CN1766571A - Quick determination method for methyl content in polyethylene copolymer - Google Patents
Quick determination method for methyl content in polyethylene copolymer Download PDFInfo
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- CN1766571A CN1766571A CN 200510095458 CN200510095458A CN1766571A CN 1766571 A CN1766571 A CN 1766571A CN 200510095458 CN200510095458 CN 200510095458 CN 200510095458 A CN200510095458 A CN 200510095458A CN 1766571 A CN1766571 A CN 1766571A
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Abstract
The invention relates to a method for measuring methyl content of the polyethylene copolymer. It can measure the methyl content of the ethane and dissimilar integral copolymer. It uses Fourier transformation infrared spectrometer to measure the odds ratio X of the light absorbing value of the methyl character peak 1378-1379cm-1 peak area and the light absorbing value of the polythene copolymer character peak 2100-1980cm-1 peak area, then it uses the regression formula Y=KX+b to compute the methyl content Y% (K, b is constant).
Description
One, technical field
The present invention relates to polyolefinic analytical approach, specifically, the rapid assay methods of methyl content in ethene and different monomers (propylene, butylene, the hexene) multipolymer.
Two, background technology
In recent years, in the exploitation of high-performance, differential polyvinyl resin, each major company of the world adopts the technology path of ethene and other comonomer polymerization more and more, with the polyethylene and ethylene copolymers of obtained performance excellence.Their chemical property, crystal property, rheological property and processing characteristics are more and more diversified, and this just need analyze and research to their chemical constitution.
The mensuration of methyl content in the polyethylene and ethylene copolymers can obtain the information such as content, the degree of branching of monomer in the polyethylene and ethylene copolymers, thereby polyethylene and ethylene copolymers is carried out Molecular Structure Design and adjustment provides foundation, to obtain the polymkeric substance of desired properties.When the methyl content in the polyethylene and ethylene copolymers was analyzed, at present effective method just was to use nuclear magnetic resonance spectrometer.But this instrument test time is oversize, is unfavorable for the large batch of mensuration of polyolefine material.And infra-red sepectrometry speed is fast, favorable reproducibility, and the information of reflection molecular structure is many, Fourier transform infrared spectroscopy The Application of Technology especially, the application that makes it in superpolymer research is increasing.This paper is methyl characteristic absorption data association in standard specimen and the infrared spectrum with the data of NMR method institute test sample product, has drawn the quantitative correction curve, makes assay method simplify and improve the accuracy of measuring.
Three, summary of the invention
The purpose of this invention is to provide a kind of quick, easy Fourier transform infrared spectrometer of utilizing and measure the method for methyl content in ethene and different monomers (propylene, butylene, the hexene) multipolymer, thereby obtain the molal quantity of monomer in the polymkeric substance.
Technical solution of the present invention is: quick determination method for methyl content in a kind of ethene and different monomers (propylene, butylene, the hexene) multipolymer, it is to measure ethene and different monomers (propylene, butylene, hexene) polyethylene copolymer sample methyl characteristic peak 1378-1379cm with Fourier transform infrared spectrometer
-1Peak area (is chosen the baseline scope of methyl absorption peak: 1400-1330cm
-1) absorbance and polyethylene copolymer characteristic peak 2100-1980cm
-1The ratio X of the absorbance of peak area is then to calculate the content Y% of methyl through regression formula Y=KX+b.Y% is the methyl molal quantity in 100 ethene segments.
For same instrument, the same test condition, K and b are constant among the regression formula Y=KX+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, methyl content in ethene and different monomers (propylene, butylene, the hexene) multipolymer, K and b value are values inequality among its regression formula Y=KX+b.The inventor measures the range section of polyethylene and ethylene copolymers according to conditions such as employed instruments: ethylene-propylene copolymer methyl content section, 0.1≤Y%≤13%; Second fourth multipolymer methyl content section, 0.1≤Y%≤4.7%; The own multipolymer methyl content of second section, 0.1≤Y%≤4.5%. wherein Y% is the mole percentage of methyl content.
The effect of invention
(1) this method is to measure a kind of universal method of methyl content in ethene and different monomers (propylene, butylene, the hexene) multipolymer with Fourier transform infrared spectrometer, the fast measuring of methyl content in large-scale production plant suitability for industrialized production ethene such as particularly suitable such as vapor phase method, slurry process and different monomers (propylene, butylene, the hexene) multipolymer.
(2) this method is the mensuration at methyl content in ethene and different monomers (propylene, butylene, hexene) multipolymer (bipolymer)----thermoplastics.
(3) this method is all applicable to polyethylene and ethylene copolymers pellet or powder.
(4) this method is simple and direct, quick, accurate
Four, description of drawings
Fig. 1 is the FT-IR infrared spectrogram of ethene of the present invention and different copolymer monomer (propylene, butylene, hexene)
(Figure 1A is that ethylene-propylene copolymer figure, Figure 1B are that second fourth multipolymer figure, Fig. 1 C are the own multipolymer figure of second)
Fig. 2 is the working curve of ethylene-propylene copolymer of the present invention
Fig. 3 is the working curve of second fourth multipolymer of the present invention
Fig. 4 is the working curve of the own multipolymer of second of the present invention
Five, embodiment
Further specify the present invention by the following examples:
Determining of polyethylene and ethylene copolymers standard specimen methyl content
With
13Each ethene of C-NMR nmr for the determination and different monomers (propylene, butylene, hexene) multipolymer methyl content value (being set at actual value),
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 the difference of comonomer in the polyethylene and ethylene copolymers, is divided in methyl content in the ethylene-propylene copolymer, the second fourth multipolymer methyl content three parts in methyl content, the own multipolymer of second.For simplicity, decide R=10X.
1.1 methyl content regretional analysis in the ethylene-propylene copolymer, standard working curve are formulated:
The measurement range of formula: 0.1≤Y%≤13%
| | 1# | 2# | 3# | 4# | 5# | 6# |
| Y％ 13C-NMR | 0.10 | 1.15 | 2.16 | 6.35 | 9.90 | 12.55 |
| R ratio | 0.4655 | 1.1303 | 1.4286 | 3.2353 | 5.2622 | 6.6375 |
| Regression equation | Y＝2.0425R-0.8135 | |||||
1.2 methyl content regretional analysis in the second fourth multipolymer, standard working curve are formulated:
The measurement range of formula: 0.1≤Y%≤4.7%
| Standard specimen | 7# | 8# | 9# | 10# | 11# | 12# |
| Y％ 13C-NMR | 0.1 | 0.41 | 1.1 | 2.1 | 3.72 | 4.70 |
| R ratio | 0.1554 | 0.4154 | 0.9943 | 1.8899 | 3.3386 | 4.2057 |
| Regression equation | Y＝1.1319R-0.0533 | |||||
1.3 methyl content regretional analysis in the own multipolymer of second, standard working curve are formulated:
The measurement range of formula: 0.1≤Y%≤4.5%
| Standard specimen | 13# | 14# | 15# | 16# | 17# |
| Y％ 13C-NMR | 0.1 | 0.67 | 1.91 | 2.78 | 4.42 |
| R ratio | 0.1852 | 0.3854 | 0.8254 | 1.1340 | 1.7159 |
| Regression equation | Y＝2.8211R-0.4196 | ||||
2.1 testing tool
This method is suitable for various model FT-IR Fourier transform infrared spectrometer.The used instrument of the present invention is:
(1) the German Brooker IFS 66/S of company type infrared spectrometric analyzer
Energy of light source:＞26000
Resolution: 4.0cm
-1
Scanning times: 32 times
(2) U.S. PE company: SPECAC molding press
Pressure: 0-15t
Temperature: 0-300 ℃
2.2 test condition
Test environment temperature: 25 ± 5 ℃
Test environment humidity: R≤55%
2.3 specimen is made
(1) sample pellet (or powder) is placed the metal die of SPECAC molding press of lining aluminium foil (being convenient to peeling off of diaphragm), selecting the mould frame by the Beer law is " C " frame
(2) the molding press temperature is controlled at 172 ℃ ± 2 ℃.Metal die is placed on heating and melting on the SPECAC molding press.When treating that temperature is raised to 172 ℃ ± 2 ℃, be forced into (gauge pressure) behind the 4t, unload immediately and be depressed into " O ", and take out the cooling box that metal die places chilled water, be cooled to room temperature
(3) diaphragm of sample in the taking-up metal die measures diaphragm thickness with slide calliper rule.Diaphragm thickness control 52-53 μ m, parallel plate thickness difference＜0.2 μ m.Otherwise compacting is after made sample diaphragm is qualified, to be measured again.
2.4 testing procedure
(1) whether the temperature of checkout environment, humidity meet the requirements, and operate under the constant temperature of stipulating, constant humidity condition
(2) after the FT-IR infrared spectrometer was started shooting 30 minutes, the energy of inspection apparatus, whether resolution, signal to noise ratio (S/N ratio) reach the given index of instrument, carry out the scanning of 0%, 100% transmitance and background noise.After normal, enter next step operation
(3) polyethylene specimen is made, and the strict accuracy of controlling heating-up temperature and measuring with the assurance methyl content pressing time
(4) set FT-IR infrared spectrometer wave-number range at 4500～350cm
-1, and carry out background scans.After normal, carry out sample test
(5) testing sample that will suppress, that meet the requirements inserts on the FT-IR infrared spectrograph sample test bracket, measures the transmitted infrared light spectrogram, and deposits computing machine in, and is pending
2.5 test result, calculating
(1) gained polyethylene and ethylene copolymers transmitted infrared light spectrogram is converted to the absorbance infrared spectrogram.
(2) on FT-IR absorbance infrared spectrogram, utilize computing machine to calculate 2100-1980cm respectively
-1Peak area absorbance and 1378-1379cm
-1Peak area (is chosen the baseline scope of methyl absorption peak: 1400-1330cm
-1) absorbance.(referring to Fig. 1)
(3) calculate A (1378-1379)/A (2100-1980) peak area absorbance ratio and enlarge 10 times the R value.
(4) find corresponding methyl content according to R value size from working curve, or will calculate the methyl content of this sample in the R value substitution regression equation.(do above-mentioned test with a plurality of standard models, then can calculate K and b value in the regression formula)
2.5.1 ethylene-propylene copolymer regression equation
Methyl content express-analysis in the sample 3# ethylene-propylene copolymer
13The C-NMR method is measured (actual value): 3#=2.16 (mol%)
(1) different print FT-IR measured values
| 3#-1 | 3#-2 | 3#-3 | 3#-4 | 3#-5 | |
| R ratio | 1.4286 | 1.3821 | 1.3768 | 1.4706 | 1.4615 |
| Y％ | 2.07 | 1.98 | 1.97 | 2.16 | 2.14 |
| Absolute error | -0.09 | -0.18 | -0.19 | 0 | -0.02 |
Mean value Y=2.06mol%
Mean absolute error: 2.06-2.16=-0.1
Relative error: 0.1/2.16*100%=4.6%
(2) same print difference FT-IR measured value
| 3#-2-1 | 3#-2-2 | 3#-2-3 | 3#-2-4 | 3#-2-5 | |
| R ratio | 1.325 | 1.3243 | 1.3050 | 1.3126 | 1.3058 |
| Y％ | 1.86 | 1.86 | 1.82 | 1.84 | 1.82 |
| Absolute error | -0.3 | -0.3 | -0.34 | -0.32 | -0.34 |
Mean value Y=1.84mol%
Mean absolute error: 1.84-2.16=-0.32
Relative error: 0.32/2.16*100%=1.5%
2.5.2 second fourth multipolymer regression equation
Methyl content express-analysis in the sample 10# second fourth multipolymer
13The C-NMR method is measured (actual value): 10#=2.1 (mol%)
(1) different print FT-IR measured values
| 10#-1 | 10#-2 | 10#-3 | 10#-4 | 10#-5 | |
| R ratio | 2.1263 | 2.1439 | 2.0378 | 1.9758 | 1.8520 |
| Y％ | 2.35 | 2.37 | 2.25 | 2.18 | 2.04 |
| Absolute error | 0.25 | 0.27 | 0.15 | 0.08 | -0.06 |
Mean value Y=2.24mol%
Mean absolute error: 2.24-2.1=0.14
Relative error: 0.14/2.1*100%=6.7%
(2) same print difference FT-IR measured value
| 10#-2-1 | 10#-2-2 | 10#-2-3 | 10#-2-4 | 10#-2-5 | |
| R ratio | 1.9758 | 1.8623 | 2.1066 | 1.8998 | 2.0986 |
| Y％ | 2.18 | 2.05 | 2.34 | 2.09 | 2.32 |
| Absolute error | 0.08 | -0.05 | 0.24 | -0.01 | 0.22 |
Mean value Y=2.20mol%
Mean absolute error: 2.20-2.1=0.10
Relative error: 0.1/2.1*100%=4.8%
2.5.3 the own multipolymer regression equation of second
Methyl content express-analysis in the own multipolymer of sample 16# second
13The C-NMR method is measured (actual value): 16#=2.78 (mol%)
(1) different print FT-IR measured values
| 16#-1 | 16#-2 | 16#-3 | 16#-4 | 16#-5 | |
| R ratio | 1.1462 | 1.0792 | 1.0613 | 1.1370 | 1.1267 |
| Y％ | 2.81 | 2.63 | 2.57 | 2.79 | 2.76 |
| Absolute error | 0.03 | -0.15 | -0.21 | 0.01 | -0.02 |
Mean value Y=2.71mol%
Mean absolute error: 2.71-2.78=-0.07
Relative error: 0.07/2.78*100%=2.5%
(2) same print difference FT-IR measured value
| 16#-3-1 | 16#-3-2 | 16#-3-3 | 16#-3-4 | 16#-3-5 | |
| R ratio | 1.0613 | 1.0988 | 1.1103 | 1.0879 | 1.1093 |
| Y％ | 2.57 | 2.68 | 2.71 | 2.65 | 2.71 |
| Absolute error | -0.21 | -0.10 | -0.07 | -0.13 | -0.07 |
Mean value Y=2.66mol%
Mean absolute error: 2.66-2.78=-0.12
Relative error: 0.12/2.78*100%=4.3%
Claims (2)
1, quick determination method for methyl content in the polyethylene and ethylene copolymers is characterized in that polyethylene and ethylene copolymers is prepared into the infrared spectrometer specimen, measures methyl characteristic peak 1378-1379cm in the polyethylene and ethylene copolymers sample with Fourier transform infrared spectrometer
-1Peak area, and choose the baseline scope 1400-1330cm of methyl absorption peak
-1Absorbance and polyethylene copolymer characteristic peak 2100-1980cm
-1The ratio X of the absorbance of peak area calculates the content Y% of methyl then with regression formula Y=KX+b; K and b are constant, try to achieve by the infrared spectrum of standard model, and the content of standard model is measured with standard law.
2, quick determination method for methyl content in the polyethylene and ethylene copolymers is characterized in that standard law is
13The C-NMR method is used for measuring the accurate content of polyethylene and ethylene copolymers methyl content.
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN102297820A (en) * | 2010-06-25 | 2011-12-28 | 中国石油天然气股份有限公司 | Method for measuring content of short chain branch in polyethylene copolymer |
| CN101750279B (en) * | 2008-11-28 | 2012-04-04 | 上海宝钢工业检测公司 | Infrared peak area ratio determination method for content of PVDF resin in fluorocarbon color coated sheet coating |
| CN105301029A (en) * | 2015-09-17 | 2016-02-03 | 常州大学 | Method for measuring glycolide and D, L-lactide copolymer monomer conversion rate |
| CN111521577A (en) * | 2020-04-29 | 2020-08-11 | 清华大学合肥公共安全研究院 | Infrared spectrum quantitative analysis method taking carbon dioxide peak area as reference |
| CN115639165A (en) * | 2022-11-01 | 2023-01-24 | 山东京博石油化工有限公司 | Method for detecting comonomer content in polyolefin elastomer |
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| CN1124483C (en) * | 2000-01-24 | 2003-10-15 | 中国石化集团扬子石油化工有限责任公司 | Quick determination method for ethylene content in ethylene-propylene copolymerization of polypropylene |
| CN1152245C (en) * | 2001-02-28 | 2004-06-02 | 中国石化集团扬子石油化工有限责任公司 | Fast test method of ethylene-propylene rubber content in ethylene-propylene copolymer |
| CN1200266C (en) * | 2003-05-26 | 2005-05-04 | 中国科学院上海技术物理研究所 | Method of detecting chemical medicine component in Chinese medicine via infrared spectrum |
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- 2005-11-17 CN CNB2005100954580A patent/CN100445728C/en not_active Expired - Fee Related
Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101750279B (en) * | 2008-11-28 | 2012-04-04 | 上海宝钢工业检测公司 | Infrared peak area ratio determination method for content of PVDF resin in fluorocarbon color coated sheet coating |
| CN102297820A (en) * | 2010-06-25 | 2011-12-28 | 中国石油天然气股份有限公司 | Method for measuring content of short chain branch in polyethylene copolymer |
| CN102297820B (en) * | 2010-06-25 | 2014-08-06 | 中国石油天然气股份有限公司 | Method for measuring content of short chain branch in polyethylene copolymer |
| CN105301029A (en) * | 2015-09-17 | 2016-02-03 | 常州大学 | Method for measuring glycolide and D, L-lactide copolymer monomer conversion rate |
| CN111521577A (en) * | 2020-04-29 | 2020-08-11 | 清华大学合肥公共安全研究院 | Infrared spectrum quantitative analysis method taking carbon dioxide peak area as reference |
| CN115639165A (en) * | 2022-11-01 | 2023-01-24 | 山东京博石油化工有限公司 | Method for detecting comonomer content in polyolefin elastomer |
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