슬라이드 1

Size: px

Start display at page:

Download "슬라이드 1"

혜옥 내
6 years ago
Views:

1 Appendix D. 다양한검출기 for Polymers A. Multiple Distributions Molar Mass Distribution (MMD) Chemical Composition Distribution (CCD) Molecular Architecture Distribution (MAD) Functional Type Distribution (FTD) Structural Distribution B. Analytical Approaches Multiple Separation Methods (2D) : LC+ GPC, Hyphenated Techniques : SEC RI/FTIR, Temperature Rising Elution Fractionation/LS, Information Rich Detections : IR, NMR, MS, Software : Statistics/mw,, ID_Homologues/Species, 기타 : GC, FFF, Ultracentrifugation, Osmometry, PSA, PDA Viscometer LSD RID MS NMR/IR Chromophore Mw Conc. Mn Function Mv, g Uni. Cal. Structure Rg, g Absolute mw Structure End group Repeat groups By-products, ID 1

2 SEC/GPC Column

3 SEC(GPC/GFC) 예비작업 1. Sample Solvent Screening Solubility : Aqueous/Organic solvents/buffers, Sample Dissolution : weight/volume 희박용액 : mw 1M 이상 /0.01%, 100K/ 약 0.1%, 10K 이하 /0.2%, Hydrodynamic Volume Temperature, Viscosity, 2. Column Screening No Interaction w/sample, Solubility : Aqueous Column, Organic Column, Aqueous/Organic Column Hydrodynamic Volume(MW) : Pore Size( Linear, 100/1000/10,000A/, ) Column Temperature, Solvent Suitability/Viscosity, 3. Standard Screening Dextran, Polyacrylic Acid, Polybutadiene, Polycarbonate, Polydimethylsiloxane, Polyethylene, Polyethylene glycol, Polyethylene oxide, Poly(methacrylic acid Sodium salt, Poly(methyl methacrylate), Polypropylene glycol, Polystyrene, Poly(2-vinylpyridine), Pullulan, Poly(styrenesulfonic acid Sodium salt), Polyvinyl alcohol, Poly(vinyl chloride), => Maker 자료 3

4 SEC(GPC/GFC) Data Acquisition/Calibration/Data Report Calibration Curve : Relative/Universal Log MW/Elution Volume Vt=Vo+Ve(Vp) SD Mz, Mv, Mw, Mn PD, MWD, Slice Report Start/End_Int/BL Overlay 4

5 SEC(GPC/GFC) 고분자구조특성, 물성 / 활성 Bio Activity? 5

6 Agilent PL-GPC220 장비명 : 고온용 GPC System 제작사 : Agilent Technologies 모델 : PL-GPC220 에이치아이코퍼레이션

7 PL-GPC220 기기구성 Oven(max.220 ); Triple Detectors, Column & Injector Solvent Module: (32 유지 ) Solvent/waste bottle Heated waste line Autosampler(max. 220 ); Dual zone heating 40 vials/ 2mL Isocratic Pump & 2-ch Degasser

8 PL-GPC 220 Plumbing Diagram Triple Detectors Heated Waste Line RI Detector S R Viscometer Purge Column Purge Valve Condensation Trap Waste Light Scattering Solvent Columns Syringe Pump purge In Out Autosampler Carousel Control Drawer HPLC Pump Degasser

9 주요사양 Component Parameters Description Pump Flow range Flow rate precision ml/min < 0.07% Oven Temperature range Temperature stability Column capacity 30 to 220 ºC < 0.05 C/h mm columns Autosampler RI Detector Light Scattering Detector Viscometer Detector Carousel Injection volume Precision* Differential refractometer Cell volume Sensitivity Wavelength Scattering Angles Sample Cell Volume Laser Molecular Weight Range Measuring principle Sensitivity Capillary Dimensions 40 2 ml vials Flushed fixed loop, μl ~ 1% Deflection 8 μl RIU/mV 890 ± 50 nm 15, μl 20mW semiconductor 685nm 10E3-10E7 g/mol (typically) Four capillary Bridge 2 x 10-5 ηsp 0.25mm ID x 610 mm

10 Wf / dlogm 분자량분포도 - 평균분자량 M n M P M w Polydispersity (Pd) = Mw/Mn M Z M Z+! Log Molecular Weight

11 Polymer Characterization 열적특성 (Tg, Tm) 분자량 & 분자량분포 기계적특성 ( 강도, 탄성율 ) 유변학적특성 ( 점도, 흐름성 )

12 GPC 분석의중요성 GPC 는고분자물질의분자량및분포도를측정할수있는유일한방법이다. GPC 로측정한분자량분포도곡선. 분자량분포도즉 Mw / Mn 비가감소하여도고분자의 strength 와 toughness 는증가한다 고분자의 Mw / Mn 이감소하면사출이나압출등의공정은점점더까다로워진다 GPC 는고분자재료의물성과생산공정을예측할수있는핵심적인 정보를제공한다. log M

13 분자량이고분자의물성미치는영향 TENSILE STRENGTH HARDNESS BRITTLENESS FLOW PROPERTIES FLEX LIFE STIFFNESS EXTRUDABILITY MOLDING PROPERTIES

$검출기특성 : 굴절률검출기 (Refractive Index Detector)$

14 검출기특성 : 굴절률검출기 (Refractive Index Detector) 이검출기는순수한이동상과고분자용액간의굴절율의차이에반응한다. 따라 굴절률검출기는용액의농도를측정한다.

$검출기특성 : 굴절률검출기 (Refractive Index Detector) Conventional GPC 에서측정시료의분자량은표준시료의크기와비교하여계산한다.$

15 검출기특성 : 굴절률검출기 (Refractive Index Detector) Conventional GPC 에서측정시료의분자량은표준시료의크기와비교하여계산한다. 칼럼은분자크기를기준으로분리가이루어진다 분자량기준이아님. 종류가다른고분자는용매에대해각각다르게작용한다. 두종류의고분자가분자량이같아도용액에서각기다른크기를갖을수있다.

16 Column calibration curve 여러개의 narrow standards 를섞어서주입하면, system calibrate 시간이단축된다. Injection 1 Injection 2 각크로마토그람 Standards 피크는정확한 RT 를얻을수있도록선택하여사용한다.

17 검출기특성 : 점도검출기 (Four Capillary Viscometer) 4 개의캐필러리브리지와 1 개의 Hold-Up Column, 2 개의압력센서를갖는 GPC 용점도계이다. Intrinsic Viscosity 분포도를측정한다.(Mark-Houwink Plot) Universal Calibration 을통해 True MW 를구한다. sp 0 0 P in 4 P 2 P Since c is close to zero: lim c 0 c sp

18 Log(Intrinsic Viscosity) 검출기특성 : 점도검출기 (Four Capillary Viscometer) Long Chain Branching Analysis Mark-Houwink Plot Mark Houwink Slope Linear PE 0.78 Light Branching 0.56 Heavy Branching (1) 0.26 Heavy Branching (2) 0.27 Linear Lightly Branched Log(Molecular Weight) Heavily Branched

19 검출기특성 : 광산란검출기 (Light Scattering) 동적광산란에서, 입사광은용액내의고분자사슬과상호작용을한다. 입사광은전자를여기하며, 그결과탄성산란의경우고분자는입사광과같은파장으로발광하나그세기는다르다.

20 검출기특성 : 광산란검출기 (Light Scattering) 용액내시료에서잉여산란된빛은분자량과농도의곱에비례한다. R (q) = C M (dn/dc) 2 P (q) K (q) Light Scattering Detector 15º static LS detector 90º static LS detector laser source beam dump focusing lens

21 GPC 용 Triple Detector 의특성 종류특성측정항목비고 Concentration detector (RI, FTIR) 상대분자량 (Conventional MW) - 수평균분자량 (Mn) - 중량평균 (Mw) - 체적평균분자량 (Mz) - 분자량분포도 (MWD) 상대분자량은표준시료 ( 예,PS) 로만든검량선에비교하여분자량을계산한다. 재현성이매우좋고측정물질의상대분자량을계산하며, 실제분자량은알수없다. Viscometer Detector Light Scattering Detector 고유점도 (IV) 측정분지도 (Long Chain Branching) 절대분자량 (Absolute MW) 분자크기 (Rg: nm) 점도검출기사용으로 M-H Plot (logmw vs logiv) 을구할수있으며, 여기에서 Branching 이계산된다. 광산란검출기는절대분자량을측정하는유일한방법이며거대분자측정에특히장점을갖는다. 분자크기도함께측정된다.

22 Polyethylene samples HDPE, LLDPE, LDPE Molecular weight distribution for polyethylenes, (HDPE-black, LLDPE-blue, LDPE-red). Mark-Houwink Plot for polyethylenes, (HDPE-black, LLDPE-blue, LDPE-red).

23 Triple Detection Data Absolute Molecular Weight High MW detection by LS detector Figure 1. Raw Data Chromatograms obtained from analysis of LDPE sample (RI, LS 15º (x5), LS 90º, ViscDP). Mp Mn Mw Mz Mz+1 Mv PD IVw Rgw 94,400 25, , ,747 1,785, ,

24 Viscometer Data Branching Analysis Molecular Weight Distribution Mark-Houwink Plot Linear reference Branching Factor Branching Number

25 시료전처리장치 PL-SP 260 고분자시료를고온에서용해및필터링한다최고온도 : 260 도 Hand Pipettor & filtering system Shaker / Agitator Thermostated Sample Blocks Temperature and Shaker Controls

FOR FILTER CARTRIDGE FILTER CARTRIDGE Colour coded to indicate porosity 4

26 PL-SP 260 전용의핸드피펫 녹인시료의불순물제거용 SUS Filter: 0.5um/2um, Glass fiber filter: 1um CLAMPING LEVER DISPLACEMENT BUTTON SLOT FOR FILTER CARTRIDGE FILTER CARTRIDGE Colour coded to indicate porosity 4 Frit/filters per cartridge Clear centre hole for cleaning and for transfering samples without filtration

27 PL-SP 260 필터링 A B C D A. Sample unfiltered and transferred by pipettor B. Sample filtered through 1 µm glass fibre membrane C. Sample filtered through 2 µm Stainless Steel Frit D. Sample filtered through 0.5 µm Stainless Steel Frit gives high resistance, and very little carbon is filtered out

한약재품질표준화연구사업단 강활 ( 羌活 ) Osterici seu Notopterygii Radix et Rhizoma 생약연구과

한약재품질표준화연구사업단 강활 ( 羌活 ) Osterici seu Notopterygii Radix et Rhizoma 생약연구과 - 2 - - 3 - KP 11 Osterici seu Notopterygii Radix et Rhizoma Ostericum koreanum Maximowicz, Notopterygium incisum Ting, Notopterygium