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Synthesis and crystalline structure of poly(p-phenylene alkylene)s and poly(p-phenylene co-alkylenes)s by Kumada coupling reaction of α,ω-dibromoalkane and p-dichlorobenzene

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Abstract

Poly(p-phenylene alkylene)s were synthesized by Kumada coupling reaction of α,ω-dibromoalkane (BR) (1,6-dibromohexane (BH), 1,8-dibromooctane (BO), 1,10-dibromodecane (BD), 1,12-dibromododecane (BDD)), and p-dichlorobenzene (CB). The corresponding poly(p-phenylene alkylene)s (PPPRs) with low molecular weight were obtained in moderate yields. Polymer chain ends of methyl group was detected in 13CNMR spectroscopy, indicating preferential termination of BR. Wide angle X-ray diffraction (WAXD) profile of the poly(p-phenylene hexylene) (PPPH) showed a diffraction peak at 2θ = 20.4°. Poly(p-phenylene octylene) (PPPO), poly(p-phenylene decylene) PPPD, and poly(p-phenylene dodecylene) PPPDD showed the different WAXD profiles from that of PPPH, and the diffraction peaks at around 2θ = 18° and 24° were detected in their WAXD profiles. PPPD and PPPDD also showed a diffraction peak at 2θ = 21.6°, which was not detected in the WAXD profile of PPPO. FT-IR spectra in the frequency region, 710–740 cm−1, of methylene rocking vibration of the PPPRs indicated hexagonal crystal in PPPH and triclinic-based crystal in PPPO, PPPD, and PPPDD. All the PPPRs showed melting point, which decreased with increasing of methylene length of the BR used as following, PPPH: 131.2 °C, PPPO: 91.1 °C, PPPD: 84.6 °C, PPPDD: 80.1 °C,. Poly(p-phenylene co-alkylenes)s (PPPCRs) were newly prepared by polymerizations of two kinds of BRs, BH/BO, BH/BD, or BO/BD, with CB. The PPPCRs showed the lower melting temperatures than those of the corresponding PPPRs. The WAXD profiles of the PPPCRs showed the diffraction peaks derived from both the corresponding PPPRs, and their intensities were depended on the feed ratios of the BRs.

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References

  1. Galdi N, Buonerba A, Oliva L (2016) Olefin-styrene copolymers. Polymers 8:405. https://doi.org/10.3390/polym8110405

    Article  CAS  PubMed Central  Google Scholar 

  2. Haider N, Exposito T, Munoz-Escalona A, Ramos J, Vega JF (2006) Synthesis and properties pf ethylene/styrene copolymers produced by metallocene catalysts. J Appl Polym Sci 102:3420–3429. https://doi.org/10.1002/app.24147

    Article  CAS  Google Scholar 

  3. Chen H, Guest MJ, Chum S, Hilener A, Baer E (1998) Classification of ethylene-styrene interpolymers based on comonomer content. J Appl Polym Sci 70:109–119. https://doi.org/10.1002/(SICI)1097-4628(19981003)70:1%3c109::AID-APP11%3e3.0.CO;2-2

    Article  CAS  Google Scholar 

  4. Steiger D, Tervoort T, Weder C, Smith P (2000) Poly(p-phenylene alkylene)s – A forgotten class of polymers. Macromol Rapid Commun 21:405–422. https://doi.org/10.1002/(SICI)1521-3927(20000501)21:8%3c405::AID-MARC405%3e3.0.CO;2-J

    Article  CAS  Google Scholar 

  5. Sauty NF, da Silva GC, Graf R, Wagner KB (2015) Unveiling the hyperbolic thermal behaviour of poly(p-phenylene alkylene)s. Polym Chem 6:6073–6082. https://doi.org/10.1039/C5PY00625B

    Article  CAS  Google Scholar 

  6. Cramer E, Percec VJ (1990) Phase transfer Pd(0) catalyzed polymerization reactions. III. Polymerization by cross-coupling of alkyl-boron compounds and aromatic halides catalyzed by PdCl2(dppf) and bases. Polym Sci Part A Polym Chem 28:3029–3046. https://doi.org/10.1002/pola.1990.080281112

    Article  CAS  Google Scholar 

  7. Steiger D, Ehrenstein M, Weder C, Smith P (1998) Synthesis and Properties of Poly(p-phenylene Octylene). Macromolecules 31:1254–1260. https://doi.org/10.1021/ma971373w

    Article  CAS  Google Scholar 

  8. Ueda M, Ichikawa F (1990) Synthesis of aromatic poly(ether ketone)s by nickel-catalyzed coupling polymerization of aromatic dichloride. Macromoleules 23:926–930. https://doi.org/10.1021/ma00206a003

    Article  CAS  Google Scholar 

  9. Percec V, Bae JY, Zhao M, Hill DH (1995) Synthesis of functional polyphenylenes from substituted hydroquinones via nickel(0)-catalyzed polymerization of their bismesylates. Maromoleules 28:6726–6734. https://doi.org/10.1021/ma00124a005

    Article  CAS  Google Scholar 

  10. Sung TC, Kantor SW (1992) Atkins E D T (1992) Thermotropic hydrocarbon main-chain liquid crystalline polymers based on a biphenyl mesogen: synthesis and characterization. Maromoleules 25:2789–2795. https://doi.org/10.1021/ma00037a001

    Article  Google Scholar 

  11. Sung TC, Mallon JJ, Atkins EDT, Kantor SW (eds) (1990) Liquid-Crystalline Polmers. ACS, Washington DC

    Google Scholar 

  12. Naga N, Tsubooka M, Suehiro S, Imanishi Y (2002) Crystalline structure and thermal property of polyethylene and isotactic polypropylene containing cyclopentane units in the main chain. Macromolecules 35:3041–3047. https://doi.org/10.1021/ma0117312

    Article  CAS  Google Scholar 

  13. Naga N, Tsubooka M, Sone M, Tashiro K, Imanishi Y (2002) Crystalline structure of polyethylene containing 1,2- or 1,3-disubstituted cyclopentane units in the main chain. Macromolecules 35:9999–10003. https://doi.org/10.1021/ma021323d

    Article  CAS  Google Scholar 

  14. Naga N, Kikuchi G, Toyota A (2006) Synthesis and crystalline structure of polyethylene containing 1,3-cyclopentane units in the main chain by ring-opening methathesis copolymerization of cycloolefins following hydrogenation reaction. Polymer 47:6081–6090. https://doi.org/10.1016/j.polymer.2006.06.015

    Article  CAS  Google Scholar 

  15. Naga N, Arai R, Kikuchi G, Toyota A, Noguchi K, Sone M, Shirae F, Gotoh T, Kurosu H (2011) Crystalline structure of polyethylene containing vinylene units in the main chain. Polymer 52:4857–4866. https://doi.org/10.1016/j.polymer.2011.08.058

    Article  CAS  Google Scholar 

  16. Boz E, Wagener KB, Ghosal A, Fu R, Alamo RG (2006) Synthesis and crystallization of precision ADMET polyolefins containing halogens. Macromolecules 39:4437–4447. https://doi.org/10.1021/ma0605088

    Article  CAS  Google Scholar 

  17. Gunter L, Wegner G, Smith JA, Wagener KB (2004) Morphology and packing behavior of model ethylene/propylene copolymers with procise methylene branch placement. Colloid Polym Sci 282:773–781. https://doi.org/10.1007/s00396-004-1091-6

    Article  CAS  Google Scholar 

  18. Boz E, Nemeth AJ, Wagener KB, Jeon K, Smith R, Nazirov F, Bockstaller MR, Alamo RG (2008) Well-defined precision ethylene/vinyl fluoride polymers: Synthesis and crystalline properties. Macromolecules 41:1647–1653. https://doi.org/10.1021/ma071403n

    Article  CAS  Google Scholar 

  19. Rojas G, Unci B, Wei Y, Wagener KB (2009) Precision polyethylene: Changes in morphology as a function of alkyl bramch size. J Am Chem Soc 131:17376–17386. https://doi.org/10.1021/ja907521p

    Article  CAS  PubMed  Google Scholar 

  20. Inci B, Lieberwirth I, Steffen W, Mezger M, Graf R, Landfester K, Wagener KB (2012) Decreasing the alkyl branch frequency in precision polyethylene: effect of alkyl branch size on nanoscale morphology. Macrmolecules 45:3367–3376. https://doi.org/10.1021/ma3002577

    Article  CAS  Google Scholar 

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Authors and Affiliations

  1. Department of Applied Chemistry, College of Engineering, Material Science Course, Shibaura Institute of Technology, 3-7-15 Toyosu, Koto-ku, Tokyo, 135-8548, Japan

    Naofumi Naga, Shingo Okado & Yui Ohara

  2. Graduate School of Engineering and Science, Shibaura Institute of Technology, 3-7-5 Toyosu, Koto-ku, Tokyo, 135-8548, Japan

    Naofumi Naga

  3. Instrumentation Analysis Center, Tokyo University of Agriculture and Technology, 2-24-16, Naka-cho, Koganei, Tokyo, 184-8588, Japan

    Keiichi Noguchi

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  1. Naofumi Naga
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  2. Shingo Okado
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  4. Keiichi Noguchi
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Contributions

Conceptualization, N.N.; analysis, K.N.; investigation, N.N., S.O., and Y.O.; writing—original draft preparation, N.N.; writing—review and editing, K.N.; supervision, N.N.; project administration, N.N. All authors have read and agreed to the published version of the manuscript.

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Correspondence to Naofumi Naga.

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Naga, N., Okado, S., Ohara, Y. et al. Synthesis and crystalline structure of poly(p-phenylene alkylene)s and poly(p-phenylene co-alkylenes)s by Kumada coupling reaction of α,ω-dibromoalkane and p-dichlorobenzene. J Polym Res 29, 13 (2022). https://doi.org/10.1007/s10965-021-02849-8

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