deuterated solvent is one or more of heavy hydrogen dimethyl sulfoxide (DMSO-d 6), deuterated chloroform, and deuterated acetonitrile.
29. The detection method of claim 18, wherein the deuterated solvent is one or more of heavy hydrogen dimethyl sulfoxide (DMSO-d 6), deuterated chloroform, and deuterated acetonitrile.
30. The detection method of claim 23, wherein the deuterated solvent is heavy hydrogen dimethyl sulfoxide (DMSO-d 6).
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JP2003344322A (en) * 2002-05-29 2003-12-03 Inoac Corp Method of measuring cross-link density in foam
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