KR20020041155A - Method for analyzing two-dimensional molecular weight distribution of polyolefine - Google Patents
Method for analyzing two-dimensional molecular weight distribution of polyolefine Download PDFInfo
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- KR20020041155A KR20020041155A KR1020000070929A KR20000070929A KR20020041155A KR 20020041155 A KR20020041155 A KR 20020041155A KR 1020000070929 A KR1020000070929 A KR 1020000070929A KR 20000070929 A KR20000070929 A KR 20000070929A KR 20020041155 A KR20020041155 A KR 20020041155A
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- 229920000098 polyolefin Polymers 0.000 title claims abstract description 17
- 238000000034 method Methods 0.000 title claims abstract description 9
- 238000005227 gel permeation chromatography Methods 0.000 claims abstract description 6
- 238000013365 molecular weight analysis method Methods 0.000 claims description 7
- 238000000926 separation method Methods 0.000 claims description 7
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 6
- RELMFMZEBKVZJC-UHFFFAOYSA-N 1,2,3-trichlorobenzene Chemical compound ClC1=CC=CC(Cl)=C1Cl RELMFMZEBKVZJC-UHFFFAOYSA-N 0.000 claims description 4
- 239000005909 Kieselgur Substances 0.000 claims description 4
- 238000011088 calibration curve Methods 0.000 claims description 4
- 238000010828 elution Methods 0.000 claims description 3
- 238000010583 slow cooling Methods 0.000 claims description 3
- 239000013078 crystal Substances 0.000 claims description 2
- 230000014759 maintenance of location Effects 0.000 claims description 2
- 239000000741 silica gel Substances 0.000 claims description 2
- 229910002027 silica gel Inorganic materials 0.000 claims description 2
- 230000000630 rising effect Effects 0.000 claims 1
- 238000002834 transmittance Methods 0.000 claims 1
- 238000002425 crystallisation Methods 0.000 abstract description 7
- 230000008025 crystallization Effects 0.000 abstract description 7
- 239000000463 material Substances 0.000 abstract description 7
- 239000002131 composite material Substances 0.000 abstract 1
- 238000005303 weighing Methods 0.000 abstract 1
- 238000011161 development Methods 0.000 description 3
- 239000004743 Polypropylene Substances 0.000 description 2
- MVPPADPHJFYWMZ-UHFFFAOYSA-N chlorobenzene Chemical compound ClC1=CC=CC=C1 MVPPADPHJFYWMZ-UHFFFAOYSA-N 0.000 description 2
- 229920001577 copolymer Polymers 0.000 description 2
- 230000007717 exclusion Effects 0.000 description 2
- 239000000203 mixture Substances 0.000 description 2
- 229920000642 polymer Polymers 0.000 description 2
- 238000006116 polymerization reaction Methods 0.000 description 2
- -1 polypropylene Polymers 0.000 description 2
- 229920001155 polypropylene Polymers 0.000 description 2
- 238000011160 research Methods 0.000 description 2
- 239000002904 solvent Substances 0.000 description 2
- 238000001228 spectrum Methods 0.000 description 2
- PBKONEOXTCPAFI-UHFFFAOYSA-N 1,2,4-trichlorobenzene Chemical compound ClC1=CC=C(Cl)C(Cl)=C1 PBKONEOXTCPAFI-UHFFFAOYSA-N 0.000 description 1
- 230000005526 G1 to G0 transition Effects 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- 238000000149 argon plasma sintering Methods 0.000 description 1
- 239000003054 catalyst Substances 0.000 description 1
- 238000004587 chromatography analysis Methods 0.000 description 1
- 239000011248 coating agent Substances 0.000 description 1
- 238000000576 coating method Methods 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 229920001002 functional polymer Polymers 0.000 description 1
- 239000000499 gel Substances 0.000 description 1
- 230000010354 integration Effects 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- 238000000691 measurement method Methods 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- 239000011347 resin Substances 0.000 description 1
- 229920005989 resin Polymers 0.000 description 1
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- G01—MEASURING; TESTING
- G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
- G01N30/00—Investigating or analysing materials by separation into components using adsorption, absorption or similar phenomena or using ion-exchange, e.g. chromatography or field flow fractionation
- G01N30/02—Column chromatography
- G01N30/86—Signal analysis
- G01N30/8603—Signal analysis with integration or differentiation
- G01N30/8606—Integration
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- 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
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Abstract
Description
본 발명은 폴리올레핀의 이차원 분자량 분석방법에 관한 것으로, 보다 상세하게는 폴리올레핀의 곁가지 성상, 입체규칙성정도, 코모노머, 결정화크기 등에 따른 분자량 분석이 가능한 방법에 관한 것이다.The present invention relates to a two-dimensional molecular weight analysis method of a polyolefin, and more particularly, to a method capable of molecular weight analysis according to the side properties, stereoregularity, comonomer, crystallization size and the like of the polyolefin.
기존에는 폴리올레핀의 분자량을 관찰하기 위해서 시료를 140℃ 이상의 고온에서 클로로벤젠 또는 그 유도체 등의 용매에 0.1%의 농도로 용해시킨 후 서로 다른 크기로 되어있는 정지상의 믹스드컬럼을 통과시켜 시료의 크기에 따라 배제시키는 원리를 이용하여 주어진 표준시료의 보정곡선을 이용하여 측정하거나, 모세관 용융점도 및 광산란장치 등을 이용하여 관찰하는 방법을 주로 사용하여 왔다. 그러나 이러한 방법으로는 일차원적인 단일 크로마토 스팩트럼만이 관찰되어지기 때문에 부분적이거나 특정한 부분을 포함한 전체 시료의 상세한 이차원적인 분자량 분석이 불가하므로 이와 같은 문제점을 개선한 폴리올레핀의 새로운 분자량측정기술의 평가방법이 절실히 요구되고 있는 실정이다Conventionally, in order to observe the molecular weight of polyolefin, the sample is dissolved at a concentration of 0.1% in a solvent such as chlorobenzene or a derivative thereof at a high temperature of 140 ° C. or higher, and then passed through a mixed column of stationary phases having different sizes. By using the principle of exclusion according to the measurement method using a calibration curve of a given standard sample, or by using a capillary melt viscosity and light scattering apparatus, etc. have been mainly used. However, since only one-dimensional single chromatographic spectrum is observed with this method, detailed two-dimensional molecular weight analysis of the entire sample including partial or specific parts is not possible. It is a fact required
본 발명은 상기와 같은 종래 기술의 문제점을 해결하기 위한 것으로, 폴리올레핀의 곁가지 성상, 입체규칙성정도, 코모노머, 결정화크기 등에 따른 분자량 분석이 가능하도록 이차원적으로 전개하여 분자량 및 그 분포를 관찰한 전혀 새로운 폴리올레핀 분자량의 분석방법을 제공함을 목적으로 한다.The present invention is to solve the problems of the prior art as described above, to observe the molecular weight and its distribution by two-dimensionally developed to enable molecular weight analysis according to the side properties of the polyolefin, degree of stereoregularity, comonomer, crystallization size, etc. It is an object to provide an entirely new method for analyzing polyolefin molecular weight.
즉, 본 발명은 폴리올레핀을 열승온 용출분리하고, 분리된 시료 각각의 로그함수 분자량과 무게분율을 겔투과크로마토그래피를 사용하여 측정한 후, 이를 이차원 평면의 X, Y축에 각각 도시하는 것을 특징으로 하는 폴리올레핀의 이차원 분자량 분석방법에 관한 것이다.That is, the present invention is characterized in that the polyolefin is subjected to heat eluting separation, and the log function molecular weight and weight fraction of each separated sample are measured using gel permeation chromatography, and then plotted on the X and Y axes of the two-dimensional plane, respectively. It relates to a two-dimensional molecular weight analysis method of polyolefin.
도 1은 본 발명의 실시예 1에 의해 측정된 폴리프로필렌 임팩트 코폴리머의 이차원 분자량을 이차원 스팩트럼으로 나타낸 도면이다.BRIEF DESCRIPTION OF THE DRAWINGS Fig. 1 is a diagram showing two-dimensional spectra of two-dimensional molecular weight of a polypropylene impact copolymer measured by Example 1 of the present invention.
이하 본 발명을 보다 상세하게 설명하면 다음과 같다.Hereinafter, the present invention will be described in more detail.
본 발명에 따른 폴리올레핀의 2차원 분자량 분석방법은 시료를 일정한 농도로 유지해 가면서 곁가지 성상별, 입체규칙성 정도별, 코모노머 조성별, 결정화 크기별로 관찰하고자 하는 영역으로 나누어 용출분리한 다음, 겔퍼미에션 크로마토크라피에 용출분리된 시료를 일정량 주입후 일정 한 유속으로 칼럼을 통과시키면서 시료의 크기에 따라 배제시키며 머무는 시간을 측정하고, 표준검량선을 이용하여 시료의 분자량 및 그 분포를 각각 계산한 뒤 한 평면상에 일정한 간격의 주파수를 곱하여 X축은 로그함수 분자량(Log Mw)으로 Y축은 무게분율함수(dw.f/dLogMw)로 나타내어 2차원으로 전개시켜서 분자량 및 그 분포를 분석하는 것이다.Two-dimensional molecular weight analysis method of the polyolefin according to the present invention, while maintaining the sample at a constant concentration by dividing the area to be observed by each side properties, stereoregularity degree, comonomer composition, crystallization size, eluting separation, gel perme After injecting a certain amount of the sample eluted into Sean chromatography, while passing through the column at a constant flow rate, the exclusion time was measured according to the size of the sample, and the molecular weight and the distribution of the sample were calculated using a standard calibration curve. By multiplying the frequency at regular intervals on one plane, the X-axis is represented by the log function molecular weight (Log Mw) and the Y-axis is represented by the weight fraction function (dw.f / dLogMw) in two dimensions to analyze the molecular weight and its distribution.
상기 분석방법에서 시료를 그 성상별로 용출분리시키는 방법으로는 트리클로로벤젠 등의 용매에 용해시킨 고분자 용액을 규조토 또는 실리카겔 등이 충진된 컬럼에 주입하여 서냉결정화 과정을 통하여 규조토 또는 실리카겔 등으로 1∼3% 농도로 코팅시키고, 이를 이동상인 트리클로로벤젠의 유속을 5∼12ml/min, 승온속도를 300∼600℃/hr로 유지시키며 분리하고자 하는 용출온도에 다다르게 되면 적외선 센서를 이용하여 초기 투과도 기준 5∼20% 차이내에서 5ml 정도를 용출분리시키는 방법을 이용한다. 이때의 분리구간은 온도차이로 결정하게 되는데, 초기 30∼70℃ 영역에서는 초기온도보다 20℃ 차이의 간격을 두고 분리하며, 70∼90℃에서는 5∼7℃ 간격을 두고 분리하고, 90∼105℃ 영역에서는 3℃ 간격으로 분리시키며, 105∼140℃에서는 10∼20℃ 간격을 두고 분리시킴이 바람직하다. 분리된 시료는 150℃ 등온상태를 유지시켜 시료가 석출되지 않도록 한다. 곁가지 성상, 입체규칙성, 코모노머 조성, 결정화 크기 등과 같은 각 성상에 따른 시료의 분리는 상기에서 컬럼 내에 충진되는 물질의 종류, 이동상으로 사용되는 물질의 종류 및 컬럼을 통과하는 이동상의 속도 등의 조건을 변화시킴으로써 가능하다.In the above method, the sample is eluted and separated according to its properties. A polymer solution dissolved in a solvent such as trichlorobenzene is injected into a column filled with diatomaceous earth or silica gel, and then subjected to slow cooling crystallization. Coating at 3% concentration and maintaining the flow rate of trichlorobenzene as a mobile phase at 5-12 ml / min and the temperature increase rate at 300-600 ° C./hr. Elution separation of about 5ml within a 5-20% difference is used. At this time, the separation section is determined by the temperature difference.In the initial 30 ~ 70 ℃ area, it is separated by 20 ℃ difference from the initial temperature, and in 70 ~ 90 ℃, it is separated by 5 ~ 7 ℃ interval and 90 ~ 105 It is preferable to separate at intervals of 3 ° C. in the temperature range and at intervals of 10 to 20 ° C. at 105 to 140 ° C. The separated sample is maintained at 150 ° C to prevent the sample from being precipitated. The separation of the sample according to each property such as side branch property, stereoregularity, comonomer composition, crystallization size, etc. may be based on the type of material filled in the column, the type of material used as the mobile phase, and the speed of the mobile phase passing through the column. It is possible by changing the conditions.
분리된 시료들은 겔퍼미에션크로마토그라피를 이용하여 각각의 분자량과 분포를 측정하게 된다. 분자량 측정시 칼럼은 선형의 믹스드 칼럼 2개 이상을 조합하여 사용한다. 이때의 온도는 130∼170℃, 이동상의 유속은 0.5∼3ml/min으로 조절하여 컬럼 속을 통과시키며 크기별로 배제시킨 뒤 컬럼에 머무는 시간과 무게분율을 측정하고 표준시료로 보정된 검량선을 이용하여 로그함수로 된 분자량과 무게분율을 구하게 된다. 적분시 초기값과 마지막 값을 일치시켜 적분하며 얻어진 함수에 적합한 주파수를 곱하여 이차원 평면상에서 X축으로는 로그함수 분자량을, Y축으로는 그에 대응하는 무게분율을 전개시켜 나타낸다. 이때 온도상승에 따라 용출분리된 X1, X2, X3, X4 …Xn의 각각의 시료의 로그함수 분자량과 무게분율을 2차원 평면상에서 각각 도시함으로써 폴리올레핀의 이차원 분자량과 분포를 관찰할 수 있게 된다.The separated samples were subjected to gel permeation chromatography to determine their molecular weight and distribution. The column is used in combination with two or more linear mixed columns for molecular weight measurement. The temperature at this time is 130 ~ 170 ℃, the flow rate of the mobile phase is adjusted to 0.5 ~ 3ml / min, passed through the column, excluded by size, and the time and weight fraction staying in the column are measured and the calibration curve calibrated with the standard sample is used. The molecular weight and weight fraction of the logarithm function are obtained. The integral and the initial value at the time of integration are integrated and multiplied by a frequency suitable for the obtained function to develop a logarithm molecular weight on the X axis and a corresponding weight fraction on the Y axis. At this time, X1, X2, X3, X4... By showing the logarithm molecular weight and weight fraction of each sample of Xn on a two-dimensional plane, the two-dimensional molecular weight and distribution of the polyolefin can be observed.
이하 실시예를 통하여 본 발명을 보다 상세하게 설명하고자 하나, 하기 실시예는 설명의 목적을 위한 것으로 본 발명을 제한하기 위한 것이 아니다.Hereinafter, the present invention will be described in more detail with reference to the following examples. The following examples are provided for the purpose of description and are not intended to limit the present invention.
실시예 1Example 1
알파에틸렌이 블록킹된 폴리프로필렌 임팩트 코폴리머(삼성종합화학社 BJ500 Grade)를 트리클로로벤젠에 용해시키고 이를 규조토가 충진된 컬럼에 침적시켜 서냉결정하여 규조토로 코팅시켰다. 트리클로로벤젠을 이동상으로 하여 유속을8ml/min, 승온속도를 400℃/hr로 조절하면서, 40∼80℃ 구간에서는 X1을, 80∼90℃ 구간에서는 X2를, 90∼95℃ 구간에서는 X3를, 95∼100℃ 구간에서는 X4를, 100∼105℃ 구간에서는 X5를, 105∼110℃ 구간에서는 X6을, 110∼120℃ 구간에서는 X7을, 120∼135℃ 구간에서는 X8을 각각 용출분리하였다. 분리된 X1, X2, X3, X4 …X8 시료를 겔투과크로마토그래피를 사용하여 이동상의 속도를 1ml/min, 온도를 140℃로 조절하면서 칼럼을 통하여 통과시켜 무게분율과 머무는 시간을 측정하고, 표준검량선을 사용하여 무게분율과 로그함수 분자량을 계산하고 이를 2차원 평면상에 도시하여 도 1에 나타내었다.Alpha ethylene-blocked polypropylene impact copolymer (BJ500 Grade, Samsung General Chemicals Co., Ltd.) was dissolved in trichlorobenzene and deposited on a diatomaceous earth-filled column, followed by slow cooling crystals and coated with diatomaceous earth. Using trichlorobenzene as the mobile phase, the flow rate was controlled to 8 ml / min and the temperature increase rate to 400 ° C./hr, X1 in the 40-80 ° C section, X2 in the 80-90 ° C section, and X3 in the 90-95 ° C section. , Eluting and separating X4 in the section of 95 to 100 ° C, X5 in the section of 100 to 105 ° C, X6 in the section of 105 to 110 ° C, X7 in the section of 110 to 120 ° C, and X8 in the section of 120 to 135 ° C. Separated X1, X2, X3, X4... X8 sample was passed through a column using gel permeation chromatography at a rate of 1 ml / min and a temperature of 140 ° C. to measure the weight fraction and retention time, and the standard weight curve was used to determine the weight fraction and log function molecular weight. Is calculated and shown in FIG. 1 on a two-dimensional plane.
상기와 같은 본 발명에 의하면 폴리올레핀을 비롯한 결정성 고분자 제품의 입체규칙성, 결정화 크기분포, 코모노머분포 변화 따른 분자량과 분포를 이차원 구조로 상세하게 관찰이 가능하게 되므로 중합연구 및 구조물성, 가공해석이 용이해 짐은 물론 신촉매개발과 중합공정연구, 기능성 고분자 제품의 개발에 수지제품개발에 획기적인 정보를 제공할 수 있다.According to the present invention as described above it is possible to observe the molecular weight and distribution according to the stereoregularity, crystallization size distribution, comonomer distribution changes in two-dimensional structure of the crystalline polymer products, including polyolefin in detail, polymerization research, structural properties, processing analysis In addition to facilitating this, it is possible to provide breakthrough information in the development of resin products for new catalyst development, polymerization process research, and development of functional polymer products.
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