GPC/SEC Greg Saunders Ben MacCreath
GPC/SEC... 3 GPC... 4 GPC... 5 Agilent PL-SP 260VS... 6 Agilent PL-GPC 220 GPC/SEC... 7 Agilent Cirrus GPC GPC... 9... 10 GPC/SEC... 11 GPC Agilent PLgel Olexis... 12... 14... 15 1... 16 2... 17... 19 GPC... 19 GPC... 19 GPC...20 GPC GPC GPC GPC...20...21 Cirrus GPC...22 (LLDPE)...24 GPC/FT-IR...25...27 2
GPC/SEC [ ] 2 (GPC (SEC) ) 1 () 10 % 1. (Mw) Mw Mw + + + + + - + + - + + + Polymer Laboratories (PL) 1976 GPC/SEC 30 PLgel PL -OH PlusPore PLgel Olexis PolarGel EasiVial PL PL GPC SEC GPC 3
GPC 1,2,4- (TCB) 1 4 GPC 135 170 ºC 4
GPC 1 ( ) GPC/SEC 1. GPC 5
( 2)TCB 2. (mg/ml) (ºC) (h) 2 3 150 1 PE PP Agilent PL-SP 260VS 2 150 4 0.25 0.5 150 4 8 PL-SP 260VS GPC 30 260 ºC ( 2 ºC) 85 230 ( 10 %) rpm PL-SP 260VS Agilent PL-SP 260VS ( ) ( 2) 2 : ( 1 µm) ( 2) ( 0.5 5 10 µm) 20 ml () PL-GPC 220 2 ml 4 ml 1 2 2. 1. 2. 1 µm 6
Agilent PL-GPC 220 GPC/SEC PL-GPC 220 PL-GPC 220 PL-GPC 220 30 220 ºC 0.05 ºC GPC PL-GPC 220 THF 140 ºC TCB 0.07 % RI (RI) GPC/SEC RI 220 ºC / ( 3) : : 2 x Agilent PLgel 10 µm MIXED-B 300 x 7.5 mm ( PL1110-6100) 1 ml/min : 200 µl : PL-GPC 220 1. Mp = 1,460,000 = 0.62 mg/ml 2. Mp = 9,860 = 1.08 mg/ml TCB CN 1 2 10 24 6 300 x 7.5 mm GPC 12 18 3. / GPC/SEC Agilent PL-GPC 220 GPC/SEC 7
GPC TREF ( ) FT-IR ( ) ELSD ( ) 4 RI PC 220 ºC PL-GPC 220 PC PC PL-GPC 220 PL-GPC 220 RI PL-GPC 220 PL-GPC 220 2 L 13 L 30 ºC ( 5) ( 4) 5. Agilent PL-GPC 220 GPC/SEC 4. PL-GPC 220 PL-GPC 220 8
2 ml 39 1 % RSD 220 ºC Agilent Cirrus GPC GPC Cirrus GPC/ Polymer Laboratories 1980 GPC Cirrus GPC GPC LC Cirrus GPC LC GPC Cirrus Agilent PL DataStream Cirrus GPC FT-IR (SCB) GPC PC GPC 1 Workbook Cirrus : Cirrus 3 MW % Cirrus QC/ 9
Cirrus GPC/ SEC ISO 9001:2000 () GPC (Mp) 3 3. Agilent EasiCal Agilent EasiVial GPC/SEC Yes Yes Yes Yes Yes Yes Yes Yes Yes 10
GPC/SEC GPC/SEC 1. GPC/SEC 2. ( ) 3. 2 ( ) PLgel Olexis PLgel Olexis ( ) PLgel 10 µm MIXED-B PLgel MIXED-A PLgel MIXED-B LS PLgel MIXED-A LS PLgel 5 µm MIXED-C PLgel 5 µm MIXED-D PLgel MIXED-A PLgel MIXED-B PLgel () PLgel 5 µm 500Å PLgel () PLgel 5 µm 100Å PLgel PLgel Olexis PLgel 20 µm 4 13 µm 3 10 µm 3 5 µm 2 (PS) (PE) PLgel Olexis 13 µm EasiVial PE 11
GPC PLgel Olexis Agilent PLgel Olexis PLgel Olexis 100,000,000 g/mol (THF ) 13 µm 220 ºC PLgel 30,000 /m 13 µm ( 6) PLgel Olexis PLgel Olexis 100,000,000 g/mol ( 7) Log M 7.2 2.70 0.350 0.950 7. PLgel Olexis X 6. PLgel Olexis 12
1 PLgel Olexis ( 8) 7 Log M 2 14 ( ) 24 8. PLgel Olexis TCB PLgel Olexis 13
PLgel PL-GPC 220 (MWD) PLgel Olexis : : : : 3 x PLgel Olexis 300 x 7.5 mm ( PL1110-6400) TCB + 0.015 % BHT 1 ml/min : 200 µl : 160 ºC : PL-GPC 220 (RI) + PLgel Olexis MWD ( 9) PLgel Olexis dw/d Log M 9. PLgel Olexis 10 PLgel Olexis dw/d Log M 1 0 3 Log M 7 1 0 PLgel Olexis ( 11) 1 dw/d Log M 3 Log M 7 10. PLgel Olexis 0 3 Log M 7 11. PLgel Olexis 14
2 GPC GPC GPC 12 3 : : : : 2 x Agilent PLgel 5 µm 100Å 300 x 7.5 mm ( PL1110-6520) TCB 1 ml/min : 145 ºC : PL-GPC 220 1. C 36 H 64 2. C 22 H 46 3. C 14 H 30 2 3 13 : : : : 2 x Agilent PLgel 3 µm 100Å 300 x 7.5 mm ( PL1110-6320) TCB : 20 µl 0.8 ml/min : 145 ºC : PL-GPC 220 1. C 36 2. C 24 3. C 20 4. C 16 5. C 12 5 3 1 2 4 0 25 13. PLgel 100Å GPC 4,000 ( ) 400,000 PLgel MIXED-D 5 µm 1 10 17 12. PLgel 15
14 PLgel 5 µm MIXED-D : : : : 2 x Agilent PLgel 5 µm MIXED-D 300 x 7.5 mm ( PL1110-6504) TCB 1 ml/min : 200 µl : 160 ºC : PL-GPC 220 1 (HDPE) PL-SP 260VS 2 mg/ml 160 ºC 2 8 PL-GPC 220 PL-GPC 220 160 ºC 80 ºC ( 16) : : : 3 x PLgel 10 µm MIXED-B 300 x 7.5 mm ( PL1110-6100) TCB + 0.0125 % BHT 1 ml/min : 200 µl : 160 ºC : PL-GPC 220 0 21 14. 5 32 15 16. HDPE 8 : 2 x PLgel 5 µm MIXED-D 300 x 7.5 mm ( PL1110-6504) : THF : 1 ml/min : 40 ºC : RI 9 22 15. PLgel 5 µm MIXED-D 16
4 TCB 1 = K x 12.1 x 10-5 = 0.707 TCB 2 = K x 40.6 x 10-5 = 0.725 4. HDPE 8 Mn Mp Mw 1 17,289 76,818 333,851 2 16,988 77,434 335,496 3 17,428 77,514 332,616 4 17,521 77,052 335,635 5 17,348 76,520 334,212 6 17,487 77,728 333,511 7 16,898 77,578 335,642 8 17,457 77,288 334,923 17,302 77,241 334,485 220 387 1,048 % 1.3 0.5 0.3 2 (HDPP) PL-SP 260VS 1.5 mg/ml 160 ºC 2 6 PL-GPC 220 PL-GPC 220 160 ºC 80 ºC 18 HDPP 6 7 32 18. HDPP 6 17 HDPE 8 PLgel 10 µm MIXED-B PL-GPC 220 dw/d Log M 2 Log M 7 17. HDPE 8 17
5 TCB 1 = K x 12.1 x 10-5 = 0.707 TCB 2 = K x 19.0 x 10-5 = 0.725 5. HDPP 6 Mp Mn Mw 1 127,132 65,086 185,795 2 131,893 65,089 185,236 3 128,673 66,802 186,202 4 132,062 67,417 188,048 5 131,625 69,320 188,679 6 130,227 69,677 186,188 130,202 67,232 186,691 1,693 1,815 1,239 % 0.13 2.70 0.66 : : : 3 x PLgel 10 µm MIXED-B 300 x 7.5 mm ( PL1110-6100) TCB + 0.0125 BHT 1 ml/min : 200 µl : 160 ºC : PL-GPC 220 19 HDPP 6 PLgel 10 µm MIXED-B PL-GPC 220 dw/d Log M 3 Log M 7 19. HDPP 6 1 H. Coll and D. K. Gilding (1970) Universal calibration in GPC: a study of polystyrene, poly- -methylstyrene, and polypropylene. Journal of Polymer Science Part A-2: Polymer Physics, 8, 89-103. 2 T. G. Scholte, N. L. J. Meijerink, H. M. Schoffeleers and A.M.G. Brands (1984) Mark-Houwink equation and GPC calibration for linear short chain branched polyolefins, including polypropylene and ethylene-propylene copolymers. Journal of Applied Polymer Science, 29, 3763. 18
GPC GPC GPC PL-GPC 220 GPC GPC 1 2 ( x ) 1 : x 2 : Log (MW x ) VS. log ( ) VS. PLgel Olexis ( 20) 9 Log (Mw x IV) 0 14 24 ( ) GPC PL-GPC 220 GPC GPC 3 3 : R = CM (dn/dc) 2 P K R CM x dn/dc P K 15º 90º 2 10 nm 20. PLgel Olexis GPC 19
GPC PL-GPC 220 GPC 15º 90º 2 10 nm GPC GPC GPC GPC GPC GPC GPC GPC GPC GPC GPC GPC GPC 20
GPC LDPE 1930 ( 2 %) GPC LDPE HDPE LDPE HDPE LDPE HDPE LLDPE LLDPE LDPE GPC LLDPE 24 GPC-FT-IR GPC Rg IV ( ) ( ) ( ) 4 (MW ) (MW ) 4 : g = Rg Rg g = g = g (1/ ) IV IV MW MW () = 0.5 1.5 0.75 g ( g ( 0.75) ) ( 1000 ) 5 3 5 : g = [(1 + B n /7) 1/2 + 4B n /9 ] -1/2 B n = 1000 21
1000 ( ) 22 3 0.7 PL-GPC 220 LDPE HDPE LLDPE Log IV 0 : : : 3 x PLgel Olexis 300 x 7.5 mm ( PL1110-6400) TCB + 0.015 % BHT 1.0 ml/min : 200 µl : 160 ºC : PL-GPC 220 (RI) + + Cirrus GPC 21 3 1.0 dw/d Log M 0.0 1 Log M 9 21. 3 (HDPE LLDPE LDPE ) -1.4 3.5 Log M 6.5 22. 3 (HDPE LLDPE LDPE ) HDPE LLDPE K () () GPC LDPE HDPE LLDPE LDPE Cirrus GPC ( 6 ) 22
PL-GPC 220 GPC/3 (HDPE 1 LDPE 2 ) 2 1 SRM 1475 Cirrus GPC 23 3 24 3 2 6 g ( ) : : : : 3 x PLgel Olexis 300 x 7.5 mm ( PL1110-6400) TCB + 0.015 % BHT 1.0 ml/min : 200 µl : 160 ºC : dw/d Log M 1.0 0.0 PL-GPC 220 (RI) + 23. 3 ( ) 1.5 2 Log M 8 6 : g = IV IV 1/ Log IV 0-1.5 2 Log M 8 24. 3 23
1 g ( ) 2 g g 1000 Cirrus GPC 25 26 g g 25. 3 g ( ) 1.0 0.0 4.0 Log Mw 6.5 120 2 1 2 (LLDPE) (FT-IR) FT-IR FT-IR FT-IR 1 GPC PL-HTGPC-FT-IR PL-GPC 220 FT-IR 0.5 ºC 175 ºC FT-IR MCT () 0 4.0 Log Mw 7.0 26. 3 () 24
GPC/FT-IR ( 135 ºC ) GPC (TCB) TCB >C-H 3,500 2,700 cm -1 FT-IR GPC CH >C-H >CH 2 CH 3 CH 3 >CH 2 (SCB) 1 SCB 6 GPC SCB SCB CH 3 >CH 2 SCB SCB FT-IR GPC ( ) SCB GPC/FT-IR Agilent FT-IR PL-GPC 220 : : : 200 µl : 2 x PLgel Olexis 300 x 7.5 mm ( PL1110-6400) (BHT ) 1.0 ml/min : 160 ºC : Agilent Resolutions Pro 8.0 cm -1 11 16 3,500 2,700 cm -1 : Agilent PL-HTGPC-FT-IR MCT Agilent FT-IR Cirrus GPC-FT-IR SCB SCB FT- IR 27 FT-IR 0.6 dw/d Log M 0 0 1.5 Log Mw 6 27. 0.3 CH 3 /CH 2 1 P.J. DesLauriers, D.C. Rohlfing and E.T. Shieh (2002) Quantifying short chain branching microstructures in ethylene-1-olephin copolymers using size exclusion chromatography and Fourier transform infrared spectroscopy (SEC-FTIR). Polymer, 43, 159-170. 25
Agilent PLgel 3 µm 100Å 300 x 7.5 mm Agilent PLgel 5 µm 100Å 300 x 7.5 mm Agilent PLgel 5 µm MIXED-D 300 x 7.5 mm Agilent PLgel 10 µm MIXED-B 300 x 7.5 mm PLgel 10 µm MIXED-B LS 300 x 7.5 mm PLgel 20 µm MIXED-A 300 x 7.5 mm PLgel 20 µm MIXED-A LS 300 x 7.5 mm Agilent PLgel Olexis 300 x 7.5 mm Agilent PS-H EasiVial 2 ml Agilent PS-M EasiVial 2 ml Agilent E-M-10 10 x 0.2 g Agilent E-MW-10 10 x 0.1 g Agilent E-SCB 10 x 0.1 g PL1110-6320 PL1110-6520 PL1110-6504 PL1110-6100 PL1110-6100LS* PL1110-6200 PL1110-6200LS* PL1110-6400 PL2010-0201 PL2010-0301 PL2650-0101 PL2650-0102 PL2650-0103 Agilent PL-SP 260VS ** Agilent PL-GPC 220 GPC/SEC Agilent PL-HTGPC-FT-IR** Agilent PL-BV 400HT Agilent PL-HTLS 15/90 Agilent ** Agilent Cirrus GPC Agilent Cirrus GPC Agilent GPC-FT-IR SCB * PL0820-0000 PL0810-3050 PL0640-1200 PL0570-2020 PL0570-2000 PL0570-2300 ** 26
GPC FT-IR 600-IR 600-IR (ATR) Agilent ATR Agilent 600-IR NMR Agilent NMR 1D 2D NMR 2D NMR Agilent 400-MR DirectDrive DirectDigital 400-MR Agilent 600-IR 27
www.agilent.com/chem/jp 0120-477-111 Agilent Technologies, Inc. 2011 Printed in Japan January 28, 2011 5990-6971JAJP