nach oben

Erschienen in:

2011 | OriginalPaper | Buchkapitel

Theory of Random Copolymer Fractionation in Columns

verfasst von : Sabine Enders

Erschienen in: Polymer Thermodynamics

Verlag: Springer Berlin Heidelberg

Einloggen

Aktivieren Sie unsere intelligente Suche, um passende Fachinhalte oder Patente zu finden.

search-config

KI-gestützte Suche

Aus

Abstract

Random copolymers show polydispersity both with respect to molecular weight and with respect to chemical composition, where the physical and chemical properties depend on both polydispersities. For special applications, the two-dimensional distribution function must adjusted to the application purpose. The adjustment can be achieved by polymer fractionation. From the thermodynamic point of view, the distribution function can be adjusted by the successive establishment of liquid–liquid equilibria (LLE) for suitable solutions of the polymer to be fractionated. The fractionation column is divided into theoretical stages. Assuming an LLE on each theoretical stage, the polymer fractionation can be modeled using phase equilibrium thermodynamics. As examples, simulations of stepwise fractionation in one direction, cross-fractionation in two directions, and two different column fractionations (Baker–Williams fractionation and continuous polymer fractionation) have been investigated. The simulation delivers the distribution according the molecular weight and chemical composition in every obtained fraction, depending on the operative properties, and is able to optimize the fractionation effectively.

Sie haben noch keine Lizenz? Dann Informieren Sie sich jetzt über unsere Produkte:

Springer Professional "Wirtschaft+Technik"

Online-Abonnement

Mit Springer Professional "Wirtschaft+Technik" erhalten Sie Zugriff auf:

über 102.000 Bücher
über 537 Zeitschriften

aus folgenden Fachgebieten:

Automobil + Motoren
Bauwesen + Immobilien
Business IT + Informatik
Elektrotechnik + Elektronik
Energie + Nachhaltigkeit
Finance + Banking
Management + Führung
Marketing + Vertrieb
Maschinenbau + Werkstoffe
Versicherung + Risiko

Jetzt Wissensvorsprung sichern!

Jetzt informieren

Springer Professional "Technik"

Online-Abonnement

Mit Springer Professional "Technik" erhalten Sie Zugriff auf:

über 67.000 Bücher
über 390 Zeitschriften

aus folgenden Fachgebieten:

Automobil + Motoren
Bauwesen + Immobilien
Business IT + Informatik
Elektrotechnik + Elektronik
Energie + Nachhaltigkeit
Maschinenbau + Werkstoffe

Jetzt Wissensvorsprung sichern!

Jetzt informieren

Vorheriges Kapitel Interfacial Tension in Binary Polymer Blends and the Effects of Copolymers as Emulsifying Agents

Nächstes Kapitel Computer Simulations and Coarse-Grained Molecular Models Predicting the Equation of State of Polymer Solutions

Rätzsch MT, Kehlen H (1989) Continuous thermodynamics of polymer systems. Prog Polym Sci 14:1–46CrossRef

Wohlfarth C, Rätzsch MT (1990) Continuous thermodynamics of copolymer systems. Adv Polym Sci 98:49–114

Rätzsch MT, Kehlen H, Browarzik D (1985) Liquid–liquid equilibrium of polydisperse copolymer solutions. Multivariate distribution functions in continuous thermodynamics. J Macromol Sci Chem A 22:1679–1680CrossRef

Rätzsch MT, Browarzik D, Kehlen H (1989) Refined continuous thermodynamic treatment for the liquid–liquid equilibrium of copolymer solutions. J Macromol Sci Chem A 26:903–920CrossRef

Rätzsch MT, Kehlen H, Browarzik D, Schirutschke M (1986) Cloud-point curves for the system copoly(ethylene-vinyl acetate) plus methylacetate. Measurement and prediction by continuous thermodynamics. J Macromol Sci Chem A 23:1349–1361CrossRef

Rätzsch MT, Browarzik D, Kehlen H (1990) Liquid–liquid equilibrium of copolymer solutions with broad and asymmetric chemical distribution. J Macromol Sci Chem A 27:809–830CrossRef

Browarzik C, Browarzik D, Kehlen H (2001) Phase-equilibrium calculation for solutions of poly(ethylene-co-vinyl acetate) copolymers in supercritical ethylene using a cubic equation of state. J Supercrit Fluids 20:73–88CrossRef

Browarzik D, Rätzsch MT, Wohlfarth C (2003) High pressure phase equilibria in the system ethylene + vinylacetate + (ethylene vinylacetate) copolymer treated by continuous thermodynamics. Acta Polymerica 40:457–462CrossRef

Koningsveld R (1970) Preparative and analytical aspects of polymer fractionation. Adv Polym Sci 7:1–69CrossRef

10.

Tung LH (ed) (1977) Fractionation of synthetic polymers. Marcel Dekker, New York

11.

Koningveld R, Stockmayer WH, Nies E (2001) Polymer phase diagrams. Oxford University Press, Oxford

12.

Provder T, Whited M, Huddleston D, Kuo CY (1997) Characterization of compositional heterogeneity in copolymers and coatings systems by GPC/FTIR. Prog Org Coating 32:155–165CrossRef

13.

Pratt JA, McHugh MA (1996) Supercritical-fluid fractionation of poly(ethylene-co-acrylic acid). J Supercrit Fluids 9:61–66CrossRef

14.

Scholsky KM, O’Connor KM, Weiss CS, Krukonis VJ (1987) Characterization of copolymers fractionated using supercritical fluids. J Appl Polym Sci 33:2925–2934CrossRef

15.

Pratt JA, Lee SH, McHugh MA (1993) Supercritical fluid fractionation of copolymers based on chemical composition and molecular weight. J Appl Polym Sci 49:953–966CrossRef

16.

Glöckner G, Kroschwitz H, Meissner C (1982) HP precipitation chromatography of styrene–acrylonitrile copolymers. Acta Polymerica 33:614–616CrossRef

17.

Glöckner G, van den Berg JHM, Meijerink NLJ, Scholte TG, Koningsveld R (1984) Size exclusion and high-performance precipitation liquid chromatography of styrene–acrylonitrile copolymers. Macromolecules 17:962–967CrossRef

18.

Glöckner G, van den Berg JHM (1987) Copolymer fractionation by gradient high-performance liquid chromatography. J Chromatogr 384:135–144CrossRef

19.

Glöckner G, Ilchmann D (1984) Hochdruck-Fällungschromatographie von α-Methylstyren/Acrylnitril-Copolymeren. Acta Polymerica 35:680–683CrossRef

20.

Mori S, Uno Y (1987) Operational variables for the separation of styrene–methyl methacrylate copolymers according to chemical composition by liquid adsorption chromatography. Anal Chem 59:90–94CrossRef

21.

Teramachi S, Hasegawa A, Shima Y, Akatsuja M, Nakajima M (1979) Separation of styrene–methyl acrylate copolymer according to chemical composition, using high-speed liquid chromatography. Macromolecules 12:992–996CrossRef

22.

Glöckner G (1987) Quantitative aspects of gradient HPLC of copolymers from styrene and ethyl methacrylate. Chromatographia 23:517–524CrossRef

23.

Glöckner G, Stickler M, Wunderlich W (1987) Investigation of copolymers of styrene and ethyl methacrylate by size exclusion chromatography and gradient HPLC. Fresenius Z Anal Chem 328:67–81CrossRef

24.

Glöckner G, Barth HG (1990) Use of high-performance liquid chromatography for the characterization of synthetic copolymers. J Chromatogr 499:645–654CrossRef

25.

Glöckner G, Stickler M, Wunderlich W (1989) Separation of stat-copoly(styrene/2-methoxyethyl methacrylate) samples according to composition by gradient high-performance liquid chromatography. J Appl Polym Sci 37:3147–3161CrossRef

26.

Xu Z, Yuang P, Zhong J, Jiang E, Wu M, Fetters LJ (1989) The characterization of a poly(ethylene terephthalate)–poly(tetramethylene ether) multiblock copolymer via cross fractionation and size exclusion chromatography. J Appl Polym Sci 37:3195–3204CrossRef

27.

Stejskal J, Strakova D, Kratochvil P, Smith SD, McGrath JE (1989) Chemical composition distribution of a graft copolymer prepared from macromonomer: fractionation in demixing solvents. Macromolecules 22:861–865CrossRef

28.

Dong Q, Fan ZQ, Fu ZS, Xu JT (2007) Fractionation and characterization of an ethylene–propylene copolymer produced with a MgCl₂/SiO₂/TiCl₄ diester type Ziegler–Natta catalyst. J Appl Polym Sci 107:1301–1309CrossRef

29.

Podešva J, Stejskal J, Prochăzka O, Špaček P, Enders S (1993) Fractionation of a statistical copolymer in a demixing-solvent system: theory and experiment. J Appl Polym Sci 48:1127–1135CrossRef

30.

Kakugo M, Miyatake T, Mizunuma K (1991) Chemical composition distribution of ethylene-1-hexane copolymer prepared with TiCl₃–Al(C₂H₅)₂Cl catalyst. Macromolecules 24:1469–1472CrossRef

31.

van Asten AC, van Dam RJ, Kok WT, Tijssen R, Poppe H (1995) Determination of the compositional heterogeneity by polydisperse polymer samples by the coupling of size-exclusion chromatography and thermal field-flow fractionation. J Chromatogr A 703:245–263CrossRef

32.

Hwang SW, Kim E, Shin C, Kim JH, Ryu DY, Park S, Chang T (2007) Unusual sensitivity of closed-loop phase behavior to chain size and distribution. Macromolecules 40:8066–8070CrossRef

33.

Ogawa T (1990) Fractionation and characterization of polyacetal copolymers by column elution method. J Appl Polym Sci 40:1519–1527CrossRef

34.

Zhang M, Lynch DT, Wanke SE (2000) Characterization of commercial linear low-density polyethylene by TREF-DSC and TREF-SEC cross fractionation. J Appl Polym Sci 75:960–967CrossRef

35.

Kong J, Fab X, Xie Y, Qiao W (2004) Study on molecular chain heterogeneity of linear low-density polyethylene by cross-fractionation of temperature rising elution fractionation and successive self-nucleation/annealing thermal fractionation. J Appl Polym Sci 94:1710–1718CrossRef

36.

van den Glöckner G, Berg JHM, Meijerink NLJ, Scholte TG, Koningsveld R (1984) Two-dimensional analysis of copolymers by size-exclusion chromatography and gradient-elution reversed-phase precipitation chromatography. J Chromatogr 317:615–624CrossRef

37.

Cho KH, Park YH, Jeon SJ, Kim WS, Lee DW (1997) Retention behavior of copolymers in thermal field-flow fractionation and gel permeation chromatography. J Liq Chromatogr Relat Technol 20:2741–2756CrossRef

38.

Nakano S, Goto Y (1981) Development of automatic cross fractionation: combination of crystallizability fractionation and molecular weight fractionation. J Appl Polym Sci 26:4217–4231CrossRef

39.

Springer H, Hengse A, Hinrichsen G (1990) Fractionation and characterization of a 1-butene linear low density polyethylene. J Appl Polym Sci 40:2173–2188CrossRef

40.

Baker CA, Williams RJP (1956) A new chromatographic procedure and its application to high polymers. J Chem Soc:2352–2362

41.

Barker PE, Hatt BW, Williams AN (1978) Fractionation of a polymer using a preparative-scale continuous chromatograph. Chromatographia 11:487–493CrossRef

42.

Gerrissen H, Roos J, Wolf BA (1985) Continuous fractionation and solution properties of PVC. 1. Continuous fractionation, characterization. Makromol Chemie 186:735–751CrossRef

43.

Kalal J, Marousek V, Svec F (1974) Fraktionierung von Vinylchlorid/Vinylacetat Copolymeren. Angew Makromol Chem 38:45–55CrossRef

44.

Mencer HJ, Kunst B (1978) A modified column method of polymer fractionation. Colloid Polym Sci 256:758–760

45.

Wu AH, Prausnitz JM (1990) Fractionation of polydisperse polymer using an antisolvent. Application of continuous thermodynamics. J Appl Polym Sci 39:629–637CrossRef

46.

Rätzsch MT, Kehlen H, Tschersich L (1989) Application of continuous thermodynamics to polymer fractionation. J Macromol Sci Chem A26:921–935CrossRef

47.

Rätzsch MT, Enders S, Tschersich L, Kehlen H (1991) Polymer fractionation calculations using refined free energy relations. J Macromol Sci Chem A28:31–46CrossRef

48.

Rätzsch MT, Kehlen H, Tschersich L, Wolf BA (1991) Application of continuous thermodynamics to polymer fractionation. Pure Appl Chem 63:1511–1518CrossRef

49.

Weinmann K, Wolf BA, Rätzsch MT, Tschersich L (1992) Theory-based improvements of the CPF (continuous polymer fractionation) demonstrated for poly(carbonate). J Appl Polym Sci 45:1265–1279CrossRef

50.

Rätzsch MT, Tschersich L, Kehlen H (1990) Simulation of Baker–Williams fractionation by continuous thermodynamics. J Macromol Sci A27:999–1013

51.

Folie B (1996) Single-stage fractionation of poly(ethylene-co-vinyl acetate) in supercritical ethylene with SAFT. AIChE J 42:3466–3476CrossRef

52.

Litmanovich AD, Shtern VY (1967) On the cross-fractionation of copolymers. J Polym Sci C 16:1375–1382

53.

Ogawa T, Inaba T (1974) Analysis of the fractionation of ethylene–propylene copolymerization products. J Appl Polym Sci 18:3345–3363CrossRef

54.

Flory PJ (1953) Principles of polymer chemistry. Cornell University Press, Ithaca

55.

Barker JA (1952) Cooperative orientation effects in solutions. J Chem Phys 20:1526–1531CrossRef

56.

Stockmayer WH (1945) Distribution of chain lengths and compositions in copolymers. J Chem Phys 13:199–207CrossRef

57.

Becker F, Buback M, Latz H, Sadowski G, Tumakaka F (2004) Cloud-point curves of ethylene-(meth)acrylate copolymers in fluid ethene up to high pressures and temperature – experiment study and PC-SAFT modeling. Fluid Phase Equilib 215:263–282CrossRef

58.

Kleiner M, Tumakaka F, Sadowski G, Latz H, Buback M (2006) Phase equilibria in polydisperse and associating copolymer solutions: poly(ethylene-co-(meth)acrylic acid)–monomer mixture. Fluid Phase Equilib 241:113–123CrossRef

59.

Gross J, Spuhl O, Tumakaka F, Sadowski G (2003) Modeling copolymer systems using the perturbed-chain SAFT equation of state. Ind Eng Chem Res 42:1266–1274CrossRef

60.

Wohlfarth C, Rätzsch MT (1987) Kontinuierliche Thermodynamik des Entmischungsgleichgewichtes: Berechnung der Schattenkurve im System Ethylen + Vinylacetat + (Ethylen-Vinylazetat)-Copolymer. Acta Polymerica 38:156–158CrossRef

61.

Browarzik D, Kehlen H (1996) Stability of polydisperse fluid mixtures. Fluid Phase Equilib 123:17–28CrossRef

62.

Teramachi S, Tomioka H, Sotokawa M (1972) Phase-separation phenomena of copolymer solutions and fractionation of copolymers by chemical composition. J Macromol Sci A6:97–107

63.

Teramachi S, Nagasawa M (1968) The fractionation of copolymers by chemical composition. J Macromol Sci A2:1169–1179

64.

Rosenthal AJ, White BB (1952) Fractionation of cellulose acetate. Ind Eng Chem 44:2693–2696CrossRef

65.

Teramachi S, Kato Y (1971) Study of the distribution of chemical composition in low-conversion copolymer by cross-fractionation. Macromolecules 4:54–56CrossRef

66.

Teramachi S, Hasegawa A, Hasegawa S, Ishibe T (1981) Determination of chemical composition distribution in a high-conversion copolymer of styrene and methyl acrylate by cross fractionation. Polym J 4:319–323CrossRef

67.

Teramachi S, Hasegawa A, Yoshida S (1982) Comparison of cross fractionation and TLC methods in the determination of the compositional distribution of statistical copolymer. Poly J 14:161–164CrossRef

68.

Spychaj T (1987) Solvent/non-solvent solubility and polarity parameters in fractional separation of oligomers 2. Epoxy resins. Angew Makromol Chem 149:127–138CrossRef

69.

Spychaj T, Hamielec AE (1988) Solvent/non-solvent solubility and polarity parameters in fractional separation of oligomers 2. Styrene–acrylic acid copolymer. Angew Makromol Chem 157:137–151CrossRef

70.

Stejskal J, Kratochvil P (1978) Fractionation of a model random copolymer in various solvent systems. Macromolecules 11:1097–1103CrossRef

71.

Stejskal J, Kratochvil P, Strakova D (1981) Study of the statistical chemical heterogeneity of copolymers by cross fractionation. Macromolecules 14:150–154CrossRef

72.

Bodor G, Dalcolmo HJ, Schröter O (1989) Structural and property correlation of ethylene-α-olefin copolymers. Colloid Polym Sci 267:480–493CrossRef

73.

Arranz F, Sanchez-Chaves M (1985) Chemical heterogeneity of a partially modified dextran with ethyl carbonate groups. Angew Makromol Chem 135:139–149CrossRef

74.

Teramachi S, Fukao T (1974) Cross fractionation of styrene–acrylonitrile copolymer. Polym J 6:532–536CrossRef

75.

Teramachi S, Kato Y (1970) Cross fractionation of styrene–butadiene copolymer. J Macromol Sci A4:1785–1796

76.

Smith WV (1970) Precipitation chromatography theory. J Polym Sci A 2(8):207–224

77.

Mac Lean DL, White JL (1972) The precipitation chromatographic column: theory, critique and method of design. Polymer 13:124–132CrossRef

78.

Geerissen H, Roos J, Wolf BA (1985) Continuous fractionation and solution properties of PVC, 1. Continuous fractionation, characterization. Makromol Chem 186:735–751CrossRef

79.

Geerissen H, Schützeichel P, Wolf BA (1990) Large scale fractionation of polyethylene by means of the continuous polymer fractionation (CPF) method. Makromol Chem 191:659–670CrossRef

80.

Gosch CI, Haase T, Wolf BA, Kulicke WM (2002) Molar mass distribution and size of hydroxyethyl starch fractions obtained by continuous polymer fractionation. Starch/Stärke 54:375–384CrossRef

81.

Hagenaars AC, Pesce JJ, Bailly C, Wolf BA (2001) Characterization of melt-polymerized polycarbonate: preparative fractionation, branching distribution and simulation. Polymer 42:7653–7661CrossRef

82.

Haberer M, Wolf BA (1995) Continuous fractionation of poly(acrylic acid). Angew Makromol Chem 228:179–184CrossRef

83.

Geerissen H, Roos J, Schützeichel P, Wolf BA (1987) Continuous fractionation and solution properties of PIB. I. Search for the best mixed solvent and first results of the continuous polymer fractionation. J Appl Polym Sci 34:271–285CrossRef

84.

Geerissen H, Schützeichel P, Wolf BA (1987) Continuous fractionation and solution properties of PIB. II. CPF optimization. J Appl Polym Sci 34:287–305CrossRef

85.

Samadi F, Eckelt J, Wolf BA, López-Villanueva FJ, Frey H (2007) Branched versus linear polyisoprene: fractionation and phase behavior. Eur Poly J 43:4236–4243CrossRef

86.

Eckelt J, Haase T, Loske S, Wolf BA (2004) Large scale fractionation of macromolecules. Macromol Mater Eng 289:393–399CrossRef

87.

Xiong X, Eckelt J, Wolf BA, Zhang Z, Zhang L (2006) Continuous spin fractionation and characterization by size-exclusion chromatography for styrene–butadiene block copolymers. J Chromatogr A 1110:53–60CrossRef

88.

Hagenaars AC, Bailly C, Schneider A, Wolf BA (2002) Preparative fractionation and characterization of polycarbonate/eugenol-siloxane copolymers. Polymer 43:2663–2669CrossRef

89.

Schmiedbauer J, Sybert PD (2000) In: Legrand DG, Bendler JT (eds) Handbook of polycarbonate science and technology. Marcel Dekker, New York

90.

Schiruschke M (1976) Quellungsmessungen an Hochpolymeren. Diploma thesis, Technical University Merseburg

Titel: Theory of Random Copolymer Fractionation in Columns
verfasst von: Sabine Enders
Verlag: Springer Berlin Heidelberg
Buch: Polymer Thermodynamics
Print ISBN: 978-3-642-17681-4

Electronic ISBN: 978-3-642-17682-1

Copyright-Jahr: 2011
DOI: https://doi.org/10.1007/12_2010_92

Premium Partner

Marktübersichten

Die im Laufe eines Jahres in der „adhäsion“ veröffentlichten Marktübersichten helfen Anwendern verschiedenster Branchen, sich einen gezielten Überblick über Lieferantenangebote zu verschaffen.

Zur Marktübersicht