Hydroxyl-terminated Polyethylenes Bearing Functional Side Groups: Facile Synthesis and Their Properties

Wan-Bin Zhang; Jie Luo; Yan-Meng Wang; Xiu-Zhong Zhu; Ce Zhang; Jing Liu; Mei-Le Ni; Guang-Hua Zhang

doi:10.1007/s10118-021-2572-5

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Hydroxyl-terminated Polyethylenes Bearing Functional Side Groups: Facile Synthesis and Their Properties

ARTICLE | Updated：2021-05-31

- Hydroxyl-terminated Polyethylenes Bearing Functional Side Groups: Facile Synthesis and Their Properties
- Chinese Journal of Polymer Science Vol. 39, Issue 8, Pages: 994-1003(2021)
- Affiliations：
  
  a.Shaanxi Collaborative Innovation Center of Industrial Auxiliary Chemistry and Technology, Shaanxi University of Science & Technology, Xi’an 710021, China
  b.Shaanxi Key Laboratory of Chemical Additives for Industry, College of Chemistry and Chemical Engineering, Shaanxi University of Science & Technology, Xi’an 710021, China
  c.School of Light Industry and Engineering, Qi Lu University of Technology (Shandong Academy of Sciences), Jinan 250353, China
- Author bio：
  
  zhangwanbin@sust.edu.cn (W.B.Z.)
  zhanggh@sust.edu.cn (G.H.Z.)
- Funds：
- DOI：10.1007/s10118-021-2572-5
  CLC：
- Received：09 December 2020，
  
  Revised：2021-2-6，
  
  Accepted：23 February 2021，
  
  Online First：31 May 2021，
  
  Published：18 June 2021
- Accepted：
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Zhang, W. B.; Luo, J.; Wang, Y. M.; Zhu, X. Z.; Zhang, C.; Liu, J.; Ni, M. L.; Zhang, G. H. Hydroxyl-terminated polyethylenes bearing functional side groups: facile synthesis and their properties. Chinese J. Polym. Sci. 2021, 39, 994–1003

Wan-Bin Zhang, Jie Luo, Yan-Meng Wang, et al. Hydroxyl-terminated Polyethylenes Bearing Functional Side Groups: Facile Synthesis and Their Properties[J]. Chinese Journal of Polymer Science, 2021, 39(8): 994-1003.
Zhang, W. B.; Luo, J.; Wang, Y. M.; Zhu, X. Z.; Zhang, C.; Liu, J.; Ni, M. L.; Zhang, G. H. Hydroxyl-terminated polyethylenes bearing functional side groups: facile synthesis and their properties. Chinese J. Polym. Sci. 2021, 39, 994–1003 DOI： 10.1007/s10118-021-2572-5.

Wan-Bin Zhang, Jie Luo, Yan-Meng Wang, et al. Hydroxyl-terminated Polyethylenes Bearing Functional Side Groups: Facile Synthesis and Their Properties[J]. Chinese Journal of Polymer Science, 2021, 39(8): 994-1003. DOI： 10.1007/s10118-021-2572-5.

摘要

Abstract

A series of hydroxyl-terminated polyethylenes (HTPE) bearing various functional side groups (

e.g.

carboxyl

ester and butane groups) were synthesized by the combination of ring-opening metathesis polymerization (ROMP) and visible light photocatalytic thiol-ene reaction. The products are named as

-dihydroxyl-poly[(propionyloxythio)methinetrimethylene] (HTPE

carboxyl

)

-dihydroxyl-poly[(methylpropionatethio)methinetrimethylene] (HTPE

ester

) and

-dihydroxyl-poly[(butylthio) methinetrimethylene] (HTPE

butane

)

respectively. The investigation of ROMP indicated that the molecular weight of resultant hydroxyl-terminated polybutadiene (HTPB) can be tailored by varying the feed ratios of monomer to chain transfer agent (CTA). The exploration of the photocatalytic thiol-ene reaction between HTPB precursor and methyl 3-mercaptopropionate revealed that blue light as well as oxygen accelerated the reaction.

H-NMR and

C-NMR results verified all the double bonds in HTPB can be modified

and the main chain of resultant polymer can be considered as polyethylene. Subsequently

relationship between the structure of side groups and the thermal properties of functional PEs was studied. And the results suggested that the

was in the order of HTPE

butane

HTPE

ester

HTPE

carboxyl

. Greater interaction between side groups resulted in higher

. Moreover

all the functional PE samples exhibited poor thermostability as compared to HTPB. Finally

the promising applications for functional PEs were explored. HTPE

carboxyl

can be utilized as a smart material with pH-responsive properties due to its pH-dependent ionization of carboxyl side groups. HTPE

butane

can be employed as a macro-initiator for building the triblock copolymer due to the presence of active hydroxyl end groups. HTPE

ester

can serve as a plasticizer for PVC which can enhance the ductility of PVC without obviously sacrificing strength.

关键词

Keywords

references

Tellers, J.; Zych, A.; Neuteboom, P.; Soliman, M.; Vachon, J . Polyolefin copolymer PE-HEMA with increased metal adhesion properties . Eur. Polym. J. , 2020 . 131 109721 DOI: 10.1016/j.eurpolymj.2020.109721 http://doi.org/10.1016/j.eurpolymj.2020.109721 .

Báez, J. E.; Ramírez-Hernández, A.; Marcos-Fernández, Á . Synthesis, characterization, and degradation of poly(ethylene- b - ε -caprolactone) diblock copolymer . Polym. Adv. Technol. , 2010 . 21 55 - 64 . .

Lee, H. J.; Baek, J. W.; Kim, T. J.; Park, H. S.; Moon, S. H; Park, K. L.; Bae, S. M.; Park, J.; Lee, B. Y . Synthesis of long-chain branched polyolefins by coordinative chain transfer polymerization . Macromolecules , 2019 . 52 9311 - 9021 . DOI: 10.1021/acs.macromol.9b01705 http://doi.org/10.1021/acs.macromol.9b01705 .

Peng, B.; Jiang, Y.; Zhu, A . A novel modification of carbon nanotubes for improving the electrical and mechanical properties of polyethylene composites . Polym. Test. , 2019 . 74 72 - 76 . DOI: 10.1016/j.polymertesting.2018.12.018 http://doi.org/10.1016/j.polymertesting.2018.12.018 .

Ramírez-Hernández, A.; Hernández-Mota, C. E.; Páramo-Calderón, D. E.; González-García, G.; Báez-García, E.; Rangel-Porras, G.; Vargas-Torres, A.; Aparicio-Saguilán, A . Thermal, morphological and structural characterization of a copolymer of starch and polyethylene . Carbohyd. Res. , 2020 . 488 107907 DOI: 10.1016/j.carres.2020.107907 http://doi.org/10.1016/j.carres.2020.107907 .

Alshumrani, R. A.; Hadjichristidis, N . Well-defined non-linear polyethylene-based macromolecular architectures . J. Polym. Sci. Part A: Polym. Chem. , 2018 . 56 2129 - 2136 . DOI: 10.1002/pola.29173 http://doi.org/10.1002/pola.29173 .

Ntetsikas, K.; Zapsas, G.; Bilalis, P.; Gnanou, Y.; Feng, X. Y.; Thomas, E. L.; Hadjichristidis, N . Complex star architectures of well-defined polyethylene-based Co/terpolymers . Macromolecules , 2020 . 53 4355 - 4365 . DOI: 10.1021/acs.macromol.0c00668 http://doi.org/10.1021/acs.macromol.0c00668 .

Kimani, S. M.; Thompson, R. L.; Hutchings, L. R.; Clarke, N.; Billah, S. M. R.; Sakai, V. G.; Rogers, S. E . Multihydroxyl end functional polyethylenes: synthesis, bulk and interfacial properties of polymer surfactants . Macromolecules , 2014 . 47 2062 - 2071 . DOI: 10.1021/ma402158b http://doi.org/10.1021/ma402158b .

Tian, B. Z.; Cai, Y. Q.; Zhang, X. W.; Fan, H.; Li, B. G . Design of well-defined polyethylene- g -poly-methyltrifluorosiloxane graft copolymers via direct copolymerization of ethylene with polyfluorosiloxane macromonomers . Ind. Eng. Chem. Res. , 2020 . 59 4557 - 4567 . DOI: 10.1021/acs.iecr.0c00029 http://doi.org/10.1021/acs.iecr.0c00029 .

Bergerbit, C.; Baffie, F.; Wolpers, A.; Dugas, P.; Boyron, O.; Taam, M.; Lansalot, M.; Monteil, V.; D'Agosto, F . Ethylene polymerization-induced self-assembly (PISA) of poly(ethylene oxide)-block-polyethylene copolymers via RAFT . Angew. Chem. Int. Ed. , 2020 . 132 10471 - 10476 . DOI: 10.1002/ange.202001741 http://doi.org/10.1002/ange.202001741 .

Han, C. J; Lee, M. S.; Byun, D.; Kim, S. Y . Synthesis of hydroxy-terminated polyethylene via controlled chain transfer reaction and poly(ethylene- b -caprolactone) block copolymer . Macromolecules , 2002 . 35 8923 - 8925 . DOI: 10.1021/ma025565p http://doi.org/10.1021/ma025565p .

Demarteau, J.; Scholten, P. B. V.; Kermagoret, A.; Winter, J. D.; Meier, M. A. R.; Monteil, V.; Debuigne, A.; Detrembleur, C . Functional polyethylene (PE) and PE-based block copolymers by organometallic-mediated radical polymerization . Macromolecules , 2019 . 52 9053 - 9063 . DOI: 10.1021/acs.macromol.9b01741 http://doi.org/10.1021/acs.macromol.9b01741 .

Chen, M.; Chen, C. L . A versatile ligand platform for palladium- and nickel-catalyzed ethylene copolymerization with polar monomers . Angew. Chem. Int. Ed. , 2018 . 130 3148 - 3152 . DOI: 10.1002/ange.201711753 http://doi.org/10.1002/ange.201711753 .

Cui, D. M . Studies on homo- and co-polymerizations of polar and non-polar monomers using rare-earth metal catalysts . Acta Polymerica Sinica (in Chinese) , 2020 . 51 12 - 29 . .

Feng, Y. C.; Jie, S. Y.; Li, B . Synthesis of ethylene/vinyl ester copolymers with pendent linear branches via ring-opening metathesis polymerization of fatty acid-derived cyclooctenes . J. Polym. Sci., Part A: Polym. Chem. , 2017 . 55 2211 - 2220 . DOI: 10.1002/pola.28606 http://doi.org/10.1002/pola.28606 .

Scherman, O. A.; Walker, R.; Grubb, R. H . Synthesis and characterization of stereoregular ethylene-vinyl alcohol copolymers made by ring-opening metathesis polymerization . Macromolecules , 2005 . 38 9009 - 9014 . DOI: 10.1021/ma050686l http://doi.org/10.1021/ma050686l .

Franssen, N. M. G.; Reek, J. N. H.; Bruin, B . Synthesis of functional ‘polyolefins’: state of the art and remaining challenges . Chem. Soc. Rev. , 2013 . 42 5809 - 5832 . DOI: 10.1039/c3cs60032g http://doi.org/10.1039/c3cs60032g .

Rakotonirina, M. D.; Baron, M.; Siri, D.; Gaudel-Siri, A.; Quinebeche, S.; Flat, J.; Gigmes, D.; Cassagnau, P.; Beyou, E.; Guillaneuf, Y . Acyloxyimide derivatives as efficient promoters of polyolefin C–H functionalization: application in the melt grafting of maleic anhydride onto polyethylene . Polym. Chem. , 2019 . 10 4336 - 4345 . DOI: 10.1039/C9PY00672A http://doi.org/10.1039/C9PY00672A .

Hong, M.; Liu, S. R.; Li, B. X.; Li, Y. S . Application of thiol-ene click chemistry to preparation of functional polyethylene with high molecular weight and high polar group content: influence of thiol structure and vinyl type on reactivity . J. Polym. Sci., Part A: Polym. Chem. , 2012 . 50 2499 - 2506 . DOI: 10.1002/pola.26026 http://doi.org/10.1002/pola.26026 .

Hu, H.; You, J.; Gan, W. P.; Zhou, J. P.; Zhang, L . Synthesis of allyl cellulose in NaOH/urea aqueous solutions and its thiol-ene click reactions . Polym. Chem. , 2015 . 6 3543 - 3548 . DOI: 10.1039/C5PY00301F http://doi.org/10.1039/C5PY00301F .

Song, W. Q.; Liu, Y. Y.; Qian, L. W.; Niu, L. Y.; Xiao, L. Q.; Hou, Y.; Wang, Y.; Fan, X. D . Hyperbranched polymeric ionic liquid with imidazolium backbones for highly efficient removal of anionic dyes . Chem. Eng. J. , 2015 . 287 482 - 491 . .

Tyson, E. L.; Ament, M. S.; Yoon, T. P . Transition metal photoredox catalysis of radical thiol-ene reactions . J. Org. Chem. , 2013 . 78 2046 - 2050 . DOI: 10.1021/jo3020825 http://doi.org/10.1021/jo3020825 .

Xu, J. T.; Boyer, C . Visible light photocatalytic thiol–ene reaction: an elegant approach for fast polymer postfunctionalization and step-growth polymerization . Macromolecules, , 2015 . 48 520 - 529 . DOI: 10.1021/ma502460t http://doi.org/10.1021/ma502460t .

Zhu, X. Z.; Fan, X. D.; Zhao, N.; Liu, J.; Min, X.; Wang, Z. Z . Comparative study of structures and properties of HTPBs synthesized via three different polymerization methods . Polym. Test. , 2018 . 68 201 - 207 . DOI: 10.1016/j.polymertesting.2018.04.015 http://doi.org/10.1016/j.polymertesting.2018.04.015 .

Wang, H. T.; Bethea, T. W.; Harwood, H. J . Carbon-13 NMR spectra of isomerized polybutadienes . Macromolecules , 1993 . 26 715 - 720 . DOI: 10.1021/ma00056a024 http://doi.org/10.1021/ma00056a024 .

Wen, J. Q.; Zhang, X. Q.; Dai, Q. Q . Synthesis of polybutadienes with controllable microstructure by a novel binary Nd(3-NBSO 3 ) 3 /alkylaluminum catalyst system . Chinese J. Polym. Sci. , 2015 . 33 475 - 480 . DOI: 10.1007/s10118-015-1600-8 http://doi.org/10.1007/s10118-015-1600-8 .

Silverstein, J. S.; Casey, B. J.; Natoli, M. E.; Dair, B. J.; Kofinas, P . Rapid modular synthesis and processing of thiol-ene functionalized styrene-butadiene block copolymers . Macromolecules , 2012 . 45 3161 - 3167 . DOI: 10.1021/ma300304h http://doi.org/10.1021/ma300304h .

Brummelhuis, N. T.; Diehl, C.; Schlaad, H . Thiol-ene modification of 1,2-polybutadiene using UV light or sunlight . Macromolecules , 2008 . 41 9946 - 9947 . DOI: 10.1021/ma802047w http://doi.org/10.1021/ma802047w .

Zhang, W. B.; Zhang, G. H.; Du, L.; Zhang, C.; Li, L.; Zhu, J. F.; Pei, J.; Wu, J . Synthesis of hydroxyl-terminated polybutadiene bearing pendant carboxyl groups by combination of anionic polymerization and blue light photocatalytic thiol-ene reaction and its pH-triggered self-assemble behavior . React. Funct. Polym. , 2018 . 127 161 - 167 . DOI: 10.1016/j.reactfunctpolym.2018.04.003 http://doi.org/10.1016/j.reactfunctpolym.2018.04.003 .

Liu, D.; Jiang, P. P.; Nie, Z. X.; Wang, H. Y.; Dai, Z. D.; Deng, J. N.; Cao, Z. L . Synthesis of an efficient bio-based plasticizer derived from waste cooking oil and its performance testing in PVC . Polym. Test. , 2020 . 90 106625 DOI: 10.1016/j.polymertesting.2020.106625 http://doi.org/10.1016/j.polymertesting.2020.106625 .

Tyson, E. L.; Niemeyer, Z. L.; Yoon, T. P . Redox mediators in visible light photocatalysis: photocatalytic radical thiol-ene additions . J. Org. Chem. , 2014 . 79 1427 - 1436 . DOI: 10.1021/jo500031g http://doi.org/10.1021/jo500031g .

Passaglia, E.; Coiai, S.; Ciardelli, F.; Galimberti, M.; Passaglia, E . Thiol-ene radical addition of L-cysteine derivatives to low molecular weight polybutadiene . Macromol. Chem. Phys. , 2009 . 210 1471 - 1483 . DOI: 10.1002/macp.200900164 http://doi.org/10.1002/macp.200900164 .

Zhang, W. B.; Fan, X. D.; Tian, W.; Chen, H.; Zhu, X. Z.; Zhang, H. T . Preparation of a P(THF- co -PO)- b -PB- b -P(THF- co -PO) triblock copolymer via cationic ring-opening polymerization and its use as a thermoset polymer . RSC Adv. , 2015 . 5 66073 - 66081 . DOI: 10.1039/C5RA10407F http://doi.org/10.1039/C5RA10407F .

Zhou, Q. Z.; Jie, S. Y.; Li, B. G . Preparation of hydroxyl-terminated polybutadiene with high cis -1,4 content . Ind. Eng. Chem. Res. , 2014 . 53 17884 - 17893 . DOI: 10.1021/ie503652g http://doi.org/10.1021/ie503652g .

Forens, A.; Roos, K.; Dire, C.; Gadenne, B.; Carlotti, S . Anionic polymerization of butadiene using lithium/potassium multi-metallic systems: influence on polymerization control and polybutadiene microstructure . Chinese J. Polym. Sci. , 2019 . 38 357 - 362 . .

Gao, Y. Y.; Hu, F. Y.; Liu, J.; Wang, Z . Moecular dynamics simulation of the glass transition temperature of fullerene filled cis -1,4-polybutadiene nanocomposites . Chinese J. Polym. Sci. , 2018 . 36 119 - 128 . DOI: 10.1007/s10118-018-2015-0 http://doi.org/10.1007/s10118-018-2015-0 .

Zhang, Y.; Zhang, X. M.; Song, Y. C.; Wang, J. H . Enhanced performance of calcium-enriched coal ash for the removal of humic acids from aqueous solution . Fuel , 2015 . 141 93 - 98 . DOI: 10.1016/j.fuel.2014.10.054 http://doi.org/10.1016/j.fuel.2014.10.054 .

Huang, Y. W.; Yan, J. Y.; Peng, S. Y.; Tang, Z. L.; Tan, C. Y.; Ling, J. B.; Lin, W. J.; Lin, X. F.; Zu, X. H.; Yi, G. B . pH/Reduction dual-stimuli-responsive cross-linked micelles based on multi-functional amphiphilic star copolymer: synthesis and controlled anti-cancer drug release . Polymers , 2020 . 12 82 DOI: 10.3390/polym12010082 http://doi.org/10.3390/polym12010082 .

Pereira, V. A.; Fonseca, A. C.; Costa, C. S. M. F.; Ramalho, A.; Coelho, J. F. J.; Serra, A. C . End-capped biobased saturated polyesters as effective plasticizers for PVC . Polym. Test. , 2020 . 85 106406 DOI: 10.1016/j.polymertesting.2020.106406 http://doi.org/10.1016/j.polymertesting.2020.106406 .

Sun, Z. H.; Choi, B.; Feng, A. C.; Moad, G.; Thang, S. H . Nonmigratory poly(vinyl chloride)-block-polycaprolactone plasticizers and compatibilizers prepared by sequential RAFT and ring-opening polymerization (RAFT-T-ROP) . Macromolecules , 2019 . 52 1746 - 1756 . DOI: 10.1021/acs.macromol.8b02146 http://doi.org/10.1021/acs.macromol.8b02146 .

Chen, J.; Wang, Y. G.; Huang, J. R.; Li, K.; Nie, X. A . Synthesis of tung-oil-based triglycidyl ester plasticizer and its effects on poly(vinyl chloride) soft films . ACS Sustain. Chem. Eng. , 2018 . 6 642 - 651 . DOI: 10.1021/acssuschemeng.7b02989 http://doi.org/10.1021/acssuschemeng.7b02989 .

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