WO2015057002A1 - 폴리 올레핀 분지의 분석 방법 및 이를 이용한 시스템 - Google Patents
폴리 올레핀 분지의 분석 방법 및 이를 이용한 시스템 Download PDFInfo
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- WO2015057002A1 WO2015057002A1 PCT/KR2014/009756 KR2014009756W WO2015057002A1 WO 2015057002 A1 WO2015057002 A1 WO 2015057002A1 KR 2014009756 W KR2014009756 W KR 2014009756W WO 2015057002 A1 WO2015057002 A1 WO 2015057002A1
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- polyolefin
- branch
- ratio
- pulse program
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- 229920000098 polyolefin Polymers 0.000 title claims abstract description 83
- 238000004458 analytical method Methods 0.000 title claims abstract description 25
- 238000000034 method Methods 0.000 claims abstract description 45
- 238000001228 spectrum Methods 0.000 claims abstract description 28
- 238000005481 NMR spectroscopy Methods 0.000 claims abstract description 17
- LIKMAJRDDDTEIG-UHFFFAOYSA-N 1-hexene Chemical compound CCCCC=C LIKMAJRDDDTEIG-UHFFFAOYSA-N 0.000 claims description 78
- KWKAKUADMBZCLK-UHFFFAOYSA-N 1-octene Chemical compound CCCCCCC=C KWKAKUADMBZCLK-UHFFFAOYSA-N 0.000 claims description 52
- VXNZUUAINFGPBY-UHFFFAOYSA-N 1-Butene Chemical compound CCC=C VXNZUUAINFGPBY-UHFFFAOYSA-N 0.000 claims description 49
- QQONPFPTGQHPMA-UHFFFAOYSA-N propylene Natural products CC=C QQONPFPTGQHPMA-UHFFFAOYSA-N 0.000 claims description 42
- ZGEGCLOFRBLKSE-UHFFFAOYSA-N methylene hexane Natural products CCCCCC=C ZGEGCLOFRBLKSE-UHFFFAOYSA-N 0.000 claims description 34
- IAQRGUVFOMOMEM-UHFFFAOYSA-N butene Natural products CC=CC IAQRGUVFOMOMEM-UHFFFAOYSA-N 0.000 claims description 28
- 229910052799 carbon Inorganic materials 0.000 claims description 27
- 125000004805 propylene group Chemical group [H]C([H])([H])C([H])([*:1])C([H])([H])[*:2] 0.000 claims description 22
- -1 polyethylene Polymers 0.000 claims description 21
- 239000004698 Polyethylene Substances 0.000 claims description 16
- 238000000926 separation method Methods 0.000 claims description 16
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 15
- 229920000573 polyethylene Polymers 0.000 claims description 15
- 238000003929 heteronuclear multiple quantum coherence Methods 0.000 claims description 14
- 229920001684 low density polyethylene Polymers 0.000 claims description 14
- 239000004702 low-density polyethylene Substances 0.000 claims description 14
- 238000005570 heteronuclear single quantum coherence Methods 0.000 claims description 12
- 125000004432 carbon atom Chemical group C* 0.000 claims description 10
- 238000004364 calculation method Methods 0.000 claims description 9
- 239000000178 monomer Substances 0.000 claims description 9
- 239000004743 Polypropylene Substances 0.000 claims description 4
- YWAKXRMUMFPDSH-UHFFFAOYSA-N pentene Chemical compound CCCC=C YWAKXRMUMFPDSH-UHFFFAOYSA-N 0.000 claims description 4
- 229920001083 polybutene Polymers 0.000 claims description 4
- 229920001155 polypropylene Polymers 0.000 claims description 4
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 description 22
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 21
- 239000005977 Ethylene Substances 0.000 description 15
- TVMXDCGIABBOFY-UHFFFAOYSA-N n-Octanol Natural products CCCCCCCC TVMXDCGIABBOFY-UHFFFAOYSA-N 0.000 description 12
- 230000010354 integration Effects 0.000 description 10
- 230000008878 coupling Effects 0.000 description 9
- 238000010168 coupling process Methods 0.000 description 9
- 238000005859 coupling reaction Methods 0.000 description 9
- 238000001644 13C nuclear magnetic resonance spectroscopy Methods 0.000 description 8
- 238000005259 measurement Methods 0.000 description 8
- 238000005160 1H NMR spectroscopy Methods 0.000 description 7
- 238000010586 diagram Methods 0.000 description 7
- 238000000655 nuclear magnetic resonance spectrum Methods 0.000 description 6
- 229940099514 low-density polyethylene Drugs 0.000 description 4
- 238000002474 experimental method Methods 0.000 description 3
- HZVOZRGWRWCICA-UHFFFAOYSA-N methanediyl Chemical compound [CH2] HZVOZRGWRWCICA-UHFFFAOYSA-N 0.000 description 3
- 229920000642 polymer Polymers 0.000 description 3
- 229920001903 high density polyethylene Polymers 0.000 description 2
- 239000004700 high-density polyethylene Substances 0.000 description 2
- 125000001570 methylene group Chemical group [H]C([H])([*:1])[*:2] 0.000 description 2
- 239000000203 mixture Substances 0.000 description 2
- 239000002904 solvent Substances 0.000 description 2
- 238000012360 testing method Methods 0.000 description 2
- FLDSMVTWEZKONL-AWEZNQCLSA-N 5,5-dimethyl-N-[(3S)-5-methyl-4-oxo-2,3-dihydro-1,5-benzoxazepin-3-yl]-1,4,7,8-tetrahydrooxepino[4,5-c]pyrazole-3-carboxamide Chemical compound CC1(CC2=C(NN=C2C(=O)N[C@@H]2C(N(C3=C(OC2)C=CC=C3)C)=O)CCO1)C FLDSMVTWEZKONL-AWEZNQCLSA-N 0.000 description 1
- OKTJSMMVPCPJKN-OUBTZVSYSA-N Carbon-13 Chemical compound [13C] OKTJSMMVPCPJKN-OUBTZVSYSA-N 0.000 description 1
- 229920000089 Cyclic olefin copolymer Polymers 0.000 description 1
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 1
- 239000012491 analyte Substances 0.000 description 1
- 238000011088 calibration curve Methods 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 230000003247 decreasing effect Effects 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- IGOCVOLAIVMTKD-UHFFFAOYSA-N hept-1-ene Chemical compound C=CCCCCC.C=CCCCCC IGOCVOLAIVMTKD-UHFFFAOYSA-N 0.000 description 1
- GXNDYZPMZKJDSS-UHFFFAOYSA-N hex-1-ene Chemical compound CCCCC=C.CCCCC=C GXNDYZPMZKJDSS-UHFFFAOYSA-N 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 238000002844 melting Methods 0.000 description 1
- 230000008018 melting Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 230000000704 physical effect Effects 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- 230000035945 sensitivity Effects 0.000 description 1
Images
Classifications
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- G—PHYSICS
- G01—MEASURING; TESTING
- G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
- G01N24/00—Investigating or analyzing materials by the use of nuclear magnetic resonance, electron paramagnetic resonance or other spin effects
- G01N24/08—Investigating or analyzing materials by the use of nuclear magnetic resonance, electron paramagnetic resonance or other spin effects by using nuclear magnetic resonance
- G01N24/087—Structure determination of a chemical compound, e.g. of a biomolecule such as a protein
-
- G—PHYSICS
- G01—MEASURING; TESTING
- G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
- G01N21/00—Investigating or analysing materials by the use of optical means, i.e. using sub-millimetre waves, infrared, visible or ultraviolet light
- G01N21/17—Systems in which incident light is modified in accordance with the properties of the material investigated
- G01N21/25—Colour; Spectral properties, i.e. comparison of effect of material on the light at two or more different wavelengths or wavelength bands
- G01N21/31—Investigating relative effect of material at wavelengths characteristic of specific elements or molecules, e.g. atomic absorption spectrometry
-
- G—PHYSICS
- G01—MEASURING; TESTING
- G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
- G01N33/00—Investigating or analysing materials by specific methods not covered by groups G01N1/00 - G01N31/00
- G01N33/44—Resins; Plastics; Rubber; Leather
-
- G—PHYSICS
- G01—MEASURING; TESTING
- G01R—MEASURING ELECTRIC VARIABLES; MEASURING MAGNETIC VARIABLES
- G01R33/00—Arrangements or instruments for measuring magnetic variables
- G01R33/20—Arrangements or instruments for measuring magnetic variables involving magnetic resonance
- G01R33/44—Arrangements or instruments for measuring magnetic variables involving magnetic resonance using nuclear magnetic resonance [NMR]
- G01R33/46—NMR spectroscopy
- G01R33/4625—Processing of acquired signals, e.g. elimination of phase errors, baseline fitting, chemometric analysis
-
- G—PHYSICS
- G01—MEASURING; TESTING
- G01R—MEASURING ELECTRIC VARIABLES; MEASURING MAGNETIC VARIABLES
- G01R33/00—Arrangements or instruments for measuring magnetic variables
- G01R33/20—Arrangements or instruments for measuring magnetic variables involving magnetic resonance
- G01R33/44—Arrangements or instruments for measuring magnetic variables involving magnetic resonance using nuclear magnetic resonance [NMR]
- G01R33/46—NMR spectroscopy
- G01R33/4633—Sequences for multi-dimensional NMR
Definitions
- the present invention relates to methods for analyzing polyolefin branches and systems using the same.
- branch ratio the concentration of the branches of polyolefins, such as polyethylene
- Korean Patent Publication No. 2007-0088724 discloses a method for analyzing the structure of a compound using H-NMR and 13C-NMR, but a method for analyzing the ratio between branches of a branch of polyolefin. Has not been studied.
- the present invention is to solve the problems of the prior art as described above,
- NMR Nuclear Magnetic Resonance
- the present invention is a) by using a NMR (Nuclear Magnetic Resonance) spectrometer and a pulse program for a sample containing a polyolefin containing a plurality of branches each peak of the plurality of branches are separated Peak separation module to obtain a spectrum; And b) a calculation module for calculating the inclusion ratio of the plurality of branches using the separated peaks.
- NMR Nuclear Magnetic Resonance
- the analysis method of the polyolefin branch according to the present invention a new analysis capable of analyzing the ratio between branches in the polyolefin, which can significantly reduce the measurement time and analyze even a low concentration of sample, compared to the conventional analysis method.
- the advantage is that it can provide a method.
- Example 2 is a diagram illustrating separation of NMR spectra of branches according to Example 1 of the present invention.
- Example 3 is a diagram illustrating separation of hexene and octene branched NMR spectra according to Example 1 of the present invention.
- Example 4 is a diagram showing an NMR spectrum of a sample according to Example 1 of the present invention.
- Example 5 is a diagram illustrating separation of NMR spectra of branches according to Example 2 of the present invention.
- Example 6 is a diagram showing an NMR spectrum of a sample according to Example 2 of the present invention.
- Example 7 is a diagram illustrating separation of NMR spectra of branches according to Example 3 of the present invention.
- Example 8 is a diagram illustrating separation using a two-dimensional spectrum of the branch according to Example 3 of the present invention.
- the method for analyzing polyolefin branches comprises a) using a NMR (Nuclear Magnetic Resonance) spectrometer and a pulse program on a sample comprising a polyolefin comprising a plurality of branches. Obtaining a spectrum in which the peaks of are each separated; And b) calculating an inclusion ratio of a plurality of branches using the separated peaks.
- NMR Nuclear Magnetic Resonance
- the method for analyzing polyolefin branches comprises: a) obtaining a spectrum using a NMR (Nuclear Magnetic Resonance) spectrometer for a sample including a polyolefin including a plurality of branches, and then obtaining Separating each of the peaks of the plurality of branches in the acquired spectrum.
- NMR Nuclear Magnetic Resonance
- the analyte to be analyzed in the present invention is a sample containing polyolefin, and the polyolefin may be any one of polyethylene, polypropylene, polybutene, and LDPE, and preferably polyethylene.
- the polyolefin may comprise a plurality of branches.
- a branch is a branch of the polyolefin which often connects another chain instead of hydrogen to the carbon in the main chain of the polyolefin.
- LDPE low density polyethylene
- HDPE high density polyethylene
- linear polyolefins are stronger than nonlinear polyolefins, but nonlinear polyolefins are cheaper and easier to form.
- a plurality of branches included in the polyolefin of the present invention includes a C1 branch up to a main chain, a propylene branch, a C2 branch up to a main chain, and a butene (butene).
- Branch, C3 branch up to main chain, pentene branch, C4 branch up to main chain, hexene branch, C5 branch up to main chain, including heptene heptene branch, C6 branch (C6 branch) can be represented as octene branch including the main chain.
- the branch of polyethylene is divided into short chain branch (SCB) and long chain branch (LCB).
- SCB short chain branch
- LCB long chain branch
- LCB is defined for C6 and higher branches, usually made by 1-octene comonomers.
- the polyolefin of the present invention may include both the SCB and LCB, preferably C1 to C6 propylene, Butene, Pentene, Hexene, Heptene ( Two or more branches of Heptene and Octene branches.
- the method for analyzing polyolefin branches allows the use of a Nuclear Magnetic Resonance (NMR) spectrometer and a pulse program for a sample containing polyolefins to obtain a spectrum in which the peaks of the branches are separated, respectively.
- the NMR spectrometer and pulse program may be selected according to the branching included in the polyolefin to be analyzed, and the NMR spectrometer is not particularly limited as long as it is a 1 H-NMR spectrometer.
- the Bruker BBO probehead (w / z-gradient) and the gradient are used.
- Bruker AVANCE III HD 700MHz NMR spectrometer 700mhz for proton and 176MHz for carbon
- unit [50G / cm] can be used.
- pulse program Homo-decoupling pulse program or proton-carbon hetero correlation Pulse programs using the 2D method can be used, specifically zghd.2 or zghd.3 included in Bruker's s / w Topspin v3.2, or 1 H- 13 C HMQC pulse program or 1 H- 13C HSQC pulse programs can be used.
- the measurement time when using a decoupling pulse program is about 2 to 5 minutes, and the measurement time when using a pulse program using the proton-carbon hetero correlation 2D method is about 10 to 30 minutes. .
- the polyolefin to be analyzed includes two or more branches of Hexene, Heptene, and Octene branches, a portion where the spectra of multiple branches overlap with each other using an NMR spectrometer and a pulse program. Homo-decoupling to separate the peaks to obtain spectra.
- the peaks of the Hexene, Heptene and Octene branches overlap each other in the obtained spectrum, that is, coupling (coupling) phenomenon
- the coupling peaks are removed as the coupling is removed, that is, homo-decoupling. Separate each one.
- the methyl peak of hexene (ocexene) and octene (octene) Denotes a triple coupling pattern by the methylene (CH2) peak at the next two positions.
- CH2 methylene
- the hexene and octene in a specific region can be observed by changing the decoupling position.
- the methyl peak of octene is represented by two separate singlets, through which decoupling simplifies the coupling pattern of methyl peak from triplet to singlet.
- the molar ratio can be calculated by dividing the methyl region of 0.96 ppm of hexene and octene by each integral ratio in 1 H-NMR.
- zghd.2 or zghd.3 included in Bruker's s / w Topspin v3.2 may be used.
- proton-carbon hetero may be obtained by using a 1 H- 13 C HMQC pulse program or a 1 H- 13 C HSQC pulse program.
- a two-dimensional spectrum is obtained by the correlation 2D method. More specifically, taking an example of a polyethylene comprising propylene (C1) and butene (C2), the obtained spectrum is doublet at a position where the methyl peaks of the branches of each of propylene (C1) and butene (C2) are approximately the same. ) And triplets, homo-decoupling does not show a single methyl peak of two singlets.
- the proton decoupling position (O2P) next to methyl, which is the decoupling target, is separated by about 0.1 ppm or more, so that the decoupling efficiency is remarkably decreased even when using the area decoupling pulse program.
- the carbon peak can be separated using the proton-carbon hetero correlation 2D method, the peaks of propylene (C1) and butene (C2) are separated based on the carbon peak. This will be described again in the following embodiment.
- the present invention also provides a NMR (Nuclear Magnetic Resonance) spectrometer for the case where the polyolefin to be analyzed includes two or more branches of a Propylene, Butene, Hexene, Heptene, and Octene branch, that is, a low density linear polymer such as LDPE.
- NMR Nuclear Magnetic Resonance
- the peaks can be separated by homo decoupling for the branches of Hexene, Heptene and Octene, and the proton-carbon hetero correlation 2D method for the branches of propylene and butene.
- the method for analyzing polyolefin branches according to the present invention comprises the steps of b) calculating the inclusion ratio of a plurality of branches using the separated peaks.
- the respective peaks are respectively integrated by homo decoupling or proton-carbon hetero correlation 2D method to obtain the integration values for the respective branches.
- the content ratio of the branches refers to the number of branches corresponding to the total number of branches included in the polyolefin, and preferably, the number of branches for each 1000 carbon atoms in the polyethylene may be calculated.
- the number of branches per 1000 carbons contained in the polyolefin may be calculated by the following Equation 1.
- the ratio of the integral value of the branch A and the integral value of the branch B is
- M is the integral of methyl (methyl) region of the basin A and branch B
- k a is the proton number, except for CH 3 in a basin
- k b is the proton number, excluding the CH 3 of b branches.
- Equation 1 the number of branches for each 1000 carbon atoms can be known, and through this, the coverage ratio of each branch is calculated.
- Equation 4 the number of 1-Hexene branches for 1000 carbon atoms can be obtained as shown in Equation 4 below.
- the separated peaks of the plurality of branches are 2D peaks. Integrate with the integral. Through the integrated value, it is possible to know the number of carbons included in each branch. Through this, the content of each branch is calculated, and this also calculates the number of branches in the same manner as in Equation 1 to Equation 4 above. Can be.
- the system for analyzing polyolefin branches comprises: a) using a NMR (Nuclear Magnetic Resonance) spectrometer and a pulse program on a sample comprising a polyolefin comprising a plurality of branches; A peak separation module for obtaining a spectrum in which the peaks of s) are separated from each other; And b) a calculation module for calculating an inclusion ratio of a plurality of branches using the separated peaks.
- NMR Nuclear Magnetic Resonance
- the polyolefin is any one of polyethylene, polypropylene, polybutene and LDPE, and the polyolefin is propylene, butene, butene, pentene, It may comprise two or more branches of Hexene, Heptene and Octene branches.
- the polyolefin comprising the plurality of branches comprises at least two branches of hexene, heptene and octene branches.
- a peak in the peak separation module, a peak may be separated by homo-decoupling portions where the spectra of a plurality of branches overlap each other using a pulse program.
- each pulse program is 1 H- 13 C HMQC pulse programs or 1 H- 13 C HSQC pulse programs are available.
- the calculation module the integration ratio of each branch is obtained as an integral value obtained by integrating the separated peaks of the plurality of branches, and then the respective molar ratios are calculated using the integration ratio to include the plurality of branches.
- the b) inclusion ratio of the plurality of branches of the calculation module means the number of each branch per 1000 carbons contained in the polyolefin.
- the number of each branch per 1000 carbons of the calculation module can calculate the number of each branch per 1000 carbons by the following equation (1).
- module refers to one unit for processing a specific function or operation, which may be implemented by hardware or software or a combination of hardware and software.
- Example 1 Separation of methyl peak of hexene and octene of EHOR
- Dissolve polyethylene (EHOR, BASELL Co., Ltd.) containing 1-Hexene and 1-Octene in TCE-d 2 solvent at 100 ° C, prepare a sample at a concentration of 10 mg / mL, and then, under 1H-NMR test conditions, Measured for minutes.
- the optimal decoupling center was found as follows using zghd.3 included in Bruker's s / w Topspin v3.2 as a Homo-decoupling pulse program.
- the decoupling center of the EHOR was determined to be 1.39 ppm.
- the decoupling center (Decoupling center) value to 1.39ppm
- PLW 24 26.4dB
- P31 5msec
- D31 0.5msec
- cpdprg2 hd
- 1-Hexene the integral ratio of 1-Octene was calculated as shown in FIG. 3.
- Example 2 Separation of methyl peak of propylene and butene of EHBPR
- Hexene (C4), heptene (C5), octene (C6) is shown by separating the methyl peak (methyl peak) as shown in Figure 7 by applying a homo-decoupling technique.
- Example 2 Compared to Example 1, heptene was added to show relatively low resolution, but the separation was sufficient to obtain the ratio of each methyl peak through integration.
- Propylene (C1) and Butene (C2) are shown by separating each methyl peak as shown in Figure 8 by applying a proton-carbon hetero correlation 2D technique.
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Abstract
Description
몰비 | 질량%비 | 1-Hexene의 분지의 개수/1000C | 1-Octene의 분지의 개수/1000C | ||||
Ethylene | 1-hexene | 1-octene | Ethylene | 1-hexene | 1-octene | ||
150.5 | 0.6 | 0.5 | 97.8 | 1.1 | 1.2 | 1.8 | 1.5 |
몰비 | 중량%비 | (1-Hexene)/1000C | (1-Butene)/1000C | (1- Propylene)/1000C | ||||||
Et | Hex | Bu | Pr | Et | Hex | Bu | Pr | |||
100.0 | 4.2 | 0.7 | 9.3 | 78.2 | 9.8 | 1.0 | 11.0 | 16.3 | 2.6 | 36.5 |
중량%비 | X/1000C | |||||||||
Et | Pr | Bu | Hex | Hept | Oc | Pr | Bu | Hex | Hept | Oc |
75.5 | 0.8 | 0.2 | 1.3 | 0.5 | 0.4 | 4.6 | 1.3 | 7.8 | 2.9 | 2.6 |
분석방법 | X/1000C | ||||
Pr | Bu | Hex | Hept | Oc | |
실시예 3 | 4.9 | 1.4 | 8.4 | 3.1 | 2.8 |
13C-NMR | 3.1 | 4.1 | 9.6 | 3.3 | 3.7 |
Claims (22)
- a) 복수의 분지(branch)를 포함하는 폴리 올레핀을 포함하는 시료에 대하여 NMR (Nuclear Magnetic Resonance) 분광기 및 펄스 프로그램을 이용하여 상기 복수의 분지(branch)의 피크가 각각 분리된 스펙트럼을 수득하는 단계; 및b) 상기 분리된 피크를 이용하여 복수의 분지의 포함 비율을 계산하는 단계를 포함하는 폴리 올레핀 분지의 분석 방법.
- 청구항 1에 있어서,상기 폴리 올레핀은 폴리 에틸렌, 폴리 프로필렌, 폴리 부텐 및 LDPE (저밀도 폴리 에틸렌) 중 어느 하나인 것을 특징으로 하는 폴리 올레핀 분지의 분석 방법.
- 청구항 1에 있어서,상기 폴리 올레핀은 프로필렌(propylene), 부텐(Butene), 펜텐(Pentene), 헥센(Hexene), 헵텐(Heptene) 및 옥텐(Octene) 분지 중 둘 이상의 분지(branch)를 포함하는 것을 특징으로 하는 폴리 올레핀 분지의 분석 방법.
- 청구항 3에 있어서,상기 폴리 올레핀은 헥센(Hexene), 헵텐(Heptene) 및 옥텐(Octene) 분지 중 둘 이상의 분지(branch)를 포함하는 것을 특징으로 하는 폴리 올레핀 분지의 분석 방법.
- 청구항 4에 있어서,상기 a) 단계에서, 펄스 프로그램을 이용하여 복수의 분지(branch)의 스펙트럼이 서로 겹치는(coupling) 부분을 호모 디커플링(Homo-decoupling)하여 피크를 각각 분리하는 것을 특징으로 하는 폴리 올레핀 분지의 분석 방법.
- 청구항 3에 있어서,상기 폴리 올레핀은 프로필렌(propylene) 및 부텐(Butene) 분지를 포함하는 것을 특징으로 하는 폴리 올레핀 분지의 분석 방법.
- 청구항 6에 있어서,상기 a) 단계에서, 펄스 프로그램을 이용하여 proton-carbon hetero correlation 2D 법 에 의한 2-차원의 스펙트럼을 수득한 후, 복수의 분지(branch)의 스펙트럼의 피크를 각각 분리하는 것을 특징으로 하는 폴리 올레핀 분지의 분석 방법.
- 청구항 7에 있어서,상기 펄스 프로그램은 1H-13C HMQC 펄스 프로그램 또는 1H-13C HSQC 펄스 프로그램인 것을 특징으로 하는 폴리 올레핀 분지의 분석 방법.
- 청구항 1에 있어서,상기 b) 단계에서, 상기 복수의 분지의 분리된 피크를 적분한 적분값으로 각각의 분지의 적분 비를 구한 후, 적분비를 이용하여 각각의 몰비를 구하여 복수의 분지의 포함 비율을 계산하는 것을 특징으로 하는 폴리 올레핀 분지의 분석 방법.
- 청구항 9에 있어서,상기 b) 단계에서, 상기 복수의 분지의 포함 비율은 폴리 올레핀에 포함된 탄소 1000개 당 각각의 분지의 개수인 것을 특징으로 하는 폴리 올레핀 분지의 분석 방법.
- 청구항 10에 있어서,상기 b) 단계에서, 하기 식 1에 의하여 탄소 1000개 당 각각의 분지의 개수를 계산하는 것을 특징으로 하는 폴리 올레핀 분지의 분석 방법.[식 1]탄소수 1000개에 대한 분지 A의 개수== [몰비(분지 A)×1000] / [몰비(polyolefin)×RPO + ∑ (몰비(분지 k)×Rk)](상기 식에서, 분지 k는 폴리 올레핀에 포함된 각각의 분지이고, lk는 분지 k모노머의 탄소수이고, lPO 는 폴리 올레핀 주쇄 모노머의 탄소수이다.)
- a) 복수의 분지(branch)를 포함하는 폴리 올레핀을 포함하는 시료에 대하여 NMR (Nuclear Magnetic Resonance) 분광기 및 펄스 프로그램을 이용하여 상기 복수의 분지(branch)의 피크가 각각 분리된 스펙트럼을 수득하는 피크 분리 모듈; 및b) 상기 분리된 피크를 이용하여 복수의 분지의 포함 비율을 계산하는 계산 모듈을 포함하는 폴리 올레핀 분지의 분석 시스템.
- 청구항 12에 있어서,상기 폴리 올레핀은 폴리 에틸렌, 폴리 프로필렌, 폴리 부텐 및 LDPE 중 어느 하나인 것을 특징으로 하는 폴리 올레핀 분지의 분석 시스템.
- 청구항 12에 있어서,상기 폴리 올레핀은 프로필렌(propylene), 부텐(Butene), 펜텐(Pentene), 헥센(Hexene), 헵텐(Heptene) 및 옥텐(Octene) 분지 중 둘 이상의 분지(branch)를 포함하는 것을 특징으로 하는 폴리 올레핀 분지의 분석 시스템.
- 청구항 14에 있어서,상기 폴리 올레핀은 헥센(Hexene), 헵텐(Heptene) 및 옥텐(Octene) 분지 중 둘 이상의 분지(branch)를 포함하는 것을 특징으로 하는 폴리 올레핀 분지의 분석 시스템.
- 청구항 15에 있어서,상기 a) 피크 분리 모듈에서, 펄스 프로그램을 이용하여 복수의 분지(branch)의 스펙트럼이 서로 겹치는(coupling) 부분을 호모 디커플링(Homo-decoupling)하여 피크를 각각 분리하는 것을 특징으로 하는 폴리 올레핀 분지의 분석 시스템.
- 청구항 14에 있어서,상기 폴리 올레핀은 프로필렌(propylene) 및 부텐(Butene) 분지를 포함하는 것을 특징으로 하는 폴리 올레핀 분지의 분석 시스템.
- 청구항 17에 있어서,상기 a) 피크 분리 모듈에서, 펄스 프로그램을 이용하여 proton-carbon hetero correlation 2D 법 에 의한 2-차원의 스펙트럼을 수득한 후, 복수의 분지(branch)의 스펙트럼의 피크를 각각 분리하는 것을 특징으로 하는 폴리 올레핀 분지의 분석 시스템.
- 청구항 18에 있어서,상기 펄스 프로그램은 1H-13C HMQC 펄스 프로그램 또는 1H-13C HSQC 펄스 프로그램인 것을 특징으로 하는 폴리 올레핀 분지의 분석 시스템.
- 청구항 17에 있어서,상기 b) 계산 모듈에서, 상기 복수의 분지의 분리된 피크를 적분한 적분값으로 각각의 분지의 적분 비를 구한 후, 적분비를 이용하여 각각의 몰비를 구하여 복수의 분지의 포함 비율을 계산하는 것을 특징으로 하는 폴리 올레핀 분지의 분석 시스템.
- 청구항 20에 있어서,상기 b) 계산 모듈에서, 상기 복수의 분지의 포함 비율은 폴리 올레핀에 포함된 탄소 1000개 당 각각의 분지의 개수인 것을 특징으로 하는 폴리 올레핀 분지의 분석 시스템.
- 청구항 21에 있어서,상기 b) 계산 모듈에서, 하기 식 1에 의하여 탄소 1000개 당 각각의 분지의 개수를 계산하는 것을 특징으로 하는 폴리 올레핀 분지의 분석 시스템.[식 1]탄소수 1000개에 대한 분지 A의 개수== [몰비(분지 A)×1000] / [몰비(polyolefin)×RPO + ∑ (몰비(분지 k)×Rk)](상기 식에서, 분지 k는 폴리 올레핀에 포함된 각각의 분지이고, lk는 분지 k모노머의 탄소수이고, lPO 는 폴리 올레핀 주쇄 모노머의 탄소수이다.)
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Publication number | Priority date | Publication date | Assignee | Title |
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KR20070088724A (ko) | 2004-12-22 | 2007-08-29 | 인스티튜트 프로블렘 히미체스코이 피지키 로시이스코이 아카데미 나우크 (아이피케이에이치에프 알에이엔) | 폴리올레핀계 합성 오일 베이스의 제조방법 |
KR20110015252A (ko) * | 2009-08-07 | 2011-02-15 | 세종대학교산학협력단 | 올레핀계 분절 공중합체의 제조 방법 |
Family Cites Families (7)
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JPS5512114A (en) | 1978-07-11 | 1980-01-28 | Yokohama Rubber Co Ltd:The | Adhesive composition |
JPS55121142A (en) * | 1979-03-13 | 1980-09-18 | Jeol Ltd | Pulse nuclear magnetic resonator |
JPH0892321A (ja) * | 1994-09-22 | 1996-04-09 | Asahi Chem Ind Co Ltd | 結晶性ポリプロピレン |
DE19648391C1 (de) * | 1996-11-22 | 1998-04-23 | Univ Leiden | Verfahren zum Verbessern der Auflösung in zweidimensionalen heteronuklearen Korrelationsspektren der Festkörper-NMR |
JP2003194750A (ja) | 2001-12-27 | 2003-07-09 | Sumitomo Chem Co Ltd | 樹脂のnmrスペクトルの測定方法 |
JP2004257938A (ja) * | 2003-02-27 | 2004-09-16 | Sumitomo Chem Co Ltd | パルスnmr法を用いたポリマーブレンドの相溶状態の評価方法 |
JP2006058271A (ja) | 2004-08-24 | 2006-03-02 | Sumitomo Chemical Co Ltd | 直鎖状ポリエチレンのコモノマー組成分布の測定方法 |
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Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
KR20070088724A (ko) | 2004-12-22 | 2007-08-29 | 인스티튜트 프로블렘 히미체스코이 피지키 로시이스코이 아카데미 나우크 (아이피케이에이치에프 알에이엔) | 폴리올레핀계 합성 오일 베이스의 제조방법 |
KR20110015252A (ko) * | 2009-08-07 | 2011-02-15 | 세종대학교산학협력단 | 올레핀계 분절 공중합체의 제조 방법 |
Non-Patent Citations (5)
Title |
---|
"Journal of Polymer Science: Polymer Physics", vol. 11, February 1973, pages: 275 - 287 |
HANSEN ET AL.: "Quantitative determination of comonomer content in ethene-a-alkene copolymers by solid state 1H-MAS NMR", INTERNATIONAL JOURNAL OF RESEARCH AND REVIEWS IN APPLIED SCIENCES, vol. 6, no. 4, 1 March 2011 (2011-03-01), pages 382 - 390, XP055276882 * |
KIM, YONG-AE: "Introduction of Solid NMR Spectroscopy and Application to Characterization of Polymeric Materials", POLYMER SCIENCE AND TECHNOLOGY, vol. 22, no. 1, 2011, pages 50 - 56, XP008180491 * |
KLIMKE ET AL.: "Optimisation and application of polyolefin branch quantification by melt-state 13C NMR spectroscopy", MACROMOLECULAR CHEMISTRY AND PHYSICS, vol. 207, no. 4, 24 February 2006 (2006-02-24), pages 382 - 395, XP055276877, DOI: 10.1002/MACP.200500422 * |
LIU ET AL., POLY(ETHYLENE-CO-1-OCTENE) CHARACTERIZATION BY HIGH-TEMPERATURE MULTIDIMENSIONAL NMR AT 750 MHZ, vol. 34, 2001, pages 4757 - 4767, XP055277193 * |
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