CN113514493A - Method for measuring silk grafting rate - Google Patents
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- 238000000034 method Methods 0.000 title claims abstract description 48
- 238000012360 testing method Methods 0.000 claims abstract description 34
- 238000001938 differential scanning calorimetry curve Methods 0.000 claims abstract description 24
- 238000010521 absorption reaction Methods 0.000 claims abstract description 18
- FQPSGWSUVKBHSU-UHFFFAOYSA-N methacrylamide Chemical compound CC(=C)C(N)=O FQPSGWSUVKBHSU-UHFFFAOYSA-N 0.000 claims description 20
- 238000005303 weighing Methods 0.000 claims description 11
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- BDAGIHXWWSANSR-UHFFFAOYSA-N methanoic acid Natural products OC=O BDAGIHXWWSANSR-UHFFFAOYSA-N 0.000 claims description 6
- 239000000178 monomer Substances 0.000 claims description 6
- 238000001035 drying Methods 0.000 claims description 5
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 4
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- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 4
- OSWFIVFLDKOXQC-UHFFFAOYSA-N 4-(3-methoxyphenyl)aniline Chemical compound COC1=CC=CC(C=2C=CC(N)=CC=2)=C1 OSWFIVFLDKOXQC-UHFFFAOYSA-N 0.000 claims description 3
- 235000019253 formic acid Nutrition 0.000 claims description 3
- 239000003999 initiator Substances 0.000 claims description 3
- USHAGKDGDHPEEY-UHFFFAOYSA-L potassium persulfate Chemical compound [K+].[K+].[O-]S(=O)(=O)OOS([O-])(=O)=O USHAGKDGDHPEEY-UHFFFAOYSA-L 0.000 claims description 3
- 238000005406 washing Methods 0.000 claims description 3
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- 108010022355 Fibroins Proteins 0.000 description 1
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- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical compound [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 description 1
- 230000015556 catabolic process Effects 0.000 description 1
- 230000003247 decreasing effect Effects 0.000 description 1
- 238000006731 degradation reaction Methods 0.000 description 1
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- 230000004907 flux Effects 0.000 description 1
- -1 functional group amide Chemical class 0.000 description 1
- 229920000578 graft copolymer Polymers 0.000 description 1
- 230000005484 gravity Effects 0.000 description 1
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- G01N25/00—Investigating or analyzing materials by the use of thermal means
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Abstract
The application provides a method for measuring the silk grafting rate, which belongs to the technical field of testing or analyzing materials by means of measuring the chemical or physical properties of the materials. Performing DSC test on a grafted silk sample to be detected to obtain a DSC curve, wherein a new absorption peak is marked as P1, and an absorption peak of the structure of the silk is marked as P2; interpolating the overlapped part of the P1 and the P2 in a spline baseline mode to obtain an S-shaped baseline, and calculating the unit enthalpy of the corresponding peak area of the S-shaped baseline by combining the mass of the silk sample to be grafted, wherein the unit enthalpy is marked as Q1; the corresponding unit enthalpy at the absorption peak of the structure of the silk itself is marked as Q2; and if y = Q1/Q2, the grafting ratio x of the to-be-grafted silk satisfies the following conditions:
. The method is applied to the determination of the grafting rate of the grafted silk, and the calculation of the grafting rate of the unknown grafted silk can be accurately carried out.
Description
Technical Field
The application relates to a method for measuring silk grafting ratio, belonging to the technical field of testing or analyzing materials by means of measuring chemical or physical properties of the materials.
Background
The silk integrates the advantages of softness, smoothness, excellent luster, drapability and the like, becomes a high-quality high-grade natural fiber material, is generally applied to the industrial fields of clothes, home textiles and the like, and is popular with consumers. However, since the degumming process requires the removal of nearly one-fourth of the original weight of silk (sericin), such a large specific gravity loss has prompted silk processing producers to investigate how to increase the quality of silk without affecting its quality. With continuous innovation of the technology, the traditional tin weight increment, tannin weight increment, sericin fixation weight increment and the like are developed into a grafting weight increment technology, wherein Methacrylamide (MAA) contains a functional group amide (-CONH-) which is the same as silk fibroin, and the performances of the silk in various aspects such as size stability, wear resistance, yellowing resistance, water and oil repellency, color fastness and the like are improved after grafting, so that the support of various silk manufacturers is obtained, and a methacrylamide Monomer (MAA) also becomes a silk grafting monomer which is most widely applied at present.
Regarding silk, researchers at home and abroad have compared and researched the properties of silk before and after weight increment through analysis technologies such as thermogravimetry, infrared spectroscopy, X diffraction, Differential Scanning Calorimetry (DSC) and the like, but except that the problem group (CN 201510303852) provides a quantitative relation between thermogravimetry and grafting rate, other testing technologies do not relate to the provision of a mathematical model of the grafting rate of the grafted silk. However, this is a quantitative study using the difference in degradation temperatures between silk and the grafted polymer. The silk fiber still has many other performances and remarkable characteristics, and the development of a more rapid, convenient and accurate mode for enriching the detection and identification of the grafting rate of the grafted silk by digging more index performances and characteristics of the grafted silk is a means and a technology which are very needed at the present stage.
Therefore, although some researchers also use the DSC technique to study the relationship between the change of the endothermic peak and the grafting ratio, the studied DSC data has large discreteness and insufficient systematicness, and a mathematical function relation formula of the silk grafting ratio is not clearly established and proposed, so that the grafting ratio of unknown grafted silk cannot be back-estimated by the DSC technique.
Disclosure of Invention
In view of the above, the present application provides a method for measuring the grafting ratio of methacrylamide grafted silk based on DSC, so as to obtain the corresponding relationship between the grafting ratio and the enthalpy value.
Specifically, the method is realized through the following scheme:
a method for measuring silk grafting rate comprises the following steps:
(1) weighing a to-be-detected grafted silk sample, recording the mass of the sample, and performing DSC test to obtain a DSC curve, wherein a new absorption peak generated by grafting is marked as P1, and the absorption peak of the structure of the silk is marked as P2;
(2) interpolating the overlapped part of the P1 and the P2 in a spline baseline mode to obtain an S-shaped baseline, and calculating the unit enthalpy of the corresponding peak area of the S-shaped baseline by combining the mass of the silk sample to be grafted, wherein the unit enthalpy is marked as Q1;
(3) calculating corresponding unit enthalpy at an absorption peak of the structure of the silk by combining the mass of the grafted silk sample to be detected, and recording the enthalpy as Q2;
(4) and (3) recording y as Q1/Q2, wherein the grafting ratio x of the silk to be grafted meets the following requirements:
y＝1.024x-0.071。
the principles of the present application can be summarized as follows:
differential Scanning Calorimetry (DSC) is a technique that measures the power difference and temperature of a sample and a reference at a programmed temperature. By testing the grafted silk samples with different grafting ratios at 25-400 ℃, compared with ungrafted silk, a new endothermic peak appears, and the endothermic peak is obviously caused by the grafted monomer which is reacted and grafted. Along with the increase of the grafting rate, the area of the endothermic peak at the position is gradually increased, and the area of the endothermic peak in the range of 310-330 ℃ (the temperature interval corresponding to the structure of the silk itself) has a decreasing trend, which shows that a certain relationship exists between the change area of the new endothermic peak and the grafting rate. According to the principle of DSC curve, the following results are obtained: the integral of the heat flux flowing to the sample with respect to time is equal to the enthalpy of transformation (Δ H), the DSC curve expressed with respect to temperature is always integral with time, the result of the integration is the area between the DSC curve and the baseline, and the peak area can be corresponded to by considering the mass of the test sample, i.e. the unit enthalpy. Respectively recording the unit enthalpy value corresponding to the new peak and the unit enthalpy value corresponding to the range of 310-330 ℃ as Q1 and Q2, obtaining the area ratio Q1/Q2 of the series endothermic peaks through samples with different grafting rates, and searching a mathematical function relation between the obtained value and the corresponding grafting rate (weighing method), thereby calculating the grafting rate of the grafted silk.
Further, as preferable:
the peak area of the new absorption peak P1 increases with the increase of the grafting rate, the peak position moves to the high temperature direction, and simultaneously the absorption peak P2 area of the structure of the silk is gradually reduced.
The DSC test process is as follows: weighing an ungrafted silk sample and grafted silk samples with different grafting ratios, raising the temperature to 400 ℃ at the initial temperature of 25 ℃ at the speed of 10 ℃/min under the nitrogen flow of 30ml/min, and obtaining a series of DSC curves. In the test process, the mass of the ungrafted silk sample and the mass of the grafted silk sample with different grafting ratios are preferably 4-5mg and 4-5 mg. Different from the thermogravimetric weight loss analysis and infrared spectrum absorption principle, the Differential Scanning Calorimetry (DSC) of the application utilizes the enthalpy value change of a test sample to complete the quantitative relation between the change and the grafting rate, and the difference in principle not only can complete the supplement on the quantitative analysis method of the silk grafting rate, but also can realize the multi-party verification of the inspection and detection of unknown silk samples.
Grafting silk by adopting methacrylamide, wherein the temperature range corresponding to a new absorption peak P1 is 260-290 ℃; the temperature range corresponding to the absorption peak P2 of the structure of the silk is 310-330 ℃.
In the above process, the preparation process of the grafted silk is as follows:
1) drying degummed silk to constant weight at 140 ℃;
2) controlling the input amount of a grafting monomer (preferably methacrylamide) to be 60-300%, controlling formic acid to be 3%, and treating for 40min by a suction-out method at the temperature of 85 ℃ and the bath ratio of 1:50 by taking 3% of potassium persulfate as an initiator;
3) sampling, washing with water, and drying at 140 deg.C to constant weight.
By taking methacrylamide grafted silk as a research object and adopting a Differential Scanning Calorimeter (DSC) to test methacrylamide grafted silk (polyMAA-SF) samples with different grafting ratios, the grafted silk is found to have a new endothermic peak in the range of 260-. It can be known from theory that the newly appeared peak P1 is the endothermic peak of methacrylamide polymer, while P2 is the endothermic peak of the structure of silk itself, and the integral of DSC curve over time is equal to the enthalpy of transformation (Δ H), i.e. the area between the curve and the base line. Because the two endothermic peaks are overlapped, the S-shaped base line is obtained by interpolating the endothermic peak in the range of 260-290 ℃ in the overlapped peaks in a spline base line mode according to DSC analysis, so as to obtain the corresponding enthalpy (namely the peak area), and the unit enthalpy of the corresponding peak is obtained by calculation by considering the weight of the grafted silk sample and is respectively marked as Q1 and Q2. And establishing a linear function relationship with the silk grafting rate obtained by a weighing method through the serial enthalpy ratio Q1/Q2, and accurately calculating the grafting rate of the unknown methacrylamide grafted silk through the linear function and the enthalpy ratio of a new endothermic peak obtained by DSC test.
DSC analysis is carried out on a series of grafted silk samples with different grafting rates, Origin mathematical software is used for fitting and analyzing, a functional relation between an endothermic peak and the grafting rate of silk is established, the internal rule between the grafting rate and the enthalpy performance is revealed, and the quantitative analysis method for establishing the grafting rate of the methacrylamide grafted silk based on DSC is formed. Therefore, the grafting rate of unknown methacrylamide grafted silk can be accurately calculated, the method has a good promoting effect on the identification and detection of the weight-increased silk, and meanwhile, the method has positive current significance on the development of the silk weight-increasing field.
Drawings
FIG. 1 is a DSC analysis curve of ungrafted silk;
FIG. 2 is a DSC analysis curve of 10.89% grafted silk;
FIG. 3 is a DSC analysis curve of 20.88% grafted silk;
FIG. 4 is a DSC analysis curve of 28.78% grafted silk;
FIG. 5 is a DSC analysis curve of 41.60% grafted silk;
FIG. 6 is a DSC analysis curve of 49.09% grafted silk;
FIG. 7 is a DSC analysis curve of 60.17% grafted silk;
FIG. 8 is a DSC analysis curve of 70.69% grafted silk;
FIG. 9 is a DSC analysis curve of 77.83% grafted silk;
FIG. 10 is a DSC analysis curve of 86.60% grafted silk;
FIG. 11 is a DSC analysis curve of 96.28% grafted silk;
FIG. 12 is a DSC analysis curve of 104.17% grafted silk;
FIG. 13 is a DSC analysis curve of 108.42% grafted silk;
FIG. 14 is a DSC analysis curve of 116.89% grafted silk;
FIG. 15 is a DSC analysis curve of 144.13% grafted silk;
FIG. 16 is a linear fitting relationship diagram of silk grafting ratio and endothermic peak enthalpy ratio;
FIG. 17-1 shows the first test results and curve analysis of example 1;
FIG. 17-2 shows the second test results and curve analysis of example 1;
FIGS. 17-3 are graphs showing the results of the third test in example 1;
FIGS. 17-4 are fourth test results and curve analysis of example 1;
FIG. 18-1 shows the first test results and curve analysis of example 2;
FIG. 18-2 is the second test results and curve analysis of example 2;
FIG. 18-3 shows the third test result and the curve analysis in example 2;
FIGS. 18-4 are fourth test results and curve analysis of example 2.
Detailed Description
Example 1: preparation of silk samples with different grafting ratios
Weighing 0.5g of degummed silk, and drying at 140 ℃ for 60min to constant weight W1(g) In that respect The following process is adopted for grafting treatment: the method comprises the steps of putting 60-300% of methacrylamide, taking 3% of formic acid, taking 3% of potassium persulfate as an initiator, carrying out exhaustion treatment for 40min at the temperature of 85 ℃ and the bath ratio of 1:50, taking samples, washing with water, and obtaining methacrylamide grafted silk samples (polyMAA-SF) with different grafting rates, wherein the percentage contents are the mass of the original silk. Then baking the mixture to constant weight W at 140 DEG C2(g) Each graft ratio was calculated by the following weighing method shown in the following formula (1).
In the formula (1), W1Absolute weight of silk before grafting, W2The absolute weight of the silk after grafting weight increment.
Example 2: baseline treatment and unit enthalpy analysis of DSC curves
A differential scanning calorimeter is adopted to test samples of methacrylamide grafted silk (polyMAA-SF) with different grafting ratios, the grafted silk has a new endothermic peak in the range of 260-290 ℃, which is the endothermic peak of a methacrylamide polymer and is marked as P1, and the area of the endothermic peak is increased along with the increase of the grafting ratio. Meanwhile, the endothermic peak at the temperature range of 310-330 ℃ is gradually reduced, and the endothermic peak is the endothermic peak of the structure of the silk itself and is marked as P2. Because the two peaks have overlapping effect, the S-shaped base line is obtained by interpolating the overlapping peaks in a spline base line mode according to DSC analysis, and therefore the corresponding area, namely a red area, is obtained. Considering the weight of the grafted silk sample, the specific enthalpy (corresponding area) was recorded as Q1 (red area) and Q2 (black area), respectively, and the results are shown in FIGS. 1-15 and tables 1-15.
Table 1: DSC analysis curve parameter of ungrafted silk
Table 2: DSC curve parameter of 10.89% grafted silk
Table 3: DSC curve parameter of 20.88% grafted silk
Table 4: DSC curve parameter of 28.78% grafted silk
Table 5: DSC curve parameter of 41.60% grafted silk
Table 6: DSC curve parameter of 49.09% grafted silk
Table 7: DSC curve parameter of 60.17% grafted silk
Table 8: DSC curve parameter of 70.69% grafted silk
Table 9: DSC curve parameter of 77.83% grafted silk
Table 10: DSC curve parameter of 86.60% grafted silk
Table 11: DSC curve parameter of 96.28% grafted silk
Table 12: DSC curve parameter of 104.17% grafted silk
Table 13: DSC curve parameter of 108.42% grafted silk
Table 14: DSC curve parameter of 116.89% grafted silk
Table 15: DSC curve parameter of 144.13% grafted silk
Table 16: q1, Q2 and ratio thereof of polyMAA-SF with different grafting rates
The grafting ratio and the endothermic peak enthalpy ratio in the above data were subjected to data processing, as shown in fig. 16.
The result shows that a good linear relation exists between the silk grafting rate (weighing method) and the ratio of the endothermic peak enthalpy, and the function formula is as follows:
y＝1.024x-0.071……………………(2)
in the formula: y is Q1/Q2; x is the grafting yield (gravimetric method).
As can be seen from equation (2): the endothermic peak enthalpy ratio can be obtained by adopting DSC method calculation, and the grafting rate of unknown polyMAA-SF can be accurately deduced through the linear function relation of the formula (2).
Application example 1
Sample sending unit: silk samples with a grafting rate of 24.67% from yashi forest, zhejiang, necktie and costume, inc.
The method comprises the steps of sampling four different positions of a sample with known grafting ratio (F), carrying out DSC test to obtain DSC analysis curves, carrying out baseline treatment by self-contained software to obtain the unit enthalpy and the ratio of the unit enthalpy to the ratio of each series of silks, and obtaining the results as shown in a figure 17-1, a figure 17-2, a figure 17-3, a figure 17-4, a table 17-1, a table 17-2, a table 17-3 and a table 17-4.
Table 17-1: first test result parameters of application example 1
Table 17-2: second measurement result parameter of application example 1
Tables 17 to 3: the third test result parameters of example 1 were applied
Tables 17 to 4: fourth test result parameter of application example 1
The calculated grafting rate M and the average value thereof are obtained through the linear function relation model established by the invention
The results are shown in Table 17.
Table 17: application example 1 analysis of test results of Silk samples
Note:
application example 2
Sample sending unit: silk samples with a grafting yield of 66.53% from pebae, zhejiang.
The method comprises the steps of sampling four different positions of a sample with known grafting ratio (F), carrying out DSC test to obtain DSC analysis curves, carrying out baseline treatment by self-contained software to obtain the unit enthalpy and the ratio thereof of each series of silks, and obtaining the results as shown in a figure 18-1, a figure 18-2, a figure 18-3, a figure 18-4, a table 18-1, a table 18-2, a table 18-3 and a table 18-4.
TABLE 18-1: first test result parameters of application example 2
Table 18-2: second measurement result parameter of application example 2
Tables 18 to 3: fourth test result parameter of application example 2
Tables 18 to 4: fourth test result parameter of application example 2
The calculated grafting rate M and the average value thereof are calculated and obtained through the linear function relation model established by the invention
The results are shown in Table 18.
Table 18: application example 2 analysis of test results of Silk samples
Note:
the grafting rates (weighing methods) of the weight-increased silk samples provided by the two enterprises are 24.67% and 66.53%, respectively. As can be seen from the verification tables 17 and 18 of application examples 1 and 2, the enthalpy ratios of the samples were measured by DSC, the average values thereof were substituted into the mathematical functional relational expression to calculate the corresponding grafting ratios, the relative errors with the provided grafting ratios (weighing method) were all less than 5% (within the error range of the analytical test), and other grafting ratios were selected for verification, which also gave similar results, indicating that the accurate grafting ratio of methacrylamide grafted silk could be obtained by quantitative analysis by DSC. The method can be used for making technical support for quality control of related silk enterprises in the silk weight increasing process, and can also be used for providing convenient method analysis for silk application and grafting rate detection.
The quantitative test and analysis of the silk grafting rate are realized by a DSC method, and the DSC self-contained analysis software can be directly adopted to perform baseline operation, peak area calculation and the like. Compared with a DTG analysis method, the method reduces the analysis processes of Gaussion peak separation, fitting treatment and the like, and meanwhile, a DSC test obtains a single endothermic peak, so that the treatment is simpler and more convenient and is clear at a glance.
Claims (8)
1. A method for measuring silk grafting rate is characterized by comprising the following steps:
(1) weighing a to-be-detected grafted silk sample, recording the mass of the sample, and performing DSC test to obtain a DSC curve, wherein a new absorption peak generated by grafting is marked as P1, and the absorption peak of the structure of the silk is marked as P2;
(2) interpolating the overlapped part of the P1 and the P2 in a spline baseline mode to obtain an S-shaped baseline, and calculating the unit enthalpy of the corresponding peak area of the S-shaped baseline by combining the mass of the silk sample to be grafted, wherein the unit enthalpy is marked as Q1;
(3) calculating corresponding unit enthalpy at an absorption peak of the structure of the silk by combining the mass of the grafted silk sample to be detected, and recording the enthalpy as Q2;
(4) and (3) recording y as Q1/Q2, wherein the grafting ratio x of the silk to be grafted meets the following requirements:
y＝1.024x-0.071。
2. the method for measuring silk graft ratio according to claim 1, wherein: the peak area of the new absorption peak P1 increases with the increase of the grafting rate, the peak position moves to the high temperature direction, and simultaneously the absorption peak P2 area of the structure of the silk is gradually reduced.
3. The method for measuring silk grafting rate according to claim 1, wherein DSC test process comprises: respectively weighing equal amounts of ungrafted silk samples and grafted silk samples with different grafting ratios, starting at 25 ℃, and heating to 400 ℃ at 10 ℃/min under the nitrogen flow of 30ml/min to obtain a series of DSC curves.
4. The method for measuring silk graft ratio according to claim 3, wherein: the mass of the ungrafted silk sample and the mass of the grafted silk sample with different grafting rates are respectively 4-5mg and 4-5 mg.
5. The method for measuring silk graft ratio according to claim 1, wherein: the grafted silk adopts methacrylamide grafted silk, and the temperature range corresponding to the new absorption peak P1 is 260-290 ℃.
6. The method for measuring silk graft ratio according to claim 1, wherein: the temperature range corresponding to the absorption peak P2 of the structure of the silk is 310-330 ℃.
7. A method for measuring silk graft ratio according to any of claims 1 to 6, wherein the grafted silk is prepared by the following steps:
1) drying degummed silk to constant weight at 140 ℃;
2) controlling the input amount of a grafting monomer to be 60-300%, controlling formic acid to be 3%, and treating for 40min by a suction method at the temperature of 85 ℃ and the bath ratio of 1:50 by taking 3% of potassium persulfate as an initiator;
3) sampling, washing with water, and drying at 140 deg.C to constant weight.
8. The method for measuring silk graft ratio according to claim 7, wherein: the grafting monomer is methacrylamide.
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