Abstract
This chapter provides a brief account of the discovery and gradual evolution of Ziegler-Natta catalysts for polymerization of various olefins, α-olefins, and functional olefins. The structure of first and second generation catalysts is introduced, and the different mechanisms proposed by the scientists for the polymerization of ethylene using this catalyst is discussed. Subsequently, the control of branching and mechanism to produce stereospecific poly-α-olefins is elaborated. Development of catalysts for synthesis of stereo-controlled polyolefins is discussed along with methods to determine the stereospecificity of the polymers. The evolution of metallocene-based Ziegler-Natta catalysts and the mechanism of polymerization based on these catalysts are briefed. The following section discusses about the catalyst compositions useful for polymerization of functional olefin monomers and their copolymerization with propylene. Development of catalyst compositions based on Pd, Ni, Cu, and Fe is discussed, and subsequent polymerization mechanism is included. A series of catalysts synthesized using vanadium and various chelated ligands are discussed in context of their catalytic activity and the structure of polymer formed. The last chapter unveils some of the recent advances in these categories of catalysts and future scope of the catalyst.
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References
Ziegler K, Holzkamp E, Breil H, Martin H (1955) Polymerization of ethylene and other olefins. Angew Chem 67(16):426
Natta N, Pino P, Corradini P, Danusso F, Mantica E, Mazzanti G, Moraglio G (1955) Crystalline high polymers of α-olefins. J Am Chem Soc 77(6):1708–1710
Natta G, Pino P, Mazzanti G, Giannini U, Mantica E, Peraldo M (1957) The nature of some soluble catalysts for low pressure ethylene polymerization. J Polym Sci 26(112):120–123
Furukawa J, Tsuruta T (1959) Catalytic reactivity and stereospecificity of organometallic compounds in olefin polymerization. J Polym Sci 36(130):275–186
Rodriguez LAM, van Looy HM (1966) Studies on Ziegler-Natta catalysts. Part V. Stereospecificity of the active center. J Polym Sci A Polym Chem 4(8):1971–1992
Cossee P (1960) On the reaction mechanism of the ethylene polymerization with heterogeneous Ziegler-Natta catalysts. Tetrahedron Lett 38(1):12–16
Ludlum DB, Anderson AW, Ashby CE (1958) The polymerization of ethylene by lower valent compounds of titanium. J Am Chem Soc 80(6):1380–1384
Ziegler K (1959) International Conference on Co-ordination Chemistry, London. The Chem Soc Spec Publ 12(1). Chemistry Society, London
Ivin KJ, Rooney JJ, Stewart CD, Green MLH, Mahtab R (1978) Mechanism for the stereospecific polymerization of olefins by Ziegler–Natta catalysts. J Chem Soc Chem Commun 14:604–606
Soto J, Steigerwald ML, Grubbs RH (1982) Concerning the mechanism of Ziegler-Natta polymerization: isotope effects on propagation rates. J Am Chem Soc 104(16):4479–4480
Corradini P, Barone V, Fusco R, Guerra G (1979) Analysis of models for the Ziegler-Natta stereospecific polymerization on the basis of non-bonded interactions at the catalytic site—I. The Cossee model. Eur Polym J 15(12):1133–1141
Langer AW Jr (1977) Base effects on selected Ziegler-type catalysts. Ann N Y Acad Sci 295(1):110–126
Breslow DS, Newburg NR (1959) Bis-(cyclopentadienyl)-titanium dichloride-alkylaluminum complexes as soluble catalysts for the polymerization of ethylene1,2. J Am Chem Soc 81(1):81–86
Andresen A, Cordes HG, Herwig J, Kaminsky W, Merck A, Mottweiler R, Pein J, Sinn H, Vollmer HJ (1976) Halogen-free soluble Ziegler catalysts for the polymerization of ethylene. Control of molecular weight by choice of temperature. Angew Chem 15(10):630–632
Kaminsky W, Külper K, Niedoba S (1986) Olefin polymerization with highly active soluble zirconium compounds using aluminoxane as co-catalyst. Macromol Chem 3(1):377–387
Pino P, Mulhaupt R (1980) Stereospecific polymerization of propylene: an outlook 25 years after its discovery. Angew Chem 19(11):857–875
Ewen JA (1984) Mechanisms of stereochemical control in propylene polymerizations with soluble Group 4B metallocene/methylalumoxane catalysts. J Am Chem Soc 106(21):6355–6364
Zambelli A, Locatelli P, Provasoli A, Ferro DR (1980) Correlation between 13C NMR chemical shifts and conformation of polymers. 3. Hexad sequence assignments of methylene. Spec Polyprop 13(2):267–270
Boor J Jr, Youngman EA (1966) Preparation and characterization of syndiotactic polypropylene. J Polym Sci A Polym Chem 4(7):1861–1884
Bovey FA, Tiers GVD (1960) Polymer NSR spectroscopy. II. The high resolution spectra of methyl methacrylate polymers prepared with free radical and anionic initiators. J Polym Sci 44(143):173–182
Moore EPJ (1996) Polypropylene handbook: polymerization, characterization, properties, applications. Hanser Publishers, Munich
Uehara H, Yamazaki Y, Kanamoto T (1996) Tensile properties of highly syndiotactic polypropylene. Polymer 37(1):57–64
Collette JW, Tullock CW, MacDonald RN, Buck WH, Su ACL, Harrell JR, Mulhaupt R, Anderson BR (1989) Elastomeric polypropylenes from alumina-supported tetraalkyl Group IVB catalysts. 1. Synthesis and properties of high molecular weight stereoblock homopolymers. Macromolecules 22(10):3851–3858
Corradini P, Guerra G, Pucciariello R (1985) New model of the origin of the stereospecificity in the synthesis of syndiotactic polypropylene. Macromolecules 18(10):2030–2034
Kaminsky W (1998) Highly active metallocene catalysts for olefin polymerization. J Chem Soc Dalton Trans 9:1413–1418
Wild FRWP, Zsolnai L, Huttner G, Brintzinger HH (1982) ansa-Metallocene derivatives IV. Synthesis and molecular structures of chiral ansa-titanocene derivatives with bridged tetrahydroindenyl ligands. J Organomet Chem 232(1):233–147
Tshuva EY, Goldberg I, Kol M (2000) Isospecific living polymerization of 1-hexene by a readily available nonmetallocene C2-symmetrical zirconium catalyst. J Am Chem Soc 122(43):10706–10707
Marques MM, Correia SG, Ascenso JR, Ribeiro AFG, Gomes PT, Dias AR, Foster P, Rausch MD, Chien JCW (1999) Polymerization with TMA-protected polar vinyl comonomers. I. Catalyzed by group 4 metal complexes with η5-type ligands. J Polym Sci A Polym Chem 37(14):2457–2469
Luo S, Vela J, Lief GR, Jordan RF (2007) Copolymerization of ethylene and alkyl vinyl ethers by a (phosphine- sulfonate)PdMe catalyst. J Am Chem Soc 129(29):8946–8947
Nozaki K, Kusumoto S, Noda S, Kochi T, Chung LW, Morokuma K (2010) Why did incorporation of acrylonitrile to a linear polyethylene become possible? Comparison of phosphine–sulfonate ligand with diphosphine and imine–phenolate ligands in the Pd-catalyzed ethylene/acrylonitrile copolymerization. J Am Chem Soc 132(45):16030–16042
Leicht H, Gottker-Schnetmann I, Mecking S (2013) Incorporation of vinyl chloride in insertion polymerization. Angew Chem 52(14):3963–3966
Ito S, Munakata K, Nakamura A, Nozaki K (2009) Copolymerization of vinyl acetate with ethylene by palladium/alkylphosphine–sulfonate catalysts. J Am Chem Soc 131(41):14606–14607
Johnson LK, Mecking S, Brookhart M (1996) Copolymerization of ethylene and propylene with functionalized vinyl monomers by palladium(II) catalysts. J Am Chem Soc 118(1):267–268
Gaikwad SR, Deshmukh SS, Gonnade RG, Rajamohanan PR, Chikkali SH (2015) Insertion copolymerization of difunctional polar vinyl monomers with ethylene. ACS Macro Lett 4(9):933–937
Guironnet D, Caporaso L, Neuwald B, Göttker-Schnetmann I, Cavallo L, Mecking S (2010) Mechanistic insights on acrylate insertion polymerization. J Am Chem Soc 132(12):4418–4426
Suzuki Y, Hayashi T (1997) JP Patent 10298231 to Mitsui Chemicals Inc., Japan
Stibrany RT, Schulz DN, Kacker S, Patil AO (1997) WO Patent Application 9930822 to Exxon Research and Engineering Company
Britovsek GJP, Bruce M, Gibson VC, Kimberley BS, Maddox PJ, Mastroianni S, McTavish SJ, Redshaw C, Solan GA, Stromberg S, White AJP, Williams DJ (1999) Iron and cobalt ethylene polymerization catalysts bearing 2,6-bis(imino)pyridyl ligands: synthesis, structures, and polymerization studies. J Am Chem Soc 121(38):8728–8740
Ittel SD, Johnson LK, Brookhart M (2000) Late-metal catalysts for ethylene homo- and copolymerization. Chem Rev 100(4):1169–1204
Small BL, Brookhart M (1999) Polymerization of propylene by a new generation of iron catalysts: mechanisms of chain initiation, propagation, and termination. Macromolecules 32(7):2120–2130
Small BL, Brookhart M (1998) Iron-based catalysts with exceptionally high activities and selectivities for oligomerization of ethylene to linear α-olefins. J Am Chem Soc 120(28):7143–7144
Nomura K, Warit S, Imanishi Y (1999) Olefin polymerization by the (Pybox)RuX2(ethylene)–MAO catalyst system. Macromolecules 32(14):4732–4734
Carrick WL, Kluiber RW, Bonner EF, Wartman LH, Rugg FM, Smyth JJ (1960) Transition metal catalysts. I. Ethylene polymerization with a soluble catalyst formed from an aluminum halide, tetraphenyltin and a vanadium halide. J Am Chem Soc 82(15):3883–3887
Nomura K, Zhang S (2011) Design of vanadium complex catalysts for precise olefin polymerization. Chem Rev 111(3):2342–2362
Junghanns E, Gumboldt O, Bier G (1962) Polymerization of ethylene and propylene to amorphous copolymers with catalysts made from vanadium oxychloride and aluminum haloalkylene. Makromol Chem 58(1):18–42
Christman DL, Keim GI (1968) Reactivities of nonconjugated dienes used in preparation of terpolymers in homogeneous systems. Macromolecules 1(4):358–363
Doi Y, Ueki S, Keii T (1978) “Living” coordination polymerization of propene initiated by the soluble V(acac)3-Al(C2H5)2Cl system. Macromolecules 12(5):814–819
Doi Y, Koyama T, Soga K (1985) Synthesis of a propene—methyl methacrylate diblock copolymer via “living” coordination polymerization. Makromol Chem 186(1):11–15
Ma Y, Reardon D, Gambarotta S, Yap G, Zahalka H, Lemay C (1999) Vanadium-catalyzed ethylene–propylene copolymerization: the question of the metal oxidation state in Ziegler–Natta polymerization promoted by (β-diketonate)3V. Organometallics 18(15):2773–2781
Brandsma MJR, Brussee EAC, Meetsma A, Hessen B, Teuben JH (1998) An amidinate ligand with a pendant amine functionality; synthesis of a vanadium(III) complex and ethene polymerization catalysis. Eur J Inorg Chem 1998(12):1867–1870
Brussee EAC, Meetsma A, Hessen B, Teuben JH (1998) Electron-deficient vanadium(III) alkyl and allyl complexes with amidinate ancillary ligands. Organometallics 17(18):4090–4095
Feghali K, Harding DJ, Reardon D, Gambarotta S, Yap G, Wang Q (2002) Stability of metal–carbon bond versus metal reduction during ethylene polymerization promoted by a vanadium complex: the role of the aluminum cocatalyst. Organometallics 21(5):968–976
Janas Z, Wiśniewska D, Jerzykiewicz LB, Sobota P, Drabenta K, Szczegot K (2007) Synthesis, structural studies and reactivity of vanadium complexes with tridentate (OSO) ligand. Dalton Trans:2065–2069
Hagen H, Boersma J, Lutz M, Spek AL, van Koten G (2001) Vanadium(III) and -(IV) complexes with O,N-chelating aminophenolate ligands: synthesis, characterization and activity in ethene/propene copolymerization. Eur J Inorg Chem 2001(1):117–123
Golisz SR, Bercaw JE (2009) Synthesis of early transition metal bisphenolate complexes and their use as olefin polymerization catalysts. Macromolecules 42(22):8751–8762
Lorber C, Donnadieu B, Choukroun R (2000) Synthesis and X-ray characterization of a monomeric Cp-free d1-imido–vanadium(IV) complex. Dalton Trans (24):4497–4498
Desmangles N, Gambarotta S, Bensimon C, Davis S, Zahalka HJ (1998) Preparation and characterization of (R2N)2VCl2 [R=Cy, i-Pr] and its activity as olefin polymerization catalyst. Organomet Chem 562(1):53–60
Biazek M, Czaja K (2008) Dichlorovanadium (IV) complexes with salen-type ligands for ethylene polymerization. J Polym Sci A Polym Chem 46(20):6940–6949
Hagen H, Bezemer C, Boersma J, Kooijman H, Lutz M, Spek AL, van Koten G (2000) Vanadium(IV) and -(V) complexes with O,N-chelating aminophenolate and pyridylalkoxide ligands. Inorg Chem 39(18):3970–2977
Liguori D, Centore R, Csok Z, Tuzi A (2004) Polymerization of propene and 1,3-butadiene with vanadyl(V) monoamidinate precatalysts and MAO or dialkylaluminum chloride cocatalysts. Macromol Chem Phys 205(8):1058–1063
Meppelder GM, Halbach TS, Spaniol TP, Mülhaupt R, Okuda J (2009) A vanadium(V) complex with a tetradentate [OSSO]-type bis(phenolato) ligand: synthesis, structure, and ethylene polymerization activity. J Organomet Chem 694(7):1235–1237
Redshaw C, Rowan MA, Warford L, Homden DM, Arbaoui A, Elsegood MRJ, Dale SH, Yamato T, Casas CP, Matsui S, Matsuura S (2007) Oxo- and Imidovanadium complexes incorporating methylene- and dimethyleneoxa-bridged calix[3]- and -[4]arenes: synthesis, structures and ethylene polymerisation catalysis. Chem Eur J 13(4):1090–1107
Nomura K, Sagara A, Imanishi Y (2002) Olefin polymerization and ring-opening metathesis polymerization of norbornene by (arylimido)(aryloxo)vanadium(v) complexes of the type VX2(NAr)(OAr’). Remarkable effect of aluminum cocatalyst for the coordination and insertion and ring-opening metathesis polymerization. Macromolecules 35(5):1583–1590
Wang W, Nomura K (2005) Remarkable effects of aluminum cocatalyst and comonomer in ethylene copolymerizations catalyzed by (Arylimido)(aryloxo)vanadium complexes: efficient synthesis of high molecular weight ethylene/norbornene copolymer. Macromolecules 38(14):5905–5913
Takasao G, Wada T, Thakur A, Chammingkwan P, Terano M, Taniike T (2019) Machine learning-aided structure determination for TiCl4–capped MgCl2 nanoplate of heterogeneous Ziegler–Natta catalyst. ACS Catal 9(3):2599–2609
Vittoria A, Meppelder A, Friederichs N, Busico V, Cipullo R (2020) Ziegler–Natta catalysts: regioselectivity and “hydrogen response”. ACS Catal 10(1):644–651
Yu Y, Cipullo R, Boisson C (2019) Alkynyl ether labeling: a selective and efficient approach to count active sites of olefin polymerization catalysts. ACS Catal 9(4):3098–3103
Desert X, Carpentier JF, Kirillov E (2019) Quantification of active sites in single-site group 4 metal olefin polymerization catalysis. Coord Chem Rev 386(1):50–68
Moscato BM, Zhu B, Landis CR (2010) GPC and ESI-MS analysis of labeled poly(1-hexene): rapid determination of initiated site counts during catalytic alkene polymerization reactions. J Am Chem Soc 132(41):14352–14354
Bossers KW, Valadian R, Zanoni S, Smeets R, Friederichs N, Garrevoet J, Meirer F, Weckhuysen BM (2020) Correlated X-ray ptychography and fluorescence nano-tomography on the fragmentation behavior of an individual catalyst particle during the early stages of olefin polymerization. J Am Chem Soc 142(8):3691–3695
Piovano A, Thushara KS, Morra E, Chiesa M, Groppo E (2016) Unraveling the catalytic synergy between Ti3+ and Al3+ sites on a chlorinated Al2O3: a tandem approach to branched polyethylene. Angew Chem 128(37):11369–11372
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Sinha, A.S.K., Ojha, U. (2021). Evolution of Ziegler-Natta Catalysts for Polymerization of Olefins. In: Pant, K.K., Gupta, S.K., Ahmad, E. (eds) Catalysis for Clean Energy and Environmental Sustainability. Springer, Cham. https://doi.org/10.1007/978-3-030-65021-6_21
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