Chem. J. Chinese Universities ›› 2016, Vol. 37 ›› Issue (4): 761.doi: 10.7503/cjcu20150940
• Polymer Chemistry • Previous Articles Next Articles
LI Qi1,2, ZHAO Wenjie1,*(), ZHAO Ziliang2, JI Xiangling2, BO Shuqin2, LIU Yonggang2,*(
)
Received:
2015-12-09
Online:
2016-04-10
Published:
2016-03-16
Contact:
ZHAO Wenjie,LIU Yonggang
E-mail:zhaowenjie@ccut.edu.cn;yonggang@ciac.ac.cn
Supported by:
CLC Number:
TrendMD:
LI Qi, ZHAO Wenjie, ZHAO Ziliang, JI Xiangling, BO Shuqin, LIU Yonggang. Band Broadening and Chain Conformation of Polyethylene Oxide by Gel Permeation Chromatography Coupled with Multi-angle Laser Light Scattering†[J]. Chem. J. Chinese Universities, 2016, 37(4): 761.
Sample | Supplier | 10-3 | 10-3 | 10-3 | Mw/ |
---|---|---|---|---|---|
PEG3900 | P.L.c | 4.00 | 3.91 | 3.78 | 1.03 |
PEG7800 | P.L. | 8.14 | 7.78 | 7.47 | 1.04 |
PEG8000 | S.A.d | 8.0 | |||
PEG10000 | S.A. | 10.0 | | ||
PEG12000 | P.L. | 12.3 | 12.0 | 11.3 | 1.07 |
PEO15000 | P.L. | 17.1 | 14.8 | 13.9 | 1.06 |
PEG20000 | S.A. | 20.0 | | ||
PEO25000 | P.L. | 30.2 | 25.1 | 24.1 | 1.04 |
PEG35000 | S.A. | 35.0 | | ||
PEO45000 | P.L. | 47.1 | 44.5 | 42.2 | 1.06 |
PEO75000 | P.L. | 82.0 | 74.6 | 71.0 | 1.05 |
PEO114000 | P.L. | 126.6 | 114.4 | 110.2 | 1.04 |
PEO190000 | P.L. | 203.9 | 190.3 | 177.3 | 1.07 |
PEO268000 | P.L. | 234.2 | 268.4 | 255.5 | 1.05 |
PEO293000 | P.L. | 313.0 | 293.2 | 278.0 | 1.05 |
PEO448000 | P.L. | 460.0 | 448.5 | 421.1 | 1.07 |
PEO686000 | P.L. | 635.0 | 686.5 | 628.0 | 1.09 |
PEO992000 | P.L. | 989.0 | 992.0 | 886.0 | 1.12 |
PEO1358000 | P.L. | 1243.0 | 1358.0 | 1179.0 | 1.15 |
PEO1000000 | P.S.e | 1000.0 | |
Table 1 Molecular weight of PEG/PEO samples as given by the suppliers
Sample | Supplier | 10-3 | 10-3 | 10-3 | Mw/ |
---|---|---|---|---|---|
PEG3900 | P.L.c | 4.00 | 3.91 | 3.78 | 1.03 |
PEG7800 | P.L. | 8.14 | 7.78 | 7.47 | 1.04 |
PEG8000 | S.A.d | 8.0 | |||
PEG10000 | S.A. | 10.0 | | ||
PEG12000 | P.L. | 12.3 | 12.0 | 11.3 | 1.07 |
PEO15000 | P.L. | 17.1 | 14.8 | 13.9 | 1.06 |
PEG20000 | S.A. | 20.0 | | ||
PEO25000 | P.L. | 30.2 | 25.1 | 24.1 | 1.04 |
PEG35000 | S.A. | 35.0 | | ||
PEO45000 | P.L. | 47.1 | 44.5 | 42.2 | 1.06 |
PEO75000 | P.L. | 82.0 | 74.6 | 71.0 | 1.05 |
PEO114000 | P.L. | 126.6 | 114.4 | 110.2 | 1.04 |
PEO190000 | P.L. | 203.9 | 190.3 | 177.3 | 1.07 |
PEO268000 | P.L. | 234.2 | 268.4 | 255.5 | 1.05 |
PEO293000 | P.L. | 313.0 | 293.2 | 278.0 | 1.05 |
PEO448000 | P.L. | 460.0 | 448.5 | 421.1 | 1.07 |
PEO686000 | P.L. | 635.0 | 686.5 | 628.0 | 1.09 |
PEO992000 | P.L. | 989.0 | 992.0 | 886.0 | 1.12 |
PEO1358000 | P.L. | 1243.0 | 1358.0 | 1179.0 | 1.15 |
PEO1000000 | P.S.e | 1000.0 | |
Fig.1 GPC-MALLS chromatograms of PEO448000 at a flow rate of 1.0 mL/min^The lines are Rayleigh ratios Rθ from the MALLS detector of 11 angles between 34.8° and 142.6°(from top to bottom is in the order of increasing angle).
Fig.2 Weight-averaged molecular weight Mw,i(A) and Z-averaged radius of gyration Rgz,i(B) of GPC fractions as functions of elution volume for PEO448000^The solid lines are polymer concentrationof GPC fractions as calculated from the refractive index detector signals, while the dashed lines are the LS signals at scattering angle of 90°.
Fig.3 Monodisperse calibration relation lnM of the GPC columns and the experimental relation lnMw of individual PEG/PEO samples^The monodisperse calibration relation lnM-V is showed as a long straight line, which is obtained by linear fit to the cross points [Vw, M(Vw)](solid circles). The experimental relations lnMw-V of PEG3900, PEG12000, PEO45000, PEO293000, and PEO1358000 are shown as short straight lines, which are obtained by linear fits to the GPC-MALLS data(open squares), and the corresponding cross points are encircled.
Sample | GPC | GPC-LS | GPC-LS-BBC | |||||||
---|---|---|---|---|---|---|---|---|---|---|
10-3Mw | 10-3Mn | Mw/Mn | 10-3Mw | 10-3Mn | Mw/Mn | 10-3Mw | 10-3Mn | Mw/Mn | ||
PEG3900 | 0.026 | 3.73 | 3.38 | 1.10(1.07) | 3.63 | 3.48 | 1.04(1.07) | 3.67 | 3.44 | 1.07 |
PEG7800 | 0.053 | 8.02 | 7.22 | 1.11(1.05) | 7.83 | 7.64 | 1.02(1.05) | 7.89 | 7.38 | 1.07 |
PEG8000 | 0.042 | 8.49 | 7.60 | 1.12(1.07) | 8.30 | 7.98 | 1.04(1.07) | 8.34 | 7.81 | 1.07 |
PEG10000 | 0.047 | 10.8 | 9.46 | 1.14(1.08) | 10.6 | 10.1 | 1.05(1.08) | 10.5 | 9.73 | 1.08 |
PEG12000 | 0.045 | 12.5 | 10.9 | 1.15(1.10) | 12.3 | 11.5 | 1.06(1.10) | 12.3 | 11.2 | 1.10 |
PEO15000 | 0.036 | 15.3 | 13.9 | 1.10(1.06) | 16.0 | 15.4 | 1.04(1.06) | 15.1 | 14.2 | 1.06 |
PEG20000 | 0.052 | 21.3 | 19.3 | 1.11(1.05) | 20.6 | 20.2 | 1.02(1.05) | 20.9 | 19.9 | 1.05 |
PEO25000 | 0.047 | 26.2 | 23.7 | 1.10(1.05) | 25.8 | 25.1 | 1.03(1.05) | 25.6 | 24.4 | 1.05 |
PEG35000 | 0.068 | 33.9 | 28.8 | 1.17(1.10) | 32.3 | 30.7 | 1.05(1.09) | 32.9 | 30.1 | 1.09 |
PEO45000 | 0.053 | 47.6 | 42.4 | 1.12(1.06) | 46.7 | 45.3 | 1.03(1.06) | 46.5 | 43.8 | 1.06 |
PEO75000 | 0.054 | 78.5 | 71.1 | 1.10(1.04) | 77.0 | 75.6 | 1.02(1.04) | 76.6 | 73.5 | 1.04 |
PEO114000 | 0.057 | 120.1 | 107.4 | 1.12(1.05) | 119.4 | 116.8 | 1.02(1.05) | 117.2 | 111.5 | 1.05 |
PEO190000 | 0.070 | 207.8 | 173.1 | 1.20(1.12) | 205.8 | 194.1 | 1.06(1.11) | 202.1 | 182.3 | 1.11 |
PEO268000 | 0.077 | 315.7 | 268.8 | 1.17(1.09) | 306.3 | 295.7 | 1.04(1.08) | 306.1 | 284.1 | 1.08 |
PEO293000 | 0.091 | 333.5 | 263.0 | 1.27(1.16) | 319.0 | 295.0 | 1.08(1.14) | 322.0 | 281.2 | 1.15 |
PEO448000 | 0.076 | 451.7 | 331.3 | 1.36(1.26) | 430.1 | 368.4 | 1.17(1.23) | 439.7 | 353.6 | 1.24 |
PEO686000 | 0.086 | 734.7 | 572.0 | 1.28(1.18) | 690.7 | 627.0 | 1.10(1.16) | 710.6 | 608.7 | 1.17 |
PEO992000 | 0.075 | 941.7 | 636.4 | 1.48(1.37) | 897.7 | 718.8 | 1.25(1.32) | 918.2 | 684.5 | 1.34 |
PEO1358000 | 0.089 | 1365.0 | 889.4 | 1.53(1.40) | 1246.0 | 964.5 | 1.29(1.39) | 1320.0 | 949.4 | 1.39 |
PEO1000000 | (0.133) | 981.0 | 339.2 | 2.89(2.53) | 1068.0 | 474.7 | 2.25(2.53) | 931.6 | 366.4 | 2.54 |
Table 2 Spreading factor σ02 and averaged molecular weights for PEG/PEO samples before and after band broadening correction(in parenthesis)
Sample | GPC | GPC-LS | GPC-LS-BBC | |||||||
---|---|---|---|---|---|---|---|---|---|---|
10-3Mw | 10-3Mn | Mw/Mn | 10-3Mw | 10-3Mn | Mw/Mn | 10-3Mw | 10-3Mn | Mw/Mn | ||
PEG3900 | 0.026 | 3.73 | 3.38 | 1.10(1.07) | 3.63 | 3.48 | 1.04(1.07) | 3.67 | 3.44 | 1.07 |
PEG7800 | 0.053 | 8.02 | 7.22 | 1.11(1.05) | 7.83 | 7.64 | 1.02(1.05) | 7.89 | 7.38 | 1.07 |
PEG8000 | 0.042 | 8.49 | 7.60 | 1.12(1.07) | 8.30 | 7.98 | 1.04(1.07) | 8.34 | 7.81 | 1.07 |
PEG10000 | 0.047 | 10.8 | 9.46 | 1.14(1.08) | 10.6 | 10.1 | 1.05(1.08) | 10.5 | 9.73 | 1.08 |
PEG12000 | 0.045 | 12.5 | 10.9 | 1.15(1.10) | 12.3 | 11.5 | 1.06(1.10) | 12.3 | 11.2 | 1.10 |
PEO15000 | 0.036 | 15.3 | 13.9 | 1.10(1.06) | 16.0 | 15.4 | 1.04(1.06) | 15.1 | 14.2 | 1.06 |
PEG20000 | 0.052 | 21.3 | 19.3 | 1.11(1.05) | 20.6 | 20.2 | 1.02(1.05) | 20.9 | 19.9 | 1.05 |
PEO25000 | 0.047 | 26.2 | 23.7 | 1.10(1.05) | 25.8 | 25.1 | 1.03(1.05) | 25.6 | 24.4 | 1.05 |
PEG35000 | 0.068 | 33.9 | 28.8 | 1.17(1.10) | 32.3 | 30.7 | 1.05(1.09) | 32.9 | 30.1 | 1.09 |
PEO45000 | 0.053 | 47.6 | 42.4 | 1.12(1.06) | 46.7 | 45.3 | 1.03(1.06) | 46.5 | 43.8 | 1.06 |
PEO75000 | 0.054 | 78.5 | 71.1 | 1.10(1.04) | 77.0 | 75.6 | 1.02(1.04) | 76.6 | 73.5 | 1.04 |
PEO114000 | 0.057 | 120.1 | 107.4 | 1.12(1.05) | 119.4 | 116.8 | 1.02(1.05) | 117.2 | 111.5 | 1.05 |
PEO190000 | 0.070 | 207.8 | 173.1 | 1.20(1.12) | 205.8 | 194.1 | 1.06(1.11) | 202.1 | 182.3 | 1.11 |
PEO268000 | 0.077 | 315.7 | 268.8 | 1.17(1.09) | 306.3 | 295.7 | 1.04(1.08) | 306.1 | 284.1 | 1.08 |
PEO293000 | 0.091 | 333.5 | 263.0 | 1.27(1.16) | 319.0 | 295.0 | 1.08(1.14) | 322.0 | 281.2 | 1.15 |
PEO448000 | 0.076 | 451.7 | 331.3 | 1.36(1.26) | 430.1 | 368.4 | 1.17(1.23) | 439.7 | 353.6 | 1.24 |
PEO686000 | 0.086 | 734.7 | 572.0 | 1.28(1.18) | 690.7 | 627.0 | 1.10(1.16) | 710.6 | 608.7 | 1.17 |
PEO992000 | 0.075 | 941.7 | 636.4 | 1.48(1.37) | 897.7 | 718.8 | 1.25(1.32) | 918.2 | 684.5 | 1.34 |
PEO1358000 | 0.089 | 1365.0 | 889.4 | 1.53(1.40) | 1246.0 | 964.5 | 1.29(1.39) | 1320.0 | 949.4 | 1.39 |
PEO1000000 | (0.133) | 981.0 | 339.2 | 2.89(2.53) | 1068.0 | 474.7 | 2.25(2.53) | 931.6 | 366.4 | 2.54 |
Fig.4 Dependence of the spreading factor σ02 on the molecular weight Mw of PEG/PEO samples^The straight line is a linear fit of σ02 on lgMw for all samples except PEO1000000.
Fig.5 Rgz as a function of Mw for PEO in water^PEO samples with narrow molecular weight distribution(solid squares); GPC fractions of PEO1000000(open circles); Devanand and Selser[15](upward-pointing triangles); Kawagichi et al.[16](downward-pointing triangles). The straight line indicates Rg,z=0.0272Mw0.56, while the dashed and short dashed lines are Rgz=0.0215Mw0.583 established in ref.[15] and Rgz=0.0202Mw0.580 obtained in ref.[16], respectively.
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