Citation: Xiang-Yang Song, Qiong Ma, Hao-Bo Yuan, Zheng-Guo Cai. Synthesis of Hydroxy-functionalized Ultrahigh Molecular Weight Polyethylene Using Fluorenylamidotitanium Complex[J]. Chinese Journal of Polymer Science, ;2018, 36(2): 171-175. doi: 10.1007/s10118-018-2046-6 shu

Synthesis of Hydroxy-functionalized Ultrahigh Molecular Weight Polyethylene Using Fluorenylamidotitanium Complex

State Key Laboratory for Modification of Chemical Fibers and Polymer Materials, College of Materials Science and Engineering, Donghua University, Shanghai 201620, China

Corresponding author: Zheng-Guo Cai, caizg@dhu.edu.cn
Received Date: 25 August 2017
Accepted Date: 21 September 2017
Available Online: 16 November 2017

Copolymerizations of ethylene and 1-dodecene were conducted with a series of ansa-fluorenylamidodimethyltitanium complexes, [t-BuNSiMe₂Flu]TiMe₂ (1a), [t-BuNSiMe₂(2, 7-^tBu₂Flu)]TiMe₂ (1b), and[(1-adamantyl)NSiMe₂(2, 7-^tBu₂Flu)]TiMe₂ (1c) activated by modified methylaluminoxane. The activity increased by the introduction of the alkyl groups on the fluorenyl and amido ligands, and 1c produced the highest molecular weight copolymers. Complex 1c also promoted copolymerization of ethylene and ⁱBu₃Al protected 10-undecen-1-ol with high activity (~2000 kg·mol^-1·h^-1), affording hydroxy-functionalized ultrahigh molecular weight polyethylene. The hydroxy content of the copolymers obtained was controllable by changing comonomer feed ratio. The introduction of a small amount of hydroxy group can alter the surface properties of polyethylene.
- Single-site catalyst,
- Ethylene,
- Polar monomer,
- Copolymerization,
- Hydroxy-functionalized polyethylene
1. [1]
  Kurtz, S. M. The UHMWPE Handbook, "Ultra high molecular weight polyethylene in total joint replacement", Elsevier Academic Press, New York, 2004.
2. [2]
  Dong J. Y., Hu Y.. Design and synthesis of structurally well-defined functional polyolefins via transition metal-mediated olefin polymerization chemistry[J]. Coord. Chem. Rev., 2006,250(1-2):47-65. doi: 10.1016/j.ccr.2005.05.008
3. [3]
  Franssen N. M. G., Reek J. N. H., Bruin B. D.. Synthesis of functional 'polyolefins': state of the art and remaining challenges[J]. Chem. Soc. Rev., 2013,42(13):5809-5832. doi: 10.1039/c3cs60032g
4. [4]
  Iizuka Y., Sugiyama J., Hagihara H.. Unexpected mechanical properties of functionalized polypropylene: tensile test, charpy impact tensile test, DSC, and WAXD analysis of poly(5-hexen-1-ol-co-propylene)[J]. Macromolecules, 2009,42(7):2321-2323. doi: 10.1021/ma802860b
5. [5]
  Hagihara H., Ito K., Kimata S.. Comprehensive study of altered amorphous structure in functionalized polypropylenes exhibiting high tensile strength[J]. Macromolecules, 2013,46(11):4432-4437. doi: 10.1021/ma4003837
6. [6]
  Boffa L. S., Novak B. M.. Copolymerization of polar monomers with olefins using transition-metal complexes[J]. Chem. Rev., 2000,100(4):1479-1493. doi: 10.1021/cr990251u
7. [7]
  Chen E. Y. X.. Coordination polymerization of polar vinyl monomers by single-site metal catalysts[J]. Chem. Rev., 2009,109(11):5157-5214. doi: 10.1021/cr9000258
8. [8]
  Nakamura A., Ito S., Nozaki K.. Coordination-insertion copolymerization of fundamental polar monomers[J]. Chem. Rev., 2009,109(11):5215-5244. doi: 10.1021/cr900079r
9. [9]
  Carrow B. P., Nozaki K.. Transition-metal-catalyzed functional polyolefin synthesis: effecting control through chelating ancillary ligand design and mechanistic insights[J]. Macromolecules, 2014,47(8):2541-2555. doi: 10.1021/ma500034g
10. [10]
  Aaltonen P., Lofgren B.. Synthesis of functional polyethylenes with soluble metallocene/methylaluminoxane catalyst[J]. Macromolecules, 1995,28(15):5353-5357. doi: 10.1021/ma00119a027
11. [11]
  Aaltonen P., Lofgren B.. Functionalization of polyethylenes via metallocene/methylaluminoxane catalyst[J]. Eur. Polym. J., 1997,33(8):1187-1190. doi: 10.1016/S0014-3057(97)00011-6
12. [12]
  Hakala K., Lofgren B., Helaja T.. Copolymerizations of oxygen-functionalized olefins with propylene using metallocene/methylaluminoxane catalyst[J]. Eur. Polym. J., 1998,34(8):1093-1097. doi: 10.1016/S0014-3057(97)00227-9
13. [13]
  Hakala K., Helaja T., Lofgren B.. Metallocene/ methylaluminoxane-catalyzed copolymerizations of oxygen-functionalized long-chain olefins with ethylene[J]. J. Polym. Sci., Part A: Polym. Chem., 2000,38(11):1966-1971. doi: 10.1002/(ISSN)1099-0518
14. [14]
  Marques M. M., Correia S. G., Ascenso J. R., Ribeiro A. F. G., Gomes P. T., Dias A. R., Foster P., Rausch M. D., Chien J. C. W.. Polymerization with TMA-protected polar vinyl comonomers[J]. I. catalyzed by group 4 metal complexes with eta(5)-type ligands. J. Polym. Sci., Part A: Polym. Chem., 1999,37(14):2457-2469.
15. [15]
  Hagihara H., Murata M., Uozumi T.. Alternating copolymerization of ethylene and 5-hexen-1-ol with [ethylene(1-indenyl)(9-fluorenyl)]-zirconium dichloride/ methylaluminoxane as the catalyst[J]. Macromol. Rapid Commun., 2001,22(5):353-357. doi: 10.1002/(ISSN)1521-3927
16. [16]
  Hagihara H., Tsuchihara K., Takeuchi K., Murata M., Ozaki H., Shiono T.. Copolymerization of ethylene or propylene with alpha-olefins containing hydroxyl groups with zirconocene/methylaluminoxane catalyst[J]. J. Polym. Sci., Part A: Polym. Chem., 2004,42(1):52-58. doi: 10.1002/(ISSN)1099-0518
17. [17]
  Imuta J., Kashiwa N., Toda Y.. Catalytic regioselective introduction of allyl alcohol into the nonpolar polyolefins: development of one-pot synthesis of hydroxyl-capped polyolefins mediated by a new metallocene IF catalyst[J]. J. Am. Chem. Soc., 2002,124(7):1176-1177. doi: 10.1021/ja0174377
18. [18]
  Kawahara N., Kojoh S., Matsuo S., Kaneko H., Matsugi T., Kashiwa N.. Investigation of insertion reaction of 10-undecen-1-ol protected with alkylaluminum in En(Ind)(₂)ZrCl₂/MAO catalyst system[J]. J. Mol. Catal. A: Chem., 2005,241(1-2):156-161. doi: 10.1016/j.molcata.2005.07.010
19. [19]
  Zhang X., Chen S., Li H., Zhang Z., Lu Y., Wu C., Hu Y.. Highly active copolymerization of ethylene with 10-undecen-1-ol using phenoxy-based zirconium/methylaluminoxane catalysts[J]. J. Polym. Sci., Part A: Polym. Chem., 2005,43(23):5944-5952. doi: 10.1002/(ISSN)1099-0518
20. [20]
  Zhang X., Chen S., Li H., Zhang Z., Lu Y., Wu C., Hu Y.. Copolymerizations of ethylene and polar comonomers with bis(phenoxyketimine) group Ⅳ complexes: effects of the central metal properties[J]. J. Polym. Sci., Part A: Polym. Chem., 2007,45(1):59-68. doi: 10.1002/(ISSN)1099-0518
21. [21]
  Huang Y., Yang K., Dong J. Y.. Copolymerization of ethylene and 10-undecen-1-ol using a montmorillonite-intercalated metallocene catalyst: synthesis of polyethylene/montmorillonite nanocomposites with enhanced structural stability[J]. Macromol. Rapid Commun., 2006,27(15):1278-1283. doi: 10.1002/(ISSN)1521-3927
22. [22]
  Zuo W., Zhang M., Sun W. H.. Imino-indolate half-titanocene chlorides: synthesis and their ethylene (co-)polymerization[J]. J. Polym. Sci., Part A: Polym. Chem., 2009,47(2):357-372. doi: 10.1002/pola.v47:2
23. [23]
  Fernandes M., Kaminsky W.. Copolymerization of ethylene with 2, 7-octadienyl methyl ether in the presence of metallocene and nickel diimine catalysts[J]. Macromol. Chem. Phys., 2009,210(7):585-593. doi: 10.1002/macp.v210:7
24. [24]
  Terao H., Ishii S., Mitani M., Tanaka H., Fujita T.. Ethylene/polar monomer copolymerization behavior of bis(phenoxy-imine)Ti complexes: formation of polar monomer copolymers[J]. J. Am. Chem. Soc., 2008,130(52):17636-17637. doi: 10.1021/ja8060479
25. [25]
  Hong M., Wang Y. X., Mu H. L., Li Y. S.. Efficient synthesis of hydroxylated polyethylene via copolymerization of ethylene with 5-norbornene-2-methanol using bis(beta-enaminoketonato) titanium catalysts[J]. Organometallics, 2011,30(17):4678-4686. doi: 10.1021/om200526n
26. [26]
  Yang X. H., Liu C. R., Wang C., Sun X. L., Guo Y. H., Wang X. K., Wang Z., Xie Z., Tang Y.. [(O-NS^R)]TiCl₃-catalyzed copolymerization of ethylene with functionalized olefins[J]. Angew. Chem. Int. Ed., 2009,48(43):8099-8102. doi: 10.1002/anie.v48:43
27. [27]
  Chen Z., Li J. F., Tal W. J., Sun X. J., Yang X. H., Tang Y.. Copolymerization of ethylene with functionalized olefins by[J]. Macromolecules, 2013,46(7):2870-2875. doi: 10.1021/ma400283p
28. [28]
  Shiono T.. Living polymerization of olefins with ansa-dimethylsilylene(fluorenyl)(amido) dimethyltitanium-based catalysts[J]. Polym. J., 2011,43(4):331-351. doi: 10.1038/pj.2011.13
29. [29]
  Cai Z., Su H., Shiono T.. Precise synthesis of olefin block copolymers using a syndiospecific living polymerization system[J]. Chinese J. Polym. Sci., 2013,31(4):541-549. doi: 10.1007/s10118-013-1250-7
30. [30]
  Sun Y., Xu B., Shiono T., Cai Z.. Highly active ansa-(fluorenyl)(amido)titanium-based catalysts with low load of methylaluminoxane for syndiotactic-specific living polymerization of propylene[J]. Organometallics, 2017. doi: 10.1021/acs.organomet.7b00415
31. [31]
  Cai Z., Ikeda T., Akita M., Shiono T.. Substituent effects of tert-butyl groups on fluorenyl ligand in syndiospecific living polymerization of propylene with ansa-fluorenylamidodimethyltitanium complex[J]. Macromolecules, 2005,38(20):8135-8139. doi: 10.1021/ma050898i
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