CN104730028A - Near-infrared spectral detection method for residual content of solvent in polyurethane elastic fiber filaments - Google Patents
Near-infrared spectral detection method for residual content of solvent in polyurethane elastic fiber filaments Download PDFInfo
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- CN104730028A CN104730028A CN201510107905.3A CN201510107905A CN104730028A CN 104730028 A CN104730028 A CN 104730028A CN 201510107905 A CN201510107905 A CN 201510107905A CN 104730028 A CN104730028 A CN 104730028A
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Abstract
The invention relates to a near-infrared spectral detection method for the residual content of a solvent N,N'-dimethylacetamide (DMAC) in polyurethane elastic fiber filaments. The method comprises the following steps: (1) preparing a series of acetone and DMAC solutions of different concentrations, and selecting a sufficient amount of representative calibration set samples; (2) determining a near-infrared spectral spectrogram of the calibration set samples, carrying out spectral pretreatment on a wave band, of 12,000-4,000cm<-1>, of the spectrogram, and then, establishing calibration models by adopting a partial least square method; (3) carrying out extracting pretreatment on the polyurethane elastic fiber filaments, then, determining a near-infrared spectral spectrogram of an extract, treating the wave band, of 12,000-4000cm<-1>, of the obtained spectrogram by adopting the same pretreatment method as in the step (2), and analyzing the pretreated spectrum by adopting the corresponding calibration model obtained in the step (2), thereby obtaining the content of DMAC in a polyurethane elastic fiber filament sample to be detected. The method has the advantages that the analysis process is simple and rapid, the interference resistance is strong, the analysis is non-destructive, the sampling quantity is small, and the like.
Description
Technical field
The present invention relates to a kind of for solvent N in spandex thread, the near infrared spectrum detection method of N '-dimethyl acetamide (DMAC) remaining content, belongs to technical analysis field.
Background technology
Spandex (polycarbamate) fiber is the most whippy current a kind of synthon, there is excellent breaking elongation and ultimate strength, be produce the indispensable special textile fibres of high-grade elastic textiles, there is very high using value and good development prospect.Dry spinning is urethane elastic fiber production technology the most frequently used at present, and ie in solution, under thermal current, is solidified into the method for silk because of solvent volatilization.Internal solvent diffuses to the surface the obstruction being subject to top layer cured fiber, causes solvent to volatilize completely, finally forms dissolvent residual.DMAC is the most frequently used solvent during present spandex is produced, and the massfraction of the solvent DMAC contained in solvent survival rate and spandex thread, measuring DMAC survival rate accurately can control provide reliable foundation for the spandex quality of production.
At present, the method that in spandex production, solvent survival rate quantitatively detects has washing and drying method, vapor-phase chromatography, these methods not only detect length consuming time, and detection efficiency is low, poor repeatability, other hydrophilicity condiments in spandex thread easily wash out by washing and drying method, cause result bigger than normal; Vapor-phase chromatography easily causes DMAC to run off in the process of dissolving Extraction solvent DMAC, causes Lower result; The stability of these testing results on production control has impact.Ultraviolet spectrophotometry, is undertaken quantitatively by measuring the absorbance of DMAC, reappearance better, but to instrument and reagent requirement comparatively harsh, and the sensitivity of method is lower.Sun Zhenbo etc. report infrared technique in utilization and detect the method for DMAC content in spandex thread, but the sensitivity of the method is 11.205mg/L, and the insufficient sensitivity of method is high, and the accuracy of detection for the DMAC content of low content is inadequate.Therefore, study and a kind ofly in time, accurately, detect the method for DMAC content in spandex thread fast, important practical usage can be had to raising spandex product quality and production control stability.
The main information of near infrared spectrum shows as material internal composition hydric group (comprising O-H, C-H, N-H and S-H etc.) and frequently absorbs the frequency multiplication of near infrared light and combination, can characterize the information of most organic composition and molecular structure, the composition and property being very suitable for carbon-hydrogen organic measures.Therefore, in recent years, Near Infrared Spectroscopy Detection Technology is a lot of in the numerous areas application such as agriculture, medical and chemical.But, to utilize near infrared ray actual production solvent DMAC in spandex thread to have no report containing quantifier elimination.
Summary of the invention
Technical matters: the object of the invention is to the deficiency solving currently available technology, there is provided a kind of for solvent N in spandex thread, the near infrared spectrum detection method of N '-dimethyl acetamide (DMAC) remaining content, the implementation process of this detection method is easy, and precision is high, reproducible.
Technical scheme: one of the present invention is used for solvent N in spandex thread, and the near infrared spectrum detection method of N '-dimethyl acetamide (DMAC) remaining content, comprises the steps:
1) configure the N of a series of variable concentrations, the acetone standard solution of N '-dimethyl acetamide DMAC, as calibration set sample;
2) the near infrared spectrum spectrogram of calibration set sample is measured, sweep limit 12000 ~ 4000cm
-1wave band, and spectrum spectrogram is normalized and after standardization pre-service, is associated with DMAC content in DMAC-acetone standard solution, adopt partial least square method to set up calibration model;
3) pre-service is carried out by after the spandex thread sample collection that production is taken out, the near infrared spectrum spectrogram of sample after mensuration pre-service, adopt and step 2) in identical preprocessing procedures process gained spectrogram, the spectrum spectrogram that obtains after pre-service is adopted step 2) calibration model analysis, draw DMAC content in spandex thread sample to be measured.
Described calibration set number of samples is greater than 30.
In the acetone standard solution of described DMAC, the mass concentration of DMAC is 0-10%, and solvent is acetone.
Carry out pre-service after described spandex thread sample collection, its method takes quantitative sample to add in quantitative acetone soln, ultrasonic extraction.
The method of the near infrared spectrum spectrogram of described mensuration calibration set sample uses ABB AB MB3600 Fourier Transform Near Infrared instrument, and adopt transmission mode, liquid cell dedicated test passage, each Sample Scan is averaged for 32 times and obtains.
Described sample pretreatment is: the quality taking quantitative spandex thread sample is 5-10g, and the quality of quantitative acetone is 30-60g, and ultrasonic extraction 0.5 hour, extract is preheated to 25 ± 0.5 DEG C.
After described pre-service, the best modeled wave band of spectrum spectrogram confirms as 4484-5095cm
-1, 5579-6167cm
-1, 8212-9014cm
-1, 10652-11448cm
-1four spectral ranges.
Beneficial effect: it is detection target that this method chooses remaining DMAC content in spandex thread, and set up quantitative model, method RMSECV is little, and content is the linearly dependent coefficient R of the DMAC acetone soln of 0-1.7878%
2=0.99996, content is the linearly dependent coefficient R of the DMAC acetone soln of 1.7878%-9.4362%
2=0.99964, correlativity is good, and minimal detectable concentration is 1ppm.Predict unknown sample, acquired results is satisfactory.Application near-infrared spectrum technique can carry out quantitative test to DMAC content remaining in spandex thread in conjunction with PLS method, method is accurate, the plenty of time is saved than vapor-phase chromatography, more highly sensitive than ultraviolet, middle infrared spectrophotometer, quality control efficiency can be significantly improved, shorten sense cycle, for real-time analysis technology in commercial production opens a new way.
Accompanying drawing explanation
Fig. 1 is that near-infrared spectroscopy is set up and application process;
Fig. 2 is the original near infrared light spectrogram of sample;
Calibration model main cause subnumber and the RMSECV graph of a relation of Fig. 3 a to be DMAC content be 0-1.7878%,
Calibration model main cause subnumber and the RMSECV graph of a relation of Fig. 3 b to be DMAC content be 1.7878%-9.4362%;
Calibration set DMAC content spectral predicted value and the true value correlation curve of Fig. 4 a to be DMAC content be 0-1.7878%;
Calibration set DMAC content spectral predicted value and the true value correlation curve of Fig. 4 b to be DMAC content be 1.7878%-9.4362%;
Forecast set sample DMAC content spectral predicted value and the true value correlation curve of Fig. 5 a to be DMAC content be 0-1.7878%;
Forecast set sample DMAC content spectral predicted value and the true value correlation curve of Fig. 5 b to be DMAC content be 1.7878%-9.4362%.
Embodiment
For achieving the above object, the invention provides a kind of for solvent N in spandex thread, the near infrared spectrum detection method of the remaining content of N '-dimethyl acetamide, the method comprises the steps:
1) configure the DMAC acetone soln of a series of different quality concentration, select enough representational calibration set samples;
2) the near infrared spectrum spectrogram of calibration set sample is measured, sweep limit 12000 ~ 4000cm
-1wave band, and after carrying out Pretreated spectra, be associated with DMAC content in standard solution, adopt partial least square method to set up calibration model;
3) extraction process will be carried out after the spandex thread sample collection that production is taken out, measure the near infrared spectrum spectrogram of extract, adopt the preprocessing procedures process gained spectrogram identical with step 2, the spectrum obtained after pre-service is adopted the calibration model analysis of step 2, obtain DMAC content in spandex thread sample to be measured.
In described method, solution to be measured, with transmission mode collection, imports in quartzy liquid cell by near infrared spectrum data, and liquid cell designated lane is measured, and carry out sample spectral data collection, each Sample Scan is averaged for 32 times and obtains.The spectral range of scanning is 12000 ~ 4000cm
-1.
Step 2 in described method) before spectrogram and data correlation, suitable preprocessing procedures is adopted to spectrogram, to eliminate the interference of baseline and other backgrounds, described best preprocess method is normalization and standardization.Step 3) to the preprocess method of the near infrared spectrogram of testing sample and step 2) identical.
Step 2 in described method) after carrying out Pretreated spectra, with cross validation root-mean-square deviation (RMSECV), relative deviation (RSECV) for index, Optimization Modeling parameter, adopts offset minimum binary (PLS) Return Law to set up quantitative calibration models.
Step 3 in the present invention) spectrum of described mensuration and the applicability criterion of calibration model be: the quantitative model set up forecast set sample, carry out cross-validation, with cross validation error root mean square (RMSECV) for index, determine best PLS number of principal components, then with best number of principal components and the best band chosen for parameter sets up final mask; Assay is carried out to checking collection sample, is evaluated the quality of final mask by predicted root mean square error (RMSEP) and related coefficient (r).PLS method in Horizon MB analysis software is used to carry out data processing, 15 increment product of choosing are as Prediction, cross-validation is carried out with Calibration, content is the RMSECV of the DMAC acetone soln of 0-1.7878% is 0.004112, content is the RMSECV of the DMAC acetone soln of 1.7878%-9.4362% is 0.041343, when there being forecast set sample to evaluate the detectability of PLS model, content is the RMSEP of the DMAC acetone soln of 0-1.7878% is 0.003949, content is the RMSEP of the DMAC acetone soln of 1.7878%-9.4362% is 0.032299.
Be described further near-infrared spectroscopy foundation of the present invention and application process by way of example below, this embodiment should not be construed as limitation of the present invention.
Embodiment 1:
Near-infrared spectroscopy foundation of the present invention and application process are as accompanying drawing 1, specific as follows:
The process of instrument condition and spandex performed polymer sample:
Instrument: near infrared spectrum is gathered by ABB AB of Switzerland MB3600 Fourier Transform Near Infrared instrument, and this instrument is furnished with Horizon MB analysis software, quartzy liquid cell and InGaAs detecting device.The spectrogram of each sample is resolution is 4, obtains by being averaged through 32 scanning.Sweep limit is 12000 ~ 4000cm
-1.
Sample: sample used in experiment is the spandex thread collected in spandex production run, gets extract and detects after acetone extract.
Embodiment 2:
Sample near-infrared spectral measurement:
This experiment uses quartzy liquid absorption pond, pours the DMAC acetone standard solution of variable concentrations into liquid absorption pond, constant temperature to 25 ± 0.5 DEG C, put into detection cell, carry out the spectra collection of sample, same sample is scanned 32 times, final spectrogram is obtained, as accompanying drawing 2 after average.
Embodiment 3:
Prediction:
Figure 2 shows that the raw data of spectrum, after normalization and standardization, confirm 4484-5095cm
-1, 5579-6167cm
-1, 8212-9014cm
-1, 10652-11448cm
-1four spectral detection scopes, as modeling wave band, use the segmentation of PLS method to set up quantitative calibration models.For avoiding occurring " over-fitting " phenomenon, a cross-validation method choose reasonable main cause subnumber is stayed in employing, the main cause subnumber of two sections of DMAC content that cross validation obtains as shown in Figure 3, best main cause subnumber is 4 (0-1.7878%, see Fig. 3 (a)), 5 (1.7878%-9.4362% is shown in Fig. 3 (b)).
Embodiment 4:
Analyze:
By 50 spandex performed polymer samples, wherein 33 samples are as calibration set, and 15 samples are as forecast set.The predicted value of DMAC content and the predicted value of actual value matched curve as Fig. 4, DMAC content and the coefficient R of true value in the calibration set sample corresponding with best main cause subnumber
2=0.99996 (0-1.7878% is shown in Fig. 4 (a)), R
2=0.99964 (1.7878%-9.4362% is shown in Fig. 4 (b)), concrete numerical value is in table 2, and minimal detectable concentration is 1ppm, and modeling result is desirable, reliable.
Use the newly-built sample of near infrared spectrum calibration model to 15 forecast sets to predict, the correlation curve of predicted value and true value as shown in Figure 5.Relative coefficient R
2=0.99996 (0-1.7878% is shown in Fig. 5 (a)), R
2=0.99988 (1.7878%-9.4362%, see Fig. 5 (b)), predicted root mean square error RMSEP=0.003949 (0-1.7878%), RMSEP=0.032299 (1.7878%-9.4362%) is basically identical with cross validation root-mean-square error (RMSECV), and concrete numerical value is in table 1.
Table 1
Embodiment 5:
The actual sample recovery
From producing each 3 of the spandex thread sample obtaining different process 20D, 40D, in container, quantitative DMAC solution is added respectively when extracting, detect the DMAC content of the rear extract of extraction, survey time yield (each sample measures three times), the recovery obtained is at 97.64%-100.44%, illustrate that the method is used for the quantivative approach of solvent DMAC content in spandex thread accurately and reliably, concrete data are in table 2.
Table 2
Claims (7)
1., for a near infrared spectrum detection method for the remaining content of solvent in spandex thread, it is characterized in that the method comprises the steps:
1) configure the N of a series of variable concentrations, the acetone standard solution of N '-dimethyl acetamide DMAC, as calibration set sample;
2) the near infrared spectrum spectrogram of calibration set sample is measured, sweep limit 12000 ~ 4000cm
-1wave band, and spectrum spectrogram is normalized and after standardization pre-service, is associated with DMAC content in DMAC-acetone standard solution, adopt partial least square method to set up calibration model;
3) pre-service is carried out by after the spandex thread sample collection that production is taken out, the near infrared spectrum spectrogram of sample after mensuration pre-service, adopt and step 2) in identical preprocessing procedures process gained spectrogram, the spectrum spectrogram that obtains after pre-service is adopted step 2) calibration model analysis, draw DMAC content in spandex thread sample to be measured.
2. the near infrared spectrum detection method for the remaining content of solvent in spandex thread according to claim 1, is characterized in that, described calibration set number of samples is greater than 30.
3. the near infrared spectrum detection method for the remaining content of solvent in spandex thread according to claim 1, is characterized in that, in the acetone standard solution of described DMAC, the mass concentration of DMAC is 0-10%, and solvent is acetone.
4. the near infrared spectrum detection method for the remaining content of solvent in spandex thread according to claim 1, is characterized in that, carries out pre-service after described spandex thread sample collection, and its method takes quantitative sample to add in quantitative acetone soln, ultrasonic extraction.
5. the near infrared spectrum detection method for the remaining content of solvent in spandex thread according to claim 1, it is characterized in that, the method of the near infrared spectrum spectrogram of described mensuration calibration set sample uses ABB AB MB3600 Fourier Transform Near Infrared instrument, adopt transmission mode, liquid cell dedicated test passage, each Sample Scan is averaged for 32 times and obtains.
6. the near infrared spectrum detection method for the remaining content of solvent in spandex thread according to claim 4, it is characterized in that described sample pretreatment is: the quality taking quantitative spandex thread sample is 5-10g, the quality of quantitative acetone is 30-60g, ultrasonic extraction 0.5 hour, extract is preheated to 25 ± 0.5 DEG C.
7. the near infrared spectrum detection method for the remaining content of solvent in spandex thread according to claim 1, is characterized in that, after described pre-service, the best modeled wave band of spectrum spectrogram confirms as 4484-5095cm
-1, 5579-6167cm
-1, 8212-9014cm
-1, 10652-11448cm
-1four spectral ranges.
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