Bayat 2012
Bayat 2012
Bayat 2012
ABSTRACT: In coordination polymerization of alpha-olefins utilizing Ziegler-Natta catalysts via slurry, polyolefin is produced with
other by-products such as polyethylene wax. Wax is defined as a linear short chain saturated by hydrocarbons in the relevant indus-
tries. Hexane and heptane are two of the most common suspending agents for the slurry process and wax molecules are soluble or
swollen in these kinds of liquids. After termination of polymerization, wax separates from the main product by physical processes. A
procedure for wax quantification in a laboratory reactor is suggested. Also, impacts of various factors such as reaction duration, pressure,
and cocatalyst on wax generation have been investigated. VC 2012 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 127: 1027–1031, 2013
KEYWORDS: polyethylene wax; ethylene; Ziegler-Natta catalysts; coordination polymerization; slurry phase; semibatch reactor
Received 19 June 2011; accepted 16 April 2012; published online 9 May 2012
DOI: 10.1002/app.37916
2. Transferring a hydrogen atom from the b-carbon of the (>99.9%), TEAL (Triethylaluminum) solution 1.0M in hexanes
propagating chain to the transition metal of the active site (Sigma Aldrich) and TIBAL (Triisobutylaluminum) solution
(b-hydrogen elimination): 1.0M in hexanes (Sigma Aldrich)].
Catalyst
Cl Ti ðCH2 CH2 Þn R ! Cl Ti H A Mg(OEt)2-Supported TiCl4 catalyst was used for this study.
þCH2 ¼ CH ðCH2 CH2 Þn1 R The catalyst used contains 2.7% Ti (w/w). The procedure of
preparing this type of catalyst has been described in the litera-
ture.12–15 In order to increase the dosage accuracy, the prepared
3. Transfer to organoaluminum compound (co-catalyst): catalyst was diluted 10 times with dried hexane.
The reference state which applied for this research and just the targeted
item is changed and traced.
Table III. Ethylene Pressure Effect on Wax Content and Polymer Table V. Cocatalyst Concentration and Type (Effect on Wax Content and
Specifications Polymer Specifications)
Table VI. External Donor Effect (THF - Exp 16) and Impurities Effect
Table IV. Hydrogen Pressure Effect on Wax Content and Polymer
(H2O - Exp 17) on Wax Content and Polymer Specificationsa
Specifications
donor can also significantly affect the wax quantity (see Table REFERENCES
VI). As the external donor changes, the mechanism of the 1. Natta, G.; Pino, P.; Corradini, P.; Corradini, F.; Danusso, F.;
monomer insertion to the active sites of the transition metal Mantica, E.; Mazzanti, G.; Moraglio, G. J. Am. Chem. Soc.
complex even the kinetic of the polymerization changes, there- 1955, 77, 1708.
fore the wax content varies.
2. Bohm, L. L. Polymer 1978, 19, 553.
3. Kim, I.; Choi, H. K.; Kim, J. H.; Woo, S. I. J. Appl. Polym.
The Effect of Impurities Sci. 1994, 52, 1739.
Regarding the high sensitivity of Ziegler-Natta catalysts to mois- 4. Marques, M. M. V.; Nunes, C. P.; Tait, P. J. T.; Dias, A. R. J.
ture, hexane and other components are dehydrated before use. Polym. Sci. A Polym. Chem. 1993, 31, 209.
In this experiment (Exp. No 17), fresh hexane is used without 5. Abedi, S.; Sharifi-Sanjani, N. J. Appl. Polym. Sci. 2000, 78,
any pretreatment or dehydration. Other parameters are retained 2533.
similar to Experiment No. 1 (the standard reaction condition).
6. Alt, F.; Schoneborn, P.; Bohm, L, inventors; Basell Polyole-
The initial water content of the fresh hexane was determined
fine GmbH, assignee. U.S. Pat.7,008,898 (2006).
(45 ppm). Experimental data shows that less yield and more
wax has been obtained (Table VI). 7. Finlayson, M. F.; Garrison, C. C.; Guerra, R. E.; Guest, M.
J.; Kolthammer, B. W. S.; Parikh, D. R.; Ueligger, S. M,
inventors; The Dow Chemical Company, assignee. U.S.
CONCLUSIONS Pat.6,054,544 (2000).
8. Troughton, M. J. Handbook of Plastics Joining (A Practical
In the coordination polymerization of ethylene in the slurry
Guide), 2nd ed.; Norwich, New York: William Andrew, 2008.
phase, wax is an inevitable by-product. This is the integral part
of any olefin polymerization and could be defined as the low 9. Lyons, W. C.; Plisga, G. J. Standard Handbook of Petroleum
and Natural Gas Engineering, 2nd ed.; Burlington, Massa-
molecular weight fraction of the combined polymer material.
chusetts: Elsevier, 2005.
The wax fraction depends on two principal parameters, the av-
erage molecular weight of the polymer and the presence of low 10. Natta, G.; Pasquon, I. Adv. Catal. 1959, 11, 1.
molecular weight components in the molecular weight distribu- 11. Bohm, L. L. Polymer 1978, 19, 545.
tion. The factors that affect any of these two properties affect 12. Virendra, K. G.; Marayil, R. Macromol. Chem. Phys. 1996,
the relative content of the wax. It is feasible that the quantifica- 197, 1937.
tion of wax in a laboratory reactor by gravimetery be carried 13. Franke, R.; inventor; Hoechst Aktiengesellschaft, assignee.
out in order to study different variants in conditions that the U.S. Pat.4,859,749 (1989).
total wax is separated and purified. In the semibatch reactor,
14. Bohm, L. L.; Herrmann, H. F.; Berthold, J.; Hohner, G.;
wax is generated in the early stage of reaction but continuous
Lecht, R.; Vetter, H. J., inventor; Clariant GmbH, assignee.
reactors generate steadily. Several various chemical or physical
EP Pat0,607,773 (1994).
factors are able to change the wax quantity although in view of
the fact that there is a big difference between the molecular 15. Dashti, A.; Ramazani, S. A. A.; Hiraoka, Y.; Kim, S. Y.;
Taniike, T.; Terano, M. Polym. Int. 2009, 285, 52.
weight of wax and the main product, it could be concluded that
wax is the result of chain transfer reactions to other reaction 16. Brandrup, J.; Immergut, E. H.; Grulke, E. A.; Abe, A.; Bloch,
components such as cocatalyst and particularly hydrogen. Also, D. R. Polymer Handbook, 4th ed.; New York: Wiley, 2005.
as result of deactivation of the catalyst (catalyst poisons and any 17. Sakurai, H.; Noro, J.; Kawase, A.; Fujinami, M.; Oguma, K.
impurities) the wax content increases and these kinds of reac- Anal. Sci. 2006, 22, 225.
tions have the most likely portion and were observed to occur 18. Goldenberg, A. L.; Lubetskii, S. G. Vysokomol. Soedin. 1963,
at the beginning of the reaction, especially. 5, 905.
On the basis of the results, since physical or chemical parame- 19. Standard Test Method for Water Using Volumetric Karl Fi-
ters are able to vary wax quantity, the lower and constant wax scher Titration; ASTM E 0203–08; ASTM International:
content as a by-product in continuous industrial production is West Conshohocken, PA, 2008.
an indication of desirable purity in raw materials. Also, the 20. Sacchi, M. C.; Forlini, F.; Tritto, I.; Locatelli, P.; Morini, G.;
nonexistence of catalyst poisons enhances minimum fluctua- Noristi, L.; Albizzati, E. Macromolecules 1996, 29, 3341.
tions in physical variants such as temperature, pressure, and et 21. Sacchi, M. C.; Forlini, F.; Tritto, I.; Mendichi, R.; Zannoni,
cetera. G.; Noristi, L. Macromolecules 1992, 25, 5914.
The authors express their gratitude to the department of 22. Boor, J. Ziegler-Natta Catalysts and Polymerizations; Aca-
Applied Chemistry of Amir Kabir University of Technology and demic Press: New York, 1979.
Arak Petrochemical Research Centre for their help and assis- 23. Moore, E. P. Polypropylene Handbook; Munich: Hanser,
tance in carrying out this project. 1996.