Abstract
In recent years the concept of two-dimensional exchange NMR spectroscopy, which is well-established as a tool for structural elucidation of biopolymers in solution, has successfully been applied to solid synthetic polymers. This review introduces the methodology of 2D exchange NMR in solids and illustrates its power by a number of experimental examples. Structural aspects include the packing of amorphous and frozen liquid-crystalline polymers as well as domain sizes in polymer blends. The unique information about slow molecular dynamics provided by 2D exchange NMR is demonstrated for the chain motion of polypropylene in both its crystalline and amorphous modifications. It is shown that 2D exchange NMR is also able to detect chain diffusion between crystalline and amorphous regions. As an example of new polymeric materials, the rotational motion of the discotic units in hairy rod macromolecules is presented. It is shown that the side-group motion in glassy poly(methyl methacrylate) is a rather complex process involving a coupling to a rocking motion of the main chain. Finally it is demonstrated that 2D exchange NMR can also be applied to determine the orientational distribution function in partially ordered polymers. Here a biaxially stretched film of poly(ethylene terephthalate) provides an illustrative example.
Keywords
- Nuclear Magnetic Resonance
- Nuclear Magnetic Resonance Spectroscopy
- Magic Angle Spin
- Spin Diffusion
- Isotactic Polypropylene
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References
Kroschwitz JI (1990) Concise encyclopedia of polymer science and engineering. Wiley, New York
Brandrup J, Immergut EH (1989) Polymer handbook. Wiley, New York
Mehring M (1983) Principles of high resolution NMR in solids. Springer, Berlin Heidelberg New York
Ernst RR, Bodenhausen G, Wokaun A (1987) Principles of magnetic resonance in one and two dimensions. Clarendon Press, Oxford
(a) Frydman L, Chingas GC, Lee YK, Grandinetti PJ, Eastman MA, Barrall GA, Pines A (1992) Israel J Chem 32:161; (b) Bax A, Szeverenyi NM, Maciel GE (1983) J Magn Reson 52: 147; (c) Gan Z (1992) J Am Chem Soc 114: 8307
Blümich B, Spiess HW (1988) Angew Chem Int Ed Engl 27: 1655
Spiess HW (1991) Chem Rev 91: 1321
Spiess HW (1991) Annu Rev Mater Sei 21: 131
Chmelka BF, Schmidt-Rohr K, Spiess HW (1994) In: Tycko R (ed) NMR probes of molecular dynamics. Kluwer, Minneapolis
Spiess HW, Schmidt-Rohr K (1994) In: Richert R, Blumen A (eds) Disorder effects on relaxational processes. Springer, Berlin Heidelberg New York
Komoroski RA (ed) (1986) High resolution NMR spectroscopy of synthetic polymers in bulk. VCH, New York
Koenig JL (1992) Spectroscopy of polymers. American Chemical Society, Washington
Schmidt-Rohr K, Spiess HW (1994) Multidimensional solid-state NMR and polymers. London, Academic Press
McBrierty VJ, Packer KJ (1993) Nuclear magnetic resonance in solid polymers. Cambridge University Press, Cambridge
Abragam A (1961) The principles of nuclear magnetism. Oxford University Press, Oxford
Pake GE (1948) J Chem Phys 16: 327
Schaefer J, McKay R, Stejskal E, Dixon WT (1983) J Magn Reson 52: 123
Schaefer J, Sefcik MD, Stejskal EO, McKay RA, Dixon WT, Cais RE (1984) Macromolecules 17: 1107
Schaefer J, Stejskal EO, Perchak D, Skolnick J, Yaris R (1985) Macromolecules 18: 368
Schaefer J, Stejskal E, McKay R, Dixon WT, (1984) Macromolecules 17: 1479
Schaefer J, Garbow J, Stejskal E, Lefelar JA, (1987) Macromolecules 20: 1271
Linder M, Höhener RR, Ernst RR (1980) J Chem Phys 73: 4959
Nakai T, Ashida J, Terao T (1989) Magn Reson Chem 27: 666
Schmidt-Rohr K, Wilhelm M, Johansson A, Spiess HW (1993) Magn Reson Chem 31: 352
Veeman WS (1984) In: Progress in NMR Spectroscopy 16: pp 193–235
Schaefer J, Stejskal EO, Buchdahl R (1975) Macromolecules 8: 291
Schaefer J, Stejskal EO (1976) J Am Chem Soc 98: 1031
Jeener J, Meier BH, Bachmann P, Ernst RR (1979) J Chem Phys 71: 4546
Schmidt C, Wefing S, Blümich B, Spiess HW (1986) Chem Phys Lett 130: 84
Hagemeyer A, Brombacher L, Schmidt-Rohr K, Spiess HW (1990) Chem Phys Lett 167: 583
Wefing S, Spiess HW (1988) J Chem Phys 89: 1219
Dagani R (1992) Chemical & Engineering News 70(47): 18
Cheung TTP, Gerstein BC (1981) J Appl Phys 52: 5517
Cheung TTP (1981) Phys Rev B 23: 1404
Goldman, M, Shen L (1966) Phys Rev 144: 321
Assink RA (1978) Macromolecules 11: 1233
Caravatti P, Neuenschwander P, Ernst RR (1986) Macromolecules 19: 1889
Schmidt-Rohr K, Clauss J, Blümich B, Spiess HW (1990) Magn Reson Chem 28: S3
Edzes HT, Bernards JPC (1984) J Am Chem Soc 106: 1515
Colombo MG, Meier BH, Ernst RR (1988) Chem Phys Lett 146: 189
Robyr P, Meier BH, Ernst RR (1989) Chem Phys Lett 162: 417
Henrichs PM, Linder MJ (1984) Magn Reson 58: 458
Tycko R, Dabbagh G (1992) Israel J Chem 32: 179
Schmidt C, Blümich B, Spiess HW (1988) J Magn Reson 79: 269
(a) Spiess HW (1993) Ber Bunsenges Phys Chem 97: 1294; (b) Féaux de Lacroix S (1992) Ph.D. Thesis, Mainz-Johannis Gutenberg Universität
Caravatti P, Neuenschwander P, Ernst RR (1985) Macromolecules 18: 119
Belfiore LA, Graham H, Veda E, Wang Y (1992) Polym International 28: 81
Szeverenyi NM, Bax A, Maciel GE (1983) J Am Chem Soc 105: 2579
Caravatti P, Deli JA, Bodenhausen G, Ernst RR (1982) J Am Chem Soc 104: 5506
Cross TA, Frey MH, Opella SJ (1983) J Am Chem Soc 105: 7471
Linder M, Henrichs P, Hewitt JM, Massa DJ (1985) J Chem Phys 82: 1585
Packer KJ, Pope JM, Yeung RR, Cudby MEA (1984) J Polym Sei Polym Phys Ed 22: 589
Havens JR, VanderHart DL (1985) Macromolecules 18: 1663
Colquhoun IC, Packer K (1987) Brit Polym J 19: 151
Clauss J, Schmidt-Rohr K, Spiess HW (1993) Acta Polymer 44: 1
Schmidt-Rohr K, Clauss J, Spiess HW (1992) Macromolecules 25: 3273
Tekely P, Palmas P, Mutzenhardt P (1993) Macromolecules 26: 7363
(a) Cai WZ, Schmidt-Rohr K, Egger N, Gerharz B, Spiess HW (1993) Polymer 34: 267; (b) Spiegel S, Schmidt-Rohr K, Boeffel C, Spiess HW (1994) Polymer 34: 4566
Bailey RT, North AM, Pethrick RA (1981) Molecular motions in high polymers. Clarendon, Oxford
McCrum NG, Read BE, Williams G (1991) Anelastic and dielectric effects in polymeric solids. Dover, New York
Heijboer J (1960) Kolloid Z 171: 7
Sauer JA (1971) J Polym Sei Polym Symp 32: 69
(a) Spiess HW, Sillescu HJ (1981) Magn Reson 42: 381; (b) Spiess HW (1980) J Chem Phys 72: 6755; (c) Pschorn U, Rössler E, Sillescu H, Kaufmann S, Schaefer D, Spiess HW (1991) Macromolecules 24: 398; (d) Kaufmann S, Wefing S, Schaefer D, Spiess HW (1990) J Chem Phys 1: 197
Spiess HW (1984) Adv Polym Sei 66: 23
Axelson DE, Mandelkern L, Popli R, Mathieu PJ (1983) Polym Sei Polym Phys Ed 21: 2319
Kaji A, Yamanaki A, Murano M (1990) Polymer J 22: 893
(a) Sefcik MD, Schaefer J, May FL, Raucher D, Dub SM (1983) J Polym Sei, Polym Phys Ed. 21: 1041; (b) Sefcik MD, Schaefer J (1983) J Polym Sei Polym Phys Ed 21: 1055; (c) Sefcik MD, Schaefer J, Stejskal EO, McKay RA, Dixon WT, Cais RE (1984) Macromolecules 17: 1107
Liu Y, Roy AK, Jones AA, Inglefield PT, Ogden P (1990) Macromolecules 23: 968
Boyer RF (1968) Polym Eng Sei 8: 161
Schaefer J, Stejskal EO, Buchdahl R (1977) Macromolecules 10: 384
Shieh YT, Parker AA, Marcinko JJ, Ritchey WM (1990) Polym Prepr (Am Chem Soc Div Polym Chem) 31(1): 174
Roy AK, Jones AA, Inglefield PT (1986) Macromolecules 19: 1356
Cauley BJ, Cipriani C, Ellis K, Roy AK, Jones AA, Inglefield PT, McKinley BJ, Kambour RP (1991) Macromolecules 24: 403
Spiess HW (1983) Colloid & Polymer Sei 261, 193
Spiess HW (1983) J Mol Structure 111: 119
Inglefield PT, Amici RM, O’Gara JF, Hung C-C, Jones AA (1983) Macromolecules 16: 1552
Jones AA, O’Gara JF, Inglefield PT, Bendler JT, Yee AF, Ngai KL (1983) Macromolecules 16: 658
Hutnik M, Argon AS, Suter UW (1991) Macromolecules 24: 5970
Henrichs PM, Nicely VA, Fagerburg DR (1991) Macromolecules 24: 4033
Cholli AL, Dumais J, Engel A, Jelinski LW (1984) Macromolecules 17: 2399
Dumais JJ: Cholli AL, Jelinski LW, Hedrick JL, McGrath JE (1986) Macromolecules 19:1884
Cain EJ, Gardner KH, Gabara V, Allen SR, English AD (1991) Macromolecules 24: 3721
Pschorn U, Spiess HW, Hisgen B, Ringsdorf H (1986) Makromol Chem 187: 2711
Heijboer JJ (1968) Polym Sei Part C 16: 3755
Schaefer D, Hansen M, Blümich B, Spiess HW (1991) J Non-Cryst Solids 131–133: 111
Flocke HA (1962) Kolloid Z 180: 118
Franck A, Biederbick K (1984) Kunstoff-Kompendium, 3rd ed. Vogel, Würzburg: p 277
Hagemeyer A, Schmidt-Rohr K, Spiess HW (1989) Adv Magn Reson 13: 85
Schaefer D, Spiess HW, Suter UW, Fleming WW (1990) Macromolecules 23: 3431
Wefing S, Kaufmann S, Spiess HW (1988) J Chem Phys 89: 1234
Zemke K (1994) Ph.D. Thesis, Mainz-Johannis Gutenberg Universität
Ernst RR, Bodenhausen G, Wokaun A (1987) Principles of magnetic resonance in one and two dimensions. Clarendon Press, Oxford: Chapter 9
Zemke K, Chmelka BF, Schmidt-Rohr K, Spiess HW (1991) Macromolecules 24: 6874
Flory PJ (1969) Statistical mechanics of chain molecules. Interscience, New York
Axelson DE (1986) In: Komoroski RA (ed) High resolution NMR spectroscopy of synthetic polymers in bulk. VCH, New York: Chapter 6
Fröhlich H (1942) Proc Phys Soc Lond 54: 422
Boyd RH (1985) Polymer 26: 1123
Schmidt-Rohr K (1991) Ph.D. Thesis, Mainz-Johannis Gutenberg Universität
Wilhelm M (1992) Diploma Thesis, Mainz-Johannis Gutenberg Universität: p 65
de Jong AF, Kentgens A, Veeman WS (1984) Chem Phys Lett 109: 337
Kentgens APM, de Jong AF, de Boer E, Veeman WS (1985) Macromolecules 18: 1045
Kentgens APM, de Boer E, Veeman WS (1987) J Chem Phys 109: 6859
Spiess HW, Schmidt-Rohr K (1992) Polym Prepr (Am Chem Soc Div Polym Chem) 33(1): 68
Schmidt-Rohr K, Spiess HW (1991) Macromolecules 24: 5288
Syi J-L, Mansfield ML (1988) Polymer 29: 987
Rutledge GC, Suter UW (1992) Macromolecules 25: 1546
Hoffmann JD, Williams G, Passaglia E (1966) J Polym Sci C14: 173
Opella SJ, Waugh JS (1977) J Chem Phys 66: 4919
Tonelli AE, Schilling FC (1981) Acc Chem Res 14: 233
Earl WL, VanderHart DL (1979) Macromolecules 12: 762
Schmidt-Rohr K, Kulik AS, Beckham HW, Ohlemacher A, Pawelzik U, Boeffel C, Spiess HW (1994) Macromolecules, accepted
Kulik AS, Spiess HW (1994) Makromol Chemie 195: 1755
Heijboer J (1982) In: Pethrick RA, Richards RW (eds) Static and dynamic properties of the polymeric solid state. D Reidel Publishing Company
McCrum NG, Read BE, Williams G (1991) Anelastic and dielectric effects in polymeric solids. Dover, New York: p 246
Kulik AS, Beckham HW, Schmidt-Rohr K, Radioff D, Pawelzik U, Boeffel C, Spiess HW (1994) Macromolecules, accepted
Leisen J, Boeffel C, Dong RY, Spiess HW (1993) Liquid Crystals 14: 215
Schwiegk S, Werth M, Leisen J, Wegner G, Spiess HW (1993) Acta Polym 44: 31
Chin YH, Zhang C, Wang P, Inglefield PT, Jones AA, Kambour RP, Bendler JT, White DM (1992) Macromolecules 25: 3031
Zhang C, Wang P, Jones AA, Inglefield PT, Kambour RP (1991) Macromolecules 24: 338
Shi J-F, Dickinson LC, MacKnight WJ, Chien JCW, Zhang C, Liu Y, Chin YH, Jones AA, Inglefield PT (1993) Macromolecules 26: 1008
Samuels RJ (1974) Structured polymer properties. Wiley, New York
Ward IM (1975) Structure and properties of oriented polymers. Wiley, New York
Kakudo M, Kasai N (1972) X-ray diffraction by polymers. Elsevier, New York
(a) Bower DI, Maddams WF (1989) The vibrational spectroscopy of polymers. Cambridge University Press, Cambridge: p 292; (b) Griffiths PR, de Haseth JA (1986) Fourier transform infrared spectrometry. Wiley, New York: p 437
Bower DI (1972) J Polym Sci Polym Phys Ed 10: 2135
Rodriguez F (1989) Principles of polymer systems, 3rd ed. Hemisphere Publishing Corp, New York: p 48
Bower DI (1981) J Polym Sci Polym Phys Ed 19: 93
McBrierty VJ, Ward IM (1968) Brit J Appi Phys (J Phys D) 1: 1529
Hentschel R, Sillescu H, Spiess HW (1981) Polymer 22: 1516
Röber S, Zachmann HG (1992) Polymer 33: 2061
Spiess HW (1981) In: Ward IM (ed) Developments in oriented polymers, vol 1. Applied Science Publishers, London: pp 47–78
Hentschel R, Schlitter J, Sillescu H, Spiess HW (1978) J Chem Phys 68(1): 56
Boeffel C, Spiess HW (1988) In: McArdle CB (ed) Side chain liquid crystal polymers. Blackie, Glasgow
Boeffel C, Spiess HW (1988) Macromolecules 21: 1626
Brandolini AJ, Apple T, Dybowski C, Pembleton RG (1982) Polymer 23: 39
Brandolini AJ, Alvey MD, Dybowski C (1983) J Polym Sci Polym Phys Ed 21: 2511
Hempel G, Schneider H (1982) Pure Appi Chem 54: 635
Garroway AN, Stalker DC, Mansfield P (1975) Polymer 16: 161
Henrichs PM (1987) Macromolecules 20: 2099
Schmidt-Rohr K, Hehn M, Schaefer D, Spiess HW (1992) J Chem Phys 97(4): 2247
Chmelka BF, Schmidt-Rohr K, Spiess HW (1993) Macromolecules 26: 2282
(a) Carter CM, Alderman DW, Grant DM (1985) J Magn Reson 65: 183; (b) Hughes CD, Sherwood MH, Alderman DW, Grant DM (1993) J Magn Reson 102(A): 58
Fina LJ, Koenig JL (1986) J Polym Sci Polym Phys Ed 24: 2509
Cullity BD (1978) Elements of X-ray diffraction, 2nd ed. Addison-Wesley, Reading, Massachusetts: p 295
Wilchinsky ZW (1963) Advances in X-ray analysis, vol 6. Plenum, New York: p 231
Harbison GS, Spiess HW (1986) Chem Phys Lett 124: 128
Harbison GS, Vogt V-D, Spiess HW (1987) J Chem Phys 86: 1206
Tzou D-L, Huang T-h, Abhiraman AS, Desai P (1994) J Polym Sei Polym Phys Ed, submitted
Vogt V-D, Dettenmaier M, Spiess HW, Pietralla M (1990) Colloid Polym Sei 268: 22.
(a) Tzou D-L, Huang T-h, Abhiraman AS, Desai P (1992) Polymer 33: 426; (b) Tzou D-L, Schmidt-Rohr K, Spiess HW (1994) Polymer, accepted
Hong J, Harbison GS (1990) Colloids and Surfaces 45: 313
Féaux de Lacroix S, Titman JJ, Hagemeyer A, Spiess HW (1992) J Magn Reson 97: 435
Herzfeld J, Berger AE (1980) J Chem Phys 73: 6021
Titman JJ, Féaux de Lacroix S, Spiess HW (1993) J Chem Phys 98(5): 3816
Wilhelm M, Féaux de Lacroix S, Titman JJ, Schmidt-Rohr K, Spiess HW (1993) Acta Polymer 44: 279
Sanders JKM (1993) Chem Soc Rev 1
Kümmerlen J, Sebald A (1993) J Am Chem Soc 115, 1134
Titman J, Luz Z, Spiess HW (1992) J Am Chem Soc 114: 3756, 3765
(a) Yang Y, Hagemeyer A, Blümich B, Spiess HW (1988) Chem Phys Lett 150: 1; (b) Yang Y, Hagemeyer A, Spiess HW (1989) Macromolecules 22: 1004
Frydman L, Lee YK, Emsley L, Chingas GC, Pines A (1993) J Am Chem Soc 115: 4825
Hansen M, Blümich B, Boeffel C, Spiess HW (1992) Macromolecules 25: 5542
Günther E, Blümich B, Spiess HW (1992) Macromolecules 25: 3315
Mirau P, Heffner S, Koegler G, Bovey F (1991) Polymer International 26: 29
Bielecki A, Burum DP, Rice DM, Karasz F (1991) Macromolecules 24: 4820
Burum DP, Bielecki A (1991) J Magn Reson 94: 645
Kaszynski P, Friedli AC, Michl J (1992) J Am Chem Soc 114: 601
Tzou D-L, Spiess HW, Curran S (1994) J Polym Sei, accepted
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Beckham, H.W., Spiess, H.W. (1994). Two-Dimensional Exchange NMR Spectroscopy in Polymer Research. In: Blümich, B. (eds) Solid-State NMR III Organic Matter. NMR, vol 32. Springer, Berlin, Heidelberg. https://doi.org/10.1007/978-3-642-61223-7_4
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