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Progress in Chemistry 2019, Vol. 31 Issue (7): 929-938 DOI: 10.7536/PC181205 Previous Articles   Next Articles

Olefin Polymerization with Nitrogen-Coordinated Half-Metallocene Catalyst Systems

Shuzhang Qu, Taoyi Zhang*(), Wei Wang*()   

  1. Beijing Research Institute of Chemical Industry(BRICI), SINOPec, Beijing 100013, China
  • Received: Online: Published:
  • Contact: Taoyi Zhang, Wei Wang
  • About author:
    * E-mail: (Taoyi Zhang)
    (Wei Wang)
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The recent study of the half-metallocene compounds ligated with nitrogen-containing groups as catalysts for precise olefin polymerization has been reviewed in this article. Studies have found that these nitrogen-coordinated catalysts exhibit unique properties in the polymerization of olefin monomers, especially for the copolymerization of ethylene. These catalysts can not only obtain new copolymers, which cannot be synthesized by Ziegler-Natta catalysts and traditional metallocene catalysts, but also show the copolymerization activities superior to other half-metallocene catalysts. Modification of both cyclopentadienyl fragments and anionic ancillary donor ligands is the key for the improvement of polymerization behaviors. This article relates to the homopolymerization of ethylene and the copolymerization of ethylene with α-olefins(hexene-1, octene-1, etc.), styrene and cyclic olefins(norbornene, tetracyclododecene, etc).

Key words: nitrogen-coordinated half-metallocene, olefin polymerization, copolymerization
Fig. 1 Half-metallocene with amino ligand
Table 1 Ethylene polymerization by 25~29[24][a]
Cat. T
(℃)		 Al/Ti
mol. ratio		 Activity[b] Mη[c]
10-4		 Tm[d]
(℃)
25[e] 20 200 316 371.5 137.9
25[e] 35 200 330 105.5 136.5
26[e] 20 200 340 383.5 137.7
26[e] 35 200 354 138.8 136.9
27[e] 20 200 220 325.4 136.8
27[e] 35 200 231 103.3 136.4
28 20 200 1852 94.1 138.9
28 35 200 1974 70.6 138.1
28 50 200 1270 55.9 139.0
28 35 300 1692 83.5 139.5
28 35 400 1594 68.3 140.1
29 20 200 1806 96.8 139.3
29 35 200 1924 82.1 139.0
29 35 300 1856 58.4 137.9
Table 2 Ethylene-hexene-1 copolymerization by 25~29[24][a]
Cat. 1-Hex
(mol·L-1)		 Activity[b] Incorpor.[c]
(mol %)		 Mw[d]
×10-4		 pdi[d] rErH[e]
25[f] 1.5 142 9.5 15.72 3.41 -
26[f] 1.5 152 10.0 10.42 3.62 0.547
27[f] 1.5 72 8.7 10.04 3.53 -
28 0.5 3364 18.4 26.33 2.42 0.485
28 1.5 3608 31.8 20.14 2.55 0.393
29 1.5 1610 35.9 17.45 3.31 0.437
Table 3 Ethylene polymerization of 30~39[25]
Cat. Activity (kg-PE/mol-Ti-h) Mn×10-3 pdi
30[a] 5550 22.7 2.4
31[a] 1500 20.7 2.4
32[a] 1740 22.8 2.3
33[a] 1950 21.8 2.3
34[a] 330 2.18 2.2
35[a] 750 2.61 2.1
36[a] 930 2.91 3.6
37[a] 1410 3.17 1.7
38[b] 10 020 112 2.5
39[b] 8100 160 2.8
Fig. 2 Half-metallocene with ketimide ligand
Fig. 3 Half-metallocene with phosphinimide ligand
Table 4 Comparison for ethylene-octene-1 copolymerization by 97, 98 and Cp*Ti[NP(tBu)3]C12[38][a]
Cat. Activity[b] Incorpor. (mol %)[c] Mw ×10-3 pdi
97 9.0 8 543 2.44
98 8.0 8 752 2.17
—[d] 23 5 204 3.32
Fig. 4 Half-metallocene with other types of N-containing ligand
[1]
Gladysz J A . Chem. Rev., 2000,100(4):1167.
[2]
Gibson V C, Spitzmesser S K . Chem. Rev., 2003,103(1):283.
[3]
Rodriguez-Delgado A, Chen E Y A . Macromolecules, 2005,38(7):2587.
[4]
Kaminsky W . Adv. Catal., 2001,46(02):89.
[5]
Klosin J, Fontaine P P, Figueroa R . Acc. Chem. Res., 2015,48(7):2004.
[6]
Collins R A, Russell A F, Mountford P . Appl. Petrochem. Res., 2015,5(3):153.
[7]
Alt H G, Koppl A . Chem. Rev., 2000,100(4):1205.
[8]
Nomura K, Liu J Y, Padmanabhan S, Kitiyanan B . J. Mol. Catal. A: Chem., 2007,267:1.
[9]
Makio H, Terao H, Iwashita A, Fujita T, . Chem. Rev., 2011,111:2363.
[10]
Ittel S D, Johnson L K, Brookhart M . Chem. Rev., 2000,100(4):1169.
[11]
McKnight A L, Waymouth R M . Chem. Rev., 2010,30(4):2587.
[12]
Nomura K, Naga N, Miki M, Yanagi K, Imai A . Organometallics, 1998,17(11):2152.
[13]
Stephan D W, Guérin F, Spence R E V H, Koch L, Gao X, Brown S J, Swabey J W, Wang Q, Xu W, Zoricak P, Harrison D G . Organometallics, 2000,18(11):2046.
[14]
Kretschmer W P, Dijkhuis C, Meetsma A, Hessen B, Teuben J H . Chem. Commun., 2002,114(6):608.
[15]
Zhang S, Piers W E, Gao X, Parvez M . J.Am. Chem. Soc., 2000,122(23):5499.
[16]
Jayaratne K C, Sita L R . J.Am. Chem. Soc., 2000,122(5):958.
[17]
Wang W, Zheng G, Wang H T . e-Polymers, 2014,14:277.
[18]
王伟(Wang W), 郑刚(Zheng G) . 化学进展 (Progress in Chemistry), 2009,21(4):677.
[19]
Rusli W, Tay B Y, Stubbs L P, Meurs M V, Tan J, Jacob C, Chia S C, Woo Y L, Wang C . J.Organomet. Chem., 2011,696(11):2414.
[20]
Dureen M A, Brown C C, Morton J G, Stephan D W . Dalton Trans., 2011,40(12):2861.
[21]
Rajesh A, Sivaram S . Polymer. Eng. Sci., 2011,51(10):2103.
[22]
米普科(Mi P K), 孔晓娟(Kong X J), 许胜(Xu S), 朱玉玲(Zhu Y L), 任迎春(Ren Y C) . 分子催化 (Journal of Molecular Catalysis(China)), 2012,26(6):493.
[23]
Nomura K, Fujii K . Macromolecules, 2003,36(8):2633.
[24]
Liu, K, Wu Qn, Gao W, Mu Y, Ye L . WEur. J. Inorg. Chem., 2011(12):1901.
[25]
Saeed I, Katao S, Nomura K . Organometallics, 2009,28(1):111.
[26]
Narayana G V, Xu G, Wang D, Frey W, Buchmeiser M R . ChemPlusChem, 2014,79(1):151.
[27]
Narayana G V, Xu G, Wang D, Speiser M, Frey W, Buchmeiser M R . Macromol. Chem. Phys., 2014,215(20):2007.
[28]
Xu G, Narayana G V, Speiser M, Wang D, Zhou Y L, Buchmeiser M R . Macromol. Chem. Phys., 2014,215(9):893.
[29]
Park J H, Do S H, Cyriac A, Yun H, Lee B Y . Dalton Trans., 2010,39(41):9994.
[30]
Kim S H, Park J H, Song B G, Yoon S W, Go M J, Lee J S, Lee B Y . Catalysts, 2013,3:104.
[31]
Dias A R, Duarte M T, Fernandes A C, Fernandes S, Marques M M, Martins A M, Silva J F, Rodrigues S S . J.Organomet. Chem., 2004,689(1):203.
[32]
Nomura K, Fujita K, Fujiki M . J. Mol. Catal. A, 2004,220(2):133.
[33]
Nomura K, Yamada J, Wang W, Liu J . J.Organomet. Chem., 2007,692(21):4675.
[34]
Itagaki K, Nomura K . Macromolecules, 2009,42(14):5097.
[35]
Nomura K, Kakinuki K, Fujiki M, Itagaki K . Macromolecules, 2008,41(23):8974.
[36]
Zhao W, Nomura K . Macromolecules, 2016,49(1):59.
[37]
Zhang H, Nomura K . J.Am. Chem. Soc., 2005,127(26):9364. https://www.ncbi.nlm.nih.gov/pubmed/15984852

doi: 10.1021/ja052198z pmid: 15984852
[38]
Park E S, Ji H P, Yun H, Lee B Y . J.Organomet. Chem., 2011,696(11):2451.
[39]
Nomura K, Fukuda H, Katao S, Fujiki M, Kim H J, Kim DH, Zhang S . Dalton Trans., 2011,40(31):7842.
[40]
Nomura K, Fukuda H, Apisuk W, Trambitas A J, Kitiyanan B, Tamm M . J. Mol. Catal. A., 2012, 363-364(12):501.
[41]
Nomura K, Fukuda H, Matsuda H, Katao S, Patamma S . J.Organomet. Chem., 2015,798:375.
[42]
Nomura K, Patamma S, Matsuda H, Katao S, Tsutsumia K, Fukudab H . RSC Adv., 2015,5(79):64503.
[43]
Apisuk W, Trambitas A G, Kitiyanan B, Tamm M, Nomura K . J. Polym. Sci. A, 2013,51(12):2575.
[44]
Apisuk W, Ito H, Nomura K . J. Polym. Sci. A, 2016,54(17):2662.
[45]
Stelzig S H, Tamm M, Waymouth R M . J. Polym. Sci. A, 2008,46(18):6064.
[46]
Ijpeij E G, Coussens B, Zuideveld M A, Doremaele GH, Mountford P, Lutz M, Spek AL . Chem. Commun., 2010,46(19):3339.
[47]
Collins R A, Russell A F, Scott R T W, Bernardoet R, Doremaele G H J, Berthoud A, Mountford P . Organometallics, 2017,36:2167.
[48]
Varga V, Večeča M, Gyepes R, Pinkas J, Horáček M, Merna J, Lamač M . Chemcatchem, 2017,9(16):3270.
[49]
Stephan D W, Stewart J C, Guérin F, Spence R E H, Xu W, Harrison D G . Organometallics, 1999,18(7):1116.
[50]
Spence R E H, Stephan D W, Brown S J, Wurz R P, Jeremic D . US 6355744, 2000.
[51]
Carraz C A, Stephan D W . Organometallics, 2000,19(19):3791.
[52]
Yue N L S, Stephan D W . Organometallics, 2001,20(11):2303.
[53]
Stephan D W, Stewart J C, Guérin F, Courtenay S, Kickham J, Hollink E, Beddie C, Hoskin A, Graham T, Wei PR, Spence R E H, Xu W, Koch L, Gao X L, Harrison D G . Organometallics, 2003,22(9):1937.
[54]
Hollink E, Wei P, Stephan D W . Organometallics, 2004,23(7):1562.
[55]
Alhomaidan O, Bai G, Stephan D W . Organometallics, 2008,27(27):6343.
[56]
Ramos A, Stephan D W . Dalton Trans., 2010,39(5):1328.
[57]
Yadav K, McCahill J S, Bai G, Stephan D W . Dalton Trans, 2009,9(9):1636.
[58]
Hollink E, Wei P, Stephan D W . Can. J. Chem., 2004,82(8):1304.
[59]
Beddie C, Wei P, Stephan D W . Can. J. Chem., 2006,84(5):755.
[60]
Huang J L, Lian B, Qian Y L, Zhou W Z, Chen W, Zheng G . Macromolecules, 2002,35(13):4871.
[61]
Yan Q, Yang W H, Chen L Q, Wang L, Redshaw C, Sun W H . J.Organomet. Chem., 2014,753(1):34.
[62]
Huang W, Sun W H, Redshaw C . Dalton Trans., 2011,40(25):6802.
[63]
Huang W, Li B X, Wang Y H, Zhang W J, Wang L, Li Y S, Sun W H, Redshaw C . Catal. Sci. Technol., 2011,1:1208.
[64]
Huang W, Zhang W J, Sun W H, Wang L, Redshaw C . Catal. Sci. Technol., 2012,2(10):2090.
[65]
Zuo W W, Zhang M, Sun W H . J. Polym. Sci. A, 2009,47(2):357.
[66]
Liu S R, Li B X, Liu J Y, Li Y S . Polymer, 2010,51(9):1921.
[67]
Shi X C, Jin G X . Dalton Trans., 2011,40(44):11914.
[68]
Qiao Y L, Hu P, Jin G X . Chinese J. Polym. Sci., 2013,31(5):760.
[69]
Larocque T G, Dastgir S, Lavoie G G . Organometallics, 2013,32(15):4314.
[70]
Bott R K J, Hughes D L, Bochmann M, Schormann M, Lancaster S . J.Organomet. Chem., 2003,665(1/2):135.
[71]
Chen Q H, Huang J L, Yu J . Inorg. Chem. Commun., 2005,8(5):444.
[72]
Coles S R, Clarkson G J, Gott A L, Munslow L J, Spitzmesser S K, Scott P . Organometallics, 2006,25(26):6019.
[73]
Zhang J, Lin Y J, Jin G X . Organometallics, 2007,26(16):4042.
[74]
Zhang H, Katao S, Nomura K, Huang J L . Organometallics, 2007,26(24):5967.
[75]
Zuo W W, Zhang S, Sun W H . J. Polym. Sci. A, 2008,46(10):3396.
[76]
Zhang W J, Huang W, Liang T L, Sun W H . Chinese J. Polym. Sci., 2013,31(4):601.
[77]
Zhang Q, Tao X, Gao W, Song T T, Mu Y . J.Organomet. Chem., 2016,804:18.
[78]
Qi C H, Zhang S B, Sun J H . J.Organomet. Chem., 2005,690(12):2941.
[79]
Dove A P, Xie X, Waymouth R M . Chem. Commun., 2005,( 16):2152.
[80]
Dove A P, Kiesewetter E T, Ottenwaelder X, Waymouth R M . Organometallics, 2009,28(2):405.
[81]
Liu S, Sun W H, Zeng Y, Wang D, Zhang W J, Li Y . Organometallics, 2010,29(11):2459.
[82]
Harkness M B, Alvarado E, Badaj A C, Skrela B C, Fan L, Lavoie G G . Organometallics, 2013,32(11):3309.
[83]
Nomura K, Fukuda H, Katao S, Fujiki M, Kim H J, Kim D H, Saeed I . Macromolecules, 2011,44(7):1986.
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