CN104266998A - Near-infrared spectrum detection method for isocyanate group content in spandex prepolymer - Google Patents
Near-infrared spectrum detection method for isocyanate group content in spandex prepolymer Download PDFInfo
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- CN104266998A CN104266998A CN201410588723.8A CN201410588723A CN104266998A CN 104266998 A CN104266998 A CN 104266998A CN 201410588723 A CN201410588723 A CN 201410588723A CN 104266998 A CN104266998 A CN 104266998A
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Abstract
The invention relates to a near-infrared spectrum method for detecting the isocyanate group content in a spandex prepolymer. The method comprises the following steps: (1) collecting a spandex prepolymer sample, selecting an enough quantity of representative calibration set samples, and detecting the isocyanate group content in the samples by a chemical titration method; (2) measuring near-infrared spectrograms of the correction set samples, performing spectrum preprocessing on wave bands from 9,0000 to 4,000cm<-1> of the spectrograms, associating the isocyanate group content, which is measured by the chemical titration method, of the samples, and constructing a correction model by a partial least square method; (3) measuring a near-infrared spectrogram of the spandex prepolymer sample to be detected, processing the wave bands from 9,0000 to 4,000cm<-1> of the spectrograms by the preprocessing method which is the same as that in the step (2), and substituting an absorbancy value obtained by preprocessing into the correction model in the step (2) to obtain the isocyanate group content in the spandex prepolymer sample to be detected. The near-infrared spectrum method has the advantages of simple and quick analysis process, high interference resistance, lossless analysis, small sampling amount and the like.
Description
Technical field
The present invention relates to a kind of near infrared spectrum detection method for isocyanate group content in spandex performed polymer, belong 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.And in spandex production run in prepolymerization thing (i.e. performed polymer) isocyanates (NCO) content directly can affect the important indicators such as the ultimate strength of spandex product and breaking elongation, the isocyanate group content therefore measuring spandex performed polymer rapidly and accurately to become in spandex production run an important technology.
At present, the assay method of isocyanate group is mainly divided into chemical analysis and instrumental method.Chemical analysis uses the toxic chemical such as toluene, di-n-butylamine usually, and detect and produce a large amount of waste liquids, environmental pollution is larger; Detect length consuming time, less stable simultaneously, have impact to the stability of production control.Therefore, study a kind of can in time, accurately, detect the method for isocyanate group content in performed polymer fast, to determining that spandex synthetic reaction terminal and production control stability have important practical usage.
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.Lou Chunhua etc. adopt infra-red sepectrometry to determine the absorption value ratio of isocyanate group addition product Zhong Liangzhong functional group rapidly and accurately, thus isocyanate group content in mensuration system, and finally calculate the enclosed of isocyanate group.But, utilize the research of isocyanate group content in spandex performed polymer near infrared ray actual production to have no report.
Summary of the invention
Technical matters: the object of the invention is to the deficiency solving currently available technology, a kind of near infrared spectrum detection method for isocyanate group content in spandex performed polymer is provided.The implementation process of this detection method is easy, and precision is high, reproducible.
Technical scheme: of the present inventionly a kind ofly to comprise the steps: for the near infrared spectrum detection method of isocyanate group content in spandex performed polymer
1) collect spandex performed polymer sample, select enough representational calibration set samples, detect the mass concentration of isocyanate group in sample with chemical titration;
2), after sample pretreatment, the near infrared spectrum spectrogram of calibration set sample is measured, sweep limit 9000 ~ 4000cm
-1wave band, and after carrying out Pretreated spectra, in this sample recorded with chemical titration, isocyanate group content is associated, and adopts partial least square method to set up calibration model;
3) the near infrared spectrum spectrogram of spandex performed polymer sample to be measured is measured, adopt the preprocessing procedures process gained spectrogram identical with step 2, the absorbance obtained after pre-service is substituted into the calibration model of step 2, obtain isocyanate group content in spandex performed polymer sample to be measured.
Described calibration set sample number is greater than 50.
The mass concentration of the described spandex performed polymer sample for infrared diaphanoscopy is 2.0%-3.0%, and solvent is dimethyl acetamide.
Described sample pretreatment is evacuation and centrifugal degassing, be preheated to 45 ± 0.5 DEG C.
The assay method of described near infrared light spectrogram uses Thermo company Antaris II 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 step 1) in the testing conditions of chemical titration be:
Sample preparation: 1g spandex performed polymer is dissolved in the mixed solution of 25mL ethyl acetate and 10mL di-n-butylamine;
Titrant: 0.5M HCl;
Mass concentration computing formula: NCO%=(V-V
1) × c
hCl× 42.02 × 100%/m
Wherein, V-blank consumes the volume (L) of hydrochloric acid;
V
1-sample consumes the volume (L) of titrant;
M-sample quality (g).
The pretreated method of described near infrared spectrum spectrogram is First derivative spectrograply or Norris derivative smoothing filtering technique.
After described pre-service, the best modeled wave band of spectrogram confirms as 4690-4539cm
-1, 6236-5881cm
-1, 8917-8364cm
-1three spectral detection scopes.
Beneficial effect: it is detection target that this method chooses isocyanate group content in spandex performed polymer, and set up quantitative model, method RMSECV is little, and r=0.9996 correlativity is good.And unknown sample is predicted, acquired results is satisfactory.Application near-infrared spectrum technique can carry out quantitative test to isocyanate group content in spandex performed polymer in conjunction with PLS method, method is accurate, the plenty of time is saved than chemical titration, 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;
Fig. 3 is first derivative spectrum figure;
Fig. 4 is isocyanate group content calibration model main cause subnumber and RMSECV graph of a relation;
Fig. 5 is calibration set isocyanate group content spectral predicted value and true value correlation curve;
Fig. 6 is forecast set sample isocyanate group content spectral predicted value and true value correlation curve.
Embodiment
For achieving the above object, the invention provides a kind of near infrared spectrum detection method for isocyanate group content in spandex performed polymer, the method comprises the steps:
1) collect spandex performed polymer sample, select enough representational calibration set samples, detect isocyanate group mass concentration in sample with chemical titration;
2), after sample pretreatment, the near infrared spectrum spectrogram of calibration set sample is measured, sweep limit 9000 ~ 4000cm
-1wave band, and after carrying out Pretreated spectra, determine best modeled wave band, in this sample obtained with chemical titration side, isocyanate group content is associated, and adopts partial least square method to set up calibration model;
3) the near infrared spectrum spectrogram of spandex performed polymer sample to be measured is measured, adopt best modeled wave band in the preprocess method process gained spectrogram identical with step 2, the absorbance obtained after pre-service is substituted into the calibration model of step 2, obtain isocyanate group content in spandex performed polymer sample to be measured.
In detection of the present invention, for detection target be isocyanate group content in spandex performed polymer, step 1) establish chemical titration to detect this group, comprise following condition:
Sample preparation: 1g spandex performed polymer is dissolved in the mixed solution of 25mL ethyl acetate and 10mL di-n-butylamine;
Titrant: 0.5M HCl;
Mass concentration computing formula: NCO%=(V-V
1) × c
hCl× 42.02 × 100%/m
Wherein, V-blank consumes the volume (L) of hydrochloric acid;
V
1-sample consumes the volume (L) of titrant;
M-sample quality (g)
The detected value of this chemical titration is namely as detection truth-value.
In described method, spandex prepolymer solution, 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 9000 ~ 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 first order derivative, Norris derivative smoothing filtering technique.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).Use PLS method in TQ Analyst analysis software to carry out data processing, 26 increment product of choosing, as Prediction, carry out cross-validation with Calibration, and RMSECV is 0.00533.When there being forecast set sample to evaluate the detectability of PLS model, RMSEP is 0.00669.
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:
1, the process of instrument condition and spandex performed polymer sample:
Instrument: near infrared spectrum is gathered by Thermo company of U.S. Antaris II Fourier Transform Near Infrared instrument, and this instrument is furnished with TQ Analyst analysis software, quartzy liquid cell and InGaAs detecting device.The spectrogram of each sample obtains by being averaged through 32 scanning.Sweep limit is 9000 ~ 4000cm
-1
Sample: sample used in experiment is the prepolymer product of collecting in spandex production run, performed polymer dissolves through chemical titration analysis through ethyl acetate and di-n-butylamine mixed liquor.
Embodiment 2:
Chemical titration detects and comprises following condition:
1) sample preparation: 1g spandex performed polymer is dissolved in the mixed solution of 25mL ethyl acetate and 10mL di-n-butylamine;
2) titrant: 0.5M HCl;
3) mass concentration computing formula: NCO%=(V-V
1) × C
hCl× 42.02 × 100%/m
The detected value of this chemical titration is namely as detection truth-value.
Table 1 is chemical analysis detection precision.
Table 1
Embodiment 3:
Sample near-infrared spectral measurement:
This experiment uses quartzy liquid absorption pond, pours spandex performed polymer into liquid absorption pond, after evacuation and centrifugal degassing process, be preheated to 45 ± 0.5 DEG C, put into detection cell, carry out the spectra collection of sample, same sample is scanned 32 times, after average, obtain final spectrogram, as accompanying drawing 2.
Embodiment 4:
Prediction:
Figure 2 shows that the raw data of spectrum, after first order derivative process, obtain first derivative spectrum figure (Fig. 3), confirm 4690-4539cm
-1, 6236-5881cm
-1, 8917-8364cm
-1three spectral detection scopes, as modeling wave band, use PLS method to set up quantitative calibration models.For avoiding occurring " over-fitting " phenomenon, adopt and stay a cross-validation method choose reasonable main cause subnumber, as shown in Figure 4, best main cause subnumber is 5 to the main cause subnumber of the isocyanate group content that cross validation obtains.
Embodiment 5:
Analyze:
By 80 spandex performed polymer samples, wherein 54 samples are as calibration set, and 26 samples are as forecast set.The predicted value of the sample isocyanate group content corresponding with best main cause subnumber and actual value matched curve are as Fig. 5, and the predicted value of isocyanate group and correlation coefficient r=0.9997 of true value, concrete numerical value is in table 2, and modeling result is desirable, reliable.
Use the newly-built sample of near infrared spectrum calibration model to 26 forecast sets to predict, the correlation curve of predicted value and true value as shown in Figure 6.Relative coefficient r=0.9996, predicted root mean square error RMSEP=0.00669, basically identical with cross validation root-mean-square error (RMSECV), concrete numerical value is in table 2.
Table 2
Claims (8)
1., for a near infrared spectrum detection method for isocyanate group content in spandex performed polymer, it is characterized in that the method comprises the steps:
1) collect spandex performed polymer sample, select enough representational calibration set samples, detect the mass concentration of isocyanate group in sample with chemical titration;
2), after sample pretreatment, the near infrared spectrum spectrogram of calibration set sample is measured, sweep limit 9000 ~ 4000 cm
-1wave band, and after carrying out Pretreated spectra, in this sample recorded with chemical titration, isocyanate group content is associated, and adopts partial least square method to set up calibration model;
3) measure the near infrared spectrum spectrogram of spandex performed polymer sample to be measured, adopt the preprocessing procedures process gained spectrogram identical with step 2
, the absorbance obtained after pre-service is substituted into the calibration model of step 2, obtain isocyanate group content in spandex performed polymer sample to be measured.
2. the near infrared spectrum detection method for isocyanate group content in spandex performed polymer according to claim 1, is characterized in that, described calibration set sample number is greater than 50.
3. the near infrared spectrum detection method for isocyanate group content in spandex performed polymer according to claim 1, is characterized in that, the mass concentration of the described spandex performed polymer sample for infrared diaphanoscopy is 2.0%-3.0%, and solvent is dimethyl acetamide.
4. the near infrared spectrum detection method for isocyanate group content in spandex performed polymer according to claim 1, is characterized in that, described sample pretreatment, is evacuation and centrifugal degassing, is preheated to 45 ± 0.5 DEG C.
5. the near infrared spectrum detection method for isocyanate group content in spandex performed polymer according to claim 1, it is characterized in that, the assay method of described near infrared light spectrogram uses Thermo company Antaris II 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 isocyanate group content in spandex performed polymer according to claim 1, it is characterized in that, the testing conditions of the chemical titration in described step 1) is:
Sample preparation: 1 g spandex performed polymer is dissolved in the mixed solution of 25 mL ethyl acetate and 10 mL di-n-butylamines;
Titrant: 0.5 M HCl;
Mass concentration computing formula: NCO%=(V-V
1) × c
hCl× 42.02 × 100%/m
Wherein, V-blank consumes the volume (L) of hydrochloric acid;
V
1-sample consumes the volume (L) of titrant;
M-sample quality (g).
7. the near infrared spectrum detection method for isocyanate group content in spandex performed polymer according to claim 1, is characterized in that, the pretreated method of described near infrared spectrum spectrogram is First derivative spectrograply or Norris derivative smoothing filtering technique.
8. the near infrared spectrum detection method for isocyanate group content in spandex performed polymer according to claim 1 or 7, is characterized in that, after described pre-service, the best modeled wave band of spectrogram confirms as 4690-4539 cm
-1, 6236-5881 cm
-1, 8917-8364 cm
-1three spectral detection scopes.
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN104730028A (en) * | 2015-03-12 | 2015-06-24 | 浙江华峰氨纶股份有限公司 | Near-infrared spectral detection method for residual content of solvent in polyurethane elastic fiber filaments |
| CN104730029A (en) * | 2015-03-12 | 2015-06-24 | 浙江华峰氨纶股份有限公司 | Method for simultaneously detecting solvent and moisture in polyurethane elastic fiber production solvent recovery system |
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| CN114112965A (en) * | 2020-08-31 | 2022-03-01 | 万华化学集团股份有限公司 | Method for detecting trace moisture in isocyanate and application of method in online monitoring |
| CN114112965B (en) * | 2020-08-31 | 2024-04-09 | 万华化学集团股份有限公司 | Method for detecting trace moisture in isocyanate and application of method in online monitoring |
| CN112881334A (en) * | 2021-01-20 | 2021-06-01 | 山东非金属材料研究所 | Method for detecting itaconic acid content in poly (acrylonitrile-itaconic acid) |
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Application publication date: 20150107 |