CN1260483A - Quick determination method for ethylene content in ethylene-propylene copolymerization of polypropylene - Google Patents

Quick determination method for ethylene content in ethylene-propylene copolymerization of polypropylene Download PDF

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CN1260483A
CN1260483A CN 00112047 CN00112047A CN1260483A CN 1260483 A CN1260483 A CN 1260483A CN 00112047 CN00112047 CN 00112047 CN 00112047 A CN00112047 A CN 00112047A CN 1260483 A CN1260483 A CN 1260483A
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ethylene
copp
ethene
content
ethylene contents
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CN1124483C (en
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赵玉镶
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Sinopec Yangzi Petrochemical Co Ltd
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Sinopec Yangzi Petrochemical Co Ltd
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Abstract

The rapid testing method of ethylene content is characterized by using Fourier transform infrared spectrometer to measure out ratio value X of absorbancy value of peak area of ethylene characteristic peak 720 cm(-1) of ethylene-propylene copolymer polypropylene sample and absorbancy value of peak area of copolymer polypropylene characteristic peak 4500-3955 cm(-1), then using regression formula Y=ax+b to calculate the ethylene content Y%, in the regression formula Y=ax+b, a and b are constant, they can be obtained by means of IR spectrum of standard sample.

Description

Ethylene contents rapid test method in the ethylene, propylene COPP
The present invention relates to polyolefinic analytical approach, specifically, the mensuration of ethylene contents in the ethylene, propylene COPP.
Isotactic polypropylene is a kind of crystalline high polymer, and its impact flexibility is lower, and especially the fragility under the low temperature has limited its use greatly.Therefore, people adopt the method for adding toughness material blend or copolymerization that it is carried out modification, to reach request for utilization.
Second third COPP is an ethene and propylene Ziegler-natta catalyst copolymerization suitability for industrialized production product, also claims " ethylene-propylene block copolymer ", and its many character, particularly impact strength increases significantly than isotactic polypropylene.
In second third COPP, the addition of ethene, existence and the morphosis of final COPP of ethene on final polymer molecular chain is very big to macroscopical mechanical property influence of polymkeric substance, the final usability of decision COPP.So, simple and direct, measure ethylene contents in second third COPP quickly and accurately, it is one of technology controlling and process key parameter during COPP is produced, being requisite internal control index in the product inspection, also is industrial large-scale production plant long-period stable operation and to produce good COPP material necessary.
The ethene quantitative analysis method is a lot of in second third COPP, as chemical analysis, radioisotope method, homopolymer blend method, model compound method, nuclear magnetic resonance method.Chemical analysis, radioisotope method, model compound method, because the running program complexity does not reach the express-analysis requirement, in suitability for industrialized production, seldom use.Homopolymer blend thing method is because seldom use of test error.Because the raising of NMR sensitivity and resolution is used 13C-NMR method research copolymerized type propene polymer sequential structure and composition, quantitative test copolymer ethylene content is owing to NMR instrument costliness exactly, the analytical instrument complicated operation, analytical cycle is long, simple and direct requirement fast in the big production of incompatible industry.
The purpose of this invention is to provide a kind of quick, easy Fourier transform infrared spectrometer of utilizing and measure the method for ethylene contents in second third COPP.
Technical scheme of the present invention is as follows.
Ethylene contents rapid assay methods in a kind of ethylene, propylene COPP, it is to measure the second third COPP sample ethene characteristic peak 720cm with Fourier transform infrared spectrometer -1The absorbance and the COPP characteristic peak 4500～3955cm of peak area -1The ratio X of absorbance of peak area, calculate the content Y% of ethene then with the regression formula Y=ax+b that draws through regretional analysis.Y% is the mass percent that contains ethene in the ethylene, propylene COPP.
For same instrument, the same test condition, a and b are constant among the regression formula Y=ax+b, and they can be tried to achieve by the infrared spectrum of standard model, and standard model can be used 13The C-NMR method is measured and is obtained.
Assay method of the present invention, when ethylene contents in the ethylene, propylene COPP in different range sections, a among its regression formula Y=ax+b and b value can be values inequality.The inventor is divided into three content sections according to conditions such as employed instruments with ethylene contents, promptly high ethylene contents section: 12%＜C 2 =M%≤30%, middle ethylene contents section: 3%＜C 2 =M%≤12%, low ethylene content section: 0.3%＜C 2 =M%≤3%.
The characteristics of this method are:
(1) this method is to measure a kind of universal method of ethylene contents in second third COPP with Fourier transform infrared spectrometer, and particularly suitable is such as the fast measuring of large-scale production plant suitability for industrialized production second third COPPs such as vapor phase method, slurry process.
(2) this method is at second third COPP (bipolymer)---the mensuration of ethylene contents in the thermoplastics.
(3) this method is all applicable to second third COPP pellet or powder.
(4) this method is simple and direct, quick, accurate.
Fig. 1 is the FT-IR infrared spectrogram of second third COPP;
Fig. 2 is the working curve of high ethylene contents;
Fig. 3 is the working curve of middle ethylene contents;
Fig. 4 is the working curve of low ethylene content.
Further specify the present invention by the following examples.Embodiment 1
Determining of the second third COPP standard specimen ethylene contents
With 13Each second third COPP standard specimen ethylene contents value (being set at actual value) of C-NMR nmr for the determination, 13The C-NMR nmr for the determination is finished by the approved qualified Chinese University of Science and Technology structured testing center (national open laboratory) of State Metrological Bureau.
This method is looked ethylene contents difference in second third COPP, is divided into high ethylene contents, middle ethylene contents, low ethylene content three parts.For simplicity, decide R=10x.
1.1 high ethylene contents regretional analysis, standard working curve are formulated:
The measurement range of formula: 12%＜C 2 =M%≤30%
The regression equation of the high ethylene contents of table 1.
Standard specimen ??YZ01 # ??YZ02 # ??YZ03 # ??YZ04 # ??YZ05 # ??YZ06 #
??C 2 ＝m％ 13C-NMR ????7.80 ????8.22 ????9.38 ????12.59 ????17.93 ????24.30
R ratio ????0.5472 ????0.5930 ????0.6778 ????0.9034 ????1.0753 ????1.4832
Regression equation ????Y＝18.2292R-2.6714
R value scope ????0.8048＜R≤1.7923
1.2 middle ethylene contents regretional analysis, standard working curve are formulated:
The measurement range of formula: 3%＜C 2 =M%≤12%
The regression equation of ethylene contents in the table 2.
Standard specimen ????YZ07 # ????YZ08 # ????YZ09 # ????YZ10 #
????C 2 ＝m％ ?? 13C-NMR ????11.87 ????10.60 ????5.59 ????3.75
R ratio ????0.6084 ????0.4238 ????0.2113 ????0.1320
Regression equation ????Y＝17.6584R+1.8802
R value scope ????0.1091＜R≤0.8048
1.3 low ethylene content regretional analysis, standard working curve are formulated:
The measurement range of formula: 0.3%≤C 2 =M%≤3%
Table 3. low ethylene content regression equation
Standard specimen ??YZ09 # ??YZ10 # ??YZ11 #
??C 2 ＝m％ ? 13C-NMR ????5.59 ????3.75 ????0.36
R ratio ????0.2113 ????0.1320 ????0.0106
Regression equation ????Y＝26.2143R+0.1409
R value scope ????0.0061＜R≤0.1091
Embodiment 22.1 testing tools
This method is suitable for various model FT-IR Fourier transform infrared spectrometer.The used instrument of the inventor is:
(1) U.S. PE company 1760 type Fourier transform infrared spectrometer
Energy of light source:＞30000
Resolution: 4.0cm -1
Scanning times: 20 times
(2) U.S. PE company, the SPECAC molding press:
Pressure: 0～15t (making service pressure is 4t)
Temperature: 0～300 ℃ of (temperature is 180 ℃ during use) 2.2 test condition
Test environment temperature: 25 ± 3 ℃
Test environment humidity: RH≤60%2.3 specimen are made:
(1) the sample pellet is placed metal die put on 180 ℃ ± 1 ℃ warm table, fusion 3 minutes is until 180 ℃, is forced into 4t constant temperature and takes out after 10 minutes and put cooling box (water-cooled) and be cooled to room temperature, and it is to be measured to take out film.
(2) film sample thickness 220-250 μ m selects the supporting press box of SPECAC molding press " E " frame for use.
(3) with prefabricated 5 earlier in powder sample, per then 2.5 be one group be copied into 2 to be measured.2.4 sample test step
(1) whether temperature, the humidity of checkout environment meets the requirements before the test, operate under the constant temperature of stipulating, constant humidity condition.
(2) FT-IR infrared spectrometer start, stablize 30 minutes after, whether inspection apparatus resolution, energy, signal to noise ratio (S/N ratio) reach the given index of producer, carry out the scanning of 0%, 100% transmitance and background noise then, enter next step test operation after normal.
(3) the second third COPP sample is suppressed the identical diaphragm of thickness by the sample preparation requirement, two of every sample systems are done parallel testing and are used.Diaphragm thickness differs≤5 μ m, otherwise from new compacting to conforming with thickness requirement.
(4) FT-IR infrared spectrometer wave-number range is set in 4500～450cm -1, carry out background scans.
(5) again the print that suppresses is inserted on the FT-IR sample fixed support, measure the transmissivity infrared spectrogram.Deposit processing to be calculated after test is finished.2.5 test result, calculating
(1) the gained second third COPP transmitted infrared light spectrogram is converted to the absorbance infrared spectrogram.
(2) on FT-IR absorbance infrared spectrogram, utilize computing machine to calculate 4500～3955cm respectively -1Peak area absorbance and 720cm -1The absorbance of peak-to-peak area.(referring to Fig. 1)
(3) calculate A 720/ A 4500～3955The peak area absorbance ratio and enlarge 10 times the R value.
(4) find corresponding ethylene contents according to R value size from working curve, or will calculate the ethylene contents of this sample in the R value substitution regression equation.
(do above-mentioned test with a plurality of standard models, then can calculate a and b value in the regression formula) 2.5.1 high-load ethene is analyzed regression equation
Sample YZ504 #Ethylene contents express-analysis in second third COPP
13C-NMR measures the different print FT-IR of (actual value): u=24.3 (m%) (1) measured value
The different print FT-IR of table 4. measured value
Print ????1 ????2 ????3 ????4 ????5 ????6 ????7 ????8 ????9
R ratio 1.4653 ?1.5274 ?1.4636 ?1.4509 ?1.4788 ?1.5011 ?1.5076 ?1.4881 ?1.5255
?C 2 ＝m％ 24.04 ?25.17 ?24.01 ?23.78 ?24.28 ?24.69 ?24.81 ?24.45 ?25.14
Absolute error -0.26 ?0.87 ?-0.29 ?-0.52 ?-0.02 ?0.39 ?0.51 ?0.15 ?0.84
Mean value Y=24.49m% mean absolute error: 24.49-24.30=0.19 relative error: 0.19/24.3 * 100%=0.7%
(1) same print difference FT-IR measured value
Table 5. is with sheet difference FT-IR measured value
Print ????1 ????2 ????3 ????4 ????5
R ratio ??1.4972 ??1.5108 ??1.5376 ??1.5297 ??1.5047
??C 2 ＝m％ ??24.63 ??24.84 ??25.37 ??25.26 ??24.74
Absolute error ??0.33 ??0.54 ??1.07 ??0.96 ??0.44
Y＝24.97m％
Mean absolute error: 24.97-24.3=0.67 (m%)
Relative error: content ethene regression equation among 0.67/24.3 * 100%=2.76%2.5.2
Sample YZ502 #Ethylene contents express-analysis in second third COPP
13C-NMR measures the different print FT-IR of (actual value): u=9.94m% (1) measured value
The different print FT-IR of table 6. measured value
Print ????1 ????2 ????3 ????4 ????5 ????6 ????7 ????8 ????9
R ratio 0.5301 ?0.5331 ?0.5303 ?0.5398 ?0.5609 ?0.5421 ?0.5216 ?0.5356 ?0.5383
?C 2 ＝m％ 11.24 11.29 ?11.24 11.41 ?11.79 ?11.45 ?11.09 11.34 11.39
Absolute error 1.30 ?1.35 ?1.30 ?1.47 ?1.85 ?1.51 ?1.15 ?1.40 ?1.45
Mean value Y=11.36m% mean absolute error: 11.36-9.94=1.42 relative error: 1.42/9.94 * 100%=14.29%
(2) same print difference FT-IR measured value
Table 7. is with sheet difference FT-IR measured value
Print ????1 ????2 ????3 ????4 ????5
R ratio 0.5423 ?0.5416 0.5476 0.5508 0.5473
C 2 ＝m％ 11.45 11.44 11.55 ?11.60 ?11.55
Absolute error 1.51 ?1.50 1.61 ?1.66 ?1.61
Y＝11.52m％
Mean absolute error: 11.52-9.94=1.58 (m%)
Relative error: 1.58/9.94 * 100%=15.90%2.5.3 low content ethene regression equation
Sample YZ501 #Ethylene contents express-analysis in second third COPP
13C-NMR measures the different print FT-IR of (actual value): u=0.75m% (1) measured value
The different print FT-IR of table 8. measured value
Print ????1 ????2 ????3 ????4 ????5 ????6 ????7 ????8 ????9
R ratio 0.0256 ?0.0273 ?0.0256 ?0.0233 ?0.0230 ?0.0241 ?0.0210 ?0.0219 ?0.0257
?C 2 ＝m％ 0.81 ?0.85 ?0.81 ?0.75 ?0.75 ?0.78 ?0.69 ?0.72 ?0.81
Absolute error 0.06 ?0.10 ?0.06 ?0.00 ?0.00 ?0.03 -0.06 -0.03 ?0.06
Mean value Y=0.77m% mean absolute error: 0.77-0.75=0.02 relative error: 0.02/0.75 * 100%=2.67%
(2) same print difference FT-IR measured value
Table 9. is with sheet difference FT-IR measured value
Print ????1 ????2 ????3 ????4 ????5
R ratio 0.0256 ?0.0273 ?0.0222 ?0.0219 ?0.0212
?C 2 ＝m％ 0.81 ?0.85 ?0.73 ?0.72 ?0.69
Absolute error 0.06 ?0.10 -0.02 -0.03 -0.06
Y＝0.76m％
Mean absolute error: 0.76-0.75=0.01 (m%)
Relative error: 0.01/0.75 * 100%=1.33%.

Claims (3)

1. ethylene contents rapid assay methods in the ethylene, propylene COPP is characterized in that measuring the second third COPP sample ethene characteristic peak 720cm with Fourier transform infrared spectrometer -1The absorbance and the multipolymer characteristic peak 4500～3955cm of peak area -1The ratio x of absorbance of peak area, calculate the content Y% (mass percent) of ethene then with the regression formula Y=ax+b that draws through regretional analysis, a in the regression formula and the value of b are tried to achieve by standard model.
2. assay method according to claim 1 is characterized in that ethylene contents sections different in the ethylene, propylene COPP, and a in the regression formula has different values with b.
3. assay method according to claim 2 is characterized in that the content of ethene in the ethylene, propylene COPP is divided into three content sections: high ethylene contents, containing the ethene amount is 12%＜C 2 =M%≤30%, middle ethylene contents, containing the ethene amount is 3%＜C 2 =M%≤12%, low ethylene content, containing the ethene amount is 0.3%＜C 2 =M%≤3%.
CN 00112047 2000-01-24 2000-01-24 Quick determination method for ethylene content in ethylene-propylene copolymerization of polypropylene Expired - Fee Related CN1124483C (en)

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Cited By (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN100445728C (en) * 2005-11-17 2008-12-24 中国石化扬子石油化工有限公司 Quick determination method for methyl content in polyethylene copolymer
CN106248612A (en) * 2015-06-10 2016-12-21 中国石油天然气股份有限公司 The assay method of co-monomer content in second the third fourth ternary polymerized polypropylene
CN108254334A (en) * 2017-12-29 2018-07-06 黄河三角洲京博化工研究院有限公司 A kind of method of each composition quality content in detection polyolefin
CN108362658A (en) * 2018-03-07 2018-08-03 苏州艾驰博特检测科技有限公司 Talcum powder content analysis and analysis method in a kind of polypropylene plastics
CN112485215A (en) * 2020-11-12 2021-03-12 北方华锦化学工业股份有限公司 Method for quantitatively analyzing ethylene content in impact-resistant polypropylene by infrared spectroscopy

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CN103267741B (en) * 2013-05-03 2015-05-20 浙江大学 Method for discriminating and modifying four-arm star-type SBS and line-type SBS for asphalt by infrared spectroscopy

Cited By (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN100445728C (en) * 2005-11-17 2008-12-24 中国石化扬子石油化工有限公司 Quick determination method for methyl content in polyethylene copolymer
CN106248612A (en) * 2015-06-10 2016-12-21 中国石油天然气股份有限公司 The assay method of co-monomer content in second the third fourth ternary polymerized polypropylene
CN106248612B (en) * 2015-06-10 2018-08-10 中国石油天然气股份有限公司 The assay method of co-monomer content in second the third fourth ternary polymerized polypropylene
CN108254334A (en) * 2017-12-29 2018-07-06 黄河三角洲京博化工研究院有限公司 A kind of method of each composition quality content in detection polyolefin
CN108254334B (en) * 2017-12-29 2020-12-22 黄河三角洲京博化工研究院有限公司 Method for detecting mass content of each component in polyolefin
CN108362658A (en) * 2018-03-07 2018-08-03 苏州艾驰博特检测科技有限公司 Talcum powder content analysis and analysis method in a kind of polypropylene plastics
CN112485215A (en) * 2020-11-12 2021-03-12 北方华锦化学工业股份有限公司 Method for quantitatively analyzing ethylene content in impact-resistant polypropylene by infrared spectroscopy

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