ORIGINAL_ARTICLE
Discovery and development of metallocene-based polyolefins with special properties
Beside Ziegler-Natta and Phillips catalysts the development of methylaluminoxane (MAO) as cocatalyst in combination with metallocenes or other transition metal complexes for the polymerization of olefins has widely increased the possibilities in controlling the polymer composition, polymer structure, tacticity and special properties with high precision. These catalysts allow the synthesis of isotactic, isoblock, syndiotactic, stereoblockor atactic polymers, as well as polyolefin composite materials with superior properties such as film clarity, tensile strength and lower content of extractables. Metallocene and other single site catalysts are able to copolymerize ethene and propene with short and long chained a-olefins, cyclic olefins, or polar vinyl monomers such as ethers, alcohols or esters, especially, if the polar monomers are protected by aluminum alkyls. Different vinyl ethers such as vinyl-ethyl ether, vinyl-propyl ether, vinyl-hexyl ether, and 2,7-octadienyl methyl ether (MODE) were copolymerized with olefins using triisobutyl aluminum as protecting agents. Polar monomers could be incorporated into the polymer chain by up to 16 mol%. Such copolymers show better gas barrier and surface properties, as well as solvent resistance and they are suitable for blends of polyolefins with polyethers and other polar polymers because of an excellent adhesion of the two polymers.
http://poj.ippi.ac.ir/article_1101_523ff56639af51a3fae73ac5028adeca.pdf
2015-01-01
1
16
10.22063/poj.2015.1101
Methylaluminoxane
metallocene catalysts
olefin copolymerization
polar monomers
vinyl ethers
Walter
Kaminsky
kaminsky@chemie.uni-hamburg.de
1
Institute for Technical and Macromolecular Chemistry, University of Hamburg Bundesstr. 45, 20146 Hamburg, Germany
LEAD_AUTHOR
Mercia
Fernandes
2
Institute for Technical and Macromolecular Chemistry, University of Hamburg Bundesstr. 45, 20146 Hamburg, Germany
AUTHOR
Kaminsky W (2008) Trends in polyolefin chemistry. Macromol Chem Phys 209: 459-466
1
Kaminsky W, Vollmer H-J, Heins E, Sinn H (1970) The formation of dimetalloalkylene, a unavoidable Side Reaction in homogeneous Ziegler-Catalysts Makromol Chem 175: 443-456
2
Mottweiler R (1975) Investigation of the reaction of biscylopentadienyl titanium compounds and aluminum alkyls, in the presents of ethylene. Thesis, University of Hamburg
3
Andresen A, Cordes H-G, Herwig J, Kaminsky W, Merck A, Mottweiler R, Pein J, Sinn H, Vollmer H-J, (1976) Halogen-free soluble Ziegler catalysts for the polymerization of ethylene. Control of molecular weight by choice of temperature. Angew Chem Int Ed Engl 15: 630-631
4
Kaminsky W (2004) The discovery of metallocene catalysts and their present state of the art. J Polym Sci Part A: Polym Chem 42: 3911-3921
5
Kaminsky W (2012) Discovery of methylaluminoxane as cocatalyst for olefin polymerization. Macromolecules 45: 3289-3297
6
Bliemeister J, Hagendorf W, Harder A, Heitmann B, Schimmel I, Schmedt E, Schnuchel W, Sinn H, Tikwe L, vThienen N, Urlass K, Winter H, Zarncke O (1995) The role of MAO activators. In: Ziegler catalysts, Fink G, Mülhaupt P, Brintzinger HH (eds), Springer, Berlin, 57-82
7
Eilertsen JL, Rytter E, Ystenes (1999) In situ FTIR spectroscopy shows no evidence of reaction between MAO and TMA. In: metalorganic catalysts for synthesis and polymerization, Kaminsky W (ed), Springer, Berlin, 136-141
8
Yang X, Stern CL, Marks TJ (1991) Models for organometallic molecule-support complexes. Very large counterion modulation of cationic actinide alkyl reactivity. Organometallics 10: 840-842
9
Bochmann M (2010) The chemistry of catalyst activation: The case of group 4 polymerization catalysts. Organometallics 29: 4711-4740
10
Scheirs J, Kaminsky W (eds.) (2000) Metallocene based polyolefins: Preparation, properties, and technology, Wiley, Chichester, UK, Vols. 1 and 2
11
Zhang J, Wang X, Jin G-X (2006) Polymerized metallocene catalysts and late transition metal catalysts for ethylene polymerization. Coordination Chem Rev 250: 95-109
12
Coates GW (2000) Precise control of polyolefin stereochemistry using single-site metal catalysts. Chem Rev 100: 1223-1252
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Rieger B, Baugh LS, Kacker S, Striegler S (eds) (2003) Late transition metal polymerization catalysis, Wiley-VCH, Weinheim
14
Razavi A, Thewalt U (2006) Site selective ligand modification and tactic variation in polypropylene chains produced with metallocene catalysts. Coordination Chem Rev 250: 155-169
15
Kaminsky W (ed.) (2005) Olefin polymerization. Macromol Symp 236
16
Kaminsky W, Luinstra GA (2010) Olefin polymerization by metallocene catalysis. Edition Ostwald: On Catalysis. Reschetilowski W, Hönle (eds) VWB-press, Berlin Vol 2, 186-214
17
Nomura K, Liu KJ (2011) Half-titanocenes for precise olefin polymerization: Effect of ligand substituents and some mechanistic aspects. Dalton Trans 40: 7666-7682
18
Kaminsky W (Ed) (2013) Polyolefins: 50 years after Ziegler and Natta. Vol I and II, Advances in Polymer Science 257 and 258, Springer, Heidelberg
19
Delferro M, Marks TJ (2011) Multinuclear olefin polymerization catalysts. Chem Rev 111: 2450-2485
20
Brintzinger HH, Fischer D, Mülhaupt R, Waymouth RM (1995) Stereospecific olefin polymerization with chiral metallocene catalysts. Angew Chem Int Ed Engl 34:1143-1170
21
Alt GH, Milius W, Palackal SJ (1994) Bridged bis(fluorenyl) complexes of zirconium and hafnium as highly reactive catalysts in homogeneous olefin polymerization. J Organomet Chem 472: 113-118
22
Kaminsky W, Engehausen R, Zoumis K, Spaleck W, Rohrmann J (1992) Standardized polymerization of ethylene and propene with bridged and unbridged metallocene derivates: A comparism. Makromol Chem 193: 1643-1651
23
Kaminsky W (1996) New polymers by metallocene catalysis. Macromol Chem Phys 197: 3907-3945
24
Okuda J, Schattenmann FJ, Wocadlo S, Massa W (1995) Synthesis and characterization of zirconium complexes containing a linked amido fluorenyl ligand. Organometallics 14: 789-795
25
Kawai K, Fujita T (2009) Metal catalysts in olefin polymerization. Top Organomet Chem 26: 3-46
26
Damavandi S, Zohuri GH, Ahmadjo S, Sandaroos R, Shamekhi MA (2014) Synthesis of high molecular weight polyethylene using FI catalysts. Polyolefins J 1: 25-32
27
Hlatky GG (2000) Heterogeneous single-site catalysts for olefin polymerization. Chem Rev 100: 1347-1376
28
Wild FR, Zsolnai L, Huttner G, Brintzinger HH (1982) ansa-metallocene derivates. IV. Synthesis and molecular structure of chiral ansa-titanocene derivates with bridged tetrahydroindenyl ligands. J Organomet Chem 232: 233-247
29
Kaminsky W, Külper K, Brintzinger HH, Wild FR (1985) Polymerization of propene and butane with a chiral zirconocene and methylalumoxane as cocatalyst. Angew Chem Int Ed Engl 24: 507- 508
30
Ewen JA, Jones RL, Razavi A, Ferrara JP (1988) Syndiospecific propylene polymerization with group IVB metallocenes. J Am Chem Soc 110: 6255-6256
31
Razavi A (2013) Syndiotactic polypropylene: Discovery, development, and industrialization via bridged metallocene catalysts. Adv Polym Sci 258: 43-116
32
Resconi l, Cavallo L, Fait A, Piemontesi F (2000) Selectivity in propene polymerization with metallocene catalysts. Chem Rev 100: 1253-1345
33
McNally T, Poetschke P Eds. (2011) Polymercarbon nanotube composites: Preparation, properties, and applications. Woodhead Publishing, Cambridge, UK
34
Alexandre M, Martin E, Dubois P, Marti MG, Jerome R (2001) Polymerization filling technique: an efficient way to improve the mechanical properties of polyethylene composites. Chem Mater 13: 236-237
35
Kaminsky W (2014) Metallocene based polyolefin nanocomposites. Materials 7: 5069-5108
36
Kaminsky W, Funck A, Klinke C (2008) In-situ polymerization of olefins on nanoparticles or fibers by metallocene catalysts. Top Catal 48: 84-90
37
Funck A, Kaminsky W (2007) Polypropylene carbon nanotube composites by in-situ polymerization with metallocene/MAO catalysts.Composites Sci and Technol 67: 906-915
38
Lozano K, Bonilla-Rios J, Barrera EV (2001) Nanofiber reinforced thermoplastic composites: Thermoanalytic and mechanical analysis. J Appl Polym Sci 80: 1162-1172
39
Stadler FJ, Arikan-Conley B, Kaschta J, Kaminsky W, Münstedt H (2011) Synthesis and characterization of novel ethylene-graft-ethylene/ propylene copolymers. Macromolecules 44: 5053-5063
40
Kaminsky W, Boggioni L, Tritto I (2012) Cycloolefin polymerization. Polym Sci A comp Ref 3: 843-873
41
Frediani M, Bianchini C, Kaminsky W (2006) Low density polyethylene by tandem catalysis with single site Ti(IV)/Co(II) catalysts. Kinet Catal 47: 207-212
42
Arikan B, Stadler FJ, Kaschta J, Münstedt H, Kaminsky W (2007) Synthesis and characterization of novel ethene-graft ethene/ propene copolymers. Macromol Rapid Commun 28: 1472-1478
43
Kaminsky W, Spiehl R (1989) Copolymerization of cycloalkenes with ethylene in presence of chiral zirconocene catalysts. Makromol Chem 190: 515-526
44
Boggioni L, Tritto I (2014) Propene- cycloolefin polymerization. Polyolefins J 1:61-75
45
Kaminsky W, Tran PD, Werner R (2004) New polymers by copolymerization of ethylene and norbornene with metallocene catalysts. Macromol Symp 213: 101-108
46
Seppälä J, Kokko E, Lehmus P, Malmberg AP, Hakala K, Lipponen S, Löfgren B (2013) Funktional polyolefins through polymerization by using bis(indenyl)zirkonium catalysts. Adv Polym Sci 2013: 179-232
47
Kesti MR, Coates GW, Waymouth RM, (1992) Homogeneous Ziegler-Natta polymerization of functionalized monomers catalyzed by cationic Group IV metallocenes. J Am Chem Soc 114: 9679-9680
48
Kaminsky W, Fernandez M (2008) New polymers by copolymerization of olefins with bio oil components. Eur J Lipid Sci Technol 110: 841- 845
49
Busico V, Cipullo R, Corradini P (1993) Macromol Chem Rapid Commun 117: 195.
50
Stadler FJ, Arikan B, Kaschta J, Kaminsky W (2010) Long-chain branches in syndiotactic polypropene induced by vinyl chloride. Macromol Chem Phys 211: 1472-1481
51
Kaminsky W, Funck A, Hähnsen H (2009) New application for metallocene catalysts in olefin polymerization. J Chem Soc Dalton Trans 2009: 8803-8810
52
Imuta J, Kashiwa N, Toda Y (2002) Catalytic regioselective introduction of allyl alcohol into the nonpolar polyolefins: Development of one pot synthesis of hydroxyl-capped polyolefins mediated by a new FI catalyst. J Am Chem Soc 124: 1176-1177
53
Lipponen S, Seppälä J (2011) Ethylenebis(indenyl)zirconium dichlo-ride/Methylaluminoxane catalyzed copolymerization of ethylene and 1- alkenen-trimethylsilanes. Organometallics 30: 528-533
54
Busico V (2009) Metal-catalysed olefin polymerisation into the new millenium: A perspective outlook. Dalton Trans 41: 8794-8802
55
ORIGINAL_ARTICLE
Intelligent catalysts for ethylene oligomerization and polymerization
EEthylene polymerization catalysts became available in an enormous variety. The challenge in this research is to find catalysts that are able to connect ethylene molecules in such a way that not only linear chains are produced but variations like branched materials that possess very interesting mechanical properties like linear low density polyethylene (LLDPE). In this contribution, three different types of catalysts are presented that are able to do not only one job at a time but three. These are “intelligent catalysts”. Catalysts of type 1 are homogeneous metallocene complexes that can be activated with methylaluminoxane (MAO).With ethylene they produce their own support and they become heterogeneous catalysts (self-immobilization) and they prevent fouling in polymerization reactors. The produced resin has evenly distributed ethyl branches (without a comonomer) with unique properties and the MAO that is necessary in the activation step can be recycled. Catalysts of type 2 are dinuclear complexes with two different active sites. One centre can oligomerize ethylene and the other one can copolymerize the in statu nascendi produced oligomers with ethylene to give branched LLDPE (a molecule as the smallest reactor for LLDPE) and/or bimodal resins.Catalysts of type 3 are MAO activated iron di (imino) pyridine complexes that are able to oligomerize ethylene to give not only oligomers with even numbered carbon atoms but also odd numbered ones. In this reaction, one catalyst does three jobs at a time: oligomerization, isomerization and metathesis of ethylene.
http://poj.ippi.ac.ir/article_1103_20f89a7cabeb6cd51ccc47d9a9f24910.pdf
2015-01-01
17
25
10.22063/poj.2015.1103
multi talented catalysts
oligomerization
polymerization
metathesis of ethylene
metallocene catalysts
di(imino) pyridine catalysis
Helmut G.
Alt
helmut.alt@uni-bayreuth.de
1
Laboratorium für Anorganische Chemie Universität Bayreuth, 95440 Bayreuth, Germany
LEAD_AUTHOR
Severn JR, Chadwick JC, Duchateau R, Friederichs N (2005) bound but not gagged immobilizing single-site α-olefin polymerization catalysts. Chem Rev 105: 4073-147
1
Kaminsky W (2008) Google archiv. Aktuelle wochenschau.de 48. Woche
2
Alt HG, Köppl A (2000) Effect of the nature of metallocene complexes of group IV metals on their performance in catalytic ethylene and propylene polymerization. Chem Rev 100:1205- 1222
3
Severn JR, Chadwick JC (2008) Tailor-Made Polymers, Wiley-VCH
4
Sinn H, Kaminsky W, Vollmer HJ (1980) Lebende Polymere bei Ziegler Katalysatoren extremer Produktivität. Angew Chem 92: 396- 402
5
Sinn H, Kaminsky W (1980) Ziegler-Natta catalysis. Adv Organomet Chem 18: 99-149
6
Alt HG, Milius W, Palackal SJ (1994) Verbrückte Bis(fluorenyl)komplexe des Zirconiums und Hafniums als hochreaktive Katalysatoren bei der homogenen Olefinpolymerisation. Die Molekülstrukturen von (C13H9-C2H4-C13H9) und (η5:η5-C13H8-C2H4 -C13H8)ZrCl2. J Organomet Chem 472:113-118
7
Alt HG, Samuel E (1998) Fluorenyl complexes of zirconium and hafnium as catalysts for olefin polymerization. Chem Soc Rev 27: 323-329
8
Peifer B, Milius W, Alt HG (1998) Verbrückte indenyliden–cyclopentadienylidenkomplexe des typs (C9H5CH2Ph–X–C5H4)MCl2 (X=CMe2, SiMe2; M=Zr, Hf) als Metallocenkatalysatoren für die Ethylenpolymerisation. Die Molekülstrukturen von (C9H5CH2Ph–CMe2–C5H4)MCl2 (M=Zr, Hf). J Organomet Chem 558: 111-121
9
Alt HG, Jung M (1999) C2-bridged metallocene dichloride complexes of the types (C13H8–CH2CHR– C9H6−nR′n)ZrCl2 and (C13H8–CH2CHR–C13H8) MCl2 (n=0, 1; R=H, alkenyl; R′=alkenyl, benzyl; M=Zr, Hf) as self-immobilizing catalyst precursors for ethylene polymerization. J Organomet Chem 580: 1-16
10
Alt HG (1999) The heterogenization of homogeneous metallocene catalysts for olefin polymerization. J. Chem. Soc., Dalton Trans: 1703-1710
11
Alt HG (2005) Self-immobilizing catalysts and cocatalysts for olefin polymerization. Dalton Trans: 3271-3276
12
Licht A, Alt HG (2002) Synthesis of novel metallacyclic zirconocene complexes from ω-alkenyl-functionalized zirconocene dichloride complexes and their use in the α-olefin polymerization. J Organomet Chem 648: 134-148
13
Alt HG (2006) Metallacyclic metallocene complexes as catalysts for olefin polymerization. Coord Chem Rev 250: 2-17
14
Görl C, Alt HG (2007) Iron complexes with ω-alkenyl substituted bis(arylimino) pyridine ligands as catalyst precursors for the oligomerization and polymerization of ethylene. J Mol Cat A Chem 273: 118-132
15
Görl C, Alt HG (2007) The combination of mononuclear metallocene and phenoxyimine complexes to give trinuclear catalysts for the polymerization of ethylene. J Organomet Chem 692: 5727-5753
16
Görl C, Alt HG (2007) Influence of the para-substitution in bis(arylimino)pyridine iron complexes on the catalytic oligomerization and polymerization of ethylene. J Organomet Chem 692:4580-45925
17
Kestel-Jakob A, Alt HG (2007) Boryl-substituted zirconocene dichloride complexes as catalyst precursors for homogeneous ethylene polymerization. Z Naturforsch 62b: 314-322
18
Ostoja Starzewski KHA, Kelly WM, Stumpf A, Freitag D (1999) Donor/acceptor metallocenes: A new structure principle in catalyst design. Angew. Chem Int Ed 38: 2439-2443
19
Ostoja Starzewski KHA (2004) D/A-metallocenes: The new dimension in catalyst design. Macromol Symp 213: 47-56
20
Schilling M, Bal R, Görl C, Alt HG (2007) Heterogeneous catalyst mixtures for the polymerization of ethylene. Polymer 48: 7461- 7475
21
Böhmer I, Alt HG (2009) Influence of triphenylphosphine on the activity of heterogeneous iridium, rhodium and platinum containing catalysts for the dehydrogenation of saturated hydrocarbons. J Organomet Chem 694:1001-1010
22
Taubmann S, Alt HG (2008) Catalytic dehydrogenation of cyclooctane in homogeneous solution with titanium, zirconium and hafnium complexes containing N,O-chelating ligands. J Mol Cat A Chem 289: 49-56
23
Alt HG, Denner CE, Taubmann S (2009) "Like Phoenix from the ashes"! Thermally decomposed metallocene complexes as catalysts for CH activation reactions. JJC 4: 45-54
24
ORIGINAL_ARTICLE
Kinetics of ethylene polymerization over titanium-magnesium catalysts: The reasons for the observed second order of polymerization rate with respect to ethylene
The data on the effect of ethylene concentration on polymerization rate for several modifications of modern highly active titanium–magnesium catalysts TiCl4/MgCl2 are presented. These catalysts differ in titanium content and conditions of support preparation, activities, and the shape of kinetic curves. It is found that the observed order of polymerization rate with respect to ethylene in the range of ethylene pressures of 0.5–6 bar is 1.8-2.1 for all catalysts used (polymerization at 80°C, AlEt3 used as a cocatalyst). When AlEt3 was replaced with Al(i-Bu)3, the reaction order decreased to 1.3-1.4. In order to elucidate the possible reasons for the observed high order with respect to ethylene, we analyzed the data on the effect of monomer concentration on the molecular weight of polyethylene. The results gave grounds for suggesting that the observed order with respect to monomer is attributable to the effect of ethylene concentration on the number of active sites. The possible reaction scheme explaining the nonlinear dependence of the polymerization rate on monomer concentration was proposed based on these data.
http://poj.ippi.ac.ir/article_1112_840c6ae654868497d0f86c19a8e68343.pdf
2015-01-01
27
38
10.22063/poj.2015.1112
Polyethylene (PE)
polymerization kinetics
Ziegler-Natta polymerization
molecular weight distribution / molar mass distribution
Mikhail
Matsko
matsko@catalysis.ru
1
Boreskov Institute of Catalysis, Siberian Branch of the Russian Academy of Sciences, Prospekt Akademika Lavrentieva 5, Novosibirsk 630090, Russia
LEAD_AUTHOR
Vladimir
Zakharov
zva@catalysis.ru
2
Boreskov Institute of Catalysis, Siberian Branch of the Russian Academy of Sciences, Prospekt Akademika Lavrentieva 5, Novosibirsk 630090, Russia
AUTHOR
Marina
Nikolaeva
nikami@catalysis.ru
3
Boreskov Institute of Catalysis, Siberian Branch of the Russian Academy of Sciences, Prospekt Akademika Lavrentieva 5, Novosibirsk 630090, Russia
AUTHOR
Tatiana
Mikenas
mikenas@catalysis.ru
4
Boreskov Institute of Catalysis, Siberian Branch of the Russian Academy of Sciences, Prospekt Akademika Lavrentieva 5, Novosibirsk 630090, Russia
AUTHOR
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3
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19
Chakravarti S, Ray WH (2001) Kinetic study of olefin polymerization with a supported metallocene catalyst. II. Ethylene/1-hexene copolymerization in gas phase. J Appl Polym Sci 80: 1096-1119
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30
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31
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32
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37
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39
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40
Bukatov GD, Zakharov VA, Barabanov AA (2005) Mechanism of olefin polymerization on supported Ziegler-Natta catalysts based on data on the number of active centers and propagation rate constants. Kinet Catal 46: 166-176
41
McKenna TFL, Di Martino A, Weickert G, Soares JBP (2010) Particle growth during the polymerisation of olefins on supported catalysts, 1-Nascent polymer structures. Macromol React Eng 4: 40-64
42
Nikolaeva MI, Mikenas TB, Matsko MA, Echevskaya LG, Zakharov VA (2011) Ethylene polymerization over supported titanium-magnesium catalysts: Effect of polymerization parameters on the molecular weight distribution of polyethylene. J Appl Polym Sci 122: 3092- 3101
43
Echevskaya LG, Matsko MA, Mikenas TB, Nikitin VE, Zakharov VA (2006) Supported titanium-magnesium catalysts with different titanium content: Kinetic peculiarities at ethylene homopolymerization and copolymerization and molecular weight characteristics of polyethylene. J Appl Polym Sci 102: 5436-5442
44
ORIGINAL_ARTICLE
Estimation of pyrolysis product of LDPE degradation using different process parameters in a stirred reactor
Pyrolysis of low density polyethylene (LDPE) by equilibrium fluid catalytic cracking (FCC) was studied in a stirred reactor under different process parameters. In this work, the effect of process parameters such as degradation temperature (420-510°C), catalyst/polymer ratio (0-60%), carrier gas type (H2, N2, ethylene, propylene, Ar and He), residence time and agitator speed (0-300 rpm) on the condensate yield (liquid, gas and coke) and product composition were considered. Reaction products were determined by GC analysis and shown to contain naphthenes (cycloalkanes), paraffins (alkanes), olefins (alkenes) and aromatics. Higher temperature and more catalyst amount enhanced LDPE cracking. The maximum “fuel like” condensed product yield was attained at 450°C and 10% catalyst, respectively and gaseous products increased with increases in temperature. Hydrogen as a reactive carrier gas increased the condensed and paraffinic product yield. Appropriate heat transfer (by stirring) increased the catalyst efficiency in a stirred reactor.
http://poj.ippi.ac.ir/article_1102_1e2b6565bb9019394cb665fbf6453049.pdf
2015-01-01
39
47
10.22063/poj.2015.1102
LDPE
pyrolysis
fluid catalytic cracking (FCC)
stirred reactor
carrier gas
agitator speed
Mehrdad
Seifali Abbas-Abadi
mehrdad.seifali@ugent.be
1
Chemical Engineering, Energy Department, Kermanshah University of Technology, P.O. Box 67178-3766, Kermanshah, Iran
LEAD_AUTHOR
Mehdi
Nekoomanesh Haghighi
m.nekoomanesh@ippi.ac.ir
2
Polymerization Engineering, Iran Polymer and Petrochemical Institute (IPPI), P.O. Box 14965/115, Tehran, Iran
AUTHOR
Armando G.
McDonald
armandm@uidaho.edu
3
Department of Forest, Rangeland and Fire Sciences, University of Idaho, PO Box 441132, Moscow, ID 83844-1132, USA
AUTHOR
Hamid
Yeganeh
h.yeganeh@ippi.ac.ir
4
Polymerization Engineering, Iran Polymer and Petrochemical Institute (IPPI), P.O. Box 14965/115, Tehran, Iran
AUTHOR
U.S. Environmental Protection Agency (2010) Municipal solid waste generation, recycling, and disposal in the United States: Facts and figures, Washington D.C.http://www.epa.gov
1
U.S. Environmental Protection Agency (2010) solid waste management and greenhouse gases: A life-cycle assessment of emissions and sinks, Washington D.C., http://www.epa.gov
2
Aguado J, Serrano D (1999) in Feedstock recycling of plastic wastes, the royal society of chemistry, Clark J H (Ed.), Cambridge, UK
3
Aboulkas A, Harfi KE, Bouadili AE (2010) Thermal degradation behaviors of polyethylene and polypropylene. Part I: Pyrolysis kinetics and mechanisms. Energ Convers Manag 51: 1363- 1369
4
Rotliwala YC, Parikh PA, (2012) Thermal coprocessing of high density polyethylene with coal, fly ashes, and biomass: Characterization of liquid products. Energy Sources Part A: Recovery Util Environ 34: 1055-1066
5
Mishra N, Das G, Ansaldo A, Genovese A, Malerba M, Povia M, Ricci D, Di Fabrizio E, Zitti ED, Sharon M (2012) Pyrolysis of waste polypropylene for the synthesis of carbon nanotubes. J Anal Appl Pyrol 94: 91-98
6
Park HJ, Yim JH, Jeon JK, Kim JM, Yoo KS, Park YK (2008) Pyrolysis of polypropylene over mesoporous MCM-48 material. J Phys Chem Sol 69: 1125-1128
7
Usman MA, Alaje TO, Ekwueme VI, Adekoya TE (2012) Catalytic degradation of water sachet waste (LPDE) using mesoporous silica KIT-6 modified with 12-Tungstophosphoric Acid. J Petrol Coal 54: 85-90
8
Olazar M, Lopez G, Amutio M, Elordi G, Aguado R, Bilbao J (2009) Influence of FCC catalyst steaming on HDPE pyrolysis product distribution. J Anal Appl Pyro 85: 359–365
9
Degnan TF (2000) Applications of zeolites in petroluem refining. Top Catal 13: 349-356
10
Zhou Q, Wang YZ, Tang C, Zhang YH (2003) Modifications of ZSM-5 zeolites and their applications in catalytic degradation of LDPE. Polym Degrad Stab 80: 23-30
11
Nisar J, ALI M, Awan IA (2011) Catalytic thermal decomposition of polyethylene by pyrolysis gas chromatography. J Chil Chem Soc 56: 653-655
12
Jan MR, Shah J, Gulab H (2010) Catalytic degradation of waste high-density polyethylene into fuel products using BaCO3 as a catalyst. Fuel Process Technol 91: 1428-1437
13
Seifali Abbas-Abadi M, Nekoomanesh Haghighi M, Yeganeh H (2012) The effect of temperature, catalyst, different carrier gases and stirrer on the produced transportation hydrocarbons of LLDPE degradation in a stirred reactor. J Anal Appl Pyrol 95: 198-204
14
Seifali Abbas-Abadi M, Nekoomanesh Haghighi M, Yeganeh H (2012) Evaluation of pyrolysis product of virgin high density polyethylene degradation using different process parameters in a stirred reactor. Fuel Process Technol 109: 90-95
15
Seifali Abbas-Abadi M, Nekoomanesh Haghighi M, Yeganeh H, McDonald AG (2014) Evaluation of pyrolysis process parameters on polypropylene degradation products. J Anal Appl Pyrol 109: 272-277
16
Ahmad E, Chadar S, Tomar SS, Akram MK (2009) Catalytic degradation of waste plastic into fuel oil. Int J Petrol Sci Technol 3: 25-34
17
Jung SH, Cho MH, Kang BS, Kim JS (2010) Pyrolysis of a fraction of waste polypropylene and polyethylene for the recovery of BTX aromatics using a fluidized bed reactor”. Fuel Process Technol 91: 277-284
18
Salman M, Rehman R, Shafique U, Mahmud T, Ali B, (2012) Comparative thermal and catalytic recycling of low density polyethylene into diesellike oil using different commercial catalysts, J Environ Agric Food Chem 11: 96-105
19
Almustapha MN, Andrésen JM (2012) Recovery of valuable chemicals from high density polyethylene (HDPE) Polymer: a catalytic approach for plastic waste recycling. Int J Environ Sci Develop 3: 3
20
Tiwari DC, Ahmad E, Kumar Singh KK, (2009) Catalytic degradation of waste plastic into fuel range hydrocarbons. Int J Chem Res 1: 31-36
21
Ali MF, Qureshi MS (2011) Catalyzed pyrolysis of plastics: A thermogravimetric study, African J Pure Appl Chem 5: 284-292
22
Bajus M, Hájeková E (2010) Thermal cracking of the model seven components mixed plastics into bvcoils/waxes. J Petrol Coal 52: 164-172
23
Marcilla A, Go´mez A, Reyes-Labarta JA, Giner A (2003) Catalytic pyrolysis of polypropylene using MCM-41: kinetic model. Polym Degrad Stabil 80: 233-240
24
de la Puente G, Klocker C, Sedran U (2002) Conversion of waste plastics into fuels recycling polyethylene in FCC. Appl Catal B: Environ 36: 279-285
25
Lee KH (2008) Composition of aromatic products in the catalytic degradation of the mixture of waste polystyrene and high-density polyethylene using spent FCC catalyst. Polym Degrad Stabil 93: 1284-1289
26
Williams PT, Slaney E (2007) Analysis of products from the pyrolysis and liquefaction of single plastics and waste plastic mixtures. Res Conserv Recyc 51: 754-769
27
Kim SS, Kim S (2004) Pyrolysis characteristics of polystyrene and polypropylene in a stirred batch reactor. Chem Eng J 98: 53-60
28
Osueke CO, Ofondu IO (2011) Conversion of waste plastics (polyethylene) to fuel by means of pyrolysis. Int J Adv Eng Sci Technol 4: 21-24
29
Green AES, Sadrameli SM (2004) Analytical representations of experimental polyethylene pyrolysis yields. J Anal Appl Pyrol 72: 329-335
30
Lin YH, Yang MH (2007) Catalytic pyrolysis of polyolefin waste into valuable hydrocarbons over reused catalyst from refinery FCC units. Appl Catal A: General 328: 132-139
31
Simon CM, Kaminsky W (1998) Chemical recycling of polytetrafluoroethylene by pyrolysis. Polym Degrad Stabil 62:1-7
32
Willams PT, Nazzal JM (1995) Polycyclic aromatic compounds in shale oils: Influence of process conditions. J Anal Appl Pyrol 35: 181-197
33
Lin HT, Huang MS, Luo JW, Lin LH, Lee CM, Ou KL (2010) Hydrocarbon fuels produced by catalytic pyrolysis of hospital plastic wastes in a fluidizing cracking process. Fuel Process Technol 91: 1355-1363
34
Lin YH, Hwu WH, Ger MD, Yeh TF , Dwyer J, (2001) A combined kinetic and mechanistic modeling of the catalytic degradation of polymers. J Mol Catal A: Chem 171: 143-151
35
You, YS, Kim JH, Seo G, (2000) Liquid-Phase catalytic degradation of polyethylene wax over MFI zeolites with different particle sizes. Polym Degrad Stabil 70: 365-371
36
Xiao J, Wei J (1992) Diffusion mechanism of hydrocarbons in zeolites - I. Theory. Chem Eng Sci 47: 1123-1141
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Marcilla A, Garcý´a-Quesada JC, Sa´nchez S, Ruiz R (2005) Study of the catalytic pyrolysis behavior of polyethylene–polypropylene mixtures. J Anal Appl Pyrol 74: 387-392
38
ORIGINAL_ARTICLE
High porosity polyethylene aerogels
Monolithic aerogels of high molecular weight polyethylene (Mw= 3x106- 6x106 g/mol) have been prepared by solvent extraction with supercritical carbon dioxide from thermoreversible gels prepared in decalin. These low density and highly porous aerogels present an apparent porosity up to 90%. The aerogel morphology observed by scanning electron microscopy (SEM) is characterized by spherulitic structures being interconnected by fibers. X-ray diffraction experiments show that PE aerogels are highly crystalline with a degree of crystallinity of c.a. 80% and PE chains being packed into the typical orthorombic unit cell. Combined SEM and N2 sorption investigations show that PE aerogels are essentially macroporous with a small amount of mesopores. The oil-sorption performance of polyethylene aerogels has been also evaluated in this study in order to assess a possible use of these materials for oil spillage recovery and results show that aerogel macropores allow a very fast sorption kinetics with a 100% oil weight uptake obtained in less than 1 minute.
http://poj.ippi.ac.ir/article_1113_c42d9484e92cd75269739edfc7d85067.pdf
2015-01-01
49
55
10.22063/poj.2015.1113
polyethylene
thermoreversible gels, aerogels
supercritical carbon dioxide
oil spillage recovery
Christophe
Daniel
cdaniel@unisa.it
1
Dipartimento di Chimica e Biologia e Unità INSTM, Università degli Studi di Salerno Via Giovanni Paolo II,132- 84084 Fisciano (SA), Italy
AUTHOR
Simona
Longo
slongo@unisa.it
2
Dipartimento di Chimica e Biologia e Unità INSTM, Università degli Studi di Salerno Via Giovanni Paolo II,132- 84084 Fisciano (SA), Italy
AUTHOR
Gaetano
Guerra
gguerra@unisa.it
3
Dipartimento di Chimica e Biologia e Unità INSTM, Università degli Studi di Salerno Via Giovanni Paolo II,132- 84084 Fisciano (SA), Italy
LEAD_AUTHOR
Wu D, Xu F, Sun B, Fu R , He H, Matyjaszewski K (2012) Design and preparation of porous polymers. Chem Rev 112: 3959-4015
1
Colton JS (1989) The nucleation of microcellular foams in semi crystalline thermoplastics. Mater Manuf Process 4: 253-262
2
Doroudiani S, Park CB, Kortschot MT (1998) Processing and characterization of microcellular foamed high-density polythylene/isotactic polypropylene blends. Polym Eng Sci 38: 1205- 1215
3
Nofar M, Guo Y, Park CB (2013) Effects of saturation temperature/pressure on melting behavior and cell structure of expanded polypropylene bead. Ind Eng Chem Res 52: 2297−2303
4
Bush PJ, Pradhan D, Ehrlich P (1991) Lamellar structure and organization in polyethylene gels crystallized from supercritical solution in propane. Macromolecules 24:1439-1440
5
Pradhan D, Ehrlich P (1995) Morphologies of microporous polyethylene and polypropylene crystallized from solution in supercritical propane. J Polym Sci Polym Phys 33: 1053-1063
6
Whaley PD, Kulkarni S, Ehrlich P, Stein RS, Winter HH, Conner WC, Beaucage G (1998) Isotactic polypropylene foams crystallized from compressed propane solutions. J Polym Sci Polym Phys 36: 617-627
7
Winter HH, Gappert G, Ito H (2002) Rigid pore structure from highly swollen polymer gels. Macromolecules 35: 3325-3327
8
Pekala RW (1989) Organic aerogels from polycondensation of resorcinol with formaldehyde. J Mater Sci 24: 3221-3227
9
Pekala RW, Alviso CT, Lu X, Gross J, Fricke J (1995) New organic aerogels based upon a phenolic-furfural reaction. J Non-Cryst Solids 188: 34-40
10
Daniel C, Alfano D, Venditto V, Cardea S, Reverchon E, Larobina D, Mensitieri G, Guerra G (2005) Aerogels with a microporous crystalline host phase. Adv Mater 17: 1515-1518
11
Daniel C, Sannino D, Guerra G (2008) Syndiotactic polystyrene aerogels: Adsorption in amorphous pores and absorption in crystalline nanocavities. Chem Mater 20: 577-582
12
Daniel C, Giudice S, Guerra G (2009) Syndiotatic polystyrene perogels with beta, gamma and epsilon crystalline phases. Chem Mater 21: 1028−1034
13
Guenet JM, Parmentier J, Daniel C (2011) Porous materials from polyvinylidene fluoride/solvent molecular compounds. Soft Mater 9: 280-294
14
Cardea S, Gugliuzza A, Sessa M, Aceto MC, Drioli, E, Reverchon E (2009) Supercritical gel drying: A powerful tool for tailoring symmetric porous PVDF-HFP membranes. ACS Appl Mater Interfaces 1: 171-180
15
Daniel C, Vitillo JG, Fasano G, Guerra G (2011) Aerogels and polymorphism of isotactic poly(4- methyl-pentene-1). ACS Appl Mater Interfaces 3: 969-977
16
Daniel C, Longo S, Cardea S, Vitillo JG , Guerra G (2012) Monolithic nanoporous–crystalline aerogels based on PPO. RSC Adv 2: 12011-12018
17
Longo S, Vitillo JG, Daniel C, Guerra G (2013) Monolithic aerogels based on poly(2,6- diphenyl-1,4-phenylene oxide) and syndiotactic polystyrene. ACS Appl Mater Interfaces 5: 5493−5499
18
Pennings AJ (1977) Bundle-like nucleation and longitudinal growth of fibrillar polymer crystals from flowing solutions. J Polym Sci Polym Symp 59: 55-86
19
Barham PJ, Hill MJ , Keller A, (1980) Gelation and the production of surface grown polyethylene fibres. Colloid Polym Sci 258: 899-908
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Smith P, Lemstra PJ, Pijpers JPL, Kiel AM (1981) Ultra-drawing of high molecular weight polyethylene cast from solution. Colloid Polym Sci 259: 1070-1080
21
Narh KA, Barham PJ, Keller A (1982) Effect of stirring on the gelation behavior of high-density polyethylene solutions. Macromolecules 15:464- 469
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Rouquerol J, Avnir D, Fairbridge CW, Everett DH, Haynes JH, Pernicone N, Ramsay JDF, Sing KSW, Unger KK (1994) Recommendations for the characterization of porous solids, Pure Appl Chem 66: 1739-1758
23
Wang X, Jana SC (2013) Synergistic hybrid organic-inorganic aerogels. ACS Appl Mater Interfaces 5: 6423-6429
24
Daniel C, Longo S, Ricciardi R, Reverchon E, Guerra G (2013) Monolithic nanoporous crystalline aerogels. Macromol Rapid Commun 34:1194-1207
25
Wei QF, Mather RR, Fotheringham AF, Yang RD (2003) Evaluation of nonwoven polypropylene oil sorbents in marine oil-spill recovery. Mar Pollut Bull 46: 780-783
26
ORIGINAL_ARTICLE
Active site nature of magnesium dichloride-supported titanocene catalysts in olefin polymerization
Heterogeneous Ziegler-Natta and homogeneous metallocene catalysts exhibit greatly different active sitenature in olefin polymerization. In our previous study, it was reported that MgCl2-supported titanocenecatalysts can generate both Ziegler-Natta-type and metallocene-type active sites according to the type of activators.The dual active site nature of the supported titanocene catalysts was further explored in the present study: The influence of the ligand structure of titanocene precursors was studied on the nature of active sites when supported on MgCl2 in ethylene and propylene homopolymerization, and ethylene/1-hexene copolymerization. It was found that the reducibility of titanocene precursors by alkylaluminum is closely related to the appearance of the dual active site nature, while the kind of olefin did not affect the type of active sites formed during polymerization. The Ziegler-Natta-type active sites produced poorly isotactic polypropylene and less branched polyethylene, while the metallocene-type active sites produced atactic polypropylene and exhibited much higher incorporation efficiency for 1-hexene.
http://poj.ippi.ac.ir/article_1114_8babadc8ab720401083d91a682318328.pdf
2015-01-01
57
63
10.22063/poj.2015.1114
metallocene catalysts
Ziegler-Natta polymerization
poly(propylene) (PP)
Toshiaki
Taniike
taniike@jaist.ac.jp
1
School of Materials Science, Japan Advanced Institute of Science and Technology, 1-1 Asahidai, Nomi, Ishikawa 923-1292, Japan
AUTHOR
Keisuke
Goto
k.goto@jaist.ac.jp
2
School of Materials Science, Japan Advanced Institute of Science and Technology, 1-1 Asahidai, Nomi, Ishikawa 923-1292, Japan
AUTHOR
Minoru
Terano
terano@jaist.ac.jp
3
School of Materials Science, Japan Advanced Institute of Science and Technology, 1-1 Asahidai, Nomi, Ishikawa 923-1292, Japan
LEAD_AUTHOR
Goto K, Taniike T, Terano M (2013) Dualactive- site nature of magnesium dichloridesupported cyclopentadienyl titanium chloride catalysts switched by an activator in propylene polymerization. Macromol Chem Phys 214: 1011-1018
1
Sinn H, Kaminsky W (1980) Ziegler-Natta catalysis. Adv Organomet Chem 18: 99-149
2
Albizzati E, Giannini U, Collina G, Noristi L, Resconi, L (1996) Catalysts and polymerizations. In polypropylene handbook, Moore EP Ed. 11-98
3
Jordan RF, Bajgur CS, Willett R, Scott, B (1986) Ethylene polymerization by a cationic dicyclopentadienyl zirconium(IV) alkyl complex. J Am Chem Soc 108: 7410-7411
4
Yang X, Stern CL, Marks TJ (1991) Cationlike homogeneous olefin polymerization catalysts based upon zirconocene alkyls and tris(pentafluorophenyl)borane. J Am Chem Soc 113: 3623-3625
5
Busico V, Cipullo R (2001) Microstructure of polypropylene. Prog Polym Sci 26: 443-533
6
Severn JR, Chadwick JC, Duchateau R, Friederichs N (2005) “Bound but not gagged” -immobilizing single-site a-olefin polymerization catalysts. Chem Rev 105: 4073-4147
7
Kaminaka M, Soga. K (1991) Polymerization of propene with the catalyst systems composed of Al2O3- or MgCl2-supported Et[IndH4]2ZrCl2 and AlR3 (R = CH3, C2H5). Die Makromol Chem Rapid Commun 12: 367-372
8
Huang YH, Yu Q, Zhu S, Rempel GL, Li L (1999) ESR studies on oxidation state of titanocene and zirconocene catalysts. J Polym Sci Part A: Polym Chem 37: 1465-1472
9
Chien JCW (1999) Supported metallocene polymerization catalysis. Top Catal 7: 23-36
10
Fregonese D, Mortara S, Bresadola S (2001) Ziegler–Natta MgCl2-supported catalysts: relationship between titanium oxidation states distribution and activity in olefin polymerization. J Mol Catal A: Chem 172: 89-95
11
Senso N, Praserthdam P, Jongsomjit B, Taniike T, Terano M (2011) Effects of Ti oxidation state on ethylene, 1-hexene comonomer polymerization by MgCl2-supported Ziegler-Natta catalysts. Polym Bull 67:1979-1989
12