Branched Polyethylenes Fractionated in Supercritical Propane

Frederic Pelascini; Simoni Plentz-Meneghetti; Pierre J. Lutz; Val Krukonis; Kara Williams

Macromolecular Research, Vol.18, No.5, 449-457, May, 2010

DOI10.1007/s13233-010-0513-1 Export Citation

Branched Polyethylenes Fractionated in Supercritical Propane

Frederic Pelascini, Simoni Plentz-Meneghetti¹, Pierre J. Lutz^†, Val Krukonis², and Kara Williams²

University of Strasbourg — Institute Charles SADRON (UPR CNRS 22), 23 rue du Loess, F-67034, Strasbourg Cedex 2, France
¹Instituto de Química e Biotecnoligia, UFAL, Av. Lourival de Melo Mota, s/n, 57072-970, Maceio-AL, Brazil
²Phasex Corporation, USA, Lawrence

E-mail:

A series of polyethylenes (PEs), were synthesized in the presence of a palladium catalyst containing bulky diimine ligands (VERSIPOL(TM)) yielding amorphous PEs. The different PE samples were characterized by Size Exclusion Chromatography (SEC) with on line light scattering, NMR, viscometry or small angle neutron scattering (SANS) techniques to assess the molar mass, molar mass distribution (MMD), radius of gyration (or hydrodynamic radius) and degree of branching. Selected PE samples were fractionated in supercritical propane by isothermal increasing the pressure profile. In most cases, PE fractions with a sharper MMD than the original PEs were obtained. The average absolute molar masses of the resulting fractions increased steadily with increasing extraction pressure. Their dilute solution properties were compared with those of unfractionated PEs. Structural analyses confirmed the homogeneity of the degree of branching within a raw PE sample.

Keywords:supercritical fluids;branched PEs;dilute solution properties;palladium

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[2] Johnson LK, Mecking S, Brookhart M, J. Am. Chem. Soc., 118(1), 267 (1996)

[3] Mohring VM, Fink G, Anal. Chem., 97, 982 (1985)

[4] Guan Z, Cotts PM, McCord EF, McLain SJ, Science, 283, 2059 (1999)

[5] Cotts PM, Guan ZB, McCord E, McLain S, Macromolecules, 33(19), 6945 (2000)

[6] Meneghetti SP, Kress J, Lutz PJ, Macromol. Chem. Phys., 201, 1823 (2000)

[7] Lutz PJ, Meneghetti SP, Kress J, Krukonis V, Muller R, Brennan V, Polym. Mater. Sci. Eng., 84, 324 (2001)

[8] Ye ZB, Zhu SP, Macromolecules, 36(7), 2194 (2003)

[9] Ye Z, AlObaidi F, Zhu S, Macromol. Chem. Phys., 205, 897 (2004)

[10] Plentz-Meneghetti S, Kress J, Peruch F, Lapp A, Duval M, Muller R, Lutz PJ, Polymer, 46(21), 8913 (2005)

[11] Britto LD, Soares JBP, Penlidis A, Krukonis V, J. Polym. Sci. A: Polym. Chem., 97, 553 (1999)

[12] Folie B, Kelchtermans M, Shutt JR, Schonemann H, Krukonis V, J. Appl. Polym. Sci., 64(10), 2015 (1997)

[13] Meilchen MA, Kulikowski KJ, McHugh MA, Polym. Prepr. (American Chemical Society, Div. of Polym. Chem.), 31, 671 (1990).

[14] Watkins JJ, Krukonis V, Condo PD, Pradhan D, Ehrlich P, J. Supercrit. Fluids, 4, 24 (1991)

[15] Pratt JA, Lee SH, McHugh MA, J. Appl. Polym. Sci., 49, 953 (1993)

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[17] Cheng J, Fan YH, Zhan YF, Sep. Sci. Technol., 29(14), 1779 (1994)

[18] Pratt JA, McHugh MA, J. Supercrit. Fluids, 9(1), 61 (1996)

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[20] Wang J, Chen J, Yang Y, Xuebao H (Chinese Edition), 55, 689 (2004).

[21] Barbosa S, Diaz M, Mabe G, Brignole EA, Capiati N, J. Polym. Sci. B: Polym. Phys., 43(17), 2361 (2005)

[22] Kliegman JM, Barnes RK, J. Org. Chem., 35, 3140 (1970)

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[24] Brookhart M, Grant B, Volpe AFJ, Organometallics, 11, 3920 (1992)

[25] Rulke RE, Ernsting JM, Spek AL, Elsevier CJ, Van Leuven PWNM, Vrieze K, Inorg. Chem., 32, 5769 (1993)

[26] McHugh M, Krukonis V, Supercritical Fluid Extraction-Principles and Pratice, 2nd Edition, Boston, Butterworth-Heinemann, 1994.

[27] Breitling F, Lahitte JF, Peruch F, Meneghetti SP, Isel F, Lutz PJ, Polym. Prepr. (American Chemical Society, Div. of Polym. Chem.), 41, 1889 (2000).

[28] Burchard W, Adv. Polym. Sci., 143, 113 (1999)

[29] Higgins J, Benoit H, Polymers and Neutron Scattering, Lovesey SW, Mitchell EWJ, Eds., Oxford Science Publication, Oxford, 1994.

[30] Hadziioannou G, Cotts PM, Ten Brinke G, Han CC, Lutz PJ, Strazielle C, Rempp P, Kovacs AJ, Macromolecules, 20, 493 (1987)